JP2007057587A - Photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in developability and in performance of a cured film, and a photo-solder resist for a printed circuit board. <P>SOLUTION: The alkali developable photosensitive resin composition contains a hydrophilic polymer (A), a polyfunctional acrylate monomer (B), a photopolymerization initiator (C) and host molecules (D) having inclusion ability, wherein cyclodextrin may be used as the component (D) and its content is preferably 0.1-15 wt.% based on the solid content of the photosensitive resin composition. The photo-solder resist comprises the photosensitive resin composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition. Specifically, the present invention relates to a photo solder resist for a printed wiring board.

  Photosensitive resin compositions are widely used for various applications. In a printed wiring board, a photosensitive resin composition is widely used as a photo solder resist as a permanent protective film for a circuit. Photo solder resist is a film formed on the entire surface excluding the part to be soldered of the circuit conductor, and when wiring electronic parts on the printed circuit board, it prevents solder from adhering to unnecessary parts, It is used as a protective coating that prevents the circuit from being directly exposed to air. Currently, liquid photo solder resists are widely used as photo solder resists for printed wiring boards from the viewpoints of high precision, high density, and environmental problems.

  As this liquid photo solder resist, for example, Patent Document 1 and Patent Document 2 propose a solder resist ink composition mainly composed of a partial reaction product of a novolak epoxy resin with acrylic acid. However, these compositions have problems such as insufficient cured film performance after exposure and stickiness (tack) remaining after the formation of the coating film.

Patent Document 3 proposes a photosensitive resin composition comprising as a main component a reaction product of an adduct of a novolak type epoxy resin and an unsaturated monocarboxylic acid and a polybasic acid anhydride. It is disclosed that it can also be used as a resist. However, this photosensitive resin composition has insufficient developability and has problems such as uneven development in unexposed areas when ink is left for a long time.
As described above, an alkali-developable photo solder resist having both curability and developability has not yet been obtained.
JP-A-60-208337 JP-A-61-59447 Japanese Patent Publication No. 1-54390

  An object of the present invention is to provide a photosensitive resin composition excellent in alkali developability and cured coating film performance.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention relates to an alkali developable photosensitive resin composition comprising a hydrophilic polymer (A), a polyfunctional acrylate monomer (B), a photopolymerization initiator (C), and a host molecule (D) having an inclusion ability. And a photo solder resist for a printed wiring board comprising the photosensitive resin composition.

The photosensitive resin composition of the present invention has the following effects.
・ Excellent alkali developability.
-Excellent cured film performance.

  The photosensitive resin composition of the present invention comprises a hydrophilic polymer (A), a polyfunctional acrylate monomer (B), a photopolymerization initiator (C), and a host molecule (D) having inclusion ability (hereinafter simply referred to as (D In particular, by containing (D), a photosensitive resin composition having both cured coating film performance and alkali developability is obtained. It is what

In the present invention, the host molecule (D) having an inclusion ability refers to a molecule having a property of taking another atom or molecule (hereinafter sometimes referred to as a guest) into a vacancy formed by itself.
As the driving force that causes the inclusion, hydrophobic interaction, ionic interaction, hydrogen bond, van der Waals force, and the like are considered.
In the photosensitive resin composition of the present invention, it is considered that (D) takes in an alkali metal ion as a guest and, as a result, exhibits an effect particularly excellent in alkali developability.

Specific examples of (D) include cyclic D-glucans (cyclodextrin, carbohydrates composed of D-glucopyranose groups, etc.), cyclophanes (cyclophane, azacyclophane, etc.), calixarene, crown A single molecule such as ether, spherand, capitand, etc., which has inclusion ability, urea, thiourea, deoxycholic acid, apocholic acid, cholic acid, dinitrodiphenyl, hydroquinone, perhydrotriphenylene, tri-o-thymoid, oxyflavan, Examples thereof include those having inclusion ability in multimolecular systems such as dicyanoammine nickel, dioxytriphenylmethane, methylnaphthalene, spirocoumarin, and perhydrotriphenylene.
Furthermore, natural polymers such as cellulose, starch, chitin, chitosan, proteins, synthetic polymers such as polyvinyl alcohol, and polymers having the above inclusion ability and a polymer suspended as a pendant substituent (polymer grafted onto polyvinyl alcohol). (Dextrin, cyclodextrin grafted on vinyl acetate, etc.) also have an inclusion ability and can be mentioned as a specific example of (D).
Among these, preferred are single molecules having inclusion ability, more preferred are cyclic D-glucans, and particularly preferred is cyclodextrin.

The content of (D) based on the weight of the solid content of (Q) is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% (below) from the viewpoint of both alkali developability and curability. In the above,% represents% by weight unless otherwise specified), particularly preferably 2 to 5%. If it is 0.1% or more, the alkali developability can be exhibited more favorably, and if it is 15% or less, the cured coating film performance can be exhibited more favorably.
In the present specification, the “solid content” means a component obtained by removing the solvent from the composition.

The hydrophilicity index in the hydrophilic polymer (A) in the present invention (hereinafter sometimes simply referred to as (A)) is defined by HLB. Generally, the larger this value, the higher the hydrophilicity.
Although the preferable range of the HLB value of (A) varies depending on the resin skeleton of (A) (for example, vinyl resin, epoxy resin, polyester resin, etc.), it is preferably 4-19, more preferably 5-18. Especially preferably, it is 6-17. When it is 4 or more, developability of the photo solder resist is further improved, and when it is 19 or less, the water resistance of the cured product is further improved. In addition, HLB in this invention is an HLB value by the Oda method, is a hydrophilicity-hydrophobicity balance value, and can be calculated from the ratio of the organic value and inorganic value of an organic compound.
HLB≈10 × inorganic / organic In addition, the inorganic value and the organic value are described on page 501 of the document “Synthesis of Surfactant and its Application” (published by Tsuji Shoten, written by Oda, Teramura); It is described in detail on page 198 of “Introduction to New Surfactants” (Takehiko Fujimoto, published by Sanyo Chemical Industries, Ltd.).
Moreover, the solubility parameter (hereinafter referred to as SP value) of (A) is preferably 7 to 14, more preferably 8 to 13, and particularly preferably 11 to 13. When it is 7 or more, the developability can be further improved, and when it is 14 or less, the water resistance of the cured product is further improved.

The SP value in the present invention is calculated by the method described in the following document proposed by Fedors et al.
"POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pp. 147-154)"
Those with close SP values are easy to mix with each other (highly dispersible), and those with a distant numerical value are indexes indicating that they are difficult to mix.

(A) preferably has a carboxyl group from the viewpoint of developability. The carboxyl group content is indicated by an acid value.
When the acid value of (A) is 10 mgKOH / g or more, developability is more likely to be exhibited, and when it is 500 mgKOH / g or less, the water resistance of the cured product can be further improved.

The acid value in the present invention can be measured by an indicator titration method using an alkaline titration solution.
The method is as follows.
(I) About 1 g of a sample is precisely weighed and placed in an Erlenmeyer flask, and then a neutral methanol / acetone solution (a mixture of acetone and methanol at 1: 1 (volume ratio)) is added and dissolved.
(Ii) Add several drops of phenolphthalein indicator and titrate with 0.1 mol / L potassium hydroxide titration solution. The end point of neutralization is defined as the time when the indicator is slightly red for 30 seconds.
(Iii) Determine using the following equation.
Acid value (KOHmg / g) = (A × f × 5.61) / S
However, A: The number of mL of 0.1 mol / L potassium hydroxide titration solution.
f: Potency of 0.1 mol / L potassium hydroxide titration solution
S: Sampling (g)

Examples of (A) include a hydrophilic vinyl polymer (A1) (hereinafter sometimes simply referred to as (A1)) and a hydrophilic epoxy polymer (A2) (hereinafter simply referred to as (A2)). ), Hydrophilic polyester resins, hydrophilic polyamide resins, hydrophilic polycarbonate resins, and hydrophilic polyurethane resins. (A) may be used by 1 type and may use 2 or more types together.
Of these, (A1) and (A2) are preferred from the viewpoint of the hardness of the resulting cured product and the ease of production.

Examples of (A1) include those having a hydrophilic group in the side chain and / or terminal of the vinyl polymer molecule.
Examples of the hydrophilic group include a carboxyl group, a hydroxyl group, a sulfonic acid group, an amino group, an amide group, a polyether group, and a combination of two or more of these.
In order to exhibit sufficient developability, those having a hydrophilic group, particularly a carboxyl group in the side chain are preferred.

  A preferred production method of (A1) is a vinyl monomer having a hydrophilic group (a) (hereinafter sometimes simply referred to as (a)) and, if necessary, a hydrophobic group-containing vinyl monomer (b) (hereinafter simply referred to as (b) ) May be represented by vinyl polymerization.

Examples of the vinyl monomer (a) having a hydrophilic group include the following vinyl monomers (a1) to (a7).
(A1) Hydroxyl-containing vinyl monomer:
Hydroxyalkyl (meth) acrylate [2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, etc.], polyalkylene glycol mono (meth) acrylate [polyethylene glycol mono (meta ) Acrylate etc.], alkylol (meth) acrylamide [N-methylol (meth) acrylamide etc.], hydroxystyrene and 2-hydroxyethylpropenyl ether.
Among (a1), preferred is hydroxyalkyl (meth) acrylate, particularly 2-hydroxyethyl (meth) acrylate, from the viewpoint of alkali developability.

(A2) Carboxyl group-containing vinyl monomer:
Unsaturated monocarboxylic acids [such as (meth) acrylic acid, crotonic acid and cinnamic acid], unsaturated polyvalent (2-4 valent) carboxylic acids [such as (anhydrous) maleic acid, itaconic acid, fumaric acid and citraconic acid], Unsaturated polyvalent carboxylic acid alkyl (alkyl group having 1 to 10 carbon atoms) ester [maleic acid monoalkyl ester, fumaric acid monoalkyl ester, citraconic acid monoalkyl ester, etc.] and salts thereof [alkali metal salt (sodium salt) And potassium salts, etc.), alkaline earth metal salts (calcium salts and magnesium salts, etc.), amine salts and ammonium salts, etc.].
Of (a2), preferred is an unsaturated monocarboxylic acid from the viewpoint of hydrophilicity, and more preferred is (meth) acrylic acid.
(A3) Sulphonic acid group-containing vinyl monomer:
Examples thereof include vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, α-methyl styrene sulfonic acid, 2- (meth) acryloylamido-2-methylpropane sulfonic acid, and salts thereof. Examples of the salt include alkali metal (sodium and potassium) salts, alkaline earth metal (calcium and magnesium) salts, primary to tertiary amine salts, ammonium salts and quaternary ammonium salts.

(A4) Amino group-containing vinyl monomer:
Tertiary amino group-containing (meth) acrylates [dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate)] and the like.
(A5) Amide group-containing vinyl monomer:
(Meth) acrylamide, N-alkyl (C1-6) (meth) acrylamide, diacetone acrylamide, N, N'-methylene-bis (meth) acrylamide, N, N-dialkyl (C1-6) or Diaralkyl (7 to 15 carbon atoms) (meth) acrylamide (for example, N, N-dimethylacrylamide and N, N-dibenzylacrylamide), methacrylformamide, N-methyl-N-vinylacetamide, cinnamic amide and cyclic amide (N-vinylpyrrolidone, N-allylpyrrolidone, etc.).
(A6) a quaternary ammonium base-containing vinyl monomer;
A quaternized product of a tertiary amino group-containing vinyl monomer having 6 to 50 carbon atoms (preferably 8 to 20 carbon atoms, such as methyl chloride, dimethyl sulfate, benzyl chloride and dimethyl carbonate), for example, dimethyl Examples include quaternized aminoethyl (meth) acrylate, quaternized diethylaminoethyl (meth) acrylate, quaternized dimethylaminoethyl (meth) acrylamide, and quaternized diethylaminoethyl (meth) acrylamide.
(A7) Polyether group-containing vinyl monomer:
Alkoxy (alkoxy group having 1 to 8 carbon atoms) polyalkylene (alkylene group having 2 to 4 carbon atoms) glycol mono (meth) acrylate [methoxypolyethylene glycol (degree of polymerization 2 to 40) mono (meth) acrylate and methoxypolypropylene glycol ( Polymerization degree 2-30) mono (meth) acrylate, etc.].

Of these, (a) is preferably (a1) and (a2), particularly (a2) from the viewpoint of imparting sufficient developability.

Examples of the hydrophobic group-containing vinyl monomer (b) include the following nonionic monomers (b1) to (b6).

(B1) (meth) acrylic acid ester;
C1-C20 alkyl (meth) acrylate of an alkyl group [for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, etc.]; alicyclic group-containing (meth) acrylate [dicyclopentanyl (meth) acrylate, sidiclopentenyl (meth) acrylate, isobornyl (meth) acrylate, etc. ];

(B2) an aromatic hydrocarbon monomer;
And hydrocarbon monomers having a styrene skeleton [for example, styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, and benzylstyrene] and vinylnaphthalene. It is done.
(B3) carboxylic acid vinyl ester;
Examples thereof include those having 4 to 50 carbon atoms, such as vinyl acetate, vinyl propionate and vinyl butyrate.
(B4) vinyl ether monomers;
Those having 3 to 50 (preferably 6 to 20) carbon atoms such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether and the like can be mentioned.
(B5) vinyl ketone monomer;
Examples thereof include those having 4 to 50 carbon atoms, such as vinyl methyl ketone, vinyl ethyl ketone, and vinyl phenyl ketone.
(B6) a halogen atom-containing monomer;
Examples thereof include those having 2 to 50 (preferably 2 to 20) carbon atoms, such as vinyl chloride, vinyl bromide, vinylidene chloride, chlorostyrene and bromostyrene.

  Preferred among (b) is (b1) from the viewpoint of curability, and more preferred is an alicyclic group-containing (meth) acrylate.

  In (A1), the charged monomer molar ratio of (a) / (b) is usually from 10 to 100/0 to 90, preferably from 10 to 80/20 to 90, more preferably from the viewpoint of curability and developability. ~ 85 / 15-75.

(A1) may contain a (meth) acryloyl group in the side chain for the purpose of further improving curability in the polymer having (a) and, if necessary, (b) as a constituent monomer.
Examples of the method of incorporating a (meth) acryloyl group in the side chain include the following methods (1) and (2).
(1): A polymer is produced using a monomer having a group capable of reacting with an isocyanate group (such as a hydroxyl group or a primary or secondary amino group) in at least a part of (a), and then (meth) A method of reacting a compound having an acryloyl group and an isocyanate group (such as acryloylethyl isocyanate);
(2); producing a polymer using a monomer having a group capable of reacting with an epoxy group (hydroxyl group, carboxyl group, primary or secondary amino group, etc.) in at least a part of (a); A method of reacting a compound having a (meth) acryloyl group and an epoxy group (such as glycidyl acrylate).

  The number average molecular weight of (A1) (hereinafter abbreviated as Mn. Measured value by gel permeation chromatography) is preferably 500 to 500,000 from the viewpoint of hardness and developability when it becomes a cured product. Preferably it is 1,000-100,000, Most preferably, it is 3,000-20,000.

(A1) can be obtained by performing polymerization with a radical polymerization initiator after diluting the monomer with a solvent (E4) (hereinafter sometimes simply referred to as (E4)) if necessary. Solvents (E4) include glycol ethers (such as ethylene glycol monoalkyl ether and propylene glycol monoalkyl ether), ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone), and esters (butyl acetate, ethylene glycol alkyl). Ether acetate and propylene glycol alkyl ether acetate). Of (E4), ketones and esters are preferred.
When (E4) is used, the amount used is not particularly limited, but is usually 1 to 400%, preferably 5 to 300%, particularly preferably 10 to 200% based on the total weight of the monomers.
Examples of the polymerization initiator include peroxides and azo compounds.
Peroxides include inorganic peroxides (eg, hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, etc.) and organic peroxides (eg, benzoyl peroxide, di-t-butyl peroxide, Cumene hydroperoxide, lauryl peroxide, etc.). Examples of the azo compound include azobis (2,4-dimethylvaleronitrile), azobisisobutyronitrile, azobis (2-methylbutyronitrile), azobiscyanovaleric acid and its salts (for example, hydrochloride), and azobis (2 -Amidinopropane) hydrochloride and the like. Preferred is an azo compound. As a usage-amount of a polymerization initiator, 0.0001-20% is preferable normally based on the total weight of a monomer, More preferably, it is 0.001-15%, Most preferably, it is 0.005-10%. The reaction temperature and reaction time are appropriately determined depending on the type of radical polymerization initiator.

  As described above, the hydrophilicity index of (A) is defined by HLB. Of these, the HLB value of (A1) is preferably 9 to 19, more preferably 10 to 18, particularly preferably 11 to 17. It is. If the HLB of (A1) is 9 or more, developability can be further improved.

  The epoxy-based polymer (A2) in the present invention (A) (hereinafter sometimes simply referred to as (A2)) has an epoxy resin skeleton containing a functional group having hydrophilicity such as a hydroxyl group or a carboxyl group. It is a polymer.

A preferred production method of (A2) is to open an epoxy group by reacting an acryloyl group-containing monocarboxylic acid with an epoxy group in an epoxy resin (A2 ₀ ) (hereinafter sometimes simply referred to as (A2 ₀ )). This is a method in which a hydroxyl group is generated by ringing, and a polyvalent carboxylic acid or a polyvalent carboxylic acid anhydride (e) (hereinafter sometimes simply referred to as (e)) is reacted with a part of the hydroxyl group.

Examples of (A2 ₀ ) include aliphatic epoxy resins [eg, Etototo YH-300, PG-202, PG-207 (all manufactured by Tohto Kasei Co., Ltd.)] and alicyclic epoxy resins [eg, CY-179, CY-177. CY-175 (all manufactured by Asahi Kasei Epoxy Co., Ltd.)] and aromatic epoxy resins [eg, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A epoxy resin, biphenyl type epoxy resin and glycidyl modified polyvinylphenol] Can be mentioned.
Among (A2 ₀ ), an aromatic epoxy resin is preferable from the viewpoint of curability.
Examples of the acryloyl group-containing monocarboxylic acid include acrylic acid.
Examples of the polyvalent carboxylic acid and the polyvalent carboxylic acid anhydride (e) include the unsaturated polyvalent carboxylic acids and their anhydrides in the aforementioned (a), and saturated polyvalent (2-6 valent) carboxylic acids ( Aliphatic saturated polycarboxylic acids such as oxalic acid, succinic acid, phthalic acid, adipic acid, dodecanedioic acid, dodecenyl succinic acid, pentadecenyl succinic acid and octadecenyl succinic acid; tetrahydrophthalic acid, hexahydrophthalic Acids, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid, aromatic polycarboxylic acids such as biphenyltetracarboxylic acid and naphthalenetetracarboxylic acid) and their anhydrides (eg, succinic anhydride, dodecenyl succinic anhydride, Aliphatic saturated polycarboxylic acids such as pentadecenyl succinic anhydride and octadecenyl succinic anhydride Water, aromatics such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, biphenyltetracarboxylic anhydride and naphthalenetetracarboxylic anhydride Polyvalent carboxylic acid anhydride). A saturated polycarboxylic acid anhydride is preferable from the viewpoint of reactivity and developability.

In the production of (A2), the charged weight ratio of acrylic acid / (A2 ₀ ) is preferably a charged weight ratio of acrylic acid such that the concentration of the acryloyl group in (A2) is 1.0 mmol / g or more. . From the above viewpoint, the weight ratio of acrylic acid / (A2 ₀ ) is preferably 0.072 or more / 1, and more preferably 0.079 to 0.72 / 1.
The reaction temperature in the reaction between (A2 ₀ ) and acrylic acid is not particularly limited, but is preferably 70 to 110 ° C. The reaction time is not particularly limited, but is preferably 5 to 30 hours. Further, if necessary, a catalyst (for example, triphenylphosphine) and a radical polymerization inhibitor (hydroquinone, p-methoxyphenol, etc.) may be used.
The charge equivalent of (e) relative to the weight of the acrylic acid adduct of (A2 ₀ ) is the charge equivalent of (e) such that the acid value of (A2) is preferably 10 to 500 mgKOH / g. For example, when (e) is a divalent carboxylic acid or an anhydride thereof, the weight of the charged equivalent of (e) / acrylic acid adduct of (A2 ₀ ) is preferably 0.18 to The amount is 8.9 meq / g, more preferably 0.53 to 7.1 meq / g.
The reaction temperature in the reaction of the acrylic acid adduct of (A2 ₀ ) and (e) is not particularly limited, but is preferably 70 to 110 ° C. The reaction time is not particularly limited, but is preferably 3 to 10 hours.

  Mn of (A2) is usually 500 to 3,000, preferably 1,000 to 2,800, particularly preferably 1,500 to 2,500, from the viewpoints of hardness and developability when it becomes a cured product. is there.

  The HLB value of (A2) is preferably 4 to 14, more preferably 5 to 13, and particularly preferably 6 to 12. If the HLB of (A2) is 4 or more, developability can be further improved.

The photosensitive resin composition (Q) of the present invention contains (A) preferably 10 to 50%, more preferably 15 to 45%, particularly preferably 20 to 40% based on the solid content of (Q). To do.
If it is 10% or more, the developability can be further improved, and if it is 50% or less, the hardness of the cured product is further improved.

  In the present invention, the polyfunctional acrylate monomer (B) used as one component in (Q) (hereinafter sometimes simply referred to as (B)) is an ordinary polyfunctional acrylate monomer. Used without limitation, bifunctional acrylate (B1), trifunctional acrylate (B2) and 4-6 functional acrylate (B3) can be mentioned. (B) may be used alone or in combination of two or more.

  Examples of the bifunctional acrylate (B1) include ethylene glycol diacrylate, diethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, glycerin diacrylate, 1 , 4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 2- Butyl-2-ethyl-1,3-propanediol diacrylate, dimethylol-tricyclodecane diacrylate, ethylene of bisphenol A Diacrylate of xide adduct, diacrylate of propylene oxide adduct of bisphenol A, trimethylolpropane acrylic acid benzoate, bisphenol A diglycidyl ether acrylic acid adduct, hydroxypivalic acid neopentyl glycol diacrylate, 2-acryloyl Examples include loxyethyl acid phosphate.

  Examples of the trifunctional acrylate (B2) include glycerin triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, triacrylate of trimethylolpropane ethylene oxide adduct, and the like.

  Examples of the 4- to 6-functional acrylate (B3) include pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like.

  Of these, (B2) and (B3) are preferable, and most preferable are dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and combinations thereof from the viewpoint of curability. Examples of (B) that can be easily obtained from the market include Aronix M-101, M-208, M-240, M-305, and M-400 (manufactured by Toagosei Co., Ltd.).

Moreover, (B) in this invention may contain the photosensitive acrylic oligomer (B4) in the one part. Examples of (B4) include urethane acrylate, polyester acrylate, and polyether acrylate having Mn of 1,000 or less and containing no carboxyl group and having two or more acryloyl groups in one molecule.
The content of (B4) in (B) is preferably 50% or less, more preferably 30% or less.

  The content of (B) based on the weight of the solid content of (Q) is preferably 10 to 60%, more preferably 20 to 55%, and particularly preferably 25 to 50%. If it is 10% or more, the hardness of the cured product is further preferred, and if it is 60% or less, the developability is further improved.

  As the photopolymerization initiator (C) used as one component in (Q) (hereinafter sometimes simply referred to as (C)), a photoradical polymerization initiator is used. For example, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, methyl benzoyl formate, isopropyl thioxanthone, 4,4-bis (dimethylamino) benzophenone 3,3-dimethyl-4-methoxy-benzophenone, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, tert-butylanthraquinone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, acetophenone, 2,2- Dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydride Xyl-2-methylpropiophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholino-1-propanone, 2-chlorothioxanthone, diethylthioxanthone, isopropylthioxanthone, diisopropylthioxanthone, Michler's ketone, benzyl- 2,4,6- (trihalomethyl) triazine, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5- Bis (9-acridinyl) pentane, 1,3-bis (9-acridinyl) propane, dimethylbenzyl ketal, trimethylbenzoyldiphenylphosphine oxide, tribromomethylphenylsulfone and 2-benzyl-2-dimethylamino-1- (4 Morpholinophenyl) - butan-1-one, and the like. (C) may be used alone or in combination of two or more.

  As (C), a commercially available product can be easily obtained. Examples thereof include Irgacure 907 and Irgacure 369 (manufactured by Ciba Specialty Chemicals).

  The content of (C) based on the weight of the solid content of (Q) is preferably 0.0001 to 20%, more preferably 0.001 to 15%, and particularly preferably 0.005 to 10%. If it is 0.0001% or more, the hardness of the cured product can be exhibited more favorably, and if it is 20% or less, developability can be exhibited more favorably.

(Q) may further contain other components (E) as necessary.
(E) includes inorganic fine particles (E1), sensitizer (E2), polymerization inhibitor (E3), solvent (E4), organic pigment (E5), and other additives (E6) (for example, chemical plating suppression) Agents, silane coupling agents, leveling agents, dyes, fluorescent brighteners, yellowing inhibitors, antioxidants, antifoaming agents, deodorants, fragrances, bactericides, fungicides, fungicides, etc.) Can be mentioned.

As the inorganic fine particles (E1), any inorganic fine particles can be used without particular limitation. A preferred volume average particle diameter of (E1) is 1 to 5,000 nm.
The volume average particle diameter is further preferably different depending on the purpose of addition, and for the purpose of improving the hardness of the cured product, the more preferable range is 1 to 300 nm, and the particularly preferable range is 1 to 100 nm. In the case of adding as, a more preferable range is 100 to 5,000 nm, and a particularly preferable range is 200 to 5,000 nm.
The volume average particle size can be measured, for example, using toluene as a solvent with a laser scattering particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.).
Examples of (E1) include metal oxide (E11), metal salt (E12), other inorganic substances (E13), and combinations thereof.
Examples of (E11) include titanium oxide, silicon oxide, and aluminum oxide.
Examples of (E12) include alkaline earth metal carbonates (calcium carbonate, magnesium carbonate, barium carbonate, etc.) and alkaline earth metal sulfates (calcium sulfate, barium sulfate, etc.).
Examples of (E13) include mica, kaolin, talc, aluminum silicate, and clay.
Of these, (E1) is preferably (E11) in the case of improving the hardness of the cured product, particularly silicon oxide in the form of fine particles (for example, a volume average particle diameter of 1 to 100 nm) from the viewpoint of heat resistance and chemical resistance. When used as a pigment, alkaline earth metal sulfate (especially barium sulfate) in (E12) and talc in (E13).

The content of (E1) based on the weight of the solid content of (Q) is usually 50% or less, preferably 0.5 to 50%. More preferably, it is 1 to 45%, particularly preferably 2 to 40%.
The content of (E1) has a more preferable range depending on the purpose of addition, and a more preferable range for the purpose of improving the hardness of the cured product is 0.5 to 20%, and a particularly preferable range is 0.5. When added as a pigment, a more preferable range is 1 to 45%, and a particularly preferable range is 2 to 40%.

  As the sensitizer (E2), nitro compounds (for example, anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzanthrone, p, p'-tetramethyldiaminobenzophenone, carbonyl compounds such as chloranil, nitrobenzene, p -Dinitrobenzene and 2-nitrofluorene), aromatic hydrocarbons (eg anthracene and chrysene), sulfur compounds (eg diphenyl disulfide etc.) and nitrogen compounds (eg nitroaniline, 2-chloro-4-nitroaniline) , 5-nitro-2-aminotoluene, tetracyanoethylene and the like.

  The usage-amount of the sensitizer (E2) with respect to the weight of a photoinitiator (C) is 100% or less normally, Preferably it is 0.5-80%, Most preferably, it is 1-70%.

  There is no limitation in particular as a polymerization inhibitor (E3), What is used for normal reaction is used. Specifically, diphenylhydrazyl, tri-p-nitrophenylmethyl, N- (3-N-oxyanilino-1,3-dimethylbutylidene) aniline oxide, p-benzoquinone, p-tert-butylcatechol, nitrobenzene, Examples include picric acid, dithiobenzoyl disulfide, and copper (II) chloride.

  The content of the polymerization inhibitor (E3) based on the weight of the solid content of (Q) is preferably 1.0% or less, more preferably 0.01 to 0.5%, particularly preferably 0.02 to 0.00. 1%.

  As a solvent (E4), the thing similar to the solvent (D4) used for manufacture of the above-mentioned (A1) can be used. When the solvent (E4) is used, the amount used is not particularly limited, but is preferably 5 to 500%, more preferably 7.5 to 100%, particularly preferably based on the weight of the solid content of (Q). Is 10 to 50%.

  As the organic pigment (E5), ordinary ones can be used, and examples thereof include phthalocyanine blue, phthalocyanine green, carbon black and the like, and these can be used alone or in combination.

  The amount of (E5) used relative to the weight of the solid content of (Q) is usually 5% or less, preferably 0.5 to 3%.

  As the chemical plating inhibitor, ordinary ones can be used, and examples thereof include triazole, benzotriazole, azidotoluene, thiourea, mercaptobenzothiazole and the like. A normal thing can be used as a leveling agent, for example, Monsanto Modaflow etc. can be used. A normal thing can be used as an antifoamer, for example, a silicone oil type antifoamer is mentioned.

The photosensitive resin composition (Q) of the present invention can be obtained, for example, by mixing the above-described components with a known mixing device such as a planetary mixer.
The photosensitive resin composition (Q) of the present invention obtained as described above is usually liquid at room temperature, and its viscosity is 0.1 mPa · s to 10,000 mPa · s at 25 ° C., preferably 1 mPa. S to 8,000 mPa · s. The viscosity can be measured with a BL type viscometer.

Another embodiment of the present invention is a photo solder resist for a printed wiring board comprising the photosensitive resin composition (Q).
The photo solder resist of the present invention includes various copper-clad laminates for printed wiring boards, metal plates such as aluminum plates, and plastic plates without copper foil (paper base phenol resin laminate, glass cloth base polyester resin laminate) , Glass cloth base epoxy resin laminate, polysulfone resin laminate, polyether sulfone resin laminate, polyetherimide resin laminate, glass cloth base teflon resin laminate, polyimide resin laminate, etc. .

  The film thickness of the photo solder resist is usually 0.5 to 500 μm, preferably 5 to 100 μm.

  Application methods of the photo solder resist include a method of applying with a screen printer, a roll coater, a curtain coater, a method of applying with a spray, a brush, a spatula, etc., and a method of immersing.

As the developer, an alkaline solution is usually used.
Alkaline components contained in the alkaline solution include alkali metal (such as sodium, potassium and lithium) hydroxides and carbonates, alkaline earth metal (such as calcium and magnesium) hydroxides, and amines (primary amine, 2 A tertiary amine, a tertiary amine, a quaternary ammonium salt, etc.). The pH of the alkaline solution is usually 7.1-12.
The concentration of the alkaline component in the alkaline solution is usually 0.001 to 30%.
Examples of the solvent in the alkaline solution include water, hydrophilic alcohol-based organic solvents, and mixed solvents thereof.
As water, normal industrial water, clean water or ion-exchanged water can be used.
Examples of hydrophilic alcohol-based organic solvents include aliphatic alcohols such as methanol, ethanol, n-propanol, i-propanol, and n-butanol), cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve, and carbitols such as methyl carbitol and ethyl carbe. Bitol etc. can be used.
The ratio of the water / hydrophilic alcohol-based organic solvent in the case of the mixed solvent is not particularly limited, but is preferably 10 to 100% / 0 to 90%, more preferably 50 to 80% / 20 to 50%.
The developer may further contain a surfactant and a small amount of an acid component (organic acid or inorganic acid).
As the surfactant, usual cationic surfactants, anionic surfactants, and nonionic surfactants can be used. The surfactant is used at a concentration of usually 0.01 to 2%, preferably 0.05 to 1% in the developer.
Examples of inorganic acids include boric acid, phosphoric acid, hydrochloric acid, and sulfuric acid, and examples of organic acids include acetic acid, formic acid, tartaric acid, and hydroxyacetic acid.
The inorganic acid and the organic acid are used in a concentration of 0 to 10%, preferably 0.5 to 5%, with the concentration in the developer being less than the equivalent of the alkaline component.

  Examples of the developing method include methods such as showering, spraying and dipping. Of these, spray is preferred.

  As the curing method, a method by irradiation with light or electron beam is usually mentioned, but thermal curing may be used in combination. Preferably, a combination of the two methods of curing by light irradiation and then curing by light irradiation is preferable.

The following irradiation light sources are suitable for curing with light. For example, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, metal halogen lamp, electron beam irradiation device, X-ray irradiation device, laser (argon laser, dye laser, nitrogen laser, helium cadmium laser, etc.) There is. Of these, high pressure mercury lamps and ultrahigh pressure mercury lamps are preferred.
As the heating device, a normal air circulation dryer, an electric furnace, a gas furnace, a far infrared furnace, or the like can be used.
The heat curing temperature is usually 150 ° C. or higher, preferably 180 ° C. to 250 ° C. The curing time is 10 minutes to 120 minutes, preferably 45 minutes to 90 minutes.

    In addition to the photo solder resist, the photosensitive resin composition of the present invention can also be used for applications such as a photoresist for a liquid crystal display substrate, an etching resist for a printed wiring board, and a plating resist for a printed wiring board.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these. Hereinafter, the part means part by weight.
[Preparation of hydrophilic polymer]
<Production Example 1>
In a glass Kolben equipped with a heating / cooling / stirring device, a reflux condenser, a dropping funnel and a nitrogen introduction pipe, 50 parts (0.22 mole) of isobornyl methacrylate, 30 parts (0.23 mole) of 2-hydroxyethyl methacrylate ), 20 parts (0.23 mole part) of methacrylic acid, and 150 parts of cyclohexanone were heated to 80 ° C. A solution in which 30 parts of azobisisobutyronitrile (V-60: Wako Pure Chemical Industries, Ltd., hereinafter referred to as AIBN) prepared in advance is dissolved in 120 parts of cyclohexanone after replacing the gas phase part in the system with nitrogen. 150 parts are dropped into Kolben at 80 ° C. over 10 minutes, and further reacted at the same temperature for 3 hours to obtain a hydrophilic polymer having a hydroxyl group and a carboxyl group (A-1: Mn: 12,000, SP value: 11.1). 86, HLB value: 11.98, acid value: 102 mgKOH / g) (resin content 25%).
Mn is a value in terms of polystyrene measured by the GPC method using a GPC measuring device (HLC-8120GPC, manufactured by Tosoh Corporation) and a column (two TSKgel GMHXL + TSKgel Multipore HXL-M, manufactured by Tosoh Corporation). Asked. The SP value, HLB value, and acid value were determined as described above. The same measurement method applies to the following production examples.

<Production Example 2>
In the same Kolben as in Production Example 1, isobonyl methacrylate 60 parts (0.27 mol part), 2-hydroxyethyl methacrylate 20 parts (0.15 mol part), methacrylic acid 20 parts (0.23 mol part), and 150 parts of cyclohexanone was charged and heated to 80 ° C. After substituting the gas phase part in the system with nitrogen, 55 parts of a solution prepared by dissolving 5 parts of AIBN prepared in advance in 50 parts of cyclohexanone was dropped into Kolben at 80 ° C. over 10 minutes, and further 3 at the same temperature. Reacted for hours. Thereafter, the resin content is diluted with cyclohexanone to 25%, the temperature is adjusted to 60 ° C., and a hydrophilic polymer having a hydroxyl group and a carboxyl group (A-2: Mn: 21,000, SP value: 12.24). A cyclohexanone solution having an HLB value of 12.38 and an acid value of 138 mgKOH / g was obtained (resin content was 25%).

<Production Example 3>
In the same Kolben as in Production Example 1, 200 parts of cresol novolac type epoxy resin “EOCN-1020” (manufactured by Nippon Kayaku, epoxy equivalent 200 g / eq) and 245 parts of propylene glycol monomethyl ether acetate are charged and heated to 110 ° C. It was dissolved uniformly. Subsequently, 76 parts (1.07 mol part) of acrylic acid, 2 parts of triphenylphosphine, and 0.2 part of p-methoxyphenol were charged and reacted at 110 ° C. for 10 hours. The reaction product was further charged with 91 parts (0.60 mol part) of tetrahydrophthalic anhydride, reacted at 90 ° C. for 5 hours, and a hydrophilic polymer having a hydroxyl group and a carboxyl group (A-3: Mn: 2,200, SP value: A propylene glycol monomethyl ether acetate solution (11.26, HLB value: 6.42, acid value: 91 mg KOH / g) was obtained (resin content was 60%).

<Examples 1-4 and Comparative Examples 1-3>
[Preparation of photo solder resist]
The materials shown in Table 1 were charged in a glass container, and the mixture was stirred until it became uniform. Further, an additive was added and kneaded by a three-roll mill to prepare a photo solder resist.
In addition, each symbol in Table 1 indicates the following.

A-1 solution: hydrophilic polymer (from Production Example 1)
A-2 solution: hydrophilic polymer (Production Example 2)
A-3 solution: hydrophilic polymer (of Production Example 3)
B-1: (Polyfunctional acrylate monomer)
“Neomer DA-600” (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate: Sanyo Chemical Industries, Ltd.)
C-1: (Photopolymerization initiator)
“Irgacure 907” (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one: manufactured by Ciba Specialty Chemicals Co., Ltd.)
D-1 (host molecule having inclusion ability)
: Β-cyclodextrin (manufactured by Cyclochem)
D-2 (host molecule having inclusion ability)
: Γ-cyclodextrin (manufactured by Cyclochem)
E1-1 (Inorganic fine particles)
: Barium sulfate (volume average particle diameter = 500 nm)
E4-1 (solvent)
: Propylene glycol monomethyl ether acetate

The photo solder resists obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated by the following evaluation methods. The results are shown in Table 1.
(1) Developability: A photo solder resist is applied on the entire surface of the patterned copper foil substrate, the coating film is dried at 80 ° C. for 90 minutes, and development by spray development with 1% sodium carbonate aqueous solution is performed. Sex was evaluated.
A: There is no residue visually.
○: There is a slight residue visually.
Δ: There are many residues by visual inspection.
X: A pattern was not visually formed.

(2) Coating film performance: A photo solder resist was coated on the entire surface of the patterned copper foil substrate and dried at 80 ° C. for 20 minutes. Next, a negative film was adhered to the substrate, and after exposure, a pattern was formed by developing with a 1% aqueous sodium carbonate solution. Next, this substrate was thermally cured at 150 ° C. for 60 minutes to produce an evaluation substrate having a cured coating film, and the coating film performance was evaluated.

(A) Hardness ·· Measured according to JIS K-5400 6.14.
(B) Solder heat resistance ·· An evaluation substrate having a cured coating film is immersed in a soldering iron at 260 ° C. for 30 seconds according to the test method of JIS C 6481, and then a peeling test with a cellophane tape is set as one cycle, and a total of 1 to 3 cycles The state of the coated film after observation was observed to evaluate the heat resistance.
A: There is no change in the coating film after 3 cycles.
○: Slightly changed after 3 cycles.
Δ: Change after 2 cycles.
X: Peeling occurs after 1 cycle.

(C) Acid-resistant ·· An evaluation substrate having a cured coating film was immersed in a 10% sulfuric acid aqueous solution at room temperature for 30 minutes, washed with water, then subjected to a peeling test using a cellophane adhesive tape, and the resist layer was peeled off and observed for discoloration. The acid resistance was evaluated.
(Double-circle): A change is not recognized at all.
○: Only slightly changed.
Δ: Remarkably changed.
X: The coating film was swollen and peeled off.

(D) Solvent resistance ·· An evaluation substrate having a cured coating film was immersed in methylene chloride at room temperature for 30 minutes, washed with water, then subjected to a peeling test using a cellophane adhesive tape, and the resist layer was observed for peeling and discoloration. Solvent properties were evaluated.
(Double-circle): A change is not recognized at all.
○: Only slightly changed.
Δ: Remarkably changed.
X: The coating film was swollen and peeled off.

  As can be seen from Table 1, by using the photo solder resist of the present invention, a solder resist film having good developability and excellent cured coating film performance (hardness, heat resistance, etc.) can be formed.

  According to the present invention, a photosensitive resin that can form an image by ultraviolet exposure and development with a dilute alkaline aqueous solution, has excellent developability, and can provide a pattern having excellent cured film performance such as hardness and heat resistance. Since the composition can be provided, it can be used as a solder resist for producing a printed wiring board, a photoresist for a liquid crystal display substrate, an etching resist for a printed wiring board, and a plating resist for a printed wiring board.

Claims (6)

  A photosensitive resin composition capable of alkali development containing a hydrophilic polymer (A), a polyfunctional acrylate monomer (B), a photopolymerization initiator (C), and a host molecule (D) having inclusion ability.   The photosensitive resin composition according to claim 1, wherein the content of the host molecule (D) having inclusion ability is 0.1 to 15% by weight based on the solid content of the photosensitive resin composition.   The photosensitive resin composition according to claim 1, wherein the host molecule (D) having an inclusion ability is cyclodextrin.   The photosensitive resin composition according to any one of claims 1 to 3, further comprising inorganic fine particles (E1), wherein the content of (E1) is 0.5 to 50% by weight based on the weight of the solid content of the photosensitive resin composition. object.   The photosensitive resin composition according to claim 4, wherein the volume average particle diameter of the inorganic fine particles (E1) is 1 to 5,000 nm.   The photo solder resist for printed wiring boards which consists of the photosensitive resin composition in any one of Claims 1-5.