TWI396715B - Resin composition, protection film of color filter and producing thereof - Google Patents

Description

Resin composition, protective film for color filter and method of forming same

The present invention relates to a resin composition, a method of forming a protective film for a color filter from the resin composition, and a color filter protective film. More specifically, it relates to a resin composition suitable as a material for forming a protective film for a color filter for a liquid crystal display element (LCD) and a color filter for a charge coupled device (CCD), and protection using the resin composition A film forming method and a protective film formed of the composition.

The radiation device such as an LCD or a CCD is subjected to immersion treatment of the display element with a solvent, an acid or an alkali solution or the like in the manufacturing step thereof, and when the wiring electrode layer is formed by sputtering, the surface of the element is locally subjected to a high temperature. Thus, in order to prevent deterioration or damage of the components caused by such treatment, a protective film formed of a film resistant to these treatments is provided on the surface of the member.

Such a protective film is required to have the following properties: high adhesion to a substrate or a lower layer and a layer formed on the protective film for forming the protective film; the film itself is smooth and high in strength; has transparency; high heat resistance and light resistance; After a long period of time, coloring, yellowing, whitening, and the like are not deteriorated, and water resistance, solvent resistance, acid resistance, and alkali resistance are excellent. As a material which forms a protective film satisfying various characteristics, for example, a thermosetting composition containing a polymer having a glycidyl group is known (see Patent Document 1 and Patent Document 2).

Further, when such a protective film is used as a protective film for a color filter of a color liquid crystal display device and a charge coupling element, it is generally required to planarize a color filter step layer formed on the base substrate.

Further, in a color liquid crystal display device such as an STN (Super Twisted Nematic) type or a TFT (Thin Film Transistor) type color liquid crystal display element, in order to keep the gap of the liquid crystal layer unit uniform, a bead-shaped separator is spread on the protective film. Based on the fit, the panel is attached. Then, the liquid crystal cell is sealed by thermocompression sealing material, but at this time, under such heat and pressure, there is a problem that the protective film of the bead portion is dented, resulting in inaccurate cell gap.

In particular, when manufacturing an STN type color liquid crystal display element, the bonding precision of the color filter and the opposite substrate must be very strict, and thus the protective film needs to have a very high level of planarization performance and heat resistance and withstand voltage.

In the formation of such a protective film, it is convenient to use a thermosetting composition which has the advantage that a protective film excellent in hardness can be formed by a simple method, but a protective film resin composition for expressing the above various characteristics The substance has a highly reactive crosslinking group or a catalyst which makes it form a strong crosslink, and thus there is a problem that the shelf life of the composition itself is very short, and the treatment is very troublesome. That is to say, the coating property of the composition itself is not only deteriorated with time, but also the coating machine must be frequently maintained, cleaned, etc., which is cumbersome in operation.

It has not been known that a protective film which satisfies the above-described various performances and which satisfies the above-described various performances of the protective film such as transparency can be easily formed, and which is excellent in storage stability of the composition.

Further, Patent Document 3 discloses a thermosetting composition including a latent carboxyl compound used in a coating, an ink, a binder, and a molded article, but does not disclose any aspect relating to a color filter protective film.

[Patent Document 1] JP-A-2001-91732 (Patent Document 3)

The present invention has been made in view of the above circumstances, and an object thereof is to provide a composition capable of forming a cured film having high flatness on a substrate even if it has a low surface flatness, and is suitable for forming transparency. And a protective film for an optical device having excellent surface hardness, heat resistance, pressure resistance, acid resistance, alkali resistance, and sputtering resistance, and excellent in storage stability as a composition; and providing the above composition A method of forming a protective film, and a protective film formed of the above composition.

The present invention relates to a resin composition characterized by being polymerizable unsaturated compound having an oxiranyl group or an oxetanyl group with respect to 100 parts by weight of (A): (a1) and (a2) The copolymer of the polymerizable unsaturated compound other than the above (a1) contains 0.01 to 50 parts by weight of (B) a phosphate ester having a structure represented by the following formula (1).

[X in the formula (1) represents an integer of 0-2. R ¹ represents a hydrogen atom or an organic group in which an atom adjacent to the phosphorus atom is a carbon atom. R ² represents an organic group in which an atom adjacent to an oxygen atom is a carbon atom. ]

Wherein the component (B) is preferably an alkyl group, an aryl group, a benzyl group having 1 to 18 carbon atoms or a terminal or side chain having ^{1 to 10} carbon atoms in the formula (1) The alkoxy group of 4 has an alkyl group having 1 to 8 carbon atoms or an acetate group, and R ² is an alkyl group having 1 to 18 carbon atoms or an aryl group or a benzyl group.

Further, specific examples of the component (B) include trimethyl phosphate and/or triethyl phosphate.

The resin composition of the present invention may further contain 0.0001 to 20 parts by weight of a (C) Lewis acid catalyst per 100 parts by weight of the component (A).

Furthermore, the resin composition of the present invention may further contain 3 to 200 parts by weight of (D) a cationically polymerizable compound (excluding the component (A) above) with respect to 100 parts by weight of the component (A).

The resin composition of the present invention can be used to form a protective film of a color filter.

Next, the present invention relates to a method of forming a color filter protective film, which is characterized in that a coating film is formed by using the above resin composition, followed by heat treatment.

Further, the present invention relates to a protective film of a color filter formed of the above resin composition.

According to the present invention, it is possible to provide a resin composition capable of forming a cured film having high flatness on the substrate even in a substrate having a low surface flatness, and is suitable for forming transparency, surface hardness, and heat resistance. A protective film for an optical device excellent in various resistances such as pressure resistance, acid resistance, alkali resistance, and sputtering resistance, and excellent in storage stability of the composition; and a method of forming a protective film using the resin composition And a protective film formed of the above composition.

Hereinafter, each component of the resin composition of the present invention will be described.

(A) copolymer

The (A) copolymer of the present invention contains a polymerized unit derived from (a1) a polymerizable unsaturated compound having an oxiranyl group or an oxypropylene group, and a polymerization unit derived from (a2) the above (a1). Polymeric unsaturated compound Aggregation unit.

In the (A) copolymer, the (a1) polymerizable unsaturated compound is not particularly limited as long as it has an oxiranyl group or an propylene oxide group and a polymerizable unsaturated group.

For example, examples of the polymerizable unsaturated compound containing an oxirane group include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, glycidyl α-n-propyl acrylate, and α. - glycidyl butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, methacrylic acid -6,7-epoxyheptyl ester, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-ethylene Glycidyl glycidyl ether and the like.

Further, examples of the polymerizable unsaturated compound containing an oxypropylene group include 3-methyl-3-(methyl)propenyloxymethyl propylene oxide and 3-ethyl-3-(methyl). Propylene methoxymethyl propylene oxide and the like.

Among them, from the viewpoint of improving the copolymerization reactivity and the heat resistance and surface hardness of the obtained protective film or insulating film, it is preferred to use glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl ester, ortho- Vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like.

(A) The copolymer contains, in addition to the component (a1), a polymer unit derived from (a2) a polymerizable unsaturated compound other than the above (a1). (a2) The polymerizable unsaturated compound may, for example, be an alkyl (meth)acrylate, a cycloalkyl (meth)acrylate, an aryl (meth)acrylate, an unsaturated dicarboxylic acid diester, or a bicyclic unsaturated group. a compound, a maleimide compound, an unsaturated aromatic compound, a conjugated diene compound, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated dicarboxylic acid anhydride, an acetal, a ketal Structure of unsaturated compounds, etc.

Specific examples of the (a2) polymerizable unsaturated compound include, for example, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and (methyl). 3-hydroxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-methyl propylene oxime Ethyl glucoside, 4-hydroxyphenyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, dibutyl (meth) acrylate Ester, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, tridecyl (meth)acrylate, (methyl) ) n-octadecyl acrylate, tert-butoxy (meth) acrylate, 1-dimethyl(iso)propyl (meth) acrylate, 1-dimethyl(iso)butyl (a) Acrylate, 1-dimethyl(iso)octyl (meth) acrylate, 1-methyl-1-ethylethyl (meth) acrylate, 1-methyl-1-ethyl ( Isopropyl (meth) acrylate, 1-methyl-1- Ethyl (iso)butyl (meth) acrylate, 1-methyl-1-ethyl (iso) octyl acrylate, 1-diethyl (isopropyl) propyl (meth) acrylate, 1- Diethyl (iso)butyl (meth) acrylate, 1-diethyl (iso) octyl (meth) acrylate, etc.; (meth) acrylate cycloalkyl ester can be exemplified by (meth)acrylic acid ring hexyl ester, (meth) acrylate, 2-methyl-cyclohexyl ester, (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6]} decan-8-yl ester, (meth) acrylate, tricyclo [5.2.1.0 ^{2 , 6} ]decane-8-yloxyethyl ester, isobornyl (meth)acrylate, 1-methylcyclopropyl (meth)acrylate, 1-methylcyclobutyl (meth)acrylate Alkyl ester, 1-methylcyclopentyl (meth)acrylate, 1-methylcyclohexane (meth)acrylate, 1-methylcycloheptyl (meth)acrylate, ( 1-methylcyclooctylalkyl (meth)acrylate, 1-methylcyclononyl (meth)acrylate, 1-ethylcyclodecyl (meth)acrylate, (meth)acrylic acid 1 -ethylcyclopropyl ester, 1-ethylcyclobutyl (meth)acrylate, 1-ethylcyclopentane (meth)acrylate Base ester, 1-ethylcyclohexane (meth)acrylate, 1-ethylcycloheptyl (meth)acrylate, 1-ethylcyclooctyl (meth)acrylate, (A) 1-ethylcyclodecyl acrylate, 1-ethylcyclodecyl (meth) acrylate, 1-(isopropyl)cyclopropyl (meth) acrylate, (meth) acrylate 1-(Isopropyl)cyclobutylalkyl ester, 1-(iso)propylcyclopentyl (meth)acrylate, 1-(iso)propylcyclohexane (meth)acrylate, ( 1-(Isopropyl)cycloheptyl (meth)acrylate, 1-(iso)propylcyclooctyl (meth)acrylate, 1-(iso)propylcyclodecane (meth)acrylate Base ester, 1-(iso)propylcyclodecyl (meth)acrylate, 1-(iso)butylcyclopropane (meth)acrylate, 1-(iso)butyl (meth)acrylate Cyclobutane, 1-(iso)butylcyclopentyl (meth)acrylate, 1-(iso)butylcyclohexyl (meth)acrylate, 1-(meth)acrylate Isobutylcycloheptyl ester, 1-(iso)butylcyclooctyl (meth)acrylate, 1-(iso)butylcycloalkyl (meth)acrylate, (methyl) Propylene 1-(Isobutyl)cyclodecylalkyl ester, 1-(iso)pentylcyclopropane (meth)acrylate, 1-(iso)pentylcyclobutane (meth)acrylate, (A) 1-(iso)pentylcyclopentyl acrylate, 1-(iso)pentylcyclohexyl (meth) acrylate, 1-(iso)pentylcycloheptyl (meth) acrylate Ester, 1-(iso)pentylcyclooctyl (meth)acrylate, 1-(iso)pentylcyclodecyl (meth)acrylate, 1-(iso)pentyl (meth)acrylate Cyclodecylalkyl ester, 1-(iso)hexylcyclopropane (meth)acrylate, 1-(iso)hexylcyclobutyl (meth)acrylate, 1-(iso)hexyl (meth)acrylate Cyclohexane ester, 1-(iso)hexylcycloheptyl (meth)acrylate, 1-(iso)hexylcyclooctyl (meth)acrylate, 1-(iso)(meth)acrylate Hexylcyclodecylalkyl ester, 1-(iso)hexylcyclodecyl (meth)acrylate, 1-(iso)heptylcyclopropyl (meth)acrylate, 1-(iso)(meth)acrylate Heptylcyclobutylalkyl ester, 1-(iso)heptylcycloheptyl (meth)acrylate, 1-(iso)heptylcyclooctyl (meth)acrylate, (meth) propylene 1-(Iso)heptylcyclodecylalkyl ester, 1-(iso)heptylcyclodecyl (meth)acrylate, 1-(iso)octylcyclopropane (meth)acrylate, (A) 1-(iso)octylcyclobutane acrylate, 1-(iso)octylcyclooctyl (meth) acrylate, 1-(iso)octylcycloheptyl (meth) acrylate Ester, 1-(iso)octylcyclodecyl (meth)acrylate, 1-(iso)octylcyclodecyl (meth)acrylate, 2-ethyltricyclo[3.3.1.1 ^{3 , 7} ]decane-2-yl-(meth)acrylate, 2-methyltricyclo[3.3.1.1 ^{3 , 7} ]decane-2-yl-(meth)acrylate, 1-ethyltricyclopropane [3.3.1.1 ^{3 , 7} ]decane-1-yl-(meth)acrylate, 3-hydroxytricyclo[3.3.1.1 ^{3 , 7} ]decane-1-yl-(meth)acrylate, etc.; The alkyl moiety of the cycloalkyl acrylate may also be a lactone structure, an indoleamine structure or an acetal structure. As an example, 2-ethyl-γ-butyrolactone-2-yl-(meth)acrylate, 2-methyl-γ-butyrolactone-2-yl-(meth)acrylate, 2- Ethyl-γ-butyrolactone-3-yl-(meth) acrylate, 2-methyl-γ-butyrolactone-3-yl-(meth) acrylate, 2-ethyl-γ-butyl Lactone-4-yl-(meth) acrylate, 2-methyl-γ-butyrolactone-4-yl-(meth) acrylate, 2-ethyl-δ-valerolactone-2-yl -(Meth)acrylate, 2-ethyl-δ-valerolide-3-yl-(meth)acrylate, 2-ethyl-δ-valerolactone-4-yl-(meth)acrylic acid Lactones, lactones such as 2-ethyl-δ-valerolactone-5-yl-(meth)acrylate; 2-ethyl-γ-butylidene-2-yl-(methyl) Acrylate, 2-methyl-γ-butylidene-2-yl-(meth) acrylate, 2-ethyl-γ-butylidene-3-yl-(meth) acrylate, 2 -Methyl-γ-butylidene-3-yl-(meth) acrylate, 2-ethyl-γ-butylidene-4-yl-(meth) acrylate, 2 -Methyl-γ-butylidene-4-yl-(meth) acrylate, 2-ethyl-δ-pentalin-2-yl-(meth) acrylate, 2-ethyl- Δ-valeroindol-3-yl-(meth) acrylate, 2-ethyl-δ-pentalin-4-yl-(meth) acrylate, 2-ethyl-δ-pentene An indoleamine or the like such as amidoxime-5-yl-(shenyl) acrylate; the acetal structure includes tetrahydro-2H-pyran-2-yl ester and the like.

Examples of the aryl (meth)acrylate include phenyl methacrylate and benzyl methacrylate; and examples of the unsaturated dicarboxylic acid diester include diethyl maleate and diethyl fumarate. Ester, diethyl itaconate, etc.; as bicyclic unsaturated compounds, bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-B Bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6 -dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2 .1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5 ,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5- Ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, etc.; as a maleimide compound, phenyl Maleic imine, cyclohexyl Kamalimide, benzyl maleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide Butyrate, N-succinimide-6-maleimide caproate, N-succinimide-3-maleimide propionate, N-(9-acridinyl) And the like, and the unsaturated aromatic compound may, for example, be styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene or p-methoxy. Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like; as the unsaturated monocarboxylic acid Examples thereof include acrylic acid, methacrylic acid, and crotonic acid; and examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like; and unsaturated dicarboxylic acid; Examples of the acid anhydride include acid anhydrides of the above respective dicarboxylic acids; and examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, chloroethylene, vinylidene chloride, and acrylamide. Methyl acrylamide, and vinyl acetate.

Among them, styrene, methacrylic acid tricyclo [5.2.1.0 ^{2 , 6} ]decane-8-yl ester, p-methoxystyrene, acrylic acid 2- are preferred from the viewpoints of copolymerization reactivity, heat resistance and the like. Methylcyclohexyl ester, 1,3-butadiene, bicyclo[2.2.1]hept-2-ene, N-cyclohexylmaleimide, methacrylic acid, 1-ethylcyclopentane methacrylate A base ester, 2-methyl-2-propionic acid, tetrahydro-2H-pyran-2-yl ester or the like.

They can be used singly or in combination.

(A) The copolymer is a structural unit derived from a monomer of a polymerizable unsaturated compound, preferably containing 5 to 95% by weight (a1), 95 to 5% by weight (a2), more preferably 20 to 95% by weight (a1) 80% by weight (a2), most preferably 30-90% by weight (a1), 70-10% by weight (a2) [where (a1) + (a2) = 100% by weight]. At the content of this range, good planarization performance and heat resistance can be achieved.

As preferred specific examples of the (A) copolymer, for example, a styrene/glycidyl methacrylate copolymer, a styrene/trimethyl methacrylate [5.2.1.0 ^{2 , 6} ]decane-8-yl group can be cited. Ester/glycidyl methacrylate copolymer, styrene/N-cyclohexylmaleimide/glycidyl methacrylate copolymer, styrene/N-phenylmaleimide/methacrylic acid shrinkage Glyceride copolymer, N-cyclohexylmaleimide/glycidyl methacrylate copolymer, N-phenylmaleimide/glycidyl methacrylate copolymer, styrene/methacrylic acid Ring [5.2.1.0 ^{2 , 6} ]decane-8-yl ester/methacrylic acid/glycidyl methacrylate copolymer, styrene/N-cyclohexylmaleimide/methacrylic acid/methacrylic acid Glycidyl ester copolymer, styrene/N-phenylmaleimide/methacrylic acid/glycidyl methacrylate copolymer, styrene/methacrylic acid tricyclo [5.2.1.0 ^{2 , 6} ]decane -8-yl ester/1-ethylcyclohexane methacrylate/glycidyl methacrylate copolymer, styrene/N Cyclohexylmaleimide/1-ethylcyclohexane methacrylate/glycidyl methacrylate copolymer, styrene/N-phenylmaleimide/1-ethyl methacrylate Cyclohexane ester/glycidyl methacrylate copolymer, styrene/trimethyl methacrylate [5.2.1.0 ^{2 , 6} ]decane-8-yl ester / 1-ethylcyclopentanyl methacrylate Ester/glycidyl methacrylate copolymer, styrene/N-cyclohexylmaleimide/1-ethylcyclopentyl methacrylate/glycidyl methacrylate copolymer, styrene/N -Phenylmaleimide/1-ethylcyclopentyl methacrylate/glycidyl methacrylate copolymer, styrene/trimethyl methacrylate [5.2.1.0 ^{2 , 6} ] decane- 8-Base Ester/1-Methylcyclohexyl Methacrylate/Glycidyl Methacrylate Copolymer, Styrene/N-Cyclohexylmaleimide/1-Methylcyclohexane Glycol/glycidyl methacrylate copolymer, styrene/N-phenylmaleimide/1-methylcyclohexane methacrylate/glycidyl methacrylate Copolymer, styrene / methacrylic acid tricyclo [5.2.1.0 ^{2, 6]} decan-8-yl methacrylate / tetrahydro -2H- pyran-2-yl acrylate / glycidyl methacrylate copolymers, styrene Ethylene/N-cyclohexylmaleimide/tetrahydro-2H-pyran-2-yl ester/glycidyl methacrylate copolymer, styrene/N-phenylmaleimide/tetrahydro- 2H-pyran-2-yl ester/glycidyl methacrylate copolymer and the like.

(A) The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (the elution solvent is tetrahydrofuran) is preferably from 1,000 to 100,000, more preferably from 2,000 to 50,000. Good for 3000-40000. In this case, if the Mw is less than 1,000, the coating property of the composition may not be sufficiently good, or the heat resistance of the formed protective film may be insufficient. On the other hand, if the Mw exceeds 100,000, the flattening property may be insufficient. Good situation.

Further, the molecular weight distribution (Mw/Mn) of the (A) copolymer is preferably 5.0 or less, more preferably 3.0 or less.

Such (A) copolymer may be obtained by a known method such as radical polymerization in the presence of a (a1) polymerizable unsaturated compound and (a2) another polymerizable unsaturated compound in the presence of a suitable solvent and a suitable polymerization initiator. And synthesis.

For example, the above-mentioned radical polymerization may be carried out by using (a1) a polymerizable unsaturated compound such as 5-95 parts by weight of glycidyl methacrylate and 95 to 5 parts by weight of (a2) other polymerizable unsaturated compound of styrene [ Wherein (a1)+(a2)=100 parts by weight] is mixed in 100-400 parts by weight of a solvent such as ethyl cellosolve acetate or propylene glycol monomethyl ether acetate, relative to 100 parts by weight of the monomer component a total amount of 0.5 to 15 parts by weight of a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or 2,2'-azo (2,4-dimethylvaleronitrile) as a polymerization initiator. It is obtained by polymerization at 70-100 ° C for 3-10 hours.

(B) Phosphate ester

The (B) phosphate ester used in the present invention has a structure represented by the above formula (1).

In the component (B), R ¹ in the above formula (1) is preferably an alkyl group having 1 to 18 carbon atoms, an aryl group, a benzyl group or an alkyl group having a carbon atom number of 1 or a side chain. The alkoxy group of -4 has an alkyl group having 1 to 8 carbon atoms or an acetate group, and R ^{2 is} preferably an alkyl group having 1 to 18 carbon atoms or an aryl group or a benzyl group.

When the component (B) is trimethyl phosphate and/or triethyl phosphate, it is preferable from the viewpoints of smoothness of the surface of the film, intermittent time, and the like.

As the (B) phosphate ester, in the above formula (1), when X = 0, tris(octadecyl) phosphate, dioctadecyl phosphate, and monooctadecyl group are exemplified. Phosphate ester, tri(iso)butyl phosphate, di(iso)butyl phosphate, mono(iso)butyl phosphate, tris(isopropyl) phosphate, di(iso)propyl phosphate, single ( Isopropyl phosphate, triethyl phosphate, diethyl phosphate, monoethyl phosphate, trimethyl phosphate, dimethyl phosphate, monomethyl phosphate, triphenyl phosphate, two Phenyl phosphate, monophenyl phosphate, tribenzyl phosphate, dibenzyl phosphate, monobenzyl phosphate, and the like.

Further, in the above formula (1), when X = 1 and R ¹ is a hydrogen atom, specific examples of the (B) phosphoric acid ester include dioctadecyl phosphonate and phosphonic acid mono Octaalkyl ester, di(iso)butyl phosphonate, mono(iso)butyl phosphonate, di(iso)propyl phosphonate, mono (iso)propyl phosphonate, diethyl phosphonate And monoethyl phosphonate, dimethyl phosphonate, monomethyl phosphonate, diphenyl phosphonate, monophenyl phosphonate, dibenzyl phosphonate, monobenzyl phosphonate, and the like.

Further, in the above formula (1), when X=1, and the atom adjacent to the phosphorus atom of R ¹ is a carbon atom, specific examples of the (B) phosphate ester include trimethyl phosphate and two. Ethyl phthalic acid imine methyl phosphate, tripropylene methoxyethyl phosphate, dipropylene methoxyethyl phosphate, mono propylene oxyethyl phosphate, and the like.

The amount of the component (B) to be added is 0.01 to 50 parts by weight, preferably 0.1 to 30 parts by weight, more preferably 0.5 to 10 parts by weight per 100 parts by weight of the component (A). When it is less than 0.01 part by weight, sufficient hardness cannot be obtained, and on the other hand, if it exceeds 50 parts by weight, the intermittent time is prolonged.

(C) Lewis acid catalyst

The resin composition of the present invention must have the above components (A) to (B), and may further contain (C) a Lewis acid catalyst. (C) The Lewis acid catalyst exerts a function of promoting hardening in the resin composition of the present invention.

As the (C) Lewis acid catalyst used in the present invention, diethyl zinc, diphenyl zinc, zinc chloride, diisobutylphenyl aluminum, diethyl aluminum ethane sulfide, diethyl ether can be cited. Phenyl aluminum, dimethyl aluminum methoxy compound, triphenyl aluminum, tribenzyl aluminum, tri-tert-butyl aluminum, N-nitrosophenyl hydroxylamine aluminum salt, diethyl dichlorodecane, 1, 1-Dimethyl-1-indole heterocyclopentane, tetraethyl decane, tetramethyl decane, triphenylchlorodecane, trimethylchlorodecane, chlorotribenzyl zirconium, zirconium chloride, triethylene oxychloride Base cyclopentadienyl zirconium, dichlorobis(cyclopentadienyl)zirconium, dibutyltin dilaurate, dibutyltin dioctanoate, trimethylchlorostannane, trimethylmethoxystannane, chlorine Tribenzyl titanium, titanium chloride, chlorobis(cyclopentadienyl)titanium, titanocene, trichloromethyltitanium, chlorotris(triphenylphosphine)nickel, tetrakis(triphenylphosphine)nickel, Nickel nickel, diethyl chloroborane, diisopropyl chloroborane, diphenyl chloroborane, dibutyl chloroborane, and the like.

The amount of the (C) Lewis acid catalyst added is 0.0001 to 20 parts by weight, preferably 0.001 to 10 parts by weight, more preferably 0.005 to 5 parts by weight per 100 parts by weight of the component (A). When the amount is less than 0.0001 part by weight, a sufficient promoting effect cannot be obtained. On the other hand, if it exceeds 20 parts by weight, precipitation may occur to cause cracking of the surface of the film.

(D) cationically polymerizable compound

The resin composition of the present invention must have the above components (A) to (B), and may further contain (D) a cationically polymerizable compound (wherein the above component (A) is excluded). (D) The cationically polymerizable compound functions to increase the film hardness in the resin composition of the present invention.

The (D) cationically polymerizable compound used in the present invention is a compound having two or more oxirane groups or propylene oxide groups in the molecule (excluding the above component (A)). The compound having two or more oxirane groups or propylene oxide groups in the molecule may, for example, be a compound having two or more epoxy groups in the molecule or a compound having a 3,4-epoxycyclohexyl group.

In addition, examples of the compound having two or more epoxy groups in the molecule include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and hydrogenated bisphenol A condensed water. Glycerol ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, bromobisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether Diglycidyl ethers of bisphenol compounds; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether a polyglycidyl ether of a polyhydric alcohol such as polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether; or one or more epoxy resins added to an aliphatic polyol such as ethylene glycol, propylene glycol or glycerin; a polyglycidyl ether of a polyether polyol obtained by an alkane; a phenol novolak type epoxy resin; a cresol novolac type epoxy resin; a polyphenol type epoxy resin; a diglycidyl ester of an aliphatic long-chain dibasic acid; Glycidyl esters of higher fatty acids; large epoxidation Soybean oil, epoxidized linseed oil, etc.

As a commercial item of the compound having two or more epoxy groups in the above-mentioned molecule, for example, EPIKOTE 1001, EPIKOTE 1002, EPIKOTE 1003, EPIKOTE 1004, EPIKOTE 1007, EPIKOTE 1009, EPIKOTE 1010, EPIKOTE 828 (above by Japan Epoxy) may be mentioned. Examples of the bisphenol F-type epoxy resin include EPIKOTE 807 (produced by Japan Epoxy Resins Co., Ltd.); and examples of the phenol novolak type epoxy resin include EPIKOTE 152, EPIKOTE 154, and EPIKOTE 157 S65 (above Japan Epoxy Resins Co., Ltd., EPPN 201, EPPN 202 (manufactured by Nippon Kayaku Co., Ltd.), etc.; as cresol novolac type epoxy resin, EOCN 102, EOCN 103S, EOCN 104S, 1020, 1025 1027 (the above is produced by Nippon Kayaku Co., Ltd.), EPIKOTE 180S75 (produced by Japan Epoxy Resins Co., Ltd.), etc., and as the polyphenol type epoxy resin, EPIKOTE 1032H60 and EPIKOTEXY-4000 (above by Japan Epoxy Resins) ))); as a cyclic aliphatic epoxy resin, CY-175, CY-177, CY-179, Araldit CY-182, Araldit CY-192, 184 (above) Ciba Specialty Chemicals Co., Ltd., ERL-4234, 4299, 4221, 4206 (manufactured by UCC Corporation), Shodain 509 (produced by Showa Denko Co., Ltd.), EPICRONE 200, EPICRONE 400 (above by Dainippon Ink ( (Production), EPIKOTE871, EPIKOTE872 (above produced by Japan Epoxy Resins Co., Ltd.), ED-5661, ED-5662 (produced by Celanese Co., Ltd.), etc.; as an aliphatic polyglycidyl ether, Epolaid 100MF can be cited. (produced by Kyoeisha Chemical Co., Ltd.), Epiol TMP (produced by Nippon Oil & Fat Co., Ltd.), and the like.

Examples of the compound having two or more 3,4-epoxycyclohexyl groups in the molecule include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, and 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate Ester, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6' -Methylcyclohexanecarboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol bis(3,4-epoxycyclohexyl Methyl)ether, methylene bis(3,4-epoxycyclohexanecarboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxy ring Alkyl carboxylate and the like.

Among such (D) cationically polymerizable compounds, a phenol novolak type epoxy resin and a polyphenol type epoxy resin are preferable.

The amount of the (D) cationically polymerizable compound in the resin composition of the present invention is preferably from 3 to 200 parts by weight, more preferably from 5 to 100 parts by weight, particularly preferably from 10 to 50 parts by weight per 100 parts by weight of the component (A). Share. When the amount of the (D) cationically polymerizable compound is more than 200 parts by weight, there is a problem that the coating property of the composition is problematic. On the other hand, if the amount is less than 3 parts by weight, the hardness of the obtained protective film may be insufficient. Happening.

(E) Adhesive additives

In order to improve the adhesion between the formed protective film and the substrate, (E) a bonding aid may be added to the resin composition of the present invention.

As such (E) bonding assistant, for example, a functional decane coupling agent having a reactive substituent can be used. Examples of the reactive substituent include a carboxylic acid group, a methacryl fluorenyl group, an isocyanate group, and an epoxy group.

Specific examples of the (E) adhesion aid include, for example, trimethoxydecyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, and vinyl trimethyl. Oxydecane, γ-isocyanate propyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, γ-glycidoxypropyl triethoxy decane, β-(3, 4 - Epoxycyclohexyl)ethyltrimethoxydecane, and the like.

The (E) adhesion aid is preferably used in an amount of 30 parts by weight or less, more preferably 25 parts by weight or less, particularly preferably 5 to 20 parts by weight per 100 parts by weight of the (A) copolymer. If the amount of the (E) adhesion aid exceeds 30 parts by weight, the heat resistance of the obtained protective film may be insufficient.

(F) surfactant

In order to improve the coating property of the resin composition of the present invention, (F) a surfactant may be added to the resin composition of the present invention.

Examples of such a (F) surfactant include a fluorine-based surfactant, a polyoxyalkylene surfactant, a nonionic surfactant, and other surfactants.

Examples of the fluorine-based surfactant include BM-1000, BM-1100, manufactured by BM CHIMIE Co., Ltd., and MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173, and MEGAFAC, manufactured by Dainippon Ink and Chemicals, Inc. F183, Sumitomo 3M Co., Ltd. produced under the trade names FLUORAD FC-135, FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431, NEOS, and the trade names Ftergent 250, Ftergent 251, Ftergent 222F, FTX-218 and Asahi Glass Co., Ltd. are sold under the trade names SARFRON S-112, SARFRON S-113, SARFRON S-131, SARFRON S-141, SARFRON S-145, SARFRON S-382, SARFRON SC-101, SARFRON SC. -102, SARFRON SC-103, SARFRON SC-104, SARFRON SC-105, SARFRON SC-106 and other commercial products.

Examples of the polysiloxane surfactants include, for example, those produced by Toray Dow Corning Silicone Co., Ltd. under the trade names of SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, and DC-57. DC-190, a trade name of KP341 produced by Shin-Etsu Chemical Co., Ltd., and a commercial item such as EFTOP EF301, EFTOP EF303, and EFTOP EF352, which are produced by New Akita Chemicals Co., Ltd.

Examples of the nonionic surfactant include polyethylene oxide alkyl ethers, polyethylene oxide aryl ethers, and polyethylene oxide dialkyl esters.

Examples of the polyoxirane alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and the like, and polyethylene oxide aryl ether. Examples thereof include polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether. Examples of the polyethylene oxide dialkyl esters include polyoxyethylene dilaurate and polyoxyethylene. Distearate and the like.

For the other surfactants, the product name (meth)acrylic copolymer Polyfro No. 57, Polyfro No. 90, etc., which are produced by Kyoei Kogyo Co., Ltd., may be mentioned.

The amount of the (F) surfactant to be added is preferably 5 parts by weight or less, more preferably 2 parts by weight or less, particularly preferably 0.001 to 1.0 part by weight per 100 parts by weight of the component (A). When the amount of the (F) surfactant is more than 5 parts by weight, there is a case where the coating film is easily cleaved in the coating step.

(G) heat-sensitive acid generator

In order to increase the film strength, a heat-sensitive acid generator may be added to the resin composition of the present invention. Examples of the (G) heat-sensitive acid generator include an onium salt, a benzothiazolium salt, an ammonium salt, and an onium salt. Among them, an onium salt or a benzothiazole salt is preferably used.

Specific examples of the above sulfonium salt include 4-ethyl phenyl phenyl hexafluoroantimonate, 4-ethyl methoxy phenyl dimethyl hexafluoro arsenate, and dimethyl-4. -(Benzyloxycarbonyloxy)phenylphosphonium hexafluoroantimonate, dimethyl-4-(benzylideneoxy)phenylphosphonium hexafluoroantimonate, dimethyl-4-(benzonitrile) An alkyl sulfonium salt such as phenyl hydrazine hexafluoroarsenate or dimethyl-3-chloro-4-ethoxy phenyl phenyl hexafluoroantimonate; benzyl-4-hydroxyphenyl Methyl hydrazine hexafluoroantimonate, benzyl-4-hydroxyphenylmethyl sulfonium hexafluorophosphate, 4-acetoxyphenylbenzyl methyl hexafluoroantimonate, benzyl-4-methyl Oxyphenylmethyl hydrazine hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethyl hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethyl fluorene a benzyl sulfonium salt such as fluoroarsenate or 4-methoxybenzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate; dibenzyl-4-hydroxyphenylphosphonium hexafluoroantimonate, dibenzyl 4-hydroxyphenylphosphonium hexafluorophosphate, 4-ethyloxyphenyl dibenzyl hexafluoroantimonate, dibenzyl-4 Methoxyphenylphosphonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylphosphonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-third Dibenzyl sulfonium salt such as phenyl hydrazine hexafluoroantimonate or benzyl-4-methoxybenzyl-4-hydroxyphenyl sulfonium hexafluorophosphate; p-chlorobenzyl-4-hydroxyphenyl Hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, p- Nitrobenzyl-3-methyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, o-chloro A substituted benzyl sulfonium salt or the like such as benzyl-3-chloro-4-hydroxyphenylmethylphosphonium hexafluoroantimonate.

Among them, 4-ethenyloxy phenyl dimethyl hexafluoroarsenate, benzyl-4-hydroxyphenylmethyl hexafluoroantimonate, 4-ethenyloxyphenyl benzyl is preferably used. Methyl hydrazine hexafluoroantimonate, dibenzyl-4-hydroxyphenyl hexafluoroantimonate, 4-ethenyloxyphenylbenzyl hexafluoroantimonate, and the like.

Examples of the above benzothiazolium salt include 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, and 3-benzylbenzothiazolium tetrafluoroborate. , 3-(p-methoxybenzyl)benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, 3-benzyl-5-chloro Benzylbenzothiazolium salt such as benzothiazolium hexafluoroantimonate.

Among them, 3-benzylbenzothiazolium hexafluoroantimonate or the like is preferably used.

As a commercially available product which is suitable for use as the (G) heat-sensitive acid generator, the alkyl sulfonium salt can be exemplified by the trade names of ADEKA OPTON CP-66 and CP-77 manufactured by Asahi Kasei Kogyo Co., Ltd.

In addition, as the benzyl hydrazine, trade names of SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, and SI can be cited. -100L, SI-110L.

Among them, from the viewpoint that the obtained protective film has high surface hardness, it is preferably SI-80, SI-100, and SI-110.

The amount of the heat-sensitive acid generator (G) is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, even more preferably 0.1 to 5 parts by weight per 100 parts by weight of the component (A). If it exceeds 20 parts by weight, precipitation may occur and the film surface may be cleaved.

Modification and solvent of resin composition

The resin composition of the present invention can be prepared by preferably dissolving or dispersing the above components in a suitable solvent. As the solvent to be used, a solvent which can dissolve or disperse each component of the composition and does not react with each component is preferably used.

Examples of such a solvent include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, and propylene glycol monoalkanes. Alkyl ethers, propylene glycol alkyl ether acetates, propylene glycol alkyl ether propionates, aromatic hydrocarbons, ketones, esters, and the like.

Specific examples of the alcohols include methanol, ethanol, and benzyl alcohol; examples of the ethers include tetrahydrofuran; and examples of the glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Examples of the diol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and the like; Examples of the glycol monoalkyl ethers include diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; and diethylene glycol dialkyl ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and Examples of the propylene glycol monomethyl ethers include propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether; and propylene glycol alkyl ether acetates include propylene glycol methyl ether acetate. Propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc.; propylene glycol alkyl ether propionate can be exemplified by propylene glycol methyl ether propionate, propylene glycol diethyl ether acetate, propylene glycol Ether acetate, propylene glycol butyl ether acetate, etc.; as aromatic Examples thereof include toluene and xylene; and examples of the ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and methyl isoamyl ketone; and esters. Examples thereof include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, and 2-hydroxy-2-methylpropionic acid. Ethyl ester, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, Propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, Butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, C Propyl oxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 2- Methyl oxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-B Ethyl oxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butyl Propyl oxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methyl Butyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-propane Methyl oxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, 3-butyl Ethyl oxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and the like.

Among them, preferred are alcohols, diethylene glycols, propylene glycol alkyl acetates, ethylene glycol alkyl ether acetates, diethylene glycol dialkyl ethers, particularly preferably benzyl alcohol, diethylene glycol Methyl ether, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, diglyme, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether.

The amount of the solvent used is preferably from 1 to 50% by weight, more preferably from 5 to 40%, based on the total solid content of the composition of the present invention (the amount obtained by removing the solvent from the total amount of the solvent-containing composition). The range of % by weight.

Further, a high boiling point solvent may be used in combination with the above solvent. As the high boiling point solvent which can be used in combination here, for example, N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N can be mentioned. , N-dimethylacetamide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like.

The amount of use in combination with a high boiling point solvent is preferably 90% by weight or less, and more preferably 80% by weight or less based on the total amount of the solvent.

The composition prepared as above may be used after being filtered by a micropore filter having a pore diameter of 0.2 to 3.0 μm, preferably a pore diameter of about 0.2 to 0.5 μm.

Color filter protective film formation

Next, a method of forming a color filter protective film using the resin composition of the present invention will be described.

That is, the resin composition solution of the present invention is applied onto the surface of the substrate, and the solvent is removed by prebaking to form a coating film, followed by heat treatment to form a target color filter protective film.

As the substrate which can be used as the above substrate, for example, a substrate such as glass, quartz, rhodium or resin can be used. Examples of the resin include a ring-opening polymer of polyethylene terephthalate, polybutylene terephthalate, polyether fluorene, polycarbonate, polyimine, and cyclic olefin, and hydrogenated products thereof. Resin.

As the coating method, a suitable method such as a spray coating method, a roll coating method, a spin coating method, a bar coating method, or an inkjet method can be employed, and it is particularly suitable for coating by a spin coater, a non-rotating coater, or a slit die coater. apply.

The conditions for the prebaking described above vary depending on the type of each component, the blending ratio, and the like, and usually, a condition of about 1 to 15 minutes at 70 to 90 ° C can be employed. The thickness of the coating film is preferably from 0.15 to 8.5 μm, more preferably from 0.15 to 6.5 μm, still more preferably from 0.15 to 4.5 μm. Further, the thickness of the coating film described herein is understood to be the thickness after removal of the solvent.

The heat treatment after the formation of the coating film can be carried out in a suitable heating device such as a hot plate or a clean oven. The treatment temperature is preferably about 150-250 ° C, the heating time, when using the heating plate, the treatment time can be 5-30 minutes, and when the oven is used, 30-90 minutes can be used.

Further, when a radiation-sensitive acid generator is used in the resin composition, the radiation-sensitive resin composition may be applied onto a substrate, and the solvent may be removed by prebaking to form a coating film, followed by irradiation treatment (exposure treatment). Then, heat treatment is performed to form a target protective film.

The radiation-sensitive acid generator which generates an acid by irradiation with radiation used in the present invention can promote the reaction by the action of an acid generated by exposure. Examples of such an acid generator include (1) a phosphonium salt, (2) a halogen-containing compound, (3) a diazoketone compound, (4) an anthracene compound, and (5) a sulfonic acid compound. Examples of such acid generators include the following.

(1) Examples of the onium salt include an iodonium salt, a phosphonium salt, a phosphonium salt, a diazonium salt, a pyridinium salt, and the like. Specific examples of the preferred phosphonium salt include diphenyliodonium trifluoromethanesulfonate, diphenyliodoniumsulfonate, diphenyliodonium dodecylbenzenesulfonate, and 4-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium dodecylbenzenesulfonate, bis(4-tert-butylphenyl) Iodine naphthalenesulfonate, bis(4-t-butylphenyl)iodonium hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenyl Base naphthalene sulfonate, (hydroxyphenyl)benzyl indolyl sulfonate, 1-(naphthylethylidenemethyl)thiophene trifluoromethanesulfonate, cyclohexylmethyl (2-oxo ring) Hexyl)trifluoromethanesulfonate, dicyclohexyl(2-oxocyclohexyl)phosphonium triflate, dimethyl(2-oxocyclohexyl)phosphonium triflate, dimethyl (4-hydroxynaphthyl) anthracene trifluoromethanesulfonate, dimethyl (4-hydroxynaphthyl) anthracene tosylate, dimethyl (4-hydroxynaphthyl) anthracene dodecylbenzenesulfonic acid Salt, dimethyl (4-hydroxynaphthyl) anthracene naphthalene sulfonate, diphenyl iodonium hexafluoroantimonate, triphenyl camphorsulfonate, (4- Hydroxyphenyl)benzylmethylindole tosylate or the like.

(2) The halogen-containing compound may, for example, be a halogenated alkyl group-containing hydrocarbon compound or a halogenated alkyl group-containing heterocyclic compound. Specific examples of preferred halogen-containing compounds include phenyl-bis(trifluoromethyl)-s-three. Methoxyphenyl-bis(trifluoromethyl)-s-three Naphthyl-bis(trifluoromethyl)-s-three Equivalent (trifluoromethyl)-s-three a derivative, or 1,1-bis(4-chlorophenyl)-2,2,2-trifluoroethane or the like.

(3) Examples of the diazoketone compound include a 1,3-diketone-2-diazo compound, a diazonium quinone compound, and a diazonaphthoquinone compound. Specific examples of the preferred diazoketone compound include 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazo-5-sulfonyl chloride, 2,3. 1,2-naphthoquinonediazo-4-sulfonate of 4,4'-tetrahydrobenzophenone or 1,2-naphthoquinonediazo-5-sulfonate, 1,1,1-three 1,2-naphthoquinonediazo-4-sulfonate or 1,2-naphthoquinonediazo-5-sulfonate of (4-hydroxyphenyl)ethane.

(4) Examples of the ruthenium compound include β-ketooxime, β-sulfonylhydrazine, or an α-diazonium compound of these compounds. Specific examples of the preferred ruthenium compound include 4-tris(benzhydrylmethyl)fluorene. Benzobenzidine methyl hydrazine, bis(phenylsulfonyl) methane, and the like.

(5) Examples of the sulfonic acid compound include an alkylsulfonate, an alkylsulfonimide, a halogenated alkylsulfonate, an arylsulfonate, and an imidesulfonate. Specific examples of preferred sulfonic acid compounds include benzoin tosylate, tris(trifluoromethanesulfonate) of pyroic acid, and nitrobenzyl-9,10-diethoxy. Indole-2-sulfonate, trifluoromethanesulfonium bicyclo[2.2.1]heptane-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide triflate, 1,8-naphthalene dicarboxy quinone imine trifluoromethanesulfonate or the like.

Among these acid generators, particularly preferred are diphenyliodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, and triphenylsulfonium trifluoromethanesulfonic acid. Salt, cyclohexylmethyl (2-oxocyclohexyl)phosphonium triflate, dicyclohexyl (2-oxocyclohexyl)phosphonium triflate, dimethyl (2-oxo ring) Hexyl)trifluoromethanesulfonate, 1-(naphthylethylidenemethyl)thiophene trifluoromethanesulfonate, 4-hydroxynaphthyldimethylsulfonium trifluoromethanesulfonate, dimethyl (4 -hydroxynaphthyl)indole trifluoromethanesulfonate, trifluoromethanesulfonylbicyclo[2.2.1]heptane-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoride Methanesulfonate, 1,8-naphthalenedicarboxyimine triflate, and the like.

In the present invention, the acid generators may be used singly or in combination of two or more kinds.

The amount of the acid generator is usually 0.1 to 10 parts by weight, preferably 0.5 to 7 parts by weight, per 100 parts by weight of the (A) copolymer. In this case, when the amount of the acid generator is less than 0.1 part by weight, a sufficient reaction promoting effect cannot be obtained. On the other hand, if it exceeds 10 parts by weight, the transparency may be lowered.

Examples of the radiation used in the radiation irradiation treatment include visible light rays, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays, and ultraviolet rays having a wavelength of 190 to 450 nm are preferable.

The exposure amount is usually from 100 to 20,000 J/m ² , preferably from 150 to 10,000 J/m ² .

After the irradiation of the radiation, further heat treatment is performed. The heating temperature at this time is preferably about 150 to 250 ° C, and as the heating means, a suitable device such as a hot plate or a clean oven can be used. Heating time, 5-30 minutes of processing time can be used when using the hot plate, and 15-90 minutes can be used when using the oven.

Protective film for color filters

The protective film thus formed preferably has a film thickness of from 0.1 to 8 μm, more preferably from 0.1 to 6 μm, still more preferably from 0.1 to 4 μm. Further, when the protective film of the present invention is formed on a substrate having a color filter step layer, the above film thickness is understood to be the thickness from the uppermost portion of the color filter.

As can be seen from the following examples, the protective film of the present invention is suitably used for satisfying adhesion, surface hardness, transparency, heat resistance, light resistance, solvent resistance, etc., and does not load even under heat. A protective film for a device which is recessed and which has excellent planarization performance for a ladder layer of a color filter formed on a base substrate.

In particular, since it is encountered in the case where heating of more than 250 ° C is encountered in the panel manufacturing step, the protective film of the present invention has heat resistance which is sufficiently tolerated in this case, and thus is ensured at 270 ° C as well. Sufficient dimensional stability.

Thermal dry film

In the resin composition of the present invention, a heat-sensitive dry film can be obtained by laminating the heat-sensitive layer of the heat-sensitive resin composition of the present invention on a base film, preferably on a permeable base film.

The heat-sensitive dry film can be formed by applying a heat-sensitive resin composition to a base film as a liquid composition, followed by drying to laminate a heat-sensitive layer.

As the base film of the heat-sensitive dry film, for example, a polyethylene terephthalate (PET) film, a synthetic resin film such as polyethylene, polypropylene, polycarbonate, or polyvinyl chloride can be used.

The thickness of the base film is preferably from 15 to 125 μm.

The coating method for laminating the heat-sensitive layer on the base film is not particularly limited, and for example, an appropriate method such as an applicator coating method, a bar coating method, a roll coating method, or a curtain coating method can be employed.

The thickness of the obtained heat sensitive layer is preferably about 1 to 30 μm.

Further, the heat-sensitive dry film can be further deposited by laminating a film on the heat-sensitive layer when it is not used.

The film is intended to stably protect the heat sensitive layer when not in use, and is removed during use. Therefore, the film must have a moderate mold release property so that it does not peel off when not in use, and can be easily peeled off during use. As the film which satisfies such a condition, for example, a film in which a polysiloxane-based release agent is applied or sintered on the surface of a synthetic resin film such as a PET film, a polypropylene film, a polyethylene film or a polyvinyl chloride can be used.

It is sufficient that the thickness of the film is usually about 25 μm.

When the dry film method is used, when the film is laminated, the film is peeled off, and the heat sensitive layer is placed on the substrate side by a normal pressure hot roll pressing method, a vacuum hot roll pressing method, and a vacuum heat. a heat-sensitive dry film is pressed against the substrate under appropriate pressure and pressure by a suitable pressing method, and the heat-sensitive layer is transferred onto the surface of the substrate to form a heat-sensitive resin composition on the substrate. Laminating.

The heat-sensitive dry film thus obtained can be applied to a protective film for an optical device such as a protective film for a color filter.

[Examples]

The present invention will be more specifically described below by way of Synthesis Examples and Examples, but the present invention is not limited to the following examples.

Copolymer manufacturing Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Next, 50 parts by weight of glycidyl methacrylate and 50 parts by weight of styrene were added, and after replacing with nitrogen, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-1). The solid content concentration of the obtained polymer solution was 32.9% by weight.

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Next, 50 parts by weight of (3-ethyl-3-oxoethyl)methyl methacrylate and 50 parts by weight of styrene were added, and after replacing with nitrogen, Start stirring slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-2). The solid content concentration of the obtained polymer solution was 33.2% by weight.

Synthesis Example 3

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Next, 40 parts by weight of glycidyl methacrylate, 40 parts by weight of methacrylic acid, 10 parts by weight of styrene, and 10 parts by weight of tricyclo[5.2.1.0 ^{2 , 6} ]decane-8-yl methacrylate were added. After replacing with nitrogen, slow stirring was started. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-3). The solid content concentration of the obtained polymer solution was 33.2% by weight.

Synthesis Example 4

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Next, 40 parts by weight of glycidyl methacrylate, 40 parts by weight of 1-ethylcyclohexyl methacrylate, 10 parts by weight of styrene, and 10 parts by weight of N-cyclohexylmaleimide, with nitrogen, were added. After the replacement, slow stirring was started. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-4). The solid content concentration of the obtained polymer solution was 33.2% by weight.

Synthesis Example 5

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Next, 40 parts by weight of glycidyl methacrylate, 20 parts by weight of styrene, and 20 parts by weight of N-cyclohexylmaleimide, 20 parts by weight of 2-methyl-2-propionic acid tetrahydro-2H-pyrene were added. The butan-2-yl-ester was slowly stirred after replacement with nitrogen. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-5). The resulting polymer solution had a solid content concentration of 29.9% by weight.

Modification and evaluation of resin composition Example 1

A solution containing the copolymer (A-1) obtained in the above Synthesis Example 1 (corresponding to an amount containing 100 parts by weight of the copolymer (A-1) (solid content)), 5.0 parts by weight (B) of three positive 18 Alkyl phosphate and 0.1 parts by weight of (C) N-nitrosophenylhydroxylamine Al salt, 10.0 parts by weight of (D) bisphenol A phenolic epoxy resin, 5.0 parts by weight of (E) gamma-glycidoxy Propyl trimethoxy decane, 0.1 part by weight of (F) surfactant SH-28PA (manufactured by Toray Dow Corning Silicone Co., Ltd.), and then propylene glycol monomethyl ether acetate to have a solid content concentration of 20% by weight. Then, it was filtered with a micropore filter having a pore size of 0.5 μm to prepare a resin composition.

The composition was applied onto a SiO ₂ -impregnated glass substrate by a spin coater, and then prebaked on a hot plate at 80 ° C for 5 minutes to form a coating film, which was further heat-treated in an oven at 230 ° C for 60 minutes to obtain a film. A protective film having a thickness of 2.0 μm.

Evaluation of protective film

(1) Evaluation of Transparency A substrate having a protective film formed as above was measured for a transmittance of 400 to 800 nm by using a spectrophotometer (150-20 type double beam (manufactured by Hitachi, Ltd.)). The minimum values of transmittance at 400-800 nm are listed in Table 1. When the value is 95% or more, the transparency of the protective film can be referred to as good.

(2) Evaluation of heat-resistant dimensional stability The substrate having the protective film formed as above was heated in an oven at 250 ° C for 1 hour, and the film thickness before and after heating was measured. The heat-resistant dimensional stability calculated according to the following formula is shown in Table 1. When the value is 95% or more, it can be said that the heat resistance dimensional stability is good.

Heat resistant dimensional stability = [(film thickness after heating) / (film thickness before heating)] × 100 (%)

(3) Evaluation of heat-resistant discoloration The substrate having the protective film formed as described above was heated in an oven at 250 ° C for 1 hour, and the transparency before and after heating was measured in the same manner as in the above (1). The heat discoloration property calculated by the following formula is shown in Table 1. When the value is 5% or less, it means that the heat discoloration resistance is good.

Heat-resistant discoloration = light transmittance before heating - light transmittance after heating (%)

(4) Measurement of surface hardness The surface of the protective film was measured by the 8.4.1 pencil scratch hardness test of JIS K-5400-1990 on the substrate having the protective film formed as above. This value is listed in Table 1. When the value is 4H or harder, it means that the surface hardness is good.

(5) Determination of dynamic micro hardness Shimadzu Dynamic microhardness meter DUH-201 ((Shimadzu Corporation)) manufactured on a substrate having the protective film formed as described above by edges of 115 ° triangular indenter (Herocobitch type) pressure Into the test, the dynamic microhardness of the protective film was measured under the measurement conditions of a load: 0.1 gf, a speed: 0.0145 gf/sec, a holding time: 5 sec, a temperature of 23 ° C, and 140 ° C. The results are shown in Table 1.

(6) Adhesion evaluation After the pressure cooker test (120 ° C, humidity 100%, 4 hours) on the substrate having the protective film formed as above, it was evaluated by the 8.5.3 adhesive square method of JIS K-5400-1990. Adhesion of the protective film (adhesion to SiO ₂ ). In the 100 squares, the number of residual squares is listed in Table 1.

In addition, the SiO ₂ -impregnated glass substrate was replaced with a Cr substrate, and a protective film having a film thickness of 2.0 μm was formed in the same manner as described above, and evaluated by the above-described checker tape method. The results are shown in Table 1.

(7) Evaluation of flattening property A pigment-based color resist (trade name "JCR RED 689", "JCR GREEN 706", "CR 8200B") was coated on a SiO ₂ -impregnated glass substrate by a spin coater, and the above was performed by JSR ( (produced), prebaked on a hot plate at 90 ° C for 150 seconds to form a coating film. Then, using a mask of a predetermined pattern, an exposure machine Canon PLA 501F (manufactured by Canon Co., Ltd.) was used, and a ghi line (intensity ratio of wavelength 436 nm, 405 nm, 365 nm = 2.7:2.5:4.8) was applied to 2,000 in terms of i-line conversion. The exposure amount of J/m ² was irradiated, and then developed with a 0.05% potassium hydroxide solution, rinsed in ultrapure water for 60 seconds, and then heat treated in an oven at 230 ° C for 30 minutes to form red, green, and Striped color filter with blue and blue colors (bandwidth is 100μm).

The unevenness of the surface of the substrate on which the color filter was formed was measured by a surface roughness meter "α-Step" (trade name, manufactured by Tencor), and it was 1.0 μm. In addition, the measurement was performed under the condition that the measurement length was 2,000 μm, the measurement range was 2,000 μm square, and the number of measurement points was n=5. That is, the measurement direction is the short-axis direction and red of the strip line in the red, green, and blue directions. Red, green. Green blue. The two directions of the long axis direction of the blue color strip line are measured in n=5 in each direction (the total number of n is 10).

Next, the composition for forming a protective film was applied by a spin coater, and then prebaked on a hot plate at 90 ° C for 5 minutes to form a coating film, which was further heat-treated in an oven at 230 ° C for 60 minutes to form a color filter. A protective film having a film thickness of 2.0 μm on the sheet. Here, the film thickness as referred to herein means the thickness of the uppermost layer of the color filter formed on the substrate.

The surface unevenness of the protective film was measured by the contact type film thickness measuring device "α-Step" (manufactured by Tencor Japan Co., Ltd.) on the substrate having the protective film formed on the color filter. In addition, the measurement was performed under the condition that the measurement length was 2,000 μm, the measurement range was 2,000 μm square, and the number of measurement points was n=5. That is, the measurement direction is the short-axis direction and red of the strip line in the red, green, and blue directions. Red, green. Green blue. The two directions of the long axis direction of the blue color strip line are measured in n=5 in each direction (the total number of n is 10). The ten average values of the height difference (nm) of the highest part and the lowest part of each measurement are shown in Table 1. When the value is 300 nm or less, it can be said that the planarization property is good.

(8) Evaluation of storage stability The viscosity of the resin composition for forming a protective film prepared in Example 1 was measured by an ELD-type viscometer manufactured by Tokyo Keiki Co., Ltd. Then, the composition was allowed to stand at 25 ° C while measuring the solution viscosity at 25 ° C daily. The number of days required to increase the viscosity by 5% was determined based on the viscosity immediately after the preparation, and the number of days is shown in Table 1. When the number of days is 20 days or more, it can be said that the storage stability is good.

Examples 2 to 17 and Comparative Examples 1 to 2

The types and amounts of the components of the composition are as shown in Tables 1 to 2, and were prepared in the same manner as in Example 1 except that the solid content concentrations shown in Tables 1 to 2 were used in the solvents listed in Tables 1 to 2. Resin composition.

Using the resin composition for forming a protective film prepared as described above, a protective film was formed in the same manner as in Example 1 and evaluated. The results are shown in Tables 1 to 2.

Example 18~20

The type and amount of each component of the composition are as shown in Table 2. The resin composition was prepared in the same manner as in Example 1 except that the solid content concentration shown in Table 2 was prepared using the solvents listed in Table 2.

The resin composition was prepared in the same manner as in Example 1 except that the coating was applied by a slot coater instead of the spin coater to form a protective film. The results are shown in Table 2.

In Tables 1 to 2, (A) component, (C) component Lewis acid metal catalyst, (D) component cationically polymerizable compound, (E) adhesion aid, (F) surfactant, and (S) The abbreviations of the solvents represent the following materials: (A) Component: ST = styrene GMA = glycidyl methacrylate O-MA = (3-ethyl-3-oxyethyl) methyl methacrylate CHMI = N-cyclohexylmaleimide MA=methacrylic acid M-THP=1-ethylcyclohexane methacrylate ECPMA=2-methyl-2-propionic acid tetrahydro-2H-pyran-2 -Base ester C-1: Zinc chloride C-2: N-nitrosophenylhydroxylamine Al salt D-1: Bisphenol A phenolic epoxy resin manufactured by Japan Epoxy Resins Co., Ltd., trade name: EPIKOTE 157S65 E-1: γ-glycidoxypropyltrimethoxydecane F-1: Polyoxane type surfactant Toray Dowcorning Silicone Dowcorning Co., Ltd., trade name: SH-28PA) S-1: propylene glycol Monomethyl ether acetate

Industrial applicability

The resin composition of the present invention can form a cured film having high flatness on the substrate even in a substrate having low surface flatness, and is suitable for use as transparency, high surface hardness, heat resistance and pressure resistance, and acid resistance. A protective film for an optical device such as a color filter for a liquid crystal display element (LCD) or a color filter for a charge coupled device (CCD), which is excellent in various resistances such as alkali resistance and sputter resistance.

Claims (9)

A resin composition characterized by having 100% by weight of (A): (a1) a polymerizable unsaturated compound having an oxiranyl group or an oxetanyl group and (a2) the above (a1) a copolymer of a polymerizable unsaturated compound other than the above, containing 0.01 to 50 parts by weight of (B) a phosphate ester having a structure represented by the following formula (1), X in the formula (1) represents an integer of 0 to 2, R ¹ represents a hydrogen atom or an organic group in which an atom adjacent to the phosphorus atom is a carbon atom, and R ² represents an organic atom in which an atom adjacent to the oxygen atom is a carbon atom. Group. The resin composition of claim 1, wherein R ¹ in the formula (1) of the component (B) is an alkyl group, an aryl group, a benzyl group or an alkyl terminal or a side chain having 1 to 18 carbon atoms; An alkyl group having 1 to 8 carbon atoms or an acetate group having an alkoxy group having 1 to 4 carbon atoms, and R ² is an alkyl group or an aryl group or a benzyl group having 1 to 18 carbon atoms . The resin composition of claim 1, wherein the component (B) is trimethyl phosphate and/or triethyl phosphate. The resin composition of claim 1, wherein the resin composition further contains 0.0001 to 20 parts by weight of the (C) Lewis acid catalyst based on 100 parts by weight of the component (A). The resin composition of claim 1, wherein the resin composition further contains 3 to 200 parts by weight of (D) a cationically polymerizable compound (excluding the above component (A)) per 100 parts by weight of the component (A). The resin composition of the fourth aspect of the invention is further contained in an amount of from 3 to 200 parts by weight (D) of the cationically polymerizable compound (excluding the component (A) above) per 100 parts by weight of the component (A). The resin composition according to any one of claims 1 to 6, which is used for forming a protective film of a color filter. A method of forming a protective film for a color filter, characterized in that a coating film is formed on a substrate using a resin composition as in claim 7 of the patent application, and then heat-treated. A protective film for a color filter formed of a resin composition as in claim 7 of the patent application.