JP2006070248A - Curable triazine composition for electronic component, method for producing the same and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a triazine composition containing a compound curable with heat or light and having a sealing material for electronic components or a varnish for the electronic components affording a cured product having excellent heat and tinning resistances as applications and to provide a method for producing the composition. <P>SOLUTION: The curable triazine composition is characterized as comprising (A) a triazine compound represented by general formula (1) [äwherein, R<SB>1</SB>s denote each independently a bivalent organic group; X<SP>1</SP>s denote each independently a monovalent organic group; X<SP>2</SP>s denote each an oxygen atom, a sulfur atom or a group represented by general formula (2) (wherein, R<SP>2</SP>denotes a hydrogen atom, a 1-12C alkyl group, an aryl group or an aralkyl group); and n denotes an integer of 2-100}; in which a part or all of the existing n X<SP>1</SP>s have each a curable group curable with heat or light]. The curable triazine composition has a sealing material for the electronic components and/or the varnish for the electronic components as the applications. The method for producing the composition and a cured product thereof are provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a curable triazine composition containing a triazine compound that can be cured by heat or light and used for a sealing material for electronic parts and a varnish for electronic parts, a method for producing the same, and a cured product thereof.

In recent years, in the field of electronic components, materials that can withstand lead-free solder and tin plating in addition to heat resistance, electrical characteristics, and the like that have been conventionally required have been demanded.
As a sealing material for electronic parts such as an insulating protective film, a curable resin composition in which a photopolymerization initiator, a thermosetting resin, a diluent and the like are blended with a photosensitive prepolymer such as a urethane (meth) acrylate compound, Disclosed as a supplement to the lack of physical properties of conventional epoxy (meth) acrylate resins and melamine resins (Japanese Patent Application Laid-Open No. 2004-062057: Patent Document 4), but has a drawback of poor tin plating resistance. .

  On the other hand, triazine resins such as polycyanurate resin, polythiocyanurate resin, and polyguanamine resin that contain a triazine skeleton in the structure are known as resins having excellent heat resistance and flame retardancy. As an example, Japanese Patent Laid-Open No. 10-287745 (Patent Document 1) describes polycyanurate resins and polyguanamine resins, and Japanese Patent Laid-Open No. 2002-47345 (Patent Document 2) describes polythiocyanurate resins. Yes. However, these triazine resins do not have a curable group as used in the present invention.

  JP-A-60-91349 (Patent Document 3) discloses a triazine resin having an allyl group as a curable group and discloses a composition that is cured with an electron beam. There is no description of a curable triazine composition for use in a sealing material for electronic parts and a varnish for electronic parts, which contains a triazine compound that can be cured by heat or light.

JP-A-10-287745 JP 2002-47345 A JP-A-60-91349 JP 2004-062057 A

  The present invention has good heat resistance, electrical properties, flame retardancy, tin plating resistance, etc., and gives a cured product particularly excellent in heat resistance, tin plating resistance, etc. The present invention provides a triazine compound that can be cured by heat or light, a composition, and a method for producing the same.

［式中、Ｒ¹はそれぞれ独立して２価の有機基を表わし、Ｘ¹はそれぞれ独立して１価の有機基を表わし、Ｘ²は酸素原子、硫黄原子、または一般式（２）

（式中、Ｒ²は水素原子、炭素数１〜１２のアルキル基、アリール基、またはアラルキル基を表わす。）で示される基を表わし、ｎは２〜１００の整数を表わす。］で示されるトリアジン化合物であって、ｎ個存在するＸ¹の一部または全てが熱または光で硬化可能な硬化性基を有するトリアジン化合物、及び硬化剤を含むことを特徴とする硬化性トリアジン組成物。
２． 一般式（３）

（式中、Ｘ¹は熱または光で硬化可能な硬化性基を含む１価の有機基を表わし、Ｘ³はハロゲン原子を表わす。）で示される１種または２種以上のジハロトリアジン化合物に、アルコール性水酸基、チオール基、アミノ基、モノ置換アミノ基、またはフェノール性水酸基を１分子に２以上有する化合物から選ばれる１種以上の化合物を反応させて得られたトリアジン化合物に硬化剤を配合させてなる前記１に記載の硬化性トリアジン組成物。
３． 一般式（４）

（式中、Ｘ¹は熱または光で硬化可能な硬化性基を含む１価の有機基を表わす。）で示される１種または２種以上のトリアジンジチオール化合物に一般式（５）

（式中、Ｒ¹は２価の有機基を表わし、Ｘ⁴はハロゲン原子、メタンスルホニルオキシ基、トリフルオロメタンスルホニルオキシ基またはｐ−トルエンスルホニルオキシ基を表わす。）で示される１種以上の化合物を反応させて得られたトリアジン化合物に硬化剤を配合させてなる前記１に記載の硬化性トリアジン組成物。
４． 一般式（４）

（式中、Ｘ¹は熱または光で硬化可能な硬化性基を含む１価の有機基を表わす。）で示される１種または２種以上のトリアジンジチオール化合物に２官能のα，β−不飽和カルボニル化合物を１種以上反応させて得られたトリアジン化合物に硬化剤を配合させてなる前記１に記載の硬化性トリアジン組成物。
５． 一般式（１）中のｎ個のＲ¹が下記式（６）〜（９）及び（５５）〜（５７）

（式中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶はそれぞれ独立して、水素原子、フッ素原子、塩素原子、臭素原子、炭素数１〜１２のアルキル基、アラルキル基、パーフルオロアルキル基、シクロヘキシル基、またはフェニル基を表わす。）

（式中、４個のＲ⁷はそれぞれ独立して水素原子またはメチル基を表わす。）

（式中、４個のＲ³⁰はそれぞれ独立して水素原子またはメチル基を表わす。）

（式中、４個のＲ³¹はそれぞれ独立して水素原子またはメチル基を表わす。）

（式中、４個のＲ³²はそれぞれ独立して水素原子またはメチル基を表わす。）
で示される少なくとも一つから選択される基である前記１に記載の硬化性トリアジン組成物。
６． 一般式（１）中のｎ個のＲ¹が下記式（５８）〜（６０）

で示される少なくとも一つから選択される基である前記１に記載の硬化性トリアジン組成物。
７． 一部または全てのＸ¹が、アリル基、ビニル基、（メタ）アクリロイル基、エポキシ基、オキセタニル基、カルボキシル基、酸無水物基、アミノ基、チオール基、及びブロック化されていてもよいイソシアネート基から選ばれる１種以上を有する１価の有機基である前記１〜６のいずれかに記載の硬化性トリアジン組成物。
８． 一部または全てのＸ¹がアリル基を有し、前記硬化剤として有機過酸化物を含む前記１〜７のいずれかに記載の硬化性トリアジン組成物。
９． 一部または全てのＸ¹がビニル基または（メタ）アクリロイル基を有し、前記硬化剤としてアゾ化合物を含む前記１〜７のいずれかに記載の硬化性トリアジン組成物。
１０． 一部または全てのＸ¹がエポキシ基を有し、前記硬化剤としてアミン、カルボン酸または酸無水物の多官能化合物を含む前記１〜７のいずれかに記載の硬化性トリアジン組成物。
１１． 一部または全てのＸ¹がオキセタニル基を有し、前記硬化剤として式（４９）

（式中、［Ａ］^h+はオニウムイオン、［Ｘ］^h-は陰イオン、ｈは整数を表わす。）
で示されるオニウム塩を含む前記１〜７のいずれかに記載の硬化性トリアジン組成物。
１２． 一部または全てのＸ¹がカルボキシル基または酸無水物基を有し、前記硬化剤としてエポキシ化合物、オキセタン化合物、アミン化合物またはイソシアネート化合物の多官能化合物を含む前記１〜７のいずれかに記載の硬化性トリアジン組成物。
１３． 一部または全てのＸ¹がアミノ基を有し、前記硬化剤としてエポキシ化合物、イソシアネート化合物、酸無水物またはα，β−不飽和カルボニル化合物の多官能化合物を含む前記１〜７のいずれかに記載の硬化性トリアジン組成物。
１４． 一部または全てのＸ¹がチオール基を有し、前記硬化剤としてポリエン化合物を含む前記１〜７のいずれかに記載の硬化性トリアジン組成物。
１５． 一部または全てのＸ¹がブロック化されていてもよいイソシアネート基を有し、前記硬化剤としてアミン化合物もしくはカルボン酸化合物の多官能化合物または酸無水物を含む前記１〜７のいずれかに記載の硬化性トリアジン組成物。
１６． さらに溶媒を含む前記１〜１５のいずれかに記載の硬化性トリアジン組成物。
１７． 前記溶媒が、エーテル系溶媒、含硫黄系溶媒、エステル系溶媒、ケトン系溶媒及び芳香族炭化水素系溶媒から選ばれた1種以上である前記１６に記載の硬化性トリアジン組成物。
１８． さらに有機または無機の微粒子を配合することを特徴とする前記１６または１７に記載の硬化性トリアジン組成物。
１９． 前記有機または無機の微粒子が、シリカ（ＳｉＯ₂）、アルミナ（Ａｌ₂Ｏ₃）、チタニア（ＴｉＯ₂）、酸化タンタル（Ｔａ₂Ｏ₅）、ジルコニア（ＺｒＯ₂）、窒化珪素（Ｓｉ₃Ｎ₄）、チタン酸バリウム（ＢａＯ・ＴｉＯ₂）、炭酸バリウム（ＢａＣＯ₃）、チタン酸鉛（ＰｂＯ・ＴｉＯ₂）、チタン酸ジルコン酸鉛（ＰＺＴ）、チタン酸ジルコン酸ランタン鉛（ＰＬＺＴ）、酸化ガリウム（Ｇａ₂Ｏ₃）、スピネル（ＭｇＯ・Ａｌ₂Ｏ₃）、ムライト（３Ａｌ₂Ｏ₃・２ＳｉＯ₂）、コーディエライト（２ＭｇＯ・２Ａｌ₂Ｏ₃／５ＳｉＯ₂）、タルク（３ＭｇＯ・４ＳｉＯ₂・Ｈ₂Ｏ）、チタン酸アルミニウム（ＴｉＯ₂−Ａｌ₂Ｏ₃）、イットリア含有ジルコニア（Ｙ₂Ｏ₃−ＺｒＯ₂）、珪酸バリウム（ＢａＯ・８ＳｉＯ₂）、窒化ホウ素（ＢＮ）、炭酸カルシウム（ＣａＣＯ₃）、硫酸カルシウム（ＣａＳＯ₄）、酸化亜鉛（ＺｎＯ）、チタン酸マグネシウム（ＭｇＯ・ＴｉＯ₂）、硫酸バリウム（ＢａＳＯ₄）、有機ベントナイト、カーボン（Ｃ）、ポリイミド樹脂若しくはその前駆体、ポリアミドイミド樹脂若しくはその前駆体、及びポリアミド樹脂から選ばれる１種以上である前記１８に記載の硬化性トリアジン組成物。
２０． 前記有機または無機の微粒子が平均粒子径５０μｍ以下である前記１９に記載の硬化性トリアジン組成物。
２１． ２５℃における粘度が０．５〜５００Ｐａ・ｓであり、かつチキソトロピー係数が１．１以上であることを特徴とする前記１８〜２０のいずれかに記載の硬化性トリアジン組成物。
２２． 一般式（３）

（式中、Ｘ¹は熱または光で硬化可能な硬化性基を含む１価の有機基を表わし、Ｘ³はハロゲン原子を表わす。）で示される１種または２種以上のジハロトリアジン化合物に、アルコール性水酸基、チオール基、アミノ基、モノ置換アミノ基、またはフェノール性水酸基を１分子に２以上有する化合物から選ばれる１種以上の化合物を反応させて得られたトリアジン化合物に硬化剤を配合させることを特徴とする前記２に記載の硬化性トリアジン組成物の製造方法。
２３． 一般式（４）

（式中、Ｘ¹は熱または光で硬化可能な硬化性基を含む１価の有機基を表わす。）で示される１種または２種以上のトリアジンジチオール化合物に一般式（５）

（式中、Ｒ¹は２価の有機基を表わし、Ｘ⁴はハロゲン原子、メタンスルホニルオキシ基、トリフルオロメタンスルホニルオキシ基またはｐ−トルエンスルホニルオキシ基を表わす。）で示される１種以上の化合物を反応させて得られた硬化性トリアジン化合物に硬化剤を配合させることを特徴とする前記３に記載の硬化性トリアジン組成物の製造方法。
２４． 一般式（４）

（式中、Ｘ¹は熱または光で硬化可能な硬化性基を含む１価の有機基を表わす。）で示される１種または２種以上のトリアジンジチオール化合物に２官能のα，β−不飽和カルボニル化合物を１種以上反応させて得られた硬化性トリアジン化合物に硬化剤を配合させることを特徴とする前記４に記載の硬化性トリアジン組成物の製造方法。
２５． （Ａ）一般式（１）

［式中、Ｒ¹はそれぞれ独立に２価の有機基を表わし、Ｘ¹はそれぞれ独立に１価の有機基を表わし、Ｘ²は酸素原子、硫黄原子、または一般式（２）

（式中、Ｒ²は水素原子または炭素数１〜１２のアルキル基、アリール基、またはアラルキル基を表わす。）で示される基を表わし、ｎは２〜１００の整数を表わす。］で示され、ｎ個存在するＸ¹の一部または全てが熱または光で硬化可能な硬化性基を有するトリアジン化合物において、Ｒ¹で表される２価の有機基が下記式（５８）、（５９）または（６０）

で表される有機基であり、
Ｘ¹で表される１価の有機基がエチレン性炭素−炭素二重結合を有する有機基であり、Ｘ²が酸素原子または硫黄原子であることを特徴とするトリアジン化合物。
２６． 前記１〜２１のいずれかに記載の硬化性トリアジン組成物を硬化してなる硬化物。
２７． 前記１〜２１のいずれかに記載の硬化性トリアジン組成物を含む電子部品用封止材料。
２８． 前記１〜２１のいずれかに記載の硬化性トリアジン組成物を含む電子部品用ワニス。 The present invention
1. (A) General formula (1)

[In the formula, each R ¹ independently represents a divalent organic group, each X ¹ independently represents a monovalent organic group, and X ² represents an oxygen atom, a sulfur atom, or a general formula (2)

(Wherein R ² represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, or an aralkyl group), and n represents an integer of 2 to 100. A triazine compound represented by, curable triazine, which comprises a triazine compound of part or all X ¹ n number exists with a curable curable groups by heat or light, and a curing agent Composition.
2. General formula (3)

(Wherein X ¹ represents a monovalent organic group containing a curable group curable with heat or light, and X ³ represents a halogen atom), or one or more dihalotriazine compounds And a triazine compound obtained by reacting at least one compound selected from a compound having two or more alcoholic hydroxyl groups, thiol groups, amino groups, mono-substituted amino groups, or phenolic hydroxyl groups per molecule with a curing agent. 2. The curable triazine composition as described in 1 above, which is formulated.
3. General formula (4)

(Wherein X ¹ represents a monovalent organic group containing a curable group curable by heat or light) and one or more triazinedithiol compounds represented by the general formula (5)

(Wherein R ¹ represents a divalent organic group, and X ⁴ represents a halogen atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group or a p-toluenesulfonyloxy group). 2. The curable triazine composition as described in 1 above, wherein a curing agent is blended with a triazine compound obtained by reacting.
4). General formula (4)

(Wherein X ¹ represents a monovalent organic group containing a curable group curable with heat or light) and one or more triazinedithiol compounds represented by 2. The curable triazine composition according to 1 above, wherein a curing agent is added to a triazine compound obtained by reacting at least one saturated carbonyl compound.
5. Formula (1) n number of R ¹ is represented by the following formula (6) to (9) and (55) - (57)

(Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 12 carbon atoms, an aralkyl group, a perfluoroalkyl group, Represents a cyclohexyl group or a phenyl group.)

(In the formula, four R ^{7 s} each independently represent a hydrogen atom or a methyl group.)

(In the formula, each of four R ³⁰ independently represents a hydrogen atom or a methyl group.)

(In the formula, four R ^{31 s} each independently represent a hydrogen atom or a methyl group.)

(In the formula, four R ^{32 s} each independently represent a hydrogen atom or a methyl group.)
2. The curable triazine composition according to 1 above, which is a group selected from at least one of
6). Formula (1) n number of R ¹ is represented by the following formula in (58) - (60)

2. The curable triazine composition according to 1 above, which is a group selected from at least one of
7). Some or all of X ¹ may be allyl group, vinyl group, (meth) acryloyl group, epoxy group, oxetanyl group, carboxyl group, acid anhydride group, amino group, thiol group, and optionally blocked isocyanate The curable triazine composition according to any one of 1 to 6, which is a monovalent organic group having one or more selected from a group.
8). The curable triazine composition according to any one of 1 to 7, wherein some or all of X ¹ has an allyl group and includes an organic peroxide as the curing agent.
9. The curable triazine composition according to any one of 1 to 7, wherein some or all of X ¹ has a vinyl group or a (meth) acryloyl group and includes an azo compound as the curing agent.
10. The curable triazine composition according to any one of 1 to 7 above, wherein some or all of X ¹ have an epoxy group and include a polyfunctional compound of amine, carboxylic acid or acid anhydride as the curing agent.
11. Part or all of X ¹ has an oxetanyl group, and the curing agent is represented by the formula (49)

(In the formula, [A] ^{h +} represents an onium ion, [X] ^h- represents an anion, and h represents an integer.)
The curable triazine composition according to any one of 1 to 7 above, which comprises an onium salt represented by the formula:
12 A part or all of X ¹ has a carboxyl group or an acid anhydride group, and the curing agent includes an epoxy compound, an oxetane compound, an amine compound, or a polyfunctional compound of an isocyanate compound as described in any one of 1 to 7 above. Curable triazine composition.
13. Any one or all of X ¹ have an amino group, and the curing agent includes an epoxy compound, an isocyanate compound, an acid anhydride, or a polyfunctional compound of an α, β-unsaturated carbonyl compound. The curable triazine composition described.
14 The curable triazine composition according to any one of 1 to 7, wherein a part or all of X ¹ has a thiol group and includes a polyene compound as the curing agent.
15. A part or all of X ¹ has an optionally blocked isocyanate group, and the curing agent includes a polyfunctional compound of an amine compound or a carboxylic acid compound or an acid anhydride as described above. A curable triazine composition.
16. Furthermore, the curable triazine composition in any one of said 1-15 containing a solvent.
17. 17. The curable triazine composition according to 16, wherein the solvent is at least one selected from an ether solvent, a sulfur-containing solvent, an ester solvent, a ketone solvent, and an aromatic hydrocarbon solvent.
18. 18. The curable triazine composition as described in 16 or 17 above, further comprising organic or inorganic fine particles.
19. The organic or inorganic fine particles are silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), silicon nitride (Si ₃ N _4). ), Barium titanate (BaO · TiO ₂ ), barium carbonate (BaCO ₃ ), lead titanate (PbO · TiO ₂ ), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga ₂ O ₃ ), spinel (MgO.Al ₂ O ₃ ), mullite (3Al ₂ O ₃ .2SiO ₂ ), cordierite (2MgO.2Al ₂ O ₃ / 5SiO ₂ ), talc (3MgO.4SiO _2. H ₂ O), aluminum titanate _{(TiO 2 -Al 2 O 3)} , yttria-containing zirconia _{(Y 2 O 3 -ZrO 2)} , barium silicate (BaO · 8SiO _2), Boron nitride (BN), calcium carbonate (CaCO ₃ ), calcium sulfate (CaSO ₄ ), zinc oxide (ZnO), magnesium titanate (MgO · TiO ₂ ), barium sulfate (BaSO ₄ ), organic bentonite, carbon (C) 19. The curable triazine composition as described in 18 above, which is one or more selected from polyimide resin or a precursor thereof, polyamideimide resin or a precursor thereof, and a polyamide resin.
20. 20. The curable triazine composition as described in 19 above, wherein the organic or inorganic fine particles have an average particle size of 50 μm or less.
21. 21. The curable triazine composition as described in any one of 18 to 20 above, having a viscosity at 25 ° C. of 0.5 to 500 Pa · s and a thixotropic coefficient of 1.1 or more.
22. General formula (3)

(Wherein X ¹ represents a monovalent organic group containing a curable group curable with heat or light, and X ³ represents a halogen atom), or one or more dihalotriazine compounds And a triazine compound obtained by reacting at least one compound selected from a compound having two or more alcoholic hydroxyl groups, thiol groups, amino groups, mono-substituted amino groups, or phenolic hydroxyl groups per molecule with a curing agent. 3. The method for producing a curable triazine composition as described in 2 above, which comprises blending.
23. General formula (4)

(Wherein X ¹ represents a monovalent organic group containing a curable group curable by heat or light) and one or more triazinedithiol compounds represented by the general formula (5)

(Wherein R ¹ represents a divalent organic group, and X ⁴ represents a halogen atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group or a p-toluenesulfonyloxy group). 4. The method for producing a curable triazine composition as described in 3 above, wherein a curing agent is added to the curable triazine compound obtained by reacting the curable triazine compound.
24. General formula (4)

(Wherein X ¹ represents a monovalent organic group containing a curable group curable with heat or light) and one or more triazinedithiol compounds represented by 5. The method for producing a curable triazine composition as described in 4 above, wherein a curing agent is added to the curable triazine compound obtained by reacting at least one saturated carbonyl compound.
25. (A) General formula (1)

[Wherein, R ¹ independently represents a divalent organic group, X ¹ independently represents a monovalent organic group, and X ² represents an oxygen atom, a sulfur atom, or a general formula (2)

(Wherein R ² represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, an aryl group, or an aralkyl group), and n represents an integer of 2 to 100. And a divalent organic group represented by R ¹ is represented by the following formula (58), wherein a part or all of n X ¹ presents a curable group that can be cured by heat or light. , (59) or (60)

An organic group represented by
A triazine compound, wherein the monovalent organic group represented by X ¹ is an organic group having an ethylenic carbon-carbon double bond, and X ² is an oxygen atom or a sulfur atom.
26. Hardened | cured material formed by hardening | curing the curable triazine composition in any one of said 1-21.
27. The sealing material for electronic components containing the curable triazine composition in any one of said 1-21.
28. The varnish for electronic components containing the curable triazine composition in any one of said 1-21.

  The curable triazine composition of the present invention has good heat resistance, electrical properties, flame retardancy, tin plating resistance, etc., and gives a cured product particularly excellent in heat resistance, tin plating resistance, etc. It can preferably be used as a sealing material or an electronic component varnish.

で示されるトリアジン化合物及び（Ｂ）硬化剤を含有する。 The triazine composition of the present invention comprises (A) the general formula (1)

And a (B) curing agent.

In the general formula (1), R ¹ represents a divalent organic group. Preferred examples of R ¹ include alkylene groups having 1 to 12 carbon atoms, alkenylene groups, alkynylene groups, cycloalkylene groups, arylene groups, aralkylene groups, and groups represented by the following formulas (6) to (46).

（式中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶はそれぞれ独立して、水素原子、フッ素原子、塩素原子、臭素原子、炭素数１〜１２のアルキル基、アラルキル基、パーフルオロアルキル基、シクロヘキシル基、またはフェニル基を表わす。）

(Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 12 carbon atoms, an aralkyl group, a perfluoroalkyl group, Represents a cyclohexyl group or a phenyl group.)

（式中、Ｒ⁷は水素原子またはメチル基を表わし、互いに同一でも異なっていてもよい。）

(Wherein R ⁷ represents a hydrogen atom or a methyl group, and may be the same or different from each other.)

（式中、Ｒ⁸及びＲ⁹はそれぞれ独立して水素原子またはメチル基を表わし、ｋ、ｍはそれぞれ０または整数を表わし、１≦ｋ＋ｍ≦１８である。）

(In the formula, R ⁸ and R ⁹ each independently represent a hydrogen atom or a methyl group, k and m each represents 0 or an integer, and 1 ≦ k + m ≦ 18.)

（式中、ｐは１〜５０の整数を表わす。）

（式中、ｑは１〜５０の整数を表わす。）

（式中、ｒは１〜５０の整数を表わす。）

(In the formula, p represents an integer of 1 to 50.)

(In the formula, q represents an integer of 1 to 50.)

(In the formula, r represents an integer of 1 to 50.)

（式中、Ｒ¹⁰は２価の有機基を表わし、好ましいＲ¹⁰の例としては、炭素数１〜１２のアルキレン基、シクロアルキレン基、アルケニレン基、アリーレン基、アラルキレン基または前記式（１０）〜（１７）で示される基が挙げられる。ｓは１〜５０の整数を表わす。）

（式中、Ｒ¹¹、Ｒ¹²は２価の有機基を表わし、好ましいＲ¹¹、Ｒ¹²の例としては、炭素数１〜１２のアルキレン基、シクロアルキレン基、アルケニレン基、アリーレン基、アラルキレン基または式（１０）〜（１７）で示される基が挙げられる。ｔは１〜５０の整数を表わす。)

(In the formula, R ¹⁰ represents a divalent organic group, and preferred examples of R ¹⁰ include an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an alkenylene group, an arylene group, an aralkylene group, or the above formula (10). And a group represented by (17), where s represents an integer of 1 to 50.)

(In the formula, R ¹¹ and R ¹² represent a divalent organic group, and preferred examples of R ¹¹ and R ¹² include an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an alkenylene group, an arylene group, and an aralkylene group. Or groups represented by formulas (10) to (17), where t represents an integer of 1 to 50.)

（式中、ｕは１〜５０の整数を表わす。）

（式中、ｖは１〜５０の整数を表わす。）

(In the formula, u represents an integer of 1 to 50.)

(In the formula, v represents an integer of 1 to 50.)

（式中、ｗ、ｘはそれぞれ０または整数を表わし、１≦ｗ＋ｘ≦５０である。）

（式中、ｙは１〜５０の整数を表わす。）

(In the formula, w and x each represents 0 or an integer, and 1 ≦ w + x ≦ 50.)

(In the formula, y represents an integer of 1 to 50.)

（式中、ｚは１〜５０の整数を表わす。）

(In the formula, z represents an integer of 1 to 50.)

（式中、Ｒ¹³は水素原子またはメチル基を表わし、互いに同一でも異なっていてもよい。）

(Wherein R ¹³ represents a hydrogen atom or a methyl group, and may be the same or different from each other.)

（式中、ａは１〜５の整数を表わす。）

(Wherein, a represents an integer of 1 to 5)

（式中、Ｒ¹⁴は水素原子またはメチル基を表わし、互いに同一でも異なっていてもよい。）

（式中、Ｒ¹⁵は水素原子またはメチル基を表わし、互いに同一でも異なっていてもよい。）

(Wherein R ¹⁴ represents a hydrogen atom or a methyl group, and may be the same or different from each other.)

(Wherein R ¹⁵ represents a hydrogen atom or a methyl group, and may be the same or different from each other.)

（式中、Ｒ¹⁶は水素原子またはメチル基を表わし、互いに同一でも異なっていてもよい。）

（式中、Ｒ¹⁷は水素原子またはメチル基を表わし、互いに同一でも異なっていてもよい。）

(In the formula, R ¹⁶ represents a hydrogen atom or a methyl group, and may be the same or different from each other.)

(Wherein R ¹⁷ represents a hydrogen atom or a methyl group, and may be the same or different from each other.)

（式中、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰はそれぞれ独立して水素原子またはメチル基を表わし、ｂ、ｃは０または整数を表わし、２≦ｂ＋ｃ≦２０である。）

（式中、Ｒ²¹は水素原子またはメチル基を表わし、互いに同一でも異なっていてもよく、ｄは１〜５０の整数を表わす。）

(Wherein R ¹⁸ , R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or a methyl group, b and c each represents 0 or an integer, and 2 ≦ b + c ≦ 20)

(In the formula, R ²¹ represents a hydrogen atom or a methyl group, which may be the same or different, and d represents an integer of 1 to 50.)

（式中、Ｒ²²は水素原子またはメチル基を表わし、互いに同一でも異なっていてもよく、ｅは１〜５０の整数を表わす。）

（式中、Ｒ²³は水素原子またはメチル基を表わし、互いに同一でも異なっていてもよく、ｆは１〜５０の整数を表わす。）

(In the formula, R ²² represents a hydrogen atom or a methyl group, which may be the same or different, and e represents an integer of 1 to 50.)

(In the formula, R ²³ represents a hydrogen atom or a methyl group, which may be the same or different from each other, and f represents an integer of 1 to 50.)

（式中、Ｒ²⁴は水素原子またはメチル基を表わし、互いに同一でも異なっていてもよく、Ｒ²⁵は炭素数１〜１２のアルキレン基、アルケニレン基、アルキニレン基、シクロアルキレン基、アラルキレン基または前記式（１０）〜（１７）で示される基を表わし、ｇは１〜５０の整数を表わす。）

（式中、Ｒ²⁶は水素原子またはメチル基を表わし、互いに同一でも異なっていてもよく、ｕは１〜５０の整数を表わす。）

(Wherein R ²⁴ represents a hydrogen atom or a methyl group, and may be the same or different from each other, and R ²⁵ represents an alkylene group having 1 to 12 carbon atoms, an alkenylene group, an alkynylene group, a cycloalkylene group, an aralkylene group, or Represents a group represented by formulas (10) to (17), and g represents an integer of 1 to 50.)

(In the formula, R ²⁶ represents a hydrogen atom or a methyl group, which may be the same or different, and u represents an integer of 1 to 50.)

（式中、Ｒ²⁷は水素原子またはメチル基を表わし、互いに同一でも異なっていてもよく、ｖは１〜５０の整数を表わす。）

（式中、Ｒ²⁸は水素原子またはメチル基を表わし、互いに同一でも異なっていてもよく、ｗ、ｘはそれぞれ０または整数を表わし、１≦ｗ＋ｘ≦５０である。）

(In the formula, R ²⁷ represents a hydrogen atom or a methyl group, which may be the same or different, and v represents an integer of 1 to 50.)

(In the formula, R ²⁸ represents a hydrogen atom or a methyl group, which may be the same or different from each other, and w and x each represents 0 or an integer, and 1 ≦ w + x ≦ 50.)

（式中、Ｒ²⁹は２価の有機基を表わし、好ましくは炭素数１〜１２のアルキレン基、アリーレン基、アラルキレン基または前記式（１０）〜（３３）で示される基である。）
一般式（１）中にｎ個存在するこれらの置換基（Ｒ¹の具体例）は、単一でもよく、また２種類以上の組み合わせでもよい。

(In the formula, R ²⁹ represents a divalent organic group, preferably an alkylene group having 1 to 12 carbon atoms, an arylene group, an aralkylene group, or a group represented by the above formulas (10) to (33).)
These n substituents (specific examples of R ¹ ) present in the general formula (1) may be single or a combination of two or more.

In the general formula (1), X ¹ represents a monovalent organic group, part or all of which is a group containing a curable group curable by heat or light. Examples of preferred curable groups include allyl groups, vinyl groups, (meth) acryloyl groups, epoxy groups, oxetanyl groups, carboxyl groups, acid anhydride groups, amino groups, thiol groups, and optionally blocked isocyanate groups. Etc. Preferable specific examples of X ¹ containing an allyl group include an allyloxy group, an allylamino group, a diallylamino group, and an allyloxyalkyl group. Preferable specific examples of X ¹ containing a vinyl group include (2-vinyloxy) ethyloxy group and (4-vinyloxy) cyclohexyloxy group. A preferred specific example of X ¹ containing a (meth) acryloyl group includes a 2- (meth) acryloylethyloxy group. Examples of preferred specific X ¹ containing an epoxy group include a glycidyloxy group. A preferred specific example of X ¹ containing an oxetanyl group is a (3-ethyl-3-oxetanyl) methyloxy group. Specific examples of preferred X ¹ containing a carboxyl group include 1-carboxy-3-methylpropylamino group, 1-carboxyethylamino group, 2-carboxyethylamino group, 1,2-dicarboxyethylamino group, [1-carboxy- (4-hydroxyphenyl) ethyl] amino group, (carboxymethyl) amino group, 2- (3-carboxypropanoyloxy) ethyloxy group, 2- (3-carboxy-2-propenoyloxy) ethyloxy group, Examples include 2- (2-carboxybenzoyloxy) ethyloxy group, 2- (2,4-dicarboxybenzoyloxy) ethyloxy group, and 2- (2,5-dicarboxybenzoyloxy) ethyloxy group. Examples of preferable specific X ¹ containing an acid anhydride group include a 2- [2,4,5-tricarboxy-4,5-anhydrobenzoyloxy] ethyloxy group. Preferable specific examples of X ¹ containing an amino group include (2-aminoethyl) amino group, (4-aminophenyl) amino group, and (3-aminophenyl) amino group. Specific preferred examples of X ¹ containing a thiol group include (2-mercaptoethyl) thio group.

Preferable specific examples of X ¹ containing an isocyanate group which may be blocked include an isocyanate compound represented by the following formula (47) and a blocked product thereof.

These X ¹ can be used alone or in combination of two or more.
Further, a part of X ¹ may be a group having no curable group. Examples of such preferable X ¹ include alkoxy groups having 1 to 6 carbon atoms, phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2-methoxyphenoxy group, 4-methoxyphenoxy group. Examples include phenoxy group, benzyloxy group, diethylamino group, diisopropylamino group, diphenylamino group, benzylamino group, and thiophenoxy group. These can be used alone or in combination.

In the curable triazine composition of the present invention, among all X ¹ contained in the triazine compound represented by the general formula (1), X ¹ having a curable group is preferably 5 mol% or more. When X ¹ is less than 5 mol%, the curability decreases.

で示される基を表わす。一般式（２）中、Ｒ²は水素原子、炭素数１〜６のアルキル基、アリール基、またはアラルキル基を表わす。好ましいＲ²の例としてはメチル基、エチル基、フェニル基、ベンジル基が挙げられる。これらは単独で、または２種類以上を組み合わせて使用することができる。 In the general formula (1), X ² represents an oxygen atom, a sulfur atom, or the general formula (2).

Represents a group represented by In the general formula (2), R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, or an aralkyl group. Examples of preferable R ² include a methyl group, an ethyl group, a phenyl group, and a benzyl group. These can be used alone or in combination of two or more.

  In the general formula (1), n represents an integer of 2 to 100, preferably 2 to 50, and more preferably 5 to 30. When n is 1, the cured product obtained by curing the triazine compound represented by the general formula (1) has a low cross-linking density, and the properties such as heat resistance are lowered, and those exceeding 100 are difficult to produce.

で示されるジハロトリアジン化合物に、アルコール性水酸基、チオール基、アミノ基、モノ置換アミノ基、またはフェノール性水酸基を１分子に２以上有する化合物、例えばジオール化合物、ジチオール化合物、ジアミン化合物、２官能のフェノール化合物、または２官能のチオフェノール化合物から選ばれる１種以上の化合物（以下「ジオール化合物等」と略記する。）を反応させて得られる。
前記一般式（３）中、Ｘ¹は前記一般式（１）中のＸ¹と同様の基を表わす。また、Ｘ³はフッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子を表わし、原料の入手性等から塩素原子が好ましい。 The triazine compound represented by the general formula (1) is, for example, the general formula (3)

A compound having two or more alcoholic hydroxyl groups, thiol groups, amino groups, mono-substituted amino groups, or phenolic hydroxyl groups per molecule, such as diol compounds, dithiol compounds, diamine compounds, and bifunctional dihalotriazine compounds represented by It is obtained by reacting one or more compounds selected from a phenol compound or a bifunctional thiophenol compound (hereinafter abbreviated as “diol compound etc.”).
In the general formula (3), X ¹ represents the same group as X ¹ in the general formula (1). X ³ represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a chlorine atom is preferred from the viewpoint of availability of raw materials.

  The dihalotriazine compound represented by the general formula (3) is, for example, one or more compounds selected from an alcohol compound, a thiol compound, an amine compound, a phenol compound, and a thiophenol compound (hereinafter referred to as cyanuric halide such as cyanuric chloride). Abbreviated as “alcohol compound etc.”).

  Examples of preferred alcohol compounds that can be used in the reaction with the cyanuric halide include methanol, ethanol, isopropanol, allyl alcohol, glycidol, ethylene glycol, ethylene glycol monovinyl ether, 1,4-butanediol monovinyl ether, cyclohexane Examples include methanol monovinyl ether, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-ethyl-3-hydroxymethyl oxetane.

Examples of preferred thiol compounds that can be used for the reaction with the cyanuric halide include 1,2-propanedithiol.
Examples of preferred amine compounds that can be used for the reaction with the cyanuric halide include diethylamine, diisopropylamine, diallylamine, allylmethylamine, N-methylaniline, valine, alanine, β-alanine, aspartic acid, glycine and the like. Can be mentioned.

  Examples of preferred phenol compounds that can be used for the reaction with the cyanuric halide include phenol, o-cresol, m-cresol, p-cresol, p-methoxyphenol, α-naphthol, β-naphthol, and 4-hydroxy. Biphenyl and 2-hydroxybiphenyl may be mentioned.

Examples of preferred thiophenol compounds that can be used for the reaction with the cyanuric halide include thiophenol.
The reaction of the cyanuric halide with an alcohol compound or the like can be efficiently performed using a base. At this time, it is preferable to use 1.0-20 mol of alcohol compounds etc. with respect to 1 mol of cyanuric halides from points, such as reaction yield and economical efficiency.

  Examples of preferable bases that can be used in the reaction include inorganic bases such as alkali hydroxide, alkali carbonate, alkali hydrogen carbonate, alkali fluoride, alkali hydride, alkali metal, pyridine and derivatives thereof, and aliphatic tertiary. And organic bases such as amines. Examples of the alkali hydroxide include sodium hydroxide and potassium hydroxide. Examples of the alkali carbonate include sodium carbonate and potassium carbonate. Examples of the alkali hydride include sodium hydride. Examples of the alkali metal include sodium metal, and examples of the aliphatic tertiary amine include triethylamine and tri-n-propylamine. From the viewpoint of reaction rate and economy, the base is 0.5 to 30 moles for a monovalent base with respect to 1 mole of cyanuric halide, 0.25 to 15 moles for a divalent base, and more preferably 1.0 to 1.0 mole for a monovalent base. It is preferable to use 20 to 10 mol of divalent base. Moreover, alkali hydroxide or alkali carbonate can be added to the reaction system as an aqueous solution. At this time, the concentration of alkali hydroxide or alkali carbonate is preferably 10 to 70% by mass.

  The reaction temperature of the reaction is preferably −20 to 150 ° C. from the viewpoint of reaction rate and side reaction prevention. When adding a base, it is preferable to add the base at such a rate that this temperature range can be maintained. . The reaction pressure is not particularly limited, and may be any of normal pressure, pressurization, and reduced pressure. The reaction time is usually 1 to 30 hours. In addition, the cyanuric halide may be charged all at once, or may be added to the reaction mixture sequentially in several times. Also in this case, it is preferable to add so as not to exceed the above reaction temperature range.

  The reaction can be performed in the absence of a solvent, but is preferably performed in a suitable reaction solvent. Examples of preferable reaction solvents include aromatic hydrocarbons such as toluene and xylene, ethers such as tetrahydrofuran, dibutyl ether and 1,4-dioxane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, chloroform, dichloromethane and the like. Examples include aprotic polar solvents such as halogenated hydrocarbon solvents, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidone, dimethyl sulfoxide. These solvents are used alone or in combination of two or more. It is preferable that the usage-amount (total amount) is 300 mL-10L with respect to 1 mol of cyanuric halides from points, such as reaction efficiency and economical efficiency.

  In the above reaction, when an aqueous solution of an inorganic base is used as the base and a reaction solvent that is not mixed with the aqueous solution of the inorganic base is used, it is also preferable to use a phase transfer catalyst in order to promote the reaction. Examples of preferred phase transfer catalysts used at this time include tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetramethylammonium sulfate, benzyltriethylammonium chloride, decyltrimethylammonium. Quaternary ammonium salts such as bromide, dodecyltrimethylammonium bromide, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide and cetyltributylammonium bromide, quaternary phosphonium salts such as tetrabutylphosphonium bromide and cetyltributylphosphonium bromide, 15-crown- 5,18-crown-6, benzo-18-crown- , Dibenzo-18-crown-6 crown ether such as dibenzo-24-crown -8 include cryptands such as cryptand [2.2.2]. These can be used alone or in combination of two or more.

  When performing the said reaction, a polymerization inhibitor can also be added as needed. Examples of preferred polymerization inhibitors include hydroquinone, 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol stearyl-β- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl) -6-t-butylphenol), bisphenol compounds such as 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate G] High molecular phenols such as methane, tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione, tocopherol Compounds, phenothiazine, dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, sulfur compounds, triphenyl phosphite, diphenyl Examples thereof include phosphorus compounds such as isodecyl phosphite and phenyl diisodecyl phosphite. These can be used alone or in combination of two or more.

  The dihalotriazine compound thus obtained may be used as it is, and if necessary, acid anhydride modification, acid chloride modification, diisocyanate modification, epichlorohydrin modification and subsequent dehydrochlorination reaction, olefin oxidation epoxidation. You may use after performing etc.

Examples of preferred acid anhydrides used at this time include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, dicarboxylic anhydrides such as phthalic anhydride, tricarboxylic anhydrides such as trimellitic anhydride, pyromellitic Acid dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-bisphenyltetracarboxylic dianhydride, 2,2 ′, 3,3 '-Biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 1,1 -Bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3 4-di Ruboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4- Tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 2,3,2 ′, 3′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5 -Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2, 7-dichloronaphtha Len-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-terolachlornaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8, 9,10-tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride, bis (3,4- Dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1, 3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic acid monoester anhydride), 2,2-bis (3,4-dicarboxyphenyl) hexaful Lopropane dianhydride, 2,2-bis {4- (3,4-dicarboxypheno) phenyl} hexafluoropropane dianhydride, 2,2-bis {4- (3,4-dicarboxypheno) phenyl} Propane dianhydride, 4,4-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzene bis (trimellitate anhydride), 1,3- Bis (2-hydroxyhexafluoroisopropyl) benzene bis (trimellitic anhydride), 1,2- (ethylene) bis (trimellitic anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- ( Tetramethylene) bis (trimellitate anhydride), 1,5- (pentamethylene) bis (trimellitate anhydride) 1,6- (hexamethylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitic anhydride), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9- ( Nonamethylene) bis (trimellitate anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12- (dodecamethylene) bis (trimellitate anhydride), 1,16- (hexacamame) bis (trimellitate) Anhydride), 1,18- (octadecamethylene) bis (trimellitate anhydride), ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, pyrazine-2,3, 5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, decahydronaphthalene 1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid Dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic Acid dianhydride, bis {exobicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride} sulfone, bicyclo [2.2.2] -oct (7) -ene-2,3 5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5 -Acid dianhydrides such as tetracarboxylic dianhydrides Tetracarboxylic acid dianhydride and the like.
Examples of preferable acid chlorides include trimellitic anhydride chloride.

  Examples of preferred diisocyanate compounds include diphenylmethane-2,4′-diisocyanate, 3,2′- or 3,3′- or 4,2′- or 4,3′- or 5,2′- or 5 , 3'- or 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- Or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane -3,3'-diiso Anate, diphenylmethane-3,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2 , 6-diisocyanate, naphthalene-2,6-diisocyanate, aromatic diisocyanates such as 4,4 ′-[2,2-bis (4-phenoxyphenyl) propane] diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene Aliphatic diisocyanates such as 1,6-diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, transcyclohexa 1,4-diisocyanate, alicyclic diisocyanate hydrogenated m- xylylene diisocyanate, etc., m- xylylene diisocyanate, p- xylylene diisocyanate.

（式中、Ｒ⁸及びＲ⁹はそれぞれ独立して水素原子またはメチル基を表わし、ｋ、ｍは０または整数を表わし、２≦ｋ＋ｍ≦２０である。）
で示される化合物等の芳香族系グリコールエーテル、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、ポリカーボネートジオール、（水添）ポリブタジエンジオール等の高分子量ジオールが挙げられる。 Examples of the diol compound that can be used for the reaction with the dihalotriazine compound include ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. 2-methyl-1,3-propanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,2-dimethyl-1,3- Alkylene diols such as propanediol, neopentyl glycol, 2-methyl-1,3-butanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclo Xanthdiol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol 2,3-dihydroxynorbornane, 2,5-dihydroxynorbornane, 2,6-dihydroxynorbornane, 2,7-dihydroxynorbornane, dihydroxydicyclopentadiene, hydrogenated bisphenol A and other alicyclic diols, diethylene glycol, triethylene glycol Aliphatic glycol ethers such as tetraethylene glycol, dipropylene glycol, 2,2-bis [4- (2-hydroxyethyloxy) cyclohexyl] propane, 1,4-bis (2-hydroxyethyloxy) ) Benzene, the following general formula (48)

(In the formula, R ⁸ and R ⁹ each independently represent a hydrogen atom or a methyl group, k and m each represents 0 or an integer, and 2 ≦ k + m ≦ 20.)
And high molecular weight diols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycarbonate diol, and (hydrogenated) polybutadiene diol.

Examples of the dithiol compound that can be used for the reaction with the dihalotriazine compound include 1,2-ethanedithiol.
Examples of the diamine compound that can be used for the reaction with the dihalotriazine compound include ethylenediamine, tetramethylenediamine, hexamethylenediamine, and N, N′-dimethyl, diethyl, diphenyl, and dibenzyl of these diamines. Aliphatic diamine, m-xylylenediamine, p-xylylenediamine, and xylylenediamines such as N, N′-dimethyl, diethyl, diphenyl, and dibenzyl, piperazine, 2,5-dimethylpiperazine Piperazines such as 1,3-di (4-piperidyl) propane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3, 4′-diaminodiphenyl ether, , 3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenyl Sulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 2,2-bis (3-aminophenyl) propane, 2,2-bis (3 4'-diaminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (3,4'-diaminophenyl) Hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1,3 Bis (3-aminophenyl) benzene, 1,4-bis (4-aminophenyl) benzene, 3,3 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 3,4 ′-[1 , 4-phenylenebis (1-methylethylidene)] bisaniline, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 2,2-bis [4- (3-aminophenoxy) phenyl ] Propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- ( 4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl Nyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 9,9-bis (4-aminophenyl) fluorene and its N, N ′ -Aromatic diamines such as dimethyl, diethyl, diphenyl and dibenzyl.

  Examples of preferable bifunctional phenol compounds that can be reacted with the dihalotriazine compound include hydroquinone, catechol, resorcinol, 1,2-dihydroxycinaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1 , 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,2′-biphenol, 4,4′-biphenol, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) -4-methylbutane, 1,1-bis (4- Hydroxyphenyl) decane, 2,2-bis [(4- Roxy-3-phenyl) phenyl] propane, 2-phenyl-2,2-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) ) Cyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol, bis (4-hydroxy-3,5-dimethylphenyl) methane 1,1-bis (4-hydroxy-3,5-dimethylphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxy-3,5-dimethyl) Phenyl) phenylmethane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclopentane, 1,1-bis (4-hydroxy-) 3,5-dimethylphenyl) cyclohexyne and 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene.

Examples of preferable bifunctional thiophenols that can be reacted with the dihalotriazine compound include 4-t-butyl-1,2-dimercaptobenzene and 4,4′-thiodibenzenethiol.
A compound having both a hydroxyl group and an amino group such as monoethanolamine and m-aminophenol can also be used.

  The reaction between the dihalotriazine compound and the diol compound or the like is preferably carried out at a total of 0.5 to 1.5 mol, more preferably 0.8 to 1.2 mol, with respect to 1 mol of the dihalotriazine compound. In the range where the total of diol compounds, etc. is less than 0.5 mol or more than 1.5 mol, the molecular weight of the obtained triazine compound does not increase, and the flexibility of the cured product of the curable triazine composition obtained by blending this, etc. Characteristics are degraded.

  The reaction between the dihalotriazine compound and the diol compound is preferably performed in an organic solvent. Examples of preferable organic solvents include those exemplified as those that can be used in the reaction of the cyanuric halide with an alcohol compound or the like. The amount of the organic solvent to be used is preferably 0.1 to 10 L, more preferably 0.5 to 5 L, with respect to 1 mol of the dihalotriazine compound, from the viewpoint of reaction rate and economy.

The reaction between the dihalotriazine compound and the diol compound is preferably performed in the presence of a base as an acid acceptor. Examples of preferred acid acceptors include the bases exemplified as those that can be used in the reaction between the cyanuric halide and alcohol, and aqueous solutions thereof.
The amount of the acid acceptor used is 2 to 20 moles for the monovalent acid acceptor and 1 to 10 moles for the divalent acid acceptor with respect to 1 mole of the dihalotriazine, from the viewpoint of reaction rate, economy and the like. It is preferable.

  When the reaction between the dihalotriazine compound and the diol compound is performed using an alkaline aqueous solution as the acid acceptor, a phase transfer catalyst may be added to the reaction system. Examples of preferred phase transfer catalysts include those exemplified as those that can be used in the reaction of the cyanuric halide with alcohol or the like. The amount of the catalyst used is preferably 1 to 100 mol% with respect to the dihalotriazine compound from the viewpoints of reaction rate and economy.

  The reaction between the dihalotriazine compound and the diol compound is preferably performed within a range of 0 to 200 ° C. and at a temperature at which the curable group in the dihalotriazine compound is sufficiently stable. When the temperature is 0 ° C. or lower, the reaction proceeds slowly, and when the temperature exceeds 200 ° C., the produced triazine compound may be hydrolyzed. Further, when the curable group in the dihalotriazine compound exceeds a sufficiently stable temperature, the reaction system may be gelled. Therefore, the upper limit temperature needs to be determined in consideration of which functional group is used.

  When the reaction between the dihalotriazine compound and the diol compound is performed, a polymerization inhibitor may be added as necessary. Examples of preferable polymerization inhibitors include those exemplified as those that can be used in the reaction of the dihalotriazine compound with alcohol or the like. These can be used alone or in combination of two or more.

The triazine compound represented by the general formula (1) can also be obtained by the following method. That is, compounds having two or more alcoholic hydroxyl groups, thiol groups, amino groups, mono-substituted amino groups, or phenolic hydroxyl groups per molecule in cyanuric halides such as cyanuric chloride, such as diol compounds, dithiol compounds, diamine compounds, 2 After reacting one or more compounds selected from a functional phenol compound or a bifunctional thiophenol compound (hereinafter abbreviated as “diol compound etc.”), an alcohol compound, a thiol compound, an amine compound, a phenol compound, It can be obtained by reacting one or more compounds selected from thiophenol compounds (hereinafter abbreviated as “alcohol compounds etc.”).
Examples of preferred diol compounds that can be used at this time include those exemplified as those that can be used to obtain the triazine compound represented by the general formula (1) by reacting with the dihalotriazine compound. It is done.

  The reaction between the cyanuric halide and the diol compound is preferably carried out at a total of 0.8 to 1.2 mol of the diol compound per 1 mol of the dihalotriazine compound. When the total amount of diol compounds is less than 0.8 mol or exceeds 1.2 mol, the molecular weight of the resulting triazine compound does not increase, and the properties such as flexibility of the cured product of the curable triazine composition obtained by blending this May decrease.

  The reaction between the cyanuric halide and the diol compound is preferably performed in an organic solvent. Examples of preferable organic solvents include those exemplified as those that can be used in the reaction of the cyanuric halide with an alcohol compound or the like. The amount of the organic solvent to be used is preferably 0.5 to 10 L with respect to 1 mole of cyanuric halide from the viewpoint of reaction rate and economical viewpoint.

The reaction between the cyanuric halide and the diol compound is preferably performed in the presence of an acid acceptor. Examples of preferred acid acceptors include those exemplified as those that can be used in the reaction of the cyanuric halide with alcohol and the like, and aqueous solutions thereof.
The amount of the acid acceptor used is 2 to 20 mol for the monovalent acid acceptor and 1 to 10 mol for the divalent acid acceptor with respect to 1 mol of cyanuric halide from the viewpoint of reaction rate, economy and the like. It is preferable.

  When the reaction between the cyanuric halide and the diol compound is performed using an alkaline aqueous solution as the acid acceptor, a phase transfer catalyst may be added to the reaction system. Examples of preferred phase transfer catalysts include those exemplified as those that can be used in the reaction of the cyanuric halide with alcohol or the like. The amount of the catalyst used is preferably 1 to 100 mol% with respect to the dihalotriazine compound from the viewpoints of reaction rate and economy.

  The reaction between the cyanuric halide and the diol compound is preferably performed within a range of 0 to 150 ° C. When the temperature is 0 ° C. or lower, the progress of the reaction is slow, and when the temperature exceeds 150 ° C., the generated triazine compound may be hydrolyzed or gelled.

  When the reaction between the cyanuric halide and the diol compound is performed, a polymerization inhibitor may be added as necessary. Examples of preferable polymerization inhibitors include those exemplified as those that can be used in the reaction of the cyanuric halide with alcohol or the like. These can be used alone or in combination of two or more.

  Examples of preferred alcohol compounds to be reacted after reacting the cyanuric halide with a diol compound and the like are for reacting with the cyanuric halide to produce the dihalotriazine compound represented by the general formula (3). What was illustrated as what can be used for is mentioned. At this time, the alcohol compound or the like may be directly added to the reaction system of the cyanuric halide and the diol compound or may be reacted again after taking out the product once. Further, from the viewpoint of reaction yield, economy and the like, it is preferable to perform the total of alcohol compounds and the like as 1 to 5 moles per 1 mole of cyanuric halide.

  When the cyano compound is reacted with the cyanuric halide, the alcohol compound is preferably reacted in an organic solvent. Examples of preferable organic solvents include those exemplified as those that can be used in the reaction of the cyanuric halide with an alcohol compound or the like. The amount of the organic solvent to be used is preferably 0.2 to 10 L with respect to 1 mol of cyanuric halide from the viewpoint of reaction rate and economical viewpoint.

When the cyano compound is reacted with the cyanuric halide, the alcohol compound is preferably reacted in the presence of an acid acceptor. Examples of preferred acid acceptors include those exemplified as those that can be used in the reaction of the cyanuric halide with alcohol and the like, and aqueous solutions thereof.
The amount of the acid acceptor to be used is 1 to 20 moles for the monovalent acid acceptor and 0.5 to 10 moles for the divalent acid acceptor with respect to 1 mole of cyanuric halide from the viewpoint of reaction rate and economy. It is preferable.

  When reacting an alcohol compound or the like after reacting the cyanuric halide with a diol compound or the like, a phase transfer catalyst may be added to the reaction system when an alkaline aqueous solution is used as the acid acceptor. Examples of preferred phase transfer catalysts include those exemplified as those that can be used in the reaction of the cyanuric halide with alcohol or the like. The amount of these catalysts used is preferably 1 to 100 mol% with respect to the cyanuric halide from the viewpoints of reaction rate and economy.

  After reacting the cyanuric halide with a diol compound or the like and then reacting the alcohol compound or the like, it is preferably performed within a range of 0 to 200 ° C. When the temperature is 0 ° C. or lower, the progress of the reaction is slow, and when the temperature exceeds 200 ° C., the produced triazine compound may be hydrolyzed. Further, if the curable group in the dihalotriazine compound exceeds a sufficiently stable temperature, the reaction system may be gelled.

  After reacting the cyanuric halide with a diol compound or the like and then reacting the alcohol compound or the like, a polymerization inhibitor may be added as necessary. Examples of preferable polymerization inhibitors include those exemplified as those that can be used in the reaction of the dihalotriazine compound with alcohol or the like. These can be used alone or in combination of two or more.

で示されるトリアジンジチオール化合物に、一般式（５）

で示される化合物または２官能のα，β−不飽和カルボニル化合物を反応させて得ることができる。 The triazine compound represented by the general formula (1) can also be obtained by the following method. That is, the general formula (4)

A triazine dithiol compound represented by general formula (5):

Or a bifunctional α, β-unsaturated carbonyl compound.

X ¹ in the general formula (4) represents the same group as X ¹ in the general formula (1).
The triazine dithiol compound represented by the general formula (4) can be obtained, for example, by reacting the dihalotriazine compound represented by the general formula (3) with an alkali hydrosulfide or an alkali sulfide.

  The reaction between the dihalotriazine compound and the alkali hydrosulfide or alkali sulfide is preferably performed in an organic solvent. Examples of preferable organic solvents that can be used at this time include alcohols such as methanol, ethanol and isopropyl alcohol, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3- Examples include amide solvents such as dimethyl-2-imidazolidone. These organic solvents can be used individually or in combination of 2 or more types, and it is preferable to use 0.1-5L with respect to 1 mol of said dihalotriazine compounds.

  In the reaction of the halotriazine compound with alkali hydrosulfide or alkali sulfide, the alkali hydrosulfide or alkali sulfide is used in an amount of 2 to 10 moles with respect to 1 mole of the dihalotriazine compound from the viewpoint of reaction yield and economy. Is preferred. From the viewpoint of reaction efficiency, the alkali hydrosulfide or alkali sulfide is preferably added after being dissolved in water. At this time, the concentration of alkali hydrosulfide or alkali sulfide is preferably 10 to 70% by mass.

In the reaction of the dihalotriazine compound with alkali hydrosulfide or alkali sulfide, the reaction temperature is preferably -20 to 50 ° C.
In the reaction of the dihalotriazine compound with alkali hydrosulfide or alkali sulfide, a polymerization inhibitor can be added as necessary. Examples of preferable polymerization inhibitors include those exemplified as those that can be used in the reaction of the dihalotriazine compound with an alcohol compound or the like.

In the general formula (5), R ¹ represents the same group as R ¹ in the general formula (1).
In the general formula (5), X ⁴ represents a fluorine atom, a chlorine atom, a bromine atom, a halogen atom of an iodine atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group or a p-toluenesulfonyloxy group, preferably a bromine atom. Methanesulfonyloxy group or p-toluenesulfonyloxy group.

  Examples of preferable specific compounds represented by the general formula (5) include 1,2-dibromoethane, 1,2-dibromopropane, 1,3-dibromopropane, 1,3-dibromobutane, 1,4. Reacting with dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 1,10-dibromodecane, 1,4-dichlorobenzene, p, p′-dibromobiphenyl, and the dihalotriazine compound; The methanesulfonyl acid ester and p-toluenesulfonic acid ester of what was illustrated as a preferable diol compound which can be used in order to manufacture the triazine compound shown by the said General formula (1) are mentioned. These may be used alone or in combination of two or more.

  Examples of preferable bifunctional α, β-unsaturated carbonyl compounds to be reacted with the triazine dithiol compound represented by the general formula (4) include bismaleimide and the dihalotriazine compound to react with the general formula ( The (meth) acrylic acid ester of what was illustrated as a preferable diol which can be used in order to manufacture the triazine compound shown by 1) is mentioned. These may be used alone or in combination of two or more.

  In the reaction of the triazine dithiol compound with the compound represented by the general formula (5) or the α, β-unsaturated carbonyl compound, the compound represented by the general formula (5) or the α, β-unsaturated carbonyl compound is The amount of the triazine dithiol compound is preferably 0.5 to 1.5 mol with respect to 1 mol. In the range where the compound represented by the general formula (5) or the α, β-unsaturated carbonyl compound is less than 0.5 mol or more than 1.5 mol, the molecular weight of the obtained triazine compound does not increase, and the curing obtained by blending it is obtained. The properties such as flexibility of the cured product of the functional triazine composition are lowered.

  The reaction of the triazine dithiol compound with the compound represented by the general formula (5) or the bifunctional α, β-unsaturated carbonyl compound is preferably performed in an organic solvent. Examples of preferable organic solvents include aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene, and benzonitrile, chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, dichlorobenzene, and the like. Listed are ether solvents such as halogen solvents, tetrahydrofuran, dioxane and the like. The amount of the organic solvent to be used is preferably 0.5 to 10 L with respect to 1 mol of the triazine dithiol compound represented by the general formula (4) from the viewpoint of reaction rate and economy.

  The reaction of the triazine dithiol compound with the compound represented by the general formula (5) or the bifunctional α, β-unsaturated carbonyl compound is preferably performed in the presence of a base catalyst. Examples of preferred base catalysts include those exemplified as those that can be used in the reaction of the cyanuric halide with alcohol or the like. The amount used is preferably 1 mmol to 5 mol for the monovalent base and 0.5 mmol to 2.5 mol for the divalent base with respect to 1 mol of triazinedithiol from the viewpoints of reaction rate, side reaction prevention, economy and the like. .

  When the reaction of the triazine dithiol compound with the compound represented by the general formula (5) or the bifunctional α, β-unsaturated carbonyl compound is carried out in a two-phase system of an organic solvent and water, a reaction system A phase transfer catalyst may be added therein. Examples of preferred phase transfer catalysts include those exemplified as those that can be used in the reaction of the dihalotriazine compound with a diol compound or the like.

  The reaction between the triazine dithiol compound and the compound represented by the general formula (5) or the bifunctional α, β-unsaturated carbonyl compound is within a range of 0 to 200 ° C. and curing in the triazine dithiol compound. It is preferable to carry out the reaction at a temperature below the sufficiently stable functional group. If the temperature is lower than 0 ° C, the reaction proceeds slowly, and if the temperature exceeds 200 ° C, the triazine resin may be hydrolyzed. Further, when the curable group in the triazine dithiol compound exceeds a sufficiently stable temperature, the reaction system may be gelled. For example, when the curable group is an allyl group, the reaction temperature is preferably 200 ° C. or lower, and when the acryloyl group is an acryloyl group, the reaction temperature is preferably 150 ° C. or lower.

  When the triazine dithiol compound is reacted with the compound represented by the general formula (5) or the bifunctional α, β-unsaturated carbonyl compound, a polymerization inhibitor may be added as necessary. Examples of preferable polymerization inhibitors include those exemplified as those that can be used in the reaction of the cyanuric halide with alcohol or the like. These can be used alone or in combination of two or more.

In the present invention, the reaction of the dihalotriazine compound represented by the general formula (3) with a diol compound or the like, or the triazine dithiol compound represented by the general formula (4) and the compound represented by the general formula (5) Alternatively, the triazine compound represented by the general formula (1) obtained by the reaction with an α, β-unsaturated compound may be modified with an acid anhydride, an acid chloride, a diisocyanate, an epichlorohydrin, and subsequently removed as necessary. It can also be used after carrying out hydrochloric acid reaction, olefin epoxidation of olefin and the like.
Examples of the acid anhydride acid chloride and diisocyanate that can be used at this time include those exemplified as those that can be used for modification of the dihalotriazine compound.

In the present invention, the triazine compound represented by the general formula (1) and containing a curable group that can be cured by heat or light in some or all of X ¹ may be used alone or in combination of two or more. Can be used.

In this invention, the example and preferable usage-amount of the hardening | curing agent which are (B) components are as follows.
(A) When curable group is allyl group It is preferable to use a thermal radical polymerization initiator as the curing agent.
As preferable thermal radical polymerization initiators, methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetate peroxide, acetyl acetate peroxide, 1,1-bis (t-butylperoxy) butane, 1,1- Bis (t-butylperoxy) -cyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane 1,1-bis (t-butylperoxy) cyclododecane, 1,1-bis (t-hexylperoxy) -cyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5- Trimethylcyclohexane, 2,2-bis (4,4-di-t-butylperoxy (Cyclohexyl) propane, t-butyl hydroperoxide, t-hexyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-methane hydroperoxide, diisopropylbenzene hydroperoxide , Di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, α, α′-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t -Butylperoxy) hexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,3,5-trimethylhexanoyl peroxide, octanoyl peroxide , Lauroyl peroxide, Thearoyl peroxide, succinic acid peroxide, m-toluoyl benzoyl peroxide, benzoyl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydi Carbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-s-butylperoxydicarbonate, di (3-methyl -3-methoxybutyl) peroxydicarbonate, α, α′-bis (neodecanoylperoxy) diisopropylbenzene, t-butylperoxyneodecanoate, t-hexylperoxyneodecanoate, 1,1 , 3,3-te Tramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, cumylperoxyneodecanoate, t-butylperoxypivalate, t-hexylperoxypivalate, t -Butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5- Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexa Noate, t-butyl peroxyisopropyl monocarbonate, t-hexyl peroxyisopropyl mono Carbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butylperoxyallyl monocarbonate, t-butylperoxyisobutyrate, t-butylperoxymalate, t-butylperoxybenzoate, t-hexyl Peroxybenzoate, t-butylperoxy-m-toluylbenzoate, t-butylperoxylaurate, t-butylperoxyacetate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl-2,5 -Bis (m-toluylperoxy) hexane, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butyltrimethylsilyl peroxide, 3,3 ', 4,4'-tetra (t- Butylperoxycarbonyl) benzophenone, 2,3-dimethyl-2,3-di An organic peroxide such as phenylbutane can be used.
These can be used alone or in combination of two or more, and it is preferably used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the triazine compound (A).

(B) When curable group is vinyl group or (meth) acryloyl group It is preferable to use a thermal radical polymerization initiator or a photo radical polymerization initiator as the curing agent.
Preferred examples of the thermal radical polymerization initiator include organic peroxides exemplified in (a), 1-[(1-cyano-1-methylethyl) azo] formamide, 1,1′-azobis (cyclohexane-1-carbohydrate). Nitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2, 2-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis [N- (4-chlorophenyl) -2-methylpropio Amidine] dihydrochloride, 2,2′-azobis [N- (4-hydrophenyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (2-propenyl) propionamidine Dihydrochloride, 2,2′-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydro Chloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2 ′ -Azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis {2- [ -(2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2′-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepine-2) -Yl) propane] dihydrochloride, 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (5- Hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2′-azobis (2-methylpropionamide), 2,2′-azobis [2-methyl-N- ( 2-hydroxyethyl) propionamide], 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2 , 2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide}, 2,2′-azobis (2-methylpropane), 2,2′-azobis (2, 4,4-trimethylpentane), dimethyl 2,2′-azobis (2-methylpropionate), 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis [2- (hydroxymethyl) ) Propionitrile] and the like. These can be used alone or in combination of two or more.
These thermal radical polymerization initiators are preferably used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the triazine compound (A).

Preferred photo radical polymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-phenyl-1-phenyl. Propan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 Acetophenone initiators such as benzoin, benzoin methyl ether Benzoin initiators such as benzoin isopropyl ether, benzoin isobutyl ether, benzyl methyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'- Methyldiphenyl sulfide, 3,3′-dimethyl-4-methoxybenzophenone, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxy Benzophenone initiators such as carbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4 Thioxanthone initiators such as diisopropylthioxanthone, isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 2,4-dichlorothioxanthone, α-acyloxime ester, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone Ketone initiators such as camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ′, 4 ″ -diethylisophthalophenone, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5, Imidazole initiators such as 5′-tetraphenyl-1,2′-imidazole, acylphosphine oxide initiators such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, carbazole initiators, triphenylphosphonium hexafluoroanti Monet Triphenylphosphonium hexafluorophosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, (2,4-cyclopentadien-1-yl) [(1-methylethyl And onium salts of Lewis acids such as benzene] -iron-hexafluorophosphate.
These photopolymerization initiators are preferably used in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of the triazine compound (A).

(C) When the curable group is an epoxy group It is preferable to use a compound having a functional group that reacts with an epoxy group, such as a polyfunctional amine, carboxylic acid, or acid anhydride, particularly an acid anhydride, as the curing agent.
Examples of preferred amines are exemplified as diamine compounds that can be used to produce the triazine compound represented by the general formula (1) by reacting with the dihalotriazine compound represented by the general formula (3). In addition to those, triamine compounds such as diethylenetriamine, tetraamine compounds such as triethylenetetramine, and melamines such as melamine, acetoguanamine, and benzoguanamine. These can be used alone or in combination of two or more.

  Examples of carboxylic acids include succinic acid, maleic acid, fumaric acid, adipic acid, tetrahydrophthalic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and other dicarboxylic acid compounds, trimellitic acid , Tricarboxylic acids such as trimesic acid, pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-bisphenyltetracarboxylic acid, 2,2 ′, 3 , 3′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1-bis (3,4- Dicarboxyphenyl) ethane, bis (2,3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) Nyl) sulfone, 3,4,9,10-perylenetetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, benzene-1,2,3,4-tetracarboxylic acid, 3,4,3 ′, 4′-benzophenone tetracarboxylic acid, 2,3,2 ′, 3′-benzophenone tetracarboxylic acid, 2,3,3 ′, 4′-benzophenone tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,6-dichloronaphthalene-1, 4,5,8-tetracarboxylic acid, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid, 2,3,6,7-tetrachloronaphthalene-1,4,5,8- Tetracarbo Acid, phenanthrene-1,8,9,10-tetracarboxylic acid, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) methylphenylsilane, bis (3,4- Dicarboxyphenyl) diphenylsilane, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyl Dicyclohexane, p-phenylenebis (trimellitic acid monoester acid), 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis {4- (3,4-dicarboxypheno) ) Phenyl} hexafluoropropane, 2,2-bis {4- (3,4-dicarboxypheno) phenyl} propane, 4,4-bis ( , 4-dicarboxyphenoxy) diphenyl sulfide, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzene bis (trimellitate), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzene bis (trimellitate), 1, 2- (ethylene) bis (trimellitate), 1,3- (trimethylene) bis (trimellitate), 1,4- (tetramethylene) bis (trimellitate), 1,5- (pentamethylene) bis (trimellitate), 1, 6- (hexamethylene) bis (trimellitate), 1,7- (heptamethylene) bis (trimellitate), 1,8- (octamethylene) bis (trimellitate), 1,9- (nonamethylene) bis (trimellitate), 1 , 10- (Decamethylene) bis (trimellitate) 1,12- (dodecamethylene) bis (trimellitate), 1,16- (hexadecamethylene) bis (trimellitate), 1,18- (octadecamethylene) bis (trimellitate), ethylenetetracarboxylic acid, 1,2 , 3,4-Butanetetracarboxylic acid, pyrazine-2,3,5,6-tetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, decahydronaphthalene-1,4,5,8- Tetracarboxylic acid, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid, cyclopentane-1,2,3,4-tetra Carboxylic acid, pyrrolidine-2,3,4,5-tetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, bis {exobicyclo [2.2.1] heptane- 2,3-dicarboxylic acid} sulfone, bicyclo [2.2.2] -oct (7) -ene-2,3,5,6-tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl)- Resins having two or more carboxyl groups such as tetracarboxylic acid such as 3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetrahydrofuran-2,3,4,5-tetracarboxylic acid, and polyacrylic acid Can be mentioned. These can be used alone or in combination of two or more.

Furthermore, what was illustrated as what can be used for the modification | denaturation of the dihalotriazine compound shown by the said General formula (3) as an example of an acid anhydride is mentioned. These can be used alone or in combination of two or more.
These curing agents are preferably used in an amount of 5 to 200 parts by mass with respect to 100 parts by mass of the triazine compound (A).

Moreover, when using an acid anhydride as a hardening | curing agent, it is preferable to add a hardening accelerator.
Preferred curing accelerators include benzyldimethylamine (BDMA), 1-benzyl-2-phenylimidazole, 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxyimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2,4-diamino-6- [2-methylimidazolyl- (1)]-ethyl-s-triazine, 1-cyanoethyl-2-undecylimidazole, 2-ethyl-4-methylimidazole, 1, Amine compounds such as 8-diazabicyclo [5.4.0] undecene-7 and their salt compounds, phosphine compounds such as triphenylphosphine and tris- (2,6-dimethoxyphenyl) phosphine and their salt compounds, organic metals Salt.
These curing accelerators can be used alone or in combination of two or more, and it is preferably used in an amount of 0 to 20 parts by mass with respect to 100 parts by mass of the triazine compound (A).

で示されるオニウム塩を用いることが好ましい。 (D) When curable group is oxetanyl group It is preferable to use a photocationic polymerization initiator or a thermal cationic polymerization initiator as a curing agent.
As the cationic photopolymerization initiator, the formula (49)

It is preferable to use the onium salt shown by these.

In the formula (49), [A] ^{h +} is diphenyliodonium, 4-methoxydiphenyliodonium, bis (4-methylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (dodecylphenyl) iodonium, triphenyl Sulfonium, diphenyl-4-thiophenoxyphenylsulfonium, bis [4- (diphenylsulfonio) -phenyl] sulfide, bis [4- (di (4- (2-hydroxyethyl) phenyl) sulfonio) -phenyl] sulfide, represents an onium ion such as η5-2,4- (cyclopentagenyl) [1,2,3,4,5,6-η- (methylethyl) benzene] -iron (1+), [X] ^h- Are tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, Halogenated complexes such as oxafluoroarsenate and hexachloroantimonate, tetra (fluorophenyl) borate, tetra (difluorophenyl) borate, tetra (trifluorophenyl) borate, tetra (tetrafluorophenyl) borate, tetra (pentafluorophenyl) Aromatic anions such as borate, tetra (perfluorophenyl) borate, tetra (trifluoromethylphenyl) borate, tetra (di (trifluoromethyl) phenyl) borate, perchlorate ion, trifluoromethanesulfonate ion, toluenesulfone Represents anions such as acid ions and trinitrotoluenesulfonate ions.

  These photocationic polymerization initiators can be used singly or in combination of two or more, and preferably used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the triazine compound (A).

  Thermal cationic polymerization initiators include metal chelate compounds such as aluminum trisacetylacetonate or dialkylbenzylsulfonium, benzyl-4-hydroxyphenylmethylsulfonium, hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium, hexafluoroantimonate Sulfonium salt compounds such as benzyl-4-methoxyphenylmethylsulfonium, hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium, hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium Is preferably used.

  A compound having a functional group to be added to the oxetane ring, such as carboxylic acid or acid anhydride, can also be used. Examples of preferred carboxylic acids and acid anhydrides include those exemplified in (c). At this time, it is preferable to use 5-200 mass parts of carboxylic acid or acid anhydride with respect to 100 mass parts of the triazine compound of (A).

  Further, when a carboxylic acid or acid anhydride is used as a curing agent, it is preferable to use a curing accelerator. Preferred curing accelerators include tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, onium salts such as benzyltriphenylphosphonium chloride, triethylamine, tributylamine, 1,8-diazabicyclo [5.4.0] amines such as undecene-7, crown ether complexes, triphenylphosphine and the like. These can be used alone or in combination of two or more. At this time, it is preferable that 0.1-20 mass parts is used for the quantity of a hardening accelerator with respect to 100 mass parts of triazine compounds of resin (A).

(E) When the curable group is a carboxyl group or an acid anhydride group As a curing agent, a functional group that reacts with a carboxyl group or an acid anhydride group, such as a polyfunctional epoxy compound, oxetane compound, amine compound, isocyanate compound, etc. It is preferable to use a compound having the same.

  Various epoxy resins can be used as the epoxy compound. Specific examples include polyglycidyl ethers such as ethylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, neopentyl glycol diglycidyl ether, epoxy resins having a triazine ring such as triglycidyl cyanurate and triglycidyl isocyanurate, Examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxy novolac resin, phenol novolac type epoxy resin, and orthocresol novolac type epoxy resin.

These epoxy compounds can be used alone or in combination of two or more, and it is preferable to use 5 to 200 parts by mass in total with respect to 100 parts by mass of the triazine compound (A).
Moreover, when using an epoxy compound as a hardening | curing agent, 0.1-20 mass parts is used together with 100 parts by mass of the triazine compound of (A), as the curing accelerator, those exemplified as the curing accelerator in (c). Is preferred.

Examples of the oxetane compound include compounds represented by the following formulas (50) to (54).

（式中、ｉは１〜３の整数を表わす。）

(Wherein i represents an integer of 1 to 3)

These oxetane compounds can be used alone or in combination of two or more, and it is preferable to use 5 to 200 parts by mass in total with respect to 100 parts by mass of the triazine compound (A).
Moreover, when using an oxetane compound as a hardening | curing agent, it is preferable to use a hardening accelerator. As an example of a preferable hardening accelerator, what was illustrated as a hardening accelerator by (d) is mentioned, It is preferable to use 0.1-20 mass parts with respect to the triazine compound of (A).

  As an example of an amine compound, what was illustrated as an amine compound which can be used by (c) is mentioned. These amine compounds can be used alone or in combination of two or more, and it is preferable to use 5 to 200 parts by mass in total with respect to 100 parts by mass of the triazine compound (A).

As an example of an isocyanate compound, the diisocyanate compound illustrated as what can be used for modification | denaturation of the dihalotriazine compound shown by the said General formula (3) is mentioned.
These isocyanate compounds can be used alone or in combination of two or more, and it is preferable to use 5 to 200 parts by mass in total with respect to 100 parts by mass of the triazine compound (A).

(F) When the curable group is an amino group As a curing agent, a compound having a functional group that reacts with an amino group, such as a polyfunctional epoxy compound, an isocyanate compound, an acid anhydride, or an α, β-unsaturated carbonyl compound Is preferably used.

  As an example of an epoxy compound, what was illustrated as what can be used by (d) is mentioned. These epoxy compounds can be used alone or in combination of two or more, and it is preferable to use 5 to 200 parts by mass with respect to 100 parts by mass of the triazine compound (A).

  Examples of the isocyanate compound include those exemplified as those that can be used to modify the dihalotriazine compound represented by the formula (3). These isocyanate compounds can be used individually or in combination of 2 or more types, It is preferable to use 5-200 mass parts with respect to 100 mass parts of the triazine compound of (A).

  As an example of an acid anhydride, what was illustrated as what can be used by (c) is mentioned. These acid anhydrides can be used alone or in combination of two or more, and it is preferably used in an amount of 5 to 200 parts by mass with respect to 100 parts by mass of the triazine compound (A).

Examples of α, β-unsaturated carbonyl compounds are those that can be used to produce the triazine compound represented by the general formula (1) by reacting with the triazine dithiol compound represented by the general formula (4). (Meth) acrylate of alkyl-modified dipentaerythritol, (meth) acrylate of ε-caprolactone-modified dipentaerythritol, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta Examples include poly (meth) acrylates such as erythritol penta (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol triacrylate. That.
These α, β-unsaturated carbonyl compounds can be used alone or in combination of two or more, and it is preferably used in a total of 5 to 200 parts by mass with respect to 100 parts by mass of the triazine compound (A).

(G) When curable group is thiol group It is preferable to use polyene compounds such as polybutadiene, polyisoprene, and natural rubber as the curing agent. These polyene compounds can be used alone or in combination of two or more, and it is preferable to use 5 to 200 parts by mass in total with respect to 100 parts by mass of the triazine compound (A).

(H) When the curable group is a (blocked) isocyanate group It is preferable to use a compound having an active proton such as a polyfunctional amine compound or a carboxylic acid compound or an acid anhydride as the curing agent.

  Preferable amine compounds include those exemplified as those that can be used in (c). These amine compounds can be used alone or in combination of two or more, and it is preferable to use 5 to 200 parts by mass in total with respect to 100 parts by mass of the triazine compound (A).

  Examples of the carboxylic acid compound and the acid anhydride include those exemplified as those that can be used in (c). These carboxylic acid compounds or acid anhydrides can be used alone or in combination of two or more, and it is preferable to use 5 to 200 parts by mass in total with respect to 100 parts by mass of the triazine compound (A).

The curable triazine composition of the present invention contains (A) a triazine compound represented by the general formula (1), (B) a curing agent, and other components such as a flame retardant and a reactive diluent as necessary. You can also
At this time, as the flame retardant, it is particularly preferable to use a non-halogen flame retardant such as a phosphorus flame retardant, a triazine compound such as melamine, or an inorganic flame retardant such as aluminum hydroxide.

In the present invention, when the varnish for electronic parts is used, it is further varnished by adding a solvent. Preferred solvents for varnishing include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, diethylene glycol Ether solvents such as dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, sulfur-containing solvents such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, sulfolane, γ-butyrolactone, cellosolve acetate, propylene glycol monomethyl ether Ester solvents such as acetate and diethylene glycol monoethyl ether acetate, ketone solvents such as cyclohexanone and methyl ethyl ketone, toluene, Aromatic hydrocarbon solvents and the like such as cyclohexylene, particularly preferably an ether solvent, sulfur-containing solvents, ester solvents, ketone solvents, and aromatic hydrocarbon solvents and the like.
These solvents can be used alone or in combination of two or more, and the amount used thereof is 100 parts by mass in total of the flame retardant and reactive diluent as required in addition to the triazine compound curing agent of (A). It is preferable to set it as 20-400 mass parts with respect to.

The inorganic and / or organic fine particles used as the component (D) in the present invention are not particularly limited as long as they are dispersed in the varnished composition as the component (C) to form a paste. Examples of such inorganic fine particles include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), and silicon nitride (Si). ₃ N ₄ ), barium titanate (BaO · TiO ₂ ), barium carbonate (BaCO ₃ ), lead titanate (PbO · TiO ₂ ), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT) , gallium oxide (Ga ₂ O _3), spinel _{(MgO · Al 2 O 3)} , mullite _{(3Al 2 O 3 · 2SiO 2} ), cordierite _{(2MgO · 2Al 2 O 3 /} 5SiO 2), talc (3MgO · 4SiO ₂ · H ₂ O), aluminum titanate (TiO ₂ —Al ₂ O ₃ ), yttria-containing zirconia (Y ₂ O ₃ —ZrO ₂ ), barium silicate (BaO · 8S) iO ₂ ), boron nitride (BN), calcium carbonate (CaCO ₃ ), calcium sulfate (CaSO ₄ ), zinc oxide (ZnO), magnesium titanate (MgO · TiO ₂ ), barium sulfate (BaSO ₄ ). Organic bentonite, carbon (C), and the like can be used, and one or more of these can also be used.

  The organic fine particles used in the present invention are not particularly limited as long as they are dispersed in the varnished composition to form a paste. Such organic fine particles are preferably heat-resistant resin fine particles having an amide bond, an imide bond, an ester bond or an ether bond. The heat-resistant resin is preferably a polyimide resin or a precursor thereof, a polyamideimide resin or a precursor thereof, or fine particles of a polyamide resin from the viewpoint of heat resistance and mechanical properties.

  In the curable triazine resin composition having thixotropic properties of the present invention, organic fine particles that are insoluble in a solvent are used, but as a whole, before heat drying, (A) the above general formula (1) The organic fine particles exist as a heterogeneous layer with respect to the varnish containing the curable triazine compound and (B) the curing agent, and a uniform layer containing the curable trizine compound and the organic fine particles is formed after heat curing. What was blended as described above is preferably used.

As the inorganic and / or organic fine particles in the present invention, those having an average particle size of 50 μm or less and a maximum particle size of 100 μm or less are preferably used. When the average particle diameter exceeds 50 μm, it becomes difficult to obtain a paste having a thixotropic coefficient of 1.1 or more, which will be described later, and when the maximum particle diameter exceeds 100 μm, the appearance and adhesion of the coating film tend to be insufficient.
As a method for dispersing inorganic and / or organic fine particles in the varnish of the present invention, roll kneading, mixer mixing, etc., which are usually performed in the paint field, are applied, and any method can be used as long as sufficient dispersion is performed.

In the resin composition for electronic parts having thixotropy according to the present invention, it is preferable that the viscosity with a rotary viscometer is 0.5 to 500 Pa · s at 25 ° C. and the thixotropy coefficient is 1.1 or more.
Here, the viscosity of the paste is expressed as a viscosity of 5 rpm measured using an E-type viscometer (EHD-R, rotor No. 7 manufactured by Tokyo Keiki Co., Ltd.). The thixotropy coefficient (TI value) of the paste is expressed as the apparent viscosity of the paste measured at the same rotational speeds of 0.5 rpm and 5 rpm, and the ratio η0.5 / η5 of η0.5 and η5.

  When the viscosity is less than 0.5 Pa · s, there is a tendency that the flow after printing becomes large and the film thickness becomes thin. If the viscosity exceeds 500 Pa · s, the transferability of the resin composition to the substrate tends to decrease and voids and pinholes in the printed film tend to increase. If the thixotropy coefficient is less than 1.1, the stringing of the paste increases, the flow of the paste after printing increases, and the film thickness also tends to be reduced.

  In the resin composition for electronic parts of the present invention, the amount of the inorganic and / or organic fine particles used as the component (D) is in the range of 1 to 90 parts by mass with respect to 100 parts by mass of the varnish of the component (C). Is preferred. When the amount is less than this, the viscosity and thixotropy coefficient of the resin composition are lowered, the stringing is increased, the flow-out after printing is increased, and the film thickness tends to be reduced. On the other hand, when the amount is larger than this, the viscosity and thixotropy coefficient of the resin composition increase, and the transferability to the substrate tends to decrease and voids and pinholes in the printed film tend to increase.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

Example 1
(1-1) Synthesis of Triazine Compound A 200 mL four-necked flask equipped with a rotor, a condenser tube, a nitrogen inlet tube and a thermometer was added with bisphenol F (o, m, p-substituted mixture, Honshu Chemical Industry Co., Ltd. )) 10.0 g (50 mmol) and N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) 100 mL were charged and dissolved. At 25 ° C., 27.6 g (200 mmol) of potassium carbonate (manufactured by Junsei Chemical Industry Co., Ltd.) was added and stirred for 30 minutes. At 0 ° C., 10.3 g (50 mmol) of 2-allyloxy-4,6-dichloro-1,3,5-triazine was added dropwise and reacted at 25 ° C. for 48 hours. The reaction solution was added dropwise to 2 L of water, and the resulting precipitate was filtered off and stirred in water at 60 ° C. for 7 hours to remove the incorporated solvent. Furthermore, it dried at 70 degreeC with the vacuum dryer for 8 hours, and obtained 15.5g of white powdery resin. When the molecular weight was measured by gel permeation chromatography (hereinafter referred to as GPC), the number average molecular weight (polystyrene conversion) was 4700.
When this powdery resin was directly subjected to thermogravimetric analysis (TGA method), the 5% weight reduction temperature was 320 ° C.
(1-2) Preparation of curable triazine composition 2,5-dimethyl-2,5-bis (t-butylperoxy) with respect to 100 parts by mass of the powdery resin obtained in (1-1) 2 parts by mass of hexane (trade name: Perhexa 25B, manufactured by NOF Corporation) was added and dissolved in γ-butyrolactone to obtain a curable triazine resin composition having a nonvolatile content of 25% by mass.
(1-3) Coating and curing of curable triazine composition Iupicel N grade immersed in acidic degreasing agent (AC-401) for 1 minute at 25 ° C, washed with ion-exchanged water, and then dried at 70 ° C for 3 minutes The curable triazine resin composition obtained in (1-2) was applied onto SE1310 (single-sided copper laminate manufactured by Ube Industries, Ltd.) using a bar coater. The obtained coated substrate was dried at 80 ° C. for 30 minutes and then heat-cured at 160 ° C. for 1 hour.
(1-4) Evaluation of cured product The substrate with the cured film obtained in (1-3) is rinsed with ion-exchanged water, and immersed in ICP Clean 91 (Okuno Pharmaceutical Co., Ltd.) for 1 minute at 30 ° C. After acid degreasing and washing with ion-exchanged water, it was immersed in 10% by mass sulfuric acid at 30 ° C. for 1 minute for pickling and washed with ion-exchanged water. The substrate was thoroughly drained, then immersed in TINPOSIT LT-34 (tin plating solution, manufactured by Rohm & Haas) heated to 70 ° C. for 3 minutes, and further immersed in ion-exchanged water at 70 ° C. for 3 minutes. Next, heat treatment was performed in a box oven at 120 ° C. for 100 minutes. In the obtained plated substrate, a slight amount of plating was observed, but no discoloration of the cured film or copper foil was observed.

Example 2
(2-1) Synthesis of triazine compound Bisphenol F (p, p'-) instead of bisphenol F (o, m, p-substituted mixture, manufactured by Honshu Chemical Industry Co., Ltd.) described in (1-1) above. Body, manufactured by Honshu Chemical Industry Co., Ltd.) and synthesized in the same manner as in (1-1) to obtain 15.8 g of a white powdery resin. When the molecular weight was measured by GPC, the number average molecular weight (polystyrene conversion) was 3600.
The obtained powdery resin was analyzed using ¹ H-NMR and ¹³ C-NMR (both solvents were deuterated chloroform and the measuring instrument was JEOL (JEOL Ltd. AL-400)). As shown in FIG. From these analyses, the obtained resin is a triazine compound in which X ¹ is an allyloxy group, X ² is an oxygen atom, R ¹ is an organic group represented by the formula (59), and n is 11 in the general formula (1). It was confirmed that there was.
The obtained powdery resin was directly subjected to thermogravimetric analysis (TGA method). As a result, the 5% weight reduction temperature was 315 ° C.
(2-2) Preparation of curable triazine composition Using the powdery resin obtained in (2-1), the same adjustment as in (1-2) above was performed, and a curable triazine having a nonvolatile content of 20% by mass. A resin composition was obtained.
(2-3) Coating and curing of curable triazine composition Using the curable triazine composition obtained in (2-2), coating and curing were performed in the same manner as in (1-3) above.
(2-4) Evaluation of hardened | cured material Using the board | substrate with a cured film obtained by (2-3), hardened | cured material was evaluated similarly to said (1-4). In the plated substrate obtained here, a slight amount of plating was observed, but no discoloration of the cured film or copper foil was observed.

Example 3
(3-1) Synthesis of triazine compound 4,4′-dihydroxyphenyl ether instead of bisphenol F (o, m, p-substituted mixture, manufactured by Honshu Chemical Industry Co., Ltd.) described in (1-1) above (Product name: SPECIANOL DPE-H, manufactured by Dainippon Ink & Chemicals, Inc.) 10.1 g (50 mmol) was used for synthesis in the same manner as in (1-1) to obtain 15.8 g of a white powdery resin. . When the molecular weight was measured by GPC, the number average molecular weight (in terms of polystyrene) was 2500.
When this powdery resin was directly subjected to thermogravimetric analysis (TGA method), the 5% weight loss temperature was 289 ° C.
(3-2) Preparation of curable triazine composition Using the powdery resin obtained in (3-1), the same adjustment as in (1-2) above was performed, and a curable triazine having a nonvolatile content of 20% by mass. A resin composition was obtained.
(3-3) Coating and curing of curable triazine composition Using the curable triazine composition obtained in (3-2), coating and curing were performed in the same manner as in (1-3) above.
(3-4) Evaluation of hardened | cured material Using the board | substrate with a cured film obtained by (2-3), hardened | cured material was evaluated similarly to said (1-4). In the plated substrate obtained here, the penetration of the plating and the discoloration of the cured film and the copper foil were only slightly observed.

Comparative Example In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 600 g of carbitol acetate as a synthesis solvent, polycaprolactone diol as a polymer polyol (trade name: PLACEL 212, manufactured by Daicel Chemical Industries, Ltd., molecular weight 1250) 375.0 g ( = 0.3 mol), 40.2 g (= 0.3 mol) of dimethylolpropionic acid as a dihydroxyl compound having a carboxyl group, 155.4 g (= 0.7 mol) of isophorone diisocyanate by polyisocyanate, and 2 as an acrylate having a hydroxyl group -23.8 g (= 0.2 mol) of hydroxyethyl acrylate, and 0.1 g each of p-methoxyphenol and di-t-butyl-hydroxytoluene were added. The mixture was heated to 60 ° C. with stirring and stopped, and 0.16 g of dibutyltin dilaurate was added. When the temperature in the reaction vessel starts to decrease, the mixture is heated again and stirred at 80 ° C., and the reaction is terminated after confirming that the absorption spectrum of the isocyanate group (2280 cm ⁻¹ ) has disappeared in the infrared absorption spectrum. A thick liquid urethane acrylate compound was obtained. The number average molecular weight of the obtained urethane acrylate was 25,000, the acid value was 40 mgKOH / g, and the solid content concentration was 50% by mass.
This urethane acrylate and epoxy resin (trade name: Epicoat 828, manufactured by Japan Epoxy Resin Co., Ltd.) were blended so that the epoxy group / carboxyl group = 1.1 equivalents, and melamine (Nissan Chemical Industry Co., Ltd.) was further added. 8 mass parts was added with respect to 100 mass parts of epoxy resins, and the curable resin composition was obtained.
Using this curable resin composition, a substrate with a cured film was obtained by the same operation as (1-3) of Example 1, and the tin plating property was evaluated in the same manner as (1-4). As a result, the penetration of the plating was clearly observed, and the peeling of the cured film was noticeable.

  The curable triazine composition obtained from the present invention gives a cured product excellent in heat resistance, tin plating resistance and the like, and can be preferably used as a sealing material for electronic parts and / or a varnish for electronic parts.

4 is a chart showing the analysis results of ¹ H-NMR (solvent: deuterated chloroform) of the powdery resin obtained in Example 2. FIG. 6 is a chart showing ¹³ C-NMR (solvent: deuterated chloroform) analysis results of the powdered resin obtained in Example 2. FIG.

Claims (28)

(A) General formula (1)

[In the formula, each R ¹ independently represents a divalent organic group, each X ¹ independently represents a monovalent organic group, and X ² represents an oxygen atom, a sulfur atom, or a general formula (2)

(Wherein R ² represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, or an aralkyl group), and n represents an integer of 2 to 100. A triazine compound represented by, curable triazine, which comprises a triazine compound of part or all X ¹ n number exists with a curable curable groups by heat or light, and a curing agent Composition. General formula (3)

(Wherein X ¹ represents a monovalent organic group containing a curable group curable with heat or light, and X ³ represents a halogen atom), or one or more dihalotriazine compounds And a triazine compound obtained by reacting one or more compounds selected from compounds having two or more alcoholic hydroxyl groups, thiol groups, amino groups, mono-substituted amino groups, or phenolic hydroxyl groups in one molecule with a curing agent. The curable triazine composition according to claim 1, which is blended. General formula (4)

(Wherein X ¹ represents a monovalent organic group containing a curable group curable by heat or light) and one or more triazinedithiol compounds represented by the general formula (5)

(Wherein R ¹ represents a divalent organic group, and X ⁴ represents a halogen atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group or a p-toluenesulfonyloxy group). The curable triazine composition according to claim 1, wherein a curing agent is blended with a triazine compound obtained by reacting the above. General formula (4)

(Wherein X ¹ represents a monovalent organic group containing a curable group curable by heat or light) and one or more triazinedithiol compounds represented by The curable triazine composition according to claim 1, wherein a curing agent is added to a triazine compound obtained by reacting at least one saturated carbonyl compound. Formula (1) n number of R ¹ is represented by the following formula (6) to (9) and (55) - (57)

(Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 12 carbon atoms, an aralkyl group, a perfluoroalkyl group, Represents a cyclohexyl group or a phenyl group.)

(In the formula, four R ^{7 s} each independently represent a hydrogen atom or a methyl group.)

(In the formula, each of four R ³⁰ independently represents a hydrogen atom or a methyl group.)

(In the formula, four R ^{31 s} each independently represent a hydrogen atom or a methyl group.)

(In the formula, four R ^{32 s} each independently represent a hydrogen atom or a methyl group.)
The curable triazine composition according to claim 1, which is a group selected from at least one of the following: Formula (1) n number of R ¹ is represented by the following formula in (58) - (60)

The curable triazine composition according to claim 1, which is a group selected from at least one of the following: Some or all of X ¹ are allyl group, vinyl group, (meth) acryloyl group, epoxy group, oxetanyl group, carboxyl group, acid anhydride group, amino group, thiol group, and optionally blocked isocyanate The curable triazine composition according to claim 1, which is a monovalent organic group having one or more selected from a group. The curable triazine composition according to any one of claims 1 to 7, wherein a part or all of X ¹ has an allyl group and includes an organic peroxide as the curing agent. The curable triazine composition according to any one of claims 1 to 7, wherein a part or all of X ¹ has a vinyl group or a (meth) acryloyl group and includes an azo compound as the curing agent. The curable triazine composition according to any one of claims 1 to 7, wherein a part or all of X ¹ has an epoxy group and includes a polyfunctional compound of amine, carboxylic acid or acid anhydride as the curing agent. Part or all of X ¹ has an oxetanyl group, and the curing agent is represented by the formula (49)

(In the formula, [A] ^{h +} represents an onium ion, [X] ^h- represents an anion, and h represents an integer.)
The curable triazine composition according to any one of claims 1 to 7, comprising an onium salt represented by the formula: A part or all of X < ¹ > has a carboxyl group or an acid anhydride group, and contains the polyfunctional compound of an epoxy compound, an oxetane compound, an amine compound, or an isocyanate compound as said hardening | curing agent. A curable triazine composition. Having some or all of the X ¹ amino group, the epoxy compound as a curing agent, an isocyanate compound, any one of claims 1 to 7 comprising the multifunctional compound of the acid anhydride or alpha, beta-unsaturated carbonyl compounds The curable triazine composition described in 1. The curable triazine composition according to any one of claims 1 to 7, wherein a part or all of X ¹ has a thiol group and includes a polyene compound as the curing agent. A part or all of X ¹ has an isocyanate group which may be blocked, and contains the polyfunctional compound or acid anhydride of an amine compound or a carboxylic acid compound as the curing agent. The curable triazine composition described.   The curable triazine composition according to any one of claims 1 to 15, further comprising a solvent.   The curable triazine composition according to claim 16, wherein the solvent is at least one selected from an ether solvent, a sulfur-containing solvent, an ester solvent, a ketone solvent, and an aromatic hydrocarbon solvent.   18. The curable triazine composition according to claim 16 or 17, further comprising organic or inorganic fine particles. The organic or inorganic fine particles are silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), silicon nitride (Si ₃ N _4). ), Barium titanate (BaO · TiO ₂ ), barium carbonate (BaCO ₃ ), lead titanate (PbO · TiO ₂ ), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga ₂ O ₃ ), spinel (MgO.Al ₂ O ₃ ), mullite (3Al ₂ O ₃ .2SiO ₂ ), cordierite (2MgO.2Al ₂ O ₃ / 5SiO ₂ ), talc (3MgO.4SiO _2. H ₂ O), aluminum titanate _{(TiO 2 -Al 2 O 3)} , yttria-containing zirconia _{(Y 2 O 3 -ZrO 2)} , barium silicate (BaO · 8SiO _2), Boron nitride (BN), calcium carbonate (CaCO ₃ ), calcium sulfate (CaSO ₄ ), zinc oxide (ZnO), magnesium titanate (MgO · TiO ₂ ), barium sulfate (BaSO ₄ ), organic bentonite, carbon (C) The curable triazine composition according to claim 18, wherein the curable triazine composition is at least one selected from the group consisting of a polyimide resin or a precursor thereof, a polyamideimide resin or a precursor thereof, and a polyamide resin.   The curable triazine composition according to claim 19, wherein the organic or inorganic fine particles have an average particle diameter of 50 μm or less.   21. The curable triazine composition according to claim 18, wherein the curable triazine composition has a viscosity at 25 ° C. of 0.5 to 500 Pa · s and a thixotropic coefficient of 1.1 or more. General formula (3)

(Wherein X ¹ represents a monovalent organic group containing a curable group curable with heat or light, and X ³ represents a halogen atom), or one or more dihalotriazine compounds And a triazine compound obtained by reacting at least one compound selected from a compound having two or more alcoholic hydroxyl groups, thiol groups, amino groups, mono-substituted amino groups, or phenolic hydroxyl groups per molecule with a curing agent. The method for producing a curable triazine composition according to claim 2, wherein the composition is blended. General formula (4)

(Wherein X ¹ represents a monovalent organic group containing a curable group curable by heat or light) and one or more triazinedithiol compounds represented by the general formula (5)

(Wherein R ¹ represents a divalent organic group, and X ⁴ represents a halogen atom, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group or a p-toluenesulfonyloxy group). The method for producing a curable triazine composition according to claim 3, wherein a curing agent is added to the curable triazine compound obtained by reacting the curable triazine compound. General formula (4)

(Wherein X ¹ represents a monovalent organic group containing a curable group curable by heat or light) and one or more triazinedithiol compounds represented by The method for producing a curable triazine composition according to claim 4, wherein a curing agent is added to the curable triazine compound obtained by reacting at least one saturated carbonyl compound. (A) General formula (1)

[Wherein, R ¹ independently represents a divalent organic group, X ¹ independently represents a monovalent organic group, and X ² represents an oxygen atom, a sulfur atom, or a general formula (2)

(Wherein R ² represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, an aryl group, or an aralkyl group), and n represents an integer of 2 to 100. And a divalent organic group represented by R ¹ is represented by the following formula (58), wherein a part or all of n X ¹ presents a curable group that can be cured by heat or light. , (59) or (60)

An organic group represented by
A triazine compound, wherein the monovalent organic group represented by X ¹ is an organic group having an ethylenic carbon-carbon double bond, and X ² is an oxygen atom or a sulfur atom.   Hardened | cured material formed by hardening | curing the curable triazine composition in any one of Claims 1-21.   The sealing material for electronic components containing the curable triazine composition in any one of Claims 1-21. The varnish for electronic components containing the curable triazine composition in any one of Claims 1-21.

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