JPS6226329B2 - - Google Patents
Info
- Publication number
- JPS6226329B2 JPS6226329B2 JP8792878A JP8792878A JPS6226329B2 JP S6226329 B2 JPS6226329 B2 JP S6226329B2 JP 8792878 A JP8792878 A JP 8792878A JP 8792878 A JP8792878 A JP 8792878A JP S6226329 B2 JPS6226329 B2 JP S6226329B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- composition
- unsaturated polyester
- parts
- mol
- 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
- 150000001451 organic peroxides Chemical class 0.000 claims description 5
- 239000011342 resin composition Substances 0.000 claims description 5
- 229920001187 thermosetting polymer Polymers 0.000 claims description 5
- 125000002081 peroxide group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229920006337 unsaturated polyester resin Polymers 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- 238000005452 bending Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- NIDNOXCRFUCAKQ-RNGGSSJXSA-N (1r,2r,3s,4s)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@@H]2C=C[C@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-RNGGSSJXSA-N 0.000 description 1
- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 1
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical compound CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZNHPPXDUJKXBNM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)hexane Chemical compound CC(C)(C)OOC(C)CCC(C)OOC(C)(C)C ZNHPPXDUJKXBNM-UHFFFAOYSA-N 0.000 description 1
- OXGOEZHUKDEEKS-UHFFFAOYSA-N 3-tert-butylperoxy-1,1,5-trimethylcyclohexane Chemical compound CC1CC(OOC(C)(C)C)CC(C)(C)C1 OXGOEZHUKDEEKS-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 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
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 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
- 238000002156 mixing Methods 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)
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 excellent 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
性に限度があり、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, their storage stability is limited, and 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からなる組成物の一連の研究
中に見出した現象の利用である。 The present invention completely eliminates the crosslinking monomer of conventional unsaturated polyester resins and makes use of a phenomenon discovered during a series of studies on compositions consisting of so-called unsaturated polyesters and organic peroxides.
すなわち、本発明は、(a)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85〜99重量部および(b)二つの過酸化物基を
有する有機過酸化物15〜１重量部からなる熱硬化
性樹脂組成物に関し、上記の(a)は、通常の不飽和
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、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。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％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比も特に限定しない
が、1.10／0.90〜0.90／1.10程度で良い。 That is, the present invention comprises (a) 85 to 99 parts by weight of an unsaturated polyester modified with 3,6-endomethylenetetrahydrophthalic acid and (b) 15 to 1 part by weight of an organic peroxide having two peroxide groups. Regarding the thermosetting resin composition, the above-mentioned (a) is a general unsaturated polyester, that is, a liquid with an acid value of 100 to 0 obtained by a dehydration condensation reaction of an unsaturated acid, a saturated acid, and a polyhydric alcohol. It is a solid polyester, and it is necessary to use 3,6-endomethylenetetrahydrophthalic acid as one of its saturated acid components. The molar ratio of unsaturated acid/saturated acid is 1.00/
9.00-9.00/1.00 is preferable, 3.6 in saturated acid
-The ratio of endomethylenetetrahydrophthalic acid is
30-70% is preferred. Further, the ratio of acid groups of all acids/hydroxyl groups of polyhydric alcohol is not particularly limited, but may be about 1.10/0.90 to 0.90/1.10.
また、上記の(b)は、二つの過酸化物基を有する
有機過酸化物であるが、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、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。 Further, the above (b) is an organic peroxide having two peroxide groups, and is usually stable at room temperature or above, and one that decomposes at 100 to 200°C is particularly preferable. 2,5 dimethyl-2,5-di(t-butylperoxy)hexane, 2,5 dimethyl-2,
5-di(t-butylperoxy)hexyne, di-
Used are t-butylperoxy-3,3,5-trimethylcyclohexane, α,α'-di-t-butylperoxydi-p-diisopropylbenzene, and the like.
これら(a)／(b)の配合比は、85／15〜99／１（重
量比）で良く、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) may be 85/15 to 99/1 (weight ratio), and the heat curing temperature is 100 to 230℃.
A range of is preferred.
本発明の応用にあたつては、本発明の組成物に
補強基材、充填剤、顔料など、今日不飽和ポリエ
ステル樹脂の利用で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。 In the application of the present invention, the composition of the present invention may contain any materials currently used in the use of unsaturated polyester resins (excluding crosslinkable monomers), such as reinforcing base materials, fillers, and pigments. It can be used for.
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 by weight.
実施例 １
無水マレイン酸0.50モル、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、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, 0.50 mol of 3,6-endomethylenetetrahydrophthalic anhydride, and 1.05 mol of propylene glycol in a nitrogen gas stream,
95 parts of unsaturated polyester with an acid value of 20 obtained by heating and condensation at 210°C and 2.5 dimethyl-2.
Composition A was prepared by dissolving the mixture with 5 parts of 5-di(t-butylperoxy)hexane (trade name: Perhexa 25B, manufactured by NOF Corporation).
組成物Ａを50ｇ、溶量100mlのガラスビーカに
とり220℃の油槽に入れたところ、5.5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 220° C. oil bath in a glass beaker containing 50 g of composition A, gelation started in 5.5 minutes and completely hardened in about 10 minutes.
比較例
無水マレイン酸0.50モル、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
流中で210℃に加熱、縮合させて得られた酸価22
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
（商品名パーヘキサ25B）５部を相溶させ、組成
物A′とした。これを直径16mmの試験管に10ｇと
り、160℃で20分間加熱した。Comparative example Acid value 22 obtained by heating and condensing 0.50 mol of maleic anhydride, 0.50 mol of phthalic anhydride, and 1.05 mol of propylene glycol at 210°C in a nitrogen gas stream.
95 parts of unsaturated polyester and 2,5-dimethyl-
5 parts of 2,5-di(t-butylperoxy)hexane (trade name: Perhexa 25B) were dissolved to form a composition A'. 10g of this was placed in a 16mm diameter test tube and heated at 160°C for 20 minutes.
冷却後、アセトンを20ｇ加え試験管の内容を溶
解させた。約１ｇのゲル分を残して溶解した。 After cooling, 20 g of acetone was added to dissolve the contents of the test tube. It was dissolved leaving about 1 g of gel.
実施例 ２
前記実施例１の組成物Ａを10×10×120mmの棒
状に金型中で注型成形した。Example 2 Composition A of Example 1 was cast into a rod shape of 10 x 10 x 120 mm in a mold.
硬化は、180℃20分行なわしめたところ、硬化
樹脂の物性は、曲げ強さ10.1Kg／mm2熱変形温度
150℃とすぐれた耐熱性を示した。 Curing was performed at 180℃ for 20 minutes, and the physical properties of the cured resin were: bending strength: 10.1Kg/mm 2 heat distortion temperature
It showed excellent heat resistance of 150℃.
なお、組成物Ａを常温で保管して３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３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
る。 In addition, Composition A can be stored at room temperature for 3 months with almost no loss in stability, and even when stored in an atmosphere of 40°C to 50°C, it is sufficiently stable for more than 3 months.
It seems that there is a good chance that it will continue for 6 to 12 months or more.
実施例 ３
フマル酸0.40モル、３・６−エンドメチレンテ
トラヒドロフタル酸（日立化成工業社製商品名ハ
イミツク酸）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、220℃に加熱、縮合
せしめてえられた酸価25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 3,6-endomethylenetetrahydrophthalic acid (trade name: Himic acid, manufactured by Hitachi Chemical Co., Ltd.), 1.05 mol of ethylene glycol
Unsaturated polyester 90 with an acid value of 25 obtained by heating and condensing moles at 220°C in a nitrogen gas stream.
Composition B was obtained by dissolving 10 parts of 2,5 dimethyl-2,5-di(t-butylperoxy)hexyne (trade name: Perhexine 25B, manufactured by NOF Corporation).
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165℃、曲げ強
さ11.5Kg／mm2であり、また組成物Ｂの45℃貯蔵安
定中、3.5ケ月の間ゲル化することなく、一定の
応用物性が得られた。 To give an example of measuring the physical properties of the cured resin of Composition B (cured product at 220°C for 20 minutes), the heat distortion temperature is 165°C, the bending strength is 11.5Kg/ mm2 , and the composition B is stable during storage at 45°C. Certain applied physical properties were obtained without gelation for 3.5 months.
本発明によれば、架橋性単量体を用いることな
く、貯蔵安定性のすぐれた、硬化樹脂物性とくに
熱変形温度の高い、熱硬化性樹脂組成物が得られ
る。 According to the present invention, a thermosetting resin composition with excellent storage stability and cured resin physical properties, particularly a high heat distortion temperature, can be obtained without using a crosslinkable monomer.
Claims (1)
タル酸で変性した不飽和ポリエステル85〜99重
量部および (b) 二つの過酸化物基を有する有機過酸化物15〜
１重量部からなる熱硬化性樹脂組成物。[Scope of Claims] 1 (a) 85 to 99 parts by weight of an unsaturated polyester modified with 3,6-endomethylenetetrahydrophthalic acid and (b) 15 to 99 parts by weight of an organic peroxide having two peroxide groups
A thermosetting resin composition consisting of 1 part by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8792878A JPS5516012A (en) | 1978-07-19 | 1978-07-19 | Thermosetting resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8792878A JPS5516012A (en) | 1978-07-19 | 1978-07-19 | Thermosetting resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5516012A JPS5516012A (en) | 1980-02-04 |
| JPS6226329B2 true JPS6226329B2 (en) | 1987-06-08 |
Family
ID=13928569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8792878A Granted JPS5516012A (en) | 1978-07-19 | 1978-07-19 | Thermosetting resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5516012A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH088693Y2 (en) * | 1991-02-25 | 1996-03-13 | シンコハンガー株式会社 | Hanger |
-
1978
- 1978-07-19 JP JP8792878A patent/JPS5516012A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5516012A (en) | 1980-02-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2618616A (en) | Modified alkyd resins and composi | |
| US2852487A (en) | Polymerizable solution of an allyl ether and an unsaturated alkyd resin | |
| US2475731A (en) | Copolymerization products of styrene and adduct modified glycolmaleate resins | |
| BR0315525B1 (en) | Air-drying waterborne resin composition, method for producing an air-drying waterborne resin composition and use of an amphiphilic air-drying dentritic polymer | |
| Gaw et al. | Preparation of polyimide-epoxy composites | |
| US3933939A (en) | Polyester with epoxy monomer, and a cross-linking monomer | |
| JPH0611771B2 (en) | Copolymer using isoimide and method for producing the same | |
| US2537949A (en) | Modified alkyd resins and coating compositions containing the same in admixture withreadily copolymerizable vinyl monomers | |
| JPS6226329B2 (en) | ||
| US3646160A (en) | Polyesters containing tertiary nitrogen atoms | |
| JPH054965B2 (en) | ||
| JPH0128061B2 (en) | ||
| US2590653A (en) | Tall oil modified alkyd resins and process for preparing the same | |
| JPH10298431A5 (en) | ||
| US3060147A (en) | Polyester resin compositions | |
| US3558535A (en) | Coating compositions comprising an epoxidized fatty ester of a cyclic polyol and an acidic polyester | |
| US3270089A (en) | Flame-retardant compounds as crosslinking monomers | |
| McGary Jr et al. | Resins from endo‐dicyclopentadiene dioxide | |
| US6200645B1 (en) | Polyester resin impregnating and coating solutions and their use | |
| US2726223A (en) | Modified polyester resins | |
| JPH0214941B2 (en) | ||
| JPH0812875A (en) | Production of polyphenylene oxide-based molding material | |
| JP4947333B2 (en) | Resin composition for electrical insulation and method for producing electrical equipment insulator using the same | |
| US3719622A (en) | Rapid drying alkyd coating modified with amino aromatic carboxylic acid | |
| KR100708359B1 (en) | Casting resins and uses thereof |