Polymer film composition, polymer film, and laminate

Abstract

The invention provides a polymer film composition, a polymer film and a laminate. The polymeric membrane composition is prepared from the following components in parts by weight: 100 parts of matrix resin, 0.01 to 5 parts of photoacid generator and 0.01 to 5 parts of acid-sensitive dye. According to the polymeric membrane composition disclosed by the invention, the photo-acid generator and the acid-sensitive dye are introduced, so that patterning and colorization can be realized on the polymeric membrane. Especially for the application scene of lamination and crosslinking, the polymeric membrane composition can be patterned after lamination and crosslinking, so that the polymeric membrane composition is higher in universality.

Description

Technical Field

[0001] The present invention relates to the technical field of glass interlayer adhesive films, and in particular to a polymer film composition, a polymer film and a laminate. Background Art

[0002] The application scenarios of polymer films made of polymers are constantly expanding, from the initial packaging films to photovoltaic films, automotive glass films and other fields. Now, patterning and coloring on polymer films are widely concerned as new demands. For example, in the automotive field, adding colors and patterns to glass interlayer films to make atmosphere glass; in the photovoltaic field, the white patterning of the film in the gaps between cells can improve the power generation efficiency of solar cells, and the patterned film can meet the needs of integrated and beautiful photovoltaic buildings. Therefore, patterning and coloring of polymer films has great application prospects.

[0003] At present, there are generally two technical solutions to achieve patterning and coloring of polymer films. One technical solution is to transfer the pattern onto glass that matches the polymer film, but this method requires improving the glass production process (such as preparing patterned alcohol paper in advance, transferring it to the glass body, and finally tempering it). This process is not only complex and costly, but also not universal; another technical solution is to use a multi-layer polymer film composite method. However, this method not only needs to consider bonding the multi-layer structure, but also needs to consider the matching problems between layers (such as torque, elongation at break, etc.). If subsequent lamination and cross-linking are required, the fluidity of the polymer film is poor or the surface is uneven during lamination, which will make the pattern display uneven, resulting in poor display effect. In addition, the above processes all have the problems of complex process and high cost. Summary of the invention

[0004] The main purpose of the present invention is to provide a polymer film composition, a polymer film and a laminate, so as to solve the problems of complex process and high cost in the process of realizing patterning and colorization on the polymer film in the prior art.

[0005] To achieve the above object, according to one aspect of the present invention, a polymer film composition is provided, which comprises, by weight: 100 parts of a base resin, 0.01 to 5 parts of a photoacid generator, and 0.01 to 5 parts of an acid-sensitive dye.

[0006] Furthermore, the molar ratio of the photoacid generator to the acid-sensitive dye is 0.1 to 50:1, preferably 0.5 to 10:1.

[0007] Further, the photoacid generator is selected from any one or more of diazonium salt photoacid generators, onium salt photoacid generators, sulfonate photoacid generators, organic polyhalogen compound photoacid generators, Ru(II) complex photoacid generators based on 4,4'-bis(chloromethyl)-2,2'-bipyridine, and thioxanthone sulfonate photoacid generators; and / or, the diazonium salt photoacid generator is selected from any one or more of diazosulfate, diazohydrochloride, diazosulfonate, diazofluoroborate, and diazofluorophosphate; and / or, the onium salt photoacid generator is selected from tert-butylphenyl iodonium salt, perfluorooctanesulfonic acid, triphenylsulfonium perfluorooctanesulfonic acid, Any one or more of fluorobutanesulfonic acid and triphenylsulfonium trifluorosulfonic acid; and / or, the sulfonate photoacid generator is selected from any one or more of N-toluenesulfonyloxyphthalimide, N-trifluoromethanesulfonyloxysuccinimide, N-trifluoromethanesulfonyloxynaphthalimide, dinitrobenzyl p-toluenesulfonate and p-toluenesulfonate of α-hydroxymethylbenzoin; and / or, the organic polyhalogen compound photoacid generator is selected from any one or more of trichloroacetophenone, tribromomethylphenylsulfone, 4-phenoxydichloroacetophenone and 4,6-bis(trichloromethyl)-1,3,5-triazine derivatives.

[0008] Furthermore, the acid-sensitive dye is selected from any one or more of triphenylmethane compounds, phenothiazine compounds and fluoran compounds; and / or the triphenylmethane compound is crystal violet lactone and / or phenolphthalein; and / or the phenothiazine compound is benzoyl leuco-methylene blue; and / or the fluoran compound is 2-phenylamino-3-methyl-6-diethylaminofluoran and / or 2-phenylamino-3-methyl-6-dibutylaminofluoran.

[0009] Furthermore, under the ultraviolet light wavelength of 350-450nm, the photoacid generator is a diazonium salt photoacid generator, the acid-sensitive dye is a triphenylmethane compound, and the molar ratio of the diazonium salt photoacid generator to the triphenylmethane compound is 1-50:1.

[0010] Furthermore, under the ultraviolet light wavelength of 150-300nm, the photoacid generator is a sulfonate photoacid generator, the acid-sensitive dye is a phenothiazine compound, and the molar ratio of the sulfonate photoacid generator to the phenothiazine compound is 0.1-30:1.

[0011] Furthermore, under the ultraviolet light wavelength of 100-300nm, the photoacid generator is an onium salt photoacid generator, the acid-sensitive dye is a fluorane compound, and the molar ratio of the onium salt photoacid generator to the fluorane compound is 1-20:1.

[0012] Further, the matrix resin is selected from any one or more of ethylene-vinyl acetate copolymer, ethylene-α-olefin copolymer, polyvinyl butyral, polyvinyl chloride and polyurethane; and / or, the polymer film composition further comprises any one or more of a silane coupling agent and a light stabilizer; preferably, the silane coupling agent is selected from γ-glycidyloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(2-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane. any one or more of alkane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane; preferably, the light stabilizer is selected from 1,5,8,12-tetrakis[4,6-bis(N-butyl-N-1,2,2,6,6-pentamethyl-4-piperidinylamino)-1,3,5-triazine-2-yl]-1,5,8,12-tetraazadodecane, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) Sebacate, poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinylethanol) succinate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino], 1,6-hexanediamine N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl), 2,4, Any one or more of 6-trichloro-1,3,5-triazine, poly(6-morpholinyl-5-triazine-2,4-diyl)(2,2,6,6-tetramethylpiperidinyl)iminohexamethylene[(2,2,6,6-tetramethylpiperidinyl)-imino], 2,2,6,6-tetramethyl-4-piperidinyl stearate and N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-N,N'-dialdehyde hexamethylenediamine; and / or, the polymer film composition further comprises an auxiliary agent; preferably, the auxiliary agent is selected from any one or more of a crosslinking agent, a co-crosslinking agent and an antioxidant.

[0013] According to another aspect of the present invention, a polymer film is provided, which is obtained by sequentially mixing and melt extruding a polymer film composition, and the polymer film composition is the above-mentioned polymer film composition.

[0014] According to another aspect of the present invention, there is provided a laminate comprising at least two layers of glass and at least one layer of polymer film, wherein the polymer film is the above-mentioned polymer film.

[0015] By applying the technical solution of the present invention, the polymer film composition of the present application introduces a photoacid generator and an acid-sensitive dye, which can realize patterning and colorization on the polymer film. The photoacid generator will decompose and generate hydrogen ions (H + ), while acid-sensitive dyes have no color under alkaline or neutral conditions, but when reacted with H generated by a photoacid generator + After combination, different colors can be produced. At the same time, by changing the amount of photoacid generator added, the depth of the color can be changed; by changing the type of acid-sensitive dye, the type of color can be changed. Therefore, the present invention controls the position of ultraviolet light irradiation, so that different patterns and colors can be produced at specific positions of the polymer film. Especially for the application scenario of lamination and cross-linking, the polymer film composition of the present invention can be patterned after lamination and cross-linking, so the polymer film composition of the present invention is more universal. DETAILED DESCRIPTION

[0016] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0017] As analyzed in the background technology of this application, the prior art has problems such as complex processes and high costs for patterning and coloring on polymer films. In order to solve the above problems, this application provides a polymer film composition, a polymer film and a laminate.

[0018] In a typical embodiment of the present application, a polymer film composition is provided, which comprises, by weight, 100 parts of a base resin, 0.01 to 5 parts of a photoacid generator, and 0.01 to 5 parts of an acid-sensitive dye.

[0019] The polymer film composition of the present application introduces a photoacid generator and an acid-sensitive dye, which can realize patterning and colorization on the polymer film. The photoacid generator decomposes to generate hydrogen ions (H + ), while acid-sensitive dyes have no color under alkaline or neutral conditions, but when reacted with H generated by a photoacid generator + After combination, different colors can be produced. At the same time, by changing the amount of photoacid generator added, the depth of the color can be changed; by changing the type of acid-sensitive dye, the type of color can be changed. Therefore, the present invention controls the position of ultraviolet light irradiation, so that different patterns and colors can be produced at specific positions of the polymer film. Especially for the application scenario of lamination and cross-linking, the polymer film composition of the present invention can be patterned after lamination and cross-linking, so the polymer film composition of the present invention is more universal.

[0020] In one embodiment of the present application, the molar ratio of the photoacid generator to the acid-sensitive dye is 0.1 to 50:1, preferably 0.5 to 10:1.

[0021] It is preferred to control the molar ratio of the photoacid generator to the acid-sensitive dye within the above range, which helps the photoacid generator to decompose under ultraviolet light to produce an appropriate amount of H + , which helps the acid-sensitive dye to + Combined, this in turn helps produce different colors.

[0022] In one embodiment of the present application, the photoacid generator is selected from any one or more of diazonium salt photoacid generators, onium salt photoacid generators, sulfonate photoacid generators, organic polyhalogen compound photoacid generators, Ru(II) complex photoacid generators based on 4,4'-bis(chloromethyl)-2,2'-bipyridine, and thioxanthone sulfonate photoacid generators; and / or, the diazonium salt photoacid generator is selected from any one or more of diazonium sulfate, diazonium hydrochloride, diazonium sulfonate, diazonium fluoroborate, and diazonium fluorophosphate; preferably, the diazonium sulfate is benzene diazonium sulfate and / or p-toluene diazonium sulfate, preferably, the diazonium hydrochloride is benzene diazonium hydrochloride and / or p-toluene diazonium hydrochloride, preferably, the diazosulfonate is benzene diazonium sulfonate and / or p-toluene diazonium sulfonate, and preferably, the diazonium fluoroborate is benzene diazonium fluoroborate and / or p-toluene diazonium phosphate. Toluene diazonium fluoroborate, preferably the diazonium fluorophosphate is benzene diazonium fluorophosphate and / or p-toluene diazonium fluorophosphate; and / or, the onium salt photoacid generator is selected from any one or more of tert-butylphenyl iodonium salt perfluorooctane sulfonic acid, triphenylsulfonium perfluorobutane sulfonic acid and triphenylsulfonium trifluorosulfonic acid; and / or, the sulfonate photoacid generator is selected from any one or more of N-p-toluenesulfonyloxyphthalimide, N-trifluoromethanesulfonyloxysuccinimide, N-trifluoromethanesulfonyloxynaphthalimide, dinitrobenzyl p-toluenesulfonate and p-toluenesulfonate of α-hydroxymethylbenzoin; and / or, the organic polyhalogen compound photoacid generator is selected from any one or more of trichloroacetophenone, tribromomethylphenyl sulfone, 4-phenoxydichloroacetophenone and 4,6-bis(trichloromethyl)-1,3,5-triazine derivatives.

[0023] It is preferred to control the type of the photoacid generator within the above range, which helps to promote the decomposition of the photoacid generator under ultraviolet light of different wavelengths to produce H + , which helps to improve its compatibility with acid-sensitive dyes and form richer colors and patterns under different ultraviolet light irradiation.

[0024] In one embodiment of the present application, the acid-sensitive dye is selected from any one or more of triphenylmethane compounds, phenothiazine compounds and fluoran compounds; and / or the triphenylmethane compound is crystal violet lactone and / or phenolphthalein; and / or the phenothiazine compound is benzoyl leuco-methylene blue; and / or the fluoran compound is 2-phenylamino-3-methyl-6-diethylaminofluoran and / or 2-phenylamino-3-methyl-6-dibutylaminofluoran.

[0025] It is preferred to control the type of acid-sensitive dye within the above range, which helps to improve its compatibility with different photoacid generators.

[0026] In one embodiment of the present application, under ultraviolet light wavelength of 350-450nm, the photoacid generator is a diazonium photoacid generator, the acid-sensitive dye is a triphenylmethane compound, and the molar ratio of the diazonium photoacid generator to the triphenylmethane compound is 1-50:1.

[0027] It is preferred that the types and molar ratios of the photoacid generator and the acid-sensitive dye are within the above ranges, which helps the photoacid generator to generate H under ultraviolet light wavelengths of 350 to 450 nm. + Diazonium salt-based photoacid generators are most sensitive to this wavelength, which helps to generate H more efficiently. + The acid-sensitive dye triphenylmethane compounds and diazonium salt photoacid generators are more compatible, so that patterns and colors can be produced more efficiently and controllably, thereby making the color development effect of polymer film products better.

[0028] In one embodiment of the present application, under an ultraviolet light wavelength of 150 to 300 nm, the photoacid generator is a sulfonate photoacid generator, the acid-sensitive dye is a phenothiazine compound, and the molar ratio of the sulfonate photoacid generator to the phenothiazine compound is 0.1 to 30:1.

[0029] It is preferred that the types and molar ratios of the photoacid generator and the acid-sensitive dye are within the above ranges, which helps the photoacid generator to generate H under ultraviolet light wavelengths of 150 to 300 nm. + Under the action of light, the sulfonate photoacid generator releases acid, and the phenothiazine compound reacts with the released acid to form a complex. This complex helps to improve the photosensitivity and film-forming effect of the polymer film.

[0030] In one embodiment of the present application, under ultraviolet light wavelength of 100-300nm, the photoacid generator is an onium salt photoacid generator, the acid-sensitive dye is a fluorane compound, and the molar ratio of the onium salt photoacid generator to the fluorane compound is 1-20:1.

[0031] It is preferred that the types and molar ratios of the photoacid generator and the acid-sensitive dye are within the above ranges, which helps the photoacid generator to generate H under ultraviolet light wavelengths of 100 to 300 nm. + Under light conditions, salt photoacid generators will release acidic substances, stimulating the cleavage of the lactone ring in the molecular structure of fluorane compounds, thereby producing color. In addition, the reduction of molecular cohesive energy helps to improve the processing performance of polymer films. The matching of onium salt photoacid generators and fluorane compounds helps to improve the processing efficiency and performance of polymer films.

[0032] In one embodiment of the present application, the matrix resin is selected from any one or more of ethylene-vinyl acetate copolymer, ethylene-α-olefin copolymer, polyvinyl butyral, polyvinyl chloride and polyurethane; and / or, the polymer film composition further includes any one or more of a silane coupling agent and a light stabilizer; preferably, the silane coupling agent is selected from γ-glycidyloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(2-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, 3- Any one or more of mercaptopropyl trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane and N-(β-aminoethyl)-γ-aminopropyl triethoxysilane; preferably, the light stabilizer is selected from 1,5,8,12-tetrakis[4,6-bis(N-butyl-N-1,2,2,6,6-pentamethyl-4-piperidinylamino)-1,3,5-triazine-2-yl]-1,5,8,12-tetraazadodecane, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinylamino)-1,3,5-triazine-2-yl]-1,5,8,12-tetraazadodecane succinic acid (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinylethanol) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino], 1,6-hexanediamine N,N'-bis(2,2,6,6-tetramethyl-4 -piperidinyl), 2,4,6-trichloro-1,3,5-triazine, poly(6-morpholinyl-5-triazine-2,4-diyl)(2,2,6,6-tetramethylpiperidinyl)iminohexamethylene[(2,2,6,6-tetramethylpiperidinyl)-imino], 2,2,6,6-tetramethyl-4-piperidinyl stearate and N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-N,N'-dialdehyde hexamethylenediamine; preferably, the weight portion of the silane coupling agent is 0.1 to 5 parts, and the weight portion of the light stabilizer is preferably 0.1 to 5 parts; and / or, the polymer film composition further comprises an auxiliary agent; preferably, the auxiliary agent is selected from any one or more of a crosslinking agent, a co-crosslinking agent and an antioxidant; wherein, the crosslinking agent is preferably selected from tert-amyl peroxybenzoate, tert-butyl peroxybenzoate, di-tert-butyl peroxide, 1,1-di-tert-butyl peroxy-3,3,5-trimethylcyclohexane, tert-butyl peroxyisopropyl carbonate, tert-amyl peroxyacetate, tert-amyl peroxy (2-ethylhexyl) carbonate, 3,5,5- Any one or more of trimethylhexanoate, 1,1-di-tert-butylperoxycyclohexane, 2,2-bis(tert-butylperoxide)butane, tert-butylperoxypentylacetate, 1,1-di(tert-amylperoxy)cyclohexane and 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, and / or, the auxiliary crosslinking agent is selected from triallyl cyanurate, trimethylolpropane trimethacrylate, triallyl isocyanurate, ethoxylated pentaerythritol tetraacrylate, ethoxylated trimethylolpropane trimethacrylate, any one or more of propane triacrylate, pentaerythritol tetraacrylate and pentaerythritol triacrylate, and / or the antioxidant is selected from pentaerythritol tetra(β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), isooctyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, 2,6-di-tert-butyl-p-cresol, tris(2,4-di-tert-butylphenyl)phosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite and 2,2'-methylenebis(4-methyl-6-tert-butylphenol) any one or more thereof; preferably, the weight proportion of the auxiliary agent is 0.1 to 5 parts. .

[0033] The type of the preferred base resin is within the above range, which helps to improve the processing performance of the polymer film composition, thereby achieving a better film-forming effect; the type of the preferred auxiliary agent is within the above range, which helps to make the auxiliary agent and the base resin, acid generator, and acid-sensitive dye more matched, thereby making the overall performance of the polymer film product better and achieving a better color development effect.

[0034] In another typical embodiment of the present application, a polymer film is provided, which is obtained by sequentially mixing and melt extruding a polymer film composition, and the polymer film composition is the above-mentioned polymer film composition.

[0035] The polymer film obtained by mixing and melt-extruding the polymer film composition in sequence can produce patterns and colors at specific locations and has stronger universality.

[0036] In another typical embodiment of the present application, a laminate is provided, comprising at least two layers of glass and at least one layer of polymer film, wherein the polymer film is the polymer film described above.

[0037] The laminate including the polymer film can produce patterns and colors at specific positions by simply changing the position of ultraviolet light. The glass and the polymer film are cross-linked and bonded by thermal curing, and the thermal curing temperature is preferably 130 to 170°C and the thermal curing time is 10 to 30 minutes. The laminate can be a laminated glass or double-glass photovoltaic module.

[0038] Among them, it is preferred to obtain double-layer glass by stacking and thermally curing the front layer of glass, the polymer film and the rear layer of glass in sequence. Patterns and colors can be generated at specific locations simply by changing the position of the ultraviolet light, which is particularly suitable for lamination and cross-linking application scenarios.

[0039] The beneficial effects of the present application will be further illustrated below in conjunction with embodiments.

[0040] Example 1

[0041] The polymer film composition comprises, by weight, 100 parts of a matrix resin ethylene-vinyl acetate copolymer, 0.5 parts of a silane coupling agent γ-methacryloxypropyl trimethoxysilane, 0.6 parts of a light stabilizer 2,2,6,6-tetramethyl-4-piperidinyl stearate, 0.8 parts of a photoacid generator triphenylsulfonium perfluorobutane sulfonic acid, 1.0 parts of an acid-sensitive dye 2-phenylamino-3-methyl-6-dibutylaminofluorane (the molar ratio of the photoacid generator to the acid-sensitive dye is 0.76:1), 0.5 parts of a crosslinking agent tert-amyl peroxy (2-ethylhexyl) carbonate, 0.8 parts of an auxiliary crosslinking agent triallyl isocyanurate and 0.3 parts of an antioxidant tetrakis (β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate) pentaerythritol. The above components are mixed, cast and extruded at 90°C, cooled, slit and rolled up to obtain a polymer film.

[0042] The glass, polymer film, and glass are stacked in the order of lamination under a laminator at a lamination condition of 145°C / 16min. After the lamination is completed, ultraviolet rays with a wavelength of 248nm are directed at the position where patterns and colors need to be produced to obtain laminated glass with colors and patterns.

[0043] Example 2

[0044] The difference from Example 1 is that the wavelength of the ultraviolet light is 100 nm, and finally a polymer film and laminated glass are obtained.

[0045] Example 3

[0046] The difference from Example 1 is that the wavelength of the ultraviolet light is 300 nm, and finally a polymer film and laminated glass are obtained.

[0047] Example 4

[0048] The difference from Example 1 is that the wavelength of the ultraviolet light is 350 nm, and finally a polymer film and laminated glass are obtained.

[0049] Example 5

[0050] The difference from Example 1 is that, in parts by weight, the polymer film composition includes: 100 parts of a base resin ethylene-vinyl acetate copolymer, 0.1 parts of a silane coupling agent γ-methacryloxypropyltrimethoxysilane, 0.1 parts of a light stabilizer 2,2,6,6-tetramethyl-4-piperidine stearate, 5 parts of a photoacid generator triphenylsulfonium perfluorobutane sulfonic acid, 5 parts of an acid-sensitive dye 2-phenylamino-3-methyl-6-dibutylaminofluorane (the molar ratio of the photoacid generator to the acid-sensitive dye is 0.95:1), 1.5 parts of a cross-linking agent tert-amyl peroxy (2-ethylhexyl) carbonate, 2.5 parts of a co-cross-linking agent triallyl isocyanurate and 1 part of an antioxidant tetrakis (β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate) pentaerythritol, and finally a polymer film and a laminated glass are obtained.

[0051] Example 6

[0052] The difference from Example 1 is that, in parts by weight, the polymer film composition includes: 100 parts of a base resin ethylene-vinyl acetate copolymer, 5 parts of a silane coupling agent γ-methacryloxypropyltrimethoxysilane, 5 parts of a light stabilizer 2,2,6,6-tetramethyl-4-piperidine stearate, 0.01 parts of a photoacid generator triphenylsulfonium perfluorobutane sulfonic acid, 0.01 parts of an acid-sensitive dye 2-phenylamino-3-methyl-6-dibutylaminofluorane (the molar ratio of the photoacid generator to the acid-sensitive dye is 0.95:1), 0.02 parts of a cross-linking agent tert-amyl peroxy (2-ethylhexyl) carbonate, 0.05 parts of a co-cross-linking agent triallyl isocyanurate and 0.03 parts of an antioxidant tetrakis (β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate) pentaerythritol, and finally a polymer film and a laminated glass are obtained.

[0053] Example 7

[0054] The difference from Example 1 is that, at an ultraviolet light wavelength of 248 nm, the molar ratio of the photoacid generator triphenylsulfonium perfluorobutane sulfonic acid and the acid-sensitive dye 2-phenylamino-3-methyl-6-dibutylaminofluoran is 0.1:1, and the added weight portions are 0.1 part and 0.95 part respectively, and finally a polymer film and a laminated glass are obtained.

[0055] Example 8

[0056] The difference from Example 1 is that, under an ultraviolet light wavelength of 248 nm, the molar ratio of the photoacid generator triphenylsulfonium perfluorobutane sulfonic acid and the acid-sensitive dye 2-phenylamino-3-methyl-6-dihydrofluoran is 1:1, and the added weight portions are 1 part and 0.95 parts respectively, and finally a polymer film and a laminated glass are obtained.

[0057] Example 9

[0058] The difference from Example 1 is that, at an ultraviolet light wavelength of 248 nm, the molar ratio of the photoacid generator triphenylsulfonium perfluorobutane sulfonic acid and the acid-sensitive dye 2-phenylamino-3-methyl-6-dibutylaminofluoran is 20:1, and the added weight portions are 1 part and 0.047 parts respectively, and finally a polymer film and a laminated glass are obtained.

[0059] Example 10

[0060] The difference from Example 1 is that, at an ultraviolet light wavelength of 248 nm, the molar ratio of the photoacid generator triphenylsulfonium perfluorobutane sulfonic acid and the acid-sensitive dye 2-phenylamino-3-methyl-6-dibutylaminofluoran is 55:1, and the added weight portions are 4 parts and 0.07 parts respectively, and finally a polymer film and a laminated glass are obtained.

[0061] Embodiment 11

[0062] The difference from Example 1 is that, under an ultraviolet light wavelength of 350 nm, the molar ratio of the photoacid generator p-toluene diazonium sulfate and the acid-sensitive dye crystal violet lactone is 1:1, and the added weight portions are 1 part and 1.92 parts respectively, and finally a polymer film and a laminated glass are obtained.

[0063] Example 12

[0064] The difference from Example 11 is that, at an ultraviolet light wavelength of 350 nm, the molar ratio of the photoacid generator p-toluene diazonium sulfate and the acid-sensitive dye crystal violet lactone is 50:1, and the added weight portions are 2.6 parts and 0.1 parts respectively, and finally a polymer film and laminated glass are obtained.

[0065] Example 13

[0066] The difference from Example 11 is that, at an ultraviolet light wavelength of 350 nm, the molar ratio of the photoacid generator p-toluene diazonium sulfate and the acid-sensitive dye crystal violet lactone is 55:1, and the added weight portions are 2.86 parts and 0.1 parts respectively, and finally a polymer film and laminated glass are obtained.

[0067] Embodiment 14

[0068] The difference from Example 11 is that the wavelength of the ultraviolet light is 450 nm, and a polymer film and laminated glass are finally obtained.

[0069] Embodiment 15

[0070] The difference from Example 11 is that the wavelength of the ultraviolet light is 300 nm, and finally a polymer film and laminated glass are obtained.

[0071] Example 16

[0072] The difference from Example 1 is that, at an ultraviolet light wavelength of 150 nm, the molar ratio of the photoacid generator N-toluenesulfonyloxyphthalimide and the acid-sensitive dye benzoyl leuco-methylene blue is 0.1:1, and the added weight portions are 0.08 parts and 1 part respectively, and finally a polymer film and laminated glass are obtained.

[0073] Embodiment 17

[0074] The difference from Example 11 is that, at an ultraviolet light wavelength of 150 nm, the molar ratio of the photoacid generator N-toluenesulfonyloxyphthalimide and the acid-sensitive dye benzoyl leuco-methylene blue is 30:1, and the added weight portions are 1.22 parts and 1 part respectively, and finally a polymer film and laminated glass are obtained.

[0075] Embodiment 18

[0076] The difference from Example 11 is that, at an ultraviolet light wavelength of 150 nm, the molar ratio of the photoacid generator N-toluenesulfonyloxyphthalimide and the acid-sensitive dye benzoyl leuco-methylene blue is 60:1, and the added weight portions are 2.44 parts and 0.1 parts respectively, and finally a polymer film and laminated glass are obtained.

[0077] Embodiment 19

[0078] The difference from Example 17 is that the wavelength of the ultraviolet light is 300 nm, and a polymer film and laminated glass are finally obtained.

[0079] Embodiment 20

[0080] The difference from Example 17 is that the wavelength of the ultraviolet light is 350 nm, and a polymer film and laminated glass are finally obtained.

[0081] Embodiment 21

[0082] The difference from Example 17 is that the wavelength of the ultraviolet light is 100 nm, and a polymer film and laminated glass are finally obtained.

[0083] Embodiment 22

[0084] The difference from Example 7 is that, at an ultraviolet light wavelength of 248 nm, the molar ratio of the photoacid generator trichloroacetophenone and the acid-sensitive dye benzoyl leuco-methylene blue is 0.1:1, and the added weight portions are 0.1 parts and 1.75 parts respectively, and finally a polymer film and a laminated glass are obtained.

[0085] Comparative Example 1

[0086] The difference from Example 1 is that, in parts by weight, the polymer film composition includes: 100 parts of a base resin ethylene-vinyl acetate copolymer, 0.5 parts of a silane coupling agent γ-methacryloxypropyltrimethoxysilane, 0.6 parts of a light stabilizer 2,2,6,6-tetramethyl-4-piperidinyl stearate, 1.0 parts of an acid-sensitive dye 2-phenylamino-3-methyl-6-dibutylaminofluoran, 0.5 parts of a cross-linking agent tert-amyl peroxy (2-ethylhexyl) carbonate, 0.8 parts of a co-cross-linking agent triallyl isocyanurate and 0.3 parts of an antioxidant tetrakis (β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), and finally a polymer film and a laminated glass are obtained.

[0087] Comparative Example 2

[0088] The difference from Example 1 is that, in parts by weight, the polymer film composition includes: 100 parts of a base resin ethylene-vinyl acetate copolymer, 0.5 parts of a silane coupling agent γ-methacryloxypropyltrimethoxysilane, 0.6 parts of a light stabilizer 2,2,6,6-tetramethyl-4-piperidine stearate, 0.8 parts of a photoacid generator triphenylsulfonium perfluorobutane sulfonic acid, 0.5 parts of a cross-linking agent tert-amyl peroxy (2-ethylhexyl) carbonate, 0.8 parts of a co-cross-linking agent triallyl isocyanurate and 0.3 parts of an antioxidant tetrakis (β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate) pentaerythritol, and finally a polymer film and a laminated glass are obtained.

[0089] Comparative Example 3

[0090] The polymer film composition comprises, by weight, 100 parts of a matrix resin ethylene-vinyl acetate copolymer, 0.5 parts of a silane coupling agent γ-methacryloxypropyl trimethoxysilane, 0.6 parts of a light stabilizer 2,2,6,6-tetramethyl-4-piperidinyl stearate, 6.0 parts of a photoacid generator triphenylsulfonium perfluorobutane sulfonic acid, 6.0 parts of an acid-sensitive dye 2-phenylamino-3-methyl-6-dibutylaminofluoran, 0.5 parts of a crosslinking agent tert-amyl peroxy (2-ethylhexyl) carbonate, 0.8 parts of an auxiliary crosslinking agent triallyl isocyanurate and 0.3 parts of an antioxidant tetrakis (β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate) pentaerythritol, and finally a polymer film and a laminated glass are obtained.

[0091] Test method:

[0092] 1. Tests on tensile strength, elongation at break, and adhesion between polymer film and glass: The test methods refer to the standard GB / T29848 "Ethylene-vinyl acetate copolymer (EVA) film for photovoltaic module encapsulation".

[0093] 2. Pattern uniformity test: Design the same pattern for color display, select a specific point in the middle and edge of the pattern, record the actual distance between the two points △E2, and the theoretical distance between the two points is recorded as △E1, with D = |△E 2- △E1| / △E1*100% represents the pattern uniformity. The closer D is to 0, the better the uniformity.

[0094] 3. Maximum drop ball height test: The front glass, polymer film and rear glass are stacked and thermally cured in sequence to obtain laminated glass, which is then tested in accordance with Article 7:11 of GB15763.3-2009 "Architectural Safety Glass Part 3: Laminated Glass" and the maximum drop ball height that meets the requirements is recorded.

[0095] The performance of the polymer film and laminated glass was tested, and the test results are shown in Table 1.

[0096] Table 1

[0097]

[0098]

[0099] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0100] The polymer film composition of the present application introduces a photoacid generator and an acid-sensitive dye, which can realize patterning and colorization on the polymer film. The photoacid generator decomposes to generate hydrogen ions (H + ), while acid-sensitive dyes have no color under alkaline or neutral conditions, but when reacted with H generated by a photoacid generator + After combination, different colors can be produced. At the same time, by changing the amount of photoacid generator added, the depth of the color can be changed; by changing the type of acid-sensitive dye, the type of color can be changed. Therefore, the present invention controls the position of ultraviolet light irradiation, so that different patterns and colors can be produced at specific positions of the polymer film. Especially for the application scenario of lamination and cross-linking, the polymer film composition of the present invention can be patterned after lamination and cross-linking, so the polymer film composition of the present invention is more universal.

[0101] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A polymer film composition, characterized in that In parts by weight, the polymer film composition comprises: 100 parts of base resin; 0.01 to 5 parts of a photoacid generator; 0.01 to 5 parts of acid-sensitive dye.

2. The polymer film composition according to claim 1, characterized in that The molar ratio of the photoacid generator to the acid-sensitive dye is 0.1 to 50:1, preferably 0.5 to 10:

1.

3. The polymer film composition according to claim 1 or 2, characterized in that: The photoacid generator is selected from any one or more of a diazonium salt photoacid generator, an onium salt photoacid generator, a sulfonate photoacid generator, an organic polyhalogen compound photoacid generator, a Ru(II) complex photoacid generator based on 4,4'-bis(chloromethyl)-2,2'-bipyridine, and a thioxanthone sulfonate photoacid generator; and / or, the diazonium salt photoacid generator is selected from any one or more of diazonium sulfate, diazonium hydrochloride, diazonium sulfonate, diazonium fluoroborate and diazonium fluorophosphate; And / or, the onium salt photoacid generator is selected from any one or more of tert-butylphenyl iodonium salt perfluorooctane sulfonic acid, triphenyl sulfonium perfluorobutane sulfonic acid and triphenyl sulfonium trifluorosulfonic acid; and / or, the sulfonate photoacid generator is selected from any one or more of N-toluenesulfonyloxyphthalimide, N-trifluoromethanesulfonyloxysuccinimide, N-trifluoromethanesulfonyloxynaphthalimide, dinitrobenzyl p-toluenesulfonate and p-toluenesulfonate of α-hydroxymethylbenzoin; And / or, the organic polyhalogen compound photoacid generator is selected from any one or more of trichloroacetophenone, tribromomethylphenyl sulfone, 4-phenoxydichloroacetophenone and 4,6-bis(trichloromethyl)-1,3,5-triazine derivatives.

4. The polymer film composition according to claim 3, characterized in that The acid-sensitive dye is selected from any one or more of triphenylmethane compounds, phenothiazine compounds and fluoran compounds; and / or the triphenylmethane compound is crystal violet lactone and / or phenolphthalein; and / or the phenothiazine compound is benzoyl leuco-methylene blue; and / or the fluoran compound is 2-phenylamino-3-methyl-6-diethylaminofluoran and / or 2-phenylamino-3-methyl-6-dibutylaminofluoran.

5. The polymer film composition according to claim 4, characterized in that Under ultraviolet light wavelength of 350-450nm, the photoacid generator is the diazonium salt photoacid generator, the acid-sensitive dye is the triphenylmethane compound, and the molar ratio of the diazonium salt photoacid generator to the triphenylmethane compound is 1-50:

1.

6. The polymer film composition according to claim 4, characterized in that: Under ultraviolet light wavelength of 150-300nm, the photoacid generator is the sulfonate photoacid generator, the acid-sensitive dye is the phenothiazine compound, and the molar ratio of the sulfonate photoacid generator to the phenothiazine compound is 0.1-30:

1.

7. The polymer film composition according to claim 4, characterized in that: Under ultraviolet light wavelength of 100-300nm, the photoacid generator is the onium salt photoacid generator, the acid-sensitive dye is a fluorane compound, and the molar ratio of the onium salt photoacid generator to the fluorane compound is 1-20:

1.

8. The polymer film composition according to any one of claims 1 to 7, characterized in that The base resin is selected from any one or more of ethylene-vinyl acetate copolymer, ethylene-α-olefin copolymer, polyvinyl butyral, polyvinyl chloride and polyurethane; And / or, the polymer film composition further comprises any one or more of a silane coupling agent and a light stabilizer; preferably, the silane coupling agent is selected from any one or more of γ-glycidyloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltri(2-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane; Preferably, the light stabilizer is selected from 1,5,8,12-tetrakis[4,6-bis(N-butyl-N-1,2,2,6,6-pentamethyl-4-piperidinylamino)-1,3,5-triazine-2-yl]-1,5,8,12-tetraazadodecane, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol) succinate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[ Any one or more of (2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino], 1,6-hexanediamine N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl), 2,4,6-trichloro-1,3,5-triazine, poly(6-morpholinyl-5-triazine-2,4-diyl)(2,2,6,6-tetramethylpiperidinyl)iminohexamethylene[(2,2,6,6-tetramethylpiperidinyl)-imino], 2,2,6,6-tetramethyl-4-piperidinyl stearate and N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-N,N'-dialdehyde hexanediamine; And / or, the polymer film composition further comprises an auxiliary agent; preferably, the auxiliary agent is selected from any one or more of a cross-linking agent, a co-cross-linking agent and an antioxidant.

9. A polymer film, obtained by sequentially mixing and melt extruding a polymer film composition, characterized in that: The polymer film composition is the polymer film composition according to any one of claims 1 to 8.

10. A laminate comprising at least two layers of glass and at least one layer of polymer film, characterized in that: The polymer film is the polymer film according to claim 9.

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