JP2004323864A - Preparation process of phosphazene-modified phenolic resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a preparation process of a new phenolic resin useful as a flame-retardant for a synthetic resin. <P>SOLUTION: A phosphazene-modified phenolic resin is prepared by carrying out a polycondensation reaction between a phosphazene compound of formula (1a) [wherein R<SP>1</SP>is a hydrogen atom or a hydroxyl group; Y<SP>1</SP>is a group: -N=P(XR)<SB>3</SB>or the like; Y<SP>2</SP>is a group: -P(XR)<SB>4</SB>or the like; X is an oxygen atom or the like; R is a substituted or unsubstituted 1-15C alkyl group or the like; n and m are each an integer between 0 and 9999; and R<SP>6</SP>is a 1-15C alkyl group], and an aldehyde of a formula (4): A=O [wherein A is a group: -CHR<SP>2</SP>- or the like and R<SP>2</SP>is a hydrogen atom or the like]. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a phosphazene-modified phenol resin.

  Synthetic resins are widely used as parts materials for these products in the fields of electric and electronic products such as OA equipment, office equipment, and communication equipment due to their excellent moldability, mechanical properties, appearance, and the like. I have. These component materials are required to have a high degree of flame retardancy so that problems such as heat generation and ignition do not occur.

  In recent years, a technique has been proposed for immobilizing a flame retardant on a resin via a chemical bond such as a covalent bond in order to impart excellent flame retardancy to the synthetic resin without deteriorating the physical properties of the synthetic resin. .

  For example, Patent Literatures 1 and 2 disclose a phenol resin in which a flame retardant having a phosphorus atom is incorporated in a phenol resin, and a resin composition in which the phenol resin is mixed with an epoxy resin.

However, these resin compositions have insufficient heat resistance, moisture resistance, and the like, and are unsuitable for use in electronic component materials that require high reliability.
JP 2001-181374 A JP 2001-220427 A

  An object of the present invention is to provide a novel phenol resin useful as a flame retardant for a synthetic resin.

The present inventors have conducted intensive studies to solve the above problems, and as a result, succeeded in obtaining a novel phenol resin useful as a flame retardant for various synthetic resins, and completed the present invention.
1. The present invention has the general formula

［式中、Ｒは、Ｃ_1-15アルキル基、Ｃ_3-15シクロアルキル基、Ｃ_2-15アルケニル基、Ｃ_6-20アリール基又はフェノール樹脂残基を示す。

[In the formula, R represents a C _1-15 alkyl group, a C _3-15 cycloalkyl group, a C _2-15 alkenyl group, a C _6-20 aryl group or a phenol resin residue.

R ¹ represents a hydrogen atom or a hydroxyl group.

A represents a group —CHR ² — or a group — (CH ₂ O) _a —CH ₂ —. Here, R ² is a hydrogen atom, a C _1-6 alkyl group, a C _2-4 alkenyl group, a C _3-6 cycloalkyl group or a C _1-6 alkyl group, a C _3-6 cycloalkyl group or a hydroxy as a substituent. A phenyl group which may have a group is shown. a shows the integer of 1-5.

  X represents an oxygen atom or a sulfur atom.

Y ¹ represents a group -N = P (XR) ₃ or a group -N = P (X) XR, and Y ² represents a group -P (XR) ₄ or a group -P (X) (XR) ₂ . Further, Y ¹ and Y ² may be bonded to each other to form a ring.

n and m each represent an integer of 0 to 9999. However, 2 ≦ m + n ≦ 9999. ]
Is a phosphazene-modified phenol resin containing a group represented by the following formula as a structural unit.
2. The present invention has the general formula

［式中、Ｒ¹及びＡは上記に同じ。Ｒ³は、水素原子、Ｃ_1-6アルキル基、Ｃ_3-6シクロアルキル基、Ｃ_2-6アルケニル基、Ｃ_3-7シクロアルケニル基、Ｃ_2-6アルキニル基、Ｃ_6-18アリール基、水酸基、メルカプト基、ジ置換アミノ基、シアノ基、ニトロ基、スルホン基、Ｃ_2-10ポリエーテル基、シロキサン基、酸アミド基又は酸イミド基を示す。ｂは０〜３の整数を示す。］
で表される基及び一般式

Wherein R ¹ and A are the same as above. R ³ is a hydrogen atom, a C _1-6 alkyl group, a C _3-6 cycloalkyl group, a C _2-6 alkenyl group, a C _3-7 cycloalkenyl group, a C _2-6 alkynyl group, a C _6-18 aryl group A hydroxyl group, a mercapto group, a disubstituted amino group, a cyano group, a nitro group, a sulfone group, a _C2-10 polyether group, a siloxane group, an acid amide group or an acid imide group. b shows the integer of 0-3. ]
A group represented by the general formula

［式中、Ａは上記に同じ。Ｒ⁴は、同一又は異なって、水素原子、メチル基又はヒドロキシメチル基を示す。Ｒ⁵は水素原子、アミノ基、ヒドロキシメチルアミノ基、ジ（ヒドロキシメチル）アミノ基、Ｃ_1-6アルキル基、フェニル基又はアルキルフェニル基を示す。］
で表される基からなる群より選ばれる少なくとも１種の基を構成単位として含有する上記１に記載のホスファゼン変性フェノール樹脂である。
３．本発明は、一般式（１）の基において、同一又は異なるリン原子に結合する２つのＲが互いに結合し、ｏ−フェニレン基、ｍ−フェニレン基、ｐ−フェニレン基又は一般式

Wherein A is the same as above. R ⁴ is the same or different and represents a hydrogen atom, a methyl group or a hydroxymethyl group. R ⁵ represents a hydrogen atom, an amino group, a hydroxymethylamino group, a di (hydroxymethyl) amino group, a C _1-6 alkyl group, a phenyl group or an alkylphenyl group. ]
2. The phosphazene-modified phenol resin according to the above 1, which contains at least one group selected from the group consisting of groups represented by the following formulas as a constituent unit.
3. In the present invention, in the group represented by the general formula (1), two Rs bonded to the same or different phosphorus atoms are bonded to each other to form an o-phenylene group, an m-phenylene group, a p-phenylene group or a general formula

［式中、Ｚは、−Ｃ（ＣＨ₃）₂−、−ＳＯ₂−、−Ｓ−又は−Ｏ−を示す。ｃは０又は１を示す。］
で表される架橋基を形成している上記１又は２に記載のホスファゼン変性フェノール樹脂である。
４．本発明は、架橋基を形成するＲの割合が、Ｒの総数の０．０１〜３０％であり、残りのＲはＣ_1-15アルキル基、Ｃ_3-15シクロアルキル基、Ｃ_2-15アルケニル基又はＣ_6-20アリール基である上記３に記載のホスファゼン変性フェノール樹脂である。
５．本発明は、ＲがＣ_1-6アルキル基又はフェニル基であり、Ｘが酸素原子である上記１、２又は４に記載のホスファゼン変性フェノール樹脂である。
６．本発明は、重量平均分子量が８００〜１２０００００である上記１〜５に記載のホスファゼン変性フェノール樹脂である。
７．本発明は、フェノール樹脂残基が、一般式

[Wherein, Z represents —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, or —O—. c represents 0 or 1. ]
3. The phosphazene-modified phenol resin according to the above 1 or 2, which forms a crosslinking group represented by
4. In the present invention, the proportion of R forming a crosslinking group is 0.01 to 30% of the total number of R, and the remaining R is a C _1-15 alkyl group, a C _3-15 cycloalkyl group, a C _2-15. 4. The phosphazene-modified phenol resin according to the above 3, which is an alkenyl group or a C _6-20 aryl group.
5. The present invention is the phosphazene-modified phenol resin according to the above 1, 2 or 4, wherein R is a C _1-6 alkyl group or a phenyl group, and X is an oxygen atom.
6. The present invention is the phosphazene-modified phenol resin according to any one of the above items 1 to 5, which has a weight average molecular weight of 800 to 1200000.
7. In the present invention, the phenol resin residue has a general formula

［式中、Ｒ¹、Ｒ³、Ａ及びｂは上記に同じ。］
で表される基の１種又は２種以上の繰返し単位で構成される重量数平均分子量２００〜１００００のフェノール樹脂から１個の水素原子が脱離した基である上記１〜６のいずれかに記載のホスファゼン変性フェノール樹脂である。
８．本発明は、一般式

Wherein R ¹ , R ³ , A and b are the same as above. ]
Any one of the above 1 to 6, which is a group in which one hydrogen atom is eliminated from a phenol resin having a weight average molecular weight of 200 to 10,000 composed of one or more kinds of repeating units of the group represented by The phosphazene-modified phenol resin described in the above.
8. The present invention has the general formula

［式中、Ａ、Ｒ⁴及びＲ⁵は上記に同じ。］
で表される基から選ばれる１種又は２種以上の構成単位を含有する上記７に記載のホスファゼン変性フェノール樹脂である。
９．本発明は、Ｒ³が水素原子、Ｃ_1-4アルキル基、水酸基又はフェニル基であり、ｂが１又は２であり、且つＡが基−ＣＨＲ²を示し、Ｒ²が水素原子、Ｃ_1-6アルキル基、Ｃ_2-4アルケニル基、フェニル基又はヒドロキシフェニル基である上記７又は８に記載のホスファゼン変性フェノール樹脂である。
１０．本発明は、一般式（１ａ）

Wherein A, R ⁴ and R ⁵ are the same as above. ]
8. The phosphazene-modified phenol resin according to the above 7, which contains one or more structural units selected from the groups represented by
9. In the present invention, R ³ is a hydrogen atom, a C _1-4 alkyl group, a hydroxyl group or a phenyl group, b is 1 or 2, and A represents a group —CHR ² , R ² is a hydrogen atom, C _{1 9.} The phosphazene-modified phenol resin according to the above 7 or 8, which is a _-6 alkyl group, a _C2-4 alkenyl group, a phenyl group or a hydroxyphenyl group.
10. The present invention provides a compound represented by the general formula (1a):

［式中、Ｒ¹、Ｙ¹、Ｙ²、Ｘ、ｍ及びｎは上記に同じ。Ｒ⁶は、Ｃ_1-15アルキル基、Ｃ_3-15シクロアルキル基、Ｃ_2-15アルケニル基又はＣ_6-20アリール基を示す。］
で表されるホスファゼン化合物と、一般式（４）
Ａ＝Ｏ （４）
［式中、Ａは上記に同じ。］
で表されるアルデヒドとを重縮合反応させることにより製造できるホスファゼン変性フェノール樹脂である。
１１．本発明は、(1) 一般式（１ａ）

[Wherein, R ¹ , Y ¹ , Y ² , X, m and n are the same as above. R ⁶ represents a C _1-15 alkyl group, a C _3-15 cycloalkyl group, a C _2-15 alkenyl group or a C _6-20 aryl group. ]
A phosphazene compound represented by the general formula (4)
A = O (4)
Wherein A is the same as above. ]
Is a phosphazene-modified phenol resin that can be produced by a polycondensation reaction with an aldehyde represented by
11. The present invention relates to (1) a compound represented by the general formula (1a):

［式中、Ｒ¹、Ｙ¹、Ｙ²、Ｘ、ｍ及びｎは上記に同じ。Ｒ⁶は、Ｃ_1-15アルキル基、Ｃ_3-15シクロアルキル基、Ｃ_2-15アルケニル基又はＣ_6-20アリール基を示す。］
で表されるホスファゼン化合物、(2) 一般式（２ａ）

[Wherein, R ¹ , Y ¹ , Y ² , X, m and n are the same as above. R ⁶ represents a C _1-15 alkyl group, a C _3-15 cycloalkyl group, a C _2-15 alkenyl group or a C _6-20 aryl group. ]
A phosphazene compound represented by the general formula (2a):

［式中、Ｒ¹、Ｒ³及びｂは上記に同じ。］
で表される芳香族化合物及び一般式（３ａ）

Wherein R ¹ , R ³ and b are the same as above. ]
And an aromatic compound represented by the general formula (3a):

［式中Ｒ⁴及びＲ⁵は上記に同じ。］
で表されるトリアジン化合物からなる群より選ばれた少なくとも１種並びに (3) 一般式（４）
Ａ＝Ｏ （４）
［式中、Ａは上記に同じ。］
で表されるアルデヒドを重縮合反応させることにより製造できるホスファゼン変性フェノール樹脂である。
１２．本発明は、(1) 一般式（１ａ）

Wherein R ⁴ and R ⁵ are the same as above. ]
And at least one selected from the group consisting of triazine compounds represented by the following formulas:
A = O (4)
Wherein A is the same as above. ]
Is a phosphazene-modified phenol resin that can be produced by subjecting an aldehyde represented by the following to a polycondensation reaction.
12. The present invention relates to (1) a compound represented by the general formula (1a):

［式中、Ｒ¹、Ｙ¹、Ｙ²、Ｘ、ｍ及びｎは上記に同じ。Ｒ⁶は、Ｃ_1-15アルキル基、Ｃ_3-15シクロアルキル基、Ｃ_2-15アルケニル基又はＣ_6-20アリール基を示す。］
で表されるホスファゼン化合物、(2) 一般式（２ａ）

[Wherein, R ¹ , Y ¹ , Y ² , X, m and n are the same as above. R ⁶ represents a C _1-15 alkyl group, a C _3-15 cycloalkyl group, a C _2-15 alkenyl group or a C _6-20 aryl group. ]
A phosphazene compound represented by the general formula (2a):

［式中、Ｒ¹、Ｒ³及びｂは上記に同じ。］
で表される芳香族化合物及び (3) 一般式（４）
Ａ＝Ｏ （４）
［式中、Ａは上記に同じ。］
で表されるアルデヒドを重縮合反応させることにより製造できるホスファゼン変性フェノール樹脂である。
１３．本発明は、(1) 一般式（１ａ）

Wherein R ¹ , R ³ and b are the same as above. ]
An aromatic compound represented by the general formula (4):
A = O (4)
Wherein A is the same as above. ]
Is a phosphazene-modified phenol resin that can be produced by subjecting an aldehyde represented by the following to a polycondensation reaction.
13. The present invention relates to (1) a compound represented by the general formula (1a):

［式中、Ｒ¹、Ｙ¹、Ｙ²、Ｘ、ｍ及びｎは上記に同じ。Ｒ⁶は、Ｃ_1-15アルキル基、Ｃ_3-15シクロアルキル基、Ｃ_2-15アルケニル基又はＣ_6-20アリール基を示す。］
で表されるホスファゼン化合物、(2) 一般式（３ａ）

[Wherein, R ¹ , Y ¹ , Y ² , X, m and n are the same as above. R ⁶ represents a C _1-15 alkyl group, a C _3-15 cycloalkyl group, a C _2-15 alkenyl group or a C _6-20 aryl group. ]
A phosphazene compound represented by the general formula (3a):

［式中Ｒ⁴及びＲ⁵は上記に同じ。］
で表されるトリアジン化合物及び (3) 一般式（４）
Ａ＝Ｏ （４）
［式中、Ａは上記に同じ。］
で表されるアルデヒドを重縮合反応させることにより製造できるホスファゼン変性フェノール樹脂である。
１４．本発明は、一般式（２ａ）

Wherein R ⁴ and R ⁵ are the same as above. ]
And a triazine compound represented by the general formula (4):
A = O (4)
Wherein A is the same as above. ]
Is a phosphazene-modified phenol resin that can be produced by subjecting an aldehyde represented by the following to a polycondensation reaction.
14． The present invention provides a compound represented by the general formula (2a):

［式中、Ｒ¹、Ｒ³及びｂは上記に同じ。］
で表される芳香族化合物及び一般式（４）
Ａ＝Ｏ （４）
［式中、Ａは上記に同じ。］
で表されるアルデヒドを重縮合反応させ、次いで得られるフェノール樹脂に、一般式（８）

Wherein R ¹ , R ³ and b are the same as above. ]
An aromatic compound represented by the general formula (4):
A = O (4)
Wherein A is the same as above. ]
Is subjected to a polycondensation reaction, and then the resulting phenolic resin is treated with a general formula (8)

［式中、Ｙ¹及びＹ²は上記に同じ。ｌは３〜１００００の整数を示す。Ｒ⁸は基−ＸＲ（式中Ｘ及びＲは上記に同じ）又はハロゲン原子を示す。但し、ｌ×２個のＲ⁸のうち、少なくとも一つはハロゲン原子を示すものとする。］
で表される鎖状又は環状ホスホニトリルハライドを、塩基性物質の存在下に反応させることによって製造できるホスファゼン変性フェノール樹脂である。
１５．本発明は、一般式（２ａ）

Wherein Y ¹ and Y ² are the same as above. l represents an integer of 3 to 10000. R ⁸ represents a group —XR (where X and R are the same as above) or a halogen atom. However, at least one of l × 2 R ⁸ represents a halogen atom. ]
Is a phosphazene-modified phenol resin that can be produced by reacting a linear or cyclic phosphonitrile halide represented by the formula (1) in the presence of a basic substance.
15. The present invention provides a compound represented by the general formula (2a):

［式中、Ｒ¹、Ｒ³及びｂは上記に同じ。］
で表される芳香族化合物、一般式（３ａ）

Wherein R ¹ , R ³ and b are the same as above. ]
An aromatic compound represented by the general formula (3a):

［式中Ｒ⁴及びＲ⁵は上記に同じ。］
で表されるトリアジン化合物及び一般式（４）
Ａ＝Ｏ （４）
［式中、Ａは上記に同じ。］
で表されるアルデヒドを重縮合反応させ、次いで得られるフェノール樹脂に、一般式（８）

Wherein R ⁴ and R ⁵ are the same as above. ]
And a triazine compound represented by general formula (4):
A = O (4)
Wherein A is the same as above. ]
Is subjected to a polycondensation reaction, and then the resulting phenolic resin is treated with a general formula (8)

［式中、Ｙ¹及びＹ²は上記に同じ。ｌは３〜１００００の整数を示す。Ｒ⁸は基−ＸＲ（式中Ｘ及びＲは上記に同じ）又はハロゲン原子を示す。但し、ｌ×２個のＲ⁸のうち、少なくとも一つはハロゲン原子を示すものとする。］
で表される鎖状又は環状ホスホニトリルハライドを、塩基性物質の存在下に反応させることによって製造できるホスファゼン変性フェノール樹脂である。
１６．本発明は、上記１〜１５のいずれかに記載のホスファゼン変性フェノール樹脂からなる難燃剤である。
１７．本発明は、合成樹脂及び上記１〜１５のいずれかに記載のフェノール樹脂を含有する難燃性樹脂組成物である。
１８．本発明は、合成樹脂がポリエステル、ＡＢＳ樹脂、ポリカーボネート、変性ポリフェニレンエーテル、ポリアミド及びポリイミドからなる群より選ばれる熱可塑性樹脂又はポリウレタン、フェノール樹脂、メラミン樹脂及びエポキシ樹脂からなる群より選ばれる熱硬化性樹脂である上記１７に記載の難燃性樹脂組成物である。
１９．本発明は、合成樹脂が熱硬化性樹脂である上記１８に記載の難燃性樹脂組成物である。
２０．本発明は、熱硬化性樹脂がエポキシ樹脂である上記１９に記載の難燃性樹脂組成物である。
２１．本発明は、上記１〜１５のいずれかに記載のフェノール樹脂を成形してなる難燃性樹脂成形体である。
２２．本発明は、上記１７〜２０のいずれかに記載の難燃性樹脂組成物を成形してなる難燃性樹脂成形体である。
２３．本発明は、一般式（１ａ）

Wherein Y ¹ and Y ² are the same as above. l represents an integer of 3 to 10000. R ⁸ represents a group —XR (where X and R are the same as above) or a halogen atom. However, at least one of l × 2 R ⁸ represents a halogen atom. ]
Is a phosphazene-modified phenol resin that can be produced by reacting a linear or cyclic phosphonitrile halide represented by the formula (1) in the presence of a basic substance.
16. The present invention is a flame retardant comprising the phosphazene-modified phenol resin according to any one of the above 1 to 15.
17. The present invention is a flame-retardant resin composition containing a synthetic resin and the phenol resin described in any one of 1 to 15 above.
18. In the present invention, the synthetic resin is a thermoplastic resin selected from the group consisting of polyester, ABS resin, polycarbonate, modified polyphenylene ether, polyamide and polyimide, or a thermosetting resin selected from the group consisting of polyurethane, phenol resin, melamine resin and epoxy resin. 18. The flame-retardant resin composition according to the above 17, which is a resin.
19. The present invention provides the flame-retardant resin composition according to the above item 18, wherein the synthetic resin is a thermosetting resin.
20. The present invention is the flame-retardant resin composition according to the above item 19, wherein the thermosetting resin is an epoxy resin.
21. The present invention is a flame-retardant resin molded article obtained by molding the phenol resin according to any one of the above 1 to 15.
22. The present invention is a flame-retardant resin molded product obtained by molding the flame-retardant resin composition according to any of the above items 17 to 20.
23. The present invention provides a compound represented by the general formula (1a):

［式中、Ｒ¹、Ｙ¹、Ｙ²、Ｘ、ｍ及びｎは上記に同じ。Ｒ⁶は、Ｃ_1-15アルキル基、Ｃ_3-15シクロアルキル基、Ｃ_2-15アルケニル基又はＣ_6-20アリール基を示す。］
で表されるホスファゼン化合物と、一般式（４）
Ａ＝Ｏ （４）
［式中、Ａは上記に同じ。］
で表されるアルデヒドとを重縮合反応させることによりホスファゼン変性フェノール樹脂を製造するホスファゼン変性フェノール樹脂の製造方法である。
２４．本発明は、(1) 一般式（１ａ）

[Wherein, R ¹ , Y ¹ , Y ² , X, m and n are the same as above. R ⁶ represents a C _1-15 alkyl group, a C _3-15 cycloalkyl group, a C _2-15 alkenyl group or a C _6-20 aryl group. ]
A phosphazene compound represented by the general formula (4)
A = O (4)
Wherein A is the same as above. ]
This is a method for producing a phosphazene-modified phenol resin by producing a phosphazene-modified phenol resin by a polycondensation reaction with an aldehyde represented by the following formula.
24. The present invention relates to (1) a compound represented by the general formula (1a):

［式中、Ｒ¹、Ｙ¹、Ｙ²、Ｘ、ｍ及びｎは上記に同じ。Ｒ⁶は、Ｃ_1-15アルキル基、Ｃ_3-15シクロアルキル基、Ｃ_2-15アルケニル基又はＣ_6-20アリール基を示す。］
で表されるホスファゼン化合物、(2) 一般式（２ａ）

[Wherein, R ¹ , Y ¹ , Y ² , X, m and n are the same as above. R ⁶ represents a C _1-15 alkyl group, a C _3-15 cycloalkyl group, a C _2-15 alkenyl group or a C _6-20 aryl group. ]
A phosphazene compound represented by the general formula (2a):

［式中、Ｒ¹、Ｒ³及びｂは上記に同じ。］
で表される芳香族化合物及び一般式（３ａ）

Wherein R ¹ , R ³ and b are the same as above. ]
And an aromatic compound represented by the general formula (3a):

［式中Ｒ⁴及びＲ⁵は上記に同じ。］
で表されるトリアジン化合物からなる群より選ばれた少なくとも１種並びに (3) 一般式（４）
Ａ＝Ｏ （４）
［式中、Ａは上記に同じ。］
で表されるアルデヒドを重縮合反応させることによりホスファゼン変性フェノール樹脂を製造するホスファゼン変性フェノール樹脂の製造方法である。
２５．本発明は、(1) 一般式（１ａ）

Wherein R ⁴ and R ⁵ are the same as above. ]
And at least one selected from the group consisting of triazine compounds represented by the following formulas:
A = O (4)
Wherein A is the same as above. ]
This is a method for producing a phosphazene-modified phenol resin by producing a phosphazene-modified phenol resin by subjecting an aldehyde represented by the following to a polycondensation reaction.
25. The present invention relates to (1) a compound represented by the general formula (1a):

［式中、Ｒ¹、Ｙ¹、Ｙ²、Ｘ、ｍ及びｎは上記に同じ。Ｒ⁶は、Ｃ_1-15アルキル基、Ｃ_3-15シクロアルキル基、Ｃ_2-15アルケニル基又はＣ_6-20アリール基を示す。］
で表されるホスファゼン化合物、(2) 一般式（２ａ）

[Wherein, R ¹ , Y ¹ , Y ² , X, m and n are the same as above. R ⁶ represents a C _1-15 alkyl group, a C _3-15 cycloalkyl group, a C _2-15 alkenyl group or a C _6-20 aryl group. ]
A phosphazene compound represented by the general formula (2a):

［式中、Ｒ¹、Ｒ³及びｂは上記に同じ。］
で表される芳香族化合物及び (3) 一般式（４）
Ａ＝Ｏ （４）
［式中、Ａは上記に同じ。］
で表されるアルデヒドを重縮合反応させることによりホスファゼン変性フェノール樹脂を製造するホスファゼン変性フェノール樹脂の製造方法である。
２６．本発明は、(1) 一般式（１ａ）

Wherein R ¹ , R ³ and b are the same as above. ]
An aromatic compound represented by the general formula (4):
A = O (4)
Wherein A is the same as above. ]
This is a method for producing a phosphazene-modified phenol resin by producing a phosphazene-modified phenol resin by subjecting an aldehyde represented by the following to a polycondensation reaction.
26. The present invention relates to (1) a compound represented by the general formula (1a):

［式中、Ｒ¹、Ｙ¹、Ｙ²、Ｘ、ｍ及びｎは上記に同じ。Ｒ⁶は、Ｃ_1-15アルキル基、Ｃ_3-15シクロアルキル基、Ｃ_2-15アルケニル基又はＣ_6-20アリール基を示す。］
で表されるホスファゼン化合物、(2) 一般式（３ａ）

[Wherein, R ¹ , Y ¹ , Y ² , X, m and n are the same as above. R ⁶ represents a C _1-15 alkyl group, a C _3-15 cycloalkyl group, a C _2-15 alkenyl group or a C _6-20 aryl group. ]
A phosphazene compound represented by the general formula (3a):

［式中Ｒ⁴及びＲ⁵は上記に同じ。］
で表されるトリアジン化合物及び (3) 一般式（４）
Ａ＝Ｏ （４）
［式中、Ａは上記に同じ。］
で表されるアルデヒドを重縮合反応させることによりホスファゼン変性フェノール樹脂を製造するホスファゼン変性フェノール樹脂の製造方法である。
２７．本発明は、一般式（２ａ）

Wherein R ⁴ and R ⁵ are the same as above. ]
And a triazine compound represented by the general formula (4):
A = O (4)
Wherein A is the same as above. ]
This is a method for producing a phosphazene-modified phenol resin by producing a phosphazene-modified phenol resin by subjecting an aldehyde represented by the following to a polycondensation reaction.
27. The present invention provides a compound represented by the general formula (2a):

［式中、Ｒ¹、Ｒ³及びｂは上記に同じ。］
で表される芳香族化合物及び一般式（４）
Ａ＝Ｏ （４）
［式中、Ａは上記に同じ。］
で表されるアルデヒドを重縮合反応させ、次いで得られるフェノール樹脂に、一般式（８）

Wherein R ¹ , R ³ and b are the same as above. ]
An aromatic compound represented by the general formula (4):
A = O (4)
Wherein A is the same as above. ]
Is subjected to a polycondensation reaction, and then the resulting phenolic resin is treated with a general formula (8)

［式中、Ｙ¹及びＹ²は上記に同じ。ｌは３〜１００００の整数を示す。Ｒ⁸は基−ＸＲ（式中Ｘ及びＲは上記に同じ）又はハロゲン原子を示す。但し、ｌ×２個のＲ⁸のうち、少なくとも一つはハロゲン原子を示すものとする。］
で表される鎖状又は環状ホスホニトリルハライドを、塩基性物質の存在下に反応させることによりホスファゼン変性フェノール樹脂を製造するホスファゼン変性フェノール樹脂の製造方法である。
２８．本発明は、一般式（２ａ）

Wherein Y ¹ and Y ² are the same as above. l represents an integer of 3 to 10000. R ⁸ represents a group —XR (where X and R are the same as above) or a halogen atom. However, at least one of l × 2 R ⁸ represents a halogen atom. ]
A phosphazene-modified phenol resin is produced by reacting a chain or cyclic phosphonitrile halide represented by the formula (1) in the presence of a basic substance.
28. The present invention provides a compound represented by the general formula (2a):

［式中、Ｒ¹、Ｒ³及びｂは上記に同じ。］
で表される芳香族化合物、一般式（３ａ）

Wherein R ¹ , R ³ and b are the same as above. ]
An aromatic compound represented by the general formula (3a):

［式中Ｒ⁴及びＲ⁵は上記に同じ。］
で表されるトリアジン化合物及び一般式（４）
Ａ＝Ｏ （４）
［式中、Ａは上記に同じ。］
で表されるアルデヒドを重縮合反応させ、次いで得られるフェノール樹脂に、一般式（８）

Wherein R ⁴ and R ⁵ are the same as above. ]
And a triazine compound represented by general formula (4):
A = O (4)
Wherein A is the same as above. ]
Is subjected to a polycondensation reaction, and then the resulting phenolic resin is treated with a general formula (8)

［式中、Ｙ¹及びＹ²は上記に同じ。ｌは３〜１００００の整数を示す。Ｒ⁸は基−ＸＲ（式中Ｘ及びＲは上記に同じ）又はハロゲン原子を示す。但し、ｌ×２個のＲ⁸のうち、少なくとも一つはハロゲン原子を示すものとする。］
で表される鎖状又は環状ホスホニトリルハライドを、塩基性物質の存在下に反応させることによりホスファゼン変性フェノール樹脂を製造するホスファゼン変性フェノール樹脂の製造方法である。

Wherein Y ¹ and Y ² are the same as above. l represents an integer of 3 to 10000. R ⁸ represents a group —XR (where X and R are the same as above) or a halogen atom. However, at least one of l × 2 R ⁸ represents a halogen atom. ]
A phosphazene-modified phenol resin is produced by reacting a chain or cyclic phosphonitrile halide represented by the formula (1) in the presence of a basic substance.

The phenolic resin of the present invention In this specification, each group represented by R is specifically as follows.

_{Examples of the} C _1-15 alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, and an n-alkyl group. A heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, etc. A linear or branched alkyl group can be mentioned.

_{Examples of the} C _3-15 cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclopentyl group, a methylcyclohexyl group, a cycloheptyl group, and an octahydronaphthyl group.

_{Examples of the} C _2-15 alkenyl group include an ethenyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a sec-butenyl group, a 1-pentenyl group, a 1-hexenyl group, a 2-heptenyl group, and a 3-octenyl group. Linear or branched having 2 to 15 carbon atoms, such as a 1-nonel group, a 1-decenyl group, a 3-undecenyl group, a 2-dodecenyl group, a 4-tridecenyl group, a 5-tetradecenyl group, and a 1-pentadecenyl group. And the alkenyl group of

_Examples of the C _6-20 aryl group include a phenyl group, a naphthyl group, an anthryl group and a phenanthryl group.

Examples of the substituent for the C _1-15 alkyl group, C _3-15 cycloalkyl group and C _2-15 alkenyl group represented by R include a hydroxyl group, a mercapto group, a C _1-6 alkoxy group and a C _2-7 alkoxy group. Carbonyl group, C _2-7 alkoxycarbonyloxy group, C _2-7 alkylcarbonyloxy group, amino group, mono-substituted amino group, di-substituted amino group, nitro group, C _2-6 nitroalkynyl group, cyano group, thiocyano group , C _3-7 Shianoarukiniru group, a sulfonic group, general formula ^{R a - (O-R b} ) d -O- ( wherein R ^a is C _1-5 alkyl group, C _6-10 aryl group, C _{5- Represents} an ₈ cycloalkyl group, a C _7-18 alkylaryl group or a C _7-18 aralkyl group, R ^b represents a C _1-5 difunctional aliphatic hydrocarbon group, and d represents an integer of 1 to 70. ), A polyether group, a pyrrolidyl group, a piperidino group, a morpholino group, etc. And unsaturated heterocyclic groups such as a furyl group, a pyridyl group, and a thienyl group.

Among these substituents, examples of the group substituted with a mono-substituted amino group and a di-substituted amino group include a C _1-6 alkyl group and a C _6-10 aryl group. The groups may combine with each other to form a C _1-6 alkylene group, a C _6-10 arylene group and the like.

The C _1-15 alkyl group and C _3-15 cycloalkyl group represented by R include a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _2-6 nitroalkenyl group, A C _3-7 cyanoalkenyl group or the like may be substituted.

The C _2-15 alkenyl group represented by R includes, in addition to the above substituents, a C _1-6 alkyl group, a C _2-6 alkynyl group, a C _1-6 nitroalkyl group, a C _2-7 cyanoalkyl group and the like. May be replaced.

Examples of the substituent of the C _6-20 aryl group represented by R include a hydroxyl group, a mercapto group, a C _1-6 alkoxy group, a C _2-7 alkoxycarbonyl group, a C _2-7 alkoxycarbonyloxy group, a C _{2- 7} alkylcarbonyloxy group, amino group, mono-substituted amino group, di-substituted amino group, nitro group, C _2-6 nitroalkynyl group, cyano group, thiocyano group, C _2-7 cyanoalkynyl group, sulfone group, general formula R ^{a - (O-R b)} d -O- polyether group (which. wherein R ^a, R ^b and d are as defined above) represented by, a pyrrolidyl group, a piperidino group, a saturated heterocyclic group such as morpholino group , A furyl group, a pyridyl group, an unsaturated heterocyclic group such as a thienyl group, a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _2-7 cyanoalkyl group, a C _3-7 Cyanoalkenyl group, C _1-6 nitroalkyl group, C _2- Examples include a _6- nitroalkenyl group, a C _3-6 cycloalkyl group, an aryl group, an aryloxy group, an aryloxycarbonyl group, an arylcarbonyloxy group, an aryloxycarbonyloxy group, a nitroaryl group, and a cyanoaryl group. One or more of these substituents can be substituted on the aromatic ring.

  In the present specification, the phenol resin residue represented by R is a group in which one hydrogen atom has been eliminated from a known phenol resin. As a specific example, for example, general formula (2)

［式中、Ｒ¹、Ｒ³、Ａ及びｂは上記に同じ。］
で表される基の１種又は２種以上の繰返し単位で構成される重量平均分子量２００〜１００００、好ましくは２００〜３０００、より好ましくは２００〜２０００のフェノール樹脂から１個の水素原子が脱離した基等を挙げることができる。

Wherein R ¹ , R ³ , A and b are the same as above. ]
One hydrogen atom is eliminated from a phenol resin having a weight average molecular weight of 200 to 10,000, preferably 200 to 3,000, more preferably 200 to 2,000, which is composed of one or more kinds of repeating units of the group represented by And the like.

  The phenol resin residue is represented by the general formula (3)

［式中、Ａ、Ｒ⁴及びＲ⁵は上記に同じ。］
で表される基の少なくとも１種を繰返し単位として含有してもよい。

Wherein A, R ⁴ and R ⁵ are the same as above. ]
May be contained as a repeating unit.

  The phenolic resin containing at least one of the groups represented by the general formula (2) and at least one of the groups represented by the general formula (3) as a repeating unit includes a group represented by the general formula (1) Based on the total amount of the group represented by the general formula (3), the group represented by the general formula (1) is contained in an amount of 4 to 98 mol%, preferably 16 to 98 mol%, and the remainder is 1 (100% ), 40 to 99%, preferably 50 to 91% thereof is a group represented by the general formula (2).

Among the groups represented by the general formula (2), R ¹ is a hydrogen atom or a hydroxyl group, R ³ is a hydrogen atom, a C _1-4 alkyl group, a hydroxyl group or a phenyl group, and A is a group —CHR ² R ² is preferably a hydrogen atom, a C _1-6 alkyl group, a C _2-4 alkenyl group, a phenyl group or a hydroxyphenyl group, and b is preferably from 0 to 2. Among them, R ¹ is a hydrogen atom or a hydroxyl group, R ³ is a hydrogen atom, a C _1-4 alkyl group, a hydroxyl group or a phenyl group, A is a group —CHR ² , R ² is a hydrogen atom, C ² Particularly preferred are _1-4 alkyl groups, phenyl groups or hydroxyphenyl groups, wherein b is 0 to 2.

Among the groups represented by the general formula (3), R ⁴ is a hydrogen atom or a hydroxymethyl group, R ⁵ is a hydrogen atom, an amino group, a hydroxymethylamino group or a phenyl group, and A is a group —CHR ² Wherein R ² is a hydrogen atom, a C _1-6 alkyl group, a C _2-4 alkenyl group, a phenyl group or a hydroxyphenyl group. Furthermore, among them, R ⁴ is a hydrogen atom or a hydroxymethyl group, R ⁵ is an amino group, a hydroxymethylamino group or a phenyl group, A is a group —CHR ² , R ² is a hydrogen atom, C _1- Those which are ₄ alkyl groups, phenyl groups or hydroxyphenyl groups are particularly preferred.

  In the group of the general formula (1), two Rs bonded to the same or different phosphorus atoms are bonded to each other to form an o-phenylene group, an m-phenylene group, a p-phenylene group or a general formula

［式中、Ｚは、−Ｃ（ＣＨ₃）₂−、−ＳＯ₂−、−Ｓ−又は−Ｏ−を示す。ｃは０又は１を示す。］
で表される架橋基を形成していてもよい。架橋基を形成するＲの割合は特に制限はないが、通常Ｒの総数の０．０１〜３０％であり、残りのＲはＣ_1-15アルキル基、Ｃ_3-15シクロアルキル基、Ｃ_2-15アルケニル基又はＣ_6-20アリール基であるのがよい。

[Wherein, Z represents —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, or —O—. c represents 0 or 1. ]
May form a crosslinking group represented by The ratio of R forming the crosslinking group is not particularly limited, but is usually 0.01 to 30% of the total number of R, and the remaining R is a C _1-15 alkyl group, a C _3-15 cycloalkyl group, a C _{2 It} is preferably a _-15 alkenyl group or a C _6-20 aryl group.

In the present specification, each group represented by R ³ is specifically as follows.

_{Examples of the} C _1-6 alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl. Examples thereof include linear or branched alkyl groups of formulas (1) to (6). The alkyl group may have preferably one or two or more of the same substituent (s) as the C _1-15 alkyl group represented by R.

_{Examples of the} C _3-6 cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclopentyl group, and the like. The cycloalkyl group may have preferably one or two or more of the same substituent (s) as the C _3-15 cycloalkyl group represented by R.

_{Examples of the} C _2-6 alkenyl group include an ethenyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a sec-butenyl group, and a 1-pentenyl group. , 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, etc. Or branched alkenyl groups. The alkenyl group may have one or more, preferably one or two, of the same substituents as the C _2-15 alkenyl group represented by R.

_{Examples of the} C _3-7 cycloalkenyl group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a methylcyclopentenyl group, and a methylcyclohexenyl group. The cycloalkenyl group may have preferably one or two or more of the same substituent (s) as the C _2-15 alkenyl group represented by R.

Examples of the C _2-6 alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-pentynyl group, a 2-pentynyl group, and a 3-pentynyl group. And linear alkynyl groups such as a 4-pentynyl group, a 1-hexynyl group, a 2-hexynyl group, a 3-hexynyl group, a 4-hexynyl group, and a 5-hexynyl group. The alkynyl group preferably has one or two or more of the same substituents (excluding C _2-6 alkynyl group) as the C _2-15 alkenyl group represented by R, Good. Further, it may have a C _2-6 alkenyl group as a substituent.

_{Examples of the} C _6-18 aryl group include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. The aryl group may have, on its aromatic ring, preferably one or two or more of the same substituent (s) as the C _6-20 aryl group represented by R.

Examples of the di-substituted amino group include those substituted with a C _1-6 alkyl group and a C _6-10 aryl group. In the di-substituted amino group, two substituents are bonded to each other to form a C _1-6 alkylene group. , C _6-10 arylene groups and the like.

As the C _2-10 polyether group, a compound represented by the general formula R ^c — (O—R ^d ) _e —O— (where R ^c represents a C _1-6 alkyl group, a phenyl group, a C _3-6 cycloalkyl group, _{Represents a 7-9} alkylaryl group or a C _7-9 aralkyl group, R ^d represents a C _1-5 difunctional aliphatic hydrocarbon group, and e represents an integer of 1 to 9.) And polyether groups.

Examples of the C _1-6 alkyl group represented by R ^c, may include, for example, the same as the C _1-6 alkyl group represented by R ^3.

As the C _3-6 cycloalkyl group, for example, those similar to the C _3-6 cycloalkyl group represented by R ³ can be mentioned.

Examples of the C _7-9 alkylaryl group include a tolyl group, an ethylphenyl group, an n-propylphenyl group, an isopropylphenyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, and a 2,5-dimethyl group. On a benzene ring such as a phenyl group, a 2,6-dimethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 3,6-dimethylphenyl group, a 2,4,6-trimethylphenyl group; And an alkylphenyl group in which 1 to 3 linear or branched alkyl groups having 1 to 3 carbon atoms are substituted.

As the _C7-9 aralkyl group, for example, benzyl group, phenethyl group, 1-phenylpropyl group, 2-phenylpropyl group, 3-phenylpropyl group, 1-phenyl-1-methylethyl group, 1-methyl-2 An arylalkyl group in which the alkyl portion is a linear or branched alkyl having 1 to 3 carbon atoms, such as a -phenylethyl group.

Examples of the C _1-5 bifunctional aliphatic hydrocarbon group represented by R ^d include a methylene group, an ethylmethylene group, a diethylmethylene group, a methylmethylene group, an ethylmethylmethylene group, an ethylene group, a trimethylene group, Straight-chain or branched alkylene groups having 1 to 5 carbon atoms, such as -methyltrimethylene group, 2,2-dimethyltrimethylene group, 1-methyltrimethylene group, tetramethylene group, pentamethylene group and the like. Can be.

Specific examples of the C _2-10 polyether group include, for example, 2-oxapropyloxy group, 2,4-dioxapentyloxy group, 2,4,6-trioxaheptyloxy group, 2,4,6- Examples include a trioxa-7-phenoxyheptyloxy group, a 2-oxa-3- (4-methylphenoxy) propyloxy group, and a 2-oxa-3-benzyloxypropyloxy group.

  As the siloxane group, a general formula

［式中、Ｒ^e及びＲ^fは、同一又は異なって、Ｃ_1-6アルキル基、Ｃ_2-6アルケニル基又はＣ_6-18アリール基を示し、Ｒ^gは、Ｃ_1-6アルキル基、Ｃ_6-18アリール基、アミノ基、アクリル基又はグリシジル基を示す。ｆは０〜６の整数、ｇは０〜１０の整数、ｈは０又は１を示す。］
で表されるシロキサン基が挙げられる。ここで、Ｃ_1-6アルキル基としては、例えばＲ³で示されるＣ_1-6アルキル基と同様のものを挙げることができる。Ｃ_2-6アルケニル基としては、例えばＲ³で示されるＣ_2-6アルケニル基と同様のものを挙げることができる。Ｃ_6-18アリール基としては、例えばＲ³で示されるＣ_6-18アリール基と同様のものを挙げることができる。

Wherein R ^e and R ^f are the same or different and represent a C _1-6 alkyl group, a C _2-6 alkenyl group or a C _6-18 aryl group, and R ^g represents a C _1-6 alkyl group, C _{6-18 represents an} aryl group, an amino group, an acryl group or a glycidyl group. f represents an integer of 0 to 6, g represents an integer of 0 to 10, and h represents 0 or 1. ]
And a siloxane group represented by Here, as the C _1-6 alkyl group, for example, those similar to the C _1-6 alkyl group represented by R ³ can be mentioned. As the C _2-6 alkenyl group, for example, those similar to the C _2-6 alkenyl group represented by R ³ can be mentioned. As the C _6-18 aryl group, for example, those similar to the C _6-18 aryl group represented by R ³ can be mentioned.

As the acid amide group, a general formula
^{-N (R h) -C (=} O) -R i
[Wherein, R ^h and R ⁱ are the same or different and each represent a hydrogen atom, a C _1-6 alkyl group or a C _6-18 aryl group. ]
And an acid amide group represented by Here, as the C _1-6 alkyl group, for example, those similar to the C _1-6 alkyl group represented by R ³ can be mentioned. As the C _6-18 aryl group, for example, those similar to the C _6-18 aryl group represented by R ³ can be mentioned.

  Specific examples of the acid amide group include an acetamido group, a hexaneamide group, a benzamide group, an N-methylbenzamide group, an N-phenylacetamido group, an N-phenyltolylamido group, and the like.

  Examples of the acid imide group include a maleimide group, a succinimide group, a phthalimide group, and a 1,2-cyclohexanedicarboximide group.

In the present specification, each group represented by R ² is specifically as follows.

As the C _1-6 alkyl group includes, for example, the same as the C _1-6 alkyl group represented by R ^3.

_{Examples of the} C _2-4 alkenyl group include those having 2 carbon atoms such as an ethenyl group, a 1-propenyl group, a 2-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, and a sec-butenyl group. To 4 linear or branched alkenyl groups.

C _3-6 cycloalkyl group may include, for example similar to the C _3-6 cycloalkyl group represented by R ^3.

The phenyl group which may have a C _1-6 alkyl group, a C _3-6 cycloalkyl group or a hydroxy group as a substituent includes a phenyl group; a tolyl group, a dimethylphenyl group, an ethylphenyl group, an ethylmethylphenyl group, and a diethyl group. Phenyl group, n-propylphenyl group, isopropylphenyl group, isopropylmethylphenyl group, isopropylethylphenyl group, diisopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group An alkylphenyl group in which a linear or branched alkyl group having 1 to 6 carbon atoms is substituted on a benzene ring such as an n-hexylphenyl group by 1 to 3, preferably 1 or 2; a cyclopropylphenyl group; Butylphenyl group, cyclopentylphenyl group, cyclone A cycloalkylphenyl group in which a cycloalkyl group having 3 to 6 carbon atoms is substituted on a benzene ring such as a hexylphenyl group or a methylcyclopentylphenyl group; an o-hydroxyphenyl group, an m-hydroxyphenyl group, a p-hydroxyphenyl group, etc. A hydroxyphenyl group in which 1 to 3, preferably 1 or 2 hydroxy groups are substituted on the benzene ring can be mentioned.

Examples of the group — (CH ₂ O) _a —CH ₂ — include a group —CH ₂ OCH ₂ — and a group —CH ₂ OCH ₂ OCH ₂ —.

In the present specification, each group represented by R ⁵ is specifically as follows.

As the C _1-6 alkyl group includes, for example, the same as the C _1-6 alkyl group represented by R ^3.

  Examples of the alkylphenyl group include a tolyl group, a dimethylphenyl group, an ethylphenyl group, an ethylmethylphenyl group, a diethylphenyl group, an n-propylphenyl group, an isopropylphenyl group, an isopropylmethylphenyl group, an isopropylethylphenyl group, a diisopropylphenyl group, an alkylphenyl group in which one or two linear or branched alkyl groups having 1 to 4 carbon atoms are substituted on the benzene ring, such as an n-butylphenyl group, a sec-butylphenyl group, and a tert-butylphenyl group; Can be mentioned.

  The phosphazene-modified phenol resin of the present invention (hereinafter, simply referred to as “phenol resin”) contains at least one kind of a group represented by the general formula (1) (hereinafter, referred to as “structural unit (1)”) as an essential repeating unit. I do.

  The phenolic resin includes, in addition to the structural unit (1), at least one kind of a group represented by the general formula (2) (hereinafter, referred to as a “structural unit (2)”) and / or a compound represented by the general formula (3). At least one of the following groups (hereinafter, referred to as “structural unit (3)”).

  Preferred phenolic resins contain at least one of the structural units (1), at least one of the structural units (2) and at least one of the structural units (3).

  In the phenol resin containing the structural unit (1) and the structural unit (2), the structural unit (1) is 6 to 99 mol%, preferably, based on the total amount of the structural unit (1) and the structural unit (2). It contains 28 to 99 mol%.

  In the phenol resin containing the structural unit (1) and the structural unit (3), the structural unit (1) is 16 to 99 mol%, preferably, based on the total amount of the structural unit (1) and the structural unit (3). It contains 28 to 99 mol%.

  The phenol resin containing the structural unit (1), the structural unit (2) and the structural unit (3) is based on the total amount of the structural unit (1), the structural unit (2) and the structural unit (3). When the content of (1) is 4 to 98 mol%, preferably 16 to 98 mol%, and the remainder is 1 (100%), 40 to 99%, preferably 50 to 91% of the content is from the structural unit (2). Become.

  The polymerization degree of the phenol resin is usually 2 to 4000, preferably 3 to 100. Further, the weight average molecular weight is usually 800 to 1200000, preferably 800 to 25000, and more preferably 800 to 6000.

In the structural unit (1), (2m + 2n + 1) Rs are the same or different and each is a C _1-6 alkyl group or a phenyl group, X is an oxygen atom, 2 ≦ m + n ≦ 99, and A is a group —CHR ² —, wherein R ² is a hydrogen atom, a C _1-6 alkyl group, a C _2-4 alkenyl group, a phenyl group or a hydroxyphenyl group.

Among them, (2m + 2n + 1) Rs are the same or different and are a C _1-4 alkyl group or a phenyl group, X is an oxygen atom, 2 ≦ m + n ≦ 29, and A is a group —CHR ² —. , R ² is preferably a hydrogen atom, a C _1-4 alkyl group, a phenyl group or a hydroxyphenyl group. In the structural unit (2), R ¹ is a hydrogen atom or a hydroxyl group, and R ³ is a hydrogen atom. , A C _1-4 alkyl group, a hydroxyl group or a phenyl group, A is a group —CHR ² , and R ² is a hydrogen atom, a C _1-6 alkyl group, a C _2-4 alkenyl group, a phenyl group or a hydroxyphenyl group And b is preferably from 0 to 2.

Among them, R ¹ is a hydrogen atom or a hydroxyl group, R ³ is a hydrogen atom, a C _1-4 alkyl group, a hydroxyl group or a phenyl group, A is a group —CHR ² , R ² is a hydrogen atom, C _{1 A -4} alkyl group, phenyl group or hydroxyphenyl group, wherein b is 0 to 2, is particularly preferred.

In the structural unit (3), R ⁴ is a hydrogen atom or a hydroxymethyl group, R ⁵ is a hydrogen atom, an amino group or a hydroxymethylamino group, A is a group —CHR ² , and R ² is a hydrogen atom. Those which are atoms, C _1-6 alkyl groups, C _2-4 alkenyl groups, phenyl groups or hydroxyphenyl groups are preferred.

Among them, R ⁴ is a hydrogen atom or a hydroxymethyl group, R ⁵ is an amino group, a hydroxymethylamino group or a phenyl group, A is a group —CHR ² , R ² is a hydrogen atom, C _1-4 Those which are an alkyl group, a phenyl group or a hydroxyphenyl group are particularly preferred.

  Further, the phenol resin has the general formula

［式中、Ａは上記に同じ。］
で表される基を含有することができる。この基においても、Ａが基−ＣＨＲ²であり、Ｒ²が水素原子、Ｃ_1-6アルキル基、Ｃ_2-4アルケニル基、フェニル基又はヒドロキシフェニル基であるものが好ましく、更にＡが基−ＣＨＲ²であり、Ｒ²が水素原子、Ｃ_1-4アルキル基、フェニル基又はヒドロキシフェニル基であるものが特に好ましい。

Wherein A is the same as above. ]
Can be contained. Also in this group, A is preferably a group —CHR ² , and R ² is preferably a hydrogen atom, a C _1-6 alkyl group, a C _2-4 alkenyl group, a phenyl group or a hydroxyphenyl group. —CHR ² , wherein R ² is a hydrogen atom, a C _1-4 alkyl group, a phenyl group or a hydroxyphenyl group is particularly preferred.

  The phenolic resin of the present invention can be produced, for example, by the following method.

Method A for producing phenolic resin
The phenolic resin of the present invention is, for example, a compound represented by formula (1a)

［式中、Ｒ¹、Ｙ¹、Ｙ²、Ｘ、ｍ及びｎは上記に同じ。Ｒ⁶は、ハロゲン原子、Ｃ_1-15アルキル基、Ｃ_3-15シクロアルキル基、Ｃ_2-15アルケニル基又はＣ_6-20アリール基を示す。］
で表されるホスファゼン化合物と、一般式（４）
Ａ＝Ｏ （４）
［式中、Ａは上記に同じ。］
で表されるアルデヒドとを重縮合反応させることにより製造できる。

[Wherein, R ¹ , Y ¹ , Y ² , X, m and n are the same as above. R ⁶ represents a halogen atom, a C _1-15 alkyl group, a C _3-15 cycloalkyl group, a C _2-15 alkenyl group or a C _6-20 aryl group. ]
A phosphazene compound represented by the general formula (4)
A = O (4)
Wherein A is the same as above. ]
Can be produced by a polycondensation reaction with an aldehyde represented by

In the general formula (1a), examples of the halogen atom represented by R ⁶ include chlorine, fluorine, bromine, iodine, and the like. Of these, chlorine is preferable. The groups other than the halogen atom represented by R ⁶ may be the same as the respective groups represented by R.

  In the polycondensation of the phosphazene compound (1a) and the aldehyde (4), the compound represented by the general formula (2a) is added together with the phosphazene compound (1a).

［式中、Ｒ¹、Ｒ³及びｂは上記に同じ。］
で表される芳香族化合物（２ａ）及び／又は一般式（３ａ）

Wherein R ¹ , R ³ and b are the same as above. ]
And / or an aromatic compound (2a) represented by the general formula (3a):

［式中Ｒ⁴及びＲ⁵は上記に同じ。］
で表されるトリアジン化合物（３ａ）を使用することができる。これらの化合物をホスファゼン化合物（１ａ）と使用すると、構成単位（１）の他に構成単位（２）及び／又は構成単位（３）を含有するフェノール樹脂を製造することができる。

Wherein R ⁴ and R ⁵ are the same as above. ]
The triazine compound (3a) represented by the following formula can be used. When these compounds are used together with the phosphazene compound (1a), a phenol resin containing the structural unit (2) and / or the structural unit (3) in addition to the structural unit (1) can be produced.

  In the following, the phosphazene compound (1a), the aromatic compound (2a), and the triazine compound (3a) may be collectively referred to as "monomer components" as necessary.

  The reaction between the phosphazene compound (1a) and the aldehyde (4) is carried out in the presence of a basic catalyst or an acidic catalyst, in an organic solvent or without a solvent, preferably without a solvent.

Phosphazene compound (1a) having no phenolic hydroxyl group (R ¹ = hydrogen atom in general formula (1a)) and / or aromatic compound (2a) having no phenolic hydroxyl group (R ¹ in general formula (2a) When a hydrogen atom is used, the polycondensation is preferably performed in the presence of an acidic catalyst, as in the case of producing a toluene resin or a xylene resin. When the triazine compound (3a) is used, the polycondensation reaction is preferably performed in the presence of a basic catalyst.

  Further, when the phosphazene compound (1a) having no phenolic hydroxyl group and / or the aromatic compound (2a) having no phenolic hydroxyl group is used in combination with the triazine compound (3a), these compounds are simultaneously reacted. Can be done. However, considering the reaction efficiency, the polycondensation reaction of the aromatic compound (2a) proceeds first in the presence of an acidic catalyst, and then the polycondensation reaction of the triazine compound (3a) in the presence of a basic catalyst. The polycondensation reaction of the triazine compound (3a) in the presence of a basic catalyst, and then the polycondensation reaction of the aromatic compound (2a) in the presence of an acidic catalyst. Is good.

  When the phosphazene compound (1a) and the aromatic compound (2a) are used in combination, the amount of the aromatic compound (2a) used is usually 0.01 to 15 mol, preferably 0 to 1 mol per 1 mol of the phosphazene compound (1a). It may be from 0.01 to 2.5 mol.

  When the phosphazene compound (1a) and the triazine compound (3a) are used in combination, the amount of the triazine compound (3a) to be used is generally 0.01 to 5 mol, preferably 0.01 mol, per 1 mol of the phosphazene compound (1a). The amount may be up to 2.5 mol.

  When the phosphazene compound (1a), the aromatic compound (2a) and the triazine compound (3a) are used in combination, the amount of the aromatic compound (2a) and the triazine compound (3a) used is the total amount of the phosphazene compound (1a) The amount is usually 0.02 to 20 mol, preferably 0.02 to 5 mol, per 1 mol. At this time, the use ratio of the aromatic compound (2a) and the triazine compound (3a) is not particularly limited, but is usually 0.01 to 1.5 mol, preferably 0 to 1 mol of the aromatic compound (2a). 0.1 to 1 mol of the triazine compound (3a) may be used.

  The amount of the aldehyde (4) to be used can be appropriately selected according to the type of the monomer component, the usage ratio, and the like. For example, when the monomer component contains a compound having a phenolic hydroxyl group (such as a phosphazene compound (1a) or an aromatic compound (2a)) and / or an amino group-containing compound (such as a triazine compound (3a)). The aldehyde (4) is usually added in an amount of 0.2 to 1.6 times, preferably 0.4 to 0.9 times, more preferably 0 to 1 times the total number of moles of the phenolic hydroxyl groups and amino groups. It may be used in a molar amount of 0.5 to 0.85 times. When the compound having a phenolic hydroxyl group and the compound having an amino group are not contained in the monomer component, the aldehyde (4) is added to the total moles of the aromatic ring contained in the monomer component. Usually, 0.2 to 10.0 times molar equivalent, preferably 0.5 to 5.0 times molar equivalent, more preferably 0.5 to 3.0 times molar equivalent may be used.

  In the reaction between the monomer component such as the phosphazene compound (1a) and the aldehyde (4), known organic solvents can be widely used, for example, aromatic hydrocarbons (benzene, toluene, xylene, chlorobenzene, dichlorobenzene, etc.). , Alcohol (methanol, ethanol, propanol, isopropanol, etc.), ether (diethyl ether, dioxane, tetrahydrofuran, diphenyl ether, anisole, etc.), ketone (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ester (ethyl acetate, butyl acetate, etc.) ), Alicyclic hydrocarbons (such as cyclohexane and petroleum ether), and halogenated hydrocarbons (such as chloroform, methylene chloride, carbon tetrachloride, and tetrachloroethane). Of these, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, and dichlorobenzene are preferred.

  In the reaction between the monomer component such as the phosphazene compound (1a) and the aldehyde (4), known basic catalysts can be widely used, for example, alkali metal hydroxides (such as sodium hydroxide and potassium hydroxide), Alkaline earth metal hydroxide (barium hydroxide, etc.), alkali metal carbonate (sodium carbonate, etc.), alkali metal oxide (sodium oxide, potassium oxide, etc.), alkaline earth metal oxide (barium oxide, etc.), Primary to tertiary amines (ammonia, ethylamine, diethylamine, triethylamine and the like), hexamethylenetetramine and the like can be mentioned. Among these basic catalysts, primary to tertiary amines and the like are preferable in consideration of the moisture resistance, electric characteristics, and the like of a resin composition obtained by blending the phenolic resin of the present invention with various synthetic resins. These basic catalysts can be used alone or in combination of two or more.

  As the acidic catalyst, known catalysts can be widely used. For example, inorganic acids (hydrochloric acid, sulfuric acid, sulfonic acid, etc.), organic acids (oxalic acid, acetic acid, etc.), divalent metal salts (Lewis acid, zinc acetate, lead acetate, naphthene, etc.) Zinc oxide and the like). Among these acidic catalysts, inorganic acids such as hydrochloric acid and organic acids such as oxalic acid and acetic acid are preferable in consideration of the moisture resistance, electric properties, and the like of a resin composition obtained by blending the phenolic resin of the present invention with various synthetic resins. These acidic catalysts can be used alone or in combination of two or more.

  The amount of the basic catalyst and the acidic catalyst used is not particularly limited, and may be a wide range depending on various conditions such as the type and amount of the monomer component used, the presence or absence of a reaction solvent, the desired physical properties of the phenol resin to be obtained, and the intended use. However, it is usually from 0.01 to 50 mol%, preferably from 0.05 to 5 mol%, based on the total number of moles of the monomer components used.

  The reaction temperature and time can be appropriately selected from a wide range according to the type of the monomer component, the presence or absence of the solvent, the type of the solvent, and the like. The reaction is usually carried out at room temperature to the boiling point of the monomer component or at a temperature between the azeotropic point of the monomer component and water, preferably at the lower temperature of the boiling point of the monomer component or the azeotropic point of the monomer component and water under reflux. The reaction is usually completed in 1 to 24 hours, preferably 1 to 15 hours. The phenolic resin of the present invention can be obtained by purifying the reaction mixture obtained by this reaction according to an ordinary method such as distillation.

  In the above polycondensation reaction, each compound used as a starting compound is specifically as follows.

  Specific examples of the aldehyde (4) include, for example, formaldehyde, acetaldehyde, propanal, 2,2-dimethylpropanal, 1-butanal, 2-butanal, 1-pentanal, 2-pentanal, hexanal, heptanal, pentenal, cyclohexane Propane carbaldehyde, cyclobutane carbaldehyde, cyclopentane carbaldehyde, cyclohexane carbaldehyde, methylcyclopentane carbaldehyde, benzaldehyde, o-salicylaldehyde, m-salicylaldehyde, p-salicylaldehyde, methylbenzaldehyde, dimethylbenzaldehyde, ethylbenzaldehyde, ethyl Methylbenzaldehyde, diethylbenzaldehyde, n-propylbenzaldehyde, isopropylbenzaldehyde, Sopropylmethylbenzaldehyde, isopropylethylbenzaldehyde, diisopropylbenzaldehyde, n-butylbenzaldehyde, sec-butylbenzaldehyde, tert-butylbenzaldehyde, n-pentylbenzaldehyde, n-hexylbenzaldehyde, cyclopropylbenzaldehyde, cyclobutylbenzaldehyde, cyclopentylbenzaldehyde, cyclohexylbenzaldehyde , Methylcyclopentylbenzaldehyde, acrylaldehyde, crotonaldehyde and the like.

  Among these, formaldehyde, acetaldehyde, propanal, 1-butanal, 2-butanal, hexanal, heptanal, pentenal, benzaldehyde, o-salicylaldehyde, m-salicylaldehyde, p-salicylaldehyde, acrylaldehyde, crotonaldehyde and the like are preferable. .

  In the present invention, paraformaldehyde, paraacetaldehyde, sym-trioxane, furfural and the like can be used instead of the aldehyde (4) exemplified above.

  The aldehyde (4) and the aldehyde used in place of it can be used alone or in combination of two or more.

  The phosphazene compound (1a) is known, and is produced, for example, according to the method described in Macromolecules, 1992, 25 (10), 2569-2574, JP-A-3-163090, JP-A-2000-198793, and the like.

  The phosphazene compound (1a) is, for example, represented by the general formula (5)

［式中、Ｙ¹及びＹ²は上記に同じ。Ｒ⁷はハロゲン原子を示す。ｌは３〜１００００の整数を示す。］
で表される鎖状又は環状ホスホニトリルジハライド、一般式（６）
ＲＸＨ （６）
［式中Ｒ及びＸは上記に同じ。］
で表される化合物及び一般式（７）

Wherein Y ¹ and Y ² are the same as above. R ⁷ represents a halogen atom. l represents an integer of 3 to 10000. ]
A chain or cyclic phosphonitrile dihalide represented by the general formula (6)
RXH (6)
Wherein R and X are the same as above. ]
And a compound represented by the general formula (7)

［式中、Ｒ¹及びＸは上記に同じ。］
で表される化合物を、塩基性物質の存在下に反応させることにより製造できる。

Wherein R ¹ and X are the same as above. ]
Can be produced by reacting the compound represented by the formula in the presence of a basic substance.

  The phosphazene compound (1a) can also be produced by reacting the linear or cyclic phosphonitrile dihalide (5) with an alkali metal salt of the compound (6) and an alkali metal salt of the compound (7).

  Phosphonitrile dihalide (5) is described, for example, in INORGANIC POLYMER (James E. Mark, Harry R. Allcock and Robert West, published in 1992, Prentice-Hall, Inc.), PHOSPHORUS-NITROGEN COMPOUNDS (HRALLCOCK, 1972). Annual report, ACADEMIC PRESS), “91-1 Inorganic Polymer Study Group: Theme: New Trends in Phosphazene” (Presentation: The Society of Polymer Science, Japan Society of Inorganic Polymer Study, Date: May 21, 1991 (Tue) ) 10: 00-16: 45, 3F conference room, Riken Kaikan, Tokyo University of Science), JP-A-57-87427, JP-B-58-19604, JP-B-61-1363, and many other known documents. It is described in.

  The phosphonitrile dihalide (5) is usually obtained as a mixture of several to several tens of linear and cyclic oligomers and / or polymers having different degrees of polymerization, as described in the above documents. . Therefore, the phosphazene compound obtained by substituting the halogen atom of the phosphonitrile dihalide (5) with another arbitrary group has several to several tens of compounds having the same composition ratio as that of the raw material phosphonitrile dihalide and different degrees of polymerization. As a mixture of linear or cyclic oligomers and / or polymers. The specific n number of chain or cyclic oligomers or polymers can be obtained by purifying the mixture by ordinary means such as recrystallization or column chromatography.

1 of the chain phosphonitrile dihalide (5) is 3 to 10,000, preferably 3 to 1,000, and more preferably 3 to 100. The P-terminal is usually substituted with a group -N = P (R ⁷ ) ₃ . On the other hand, the N-terminal is usually substituted with a group -P (R ⁷ ) ₄ (wherein R ⁷ represents a halogen atom as described above). This terminal group is a group -N = P (XR) ₃ or a group -N = P (= X) XR at the P-terminal and a group -P (XR) ₄ or a group at the N-terminal by a reaction with the compound (6). -P (= X) (XR) ₂ (wherein R and X are the same as above).

  1 of the cyclic phosphonitrile dihalide (5) is 3 to 25, preferably 3 to 14, and more preferably 3 to 8. When phosphonitrile dihalide is synthesized according to a known method, among the resulting cyclic substances, those having l = 3 to 8 usually account for 50 to 98 mol%, which is particularly practical.

  Among the phosphazene compounds (1a) thus obtained, R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, and X represents an oxygen atom, in consideration of heat resistance and moisture resistance of the obtained phenol resin. And R is preferably an alkyl group or a phenyl group having 1 to 4 carbon atoms, and X is particularly preferably an oxygen atom.

  In the phosphazene compound (1a), when two Rs bonded to the same or different phosphorus atoms are bonded to each other to form a cross-linking group, the group includes a p-phenylene group, 4,4 ′-(2,2- A dimethyl) methylbisphenylene group and a 4,4′-sulfonylbisphenylene group are preferred.

  Specific examples of the phosphazene compound (1a) include, for example, 2- (4′-hydroxyphenyl) -2,4,4,6,6-pentaphenoxycyclotriphosphazene, 2,2-di (4′-hydroxyphenyl) ) -4,4,6,6-tetraphenoxycyclotriphosphazene, 2,4-di (4′-hydroxyphenyl) -2,4,6,6-tetraphenoxycyclotriphosphazene, 2,2,4-tri (4'-hydroxyphenyl) -4,6,6-triphenoxycyclotriphosphazene, 2,4,6-tri (4'-hydroxyphenyl) -2,4,6-triphenoxycyclotriphosphazene, 2,2 , 4.6-Tetra (4'-hydroxyphenyl) -4,6-diphenoxycyclotriphosphazene, 2,2,4,4-tetra (4'-hydroxy Enyl) -6,6-diphenoxycyclotriphosphazene, 2,2,4,4,6-penta (4'-hydroxyphenyl) -6-phenoxycyclotriphosphazene, 2,2,4,4,6,6 Cyclotriphosphazene substituted with a 4'-hydroxyphenyl group and / or a phenoxy group, such as -hexa (4'-hydroxyphenyl) cyclotriphosphazene; 2- (4'-hydroxyphenyl) -2,4,4,6; 6,8,8-heptaphenoxycyclotetraphosphazene, 2,2-di (4′-hydroxyphenyl) -4,4,6,6,8,8-hexaphenoxycyclotetraphosphazene, 2,4-di (4 '-Hydroxyphenyl) -2,4,6,6,8,8-hexaphenoxycyclotetraphosphazene, 2,6-di (4'-hydroxyphenyl ) -2,4,4,6,8,8-hexaphenoxycyclotetraphosphazene, 2,2,4-tri (4'-hydroxyphenyl) -4,6,6,8,8-pentaphenoxycyclotetraphosphazene 2,2,6-tri (4'-hydroxyphenyl) -4,4,6,8,8-pentaphenoxycyclotetraphosphazene, 2,4,6-tri (4'-hydroxyphenyl) -2,4 , 6,8,8-pentaphenoxycyclotetraphosphazene, 2,2,4,4-tetra (4'-hydroxyphenyl) -6,6,8,8-tetraphenoxycyclotetraphosphazene, 2,2,4 6-tetra (4'-hydroxyphenyl) -4,6,8,8-tetraphenoxycyclotetraphosphazene, 2,2,4,8-tetra (4'-hydroxyphenyl)- 4,6,6,8-tetraphenoxycyclotetraphosphazene, 2,4,6,8-tetra (4′-hydroxyphenyl) -2,4,6,8-tetraphenoxycyclotetraphosphazene, 2,2,4 , 4,6-penta (4'-hydroxyphenyl) -6,8,8-triphenoxycyclotetraphosphazene, 2,2,4,6,8-penta (4'-hydroxyphenyl) -4,6,8 -Triphenoxycyclotetraphosphazene, 2,2,4,6,6-penta (4'-hydroxyphenyl) -4,8,8-triphenoxycyclotetraphosphazene, 2,2,4,4,6,6- Hexa (4'-hydroxyphenyl) -8,8-diphenoxycyclotetraphosphazene, 2,2,4,4,6,8-hexa (4'-hydroxyphenyl) -6,8- Phenoxycyclotetraphosphazene, 2,2,4,6,6,8-hexa (4′-hydroxyphenyl) -4,8-diphenoxycyclotetraphosphazene, 2,2,4,4,6,6,8- 4′- such as hepta (4′-hydroxyphenyl) -8-phenoxycyclotetraphosphazene and 2,2,4,4,6,6,8,8-octa (4′-hydroxyphenyl) -cyclotetraphosphazene Substituted cyclophosphazene such as cyclotetraphosphazene substituted with hydroxyphenyl group and / or phenoxy group, cyclopentaphosphazene substituted with 4′-hydroxyphenyl group and / or phenoxy group, cyclohexaphosphazene, cycloheptaphosphazene, cyclooctaphosphazene; 4'-hydroxyphenyl group and / or phenoxy There may be mentioned substituted and linear phosphazene compound having Cyclophosphazene same number of phosphorus atoms, mixtures of two or more of these. In the cyclic or chain phosphazene compound substituted with the 4′-hydroxyphenyl group and / or the phenoxy group, a part or all of the 4′-hydroxyphenyl group is replaced with a 2′-hydroxyphenyl group and / or a 3′-group. A single substance or a mixture selected from the group consisting of a cyclic phosphazene compound or a chain phosphazene compound substituted with a hydroxyphenyl group can be exemplified.

  The basic substance is not particularly limited as long as it can neutralize hydrogen halide generated during the reaction and is inactive with respect to the starting compound. For example, tertiary amines (trimethylamine, triethylamine, pyridine and the like), Alkali metal hydroxide (sodium hydroxide, potassium hydroxide, etc.), alkaline earth metal hydroxide (calcium hydroxide, etc.), alkali metal carbonate (sodium carbonate, potassium carbonate, cesium carbonate, etc.), alkaline earth metal Carbonates (such as calcium carbonate) can be mentioned. Of these, triethylamine, pyridine, sodium carbonate, potassium carbonate, cesium carbonate and the like are preferable in consideration of the reaction rate, the yield and stability of the target product, and the like. The amount of the basic substance used may be 1.0 to 20 equivalents, preferably 1.1 to 10 equivalents, based on the total number of moles of halogen atoms in the phosphonitrile dihalide (5).

  When this reaction is performed in an organic solvent, for example, usually in an organic solvent such as aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated aromatic hydrocarbons such as monochlorobenzene and dichlorobenzene. The reaction is usually performed at a temperature of room temperature to 150 ° C., preferably 80 to 140 ° C., and is completed usually in 1 to 12 hours, preferably 3 to 7 hours.

  Specific examples of the aromatic compound (2a) include, for example, phenol, methylphenol, dimethylphenol, trimethylphenol, hydroxymethylphenol, di (hydroxymethyl) phenol, tri (hydroxymethyl) phenol, hydroquinone, catechol, resorcinol, o Phenols such as -cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 3,5-xylenol, p-phenylphenol, bisphenol A, bisphenol F, benzene, toluene, xylene, Trimethylbenzene, tetramethylbenzene, hydroxymethylbenzene, di (hydroxymethyl) benzene, tri (hydroxymethyl) benzene, hydroxymethylmethylbenzene, hydroxymethyldimethylbenzene Zen, di (hydroxymethyl) benzene, and the like, such as methyl benzene. Among them, phenols such as phenol, hydroquinone, catechol, resorcinol, 3,5-xylenol, p-methylphenol, p-ethylphenol and p-phenylphenol, and benzenes such as benzene, toluene and xylene are preferred. As the aromatic compound (2a), one type can be used alone, or two or more types can be used in combination.

  Specific examples of the triazine compound (3a) include, for example, guanamine derivatives such as melamine, benzoguanamine, and acetoguanamine. As the triazine compound (3a), one type can be used alone, or two or more types can be used in combination.

Production method B of phenolic resin
The phenolic resin of the present invention comprises a phenolic resin obtained by polycondensing an aromatic compound (2a) and an aldehyde (4) or an aromatic compound (2a), a triazine compound (3a) and an aldehyde (4) with a compound represented by the general formula (8): )

［式中、Ｙ¹、Ｙ²及びｌは上記に同じ。Ｒ⁸は基−ＸＲ（式中Ｘ及びＲは上記に同じ）又はハロゲン原子を示す。但し２ｌ個のＲ⁸のうち、少なくとも一つはハロゲン原子を示すものとする。］
で表される鎖状又は環状ホスホニトリルハライドとを、塩基性物質の存在下に反応させることによって製造できる。

Wherein Y ¹ , Y ² and 1 are the same as above. R ⁸ represents a group —XR (where X and R are the same as above) or a halogen atom. However, at least one of the 2l R ⁸ is a halogen atom. ]
Can be produced by reacting a linear or cyclic phosphonitrile halide represented by the following formula in the presence of a basic substance.

  As the phenol resin used as a raw material, any known phenol resin containing an aromatic compound (2a) and an aldehyde (4) or an aromatic compound (2a), a triazine compound (3a) and an aldehyde (4) as monomer components is used. It is possible to use commercially available products.

  The linear or cyclic phosphonitrile dihalide (8) can be produced by reacting the phosphonitrile dihalide (5) with the compound (6) in the presence of a basic substance. Alternatively, it can be produced by reacting phosphonitrile dihalide (5) with an alkali metal salt of compound (6).

  Further, the chain or cyclic phosphonitrile dihalide (8) is produced, for example, according to the method described in JP-A-2000-198793.

  Specific examples of the phosphonitrile halide (8) include, for example, 2-chloro-2,4,4,6,6-pentaphenoxycyclotriphosphazene, 2,2-dichloro-4,4,6,6-tetraphenoxy Cyclotriphosphazene, 2,4-dichloro-2,4,6,6-tetraphenoxycyclotriphosphazene, 2,2,4-trichloro-4,6,6-triphenoxycyclotriphosphazene, 2,4,6- Trichloro-2,4,6-triphenoxycyclotriphosphazene, 2,2,4,6-tetrachloro-4,6-diphenoxycyclotriphosphazene, 2,2,4,4-tetrachloro-6,6- Cyclotriphosphazene substituted by chlorine and / or phenoxy group such as diphenoxycyclotriphosphazene, 2-chloro-2,4,4,6,6,8 8-heptaphenoxycyclotetraphosphazene, 2,2, -dichloro-4,4,6,6,8,8-hexaphenoxycyclotetraphosphazene, 2,4-dichloro-2,4,6,6,8,8 -Hexaphenoxycyclotetraphosphazene, 2,6-dichloro-2,4,4,6,8,8-hexaphenoxycyclotetraphosphazene, 2,2,4-trichloro-4,6,6,8,8-pentane Phenoxycyclotetraphosphazene, 2,2,6-trichloro-4,4,6,8,8-pentaphenoxycyclotetraphosphazene, 2,4,6-trichloro-2,4,6,8,8-pentaphenoxycyclo Tetraphosphazene, 2,2,4,4-tetrachloro-6,6,8,8-tetraphenoxycyclotetraphosphazene, 2,2,4,6-te Lachloro-4,6,8,8-tetraphenoxycyclotetraphosphazene, 2,2,4,8-tetrachloro-4,6,6,8-tetraphenoxycyclotetraphosphazene, 2,4,6,8-tetra Chloro-2,4,6,8-tetraphenoxycyclotetraphosphazene, 2,2,4,4,6-pentachloro-6,8,8-triphenoxycyclotetraphosphazene, 2,2,4,6,8- Pentachloro-4,6,8-triphenoxycyclotetraphosphazene, 2,2,4,6,6-pentachloro-4,8,8-triphenoxycyclotetraphosphazene, 2,2,4,4,6,6- Hexachloro-8,8-diphenoxycyclotetraphosphazene, 2,2,4,4,6,8-hexachloro-6,8-diphenoxycyclotetraphosphazene Cyclotetraphosphazene substituted with chlorine and / or phenoxy groups, such as 2,2,4,6,6,6,8-hexachloro-4,8-diphenoxycyclotetraphosphazene, cyclocyclophosphine substituted with chlorine and / or phenoxy groups Substituted cyclophosphazenes such as pentaphosphazene, cyclohexaphosphazene, cycloheptaphosphazene, and cyclooctaphosphazene; chain phosphazene compounds having a chlorine and / or phenoxy group substituted and having the same repetition number as the cyclophosphazene; Mixtures and the like can be mentioned. In the above-mentioned cyclic or chain phosphazene compounds substituted with chlorine and / or phenoxy groups, a single substance selected from cyclic phosphazene compounds or chain phosphazene compounds in which part or all of chlorine is replaced by bromine, and two kinds thereof. Examples thereof include the above mixtures. One type of the phosphonitrile halide (8) can be used alone, or two or more types can be used in combination.

  When the phenol resin to be reacted with the phosphonitrile halide (8) is a polycondensate of the aromatic compound (2a) and the aldehyde (4), the phosphonitrile halide ( It is used so that the total number of moles of the halogen atoms in 8) is less than 1.0, preferably 0.05 to 0.99, in a molar ratio.

  When the phenol resin to be reacted with the phosphonitrile halide (8) is a polycondensate of the aromatic compound (2a), the triazine compound (3a) and the aldehyde (4), the hydroxyl group and the amino group in the phenol resin The phosphonitrile halide (8) is used in such a manner that the total number of halogen atoms of the phosphonitrile halide (8) is less than 1.0, preferably 0.05 to 0.99, based on the total total number of moles.

  In any case, when the molar ratio exceeds 1.0, halogen atoms may remain in the obtained phenol resin.

  The basic substance is not particularly limited as long as it can neutralize the hydrogen halide generated by the reaction between the phenol resin and the phosphonitrile halide (8) and is inactive against them. Any of these can be used. Among them, triethylamine, pyridine, sodium carbonate, potassium carbonate, cesium carbonate and the like are preferable in consideration of the reaction rate, the yield of the target substance, stability and the like. The amount of the basic substance used may be 1.0 to 20 equivalents, preferably 1.1 to 10 equivalents, based on the total number of moles of halogen atoms in the phosphonitrile halide (8).

  When the reaction is carried out in an organic solvent, the organic solvent is not particularly limited, but is preferably one capable of dissolving at least one of a phenol resin and phosphonitrile halide (8), and particularly preferably one capable of dissolving both. Specific examples include ethers such as tetrahydrofuran, ketones such as acetone and methyl isobutyl ketone, and aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene. The amount of the organic solvent used is not particularly limited, and the range in which the reaction proceeds smoothly may be appropriately selected according to the type and amount of the starting compound, the type of the organic solvent, and the like. When an organic solvent is used, the reaction is usually carried out at a temperature from room temperature to the boiling point of the organic solvent used, preferably around the boiling point of the organic solvent, and is completed usually in 1 to 48 hours, preferably in 1 to 36 hours.

  When the reaction is performed in the absence of a solvent, the reaction is desirably performed at a temperature or higher at which at least one of the phenol resin and the phosphonitrile halide (8) can be dissolved. The reaction time may be appropriately selected from a wide range depending on the type and amount of the starting compound, the type of the basic substance, and the like, and is usually 1 to 48 hours, preferably 1 to 36 hours.

  The phenolic resin of the present invention thus obtained can be easily isolated and purified from the reaction mixture by ordinary means such as extraction. When the halogen atom of the phosphonitrile halide (8) remains in the obtained phenol resin, the phenol resin is treated with the phosphonitrile dihalide (5) and the compound (6) or a metal salt thereof. Similarly to the reaction, the compound (6) may be reacted in the presence of a basic substance, or an alkali metal salt of the compound (6) may be reacted with the phenol resin. The amount of compound (6) or an alkali metal salt thereof to be used is at least 1 equivalent to the number of moles of unreacted halogen atoms.

Use of phenolic resin The phenolic resin of the present invention exhibits excellent flame retardancy and can be suitably used as a flame retardant for synthetic resins.

  Further, among the phenolic resins of the present invention, those having a phenolic hydroxyl group in the molecule are particularly useful as a flame-retardant curing agent for epoxy resins, and provide excellent flame-retardant properties without impairing the good properties inherent to epoxy resins. Properties can be imparted.

  The present invention provides a flame-retardant resin composition obtained by mixing one or more of the phenolic resins of the present invention with a synthetic resin.

The synthetic resin is not particularly limited, and any known resin can be used. For example, polyethylene, polypropylene, polyisoprene, chlorinated polyethylene, polyvinyl chloride, polybutadiene, polystyrene, impact-resistant polystyrene, acrylonitrile-styrene resin (AS) Resin), acrylonitrile-butadiene-styrene resin (ABS resin), methyl methacrylate-butadiene-styrene resin (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin), acrylonitrile-acryl rubber-styrene resin (AAS resin) ), Polymethyl (meth) acrylate, polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polycarbonate, polyf Nylene ether, modified polyphenylene ether, polyamide (aliphatic and / or aromatic), polyphenylene sulfide, polyimide, polyether ether ketone, polysulfone, polyarylate, polyether ketone, polyether nitrile, polythioether sulfone, polyether sulfone , Polybenzimidazole, polycarbodiimide, polyamide imide, polyether imide, thermoplastic resin such as liquid crystal polymer, polyurethane, phenol resin, melamine resin, urea resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, epoxy resin (bisphenol Epoxy resin, bisphenol-A epoxy resin, bisphenol-F epoxy resin, bisphenol-AD epoxy resin, bisphenol- Epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, cycloaliphatic epoxy resin, glycidyl ester epoxy resin, glycidyl ether epoxy resin, polyfunctional epoxy resin, glycidylamine epoxy resin, heterocyclic epoxy resin , Dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, amorphous epoxy resin, biphenyl type epoxy resin, polyfunctional type epoxy resin, urethane modified epoxy resin, brominated bisphenol-A type epoxy resin etc.) Resins can be mentioned.

  Among these, thermoplastic resins such as polyester, ABS resin, polycarbonate, modified polyphenylene ether, polyamide, and polyimide, and thermosetting resins such as polyurethane, phenol resin, melamine resin, and epoxy resin are preferable.

  One of the above synthetic resins can be used alone, or two or more can be used in combination.

  The blending amount of the phenolic resin of the present invention in the flame-retardant resin composition of the present invention can be appropriately selected from a wide range according to the type of the synthetic resin, the use of the obtained flame-retardant composition, and the like. For example, when the synthetic resin is a thermoplastic resin, 0.1 to 50 parts by weight, preferably 0.5 to 40 parts by weight, and more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the thermoplastic resin. Is good. Further, for the thermosetting resin, it is usually 5 to 500 parts by weight, preferably 30 to 450 parts by weight, and more preferably 50 to 400 parts by weight based on 100 parts by weight of the thermosetting resin. .

  The flame-retardant resin composition of the present invention may contain a fluororesin. Known fluororesins can be used, for example, polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (PFA), Examples include tetrafluoroethylene-ethylene copolymer (ETFE), poly (trifluorochloroethylene) (CTFE), and polyvinylidene (PVdF). Among these, PTFE is preferred. One type of fluororesin can be used alone, or two or more types can be used in combination.

  The compounding amount of the fluororesin is not particularly limited, and may be a wide range depending on various conditions such as the type and amount of the synthetic resin, the phosphazene-modified phenol resin, other additives, and the use of the obtained flame-retardant resin composition. It can be selected as appropriate. The amount of the fluororesin is usually about 0.01 to 5.0 parts by weight, preferably about 0.1 to 1.2 parts by weight, per 100 parts by weight of the synthetic resin.

  Further, the flame-retardant resin composition of the present invention may be appropriately combined with various conventionally known resin additives as long as the excellent properties are not impaired.

  Known inorganic fillers can be used as the inorganic filler for enhancing the anti-dripping effect and improving the mechanical strength of the resin composition.For example, mica, kaolin, talc, silica, clay, barium sulfate, barium carbonate, calcium carbonate, Calcium sulfate, barium sulfate, aluminum hydroxide, magnesium hydroxide, calcium silicate, titanium oxide, zinc oxide, zinc borate, glass beads, glass balloons, glass flakes, hydrotalcite, fibrous alkali metal titanate (potassium titanate) Fiber, sodium titanate fiber, etc.), fibrous borate (aluminum borate fiber, magnesium borate fiber, zinc borate fiber, etc.), zinc oxide fiber, titanium oxide fiber, magnesium oxide fiber, gypsum fiber, aluminum silicate fiber, Calcium silicate fiber, silicon carbide fiber, titanium carbide Fiber, silicon nitride fiber, titanium nitride fibers, carbon fibers, alumina fibers, alumina - silica fibers, zirconia fibers, quartz fibers, flaky titanate, and the flaky titanium dioxide and the like. Among them, those having shape anisotropy such as fibrous material, mica, flaky (or plate-like) titanate, and flaky titanium oxide are preferable, and fibrous alkali metal titanate, fibrous borate are preferable. , Zinc oxide fiber, calcium silicate fiber, flaky titanate, flaky titanium oxide and the like are particularly preferred. One inorganic filler can be used alone, or two or more inorganic fillers can be used in combination.

  Further, for the purpose of suppressing the deterioration of the resin, the surface of the inorganic filler may be covered with a silane coupling agent. The amount of the inorganic filler is not particularly limited, and various conditions such as the type of the resin to be mixed, the amount of the phenolic resin of the present invention, the type and the amount of the other additives, and the use of the obtained flame-retardant resin composition are used. Can be selected from a wide range as appropriate. In consideration of the balance between the improvement in flame retardancy and the improvement in mechanical properties, the amount of the inorganic filler is usually about 0.01 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the synthetic resin. It may be about the degree.

  The flame retardant resin composition of the present invention may contain a flame retardant or an anti-dripping agent as long as the preferable properties are not impaired. The flame retardant or the anti-dripping agent is not particularly limited, and known ones can be used, and examples thereof include a phosphazene compound, an organic phosphorus compound, phosphorus, and an inorganic flame retardant. These may be used alone or in combination of two or more.

  Further, the flame-retardant resin composition of the present invention may contain one or more general resin additives as long as the preferable properties are not impaired. The resin additive is not particularly restricted but includes, for example, ultraviolet absorbers (benzophenones, benzotriazoles, cyanoacrylates, triazines, etc.), light stabilizers (hindered amines, etc.), antioxidants (hindered phenols, etc.). , Organic phosphorus peroxide decomposers, organic sulfur peroxide decomposers, etc.), light shielding agents (rutile titanium oxide, zinc oxide, chromium oxide, cerium oxide, etc.), metal deactivators (benzotriazoles, etc.) , Quencher (organic nickel, etc.), antifogging agent, antifungal agent, antibacterial agent, deodorant, plasticizer, antistatic agent, surfactant, polymerization inhibitor, crosslinker, pigment, dye, sensitizer, curing Agents, curing accelerators, diluents, flow control agents, defoamers, foaming agents, leveling agents, adhesives, adhesives, tackifiers, lubricants, release agents, lubricants, nucleating agents, reinforcing agents, Compatibilizer, conductive agent, Chi-blocking agent, anti-tracking agents, phosphorescent agents, various stabilizers.

  Further, the flame-retardant resin composition of the present invention using an epoxy resin as a synthetic resin, in particular, 30 to 500 parts by weight, preferably 50 to 450 parts by weight of the phenol resin of the present invention, based on 100 parts by weight of the epoxy resin, is cured. The flame-retardant resin composition of the present invention comprising 0.01 to 50 parts by weight of an accelerator, preferably 0.05 to 10 parts by weight and 0.01 to 300 parts by weight of an inorganic filler, preferably 1 to 100 parts by weight It is very suitable as a material for electronic components, more specifically, as a sealing material or substrate material for electronic components such as ICs. In this composition, together with the phenolic resin of the present invention, a general phenolic resin conventionally used as a curing agent for an epoxy resin (a resin obtained by condensing or co-condensing phenols and aldehydes under an acidic catalyst) May be used.

  Known curing accelerators can be used, for example, diazabicycloalkenes such as 1,8-diazabicyclo (5,4,0) undecene-7 and derivatives thereof, triethylenediamine, benzyldimethylamine, triethanolamine, Tertiary amines such as dimethylaminoethanol and tris (dimethylaminomethyl) phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole and 2-heptadecylimidazole; tributylphosphine; Organic phosphines such as methyldiphenylphosphine and triphenylphosphine; tetra-substituted phosphonium / tetra-substituted borates such as tetraphenylphosphonium / tetraphenylborate; 2-ethyl-4-methylimidazole / tetraphenyl Borate, may be mentioned tetraphenyl boron salts such as N- methylmorpholine tetraphenylborate. As the curing accelerator, one type can be used alone, or two or more types can be used in combination.

  Known inorganic fillers can be used. Examples thereof include fused silica, crystalline silica, alumina, talc, aluminum nitride, boron nitride, silicon nitride, titanium oxide, barium sulfate, and other spherical / powder materials. And spherical / powder materials such as fused silica, crystalline silica, alumina and aluminum nitride are preferred. One inorganic filler can be used alone, or two or more inorganic fillers can be used in combination. Surface treatment may be performed using a silane coupling agent.

  The flame-retardant resin composition of the present invention can be produced by mixing and / or kneading a predetermined amount or an appropriate amount of the synthetic resin, the phenolic resin of the present invention, and other additives by a known method. In particular, a melt blending method in which heating is performed by an extruder or the like, a solution mixing method in which all components are uniformly dissolved or dispersed in a solvent, and the like can be preferably used.

  According to the melt blending method, a mixture of each component in the form of powder, beads, flakes or pellets is mixed with an extruder such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a pressure kneader, a two-roll or a three-roll. Mixing and / or kneading using a kneader or the like.

  Further, in the solution mixing method, as a solvent, a halogen-based solvent such as dichloromethane, chloroform, and trichloroethylene; an aromatic solvent such as benzene, toluene, and xylene; a ketone-based solvent such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; dimethylformamide; Dimethyl sulfoxide and the like can be mentioned. These solvents can be used alone or in combination of two or more.

  The flame-retardant resin composition of the present invention can be formed into a desired shape according to its use. The molding method is not particularly limited. Usually, a casting method of dissolving the resin composition in a solvent used in the above-described solution mixing method and molding it into a desired shape, and a heat melting method of heating and melting the resin composition to form the resin composition are used. The casting method and the heat melting method may be performed alone. Moreover, you may perform it combining each.

  For example, several to several tens of films of the flame-retardant resin composition prepared by a casting method are laminated, and heated and melted by a heat melting method, for example, a press molding machine to obtain a sheet.

  In addition, for example, by a known molding method such as press molding, injection molding, extrusion molding, cast molding, or by curing by irradiating heat or ultraviolet rays or electron beams depending on the application, a single layer or a plurality of layers Molded articles of any shape such as resin plates, sheets, films and spherical, square and irregularly shaped articles.

  The molded article made of the flame-retardant resin composition of the present invention can be applied to all fields in which synthetic resin can be used. For example, electric / electronic / communication equipment, precision equipment, transportation equipment such as automobiles, textile products, various manufacturing Examples include machinery, food packaging films and containers, agriculture, forestry and fisheries, construction materials, medical supplies, and components of furniture.

  As a specific application, in electric / electronic / communication equipment, for example, a printer, a computer, a word processor, a keyboard, a small information terminal (PDA), a telephone, a mobile phone, a facsimile, a copying machine, an electronic cash register (ECR) ), Calculators, electronic organizers, electronic dictionaries, cards, holders, stationery, etc., office and office automation equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, kotatsu and other home appliances, televisions, VTRs , Video cameras, camcorders, radios with cassettes, tape recorders, minidisc players, CD players, DVD players, LD players, speakers, liquid crystal displays and their drivers, AV equipment such as EL displays, plasma displays, connectors, relays, capacitors, Switch, print base Materials, coil bobbins, semiconductor sealing materials, batteries and their separators or their sealing materials, CCDs, LEDs, electric wires, cables, transformers, motors, antenna coils, deflection yokes, distribution boards, clocks, and other electric and electronic components Communication equipment such as a contact data carrier package system and a smart card / smart tag.

  Next, the use of the present flame retardant resin composition in electric / electronic component materials will be described in more detail.

  (1) As a printed board material, a prepreg obtained by impregnating a base material such as glass, paper, or aramid fiber cloth with the flame-retardant resin composition of the present invention, and the prepreg processed into a wiring board (glass / paper) / Aramid) substrate, copper-clad laminate, composite copper-clad laminate, flexible copper-clad laminate, substrate for build-up type multilayer printed wiring board, resin film with carrier, flexible printed wiring board, bonding sheet, etc. . Printed circuit board materials using the flame-retardant resin composition of the present invention may be of any type, from rigid or flexible, or from sheet or film to plate-like substrates. As a material for a printed circuit board, a known method can be suitably used without limitation.

  (2) Further, with the recent miniaturization, high capacity, and multi-functionality of electric and electronic devices, printed wiring boards have a multilayer structure, and a resin layer in which insulating properties are imparted to interlayer resin layers between layers. (Interlayer insulating film (layer), insulating adhesive layer), resin layer in which the interlayer resin layer between each layer is provided with conductivity or anisotropic conductivity (interlayer conductive film (layer), conductive adhesive layer, interlayer A function-imparting film (layer) such as a conductive film (layer), an anisotropic conductive adhesive layer), and a dielectric constant control or conductivity control film (layer) is required. In addition, components such as IC elements, solder balls, lead frames, heat spreaders, and stiffeners, adhesive (adhesive) adhesive layers for bonding the function-imparting films (layers) and the like to each other, and surface protective layers such as coverlay films are also provided. Is needed. In addition, functions such as resin bumps (including resin-coated bumps), conductive resin layers inside through holes, and stress relaxation resin layers formed for the purpose of protecting elements from various thermal and mechanical external stresses. An application layer is also needed. The flame-retardant resin composition of the present invention can be suitably used in these various interlayer forming layers / parts without any restrictions.

  (3) Regarding the semiconductor encapsulating material described above, a semiconductor element mounting method (for example, lead frame package, SOP (Small Outline Package), SOJ (Small Outline J-leaded Package), QFP type (Quad Flat Package), Surface mounting package represented by BGA (Ball Grid Array), various miniaturized CSP (chip size package), etc. and connection method with circuits (wire bonding, TAB (Tape Automated Bonding) connection, flip chip There are various types of sealing materials depending on differences in connection and processes, and the performance required for the sealing materials is also diverse.The properties of the sealing resin are the same as those used in conventional molding compounds. Capillary flow type liquid sealing material used as an underfill material and secondary under for secondary mounting Film and paste sealing such as compression flow type ACF (Anisotropic Conductive Film), NCF (Non Conductive Film), ACP (Anisotropic Conductive Paste), NCP (Non Conductive Paste), etc. The present flame-retardant resin composition can be suitably used in any type of sealing material without limitation, without reducing the performance required of the sealing material. In addition, the flame retardancy of the sealing resin can be sufficiently exhibited.

  (4) Battery sealing parts, transformer insulating materials, motor insulating materials, and antenna coil insulating materials are particularly called casting materials because they are mainly filled with resin and sealed. This cast material is required to have various performances such as high heat dissipation (thermal conductivity), heat resistance, and impact resistance. The flame-retardant resin composition of the present invention can be suitably used without limitation in these casting material applications.

  (5) In addition, lead-free solder has been demanded from recent approaches to environmental issues, and Sn / Ag / Cu, Sn / Ag / (Bi), Sn / Zn / (Bi), Sn / Ag / Cu / Bi based solders have been proposed as lead-free solders, but their flow or reflow temperature is 10 to 20 ° C. higher than the flow or reflow temperature of general Pb / Sn based eutectic solder. Has become. Therefore, it is desired to improve the heat resistance of a resin used for an electric / electronic component as a substrate material or a sealing material. The flame-retardant resin composition of the present invention can be suitably used without any limitation even in these electric and electronic parts requiring particularly heat resistance.

  (6) The flame retardancy of the present invention can be applied to various displays such as the above-described liquid crystal display, EL display, plasma display, active matrix liquid crystal display, and optical materials such as photocouplers and optoisolators. The conductive resin composition can be suitably used without any limitation. For example, an adhesive (layer) or insulation between components such as a polarizing plate / glass substrate / (transparent) electrode substrate / alignment film / liquid crystal layer / filter / reflection plate / conductive substrate / conductive film for electrode / barrier layer. Examples include layers, spacers, and resin parts such as sealing materials.

  In addition, other uses include various chairs and seat stuffing, dressings, belts, ceiling and wall coverings, coachable tops, armrests, door trims, rear package trays, carpets, mats, sun visors, wheel covers, mattress covers, Airbags, insulating materials, hanging hands, hanging straps, electric wire covering materials, electric insulating materials, paints, can inner surface paints, can inner cover paints, adhesives, touch panels, hearing aids, coating materials, ink (toner), sealing materials, Upholstery, flooring, corner walls, carpets, wallpaper, wall coverings, exterior materials, interior materials, roofing materials, soundproofing boards, heat insulating boards, window materials, sealing materials between window glass and window frames, water and concrete Anti-corrosion materials such as automobiles, vehicles, ships, bridges, aircraft and civil engineering / building materials, clothing, curtains, sheets, plywood, plywood, carpets, entrance mats, food packaging fills And containers, agriculture, forestry and fisheries, medical supplies, aerospace composite materials, sheets, buckets, hoses, containers, glasses, bags, cases, goggles, skis, snowboards, skateboards, rackets, tents, musical instruments, etc. Life and sports goods.

  The phenol resin of the present invention is a halogen-free flame-retardant phenol resin, and is useful as a raw material of a flame-retardant molded article.

  The phenolic resin of the present invention is useful as a flame retardant for synthetic resins. When the phenolic resin of the present invention is added to a synthetic resin, the synthetic resin has a high degree of equivalent to V-0 of UL-94 standard without substantially reducing the physical properties of the synthetic resin, particularly, moisture resistance and heat resistance. Flame retardancy can be imparted.

  In particular, when the phenolic resin of the present invention is mixed with an epoxy resin for electronic component materials, physical properties inherent to the epoxy resin, such as moisture resistance, heat resistance, adhesion, and mechanical strength, are hardly impaired.

  The phenolic resin of the present invention is extremely suitable as a flame retardant for an epoxy resin as an electronic component material requiring high reliability.

  Hereinafter, the present invention will be specifically described with reference to Synthesis Examples, Examples, and Comparative Examples. Unless otherwise specified, “%” and “part” mean “% by weight” and “part by weight”, respectively.

The phosphazene compound obtained in the synthesis example was measured for ¹ H-NMR spectrum and ³¹ P-NMR spectrum (measured by dissolving the obtained compound in deuterated chloroform or deuterated dimethyl sulfoxide), CHN elemental analysis, and phosphorus The elemental phosphorus was analyzed by vanadium molybdate absorption spectrophotometry and identified from these results. Further, the weight average molecular weight was determined by gel permeation chromatography (GPC) measurement.

Synthesis Example 1 (Synthesis of dichlorophosphazene)
In a 10-liter flask equipped with a reflux condenser, a thermometer and a stirrer, weigh 365 g (6.8 mol) of ammonium chloride, 1290 g (6.2 mol) of phosphorus pentachloride and 5 g (0.06 mol) of zinc oxide. Then, 5000 ml of chlorobenzene was added and mixed to obtain a dispersion. The dispersion was refluxed (132 ° C.) for 120 minutes to complete the reaction. The reaction solution was subjected to suction filtration to remove unreacted ammonium chloride, and about 3.5 liters of chlorobenzene was distilled off from the filtrate under a reduced pressure of 1.3 to 2.7 hPa and a temperature of 30 to 40 ° C. The obtained colorless and transparent chlorobenzene solution (2347 g) was subjected to ³¹ P-NMR spectrum measurement and concentration analysis by gas chromatography, and this solution was a 30% chlorobenzene solution of dichlorophosphazene oligomer (l-mer). It was confirmed that the composition was 59% trimer, 15% tetramer, 10% pentamer and hexamer, 3% heptamer and 3% octamer or more: 13%. Yield 98.0% (based on phosphorus pentachloride).

  Further, the chlorobenzene solution of the dichlorophosphazene oligomer obtained above is further concentrated under a reduced pressure of 1.3 to 2.7 hPa and a temperature of 30 to 40 ° C., and then recrystallized, whereby hexachlorocyclotriphosphazene and octaoctane are obtained. 405 g of a mixture with chlorocyclotetraphosphazene were obtained. The composition was 76% trimer and 24% tetramer.

  The mixture was recrystallized three times using n-hexane to obtain 250 g of hexachlorocyclotriphosphazene having a purity of 99.9%.

Synthesis Example 2 (Synthesis of phosphazene having methoxy group)
In a 10-liter flask equipped with a reflux condenser, a thermometer, and a stirrer, 1871 g (15.07 mol) of p-methoxyphenol was weighed, 6000 ml of tetrahydrofuran (hereinafter, referred to as "THF") was added, and the mixture was stirred until uniform. . Then, 315 g (13.7 g-atm) of metallic sodium was charged at 50 ° C. or lower, and after the addition was completed, the temperature was raised to 60 ° C. over 1 hour, and then stirred at 60 ° C. to 68 ° C. for 4 hours to obtain p-methoxy. A THF solution of phenol sodium salt was obtained.

  Also, 1702 g (18.08 mol) of phenol was weighed and placed in a 10-liter flask equipped with a reflux condenser, a thermometer and a stirrer, and 6000 ml of THF was added to dissolve. Then, 378 g (16.4 g atom) of metallic sodium was charged at 50 ° C. or lower, and after the addition was completed, the temperature was raised to 60 ° C. over 1 hour, followed by stirring at 60 ° C. to 68 ° C. for 4 hours to obtain sodium phenolate. To give a THF solution.

  Separately, in a 20-liter flask, 5292 g (13.70 mol) of the 30% dichlorophosphazene oligomer chlorobenzene solution of Synthesis Example 1 was weighed, and the THF solution of the above p-methoxyphenol sodium salt was further kept at 30 ° C. or lower. The mixture was slowly added dropwise, and after the addition, the mixture was stirred at 30 ° C. or lower for 1 hour, and further heated and stirred under solvent reflux (70 ° C.) for 3 hours. The reaction solution is once cooled, and the above-mentioned THF solution of sodium phenolate is slowly added dropwise while maintaining the temperature at 30 ° C. or lower. After the addition, the temperature is further increased to 30 ° C. or lower for 1 hour, and the solvent is refluxed (70 ° C.). Stirred for 10 hours. After completion of the reaction, the reaction mixture was filtered and concentrated, redissolved in 10 liters of chlorobenzene, washed three times with a 5% aqueous sodium hydroxide solution and once with 5% hydrochloric acid, and neutralized and washed twice with water. Thereafter, chlorobenzene was distilled off under reduced pressure to obtain 3,447 g of a brown oily substance.

^From the results of ¹ H-NMR spectrum and ³¹ P-NMR spectrum measurement, CHN elemental analysis and phosphorus content measurement, the brown oil obtained above was found to be [N = P (OPh) _0.97 (OC ₆ H ₄ OCH _{3 1.03} ] _l
(The composition of the l-mer is 59% for trimer, 15% for tetramer, 10% for pentamer and hexamer, 3% for heptamer and 13% for more than octamer.)
Was confirmed to be a phosphazene compound having a methoxy group represented by Yield 96.0%. Weight average molecular weight 1090.

Synthesis Example 3 (Synthesis of phosphazene having methoxy group)
The procedure of Synthesis Example 2 was repeated, except that 2209 g (18.08 mol) of p-ethylphenol was used instead of phenol to prepare the sodium salt of p-ethylphenol, to obtain 3928 g of a brown oil.

^From the results of ¹ H-NMR spectrum and ³¹ P-NMR spectrum measurement, CHN elemental analysis and phosphorus content measurement, the brown oily compound obtained above was found to be [N = P (OC ₆ H ₄ C ₂ H ₅ ) _0.99 (OC ₆ H ₄ OCH ₃ ) _1.01 ] _l
(The composition of the l-mer is 59% for trimer, 15% for tetramer, 10% for pentamer and hexamer, 3% for heptamer and 13% for more than octamer.)
Was confirmed to be a phosphazene compound having a methoxy group represented by Yield 97.1%. Weight average molecular weight 1210.

Synthesis Example 4 (Synthesis of phosphazene having methoxy group)
The same operation as in Synthesis Example 2 was carried out except that 3259 g (15.07 mol) of 2-phenoxy-4-methoxyphenol was used instead of p-methoxyphenol to prepare a sodium salt of 2-phenoxy-4-methoxyphenol, 4619 g of a brown oil were obtained.

^From the results of ¹ H-NMR spectrum and ³¹ P-NMR spectrum measurement, CHN elemental analysis and phosphorus content measurement, the brown oily compound obtained above was found to be [N = P (OC ₆ H ₄ C ₂ H ₅ ) _0.99 (OC ₆ H ₃ (OPh-m) (OCH ₃ -p) _1.01 ] _l
(The composition of the l-mer is 59% for trimer, 15% for tetramer, 10% for pentamer and hexamer, 3% for heptamer and 13% for more than octamer.)
Was confirmed to be a phosphazene compound having a methoxy group represented by 95.1% yield. Weight average molecular weight 1480.

Synthesis Example 5 (Synthesis of phosphazene having methoxy group)
1250 g (10.0 mol) of p-methoxyphenol was weighed and placed in a 10-liter flask equipped with a reflux condenser, a thermometer, and a stirrer. Thereto, 210 g (9.1 g atom) of metallic sodium was charged at 50 ° C. or less, and after the addition was completed, the temperature was raised to 60 ° C. over 1 hour, followed by stirring at 60 ° C. to 68 ° C. for 4 hours to obtain p-methoxy. A THF solution of phenol sodium salt was obtained.

  Further, 2080 g (22.1 mol) of phenol was weighed and placed in a 10-liter flask equipped with a reflux condenser, a thermometer and a stirrer, and 7000 ml of THF was added to dissolve. Then, 462 g (20.1 g atom) of metallic sodium is charged at a temperature of 50 ° C. or less, and after the completion of the charging, the temperature is raised to 60 ° C. over 1 hour, followed by stirring at 60 ° C. to 68 ° C. for 4 hours to obtain sodium phenolate To give a THF solution.

  Separately, in a 20-liter flask, 7938 g (13.70 mol) of a 20% chlorobenzene solution of hexachlorocyclotriphosphazene of Synthesis Example 1 was weighed, and while keeping the temperature at 30 ° C. or lower, the sodium salt of p-methoxyphenol obtained above was measured. The THF solution was slowly added dropwise, and after the addition, the mixture was stirred at 30 ° C. or lower for 1 hour, further heated and stirred under solvent reflux (70 ° C.) for 5 hours. After the reaction solution was once cooled, the THF solution of sodium phenolate obtained above was slowly added dropwise while maintaining the temperature at 30 ° C. or lower. After the addition, the temperature was further raised to 30 ° C. or lower for 1 hour, and the solvent was refluxed (70 ° C.). C) for 20 hours. After completion of the reaction, the same post-treatment as in Synthesis Example 2 was performed to obtain 3378 g of a brown oily substance.

^From the results of ¹ H-NMR spectrum and ³¹ P-NMR spectrum measurement, CHN elemental analysis, and phosphorus content measurement, the brown oil obtained above was identified as [N = P (OPh) _1.32 (OC ₆ H ₄ OCH _{3 0.68} ] ₃
Was confirmed to be a phosphazene compound having a methoxy group represented by Yield 98.0%.

Synthesis Example 6 (Synthesis of phosphazene partially containing reactive chlorine)
313.7 g (3.33 mol) of phenol was weighed and placed in a 1-liter flask equipped with a reflux condenser, a thermometer, and a stirrer, and 500 ml of THF was added thereto, followed by stirring until the mixture became homogeneous. Then, 76.6 g (3.33 g atom) of metallic sodium was charged at 50 ° C. or less, and after the completion of the charging, the temperature was raised to 60 ° C. over 1 hour, and then the mixture was stirred at 60 ° C. to 68 ° C. for 4 hours. A solution of the phenolate in THF was obtained.

  Separately, 772.6 g (2.00 mol) of a 30% dichlorophosphazene oligomer chlorobenzene solution of Synthesis Example 1 was weighed and placed in a 2 liter flask equipped with a reflux condenser, a thermometer and a stirrer, and kept at 30 ° C. or lower. The THF solution of sodium phenolate obtained above was slowly added dropwise, and after the addition, the mixture was stirred at 30 ° C. or lower for 3 hours, further heated, and stirred under solvent reflux (70 ° C.) for 10 hours. After completion of the reaction, the reaction mixture was filtered and concentrated, redissolved in 1.5 liter of chlorobenzene, washed once with a 5% aqueous sodium hydroxide solution and once with 5% hydrochloric acid, and neutralized and washed twice with water. Thereafter, chlorobenzene was distilled off under reduced pressure to obtain 390.4 g of a pale yellow oil.

From the results of ¹ H-NMR spectrum and ³¹ P-NMR spectrum measurement, hydrolyzable chlorine measurement, CHN elemental analysis and phosphorus content measurement, the pale yellow oil obtained above was identified as [N = P (OPh) _1.67 (Cl) _0.33 ] _l (The composition of the l-mer is as follows: 59% trimer, 15% tetramer, 10% pentamer and hexamer, 10% heptamer: 3% And octamer or more: 13%). 92.0% yield. Weight average molecular weight 880.

Synthesis Example 7 (Synthesis of phosphazene partially containing reactive chlorine)
A sodium salt of p-phenylphenol was prepared using 227.0 g (1.33 mol) of p-phenylphenol instead of phenol, and 20% hexachlorocyclotriphosphazene and 20% of chlorobenzene solution of 30% dichlorophosphazene oligomer were used. A pale yellow oil was obtained by performing the same operation as in Synthesis Example 6 except that 1159 g (2.00 mol) of a chlorobenzene solution (trimer: 76%, tetramer: 24%) of a mixture of octachlorocyclotetraphosphazene was used. 364.2 g were obtained.

^From the results of ¹ H-NMR spectrum and ³¹ P-NMR spectrum measurement, hydrolyzable chlorine measurement, CHN elemental analysis, and phosphorus content measurement, the pale yellow oily compound obtained above was identified as [N = P (OC ₆ H ₄ -C ₆ H ₅ ) _0.66 (Cl) _1.34 ] _l (the composition of the monomer is partially 76% of trimer and 24% of tetramer). It was confirmed to be a phosphazene compound. 89.2% yield.

Synthesis Example 8 (Synthesis of phosphazene having hydroxy group)
In a 20-liter flask equipped with a reflux condenser, a thermometer, and a stirrer, 1048 g (4.00 mol) of the methoxy group-containing phosphazene compound of Synthesis Example 2 was weighed, and 8000 ml of methylene chloride was added, and the mixture was stirred until uniform. did. A solution prepared by dissolving 1290 g (5.15 mol) of boron tribromide in methylene chloride and adjusting the concentration to 1 mol / liter was weighed into a dropping funnel, and was slowly charged at 30 ° C. or lower. After the addition was completed, the mixture was stirred at room temperature for 4 hours. 5000 ml of deionized water was slowly dropped into the reaction solution while maintaining the temperature at 30 ° C. or lower, and the mixture was stirred at 30 ° C. or lower for 1 hour. After completion of the reaction, the reaction mixture dispersion was filtered, and the brown solid filtered off was redissolved in 10 liters of ethyl acetate, washed three times with water, and after neutralization, further washed three times with water. Thereafter, ethyl acetate was distilled off under reduced pressure to obtain 970 g of a brown solid.

^From the results of ¹ H-NMR spectrum and ³¹ P-NMR spectrum measurement, hydroxyl equivalent measurement, CHN elemental analysis, and phosphorus content measurement, the brown solid compound obtained above was found to be [N = P (OPh) _0.95 (OC ₆ H ₄ OH) _1.05 ] _l (The composition of the l-mer is as follows: 59% trimer, 15% tetramer, 10% pentamer and hexamer, 10% heptamer: 3% and 8 mers Phosphazene compound having a hydroxy group represented by the following formula: Yield 97.8%. Weight average molecular weight 1030.

Synthesis Example 9 (Synthesis of phosphazene having hydroxy group)
Same as Synthesis Example 7 except that 1157 g (4.00 mol) of the phosphazene compound of Synthesis Example 3 was used instead of the phosphazene compound of Synthesis Example 2 and the amount of boron tribromide was changed to 1265 g (5.05 mol). The operation was performed to obtain 1090 g of a brown solid.

^{As a result of 1} H-NMR spectrum and ³¹ P-NMR spectrum measurement, hydroxyl equivalent measurement, CHN elemental analysis and phosphorus content measurement, the brown solid compound was [N = P (OC ₆ H ₄ C ₂ H ₅ ) _1.00 (OC ₆ H ₄ OH) _1.00 ] _l (The composition of the l-mer is as follows: trimer: 59%, tetramer: 15%, pentamer and hexamer: 10%, heptamer: 3% and Octamer or more: 13%). Yield 99.0%. Weight average molecular weight 1150.

Synthesis Example 10 (Synthesis of phosphazene having hydroxy group)
The same operation as in Synthesis Example 8 was performed except that 1265 g (5.05 mol) of the phosphazene compound of Synthesis Example 4 was used instead of the phosphazene compound of Synthesis Example 2 and 1265 g (4.00 mol) of boron tribromide was used. 1338 g of a brown solid were obtained.

^{As a result of 1} H-NMR spectrum and ³¹ P-NMR spectrum measurement, hydroxyl equivalent measurement, CHN elemental analysis and phosphorus content measurement, the brown solid compound obtained above was found to be [N = P (OPh) _0.99 (OC ₆ H ₃ (OPh-m) (OH-p)) _1.01 ] _l
(The composition of the l-mer is 59% for trimer, 15% for tetramer, 10% for pentamer and hexamer, 3% for heptamer and 13% for more than octamer.)
It was confirmed to be a phosphazene compound having a hydroxy group represented by Yield 98.3%. Weight average molecular weight 1420.
Synthesis Example 11 (Synthesis of phosphazene having hydroxy group)
Same as Synthesis Example 8 except that 1006 g (4.00 mol) of the phosphazene compound of Synthesis Example 5 was used instead of the phosphazene compound of Synthesis Example 2 and the amount of boron tribromide used was 852 g (2.72 mol). The operation was performed to obtain 953 g of a brown solid.

^{As a result of 1} H-NMR spectrum and ³¹ P-NMR spectrum measurement, hydroxyl equivalent measurement, CHN elemental analysis, and phosphorus content measurement, the brown solid compound obtained above was found to be [N = P (OPh) _1.33 (OC ₆ H ₄ OH) _0.67 ] ₃
It was confirmed to be a phosphazene compound having a hydroxy group represented by Yield 98.5%.

Synthesis Example 12 (Synthesis of phosphazene having methoxy group)
In a 200 ml flask equipped with a reflux condenser, a thermometer and a stirrer, 51.4 g (0.37 mol) of p-methoxybenzenethiol was weighed, and 75 ml of THF was added and stirred until uniform. 7.7 g (0.33 gram atom) of metallic sodium was charged therein at 50 ° C. or lower, and after the addition was completed, the temperature was raised to 60 ° C. over 1 hour, and then the mixture was stirred at 60 ° C. to 68 ° C. for 4 hours. A THF solution of -methoxybenzenethiol sodium salt was obtained.

  Also, 88.9 g (0.81 mol) of thiophenol was weighed and placed in a 300 ml flask equipped with a reflux condenser, a thermometer and a stirrer, and dissolved by adding 100 ml of THF. Thereto, 16.9 g (0.73 g atom) of metallic sodium was charged at 50 ° C. or less, and after the addition was completed, the temperature was raised to 60 ° C. over 1 hour, followed by stirring at 60 ° C. to 68 ° C. for 4 hours. A THF solution of phenol sodium salt was obtained.

  Separately, 290 g (0.50 mol) of a 20% chlorobenzene solution of hexachlorocyclotriphosphazene of Synthesis Example 1 was weighed and placed in a 1-liter flask, and the sodium p-methoxybenzenethiol obtained above was kept at 30 ° C. or lower. A THF solution of the salt was slowly added dropwise, and after the addition, the mixture was stirred at 30 ° C. or lower for 1 hour, and further heated at dw under reflux of the solvent (70 ° C.) for 5 hours. After the reaction solution was once cooled, the THF solution of the thiophenol sodium salt obtained above was slowly added dropwise while maintaining the temperature at 30 ° C. or lower. After the addition, the temperature was further raised to 30 ° C. or lower for 1 hour, and the solvent was refluxed ( (70 ° C) for 20 hours. After completion of the reaction, the same post-treatment as in Synthesis Example 2 was performed to obtain 135 g of a brown oily substance.

^From the results of ¹ H-NMR spectrum and ³¹ P-NMR spectrum measurement, CHN elemental analysis and phosphorus content measurement, the brown oily compound obtained above was found to be [N = P (SPh) _1.32 (SC ₆ H ₄ OCH _{3 0.68} ] ₃
Was confirmed to be a phosphazene compound having a methoxy group represented by 95.3% yield.

Synthesis Example 13 (Synthesis of phosphazene having methoxy group)
3501 g of a brown oil was obtained by performing the same operation as in Synthesis Example 2 except that 1871 g (15.07 mol) of o-methoxyphenol was used instead of p-methoxyphenol to prepare a sodium salt of o-methoxyphenol. Was.

^From the results of ¹ H-NMR spectrum and ³¹ P-NMR spectrum measurement, CHN elemental analysis and phosphorus content measurement, the brown oily compound obtained above was found to be [N = P (OC ₆ H ₅ ) _0.97 (OC ₆ H ₄ -ortho-OCH ₃ ) _1.03 ] _l (The composition of the l-mer is 59% trimer, 15% tetramer, 10% pentamer and hexamer, 10% heptamer, 3% and Octamer or more: 13%). Yield 97.5%. Weight average molecular weight 1090.

Synthesis Example 14 (Synthesis of phosphazene having methoxy group)
In a 10-liter flask equipped with a reflux condenser, a thermometer, and a stirrer, weigh 904.5 g (9.60 mol) of phenol and 22.0 g (0.20 mol) of hydroquinone, and add 5000 ml of THF to make the mixture uniform. Until it has been stirred. 229.9 g (10.00 g atom) of metallic sodium was charged therein at 50 ° C. or lower, and after completion of the charging, the temperature was raised to 60 ° C. over 1 hour, followed by stirring at 60 ° C. to 68 ° C. for 4 hours to obtain phenol. And a THF solution of sodium salt of hydroquinone.

  Further, 1502.1 g (12.10 mol) of p-methoxyphenol was weighed and placed in a 10-liter flask equipped with a reflux condenser, a thermometer, and a stirrer, and dissolved by adding 5000 ml of THF. 252.9 g (11.00 gram atom) of metallic sodium was added thereto at 50 ° C. or lower, and after the addition was completed, the temperature was raised to 60 ° C. over 1 hour, followed by stirring at 60 ° C. to 68 ° C. for 4 hours. -A THF solution of sodium methoxyphenol was obtained.

  Separately, 5794 g (10.00 mol) of a 20% chlorobenzene solution (trimer: 76%, tetramer: 24%) of a mixture of hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene of Synthesis Example 1 in a 20-liter flask. ), And the THF solution of the sodium salt of phenol and hydroquinone obtained above was slowly added dropwise thereto while maintaining the temperature at 30 ° C or lower. Stirred under (70 ° C.) for 5 hours. After once cooling the reaction solution, the THF solution of the above-obtained sodium salt of p-methoxyphenol was slowly added dropwise while maintaining the temperature at 30 ° C or lower. After the addition, the temperature was further increased to 30 ° C or lower for 1 hour, and the solvent was refluxed. Stirred under (70 ° C.) for 20 hours. After completion of the reaction, the same post-treatment as in Synthesis Example 2 was performed to obtain 2441 g of a brown oily substance.

^From the results of ¹ H-NMR spectrum and ³¹ P-NMR spectrum measurement, CHN elemental analysis and phosphorus content measurement, the brown oily compound obtained above was found to be [N = P (OPh) _0.96 (—OC ₆ H ₄ O −) _0.02 (OC ₆ H ₄ OCH ₃ ) _1.00 ] _l (the monomer composition is a phosphazene compound having a methoxy group represented by a trimer of 76% and a tetramer of 24%). confirmed. Yield 93.9%.

Synthesis Example 15 (Synthesis of phosphazene having hydroxy group)
In a 2 liter flask equipped with a reflux condenser, a thermometer, and a stirrer, 70.9 g (0.25 mol) of the phosphazene compound of Synthesis Example 12 was weighed, and 1250 ml of methylene chloride was added, followed by stirring until the mixture became homogeneous. A solution prepared by dissolving 53.2 g (0.21 mol) of boron tribromide in methylene chloride to a concentration of 1 mol / liter was weighed into a dropping funnel, and was slowly charged at 30 ° C. or lower. After completion of the addition, the mixture was stirred at room temperature for 4 hours, then, while maintaining the temperature at 30 ° C or lower, 100 ml of deionized water was slowly dropped into the reaction solution, and the mixture was stirred at 30 ° C or lower for 1 hour. After completion of the reaction, the reaction mixture dispersion was filtered, and the brown solid filtered off was redissolved in 1 liter of ethyl acetate, washed three times with water, and after neutralization, further washed three times with water. Thereafter, ethyl acetate was distilled off under reduced pressure to obtain 68.5 g of a brown solid.

^From the results of ¹ H-NMR spectrum and ³¹ P-NMR spectrum measurement, hydroxyl equivalent measurement, CHN elemental analysis, and phosphorus content measurement, the brown solid compound obtained above was found to be [N = P (SPh) _1.32 (SC ₆ H ₄ OH) _0.68 ] _3, which was confirmed to be a phosphazene compound having a hydroxy group. 99.9% yield.

Synthesis Example 16 (Synthesis of phosphazene having hydroxy group)
Same as Synthesis Example 8 except that 1048 g (4.00 mol) of the phosphazene compound of Synthesis Example 13 was used instead of the phosphazene compound of Synthesis Example 2 and the amount of boron tribromide was changed to 1290 g (5.15 mol) Was carried out to obtain 974 g of a brown solid.

^From the results of ¹ H-NMR spectrum and ³¹ P-NMR spectrum measurement, hydroxyl equivalent measurement, CHN elemental analysis, and phosphorus content measurement, the brown solid compound obtained above was identified as [N = P (OC ₆ H ₅ ) _0.98 (OC ₆ H ₄ OH-o) _1.02 ] ₁ (The composition of the l-mer is as follows: trimer: 59%, tetramer: 15%, pentamer and hexamer: 10%, heptamer: 3% and octamer or more: 13%). Yield 98.4%. Weight average molecular weight 1030.

Synthesis Example 17 (Synthesis of phosphazene having hydroxy group)
Same as Synthesis Example 8 except that 1040 g (4.00 mol) of the phosphazene compound of Synthesis Example 14 was used instead of the phosphazene compound of Synthesis Example 2, and the amount of boron tribromide was changed to 1253 g (5.00 mol). Was carried out to obtain 975.8 g of a brown solid.

^From the results of ¹ H-NMR spectrum and ³¹ P-NMR spectrum measurement, hydroxyl equivalent measurement, CHN elemental analysis, and phosphorus content measurement, the brown solid compound obtained above was found to be [N = P (OPh) _0.96 (− A phosphazene compound having a hydroxy group represented by the formula: OC ₆ H ₄ O—) _0.02 (OC ₆ H ₄ OH) _1.00 ] _l (the composition of a monomer is 76% of a trimer and 24% of a tetramer) Was confirmed. 99.2% yield.

Synthesis Example 18 (Synthesis of phenoxyphosphazene)
2174 g (23.10 mol) of phenol was weighed and placed in a 20-liter flask equipped with a reflux condenser, a thermometer, and a stirrer, and 10 liters of THF was added thereto, followed by stirring until the mixture became uniform. At that time, 482.8 g (21.00 mol) of metallic sodium was charged at a temperature of 50 ° C. or less, and after the addition was completed, the temperature was raised to 60 ° C. over 1 hour. A solution of the THF in THF was obtained. While maintaining the temperature at 30 ° C. or lower, 5794 g (10.00 mol) of a 20% chlorobenzene solution of hexachlorocyclotriphosphazene of Synthesis Example 1 was slowly added dropwise. After the addition, the temperature was further increased to 30 ° C. or lower for 1 hour, and the solvent was further added. The mixture was stirred at reflux (70 ° C.) for 10 hours. After completion of the reaction, the same post-treatment as in Synthesis Example 2 was performed to obtain a brown oily substance. This was recrystallized using 10 liters of n-hexane to obtain 2196 g of white crystals.

^From the results of ¹ H-NMR spectrum and ³¹ P-NMR spectrum measurement, CHN elemental analysis and phosphorus content measurement, the white crystalline compound obtained above was a phenoxy compound represented by [N = P (OPh) ₂ ] ₃ It was confirmed to be a phosphazene compound. 95.0% yield.

Example 1 (Synthesis of modified phenolic resin: Production method A)
In a 1 liter flask equipped with a reflux condenser, a thermometer and a stirrer, 236.2 g (0.95 mol) of the phosphazene compound of Synthesis Example 8, 67.6 g (0.81 mol) of a 36% aqueous solution of formalin, and oxalic acid dihydrate After 1.3 g (0.01 mol) of the hydrate was weighed and reacted at 95 to 100 ° C. for 3 hours, the pressure in the reactor was reduced to remove water to obtain a novolak phenol resin. Hydroxyl equivalent 234 g / eq. , Phosphorus content 12.0%, nitrogen content 5.4%.

Example 2 (Synthesis of Modified Phenolic Resin: Production Method A)
In a 1-liter flask equipped with a reflux condenser, a thermometer, and a stirrer, 248.0 g (1.00 mol) of the phosphazene compound of Synthesis Example 8, 188.2 g (2.00 mol) of phenol, and a 36% aqueous solution of formalin 203. 5 g (2.44 mol) and 3.9 g (0.03 mol) of oxalic acid dihydrate were weighed out and reacted at reflux temperature for 2 hours. The water was removed to obtain a novolak type phenol resin. Hydroxyl equivalent 151 g / eq. , Phosphorus content 6.6%, nitrogen content 3.0%.

The phosphazene compound of Synthesis Example 8 as a raw material has a chemical structure of the formula [N = P (OPh) _0.95 (OC ₆ H ₄ OH) _1.05 ] ₁ . Here, the composition of the l-mer is as follows: trimer: 59%, tetramer: 15%, pentamer and hexamer: 10%, heptamer: 3% and more than octamer: 13%. is there. In the case of the trimer, since the cyclotriphosphazene ring has an average of about three hydroxyphenoxy groups, the phenol resin of the present invention has a phenol having a weight average molecular weight of about 700 on the phenyl ring of these hydroxyphenoxy groups. It can be inferred that the resin residue (substituted by the group represented by the above general formula (2) in which R ¹ is a hydroxyl group, R ³ is a hydrogen atom, and A is a methylene group) is substituted.

Example 3 (Synthesis of Modified Phenolic Resin: Production Method A)
In a 1-liter flask equipped with a reflux condenser, a thermometer, and a stirrer, 275.2 g (1.00 mol) of the phosphazene compound of Synthesis Example 9, 216.3 g (2.00 mol) of p-cresol, and 248.3 g of benzaldehyde (2.34 mol) and 0.2 ml of 36% concentrated hydrochloric acid were weighed and reacted at reflux temperature for 2 hours. Then, the pressure inside the reactor was reduced to remove unreacted p-cresol and generated water, and the novolak type A phenol resin was obtained. Hydroxyl equivalent 230 g / eq. , Phosphorus content 4.4%, nitrogen content 2.0%.

Example 4 (Synthesis of Modified Phenolic Resin: Production Method A)
In a 1 liter flask equipped with a reflux condenser, a thermometer, and a stirrer, 340.4 g (1.00 mol) of the phosphazene compound of Synthesis Example 10, 188.2 g (2.00 mol) of phenol, and a 36% aqueous solution of formalin 203 After measuring 0.4 g (2.44 mol) and 3.8 g (0.03 mol) of oxalic acid dihydrate and reacting at reflux temperature for 2 hours, the pressure was reduced in the reactor to reduce unreacted phenol and the formation of phenol. The water was removed to obtain a novolak type phenol resin. Hydroxyl equivalent 185 g / eq. , Phosphorus content 5.6%, nitrogen content 2.5%.

Example 5 (Synthesis of Modified Phenolic Resin: Production Method A)
36.0 g (0.43 mol) of a 36% aqueous formalin solution was added to a 500 ml flask equipped with a reflux condenser, a thermometer and a stirrer, and 30 g of concentrated sulfuric acid was slowly added while cooling the flask. Then, 26.5 g (0.25 mol) of xylene was charged, and the reaction was carried out under reflux for 5 hours. After completion of the reaction, toluene was added to the reaction mixture, and the organic layer was washed by an extraction operation. The organic layer was concentrated, and the solvent was distilled off to obtain a xylene formaldehyde resin.

  Next, 25.0 g of xylene formaldehyde resin, 241.9 g (1.00 mol) of the phosphazene compound of Synthesis Example 11, and 188.2 g of phenol (2.10 g) were placed in a 1-liter flask equipped with a reflux condenser, a thermometer and a stirrer. 00 mol), 63.3 g (2.00 mol) of 95% paraformaldehyde, and 4.6 g (0.03 mol) of p-toluenesulfonic acid, and reacted at reflux temperature for 4 hours. The pressure was reduced to remove unreacted phenol and generated water to obtain a novolak-type phenol resin. Hydroxyl equivalent 175 g / eq. , Phosphorus content 6.5%, nitrogen content 2.9%.

The phosphazene compound of Synthesis Example 11, which is a raw material, has a chemical structure of the formula [N = P (OPh) _1.33 (OC ₆ H ₄ OH) _0.67 ] ₃ . Since the cyclotriphosphazene ring has an average of about two hydroxyphenoxy groups, the phenol resin of the present invention has a phenol resin residue having a weight average molecular weight of about 1900 (R ¹⁾ on the phenyl ring of these hydroxyphenoxy groups. Is a hydroxyl group, R ³ is a hydrogen atom, A is a methylene group, a group represented by the above general formula (2) and R ¹ is a hydrogen atom, R ³ is a methyl group, b is 2, and A is a methylene group. It can be inferred that the group represented by the general formula (2) is a structural unit, and the ratio of these structural units is the former: the latter = 8: 1).

Example 6 (Synthesis of Modified Phenolic Resin: Production Method B)
In a 2 liter flask equipped with a reflux condenser, a thermometer and a stirrer, 105.0 g (0.50 mol) of the phosphazene compound of Synthesis Example 6 and a phenol novolak resin (hydroxyl equivalent: 105 g / eq., Trade name: SP941) And 105.0 g of Asahi Organic Materials Industry Co., Ltd.) were weighed and dissolved by adding 500 ml of acetone. Thereto, 162.9 g (0.50 mol) of cesium carbonate was added and reacted at reflux temperature for 4 hours. After the reaction solution was once cooled, 47.1 g (0.50 mol) of phenol was added to the reactor, and the reaction was performed again at the reflux temperature for 1 hour. After completion of the reaction, the reaction solution was filtered, acetone was distilled off under reduced pressure, and then redissolved in methyl isobutyl ketone. After washing once with 5% hydrochloric acid and twice after neutralization, the solvent was distilled off to obtain a brown resin. Hydrolysable chlorine content 0.001%, hydroxyl equivalent 244 g / eq. , Phosphorus content 7.5%, nitrogen content 3.4%.

Example 7 (Synthesis of modified phenolic resin: Production method B)
In a 2 liter flask equipped with a reflux condenser, a thermometer and a stirrer, 102.5 g (0.50 mol) of the phosphazene compound of Synthesis Example 7 and a triazine-modified phenol novolak resin (hydroxyl equivalent 125 g / eq., Nitrogen content) 105.0 g of 12%, trade name: LA-7054, manufactured by Dainippon Ink and Chemicals, Inc. was weighed and dissolved by adding 1000 ml of acetone. 438.4 g (1.35 mol) of cesium carbonate was added thereto and reacted at reflux temperature for 4 hours. After the reaction solution was once cooled, 47.1 g (0.50 mol) of phenol was added to the reactor, and the reaction was performed again at the reflux temperature for 1 hour. After completion of the reaction, the reaction solution was filtered, acetone was distilled off under reduced pressure, and then redissolved in methyl isobutyl ketone. After washing once with 5% hydrochloric acid and twice after neutralization, the solvent was distilled off to obtain a brown resin. Hydrolysable chlorine content 0.001%, hydroxyl equivalent 615 g / eq. , Phosphorus content 7.6%, nitrogen content 10.8%.

Example 8 (Synthesis of Modified Phenolic Resin: Production Method A)
In a 1-liter flask equipped with a reflux condenser, a thermometer and a stirrer, 247.5 g (1.00 mol) of the phosphazene compound of Synthesis Example 16, 188.2 g (2.00 mol) of phenol, and a 36% aqueous solution of formalin 201. 5 g (2.42 mol) and 1.0 g (0.01 mol) of triethylamine were added and reacted at 80 ° C. for 3 hours. After completion of the reaction, 63.1 g (0.50 mol) of melamine was added to the reaction mixture, and the mixture was reacted at reflux temperature for 4 hours. Then, the pressure inside the reactor was reduced to remove unreacted phenol and generated water. A phenolic resin was obtained. Hydroxyl equivalent 174 g / eq. , Phosphorus content 5.9%, nitrogen content 10.5%.

Example 9 (Synthesis of Modified Phenolic Resin: Production Method A)
In a 1-liter flask equipped with a reflux condenser, a thermometer, and a stirrer, 245.9 g (1.00 mol) of the phosphazene compound of Synthesis Example 17, 10.0 g of the xylene formaldehyde resin obtained in the middle of Example 5, phenol 178.8 g (1.90 mol), 205.6 g (2.47 mol) of a 36% aqueous solution of formalin and 1.0 g (0.01 mol) of triethylamine were added and reacted at 80 ° C. for 3 hours. After completion of the reaction, 56.2 g (0.30 mol) of benzoguanamine was added to the reaction mixture, and the mixture was reacted at reflux temperature for 4 hours. Then, the pressure inside the reactor was reduced to remove unreacted phenol and produced water. A phenolic resin was obtained. Hydroxyl equivalent 180 g / eq. , Phosphorus content 6.0%, nitrogen content 4.8%.

Example 10 (Synthesis of Modified Phenolic Resin: Production Method B)
In a 100 ml flask equipped with a reflux condenser, a thermometer and a stirrer, 52.0 g (0.23 mol) of the phosphazene compound of Synthesis Example 18, 30.0 g (0.95 mol) of 95% paraformaldehyde and 85% phosphoric acid 35 g was added and the reaction was carried out under reflux for 10 hours. After completion of the reaction, toluene was added to the reaction mixture, and the organic layer was washed by an extraction operation. The organic layer was concentrated, and the solvent was distilled off to obtain a brown resin. Analysis of this brown resin by gel permeation chromatography confirmed the formation of an oligomer having [N = P (OPh) ₂ ] ₃ units as the minimum structural unit.

  Next, 50.0 g of the brown resin obtained above, 124.0 g (0.50 mol) of the phosphazene compound of Synthesis Example 7 and phenol 94. were placed in a 1-liter flask equipped with a reflux condenser, a thermometer and a stirrer. 1 g (1.00 mol), 12.9 g (0.14 mol) of sym-trioxane and 1.9 g (0.02 mol) of oxalic acid dihydrate were weighed and reacted at reflux temperature for 4 hours. The pressure in the vessel was reduced to remove unreacted phenol and produced water, to obtain a novolak type phenol resin. Hydroxyl equivalent 179 g / eq. , Phosphorus content 7.3%, nitrogen content 3.3%.

Example 11 (Synthesis of Modified Phenolic Resin: Production Method A)
In a 500 ml flask equipped with a reflux condenser, a thermometer and a stirrer, 54.8 g (0.20 mol) of the phosphazene compound of Synthesis Example 15, 43.3 g (0.40 mol) of o-cresol, and 54.0 g of salicylaldehyde (0.44 mol) and 1.00 g (0.01 mol) of p-toluenesulfonic acid were weighed and reacted at reflux temperature for 2 hours. The water was removed to obtain a novolak type phenol resin. Hydroxyl equivalent 150 g / eq. , Phosphorus content 4.4%, nitrogen content 1.9%.

Table 1 shows the composition ratio (mol%) and the weight-average molecular weight of the phenolic resins obtained in Examples 1 to 11 above.

Examples 12 to 33 and Comparative Examples 1 to 4
A predetermined amount of each component shown in Table 1 was mixed and kneaded using a twin-screw heating roll at a kneading temperature of 80 to 90 ° C. and a kneading time of 15 minutes to obtain a molding composition.

Details of each component used are as follows.
Epoxy resin:
Cresol novolak type epoxy resin (trade name: Epicoat 180S65, softening point: 67 ° C., epoxy equivalent: 209 g / eq., Manufactured by Japan Epoxy Resin Co., Ltd.), biphenyl skeleton type epoxy resin (trade name: Epicoat YX4000H, melting point: 105 ° C, epoxy equivalent: 194 g / eq., Manufactured by Japan Epoxy Resin Co., Ltd.)
-Brominated bisphenol A type epoxy resin (trade name: Epicoat 5050, softening point: 80 ° C, epoxy equivalent: 375 g / eq., Bromine content: 48%, manufactured by Japan Epoxy Resin Co., Ltd.)
Curing agent:
Phenol novolak resin (trade name: SP941, softening point: 84 ° C, hydroxyl equivalent: 105 g / eq., Manufactured by Asahi Organic Materials Co., Ltd.)
-Phenol aralkyl resin (trade name: Millex XLC-4L, softening point: 63 ° C, hydroxyl equivalent: 168 g / eq, manufactured by Mitsui Chemicals, Inc.)
Triazine-modified phenol novolak resin (trade name: LA-7054, hydroxyl equivalent: 125 g / eq, nitrogen content: 12%, manufactured by Dainippon Ink and Chemicals, Inc.)
Curing catalyst: triphenylphosphine (reagent manufactured by Wako Pure Chemical Industries, Ltd.)
Silica component: spherical fused silica (trade name: YXK-35R, manufactured by Tatsumori Co., Ltd.)
Other additives:
-Carnauba wax (trade name: Carnauba wax special No. 1, manufactured by Kato Hiroyuki Co., Ltd.)
・ Carbon black (trade name: MA-600, manufactured by Mitsubishi Chemical Corporation)
-Γ-glycidoxypropyltrimethoxysilane (trade name: A-187, manufactured by Nippon Unicar Co., Ltd.)
Triphenyl phosphate (phosphorus content 9.5%, phosphorus-containing flame retardant, manufactured by Wako Pure Chemical Industries, Ltd.)
-Antimony trioxide (flame retardant, manufactured by Wako Pure Chemical Industries, Ltd.)

実施例１２〜３３及び比較例１〜４の成形用組成物の特性を、次に示す方法で評価した。

The characteristics of the molding compositions of Examples 12 to 33 and Comparative Examples 1 to 4 were evaluated by the following methods.

(1) Hot Hardness A disk having a diameter of 50 mm × thickness of 3 mm was molded by a transfer press under the conditions of 175 ° C., 7 MPa, and 90 seconds. The hardness of the molded product immediately after molding was measured using a Shore hardness tester (trade name: Shore D type hardness tester, manufactured by Shimadzu Corporation). The higher the value of the hardness when heated, the better the evaluation.

(2) Water Absorption A disk having a diameter of 50 mm and a thickness of 3 mm was prepared from the molding composition according to JIS K-6911. The disc was left under the conditions of 85 ° C. and 85% RH for 24 hours and 168 hours, and the water absorption (%) was determined from the weight change before and after leaving. The smaller the numerical value of the water absorption, the better.

(3) Adhesion A test piece of 100 mm × 70 mm × 3 mm was formed on a 30 mm thick aluminum foil by a transfer press under the conditions of 180 ° C., 7 MPa, and 90 seconds using the molding composition. For this test piece, the peel strength of the aluminum foil in the vertical direction was measured. The larger the peel strength value (N / m), the better.

(4) Flame retardancy A test piece having a thickness of 1/16 inch, a length of 5 inches and a width of 0.5 inch was prepared from the above molding composition, and a flame retardancy evaluation test was conducted based on the UL-94 standard. Was done.

(5) Reflow crack resistance From the above molding composition, a 54-pin GFP (outer dimensions 20 mm × 14 mm × 2 mm, lead frame 42 alloy, semiconductor element dimensions 8 mm × 10 mm) was used at 175 ° C., 7 MPa, and 90 seconds. It was prepared by transfer molding. This was absorbed under the conditions of 85 ° C. and 85% RH, and reflow treatment was performed at 215 ° C. for 90 seconds at predetermined intervals, and the presence or absence of cracks was observed to determine the rate of occurrence of package cracks. The smaller the value of the package crack occurrence rate (the number of crack occurrence packages / the number of measurement packages), the better.

  Table 3 shows the results.

実施例１２〜３３の成形用組成物の成形体は、比較例１〜４のそれに比し、熱時硬度、吸水率及び耐リフロークラック性が優れており、耐湿性が良好であることが、表３からわかる。
実施例３４〜４４及び比較例５〜６
表４に示す所定量の各成分を混合し、本発明の成形用組成物を製造した。

The molded articles of the molding compositions of Examples 12 to 33 are superior to those of Comparative Examples 1 to 4, and are excellent in hot hardness, water absorption and reflow crack resistance, and have good moisture resistance. It can be seen from Table 3.
Examples 34 to 44 and Comparative Examples 5 to 6
A predetermined amount of each component shown in Table 4 was mixed to produce a molding composition of the present invention.

Details of each component used are as follows.
Epoxy resin:
・ Cresol novolak epoxy resin (Epicoat 180S65)
Curing agent:
・ Phenol aralkyl resin (Mirex XLC-4L)
・ Triazine-modified phenol novolak resin (LA-7054)
Other additives:
・ Triphenyl phosphate (phosphorus content 9.5%, phosphorus-containing flame retardant)

実施例３４〜４４及び比較例５〜６で得られた成形用組成物の特性を、次に示す方法で評価した。

The characteristics of the molding compositions obtained in Examples 34 to 44 and Comparative Examples 5 to 6 were evaluated by the following methods.

(1) Flame retardancy A test piece having a thickness of 1/16 inch, a length of 5 inches and a width of 0.5 inches was prepared from the above molding composition, and a flame retardancy evaluation test was conducted based on the UL-94 standard. Was done.

(2) Solder heat resistance Test pieces having a thickness of 1.5 mm, a length of 5 cm, and a width of 5 cm were prepared from the molding composition. The test piece was boiled for 2 hours, immersed in a solder bath at 260 ° C. for 120 seconds, and observed for abnormal appearance after immersion.

(3) Peel strength (peeling strength)
A varnish was prepared by adding 0.5 times the amount of dimethylformamide to the molding composition.

  Using this varnish, 100 parts of glass cloth (manufactured by Nitto Boseki Co., Ltd., 0.18 mm in thickness) is impregnated with 80 parts of a varnish solid content, dried with a dryer at 150 ° C. for 5 minutes, and resin content. A 44% prepreg was prepared.

  Six prepregs were stacked, a copper foil having a thickness of 35 mm was stacked on top and bottom, and heated and pressed at 190 ° C. and 3.9 MPa for 120 minutes to obtain a double-sided copper-clad laminate having a thickness of 1.2 mm.

  The peel strength was measured using the obtained laminate according to JIS-C-6481.

  Table 5 shows the results.

本発明の実施例３４〜４４の成形用組成物の成形体は、比較例５〜６のそれに比し、半田耐熱性及びピール強度に優れていることが、表５から判る。

Table 5 shows that the molded articles of the molding compositions of Examples 34 to 44 of the present invention are superior to those of Comparative Examples 5 to 6 in solder heat resistance and peel strength.

  From the above results, it has been clarified that the phenolic resin of the present invention exhibits excellent flame retardancy and can be suitably used as an additive for various materials, especially synthetic resins for electronic materials.

Claims (4)

General formula (1a)

[In the formula, R ¹ represents a hydrogen atom or a hydroxyl group.
Y ¹ represents a group -N = P (XR) ₃ or a group -N = P (X) XR, and Y ² represents a group -P (XR) ₄ or a group -P (X) (XR) ₂ . Further, Y ¹ and Y ² may be bonded to each other to form a ring.
X represents an oxygen atom or a sulfur atom.
R represents a substituted or unsubstituted C _1-15 alkyl group, a substituted or unsubstituted C _3-15 cycloalkyl group, a substituted or unsubstituted C _2-15 alkenyl group, or a substituted or unsubstituted C _6-20 aryl Represents a group.
n and m each represent an integer of 0 to 9999. However, 2 ≦ m + n ≦ 9999.
R ⁶ represents a C _1-15 alkyl group, a C _3-15 cycloalkyl group, a C _2-15 alkenyl group or a C _6-20 aryl group. ]
A phosphazene compound represented by the general formula (4)
A = O (4)
[Wherein, A represents a group —CHR ² — or a group — (CH ₂ O) _a —CH ₂ —. Here, R ² represents a hydrogen atom, a C _1-6 alkyl group, a C _2-4 alkenyl group, a C _3-6 cycloalkyl group or a C _1-6 alkyl group, a C _3-6 cycloalkyl group or a substituent. Shows a phenyl group which may have a hydroxy group. a shows the integer of 1-5. ]
A method for producing a phosphazene-modified phenol resin, comprising producing a phosphazene-modified phenol resin by subjecting a polycondensation reaction to an aldehyde represented by the formula: (1) General formula (1a)

[In the formula, R ¹ represents a hydrogen atom or a hydroxyl group.
Y ¹ represents a group -N = P (XR) ₃ or a group -N = P (X) XR, and Y ² represents a group -P (XR) ₄ or a group -P (X) (XR) ₂ . Further, Y ¹ and Y ² may be bonded to each other to form a ring.
X represents an oxygen atom or a sulfur atom.
R represents a substituted or unsubstituted C _1-15 alkyl group, a substituted or unsubstituted C _3-15 cycloalkyl group, a substituted or unsubstituted C _2-15 alkenyl group, or a substituted or unsubstituted C _6-20 aryl Represents a group.
n and m each represent an integer of 0 to 9999. However, 2 ≦ m + n ≦ 9999.
R ⁶ represents a C _1-15 alkyl group, a C _3-15 cycloalkyl group, a C _2-15 alkenyl group or a C _6-20 aryl group. ]
(2) General formula (2a)

Wherein R ¹ is the same as above.
R ³ represents a hydrogen atom, a substituted or unsubstituted C _1-6 alkyl group, a substituted or unsubstituted C _3-6 cycloalkyl group, a substituted or unsubstituted C _2-6 alkenyl group, a substituted or unsubstituted C _2-6 alkenyl group; _3-7 cycloalkenyl group, substituted or unsubstituted C _2-6 alkynyl group, substituted or unsubstituted C _6-18 aryl group, hydroxyl group, mercapto group, disubstituted amino group (where two substituents on the amino group are May combine with each other to form a C _1-6 alkylene group or a C _6-10 arylene group), a cyano group, a nitro group, a sulfone group, a C _2-10 polyether group, a siloxane group, an acid amide group or an acid Indicates an imide group.
b shows the integer of 0-3. ]
And an aromatic compound represented by the general formula (3a):

Wherein R ⁴ is the same or different and represents a hydrogen atom, a methyl group or a hydroxymethyl group. R ⁵ represents a hydrogen atom, an amino group, a hydroxymethylamino group, a di (hydroxymethyl) amino group, a C _1-6 alkyl group, a phenyl group or an alkylphenyl group. ]
At least one selected from the group consisting of triazine compounds represented by
(3) General formula (4)
A = O (4)
[Wherein, A represents a group —CHR ² — or a group — (CH ₂ O) _a —CH ₂ —. Here, R ² is a hydrogen atom, a C _1-6 alkyl group, a C _2-4 alkenyl group, a C _3-6 cycloalkyl group or a C _1-6 alkyl group, a C _3-6 cycloalkyl group or a substituent. Shows a phenyl group which may have a hydroxy group. a shows the integer of 1-5. ]
A phosphazene-modified phenol resin is produced by subjecting an aldehyde represented by the formula to a polycondensation reaction. (1) General formula (1a)

[In the formula, R ¹ represents a hydrogen atom or a hydroxyl group.
Y ¹ represents a group -N = P (XR) ₃ or a group -N = P (X) XR, and Y ² represents a group -P (XR) ₄ or a group -P (X) (XR) ₂ . Further, Y ¹ and Y ² may be bonded to each other to form a ring.
X represents an oxygen atom or a sulfur atom.
R represents a substituted or unsubstituted C _1-15 alkyl group, a substituted or unsubstituted C _3-15 cycloalkyl group, a substituted or unsubstituted C _2-15 alkenyl group, or a substituted or unsubstituted C _6-20 aryl Represents a group.
n and m each represent an integer of 0 to 9999. However, 2 ≦ m + n ≦ 9999.
R ⁶ represents a C _1-15 alkyl group, a C _3-15 cycloalkyl group, a C _2-15 alkenyl group or a C _6-20 aryl group. ]
A phosphazene compound represented by
(2) General formula (2a)

Wherein R ¹ is the same as above.
R ³ represents a hydrogen atom, a substituted or unsubstituted C _1-6 alkyl group, a substituted or unsubstituted C _3-6 cycloalkyl group, a substituted or unsubstituted C _2-6 alkenyl group, a substituted or unsubstituted C _2-6 alkenyl group; _3-7 cycloalkenyl group, substituted or unsubstituted C _2-6 alkynyl group, substituted or unsubstituted C _6-18 aryl group, hydroxyl group, mercapto group, disubstituted amino group (where two substituents on the amino group are May combine with each other to form a C _1-6 alkylene group or a C _6-10 arylene group), a cyano group, a nitro group, a sulfone group, a C _2-10 polyether group, a siloxane group, an acid amide group or an acid Indicates an imide group.
b shows the integer of 0-3. ]
An aromatic compound represented by
(3) General formula (4)
A = O (4)
[Wherein, A represents a group —CHR ² — or a group — (CH ₂ O) _a —CH ₂ —. Here, R ² represents a hydrogen atom, a C _1-6 alkyl group, a C _2-4 alkenyl group, a C _3-6 cycloalkyl group or a C _1-6 alkyl group, a C _3-6 cycloalkyl group or a substituent. Shows a phenyl group which may have a hydroxy group. a shows the integer of 1-5. ]
A phosphazene-modified phenol resin is produced by subjecting an aldehyde represented by the formula to a polycondensation reaction. (1) General formula (1a)

[In the formula, R ¹ represents a hydrogen atom or a hydroxyl group.
Y ¹ represents a group -N = P (XR) ₃ or a group -N = P (X) XR, and Y ² represents a group -P (XR) ₄ or a group -P (X) (XR) ₂ . Further, Y ¹ and Y ² may be bonded to each other to form a ring.
X represents an oxygen atom or a sulfur atom.
R represents a substituted or unsubstituted C _1-15 alkyl group, a substituted or unsubstituted C _3-15 cycloalkyl group, a substituted or unsubstituted C _2-15 alkenyl group, or a substituted or unsubstituted C _6-20 aryl Represents a group.
n and m each represent an integer of 0 to 9999. However, 2 ≦ m + n ≦ 9999.
R ⁶ represents a C _1-15 alkyl group, a C _3-15 cycloalkyl group, a C _2-15 alkenyl group or a C _6-20 aryl group. ]
A phosphazene compound represented by
(2) General formula (3a)

Wherein R ⁴ is the same or different and represents a hydrogen atom, a methyl group or a hydroxymethyl group. R ⁵ represents a hydrogen atom, an amino group, a hydroxymethylamino group, a di (hydroxymethyl) amino group, a C _1-6 alkyl group, a phenyl group or an alkylphenyl group. ]
And a triazine compound represented by
(3) General formula (4)
A = O (4)
[Wherein, A represents a group —CHR ² — or a group — (CH ₂ O) _a —CH ₂ —. Here, R ² represents a hydrogen atom, a C _1-6 alkyl group, a C _2-4 alkenyl group, a C _3-6 cycloalkyl group or a C _1-6 alkyl group, a C _3-6 cycloalkyl group or a substituent. Shows a phenyl group which may have a hydroxy group. a shows the integer of 1-5. ]
A phosphazene-modified phenol resin is produced by subjecting an aldehyde represented by the formula to a polycondensation reaction.