TW201708302A - Alkali-soluble resin - Google Patents

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

This invention relates to an alkali soluble resin.

Generally, it is used as a resist material for forming an ITO electrode of a liquid crystal display (LCD), an organic EL display, or an interlayer insulating film, a circuit protective film, a color filter for color filter manufacturing, and a coloring pigment dispersion resist. The EL display uses a permanent film forming material such as a partition wall material, and a radiation sensitive resin composition is widely used. Among them, in recent years, liquid crystal displays have been in high demand in television applications and the like, and in the manufacturing steps, a radiation sensitive resin composition is often used.

As a radioactive resin composition, for example, Patent Document 1 proposes a photosensitive resin composition for a black resist containing an unsaturated group-containing compound as an essential component, and the unsaturated group-containing compound is made of The reaction product of an epoxy compound having two glycidyl ether groups derived from a bisphenol and (meth)acrylic acid is further reacted with a polyvalent carboxylic acid or an anhydride thereof. However, this composition is excellent in alkali solubility, but has insufficient development liquid resistance, fine line adhesion, and pattern linearity, and has a large film shrinkage. Therefore, there is room for improvement in such aspects.

Prior technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2004-361736

An object of the present invention is to provide an alkali-soluble resin which can be suitably used for obtaining an alkali-soluble radiation sensitive resin which is excellent in alkali solubility, developer resistance, fine line adhesion, and pattern linearity and which has a small film shrinkage. Composition.

The inventors of the present invention have intensively studied to solve the above problems, and have found that (b) (a) a (meth) acrylate having a cyclic structure and having a hydroxyl group, and (c) a carboxylic acid or an acid anhydride thereof, The alkali-soluble resin obtained by the reaction of the (meth) acrylate monomer can be suitably used for obtaining an alkali-soluble type which is excellent in alkali solubility, developer resistance, fine line adhesion, and pattern linearity and which has a small film shrinkage. The radiation sensitive resin composition was irradiated, thereby completing the present invention.

That is, the alkali-soluble resin of the first invention of the present invention is characterized in that (a) a (meth) acrylate having a cyclic structure and having a hydroxyl group, (b) a (meth) acrylate monomer, and (c) A carboxylic acid or an anhydride thereof is obtained by reaction.

The alkali-soluble resin of the first invention of the present invention is preferably (c) a carboxylic acid or an anhydride thereof (C1) a tetracarboxylic acid or an acid dianhydride thereof, and (c2) a dicarboxylic acid or an anhydride thereof.

The alkali-soluble resin of the first invention of the present invention is preferably (a) a (meth) acrylate having a cyclic structure and having a hydroxyl group, (b) a (meth) acrylate monomer, and (c1) a tetracarboxylate. The reaction is carried out by reacting an acid or an acid dianhydride thereof, followed by reacting the (c2) dicarboxylic acid or its anhydride.

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

The alkali-soluble resin of the first invention of the present invention preferably has a (b) (meth) acrylate monomer having a hydroxyl group.

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

(In the formula (1), X represents (a) a residue having a cyclic structure and having a hydroxyl group (meth) acrylate other than a hydroxyl group, and Y represents a carboxyl group of (c2) a dicarboxylic acid or an anhydride thereof or a residue other than an acid anhydride group, Z represents a residue other than a carboxyl group or an acid anhydride group of (c1) a tetracarboxylic acid or an acid dianhydride thereof, and A represents a hydroxyl group of a (b) (meth) acrylate monomer having a hydroxyl group. The external residue, n represents an integer from 1 to 20).

The alkali-soluble resin of the third invention of the present invention is characterized by the following formula (2):

(In the formula (2), X represents (a) a residue having a cyclic structure and having a hydroxyl group (meth) acrylate other than a hydroxyl group, and Z represents a (c1) addition of a tetracarboxylic acid or an acid dianhydride thereof. A residue other than a carboxyl group or an acid anhydride group, A represents a residue other than a hydroxyl group of the (b) (meth) acrylate monomer having a hydroxyl group, and n represents an integer of 1 to 20).

The alkali-soluble resin of the first to third inventions of the present invention preferably has (a) a (meth) acrylate having a cyclic structure and having a hydroxyl group and having a bisphenol skeleton.

The alkali-soluble resin of the first to third inventions of the present invention is preferably a (b) (meth) acrylate monomer which is a polyfunctional (meth) acrylate monomer.

The alkali-soluble resin of the first to third inventions of the present invention, in addition to (a) having a cyclic structure and having a hydroxyl group (meth) acrylate and (c) a carboxylic acid or an anhydride thereof, also (b) ( Since the methyl group acrylate monomer is obtained by reaction, it can be suitably used for alkali-soluble radiation sensitivity which is excellent in alkali solubility, development liquid resistance, fine line adhesion, and pattern linearity and film shrinkage is small. Resin composition.

"Alkyl Soluble Resin of the First Invention of the Invention"

The alkali-soluble resin of the first invention of the present invention is characterized in that (a) a (meth) acrylate having a cyclic structure and having a hydroxyl group, (b) A (meth) acrylate monomer and (c) a carboxylic acid or an anhydride thereof are obtained by reaction.

<(a) component>

The cyclic structure of (a) a (meth) acrylate having a cyclic structure and having a hydroxyl group (hereinafter also referred to simply as (a) component) means a structure in which atoms constituting a molecule are bonded in a ring shape. The cyclic structure is not particularly limited, and examples thereof include an aromatic ring, an alicyclic ring, a fused ring, and a heterocyclic ring. These may be present alone in the component (a), or may be present in combination of two or more.

The component (a) is not particularly limited, and examples thereof include bisphenol oxime (epoxy) acrylate, biscresol oxime (epoxy) acrylate, and bisphenylphenol oxime (epoxy) acrylate. Bisphenol A type (epoxy) acrylate, bisphenol AP type (epoxy) acrylate, bisphenol F type (epoxy) acrylate and the like (epoxy) acrylate containing bisphenol skeleton; containing trisphenol skeleton (epoxy) acrylate; (epoxy) acrylate containing tetraphenol skeleton; (epoxy) acrylate containing naphthalene skeleton; (epoxy) acrylate containing phenolic skeleton; adamantane skeleton (epoxy ) acrylate; (epoxy) acrylate containing isocyanuric acid skeleton. These may be used alone or in combination of two or more.

Further, in the present specification, (meth) acrylate means an ester of (meth)acrylic acid with a hydroxyl group-containing compound or an epoxy group-containing compound. Further, in the present specification, (meth)acrylic means acrylic acid or methacrylic acid.

The component (a) preferably has a bisphenol skeleton and more preferably has an anthracene skeleton in terms of heat resistance, adhesion, and chemical resistance when the cured film is formed.

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

<(b) component>

The (b) (meth) acrylate monomer (hereinafter also referred to simply as the component (b)) is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate and (meth)acrylic acid. 2-hydroxypropyl ester, 3-hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(methyl) Acrylate, tetraethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane di Methyl) acrylate, trimethylolpropane mono(meth) acrylate, trimethylolethane tri(meth) acrylate, trimethylolethane di(meth) acrylate, trishydroxyl Ethyl mono (meth) acrylate, neopentyl alcohol mono (meth) acrylate, neopentyl alcohol di (meth) acrylate, neopentyl alcohol tri (meth) acrylate, neopentyl Alcohol tetra(meth)acrylate, dipentaerythritol mono(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, two new Pentaerythritol tetra(meth)acrylate, dipentaerythritol five ( (meth) acrylate monomer having no cyclic structure such as acrylate, dipentaerythritol hexa(meth) acrylate or glycerol (meth) acrylate; or isocyanuric acid epoxy B a (meth) acrylate monomer having a cyclic structure such as an alkane-modified di(meth) acrylate or a 2-hydroxy-3-phenoxypropyl acrylate; or a dendrimer-type acrylate, hyperbranched Acrylate and the like. These may be used alone or in combination of two or more. Among these, a (meth) acrylate monomer, a dendrimer acrylate, or a hyperbranched acrylate which does not have a cyclic structure is preferably used.

Since the component (b) is a reaction for synthesizing an alkali-soluble resin, it preferably has a hydroxyl group, an epoxy group, an amine group or the like as a reactive functional group, and particularly preferably has a hydroxyl group.

In the case where the component (b) has a reactive functional group, the reactive functional group The number is not particularly limited, but is preferably 1 to 5, more preferably 1 in 1 molecule. Further, the number of the carbon-carbon double bonds (C=C bond) of the component (b) is not particularly limited, but is preferably 1 to 5, more preferably 3 to 5 in one molecule.

The component (b) is preferably a polyfunctional (meth) acrylate monomer in terms of excellent film hardenability. Here, the term "multifunctional" means having two or more carbon-carbon double bonds in one molecule.

<(c) component>

The (c) carboxylic acid or its anhydride (hereinafter also referred to simply as the component (c)) is not particularly limited, and a known compound can be used.

In terms of adjustability, the component (c) is preferably (c1) a tetracarboxylic acid or an acid dianhydride thereof (hereinafter also referred to simply as a component (c1)), and (c2) a dicarboxylic acid or an anhydride thereof ( Hereinafter also referred to as (c2) component).

The component (c1) is not particularly limited, and examples thereof include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, and diphenylsulfonic acid tetracarboxylic acid. 4,4'-hexafluoropropylenediphthalic acid, 1,2,4,5-cyclohexanetetracarboxylic acid or the like or the acid dianhydride or the like. These may be used alone or in combination of two or more.

The component (c2) is not particularly limited, and examples thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and methyl group. Methylenetetrahydrophthalic acid, chlorobridge acid, methyltetrahydrophthalic acid, succinic acid, glutaric acid, trimellitic acid, etc. or the like. These may be used alone or in combination of two or more.

<Reaction of (a) to (c) components>

In the reaction of the components (a) to (c), the order of addition of each component is not particularly limited, for example, When the component (c1) and the component (c2) are used as the component (c), a method of reacting the component (a), the component (b), and the component (c1), and then reacting the component (c2) may be mentioned; Alternatively, a method in which the component (a) is reacted with the component (c1), and then the component (b) and the component (c2) are reacted.

In the reaction of the components (a) to (c), the amount of each component used is not particularly limited, and it is advantageous to carry out the reaction in such a manner that the hydroxyl group is 100 mol with respect to the hydroxyl group of the component (a). The reactive functional group of the component (b) is usually 1 to 60 mole parts, preferably 3 mole parts or more and less than 30 mole parts, and the carboxyl group or the acid anhydride group of the component (c) is usually converted into an acid anhydride group. It is 30 to 100 moles, preferably 50 moles or more and less than 100 moles. Here, the acid anhydride group is a -CO-O-CO- group, and two carboxyl groups defined as a tetracarboxylic acid or a dicarboxylic acid correspond to one acid anhydride group. When the reactive functional group of the component (b) is less than 1 part by mole, the developability is deteriorated, and even if more than 60 moles are used, the developability is deteriorated in the same manner. In addition, when the carboxyl group or the acid anhydride group of the component (c) is less than 30 mole parts in terms of an acid anhydride group, it is difficult to sufficiently increase the molecular weight and sufficiently introduce a polymerizable double bond group required for high sensitivity, and even if more than 100 moles are used. In the same manner, not only the molecular weight could not be increased, but also the unreacted material remained, which was a cause of deterioration in developability. Further, in particular, when the component (c1) and the component (c2) are used as the component (c), the ratio of the component (c1) to the component (c2) is selected within the following range: usually 99 in terms of a molar ratio: 1~10:90, preferably 95:5~20:80. When the molar ratio of the component (c2) is less than 1, the resin viscosity is high and the workability is deteriorated, and the molecular weight is too large. Therefore, the unexposed portion is not dissolved in the developer and the target pattern cannot be obtained. Further, when the molar ratio of the component (c2) exceeds 90, the molecular weight is small, so that there is a problem that residual sticking occurs on the coating film after prebaking.

The reaction temperature of the components (a) to (c) is not particularly limited, and is preferably 80 to 130. °C, more preferably 90~110 °C. When the reaction temperature is less than 80 ° C, the reaction does not proceed smoothly and the unreacted material remains. If it exceeds 130 ° C, the polymerization of the component (a) and the component (b) is locally caused, and the molecular weight is rapidly increased. . The reaction time is not particularly limited, but is preferably 2 to 24 hours, more preferably 4 to 20 hours. When the reaction time is less than 2 hours, the reaction does not proceed sufficiently and the unreacted material remains. If it exceeds 24 hours, the polymerization of the component (a) and the component (b) is locally caused, and the molecular weight is rapidly increased. .

The reaction of the components (a) to (c) may be carried out in the presence of a solvent or a catalyst as needed. Further, in the reaction, in addition to the components (a) to (c), other monomers may be optionally reacted. The other monomer is not particularly limited, and examples thereof include a polyhydric alcohol, an epoxy compound, an isocyanate compound, and a decane coupling agent. These may be used alone or in combination of two or more.

"Alkyl Soluble Resin of Second Invention of the Invention"

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

(In the formula (1), X represents (a) a residue having a cyclic structure and having a hydroxyl group (meth) acrylate other than a hydroxyl group, and Y represents a carboxyl group of (c2) a dicarboxylic acid or an anhydride thereof or a residue other than an acid anhydride group, Z represents a residue other than a carboxyl group or an acid anhydride group of (c1) a tetracarboxylic acid or an acid dianhydride thereof, and A represents a hydroxyl group of a (b) (meth) acrylate monomer having a hydroxyl group. The external residue, n represents an integer from 1 to 20).

The components (a), (b), (c1), and (c2) are the same as the alkali-soluble resin of the first invention of the present invention.

"Alkyl Soluble Resin of the Third Invention of the Invention"

The alkali-soluble resin of the third invention of the present invention is characterized by the following formula (2):

(In the formula (2), X represents (a) a residue having a cyclic structure and having a hydroxyl group (meth) acrylate other than a hydroxyl group, and Z represents a (c1) addition of a tetracarboxylic acid or an acid dianhydride thereof. A residue other than a carboxyl group or an acid anhydride group, A represents a residue other than a hydroxyl group of the (b) (meth) acrylate monomer having a hydroxyl group, and n represents an integer of 1 to 20).

The components (a), (b) and (c1) are the same as the alkali-soluble resin of the first invention of the present invention.

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

The weight average molecular weight of the alkali-soluble resin of the first to third inventions of the present invention is not particularly limited, but is preferably 1,000 to 50,000, more preferably 1,000 to 20,000, and still more preferably It is 1,000 to 10,000. When the weight average molecular weight is less than 1,000, there is a problem that residual adhesion occurs on the coating film after prebaking, and if it exceeds 50,000, not only the resin viscosity is high, but workability is deteriorated, and the unexposed portion is not dissolved. In the case of a developer, the target pattern cannot be obtained.

"Alkaline Soluble Radiation Sensitive Resin Composition"

In the following, an alkali-soluble radiation-sensitive resin composition containing the alkali-soluble resin (hereinafter also referred to as (A) component) of any one of the first to third aspects of the invention (A) will be described.

Here, the term "radiation sensitivity" refers to a property of causing a chemical reaction by various kinds of radiation, and such radiation may be, for example, visible light, ultraviolet light, electron beam, X-ray, or alpha ray, as long as the wavelength is longer. Beta rays, and gamma rays. Among these, in terms of economy and efficiency, ultraviolet light is the best radiation. As the ultraviolet light, ultraviolet light oscillated from a lamp such as a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an arc lamp, or a xenon lamp can be suitably used. Radiation, which has a shorter wavelength than ultraviolet light, is chemically reactive and theoretically superior to ultraviolet light, but from the viewpoint of economy, ultraviolet light is practical.

The alkali-soluble radiation sensitive resin composition may optionally contain other components in addition to the component (A). The other component is not particularly limited, and examples thereof include (B) a compound having an epoxy group (hereinafter also referred to simply as a component (B)), (C) a photopolymerization initiator, and/or a photosensitizer (hereinafter). Also referred to as (C) component), (D) photopolymerizable monomer and/or oligomer (hereinafter also referred to as (D) component), solvent, pigment, epoxy hardening accelerator, thermal polymerization inhibitor, Antioxidants, adhesion aids, surfactants, defoamers, and the like.

The component (B) is not particularly limited, and examples thereof include a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol. S-type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin and other epoxy a resin; or phenyl glycidyl ether, p-butyl phenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, glycidyl methacrylate, etc. having at least 1 a compound of an epoxy group or the like. These may be used alone or in combination of two or more.

In the case where the alkali-soluble radiation-sensitive resin composition contains the component (B), the content thereof is not particularly limited, but is preferably 5 to 50 parts by weight, more preferably 100 parts by weight based on 100 parts by weight of the component (A). 10 to 30 parts by weight. When the content is less than 5 parts by weight, the properties after curing, in particular, the alkali resistance may be insufficient. When the amount is more than 50 parts by weight, cracking may occur during curing, and the adhesion may be easily lowered.

The component (C) is not particularly limited, and examples thereof include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, and dichlorobenzene. Acetophenone, trichloroacetophenone, acetophenone such as p-tert-butylacetophenone; or benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobiphenyl Benzophenones such as ketones; or benzoin, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.; or benzoin dimethyl ketal, sulfur 2-chlorosulfur 2,4-diethyl sulphide 2-methylsulfide 2-isopropylsulfur a sulfur compound; or a quinone such as 2-ethyl hydrazine, octamethyl hydrazine, 1,2-benzopyrene, 2,3-diphenyl hydrazine; or azobisisobutyronitrile An organic peroxide such as benzamidine oxide or cumene peroxide; or 2-mercaptobenzimidazole or 2-mercaptobenzoene a thiol compound such as azole or 2-mercaptobenzothiazole. These may be used alone or in combination of two or more.

In the case where the alkali-soluble radiation sensitive resin composition contains the component (C), the content thereof is not particularly limited, but is preferably 0.1 to 30 parts by weight, more preferably 100 parts by weight based on the component (A). 1 to 20 parts by weight. When the content is less than 0.1 part by weight, the speed of photopolymerization may be slow and the sensitivity may be lowered. When the content is more than 30 parts by weight, it is difficult for light to reach the substrate. There is a case where the adhesion between the substrate and the resin is deteriorated.

The component (D) is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. , ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1, 4-butanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane mono(meth)acrylic acid Ester, trimethylolethane tri(meth)acrylate, trimethylolethane di(meth)acrylate, trimethylolethane mono(meth)acrylate, pentaerythritol mono( Methyl) acrylate, neopentyl alcohol di(meth) acrylate, neopentyl alcohol tri (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol single (A) Acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol (meth) acrylate, dipentaerythritol hexa(methyl) propyl Ethacrylate, glycerol (meth) acrylate, and the like. These may be used alone or in combination of two or more.

In the case where the alkali-soluble radiation-sensitive resin composition contains the component (D), the content thereof is not particularly limited, but is preferably 50 parts by weight or less, more preferably 40% by weight based on 100 parts by weight of the component (A). Parts by weight or less. If the content exceeds 50 parts by weight, there is a problem that the tackiness after prebaking is problematic.

The solvent is not particularly limited, and examples thereof include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol. Glycol ethers such as monoethyl ether; ethylene glycol alkyl ether acetate such as cyproterone acetate, acetaminophenacetate; diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol Diethylene glycol such as glyceryl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether or diethylene glycol monobutyl ether; Propylene glycol alkyl ether acetates such as alcohol methyl ether acetate, propylene glycol diethyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxyl Ketones such as -4-methyl-2-pentanone; and ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, B Ethyl oxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropane An ester such as methyl ester, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate or ethyl lactate. These may be used alone or in combination of two or more.

In the case where the alkali-soluble radiation sensitive resin composition contains a solvent, the content thereof is not particularly limited, and varies depending on the target viscosity. Preferably, the solid content concentration of the alkali-soluble radiation sensitive resin composition is 1 The amount of ~50% by weight is more preferably 5 to 30% by weight.

The pigment is not particularly limited, and examples thereof include carbon black, chromium oxide, iron oxide, titanium black, nigrosine, cyanine black, and tanning black. These may be used alone or in combination of two or more.

In the case where 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, more preferably 80 to 120 parts by weight based on 100 parts by weight of the component (A). Parts by weight. When the content is less than 50 parts by weight, the light-shielding property may be insufficient. When the amount is more than 150 parts by weight, the content of the alkali-soluble resin which is originally a binder is reduced, so that the development property is impaired and the film forming ability is affected. Defects such as damage.

The alkali-soluble radiation-sensitive resin composition preferably contains the component (B) and (C) in addition to the component (A) in terms of sufficiently improving the properties after hardening. ingredient.

The alkali-soluble radiation-sensitive resin composition is preferably contained in an amount of 50 parts by weight based on 100 parts by weight of the component (A), in addition to the component (A). )ingredient.

The alkali-soluble radiation-sensitive resin composition contains the alkali-soluble resin of any one of the first to third aspects of the invention, and therefore has excellent alkali solubility, developer resistance, fine line adhesion, and pattern linearity, and the film The shrinkage is small.

Hardened

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

The method of curing the alkali-soluble radiation-sensitive resin composition is not particularly limited, and examples thereof include a method such as a dipping method, a spray method, or a slit coater or a spin coater. In one method, a solution of an alkali-soluble radiation sensitive resin composition is applied onto a substrate or the like, dried, and irradiated with light (including ultraviolet rays, radiation, etc.), followed by development treatment and post-baking.

Since the hardened material is obtained by curing the above-described alkali-soluble radiation sensitive resin composition, it is excellent in development liquid resistance, fine line adhesion, and pattern linearity, and film shrinkage is small.

Hardened film

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

The film thickness of the cured film is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 1 to 5 μm. When the film thickness is less than 0.1 μm, the light-shielding property may be insufficient, and if it exceeds 10 In the case of μm, there is a case where the entire film is not sufficiently cured.

The use of the cured film is not particularly limited, and examples thereof include a protective film or an interlayer insulating film such as a color filter, a liquid crystal display device, an integrated circuit device, and a solid-state imaging device, a color resist, and a printed wiring board. Solder resists, etc.

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

Color Filter

The above cured film can be made into a color filter.

Since the color filter contains the cured film described above, it is excellent in developer liquid resistance, fine line adhesion, and pattern linearity, and has small film shrinkage.

[Examples]

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the following examples. In the following, "parts" or "%" means "parts by weight" or "% by weight" unless otherwise stated.

(Example 1)

133.9 g of bisphenol oxime epoxy acrylate methoxybutyl acetate solution and 9.0 g and 3,3',4 of pentaerythritol (tri/tetra) acrylate were mixed in a 300 ml separable flask. 11.7 g of 4'-biphenyltetracarboxylic dianhydride was gradually heated to react 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 8.6 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, and the reaction was carried out at 90 to 95 ° C. In an hour, an alkali-soluble resin 1 was obtained. The disappearance of the acid anhydride was confirmed by IR spectroscopy. Moreover, the solid content component of the alkali-soluble resin 1 obtained was 56.2%, and the acid value was 49.9 mgKOH/g (88.8 mgKOH/ in terms of solid content). g), the weight average molecular weight is 3,500.

(Example 2)

Mixing 133.9 g of bisphenol oxime epoxy acrylate methoxybutyl acetate solution and 11.7 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride in a 300 ml separable flask, gradually The mixture was heated to react 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 neopentyl alcohol (tri/tetra) acrylate and 1,2,3,6-tetrahydrophthalic acid were mixed. 8.6 g of an acid anhydride was allowed to react 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 spectroscopy. The alkali-soluble resin 2 obtained had a solid content of 56.6%, an acid value of 49.6 mgKOH/g (87.6 mgKOH/g in terms of solid content), and a weight average molecular weight of 3,900.

(Example 3)

133.9 g of bisphenolphthalein type epoxy acrylate methoxybutyl acetate solution and 9.0 g of dipentaerythritol (penta/hexa) acrylate and 3,3',4 were mixed in a 300 ml separable flask. 11.7 g of 4'-biphenyltetracarboxylic dianhydride was gradually heated to react 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 8.6 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, and the reaction was carried out at 90 to 95 ° C. In an hour, an alkali-soluble resin 3 was obtained. The disappearance of the acid anhydride was confirmed by IR spectroscopy. In addition, the solid content component of the alkali-soluble resin 3 obtained was 56.8%, the acid value was 49.3 mgKOH/g (86.8 mgKOH/g in terms of solid content), and the weight average molecular weight was 3,700.

(Example 4)

Mixing 133.9 g of bisphenol oxime epoxy acrylate methoxybutyl acetate solution and 11.7 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride in a 300 ml separable flask, gradually Warm up to make it at 100 The reaction was carried out at ~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 1,2,3,6-tetrahydroortylene were mixed. 8.6 g of formic anhydride was allowed to react 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 spectroscopy. Moreover, the solid content component of the alkali-soluble resin 4 obtained was 56.9%, the acid value was 48.4 mgKOH/g (85.1 mgKOH/g in terms of solid content), and the weight average molecular weight was 3,800.

(Example 5)

131.4 g of methoxybutyl acetate solution of adamantane triol monoacrylate and 8.5 g of neopentyl alcohol (tri/tetra) acrylate and 3,3',4,4 in a 300 ml separable flask 11.-g of biphenyltetracarboxylic dianhydride was gradually heated to react 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 8.1 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, and the reaction was carried out at 90 to 95 ° C. In an hour, an alkali-soluble resin 5 was obtained. The disappearance of the acid anhydride was confirmed by IR spectroscopy. The alkali-soluble resin 5 obtained 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)

131.4 g of methoxybutyl acetate solution of adamantane triol monoacrylate and 11.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride were mixed in a 300 ml separable flask, and gradually warmed up. It was allowed to react 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 neopentyl alcohol (tri/tetra) acrylate and 1,2,3,6-tetrahydrophthalic acid were mixed. 8.1 g of an acid anhydride was allowed to react 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 spectroscopy. Further, the solid content of the obtained alkali-soluble resin 6 is 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)

138.6 g of bisphenolphthalein type epoxy acrylate methoxybutyl acetate solution and 9.0 g of neopentyl alcohol (tri/tetra) acrylate and pyromic acid dianhydride 9.0 were mixed in a 300 ml separable flask. g, gradually warming up and reacting 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 8.9 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, and the reaction was carried out at 90 to 95 ° C. In an hour, an alkali-soluble resin 7 was obtained. The disappearance of the acid anhydride was confirmed by IR spectroscopy. Further, 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)

138.6 g of a bisphenol oxime type epoxy acrylate methoxybutyl acetate solution and 9.0 g of pyromellitic dianhydride were mixed in a 300 ml separable flask, and the temperature was gradually increased to react at 100 to 105 ° C. 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 neopentyl alcohol (tri/tetra) acrylate and 1,2,3,6-tetrahydrophthalic acid were mixed. 8.9 g of an acid anhydride was allowed to react 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 spectroscopy. Further, 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)

Mixing trimethyl phenol methane acrylate methacrylate in a 300 ml separable flask 145.6 g of a basal acetate solution and 9.0 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride were gradually heated to carry out a reaction 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 1,2,3,6-tetrahydroortylene were mixed. 4.6 g of formic anhydride was allowed to react 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 spectroscopy. Further, the obtained alkali-soluble resin 9 had a solid content of 55.8%, an acid value of 31.4 mgKOH/g (56.4 mgKOH/g in terms of solid content), and a weight average molecular weight of 5,300.

(Embodiment 10)

Mixing 136.6 g of bisphenol A novolac type epoxy acrylate methoxybutyl acetate solution and 3,3',4,4'-biphenyltetracarboxylic dianhydride 2.3 g in a 300 ml separable flask The temperature was gradually increased and allowed to react 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 1,2,3,6-tetrahydroortylene were mixed. 16.4 g of formic anhydride was allowed to react 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 spectroscopy. Further, 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)

147.4 g of bisphenol oxime epoxy acrylate methoxybutyl acetate solution and 12.9 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride were mixed in a 300 ml separable flask. The mixture was heated to react at 100 to 105 ° C for 14 hours. After confirming the disappearance of the acid anhydride, 10.3 g of methoxybutyl acetate was added for dilution, and 9.5 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, and the reaction was carried out at 90 to 95 ° C. In an hour, an alkali-soluble resin 11 was obtained. The disappearance of the acid anhydride was confirmed by IR spectroscopy. Again The alkali-soluble resin 11 obtained 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)

144.6 g of a solution of adamantane triol monoacrylate methoxybutyl acetate and 12.2 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride were mixed in a 300 ml separable flask, and gradually warmed up. It was allowed to react at 100 to 105 ° C for 14 hours. After confirming the disappearance of the acid anhydride, 4.1 g of methoxybutyl acetate was added for dilution, and 8.9 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, and the reaction was carried out at 90 to 95 ° C. The alkali-soluble resin 12 was obtained in an hour. The disappearance of the acid anhydride was confirmed by IR spectroscopy. The alkali-soluble resin 12 obtained 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)

152.5 g of bisphenol oxime epoxy acrylate methoxybutyl acetate solution and 9.9 g of pyromellitic dianhydride were mixed in a 300 ml separable flask, and the temperature was gradually increased to react at 100 to 105 ° C. 14 hours. After confirming the disappearance of the acid anhydride, 7.8 g of methoxybutyl acetate was added for dilution, and 9.8 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, and the reaction was carried out at 90 to 95 ° C. In an hour, an alkali-soluble resin 13 was obtained. The disappearance of the acid anhydride was confirmed by IR spectroscopy. The alkali-soluble resin 13 obtained 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.

(Admixing Examples 1 to 10 and Comparative Blending 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 at a weight ratio shown in Table 1 below to prepare an alkali-soluble radiation-sensitive resin composition.

The alkali-soluble, anti-developing liquid, and fine-line adhesiveness of the alkali-soluble radiation-sensitive resin composition obtained in the blending examples 1 to 10 and the comparative blending examples 1 to 4 were evaluated by the following methods. The pattern is linear and the film shrinks. The results are shown in Table 1 below.

(alkali solubility)

The pre-baked coating film which was not subjected to the exposure treatment was immersed in a 0.5% by weight aqueous potassium hydroxide solution for 30 seconds to be developed, and the developed glass substrate was enlarged to 50 times, and the remaining resin was visually confirmed. The alkali solubility was evaluated in three grades.

○: The alkali solubility is good (the alkali-soluble radiation sensitive resin composition does not remain on the glass at all)

△: poor alkali solubility (slightly residual alkali-soluble radiation sensitive resin composition on glass)

×: poor alkali solubility (a large amount of residual alkali-soluble radiation sensitive resin composition on glass)

(anti-developing liquidity)

The entire surface-coated coating film was immersed in a 0.5% by weight aqueous potassium hydroxide solution for 3 minutes to be developed, and the developed glass substrate was enlarged to 50 times, and the state of the coating film was visually confirmed, thereby achieving the following three levels. Evaluation of development resistance to liquidity.

○: Good anti-developing liquidity (no cracks in the coating film at all)

△: Poor development resistance (slightly cracked in the coating film)

×: Poor development resistance (a large number of cracks in the coating film)

(fine line adhesion)

The coating film which was subjected to the exposure treatment using a negative mask was immersed in a 0.5 wt% potassium hydroxide aqueous solution for 30 seconds to be developed, and the developed glass substrate was enlarged to 50 times, and the line pattern was visually confirmed, thereby The three levels were evaluated for fine line adhesion.

○: Fine line adhesion is good (no line peeling from the substrate to form a line pattern)

△: The fine line adhesion is poor (although a line pattern is formed, a pattern is missing)

×: Fine line adhesion is poor (stripping from the substrate without forming a line pattern)

(pattern linearity)

The coating film which was subjected to the exposure treatment using a negative mask was immersed in a 0.5 wt% potassium hydroxide aqueous solution for 30 seconds to be developed, and the developed glass substrate was enlarged to 50 times, and the line pattern was visually confirmed, thereby Three levels are evaluated for pattern linearity.

○: The pattern has good linearity (no fluctuation on the edge of the line)

△: The pattern has poor linearity (the edge of the line is slightly fluctuated)

×: The pattern has poor linearity (there is a large amount of fluctuation at the edge of the line)

(film shrinkage)

The coating film subjected to the exposure and development treatment was baked at 230 ° C for 30 minutes, and it was confirmed that the film was thinned before and after the post-baking, whereby the film shrinkage was evaluated in the following three levels.

○: The film shrinks well (the film is thinner)

△: poor film shrinkage (slightly thinned film)

×: poor film shrinkage (more film thinning)

Further, the tetramethylbiphenyl type epoxy resin used was manufactured by Oil-Solid Shell Co., Ltd., and its trade name was "Epikote YX-4000", and the epoxy equivalent was 193. Further, the photopolymerization initiator was manufactured by BASF Corporation under the trade name "Irgacure-907".

From the results of Table 1, it is understood that the blending examples 1 to 10 of the alkali-soluble resins of the first to third inventions of the present invention obtained by reacting the components (b) in addition to the components (a) and (c) are used. In comparison with the blending examples 1 to 4 in which the alkali-soluble resin which does not react the component (b) is used, the development liquid resistance, the fine line adhesion, and the pattern linearity are more excellent, and the film shrinkage is also smaller.

Claims (9)

An alkali-soluble resin obtained by reacting (a) a (meth) acrylate having a cyclic structure and having a hydroxyl group, (b) a (meth) acrylate monomer, and (c) a carboxylic acid or an anhydride thereof . The alkali-soluble resin of the first aspect of the invention, wherein the (c) carboxylic acid or an anhydride thereof is (c1) a tetracarboxylic acid or an acid dianhydride thereof, and (c2) a dicarboxylic acid or an anhydride thereof. An alkali-soluble resin as claimed in claim 2, wherein (a) a (meth) acrylate having a cyclic structure and having a hydroxyl group, (b) a (meth) acrylate monomer, and (c1) a tetracarboxylate The reaction is carried out by reacting an acid or an acid dianhydride thereof, followed by reacting the (c2) dicarboxylic acid or its anhydride. An alkali-soluble resin according to claim 2, wherein (a) a (meth) acrylate having a cyclic structure and having a hydroxyl group is reacted with (c1) a tetracarboxylic acid or an acid dianhydride thereof, and then (b) The (meth) acrylate monomer is obtained by reacting (c2) a dicarboxylic acid or an anhydride thereof. The alkali-soluble resin according to any one of claims 1 to 4, wherein the (b) (meth) acrylate monomer has a hydroxyl group. An alkali-soluble resin represented by the following formula (1): (In the formula (1), X represents (a) a residue having a cyclic structure and having a hydroxyl group (meth) acrylate other than a hydroxyl group, and Y represents a carboxyl group of (c2) a dicarboxylic acid or an anhydride thereof or a residue other than an acid anhydride group, Z represents a residue other than a carboxyl group or an acid anhydride group of (c1) a tetracarboxylic acid or an acid dianhydride thereof, and A represents a hydroxyl group of a (b) (meth) acrylate monomer having a hydroxyl group. The external residue, n represents an integer from 1 to 20). An alkali-soluble resin represented by the following formula (2): (In the formula (2), X represents (a) a residue having a cyclic structure and having a hydroxyl group (meth) acrylate other than a hydroxyl group, and Z represents a (c1) addition of a tetracarboxylic acid or an acid dianhydride thereof. A residue other than a carboxyl group or an acid anhydride group, A represents a residue other than a hydroxyl group of the (b) (meth) acrylate monomer having a hydroxyl group, and n represents an integer of 1 to 20). The alkali-soluble resin according to any one of claims 1 to 7, wherein (a) the (meth) acrylate 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) acrylate monomer is a polyfunctional (meth) acrylate monomer.