CA1340126C - Polycondensation and/or additon product containing carboxyl groups and tertiary amino groups, coating agents based thereon, and the use thereof - Google Patents
Polycondensation and/or additon product containing carboxyl groups and tertiary amino groups, coating agents based thereon, and the use thereofInfo
- Publication number
- CA1340126C CA1340126C CA000545598A CA545598A CA1340126C CA 1340126 C CA1340126 C CA 1340126C CA 000545598 A CA000545598 A CA 000545598A CA 545598 A CA545598 A CA 545598A CA 1340126 C CA1340126 C CA 1340126C
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- CA
- Canada
- Prior art keywords
- component
- acid
- polyester
- amino group
- tertiary amino
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
Abstract
The invention is a coating composition which comprises a polyester containing carboxyl groups and tertiary amino groups, which polyester has an acid number from 5 to 200 and an amino number from 3 to 150, and a crosslinking agent which is an epoxy resin containing on average more than one epoxy group per molecule, the ratio of the number of free carboxyl groups in the polyester to the number of epoxy groups in the epoxy resin being in the range from 1:5 to 5:1. The composition is useful for automobile refinishing of automobile bodies and as a topcoat, filler, varnish, primer or undercoat.
Description
1 3 !~ O 1 2 ~
,, The present invention relates to coating compositions comprising a polyester containing carboxyl groups and tertiary amino groups and the use thereof.
It is known that compounds which contain an epoxy ring react with compounds containing carboxyl groups, with ring opening. When compounds containing more than one epoxy group and more than one carboxyl group are used, the reaction proceeds with formation of polymeric esters which contain secondary hydroxyl groups. Products of this polymer formation are known under the term "acid-curing epoxy resins".
It is known that this epoxy-carboxy reaction can be catalyzed by suitable basic compounds. Suitable basic catalysts are, for example, diazabicyclooctane, diazabicyclononene, diazabicycloundecene, imidazole derivatives, such as 3-methyl-, phenyl- or cyclohexylimidazole, trialkylamines, such as triethyl-, tributyl- or tricyclohexyl-amine, N,N'-dialkylpiperazines, trialkyl- or triaryl-phosphines, hydroxides, carbonates and salts of , - 2 - 13-~126 organic ac;ds of the alkali metals, such as lithium hy-droxide, potassium carbonate, sodium benzoate and lithium benzoate. Further suitable catalysts are chelates of magnesium, aluminum and titanium.
S EP-B-2,284 discloses a reactive, curable polymer mixture based on epoxy compounds and polycarboxylic acid units. By using polycarboxylic acids which are modified vith primary amino groups, polycarboxylic acid units con-taining primary amino groups are obtained. The dis-advantage in this case is the danger of gelling. In order to achieve low curing temperatures and short curing times, external catalysts are necessary.
EP-B-51,275 discloses a reactive, curable binder mixture based on epoxy compounds, polycarboxylic acid units based on poLymerization and/or condensation prod-ucts, and a catalyst component in the form of alkali metal and alkaline-earth metal salts of a polycarboxylic acid unit. The mixtures cure completely at room tempera-ture or at slightly elevated temperature and can be used, in particular, for metal-effect paintwork. In this case, the curing catalyst is incorporated into the binder in the form of an alkali metal salt or an alkaline-earth metal salt. Although an internal catalyst is involved in this case, incompatibility problems may occur.
EP-B-5,868 discloses a water-soluble reactive binder which can be obtained from cyclic polycarboxylic acid compounds, salt-forming substances, such as, for ex-ample organic bases, polymers containing hydroxyl groups, and epoxy compounds. The ind;vidual binder components 13 1~126 can be present ln chemlcally bound form. The mlxtures cure at room temperature, and they are preferably used ln the form of thelr aqueous solutlons. Organic bases, such as, for example, tertlary amlno compounds, cause the water-solublllty of the blnder system. In order to accelerate curlng of the blnder mlxture, an external catalyst must be used, whlch ls assoclated wlth severe problems wlth respect to compatlblllty.
The present lnventlon seeks to provlde a coatlng composltlon based on acld-curlng epoxy reslns, where complete curlng of the coatlng agent should occur at a sufflclently hlgh rate and at the lowest posslble temperatures. The fllms produced should have good or even lmproved propertles ln respect of hardness and elastlclty. It should be posslble to omlt the use of an external catalyst ln order to avold lncompatlblllty problems.
Accordlngly, the present lnventlon provldes a method of reflnlshlng an automoblle body or body part whlch comprlses applylng to the body or body part a coatlng composltlon whlch comprlses a polyester contalnlng carboxyl groups and tertlary amlno groups, whlch polyester has an acld number from 5 to 200 and an amlno number from 3 to 150, and a crossllnklng agent whlch ls an epoxy resln contalnlng on average more than one epoxy group per molecule, the ratlo of the number of free carboxyl groups ln the polyester to the number of epoxy groups ln the epoxy resln belng ln the range from 1:5 to 5:1 whereln the polyester ls the product of reactlon between a polycarboxyllc acld or anhydrlde component D
13~0126 a), and a polyol component b) and one or both of the components a) and b) contalns tertlary amlno groups.
A polyester has an acld number from 5 to 200, preferably lO to 130, and an amlne number from 3 to 150, preferably lO to lO0.
Sultable polycarboxyllc aclds (component a) are, for example, phthallc acld, lnsophthallc acld, terephthallc acld, halophthallc aclds, such as tetrachloro or tetrabromophthallc acld, hexahydrophthallc acld, adlplc acld, sebaclc acld, fumarlc acld, malelc acld, endomethylenetetrahydrophthallc acld, trlmellltlc acld, and anhydrldes of the aclds mentloned, where these exlst.
Monocarboxyllc aclds, such as, for example, benzolc acld, tert.-butylbenzolc acld, laurlc acld, lsononanolc acld, and fatty aclds of naturally occurrlng olls, may also be employed, lf approprlate, together wlth the polycarboxyllc aclds.
Sultable alcohol components b) are polyhydrlc alcohols, such as ethylene glycol, propanedlols, butanedlols, pentanedlols, hexanedlols, neopentyl glycol, dlethylene glycol, cyclohexanedlmethanol, trlmethylpentanedlol, dltrlmethylolpropane, trlmethylolethane, trlmethylolpropane, glycerol; pentaerythrltol, dlpentaerythrltol, trlshydroxyethyl lsocyanurate, polyethylene glycol and polypropylene glycol, lf approprlate together wlth monohydrlc alcohols, such as, for example, butanol, octanol, lauryl alcohol or ethoxylated or propoxylated phenols.
As component a) (carboxyllc acld compound), amlnocarboxyllc aclds contalnlng at least one tertlary amlno group may be used lnter alla or excluslvely.
- 4a -~ 5 ~ 13401~5 Examples of these are: pyridine-2-carboxylic acid, pyridine-3-carboxylic acid, pyridine-4-carboxylic acld, dimethylaminobenzoic acid and pyridine-2,6-dicarboxyLic acid. In this case, nicotinic acid, i.e. pyridine-3-carboxylic acid, is preferably used, since this is a veryreactive aminocarboxylic acid with respect to catalyzing the acid/epoxy reaction.
As component a), the product of the reaction of an amino alcohol containing at least one ter!;iary amino group with a polycarboxylic anhydride can advantageously be used. The product of the reaction of 2-hydroxyethyl-pyridine with phthalic anhydride may be mentioned as an example of such a reaction product.
As component a), the product of the reaction of a polyamine containing at least one tertiary and at least one primary or secondary amino group with a poly-carboxylic anhydride is preferably used.
As the alcohol component b), amino alcohols con-taining at least one tertiary amino group may be used inter alia or, alternatively, exclusively. Examples of such amino alcohols which may be mentioned are 2-hydroxyethylpyridine and dimethylaminopropanol. As the alcohol component b), products of the reaction of epoxy resins with carboxylic acids and/or amines are preferably employed.
As the modifying component c), polyisocyanates and/or diepoxide compounds, if appropriate also mono-isocyanates and/or monoepoxide compounds, are preferably used. Suitable polyisocyanates are, for example, the 1~ 40120 toluylene diisocyanates, hexamethylene diisocyanate and isophorone diisocyanate. Diepoxide compounds are taken to mean epoxy resins containing on average about two epoxide groups per molecule.
Suitable monoepoxide compounds are, for example, olefin oxides, such as octylene oxide, butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, styryl oxide, glycidyl methacrylate, vinylcyclo-hexene monoxide, dipentene monoxide, a-pinene oxide and glycidyl esters of tertiary carboxylic acids.
It is particularly advantageous when, as the alcohol component b~, the product of the reaction of low-molecular-weight epoxy resins with polycarboxylic acids and/or polycarboxylic anhydrides and aminocarboxylic acids containing at least one tertiary amino group and/or polyamines containing at least one tertiary and at least one primary or secondary amino group is used, esterification subsequently being carried out, if appropriate, with the acid and the alcohol component and modification, if appropriate, with polyisocyanates. Low-molecular-weight epoxy resins are taken to mean epoxy resins having a molecular weight of below about 2000.
Component c) can lnclude monoisocyanates containing at least one tertiary amino group. These can be prepared, for example, by reacting suitable diisocyanates, such as isophorone diisocyanate, with aminoalcohols containing a tertiary amino group, such as, for example, hydroxyethylpyridine or dimethyl-aminoethanol, or with polyamines containing at least one tertiary and at least one secondary or primary amino group. The monoiso-cyanates are bound to the binder system by reaction with freehydroxyl groups of the polycondensation and/or additlon product, with formation of a urethane bond.
Polyamines containing at least one tertiary and at least one primary or secondary amino group are also advantageously used.
Dimethylaminopropylmethylamine may be mentioned as an example of such polyamines.
As the alcohol component, the product of the ring-opening of epoxy resins using hydrogen-active compounds can also preferably be used. Thus, for example, diepoxides, such as the known Epikote* types, can firstly be reacted in steps with dicarboxylic acids, such as, for example, pyridine-2,6-dicarboxylic acid, to form a precursor, which is then further employed as the alcohol component.
It is in any case essential to the invention that the final product obtained has an acid number in the range from 5 to 200 and an amine number in the range from 3 to 150.
It is preferred to use a polyester obtainable from a) one or more polycarboxylic acids or anhydrides thereof, ~0 if appropriate together with one or more monocarboxylic acids, b) one or more polyols, if appropriate together with one or more monools, components a) and/or b) containing ethylenically unsaturated double bonds, if appropriate further modifying components, and one or more mercapto compound containing at least one *Trade Mark 1~012~
tertiary amino group, with the proviso that the product contains tertlary amino groups which originate essentially or entirely from the mercapto compound. As component a) in this case, maleic anhydride or unsaturated fatty acids, for example, are used; an unsaturated alcohol which is suitable as component b) is, for example, 1,4-butenediol. In this case, the mercapto groups of the aminomercaptan containing a tertiary amino group add to the double bonds which are introduced into the binder by means of component a) and/or b).
The polyesters used in the coating composition according to the invention are preferably obtainable by reacting a rela-tively high-molecular-weight epoxy resin containing on average at least three epoxy groups per molecule with a polycarboxylic acid and/or polycarboxylic anhydride and with an aminocarboxylic acid containing at least one tertiary amino group and/or polyamine containing at least one tertiary and at least one primary or secondary amino group. As relatively high-molecular-weight epoxy resins containing on average at least three epoxy groups per molecule, epoxidized novolaks can be employed, for example. These are formed by reacting novolaks with epichlorohydrin.
The polyester used in the coating composition of the invention can be obtained by a process wherein the reaction of a) one or more polycarboxylic acids or anhydrides thereof, if appropriate together with one or more monocarboxylic acids, b) one or more polyols, if appropriate together with one or more monools, and, if appropriate, 134012~
c) one or more further modifying components capable of reacting with the reaction product from a), and b) is carried out simultaneously or stepwise by means of esterification and/or transesterification and/or addition reactions, with the proviso that the final product contains tertiary amino groups which originate from component a) and/or b) and/or c), and the reaction product from a), b), if appropriate c) has an acid number from 5 to 200, preferably 10 to 130, and an amine number from 3 to 150, preferably 10 to 100.
Suitable compounds of component a) are phthalic acid, isophthalic acid, terephthalic acid, halophthalic acids, such as tetrachloro- or tetrabromophthalic acid,. hexahydrophthalic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, endo-methylenetetrahydrophthalic acid, trimellitic acid, and anhydrides of the acids mentioned, if these exist. Suitable monocarboxylic acids which can be employed together with the polycarboxylic acids are, for example, benzoic acid, tert.-butylbenzoic acid, lauric acid, isononanoic acid and fatty acids of naturally occurring oils.
Suitable alcohol components b) are polyhydric alcohols, such as ethylene glycol, propanediols, butane-diols, pentanediols, hexanediols, neopentyl glycol, di-ethylene glycol, cyclohexanedimethanol, trimethylpentane-diol, ditrimethylolproPane~ trimethylolethane, trimethylol-propane, glycerol, pentaerythritol, dipentaerythritol ortrishydroxyethyl isocyanurate, if appropriate together with monohydric alcohols, such as, for example, butanol, octanol, lauryl alcohol and ethoxylated or propoxylated phenols.
As the carboxylic acid component a), amino-carboxylic acids contain;ng at least one tertiary amino group can be used, inter alia or exclusively. In this case, pyridine-3-carboxylic acid, i.e. nicotinic acid, is preferably used. The product of the reaction of an amino-alcohol containing at least one tertiary amino group with a polycarboxylic anhydride is also suitable as the car-boxylic acid component a). The product of the reaction of 2-hydroxyethylpyridine with phthalic anhydride may be mentioned as an example of such products.
It is particularly advantageous when the acid component used is the product of the reaction of a poly-amine containing at least one tertiary and at least one primary or secondary amino group with a polycarboxylic anhydride.
The tertiary amino group can also be introduced into the binder through the alcohol component b), for example. In this case, an aminoalcohol containing at least one tertiary amino group is employed as component b). Examples of amino alcohols containing at least one 1~4012~
tertiary amino group are 2-hydroxyethylpyridlne and dimethylamino-propanol.
According to the process according to the invention, a product of the reaction of epoxy resins with carboxylic acids and/or amines can be used as the alcohol component b).
It is preferred when polyisocyanates and/or diepoxide compounds, if appropriate also monoisocyanates and/or monoepoxide compounds, are employed as the modifying component c).
A preferred embodiment of the process according to the invention comprises using the product of the reaction of low-molecular weight epoxy resins with polycarboxylic acids and/or polycarboxylic anhydrides and aminocarboxylic acids containing at least one tertiary amino group and/or polyamines containing at least one tertiary and at least one primary or secondary amino group as component b), esterification subsequently being carried out, if appropriate, with components a) and b) and modification, if appropriate, with polyisocyanates.
When epoxy resins are used, low-chlorine types should be employed since, otherwise, strong discolouration of the products can occur.
As an alternative component c), a monoisocyanate containing at least one tertiary amino group is preferably used.
This can be prepared, for example, by reacting diisocyanates, such as, for example, isophorone diisocyanate, with aminoalcohols containing a tertiary amino group, such as, for example, hydroxy-ethylpyridine or dimethylaminoethanol, or with polyamines contain-ing at least one tertiary and at least one secondary or primary 13~012~
amino group. This component c) is bound to the binder system through reaction with free hydroxyl groups of the product formed previously, with formation of a urethane bond.
It is particularly advantageous when, as component c), a polyamine containing at least one tertiary and at least one primary or secondary amino group is used. An example of such a polyamine is dimethylaminopropylmethylamine.
A preferred embodiment of the process according to the invention comprises reacting a) one or more polycarboxylic acids or anhydrides thereof, if appropriate together with one or more monocarboxylic acids, b) one or more polyols, if appropriate together with one or more monools, components a) and/or b) containing ethylenic double bonds, and, if appropriate, c) further modifying components, including one or more mercapto compounds containing at least one tertiary amino group, with the proviso that the product contains tertiary amino groups which originate essentially or entirely from the mercapto compounds.
In this case, the SH group of the mercapto compound adds to the ethylenically unsaturated double bonds which originate from components a) and~or b). Examples of polycarboxylic acids or anhydrides thereof or monocarboxylic acids containing ethylenically unsaturated double bonds are maleic anhydride and ethylenically unsaturated fatty acids.
An example of a polyol component containing a polymeriz-able double bond is 1,4-butenediol.
, .~
134012~
A preferred process for the preparation of polyesters containing carboxyl groups and tertiary amino groups comprises reacting relatively high-molecular-weight epoxy resins containing on average at least three epoxy groups per molecule with polycarboxylic acids and/or polycarboxylic anhydrides and with an aminocarboxylic acid containing at least one tertiary amino group and/or polyamines containing at least one tertiary and at least one primary or secondary amino group.
The epoxy resins employed in this process are advan-tageously epoxidized novolaks.
If the tertiary amino group is to be introduced into thebinder system malnly or entirely through component c), a preferred embodiment of the process according to the invention comprises initially preparing a reaction product having an acid number of 5 to 200, preferably 10 to 130, by reaction of components a) and b), the reaction product subsequently being further reacted with component c) until the desired amine number is achieved.
A further preferred process variant comprises condensing or adding, in a first stage, components a), b) and, if approp-riate, c) to form a product having an acid number of 1 to 50,preferably 5 to 20, and further reacting this product, in a second stage, with polycarboxylic anhydrides until an acid number of 5 to 200, preferably 10 to 130, is produced.
Excessive discolouration of the products during the con-densation is avoided by adding antioxidants or reducing agents, such as, for example, hypophosphorous acid.
The coating composition of the present invention can 13~012~
also contain organic solvents, conventional additives and auxiliaries, if appropriate pigments, together with the polyester, prepared by the process described above, and, as crosslinking agent, an epoxy resin containing on average more than one epoxy group per molecule, the ratio of the free carboxyl groups in the polycondensation and/or addition product to the number of epoxy groups in the epoxy resin being in the range from 1:5 to 5:1.
Examples of suitable epoxy resins are products of the condensation of epichlorohydrin and bisphenol A, for example cycloaliphatic bisepoxides, epoxidized polybutadienes, which are produced by reacting commercially available polybutadiene oils with peracids or organic acid/H2O2 mixtures, epoxidation products of naturally occurring fats, oils, fatty acid derivatives, modified oils, novolaks containing epoxy groups, glycidyl ethers of a polyhydric alcohol, for example ethylene glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, trimethylol-propane polyglycidyl ether and pentaerythritol polyglycidyl ether, and suitable acrylate resins containing oxirane side groups.
Furthermore, the crosslinking agents can advantageously also be products of the reaction of polyepoxides containing hydroxyl groups with di- or polyisocyanates, as are produced, for example, by reacting OH-functional epoxides, such as, for example, sorbitol polyglycidyl ethers, with isophorone diisocyanate.
Suitable solvents are, for example, toluene, xylene, butanol, ethyl acetate, butyl acetate, pentyl acetate, dimethyl glutarate, dimethyl succinate, 1-methoxy-2 propyl acetate, 2-ethylhexanol, ethylene glycol diacetate, ethylene glycol monoethyl . ~
134012~
and monobutyl ether or the acetates thereof, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, naphthas containing aromatics, cyclohexanone, methyl ethyl ketone, acetone, butyl acetoxyglycolate and ethyl acetoxyglycolate. Suitable additives and auxiliaries are, for example, fillers, such as, for example, talcum, mica, kaolin, chalk, quartz sand, asbesto~
powder, barium sulfate, silicates, glass fibers, sedimentation inhibitors such as, for example, finely divided silica, bentonite, colloidal silicates and the like.
10The present invention also relates to a process for the preparation of the abovementioned coating agents, wherein the polyester, prepared by the process described above, the epoxy resin containing on average more than one epoxy group per molecule, and organic solvents, conventional additives and ~ auxiliaries and, if appropriate, pigments are processed by mixing and, if appropriate, dispersing to form a coating composition, the ratio of the free carboxyl groups in the polyester to the number of epoxy groups in the epoxy resin being in the range 1:5 to 5~1.
The coating agents according to the invention can be applied to a very wide variety of substrates. Suitable substrates are, for example, metals, such as iron, zinc, titanium, copper, aluminum, steel, brass, bronze, magnesium or the like, and furthermore ceramics, wood, glass, concrete and plastics.
The coating agents according to the invention cure at relatively low temperature, i.e. at room temperature or at slightly elevated temperatures. The low curing temperature and the short curing time can be attributed to the presence of an 13 iO126 internal catalyst in the binder system. If short curing times and low curing temperatures are desired, a polyester product having a relatively high amine number is employed.
By suitable choice of the alcohol component, the acid component and the modifying components, the properties of the final product in respect of hardness, elasticity and reactivity can be controlled in an excellent fashion.
Aromatic acid components lead to products having relatively great hardness, whereas cycloaliphatic or aliphatic acid components lead to relatively elastic films.
By using suitable monocarboxylic acids, the hardness and elasticity can likewise be influenced.
Relatively hard films are obtained when benzoic acid is used, whereas essentially softer films are obtained when fatty acids are used. The use of hexanediols as the al-cohol components leads to elastic films, whereas, in con-trast, the use of neopentyl glycol and pentaerythritolleads to relatively hard coatings.
Aromatic tertiary amino groups in the binder sys-tem have a higher catalytic activity than aliphatic or araliphatic amino groups.
Due to the low curing temperatures and the short curing times, the coating àgents according to the in-vention are preferably used for automobile refinishing.
In addition, they are highly suitable as top coats, fillers, varnishes, primers or undercoats.
The choice of the epoxy resin depends on the intended use. When used as a top coat, aliphatic epoxy resins are preferably used, and aromatic epoxy resins are also suitable for undercoats.
The problem of discoloration which may occur on use as a varnish can be avoided by incorporating prefer-ably aliphatic tertiary amino groups into the binder sys-tem. In the case of varnishes, low-chlorine or chlorine-free epoxy resins should be employed; discoloration phenomena do not then occur.
The films obtained from the binders or coating agents according to the invention have excellent proper-ties in respect of hardness, elasticity and reactivity.
A further advantage is that the use of an external cata-lyst can be omitted.
- 18 - 134012~
If curing is to be carried out under baking con-ditions, i.e. at temperatures of at least 100~C, the coating agent according to the invention can additionally contain a heat-curable ether- and/or amino- and/or OH
group-containing synthetic resin, such as, for example, phenol or amino resins.
The invention is illustrated in greater detail below with reference to illustrative embodiments. Parts denote parts by weight, unless otherwise stated.
Example 1:
Preparation of polyester resin I
1110.7 parts of phthalic anhydride, 742.1 parts of trimethylol propane, 187.2 parts of pyridine-3-carboxylic acid and 139.2-parts of 2-ethylhexanoic acid are heated slowly, with addition of 87 parts of xylene as entrainer, in a 4 liter polycondensation kettle equipped with stirrer and water separator, and the condensation reaction is carried out at 200-205~C to an acid number of about 70. After cooling and partially dissolving with 420 parts of xylene, 420 parts of methoxypropanol and 420 parts of butyl acetate (98/100), a solution of the acidic polyester having an acid number of 66, a viscosity (original) of 27 dPa.s and a solids content of 60 % is obtained.
Example 2:
Preparation of polyester -resin II
880 parts of phthalic anhydride, 247.2 parts of tri-methylhexanoic acid, 192.5 parts of pyridine-3-carboxylic acid and 838.7 parts of trimethylolpropane are heated - 19 - 134012~
slowly to 205~C, w;th addition of 86 parts of xylene as entrainer and 0.648 parts of hypophosphorous acid, in a polycondensation kettle equipped with stirrer and water separator, and the condensation reaction is car-ried out to 205-210~C to an acid number of about 12.
The mixture is then cooled to 130~C and partly dis-solved with 396 parts of xylene. 325 parts of phthalic anhydride are subsequently added, and the addition reaction with the hydroxyl groups of the polyester is carried out at 130~C. When the addition reaction is complete, the reaction mixture is partially dissolved with 281 parts of xylene and 763 parts of butanol.
The resin solution thus obtained has a solids content of 63 %, an acid number of 64 and a viscosity of 27 dPa.s (original).
Example 3:
Preparation of polyester resin III
493 parts of isophthalic acid, 440 of phthalic anhydride, 247.2 parts of trimethylhexanoic acid, 192.5 parts of pyridine-3-carboxylic acid and 838.7 parts of trimethylolpropane are heated slowly to about 200~C, with addition of 88 parts of xylene as entrainer and 0.6634 parts of hypophosphorous acid, in a poly-condensation kettle, and the condensation reaction is carried out at 200-210~C to an acid number of 20. The mixture is cooled to 130~C and partially dissolved with 532 parts of xylene. 450 parts of phthalic anhydride are than added, and the addition reaction with the polyester is carried out at 130~C. After addition of 376 parts of . .
- zo - 13~012~
xylene and 995 parts of butanol, the polyester solution obtained has a solids content of 59 %, an acid number of 88.5 and a viscosity of 11 dPa.s (original).
Example 4:
Preparation of polyester resin IV
315.6 parts of phthalic anhydride and 131.1 parts of 2-hydroxyethylpyridine are kept at 140-150~C for 4 hours in a polycondensation kettle, and, at 140~C, 409.4 parts of trimellitic anhydride, 310.5 parts of neopentyl glycol, 285.7 parts of trimethylolpropane, 130.1 parts of benzoic acid and 168.5 of trimethylhexanoic acid and 0.525 parts of hypophosphorous acid and, as entrainer, 70 parts of xylene are then added. The mixture is heated to 175~C and the condensation reaction is carried out to an acid number of about 84. After cooling and partially dissolving with 557 parts of xylene and 557 parts of butanol, a polyester solu-tion having a solids content of 57 %, acid number of 84 and a viscosity (original) of 21 dPa.s is obtained.
Example 5:
Preparation of polyester resin V
443.5 parts of isophthalic acid, 411.4 parts of hexahydrophthalic acid, 105.5 parts of isononanoic acid, 333 parts of para-tert.butylbenzoic acid, 304.8 parts of 4-(N,N-dimethylamino)-benzoic acid, 537 parts of tri-methylolpropane, 263.4 parts of pentaerythritol and0.959 parts of hypophosphorous acid, and also 96 parts of xylene as entrainer, are heated slowly to 195~C in a polycondensation kettle, and the condensation reaction is carried out at 195-205~C to an acid number of 15. The z 13~01~6 mixture is subsequently cooled and partially d;ssolved with 305 parts of xylene. 169.4 parts of hexahydro-phthalic acid and 116 parts of xylene are added to 1172 parts of this resin solution, and the addition reaction S between the anhydride and the polyester is carried out at 140~C. After partially dissolving with 390 parts of xylene and 98 parts of butanol, a resin solution having a solids content of 61 %, an acid number of 68 and a vis-cosity (original) of 26.5 dPa.s is obtained. (The viscosity of a solution diluted with xylene to a solids content of S0 % is 4.3 dPa.s.) Example 6:
Preparation of polyester resin VI
230 parts of pyridine-3-carboxylic acid, 333 parts of 4-tert.-butylbenzoic acid, 105.5 parts of iso-nonanoic acid, 443.5 parts of isophthalic acid, 411.4 parts of hexahydrophthalic acid, 537 parts of trimethyl-propane, 263.4 parts of pentaerythritol, 0.93 parts of hypophosphorous acid, and 93 parts of xylene as entrainer are heated slowly to 220~C in a polycondensation ket-tle, and the condensation reaction is carried out to an acid number of 20.2. After cooling and partially dis-soLving w;th 1-methoxy-2-propyl acetate, 444 parts of trimellitic anhydride are added. The mixture is kept at 140~C until an acid number (alcoholic) of 126 is reached.
290 parts of a glycidyl ester of a C10-~,~' alkylalkane-A carboxylic acid (e.g. Cardura E 10) are added to 1800parts of this polyester solution, and the mixture is kept at 85-90~C until an acid number of 65 is reached.
- ~ - 22 ~ I3 ~0 12 Addition of 150 parts of xylene, 150 parts of 1-methoxy-2-propyl acetate and 750 parts of methoxy-propanol leads to a carboxyl group-containing polyester solution having a solids content of 50.5 ~, an acid num-ber of 69 and a viscosity of 19 dPa.s.
Example 7:
Preparation of polyester resin VII
518.2 parts of isophthalic acid, 481 parts of hexahydrophthalic acid, 627.5 parts of trimethylol-propane, 324.7 parts of neopentyl glycol, Z49.6 parts ofpyridine-3-carboxylic acid, 1.1 parts of t;n(II) octoate and 88 parts of xylene as entrainer are heated slowly to 200~C in a polycondensation kettle, and the condensation reaction is carried out at 200-210~C to an acid number of t1. The mixture is then cooled to 140~C, and the addi-tion reaction with 369.6 parts of hexahydrophthalic acid is carried out at 140~C until an acid number of 73.5 is reached. The mixture is partially dissolved with 500 parts of 1-methoxy-2-propyl acetate and 423 parts of xylene. 1240 parts of this polyester solution are heated to 120~C, and 80.3 parts of iso-phorone diisocyanate are added within 30 minutes at 120~C. The mixture is partial-ly dissolved with 580 parts of methoxypropanol, and the resin solution obtained has a solids content of 55 ~, an acid number of 58 and a viscosity of 25 dPa.s (original).
Example 8:
Preparation of polyester resin VIII
469.2 parts of phthalic anhydride, 263.1 parts of isophthalic acid, 456.7 parts of trimethylolpropane, - 23 - 13'1012~
538.9 parts of epoxy resin (based on bisphenol A, epoxy equivalent weight 190), 187.8 parts of isononanoic acid, 175.5 parts of pyridine-3-carboxylic acid, 0.627 parts of hypophosphorous acid and 84 parts of xylene as entrainer are heated slowly to 200~C in a polycondensation kettle, and the condensation reaction is carried out to an acid number of 45. After cooling to 130~C, 390 parts of xylene and 247 parts of phthalic anhydride are added.
The temperature is kept at 130~C until an acid number of 87 is reached. The mixture is then partially dis-solved with 234 parts of xylene and 708 parts of butanol.
The carboxyl group-containing polyester resin solution has an acid number of 86, a solids content of 62 Z and a viscosity (diluted with xylene to 50 %) of 5.2 dPa.s.
The polyester solutions from examples I to VIII
are mixed with various epoxy resins. The mixtures formed from polyester solutions I, II, III, IV, V, VI and VIII
are adjusted to a solids content of 55 % using xylene, but, in contrast, the mixture made from polyester resin VII is adjusted to a solids content of 50 %. The mixtures are knife-coated onto glass sheets (200 ~m wet film).
The film is cured either at room temperature only or at room temperature after drying for 30 minutes at 60~C.
Crosslinking takes place with epoxy resins A, B or C.
A: Aromatic epoxy resin based on bisphenol A, epoxy equivalent weight 450.
B: Aromatic epoxy resin based on the glycidyl ether of a novolak, epoxy equivalent weight 178.
C: Aliphatic epoxy resin based on a polyglycidyl ether - 24 - 134012~
of a polyol ~sorbitol), epoxy equivalent weight 180.
.
- 25 - I3l10I2 Example Polyester Epoxy Mixing ratio Drying resin resin solidtsolid conditions a I A 64/36 30 min/60~C
b IV P 79/21 30 min/60~C
c V ~ 82/18 30 min/60~C
d VII ~ 85/15 30 min/60~C
e VI C 80/20 RT
f III C 74/26 RT
g II C 81/19 RT
h VIII 9 79/21 RT
Example Pendulum hardness Double wipes with methyl after 6 daysethyl ketone after 6 days (sec~
a 162 160 b 81 120 c 94 30 d 137 200 e 84 200 f 203 145 h (8 days) 150 200 g after Z days after 2 days h after 3 days after 3 days
,, The present invention relates to coating compositions comprising a polyester containing carboxyl groups and tertiary amino groups and the use thereof.
It is known that compounds which contain an epoxy ring react with compounds containing carboxyl groups, with ring opening. When compounds containing more than one epoxy group and more than one carboxyl group are used, the reaction proceeds with formation of polymeric esters which contain secondary hydroxyl groups. Products of this polymer formation are known under the term "acid-curing epoxy resins".
It is known that this epoxy-carboxy reaction can be catalyzed by suitable basic compounds. Suitable basic catalysts are, for example, diazabicyclooctane, diazabicyclononene, diazabicycloundecene, imidazole derivatives, such as 3-methyl-, phenyl- or cyclohexylimidazole, trialkylamines, such as triethyl-, tributyl- or tricyclohexyl-amine, N,N'-dialkylpiperazines, trialkyl- or triaryl-phosphines, hydroxides, carbonates and salts of , - 2 - 13-~126 organic ac;ds of the alkali metals, such as lithium hy-droxide, potassium carbonate, sodium benzoate and lithium benzoate. Further suitable catalysts are chelates of magnesium, aluminum and titanium.
S EP-B-2,284 discloses a reactive, curable polymer mixture based on epoxy compounds and polycarboxylic acid units. By using polycarboxylic acids which are modified vith primary amino groups, polycarboxylic acid units con-taining primary amino groups are obtained. The dis-advantage in this case is the danger of gelling. In order to achieve low curing temperatures and short curing times, external catalysts are necessary.
EP-B-51,275 discloses a reactive, curable binder mixture based on epoxy compounds, polycarboxylic acid units based on poLymerization and/or condensation prod-ucts, and a catalyst component in the form of alkali metal and alkaline-earth metal salts of a polycarboxylic acid unit. The mixtures cure completely at room tempera-ture or at slightly elevated temperature and can be used, in particular, for metal-effect paintwork. In this case, the curing catalyst is incorporated into the binder in the form of an alkali metal salt or an alkaline-earth metal salt. Although an internal catalyst is involved in this case, incompatibility problems may occur.
EP-B-5,868 discloses a water-soluble reactive binder which can be obtained from cyclic polycarboxylic acid compounds, salt-forming substances, such as, for ex-ample organic bases, polymers containing hydroxyl groups, and epoxy compounds. The ind;vidual binder components 13 1~126 can be present ln chemlcally bound form. The mlxtures cure at room temperature, and they are preferably used ln the form of thelr aqueous solutlons. Organic bases, such as, for example, tertlary amlno compounds, cause the water-solublllty of the blnder system. In order to accelerate curlng of the blnder mlxture, an external catalyst must be used, whlch ls assoclated wlth severe problems wlth respect to compatlblllty.
The present lnventlon seeks to provlde a coatlng composltlon based on acld-curlng epoxy reslns, where complete curlng of the coatlng agent should occur at a sufflclently hlgh rate and at the lowest posslble temperatures. The fllms produced should have good or even lmproved propertles ln respect of hardness and elastlclty. It should be posslble to omlt the use of an external catalyst ln order to avold lncompatlblllty problems.
Accordlngly, the present lnventlon provldes a method of reflnlshlng an automoblle body or body part whlch comprlses applylng to the body or body part a coatlng composltlon whlch comprlses a polyester contalnlng carboxyl groups and tertlary amlno groups, whlch polyester has an acld number from 5 to 200 and an amlno number from 3 to 150, and a crossllnklng agent whlch ls an epoxy resln contalnlng on average more than one epoxy group per molecule, the ratlo of the number of free carboxyl groups ln the polyester to the number of epoxy groups ln the epoxy resln belng ln the range from 1:5 to 5:1 whereln the polyester ls the product of reactlon between a polycarboxyllc acld or anhydrlde component D
13~0126 a), and a polyol component b) and one or both of the components a) and b) contalns tertlary amlno groups.
A polyester has an acld number from 5 to 200, preferably lO to 130, and an amlne number from 3 to 150, preferably lO to lO0.
Sultable polycarboxyllc aclds (component a) are, for example, phthallc acld, lnsophthallc acld, terephthallc acld, halophthallc aclds, such as tetrachloro or tetrabromophthallc acld, hexahydrophthallc acld, adlplc acld, sebaclc acld, fumarlc acld, malelc acld, endomethylenetetrahydrophthallc acld, trlmellltlc acld, and anhydrldes of the aclds mentloned, where these exlst.
Monocarboxyllc aclds, such as, for example, benzolc acld, tert.-butylbenzolc acld, laurlc acld, lsononanolc acld, and fatty aclds of naturally occurrlng olls, may also be employed, lf approprlate, together wlth the polycarboxyllc aclds.
Sultable alcohol components b) are polyhydrlc alcohols, such as ethylene glycol, propanedlols, butanedlols, pentanedlols, hexanedlols, neopentyl glycol, dlethylene glycol, cyclohexanedlmethanol, trlmethylpentanedlol, dltrlmethylolpropane, trlmethylolethane, trlmethylolpropane, glycerol; pentaerythrltol, dlpentaerythrltol, trlshydroxyethyl lsocyanurate, polyethylene glycol and polypropylene glycol, lf approprlate together wlth monohydrlc alcohols, such as, for example, butanol, octanol, lauryl alcohol or ethoxylated or propoxylated phenols.
As component a) (carboxyllc acld compound), amlnocarboxyllc aclds contalnlng at least one tertlary amlno group may be used lnter alla or excluslvely.
- 4a -~ 5 ~ 13401~5 Examples of these are: pyridine-2-carboxylic acid, pyridine-3-carboxylic acid, pyridine-4-carboxylic acld, dimethylaminobenzoic acid and pyridine-2,6-dicarboxyLic acid. In this case, nicotinic acid, i.e. pyridine-3-carboxylic acid, is preferably used, since this is a veryreactive aminocarboxylic acid with respect to catalyzing the acid/epoxy reaction.
As component a), the product of the reaction of an amino alcohol containing at least one ter!;iary amino group with a polycarboxylic anhydride can advantageously be used. The product of the reaction of 2-hydroxyethyl-pyridine with phthalic anhydride may be mentioned as an example of such a reaction product.
As component a), the product of the reaction of a polyamine containing at least one tertiary and at least one primary or secondary amino group with a poly-carboxylic anhydride is preferably used.
As the alcohol component b), amino alcohols con-taining at least one tertiary amino group may be used inter alia or, alternatively, exclusively. Examples of such amino alcohols which may be mentioned are 2-hydroxyethylpyridine and dimethylaminopropanol. As the alcohol component b), products of the reaction of epoxy resins with carboxylic acids and/or amines are preferably employed.
As the modifying component c), polyisocyanates and/or diepoxide compounds, if appropriate also mono-isocyanates and/or monoepoxide compounds, are preferably used. Suitable polyisocyanates are, for example, the 1~ 40120 toluylene diisocyanates, hexamethylene diisocyanate and isophorone diisocyanate. Diepoxide compounds are taken to mean epoxy resins containing on average about two epoxide groups per molecule.
Suitable monoepoxide compounds are, for example, olefin oxides, such as octylene oxide, butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, styryl oxide, glycidyl methacrylate, vinylcyclo-hexene monoxide, dipentene monoxide, a-pinene oxide and glycidyl esters of tertiary carboxylic acids.
It is particularly advantageous when, as the alcohol component b~, the product of the reaction of low-molecular-weight epoxy resins with polycarboxylic acids and/or polycarboxylic anhydrides and aminocarboxylic acids containing at least one tertiary amino group and/or polyamines containing at least one tertiary and at least one primary or secondary amino group is used, esterification subsequently being carried out, if appropriate, with the acid and the alcohol component and modification, if appropriate, with polyisocyanates. Low-molecular-weight epoxy resins are taken to mean epoxy resins having a molecular weight of below about 2000.
Component c) can lnclude monoisocyanates containing at least one tertiary amino group. These can be prepared, for example, by reacting suitable diisocyanates, such as isophorone diisocyanate, with aminoalcohols containing a tertiary amino group, such as, for example, hydroxyethylpyridine or dimethyl-aminoethanol, or with polyamines containing at least one tertiary and at least one secondary or primary amino group. The monoiso-cyanates are bound to the binder system by reaction with freehydroxyl groups of the polycondensation and/or additlon product, with formation of a urethane bond.
Polyamines containing at least one tertiary and at least one primary or secondary amino group are also advantageously used.
Dimethylaminopropylmethylamine may be mentioned as an example of such polyamines.
As the alcohol component, the product of the ring-opening of epoxy resins using hydrogen-active compounds can also preferably be used. Thus, for example, diepoxides, such as the known Epikote* types, can firstly be reacted in steps with dicarboxylic acids, such as, for example, pyridine-2,6-dicarboxylic acid, to form a precursor, which is then further employed as the alcohol component.
It is in any case essential to the invention that the final product obtained has an acid number in the range from 5 to 200 and an amine number in the range from 3 to 150.
It is preferred to use a polyester obtainable from a) one or more polycarboxylic acids or anhydrides thereof, ~0 if appropriate together with one or more monocarboxylic acids, b) one or more polyols, if appropriate together with one or more monools, components a) and/or b) containing ethylenically unsaturated double bonds, if appropriate further modifying components, and one or more mercapto compound containing at least one *Trade Mark 1~012~
tertiary amino group, with the proviso that the product contains tertlary amino groups which originate essentially or entirely from the mercapto compound. As component a) in this case, maleic anhydride or unsaturated fatty acids, for example, are used; an unsaturated alcohol which is suitable as component b) is, for example, 1,4-butenediol. In this case, the mercapto groups of the aminomercaptan containing a tertiary amino group add to the double bonds which are introduced into the binder by means of component a) and/or b).
The polyesters used in the coating composition according to the invention are preferably obtainable by reacting a rela-tively high-molecular-weight epoxy resin containing on average at least three epoxy groups per molecule with a polycarboxylic acid and/or polycarboxylic anhydride and with an aminocarboxylic acid containing at least one tertiary amino group and/or polyamine containing at least one tertiary and at least one primary or secondary amino group. As relatively high-molecular-weight epoxy resins containing on average at least three epoxy groups per molecule, epoxidized novolaks can be employed, for example. These are formed by reacting novolaks with epichlorohydrin.
The polyester used in the coating composition of the invention can be obtained by a process wherein the reaction of a) one or more polycarboxylic acids or anhydrides thereof, if appropriate together with one or more monocarboxylic acids, b) one or more polyols, if appropriate together with one or more monools, and, if appropriate, 134012~
c) one or more further modifying components capable of reacting with the reaction product from a), and b) is carried out simultaneously or stepwise by means of esterification and/or transesterification and/or addition reactions, with the proviso that the final product contains tertiary amino groups which originate from component a) and/or b) and/or c), and the reaction product from a), b), if appropriate c) has an acid number from 5 to 200, preferably 10 to 130, and an amine number from 3 to 150, preferably 10 to 100.
Suitable compounds of component a) are phthalic acid, isophthalic acid, terephthalic acid, halophthalic acids, such as tetrachloro- or tetrabromophthalic acid,. hexahydrophthalic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, endo-methylenetetrahydrophthalic acid, trimellitic acid, and anhydrides of the acids mentioned, if these exist. Suitable monocarboxylic acids which can be employed together with the polycarboxylic acids are, for example, benzoic acid, tert.-butylbenzoic acid, lauric acid, isononanoic acid and fatty acids of naturally occurring oils.
Suitable alcohol components b) are polyhydric alcohols, such as ethylene glycol, propanediols, butane-diols, pentanediols, hexanediols, neopentyl glycol, di-ethylene glycol, cyclohexanedimethanol, trimethylpentane-diol, ditrimethylolproPane~ trimethylolethane, trimethylol-propane, glycerol, pentaerythritol, dipentaerythritol ortrishydroxyethyl isocyanurate, if appropriate together with monohydric alcohols, such as, for example, butanol, octanol, lauryl alcohol and ethoxylated or propoxylated phenols.
As the carboxylic acid component a), amino-carboxylic acids contain;ng at least one tertiary amino group can be used, inter alia or exclusively. In this case, pyridine-3-carboxylic acid, i.e. nicotinic acid, is preferably used. The product of the reaction of an amino-alcohol containing at least one tertiary amino group with a polycarboxylic anhydride is also suitable as the car-boxylic acid component a). The product of the reaction of 2-hydroxyethylpyridine with phthalic anhydride may be mentioned as an example of such products.
It is particularly advantageous when the acid component used is the product of the reaction of a poly-amine containing at least one tertiary and at least one primary or secondary amino group with a polycarboxylic anhydride.
The tertiary amino group can also be introduced into the binder through the alcohol component b), for example. In this case, an aminoalcohol containing at least one tertiary amino group is employed as component b). Examples of amino alcohols containing at least one 1~4012~
tertiary amino group are 2-hydroxyethylpyridlne and dimethylamino-propanol.
According to the process according to the invention, a product of the reaction of epoxy resins with carboxylic acids and/or amines can be used as the alcohol component b).
It is preferred when polyisocyanates and/or diepoxide compounds, if appropriate also monoisocyanates and/or monoepoxide compounds, are employed as the modifying component c).
A preferred embodiment of the process according to the invention comprises using the product of the reaction of low-molecular weight epoxy resins with polycarboxylic acids and/or polycarboxylic anhydrides and aminocarboxylic acids containing at least one tertiary amino group and/or polyamines containing at least one tertiary and at least one primary or secondary amino group as component b), esterification subsequently being carried out, if appropriate, with components a) and b) and modification, if appropriate, with polyisocyanates.
When epoxy resins are used, low-chlorine types should be employed since, otherwise, strong discolouration of the products can occur.
As an alternative component c), a monoisocyanate containing at least one tertiary amino group is preferably used.
This can be prepared, for example, by reacting diisocyanates, such as, for example, isophorone diisocyanate, with aminoalcohols containing a tertiary amino group, such as, for example, hydroxy-ethylpyridine or dimethylaminoethanol, or with polyamines contain-ing at least one tertiary and at least one secondary or primary 13~012~
amino group. This component c) is bound to the binder system through reaction with free hydroxyl groups of the product formed previously, with formation of a urethane bond.
It is particularly advantageous when, as component c), a polyamine containing at least one tertiary and at least one primary or secondary amino group is used. An example of such a polyamine is dimethylaminopropylmethylamine.
A preferred embodiment of the process according to the invention comprises reacting a) one or more polycarboxylic acids or anhydrides thereof, if appropriate together with one or more monocarboxylic acids, b) one or more polyols, if appropriate together with one or more monools, components a) and/or b) containing ethylenic double bonds, and, if appropriate, c) further modifying components, including one or more mercapto compounds containing at least one tertiary amino group, with the proviso that the product contains tertiary amino groups which originate essentially or entirely from the mercapto compounds.
In this case, the SH group of the mercapto compound adds to the ethylenically unsaturated double bonds which originate from components a) and~or b). Examples of polycarboxylic acids or anhydrides thereof or monocarboxylic acids containing ethylenically unsaturated double bonds are maleic anhydride and ethylenically unsaturated fatty acids.
An example of a polyol component containing a polymeriz-able double bond is 1,4-butenediol.
, .~
134012~
A preferred process for the preparation of polyesters containing carboxyl groups and tertiary amino groups comprises reacting relatively high-molecular-weight epoxy resins containing on average at least three epoxy groups per molecule with polycarboxylic acids and/or polycarboxylic anhydrides and with an aminocarboxylic acid containing at least one tertiary amino group and/or polyamines containing at least one tertiary and at least one primary or secondary amino group.
The epoxy resins employed in this process are advan-tageously epoxidized novolaks.
If the tertiary amino group is to be introduced into thebinder system malnly or entirely through component c), a preferred embodiment of the process according to the invention comprises initially preparing a reaction product having an acid number of 5 to 200, preferably 10 to 130, by reaction of components a) and b), the reaction product subsequently being further reacted with component c) until the desired amine number is achieved.
A further preferred process variant comprises condensing or adding, in a first stage, components a), b) and, if approp-riate, c) to form a product having an acid number of 1 to 50,preferably 5 to 20, and further reacting this product, in a second stage, with polycarboxylic anhydrides until an acid number of 5 to 200, preferably 10 to 130, is produced.
Excessive discolouration of the products during the con-densation is avoided by adding antioxidants or reducing agents, such as, for example, hypophosphorous acid.
The coating composition of the present invention can 13~012~
also contain organic solvents, conventional additives and auxiliaries, if appropriate pigments, together with the polyester, prepared by the process described above, and, as crosslinking agent, an epoxy resin containing on average more than one epoxy group per molecule, the ratio of the free carboxyl groups in the polycondensation and/or addition product to the number of epoxy groups in the epoxy resin being in the range from 1:5 to 5:1.
Examples of suitable epoxy resins are products of the condensation of epichlorohydrin and bisphenol A, for example cycloaliphatic bisepoxides, epoxidized polybutadienes, which are produced by reacting commercially available polybutadiene oils with peracids or organic acid/H2O2 mixtures, epoxidation products of naturally occurring fats, oils, fatty acid derivatives, modified oils, novolaks containing epoxy groups, glycidyl ethers of a polyhydric alcohol, for example ethylene glycol diglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, trimethylol-propane polyglycidyl ether and pentaerythritol polyglycidyl ether, and suitable acrylate resins containing oxirane side groups.
Furthermore, the crosslinking agents can advantageously also be products of the reaction of polyepoxides containing hydroxyl groups with di- or polyisocyanates, as are produced, for example, by reacting OH-functional epoxides, such as, for example, sorbitol polyglycidyl ethers, with isophorone diisocyanate.
Suitable solvents are, for example, toluene, xylene, butanol, ethyl acetate, butyl acetate, pentyl acetate, dimethyl glutarate, dimethyl succinate, 1-methoxy-2 propyl acetate, 2-ethylhexanol, ethylene glycol diacetate, ethylene glycol monoethyl . ~
134012~
and monobutyl ether or the acetates thereof, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, naphthas containing aromatics, cyclohexanone, methyl ethyl ketone, acetone, butyl acetoxyglycolate and ethyl acetoxyglycolate. Suitable additives and auxiliaries are, for example, fillers, such as, for example, talcum, mica, kaolin, chalk, quartz sand, asbesto~
powder, barium sulfate, silicates, glass fibers, sedimentation inhibitors such as, for example, finely divided silica, bentonite, colloidal silicates and the like.
10The present invention also relates to a process for the preparation of the abovementioned coating agents, wherein the polyester, prepared by the process described above, the epoxy resin containing on average more than one epoxy group per molecule, and organic solvents, conventional additives and ~ auxiliaries and, if appropriate, pigments are processed by mixing and, if appropriate, dispersing to form a coating composition, the ratio of the free carboxyl groups in the polyester to the number of epoxy groups in the epoxy resin being in the range 1:5 to 5~1.
The coating agents according to the invention can be applied to a very wide variety of substrates. Suitable substrates are, for example, metals, such as iron, zinc, titanium, copper, aluminum, steel, brass, bronze, magnesium or the like, and furthermore ceramics, wood, glass, concrete and plastics.
The coating agents according to the invention cure at relatively low temperature, i.e. at room temperature or at slightly elevated temperatures. The low curing temperature and the short curing time can be attributed to the presence of an 13 iO126 internal catalyst in the binder system. If short curing times and low curing temperatures are desired, a polyester product having a relatively high amine number is employed.
By suitable choice of the alcohol component, the acid component and the modifying components, the properties of the final product in respect of hardness, elasticity and reactivity can be controlled in an excellent fashion.
Aromatic acid components lead to products having relatively great hardness, whereas cycloaliphatic or aliphatic acid components lead to relatively elastic films.
By using suitable monocarboxylic acids, the hardness and elasticity can likewise be influenced.
Relatively hard films are obtained when benzoic acid is used, whereas essentially softer films are obtained when fatty acids are used. The use of hexanediols as the al-cohol components leads to elastic films, whereas, in con-trast, the use of neopentyl glycol and pentaerythritolleads to relatively hard coatings.
Aromatic tertiary amino groups in the binder sys-tem have a higher catalytic activity than aliphatic or araliphatic amino groups.
Due to the low curing temperatures and the short curing times, the coating àgents according to the in-vention are preferably used for automobile refinishing.
In addition, they are highly suitable as top coats, fillers, varnishes, primers or undercoats.
The choice of the epoxy resin depends on the intended use. When used as a top coat, aliphatic epoxy resins are preferably used, and aromatic epoxy resins are also suitable for undercoats.
The problem of discoloration which may occur on use as a varnish can be avoided by incorporating prefer-ably aliphatic tertiary amino groups into the binder sys-tem. In the case of varnishes, low-chlorine or chlorine-free epoxy resins should be employed; discoloration phenomena do not then occur.
The films obtained from the binders or coating agents according to the invention have excellent proper-ties in respect of hardness, elasticity and reactivity.
A further advantage is that the use of an external cata-lyst can be omitted.
- 18 - 134012~
If curing is to be carried out under baking con-ditions, i.e. at temperatures of at least 100~C, the coating agent according to the invention can additionally contain a heat-curable ether- and/or amino- and/or OH
group-containing synthetic resin, such as, for example, phenol or amino resins.
The invention is illustrated in greater detail below with reference to illustrative embodiments. Parts denote parts by weight, unless otherwise stated.
Example 1:
Preparation of polyester resin I
1110.7 parts of phthalic anhydride, 742.1 parts of trimethylol propane, 187.2 parts of pyridine-3-carboxylic acid and 139.2-parts of 2-ethylhexanoic acid are heated slowly, with addition of 87 parts of xylene as entrainer, in a 4 liter polycondensation kettle equipped with stirrer and water separator, and the condensation reaction is carried out at 200-205~C to an acid number of about 70. After cooling and partially dissolving with 420 parts of xylene, 420 parts of methoxypropanol and 420 parts of butyl acetate (98/100), a solution of the acidic polyester having an acid number of 66, a viscosity (original) of 27 dPa.s and a solids content of 60 % is obtained.
Example 2:
Preparation of polyester -resin II
880 parts of phthalic anhydride, 247.2 parts of tri-methylhexanoic acid, 192.5 parts of pyridine-3-carboxylic acid and 838.7 parts of trimethylolpropane are heated - 19 - 134012~
slowly to 205~C, w;th addition of 86 parts of xylene as entrainer and 0.648 parts of hypophosphorous acid, in a polycondensation kettle equipped with stirrer and water separator, and the condensation reaction is car-ried out to 205-210~C to an acid number of about 12.
The mixture is then cooled to 130~C and partly dis-solved with 396 parts of xylene. 325 parts of phthalic anhydride are subsequently added, and the addition reaction with the hydroxyl groups of the polyester is carried out at 130~C. When the addition reaction is complete, the reaction mixture is partially dissolved with 281 parts of xylene and 763 parts of butanol.
The resin solution thus obtained has a solids content of 63 %, an acid number of 64 and a viscosity of 27 dPa.s (original).
Example 3:
Preparation of polyester resin III
493 parts of isophthalic acid, 440 of phthalic anhydride, 247.2 parts of trimethylhexanoic acid, 192.5 parts of pyridine-3-carboxylic acid and 838.7 parts of trimethylolpropane are heated slowly to about 200~C, with addition of 88 parts of xylene as entrainer and 0.6634 parts of hypophosphorous acid, in a poly-condensation kettle, and the condensation reaction is carried out at 200-210~C to an acid number of 20. The mixture is cooled to 130~C and partially dissolved with 532 parts of xylene. 450 parts of phthalic anhydride are than added, and the addition reaction with the polyester is carried out at 130~C. After addition of 376 parts of . .
- zo - 13~012~
xylene and 995 parts of butanol, the polyester solution obtained has a solids content of 59 %, an acid number of 88.5 and a viscosity of 11 dPa.s (original).
Example 4:
Preparation of polyester resin IV
315.6 parts of phthalic anhydride and 131.1 parts of 2-hydroxyethylpyridine are kept at 140-150~C for 4 hours in a polycondensation kettle, and, at 140~C, 409.4 parts of trimellitic anhydride, 310.5 parts of neopentyl glycol, 285.7 parts of trimethylolpropane, 130.1 parts of benzoic acid and 168.5 of trimethylhexanoic acid and 0.525 parts of hypophosphorous acid and, as entrainer, 70 parts of xylene are then added. The mixture is heated to 175~C and the condensation reaction is carried out to an acid number of about 84. After cooling and partially dissolving with 557 parts of xylene and 557 parts of butanol, a polyester solu-tion having a solids content of 57 %, acid number of 84 and a viscosity (original) of 21 dPa.s is obtained.
Example 5:
Preparation of polyester resin V
443.5 parts of isophthalic acid, 411.4 parts of hexahydrophthalic acid, 105.5 parts of isononanoic acid, 333 parts of para-tert.butylbenzoic acid, 304.8 parts of 4-(N,N-dimethylamino)-benzoic acid, 537 parts of tri-methylolpropane, 263.4 parts of pentaerythritol and0.959 parts of hypophosphorous acid, and also 96 parts of xylene as entrainer, are heated slowly to 195~C in a polycondensation kettle, and the condensation reaction is carried out at 195-205~C to an acid number of 15. The z 13~01~6 mixture is subsequently cooled and partially d;ssolved with 305 parts of xylene. 169.4 parts of hexahydro-phthalic acid and 116 parts of xylene are added to 1172 parts of this resin solution, and the addition reaction S between the anhydride and the polyester is carried out at 140~C. After partially dissolving with 390 parts of xylene and 98 parts of butanol, a resin solution having a solids content of 61 %, an acid number of 68 and a vis-cosity (original) of 26.5 dPa.s is obtained. (The viscosity of a solution diluted with xylene to a solids content of S0 % is 4.3 dPa.s.) Example 6:
Preparation of polyester resin VI
230 parts of pyridine-3-carboxylic acid, 333 parts of 4-tert.-butylbenzoic acid, 105.5 parts of iso-nonanoic acid, 443.5 parts of isophthalic acid, 411.4 parts of hexahydrophthalic acid, 537 parts of trimethyl-propane, 263.4 parts of pentaerythritol, 0.93 parts of hypophosphorous acid, and 93 parts of xylene as entrainer are heated slowly to 220~C in a polycondensation ket-tle, and the condensation reaction is carried out to an acid number of 20.2. After cooling and partially dis-soLving w;th 1-methoxy-2-propyl acetate, 444 parts of trimellitic anhydride are added. The mixture is kept at 140~C until an acid number (alcoholic) of 126 is reached.
290 parts of a glycidyl ester of a C10-~,~' alkylalkane-A carboxylic acid (e.g. Cardura E 10) are added to 1800parts of this polyester solution, and the mixture is kept at 85-90~C until an acid number of 65 is reached.
- ~ - 22 ~ I3 ~0 12 Addition of 150 parts of xylene, 150 parts of 1-methoxy-2-propyl acetate and 750 parts of methoxy-propanol leads to a carboxyl group-containing polyester solution having a solids content of 50.5 ~, an acid num-ber of 69 and a viscosity of 19 dPa.s.
Example 7:
Preparation of polyester resin VII
518.2 parts of isophthalic acid, 481 parts of hexahydrophthalic acid, 627.5 parts of trimethylol-propane, 324.7 parts of neopentyl glycol, Z49.6 parts ofpyridine-3-carboxylic acid, 1.1 parts of t;n(II) octoate and 88 parts of xylene as entrainer are heated slowly to 200~C in a polycondensation kettle, and the condensation reaction is carried out at 200-210~C to an acid number of t1. The mixture is then cooled to 140~C, and the addi-tion reaction with 369.6 parts of hexahydrophthalic acid is carried out at 140~C until an acid number of 73.5 is reached. The mixture is partially dissolved with 500 parts of 1-methoxy-2-propyl acetate and 423 parts of xylene. 1240 parts of this polyester solution are heated to 120~C, and 80.3 parts of iso-phorone diisocyanate are added within 30 minutes at 120~C. The mixture is partial-ly dissolved with 580 parts of methoxypropanol, and the resin solution obtained has a solids content of 55 ~, an acid number of 58 and a viscosity of 25 dPa.s (original).
Example 8:
Preparation of polyester resin VIII
469.2 parts of phthalic anhydride, 263.1 parts of isophthalic acid, 456.7 parts of trimethylolpropane, - 23 - 13'1012~
538.9 parts of epoxy resin (based on bisphenol A, epoxy equivalent weight 190), 187.8 parts of isononanoic acid, 175.5 parts of pyridine-3-carboxylic acid, 0.627 parts of hypophosphorous acid and 84 parts of xylene as entrainer are heated slowly to 200~C in a polycondensation kettle, and the condensation reaction is carried out to an acid number of 45. After cooling to 130~C, 390 parts of xylene and 247 parts of phthalic anhydride are added.
The temperature is kept at 130~C until an acid number of 87 is reached. The mixture is then partially dis-solved with 234 parts of xylene and 708 parts of butanol.
The carboxyl group-containing polyester resin solution has an acid number of 86, a solids content of 62 Z and a viscosity (diluted with xylene to 50 %) of 5.2 dPa.s.
The polyester solutions from examples I to VIII
are mixed with various epoxy resins. The mixtures formed from polyester solutions I, II, III, IV, V, VI and VIII
are adjusted to a solids content of 55 % using xylene, but, in contrast, the mixture made from polyester resin VII is adjusted to a solids content of 50 %. The mixtures are knife-coated onto glass sheets (200 ~m wet film).
The film is cured either at room temperature only or at room temperature after drying for 30 minutes at 60~C.
Crosslinking takes place with epoxy resins A, B or C.
A: Aromatic epoxy resin based on bisphenol A, epoxy equivalent weight 450.
B: Aromatic epoxy resin based on the glycidyl ether of a novolak, epoxy equivalent weight 178.
C: Aliphatic epoxy resin based on a polyglycidyl ether - 24 - 134012~
of a polyol ~sorbitol), epoxy equivalent weight 180.
.
- 25 - I3l10I2 Example Polyester Epoxy Mixing ratio Drying resin resin solidtsolid conditions a I A 64/36 30 min/60~C
b IV P 79/21 30 min/60~C
c V ~ 82/18 30 min/60~C
d VII ~ 85/15 30 min/60~C
e VI C 80/20 RT
f III C 74/26 RT
g II C 81/19 RT
h VIII 9 79/21 RT
Example Pendulum hardness Double wipes with methyl after 6 daysethyl ketone after 6 days (sec~
a 162 160 b 81 120 c 94 30 d 137 200 e 84 200 f 203 145 h (8 days) 150 200 g after Z days after 2 days h after 3 days after 3 days
Claims (23)
1. A method of refinishing an automobile body or body part which comprises applying to the body or body part a coating composition which comprises a polyester containing carboxyl groups and tertiary amino groups, which polyester has an acid number from 5 to 200 and an amino number from 3 to 150, and a crosslinking agent which is an epoxy resin containing on average more than one epoxy group per molecule, the ratio of the number of free carboxyl groups in the polyester to the number of epoxy groups in the epoxy resin being in the range from 1:5 to 5:1 wherein the polyester is the product of reaction between a polycarboxylic acid or anhydride component a), and a polyol component b) and one or both of the components a) and b) contains tertiary amino groups.
2. A method according to claim 1 wherein the polyester is the product of reaction between a polycarboxylic acid or anhydride component a), a polyol component b) and another component c) which is an isocyanate or an epoxide capable of reacting with the product of the components a) and b) and at least one of the components a), b) and c) contains tertiary amino groups.
3. A method according to claim 1 wherein in the reaction between the components a) and b) a monocarboxylic acid is also present.
4. A method according to claim 1 wherein in the reaction between the components a) and b) a monool is also present.
5. A method according to claim 1 wherein the polyester has an acid number from 10 to 130 and an amine number from 10 to 100.
6. A method according to claim 1 wherein the component a) contains at least one tertiary amino group.
7. A method according to any one of claims 1 to 6 wherein the component a) comprises pyridine-3-carboxylic acid.
8. A method according to any one of claims 1 to 6 wherein component a) comprises the product of the reaction of an aminoalcohol containing at least one tertiary amino group with a polycarboxylic anhydride.
9. A method according to any one of claims 1 to 6 wherein component a) comprises the product of the reaction of a polyamine containing at least one tertiary and at least one primary or secondary amino group with a polycarboxylic anhydride.
10. A method according to any one of claims 1 to 6 wherein component b) comprises an amino alcohol containing at least one tertiary amino group.
11. A method according to any one of claims 1 to 6 wherein component b) comprises the product of the reaction of an epoxy resin with a carboxylic acid or amine.
12. A method according to claim 2 wherein component c) comprises a polyisocyanate or a diepoxy compound.
13. A method according to claim 2 wherein component c) comprises a monoisocyanate or monoepoxy compound.
14. A method according to any one of claims 1 to 6 wherein component b) comprises the product of reaction between a low molecular weight epoxy resin and one or more reactants selected from the group consisting of polycarboxylic acids, polycarboxylic anhydrides, aminocarboxylic acids containing at least one tertiary amino group and polyamines containing at least one tertiary and at least one primary or secondary amino group.
15. A method according to any one of claims 1 to 6 wherein component b) comprises the product of reaction between a low molecular weight epoxy resin and one or more reactants selected from the group consisting of polycarboxylic acids, polycarboxylic anhydrides, aminocarboxylic acids containing at least one tertiary amino group and polyamines containing at least one tertiary and at least one primary or secondary amino group, which product is modified by reaction with a polyisocyanate.
16. A method according to claim 2 wherein component c) comprises a monoisocyanate containing at least one tertiary amino group.
17. A method according to claim 2 wherein component c) comprises a polyamine containing at least one tertiary and at least one primary or secondary amino group.
18. A method according to claim 1 wherein the polyester is a polyester obtainable by reacting a polycarboxylic acid or anhydride a), a polyol component b) at least one of components a) and b) containing ethylenic double bonds and a mercapto compound containing tertiary amino groups, the polyester product containing tertiary amino groups originating from the mercapto compound.
19. A method according to claim 18 wherein component a) also contains one or more monocarboxylic acids.
20. A method according to claim 18 wherein component b) also contains one or more monools.
21. A method according to claim 1 wherein the polyester is a polyester obtainable by reacting a relatively high molecular weight epoxy resin containing on average at least 3 epoxy groups per molecule with one or more reactants selected from polycarboxylic acids and polycarboxylic acid anhydrides and one or more reactants selected from aminocarboxylic acids containing at least one tertiary amino group.
22. A method according to claim 21 wherein the aminocarboxylic acid containing at least one tertiary amino group also contains at least one primary or secondary amino group.
23. A method according to any one of claims 1 to 6 for refinishing an automobile body as a topcoat, filler, varnish, primer or undercoat.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3629470.5 | 1986-08-29 | ||
| DE19863629470 DE3629470A1 (en) | 1986-08-29 | 1986-08-29 | CARBOXYL GROUPS AND TERTIAL AMINO GROUPS CONTAINING POLYCONDENSATION AND / OR ADDITION PRODUCT, COATING AGENTS BASED ON THE SAME AND THEIR USE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1340126C true CA1340126C (en) | 1998-11-10 |
Family
ID=6308500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000545598A Expired - Fee Related CA1340126C (en) | 1986-08-29 | 1987-08-28 | Polycondensation and/or additon product containing carboxyl groups and tertiary amino groups, coating agents based thereon, and the use thereof |
Country Status (8)
| Country | Link |
|---|---|
| US (2) | US5179191A (en) |
| EP (2) | EP0257402B1 (en) |
| AT (1) | ATE82760T1 (en) |
| BR (1) | BR8707805A (en) |
| CA (1) | CA1340126C (en) |
| DE (2) | DE3629470A1 (en) |
| ES (1) | ES2036197T3 (en) |
| WO (1) | WO1988001629A1 (en) |
Families Citing this family (54)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3806641A1 (en) * | 1988-03-02 | 1989-09-14 | Basf Lacke & Farben | COATING AGENTS BASED ON CARBOXYL GROUPS AND POLYCONDENSATION AND / OR ADDITION PRODUCTS CONTAINING AMINO GROUPS AND THEIR USE |
| DE4222012A1 (en) * | 1991-12-21 | 1993-06-24 | Hoechst Ag | AQUEOUS FILLER COMPOSITION |
| US5559169A (en) * | 1994-12-15 | 1996-09-24 | Cabot Corporation | EPDM, HNBR and Butyl rubber compositions containing carbon black products |
| IL116377A (en) | 1994-12-15 | 2003-05-29 | Cabot Corp | Reaction of carbon black with diazonium salts, resultant carbon black products and their uses |
| IL116378A (en) * | 1994-12-15 | 2003-05-29 | Cabot Corp | Non-aqueous coating or ink composition with improved optical properties containing modified carbon product and method of preparation of the composition |
| IL116379A (en) * | 1994-12-15 | 2003-12-10 | Cabot Corp | Aqueous inks and coatings containing modified carbon products |
| US5575845A (en) * | 1994-12-15 | 1996-11-19 | Cabot Corporation | Carbon black products for coloring mineral binders |
| IL116376A (en) * | 1994-12-15 | 2001-03-19 | Cabot Corp | Aqueous ink jet ink compositions containing modified carbon products |
| US5571311A (en) * | 1994-12-15 | 1996-11-05 | Cabot Corporation | Ink jet ink formulations containing carbon black products |
| US5554739A (en) * | 1994-12-15 | 1996-09-10 | Cabot Corporation | Process for preparing carbon materials with diazonium salts and resultant carbon products |
| US5807494A (en) | 1994-12-15 | 1998-09-15 | Boes; Ralph Ulrich | Gel compositions comprising silica and functionalized carbon products |
| US6028137A (en) | 1995-05-22 | 2000-02-22 | Cabot Corporation | Elastomeric compounds incorporating silicon-treated carbon blacks |
| HUP9802554A3 (en) | 1995-05-22 | 1999-04-28 | Cabot Corp | Elastomeric compounds incorporating partially coated carbon blacks |
| US5622557A (en) | 1995-05-22 | 1997-04-22 | Cabot Corporation | Mineral binders colored with silicon-containing carbon black |
| US6323273B1 (en) | 1995-05-22 | 2001-11-27 | Cabot Corporation | Elastomeric compounds incorporating silicon-treated carbon blacks |
| US5958999A (en) | 1996-04-05 | 1999-09-28 | Cabot Corporation | Ink compositions and method for generating images produced therefrom |
| US20020056686A1 (en) * | 1996-06-14 | 2002-05-16 | Agathagelos Kyrlidis | Chromatography and other adsorptions using modified carbon adsorbents |
| WO1997047382A1 (en) * | 1996-06-14 | 1997-12-18 | Cabot Corporation | Modified carbon adsorbents and processes for adsorption using the same |
| US5707432A (en) | 1996-06-14 | 1998-01-13 | Cabot Corporation | Modified carbon products and inks and coatings containing modified carbon products |
| US5747562A (en) | 1996-06-14 | 1998-05-05 | Cabot Corporation | Ink and coating compositions containing silicon-treated carbon black |
| US5698016A (en) * | 1996-06-14 | 1997-12-16 | Cabot Corporation | Compositions of modified carbon products and amphiphilic ions and methods of using the same |
| EP0939781A1 (en) * | 1996-11-25 | 1999-09-08 | Shell Internationale Researchmaatschappij B.V. | Acid functional and epoxy functional polyester resins |
| US5919855A (en) | 1997-02-11 | 1999-07-06 | Cabot Corporation | Use of modified carbon black in gas-phase polymerizations |
| US6444018B1 (en) * | 1998-06-25 | 2002-09-03 | Xerox Corporation | Phase change ink carrier compositions containing anhydride/amino alcohol-based adducts |
| DE10054504A1 (en) * | 2000-11-03 | 2002-05-16 | Alfred Krueger | Production of high-molecular weight cyclic dicarboxylic acid for use e.g. in epoxy coating material, involves reacting diacid anhydride with diol to form a half-ester and then reacting with more anhydride, using a cyclic reactant |
| US7842382B2 (en) | 2004-03-11 | 2010-11-30 | Knauf Insulation Gmbh | Binder compositions and associated methods |
| JP2008516071A (en) * | 2004-10-13 | 2008-05-15 | クナーフ インシュレーション ゲーエムベーハー | Polyester binding composition |
| DK2574639T3 (en) * | 2005-07-26 | 2019-07-15 | Knauf Insulation Gmbh | Method for making glass fiber insulation products |
| EP2108006B8 (en) | 2007-01-25 | 2020-11-11 | Knauf Insulation GmbH | Binders and materials made therewith |
| US7854980B2 (en) * | 2007-01-25 | 2010-12-21 | Knauf Insulation Limited | Formaldehyde-free mineral fibre insulation product |
| EP2109594A1 (en) * | 2007-01-25 | 2009-10-21 | Knauf Insulation Limited | Mineral fibre insulation |
| CN101668713B (en) | 2007-01-25 | 2012-11-07 | 可耐福保温材料有限公司 | Mineral fibre board |
| WO2008089847A1 (en) | 2007-01-25 | 2008-07-31 | Knauf Insulation Limited | Composite wood board |
| EP2137223B1 (en) | 2007-04-13 | 2019-02-27 | Knauf Insulation GmbH | Composite maillard-resole binders |
| FR2917612B1 (en) * | 2007-06-21 | 2009-08-21 | Oreal | COSMETIC OR PHARMACEUTICAL COMPOSITION COMPRISING A POLYCONDENSATE, COSMETIC PROCESSING PROCESS, POLYCONDENSATE AND PROCESS FOR PREPARING |
| EP2700664B1 (en) * | 2007-07-05 | 2018-10-10 | Knauf Insulation | Hydroxymonocarboxylic acid-based maillard binder |
| GB0715100D0 (en) | 2007-08-03 | 2007-09-12 | Knauf Insulation Ltd | Binders |
| EP2462169B1 (en) | 2009-08-07 | 2019-02-27 | Knauf Insulation | Molasses binder |
| PT2566904T (en) | 2010-05-07 | 2021-08-30 | Knauf Insulation | Carbohydrate polyamine binders and materials made therewith |
| KR101835899B1 (en) | 2010-05-07 | 2018-03-07 | 크나우프 인설레이션, 인크. | Carbohydrate binders and materials made therewith |
| EP2576882B1 (en) | 2010-06-07 | 2015-02-25 | Knauf Insulation | Fiber products having temperature control additives |
| US20140186635A1 (en) | 2011-05-07 | 2014-07-03 | Knauf Insulation | Liquid high solids binder composition |
| GB201206193D0 (en) | 2012-04-05 | 2012-05-23 | Knauf Insulation Ltd | Binders and associated products |
| GB201214734D0 (en) | 2012-08-17 | 2012-10-03 | Knauf Insulation Ltd | Wood board and process for its production |
| PL2928936T3 (en) | 2012-12-05 | 2022-12-27 | Knauf Insulation Sprl | Binder |
| US11401204B2 (en) | 2014-02-07 | 2022-08-02 | Knauf Insulation, Inc. | Uncured articles with improved shelf-life |
| GB201408909D0 (en) | 2014-05-20 | 2014-07-02 | Knauf Insulation Ltd | Binders |
| CN106031844B (en) * | 2015-03-20 | 2020-01-07 | 江西永丰博源实业有限公司 | Desulfurization and denitrification agent |
| GB201517867D0 (en) | 2015-10-09 | 2015-11-25 | Knauf Insulation Ltd | Wood particle boards |
| GB201610063D0 (en) | 2016-06-09 | 2016-07-27 | Knauf Insulation Ltd | Binders |
| GB201701569D0 (en) | 2017-01-31 | 2017-03-15 | Knauf Insulation Ltd | Improved binder compositions and uses thereof |
| GB201804907D0 (en) | 2018-03-27 | 2018-05-09 | Knauf Insulation Ltd | Composite products |
| GB201804908D0 (en) | 2018-03-27 | 2018-05-09 | Knauf Insulation Ltd | Binder compositions and uses thereof |
| CN110615889B (en) * | 2019-09-19 | 2021-06-08 | 擎天材料科技有限公司 | Polyester resin for crystallography powder coating and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3128265A (en) * | 1960-04-25 | 1964-04-07 | Eastman Kodak Co | Resinous compositions comprising mixtures of polyesters containing quaternized aminegroups and epoxy resins |
| DE1794233A1 (en) * | 1967-02-10 | 1971-10-28 | Alfred Krueger | Insulating coating agents with high heat resistance |
| US3493414A (en) * | 1967-10-12 | 1970-02-03 | Ashland Oil Inc | Epoxy/polyester compositions |
| US3575901A (en) * | 1969-04-04 | 1971-04-20 | Mobil Oil Corp | Polyester and alkyd resins including tertiary alkyl manoamine component |
| FR2041667A5 (en) * | 1969-05-30 | 1971-01-29 | Protex | |
| DE2161253A1 (en) * | 1971-12-10 | 1973-06-28 | Basf Ag | Basically modified alkyd resins - used as lacquer binders |
| DE3007930A1 (en) * | 1980-03-01 | 1981-09-24 | Henkel KGaA, 4000 Düsseldorf | NEW POLYESTER COMPOUNDS, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A TEXTILE SOFTENER |
| JPS59142220A (en) * | 1983-02-04 | 1984-08-15 | Dainippon Ink & Chem Inc | Room temperature-curable resin composition |
-
1986
- 1986-08-29 DE DE19863629470 patent/DE3629470A1/en not_active Withdrawn
-
1987
- 1987-08-06 ES ES198787111391T patent/ES2036197T3/en not_active Expired - Lifetime
- 1987-08-06 WO PCT/EP1987/000429 patent/WO1988001629A1/en not_active Application Discontinuation
- 1987-08-06 DE DE8787111391T patent/DE3782778D1/en not_active Expired - Fee Related
- 1987-08-06 EP EP87111391A patent/EP0257402B1/en not_active Expired - Lifetime
- 1987-08-06 EP EP87905438A patent/EP0322410A1/en active Pending
- 1987-08-06 US US07/328,583 patent/US5179191A/en not_active Expired - Lifetime
- 1987-08-06 AT AT87111391T patent/ATE82760T1/en not_active IP Right Cessation
- 1987-08-06 BR BR8707805A patent/BR8707805A/en not_active IP Right Cessation
- 1987-08-28 CA CA000545598A patent/CA1340126C/en not_active Expired - Fee Related
-
1993
- 1993-01-08 US US08/002,291 patent/US5336753A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE3782778D1 (en) | 1993-01-07 |
| EP0257402A1 (en) | 1988-03-02 |
| DE3629470A1 (en) | 1988-03-10 |
| US5179191A (en) | 1993-01-12 |
| EP0257402B1 (en) | 1992-11-25 |
| US5336753A (en) | 1994-08-09 |
| EP0322410A1 (en) | 1989-07-05 |
| BR8707805A (en) | 1989-08-15 |
| ES2036197T3 (en) | 1993-05-16 |
| ATE82760T1 (en) | 1992-12-15 |
| WO1988001629A1 (en) | 1988-03-10 |
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