JP2003165830A - Photopolymerizable unsaturated resin, method for producing the same and alkali-soluble radiation- sensitive resin composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide both a photopolymerizable unsaturated resin and an alkali- soluble radiation-sensitive resin composition comprising the resin. <P>SOLUTION: This photopolymerizable unsaturated resin is represented by general formula (1) [wherein, X denotes a bisphenol (or a biscresol) fluorene epoxy acrylic acid derivative; n denotes an integer of 1-20; Y denotes a residue after removing an acid anhydride group from a dicarboxylic acid anhydride; and Z denotes a residue after removing acid anhydride groups from a tetracarboxylic acid dianhydride] and has ≥1,500 number-average molecular weight. The resin is obtained by reacting the dicarboxylic acid anhydride with the tetracarboxylic acid dianhydride so as to provide (1:99) to (65:35) molar ratio. The alkali-soluble radiation-sensitive resin composition comprises the resin. A film obtained from the composition has excellent characteristics such as heat resistance, transparency, exposure, developability and chemical resistance. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel photopolymerizable unsaturated resin, a method for producing the same, and an alkali-soluble radiation-sensitive resin composition using the same. More specifically, the present invention is a photopolymerizable unsaturated resin useful as a photopolymerizable component in an alkali-soluble radiation-sensitive resin composition that is suitably used for various purposes, and a method for efficiently producing the same. And a protective film for a color filter, a liquid crystal display device, an integrated circuit device, a solid-state imaging device, etc., which contains a photopolymerizable unsaturated resin and provides a cured film excellent in heat resistance, transparency, adhesion, chemical resistance, and the like. The present invention relates to an alkali-soluble radiation-sensitive resin composition suitable as a material for forming an interlayer insulating film, a binder composition for a color resist, a solder resist used in manufacturing a printed wiring board, and the like.

[0002]

2. Description of the Related Art Conventionally, a screen printing method has been used for forming a protective film for a color filter, a liquid crystal display device, an integrated circuit device, a solid-state image pickup device, an eyebrow insulating film or a resist pattern on a printed wiring board. However, this screen printing method cannot support recent high-density devices. For this reason, dry film type photoresists and liquid resists have been proposed, but in the case of dry film type photoresists, bubbles are likely to be generated during thermocompression bonding, heat resistance and adhesion are not sufficient, and the cost is low. There are problems such as being expensive.

On the other hand, in the liquid resist, there is sticking after the pre-baking, which causes mask stains.
There is a problem that the contact exposure method, which is advantageous for improving the contrast of the pattern shape, cannot be applied. Further, since the commercially available ones currently use an organic solvent as a developing solution, there is a problem of air pollution and the solvent is expensive. Further, Japanese Patent Application Laid-Open No. 61-243869 discloses a radiation-sensitive resin composition which can be developed with a weak alkaline aqueous solution containing a phenol novolac resin as a main component, but is sufficiently resistant to high temperature, acidic and alkaline conditions. It is not durable, and there is a problem in that the adhesion with the substrate decreases after processing.

Therefore, in order to solve such a problem, a photopolymerizable compound whose cured product has a fluorene skeleton excellent in transparency and heat resistance has recently been proposed.
However, although this photopolymerizable compound can solve the above problems to some extent by using it, it does not sufficiently satisfy the required performance.

For example, Japanese Patent Laid-Open No. 4-345673,
JP-A-4-345608, JP-A-4-35545
No. 0 and JP-A-4-363311 disclose heat-resistant liquid resists and color filter materials using a reaction product of an epoxy acrylate having a bisphenolfluorene structure and an acid anhydride, but these are also disclosed. Similarly, there is sticking after pre-baking, which causes mask stains, and therefore not only the problem that the contact exposure method, which is advantageous in improving the contrast of the pattern shape, cannot be applied, but also the carboxyl group content increases, so that the alkali of the cured product There is a problem that the solubility becomes high and the developability is poor.

Further, the epoxy resin disclosed in Japanese Patent Laid-Open No. 4-345673 has a low solubility in an ordinary organic solvent, and the solvent is limited and it is difficult to form a film thickness when used as a liquid resist. There are drawbacks. Also, when a coating film prepared by printing or solid coating with a roll coater is heat-cured, sticking remains after removing the solvent by prebaking, resulting in poor workability.

On the other hand, JP-A-5-339356, JP-A-6-1938 and JP-A-7-3122 disclose epoxy acrylate compounds having a bisphenolfluorene structure, an acid anhydride, and an acid dianhydride. Are simultaneously reacted to increase the molecular weight, and a carboxyl group is introduced, the general formula (7):

[0008]

[Chemical 9]

(Where X is equation (8):

[0010]

[Chemical 10]

The group represented by, Y is a residue of the acid anhydride excluding the acid anhydride group, Z is a residue of the acid dianhydride excluding the acid anhydride group, and m and k are It shows the degree of polymerization, m / k
A photopolymerizable unsaturated compound represented by a molar ratio of 1/99 to 90/10) is disclosed.

However, when this compound is used,
Although the sticking after prebaking is eliminated, in the compound, since the acid anhydride not only reacts with the hydroxyl group of the epoxy acrylate but also participates in the condensation reaction, it becomes difficult to control the molecular weight and the acid value. When the solid content concentration increases, the solution viscosity of the resist increases, so that not only the workability at the time of solid content dissolution, filtration, or coating deteriorates, but also the film thickness on the surface of the substrate varies due to the deterioration of coating characteristics, resulting in development. There is a concern that the characteristics may vary.

Further, Japanese Patent Application Laid-Open No. 9-325494 discloses a composition containing an epoxy acrylate compound having a bisphenolfluorene structure and an acid dianhydride alone as a main component and containing a carboxyl group-containing alternating copolymer as a main component. However, in this composition, a large amount of unreacted epoxy acrylate compound remains, which may reduce water resistance, solvent resistance, and alkali solubility. In order to reduce the amount of unreacted epoxy acrylate compound, it is preferable to increase the use ratio of acid dianhydride, but in this case, since the molecular weight increases, the solution viscosity becomes high and the workability is likely to be significantly deteriorated.

[0014]

Under these circumstances, the present invention efficiently produces a photopolymerizable unsaturated resin which does not have the above-mentioned drawbacks and whose molecular weight can be easily controlled. Method, and containing the photopolymerizable unsaturated resin, the coating becomes sticking-free after prebaking, and the cured film after light irradiation has heat resistance (small film shrinkage after heat treatment), transparency, adhesion, and hardness. A radiation-sensitive resin composition which has excellent chemical resistance (small film shrinkage after immersion in an alkaline solution), can be developed with a weak alkaline aqueous solution, and whose viscosity can be easily adjusted to an appropriate solution viscosity. It was made for the purpose of providing.

[0015]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that an epoxy (meth) acrylate having a bisphenolfluorene skeleton is reacted with a tetracarboxylic dianhydride. By using a two-step reaction in which the terminal hydroxyl group is blocked with a dicarboxylic acid anhydride after being made into an oligomer by the above method, a novel photopolymerizable unsaturated resin having a carboxyl group which does not have the above-mentioned drawbacks and whose molecular weight can be easily controlled is obtained. Being done, and
This photopolymerizable unsaturated resin, a compound containing an epoxy group, and a composition containing a photopolymerization initiator, as a radiation-sensitive resin composition, was found to be suitable for the purpose, based on this finding The invention was completed.

That is, the present invention has the general formula (1):

[0017]

[Chemical 11]

(Where X is the general formula (2):

[0019]

[Chemical 12]

A group represented by the formula (in the formula, R _1's each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen group, and R _2's each independently represent Represents a hydrogen atom or a methyl group), and n is 1 to 20.
And Y is a residue of the dicarboxylic acid anhydride excluding the acid anhydride group, and Z is a residue of the tetracarboxylic dianhydride excluding the acid anhydride group). Is 1,
A photopolymerizable unsaturated resin of 500 or more, which is obtained by reacting a dicarboxylic acid anhydride and a tetracarboxylic acid dianhydride in a molar ratio of 1:99 to 65:35. Provide an unsaturated resin.

The present invention also has the general formula (3):

[0022]

[Chemical 13]

An epoxy compound represented by the formula (4) is reacted with (meth) acrylic acid to give a compound represented by the general formula (4):

[0024]

[Chemical 14]

After obtaining a (meth) acrylic acid ester derivative represented by the formula (5):

[0026]

[Chemical 15]

A tetracarboxylic acid dianhydride represented by the formula (wherein Z is a residue of the tetracarboxylic acid dianhydride excluding the acid anhydride group) is reacted, and then the general formula (6):

[0028]

[Chemical 16]

The dicarboxylic acid anhydride represented by the formula (wherein Y is a residue of the dicarboxylic acid anhydride excluding the acid anhydride group) is a dicarboxylic acid anhydride and a tetracarboxylic acid dianhydride. A general formula (1): characterized by adding and reacting at a ratio of 1:99 to 65:35.

[0030]

[Chemical 17]

(Where X is the general formula (2):

[0032]

[Chemical 18]

The group represented by, R ₁ , R ₂ , Y and Z are the same as described above, and n is an integer of 1 to 20), and the number average molecular weight is 1500 or more. A method for producing an unsaturated resin is provided.

The present invention further includes (A) the photopolymerizable unsaturated resin, (B) a compound having an epoxy group, and (C).
An alkali-soluble radiation-sensitive resin composition containing a photopolymerization initiator is provided.

In a preferred embodiment, the alkali-soluble radiation-sensitive resin composition of the present invention further comprises (D)
At least one selected from photopolymerizable monomers and oligomers is contained in an amount of 50 parts by weight or less per 100 parts by weight of the component (A).

[0036]

BEST MODE FOR CARRYING OUT THE INVENTION The photopolymerizable unsaturated resin of the present invention is
General formula (1):

[0037]

[Chemical 19]

(Wherein X, Y, Z and n are as described above), and a new resin having a number average molecular weight of 1500 or more (hereinafter sometimes referred to as the resin of the present invention). is there. As will be described later in detail, for example, this resin is reacted with a (meth) acrylic acid ester derivative and tetracarboxylic acid dianhydride (residue is Z), and then dicarboxylic acid anhydride (residue is Y). , Dicarboxylic acid anhydride and tetracarboxylic acid dianhydride are added at a molar ratio of 1:99 to 65:35 and reacted.

The resin of the present invention is characterized in that it has a structure in which hydroxyl groups at both ends are blocked by a dicarboxylic acid anhydride, and that the dicarboxylic acid anhydride residue is substantially not present in the polymer chain. On the other hand, the photopolymerizable unsaturated compound represented by the general formula (7) described in JP-A-5-339356 is a resin of the present invention in that it has a dicarboxylic acid anhydride residue in the polymer chain. In addition, unlike the resin of the present invention, the terminal hydroxyl group is not always blocked with a dicarboxylic acid anhydride. This production method of the general formula (7) is obtained by simultaneously reacting an epoxy acrylate compound having a bisphenolfluorene structure with an acid anhydride and an acid dianhydride, and is different from the method of the present invention.

The photopolymerizable unsaturated resin represented by the general formula (1) can be produced extremely efficiently according to the following method. First, general formula (3):

[0041]

[Chemical 20]

An epoxy compound (3) represented by is prepared. In this epoxy compound (3), R _1's are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,
Represents a phenyl group or a halogen group. As the alkyl group having 1 to 5 carbon atoms, a methyl group or an ethyl group is preferably used. A methyl group is more preferably used, and a biscresolfluorene type epoxy compound in which both R ₁ are methyl groups is preferably used. As a halogen group, B
r, Cl and F are preferably used.

The epoxy compound represented by the general formula (3) can be easily obtained, for example, by reacting bisphenolfluorene or biscresolfluorene with epihalohydrin such as epichlorohydrin. A commercial item is also used as the bisphenol fluorene type epoxy compound.

Next, the epoxy compound of the general formula (3) is reacted with (meth) acrylic acid to give the general formula (4).

[0045]

[Chemical 21]

A (meth) acrylic acid ester derivative represented by is obtained. The epoxy compound represented by the general formula (3) may be used alone or in combination of two or more kinds. Further, acrylic acid and methacrylic acid may be used in combination.

Next, the obtained (meth) acrylic acid ester derivative represented by the general formula (4) and the general formula (5):

[0048]

[Chemical formula 22]

In a suitable solvent, a tetracarboxylic dianhydride represented by the formula: wherein Z is the same as above,
React.

After completion of this reaction, the reaction product and the compound of the general formula (6):

[0051]

[Chemical formula 23]

The dicarboxylic acid anhydride represented by the formula (Y is the same as above) is reacted in a suitable solvent.

In this reaction, it is necessary to add and react the dicarboxylic acid anhydride and the tetracarboxylic acid dianhydride used in the reaction in a molar ratio of 1:99 to 65:35. . Preferably 5: 95-60:
The ratio is 40, more preferably 5:99 to 5
It is 0:50. That is, the dicarboxylic acid in the total acid anhydride to be added needs to be 1 mol% to 65 mol%. When the proportion of the dicarboxylic acid anhydride is less than 1 mol% of the total acid anhydride, the molecular weight tends to be high and the resin viscosity tends to be high. If the resin viscosity is high, the workability during the preparation of the resist solution will be poor.If the molecular weight is large, the resin in the unexposed area will not dissolve in the developer when the film is formed, and the desired pattern will be obtained when developed. The problem of not presenting is likely to occur. Further, when the proportion of the dicarboxylic acid anhydride exceeds 65 mol% of the total acid anhydride, the molecular weight of the obtained resin becomes small and sticking remains in the coating film after prebaking, or heat resistance or solvent resistance. There may be a problem with sex.

As the solvent used for the reaction of the (meth) acrylic acid ester derivative with the dicarboxylic acid anhydride or the tetracarboxylic acid dianhydride, each component used in the reaction and the reaction product can be dissolved, and As long as it has no adverse effect, it can be used without particular limitation. For example, a cellosolve-based solvent such as ethyl cellosolve acetate or butyl cellosolve acetate can be preferably used.

The reaction is preferably carried out at a temperature at which the tetracarboxylic dianhydride and dicarboxylic acid anhydride and the hydroxyl group in the (meth) acrylic acid ester derivative of the formula (4) react quantitatively. For example, in the reaction of a (meth) acrylic acid ester derivative and a tetracarboxylic acid dianhydride, it is usually 100 to 130 ° C., preferably 115 to 1
It is carried out at 25 ° C. When the reaction temperature exceeds 130 ° C,
Polymerization of the (meth) acrylic acid ester derivative partially occurs, causing a sharp increase in the molecular weight.
If the amount is less than the range, the reaction may not proceed smoothly and unreacted tetracarboxylic acid dianhydride may remain.

The reaction of the reaction product of the (meth) acrylic acid ester derivative with the tetracarboxylic acid dianhydride and the dicarboxylic acid anhydride is preferably carried out at 80 to 110 ° C, more preferably 80 to 90 ° C. Done in. When the reaction temperature exceeds 110 ° C, condensation of carboxyl groups and hydroxyl groups occurs, which causes an increase in molecular weight.
If the amount is less than the range, the reaction may not proceed smoothly, and unreacted dicarboxylic acid anhydride may remain.

In the production of the resin of the present invention, (meth)
The total amount of acid anhydride groups of tetracarboxylic dianhydride and dicarboxylic acid anhydride is 0.6 to 1 equivalent, preferably 0.75 equivalent or more and less than 1 equivalent per 1 equivalent of hydroxyl group of the acrylic acid ester derivative. It is preferable to react in a ratio. When the total amount of acid anhydride groups is less than 0.6 equivalent, it is difficult to sufficiently introduce the polymerizable double bond group necessary for sufficiently increasing the molecular weight and achieving high sensitivity. On the contrary, when the acid anhydride group exceeds 1 equivalent, not only the molecular weight becomes difficult to increase, but also unreacted tetracarboxylic dianhydride or dicarboxylic acid anhydride remains, which deteriorates the developability. It causes to invite.

Examples of the tetracarboxylic acid dianhydride represented by the general formula (5) include pyromellitic dianhydride,
Examples thereof include aromatic polyvalent carboxylic acid anhydrides such as benzophenone tetracarboxylic acid dianhydride, biphenyl tetracarboxylic acid dianhydride and biphenyl ether tetracarboxylic acid dianhydride.

Examples of the dicarboxylic acid anhydride represented by the general formula (6) include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Examples thereof include methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride and glutaric anhydride.

The molecular weight and acid value of the photopolymerizable unsaturated resin of the present invention can be controlled by controlling the reaction conditions when the (meth) acrylic acid ester derivative and the tetracarboxylic acid dianhydride are reacted to give the general formula ( The value of n in 1) can be adjusted.

The alkali-soluble radiation-sensitive resin of the present invention can be mixed with a photopolymerization initiator and cured to give a cured product having high transparency and excellent heat resistance.

Next, the alkali-soluble radiation-sensitive resin composition of the present invention comprises (A) the photopolymerizable unsaturated resin of the present invention,
It is obtained by blending (B) a compound having an epoxy group and (C) a photopolymerization initiator.

As the photopolymerizable unsaturated resin as the component (A),
The resin of the present invention may be used alone or in combination of two or more kinds. For example, a bisphenol fluorene type resin and a biscresol fluorene type resin may be combined and used as the photopolymerizable unsaturated resin of the component (A).

As the compound having an epoxy group as the component (B), a compound having at least one epoxy group is used. For example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, and other epoxy resins,
Phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate,
Examples thereof include diglycidyl isocyanurate, allyl glycidyl ether, and glycidyl methacrylate.
As the compound of the component (B), the compound of the component (B) may be used alone or in combination of two or more kinds.

The photopolymerization initiator as the component (C) is the above-mentioned (A).
It is a compound that acts as a photopolymerization initiator of the component, and (D) component (described later) such as a photopolymerizable monomer or an oligomer contained as necessary, and / or a compound having a sensitizing effect. As the component (C), for example, acetophenones such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p-tert-butylacetophenone, Benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, thioxanthene Sulfur compounds such as 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, and 2-isopropylthioxanthene, , 2-ethylanthraquinone, octamethylanthraquinone, 1,2-
Anthraquinones such as benzanthraquinone and 2,3-diphenylanthraquinone, organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2 Examples thereof include thiol compounds such as mercaptobenzothiazole.

These compounds may be used alone or in combination of two or more. Also,
A compound which does not act as a photopolymerization initiator by itself, but which can increase the ability of the photopolymerization initiator by using it in combination with the above compound, can be added. Examples of such compounds include tertiary amines such as triethanolamine, which are effective when used in combination with benzophenone.

The radiation-sensitive resin composition of the present invention comprises (A)
It is preferable to contain 5 to 50 parts by weight of the component (B) and 0.1 to 30 parts by weight of the component (C) per 100 parts by weight of the component, and particularly 10 to 30 parts by weight of the component (B) and It is preferable to contain the component (C) in an amount of 1 to 20 parts by weight. When the content of the component (B) is less than 5 parts by weight based on 100 parts by weight of the component (A), the properties of the composition of the present invention after curing, particularly alkali resistance, are insufficient and exceed 100 parts by weight. In that case, cracking occurs during curing, and the adhesiveness is likely to decrease. Further, if the content of the component (C) is less than 0.1 parts by weight per 100 parts by weight of the component (A), the photopolymerization rate tends to be slow and the sensitivity tends to be lowered. On the other hand, when the amount exceeds 30 parts by weight, it is difficult for light to reach the substrate, so that the adhesion between the substrate and the resin tends to deteriorate.

In the resin composition of the present invention, if necessary, as the component (D), a monomer or oligomer which can be polymerized by light can be added in accordance with the physical properties of its intended use. Examples of such a light-polymerizable monomer or oligomer include the following monomers and oligomers. For example, monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate, or ethylene glycol di (meth) acrylate, diethylene glycol di (meth). ) Acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol Di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra ( Data) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate of a (meth) acrylic acid esters. These monomers or oligomers may be used alone or in combination of two or more.

The monomer or oligomer as the component (D) acts as a viscosity modifier or a photo-crosslinking agent, and is blended, if necessary, within a range that does not impair the properties of the resin composition of the present invention. . Usually, at least one of the above-mentioned monomers and oligomers is added in an amount of 50 parts by weight or less based on 100 parts by weight of the photopolymerizable unsaturated resin as the component (A). If the amount of the monomer or oligomer used exceeds 50 parts by weight, the sticking property after prebaking may be a problem.

In the radiation-sensitive resin composition of the present invention, if necessary, for example, an epoxy group curing accelerator, a thermal polymerization inhibitor, an antioxidant, an adhesion aid, etc., as long as the object of the present invention is not impaired. , A surfactant, an antifoaming agent and the like are added.

Examples of the epoxy group curing accelerator include amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts, and methylol group-containing compounds. By mixing a small amount of an epoxy group curing accelerator and heating the coating film, the resulting resist coating has heat resistance, solvent resistance, acid resistance, plating resistance, adhesion,
Various characteristics such as electric characteristics and hardness are improved.

As the thermal polymerization inhibitor, hydroquinone,
Hydroquinone monomethyl ether, pyrogallol, t
Examples include ert-butylcatechol and phenothiazine.

By adding an adhesion aid, the adhesiveness of the resulting composition is improved. As an adhesion aid,
Preferably, a silane compound (functional silane coupling agent) having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group or an epoxy group is used. Specific examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane and γ-glycine. Sidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned.

Examples of the defoaming agent include silicone type,
Examples thereof include fluorine-based and acrylic-based compounds.

By adding a surfactant,
The obtained composition is easy to apply, and the flatness of the obtained film is improved. As the surfactant, for example, BM-10
00 (manufactured by BM Chemie), Megafac F142D, F172, F173 and F183 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-135, FC.
-170C, Florard FC-430 and FC-4
31 (Sumitomo 3M Limited), Surflon S-11
2, S-113, S-131, S-141 and S-145 (manufactured by Asahi Glass Co., Ltd.), SH-28PA, S.
H-190, SH-193, SZ-6032, SF-8
428, DC-57 and DC-190 (manufactured by Toray Silicone Co., Ltd.) and the like.

In the radiation-sensitive resin composition of the present invention, the above-mentioned component (A), component (B), component (C) and optionally component (D) or other additives are usually added to an organic solvent. It can be prepared by dissolving and mixing uniformly. Such an organic liquid agent is not particularly limited as long as it does not react with each component in the composition and is soluble in each other. For example, 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, ethylene glycol monoethyl ether; methyl cellosolve acetate, ethyl cellosolve acetate, etc. Ethylene glycol alkyl ether acetates; diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and other diethylene glycols; propylene glycol methyl ether Ether acetate, propylene glycol alkyl ether acetates such as propylene glycol ethyl ether acetate: toluene, aromatic hydrocarbons such as xylene;
Ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; and ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methyl Ethyl propionate,
Ethyl ethoxy acetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3
-Esters such as methyl ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate and the like can be mentioned.

Of these, glycol ethers, alkylene glycol alkyl ether acetates, diethylene glycol dialkyl ethers, ketones and esters are preferable, and ethyl 3-ethoxypropionate, ethyl lactate, propylene glycol monomethyl ether acetate are particularly preferable. Ethylene glycol monoethyl ether acetate and methyl amyl ketone. These solvents may be used alone,
You may mix and use 2 or more types.

The composition of the present invention thus prepared is usually used after being filtered with, for example, a Millipore filter having a pore size of about 1.0 to 0.2 μm.

As a method for applying the solution of the radiation-sensitive resin composition of the present invention to a substrate, any method such as a dipping method, a spray method, a roller coater, a slit coater, a bar coater, and a spinner can be used. Can also be adopted. By these methods, the resin composition solution is applied to a thickness of about 1 to 30 μm, and then the solvent is removed to form a film.

The radiation used in the radiation-sensitive resin composition of the present invention includes visible light, ultraviolet light, and
Electron beams, X-rays, α-rays, β-rays, γ-rays and the like can be used. Of these, ultraviolet rays are the most preferable radiations from the viewpoint of economy and efficiency.
Ultraviolet light emitted from a lamp such as a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, or an arc lamp or a xenon lamp can be preferably used as the ultraviolet ray used in the present invention. The radiation having a shorter wavelength than that of ultraviolet rays has high chemical reactivity and is theoretically superior to ultraviolet rays, but ultraviolet rays are practical from the viewpoint of economy.

The photosensitive layer made of the resin composition provided on the substrate is selectively exposed with the above-mentioned radiation, and then developed with a developing solution to remove the non-irradiated portion to form a thin film. Patterning is performed. Examples of the developing method include a puddle method, a dipping method, and a rocking dipping method.

Examples of the developing solution include an alkaline aqueous solution and an organic solvent capable of dissolving the composition of the present invention.

As the base used for preparing the alkaline aqueous solution, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate,
Ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, pyrelidine, 1 , 8-diazabicyclo (5,4,0) -7-undecene, 1,5-diazabicyclo (4,3,0) -5-
Nonane is mentioned, and sodium carbonate and tetramethylammonium hydroxide are preferable.

Further, if necessary, an aqueous solution prepared by adding an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol or ethylene glycol, a surfactant and the like to the above alkaline aqueous solution can be used as a developing solution.

The development of the resin composition of the present invention is usually 10 to 10.
It can be carried out at a temperature of 50 ° C., preferably 20 to 40 ° C., using a commercially available developing machine or ultrasonic cleaning machine.

After the alkali development, it is desirable to heat and apply an epoxy curing treatment in order to improve the alkali resistance. In the resin composition of the present invention, by heat treatment, not only the durability to strong alkaline water is significantly improved, but also various properties such as adhesion to glass, metal such as copper, heat resistance, surface hardness, etc. improves. With respect to the heating temperature and the heating time under the heat curing conditions, for example, 80 to 200 ° C. and 10 to 120 minutes can be mentioned.

Next, one example of the method for producing a film by photopolymerization of the radiation-sensitive resin composition of the present invention will be described.

First, a resist solution containing the resin composition is coated on a substrate by an arbitrary method. Although spin coating is used in the examples, coating methods such as dip coating, bar coating, roll coating, and slit coating can of course be used. After coating the resist solution, pre-baking is performed to evaporate the solvent. next,
Contact exposure is carried out using an ultra-high pressure mercury lamp or the like, and the unexposed area is developed with an aqueous solution of sodium carbonate of about 1% by weight and further washed with water. Then, the coating film is completely dried by post-baking at a temperature of about 200 ° C., and a desired coating film having excellent heat resistance, transparency, adhesiveness, hardness, solvent resistance, alkali resistance and the like can be obtained.

The radiation-sensitive resin composition of the present invention is useful as an insulating film, an insulating paint, an adhesive, a printing ink, a coating agent, etc., especially as a color filter material used in a liquid crystal display device or a solid-state image pickup device. . Also,
The cured product has excellent hardness, solder heat resistance, transparency, acid resistance,
It exhibits alkali resistance, solvent resistance, insulation resistance, electrolytic corrosion resistance, and plating resistance, as well as film smoothness and adhesion to substrates when used as a coating agent.

For example, as a color filter material, the resin composition of the present invention can be suitably used as a color filter protective film by blending a leveling agent and the like. In this case, ITO (indium tin oxide) can be sputtered on the protective film at a high temperature of 250 ° C., and it can sufficiently withstand strong acid and strong alkali treatment during patterning of ITO. The conventional protective film has an I
Considering that TO could not be sputtered, the resin composition of the present invention is also excellent in this respect.

By mixing a pigment or carbon black into the above composition, it can be suitably used as a color resist ink or a black matrix resist ink. In this case, a known organic pigment or inorganic pigment can be used as the pigment.

The cured film obtained by curing the composition of the present invention is excellent in heat resistance, transparency, adhesion to a substrate, acid resistance, alkali resistance, solvent resistance, surface hardness and the like. Furthermore, since this cured film is an organic coating film, it has a low dielectric constant. Therefore, the composition of the present invention can be used in many applications other than the above color filters. For example,
Materials for protective films of electronic parts (for example, materials for forming protective films used in liquid crystal display devices including color filters, integrated circuit devices, solid-state imaging devices, etc.);
Or a material for forming a flattening film; a solder resist used in the production of a printed wiring board; or an alkali-soluble photosensitive composition suitable for forming columnar spacers that substitute for bead spacers in liquid crystal display devices; Used for. Furthermore, the composition of the present invention is used for various optical parts (lenses, LEDs, plastic films, substrates,
Suitable for materials such as optical discs; coating agents for forming a protective film for the optical parts; adhesives for optical parts (adhesives for optical fibers, etc.); coating agents for manufacturing polarizing plates; photosensitive resin compositions for hologram recording, etc. Used for.

[0093]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Example 1: Production of resin 1) In a 500 mL four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235) and 110 mg of tetramethylammonium chloride, 2,6-di-te.
100 mg of rt-butyl 4-methylphenol and 72.0 g of acrylic acid were charged, and this was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 mL / min.
Next, the temperature is gradually raised while the solution becomes cloudy,
It was heated to 0 ° C. and completely dissolved. Here, the solution gradually became a transparent viscous paste, but the stirring was continued as it was. During this period, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target. Then, the mixture was cooled to room temperature to obtain a colorless and transparent bisphenolfluorene type epoxy acrylate represented by the formula (4).

Then, the above-obtained bisphenolfluorene type epoxy acrylate 30 is obtained.
After adding and dissolving 600 g of propylene glycol monomethyl ether acetate to 7.0 g, 80.5 g of benzophenone tetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually heated to 110
Reacted at ~ 115 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and allowed to react at 90 ° C. for 6 hours to obtain a resin 1 (represented by the general formula (1). In the formula, Y / Z molar ratio = 50.
0 / 50.0) was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.

Example 2 Production of Resin 2 Using 307.0 g of the bisphenol fluorene type epoxy acrylate produced in Example 1, 600 g of propylene glycol monomethyl ether acetate was added to form a solution,
Benzophenone tetracarboxylic dianhydride 104.7 g
And 1 g of tetraethylammonium bromide were mixed and gradually heated to react at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 15.2 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and allowed to react at 90 ° C. for 6 hours to obtain a resin 2 (represented by the general formula (1). Where Y /
Z molar ratio = 23.5 / 76.5) was obtained. The disappearance of the acid anhydride was confirmed by the IR spectrum as in Example 1 above.

Example 3 Production of Resin 3 Using 307.0 g of the bisphenol fluorene type epoxy acrylate produced in Example 1, 600 g of propylene glycol monomethyl ether acetate was added to form a solution,
67.6 g of benzophenone tetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide were mixed, gradually heated and reacted at 110 to 115 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 48.6 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to give a resin 3 ( Where Y /
Z molar ratio = 60/40) was obtained. IR disappearance of acid anhydride
Confirmed by spectrum.

Example 4 Production of Resin 4 Using 307.0 g of the bisphenol fluorene type epoxy acrylate produced in Example 1, 600 g of propylene glycol monomethyl ether acetate was added to form a solution,
96.6 g of benzophenone tetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually heated to react at 110 to 115 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 45.6 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and allowed to react at 90 ° C. for 6 hours to obtain a resin 4 (represented by the general formula (1)). Where Y /
Z molar ratio = 50.0 / 50.0) was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.

Example 5 Production of Resin 5 In a 500 mL four-necked flask, 244 g of a biscresolfluorene type epoxy resin (epoxy equivalent 244), 110 mg of tetramethylammonium chloride and 2,6-di-te.
100 mg of rt butyl 4-methylphenol and 72.0 g of acrylic acid were charged. The mixture was heated to 90 to 100 ° C. while blowing air at a rate of 25 mL / min to obtain a cloudy solution. The temperature of this cloudy solution is gradually raised to 1
Heated to 20 ° C. The cloudy solution became increasingly clear and viscous as the temperature increased. After clouding, the acid value was measured at regular intervals, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. 12 until the acid value reaches the target
It took time. Then, the mixture was cooled to room temperature to obtain a colorless and transparent solid biscresolfluorene type epoxy acrylate represented by the general formula (4).

Then, the above-mentioned biscresolfluorene type epoxy acrylate 316 thus obtained is obtained.
To g, 600 g of propylene glycol monomethyl ether acetate was added and dissolved, and then 80.5 g of benzophenone tetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually heated to 110 to 11
The reaction was carried out at 5 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 1,2,3,6-tetrahydrophthalic anhydride 38.
0 g were mixed and reacted at 90 ° C. for 6 hours to give the compound represented by the general formula (1)
Resin 5 represented by the formula (in the formula, Y / Z molar ratio = 50.0 / 5
0.0) was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.

Comparative Example 1 Production of Resin 6 Using 307.0 g of the bisphenol fluorene type epoxy acrylate produced in Example 1, 600 g of propylene glycol monomethyl ether acetate was added to form a solution,
Benzophenone tetracarboxylic acid dianhydride 102.3 g
And 1 g of tetraethylammonium bromide were mixed and gradually heated to react at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 0.5 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to give a resin 6 represented by the general formula (1). Obtained. However, this resin 6 has a Y / Z molar ratio of 0.8 / 9 in the formula.
It is 9.2 and is a resin that does not fall within the scope of the present invention.
The disappearance of the acid anhydride was confirmed by IR spectrum.

Comparative Example 2 Production of Resin 7 Using 307.0 g of the bisphenol fluorene type epoxy acrylate produced in Example 1, 600 g of propylene glycol monomethyl ether acetate was added to form a solution,
48.3 g of benzophenone tetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually heated to react at 110 to 115 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 68.4 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to give a resin 7 represented by the general formula (1). Obtained. The disappearance of the acid anhydride was confirmed by IR spectrum. This resin 7
In the formula, Y / Z molar ratio = 75/25, which is a resin that does not fall within the scope of the present invention.

Comparative Example 3 Production of Resin 8 Using 307.0 g of the bisphenol fluorene type epoxy acrylate produced in Example 1, 600 g of propylene glycol monomethyl ether acetate was added to form a solution,
80.5 g of benzophenone tetracarboxylic dianhydride,
1,2,3,6-tetrahydrophthalic anhydride 38.0
g, and 1 g of tetraethylammonium bromide are mixed,
The temperature is gradually raised and the reaction is performed at 110 to 115 ° C. for 6 hours, and then the resin 8 represented by the general formula (7) (in the formula, Y / Z molar ratio = 5) is used.
0.0 / 50.0) was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum. This resin 8 does not have the structure of the resin of the present invention.

Comparative Example 4 Production of Resin 9 Using 307.0 g of the bisphenolfluorene type epoxy acrylate produced in Example 1, 300 g of propylene glycol monomethyl ether acetate was added to form a solution,
114 g of 1,2,3,6-tetrahydrophthalic anhydride,
And 1 g of tetraethylammonium bromide were mixed, the temperature was gradually raised, and the reaction was carried out at 90 to 100 ° C. for 4 hours to obtain a resin 9. The disappearance of the acid anhydride was confirmed by IR spectrum.

Table 1 shows the equivalent ratios and properties of the resins 1 to 5 obtained in Examples 1 to 5 and the resins 6 to 9 obtained in Comparative Examples 1 to 4 at the time of production.

[0106]

[Table 1]

The equivalence ratio and each evaluation item in Table 1 are as follows. 1) The equivalent ratio represents the equivalent ratio of bisphenol (or biscresol) fluorene type epoxy acrylate / benzophenone tetracarboxylic dianhydride / 1,2,3,6-tetrahydrophthalic anhydride. 2) To measure the resin acid value, 1 g of the sample was precisely weighed in a 100 ml Erlenmeyer flask, 30 ml of acetone was added and dissolved, and then bromothymol blue solution was used as an indicator.
The titration was performed with a 1 M NaOH aqueous solution. 3) The number average molecular weight is a conversion value measured by a gel permeation chromatography method. 4) Solution viscosity is 50% by weight of resin using B type viscometer
Was dissolved in propylene glycol monomethyl ether acetate so that

As is clear from the results shown in Table 1, the resins 1 to 5 according to the present invention show almost the same theoretical value and actual measured value of the resin acid value, so that a condensation reaction occurs during the reaction. However, it is considered that the resin having the structure represented by the general formula (1) is obtained. Further, it was not confirmed that the molecular weight increased with time, and it was proved that the production method was stable even in industrialization.

On the other hand, the resin 6 has a Y / Z molar ratio of 1/9.
Since it was smaller than 9, the molecular weight was large and the viscosity was also high. The resin 7 has a Y / Z molar ratio of 65/35.
Larger, smaller molecular weight and lower solution viscosity. Further, as shown in the physical properties (decrease in acid value, increase in viscosity) of the resin 8, even if the mixing ratio of acid anhydride / acid dianhydride is the same, the molecular weight of the resin 8 increases due to the condensation reaction, and The viscosity has increased. It was confirmed that this tendency increased as the reaction time increased. Also, resin 9
Had a low molecular weight and a low solution viscosity.

(Examples 6 to 12 and Comparative Examples 5 to 8) The photopolymerizable unsaturated resins (resins 1 to 9) obtained in Examples 1 to 5 and Comparative Examples 1 to 4 are used and shown in Table 2. A resist solution having a composition was prepared. In addition, Example 13 is a 1: 1 composition of resin 1 (bisphenol fluorene type resin) and resin 5 (biscresol fluorene type resin).

[0111]

[Table 2]

The tetramethylbiphenyl type epoxy resin used is "Epicoat YX-4000", trade name, manufactured by Yuka Shell Co., Ltd., with an epoxy equivalent of 193. Irgacure 907 is manufactured by Ciba Specialty Chemicals.

The obtained resist solution was applied on a glass substrate using a spinner and then prebaked on a hot plate at 90 ° C. for 120 seconds to form a coating film having a thickness of about 2 μm. A mask having a predetermined pattern is placed on this coating film, and a wavelength of 4
100 nm of ultraviolet rays with a light intensity of 9.5 mW / cm ² at 05 nm
The coating film was irradiated and exposed so that the energy amount was 0 mJ / cm ² . After the irradiation, development treatment was carried out at 25 ° C. for 30 seconds using a 1 wt% sodium carbonate aqueous solution to remove the unexposed portion of the coating film. Then, a rinse treatment was performed with ultrapure water. The glass substrate having the thin film subjected to the exposure treatment and the development treatment was left in an oven at 200 ° C. for 30 minutes (post-baking treatment), and the thin film was heat-cured to obtain a heat-cured film.

The above-mentioned coating film formation, exposure / development and heating steps, and the heat-cured film thus obtained were evaluated for the respective resins as follows.

(1) Drying property of coating film The drying property of the coating film after prebaking was measured according to JIS-K-5.
It evaluated according to 400. The evaluation criteria are as follows. ○: No sticking is observed. Δ: Slight sticking is observed. X: Remarkably sticking is recognized.

(2) Developability With respect to the developability with respect to an alkaline aqueous solution, the pre-baked coating film which has not been subjected to the exposure treatment is immersed in an aqueous solution of 1% by weight of sodium carbonate for 30 seconds for development, and the glass substrate after development is exposed to 50%.
It was magnified twice and the remaining resin was visually evaluated. The evaluation criteria are as follows. ◯: Good developability (no resist left on the glass) Δ: Poor developability (some resist left on the glass) X: Poor developability (on the glass) A lot of resist remains)

(3) Exposure sensitivity In the exposure / development process, a step tablet (a negative mask having an optical density of 12 steps) was brought into close contact with the coating film as a mask for exposure / development. Then, the number of steps of the remaining step tablets was counted. The numbers in Table 3 are the number of steps. In this evaluation method, the higher the sensitivity, the greater the number of remaining stages.

(4) Hardness of coating film The hardness of the coating film (heat-curing film) is JIS-K-5400.
It measured according to the test method of. Using a pencil hardness tester,
The highest hardness that does not scratch the coating when a load of 9.8 N was applied to the heat-cured film was defined as the hardness. The pencil used as a control is "Mitsubishi High Uni."

(5) Adhesion Adhesion between the coating film (heat-cured film) and the glass substrate was measured by a peeling test. The coating film was cross-cut so as to make at least 100 squares, then peeled off using Cellotape (registered trademark), and the state of cross-cut was evaluated by magnifying 50 times with an optical microscope. . The evaluation criteria are as follows. ◯: No peeling is observed. X: Peeling is recognized even a little.

(6) The heat-resistant heat-cured film was placed in an oven at 250 ° C. for 3 hours to be subjected to cure baking, and the rate of change in film thickness before and after cure baking ((film thickness before cure bake−film thickness after cure bake) /
(Film thickness before cure bake)) × 100 was determined. The evaluation criteria are as follows. ◯: Heat resistance is excellent (film thickness change rate of less than 5%) Δ: Heat resistance is somewhat good (film thickness change rate of 5% to less than 10%) ×: Heat resistance is poor (film thickness change rate of 10%) that's all)

(7) Chemical resistance The heat cured film was immersed in the following chemicals under the following conditions. (i) Acidic solution: Immersed in 5 wt% HCl aqueous solution for 24 hours at room temperature (ii) Alkaline solution ii-1: Immersed in 5 wt% NaOH aqueous solution for 24 hours at room temperature ii-2: In 4 wt% KOH aqueous solution Immersion at 50 ° C. for 10 minutes ii-3: Immersion in 1% by weight NaOH aqueous solution at 80 ° C. for 5 minutes (iii) Solvent iii-1: N-methyl pyrrolidone immersion at 40 ° C. for 10 minutes iii-2: N-methyl The rate of change in film thickness before and after immersion in pyrrolidone for 5 minutes at 80 ° C. ((film thickness before immersion-film thickness after immersion) / (film thickness before immersion)) × 100 was determined. The evaluation criteria are as follows. ◯: Excellent chemical resistance (film thickness change rate of less than 5% in all solutions) Δ: Chemical resistance slightly good (film thickness change rate of 5% or more and less than 10% in any solution) ×: The chemical resistance is inferior (thickness change rate of 10% or more in any solution). The above results are shown in Table 3.

[0122]

[Table 3]

In Comparative Example 5, the unexposed portion was not dissolved during patterning and patterning could not be performed. Therefore, the subsequent evaluation was stopped.

As is clear from the results in Table 3, Example 6
The resins of .about.12 were able to achieve the desired physical properties. Further, the composition of the resin 1 (bisphenol fluorene type resin) and the resin 5 (biscresol fluorene type resin) of Example 13 could also achieve good physical properties. However, as in Comparative Example 5, at the molar ratio of Y / Z = 0.8 / 99.2, the unexposed portion was not dissolved in the developing solution because the molecular weight of the resin was too large, and I can't get the pattern. Further, as in Comparative Example 6, at the molar ratio of Y / Z = 75/25, the molecular weight of the resin becomes too small, which is contrary to Comparative Example 5, so that the change in film thickness after cure bake, and further after post bake. The film thickness changes significantly after immersion in a solvent, resulting in poor heat resistance and solvent resistance.

From the above results, the radiation-sensitive resin composition of the present invention has heat resistance, transparency, adhesion, hardness, solvent resistance,
It was found that a protective film excellent in alkali resistance and the like can be provided.

[0126]

INDUSTRIAL APPLICABILITY The photopolymerizable unsaturated resin of the present invention is useful as a photopolymerizable component in an alkali-soluble radiation-sensitive resin composition which is preferably used for various purposes.

The radiation-sensitive resin composition of the present invention contains this photopolymerizable unsaturated resin, and has a heat resistance higher than that of conventional resins.
A coating film having excellent transparency can be formed. In addition, the coating film after pre-baking is free from sticking, contact exposure is possible, and the resolution is improved. Moreover, since the cured film obtained by heating is excellent in acid resistance, alkali resistance, solvent resistance, surface hardness, etc., it is not only useful for permanent protection masks such as solder resists, but also for printed wiring. It can be used in a wide range of fields such as plate-related etching resists, interlayer insulating materials, radiation-sensitive adhesives, paints, photosensitive liquids for screen printing and resist inks.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kei Kitano             236 Nakai, Tatsuno-cho, Tatsuno-shi, Hyogo Nagase             Chemtex Co., Ltd. Harima No. 1 Factory F term (reference) 2H025 AA04 AA08 AA10 AA13 AA14                       AB13 AB15 AB16 AB17 AC01                       AD01 BC32 BC42 BC74 BC85                       CA01 CA18 CA30 CC20 FA03                       FA17 FA29                 4J029 AA07 AB01 AC01 AD01 AE11                       CA04 CB04A FC35 GA02                       GA13 GA17 GA22 GA23 HA01                       HB06                 4J036 AA01 DA04 DA05 DA09 DB14                       DB17 DB21 DB22 DB23 DC02                       DC41 EA01 EA02 EA03 EA04                       EA10 HA01 HA02 HA03 JA09

Claims (4)

[Claims] 1. General formula (1): (In the formula, X is a general formula (2): (In the formula, R _1's each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen group, and R _2's each independently represent a hydrogen atom or A methyl group), n is an integer of 1 to 20, Y is a residue excluding the acid anhydride group of the dicarboxylic acid anhydride, and Z is an acid anhydride group of the tetracarboxylic acid dianhydride. A photopolymerizable unsaturated resin having a number average molecular weight of 1,500 or more and a dicarboxylic acid anhydride and a tetracarboxylic acid dianhydride in a molar ratio of 1: 9.
A photopolymerizable unsaturated resin obtained by reacting so as to have a ratio of 9 to 65:35. 2. General formula (3): An epoxy compound represented by the formula (4) is reacted with (meth) acrylic acid to give a compound represented by the general formula (4): After the (meth) acrylic acid ester derivative represented by the formula (5) is obtained, this is represented by the general formula (5): (In the formula, Z is a residue of the tetracarboxylic dianhydride excluding the acid anhydride group), and reacted with a tetracarboxylic dianhydride, and then the compound represented by the general formula (6): (In the formula, Y is a residue of the dicarboxylic acid anhydride excluding the acid anhydride group), and the dicarboxylic acid anhydride and the tetracarboxylic acid dianhydride have a molar ratio of 1 : 99 to 65:35, and the reaction is carried out by adding it in the general formula (1): (In the formula, X is a general formula (2): The group represented by, R ₁ , R ₂ , Y and Z are the same as above, and n is an integer of 1 to 20), and the number average molecular weight is a photopolymerizable unsaturated resin of 1500 or more. Manufacturing method. 3. An alkali-soluble radiation-sensitive resin containing (A) the photopolymerizable unsaturated resin according to claim 1, (B) a compound having an epoxy group, and (C) a photopolymerization initiator. Composition. 4. Further, at least one selected from (D) photopolymerizable monomer and oligomer is contained in a ratio of 50 parts by weight or less per 100 parts by weight of component (A).
The alkali-soluble radiation-sensitive resin composition according to claim 3.