JPH09325493A - Alkali developable resin composition excellent in flexibility and image forming material using the same - Google Patents

Abstract

(57) [Summary] (Corrected) [PROBLEMS] To provide an alkali developable resin composition having high sensitivity and excellent flexibility. Further, by using this resin composition, an image forming material suitable for applications such as a color filter is provided. SOLUTION: An adduct of diglycidyl ether and (meth) acrylic acid and an acid anhydride are mixed in an amount of 0.3 ≦ X ≦ 0.9.
(However, the charge ratio X = {the number of moles of acid anhydride groups in the charge acid anhydride} / {the number of moles of hydroxyl groups in the charge adduct}) is reacted, and then the resulting acid-modified unsaturated resin and diisocyanate are obtained. 0.05 ≦ Y <1 (however, the charging ratio Y = [{mol number of isocyanate group of diisocyanate compound charged} / {mol number of hydroxyl group of charged adduct}]] × {1 / (1-X) }) Alkali-developing resin composition obtained by reacting at a charging ratio of. Also,
A color filter material and an insulating material obtained by using the alkali developable resin composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material which can be cured by irradiation with ultraviolet rays or electron beams and can form a negative pattern by alkali development treatment. Resin composition, color filter ink, black matrix ink and color filter comprising these,
Further, it is useful as an insulating insulating film for a printed wiring board or MCM (multi-chip module), and is particularly suitable for flexible film substrates and thin film metal substrates. The image forming material used.

[0002]

2. Description of the Related Art Conventionally, a screen printing method using a thermosetting resin and a spin coating method have been widely used to form an image element of this type, its protective film and an insulating pattern of a printed wiring board. Has been done. In recent years, along with changes such as high definition of liquid crystal displays and high density mounting of semiconductor elements, it is required to form fine patterns with high precision by lithography. Also,
Even for the obtained coating film or pattern, strict performance is required for properties such as hardness, solder heat resistance, transparency, adhesion, acid resistance, alkali resistance, solvent resistance, insulation resistance, and flatness. . Further, along with the development of mobile and mobile communication of information equipment terminals, displays using light and deformable film substrates and thin film metal substrates, coating materials for printed wiring boards, and negative pattern forming materials are also required. There is.

For example, a color filter ink having a high color purity is required to meet the demand for high definition of the color filter. As a method for increasing the color purity, there is a method in which a pigment having a high color purity is dispersed in a resin at a high concentration. However, the ultraviolet rays necessary for pattern formation are blocked, so that the sensitivity is lowered. For this reason, many photopolymerization initiators have been added to the negative pattern forming material, but the line thickening of the pattern due to heat fogging and the residue of the dissolved portion pose a problem.

There is also a demand for a high light-shielding resin black matrix having low reflection for high definition of the color filter. This product is prepared by dispersing a light absorbing black pigment or several kinds of mixed color pigments in a negative pattern forming material, and similarly, ultraviolet rays necessary for pattern formation are blocked, resulting in low sensitivity. I can't. Therefore, for the recently demanded black matrix ink that blocks 99.9% or more of light, a highly sensitive photosensitive resin capable of forming a fine pattern with high precision is required.

Further, liquid crystal displays are becoming widespread as displays for notebook type personal computers and portable devices due to their low power consumption. A glass substrate with excellent flatness and dimensional stability is used as the substrate of the display, but since the thickness is at least 0.7 mm and the weight of the display becomes heavy, it is required to make a substrate film. There is.

[0006] For insulating materials for printed wiring boards and semiconductors, a thick film of about several tens of μm is required for frequency compatibility, insulation resistance and reliability. In the case of a thick film, cracks and separation from the substrate are likely to occur especially when a deformation stress is applied. However, at the present time, it has not been possible to achieve both flexibility and adhesion to the coating film, low moisture absorption, heat cycle property, and the like.

In general, the pattern-forming material used for such an application is a polyfunctional photocurable monomer having a polymerizable unsaturated bond, an alkali-soluble binder resin, and a composition of them and a photopolymerization initiator. Is used. For example,
JP-A-61-213213 and JP-A-1-1524
Japanese Patent Publication No. 49 discloses application as a material for a color filter. The binder resin exemplified in these publications is a (meth) acrylic acid or (meth) acrylic acid ester having a carboxyl group, a copolymer of maleic anhydride and another polymerizable monomer, and has in its molecule It has a carboxyl group that expresses alkali developability, but it does not have a polymerizable unsaturated bond, and it induces a difference in solubility between light-irradiated and unirradiated areas by photopolymerization of polyfunctional photo-curable monomers, and negative pattern Is formed. For this reason,
Since the obtained cured coating film requires a surface hardness of 2H or higher for pencil hardness, it has a problem that it lacks flexibility and lacks adhesion to a film substrate or the like.

Further, in each of JP-A-4-340965, JP-A-4-345673, JP-A-4-345608, JP-A-4-355450, and JP-A-4-363331, one molecule is included in one molecule. It has been disclosed that an alkali-developable unsaturated compound having a polymerizable unsaturated double bond and a carboxyl group is effective for forming a negative pattern such as a heat-resistant liquid resist and a color filter. However, since a monofunctional acid anhydride such as tetrahydroxyphthalic anhydride is used as the acid anhydride, the obtained alkali-developable unsaturated compound is obtained by adding 1 molecule of diacrylate and 1 molecule or 2 molecules of acid anhydride. Since this compound is a monomer having a molecular structure, its sensitivity is low, and a pattern with a high light-shielding degree cannot be formed especially as a black resist resin containing a high-concentration light-shielding agent.

Further, JP-A-5-339356, JP-A-5-146132, and PCT / JP93 / 0053.
Each of the publications of No. 6 discloses an alkali developable unsaturated resin obtained by copolymerizing a dihydroxypropyl acrylate compound with an acid monoanhydride and an acid dianhydride.
In this case, the oligomerization proceeds due to the addition reaction of the acid dianhydride and the dihydroxy compound, but the acid monoanhydride coexisting in the reaction system hinders the oligomerization.
There is a problem that the molecular weight of the alkali-developable unsaturated resin is reduced and the molecular structure is made nonuniform, the sensitivity is reduced and the development margin is narrow.

By the way, the hardness is preferably as high as possible from the viewpoint of improving the durability of the coating film, but on the contrary, it acts so as to reduce the bendability. Therefore, it is extremely difficult to achieve both a high level of hardness and a high level of bendability in a coating film obtained from the above materials. There are many publicly known examples of coating agents for metal materials and plastic materials, and it is known that they have excellent hardness or bendability, but they are not sufficient in terms of satisfying both physical properties at the same time. I can't say. For example, JP-A-2-102279 and JP-A-3-258374.
Although the publication is also known, the coating films obtained by these methods have good bendability but insufficient hardness,
It does not combine bendability and hardness at a high level.

[0011]

Therefore, the present inventors have diligently studied an alkali-developable resin composition and an image-forming material having both excellent surface hardness and bendability, and as a result, diglycidyl ether was obtained. An alcoholic hydroxyl group is left in the acid-modified unsaturated resin obtained by reacting an acid anhydride with an adduct with (meth) acrylic acid, and the diisocyanate compound is reacted using the remaining alcoholic hydroxyl group. As a result, an alkali-developable polyfunctional urethane acrylate resin composition having heat, photocurability and flexibility can be obtained, and by using this, only surface hardness and bending resistance are excellent. The present invention has been completed by finding that a negative type image forming material having excellent adhesiveness can be obtained.

Therefore, an object of the present invention is to provide an alkali developable resin composition having high sensitivity and excellent flexibility. Another object of the present invention is composed of such an alkali-developable resin composition, and is excellent not only in heat resistance, chemical resistance, crack resistance, transparency, insulation, and hardness but also in resistance. An object of the present invention is to provide a cured film having excellent bendability (flexibility at the time of bending) and adhesion, and to provide an image forming material suitable for applications such as color filters and insulating films.

[0013]

That is, according to the present invention, an adduct of diglycidyl ether and (meth) acrylic acid and an acid anhydride are mixed in an amount of 0.3 ≦ X ≦ 0.9 (however, a charging ratio X = {Mol number of acid anhydride group of charged acid anhydride} / {mol number of hydroxyl group of charged adduct}), and then the obtained acid-modified unsaturated resin and diisocyanate compound are mixed with each other. 05 ≦ Y <1 (however, charging ratio Y = [{mol number of isocyanate group of charging diisocyanate compound} / {mol number of hydroxyl group of charging adduct}] × {1 / (1-X)}) It is an alkali developable resin composition excellent in flexibility obtained by reaction. Further, the present invention is a material for a color filter obtained by using such an alkali developable resin composition having excellent flexibility, and an insulating material.

In order to obtain the alkali developable resin composition of the present invention, first, various diglycidyl ethers and (meth)
An acid anhydride is reacted with an adduct with acrylic acid at a predetermined charging ratio. An example of the reaction for obtaining the alkali developable resin composition of the present invention is as follows.

Embedded image

Specific examples of various adducts of diglycidyl ether and (meth) acrylic acid used here include glycidyl ethers such as ethylene glycol, diethylene glycol, polyethylene glycol, glycerin, hydrogenated bisphenol A, and the like. Are exemplified by dihydroxypropyl acrylate resins which are addition compounds obtained by reacting various bisphenol diglycidyl ethers with (meth) acrylic acid.

Then, specific examples of the bisphenol component constituting various diglycidyl ethers used in the production of this dihydroxypropyl acrylate resin include:
Bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4 -Hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) Hexafluoropropane, bis (4-
Hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5
-Dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,
5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) ) Propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-)
3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-
Hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,
9-bis (4-hydroxyphenyl) fluorene, 9,
9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-)
3-Bromophenyl) fluorene, 9,9-bis (4-
Hydroxy-3-fluorophenyl) fluorene, 9,
9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) Fluorene, 9,
9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, 4,4'-biphenol, 3,3'-
Biphenol etc. are mentioned.

Further, since the adduct of diglycidyl ether and (meth) acrylic acid is derived from an epoxy compound by a production method which will be illustrated later, a small amount of an oligomer unit is mixed in. There is no problem in the performance of the developable resin composition.

Examples of the acid anhydride to be reacted with the adduct of diglycidyl ether and (meth) acrylic acid include, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride and tetrahydroanhydride. Phthalic acid, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenylethertetracarboxylic dianhydride Aromatic polyvalent carboxylic acid anhydrides such as anhydrides, and aromatic polyvalent carboxylic acid anhydrides in which a substituent such as an alkyl group or a halogen group is substituted on the aromatic ring of these aromatic polyvalent carboxylic acid anhydrides. .

The reaction of reacting the adduct of diglycidyl ether with (meth) acrylic acid with the acid anhydride to obtain an acid-modified unsaturated resin as an intermediate is 0.3≤X≤0.9.
(However, the charge ratio X = {the number of acid anhydride groups in the charge acid anhydride} / {the number of hydroxyl groups in the charge adduct}}, and the reaction is carried out for the purpose of adjusting the viscosity. It is carried out under heating in a solvent having a boiling point higher than the temperature. In the present invention, the charging ratio means the ratio of raw materials used, and the raw materials added by means such as dropping during the reaction can be taken into consideration.

Here, the number of moles of acid anhydride group means the number of moles of acid anhydride group (-CO-O-CO-). For example, in the case of 1 mole of methyltetrahydrophthalic anhydride, the number of moles of acid anhydride group is With 1 mol and 1 mol of biphenyltetracarboxylic dianhydride, the number of mols of acid anhydride groups is defined as 2 mol. When the charging ratio X is less than 0.3, the developing time becomes long, which is not preferable, and when it is more than 0.9, the desired flexibility and sensitivity improving effects due to isocyanate modification described later cannot be obtained.

The reaction temperature at the time of producing the acid-modified unsaturated resin as an intermediate is 90 to 140 ° C., preferably 1
The reaction time is 2 to 20 hours, preferably 2 to 12 hours. When the reaction temperature is lower than 90 ° C., the reaction time becomes longer than 20 hours, and unreacted acid anhydride remains, which is not preferable. On the other hand, if the temperature exceeds 140 ° C, gelation due to the reaction of the polymerizable unsaturated group and coloring of the resin are likely to occur, which is not suitable.

As the reaction solvent, a solvent having no hydroxyl group and having a temperature higher than the reaction temperature, for example, a cellosolve solvent such as ethyl cellosolve acetate or butyl cellosolve acetate, diglyme, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, etc. The high boiling point ether or ester solvents, ketone solvents such as cyclohexanone and diisobutyl ketone, etc. are preferably used.

For the purpose of accelerating the reaction, a known reaction catalyst such as tetraethylammonium bromide may be used in the range of 0.001 to 1% by weight with respect to the adduct.
For the purpose of imparting the thermal stability of the polymerizable unsaturated group, a polymerization inhibitor such as di-t-butylhydrocitoluene may be used in an amount of 0.1% by weight or less based on the adduct.

In the present invention, the acid-modified unsaturated resin obtained above is mixed with a diisocyanate compound in an amount of 0.05≤Y <1 (however, charging ratio Y = [{mol of isocyanate group of charging diisocyanate compound} / { The number of moles of the hydroxyl group of the charged adduct}] ÷ {1 / (1-X)}) is used for the reaction.

The diisocyanate which can be used in the present invention is a diisocyanate having two isocyanate groups in one molecule, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-diphenylene diisocyanate, xylylene diisocyanate, etc., alone or in combination of two or more. Can be used. Aliphatic diisocyanates are particularly suitable for the purpose of imparting flexibility.

Regarding the charging ratio Y, it is 0.
If it is less than 05, the desired effect of flexibility and sensitivity improvement due to the isocyanate modification cannot be obtained, and conversely, if it is 1 or more, problems such as the generation of insoluble matter due to the reaction between unreacted isocyanate and water, etc. occur. There are cases.

This reaction is accomplished by a normal urethane reaction and is preferably carried out under a nitrogen atmosphere in the temperature range of 50 to 150 ° C, more preferably 60 to 100 ° C. If the reaction temperature is lower than 50 ° C, the reaction rate of the isocyanate group is low, and if it is higher than 150 ° C, the isocyanate groups may react with each other and at the same time, the acryloyl group in the acid-modified unsaturated resin may cause radical polymerization. This is not preferable because the product of 1 may not be obtained.

Although this reaction proceeds even without a catalyst, a catalyst may be used for the purpose of promoting the reaction. As the catalyst used for this purpose, titanium compounds such as tetrabutyl titanate, tetrapropyl titanate and tetraethyl titanate, and organic tin compounds such as tin octylate, dibutyltin oxide and dibutyltin dilaurate can be used. The amount used is about 0.01 to 10.00 ppm with respect to the total amount of the resin charged.

The image-forming material of the present invention comprises, as an essential component, a photopolymerization initiator, a cross-linking agent such as a polyfunctional acrylate monomer and an oligomer, and the like in the alkali developable resin composition.
It is prepared by mixing an epoxy resin and a solvent for adjusting viscosity, a pigment for coloring, a filler, a leveling agent, etc. according to the application, and coating this on a substrate such as glass or a silicon wafer, and the solvent at 50 to 150 ° C. A negative pattern is formed by heating and removing to form a coating film, followed by curing with an actinic ray such as ultraviolet rays through a negative mask and developing in an alkaline developer.

As the photopolymerization initiator used together with the alkali developing resin of the present invention as a constituent of the image forming material, for example, benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2- Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-methyl-1- {4- (methylthio) phenyl} -2-morpholinopropan-1-one, N, N-dimethylaminoacetophenone, 2 -Methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethylketane Le, benzophenone, methyl benzophenone, 2-trichloromethyl -5 chromatography (P- methoxystyryl) over 1,3,4 chromatography oxadiazole, 4,
4′-bisdiethylaminobenzophenone, 2-trichloromethyl-S-triazine and the like can be mentioned.
These may be used alone or in combination of two or more. Further, such a photopolymerization initiator is N, N-
Known photosensitizers such as dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine and triethylamine can be used alone or in combination of two or more kinds. The amount of the photopolymerization initiator used is 0.5 to 20% by weight, preferably 1 to 15% by weight, based on the alkali developable resin composition of the present invention.

Further, the alkali-developable resin composition of the present invention may be blended with a monomer or oligomer having an ethylenically unsaturated group capable of photopolymerization according to the purpose of use. In particular, for higher sensitivity, it is preferable to have two or more double bonds in one molecule so that they can be polymerized. Specific examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2
A monomer having a hydroxyl group such as ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate Examples thereof include (meth) acrylic acid esters such as acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, and the like. These compounds may be used alone or in combination of two or more.

Further, for the purpose of improving the adhesion between the obtained negative pattern and the substrate and improving the alkali resistance, it is desirable to mix a compound having an epoxy group with the image forming material. Examples of the compound having an epoxy group include phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin,
Epoxy resins such as bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl Examples thereof include compounds having at least one epoxy group such as ether and glycidyl methacrylate.

Further, the image forming material of the present invention may contain an epoxy group curing accelerator, a polymerization inhibitor, a plasticizer, if necessary.
Additives such as a leveling agent and an antifoaming agent can be added. Examples of the epoxy group curing accelerator include amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts, and methylol group-containing compounds. These are used together in small amounts to heat the coating film. By doing so, it is possible to further improve various properties such as heat resistance, solvent resistance, acid resistance, plating resistance, adhesion, electrical characteristics and hardness of the obtained resist film.

Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl. Examples of the defoaming agent and the leveling agent include silicon-based, fluorine-based, and acrylic compounds. Further, depending on the use, a filler such as silica may be added for the purpose of lowering the thermal expansion of the cured product, improving the elastic modulus, lowering the moisture absorption and the like.

The image-forming material of the present invention can be obtained by further dissolving it in a solvent capable of dissolving the resin and additives as required, and further mixing a pigment, a filler and the like. The solvent used for this purpose is not particularly limited as long as it dissolves the resin component and does not react with the resin component and the additive.

For example, as a material for a color filter, when it is a protective film for a color filter,
It is composed of the alkali developable resin composition of the present invention, a photopolymerization initiator, a polyfunctional acrylate, an epoxy resin, a solvent, a leveling agent, and the like, and when it is a color filter ink, in addition to the above components, A pigment for coloring the coating film is used. Known pigments include organic pigments and inorganic pigments.

The image forming material of the present invention is also suitably used as a black ink for a black matrix. The image forming material of the present invention is 99.9% or more (shading ratio OD ≧
It is possible to form a good pattern even with the light-shielding material composition of 3) (80 parts by weight or more of carbon black with respect to 100 parts by weight of the resin component), which is suitable for a black ink for a resin black matrix. .

The insulating film is generally applied with a film thickness of 10 μm or more in order to increase the volume resistivity and prevent conduction due to defects or the like. Also in this application, a highly sensitive photosensitive resin for forming a fine pattern with a thick film is required. That is, it becomes necessary to cure to a deep part. For this reason, the addition of a large amount of photopolymerization initiator is not effective due to absorption by the photopolymerization initiator itself, and leads to poor adhesion to the substrate and reduced reliability of the formation pattern due to the residual photopolymerization initiator. According to the present invention, it is possible to form a thick negative fine pattern with a conventional photopolymerization initiator amount. In addition, since it exhibits excellent heat resistance, it also has excellent durability against heat history during mounting of these circuit elements.

The image forming material of the present invention is a flexible organic film as a substrate, such as polycarbonate,
When using polyester, polyether sulfone, tetraacetyl cellulose, etc., or a metal thin film of aluminum or copper,
It can be suitably used because cracking and peeling from the substrate hardly occur during the bending.

[0040]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below based on Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples. The molecular weight of the obtained alkali-developable resin composition is a value obtained by gel permeation chromatography with an RI (refractive index) detector using tetrahydrofuran as a developing solvent, and all the molecular weights shown are in terms of polystyrene. Is the weight average molecular weight.

Synthesis Example 1 75.0 g of bisphenolfluorene type epoxy resin (epoxy equivalent: 257) was put in a 500 ml four-necked flask.
And triethylbenzyl ammonium chloride 130
mg and tetraethylammonium bromide 0.27
g, 29 mg of 2,6-di-isobutylphenol,
Acrylic acid (21.0 g) and propylene glycol monomethyl ether acetate (17.0 g) were charged, and 100 to 10 while blowing dry air at a rate of 25 ml / min.
The mixture was reacted with stirring at 5 ° C. for 16 hours while heating.

The resin thus obtained was further diluted with 79 g of propylene glycol monomethyl ether acetate to give a pale yellow transparent dihydroxypropyl acrylate resin solution having a solid content of 50% by weight (an epoxy equivalent of 2 in terms of solid content).
1,300 and an acid value of 1.28 mg KOH / g) were obtained.

Example 1 In a 300 ml four-necked flask, 96.0 g of the resin solution obtained in the above Synthesis Example 1, 10.8 g of biphenyltetracarboxylic dianhydride, and 5.6 tetrahydrophthalic anhydride.
g, and stir with heating at 115 to 120 ° C. to 4
After reacting for a time, a transparent pale yellow resin solution was obtained. The weight average molecular weight of the obtained acid-modified unsaturated resin was 4,300.

After further diluting 40.0 g of the acid-modified unsaturated resin solution with 24.8 g of propylene glycol monomethyl ether acetate, 1.44 g of hexamethylene diisocyanate was added dropwise and stirred at 65 ° C. under heating to 4 The reaction was carried out for a time to obtain a pale yellow viscous resin solution having a weight average molecular weight of 6900.

15.8 g of the obtained resin solution and DPHA
(Nippon Kayaku Co., Ltd .: dipentaerythritol hexaacrylate) 2.54 g and YX4000H (Okaka Shell: tetramethylbiphenyl diglycidyl ether)
1.6 g and Irgacure 907 [manufactured by Ciba Geigy:
2-methyl-1- (4-methylthiophenyl) -2-morpholinopropen-1-one] 0.252 g and EA
BF (Hodogaya Chemical Co., Ltd .: N, N, N ', N'-tetraethyl-4,4'-diaminobiphenyl) 0.05 g
Sila Ace S510 (manufactured by Chisso Corporation: 3-glycidoxypropyltrimethoxysilane) 0.17 g, and propylene glycol monomethyl ether acetate 14.
3g was mixed and stirred to obtain a uniform solution. This solution was pressure filtered using a 0.2 micron Teflon membrane filter to prepare an image forming material.

The obtained image-forming material was spin-coated on a glass substrate and exposed to 200 mJ / cm ^{2 on} the basis of i-line, and then 2% in a 0.7% by weight diethanolamine aqueous solution.
Development was carried out at 8 ° C. Furthermore, the obtained pattern is 200
Post-baking was performed at 0 ° C. for 1 hour to obtain a coating film having a thickness of 2 μm. The resulting coating film was examined for development characteristics, sensitivity, adhesiveness, pencil hardness, and heat resistance by the following methods. The results are shown in Table 1.

(1) Development characteristics Development time: Time (seconds) until a negative pattern is formed
Asked. Fine workability: When the negative line of 5 μm could be formed, it was evaluated as ◯. Surface roughness of negative pattern: The surface of a 20 mm square pattern was visually observed, and when there was no roughness, it was marked with O, and when there was roughness, it was marked with X.

(2) Sensitivity Using a wedge filter as a sensitivity mask, 100 m
It was determined from the residual film angle after exposure to J / cm ² and immersion in a 0.7 wt% diethanolamine aqueous solution at 28 ° C. for a predetermined development time. Sensitivity 1 corresponds to the required irradiation dose for which the remaining film ratio is 100%, and sensitivity 2 corresponds to the minimum irradiation amount for which the remaining film ratio is 0%. The higher the sensitivity and the smaller the difference between the two sensitivities, the wider the development margin can be made.

(3) Adhesiveness A 20 mm square negative pattern after post-baking is applied to JIS.
According to K5400, a cross cut was made so as to make at least 100 cross-cuts, and then a peeling test was performed using cellophane tape, and the state of peeling of the cross-cuts was visually observed to check the adhesion to the glass substrate.

(4) Pencil hardness test Using a Mitsubishi Uni for pencil hardness test, JIS K5400
It went according to.

(5) Heat resistance test Light transmittance 1 at 400 nm immediately after post-baking
Then, the light transmittance 2 at 400 nm before and after the treatment for 1 hour in an oven at 250 ° C. and the film thickness reduction were measured.

Further, a chromate-treated electrogalvanized steel sheet (0.5 mm thick) and a polyether sulfone film (PES film: 100 μm thick, manufactured by Sumitomo Bakelite) were used as the base material, and the above image-forming material was made to have a thickness of 7
After coating with a spin coater to a thickness of μm and heating at 80 ° C. for 3 minutes, 200 mJ / cm ² exposure is performed to form a pattern in the same manner, and post baking is performed at 200 ° C. for 30 minutes to obtain a 6 micron film. A thick coating film was obtained.

With respect to the obtained coating film, the adhesion was examined by the method (3) and the bending resistance was examined by the following method. The results are shown in Table 1. (6) Bending resistance test A plate with the same thickness as the test piece is sandwiched, and the coated surface is on the outside 20
The film was bent with a vise at an angle of 180 ° C., the state of the coating film at the bent portion was observed with a magnifying glass, and the minimum number of plates that could be bent without cracks was evaluated.

Example 2 An alkali developable resin composition was prepared in the same manner as in Example 1 except that 2.58 g of hexamethylene diisocyanate was used. The obtained alkali developable resin composition was a light yellow viscous resin solution having a weight average molecular weight of 7,700. Further, an image forming material was prepared to form a coating film, and the developing characteristics, sensitivity, adhesion, pencil hardness, heat resistance, and bending resistance were examined. The results are shown in Table 1.

Example 3 An alkaline developable resin composition was prepared in the same manner as in Example 1 except that 1.49 g of 2,4-tolylene diisocyanate was used. The obtained alkali developable resin composition was a pale yellow viscous resin solution having a weight average molecular weight of 6,400. Further, prepare an image forming material to form a coating film,
The development characteristics, sensitivity, adhesion, pencil hardness, heat resistance, and bending resistance were examined. The results are shown in Table 1.

Example 4 35.3 g of bisphenol A dihydroxypropyl acrylate resin (manufactured by Aldrich) and biphenyltetracarboxylic dianhydride 1 in a 300 ml four-necked flask.
0.8 g, tetrahydrophthalic anhydride 5.6 g, propylene glycol monomethyl ether acetate 4
3.7 g was charged, and the mixture was stirred under heating and reacted for 4 hours to obtain a transparent acid-modified unsaturated resin solution.

Further 18.6 g of 30.0 g of the resin solution
Hexamethylene diisocyanate 1.4 after dilution with propylene glycol monomethyl ether acetate
4 g was added dropwise, the mixture was stirred at 65 ° C. under heating and reacted for 4 hours to obtain a pale yellow viscous resin solution having a weight average molecular weight of 5,800.

An image forming material was prepared in the same manner as in Example 1 by using 15.8 g of the obtained resin solution, and a coating film was further formed thereon, and development characteristics, sensitivity, adhesion, pencil hardness, heat resistance, and resistance The bendability was examined. The results are shown in Table 1.

Comparative Example 1 An image forming material having the same composition as in Example 1 was prepared by using 10.5 g of the acid-modified unsaturated resin solution before isocyanate modification prepared in Example 1. Further, an image forming material was prepared to form a coating film, and the developing characteristics, sensitivity, adhesion, pencil hardness, heat resistance, and bending resistance were examined. The results are shown in Table 1.

Comparative Example 2 An image forming material having the same composition as in Example 1 was prepared by using 10.5 g of the acid-modified unsaturated resin solution before isocyanate modification prepared in Example 4. Further, an image forming material was prepared to form a coating film, and the developing characteristics, sensitivity, adhesion, pencil hardness, heat resistance, and bending resistance were examined. The results are shown in Table 1.

As is clear from the results shown in Table 1, Examples 1 to 3 have higher sensitivity than Comparative Example 1, and
It can be seen that a coating film excellent in adhesion and bending resistance can be obtained while maintaining hardness. In the case of Example 4,
As compared with Comparative Example 2, a coating film having high sensitivity and excellent adhesion and bending resistance while maintaining hardness was obtained.

[0062]

[Table 1]

Example 5 Propylene glycol monomethyl ether acetate 7
In a mixed solvent of 2.7 g and 68.5 g of cyclohexanone,
Irgacure 907 (Ciba Geigy) 1.28 g
And TAZ-110 (Midori Chemical Co., Ltd.) 2.14
g, EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) 0.42 g, solution 53 g of the isocyanate-modified alkali-developable resin composition obtained in Example 1, and DPHA (manufactured by Nippon Kayaku Co., Ltd.) 12 0.8 g was added and stirred to obtain a uniform solution.

20.0 g of the homogeneous solution and carbon black dispersion (made by Sanyo Dye Co., Ltd .: SF black, carbon concentration 2)
0.6%) 20.0 g was mixed and stirred for about 30 minutes to prepare a photosensitive black ink. The viscosity of this product is 7c
It was P (25 degreeC).

The photosensitive black ink thus obtained was spin-coated on a 5-inch square glass substrate, and then placed on a hot plate 6
Dry at 0 ° C for 1 minute, apply a negative mask to 500mJ
/ Cm ² (based on 365 nm ray) was exposed. Furthermore, the coating film was placed in a 0.08% by weight NaCO ₃ aqueous solution at 23 ° C.
The pattern was developed until the pattern was observed with, and rinsed with pure water to remove the residual ink. The black negative pattern obtained was post-baked at 200 ° C. for 30 minutes.

The black negative pattern thus obtained was evaluated as follows. Table 2 shows the results. [Shading rate] Using a digital luminance meter S100 (visual sensitivity calibration) made by Minolta, a backlight (VIEWPET TOPPN CV-11
) From the brightness I ₀ of the glass substrate placed on the substrate and the brightness I through the light-shielding film after post-baking without developing and rinsing only with the above exposure, it was calculated by the following formula. Light-shielding rate (OD) = log (I / I ₀ ).

[Sensitivity] Using a wedge filter as a mask, exposure was carried out at 500 mJ / cm ² and development was performed in a 0.08 wt% NaCO ₃ aqueous solution at 23 ° C. for 15 seconds. Sensitivity 1 corresponds to the required irradiation dose for 100% remaining film ratio, and sensitivity 2 corresponds to the minimum irradiation amount for 0% remaining film ratio.

[Development characteristics] After exposure to 500 mJ / cm ^{2 and} development in a 0.08 wt% NaCO ₃ aqueous solution at 23 ° C. for a predetermined time, the negative pattern was observed as follows. Development residue: The development residue around the negative pattern was observed with a microscope. Residual film and thin line: 20 μm wide grid (80 μm window to be removed)
The corners were observed with a microscope, and the residual film was evaluated as ◯ for the residual film and as for the existence of the residual film, and for the line thinning as ◯ when within 20 ± 1 μm and as x when less than 19 μm. Fine workability: Shown by the minimum width of the negative line that can be formed, 2
It must be less than 0 μm. Surface roughness of negative pattern: The surface of a 20 mm square pattern was visually observed, and when there was no roughness, it was marked with O, and when there was roughness, it was marked with X. Development margin: The minimum development time at which a negative pattern appears and the residual film disappears within a 20 μm wide grid (80 μm square in the window to be removed) and the longest development time at which all of the above evaluation items pass.

[Adhesiveness with Glass Substrate] After post-baking, a 20 mm square negative pattern was cross-cut so as to make at least 100 cross-cuts, and then a peeling test was performed using cellophane tape to peel off the cross-cuts. By visually observing the state of, the evaluation was ◯: no peeling was observed at all, and x: peeling was observed at all.

Comparative Example 3 An image forming material having the same composition as in Example 5 was prepared using the acid-modified unsaturated resin solution before isocyanate modification prepared in Example 1. Further, an image forming material was prepared to form a coating film, and the light shielding rate, the sensitivity, the developing characteristics, and the adhesion to the glass substrate were examined. Table 2 shows the results.

[0071]

[Table 2]

As is clear from the results of Table 2, the black light-shielding film of Example 5 exhibits a light-shielding rate of 3.5 at a thickness of 1 μm,
It was also found that the sensitivity was high and the development margin was 30 to 70 seconds, which was sufficiently wide. Further, a negative pattern was sufficiently obtained even with an exposure amount of 200 mJ / cm ² . Further, it was found that a good black matrix pattern can be formed while having a sufficient light-shielding rate as compared with Comparative Example 3, and it can be suitably used as a black matrix of a color filter for a liquid crystal display.

Example 6 An image forming material was prepared in the same manner as in Example 1 except that the amount of propylene glycol monomethyl ether acetate used in preparing the image forming material was 10.0 g.

The obtained image-forming material was applied as a coating agent on a silicon wafer by spin coating,
After drying at 0 ° C. for 5 minutes, exposure to 200 mJ / cm ^{2 on} the basis of i-line was performed, followed by 2% in 0.7 wt% diethanolamine aqueous solution.
It was developed at 5 ° C. and post-baked at 200 ° C. for 1 hour. As a result of observing a pattern corresponding to a 10 μm line / space size with a negative mask having a film thickness of 10 μm after post-baking, a good 10 μm line / space was formed.

The insulation resistance of the coating film on which no pattern was formed was 1015 Ω, and the dielectric breakdown voltage was 220V. Further, as a result of thermogravimetric analysis, it was found that the weight loss starting temperature was 320 ° C. and that the sample had sufficient heat resistance. From these facts, it was found that the material of Example 6 was useful for an insulating film, particularly for an insulating film which requires fine pattern formation for MCM.

[0076]

The alkali-developable resin composition of the present invention and the image-forming material formed using the same have high sensitivity during pattern formation and are excellent in productivity, and the obtained pattern has heat resistance and It has excellent surface hardness, as well as excellent bending resistance and adhesiveness, and can be suitably used as an image forming material such as a color filter or an insulating film.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location H05K 3/46 H05K 3/46 T

Claims (3)

[Claims] 1. An addition product of diglycidyl ether and (meth) acrylic acid and an acid anhydride are expressed as follows: 0.3 ≦ X ≦ 0.9 (wherein the charge ratio X = {acid anhydride of charge acid anhydride) The number of moles of the group} / {the number of moles of the hydroxyl group of the charge adduct}), and then the resulting acid-modified unsaturated resin and diisocyanate compound are mixed in a ratio of 0.05 ≦ Y <1 (however, the charge ratio Y = [{mol number of isocyanate group of charged diisocyanate compound} / {mol number of hydroxyl group of charged adduct}] × {1 / (1-X)}), which is excellent in flexibility obtained by reacting Alkali developable resin composition. 2. A material for a color filter using the resin composition according to claim 1. 3. An insulating material using the resin composition according to claim 1.