KR20070108919A - Flame-retardant composition for solder resist and cured product thereof - Google Patents

Abstract

There is provided a flame retardant composition for a solder resist which is halogen-free and has a high level of flame retardance and flexibility, while exhibiting excellent heat resistance, moisture resistance and high-temperature reliability. The flame retardant composition for a solder resist according to the invention comprises (A) an alkali-soluble resin comprising either or both (A1) a carboxyl group-containing epoxy (meth)acrylate or (A2) a carboxyl group-containing urethane (meth)acrylate obtained by reacting an epoxy resin with two or more epoxy groups in the molecule (a), an unsaturated group-containing monocarboxylic acid (b) and a polybasic acid anhydride (c), (B) a compound having an ethylenic unsaturated group in the molecule, (C) a photopolymerization initiator, (D) a phosphorus-containing epoxy resin having a specific structure and (E) a hydrated metal compound. The composition of the invention can be suitably used as a solder resist or cover lay film for an FPC.

Description

Flame retardant composition for soldering resists and its cured product {FLAME-RETARDANT COMPOSITION FOR SOLDER RESIST AND CURED PRODUCT THEREOF}

The present invention relates to a halogen-free flame retardant curing composition that is sensitive to active energy rays and developable with a dilute aqueous alkali solution, which is used for printed circuit boards as solder resists, photosensitive coverlays, interlayer insulating films, and the like. In this case, the coating film not only has excellent flame resistance but also has excellent flexibility, adhesion, electroless gold plating resistance and insulation.

BACKGROUND OF THE INVENTION In the manufacture of a conventional printed circuit board, various substrate protection means such as a resist during etching and a solder resist used in the soldering step have been required. In addition, in the manufacturing process of a printed circuit board (flexible printed circuit board, FPC) such as a film, which is used in a miniaturization apparatus, a soldering resist is required for protection of an unrelated circuit in a soldering step performed for installation of a component. do.

Such substrate protection means has conventionally included cover layer films obtained through lamination of polyimide films punched in a predetermined form, and cover coats obtained by printing an ink composed of a heat resistant material. Coverlay films and cover coats also act as protective films for solder circuits, and therefore must exhibit heat resistance and insulation at soldering, as well as flexibility to prevent cracking due to warping during stacking of substrates.

Cover lay films formed by punching a polyimide film satisfy the above required characteristics and are thus most widely used in recent years, but require expensive dies for punching molding, and difficult to form complicated patterns as well as Placement and attachment methods also have much more expensive problems. Cover coats require a drying step for screen printing, resulting in high manufacturing costs and poor operability.

As a method for solving these problems, a method of coating a photosensitive composition in liquid form to a substrate or attaching to a substrate in the form of a film is proposed. The method easily forms a cover coat and coverlay of a fine pattern by exposing, developing, and heating a photolithography after coating a substrate, and various types of photosensitive compositions have been developed.

However, in the conventional photosensitive composition, there is no photosensitive composition which satisfies all the properties required for the use of FPC. For example, the photosensitive composition containing the prepolymer obtained by the addition reaction of polybasic acid anhydride and a novolak-type epoxy vinyl ester resin, a photoinitiator, a diluent, and an epoxy resin (Japanese Patent Laid-Open No. Hei 1-54390 (refer patent document 1). Although)) is shown, although such a composition satisfies heat resistance and insulation, it is not flexible and therefore not suitable for FPC. In addition, a binder system containing a low molecular weight copolymer which is a reaction product of a copolymer formed from an ethylenically unsaturated carboxylic anhydride with an ethylenically unsaturated comonomer and an amine, and a carboxylic acid-containing high molecular weight copolymer is used as an acrylated urethane monomer component, a photopolymerization initiator, and Although the photosensitive composition obtained by mixing a block diisocyanate crosslinking agent (Unexamined-Japanese-Patent No. 7-278492 (patent document 2)) is shown, this composition is not flame retardant and its use is restrict | limited.

As a conventional method of imparting flame resistance to a photosensitive composition, a method using a flame retardant system obtained by combining a halogenated flame retardant such as a brominated epoxy resin with a secondary flame retardant such as antimony trioxide (Japanese Patent Laid-Open No. 9-325490) Japanese Patent Laid-Open No. 9-352490 (see Patent Document 3). However, these flame retardant systems often exhibit inferior reliability at high temperature conditions, and when antimony compounds are used, it becomes necessary to consider environmental issues regarding waste disposal of resins. In addition, the added flexibility is impaired when the brominated epoxy resin is added in an amount sufficient to exhibit a flame retardant effect.

On the other hand, a method using phosphoric acid esters as a flame retardant (Japanese Patent Laid-Open No. 9-235449 (see Patent Document 5), Japanese Patent Laid-Open No. 10-306201 (see Patent Document 6), Japanese Patent Laid-Open Publication No. 11-271967) (See Patent Document 7)), but since the flame retardant effect is weak when phosphate esters are used alone, a large amount of phosphate ester must be used on the surface of the cured film to achieve the flame retardant effect. There was a problem that the phosphate ester leaked from the surface of the cured film. Although a flame retardant photocuring / thermosetting resin composition (Japanese Patent Laid-Open No. 2003-192763 (see Patent Document 8)) containing a specific cycloalkylene phosphine derivative is also shown, the specific cycloalkylene phosphine derivative Solubility in common organic solvents is small or insoluble. As a result, sufficient grinding steps are required for use in fine printed circuit boards having circuit leads and spaces of 25 μm or less.

Moreover, the reaction product obtained by reaction of the reaction product of novolak-type phenol resin and alkylene oxide, and unsaturated group containing monocarboxylic acid contains the carboxyl group-containing photosensitive resin obtained by reaction with polybasic acid anhydride, and a specific organic phosphorus compound. Although a flame retardant photocuring / thermosetting resin composition (Japanese Patent Laid-Open No. 2003-277470 (see Patent Literature 9)) has been proposed, these have problems of poor PCT resistance and electroless gold plating resistance.

As such, it is not easy to obtain a resist film having not only excellent solder heat resistance, moisture resistance, and high temperature stability but also excellent flame resistance, flexibility, and non-tackiness satisfying UL standards, and thus further development is required.

[Patent Document 1] Japanese Patent Publication No. Hei 1-54390

[Patent Document 2] Japanese Patent Application Laid-Open No. 7-278492

[Patent Document 3] Japanese Patent Application Laid-Open No. 9-325490

[Patent Document 4] Japanese Patent Application Laid-Open No. 11-242331

[Patent Document 5] Japanese Patent Application Laid-Open No. 9-235449

[Patent Document 6] Japanese Patent Publication No. 10-306201

[Patent Document 7] Japanese Patent Publication No. 11-271967

[Patent Document 8] Japanese Patent Publication No. 2003-192763

[Patent Document 9] Japanese Patent Publication No. 2003-277470

An object of the present invention is a halogen-free, heat-resistant composition having a good level of flame resistance, flexibility and tack-free, but also excellent soldering heat resistance, moisture resistance and high temperature reliability, in particular coverlay film for FPC, solder It is providing a flame retardant composition that can be suitably used as a resist or the like. Another object of the present invention is to provide a method capable of satisfactorily forming a heat resistant protective film using the flame retardant composition.

As a result of intensive research, the present inventors have found that the above problems can be solved by using a flame retardant together with a predetermined composition, and completed the present invention based thereon. Specifically, the present invention relates to a flame retardant composition for soldering resists shown in the following [1] to [34] and a cured product thereof.

[1] (A) Carboxyl group-containing epoxy (meth) obtained by reaction of (a) epoxy resin having two or more epoxy groups in (a) molecule, (b) unsaturated group-containing monocarboxylic acid, and (c) polybasic acid anhydride Alkali-soluble resin containing at least 1 type of) acrylate or (A2) carboxyl group-containing urethane (meth) acrylate;

(B) a compound having an ethylenically unsaturated group in the molecule;

(C) photoinitiator;

(D) The epoxy resin (d) having two or more epoxy groups in the molecule is represented by the following general formula (1) or (2):

{Wherein each R independently represents a hydrogen atom or an organic group having 1 to 6 carbon atoms containing no halogen, and Ar represents a reaction moiety of a quinone compound represented by the following general formula (3) or (4):

(Wherein each R independently represents a hydrogen atom or an organic group having 1 to 6 carbon atoms containing no halogen, and m represents an integer of 0 to 3)}

Or a phosphorus-containing epoxy resin obtained by reacting with a phosphorus-containing compound represented by the following General Formula (5) or (6):

{Wherein each R independently represents a hydrogen atom or an organic group of 1 to 6 carbon atoms containing no halogen}; And

(E) A flame retardant composition for soldering resists, containing a hydrated metal compound.

[2] The flame retardant composition for soldering resist according to the above [1], wherein the carboxyl group-containing epoxy (meth) acrylate (A1) is a carboxyl group-containing bisphenol-type epoxy (meth) acrylate (A1-1).

[3] The solid content acid value of the alkali-soluble resin (A) is 30 to 150 mgKOH / g, the weight average molecular weight is 4000 to 40000, and the glass transition temperature is -60 to 60 ° C. Flame retardant composition for soldering resist.

[4] The above-mentioned [1], wherein the polybasic acid anhydride (c) is a phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, and methylendomethylenetetrahydro A flame retardant composition for soldering resists, characterized in that the polybasic acid anhydride selected from the group consisting of phthalic anhydride.

[5] The flame retardant composition for soldering resists according to the above [1], wherein 30 to 100% by weight of the alkali-soluble resin (A) is a carboxyl group-containing urethane (meth) acrylate (A2).

[6] The flame retardant composition for soldering resist according to the above [1], wherein the compound (B) having an ethylenically unsaturated group in the molecule is a urethane acrylate (B-1).

[7] The flame retardant composition for soldering resist according to the above [1], wherein 70 to 100% by weight of the compound (B) having an ethylenically unsaturated group in the molecule is a compound having two ethylenically unsaturated groups in the molecule. .

[8] The flame retardant composition for soldering resist according to the above [1], wherein 20 to 95% by weight of the photopolymerization initiator (C) is a phosphorus-containing photopolymerization initiator.

[9] The flame retardant composition for soldering resists according to the above [1], wherein an epoxy equivalent of the phosphorus-containing epoxy resin (D) is 200 to 700 g / eq.

[10] The flame retardant composition for soldering resist according to the above [1], wherein the phosphorus content of the phosphorus-containing epoxy resin (D) is in a range of 1 to 9% by weight.

[11] The flame retardant composition for solder resist according to the above [1], wherein the content of the phosphorus-containing epoxy resin (D) in the solid content of the flame retardant composition for solder resist is 5 to 40% by weight.

[12] The flame retardant composition for soldering resists according to the above [1], wherein the endothermic amount at the time of thermal decomposition of the hydrated metal compound (E) is 400 to 2500 J / g.

[13] The flame retardant composition for soldering resist according to the above [1], wherein the hydrated metal compound (E) is at least one of aluminum hydroxide and magnesium hydroxide.

[14] The flame retardant composition for solder resist according to the above [1], wherein the content of the hydrated metal compound (E) is 5 to 40% by weight in the solid content of the flame retardant compound for solder resist.

[15] The flame retardant composition for solder resist according to the above [1], wherein the hydrated metal compound (E) is a hydrated metal compound treated with a coupling agent at a ratio of 0.3 to 3.0% by weight.

[16] The flame retardant composition for soldering resist according to the above [1], further comprising an organic solvent (F).

[17] The flame retardant composition for soldering resists according to the above [1], further comprising an epoxy resin (G) other than the phosphorus-containing epoxy resin (D).

[18] The flame retardant composition for soldering resists according to the above [1], further comprising a phosphate ester compound (H) having a melting point of 75 to 150 ° C.

[19] The flame retardant composition for soldering resists according to the above [1], further comprising an epoxy thermosetting accelerator (I).

[20] The flame retardant composition for soldering resists according to the above [19], wherein the epoxy thermosetting accelerator (I) has a triazine skeleton.

[21] The flame retardant composition for soldering resists according to the above [1], further comprising a colorant (J) containing no halogen.

[22] The blending ratio of the flame retardant composition for soldering resists according to the above [21] is 30 to 70 wt% of the alkali-soluble resin (A), 3 to 20 wt% of the compound (B) having an ethylenically unsaturated group in the molecule; 1-10 weight% of photoinitiators (C), 5-25 weight% of phosphorus containing epoxy resins (D), 5-30 weight% of hydration metal compounds (E), 10-60 weight% of organic solvents (F), phosphorus containing epoxy 0-10 weight% of epoxy resins (G) other than resin (D), 2-10 weight% of phosphate ester compounds (H), 0.1-3 weight% of epoxy thermosetting accelerators (I), and 0.05-2 weight of coloring agents (J) The flame retardant composition for soldering resists, which is%.

[23] The flame retardant composition for solder resists according to the above [1], wherein the phosphorus content of the solid content of the flame retardant composition for solder resists is 1.0 to 5.0% by weight.

[24] The flame retardant composition for soldering resists according to the above [1], wherein the viscosity is 500 to 500000 mPa · s (25 ° C).

[25] A cured composition obtained by curing the flame retardant composition for soldering resist according to any one of [1] to [24].

[26] A flame retardant composition for soldering resists according to any one of [1] to [24] is coated on a substrate and dried at a temperature of 50 to 120 ° C. for 1 to 30 minutes to have a thickness of 5 to 100 μm. , Exposure, development and thermosetting are carried out.

[27] A flame retardant coverlay film comprising a photosensitive layer formed from a flame retardant composition for soldering resist according to any one of the above [1] to [24] on a support.

[28] The flame retardant coverlay film of [27], wherein the support is a polyester film.

[29] A method for producing a flame retardant coverlay film, wherein the flame retardant composition for soldering resist according to any one of [1] to [24] is coated on a support and dried to form a photosensitive layer.

[30] An insulating protective film containing the flame retardant composition for soldering resist according to any one of the above [1] to [24].

[31] A printed circuit board comprising the insulation protective film according to the above [30].

[32] A flexible printed circuit board comprising the insulating protective film according to the above [30].

[33] An attaching step of attaching the photosensitive layer of the flame retardant coverlay film described in the above [27] to a substrate, an exposing step of exposing the photosensitive layer, a developing step following the exposing step, and a thermosetting for thermal curing the photosensitive layer. Method of manufacturing a printed circuit board comprising the step.

[34] An electronic component comprising the curable composition according to the above [25].

The method for obtaining the carboxyl group-containing epoxy (meth) acrylate (A1) used in the present invention may be a reaction between an epoxy resin (a), an unsaturated group-containing monocarboxylic acid (b) and a polybasic acid anhydride (c). Since the present invention shows excellent flame retardant effect even without halogen, the epoxy resin (a) used herein is preferably an epoxy resin containing no halogen atom. Epoxy resins that do not contain halogen atoms are epoxy resins that do not contain halogen atoms in the starting phenol resin that reacts with epichlorohydrin in the manufacture of epoxy resins, or are epoxy resins that are not substantially transformed into halogen atoms. That is, chlorine contained by the general use of epichlorohydrin may be contained, and specifically, it is preferable to have a halogen atom in the quantity of about 5000 ppm or less.

More specifically, bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, tetramethyl bisphenol A type epoxy resins, and bisphenol S type epoxy resins, reso Bifunctional epoxy resins such as lecinol diglycidyl ether, 1,6-dihydroxynaphthalene diglycidyl ether and dimethylbisphenol C diglycidyl ether, 1,6-diglycidyloxynaphthalene type Epoxy resins, 1- (2,7-diglycidyloxynaphthyl) -1- (2-glycidyloxynaphthyl) methane, 1,1-bis (2,7-diglycidyloxynaph Naphthalene-based epoxy resins such as butyl) methane, and 1,1-bis (2,7-diglycidyloxynaphthyl) -1-phenyl-methane, phenol novolac-type epoxy resins, orthocresol novolac Novolacs such as epoxy resins, bisphenol A novolac epoxy resins and bisphenol AD novolac resins Cyclic aliphatic compounds such as epoxy resins, cyclohexene oxide group-containing epoxy resins, tricyclodecene oxide group-containing epoxy resins, cyclopentene oxide group-containing epoxy resins, and epoxidized dicyclopentadiene type phenol resins. Epoxy resins, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, diglycidyl p-oxybenzoic acid, dimer acid glycidyl ester and triglycidyl ester Such glycidyl ester type epoxy resins, diglycidyl aniline, tetraglycidylamino diphenylmethane, triglycidyl-p-aminophenol, tetraglycidyl methacrylate diamine, diglycidyl toluidine and tetraglycidyl Glycidyl amine type epoxy resins such as cydyl bisaminomethylcyclohexane, diglycidyl hydantoin and glycidylglycidoxy Such as hydantoin type epoxy resins, heterocyclic epoxy resins such as triallyl isocyanurate and triglycidyl isocyanurate, fluoroglycinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether , Trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl ether, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2 , 3-epoxypropoxy) phenyl] ethyl] phenyl] propane and l, 3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [ Trifunctional epoxy resins such as 4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol, and tetrahydroxyphenylethane tetraglycidyl ether And tetrafunctional epoxy resins such as tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxy biphenyl.

The said epoxy resin (a) may be limited to 1 type, or 2 or more types may be combined. In addition, a part of each of the epoxy resins is n-butylglycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenylglycidyl ether, cresyl glycidyl ether, It may be used together with monofunctional epoxy compounds such as glycidyl methacrylate or vinylcyclohexene monooxide. Among them, bisphenol A type epoxy resins and / or bisphenol F type epoxy resins are particularly preferable.

Representative examples of the unsaturated group-containing monocarboxylic acid (b) include acrylic acid and methacrylic acid, as well as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and trimethylolpropane Contains hydroxy groups such as di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, phenylglycidyl (meth) acrylate and (meth) acrylic acid caprolactone additives (meth Unsaturated dibasic acid anhydride additives of) acrylates may be mentioned. Especially among these, acrylic acid and / or methacrylic acid are preferable. An unsaturated group containing monocarboxylic acid may be used independently, or may be used in combination of 2 or more type.

Representative examples of the polybasic acid anhydride (c) include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyl Aromatic polyhydric carboxylic acid anhydrides such as endomethylenetetrahydrophthalic anhydride, chloric acid anhydride, and dibasic acid anhydrides such as methyltetrahydrophthalic acid, trimellitic anhydride, pyromellitic anhydride and benzophenonetetracarboxylic acid anhydride, and 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-ene-l, 2-dicarboxylic acid anhydride and endobicyclo- [2,2,1] -hepto-5-ene-2 And 3-dicarboxylic acid anhydrides. Among them, in curing of the solder resist flame retardant composition, from the viewpoint of PCT resistance and HHBT resistance, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, and methylendomethylene Preference is given to polybasic acid anhydrides selected from the group consisting of tetrahydrophthalic anhydride. Tetrahydrophthalic anhydride and hexahydrophthalic anhydride are particularly preferred. These may be used independently and may combine 2 or more types.

The reaction between the epoxy resin (a), the unsaturated group-containing monocarboxylic acid (b) and the polybasic acid anhydride (c) may be performed after the unsaturated group-containing monocarboxylic acid (b) and the epoxy resin (a) react. Either the first method in which anhydride (c) reacts with it or the second method in which epoxy resin (a), unsaturated group-containing monocarboxylic acid (b) and polybasic acid anhydride (c) react simultaneously. The reaction is preferably carried out so that the unsaturated group-containing monocarboxylic acid (b) per equivalent of the epoxy group of the epoxy resin (a) is in the range of about 0.7 to 1.4 moles, more preferably about 0.9 to 1.1 moles. The reaction between the product (I) of the reaction and the polybasic acid anhydride (c) is carried out so that the ratio of the polybasic acid anhydride (c) per 1 equivalent of the hydroxyl group of the reaction product (I) is about 0.1-1 equivalent. desirable. These reactions are all carried out in the presence or absence of a reaction solvent, preferably a photopolymerization initiator such as hydroquinone, methylhydroquinone or oxygen is present, the reaction temperature is about 50 to 150 ° C, and the reaction time is about 1 to 10 hours. Examples of preferred reaction solvents include aromatic hydrocarbons such as benzene, toluene and xylene; Ketones such as methyl isobutyl ketone and methyl ethyl ketone; hydrocarbons such as n-hexane, cyclohexane and methylcyclohexane; Ethers such as diisopropyl ether; And acetic acid esters such as ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate and dipropylene glycol monomethyl ether acetate Are listed. These solvents may be used alone or in combination of two or more thereof.

The carboxyl group-containing urethane (meth) acrylate (A2) includes, as structural units, units derived from hydroxy group-containing (meth) acrylate compounds (d), units derived from diols (e), and units derived from diisocyanates (f). The compound containing is mentioned. In this type of compound, both ends are composed of units derived from hydroxy group-containing (meth) acrylates (d), and between both ends are units derived from diols (e) linked by urethane bonds and diisocyanates (f). Units derived from are placed. Several of the repeating units linked by the urethane bond have a structure containing a carboxyl group.

Specifically, the carboxyl group-containing urethane (meth) acrylate (A2) is-(ORbO-CONHRcNHCO) _n- [where ORbO represents a dehydrogenation moiety of diol (e), Rc is a deisocyanate moiety of diisocyanate (f) Is displayed. The carboxyl group-containing urethane (meth) acrylate (A2) may be prepared by the reaction of at least hydroxy group-containing (meth) acrylate (d), diol (e) and diisocyanate (f), diol (e) and Either or both of the diisocyanates (f) must be compounds having a carboxyl group. Preferably, carboxyl group-containing diols are used.

By using a carboxyl group-containing compound for diol (e) and / or diisocyanate (f), it becomes possible to produce a urethane (meth) acrylate compound (A2) in which a carboxyl group is present in Rb or Rc.

When using two or more different compounds for either or both of diol (e) and / or diisocyanate (f), there will be a plurality of repeating groups and the regularity of the repeating groups is completely arbitrary for that purpose. May be selected from a block or a ubiquitous one.

As hydroxy group containing (meth) acrylate (d), 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and caprolactone of the said (meth) acrylates Or alkylene oxide additives, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, glycidyl methacrylate-acrylic acid additive, trimethylolpropane (meth) acrylate, trimethylol di (meth) acrylate , Pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, trimethylolpropane-alkylene oxide additive, di (meth) acrylate, and the like. Can be mentioned. These hydroxy group-containing (meth) acrylates (d) may be used alone, or may be used in combination of two or more thereof. Among them, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate are preferred, and 2-hydroxyethyl (meth) acrylate is most preferred.

The said diol (e) is a compound which forms the repeating unit of a carboxyl group-containing urethane (meth) acrylate compound (A2) with an isocyanate (f). The diol (e) used may be a branched or linear compound having two alcoholic hydroxyl groups. Specifically, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 1,6 And low molecular weight diols such as -hexanediol, 1,4-cyclohexanedimethanol and hydrquinone. Also mentioned are high molecular weight diols, for example polyester diols, hexamethylene obtained from esters of polyether diols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol, polyhydric alcohols and polybasic acids. Polycarbonate diols such as carbonate and pentamethylene carbonate, and polylactone diols such as polycaprolactone diols and polybutyrolactone diols. It is preferable to use diol having a number average molecular weight of about 300 to 2000 because it further improves the flexibility of the cured film obtained from the photosensitive composition.

Carboxyl group-containing diols include dimethylol propionic acid and dimethylol butanoic acid. The diol to be used may be one or a combination of two or more kinds thereof, and it is preferable to use a diol having a number average molecular weight of about 300 to 2000 and dimethylolpropionic acid and / or dimethylolbutanoic acid in combination.

As the diisocyanate (f) used in the present invention, specifically, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, (o , m or p) -xylene diisocyanate, methylenebis (cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate and 1, And diisocyanates such as 5-naphthalene diisocyanate. You may use these diisocyanate individually or in combination of 2 or more types.

The carboxyl group-containing urethane (meth) acrylate compound (A2) is a method in which (1) a hydroxy group-containing (meth) acrylate (d), diol (e) and diisocyanate (f) are mixed and reacted at once, (2) diol reacting (e) with diisocyanate (f) to produce a urethane isocyanate prepolymer containing at least one isocyanate group per molecule, and then reacting the urethane isocyanate prepolymer with a hydroxy group-containing (meth) acrylate (d), or (3) A method of reacting a hydroxy group-containing (meth) acrylate (d) with a diisocyanate (f) to prepare a urethane isocyanate prepolymer containing at least one isocyanate group per molecule, and then reacting the prepolymer with a diol (e). It can be prepared by.

It is preferable that content of a carboxyl group-containing urethane (meth) acrylate compound (A2) in alkali-soluble resin (A) is about 30 to 100 weight%.

The solid acid value of the alkali-soluble resin (A) is preferably in the range of about 30 to 150 mgKOH / g, more preferably in the range of about 40 to 120 mgKOH / g. If the solid acid value is less than about 30 mgKOH / g, alkali solubility may be deteriorated, and if the solid acid value is more than 150 mgKOH / g, depending on the combination of components of the flame retardant composition for solder resist, alkali resistance, or electrical Resist properties such as properties may be reduced. The said solid content acid value is the pure acid value of alkali-soluble resin (A).

It is preferable that the weight average molecular weights of the said alkali-soluble resin (A) are about 4000-400000. The weight average molecular weight is a value measured by gel permeation chromatography in terms of polystyrene. If the weight average molecular weight is less than about 4000, the ductility and strength of the cured film of the photosensitive composition may be weakened, and if the value exceeds about 40000, alkali solubility may be deteriorated.

It is preferable that it is -60-60 degreeC, and, as for the glass transition temperature of the said alkali-soluble resin (A), it is more preferable that it is -40-60 degreeC. In a nitrogen atmosphere, the temperature was increased from about 120 ° C. to 180 ° C. by DSC in a nitrogen atmosphere, held at about 180 ° C. for about 3 minutes, and then at about −10 ° C./min. The glass transition temperature is determined by cooling to 120 ° C. and recording the inflection point. If the glass transition temperature is higher than 60 ° C., sufficient flexibility of the cured flame retardant composition for solder resist may not be achieved, and if the glass transition temperature is less than −60 ° C., the soldering heat resistance of the cured flame retardant composition for solder resist may become low. will be.

You may use (meth) acrylate etc. as a compound (B) which has an ethylenically unsaturated bond in a molecule | numerator. As (meth) acrylates, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) Acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate Alkyl (meth) acrylates such as lauryl (meth) acrylate and stearyl (meth) acrylate;

Alicyclic compounds such as cyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate and dicyclopentyloxyethyl (meth) acrylate ( Meta) acrylates; With benzyl (meth) acrylate, phenyl (meth) acrylate, phenylcarbitol (meth) acrylate, nonylphenyl (meth) acrylate, nonylphenylcarbitol (meth) acrylate and nonylphenoxy (meth) acrylate Same aromatic (meth) acrylates; Amino group-containing (meth) acrylates such as 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate and 2-tert-butylaminoethyl (meth) acrylate;

Personnel-containing methacrylates such as methacryloxyethyl phosphate, bis-methacryloxyethyl phosphate, methacryloxy ethylphenyl acid phosphate (phenyl P); ethylene glycol di (meth) acrylate, diethylene glycol di (meth ) Acrylate, triethylene glycol di (meth) acrylate, tetraethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate , Tripropylene glycol di (meth) acrylate, 1,4-butane diol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6- Diacrylates such as hexanediol di (meth) acrylate and bis-glycidyl (meth) acrylate;

Polyacrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate; Bisphenol S ethylene oxide 4 mole modified diacrylate, bisphenol A ethylene oxide 4 mole modified diacrylate, fatty acid modified pentaerythritol diacrylate, trimethylolpropane propylene oxide 3 mole modified triacrylate and trimethylolpropane propylene Modified polyol polyacrylates such as oxide 6 mole modified triacrylate; And bis (acryloyloxyethyl) monohydroxyethyl isocyanurate, tris (acryloyloxyethyl) isocyanurate and ε-caprolactone modified tris (acryloyloxyethyl) isocyanurate Isocyanuric acid skeleton-containing polyacrylates;

polyester acrylates such as α, ω-diacryloyl- (bisethyleneglycol) -phthalate and α, ω-tetraacryloyl- (bistrimethylolpropane) -tetrahydrophthalate; Allyl (meth) acrylate; Polycaprolactone (meth) acrylates; (Meth) acryloyloxyethyl phthalate; (Meth) acryloyloxyethyl succinate; And phenoxyethyl acrylate. In addition, N-vinyl compounds such as N-vinylpyrrolidone, N-vinylformamide and N-vinylacetamide, epoxy acrylates, urethane acrylates and the like can also be used. Of these, urethane acrylates are preferred because of low adhesiveness. The content of compound (B) having two or more unsaturated bonds in the molecule is preferably about 3 to 20% by weight of the flame retardant composition for soldering resist.

Examples of the photopolymerization initiator (C) used in the present invention include benzoin alkyl ethers such as benzoin, benzoin methyl ether and benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone Acetophenones such as 2,2-diethoxy-2-phenylacetophenone and 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoamino Aminoacetophenones such as propaneone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and N, N-dimethylaminoacetophenone, 2-methylanthraquinone , Anthraquinones such as 2-tert-butylanthraquinone, 2-amylanthraquinone and 2-aminoanthraquinone, thioxanthones such as 2,4-diethylthioxanthone and 2,4-diisopropylthioxane Ketals such as leuton, acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone, 4,4'-bisdiethylaminobenzophenone and 4-benzoyl-4'-methyldiphenyl sulfide; Silver benzophenones, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2 And 4,4-trimethyl-phenylphosphine oxide. You may use these photoinitiators individually or in combination of 2 or more types.

If desired, photosensitizers or photoinitiation aids may be used, such as quaternary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethylamine or triethanolamine. In addition, you may use these individually or in combination of 2 or more types. In addition, a titanocene compound such as IRGACURE784 (Ciba Specialty Chemicals) that absorbs in the visible region may be used. A photoinitiator and a photosensitive agent (photoinitiation adjuvant) are not limited to these, Any can be used individually or in combination.

In view of flame resistance, the photopolymerization initiator (C) is 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide or bis (2,6-dimeth It is preferable to contain phosphorus containing compounds, such as oxybenzoyl) -2,4,4-trimethyl- pentylphosphine oxide, and it is preferable that the quantity is 20 to 95 weight% of a photoinitiator. The content of the photopolymerization initiator (C) is preferably about 1 to 10% by weight, more preferably 2 to 8% by weight of the solid content of the flame retardant composition for soldering resist. If the content of the photopolymerization initiator is less than about 1% by weight, curing may be insufficient even upon active energy ray irradiation, it may be necessary to increase the irradiation time, or it may be difficult to achieve sufficient cured film properties. On the other hand, adding a photopolymerization initiator in excess of about 10% by weight is not effective for photocuring properties and economically undesirable.

The method of obtaining the phosphorus containing epoxy resin (D) used for this invention is not specifically limited, For example, it is represented by following General formula (1) or (2):

{Wherein each R independently represents a hydrogen atom or an organic group having 1 to 6 carbon atoms containing no halogen, and Ar represents a reaction moiety of a quinone compound represented by the following general formula (3) or (4):

(Wherein each R independently represents an organic group having 1 to 6 carbon atoms which does not contain a hydrogen atom or a halogen)}

Or by reacting a phosphorus-containing compound represented by the following general formula (5) or (6) with an epoxy resin (d) having two or more epoxy groups in a molecule:

Although the epoxy resin (d) which has two or more epoxy groups in a molecule | numerator is not specifically limited, Since this invention shows the outstanding flame retardant effect even without halogen, it is preferable that it does not contain a halogen atom. Epoxy resins that do not contain halogen atoms are epoxy resins that do not contain halogen atoms in the starting phenol resin that reacts with epichlorohydrin in the manufacture of epoxy resins, or are epoxy resins that are not substantially transformed into halogen atoms. That is, chlorine contained by the general use of epichlorohydrin may be contained, and it is preferable that the content of a halogen atom is 5000 ppm or less specifically ,. As such an epoxy resin, the epoxy resin (a) used for the synthesis | combination of said carboxyl group-containing epoxy (meth) acrylate (A1) is mentioned. The epoxy resin to be used is not limited to one kind, two or more kinds may be used in combination, or various modified forms may be used.

Examples of the phosphorus-containing compound (d) include 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide (HCA-HQ, Sanko Chemical Industry Co., Ltd.). Products), 9,10-dihydro-9-oxa-10-phosphafaphenanthrene-10-oxide (HCA, Sanko Chemical Industry Co., Ltd.) and diphenylphosphine oxide are preferred.

The reaction of the epoxy resin (d) with the compound of formula (1), formula (2), formula (5) or formula (6) may be carried out by mixing and stirring at a temperature of about 20 to 200 ° C. Can be. Here, the phosphorus containing compound represented by General formula (1) or (2) is also a phosphorus containing compound (d) and general formula (3) or (4) represented by General formula (5) or (6) in a reaction system. You may generate | occur | produce by reaction with the quinone represented by. In this case, an organic solvent and a catalyst may be used.

The reaction may proceed in the presence of an organic solvent as necessary. The organic solvent used is not particularly limited, but for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol, n-butanol, methoxypropanol, methyl cellulose solver, ethyl cellulose Solves, ethyl carbitol, ethyl acetate, xylene, toluene, cyclohexanone and N, N-dimethylformamide are preferred.

The finally obtained phosphorus-containing epoxy resin (D) preferably has an epoxy equivalent value of about 200 to 1000 grams / equivalent (hereinafter abbreviated as "g / eq"), but the composition is a solder resist or photosensitive coverlay film. It is more preferable that it is about 200-700 g / eq from a viewpoint of balance with alkali developability, adhesiveness to a board | substrate, and heat resistance when used.

The phosphorus content of the phosphorus-containing epoxy resin (D) is not particularly limited. For example, it is preferable that the phosphorus-containing epoxy resin (D) is about 1 to 9% by weight in order to remarkably improve the flame retardant effect. It is preferable that it is about 2-6 weight% from a viewpoint.

The content of the phosphorus-containing epoxy resin (A) in the solid content of the flame retardant composition for soldering resist is not particularly limited, but is preferably 5 to 40% by weight from the viewpoint of remarkable improvement of the flame retardant effect.

The hydrated metal compound (E) used in the present invention may have crystal water in an amount of about 12 to 60% by weight based on thermal analysis, but is not limited to these conditions.

In view of the flame retardant effect, it is preferable to use a hydrated metal compound having a calorific value of about 400 to 2500 J / g, more preferably about 600 to 2500 J / g.

Specific examples of such a hydrated metal compound include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, dosonite, calcium aluminate, dihydrate gypsum, zinc borate, barium metaborate, zinc tinate, kaolin, vermiculite, and the like. Among these, aluminum hydroxide and magnesium hydroxide are preferable.

Although the magnitude | size of the hydration metal compound (E) used by this invention is not specifically limited, It is preferable that average particle size is 40 micrometers or less, and it is more preferable that it is 2 micrometers or less. If the average particle size exceeds 40 μm, the transparency of the resist film may decrease, thereby reducing light transmittance or deteriorating the appearance and flatness of the coated film surface.

It is particularly preferable for the hydrated metal compound (E) used in the present invention to have a surface treated by polar surface treatment from the viewpoint of improving moisture resistance and HHBT resistance at the time of curing the solder resist. Examples of such polar surface treating agents include silane coupling agents or titanic acid coupling agents such as epoxysilanes, aminosilanes, vinylsilanes, mercaptosilanes and imidazolesilanes.

The content of the hydrated metal compound (E) used in the present invention is not particularly limited, but is preferably in the range of about 5 to 40% by weight in the solid content of the flame retardant composition for soldering resists. When the content of the hydrated metal compound in the solid content of the flame retardant composition for soldering resist is less than about 5% by weight, the flame retardant effect may be lowered, and when it exceeds 40% by weight, the flexibility of the cured film may be lowered.

The flame retardant composition for soldering resists according to the present invention can be prepared by mixing the above components by a conventional method using a triple roll mill or bead mill. The feed mixing method is not particularly limited, and for example, some of the components may be mixed before mixing the remaining components, or all of the components may be mixed at once. Moreover, you may add an organic solvent (F) to the flame retardant composition for soldering resists for viscosity adjustment as needed. By adjusting the viscosity in this way, it becomes easy to apply on the object not only by printing but also by roll coat, spin coat, screen coat, curtain coat and the like.

Examples of the organic solvent (F) include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Ester solvents such as ethyl acetate, ethyl acetoacetate, γ-butyrolactone and butyl acetate; Alcohol solvents such as butanol and benzyl alcohol; Cellulosolve and carbitol solvents and their esters and ether derivatives; Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; Dimethyl sulfoxide; Phenolic solvents such as phenol and cresol; Nitro compound solvents, toluene, xylene, hexamethylbenzene and cumene aromatic compounds; And aromatic or alicyclic solvents composed of hydrocarbons such as tetralin, decalin and dipentene. You may use these individually or in mixture of 2 or more types.

It is preferable to adjust the amount of the organic solvent (F) used so that the viscosity of the thermosetting composition for soldering resist becomes about 500-500,000 mPa * s (measured with a Brookfield viscometer at 25 degreeC). The value is more preferably 800 to 30,000 mPa · s. This range of viscosities is more convenient and suitable for coating and printing on objects. The preferred amount of the organic solvent (F) for calculating the viscosity in the solid content of the flame retardant composition for soldering resist is about 10 to 60% by weight. If the amount is greater than about 60% by weight, the solid concentration decreases, and if the photosensitive composition is printed onto the substrate, it may not be possible to obtain a sufficient film thickness in one printing, ie several printing processes are required.

The flame retardant composition for soldering resists according to the present invention may further use an epoxy resin (G) other than the phosphorus-containing epoxy resin (D) within a range that does not deteriorate flame resistance.

Specific examples of the epoxy resin (G) other than the phosphorus-containing epoxy resin (D) include those listed above. These epoxy resins are not limited to using only 1 type, You may use in combination of 2 or more types, or you may use these various modified forms.

The flame-retardant composition for soldering resists which concerns on this invention may contain the phosphate ester compound (H) whose melting | fusing point is about 45-150 degreeC as needed. In particular, when the flexibility of the cured flame retardant composition for soldering resists is insufficient, it is preferable to use a phosphate ester compound (H) to increase the flexibility without deteriorating the flame resistance. Specific examples include PX-200, PX-201 and PX-202 from Daihachi Chemical Industry Co., Ltd. You may use these phosphoric acid ester compounds (H) individually or in mixture of 2 or more types. The said phosphoric acid ester compound (H) is not contained in phosphorus containing epoxy resin (D).

When using the phosphate ester compound (H), the ratio is not particularly limited, but is preferably about 2 to 10% by weight, more preferably 2 to 8% by weight, based on the solid content of the flame retardant composition for soldering resists. . If the ratio of the phosphate ester compound (H) is too low, flame resistance and flexibility may become insufficient, whereas if too high, leakage (bleed bleed) may occur on the surface of the phosphate ester compound when the curing composition is stored for a long time. have.

The flame retardant composition for soldering resists according to the present invention may further contain an epoxy thermosetting accelerator in order to accelerate the curing of the epoxy resin (G) other than the phosphorus-containing epoxy resin (D) or the phosphorus-containing epoxy resin. For example, acid anhydrides such as amines, quaternary ammonium salts, cyclic aliphatic acid anhydrides, aliphatic acid anhydrides and aromatic acid anhydrides and nitrogen-containing heterocyclic compounds such as polyamides, imidazoles, triazine compounds, and the like, urea Compounds or organometallic compounds can be used.

The amines include aliphatic and aromatic primary, secondary and tertiary amines. Examples of aliphatic amines include polymethylenediamine, polyetherdiamine, diethylenetriamine, triethylenetriamine, tetraethylenepentamine, triethylenetetramine, dimethylaminopropylamine, mensendiamine, aminoethylethanolamine, bis (hexamethylene Triamine, 1,3,6-trisaminomethylhexane, tributylamine, 1,4-diazabicyclo [2,2,2] octane and 1,8-diazabicyclo [5,4,0] ound Sen-7-yen. Examples of aromatic amines include metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylmethane, diaminodiphenylsulfone and benzyldimethyldiamine.

Examples of quaternary ammonium salts include quaternary ammonium salts, tetrabutylammonium ions, tetrahexylammonium ions, dihexyldimethylammonium ions, dioctyldimethylammonium ions, hexatrimethylammonium ions, octatrimethylammonium ions, and dodecyltrimethylammonium ions. , Hexadecyltrimethylammonium ion, stearyltrimethylammonium ion, docosenyltrimethylammonium ion, cetyltrimethylammonium ion, cetyltriethylammonium ion, hexadecylammonium ion, tetradecyldimethylbenzylammonium ion, stearyldimethylbenzylammonium ion, Quaternary alkylaminopropylamines containing dioleyldimethylammonium ion, N-methyldiethanollaurylammonium ion, dipropanol monomethyllaurylammonium ion, dimethylmonoethanollaurylammonium ion and polyoxyethylene dodecyl monomethylammonium ion Can be mentioned.

Acid anhydrides include phthalic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, aromatic acid anhydrides such as ethylene glycol bis (trim anhydride) and glycol tris (trim anhydride), and maleic anhydride, succinic anhydride, Methylnadic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, a polyadip anhydride, chloric anhydride, tetrabromophthalic anhydride, etc. are mentioned. Examples of the polyamides include polyamides containing primary or secondary amino groups obtained by condensation of polyamines such as diethylenetriamine or triethylenetetraamine with dimer acid.

Specific examples of imidazoles include imidazole, 2-ethyl-4methylimidazole, N-benzyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidarrolinium trimellitate and 2 -Methyl imidazolinium isocyanurate is mentioned.

The triazine compound is a compound having a six-membered ring having three nitrogen atoms, and examples thereof include a melamine compound, a cyanuric acid compound, and a cyanuric acid-melamine compound. Specifically, the melamine compounds include melamine, N-ethylenemelamine, and N, N ', N "-trifenmelamine. Examples of cyanuric acid compounds include cyanuric acid, isocyanuric acid, and trimethyl cyanurate. , Tris-methyl isocyanurate, triethyl cyanurate, tris-ethyl isocyanurate, tri (n-propyl) cyanurate, tris (n-propyl) isocyanurate, diethyl cyanurate, N, N'-diethyl isocyanurate, methyl cyanurate, and methyl isocyanurate The cyanuric-melamine compound includes an equivalent mixture of a melamine compound and a cyanuric acid compound. Examples of the urea compounds include toluene bis (dimethylurea), 4,4'-methylene bis (phenyldimethylurea), and phenyldimethylurea.

Examples of the organometallic compound include organic acid metal salts, 1,3-diketone metal chelates, and metal alkoxides. Specifically, organic acid metal salts such as dibutyltin, dilaurate, dibutyltin maleate and zinc 2-ethylhexanoate, 1,3-diketone metal chelates such as nickel acetylacetonate and zinc acetylacetonate, and Metal alkoxides such as titanium tetrabutoxide, zirconium tetrabutoxide and aluminum butoxide.

It is preferable that the said epoxy thermosetting accelerator (I) is a compound which has a triazine structure. The addition amount is a catalytic amount, and it is preferable that it is about 0.1 to 3 weight% of the flameproof composition for soldering resist specifically ,.

Moreover, you may use the coloring agent (J) which does not contain a halogen in the flameproof composition for soldering resists of this invention as needed.

The mixing ratio in the flameproof composition for soldering resists according to the present invention is 30 to 70% by weight of the alkali-soluble resin (A), 3 to 20% by weight of the compound having an ethylenically unsaturated group in the molecule, and a photopolymerization initiator (C) 1 to 10. Weight%, 5-25 weight% of phosphorus containing epoxy resin (D), 5-30 weight% of hydration metal compounds (E), 10-60 weight% of organic solvents (F), and epoxy resins other than phosphorus containing epoxy resin (D) It is preferable that they are 0-10 weight% (G), 2-10 weight% of phosphate ester compounds (H), 0.1-3 weight% of epoxy thermosetting accelerators (I), and 0.05-2 weight% of coloring agents (J).

The thermosetting composition for soldering resists according to the present invention may further contain a flow characteristic regulator for controlling flow characteristics. The flow characteristic modifier is preferably capable of appropriately adjusting the flow characteristics of the photosensitive composition when the photosensitive composition is coated with the object by a roll coat, spin coat, screen coat, curtain coat or the like. Examples of the flow control agent include inorganic or organic fillers, waxes or surfactants. Specific examples of the inorganic fillers include talc, barium sulfate, barium titanate, silica, alumina, clay, magnesium carbonate, calcium carbonate and silicate compounds. Specific examples of the organic filler include silicone resins, silicone rubbers and fluorine resins. Specific examples of the wax include polyamide waxes and polyethylene oxide waxes. Specific examples of the surfactant include silicone oils, higher fatty acid esters and amides. These flow characteristic regulators can be used individually or in combination of 2 or more types. Use of inorganic fillers is advantageous for improving the binding properties and hardness as well as the flow characteristics of the photosensitive composition.

If necessary, additives such as pigments, thermal polymerization inhibitors, thickeners, antifoaming agents, leveling agents and tackifiers may be added to the flame retardant composition for soldering resists according to the present invention. Thermal polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, tert-butyl catechol, pyrogallol, phenothiazine, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) Propionate], pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], and the like. Thickeners include laminated silicates such as hectorite, montmorillonite, saponite, stebencite, tetrasilicone mica, and tiniolite, and intercalation compounds obtained by organic cation treatment of these interlayer compounds, silica and organic silica, Polyvinyl alcohol and cellulose derivatives. Defoamers are used to remove bubbles formed during printing, application and curing, and specific examples thereof include acrylic and silicone surfactants. Leveling agents are used to remove the unevenness of the film surface formed during printing and application, and specifically, acrylic and silicone surfactants may be mentioned. Examples of the tackifier include imidazole series, thiazole series, triazole series and silane coupling agents. Other additives include, for example, sunscreens or antifoaming agents for storage stability, and these may be added in an amount that does not impair the functions and effects of the present invention.

The flame retardant composition for soldering resists of the present invention is applied to a substrate or the like in an appropriate thickness, heat treated, dried, and then thermally cured for exposure, development and curing to obtain a cured composition. Since the flame retardant composition for soldering resists according to the present invention can be used for various purposes, and a cured film having heat resistance, hardness, dimensional stability and flexibility can be formed, which is difficult to decompose, an insulation protective coating for a printed circuit board Suitable as an insulating protective coating for FPC substrates. At the time of forming the insulating protective film, the photosensitive composition is applied on the substrate on which the circuit is formed to have a thickness of about 10 to 100 μm, heat-treated at about 50 to 120 ° C. for 1 to 30 minutes, and dried using a negative mask. It is possible to employ a method of exposing with an exposure pattern of, removing the unguided portion with an alkaline developer, and developing it, followed by thermosetting at about 100 to 180 ° C. for about 20 to 60 minutes for curing. Moreover, the said flame-retardant composition for soldering resists can be used as an interlayer insulation resin layer of a multilayer printed circuit board, for example.

The active light used for the exposure may be an active light emitted from a known active light source such as carbon arc, mercury vapor arc, xenon arc lamp or various laser devices. The sensitivity of the photopolymerization initiator (C) in the photosensitive layer is generally the largest in the ultraviolet region, and therefore it is preferable that the active light source effectively emits ultraviolet rays. Of course, if the photopolymerization initiator (C) is sensitive to visible light, for example 9,10-phenanthrenequinone, instead of the above-mentioned active light source, it is emitted from a light source such as a photographic flood lamp or a solar lamp. Visible light can be used as actinic light. The developing solution may be an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amine.

The flame retardant composition for soldering resists of the present invention may be used as a photosensitive layer of a photosensitive coverlay film. The photosensitive coverlay film has a photosensitive layer composed of a photosensitive composition on a support made of a polymer film or the like. It is preferable that the thickness of the dried photosensitive layer is 5-70 micrometers. Examples of the polymer film that can be used as the support include films made of polyesters such as polyethylene terephthalate and aliphatic polyesters, or polyolefin resins such as polypropylene and low density polyethylene, and polyethylene terephthalate, among them low density polyethylene and Preference is given to films made of polypropylene. The polymer film should be a layer removed from the photosensitive layer, and therefore should be one that can be easily removed from the photosensitive layer. The thickness of the said polymer film is 5-100 micrometers in general, and 10-30 micrometers is preferable.

The photosensitive coverlay film may be prepared by a photosensitive layer forming step of applying and drying the photosensitive composition on a support. By forming a cover film on the formed photosensitive layer, the support body, the photosensitive layer, and the cover film are laminated and included in this order, and the photosensitive coverlay film which has a film on both surfaces of the photosensitive layer can be manufactured. Since the cover film is peeled off from the photosensitive coverlay film in use, the photosensitive layer can be protected by providing the cover film on the photosensitive layer until use, thereby providing a photosensitive coverlay film having excellent handleability. As the cover film, a material such as the polymer film for the support may be used, and the cover film and the support may be made of the same or different materials and have the same or different thicknesses.

In order to use the photosensitive coverlay film in forming the insulating protective coating for a printed circuit board, first, an attaching step of attaching the photosensitive layer of the photosensitive coverlay film to the substrate is performed. When using the photosensitive coverlay film provided with a cover film, the cover film is peeled off for exposing the photosensitive layer before contacting the substrate. The photosensitive layer and the substrate are then thermocompressed at a temperature of about 40-120 ° C. with a pressure laminator or a vacuum pressure laminator to laminate the photosensitive layer on the substrate. Subsequently, an exposure step of exposing the photosensitive layer in a predetermined exposure pattern using a negative mask is performed. Then, the support film is peeled off from the photosensitive layer. Then, a developing step of removing the non-exposed part by developing with a developing solution and a thermosetting step of thermosetting the photosensitive layer are performed to provide a printed circuit having an insulating protective film on the surface of the substrate. Prepare the substrate. You may use such a photosensitive coverlay film in order to form the interlayer insulation resin layer of a multilayer printed circuit board. The actinic light and the developing solution used for exposure may be the same as described above.

The flame retardant composition for soldering resists of the present invention has not only the performance required for the formation of photosensitive coatings such as photosensitivity, developability and lifetime, but also the performance required for insulation protective coatings such as flame resistance, insulation, heat resistance, hardness and dimensional stability. It can satisfy simultaneously and can also form a flexible cured film. In particular, it does not contain halogen, it is flame-retardant and flexible, phosphorus containing epoxy resin (D), a hydrated metal compound (E), and phosphoric acid ester (H) and phosphorus containing which have melting | fusing point of about 75-150 degreeC as needed. Such photosensitive compositions obtained by using a combination of photopolymerization initiators are most suitable for use as insulation protective coatings for thin circuit boards such as flexible printed circuit boards.

Example

The present invention will be described in more detail through examples and comparative examples. In the examples, "parts" and "%" are based on weight unless otherwise indicated. The phosphorus content of the phosphorus containing epoxy compound (D) was measured by the following method.

Phosphorus content measurement method

25 ml nitric acid and 10 ml perchloric acid are added to 1 g of sample and heated to dissolve to an amount of 5-10 ml, then the solution is diluted with midstream in a 1000 ml graduated flask. 10 ml of the sample solution is placed in a 100 ml flask, 10 ml of nitric acid, 10 ml of 0.25% ammonium vanadate solution and 10 ml of 5% ammonium molybdate solution are added, distilled water is added to the mark and the mixture is diluted. After shaking, the solution was placed in a quartz cell, and the absorbance of the sample and the phosphorus standard solution was measured using a spectrophotometer as a control at a wavelength of 400 nm. Phosphorus standard solution is 10 ml of potassium phosphate solution prepared at distilled water at P = 0.1 mg / ml, and placed in a 100 ml graduated flask and diluted with distilled water.

Subsequently, the phosphorus content is obtained from the following formula.

Phosphorus content (%) = absorbance of sample / absorbance of phosphorus standard solution / sample (g)

[ Synthesis Example  1] < PUA -1>

85.0 g (= 0.1 mole) of polytetramethylene glycol (PTG-850SN, manufactured by Hodogaya Chemical Co., Ltd., molecular weight: 850), 93.8 g (= 0.7 mole) of dimethylolpropionic acid as a hydroxy group-containing dihydroxy compound, and di 199.8 g (= 0.9 mole) of isophorone diisocyanate as isocyanate was weighed and the components were heated at 50 ° C. 150 mg of di-n-butyltin lauryl was added to the mixture and heated at 80 ° C. Then, 90 mg of each of sickle, p-methoxyphenol and di-t-butylhydroxytoluene were put into a reactor, and then 24.4 g (= 0.21 mol) of 2-hydroxyethyl acrylate as a hydroxy group-containing (meth) acrylate was added. Added. Stirring was continued at 80 ° C, and after confirming that the isocyanate group absorption peak (2280 cm ^-1 ) disappeared from the infrared absorption spectrum, the reaction was terminated to obtain a carboxyl group-containing urethane acrylate. Diethylene glycol monoethyl ether acetate was used as the solvent for synthesis. In this way, a tacky liquid urethane acrylate (PUA-1) having a solid acid value of 90 mgKOH / g and a solid content concentration of 50% by weight was obtained. The weight average molecular weight was 17,200 and the viscosity (25 ° C.) was 11,000 mPa · s. Glass transition temperature was 52 degreeC.

[ Synthesis Example  2] <D-1>

100 parts of bisphenol F-type epoxy resin (EPICLON830S: Dainippon Ink & Chemicals, Inc.) of epoxy equivalent 172g / eq, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphapé 37 parts by weight of n-Tren-10-oxide (HCA-HQ, Sanko Chemical Industry Co., Ltd.) and 0.5 part of triphenylphosphine as a catalyst were reacted at 140 ° C for 5 hours, so that the phosphorus content (solid content) was 2.6% by weight. % And an epoxy equivalent (solid content) of 434 g / eq was obtained phosphorus containing epoxy resin. Diethylene glycol monoethyl ether acetate was added and the mixture was heated to 80 ° C. to obtain a solution having a solid content of 75% by weight. This solution was named Resin (D-1).

[ Synthesis Example  3] <D-2>

100 parts of bisphenol-A epoxy resin (EPIKOTE828: product of Japan Epoxy Resin Co., Ltd.) of epoxy equivalent 186g / eq, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10 phosphape 30 parts of antrene-10-oxide (HCA-HQ, Sanko Chemical Industry Co., Ltd.) and 0.5 parts of triphenylphosphine as catalysts were reacted at 140 ° C. for 5 hours to obtain a phosphorus content (solid content) of 2.2% by weight. % And a phosphorus containing epoxy resin whose epoxy equivalent (solid content) is 411 g / eq. Diethylene glycol monoethyl ether acetate was added and heated to 80 ° C. to obtain a solution having a solid content of 75% by weight. This solution was named Resin (D-2).

[ Synthesis Example  4] <D-3>

100 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene (KAYARAD EOCN-104S manufactured by Nippon Kayaku Co., Ltd.) with an epoxy equivalent of 219 g / eq 40 parts of 10-oxide (HCA, Sanko Chemical Industry Co., Ltd.), 0.5 parts of triphenylphosphine as catalyst and 47 parts of diethylene glycol monoethyl ether acetate as solvent were reacted at 140 DEG C for 5 hours, A phosphorus-containing epoxy resin having a content (solid content) of 4.1 wt% and an epoxy equivalent weight (solid content) of 369 g / eq was obtained. This solution was named Resin (D-3).

Example  1-5, Comparative example  1-4 ( Solder For resist Flame retardant  Preparation of the composition)

After combining the components in the ratio (weight%) listed in Table 1 below, the mixture was passed through a triple roll mill three times to prepare a base resin and a curing agent. While producing in a triple roll mill, diethylene glycol monoethyl ether acetate / petroleum naphtha = 60/40 wt% was added as a solvent to adjust the base resin solids concentration to 71 wt% and the hardener solids concentration to 80 wt%.

The following evaluation was performed about each of the obtained flame retardant compositions.

Preparation of Laminated Test Pieces

The substrate was coated with an ink obtained by screen printing with a 100 mesh polyester plate and mixing the base resin and the curing agent. It was cured in a hot air circulation dryer at 70 ° C. and dried for 30 minutes. The substrate used for evaluation was following (1) or (2).

(1) A printed substrate (UPISEL ^™ N, Ube Kosan Co., Ltd.) consisting of a polyimide film (25 μm thick) laminated on one side with copper foil (16 μm thick), washed with 10% aqueous ammonium sulfate solution. Rinse with water and dry with air stream.

(2) 25 μm-thick polyimide film (CAPTONE ^™ 10OH, Toray-DuPont Co., Ltd.)

Exposure, development, and Thermosetting

Each laminated test piece obtained at 500 mJ / cm 2 (measured at a wavelength of 365 nm) was exposed using an exposure apparatus HMW-680GW (manufactured by Oak Technologies) equipped with a metal halide lamp. Next, by spraying with a 1% by weight aqueous solution of sodium carbonate for 60 seconds at a temperature of 30 ℃ and a spray pressure of 0.2MPa, by spraying for 60 seconds with water at a temperature of 30 ℃ and a spray pressure of 0.15MPa to remove the non-exposed part, The heat treatment was performed at 150 ° C. for 60 minutes to obtain an FPC laminated substrate (used as the evaluation substrate 1) and a polyimide laminated substrate (used as the evaluation substrate 2).

Hitachi 21-step tablet was used as a negative pattern for exposure in the preparation of the photosensitive evaluation sample. In the preparation of the soldering heat resistance evaluation sample, a copper foil left in a 1 cm x 1 cm square and a 2 cm long 1 mm / 1 mm (line / space) pattern within a 4 cm x 6 cm region was used as a negative pattern. The preparation of the other evaluation samples did not use negative patterns.

Physical property evaluation

Physical properties were evaluated by the following method. The results are shown in Table 2. "Combustibility" and "flexibility" in each evaluation were measured using a polyimide laminated substrate, and other evaluations were performed using an FPC substrate.

evaluation

combustibility

Combustible test pieces were manufactured by the following method. The ink obtained by mixing the base resin and the curing agent was screen printed with a 100 mesh polyester plate on one side of a 25 μm thick and 200 mm × 50 mm polyimide film (CAPTONE ^™ 10OH, Toray-DuPont Co., Ltd.). It was cured in a hot air circulation dryer at 70 ° C. and dried for 30 minutes. The ink was then printed in the same way on the other side of the test piece, cured again in a hot air circulation dryer at 70 ° C. and dried for 30 minutes. After irradiating ultraviolet rays at 500 mJ / cm 2, alkali development was carried out and thermally cured at 150 ° C. for 60 minutes. The sample was adjusted to a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to use as a sample for the combustibility test. Combustion characteristics were evaluated by the method by the Tests for Flammability of Plastic Materials (94UL-VTM) of the US Underwriters Laboratories Inc. (UL).

The abbreviations "VTM" and "NOT" in Table 2 are shown below.

VTM-O: Class that meets all of the following requirements.

(1) The flame burning time after each combustor deflammation does not exceed 10 seconds in all specimens.

(2) The total flame combustion time after applying a total of 10 combustor flames to each of the five test specimens shall not exceed 50 seconds.

(3) Flame burning or glowing burning does not reach the 125mm indicator line.

(4) Flame loads do not ignite cotton wool.

(5) The total flame and glowing burning time in each specimen after the removal of the second chlorine flame does not exceed 30 seconds.

(6) If only one of the five specimens in a pair does not meet the above requirements or if the total flame combustion time is within the range of 51 to 55 seconds, retest and all five specimens shall be subjected to (1) to (5). Satisfy requirements.

VTM-1: Class that meets all of the following requirements.

(1) For all specimens, the flame burning time after each combustor deflammation does not exceed 30 seconds.

(2) The total flame burning time after applying a total of 10 combustor flames to each of the five test specimens shall not exceed 250 seconds.

(3) Flame burning or glowing burning does not reach the 125mm indicator line.

(4) Flame loads do not ignite cotton wool.

(5) The total flame and glowing burning time in each specimen after the removal of the second chlorine flame does not exceed 60 seconds.

(6) If only one of the five specimens of a set does not meet the above requirements or if the total flame combustion time is within the range of 251 to 255 seconds, retest and all five specimens shall be Satisfy requirements.

VTM-2: Class that meets all of the following requirements.

(1) For all specimens, the flame burning time after each combustor deflammation does not exceed 30 seconds.

(2) The total flame burning time after applying a total of 10 combustor flames to each of the five test specimens shall not exceed 250 seconds.

(3) Flame burning or glowing burning does not reach the 125mm indicator line.

(4) Flame loads may ignite cotton wool.

(5) The total flame and glowing burning time in each specimen after the removal of the second chlorine flame does not exceed 60 seconds.

(6) If only one of the five specimens of a set does not meet the above requirements or if the total flame combustion time is within the range of 251 to 255 seconds, retest and all five specimens shall be Satisfy requirements.

NOT: If none of the above classes apply.

Sticky

The flame retardant composition for soldering resist was printed on an FPC substrate, dried at 70 ° C. for 30 minutes, and then cooled for 30 minutes, and the test piece obtained was used for evaluation of the photosensitive layer surface tack through finger contact at room temperature according to the following criteria.

A: No attachment at all

B: only slight attachment

C: attachment exists

Developability

The flame retardant composition for soldering resist was printed and dried to obtain an FPC laminated substrate, which was developed at a temperature of 30 ° C. and a spray pressure of 0.2 MPa using a 1 wt% aqueous sodium carbonate solution as a developer, followed by a spray pressure of 0.2 MPa. Washed under conditions for 1 minute. The developing residue was visually observed. The symbol shown in the said Table 2 is as follows.

A: developed successfully

C: Developmental residue is observed

Photosensitivity

The Hitachi 21-stage tablet was stacked on the sample as a negative pattern, and then exposed (500 mJ / cm 2) and developed to record the number of steps of the step tablet of the photocured film formed on the obtained FPC laminated substrate, thereby reducing the photosensitivity of the curable flame retardant composition. Evaluated. The photosensitivity is represented by the number of steps of the step tablet, and the higher number of steps of the step tablet indicates higher photosensitivity.

Flexibility

With the photosensitive layer in which the cured film was formed, the polyimide laminated substrate was folded 180 ° for 1 second at a pressure of 0.5 MPa. The presence of cracks in the cured film was investigated using a 30x optical microscope.

A: There is no crack in the cured film

C: cured film cracked

Breed

After storing the polyimide laminated substrate for 2 months in a thermostat at 40 ° C., the specimen surface was evaluated through finger contact and visual observation according to the following criteria. The symbol shown in the said Table 2 is as follows.

A: No adhesion and bleed observed

C: Adhesion or bleed is observed

Soldering  Heat resistance

According to JIS C-6481 test method, a rosin-based flux was applied to the surface of the FPC laminated substrate, floated in a 260 ° C. solder bath for 5 seconds, and the cured film was visually observed after each cycle while repeating these cycles. blistering) "and" solder precipitation "or other forms of change; The maximum number of cycles without change was recorded.

PCT  tolerance

The FPC laminated substrate on which the resist coating was formed under the above conditions was treated with a PCT apparatus (ESPEC HAST CHAMBER EHS-411M Tabai Corp.) for 96 hours under the condition of 121 ° C. and 0.2 MPa to evaluate the state of the cured coating.

A: No peeling, coloring or dissolution

B: peeling, coloring or dissolution

C: Extensive peeling, coloring or dissolution

Effects of the Invention

The flame retardant composition for soldering resists according to the present invention is excellent in developability and photosensitivity for forming a solder resist pattern by selectively irradiating active light through a patterned film and developing a non-exposed part, and the resulting cured composition contains halogen. Since it does not contain, it is excellent in flame resistance and satisfies both the requirements of flexibility and non-tackiness, and is particularly suitable for FPC liquid solder resist ink compositions or photosensitive coverlay films.

Claims (34)

(A) Carboxyl group-containing epoxy (meth) acrylate obtained by reaction of (a) epoxy resin which has 2 or more types of epoxy groups in a molecule, (b) unsaturated group containing monocarboxylic acid, and (c) polybasic acid anhydride. Or (A2) alkali-soluble resins containing at least one kind of carboxyl group-containing urethane (meth) acrylate; (B) a compound having an ethylenically unsaturated group in the molecule; (C) photoinitiator; (D) The epoxy resin (d) having two or more epoxy groups in the molecule is represented by the following general formula (1) or (2):

{Wherein each R independently represents a hydrogen atom or an organic group having 1 to 6 carbon atoms containing no halogen, and Ar represents a reaction moiety of a quinone compound represented by the following general formula (3) or (4):

(Wherein each R independently represents a hydrogen atom or an organic group having 1 to 6 carbon atoms containing no halogen, and m represents an integer of 0 to 3)} Or a phosphorus-containing epoxy resin obtained by reacting with a phosphorus-containing compound represented by the following General Formula (5) or (6):

{Wherein each R independently represents a hydrogen atom or an organic group of 1 to 6 carbon atoms containing no halogen}; And (E) A flame retardant composition for soldering resists, containing a hydrated metal compound. The flame retardant composition for soldering resists according to claim 1, wherein the carboxyl group-containing epoxy (meth) acrylate (A1) is a carboxyl group-containing bisphenol type epoxy (meth) acrylate (A1-1). The solid acid value of said alkali-soluble resin (A) is 30-150 mgKOH / g, the weight average molecular weight is 4000-400000, and a glass transition temperature is -60-60 degreeC. Softener composition. 2. The polybasic acid anhydride (c) according to claim 1, wherein the polybasic acid anhydride (c) is composed of a phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, and methylendomethylenetetrahydrophthalic anhydride A flame retardant composition for soldering resists, characterized in that the polybasic acid anhydride selected from the group. The flame retardant composition for soldering resists according to claim 1, wherein 30 to 100% by weight of the alkali-soluble resin (A) is a carboxyl group-containing urethane (meth) acrylate (A2). The flame retardant composition for soldering resists according to claim 1, wherein the compound (B) having an ethylenically unsaturated group in the molecule is urethane acrylate (B-1). The flame retardant composition for soldering resists according to claim 1, wherein 70 to 100% by weight of the compound (B) having an ethylenically unsaturated group in the molecule is a compound having two ethylenically unsaturated groups in the molecule. The flame retardant composition for soldering resists according to claim 1, wherein 20 to 95% by weight of the photopolymerization initiator (C) is a phosphorus-containing photopolymerization initiator. The flame retardant composition for soldering resists according to claim 1, wherein an epoxy equivalent of the phosphorus-containing epoxy resin (D) is 200 to 700 g / eq. The flame retardant composition for soldering resists according to claim 1, wherein the phosphorus content of the phosphorus-containing epoxy resin (D) is in a range of 1 to 9% by weight. The flame retardant composition for soldering resists according to claim 1, wherein the content of the phosphorus-containing epoxy resin (D) in the solid content of the flame retardant composition for soldering resists is 5 to 40% by weight. The flame retardant composition for soldering resists according to claim 1, wherein the endothermic amount at the time of thermal decomposition of the hydrated metal compound (E) is 400 to 2500 J / g. The flame retardant composition for soldering resists according to claim 1, wherein the hydrated metal compound (E) is aluminum hydroxide or magnesium hydroxide. The flame retardant composition for soldering resists according to claim 1, wherein the content of the hydrated metal compound (E) is 5 to 40% by weight in the solid content of the flame retardant compound for soldering resists. The flame retardant composition for soldering resists according to claim 1, wherein the hydrated metal compound (E) is a hydrated metal compound treated with a coupling agent at a ratio of 0.3 to 3.0% by weight. The flame retardant composition for soldering resists according to claim 1, further comprising an organic solvent (F). The flame retardant composition for soldering resists according to claim 1, further comprising an epoxy resin (G) other than the phosphorus-containing epoxy resin (D). The flame retardant composition for soldering resists according to claim 1, further comprising a phosphate ester compound (H) having a melting point of 75 to 150 ° C. The flame retardant composition for soldering resists according to claim 1, further comprising an epoxy thermosetting accelerator (I). The flame retardant composition for soldering resists according to claim 19, wherein the epoxy thermosetting accelerator (I) has a triazine skeleton. The flame retardant composition for soldering resists according to claim 1, further comprising a colorant (J) containing no halogen. The mixing ratio of the flame retardant composition for soldering resists according to claim 21 is 30 to 70% by weight of the alkali-soluble resin (A), 3 to 20% by weight of the compound (B) having an ethylenically unsaturated group in the molecule, and a photopolymerization initiator (C ) 1 to 10% by weight, phosphorus-containing epoxy resin (D) 5 to 25% by weight, hydrated metal compound (E) 5 to 30% by weight, organic solvent (F) 10 to 60% by weight, phosphorus-containing epoxy resin (D) 0-10 weight% of other epoxy resins (G), 2-10 weight% of phosphate ester compounds (H), 0.1-3 weight% of epoxy thermosetting accelerators (I), and 0.05-2 weight% of coloring agents (J), It is characterized by the above-mentioned. Flame retardant composition for soldering resists to be used. The flame retardant composition for soldering resists according to claim 1, wherein the phosphorus content of the solid content of the flame retardant composition for soldering resists is 1.0 to 5.0% by weight. The flame retardant composition for soldering resists according to claim 1, wherein the viscosity is 500 to 500000 mPa · s (25 ° C). The hardening composition obtained by hardening | curing the flame retardant composition for soldering resists in any one of Claims 1-24. The flame retardant composition for soldering resists according to any one of claims 1 to 24 is coated on a substrate and dried at a temperature of 50 to 120 ° C. for 1 to 30 minutes to have a thickness of 5 to 100 μm, followed by exposure, Process for curing the flame retardant composition, characterized by performing development and heat curing. A flame retardant coverlay film comprising a photosensitive layer formed from a flame retardant composition for soldering resists according to any one of claims 1 to 24 on a support. 28. The flame retardant coverlay film of claim 27, wherein said support is a polyester film. A flame retardant coverlay film manufacturing method characterized by coating the flame retardant composition for soldering resist according to any one of claims 1 to 24 on a support, and drying to form a photosensitive layer. The flame retardant composition for soldering resists of any one of Claims 1-24 is contained, The insulation protective film characterized by the above-mentioned. The insulating protective film of Claim 30 is contained, The printed circuit board characterized by the above-mentioned. The insulating protective film of Claim 30 is included, The flexible printed circuit board characterized by the above-mentioned. 28. An attaching step of attaching a photosensitive layer of the flame retardant coverlay film of claim 27 to a substrate, an exposing step of exposing the photosensitive layer, a developing step following the exposing step, and a thermosetting step of thermosetting the photosensitive layer. The manufacturing method of the printed circuit board characterized by the above-mentioned. An electronic component comprising the curable composition according to claim 25.