JPH02279712A - Curable resin composition - Google Patents
Curable resin compositionInfo
- Publication number
- JPH02279712A JPH02279712A JP10128189A JP10128189A JPH02279712A JP H02279712 A JPH02279712 A JP H02279712A JP 10128189 A JP10128189 A JP 10128189A JP 10128189 A JP10128189 A JP 10128189A JP H02279712 A JPH02279712 A JP H02279712A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- acid
- resin composition
- unsaturated polyester
- curable resin
- 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.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 18
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 18
- 239000000194 fatty acid Substances 0.000 claims abstract description 18
- 229930195729 fatty acid Natural products 0.000 claims abstract description 18
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 18
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 18
- 229920006305 unsaturated polyester Polymers 0.000 claims abstract description 18
- 239000000539 dimer Substances 0.000 claims abstract description 15
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 13
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 150000002009 diols Chemical class 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 9
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 6
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005809 transesterification reaction Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 abstract description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 9
- 238000010292 electrical insulation Methods 0.000 abstract description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000944 linseed oil Substances 0.000 abstract description 6
- 235000021388 linseed oil Nutrition 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 3
- 239000003063 flame retardant Substances 0.000 abstract description 2
- 239000003112 inhibitor Substances 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract 1
- 239000000945 filler Substances 0.000 abstract 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 description 3
- 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 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
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 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
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の目的１
（産業上の利用分野）
本発明は、電気４１Ｉｉ器等の充填に用いる柔軟性、密
着性、電気絶縁性に優れた硬化性ＭＩＡ詣組成物に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Objective of the Invention 1 (Field of Industrial Application) The present invention relates to a curable MIA composition having excellent flexibility, adhesion, and electrical insulation properties for use in filling electrical 41Ii containers, etc. .
（従来の技術）
従来、電気Ｉｆｉ器、特に蛍光灯安定器の充填用として
不飽和ポリエステル樹脂が多く使用されている。(Prior Art) Conventionally, unsaturated polyester resins have been widely used for filling electric Ifi devices, especially fluorescent lamp ballasts.
（発明が解決しようとする課題）
安定器に使用されている従来の不飽和ポリエステル樹脂
は、その硬化物が硬い場合には、体積収縮率が大きく、
硬化物が安定器のケースから剥離して、鳴音を生じなり
、熱放散性が不十分となる欠点がある。 一方、従来の
アマニ油脂肪酸などで変性した不飽和ポリエステル樹脂
であって硬化物が柔軟なものは、高温での電気絶縁性か
悪く、またその柔軟性が経時変化して硬くなる欠点があ
り、いずれにせよ満足すべきものはなかった。(Problems to be Solved by the Invention) Conventional unsaturated polyester resins used in stabilizers have a large volumetric shrinkage rate when the cured product is hard.
Disadvantages include that the cured product peels off from the ballast case, causing noise and insufficient heat dissipation. On the other hand, conventional unsaturated polyester resins modified with linseed oil fatty acids etc., which have a flexible cured product, have poor electrical insulation properties at high temperatures, and also have the disadvantage that their flexibility changes over time and becomes hard. In any case, there was nothing to be satisfied with.
本発明は、上記の欠点を解消するためになされたもので
、柔軟性、密着性、電気絶縁性に優れ、鳴音や剥離がな
く、柔軟性の経時変化が少ない硬化性樹脂組成物を提供
しようとするものである。The present invention was made to eliminate the above-mentioned drawbacks, and provides a curable resin composition that has excellent flexibility, adhesion, and electrical insulation, does not cause noise or peeling, and has little change in flexibility over time. This is what I am trying to do.
［発明の構成］
（課題を解決するための手段）
本発明者らは、上記の目的を達成しようと鋭意検討を重
ねた結果、後述する組成物が上記目的を達成することを
見いだし本発明を完成したものである。[Structure of the Invention] (Means for Solving the Problems) As a result of intensive studies aimed at achieving the above object, the present inventors have discovered that the composition described below achieves the above object, and have devised the present invention. It is completed.
すなわち、本発明は、
＜Ａ） ＜ａ ）不飽和結合を有することある脂肪酸
及びそのダイマー酸、
（ｂ）ポリエチレンテレフタレートと、ジオール若しく
はトリオールとのエステル交換化成分、
（ｃ）不飽和結合を有することあるジカルボン酸、並び
に
（ｄ ）ジオールを反応させて得られる不飽和ポリエス
テルに、
（Ｂ）重合性ビニル系単量体
を配合してなることを特徴とする硬化性樹脂組成物であ
る。That is, the present invention provides <A) <a) a fatty acid and its dimer acid that may have an unsaturated bond, (b) a transesterification component between polyethylene terephthalate and a diol or triol, (c) a component that has an unsaturated bond This is a curable resin composition characterized by blending (B) a polymerizable vinyl monomer with an unsaturated polyester obtained by reacting a certain dicarboxylic acid and (d) a diol.
本発明に用いる（Ａ＞不飽和ポリエステルの反応成分は
、＜ａ）不飽和結合を有することある脂肪酸及びそのダ
イマー酸、（ｂ）ポリエチレンテレフタレートと、ジオ
ール若しくはトリオールとのエステル交換化成分、（ｃ
）不飽和結合を有することあるジカルボン酸、並びに（
ｄ ）ジオールを必須とする。The reaction components of the (A) unsaturated polyester used in the present invention are <a) a fatty acid and its dimer acid that may have an unsaturated bond, (b) a transesterification component between polyethylene terephthalate and a diol or triol, (c)
) dicarboxylic acids that may have unsaturated bonds, and (
d) Diol is required.
（ａ）脂肪酸およびダイマー酸としては、大豆脂脂肪酸
、アマニ油脂肪酸、トール油脂肪酸、オリーブ油脂肪酸
等に、これらのダイマー酸を併用したものが挙げられ、
それらは単独又は２種以上混合して使用することができ
る。 ダイマー酸としては、その含有量が４０１１！量
％以上で、中和価１７０〜２００．鹸化価１９０〜２０
０のものが望ましい。(a) Fatty acids and dimer acids include soybean fat fatty acids, linseed oil fatty acids, tall oil fatty acids, olive oil fatty acids, etc., and combinations of these dimer acids,
They can be used alone or in combination of two or more. As a dimer acid, its content is 4011! % or more, neutralization value 170-200. Saponification value 190-20
A value of 0 is desirable.
（ｂ）ポリエチレンテレフタレートのエステル交換化成
分としては、テレフタル酸とエチレングリコールとの重
縮合反応等によって得られる、例えば次の構造式を有す
る線状のポリエステル樹脂（ポリエチレンテレフタレー
ト）に、
ジエチレングリコールなどジオール又はグリセリンなど
トリオールと、鉛、亜鉛などの金属酸化物、アルキルチ
タン化合物等の触媒とを加え、２２０°Ｃといった適宜
温度でエステル交換をして得られる混合成分であり、こ
れらはりカルボン酸又はジオール成分として使用するも
のである。(b) As the transesterification component of polyethylene terephthalate, for example, a linear polyester resin (polyethylene terephthalate) having the following structural formula, which is obtained by a polycondensation reaction of terephthalic acid and ethylene glycol, and a diol such as diethylene glycol or It is a mixed component obtained by adding a triol such as glycerin, a metal oxide such as lead or zinc, or a catalyst such as an alkyl titanium compound, and transesterifying the mixture at an appropriate temperature such as 220°C. It is used as a.
（ｃ）ジカルボン酸としては、無水マレイン酸、マレイ
ン酸、フマール酸、イタコン酸等の不飽和ジカルボン酸
、及び、フタル酸、テトラハイドロフタル酸、イソフタ
ル酸、エンドメチレンテトラハイドロフタル酸、マロン
酸、アジピン酸、これらの無水物等の飽和ジカルボン酸
が挙げられ、単独又は２種以上混合して使用することが
できる。(c) Dicarboxylic acids include unsaturated dicarboxylic acids such as maleic anhydride, maleic acid, fumaric acid, and itaconic acid, and phthalic acid, tetrahydrophthalic acid, isophthalic acid, endomethylenetetrahydrophthalic acid, malonic acid, Examples include saturated dicarboxylic acids such as adipic acid and anhydrides thereof, which can be used alone or in combination of two or more.
（ｄ ）ジオールとしては、エチレングリコール、ジエ
チレングリコール、プロピレングリコール、グリセリン
、トリス−２−ヒドロキシエチルイソシアヌレート等が
挙げられ、これらは単独又は２種以上選択して使用する
ことができる。(d) Diols include ethylene glycol, diethylene glycol, propylene glycol, glycerin, tris-2-hydroxyethyl isocyanurate, and the like, and these can be used alone or in combination of two or more.
＜ａ）脂肪酸及びそのダイマー酸の配合割合は、不飽和
ポリエステルの３０〜６０重量３％配合することが望ま
しい、 その配合割合が３０重量％未満では樹脂組成物
に十分な柔軟性をもたせることができず、また６０重量
％を超えると硬化性や電気絶縁性が不十分となり好まし
くない、 またダイマー酸は、脂肪酸およびダイマー酸
量の１０重量％以上含有するように配合す・ることが望
ましい。 それは、１０重量％未満では柔軟性の経時変
化が大きくなり好ましくないからである。 また、（ｂ
）ポリエチレンテレフタレートの配合割合は、不飽和ポ
リエステルの１０〜３０を量％含有するように配合する
ことが望ましい。 その配合割合が１０重量％未満では
電気絶縁性が劣り、また経済的ではない。<a) The blending ratio of fatty acids and their dimer acids is preferably 30 to 60% by weight of the unsaturated polyester. If the blending ratio is less than 30% by weight, the resin composition may not have sufficient flexibility. Moreover, if it exceeds 60% by weight, curability and electrical insulation properties will be insufficient, which is undesirable. Furthermore, it is desirable to blend the dimer acid so that it is contained in an amount of 10% by weight or more based on the amount of fatty acid and dimer acid. This is because if it is less than 10% by weight, the change in flexibility over time becomes large, which is not preferable. Also, (b
) The blending ratio of polyethylene terephthalate is preferably such that it contains 10 to 30% by weight of unsaturated polyester. If the blending ratio is less than 10% by weight, the electrical insulation properties will be poor and it will be uneconomical.
また３０重ｉ％を超えると高粘度で重合°性ビニル系単
量体に溶解しにくくなり好ましくないからである。Moreover, if it exceeds 30% by weight, it is undesirable because it has a high viscosity and becomes difficult to dissolve in the polymerizable vinyl monomer.
本発明に用いる（Ｂ）重合性ビニル系単量体としては、
スチレン、ビニルトルエン、メタアクリル酸エステル、
アクリル酸エステル等が挙げられ、これらは単独又は２
種以上混合して使用することができる。 ＠合作ビニル
系単量体の配合割合は、硬化性樹脂組成物に対して１０
〜６０重量％含有するように配合することが望ましい。As the (B) polymerizable vinyl monomer used in the present invention,
Styrene, vinyltoluene, methacrylic acid ester,
Examples include acrylic esters, which may be used alone or in combination
Can be used in combination of more than one species. @Cooperative The blending ratio of vinyl monomer is 10% to the curable resin composition.
It is desirable to blend it so that it contains up to 60% by weight.
その配合割合が１０重量％未満では粘度が増大して流
動性が悪くなり、また６０重量％を超えると柔軟性、密
着性が低下し好ましくない。If the blending ratio is less than 10% by weight, the viscosity will increase and fluidity will deteriorate, and if it exceeds 60% by weight, flexibility and adhesion will decrease, which is not preferred.
本発明の硬化性樹脂組成物を安定化するなめ、反応の際
また重合性ビニル系単量体を相溶させる時に、ハイドロ
キノン、ｐ−ｔｅｒｔブチルカテコール、バラベンゾキ
ノン等の重合禁止剤を添加させることができる。 そし
て、この組成物を硬化させるための触媒として過酸化ベ
ンゾイル、メチルエチルゲトンパーオキサイド等の過酸
化物を使用することができる。 また、ナフテン酸金属
塩またはアミン系化合物を促進剤として使用することが
できる。 本発明の硬化性樹脂組成物は、まずポリエチ
レンテレフタレートのエステル交換化を行い、その後各
成分を配合して不飽和ポリエステルを得て、次いで重合
性ビニル系単量体を配合して製造することができる。
そして本発明の目的に反しない限りにおいて、タルク、
シリカ、アルミナ、珪砂等の各種無機質粉末、難燃剤等
を配合し電気機器等の充填用として使用することができ
る。In order to stabilize the curable resin composition of the present invention, a polymerization inhibitor such as hydroquinone, p-tert-butylcatechol, or rosebenzoquinone is added during the reaction or when making the polymerizable vinyl monomer compatible. I can do it. As a catalyst for curing this composition, peroxides such as benzoyl peroxide and methyl ethyl getone peroxide can be used. Also, naphthenic acid metal salts or amine compounds can be used as accelerators. The curable resin composition of the present invention can be produced by first transesterifying polyethylene terephthalate, then blending each component to obtain an unsaturated polyester, and then blending a polymerizable vinyl monomer. can.
And as long as it does not contradict the purpose of the present invention, talc,
It can be mixed with various inorganic powders such as silica, alumina, silica sand, flame retardants, etc. and used for filling electrical equipment, etc.
（作用）
ダイマー酸を配合しな脂肪酸を用いることによって組成
物に柔軟性を付与し、また密着性の経時変化を少なくす
る。 さらに組成物の分子電格内にポリエチレンテレフ
タレートのエステル交換化成分を導入することによって
電気絶縁性、耐熱性を向上させることができる。(Function) By using a fatty acid without adding dimer acid, flexibility is imparted to the composition, and changes in adhesion over time are reduced. Furthermore, electrical insulation and heat resistance can be improved by introducing a transesterified component of polyethylene terephthalate into the molecular electric potential of the composition.
（実施例）
次に、本発明を実施例によって説明するが、本発明は下
記の実施例によって限定されるものではない、 以下の
実施例および比較例において「部」とは「重量部」を意
味する。(Example) Next, the present invention will be explained by examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, "parts" means "parts by weight". means.
実施例 １
ポリエチレンテレフタレート １０６部、ジエチレング
リコール１２３．６部、およびテトラブチルチタネート
Ｏ，ＯＳ部を、２２０℃で２時間エステル交換化反応を
行い冷却しな、 次いでアマニ油脂肪酸７０部、ダイマ
ー酸としてＤＡ−５００にツカ合成社製、商品名）
２１７．５部、および無水マレイン酸４９部を配合し、
１９５°Ｃで反応させて酸価１９．Ｏの不飽和ポリエス
テルを得な、 この不飽和ポリエステルに、ハイドロキ
ノン０．２５部とスチレンモノマー３００部を加えて溶
解させ、さらに６％ナフテン酸コバルト溶液３．５部を
添加混合して、硬化性樹脂組成物を製造した。Example 1 106 parts of polyethylene terephthalate, 123.6 parts of diethylene glycol, and parts of tetrabutyl titanate O,OS were subjected to a transesterification reaction at 220° C. for 2 hours without cooling, and then 70 parts of linseed oil fatty acid and DA as dimer acid were transesterified. -500 manufactured by Tsuka Gosei Co., Ltd., product name)
217.5 parts and 49 parts of maleic anhydride are blended,
React at 195°C to achieve an acid value of 19. To obtain an unsaturated polyester of O, add 0.25 parts of hydroquinone and 300 parts of styrene monomer to this unsaturated polyester and dissolve it, and then add and mix 3.5 parts of a 6% cobalt naphthenate solution to obtain a curable polyester. A resin composition was produced.
実施例 ２
ポリエチレンテレフタレート９９部、ジエチレングリコ
ール７２部、およびテトラブチルチタネート０．０５部
を、２２０℃で２時間エステル交換化反応を行い冷却し
な、 次いでプロピレングリコール３２部、アマニ油脂
肪酸４５部、無水テトラハイドロフタル酸５４部、ダイ
マー酸く前出）１６２部、および無水マレイン酸５３．
１部を配合して、１９５℃で反応させて酸価１８．０の
不飽和ポリエステルを得た。Example 2 99 parts of polyethylene terephthalate, 72 parts of diethylene glycol, and 0.05 part of tetrabutyl titanate were transesterified at 220°C for 2 hours without cooling, and then 32 parts of propylene glycol, 45 parts of linseed oil fatty acid, and anhydrous 54 parts of tetrahydrophthalic acid, 162 parts of dimer acid (see above), and 53 parts of maleic anhydride.
1 part was blended and reacted at 195°C to obtain an unsaturated polyester with an acid value of 18.0.
この不飽和ポリエステルに、ハイドロキノン０１２５部
とスチレンモノマー２８８部を加えて溶解させ、さらに
６％ナフテン酸コバルト溶液３．０部を添加混合して、
硬化性樹脂組成物を製造した。0.125 parts of hydroquinone and 288 parts of styrene monomer were added and dissolved in this unsaturated polyester, and 3.0 parts of a 6% cobalt naphthenate solution was added and mixed.
A curable resin composition was produced.
実施例 ３
ポリエチレンテレフタレート １４４部、グリセリン４
４．４部、およびテトラブチルチタネート（１，０５部
を、２２０℃で２時間エステル交換化反応を行い冷却し
た。 次いでプロピレングリコール５２．８１、大豆油
脂肪酸１２０部、ダイマー＊＜前出）８４部、および無
水マレイン６８４部を配合して、 １９５ ’Ｃで反応
させ酸価１８．２の不飽和ポリエステルを得な。Example 3 144 parts of polyethylene terephthalate, 4 parts of glycerin
4.4 parts, and 1.05 parts of tetrabutyl titanate were subjected to transesterification reaction at 220° C. for 2 hours and cooled. Next, 52.81 parts of propylene glycol, 120 parts of soybean oil fatty acid, dimer * < above) 84 1 part and 684 parts of maleic anhydride were reacted at 195'C to obtain an unsaturated polyester having an acid value of 18.2.
この不飽和ポリエステルに、ハイドロキノン０．２４部
とスチレンモノマー２７６部を加えて溶解させ、さらに
６％ナフテン酸コバルト溶液３．２部を添加混合して、
硬化性樹脂組成物を製造しな。To this unsaturated polyester, 0.24 parts of hydroquinone and 276 parts of styrene monomer were added and dissolved, and further 3.2 parts of 6% cobalt naphthenate solution was added and mixed.
Manufacture a curable resin composition.
実施例 ４
ポリエチレンテレフタレート １４４部、ジエチレング
リコール７２部、およびアルキルナタネ−１−０，０５
部を、２２０℃で２時間エステル交換化反応を行い冷却
しな、 次いでエチレングリコール４４．６部、無水テ
トラハイドロツタルミ４８部、ダイマー酸く前出）１６
８部、および無水マレイン酸５９部を配合して、１９５
℃で反応させて酸価１７．ｏの不飽和ポリエステルを得
た。 この不飽和ポリエステルに、ハイドロキノン０．
２４部とスチレンモノマー２８２部を加えて溶解させ、
さらに６％ナフテン酸コバルト溶液３．２部を添加混合
して、硬化性樹脂組成物を製造しな。Example 4 144 parts of polyethylene terephthalate, 72 parts of diethylene glycol, and alkyl rapeseed 1-0,05
1 part was subjected to transesterification reaction at 220°C for 2 hours without cooling, followed by 44.6 parts of ethylene glycol, 48 parts of anhydrous tetrahydrotutaluminum, and 16 parts of dimer acid (see above).
8 parts and 59 parts of maleic anhydride to make 195
The acid value was 17. o unsaturated polyester was obtained. Hydroquinone 0.0% is added to this unsaturated polyester.
24 parts and 282 parts of styrene monomer were added and dissolved,
Further, 3.2 parts of a 6% cobalt naphthenate solution was added and mixed to produce a curable resin composition.
比較例゛
無水フタル酸４０．０部、無水マレイン酸６０．０部、
アマニ油脂肪酸２７５部、プロピレングリコール１２０
部、ハイドロキノン０．０４部を、１６０℃で１時間、
次いで１９５℃で反応させて＊ｍ２ｏの不飽和ポリエス
テルを得た。 この不飽和ポリエステルに、ハイドロキ
ノン０．１８部とスチレンモノマー２６０部を加えて溶
解させ、さらに６％ナフテン酸コバルト溶液３．０部を
添加混合して、硬化性樹脂組成物を製造した。Comparative example 40.0 parts of phthalic anhydride, 60.0 parts of maleic anhydride,
Linseed oil fatty acid 275 parts, propylene glycol 120 parts
1 part and 0.04 part of hydroquinone at 160°C for 1 hour.
Then, a reaction was carried out at 195°C to obtain an unsaturated polyester of *m2o. 0.18 parts of hydroquinone and 260 parts of styrene monomer were added and dissolved in this unsaturated polyester, and 3.0 parts of a 6% cobalt naphthenate solution was added and mixed to produce a curable resin composition.
実施例１〜４および比較例で製造した硬化性樹脂組成物
に、第１表に示した過酸化物（メチルエチルケトンパー
オキサイド）、無機質充填剤（シリカ粉末）を加えて硬
化させた。 この組成物のゴム硬度、経時変化後のゴム
硬度、ケースとの密着性、および体積抵抗率を試験した
ので結果を第１表に示した。 本発明の硬化物はいずれ
も各試験において優れており、本発明の効果を確認する
ことができた。A peroxide (methyl ethyl ketone peroxide) and an inorganic filler (silica powder) shown in Table 1 were added to the curable resin compositions produced in Examples 1 to 4 and Comparative Example, and the compositions were cured. This composition was tested for rubber hardness, rubber hardness after aging, adhesion to the case, and volume resistivity, and the results are shown in Table 1. All of the cured products of the present invention were excellent in each test, and the effects of the present invention could be confirmed.
［発明の効果］
以上の説明および第１表から明らかなように、本発明の
硬化性樹脂組成物は、その特定の配合によって、柔軟性
、密着性、電気絶縁性に優れ、鳴音やケースからの剥離
がなく、経時変化による柔軟性の変化が少なく、安価で
あるなど数々の長所を有しており、電気機器等のコイル
の充填用として好適なものである。[Effects of the Invention] As is clear from the above explanation and Table 1, the curable resin composition of the present invention has excellent flexibility, adhesion, and electrical insulation properties, and reduces noise and cases due to its specific formulation. It has many advantages such as no peeling, little change in flexibility due to aging, and low cost, making it suitable for filling coils in electrical equipment and the like.
Claims (1)
びそのダイマー酸、（ｂ）ポリエチレンテレフタレート
とジオール若しくはトリオールとのエステル交換化成分
、（ｃ）不飽和結合を有することあるジカルボン酸、並
びに（ｄ）ジオールを反応させて得られる不飽和ポリエ
ステルに、 （Ｂ）重合性ビニル系単量体 を配合してなることを特徴とする硬化性樹脂組成物。[Scope of Claims] 1 (A) (a) A fatty acid and its dimer acid which may have an unsaturated bond, (b) a transesterification component between polyethylene terephthalate and a diol or triol, (c) a compound having an unsaturated bond A curable resin composition characterized by blending (B) a polymerizable vinyl monomer with an unsaturated polyester obtained by reacting a certain dicarboxylic acid and (d) a diol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10128189A JPH02279712A (en) | 1989-04-20 | 1989-04-20 | Curable resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10128189A JPH02279712A (en) | 1989-04-20 | 1989-04-20 | Curable resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02279712A true JPH02279712A (en) | 1990-11-15 |
Family
ID=14296481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10128189A Pending JPH02279712A (en) | 1989-04-20 | 1989-04-20 | Curable resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02279712A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60166312A (en) * | 1984-02-09 | 1985-08-29 | Dainippon Ink & Chem Inc | Production of synthetic resin for coating |
| JPS63199751A (en) * | 1987-02-16 | 1988-08-18 | Toshiba Chem Corp | Electrical insulating resin composition |
-
1989
- 1989-04-20 JP JP10128189A patent/JPH02279712A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60166312A (en) * | 1984-02-09 | 1985-08-29 | Dainippon Ink & Chem Inc | Production of synthetic resin for coating |
| JPS63199751A (en) * | 1987-02-16 | 1988-08-18 | Toshiba Chem Corp | Electrical insulating resin composition |
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