JPH0128061B2 - - Google Patents
Info
- Publication number
- JPH0128061B2 JPH0128061B2 JP5343580A JP5343580A JPH0128061B2 JP H0128061 B2 JPH0128061 B2 JP H0128061B2 JP 5343580 A JP5343580 A JP 5343580A JP 5343580 A JP5343580 A JP 5343580A JP H0128061 B2 JPH0128061 B2 JP H0128061B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- unsaturated polyester
- parts
- composition
- substituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920006305 unsaturated polyester Polymers 0.000 claims description 8
- 239000011342 resin composition Substances 0.000 claims description 7
- 150000001451 organic peroxides Chemical class 0.000 claims description 6
- 229920001187 thermosetting polymer Polymers 0.000 claims description 5
- 239000002253 acid Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000000178 monomer Substances 0.000 description 4
- 229920006337 unsaturated polyester resin Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical compound CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
【発明の詳細な説明】
本発明は熱硬化性樹脂組成物に関し、その目的
とするところは貯蔵安定性のよい、優れた硬化樹
脂特性を有する新規な熱硬化性樹脂組成物を提供
することにある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin composition, and an object thereof is to provide a novel thermosetting resin composition having good storage stability and excellent cured resin properties. be.
不飽和ポリエステル樹脂すなわち、不飽和ポリ
エステルと架橋性単量体との混合物は、有機過酸
化物などの重合開始剤を用い、常温あるいは加熱
により硬化させ、今日、多種多様な用途で用いら
れている。しかし、このような不飽和ポリエステ
ル樹脂は、架橋性単量体を含むため、貯蔵安定性
に限界があり、常温下では、通常３〜12ケ月程度
とみられる。 Unsaturated polyester resins, that is, mixtures of unsaturated polyesters and crosslinkable monomers, are cured at room temperature or by heating using polymerization initiators such as organic peroxides, and are used in a wide variety of applications today. . However, since such unsaturated polyester resins contain crosslinkable monomers, there is a limit to their storage stability, which is generally estimated to last about 3 to 12 months at room temperature.
本発明は、従来の不飽和ポリエステル樹脂の架
橋性単量体を全く廃し、いわゆる不飽和ポリエス
テルと有機過酸化物とからなる組成物の一連の研
究中になされたものである。 The present invention was made during a series of studies on compositions consisting of so-called unsaturated polyesters and organic peroxides, completely eliminating the use of crosslinking monomers in conventional unsaturated polyester resins.
すなわち、本発明は、(a)モノまたはジアルキル
置換３，６−エンドメチレンテトラヒドロフタル
酸で変性した不飽和ポリエステル(b)有機過酸化物
を含有してなる熱硬化性樹脂組成物に関し、上記
の(a)は、不飽和ポリエステルすなわち、不飽和
酸、飽和酸および多価アルコールの脱水縮合反応
で得られる一般に酸価100〜０の液状〜固形状の
ポリエステルであり、その飽和酸成分の一つとし
て、モノまたはジアルキル置換３，６−エンドメ
チレンテトラヒドロフタル酸を用いることが必要
である。 That is, the present invention relates to a thermosetting resin composition comprising (a) an unsaturated polyester modified with mono- or dialkyl-substituted 3,6-endomethylenetetrahydrophthalic acid and (b) an organic peroxide. (a) is an unsaturated polyester, which is generally a liquid to solid polyester with an acid value of 100 to 0 obtained by dehydration condensation reaction of an unsaturated acid, a saturated acid, and a polyhydric alcohol, and is one of its saturated acid components. As such, it is necessary to use mono- or dialkyl-substituted 3,6-endomethylenetetrahydrophthalic acid.
本発明においてはモノまたはジアルキル置換
３，６−エンドメチレンテトラヒドロフタル酸と
しては、これらの無水物も用いることができ、さ
らに必要に応じてフタル酸、無水フタル酸、イソ
フタル酸、テレフタル酸、３，６−エンドメチレ
ン−１，２，３，６テトラヒドロフタル酸、３，
６−エンドメチレン−１，２，3.6−テトラヒド
ロ無水フタル酸等の飽和酸を併用してもよい。モ
ノまたはジアルキル置換３，６−エンドメチレン
テトラヒドロフタル酸としては、３〜５の位置が
メチル基、エチル基等で置換されたものが用いら
れる。不飽和酸／飽和酸のモル比は、1.00／9.00
〜9.00／1.00が好ましく、飽和酸中のモノまたは
ジアルキル置換３，６−エンドメチレンテトラヒ
ドロフタル酸の比率は、30〜70モル％が好まし
い。また全酸の酸基／多価アルコールのヒドロキ
シル基のモル比も特に限定しないが1.10／0.90〜
0.90／1.10の範囲が好ましい。 In the present invention, as the mono- or dialkyl-substituted 3,6-endomethylenetetrahydrophthalic acid, anhydrides of these can also be used, and if necessary, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 3, 6-endomethylene-1,2,3,6-tetrahydrophthalic acid, 3,
A saturated acid such as 6-endomethylene-1,2,3.6-tetrahydrophthalic anhydride may be used in combination. As the mono- or dialkyl-substituted 3,6-endomethylenetetrahydrophthalic acid, one in which the 3 to 5 positions are substituted with a methyl group, ethyl group, etc. is used. The molar ratio of unsaturated acid/saturated acid is 1.00/9.00
~9.00/1.00 is preferred, and the ratio of mono- or dialkyl-substituted 3,6-endomethylenetetrahydrophthalic acid in the saturated acid is preferably 30-70 mol%. Also, the molar ratio of acid groups of total acids/hydroxyl groups of polyhydric alcohol is not particularly limited, but is 1.10/0.90~
A range of 0.90/1.10 is preferred.
また上記の(b)は、今日一般に用いられている有
機過酸化物が用いられ、通常、常温以上で安定な
ものであり、100〜200℃で分解するものが特に好
ましい。２，５−ジメチル−２，５−ジ（ｔ−ブ
チルパーオキシ）ヘキサン、２，５ジメチル−
２，５−ジ（ｔ−ブチルパーオキシ）ヘキシンな
どが用いられ、ほかにジ−ｔ−ブチルパーオキシ
−３，３，５−トリメチルシクロヘキサン、α，
α−ジ−ｔブチルパーオキシジｐ−ジイソプロピ
ルベンゼン等が使用される。 For the above (b), an organic peroxide commonly used today is used, and it is usually stable at room temperature or higher, and those that decompose at 100 to 200°C are particularly preferable. 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-
2,5-di(t-butylperoxy)hexane is used, and in addition, di-t-butylperoxy-3,3,5-trimethylcyclohexane, α,
α-di-t-butylperoxydi-p-diisopropylbenzene and the like are used.
これら、(a)／(b)の配合比は、85／15〜99／１
（重量部）が好ましくまた、加熱硬化温度は100〜
230℃の範囲が好ましい。 The blending ratio of (a)/(b) is 85/15 to 99/1
(parts by weight) is preferable, and the heat curing temperature is 100~
A range of 230°C is preferred.
本発明になる樹脂組成物には、補強基材、充填
剤、顔料、カツプリング剤や離型剤など、今日、
不飽和ポリエステル樹脂の利用の際に用いられて
いる材料（架橋性単量体を除く）を自由に用いる
ことができる。 The resin composition of the present invention currently contains reinforcing base materials, fillers, pigments, coupling agents, mold release agents, etc.
Materials used in the use of unsaturated polyester resins (excluding crosslinkable monomers) can be freely used.
以下本発明を実施例により説明する。部とある
のは、重量部である。 The present invention will be explained below with reference to Examples. Parts are parts by weight.
実施例 １
無水マレイン酸0.50モル、３−メチル−３，６
−エンドメチレンテトラヒドロ無水フタル酸0.50
モル、プロピレングリコール1.05モルを窒素ガス
気流中にて、210℃に加熱、脱水、縮合せしめて
えられた酸価20の不飽和ポリエステル95部と２，
５ジメチル−２，５−ジ（ｔ−ブチルパーオキ
シ）ヘキサン（日本油脂社製商品名パーヘキサ
25B）５部とを相溶させ、組成物Ａとした。Example 1 0.50 mol of maleic anhydride, 3-methyl-3,6
- Endomethylenetetrahydrophthalic anhydride 0.50
95 parts of unsaturated polyester with an acid value of 20 obtained by heating, dehydrating, and condensing 1.05 moles of propylene glycol at 210°C in a nitrogen gas stream and 2.
5-dimethyl-2,5-di(t-butylperoxy)hexane (trade name: Perhexa, manufactured by NOF Corporation)
Composition A was obtained by dissolving 5 parts of 25B).
組成物Ａを50ｇ、容量100mlのガラスビーカに
とり220℃の油槽に入れたところ5.3分でゲル化開
始、約10分で完全に硬化した。 When 50 g of Composition A was placed in a 100 ml glass beaker and placed in an oil bath at 220°C, gelation started in 5.3 minutes and completely hardened in about 10 minutes.
実施例 ２
前記実施例１の組成物Ａを10×10×120mmの棒
状に金型の中で注型成形した。硬化は、180℃20
分行なわせたところ硬化樹脂の物性は、曲げ強さ
10Kg／mm2であり、一方熱変形温度は148℃とすぐ
れた耐熱性を示した。Example 2 The composition A of Example 1 was cast into a rod shape of 10 x 10 x 120 mm in a mold. Curing is at 180℃20
The physical properties of the cured resin were determined by the bending strength.
10Kg/mm 2 , and the heat distortion temperature was 148℃, showing excellent heat resistance.
なお、組成物Ａを常温で保管して６ケ月間、ほ
とんど安定性をそこなうことなく40℃〜50℃の雰
囲気の貯蔵でも安定性は６ケ月以上十分あり、６
〜12ケ月以上も十分見込みがあるものとみられ
た。 In addition, Composition A has been stored at room temperature for 6 months, and even when stored in an atmosphere of 40°C to 50°C, it has sufficient stability for more than 6 months, with almost no loss of stability.
The outlook seemed promising for ~12 months or more.
実施例 ３
フマル酸0.40モル、４−メチル−３，６−エン
ドメチレンテトラヒドロ無水フタル酸0.60モル、
エチレングリコール1.05モルを窒素ガス気流中に
て20℃に加熱、縮合せしめてえられた酸価24の不
飽和ポリエステル90部と２，５ジメチル−２，５
−ジ（ｔ−ブチルパーオキシ）ヘキシン（日本油
脂社製商品名パーヘキシン25B）10部とを相溶さ
せ、組成物Ｂとした。Example 3 0.40 mol of fumaric acid, 0.60 mol of 4-methyl-3,6-endomethylenetetrahydrophthalic anhydride,
90 parts of unsaturated polyester with an acid value of 24 obtained by heating and condensing 1.05 mol of ethylene glycol at 20°C in a nitrogen gas stream and 2,5 dimethyl-2,5
- 10 parts of di(t-butylperoxy)hexine (trade name: Perhexine 25B, manufactured by Nippon Oil & Fats Co., Ltd.) to obtain Composition B.
組成物Ｂの硬化樹脂（220℃ 20分 硬化物）
の物性測定例を挙げると熱変形温度160℃、曲げ
強さ11.2Kg／mm2であり、また組成物Ｂは45℃貯蔵
中、6.5ケ月の間ゲル化することなく、一定の応
用物性のものがえられた。 Cured resin of composition B (cured product at 220°C for 20 minutes)
As an example of physical property measurement, composition B has a heat distortion temperature of 160°C and a bending strength of 11.2 kg/mm 2 . Composition B did not gel for 6.5 months when stored at 45°C, and had certain applied physical properties. It was raised.
本発明になる硬化性樹脂組成物は、貯蔵安定性
にすぐれ、これによつて熱変形温度の高い硬化物
が得られる。 The curable resin composition of the present invention has excellent storage stability, and as a result, a cured product having a high heat distortion temperature can be obtained.
Claims (1)
ドメチレンテトラヒドロフタル酸で変性した不
飽和ポリエステル (b) 有機過酸化物を含有してなる熱硬化性樹脂組
成物。 ２ モノまたはジアルキル置換３，６−エンドメ
チレンテトラヒドロフタル酸で変性した不飽和ポ
リエステルを85〜99重量部、有機過酸化物を15〜
１重量部としてなる特許請求の範囲第１項記載の
熱硬化性樹脂組成物。[Scope of Claims] 1. A thermosetting resin composition comprising: (a) an unsaturated polyester modified with mono- or dialkyl-substituted 3,6-endomethylenetetrahydrophthalic acid; and (b) an organic peroxide. 2 85 to 99 parts by weight of an unsaturated polyester modified with mono- or dialkyl-substituted 3,6-endomethylenetetrahydrophthalic acid, and 15 to 99 parts by weight of an organic peroxide.
1 part by weight of the thermosetting resin composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5343580A JPS56149416A (en) | 1980-04-21 | 1980-04-21 | Thermosetting resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5343580A JPS56149416A (en) | 1980-04-21 | 1980-04-21 | Thermosetting resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56149416A JPS56149416A (en) | 1981-11-19 |
| JPH0128061B2 true JPH0128061B2 (en) | 1989-05-31 |
Family
ID=12942760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5343580A Granted JPS56149416A (en) | 1980-04-21 | 1980-04-21 | Thermosetting resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56149416A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3305222A1 (en) * | 1983-02-16 | 1984-08-16 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING MOLDING MATERIALS FROM UNSATURATED POLYESTER RESINS |
-
1980
- 1980-04-21 JP JP5343580A patent/JPS56149416A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56149416A (en) | 1981-11-19 |
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