TWI569100B - Negative type photosensitive resin composition - Google Patents

Description

Negative photosensitive resin composition

The present invention relates to a negative photosensitive resin composition and a cured film obtainable therefrom. More specifically, the present invention relates to a photosensitive resin composition suitable for use in a display material, a cured film, and various materials using the cured film.

An epoxy cationic polymerization-based UV-curing resin containing an epoxy compound and a photo-acid generator is known to have high transparency and can be thickened (for example, Patent Document 1). However, since it adheres to a coating film after exposure after coating, it is inferior in handleability. Further, since it cannot be developed by an aqueous alkaline solution, it is necessary to develop an image with an organic solvent. The alkali-developing system is considered to be feasible when a carboxyl group is introduced into the polymer. However, when a monomer having an epoxy group is copolymerized with a monomer having a carboxyl group, a reaction between an epoxy group and a carboxyl group is likely to occur during polymerization. It is difficult to control the synthesis of the polymer. Further, even if the reaction is controlled, the polymer can be synthesized, and its storage stability is low.

As a system which is feasible as a base image, a polymer having an acrylonitrile group, a radical containing a polyfunctional propylene group monomer and a photoradical initiator is known. A negative type material of a polymerization system (for example, Patent Document 2). In the present invention, alkali development is possible by introducing a carboxyl group to a polymer, but in terms of thick film formation, high viscosity is required and workability is poor. Further, the problem is that since it is polymerized into a radical system, it is easily blocked by oxygen on the surface during photocuring, and becomes a film which greatly reduces the surface.

On the other hand, the positive material has a high degree of resolution, but it is difficult to form a thick film and has low transparency (for example, Patent Document 3).

From this point of view, it is possible to have a highly transparent alkali-developing material and a material having high workability at the time of thick film formation.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] International Patent Application Publication No. WO2008/007764

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-302389

[Patent Document 3] Japanese Patent Laid-Open No. Hei 8-339082

The present invention has been made in view of the above-mentioned matters, and can provide a film which can be thickened and which is not adhered before exposure, and can be formed into a pattern with high resolution by alkali development, and the coating film has high transparency. On the other hand, a negative photosensitive resin composition having a small shrinkage after post-baking is used.

The inventors of the present invention have devoted themselves to research in order to solve the above problems, and as a result, have completed the present invention.

In other words, as a first aspect, a negative photosensitive resin composition containing the following (A) component, (B) component, and (C) solvent: (A) component: at least (i) N-alkane a monomer mixture of oxymethyl (meth) acrylamide, and (ii) a monomer having an alkali-soluble group, a copolymer copolymerized, (B) component: photoacid generator, (C) component: solvent According to a second aspect, the negative photosensitive resin composition of the first aspect, wherein the (A) component (ii) having an alkali-soluble group is maleimide, as the third In the negative-type photosensitive resin composition of the first aspect or the second aspect, the component (D) further contains 0.1 to 10 parts by mass of a sensitizer based on 100 parts by mass of the photosensitive resin composition. According to a fourth aspect, the negative photosensitive resin composition according to the first aspect or the second aspect, wherein the (E) component further contains a polymer having a hydroxyl group, and the fifth aspect is described in the first aspect. The negative photosensitive resin composition of the third aspect, wherein the component (A) is a monomer mixture further containing a monomer having a hydroxyl group The copolymer which is copolymerized, as the sixth viewpoint, the negative type described in the first to fifth viewpoints The photosensitive resin composition is obtained by using the negative photosensitive resin composition of any one of the first aspect to the sixth aspect, as a component (F). The eighth aspect of the invention is the interlayer insulating film for a liquid crystal display comprising the cured film of the seventh aspect, and the optical filter comprising the cured film described in the seventh aspect. .

The photosensitive resin composition of the present invention can be alkali-developed without adhesion before exposure, and can form a highly transparent and high-resolution coating film pattern even in a thick film. Therefore, it is most suitable as a structure for an optical member. use.

The negative photosensitive resin composition of the present invention is a photosensitive resin composition containing the following components (A), (B) and (C) a solvent.

(A) component: copolymerization of a monomer mixture containing at least (i) N-Alkoxymethylmethacrylamide and (ii) a monomer having an alkali-soluble group And (B) component: photoacid generator, (C) solvent.

<(A) component>

The component (A) will contain at least (i) N-alkoxymethyl (methyl) propyl A copolymer obtained by copolymerizing a monomer mixture of N-Alkoxymethylmethacrylamide and (ii) an alkali-soluble group-containing monomer.

In the present invention, the copolymer refers to a polymer obtained by copolymerization using a monomer having an unsaturated double bond such as acrylate, methyl acrylate, acrylamide, methacrylamide or styrene.

The copolymer of the component (A) is preferably a copolymer having such a structure, and the skeleton of the main chain of the polymer constituting the copolymer and the kind of the side chain are not particularly limited.

However, if the copolymer of the component (A) is an excessively large number average molecular weight of more than 100,000, the developability of the unexposed portion is lowered, and if the number average molecular weight is less than 2,000, the hardening of the exposed portion is caused. If it is not sufficient, there is a case where the component is eluted at the time of development. Thus, the number average molecular weight is in the range of 2,000 to 100,000.

The (i) N-alkoxymethyl (meth) acrylamide used for the component (A) is represented by the structure of the formula (1):

(wherein R ¹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, wherein R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

Specific examples of such monomers include N-(methoxymethyl)propenylamine, N-(methoxymethyl)methacrylamide, and N-(n-butoxy). Methyl) acrylamide, N-(n-butoxymethyl)methacrylamide, N-(isobutoxymethyl) acrylamide, N-(isobutoxymethyl) A Acrylamide and the like.

The (ii) single-system having an alkali-soluble group used for (A) component is a monomer which has a carboxyl group, a phenolic hydroxyl group, an acid anhydride group, and a maleic imine group.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloxy)ethyl)phthalate, and mono-(2-(methacryl).醯oxy)ethyl)phthalate, N-(carbonylbenzene)maleimide, N-(carbonylbenzene)methacrylamide, N-(carbonylbenzene)acrylamide, 4 vinyl Benzoic acid, etc.

Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl). ) Maleidin and the like.

Examples of the single system having an acid anhydride group include maleic anhydride, Itaconic anhydride, and the like.

As a single system which has a maleic imine group, a maleimide is mentioned, for example.

Further, in the present invention, when a copolymer having a specific functional group is obtained, a monomer having a specific functional group may be used in combination with a monomer capable of copolymerization.

Specific examples of such a monomer include an acrylate compound, a methacrylate compound, an N-substituted maleimide compound, an acrylonitrile, an acrylamide compound, a methacrylamide compound, and styrene. Chemical And vinyl compounds.

Specific examples of the above monomers are given below, but are not limited to these.

Examples of the acrylate compound include methacrylate, ethacrylate, isopropyl acrylate, benzyl acrylate, naphthalene acrylate, mercapto acrylate, mercapto methacrylate, and phenyl. Acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxy triethylene glycol acrylate Ester, 2-ethoxyethyl acrylate, Tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-gold Alkyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl Acrylate, diethylene glycol monoacrylate, caprolactone 2-(acryloxy)ethyl ester, poly(ethylene glycol) diethyl ether acrylate, 5-propenyloxy-6-hydroxynorbornene -2-carbonyl (Carboxylic)-6-lactone, propylene oxime ethyl isocyanate and 8-ethyl-8-tricyclodecyl acrylate, glycidol Ester.

Examples of the methacrylate compound include methyl methacrylate, methyl ethacrylate, methyl isopropyl acrylate, methyl benzyl acrylate, methyl naphthalene acrylate, methyl methacrylate, and hydrazine. Methyl methacrylate, methyl phenyl acrylate, methyl 2,2,2-trifluoroethyl acrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2 - methoxyethyl methacrylate, methoxy triethylene glycol Methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofuran methyl acrylate, 3-methoxybutyl methacrylate, methyl 2-methyl-2-adamantyl methacrylate, γ-butane Ester methyl acrylate, methyl 2-propyl-2-adamantyl acrylate, methyl 8-methyl-8-tricyclodecyl acrylate, methyl 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate Ester, methyl 4-hydroxybutyl acrylate, methyl 2,3-dihydroxypropyl acrylate, methyl diethylene glycol monoacrylate, 2-caprolactone 2-(methacryloxy)ethyl ester, poly (Glycol) diethyl ether methyl acrylate, 5-methylpropenyloxy-6-hydroxynorbornene-2-carbonyl (Carboxylic)-6-lactone, methacrylic acid ethyl isocyanate and 8-ethyl -8-tricyclomethyl methacrylate, glycidyl acrylate, and the like.

Examples of the N-substituted maleimide compound include N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

Examples of the styrene compound include styrene, methyl styrene, chlorostyrene, and bromostyrene.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl onion, vinyl biphenyl, vinyl carbazole, and 2-hydroxyethyl vinyl ether. Phenyl vinyl ether and propyl vinyl ether.

The method of obtaining a copolymer having a specific functional group used in the present invention is not particularly limited, for example, by a monomer having a specific functional group, a monomer having a further copolymerizable non-reactive functional group, and A polymerization initiator or the like is allowed to coexist in a solvent as desired, and is obtained by subjecting it to a polymerization reaction at a temperature of from 50 to 110 °C. The solution used at that time The agent is not particularly limited as long as it is a monomer constituting a propylene-based copolymer having a specific functional group and a propylene-based copolymer having a specific functional group. Specific examples thereof include a solvent described in the solvent (C) to be described later.

The propylene-based copolymer having a specific functional group obtained in this manner is usually in a solution state in which it has been dissolved in a solvent.

Further, the solution of the copolymer obtained in the above manner is charged with diethyl ether or water under stirring to reprecipitate, and the resulting precipitate is filtered, washed, and then under normal pressure or reduced pressure. It can be used as a powder of a copolymer at room temperature or by heating and drying. By such an operation, the polymerization initiator or the unreacted monomer which coexists with the copolymer can be removed, and as a result, a powder of the purified copolymer can be obtained. In the case where the purification is not sufficiently performed in one operation, it is preferred to re-dissolve the obtained powder and repeat the above operation.

In the present invention, the polymerization solvent of the above propylene-based copolymer may be used as it is, or the powder may be dissolved in a solvent (C) to be described later as a solution.

Further, in the present invention, the copolymer of the component (A) may be a mixture of a plurality of specific copolymers.

The copolymerization ratio of the monomer is preferably N-alkoxymethyl(meth)acrylamide/alkaline soluble monomer/other substance = 10 to 60/10 to 40/0 to 80 parts by weight. When the amount of the alkali-soluble monomer is too small, the unexposed portion tends to be a residual film or residue which is not dissolved in the developing solution. In too many cases, the hardenability of the exposed portion is insufficient and the pattern cannot be formed. Capability. When the N-alkoxymethyl (meth) acrylamide is too small, the photocurability is insufficient and there is a possibility that the exposed portion is dissolved at the time of development. In an excessive case, the solubility of the unexposed portion may be insufficient to cause a residual film or residue.

<(B) component>

The component (B) is a photoacid generator. The type of the acid used in the thermosetting resin composition of the present invention is not particularly limited. Specific examples of such a photoacid generator include the following.

Further, examples of the photoacid generator of the component (B) include diphenyliodonium chloride, diphenyliodoniumtrifluoromethanesulphonate, and diphenyliodonium methanesulfonate. , diphenyliodotoluenesulfonate, diphenyliodobromide, diphenyliodonium Tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, Bis(p-tert-butylphenyl)iodohexafluorophosphate, bis(p-tert-butylphenyl)iodomethanesulfonate, bis(p-tert-butylphenyl)iodotosylate, double P-tert-butylphenyl)iodotrifluoromethanesulfonate, bis(p-tert-butylphenyl)iodotetrafluoroborate, bis(p-tert-butylphenyl)iodine chloride, double (p- Chlorophenyl) iodine chloride, bis(p-chlorophenyl)iodotetrafluoroborate, three Triphenylsulfonium chloride, barium triphenyl borate, triphenylsulfonium trifluoromethanesulfonate, tris(p-methoxyphenyl)phosphonium tetrafluoroborate, tris(p-methoxy Phenyl)phosphonium hexafluorophosphonate, tris(p-ethoxyphenyl)phosphonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tris(p-methoxyphenyl) Tetrafluoroborate, tris(p-methoxyphenyl)phosphonium hexafluorophosphonate, tris(p-ethoxyphenyl)phosphonium tetrafluoroborate, and the like.

The content of the component (B) of the negative photosensitive resin composition of the present invention is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, more preferably 100 parts by mass of the component (A). It is 2 to 10 parts by mass. In the case where the ratio is less than 0.5 part by mass, there is a case where the photoreactivity is lowered and the sensitivity is lowered. On the other hand, when it exceeds 20 parts by mass, the transmittance of the formed coating film may be lowered, and the storage stability of the solution may be lowered.

<(C) Solvent>

The component (A) and the component (B) to be used in the present invention are dissolved, and the component (D), the component (E), and the component (F) to be added, which are added as desired, are dissolved. The solvent and the structure of such a solvent are not particularly limited.

Examples of such a solvent (C) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, and diethyl ether. Glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, Cyclohexanone, 2-butyl Ketone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, B Ethyl oxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropane Ethyl acetate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide , N,N-dimethylacetamide and N-methylpyrrolidone.

These solvents may be used singly or in combination of two or more.

Among these (C) solvents, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, etc., have good coating properties and high safety. It is ideal. These solvents are generally used as a solvent for a photoresist material.

<(D) component>

The component (D) is a sensitizer. When the coating film composed of the negative photosensitive resin composition of the present invention is exposed and the reaction rate of the photoacid generator of the component (B) is small, the reaction rate can be improved by adding a sensitizer. Examples of such a sensitizer include 9,10-dibutoxy fluorene, 9-hydroxymethyl hydrazine, Thioxanthone, 2-isopropyl ketoxime, and 4-isopropyl ketone. Tons of ketone, 2-chlorosultone, 2,4-diethyl ketoxime, hydrazine, 1,2-dihydroxyindole, 2-ethyl hydrazine, 1,4-diethoxynaphthalene, etc. .

As the component (D), one type or two or more types of the above-mentioned sensitizers may be used in combination.

The amount of the sensitizer added is usually 0.1 to 10 parts by mass, preferably 0.1 to 8 parts by mass, per 100 parts by mass of the component (A). If the amount of the sensitizer is too large as compared with the above, the transparency of the coating film may be lowered.

<(E) component>

The component (E) is a polymer having a hydroxyl group. Examples of the polymer having a hydroxyl group include a polymer obtained by polymerizing a monomer having a hydroxyl group, cellulose, hydroxypropylcellulose, a polymer obtained by copolymerizing a diepoxy group and a dicarboxylic acid, and a polymer obtained by copolymerizing an epoxy group and a diphenol, a polyester polyol, a polyether polyol, a polycaprolactone polyol, or the like, but is preferably a polymer obtained by polymerizing a monomer having a hydroxyl group or a hydroxypropane Cellulose.

The monomer having the above-mentioned hydroxyl group may be a monomer having a hydroxyl group among the copolymerizable monomers exemplified in the above component (A), either alone or in combination with a copolymerizable monomer. Polymerized copolymer.

Among the copolymerizable monomers exemplified in the component (A), a single system having a hydroxyl group may, for example, be 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate or 4-hydroxybutyl acrylate. 2,3-Di-hydroxypropyl acrylate and 5-propenyloxy-6-hydroxynorbornene-2-carbonyl (Carboxylic)-6-lactone, 2-hydroxyethyl methacrylate, 2- Methyl hydroxypropyl acrylate, methyl 4-hydroxybutyl acrylate, methyl 2,3-dihydroxypropyl acrylate, and 5-methylpropenyloxy-6-hydroxynorbornene-2-carbonyl (Carboxylic) -6-lactone Wait.

Examples of the copolymerizable monomer include a copolymerizable monomer exemplified as the component (A).

The polymer having these hydroxyl groups may be used singly or in combination of two or more.

The content of the polymer of the hydroxyl group of the component (E) of the negative photosensitive resin composition of the present invention is preferably 5 to 150 parts by mass, more preferably 10 parts by mass based on 100 parts by mass of the copolymer of the component (A). Up to 120 parts by mass. In the case where the ratio is much smaller than the above, the sensitivity of the negative photosensitive resin composition is lowered. On the other hand, when the ratio is too large, the development of the unexposed portion is lowered. The cause of the residual film or residue.

<(F) component>

The crosslinking agent which is the component (F) of the present invention is preferably a crosslinking agent obtained by reacting the component (B) with an acid produced by the component (B). The crosslinking agent may, for example, be a compound such as an epoxy compound or a methylol compound, and is preferably a methylol compound.

Specific examples of the above-mentioned methylol compound include compounds such as alkoxymethylated acetylene urea, alkoxymethylated benzene melamine, and alkoxymethylated melamine.

Specific examples of the alkoxymethylated acetylene urea include 1,3,4,6-tetrakis(methoxymethyl)acetylene urea and 1,3,4,6-tetra(butoxymethyl). Acetylene urea, 1,3,4,6-tetrakis (hydroxymethyl) acetylene urea, 1,3-bis (hydroxyl) Base, urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl) -4,5-dihydroxy-2-imidazolidinone and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone. As a commercial product, a compound such as acetylene urea compound (trade name: Cymel (registered trademark) 1170, powder link (registered trademark) 1174), methylated urea resin (trade name: UFR (registered name) Trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea/formaldehyde resin manufactured by Dainippon INK Chemical Industry Co., Ltd. (high condensation type) , trade name: BECKAMINE (registered trademark) J-300S, with P-955, with N).

Specific examples of the alkoxymethylated benzene melamine include tetramethoxymethylbenzene melamine. As a commercial item, Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade name: NIKALAC (registered trademark) BX-4000, same as BX-37, and BL- 60, with BX-55H) and so on.

Specific examples of the alkoxymethylated melamine include hexylmethoxymethylmelamine. As a commercial item, a methoxymethyl melamine compound (trade name: Cymel (registered trademark) 300, the same 301, the same 303, the same 350) and a butoxymethyl melamine compound (produced by Mitsui Cytec Co., Ltd.) are mentioned. Trade name: MAICOAT (registered trademark) 506, same as 508), Sanwa Chemical methoxymethyl melamine compound (trade name: NIKALAC (registered trademark) MW-30, same MW-22, same MW-11, same MS-001, same as MX-002, same MX-730, same MX- 750, MX-035), butoxymethyl melamine compound (trade name: NIKALAC (registered trademark) MX-45, same MX-410, same MX-302).

Further, a compound obtained by condensing a melamine compound, a urea compound, an acetylene urea compound, and a benzene melamine compound in which a hydrogen atom of such an amine group is replaced with a methylol group or an alkoxymethyl group may be used. For example, a high molecular weight compound produced from a melamine compound and a benzoguanamine compound described in U.S. Patent No. 6,323,310. The commercially available product of the above-mentioned melamine compound is a product name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and the like, and a commercially available product of the phenyl melamine compound is a product name: Cymel (registered) Trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.).

These crosslinking agents can be used individually or in combination of 2 or more types.

The content of the crosslinking agent of the component (F) of the negative photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass, more preferably 10 to 10 parts by mass based on 100 parts by mass of the copolymer of the component (A). 80 parts by mass. In the case where the ratio is much smaller than the above, the photocurability of the negative photosensitive resin composition is lowered, and on the other hand, in the case where it is excessively large, the development of the unexposed portion is low. This is the cause of the residual film or residue.

<Other additives>

Further, the negative photosensitive resin composition of the present invention may further contain an inhibitor, a surfactant, or the like as long as it does not impair the effects of the present invention. A rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, and a dissolution promoter such as a polyvalent phenol or a polyvalent carboxylic acid.

<negative photosensitive resin composition>

The negative photosensitive resin composition of the present invention dissolves the polymer of the component (A) and the photoacid generator of the component (B) in the solvent (C), and further increases the component (D) according to individual requirements. One or more of the sensitizer, the polymer having a hydroxyl group of the component (E), the crosslinking agent of the component (F), and other additives.

Among them, preferred examples of the negative photosensitive resin composition of the present invention are as follows.

[1]: A negative photosensitive resin composition containing 0.5 to 20 parts by mass of the component (B) based on 100 parts by mass of the component (A) and having the component (C) dissolved in the solvent.

[2] The composition of the above [1] further contains 0.1 to 10 parts by mass of the negative photosensitive resin composition of the component (D), based on 100 parts by mass of the component (A).

[3] The composition of the above [1] or [2] further contains 5 to 150 parts by mass of the negative photosensitive resin composition of the component (E), based on 100 parts by mass of the component (A).

[4] The composition of the above [1] to [3] further contains 5 to 100 parts by mass of the negative photosensitive resin composition of the component (F), based on 100 parts by mass of the component (A).

The ratio of the solid content of the negative photosensitive resin composition of the present invention, The components are not particularly limited as long as they are uniformly dissolved in the solvent, and are, for example, 1 to 80% by mass, or, for example, 5 to 60% by mass or 10 to 50% by mass. Here, the solid fraction refers to a substance obtained by removing (C) a solvent from the entire composition of the negative photosensitive resin composition.

The preparation method of the negative photosensitive resin composition of the present invention is not particularly limited, and examples of the preparation method include, for example, dissolving (A) component (copolymer) in (C) solvent and component (B) ( The photoacid generator is mixed in the solution in a specific ratio as a method of a uniform solution, or at the appropriate stage of the preparation method, (D) component (sensitizer), (E) is added as necessary. A method of mixing a component (a polymer having a hydroxyl group), a component (F) (crosslinking agent), and other additives.

When the negative photosensitive resin composition of the present invention is prepared, a solution of a specific copolymer obtained by a polymerization reaction in a solvent (C) can be used as it is, in which case a solution of the component (A) is used. When a component (B) which is the same as the above is added to form a uniform solution, it is also preferable to further add (C) a solvent for the purpose of adjusting the concentration. In this case, the solvent (C) used in the formation of the specific copolymer may be the same as or different from the solvent (C) used for adjusting the concentration in the preparation of the negative photosensitive resin composition.

Then, a solution of the prepared negative photosensitive resin composition is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

<Coating film and hardened film>

The negative photosensitive resin composition of the present invention is applied to a semiconductor substrate (for example, a ruthenium/ruthenium oxide-coated substrate, a tantalum nitride substrate, or a metal-coated substrate such as aluminum, molybdenum, or chromium, a glass substrate, or a quartz substrate, Coating on the ITO substrate or the like by spin coating, flow coating, roll coating, slit coating, slit continuous coating, inkjet coating, etc., followed by heating plate or oven The coating film can be formed by performing preliminary drying. Thereafter, the coating film is heat-treated to form a negative photosensitive resin film.

As a condition for this heat treatment, for example, a suitable heating temperature and a heating time are selected from a temperature of 70 ° C to 160 ° C and a time of 0.3 to 60 minutes. The heating temperature and the heating time are preferably from 80 ° C to 140 ° C for 0.5 to 10 minutes.

In addition, the film thickness of the negative photosensitive resin film formed of the negative photosensitive resin composition is, for example, 0.1 to 30 μm, or 0.5 to 20 μm, and more preferably 1 to 15 μm.

The negative photosensitive resin film formed of the negative photosensitive resin composition of the present invention is exposed to light such as ultraviolet rays, ArF, KrF, or F ₂ laser light by using a mask having a specific pattern. The action of the acid generated by the photoacid generator (PAG) of the component (B) contained in the photosensitive resin film is such that the exposed portion of the film becomes an insoluble matter in the alkali developing solution.

Next, post-exposure heating (PEB) is performed on the negative photosensitive resin film. As a heating condition in this case, for example, a heating temperature suitably selected from a temperature of 70 ° C to 150 ° C and a time of 0.3 to 60 minutes is employed. Degree and heating time.

Thereafter, development was carried out using an alkali developing solution. Thereby, in the negative photosensitive resin film, the unexposed portion is removed, and a pattern-like relief is formed.

Examples of the alkali developing solution to be used include an aqueous solution of an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, and a hydrogen peroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline. An aqueous alkaline solution such as an aqueous solution of a fourth-order ammonium, an aqueous amine solution such as ethanolamine, propylamine or ethylenediamine. Further, a surfactant or the like may be added to these developing solutions.

Among the above, an aqueous solution of 0.1 to 2.38 mass% of tetraethylamine hydroxide is generally used as a developing solution for a photoresist, and the alkali developing solution is also used in the photosensitive resin composition of the present invention. It causes a problem such as swelling and is well developed.

Further, as the developing method, a coating liquid method, a dipping method, a shaking dipping method, or the like can be used. The development time at this time is usually 15 to 180 seconds.

After the development, the negative photosensitive resin film is washed with running water for, for example, 20 to 90 seconds, and then air-dried by using compressed air or compressed nitrogen or by spinning. The moisture on the substrate is then used to obtain a patterned film.

Next, such a pattern forming film can be obtained by post-baking for thermal curing, specifically by heating using a hot plate, an oven, or the like, thereby obtaining heat resistance, transparency, flatness, and A film that is excellent in low water absorption, chemical resistance, and the like, and has a good undulating pattern.

As the post-baking, generally, the heating temperature selected in the range of 140 ° C to 250 ° C is used, which is 5 to 30 minutes in the case of a hot plate, and 30 to 90 minutes in the case of an oven. Methods.

Then, by such post-baking, a cured film having a good pattern shape as a target can be obtained.

As described above, the negative photosensitive resin composition of the present invention can be adhered without exposure before exposure, and can be alkali-developed, and a film thickness of about 10 μm is sufficient high sensitivity and an exposed portion at the time of development. The degree of film thinning is very small, and a coating film having a fine pattern can be formed. Further, this cured film is excellent in transparency, heat resistance, and solvent resistance. Therefore, a film such as an interlayer insulating film, a protective film, an insulating film, an optical film, or the like can be suitably used for a liquid crystal display, an organic EL display, a touch panel element, or the like.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto.

[Abbreviations used in the examples]

The meaning of the abbreviations used in the following examples are as follows.

MAA: Methacrylic acid

MI: Maleate

MMA: Methyl methacrylate

BMAA: N-(n-butoxymethyl) acrylamide

HEMA: 2-hydroxyethyl methacrylate

GMA: glycidyl methacrylate

ST: Styrene

AIBN: azobisisobutyronitrile

PAG1: TPS-TF (manufactured by Toyo Seisaku Co., Ltd.) (Compound name: triphenylsulfonium trifluoromethanesulfonate)

PAG2: GSID-26-1 (manufactured by BASF) (compound represented by the above formula (79))

PAG3: IRGACURE 369 (manufactured by BASF) (photopolymerization initiator)

CYM: Cymel 303 (product name) manufactured by SAITEK JAPAN (Compound name: hexylmethoxymethyl melamine)

HMA: 9-hydroxymethyl hydrazine

HPC: Hydroxypropyl cellulose

DPHA: diisopentyl alcohol pentyl/hexyl acrylate

BTEAC: Chlorotriphenylamine

PGME: propylene glycol monomethyl ether

PGMEA: propylene glycol monomethyl ether acetate

JE: JER157S70 made by Japan epoxy resin company

[Measurement of number average molecular weight and weight average molecular weight]

The number average molecular weight and the weight average molecular weight of the specific copolymer and the specific crosslinked body obtained according to the following synthesis examples, using Japanese spectroscopic GPC apparatus (Shodex (registered trademark) column KF803L and KF 804L) manufactured by the company was measured under the conditions that the elution solvent tetrahydrofuran was eluted at a flow rate of 1 ml/min and flowed through a column (column temperature of 40 ° C). In addition, the number average molecular weight (hereinafter referred to as Mn) and the weight average molecular weight (hereinafter referred to as Mw) described below are expressed in terms of polystyrene.

<Synthesis Example 1>

As a monomer component constituting the copolymer, MI (26.0 g), BMAA (45.0 g), and ST (29.0 g) were used, and AIBN (2 g) was used as a radical polymerization initiator, by making these components in a solvent PGME ( The polymerization reaction was carried out in 238 g) to obtain a copolymer solution (copolymer concentration: 30% by mass) (P1) of Mn 4,300 and Mw 9,800. Further, the polymerization temperature was adjusted to a temperature of from 60 ° C to 90 ° C.

<Synthesis Example 2>

As a monomer component constituting the copolymer, MAA (20.0 g), BMAA (50.0 g), and ST (30.0 g) were used, and AIBN (2 g) was used as a radical polymerization initiator, by making these components in a solvent PGME ( The polymerization reaction was carried out in 238 g) to obtain a copolymer solution (copolymer concentration: 30% by mass) (P2) of Mn 4,000 and Mw 9,200. Further, the polymerization temperature was adjusted to a temperature of from 60 ° C to 90 ° C.

<Synthesis Example 3>

As a monomer component constituting the copolymer, MAA (20.0 g), BMAA (50.0 g), and HEMA (30.0 g) were used, and AIBN (2 g) was used as a radical polymerization initiator, by making these components in a solvent PGME ( The polymerization was carried out in 238 g) to obtain a copolymer solution (copolymer concentration: 30% by mass) (P3) of Mn 4,800 and Mw 10,500. Further, the polymerization temperature was adjusted to a temperature of from 60 ° C to 90 ° C.

<Synthesis Example 4>

As a monomer component constituting the copolymer, MAA (20.0 g), HEMA (40.0 g), MMA (40.0 g) were used, and AIBN (2 g) was used as a radical polymerization initiator, by making these components in a solvent PGME ( The polymerization reaction was carried out in 238 g) to obtain a copolymer solution (copolymer concentration: 30% by mass) (P4) of Mn3,900 and Mw8,500. Further, the polymerization temperature was adjusted to a temperature of from 60 ° C to 90 ° C.

<Comparative Synthesis Example 1>

As a monomer component constituting the copolymer, MAA (50.0 g) and MMA (50.0 g) were used, and AIBN (2 g) was used as a radical polymerization initiator, and these components were polymerized in a solvent PGMEA (120 g). Thus, a copolymer solution (copolymer concentration: 40% by mass) was obtained. Further, the polymerization temperature was adjusted to a temperature of from 60 ° C to 90 ° C. By adding GMA (33.0 g), BTEAC (1.1 g), and PGMEA (49.5 g) to 200 g of the copolymer, the reaction was carried out to obtain Mn8,700, Mw22,000 (A) component (specific copolymer). Solution Polymer concentration: 40.5 mass%) (P5). Further, the reaction temperature was adjusted to 90 to 120 °C.

<Comparative Synthesis Example 2>

As a monomer component constituting the copolymer, MAA (30.0 g), GMA (50.0 g), and ST (20.0 g) were used, and AIBN (2 g) was used as a radical polymerization initiator, by making these components in a solvent PGME ( In 238 g), the polymerization reaction was carried out at a temperature of 60 ° C to 90 ° C, but gelation occurred during the polymerization reaction, and it was not possible to be used in the evaluation described later.

<Examples 1 to 7 and Comparative Examples 1 to 2>

According to the composition shown in Table 1 below, the component (B), the solvent (C), and the component (D) are added to the solution of the component (A), and the components (E) and (F) are added. The mixture was mixed at a specific ratio, and stirred at room temperature for 3 hours to obtain a uniform solution, and the negative photosensitive resin compositions of the respective examples and comparative examples were prepared.

With respect to the obtained negative photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 and 2, the film thickness after the prebaking, the presence or absence of adhesion, the transmittance, the resolution, and the sensitivity were individually measured.

[Evaluation of film thickness after prebaking]

After the negative photosensitive resin composition was applied onto a tantalum wafer using a spin coater, it was prebaked on a hot plate at a temperature of 110 ° C for 120 seconds to form a coating film. The film thickness of this coating film was measured using F20 by FILMETRICS.

[Evaluation of Transmission Rate]

After the negative photosensitive resin composition was applied onto a quartz substrate using a spin coater, it was prebaked on a hot plate at a temperature of 110 ° C for 120 seconds to form a coating film. With respect to this coating film, ultraviolet rays having a light intensity of 5.5 mW/cm ² at a wavelength of 365 nm were irradiated for 36 seconds by a Canon ultraviolet irradiation device PLA-600FA. The film was exposed to a hot plate at 95 ° C for 120 seconds, and then heated, and then post-baked in an oven at a temperature of 150 ° C for 15 minutes to form a cured film. The cured film was measured for transmittance at a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, model: SIMADSU UV-2550).

[evaluation of resolution]

After the negative photosensitive resin composition was applied onto an alkali-free glass using a spin coater, it was prebaked on a hot plate at a temperature of 110 ° C for 120 seconds to form a coating film. With respect to this coating film, ultraviolet rays having a light intensity of 5.5 mW/cm ² having a wavelength of 365 nm were transmitted through a mask of a line and space pattern by a Canon ultraviolet irradiation apparatus PLA-600FA, and irradiated at 190 mJ/cm ² . Thereafter, the film was heated on the hot plate at a temperature of 110 ° C for 120 seconds. Thereafter, development was carried out by immersing in an aqueous solution of 2.38 mass% of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 60 seconds, and then washing with ultrapure water for 20 seconds to form a pattern. The produced pattern was sintered in a 150 ° C oven for 15 minutes, and observed by SEM, and the line width of the pattern was the minimum pattern size corresponding to the line width of the mask as the resolution.

[Evaluation of sensitivity]

After the negative photosensitive resin composition was applied onto an alkali-free glass using a spin coater, it was prebaked on a hot plate at a temperature of 110 ° C for 120 seconds to form a coating film. For this coating film, ultraviolet rays having a light intensity of 5.5 mW/cm ² at a wavelength of 365 nm were transmitted through a mask of a line and space of 20 μm by a Canon ultraviolet irradiation device PLA-600FA at 50 mJ/cm. ² scales to illuminate. Thereafter, the film was heated on the hot plate at a temperature of 110 ° C for 120 seconds. Thereafter, development was carried out by immersing in a 2.38 mass% TMAH aqueous solution for 60 seconds, and then washing with ultrapure water for 20 seconds to form a pattern. The lowest exposure amount that can form a pattern of 20 μm is set as the sensitivity.

[Results of evaluation]

The results of the above evaluations are shown in Table 2 below.

As judged by the results shown in Table 2, the negative photosensitive resin compositions of Examples 1 to 7 can be coated with a thick film of 10 μm or more, and a high transmittance can be obtained even in a thick film. It can also perform alkali imaging to maintain high resolution and sensitivity.

In Comparative Example 1, the film thickness was not increased, and the residual film ratio after post-baking was also as low as 90% or less. Regarding Comparative Example 2, adhesion occurred after prebaking, and it was not possible to develop with an alkali developing solution.

[Industrial Applicability]

The negative-type photosensitive resin composition of the present invention is suitable as a protective film, a planarizing film, and an insulating film formed on various displays such as a thin film transistor (TFT) liquid crystal display device, an organic EL device, and a touch panel device. The material of the cured film is particularly suitable as an interlayer insulating film for forming a TFT-type liquid crystal element, a protective film for a color filter, an array planarizing film, an interlayer insulating film of a capacitive touch panel, and an organic EL element. A material such as an insulating film or a structural sheet of an antireflection layer on the display surface.

Claims (8)

A negative photosensitive resin composition comprising the following components (A), (B) and (C), and component (A) comprising at least (i) N-alkoxymethyl (methyl) a monomer mixture of N-Alkoxymethylmethacrylamide and (ii) a monomer having an alkali-soluble group, a copolymer copolymerized, and a monomer having an alkali-soluble group is a copolymer of maleimide (B) component: photoacid generator, (C) solvent. The negative photosensitive resin composition according to the first aspect of the invention, wherein the component (D) further contains 0.1 to 10 parts by mass of a sensitizer based on 100 parts by mass of the photosensitive resin composition. The negative photosensitive resin composition as described in claim 1, wherein the (E) component further contains a polymer having a hydroxyl group. The negative photosensitive resin composition according to the first aspect of the invention, wherein the component (A) is a copolymer obtained by further copolymerizing a monomer mixture containing a monomer having a hydroxyl group. The negative photosensitive resin composition as described in claim 1, wherein the component (F) further contains a crosslinking agent. A cured film obtained by using the negative photosensitive resin composition according to any one of the first to fifth aspects of the invention. An interlayer insulating film for a liquid crystal display comprising the cured film described in claim 6 of the patent application. An optical filter characterized by the sixth item of the patent application scope The cured film described is composed of.