JP3922806B2 - Thermosetting resin composition and molding material using the same - Google Patents

Description

（ただし、式中、Ｘは複素環式含窒素化合物を表す。また、式中Ｚ₁は芳香族、または環式脂肪族で、Ｙ₁、Ｙ₂は１価のプロトン供与性置換基がプロトンを放出してなる基であり、同一分子内の置換基Ｙ₁、Ｙ₂がホウ素原子と結合してキレート構造を形成するものである。式中Ｚ₂は芳香族、または環式脂肪族で、Ｙ₃、Ｙ₄は１価のプロトン供与性置換基がプロトンを放出してなる基であり、同一分子内の置換基Ｙ₃、Ｙ₄がホウ素原子と結合してキレート構造を形成するものである。Ｚ₁、Ｚ₂は同一でも異なっていてもよく、Ｙ₁、Ｙ₂、Ｙ₃、Ｙ₄は互いに同一でも異なっていてもよい。）
前記一般式［１］で表されるオニウムボレートの置換基Ｙ ₁ −Ｚ ₁ −Ｙ ₂ 及びＹ ₃ −Ｚ ₂ −Ｙ ₄ は、分子内にカルボキシル基を少なくとも２個有するカルボン酸がプロトンを放出してなる基、分子内にカルボキシル基を少なくとも１個と水酸基を少なくとも１個有するカルボン酸がプロトンを放出してなる基、または分子内に少なくとも２個の水酸基を有し、カルボキシル基を有さないフェノール化合物がプロトンを放出してなる基である熱硬化性樹脂組成物、
およびこれを用いた成形材料である。
【０００５】
【発明の実施の形態】
前述のように、フェノール樹脂成形材料の成形時間を短縮するため、ブレンステッド酸等の硬化促進効果を有する触媒を添加することは一般に行われているが、さらなる硬化性の向上が必要とされている。
本発明においてはこのような課題を解決するため、硬化促進効果を有する触媒について鋭意検討した結果、一般式［１］で表されるオニウムボレートを用いることにより解決できた。
【０００６】
本発明で用いるノボラック型フェノール樹脂（ａ）は、フェノール類とホルムアルデヒド類との反応で得られる通常のノボラック型フェノール樹脂が用いられる。該当するノボラック型フェノール樹脂のフェノール類としては、フェノール、クレゾール、キシレノール、ナフトール、ｐ−ｔ−ブチルフェノール、ビスフェノールＡ、レゾルシノールなどの１価ならびに多価フェノール類、及びそれらの置換体の１種、または２種以上を例示することが出来る。一方、該当するホルムアルデヒド類としてはホルムアルデヒド、パラホルムアルデヒドなどを例示することが出来る。また、本発明のノボラック型フェノール樹脂は芳香族炭化水素樹脂、ジメトキシパラキシレン、ジシクロペンタジエンなどで適宜変性した物を用いることができる。
【０００７】
本発明で用いるヘキサメチレンテトラミン（ｂ）はノボラック型フェノール樹脂１００重量部に対してヘキサメチレンテトラミンを好ましくは７〜３０重量部、より好ましくは１２〜２０重量部配合する。７重量部以下の場合は架橋密度が低くなり、３０重量部以上の場合は過剰のヘキサメチレンテトラミンが架橋反応を阻害し架橋密度が低下し物性に悪影響を及ぼす。
【０００８】
本発明で用いるオニウムボレートは前記のような一般式［１］で表される。式中Ｘは複素環式含窒素化合物を表し、プロトンが付加してオニウムカチオン［ＨＸ］＋を形成する。このような化合物Ｘの例としては、例えばジアザビシクロアルケン類、イミダゾール類、イミダゾリジン類、オキサジン類、オキサゾール類、ピロール類、チアゾール類、ピリジン類、ピラジン類、モルホリン類、ピリダジン類、ピリミジン類、ピラゾール類、キノキサリン類、キナゾリン類、フタロジン類、キノリン類、プリン類、インダゾール類、インドール類、インドラジン類、フェナジン類、フェナルシン類、フェノチアジン類、ピロリン類、インドリン類、ピペリジン類、ピペラジン類、ピロリジン類等の化合物を挙げることができる。
上記複素環式含窒素化合物の中で、ジアザビシクロアルケン類やイミダゾール類が特に好適であり、具体的な例としては、ジアザビシクロアルケン類の例としては１，５−ジアザビシクロ［４．３．０］−５−ノネン、１，５−ジアザビシクロ［４．４．０］−５−デセン、１，８−ジアザビシクロ［５．４．０］−７−ウンデセン等が挙げられ、またイミダゾール類の例としては、２−メチルイミダゾール、２−エチルイミダゾール、２−フェニルイミダゾール、２−エチル−４メチルイミダゾール、２−フェニル−４メチルイミダゾール、１−ベンジルイミダゾール、２−シアノイミダゾール等を挙げることができる。その他ヘキサメチレンテトラミンも有効である。
【０００９】
本発明の一般式[１]で置換基Ｙ₁−Ｚ₁−Ｙ₂およびＹ₃−Ｚ₂−Ｙ₄を与えるプロトン供与体ＨＹ₁−Ｚ₁−Ｙ₂ＨおよびＨＹ₃−Ｚ₂−Ｙ₄Ｈとしては、分子内にカルボキシル基を少なくとも２個有する芳香族カルボン酸か、または分子内にカルボキシル基を少なくとも１個と水酸基を少なくとも１個有する芳香族カルボン酸か、または分子内に少なくとも２個の水酸基を有し、カルボキシル基を有さないフェノール化合物であり、また２個の置換基Ｙ₁とＹ₂およびＹ₃とＹ₄は、互いにそれぞれ隣接していることがさらに好ましい。分子内にカルボキシル基を少なくとも２個有する芳香族カルボン酸の例としてはフタル酸、１，８−ナフタル酸、２，３−ピリジンジカルボン酸、トリメリト酸、ピロメリト酸、１，４，５，８−ナフタレンテトラカルボン酸等、分子内にカルボキシル基を少なくとも１個と水酸基を少なくとも１個有する芳香族カルボン酸の例としてはサリチル酸、３−ヒドロキシ−２−ナフトエ酸、２−ヒドロキシビフェニル−３−カルボン酸、４−ヒドロキシビフェニル−３−カルボン酸、２，２−ビフェノール−４−カルボン酸等、また分子内に少なくとも２個の水酸基を有し、カルボキシル基を有さないフェノール化合物の例としては、カテコール、レゾルシノール、２，３−ジヒドロキシナフタレン、２，２′−ビフェノール等を挙げることができる。上記化合物が一例として挙げられるが、もちろんこれらに限定されるものではない。
【００１０】
本発明の請求項１〜５記載の熱硬化性樹脂組成物において、オニウムボレート（ｃ）のノボラック型フェノール樹脂（ａ）に対する配合量は、ノボラック型フェノール樹脂１００重量部に対して０．０１〜２０重量部であることが望ましい。オニウムボレート（ｃ）のノボラック型フェノール樹脂に対する配合量が２０重量部より大きくなると硬化性は優れるものの熱安定性が低下し、成形不可能となる。一方、オニウムボレート（ｃ）のノボラック型フェノール樹脂（ａ）に対する配合量が０．０１重量部より小さくなると満足な速硬化性が得られなくなる。
請求項１のオニウムボレート（ｃ）はノボラック型フェノール樹脂とヘキサメチレンテトラミン硬化系における硬化促進剤として作用するが、このオニウムボレート（ｃ）と従来より硬化促進剤として使用されている公知の酸触媒を併用することももちろん可能である。
【００１１】
本発明の成形材料に用いる充填材としては木粉、パルプ粉、各種織物粉砕物、熱硬化性樹脂硬化物・成形品の粉砕品などの有機質のもの、シリカ、アルミナ、水酸化アルミニウム、ガラス、タルク、クレー、マイカ、炭酸カルシウム、カーボン等の無機質の粉末のもの、ガラス繊維、カーボン繊維などの無機質繊維が用いられ、これらの１種、または２種以上を用いることができる。これらの充填材は樹脂（ノボラック型フェノール樹脂＋ヘキサメチレンテトラミン＋オニウムボレート）１００重量部に対して２５〜１５０重量部配合して用いられる。また、成形材料の製造方法としては、加熱ロール等フェノール樹脂成形材料に一般的に用いられる装置により、混練して製造する。
【００１２】
【実施例】
以下、実施例に基づき本発明を詳細に説明するが、本発明はこれによって何ら限定されるものではない。
【００１３】
「実施例１」
ノボラック型フェノール樹脂（数平均分子量８１０）１００重量部に対し、ヘキサメチレンテトラミンを１６重量部添加し、硬化促進剤として化学式[２]で表されるＤＢＵ−ＢＳＡを８重量部加えて、充填材として木粉と熱硬化性樹脂硬化物粉末を配合し、加熱ロールにより混練して、熱硬化性樹脂成形材料を得た。この熱硬化性樹脂成形材料をトランスファー成形によりテストピースを作成し、硬化特性を測定した。
【化２】

【００１４】
「実施例２」
実施例１の硬化促進剤ＤＢＵ−ＢＳＡ、８重量部に替え、硬化促進剤として化学式[３]で表されるＤＢＵ−ＢＤＨＮ、８．８重量部加えた以外は、全て実施例１と同様にして熱硬化性樹脂成形材料を得、トランスファー成形によりテストピースを作成し、硬化特性を測定した。
【化３】

【００１５】
「実施例３」
実施例１の硬化促進剤ＤＢＵ−ＢＳＡ、８重量部に替え硬化促進剤として化学式[４]で表されるＤＢＵ−ＢＨＮＡ、９．８重量部加えた以外は全て実施例１と同様にして熱硬化性樹脂成形材料を得、トランスファー成形によりテストピースを作成し、硬化特性を測定した。
【化４】

【００１６】
「実施例４」
実施例１の硬化促進剤ＤＢＵ−ＢＳＡ、８重量部に替え硬化促進剤として化学式[５]で表される２ＭＺ−ＢＳＡ、６．７重量部加えた以外は全て実施例１と同様にして熱硬化性樹脂成形材料を得、トランスファー成形によりテストピースを作成し、硬化特性を測定した。
【化５】

【００１７】
「実施例５」
実施例１の硬化促進剤ＤＢＵ−ＢＳＡ、８重量部に替え硬化促進剤として化学式[６]で表されるＨＥＸＡ−ＢＳＡ、７．８重量部加えた以外は全て実施例１と同様にして熱硬化性樹脂成形材料を得、トランスファー成形によりテストピースを作成し、硬化特性を測定した。
【化６】

【００１８】
「比較例１」
ノボラック型フェノール樹脂（数平均分子量８１０）１００重量部に対し、ヘキサメチレンテトラミンを１６重量部を加えて、充填材として木粉と熱硬化性樹脂硬化物粉末を配合し、加熱ロールにより混練して、熱硬化性樹脂組成物を得た。この成形材料をトランスファー成形によりテストピースを作成し、硬化特性を測定した。
【００１９】
「比較例２」
比較例１に、サリチル酸５．１重量部、ホウ酸１．１重量部を更に添加した以外は全て比較例１と同様にして、熱硬化性樹脂組成物を得た。この成形材料をトランスファー成形によりテストピースを作成し、硬化特性を測定した。
【００２０】
「比較例３」
比較例２のサリチル酸、５．１重量部に替え２，３−ジヒドロキシナフタレン、５．９重量部とした以外は全て比較例２と同様にして熱硬化性樹脂成形材料を得、トランスファー成形によりテストピースを作成し、硬化特性を測定した。
【００２１】
「比較例４」
比較例２のサリチル酸、５．１重量部に替え２−ヒドロキシナフトエ酸を６．９重量部とした以外は全て比較例２と同様にして熱硬化性樹脂成形材料を得、トランスファー成形によりテストピースを作成し、硬化特性を測定した。
【００２２】
各実施例および比較例により得られた成形材料についての硬化特性は以下の方法により測定した。
【００２３】
（１）バーコル硬度：トランスファー成形にて１７５℃で２０秒後にテストピースを金型から取り出し、取り出したあと１０秒後のテストピース表面の硬度をバーコル硬度計９３５型を用いて測定した。
（２）曲げ強さ：トランスファー成形にて１７５℃で１８０秒間硬化させ、ＪＩＳ Ｋ ６９１１に準じて常温（２５℃雰囲気下）、１２０℃雰囲気下において測定した。
【００２４】
実施例１〜５及び比較例１〜４で得られた熱硬化性組成物の特性を表１に示す。
【表１】

【００２５】
表１から、実施例１〜５に示した本発明の熱硬化性樹脂組成物はバーコル硬度を比較すると、比較例１の従来の熱硬化性樹脂組成物と比較して短時間で優れた表面硬度、つまり速硬化性を有することはもちろん、実施例１〜５と系内に同モル数の酸成分を含有するように配合した比較例２〜４と比較しても優れた硬化性を有することがわかる。これは、従来のように酸成分を単独で添加する方法より一般式［１］で示されるようなオニウムボレートとして添加する方法が有効であることを示している。
【化１】

また、酸成分を添加した比較例２〜４の１２０℃における曲げ強度は比較例１と比べ低下しているが、オニウムボレートを添加した実施例１〜５は同等である。
【００２６】
【発明の効果】
上記の実施例からも明らかなように、本発明によって得られる熱硬化性樹脂組成物は硬化性の向上に極めて優れており、本発明の熱硬化性樹脂組成物を利用すれば成形時における硬化時間の短縮が可能であり、生産ラインのハイサイクル化がを達成できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thermosetting resin composition having excellent curability and a molding material using the same. More specifically, the present invention relates to a thermosetting resin that can be quickly cured when heated at the time of molding to give good moldability and a high-quality molded product.
[0002]
[Prior art]
Phenolic resin molding materials have excellent heat resistance, durability, electrical performance, and mechanical performance, so they are widely used in automotive parts, electronic / electrical parts, mechanical parts, and kitchen parts. The molding time when molding these molding materials has a great influence on the production cost. That is, if the curing time is shortened compared to the current situation, a high cycle of the production line can be achieved, workability can be improved, and production cost can be reduced. Conventionally, various improvements of the thermosetting resin composition have been made in order to shorten the curing time of the phenol resin molding material.
The method of adding Bronsted acid is an example of improving curability, and although it is possible to shorten the curing time to some extent, further improvement in curability is required.
[0003]
[Problems to be solved by the invention]
The present invention relates to a thermosetting resin composition having excellent curability and a molding material using the same. More specifically, the present invention is directed to a thermosetting resin composition that can be quickly cured when heated at the time of molding and can provide good moldability and a high-quality molded product, and a molding material using the same. As a result of studies, the present invention has been completed.
[0004]
[Means for Solving the Problems]
That is, the present invention is a thermosetting resin composition containing (a) a novolak-type phenol resin, (b) hexamethylenetetramine, and (c) an onium borate represented by the general formula [1] as essential components ,
[Chemical 1]

(Wherein, X represents a heterocyclic nitrogen-containing compound. In the formula, Z ₁ is aromatic or cycloaliphatic, and Y ₁ and Y ₂ are protons having a monovalent proton-donating substituent. In which the substituents Y ₁ and Y ₂ in the same molecule combine with a boron atom to form a chelate structure, wherein Z ₂ is aromatic or cycloaliphatic. , Y ₃ and Y ₄ are groups in which a monovalent proton-donating substituent releases a proton, and the substituents Y ₃ and Y ₄ in the same molecule are combined with a boron atom to form a chelate structure. Z ₁ and Z ₂ may be the same or different, and Y ₁ , Y ₂ , Y ₃ and Y ₄ may be the same or different from each other.)
In the onium borate substituents Y ₁ -Z ₁ -Y ₂ and Y ₃ -Z ₂ -Y ₄ represented by the general formula [1], a carboxylic acid having at least two carboxyl groups in the molecule releases protons. A group formed by releasing a proton from a carboxylic acid having at least one carboxyl group and at least one hydroxyl group in the molecule, or having at least two hydroxyl groups in the molecule and having a carboxyl group A thermosetting resin composition in which no phenolic compound is a group formed by releasing protons,
And a molding material using the same.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
As described above, in order to shorten the molding time of the phenol resin molding material, it is generally performed to add a catalyst having a curing acceleration effect such as Bronsted acid, but further improvement in curability is required. Yes.
In the present invention, in order to solve such a problem, as a result of intensive studies on a catalyst having a curing accelerating effect, it has been solved by using an onium borate represented by the general formula [1].
[0006]
As the novolac type phenol resin (a) used in the present invention, a normal novolac type phenol resin obtained by a reaction between phenols and formaldehydes is used. As the phenols of the corresponding novolac type phenol resin, monovalent and polyhydric phenols such as phenol, cresol, xylenol, naphthol, pt-butylphenol, bisphenol A, resorcinol, and one of their substitutions, or Two or more types can be exemplified. On the other hand, examples of the corresponding formaldehydes include formaldehyde and paraformaldehyde. In addition, the novolac type phenolic resin of the present invention may be a product appropriately modified with an aromatic hydrocarbon resin, dimethoxyparaxylene, dicyclopentadiene or the like.
[0007]
The hexamethylenetetramine (b) used in the present invention is preferably 7 to 30 parts by weight, more preferably 12 to 20 parts by weight of hexamethylenetetramine with respect to 100 parts by weight of the novolak type phenol resin. When the amount is 7 parts by weight or less, the crosslinking density is lowered, and when the amount is 30 parts by weight or more, excess hexamethylenetetramine inhibits the crosslinking reaction, the crosslinking density is lowered, and the physical properties are adversely affected.
[0008]
The onium borate used in the present invention is represented by the general formula [1] as described above. In the formula, X represents a heterocyclic nitrogen-containing compound, and a proton is added to form an onium cation [HX] +. Examples of such compound X include, for example, diazabicycloalkenes, imidazoles, imidazolidines, oxazines, oxazoles, pyrroles, thiazoles, pyridines, pyrazines, morpholines, pyridazines, pyrimidines. , Pyrazoles, quinoxalines, quinazolines, phthalazines, quinolines, purines, indazoles, indoles, indoladines, phenazines, phenalsines, phenothiazines, pyrrolines, indolines, piperidines, piperazines, pyrrolidines And the like.
Of the above heterocyclic nitrogen-containing compounds, diazabicycloalkenes and imidazoles are particularly suitable. Specific examples of the diazabicycloalkenes include 1,5-diazabicyclo [4.3. .0] -5-nonene, 1,5-diazabicyclo [4.4.0] -5-decene, 1,8-diazabicyclo [5.4.0] -7-undecene, etc. Examples include 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4methylimidazole, 2-phenyl-4methylimidazole, 1-benzylimidazole, 2-cyanoimidazole and the like. . In addition, hexamethylenetetramine is also effective.
[0009]
Proton donors HY ₁ -Z ₁ -Y ₂ H and HY ₃ -Z ₂ -Y giving the substituents Y ₁ -Z ₁ -Y ₂ and Y ₃ -Z ₂ -Y ₄ in the general formula [1] of the present invention ₄ the H, at least a carboxyl group in the molecular or aromatic carboxylic acids having at least two, or a carboxyl group in the molecule at least one a hydroxyl group or an aromatic carboxylic acid having at least one, or in a molecule More preferably, it is a phenol compound having two hydroxyl groups and no carboxyl group , and the two substituents Y ₁ and Y ₂ and Y ₃ and Y ₄ are adjacent to each other. Examples of aromatic carboxylic acids having at least two carboxyl groups in the molecule include phthalic acid, 1,8-naphthalic acid, 2,3-pyridinedicarboxylic acid, trimellitic acid, pyromellitic acid, 1,4,5,8- Examples of aromatic carboxylic acids having at least one carboxyl group and at least one hydroxyl group in the molecule such as naphthalenetetracarboxylic acid include salicylic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxybiphenyl-3-carboxylic acid Examples of phenol compounds having 4-hydroxybiphenyl-3-carboxylic acid, 2,2-biphenol-4-carboxylic acid, etc., and having at least two hydroxyl groups in the molecule and no carboxyl group include catechol , Resorcinol, 2,3-dihydroxynaphthalene, 2,2'-biphenol, etc. That. Although the said compound is mentioned as an example, of course, it is not limited to these.
[0010]
In the thermosetting resin composition according to claims 1 to 5 of the present invention, the amount of the onium borate (c) to the novolac type phenol resin (a) is 0.01 to 100 parts by weight of the novolac type phenol resin. 20 parts by weight is desirable. When the blending amount of onium borate (c) with respect to the novolac type phenol resin is larger than 20 parts by weight, the curability is excellent, but the thermal stability is lowered and the molding becomes impossible. On the other hand, when the blending amount of the onium borate (c) with respect to the novolac type phenol resin (a) is less than 0.01 parts by weight, satisfactory fast curability cannot be obtained.
The onium borate (c) of claim 1 acts as a curing accelerator in a novolak-type phenolic resin and a hexamethylenetetramine curing system. The onium borate (c) and a known acid catalyst conventionally used as a curing accelerator. Of course, it is also possible to use together.
[0011]
Fillers used for the molding material of the present invention include wood powder, pulp powder, various pulverized fabrics, organic materials such as pulverized thermosetting resin cured products and molded products, silica, alumina, aluminum hydroxide, glass, Inorganic powders such as talc, clay, mica, calcium carbonate, and carbon, and inorganic fibers such as glass fiber and carbon fiber are used, and one or more of these can be used. These fillers are used by blending 25 to 150 parts by weight with respect to 100 parts by weight of the resin (novolak type phenol resin + hexamethylenetetramine + onium borate). Moreover, as a manufacturing method of a molding material, it knead | mixes and manufactures with the apparatus generally used for phenol resin molding materials, such as a heating roll.
[0012]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited at all by this.
[0013]
"Example 1"
16 parts by weight of hexamethylenetetramine is added to 100 parts by weight of novolak-type phenolic resin (number average molecular weight 810), and 8 parts by weight of DBU-BSA represented by the chemical formula [2] is added as a curing accelerator. Wood powder and thermosetting resin cured product powder were blended and kneaded with a heating roll to obtain a thermosetting resin molding material. A test piece was prepared from the thermosetting resin molding material by transfer molding, and the curing characteristics were measured.
[Chemical 2]

[0014]
"Example 2"
Except for adding 8 parts by weight of the curing accelerator DBU-BSA of Example 1 and adding 8.8 parts by weight of DBU-BDHN represented by the chemical formula [3] as a curing accelerator, all are the same as in Example 1. Thus, a thermosetting resin molding material was obtained, a test piece was prepared by transfer molding, and the curing characteristics were measured.
[Chemical 3]

[0015]
"Example 3"
Except for adding 8 parts by weight of the curing accelerator DBU-BSA of Example 1 and 9.8 parts by weight of DBU-BHNA represented by the chemical formula [4] as a curing accelerator, heat was obtained in the same manner as in Example 1. A curable resin molding material was obtained, a test piece was prepared by transfer molding, and the curing characteristics were measured.
[Formula 4]

[0016]
Example 4
Except for adding 8 parts by weight of the curing accelerator DBU-BSA of Example 1 and 2MZ-BSA represented by the chemical formula [5] as a curing accelerator, 6.7 parts by weight, the same procedure as in Example 1 was followed. A curable resin molding material was obtained, a test piece was prepared by transfer molding, and the curing characteristics were measured.
[Chemical formula 5]

[0017]
"Example 5"
Except for adding 8 parts by weight of the curing accelerator DBU-BSA of Example 1 and adding 7.8 parts by weight of HEXA-BSA represented by the chemical formula [6] as a curing accelerator, heat was obtained in the same manner as in Example 1. A curable resin molding material was obtained, a test piece was prepared by transfer molding, and the curing characteristics were measured.
[Chemical 6]

[0018]
“Comparative Example 1”
16 parts by weight of hexamethylenetetramine is added to 100 parts by weight of novolak-type phenolic resin (number average molecular weight 810), wood powder and thermosetting resin cured powder are blended as a filler, and kneaded with a heating roll. A thermosetting resin composition was obtained. A test piece was prepared from this molding material by transfer molding, and the curing characteristics were measured.
[0019]
"Comparative Example 2"
A thermosetting resin composition was obtained in the same manner as Comparative Example 1 except that 5.1 parts by weight of salicylic acid and 1.1 parts by weight of boric acid were further added to Comparative Example 1. A test piece was prepared from this molding material by transfer molding, and the curing characteristics were measured.
[0020]
“Comparative Example 3”
A thermosetting resin molding material was obtained in the same manner as in Comparative Example 2 except that salicylic acid in Comparative Example 2 was changed to 5.1 parts by weight and changed to 2,3-dihydroxynaphthalene and 5.9 parts by weight. Pieces were made and the curing properties were measured.
[0021]
“Comparative Example 4”
A thermosetting resin molding material was obtained in the same manner as in Comparative Example 2 except that salicylic acid in Comparative Example 2 was changed to 5.1 parts by weight and 6.9 parts by weight of 2-hydroxynaphthoic acid was used. And the curing characteristics were measured.
[0022]
The curing characteristics of the molding materials obtained in each example and comparative example were measured by the following method.
[0023]
(1) Barcol hardness: The test piece was taken out of the mold after 20 seconds at 175 ° C. by transfer molding, and the hardness of the test piece surface after 10 seconds was measured using a Barcol hardness meter 935 type.
(2) Bending strength: Cured at 175 ° C. for 180 seconds by transfer molding, and measured at normal temperature (25 ° C. atmosphere) and 120 ° C. atmosphere according to JIS K 6911.
[0024]
Table 1 shows the characteristics of the thermosetting compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 4.
[Table 1]

[0025]
From Table 1, the thermosetting resin compositions of the present invention shown in Examples 1 to 5 have a superior surface in a short time compared to the conventional thermosetting resin composition of Comparative Example 1 when comparing the Barcol hardness. Not only has hardness, that is, fast curability, but also has excellent curability compared to Examples 1 to 5 and Comparative Examples 2 to 4 formulated so as to contain the same mole number of acid components in the system. I understand that. This shows that the method of adding onium borate as shown by the general formula [1] is more effective than the conventional method of adding the acid component alone.
[Chemical 1]

Moreover, although the bending strength in 120 degreeC of Comparative Examples 2-4 which added the acid component is falling compared with the comparative example 1, Examples 1-5 which added onium borate are equivalent.
[0026]
【The invention's effect】
As is clear from the above examples, the thermosetting resin composition obtained by the present invention is extremely excellent in improving the curability, and if the thermosetting resin composition of the present invention is used, it is cured at the time of molding. The time can be shortened and a high cycle of the production line can be achieved.

Claims (5)

(A) a novolac type phenolic resin, (b) hexamethylenetetramine, and (c) a thermosetting resin composition having an onium borate represented by the general formula [1] as essential components ,

(Wherein, X represents a heterocyclic nitrogen-containing compound. In the formula, Z ₁ is aromatic or cycloaliphatic, and Y ₁ and Y ₂ are protons having a monovalent proton-donating substituent. In which the substituents Y ₁ and Y ₂ in the same molecule combine with a boron atom to form a chelate structure, wherein Z ₂ is aromatic or cycloaliphatic. , Y ₃ and Y ₄ are groups in which a monovalent proton-donating substituent releases a proton, and the substituents Y ₃ and Y ₄ in the same molecule are combined with a boron atom to form a chelate structure. Z ₁ and Z ₂ may be the same or different, and Y ₁ , Y ₂ , Y ₃ and Y ₄ may be the same or different from each other.)
In the onium borate substituents Y ₁ -Z ₁ -Y ₂ and Y ₃ -Z ₂ -Y ₄ represented by the general formula [1], a carboxylic acid having at least two carboxyl groups in the molecule releases protons. A group formed by releasing a proton from a carboxylic acid having at least one carboxyl group and at least one hydroxyl group in the molecule, or having at least two hydroxyl groups in the molecule and having a carboxyl group A thermosetting resin composition which is a group formed by releasing a proton from a phenol compound. The thermosetting according to claim 1, wherein the heterocyclic nitrogen-containing compound represented by X in the onium borate represented by the general formula [1] is one selected from diazabicycloalkenes. Resin composition. 2. The thermosetting resin composition according to claim 1, wherein the heterocyclic nitrogen-containing compound represented by X in the onium borate represented by the general formula [1] is one selected from imidazoles. object. The thermosetting resin composition according to claim 1, wherein the heterocyclic nitrogen-containing compound represented by X in the onium borate represented by the general formula [1] is hexamethylenetetramine. A molding material using the thermosetting resin composition according to any one of claims 1 to 4 .