JP4389583B2 - Radiation sensitive resin composition - Google Patents

Description

  The present invention relates to a radiation-sensitive resin composition, a spacer formed using the radiation-sensitive resin composition, and a method for producing the same.

  The liquid crystal panel uses spacer particles such as glass beads and plastic beads having a predetermined particle size to keep the distance between the two substrates constant. These spacer particles are randomly scattered on the glass substrate. Therefore, when the spacer is present in the effective pixel portion, there are problems that the reflection of the spacer and the contrast of the liquid crystal panel are lowered due to scattering of incident light. In order to solve these problems, a method of forming a spacer by photolithography using a radiation sensitive resin composition has been performed. (See, for example, Patent Document 1)

As a radiation-sensitive resin composition for forming the spacer, a composition using a copolymer of an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound such as a glycidyl acrylate group is known (for example, , Refer to Patent Document 2, etc.) In order to impart alkali developability, a considerable amount of carboxylic acid or an alternative acid component is required, so that an epoxy group reacts during storage and thickens and solidifies. Has the disadvantages.
In addition, with the increase in definition of display elements, the spacers are also required to have high resolution.
Furthermore, it is also known that when the solvent resistance of the spacer is poor, the yield decreases and the productivity decreases.

JP 2001-92128 A, page 2, line 2-5 Japanese Patent Laid-Open No. 11-174673, page 3, left column, lines 9-25

  An object of the present invention is to provide a highly sensitive radiation-sensitive resin composition having good storage stability and capable of forming a spacer with high resolution and good solvent resistance.

As a result of intensive studies, the present inventor has found that conventional problems can be solved by using a binder resin having a specific structure, and has led to the present invention.
That is, the present invention relates to a radiation sensitive resin composition containing a binder resin (A), a compound (B) having an ethylenically unsaturated bond and capable of addition polymerization, and a photopolymerization initiator (C). Is a radiation-sensitive resin composition for forming a spacer, which is at least one resin selected from the group consisting of the following (AA) to (AC).
A resin (AA) obtained by a reaction between an acrylic resin (A1) containing a carboxyl group and a compound (A21) having both an alicyclic epoxy group and a mono (meth) acrylate group in the molecule;
A mono (meth) acrylate compound (A221) having a glycidyl group and a mono (meth) acrylate compound (A222) having a tricyclodecane skeleton or a monocyclopentadiene skeleton to an acrylic resin (A1) containing a carboxyl group A resin (AB) obtained by reacting a (meth) acrylate compound (A223), and further reacting a monocarboxylic acid having an unsaturated group with the obtained resin (A22);
Provided is a resin (AC) obtained by further reacting the above resin (AB) with carboxylic anhydride.
Further, the present invention provides a spacer formed from the radiation-sensitive resin composition, a liquid crystal display device including the spacer, and a layer formed of the radiation-sensitive resin composition on a substrate, and a solvent. After the removal, there is provided a method for producing a spacer, wherein the layer is exposed through a mask and then developed to form a pattern and further heated.

  According to the radiation sensitive resin composition of the present invention, it is possible to form a spacer with high resolution and good solvent resistance. Moreover, since the solvent resistance is good, the productivity of TFTs, color filters, etc. can be improved. Furthermore, since storage stability is favorable, it can preserve | save for a long time rather than the conventional product.

As the binder resin (A) in the radiation sensitive resin composition of the present invention, at least one resin selected from the group consisting of the following (AA) to (AC) is used.
A resin (AA) obtained by a reaction between an acrylic resin (A1) containing a carboxyl group and a compound (A21) having both an alicyclic epoxy group and a mono (meth) acrylate group in the molecule;
Mono (meth) acrylate compound (A221) having glycidyl group and mono (meth) acrylate compound (A2222) having tricyclodecane skeleton (A2221) or dicyclopentadiene skeleton to acrylic resin (A1) containing carboxyl group And a resin (AB) obtained by reacting the obtained resin (A222) with a monocarboxylic acid having an unsaturated group,
Resin (AC) obtained by further reacting the above-mentioned resin (AB) with polyvalent carboxylic acid anhydride (A24).

As the acrylic resin (A1) containing a carboxyl group used for the binder resin (A) contained in the radiation-sensitive resin composition of the present invention, for example, a structural unit (A11) derived from an unsaturated carboxylic acid, And a copolymer with a structural unit (A12) derived from a compound having a carbon-carbon unsaturated bond.
Examples of the structural unit (A11) derived from the unsaturated carboxylic acid include unsaturated carboxylic acids having at least one carboxyl group in the molecule such as unsaturated monocarboxylic acid and unsaturated dicarboxylic acid, Specific examples include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid and the like. Here, the description of (meth) acrylic acid in this specification represents acrylic acid and / or methacrylic acid.
Examples of the structural unit (A12) derived from the compound having a carbon-carbon unsaturated bond include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Unsaturated carboxylic acid esters such as benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate or dicyclopentanyl (meth) acrylate;
Unsaturated alkyl carboxylic acid aminoalkyl esters such as aminoethyl (meth) acrylate;
Carboxylic acid vinyl esters such as vinyl acetate or vinyl propionate;
Aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene;
Examples thereof include structural units derived from vinyl cyanide compounds such as acrylonitrile, methacrylonitrile or α-chloro (meth) acrylonitrile. Here, description of (meth) acrylate in this specification represents acrylic ester and / or methacrylic ester.
The structural unit (A11) derived from the unsaturated carboxylic acid and the structural unit (A12) derived from the compound having a carbon-carbon unsaturated bond are each one or more of units derived from the exemplary compound. Can be used in combination.
Examples of the acrylic resin (A1) include styrene / methacrylic acid copolymer, benzyl methacrylate / methacrylic acid copolymer, methyl methacrylate / methacrylic acid copolymer, cyclohexyl methacrylate / methacrylic acid copolymer, Nyl methacrylate / methacrylic acid copolymer, dicyclopentanyl methacrylate / methacrylic acid copolymer, and the like. In particular, a benzyl methacrylate / methacrylic acid copolymer is preferable.
The content of the structural unit (A11) derived from the unsaturated carboxylic acid in the acrylic resin (A1) is preferably 5 to 50% by mass fraction, and more preferably 10 to 40%. . When the content of (A11) is in the above range, a sufficient amount of compound (A21) having both an alicyclic epoxy group and an unsaturated bond can be introduced, the degree of curing of the resin is improved, and the spacer As such, the reliability tends to be improved, which is preferable.

  Examples of the compound (A21) having both an alicyclic epoxy group and an unsaturated bond in the molecule include compounds represented by the following formulas (1) to (22).

[In the formulas (1) to (22), R ¹ represents a hydrogen atom or a hydrocarbon having 1 to 6 carbon atoms, R ² represents a divalent hydrocarbon group having 1 to 8 carbon atoms, and R ³ represents carbon. The bivalent unitary hydrogen group of number 1-20 is shown. However, R ^{1 to} R ³ may be the same or different. n represents an integer of 0 to 10. ]

  Here, the alicyclic epoxy group in the present invention refers to an epoxy group formed by bonding one oxygen to two adjacent carbon atoms on the ring of the alicyclic hydrocarbon compound.

As the compound (A21) having both an alicyclic epoxy group and an unsaturated bond in the molecule, those having an unsaturated bond derived from an acrylate group are preferred, and 3,4-epoxycyclohexylmethyl acrylate is particularly preferred.
Moreover, the compound (A21) which has both an alicyclic epoxy group and an unsaturated bond in a molecule | numerator can be used individually or in combination of 2 or more types.

  The acrylic resin (A1) containing a carboxyl group in the binder resin (A) used in the radiation-sensitive resin composition of the present invention, and a compound having both an alicyclic epoxy group and a mono (meth) acrylate group in the molecule In the resin (AA) obtained by the reaction with (A21), the constituent ratio of (A21) in the resin (AA) obtained by the reaction between (A1) and (A21) is the mole fraction in all constituent units. From 5 to 40%, preferably from 10 to 40%, more preferably from 15 to 40%. When (A21) is in the above range, sufficient curability is obtained and the reliability as a spacer tends to be improved, which is preferable.

  A mono (meth) acrylate compound (A221) having a glycidyl group and a mono (meth) acrylate compound (A223) having a tricyclodecane skeleton (A222) or a dicyclopentadiene skeleton on an acrylic resin (A1) containing a carboxyl group And a resin (AB) obtained by further reacting a monocarboxylic acid (A23) having an unsaturated group with a resin (A22) obtained by reacting with a mono (meth) acrylate compound (A221) having a glycidyl group. ) Include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and the like. Among them, glycidyl acrylate and glycidyl methacrylate are preferable.

  Examples of the mono (meth) acrylate compound (A223) having a tricyclodecane skeleton (A222) or dicyclopentadiene skeleton include dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl ( And meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate. These can be used alone or in combination.

  Specific examples of the unsaturated carboxylic acid (A23) include acrylic acid and methacrylic acid. Acrylic acid and methacrylic acid can be used alone or in combination. In addition to these acrylic acid and methacrylic acid, other acids can be used. Specifically, as the other acid, at least one carboxylic acid selected from other unsaturated carboxylic acids such as crotonic acid, itaconic acid, maleic acid and fumaric acid can be used in combination. A monomer containing a hydroxy group and a carboxyl group in the same molecule, such as α- (hydroxymethyl) acrylic acid, can also be used in combination.

  The polyvalent carboxylic acid anhydride (A24) is used for imparting alkali developability to the binder resin. Specifically, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride Examples thereof include polyvalent carboxylic acid anhydrides such as acid, benzophenone tetracarboxylic acid anhydride, and biphenyl tetracarboxylic acid anhydride. Tetrahydrophthalic anhydride or succinic anhydride is preferable. These can be used alone or in combination of two or more.

  Here, in this specification, description of (meth) acrylate represents an acrylate and / or a methacrylate. Moreover, the description of (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  The amount of the compound (A2) having both an alicyclic epoxy group and an unsaturated bond in the molecule is such that the double bond amount of the obtained unsaturated group-containing acrylic resin is preferably 1.0 to 4 per 1 kg of the resin. It is set to be in the range of 0.0 mol, more preferably 1.5 to 3.0 mol. When the double bond amount is in the above range, sufficient curability tends to be obtained, which is preferable.

A mono (meth) acrylate compound (A221) having a glycidyl group and tricyclodecane in the acrylic resin (A1) containing a carboxyl group in the binder resin (A) used in the radiation-sensitive resin composition of the present invention. Mono- (meth) acrylate compound (A222) having a skeleton or mono- (meth) acrylate compound (A223) having a dicyclopentadiene skeleton are reacted with a resin (A22) obtained by reacting with a mono (meth) acrylate compound (A22) having a dicyclopentadiene skeleton. In the resin (AB) obtained by reacting the carboxylic acid (A23), the constituent ratio of (A1), (A221) and (A222) or (A223) and (A23) is in the following range in terms of molar fraction: Is preferred.
Structural unit derived from (A1); Structural unit derived from 5 to 96 mol% acrylate (A221); Structural unit derived from 2 to 55 mol% epoxy (A222) or (A223); A structural unit derived from (A23); 0.5-0.5 with respect to 1.0 equivalent of an epoxy group in a resin obtained by polymerizing (A-1), (A221) and (A222) or (A223) 1.0 equivalent, preferably 0.2 to 0.9 equivalent.
When the component ratio of each component is in the above range, sufficient curability is obtained and the reliability as a spacer tends to be improved, which is preferable.

  In the resin (AC) obtained by further reacting the polycarboxylic acid anhydride (A24) with the resin (AB) in the binder resin (A) used in the radiation-sensitive resin composition of the present invention, The amount is preferably 50 to 100%, more preferably 60 to 100% in terms of a mole fraction with respect to the amount of hydroxyl group produced when (AB) is reacted. When the amount of (A24) used is in the above range, higher developability tends to be obtained, which is preferable.

In the reaction between (A1) and (A21), the epoxy group contained in (A21) reacts with the carboxyl group contained in the acrylic resin of (A1), and the resin obtained after the reaction contains an epoxy. The group disappears and does not exist. For this reason, since the epoxy group in resin does not react during a storage period, the radiation sensitive resin composition containing the obtained resin does not deteriorate the storage stability due to the reaction of the epoxy group.
In addition, a mono (meth) acrylate compound (A221) having a glycidyl group and a mono (meth) acrylate compound (A222) having a tricyclodecane skeleton or a dicyclopentadiene skeleton in an acrylic resin (A1) containing a carboxyl group In a resin (AB) obtained by reacting a monocarboxylic acid (A23) having an unsaturated group with a resin (A22) obtained by reacting a mono (meth) acrylate compound (A223) having The epoxy group disappears and does not exist. For this reason, since the epoxy group in resin does not react during a storage period, the radiation sensitive resin composition containing the obtained resin does not deteriorate the storage stability due to the reaction of the epoxy group.
Furthermore, the storage stability of the resin (AC) obtained by further reacting the resin (AB) with carboxylic anhydride is also good.

The acid value of the binder resin (A) used in the radiation-sensitive resin composition of the present invention is preferably 50 to 170, and more preferably 70 to 140.
As for the combination of (A1) and (A2), for example, the combination of the components specifically exemplified in the above (A1) and (A2) can be mentioned, and (A1) styrene / methacrylic acid copolymer is preferable. And (A2) 3,4-epoxycyclohexylmethyl acrylate, benzyl methacrylate / methacrylic acid copolymer, and (A2) 3,4-epoxycyclohexylmethyl acrylate.

  The polystyrene-reduced weight average molecular weight of the binder resin (A) used in the radiation-sensitive resin composition of the present invention by GPC measurement method is usually 1,000 or more and 50,000 or less, preferably 1,500 or more and 20,000 or less. It is. When the weight average molecular weight in terms of polystyrene is in the above range, the pattern resolution tends to be improved, which is preferable. The acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the binder resin, and can usually be determined by titrating with an aqueous potassium hydroxide solution.

  The content of the binder resin (A) is a mass fraction with respect to the solid content of the radiation-sensitive resin composition, and is usually 20% or more and 80% or less, preferably 35% or more and 70% or less. .

  The compound (B) having an ethylenically unsaturated bond and capable of addition polymerization used in the radiation-sensitive resin composition of the present invention includes, for example, at least one ethylenically unsaturated bond at the terminal, preferably 2 or more. It may be a monomer, a prepolymer such as a dimer, a trimer or an oligomer, a mixture thereof or a copolymer thereof.

  Examples of the monomers include esters of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid with aliphatic polyhydric alcohol compounds, and unsaturated carboxylic acids and aliphatic polyhydric compounds. And amides with a polyvalent amine compound.

Examples of the ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound include, for example, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, Neopentyl glycol diacrylate, trimethylol propane triacrylate, trimethylol propane tri (acryloyloxypropyl) ether, trimethylol ethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate Acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate Over DOO, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, acrylic acid esters, such as sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer;
Tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, penta Erythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl Dimethyl meta Bis - methacrylic acid ester such as [p- (methacryloxyethoxy) phenyl] dimethyl methane;
Ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetrataconate, etc. Itaconic acid ester of
Crotonic acid esters such as ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate;
Isocrotonic acid esters such as ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate;
Examples thereof include maleic esters such as ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylamide, and diethylenetriamine. Examples include trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.

  Other examples of the monomer include a vinyl urethane compound obtained by adding a vinyl monomer represented by the formula (23) to a polyisocyanate compound having two or more isocyanate groups in one molecule.

[In Formula (23), R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group. ]

The vinyl urethane compound is preferably a compound containing two or more polymerizable vinyl groups in one molecule (Japanese Patent Publication No. 48-41708). Further, urethane acrylates as described in JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, etc. Polyfunctional acrylates and methacrylates such as polyester acrylates are also included. Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.
The content of the compound (B) having an ethylenically unsaturated bond and capable of addition polymerization is generally 10% or more and 75% or less, preferably 10% or more and 75% or less, in terms of mass fraction with respect to the solid content of the radiation sensitive resin composition. It is 15% or more and 60% or less. When the content of the compound (B) having an ethylenically unsaturated bond and capable of addition polymerization is in the above range, the pattern strength and smoothness tend to be good, which is preferable.

  As the photopolymerization initiator (C) used in the radiation sensitive resin composition of the present invention, an active radical is generated by irradiation with light, and polymerization of a compound having an ethylenically unsaturated bond and capable of addition polymerization is performed. Is not particularly limited as long as it is a compound capable of initiating acetophenone photopolymerization initiator, benzoin photopolymerization initiator, benzophenone photopolymerization initiator, thioxanthone photopolymerization initiator, triazine photopolymerization initiator An oxadiazole photopolymerization initiator and the like can be used.

  Examples of the acetophenone photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, and 2-hydroxy-2-methyl-1- [4. -(2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2- And oligomers of dimethylamino-1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one.

  Examples of the benzoin photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

  Examples of the thioxanthone photopolymerization initiator include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the triazine photopolymerization initiator include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p -Dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4,6- Bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl)- 4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2- Toxiethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl -S-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6- Methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2 -(4,7 Dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2 -(4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6 -Di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [PN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl ] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN- Ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s- Triazine, 4- (p-N-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] 2,6 -Di (trichloromethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-tri 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2 , 6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N- (Ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di ( Trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro- p-N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) aminophenyl] -2 , 6-Di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4 -[M-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylaminophenyl) ) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (M-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2, 6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro Til) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN- Chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine 4- (m-fluoro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- Such as o- Fluorochemicals -p-N-chloroethyl aminophenyl) -2,6-di (trichloromethyl) -s-triazine.

  Examples of the oxadiazole-based photopolymerization initiator include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-butoxystyryl) -1,3 4-oxadiazole, 2-trichloromethyl-5- (p-hydroxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-chlorostyryl) -1,3,4 Oxadiazole, 2-trichloromethyl-5- (p-methoxyphenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-butoxyphenyl) -1, , 4-oxadiazole, 2-trichloromethyl-5- (2-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (β- (2-benzofuryl) vinyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (β- (6-methoxy-2-benzofuryl) vinyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (2- And benzofuryl) -1,3,4-oxadiazole.

Examples of the photopolymerization initiator (C) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2′-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. can also be used. .
Among them, preferred photopolymerization initiators include 1- (4-morpholinophenyl) -2-benzyl-2-dimethylaminobutan-1-one, [2,4-bis (trichloromethyl) -6-piperonyl-1, 3,5-triazine] and the like.

The radiation sensitive resin composition of the present invention may contain a photopolymerization initiation aid. Examples of the photopolymerization initiation assistant include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoate. 2-ethylhexyl acid, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 9, Examples include 10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. These photopolymerization initiation assistants can be used alone or in combination of two or more.
When using the said photoinitiator adjuvant, the usage-amount is 0.01 to 10 mol normally with respect to 1 mol of photoinitiators.

  The total use amount of the photopolymerization initiator (C) and the photopolymerization initiation assistant in the radiation-sensitive resin composition of the present invention is a mass fraction with respect to the solid content of the radiation-sensitive resin composition, and is usually 0.01. % To 30%, preferably 0.1% to 15%.

The radiation sensitive resin composition of the present invention is usually used in a state where it is mixed with a solvent (D) and diluted. Examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;
Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate;
Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone;
Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin;
Esters such as methyl 2-hydroxyisobutanoate, methyl lactate, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate;
and cyclic esters such as γ-butyrolactone. Preferable solvents include propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, methyl 2-hydroxyisobutanoate, ethyl lactate, etc. Among them, propylene glycol monomethyl ether acetate and ethyl 3-ethoxypropionate are preferable.
The said solvent (D) is used individually or in mixture of 2 or more types, respectively.
Content of the solvent (D) in the radiation sensitive resin composition of this invention is a mass fraction with respect to the total amount of a radiation sensitive resin composition, and is 50-50% normally, Preferably it is 60-90%. It is.

The radiation-sensitive resin composition of the present invention may further comprise other components as necessary, for example, thermal polymerization inhibitors, dissolution inhibitors, dissolution accelerators, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers. In addition, additives such as an adhesion improver may be contained.
The radiation sensitive resin composition of the present invention includes, for example, a solution obtained by dissolving a binder resin (A) in a solvent (D), a compound (B) having an ethylenically unsaturated bond, and an ethylenically unsaturated bond. And a solution in which addition-polymerizable compound (B) is dissolved in solvent (D) and a solution in which photopolymerization initiator (C) or photopolymerization initiator (C) is dissolved in solvent (D) are mixed Can be manufactured. After mixing, a solvent (D) may be further added. After mixing, it is preferable to remove solid matter by filtration. For example, it is preferable to filter using a filter having a pore size of 3 μm or less, preferably about 0.1 μm or more and 2 μm or less. The solvent used for each component may be the same or different as long as it is compatible.

In order to form a spacer using the radiation sensitive resin composition of the present invention, for example, a layer (1) made of the radiation sensitive resin composition of the present invention is formed on a substrate (2) (FIG. 1 ( a)) The layer (1) is exposed to radiation (4) through a mask (3) and exposed (FIG. 1 (b)), and then developed (FIG. 1 (c)).
Examples of the substrate (2) include resin substrates such as a transparent glass plate and a silicon wafer, as well as a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, and a polyimide substrate. Examples of the substrate include a substrate in which a color filter on which a TFT circuit or ITO wiring is formed in advance is formed on the substrate.

  The layer (1) comprising the radiation-sensitive resin composition can be formed by a usual method, for example, a method of applying the radiation-sensitive resin composition of the present invention on the substrate (2). The coating is performed by a known coating method such as a spin coating method (spin coating method), a casting coating method, a roll coating method, a slit & spin coating method, or a coating method using a liquid-saving coater. The radiation-sensitive resin composition layer (1) can be formed by coating on a substrate or the like and then volatilizing the solvent by heating drying (pre-baking) or drying under reduced pressure. The said radiation sensitive resin composition layer (1) is a layer which consists of solid content of a radiation sensitive resin composition, and the thing whose thickness is about 1-6 micrometers is normally formed.

Subsequently, a radiation (4) is irradiated to a radiation sensitive resin composition layer (1) through a mask (3). The pattern of the mask (3) is appropriately selected according to the spacer pattern. Usually, the size of the spacer pattern is 1 to 50 μm. If the number of display pixels is increased, the spacer pattern is reduced and can be appropriately determined.
As the shape of the spacer pattern, a horizontal cross section with respect to the substrate surface may be a polygon such as a triangle or a quadrangle, a circle or an ellipse, and a vertical cross section with respect to the substrate surface may be a rectangle or a trapezoid.
As radiation radiated to the radiation-sensitive resin composition layer, for example, ultraviolet rays such as g-line and i-line are used. The radiation is preferably irradiated using, for example, a mask aligner or a stepper (not shown).

  Develop after exposure. Development can be performed on the radiation-sensitive resin composition layer (1) after exposure by, for example, a paddle method, a dipping method, a shower method, or the like. As the developer, an alkaline aqueous solution is used as usual. As an alkaline aqueous solution, an aqueous solution of an alkaline compound is used as usual, and the alkaline compound may be an inorganic alkaline compound or an organic alkaline compound.

  Examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, and silicic acid. Examples include sodium, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia.

  Examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Is mentioned. The alkaline compounds are used alone or in combination of two or more. The developer usually contains 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass of the alkaline compound per 100 parts by mass of the developer.

  The developer may contain a surfactant. Examples of the surfactant include nonionic surfactants, cationic surfactants, and anionic surfactants.

  Examples of the nonionic surfactant include polyoxyethylene derivatives such as polyoxyethylene alkyl ether, polyoxyethylene aryl ether, and polyoxyethylene alkyl aryl ether, oxyethylene / oxypropylene block copolymers, and sorbitan fatty acid esters. , Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

  Examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and quaternary ammonium salts such as lauryltrimethylammonium chloride.

  Examples of the anionic surfactant include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, kill sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, Examples thereof include alkyl aryl sulfonates such as sodium dodecyl naphthalene sulfonate. These surfactants are used alone or in combination of two or more.

  Further, the developer may contain an organic solvent. Examples of the organic solvent include water-soluble organic solvents such as methanol and ethanol.

  Of the radiation-sensitive resin composition layer (1), the radiation non-irradiated region (12) that was not irradiated with radiation in the previous exposure was dissolved in the developer by the development, and the radiation irradiated region ( 11) remains without being dissolved in the developer to form a negative pattern (5).

  After development, it is usually washed with water and dried. It is preferable that after the drying, a heat treatment (post-baking) is further performed in that the heat resistance and solvent resistance of the pattern are improved. Heating is performed by a method in which the substrate after irradiation with radiation over the entire surface is heated by a heating device such as a hot plate or a clean oven. The heating temperature is usually about 150 ° C to 250 ° C, preferably about 180 ° C to 240 ° C, and the heating time is usually about 5 minutes to 120 minutes, preferably about 15 minutes to 90 minutes. By heating, the pattern is further cured, and a spacer having excellent heat resistance, solvent resistance and the like is formed.

  The spacer formed in this way is useful, for example, as a TFT substrate, a spacer constituting a color filter substrate, or a dot spacer for a touch panel.

  While the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and includes the meaning equivalent to the terms of the claims and all modifications within the scope. EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

Example 1
Binder resin (A) [benzyl methacrylate / methacrylic acid copolymer (A1) (molar ratio during polymerization = 60: 40) 300 parts by mass and 3,4-epoxycyclohexylmethyl acrylate (A21) 112 parts by mass Resin (AA) obtained as a product, acid value is 133, polystyrene equivalent weight average molecular weight (Mw) is 25,000] 70 parts by mass,
30 parts by mass of compound (B) [dipentaerythritol hexaacrylate] having an ethylenically unsaturated bond and capable of addition polymerization,
Photopolymerization initiator (C) [2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine] 3 parts by mass and solvent [propylene glycol monomethyl ether acetate] 240 parts by mass were mixed at 23 ° C. Thereafter, the mixture was filtered under pressure through a cartridge filter having a pore diameter of 0.5 μm to obtain a radiation sensitive resin composition as a filtrate.

In addition, the measurement conditions of said polystyrene conversion weight average molecular weight are as follows.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL, TSK-GELG4000HXL in-line column temperature; 40 ° C
Mobile phase solvent; tetrahydrofuran flow rate; 1.0 ml / min
Injection volume: 50 μl
Detector; RI
Measurement sample concentration: 0.6% by mass (solvent: tetrahydrofuran)
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

  Moreover, about the measurement of the acid value of said binder polymer, it measured as the quantity (mg) of potassium hydroxide required in order to neutralize 1 g of acrylic acid type polymers.

The radiation-sensitive resin composition obtained above is spin-coated on a 4-inch silicon wafer (2), and heated (prebaked) at 100 ° C. for 2 minutes using a hot plate, the radiation-sensitive resin composition layer (1 ) And the film thickness was measured using a film thickness meter [Lambda Ace (Dainippon Screen Mfg. Co., Ltd.)], and it was 4.0 μm (FIG. 1 (a)).
Thereafter, an i-line stepper [NSR-1755i7A (NA = 0.5) (manufactured by Nikon Corporation)] was used for the obtained radiation-sensitive resin composition layer (1) through a mask (3). Radiation (4) was irradiated and exposed (FIG. 1 (b)). As the mask (3), a mask for forming a cylindrical pattern having a diameter of 1 μm, 2 μm, and 3 μm was used.

After exposure, the film was developed with a 23 ° C. aqueous tetramethylammonium hydroxide solution (containing 0.2 parts by mass of tetramethylammonium hydroxide in 100 parts by mass) for 60 seconds, and then washed with ultrapure water. , Dried. In the pattern after development, when the exposure amount in the mask exposure in which the dot diameter is 3 μm is defined as the effective sensitivity, the effective sensitivity is 70 mJ / cm ² and the resolution is 2 μm. After drying, the substrate was heated in a clean oven at 220 ° C. for 30 minutes to form a spacer pattern (5) (FIG. 1 (c)).
The obtained spacer pattern (5) had a thickness of 3.2 μm and a good cylindrical cross-sectional shape.
Further, the substrate on which the spacer pattern was formed was immersed in methyl ethyl ketone or N-methylpyrrolidone (23 ° C.) for 30 minutes and subjected to a solvent resistance test. As a result, no change was observed before and after the immersion.

  Moreover, even if the obtained radiation sensitive resin composition was stored at 23 ° C. for 2 months, the radiation sensitive resin composition did not thicken. Furthermore, the evaluation result obtained using the radiation-sensitive resin composition immediately after preparation is equivalent to the evaluation result obtained using the radiation-sensitive resin composition stored at 23 ° C. for 2 months. And storage stability was good.

Example 2
Example 1 except that the photopolymerization initiator is changed to 3 parts by mass of 1- (4-morpholinophenyl) -2-benzyl-2-dimethylaminobutan-1-one and 3 parts by mass of 4,4′-diethylaminobenzophenone. The same operation was performed to obtain a radiation sensitive resin composition.
As a result of performing the same operation as in Example 1, the resolution of the spacer pattern (5) obtained with an effective sensitivity of 60 mJ / cm ² was 2 μm and the thickness (T1) was 3.1 μm.
The substrate on which the spacer pattern was formed was immersed in methyl ethyl ketone or N-methylpyrrolidone (23 ° C.) for 30 minutes and subjected to a solvent resistance test. As a result, no change was observed before and after the immersion.

Comparative Example 1
Example 1 except that the binder resin is replaced with a methacrylic acid / benzyl methacrylate copolymer (mass composition ratio; 20/80, polystyrene-equivalent weight average molecular weight (Mw) is 25,000, acid value is 110 mg KOH / g). The radiation sensitive resin composition was obtained by operating.
As a result of performing the same operation as in Example 1, the obtained spacer pattern had a cross section perpendicular to the substrate surface, a semicircular cross section having a sufficient film thickness, and a good columnar shape. A spacer shape was not obtained. Moreover, as a result of performing a solvent resistance test by immersing in methyl ethyl ketone (23 ° C.) for 30 minutes, the film was swollen after immersion.

Comparative Example 2
A methacrylic acid / glycidyl methacrylate / styrene copolymer (mass composition ratio; 20/50/30, polystyrene-reduced weight average molecular weight (Mw) is 21,000) is 100 parts by mass, and the same operation as in Example 1 is carried out. As a result, a radiation sensitive resin composition was obtained.
Binder resin (A) [methacrylic acid / glycidyl methacrylate / styrene copolymer (mass composition ratio: 20/50/30, weight average molecular weight (Mw) in terms of polystyrene is 21,000)] 100 parts by mass,
80 parts by mass of compound (B) [dipentaerythritol hexaacrylate] having an ethylenically unsaturated bond and capable of addition polymerization,
Photopolymerization initiator (C) [1- (4-morpholinophenyl) -2-benzyl-2-dimethylaminobutan-1-one] 25 parts by mass and solvent [diethylene glycol dimethyl ether] 381 parts by mass were mixed at 23 ° C. Thereafter, the mixture was filtered under pressure through a cartridge filter having a pore diameter of 0.5 μm to obtain a radiation sensitive resin composition as a filtrate.
As a result of performing the same operation as in Example 1, a good columnar spacer was obtained. However, when the radiation-sensitive resin composition was stored at 23 ° C. for 3 weeks, deterioration due to thickening was observed, and the same evaluation as in Example 1 was performed using this, immediately after preparation of the radiation-sensitive resin composition. The initial performance obtained was not reproduced and the storage stability was poor.

  The radiation sensitive resin composition of this invention can be used for formation of spacers, such as a color filter.

It is a schematic diagram which shows the process of forming a transparent film using the radiation sensitive resin composition of this invention.

Explanation of symbols

1: Radiation sensitive resin composition layer 11: Radiation non-irradiated area 12: Radiation irradiated area 2: Substrate 3: Mask 4: Radiation 5: Transparent film

Claims (6)

In the radiation-sensitive resin composition containing the binder resin (A), the compound (B) having an ethylenically unsaturated bond and capable of addition polymerization, and the photopolymerization initiator (C), the binder resin (A) is: A radiation-sensitive resin composition for spacer formation, which is a resin of AA ) .
Resin (AA) obtained by reaction of acrylic resin (A1) containing carboxyl group and compound (A21) having both alicyclic epoxy group and mono (meth) acrylate group in the molecule   In a resin (AA) obtained by a reaction between an acrylic resin (A1) containing a carboxyl group and a compound (A21) having both an alicyclic epoxy group and a mono (meth) acrylate group in the molecule, (A1) 2. The radiation-sensitive radiation for forming a spacer according to claim 1, wherein the constituent ratio of (A21) in the resin (AA) obtained by the reaction between (A21) and (A21) is 5 to 40% in terms of mole fraction in all constituent units. Resin composition.   The content of the compound (B) having an ethylenically unsaturated bond and capable of addition polymerization is 25% or more and 250% or less in terms of mass fraction with respect to the content of the binder resin (A). The radiation-sensitive resin composition for forming a spacer described in 1.   The spacer formed with the radiation sensitive resin composition in any one of Claims 1-3.   A liquid crystal display device comprising the spacer according to claim 4.   A layer comprising the radiation-sensitive resin composition according to any one of claims 1 to 3 is formed on a substrate, and after removing the solvent, the layer is exposed through a mask and then developed to form a pattern. And further heating the spacer.

Images