KR102027756B1 - Negative photosensitive resin composition - Google Patents

Abstract

[Problem] Thick film can be formed, there is no adhesion even before exposure, pattern formation is possible by high resolution by alkali development, and the resulting coating film has high transparency and small shrinkage even after postbaking. to provide.
[Solution] The negative photosensitive resin composition containing the following (A) component, (B) component, and (C) solvent. (A) component: The copolymer which copolymerized the monomer mixture containing at least (i) N-alkoxymethyl (meth) acrylamide and the monomer which has (ii) alkali-soluble group, (B) component: Photo-acid generator, (C )solvent.

Description

Negative photosensitive resin composition {NEGATIVE PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a negative photosensitive resin composition and a cured film obtained therefrom. In more detail, this invention relates to the photosensitive resin composition suitable for the use of a display material, its cured film, and various materials using this cured film.

It is known that epoxy cation polymerization type UV curable resin containing an epoxy compound and a photo-acid generator is high in transparency, and can be thickened (for example, patent document 1). However, since there is tackiness in a coating film after application | coating and before exposure, handleability is bad. Moreover, since image development by aqueous alkali solution is not possible, image development by the organic solvent is essential. Although alkali development was considered to be possible by introducing a carboxyl group into a polymer, in copolymerization of the monomer which has an epoxy group, and the monomer which has a carboxyl group, reaction of an epoxy group and a carboxyl group occurs easily during superposition | polymerization, and synthesis control of a polymer is difficult. In addition, the storage stability is low even if the polymer is synthesized by controlling the reaction.

As an alkali development is possible, the negative-type material of the radical polymerization system containing the polymer which has an acryloyl group, a polyfunctional acryl monomer, and an optical radical initiator is known (for example, patent document 2). In this invention, although alkali image development is possible by introducing a carboxyl group into a polymer, in order to thicken, high viscosity is required and handling property is bad. Moreover, since polymerization is radical type | system | group, it is easy to receive oxygen inhibition of the surface at the time of photocuring, and there existed a problem that the film | membrane reduction of the surface became large.

On the other hand, the positive material has a high resolution but is difficult to thicken and has low transparency (for example, Patent Document 3).

From these points, a material with high transparency, alkali development and high handleability is desired even when thickening.

International Patent Application Publication WO2008 / 007764 Pamphlet Japanese Patent Application Laid-Open No. 2004-302389 Japanese Patent Application Laid-Open No. H8-339082

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is capable of forming a thick film, without adhesion even before exposure, and capable of forming a pattern at a high resolution by alkali development, and the resulting coating film has high transparency and small shrinkage after postbaking. It is providing a negative photosensitive resin composition.

MEANS TO SOLVE THE PROBLEM This inventor discovered this invention as a result of earnestly researching in order to solve the said subject.

That is, as a 1st viewpoint, the negative photosensitive resin composition containing the following (A) component, (B) component, and (C) solvent:

(A) component: The copolymer which copolymerized the monomer mixture containing at least (i) N-alkoxymethyl (meth) acrylamide and the monomer which has (ii) alkali-soluble group,

(B) Component: photoacid generator,

(C) component: a solvent,

As a 2nd viewpoint, the negative photosensitive resin composition as described in a 1st viewpoint whose monomer which has (ii) alkali-soluble group of (A) component is maleimide,

As a 3rd viewpoint, The negative photosensitive resin composition as described in a 1st viewpoint or a 2nd viewpoint which further contains 0.1-10 mass parts as a (D) component based on 100 mass parts of photosensitive resin compositions,

As a 4th viewpoint, the negative photosensitive resin composition as described in a 1st viewpoint or a 2nd viewpoint which further contains the polymer which has a hydroxyl group as (E) component,

As a 5th viewpoint, (A) component is a negative photosensitive resin composition as described in a 1st viewpoint thru | or a 3rd viewpoint which is a copolymer which copolymerized the monomer mixture which further contains a monomer which has a hydroxyl group,

As a 6th viewpoint, The negative photosensitive resin composition as described in a 1st viewpoint thru | or a 5th viewpoint which further contains a crosslinking agent as (F) component,

As a 7th viewpoint, the cured film obtained using the negative photosensitive resin composition in any one of a 1st viewpoint-a 6th viewpoint,

As an 8th viewpoint, the interlayer insulation film for liquid crystal displays which consists of a cured film as described in a 7th viewpoint,

As a ninth viewpoint, the optical filter which consists of a cured film as described in a 7th viewpoint,

It is about.

The photosensitive resin composition of this invention is optimal for formation of a structure as an optical member by the point which does not have adhesion before exposure, alkali development is possible, and the coating film pattern with high transparency and resolution can be formed also in a thick film.

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

(A) component: The copolymer which copolymerized the monomer mixture containing at least (i) N-alkoxymethyl (meth) acrylamide and the monomer which has (ii) alkali-soluble group,

(B) Component: photoacid generator,

(C) Solvent.

<(A) component>

(A) component is a copolymer which copolymerized the monomer mixture containing at least (i) N-alkoxymethyl (meth) acrylamide and the monomer which has (ii) alkali-soluble group.

In the present invention, the copolymer refers to a polymer obtained by copolymerization using a monomer having an unsaturated double bond such as acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide and styrene.

The copolymer of (A) component should just be a copolymer which has such a structure, and it does not specifically limit about the kind of backbone, side chain, etc. of the main chain of the polymer which comprises a copolymer.

However, if the copolymer of the component (A) has an excessive number average molecular weight of 100,000 or more, the developability of the unexposed portion is lowered. If the number average molecular weight is less than 2,000, the curing of the exposed portion is insufficient and development occurs. In some cases, components may elute. Therefore, the number average molecular weight is in the range of 2,000 to 100,000.

(I) N-alkoxymethyl (meth) acrylamide used for (A) component is represented by the structure of Formula (1):

[Formula 1]

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

Specific examples of these monomers include N- (methoxymethyl) acrylamide, N- (methoxymethyl) methacrylamide, N- (n-butoxymethyl) acrylamide, and N- (n-butoxymethyl) Methacrylamide, N- (isobutoxymethyl) acrylamide, N- (isobutoxymethyl) methacrylamide, and the like.

As a monomer which has an alkali-soluble group (ii) used for (A) component, the monomer which has a carboxyl group, a phenolic hydroxyl group, an acid anhydride group, and a maleimide group is mentioned.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, and mono- (2- (methacryloyloxy) ethyl) phthalate. , N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, tetravinyl benzoic acid and the like.

As a monomer which has a phenolic hydroxyl group, hydroxy styrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide, etc. are mentioned, for example. Can be.

As a monomer which has an acid anhydride group, maleic anhydride, itaconic anhydride, etc. are mentioned, for example.

As a monomer which has a maleimide group, maleimide is mentioned, for example.

Moreover, in this invention, when obtaining the copolymer which has a specific functional group, the monomer copolymerizable with the monomer which has a specific functional group can be used together.

As an example of such a monomer, an acrylic acid ester compound, a methacrylic acid ester compound, an N-substituted maleimide compound, an acrylonitrile, an acrylamide compound, a methacrylamide compound, a styrene compound, a vinyl compound, etc. are mentioned.

Hereinafter, although the specific example of the said monomer is given, it is not limited to these.

As said acrylate ester compound, For example, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2, 2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxy ethyl acrylate, methoxy triethylene glycol acrylate, 2-ethoxy ethyl acrylate , Tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acryl Latex, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, diethylene glycol Recall monoacrylate, caprolactone 2- (acryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6- Lactone, acryloyl ethyl isocyanate, 8-ethyl-8- tricyclodecyl acrylate, glycidyl acrylate, etc. are mentioned.

As said methacrylic acid ester compound, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, for example. Methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, Methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ- Butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate , 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether Methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, methacryloylethyl isocyanate, and 8-ethyl-8-tricyclodecyl methacrylate Glycidyl methacrylate, and the like.

As said N-substituted maleimide compound, N-methyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, etc. are mentioned, for example.

As said styrene compound, styrene, methyl styrene, chloro styrene, bromostyrene, etc. are mentioned, for example.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether. Can be mentioned.

Although the method of obtaining the copolymer which has a specific functional group used for this invention is not specifically limited, For example, the monomer which has a specific functional group, the monomer which has a non-reactive functional group copolymerizable elsewhere, and the solvent which coexisted the polymerization initiator etc. as needed. It is obtained by making a polymerization reaction in the temperature of 50-110 degreeC in the inside. At this time, the solvent used will not be specifically limited if the monomer which comprises the acrylic copolymer which has a specific functional group, and the acrylic copolymer which has a specific functional group are melt | dissolved. As a specific example, the solvent described in the (C) solvent mentioned later is mentioned.

The acrylic copolymer which has a specific functional group obtained in this way is a state of the solution melt | dissolved in the solvent normally.

In addition, the solution of the copolymer obtained as described above is added under stirring with diethyl ether, water or the like to reprecipitate, and the produced precipitate is filtered and washed, and then dried under normal pressure or reduced pressure, followed by air drying. It can be made into powder of coalescence. By such an operation, the polymerization initiator and unreacted monomer which coexist with a copolymer can be removed, As a result, the powder of the refined copolymer can be obtained. When it cannot fully refine | purify by operation once, the obtained powder may be redissolved in a solvent and the said operation may be repeated.

In this invention, the polymerization solution of the said acryl copolymer may be used as it is, or the powder may be redissolved in the solvent (C) mentioned later, for example, and may be used as a solution state.

In addition, in this invention, the copolymer of (A) component may be a mixture of several types of specific copolymers.

As a copolymerization ratio of a monomer, N-alkoxymethyl (meth) acrylamide / alkali-soluble monomer / other = 10-60 / 10-40/0-80 weight part is preferable. When there are too few alkali-soluble monomers, an unexposed part will not melt | dissolve in a developing solution and it will be easy to cause a residual film or a residue. In too many cases, there is a possibility that the curability of the exposed portion is insufficient and a pattern is not formed. When there is too little N-alkoxymethyl (meth) acrylamide, there exists a possibility that photocurability may run out and an exposure part may melt | dissolve at the time of image development. In too many cases, there is a possibility that the solubility of the unexposed part is insufficient, which may cause residual film or residue.

<(B) component>

(B) component is a photo-acid generator. The kind of acid used for the thermosetting resin composition of this invention is not specifically limited. The following are mentioned as a specific example of such a photo-acid generator.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

Moreover, as a photo-acid generator of (B) component, diphenyl iodonium chloride, diphenyl iodonium trifluoromethane sulfonate, diphenyl iodonium mesylate, diphenyl iodonium tosylate, diphenyl iodonium bromide, di Phenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluoro antimonate, diphenyl iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p- tert-butylphenyl) iodonium mesylate, bis (p-tert-butylphenyl) iodonium tosylate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl Iodide tetrafluoroborate, bis (p-tert-butylphenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodium tetrafluoroborate, triphenylsulfonium Chloride, tree Nylsulfonium bromide, triphenylsulfonium trifluoromethanesulfonate, tri (p-methoxyphenyl) sulfoniumtetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphonate, tri (p -Ethoxyphenyl) sulfonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tri (p-methoxyphenyl) phosphoniumtetrafluoroborate, tri (p-methoxyphenyl) phosphonium hexa Fluorophosphonates, tri (p-ethoxyphenyl) phosphoniumtetrafluoroborate, and the like.

Content of (B) component in the negative photosensitive resin composition of this invention becomes like this. Preferably it is 0.5-20 mass parts, More preferably, it is 1-15 mass parts with respect to 100 mass parts of (A) component. Preferably it is 2-10 mass parts. When this ratio is less than 0.5 mass part, photoreactivity may fall and a sensitivity may fall. Moreover, when it exceeds 20 mass parts, the transmittance | permeability of the formed coating film may fall, or the storage stability of a solution may fall.

<(C) solvent>

It dissolves (A) component and (B) component which are used for this invention, and also melt | dissolves the below-mentioned (D) component, (E) component, (F) component etc. which are added as needed, and have such a solubility. If it is a solvent, the kind, structure, etc. will not be specifically limited.

Examples of such a solvent (C) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene 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-butanone, 3-methyl-2- Pentanone, 2-pentanone, 2-heptanone, gamma -butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl oxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, And the like can be set acid ethyl acetate, butyl acetate, ethyl lactate, lactic acid butyl, N, N- dimethylformamide, N, N- dimethylacetamide and N- methylpyrrolidone.

These solvents can be used individually by 1 type or in combination of 2 or more types.

Among these (C) solvents, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and the like are preferred from the viewpoint of good coating properties and high safety. These solvents are generally used as a solvent for photoresist materials.

<(D) component>

(D) component is a sensitizer. When the reaction rate of the photo-acid generator which is (B) component is small with respect to the wavelength which exposes the coating film which consists of a negative photosensitive resin composition of this invention, reaction rate can be improved by adding a sensitizer. As a specific example of such a sensitizer, 9,10- dibutoxy anthracene, 9-hydroxymethyl anthracene, thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2-chloro thioxanthone And 2,4-diethyl thioxanthone, anthraquinone, 1,2-dihydroxyanthraquinone, 2-ethylanthraquinone, 1,4-diethoxynaphthalene, and the like.

As (D) component, it can use combining 1 type, or 2 or more types in the said sensitizer.

It is preferable that it is 0.1-10 mass parts normally with respect to 100 mass parts of (A) component, and, as for the addition amount of these sensitizers, More preferably, it is 0.1-8 mass parts. When the amount of the sensitizer is excessively larger than the above, the transparency of the coating film may be lowered.

<(E) component>

(E) component is a polymer which has a hydroxyl group. As a polymer which has a hydroxyl group, for example, a polymer obtained by copolymerizing a monomer having a hydroxyl group, cellulose, hydroxypropyl cellulose, a polymer obtained by copolymerizing diepoxy and dicarboxylic acid, and a polymer obtained by copolymerizing diepoxy and diphenol And polyester polyols, polyether polyols, polycaprolactone polyols, and the like. Preferably, the polymer is a polymer obtained by polymerizing a monomer having a hydroxy group, or hydroxypropyl cellulose.

As a polymer which superposed | polymerized the monomer which has the above-mentioned hydroxyl group, the polymer which copolymerized the monomer which has a hydroxyl group among the copolymerizable monomers mentioned in (A) component mentioned above or the monomer which can copolymerize is mentioned.

As a monomer which has a hydroxyl group among the copolymerizable monomers mentioned in (A) component, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2, 3- dihydroxy Propyl acrylate and 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxy Butyl methacrylate, 2,3-dihydroxypropyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, and the like.

As a monomer which can be copolymerized, the monomer which can be copolymerized mentioned in (A) component is mentioned, for example.

The polymer which has these hydroxyl groups can be used individually or in combination of 2 or more types.

It is preferable that content of the polymer which has a hydroxyl group of (E) component in the negative photosensitive resin composition of this invention is 5-150 mass parts based on 100 mass parts of copolymers of (A) component, More preferably, Is 10-120 mass parts. When this ratio is less than the above, the sensitivity of the negative photosensitive resin composition may fall, while when it is excessive than the above, developability of an unexposed part may fall and it may be a cause of a residual film or a residue.

<(F) component>

As a crosslinking agent which is (F) component of this invention, what is necessary is just a crosslinking agent which can react with (A) component with the acid which generate | occur | produced in (B) component. As such a crosslinking agent, compounds, such as an epoxy compound and a methylol compound, are mentioned, Preferably it is a methylol compound.

As a specific example of the methylol compound mentioned above, compounds, such as an alkoxy methylation glycoluril, the alkoxy methylation benzoguanamine, and the alkoxy methylation melamine, are mentioned.

As a specific example of the alkoxy methylation glycoluril, For example, 1,3,4,6- tetrakis (methoxymethyl) glycoluril, 1,3,4,6- tetrakis (butoxymethyl) glycoluril, 1,3,4,6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1 , 3,3-tetrakis (methoxymethyl) urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl ) -4,5-dimethoxy-2-imidazolinone etc. are mentioned. Commercially available products include compounds such as glycoluril compounds (trade name: CYMEL® 1170, POWDERLINK® 1174) manufactured by Mitsui Cytec, Ltd., methylated urea resins (trade name: UFR® 65), butylated urea Resin (brand name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde-based resin (high condensation type, brand name: BECKAMINE (trademark) made by Dainippon Ink and Chemicals, Inc.) J-300S, BECKAMINE P-955, BECKAMINE N), etc. are mentioned.

Specific examples of the alkoxy methylated benzoguanamine include tetramethoxymethylbenzoguanamine and the like. As a commercial item, Mitsui Cytec, Ltd. (brand name: CYMEL (registered trademark) 1123), SANWA Chemical Co., Ltd. (brand name: NIKALAC (registered trademark) BX-4000, NIKALAC BX-37, NIKALAC BL-60, NIKALAC BX-55H) etc. are mentioned.

As a specific example of the alkoxy methylation melamine, hexamethoxy methyl melamine etc. are mentioned, for example. As a commercial item, the methoxymethyl-type melamine compound (brand name: CYMEL (registered trademark) 300), CYMEL 301, CYMEL 303, CYMEL 350, a butoxymethyl-type melamine compound (brand name: MYCOAT (trademark) 506 made by Mitsui Cytec, Ltd. , MYCOAT 508), a methoxymethyl melamine compound manufactured by Sanwa Chemical Industrial Co., Ltd. (brand name: NIKALAC® MW-30, NIKALAC MW-22, NIKALAC MW-11, NIKALAC MS-001, NIKALAC MX- 002, NIKALAC MX-730, NIKALAC MX-750, NIKALAC MX-035), butoxymethyl type melamine compound (brand name: NIKALAC® MX-45, NIKALAC MX-410, NIKALAC MX-302), etc. are mentioned. have.

Moreover, the compound obtained by condensing the melamine compound, the urea compound, the glycoluril compound, and the benzoguanamine compound in which the hydrogen atom of such an amino group was substituted by the methylol group or the alkoxy methyl group may be sufficient. For example, a high molecular weight compound prepared from the melamine compound and the benzoguanamine compound described in US Pat. As a commercial item of the said melamine compound, a brand name: CYMEL (registered trademark) 303 (made by Mitsui Cytec, Ltd.), etc. are mentioned, As a commercial item of the said benzoguanamine compound, a brand name: CYMEL (registered trademark) 1123 (Mitsui) Cytec, Ltd.) etc. are mentioned.

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

It is preferable that content of the crosslinking agent of (F) component in the negative photosensitive resin composition of this invention is 5-100 mass parts based on 100 mass parts of copolymers of (A) component, More preferably, it is 10-80 It is a mass part. When this ratio is less than the above, the photocurability of a negative photosensitive resin composition may fall, but when it is excessive than the above, developability of an unexposed part may fall and it may be a cause of a residual film or a residue. .

<Other additives>

In addition, as long as the negative photosensitive resin composition of this invention does not impair the effect of this invention, a tea (quencher; quencher), surfactant, a rheology regulator, a pigment, dye, a storage stabilizer, an antifoamer, as needed. Or dissolution accelerators such as polyhydric phenol and polycarboxylic acid.

<Negative photosensitive resin composition>

The negative photosensitive resin composition of this invention melt | dissolved the polymer of (A) component and the photo-acid generator of (B) component in the (C) solvent, and if necessary, respectively, the sensitizer of (D) component, (E It is a composition which can further contain 1 or more types of the polymer which has a hydroxyl group of a) component, the crosslinking agent of (F) component, and other additives.

Especially, the preferable example of the negative photosensitive resin composition of this invention is as follows.

[1]: The negative photosensitive resin composition which contains 0.5-20 mass parts (B) component based on 100 mass parts of (A) component, and these components melt | dissolved in (C) solvent.

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

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

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

Although the ratio of solid content in the negative photosensitive resin composition of this invention is not specifically limited as long as each component is melt | dissolving uniformly in a solvent, For example, it is 1-80 mass%, For example, 5-5 It is 60 mass% or 10-50 mass%. Here, solid content means what remove | excluding the (C) solvent from all the components of a negative photosensitive resin composition.

Although the preparation method of the negative photosensitive resin composition of this invention is not specifically limited, As this preparation method, (A) component (copolymer) is melt | dissolved in the (C) solvent and it is (B) in this solution, for example. Method (D) component (sensitizer) and (E) component (hydroxy group are mixed as needed in the method of mixing a component (photoacid generator) in a predetermined ratio and making it into a uniform solution, or a suitable step of this preparation method. The polymer which has), (F) component (crosslinking agent), and the other additive are added, and the method of mixing is mentioned.

In preparation of the negative photosensitive resin composition of this invention, the solution of the specific copolymer obtained by the polymerization reaction in (C) solvent can be used as it is, and in this case, it is similar to the above in the solution of this (A) component. When (B) component etc. are put and it is set as a uniform solution, you may add further (C) solvent for the purpose of concentration adjustment. At this time, the (C) solvent used in the formation process of a specific copolymer and the (C) solvent used for density | concentration adjustment at the time of preparation of a negative photosensitive resin composition may be the same, and may differ.

And it is preferable to use, after filtering the solution of the prepared negative photosensitive resin composition using the filter etc. which have a pore diameter of about 0.2 micrometer.

<Film and Cured Film>

The negative photosensitive resin composition of the present invention may be a semiconductor substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a metal, for example, a substrate coated with aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, Coated with ITO substrate) by rotating coating, flow coating, roll coating, slit coating, slit rotating coating, inkjet coating, or the like, and then preliminarily drying in a hot plate or oven to form a coating film. can do. Then, the negative photosensitive resin film is formed by heat-processing this coating film.

As conditions of this heat processing, the heating temperature and heating time suitably selected within the range of the temperature of 70-160 degreeC and time 0.3-60 minutes are employ | adopted, for example. Heating temperature and a heat time become like this. Preferably they are 80 degreeC-140 degreeC, and 0.5 to 10 minutes.

Moreover, the film thickness of the negative photosensitive resin film formed from a negative photosensitive resin composition is 0.1-30 micrometers, for example, 0.5-20 micrometers, and is 1-15 micrometers, for example.

Contained in when the film is a negative photosensitive resin is formed from a negative-working photosensitive resin composition of the invention, using a mask having a predetermined pattern ultraviolet light, ArF, KrF, F ₂ exposure to light such as laser light, a negative type photosensitive resin film By the action of the acid generated from the photoacid generator (PAG) of component (B), the exposed portion in the film becomes insoluble in the alkaline developer.

Next, post-exposure heating (PEB) is performed with respect to the negative photosensitive resin film. As conditions for heating in this case, the heating temperature and heating time suitably selected from the range of the temperature of 70 degreeC-150 degreeC, and 0.3-60 minutes of hours are employ | adopted.

Then, image development is performed using alkaline developing solution. Thereby, the part which is not exposed in a negative photosensitive resin film is removed, and a pattern-shaped relief is provided.

Examples of the alkaline developer that may be used include, for example, aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, ethanolamine, and propyl. Alkaline aqueous solutions, such as amine aqueous solution, such as an amine and ethylenediamine, are mentioned. Moreover, surfactant etc. can also be added to these developing solutions.

Among the above, tetraethylammonium hydroxide 0.1-2.38 mass% aqueous solution is generally used as a developing solution of a photoresist, and also in the photosensitive resin composition of this invention, it is favorable, without causing a problem, such as swelling, using this alkaline developing solution. Can be developed.

As the developing method, any of a puddle method, a dipping method and a rocking dipping method can be used. The developing time at this time is 15 to 180 second normally.

After the development, the negative photosensitive resin film is washed with running water for 20 to 90 seconds, and then air dried by using compressed air or compressed nitrogen or by spinning to remove moisture on the substrate, and A patterned film is obtained.

Subsequently, post-baking is performed on the pattern forming film for thermosetting, and specifically, by heating using a hot plate, an oven, or the like, it is excellent in heat resistance, transparency, planarization property, low water absorption, chemical resistance, and the like. A film having a good relief pattern is obtained.

The postbaking is generally employed at a heating temperature selected within the range of 140 ° C. to 250 ° C. for 5 to 30 minutes on a hotplate and 30 to 90 minutes on an oven.

And the postbaking can obtain the cured film which has a favorable pattern shape made into the objective.

As described above, with the negative photosensitive resin composition of the present invention, there is no adhesion before exposure, alkali development is possible, and even if the film thickness of about 10 μm is sufficiently high sensitivity, the film reduction of the exposed portion at the time of development is very small, and a fine pattern is obtained. The coating film which has is formed. Furthermore, this cured film is excellent in transparency, heat resistance, and solvent resistance. Therefore, it can be used suitably for various films, such as an interlayer insulation film, a protective film, an insulation film, an optical film, etc. in a liquid crystal display, an organic EL display, a touch panel element, etc.

Example

Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to this Example.

[Abbreviated sign used in the embodiment]

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

MAA: methacrylic acid

MI: maleimide

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 Gosei Co., Ltd.) (Compound name: triphenylsulfonium trifluoromethanesulfonate)

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

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

CYM: CYMEL 303 (product name) (compound name: hexamethoxymethylmelamine) made by Cytec Japan Limited.

HMA: 9-hydroxymethylanthracene

HPC: hydroxypropyl cellulose

DPHA: dipentaerythritol penta / hexaacrylate

BTEAC: benzyltriethylammonium chloride

PGME: Propylene Glycol Monomethyl Ether

PGMEA: propylene glycol monomethyl ether acetate

JE: JER157S70 made in Japan Epoxy Resins Co., Ltd.

[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 product obtained according to the following synthesis examples were obtained by using the GPC apparatus manufactured by JASCO Corporation (Shodex® columns KF803L and KF804L) to elute solvent tetrahydrofuran. It measured on condition that it flowed in the column (column temperature 40 degreeC) and eluted at a flow volume of 1 ml / min. In addition, the following number average molecular weight (henceforth Mn) and weight average molecular weight (henceforth Mw) are represented by polystyrene conversion value.

Synthesis Example 1

As the 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 the radical polymerization initiator, and these were polymerized in solvent PGME (238 g). By making it react, the copolymer solution (copolymer concentration: 30 mass%) which is Mn4,300 and Mw9,800 was obtained (P1). In addition, polymerization temperature was adjusted to the temperature of 60 degreeC-90 degreeC.

Synthesis Example 2

As the monomer component constituting the copolymer, MAA (20.0 g), BMAA (50.0 g) and ST (30.0 g) were used, AIBN (2 g) was used as a radical polymerization initiator, and these were polymerized in solvent PGME (238 g). By reacting, the copolymer solution (copolymer concentration: 30 mass%) which is Mn4,000 and Mw9,200 was obtained (P2). In addition, polymerization temperature was adjusted to the temperature of 60 degreeC-90 degreeC.

Synthesis Example 3

As the monomer component constituting the copolymer, MAA (20.0 g), BMAA (50.0 g), HEMA (30.0 g) were used, AIBN (2 g) was used as the radical polymerization initiator, and these were polymerized in solvent PGME (238 g). By reacting, the copolymer solution (copolymer concentration: 30 mass%) which is Mn4,800 and Mw10,500 was obtained (P3). In addition, polymerization temperature was adjusted to the temperature of 60 degreeC-90 degreeC.

Synthesis Example 4

As the monomer component constituting the copolymer, MAA (20.0 g), HEMA (40.0 g), MMA (40.0 g) were used, AIBN (2 g) was used as the radical polymerization initiator, and these were polymerized in solvent PGME (238 g). By reacting, the copolymer solution (copolymer concentration: 30 mass%) which is Mn3,900 and Mw8,500 was obtained (P4). In addition, polymerization temperature was adjusted to the temperature of 60 degreeC-90 degreeC.

Comparative Example 1

As the monomer component constituting the copolymer, MAA (50.0 g) and MMA (50.0 g) were used, AIBN (2 g) was used as a radical polymerization initiator, and these were polymerized in a solvent PGMEA (120 g) to obtain a copolymer solution ( Copolymer concentration: 40 mass%). In addition, polymerization temperature was adjusted to the temperature of 60 degreeC-90 degreeC. A solution of (A) component (specific copolymer) of Mn8,700 and Mw22,000 (specific copolymer) by adding GMA (33.0 g), BTEAC (1.1 g), and PGMEA (49.5 g) to 200 g of this copolymer to react. Concentration: 40.5 mass%) (P5). In addition, reaction temperature was adjusted to 90-120 degreeC.

Comparative Example 2

As the monomer component constituting the copolymer, MAA (30.0 g), GMA (50.0 g), ST (20.0 g) were used, and AIBN (2 g) was used as the radical polymerization initiator, and these were heated in solvent PGME (238 g). The polymerization was carried out at 60 ° C to 90 ° C, but it gelled during the polymerization reaction and could not be used for subsequent evaluation.

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

According to the composition shown in following Table 1, (B) component, (C) solvent, and (D) component, and (E) component and (F) component are mixed with the solution of (A) component at predetermined ratio, The negative photosensitive resin composition of each Example and each comparative example was prepared by stirring at room temperature for 3 hours and making it a uniform solution.

TABLE 1

About each obtained negative photosensitive resin composition of Examples 1-7 and Comparative Examples 1 and 2, the film thickness after prebaking, the presence or absence of adhesion, the transmittance | permeability, the resolution, and the sensitivity were measured, respectively.

[Evaluation of film thickness after prebaking]

After apply | coating a negative photosensitive resin composition on a silicon wafer using a spin coater, it prebaked at the temperature of 110 degreeC for 120 second on the hotplate, and formed the coating film. The film thickness of this coating film was measured using F20 by Filmetrics, Inc.

[Evaluation of Transmittance]

The negative photosensitive resin composition was applied onto a quartz substrate using a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film. This coating film was irradiated with ultraviolet-ray with a light intensity of 5.5 mW / cm <^2> for 36 second by Canon Inc. ultraviolet irradiation device PLA-600FA. After the film was subjected to post-exposure heating on a hot plate at a temperature of 95 ° C. for 120 seconds, it was postbaked in an oven at a temperature of 150 ° C. for 15 minutes to form a cured film. The transmittance | permeability of the wavelength of 400 nm was measured for this cured film using the ultraviolet visible spectrophotometer (SIMADSU UV-2550 model number by Shimadzu Corporation).

[Evaluation of resolution]

After apply | coating a negative photosensitive resin composition on the alkali free glass using a spin coater, it prebaked on the hotplate for 120 second at the temperature of 110 degreeC, and formed the coating film. The coating film on the Canon Inc. The UV irradiation device was examined PLA-600FA to 190mJ / cm ² in the light intensity of the 365nm through a mask of a 5.5mW / cm ² of ultraviolet rays by the line and space pattern. Then, the post-exposure heating was performed on the hotplate for 120 second at the temperature of 110 degreeC. Then, the image development was performed by immersing in 2.38 mass% tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution for 60 seconds, and then a pattern was formed by performing flowing water washing for 20 seconds with ultrapure water. SEM observation was performed about the produced pattern baked in 150 degreeC oven for 15 minutes, and the minimum pattern size which the line width of a pattern matches the line width of a mask was made into the resolution.

[Evaluation of sensitivity]

After apply | coating a negative photosensitive resin composition on the alkali free glass using a spin coater, it prebaked on the hotplate for 120 second at the temperature of 110 degreeC, and formed the coating film. In the film Canon Inc. The ultraviolet irradiation apparatus for the light intensity at 365nm 5.5mW / cm ² of ultraviolet rays by a PLA-600FA and irradiated through the mask for line and space pattern of 20μm by 50mJ / cm ^2. Then, the post-exposure heating was performed on the hotplate for 120 second at the temperature of 110 degreeC. After developing by immersing in 2.38 mass% TMAH aqueous solution for 60 second after that, the pattern was formed by performing flowing water washing for 20 second with ultrapure water. The minimum exposure amount in which the 20 micrometer pattern is formed was made into the sensitivity.

[Evaluation results]

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

TABLE 2

As can be seen from the results shown in Table 2, all of the negative photosensitive resin compositions of Examples 1 to 7 can be applied on a thick film of 10 μm or more, and high transmittance and alkali development are possible even on a thick film. Was keeping up.

About the comparative example 1, it was not thickened and the residual film rate after postbaking was also low as 90% or less. In Comparative Example 2, adhesion occurred after prebaking, and development was not possible with an alkaline developer.

Industrial availability

The negative photosensitive resin composition which concerns on this invention is suitable as a material which forms the cured film, such as a protective film, a planarization film, and an insulating film in various displays, such as a thin film transistor (TFT) type liquid crystal display element, an organic EL element, and a touch panel element. In particular, it is also suitable as a material for forming an interlayer insulating film of a TFT type liquid crystal element, a protective film of a color filter, an array planarization film, an interlayer insulating film of a capacitive touch panel, an insulating film of an organic EL element, a structure sheet as a display surface antireflection layer, and the like. Do.

Claims (9)

The negative photosensitive resin composition containing following (A) component, (B) component, and (C) solvent.
(A) component: The copolymer which copolymerized the monomer mixture containing at least (i) N-alkoxymethyl (meth) acrylamide and (ii) maleimide,
(B) Component: photoacid generator,
(C) Solvent. delete The method of claim 1,
The negative photosensitive resin composition which contains 0.1-10 mass parts further as a (D) component based on 100 mass parts of photosensitive resin compositions. The method of claim 1,
The negative photosensitive resin composition which further contains the polymer which has a hydroxyl group as (E) component. The method of claim 1,
The negative photosensitive resin (A) component is a copolymer which copolymerized the monomer mixture which further contains the monomer which has a hydroxyl group with said (i) N-alkoxymethyl (meth) acrylamide and (ii) maleimide. Composition. The method of claim 1,
The negative photosensitive resin composition which further contains a crosslinking agent as (F) component. The cured film obtained using the negative photosensitive resin composition of any one of Claims 1-6. The interlayer insulation film for liquid crystal displays which consists of a cured film of Claim 7. The optical filter which consists of a cured film of Claim 7.