JP2005189841A - Curable flame retardant composition for resist, method for curing the same and use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable flame retardant composition for a resist having both flame retardancy and flexibility, suitable for use as a cover lay for FPC, a solder resist, etc., and excellent in solder heat resistance, moisture resistance and high temperature reliability. <P>SOLUTION: The curable flame retardant composition for a resist contains a (co)polymer of a bromine compound shown by formula (1) and/or formula (2) and a curable resin material for a resist. There are provided a heat cured object of the resist composition, an ink containing the resist composition and a colorant, a method for curing the resist composition, an insulating protective coating and an interlayer insulating film comprising the resist composition, and a printed wiring board with the film. In the formulae, R represents H or methyl; and X<SP>1</SP>-X<SP>10</SP>each independently represents H or Br with the proviso that at least two of X<SP>1</SP>-X<SP>5</SP>and at least two of X<SP>6</SP>-X<SP>10</SP>are Br. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a curable flame retardant composition for resist for forming a protective film used in the production of a printed wiring board and the like, a curing method thereof, and an application.

  In the production of a printed wiring board, various substrate protection means such as a resist used during etching and a solder resist used in a soldering process have been conventionally required. Solder for protecting irrelevant wiring in the soldering process for component mounting even in the manufacturing process of film-like printed wiring boards (flexible printed wiring boards; abbreviated as FPC) used for small devices A resist is required.

  As a protection means for such a substrate, conventionally, a cover lay in which a polyimide film punched into a predetermined mold is laminated has been used. This coverlay also serves as a protective film for the wiring after soldering, and is required to have heat resistance and insulation during soldering and flexibility so that cracks do not occur when the board is assembled. Furthermore, the FPC used for devices other than battery-driven devices also requires flame retardancy.

  Coverlays formed by punching a polyimide film satisfy the above requirements and are most frequently used at present. However, expensive molds are required for punching, and the punched film is manually positioned. In addition, there is a problem that the cost is increased because of the bonding and bonding, and the formation of a fine pattern is difficult.

  As a method for solving these problems, there has been proposed a method in which a photosensitive resin composition is applied in a liquid form on a substrate or attached as a film. According to this method, after forming a coating film on a substrate, a fine pattern coverlay can be easily formed by exposure, development, and heating by photographic technology. Has been.

  However, none of the conventional photosensitive resin compositions satisfy all these characteristics required for FPC. For example, a photosensitive resin composition comprising a prepolymer obtained by addition reaction of a polybasic acid anhydride to a novolak-type epoxy vinyl ester resin, a photopolymerization initiator, a diluent, and an epoxy compound has been proposed (Japanese Patent Publication No. 1-54390). Gazette: Patent Document 1), which has good heat resistance and insulation, but is not flexible and unsuitable for FPC. In addition, a binder system comprising a low molecular weight copolymer, which is a reaction product of a copolymer formed from an ethylenically unsaturated dicarboxylic acid anhydride and an ethylenically unsaturated comonomer, and an amine, and a carboxylic acid-containing high molecular weight copolymer is added to an acrylic resin. A photosensitive resin composition containing a fluorinated urethane monomer component, a photoinitiator, and a block polyisocyanate crosslinking agent has been proposed (Japanese Patent Laid-Open No. 7-278492: Patent Document 2), which has no flame retardancy, There was a problem that the use was limited.

As a method for imparting flame retardancy to the photosensitive resin composition, a conventional flame retardant such as a brominated epoxy resin or a flame retardant system in combination with a flame retardant aid such as antimony trioxide is used. There was a method (Japanese Patent Laid-Open No. 9-325490: Patent Document 3, Japanese Patent Laid-Open No. 11-242331: Patent Document 4, etc.). However, these flame retardant systems may be inferior in reliability in a high temperature environment, and when using an antimony compound, it is necessary to consider environmental issues regarding the waste treatment of the resin. Furthermore, the brominated epoxy resin has a large problem that flexibility is impaired and thermosetting property is lowered when an amount capable of obtaining a sufficient flame retardancy is added.
In this way, it is easy to obtain a resist that has both high flame resistance and flexibility enough to meet the standards of the UL standard (Underwriters Laboratories requirements), and excellent in soldering heat resistance, moisture resistance, high temperature reliability, etc. Instead, further improvements were desired.

Japanese Patent Publication No. 1-54390 JP 7-278492 A JP-A-9-325490 JP-A-11-242331

  The present invention provides a curable flame retardant composition for resist, particularly a coverlay and solder for FPC, which has both a high level of flame retardancy and flexibility and is excellent in solder heat resistance, moisture resistance and high temperature reliability. It is an object to provide a curable flame retardant composition for a resist that can be suitably used as a resist or the like.

（式中、Ｒは水素原子またはメチル基を表わし、Ｘ¹、Ｘ²、Ｘ³、Ｘ⁴及びＸ⁵はそれぞれ独立して水素原子または臭素原子を表わすが、Ｘ¹〜Ｘ⁵の少なくとも２個は臭素原子である。）及び／または式（２）

（式中、Ｘ⁶、Ｘ⁷、Ｘ⁸、Ｘ⁹及びＸ¹⁰はそれぞれ独立して水素原子または臭素原子を表わすが、Ｘ⁶〜Ｘ¹⁰の少なくとも２個は臭素原子である。）
で示される臭素化合物の重合体または共重合体、及び硬化性樹脂材料を含有することを特徴とするレジスト用硬化性難燃組成物。
２．式（１）及び／または式（２）で示される臭素化合物の重合体または共重合体の重量平均粒径が０．１〜１０μｍである前記１記載のレジスト用硬化性難燃組成物。
３．式（１）及び／または式（２）で示される臭素化合物の重合体または共重合体の配合量が硬化性樹脂材料１００質量部に対して１０〜１００質量部である前記１記載のレジスト用硬化性難燃組成物。
４．硬化性樹脂材料が、熱硬化性樹脂材料である前記１記載のレジスト用硬化性難燃性組成物。
５．硬化性樹脂材料が、熱硬化性樹脂材料及び光硬化性樹脂材料の組み合わせからなる前記１記載のレジスト用硬化性難燃組成物。
６．熱硬化性樹脂材料が、エポキシ樹脂である前記４または５記載のレジスト用硬化性難燃組成物。
７．エポキシ樹脂の硬化剤として、アミン化合物、カルボキシル基を有する化合物、酸無水物基を有する化合物及びフェノール性水酸基を有する化合物からなる群から選択される少なくとも１種の化合物を含有する前記６記載のレジスト用硬化性難燃組成物。
８．さらに、熱硬化触媒を含有する前記７記載のレジスト用硬化性難燃組成物。
９．光硬化性樹脂材料が、エチレン性不飽和末端基を有する感光性プレポリマー（Ａ）、前記感光性プレポリマー（Ａ）を除くエチレン性不飽和基を有する化合物（Ｂ）及び光重合開始剤（Ｃ）を含有する前記５に記載のレジスト用硬化性難燃組成物。
１０．前記１乃至９のいずれか１項に記載のレジスト用硬化性難燃組成物の硬化物。
１１．前記１乃至９のいずれか１項に記載のレジスト用硬化性難燃組成物と着色剤とを含有することを特徴とするインク。
１２．前記４、６、７または８のいずれか１項に記載のレジスト用硬化性難燃組成物を基板に１０〜１００μｍの厚みで塗布した後、１００〜２００℃の温度で１０〜６０分熱処理して硬化させることを特徴とするレジスト用硬化性難燃組成物の硬化方法。
１３．前記５乃至９のいずれか１項に記載のレジスト用硬化性難燃組成物を基板に１０〜１００μｍの厚みで塗布した後、６０〜１００℃の温度で、５〜３０分間程度で熱処理して溶剤を乾燥した後、露光・現像後、１００〜２００℃の温度で、１０〜６０分間熱処理して硬化させることを特徴とするレジスト用硬化性難燃組成物の硬化方法。
１４．前記１乃至９のいずれか１項に記載のレジスト用硬化性難燃組成物の硬化物からなることを特徴とする絶縁保護皮膜。
１５．前記１乃至９のいずれか１項に記載のレジスト用硬化性難燃組成物の硬化物からなることを特徴とする層間絶縁膜。
１６．前記１４記載の絶縁保護皮膜を有することを特徴とするプリント配線板。
１７．前記１５記載の層間絶縁膜を有することを特徴とするプリント配線板。 As a result of intensive studies, the present inventors have found that the above-described problems can be solved by using a flame retardant imparting agent having a specific composition, and have completed the present invention. That is, this invention relates to the curable flame-retardant composition for resists described below, a method for curing the composition, and applications.
1. Formula (1)

(In the formula, R represents a hydrogen atom or a methyl group, and X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represents a hydrogen atom or a bromine atom, but at least 2 of X ^{1 to} X ⁵ Are bromine atoms) and / or formula (2)

(In the formula, X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ each independently represent a hydrogen atom or a bromine atom, but at least two of X ^{6 to} X ¹⁰ are bromine atoms.)
A curable flame retardant composition for a resist comprising a polymer or copolymer of a bromine compound represented by the formula (I) and a curable resin material.
2. 2. The curable flame retardant composition for a resist according to 1, wherein the bromine compound polymer or copolymer represented by the formula (1) and / or the formula (2) has a weight average particle diameter of 0.1 to 10 μm.
3. 2. The resist composition according to 1 above, wherein the amount of the polymer or copolymer of the bromine compound represented by the formula (1) and / or the formula (2) is 10 to 100 parts by mass with respect to 100 parts by mass of the curable resin material. Curable flame retardant composition.
4). 2. The curable flame retardant composition for resists according to 1 above, wherein the curable resin material is a thermosetting resin material.
5). 2. The curable flame retardant composition for a resist according to 1, wherein the curable resin material is a combination of a thermosetting resin material and a photocurable resin material.
6). 6. The curable flame retardant composition for resists according to 4 or 5, wherein the thermosetting resin material is an epoxy resin.
7). 7. The resist according to 6 above, which contains at least one compound selected from the group consisting of an amine compound, a compound having a carboxyl group, a compound having an acid anhydride group, and a compound having a phenolic hydroxyl group as a curing agent for an epoxy resin. Curable flame retardant composition.
8). The curable flame retardant composition for a resist according to the above 7, further comprising a thermosetting catalyst.
9. The photocurable resin material is a photosensitive prepolymer (A) having an ethylenically unsaturated terminal group, a compound (B) having an ethylenically unsaturated group excluding the photosensitive prepolymer (A), and a photopolymerization initiator ( 6. The curable flame retardant composition for resists according to 5 above, which contains C).
10. Hardened | cured material of the curable flame-retardant composition for resists of any one of said 1 thru | or 9.
11. 10. An ink comprising the resist curable flame retardant composition according to any one of 1 to 9 and a colorant.
12 After apply | coating the curable flame retardant composition for resists of any one of said 4, 6, 7 or 8 to a board | substrate with the thickness of 10-100 micrometers, it heat-processes for 10 to 60 minutes at the temperature of 100-200 degreeC. A method for curing a curable flame retardant composition for resist, characterized by comprising:
13. After apply | coating the curable flame retardant composition for resists of any one of said 5 thru | or 9 to a board | substrate with the thickness of 10-100 micrometers, it heat-processes at the temperature of 60-100 degreeC for about 5 to 30 minutes. A method for curing a curable flame retardant composition for resists, comprising drying a solvent, and then heat-curing at a temperature of 100 to 200 ° C. for 10 to 60 minutes after exposure and development.
14 10. An insulating protective film comprising a cured product of the curable flame retardant composition for resist according to any one of 1 to 9 above.
15. 10. An interlayer insulating film comprising a cured product of the curable flame retardant composition for resist according to any one of 1 to 9 above.
16. 15. A printed wiring board comprising the insulating protective film as described in 14 above.
17. 16. A printed wiring board comprising the interlayer insulating film as described in 15 above.

  The resist curable flame retardant composition of the present invention can form a protective film having excellent flame retardancy and flexibility, and solder heat resistance, and is particularly suitable for forming FPC coverlays, solder resists, and the like. Can be used.

  Hereinafter, the present invention will be described in detail. The resist curable flame retardant composition of the present invention comprises a flame retardant imparting agent and a curable resin material.

式中、Ｒは水素原子またはメチル基を表わし、Ｘ¹、Ｘ²、Ｘ³、Ｘ⁴及びＸ⁵はそれぞれ独立して水素原子または臭素原子を表わすが、Ｘ¹〜Ｘ⁵の少なくとも２個は臭素原子である。

式中、Ｘ⁶、Ｘ⁷、Ｘ⁸、Ｘ⁹及びＸ¹⁰はそれぞれ独立して水素原子または臭素原子を表わすが、Ｘ⁶〜Ｘ¹⁰の少なくとも２個は臭素原子である。 I. Flame retardancy imparting agent [bromine compound (co) polymer]
As the flame retardant imparting agent of the curable flame retardant composition for resists of the present invention, a polymer or copolymer of a bromine compound represented by formula (1) and / or formula (2) (hereinafter referred to as (co)). Abbreviated polymer)).

In the formula, R represents a hydrogen atom or a methyl group, and X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a bromine atom, but at least two of X ^{1 to} X ⁵ Is a bromine atom.

In the formula, X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ each independently represent a hydrogen atom or a bromine atom, but at least two of X ^{6 to} X ¹⁰ are bromine atoms.

  Usually, in order to efficiently impart flame retardancy to the curable resin material, it is important to uniformly mix and dissolve the compound having a bromine atom in the resin material. However, if a necessary amount of a flame retardant containing a bromine atom is blended and dissolved to cure the curable resin material, the cured coating film becomes hard and is not particularly suitable as a resist material for a flexible substrate. On the other hand, the compound represented by the formula (1) of the present invention or the (co) polymer of the compound represented by the formula (2) has a remarkably low solubility in the curable resin material used in the present invention. It exists as a state dispersed in the resin material. As a result, the flexibility can be maintained even when the necessary amount that exhibits flame retardancy is blended and cured.

Here, specific examples of the compound represented by the formula (1) include dibromobenzyl (meth) acrylate, tribromobenzyl (meth) acrylate, tetrabromobenzyl (meth) acrylate, and pentabromobenzyl (meth) acrylate. (Hereinafter, acrylate and methacrylate are collectively referred to as “(meth) acrylate”, and acrylic acid and methacrylic acid are collectively referred to as “(meth) acrylic acid”).
Specific examples of the compound represented by the formula (2) include dibromostyrene, tribromostyrene, tetrabromostyrene, and pentabromostyrene.

  In addition, the compound represented by the formula (1) and / or the formula (2) is copolymerized with another compound (a) having another ethylenically unsaturated group as long as the solubility in the curable resin material does not increase. It doesn't matter. Specific examples of the compound (a) having such an ethylenically unsaturated group include the following compounds.

  Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, Cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acrylonitrile, glycidyl (meth) acrylate, allyl glycidyl ether, 2- Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, trifluoroethyl acrylate, 2, , 3,3-tetrafluoropropyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, (Meth) acryloyloxyethyl hexahydrophthalic acid, (meth) acrylates such as (meth) acrylic acid dimer, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, Compounds having an amide group such as N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N- (meth) acryloylmorpholine, styrene , Α-methyls Tylene, (o, m, p-) methylstyrene (o, m, p-) hydroxystyrene, vinyl acetate, maleic acid, dimethyl maleate, diethyl maleate, fumaric acid, dimethyl fumarate, diethyl fumarate, itaconic acid Vinyl compounds such as

The ratio of copolymerization of the compound represented by formula (1) and / or formula (2) and the compound (a) having an ethylenically unsaturated group is the compound represented by formula (1) and / or formula (2): It is compound (a) which has an ethylenically unsaturated group = 99-50: 1-50 (mass ratio). When the ratio of the compound represented by the formula (1) and / or the formula (2) is less than 50% by mass, the solubility in the curable resin material is increased, and the flexibility of the cured coating film is lost. Preferably it is 70 mass% or more.
When a (co) polymer of a bromine compound represented by the formula (1) and / or formula (2), which is a flame retardant imparting agent, is added to the curable resin material, a roll mill such as a two-roll mill or a three-roll mill is used as it is. It may be kneaded with a kneader or the like, but it is more preferable to blend after finely pulverizing in advance because the smoothness of the coating film is improved.

  Examples of the equipment for performing such pulverization treatment include a bead mill such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill. The bead diameter (diameter) used in these bead mills is preferably 0.2 to 1.5 mm, more preferably 0.4 to 1.0 mm. If it is less than 0.2 mm, the weight of one bead becomes too small, so the pulverization energy of one bead becomes small, and the pulverization of the flame retardancy imparting agent does not proceed. If the thickness exceeds 1.5 mm, the number of collisions between the beads decreases, and it becomes difficult to pulverize the flame retardant imparting agent in a short time. The material of the beads is preferably a ceramic such as zirconia or alumina, or a material having a specific gravity of 4 or more, such as stainless steel, because the grinding efficiency is increased.

  The temperature during pulverization is preferably in the range of 10 to 60 ° C, more preferably from room temperature to 50 ° C. If it is less than 10 ° C., moisture in the atmosphere is mixed into the dispersion due to condensation, which is not preferable. On the other hand, when the temperature exceeds 60 ° C., alteration such as thickening occurs, which is not preferable.

  As a solvent that can be used at the time of fine pulverization by a bead mill, a (co) polymer of a bromine compound represented by the formula (1) and / or the formula (2) that is a flame retardant imparting agent does not dissolve, and curing that is blended later Any compound that is inactive with respect to the conductive resin material can be used without any problem. Such solvents include methanol, ethanol, isopropanol, toluene, xylene, ethylbenzene, cyclohexane, isophorone, cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl Ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone, , N- dimethylformamide, N- methylpyrrolidone and the like. You may use these individually or in combination of 2 or more types. If there is no problem in terms of viscosity, a curable resin material may be used as a solvent during pulverization.

  The weight average particle size of the flame retardant imparting agent thus finely pulverized is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm. If it is smaller than 0.1 μm, reaggregation of the flame retardancy imparting agent becomes large. On the other hand, if it exceeds 10 μm, the resolution required for the resist cannot be obtained, or the smoothness of the coating film decreases. The weight average particle diameter here is a value measured by a laser diffraction type light scattering light analyzer, and a specific example of such an apparatus is a Microtrac MKII type particle size analyzer SRA type (Nikkiso Co., Ltd.). .

II. Curable resin material The curable resin material used in the present invention may be any material that is used as a resist resin material, such as a thermosetting resin material or a photocurable resin material.

II-1. Thermosetting resin materials Specifically, epoxy resins, phenol resins, silicone resins, melamine derivatives (for example, hexamethoxymelamine, hexabutoxylated melamine, condensed hexamethoxymelamine, etc.), urea compounds (for example, dimethylol urea, etc.) Bisphenol compounds (for example, tetramethylol / bisphenol A), oxazoline compounds, oxetane compounds, and the like. These thermosetting resins can be used alone or in combination of two or more.
Among these, epoxy resins are preferable from the viewpoints of long-term insulating properties, heat resistance, and processability.

II-1- (1). Epoxy resin Epoxy resin is a compound containing two or more oxirane groups in one molecule. Specifically, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F Type epoxy resin, novolak type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, N-glycidyl type epoxy resin, bisphenol A novolak type epoxy resin, rubber-modified epoxy resin, dicyclopentadiene phenolic type epoxy resin, silicon Examples thereof include an epoxy compound having two or more epoxy groups in one molecule such as a modified epoxy resin and an ε-caprolactone-modified epoxy resin. Furthermore, bisphenol S type epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, bixylenol type epoxy resin, biphenyl type epoxy resin and the like can be mentioned. In the present invention, these epoxy resins can be used alone or in combination of two or more.

Examples of the curing catalyst for these epoxy resins include compounds having an action of promoting the polymerization of epoxy groups such as tertiary amines and imidazole compounds.
Examples of the epoxy resin curing agent include primary or secondary amine compounds, compounds having a carboxyl group, acid anhydride compounds, compounds having a functional group added to an epoxy group such as a phenol compound.

  Specific examples of the tertiary amine compound include triethylamine, dimethylcyclohexylamine, N, N-dimethylpiperazine, benzyldimethylamine, 2- (N, N-dimethylaminomethyl) phenol, 2,4,6-tris (N, N-dimethylaminomethyl) phenol, 1,8-diazabiscyclo (5.4.0) undecene-1, and the like.

Specific examples of the imidazole compound include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole. 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6- [2′-methyl Imidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2-methylimidazole isocyanuric acid addition , 2-phenylimidazole / isocyanuric acid adduct, 2 , 4-Diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine / isocyanuric acid adduct and the like.
More detailed specific examples of these tertiary amine compounds and imidazole compounds are described in “New Development of Epoxy Resin Curing Agent” (CMC Co., Ltd., published in 1994), pages 94-107.

Specific examples of the primary or secondary amine compound include ethylenediamine, triethylenetetramine, polyoxypropylenediamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, norbornenediamine, Aliphatic amines such as 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5.5) undecane, m-xylylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenyl Aromatic amines such as sulfone and α, α′-bis (4-aminophenyl) -p-diisopropylbenzene are exemplified. Further details are described in “New Development of Epoxy Resin Curing Agent” (CMC Co., Ltd., published in 1994), pages 41-93.
Specific examples of the compound having a carboxyl group include phthalic acid, isophthalic acid, maleic acid, succinic acid, itaconic acid, dodecenyl succinic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, endo Methylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, trimellitic acid, hydromellitic acid, benzophenonetetracarboxylic acid, azelaic acid, polydodecanedioic acid, 7,12-dimethyl-7,11-octadecadien-1,18- Low molecular weight polycarboxylic acids such as dicarboxylic acids, oligomers such as epoxy (meth) acrylates having carboxyl groups, urethane (meth) acrylates having carboxyl groups, and acrylic copolymers having carboxyl groups in the side chains Chromatography, and the like.

  Acid anhydride compounds include maleic anhydride, succinic anhydride, itaconic anhydride, dodecenyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride , Endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bis (anhydrotrimellilate), Examples thereof include glycerol tris (anhydro trimellitate), polyazeline acid anhydride, polydodecanedioic acid anhydride, 7,12-dimethyl-7,11-octadecadien-1,18-dicarboxylic acid partial anhydride, and the like. Further details are described in “New Development of Epoxy Resin Curing Agent” (CMC Co., Ltd., published in 1994), pages 117-145.

Specific examples of the phenol compound include bisphenol F, bisphenol A, bisphenol S, phenol novolak, o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, poly-p-vinylphenol, bisphenol A type. And novolak. Further details are described in “New Development of Epoxy Resin Curing Agent” (CMC Co., Ltd., published in 1994), pages 149-162.
In order to increase the reactivity of the acid anhydride compound and the phenol compound with the epoxy group, the above-described tertiary amine compound or imidazole compound may be added.

II-2. Photocurable resin material The photocurable resin material is not particularly limited as long as it can be cured by visible light, ultraviolet light or the like, but preferably a photosensitive prepolymer (A) having an ethylenically unsaturated terminal group, It consists of a compound (B) having an ethylenically unsaturated group excluding the photosensitive prepolymer (A), and a photopolymerization initiator (C).

II-2- (1). Photosensitive prepolymer (A)
The photosensitive prepolymer (A) used in the present invention has an ethylenically unsaturated end group derived from an acrylic monomer. Examples of the photosensitive prepolymer include polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polybutadiene (meth) acrylate, silicon (meth) acrylate, melamine (meth) acrylate, and the like.

The photosensitive prepolymer (A) of the present invention is not particularly limited as long as it has an ethylenically unsaturated group in the molecule, but has a carboxyl group and at least two ethylenically unsaturated bonds in one molecule. Is more preferable. By having a carboxyl group, it is possible to obtain alkali developability and reactivity with an epoxy resin, and by having two or more ethylenically unsaturated groups, high photosensitivity can be obtained.
Specifically, an epoxy (meth) acrylate compound having a carboxyl group (EA) or a urethane having a carboxyl group (meth) is particularly preferable in terms of a balance between long-term insulating properties, heat resistance, adhesion, and flexibility. An acrylate compound (UA) is mentioned.

<Epoxy (meth) acrylate compound (EA) having carboxyl group>
Although it does not specifically limit as an epoxy (meth) acrylate compound which has a carboxyl group in this invention, The epoxy obtained by making the reaction material of an epoxy compound and unsaturated group containing monocarboxylic acid react with an acid anhydride. (Meth) acrylate compounds are suitable.

  Although it does not specifically limit as an epoxy compound, A bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a phenol novolac type epoxy compound, a cresol novolak type epoxy compound, an aliphatic epoxy compound, etc. The epoxy compound is mentioned. These may be used alone or in combination of two or more.

  Examples of the unsaturated group-containing monocarboxylic acid include acrylic acid, a dimer of acrylic acid, methacrylic acid, cinnamic acid, and crotonic acid. In addition, a half ester compound that is a reaction product of a hydroxyl group-containing acrylate and a saturated or unsaturated dibasic acid anhydride, a half ester that is a reaction product of an unsaturated group-containing monoglycidyl ether and a saturated or unsaturated dibasic acid Also included are compounds. These unsaturated group-containing monocarboxylic acids can be used alone or in combination of two or more.

  Acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydro And dibasic acid anhydrides such as phthalic anhydride, chlorendic anhydride, and methyltetrahydrophthalic anhydride. These may be used alone or in combination of two or more.

  Although the molecular weight of the epoxy (meth) acrylate compound having a carboxyl group thus obtained is not particularly limited, the number average molecular weight is preferably 1000 to 40000, more preferably 2000 to 5000. Here, the number average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography.

  The acid value of the epoxy (meth) acrylate compound (meaning the solid content acid value, measured in accordance with JIS K0070, the same applies hereinafter) is preferably 10 mgKOH / g or more, and is in the range of 45 to 160 mgKOH / g. More preferably, the range of 50 to 140 mgKOH / g is particularly preferable because the balance between alkali solubility and alkali resistance of the cured film is good. When the acid value is less than 10 mgKOH / g, the alkali solubility is deteriorated. On the other hand, when the acid value is too large, the resist such as the alkali resistance of the cured film and the electrical characteristics depending on the combination of the constituent components of the curable flame retardant composition for resist. As a result, it may become a factor of lowering the characteristics.

<Urethane (meth) acrylate compound having carboxyl group (UA)>
The urethane (meth) acrylate compound having a carboxyl group in the present invention is a compound including, as constituent units, a (meth) acrylate-derived unit having a hydroxyl group, a polyol-derived unit, and a polyisocyanate-derived unit. More specifically, both terminals are composed of (meth) acrylate-derived units having hydroxyl groups, and the terminals are composed of repeating units composed of polyol-derived units and polyisocyanate-derived units linked by urethane bonds. And a structure in which a carboxyl group is present in this repeating unit.

  That is, the urethane (meth) acrylate compound having a carboxyl group is Ra- (CONHRcNHCO-ORbO-OCNHRcNHCOO) n-Ra [wherein Ra is a (meth) acrylate-derived unit having a hydroxyl group, ORbO is dehydration of polyol. An elementary residue, Rc, represents a deisocyanate residue of polyisocyanate. ] Is shown.

  The urethane (meth) acrylate compound having a carboxyl group can be produced by reacting at least a (meth) acrylate having a hydroxyl group, a polyol, and a polyisocyanate. Here, at least one of a polyol and a polyisocyanate is used. On the other hand, it is necessary to use a compound having a carboxyl group. Preferably, a polyol having a carboxyl group is used. Thus, by using a compound having a carboxyl group as the polyol and / or polyisocyanate, a urethane (meth) acrylate compound having a carboxyl group in Rb or Rc can be produced. In the above formula, n is preferably about 1 to 200, and more preferably 2 to 30. When n is in such a range, the flexibility of the cured film made of the curable flame retardant composition for resist is more excellent.

  In addition, when at least one of polyol and polyisocyanate is used in two or more types, the repeating unit represents a plurality of types, but the regularity of the plurality of units depends on the purpose such as complete random, block, localization, etc. Can be selected as appropriate.

  As the (meth) acrylate having a hydroxyl group used in the urethane (meth) acrylate compound (UA) having a carboxyl group, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, Ε-caprolactone or alkylene oxide adduct of each (meth) acrylate, glycerin mono (meth) acrylate, glycerin di (meth) acrylate, glycidyl methacrylate-acrylic acid adduct, trimethylolpropane mono (meth) acrylate, trimethylolpropane Di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tri (meth) Acrylate, trimethylolpropane - alkylene oxide adduct - di (meth) acrylate.

  These (meth) acrylates having a hydroxyl group can be used alone or in combination of two or more. Among these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are preferable, and 2-hydroxyethyl (meth) acrylate is more preferable. When 2-hydroxyethyl (meth) acrylate is used, it is easier to synthesize a urethane (meth) acrylate compound (UA) having a carboxyl group.

  As a polyol used for the urethane (meth) acrylate compound (UA) having a carboxyl group, a polymer polyol and / or a dihydroxyl compound can be used. As the polymer polyol, units derived from polyether diols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyester polyols obtained from esters of polyhydric alcohols and polybasic acids, hexamethylene carbonate, pentamethylene carbonate, etc. And polylactone diols such as polycarbonate diol, polycaprolactone diol, and polybutyrolactone diol.

  In addition, when using a polymer polyol having a carboxyl group, for example, a compound synthesized such that a tribasic or higher polybasic acid such as (anhydrous) trimellitic acid coexists in the synthesis of the polymer polyol so that the carboxyl group remains. Etc. can be used.

  As the dihydroxyl compound, a branched or linear compound having two alcoholic hydroxyl groups can be used, and it is particularly preferable to use a dihydroxy aliphatic carboxylic acid having a carboxyl group. Examples of such a dihydroxyl compound include dimethylolpropionic acid and dimethylolbutanoic acid. By using a dihydroxy aliphatic carboxylic acid having a carboxyl group, the carboxyl group can be easily present in the urethane (meth) acrylate compound. The dihydroxyl compounds can be used alone or in combination of two or more, and may be used together with the polymer polyol.

  Moreover, when using together the polymer polyol which has a carboxyl group, or when using what has a carboxyl group as polyisocyanate mentioned later, ethylene glycol, diethylene glycol, propylene glycol, 1, 4- butanediol, 1, 3- Dihydroxy compounds having no carboxyl group such as butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol May be used.

  Specific examples of the polyisocyanate used in the urethane (meth) acrylate compound (UA) having a carboxyl group include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, ( o, m, or p) -xylene diisocyanate, methylene bis (cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, etc. Diisocyanate is mentioned. These polyisocyanates can be used alone or in combination of two or more. Moreover, the polyisocyanate which has a carboxyl group can also be used.

  Although the molecular weight of the urethane (meth) acrylate compound (UA) having a carboxyl group used in the present invention is not particularly limited, the number average molecular weight is preferably 1000 to 40000, more preferably 8000 to 30000. Here, the number average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography. The acid value of the urethane (meth) acrylate is preferably 5 to 150 mgKOH / g, more preferably 30 to 120 mgKOH / g.

  If the number average molecular weight of the urethane (meth) acrylate compound having a carboxyl group is less than 1000, the elongation and strength of the cured film made of the curable flame retardant composition for resist may be impaired, and if it exceeds 40000, it becomes hard and flexible. There is a risk of reducing the performance. Moreover, when the acid value is less than 5 mgKOH / g, the alkali solubility of the curable flame retardant composition for resist may be deteriorated, and when it exceeds 150 mgKOH / g, the alkali resistance and electrical characteristics of the cured film may be deteriorated. .

II-2- (2). Compound (B) having an ethylenically unsaturated group
The compound having an ethylenically unsaturated group contained in the photocurable material in the curable flame retardant composition for resist is other than the photosensitive prepolymer (A), and the viscosity of the curable flame retardant composition for resist is It is used for the purpose of adjusting the physical properties such as heat resistance and flexibility when the resist curable flame retardant composition is used as a cured product. Preferably (meth) acrylic acid ester is used.

  Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate , Alkyl (meth) such as hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate Acrylate: cyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) Alicyclic, such as acrylate (meth) acrylate;

  Aromatic (meth) acrylates such as benzyl (meth) acrylate, phenyl (meth) acrylate, phenyl carbitol (meth) acrylate, nonylphenyl (meth) acrylate, nonylphenyl carbitol (meth) acrylate, nonylphenoxy (meth) acrylate, etc. 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, butanediol mono (meth) acrylate, glycerol (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, polyethylene glycol (meta ) Acrylate, or (meth) acrylate having a hydroxyl group such as glycerol di (meth) acrylate;

  (Meth) acrylates having amino groups such as 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-tert-butylaminoethyl (meth) acrylate; methacryloxyethyl phosphate, bis-methacrylic Methacrylate having phosphorus atoms such as loxyethyl phosphate, methacrylooxyethyl phenyl acid phosphate; 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, tripro Lenglycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) ) Diacrylates such as acrylate, bis-glycidyl (meth) acrylate;

  Polyacrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate; bisphenol S ethylene oxide 4 mol addition diacrylate, bisphenol A ethylene oxide 4 mol addition di Modified polyol polyacrylates such as acrylate, fatty acid-modified pentaerythritol diacrylate, trimethylolpropane propylene oxide 3 mol addition triacrylate, trimethylolpropane propylene oxide 6 mol addition triacrylate;

  Polyacrylates having an isocyanuric acid skeleton such as bis (acryloyloxyethyl) monohydroxyethyl isocyanurate, tris (acryloyloxyethyl) isocyanurate, and ε-caprolactone-added tris (acryloyloxyethyl) isocyanurate; glycidyl (meth) acrylate; allyl (Meth) acrylate; polycaprolactone (meth) acrylate; (meth) acryloyloxyethyl phthalate; (meth) acryloyloxyethyl succinate; 2-hydroxy-3-phenoxypropyl (meth) acrylate; phenoxyethyl (meth) acrylate, etc. Can be mentioned.

  In addition, N-vinyl compounds such as N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, etc. also have an ethylenically unsaturated group. Can be suitably used.

  The compounding ratio of the photosensitive prepolymer (A) and the compound (B) having an ethylenically unsaturated group is (A) :( B) = 95: 5 to 50:50, preferably 90:10 in mass ratio. 60:40, more preferably 85:15 to 70:30 (a total of 100). When the blending amount of the component (A) exceeds 95% by mass, the solder heat resistance of the cured film made of the curable flame retardant composition for resist may be lowered, and the blending amount of the component (A) is less than 50% by mass. When it becomes, there exists a tendency for the alkali solubility of the curable flame-retardant composition for resists to fall.

II-2- (3). Photopolymerization initiator (C)
The photopolymerization initiator (C) used in the present invention is a compound that generates active radicals upon light irradiation and initiates radical polymerization of a compound having an ethylenically unsaturated group.
Such compounds include benzophenone, benzoylbenzoic acid, 4-phenylbenzophenone, hydroxybenzophenone, benzophenones such as 4,4'-bis (diethylamino) benzophenone, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, benzoin Benzoin alkyl ethers such as isobutyl ether, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-methyl-1- [4- (methylthio) phenyl Acetofol such as 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone-1 Enones, thioxanthenes such as thioxanthene, 2-chlorothioxanthene, 2-methylthioxanthene, 2,4-dimethylthioxanthene, alkylanthraquinones such as ethylanthraquinone, butylanthraquinone, 2,4,6-trimethylbenzoyldiphenyl Examples include acylphosphine oxides such as phosphine oxide. These can be used alone or as a mixture of two or more. Furthermore, if necessary, a photosensitizer can be used in combination.

  The blending amount of these photopolymerization initiators (C) is 0.001 with respect to a total of 100 parts by mass of the photocuring component composed of the photosensitive prepolymer (A) and the compound (B) having an ethylenically unsaturated group. 1 mass part-20 mass parts are preferable, and 0.2 mass part-10 mass parts are more preferable. When the blending amount of the photopolymerization initiator is less than 0.1 parts by mass, curing may be insufficient.

III. Other additives
III-1. Flame retardant imparting agent (D) other than (co) polymer of bromine compound represented by formula (1) and / or formula (2)
In the curable flame retardant composition for resists of the present invention, a flame retardant imparting agent (D) other than the (co) polymer of the bromine compound represented by formula (1) and / or formula (2) is blended. It doesn't matter.
Examples of the flame retardant imparting agent include bromine compounds (D1) other than (co) polymers of bromine compounds represented by formula (1) and / or formula (2), hydrated metal compounds (D2), phosphorus Examples thereof include a compound (D3) and an antimony compound (D4).

  The bromine compound (D1) other than the (co) polymer of the bromine compound represented by the formula (1) and / or the formula (2) is preferably a compound having a bromine content of 40% by mass or more from the viewpoint of flame retardancy. The compound is preferably 45% by mass. Specific examples thereof include brominated bisphenol A type epoxy resin, brominated cresol novolac type epoxy resin, tetrabromobisphenol A carbonate oligomer, tetrabromobisphenol A, tetrabromobisphenol A-bis (2,3-dibromopropyl ether). Tetrabromobisphenol A-bis (allyl ether), tetrabromobisphenol A-bis (bromoethyl ether), tetrabromobisphenol A-bis (ethoxylate), tetrabromobisphenol S, tetrabromobisphenol S-bis (2,3 -Dibromopropyl ether), brominated phenyl glycidyl ether, hexabromobenzene, pentabromotoluene, hexabromocyclododecane, decabromodiphenyl oxide, Kutabromodiphenyl oxide, ethylenebis (pentabromophenyl), ethylenebis (tetrabromophthalimide), tetrabromophthalic anhydride, tribromophenol, tris (tribromophenoxy) triazine, polydibromophenylene oxide, bis (tribromophenoxyethane) , Tribromoneopentyl glycol, dibromoneopentyl glycol, pentabromobenzyl acrylate, dibromostyrene, tribromostyrene and the like.

  The hydrated metal compound (D2) is a metal compound having water of crystallization, and examples thereof include those in which the amount of bound water per mole by thermal analysis is in the range of 12 to 60% (mass%), but is not limited thereto. It is not something. From the viewpoint of flame retardancy and the like, preferably, a hydrated metal compound having an endothermic amount at the time of thermal decomposition of 400 J / g or more, preferably 600 to 2500 J / g is used. Specific examples of such hydrated metal compounds include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, dosonite, calcium aluminate, dihydrate gypsum, zinc borate, barium metaborate, zinc hydroxystannate, kaolin. And vermiculite. Of these, aluminum hydroxide or magnesium hydroxide is particularly preferred.

  The particle size of the hydrated metal compound used in the present invention is not particularly limited, but the average particle size is preferably 40 μm or less, and more preferably 2 μm or less. When the average particle diameter exceeds 40 μm, the transparency of the cured resist film is deteriorated and the light transmittance may be lowered, or the appearance and smoothness of the coating film surface may be impaired.

  The hydrated metal compound (D2) used in the present invention is particularly preferably subjected to surface treatment with a polar surface treatment agent from the viewpoint of improving transparency. Examples of the surface treatment agent having such polarity include silane coupling agents and titanate coupling agents such as epoxy silane, amino silane, vinyl silane, and mercapto silane.

  The phosphorus compound (D3) used in the present invention is preferably a compound having a chemical structure of “P—O—R” (R is an organic group), and usually has a phosphorus atom of trivalent or pentavalent. used. Trivalent compounds include phosphite compounds, phosphonite compounds, and phosphinite compounds. On the other hand, those having a pentavalent phosphorus atom include phosphate compounds, phosphonate compounds, and phosphinate compounds. Among these, a phosphate ester compound having a pentavalent phosphorus atom is preferably used from the viewpoint of storage stability.

The organic group forming the ester of these phosphate ester compounds may be any of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group, etc., of which an aromatic hydrocarbon group It is preferable from the viewpoint of flame retardancy and solder heat resistance.
Examples of such phosphate ester compounds include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, resorcinol bis (diphenol) phosphate, bisphenol A bis (diphenyl phosphate), 2-ethylhexyl diphenyl phosphate, and the like. Is mentioned.
In addition to the phosphorus compounds, those having a structure of “—P (R) ₂ ═N—” (R is an organic group) such as phosphazene compounds can be used without any problem.

  Specific examples of the antimony compound (D4) used in the present invention include antimony trioxide, antimony tetraoxide, antimony pentoxide, and sodium antimonate.

III-2. Organic Solvent The curable flame retardant composition for resists of the present invention may be used by adding an organic solvent as necessary for adjusting the viscosity. By adjusting the viscosity in this manner, it becomes easy to apply or print on an object by roller coating, spin coating, screen coating, curtain coating, or the like.

  As organic solvents, isopropanol, 1-butanol, toluene, xylene, ethylbenzene, cyclohexane, isophorone, ethylene glycol monoacetate, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n -Butyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, diethylene glycol ethyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, isoamyl acetate , Lactic acid Chill, acetone, methyl ethyl ketone, cyclohexanone, N, N- dimethylformamide, N- methylpyrrolidone and the like. You may use these individually or in combination of 2 or more types.

  The amount of the organic solvent used is preferably adjusted so that the viscosity of the curable flame retardant composition for resist is 500 to 500,000 mPa · s (measured at 25 ° C. with a Brookfield Viscometer). More preferably, it is 1,000 to 500,000 mPa · s. Such a viscosity is more suitable for application and printing on an object and is easier to use. Moreover, the preferable usage-amount of the organic solvent in order to set it as such a viscosity is 1.5 mass times or less of solid content other than an organic solvent. If it exceeds 1.5 mass times, the solid content concentration will be low, and when printing this resist curable flame retardant composition on a substrate etc., sufficient film thickness will not be obtained by one printing, printing many times May be required.

III-3. Other additives A colorant may be further added to the resist curable flame retardant composition of the present invention to be used as an ink. Examples of the colorant include phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and the like. Also when used as an ink, the viscosity is preferably 500 to 500,000 mPa · s (measured at 25 ° C. using a B-type viscometer).

  In the resist curable flame retardant composition of the present invention, a flow regulator can be further added for the purpose of adjusting the fluidity. The fluidity modifier is, for example, the fluidity of the resist curable flame retardant composition when the resist curable flame retardant composition is applied to an object by roller coating, spin coating, screen coating, curtain coating, or the like. Can be adjusted as appropriate. Examples of the flow regulator include inorganic and organic fillers, waxes, surfactants, and the like.

  Specific examples of the inorganic filler include talc, barium sulfate, barium titanate, silica, alumina, clay, magnesium carbonate, calcium carbonate, aluminum hydroxide, and a silicate compound. Specific examples of the organic filler include silicon resin, silicon rubber, and fluorine resin. Specific examples of the wax include polyamide wax and oxidized polyethylene wax. Specific examples of the surfactant include silicone oil, higher fatty acid ester, amide and the like. These fluidity modifiers can be used alone or in combination of two or more. Of these, the use of inorganic fillers is preferable because not only the fluidity of the curable flame retardant composition for resists but also properties such as adhesion and hardness can be improved.

Moreover, additives, such as a thermal-polymerization inhibitor, a thickener, a defoaming agent, a leveling agent, an adhesiveness imparting agent, can be added to the curable flame retardant composition for resist as necessary. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, phenothiazine and the like. Examples of the thickener include asbestos, olben, benton, montmorillonite and the like. The antifoaming agent is used for eliminating bubbles generated at the time of printing, coating, and curing, and specific examples include acrylic and silicon surfactants. The leveling agent is used to lose the unevenness on the surface of the film generated during printing and coating, and specifically includes an acrylic or silicon surfactant. Examples of the adhesion imparting agent include imidazole, thiazole, triazole, and silane coupling agents.
Further, for storage stability, an ultraviolet inhibitor, a plasticizer, and the like can be added within a range that does not impair the gist of the present invention.

IV. Method for Producing Resist Curable Flame Retardant Composition The resist curable flame retardant composition of the present invention can be produced by mixing the above-described components in a usual manner. The mixing method is not particularly limited, and a part of the components may be mixed and then the remaining components may be mixed, or all the components may be mixed at once.
Specifically, after mixing each of the above-described components, it is produced using a known kneading method such as a kneader, three rolls, or a bead mill.

V. Cured product and application of curable flame retardant composition for resist The curable flame retardant composition for resist of the present invention has an appropriate thickness on a substrate or the like when the resin material is composed only of a thermosetting resin material. A cured product can be obtained by heat treatment as it is after coating.
In addition, when the resin material is composed of a thermosetting resin material and a photocurable resin material, it is coated on the substrate with an appropriate thickness, then dried with a solvent, cured by exposure, alkali development, and heat treatment. A cured product can be obtained.

  The resist curable flame retardant composition of the present invention can be used for various applications, in particular, flame retardancy is required, thermosetting, photocuring, adhesion to a substrate, insulation, heat resistance, Since various properties that decrease when a normal flame retardant such as warp deformability and flexibility are blended do not decrease, it is suitable for use as an insulating protective coating on a printed wiring board.

  When an insulating protective film is formed, the following method can be used. When the resin material of the resist curable flame retardant composition is composed only of the thermosetting resin material, the resist curable flame retardant composition was applied to a thickness of 10 to 100 μm on the substrate on which the circuit was formed. Then, an insulating protective film can be formed by heat treatment for 10 to 60 minutes in a temperature range of 100 to 200 ° C. and curing.

  When the resin material of the curable flame retardant composition for resist is composed of a photocurable resin material and a thermosetting resin material, the resist material is applied with a thickness of 10 to 100 μm, and then in a temperature range of 60 to 100 ° C., 5 After heat treatment for about 30 minutes and drying, exposure is performed through a negative mask provided with a desired exposure pattern, and unexposed portions are removed with a developing solution and developed, and in a temperature range of 100 to 200 ° C., 10 An insulating protective film can be formed by curing by heat treatment for ˜60 minutes. Here, as the active light used for the exposure, active light generated from a known light source such as a carbon arc, a mercury vapor arc, a xenon arc, or the like is used. Since the sensitivity of the photopolymerization initiator (C) contained in the photosensitive layer is usually maximum in the ultraviolet region, the active light source preferably emits ultraviolet rays effectively in that case. As the developer, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, trimethylammonium hydroxide, sodium phosphate, sodium silicate, ammonia, amines and the like can be used.

This resist curable flame retardant composition is used not only for flame retardancy but also for insulating protective coatings on FPC boards because the flexibility and flexibility of a cured product often seen when a flame retardant is added is not reduced. Especially suitable for. Further, for example, it may be used as an insulating resin layer between layers of a multilayer printed wiring board.
The curable flame retardant composition for resist of the present invention is preferably used in the form of an ink containing an organic solvent, but after applying the ink on a support film such as polyethylene terephthalate and drying the organic solvent, You may use it with the form of the dry film which bonded the cover film together.

  When the curable flame retardant composition for resists of the present invention is used, high flexibility is maintained despite having excellent flame retardancy including a flame retardant, and heat is different from the case where other flame retardant is blended. It is possible to form a cured film that does not deteriorate the curability and photocurability, and further satisfies performances such as heat resistance, electrical insulation, and adhesion to the wiring board. This cured film is particularly excellent in flame retardancy, flexibility, and electrical insulation. Therefore, even when used for a thin wiring board such as an FPC board, curling does not occur, and a flexible insulating protective film excellent in electrical performance and handleability can be formed.

  Hereinafter, the present invention will be specifically described with reference to production examples and examples, but the present invention is not limited to these examples.

Production Example 1: Synthesis of Photosensitive Prepolymer (EA-1) Having Carboxyl Group Into a flask equipped with a gas introduction tube, a stirrer, a cooling tube and a thermometer, a bisphenol A type epoxy compound (manufactured by Asahi Ciba Co., Ltd.) Product name: Araldite # 2600) 291 g, bisphenol A 129 g and 0.20 g of triethylamine as a catalyst were charged and reacted at 150 to 160 ° C. for 1 hour to obtain a bisphenol A type epoxy compound having a softening point of 97 ° C. and an epoxy equivalent of 1000 It was. This was charged with 30 g of acrylic acid, 0.45 g of monomethyl ether hydroquinone as an inhibitor and 1.65 g of triphenylphosphine as an esterification catalyst, and reacted at 120 ° C. for 5 hours to obtain a reaction product having an acid value of 1 mg KOH / g. . Further, 168 g of tetrahydrophthalic anhydride was added thereto and reacted at 120 ° C. until the acid value became 100 mgKOH / g. This reaction took 3 hours. As a solvent, 265 g of ethylene glycol monomethyl ether acetate and 114 g of Supersol # 1800 manufactured by Mitsubishi Oil Co., Ltd. were added to obtain an epoxy acrylate resin (EA-1) having a solid content concentration of 62% by mass.

Production Example 2: Synthesis of photosensitive prepolymer (UA-1) having a carboxyl group In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, polytetramethylene glycol (Hodogaya Chemical Co., Ltd., PTMG-850, molecular weight 850) was prepared. ) 2550 g (3 mol), dimethylolpropionic acid 670 g (5 mol) as the dihydroxyl compound having a carboxyl group, 1776 g (8 mol) of isophorone diisocyanate as the polyisocyanate and 2-hydroxyethyl acrylate as the (meth) acrylate having a hydroxyl group 238 g (2.05 mol), 3490 g of ethylene glycol monomethyl ether acetate as a reaction solvent, and 1.0 g each of p-methoxyphenol and di-t-butyl-hydroxytoluene were added. I entered. The mixture was heated to 60 ° C. with stirring and stopped, and 1.6 g of dibutyltin dilaurate was added. When the temperature in the reaction vessel starts to decrease, the mixture is heated again and stirred at 80 ° C., and the reaction is terminated after confirming that the absorption spectrum of the isocyanate group (2280 cm ⁻¹ ) has disappeared in the infrared absorption spectrum. A carboxyl group-containing photosensitive prepolymer (UA-1) having a solid content acid value of 46 mgKOH / g and a solid content concentration of 60% was obtained. The viscosity (25 ° C.) of this product was 25 Pa · s.

Production Example 3 Preparation of Flame Retardant (PBBA) Dispersion Masterbatch Poly (pentabromobenzyl acrylate) Bromine (PBBA) (trade name PBB-PA, bromine content 69% by mass, Bromochem Far East Co., Ltd.) 40 g, 40 g of diethylene glycol monoethyl ether acetate and 150 g of zirconia beads having a diameter of 1 mm were placed in a 160 ml stainless steel can and pulverized for 4 hours with a paint shaker (manufactured by Asada Tekko Co., Ltd.). Thereafter, the zirconia beads were separated by filtration to obtain a PBBA master batch having a PBBA content of 50% by mass. From this pulverization treatment, the weight average particle diameter, which was 94 μm before pulverization, became 3.4 μm. The weight average particle diameter was measured with a laser diffraction light scattering light analyzer Microtrac MKII type particle size analyzer SRA type (Nikkiso Co., Ltd.).

Production Example 4: Preparation of flame retardant (PBS) dispersion masterbatch Other than using brominated polystyrene (PBS) (trade name PYRO-CHEK68, bromine content 68% by mass, Albemarle Japan Co., Ltd.) instead of PBBA Obtained a PBS master batch in exactly the same manner as in Production Example 3. From this pulverization treatment, the weight average particle diameter, which was 120 μm before pulverization, became 4.4 μm.

Examples 1-2 and Comparative Examples 1-2: Preparation of Curable Flame Retardant Composition Three roll mills (manufactured by Kodaira Seisakusho Co., Ltd.) were separately prepared with the main component and curing agent in the blending ratio (unit: parts by mass) shown in Table 1. The thermosetting flame retardant compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were prepared by kneading and passing 3 times through the model RIII-1RM-2).

Examples 3 to 6 and Comparative Examples 3 to 4: Preparation of light / thermosetting flame retardant composition Three roll mills (Co., Ltd.) were separately prepared with the main component and curing agent in the blending ratio (unit: parts by mass) shown in Table 2. The photo-thermosetting flame retardant compositions of Examples 3 to 6 and Comparative Examples 3 to 4 were prepared by passing the mixture three times through Kodaira Seisakusho, model RIII-1RM-2).

<Evaluation of thermosetting flame retardant composition>
[Preparation of evaluation sample]
After blending and mixing the main component and curing agent of the flame retardant thermosetting composition shown in Table 1 at the ratios shown in Table 1, respectively, the film thickness after drying on the evaluation substrate is about 20 μm. It was applied by screen printing with a 150 mesh polyester plate and thermally cured at 150 ° C. The thermosetting time was defined as the time when each sample became “◯” in the evaluation of thermosetting. The following substrates (1) to (3) were used as evaluation substrates.
Substrate (1) Printed circuit board (upicel (registered trademark) N, manufactured by Ube Industries) made by laminating a polyimide film (thickness: 50 μm) on one side of copper foil (thickness: 35 μm) is washed with 1% aqueous sulfuric acid. And then washed with water and dried by air flow,
Substrate (2) 25 μm-thick polyimide film [Kapton (registered trademark) 100H, manufactured by Toray DuPont Co., Ltd.]
Substrate (3) Commercial substrate (IPC-C).

[Evaluation of the physical properties]
Table 3 shows the physical property evaluation results of thermosetting, flexibility, soldering heat resistance, flammability and electrical insulation (insulation resistance) carried out as follows.

-Thermosetting The board | substrate (2) which apply | coated the thermosetting flame retardant composition of Examples 1-2 and Comparative Examples 1-2 was put into a 150 degreeC hot-air circulation type dryer, and 20 minutes, 40 minutes, and 60, respectively. Partial heat curing was performed. Furthermore, several drops of ethyl acetate were added to the heat-cured coating film, and the state of the coating film after rubbing with Kimwipe was visually observed and evaluated according to the following criteria. If cured, no change is seen in the coating.
○: No change is seen in the coating film,
Δ: Whitening of the coating film
X: The coating film is dissolved.

-Flexibility The presence / absence of whitening of the cured film by applying the thermosetting flame retardant composition of Examples 1-2 and Comparative Examples 1-2 and thermosetting the substrate (2) by bending the coating surface outward at 180 ° And the flexibility was evaluated according to the following criteria.
○: No whitening of the cured film,
X: The cured film is whitened or cracked.

-Solder heat resistance According to the test method of JIS-C-6481, the board | substrate (1) which apply | coated and thermoset the thermosetting flame retardant composition of Examples 1-2 and Comparative Examples 1-2 was soldered at 260 degreeC. The cured film was visually observed and floated for 5 seconds, and the cured film was evaluated with the maximum number of cycles determined to be free of “bulge” and “solder retraction” and no change. .

・ Flammability A flammability test piece was prepared by the following method. A thermosetting flame retardant composition layer having a thickness of 20 μm was provided on both surfaces of a substrate (2) having a thickness of 25 μm and 200 mm × 50 mm to prepare a sample for a flame retardant test. As for the combustion characteristics, flame retardancy was evaluated by a method based on a flame retardant test standard 94UL-VTM test for polymer materials of Underwriters Laboratories Inc. (abbreviated as UL) in the United States. “VTM” and “NOT” in Table 3 are based on the following criteria.

VTM-0: satisfies all the following requirements;
(1) All the test pieces do not burn in flames for more than 10 seconds after stopping each flame contact.
(2) A total of 10 flames should be contacted with 5 test pieces in each group, and the total flame burning time should not exceed 50 seconds.
(3) The flame or red heat combustion must not reach the 125 mm mark.
(4) Absorbent cotton should not be ignited by flammable drops.
(5) After stopping the second flame contact, the sum of the flame and red heat combustion of each sample shall not exceed 30 seconds.
(6) If only one of the five test pieces in the set is not suitable for the requirement, or if the total flame time is in the range of 51 to 55 seconds, then another five test pieces are tested. And all satisfy (1) to (5).

VTM-1: All of the following requirements are satisfied (1) All specimens do not burn in flames for more than 30 seconds after stopping each flame contact.
(2) A total of 10 flames should be applied to each group of 5 test pieces, and the total flammable combustion time shall not exceed 250 seconds.
(3) The flame or red heat combustion must not reach the 125 mm mark.
(4) Absorbent cotton should not be ignited by flammable drops.
(5) After stopping the second flame contact, the sum of the flaming and red heat combustion of each sample should not exceed 60 seconds.
(6) When only one set of five test pieces is not suitable for the requirement, or when the total flame time is in the range of 251 seconds to 255 seconds, another five test pieces are tested. And all satisfy (1) to (5).

VTM-2: All of the following requirements are satisfied (1) All test pieces do not burn in flames for more than 30 seconds after stopping each flame contact.
(2) A total of 10 flames should be applied to each group of 5 test pieces, and the total flammable combustion time shall not exceed 250 seconds.
(3) The flame or red heat combustion must not reach the 125 mm mark.
(4) Absorbent cotton may be ignited by the flamed drop.
(5) After stopping the second flame contact, the sum of the flaming and red heat combustion of each sample should not exceed 60 seconds.
(6) When only one set of five test pieces is not suitable for the requirement, or when the total flame time is in the range of 251 seconds to 255 seconds, another five test pieces are tested. And all satisfy (1) to (5).

NOT: If you do not pass any of the above classes

・ Electrical insulation (insulation resistance)
The thermosetting flame retardant composition layers of Example 1 and Comparative Examples 1 and 2 were provided on the substrate (3), and the laminate was left for 192 hours in an atmosphere of 85 ° C. and 85% relative humidity. Insulation resistance was measured before and after the treatment to evaluate electrical insulation. The insulation resistance value was measured by applying an electric insulation meter to the substrate before and after the treatment in accordance with JIS C5012 after applying a 100 V DC voltage for 1 minute and applying the voltage.

<Evaluation of light / thermosetting flame retardant composition>
[Preparation of evaluation sample]
After mixing and mixing the main components and curing agents of the light and thermosetting flame retardant compositions of Examples 3 to 5 and Comparative Examples 3 to 4 shown in Table 2 at the ratios shown in Table 2, respectively, on the evaluation substrate The film thickness after drying was applied by screen printing with a 150 mesh polyester plate, and the solvent was dried at 80 ° C. for 30 minutes. Each obtained sample was exposed at 500 mJ / cm ² using an exposure machine having a metal halide lamp [HMW-680GW manufactured by Oak Co., Ltd.]. Next, the unexposed portion is removed by spraying with a 1% by mass sodium carbonate aqueous solution at 30 ° C. for 30 seconds, followed by 30 seconds of water at 30 ° C., followed by heat treatment at 150 ° C. for 30 minutes. A sample for evaluation was obtained. At the time of preparing a test piece for light sensitivity evaluation, exposure was performed using a stove 21-step tablet as a negative pattern. The negative pattern was not used when producing other evaluation samples.

[Evaluation of the physical properties]
The physical properties of “flexibility”, “solder heat resistance”, “flammability” and “insulation” are evaluated in the same manner as the thermosetting flame retardant composition described above, and “photosensitivity” is determined using the substrate (1). The following method was used for evaluation. The results are shown in Table 4.

・ Photosensitivity By layering Hitachi Chemical's 21-step step tablet on the sample as a negative pattern, exposing and developing, and measuring the number of steps of the step tablet of the photocured film formed on the resulting copper-clad laminate The photosensitivity of the curable flame retardant composition was evaluated. The photosensitivity is indicated by the number of steps of the step tablet, and the higher the number of steps of the step tablet, the higher the photosensitivity.

Claims (17)

Formula (1)

(In the formula, R represents a hydrogen atom or a methyl group, and X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represents a hydrogen atom or a bromine atom, but at least 2 of X ^{1 to} X ⁵ Are bromine atoms) and / or formula (2)

(In the formula, X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ each independently represent a hydrogen atom or a bromine atom, but at least two of X ^{6 to} X ¹⁰ are bromine atoms.)
A curable flame retardant composition for a resist comprising a polymer or copolymer of a bromine compound represented by the formula (I) and a curable resin material.   2. The curable flame retardant composition for a resist according to claim 1, wherein the polymer or copolymer of the bromine compound represented by the formula (1) and / or the formula (2) has a weight average particle diameter of 0.1 to 10 μm.   The resist according to claim 1, wherein the blending amount of the polymer or copolymer of the bromine compound represented by the formula (1) and / or the formula (2) is 10 to 100 parts by mass with respect to 100 parts by mass of the curable resin material. Curable flame retardant composition.   The curable flame-retardant composition for a resist according to claim 1, wherein the curable resin material is a thermosetting resin material.   The curable flame retardant composition for a resist according to claim 1, wherein the curable resin material is a combination of a thermosetting resin material and a photocurable resin material.   The curable flame retardant composition for a resist according to claim 4 or 5, wherein the thermosetting resin material is an epoxy resin.   The epoxy resin curing agent contains at least one compound selected from the group consisting of amine compounds, compounds having a carboxyl group, compounds having an acid anhydride group, and compounds having a phenolic hydroxyl group. Curable flame retardant composition for resist.   Furthermore, the curable flame-retardant composition for resists of Claim 7 containing a thermosetting catalyst.   The photocurable resin material is a photosensitive prepolymer (A) having an ethylenically unsaturated terminal group, a compound (B) having an ethylenically unsaturated group excluding the photosensitive prepolymer (A), and a photopolymerization initiator ( The curable flame retardant composition for a resist according to claim 5, comprising C).   Hardened | cured material of the curable flame-retardant composition for resists of any one of Claims 1 thru | or 9.   An ink comprising the resist curable flame retardant composition according to any one of claims 1 to 9 and a colorant.   After apply | coating the curable flame-retardant composition for resists of any one of Claim 4, 6, 7 or 8 to a board | substrate with the thickness of 10-100 micrometers, it heat-processes for 10 to 60 minutes at the temperature of 100-200 degreeC. A method for curing a curable flame retardant composition for a resist, characterized by comprising:   The resist curable flame retardant composition according to any one of claims 5 to 9 is applied to a substrate with a thickness of 10 to 100 µm, and then heat-treated at a temperature of 60 to 100 ° C for about 5 to 30 minutes. A method for curing a curable flame retardant composition for a resist, comprising: drying the solvent, then exposing to light and developing, and then curing by heat treatment at a temperature of 100 to 200 ° C. for 10 to 60 minutes.   An insulating protective film comprising a cured product of the curable flame retardant composition for resist according to any one of claims 1 to 9.   An interlayer insulating film comprising a cured product of the curable flame retardant composition for resists according to any one of claims 1 to 9.   A printed wiring board comprising the insulating protective film according to claim 14. A printed wiring board comprising the interlayer insulating film according to claim 15.