JP2006083289A - Epoxy resin, epoxy resin composition and alkali-development type photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alkali-development type photosensitive resin composition having a wide span of drying control, good dry-touch feeling after drying, and good developability without reducing heat resistance; and to provide a new epoxy resin to be contained therein. <P>SOLUTION: The epoxy resin composition contains an epoxy resin (X) obtained by reacting a polyfunctional epoxy resin (Y) containing two or more epoxy groups in average in one molecule, with an aromatic monoisocyanates (a), and having an oxazolidone ring, and a curing agent. The epoxy resin (X) is obtained by reacting the polyfunctional epoxy resin (Y) containing two or more epoxy groups in average in one molecule, with the aromatic monoisocyanates (a), and has the oxazolidone ring. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is an epoxy resin, an epoxy resin composition useful for composite materials, adhesives, paints, etc., including electrical and electronic component insulating materials such as printed wiring boards and semiconductor encapsulants, and conductive paste fiber reinforced composite materials, The present invention relates to a prepreg and a cured product thereof, and in particular, an alkali development type photosensitive resin composition used as an interlayer insulating material of a printed wiring board, and further has a wide dry management width and good without reducing heat resistance. The present invention relates to an epoxy resin that can be suitably used for an alkali-developable photosensitive resin composition having resolution.

  A printed wiring board is for mounting a circuit pattern on a circuit board by soldering an electronic component to the soldering land of the pattern, and the circuit part excluding the soldering land is permanent. It is coated with a solder resist film as a protective film. This prevents solder from adhering to unnecessary parts when soldering electronic components to a printed wiring board, and prevents circuit conductors from being directly exposed to air and being corroded by oxidation or humidity. . Conventionally, a solder resist film has been mainly formed by patterning a solution composition on a substrate by a screen printing method, drying the solvent composition, and then curing it with ultraviolet rays or heat.

  However, recently, with the demand for improving the wiring density of printed wiring boards (fine densification), solder resist compositions (also called solder resist ink compositions) are also required to have high resolution and high precision. A liquid photo solder resist method (photo development method) has been proposed from the screen printing method regardless of the industrial substrate. For example, JP-A-50-144431 and JP-A-51-40451 disclose a solder resist composition comprising a bisphenol type epoxy acrylate, a sensitizer, an epoxy compound, an epoxy curing agent, and the like. These solder resist compositions are applied to the entire surface of a liquid composition, which is a photosensitive resin composition, on a printed wiring board, and after volatilizing the solvent, it is exposed to remove unexposed portions using an organic solvent, Develop. However, the removal (development) of unexposed areas with organic solvents is not only dangerous for the environment and fire, but also has a problem of environmental pollution, especially because it uses a large amount of organic solvent. Since the impact has been greatly closed up recently, it is difficult to take countermeasures.

  In order to solve these problems, an alkali-developable photosensitive resin composition that can be developed with a dilute alkaline aqueous solution, a reaction product of a novolak epoxy resin and an unsaturated monocarboxylic acid, and a saturated or unsaturated polybasic acid anhydride There has been proposed a photocurable resist ink composition that can be developed with a dilute alkaline aqueous solution containing an active energy ray-curable resin obtained by reacting a product with a photopolymerization initiator (see, for example, Patent Document 1). .)

  These solder resist compositions are usually diluted in a solvent, and after applying this, the solvent is removed under conditions within the dry control range, and the resulting coating film is exposed and developed to form a desired resist pattern. After being formed, it is cured by heat to form a resist film having excellent adhesion, hardness, heat resistance, chemical resistance, electrical insulation and the like. This drying control width is the management of the thermal tolerance limit of the coating film curing degree that can be removed during development of the unexposed part during coating film drying. If the drying management width is narrow, that is, the temperature rises due to heat. If the allowable range is narrow, the resin composition of the coating film is cured by the time or temperature exceeding the allowable range in the drying process of applying the alkali-developable photosensitive resin composition to the printed wiring board and removing the solvent. Then, after exposure and development, there arises a problem that the unexposed part is hardly removed by the developer. For this reason, the drying time and drying temperature are limited, and the number of coatings must be restricted, and the tackiness remains due to the remaining solvent, resulting in problems such as deterioration of the dryness to touch. In particular, since the above-described high resolution and high accuracy are serious problems, it is strongly desired to improve the drying management width.

JP-A 61-243869

  In view of the above problems, the present invention provides an alkali development type photosensitive resin composition having a wide drying control range, good dryness to touch after drying, and further good developability without reducing heat resistance, An object of the present invention is to provide a novel epoxy resin contained therein.

  As a result of intensive studies to solve the above problems, the inventors of the present invention contain an oxazolidone ring obtained by reacting a specific ratio of epoxy groups in an epoxy resin with isocyanate groups in aromatic monoisocyanates. The epoxy resin to be used is a novel resin, and the epoxy resin composition containing the epoxy resin, the epoxy resin, the carboxyl group-containing photopolymerizable unsaturated compound (A) and the photopolymerization initiator (C) are alkali-developable. The present inventors have found that a photosensitive resin composition can solve the above problems, and have reached the present invention. That is, the present invention is as follows.

  That is, the present invention is an epoxy containing an oxazolidone ring obtained by reacting a polyfunctional epoxy resin (Y) containing two or more epoxy groups on average in one molecule with an aromatic monoisocyanate (a). An epoxy resin composition comprising a resin (X) and a curing agent.

  The present invention also relates to an epoxy containing an oxazolidone ring obtained by reacting a polyfunctional epoxy resin (Y) containing two or more epoxy groups on average in one molecule with an aromatic monoisocyanate (a). There is also provided an alkali development type photosensitive resin composition comprising a resin (X), a carboxyl group-containing photopolymerizable unsaturated compound (A), and a photopolymerization initiator (C).

  The present invention also relates to an epoxy containing an oxazolidone ring obtained by reacting a polyfunctional epoxy resin (Y) containing two or more epoxy groups on average in one molecule with an aromatic monoisocyanate (a). Resin (X) is also provided.

  The alkali development type photosensitive resin composition of the present invention drastically improves the drying control width (or development life) and developability by using an epoxy resin containing an oxazolidone ring as a thermosetting component, and A solder resist film excellent in heat resistance of the cured product can be formed with good workability.

Hereinafter, the contents of the present invention will be described in detail.
Epoxy resin containing an oxazolidone ring obtained by reacting a polyfunctional epoxy resin (Y) containing two or more epoxy groups on average in the molecule of the present invention with aromatic monoisocyanates (a) (X ) Is an epoxy resin (X) containing an oxazolidone ring. Examples of the polyfunctional epoxy resin (Y) used in the present invention include glycidyl ethers, glycidyl esters, glycidyl amines, linear aliphatic epoxides, and alicyclic epoxides. Examples of the glycidyl ethers include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, and tetrachlorobisphenol A. Bisphenol-type epoxy resins obtained by glycidylating bisphenols such as tetrafluorobisphenol A; other 2 such as resorcin, hydroquinone, catechol, biphenol, tetramethylbiphenol, dihydroxynaphthalene, 9,9-bis (4-hydroxyphenyl) fluorene Epoxy resin obtained by glycidylation of polyhydric phenols; 1,1,1-tris (4-hydroxyphenyl) methane, 4,4 Epoxy resin obtained by glycidylation of trisphenols such as (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol; 1,1,2,2, -tetrakis (4 -Epoxy resin obtained by glycidylating tetrakisphenols such as hydroxyphenyl) ethane; phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak, naphthol novolak, phenol-cresol co-condensed novolak, naphthol- Novolac-type epoxy resins obtained by glycidylating novolaks such as phenol-condensed novolak and naphthol-cresol-compacted novolak; naphthol aralkyl obtained by glycidylating naphthol aralkyl resins Epoxy resins; dicyclopentadiene - glycidyl the phenol addition type resins and dicyclopentadiene - phenol addition reaction type epoxy resins.

  Examples of glycidyl esters include hexahydrophthalic acid and diglycidyl esters of dimer acid. Examples of the glycidylamines include diaminodiphenylmethane, metaxylenediamine, 1,3-bisaminomethylcyclohexane, and a compound obtained by glycidylating aminophenol.

  Examples of the linear aliphatic epoxides include epoxidized polybutadiene and epoxidized soybean oil. Examples of the alicyclic epoxide include 3,4-epoxy-6-methylcyclohexylcarboxylate, 3,4-epoxycyclohexylcarboxylate, and the like. Furthermore, triglycidyl isocyanurate can also be used as the polyfunctional epoxy resin (Y).

  These polyfunctional epoxy resins (Y) may be used alone or in combination of two or more. Among these, preferable polyfunctional epoxy resins (Y) are glycidyl ethers, and more preferably, at least one novolac epoxy resin selected from phenol novolac epoxy resins and cresol novolac epoxy resins. It is done. More preferably, the one having good touch-drying properties after temporary drying is a phenol novolac epoxy resin having a softening point in the range of 70 to 110 ° C or a cresol novolac epoxy resin having a softening point in the range of 70 to 110 ° C. Novolak type epoxy resin. Moreover, it is a novolak-type epoxy resin of the range of semisolid-softening point 80 degreeC among these that solder heat resistance becomes favorable.

  As aromatic monoisocyanates (a) used in the present invention, phenyl isocyanate, tolyl isocyanate, xylyl isocyanate, trimethylphenyl isocyanate, acetylphenyl isocyanate, ethoxyphenyl isocyanate, cyanophenyl isocyanate, dimethoxyphenyl isocyanate, naphthyl isocyanate, Biphenylyl isocyanate, phenoxyphenyl isocyanate, fluorophenyl isocyanate, bromophenyl isocyanate, benzenesulfonyl isocyanate, toluenesulfonyl isocyanate and the like can be mentioned. Two or more of these aromatic monoisocyanates can be used in combination.

  In addition, for the purpose of adjusting compatibility and drapeability, aliphatic monoisocyanates such as methyl isocyanate, ethyl isocyanate, butyl isocyanate, hexane isocyanate and octadecyl isocyanate, and alicyclic monoisocyanates such as cyclohexyl isocyanate and adamantyl isocyanate are used. Can be used together.

  A polyisocyanate compound can be used together with aromatic monoisocyanates. Examples of the polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, 2,2,4 (or 2,4,4) -trimethyl-1,6-diisocyanatohexane, and lysine. Aliphatic diisocyanates such as diisocyanates. Cycloaliphatic diisocyanates such as isophorone diisocyanate, 1,3-bis (isocyanatomethyl) -cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate. Examples thereof include aromatic diisocyanates such as tetramethylxylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, and xylylene diisocyanate. The amount of the polyisocyanate compound used is preferably such that the isocyanate in the polyisocyanate compound is 0.5 equivalent or less with respect to 1 equivalent of the isocyanate in the aromatic monoisocyanate, more preferably 0.2 equivalent. It is as follows.

  The amount of the aromatic monoisocyanate (a) used is such that the isocyanate group is 0.05 to 0.5 equivalent with respect to 1 equivalent of the epoxy group in the polyfunctional epoxy resin (Y). Preferably, it is 0.05 to 0.3 equivalent.

  The reaction of these isocyanate groups with epoxy groups is described in Iwakura et al. Polymer Sci. Part A-1, 4, 751 (1966) can be carried out by a known method. Basically, an appropriate amount of these two components is put in a container in the presence or absence of an appropriate solvent, and heated and stirred. do it.

  In addition, the isocyanate group in the aromatic monoisocyanates (a) reacts with the epoxy group to form an oxazolidone ring, and in part, as a side reaction, the formation of a urethane bond with the alcoholic hydroxyl group in the epoxy resin And isocyanurate ring formation by cyclization trimerization of isocyanate groups.

  The production of the epoxy resin (X) of the present invention is usually carried out in the presence of a catalyst. Examples of the catalyst include metal alcoholates such as butoxylithium and methoxysodium, Lewis acids such as lithium chloride and aluminum chloride, and mixtures of Lewis acids and Lewis bases such as triphenylphosphine oxide, tetramethylammonium, tetraethylammonium, and tetrabutyl. Chlorides such as ammonium and benzyltributylammonium, bromide, iodide, tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, benzyltributylphosphonium and other quaternary ammonium salts such as bromide, iodide and acetate, triethylamine, N, N-dimethyl Benzylamine, 1,8-diazabicyclo [5.4.0] undecene-7,1,4-diazabicyclo [2.2.2] o Tertiary amines such as Tan, 2-ethyl-4-methylimidazole, imidazoles such as 2-phenylimidazole, and the like. Two or more kinds of catalysts may be used in combination. As the catalyst, quaternary ammonium salts, quaternary phosphonium salts and tertiary amines are particularly preferred. The amount of the catalyst used is usually in the range of 5 ppm to 2% by weight with respect to the polyfunctional epoxy resin (Y). Preferably, it is 20 ppm to 0.5% by weight. The catalyst can also be used after diluted in a suitable solvent.

  The production of the epoxy resin (X) of the present invention can be carried out without a solvent or in the presence of a suitable solvent. When using solvents, N, N-dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylacetamide, methyl ethyl ketone, methyl isobutyl ketone, mesitylene, xylene, toluene, methyl cellosolve acetate Solvents free from active hydrogen such as ethyl diglycol acetate and tetrahydrofuran are preferred.

  The reaction temperature is usually 80 ° C to 220 ° C. Preferably it is 100 degreeC-200 degreeC, More preferably, it is 120 degreeC-190 degreeC. If the reaction temperature is too low, the activity of the catalyst is low, and side reactions such as formation of isocyanurate rings occur. Moreover, even if the reaction temperature is too high, the activity of the catalyst is lowered and the side reaction proceeds.

  In the production of the epoxy resin (X) of the present invention, the polyfunctional epoxy resin (Y) is heated to a predetermined temperature, and after removing moisture in the resin as much as possible by blowing dry air or nitrogen, drying under reduced pressure, etc., Aromatic monoisocyanates (a) and a catalyst are preferably added. The aromatic monoisocyanates (a) and the catalyst may be added simultaneously at the same time, but it is preferable to add them separately, simultaneously, in several times, or continuously. In the case of continuous charging, the charging time is preferably 0.5 to 10 hours, more preferably 0.5 to 5 hours. When the charging time is short, the amount of isocyanurate ring produced may increase.

  The epoxy resin (X) of the present invention comprises 5 to 50 equivalent%, preferably 5 to 30 equivalent%, of the epoxy group in the polyfunctional epoxy resin (Y) and the isocyanate group in the aromatic monoisocyanate (a). It reacts to form an oxazolidone ring. If the amount is less than 5 equivalent%, the effect is small, and an alkali development type photosensitive resin composition having a wide drying control range cannot be obtained. On the other hand, when it exceeds 50 equivalent%, the heat resistance and mechanical properties of the cured product are lowered.

  Among the epoxy groups in this polyfunctional epoxy resin (Y), the proportion of those involved in oxazolidone ring formation is determined by, for example, a method of measuring the Oxd conversion rate by a chemical method described later in the Examples section, infrared spectroscopy It can be known by a method of quantification using an instrumental analytical method such as a method and nuclear magnetic resonance spectroscopy.

  Moreover, it is preferable that the epoxy equivalent of the said epoxy resin (X) is a thing of the range of 220-300 g / equivalent from the point from which the effect of this invention becomes remarkable.

  Epoxy resin containing an oxazolidone ring obtained by reacting a polyfunctional epoxy resin (Y) containing two or more epoxy groups on average in the molecule of the present invention with aromatic monoisocyanates (a) (X ), An epoxy resin containing an oxazolidone ring has a urethane bond obtained by a reaction between a part of alcoholic hydroxyl groups in the polyfunctional epoxy resin (Y) and an isocyanate group in the aromatic monoisocyanates (a). You may contain. The urethane bond amount is preferably 10 equivalent% or less, more preferably 5 equivalent% or less of the content of the oxazolidone ring. When there are many urethane bond amounts, the melt viscosity of an oxazolidone ring containing epoxy resin will become high.

  The epoxy resin of the present invention can contain (b) an isocyanurate ring in which the isocyanate group in the isocyanate compound is cyclized and trimerized. The content of the isocyanurate ring is preferably 10 equivalent% or less of the content of the oxazolidone ring, more preferably 5 equivalent% or less, still more preferably 1 equivalent% or less. When there are too many isocyanurate rings, when manufacturing an oxazolidone ring containing epoxy resin, polymerization stability will fall or the melt viscosity of an oxazolidone ring containing epoxy resin will become high. The oxazolidone ring-containing epoxy resin of the present invention preferably contains substantially no isocyanate group.

  The amount of hydrolyzable chlorine in the epoxy resin (X) containing an oxazolidone ring of the present invention is not particularly limited, but for example, when used for electric / electronic applications, 500 ppm or less is preferable.

  In the epoxy resin (X) of the present invention, a part of the epoxy group can be modified with the modifying agent (c) to obtain an oxazolidone ring-containing modified epoxy resin.

  The modifier (c) used in the present invention is not particularly limited as long as it is a compound having a functional group that reacts with an epoxy group. For example, phenol such as xylenol, t-butylphenol, nonylphenol, bisphenol A, hydroquinone and the like. Alcohols such as n-butanol, butyl cellosolve, polyethylene glycol monoethyl ether, ethylene glycol, polypropylene glycol, butylamine, octylamine, diethylamine, methylbutylamine, monoethanolamine, diethanolamine, N-methylethanolamine, triethylamine hydrochloride, N, N-dimethylethanolamine acetate, amines such as dimethylketimine of aminoethylethanolamine, acetic acid, lactic acid, 2-ethylhexanoic acid, lauric acid, 2-hydroxystearic acid, benzoic acid, carboxylic acids such as dimethanolpropionic acid, sulfides such as diethyl disulfide / acetic acid mixture, mercaptans such as γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, etc., acrylic Examples thereof include unsaturated carboxylic acids such as acid and methacrylic acid. Two or more of these modifiers (c) can be used in combination.

  Further, the amount of modification by the modifying agent (c) is not particularly limited, but is preferably selected according to the cured form of the modified oxazolidone ring-containing modified epoxy resin obtained by modification. When the cured form of the oxazolidone ring-containing modified epoxy resin is cured using an epoxy group, the amount of modification is preferably 50 equivalent% or less with respect to the epoxy group, since the crosslinking density decreases when the modification amount increases. More preferably, it is 1-40 equivalent%. When the curing form of the modified oxazolidone ring-containing epoxy resin uses a crosslinkable group incorporated by modification or a secondary hydroxyl group generated by modification, the crosslinking density does not increase if the modification amount is small. 50 equivalent% or more is preferable with respect to group. More preferably, it is 60-100 equivalent%.

  For example, after modification with amines, conversion to an ionic group such as conversion of an amino group into an ammonium salt using acetic acid or the like can be performed.

  The epoxy resin (X) of the present invention can be mixed with a curing agent (d) to form a curable composition. Although it does not specifically limit as a hardening | curing agent to combine, For example, hardening | curing agents, such as an amine compound, an acid anhydride type compound, an amide type compound, a phenol type compound, can be used. Examples of these amine compounds include ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, and other aliphatic polyamines, metaxylylenediamine, diaminodiphenylmethane, and phenylene. Aromatic polyamines such as diamine, alicyclic polyamines such as 1,3-bis (aminomethyl) cyclohexane, isophoronediamine, norbornanediamine, etc., and dimer of dicyandiamide and linolenic acid and ethylenediamine are synthesized. A polyamide resin is mentioned.

  Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride. And methyl hexahydrophthalic anhydride.

  The phenolic compounds include phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane. Examples thereof include resins, tetraphenylolethane resins, naphthol novolak resins, naphthol-phenol co-condensed novolak resins, naphthol-cresol co-condensed novolak resins, biphenyl-modified phenol resins, aminotriazine-modified phenol resins, and modified products thereof. Examples of the latent catalyst include imidazole, BF3-amine complex, and guanidine derivatives.

  Further, these amine compounds, acid anhydride compounds, amide compounds, phenol compounds and the like curing agents may be used alone or in combination of two or more.

  In the epoxy resin composition of the present invention, the amount of the curing agent used is that the curing proceeds smoothly and good cured physical properties are obtained. Therefore, the silyl ether in the entire curing agent with respect to 1 equivalent of the epoxy group of the epoxy resin. The amount in which the total of the groups and active hydrogen groups is 0.5 to 1.5 equivalents is preferred.

  Moreover, a hardening accelerator can also be further used for the epoxy resin composition of this invention suitably. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like. The above combination is also possible. For example, as a semiconductor sealing material, phosphorus-based triphenylphosphine and amine-based DBU are preferable because of excellent curability, heat resistance, electrical characteristics, moisture resistance reliability, and the like.

    The addition amount is not particularly limited, but is preferably in the range of 0.05 to 10% by weight with respect to the total amount of the epoxy resin and the curing agent.

  The curable composition of this invention can contain a solvent as needed. Examples of the solvent include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, naphtha, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ethyl acetate, acetic acid-n-butyl, ethylene diglycol acetate, An ester such as propylene glycol monomethyl ether acetate, an alcohol such as methanol, isopropanol, n-butanol, butyl cellosolve, and butyl carbitol, water, and the like can be appropriately selected according to the purpose and use. These solvents may be used alone or in combination of two or more.

  In the curable composition of the present invention, pigments, fillers, additives and the like commonly used in the technical field as shown below can be used. For example, organic pigments such as quinacridone, azo, and phthalocyanine, inorganic pigments such as titanium oxide, metal foil pigments, rust preventive pigments, barium sulfate, calcium carbonate, spherical fused silica, crushed fused silica, crystalline silica, alumina , Fillers such as silicon nitride, aluminum hydroxide, carbon black, talc and clay, UV absorbers such as hindered amines, benzotriazoles and benzophenones, oxidations such as hindered phenols, phosphoruss, sulfurs and hydrazides Examples thereof include additives such as inhibitors, silane-based and titanium-based coupling agents, leveling agents, rheology control agents, pigment dispersants, repellency inhibitors, antifoaming agents, and the like. Moreover, reinforcing materials, such as glass fiber, glass cloth, and carbon fiber, can be contained as needed. Moreover, a flame retardant imparting agent can be added as necessary. Various flame retardants can be used as the flame retardant, such as halogen compounds such as decabromodiphenyl ether and tetrabromobisphenol A, phosphorus atom-containing compounds such as red phosphorus and various phosphate compounds, melamine or derivatives thereof, etc. Examples thereof include inorganic flame retardant compounds such as nitrogen atom-containing compounds, aluminum hydroxide, magnesium hydroxide, zinc borate, and calcium borate.

  The epoxy resin (X) of the present invention can be mixed with a carboxyl group-containing photopolymerizable unsaturated compound (A) and a photopolymerization initiator (C) to form an alkali development type photosensitive resin composition.

  The effect of the present invention is remarkable when the epoxy equivalent of the epoxy resin (X) containing an oxazolidone ring used in the alkali development type photosensitive resin composition of the present invention is in the range of 220 to 300 g / equivalent. It is preferable from the point of becoming.

  The softening point of the epoxy resin (X) containing an oxazolidone ring used in the alkali development type photosensitive resin composition of the present invention is preferably in the range of 50 ° C to 150 ° C. The contact dryness is good in the range of 70 to 150 ° C., and the solder heat resistance is good in the range of 50 to 130 ° C.

  The carboxyl group-containing photopolymerizable unsaturated compound (A) used in the alkali-developable photosensitive resin composition of the present invention is not particularly limited, but reacts with a polyfunctional epoxy acrylate compound and an acid anhydride compound. What is obtained is preferably obtained. Here, as the polyfunctional epoxy acrylate compound, any one obtained by reacting a conventionally known polyfunctional epoxy resin with an unsaturated carboxylic acid can be used.

  As the polyfunctional epoxy resin used here, resorcinol type epoxy resin; bisphenol type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin; dihydroxynaphthalene type epoxy resin, binaphthol type epoxy Naphthalene type epoxy resin such as resin; biphenol type epoxy resin such as biphenol type epoxy resin and tetramethylbiphenol type epoxy resin; phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, naphthol novolak type epoxy resin Resin, novolac epoxy resin such as alkylphenol novolac epoxy resin; phenol-dicyclopentadiene epoxy resin, etc. It is below. Among these, a novolak type epoxy resin is particularly preferable from the viewpoints of alkali solubility and heat resistance, and a cresol novolak type epoxy resin is particularly preferable. The unsaturated carboxylic acid to be reacted with the polyfunctional epoxy resin is not particularly limited as long as it contains one or more double bonds and carboxylic acid in one molecule, but specifically acrylic acid. And methacrylic acid.

  The carboxyl group-containing photopolymerizable unsaturated compound (A) is obtained by reacting an acid anhydride compound with a polyfunctional epoxy acrylate compound obtained by reacting the polyfunctional epoxy resin with an unsaturated carboxylic acid. Acid anhydride compounds that can be used here include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone Examples thereof include polybasic acid anhydrides such as tetracarboxylic dianhydride, ethylene glycol bistrimellitic dianhydride, biphenyl tetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride.

The ratio of the acid anhydride compound to be reacted is not particularly limited, but the acid anhydride group is 0.2 to 2.5 mol with respect to one hydroxyl group equivalent of the carboxyl group-containing photopolymerizable unsaturated compound. It is preferable. That is, in the range of 0.2 mol or more, the solubility in an alkaline aqueous solution is improved, and in the range of 2.5 mol or less, the stability is good.
Such a carboxyl group-containing photopolymerizable unsaturated compound (A) preferably has an acid value in the range of 30 to 200 mgKOH / g. That is, when the acid value is in the range of 200 mgKOH / g or less, the cured film has excellent properties such as alkali resistance and electrical properties, and when it is 30 mgKOH / g or more, the solubility in the aqueous alkali solution is further improved.

  Next, the photopolymerization initiator (C) used in the composition of the present invention is not particularly limited, and is generally used as a photopolymerization initiator for a photopolymerizable unsaturated compound having an ethylene bond. Can be used. Specific examples of such photopolymerization initiator (C) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, and p-tert-butylacetophenone. Acetophenones such as benzophenone, 2-chlorobenzophenone, benzophenones such as p, p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal Sulfur compounds such as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, Anthraquinones such as luanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, organic peroxides such as benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimigzole, 2-mercapto Examples thereof include thiol compounds such as benzoxazole and 2-mercaptobenzothiazole, and azobisisobutylnitrile. These compounds may be used alone or in combination of two or more. In addition, a compound that does not act as a photopolymerization initiator per se, but that can increase the ability of the photopolymerization initiator by using it in combination with the above-mentioned compound can also be added. Examples of such compounds include tertiary amines such as triethanolamine which are effective when used in combination with benzophenone.

  The alkali-developable photosensitive resin composition of the present invention includes a carboxyl group-containing photopolymerizable unsaturated compound (A), an epoxy resin (X) containing an oxazolidone ring, and a photopolymerization initiator (C). As an essential component, the mixing ratio of these components is not particularly limited, but an epoxy containing an oxazolidone ring with respect to 100 parts by weight of the carboxyl group-containing photopolymerizable unsaturated compound (A). The resin (X) component is preferably 5 to 50 parts by weight, and the photopolymerization initiator (C) component is preferably 0.1 to 30 parts by weight from the point that the effect of the present invention becomes remarkable. That is, with respect to 100 parts by weight of the compound (A), the epoxy resin (X) component containing an oxazolidone ring has 5 parts by weight or more, and the alkali resistance of the cured product becomes better. The property is further improved. Further, when the photopolymerization initiator (C) component is used in an amount of 0.1 part by weight or more based on 100 parts by weight of the compound (A), the speed of photopolymerization is increased and the sensitivity is improved. On the other hand, when the amount is 30 parts by weight or less, light easily reaches the bottom of the resin layer, so that the development margin can be expanded and the adhesion to the substrate is improved.

  Among these, 10-30 parts by weight of an epoxy resin (B) component containing an epoxy resin (X) containing an oxazolidone ring, particularly with respect to 100 parts by weight of a carboxyl group-containing photopolymerizable unsaturated compound (A), It is preferable that the amount of the photopolymerization initiator (C) component is 1 to 20 parts by weight from the viewpoint that the balance of each performance described above is further improved.

  The alkali development type photosensitive resin composition of the present invention may be used in combination with an epoxy resin other than the epoxy resin (X) containing an oxazolidone ring as the curing agent component of the carboxyl group-containing photopolymerizable unsaturated compound (A). Good. The epoxy resin other than the epoxy resin (X) containing an oxazolidone ring to be used in combination is not particularly limited, but bisphenol A type epoxy resin, bisphenol F type epoxy resin, resorcin type epoxy resin, bisphenol S type epoxy resin, dihydroxynaphthalene type Epoxy resin, binaphthol type epoxy resin, biphenol type epoxy resin, tetramethylbiphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, naphthol novolak type epoxy resin, alkylphenol type epoxy resin, etc. Is mentioned. In order to impart flame retardancy, it is preferable to use a brominated epoxy resin that is a bromine-substituted product of the above epoxy resin. Specific examples include tetrabromobisphenol A and brominated phenol novolac type epoxy resins. In this case, it is preferable to use a brominated epoxy resin so that the bromine content in the resin composition is in the range of 3 to 30% by weight. That is, in the range of 3% by weight or more, the flame retardant effect is remarkably good, and in the case of 30% by weight or less, the occurrence of blistering of the plating film when the amount of bromine is excessive can be prevented.

  In addition to the above components, the alkali-developable photosensitive resin composition of the present invention can be blended with another photopolymerizable unsaturated compound (D) having an ethylene bond in accordance with the intended physical properties. The blending amount of the photopolymerizable unsaturated compound (D) having another ethylene bond in that case has a range of 50 parts by weight or less with respect to 100 parts by weight of the carboxyl group-containing photopolymerizable unsaturated compound (A) component. From the viewpoint of tackiness after precuring. Examples of such a photopolymerizable unsaturated compound include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-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, trimethylolethanetri (Meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Sri Tall tetra (meth) acrylate, di pentaerythritol hexa (meth) acrylate, glycerol (meth) (meth) acrylic acid esters such as acrylate.

  In addition, the alkali development type photosensitive resin composition of the present invention contains various additives such as an epoxy group curing accelerator, a thermal polymerization inhibitor, a plasticizer, a leveling agent, an antifoaming agent, and an extender if necessary. be able to. Examples of the epoxy group curing accelerator include amine compounds, imidazole compounds, carboxylic acids, phenols, quaternary ammonium salts, methylol group-containing compounds, and the like. Thus, it is possible to improve various characteristics such as heat resistance, solvent resistance, acid resistance, plating resistance, adhesion, electrical characteristics, and hardness of the obtained insulating coating.

  As the thermal polymerization inhibitor, for example, hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, etc., as the plasticizer, for example, dibutyl phthalate, dioctyl phthalate, tricresyl etc., as the antifoaming agent, leveling agent, For example, silicon-based, fluorine-based, acrylic-based compounds and the like, and examples of extender pigments include silica, alumina, talc, calcium carbonate, clay, and aerosil. The alkali development type photosensitive resin composition of the present invention described in detail above is suitably used as an interlayer insulating material for build-up multilayer substrates and a permanent insulating protective film for printed wiring boards, and particularly as an interlayer insulating material for build-up multilayer substrates. Useful.

  Below, the method used from the alkali development type photosensitive resin composition of this invention as an interlayer insulation material of a buildup multilayer substrate is illustrated. First, the above-described components are kneaded with a three-roll mill or the like to prepare an alkali development type photosensitive resin composition. The photosensitive resin composition is applied on the substrate by an arbitrary method such as screen printing, and then dried to evaporate the solvent and make the coating film tack-free. After drying, a desired mask pattern is placed in a contact (contact) or off-contact (non-contact) state on a substrate on which a coating film of the composition has been formed, and ultraviolet rays are selectively irradiated. The components of the composition coating film in the region exposed to ultraviolet rays are photopolymerized to take a crosslinked structure and become insoluble. The desired pattern developed is obtained by removing the non-exposed areas with an aqueous alkaline solution. As the alkaline aqueous solution, an aqueous solution of alkanolamine such as 0.1 to 10% by weight of potassium hydroxide, sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, monoethanolamine or the like is used. The pattern thus obtained is subjected to heat treatment at 100 to 200 ° C. or ultraviolet irradiation to improve the coating film strength, and then signal wiring is formed by electroless plating, via hole inner surface plating, etc. Thus, a printed wiring board excellent in moisture resistance reliability and heat resistance can be obtained.

  The present invention will be described in more detail based on examples and comparative examples, but the technical scope and embodiments of the present invention are not limited thereto. “Parts” or “%” in Examples and Comparative Examples are based on weight unless otherwise specified. The property value test of the resin of this example was performed by the method described below.

(1) Epoxy equivalent: It is the weight (g) of a resin containing 1 equivalent of an epoxy group, and was determined according to JIS K-7236.
(2) Softening point: compliant with JIS K-7234 (ring and ball method).
(3) Oxd conversion rate: equivalent percentage of the epoxy group forming the oxazolidone ring with respect to the original epoxy group, and in the oxazolidone ring formation reaction of this example, in addition to the reaction in which the epoxy group forms an oxazolidone ring, Since it is not substantially used, the epoxy equivalent (referred to as EpY) and weight (referred to as WtY) of the polyfunctional epoxy resin (Y) used, and the epoxy equivalent (EpX) of the resulting epoxy resin (X) containing the oxazolidone ring ) And weight (referred to as WtX), and the following formula was used.
Oxd conversion rate = [100− (WtX / EpX) / (WtY / EpY)] × 100

In addition, the epoxy resin containing the oxazolidone ring described in Examples 2 and 8 (polyfunctional epoxy resin (Y) containing two or more epoxy groups on average in one molecule and aromatic monoisocyanates (a The formation of the oxazolidone ring in the epoxy resin (X) containing an oxazolidone ring obtained by reacting) was confirmed by the presence of the FT-IR absorbance peak (1753 to 1756 cm ⁻¹ ) in FIGS. 1 and 2. Measurement conditions and IR chart examples are described below.

Measurement conditions Measurement equipment: FT / IR-500 (manufactured by JASCO), measurement mode: absorbance, integration number: 100 times, apodization: Cosine, gain: 16, resolution: 4 cm ⁻¹ , aperture diameter: 5.0 mm, zero filling : X 2

Example 1
A separable flask containing 214 parts of a cresol novolac-type epoxy resin (EPICLON N-695 (manufactured by Dainippon Ink and Chemicals) (softening point 95 ° C., epoxy equivalent 214 g / equivalent)), a stirrer, thermometer, reflux condenser, A nitrogen blowing tube was attached and the temperature was raised to 150 ° C. with stirring while blowing nitrogen into the flask, and stirring was continued for 30 minutes after reaching 150 ° C. While maintaining the reaction temperature at 150 ° C., 6 parts of phenyl isocyanate and tetra A mixture of 0.05 part of butylammonium chloride (Wako Pure Chemical) was added dropwise over 2 hours, after which the stirring was continued for 6 hours while maintaining the reaction temperature at 150 ° C., and an oxazolidone ring-containing epoxy resin ( Table 1 shows the characteristic values of the epoxy resin containing the obtained oxazolidone ring. Show.

Example 2
An oxazolidone ring-containing epoxy resin (X2) was obtained in the same manner as in Example 1 except that 6 parts of phenyl isocyanate was changed to 18 parts of phenyl isocyanate. The characteristic values of the epoxy resin containing the obtained oxazolidone ring are shown in Table 1.

Example 3
An oxazolidone ring-containing epoxy resin (X3) was obtained in the same manner as in Example 1 except that 6 parts of phenyl isocyanate was changed to 36 parts of phenyl isocyanate. The characteristic values of the epoxy resin containing the obtained oxazolidone ring are shown in Table 1.

Example 4
An oxazolidone ring-containing epoxy resin (X4) was obtained in the same manner as in Example 1 except that 6 parts of phenyl isocyanate was changed to 60 parts of phenyl isocyanate. The characteristic values of the epoxy resin containing the obtained oxazolidone ring are shown in Table 1.

Example 5
An oxazolidone ring-containing epoxy resin (X5) was obtained in the same manner as in Example 1 except that 6 parts of phenyl isocyanate was changed to 22 parts of xylyl isocyanate. The characteristic values of the epoxy resin containing the obtained oxazolidone ring are shown in Table 1.

Example 6
An oxazolidone ring-containing epoxy resin (X6) was obtained in the same manner as in Example 1 except that 6 parts of phenyl isocyanate was changed to 25 parts of naphthyl isocyanate. The characteristic values of the epoxy resin containing the obtained oxazolidone ring are shown in Table 1.

Example 7
Cresol novolak type epoxy resin (EPICLON N-695) was changed to 200 g of cresol novolak type epoxy resin (EPICLON N-655-EXP-S (Dainippon Ink Chemical Co., Ltd.) (softening point 58 ° C., epoxy equivalent 200 g / equivalent)) Except for the above, an oxazolidone ring-containing epoxy resin (X7) was obtained in the same manner as in Example 2. Table 1 shows the characteristic values of the obtained epoxy resin containing an oxazolidone ring.

Example 8
Except that the cresol novolac type epoxy resin (EPICLON N-695) was changed to 188 g of phenol novolak type epoxy resin (EPICLON N-775 (Dainippon Ink and Chemicals) (softening point 74 ° C., epoxy equivalent 188 g / equivalent)) An oxazolidone ring-containing epoxy resin (X8) was obtained in the same manner as in Example 2. Table 1 shows the characteristic values of the obtained epoxy resin containing an oxazolidone ring.

Example 9
Example 2 except that cresol novolac type epoxy resin (EPICLON N-695) was changed to 181 g of phenol novolak type epoxy resin (EPICLON N-740 (Dainippon Ink and Chemicals) (semi-solid, epoxy equivalent 181 g / equivalent)) In the same manner as above, an oxazolidone ring-containing epoxy resin (X9) was obtained, and the characteristic values of the obtained epoxy resin containing an oxazolidone ring are shown in Table 1.

Example 10
Cresol novolac type epoxy resin (EPICLON N-695) was changed to 276 g of dicyclopentadiene-phenol addition reaction type epoxy resin (EPICLON HP-7200HH (Dainippon Ink and Chemicals) (softening point 89 ° C., epoxy equivalent 276 g / equivalent)) Except that, an oxazolidone ring-containing epoxy resin (X10) was obtained in the same manner as in Example 2. Table 1 shows the characteristic values of the obtained epoxy resin containing an oxazolidone ring.

Synthesis example 1
A separable flask containing 214 parts of a cresol novolac type epoxy resin (EPICLON N-695 (manufactured by Dainippon Ink and Chemicals) (softening point 95 ° C., epoxy equivalent 214 g / equivalent)), a stirrer, thermometer, reflux condenser, A nitrogen blowing tube was attached and the temperature was raised to 150 ° C. with stirring while blowing nitrogen into the flask, and stirring was continued for 30 minutes after reaching 150 ° C. While maintaining the reaction temperature at 150 ° C., 22 parts of β-naphthol and tetra A mixture of 0.05 part of butylammonium chloride (Wako Pure Chemical) was added dropwise over 2 hours, after which the stirring was continued for 6 hours while maintaining the reaction temperature at 150 ° C., and β-naphthol-modified epoxy resin was added. The characteristic values of the obtained β-naphthol-modified epoxy resin are shown in Table 1.

Synthesis example 2
(Synthesis of carboxyl group-containing photopolymerizable unsaturated compound)
Add 214 g of EPICLON N-695 (epoxy equivalent = 214, manufactured by Dainippon Ink & Chemicals, Inc.), a cresol novolac type epoxy resin, to a four-necked flask equipped with a stirrer and reflux condenser, add 206 g of carbitol acetate and dissolve by heating. did. Next, 0.1 g of hydroquinone as a polymerization inhibitor and 2.0 g of triphenylphosphine as a reaction catalyst were added. This mixture was heated to 95 to 105 ° C., and 72 g of acrylic acid was gradually added dropwise to react for 16 hours. The obtained reaction product was cooled to 80 to 90 ° C., 91.2 g of tetrahydrophthalic anhydride was added and reacted for 8 hours. After cooling, the product was taken out. The carboxyl group-containing photopolymerizable unsaturated compound thus obtained had a non-volatile content of 65% and a solid acid value of 87.5 mgKOH / g. Hereinafter, this reaction product solution is referred to as A varnish.
Example 10

  To 100 g of the A varnish obtained above, 35 g of the epoxy resin (X1) obtained in Example 1 above, 8 g of dipentaerythritol hexaacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- 5 g of propan-1-one, 1 g of 2,4-diethylthioxanthone, 10 g of silica, 13 g of barium sulfate and 1 g of phthalocyanine green were mixed and dispersed with three rolls to prepare an alkali developing photosensitive resin composition (A).

Example 11
To 100 g of the A varnish obtained above, 39 g of the epoxy resin (X2) obtained in Example 2 above, 8 g of dipentaerythritol hexaacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- 5 g of propan-1-one, 1 g of 2,4-diethylthioxanthone, 10 g of silica, 13 g of barium sulfate, and 1 g of phthalocyanine green were mixed and dispersed with three rolls to prepare an alkali developing photosensitive resin composition (B).

Example 12
To 100 g of the A varnish obtained above, 51 g of the epoxy resin (X3) obtained in Example 3 above, 8 g of dipentaerythritol hexaacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- 5 g of propan-1-one, 1 g of 2,4-diethylthioxanthone, 10 g of silica, 13 g of barium sulfate and 1 g of phthalocyanine green were mixed and dispersed with three rolls to prepare an alkali developing type photosensitive resin composition (C).

Example 13
To 100 g of the A varnish obtained above, 79 g of the epoxy resin (X4) obtained in Example 4 above, 8 g of dipentaerythritol hexaacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- 5 g of propan-1-one, 1 g of 2,4-diethylthioxanthone, 10 g of silica, 13 g of barium sulfate and 1 g of phthalocyanine green were mixed and dispersed with three rolls to prepare an alkali developing type photosensitive resin composition (D).

Example 14
To 100 g of the A varnish obtained above, 40 g of the epoxy resin (X5) obtained in Example 5 above, 8 g of dipentaerythritol hexaacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- 5 g of propan-1-one, 1 g of 2,4-diethylthioxanthone, 10 g of silica, 13 g of barium sulfate and 1 g of phthalocyanine green were mixed and dispersed with three rolls to prepare an alkali developing type photosensitive resin composition (E).

Example 15
To 100 g of the A varnish obtained above, 40 g of the epoxy resin (X6) obtained in Example 6 above, 8 g of dipentaerythritol hexaacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- 5 g of propan-1-one, 1 g of 2,4-diethylthioxanthone, 10 g of silica, 13 g of barium sulfate and 1 g of phthalocyanine green were mixed and dispersed with three rolls to prepare an alkali developing type photosensitive resin composition (F).

Example 16
To 100 g of the A varnish obtained above, 35 g of the epoxy resin (X7) obtained in Example 7 above, 8 g of dipentaerythritol hexaacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- 5 g of propan-1-one, 1 g of 2,4-diethylthioxanthone, 10 g of silica, 13 g of barium sulfate and 1 g of phthalocyanine green were mixed and dispersed with three rolls to prepare an alkali developing type photosensitive resin composition (G).

Example 17
To 100 g of the A varnish obtained above, 36 g of the epoxy resin (X8) obtained in Example 8 above, 8 g of dipentaerythritol hexaacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- 5 g of propan-1-one, 1 g of 2,4-diethylthioxanthone, 10 g of silica, 13 g of barium sulfate and 1 g of phthalocyanine green were mixed and dispersed with three rolls to prepare an alkali developing type photosensitive resin composition (E).

Example 18
To 100 g of the A varnish obtained above, 35 g of the epoxy resin (X9) obtained in Example 9 above, 8 g of dipentaerythritol hexaacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- 5 g of propan-1-one, 1 g of 2,4-diethylthioxanthone, 10 g of silica, 13 g of barium sulfate and 1 g of phthalocyanine green were mixed and dispersed with three rolls to prepare an alkali developing type photosensitive resin composition (F).

Example 19
To 100 g of the A varnish obtained above, 50 g of the epoxy resin (X10) obtained in Example 9 above, 8 g of dipentaerythritol hexaacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- 5 g of propan-1-one, 1 g of 2,4-diethylthioxanthone, 10 g of silica, 13 g of barium sulfate and 1 g of phthalocyanine green were mixed and dispersed with three rolls to prepare an alkali developing type photosensitive resin composition (G).

Comparative Example 1
To 100 g of the A varnish obtained above, EPICLON N-695, a cresol novolak type epoxy resin (Dainippon Ink & Chemicals, softening point 95 ° C., epoxy equivalent 214 g / equivalent) 32 g, dipentaerythritol hexaacrylate 8 g, 2- 3 g of methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 1 g of 2,4-diethylthioxanthone, 10 g of silica, 13 g of barium sulfate, and 1 g of phthalocyanine green are mixed and dispersed in three rolls. Then, an alkali development type photosensitive resin composition (H) was prepared.

Comparative Example 2
To 100 g of the above obtained A varnish, 29 g of phenol novolac type epoxy resin EPICLON N-775 (manufactured by Dainippon Ink and Chemicals, softening point 74 ° C., epoxy equivalent 188 g / equivalent), dipentaerythritol hexaacrylate 8 g, 2- 3 g of methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 1 g of 2,4-diethylthioxanthone, 10 g of silica, 13 g of barium sulfate, and 1 g of phthalocyanine green are mixed and dispersed in three rolls. Thus, an alkali development type photosensitive resin composition (I) was prepared.

Comparative Example 3
To 100 g of the A varnish obtained above, phenol novolac type epoxy resin EPICLON N-740 (Dainippon Ink & Chemicals, semi-solid, epoxy equivalent 181 g / equivalent) 27 g, dipentaerythritol hexaacrylate 8 g, 2-methyl- 1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one 5 g, 2,4-diethylthioxanthone 1 g, silica 10 g, barium sulfate 13 g, and phthalocyanine green 1 g were mixed and dispersed with three rolls. An alkali development type photosensitive resin composition (J) was prepared.

Comparative Example 4
To 100 g of the A varnish obtained above, phenol novolac type epoxy resin EPICLON HP-7200HH (Dainippon Ink & Chemicals, softening point 89 ° C., epoxy equivalent 276 g / equivalent) 42 g, dipentaerythritol hexaacrylate 8 g, 2- 3 g of methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 1 g of 2,4-diethylthioxanthone, 10 g of silica, 13 g of barium sulfate, and 1 g of phthalocyanine green are mixed and dispersed in three rolls. Then, an alkali development type photosensitive resin composition (K) was prepared.

Comparative Example 5
To 100 g of the A varnish obtained above, 42 g of the modified epoxy resin obtained in Synthesis Example 1 above, 8 g of dipentaerythritol hexaacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane- 1-one 5 g, 2,4-diethylthioxanthone 1 g, silica 10 g, barium sulfate 13 g, and phthalocyanine green 1 g were mixed and dispersed by three rolls to prepare an alkali developing photosensitive resin composition (L).

Comparative Example 6
To 100 g of the A varnish obtained above, 19 g of alkyl monoglycidyl ether (YED-111) (manufactured by Japan Epoxy Resin, epoxy equivalent 290 g / eq), EPICLON N-695 (Dainippon Ink Chemical Co., Ltd.) Co., Ltd., epoxy equivalent = 214) 19 g, dipentaerythritol hexaacrylate 8 g, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one 5 g, 2,4-diethylthioxanthone 1 g, 10 g of silica, 13 g of barium sulfate, and 1 g of phthalocyanine green were mixed and dispersed with three rolls to prepare an alkali developing type photosensitive resin composition (M).

  Tables 2 and 3 show the thermal management width of the coating film of this composition and the evaluation results of the coating film performance after post-curing.

Performance evaluation:
(1) Touch-drying property after temporary drying Each alkali-developable photosensitive resin composition of Examples 11 to 20 and Comparative Examples 1 to 6 is applied on the entire surface of a panned copper foil substrate by screen printing. And the board | substrate dried at 80 degreeC for 20 minutes was created, and the finger touch dryness of the coating-film surface was evaluated.
○: No sticky △: Slightly sticky ×: Some solid

(2) Drying management width Each of the alkali development type photosensitive resin compositions of Examples 11 to 20 and Comparative Examples 1 to 6 was applied on the entire surface of the patterned copper foil substrate by screen printing at 80 ° C. Prepare substrates with different drying times at 5 minute intervals. A negative film was applied to the substrate, the solder resist pattern was exposed, developed with a 1% Na ₂ CO ₃ aqueous solution at a spray pressure of 2 kg / cm ² for 1 minute, and the drying control width (the longest drying time that can be developed) was examined.

(3) Developability A printed wiring board in which each of the alkali development type photosensitive resin compositions of Examples 11 to 20 and Comparative Examples 1 to 6 is patterned in a degreased and washed 0.318 mm pitch comb electrode shape. Is screen-printed on the entire surface to a thickness of 15 to 20 μm, then dried at 80 ° C. for 20 minutes, a negative film having a resist pattern is adhered to the coating film, and irradiated with ultraviolet rays having an integrated luminous intensity of 500 mJ / cm ² did. Next, development was performed using a 1% sodium carbonate aqueous solution at a liquid temperature of 30 ° C. for 30 seconds and 60 seconds at a spray pressure of 2.0 kg / cm ² , and the unexposed portion was visually evaluated according to the following criteria.
○: The ink is completely removed and there is no residue.
Δ: There is a slight residue.
X: There is a part which is not developed.

(4) Solder heat resistance Printed wiring in which each alkali development type photosensitive resin composition of Examples 11 to 20 and Comparative Examples 1 to 6 is patterned into a 0.318 mm pitch comb-shaped electrode that has been degreased and washed. Screen-printed on the entire surface to a thickness of 15 to 20 μm on the substrate, then dried at 80 ° C. for 20 minutes, a negative film having a resist pattern is adhered to the coating film, and irradiated with ultraviolet rays having an integrated luminous intensity of 500 mJ / cm ² Exposed. Next, after developing with a spray pressure of 2.0 kg / cm ² for 30 seconds and 60 seconds using a 1% aqueous sodium carbonate solution at a liquid temperature of 30 ° C., the substrate is further thermally cured at 150 ° C. for 60 minutes to be evaluated. Was made. A rosin-based flux was applied to this evaluation substrate, immersed in a solder bath set at 260 ° C. for 30 seconds in advance, and the flux was washed with trichloroethane. Then, the resist film was visually evaluated for swelling / peeling / discoloration.

◎: No change at all ○: Slightly discolored △: Slightly swollen, peeled or discolored ×: Resist film swelled or peeled

  The results of the above tests are summarized in Table 2 (Examples) and Table 3 (Comparative Examples).

  As is apparent from the results shown in Table 2, the alkali-developable photosensitive resin compositions of Examples 10 to 19 of the present invention are excellent in the touch-drying property, the dry management width and the developability after temporary drying, And the resist film formed using them was excellent also in various characteristics requested | required of solder resists, such as solder heat resistance. In particular, when Example 15 and Comparative Example 5 are compared, although the epoxy equivalent is almost the same, Example 15 is superior in drying control width, developability, and heat resistance. It can be seen that this is not simply due to the high epoxy equivalent and low reactivity.

The molecule obtained in Example 2 contains an oxazolidone ring obtained by reacting an aromatic monoisocyanate (a) with a polyfunctional epoxy resin (Y) containing two or more epoxy groups on average. It is an infrared absorption spectrum of an epoxy resin (X2). The molecule obtained in Example 8 contains an oxazolidone ring obtained by reacting an aromatic monoisocyanate (a) with a polyfunctional epoxy resin (Y) containing two or more epoxy groups on average in one molecule. It is an infrared absorption spectrum of an epoxy resin (X8).

Claims (20)

Epoxy resin (X) containing oxazolidone ring obtained by reacting polyfunctional epoxy resin (Y) containing two or more epoxy groups on average in one molecule with aromatic monoisocyanates (a) and curing An epoxy resin composition comprising an agent. The epoxy resin composition according to claim 1, wherein the epoxy resin (Y) is a novolac type epoxy resin. The epoxy resin composition according to claim 1, wherein the aromatic monoisocyanate (a) is phenyl isocyanate. The reaction ratio [(Y) / (a)] (equivalent ratio) between the epoxy group and the aromatic monoisocyanates (a) in the polyfunctional epoxy resin (Y) is 1 / 0.05 to 1 / 0.0. The epoxy resin composition according to claim 1, which is 30. Hardened | cured material obtained by hardening the epoxy resin composition as described in any one of Claims 1-5. The epoxy resin composition of Claim 1 prepared for the resin composition for printed circuit boards. The epoxy resin composition of Claim 1 prepared for the sealing material of an electronic component. The epoxy resin composition according to claim 1, which is prepared as a conductive paste. The epoxy resin composition of Claim 1 prepared for interlayer insulation materials. The epoxy resin composition according to claim 1, which is prepared for a fiber-reinforced composite material. Epoxy resin (X) and carboxyl containing oxazolidone ring obtained by reacting polyfunctional epoxy resin (Y) containing two or more epoxy groups on average in one molecule with aromatic monoisocyanates (a) An alkali-developable photosensitive resin composition comprising a group-containing photopolymerizable unsaturated compound (A) and a photopolymerization initiator (C). The alkali-developable photosensitive resin composition according to claim 11, wherein the epoxy resin (X) has a softening point in the range of 50 to 150 ° C. The epoxy equivalent of the epoxy resin (X) is 220 to 300 g / eq. The alkali-developable photosensitive resin composition according to claim 11, wherein The alkali-developable photosensitive resin composition according to claim 11, 12 or 13, further comprising a photopolymerizable unsaturated compound (D) having an ethylene bond. A resist ink using the alkali development type photosensitive resin composition according to claim 11. A printed wiring board formed with a circuit using the resist ink according to claim 15. An epoxy resin (X) containing an oxazolidone ring obtained by reacting a polyfunctional epoxy resin (Y) containing two or more epoxy groups on average in one molecule with an aromatic monoisocyanate (a). The epoxy resin (X) according to claim 17, wherein the polyfunctional epoxy resin (Y) is a phenol novolac type epoxy resin and / or a cresol novolac type epoxy resin. The epoxy resin (X) according to claim 18, wherein the aromatic monoisocyanate (a) is phenyl isocyanate. The reaction ratio [(Y) / (a)] (equivalent ratio) between the epoxy group and the aromatic monoisocyanates (a) in the polyfunctional epoxy resin (Y) is 1 / 0.05 to 1 / 0.0. The epoxy resin according to claim 17, which is 30.

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