WO2016175160A1

WO2016175160A1 - Alkali-soluble resin

Info

Publication number: WO2016175160A1
Application number: PCT/JP2016/062870
Authority: WO
Inventors: 壮六人部
Original assignee: ナガセケムテックス株式会社
Priority date: 2015-04-28
Filing date: 2016-04-25
Publication date: 2016-11-03
Also published as: CN107531880A; TWI690543B; JPWO2016175160A1; KR20170141197A; TW201708302A

Abstract

The present invention addresses the problem of providing an alkali-soluble resin which can be used suitably for the production of an alkali-soluble radiation-sensitive resin composition having excellent alkali solubility, resistance to a developing solution, thin line adhesion and rectilinear propagation of patterns and undergoing a small degree of film shrinkage. The alkali-soluble resin according to the present invention is characterized by being produced by reacting (a) a (meth)acrylic acid ester having a cyclic structure and having a hydroxy group, (b) a (meth)acrylic acid ester monomer and (c) a carboxylic acid or an acid anhydride thereof with one another.

Description

Alkali-soluble resin

The present invention relates to an alkali-soluble resin.

In general, resist materials for forming ITO electrodes such as liquid crystal displays (LCD) and organic EL displays, interlayer insulating films, circuit protective films, color pigment dispersion resists for manufacturing color filters for liquid crystal displays, partition materials for organic EL displays, etc. As a permanent film forming material, a radiation sensitive resin composition is widely used. Among these, in recent years, the demand for liquid crystal displays is increasing for television applications and the like, and radiation-sensitive resin compositions are frequently used in the manufacturing process.

As a radiation sensitive resin composition, for example, Patent Document 1 discloses a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and (meth) acrylic acid, a polybasic acid carboxylic acid or There has been proposed a photosensitive resin composition for black resist containing an unsaturated group-containing compound obtained by reacting with the anhydride as an essential component. However, although the composition is excellent in alkali solubility, there is room for improvement in these respects because the developer resistance, fine wire adhesion and pattern straightness are not sufficient, and the film shrinkage is large.

JP 2004-361636 A

The present invention provides an alkali-soluble resin suitably used for obtaining an alkali-soluble radiation-sensitive resin composition having excellent alkali solubility, developer resistance, fine wire adhesion, and pattern straightness, and small film shrinkage. For the purpose.

As a result of intensive studies to solve the above problems, the present inventors have found that (a) a (meth) acrylic acid ester having a cyclic structure and a hydroxyl group, and (c) a carboxylic acid or an acid anhydride thereof. In addition, the alkali-soluble resin obtained by reacting the (b) (meth) acrylic acid ester monomer is excellent in alkali solubility, developer resistance, fine wire adhesion and pattern straightness, and is alkali-soluble with little film shrinkage. The present invention has been completed by finding that it can be suitably used for obtaining a mold-type radiation-sensitive resin composition.

That is, the alkali-soluble resin of the first invention is
(A) a (meth) acrylic acid ester having a cyclic structure and a hydroxyl group,
(B) a (meth) acrylic acid ester monomer, and
(C) It is obtained by reacting a carboxylic acid or an acid anhydride thereof.

In the alkali-soluble resin of the first aspect of the present invention, (c) carboxylic acid or acid anhydride thereof is (c1) tetracarboxylic acid or acid dianhydride, and (c2) dicarboxylic acid or acid anhydride thereof. It is preferable.

The alkali-soluble resin of the first invention comprises (a) a (meth) acrylic acid ester having a cyclic structure and a hydroxyl group, (b) a (meth) acrylic acid ester monomer, and (c1) a tetracarboxylic acid or It is preferably obtained by reacting with the acid dianhydride and then reacting with (c2) dicarboxylic acid or the acid anhydride.

The alkali-soluble resin of the first invention comprises (a) a (meth) acrylic acid ester having a cyclic structure and a hydroxyl group, and (c1) a tetracarboxylic acid or an acid dianhydride thereof, and then ( b) It is preferably obtained by reacting a (meth) acrylic acid ester monomer with (c2) dicarboxylic acid or an acid anhydride thereof.

In the alkali-soluble resin of the first invention, it is preferable that the (b) (meth) acrylic acid ester monomer has a hydroxyl group.

The alkali-soluble resin of the second invention is
The following general formula (1):

(In general formula (1), X represents a residue excluding the hydroxyl group of (meth) acrylic acid ester having (a) a cyclic structure and having a hydroxyl group, and Y is (c2) dicarboxylic acid or an acid anhydride thereof. Z represents a residue excluding the carboxyl group or acid anhydride group of (c1) tetracarboxylic acid or its acid dianhydride, and A represents a hydroxyl group. (B) represents a residue excluding the hydroxyl group of the (meth) acrylic acid ester monomer, and n represents an integer of 1 to 20.

The alkali-soluble resin of the third present invention has the following general formula (2):

(In general formula (2), X represents a residue excluding the hydroxyl group of (meth) acrylic acid ester having (a) a cyclic structure and having a hydroxyl group, and Z represents (c1) tetracarboxylic acid or its acid diacid. Represents a residue obtained by removing a carboxyl group or an acid anhydride group of an anhydride, A represents a residue obtained by removing a hydroxyl group of a (b) (meth) acrylic acid ester monomer having a hydroxyl group, and n is an integer of 1 to 20 It is expressed by the following.)

In the alkali-soluble resins of the first to third inventions, it is preferable that (a) the (meth) acrylic acid ester having a cyclic structure and having a hydroxyl group has a bisphenol skeleton.

In the alkali-soluble resins of the first to third inventions, the (b) (meth) acrylic acid ester monomer is preferably a polyfunctional (meth) acrylic acid ester monomer.

The alkali-soluble resins of the first to third inventions include (a) a (meth) acrylic acid ester having a cyclic structure and a hydroxyl group, and (c) a carboxylic acid or an acid anhydride thereof, b) Since it is obtained by reacting a (meth) acrylic acid ester monomer, it is excellent in alkali solubility, developer resistance, fine wire adhesion and pattern straightness, and has an alkali-soluble radiation sensitivity with little film shrinkage. It is suitably used for obtaining a resin composition.

<< Alkali-soluble Resin of First Invention >>
The alkali-soluble resin of the first invention is
(A) a (meth) acrylic acid ester having a cyclic structure and a hydroxyl group,
(B) a (meth) acrylic acid ester monomer, and
(C) It is obtained by reacting a carboxylic acid or an acid anhydride thereof.

<(A) component>
(A) The cyclic structure of a (meth) acrylic acid ester having a cyclic structure and a hydroxyl group (hereinafter also simply referred to as component (a)) refers to a structure in which atoms constituting the molecule are bonded cyclically. . Although it does not specifically limit as a cyclic structure, For example, an aromatic ring, an alicyclic ring, a condensed ring, a heterocyclic ring, etc. are mentioned. These may exist alone in the component (a), or two or more of them may coexist.

Although it does not specifically limit as (a) component, For example, bisphenol fluorene type (epoxy) acrylate, biscresol fluorene type (epoxy) acrylate, bisphenyl phenol fluorene type (epoxy) acrylate, bisphenol A type (epoxy) acrylate, bisphenol AP type (epoxy) acrylate, bisphenol F type (epoxy) acrylate and other bisphenol skeleton containing (epoxy) acrylate, trisphenol skeleton containing (epoxy) acrylate, tetraphenol skeleton containing (epoxy) acrylate, naphthalene skeleton containing (epoxy) acrylate, Novolac skeleton containing (epoxy) acrylate, adamantane skeleton containing (epoxy) acrylate, isocyanuric acid skeleton containing (epoxy) Relate and the like. These may be used alone or in combination of two or more.

In this specification, (meth) acrylic acid ester refers to an ester of (meth) acrylic acid and a hydroxyl group-containing compound or an epoxy group-containing compound. Moreover, in this specification, (meth) acrylic acid shall mean acrylic acid or methacrylic acid.

The component (a) preferably has a bisphenol skeleton, more preferably a fluorene skeleton, because it has excellent heat resistance, adhesion, and chemical resistance when formed into a cured film.

The number of hydroxyl groups contained in the component (a) is not particularly limited, but is preferably 2 to 5 and more preferably 2 in one molecule. Further, the number of carbon-carbon double bonds (C═C bonds) contained in component (a) is not particularly limited, but is preferably 1 to 4 in one molecule, and is 1 to 2 Is more preferable.

<(B) component>
The (b) (meth) acrylic acid ester monomer (hereinafter also simply referred to as the component (b)) is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 -Hydroxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane mono (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylo Luethane di (meth) acrylate, trimethylolethane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate , (Meth) acrylic acid ester monomers that do not have a cyclic structure, such as glycerol (meth) acrylate, and isocyanuric acid ethyl Emissions oxide-modified di (meth) acrylate, 2-hydroxy-3 and phenoxy having a cyclic structure such as acrylate (meth) acrylic acid ester monomer, dendrimeric acrylates, hyperbranched acrylate. These may be used alone or in combination of two or more. In these, it is preferable to use the (meth) acrylic acid ester monomer which does not have a cyclic structure, a dendrimer type acrylate, and a hyperbranch type acrylate.

The component (b) preferably has a hydroxyl group, an epoxy group, an amino group or the like as the reactive functional group, and particularly preferably has a hydroxyl group, in order to be used for a reaction when synthesizing the alkali-soluble resin.

When the component (b) has a reactive functional group, the number of reactive functional groups is not particularly limited, but is preferably 1 to 5 and more preferably 1 in one molecule. Further, the number of carbon-carbon double bonds (C═C bonds) contained in component (b) is not particularly limited, but is preferably 1 to 5 in one molecule, and 3 to 5 in number. Is more preferable.

The component (b) is preferably a polyfunctional (meth) acrylic acid ester monomer because of excellent film curability. Here, polyfunctional means having two or more carbon-carbon double bonds in one molecule.

<(C) component>
(C) As carboxylic acid or its acid anhydride (henceforth only (c) component), it does not specifically limit and a well-known compound can be used.

Since component (c) can adjust developability, (c1) tetracarboxylic acid or its acid dianhydride (hereinafter also simply referred to as (c1) component) and (c2) dicarboxylic acid or its acid anhydride ( Hereinafter, it is preferably simply referred to as the component (c2).

The component (c1) is not particularly limited. For example, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, biphenylethertetracarboxylic acid, diphenylsulfonic acid tetracarboxylic acid, 4,4′-hexafluoropropylidene Examples thereof include bisphthalic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and acid dianhydrides thereof. These may be used alone or in combination of two or more.

The component (c2) is not particularly limited. For example, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, Examples thereof include succinic acid, glutaric acid, trimellitic acid, and acid anhydrides thereof. These may be used alone or in combination of two or more.

<Reaction of components (a) to (c)>
In the reaction of the components (a) to (c), the order of addition of each component is not particularly limited. For example, when the components (c1) and (c2) are used as the component (c), the components (a) and (c) a method of reacting the component b) with the component (c1) and then reacting with the component (c2); reacting the component (a) with the component (c1); and then reacting the component (b) with the component (c2) Examples include a method of reacting components.

In the reaction of the components (a) to (c), the amount of each component used is not particularly limited, but the reactive functional group of the component (b) is usually 1 to 100 mol parts of the hydroxyl group of the component (a). 60 mol parts, preferably 3 mol parts or more and less than 30 mol parts, and the carboxyl group or acid anhydride group of component (c) is usually 30 to 100 mol parts, preferably 50 mol parts or more and 100 mol in terms of acid anhydride groups. It is advantageous to carry out the reaction so that the ratio is less than the molar part. Here, the acid anhydride group is a —CO—O—CO— group, and it is defined that two carboxyl groups of tetracarboxylic acid or dicarboxylic acid correspond to one acid anhydride group. If the reactive functional group of the component (b) is less than 1 mol part, it will cause deterioration of developability, and if it exceeds 60 mol parts, it will also cause deterioration of developability. In addition, when the carboxyl group or acid anhydride group of component (c) is less than 30 mole parts in terms of acid anhydride group, the molecular weight is sufficiently increased to sufficiently introduce the polymerizable double bond group necessary for high sensitivity. In addition, even when used in excess of 100 parts by mole, not only an increase in molecular weight can be obtained, but also unreacted substances remain, causing deterioration of developability. Further, particularly when the components (c1) and (c2) are used as the component (c), the ratio of the component (c1) to the component (c2) is usually 99: 1 to 10:90, preferably Is selected in the range of 95: 5 to 20:80. When the molar ratio of the component (c2) is less than 1, not only does the resin viscosity increase and workability deteriorates, but the molecular weight becomes too large, so that the unexposed area does not dissolve in the developer and the target pattern is It may not be obtained. On the other hand, when the molar ratio of the component (c2) exceeds 90, the molecular weight is small, and thus there may be a problem that sticking remains in the coating film after pre-baking.

The reaction temperature of the components (a) to (c) is not particularly limited, but is preferably 80 to 130 ° C, more preferably 90 to 110 ° C. If the reaction temperature is less than 80 ° C, the reaction does not proceed smoothly and unreacted products may remain. If the reaction temperature exceeds 130 ° C, polymerization of the components (a) and (b) occurs in part. It causes the molecular weight to increase rapidly. The reaction time is not particularly limited, but is preferably 2 to 24 hours, and more preferably 4 to 20 hours. If the reaction time is less than 2 hours, the reaction does not proceed sufficiently and unreacted products may remain. If it exceeds 24 hours, polymerization of the component (a) and the component (b) occurs in part. It causes the molecular weight to increase rapidly.

The reaction of the components (a) to (c) may be performed in the presence of a solvent, a catalyst or the like, if necessary. In the reaction, in addition to the components (a) to (c), other monomers may optionally be reacted. Although it does not specifically limit as another monomer, For example, a polyhydric alcohol, an epoxy compound, an isocyanate compound, a silane coupling agent etc. are mentioned. These may be used alone or in combination of two or more.

<< Alkali-soluble Resin of Second Invention >>
The alkali-soluble resin of the second invention has the following general formula (1):

About (a), (b), (c1), (c2) component, it is the same as that of the alkali-soluble resin of 1st this invention.

<< Alkali-soluble resin of the third invention >>
The alkali-soluble resin of the third present invention has the following general formula (2):

About (a), (b), (c1) component, it is the same as that of the alkali-soluble resin of 1st this invention.

The acid value of the alkali-soluble resins of the first to third inventions is not particularly limited, but is preferably 30 to 120 mgKOH / g, and more preferably 50 to 110 mgKOH / g. When the acid value is less than 30 mgKOH / g, the solubility of the unexposed portion in the developer is lowered, and not only the time required for development is lengthened, but the target pattern may not be obtained. If it exceeds g, the solubility of the unexposed portion in the developer becomes too high, the development margin cannot be obtained, and the target pattern may not be obtained.

The weight average molecular weight of the alkali-soluble resins of the first to third inventions is not particularly limited, but is preferably 1,000 to 50,000, more preferably 1,000 to 20,000, More preferably, it is 1,000 to 10,000. When the weight average molecular weight is less than 1,000, there may be a problem that sticking remains in the coating film after pre-baking. When the weight average molecular weight exceeds 50,000, not only does the resin viscosity increase and workability deteriorates, but also The exposed part does not dissolve in the developer, and the target pattern may not be obtained.

<< Alkali-soluble radiation-sensitive resin composition >>
Hereinafter, an alkali-soluble radiation-sensitive resin composition containing (A) any one of the first to third alkali-soluble resins of the present invention (hereinafter also simply referred to as component (A)) will be described.

Here, radiation sensitivity refers to the property of causing chemical reaction by various types of radiation, and as such radiation, visible light, ultraviolet light, electron beam, X-ray, α-ray, β Line and gamma ray. Among these, ultraviolet rays are the most preferable radiation from the viewpoint of economy and efficiency. As the ultraviolet light, ultraviolet light oscillated from a lamp such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, an arc lamp, or a xenon lamp can be preferably used. Radiation having a shorter wavelength than ultraviolet rays has high chemical reactivity and is theoretically superior to ultraviolet rays, but ultraviolet rays are practical from the viewpoint of economy.

The alkali-soluble radiation sensitive resin composition may optionally contain other components in addition to the component (A). Examples of other components include, but are not limited to, for example, (B) a compound having an epoxy group (hereinafter, also simply referred to as (B) component), (C) a photopolymerization initiator and / or a photosensitizer (hereinafter, referred to as “component”). (Also referred to simply as (C) component), (D) photopolymerizable monomer and / or oligomer (hereinafter also referred to simply as (D) component), solvent, pigment, epoxy group curing accelerator, thermal polymerization inhibitor, antioxidant , Adhesion aids, surfactants, antifoaming agents and the like.

Although it does not specifically limit as (B) component, For example, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a biphenyl type epoxy resin, fat Examples include epoxy resins such as cyclic epoxy resins, and compounds having at least one epoxy group such as phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, and glycidyl methacrylate. . These may be used alone or in combination of two or more.

When the alkali-soluble radiation-sensitive resin composition contains the component (B), the content is not particularly limited, but is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the component (A). More preferably, it is 10 to 30 parts by weight. If the content is less than 5 parts by weight, the properties after curing, particularly alkali resistance, may be insufficient. If it exceeds 50 parts by weight, cracking may occur during curing, and the adhesion may easily decrease. is there.

The component (C) is not particularly limited. For example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, etc. Acetophenones, benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, Benzyldimethyl ketal, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthate Sulfur compounds such as ethylene, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, etc. Organic peroxides, and thiol compounds such as 2-mercaptobenzoimidar, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole. These may be used alone or in combination of two or more.

When the alkali-soluble radiation sensitive resin composition contains the component (C), the content is not particularly limited, but is 0.1 to 30 parts by weight with respect to 100 parts by weight of the component (A). It is preferably 1 to 20 parts by weight. If the content is less than 0.1 parts by weight, the speed of photopolymerization becomes slow and the sensitivity may be lowered. If the content exceeds 30 parts by weight, it is difficult for light to reach the substrate. Adhesion may deteriorate.

The component (D) is not particularly limited. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol Di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate , Trimethylolpropane mono (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolethane di (meth) acrylate, trimethylolethane mono (meth) ) Acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) ) Acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate and the like. These may be used alone or in combination of two or more.

When the alkali-soluble radiation-sensitive resin composition contains the component (D), the content is not particularly limited, but is preferably 50 parts by weight or less with respect to 100 parts by weight of the component (A). More preferably, it is 40 parts by weight or less. When the content exceeds 50 parts by weight, there may be a problem in sticking property after pre-baking.

Examples of the solvent include, but are not limited to, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether. Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2 Ketones such as pentanone; and ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-2 -Methyl methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate Butyl acetate, methyl lactate, and esters such as ethyl lactate. These may be used alone or in combination of two or more.

When the alkali-soluble radiation-sensitive resin composition contains a solvent, the content is not particularly limited and varies depending on the target viscosity, but the solid content concentration of the alkali-soluble radiation-sensitive resin composition Is preferably 1 to 50% by weight, more preferably 5 to 30% by weight.

Although it does not specifically limit as a pigment, For example, carbon black, chromium oxide, iron oxide, titanium black, aniline black, cyanine black, perylene black, etc. are mentioned. These may be used alone or in combination of two or more.

When the alkali-soluble radiation-sensitive resin composition contains a pigment, the content thereof is not particularly limited, but is preferably 50 to 150 parts by weight with respect to 100 parts by weight of component (A), 80 to More preferably, it is 120 parts by weight. When the content is less than 50 parts by weight, the light-shielding property may not be sufficient. When the content exceeds 150 parts by weight, the content of the alkali-soluble resin as the original binder decreases, so that the development characteristics are impaired and the film An undesired problem that the forming ability is impaired may occur.

Since the alkali-soluble radiation-sensitive resin composition can sufficiently bring out the properties after curing, it is preferable that the alkali-soluble radiation-sensitive resin composition further includes a component (B) and a component (C) in addition to the component (A).

Since the alkali-soluble radiation-sensitive resin composition can sufficiently bring out the characteristics after curing, in addition to the component (A), the component (D) is further added to 50 parts by weight with respect to 100 parts by weight of the component (A). It is preferable to include the following.

Since the alkali-soluble radiation-sensitive resin composition contains the alkali-soluble resin according to any one of the first to third aspects of the invention, the alkali-soluble radiation-sensitive resin composition is excellent in alkali solubility, developer resistance, fine wire adhesion, and pattern straightness, Small film shrinkage.

<< cured product >>
Hereinafter, a cured product obtained by curing the above alkali-soluble radiation-sensitive resin composition will be described.

The method for curing the alkali-soluble radiation-sensitive resin composition is not particularly limited, but a solution of the alkali-soluble radiation-sensitive resin composition may be a dipping method, a spray method, a slit coater, a spinner, etc. Examples thereof include a method of applying to a substrate or the like by any method, drying, irradiating light (including ultraviolet rays, radiation, etc.), and then performing a development treatment and post-baking.

Since the cured product is obtained by curing the above-mentioned alkali-soluble radiation-sensitive resin composition, it is excellent in developer resistance, fine line adhesion and pattern straightness, and has a small film shrinkage.

<< cured film >>
Hereinafter, a cured film obtained by curing the above alkali-soluble radiation-sensitive resin composition will be described. The method for curing the alkali-soluble radiation-sensitive resin composition is as described above.

The thickness of the cured film is not particularly limited, but is preferably 0.1 to 10 μm, and more preferably 1 to 5 μm. When the film thickness is less than 0.1 μm, the light shielding property may not be sufficient, and when it exceeds 10 μm, the entire film may not be sufficiently cured.

The use of the cured film is not particularly limited, but protective films such as color filters, liquid crystal display elements, integrated circuit elements, solid-state imaging elements, interlayer insulating films, color resists, solder resists used in the production of printed wiring boards, etc. Can be mentioned.

Since the cured film is obtained by curing the above-described alkali-soluble radiation-sensitive resin composition, it is excellent in developer resistance, fine line adhesion and pattern straightness, and has little film shrinkage.

<< Color filter >>
The cured film described above can be a color filter.
Since the color filter is composed of the above-described cured film, the color filter is excellent in developer resistance, fine line adhesion, and pattern straightness, and the film shrinkage is small.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to a following example. Hereinafter, “part” or “%” means “part by weight” or “% by weight”, respectively, unless otherwise specified.

(Example 1)
In a 300 ml separable flask, 133.9 g of methoxybutyl acetate solution of bisphenolfluorene type epoxy acrylate and 9.0 g of pentaerythritol (tri / tetra) acrylate and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 11.7 g was mixed, and the temperature was gradually raised and reacted at 100 to 105 ° C. for 14 hours. After confirming the disappearance of the acid anhydride, dilute by adding 16.7 g of methoxybutyl acetate, mix 8.6 g of 1,2,3,6-tetrahydrophthalic anhydride, and react at 90-95 ° C. for 4 hours. An alkali-soluble resin 1 was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum. The obtained alkali-soluble resin 1 had a solid content of 56.2%, an acid value of 49.9 mgKOH / g (88.8 mgKOH / g in terms of solid content), and a weight average molecular weight of 3,500.

(Example 2)
In a 300 ml separable flask, 133.9 g of a methoxybutyl acetate solution of bisphenolfluorene type epoxy acrylate and 11.7 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride were mixed, and the temperature was gradually raised. And reacted at 100 to 105 ° C. for 14 hours. After confirming the disappearance of the acid anhydride, 16.7 g of methoxybutyl acetate was added for dilution, and 9.0 g of pentaerythritol (tri / tetra) acrylate and 8.6 g of 1,2,3,6-tetrahydrophthalic anhydride were added. The mixture was mixed and reacted at 90 to 95 ° C. for 4 hours to obtain an alkali-soluble resin 2. The disappearance of the acid anhydride was confirmed by IR spectrum. Moreover, the solid content of the obtained alkali-soluble resin 2 was 56.6%, the acid value was 49.6 mgKOH / g (87.6 mgKOH / g in terms of solid content), and the weight average molecular weight was 3,900.

(Example 3)
In a 300 ml separable flask, 133.9 g of methoxybutyl acetate solution of bisphenolfluorene type epoxy acrylate and 9.0 g of dipentaerythritol (penta / hexa) acrylate and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 11.7 g of the product was mixed, and the temperature was gradually raised and reacted at 100 to 105 ° C. for 14 hours. After confirming the disappearance of the acid anhydride, dilute by adding 16.7 g of methoxybutyl acetate, mix 8.6 g of 1,2,3,6-tetrahydrophthalic anhydride, and react at 90-95 ° C. for 4 hours. An alkali-soluble resin 3 was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum. The obtained alkali-soluble resin 3 had a solid content of 56.8%, an acid value of 49.3 mgKOH / g (86.8 mgKOH / g in terms of solid content), and a weight average molecular weight of 3,700.

Example 4
In a 300 ml separable flask, 133.9 g of a methoxybutyl acetate solution of bisphenolfluorene type epoxy acrylate and 11.7 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride were mixed, and the temperature was gradually raised. And reacted at 100 to 105 ° C. for 14 hours. After confirming the disappearance of the acid anhydride, 16.7 g of methoxybutyl acetate was added for dilution, and 9.0 g of dipentaerythritol (penta / hexa) acrylate and 8.6 g of 1,2,3,6-tetrahydrophthalic anhydride. Were mixed and reacted at 90 to 95 ° C. for 4 hours to obtain an alkali-soluble resin 4. The disappearance of the acid anhydride was confirmed by IR spectrum. The obtained alkali-soluble resin 4 had a solid content of 56.9%, an acid value of 48.4 mgKOH / g (85.1 mgKOH / g in terms of solid content), and a weight average molecular weight of 3,800.

(Example 5)
In a 300 ml separable flask, 131.4 g of methoxybutyl acetate solution of adamantanetriol monoacrylate and 8.5 g of pentaerythritol (tri / tetra) acrylate and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 11 0.1 g was mixed, the temperature was gradually raised, and the mixture was reacted at 100 to 105 ° C. for 14 hours. After confirming the disappearance of the acid anhydride, dilute by adding 10.7 g of methoxybutyl acetate, mix 8.1 g of 1,2,3,6-tetrahydrophthalic anhydride, and react at 90-95 ° C. for 4 hours. An alkali-soluble resin 5 was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum. The obtained alkali-soluble resin 5 had a solid content of 56.7%, an acid value of 49.7 mgKOH / g (87.7 mgKOH / g in terms of solid content), and a weight average molecular weight of 3,200.

(Example 6)
In a 300 ml separable flask, 131.4 g of a methoxybutyl acetate solution of adamantanetriol monoacrylate and 11.1 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride were mixed, and the temperature was gradually raised. The reaction was carried out at 100 to 105 ° C. for 14 hours. After confirming the disappearance of the acid anhydride, 10.7 g of methoxybutyl acetate was added for dilution, and 8.5 g of pentaerythritol (tri / tetra) acrylate and 8.1 g of 1,2,3,6-tetrahydrophthalic anhydride were added. The mixture was mixed and reacted at 90 to 95 ° C. for 4 hours to obtain an alkali-soluble resin 6. The disappearance of the acid anhydride was confirmed by IR spectrum. Moreover, the solid content of the obtained alkali-soluble resin 6 was 56.1%, the acid value was 48.2 mgKOH / g (85.9 mgKOH / g in terms of solid content), and the weight average molecular weight was 3,300.

(Example 7)
In a 300 ml separable flask, 138.6 g of a methoxybutyl acetate solution of bisphenolfluorene type epoxy acrylate, 9.0 g of pentaerythritol (tri / tetra) acrylate, and 9.0 g of pyromellitic anhydride were mixed and gradually heated. The reaction was carried out at 100 to 105 ° C. for 14 hours. After confirming the disappearance of the acid anhydride, dilute by adding 14.5 g of methoxybutyl acetate, mix with 8.9 g of 1,2,3,6-tetrahydrophthalic anhydride, and react at 90-95 ° C. for 4 hours. An alkali-soluble resin 7 was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum. The obtained alkali-soluble resin 7 had a solid content of 55.8%, an acid value of 48.9 mgKOH / g (87.6 mgKOH / g in terms of solid content), and a weight average molecular weight of 3,800.

(Example 8)
In a 300 ml separable flask, 138.6 g of a methoxybutyl acetate solution of bisphenolfluorene type epoxy acrylate and 9.0 g of pyromellitic anhydride were mixed, gradually heated to react at 100 to 105 ° C. for 14 hours. After confirming the disappearance of the acid anhydride, 14.5 g of methoxybutyl acetate was added for dilution, and 9.0 g of pentaerythritol (tri / tetra) acrylate and 8.9 g of 1,2,3,6-tetrahydrophthalic anhydride were added. The mixture was mixed and reacted at 90 to 95 ° C. for 4 hours to obtain an alkali-soluble resin 8. The disappearance of the acid anhydride was confirmed by IR spectrum. The obtained alkali-soluble resin 8 had a solid content of 56.5%, an acid value of 47.7 mgKOH / g (84.4 mgKOH / g in terms of solid content), and a weight average molecular weight of 4,000.

Example 9
In a 300 ml separable flask, 145.6 g of a methoxybutyl acetate solution of trisphenolmethane type epoxy acrylate and 9.0 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride were mixed, and the temperature was gradually raised. The reaction was carried out at 100 to 105 ° C. for 14 hours. After confirming the disappearance of the acid anhydride, 16.6 g of methoxybutyl acetate was added for dilution, and 9.0 g of dipentaerythritol (penta / hexa) acrylate and 4.6 g of 1,2,3,6-tetrahydrophthalic anhydride. And reacted at 90 to 95 ° C. for 4 hours to obtain an alkali-soluble resin 9. The disappearance of the acid anhydride was confirmed by IR spectrum. Moreover, the solid content of the obtained alkali-soluble resin 9 was 55.8%, the acid value was 31.4 mgKOH / g (56.4 mgKOH / g in terms of solid content), and the weight average molecular weight was 5,300.

(Example 10)
In a 300 ml separable flask, 136.6 g of a methoxybutyl acetate solution of bisphenol A novolak type epoxy acrylate and 2.3 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride were mixed and gradually heated. The reaction was carried out at 100 to 105 ° C. for 14 hours. After confirming the disappearance of the acid anhydride, 20.4 g of methoxybutyl acetate was added for dilution, and 9.0 g of dipentaerythritol (penta / hexa) acrylate and 16.4 g of 1,2,3,6-tetrahydrophthalic anhydride. And reacted at 90 to 95 ° C. for 4 hours to obtain an alkali-soluble resin 10. The disappearance of the acid anhydride was confirmed by IR spectrum. The obtained alkali-soluble resin 10 had a solid content of 54.9%, an acid value of 43.6 mgKOH / g (79.4 mgKOH / g in terms of solid content), and a weight average molecular weight of 42,100.

(Comparative Example 1)
In a 300 ml separable flask, 147.4 g of a methoxybutyl acetate solution of bisphenolfluorene type epoxy acrylate and 12.9 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride are mixed, and the temperature is gradually raised. And reacted at 100 to 105 ° C. for 14 hours. After confirming the disappearance of the acid anhydride, dilute by adding 10.3 g of methoxybutyl acetate, mix with 9.5 g of 1,2,3,6-tetrahydrophthalic anhydride, and react at 90-95 ° C. for 4 hours. An alkali-soluble resin 11 was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum. The obtained alkali-soluble resin 11 had a solid content of 55.1%, an acid value of 56.9 mgKOH / g (103.3 mgKOH / g in terms of solid content), and a weight average molecular weight of 4,100.

(Comparative Example 2)
In a 300 ml separable flask, 144.6 g of a methoxybutyl acetate solution of adamantanetriol monoacrylate and 12.2 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride were mixed, and the temperature was gradually raised. The reaction was carried out at 100 to 105 ° C. for 14 hours. After confirming the disappearance of the acid anhydride, it was diluted by adding 4.1 g of methoxybutyl acetate, mixed with 8.9 g of 1,2,3,6-tetrahydrophthalic anhydride, and reacted at 90-95 ° C. for 4 hours. An alkali-soluble resin 12 was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum. The obtained alkali-soluble resin 12 had a solid content of 56.3%, an acid value of 56.4 mgKOH / g (100.2 mgKOH / g in terms of solid content), and a weight average molecular weight of 3,600.

(Comparative Example 3)
In a 300 ml separable flask, 152.5 g of a methoxybutyl acetate solution of bisphenolfluorene type epoxy acrylate and 9.9 g of pyromellitic anhydride were mixed, gradually heated to react at 100 to 105 ° C. for 14 hours. After confirming the disappearance of the acid anhydride, dilute by adding 7.8 g of methoxybutyl acetate, mix 9.8 g of 1,2,3,6-tetrahydrophthalic anhydride, and react at 90-95 ° C. for 4 hours. An alkali-soluble resin 13 was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum. The obtained alkali-soluble resin 13 had a solid content of 55.4%, an acid value of 57.4 mgKOH / g (103.6 mgKOH / g in terms of solid content), and a weight average molecular weight of 4,300.

(Formulation Examples 1 to 10 and Comparative Formulation Examples 1 to 4)
Using the alkali-soluble resins 1 to 13 obtained in Examples 1 to 10 and Comparative Examples 1 to 3, the components were mixed in the weight ratios shown in Table 1 below to prepare alkali-soluble radiation-sensitive resin compositions. did.

For the alkali-soluble radiation-sensitive resin compositions obtained in Formulation Examples 1 to 10 and Comparative Formulation Examples 1 to 4, the alkali solubility, developer resistance, fine wire adhesion, pattern straightness, and film shrinkage are as follows. The method was evaluated. The results are shown in Table 1 below.

(Alkali solubility)
A pre-baked coating film that has not been exposed to light is developed by immersing it in a 0.5% by weight aqueous potassium hydroxide solution for 30 seconds, the glass substrate after development is magnified 50 times, and the remaining resin is visually confirmed. Thus, alkali solubility was evaluated in the following three stages.
○: Good alkali solubility (no alkali-soluble radiation-sensitive resin composition remains on the glass)
Δ: Poor alkali solubility (a slight amount of alkali-soluble radiation-sensitive resin composition remains on the glass)
X: Those having poor alkali solubility (a lot of alkali-soluble radiation-sensitive resin composition remains on the glass)

(Developer resistance)
The coating film exposed to the entire surface is developed by immersing it in a 0.5% by weight aqueous potassium hydroxide solution for 3 minutes, and the glass substrate after development is magnified 50 times to visually check the state of the coating film. Thus, developer resistance was evaluated in the following three stages.
○: Good developer resistance (no cracks in the coating film)
Δ: poor developer resistance (slightly cracked coating)
X: poor developer resistance (coating film with many cracks)

(Fine wire adhesion)
Develop a film that has been exposed using a negative mask by immersing it in a 0.5% by weight aqueous potassium hydroxide solution for 30 seconds, enlarge the glass substrate after development 50 times, and visually check the line pattern. Thus, the fine wire adhesion was evaluated in the following three stages.
○: Fine line adhesion (line pattern formed without peeling from substrate)
Δ: Fine line adhesion is poor (line pattern is formed but pattern chipping occurs)
X: Those with poor thin-line adhesion (separated from the substrate and no line pattern was formed)

(Pattern straightness)
Develop a film that has been exposed using a negative mask by immersing it in a 0.5% by weight aqueous potassium hydroxide solution for 30 seconds, enlarge the glass substrate after development 50 times, and visually check the line pattern. Thus, the pattern straightness was evaluated in the following three stages.
○: Good pattern straightness (line edge is not rattling)
Δ: The pattern straightness is poor (the edge of the line is slightly wobbled)
X: Pattern straightness is poor (a lot of line edge is not smooth)

(Membrane shrinkage)
The coating film subjected to the exposure / development treatment was post-baked at 230 ° C. for 30 minutes, and film shrinkage before and after the post-baking was confirmed to evaluate film shrinkage in the following three stages.
○: Good film shrinkage (low film slippage)
Δ: Film shrinkage is poor (film is slightly slippery)
X: Those with poor film shrinkage (those with many film slips)

The tetramethylbiphenyl type epoxy resin used is a product name “Epicoat YX-4000” manufactured by Yuka Shell Co., Ltd., and an epoxy equivalent of 193. The photopolymerization initiator is trade name “Irgacure 907” manufactured by BASF.

From the results shown in Table 1, Formulation Examples 1 to 10 using the alkali-soluble resins of the first to third inventions obtained by reacting the component (b) in addition to the components (a) and (c) It can be seen that, compared with Comparative Formulation Examples 1 to 4 using an alkali-soluble resin not reacted with the component (b), the developer resistance, fine wire adhesion and pattern straightness are excellent, and the film shrinkage is small.

Claims

(A) a (meth) acrylic acid ester having a cyclic structure and a hydroxyl group,
(B) a (meth) acrylic acid ester monomer, and
(C) An alkali-soluble resin obtained by reacting a carboxylic acid or an acid anhydride thereof.
The alkali-soluble resin according to claim 1, wherein (c) the carboxylic acid or its acid anhydride is (c1) a tetracarboxylic acid or its acid dianhydride, and (c2) a dicarboxylic acid or its acid anhydride.
(A) a (meth) acrylic acid ester having a cyclic structure and a hydroxyl group, (b) a (meth) acrylic acid ester monomer, (c1) a tetracarboxylic acid or an acid dianhydride thereof, (C2) The alkali-soluble resin according to claim 2, obtained by reacting dicarboxylic acid or an acid anhydride thereof.
(A) a (meth) acrylic acid ester having a cyclic structure and a hydroxyl group is reacted with (c1) tetracarboxylic acid or an acid dianhydride thereof, and then (b) a (meth) acrylic acid ester monomer; (C2) The alkali-soluble resin according to claim 2, obtained by reacting dicarboxylic acid or an acid anhydride thereof.
The alkali-soluble resin according to any one of claims 1 to 4, wherein the (b) (meth) acrylic acid ester monomer has a hydroxyl group.
The following general formula (1):

(In general formula (1), X represents a residue excluding the hydroxyl group of (meth) acrylic acid ester having (a) a cyclic structure and having a hydroxyl group, and Y is (c2) dicarboxylic acid or an acid anhydride thereof. Z represents a residue excluding the carboxyl group or acid anhydride group of (c1) tetracarboxylic acid or its acid dianhydride, and A represents a hydroxyl group. (B) an alkali-soluble resin represented by (b) a residue of a (meth) acrylic acid ester monomer excluding a hydroxyl group, wherein n represents an integer of 1 to 20.
The following general formula (2):

(In general formula (2), X represents a residue excluding the hydroxyl group of (meth) acrylic acid ester having (a) a cyclic structure and having a hydroxyl group, and Z represents (c1) tetracarboxylic acid or its acid diacid. Represents a residue obtained by removing a carboxyl group or an acid anhydride group of an anhydride, A represents a residue obtained by removing a hydroxyl group of a (b) (meth) acrylic acid ester monomer having a hydroxyl group, and n is an integer of 1 to 20 An alkali-soluble resin characterized by being represented by:
The alkali-soluble resin according to any one of claims 1 to 7, wherein the (a) (meth) acrylic acid ester having a cyclic structure and having a hydroxyl group has a bisphenol skeleton.
The alkali-soluble resin according to any one of claims 1 to 8, wherein the (b) (meth) acrylic acid ester monomer is a polyfunctional (meth) acrylic acid ester monomer.