KR20170141197A - Alkali-soluble resin - Google Patents

Abstract

An object of the present invention is to provide an alkali-soluble resin which is preferably used to obtain an alkali-soluble radiation-sensitive resin composition which is excellent in alkali solubility, developer resistance, fine line adhesion and pattern straightness, and has a small film shrinkage.
The alkali-soluble resin of the present invention is obtained by reacting (a) a (meth) acrylic acid ester having a cyclic structure and further having a hydroxyl group, (b) a (meth) acrylic acid ester monomer, and (c) a carboxylic acid or an acid anhydride thereof .

Description

Alkali-soluble resin {ALKALI-SOLUBLE RESIN}

The present invention relates to an alkali-soluble resin.

In general, a permanent film such as a resist material for forming an ITO electrode such as a liquid crystal display (LCD) or an organic EL display, an interlayer insulating film, a circuit protective film, a colored pigment dispersion resist for the production of a color filter of a liquid crystal display, As a forming material, a radiation-sensitive resin composition is widely used. Among them, in recent years, the demand for liquid crystal displays has increased for television applications, etc., and radiation-sensitive resin compositions are widely used in the production process.

As a radiation-sensitive resin composition, for example, Patent Document 1 discloses a method in which a reaction product of an epoxy compound having two glycidyl ether groups derived from a bisphenol group and (meth) acrylic acid is reacted with a polybasic acid carboxylic acid or an anhydride thereof A photosensitive resin composition for a black resist containing the obtained unsaturated group-containing compound as an essential component has been proposed. However, the composition is excellent in alkali solubility but has insufficient developer resistance, fine line adhesion and pattern straightness, and has a large membrane shrinkage.

Japanese Patent Application Laid-Open No. 2004-361736

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

The inventors of the present invention have found that (a) a (meth) acrylic acid ester having a cyclic structure and also having a hydroxyl group, and (c) a carboxylic acid or an acid anhydride thereof, Soluble (meth) acrylic acid ester monomer is preferably used to obtain an alkali-soluble radiation-sensitive resin composition which is excellent in alkali solubility, developer resistance, fine line adhesion and pattern straightness, and has a small film shrinkage , Thereby completing the present invention.

That is, the alkali-soluble resin of the first invention,

(a) a (meth) acrylic ester having a cyclic structure and also having a hydroxyl group,

(b) a (meth) acrylic acid ester monomer, and

(c) a carboxylic acid or an acid anhydride thereof

And the like.

The alkali-soluble resin of the first invention of the present invention is characterized in that (c) the carboxylic acid or an acid anhydride thereof is (c1) a tetracarboxylic acid or its acid dianhydride, and (c2) a dicarboxylic acid or an acid anhydride thereof .

The alkali-soluble resin according to the first aspect of the present invention comprises (a) a (meth) acrylic acid ester having a cyclic structure and also having a hydroxyl group, (b) a (meth) acrylic acid ester monomer, (c1) a tetracarboxylic acid or And then reacting the acid dianhydride with (c2) a dicarboxylic acid or an acid anhydride thereof.

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

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

The alkali-soluble resin of the second invention contains,

(1): < EMI ID =

[Chemical Formula 1]

(Wherein X represents a residue other than the hydroxyl group of the (meth) acrylic acid ester having a cyclic structure and also having a hydroxyl group, and Y represents a carboxyl group of the dicarboxylic acid or an acid anhydride thereof (c2) Or a residue other than an acid anhydride group, and Z represents a residue other than the carboxyl group or the acid anhydride group of the tetracarboxylic acid or its acid dianhydride (c1), and A represents a hydroxyl group of the (meth) acrylic acid ester monomer having a hydroxyl group , And n represents an integer of 1 to 20).

The alkali-soluble resin of the third aspect of the present invention is an alkali-soluble resin represented by the following general formula (2)

(2)

Wherein X represents (a) a residue other than the hydroxyl group of the (meth) acrylate ester having a cyclic structure and also having a hydroxyl group, and Z represents (c1) a residue of a tetracarboxylic acid or its acid dianhydride A represents a residue other than the hydroxyl group of the (meth) acrylic acid ester monomer (b) having a hydroxyl group, and n represents an integer of 1 to 20), wherein A represents a residue other than a carboxyl group or an acid anhydride group.

The alkali-soluble resins of the first to third inventive inventions preferably have (a) a (meth) acrylic acid ester having a cyclic structure and also having a hydroxyl group, having a bisphenol skeleton.

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

The alkali-soluble resin of the first to the third inventions of the present invention comprises (a) a (meth) acrylic ester having a cyclic structure and also having a hydroxyl group, and (c) a carboxylic acid or an acid anhydride thereof, Soluble methacrylic acid ester monomer, it is preferably used for obtaining an alkali-soluble radiation-sensitive resin composition which is excellent in alkali solubility, developer resistance, fine line adhesion, pattern straightness, and film shrinkage.

<< Alkali-soluble resin of the first invention >>

The alkali-soluble resin of the first invention of the present invention,

(a) a (meth) acrylic ester having a cyclic structure and also having a hydroxyl group,

(b) a (meth) acrylic acid ester monomer, and

(c) a carboxylic acid or an acid anhydride thereof

And the like.

&Lt; Component (a) &gt;

(a) The cyclic structure of a (meth) acrylic acid ester having a cyclic structure and also having a hydroxyl group (hereinafter, simply referred to as a component (a)) refers to a structure in which the atoms constituting the molecule are cyclically bonded. The ring structure is not particularly limited, and examples thereof include an aromatic ring, an alicyclic ring, a condensed ring and a heterocyclic ring. These may be present alone in the component (a), or two or more of them may coexist.

Examples of the component (a) include, but are not limited to, bisphenol fluorene (epoxy) acrylate, biscresol fluorene (epoxy) acrylate, bisphenyl phenol fluorene (epoxy) Containing (epoxy) acrylate such as A-type (epoxy) acrylate, bisphenol AP (epoxy) acrylate and bisphenol F (epoxy) acrylate, trisphenol skeleton-containing (epoxy) acrylate, tetraphenol skeleton (Epoxy) acrylate, naphthalene skeleton-containing (epoxy) acrylate, novolac skeleton-containing (epoxy) acrylate, adamantane skeleton-containing (epoxy) acrylate, isocyanuric acid skeleton- . These may be used alone or in combination of two or more.

In the present specification, the term "(meth) acrylate" refers to an ester of (meth) acrylic acid with a compound containing a hydroxyl group or an epoxy group. In the present specification, (meth) acrylic acid refers to acrylic acid or methacrylic acid.

The component (a) preferably has a bisphenol skeleton and more preferably a fluorene skeleton because the component (a) is excellent in heat resistance, adhesion, and chemical resistance when it is used as a cured film.

The number of hydroxyl groups contained in the component (a) is not particularly limited, but is preferably 2 to 5 in one molecule, and more preferably 2 in number. 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, more preferably 1 to 2.

&Lt; Component (b) &gt;

(meth) acrylic acid ester monomer (hereinafter, also simply referred to as component (b)) is not particularly limited, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, (Meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol propane tri (meth) Acrylate, trimethylol ethane di (meth) acrylate, trimethylol ethane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (Meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol mono (meth) (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (Meth) acrylic acid ester monomer having a cyclic structure such as isocyanuric acid ethylene oxide modified di (meth) acrylate and 2-hydroxy-3-phenoxypropyl acrylate, Ester monomers, dendrimer type acrylates, hyperbranched type acrylates, and the like. These may be used alone or in combination of two or more. Among them, it is preferable to use a (meth) acrylic acid ester monomer having no cyclic structure, a dendrimer type acrylate, and a hyperbranched type acrylate.

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

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 in one molecule, and more preferably 1. The number of carbon-carbon double bonds (C = C bonds) contained in 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 because of its excellent curability of the film. Here, the polyfunctional means that two or more carbon-carbon double bonds are contained in one molecule.

&Lt; Component (c) &gt;

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

(c1) tetracarboxylic acid or its acid dianhydride (hereinafter, simply referred to as a component (c1)), and (c2) a dicarboxylic acid or its acid (Hereinafter, simply referred to as component (c2)).

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

Examples of the component (c2) include, but are not limited to, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, Glutaric acid, trimellitic acid and the like, and acid anhydrides thereof. These may be used alone or in combination of two or more.

<Reaction of components (a) to (c)

For example, when the components (c1) and (c2) are used as the component (c), the components (a) to (c) (B2) and (c1), and then reacting the component (c2), or a method of reacting the component (a) and the component (c1) c2) component, and the like.

In the reaction of the components (a) to (c), the amount of each component to be used is not particularly limited, but the reactive functional group of the component (b) is usually 1 to 60 parts by mol per 100 parts by mol of the hydroxyl group of the component (a) Preferably 3 moles or more and less than 30 moles, and the carboxyl group or the acid anhydride group of the component (c) is usually 30 to 100 moles, preferably 50 moles or more and less than 100 moles, in terms of the acid anhydride group . Here, the acid anhydride group is defined as a -CO-O-CO- group, and two carboxyl groups of a tetracarboxylic acid or dicarboxylic acid correspond to one acid anhydride group. If the amount of the reactive functional group of the component (b) is less than 1 part by mole, it will cause deterioration in developing properties. If the amount is more than 60 parts by mole, the development will be deteriorated. When the carboxyl group or the acid anhydride group of the component (c) is converted into an acid anhydride group and the amount is less than 30 parts by mole, it is difficult to sufficiently introduce the polymerizable double bond groups necessary for high sensitivity and sufficiently increase the molecular weight Is not obtained and unreacted materials remain, which causes deterioration of developability. 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 preferably from 99: 1 to 10:90, Is selected in the range of 95: 5 to 20: 80. When the molar ratio of the component (c2) is less than 1, the resin viscosity increases and the workability deteriorates. In addition, since the molecular weight becomes excessively large, the unexposed portion does not dissolve in the developer and a desired pattern may not be obtained. When the molar ratio of the component (c2) is more than 90, the molecular weight is small, so that sticking remains in the coated film after prebaking.

The reaction temperature of the components (a) to (c) is not particularly limited, but is preferably 80 to 130 ° C, and more preferably 90 to 110 ° C. If the reaction temperature is lower than 80 deg. C, the reaction may not proceed smoothly and unreacted materials may remain. When the temperature exceeds 130 deg. C, the polymerization of components (a) and (b) . The reaction time is not particularly limited, but is preferably 2 to 24 hours, more preferably 4 to 20 hours. If the reaction time is less than 2 hours, the reaction may not sufficiently proceed and unreacted materials may remain. If the reaction time exceeds 24 hours, the polymerization of the component (a) and the component (b) may partially take place, .

The reaction of the components (a) to (c) may be carried out in the presence of a solvent, a catalyst or the like, if necessary. Further, in the reaction, in addition to the components (a) to (c), other monomers may be optionally reacted. Other monomers include, but are not particularly limited to, polyhydric alcohols, epoxy compounds, isocyanate compounds, silane coupling agents, and the like. These may be used alone or in combination of two or more.

<< Second alkali-soluble resin of the present invention >>

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

(3)

(Wherein X represents a residue other than the hydroxyl group of the (meth) acrylic acid ester having a cyclic structure and also having a hydroxyl group, and Y represents a carboxyl group of the dicarboxylic acid or an acid anhydride thereof (c2) Or a residue other than an acid anhydride group, and Z represents a residue other than the carboxyl group or the acid anhydride group of the tetracarboxylic acid or its acid dianhydride (c1), and A represents a hydroxyl group of the (meth) acrylic acid ester monomer having a hydroxyl group , And n represents an integer of 1 to 20).

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

<< Third alkali-soluble resin of the present invention >>

The alkali-soluble resin of the third aspect of the present invention is an alkali-soluble resin represented by the following general formula (2)

[Chemical Formula 4]

Wherein X represents (a) a residue other than the hydroxyl group of the (meth) acrylate ester having a cyclic structure and also having a hydroxyl group, and Z represents (c1) a residue of a tetracarboxylic acid or its acid dianhydride A represents a residue other than the hydroxyl group of the (meth) acrylic acid ester monomer (b) having a hydroxyl group, and n represents an integer of 1 to 20), wherein A represents a residue other than a carboxyl group or an acid anhydride group.

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

The acid value of the alkali-soluble resin of the first to third inventive inventive inventions 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, the solubility of the unexposed portion in the developer is lowered, and the time required for development is prolonged, and a desired pattern may not be obtained. When the acid value is more than 120 mgKOH / g, The solubility of the unexposed portion in the developing solution becomes excessively high, and the developing margin is not taken, and the desired pattern may not be obtained in some cases.

The weight average molecular weight of the alkali-soluble resins of the first to third inventive inventive inventions is not particularly limited, but is preferably 1,000 to 50,000, more preferably 1,000 to 20,000, and even more preferably 1,000 to 10,000. If the weight average molecular weight is less than 1,000, sticking remains on the coated film after pre-baking. On the other hand, if the weight average molecular weight is more than 50,000, the resin viscosity increases and the workability is deteriorated. The desired pattern may not be obtained.

<< Alkali-soluble type radiation-sensitive resin composition >>

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

Here, the radiation sensitivity refers to a property of causing a chemical reaction by various kinds of radiation. Examples of such radiation include visible light, ultraviolet light, electron beam, X-ray,? -Ray,? -Ray and? There is a line. Of these, ultraviolet rays are the most preferable radiation in view of economy and efficiency. As ultraviolet rays, ultraviolet light emitted 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 with a wavelength shorter than that of ultraviolet rays has high chemical reactivity and, in theory, is superior to ultraviolet rays, but ultraviolet rays are practical from the viewpoint of economy.

The alkali-soluble type radiation-sensitive resin composition may optionally contain other components in addition to the component (A). The other components are not particularly limited, and examples thereof include a compound having an epoxy group (B) (hereinafter, simply referred to as a component (B)), a photopolymerization initiator (C) (Hereinafter also simply referred to as component (D)), a solvent, a pigment, an epoxy group curing accelerator, a thermal polymerization inhibitor, an antioxidant, an adhesion auxiliary agent, an interface Active agents, defoaming agents and the like.

Examples of the component (B) include, but are not limited to, phenol novolak type epoxy resins, cresol novolak type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, Epoxy resins such as epoxy resins, epoxy resins and alicyclic epoxy resins, epoxy resins such as phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl A compound having at least one epoxy group such as an ether or glycidyl methacrylate, 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 (B), the content thereof is not particularly limited, but is preferably 5 to 50 parts by weight, more preferably 10 to 30 parts by weight, per 100 parts by weight of the component (A) More preferable. If the content is less than 5 parts by weight, the properties after curing, particularly, the alkali resistance may be insufficient. If the content is more than 50 parts by weight, cracks may occur during curing and adhesion may be easily lowered.

The component (C) is not particularly limited, and examples thereof include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone , and p-tert-butyl acetophenone; benzophenones such as benzophenone, 2-chlorobenzophenone and p, p'-bisdimethylaminobenzophenone; benzophenones such as benzyl, benzoin, benzoin methyl ether, Benzoin isobutyl ether; benzoin ethers such as benzyl dimethyl ketal, thioxanthene, 2-chlorothioxanthene, 2,4-diethyl thioxanthene, 2-methyl thioxanthene, 2 - isopropyl thioxanthrene, and an anthraquinone such as 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone and 2,3-diphenylanthraquinone, azobisisobutyronitrile Organic peroxides such as nitrile, benzoyl peroxide, cumene peroxide and the like There may be mentioned thiol compound such as 2-mercapto benzoimidazole, 2-mercapto-benzoxazole, 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 thereof is not particularly limited, but is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight per 100 parts by weight of the component (A) More preferable. If the content is less than 0.1 part by weight, the speed of photopolymerization may decrease and the sensitivity may be lowered. If the content exceeds 30 parts by weight, the light may hardly reach the substrate, and the adhesion between the substrate and the resin may be deteriorated.

Examples of the component (D) include, but are not limited to, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) Acrylate, trimethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane mono (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylol ethane di (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol tri (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol mono (meth) acrylate, dipentaerythritol di Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and glycerol (meth) acrylate. 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 thereof is not particularly limited, but is preferably 50 parts by weight or less, more preferably 40 parts by weight or less based on 100 parts by weight of the component (A) Do. When the content is more than 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 glycol 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; Ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; Hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, Esters such as methyl, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate and ethyl lactate . These may be used alone or in combination of two or more.

When the alkali-soluble type radiation-sensitive resin composition contains a solvent, the content thereof is not particularly limited and varies depending on the desired viscosity. However, when the concentration of solids in the alkali-soluble type radiation-sensitive resin composition is from 1 to 50% by weight By weight, more preferably 5 to 30% by weight.

Examples of the pigment include, but are not limited to, carbon black, chromium oxide, iron oxide, titanium black, aniline black, cyanine black, perylene black and the like. These may be used alone or in combination of two or more.

When the alkali-soluble radiation-sensitive resin composition contains a pigment, its content is not particularly limited, but is preferably 50 to 150 parts by weight, more preferably 80 to 120 parts by weight, per 100 parts by weight of the component (A) . If the content is less than 50 parts by weight, the light shielding property may not be sufficient. If the content is more than 150 parts by weight, the content of the alkali-soluble resin as an original binder is decreased. Therefore, There is a case where an undesirable problem occurs.

The alkali-soluble type radiation-sensitive resin composition preferably further contains the component (B) and the component (C) in addition to the component (A) in that sufficient properties after curing can be obtained.

(D) is added in an amount of not more than 50 parts by weight based on 100 parts by weight of the component (A), in addition to the component (A) in that the radiation- .

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

<< Hard Goods >>

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

The method of curing the alkali-soluble radiation-sensitive resin composition is not particularly limited, but it is possible to use a solution of the alkali-soluble radiation-sensitive resin composition by any one of dipping, spraying, slit coater and spinner , A method of applying light (such as ultraviolet rays, radiation, etc.) to the substrate and then performing development processing and post-baking.

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

<< Curing membrane >>

Hereinafter, the cured film obtained by curing the above-described 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 탆, more preferably 1 to 5 탆. If the film thickness is less than 0.1 탆, the light shielding property may not be sufficient. If the film thickness exceeds 10 탆, the entire film may not be sufficiently cured.

The use of the cured film is not particularly limited, and examples thereof include a protective film such as a color filter, a liquid crystal display element, an integrated circuit element, and a solid-state imaging element, an interlayer insulating film, a color resist, and a solder resist used for manufacturing a printed wiring board.

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, pattern straightness, and film shrinkage.

<< Color Filter >>

The cured film described above may be a color filter.

Since the color filter is composed of the cured film described above, it is excellent in developer resistance, fine line adhesion, pattern straightness, and film shrinkage

Example

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the following examples. Hereinafter, &quot; part &quot; or &quot;% &quot; means &quot; part by weight &quot; or &quot;% by weight &quot;

(Example 1)

In a 300 ml separable flask, 133.9 g of a methoxybutyl acetate solution of bisphenol fluorene type epoxy acrylate, 9.0 g of pentaerythritol (tri / tetra) acrylate, and 10 g of 3,3 ', 4,4'- And 11.7 g of the carboxylic acid dianhydride were mixed, and the temperature was gradually raised, and the mixture was reacted at 100 to 105 ° C for 14 hours. After confirming disappearance of the acid anhydride, 16.7 g of methoxybutyl acetate was added to dilute and 8.6 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 to 95 ° C for 4 hours to obtain 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 bisphenol fluorene-type epoxy acrylate and 11.7 g of 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride were mixed and gradually heated The reaction was carried out at 100 to 105 ° C for 14 hours. After disappearance of the acid anhydride was confirmed, 16.7 g of methoxybutyl acetate was added to dilute, and 9.0 g of pentaerythritol (tri / tetra) acrylate and 8.6 g of 1,2,3,6-tetrahydrophthalic anhydride were mixed , And the reaction was carried out 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. The obtained alkali-soluble resin 2 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)

In a 300 ml separable flask, 133.9 g of a methoxybutyl acetate solution of bisphenol fluorene-type epoxy acrylate and 9.0 g of dipentaerythritol (penta / hexa) acrylate and 3,3 ', 4,4'-biphenyltetra And 11.7 g of carboxylic acid dianhydride were mixed, and the temperature was gradually raised, and the mixture was reacted at 100 to 105 ° C for 14 hours. After confirming disappearance of the acid anhydride, 16.7 g of methoxybutyl acetate was added to dilute and 8.6 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 to 95 ° C for 4 hours to obtain 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 bisphenol fluorene-type epoxy acrylate and 11.7 g of 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride were mixed and gradually heated The reaction was carried out at 100 to 105 ° C for 14 hours. After disappearance of the acid anhydride was confirmed, 16.7 g of methoxybutyl acetate was added to dilute, 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 a methoxybutyl acetate solution of adamantanetriol monoacrylate, 8.5 g of pentaerythritol (tri / tetra) acrylate, and 3,3 ', 4,4'-biphenyltetra And 11.1 g of carboxylic acid dianhydride were mixed, and 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, 10.7 g of methoxybutyl acetate was added to dilute and 8.1 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 to 95 캜 for 4 hours to obtain 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 acid dianhydride were mixed and gradually heated And the reaction was carried out at 100 to 105 ° C for 14 hours. After disappearance of the acid anhydride was confirmed, 10.7 g of methoxybutyl acetate was added to dilute, and 8.5 g of pentaerythritol (tri / tetra) acrylate and 8.1 g of 1,2,3,6-tetrahydrophthalic anhydride were mixed , And the reaction was carried out at 90 to 95 캜 for 4 hours to obtain an alkali-soluble resin 6. The disappearance of the acid anhydride was confirmed by IR spectrum. The obtained alkali-soluble resin 6 had a solid content of 56.1%, an acid value of 48.2 mgKOH / g (85.9 mgKOH / g in terms of solid content) and a weight average molecular weight of 3,300.

(Example 7)

138.6 g of a methoxybutyl acetate solution of bisphenol fluorene type epoxy acrylate, 9.0 g of pentaerythritol (tri / tetra) acrylate and 9.0 g of anhydrous pyromellitic acid were mixed in a 300 ml separable flask, and the temperature was gradually raised to 100 The reaction was carried out at ~ 105 ° C for 14 hours. After confirming disappearance of the acid anhydride, 14.5 g of methoxybutyl acetate was added to dilute and 8.9 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 to 95 ° C for 4 hours to obtain 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 bisphenol fluorene-type epoxy acrylate and 9.0 g of anhydrous pyromellitic acid were mixed, and the mixture was gradually heated to react at 100 to 105 ° C for 14 hours. After disappearance of the acid anhydride was confirmed, 14.5 g of methoxybutyl acetate was added to dilute, and 9.0 g of pentaerythritol (tri / tetra) acrylate and 8.9 g of 1,2,3,6-tetrahydrophthalic anhydride were mixed , And the reaction was carried out 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 trisphenol methane type epoxy acrylate and 9.0 g of 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride were mixed and gradually heated The reaction was carried out at 100 to 105 ° C for 14 hours. After disappearance of the acid anhydride was confirmed, 16.6 g of methoxybutyl acetate was added to dilute, and 9.0 g of dipentaerythritol (penta / hexa) acrylate and 4.6 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 9. The disappearance of the acid anhydride was confirmed by IR spectrum. 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.

(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 acid dianhydride were mixed and gradually heated And the reaction was carried out at 100 to 105 ° C for 14 hours. After confirming disappearance of the acid anhydride, 20.4 g of methoxybutyl acetate was added to dilute, and 9.0 g of dipentaerythritol (penta / hexa) acrylate and 16.4 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 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 bisphenol fluorene-type epoxy acrylate and 12.9 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 disappearance of the acid anhydride, 10.3 g of methoxybutyl acetate was added to dilute and 9.5 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 to 95 ° C for 4 hours to obtain 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 acid dianhydride were mixed and gradually heated And the reaction was carried out at 100 to 105 ° C for 14 hours. After confirming the disappearance of the acid anhydride, 4.1 g of methoxybutyl acetate was added to dilute and 8.9 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 to 95 캜 for 4 hours to obtain 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)

152.5 g of a methoxybutyl acetate solution of bisphenol fluorene-type epoxy acrylate and 9.9 g of anhydrous pyromellitic acid were mixed in a 300 ml separable flask, and 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, 7.8 g of methoxybutyl acetate was added to dilute and 9.8 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 to 95 캜 for 4 hours to obtain 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 respective components were mixed at the weight ratios shown in Table 1 below to prepare an alkali-soluble radiation-sensitive resin composition.

The alkali-soluble radiation-sensitive resin compositions obtained in Formulation Examples 1 to 10 and Comparative Formulation Examples 1 to 4 were evaluated for alkali solubility, developer resistance, fine line adhesion, pattern straightness, and film shrinkage by the following methods. The results are shown in Table 1 below.

(Alkali soluble)

The prebaked coating film that had not been subjected to the exposure treatment was immersed in a 0.5 wt% aqueous solution of potassium hydroxide for 30 seconds and developed. The glass substrate after development was enlarged 50 times and the remaining resin was visually observed to determine alkali solubility. Respectively.

A: Good alkali-solubility (no alkali-soluble radiation-sensitive resin composition remained on glass)

?: Poorly soluble in alkali (a residue of alkali-soluble type radiation-sensitive resin composition remained on glass)

X: A resin having poor alkali solubility (with a large amount of alkali-soluble radiation-sensitive resin composition remaining on glass)

(Developer resistance)

The coated film exposed on the entire surface was immersed in a 0.5 wt% aqueous solution of potassium hydroxide for 3 minutes to be developed. The developed glass substrate was magnified 50 times and visually confirmed the state of the coating film. Respectively.

A: Good developer resistance (no cracks in the coating film at all)

?: Poor developer resistance (a little cracks in the coating film)

X: poor developer resistance (a lot of cracks are contained in the coating film)

(Fine wire adhesion)

The coated film exposed by using a negative mask was immersed in a 0.5 wt% aqueous solution of potassium hydroxide for 30 seconds to be developed. The developed glass substrate was enlarged 50 times and the line pattern was visually observed to obtain fine line adhesion in three steps Respectively.

Good: Good adhesion to fine wires (line pattern formed without peeling off the substrate)

: Good line adhesion (line pattern formed but pattern missing)

X: poorly adhered to fine wires (one having no line pattern formed by peeling off from the substrate)

(Pattern straightness)

The coated film exposed by using a negative mask was immersed in a 0.5 wt% aqueous solution of potassium hydroxide for 30 seconds and developed. The developed glass substrate was magnified 50 times and the line pattern was visually observed. Respectively.

○: Good pattern straightness (no rattling on edge of line)

?: Poor pattern linearity (with slight rattling at the edge of the line)

X: Poor pattern straightness (with a lot of rattling on the edge of the line)

(Film shrinkage)

The coated film subjected to the exposure and development treatment was subjected to post-baking at 230 캜 for 30 minutes, and film reduction was confirmed before and after the post-baking, thereby evaluating film shrinkage in the following three steps.

Good: Good film shrinkage (less film loss)

?: Poor film shrinkage (slight decrease in film thickness)

X: The membrane shrinkage was poor (the membrane shrinkage was large)

The tetramethylbiphenyl-type epoxy resin used was Epikote YX-4000, manufactured by Yucca Shell Co., Ltd., epoxy equivalent 193. The photopolymerization initiator is "Irgacure 907" manufactured by BASF Corporation.

The results of Table 1 show that Formulation Examples 1 to 10 using the alkali-soluble resins of the first to third inventions obtained by reacting the components (a) and (c) in addition to the component (b) Compared with Comparative Formulation Examples 1 to 4 in which an alkali-soluble resin not reacted was used, it was found that the developer resistance, the fine line adhesion and the pattern straightness were excellent and the film shrinkage was small.

Claims (9)

(a) a (meth) acrylic ester having a cyclic structure and also having a hydroxyl group,
(b) a (meth) acrylic acid ester monomer, and
(c) a carboxylic acid or an acid anhydride thereof
To obtain an alkali-soluble resin. The method according to claim 1,
(c) an alkali-soluble resin in which the carboxylic acid or its acid anhydride is (c1) a tetracarboxylic acid or an acid dianhydride thereof, and (c2) a dicarboxylic acid or an acid anhydride thereof. 3. The method of claim 2,
(meth) acrylic acid ester monomer having a cyclic structure and further having a hydroxyl group, (b) a (meth) acrylic acid ester monomer, and (c1) a tetracarboxylic acid or its acid dianhydride, An alkali-soluble resin obtained by reacting a dicarboxylic acid or an acid anhydride thereof. 3. The method of claim 2,
(meth) acrylic acid ester monomer having a cyclic structure and further having a hydroxyl group, (c1) a tetracarboxylic acid or an acid anhydride thereof, (b) a (meth) acrylic acid ester monomer, and (c2) An alkali-soluble resin obtained by reacting a dicarboxylic acid or an acid anhydride thereof. 5. The method according to any one of claims 1 to 4,
(b) an alkali-soluble resin in which the (meth) acrylic acid ester monomer has a hydroxyl group. (1): &lt; EMI ID =
[Chemical Formula 1]

(Wherein X represents a residue other than the hydroxyl group of the (meth) acrylic acid ester having a cyclic structure and also having a hydroxyl group, and Y represents a carboxyl group of the dicarboxylic acid or an acid anhydride thereof (c2) Or a residue other than an acid anhydride group, and Z represents a residue other than the carboxyl group or the acid anhydride group of the tetracarboxylic acid or its acid dianhydride (c1), and A represents a hydroxyl group (meth) acrylate monomer having a hydroxyl group And n is an integer of 1 to 20). (2): &lt; EMI ID =
(2)

Wherein X represents (a) a residue other than the hydroxyl group of the (meth) acrylate ester having a cyclic structure and also having a hydroxyl group, and Z represents a residue of the (c1) tetracarboxylic acid or its acid dianhydride A represents a residue other than the hydroxyl group of the (meth) acrylic acid ester monomer (b) having a hydroxyl group, and n represents an integer of 1 to 20. The alkali solubility Suzy. 8. The method according to any one of claims 1 to 7,
(a) an alkali-soluble resin having a cyclic structure and also having a hydroxyl group, wherein the (meth) acrylic acid ester has a bisphenol skeleton. 9. The method according to any one of claims 1 to 8,
(b) an alkali-soluble resin in which the (meth) acrylic acid ester monomer is a polyfunctional (meth) acrylic acid ester monomer.