JP2003176343A - Photopolymerizable unsaturated resin, method for producing the same and alkali-soluble radiation- sensitive resin composition produced by using the resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alkali-soluble radiation-sensitive resin and a composition containing the resin. <P>SOLUTION: The photopolymerizable unsaturated resin is expressed by general formula (1) (X<SB>1</SB>, X<SB>2</SB>and X are each a bisphenol fluorene-type epoxy acrylic acid derivative; l/m is 1/99 to 99/1; (l+m) is an integer of 1-20; Y is a residue obtained by removing an acid anhydride group from a dicarboxylic acid anhydride; and Z is a residue obtained by removing acid anhydride groups from a tetracarboxylic acid dianhydride), having a number-average molecular weight of ≥1,500 and produced by reacting the dicarboxylic acid anhydride and the tetracarboxylic acid dianhydride at a molar ratio of 1:99 to 65:35. The invention further provides an alkali-soluble radiation-sensitive resin composition containing the resin. The coating film produced from the composition has excellent properties such as heat-resistance, transparency, exposure-developing property 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. Of the general formula (9):

[0008]

[Chemical 11]

(Where X is the expression (10):

[0010]

[Chemical 12]

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 p and q are It shows the degree of polymerization, p / q
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 for achieving the above-mentioned object, the present inventors have found that an epoxy (meth) acrylate having two or more kinds of bisphenolfluorene skeletons is converted into tetracarboxylic dianhydride. By using a two-step reaction in which the terminal hydroxyl group is blocked with a dicarboxylic acid anhydride after being converted into an oligomer by reaction with a novel photopolymerizable monomer having a carboxyl group which does not have the above-mentioned drawbacks and whose molecular weight is easily controlled. A saturated resin is obtained, and a composition containing the photopolymerizable unsaturated resin, a compound having an epoxy group, and a photopolymerization initiator can be adapted to the purpose as a radiation-sensitive resin composition. The present invention has been completed based on this finding. Furthermore, this resin has a single bisphenolfluorene skeleton, compared with a system in which a resin having epoxy (meth) acrylate as a starting material is mixed, without lowering the coating properties such as heat resistance, solvent resistance, and hardness, Process characteristics such as developability can be improved.

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

[0017]

[Chemical 13]

(Wherein X ₁ is the general formula (2):

[0019]

[Chemical 14]

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 X
₂ is a general formula (3):

[0021]

[Chemical 15]

A group represented by the formula (in the formula, R _3'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 _4's each independently represent A hydrogen atom or a methyl group), and R ₃ and R ₁ are different substituents, R ₂ and R ₄ may be the same or different, and X is X ₁ or X. ₂ , 1 / m is 1/99 to 99/1, and (l + m)
Is an integer of 1 to 20, Y is a residue of the dicarboxylic acid anhydride excluding the acid anhydride group, and Z is a residue of the tetracarboxylic acid dianhydride excluding the acid anhydride group). A photopolymerizable unsaturated resin having a number average molecular weight of 1,500 or more, and reacting a dicarboxylic acid anhydride and a tetracarboxylic acid dianhydride in a molar ratio of 1:99 to 65:35 A photopolymerizable unsaturated resin obtained by the above is provided.

The present invention also has the general formula (5):

[0024]

[Chemical 16]

(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. (Meth) acrylic acid ester derivative represented by the general formula (6):

[0026]

[Chemical 17]

(In the formula, each R ₃ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen group, and each R ₄ independently represents a hydrogen atom or a methyl group. Where R ₃ is a substituent different from R ₁ ) and a mixture of the (meth) acrylic acid ester derivative represented by general formula (7):

[0028]

[Chemical 18]

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 (8):

[0030]

[Chemical 19]

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

[0032]

[Chemical 20]

(In the formula, X ₁ is represented by the general formula (2):

[0034]

[Chemical 21]

A group represented by the formula (wherein R ₁ and R ₂ are the same as defined above), and X ₂ is represented by the general formula (3):

[0036]

[Chemical formula 22]

## STR3 ## wherein R ₃ and R ₄ are the same as defined above, and X is X ₁ or X ₂ . l
/ M is 1/99 to 99/1, and (l + m) is 1 to 2
It is an integer of 0. Y and Z are the same groups as described above)
And a method for producing a photopolymerizable unsaturated resin having a number average molecular weight of 1,500 or more.

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).

[0040]

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

[0041]

[Chemical formula 23]

(Wherein X, X ₁ , X ₂ , Y, Z and 1,
m is as described above) and has a number average molecular weight of 1
It is a novel resin of 500 or more (hereinafter sometimes referred to as the resin of the present invention). 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 in a molar ratio of 1: 9
It is obtained by adding and reacting at a ratio of 9 to 65:35.

The resin of the present invention is characterized in that it has a structure in which hydroxyl groups at both terminals 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 (9) 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. The method for producing the compound represented by the general formula (9) is obtained by simultaneously reacting an epoxy acrylate compound having a bisphenolfluorene structure with an acid anhydride and an acid dianhydride. Is also different.

The photopolymerizable unsaturated resin represented by the general formula (1) can be produced extremely efficiently by the following method. First, general formula (4):

[0045]

[Chemical formula 24]

An epoxy compound (4) represented by is prepared. In the epoxy compound represented by the general formula (4), each R ₁ independently represents a hydrogen atom or a carbon number of 1 to 1.
5 represents an alkyl group, 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. More preferably, a methyl group,
A phenyl group and a hydrogen atom are used, and a biscresolfluorene type in which both R ₁ are methyl groups, a bisphenylphenolfluorene type in which both R ₁ are phenyl groups, and a bisphenolfluorene type in which both R ₁ are hydrogen atoms are preferably used. The epoxy compound represented by the general formula (4) can be easily obtained, for example, by reacting bisphenolfluorene or biscresolfluorene with an epihalohydrin such as epichlorohydrin. A commercially available product may be used.

Next, the epoxy compound represented by the general formula (4) is reacted with (meth) acrylic acid to give the general formula (5):

[0048]

[Chemical 25]

A (meth) acrylic acid ester derivative (5) represented by the following formula is obtained.

Then, an epoxy compound having a substituent R ₃ instead of the substituent R ₁ of the general formula (4) is reacted with (meth) acrylic acid to give the general formula (6):

[0051]

[Chemical formula 26]

A (meth) acrylic acid ester derivative (6) represented by is obtained. R ₃ has the same meaning as described above.

Next, a mixture with the obtained (meth) acrylic acid ester derivative represented by the general formula (5) or (6) and the general formula (7):

[0054]

[Chemical 27]

The tetracarboxylic acid dianhydride represented by the formula (wherein Z is the same as above) is reacted in a suitable solvent. In this reaction, the (meth) acrylic acid ester derivative used in the reaction has a molar ratio of 1:99.
It is necessary to add and react at a ratio of ˜99: 1.

After completion of this reaction, the reaction product and the compound of the general formula (8):

[0057]

[Chemical 28]

The dicarboxylic acid anhydride represented by the formula (wherein 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 solvent such as ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl-1-acetate can be preferably used.

The reaction is preferably carried out at a temperature at which the tetracarboxylic dianhydride and dicarboxylic acid anhydride quantitatively react with the hydroxyl group in the (meth) acrylic acid ester derivative of the general formula (5). For example, in the reaction of a (meth) acrylic acid ester derivative with a tetracarboxylic dianhydride, it is usually 100 to 130 ° C., preferably 115.
Performed at ~ 125 ° C. When the reaction temperature exceeds 130 ° C., a part of the (meth) acrylic acid ester derivative is polymerized, which causes a rapid increase in the molecular weight.
If the temperature is lower than ° C, the reaction may not proceed smoothly, and unreacted tetracarboxylic dianhydride may remain.

The reaction between the reaction product of the (meth) acrylic acid ester derivative and 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)
With respect to a total of 1 equivalent of hydroxyl groups of the acrylic ester derivative, the total of acid anhydride groups of tetracarboxylic dianhydride and dicarboxylic anhydride is 0.6 to 1 equivalent, preferably 0.1.
It is preferable to react at a ratio of 75 equivalents or more and less than 1 equivalent. 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 above general formula (4) 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 (5) 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, and the general formula ( The value of (l + m) in 1) can be adjusted.

When three or more epoxy acrylic acid derivatives are used, the desired alkali-soluble radiation-sensitive resin can be obtained by reacting under the same conditions as above.

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.

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 an 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.

The radiation-sensitive resin composition of the present invention contains, for example, an epoxy group curing accelerator, a thermal polymerization inhibitor, an antioxidant, an adhesion aid, if necessary, within a range not impairing the object of the present invention. , 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.

As the defoaming agent, for example, 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 0.1 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 rays, ultraviolet rays, 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, and a surfactant 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 perform 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 substrate is coated with a resist solution containing the resin composition 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 performed 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 0.5% 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 protective film for a color filter 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.

[0099]

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 (1) In a 500 mL four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 23
5) and tetramethylammonium chloride 110m
g, 2,6-di-tert-butyl 4-methylphenol (100 mg) and acrylic acid (72.0 g) were charged, and 90 to 10 while blowing air at a rate of 25 mL / min.
It melt | dissolved by heating at 0 degreeC. Next, the temperature of the solution was gradually increased in a cloudy state and heated to 120 ° C. to completely dissolve the solution. Here, the solution gradually became transparent and viscous, but the stirring was continued as it was. During this period, the acid value was measured and 1.0 mgKOH / g
Stirring was continued until the temperature became less than 1. It took 12 hours for the acid value to reach the target. Then, the mixture was cooled to room temperature to obtain a light yellow transparent solid bisphenolfluorene type epoxy acrylate represented by the general formula (3) (R ₁ = hydrogen atom, R ₂ = hydrogen atom in the formula).

(2) In a 1000 mL four-necked flask,
Bisphenylphenol fluorene type epoxy resin 31
2 g (epoxy equivalent 312) and 450 mg triethylbenzylammonium chloride, 2,6-di-tert
Butyl 4-methylphenol (100 mg), acrylic acid (72.0 g), and propylene glycol monomethyl ether acetate (PGMEA) (500 g) as a solvent were charged, and the mixture was heated and dissolved at 90 to 100 ° C while blowing air at a rate of 25 mL / min. Next, the temperature of the solution was gradually increased in a cloudy state and heated to 120 ° C. to completely dissolve the solution. Here, the solution gradually became transparent and viscous, but the stirring was continued as it was. During this period, the acid value was measured and was 1.0
The heating and stirring were continued until it was less than mgKOH / g. It took 12 hours for the acid value to reach the target. Then, it is cooled to room temperature, and is a bisphenol fluorene type epoxy acrylate represented by the general formula (3) which is transparent in a light yellow color (R _{1 in the} formula
= Phenyl group, R ₂ = hydrogen atom) to obtain a PGMEA solution (solid content: 43.5%).

Then, 153.5 g of the bisphenol fluorene type epoxy acrylate obtained in (1),
To 442.3 g of the bisphenylphenol fluorene type epoxy acrylate PGMEA solution obtained in (2), 350 g of propylene glycol monomethyl ether acetate was added and dissolved, and then 80.5 g of benzophenone tetracarboxylic acid dianhydride and tetraethylammonium bromide. 1g are mixed and gradually heated to 110-11
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 1 represented by the formula (in the formula, R ₁ = hydrogen atom, R ₂ = hydrogen atom, R ₃ = phenyl group, R ₄ = hydrogen atom, 1 / m molar ratio = 50.0 / 50.0, Y / Z molar ratio = 50.0 / 5
0.0) PGMEA solution was obtained. IR disappearance of acid anhydride
Confirmed by spectrum.

(Example 2: Production of resin 2) Production in Example 1
Bisphenol fluorene type epoxy accrea
153.5g and bisphenylphenol fluorene type
Use 442.3 g of epoxy acrylate PGMEA solution
Propylene glycol monomethyl ether acetate
350 g of benzophenone
104.7 g of lacarboxylic acid dianhydride and tetraethyl bromide
1 g of lumonium was mixed and gradually heated to 110
The reaction was carried out at 115 ° C for 4 hours. Confirmed disappearance of acid anhydride group
Then 1,2,3,6-tetrahydrophthalic anhydride 1
5.2 g were mixed and reacted at 90 ° C. for 6 hours.
Resin 2 represented by (1) (R in the formula₁= Hydrogen atom, R_Two
= Hydrogen atom, R _Three= Phenyl group, R_Four= Hydrogen atom, l /
m = 50.0 / 50.0, Y / Z molar ratio = 23.5 / 7
6.5) A PGMEA solution was obtained. Disappearance of acid anhydride is above
It confirmed by IR spectrum like Example 1.

Example 3 Production of Resin 3 Using 153.5 g of the bisphenol fluorene type epoxy acrylate produced in Example 1 and 442.3 g of the bisphenylphenol fluorene type epoxy acrylate PGMEA solution, 350 g of propylene glycol monomethyl ether acetate was used. After adding to make a solution, 67.6 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide are mixed and gradually heated to 110-1.
The reaction was carried out at 15 ° C for 4 hours. After confirming the disappearance of the acid anhydride group, 1,2,3,6-tetrahydrophthalic anhydride 4
8.6 g were mixed and reacted at 90 ° C. for 6 hours, and the resin 3 represented by the general formula (1) (wherein R ₁ = hydrogen atom, R
₂ = hydrogen atom, R3 = phenyl group, R4 = hydrogen atom, l
/M=50.0/50.0, Y / Z molar ratio = 60/4
0) A PGMEA solution was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.

(Example 4: Production of resin 4) Production in Example 1
Bisphenol fluorene type epoxy accrea
153.5g and bisphenylphenol fluorene type
Use 442.3 g of epoxy acrylate PGMEA solution
Propylene glycol monomethyl ether acetate
350 g of benzophenone
Lacarboxylic acid dianhydride 96.6 g and tetraethyl bromide
1g of ammonium was mixed and gradually heated up to 110-1
The reaction was carried out at 15 ° C for 4 hours. Confirm disappearance of acid anhydride group
Then 1,2,3,6-tetrahydrophthalic anhydride 4
5.6 g were mixed and reacted at 90 ° C. for 6 hours.
Resin 4 represented by (1) (R in the formula₁= Hydrogen atom, R
_Two= Hydrogen atom, R _Three= Phenyl group, R_Four= Hydrogen atom, l
/M=50.0/50.0, Y / Z molar ratio = 50.0 /
50.0) PGMEA solution was obtained. The disappearance of acid anhydride is I
It was confirmed by R 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) 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, and 1
It was heated to 20 ° C. and completely dissolved. Here, the solution gradually became a transparent viscous paste, but the stirring was continued as it was. During this time,
The acid value was measured, and heating and stirring were continued until it 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 solid biscresolfluorene type epoxy acrylate represented by the general formula (3) (R ₁ = methyl group, R ₂ = hydrogen atom in the formula).

Then, the above-mentioned biscresolfluorene type epoxy acrylate 158 thus obtained.
g and the bisphenylphenol fluorene type epoxy acrylate PGMEA solution 442.3 prepared in Example 1
After adding 350 g of propylene glycol monomethyl ether acetate to g and dissolving, benzophenone tetracarboxylic acid dianhydride 80.5 g and tetraethylammonium bromide 1 g are mixed and gradually heated to 110-11.
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 (R ₁ = hydrogen atom, R ₂ = hydrogen atom, R ₃ = phenyl group, R ₄ = hydrogen atom, 1 / m molar ratio = 50/50, Y / Z molar ratio = 50.0 / 50.0)
Of PGMEA solution was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum.

Comparative Example 1: Production of Resin 6 153.5 g of the bisphenolfluorene type epoxy acrylate produced in (1) of Example 1 and the bisphenylphenolfluorene type epoxy acrylate PGMEA produced in (2) of Example 1 After adding and dissolving 350 g of propylene glycol monomethyl ether acetate to 442.3 g of the solution, benzophenone tetracarboxylic dianhydride 1
02.3 g and tetraethylammonium bromide 1 g were mixed, and the temperature was gradually raised to react at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 1, 2, 3, 6
-Mixing with 0.5 g of tetrahydrophthalic anhydride, 90 ° C
For 6 hours, the resin 6 represented by the general formula (1) (in the formula, R ₁ = hydrogen atom, R ₂ = hydrogen atom, R ₃ = phenyl group, R ₄ = hydrogen atom, 1 / m molar ratio = 50/50, Y /
A PGMEA solution having a Z molar ratio of 0.8 / 99.2) was obtained. However, this resin 6 has a Y / Z molar ratio of 0.
8 / 99.2, which is not included in the scope of the present invention. The reaction of the acid anhydride was confirmed by IR spectrum.

Comparative Example 2 Production of Resin 7 153.5 g of the bisphenol fluorene type epoxy acrylate produced in Example 1 and 442.3 g of the bisphenylphenol fluorene type epoxy acrylate PGMEA solution produced in Example 1 were mixed with propylene glycol monomethyl. After 350 g of ether acetate was added and dissolved, 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 allowed to react at 90 ° C. for 6 hours,
Resin 7 represented by the general formula (1) (in the formula, R ₁ = hydrogen atom, R ₂ = hydrogen atom, R ₃ = phenyl group, R ₄ = hydrogen atom, 1 / m molar ratio = 50/50, Y / Z molar ratio = 75.
0 / 25.0) PGMEA solution was obtained. The disappearance of the acid anhydride was confirmed by IR spectrum. This resin 7 has a Y / Z molar ratio of 75/25 in the formula, and 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 carried out at 110 to 115 ° C. for 6 hours to obtain a resin 8 represented by the general formula (9) (Y / Z molar ratio in the formula = 5.
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 bisphenol fluorene 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.

Comparative Example 5 Production of Resin 10 880 g of the solution containing the bisphenylphenolfluorene type epoxy acrylate resin produced in Example 1 was further added with 300 g of propylene glycol monomethyl ether acetate.
After adding and stirring, 80.5 g of benzophenone tetracarboxylic acid dianhydride and 1 g of tetraethylammonium bromide were mixed, and the temperature was gradually raised to react at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group,
38.0 g of 2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours, and the resin 10 represented by the general formula (1) (R ₁ = phenyl in the formula, R ₂ = hydrogen atom) ,
1 / m = 100.0 / 0, Y / Z molar ratio = 50/50)
A PGMEA solution was obtained. The disappearance of the acid anhydride is shown in Example 1 above.
Similarly to the above, it was confirmed by IR spectrum.

Comparative Example 6 Production of Resin 11 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, and then benzophenone tetracarboxylic acid dianhydride. Thing 80.5
g and 1 g of tetraethylammonium bromide were mixed, and the temperature was gradually raised to react at 110 to 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 the resin 10 ( In the formula, R ₁ = hydrogen atom, R ₂ = hydrogen atom, 1 / m = 100.0
/ 0, Y / Z molar ratio = 50/50) to obtain a PGMEA solution. The disappearance of the acid anhydride was confirmed by the IR spectrum as in Example 1 above.

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 10 obtained in Comparative Examples 1 to 6 at the time of production.

[0115]

[Table 1]

The equivalence ratio and each evaluation item in Table 1 are as follows. 1) The equivalent ratio represents the equivalent ratio of bisphenolfluorene type epoxy acrylate (total) / 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 converted value measured by a gel permeation chromatography method.

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. The solution viscosity was measured by dissolving the resin in propylene glycol monomethyl ether acetate so as to be 50% by weight and using a B-type viscometer at 25 ° C.

(Examples 6 to 12 and Comparative Examples 7 to 12) The photopolymerizable unsaturated resins (resins 1 to 9) obtained in Examples 1 to 5 and Comparative Examples 1 to 6 are used and shown in Table 2. A resist solution having a composition was prepared.

[0120]

[Table 2]

The tetramethylbiphenyl type epoxy resin used was "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 onto 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 0.5 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 process and the development process was placed in an oven at 200 ° C. for 3 days.
The thin film was left to stand for 0 minutes (post-baking treatment), and the thin film was cured by heating to obtain a cured film.

Evaluation of each resin in the above-mentioned coating film formation, exposure / development and heating steps and the resulting heat-cured film was carried out 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 The developability with respect to the alkaline aqueous solution is such that the pre-baked coating film which has not been subjected to the exposure treatment is immersed in a 0.5 wt% sodium carbonate aqueous solution 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 and cured and baked, and the rate of change in film thickness before and after the cure bake ((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 (thickness change rate of less than 3%) Δ: Heat resistance is slightly good (thickness change rate of 3% to less than 7%) ×: Heat resistance is poor (thickness change rate of 7%) 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 subsequent appearance and adhesion were evaluated. 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) ×: Inferior chemical resistance (10% or more change rate of film thickness in any solution)

The above results are shown in Table 3.

[0132]

[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 of Table 3, Example 6
Nos. 12 to 12 could achieve the desired 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 the target pattern was not formed. I can't get it. Further, at a molar ratio of Y / Z = 75/25 as in Comparative Example 6, the molecular weight of the resin becomes too small, which is contrary to Comparative Example 5,
The change in film thickness after curing and baking and the change in film thickness after immersion in a solvent after post-baking are significant, resulting in poor heat resistance and solvent resistance. When 1 / m = 100/0, a slight lack of developability and heat resistance was observed.

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.

[0136]

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 the 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.

Front page continuation (51) Int.Cl. ⁷ identification code FI theme code (reference) G03F 7/027 515 G03F 7/027 515 (72) Inventor Kei Kitano 236 Nakai, Tatsuno-cho, Tatsuno-shi, Hyogo Nagase Chemtex Corporation Harima No. 1 Factory F-term (reference) 2H025 AA04 AA06 AA07 AA08 AA10 AB06 AB13 AB15 AB16 AB17 AC01 AD01 BC14 BC32 BC42 BC74 BC85 BC92 CA01 CA18 CA28 CA30 FA03 FA17 FA29 4H006 AA01 AA03 AB46 BJ50 4J027 AB03 AB05 AB06 AB23 AB05 AB06 AB23 AB06 AB23 AB05 AB06 AB23 AB05 AB23 AB06 AB23 AB05 AB23 AB05 AB23 AB06 AB23 AB23 AB05 AB23 AB09 AB23 BA08 BA19 BA20 BA24 BA25 BA26 BA28 CA10 CB03 CB09 CB10 CC03 CD10 4J029 AA07 AB02 AC01 AD02 AE18 BF20 CA04 CA05 CB04A CD03 CG17X FC35 GA01 GA13 GA17 GA23 HA01 HB06 KI09 4J036 AD07 AD08 AD20 AF06 DB11 AF06 DB15 AF02 AF06 AF08 AJ0909

Claims (4)

[Claims] 1. General formula (1): (In the formula, X ₁ is represented by the 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 Represents a methyl group) and X ₂ is a compound represented by the general formula (3): (In the formula, R _3'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 _4's each independently represent a hydrogen atom or R ₃ is a substituent different from R ₁ , and R ₂ and R ₄ may be the same,
May be different, X is X ₁ or X ₂ , and 1 /
m is 1/99 to 99/1, and (l + m) 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 dicarboxylic acid anhydride and tetracarboxylic acid dianhydride in a molar ratio of 1:99 to 65:35. Unsaturated resin. 2. General formula (5): (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. ) And a (meth) acrylic acid ester derivative represented by the general formula (6): (In the formula, each R ₃ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a halogen group, and each R ₄ independently represents a hydrogen atom or a methyl group. , R ₃ is a substituent different from R ₁ ) and a (meth) acrylic acid ester derivative represented by the general formula (7): (In the formula, Z is a residue of the tetracarboxylic acid dianhydride excluding the acid anhydride group), and the tetracarboxylic acid dianhydride is reacted, and then the compound represented by the general formula (8): ] (In the formula, Y is a residue of the dicarboxylic acid anhydride excluding the acid anhydride group), the dicarboxylic acid anhydride and the tetracarboxylic acid dianhydride in a molar ratio General formula (1): embedded image characterized by adding and reacting at a ratio of 1:99 to 65:35. (In the formula, X ₁ is represented by the general formula (2): A group represented by: (wherein R ₁ and R ₂ are the same as above)
And X ₂ is represented by the general formula (3): Wherein R ₃ and R ₄ are the same as defined above, X is X ₁ or X ₂ , and 1 / m is 1
/ 99 to 99/1, (l + m) is an integer of 1 to 20, Y and Z are the same groups as described above, and the number average molecular weight is 1,500 or more. Method for producing unsaturated resin. 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.