TWI477556B - Curable resin composition, protective film and liquid crystal display device including the same - Google Patents

Description

Curable resin composition, protective film and liquid crystal display element containing the same

The present invention relates to a curable resin composition, a protective film formed using the composition, and a liquid crystal display element comprising the same, and particularly relates to a good stability over time, good heat and light resistance, and surface roughness. A low curable resin composition, a protective film formed using the composition, and a liquid crystal display element comprising the same.

Color filter layers have been widely used in applications such as color liquid crystal displays, color facsimile machines, color cameras, and the like. With the increasing market demand for office equipment such as color liquid crystal displays, the production technology of color filter layers has also become more diversified.

In general, the color-printed pixels on the surface of the color filter layer and the black matrix may cause irregularities, and a protective film is generally formed on the surface of the color filter layer, thereby hiding the unevenness and thereby achieving flattening. Claim. If the protective film itself is not flat, the color filter layer containing the protective film is assembled into a liquid crystal display device (LCD), and the LCD may have problems such as uneven coloration and poor LCD quality.

Secondly, there is an increasing demand for transparency of color filter layers. If the transparency of the protective film is not high enough, the color filter layer containing the protective film is assembled into an LCD, and the LCD may have problems such as insufficient brightness and poor LCD quality.

Although the prior art utilizes a pyrithion polymer and an alkyl quaternary amine to obtain a highly transparent protective film, the related literature on the above processes and materials can be found on the following day. Japanese Patent Publication No. 2007-211061 discloses a patent publication. However, the protective film obtained above has a problem of poor stability over time and poor heat-resistant light transmittance, and the protective film still has a problem of excessive surface roughness after film formation.

In view of the above, there is a need to provide a curable resin composition for improving the conventional curable resin composition and the protective film obtained therefrom due to poor stability over time, surface roughness, and heat-resistant transmittance. All kinds of shortcomings.

Therefore, one aspect of the present invention provides a curable resin composition comprising at least an alkali-soluble resin (A), a polyoxyalkylene polymer (B), and a solvent (C). Wherein the above alkali-soluble resin (A) is composed of an unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a1), an epoxy group-containing unsaturated compound (a2), and/or other unsaturated compound (a3). It is obtained by polymerization, and the above-mentioned curable resin composition has a water content of 0.01% by weight to 0.3% by weight.

Another aspect of the present invention provides a protective film which is a color filter protective film which is obtained by sequentially applying and heat-treating the above-mentioned curable resin composition.

Still another aspect of the present invention provides a liquid crystal display element comprising the above-mentioned protective film, thereby improving the conventional protective film which is susceptible to poor stability over time, poor heat-resistant light transmittance, and surface roughness. High disadvantages.

The curable resin composition of the present invention includes an alkali-soluble resin (A), a polyoxyalkylene polymer (B), and a solvent (C), which are described below.

Hereinafter, "(meth)acrylic acid" means acrylic acid and/or methacrylic acid, and "(meth)acrylate" means acrylate and/or methacrylic acid. The ester is represented by "(meth) propylene oxime" and propylene oxime and/or methacryl oxime.

Alkali soluble resin (A)

The alkali-soluble resin (A) of the present invention broadly refers to a resin which is soluble in an aqueous alkaline solution, and the structure thereof is not particularly limited. In one embodiment of the present invention, the alkali-soluble resin (A) may be a resin containing a carboxylic acid group, a phenol-novolac resin, or the like; preferably, the alkali-soluble resin (A) is The unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-1), the epoxy group-containing unsaturated compound (a-2) and/or other unsaturated compound (a-3) in the presence of a suitable polymerization initiator It is obtained by copolymerization in a solvent.

Unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-1)

The above unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-1) means a compound containing a carboxylic acid group or a carboxylic acid anhydride structure and an unsaturated bond for polymerization bonding, and the structure thereof is not particularly limited, for example, an unsaturated monocarboxylic acid. An acid compound, an unsaturated dicarboxylic acid compound, an unsaturated acid anhydride compound, a polycyclic unsaturated carboxylic acid compound, a polycyclic unsaturated dicarboxylic acid compound or a polycyclic unsaturated acid anhydride compound.

The specific examples of the above unsaturated monocarboxylic acid compound are as follows: (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-(methyl)acrylic acid ethoxylated Diester, 2-(methyl) propylene ethoxy hexahydro phthalate, 2-(meth) propylene ethoxy ethoxylate or omega (ω)-carboxy polycaprolactone Polyol monoacrylate (trade name: ARONIX M-5300, manufactured by Toagosei Co., Ltd.).

Specific examples of the above unsaturated dicarboxylic acid compound include maleic acid, fumaric acid, methyl fumaric acid, itaconic acid, citraconic acid, and the like, or an acid anhydride compound of the aforementioned unsaturated dicarboxylic acid compound.

Specific examples of the above polycyclic unsaturated carboxylic acid compound are, for example, 5-carboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5 -carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene or 5-carboxy-6-ethylbicyclo[2.2 .1] Hept-2-ene.

Specific examples of the above polycyclic unsaturated dicarboxylic acid compound are, for example, 5,6-dicarboxylic acid bicyclo[2.2.1]hept-2-ene.

The above polycyclic unsaturated dicarboxylic anhydride compound is an acid anhydride compound of the above polycyclic unsaturated dicarboxylic acid compound.

Specific examples of the above unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-1) include acrylic acid, methacrylic acid, maleic anhydride, 2-methylpropenyl ethoxy succinate, and 2-methyl propylene. Mercaptoethoxy hexahydrophthalic acid is preferred.

Further, the above unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-1) may be used singly or in combination of plural kinds. The amount of the monomer to be used in the polymerization of the alkali-soluble resin (A) is 100 parts by weight, and the amount of the above unsaturated carboxylic acid or unsaturated carboxylic anhydride compound (a-1) is from 5 parts by weight to 50 parts by weight. It is preferably from 8 parts by weight to 45 parts by weight, more preferably from 10 parts by weight to 40 parts by weight.

Epoxy-containing unsaturated compound (a-2)

The epoxy group-containing unsaturated compound (a-2) may, for example, be an epoxy group-containing (meth) acrylate compound, an epoxy group-containing α-alkyl acrylate compound or a glycidyl ether compound.

Specifically, specific examples of the above epoxy group-containing (meth) acrylate compound include: glycidyl (meth) acrylate, 2-methyl propyl propyl (meth) acrylate, (meth) acrylate 3,4-epoxybutyl acrylate, 6,7-epoxyglycol (meth) acrylate Ester, 3,4-epoxycyclohexyl (meth)acrylate or 3,4-epoxycyclohexylmethyl (meth)acrylate.

Specific examples of the above epoxy group-containing α-alkyl acrylate compound are, for example, α-ethyl methacrylate, α-n-propyl propylene acrylate, α-n-butyl butyl acrylate or α. - 6,7-epoxyheptyl ethacrylate.

Specific examples of the above-mentioned glycidyl ether compound are: o-vinylbenzylglycidylether, m-vinylbenzylglycidylcether or p-vinylbenzoic acid. P-vinylbenzylglycidylether.

Specific examples of the above epoxy group-containing unsaturated compound (a-2) include glycidyl methacrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and 6,7-cyclomethacrylate. Oxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether are preferred.

Further, the above epoxy group-containing unsaturated compound (a-2) may be used singly or in combination of plural kinds. The epoxy group-containing unsaturated compound (a-2) is used in an amount of 10 parts by weight to 80 parts by weight, based on 100 parts by weight, based on 100 parts by weight of the monomer when the alkali-soluble resin (A) is polymerized, and then 20 parts by weight. It is preferably from 70 parts by weight to more preferably from 25 parts by weight to 65 parts by weight. If the alkali-soluble resin (A) does not contain the epoxy group-containing unsaturated compound (a-2), there is a problem that the heat-resistant light transmittance is poor and the surface roughness is high.

Other unsaturated compounds (a-3)

The other unsaturated compound (a-3) described above may, for example, be an alkyl (meth)acrylate, an alicyclic (meth)acrylate, an aryl (meth)acrylate, an unsaturated dicarboxylic acid diester, A hydroxyalkyl (meth) acrylate, a polyether of (meth) acrylate, an aromatic vinyl compound or other unsaturated compound.

Specifically, the above-mentioned (meth)acrylic acid alkyl ester is specifically, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, or isopropyl (meth)acrylate. Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate or tertiary butyl (meth)acrylate.

Specific examples of the above (meth) acrylate cycloaliphatic ester are, for example, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]癸- 8-yl (meth) acrylate (or dicyclopentyl (meth) acrylate), dicyclopentyloxy (meth) acrylate, isobornyl (meth) acrylate or (meth) acrylate Tetrahydrofuran ester.

Specific examples of the above unsaturated dicarboxylic acid diester are, for example, diethyl maleate, diethyl fumarate or diethyl itaconate.

Specific examples of the above-mentioned hydroxyalkyl (meth)acrylate are 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate.

Specific examples of the polyether of the above (meth) acrylate are, for example, polyethylene glycol mono(meth)acrylate or polypropylene glycol mono(meth)acrylate.

Specific examples of the above aromatic vinyl compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene or p-methoxystyrene.

Specific examples of the above unsaturated compound include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl ethyl ester, 1,3-butadiene, and isoprene. Alkene, 2,3-dimethyl1,3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N-butyl Diterpenoidimine-3-maleimide benzoate, N-butanediamine-4-pyreneimine butyrate, N-butanediamine-6-horse Yttrium Hexanoate, N-butylenedimino-3-maleimide propionate or N-(9-acridinyl)maleimide.

Specific examples of the above other unsaturated compound (a-3) include methyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and tertiary (meth)acrylate. The ester, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentyloxy (meth)acrylate, styrene and p-methoxystyrene are preferred.

Further, the other unsaturated compound (a-3) described above may be used singly or in combination of plural kinds. The amount of the monomer used in the polymerization of the alkali-soluble resin (A) is 100 parts by weight, and the other unsaturated compound (a-3) is used in an amount of from 0 to 70 parts by weight, and then from 0 parts by weight to 55 parts by weight. Preferably, it is more preferably from 0 part by weight to 60 parts by weight.

Next, when the above-mentioned alkali-soluble resin (A) is produced, a suitable solvent may, for example, be an alcohol, an ether, a glycol ether, an ethylene glycol alkyl ether acetate, a diethylene glycol, a dipropylene glycol, a propylene glycol monoalkyl ether, Propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbon, ketone or ester, and the like.

Specific examples of the solvent for producing the alkali-soluble resin (A) include an alcohol such as methanol, ethanol, benzyl alcohol, 2-phenylethanol or 3-phenyl-1-propanol; an ether such as tetrahydrofuran; and an ethylene glycol single a glycol ether such as propyl ether, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; ethylene glycol alkyl group such as ethylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate or ethylene glycol methyl ether acetate Ether acetate; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, etc. Ethylene glycol alkyl ether acetate; dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ether and the like dipropylene glycol; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Propylene glycol monoalkyl ether such as monopropyl ether or propylene glycol monobutyl ether; propylene glycol alkyl ether acetate such as propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate; propylene glycol methyl ether Propionate, propylene glycol diethyl ether propionate, propylene glycol propyl ether propionate a propylene glycol alkyl ether propionate such as propylene glycol butyl ether propionate; an aromatic hydrocarbon such as toluene or xylene; a ketone such as methyl ethyl ketone, cyclohexanone or diacetone alcohol; methyl acetate, ethyl acetate or propyl acetate; , butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, methyl glycolate, ethyl hydroxyacetate, hydroxyl Butyl acetate, methyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2- Methyl hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxyacetic acid Propyl ester, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, butoxyacetate Ester, propyl butoxyacetate, butyl butoxyacetate, 3-methoxybutyl acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methyl Propyl oxypropionate, 2-methoxypropane Butyl ester, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, 2-butoxypropionic acid Methyl ester, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl ester, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionic acid Propyl ester, butyl 3-propoxypropionate, 3-butoxypropionic acid An ester of methyl ester, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate or the like.

Specific examples of the solvent for producing the alkali-soluble resin (A) are diethylene glycol dimethyl ether and propylene glycol methyl ether acetate, and preferably.

Further, the above-mentioned solvent for producing the alkali-soluble resin (A) may be used singly or in combination of plural kinds.

Further, when the above-mentioned alkali-soluble resin (A) is produced, a suitable polymerization initiator may be, for example, an azo compound or a peroxide, and specifically, for example, 2,2'-azobisisobutyronitrile, 2, 2 '-Azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azo Bis-2-methylbutyronitrile, 4,4'-azobis(4-cyanovaleric acid), dimethyl 2,2'-azobis(2-methylpropionate), 2,2 An azo compound such as '-azobis(4-methoxy-2,4-dimethylvaleronitrile); benzamidine peroxide, dodecyl peroxide, t-butyl peroxypivalate a peroxide of 1,1-bis(tert-butylperoxy)cyclohexane, hydrogen peroxide or the like. The above polymerization initiators for producing the alkali-soluble resin (A) may be used singly or in combination of plural kinds.

The alkali-soluble resin (A) of the present invention has a weight average molecular weight of usually 3,000 to 100,000, preferably 4,000 to 80,000, more preferably 5,000 to 60,000. The above-mentioned alkali-soluble resin (A) may be used singly or in combination of plural kinds, and a single resin or a combination of two or more resins having different molecular weights may be used to adjust the molecular weight thereof.

Polyoxane polymer (B)

The structure of the above polyoxyalkylene polymer (B) is not particularly limited, and for example, a combination of a decane monomer, a polyoxyalkylene or a decane monomer and a polyoxyalkylene can be used. It is obtained by adding water and partial condensation.

According to the above, the polyaluminoxane polymer (B) is a copolymer obtained by hydrolyzing and partially condensing a decane monomer represented by the formula (I): Si(R _a ) _z (OR _b ) _4-z (I)

In the formula (I), z represents an integer of 0 to 3; and R _a represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, and an acid anhydride. Alkyl group, alkyl group or oxyalkyl group containing propylene oxide group, and when z is represented by 2 or 3, plural R _a are each the same or different; R _b represents a hydrogen atom, and carbon number is 1 to 6. An alkyl group, a fluorenyl group having 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, and when 4-z represents 2, 3 or 4, a plurality of R _b are each the same or different.

In the definition of R _a of the formula (I), specific examples of the above alkyl group may include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, and Amaranthus, trifluoromethyl, 3,3,3-trifluoropropyl, 3-aminopropyl, 3-mercaptopropyl, 3-isocyanatepropyl, 3-epoxypropoxy, 2-( 3,4-epoxycyclohexyl)ethyl. Specific examples of the above alkenyl group may include, but are not limited to, a vinyl group, a 3-propenyloxypropyl group, a 3-methylpropenyloxypropyl group, and the like. Specific examples of the above aryl group may include, but are not limited to, phenyl, tolyl, p-hydroxyphenyl, 1-(p-hydroxyphenyl)ethyl, 2-(p-hydroxyphenyl)ethyl And 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl], naphthyl, and the like. Specific examples of the acid group-containing alkyl group may include, but are not limited to, 3-glutaric anhydride propyl group, 3-succinic anhydride propyl group, 2-succinic anhydride ethyl group, and the like.

Specific examples of the above propylene oxide group-containing alkyl group may include, but are not limited to, 2-ring Oxypropanylpentyl.

Specific examples of the above oxyalkyl group-containing oxyalkyl group may include, but are not limited to, 2-propylene oxide butyloxypropyl group, 2-propylene oxide butyloxypentyl group and the like.

In the definition of R _b of the formula (I), specific examples of the above alkyl group may include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl and the like. Specific examples of the above mercapto group may include, but are not limited to, an ethyl group. Specific examples of the above aryl group may include, but are not limited to, a phenyl group.

In the above formula (I), when z represents an integer of 0 to 3, when z is 0 (zero), the decane monomer represented by the formula (I) is a tetrafunctional decane; when z is 1, the formula ( The decane monomer represented by I) is a trifunctional decane; when z is 2, the decane monomer represented by the formula (I) is a difunctional decane; and when z is 3, the decane monomer represented by the formula (I) It is a monofunctional decane.

Specific examples of the above decane monomer may include, but are not limited to, tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, tetraphenoxysilane, and the like (tetraphenoxy silane). And other tetrafunctional decane; methyltrimethoxysilane (MTMS), methyltriethoxysilane, methyltriisopropoxysilane, methyltri-n-butoxy Trimethyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxy decane (ethyltri-n-butoxysilane), n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxydecane (n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane ), vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryoyloxypropyltrimethoxysilane, 3-methylpropenyloxypropylpropane 3-methylacryloyloxypropyltrimethoxysilane, 3-methylacryloyloxypropyltriethoxysilane, phenyltrimethoxysilane (PTMS), phenyltriethoxylate Phenyltriethoxysilane (PTES), p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2 -(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxyl) Phenylcarbonyloxy)pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane , 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3) , 4-(3-, 4-epoxycyclohexyl)ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-ethyl-3-[ [3-(Triphenyloxyindenyl)propoxy]methyl]epoxypropane {3-ethyl-3-[[3-(triphenoxysilyl)propoxy]methyl]oxetane}, commercially available from East Asia Synthetic Product: 3-ethyl-3-[[3-(trimethoxyindenyl)propoxy]methyl]epoxypropane {3-ethyl-3-[[ 3-(trimethoxysilyl)propoxy]methyl]oxetane} (trade name TMSOX-D), 3-ethyl-3-[[3-(triethoxyindolyl)propoxy]methyl]epoxypropane {3 -ethyl-3-[[3-(triethoxysilyl)propoxy]methyl]oxetane} (trade name: TESOX-D), 3-triphenoxysilyl propyl succinic anhydride, Commercial product manufactured by Shin-Etsu Chemical Co., Ltd.: 3-trimethoxysilyl propyl succinic anhydride (trade name X-12-967), commercially available from WACKER Product: 3-(triethoxysilyl)propyl succinic anhydride [trade name GF-20), 3-(trimethoxyindolyl)propyl glutaric anhydride [ 3-(trimethoxysilyl)propyl glutaric anhydride, referred to as TMSG], 3-(triethoxysilyl)propyl glutaric anhydride, 3-(triphenyloxyindenyl)propane Trifunctional decane such as 3-(triphenoxysilyl) propyl glutaric anhydride; dimethyldimethoxysilane (DMDMS), dimethyldiethoxysilane Dimethyldiacetyloxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, diisopropoxy-di(diphenyldimethoxysilane) Diisopropoxy-di(2-oxetanylpropylbutoxypropyl)silane (DIDOS), bis(3-epoxypropenylpentyl)dimethoxydecane [di(3-oxetanylpentyl) Dimethoxy silane], (di-n-butoxysilyl) di(propyl succinic anhydride), (dimethoxyindolyl) di(ethyl) (dimethoxysilyl)di(ethyl succinic anhydride); (4) monofunctional decane: trimethylmethoxysilane, tri-n-butylethoxysilane 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, di(2-ring) Oxypropanylbutoxypentyl)-2-epoxypropane pentylethoxy decane [di(2-oxetanylbutoxypentyl)-2-oxet Anylpentylethoxy silane], tris(2-oxetanylpentyl)methoxysilane, (phenoxysilyl)tris(propyl succinic anhydride)[(phenoxysilyl)tri (propyl succinic anhydride)], a difunctional decane such as (methoxysilyl) di(ethyl succinic anhydride). The above decane monomers may be used singly or in combination of two or more.

Next, the polyaluminoxane polymer (B) is a copolymer obtained by hydrolyzing and partially condensing a polyoxyalkylene represented by the formula (II):

In the formula (II), R _c , R _d , R _e and R _f each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms. Any one of the aforementioned alkyl group, alkenyl group and aryl group may optionally contain a substituent. When y is an integer from 2 to 1000, each R _c is the same or different, and each R _d is the same or different. The aforementioned alkyl groups may include, but are not limited to, methyl, ethyl, n-propyl and the like. The aforementioned alkenyl group may include, but is not limited to, a vinyl group, a acryloxypropyl group, a methacryloxypropyl group, and the like. The aforementioned aryl groups may include, but are not limited to, phenyl, tolyl, naphthyl and the like.

Next, in formula (II), above, and R _g R _h each represent a hydrogen atom, an alkyl group having a carbon number of 1 to 6 carbons, acyl of 1 to 6 carbon atoms in or aryl group of 6 to 15, wherein the the Any of the alkyl group, the fluorenyl group and the aryl group may optionally contain a substituent. The aforementioned alkyl groups may include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl and the like. The sulfhydryl group is, for example but not limited to, an ethyl group. The aforementioned aryl groups may include, but are not limited to, a phenyl group.

Further, in the formula (II), y is an integer of from 1 to 1,000, and preferably an integer of from 3 to 300 is preferred, and an integer of from 5 to 200 is more preferably.

Specific examples of the above polyoxyalkylene oxide may include, but are not limited to, 1,1,3,3-tetramethyl-1,3-dimethoxydioxane, 1,1,3,3-tetramethyl -1,3-diethoxydioxane, 1,1,3,3-tetraethyl-1,3-diethoxydioxane, decyl alcohol terminal polyoxane manufactured by Gelest Commercial product of silanol terminated polydimethylsiloxane) [trade name such as DM-S12 (molecular weight 400 to 700), DMS-S15 (molecular weight 1500~2000), DMS-S21 (molecular weight 4200), DMS-S27 (molecular weight 18000), DMS-S31 (molecular weight 26000), DMS-S32 (molecular weight 36000), DMS-S33 (molecular weight: 43,500), DMS-S35 (molecular weight: 49,000), DMS-S38 (molecular weight: 58,000), DMS-S42 (molecular weight: 77,000), PDS-9931 (molecular weight: 1,000 to 1400), and the like. The above various polyoxyalkylene oxides may be used singly or in combination of two or more.

In the production of the above polyoxyalkylene polymer (B), the mixing ratio of the above decane monomer to polyoxyalkylene is not particularly limited. Preferably, the molar ratio of Si atoms of the above decane monomer to polyoxyalkylene is from 100:0.1 to 50:50.

Next, in the production of the polyoxyalkylene polymer (B), the above-mentioned hydrolysis and partial condensation can be carried out by a general method. For example, a solvent, water or a selective catalyst may be added to a mixture of a decane monomer and/or a polysiloxane or a cerium oxide particle. Next, the mixture is heated and stirred at 50 ° C to 150 ° C for 0.5 hour to 120 hours. When stirring, by-products (alcohols, water, etc.) can be removed by distillation if necessary.

In addition, the solvent used for producing the polyoxyalkylene polymer (B) is not particularly limited, and may be the same as or different from the solvent (C) contained in the curable resin composition of the present invention. Preferably, the solvent used for producing the polyaluminoxane polymer (B) is added in an amount of 15 g to 1200 g based on the total weight of the decane monomer and/or the polyoxyalkylene, and is 20 g to 20 g. 1100 grams is preferred, and 30 grams to 1000 grams is more preferred.

Further, in the case where the hydrolyzable group contained in the above mixture is 1 mol, the amount of water for hydrolyzing may be, for example, 0.5 mol to 2 mol.

In addition, there is no particular catalyst used in the manufacture of the polyoxyalkylene polymer (B). Limitations may include, but are not limited to, acid catalysts or base catalysts. The aforementioned acid catalyst may include, but is not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or anhydride thereof, ion exchange resin, and the like. The foregoing base catalyst may include, but is not limited to, diethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, triheptylamine, trioctylamine, diethanolamine, triethanolamine, sodium hydroxide. , potassium hydroxide, an alkoxysilane containing an amine group, an ion exchange resin, and the like.

The catalyst used for producing the polyaluminoxane polymer (B) is added in an amount of from 0.005 g to 15 g, based on the total weight of the decane monomer and/or polyoxane, and is from 0.01 g to 12 g. Preferably, it is more preferably from 0.05 g to 10 g.

From the viewpoint of stability, the polyaluminoxane polymer (B) obtained by hydrolysis and partial condensation is preferably prepared by containing no by-products (such as alcohols or water) and a catalyst. The polyoxyalkylene polymer (B) can be selectively purified. The purification method described herein is not particularly limited. For example, the polyaluminoxane polymer (A) may be diluted with a hydrophobic solvent, and then the organic layer washed several times with water may be concentrated by an evaporator to remove the alcohol. Or water. Alternatively, the catalyst may be removed using an ion exchange resin.

The polysiloxane polymer (B) is used in an amount of 5 parts by weight to 100 parts by weight based on 100 parts by weight of the alkali-soluble resin (A), preferably 8 parts by weight to 90 parts by weight, more preferably 10 parts by weight. More preferably, it is 80 parts by weight. If the polyoxyalkylene polymer (B) is not used as the curable resin composition, there is a problem that the heat-resistant light transmittance is not good.

In addition to the polyaluminoxane polymer (B) which can be hydrolyzed and partially condensed by the above-described decane monomer and/or polyoxyalkylene oxide, it can also be mixed with dioxane. The silicon dioxide particles are obtained by copolymerization. The average particle diameter of the above-mentioned ceria is not particularly limited, and the average particle diameter thereof may be, for example, 2 nm to 250 nm, more preferably 5 nm to 200 nm, still more preferably 10 nm to 100 nm.

The above-mentioned cerium oxide particles can be, for example, commercially available from Catalyst Chemicals Co., Ltd. [trade name such as OSCAR 1132 (particle size 12 nm; dispersant is methanol), OSCAR 1332 (particle size 12 nm; dispersant is n-propanol) , OSCAR 105 (particle size: 60 nm; dispersant: γ -butyrolactone), OSCAR 106 (particle size: 120 nm; dispersant is diacetone alcohol), etc., and commercial products manufactured by Fuso Chemical Co., Ltd. [trade names such as Quartron PL-1-IPA (particle size 13 nm; dispersant is isopropanone), Quartron PL-1-TOL (particle size 13 nm; dispersant toluene), Quartron PL-2L-PGME (particle size 18 nm; dispersant is propylene glycol single Methyl ether), Quartron PL-2L-MEK (particle size 18 nm; dispersant is methyl ethyl ketone), etc., and a commercial product manufactured by Nissan Chemical Co., Ltd. [trade name such as IPA-ST (particle size 12 nm; dispersant is isopropyl) Alcohol), EG-ST (particle size 12nm; dispersant is ethylene glycol), IPA-ST-L (particle size 45nm; dispersant is isopropanol), IPA-ST-ZL (particle size 100nm; dispersant is Isopropyl alcohol), etc.]. The above-mentioned cerium oxide particles may be used singly or in combination of two or more.

When the above cerium oxide particles are mixed with a decane monomer and/or a polyoxyalkylene gas, there is no limitation on the amount used. In one embodiment, the molar ratio of the Si atom of the above cerium oxide particles to the Si atom of the polyoxyalkylene polymer (B) may be, for example, 1% to 50%.

Solvent (C)

The solvent (C) of the present invention is completely soluble in other organic components and The volatility must be high enough to evaporate from the dispersion at a normal pressure with a small amount of heat, especially a solvent having a boiling point of less than 150 ° C at normal pressure.

Specific examples of the solvent include benzene, toluene, and xylene; alcohols such as aromatics such as methanol and ethanol; alcohols such as methanol and ethanol; ethylene glycol monopropyl ether and diethylene glycol dimethyl ether. (diglyme), tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol ether, diethylene glycol butyl ether, etc.; ethylene glycol methyl ether acetate Ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, ethyl 3-ethoxypropionate, etc.; methyl ethyl ketone and ketones such as acetone.

The above solvent (C) is preferably used alone or in combination of diethylene glycol dimethyl ether, propylene glycol methyl ether acetate and ethyl 3-ethoxypropionate, and hardened thereby. The resin composition has better storage stability.

The solvent (C) is used in an amount of 5 parts by weight to 1000 parts by weight based on 100 parts by weight of the alkali-soluble resin (A), preferably 100 parts by weight to 900 parts by weight, more preferably 200 parts by weight to 800 parts by weight. The parts by weight are more preferred.

Thiol-containing compound (D)

The curable resin composition of the present invention may further optionally include a thiol functional group-containing compound (D), and the thiol-functional group-containing compound (D) may contain at least one thiol group in one molecule (mercapto group; -SH), however, polyfunctional thiol-containing functional compounds can also be used. The polyfunctional thiol-functional group-containing compound may, for example, contain at least two thiol groups in one molecule, and preferably contains at least three thiol groups in one molecule, and at least one molecule contains at least one molecule. 4 thiol groups are preferred.

Specific examples of the above polyfunctional thiol-functional group-containing compound may include, but are not limited to, ethylene glycol bis (thiopropionate); EGTP, butanediol bis(thiopropionic acid) Ester) [butanediol bis (thiopropionate); BDTP], trimethylolpropane tris (thiopropionate); TMTP], pentaerythritol tetrakis (thiopropionate) ;PEMP], a sulfhydryl group of tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate;THEIC-BMPA], represented by the following formula (III) Thiopropionate derivative; ethylene glycol bis(thioglycolate; EGTG), butanediol bis(thioglycolate; BDTG) a thioglycolate derivative such as hexandiol bis(thioglycolate; HDTG); 1,2-benzene dithiol, 1 , 3-phenyldithiol, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexanedithiol (1 ,6-hexamethy Lene dithiol), 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dithiol succinic acid [meso-2] , dimethyl sulphate, dimethyl thiolate a mercapto ether such as ether [di(mercaptoethyl)ether].

Specific examples of the above-mentioned thiol-functional group-containing compound (D) are preferably PEMP and THEIC-BMPA represented by the formula (III).

The compound (D) containing a thiol functional group is used in an amount of 1 part by weight to 10 parts by weight based on 100 parts by weight of the alkali-soluble resin (A), preferably 1 part by weight to 8 parts by weight, more preferably 1 part by weight It is more preferably from 6 parts by weight to 6 parts by weight. If the compound (D) having a thiol-functional group is used, there is an advantage that heat-resistant transmittance and surface roughness are better.

Additive (E)

The aforementioned curable resin composition may further optionally include an additive (E), which may include, but is not limited to, a surfactant (E-1), an adhesion promoter (E-2), a filler, a polymer compound (refer to the foregoing An alkali-soluble resin (A), an ultraviolet absorber, an anti-aggregation agent, a storage stabilizer, a heat resistance promoter, and the like.

The aforementioned surfactant may contribute to the improvement of the coatability of the aforementioned curable resin composition, and the suitable surfactant (E-1) may be, for example, a fluorine-containing surfactant or an organic barium surfactant.

Further, the terminal, main chain and side chain of the fluorosurfactant include at least a monofluoroalkyl group or a fluoroalkenyl group, which may include, but not limited to, 1, 1, 2, 2 - 4 Fluorinyl (1,1,2,2-tetrafluoropropyl)ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di(1,1,2,2-tetrafluoro Butyl)ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether, octapropylene glycol bis(1,1,2,2-tetrafluorobutyl)ether, hexapropylene glycol (1,1,2,2,3,3-hexafluoropentyl)ether, sodium perfluorododecyl sulfate, 1,1,2,2,8,8,9,9,10,10-ten Fluoric dodecane, 1,1,2,2,3,3-hexafluorodecane, sodium fluoroalkanesulfonate, sodium fluorocarbonate, sodium fluorocarbonate, fluorocarbon polyoxyethylene ether, dipropylene Alcohol tetra(fluoroalkane polyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkane betaine, fluorocarbon polyoxyethylene ether, perfluoroalkane polyoxyethylene ether, perfluoroalkyl alkanol. Further, specific examples of the fluorine-containing surfactant may include, but are not limited to, BM-1000, BM-1100 (manufactured by BM CHEMIE), Megafac F142D, F172, F173, F183, F178, F191, F471, F476 (Greater Japan ink and Chemical Industry), Fluorad FC 170C, FC-171, FC-430, FC-431 (manufactured by Sumitomo Chemical Co., Ltd.), chlorofluorocarbon S-112, S-113, S-131, S-141, S-145, S -382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (made by Asahi Glass), F Top EF301, 303, 352 (new Akita Chemicals), Ftergent FT-100, FT-110, FT-140A, FT-150, FT-250, FT-251, FTX-251, FTX-218, FT-300, FT-310, FT-400S (manufactured by NEOSU).

Specific examples of the aforementioned organic quinone surfactant may include, but are not limited to, Toray organic hydrazine, and trade names thereof are DC 3 Paint Additive (DC 3 PA), DC 7 PA, SH 11 PA, SH 21 PA, SH 28 PA, SH 29 PA, SH 30 PA, SH 190, SH 193, SZ 6032, SF-8427, SF-8428, DC 57, DC 190 (Dow Corning, manufactured by Toray Silicone), TSF-4440, TSF-4300, TSF-4445, TSF -4446, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.).

The surfactant (E-1) may also use a surfactant other than the above-mentioned fluorine-containing surfactant or organic barium surfactant, and may include, but not limited to, lauryl polyoxyethylene ether or polyoxyethylene stearic acid. a polyoxyethylene alkyl ether such as an ether or a polyoxyethylene oleyl ether; a polyoxyethylene aryl ether such as polyoxyethylene n-octyl phenyl ether or polyoxyethylene n-nonyl phenol ether; polyoxyethylene dilaurate; Polyoxyethylene dialkyl ester such as polyoxyethylene distearic acid; 3-methyl propyleneoxypropyl trimethoxy decane (trade name KBM403; manufactured by Shin-Etsu Chemical Co., Ltd.), poly flow No. 57, 95 (total Non-ionic surfactants such as Rongshe Oil Chemical Industry Co., Ltd.). The above surfactants (E-1) may be used singly or in combination of two or more.

Next, the aforementioned adhesion aid (E-2) can be used to enhance the adhesion of the curable resin composition to the substrate. Suitable adhesion promoters (E-2) may, for example, be functional decane crosslinkers, for example those comprising a carboxyl group, an alkenyl group, an isocyanate group, an epoxy group, an amine group, a fluorenyl group or a halogen.

Specific examples of the above-mentioned adhesion aid (E-2) may include, but are not limited to, p-hydroxyphenyltrimethoxydecane, 3-(meth)acryloxypropyltrimethoxydecane, ethylenetriethoxysilane. Base decane, ethylene trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, γ-isocyanate propyl triethoxy decane, 3-epoxypropoxy propyl Trimethoxy decane, 2-(3,4-epoxycyclohexane)ethyltrimethoxydecane, 3-glycidoxypropyldimethylmethoxydecane, 3-aminopropyltrimethyl Oxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane 3-巯propyltrimethoxydecane, 3-chloropropyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane. The above-mentioned adhesion aid (E-2) may be used alone or in combination of two or more.

Specific examples of the aforementioned filler may include, but are not limited to, glass, aluminum, and the like.

Specific examples of the polymer compound other than the alkali-soluble resin (A) may include, but are not limited to, polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and the like.

Specific examples of the aforementioned ultraviolet absorber may include, but are not limited to, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide, alkoxyphenone, and the like.

Specific examples of the aforementioned anti-agglomerating agent may include, but are not limited to, sodium polyacrylate and the like.

The aforementioned preservative stabilizer may include, for example, sulfur, hydrazine, hydroquinone, polyoxide, amine, nitroso compound or nitro group, and specific examples thereof may include, but are not limited to, 4-methoxyphenol, (N-nitrous acid) Alkyl-N-phenyl)hydroxylamine aluminum, 2,2-thiobis(4-methyl-.6-tert-butylphenol), 2,6-di-t-butylphenol, and the like.

The aforementioned heat resistance promoter may be, for example, an N-(alkoxymethyl)glycolide compound or N-(alkoxymethyl)melamine, and specific examples thereof may include, but are not limited to, N, N, N', N' -tetrakis(methoxymethyl)glycoluril, N,N,N',N'-tetrakis(ethoxymethyl)glycoluril, N,N,N',N'-tetra(n-propoxymethyl) Glycoluril, N, N, N', N'-tetrakis(isopropoxymethyl) glycoluril, N, N, N', N'-tetrakis (n-butoxymethyl) glycoluril, N , N, N', N'-tetrakis(t-butoxymethyl) glycoluril; preferably N-(N, N, N', N'-tetrakis(methoxymethyl) glycoluril, etc. Alkoxymethyl)glycolide compound; and N,N,N',N',N",N"-hexa(methoxymethyl)melamine, N,N,N',N',N", N"-hexa(ethoxymethyl)melamine, N,N,N',N',N",N"-hexa(n-propoxymethyl)melamine, N,N,N',N', N",N"-hexa(isopropoxymethyl)melamine, N,N,N',N',N",N"-hexa(n-butoxymethyl)melamine, N,N,N',N',N", N"-hexa(t-butoxymethyl) melamine or the like N-(alkoxymethyl)melamine. Among them, a specific example of the above heat resistance promoter is preferably N, N, N', N', N", N"-hexa(methoxymethyl) melamine, and a commercially available product such as NIKARAKKU N- 2702, MW-30M (made by Sanwa Chemical).

The above additive (E) may be used in an amount of, for example, 0 parts by weight to 10 parts by weight based on 100 parts by weight of the alkali-soluble resin (A), preferably 0 parts by weight to 6 parts by weight, more preferably 0 parts by weight. 3 parts by weight is more preferred. It should be noted that the amount of the additive (E) used in the present invention is determined and adjusted by routine experiment in the art to which the present invention pertains, and therefore the amount of the additive (E) of the present invention is It is not limited to the above.

Curable resin composition

In the curable resin composition of the present invention, the alkali-soluble resin (A), the polyoxyalkylene polymer (B), and the solvent (C) are generally placed in a stirrer and stirred to uniformly mix into a solution state. A compound (D) containing a thiol functional group, and/or a surfactant (E-1), an adhesion promoter (E-2), a filler, and a polymer compound (refer to the aforementioned alkali-soluble resin) may be added. Additives (E) such as an ultraviolet absorber, an anti-aggregation agent, a storage stabilizer, and a heat resistance promoter are uniformly mixed, and then a curable resin composition in a solution state can be prepared.

Next, the method for preparing the curable resin composition of the present invention is not particularly limited. For example, a part of the alkali-soluble resin (A) and the polyoxyalkylene polymer (B) may be previously dispersed in a part of the solvent (D). In the medium, after the dispersion is formed, the remaining portion of the alkali-soluble resin (A) and the polyoxyalkylene are further mixed. Produced by sub-(B).

It is worth mentioning that after the curable resin composition obtained above is prepared, the water removal procedure can be further carried out to lower the water content. The above-mentioned suitable water removal procedure is not particularly limited. For example, the formulated curable resin composition may be added to a molecular sieve, stirred and dehydrated, and filtered using a molecular sieve under dry nitrogen. Alternatively, the formulated curable resin composition may be blown off with dry nitrogen to remove water, and after the end of the water removal, solvent is added for replenishment.

The curable resin composition obtained above has a water content of 0.01% by weight (wt%) to 0.3% by weight after being subjected to a water removal procedure, and is preferably 0.01% by weight to 0.27% by weight, and further preferably 0.01% by weight to 0.025 wt% is more preferred. If a curable resin composition having a water content of 0.3% by weight or more is used, water causes a ring-opening reaction of an epoxy group, resulting in poor stability over time and an increase in surface roughness (due to uneven crosslinking degree). Therefore, there are problems of poor stability over time and high surface roughness. If a curable resin composition having a water content of 0.01% by weight or less is used, there is a problem that the cost is too high.

Method for forming protective film

In the method for forming a protective film of the present invention, the curable resin composition described above is applied onto a substrate, and then subjected to heat treatment such as prebaking to remove the solvent therein to form a color filter layer protective film.

Specific examples of the substrate include a substrate such as glass, quartz, rhodium, or resin. Specific examples of the above resin may include, but are not limited to, polyethylene terephalate, polyethylene terephalate, polyethersulfone, polycarbonate. ), polyimide, cycloolefin, etc. The polymer obtained by the ring opening reaction.

The coating method described above may be, for example, a spray method, a roller coating method, a spin coating method, a bar coating method, or an ink jet method. . The above coating method may preferably be carried out by a spin coater, a spin loess coating machine, a slit-die coating machine or the like.

The pre-bake conditions described above vary depending on the type of each component and the blending ratio. Usually, the pre-baking is carried out at a temperature of 70 ° C to 90 ° C for 1 minute to 15 minutes. After the prebaking, the thickness of the prebaked coating film is from 0.15 μm to 8.5 μm, preferably from 0.15 μm to 6.5 μm, more preferably from 0.15 μm to 4.5 μm. It is to be understood that the thickness of the pre-baked coating film refers to the thickness after solvent removal.

After the prebaking coating film is formed, it is heat-treated by a heating device such as a hot plate or an oven. The heat treatment temperature is usually from 150 to 250 ° C, wherein the heating time using the hot plate is from 5 minutes to 30 minutes, and the heating time using the oven is from 30 minutes to 90 minutes.

When a photoinitiator is used as the curable resin composition, if necessary, the curable resin composition may be applied onto the surface of the substrate, and the solvent may be removed by pre-baking to form a pre-baked coating film. The prebaked coating film is subjected to exposure treatment.

The light used for the above exposure treatment may be, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like, and light containing ultraviolet light having a wavelength of 190 nm to 450 nm is preferable.

The exposure amount of the above exposure treatment is preferably from 100 J/m ² to 20,000 J/m ^{2 , more} preferably from 150 J/m ² to 10,000 J/m ² .

After the above exposure treatment, it is possible to selectively perform heat treatment using a heating device such as a hot plate or an oven. The heat treatment temperature is usually from 150 to 250 ° C, wherein the heating time using the hot plate is from 5 minutes to 30 minutes, and the heating time using the oven is from 30 minutes to 90 minutes.

Color filter protective film

The film thickness of the color filter layer protective film obtained above is from 0.1 μm to 8 μm, more preferably from 0.1 μm to 6 μm, still more preferably from 0.1 μm to 4 μm. It can be understood that when the protective film of the present invention is formed on the substrate but has a height difference from the color filter layer, the film thickness of the protective film refers to the film thickness calculated from the upper surface of the color filter layer.

As will be apparent from the examples described later, the protective film of the present invention can simultaneously satisfy adhesion, surface hardness, transparency, heat resistance, light resistance, solvent resistance and the like. The protective film of the present invention can withstand weight without being recessed in a heated state, and can provide flattening when it has a height difference from the color filter layer on the lower substrate, and thus can be applied to a protective film for optical instruments.

In particular, the protective film of the present invention can be exposed to a panel process exceeding 250 ° C and ensures that dimensional stability can be effectively maintained at 270 ° C.

Method for manufacturing liquid crystal display element

The liquid crystal display element of the present invention can be produced by the following method. First, the curable resin composition of the present invention is formed into a protective film on at least one side or both sides of a transparent substrate provided with a color filter layer by the above method. then, The transparent substrate provided with the color filter layer of the protective film is disposed opposite to the intervening gap (cell gap) between the driving substrates provided with the thin film transistor (TFT), wherein the substrate is The side with the alignment film is used as the inner surface.

Thereafter, the peripheral portions of the two substrates are bonded together with a sealing agent, and a liquid crystal is filled in a gap between the surface of the substrate and the sealing agent, and the injection holes are sealed to form a liquid crystal cell. Subsequently, a liquid crystal display element was produced by laminating a polarizing plate on the outer surface of the liquid crystal cell, that is, on the other side faces of the respective substrates constituting the liquid crystal cell.

Another method of sealing is to apply a UV-curable adhesive along the end of one of the substrates, and then use a liquid crystal dispenser to drop the tiny liquid crystal onto the substrate, and then vacuum and another A stack of substrates is stacked and sealed under the illumination of a high pressure mercury lamp that emits ultraviolet light. Finally, after bonding the polarizing plates inside and outside the liquid crystal, a liquid crystal display element can be obtained.

The liquid crystal used in the above, that is, the liquid crystal compound or the liquid crystal composition is not particularly limited herein, and any liquid crystal compound and liquid crystal composition can be used.

Further, the liquid crystal alignment film used as described above is used to restrict the alignment of liquid crystal molecules, and is not particularly limited herein, and any of an inorganic substance or an organic substance may be used. The technique for forming a liquid crystal alignment film is well known to those of ordinary skill in the art to which the present invention pertains, and is not the focus of the present invention, and therefore will not be further described.

The following embodiments are used to illustrate the application of the present invention, and are not intended to limit the present invention. Those skilled in the art can make various changes without departing from the spirit and scope of the present invention. Retouching.

Synthesis Example A-1: Method for Producing Alkali Soluble Resin (A-1-1)

A nitrogen inlet, a stirrer, a heater, a condenser, and a thermometer were placed on a four-necked conical flask having a volume of 500 ml, and nitrogen gas was introduced and 240 parts by weight of the solvent diethylene glycol dimethyl ether was added in an amount shown in Table 1.

When the solvent of the four-necked flask is stirred, the temperature of the oil bath is raised to 85 ° C, and then the monomer mixture: 30 parts by weight of methacrylic acid monomer (hereinafter referred to as MAA), methacrylic acid, as shown in Table 1 30 parts by weight of a glycidyl ester monomer (hereinafter abbreviated as GMA), 20 parts by weight of a butyl methacrylate monomer (hereinafter abbreviated as TBMA), and 20 parts by weight of a styrene monomer (hereinafter abbreviated as SM) are continuously added to a four-necked cone The bottle was stirred and mixed while raising the temperature of the oil bath of the four-necked flask to 85 °C. Further, 2.4 parts by weight of a polycondensation initiator: 2,2'-azobis-2-methylbutyronitrile (hereinafter abbreviated as AMBN) is dissolved in a solvent of diethylene glycol dimethyl ether, and is divided into five equal portions. Add an aliquot to the four-necked flask at intervals of 1 hour. The reaction temperature of the whole polycondensation process is maintained at 85 ° C, and the polycondensation time lasts for 5 hours. After the polycondensation is completed, the polycondensation product is taken out from the four-necked flask, and the solvent is devolatilized to obtain an alkali-soluble resin ( A-1-1).

Synthesis Example A-1-2 to A-1-4: Method for Producing Alkali Soluble Resin (A-1-2 to A-1-4)

In the synthesis examples A-1-2 to A-1-4, the same operation method as in the synthesis example A-1-1 was used, except that the types and mixing amounts of the monomers for polycondensation were changed, and the formulation and reaction conditions thereof were used. Both are listed in Table 1.

Synthesis Example B-1: Method for Producing Polyoxane Polymer (B-1)

A nitrogen inlet, a stirrer, a heater, a condenser and a thermometer were placed on a four-necked conical flask having a volume of 500 ml, and nitrogen gas was introduced and a solvent of propylene glycol monoethyl ether (hereinafter referred to as PGEE) was added in an amount of 100 g according to the amount shown in Table 2. Diacetone alcohol (hereinafter referred to as DAA) 80 g.

When the solvent of the four-necked flask is stirred, the temperature of the oil bath is raised to 110 ° C, and then the decane monomer / polyoxane: methyl trimethoxy decane monomer (hereinafter referred to as MTMS) is shown in Table 2. 0.40 mol, phenyltrimethoxydecane monomer (hereinafter referred to as PTMS) 0.55 mol and 3-(triethoxyindenyl)propyl succinic anhydride monomer (hereinafter referred to as GF-20) 0.05 mol, It was continuously added to a four-necked flask and stirred and mixed while raising the temperature of the oil bath of the four-necked flask to 110 °C. Separately, a polycondensation initiator was used: 75 g of water and 0.40 g of oxalic acid, and divided into three equal portions, and an aliquot was added to the above four-necked flask at intervals of 1 hour. The reaction temperature of the whole polycondensation process is maintained at 110 ° C, and the polycondensation time is maintained for 3 hours. After the polycondensation is completed, the polycondensation product is taken out from the four-necked flask, and the solvent is devolatilized to obtain a polyoxane. Polymer (B-1).

Synthesis Example B-2 to B-4: Method for Producing Polyoxane Polymer (B-2 to B-4)

Synthesis Examples A-1-2 to A-1-4 used the same operation method as in Synthesis Example B-1, except that the types and mixing amounts of the monomers for polycondensation were changed, and the formulation and reaction conditions were carried out. In the second table.

Method for producing curable resin composition

Hereinafter, the curable resin compositions of Examples 1 to 10 and Comparative Examples 1 to 6 were prepared according to the third table and the fourth table, respectively.

Example 1

100 parts by weight (solid content) of the alkali-soluble resin (A-1-1) obtained in the above Synthesis Example A-1-1, and 20 parts by weight of the polyoxyalkylene polymer (B-1) obtained in Synthesis Example B-1 (solid content), 500 parts by weight of a solvent propylene glycol methyl ether acetate (hereinafter referred to as PGMEA; D-1) was added, and then dissolved and mixed by a shaking stirrer to prepare a curable resin composition. The curable resin composition was subjected to water removal by a water removal procedure, and the characteristics were measured by the respective evaluation methods described later. The results are shown in Table 3.

Examples 2 to 10 and Comparative Examples 1 to 6

Examples 2 to 10 and Comparative Examples 1 to 6 used the same operation method as the method for producing the curable resin composition of Example 1, except that Examples 2 to 10 and Comparative Examples 1 to 6 changed the composition of the curable resin. The details of the raw materials and the amount of the materials used, the water removal procedure, and the number of times of use thereof are shown in Tables 3 (Examples 2 to 10) and Table 4 (Comparative Examples 1 to 6), respectively.

The above-mentioned water removal procedures can be divided into two types, which are briefly described as follows: Water removal procedure "※": The prepared hardening composition is added to the granular 4A molecular sieve, stirred and dehydrated, and filtered by molecular sieve under dry nitrogen. .

Water removal procedure "#": The prepared hardenable composition is blown with dry nitrogen to remove water, and after the completion of the water removal, solvent is added for replenishment.

The curable resin composition of the above-mentioned Example 1, Example 5, Example 6, and Comparative Example 1 was used once by the water removal procedure of the following "※", and the curable resin composition of Example 2 and Example 10 was utilized. The water removal procedure of the following "※" was performed twice, and the curable resin compositions of Example 3, Example 7, and Comparative Example 2 were dewatered by the following "#". The procedure was carried out once, and the curable resin compositions of Example 4, Example 8 and Example 9 were subjected to the water removal procedure of the following "#" twice:

Water removal procedure "※": The prepared curable resin composition is added to a molecular sieve, stirred and dehydrated, and filtered through a molecular sieve under dry nitrogen.

Water removal procedure "#": The prepared hardening resin composition is blown with dry nitrogen to remove water, and after the completion of the water removal, solvent is added for replenishment.

Protective film formation

The various curable resin compositions prepared in Examples 1 to 10 and Comparative Examples 1 to 6 were placed in a coater (Model MS-A150; purchased from Shinko Trading) by spin coating. It was coated on a glass substrate of 100 mm × 100 mm, dried under reduced pressure at 100 mmHg for 5 seconds, and then pre-baked in an oven at 90 ° C for 2 minutes to form a pre-baked coating film having a film thickness of 2.2 μm. Then, after baking at 235 ° C for 30 minutes in an oven, a protective film having a film thickness of 1.9 μm was formed on the glass substrate.

Evaluation method

The aforementioned curable resin composition and the protective film obtained therefrom can be tested for water content, stability over time, surface roughness, and heat-resistant transmittance according to the following steps to evaluate the efficacy.

1. Water content:

Each of the curable resin compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 6 was placed in a moisture content titrator (manufactured by Mettler Co., Model E665), and then by Karl Fischer Reagent SS (hereinafter referred to as KF). The reagent SS, titration equivalent = 0.7 to 1.0 (mgH ₂ O/ml) is titrated, and the water content of the curable resin composition can be calculated according to the following formula (IV), and the results are as shown in Tables 3 to 4. Show: water content (wt%) = [KF reagent SS titration equivalent (mgH ₂ O / ml) × KF reagent SS titer (ml) / total amount of curable resin (mg)] × 10 ² (IV)

2. Stability over time:

The various curable resin compositions prepared in Examples 1 to 10 and Comparative Examples 1 to 6 were placed in an environment of 25 ° C, and the viscosity test was performed one month later, and the viscosity change rate was calculated according to the following formula (V). Evaluated according to the following criteria:

○: viscosity change rate ≦5%

△: 5% < viscosity change rate ≦ 8%

×: 8% < viscosity change rate

3. Surface roughness:

The protective films prepared in Examples 1 to 10 and Comparative Examples 1 to 6 were measured by an atomic force microscope (model: Dimension Edge AFM; manufactured by Veeco) to measure a curable resin (measurement distance was 3 μm). After calculating the surface flatness according to the following formula (VI), it is evaluated according to the following criteria: surface flatness (nm) = (δ _H ) - (δ _L ) (VI)

◎: Surface flatness <30nm

○: 30 nm ≦ surface flatness <60 nm

△: 60nm ≦ surface flatness <100nm

╳: 100nm ≦ surface flatness

4. Heat resistant transmittance:

The protective films prepared in the foregoing Examples 1 to 10 and Comparative Examples 1 to 6 were baked in an oven at 280 ° C for 30 minutes, and measured by a penetrating absorption spectrum analyzer (MCPD-Series, Otsuka Technology). The transmittance of the protective film after baking through the wavelength of 400 nm to 800 nm is at least five points, and the measured data is averaged to obtain the transmittance value corresponding to the wavelength of 400 nm, which is the data of the heat-resistant transmittance. And evaluated according to the following criteria:

◎: 95% ≦ light transmittance

○: 90% ≦ transmittance <95%

△: 80% ≦ light transmittance <90%

×: light transmittance <80%

From the results of Example 1 to Example 10 of Table 3, it is understood that the amount of the benzoic acid-soluble resin (A), the polysiloxane polymer (B), and the solvent (C) used for controlling the curable resin composition and The water content of the curable resin composition, the curable resin composition, and the protective film obtained thereof exhibit better temporal stability, surface roughness, and heat-resistant light transmittance, and thus the object of the present invention can be attained. In contrast, the cured resin composition of Comparative Example 1 to Comparative Example 6 of Table 4 and the protective film obtained thereof have less stability over time, surface roughness, and heat-resistant transmittance. ideal.

It should be noted that the present invention describes the curable resin composition of the present invention and the protective film formed thereof by exemplification of specific compounds, compositions, reaction conditions, processes, analytical methods or specific instruments, but the present invention belongs to the present invention. It is to be understood by those skilled in the art that the present invention is not limited thereto, and other compounds and compositions may be used for the curable resin composition of the present invention and the protective film formed thereof without departing from the spirit and scope of the present invention. , reaction conditions, process, analytical methods or instruments.

The present invention has been disclosed in the above embodiments, but it is not intended to limit the invention, and any one of ordinary skill in the art to which the present invention pertains can be modified and retouched without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims.

Claims (4)

A curable resin composition comprising: an alkali-soluble resin (A), wherein the alkali-soluble resin (A) is composed of an unsaturated carboxylic acid or an unsaturated carboxylic anhydride compound (a-1), and an epoxy group-containing unsaturated group The compound (a-2) and/or the other unsaturated compound (a-3) are copolymerized, and the amount of the monomer for polymerization of the alkali-soluble resin (A) is 100 parts by weight, the unsaturated carboxylic acid or The unsaturated carboxylic anhydride compound (a-1) is used in an amount of 5 parts by weight to 50 parts by weight, and the epoxy group-containing unsaturated compound (a-2) is used in an amount of 10 parts by weight to 80 parts by weight, the other The unsaturated compound (a-3) is used in an amount of from 0 part by weight to 70 parts by weight; the polyaluminoxane polymer (B) wherein the polyaluminoxane polymer (B) is represented by the formula (I) a copolymer obtained by hydrolyzing and partially condensing a decane monomer: Si(R _a ) _z (OR _b ) _4-z (I) In the formula (1), z represents an integer of 0 to 3; R _a represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkyl group having an acid anhydride group, an alkyl group containing an oxypropylene group or oxygen. An alkyl group, and when z represents 2 or 3, a plurality of R _a are each From the same or different; the R _b represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 1 to 6 carbon atoms, an aryl group having 6 to 15 carbon atoms, and when 4-z represents 2 or 3 or 4 When the plurality of R _b are the same or different, and the solvent (C); wherein the curable resin composition has a water content of 0.01% by weight to 0.3% by weight, and based on the amount of the alkali-soluble resin (A) The polyoxyalkylene polymer (B) is used in an amount of 5 parts by weight to 100 parts by weight, and the solvent (C) is used in an amount of 50 parts by weight to 1000 parts by weight per 100 parts by weight. The curable resin composition according to claim 1, further comprising at least one thiol-functional group-containing compound (D), and based on the alkali-soluble resin (A) used in an amount of 100 parts by weight, The compound (D) of the thiol functional group is used in an amount of from 1 part by weight to 10 parts by weight. A protective film obtained by sequentially applying a coating and heat treatment to a curable resin composition according to any one of claims 1 to 2, which is obtained by coating and heat treatment. . A liquid crystal display element comprising the color filter layer protective film according to item 3 of the patent application.