JP2010150397A - Unsaturated group-containing resin, manufacturing method thereof and photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an unsaturated group-containing resin having a high rate of dissolution to alkali, as well as excellent thermal discoloration, development properties, and surface smoothness, and to provide a photosensitive resin composition. <P>SOLUTION: The photosensitive resin composition including an unsaturated group-containing resin is obtained by adding (meth)acrylic acid to a bisphenol-type epoxy resin, further adding succinic anhydride and/or maleic anhydride, and then adding a bisphenol type epoxy resin, as well as an unsaturated group-containing alkali-soluble resin to which succinic anhydride and/or maleic anhydride are/is further added, and a photopolymerizable monomer and photoinitiator are also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel method for producing a resin excellent in photocurability, heat resistance and alkali solubility, and a photosensitive resin composition.

  Conventionally, as a polymer having excellent heat resistance and photopolymerizability, after adding acrylic acid to an epoxy resin, tetrahydrophthalic anhydride, etc. are added, and the epoxy resin is further reacted to increase the molecular weight. Resin (for example, refer patent document 1) etc. are proposed.

  However, the polymers synthesized in the examples of Patent Document 1 are mainly used for solder resists, for example, photosensitive resin compositions for producing color filters used for liquid crystal displays and solid-state imaging devices. When used as a binder for products, development characteristics, particularly alkali solubility during development and surface smoothness may be insufficient.

  Moreover, it became clear that it decomposed | disassembles at the time of the heating in the formation process of a film | membrane or a film, and a decomposition gas generate | occur | produces. For example, when these polymers are used as photosensitive resins for creating liquid crystal displays and printed wiring boards, decomposition products generated during heating in the manufacturing process can contaminate the heating furnace, Contamination and electrical insulation properties may be reduced.

  Moreover, the problem that the thermal coloring of the resin at the time of a heating was strong also became clear. Accordingly, there has been a demand for a resin that can improve heat resistance, facilitate the preparation of a resin composition, and improve developability and surface smoothness when used as a photosensitive resin.

JP 7-237284 A

  Therefore, the present invention provides a resin and a photosensitive resin composition that have excellent heat resistance, can reduce the gas generated during heating, have a high dissolution rate with respect to alkali, and have excellent alkali developability and surface smoothness. Objective.

  The present inventor has intensively studied to solve the above problems. As a result, (meth) acrylic acid is added to the bisphenol-type epoxy resin, succinic anhydride and / or maleic anhydride is further added, and the bisphenol-type epoxy resin is further reacted, and succinic anhydride and / or The present inventors have found that an unsaturated group-containing resin reacted with maleic anhydride, a photopolymerizable monomer, and a photosensitive resin composition containing a photopolymerization initiator can solve the problems all at once.

  That is, the present invention provides an unsaturated group-containing resin obtained by adding (meth) acrylic acid to a bisphenol-type epoxy resin, adding succinic anhydride and / or maleic anhydride, and further reacting with a bisphenol-type epoxy resin, Further, it is an alkali-soluble resin obtained by reacting succinic anhydride and / or maleic anhydride, and further a photosensitive resin composition comprising a photopolymerizable monomer and a photopolymerizable initiator as essential components. .

  The resin of the present invention has high heat resistance and little decomposition gas during thermal coloring and heating, can form an extremely excellent coating film, has a high dissolution rate in alkali and high surface smoothness. Thus, for example, it can be suitably used in photosensitive resin compositions used for the production of color filters for use in photosensitive resin compositions, various coating agents, paints, and the like, particularly for liquid crystal displays and solid-state imaging devices.

  The unsaturated group-containing resin of the present invention comprises (A) (meth) acrylic acid added to a bisphenol type epoxy resin, (B) further succinic anhydride and / or maleic anhydride added, and (C) further bisphenol type. An unsaturated group-containing resin obtained by reacting an epoxy resin, and (D) an unsaturated group-containing resin to which succinic anhydride and / or maleic anhydride is further added.

  By introducing a skeleton derived from succinic anhydride and / or maleic anhydride into the resin, the photosensitive resin composition using the unsaturated group-containing resin of the present invention has excellent heat resistance and coloration resistance. It was found to be something. This is presumed to be due to the addition of succinic anhydride and / or maleic anhydride, which is excellent in alkali solubility and extremely high in heat resistance and suppresses thermal decomposition.

  Further, the obtained unsaturated group-containing resin is further reacted with succinic anhydride and / or maleic anhydride to form a film having very excellent alkali solubility and surface smoothness. Have.

Hereinafter, the unsaturated group-containing resin will be described.
The bisphenol type epoxy resin used in the step (A) may be an epoxy resin having a bisphenol skeleton, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy. Resin. Among these, bisphenol A type epoxy resins and hydrogenated bisphenol A type epoxy resins are preferable from the viewpoints of solubility in solvents, heat decomposition resistance, heat resistance colorability, industrial availability, and the like. Among these, bisphenol A type epoxy resins are most preferable from the viewpoints of industrial availability, alkali solubility, and little coloration by heating. The epoxy equivalent of the bisphenol A type epoxy resin is preferably 100 to 500, more preferably 150 to 400, and most preferably 150 to 200. By making an epoxy equivalent into the said range, the molecular weight of the polymer obtained can be controlled to an appropriate range, and the outstanding alkali solubility can be exhibited.

  The (meth) acrylic acid used in the step (A) is a general term for acrylic acid and methacrylic acid. Either one of acrylic acid and methacrylic acid may be used in combination, but acrylic acid is preferred because it is excellent in reactivity and alkali solubility.

  Either one of the succinic anhydride and / or maleic anhydride used in the step (B) may be used in combination. Succinic anhydride is preferred in terms of low thermal coloring.

  The ratio of the bisphenol-type epoxy resin and (meth) acrylic acid used in step (A) and step (B) is not particularly limited, but the molar ratio of epoxy group to carboxyl group is 1: 0.95 to 1: 1. .1 is preferable, and 1: 1 to 1: 1.05 is particularly preferable. By making it in the above range, (meth) acrylic acid remaining can be suppressed, and side reaction between (meth) acrylic acid and epoxy resin remaining in the step (C) described later can be suppressed, and thermal decomposability and developability can be suppressed. Thus, a resin having an excellent balance of photocurability can be obtained.

  The molar ratio of succinic anhydride and / or maleic anhydride used in the step (B) to the epoxy group of the bisphenol type epoxy resin used in the step (A) is preferably 1: 1 to 1: 1. : 1-1: 1.05 is particularly preferable. By setting it as the said range, the reactivity is high, the residual amount of an acid anhydride can be reduced, and reaction in the following (C) process can fully be advanced.

  The bisphenol type epoxy resin used in the step (C) may be an epoxy resin having a bisphenol skeleton, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy. Resin. Among these, bisphenol A type epoxy resins and hydrogenated bisphenol A type epoxy resins are preferable from the viewpoints of solubility in solvents, heat decomposition resistance, heat resistance colorability, industrial availability, and the like. Among these, bisphenol A type epoxy resins are most preferable from the viewpoints of industrial availability, alkali solubility, and little coloration by heating. The epoxy equivalent of the bisphenol A type epoxy resin is preferably 100 to 500, more preferably 150 to 400, and most preferably 150 to 200. By making an epoxy equivalent into the said range, the molecular weight of the polymer obtained can be controlled to an appropriate range, and the outstanding alkali solubility can be exhibited.

  The ratio of the bisphenol type epoxy resin used in the step (C) is extremely important in the industrial production of the unsaturated group-containing resin of the present invention. That is, the molar ratio (X / Y) of the epoxy group (X) of the bisphenol type epoxy resin added in the step (C) and the succinic anhydride and / or maleic anhydride (Y) used in the step (B), It is preferable to set it to 0.5 or more and 0.85 or less. More preferably, it is 0.5 or more and 0.8 or less, and most preferably 0.5 or more and 0.75 or less. By making the molar ratio within the above range, the molecular weight of the resulting resin can be controlled to an appropriate range, the decrease in alkali solubility due to the increase in molecular weight, the increase in viscosity and gelation during synthesis can be prevented, and the heat resistance An unsaturated group-containing resin excellent in the balance between alkali solubility and alkali can be produced industrially and stably.

  Either one of succinic anhydride and / or maleic anhydride used in step (D) may be used, or both may be used together. However, succinic anhydride is less in that the resin is less colored. Is preferred. By adding an acid anhydride in the step (D), the amount of the carboxyl group of the resin can be adjusted, and it becomes possible to impart alkali solubility according to the conditions used.

  The amount of the succinic anhydride and / or maleic anhydride used in the step (D) may be appropriately set depending on the desired alkali solubility of the resin, and is not particularly limited, but is 1 to 30% by mass with respect to the resin. Preferably, 1-20 mass% is still more preferable.

  The unsaturated group-containing resin of the present invention may have monomer components other than the essential bisphenol type epoxy resin, (meth) acrylic acid, succinic anhydride, and maleic anhydride, but occupies the polymer. The total mass ratio of the essential monomer units is preferably 70% by mass or more, for example. More preferably, it is 80% by mass or more, still more preferably 90% by mass or more, and most preferably, all the components are essential monomer units. By setting the ratio of the other monomer component within the above range, a resin having an excellent balance of heat decomposition resistance, heat resistance coloring property, alkali solubility, surface smoothness and the like, which is an object of the present invention, is obtained.

  There is no restriction | limiting in particular as the method of addition reaction of the said (A) process thru | or (D) process, Although a conventionally well-known reaction method is employable, It is preferable to make it react in a solution especially.

  Also, the reaction temperature and reaction concentration (reaction concentration (%) = [total weight of monomer components / (total weight of monomer components + solvent weight)] × 100) are set to the monomer components used. Although it varies depending on the type and ratio and the molecular weight of the target polymer, the reaction temperature is preferably 60 to 150 ° C. and the reaction concentration is 20 to 100%, more preferably the reaction temperature is 80 to 130 ° C. and the reaction concentration is 30. It should be ˜80%.

  When a solvent is used in the reaction of the monomer component, a solvent inert to the acid, acid anhydride, or epoxy compound may be used as the solvent. Preferably, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate And esters such as 3-methoxybutyl acetate; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; chloroform; dimethyl sulfoxide; N-methylpyrrolidone;

  These solvents may be used alone or in combination of two or more. Of these, propylene glycol monomethyl ether acetate and diethylene glycol ethyl methyl ether are preferred from the viewpoint of industrial availability, safety to human bodies and the environment, and high solubility.

  When reacting the monomer component, it is preferable to use a catalyst usually used for the addition reaction of a carboxyl group and an epoxy group. Although it does not specifically limit as a catalyst used for the addition reaction of a carboxyl group and an epoxy group, For example, Amines, such as a triethylamine, a tributylamine, a dimethylbenzylamine; Ammonium salts, such as a tetraethylammonium chloride and a tetraethylammonium bromide; Phosphines such as phenylphosphine; phosphonium salts such as tetraphenylphosphonium chloride and tetraphenylphosphonium bromide; amide compounds such as dimethylformamide; metal salt compounds and the like.

  Among these, particularly when used as a binder for photosensitive resin compositions used in the manufacture of color filters and semiconductors used in liquid crystal displays and solid-state imaging devices, ionic substances such as salt compounds are electrically conductive. It is not preferred because of its properties, and amines and phosphines are preferred, and triethylamine, dimethylbenzylamine, and triphenylphosphine are most preferred from the viewpoint of low thermal coloring and high catalytic activity. These catalysts may be used alone or in combination of two or more.

  The amount of the catalyst used may be appropriately set according to the reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but is preferably 0.01 to 5% by mass with respect to the total monomer components. Is preferably 0.1 to 1% by mass. By setting the amount of catalyst within the above range, the resin can be less thermally colored, and the reaction rate can be controlled within an appropriate range, so that it can be stably produced with a calorific value capable of industrial heat removal.

  When reacting the monomer component, it is preferable to use a polymerization inhibitor in order to prevent gelation due to thermal polymerization of unsaturated bonds. The polymerization inhibitor is not particularly limited and known ones can be used. For example, hydroquinone, hydroquinone monomethyl ether (also called p-methoxyphenol), t-butylcatechol, 6-t-butyl-2,4- Examples thereof include phenol polymerization inhibitors such as xylenol (also known as topanol) and 2,2′-methylenebis (4-methyl-6-tert-butylphenol). The amount used is preferably 0.01 to 0.5%, more preferably 0.02 to 0.3%, based on the total monomers. By making it within the above range, a polymerization inhibiting effect can be sufficiently exerted, a gelation prevention during reaction and storage stability can be improved, and a resin free from thermal coloring and photopolymerization deterioration can be obtained. At the same time, bubbling a mixed gas of nitrogen and air or oxygen with an oxygen concentration adjusted to 5 to 10% in the reaction system is preferable because the polymerization inhibition effect can be further enhanced.

  Although the weight average molecular weight of unsaturated group containing resin of this invention is not restrict | limited in particular, Preferably it is 2000-200000, More preferably, it is 5000-100000, Most preferably, it is 5000-50000. By setting the weight average molecular weight within the above range, an appropriate viscosity is obtained, and a coating film having high alkali solubility, high heat resistance and high surface smoothness can be formed. In addition, the measurement of the weight average molecular weight of the resin of the present invention uses a column filled with polystyrene gel, which is generally used in a normal GPC method, and in the measurement method using tetrahydrofuran as an eluent, adsorption occurs in the column. The present inventors have found that the high molecular weight portion of the peak is not detected and the molecular weight cannot be accurately measured. As a result of various studies, the present inventors have used a highly polar column packed with a polyvinyl alcohol cross-linked product and the like, and added a small amount of an acidic substance such as phosphoric acid to the eluent, such as dimethylformamide or N-methylpyrrolidone. It has been found that an accurate molecular weight can be measured by using a polar solvent. A specific measuring method is shown in the examples.

  The unsaturated group-containing resin preferably has an acid value of 20 to 150 mgKOH / g, and more preferably 30 to 80 mgKOH / g. By setting the acid value in the above range, the alkali dissolution rate at the time of alkali development can be adjusted to an appropriate range without being too fast, and the coating film after curing has a high alkali resistance and has a surface on the developer. As a result, it is possible to form a good coating film in which the surface smoothness is not deteriorated by being attacked.

Next, the unsaturated group containing resin containing photosensitive resin composition of this invention is demonstrated. The photosensitive resin composition of the present invention contains the unsaturated group-containing resin, the photoreactive monomer, and the photopolymerization initiator as essential components, and, if necessary, a solvent, a colorant, a dispersant, an epoxy resin, and a surfactant. An agent, an antioxidant and the like can be blended.
As the photopolymerizable monomer, a known polyfunctional (meth) acrylate is preferable, and since it is easily available industrially and the crosslink density can be increased, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, dipenta Trifunctional or higher polyfunctional acrylates such as erythritol hexaacrylate are preferred, and pentafunctional or higher polyfunctional acrylates are particularly preferred. Although the usage-amount of a photopolymerizable monomer does not have a restriction | limiting in particular, 50 mass%-200 mass% are preferable with respect to unsaturated group containing resin.
Examples of the photopolymerization initiator include thioxanthones such as 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; acylphosphine oxides and xanthones, and the like may be used alone. Two or more types may be used.
Moreover, the content rate becomes like this. Preferably it is 0.1-50 mass% with respect to the said unsaturated group containing resin, More preferably, it is 0.5-30 mass%. Moreover, a sensitizer can also be used together as needed.
As the colorant and the dispersant, for example, known colorants and dispersants described in JP-A Nos. 2003-215322 and 2003-270428 can be used.

  Moreover, in the photosensitive resin composition of the present invention, a known alkali-soluble resin, epoxy resin, or the like may be used in combination, if necessary, but the use ratio is 0 to 50 with respect to the unsaturated group-containing resin. % By mass is preferable, and 0 to 30% by mass is more preferable.

The photosensitive resin composition of this invention may contain the solvent as a diluent as needed.
The solvent is not particularly limited as long as the unsaturated group-containing resin, the photopolymerizable monomer, and the photopolymerization initiator are uniformly dissolved and do not react. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl Esters such as ether acetate and 3-methoxybutyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; Chloroform, dimethyl sulfoxide; and the like. In addition, what is necessary is just to set content of a solvent suitably according to the optimal viscosity at the time of using.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the scope of the present invention is not limited by these Examples. Unless otherwise specified, “parts” means “parts by weight”.
In the following examples, various physical properties and the like were measured as follows.

<Weight average molecular weight>
GPC (gel) by HLC-8120GPC (manufactured by Tosoh Corporation) and column TSKgel Super AW5000 (manufactured by Tosoh Corporation) using polystyrene as a standard substance and dimethylformamide adjusted to a water concentration of 1% by mass and a phosphoric acid concentration of 8.5 mmol / kg as an eluent. The weight average molecular weight was measured by a permeation chromatography method.

<Acid value>
3 g of the resin solution was precisely weighed, dissolved in a mixed solvent of 90 g of acetone / 10 g of water, titrated with 0.1N KOH aqueous solution using thymol blue as an indicator, and the acid value per 1 g of the solid content was determined from the concentration of the solid content.

Example 1
<Synthesis of resin solution>
(A) In a separable flask with a cooling tube as a reaction vessel, 350 parts of a bisphenol A type epoxy resin (828EL manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 187 g / eq) is added, and 1 part of p-methoxyphenol is used as a polymerization inhibitor. After adding 0.1 parts of ethylenediaminetetraacetic acid as a chelating agent and heating to 115 ° C. while bubbling nitrogen and oxygen mixed gas (oxygen concentration 7%), 138 parts of acrylic acid, propylene glycol monomethyl ether acetate (PGMEA) 138 And 3.6 parts of triethylamine were added and reacted for 4 hours. (B) The reaction product was cooled to 100 ° C., 187 parts (Y = 1.87) of succinic anhydride and 221 parts of PGMEA were added and reacted for 3 hours. (C) Subsequently, 233 parts (X = 1.25) of bisphenol A type epoxy resin (828EL manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 187 g / eq) and 1000 parts of PGMEA, and 1 part of p-methoxyphenol as a polymerization inhibitor were added. After the reaction at 115 ° C. for 6 hours, the resin solution 1 was obtained by cooling to room temperature. X / Y = 0.67.

  When various physical properties of the obtained resin solution 1 were measured, the weight average molecular weight was 13,000, the solid content obtained by drying at 160 ° C. under vacuum was 40.0%, and the solid content determined by the titration method The per acid value was 48 mgKOH / g.

<Evaluation of heat resistant colorability of resin solution>
After mixing 100 parts by weight of resin solution 1 and 100 parts by weight of PGMEA, spin-coating on a glass substrate, drying at 100 ° C. for 3 minutes, heating at 220 ° C. for 20 minutes, and then coating film having a thickness of 1.5 μm 1 was formed.

  After measuring the transmittance of the coating film 1, it was further heated at 230 ° C. for 1 hour, and the transmittance was measured again. As a result, the decrease in transmittance at 400 nm was 3.3 T%.

<Adjustment of photosensitive resin composition>
12 parts of resin solution 1, 8 parts by weight of dipentaerythritol pentaacrylate, Irgacure 369 (manufactured by Ciba Geigy) as a photopolymerization initiator, 0.3 part by weight, and 79.7 parts by weight of PGMEA are mixed, and a photosensitive resin composition is prepared. Obtained.

<Evaluation of developability and surface smoothness>
The obtained photosensitive resin composition was spin-coated on a glass substrate and dried at 120 ° C. for 3 minutes to form a coating film 2 having a thickness of 2.0 μm.

The coating film 2 was exposed to 50 mJ / cm ² of UV light through a line and space photomask having a line width of 15 μm with a UV exposure apparatus (TME-150RNS manufactured by Topcon), and a spin developing machine (manufactured by Actes Co., Ltd.). ADE-3000S) was developed with a 0.05% aqueous potassium hydroxide solution for 20 seconds. As a result, the pattern shape was very good, no residue of unexposed areas was observed, and the developability was good. Further, the surface smoothness of the pattern was very good.

Example 2
(A) In a separable flask with a cooling tube as a reaction vessel, 350 parts of a bisphenol A type epoxy resin (828EL manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 187 g / eq) is placed, and 1 part of p-methoxyphenol as a polymerization inhibitor, Add 0.1 parts of ethylenediaminetetraacetic acid as a chelating agent, heat to 115 ° C while bubbling nitrogen and oxygen mixed gas (oxygen concentration 7%), add 138 parts of acrylic acid, 138 parts of PGMEA, and 3.6 parts of triethylamine. The reaction was performed for 4 hours. (B) The reaction product was cooled to 100 ° C., 187 parts (Y = 1.87) of succinic anhydride and 221 parts of PGMEA were added and reacted for 3 hours. (C) Subsequently, 262 parts (X = 1.40) of bisphenol A type epoxy resin (828 EL manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 187 g / eq) and 1042 parts of PGMEA, and 1 part of p-methoxyphenol as a polymerization inhibitor were added. , Reacted at 115 ° C. for 6 hours. X / Y = 0.75. (D) Further, 9 parts by weight of succinic anhydride was added, reacted at 110 ° C. for 3 hours, and then cooled to room temperature to obtain a resin solution 2.

  When various physical properties of the obtained polymer solution 2 were measured, the weight average molecular weight measured by GPC (gel permeation chromatography) using polystyrene as a standard substance was 25,600, obtained by drying at 160 ° C. under vacuum. The obtained solid content concentration was 41.5%, and the acid value per solid content determined by the titration method was 43 mgKOH / g.

  After 72 parts by weight of resin solution 2 and 78 parts by weight of PGMEA were mixed, spin coating was performed on a glass substrate, and the decrease in transmittance was measured in the same manner as in Example 1. As a result, it was 2.8 T%.

  Further, the same operation as in Example 1 was performed except that the resin solution 2 was used to obtain a photosensitive resin composition, and the same operation as in Example 1 was performed to measure the developability and surface smoothness. Was also very good.

Example 3
(A) In a separable flask with a cooling tube as a reaction vessel, 350 parts of a bisphenol A type epoxy resin (828EL manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 187 g / eq) is placed, and 1 part of p-methoxyphenol as a polymerization inhibitor, Add 0.1 parts of ethylenediaminetetraacetic acid as a chelating agent, heat to 115 ° C while bubbling nitrogen and oxygen mixed gas (oxygen concentration 7%), then add 138 parts of acrylic acid, 138 parts of PGMEA, and 3.6 parts of triethylamine. The reaction was performed for 4 hours. (B) The reaction product was cooled to 100 ° C., 187 parts (Y = 1.87) of succinic anhydride and 221 parts of PGMEA were added and reacted for 3 hours. (C) Subsequently, 583 parts (X = 1.17) of bisphenol A type epoxy resin (YD-901, epoxy equivalent 467 g / eq, manufactured by Tohto Kasei Co., Ltd.) and 1523 parts of PGMEA, and p-methoxyphenol 1.3 as a polymerization inhibitor Part was added and reacted at 115 ° C. for 6 hours. X / Y = 0.63. (D) Further, 9 parts by weight of succinic anhydride was added, reacted at 110 ° C. for 3 hours, and then cooled to room temperature to obtain a resin solution 3.

When various physical properties of the obtained resin solution 3 were measured, the weight average molecular weight was 19,200, the solid content concentration was 39.9%, and the acid value per solid content was 50 mgKOH / g.
The same operation as in Example 1 was performed, and the heat resistant colorability of the resin solution was measured. The results are shown in Table 1.

Further, the same operation as in Example 1 was performed to obtain a photosensitive resin composition, and developability and surface smoothness were measured.
Although a slight fringe was observed at the edge of the pattern, it was generally good. When the development time was 30 seconds, no fringes were observed and the developability was good. Further, no surface roughness was observed even at a development time of 30 seconds, and the surface smoothness was extremely good.

Comparative Example 1
(A) In a separable flask with a cooling tube as a reaction vessel, 350 parts of a bisphenol A type epoxy resin (828EL manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 187 g / eq) is placed, and 1 part of p-methoxyphenol as a polymerization inhibitor, Add 0.1 parts of ethylenediaminetetraacetic acid as a chelating agent, heat to 115 ° C while bubbling nitrogen and oxygen mixed gas (oxygen concentration 7%), then add 141 parts of acrylic acid, 141 parts of PGMEA, and 4.1 parts of triethylamine. The reaction was performed for 4 hours. (B) The reaction product was cooled to 100 ° C., 289 parts of tetrahydrophthalic anhydride and 274 parts of PGMEA were added and reacted for 3 hours. (C) Subsequently, 233 parts of bisphenol A type epoxy resin (828EL manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent of 187 g / eq), 1100 parts of PGMEA, and 1 part of p-methoxyphenol as a polymerization inhibitor were added, and at 115 ° C. for 6 hours. Reacted. (D) Further, 22 parts by weight of tetrahydrophthalic anhydride was added, reacted at 110 ° C. for 3 hours, and then cooled to room temperature to obtain a resin solution 4.

  When various physical properties of the obtained resin solution 4 were measured, the weight average molecular weight was 13,200, the solid content concentration was 39.7%, and the acid value per solid content was 59 mgKOH / g.

  After 76 parts by weight of resin solution 4 and 74 parts by weight of PGMEA were mixed, spin coating was performed on a glass substrate, and the same operation as in Example 1 was performed to measure heat resistant colorability. The results are shown in Table 1. It can be seen that the decrease in transmittance at 400 nm is larger than that in Example 1 and the thermal coloring is strong.

  Moreover, except having used the resin solution 4, operation similar to Example 1 was performed, the photosensitive resin solution was obtained, and developability and surface smoothness were measured. Part of the undissolved portion was left undissolved in the unexposed area, and the developability was poor. Further, when the development time was extended to 30 seconds, the unexposed portion remained undissolved, but fringes were observed at the edge of the pattern, and a partial pattern defect was confirmed. Further, the surface of the cured portion was rough, and the surface smoothness was poor.

Comparative Example 2
(A) In a separable flask with a cooling tube as a reaction vessel, 350 parts of a bisphenol A type epoxy resin (828EL manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 187 g / eq) is placed, and 1 part of p-methoxyphenol as a polymerization inhibitor, After adding 0.1 parts of ethylenediaminetetraacetic acid as a chelating agent and heating to 115 ° C while bubbling nitrogen and oxygen mixed gas (oxygen concentration 7%), 141 parts of acrylic acid, 141 parts of PGMEA, and 4.1 parts of triethylamine were added. The mixture was further reacted for 4 hours. (B) The reaction product was cooled to 100 ° C., 289 parts of tetrahydrophthalic anhydride and 274 parts of PGMEA were added and reacted for 3 hours. (C) Subsequently, 263 parts of a bisphenol A type epoxy resin (828 EL manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 187 g / eq), 1100 parts of PGMEA, and 1 part of p-methoxyphenol as a polymerization inhibitor were added, and 6 parts at 115 ° C. Reacted for hours. (D) Further, 51 parts by weight of tetrahydrophthalic anhydride was added, reacted at 110 ° C. for 3 hours, and then cooled to room temperature to obtain a resin solution 5.

When various physical properties of the obtained resin solution 5 were measured, the weight average molecular weight was 19,700, the solid content concentration was 40.1%, and the acid value per solid content was 57 mgKOH / g.
The resin solution 5 was subjected to the same operation as in Example 1, and the heat resistant colorability was measured. The results are shown in Table 1.

  Moreover, except having used the resin solution 5, operation similar to Example 1 was performed, the photosensitive resin composition was obtained, and developability and surface smoothness were measured. Many residues remained undissolved in the unexposed areas. Even when the development time was 30 seconds, the residue in the unexposed area was not lost and the developability was poor. Further, the surface was attacked by the developer, streaky surface roughness was observed in the direction of flow of the developer, and the surface smoothness was poor.

  From the above-mentioned Examples and Comparative Examples, it can be seen that the photosensitive resin composition using the unsaturated group-containing resin of the present invention is small in thermal coloring and excellent in alkali developability and surface smoothness.

  It is useful as a binder polymer, a thermosetting resin, and various coating materials for a photosensitive resin composition used in the production of liquid crystal displays, color filters for solid-state imaging devices, printed wiring boards, and the like.

Claims (6)

(A) (Meth) acrylic acid is added to a bisphenol-type epoxy resin,
(B) After further adding succinic anhydride and / or maleic anhydride,
(C) An unsaturated group-containing resin characterized by further adding a bisphenol-type epoxy resin. To the unsaturated group-containing resin obtained by the method according to claim 1,
(D) An unsaturated group-containing resin characterized by adding succinic anhydride and / or maleic anhydride. The unsaturated group-containing resin according to claim 1 or 2, wherein the bisphenol type epoxy resin is a bisphenol A type epoxy resin. In the step (C), the molar ratio (X / Y) of the epoxy group (X) of the bisphenol-type epoxy resin to be added and the succinic anhydride and / or maleic anhydride (Y) added in the step (B) is It is 0.5 or more and 0.85 or less, The manufacturing method of unsaturated group containing resin of Claims 1-3 characterized by the above-mentioned. A photosensitive resin composition comprising the unsaturated group-containing resin according to claim 1, a photopolymerizable monomer, and a photopolymerization initiator. A cured product obtained by curing the photosensitive resin composition according to claim 5.