KR20140022398A - Negative photosensitive resin composition - Google Patents

Abstract

[Problem] Negative photosensitive resin composition which can be thickened even with low viscosity solution, has no tack before exposure, can be patterned at high resolution by alkali development, and the resulting coating film has high transparency and small shrink after post-baking. To provide.
[Solution] A photosensitive shoe composition containing the following (A) component, (B) component, (C) component and (D) component. (A) component: The acrylic copolymer which copolymerized the monomer mixture containing at least (i) maleimide and (ii) the monomer which has an epoxy group, (B) component: photo-acid generator, (C) component: having two or more epoxy groups Compound, (D) component: A solvent.

Description

NEGATIVE PHOTOSENSITIVE RESIN COMPOSITION [0002]

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 the various materials using this cured film.

It is known that the 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 the tack enters a coating film after application | coating and before exposure, handling property is bad. Moreover, since image development by aqueous alkali solution is not possible, image development by the organic solvent is essential. Although alkali development is 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 arises easily during superposition | polymerization, and synthesis control of a polymer is difficult. Moreover, the storage stability is low even if the polymer can be 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, alkali image development is possible by introducing a carboxyl group into a polymer, but high viscosity is required in order to thicken a film, and handling property is bad. The problem was that the radical system is susceptible to surface oxygen inhibition at the time of photocuring, resulting in a large film reduction.

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

In this regard, a material having high transparency, alkali development and high handling properties is required even when thickening.

Moreover, it is known to use maleimide as alkali-soluble resin (for example, patent document 4). In this invention, although using maleimide as an alkali-soluble group is proposed, it cannot be used as a positive film permanently.

On the other hand, any kind of negative photosensitive resin composition which used maleimide as alkali-soluble resin is also known (for example, patent document 5).

International Patent Application Publication WO2008 / 007764 pamphlet Japanese Patent Application Laid-Open No. 2004-302389 Japanese Patent Laid-Open No. 8-339082 Japanese Patent Application Laid-Open No. 60-115932 Japanese Patent Publication No. 2010-15156

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is possible to form a thick film even with a low viscosity solution, and there is no tack before exposure, and a pattern can be formed at high resolution by alkali development. It is providing a small negative photosensitive resin composition after baking.

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

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

(A) component: The acrylic copolymer which copolymerized the monomer mixture containing the monomer which has at least (i) maleimide and (ii) epoxy group,

(B) component: photo-acid generator,

(C) component: the compound which has two or more epoxy groups,

(D) component: a solvent,

As a 2nd viewpoint, the photosensitive resin composition as described in a 1st viewpoint which contains 0.1-10 mass parts of sensitizers further with respect to 100 mass parts of photosensitive resin compositions as (E) component,

As a 3rd viewpoint, The photosensitive resin composition as described in a 1st viewpoint or a 2nd viewpoint which contains 1 mass% or less as (F) component further based on the gross mass of the photosensitive resin composition,

As a 4th viewpoint, the cured film obtained using the photosensitive resin composition in any one of a 1st viewpoint thru | or a 3rd viewpoint,

As a 5th viewpoint, the interlayer insulation film for liquid crystal displays which consists of a cured film as described in a 4th viewpoint,

As a 6th viewpoint, the optical filter which consists of a cured film as described in a 4th viewpoint

.

The photosensitive resin composition of this invention is optimal for formation of a structure as an optical member in that there is no tack before exposure, a transparency and the resolution are high also in a thick film, and the shrinkage of a film is small even after a postbaking can be formed.

The photosensitive resin composition of this invention is a photosensitive resin composition containing following (A) component, (B) component, (C) component, and (D) component.

(A) component: The acrylic copolymer which copolymerized the monomer mixture containing at least (i) maleimide and (ii) the monomer which has an epoxy group, Preferably the monomer which has an unsaturated double bond and an epoxy group,

(B) component: photo-acid generator,

(C) component: the compound which has two or more epoxy groups,

(D) Component: Solvent

Hereinafter, the details of each component will be described.

≪ Component (A) >

(A) A component is an acrylic copolymer which copolymerized the monomer mixture containing the monomer which has at least (i) maleimide and (ii) epoxy group.

In this invention, a copolymer refers to the polymer obtained by copolymerizing using the monomer which has unsaturated double bonds, such as acrylic acid ester, methacrylic acid ester, and styrene.

The copolymer of the component (A) may be a copolymer having such a structure, and the copolymer of the component (A) is not particularly limited with respect to the skeleton of the main chain and the type of the side chain of the polymer.

However, if the acrylic 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, while if the number average molecular weight is less than 2,000, the curing of the exposed portion is insufficient. Therefore, components may elute at the time of image development. Therefore, the number average molecular weight is in the range of 2,000 to 100,000.

(i) maleimide:

[Formula 1]

The maleimide used for (A) component is limited to the structure represented by Formula (1).

(ii) Monomers having epoxy groups:

This monomer may be a monomer having an epoxy group, but is preferably a monomer having an unsaturated double bond and an epoxy group.

Examples of the monomer having an unsaturated double bond and an epoxy group include glycidyl methacrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, Allylglycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxide and the like.

In addition, in this invention, when obtaining the acrylic copolymer which has a specific functional group (epoxy group), the monomer which has a non-reactive functional group can be used together as a monomer copolymerizable with the monomer which has a specific functional group.

As a specific example of the monomer which has a non-reactive functional group, an acrylic acid ester compound, a methacrylic acid ester compound, an N-substituted maleimide compound, an acrylonitrile, a maleic anhydride, 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 acrylic acid ester compound, 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, diethyl Lenglycol monoacrylate, caprolactone 2- (acryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic- 6-lactone, acryloylethyl isocyanate, and 8-ethyl-8- tricyclodecyl 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. Latex, 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 Yate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) Ethylether methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, methacryloylethyl isocyanate, and 8-ethyl-8-tricyclodecyl Methacrylate, and the like.

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.

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

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

Although the method of obtaining the acrylic 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 another copolymerizable non-reactive functional group, and a polymerization initiator etc. coexist as needed. It is obtained by making a polymerization reaction at the temperature of 50-110 degreeC in the solvent made. 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 (D) 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 acrylic copolymer obtained as described above is reprecipitated by stirring under diethyl ether, water or the like, and the resulting precipitate is filtered and washed, followed by normal temperature or heat drying under normal pressure or reduced pressure, thereby obtaining acrylic. It can be set as the powder of a copolymer. By such operation, the polymerization initiator and unreacted monomer which coexist with an acrylic copolymer can be removed, As a result, the powder of the refined acrylic copolymer is obtained. When it cannot fully refine | purify by one operation, what is necessary is to dissolve the obtained powder again in a solvent, and to perform said operation repeatedly.

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 (D) mentioned later, for example, and may be used as a solution state.

In addition, in this invention, the mixture of the some type of specific copolymer may be sufficient as the acrylic copolymer of (A) component.

As a copolymerization rate of a monomer, maleimide / epoxy / others = 10-60 / 10-40/0-80 weight part is preferable. When there is too little maleimide, an unexposed part will not melt | dissolve in a developing solution and it will be easy to cause a residual film or a residue. When too much, there is a possibility that the curability of an exposed part is insufficient and a pattern cannot be formed. When there are too few monomers which have an epoxy group, there exists a possibility that photocurability may run out and an exposure part may melt | dissolve at the time of image development. When too much, the solubility of an unexposed part may be insufficient and it may become a cause of a residual film or a residue.

≪ Component (B) >

(B) component is a photo-acid generator. The kind of acid used in the thermosetting resin composition of the present invention is not particularly limited. As a specific example of such a photo-acid generator,

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

[Formula 7]

[Formula 8]

[Chemical Formula 9]

[Formula 10]

Diphenyl iodonium chloride, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium mesylate, diphenyl iodonium tosylate, diphenyl iodonium bromide, diphenyl iodonium tetrafluoroborate , Diphenyl iodonium hexafluoro antimonate, diphenyl iodonium hexafluoro arsenate, bis (p-tert- butylphenyl) iodonium hexafluoro phosphate, bis (p-tert- butylphenyl) iodonium Mesylate, bis (p-tert-butylphenyl) iodonium tosylate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium tetrafluoroborate , Bis (p-tert-butylphenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium Romanoid, triphenylsulfonium trifluoromethanesulfonate, tri (p-methoxyphenyl) sulfoniumtetrafluoroborate, tri (p-methoxyphenyl) sulfonium hexafluorophosphonate, tri (p- Ethoxyphenyl) sulfoniumtetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tri (p-methoxyphenyl) phosphoniumtetrafluoroborate, tri (p-methoxyphenyl) phosphonium hexafluoro Rophosphonates, 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, 1-15 mass parts, More preferably, with respect to 100 mass parts of (A) component. Is 2-10 mass parts. When 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.

≪ Component (C) >

As an epoxy compound which has two or more epoxy groups which are (C) component of this invention, For example, tris (2, 3- epoxypropyl) isocyanurate, 1, 4- butanediol diglycidyl ether, 1,2 -Epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenylglycidyl ether, 1,1,3-tris [p -(2,3-epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis (N, N- diglycidylaniline), 3,4 -Epoxycyclohexyl methyl-3, 4- epoxycyclohexane carboxylate, trimetholethane triglycidyl ether, bisphenol-A- diglycidyl ether, pentaerythritol polyglycidyl ether, etc. are mentioned.

Moreover, the compound of a commercial item can also be used from an easy point of acquisition. Although the specific example (brand name) is given to the following, it is not limited to these: Epoxy resin which has amino groups, such as YH-434 and YH434L (made by Tohto Kasei Co., Ltd.); Epoxy resins having a cyclohexene oxide structure such as EPOLEAD GT-401, EPOLEAD GT-403, EPOLEAD GT-301, EPOLEAD GT-302, CELOXIDE 2021, CELOXIDE 3000 (manufactured by Daicel Corporation); Bisphenol A type epoxy resins such as EPIKOTE 1001, EPIKOTE 1002, EPIKOTE 1003, EPIKOTE 1004, EPIKOTE 1007, EPIKOTE 1009, EPIKOTE 1010 and EPIKOTE 828 (above, manufactured by Yuka Shell Epoxy Co. Ltd. (currently JER)); Bisphenol F-type epoxy resins such as EPIKOTE 807 (manufactured by Yuka Shell Epoxy Co. Ltd. (current JER)); Phenol novolac type epoxy resins such as EPIKOTE 152, EPIKOTE 154 (above, manufactured by Yuka Shell Epoxy Co. Ltd. (currently JER)), EPPN201, and EPPN202 (above, manufactured by Nippon Kayaku Co., Ltd.); EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, made by Nippon Kayaku Co., Ltd.), EPIKOTE 180S75 (Yuka Shell Epoxy Co. Ltd. (now JER) Cresol novolac-type epoxy resins such as those produced by the present invention; DENACOL EX-252 (made by Nagase ChemteX Corporation.), CY175, CY177, CY179, Araldite CY-182, Araldite CY-192, Araldite CY-184 (above, made by CIBA-GEIGYA.G), EPICLON 200, EPICLON 400 (more than , Alicyclic epoxy such as EPICOTE 871, EPIKOTE 872 (above, Yuka Shell Epoxy Co. Ltd. (current JER)), ED-5661, ED-5662 (above, Celanese coating, Ltd.) Suzy; DENACOL EX-611, DENACOL EX-612, DENACOL EX-614, DENACOL EX-622, DENACOL EX-411, DENACOL EX-512, DENACOL EX-522, DENACOL EX-421, DENACOL EX-313, DENACOL EX-314, Aliphatic polyglycidyl ethers such as DENACOL EX-321 (manufactured by Nagase ChemteX Corporation).

As the compound having at least two epoxy groups, a polymer having an epoxy group can also be used. Such a polymer can be used without particular limitation as long as it has an epoxy group and does not contain an N-unsubstituted maleimide in the repeating unit.

The polymer which has the said epoxy group can be manufactured by addition polymerization using the addition polymerization monomer which has an epoxy group, for example. As an example, addition polymerization polymers, such as polyglycidyl acrylate, a copolymer of glycidyl methacrylate and ethyl methacrylate, a copolymer of glycidyl methacrylate and styrene, and 2-hydroxyethyl methacrylate And polycondensation polymers, such as an epoxy novolak, are mentioned.

Or the polymer which has the said epoxy group can also be manufactured by reaction with the high molecular compound which has a hydroxyl group, and the compound which has epoxy groups, such as epichlorohydrin and glycidyl tosylate.

As a weight average molecular weight of such a polymer, it is 300-20,000, for example.

The epoxy compound which has two or more of these epoxy groups can be used individually or in combination of 2 or more types.

It is preferable that content of the epoxy compound which has two or more epoxy groups of (C) component in the negative photosensitive resin composition of this invention is 5-100 mass parts based on 100 mass parts of acrylic polymers of (A) component, More Preferably it is 10-80 mass parts. When this ratio is too small, the photocurability of a negative photosensitive resin composition may fall, On the other hand, when excessive, developability of an unexposed part may fall and it may be a cause of a residual film or a residue.

≪ (D) Solvent >

It dissolves (A) component (C) component used for this invention, and melt | dissolves the below-mentioned (E) component, (F) component etc. which are added as needed, and if it is a solvent which has such a solubility, Kind, structure, etc. are not specifically limited.

Examples of such a solvent (D) 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-methyl butyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, pyruvic acid Ethyl, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

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

Among these (D) 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.

<(E) component>

(E) 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-chlorothioxanthone, 2 , 4-diethyl thioxanthone, anthraquinone, 1,2-dihydroxyanthraquinone, 2-ethylanthraquinone, 1,4-diethoxynaphthalene, etc. are mentioned.

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

It is preferable that the addition amount of these sensitizers is 10 mass parts or less normally with respect to 100 mass parts of (A) component, More preferably, it is 8 mass parts or less. When 8 mass parts or more are used, transparency of a coating film may fall.

Moreover, it is preferable to contain 0.1-10 mass parts of addition amounts of these sensitizers with respect to 100 mass parts of photosensitive resin compositions.

<(F) component>

(F) component is an amine compound. In the negative photosensitive resin composition of this invention, an amine compound can be added and the pattern shape can be controlled in order to suppress the diffusion of the acid which generate | occur | produced from the (B) component.

Although it does not restrict | limit especially as an amine compound of (F) component, Tertiary amines, such as triethanolamine, triethylamine, tributylamine, triphenylamine, benzyl dimethylamine, and Nn-butyl diethanolamine, are preferable.

The amine compound of (F) component can be used individually by 1 type or in combination of 2 or more types.

When an amine compound is used, the content is 1.0 mass% or less normally in 100 mass% of negative photosensitive resin compositions, Preferably it is 0.5 mass% or less. When the usage-amount of the amine compound of (F) component is set to the quantity over 1.0 mass%, the sensitivity of the negative photosensitive resin composition may fall large.

<Other additives>

Moreover, as long as the negative photosensitive resin composition of this invention does not impair the effect of this invention, surfactant, a rheology regulator, a pigment, dye, a preservation stabilizer, an antifoamer, polyhydric phenol, polyhydric carboxylic acid, etc. are needed as needed. Dissolution accelerator and the like.

&Lt; Negative-type photosensitive resin composition >

In the negative photosensitive resin composition of this invention, the compound which has the acrylic polymer of (A) component, the photo-acid generator of (B) component, and two or more epoxy groups of (C) component melt | dissolved in the (D) solvent, Each is a composition which may further contain one or more of the sensitizer of (E) component, the amine compound of (F) component, and other additives as needed.

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

[1]: Based on 100 parts by mass of the component (A), 0.5 to 20 parts by mass of the component (B) and 5 to 100 parts by mass of the component (C) are contained, and these components are dissolved in the solvent (D). Photosensitive resin composition.

[2]: The negative photosensitive resin composition which contains 0.1-10 mass parts of (E) component further based on 100 mass parts of (A) component in the composition of said [1].

[3]: In the composition of [1] or [2], the negative photosensitive resin composition further contains 1 part by mass or less 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 in a solvent uniformly, For example, it is 1-80 mass%, For example, 5-60 It is mass% or 10-50 mass%. Here, solid content means what remove | excluding the (D) solvent from all the components of a negative photosensitive resin composition.

Although the manufacturing method of the negative photosensitive resin composition of this invention is not specifically limited, As this preparation method, (A) component (acryl copolymer) is melt | dissolved in the (D) solvent and it is (B) in this solution, for example. Component (photoacid generator), (C) component (compound having two or more epoxy groups) are mixed at a predetermined ratio, and the solution is made into a uniform solution, or at a suitable stage of this preparation method, if necessary, (E) The method of adding and mixing a component (sensitizer), (F) component (amine compound), and another additive further 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 (D) solvent can be used as it is, and in this case, it is the same as the above in the solution of this (A) component (B). When (a) component, (C) component, etc. are put and it is set as a uniform solution, (D) solvent can also be further added for the purpose of concentration adjustment. At this time, the (D) solvent used in the formation process of a specific copolymer and the (D) 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 hole diameter of about 0.2 micrometer.

<Film and Cured Film>

The negative photosensitive resin composition of the present invention is a semiconductor substrate (e.g., silicon / silicon dioxide coated substrate, silicon nitride substrate, metal such as aluminum, molybdenum, chromium coated substrate, glass substrate, quartz substrate, ITO On a substrate, etc.), the coating film can be formed by applying spin coating, flow coating, roll coating, slit coating, spin coating following the slit, ink jet coating, or the like, followed by preliminary drying with a hot plate or oven. . Then, the negative photosensitive resin film is formed by heat-processing this coating film.

As conditions for this heat processing, the heating temperature and heating time suitably selected from the range of the temperature of 70 degreeC-160 degreeC, and time 0.3 to 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.

In addition, 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 further.

If 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 laser light, which is contained in the negative-working photosensitive resin film ( By the action of the acid generated from the photoacid generator (PAG) of the component B), the exposed portion of the film becomes insoluble in the alkaline developer.

Subsequently, post-exposure heating (PEB) is performed on the negative photosensitive resin film. As the 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 time 0.3-60 minutes are employ | adopted.

Then, image development is performed using alkaline developing solution. As a result, the unexposed portion of the negative photosensitive resin film is removed to form a pattern-shaped relief.

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

Among these, 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, this alkaline developing solution is used satisfactorily, without causing problems, such as swelling. Can develop

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

After development, the negative photosensitive resin film is washed with running water for, for example, 20 to 90 seconds, and subsequently dried by using compressed air or compressed nitrogen or by spinning to remove moisture on the substrate, and the pattern The formed 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, low water absorption, chemical resistance, and the like. A film having a good relief pattern is obtained.

Generally as a postbaking, the method of processing for 5 to 30 minutes in the case of a hotplate, and 30 to 90 minutes in the oven is employ | adopted at the heating temperature selected from the range of temperature 140 degreeC-250 degreeC.

And by this post-baking, the cured film which has the target favorable pattern shape can be obtained.

As described above, with the negative photosensitive resin composition of the present invention, there is no tack before exposure, and even at a film thickness of about 10 μm, the sensitivity is sufficiently high, and the film reduction of the exposed portion at the time of development is very small to form a coating film having a fine pattern. Can be. In addition, the shrink caused by the post-baking is very small, and even in a large substrate, the in-plane distribution of the film thickness can be reduced. Moreover, this cured film is excellent in transparency, heat resistance, and solvent resistance. For this reason, it can use suitably for various films, such as an interlayer insulation film, a protective film, an insulating 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 these Examples.

[Abbreviation used in the examples]

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

MAA: methacrylic acid

MI: maleimide

MMA: methyl methacrylate

ECM: 3,4-epoxycyclohexylmethyl methacrylate

GMA: glycidyl methacrylate

ST: Styrene

AIBN: azobisisobutyronitrile

PAG1: GSID-26-1 (product made by BASF)

PAG2: CPI-110P (manufactured by San-Apro Ltd.)

PAG3: HS-1PG (manufactured by San-Apro Ltd.)

PAG4: IRGACURE 369 (product of BASF)

CEL: CELOXIDE P-2021 (product name) made from Daicel Corporation (compound name: 3, 4- epoxycyclohexenylmethyl-3 ', 4'- epoxycyclohexene carboxylate)

GT: EPOLEAD GT-401 (product name) made from Daicel Corporation (compound name: epoxidized butane tetracarboxylic acid tetrakis- (3-cyclohexenylmethyl) formula (epsilon) -caprolactone)

ITX: 2-isopropyl thioxanthone

TEA: triethanolamine

DPHA: dipentaerythritol penta / hexaacrylate

BTEAC: benzyltriethylammonium chloride

PGME: Propylene glycol monomethyl ether

PGMEA: Propylene glycol monomethyl ether acetate

JE: JER157S70 made by JER

CHMI: N-cyclohexylmaleimide

[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 example were used for the eluting solvent tetrahydrofuran using the GPC apparatus (Shodex (R) column KF803L and KF804L) by JASCO Corporation. It measured on the conditions that it flowed and eluted in a column (column temperature 40 degreeC) by flow volume 1 ml / min. In addition, the following number average molecular weight (henceforth Mn) and a weight average molecular weight (henceforth Mw) are shown by polystyrene conversion value.

&Lt; Synthesis Example 1 &

As the monomer component constituting the copolymer, MI (28.0 g), ECM (50.0 g) and ST (22.0 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 Mn 4,500 and Mw 10,000 was obtained (P1). In addition, polymerization temperature was adjusted to the temperature of 60 degreeC-90 degreeC.

&Lt; Synthesis Example 2 &

As monomer components constituting the copolymer, MI (30.0 g), GMA (50.0 g), and ST (20.0 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 Mn 10,000 and Mw 30,000 was obtained (P2). In addition, polymerization temperature was adjusted to the temperature of 60 degreeC-90 degreeC.

<Comparative Synthesis 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 the 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 Mn 8,700 and Mw 22,000 (specific copolymer concentration) by adding and reacting GMA (33.0 g), BTEAC (1.1 g), and PGMEA (49.5 g) to 200 g of the copolymer. 40.5 mass%) was obtained (P3). In addition, reaction temperature was adjusted to 90-120 degreeC.

&Lt; Comparative Synthesis 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 reaction was carried out at 60 ° C to 90 ° C, but it gelled during the polymerization reaction and could not be used for subsequent evaluation.

&Lt; Comparative Synthesis Example 3 >

As the monomer component constituting the copolymer, CHMI (28.0 g), ECM (50.0 g), ST (22.0 g) were used, and AIBN (2 g) was used as the radical polymerization initiator, and these were polymerized in solvent PGME (238 g). By reacting, the copolymer solution (copolymer concentration: 30 mass%) which is Mn 4,800 and Mw 12,000 was obtained (P4) Moreover, polymerization temperature was adjusted to the temperature of 60 degreeC-90 degreeC.

<Examples 1 to 7 and Comparative Examples 1 to 4>

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

[Table 1]

About the obtained negative photosensitive resin compositions of Examples 1-7 and Comparative Examples 1-4, the viscosity of the solution, the film thickness after prebaking, the transmittance | permeability, the resolution, and the residual film rate were measured, respectively.

[Evaluation of viscosity]

The viscosity was measured for the negative photosensitive resin composition at rotation speed of 10 rpm and the temperature of 25 degreeC using E-type rotational viscometer (rotor No. 1 (1 degree 34 ')).

[Evaluation of film thickness after pre-baking]

After apply | coating a negative photosensitive resin composition on a silicon wafer using a spin coater, it prebaked on the hotplate for 120 second at the temperature of 100 degreeC, and formed the coating film. The film thickness of this coating film was measured using F20 made from FILMETRICS.

[Evaluation of Transmittance]

After apply | coating a negative photosensitive resin composition on a quartz substrate using a spin coater, it prebaked on the hotplate for 120 second at the temperature of 100 degreeC, and formed the coating film. This coating film was irradiated with the ultraviolet-ray with a light intensity of 5.5 mW / cm <^2> for 36 second by Canon Inc. ultraviolet irradiation device PLA-600FA. After this film was subjected to post-exposure heating on a hot plate at a temperature of 95 ° C. for 120 seconds, post-baking was carried out in an oven at a temperature of 230 ° C. for 30 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 100 degreeC, and formed the coating film. This coating film was irradiated with 190 mJ / cm <^2> of ultraviolet-rays of 5.5 mW / cm < ² > in 365 nm through the mask of a line & space pattern by the ultraviolet-ray irradiator PLA-600FA by Canon Inc .. Thereafter, post-exposure heating was performed on a hot plate at a temperature of 95 ° C. for 120 seconds. After developing for 60 seconds by immersing in 1.0 mass% tetramethylammonium hydroxide (it is hereafter called TMAH) aqueous solution for 60 second, the pattern was formed by performing 20-second water flow washing with ultrapure water. SEM observation of the produced pattern in 30 degreeC baking at 230 degreeC was carried out, 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 Residual Rate]

After apply | coating a negative photosensitive resin composition on a silicon wafer using a spin coater, it prebaked on the hotplate for 120 second at the temperature of 100 degreeC, and formed the coating film. This coating film was irradiated with the ultraviolet-ray with a light intensity of 5.5 mW / cm <^2> for 36 second by Canon Inc. ultraviolet irradiation device PLA-600FA. After this film was subjected to post-exposure heating on a hot plate at a temperature of 95 ° C. for 120 seconds, post-baking was carried out in an oven at a temperature of 230 ° C. for 30 minutes to form a cured film. The film thickness after postbaking was measured using F20 made from FILMETRICS. The residual film ratio was calculated as (X100 after post-baking / film thickness after pre-baking).

[Results of evaluation]

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, although the negative photosensitive resin compositions of Examples 1 to 7 were all low-viscosity, coating was possible in a thick film, and even a thick film maintained high transmittance and resolution. In addition, the remaining film rate after the post-baking was all very high, 95% or more, that is, the shrinkage of the film was small.

In Comparative Example 1, the film was not thickened even at the same viscosity, and the residual film rate after the postbaking was also low at 90% or less. In Comparative Example 2, the tack entered after prebaking and could not be developed with an alkaline developer. Moreover, the negative photosensitive resin composition of the comparative example 3 which used N-substituted maleimide (cyclohexyl maleimide) as maleimide also could not develop in alkaline developing solution. In addition, the photoradical initiator IRGACURE 369 was used instead of the photo-acid generator of (B) component, and DPHA (dipentaerythritol penta / hexaacrylate) was used instead of the compound which has two or more epoxy groups of (C) component. As for the negative photosensitive resin composition of the comparative example 4, the film | membrane reduction at the time of image development was very large, and favorable resolution was not able to be obtained.

[Industrial Availability]

The negative photosensitive resin composition according to the present invention is suitable as a material for forming cured films such as protective films, planarization films, and insulating films in various displays such as thin film transistor (TFT) type liquid crystal display devices, organic EL devices, and touch panel devices. 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. .

Claims (6)

The photosensitive resin composition containing following (A) component, (B) component, (C) component, and (D) component.
(A) component: The acrylic copolymer which copolymerized the monomer mixture containing the monomer which has at least (i) maleimide and (ii) epoxy group,
(B) component: photo-acid generator,
(C) component: the compound which has two or more epoxy groups,
(D) component: A solvent.
The method of claim 1,
The photosensitive resin composition which contains 0.1-10 mass parts of sensitizers as (E) component further with respect to 100 mass parts of said photosensitive resin compositions.
3. The method according to claim 1 or 2,
The photosensitive resin composition which contains 1 mass% or less as (F) component further based on the gross mass of the said photosensitive resin composition.
The cured film obtained using the photosensitive resin composition of any one of Claims 1-3.
The interlayer insulation film for liquid crystal displays which consists of a cured film of Claim 4.
The optical filter which consists of a cured film of Claim 4.