JP5715577B2 - Polyamide or polyimide resin composition containing phosphine oxide and cured product thereof - Google Patents

Description

  The present invention relates to a curable resin composition using a phosphine oxide compound, which is a reactive compound that can be polymerized to various polymer materials, for the purpose of making the polymer material flame retardant. Examples of the application include film forming materials, solder resists in the production of printed (wiring circuit) substrates, other resist materials capable of alkali development, adhesives, lenses, displays, optical fibers, optical waveguides, holograms, and the like.

  Attempts to impart flame retardancy to molded articles, film-forming materials, etc. are widely performed. Conventionally, flame retardant materials using halogen compounds typified by bromine compounds have been widely used, but these have come to be avoided in recent years due to increasing environmental problems. As an alternative to these, studies have been made on the use of flame retardant materials such as phosphorus compounds.

  Generally, phosphorus compounds are used by simply being added to a resin composition or the like, but since the resin composition or the like bleeds out during curing or over time, a uniform flame retardant effect cannot be obtained. There is a risk that the thermal, electrical, or mechanical characteristics may be deteriorated. Therefore, in order to solve these problems, development of a flame retardant having reactivity in which a phosphorus compound is incorporated into a skeleton such as a resin is required.

  Among these, as a polymerizable (meth) acrylic monomer containing phosphorus, a phosphoric acid type compound represented by the following general formula (2) is known (Patent Document 1).

（式中、Ｒ'₁、Ｒ'₂は炭素数１〜１０の直鎖または分岐状のアルキレン基を表わし、Ｒ₃、Ｒ₄は水素原子又はメチル基を表わす。Ｒ'₁、Ｒ'₂は、互いに同一であっても、異なっていてもよい。）

(In the formula, R ′ ₁ and R ′ ₂ represent a linear or branched alkylene group having 1 to 10 carbon atoms, and R ₃ and R ₄ represent a hydrogen atom or a methyl group. R ′ ₁ and R ′ ₂ May be the same as or different from each other.)

  However, the phosphoric acid type structure (acidic group) represented by the formula (2) has some undesirable effects on the material. For example, since the acidic group promotes hydrolysis or promotes corrosion of a substrate such as a metal, the cured product does not exhibit long-term durability. In particular, when used as a permanent resist for a circuit board or the like, the presence of acidic groups is a big problem because it is used for the purpose of protecting a circuit for a long period of time.

  In applications such as solder resists that require development, generally, a liquid resin composition and a curing agent liquid containing an epoxy compound are used as a set, and these two liquids are mixed before use. Yes. At this time, when the resin composition contains a lot of acidic groups, the storage stability after mixing the two liquids and the reaction of the curing agent is promoted in the steps up to development after coating, and development is impossible. There was also a problem.

  In addition, since the phosphoric acid type compound cross-linked with the epoxy resin is hydrolyzed under high heat and humidity conditions, there are problems in reliability tests such as electrical characteristics.

  On the other hand, Patent Document 2 discloses a technique for introducing an ethylenically unsaturated group by interposing an epoxy group in a phosphine oxide having a hydroxyl group excellent in heat resistance and moisture resistance. However, this technique has a problem that the phosphine oxide bleeds out from the resin composition without sensitivity when cured with active energy rays.

  In order to impart flame retardancy to a resist material, a flame retardant having reactivity and an inorganic extender pigment have also been blended. However, since a resist material for use in a flexible circuit board is required to have high flexibility, it is difficult to add flame retardant by adding a large amount of extender pigment.

Patent Document 3 discloses a phosphine oxide compound (A) used in the present invention, and further discloses a resin composition comprising the compound (A) and a photopolymerization initiator. Patent Document 4 includes the phosphine oxide compound (A), a reactive compound (B) having two or more active energy ray reactive functional groups (specifically, an epoxy compound) and a photopolymerization initiator. A curable resin composition is disclosed.
These patent documents do not disclose a resin composition containing the phosphine oxide compound (A) and a polyamide compound or a polyimide compound.

  Many photosensitive compositions using a polyamide compound or a polyimide compound are known. However, a photosensitive composition using a polyamide compound or a polyimide compound that satisfies both satisfactory flame retardancy and high reliability is not known. In order to impart alkali solubility so that a resin composition using a polyamide compound or a polyimide compound can be patterned by development, it is common to introduce carboxylic acid, sulfonic acid, phenolic hydroxyl group, etc. into the skeleton, In order to improve the solvent solubility, a method of introducing an aliphatic skeleton can be considered, but flame retardancy is lowered in any of these methods.

JP 2000-38398 A JP 2004-143286 A Japanese Patent No. 3454544 JP 2009-256622 A

In the photosensitive resin composition containing the photosensitive phosphine oxide compound and the polyamide compound or the polyimide compound, the phosphine oxide compound is not hydrolyzed under high-humidity heat conditions, and there is a problem in reliability tests such as electrical characteristics. It is an object of the present invention to obtain a resin composition capable of forming a cured product layer that is excellent in heat resistance and moisture resistance.

  In view of the above problems, the present inventors have conducted extensive research on a photosensitive resin composition having both photosensitivity and excellent insulating properties over a long period of time. As a result, the phosphine oxide compound (A) having a specific structure and a polyamic acid ( The present inventors have found that a composition containing a polyamic acid) or an imide thereof solves the above-mentioned problems, and has completed the present invention. That is, the present invention relates to the following (1) to (15).

（式中、Ｒは水素原子又はメチル基を示す。）で表わされるホスフィンオキサイド化合物（Ａ）、及び（Ｂ）成分として、ジアミン化合物と四塩基酸二無水物を反応させて得られるポリアミド化合物又はポリイミド化合物を含む樹脂組成物。
(２) 下記式（１）

（式中、Ｒは水素原子又はメチル基を示す。）で表わされるホスフィンオキサイド化合物（Ａ）、（Ｂ）成分として、ジアミン化合物と四塩基酸二無水物を反応させて得られるポリアミド化合物又はポリイミド化合物及び、感光剤（Ｃ）又は光重合開始剤（Ｅ）を含む感光性樹脂組成物。(1) Following formula (1)

(Wherein R represents a hydrogen atom or a methyl group) As the phosphine oxide compound (A) and (B) component represented by the formula, a polyamide compound obtained by reacting a diamine compound and a tetrabasic acid dianhydride, or A resin composition containing a polyimide compound.
(2) Following formula (1)

(Wherein R represents a hydrogen atom or a methyl group) As a phosphine oxide compound (A) and (B) component represented by the formula, a polyamide compound or a polyimide obtained by reacting a diamine compound and a tetrabasic acid dianhydride The photosensitive resin composition containing a compound and a photosensitizer (C) or a photoinitiator (E).

(3) The photosensitive resin composition as described in said (2) containing the said phosphine oxide compound (A), the said (B) component, and a photosensitive agent (C).
(4) including the phosphine oxide compound (A), the component (B), a reactive compound (D) having two or more active energy ray-reactive functional groups in one molecule, and a photopolymerization initiator (E). The photosensitive resin composition as described in said (1) or (2).
(5) The photosensitive resin composition as described in said (4) containing a 2-6 functional (meth) acrylate compound as said reactive compound (D).
(6) The photosensitive resin composition according to (4) or (5), further including a polyfunctional epoxy compound as a curing agent.
(7) The photosensitive resin composition as described in any one of (4) to (6) above, which contains an acid-modified (meth) acrylate compound as the reactive compound (D).
(8) The resin composition as described in (1) to (7) above, containing 1 to 95% by mass of the phosphine oxide compound (A) and 5 to 99% by mass of the component (B) with respect to the entire resin composition.

(9) The resin composition according to (1) or the photosensitive resin composition according to any one of (2) to (8), which is a molding material.
(10) The resin composition according to (1) or the photosensitive resin composition according to any one of (2) to (8), which is a film forming material.
(11) The resin composition according to (1) or the photosensitive resin composition according to any one of (2) to (8), which is an electrically insulating material.
(12) The photosensitive resin composition according to any one of (1) or (2) to (8) above, which is a solder resist composition.
(13) A multilayer material comprising the cured product layer of the resin composition of (1) or the cured product layer of the photosensitive resin composition according to any one of (2) to (8). .
(14) A cured product of the resin composition of claim 1.
(15) A cured product of the photosensitive resin composition according to any one of claims 2 to 8.

  In the present invention, the phosphine oxide compound is not hydrolyzed under high-humidity heat conditions, a defect in a reliability test such as electrical characteristics does not occur, and a cured layer having excellent heat resistance and moisture resistance is formed. It is related with the resin composition which can do. The present invention can provide a photosensitive composition that has sufficient flame retardancy without using a large amount of the phosphine oxide compound, and further provides a cured product having excellent heat resistance and moisture resistance and good electrical insulation. . The cured product of the photosensitive resin composition of the present invention sufficiently satisfies the adhesion to the metal and the flame retardancy of the resin, has excellent heat resistance and moisture resistance, has good electrical insulation, and has long-term reliability. Excellent material. Therefore, the photosensitive resin composition of the present invention comprises a film-forming material, a solder resist for manufacturing a printed (wiring circuit) substrate, a resist material capable of alkali development, an adhesive, a lens, a display, an optical fiber, an optical waveguide, and a hologram. It is suitable as a composition for equal use.

Details of the present invention will be described below.
The present invention provides a phosphine oxide compound (A) represented by the formula (1) and a polyamide compound (B-1) or a polyimide compound obtained by reacting a diamine compound and a tetrabasic acid dianhydride as the component (B). The present invention relates to a resin composition containing (B-2).
The phosphine oxide compound (A) represented by the formula (1) used in the present invention is publicly known because its production method is described in Patent Document 3.
For example, it can be obtained by reacting the alcohol compound of formula (3) with a monocarboxylic acid compound having an ethylenically unsaturated group in the molecule (specifically, (meth) acrylic acid).

  The alcohol compound represented by the formula (3) is obtained by reacting formaldehyde with a phosphorus-containing compound having at least one active hydrogen in the molecule as in the formula (4). This compound can utilize a commercial item, for example, Sanko Co., Ltd. HCA (brand name) is mentioned.

  The monocarboxylic acid compound having an ethylenically unsaturated group in the molecule used for producing the phosphine oxide compound (A) used in the present invention has a reactivity to active energy rays in the phosphine oxide compound (A). Give. Specific examples include acrylic acid and methacrylic acid.

  The phosphine oxide compound (A) used in the present invention can be produced by dehydrating and condensing the alcohol compound and the monocarboxylic acid compound in the presence of an acid catalyst.

  The acid catalyst to be used can be arbitrarily selected from known ones such as sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, and the amount used is 0.1 to 10 mol%, preferably 0.1 mol% based on the monocarboxylic acid compound. 1 to 5 mol%.

An azeotropic solvent can be used to distill off the water produced by the reaction. The azeotropic solvent here has a boiling point of 60 to 130 ° C. and can be easily separated from water, and in particular, aliphatic hydrocarbons such as n-hexane and n-heptane, and aromatics such as benzene and toluene. The use of alicyclic hydrocarbons such as aromatic hydrocarbons and cyclohexane is preferred. The amount used is arbitrary, but is preferably 10 to 70% by mass with respect to the reaction mixture.
The reaction temperature may be in the range of 60 to 130 ° C, but is preferably 75 to 120 ° C from the viewpoint of shortening the reaction time and preventing polymerization.

  Of the monocarboxylic acid compounds, commercially available (meth) acrylic acid or the like usually has a polymerization inhibitor such as p-methoxyphenol already added, but a polymerization inhibitor is added again during the reaction. May be. Examples of such polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, Phenothiazine and the like are preferable. The usage-amount is 0.01-1 mass% with respect to the reaction raw material mixture.

In the present invention, the polyamide compound (B-1) used as the component (B) is any polyamide compound (B-1) obtained by reacting a diamine compound and tetrabasic acid dianhydride. I can do it. In addition, any known polyimide compound can be used as the polyimide compound (B-2). The polyimide compound (B-2) can be usually obtained by a dehydration cyclization reaction of the polyamide compound (B-1).
These (B) components are preferably solvent-soluble so that a flame-retardant film or layer can be formed from the resin composition of the present invention.
In the present invention, the polyamide compound (B-1) or the polyimide compound (B-2) is used in combination with the phosphine oxide compound (A) represented by the formula (1), thereby having flame retardancy. In addition, when used in electrical and electronic parts, a highly reliable and strong cured product can be obtained. That is, the amide group or imide group in the component (B) constitutes a strong crosslinked structure in combination with the monofunctional phosphine oxide compound (A). As a result, although the phosphine oxide compound (A) of formula (1) itself is easily hydrolyzed, the hydrolysis behavior and bleed-out of the phosphine oxide compound (A) are suppressed, and the resin composition of the present invention To provide a stable flame retardancy and insulation for a long time. Therefore, the resin composition of the present invention can be used for electronic or electrical parts and the like to give a cured product layer having high reliability.

  In the present invention, when the molecular weight of the polyamide compound (B-1) or the polyimide compound (B-2) is within a certain range, the coating property and solubility of the resin composition of the present invention are excellent. preferable. Usually, the molecular weight of the polyamide compound (B-1) or the polyimide compound (B-2) is in the range of 8,000 to 150,000, preferably 15,000 to 80,000 in terms of weight average molecular weight. When the molecular weight is too large, the coating property, solubility, or developability deteriorates. Moreover, when molecular weight is too small, the cured film obtained becomes weak. Adjustment of the molecular weight of this polyamide compound (B-1) or this polyimide compound (B-2) can be controlled by the molar ratio of diamine and tetrabasic acid dianhydride to be used. A suitable molecular weight is obtained when the value of the molar amount of diamine / the molar amount of tetrabasic dianhydride is in the range of 2 to 0.5, more preferably 1.1 to 0.9.

  The diamine compound used in the present invention has two amino groups in one molecule, and is used as a component for constituting a polyamide compound or a polyimide compound (B) together with a tetrabasic acid anhydride described later. The diamine compound to be used is not particularly limited and is appropriately selected according to the purpose of the resin composition of the present invention.

  Specific examples include linear aliphatic diamines such as ethylenediamine, propylenediamine, hexamethylenediamine, octamethylenediamine, and nonamethylenediamine, preferably C5-C10 linear aliphatic diamines, cyclohexyldiamine, isophorone. Cyclic aliphatic diamines such as diamine, norbornene diamine, dicyclohexane diamine, tricyclodecane diamine, diaminodicyclohexyl methane, monocyclic aromatic diamines such as phenylene diamine, dimethyl phenylene diamine, biphenylene diamine, dianisidine, bis (aminophenyl) Ether, bis (methylaminophenyl) ether, bis (hydroxyaminophenyl) ether, bis (carboxyaminophenyl) ether, bis (aminophenyl) sulfo Bicyclic aromatic diamines such as bis (aminophenyl) methane, bis (aminophenyl) propane, bis (aminophenyl) sulfide, bis (aminophenyl) hexafluoropropane, naphthalenediamine, bis (hydroxyaminophenyl) benzene , Tricyclic aromatic diamines such as bis (hydroxyaminophenoxy) benzene, polycyclic aromatic diamines such as bisaminophenylfluorene, bis [[aminophenoxy] phenyl] propane, and bis [[aminophenoxy] phenyl] sulfone And their derivatives. In addition, other diamines such as silicone diamine can also be used.

In the present invention, when a linear aliphatic diamine, a cyclic aliphatic diamine, a bicyclic aromatic diamine, or a tricyclic aromatic diamine is used, the cured product provided by the resin composition of the present invention is flexible. And flame retardancy at a high level.
Preferred diamines include linear aliphatic diamines and bicyclic or tricyclic aromatic diamines whose aromatic rings are benzene rings. More specifically, C5-C10 linear aliphatic diamines, for example, hexanediamine, octanediamine, dodecanediamine, two amino-substituted benzene rings, a direct bond or a bridging group (preferably —SO ₂ -, -O-, -C (CF ₃ ) _2- and the like), and a tricyclic aromatic diamine having a benzene ring sandwiched between them. The amino-substituted benzene ring may be substituted with a hydroxyl group in addition to the amino group. For example, biphenylenediamine, bis (aminophenyl) ether, bis (hydroxyaminophenyl) ether, bis (aminophenyl) sulfone, bis (hydroxyaminophenyl) sulfone, bis (aminophenyl) hexafluoropropane, bis (hydroxyaminophenyl) benzene And bis (hydroxyaminophenoxy) benzene. From the viewpoint of flame retardancy and flexibility of the cured product layer, a diamine in which the crosslinking group is —SO ₂ — is more preferable, and bis (aminophenyl) sulfone is most preferable.

  The tetrabasic acid dianhydride used in the present invention refers to a dianhydride of a tetracarboxylic acid compound having four carboxyl groups in one molecule. These are used as a component for constituting a polyamide compound or a polyimide compound (B) together with the diamine compound. There is no special limitation in the tetrabasic acid dianhydride used, It selects suitably according to the objective of the resin composition of this invention.

Specific examples include monocyclic aromatic tetrabasic acid dianhydrides such as pyromellitic acid anhydride, biphenyl tetracarboxylic acid anhydride, benzophenone tetracarboxylic acid dianhydride, naphthyl tetracarboxylic acid anhydride, diphenyl ether tetra Diols such as carboxylic acid anhydride, diphenylsulfone tetracarboxylic acid anhydride, ethylene glycol bistrimellitic acid anhydride, hexanediol bistrimellitic acid anhydride, diol bistrimellitic acid anhydrides (for example, hexanediol bistrimellitic acid anhydride) Bicyclic aromatic tetrabasic dianhydrides such as bistrimellitic anhydride, polycyclic aromatic tetrabasic dianhydrides such as fluorene anhydride, biphenol bistrimellitic anhydride, butanetetra Examples thereof include carboxylic acid anhydrides. Furthermore, alicyclic acid anhydrides obtained by nuclear hydrogenation of these aromatic anhydrides can also be used. In the present invention, when bicyclic aromatic tetrabasic dianhydrides and their hydrogenated products are used, both flexibility and flame retardancy can be achieved at a high level.
Preferred tetrabasic dianhydrides include two benzene rings having one carboxylic anhydride group, a direct bond or a bridging group (preferably —SO ₂ —, —O—, —C (CF ₃ ) _{2. -, - (OCH 2 CH 2} ) n - , etc.) bicyclic aromatic linked in tetrabasic acid dianhydride can be mentioned. More preferable tetrabasic acid dianhydrides include biphenyltetracarboxylic anhydride or diphenylsulfonetetracarboxylic anhydride.

Preferred examples of the polyamide compound (B-1) include polyamide compounds obtained by reacting a bicyclic or tricyclic aromatic diamine in which the aromatic ring is a benzene ring with a bicyclic aromatic tetrabasic dianhydride. be able to. More preferably, using a compound in which at least one of a bicyclic aromatic diamine and a bicyclic aromatic tetrabasic dianhydride is bonded with a direct bond, a —SO ₂ —crosslinking group, or an —O— crosslinking group. The resulting polyamide compound. More preferably, a compound in which at least one of a bicyclic aromatic diamine and a bicyclic aromatic tetrabasic dianhydride is directly bonded or bonded with a —SO ₂ —crosslinking group, for example, a diamine component, Use a ring aromatic diamine (specifically bis (aminophenyl) sulfone) or a tetracyclic acid dianhydride as a bicyclic aromatic tetrabasic dianhydride (specifically diphenylsulfone tetracarboxylic anhydride) Product) is a polyamide compound obtained.
The preferred polyimide compound (B-2) is the polyimide compound (B-2) obtained by dehydration ring closure from the preferred polyamide compound (B-1).

In the resin composition of the present invention, at least one of the polyamide compound (B-1) and the polyimide compound (B-2) may be included as the component (B), and it is determined depending on the purpose. Is preferred.
For example, in the case of a positive type, when reliability at a high temperature and high humidity (120 ° C., 85% relative humidity) is not required for a long period of time, the component (B) is added to the polyamide compound (B- By setting it as 1), it can be set as the resin composition excellent in developability, and the hardened | cured material layer which has the outstanding flame retardance can be obtained. In the case where high reliability under high temperature and high humidity (120 ° C., 85% relative humidity) is required for as long as possible, even if some developability is sacrificed, the component (B) is added to the polyimide compound ( By setting it as B-2), the hardened | cured material layer which is a flame retardance and has the said outstanding long-term reliability can be obtained.
Moreover, in the case of a negative type, even if the component (B) is the polyamide compound (B-1) or the polyimide compound (B-2), excellent developability without any inferiority. High flame resistance and high reliability effect under high temperature and high humidity can be achieved.

A polyamide compound (B-1) can be obtained by reacting the diamines with tetrabasic acid dianhydride. This reaction can be generally performed by a known method and reaction conditions.
Furthermore, a polyimide compound (B-2) can be obtained by subjecting the polyamide compound (B-1) to a dehydration condensation reaction. This reaction can also be carried out by generally known methods and reaction conditions.
In synthesizing the polyamide compound (B-1) and the polyimide compound (B-2), a solvent can be appropriately used. The solvent that can be used is not particularly limited as long as the obtained polyamide compound (B-1) and polyimide compound (B-2) can be dissolved. Specific examples include polar solvents. Among polar solvents, for example, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, ester solvents such as butyrolactone, and glycol solvents such as butyl diglycol are preferably used. Of these, amide solvents or ester solvents are more preferable, ketone solvents such as N-methylpyrrolidone and butyrolactone are more preferable, and N-methylpyrrolidone is most preferable.

  The content of each of the component (A) and the component (B) is 1 to 95% by mass of the component (A) (phosphine oxide compound (A)) with respect to the total composition (100% by mass) of the present invention, preferably 5-92 mass%, (B) component (polyamide compound (B-1) or polyimide compound (B-2)) 5-99 mass%, Preferably it is 8-95 mass%. In addition, the ratio with respect to the whole composition of this invention is a ratio of the internal ratio with respect to the total amount of this composition unless there is particular notice.

  The photosensitive agent (C) that can be used in the present invention is added for the purpose of reacting with an active energy ray and reacting to bring about a change in characteristics of the resin composition, specifically, positive photosensitive characteristics. is there. For example, patterning can be performed by changing the solubility of the resin composition of the present invention in a solvent or an alkaline aqueous solution between the active energy ray irradiated portion and the non-irradiated portion.

  For example, by using the photosensitive agent (C) that generates an acidic group with light irradiation, the solubility of the irradiated portion in a developing solution such as an alkaline aqueous solution is improved, while the non-irradiated portion is exposed to the developing solution. So-called positive photosensitive characteristics can be imparted with poor solubility.

  Specifically, quinonediazide compounds are generally used as those that give positive photosensitive characteristics. These can be obtained by esterifying a polyhydroxy compound having a plurality of phenolic hydroxyl groups with naphthoquinone diazide sulfonate. For example, 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester, 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone and 2,3,4, Examples thereof include 6-diazo-dihydro-5-oxo-1-naphthalenesulfonic acid ester of 4′-tetrahydroxybenzophenone. Specific product names include PC-5, NT-200, 4NT-300 manufactured by Toyo Gosei Co., Ltd., DTEP-300, DTEP-350 manufactured by Daito Chemix Co., Ltd., and the like.

  When using a photosensitizer (C), it is 0.5-50 mass% in the whole composition (100 mass%) of this invention, Preferably it is 1-30 mass%, More preferably, it is the range of 5-30 mass%. Can be added as appropriate.

  In the present invention, a reactive compound (D) having two or more active energy ray-reactive functional groups in one molecule can also be used. These cause the curing reaction to proceed with the irradiation of the active energy rays, and the irradiated portion is insolubilized in the developer. Since the curing reaction does not proceed in the non-irradiated part, the developability (solubility in the developer) with the developer (alkaline aqueous solution or organic solvent) is maintained. Accordingly, the reactive compound (D) imparts a so-called negative photosensitive property to the resin composition of the present invention.

  By using the reactive compound (D) having two or more active energy ray-reactive functional groups in one molecule in combination with the phosphine oxide compound (A) and the component (B), excellent flame retardancy can be obtained. It has a tough cured product. Since it has two or more active energy ray reactive functional groups in one molecule, it forms a strong cross-linked structure in combination with the monofunctional phosphine oxide compound (A) together with the component (B). The hydrolysis behavior and bleed-out of the phosphine oxide compound (A) can be suppressed, and stable flame retardancy and reliability in the long term can be derived.

In the present invention, the active energy ray-reactive functional group refers to a functional group that can react with active energy rays to form a cross-linked bond. For example, as a functional group that reacts with radicals generated by irradiation with active energy rays, polymerizable unsaturated bonds such as a (meth) acryl group, a vinyl group, and a vinyl ether group can be given. Moreover, unsaturated ether groups, such as cyclic ether groups, such as an epoxy group and an oxetane group, a vinyl ether group, etc. which react with the cation produced by active energy ray irradiation are mentioned. A reactive compound having two or more active energy ray-reactive functional groups in one molecule also includes both radical and cationic functional groups such as glycidyl (meth) acrylate in one molecule. D).
However, in the present invention, an epoxy compound may be used as a curing agent as will be described later. Usually, the curing agent is only combined in one set until use. Since it is often added to the resin composition of the present invention, the epoxy resin used as a curing agent is not included in the reactive compound (D) in the resin composition of the present invention.

  Examples of the reactive compound (D) having two or more (meth) acryl groups include (meth) acrylate compounds having 2 to 6 (meth) acryl groups. Specifically, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, glycol di (meth) acrylate, diethylene di (meth) acrylate , Polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate; adipic acid epoxy di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogenated bisphenol ethylene oxide ( Meth) acrylate, bisphenol di (meth) acrylate; ε-caprolactone modified hydroxybivalate neopentyl glycol di (meth) acrylate Dipentaerythritol poly (2-6) (meth) such as dirate, ε-caprolactone-modified dipentaerythritol hexa (meth) acrylate, ε-caprolactone-modified dipentaerythritol poly (meth) acrylate; dipentaerythritol hexa (meth) acrylate Acrylates, trimethylolpropane tri (meth) acrylate and triethylolpropane tri (meth) acrylate and their ethylene oxide adducts; pentaerythritol tri (meth) acrylate and its ethylene oxide adducts; pentaerythritol tetra (meth) acrylate and (Meth) acrylic acid ester such as ethylene oxide adduct;

  Examples of the reactive compound (D) having two or more vinyl groups include vinyl ethers such as ethylene glycol divinyl ether, styrenes such as divinylbenzene, and other vinyl compounds such as triallyl isocyanurate and trimethallyl isocyanurate. It is done.

  Moreover, as a reactive compound (D) which has a 2 or more cyclic ether group, if it is a compound which has an epoxy group and an oxetane group generally, there will be no limitation in particular. For example, alkyl diglycidyl ethers such as butyl diglycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4, -epoxycyclohexanecarboxylate (“Syracure UVR-6110” manufactured by Union Carbide Corporation) Etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (such as “ELR-4206” manufactured by Union Carbide Corporation), limonene dioxide (manufactured by Daicel Chemical Industries, Ltd.) Celoxide 3000 "), allyl cyclohexylene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxycyclohexyl-5,5-spi -3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate (such as "Syracure UVR-6128" manufactured by Union Carbide Corporation), bis (3,4-epoxycyclohexylmethyl) adipate Bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane, and the like.

  In addition to this, as the reactive compound (D), urethane (meth) acrylates having a plurality of (meth) acryl groups and urethane bonds in the same molecule, as well as a plurality of (meth) acryl groups and ester bonds in the same molecule. Polyester (meth) acrylate with epoxy resin, epoxy (meth) acrylate derived from epoxy resin, combined with multiple (meth) acrylic groups, and reactive oligomers and acid values in which these bonds are used in combination A compound having two or more active energy ray-reactive functional groups can also be used.

  The urethane (meth) acrylates that can be used as the reactive compound (D) in the present invention are a reaction product of a hydroxyl group-containing (meth) acrylate and a polyisocyanate, and other alcohols used as necessary. For example, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycerin (meta) such as glycerin mono (meth) acrylate and glycerin di (meth) acrylate ) Sugar alcohol (meth) acrylates such as acrylates, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate , Isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate , Dicyclohexane diisocyanate, and their isocyanurate, by reacting polyisocyanates such as buret reactants, the urethane (meth) acrylates.

  The epoxy (meth) acrylates that can be used as the reactive compound (D) in the present invention are carboxylate compounds of a compound having an epoxy group and (meth) acrylic acid. For example, phenol novolac type epoxy (meth) acrylate, cresol novolac type epoxy (meth) acrylate, trishydroxyphenylmethane type epoxy (meth) acrylate, dicyclopentadienephenol type epoxy (meth) acrylate, bisphenol-A type epoxy (meth) Acrylate, bisphenol-F type epoxy (meth) acrylate, biphenol type epoxy (meth) acrylate, bisphenol-A novolac type epoxy (meth) acrylate, naphthalene skeleton-containing epoxy (meth) acrylate, glyoxal type epoxy (meth) acrylate, heterocyclic ring Examples thereof include epoxy (meth) acrylates and the like, and anhydride-modified epoxy acrylates thereof.

Among these, as the reactive compound (D), a radically curable compound having a (meth) acryl group, preferably a compound having a plurality of (meth) acryl groups (also referred to as a poly (meth) acrylate compound). Preferred examples include (meth) acrylate compounds containing 2 to 6, preferably 3 to 6, (meth) acrylate groups. Preferred examples of such compounds include pentaerythritol poly (2-4) (meth) acrylate, dipentaerythritol poly (2-6) (meth) acrylate, and their ε-caprolactone adduct or ethylene oxide adduct. Can be mentioned.
The numbers after “poly” such as “poly (2-4)” indicate the number of “poly”.
In the present specification, (meth) acrylate is used in the meaning of at least one of methacrylate and acrylate. Similar expressions are also used in the same meaning.
Examples of (meth) acrylate compounds containing 2 to 6 (meth) acrylate groups (also referred to as 2 to 6 functional (meth) acrylate compounds) include ε-caprolactone-modified dipentaerythritol hexa (meth) acrylate, ε- Caprolactone-modified dipentaerythritol poly (meth) acrylate; dipentaerythritol poly (2-6) (meth) acrylate such as dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate and triethylolpropane tri (meth) ) Acrylates and their ethylene oxide adducts; pentaerythritol tri (meth) acrylate and its ethylene oxide adducts; pentaerythritol tetra (meth) acrylate and its ethylene oxide Side adducts can be mentioned.
When the reactive compound (D) includes a 2-6 functional (meth) acrylate compound, the content thereof is preferably about 50-100% by mass, more preferably 80-100%, based on the total amount of the component (D). The remaining is the other reactive compound (D). An embodiment in which all components (D) are the polyfunctional (meth) acrylate compounds is also a preferred embodiment.
In the case of the cationic curable type, the epoxy group reacts with a slight acid derived from the phosphine oxide compound (A), so that it is necessary to use a two-component mixed type.

  An acid value can also be imparted to the reactive compound (D) having two or more active energy ray-reactive functional groups. For example, when an alkaline aqueous solution development method is used in which patterning is performed by using a crosslinking reaction by light to crosslink an exposed portion and eluting an unexposed portion using an alkaline aqueous solution as a developer, the component (D) For example, by using the reactive compound (D) having an acid value, the non-exposed portion can be eluted with an alkaline aqueous solution.

  In this case, the acid value of the reactive compound (D) is usually 30 to 150 mg · KOH / g, preferably 60 to 110 mg · KOH / g. When the acid value at this time is less than 30 mg · KOH / g, the developability of the aqueous solution of the active energy ray-curable resin of the present invention is remarkably lowered, and in the worst case, development may not be possible. On the other hand, if the acid value exceeds 150 mg · KOH / g, the developability becomes too high and patterning becomes difficult.

Examples of the reactive compound (D) imparted with an acid value include compounds having both an active energy ray-reactive functional group and an acidic group such as a carboxyl group and a phenol group. Examples thereof include acid-modified (meth) acrylate compounds such as acid-modified epoxy (meth) acrylate and acid-modified urethane (meth) acrylate. In the present invention, an acid-modified epoxy (meth) acrylate compound is preferable as the acid-modified (meth) acrylate compound.
The reactive compound (D) imparted with an acid value is, for example, a method in which an acid anhydride or the like is added to the aforementioned reactive compound (D) having a hydroxyl group to introduce an acid group (an acid anhydride addition reaction type compound) And a polymer having an active energy ray-reactive functional group to a polymer obtained by (co) polymerization of a monomer having an acidic group, for example, (meth) acrylic acid or vinylphenol. It can be obtained by a method (in the case of a copolymer type compound) or the like.

  The acid anhydride used in the synthesis of the reactive compound (D) having the acid value is not particularly limited, and any compound having an acid anhydride structure in the molecule can be used. Succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydro excellent in aqueous solution developability, heat resistance, hydrolysis resistance, etc. Phthalic anhydride, trimellitic anhydride or maleic anhydride is particularly preferred.

  In the acid anhydride addition reaction type compound in the reactive compound (D) to which the acid value is given, the compound having a carboxyl group specifically includes a pentaerythritol triacrylate modified product, an acid modified phenol novolak type. Epoxy (meth) acrylate, acid-modified cresol novolac type epoxy (meth) acrylate, acid-modified trishydroxyphenylmethane type epoxy (meth) acrylate, acid-modified dicyclopentadienephenol type epoxy (meth) acrylate, acid-modified bisphenol-A type epoxy (Meth) acrylate, acid-modified bisphenol-F type epoxy (meth) acrylate, acid-modified biphenol type epoxy (meth) acrylate, acid-modified bisphenol-A novolak type epoxy (meth) acrylate, acid-modified Futaren skeleton-containing epoxy (meth) acrylate, acid-modified glyoxal type epoxy (meth) acrylate, acid-modified heterocyclic epoxy (meth) acrylate, acid-modified biphenol-type epoxy (meth) acrylate.

In the present invention, as the acid anhydride addition type reactive compound (D), acid-modified epoxy (meth) acrylate is preferable as described above. As the acid-modified epoxy (meth) acrylate, acid-modified biphenol type epoxy (meth) acrylate is more preferable. When this compound is used, flame retardancy higher than that of other acid-modified epoxy (meth) acrylates can be exhibited.
When an acid-modified (meth) acrylate compound is included as the reactive compound (D), the acid-modified (meth) acrylate compound is 30 to 80% by mass, preferably 50 to 80%, based on the total amount of the component (D). It is contained in the range of mass%, and the remainder is the other reactive compound (D).

  Specific examples of the copolymer-type compound in the reactive compound (D) to which the acid value is imparted include (meth) acrylic acid containing a carboxylic acid and vinylphenol having a phenol group alone or other single unit. For example, glycidyl (meth) acrylate or isocyanatoethyl (meth) acrylate was grafted to a polymer or copolymer obtained by polymerization or copolymerization with a monomer, and an active energy ray-reactive functional group was introduced. Compounds.

  The acid anhydride addition type compound and the copolymer type compound described above can be appropriately used depending on the application and development mode. In any case, development with an alkaline (water) solution is possible by imparting an acid value to the resin, and any of them can be used equally in the present invention.

  Especially for applications that require hardness and long-term reliability such as electrical insulation materials, the acid anhydride addition type with a high degree of freedom in the resin structure prior to acid anhydride addition is suitable, and flexibility, film-forming properties, and cost are reduced. If desired, a copolymer type is preferred.

  Of these, the functional group imparting acid value is preferably a carboxyl group rather than a phenol group. This is because they are readily available, have good developability, and have a stable cured product and are well balanced.

  Furthermore, when the resin composition of the present invention using the reactive compound (D) is used as an electrically insulating material composition, the reactive compound (D) is derived from an epoxy resin and is a functional group capable of functionalizing active energy rays. Are preferably epoxy (meth) acrylates having both in the same molecule and acid-modified products thereof. This is because they are excellent in hardness, insulation and heat resistance, which are required as an electrical insulating material.

  In this invention, when using a reactive compound (D), 10-80 mass% in the whole composition (100 mass%) of this invention, Preferably it is 20-70 mass%, More preferably, it is 30-60 mass. %, More preferably, 20-50 mass% is a reactive compound (D).

  The active energy ray-curable resin composition of the present invention comprises the phosphine oxide compound (A), the polyamide compound or polyimide compound as the component (B), and two or more active energy ray reactive functional groups in one molecule. It can obtain by mixing with the reactive compound (D) which has. In a preferred embodiment, the resin composition further contains a photosensitizer (C) or a photopolymerization initiator (E). In that case, the three components and the photosensitizer (C) or photopolymerization initiator (E ) Can be mixed to obtain the resin composition. There is no restriction | limiting in particular in the order to mix, You may mix sequentially in arbitrary orders, and may mix together at once.

  Examples of the photopolymerization initiator (E) include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2- Diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyhexylphenyl ketone, 2-methyl-1- [4- Acetophenones such as (methylthio) phenyl] -2-morpholino-propan-1-one; anthrax such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide Benzophenones such as 4,4'-bismethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide A general radical type photoinitiator is mentioned. In addition, an azo initiator such as azobisisobutyronitrile, a peroxide radical initiator sensitive to heat such as benzoyl peroxide, and the like may be used in combination. One initiator can be used alone, or two or more initiators can be used in combination.

  When the photopolymerization initiator (E) is contained, the content of the photopolymerization initiator (E) is 0.5 to 20% by mass, preferably 1 to 10% by mass with respect to the entire composition (100% by mass) of the present invention. %.

  The resin composition of the present invention has advantages and disadvantages for both the negative type and the positive type, respectively. Therefore, the resin composition is appropriately selected depending on the purpose of use of the resin composition or the production process for obtaining a cured product. preferable. In the present invention, since the phosphine oxide compound (A) has an active energy ray-reactive functional group, a negative resin composition is preferred in order to maximize the effects of the present invention.

Furthermore, in this invention, a hardening | curing agent can be added suitably according to a use. In the present invention, the curing agent plays a role of forming a strong cured film by reacting with an acid group contained in the resin in a material having negative photosensitive characteristics and intended for electrical insulation. .
In the case where the resin composition of the present invention is used as a solder resist composition, the resin composition of the present invention containing a curing agent can be used. It is preferable to use a two-component resin composition of the present invention blended so as to mix a curing agent. For example, when the solder resist composition is used, it is blended into two liquids, a main agent solution (resin composition) containing the above-mentioned components (A), (B) and (D), and a curing agent solution containing an epoxy compound. It is one of the preferable embodiments that the two-component solder resist composition is used. In use, these two liquids can be mixed and used as a mixed liquid for forming a coating film or the like.
In the present specification, “mixed” or “mixed” in “mixed” includes cases where they are mixed, but is further mixed at the time of use or the like to form a single mixture (or mixed solution). In order to be used as a), until now, the case where it is combined as a set without being mixed is included.

Examples of the curing agent include an epoxy compound. The epoxy compound is arbitrarily selected depending on the purpose of use of the cured product and the required properties, and known general epoxy compounds can be arbitrarily used.
Specifically, it is a monofunctional epoxy and an epoxy compound containing two or more epoxy groups in one molecule. An epoxy compound containing two or more epoxy groups in one molecule is preferably used. This is because a stronger cured product can be obtained than using a monofunctional epoxy compound.
The epoxy equivalent of these epoxy compounds is preferably in the range of 150 to 450 g / eq, more preferably 180 to 350 g / eq. When the epoxy equivalent is too small, the obtained cured product becomes fragile, and when it is too large, the cured product obtained is weak because the number of crosslinking sites is reduced.

  Examples of the monofunctional epoxy include phenyl glycidyl ether and glycidyl (meth) acrylate.

  Specific examples of epoxy compounds having a plurality of (two or more) epoxy groups in the molecule (also referred to as polyfunctional epoxy compounds) include novolak epoxy resins (eg, phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenols). -A novolac type epoxy resin), trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, biphenol type epoxy resin, naphthalene skeleton-containing epoxy resin, glyoxal Type epoxy resin, heterocyclic epoxy resin and the like.

Examples of the phenol novolac type epoxy resin include Epicron ^RTM N-770 (manufactured by DIC Corporation), D.I. E. N438 (made by Dow Chemical Co., Ltd.), jER154 (made by Japan Epoxy Resin Co., Ltd.), EPPN-201, RE-306 (made by Nippon Kayaku Co., Ltd.), etc. are mentioned. Examples of the cresol novolac type epoxy resin include Epicron ^RTM N-695 (manufactured by DIC Corporation), EOCN-102S, EOCN-103S, EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.), UVR-6650 (manufactured by Union Carbide Corporation). ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

Examples of the trishydroxyphenylmethane type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Company), jER E1032H60 (Japan Epoxy Resin Co., Ltd.). Manufactured) and the like. Examples of the dicyclopentadiene phenol type epoxy resin include Epicron ^RTM EXA-7200 (manufactured by DIC Corporation), TACTIX-556 (manufactured by Dow Chemical Company), and the like.

  Examples of the bisphenol type epoxy resin include jER828, jER1001 (manufactured by Japan Epoxy Resin Co., Ltd.), UVR-6410 (manufactured by Union Carbide Corporation), D.I. E. Bisphenol-A type epoxy resins such as R-331 (manufactured by Dow Chemical Co., Ltd.), YD-8125 (manufactured by Toto Kasei Co., Ltd.), NER-1202, NER-1302 (manufactured by Nippon Kayaku Co., Ltd.) Bisphenol-F type epoxy resins such as YDF-8170 (manufactured by Toto Kasei Co., Ltd.), NER-7403, NER-7604 (manufactured by Nippon Kayaku Co., Ltd.), and the like.

Examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000 and NC-3000-H (Nippon Kayaku Co., Ltd.) and bixylenol type epoxy resins such as YX-4000 (manufactured by Japan Epoxy Resin Co., Ltd.). YL-6121 (manufactured by Japan Epoxy Resin Co., Ltd.) and the like. Examples of the bisphenol A novolak type epoxy resin include Epicron ^RTM N-880 (manufactured by DIC Corporation), jER E157S75 (manufactured by Japan Epoxy Resin Corporation), and the like.

  As a naphthalene skeleton containing epoxy resin, NC-7000 (made by Nippon Kayaku Co., Ltd.), EXA-4750 (made by DIC Corporation) etc. are mentioned, for example. Examples of the glyoxal type epoxy resin include GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.). Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.). Examples of the heterocyclic epoxy resin include TEPIC (manufactured by Nissan Chemical Industries, Ltd.).

  In the photosensitive resin composition of the present invention, an embodiment in which the polyfunctional epoxy resin acting as a curing agent is used in combination with the poly (meth) acrylate compound is a preferred embodiment. The polyfunctional epoxy resin is preferably a novolak epoxy resin or a biphenol type epoxy resin from the viewpoint of developability and flame retardancy. As the novolak epoxy resin, a phenol novolak resin, a cresol novolak resin, a bisphenol A novolak epoxy resin, or the like is preferable from the viewpoint of developability and flame retardancy, and a cresol novolak resin is more preferable in some cases. From the viewpoint of flame retardancy, an embodiment in which a cresol novolac resin or a biphenol type epoxy resin is used as the polyfunctional epoxy resin is a preferred embodiment.

  When using the said hardening | curing agent, 2-50 mass% with respect to the whole composition (100 mass%) of this invention, Preferably it is 3-50 mass%, More preferably, it is 4-30 mass. %, More preferably 5 to 20% by mass. Moreover, the usage-amount of a hardening | curing agent with respect to 100 mass parts of total amounts of (A) component, (B) component, and (D) component is 5-60 mass parts normally, Preferably it is about 10-50 mass parts. When the amount is too small, the resulting cured product becomes soft, and when too large, the curability and the like are adversely affected.

  In addition, for the purpose of adapting the photosensitive resin composition of the present invention to various uses, “other components” may be added up to 70 mass% of the entire composition of the present invention. Examples of other components include additives, coloring materials, and pigment materials. Examples of other components that can be used are shown below.

  Examples of additives include thermosetting catalysts such as melamine, thixotropic agents such as aerosil, silicone leveling agents, fluorine leveling agents and antifoaming agents, hydroquinone, hydroquinone monomethyl ether and other polymerization inhibitors, stabilizers and antioxidants. Etc. can be used.

  Examples of the color pigment include organic pigments such as phthalocyanine, azo, and quinacridone, carbon black, and inorganic pigments such as titanium oxide.

  Further, as the pigment material, for example, a material not intended for coloring, so-called extender pigment can be used. Examples include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay and the like.

  Other resins that are not reactive with active energy rays (so-called inert polymers), such as other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, styrene Resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof can also be used. These are preferably used in the range of up to 40% by mass of the total composition of the present invention.

  Depending on the purpose of use, for the purpose of adjusting the viscosity, a volatile solvent may be added in the range of 70% by mass, more preferably up to 50% by mass of the total composition of the present invention. Usually, the content of the solvent is 0 to 1000 parts by weight, preferably 50 to 900 parts by weight, and more preferably 150 to 100 parts by weight of the solid content of the resin composition or photosensitive resin composition of the present invention that does not contain a solvent. It is the range of -900 mass parts. Examples of the volatile solvent include the solvents mentioned in the section on the synthesis of the polyamide compound or the polyimide compound. Preferable examples include ketone solvents such as butyrolactone and N-methylpyrrolidone. Usually, it is preferable to contain about 10 to 100 parts by mass of the solvent with respect to 100 parts by mass of the solid content of the resin composition of the present invention.

Preferred embodiments of the photosensitive resin composition of the present invention described in the item (2) of the “means for solving the problems” are described below.
1. The phosphine oxide compound (A) is 1 to 94% by mass, the component (B) is 5 to 98% by mass, and the photosensitizer (C) is 1 to 30% by mass or light based on the entire photosensitive resin composition. A photosensitive resin composition containing 1 to 20% by mass of a polymerization initiator (E).
2. 2. The photosensitive resin composition according to 1 above, wherein the total content of the phosphine oxide compound (A) and the component (B) is 80 to 99% by mass and the content of the photosensitive agent (C) is 1 to 30% by mass.
3. Reaction in which the total content of the phosphine oxide compound (A) and the component (B) is 10 to 89% by mass with respect to the entire photosensitive resin composition, and two or more active energy ray-reactive functional groups are contained in one molecule. 2. The photosensitive resin composition according to 1 above, comprising 10 to 80% by mass of the photosensitive compound (D) and 1 to 10% by mass of the photopolymerization initiator (E).
4). It contains 5 to 20% by mass of the phosphine oxide compound (A) and 5 to 40% by mass of the component (B) with respect to the entire photosensitive resin composition, and the total content of both is 15 to 49% by mass. The photosensitive resin composition according to 3 above, containing 50 to 75% by mass of the reactive compound (D) and 1 to 10% by mass of the photopolymerization initiator (E).
5. As said reactive compound (D), a 2-6 functional (meth) acrylate compound is included in 50-100 mass% with respect to the total amount of (D) component, and the remainder is said other reactive compound ( 5. The photosensitive resin composition according to 3 or 4 above, which is D).
6). As said 2-6 functional (meth) acrylate compound, an acid modified (meth) acrylate compound is included in 30-80 mass% with respect to the total amount of (D) component, and the remainder is the said other reactivity. The photosensitive resin composition as described in any one of said 3-5 which is a compound (D).

7). 7. The photosensitive resin composition according to 6 above, wherein the acid-modified (meth) acrylate compound is an acid-modified epoxy (meth) acrylate.
8). Further, as a curing agent, an epoxy compound having a plurality of epoxy groups in the molecule (polyfunctional epoxy compound) is added to the total amount of 100 parts by mass in the (A) component, the (B) component, and the (D) component. The photosensitive resin composition as described in any one of said 3-7 mix | blended in the ratio of -60 mass parts.
9. The photosensitive resin composition as described in any one of said 1-8 which contains a solvent by the content of 50-900 mass parts with respect to 100 mass parts of solid content total amount of a resin composition.
10. Component (B) is a polyamide compound (B-1) or a polyimide compound (B) obtained by a reaction of a bicyclic or tricyclic aromatic diamine whose aromatic ring is a benzene ring with a bicyclic aromatic tetrabasic acid dianhydride. -2), or the photosensitivity according to any one of (2) and (4)-(7) in "Means for Solving the Problems" above. Resin composition.
11. (B) A component is a polyamide compound (B-1) or a polyimide compound (B-2) obtained by reaction of bicyclic aromatic diamine and bicyclic aromatic tetrabasic dianhydride, and at least any one On the other hand but, -SO 2 _- two joined by a bridging group aromatic diamine or -SO 2 _- any one of the above 1 to 10 is a bicyclic aromatic tetracarboxylic acid dianhydride which is coupled with a bridging group Or the photosensitive resin composition according to any one of (2) and (4) to (7) in “Means for Solving the Problems”.
12 The bicyclic aromatic diamine bonded through a —SO ₂ — bridging group is bis (aminophenyl) sulfone, and the bicyclic aromatic tetrabasic dianhydride bonded through a —SO ₂ — bridging group is diphenyl sulfone tetracarboxylic. 12. The photosensitive resin composition as described in 11 above, which is an acid anhydride.

13. The photosensitive resin composition as described in any one of said 8-12 whose polyfunctional epoxy compound is a novolak epoxy resin or a bisphenol epoxy resin.
14. As a 2-6 functional (meth) acrylate compound, pentaerythritol poly (2-4) (meth) acrylate, dipentaerythritol poly (2-6) (meth) acrylate, and their ε-caprolactone modified products and The photosensitive resin composition as described in any one of 6 to 12 above, which contains 10 to 50% by mass of at least one selected from the group consisting of modified ethylene oxide, based on the total amount of component (D).
15. Pentaerythritol poly (2-4) (meth) acrylate, dipentaerythritol poly (2-6) (meth) acrylate, and at least one selected from the group consisting of ε-caprolactone-modified products and ethylene oxide-modified products 15. The photosensitive resin composition according to 14 above, wherein is an ethylene oxide-modified dipentaerythritol poly (2-6) (meth) acrylate.
16. The molecular weight of the polyamide compound (B-1) or polyimide compound (B-2) as the component (B) is 8,000 to 150,000, preferably 15,000 to 80,000 in terms of weight average molecular weight. The photosensitive resin composition according to any one of 1 to 15 or (2), (4) to (7) of the “Means for Solving the Problem”, or the “Problem” The resin composition according to (1) of “Means for Solving the Problem”.

  As described above, the photosensitive resin composition of the present invention can be formed into a positive photosensitive resin composition by adding the photosensitizer (C) or the photopolymerization initiator (E), or negative. It can also be set as a photosensitive resin composition of a mold. By irradiating the resin composition with active energy rays, it is possible to cause the desired characteristic change. Specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X rays, gamma rays and laser rays, particle rays such as alpha rays, beta rays and electron rays. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention.

In the present invention, the molding material is formed by placing an uncured composition in a mold, or pressing a mold to form an object, and then reacting with a positive type or a negative type, preferably a negative type by an active energy ray. It refers to a material used for the purpose of forming a negative type characteristic change by irradiating an uncured composition with a focused light such as a laser.
Specific applications include a sheet formed into a flat shape, a sealing material for protecting the element, a so-called nanoimprint material that performs fine molding by pressing a "mold" that has been micro-processed into an uncured composition, Furthermore, sealing materials and the like for the purpose of electrical insulation, which are required to have flame retardancy and high reliability and are repelled from halogen compounds, are mentioned as suitable applications.
In the present invention, the film forming material is used for the purpose of coating the surface of a substrate. Specific applications include gravure inks, flexo inks, silk screen inks, offset inks and other ink materials, hard coats, top coats, overprint varnishes, clear coats and other coating materials, laminating, optical disk and other various adhesives. Such materials include adhesive materials such as adhesives and adhesives, resist materials such as solder resists, etching resists, and resists for micromachines. Furthermore, after the film forming material is temporarily applied to the peelable substrate and formed into a film, it is bonded to the original target substrate to form a film, so-called dry film also corresponds to the film forming material. .

In the present invention, the insulating material composition means that a film layer of the composition is formed on a substrate, and the electric resistance is large even when a voltage is applied between two target portions in an electronic circuit or its components. Refers to an active energy curable resin composition that does not flow. Specific applications include overcoat materials for flexible wiring boards and interlayer insulation films for multilayer substrates, molding materials for insulation films and passivation films for solid elements in the semiconductor industry, and interlayers for semiconductor integrated circuits and multilayer printed wiring boards. It is also preferably used for an insulating material, a solder resist used for protecting the substrate, and the like. It is particularly suitable for flexible substrates that are particularly required to have high flame resistance. This is because the photosensitive resin composition of the present invention can not only provide high flame retardancy but also exhibit long-term insulation stability.
The insulating material has a portion requiring insulation and a portion requiring conduction on the substrate, and these must be patterned as necessary. At that time, a pattern may be formed by a printing method, but fine patterning is difficult and is not suitable for producing a high-density substrate. However, the photosensitive resin composition of the present invention is used to form a coating layer of the composition on a substrate, and then irradiated with active energy rays such as ultraviolet rays, so that the physical properties of irradiated and unirradiated portions By drawing using this difference, fine patterning can be performed.

  In addition, the photosensitive resin composition of the present invention is also used as an optical waveguide for which high flame retardancy is similarly required, for printed wiring boards, electrical / electronic / optical substrates such as optoelectronic substrates and optical substrates, and the like. The As a particularly suitable application, it is preferable as an insulating material that requires patterning, such as a permanent resist application such as a solder resist, taking advantage of the characteristics that can provide flame retardancy and high reliability. Higher flame retardancy is exhibited by combining the phosphine oxide compound (A) and the polyamide compound (B-1) or polyimide compound (B-2) as the component (B) used in the present invention, and further reactive. When combined with the compound (D) and the photopolymerization initiator (E), they react in the solder resist material, so that they also have an effect as a crosslinking agent. Therefore, it is possible to achieve both high flame retardancy and flexibility without adding extender pigments.

  Although the photosensitive resin composition of the present invention does not contain a halogen-based flame retardant and has a halogen compound content of 10,000 ppm or less, more preferably 5000 ppm or less, it has flame retardancy.

  The method for forming the film is not particularly limited, but an intaglio printing method such as gravure, a relief printing method such as flexo, a stencil printing method such as silk screen, a lithographic printing method such as offset, a roll coater, a knife coater, and a die coater. Various coating methods such as curtain coater, spin coater and spray coater can be arbitrarily adopted.

  The cured product of the photosensitive resin composition of the present invention is also included in the present invention. The cured product of the present invention refers to a product obtained by irradiating the photosensitive resin composition of the present invention with active energy rays and further curing.

  The multilayer material of the present invention refers to a material having at least two layers obtained by forming and curing a film of the resin composition of the present invention on a substrate.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. Moreover, unless otherwise indicated in an Example, "part" shows a mass part and "%" shows the mass%. The molecular weights of the polyamide compound and the polyimide compound were measured by gel filtration chromatography using a 10 mM lithium bromide N-methylpyrrolidone solution as an eluent. At this time, polystyrene was used as a molecular weight standard.

  Following formula (1)

(In the formula, R represents a hydrogen atom or a methyl group.)
The phosphine oxide compound (A) represented by was synthesized according to the method of Synthesis Example 1-1 below.

Synthesis Example 1-1: Synthesis of phosphine oxide compound (A) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (Sanko Stock Co., Ltd.) was added to a 2 L reactor equipped with a stirrer, a thermometer and a condenser. 216.2 g (1.0 mol) and 246.2 g of toluene (trade name, HCA) manufactured by company were charged and dissolved at a temperature of 80 to 90 ° C. Next, 30.0 g (1.0 mol) of paraformaldehyde was gradually added thereto with stirring, and reacted at a reaction temperature of 80 ° C. to 90 ° C. for 3 hours. As a result, 246.2 g of white crystals were obtained.
Next, 246.2 g (1.0 mol) of the obtained white crystals, 144.7 g (2.0 mol) of acrylic acid, 400 g of toluene, 1.5 g of methoquinone and 14.5 g of P-toluenesulfonic acid monohydrate were obtained as above. The same reactor was charged and a dehydration condensation reaction was carried out at 105 to 110 ° C. for 13 hours. The resulting reaction solution was washed twice with 10% aqueous sodium carbonate solution and once with 20% brine. Thereafter, toluene was distilled under reduced pressure to obtain 267.9 g (yield: 89.2%) of a pale yellow liquid phosphine oxide compound (A) (R = H in formula (1)) ((A) R = H). .
This phosphine oxide compound (A) exhibits the following physical properties.
Viscosity (40 ℃) 6300 CPS
Refractive index (20 ° C) 1.6145
H-NMR (measured as deuterated chloroform solution)
4.80 ppm = 2H, 5.60 ppm = 1H, 6.16 ppm = 1H, 6.45 ppm = 1H, 7.24-7.93 ppm = 8H

Synthesis Example 2-1 Synthesis of Polyamide Compound 1 In a 1 L reactor equipped with a stirrer, a thermometer, and a condenser, 121 g (0.5 mol) of bis (3-aminophenyl) sulfone as a diamine compound and N-methyl as a solvent Pyrrolidone was charged so that the solid content of the target product was 40% by weight (471 g). Further, 193 g (0.5 mol) of 3,3′-4,4′-diphenylsulfonetetracarboxylic anhydride was added as a tetrabasic dianhydride.
Then, it was made to react at 100 degreeC for 10 hours, and the polyamide compound 1 (Poly-A1) solution (solid content of 40 weight%) was obtained. The weight average molecular weight of the polyamide compound 1 (Poly-A1) was 65,000.

Synthesis Example 2-2: Synthesis of Polyimide Compound (Poly-I) To 350 g (solid content 140 g) of N-methylpyrrolidone solution of polyamide compound 1 (Poly-A1) synthesized in Synthesis Example 2-1, solid content adjustment was performed. Therefore, N-methylpyrrolidone was added to a solid content of 25% (350 g). 10 g of toluene was added as a dehydration aid. Thereafter, a dehydration imidation reaction was performed while azeotroping with toluene at 200 ° C. for 20 hours to obtain a polyimide compound (Poly-I) solution (solid content 25%). The weight average molecular weight of the polyimide compound (Poly-I) was 73,000.

Synthesis Example 2-3: Synthesis of Polyamide Compound 2 (Poly-A2) Into a 1 L reactor equipped with a stirrer, a thermometer, and a condenser, 121 g (0.5 mol) of bis (3-aminophenyl) sulfone was further added as a diamine compound. As a solvent, N-methylpyrrolidone was charged (471 g) so that the solid content of the target product was 40% by weight. Further, 147 g (0.5 mol) of a hydrogenated product of 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride was added as a tetrabasic acid dianhydride.
Then, it was made to react at 100 degreeC for 10 hours, and the polyamide compound 2 (Poly-A2) solution (solid content of 40 weight%) was obtained. The weight average molecular weight of the polyamide compound 2 (Poly-A2) was 68,000.

Synthesis Example 2-4: Synthesis of polyamide compound 3 (Poly-A3) In a 1 L reactor equipped with a stirrer, a thermometer, and a condenser, 36.1 g (0.25 mol) of 1,8-octamethylenediamine as a diamine compound and As a solvent, 393.6 g of 1,3-bis (3-aminophenoxy) benzene and N-methylpyrrolidone as a solvent were charged so that the solid content of the target product was 40% by weight. Further, 153.2 g (0.5 mol) of a hydrogenated product of 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride was added as a tetrabasic acid dianhydride.
Then, it was made to react at 100 degreeC for 10 hours, and the polyamide compound 3 (Poly-A3) solution (solid content of 40 weight%) was obtained. The weight average molecular weight of the polyamide compound 3 (Poly-A3) was 65,000.

Example 1: Preparation and Evaluation of Positive Solder Resist Composition Phosphine Oxide Compound (A) ((A) R = H) Obtained in Synthesis Example 1-1
5 g, 75 g of the polyamide compound solution (solid content 40 wt%) obtained in Synthesis Example 2-1 or 2-3, or the polyimide compound solution obtained in Synthesis Example 2-2 (solid content 25) %) And 120 g of DTEP-350 (manufactured by Daitokemix Co., Ltd.) as a photosensitizer (C) were mixed in the combinations shown in Table 1, and the photosensitive resin composition of the present invention (Examples 1-1 to 1-3) Got. This was applied to a copper circuit printed circuit board by a screen printing method so that the thickness after drying was 25 μm, and the coating film was dried with a hot air dryer at 80 ° C. for 60 minutes.
Next, the mask film on which the pattern was drawn was brought into close contact, and irradiated with ultraviolet rays using an ultraviolet exposure device (USHIO: 500 W multilight). Next, spray development (spray pressure: 0.2 MPa) was performed for 120 seconds using a 1% tetramethylammonium hydroxide aqueous solution (temperature: 30 ° C.) as a developer. After washing with water, heat treatment was performed in a hot air dryer at 150 ° C. for 60 minutes to obtain a copper circuit printed board having the cured product layer of the present invention.
Evaluation of the developability of the coating film was carried out by the method described later, and the results are shown in Table 1. Moreover, the reliability of a hardened | cured material layer and flame retardance evaluation were performed by the postscript method, and the result was shown in Table 1.

Comparative Example 1: Preparation and Evaluation of Positive Solder Resist Composition The phosphine oxide compound (A) of the present invention obtained in the synthesis example is not used, or 5 g of HCA-HQ (a flame retardant manufactured by Sanko Co., Ltd.) About the point other than using, it carried out similarly to Example 1, and obtained the photosensitive resin composition for comparison (Comparative Examples 1-1 to 1-3). It attached to the obtained resin composition, it carried out similarly to the said Example, formation of the coating film, image development, and hardening were performed, and the copper circuit printed circuit board which has a hardened | cured material layer was obtained.
The developability of the coating film was evaluated by the method shown below. The evaluation results are shown in Table 1. Moreover, the reliability of a hardened | cured material layer and flame retardance evaluation were performed by the postscript method, and the result was shown in Table 1.

(Developability evaluation)
The developability was evaluated based on the time until the pattern shape portion was completely developed, that is, the so-called break time when developing the exposed portion that passed through the pattern mask (unit: second). In addition, about what did not break within 120 seconds, it was set as x.

(Reliability evaluation)
Using a silk screen method on a polyimide substrate on which a line / space = 50/50 μm comb-shaped electrode is formed, a coating film is prepared with each composition so that the thickness becomes approximately 25 μm after curing. In the same manner as above, ultraviolet rays were irradiated to obtain a polyimide substrate having a cured product layer. The polyimide substrate with a cured product layer is placed in a high-temperature bath at 120 ° C. and 85% relative humidity, a voltage of 100 V is applied, the change in resistance value is observed from the start of the test, and the resistance value falls below 1 MΩ. The time was measured and shown in Table 1 below. It is determined that the longer the time, the longer-term reliability of the circuit can be secured.

(Flame retardance evaluation)
The flame retardancy of each non-halogen flame-retardant substrate RO-67G (thickness: 0.2 mm) manufactured by Hitachi Chemical Co., Ltd. After coating the entire surface by screen printing and curing the coating film in the same manner as in the Examples, flame retardancy was evaluated by a method based on the UL test method. The evaluation criteria are as follows.
: Equivalent to UL V-0
(The total combustion time when 5 test pieces are ignited twice each is 50 seconds or less)
○: Equivalent to UL V-1 (The total combustion time when each of the five test pieces is ignited twice is 50 to 250 seconds. There is no burning fallen object after the test)
Δ: Equivalent to UL V-2 (total burning time when 5 test pieces are ignited twice each is 50 to 250 seconds. There are burning fallen objects after the test)
×: No self-extinguishing

Table 1: Example 1 and Comparative Example 1
Example Flame-retardant compound (B) Component Development property Reliability Flame-retardant Example 1-1 (A) R = H Poly-A1 38sec 80hr 48sec ◎
Example 1-2 (A) R = H Poly-I 115 sec 270 hr 41 sec ◎
Example 1-3 (A) R = H Poly-A2 25sec 100hr 47sec ◎
Comparative Example 1-1 None Poly-A1 55sec 78hr ×
Comparative Example 1-2 None Poly-I × 78hr ×
Comparative Example 1-3 HCA-HQ Poly-A1 50sec 22hr 56sec △

Example 2 Preparation and Evaluation of Negative Solder Resist Composition 10 g of the phosphine oxide compound (A) obtained in the synthesis example and 25 g of the polyamide compound solution obtained in the synthesis example 2-1 or 2-3. Or 40 g of the polyimide compound solution obtained in Synthesis Example 2-2, 10 g of ethylene oxide-modified dipentaerythritol hexaacrylate (KAYARAD ^RTM DPEA-12X manufactured by Nippon Kayaku Co., Ltd.) as the reactive compound (D), acid Modified epoxy acrylate (oxidation: 100 mg KOH / g, KAYARAD ^RTM CCR-1159X, Nippon Kayaku Co., Ltd.) 30 g, photopolymerization initiator (E), Irgacure ^RTM 907 (Ciba Specialty Chemicals) 3 g, KAYACURE ^RTM DETX-S HP (Nippon Kayaku Co., Ltd. Company Ltd.) 0.5 g, as a curing agent, a mixture of cresol novolac type epoxy resin 8 g, to obtain an active energy ray curable resin composition of the present invention. This was applied to a copper circuit printed circuit board by a screen printing method so that the thickness after drying was 25 μm, and the coating film was dried with a hot air dryer at 80 ° C. for 60 minutes. Thereafter, in the same manner as in Example 1, a copper circuit printed board having the cured product layer of the present invention was obtained.
Evaluation of the developability of the coating film, reliability of the cured product layer, and evaluation of flame retardancy were carried out in the same manner as in Example 1.
The results are shown in Table 2.

Example 3 Preparation and Evaluation of Negative Solder Resist Composition 10 g of the reactive compound (A) of the present invention obtained in the synthesis example, 25 g of the polyamide solution obtained in the synthesis example 2-4, reaction 10 g of polyethylene glycol diacrylate (KAYARAD ^RTM PEG-400DAX made by Nippon Kayaku) as the active compound (D), acid-modified epoxy acrylate (KAYARAD ZCR-1569X solid content 65% (propylene glycol monomethyl ether acetate) made by Nippon Kayaku) 30 g, Irgacure ^RTM 907 (manufactured by Ciba Specialty Chemicals), KAYACURE ^RTM DETX-SHP (manufactured by Nippon Kayaku) 0.5 g, as a curing agent, 8 g of a biphenol type epoxy resin, as a solvent N-methylpyrrolidone Was mixed to obtain an active energy ray-curable resin composition of the present invention having a solid content of 30%. This was applied to a copper circuit printed board by a screen printing method so as to have a thickness of 25 microns, and the coating film was dried for 60 minutes by a hot air dryer at 80 ° C.
Thereafter, in the same manner as in Example 1, a copper circuit printed board having the cured product layer of the present invention was obtained. Evaluation of the developability of the coating film, reliability of the cured product layer, and evaluation of flame retardancy were carried out in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 2: Preparation and Evaluation of Negative Solder Resist Composition The reactive compound (A) of the present invention obtained in the above synthesis example is not used, or 5 g of HCA-HQ (Sanko made flame retardant) is used. Other photosensitive resin compositions were obtained according to Example 2 except for the points used. The results are shown in Table 2.

Table 2: Example 2 and Comparative Example 2
Example Flame-retardant compound B) Component Developability Reliability Flame-retardant Example 2-1 (A) R = H Poly-A1 18 sec 140 hr ◎ (45 sec)
Example 2-2 (A) R = H Poly-I 30 sec 130 hr ◎ (40 sec)
Example 3-1 (A) R = H Poly-A3 15 sec 240 hr ◎ (37 sec)
Comparative Example 2-1 None Poly-A1 25sec 150hr ×
Comparative Example 2-2 None Poly-I 45sec 170hr ×
Comparative Example 2-3 HCA-HQ Poly-A1 50sec 33hr △ (59sec)
Comparative Example 2-4 (A) R = H None 10sec 150hr ×

  As can be seen from the above results, a resin having excellent flame retardancy, reliability, and developability by using the phosphine oxide compound (A) and the component (B) (polyamide compound or polyimide compound) in the present invention in combination. It is clear that a composition can be obtained.

The photosensitive resin composition of the present invention is particularly excellent in flame retardancy, reliability and developability, which are basic characteristics as a solder resist.
These basic characteristics such as flame retardancy, reliability, and developability are universal characteristics required not only for photosensitive solder resist but also for other purposes for flame retardancy. The functional resin composition can be suitably used for a wide range of applications regardless of the application.

Claims (8)

Following formula (1)

(Wherein R represents a hydrogen atom or a methyl group) As the phosphine oxide compound (A) and (B) component represented by the formula, a polyamide compound obtained by reacting a diamine compound and a tetrabasic acid dianhydride, or A photosensitive resin composition comprising a polyimide compound and a photosensitive agent (C). Furthermore as a curing agent, the photosensitive resin composition of claim 1, wherein the polyfunctional epoxy compound is blended. The photosensitive resin composition according to claim 1, which is a molding material. The photosensitive resin composition according to claim 1 , wherein the photosensitive resin composition is a film forming material. The photosensitive resin composition according to claim 1, which is an electrically insulating material. The photosensitive resin composition according to claim 1, which is a solder resist composition. A multilayer material having a cured product layer of the photosensitive resin composition according to claim 1 . Hardened | cured material of the photosensitive resin composition of Claim 1 or Claim 2 .