KR101267111B1 - Photosensitive resin composition and method for producing photosensitive resin used therein - Google Patents

Abstract

The photosensitive resin composition of this invention reacts a polyfunctional epoxy compound and an unsaturated monobasic acid in presence of (A) trivalent organophosphorus compound, at least 1 sort (s) of zirconium naphthenate and zirconium octylate, and then reacts polybasic acid anhydride. And a photosensitive resin obtained by reacting a monoepoxy compound having an unsaturated double bond and a water-soluble monoepoxy compound, (B) an epoxy resin, (C) a photopolymerization initiator, and (D) a reactive diluent. . The photosensitive resin composition of the present invention does not contain a chromium compound, and is capable of developing by ultraviolet exposure and an aqueous alkali solution, and has high sensitivity, furthermore, good thermal stability and development control width, and a solder resist ink having excellent coating film performance. Suitable as.

Description

Photosensitive resin composition and the manufacturing method of the photosensitive resin used for the same [Photosensitive resin composition and method for producing photosensitive resin used therein}

TECHNICAL FIELD The present invention relates to a photosensitive resin composition, and more particularly, to a photosensitive resin composition which does not contain a chromium compound, is highly sensitive to ultraviolet light exposure, and the obtained coating film has good physical properties and can be developed by a rare alkali. will be.

In recent years, as a solder resist ink of various printed wiring boards, a liquid alkali photoresist ink of a alkali development type has been widely used. As a photosensitive resin of a rare alkali developing type, the acid pendant type epoxy acrylate resin obtained by making an acid anhydride react with the hydroxyl group of an epoxy acrylate resin is known, for example. Conventionally, chromium naphthenate has been used in the synthesis catalyst of such an acid pendant epoxy acrylate resin in order to obtain good thermal stability and development control width. However, it is not preferable to use a chromium compound such as chromium naphthenate as a synthesis catalyst from the point of increasing awareness of environmental problems and the waste liquid treatment after development. Thus, for example, Patent Document 1 proposes a photosensitive resin obtained by using an organophosphorus compound as a synthesis catalyst, reacting a polyfunctional epoxy resin with an unsaturated monobasic acid under predetermined conditions, and then reacting an acid anhydride. It is.

Prior art literature

Patent literature

Patent Document 1: Japanese Patent Application Laid-Open No. 2005-41958

Summary of the Invention

Problems to be solved by the invention

However, the photosensitive resin described in Patent Literature 1 cannot improve the performance such as sensitivity, thermal stability, development control width, heat resistance, solvent resistance, and the like required for the latest solder resist ink, and is still improved. There is room.

Therefore, the present invention does not contain a chromium compound and can be developed by ultraviolet exposure and an aqueous alkali solution, which is highly sensitive, and furthermore, has good thermal stability and development control width, and is suitable as a solder resist ink which exhibits excellent performance. It is an object to provide a photosensitive resin composition.

Means for solving the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the above-mentioned problem, the present inventors reacted a polyfunctional epoxy compound and an unsaturated monobasic acid in presence of a trivalent organophosphorus compound, at least 1 sort (s) of zirconium naphthenate and zirconium octylate, Then, the photosensitive resin composition which mix | blended the photosensitive resin obtained by making the monoepoxy compound which has an unsaturated double bond and the water-soluble monoepoxy compound react with the carboxyl group produced | generated by making polybasic acid anhydride react, discovered that it met the said objective, The invention has been completed.

That is, the present invention relates to reacting a polyfunctional epoxy compound with an unsaturated monobasic acid in the presence of at least one of (A) a trivalent organophosphorus compound, zirconium naphthenate and zirconium octylate, followed by reacting a polybasic acid anhydride. And a photosensitive resin obtained by reacting a monoepoxy compound having an unsaturated double bond and a water-soluble monoepoxy compound, a (B) epoxy resin, (C) a photopolymerization initiator, and (D) a reactive diluent. It is a photosensitive resin composition.

Moreover, this invention is a product obtained by the 1st process and 1st process which make a polyfunctional epoxy compound and an unsaturated monobasic acid react in presence of at least 1 sort (s) of a trivalent organophosphorus compound, zirconium naphthenate, and zirconium octylate. A second step of reacting a polybasic acid anhydride, a third step of reacting a monoepoxy compound having an unsaturated double bond with a product obtained in the second step, and a water-soluble monoepoxy compound, the method of producing a photosensitive resin.

Effects of the Invention

According to the present invention, it does not contain a chromium compound and can be developed by ultraviolet exposure and an aqueous alkali solution, and it is highly sensitive, and furthermore, it has good thermal stability and development control width, and is suitable as a solder resist ink having excellent coating performance. A resin composition can be provided.

Carrying out the invention  Form for

Hereinafter, the present invention will be described in detail.

First, the photosensitive resin composition of this invention is demonstrated.

In the photosensitive resin composition of this invention, (A) component makes a polyfunctional epoxy compound and an unsaturated monobasic acid react in presence of trivalent organophosphorus compound, at least 1 sort (s) of zirconium naphthenate and zirconium octylate, and then polybasic acid anhydride. It is a photosensitive resin obtained by making it react, and making the carboxyl group produced | generated thereby react the monoepoxy compound and water-soluble monoepoxy compound which have an unsaturated double bond.

The physical properties of the component (A) of the present invention are largely influenced by the catalyst used in the synthesis, and the development control width also tends to be affected by the catalyst. Moreover, when using a catalyst with different characteristics, each drawback tends to come out. However, the inventors have anticipated that when a trivalent organophosphorus compound is used in combination with at least one of zirconium naphthenate and zirconium octylate, It was found that the same physical properties as those obtained using a chromium-based catalyst can be obtained.

The amount of the catalyst used is preferably from 1.2 parts by mass to a total amount of at least one of trivalent organophosphorus compounds, zirconium naphthenate and zirconium octylate, with respect to 100 parts by mass of the total amount of the polyfunctional epoxy resin and the unsaturated monobasic acid. 6.0 mass parts. In that case, it is preferable to use at least 4 times of a trivalent organophosphorus compound by mass basis, and, as for at least 1 sort (s) of zirconium naphthenate and zirconium octylate, it is more preferable to use 4 times-6 times. When the total amount of at least one of the trivalent organophosphorus compound and zirconium naphthenate and zirconium octynate is too small, or the amount of at least one of zirconium naphthenate and zirconium octylate is less than four times that of the trivalent organophosphorus compound, It may not work enough as a reaction catalyst. On the other hand, when there are too many trivalent organophosphorus compounds, there exists a tendency for the thermal stability of the obtained photosensitive resin to fall, and even if there are too many at least 1 sort (s) of zirconium naphthenate and zirconium octylic acid, there is no effect suitable for a use amount, and it is not economical.

There is no restriction | limiting in particular as a polyfunctional epoxy compound used by this invention, For example, bisphenol A type, bisphenol F type, phenol novolak type, cresol novolak type, bisphenol A novolak type, cyclic aliphatic epoxy resin, hetero Epoxy resins, such as cyclic, and the thing which introduce | transduced halogen atoms, such as a bromine atom and a chlorine atom, are mentioned. Among these, cresol novolak-type epoxy resins are particularly preferable.

The unsaturated monobasic acid used in the present invention may be monobasic acid having one carboxyl group and at least one polymerizable unsaturated group, and for example, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbitanic acid, acrylic acid dimer and the like. Can be mentioned. Among them, the use of acrylic acid is particularly preferred from the viewpoint of obtaining high active energy photocurability. These unsaturated monobasic acids may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable to make these unsaturated monobasic acids react with 0.8 equivalent-1.1 equivalent with respect to 1.0 equivalent of the epoxy group of a polyfunctional epoxy compound. If the proportion of unsaturated monobasic acid is less than 0.8 equivalent, the storage stability may be deteriorated, and problems such as gelation may occur at the time of synthesis, while if it exceeds 1.1 equivalent, odor (odor) may occur and heat resistance may be caused. It tends to be lowered.

Examples of the polybasic acid anhydride used in the present invention include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and chromic anhydride. And polybasic acid anhydrides such as dibasic acid anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, and biphenyltetracarboxylic anhydride. Among them, the use of tetrahydro phthalic anhydride and hexahydro phthalic anhydride is particularly preferable from the standpoint of excellent corrosion resistance.

It is preferable that the usage-amount of these polybasic acid anhydrides becomes 0.4 mol-0.9 mol with respect to 1.0 mol of hydroxyl groups of the product obtained by making a polyfunctional epoxy compound and unsaturated monobasic acid react, and it is made to react in the ratio of 0.6 mol-0.9 mol. More preferred. When the usage-amount of polybasic acid anhydride is less than 0.4 mol, sufficient alkali developability may not be obtained. On the other hand, when it exceeds 0.9 mol, there exists a tendency for the electrical characteristics etc. of a cured coating film to fall.

As a monoepoxy compound which has an unsaturated double bond used by this invention, For example, alicyclic compounds, such as glycidyl methacrylate, glycidyl acrylate, and Daicel Kagaku Kogyo Co., Ltd. cyclomer-A200, M100 (Meth) acrylate which has a formula epoxy group is mentioned.

As a water-soluble monoepoxy compound, it is represented by the compound represented by following formula (I) (for example, Denacol (EX-145) and EX-171 by Nagase Chemtex Co., Ltd.), and following formula (II) The compound (for example, Sakamoto Yakuhin Kogyo Co., Ltd., SY-GTA80) etc. are mentioned:

In the formula, R ¹ represents an alkyl group or an aryl group, and R ² represents a polyethylene oxide or polypropylene oxide of 3 or more repeating units.

Since the monoepoxy compound which has an unsaturated double bond couple | bonded with the carboxyl group derived from polybasic acid anhydride is bound to the outermost part of resin, the reactivity at the time of ultraviolet irradiation is three-dimensionally high, and has high light sensitivity with respect to ultraviolet irradiation. In addition, the water-soluble monoepoxy compound improves the affinity of the resin to alkali, then appropriately suppresses the mobility of the unsaturated double bond of the monoepoxy compound having an unsaturated double bond, and imparts stability of the resin at the time of storage.

The amount of the monoepoxy compound having an unsaturated double bond and the water-soluble monoepoxy compound reacted with the carboxyl group produced by the reaction of the polybasic acid anhydride is 1 mole of the carboxyl group produced in consideration of the sensitivity, developability and electrical properties of the obtained photosensitive resin. It is preferable to make it react with respect to the total amount with respect to the ratio of 0.15 mol-0.25 mol. However, at that time, the amount of the water-soluble monoepoxy compound is preferably less than 0.03 mole, more preferably 0.01 mole to 0.025 mole with respect to 1 mole of the produced carboxyl group. If the total amount of the monoepoxy compound and the water-soluble monoepoxy compound having an unsaturated double bond is less than 0.15 mole, the effect of high sensitivity, which is one of the objects of the present invention, tends to be insufficient, whereas if it exceeds 0.25 mole, alkali development There is a tendency for the sex to decrease. In addition, even if the amount of the water-soluble monoepoxy compound is 0.03 mol or more, the added effect is low, and it is not practical in view of the above-mentioned alkali developability.

As an epoxy resin which is (B) component in the photosensitive resin composition of this invention, bisphenol-A epoxy resin, bisphenol F-type epoxy resin, hydrogenated bisphenol-A epoxy resin, phenol novolak-type epoxy resin, cresol novolak-type epoxy resin, and dish Clopentadiene-phenol novolac epoxy resins, phenol-cresol novolac co-condensation epoxy resins, bisphenol A novolac-type epoxy resins, bisphenol F novolac-type epoxy resins or their halogenated epoxy compounds, triphenylolmethane-type epoxy resins And polyfunctional phenols such as alkyl-substituted triphenylolmethane type epoxy resins, tetraphenylolethane type epoxy resins, and epoxy resins obtained by reacting epichlorohydrin with polyfunctional hydroxynaphthalene epichlorohydrin. Obtained epoxy resin, silicone modified epoxy resin, ε-caprolactone modified epoxy resin, epichloro It may be mentioned and gave first class or second class heterocyclic epoxy resin such as glycidyl amine type epoxy resin, triglycidyl isocyanate obtained by the reaction of the amine and the like. These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.

The compounding quantity of these epoxy resins becomes like this. Preferably it is 3 mass parts-100 mass parts, More preferably, it is 6 mass parts-75 mass parts with respect to 100 mass parts of photosensitive resin. When the compounding quantity of an epoxy resin is less than 3 mass parts, since the carboxyl group in photosensitive resin does not reach the amount which substantially reacts, water resistance, alkali resistance, and an electrical property tend to fall, and when it exceeds 100 mass parts, it is unreacted. Since the linear polymer which has an epoxy group is produced, heat resistance and solvent resistance may become inadequate.

Moreover, in order to further improve adhesiveness, chemical resistance, heat resistance, etc. of an epoxy resin, it is preferable to use an epoxy hardening | curing agent together. Examples of such epoxy curing agents include imidazole derivatives, phenol derivatives, dicyandiamide, dicyandiamide derivatives, melamine, melamine resins, hydrazide derivatives, amines, and acid anhydrides. These epoxy hardening | curing agents may be used individually by 1 type, and may be used in combination of 2 or more type. It is preferable that the compounding quantity of an epoxy hardening | curing agent is a ratio in which the active hydrogen amount of a hardening | curing agent becomes 0.5 mol-1.2 mol with respect to 1 mol of epoxy groups of an epoxy resin.

As a photoinitiator which is (C) component in the photosensitive resin composition of this invention, benzoin, such as benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, its derivatives, benzyl, benzyl dimethyl ketal, etc. Benzyl and derivatives thereof, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone Acetophenone and derivatives thereof, such as 2-methyl-1- (4-methylthiofil) -2-morpholinopropane-1-one, 2-methyl anthraquinone, 2-chloroanthraquinone and 2-ethylanthraquinone , Anthraquinones and derivatives thereof, such as 2-t-butyl anthraquinone, thioxanthones and derivatives thereof, such as thioxanthone, 2,4-dimethyl thioxanthone and 2-chlorothioxanthone, benzophenone, N, N Benzophenones such as -dimethyl aminobenzophenone and derivatives thereof. These photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, it is known that the photoinitiator effect is accelerated | stimulated by using various amine compounds together with these photoinitiators as needed, and can also be used in combination also in this invention.

The compounding quantity of these photoinitiators becomes like this. Preferably it is 0.1 mass part-20 mass parts, More preferably, it is 1 mass part-10 mass parts with respect to 100 mass parts of photosensitive resin. When the compounding quantity of a photoinitiator is less than 0.1 mass part, the effect as a photoinitiator may not fully be acquired, On the other hand, even if it exceeds 20 mass parts, there is no effect suitable for a compounding quantity, and it is not economical.

The reactive diluent which is (D) component in the photosensitive resin composition of this invention is used for the purpose of improving the coating property at the time of using curable and / or photosensitive resin composition with respect to active energy rays as a resist ink. As a reactive diluent, monomers with active energy ray-curable are preferable, and 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N-pyrrolidone, N-acryloyl morpholine, N, N- Dimethyl acrylamide, N, N-diethyl acrylamide, N, N-dimethyl aminoethyl acrylate, N, N-dimethyl aminopropyl acrylate, methoxy polyethylene glycol acrylate, ethoxy polyethylene glycol acrylate, melamine acrylate , Phenoxyethyl acrylate, phenoxypropyl acrylate, ethylene glycol diacrylate, dipropylene glycol diacrylate, polydipropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaeryte Lititol tetraacrylate, dipentaerythritol hexaacrylate, glycerin diacrylate, Isoboroyl acrylate, dicyclopentenyloxyethyl acrylate, and various methacrylates corresponding to these are mentioned. These reactive diluents may be used individually by 1 type, and may be used in combination of 2 or more type.

The compounding quantity of a reactive diluent becomes like this. Preferably it is 5 mass parts-200 mass parts, More preferably, it is 10 mass parts-100 mass parts with respect to 100 mass parts of photosensitive resin. If the compounding quantity of the reactive diluent is less than 5 parts by mass, sufficient light sensitivity may not be obtained. On the other hand, if it exceeds 200 parts by mass, the viscosity becomes too low when the photosensitive resin composition is used as a resist ink, and the curing is performed. The resistance as a coating film may become inadequate.

Moreover, a solvent can be used with a reactive diluent for adjustment of coatability. As such a solvent, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, carbitols such as ethyl cellosolve, butyl cellosolve, carbitol and butyl carbitol And ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, ethyl carbitol acetate and the like. These solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

In the case of using the photosensitive resin composition of the present invention as a liquid resist ink, in addition to the components (A) to (D) described above, if necessary, inorganic fillers such as silica, calcium carbonate, barium sulfate, clay, talc, Various additives such as coloring pigments such as phthalocyanine green, phthalocyanine blue, titanium oxide, carbon black, antifoaming agent, leveling agent, hydroquinone, resorcinol, catechol, pyrogarol, hydroquinone monomethyl ether, t-butylcatechol And polymerization inhibitors such as phenothiazine can be added.

Next, the manufacturing method of the photosensitive resin of this invention is demonstrated.

In a 1st process, a polyfunctional epoxy compound and unsaturated monobasic acid are made to react by a well-known method in presence of a trivalent organophosphorus compound, at least 1 sort (s) of zirconium naphthenate and zirconium octylate. In addition, since this reaction prevents thermal polymerization at the time of reaction, it is preferable to add well-known polymerization inhibitors, such as hydroquinone and methyl hydroquinone, in a system, and to carry out inhaling air in a system.

In 1st process, reaction temperature becomes like this. Preferably it is 60 degreeC-150 degreeC, and reaction time becomes like this. Preferably it is 5 hours-20 hours. When the polyfunctional epoxy compound is liquid, it is possible to react with a solvent, but when the polyfunctional epoxy compound is solid, it is preferable to react in a solvent. Examples of the solvent used herein include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, glycol ethers such as dipropylene glycol dimethyl ether, ethyl acetate, butyl cellosolve acetate, Esters such as carbitol acetate, ethyl carbitol acetate, butylcarbitol acetate, dipropylene glycol monomethyl ether acetate, and petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha.

In a 2nd process, polybasic acid anhydride is made to react with the product obtained by the 1st process by a well-known method. The reaction temperature in the second step is preferably 80 ° C to 120 ° C, and the reaction time is preferably 1 hour to 6 hours.

In a 3rd process, the monoepoxy compound and water-soluble monoepoxy compound which have an unsaturated double bond are made to react with the product obtained by the 2nd process by a well-known method. In 3rd process, reaction temperature becomes like this. Preferably it is 60 degreeC-150 degreeC, and reaction time becomes like this. Preferably it is 0.5 hour-20 hours.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

≪ Synthesis Example 1 &

192 parts by mass of ethylcarbitol acetate was added to a flask equipped with a stirrer, a gas introduction tube, and a reflux tube, and cresol novolac-type epoxy resin (Efototo (registered trademark) YDCN704, manufactured by Toto Kasei Kabushiki Kaisha), epoxy equivalent 206) 206 parts by mass (1 equivalent) was dissolved. Subsequently, 72 parts by mass of acrylic acid (1.0 mole), 0.23 parts by mass of hydroquinone, 0.4 parts by mass of triphenylphosphine, and 2 parts by mass of zirconium naphthenate (6% by mass of metal) were introduced, and air was introduced from the gas introduction pipe under the liquid level. The reaction was continued for 10 hours at 130 ° C. while inhaling to obtain a reactant (epoxy acrylate) having an acid value of 0.5 mgKOH / g. 111.03 parts by mass (0.73 mol) of tetrahydrophthalic anhydride was added thereto, and the mixture was further reacted at 120 ° C for 2 hours to obtain a reaction product having a solid acid value of 105.3 mgKOH / g. 22.72 parts by mass of glycidyl methacrylate (0.16 mole) and 9 parts by mass (0.02 mole) of Denacol (registered trademark) EX-145 (manufactured by Nagase Chemtex Co., Ltd., epoxy equivalent 450) were added at 120 ° C. The mixture was further reacted for 3 hours, and ethylcarbitol acetate was further added so that the nonvolatile content became 60% to obtain a photosensitive resin A having a solid acid value of 73.4 mgKOH / g.

≪ Synthesis Example 2 &

 Photosensitive resin B was obtained by the same operation as in Synthesis Example 1, except that 2 parts by mass of zirconium octylate (12 parts by mass of metal) was used instead of 2 parts by mass of naphthenate of zirconium (metal content 6% by mass).

Comparative Synthesis Example 1 (equivalent to Example 1 of Patent Document 1)

192 parts by mass of ethylcarbitol acetate was added to a flask equipped with a stirrer, a gas introduction tube, and a reflux tube, and cresol novolac-type epoxy resin (Efototo (registered trademark) YDCN704, manufactured by Toto Kasei Kabushiki Kaisha), epoxy equivalent 206) 206 parts by mass (1 equivalent) was dissolved. Next, 72 parts by mass (1.0 mol) of acrylic acid, 2.17 parts by mass of 2,6-di-t-butyl-4-methoxyphenol and 0.415 parts by mass of triphenylphosphine were added thereto, and air was sucked in from the gas inlet pipe under the liquid level. The reaction was continued for 10 hours at 130 ° C. while obtaining a reactant (epoxy acrylate) having an acid value of 1.0 mg KOH / g. 111.03 mass parts (0.73 mol) of tetrahydro phthalic anhydride and 0.707 mass part of lithium naphthenates (metal content 3%) were added to this, and it was made to react at 120 degreeC for further 2 hours, and the reaction material of 105.3 mgKOH / g of solid acid value was obtained. 22.72 parts by mass of glycidyl methacrylate (0.16 mole) and 9 parts by mass (0.02 mole) of Denacol (registered trademark) EX-145 (manufactured by Nagase Chemtex Co., Ltd., epoxy equivalent 450) were added at 120 ° C. The mixture was further reacted for 3 hours, and then ethylcarbitol acetate was added so that the nonvolatile content became 60% to obtain a photosensitive resin C having a solid acid value of 73.4 mgKOH / g.

Each component was mix | blended according to the compounding ratio shown in Table 1, it knead | mixed enough by 3 rolls, and the photosensitive resin composition was manufactured. The mass of the photosensitive resin of Table 1 was shown by the value of resin solid content.

Subsequently, the photosensitive resin composition was coated on the printed wiring board previously subjected to surface treatment by a screen printing method so as to have a thickness of 30 μm to 40 μm, preliminarily dried at 80 ° C. for 20 minutes, and then cooled to room temperature to obtain a dry coating film. This coating film was exposed at 250 mJ / cm <^2> using the oak Seisakujo ultrahigh pressure mercury lamp exposure apparatus, Then, it heated at 150 degreeC for 30 minutes using the hot air dryer, and obtained the cured coating film. Various physical property evaluation was performed about the obtained coating film according to the evaluation test method shown below. The results are shown in Table 2.

<Sensitivity>

A step tablet (Kodak 21 stage) for sensitivity measurement was installed in the dry coating film after preliminary drying, and it exposed at 250 mJ / cm <^2> using the high pressure mercury lamp exposure apparatus by Oku Seisakujo, and used the 1% sodium carbonate aqueous solution, The number of stages of the part in which the exposed part after removing image development for 60 ^second by 2.0 kgf / mm <^2> of spray pressures was measured. The higher the number of stages of the unremoved part, the higher the sensitivity.

<Development management width>

Using a dry coating film with a preliminary drying time of 20 minutes, 40 minutes, 60 minutes or 80 minutes, using a 1% aqueous sodium carbonate solution, development was carried out at a spray pressure of 2.0 kgf / mm ² , and the presence or absence of the coating film after development Was observed and evaluated based on the following criteria. Even if the drying time is long, the development control width is as good as that which can be developed.

(Circle): After 60 second of development time, there is no coating visually.

(Triangle | delta): After 120 seconds of image development time, there is no coating film visually.

X: After 120 seconds of developing time, there is a residual film visually.

<Solder Heat Resistance>

The cured coating film was floated so that the whole surface was submerged in solder according to JIS C6481, floated three times in a 260 ° C. solder bath for 10 seconds, and taken out. Then, the state of the coating film such as swelling or peeling was observed and evaluated according to the following criteria. .

○: no change in appearance.

X: There is a change in appearance.

<Contents Selling>

The coating film state after immersing a cured coating film in methylene chloride for 30 minutes was evaluated.

○: no change in appearance.

(Triangle | delta): Appearance changes slightly.

X: The coating film peeled off.

<Thermal Stability>

With respect to 100 mass parts of resin solid content of each photosensitive resin A-C, 10 mass parts of trimethylol propane triacrylates were added, it mixed for 10 minutes, and it puts into a test tube, making time until fluidity disappears at 120 degreeC as gelling time. Evaluated. The results are shown in Table 3.

Claims (5)

(A) Unsaturation in the carboxyl group produced by reacting a polyfunctional epoxy compound with an unsaturated monobasic acid in the presence of at least one of a trivalent organophosphorus compound, zirconium naphthenate and zirconium octylate, and then reacting the polybasic anhydride. A photosensitive resin composition comprising a photosensitive resin obtained by reacting a monoepoxy compound having a double bond and a water-soluble monoepoxy compound, (B) an epoxy resin, (C) a photopolymerization initiator, and (D) a reactive diluent. The method of claim 1, wherein the photosensitive resin is 0.15 mol to 0.25 mol in total amount of the monoepoxy compound having the unsaturated double bond and the water-soluble monoepoxy compound with respect to 1 mole of the carboxyl group (However, the water-soluble monoepoxy compound is Less than 0.03 mole). The photosensitive resin composition according to claim 1 or 2, wherein at least one of zirconium naphthenate and zirconium octylate is used at least four times as large as a trivalent organic compound on a mass basis. A first step of reacting a polyfunctional epoxy compound with an unsaturated monobasic acid in the presence of at least one of a trivalent organophosphorus compound, zirconium naphthenate and zirconium octylate,
A second step of reacting the polybasic acid anhydride with the product obtained in the first step,
And a third step of reacting the product obtained in the second step with the monoepoxy compound having an unsaturated double bond and the water-soluble monoepoxy compound. The method for producing a photosensitive resin according to claim 4, wherein the reaction is carried out in the first step while inhaling air.