KR20090013806A - Photosensitive resin and photosensitive resin composition - Google Patents

Abstract

A photosensitive resin which is prepared by copolymerizing rosin (meth)acrylate (a), a radically polymerizable compound having an epoxy group (b) and a radically polymerizable compound (c) exclusive of (a) and (b) and being capable of copolymerizing with the above compounds, reacting an unsaturated monobasic acid (d) with the epoxy group in the resultant copolymer, and then reacting a polybasic acid anhydride with the hydroxyl group; or a photosensitive resin which is prepared by copolymerizing rosin (meth)acrylate (a), an unsaturated monobasic acid (d) and a radically polymerizable compound (c) exclusive of (a) and (b), and reacting a radically polymerizable compound having an epoxy group (b) with the carboxyl group in the resultant copolymer; and a photosensitive resin composition containing the photosensitive resin. This photosensitive resin has a skeleton derived from rosin in the side chain thereof, exhibits the solubility in an alkali. A coating film, which is formed from the photosensitive resin composition, is excellent in the adhesion with various materials and in heat resistance, and therefore, the composition may have a high utility value in the "resist" field.

Description

Photosensitive resin and photosensitive resin composition {PHOTOSENSITIVE RESIN AND PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a photosensitive resin and a photosensitive resin composition. More specifically, it is related with the photosensitive resin which has a frame | skeleton derived from rosin in a side chain, and can form the cured coating film excellent in adhesiveness and heat resistance with various materials, and the photosensitive resin composition containing the said resin.

In recent years, active energy ray-curable resins curable with active energy rays such as ultraviolet rays or electron beams have been widely used in the fields of printing, paints, adhesives, and liquid crystals in view of resource saving and energy saving.

Also in the field of electronic materials, such as a printed wiring board, the soldering resist etc. which used resin hardened | cured by an active energy ray are used as resin for semiconductor substrates. As a material used for a printed wiring board in the photoresist method, an acid pendant novolac epoxy acrylate is generally used. For example, in Patent Document 1, unsaturated monocarboxylic acid is reacted with an epoxy resin, and then polybasic acid anhydride is reacted. Added compounds are used. Moreover, in patent document 2, the compound which added the acid anhydride to the novolak-type epoxy acrylate is used. However, when adhesiveness with a copper plating surface is not enough and it is used for a multilayer printed wiring board, there exists a subject that sufficient adhesive strength between conductor circuits is not obtained.

In addition, as a means of improving the heat resistance, moisture resistance, and electrical insulation of the resist film, Patent Document 3 discloses that a silicone-modified epoxy resin in which (meth) acrylic acid is reacted with a part of an epoxy group of a resin, and then a silicon compound having an unsaturated group is reacted. It is proposed.

Moreover, in patent document 4, the photoresist which consists of the polymer which has an epoxy group in the side chain obtained by radically polymerizing the radically polymerizable monomer which has an epoxy group, and the following polymers is proposed. As the polymer, a compound such as glycidyl (meth) acrylate is added to the side chain carboxyl group of the copolymer obtained by radical copolymerization of a radical polymerizable monomer having a carboxyl group with an acrylic acid ester and the like, and the side chain is unsaturated. (Co) polymer which reacted (meth) acrylic acid to the (co) polymer containing a radically polymerizable monomer as a unit, and added the polybasic acid anhydride, (co) polymer which added the polybasic acid anhydride to epoxy acrylate, and maleic anhydride The compound which added a compound like glycidyl (meth) acrylate to the polymer, and made the side chain unsaturated group, etc. is used.

Furthermore, epoxy obtained by reacting epichlorohydrin with a phenolic hydroxyl group of a resin having a phenol aralkyl skeleton as a main chain to glycidyl ether and reacting some glycidyl ether groups with an unsaturated monocarboxylic acid such as acrylic acid. The case where acrylate is used as a main cured resin component is also proposed (patent document 5), and the (co) polymer which added polybasic acid anhydride to such epoxy acrylate is also proposed (patent document 6). Moreover, the case where the (co) polymer which uses the (meth) acrylate which has a dicyclopentadiene frame | skeleton as a monomer component is used as a main hardening resin component is also proposed (patent document 7).

As described above, in order to improve the degree of integration of semiconductor circuits and the performance required for photosensitive resins in the field of solder resists, various improved resins as described above have been proposed in order to satisfy the difficult demands. Not obtained.

Moreover, in manufacture of color filters, such as a liquid crystal display device manufactured from the photosensitive resin which uses the above various resin etc. as a hardening component, a black matrix, a photo spacer, a protective film, etc., dispersion of a pigment or dye as an epoxy acrylate There is a problem in stability, and conventionally, acrylic copolymers containing methacrylic acid, benzyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate, and the like are known. However, heat resistance is insufficient and heating at the time of fixing the pattern It is a problem that the pyrolysate becomes outgas in the process and contaminate the substrate or the device. Moreover, when using the acrylic copolymer using alicyclic cyclohexyl methacrylate etc. in order to raise heat resistance, adhesiveness with a board | substrate may not be enough and a problem, such as peeling at the time of patterning, may arise (for example, a patent document) 8).

In order to solve the various problems which arise when using photosensitive resin, many proposals are made also about the photosensitive resin which used as a main component the resin which has frame | skeleton derived from rosin in a side chain (for example, patent documents 9-12 Etc).

However, the above publications do not describe improving the characteristics of the photosensitive resin by further modifying the resin having a skeleton derived from rosin in the side chain.

Patent Document 1: Japanese Patent Application Laid-Open No. 56-40329

Patent Document 2: Japanese Patent Application Laid-Open No. 61-243869

Patent document 3: Unexamined-Japanese-Patent No. 6-19134

Patent Document 4: Japanese Patent Application Laid-Open No. 8-211611

Patent Document 5: Japanese Patent Application Laid-Open No. 10-101770

Patent Document 6: Japanese Patent Application Laid-Open No. 2001-247649

Patent Document 7: Japanese Patent Application Laid-Open No. 2001-89533

Patent Document 8: Japanese Patent Application Laid-Open No. 9-278842

Patent Document 9: Japanese Patent Application Laid-Open No. 6-100641

Patent Document 10: Japanese Patent Laid-Open No. 2002-289039

Patent Document 11: Japanese Patent Application Laid-Open No. 2003-248307

Patent Document 12: Japanese Patent Application Laid-Open No. 2004-204103

As a result of diligent study by the present inventors under such a situation, the present invention has further modified a resin having a rosin-derived skeleton in the side chain, thereby sufficient for adhesion and heat resistance to the substrate, and a photosensitive resin having less outgassing during heating. And it discovered that the photosensitive resin composition was obtained and reached | attained this invention.

That is, the 1st of this invention is rosin (meth) acrylate (a) 5-30 mol%, the radically polymerizable compound (b) which has an epoxy group (30)-85 mol%, and copolymerizable with these (a) and ( Unsaturated to 10 to 100% of the epoxy groups in the copolymer (hereinafter referred to as Copolymer 1) obtained by copolymerizing 10 to 65 mol% of the radically polymerizable compound (c) other than b) in an amount of 100 mol% in total. After reacting monobasic acid (d), polybasic acid anhydride (e) is made to react with 5-100% of hydroxyl groups, and it provides the photosensitive resin (henceforth referred to as photosensitive resin 1).

Next, the second aspect of the present invention is radically polymerizable except for 5 to 30 mol% of rosin (meth) acrylate (a), 20 to 60 mol% of unsaturated monobasic acid (d), and (a) and (d). A radically polymerizable compound having an epoxy group in 5 to 80% of the carboxyl groups in a copolymer (hereinafter referred to as copolymer 2) obtained by copolymerizing 10 to 75 mol% of the compound (c) in an amount of 100 mol% in total ( It is to provide a photosensitive resin (hereinafter referred to as photosensitive resin 2) formed by reacting b).

Next, a third aspect of the present invention is to provide a photosensitive resin composition containing the photosensitive resins 1 and / or 2 and the reactive diluent (f) as essential components and, if necessary, containing a solvent (g).

Moreover, the fourth of the present invention further provides a photosensitive resin composition containing a solvent (g).

Best Mode for Carrying Out the Invention

First, the photosensitive resin 1 of this invention is demonstrated.

The photosensitive resin 1 has a skeleton derived from the monomer components (a), (b) and (c) in the side chain, and the copolymerization ratio thereof is (a) 5 to 30 mol%, preferably 5 to 25 mol%, More preferably 10-25 mol%, (b) 30-85 mol%, Preferably 30-70 mol%, More preferably, 40-60 mol% and (c) 10-65 mol%, Preferably 20-55 mol%, More preferably, it is 25-50 mol%, and the sum total is 100 mol%. The radical copolymer of this (a), (b) and (c) component is copolymer 1.

By setting the component (a) to 5 mol% or more, the adhesion to the substrate and the heat resistance of the coating film formed from the photosensitive resin 1 by the introduction of the rosin skeleton are improved. By setting it as 30 mol% or less, the viscosity of resin is prevented from becoming high. When the viscosity of the resin is increased, in order to reduce the viscosity, it is necessary to increase the amount of the reactive diluent (f) and the solvent (g) described below, which makes it difficult to control the properties of the product and control the curability.

By setting the component (b) to 30 to 85 mol%, the introduction amount of the epoxy group, that is, the introduction amount of the unsaturated group derived from the unsaturated monobasic acid as the component (d) described below can be adjusted, and the curability of the photosensitive resin 1 can be adjusted. I can regulate it. By making (a) component and (b) component into the above ratio, (c) component can be selected suitably within the range of 10-65 mol%.

The photosensitive resin 1 is a radical copolymerization of the above (a), (b) and (c) to form copolymer 1, and then reacts an unsaturated monobasic acid as (d) component, and then as (e) component. It is obtained by reacting anhydrous polybasic acid.

The carboxyl group of the unsaturated monobasic acid as the component (d) reacts with the side chain epoxy group derived from the component (b) to ring-open an epoxy group to form a hydroxyl group, and at the same time, an unsaturated group is given to the terminal. The anhydrous polybasic acid as the component (e) originally exists in the rosin skeleton of the hydroxyl group produced by the reaction of the carboxyl group in the component (d) and the side chain epoxy group derived from the component (b) and the rosin (meth) acrylate as the component (a). It reacts with a hydroxyl group, an acid anhydride group is ring-opened, and is converted into a carboxyl group.

The usage-amount of the unsaturated monobasic acid which is (d) component is 10-100 mol, Preferably it is 30-100 mol, More preferably, it is 50-100 mol with respect to 100 mol of side chain epoxy groups derived from (b) component.

By using the amount of the unsaturated monobasic acid at 10 mol or more, the minimum amount of the unsaturated group required for curing the resin can be introduced, and the amount of the unsaturated photobasic resin 1 of the present invention obtained by making the amount of the unsaturated monobasic acid at 100 mol or less is used. The amount of reactive unsaturated monobasic acids can be reduced.

The usage-amount of the polybasic acid anhydride which is the (e) component made to react next is the hydroxyl group which originated by reaction of the carboxyl group in (d) component and the side chain epoxy group derived from (b) component, and the hydroxyl group which exists originally in the rosin skeleton which is (a) component It is 5-100 mol, Preferably it is 10-90 mol with respect to 100 mol of total amounts of, More preferably, it is 20-90 mol. The acid value (JIS K6901) of the photosensitive resin 1 obtained can be adjusted to the range of 20-150 KOHmg / g by making the number-of-moles of anhydrous polybasic acid into the range of 5-100 mol with respect to 100 mol of hydroxyl groups. Explanation of acid value is made simultaneously in the description part of photosensitive resin 2 described later.

The radical copolymerization reaction for obtaining copolymer 1 is not particularly limited, and conventional radical polymerization methods conventionally performed can be applied.

For example, (a), (b) and (g) in a glycol ether solvent such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, a hydrocarbon solvent such as toluene or xylene, or an organic solvent having no functional group such as ethyl acetate. (c) The component is dissolved at a desired ratio, and a polymerization initiator such as azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate is mixed and refluxed. The organic solvent solution of copolymer 1 is obtained by superposing | polymerizing at about 50-130 degreeC for about 1 to 20 hours. The usage-amount of a polymerization initiator is about 0.5-20 weight part normally with respect to 100 weight part of total amounts of (a), (b) and (c) component, Preferably it is 1.0-10 weight part.

You may perform block polymerization only with (a), (b) and (c) component and a polymerization initiator, without using an organic solvent.

The usage-amount of an organic solvent is about 30-1000 weight part normally with respect to 100 weight part of total amounts of (a), (b) and (c) component, Preferably it is 50-800 weight part. By setting the usage-amount of an organic solvent to 1000 weight part or less, the molecular weight of the copolymer 1 is prevented from falling by the chain transfer action, and the solid content concentration of the finally obtained photosensitive resin 1 can be adjusted to an appropriate range.

By setting it as 30 weight part or more, abnormal polymerization reaction can be prevented and stable polymerization reaction can be advanced, and resin can be prevented from coloring or gelatinizing.

Since the photosensitive resin 1 of this invention is mainly used as electronic materials, such as a resist, as the photosensitive resin composition which mixed the reactive diluent and solvent which are described later, when copolymer 1 is manufactured by the above-mentioned radical copolymerization, propylene glycol monomethyl ether Glycol ester solvents such as acetates are preferably used.

In order to make the unsaturated monobasic acid which is (d) component react with the side chain epoxy group derived from (b) component in the copolymer 1 obtained by the radical copolymerization reaction, it is carried out as follows. That is, in order to prevent gelation by polymerization of the unsaturated monobasic acid or the resulting unsaturated group-containing copolymer, in the presence of a polymerization inhibitor such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, oxygen, and the like, triethylamine In the presence of a catalyst such as a tertiary amine, a quaternary ammonium salt such as triethylbenzylammonium chloride, a phosphorus compound such as triphenylphosphine, and a chelating compound of chromium, usually at 50 to 150 ° C, preferably at 80 to 130 ° C. Conduct the reaction. When an organic solvent is used in the radical copolymerization reaction to obtain copolymer 1, it can be used for subsequent reactions in the state of the copolymer 1 organic solvent solution.

The copolymer (1a) which has an unsaturated group and a hydroxyl group as a side chain by the above reaction, and the hydroxyl group which exists originally in the rosin skeleton of rosin (meth) acrylate which is a hydroxyl group produced by reaction of a carboxyl group and an epoxy group, and (a) component. Is obtained.

The photosensitive resin 1 of this invention is obtained by making the hydroxyl group of this copolymer (1a) react with the polybasic acid anhydride which is (e) component. Reaction of the hydroxyl group and polybasic acid anhydride of copolymer (1a) is made to react the unsaturated monobasic acid which is (d) component to the epoxy group of the side chain derived from (b) component in the said copolymer 1, and wants (e) component as it is. Both amounts are added, and about 50-150 degreeC normally, Preferably it carries out by heating at 80-130 degreeC. There is no need to add a new catalyst.

Rosin (meth) acrylate which is (a) component in the photosensitive resin 1 of this invention is a carboxyl group which exists in abies acid etc., for example, glycidyl (meth) acrylate, 3, 4- epoxycyclohexylmethyl ( An unsaturated compound having an epoxy group such as meth) acrylate is reacted to introduce a (meth) acryloyl group which is an unsaturated group.

Typical examples include rosin-modified glycidyl (meth) acrylates represented by the following formulas (1) and (2).

In said Formula (1) and Formula (2), R <^1> is a hydrogen atom or a methyl group, R <^2> is a alkylene group which may have a single bond or a C1-C30 linear or branched chain. In said Formula (1) and Formula (2), it is preferable that R <^1> is a hydrogen atom and R <^2> is a single bond most easily, and is easy to obtain.

Moreover, the rosin modified cyclohexyl methyl (meth) acrylate represented by following formula (3) or (4) is mentioned.

In said Formula (3) and Formula (4), R <^1> is a hydrogen atom or a methyl group.

Rosin is a natural product, and its ingredients differ slightly depending on the region, but usually mixtures of abietic acid, neo-abietic acid, parastric acid, levopimaric acid, dehydroabietic acid, dihydroabietic acid, tetrahydroavietic acid and the like to be. Usually, it is said that content of abiete acid and neo-abietic acid, and these dihydroxy compounds is the highest. In formula (1), when R <^2> is a single bond, it is glycidyl (meth) acrylate of abiete acid, In the said Formula (2), when R <^2> is a single bond, the glyc of neoabiete acid is Cydyl (meth) acrylate. These rosin (meth) acrylates are commercially available, for example, 2-hydroxypropyl dehydroabirate acrylate "beam set 101", "beam set 102", "beam set 115" of Arakawa Chemical, Shinnakamura Chemical. "K1000A", "UNIRESIN K900B", etc. are mentioned.

It does not specifically limit as a radically polymerizable compound which has an epoxy group which is (b) component in the photosensitive resin 1 of this invention, For example, 3, 4- epoxy which has glycidyl (meth) acrylate and an alicyclic epoxy Cyclohexylmethyl (meth) acrylate and its lactone adducts [e.g., Cychrom A200, M100 manufactured by Daicel Chemical Industries, Ltd.], 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclo Mono (meth) acrylic acid ester of hexanecarboxylate, epoxide of dicyclopentenyl (meth) acrylate, epoxide of dicyclopentenyloxyethyl (meth) acrylate, and the like. Glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate are preferably used. You may use these 1 type or 2 or more types together.

As radically polymerizable compounds other than (a) and (b) which are (c) component in the photosensitive resin 1 of this invention, if it has an ethylenically unsaturated group, it will not specifically limit. Specific examples thereof include styrene, α-, o-, m-, p-alkyl, nitro, cyano and amide derivatives of styrene; Dienes such as butadiene, 2,3-dimethylbutadiene, isoprene and chloroprene; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, la Uryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate , Isoboroyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylic Latex, tricyclodeca Oxyethyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninonyl ( Meta) acrylate, piperonyl (meth) acrylate, salicylic (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) ) Acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) Acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-iso-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) arc Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) (meth) acrylic acid esters such as acrylate; (Meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, N-di (Meth) acrylic acid amides such as isopropylamide and (meth) acrylic anthracenylamide; Vinyl compounds such as (meth) acrylic acid acrylate, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine and vinyl acetate; Unsaturated dicarboxylic acid esters such as diethyl citrate, diethyl maleate, diethyl fumarate and diethyl itaconic acid; Monomaleimides such as N-phenylmaleimide, N-cyclohexyl maleimide, N-lauryl maleimide, and N- (4-hydroxyphenyl) maleimide; N- (meth) acryloyl phthalimide etc. are mentioned. Among the above, styrene, benzyl (meth) acrylate, and monomaleimide are preferably used from the viewpoint of the strength and heat resistance of the cured coating film.

You may use together 1 type (s) or 2 or more types.

It does not specifically limit as unsaturated monobasic acid which is (d) component in the photosensitive resin 1 of this invention, For example, (meth) acrylic acid, crotonic acid, cinnamic acid, etc. are mentioned. Moreover, the polyfunctional (meth) acrylate which has one hydroxyl group and one or more (meth) acryloyl groups (for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl) (Meth) acrylate, trimethylolpropane di (meth) acrylate, etc.) and the reaction product of polybasic acid anhydride, etc. can also be used. You may use these 1 type or 2 or more types together.

Among the above, (meth) acrylic acid is preferably used. These may use together 1 type (s) or 2 or more types.

It does not specifically limit as polybasic acid anhydride which is (e) component in the photosensitive resin 1 of this invention, For example, succinic anhydride, maleic anhydride, citraconic acid, itaconic anhydride, phthalic anhydride, tetrahydro phthalic anhydride, Methyl tetrahydro phthalic anhydride, hexahydro phthalic anhydride, trimellitic anhydride, a pyromellitic dianhydride, etc. are mentioned.

In the above, tetrahydro phthalic anhydride and succinic anhydride are preferably used. You may use together 1 type (s) or 2 or more types.

Next, the photosensitive resin 2 of the present invention will be described.

Copolymer 2, which is a precursor of photosensitive resin 2, has a skeleton derived from the monomer components (a), (c) and (d) as used in the photosensitive resin 1 in the side chain, and the copolymerization ratio of (a) is 5 30 mol%, Preferably 5-25 mol%, More preferably, 10-25 mol%, (d) is 20-60 mol%, Preferably 30-55 mol%, More preferably, 40-50 10 mol%-75 mol%, Preferably it is 20-65 mol%, More preferably, it is 25-50 mol%, The sum total is 100 mol%.

The component (a) in the photosensitive resin 2 is the same as that used for the photosensitive resin 1, and the reason why the use molar ratio is 5-30 mol% is also the same as that of the photosensitive resin 1.

The component (d) in the photosensitive resin 2 is also the same compound as used for the photosensitive resin 1, but differs from the case for the photosensitive resin 1, and is used for the presence of a carboxyl group in the side chain of the copolymer 2 in the step of radical copolymerization. Therefore, unlike the case of photosensitive resin 1, the usage-amount of (d) component is the ratio of 20-60 mol% of (d) component with respect to 5-30 mol% of rosin (meth) acrylate (a).

(C) component in photosensitive resin 2 is the same as what is used by photosensitive resin 1, and the reason for making the use molar ratio 10-75 mol% is also the same as that of the photosensitive resin 1. That is, the said range is necessarily determined by the usage ratio of (a) component and (d) component.

Radical copolymerization for producing copolymer 2 is carried out under the same conditions as radical copolymerization for producing copolymer 1 except that the molar ratio of each component is different.

Copolymer 2 prepared as described above converts a part of the carboxyl groups to an unsaturated group by reacting a carboxyl group in the side chain, and then reacting this carboxyl group with a radically polymerizable compound having an epoxy group as the component (b). The usage-amount of the radically polymerizable compound which has an epoxy group (b) component is 5-80 mol with respect to 100 mol of carboxyl groups which exist in the side chain of copolymer 2. By adjusting it to 5-80 mol, the balance of a carboxyl group and an unsaturated group is good, and the hardenability of the photosensitive resin 2 and developability by alkali are suitably maintained.

The conditions when reacting the radically polymerizable compound which has the epoxy group which is (b) component in the carboxyl group in copolymer 2 react with the unsaturated monobasic acid which is (d) component in the epoxy group of copolymer 1 except the molar ratio of each component, Same condition.

Under the above conditions, the acid value (JIS K6901) of the obtained photosensitive resin 1 and photosensitive resin 2 can be adjusted to the range of 20-150 KOHmg / g, and the image development by alkali performed after apply | coating the said resin to a board | substrate You can adjust the sex. By making an acid value 20 KOHmg / g or more, the developability by alkali is prevented from falling. By setting the acid value to 150 KOHmg / g or less, the patterning can be surely performed.

The acid value is preferably 30 to 140 KOHmg / g, more preferably 40 to 130 KOHmg / g.

In the photosensitive resin 1 and photosensitive resin 2 of this invention obtained as mentioned above, the weight average molecular weight (numerical value of polystyrene conversion by GPC method) is 3000-100000 normally, Preferably it is 5000-4000. By setting the weight average molecular weight to 3000 or more, the inferior heat resistance is prevented, and by setting it to 100000 or less, the developability is prevented from decreasing.

The photosensitive resin composition is obtained by adding the reactive diluent (f) and the solvent (g) as needed to the photosensitive resin 1 and / or photosensitive resin 2 obtained as mentioned above.

The reactive diluent (f) that can be used is not particularly limited as long as it can react with the photosensitive resin 1 and / or the photosensitive resin 2. For example, Aromatic vinyl monomers, such as styrene, (alpha) -methylstyrene, (alpha)-chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate; Polycarboxylic acid monomers such as vinyl acetate and vinyl adipic acid; Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, β-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethylene glycol Di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri ( (Meth) acrylic monomers such as tri (meth) acrylate of meta) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tris (hydroxyethyl) isocyanurate ; Triallyl cyanurate, etc. are mentioned. You may use together 1 type (s) or 2 or more types.

The addition amount of reactive diluent (f) is 10-200 weight part normally with respect to 100 weight part of photosensitive resin 1 and / or photosensitive resin 2, Preferably it is 20-150 weight part.

By setting it as said range, photocurability can be maintained in an appropriate range, and also a viscosity can also be adjusted.

Depending on the kind of reactive diluent (f) used, a solvent (g) can be used further in order to reduce a viscosity.

As a solvent (g) which can be used, if it is an inert solvent which does not react with photosensitive resin 1 and / or photosensitive resin 2, and a reactive diluent (f), it can use without a restriction | limiting.

Solvents (g) which can be used include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether and dipropylene glycol monomethyl. Ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate and the like. Can be mentioned. In these, the propylene glycol monomethyl ether acetate used preferably at the said radical polymerization reaction is used preferably.

The addition amount of solvent (g) is 30-1000 weight part normally with respect to 100 weight part of photosensitive resin 1 and / or photosensitive resin 2, Preferably it is 50-800 weight part.

By setting it as the said range, a viscosity can be maintained moderately.

When the photosensitive resin composition of this invention is photocured using active light, such as an ultraviolet-ray, as an active energy ray, a photoinitiator can be added. Although it does not specifically limit as a photoinitiator which can be used, For example, benzoin, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and its alkyl ether; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4- (1-t-butyldioxy-1-methylethyl) acetophenone; Anthraquinones such as 2-methylanthraquinone, 2-amyl anthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; Thioxanthones such as 2,4-dimethyl thioxanthone, 2,4-diisopropyl thioxanthone, and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone ; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone- One; Acyl phosphine oxides, xanthones, etc. are mentioned. You may use these 1 type or 2 or more types together. The compounding quantity of a photoinitiator is 0.1-30 weight part normally with respect to 100 weight part of solid content in the photosensitive resin composition of this invention, Preferably it is 0.5-20 weight part, More preferably, it is 1-10 weight part. By setting it as 0.1-30 weight part, photocurability can be maintained in a suitable range.

Moreover, the photosensitive resin composition of this invention can contain a well-known coloring agent, an antifoamer, a coupling agent, a leveling agent, etc. as needed.

As mentioned above, since the acid value of the photosensitive resin 1 and the photosensitive resin 2 of this invention is 20-150 KOHmg / g, the resists using the photosensitive resin composition containing them can develop using aqueous alkali solution.

The photosensitive resin composition of this invention is apply | coated by the screen printing method, the roll coater method, the curtain coater method, the spray coater method, the spin coat method, etc. on a printed wiring board, for example, and photocures the required part, and the uncured thing The development is performed by washing the (unexposed) part with an aqueous alkali solution.

As the aqueous alkali solution used for development, aqueous solutions such as sodium carbonate, potassium carbonate, calcium carbonate and sodium hydroxide, and amino phenol compounds are also useful as amine compounds, but p-phenylenediamine compounds are preferably used. -Methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and an aqueous solution of sulfate, hydrochloride or p-toluenesulfonate thereof.

Low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, and the like are used as light sources used for curing the coated surface by light irradiation.

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited at all by these examples.

In addition, all parts and percentages are based on weight unless otherwise specified. The molecular weight of the copolymer is the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography).

Synthesis Example 1

137 parts of propylene glycol monomethyl ether acetates were taken to the flask provided with the stirring apparatus, the dropping lot, the condenser, the thermometer, and the gas introduction tube, and it stirred, replacing by nitrogen, and heated up at 120 degreeC.

Next, t-butylperoxy-2-ethylhexano was added to a monomer mixture consisting of 70 parts of benzyl methacrylate, 71 parts of glycidyl methacrylate, and 43 parts of rosin acrylate (Arakawa Chemical Co., Ltd. beamset 101). Eight [Japanese fats and oils perbutyl O] was added 9 parts with respect to 100 parts of monomer mixtures. This was added to the flask over 2 hours from the dropping lot, and further stirred at 120 degreeC for 2 hours, and the solution of copolymer 1 was obtained.

Subsequently, the flask was replaced with air, 35 parts of acrylic acid, 0.66 parts of triphenylphosphine and 0.15 parts of methylhydroquinone were added to the solution of Copolymer 1, and the reaction was continued at 120 ° C., where the acid value of the solid content was 0.8 KOHmg. When it became / g, reaction was complete | finished and the solution of copolymer 1a was obtained. Subsequently, 61 parts of tetrahydrophthalic anhydride were added and reacted at 115 degreeC for 2 hours, and the solution of alkali developable photosensitive resin 1 (Mw: 17000) of 76 KOHmg / g of solid content acid value was obtained.

Synthesis Example 2

Proceed as in Synthesis Example 1 except for changing propylene glycol monomethyl ether acetate to 165 parts, benzyl methacrylate to 44 parts, rosin acrylate to 108 parts, triphenylphosphine to 0.77 parts, and methylhydroquinone to 0.18 parts, respectively. A solution of alkali developable photosensitive resin 1 (Mw: 20000) having a solid acid value of 66 KOH mg / g was obtained.

Synthesis Example 3

382 parts of propylene glycol monomethyl ether acetates were taken to the flask provided with the stirring apparatus, the dropping lot, the condenser, the thermometer, and the gas introduction tube, and it stirred, replacing with nitrogen, and heated up at 120 degreeC. Next, 1 part of perbutyl O was added to 100 parts of monomer mixtures to the monomer mixture consisting of 76 parts of benzyl methacrylate, 40 parts of methacrylic acid and 43 parts of rosin acrylate (Arakawa Chemical Co., Ltd. beamset 101). . This was dripped at the flask over 2 hours from the dropping lot, and also it stirred at 120 degreeC for 2 hours, and obtained the solution of copolymer 2. Subsequently, the flask was replaced with air replacement, 21 parts of glycidyl methacrylate, 0.54 part of triphenylphosphine and 0.11 part of methylhydroquinone were added to the solution of Copolymer 2, and the reaction was continued at 120 ° C. to give a solid acid value of 97. When it became KOHmg / g, reaction was complete | finished and the solution of photosensitive resin 2 (Mw: 30000) which can be alkali-developed was obtained.

Synthesis Example 4

Proceed as in Synthesis Example 3 except for changing propylene glycol monomethyl ether acetate to 474 parts, benzyl methacrylate to 49 parts, rosin acrylate to 108 parts, triphenylphosphine to 0.66 parts, and methylhydroquinone to 0.13 parts, respectively. A solution of alkali developable photosensitive resin 2 (Mw: 38000) having a solid acid value of 80 KOH mg / g was obtained.

Synthesis Example 5

The solid acid value was 83 KOH in the same manner as in Synthesis Example 1 except that 120 parts of propylene glycol monomethyl ether acetate, 70 parts of benzyl methacrylate, 47 parts of vinyltoluene, 0.59 parts of triphenylphosphine, and 0.15 parts of methylhydroquinone were changed. The solution of mg / g alkali developable photosensitive resin 1 (Mw: 19000) was obtained.

Synthesis Example 6

Synthesis Example 1 except changing propylene glycol monomethyl ether acetate to 154 parts, benzyl methacrylate 70 parts to vinyl toluene 30 parts, rosin acrylate to 108 parts, triphenylphosphine to 0.73 parts, and methylhydroquinone to 0.17 parts, respectively. It carried out similarly and obtained the solution of alkali developable photosensitive resin 1 (Mw: 22000) of 70 KOHmg / g of solid acid value.

Synthesis Example 7

Solid content acidity 113 KOH was carried out in the same manner as in Synthesis Example 3 except that propylene glycol monomethyl ether acetate was changed to 322 parts, benzyl methacrylate 70 parts to vinyltoluene 51 parts, triphenylphosphine to 0.47 parts, and methylhydroquinone to 0.09 parts, respectively. The solution of mg / g alkali developable photosensitive resin 2 (Mw: 33000) was obtained.

Synthesis Example 8

Synthesis example except for changing propylene glycol monomethyl ether acetate to 435 parts, benzyl methacrylate 70 parts to vinyl toluene 33 parts, rosin acrylate to 108 parts, triphenylphosphine to 0.61 parts, and methylhydroquinone to 0.12 parts, respectively. It carried out similarly to 3, and obtained the solution of alkali developable photosensitive resin 2 (Mw: 39000) of solid content acid value 86 KOHmg / g.

Comparative Synthesis Example 1

Propylene glycol monomethyl ether acetate was changed to 118 parts, benzyl methacrylate to 88 parts, triphenylphosphine to 0.58 parts, and methylhydroquinone to 0.14 parts, respectively, except that rosin acrylate was not used. It carried out and obtained the solution of the comparative photosensitive resin (Mw: 12000) which is alkali developable of solid content acid value 83KOHmg / g.

Comparative Synthesis Example 2

Propylene glycol monomethyl ether acetate was changed to 321 parts, benzyl methacrylate to 93 parts, triphenylphosphine to 0.47 parts, and methylhydroquinone to 0.09 parts, respectively, except that rosin acrylate was not used. It carried out and obtained the solution of the comparative photosensitive resin (Mw: 20000) of alkali developability of solid content acid value 113KOHmg / g.

Comparative Synthesis Example 3

Synthesis example except that 96 parts of propylene glycol monomethyl ether acetate, 70 parts of benzyl methacrylate, 59 parts of vinyltoluene, 0.50 parts of triphenylphosphine, and 0.12 parts of methylhydroquinone were used, and rosin acrylate was not used. It carried out similarly to 1, and obtained the solution of the comparative photosensitive resin (Mw: 15000) which can be alkali-developed with a solid acid value of 95 KOHmg / g.

Comparative Synthesis Example 4

250 parts of propylene glycol monomethyl ether acetate, 76 parts of benzyl methacrylate, 66 parts of vinyltoluene, 38 parts of methacrylic acid, 0.38 parts of triphenylphosphine, and 0.08 parts of methylhydroquinone, respectively. Except not having been used, it carried out similarly to the synthesis example 3, and obtained the solution of the comparative photosensitive resin (Mw: 21000) which can be alkali-developed with a solid acid value of 127 KOHmg / g.

<Examples 1-8, Comparative Examples 1-4>

The solutions of the photosensitive resin obtained in the synthesis examples 1-8 were used in Examples 1-8, respectively, and the solutions of the photosensitive resin obtained in the comparative synthesis examples 1-4 were used in the comparative examples 1-4, respectively. A resin composition prepared by adding 30 parts of pentaerythritol tetraacrylate and 4 parts of 2,2-dimethoxy-2-phenylacetophenone as a photopolymerization initiator to 100 parts of solid content of each photosensitive resin solution was prepared on an glass substrate with an applicator. After wetting with a thickness of 10 μm when wet and volatilizing the low boiling point in a warm air dryer at 100 ° C., the film is exposed to 150 mJ / cm 2 through a mask, if necessary, using an ultra-high pressure mercury lamp manufactured by Oak Manufacturing Co., Ltd. Was obtained, and then alkali development was carried out.

<Heat resistance>

Each cured coating film was cut out and thermogravimetric analysis (TGA) was performed. The weight change rate when the cut sample was heated to 220 degreeC and hold | maintained for 2 hours was measured.

<Adhesiveness>

The cured coating film was subjected to a base wood test in accordance with JIS K5400, and the peeling state of 100 base woods was visually observed to evaluate the following criteria.

(Circle): Peeling is not confirmed at all.

(Triangle | delta): Peeling is confirmed by less than 10% of the whole.

X: Peeling is confirmed by 10% or more of the whole.

<Alkali Developability>

0.1% sodium carbonate aqueous solution was melt-dissolved and developed the cured coating film exposed through the mask at 23 degreeC, and the presence or absence of the coating film after water washing was observed.

(Circle): After development time 70 second, there is no coating film visually

×: After the developing time of 70 seconds, there is a coating film by eye

TABLE 1

TABLE 2

As can be seen from the results of Table 1 and Table 2, in Examples 1 to 8, the weight loss during heating is small, the peeling of the cured coating film is not confirmed, and the alkali developability is not impaired.

The cured coating film formed from the photosensitive resin of this invention is especially excellent in adhesiveness with respect to a semiconductor substrate, and since it has alkali developability, it is very useful in the resist field.

Claims (4)

Rosin (meth) acrylate (a) 5-30 mol%, radically polymerizable compound which has an epoxy group (b) 30-85 mol%, and radically polymerizable other than (a) and (b) copolymerizable with these 10 to 65 mol% of the compound (c) is copolymerized in an amount of 100 mol% in total so that the unsaturated monobasic acid (d) is reacted with 10 to 100% of the epoxy group in the copolymer obtained, and then 5 to 100 of the hydroxyl group. Photosensitive resin formed by making polybasic acid anhydride (e) react with%. Rosin (meth) acrylate (a) 5-30 mol%, unsaturated monobasic acid (d) 20-60 mol%, and radically polymerizable compounds (c) 10-75 mol% other than (a) and (d) The photosensitive resin formed by making the radical polymerizable compound (b) which has an epoxy group react with 5 to 80% of the carboxyl groups in the copolymer obtained by copolymerizing in the quantity which totals 100 mol%. The photosensitive resin composition containing the photosensitive resin of Claim 1 or 2 and a reactive diluent (f) as an essential component. The method according to claim 3, Furthermore, photosensitive resin composition containing solvent (g).