JP5493347B2 - Flame retardant resin composition - Google Patents

Description

  The present invention relates to a flame retardant resin composition which is suitable as a solder resist or plating resist for a printed wiring board, particularly a flexible printed wiring board, and is also useful as an interlayer electrical insulating material, a photosensitive optical waveguide or the like.

  Conventionally, a printed wiring board has a protective layer called a coverlay or a solder resist for the purpose of protecting a wiring circuit during or after manufacturing, such as a soldering process performed when electronic components are surface-mounted during manufacturing. Is formed.

For example, information devices such as mobile phones and digital cameras often use flexible printed wiring boards in addition to rigid wiring boards in order to increase functionality, reduce size, and the like. The flexible printed wiring board is mainly used around the bent part and connection part of equipment, so that it can develop fine pattern while maintaining high flexibility and folding resistance, flame resistance, solder heat resistance, Performances that satisfy substrate adhesion, insulation, and the like are required.
Under such circumstances, in recent years, many proposals have been made as flexible photo solder resists. For example, a resist ink composition is disclosed that includes a resin obtained by reacting succinic anhydride with an addition product of an epoxy resin having a bisphenol A skeleton in the main chain and an unsaturated group-containing monocarboxylic acid (Patent Document 1). reference). Although this is excellent in developability, photosensitivity, adhesion, heat resistance, etc., there is a problem that flexibility and folding resistance are still insufficient. Further, as a photosensitive thermosetting composition, a reaction product of a secondary hydroxyl group generated by an esterification reaction of a cresol novolak type epoxy compound and an unsaturated monocarboxylic acid and a saturated or unsaturated polybasic acid anhydride, A reaction product of the secondary hydroxyl group and an unsaturated group-containing isocyanate compound has been proposed (see Patent Document 2). Although these are very excellent in adhesion, solder heat resistance, and coating film resistance, there is a problem that flexibility and folding resistance are still insufficient.

In addition, a photosensitive element containing a polymer obtained by copolymerizing a monomer containing (meth) acrylic acid and a (meth) acrylic acid ester as a binder component has been proposed (see Patent Document 3). These are excellent in developability and resolution, but when used in flexible printed wiring board applications, sufficient adhesion, flexibility and folding resistance cannot be obtained.
Among them, a resist ink composition containing a resin having urethane as a main skeleton can solve these problems (see Patent Document 4). However, as described above, it is often necessary to impart flame retardancy when used as such an insulating material.
For this reason, halogen-based flame retardants have been used to impart flame retardancy to the protective layer, but a solder resist containing no halogen has been strongly desired from the viewpoint of the environment such as generation of harmful gases.

  In general, non-halogen flame retardants include hydrated metal compounds such as aluminum hydroxide and magnesium hydroxide, phosphorus flame retardants such as phosphate esters, phosphine oxides and polyphosphate compounds, and nitrogen flame retardants such as melamine compounds. It is done. However, when these flame retardants are used, the general physical properties required for the solder resist, such as electrical insulation and solder heat resistance, and flame retardancy cannot be achieved.

Examples of the flame retardant that solves the above problem include a phenoxyphosphazene compound (for example, Otsuka Chemical SPB-100) (see Patent Document 5). However, when the above compound is used in a resist ink composition containing a resin having urethane as the main skeleton, the compatibility between the resin having urethane as the main skeleton and the compound is very poor, and the compound bleeds out from the protective layer. There was a problem.
Japanese Patent No. 3281473 Japanese Patent No. 2707495 JP 2004-279479 A JP 2001-159815 A JP, 2005-283762, A Thus, sufficient flexibility required as a protective layer for flexible printed wiring boards, developability and solder heat resistance that can realize high-precision patterning, and a circuit protective layer are necessary. Non-halogen flame retardant resin composition that satisfies various physical properties such as electrical insulation and chemical resistance, has flame retardancy, and has no flame retardant bleed out, and cured product thereof Was not obtained.

  The present invention relates to an interlayer electrical insulating material, an optical waveguide, a printed wiring board, particularly a photo solder resist and a coverlay film for use in a flexible printed wiring board, developability capable of realizing a fine pattern, solder heat resistance, and insulation. Another object of the present invention is to provide a flame retardant resin composition that achieves both physical properties such as chemical resistance, flexibility and folding resistance, and that there is no bleeding out of the flame retardant.

  In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, a flame-retardant resin composition containing a specific carboxyl group-containing photosensitive urethane resin and a phenoxyphosphazene compound having a specific substituent. As a result, the present invention has been completed.

  The present invention relates to a flame retardant resin composition comprising a urethane resin (A) containing a carboxyl group and an ethylenically unsaturated group and a phenoxyphosphazene compound (B) represented by the following general formula (1).

General formula (1)

(However, n is an integer of 3 to 25, and one of R1 and R2 is CN and the other is H, or both are CN. The ratio of cyanophenoxy group in the above compound is phenoxy group and cyano. 2 to 98 mol % of the total of phenoxy groups.)

  Furthermore, the present invention includes 10 to 50 parts by weight of the phenoxyphosphazene compound (B) represented by the general formula (1) in 100 parts by weight of the nonvolatile content of the flame retardant resin composition. The present invention relates to a functional resin composition.

  Furthermore, the present invention relates to the flame retardant resin composition according to any one of the above inventions, which comprises a photopolymerization initiator (C).

  Furthermore, this invention relates to the flame-retardant resin composition of any one of the said invention characterized by including an ethylenically unsaturated group containing compound (D).

  Furthermore, this invention relates to the flame-retardant resin composition of any one of the said invention characterized by including a flame-retardant component (E).

  Furthermore, this invention relates to the flame-retardant resin composition of any one of the said invention characterized by including a thermosetting component (F).

  Furthermore, the present invention relates to the flame retardant resin composition according to any one of the above inventions, characterized by containing a thermosetting aid (G).

 The present invention further relates to a dry film using the flame retardant resin composition of any of the above inventions.

 Furthermore, this invention relates to the hardened | cured material formed by hardening | curing the flame-retardant resin composition of any one of said invention.

 Furthermore, the present invention relates to a printed wiring board comprising a hardened layer formed from the flame retardant resin composition of any of the above inventions on a wiring circuit.

  Furthermore, the present invention relates to a flexible printed wiring board comprising a hardened layer formed from the flame retardant resin composition of any one of the above inventions on a wiring circuit.

  According to the present invention, the sensitivity to active energy rays is excellent, a pattern can be formed by development with a dilute alkaline aqueous solution, and the cured layer obtained by thermosetting in a post-curing (post-cure) step has sufficient flexibility and is difficult. A flame retardant resin composition containing a carboxyl group-containing photosensitive urethane resin suitable for a solder resist ink excellent in flame resistance, bleed-out resistance, high insulation, adhesion, solder heat resistance, coating film resistance, etc. and cured product thereof Can be provided. The flame-retardant resin composition of the present invention can be suitably used as a solder resist for flexible printed wiring boards, coverlay films, plating resists, interlayer electrical insulation materials for wiring boards, optical waveguides, and the like.

  The flame-retardant resin composition of the present invention is required for a photo solder resist, a coverlay film, etc., has various physical properties such as developability, solder heat resistance, insulation, chemical resistance, etc. that can realize fine patterns, and flexibility. It has the characteristics that there is no bleeding out of the flame retardant.

  The carboxyl group-containing and ethylenically unsaturated group-containing urethane resin (A) of the present invention (hereinafter referred to as urethane resin (A)) will be described. Examples of the method for producing the urethane resin (A) include the following synthesis methods including those conventionally known.

  For example, a diisocyanate compound (a), a polyol compound (b), and a carboxylic acid compound (c) having two hydroxyl groups are reacted to synthesize a carboxyl group-containing urethane prepolymer (d), and then the carboxyl in the above (d) It is produced by reacting an epoxy group or oxetane group in (meth) acrylate (e) having one epoxy group or oxetane group in the molecule with respect to the group. At that time, the number of moles of the (meth) acrylate (e) having one epoxy group or oxetane group in the molecule to be reacted with respect to 1 mole of the carboxyl group in the carboxyl group-containing urethane prepolymer (d) is It can adjust suitably according to the quantity of the acid value to do.

  As another synthesis method, the carboxyl group-containing urethane prepolymer (d) is excessively mixed with the diisocyanate compound (a) during synthesis to synthesize a carboxyl group-containing urethane prepolymer (f) having an isocyanate group at the terminal, It is produced by reacting the compound (g) having one hydroxyl group and one or more ethylenically unsaturated groups with the isocyanate group in (f).

  As yet another method, the polyol compound (b) is reacted with a polybasic acid anhydride (h) having two acid anhydride groups in the molecule, and an ester bond derived from half esterification is formed in the main chain. The carboxyl group-containing polyester polyol was synthesized and reacted with diisocyanate (a) to obtain a carboxyl group-containing urethane prepolymer. Furthermore, it is produced by reacting a part of carboxyl groups in this urethane prepolymer with (meth) acrylate (e) having one epoxy group or oxetane group in the molecule.

  As another method, a polyol compound (b), a diisocyanate compound (a), and a carboxylic acid compound (c) having two hydroxyl groups in the molecule are reacted as essential components to produce a carboxyl group-containing urethane prepolymer (d ) And then reacting the carboxyl group in (d) with the epoxy group or oxetane group in (meth) acrylate (e) having one epoxy group or oxetane group in the molecule. After preparing the hydroxyl group-containing urethane prepolymer (i), the hydroxyl group in the above (i) is reacted with the acid anhydride group in the polybasic acid anhydride (j) having one acid anhydride group. By making it, the resin which has an ethylenically unsaturated group in a side chain, and also has a carboxyl group is manufactured. The resin is more preferable in terms of developability and heat resistance.

  In the present invention, examples of the diisocyanate compound (a) include aromatic diisocyanates, aliphatic diisocyanates, araliphatic diisocyanates, and alicyclic diisocyanates.

  Examples of the aromatic diisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6- Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-triphenyl And methane triisocyanate.

Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2 4,4-trimethylhexamethylene diisocyanate and the like.
Examples of the araliphatic diisocyanate include 1,4-tetramethylxylylene diisocyanate and 1,3-tetramethylxylylene diisocyanate.

  Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate [also known as isophorone diisocyanate], 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, and 1,4-cyclohexane diisocyanate. , Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanate methyl) A cyclohexane etc. can be mentioned. In the present invention, these diisocyanate compounds (a) may be used alone or in combination.

In the present invention, the polyol compound (b) refers to a compound having a weight average molecular weight of 500 or more and containing two or more hydroxyl groups.
Specifically, for example, polyethylene oxide, polypropylene oxide, block copolymer or random copolymer of ethylene oxide / propylene oxide, polytetramethylene glycol, block copolymer of tetramethylene glycol and neopentyl glycol, or random copolymer Polyether polyols such as coalescence;
Polyester polyols which are condensates of polyhydric alcohols or polyether polyols with polybasic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid;
Polycarbonate polyols obtained by reaction of glycol or bisphenol with a carbonic acid ester or reaction of phosgene with glycol or bisphenol in the presence of alkali;
Examples thereof include caprolactone-modified polyol such as caprolactone-modified polytetramethylene polyol, polyolefin polyol, polybutadiene polyol such as hydrogenated polybutadiene polyol, and polyol such as silicone polyol.
In the present invention, these polyol compounds (b) may be used alone or in combination of two or more.
In the present invention, a diol compound is preferably used as the polyol compound (b).

  In the present invention, the carboxylic acid compound (c) having two hydroxyl groups is not particularly limited as long as it is a compound having two hydroxyl groups and one or more carboxyl groups in the molecule, but for example, dimethylolbutanoic acid , Dimethylolpropionic acid, and derivatives thereof (caprolactone adduct, ethylene oxide adduct, propylene oxide adduct, etc.), 3-hydroxysalicylic acid, 4-hydroxysalicylic acid, 5-hydroxysalicylic acid, 2-carboxy-1,4- Examples include cyclohexanedimethanol. Among these, dimethylolbutanoic acid and dimethylolpropionic acid are preferable in the present invention in that the concentration of carboxyl groups in the resin can be increased. In the present invention, these carboxylic acid compounds (c) may be used alone or in combination.

  In the present invention, examples of the (meth) acrylate (e) having one epoxy group or oxetane group in the molecule include glycidyl (meth) acrylate, glycidyl cinnamic acid, 4-hydroxybutyl (meth) acrylate glycidyl ether, and oxetanyl. (Meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and the like.

  In the present invention, examples of the compound (g) having one hydroxyl group and one or more ethylenically unsaturated groups in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Examples include hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2-hydroxy-3-phenylpropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like.

  In the present invention, examples of the polybasic acid anhydride (h) having two acid anhydride groups in the molecule include pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl. Ether tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, diphenyl sulfide tetracarboxylic dianhydride, oxydiphthalic dianhydride, butanetetracarboxylic dianhydride, tetracarboxylic And acid dianhydrides, hexacarboxylic dianhydrides, perylene tetracarboxylic dianhydrides, and the like.

  The polybasic acid anhydride (j) having one acid anhydride group of the present invention is methyltetrahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylpentahydrophthalic anhydride, Examples thereof include acid anhydrides having an alicyclic structure or an aromatic ring structure such as methyltrihydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride, het acid anhydride, and tetrabromophthalic anhydride. Other acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, butyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecyl succinic anhydride, butyl maleic anhydride, pentyl malein Acid anhydride, hexyl maleic anhydride, octyl maleic anhydride, decyl maleic anhydride, dodecyl maleic anhydride, butyl glutamic anhydride, hexyl glutamic anhydride, heptyl glutamic anhydride, octyl glutamic anhydride, decyl glutamic acid Anhydride, dodecylglutamic acid anhydride, etc. are mentioned. In this invention, the polybasic acid anhydride (j) which has one acid anhydride group may be used individually by 1 type, and may use 2 or more types together.

  The acid value of the urethane resin (A) of the present invention is preferably 10 to 200 mgKOH / g, more preferably 30 to 150 mgKOH / g. When the acid value is less than 10 mgKOH / g, sufficient developability cannot be obtained. For example, the film may remain as a residue in a portion where the film is dissolved and removed during development. Moreover, when an acid value exceeds 200 mgKOH / g, the solubility of the coating film with respect to a developing solution becomes high, and even the part which wants to make it photocure and leave as a pattern is developed, and there exists a possibility that the shape of a pattern may deteriorate. The acid value is measured by potentiometric titration according to JIS K 2501.

  The ethylenically unsaturated group equivalent of the urethane resin (A) of the present invention is preferably 200 to 3000 g / eq, more preferably 300 to 2000 g / eq. When the ethylenically unsaturated group equivalent is less than 200 g / eq, the photosensitivity is excessive, the film is dissolved at the time of development, and the portion desired to be removed is cured and a good pattern shape may not be obtained. If the ethylenically unsaturated group equivalent exceeds 3000 g / eq, the photosensitivity is inferior and the portion to be cured is not sufficiently cured, and the pattern is dissolved during development, and a good pattern shape may not be obtained. In addition, the ethylenically unsaturated group equivalent is the molecular weight of the resin divided by the number of ethylenically unsaturated groups per molecule, and the molecular weight of the resin relative to one ethylenically unsaturated group, that is, in the resin Represents the reciprocal of the ethylenically unsaturated group concentration.

  It is preferable that the weight average molecular weights of the urethane resin (A) of this invention are 1000-100000, More preferably, it is 3000-60000. When the weight average molecular weight is less than 1000, sufficient solder heat resistance and flexibility may not be obtained. On the other hand, when the weight average molecular weight exceeds 100,000, the soldering heat resistance is excellent, but the developability may be deteriorated, and the viscosity and handling during coating may be deteriorated. The weight average molecular weight (Mw) is measured using a standard polystyrene calibration curve by GPC (gel permeation chromatography). The measurement conditions for GPC are as follows. Two measuring machines “HPC-8020” (manufactured by Tosoh), column “LF-604” (manufactured by Showa Denko: GPC column for rapid analysis: 6 mm ID × 150 mm size) connected in series, solvent: tetrahydrofuran, flow rate 0.6 ml / min Column temperature 40 ° C.

  The phenoxyphosphazene compound (B) of the general formula (1) of the present invention will be described.

General formula (1)

(However, n is an integer of 3 to 25, and one of R1 and R2 is CN and the other is H, or both are CN. The ratio of cyanophenoxy group in the above compound is phenoxy group and cyano. 2 to 98 mol % of the total of phenoxy groups.)

  The phenoxyphosphazene compound (B) must contain a cyanophenoxy group, and can further contain a phenoxy group. The cyanophenoxy group refers to a functional group represented by the following formula (2), and the phenoxy group refers to a functional group represented by the following formula (3). The ratio of the cyanophenoxy group in the phenoxyphosphazene compound of the general formula (1) is preferably 2 to 98% of the total of the phenoxy group and the cyanophenoxy group. If it is less than 2% or more than 98%, it is difficult to achieve both high flame retardancy and bleed-out resistance.

Formula (2)

Formula (3)

Specific examples of the phenoxyphosphazene compound represented by the general formula (1) are as follows.

Formula (4)

Formula (5)

Formula (6)

  As a flame retardant for a resin composition using a urethane resin (A), a conventional phenoxyphosphazene compound having only a phenoxy group (R1 and R2 are H in general formula (1), for example, Otsuka Chemical: SPB-100) is flame retardant. When used up to an amount that exhibits sexiness, the flame retardant bleed out. In addition, when a phenoxyphosphazene compound having a hydroxyphenoxy group and a phenoxy group (for example, Otsuka Chemical: SPH-100) is added up to an amount that exhibits flame retardancy, the problem of bleeding out does not occur, but the alkali developability is extremely low. There was a problem of becoming. However, by using the phenoxyphosphazene compound (B) containing a cyanophenoxy group according to the present invention, sufficient flexibility and folding resistance, developability and soldering heat resistance that can realize high-precision patterning, circuit protective layer As a result, it has been found that a cured product satisfying all the physical properties such as electrical insulation and chemical resistance, as well as non-halogen flame resistance, bleed-out resistance and alkali developability can be obtained.

  The phenoxyphosphazene compound (B) is preferably contained in an amount of 10 to 50 parts by weight, more preferably 30 to 45 parts by weight, in 100 parts by weight of the nonvolatile content of the flame retardant resin composition. When the amount is less than 10 parts by weight, sufficient flame retardancy may not be obtained. On the other hand, when the blending amount exceeds 50 parts by weight, there is a possibility that the solubility of the coating film in the developer is deteriorated and the solder heat resistance is deteriorated. In addition, the non volatile matter in this invention removes a solvent from a flame retardant resin composition.

  The photopolymerization initiator (C) of the present invention is not particularly limited as long as it is a known one, and examples thereof include monocarbonyl compounds, dicarbonyl compounds, acetophenone compounds, benzoin ether compounds, acylphosphine oxide compounds, aminocarbonyl compounds and the like. Can be used.

Specifically, monocarbonyl compounds include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 4- (4-methylphenylthio) phenyl. -Enetanone, 3,3'-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, 3,3'4,4'- Tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N, N-trimethylbenzenemethammonium chloride, 2-hydroxy-3- (4-benzoyl-phenoxy) -N, N, N-trimethyl-1- Propanamine hydrochloride, 4-benzoyl-N, N-dimethyl-n- [2 (1-Oxo-2-propenyloxyethyl)] metaammonium bromide, 2- / 4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone 2-hydroxy-3- (3,4-dimethyl-9-oxo-9Hthioxanthone-2-yloxy))-N, N, N-trimethyl-1-propanamine hydrochloride, benzoylmethylene-3-methylnaphtho , 2-d) thiazoline and the like.

  Examples of the dicarbonyl compound include 1,7,7-trimethyl-bicyclo [2.1.1] heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzene. Examples include acetate and 4-phenylbenzyl.

  Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- ( 4-Isopropylphenyl) 2-hydroxy-di-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one polymerization , Diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyla No-1- (4-morpholino-phenyl) butan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2- Morpholino-propanonyl) -9-butylcarbazole and the like.

  Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide.

  Examples of aminocarbonyl compounds include methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-nbutoxyethyl-4- (dimethylamino) benzoate, isoamyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethyl benzoate, 4,4′-bis-4-dimethylaminobenzophenone, 4,4′-bis-4-diethylaminobenzophenone, 2,5′-bis- (4-diethylaminobenzal) cyclopenta Non etc. are mentioned. In particular, in the present invention, when 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and thioxanthones are used in combination, the photosensitivity is extremely low but the cost is very low. This is particularly preferable. These are not limited to the above compounds, and can be used alone or in combination of two or more. Although there is no restriction | limiting in the usage-amount, it is preferable to add in the range of 1-20 weight part with respect to 100 weight part of urethane resin (A). Moreover, a well-known organic amine can also be added as a sensitizer.

  Next, the ethylenically unsaturated group-containing compound (D) other than (A) of the present invention will be described. The compound (D) is not particularly limited as long as it has an ethylenically unsaturated double bond in the structure. Examples include alkyl (meth) acrylates, alkylene glycol (meth) acrylates, compounds having a carboxyl group and an ethylenically unsaturated group, ethylenically unsaturated compounds having a hydroxyl group, and nitrogen-containing ethylenically unsaturated compounds. Moreover, a monofunctional and polyfunctional compound can be used suitably. From the viewpoint of photocurability and hard coat properties of the coating film, polyfunctional ones are preferred. Although there is no restriction | limiting in the usage-amount of the said ethylenically unsaturated group containing compound (D), It is preferable to add in 2-30 weight part with respect to 100 weight part of urethane resin (A).

  Specific examples of the monofunctional compound include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth). Acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) Acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meta When there are alkyl (meth) acrylates having 1 to 22 carbon atoms such as acrylate, nonadecyl (meth) acrylate, icosyl (meth) acrylate, heicosyl (meth) acrylate, docosyl (meth) acrylate, etc. Is preferably an alkyl group-containing (meth) acrylate having an alkyl group having 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms.

Examples of the alkylene glycol (meth) acrylate include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, and polyethylene glycol. Mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, etc. And a mono (meth) acrylate having a polyoxyalkylene chain;
Methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate , N-butoxytetraethylene glycol (meth) acrylate, n-pentoxytetraethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxytetrapropylene glycol (meth) acrylate, ethoxytetrapropylene glycol (meth) acrylate , Propoxytetrapropylene glycol (meth) acrylate, n-butoxy Tetrapropylene glycol (meth) acrylate, n-pentoxytetrapropylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, etc. Mono (meth) acrylate having an alkoxy group and a polyoxyalkylene chain;
Phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, Examples thereof include polyoxyalkylene (meth) acrylates having a phenoxy or aryloxy group at the terminal, such as phenoxytetrapropylene glycol (meth) acrylate.

  Examples of the compound having a carboxyl group and an ethylenically unsaturated group include maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, phthalic acid β- (meth) acryloxyethyl mono Ester, isophthalic acid β- (meth) acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, Cinnamic acid is mentioned.

  Examples of the ethylenically unsaturated compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxy Examples include vinylbenzene.

Examples of the nitrogen-containing ethylenically unsaturated compound include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, and N-propoxymethyl- Monoalkylol (meth) acrylamide such as (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, N, N-di (methylol) acrylamide, N-methylol-N -Methoxymethyl (meth) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethyl methacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxy Methylmetaa Rilamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) meta Acrylamide unsaturated compounds such as acrylamide, N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) methacrylamide and the like, and dimethylaminoethyl (meth) acrylate , diethylaminoethyl (meth) acrylate methyl ethyl aminoethyl (meth) acrylate, dimethylamino styrene, the unsaturated compound and counterions having a dialkylamino group such as a diethylamino styrene Cl ^-, Br ^{-, -} halogen ion or QSO ^3- such: include quaternary ammonium salts of dialkylamino group-containing unsaturated compound having a (Q alkyl group having 1 to 12 carbon atoms).

Further, other unsaturated compounds include perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2 -Perfluorooctylethyl (meth) acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) ) Acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate, etc. Perfluoroalkyl (meth) acrylates having Kill group;
Perfluoroalkyl group-containing vinyl monomers such as perfluoroalkylalkylenes such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene;
Alkoxysilyl group-containing vinyl compounds such as vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane and derivatives thereof;
Examples thereof include glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate, and these groups can be used alone or in combination.

Other fatty acid vinyl compounds include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate, vinyl stearate, etc .; alkyl vinyl ether compounds such as butyl vinyl ether, ethyl vinyl ether, etc. ;
As the α-olefin compound, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and the like;
Other vinyl compounds include allyl compounds such as allyl acetate, allyl alcohol, allylbenzene, and allyl cyanide, vinyl cyanide, vinylcyclohexane, vinyl methyl ketone, styrene, α-methylstyrene, 2-methylstyrene, chlorostyrene, and the like. ,
As an ethynyl compound, acetylene, ethynylbenzene, ethynyltoluene, 1-ethynyl-1-cyclohexanol, etc.
Can be used.

Next, a polyfunctional compound having two or more ethylenically unsaturated groups will be described.
First, an aliphatic compound is illustrated among the compounds which have an ethylenically unsaturated group. Specifically, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Bis (acryloxy neopentyl glycol) adipate, bis (methacryloxy neopentyl glycol) adipate, epichlorohydrin modified 1,6-hexanediol di (meth) acrylate: Nippon Kayaku Kayrad R-167, hydroxypivalate neopentyl glycol di (Meth) acrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol di (meth) acrylate: Nippon Kayaku Kayrad HX series alkyl type (meth) acrylate, ethylene glycol di (meth) acrylate , Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, epichlorohydrin modified ethylene glycol di (meth) acrylate: Nagase Sangyo Denacol DA (M) -811, epichlorohydrin modified diethylene glycol di (meth) acrylate: Nagase Sangyo Denacol DA (M) -851, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate , Tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin modified proleng Cold di (meth) acrylate: alkylene glycol type (meth) acrylate such as Nagase Sangyo Denacol DA (M) -911, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, neopentyl glycol modified trimethylolpropane Di (meth) acrylate: Nippon Kayaku Kayrad R-604, ethylene oxide modified trimethylolpropane tri (meth) acrylate: Sartomer SR-454, propylene oxide modified trimethylolpropane tri (meth) acrylate: Nippon Kayaku TPA- 310, epichlorohydrin-modified trimethylolpropane tri (meth) acrylate: trimethylolpropane type (meth) acrylate such as Nagase Sangyo DA (M) -321, pentae Rithritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate: Toagosei Aronix M-233, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta ( (Meth) acrylates, alkyl-modified dipentaerythritol poly (meth) acrylates: Kaprorad-modified dipentaerythritol poly (meth) acrylates such as Nippon Kayaku Kayrad D-310, 320, 330, etc .: Nippon Kayaku Kayrad DPCA-20 , 30, 60, 120, etc. Pentaerythritol type (meth) acrylate, glycerol di (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate Nagase Sangyo Denacol DA (M) -314, glycerol type (meth) acrylate such as triglycerol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, tricyclopentanyl di (meth) acrylate, cyclohexyl Di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate: cycloaliphatic (meth) acrylate such as Sanyo Kokusaku Pulp CAM-200, tris (acryloxyethyl) isocyanurate: Toa Gosei Aronix M-315, Tris (methacrylic) Isocyanurate type (meth) acrylates such as (Roxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (methacryloxyethyl) isocyanurate, etc. It is.

  Of the compounds having an ethylenically unsaturated group, aromatic compounds are exemplified. For example, diquinone or poly (meth) acrylate compounds such as hydroquinone, resorcin, catechol, pyrogallol, bisphenol A di (meth) acrylate, ethi (propi) lene oxide modified bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate Ethi (propi) lene oxide modified bisphenol F di (meth) acrylate, bisphenol S di (meth) acrylate, Ethi (propiylene oxide modified bisphenol S di (meth) acrylate, epichlorohydrin modified phthalic acid di (meth) acrylate, etc. (Meth) acrylate compounds having aromatic groups, tetrachlorobisphenol S ethyl (prop) ylene oxide modified di (meth) acrylate, tetrabromobisphenol S ethyl (propi) Such as styrenes and (meth) acrylate compound having an aromatic group substituted by a halogen atom with N'okishido modified di (meth) chlorine or atomic weight, such as acrylate.

  Furthermore, polyfunctional (meth) acrylates such as urethane (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) acrylate can be suitably used from the viewpoints of coating film strength and scratch resistance. Epoxy (meth) acrylate is obtained by esterifying an epoxy group of an epoxy resin with (meth) acrylic acid and converting the functional group to (meth) acrylate, and (meth) acrylic acid adduct to bisphenol A type epoxy resin. And (meth) acrylic acid adducts to novolac epoxy resins. Urethane (meth) acrylates are, for example, those obtained by reacting diisocyanates with (meth) acrylates having a hydroxyl group, and isocyanate group-containing urethane prepolymers obtained by reacting polyols and polyisocyanates under conditions of excess isocyanate groups. Some are obtained by reacting polymers with (meth) acrylates having a hydroxyl group. Alternatively, a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under hydroxyl-excess conditions can be obtained by reacting with a (meth) acrylate having an isocyanate group. The following can be illustrated as a commercial item.

Toa Gosei Co., Ltd .: Aronix M-400, Aronix M-402, Aronix M-310, Aronix M-408, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060;
Osaka Organic Chemical Industry Co., Ltd .: Biscote # 400;
Kayaku Sartomer Co., Ltd .: SR-295;
Made by Daicel UCB Corporation: DPHA, EBeCryl 220, EBeCryl 1290K, EBeCryl 5129, EBeCryl 2220, EBeCryl 6602;
Shin-Nakamura Chemical Co., Ltd .: NK Ester A-TMMT, NK Oligo EA-1020, NK Oligo EMA-1020, NK Oligo EA-6310, NK Oligo EA-6320, NK Oligo EA-6340, NK Oligo MA-6, NK oligo U-4HA, NK oligo U-6HA, NK oligo U-324A;
Manufactured by BASF: LAromerEA81;
San Nopco Co., Ltd .: Photomer 3016;
Arakawa Chemical Industries, Ltd .: beam set 371, beam set 575, beam set 577, beam set 700, beam set 710;
Manufactured by Negami Kogyo Co., Ltd .: Art Resin UN-3320HA, Art Resin UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN-9000H, Art Resin UN-901T, Art Resin HDP, Art Resin HDP- 3, Art Resin H61;
Nippon Synthetic Chemical Industry Co., Ltd .: Purple light UV-7600B, Purple light UV-7610B, Purple light UV-7620EA, Purple light UV-7630B, Purple light UV-1400B, Purple light UV-1700B, Purple light UV-6300B;
Kyoeisha Chemical Co., Ltd .: Light acrylate PE-4A, Light acrylate DPE-6A, UA-306H, UA-306T, UA-306I;
Nippon Kayaku Co., Ltd .: KAYARAD DPHA, KAYARAD DPHA2C, KAYARAD DPHA-40H, KAYARAD D-310, KAYARAD D-330, SR-35;
Etc.

  The flame retardant component (E) of the present invention will be described. Specifically, for example, melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium amidophosphate, ammonium polyphosphate, carbamate phosphate, carbamate polyphosphate, etc. Phosphate compounds and polyphosphate compounds, red phosphorus, organophosphate compounds, phosphazene compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, phosphoramide compounds and other phosphorus flame retardants, melamine, Triazine compounds such as melam, melem, melon, melamine cyanurate, cyanuric acid compounds, isocyanuric acid compounds, triazole compounds, tetrazole compounds, diazo compounds, nitrogen flame retardants such as urea, silane Silicon flame retardants such as compounds, metal hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide, tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, Examples thereof include inorganic flame retardants such as molybdenum oxide, antimony oxide, nickel oxide, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, and hydrated glass. In the present invention, non-halogen flame retardants such as phosphorus flame retardants and nitrogen flame retardants can be used in combination with the phenoxyphosphazene compound (B) to the extent that they do not affect various physical properties.

When adding the above phosphorus flame retardant, the total phosphorus concentration of the phenoxyphosphazene compound (B) and the phosphorus flame retardant is about 1.5 to 6% in the total nonvolatile content of the flame retardant resin composition. It is preferable to mix, and more preferably the total phosphorus concentration is 3 to 5%.
Moreover, when mix | blending the said nitrogen-type or inorganic type flame retardant, it is preferable that it is 10-50 weight part with respect to 100 weight part of urethane resins (A).

  The thermosetting component (F) of this invention is demonstrated. The thermosetting component (F) is not particularly limited as long as it has two or more functional groups capable of reacting with the functional groups contained in the urethane resin (A). In the present invention, the functional group that reacts with the thermosetting component (F) is preferably a hydroxyl group and / or a carboxyl group in the urethane resin (A). Specific examples of the thermosetting component (F) include polyisocyanate compounds, amino resins, phenol resins, and polyfunctional polycarboxylic acid anhydrides.

  The polyisocyanate compound is not particularly limited as long as it is a compound having a plurality of isocyanate groups in the molecule. Examples of polyisocyanate compounds include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane trisene. Polyisocyanate compounds such as isocyanate and polymethylene polyphenyl isocyanate, adducts of these polyisocyanate compounds and polyol compounds such as trimethylolpropane, burettes and isocyanurates of these polyisocyanate compounds, and further these polyisocyanate compounds Known polyether polyols and polymers Ester polyols, acrylic polyols, polybutadiene polyols, adducts, etc. and polyisoprene polyol and the like.

  Examples of amino resins and phenol resins include addition compounds of urea, melamine, benzoguanamine, phenol, cresols, bisphenols, and the like with formaldehyde, or partial condensates thereof.

  The polyfunctional polycarboxylic acid anhydride is a compound having two or more carboxylic acid anhydride groups and is not particularly limited, but tetracarboxylic dianhydride, hexacarboxylic dianhydride, hexacarboxylic dianhydride And polyvalent carboxylic acid anhydrides such as maleic anhydride copolymer resins. In addition, polycarboxylic acid, polycarboxylic acid ester, polycarboxylic acid half ester, and the like that can be converted into anhydrides via a dehydration reaction during the reaction are compounds having two or more carboxylic acid anhydride groups in the present invention. included.

  More specifically, as tetracarboxylic dianhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, Diphenyl sulfide tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, "Ricacid TMTA-C", "Ricacid MTA-" manufactured by Shin Nippon Chemical Co., Ltd. 10 ”,“ Licacid MTA-15 ”,“ Licacid TMEG series ”,“ Licacid TDA ”, and the like.

  Examples of maleic anhydride copolymer resins include SMA resin series manufactured by Sartomer, GSM series manufactured by Gifu Shellac Co., Ltd., styrene-maleic anhydride copolymer resins, p-phenylstyrene-maleic anhydride copolymer resins, polyethylene- Α-olefin-maleic anhydride copolymer resin such as maleic anhydride, “VEMA” (copolymer of methyl vinyl ether and maleic anhydride) manufactured by Daicel Chemical Industries, Ltd., and acrylic anhydride modified maleic anhydride (“Aurolen series”) ": Nippon Paper Chemical Co., Ltd.), maleic anhydride copolymer acrylic resin, and the like.

  Examples of the thermosetting component (F) having at least two functional groups capable of reacting with a carboxyl group include compounds (k) having two or more epoxy groups or oxetane groups, polyfunctional vinyl ether compounds, high molecular weight polycarbodiimides, Examples include aziridine compounds. Among these, the compound (k) having two or more epoxy groups or oxetane groups is very preferable from the viewpoint of curing speed and durability of the cured product.

  The compound (k) having two or more epoxy groups or oxetane groups may be a compound having two or more epoxy groups or oxetane groups in the molecule, and is not particularly limited. Specific examples of the compound having an epoxy group as the compound (k) include, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type epoxy. Resin, bisphenol F / epichlorohydrin type epoxy resin, biphenol / epichlorohydrin type epoxy resin, polyglycidyl ether of glycerin / epichlorohydrin adduct, phenol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin Resin, naphthalene type epoxy resin, ethyleneglycol / epichlorohydrin adduct polyglycidyl ether, pentaerythritol polyglycidyl ether, reso Sinor diglycidyl ether, polybutadiene diglycidyl ether, hydroquinone diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A Diglycidyl ether, polypropylene glycol diglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-di Examples thereof include glycidyl aniline and N, N-diglycidyl toluidine.

  Further, as the compound (k) having two or more epoxy groups or oxetane groups, specifically, as a compound having an oxetane group, for example, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] Biphenyl, esterified product of (2-ethyl-2-oxetanyl) ethanol and terephthalic acid, etherified product of (2-ethyl-2-oxetanyl) ethanol and phenol novolac resin, (2-ethyl-2-oxetanyl) ethanol and Examples include esterified products with polyvalent carboxylic acid compounds. Among these compounds, phenol novolac epoxy resin, cresol novolac epoxy resin, dicyclopentadiene epoxy resin, biphenol / epichlorohydrin epoxy resin, 4,4′-bis [(3-ethyl-3-oxetanyl) ) Methoxymethyl] biphenyl, esterified product of (2-ethyl-2-oxetanyl) ethanol and terephthalic acid are preferred in the present invention in terms of thermosetting and durability of the cured coating film.

  Specific examples of the polyfunctional vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, and tripropylene glycol. Divinyl ether, neopentyl glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, glycerin divinyl ether, trimethylolpropane divinyl ether, 1,4-dihydroxylcyclohexane divinyl ether, 1,4 -Dihydroxymethylcyclohexanedivinyl ether, Hyde Quinone divinyl ether, ethylene oxide modified hydroquinone divinyl ether, ethylene oxide modified resorcin divinyl ether, ethylene oxide modified bisphenol A divinyl ether, ethylene oxide modified bisphenol S divinyl ether, glycerin trivinyl ether, sorbitol tetravinyl ether, trimethylolpropane trivinyl ether, pentaerythritol Examples include trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol hexavinyl ether, dipentaerythritol polyvinyl ether, ditrimethylolpropane tetravinyl ether, and ditrimethylolpropane polyvinyl ether.

  Examples of the high molecular weight polycarbodiimides include Nisshinbo's Carbodilite series. Among these, Carbodilite V-01, 03, 05, 07, and 09 are preferable because of excellent compatibility with organic solvents.

Examples of the aziridine compound include 2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], 4,4′-bis (ethyleneiminocarbonylamino) diphenylmethane, and the like.
As other thermosetting components (F), benzoxazine compounds, benzocyclobutene compounds, maleimide compounds, nadiimide compounds, allyl nadiimide compounds, melamine compounds, guanamine compounds, blocked isocyanate compounds and the like can be used. Either can be used effectively. These photopolymerizable groups, functional groups capable of reacting with carboxyl groups, and compounds having functional groups capable of reacting with hydroxyl groups can improve the heat resistance of the coating film after curing, and are therefore used more effectively. be able to. These thermosetting components (F) may be used alone or in combination of two or more.

  The amount of the thermosetting component (F) used may be determined in consideration of the application of the flame retardant resin composition, and is not particularly limited, but with respect to 100 parts by weight of the urethane resin (A), More preferably within the range of 0.1 to 100 parts by weight, and even more preferably within the range of 0.5 to 80 parts by weight. Thereby, since the crosslinking density of a flame-retardant resin composition can be adjusted to a moderate value, the various physical properties of a flame-retardant resin composition can be improved further. When the usage-amount of a thermosetting component (F) is less than 0.1 weight part, a crosslinking density becomes low too much and the cohesion force and durability of hardened | cured material may be insufficient. Moreover, when there are more usage-amounts than 100 weight part, a crosslinking density becomes high too much, As a result, the folding resistance and flexibility of hardened | cured material may fall.

  Next, the thermal curing aid (G) of the present invention is a compound that contributes directly or catalytically to the curing reaction during thermal curing. The thermosetting aid (G) is appropriately selected depending on the thermosetting component (F) used. The curing conditions for the carboxyl group-containing photosensitive urethane resin (A) and the thermosetting component (F) can be appropriately selected depending on the thermosetting component (F) and the thermosetting auxiliary agent (G) used.

Specifically, as the thermosetting aid (G), for example,
Tertiary amines such as triethylamine, tributylamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N-methylpiperazine and / or salts thereof;
2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-dicyano-6- [2-methylimidazolyl-1] -Imidazoles such as ethyl-S-triazine and / or salts thereof;
1,5-diazabicyclo [5,4,0] -7-undecane, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,4-diabicyclo [2,2,2,] octane, etc. Diazabicyclo compounds;
Phosphines such as tributylphosphine, triphenylphosphine, tris (dimethoxyphenyl) phosphine, tris (hydroxypropyl) phosphine, tris (cyanoethyl) phosphine;
Phosphonium salts such as tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium tetraphenylborate, methyltricyanoethylphosphonium tetraphenylborate;
In addition, dicyandiamide, carboxylic acid hydrazide, and the like can be cited as compounds that are catalytic and that directly contribute to the curing reaction. Examples of the carboxylic acid hydrazide include succinic acid hydrazide and adipic acid hydrazide.

  In the present invention, when an epoxy compound is used as the thermosetting component (F), the use of dicyandiamide, carboxylic acid hydrazide, imidazoles, and diazabicyclo compounds as the thermosetting aid (G) can more efficiently perform the thermosetting reaction. It is preferable because it progresses and the resistance of the coating film is excellent.

  The flame retardant resin composition of the present invention may contain a resin other than the above-described (A) as necessary. Examples of resins other than (A) include acrylic resins, polyester resins, urethane resins, urea resins, urethane urea resins, epoxy resins, polyamide resins, and polyimide resins. From the viewpoint of developability, those containing a carboxyl group are preferable, and those having excellent compatibility with (A) are preferable. In the present invention, when a resin other than (A) is contained, it can be used singly or in combination.

  In addition, the flame retardant resin composition of the present invention is an optional component as long as the purpose is not impaired, and further includes a solvent, a dye, a pigment, an antioxidant, a polymerization inhibitor, an antifoaming agent, a leveling agent, a humectant, and a viscosity. An adjusting agent, preservative, antibacterial agent, antistatic agent, antiblocking agent, coupling agent, compatibilizing agent, ultraviolet absorber, infrared absorber, electromagnetic wave shielding agent, filler and the like can be added.

  Since the flame-retardant resin composition of the present invention is characterized by excellent alkali developability when used as a protective layer for a printed wiring board, it is used in a coating film forming process including photocuring, alkali development, and postcure. Can be suitably used. Furthermore, since it is excellent in coating-film resistance and is excellent in flexibility and bendability at the same time, it can be suitably used particularly for solder resist inks for flexible printed wiring boards and photosensitive coverlay films.

  In the flame-retardant resin composition of the present invention, metals, ceramics, glass, plastics, wood, slate and the like can be used as the substrate, and are not particularly limited. Specific types of plastic include polyester, polyolefin, polycarbonate, polystyrene, polymethyl methacrylate, triacetyl cellulose resin, ABS resin, polyamide, epoxy resin, melamine resin, and the like. Examples of the shape of the substrate include a film sheet, a plate-like panel, a lens shape, a disk shape, and a fiber shape, but are not particularly limited.

  The flame-retardant resin composition of the present invention is applied to a carrier film such as a plastic film to a uniform thickness by a known coating apparatus such as a comma coater, a blade coater, a roll coater, a die coater, a lip coater, etc. It can dry and volatilize a solvent and can be set as a dry film. In that case, in order to protect the surface, it is preferable to bond together a protective film. Although there is no restriction | limiting in particular in the thickness of the said dry film, Usually, it selects suitably in the range of 10-100 micrometers.

The flame-retardant resin composition of the present invention can be cured by irradiation with active energy rays to obtain a cured product. The active energy ray means an electromagnetic wave having a wavelength capable of reacting a photopolymerization initiator or an ethylenically unsaturated group in the flame retardant resin composition, and includes electron beam, ultraviolet ray, radiation, γ ray and the like. As an irradiation device, for example, as an ultraviolet irradiation device, as a light source, for example, a metal halide lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an electrodeless lamp, a xenon lamp, a semiconductor laser, an Ar laser, a carbon arc lamp, a tungsten lamp And pulse UV lamps. Examples of the electron beam irradiation apparatus include a thermionic emission gun, a field emission gun, and the like. Dose, although in the case of ultraviolet can be suitably set within a range of 5~2000mJ / cm ^2, a range of administrative steps likely 50~1000mJ / cm ² is more preferable.
In the case of an electron beam, 20 to 2000 KeV is preferable. Further, it is possible to use ultraviolet rays or electron beams and heat by infrared rays, far infrared rays, hot air, high frequency heating, or the like.

  The method of using the flame retardant resin composition of the present invention is, for example, forming a flame retardant resin composition as a protective layer on a conductive circuit formed on an insulating layer such as a polyimide film or a glass epoxy substrate. After forming a desired pattern on the protective layer through an exposure / development process, the cured layer is formed by heating at 100 ° C. to 200 ° C. for about 30 minutes to 2 hours as a post cure. In addition, in order to improve solder heat resistance and the like, it is possible to further irradiate active energy rays after the post cure. The flame-retardant resin composition of the present invention is preferably used in applications such as printed wiring boards, but it is flexible that requires flexibility and the like because of its excellent adhesion, flexibility, and folding resistance. More preferably, it is used as a printed wiring board.

  EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight”.

[Production Example 1]
To a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, PTG850 sn (Hodogaya Chemical Co., Ltd .: polytetramethylene glycol, weight average molecular weight = about 850, hydroxyl value = 129 mgKOH / g ) 55 parts, dimethylol butanoic acid (Nippon Kasei Co., Ltd.) 178 parts, and 375 parts of cyclohexanone as a solvent were charged, heated to 60 ° C. with stirring under a nitrogen stream, and uniformly dissolved. Subsequently, 267 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 10,000, a molecular weight distribution of 2.03, and an actually measured acid value of resin solids of 138 mgKOH / g.

  Next, the nitrogen from the nitrogen introduction tube was stopped in this flask and switched to introduction of dry air. While stirring, 85 parts of glycidyl methacrylate, 35 parts of butyl glycidyl ether, 6 parts of dimethylbenzylamine, and hydroquinone 0 as a polymerization inhibitor were added. 3 parts were added and reacted at 90 ° C. for 8 hours. A small amount of sampling was performed after cooling, and cyclohexanone was further added to adjust the solid content to 50.0% to obtain a urethane resin (A-1) solution. The ethylenically unsaturated group equivalent of resin solids by this design was 1303 g / eq, the weight average molecular weight in terms of polystyrene was 13600, the molecular weight distribution was 2.50, and the acid value of the resin solids by measurement was 33 mgKOH / g. .

[Production Example 2]
To a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, PTG850 sn (Hodogaya Chemical Co., Ltd .: polytetramethylene glycol, weight average molecular weight = about 850, hydroxyl value = 129 mgKOH / g ) 55 parts, dimethylol butanoic acid (Nippon Kasei Co., Ltd.) 178 parts, and 375 parts of cyclohexanone as a solvent were charged, heated to 60 ° C. with stirring under a nitrogen stream, and uniformly dissolved. Subsequently, 267 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 10,000, a molecular weight distribution of 2.03, and an actually measured acid value of resin solids of 138 mgKOH / g.

  Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, and 85 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. The reaction was continued for 8 hours at 90 ° C. After cooling, a small amount of sampling was performed, and cyclohexanone was further added to adjust the solid content to 50.0% to obtain a urethane resin (A-2) solution. The ethylenically unsaturated group equivalent of the resin solid content by this design was 1156 g / eq, the weight average molecular weight in terms of polystyrene was 12800, the molecular weight distribution was 2.25, and the acid value of the resin solid content by actual measurement was 68 mgKOH / g. .

[Production Example 3]
In a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, 212 parts of PTG850 (Hodogaya Chemical Co., Ltd .: polytetramethylene glycol, hydroxyl value = 129 mgKOH / g), ethylene glycol 75 Parts, pyromellitic anhydride (manufactured by Daicel Chemical Industries, Ltd.) 159 parts, dimethylbenzylamine 2 parts, cyclohexanone 375 parts as a solvent, and stirred for 10 hours at 100 ° C. with stirring in a nitrogen stream, Half-esterification reaction was performed. Subsequently, 54 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed, and the carboxyl group-containing urethane having a polystyrene-equivalent weight average molecular weight of 15200, a molecular weight distribution (weight average molecular weight / number average molecular weight) of 2.87, and an actually measured acid value of 170 mgKOH / g of resin solids. A prepolymer (d) was obtained.

  Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, 110 parts of glycidyl methacrylate, 50 parts of butyl glycidyl ether, 6 parts of dimethylbenzylamine with stirring, and hydroquinone 0 as a polymerization inhibitor. 3 parts were added and reacted at 90 ° C. for 8 hours. After cooling, a small amount of sampling is performed, and further, cyclohexanone is added to adjust the solid content to 50.0%, and the carboxyl group-containing photosensitive urethane resin (A-3) whose main skeleton is an acid anhydride-modified urethane skeleton A solution was obtained. The ethylenically unsaturated group equivalent of resin solids by this design was 852 g / eq, the weight average molecular weight in terms of polystyrene was 19,700, the molecular weight distribution was 3.26, and the acid value of resin solids by measurement was 32 mgKOH / g.

[Production Example 4]
In a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, 212 parts of PTG850 (Hodogaya Chemical Co., Ltd .: polytetramethylene glycol, hydroxyl value = 129 mgKOH / g), ethylene glycol 75 Parts, pyromellitic anhydride (manufactured by Daicel Chemical Industries, Ltd.) 159 parts, dimethylbenzylamine 2 parts, cyclohexanone 375 parts as a solvent, and stirred for 10 hours at 100 ° C. with stirring in a nitrogen stream, Half-esterification reaction was performed. Subsequently, 54 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed, and the carboxyl group-containing urethane having a polystyrene-equivalent weight average molecular weight of 15200, a molecular weight distribution (weight average molecular weight / number average molecular weight) of 2.87, and an actually measured acid value of 170 mgKOH / g of resin solids. A prepolymer (d) was obtained.

  Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, and 110 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. The reaction was continued for 8 hours at 90 ° C. After cooling, a small amount of sampling is performed, and further, cyclohexanone is added to adjust the solid content to 50.0%, and the carboxyl group-containing photosensitive urethane resin (A-4) whose main skeleton is an acid anhydride-modified urethane skeleton A solution was obtained. The ethylenically unsaturated group equivalent of the resin solid content by this design was 896 g / eq, the weight average molecular weight in terms of polystyrene was 18,800, the molecular weight distribution was 3.12, and the acid value of the resin solid content was 72 mgKOH / g as measured.

[Production Example 5]
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 106 parts of PTG850 (manufactured by Hodogaya Chemical Co., Ltd .: polytetramethylene glycol, hydroxyl value = 129 mgKOH / g), ethylene glycol 83 Parts, pyromellitic anhydride (manufactured by Daicel Chemical Industries, Ltd.) 159 parts, dimethylbenzylamine 2 parts, cyclohexanone 375 parts as a solvent, and stirred for 10 hours at 100 ° C. with stirring in a nitrogen stream, Half-esterification reaction was performed. Subsequently, 54 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed, and a carboxyl group-containing urethane having a polystyrene-equivalent weight average molecular weight of 13,000, a molecular weight distribution (weight average molecular weight / number average molecular weight) of 2.51, and an actually measured acid value of 210 mgKOH / g of resin solids. A prepolymer (d) was obtained.

  Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, 40 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. The reaction was continued for 8 hours at 90 ° C. After cooling, a small amount of sampling is performed, and cyclohexanone is further added to adjust the solid content to 50.0%, and the carboxyl group-containing photosensitive urethane resin (A-5) whose main skeleton is an acid anhydride-modified urethane skeleton A solution was obtained. The ethylenically unsaturated group equivalent of resin solids by this design was 1570 g / eq, the weight average molecular weight in terms of polystyrene was 15900, the molecular weight distribution was 3.01, and the acid value of the resin solids by measurement was 148 mgKOH / g.

[Production Example 6]
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet pipe, an inlet pipe, and a thermometer, 318 parts of polytetramethylene glycol (PTG1000SN: Hodogaya Chemical Co., Ltd .: hydroxyl value = 110 mgKOH / g, Mw = 1020) Then, 46 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 375 parts of cyclohexanone as a solvent were charged, and the temperature was raised to 60 ° C. with stirring in a nitrogen stream to dissolve the mixture uniformly. Subsequently, 136 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer solution having a polystyrene-equivalent weight average molecular weight of 19800 and an actually measured acid value of 35 mg KOH / g of the nonvolatile polymer content. Next, nitrogen from the nitrogen inlet tube of this flask was stopped, switching to introduction of dry air, 44 parts of glycidyl methacrylate, 5 parts of dimethylbenzylamine and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. The reaction was continued for 8 hours at 90 ° C. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing urethane prepolymer solution having a polystyrene-equivalent weight average molecular weight of 22,000 and an actually measured acid value of 3 mg KOH / g of the nonvolatile polymer content. Next, 31 parts of succinic anhydride was added to the flask, and the reaction was further continued for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, cyclohexanone was added to this solution to adjust the nonvolatile content to 50.0%. The urethane resin (A-6) having a carboxyl group and an ethylenically unsaturated group prepared according to this production example has an ethylenically unsaturated group equivalent of 1846 g / eq in non-volatile content, and a polystyrene equivalent weight average molecular weight of 23100. The actually measured acid value was 30 mgKOH / g.

[Production Example 7]
156 parts of polytetramethylene glycol (PTG1000SN: manufactured by Hodogaya Chemical Co., Ltd .: hydroxyl value = 110 mgKOH / g, Mw = 1020) in a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer Then, 129 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 375 parts of cyclohexanone as a solvent were charged, and the mixture was heated to 60 ° C. with stirring in a nitrogen stream, and dissolved uniformly. Subsequently, 215 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. A small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer solution having a polystyrene-equivalent weight average molecular weight of 13000 and an actually measured polymer non-volatile acid value of 98 mgKOH / g. Next, nitrogen from the nitrogen inlet tube of this flask was stopped, switching to introduction of dry air, and 111 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine, and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. The reaction was continued for 8 hours at 90 ° C. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing urethane prepolymer solution having a polystyrene-reduced weight average molecular weight of 14800 and an actually measured acid non-volatile content of 8 mgKOH / g. Next, 63 parts of succinic anhydride was added to the flask, and the reaction was further continued for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, cyclohexanone was added to this solution to adjust the nonvolatile content to 50.0%. The urethane resin (A-7) having a carboxyl group and an ethylenically unsaturated group prepared according to this production example has an ethylenically unsaturated group equivalent of 863 g / eq in non-volatile content, and a polystyrene equivalent weight average molecular weight of 15400. The actually measured acid value was 73 mgKOH / g.

[Production Example 8]
4 parts of polytetramethylene glycol (PTG1000SN: manufactured by Hodogaya Chemical Co., Ltd .: hydroxyl value = 110 mgKOH / g, Mw = 1020) was added to a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer. In addition, 201 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 375 parts of cyclohexanone as a solvent were charged, and the mixture was heated to 60 ° C. with stirring under a nitrogen stream and dissolved uniformly. Subsequently, 296 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer solution having a polystyrene-equivalent weight average molecular weight of 8900 and an actually measured polymer nonvolatile acid value of 152 mgKOH / g. Next, nitrogen from the nitrogen inlet tube of this flask was stopped, switched to introduction of dry air, 193 parts of glycidyl methacrylate, 7 parts of dimethylbenzylamine and 0.4 part of hydroquinone as a polymerization inhibitor were added while stirring. The reaction was continued for 8 hours at 90 ° C. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing urethane prepolymer solution having a polystyrene-equivalent weight average molecular weight of 9600 and an actually measured acid non-volatile content of 1 mgKOH / g. Next, 136 parts of succinic anhydride was added to the flask, and the reaction was further continued for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, cyclohexanone was added to this solution to adjust the nonvolatile content to 50.0%. The urethane resin (A-8) having a carboxyl group and an ethylenically unsaturated group prepared according to this production example has an ethylenically unsaturated group equivalent of 611 g / eq in nonvolatile content, and a weight average molecular weight in terms of polystyrene of 11000. The actually measured acid value was 92 mgKOH / g.

[Production Example 9]
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube and thermometer, 26 parts of polytetramethylene glycol (PTG1000SN: Hodogaya Chemical Co., Ltd .: hydroxyl value = 110 mgKOH / g, Mw = 1020) In addition, 387 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 382 parts of cyclohexanone as a solvent were charged, and the mixture was heated to 60 ° C. with stirring under a nitrogen stream, and dissolved uniformly. Subsequently, 587 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer solution having a polystyrene-equivalent weight average molecular weight of 9000 and an acid value of 147 mgKOH / g of the polymer nonvolatile content measured. Next, nitrogen from the nitrogen inlet tube of this flask was stopped, switching to introduction of dry air, 74 parts of glycidyl methacrylate, 11 parts of dimethylbenzylamine and 0.5 part of hydroquinone as a polymerization inhibitor were added while stirring. The reaction was continued for 8 hours at 90 ° C. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing urethane prepolymer solution having a polystyrene-equivalent weight average molecular weight of 9500 and an actually measured acid value of 109 mgKOH / g of the nonvolatile polymer content. Next, 52 parts of succinic anhydride was added to the flask, and the reaction was further continued for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, cyclohexanone was added to this solution to adjust the nonvolatile content to 50.0%. The urethane resin (A-9) having a carboxyl group and an ethylenically unsaturated group prepared according to this production example has an ethylenically unsaturated group equivalent of 2156 g / eq in non-volatile content, and a weight average molecular weight in terms of polystyrene of 10800. The actually measured acid value was 140 mgKOH / g.

[Production Example 10]
A four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet pipe, inlet pipe, thermometer, bisphenol A type epoxy having an epoxy equivalent of 650, a softening point of 81.1 ° C., and a melt viscosity (150 ° C.) of 12.5 poise 371 parts of resin, 925 parts of epichlorohydrin and 463 parts of dimethyl sulfoxide were added and dissolved uniformly, and then 52.8 parts of 98.5% sodium hydroxide was added over 100 minutes at 70 ° C. with stirring. After the addition, the reaction was further carried out at 70 ° C. for 3 hours.

  Next, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide are distilled off under reduced pressure, the reaction product containing the by-product salt and dimethyl sulfoxide is dissolved in 750 parts of methyl isobutyl ketone, and 10 parts of 30% sodium hydroxide is further added. In addition, the mixture was reacted at 70 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water. After separation of oil and water, methyl isobutyl ketone is recovered by distillation from the oil layer, and an epoxy resin having an epoxy equivalent of 287, a hydrolyzable chlorine content of 0.07%, a softening point of 64.2 ° C., and a melt viscosity (150 ° C.) of 7.1 poise. 340 parts were obtained.

  287 parts of this epoxy resin was put into a four-necked flask equipped with another stirrer, reflux condenser, nitrogen inlet pipe, inlet pipe and thermometer, and further 72 parts of acrylic acid, 0.3 part of methylhydroquinone, cyclohexanone 194 The reaction mixture was dissolved by heating and stirring at 90 ° C. Subsequently, the reaction liquid was cooled to 60 ° C., 1.7 parts of triphenylphosphine was added, and the reaction was performed at 100 ° C. for about 32 hours in the presence of oxygen to obtain a reaction product having an actually measured acid value of 1 mgKOH / g. Next, 78 parts of succinic anhydride and 42 parts of cyclohexanone were added to this and reacted at 95 ° C. for about 6 hours. After cooling, cyclohexanone was further added to adjust the solid content to 50.0%. A carboxyl group-containing photosensitive resin (1) solution in which is a bisphenol A type epoxy resin was obtained. The ethylenically unsaturated group equivalent of the resin solid content by this design was 450 eq / g, the weight average molecular weight in terms of polystyrene was 7400, the molecular weight distribution was 2.23, and the acid value of the resin solid content by actual measurement was 100 mgKOH / g. .

[Production Example 11]
To a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube, and a thermometer, 330 parts of a cresol novolac epoxy resin having an epoxy equivalent of 218 g / eq (manufactured by Toto Kasei Co., Ltd .: YDCN-702). The mixture was melted by heating at 90 to 100 ° C. and stirred. Next, 120 parts of acrylic acid, 0.6 part of hydroquinone, and 5 parts of dimethylbenzylamine were added, and the mixture was heated to 115 ° C. with stirring in the presence of oxygen and reacted for 12 hours. Next, 400 parts of cyclohexanone was added to this flask and dissolved by heating to 70 ° C.

  Next, 81 parts of succinic anhydride was added, the temperature was raised to 95 ° C., and the mixture was stirred and reacted for 8 hours. After confirming that the absorption of the acid anhydride disappeared by FT-IR measurement, the mixture was cooled to room temperature and further adjusted to a solid content of 50.0% by adding cyclohexanone, and the main skeleton was cresol novolak. A carboxyl group-containing photosensitive resin (2) solution as a skeleton was obtained. The ethylenically unsaturated group equivalent of the resin solid content by this design was 319 g / eq, the weight average molecular weight in terms of polystyrene was 11000, the molecular weight distribution was 2.90, and the acid value of the resin solid content by measurement was 85 mgKOH / g. .

[Production Example 12]
A dropping funnel was placed in a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, and 400 parts of cyclohexanone was charged into the flask, and the temperature was raised to 90 ° C. with stirring in a nitrogen atmosphere. did. In a separate container, 15 parts of methacrylic acid, 30 parts of methyl methacrylate, 30 parts of butyl methacrylate, 25 parts of benzyl methacrylate, 20 parts of azobisisobutyronitrile as a polymerization initiator and 100 parts of cyclohexanone are stirred and dissolved uniformly. did. The monomer solution was charged into a dropping funnel installed in the flask, and the monomer solution in the dropping funnel was dropped into the flask over 2 hours while stirring the flask at 90 ° C. in a nitrogen atmosphere. Stirring was continued at 90 ° C. even after completion of the dropping, and 0.5 part of azobisisobutyronitrile was charged into the flask after 2 hours from the end of the dropping. After 1 hour, 0.5 part of azobisisobutyronitrile was again added to the flask, and stirring was continued for another 2 hours. Thereafter, the flask was cooled to stop the reaction. A small amount of sampling was performed to obtain a carboxyl group-containing acrylic prepolymer having a polystyrene-equivalent weight average molecular weight of 18700, a molecular weight distribution of 2.58, and an acid value of resin solid content of 98 mgKOH / g.

  Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, and 111 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. , Reacted at 90 ° C. for 8 hours. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing acrylic prepolymer having a polystyrene-reduced weight average molecular weight of 19,900, a molecular weight distribution of 2.72, and an acid value of 5 mgKOH / g of resin solids according to the present design.

  Next, 63 parts of succinic anhydride was added to the flask and reacted for 6 hours with stirring at 90 ° C. in a dry air atmosphere. After confirming that the absorption of the acid anhydride has disappeared by FT-IR measurement, cool to room temperature, add cyclohexanone to adjust the solid content to 50.0%, and the main skeleton is acrylic resin A carboxyl group-containing photosensitive resin (3) solution was obtained. The ethylenically unsaturated group equivalent of the resin solid content by this design is 863 g / eq, the weight average molecular weight in terms of polystyrene is 22000, the molecular weight distribution is 2.81, and the acid value of the resin solid content by measurement is 70 mgKOH / g. It was.

  Table 1 shows the properties of the resins obtained in Production Examples 1 to 12.

[Example 1]
100 parts of the urethane resin (A-1) solution obtained in Production Example 1, Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd .: 2-methyl-1- [4- (methylthio) as a photopolymerization initiator (C) ) Phenyl] -2-morpholino-1-propane) 2.5 parts, DETX-S (Nippon Kayaku Co., Ltd .: 2,4-diethylthioxanthone) 1.0 part, ethylenically unsaturated group-containing compound (D Aronix M-310 (manufactured by Toagosei Co., Ltd .: trimethylolpropane PO-modified triacrylate) 4.0 parts, and thermosetting component (F) HP7200 (Dainippon Ink Chemical Co., Ltd .: dicyclopentadiene type epoxy) 15 0.0 part, 0.5 part of DICY7 (manufactured by Ajinomoto Fine Techno Co., Ltd .: dicyandiamide) as a thermosetting aid (G), and additive R812 (Nippon Aerosil Co., Ltd .: hydrophobic silica fine particles) 4.0 parts, blue paste (blue pigment / base resin (phenol resin) / solvent (carbitol acetate) = 28/12/60) 1.0 part, 45.0 parts of a cyanophenoxy group-containing phenoxyphosphazene compound (B) (the above general formula (4)) was blended as a flame retardant and kneaded with three rolls to prepare the flame retardant resin composition of the present invention.

[Example 2]
A flame retardant resin composition was prepared by the same composition as in Example 1 except that the urethane resin (A-2) solution obtained in Production Example 2 was used instead of the urethane resin (A-1) solution.

[Example 3]
Instead of the urethane resin (A-1) solution, a flame retardant resin composition was prepared by the same formulation as in Example 1 except that the urethane resin (A-3) solution obtained in Production Example 3 was used.

[Example 4]
A flame retardant resin composition was prepared by the same composition as in Example 1 except that the urethane resin (A-4) solution obtained in Production Example 4 was used instead of the urethane resin (A-1) solution.

[Example 5]
A flame retardant resin composition was prepared by the same composition as in Example 1 except that the urethane resin (A-5) solution obtained in Production Example 5 was used instead of the urethane resin (A-1) solution.

[Example 6]
A flame retardant resin composition was prepared by the same composition as in Example 1 except that the urethane resin (A-6) solution obtained in Production Example 6 was used instead of the urethane resin (A-1) solution.

[Example 7]
A flame retardant resin composition was prepared by the same formulation as in Example 1 except that the urethane resin (A-7) solution obtained in Production Example 7 was used instead of the urethane resin (A-1) solution.

[Example 8]
A flame retardant resin composition was prepared in the same manner as in Example 7 except that 17.0 parts of the cyanophenoxy group-containing phenoxyphosphazene compound (general formula (4)) was used.

[Example 9]
A flame retardant resin composition was prepared in the same manner as in Example 7 except that 25.0 parts of the cyanophenoxy group-containing phenoxyphosphazene compound (general formula (4)) was used.

[Example 10]
A flame retardant resin composition was prepared in the same manner as in Example 7, except that the cyanophenoxy group-containing phenoxyphosphazene compound (general formula (4)) was changed to 60.0 parts.

[Example 11]
A flame retardant resin composition was prepared in the same manner as in Example 7 except that 75.0 parts of the cyanophenoxy group-containing phenoxyphosphazene compound (general formula (4)) was used.

[Example 12]
A flame retardant resin composition was prepared by the same composition as in Example 1 except that the urethane resin (A-8) solution obtained in Production Example 8 was used instead of the urethane resin (A-1) solution.

[Example 13]
A flame retardant resin composition was prepared by the same composition as in Example 1 except that the urethane resin (A-9) solution obtained in Production Example 9 was used instead of the urethane resin (A-1) solution.

[Comparative Example 1]
Flame retardant containing each resin in the same manner as in Example 1 except that the carboxyl group-containing photosensitive resin (1) solution obtained in Production Example 10 was used instead of the urethane resin (A-1) solution. A resin composition was prepared.

[Comparative Example 2]
Flame retardancy containing each resin in the same manner as in Example 1 except that the carboxyl group-containing photosensitive resin (2) solution obtained in Production Example 11 was used instead of the urethane resin (A-1) solution. A resin composition was prepared.

[Comparative Example 3]
Flame retardant containing each resin in the same manner as in Example 1 except that the carboxyl group-containing photosensitive resin (3) solution obtained in Production Example 12 was used instead of the urethane resin (A-1) solution. A resin composition was prepared.

[Comparative Example 4]
Example 2 except that 45.0 parts of a phenoxy group-containing phenoxyphosphazene compound (Otsuka Pharmaceutical Co., Ltd .: SPB-100) was blended in place of 45.0 parts of the cyanophenoxy group-containing phenoxyphosphazene compound (general formula (4)). A flame retardant resin composition was prepared by the same composition.

[Comparative Example 5]
Example 4 except that 45.0 parts of a phenoxy phosphazene compound (Otsuka Pharmaceutical Co., Ltd .: SPB-100) was added instead of 45.0 parts of a cyanophenoxy group-containing phenoxyphosphazene compound (general formula (4)). A flame retardant resin composition was prepared by the same composition.

[Comparative Example 6]
Example 7 except that 45.0 parts of a phenoxyphosphazene compound (Otsuka Pharmaceutical Co., Ltd .: SPB-100) was blended in place of 45.0 parts of the cyanophenoxy group-containing phenoxyphosphazene compound (general formula (4)). A flame retardant resin composition was prepared by the same composition.

[Comparative Example 7]
Comparative Example 1 except that 45.0 parts of a phenoxyphosphazene compound (Otsuka Pharmaceutical Co., Ltd .: SPB-100) was blended in place of 45.0 parts of the cyanophenoxy group-containing phenoxyphosphazene compound (general formula (4)). A flame retardant resin composition was prepared by the same composition.

[Comparative Example 8]
Comparative Example 2 except that 45.0 parts of a phenoxy group-containing phenoxyphosphazene compound (Otsuka Pharmaceutical Co., Ltd .: SPB-100) was blended in place of 45.0 parts of the cyanophenoxy group-containing phenoxyphosphazene compound (general formula (4)). A flame retardant resin composition was prepared by the same composition.

[Comparative Example 9]
Comparative Example 3 except that 45.0 parts of a phenoxyphosphazene compound (Otsuka Pharmaceutical Co., Ltd .: SPB-100) was blended in place of 45.0 parts of the cyanophenoxy group-containing phenoxyphosphazene compound (general formula (4)) A flame retardant resin composition was prepared by the same composition.

[Comparative Example 10]
Example except that 45.0 parts of a phenoxyphosphazene compound having a hydroxyphenoxy group (Otsuka Pharmaceutical Co., Ltd .: SPH-100) was blended in place of 45.0 parts of a cyanophenoxy group-containing phenoxyphosphazene compound (general formula (4)). A flame retardant resin composition was prepared by the same formulation as in No. 2.

[Comparative Example 11]
Example except that 45.0 parts of a phenoxyphosphazene compound having a hydroxyphenoxy group (Otsuka Pharmaceutical Co., Ltd .: SPH-100) was blended in place of 45.0 parts of a cyanophenoxy group-containing phenoxyphosphazene compound (general formula (4)). A flame retardant resin composition was prepared by the same formulation as in No. 4.

[Comparative Example 12]
Example except that 45.0 parts of a phenoxyphosphazene compound having a hydroxyphenoxy group (Otsuka Pharmaceutical Co., Ltd .: SPH-100) was blended in place of 45.0 parts of a cyanophenoxy group-containing phenoxyphosphazene compound (general formula (4)). A flame retardant resin composition was prepared by the same formulation as in No. 7.

[Comparative Example 13]
A comparative example except that 45.0 parts of a phenoxyphosphazene compound having a hydroxyphenoxy group (Otsuka Pharmaceutical Co., Ltd .: SPH-100) was blended in place of 45.0 parts of a cyanophenoxy group-containing phenoxyphosphazene compound (general formula (4)). A flame retardant resin composition was prepared according to the same formulation as in No. 1.

[Comparative Example 14]
A comparative example except that 45.0 parts of a phenoxyphosphazene compound having a hydroxyphenoxy group (Otsuka Pharmaceutical Co., Ltd .: SPH-100) was blended in place of 45.0 parts of a cyanophenoxy group-containing phenoxyphosphazene compound (general formula (4)). A flame retardant resin composition was prepared by the same formulation as in No. 2.

[Comparative Example 15]
A comparative example except that 45.0 parts of a phenoxyphosphazene compound having a hydroxyphenoxy group (Otsuka Pharmaceutical Co., Ltd .: SPH-100) was blended in place of 45.0 parts of a cyanophenoxy group-containing phenoxyphosphazene compound (general formula (4)). A flame retardant resin composition was prepared by the same formulation as in No. 3.

[Create sample A]
The obtained flame-retardant resin composition was applied onto Kapton 100H (manufactured by Toray DuPont Co., Ltd .: polyimide film (25 μm thickness)) so that the dry film thickness was 20 μm, and 30 with a hot air dryer at 80 ° C. After being dried for a while, it was cooled to room temperature. This was irradiated with an integrated light quantity of 300 mJ / cm ² using an ultraviolet exposure device (USHIO INC .: “UVC-2534 / 1MNLC3-AA08”, 120 W / cm metal halide lamp, 1 light), and a hot air dryer at 150 ° C. For 1 hour. The obtained cured product was cooled to room temperature. This is designated as sample A.

[Evaluation of adhesion]
According to JIS K5400, 100 grids of 1 mm × 1 mm were made for sample A, and a peeling test was performed using cello tape (registered trademark). The peeled state of the grid was observed and evaluated according to the following criteria.
○: No peeling.
Δ: 20% or less of the grids peel off.
X: 21% or more of the grids peeled off.

[Evaluation of flexibility]
Sample A was folded 180 degrees, and then the same part was folded 180 degrees on the opposite side. The state of the coating film at that time was judged according to the following criteria.
○: No cracks are observed on the film surface.
Δ: Slight cracks are observed on the film surface.
X: The film is broken, and cracks are clearly seen on the film surface.

[Evaluation of solder heat resistance]
Sample A was immersed in a 260 ° C. solder bath (JIS C 6481) for 5 seconds as one cycle, and the number of times swelling and peeling occurred in the coating film was measured and judged according to the following criteria.
A: No swelling or peeling occurs in the coating film for 11 cycles or more.
○: Swelling or peeling occurs in the coating film in 6 to 10 cycles.
Δ: Swelling or peeling occurs in the coating film in 2 to 5 cycles.
X: Swelling or peeling occurred in the coating film in one cycle.

[Evaluation of flame retardancy]
Sample A was tested according to the UL94 flame retardant test and evaluated according to the following criteria.
The high flame retardancy is in the order of VTM-0-> VTM-0 ○> HB ◎> HB ○> ×.
VTM-0 ◎ ... VTM-0 equivalent, extinguishing time after ignition within 3 seconds.
VTM-0 ○ ... VTM-0 equivalent, extinguishing time after ignition within 3-6 seconds.
HB ◎ ... HB equivalent and extinguishes from ignition point to 25mm.
HB ○ ... HB equivalent, extinguishing from ignition point to 25-100mm.
X: Not extinguished by 100 mm in HB test, or complete combustion.

[Evaluation of bleed out]
The surface layer of Sample A which was allowed to stand at 40 ° C. for one week was observed with a microscope and evaluated according to the following criteria.
◯: The surface is not whitened and no crystal is precipitated.
X: The surface is whitened or crystals are precipitated.

[Evaluation of solvent resistance]
Sample A is immersed in methyl ethyl ketone and isopropyl alcohol for 10 minutes at room temperature. After confirming that there was no abnormality in the external appearance, a peeling test was performed using cello tape (registered trademark), and evaluation was performed according to the following criteria.
○: There is no abnormality in the appearance of the coating film, and there is no swelling or peeling.
Δ: There is slight peeling at the edge of the coating film (between the coated portion and the polyimide base material).
X: The coating film has swelling and peeling.

[Evaluation of acid resistance]
Sample A is immersed in a 10% aqueous hydrochloric acid solution at room temperature for 10 minutes. After confirming that there was no more in appearance, a peeling test with cello tape (registered trademark) was conducted, and the following criteria were evaluated.
○: There is no abnormality in the appearance of the coating film, and there is no swelling or peeling.
Δ: There is a slight swelling or peeling around the edge of the coating film (between the coated part and the polyimide base material).
X: The coating film has swelling and peeling.

[Evaluation of developability]
On the PET film, the flame retardant resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 13 were applied so that the film thickness after drying was 20 μm, and dried with hot air at 80 ° C. for 20 minutes. Dried. The dried coating film was brought into close contact with a copper-clad laminate (the copper surface was roughened by etching) by vacuum lamination (60 ° C., 0.2 MPA = 2 kg / cm ² ). Subsequently, a negative film having a resist pattern [φ100 μm hole] was brought into close contact with the PET film, and irradiated with ultraviolet rays (400 mJ / cm ² ) using an ultraviolet exposure device (EXM-1201F, short arc lamp manufactured by Oak Seisakusho). Next, the PET film was peeled off and developed with a 1% aqueous sodium carbonate solution at a spray pressure of ² kg / cm ² for 60 seconds. Thereafter, heat curing was performed with a hot air dryer at 150 ° C. for 1 hour to prepare Sample B. The hole of φ100μm was observed with a magnifying glass, the diameter of the part where the resist layer was developed and the copper surface was exposed (hole part) was measured, and the resolution was judged according to the following criteria .
◎ ・ ・ ・ 90 μm or more and 100 μm or less ○ ・ ・ ・ 80 μm or more and less than 90 μm in diameter
Δ: Diameter of 60 μm or more and less than 80 μm.
X: Diameter less than 60 μm.

<Evaluation results>
The evaluation results are shown in Table 2.

From the results of Table 2, in Comparative Examples 4, 5, and 6, when a conventional phenoxyphosphazene compound having only a phenoxy group is used, although flame retardancy and developability are excellent, bleed-out resistance can be satisfied. There wasn't. In Comparative Examples 7 and 8, although excellent in flame retardancy and bleed-out resistance, flexibility, which is the most important physical property as a protective layer for flexible printed wiring boards, could not be satisfied. When phenoxyphosphazene having a hydroxyphenoxy group is used in Comparative Examples 10 to 15, it has flame retardancy and is excellent in bleed-out resistance, but it cannot satisfy developability which is an important physical property as a solder resist. It was. Comparative Examples 1 to 3 are excellent in flame retardancy and bleed-out resistance, but Comparative Examples 1 and 2 satisfy flexibility, and Comparative Example 3 satisfies polyimide adhesion, flexibility, and solder heat resistance. could not.
From Examples 1-13, it turns out that the flame-retardant resin composition of this invention has satisfy | filled all the physical properties required for a flame-retardant resin composition.

Claims (11)

A urethane resin containing a carboxyl group and an ethylenically unsaturated group (A) , and a phenoxyphosphazene compound (B) selected from the group consisting of the following formulas (4), (5), and (6): A flame retardant resin composition.
Formula (4)

Formula (5)

Formula (6)

2. The flame retardant resin composition according to claim 1, wherein 10 to 50 parts by weight of the phenoxyphosphazene compound (B) is contained in 100 parts by weight of the nonvolatile content of the flame retardant resin composition.   The flame retardant resin composition according to claim 1, comprising a photopolymerization initiator (C).   The flame retardant resin composition according to claim 1, comprising an ethylenically unsaturated group-containing compound (D).   Furthermore, a flame retardant component (E) is included, The flame retardant resin composition in any one of Claims 1-4 characterized by the above-mentioned.   Furthermore, a thermosetting component (F) is included, The flame-retardant resin composition in any one of Claims 1-5 characterized by the above-mentioned.   Furthermore, a thermosetting auxiliary agent (G) is contained, The flame-retardant resin composition in any one of Claims 1-6 characterized by the above-mentioned.   The dry film using the flame-retardant resin composition in any one of Claims 1-7.   Hardened | cured material formed by hardening | curing the flame-retardant resin composition in any one of Claims 1-7.   A printed wiring board comprising a hardened layer formed from the flame retardant resin composition according to claim 1 on a wiring circuit. A flexible printed wiring board comprising a hardened layer formed of the flame retardant resin composition according to claim 1 on a wiring circuit.