CN1054803C - Polycarbonic acid ester resin layered products absorbing near-infrared and formed products made of same - Google Patents
Polycarbonic acid ester resin layered products absorbing near-infrared and formed products made of same Download PDFInfo
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- CN1054803C CN1054803C CN94104645A CN94104645A CN1054803C CN 1054803 C CN1054803 C CN 1054803C CN 94104645 A CN94104645 A CN 94104645A CN 94104645 A CN94104645 A CN 94104645A CN 1054803 C CN1054803 C CN 1054803C
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Abstract
To obtain a resin laminate which has excellent near infrared absorption capacity and in which instability such as fading, etc., is eliminated by integrally laminating a polycarbonate resin film on a polycarbonate resin sheet containing a specific ratio of cupric sulfide to styrene resin. A polycarbonate resin film is integrally laminated on a polycarbonate resin sheet containing 0.01-5 wt.pts. of cupric sulfide to 100 pts.wt. of polycarbonate resin thereby to form a polycarbonate resin laminate having excellent near infrared absorption capacity. Thus, instability such as fading, etc., is eliminated in the laminate and a wavy platelike molded form due to it, and photochromism in which fading occurs when it is left to stand for a long period in a dark place is obviated. Accordingly, the laminate can be applied to an optical filter, an outdoor terrace, etc.
Description
But the present invention relates to better to see through visible light, have the novel polycarbonate-based resin laminate of excellent absorption near infrared ray performance and be configured as corrugated sheet shape or the polycarbonate-based resin molded body of the absorption near infrared ray that the weatherability of section shape is good.
Have near infrared ray absorbing can light transmissive material known have in the U.S. Pat 3692688 disclosed like that, with tungsten hexachloride (WCl
6) and stannic chloride (SnCl
22H
2O) be dissolved in carry out polymerization in the methyl methacrylate slurries (monomer) and not having in fact of obtaining have vaporific have good near infrared ray absorbing can material.
In addition, up to the present, the near-infrared-absorbing material of having developed already has, and mercaptan nickel complex, the spy who reports on the chromium of reporting on the special public clear 60-42269 communique, cobalt complex salt, the special public clear 60-21294 communique opens the anthraquinone derivative, the spy that report on the clear 61-115958 communique and open the new Squarilium compound of reporting on the clear 61-218551 communique that has a very big absorbing wavelength in 700～800nm scope.
No matter be room external application or usefulness within doors, light-passing board not only uses surface plate, and uses corrugated sheet shape or section shape product, can estimate that above-mentioned various material also will be applied on corrugated sheet, the section shape product.
In the near-infrared-absorbing material in the past, if organic system, then exist poor durability, along with the variation of environment and the ability at the passing initial stage of the time problem of deterioration gradually, on the other hand, if the complexing system, though have durability, it is the absorption near infrared ray part not only, also absorbs visible light, also have the material of compound painted consumingly mostly, exist the problem that purposes is restricted.In addition, the material of any system all is absworption peak to occur in certain wavelengths, and does not almost have absorbability on the wavelength at this peak departing from.Then need Wavelength of Laser consistent as considering these materials with the laser of near-infrared wavelength record body with the absworption peak of material as light source as for example.No matter Wavelength of Laser, still the absorbing wavelength portion of near-infrared-absorbing material obtains in limited scope, so the consistent combination of the absworption peak of Wavelength of Laser and near-infrared-absorbing material can only obtain in extremely limited scope.
In addition, above-mentioned conventional art with WC1
6And SnCl
22H
2The composition that O is dissolved in behind the methyl methacrylate slurries shows avy blue, though have the character of absorption near infrared ray well, if when being placed on dark locating for a long time, will produce the problem of fading.This photochromism of slowly carrying out is disadvantageous providing aspect optical filter with certain mass and the heat absorptivity classification industrial product.
Present inventors for the near infrared range at 800～2000nm can similarly absorb, less painted and weatherability and the good near-infrared-absorbing material of durability carried out continuous research, found that to make and contain copper compound or copper compound and thiourea derivative and/or thioamide derivatives in polycarbonate-based resin or the metha crylic resin, they are made layered product, can this finish the present invention.
That is to say, the present invention relates to have the polycarbonate-based resin laminate of good near infrared ray absorbing energy, it is characterized in that it is formed by lamination metha crylic resin molding on polycarbonate-based resin plate, and polycarbonate-based resin plate constitute polycarbonate-based resin with respect to per 100 parts of weight, contain copper sulfide or the copper sulfide of 0.01～5 part of weight and the thiourea derivative and/or the thioamide derivatives of 0.001～1 part of weight of 0.01～5 part of weight.
The invention still further relates to polycarbonate-based resin laminate with good near infrared ray absorbing energy, it is characterized in that it is formed by lamination near-infrared absorbing methacrylic acid resin film on polycarbonate-based resin plate, and near-infrared absorbing methacrylic acid resin film constitute metha crylic resin with respect to per 100 parts of weight, contain copper sulfide or the copper sulfide of 0.1～50 part of weight and the thiourea derivative and/or the thioamide derivatives of 0.01～10 part of weight of 0.1～50 part of weight.
In addition, the invention still further relates to the polycarbonate-based resin laminated formed body of near-infrared absorbing that above-mentioned polycarbonate-based resin laminate with good near infrared ray absorbing energy is configured as corrugated sheet shape or section shape.
The polycarbonate-based resin that uses among the present invention makes dihydric phenol and carbonate precursor react manufacturing with solwution method or fusion method.The typical example of dihydric phenol can enumerate 2, two (4-hydroxy phenyl) propane [bisphenol-A] of 2-, two (4-hydroxy phenyl) methane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2, two (the 4-hydroxyls-3 of 2-, the 5-3,5-dimethylphenyl) propane, 2, two (4-hydroxyl-3, the 5-aminomethyl phenyl) propane of 2-, two (4-hydroxy phenyl) sulphur, two (4-hydroxy phenyl) sulfonic acid etc.Wherein preferred dihydric phenol is two (4-hydroxy phenyl) alkane hydrocarbon systems, particularly is the material of main material with the bisphenol-A.In addition, the precursor of carbonic ester can be enumerated carbonyl halides than thing, carbonyl ester or haloformate etc., specifically, is bishaloformate of carbonyl halide, diphenyl carbonate, dihydric phenol and composition thereof.
When making Merlon, can be individually or use above-mentioned dihydric phenol more than two kinds.Also can be mixed with two or more the Merlon that obtains in addition, the viscosity-average molecular weight of Merlon generally is 10,000～100,000, preferred 20,000～60,000.When making these Merlon, also can use an amount of molecular weight regulator as required, for the branching agent that improves processing characteristics, promote catalyst for reaction etc.
Metha crylic resin described in the present invention is meant that the monomer with the various esters of methacrylic acid is the condensate or the EVA of principal component, the EVA of the independent condensate of various methacrylates such as the concrete methyl methacrylate enumerated, EMA, butyl methacrylate and these methacrylates and various acrylate, acrylic acid, styrene, AMS etc.The manufacture method of these resins can be used known polymerizations such as suspension polymerisation, emulsion polymerisation, polymerisation in solution.Also can use in addition and contain these polymer materials monomers and contain monomer and the slurries of partially polymerized body.
Employed copper sulfide can be the powder thing of making according to a conventional method among the present invention, below the preferred 12 μ m of its average grain diameter, more preferably below the 10 μ m.In addition, preferably there is not the above particle of 20 μ m basically.Surpass above-mentioned scope as average grain diameter, the formed body outward appearance that then obtains degenerates, and not only the concavo-convex parallel rays permeability that makes because of the surface degenerates, and makes the rerum natura of formed body and near infrared ray absorbing also descend.
Use the thiourea derivative of following general formula (1) expression can enumerate following compounds among the present invention:
(R
1, R
2, R
3Expression is selected from the univalent perssad of hydrogen, alkyl, cycloalkyl, aryl, aralkyl and five yuan or hexa-atomic heterocyclic radical, and each group also can have substituting group, the R more than 1
1And R
2Perhaps R
2And R
3Also can be connected to form ring).
For example can enumerate 1-ethyl-3-phenylthiourea; 1; the 3-rhenocure CA; 1; the 3-diethyl thiourea; 1-ethyl-3-rubigan thiocarbamide; 1-ethyl-3-(2-ethoxy) thiocarbamide; 1-(2-thiazolyl)-3-phenylthiourea; 1; 3-distearyl acyl group thiocarbamide; 1; 3-docosyl thiocarbamide; the 1-ethyl thiourea; 1-is to bromophenyl-3-phenylthiourea; 1-(2-thiophenyl)-3-phenylthiourea; 1; two (2-ethoxy) thiocarbamides of 3-; 1-p-amino phenyl-3-phenylthiourea; 1-p-nitrophenyl-3-phenylthiourea; 1-p-hydroxybenzene-3-phenylthiourea; 1; 3-two m-chloro phenylthioureas; ethylene thiourea; thiocarbamide; 1-methyl-3-p-hydroxybenzene thiocarbamide; the 1-phenylthiourea; 1-m-nitro base thiocarbamide; 1-p-nitrophenyl thiocarbamide; 1-p-aminophenyl thiocarbamide; 1; the 3-dimethyl sulfourea; 1; the 3-dicyclohexyl thiourea; 1-phenyl-3-rubigan thiocarbamide; 1-phenyl-3-p-methoxyphenyl thiocarbamide; 1; the 1-rhenocure CA; 1; 1-dibenzyl-3-phenethyl thiocarbamide; 1-phenyl-3-(2-hydroxyethyl) thiocarbamide etc., but be not limited thereto.
The thioamide derivatives of employed available following general formula (II) expression among the present invention, example is as follows:
(R
4, R
5Expression is selected from the univalent perssad of hydrogen, alkyl, alkenyl, cycloalkyl, aryl, aralkyl and five yuan or hexa-member heterocycle base, perhaps R
5The expression alkoxyl, each group can have the substituting group more than 1, R
4And R
5Also can be connected to form ring).
N-methyl thiobenzamide for example; N-phenyl thiobenzamide; N-ethylenebis dithiocarbamate acetamide; the N-ethylenebis dithiocarbamate is to chlorobenzamide; N-propyl dithiocarbamate benzamide; N-ethylenebis dithiocarbamate stearmide; N-1-(2-thiazolyl) thiobenzamide; N-stearyl sulfo-stearmide; N-docosyl sulfo-docosane acid amides; thioacetamide; N-phenyl sulfo-is to brombenzamide; N-1-(2-thiophenyl) thiobenzamide; N-docosyl thioacetamide; N-p-aminophenyl thiobenzamide; N-p-nitrophenyl thiobenzamide; N-p-hydroxybenzene thiobenzamide; chlorphenyl thiobenzamide between N-; Thionicotinamide; thioacetyl aniline; neighbour-ethyl-N-phenyl (thiocarbamate); thiobenzamide; sulfo---nitrobenzamide; sulfo--right-nitrobenzamide; sulfo--right-aminobenzamide; N-methyl thioacetamide; N-cyclohexyl benzene formamide; N-chlorphenyl thiobenzamide; N-p-methoxyphenyl thiobenzamide; N-stearyl thiobenzamide etc., but be not limited thereto.
Employed copper sulfide, thiourea derivative and thioamide derivatives among the present invention can the transmitance through setting visual field and near infrared region change its content.The addition of copper sulfide is 0.01～5 part of weight with respect to the polycarbonate-based resin of per 100 parts of weight, and preferred 0.02～3 part of weight is 0.1～50 part of weight with respect to the metha crylic resin of per 100 parts of weight, preferred 0.2～30 part of weight.
Addition when adding thiourea derivative and thioamide derivatives is respectively: with respect to per 100 parts of polycarbonate-based resins of weight is 0.001～1 part of weight, preferred 0.002～0.5 part of weight, with respect to per 100 parts of weight methacrylic acids is that resin is 0.01～10 part of weight, preferred 0.02～5 part of weight.
In addition, the resin material that obtains as the present invention is for example when tabular, even identical its transmitance of content also changes with thickness of slab, so finally can determine content according to the transmitance of the thickness of slab of setting.
In the present invention, addition with respect to per 100 parts of polycarbonate-based resin cure copper of weight is a resin less than 0.01 part of weight or with respect to per 100 parts of weight methacrylic acids, the addition of copper sulfide is during less than 0.1 part of weight, and near infrared ray absorbing can fully improve.
On the other hand, with respect to per 100 parts of polycarbonate-based resins of weight, when the addition that the addition of copper sulfide surpasses 5 parts of weight or thiourea derivative or thioamide derivatives surpasses 1 part of weight or with respect to the metha crylic resin of per 100 parts of weight, when the addition that the addition of copper sulfide surpasses 50 parts of weight or thiourea derivative or thioamide derivatives surpasses 10 parts of weight, then can't see the rising of near infrared ray absorbing energy, and the vaporific possibility of generation in material is arranged.
Moreover, except that mentioned component, as required, in order to disperse copper sulfide better, it also is effective dispersants such as glycerine fatty acid ester as the sorbitan fatty acid ester of sorbitan single-hard ester acid ester class and glycerine monostearate class can being added in the composition of the present invention, also can cooperate proper additive in addition, for example, reinforcing agents such as fire retardant, heat stabilizer, antioxidant, light stabilizer, ultra-violet absorber, lubricant, colouring agent, inorganic filler, glass fibre etc.
Among the present invention, the mixed method of polycarbonate-based resin or metha crylic resin and copper sulfide or copper sulfide and thiourea derivative and/or thioamide derivatives, do not need special means and order, with the mixing arrangement of routine, for example hot-rolling, internal mixture or extruder can be made at an easy rate.
Polycarbonate-based resin plate itself and methacrylic acid resin film itself can be according to the usual way manufacturings.For example, can adopt T modulus method, blow-moulding process, calendaring molding method, the compression forming method of extruder, special-shaped extruding formation method waits to be made.
Plastic laminate of the present invention, be to have pressed the methacrylic acid resin film that contains copper sulfide, perhaps pressed the layered product of above-mentioned methacrylic acid resin film on the upper strata of one side at least of the polycarbonate-based resin plate that contains copper sulfide at least one surface layer of above-mentioned polycarbonate-based resin plate.Then, when this layered product is configured as ripple plate shape, can obtain by methods such as press molding (for example mould extruding, forming rolls etc.), vacuum forming, hot plate shapings.The lamination of this moment can pass through wet type lamination, dry lamination, and known methods such as extruding lamination, pressure sintering carry out.Also can adopt its extrusion molding in addition, adopt extruder respectively, on a mould, carry out Compound Extrusion simultaneously with respect to the different resins layer.Here, the suitable scope of the thickness of polycarbonate-based resin plate is 0.01～10mm, the scope of preferred 0.05～5mm.On the other hand, the scope that the metha crylic thickness of resin film is suitable is 0.01～0.2mm, preferred 0.03～0.08mm.
The thickness of polycarbonate-based resin plate is if exceed above-mentioned scope, and the intensity of layered product or corrugated sheet descends, and lacks economy, so undesirable.In addition, the metha crylic thickness of resin film is crossed when approaching, and resistance to impact descended when shaded effect was insufficient, blocked up, so also undesirable.
When being pressed in the metha crylic resin film layer on the polycarbonate-based resin, because the methacrylic acid resin film is in the blocking effect of ultra-violet (UV) band, the mechanical strengths such as hot strength, bending strength, impact strength that can significantly suppress polycarbonate-based resin descend, and significantly suppress the yellowing degree of polycarbonate-based resin.
On the other hand, the section of above-mentioned layered product is made the concavo-convex continuously of semicircle, square, platform shape, triangle etc., to make waveform.The spacing of these waveform shapes is 20～150mm normally, and its degree of depth is generally 5～100mm.The section configuration of abnormity can be made the tubular of circle and triangle sample, becomes the style of opening of hollow shape, L type, U type, semi-circular sample at the interval partition of regulation with reinforcement.
In addition, for the intensity that increases plate or when adding decorative pattern, the glass fiber mesh or the stainless steel wire mesh that can make its inside contain the square grid of about 5mm that useful glass wire is woven into form.
In addition, plastic laminate of the present invention also can be used a plurality of above assemblys, for example 2 lamination corrugated sheets and laminate make its integrated (hollow shape) with reinforcement at the interval of regulation, this is for being useful especially as the composite plate that requires certain intensity and thermal insulation, and this is a fine applicable cases of the present invention.
As mentioned above, according to the present invention, by the copper sulfide below the 12 μ m or copper sulfide and thiourea derivative and/or thioamide derivatives are added hot milling in transparent resin, can obtain having in the zone of 800～2000nm good near infrared ray absorbing about the same can polycarbonate-based resin laminate.
Be described in detail the present invention by the following examples, but the present invention is not subjected to the restriction of these embodiment.Moreover the adding proportion among the embodiment is all represented with weight.
The transmitted spectrum of the resin material that obtains in addition, spectrophotometer ((strain) Hitachi system: 323 types) measure.
Near infrared ray absorbing can judgement be with 900,1000,1100, the mean value of the absorption value of each wavelength of 1500nm represents.
Near infrared ray absorbing can be measured with following method the stability of heat, humidity, light.
Hear resistance, moisture-proof are by the near-infrared absorbing plate is placed 480 hours in 80 ℃, the baking oven of 100% relative humidity after, use spectrophotometer (1000nm) to measure the near infrared ray absorbing energy once more.Its keeping quality, the evaluation of result of calculating with following formula.
Light resistance is by after the near-infrared absorbing plate is penetrated 200 hours with UV testing machine (the fast light testing machine of the super promotion of big Japanese plastics (strain) system) illumination, uses spectrophotometer (1000nm) to measure near infrared ray absorbing once more.The evaluation of result that its keeping quality is calculated with following formula.
Heat endurance is that layered product is placed on the Geer-Evans-oven 20 minutes that is set at 230 ℃, measures the sample tone variations that obtains with Japanese electric look (strain) system colour difference meter, obtains aberration (Δ E) with L, a, b method and judges by following mode.
◎: outstanding
Zero: good
△: do not have burn (the yellow variation greatly)
*: burn is arranged
Measure the stability of polycarbonate-based resin with following method to light.
After the near-infrared absorbing plate penetrated 200 hours with UV testing machine (big Japanese plastics (strain) system super promote fast light testing machine) illumination, measure the variation of tone variations and hot strength.Calculate the conservation rate of hot strength with following formula.
Embodiment 1～14
By proportioning shown in the table 1 and weight ratio the copper sulfide of average grain diameter 8 μ m is added in the polycarbonate resin of 100 parts of weight, mixed 20 minutes with barrel mixer, by 40mm φ single lead screw ex truding briquetting machine 300 ℃ down mixing after, make the thick plate of 0.7mm, after extruding immediately with the thick methacrylic resin film lamination of the 0.05mm that squeezes out, become the thick layered product of 0.75mm.The chill-roll temperature that is used for lamination is 120 ℃.Then be configured as the plate of spacing 32mm, the dark 9mm of paddy with the waveform machine.
The laminate that mensuration obtains see through spectrum, represented the result among 800～2000nm in the table 4, can find out that the absorbent properties of near infrared region are good.Though this resin plate can see through visual field light preferably, has the unexistent good near infrared region absorbent properties of common polycarbonate resin plate.
Embodiment 15～27
The copper sulfide of average grain diameter 8 μ m is added in the metha crylic resin of 100 parts of weight with proportioning and weight ratio that table 2 is represented, after mixing 20 minutes with barrel mixer, obtain the thick film of 0.05mm [1] at 230 ℃ after mixing by 40mm φ single lead screw ex truding briquetting machine.In addition, by 40mm φ single lead screw ex truding briquetting machine 300 ℃ down mixing after, make the thick polycarbonate resin plate of 0.7mm, after just having squeezed out immediately lamination [1] obtain the thick layered product of 0.75mm.120 ℃ of temperature that are used for the chill roll of lamination are configured as the plate that obtains the plate of spacing 32mm, the dark 9mm of paddy with the waveform processing machine.
Measure the spectrum that sees through of resulting plate, table 5 is illustrated in the result among 800～2000nm, and the absorbent properties of near infrared region are good.
Comparative example 1～4
Combination matching and the condition represented with table 3, add in the polycarbonate resin by the method identical with embodiment 1～14 after, make the thick plate of 0.7mm, the methacrylic resin film that lamination 0.05mm is thick immediately after the extruding obtains the 0.75mm layered product.
The plate that mensuration obtains see through spectrum, table 5 is illustrated in the result among 800～2000nm, all has only the near infrared ray absorbing energy below 30%.
Comparative example 5～7
Combination matching and the condition represented with table 3, by the method same with embodiment 15～27, add in 100 parts of weight methacrylic acid resins after, obtain the thick film of 0.05mm [II].In addition, with 40mm φ extrusion moulding machine 300 ℃ mixing down after, make the thick polycarbonate resin plate of 0.7mm, after the extruding, lamination [II] obtains the thick layered product of 0.75mm immediately.
The plate that mensuration obtains see through spectrum, represented result in the table 5 at 800～2000nm place, all have only the near infrared ray absorbing energy below 30%.
Table 1
The thermoplastic resin prescription
| Embodiment No. | Prescription (weight ratio) | |||
| Copper sulfide | Thiourea derivative | Amide derivatives | Resin | |
| 1 | 0.06 | - - | - - | PC 100 |
| 2 | 0.1 | - - | - - | PC 100 |
| 3 | 1.0 | - - | - - | PC 100 |
| 4 | 0.1 | 1,3-rhenocure CA 0.06 | - - | PC 100 |
| 5 | 1.0 | 1,3-rhenocure CA 0.06 | - - | PC 100 |
| 6 | 0.1 | 1,3-rhenocure CA 0.1 | - - | PC 100 |
| 7 | 0.1 | 1,3-diethyl thiourea 0.06 | - - | PC 100 |
| 8 | 0.1 | 1,3-dilauryl thiocarbamide 0.06 | - - | PC 100 |
| 9 | 0.1 | - - | N-phenyl stearmide 0.06 | PC 100 |
| 10 | 0.1 | - - | N-phenyl stearmide 0.1 | PC 100 |
| 11 | 0.1 | - - | N-phenylbenzamaide 0.06 | PC 100 |
| 12 | 0.1 | 1,3-rhenocure CA 0.03 | N-phenyl stearmide 0.03 | PC 100 |
| 13 | 0.1 | 1,3-rhenocure CA 0.05 | N-phenyl stearmide 0.05 | PC 100 |
| 14 | 0.1 | 1,3-rhenocure CA 0.03 | N-phenylbenzamaide 0.03 | PC 100 |
PC: the grand E-2000 of the excellent skin of Mitsubishi's gas chemistry society's system
Table 2
The thermoplastic resin prescription
| Embodiment No. | Prescription (weight ratio) | |||
| Copper sulfide | Thiourea derivative | Amide derivatives | Resin | |
| 15 | 1.0 | - - | - - | PMMA 100 |
| 16 | 10 | - - | - - | PMMA 100 |
| 17 | 1.0 | 1,3-rhenocure CA 0.6 | - - | PMMA 100 |
| 18 | 10 | 1,3-rhenocure CA 0.6 | - - | PMMA 100 |
| 19 | 1.0 | 1,3-rhenocure CA 1.0 | - - | PMMA 100 |
| 20 | 1.0 | 1,3-diethyl thiourea 0.6 | - - | PMMA 100 |
| 21 | 1.0 | 1,3-dilauryl thiocarbamide 0.6 | - - | PMMA 100 |
| 22 | 1.0 | - - | N-phenyl stearmide 0.6 | PMMA 100 |
| 23 | 1.0 | - - | N-phenyl stearmide 1.0 | PMMA 100 |
| 24 | 1.0 | - - | N-phenylbenzamaide 0.6 | PMMA 100 |
| 25 | 1.0 | 1,3-rhenocure CA 0.3 | N-phenyl stearmide 0.3 | PMMA 100 |
| 26 | 1.0 | 1,3-rhenocure CA 0.5 | N-phenyl stearmide 0.5 | PMMA 100 |
| 27 | 1.0 | 1,3-rhenocure CA 0.3 | N-phenylbenzamaide 0.3 | PMMA 100 |
PMMA: the system Acree bit IR H-70 of mitsubishi rayon society
Table 3
The thermoplastic resin prescription
| Comparative example No | Prescription (weight ratio) | ||
| Copper sulfide/metallic copper | Thiourea derivative/amide derivatives | Resin | |
| 1 | Copper sulfide *1 0.005 | - - | PC 100 |
| 2 | The metallic copper powder *1 0.1 | - - | PC 100 |
| 3 | - - | 1,3-rhenocure CA 0.06 | PC 100 |
| 4 | - - | N-phenyl stearmide 0.06 | PC 100 |
| 5 | Copper sulfide *1 0.05 | - - | PMMA 100 |
| 6 | - - | 1,3-rhenocure CA 0.6 | PMMA 100 |
| 7 | - - | N-phenyl stearmide 0.6 | PMMA 100 |
* 1) average grain diameter: 8 μ m
Table 4
The evaluation result of near infrared ray absorbing resin
| Unit | Embodiment | ||||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | ||
| Near infrared ray absorbing | - | 62 | 80 | 84 | 92 | 95 | 97 | 94 | 93 | 94 | 97 | 94 | 93 | 97 | 95 |
| Hear resistance, moisture-proof | ％ | 92 | 92 | 91 | 80 | 87 | 82 | 80 | 88 | 82 | 89 | 87 | 89 | 88 | 87 |
| Light resistance | ％ | 91 | 87 | 87 | 82 | 86 | 82 | 82 | 83 | 82 | 81 | 81 | 86 | 86 | 83 |
| Heat endurance | △E | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
Table 5
The evaluation result of near infrared ray absorbing resin
| Unit | Embodiment | Comparative example | |||||||||||||||||||
| 15 | 16 | 17 | 18 | 19 | 20 | 21 | 22 | 23 | 24 | 25 | 26 | 27 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | ||
| Near infrared ray absorbing | - | 94 | 95 | 82 | 84 | 94 | 96 | 97 | 95 | 94 | 96 | 97 | 95 | 96 | 20 | 20 | 4 | 6 | 20 | 7 | 9 |
| Hear resistance, moisture-proof | ％ | 88 | 89 | 85 | 86 | 81 | 87 | 86 | 86 | 81 | 88 | 87 | 86 | 88 | - | - | - | - | - | - | - |
| Light resistance | ％ | 86 | 85 | 83 | 84 | 78 | 86 | 82 | 86 | 86 | 86 | 88 | 82 | 87 | - | - | - | - | - | - | - |
| Heat endurance | △E | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
Embodiment 28
Penetrate layered product that embodiment 2 obtains after 200 hours with UV testing machine (big Japanese plastics (strain) system super promote fast light testing machine) illumination, the variation of jaundice almost appears on as the polycarbonate resin of substrate in the result.In addition, the conservation rate of hot strength is 92%.
Can judge and use the methacrylic resin film for ultraviolet blocking effect height.
Comparative example 8
After the plate that obtains for obtaining the methacrylic resin film among the lamination embodiment 2 was not penetrated 200 hours with UV testing machine (big Japanese plastics (strain) system super promote fast light testing machine) illumination, the result was as the polycarbonate resin flavescence seriously of substrate.The conservation rate of hot strength is 35% in addition, and this explanation is because action of ultraviolet radiation makes polycarbonate resin be subjected to the aging of certain degree.
Can find out from table 4.5 polycarbonate resin plate of the copper sulfide that mixed can become the very strong resin laminate of near infrared ray absorbing.In addition, its near infrared ray absorbing also descends under heating, humidification or conditions of exposure hardly, for using and to preserve the stability of environmental change very high.
The metallic copper that mixes individually, the polycarbonate-based resin plate of copper sulfide, thiourea compound or the thioamide compound of the addition outside above-mentioned that perhaps mixes does not demonstrate near infrared absorbent properties in fact.
As mentioned above, polycarbonate-based resin laminate of near-infrared absorbing of the present invention and plate form body, wild effect such as do not fade, also not because this photochromism of fading of opening in dark place for a long time and occurring, shown good near infrared ray absorbing energy, had very strong absorbability in the near infrared region of 800～2000nm.Utilize these character, the aura material of optical filtering sheet, heat absorptivity is being provided, industrial product aspect such as windproof, the rain of the platform outside the room, balcony, bicycle shed, arcade, garage etc. and daylighting roof, daylighting sidewall, skylight is of great use.Owing to have heat insulation effect, also can be used to prevent to emit heat in addition from greenhouse.
Although product of the present invention contains metal, because seldom painted, so contain the layered product of these products, the outward appearance of its formed body is very beautiful.
Claims (7)
1. the polycarbonate-based resin laminate that has good near infrared ray absorbing energy, it is characterized in that it is to be formed by lamination metha crylic resin molding on polycarbonate-based resin plate, constituting of polycarbonate-based resin plate:, contain the copper sulfide of 0.01～5 part of weight with respect to the polycarbonate-based resin of per 100 parts of weight.
According to the near infrared ray absorbing of claim 1 can be good polycarbonate-based resin laminate, it is characterized in that it is by lamination metha crylic resin molding on the polycarbonate-based resin plate of at least a kind of thioamide derivatives of the compound that is selected from following general formula (II) of at least a thiourea derivative of the compound that contains the following general formula of being selected from of 0.001～1 part of weight (1) and/or 0.001-1 part weight and constitute
Wherein, R
1, R
2, R
3Expression is selected from the univalent perssad of hydrogen, alkyl, cycloalkyl, aryl, aralkyl and five yuan or hexa-atomic heterocyclic radical, and each group also can have the substituting group more than 1, R
1And R
2Perhaps R
2And R
3Also can be connected to form ring;
Wherein, R
4, R
5Expression is selected from the univalent perssad of hydrogen, alkyl, alkenyl, cycloalkyl, aryl, aralkyl and five yuan or hexa-member heterocycle base, perhaps R
5The expression alkoxyl, each group can have the substituting group more than 1, R
4And R
5Also can be connected to form ring.
According in the claim 1～2 any one have good near infrared ray absorbing can polycarbonate-based resin laminate, the particle diameter that it is characterized in that copper sulfide on average below 12 μ m, does not have the above particle of 20 μ m in fact.
4. the polycarbonate-based resin laminate that has good near infrared ray absorbing energy, it is characterized in that it is to be pressed on the polycarbonate-based resin plate by the metha crylic resin film layer to form, and the constituting of methacrylic acid resin film:, contain 0.1～50 part of weight copper sulfide with respect to the metha crylic resin of per 100 parts of weight.
According to the good near infrared ray absorbing of having of claim 4 can polycarbonate-based resin laminate, it is characterized in that it is pressed on the polycarbonate-based resin plate by the metha crylic resin film layer of a kind of thioamide derivatives in the compound that is selected from following general formula (II) of a kind of thiourea derivative and/or 0.01～10 part of weight in the compound that contains the following general formula of being selected from of 0.01～10 part of weight (I) and constitutes at least at least
Wherein, R
1, R
2, R
3Expression is selected from the univalent perssad of hydrogen, alkyl, cycloalkyl, aryl, aralkyl and five yuan or hexa-atomic heterocyclic radical, and each group also can have the substituting group more than 1, R
1And R
2Perhaps R
2And R
3Also can be connected to form ring;
Wherein, R
4, R
5Expression is selected from the univalent perssad of hydrogen, alkyl, alkenyl, cycloalkyl, aryl, aralkyl and five yuan or hexa-member heterocycle base, perhaps R
5The expression alkoxyl, each group can have the substituting group more than 1, R
4And R
5Also can be connected to form ring.
According in the claim 4～5 any one have good near infrared ray absorbing can polycarbonate-based resin laminate, the particle diameter that it is characterized in that copper sulfide on average below 12 μ m, does not have the above particle of 20 μ m in fact.
Will by in the claim 1～6 any one have good near infrared ray absorbing can polycarbonate-based resin laminate be configured as the tabular or special-shaped section shape of waveform and the polycarbonate-based resin laminated formed body of near-infrared absorbing that constitutes.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP103960/93 | 1993-04-30 | ||
| JP10396093A JP3195854B2 (en) | 1993-04-30 | 1993-04-30 | Near-infrared absorbing polycarbonate resin laminate and molded product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1094354A CN1094354A (en) | 1994-11-02 |
| CN1054803C true CN1054803C (en) | 2000-07-26 |
Family
ID=14367963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94104645A Expired - Fee Related CN1054803C (en) | 1993-04-30 | 1994-04-29 | Polycarbonic acid ester resin layered products absorbing near-infrared and formed products made of same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3195854B2 (en) |
| KR (1) | KR960008303B1 (en) |
| CN (1) | CN1054803C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010000559A1 (en) * | 2010-02-25 | 2011-08-25 | Bundesdruckerei GmbH, 10969 | Process for the verification of security or value documents with an anthraquinone dye |
| WO2013021848A1 (en) * | 2011-08-05 | 2013-02-14 | 三菱エンジニアリングプラスチックス株式会社 | Panel and panel installation structure |
| WO2014115965A1 (en) * | 2013-01-22 | 2014-07-31 | (주)비에스써포트 | Plastic molded product comprising copper-based compound microparticles and preparation method therefor |
| WO2014129291A1 (en) * | 2013-02-19 | 2014-08-28 | 富士フイルム株式会社 | Near-infrared-absorbing composition, near-infrared cut-off filter using same, camera module, and manufacturing method therefor |
| CN103274446B (en) * | 2013-04-16 | 2015-01-14 | 宁波大学 | Nano copper sulphide/barium sulphide-containing isolated membrane and preparation method thereof |
| TWI651333B (en) * | 2013-09-20 | 2019-02-21 | 可樂麗股份有限公司 | Resin composition and molded article thereof |
| CN104927333B (en) * | 2015-07-15 | 2016-11-02 | 上海锦湖日丽塑料有限公司 | A kind of polycarbonate compositions of applicable laser welding and preparation method thereof |
| CN105219091A (en) * | 2015-10-20 | 2016-01-06 | 东华大学 | A kind of copper sulfide nano material is preparing the application near infrared shielding thermal isolation film |
| CN108329862B (en) * | 2018-02-11 | 2021-01-29 | 江苏斯迪克新材料科技股份有限公司 | Mirror surface explosion-proof membrane |
| EP3831600A4 (en) * | 2018-07-27 | 2022-05-04 | Kuraray Co., Ltd. | Infrared light shielding multilayer sheet and method for producing same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4830666A (en) * | 1971-08-25 | 1973-04-23 | ||
| US4321299A (en) * | 1977-09-15 | 1982-03-23 | Nasa | Strong thin membrane structure for use as solar sail comprising substrate with reflective coating on one surface and an infra red emissivity increasing coating on the other surface |
| JPS6241266A (en) * | 1985-08-19 | 1987-02-23 | Asahi Chem Ind Co Ltd | Electrically conductive high-molecular material |
| JPH04189539A (en) * | 1990-11-26 | 1992-07-08 | Dainippon Plastics Co Ltd | Plastic laminated corrugated sheet absorbing near infrared ray |
-
1993
- 1993-04-30 JP JP10396093A patent/JP3195854B2/en not_active Expired - Fee Related
-
1994
- 1994-04-27 KR KR94008979A patent/KR960008303B1/en not_active IP Right Cessation
- 1994-04-29 CN CN94104645A patent/CN1054803C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4830666A (en) * | 1971-08-25 | 1973-04-23 | ||
| US4321299A (en) * | 1977-09-15 | 1982-03-23 | Nasa | Strong thin membrane structure for use as solar sail comprising substrate with reflective coating on one surface and an infra red emissivity increasing coating on the other surface |
| JPS6241266A (en) * | 1985-08-19 | 1987-02-23 | Asahi Chem Ind Co Ltd | Electrically conductive high-molecular material |
| JPH04189539A (en) * | 1990-11-26 | 1992-07-08 | Dainippon Plastics Co Ltd | Plastic laminated corrugated sheet absorbing near infrared ray |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1094354A (en) | 1994-11-02 |
| JP3195854B2 (en) | 2001-08-06 |
| KR960008303B1 (en) | 1996-06-24 |
| JPH06312489A (en) | 1994-11-08 |
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