KR102456796B1 - Curable resin composition, dry film, cured product and printed wiring board - Google Patents

Abstract

In addition to the characteristics as solder resists, such as solder heat resistance, the curable resin composition which also had high reflectance, a dry film, hardened|cured material, and a printed wiring board are provided. It is a curable resin composition containing (A) curable resin, (B) a white coloring agent, (C) optical brightening agent, and (D) at least any 1 sort(s) chosen from an isocyanate compound and a coupling agent. It is a dry film which has a resin layer obtained by apply|coating and drying the said curable resin composition on a film. It is a hardened|cured material obtained by hardening the resin layer obtained by apply|coating and drying the said curable resin composition or the said curable resin composition. It is a printed wiring board which has the said hardened|cured material.

Description

Curable resin composition, dry film, cured product and printed wiring board

The present invention relates to a curable resin composition (hereinafter also simply referred to as “composition”), a dry film, a cured product, and a printed wiring board, and in particular, a curable resin composition, dry film, cured product and printed wiring board for improving reflectance is about

A printed wiring board generally etches the copper foil which faced|matched a laminated board along circuit wiring, an electronic component is arrange|positioned at a predetermined place, and soldering is performed. A soldering resist film is used as a protective film of the circuit at the time of soldering an electronic component to such a printed wiring board. This soldering resist film prevents that a circuit conductor is directly exposed to air and is corroded by oxygen and moisture while preventing solder from adhering to an unnecessary part at the time of soldering. Moreover, it also functions as a permanent protective film of a circuit board. Therefore, various characteristics, such as adhesiveness, electrical insulation, solder heat resistance, solvent resistance, and chemical resistance, are calculated|required.

In addition, printed wiring boards are moving toward miniaturization (fineness), multi-layering, and single-boarding in order to achieve high density, and the mounting method is also changing to surface mounting technology (SMT). Therefore, also for a soldering resist film, the request|requirement of fine formation, high resolution, high precision, and high reliability is increasing.

As a technique for forming a pattern of such a solder resist, the photoresist method which can form a fine pattern precisely, especially, the alkali development type liquid photoresist method from consideration of an environmental aspect, etc. especially becomes mainstream.

For example, in Patent Document 1 and Patent Document 2, an unsaturated monocarboxylic acid is reacted with a novolak-type epoxy resin, and a reaction product obtained by adding a polybasic acid anhydride is used as a base polymer. A liquid resist ink that can be developed with an aqueous alkali solution. A composition is disclosed.

On the other hand, in recent years, the use of directly mounting light emitting diodes (LEDs) emitting light at low power, such as backlights of liquid crystal displays such as portable terminals, personal computers and televisions, as well as light sources of lighting fixtures, on printed wiring boards coated with a solder resist film is increasing. have.

Then, in order to utilize the light of LED efficiently, the printed wiring board which has a soldering resist film of high reflectance is calculated|required.

As a technique for raising the reflectance of a soldering resist, the white curable soldering resist composition containing carboxyl group-containing resin which does not have an aromatic ring, and rutile type titanium oxide is disclosed by patent document 3, for example.

Japanese Patent Publication No. 1-54390 Japanese Patent Publication No. Hei 7-17737 Japanese Patent Laid-Open No. 2007-322546

However, while all the conventional compositions described in the said patent documents 1-3 fully have characteristics as soldering resists, such as solder heat resistance, there was still room for improvement for obtaining a high reflectance.

Then, the objective of this invention is providing the curable resin composition, dry film, hardened|cured material, and printed wiring board which also had high reflectance in addition to characteristics as solder resists, such as solder heat resistance.

As a result of earnest examination, this inventor uses for curable resin composition together with at least any 1 type chosen from an optical brightening agent, an isocyanate compound, and a coupling agent with white coloring agents, such as titanium oxide, Solder resists, such as solder heat resistance It has been found that, in addition to the characteristic as a phosphor, a high reflectance can be achieved, the present invention has been completed.

That is, the curable resin composition of the present invention contains at least any one selected from (A) a curable resin, (B) a white colorant, (C) an optical brightener, and (D) an isocyanate compound and a coupling agent. is characterized by

Moreover, the dry film of this invention has a resin layer obtained by apply|coating and drying the said curable resin composition of this invention on a film, It is characterized by the above-mentioned.

Moreover, the hardened|cured material of this invention is obtained by hardening the resin layer obtained by apply|coating and drying the said curable resin composition of this invention, or the said curable resin composition of this invention, It is characterized by the above-mentioned.

Moreover, the printed wiring board of this invention has the said hardened|cured material of this invention, It is characterized by the above-mentioned.

ADVANTAGE OF THE INVENTION According to this invention, in addition to the characteristic as soldering resists, such as solder heat resistance, it became possible to implement|achieve the curable resin composition which also had high reflectance, a dry film, hardened|cured material, and a printed wiring board.

BRIEF DESCRIPTION OF THE DRAWINGS It is a graph which shows the relationship between the wavelength and reflectance of each composition of Examples 2 and 3 and Comparative Example 2. FIG.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

The curable resin composition of the present invention contains at least any one selected from (A) a curable resin, (B) a white colorant, (C) an optical brightener, and (D) an isocyanate compound and a coupling agent. have characteristics. Thereby, in addition to the characteristic as soldering resists, such as solder heat resistance, the curable resin composition which also had high reflectance can be obtained.

Next, each component of curable resin composition of this invention is demonstrated. In addition, in this specification, (meth)acrylate is a term generically naming an acrylate, a methacrylate, and a mixture thereof, and it is the same also about other similar expression.

[(A) curable resin]

Curable resin composition of this invention contains (A) curable resin. (A) curable resin used in this invention is (A-1) thermosetting resin or (A-2) photocurable resin, These mixtures may be sufficient as it.

((A-1) thermosetting resin)

(A-1) As a thermosetting resin, what is necessary is just resin which hardens|cures by heating and shows electrical insulation, For example, an epoxy compound, an oxetane compound, a melamine resin, a silicone resin, etc. are mentioned. In particular, in this invention, an epoxy compound and an oxetane compound can be used suitably, These may be used together.

As said epoxy compound, the well-known and usual compound which has one or more epoxy groups can be used, Especially, the compound which has two or more epoxy groups is preferable. For example, monoepoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, glycidyl (meth) acrylate, bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenolo Volak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4'-diglycidyl Ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris(2,3-epoxypropyl) isocyanurate, triglycidyl The compound which has 2 or more epoxy groups in 1 molecule, such as tris (2-hydroxyethyl) isocyanurate, is mentioned. These can be used individually or in combination of 2 or more types according to a required characteristic.

Next, an oxetane compound is demonstrated. The following general formula (I)

Specific examples of the oxetane compound containing the oxetane ring represented by (wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) include 3-ethyl-3-hydroxymethyloxetane (Toagosei ( Co., Ltd. product, brand name OXT-101), 3-ethyl-3-(phenoxymethyl)oxetane (Toagosei Co., Ltd. product, brand name OXT-211), 3-ethyl-3-(2-ethylhexyloxymethyl) ) Oxetane (manufactured by Toagosei Co., Ltd., trade name OXT-212), 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene (manufactured by Toagosei Co., Ltd., trade name) OXT-121), bis(3-ethyl-3-oxetanylmethyl)ether (Toagosei Co., Ltd. product, brand name OXT-221) etc. are mentioned. Moreover, the oxetane compound of a phenol novolak type, etc. are mentioned. These oxetane compounds may be used together with the said epoxy compound, and may be used independently.

((A-2) photocurable resin)

Next, as the photocurable resin (A-2), any resin that is cured by irradiation with active energy rays and exhibits electrical insulation properties is sufficient. In particular, in the present invention, a compound having at least one ethylenically unsaturated bond in the molecule is preferably used. do.

As a compound which has an ethylenically unsaturated bond, a well-known and usual photopolymerizable oligomer, a photopolymerizable vinyl monomer, etc. are used. Among these, as a photopolymerizable oligomer, an unsaturated polyester type oligomer, a (meth)acrylate type oligomer, etc. are mentioned. Examples of the (meth)acrylate oligomer include epoxy (meth)acrylates such as phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, and bisphenol epoxy (meth) acrylate, urethane (meth) Acrylate, epoxyurethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polybutadiene modified (meth)acrylate, etc. are mentioned.

As a photopolymerizable vinyl monomer, A well-known and usual thing, For example, Styrene derivatives, such as styrene, chlorostyrene, (alpha)-methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate, or vinyl benzoate; Vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl vinyl ethers such as ether and triethylene glycol monomethyl vinyl ether; (such as acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide meth)acrylamides; allyl compounds such as triallyl isocyanurate, diallyl phthalate, and diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isoboronyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) ) esters of (meth)acrylic acid such as acrylates; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and pentaerythritol tri(meth)acrylate; Alkoxyalkylene glycol mono(meth)acrylates, such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; Ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate , pentaerythritol tetra(meth)acrylate, and alkylene polyol poly(meth)acrylates such as dipentaerythritol hexa(meth)acrylate; Polyoxyalkylene glycol poly(es) such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane tri(meth)acrylate meth) acrylates; poly(meth)acrylates such as hydroxypivalic acid neopentyl glycol ester di(meth)acrylate; Isocyanurate-type poly(meth)acrylates, such as tris[(meth)acryloxyethyl] isocyanurate, etc. are mentioned. These can be used individually or in combination of 2 or more types according to a required characteristic.

((A-3) Carboxyl group-containing resin)

In addition, in the case of promoting a thermosetting reaction with an epoxy resin in the composition of the present invention, or when the composition of the present invention is an alkali developing type photosensitive resin composition, (A) a carboxyl group-containing resin is used as the curable resin It is preferable to do Carboxyl group-containing photosensitive resin having an ethylenically unsaturated group may be sufficient as carboxyl group-containing resin, and it may have an aromatic ring, and it is not necessary to have it.

Specific examples of the carboxyl group-containing resin that can be used in the composition of the present invention include the compounds listed below (any of oligomers and polymers may be used).

(1) Carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, or isobutylene. When this carboxyl group-containing resin has an aromatic ring, at least 1 sort(s) of an unsaturated carboxylic acid and an unsaturated group containing compound should just have an aromatic ring.

(2) Diisocyanates such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyether polyols , polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A alkylene oxide adduct diol, carboxyl group-containing urethane resin by polyaddition reaction of a diol compound such as a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group . When this carboxyl group-containing urethane resin has an aromatic ring, at least 1 sort(s) of diisocyanate, a carboxyl group-containing dialcohol compound, and a diol compound should just have an aromatic ring.

(3) Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with the terminal of a urethane resin by polyaddition reaction of a diol compound such as A-type alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group. When this carboxyl group-containing urethane resin has an aromatic ring, at least 1 sort(s) of a diisocyanate compound, a diol compound, and an acid anhydride should just have an aromatic ring.

(4) Diisocyanate and bifunctional epoxy resins such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, and biphenol type epoxy resin A photosensitive carboxyl group-containing urethane resin by polyaddition reaction of (meth)acrylate or its partial acid anhydride-modified product, a carboxyl group-containing dialcohol compound and a diol compound. When this photosensitive carboxyl group-containing urethane resin has an aromatic ring, at least one of diisocyanate, (meth)acrylate of a bifunctional epoxy resin or a partial acid anhydride modified product thereof, a carboxyl group-containing dialcohol compound and a diol compound has an aromatic ring do.

(5) During the synthesis of the resin of (2) or (4), a compound having one hydroxyl group and one or more (meth)acryloyl group is added to a molecule such as hydroxyalkyl (meth)acrylate, and the terminal ( Meth) acrylated carboxyl group-containing urethane resin. When this photosensitive carboxyl group containing urethane resin has an aromatic ring, the compound which has one hydroxyl group and one or more (meth)acryloyl group in a molecule|numerator may have an aromatic ring.

(6) Compounds having one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate during the synthesis of the resin of (2) or (4) A carboxyl group-containing urethane resin obtained by adding a (meth)acrylated terminal. When this photosensitive carboxyl group containing urethane resin has an aromatic ring, the compound which has one isocyanate group and one or more (meth)acryloyl groups in a molecule|numerator may have an aromatic ring.

(7) A photosensitive carboxyl group-containing resin in which (meth)acrylic acid is reacted with a polyfunctional epoxy resin, and dibasic acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are added to the hydroxyl group present in the side chain. When this photosensitive carboxyl group-containing resin has an aromatic ring, at least 1 sort(s) of a polyfunctional epoxy resin and a dibasic acid anhydride should just have an aromatic ring.

(8) A photosensitive carboxyl group-containing resin in which (meth)acrylic acid is reacted with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of the bifunctional epoxy resin with epichlorohydrin, and dibasic acid anhydride is added to the generated hydroxyl group. When this photosensitive carboxyl group-containing resin has an aromatic ring, at least 1 sort(s) of a bifunctional epoxy resin and a dibasic acid anhydride should just have an aromatic ring.

(9) A polyester resin containing a carboxyl group in which a dicarboxylic acid is reacted with a polyfunctional oxetane resin, and a dibasic acid anhydride is added to a primary hydroxyl group generated. When this photosensitive carboxyl group containing polyester resin has an aromatic ring, at least 1 sort(s) of polyfunctional oxetane resin, dicarboxylic acid, and dibasic acid anhydride should just have an aromatic ring.

(10) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide is reacted with an unsaturated group-containing monocarboxylic acid, and a polybasic acid anhydride is added to the obtained reaction product Carboxyl group-containing photosensitive resin obtained by making it react.

(11) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, and a polybasic acid anhydride is added to the obtained reaction product Carboxyl group-containing photosensitive resin obtained by making it react.

(12) In an epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and unsaturation such as (meth)acrylic acid A carboxyl group obtained by reacting a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic acid with the alcoholic hydroxyl group of the reaction product obtained by reacting a group-containing monocarboxylic acid containing photosensitive resin. When this photosensitive carboxyl group-containing polyester resin has an aromatic ring, at least one of an epoxy compound, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, an unsaturated group-containing monocarboxylic acid and polybasic acid anhydride is aromatic You should have a ring.

(13) In addition to any of the above (1) to (12) resins, one epoxy group and one or more (meth) A photosensitive carboxyl group-containing resin obtained by adding a compound having an acryloyl group. When this photosensitive carboxyl group containing urethane resin has an aromatic ring, the compound which has one epoxy group and one or more (meth)acryloyl groups in a molecule|numerator may have an aromatic ring.

Since the above carboxyl group-containing resin has many carboxyl groups in the side chain of a backbone/polymer, image development by a diluted alkali aqueous solution becomes possible.

Among the above, carboxyl group-containing resin obtained by copolymerization of (1) is preferable at the point which is excellent in suppression of the fall of the reflectance by heat|fever, and suppression of discoloration. In addition, the use of a carboxyl group-containing resin derived from styrene or a styrene derivative is preferable because a composition excellent in solder heat resistance can be obtained. Moreover, even if it uses a non-photosensitive thing among carboxyl group-containing resin, since the composition excellent in solder heat resistance is obtained, it is preferable.

The acid value of the carboxyl group-containing resin is preferably in the range of 20 to 200 mgKOH/g, more preferably in the range of 40 to 180 mgKOH/g. If it is in the range of 20 to 200 mgKOH/g, adhesion of the coating film is obtained, alkali development is facilitated, dissolution of the exposed part by the developer is suppressed, lines are not thinner than necessary, and normal resist pattern drawing is easy. It is preferable because it

Moreover, although the weight average molecular weight of carboxyl group-containing resin used by this invention changes with resin frame|skeleton, the range of 2,000-150,000 is preferable. If it is this range, dry to touch performance is favorable, the moisture resistance of the coating film after exposure is good, and it is hard to generate|occur|produce a film|membrane decrease at the time of image development. Moreover, if it is the range of the said weight average molecular weight, a resolution improves, developability is favorable, and storage stability becomes good. More preferably, it is 5,000-100,000. A weight average molecular weight can be measured by gel permeation chromatography.

In addition, (A) when an epoxy resin and a carboxyl group-containing resin are used together as the curable resin, the equivalent of the epoxy group contained in the epoxy resin is 2.0 or less with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin, yellowing resistance is good It is preferable, since it becomes more preferable, More preferably, it is 1.5 or less, More preferably, it is 1.0 or less. This is because there exists a tendency for discoloration easily when an epoxy group is contained.

[(B) white colorant]

(B) Titanium oxide, zinc oxide, potassium titanate, zirconium oxide, antimony oxide, lead white, zinc sulfide, lead titanate, etc. are mentioned as a white colorant, However, Titanium oxide is used from the point of the inhibitory effect of discoloration by heat is high. It is preferable to do (B) By containing a white coloring agent, the composition of this invention can be made white, and it becomes possible to obtain a high reflectance.

As titanium oxide, the titanium oxide of any structure of a rutile type, an anatase type, and a Ramsdelite type may be sufficient, and may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, Ramsdelite-type titanium oxide is Ramsdelite-type Li _{0 .} It is obtained by performing _the lithium desorption process by chemical oxidation to ₅ TiO2.

Among the above, use of rutile-type titanium oxide is preferable because heat resistance can be further improved, discoloration due to light irradiation is less likely to occur, and quality can be made difficult to deteriorate even under a severe use environment. In particular, by using aluminum oxide such as alumina or rutile-type titanium oxide surface-treated with silica, deterioration to light can be suppressed, or reflectance and heat resistance can be further improved. In addition, after the above-mentioned surface treatment, other surface treatment may be further performed. In particular, the reflectance can be further improved by further surface treatment with zirconia after surface treatment with alumina. (B) When titanium oxide is used as a white colorant, the content of rutile-type titanium oxide surface-treated with aluminum oxide in the total titanium oxide is preferably 10% by mass or more, more preferably 30% by mass or more, The upper limit is 100% by mass or less, that is, the total amount of titanium oxide may be rutile-type titanium oxide surface-treated with the aluminum oxide. As rutile type titanium oxide surface-treated with the said aluminum oxide, Ishihara Sangyo Co., Ltd. product CR-58 which is a rutile type chlorine process titanium oxide, and Ishihara Sangyo Co., Ltd. product R which is a rutile type sulfuric acid method titanium oxide is rutile, for example. -630 and the like. In addition, it is also preferable to use rutile-type titanium oxide surface-treated with silicon oxide, and even in this case, heat resistance can be further improved. Moreover, it is also preferable to use the rutile-type titanium oxide surface-treated by both aluminum oxide and silicon oxide, For example, CR-90 etc. made from Ishihara Sangyo Co., Ltd. which are rutile-type chlorine method titanium oxide are mentioned.

In addition, since anatase-type titanium oxide has a lower hardness than that of a rutile-type, when anatase-type titanium oxide is used, it becomes more favorable in the point of the moldability of a composition.

Moreover, although sulfur may contain in titanium oxide, 100 ppm or less is preferable and, as for the sulfur content, 60 ppm or less is more preferable. It is because discoloration of the peripheral part by the sulfur gas which generate|occur|produces does not generate|occur|produce that sulfur content is 100 ppm or less.

The compounding quantity of such (B) white colorant is preferably in the range of 5 to 80 mass %, more preferably in the range of 5 to 80 mass % with respect to the solid content in the resin composition (components excluding the organic solvent when the resin composition contains an organic solvent). It is the range of 10-70 mass %.

[(C) Fluorescent Brightener]

The (C) fluorescent whitening agent used for this invention increases the whiteness of the hardened|cured material of a composition, and can make it appear that it is not discolored. In this invention, as mentioned above, in curable resin composition, it becomes possible to implement|achieve high reflectance in the cured coating film by using (C) a fluorescent whitening agent with (B) a white coloring agent.

The optical brightener absorbs light with a wavelength of 200 to 400 nm and emits light with a wavelength of 400 to 500 nm. Examples of such fluorescent dyes include benzoxazoyl derivatives, coumarin derivatives, styrenebiphenyl derivatives, pyrazolone derivatives, and bis(triazinylamino)stilbendisulfonic acid derivatives. Among them, benzoxazoyl derivatives are preferable. Moreover, as a substituent which the benzoxazoyl derivative has, butyl, octyl, naphthalene, thiophene, and stilbene are preferable.

As a compounding quantity of (C) optical brightener in the composition of this invention, with respect to 100 mass parts of (A) curable resin, Preferably it is 0.01-10 mass parts, More preferably, it is 0.05-7 mass parts. (C) High reflectance can be achieved by making the compounding quantity of an optical brightener into said range.

[(D) at least any one selected from an isocyanate compound and a coupling agent]

Curable resin composition of this invention contains at least any 1 sort(s) chosen from (D) an isocyanate compound and a coupling agent. (D) By containing at least any one selected from the group consisting of an isocyanate compound and a coupling agent, absorption by the optical brightener at 400 to 420 nm is further promoted, and the effect of the optical brightener at 440 to 470 nm, that is, the reflectance is improved. can promote

((D-1) isocyanate compound)

(D-1) As an isocyanate compound, well-known isocyanate compounds, such as a monoisocyanate compound which has one isocyanate group, and polyisocyanate which has two or more isocyanate groups, can be used. In this invention, since it is excellent in storage stability, a viewpoint that workability|operativity improves a block isocyanate compound is preferable.

As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate are used.

Examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, and o-xylylene diisocyanate. , m-xylylene diisocyanate, diphenylmethylene diisocyanate, and 2,4-tolylene dimer.

Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate) and isophorone diisocyanate.

Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. Moreover, the adduct body of the isocyanate compound illustrated above, a biuret body, and an isocyanurate body are mentioned.

The blocked isocyanate group contained in the blocked isocyanate compound is a group in which an isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to form an isocyanate group.

As a block isocyanate compound, the addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. As an isocyanate compound which can react with a blocking agent, the polyisocyanate compound etc. which were mentioned above are mentioned.

As an isocyanate blocking agent, For example, Phenol type blocking agents, such as a phenol, cresol, xylenol, chlorophenol, and ethyl phenol; lactam blocking agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam and β-propiolactam; active methylene-based blocking agents such as ethyl acetoacetate and acetylacetone; Methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, glycol alcohol-based blocking agents such as butyl acid, diacetone alcohol, methyl lactate, and ethyl lactate; Oxime block agents, such as formaldehyde doxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime; mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol, and ethylthiophenol; acid amide blocking agents such as acetate amide and benzamide; imide block agents such as succinimide and maleic imide; amine blocking agents such as xylidine, aniline, butylamine, and dibutylamine; imidazole-based blocking agents such as imidazole and 2-ethylimidazole; imine-based blocking agents such as methyleneimine and propyleneimine; pyrazole-based blocking agents such as dimethylpyrazole; Maleic acid ester type blocking agents, such as diethyl maleic acid, etc. are mentioned.

As a block isocyanate compound, it is a commercially available thing, For example, Smidur (trademark) BL-3175, BL-4165, BL-1100, BL-1265, Desmodur (trademark) TPLS-2957, TPLS-2062, TPLS -2078, TPLS-2117, Desmosum 2170, Desmosum 2265 (all manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate (registered trademark) 2512, Coronate 2513, Coronate 2520 (all manufactured by Nippon Polyurethane Kogyo Co., Ltd.) ), B-830, B-815, B-846, B-870, B-874, B-882 (all manufactured by Mitsui Takeda Chemical Co., Ltd.), Duranate SBN-70D, TPA-B80E, 17B-60PX, E402-B80T (all manufactured by Asahi Kasei Chemicals), TRIXENE BI 7982, 7950, 7951, 7960, and 7961 (manufactured by Baxeneden Chemicals Limited). BI 7982 is preferred. In addition, Smidur BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

These isocyanate compounds can be used individually or in combination of 2 or more types.

((D-2) coupling agent)

(D-2) As a coupling agent, a silane-type coupling agent, a titanium-type coupling agent, a zirconium-type coupling agent, an aluminum-type coupling agent, etc. can be used. In particular, in this invention, a silane-type coupling agent can be used suitably.

The silane-based coupling agent is composed of an organic material (organic group) and silicon, and is generally XnR'(n-1)Si-R"-Y (X=hydroxyl and alkoxyl, etc., Y=vinyl group, epoxy group, styryl group, methacryloxy group, acryloxy group, amino group, ureide group, chloropropyl group, mercapto group, polysulfide group, isocyanate group, etc.). Since it has the above different reactive groups, it functions as an intermediary connecting organic materials and inorganic materials, which are usually very difficult to associate, and is used for improving the strength of composite materials, modifying resins, modifying surfaces, and the like.

The specific example of a silane coupling agent is as follows.

N-γ-(aminoethyl)-γ-aminopropyltriethoxysilane, N-γ-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltri Methoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylphenyldiethoxysilane, 2-amino-1-methylethyltriethoxysilane, N-methyl-γ- Aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-butyl-γ-aminopropylmethyldiethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane , N-β-(aminoethyl)-N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ -Glycidoxypropylmethyldimethoxysilane (3-glycidoxypropylmethyldimethoxysilane), β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ -Mercaptopropylmethyldimethoxysilane, γ-isocyanatopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, methacryloxypropyltrimethyl oxysilane, γ-polyoxyethylenepropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, etc. are mentioned, Among them, 3-glycidoxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxy Silanes are preferred.

As a commercial item of a silane coupling agent, For example, KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-9103, KBM-573, KBM- 575, KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007 (all are brand names; Shin-Etsu Silicone Co., Ltd. make) etc. are mentioned. These can be used individually or in combination of 2 or more types.

As a total compounding quantity of (D-1) isocyanate compound and (D-2) coupling agent in the composition of this invention, with respect to 100 mass parts of (A) curable resin, Preferably it is 0.01-50 mass parts, More preferably is 0.2 to 30 parts by mass. (D-1) In the case of an isocyanate compound, 0.2-20 mass parts is more preferable, on the other hand, in the case of (D-2) a coupling agent, 0.2-25 mass parts is still more preferable, 0.2-15 mass parts is especially preferable. (D-1) By making the total compounding quantity of an isocyanate compound and a (D-2) coupling agent into said range, a high reflectance and storage stability are compatible.

[At least one of (E-1) curing agent and (E-2) curing catalyst]

The composition of this invention WHEREIN: When using (A-1) a thermosetting resin, at least any 1 sort(s) of (E-1) hardening|curing agent and (E-2) hardening catalyst can further be added.

(E-1) Examples of the curing agent include polyfunctional phenol compounds, polycarboxylic acids and acid anhydrides thereof, aliphatic or aromatic primary or secondary amines, polyamide resins, and polymercapto compounds. Among them, polyfunctional phenol compounds, polycarboxylic acids, and acid anhydrides thereof are preferably used from the viewpoint of workability and insulating properties.

As a polyfunctional phenol compound, what is necessary is just a compound which has two or more phenolic hydroxyl groups in 1 molecule, A well-known and usual thing can be used. Specifically, phenol novolak resin, cresol novolak resin, bisphenol A, allylated bisphenol A, bisphenol F, bisphenol A novolak resin, vinylphenol copolymer resin, etc. are mentioned, and the reactivity is high and the effect of improving heat resistance is high. From a high point, especially a phenol novolak resin is preferable. Such a polyfunctional phenol compound is also subjected to an addition reaction with at least any one of an epoxy compound and an oxetane compound in the presence of an appropriate curing catalyst.

As polycarboxylic acid and its acid anhydride, they are a compound which has two or more carboxyl groups in 1 molecule, and its acid anhydride, For example, a copolymer of (meth)acrylic acid, a copolymer of maleic anhydride, a condensate of dibasic acid, etc. can be heard As a commercial item, the BASF Japan Co., Ltd. John Creel (brand name), the SMA resin (brand name) made by Satoma Co., Ltd., the polyazelaic anhydride by a New Nippon Rica company, etc. are mentioned.

In addition, (E-2) the curing catalyst is at least any one of an epoxy compound and an oxetane compound, and (E-1) a compound that can serve as a curing catalyst in the reaction with the curing agent, or a curing agent is not used. It is a compound that serves as a catalyst for polymerization. Specific examples of the curing catalyst include tertiary amines, tertiary amine salts, quaternary onium salts, tertiary phosphines, crown ether complexes, phosphonium ylide, and the like. Or it can be used in combination of 2 or more types.

Especially, imidazoles, such as brand name 2E4MZ, C11Z, C17Z, 2PZ, AZINE compound of imidazole, such as brand name 2MZ-A and 2E4MZ-A, isocyanur of imidazole, such as brand name 2MZ-OK and 2PZ-OK Imidazole hydroxymethyl compounds such as acid salts, trade names 2PHZ and 2P4MHZ (all trade names are manufactured by Shikoku Kasei Kogyo Co., Ltd.), dicyandiamide and its derivatives, melamine and its derivatives, diaminomaleonitrile and its derivatives, diethylene amines such as triamine, triethylenetetramine, tetraethylenepentamine, bis(hexamethylene)triamine, triethanolamine, diaminodiphenylmethane, organic acid dihydrazide, 1,8-diazabicyclo[5,4, 0] Undecene-7 (trade name DBU, manufactured by San Apro Co., Ltd.), 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane (trade name) Organic phosphine compounds, such as ATU, Ajinomoto Co., Ltd. product), or a triphenylphosphine, a tricyclohexyl phosphine, a tributyl phosphine, and a methyl diphenyl phosphine, etc. are mentioned suitably.

The compounding quantity of at least any one of these (E-1) hardening|curing agent and (E-2) curing catalyst is sufficient in a normal ratio, Preferably it is 0.01-40 with respect to 100 mass parts of (A-1) thermosetting resins. It is a mass part, More preferably, it is 0.05-30 mass parts.

[(F) antioxidant]

It is preferable that the composition of this invention contains (F) antioxidant further. (F) By containing an antioxidant, the effect of preventing oxidative deterioration of curable resin etc. and suppressing discoloration is acquired, while heat resistance improves, the effect that resolution (linewidth reproducibility) becomes favorable can also be acquired. . That is, (B) depending on the type of the white coloring agent, by reflecting and absorbing light, the resolution may be deteriorated, but (F) by containing an antioxidant, (B) regardless of the type of the white coloring agent, Good resolution can be obtained.

(F) Antioxidants include radical scavengers that invalidate generated radicals, peroxide decomposers that decompose generated peroxides into harmless substances, and prevent new radicals from being generated. One type may be used alone, or two types of antioxidants You may use combining the above.

Specifically, as (F) antioxidant acting as a radical scavenger, for example, hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t- Butyl-p-cresol, 2,2-methylene-bis(4-methyl-6-t-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) Butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3',5'- phenol-based compounds such as di-t-butyl-4-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, quinone-based compounds such as metaquinone and benzoquinone; and amine compounds such as bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate and phenothiazine. As a commercial item, IRGANOX1010 (above, BASF Japan Co., Ltd. product, brand name) etc. can be used, for example.

Moreover, as (F) antioxidant which acts as a peroxide decomposing agent, For example, phosphorus compounds, such as triphenylphosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3 and sulfur-based compounds such as 3'-thiodipropionate.

Among the above, it is preferable to use a phenolic antioxidant from the point which the inhibitory effect of discoloration, the improvement of heat resistance, and favorable resolution are further acquired.

(F) To [ the compounding quantity in the case of using antioxidant / 100 mass parts of (A) curable resin ], Preferably it is 0.01-10 mass parts, More preferably, it is 0.03-5 mass parts. (F) By making the compounding quantity of antioxidant into 0.01 mass part or more, the effect by addition of the antioxidant mentioned above can be acquired reliably, On the other hand, by setting it as 10 mass parts or less, photoreaction is not inhibited, and favorable alkali development properties can be obtained, and good properties such as dry to touch properties and coating film properties can also be ensured.

In addition, (F) antioxidant, especially a phenolic antioxidant, may exhibit a further effect by using together with a heat-resistant stabilizer, You may mix|blend a heat-resistant stabilizer with the resin composition of this invention.

Examples of the heat-resistant stabilizer include phosphorus-based, hydroxylamine-based, and sulfur-based heat-resistant stabilizers. The said heat-resistant stabilizer may be used individually by 1 type, and may use 2 or more types together.

The composition of the present invention may contain a photo-excitable inorganic filler. Examples of the photo-excitable inorganic filler include strontium aluminate and zinc sulfide, and particularly strontium aluminate can be suitably used. Moreover, it is preferable that the surface treatment by an inorganic component or an acidic liquid is given from the point which improves the reflectance of a cured coating film as for a photoexcitable inorganic filler. Silica (glass), alumina, zirconia, etc. are mentioned as an inorganic component used for surface treatment. As a method of surface treatment using an inorganic component, a well-known method can be used and it is not specifically limited.

The composition of this invention may contain a photoinitiator. In particular, when using (A-2) photocurable resin, it is preferable to add a photoinitiator.

Among the photoinitiators, acylphosphine oxide-based photoinitiators such as bisacylphosphine oxides and monoacylphosphine oxides are preferred because they have few tacks and are excellent in the effect of inhibiting discoloration.

The composition of the present invention may contain a reactive diluent solvent. The reactive diluent solvent is used to adjust the viscosity of the composition to improve workability, increase crosslinking density, or improve adhesion, and a photocurable monomer may be used. As a photocurable monomer, the said photopolymerizable vinyl monomer etc. can be used.

Moreover, the organic solvent can be contained in the composition of this invention for the objective of manufacture of a composition, viscosity adjustment at the time of apply|coating to a board|substrate or a carrier film, etc. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether glycol ethers such as acetate and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; A well-known and usual organic solvent, such as petroleum solvents, such as petroleum ether, petroleum naphtha, and solvent naphtha, can be used. These organic solvents can be used individually or in combination of 2 or more types.

Moreover, you may mix|blend with the composition of this invention other additives well-known and usual in the field|area of an electronic material. Examples of the other additives include thermal polymerization inhibitors, ultraviolet absorbers, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial/mildew agents, defoamers, leveling agents, fillers, thickeners, adhesion-imparting agents, thixotropic agents, other colorants, photoinitiators. An auxiliary agent, a sensitizer, a hardening accelerator, a mold release agent, a surface treatment agent, a dispersing agent, a dispersion auxiliary agent, a surface modifier, a stabilizer, a fluorescent substance, etc. are mentioned.

The curable resin composition of this invention may be used as a dry film, and may be used as a liquid phase. When using as a liquid phase, one-component type may be sufficient, and two or more components may be sufficient. In particular, when using two or more components, the said (A)-(D) component may be mix|blended with the same formulation, and it does not matter even if it mix|blends with a different formulation.

Next, the dry film of this invention has a resin layer obtained by apply|coating and drying the composition of this invention on a carrier film. When forming a dry film, first, the composition of the present invention is diluted with the organic solvent and adjusted to an appropriate viscosity, and then a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure It is apply|coated to a uniform thickness on a carrier film with a coater, a spray coater, etc. Then, a resin layer can be formed by drying the apply|coated composition at the temperature of 50-130 degreeC for 1 to 30 minutes normally. Although there is no restriction|limiting in particular about the coating film thickness, Usually, it is 10-150 micrometers as a film thickness after drying, Preferably it selects suitably in the range of 20-60 micrometers.

A plastic film is used as a carrier film, For example, polyester films, such as a polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, etc. can be used. Although there is no restriction|limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers.

After forming the resin layer containing the composition of the present invention on the carrier film, it is preferable to further laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film. As a peelable cover film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, the surface-treated paper etc. can be used, for example. As a cover film, when peeling a cover film, what is necessary is just to be smaller than the adhesive force of a resin layer and a carrier film.

Moreover, in this invention, a resin layer is formed by apply|coating and drying the composition of this invention on the said protective film, and you may laminate|stack a carrier film on the surface. That is, when manufacturing a dry film in this invention, you may use any of a carrier film and a protective film as a film which apply|coats the composition of this invention.

In addition, the composition of the present invention is adjusted to a viscosity suitable for the application method using, for example, the organic solvent, and applied on a substrate by a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, After coating by a method such as a curtain coating method, the dry to touch resin layer can be formed by volatilizing and drying the organic solvent contained in the composition at a temperature of about 60 to 100°C (temporary drying). In addition, in the case of a dry film in which the composition is applied on a carrier film or protective film, dried and wound as a film, the layer of the composition of the present invention is bonded onto the substrate by a laminator or the like so that it is in contact with the substrate, and then the carrier film is By peeling, a resin layer can be formed.

Examples of the base material include printed wiring boards and flexible printed wiring boards in which a circuit is formed in advance with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluororesin ㆍUses materials such as copper-clad laminates for high-frequency circuits using polyethylene/polyphenylene ether, polyphenylene oxide/cyanate, etc., copper-clad laminates of all grades (FR-4, etc.), other metal substrates, polyimide films , a PET film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, a wafer plate, and the like.

The volatilization drying performed after the composition of the present invention is applied is a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, etc. method and a method of spraying from a nozzle to a support).

The composition of the present invention is, for example, by heating to a temperature of about 100 to 180 ° C. and thermal curing to form a cured film (cured product) excellent in various properties such as heat resistance, chemical resistance, hygroscopic resistance, adhesion, electrical properties, etc. can

Moreover, by performing exposure (light irradiation) with respect to the resin layer obtained after apply|coating the composition of this invention and volatilizing the solvent, an exposure part (light-irradiated part) is hardened|cured. Specifically, by a contact or non-contact method, through a photomask on which a pattern is formed, selectively exposed to an active energy ray, or directly pattern-exposed by a laser direct exposure machine, and an unexposed portion is , 0.3-3 mass % sodium carbonate aqueous solution), a resist pattern is formed.

As the exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc. are mounted, and any device that irradiates ultraviolet rays in the range of 350 to 450 nm is sufficient, and it is also a direct drawing device (For example, a laser direct imaging device that draws an image with a laser directly from CAD data from a computer) can also be used. As a lamp light source or a laser light source of a straight drawing machine, what exists in the range of 350-410 nm of maximum wavelength may be sufficient. Although the exposure amount for image formation varies depending on the film thickness and the like, it can be generally within the range of 20 to 800 mJ/cm 2 , preferably 20 to 600 mJ/cm 2 .

As the developing method, a dipping method, a shower method, a spraying method, a brush method, etc. can be followed. As the developer, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines can be used. .

The composition of this invention is used suitably for forming a cured film on a printed wiring board, It is used for forming a permanent film more suitably, It is used for forming a soldering resist or a coverlay still more suitably. In addition, in order to form a solder dam, you may use curable resin composition of this invention. In addition, by making the composition of the present invention white, it emits light from a light emitting diode (LED) or electroluminescence (EL) used as the light source in backlights of liquid crystal displays such as lighting fixtures, portable terminals, personal computers, and televisions. It is suitably used for a reflector that reflects light.

<Example>

Hereinafter, this invention is demonstrated in more detail using an Example.

<(A-1-1) Synthesis of curable resin (varnish A)>

431 g of dipropylene glycol monomethyl ether was put into a 2000 ml flask equipped with a stirrer and a cooling tube, and it heated at 90 degreeC under nitrogen stream. 104.2 g of styrene, 296.6 g of methacrylic acid, and 23.9 g of dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.: V-601) were mixed and dissolved in 4 hours. It was added dropwise to the flask.

In this way, the non-photosensitive carboxyl group-containing resin varnish A as (A-1) curable resin was obtained. The solid content acid value of this non-photosensitive carboxyl group containing resin varnish A was 140 mgKOH/g, and solid content was 50 mass %.

<(A-2-1) Synthesis of curable resin (varnish B)>

In a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 325.0 parts by mass of dipropylene glycol monomethyl ether as a solvent was heated to 110° C., and 174.0 parts by mass of methacrylic acid, ε-caprolactone-modified methacrylic acid (average molecular weight) 314) 174.0 parts by mass, 77.0 parts by mass of methyl methacrylate, 222.0 parts by mass of dipropylene glycol monomethyl ether, and t-butylperoxy2-ethylhexanoate as a polymerization catalyst (manufactured by Nichiyu Co., Ltd., perbutyl O) The mixture of 12.0 mass parts was dripped over 3 hours, and also it stirred at 110 degreeC for 3 hours, the polymerization catalyst was deactivated, and the resin solution was obtained. After cooling this resin solution, 289.0 mass parts of cyclomer M100 manufactured by Daicel Co., Ltd., 3.0 mass parts of triphenylphosphine, and 1.3 mass parts of hydroquinone monomethyl ether are added, the temperature is raised to 100°C, and the ring-opening of the epoxy group is stirred by stirring. An addition reaction was performed and the photosensitive carboxyl group-containing resin varnish B was obtained.

Thus, the obtained photosensitive carboxyl group-containing resin varnish B had a solid content concentration of 45.5 mass% and an acid value of a solid substance of 79.8 mgKOH/g. Moreover, the weight average molecular weight (Mw) of the solid content of the obtained photosensitive carboxyl group-containing resin varnish B was 15,000.

According to the formulation shown in the table below, each component was blended and premixed with a stirrer, then dispersed with a three roll mill and kneaded to prepare a composition, respectively. Example 19 and Comparative Example 5 were prepared as a solution A (liquid 1) and a solution B (liquid 2). In addition, the compounding quantity in a table|surface shows a mass part.

About the composition of each obtained Example and a comparative example, evaluation was performed according to the following. For Example 19 and Comparative Example 5, the liquid A and the liquid B were sufficiently mixed in a ratio of 8:2 during substrate preparation. The result is shown together in the following table|surface.

(1) reflectance

The composition described in Comparative Example 3 was applied on the entire surface by screen printing on a FR-4 material, dried in a hot air circulation drying furnace at 80° C. for 30 minutes, cooled to room temperature, and then exposed through a negative mask at 600 mJ/cm 2 , after developing for 90 seconds under the conditions of 0.2 MPa, washing with water, post-curing the substrate after development at 150° C. for 60 minutes, curing it, and obtaining a cured coating film. Then, each composition described in Examples 1 to 17 and 19 and Comparative Examples 1 to 2 and 5 was applied to the entire surface by screen printing on the cured coating film, respectively, and cured in a hot air circulation drying furnace at 150° C. for 30 minutes. to obtain a substrate.

In addition, the composition described in Comparative Example 3 was applied on the entire surface by screen printing on FR-4 material, dried in a hot air circulation drying furnace at 80 ° C. for 30 minutes, cooled to room temperature, and then through a negative mask at 600 mJ/cm 2 After exposure and development for 90 seconds on conditions of 0.2 MPa, it washed with water, the board|substrate after image development was post-cured at 150 degreeC for 60 minutes, and it hardened|cured, and the cured coating film was obtained. Then, each composition described in Example 18 and Comparative Examples 3 and 4 was applied over the entire surface by screen printing on the cured coating film, dried in a hot air circulation drying furnace at 80° C. for 30 minutes, and allowed to cool to room temperature. . This board|substrate was exposed through a negative mask at an exposure amount of 600 mJ/cm<2>, using 30 degreeC 1 mass % sodium carbonate aqueous solution, under the conditions of spray pressure 0.2 MPa for 90 second, it developed and washed with water, and the board|substrate after image development was obtained. Furthermore, it was made to post-cure at 150 degreeC for 60 minutes, and it hardened|cured, and obtained the board|substrate.

About the surface of the coating film of each obtained board|substrate, the reflectance in wavelength 450nm was measured with the spectrophotometer (CM-2600d, Konica Minolta Sensing Co., Ltd. product).

In addition, about each composition of Examples 2, 3, and Comparative Example 2, the reflectance in the range of wavelength 420-470 nm was measured similarly. The result is shown in the graph of FIG.

(2) Solder heat resistance

Each composition described in Examples 1 to 17 and 19 and Comparative Examples 1 to 2 and 5 was applied to FR-4 material by screen printing, and cured in a hot air circulation drying furnace at 150° C. for 30 minutes to obtain a substrate. . Further, each composition described in Example 18 and Comparative Examples 3 and 4 was applied over the entire surface by screen printing on FR-4 material, dried in a hot air circulation drying furnace at 80° C. for 30 minutes, and allowed to cool to room temperature. This board|substrate was exposed through a negative mask at an exposure amount of 600 mJ/cm<2>, using 30 degreeC 1 mass % sodium carbonate aqueous solution, under the conditions of spray pressure 0.2 MPa for 90 second, it developed and washed with water, and the board|substrate after image development was obtained. Furthermore, it was made to post-cure at 150 degreeC for 60 minutes, and it hardened|cured, and obtained the board|substrate. A rosin-based flux was applied to each of the obtained substrates, immersed in a solder bath previously set at 260°C, the flux was washed with denatured alcohol, and then the expansion and peeling of the resist layer was visually evaluated. The judgment criteria are as follows.

(circle): Even if it repeats immersion for 10 second 3 times or more, peeling is not recognized.

x: What has swelling and peeling in a resist layer within 3 times of immersion for 10 second.

(3) storage stability

Each composition was placed in an appropriate amount in a 30 g plastic container, stored for 180 days under conditions of 10° C. or less, and the state of the composition after storage was visually evaluated. For Example 19 and Comparative Example 5, put an appropriate amount of solution A and solution B in a plastic container containing 30 g each, i) stored for 180 days under a condition of 10 ° C. or less and ii) stored for 180 days under a condition of 30 ° C or less, respectively, The state of solution A and solution B after storage was evaluated by eye, respectively. The judgment criteria are as follows.

(circle): It did not gelatinize.

x: It gelled.

-: Unrated

*1) Non-photosensitive carboxyl group-containing resin varnish A (values in the table are values of solid content)

*2) Non-photosensitive carboxyl group-containing resin varnish (values in the table are values of solid content), Lumiflon 200F, manufactured by Asahi Glass Co., Ltd. (fluorine-based resin varnish)

*3) Non-photosensitive carboxyl group-containing resin varnish (values in the table are values of solid content), X-22-3701E, manufactured by Shin-Etsu Chemical Co., Ltd. (silicone-based resin varnish)

*4) Titanium oxide (Taipeik CR-58, manufactured by Ishihara Sangyo Co., Ltd., rutile-type titanium oxide manufactured by chlorine method)

*5) Titanium oxide (Taipeik R-820, manufactured by Ishihara Sangyo Co., Ltd., rutile-type titanium oxide manufactured by sulfuric acid method)

*6) Titanium oxide (TiONA 696, manufactured by CRISTAL, rutile-type titanium oxide manufactured by chlorine method)

*7) NIKKAFLUOR SB conc., manufactured by Nippon Chemical Co., Ltd.

*8) LXS FBW MAN 01, manufactured by LANXESS

*9) Tinopal OB CO, made by BASF Japan

*10) Block isocyanate compound (TRIXENE BI 7982, manufactured by Baxeneden Chemicals Limited), solid content: 70 mass %, liquid at room temperature

*11) Block isocyanate compound (Duranate SBN-70D, manufactured by Asahi Kasei Chemicals Co., Ltd.), solid content: 70 mass %, liquid at room temperature

*12) Silane coupling agent (KBM-402, 3-glycidoxypropylmethyldimethoxysilane, manufactured by Shin-Etsu Silicone Co., Ltd.), liquid at room temperature

*13) Silane coupling agent (KBM-5103, 3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Silicone Co., Ltd.), liquid at room temperature

*14) IRGANOX1010 (phenolic), manufactured by BASF Japan

*15) KS-66, manufactured by Shin-Etsu Silicone Co., Ltd.

*16) Disperbyk-111, made by Big Chemie Japan Co., Ltd.

*17) TEPIC-HP, manufactured by Nissan Chemical High School Co., Ltd.

*18) dicyandiamide (curing catalyst)

*19) Melamine-tetrahydrophthalate (curing catalyst), manufactured by Nissan Chemical Industry Co., Ltd.

*20) Aerosil R-974, manufactured by Nippon Aerosil Co., Ltd.

*21) LMP-100, manufactured by Fuji Talc High School Co., Ltd.

*22) MFTG (tripropylene glycol monomethyl ether), manufactured by Nippon Nyukazai Co., Ltd.

*23) DPM (dipropylene glycol monomethyl ether)

*24) Melamine (curing catalyst)

*25) DA-600 (manufactured by Sanyo Kasei Corporation)

*26) Photosensitive carboxyl group-containing resin varnish B (values in the table are values of solid content)

*27) Irgacure TPO (manufactured by BASF Japan)

From the results of Examples 1 to 18 in the table above, in the curable resin composition containing at least any one of an optical brightener, an isocyanate compound, and a coupling agent together with a white colorant, while maintaining solder heat resistance and storage stability, It can be seen that the reflectance is improved. On the other hand, from the result of Comparative Examples 1-4, in curable resin composition which lacks any of the components of this invention, it turns out that a reflectance is inferior. In addition, from the results of Example 19, it can be seen that the curable resin composition of the present invention has improved reflectance while maintaining solder heat resistance and storage stability even with two components, and has excellent storage stability even under particularly strict conditions. . On the other hand, from the result of the comparative example 5, in curable resin composition lacking any of the components of this invention, even if it uses two liquids, it turns out that a reflectance is inferior.

Claims (4)

(A) curable resin, (B) white colorant, (C) optical brightener, (D) isocyanate compound, or isocyanate compound, and a coupling agent are contained, Curable resin composition characterized by the above-mentioned. It has a resin layer obtained by apply|coating and drying the curable resin composition of Claim 1 on a film, The dry film characterized by the above-mentioned. A cured product obtained by curing the resin layer obtained by coating and drying the curable resin composition according to claim 1 or the curable resin composition according to claim 1 . It has the hardened|cured material of Claim 3, The printed wiring board characterized by the above-mentioned.

Images