CN101284891B - Film-forming resin and heat reactive resin compositions with the film-resin forming - Google Patents
Film-forming resin and heat reactive resin compositions with the film-resin forming Download PDFInfo
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Abstract
The invention provides a film forming resin which comprises a unit formed by a monomer A and a unit formed by a monomer B, wherein, the monomer A is the methyl acrylate with an epoxide group, the monomer B is one or more than one of the (methyl) benzyl acrylate, the (methyl) acrylic acid phenethyl ester and the (methyl) acrylic acid phenyl ester, in the film forming resin, the mol ratio of the unit formed by the monomer A and the unit formed by the monomer B is between 1:1 and 8:1, the weight average molar mass of the film forming resin is between 5000 and 100000. The thermocuring resin compound greatly improves the hardness of a protective film for a colorful spectral filter and the heat-resistant polychromasia. In addition, the thermocuring resin compound has good storage stability; theprotective film formed by the thermocuring resin compound has good heat resistance, leveling property, light-admitting quality, anti-ITO sputtering property, etching-proof characteristic, adhesive attraction and the uniformity of the film thickness.
Description
Technical field
The invention relates to a kind of film-forming resin and contain the thermally curable resin composition of this film-forming resin, especially about a kind of thermally curable resin composition that is used for the film-forming resin of protective films of color filters and contains this film-forming resin.
Background technology
In recent years, Thin Film Transistor-LCD (TFT-LCD) is a flat panel display equipment with the fastest developing speed, and is expected to become the main flow of monitor market.The colored filter that is used for TFT-LCD comprises glass substrate, black matrix" (Black matrix), chromatic filter layer, protective membrane and transparent electrode layer (as the ITO layer); this colored filter is by make the light shield layer-black matrix" of antireflection on transparent glass substrate; make chromatic filter layer more successively with light transmission Red Green Blue; be coated with layer protecting film (Over Coat) then on this chromatic filter layer, transparent electrode layer (ITO) forms on the last sputter.
Described protective membrane is attached to the surface of chromatic filter layer, and major function is the smoothness of protecting chromatic filter layer and increasing the surface, simultaneously as the insulation layer between black matrix" and the transparent electrode layer, also has the spacer pad crystalline substance to wait effect with preventing pollution in addition.
Protective membrane on the chromatic filter layer requires that following performance is arranged: (1) protective membrane should have the surface of good levelling property; (2) protective membrane has resistivity to the high temperature sputter of ITO; (3) protective membrane should improve the good solubility-resistence of colored filter; (4) protective membrane has good adhesive properties; (5) protective membrane is transparent in visible-range; (6) protective membrane should possess the above hardness of 4H.
WO2005057285 discloses a kind of single-liquid type heat-curable epoxy resin compositions, and said composition contains film-forming resin, solidifying agent, organic solvent and the coupling agent shown in the formula (I),
A is the monomer with epoxide group described in its Chinese style (I); B is the acrylic or methacrylic acid mono that contains carboxyl; C is that vinylbenzene or carbon atoms number are acrylate or the methacrylate monomer of 1-14, for example one or more in methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl propenoate, cyclohexyl acrylate, isobornyl methacrylate, isobornyl acrylate, hydroxyethyl methylacrylate, dimethylaminoethyl methacrylate and the acrylamide; L, m, n is respectively A, B, the mole number of C.1 is 0.1-90 mole %, and m is 0-70 mole %, and n is 0.1-90 mole %.Relatively poor by the protective membrane surface hardness that said composition makes; When carrying out high temperature ITO sputter, depressed phenomenon can occur even crack, thereby cause the protective membrane unfairness easily.In addition, though this protective membrane has good light transmittance,, metachromatism takes place in easily under the temperature about 250 ℃, thereby causes protective membrane light transmission variation.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming of low, the heat-resisting discolouration difference of protective membrane hardness that is used for colored filter in the prior art, a kind of thermally curable resin composition that can obtain the film-forming resin of hardness height, protective membrane that heat-resisting discolouration is good and contain this film-forming resin is provided.
The invention provides a kind of film-forming resin, wherein, this film-forming resin contains the unit of monomer A formation and the unit that monomers B forms, described monomer A is the acrylate that contains epoxide group, described monomers B is one or more in (methyl) benzyl acrylate, (methyl) phenylethyl and (methyl) phenyl acrylate, in this film-forming resin, the unitary mol ratio that unit that described monomer A forms and described monomers B form is 1-8:1, and the weight-average molecular weight of described film-forming resin is 5000-100000.
The invention provides a kind of thermally curable resin composition, said composition contains film-forming resin and solidifying agent, and wherein, described film-forming resin is a film-forming resin provided by the invention.
The thermally curable resin composition that the application of the invention provides has improved the hardness and the heat-resisting discolouration of the protective membrane that is used for colored filter greatly.For example; the surface hardness of the protective membrane that the thermally curable resin composition that the present invention makes forms all is higher than 5H; thereby when carrying out the ITO sputter; the phenomenon that caves in and crack can not appear in the surface; can not influence the planarization of protective membrane, and the protective membrane that prior art makes only is 3H, when carrying out the ITO sputter; depressed phenomenon can appear in the surface, causes the planarization variation of protective membrane.In addition; the heat-resisting discolouration that adopts the protective membrane that thermally curable resin composition of the present invention makes is all below 4%, and the heat-resisting discolouration of the protective membrane that prior art makes is 5%, therefore; the protective membrane that prior art makes is under the higher situation of temperature, and heat-resisting discolouration is relatively poor.Therefore, the protective membrane that forms of the thermally curable resin composition that makes of the present invention all is better than the protective membrane that prior art makes on surface hardness and heat-resisting discolouration.
In addition, good by thermally curable resin composition stability in storage provided by the invention, heat impedance, levelling property, light transmission, anti-ITO sputter, anti-etching characteristic, sticking power and the film uniformity of the protective membrane that is formed by this thermally curable resin composition are all better.
Embodiment
Film-forming resin of the present invention contains the unit of monomer A formation and the unit that monomers B forms, described monomer A can be the various acrylate that contain epoxide group, for example, can be glycidyl acrylate, glycidyl methacrylate, Racemic glycidol-alpha-acrylic ethyl ester, Racemic glycidol-α-Jia Jibingxisuan ethyl ester, 3,4-epoxy butylacrylic acid ester, 3,4-epoxy butyl first acrylate, 6,7-epoxy hexane acrylate and 6, one or more in the 7-epoxy hexane methacrylic ester.Described monomers B can be one or more in (methyl) benzyl acrylate, (methyl) phenylethyl and (methyl) phenyl acrylate.In this film-forming resin, the unitary mol ratio that unit that described monomer A forms and described monomers B form is 1-8:1.The unitary content that increases monomers B formation in the film-forming resin can improve the hardness and the heat-resisting discolouration of the protective membrane of the solution formation that contains this film-forming resin; therefore, the unitary mol ratio of the unit of preferred described monomer A formation and the formation of described monomers B is 1-5:1.There is no particular limitation to the polymerization degree of described film-forming resin in the present invention; for the various polymerization degree of conventional film-forming resin polymkeric substance get final product; for example the weight-average molecular weight of described film-forming resin can be 5000-100000; in the scope of the weight-average molecular weight of above-mentioned film-forming resin, the weight-average molecular weight that suitably reduces described film-forming resin can further improve every performances such as the film uniformity of protective membrane, sticking power.Therefore, the weight-average molecular weight of film-forming resin of the present invention is preferably 10000-50000.In addition, weight-average molecular weight of the present invention is for measuring the polystyrene conversion value that obtains by gel permeation chromatography (GPC).
Can adopt polymerization process to prepare film-forming resin of the present invention.For example, monomer A, monomers B and initiator can be mixed, heat under inert gas atmosphere, polymerization reaction take place obtains film-forming resin.But the molecular weight distribution that this direct reaction obtains is inhomogeneous, and the inhomogeneous meeting of the molecular weight distribution of described film-forming resin causes the protective membrane degradation.
In order to obtain the film-forming resin of even molecular weight distribution, under the preferable case, earlier monomer A and B and initiator are mixed with organic solvent, obtain mixed solution, the amount of organic solvent described in the mixed solution is 1-3 times of gross weight of monomer A and monomers B.Under inert gas atmosphere, this mixed solution is added drop-wise in the organic solvent then, under 60-100 ℃ temperature, carry out polyreaction, the consumption of described organic solvent can be monomer A and monomers B gross weight 0.5-2 doubly, the speed that described mixed solution drips can be the 0.2-1 ml/min.Finally obtain film-forming resin solution, the organic solvent in the described film-forming resin solution can be removed, and also can not remove.In addition, the present invention is in being prepared into film resin, in order to obtain monomer A unit that forms and the unitary mol ratio that described monomers B forms is the film-forming resin of 1-8:1, can be that 1-8:1 realizes by the mol ratio of controlling the add-on of monomer A and monomers B in the preparation process.Under the preferable case, be the film-forming resin of 1-5:1 in order to obtain monomer A unit that forms and the unitary mol ratio that described monomers B forms, the mol ratio of controlling the add-on of monomer A and monomers B in the preparation process is 1-5:1.
Described organic solvent can be variously monomer A and B are fully dissolved do not influence the various organic solvents of polyreaction between monomer A and the monomers B, for example, can be in toluene, dimethylbenzene, acetone, methylethylketone, mibk, methyl isoamyl ketone, ethyl acetate, butylacetate, methylcarbonate, ethylene glycol ether acetate, isobutyl isobutyrate, propylene-glycol ethyl ether, Succinic acid dimethylester, Methyl glutarate, dimethyl adipate, 1-Methoxy-2-propyl acetate, ethylene glycol monomethyl ether acetate and the 3-ethoxyl ethyl propionate one or more.
Described initiator is conventionally known to one of skill in the art.For example, can be Diisopropyl azodicarboxylate, dimethyl-2,2 '-azo two (2-methacrylic ester) and 2,2 '-azo two (2, the 4-methyl pentane nitrile) one or more in, the consumption of described initiator gets final product for this area conventional amount used, for example is the 1-5 weight % of monomer A and monomers B total amount.
Described rare gas element can be one or more in nitrogen, helium, neon, argon gas, krypton gas, xenon and the radon gas.
Thermally curable resin composition of the present invention contains film-forming resin and solidifying agent, the film-forming resin that described film-forming resin prepares for the present invention.
According to the present invention, described solidifying agent is conventionally known to one of skill in the art.For example can be in acid anhydrides, polyamine, polyphenol and the polythiol one or more.The mixed curing agent that the preferred described solidifying agent of the present invention is acid anhydrides and phenol, described acid anhydrides can be for trimellitic anhydride, face in phthalate anhydride, tetrahydrochysene phthalate anhydride, methyl tetrahydrochysene phthalate anhydride, hexahydrophthalic anhydride and the pyromellitic acid anhydride one or more, and described phenol can be dihydroxyphenyl propane compound and/or bis-phenol sulphur compound.Total amount with solidifying agent is a benchmark, and the content of described acid anhydrides is 20-80 weight %, and the content of described phenol is 20-80 weight %.Film-forming resin with 100 weight parts is a benchmark, and the content of described solidifying agent is the 2-40 weight part.
Wherein, described dihydroxyphenyl propane compound can be a compound as the formula (1), and wherein, described R1, R2, R3, R4 can be that hydrogen atom, halogen or carbonatoms are the alkyl of 1-3 separately.Described bis-phenol sulphur compound can be a compound as the formula (2), and wherein, described R1, R2, R3, R4 can be that hydrogen atom, halogen or carbonatoms are the alkyl of 1-3.Because the dihydroxyphenyl propane compound is cheap and easy to get, therefore, preferred described phenol is the dihydroxyphenyl propane compound.Dihydroxyphenyl propane compound of the present invention and bis-phenol sulphur compound all are available commercially, for example, the trade mark that the Japanese Dongdu of described dihydroxyphenyl propane compound company that changes into produces is the resin of ST-1000, and described bis-phenol sulphur compound can be that the trade mark of SIGMA-ALORICH product is 216178 bis-phenol sulphur compound.
In addition, because acid anhydrides solvability in organic solvent is bad, dissolution rate is slower, can make thermally curable resin composition solidify the back and produce trickle particle on the surface, thereby influence the performance of protective membrane.The present inventor finds, by 1-methoxyl group-1-Ethoxyethane and acid anhydrides are used and can effectively overcome the problems referred to above, therefore, under the preferable case, also contains 1-methoxyl group-1-Ethoxyethane in the described composition.The content of described 1-methoxyl group-1-Ethoxyethane be described solidifying agent weight 1-5 doubly.
According to composition provided by the invention, described composition can also contain coupling agent and/or tensio-active agent.Described coupling agent is conventionally known to one of skill in the art.For example, can be γ-glycidyl ether oxygen propyl trimethoxy silicane, β-(3,4 epoxycyclohexyls) ethyl trimethoxy silane, γ-glycidoxypropyltrietandysilane andysilane, β-(3,4 epoxycyclohexyls) one or more in ethyl triethoxysilane, γ-glycidyl ether oxygen propyl trichlorosilane and β-epoxy radicals silicone hydride class coupling agents such as (3,4 epoxycyclohexyl) ethyl trichlorosilane.Film-forming resin with 100 weight parts is a benchmark, and the consumption of described coupling agent can be the 10-30 weight part.Described tensio-active agent is conventionally known to one of skill in the art.For example can be fluorocarbon surfactant series and/or nonionic surface active agent series.Film-forming resin with 100 weight parts is a benchmark, and the consumption of described tensio-active agent can be the 0.1-0.5 weight part.
Mix and promptly get thermally curable resin composition of the present invention removing film-forming resin behind the organic solvent and solidifying agent.Described composition also can be the film-forming resin solution that the present invention prepares directly to be mixed with solidifying agent obtain.In order to simplify preparation technology, save solvent load, preferably after making film-forming resin solution, direct and solidifying agent mixes in the present invention.
When thermally curable resin composition of the present invention also contained in 1-methoxyl group-1-Ethoxyethane, coupling agent and the tensio-active agent one or more, the preparation method of described thermally curable resin composition also comprised in film-forming resin and 1-methoxyl group-1-Ethoxyethane, coupling agent and the tensio-active agent one or more is mixed.
Use thermally curable resin composition of the present invention to carry out in the preparation of protective membrane, can directly with an organic solvent described composition be diluted formation solution, apply then, dry getting final product.
Described organic solvent can be to make film-forming resin and solidifying agent fully dissolve not various organic solvents with film-forming resin and solidifying agent reaction, for example, can be in toluene, dimethylbenzene, acetone, methylethylketone, mibk, methyl isoamyl ketone, ethyl acetate, butylacetate, methylcarbonate, ethylene glycol ether acetate, isobutyl isobutyrate, propylene-glycol ethyl ether, Succinic acid dimethylester, Methyl glutarate, dimethyl adipate, 1-Methoxy-2-propyl acetate, ethylene glycol monomethyl ether acetate and the 3-ethoxyl ethyl propionate one or more.Two or more that the preferred described organic solvent of the present invention is above-mentioned organic solvent.
At described organic solvent is under the situation of mixed solvent, and composition has good flowability, makes the protective membrane that obtains have good levelling property; simultaneously; because the boiling point of mixed solvent and rate of volatilization all change in gradient, can guarantee the protective membrane good film-forming property that obtains, surperficial zero defect.It is 6-15 milli handkerchief second that the add-on of described organic solvent makes the viscosity of said composition, is preferably 8-12 milli handkerchief second, thereby can makes composition have good flowability.Generally speaking, be benchmark with the film-forming resin of 100 weight parts, the consumption of described organic solvent is the 150-400 weight part.Need to prove, the consumption of described organic solvent comprise the amount of the organic solvent that adds when being prepared into film resin and the organic solvent that heat of dilution curable resin composition is used amount and.
Described coating and exsiccant method are conventionally known to one of skill in the art, repeat no more herein.
Further specify film-forming resin provided by the invention and adopt the thermally curable resin composition of this film-forming resin below by embodiment.
Embodiment 1
Present embodiment illustrates film-forming resin provided by the invention and contains the thermally curable resin composition of this film-forming resin.
Glycidyl methacrylate with 80 weight parts, the benzyl methacrylate of 20 weight parts, 2.5 the Diisopropyl azodicarboxylate of weight part, the ethylene glycol monomethyl ether acetate of the 1-Methoxy-2-propyl acetate of 50 weight parts and 50 weight parts mixes, obtain mixed solution, this mixed solution is placed dropping funnel, the control flow velocity is 0.5 ml/min, under nitrogen atmosphere, this mixed solution is added drop-wise in the mixed solvent of ethylene glycol monomethyl ether acetate of the 1-Methoxy-2-propyl acetate of 20 weight parts and 20 weight parts, the temperature of described mixed solvent is 80 ℃, obtains film-forming resin solution.In the preparation feedback of film-forming resin of the present invention, because this polyreaction is unique reaction that can take place, therefore, the reaction product that obtains is film-forming resin provided by the invention certainly.In the described film-forming resin, the unitary mol ratio that unit that glycidyl methacrylate forms and benzyl methacrylate form is 1-5:1.The weight-average molecular weight of described film-forming resin is 20000.Wherein, the unitary mol ratio of the unit of glycidyl methacrylate formation and benzyl methacrylate formation is by calculating.Weight-average molecular weight is for measuring the polystyrene conversion value that obtains by gel permeation chromatography (GPC).
(Japanese Dongdu changes into company will to contain the trimellitic anhydride of 6.5 weight parts and the bisphenol A epoxide resin of 6.5 weight parts, the trade mark is ST-1000) solidifying agent, the γ-glycidyl ether oxygen propyl trimethoxy silicane of 12 weight parts and the fluorocarbon surfactant (3M of 0.2 weight part, model FC4430) mixes with the whole film-forming resin solution of above-mentioned gained, add the 1-Methoxy-2-propyl acetate of 30 weight parts and the ethylene glycol monomethyl ether acetate of 30 weight parts again, stir, making soltion viscosity was 10 milli handkerchief seconds.Obtain thermally curable resin composition solution A 1.
Comparative Examples 1
Film-forming resin that this Comparative Examples explanation prior art provides and the thermally curable resin composition that adopts this film-forming resin.
Method according to embodiment 1 is prepared into film resin and thermally curable resin composition, and different is to replace benzyl methacrylate with vinylbenzene.In the film-forming resin that obtains, the unitary mol ratio that unit that glycidyl methacrylate forms and vinylbenzene form is 1-5:1.The weight-average molecular weight of the described film-forming resin that obtains is 23000.Finally obtain soltion viscosity and be the thermally curable resin composition solution D 1 of 10 milli handkerchief seconds.
Comparative Examples 2
Film-forming resin that this Comparative Examples explanation prior art provides and the thermally curable resin composition that adopts this film-forming resin.
Method according to embodiment 1 is prepared into film resin and thermally curable resin composition, and different is to replace benzyl methacrylate with methyl methacrylate.In the film-forming resin that obtains, the unitary mol ratio that unit that glycidyl methacrylate forms and methyl methacrylate form is 1-5:1.The weight-average molecular weight of the described film-forming resin that obtains is 24000.Finally obtain soltion viscosity and be the thermally curable resin composition solution D 2 of 10 milli handkerchief seconds.
Embodiment 2
Method according to embodiment 1 is prepared into film resin, and different is also to contain the 1-methoxyl group-1-Ethoxyethane of 35 weight parts in the described solidifying agent.In the film-forming resin that obtains, the unitary mol ratio that unit that glycidyl methacrylate forms and benzyl methacrylate form is 1-5:1.The weight-average molecular weight of the described film-forming resin that obtains is 21000.Finally obtaining soltion viscosity is 9 milli handkerchief thermally curable resin composition second solution A 2.
Embodiment 3
Present embodiment illustrates film-forming resin provided by the invention and adopts the thermally curable resin composition of this film-forming resin.
Racemic glycidol-α-Jia Jibingxisuan ethyl ester with 70 weight parts, the methacrylic acid phenethyl ester of 30 weight parts, 2.5 the Diisopropyl azodicarboxylate of weight part, the ethylene glycol monomethyl ether acetate of the Methyl glutarate of 60 weight parts and 40 weight parts mixes, obtain mixed solution, this mixed solution is placed dropping funnel, the control flow velocity is 1 ml/min, under nitrogen atmosphere, this mixed solution is added drop-wise in the mixed solvent of ethylene glycol monomethyl ether acetate of the Methyl glutarate of 15 weight parts and 10 weight parts, the temperature of described mixed solvent is 80 ℃, obtains film-forming resin solution.In the described film-forming resin, the unitary mol ratio that unit that Racemic glycidol-α-Jia Jibingxisuan ethyl ester forms and methacrylic acid phenethyl ester form is 1-5:1.The weight-average molecular weight of described film-forming resin is 28000.
The trimellitic anhydride of 6.5 weight parts, the bisphenol A epoxide resin mixing of 6.5 weight parts are obtained solidifying agent, this solidifying agent is joined in the above-mentioned film-forming resin solution, and then add the coupling agent of 12 weight parts, the tensio-active agent of 0.2 weight part, mix, add the Methyl glutarate of 60 weight parts and the ethylene glycol monomethyl ether acetate of 40 weight parts again, stir, making soltion viscosity was 10 milli handkerchief seconds.Obtain thermally curable resin composition solution A 3.
Embodiment 4
Present embodiment illustrates film-forming resin provided by the invention and adopts the thermally curable resin composition of this film-forming resin.
With 3 of 50 weight parts, the methacrylic acid phenethyl ester of 4-epoxy butyl first acrylate, 50 weight parts, the Diisopropyl azodicarboxylate of 2.5 weight parts, the Methyl glutarate of 60 weight parts and the ethylene glycol monomethyl ether acetate of 40 weight parts mix, obtain mixed solution, this mixed solution is placed dropping funnel, the control flow velocity is 1 ml/min, under nitrogen atmosphere, this mixed solution is added drop-wise in the mixed solvent of ethylene glycol monomethyl ether acetate of the Methyl glutarate of 15 weight parts and 10 weight parts, the temperature of described mixed solvent is 80 ℃, obtains film-forming resin solution.In the described film-forming resin, 3, the unitary mol ratio that unit that 4-epoxy butyl first acrylate forms and methacrylic acid phenethyl ester form is 1-5:1.The weight-average molecular weight of described film-forming resin is 30000.
The trimellitic anhydride of 6.5 weight parts, the bisphenol A epoxide resin mixing of 6.5 weight parts are obtained solidifying agent, this solidifying agent is joined in the above-mentioned film-forming resin solution, and then add the coupling agent of 12 weight parts, the tensio-active agent of 0.2 weight part, mix, add the Methyl glutarate of 60 weight parts and the ethylene glycol monomethyl ether acetate of 40 weight parts again, stir, making soltion viscosity was 9 milli handkerchief seconds.Obtain thermally curable resin composition solution A 4.
Embodiment 5
The performance of thermally curable resin composition solution that present embodiment explanation the present invention makes and the protective membrane that obtains by said composition solution.
(a) thermally curable resin composition solution stable storing property testing
The thermally curable resin composition solution A 1 that embodiment 1 is made stores 1 month down at 25 ℃, measure and store the front and back viscosity change, equal 5cps if viscosity changes to be less than, then stability in storage " good ", be higher than 5cps then stability in storage " poor " if viscosity changes, the result is as shown in table 1.
(b) protective membrane performance test
The thermally curable resin composition solution A 1 that embodiment 1 is made is applied on the sheet glass by desk-top sol evenning machine (the prosperous electronics technology company limited of grinding, KW-4A type), and formation thickness is 2.5 microns protective membrane B1.Then, sheet glass is placed 100 ℃ of oven dry of air dry oven 60 minutes, again through 230 ℃ of oven dry 30 minutes.Then this protective membrane is carried out following performance test, the result is as shown in table 2.
(1) heat impedance
Place air dry oven respectively at 200 ℃, 230 ℃, 260 ℃ heating 60 minutes above-mentioned sheet glass, the crackle that whether has of observing film coated surface then produces, if flawless produces, then heat impedance is " good ", then is " poor " on the contrary.
(2) levelling property
Whether there are The apparent phenomenon such as foaming, shrinkage cavity, particle to occur with opticmicroscope (optical instrument factory, Shanghai, 6JA type) sight glass sheet surface.The apparent phenomenon such as surperficial no foaming, shrinkage cavity, particle occur, and then levelling property is " good ", if there is small quantities of particles on the surface, then is " better ", if there is particle on the surface, also has foaming, shrinkage cavity, then is " poor ".
(3) light transmission
Adopt ultraviolet spectrophotometer (Shanghai flood discipline plant and instrument company limited produces model 756) to measure the transmittance of protective membrane.Wherein, transmittance is qualified product more than or equal to 97%.
(4) anti-ITO sputter
Is sheet glass sputter one layer thickness under 220 ℃ of temperature 1500
Ito thin film, the crackle situation by the observation by light microscope protective membrane then.If flawless produces, then anti-ITO sputter is " good ", then is " poor " on the contrary.
(5) anti-etching characteristic
With sputter the sheet glass of ITO be coated with last layer positive photoresist (Beijing Inst. of Chemical Reagent; the BP212 type); exposure then; with concentration is that the tetramethylammonium hydroxide aqueous solution of 2.38 weight % develops; water cleans; with mixing acid (with concentration be 37% hydrochloric acid, water, concentration be 67% nitric acid mix with the volume ratio of 50:50:3 obtain) carry out harshly, water cleans, by observation by light microscope ITO layer and protective membrane crackle situation.If flawless produces, then anti-etching characteristic is " good ", then is " poor " on the contrary.
(6) sticking power
On the protective membrane after the curing, cut six roads (long 20 millimeters) with safety razor; tool marks should see through the protective membrane degree of depth; cutting six same road tool marks (long 20 millimeters) with the vertical direction of the first six road tool marks then; form many lattices; with the light finger light touches; the protective membrane person's sticking power " good " that do not come off then is " poor " on the contrary.
(7) film uniformity
Get 4 points in different zones on glass, measure this thickness of 4 with microoptic film thickness gauge (Taiwan, MFS-MicroSpot type), calculate film uniformity according to following formula, wherein, film uniformity is qualified product smaller or equal to 5%.
Film uniformity=(thickness maximum value-thickness minimum value) ÷ (thickness maximum value+thickness minimum value) * 100%
(8) surface hardness
Surface hardness with portable pencil hardness meter (Shenzhen three promise instruments, QHQ-A type) test protective membrane.This value is 4H when above, and surface hardness is good, and when carrying out the ITO sputter, depressed phenomenon can not appear in the surface, can not destroy the planarization of protective membrane.
(9) heat-resisting discolouration
Sheet glass was heated 1 hour in 250 ℃ baking oven, identical with the testing method of above-mentioned (3), measure the light transmission before and after heating.Be calculated as follows the heat-resisting discolouration of protective membrane, this value is 5% when following, and heat-resisting discolouration is good.
Transmittance after transmittance-heating before heat-resisting discolouration=heating
Comparative Examples 3-4
The performance of thermally curable resin composition solution D 1 that Comparative Examples 1 and Comparative Examples 2 is obtained according to the method for embodiment 5 and D2 and the protective membrane that obtains by said composition solution D 1 and D2.The result as shown in Table 1 and Table 2.
Embodiment 6-8
The performance of thermally curable resin composition solution A 2-A4 that embodiment 6-8 is obtained according to the method for embodiment 5 and the protective membrane that obtains by said composition solution A 2-A4.The result as shown in Table 1 and Table 2.
Table 1
| The embodiment numbering | Embodiment 1 | Comparative Examples 1 | Comparative Examples 2 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Viscosity changes (milli handkerchief second) | 4 | 4 | 5 | 3 | 4 | 4 |
| Stability in storage | Good | Good | Good | Good | Good | Good |
As can be seen from Table 1, the stability in storage of the heat-curing composition solution A 1-A4 that makes of embodiment of the invention 1-4 is all better.
Table 2
| The composition source | Embodiment 1 | Comparative Examples 1 | Comparative Examples 2 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| The protective membrane numbering | B1 | DD1 | DD2 | B2 | B3 | B4 |
| Heat impedance | Good | Good | Good | Good | Good | Good |
| Levelling property | Better | Better | Better | Good | Better | Better |
| Light transmission (%) | 98 | 98 | 99 | 99 | 98 | 99 |
| Anti-ITO sputter | Good | Difference | Difference | Good | Good | Good |
| Anti-etching characteristic | Good | Good | Good | Good | Good | Good |
| Sticking power | Good | Good | Good | Good | Good | Good |
| Film uniformity (%) | 3 | 4 | 3 | 3 | 4 | 4 |
| Surface hardness (H) | 5 | 3 | 2 | 6 | 5 | 5 |
| Heat-resisting discolouration (%) | 4 | 6 | 7 | 3 | 3 | 4 |
As can be seen from Table 2, the protective membrane B1-B4 that makes of the heat-curing composition solution A 1-A4 that is made by embodiment of the invention 1-4 all is better than the protective membrane DD1-DD2 that the heat-curing composition solution D 1-D2 that made by Comparative Examples 1-2 makes on anti-ITO sputter, surface hardness and heat-resisting discolouration.For example, the surface hardness of the protective membrane B1-B4 that the present invention makes all is higher than 5H, and the protective membrane DD1-DD2 that Comparative Examples makes only is 3H; this hardness is below 4H, and when carrying out the ITO sputter, crackle, depressed phenomenon can appear in the surface; anti-ITO sputtering performance is poor, influences the planarization of protective membrane.In addition, the heat-resisting discolouration of protective membrane B1-B4 is all below 4%, and the heat-resisting discolouration of protective membrane DD1-DD2 is respectively 5% and 6%, therefore, its under the higher situation of temperature, the light transmission less stable.In addition, by in composition, adding 1-methoxyl group-1-Ethoxyethane, make the levelling property of the protective membrane that obtains by said composition improve.
Claims (8)
1. film-forming resin, it is characterized in that, this film-forming resin contains the unit of monomer A formation and the unit that monomers B forms, described monomer A is the acrylate that contains epoxide group, described monomers B is one or more in (methyl) benzyl acrylate, (methyl) phenylethyl and (methyl) phenyl acrylate, in this film-forming resin, the unitary mol ratio that unit that described monomer A forms and described monomers B form is 1-8: 1, and the weight-average molecular weight of described film-forming resin is 5000-100000.
2. film-forming resin according to claim 1, wherein, in this film-forming resin, the unitary mol ratio that unit that described monomer A forms and described monomers B form is 1-5: 1, the weight-average molecular weight of described film-forming resin is 10000-50000.
3. film-forming resin according to claim 1, wherein, described monomer A is glycidyl acrylate, glycidyl methacrylate, Racemic glycidol-alpha-acrylic ethyl ester, Racemic glycidol-α-Jia Jibingxisuan ethyl ester, 3,4-epoxy butylacrylic acid ester, 3,4-epoxy butyl first acrylate, 6,7-epoxy hexane acrylate and 6, one or more in the 7-epoxy hexane methacrylic ester.
4. thermally curable resin composition, said composition contains film-forming resin and solidifying agent, it is characterized in that, and described film-forming resin is any described film-forming resin among the claim 1-3.
5. composition according to claim 4 wherein, is a benchmark with the film-forming resin of 100 weight parts, and the consumption of described solidifying agent is the 2-40 weight part.
6. composition according to claim 4, wherein, described solidifying agent is the mixed curing agent that contains acid anhydrides and phenol, described acid anhydrides is one or more in trimellitic anhydride, Tetra hydro Phthalic anhydride, tetrahydrochysene phthalate anhydride, methyl tetrahydrochysene phthalate anhydride, hexahydrophthalic anhydride and the pyromellitic acid anhydride, and described phenol is dihydroxyphenyl propane compound and/or bis-phenol sulphur compound; Total amount with solidifying agent is a benchmark, and the content of described acid anhydrides is 20-80 weight %, and the content of described phenol is 20-80 weight %.
7. composition according to claim 4, wherein, said composition also contains 1-methoxyl group-1-Ethoxyethane.
8. composition according to claim 7, wherein, the content of described 1-methoxyl group-1-Ethoxyethane be described solidifying agent weight 1-5 doubly.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007100905051A CN101284891B (en) | 2007-04-09 | 2007-04-09 | Film-forming resin and heat reactive resin compositions with the film-resin forming |
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| CN2007100905051A CN101284891B (en) | 2007-04-09 | 2007-04-09 | Film-forming resin and heat reactive resin compositions with the film-resin forming |
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| Publication Number | Publication Date |
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| CN101284891A CN101284891A (en) | 2008-10-15 |
| CN101284891B true CN101284891B (en) | 2011-06-15 |
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| CN103130955B (en) * | 2013-03-07 | 2015-06-17 | 京东方科技集团股份有限公司 | Photosensitive oligomer for photoresist, preparation method and negative photoresist composition thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1227115A2 (en) * | 2001-01-24 | 2002-07-31 | TDK Corporation | Crosslinkable polymer material of low relative permittivity, and films, substrates and electronic units formed of it |
| WO2003017001A1 (en) * | 2001-08-20 | 2003-02-27 | Dongjin Semichem Co., Ltd. | Photosensitive resin composition for photoresist |
| CN1558918A (en) * | 2001-09-25 | 2004-12-29 | 大日本印刷株式会社 | Alkali-soluble maleimide copolymer and liquid crystal display comprising the same |
| JP2006176746A (en) * | 2004-11-26 | 2006-07-06 | Jsr Corp | Copolymer, resin composition, protecting film and method for forming protecting film |
| CN1818781A (en) * | 2006-03-13 | 2006-08-16 | 苏州华飞微电子材料有限公司 | Dark ultraviolet negative photoresist and filming resin |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1227115A2 (en) * | 2001-01-24 | 2002-07-31 | TDK Corporation | Crosslinkable polymer material of low relative permittivity, and films, substrates and electronic units formed of it |
| WO2003017001A1 (en) * | 2001-08-20 | 2003-02-27 | Dongjin Semichem Co., Ltd. | Photosensitive resin composition for photoresist |
| CN1558918A (en) * | 2001-09-25 | 2004-12-29 | 大日本印刷株式会社 | Alkali-soluble maleimide copolymer and liquid crystal display comprising the same |
| JP2006176746A (en) * | 2004-11-26 | 2006-07-06 | Jsr Corp | Copolymer, resin composition, protecting film and method for forming protecting film |
| CN1818781A (en) * | 2006-03-13 | 2006-08-16 | 苏州华飞微电子材料有限公司 | Dark ultraviolet negative photoresist and filming resin |
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