JPH02142847A - Unsaturated polyester resin composition for fiber-reinforced plastic - Google Patents
Unsaturated polyester resin composition for fiber-reinforced plasticInfo
- Publication number
- JPH02142847A JPH02142847A JP29368788A JP29368788A JPH02142847A JP H02142847 A JPH02142847 A JP H02142847A JP 29368788 A JP29368788 A JP 29368788A JP 29368788 A JP29368788 A JP 29368788A JP H02142847 A JPH02142847 A JP H02142847A
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated polyester
- fiber
- weight
- acid
- polyester 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
- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 title claims abstract description 15
- 229920002430 Fibre-reinforced plastic Polymers 0.000 title claims abstract description 5
- 239000011151 fibre-reinforced plastic Substances 0.000 title claims abstract description 5
- 229920006305 unsaturated polyester Polymers 0.000 claims abstract description 25
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 11
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 10
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001530 fumaric acid Substances 0.000 claims abstract description 5
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 3
- 239000011976 maleic acid Substances 0.000 claims abstract description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000000835 fiber Substances 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 239000012779 reinforcing material Substances 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 229920006231 aramid fiber Polymers 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 claims 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 238000009835 boiling Methods 0.000 abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000011521 glass Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 230000002087 whitening effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009787 hand lay-up Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- CPHURRLSZSRQFS-UHFFFAOYSA-N 3-[4-[2-[4-(3-hydroxypropoxy)phenyl]propan-2-yl]phenoxy]propan-1-ol Chemical compound C=1C=C(OCCCO)C=CC=1C(C)(C)C1=CC=C(OCCCO)C=C1 CPHURRLSZSRQFS-UHFFFAOYSA-N 0.000 description 1
- WRDNCFQZLUCIRH-UHFFFAOYSA-N 4-(7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=C1C=C2 WRDNCFQZLUCIRH-UHFFFAOYSA-N 0.000 description 1
- UUAGPGQUHZVJBQ-UHFFFAOYSA-N Bisphenol A bis(2-hydroxyethyl)ether Chemical compound C=1C=C(OCCO)C=CC=1C(C)(C)C1=CC=C(OCCO)C=C1 UUAGPGQUHZVJBQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000002928 artificial marble Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は優れた耐水性、耐熱水性、耐煮沸性。[Detailed description of the invention] (Industrial application field) The present invention has excellent water resistance, hot water resistance, and boiling resistance.
耐薬品性や機械的強度等諸性質を兼備する繊維強化プラ
スチック用不飽和ポリエステル樹脂組成物及びそれから
得られる繊維強化不飽和ポリエステル複合材に関するも
のである。The present invention relates to an unsaturated polyester resin composition for fiber-reinforced plastics that has various properties such as chemical resistance and mechanical strength, and a fiber-reinforced unsaturated polyester composite obtained from the composition.
（従来の技術）
従来から欅々の繊維強化材を不飽和ポリエステル樹脂で
含浸させた繊維強化不飽和ポリエステル複合材は機械部
品、電気器具、輸送機器、建材。(Conventional technology) Fiber-reinforced unsaturated polyester composites, which are made by impregnating key fiber-reinforced materials with unsaturated polyester resin, have been used in mechanical parts, electrical appliances, transportation equipment, and building materials.
家具２食器、玩具、スポーツ用品、タンク、容器等広範
囲に用いられている。その強化材の成形時、使用時に生
じる繊維強化材と不飽和ポリエステル樹脂の界面の剥離
を防ぐ為カップリング剤と呼ばれる添加剤が用いられて
きた。It is widely used in furniture, tableware, toys, sporting goods, tanks, containers, etc. Additives called coupling agents have been used to prevent separation of the interface between the fiber reinforcement and unsaturated polyester resin during molding and use of the reinforcement.
（発明が解決しようとする課題）
しかしこれら繊維強化不飽和ポリエステル複合材は耐水
性、耐熱水性、耐煮沸性、耐薬品性が不十分な場合ＪＩ
Ｓ Ｋ６９１１に定める耐薬品性試験や他に耐水性、耐
熱水性、耐煮沸性に関する試験を行なうと強化材と不飽
和ポリエステル樹脂硬化物の界面が白く変色するいわゆ
る白化と呼ばれる現象が起こる。特に人造大理石用等の
為に透明ゲルコート樹脂のあとに透明性の複合材がくる
とその白化が目立ち複合材としての外観的価値が失われ
る。(Problem to be solved by the invention) However, these fiber-reinforced unsaturated polyester composites have insufficient water resistance, hot water resistance, boiling resistance, and chemical resistance.
When conducting the chemical resistance test specified in S K6911 and other tests related to water resistance, hot water resistance, and boiling resistance, a phenomenon called whitening occurs in which the interface between the reinforcing material and the cured unsaturated polyester resin turns white. In particular, when a transparent composite material is placed after a transparent gel coat resin for use in artificial marble, the whitening becomes noticeable and the appearance value of the composite material is lost.
（課題を解決するための手段）
本発明は上記の問題点を解決する為に不飽和ポリエステ
ル樹脂を製造する時点に、不飽和ポリエステル樹脂を使
用する時点において添加剤としてグリシジルメタクリレ
ートを配合することを特長とするものである。(Means for Solving the Problems) In order to solve the above-mentioned problems, the present invention incorporates glycidyl methacrylate as an additive at the time of manufacturing the unsaturated polyester resin and at the time of using the unsaturated polyester resin. This is a feature.
すなわち、
（１）（Ａ）不飽和ポリエステル４０．−８０重量％及
び。That is, (1) (A) unsaturated polyester 40. -80% by weight and.
（Ｂ）重合性単量体２０−６０重量％及び（Ｃ）共催各
種添加剤からなる不飽和ポリエステル樹脂１００重量部
に
（Ｄ）グリシジルメタクリレート０．１−１０ 重量部
を配合してなる繊維強化プラスチック用不飽和ポリエス
テル樹脂組成物。Fiber reinforced by blending (D) 0.1-10 parts by weight of glycidyl methacrylate with 100 parts by weight of an unsaturated polyester resin consisting of (B) 20-60% by weight of a polymerizable monomer and (C) various additives. Unsaturated polyester resin composition for plastics.
（２） （Ａ）不飽和ポリエステル４０−８０重量％及
び（Ｂ）重合性単量体２０−６０重量％及び（Ｃ）共催
添加剤からなる不飽和ポリエステル樹脂１００重量部に
（Ｄ）グリシジルメタクリレート０．１−１０ 重量部
添加したものによってガラス繊維、カーボン繊維、アラ
ミド繊維、ボロン繊維。(2) 100 parts by weight of an unsaturated polyester resin consisting of (A) 40-80% by weight of unsaturated polyester, (B) 20-60% by weight of polymerizable monomer, and (C) co-additives, and (D) glycidyl methacrylate. 0.1-10 parts by weight of glass fiber, carbon fiber, aramid fiber, boron fiber depending on what is added.
金属繊維、有機繊維、のような強化材のいずれか１種以
上を含浸して得られる繊維強化不飽和ポリエステル複合
材。A fiber-reinforced unsaturated polyester composite material obtained by impregnating one or more reinforcing materials such as metal fibers and organic fibers.
である。It is.
（作用） まず本発明に於ける成分（Ａ）について説明する。(effect) First, component (A) in the present invention will be explained.
成分（Ａ）として用いられる不飽和ポリエステル樹脂は
、α、β−不飽和多塩基酸またはその無水物（以下両者
を併せて多塩基酸で代表する）と多価アルコール類とを
定法により反応させて得られるものであって、その分子
量は１０００−４０００、好ましくは１５００−２５０
０である。The unsaturated polyester resin used as component (A) is prepared by reacting an α,β-unsaturated polybasic acid or its anhydride (hereinafter both will be collectively referred to as polybasic acid) and a polyhydric alcohol using a conventional method. The molecular weight is 1000-4000, preferably 1500-250.
It is 0.
α、β−不飽和多塩基酸としては、例えばマレイン酸、
フマル酸あるいは無水マレイン酸等の不飽和ジカルボン
酸又はその無水物を挙げることができ、また多価アルコ
ール類としては例えばエチレングリコール、プロピレン
グリコール、ブタンジオール、ネオペンチルグリコール
、ヘキシレングリコール、ジエチレングリコール、ジプ
ロピレングリコール、グリセリン、水素化ビスフェノ−
ルＡ、２，２− ジ（４−ヒドロキシプロポキシフェニ
ル）プロパン、２，２−−ジ（４−ヒドロキシエトキシ
フェニール）プロパン等を挙げることができる。これら
成分の他に必要に応じて適宜例えばオルソフタル酸、そ
の無水物、イソフタル酸、テレフタル酸、アジピン酸、
コハク酸、テトラクロル無水フタル酸、ヘット酸等の飽
和多塩基醜を使用する事ができる。Examples of α,β-unsaturated polybasic acids include maleic acid,
Unsaturated dicarboxylic acids such as fumaric acid or maleic anhydride or their anhydrides can be mentioned, and examples of polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexylene glycol, diethylene glycol, and Propylene glycol, glycerin, hydrogenated bisphenol
2,2-di(4-hydroxypropoxyphenyl)propane, 2,2-di(4-hydroxyethoxyphenyl)propane, and the like. In addition to these ingredients, if necessary, for example, orthophthalic acid, its anhydride, isophthalic acid, terephthalic acid, adipic acid,
Saturated polybasic acids such as succinic acid, tetrachlorophthalic anhydride, and hetyl acid can be used.
本発明に於ける（Ｂ）重合性単量体としては、例えばス
チレン、ビニルトルエン、ｔ−ブチルスチレン、クロル
スチレン、ジビニルベンゼン、メチル（メタ）アクリレ
ート、メタ（メタ）アクリレート、酢酸ビニル、更にエ
チレングリコール、１．３又は１，４−ブタンジオール
、ネオペンチルグリコール等のジ（メタ）アクリレート
、トリメチロールプロパンのジまたはトリ（メタ）アク
リレート等が挙げられる。Examples of the polymerizable monomer (B) in the present invention include styrene, vinyltoluene, t-butylstyrene, chlorostyrene, divinylbenzene, methyl (meth)acrylate, meth (meth)acrylate, vinyl acetate, and ethylene Examples include di(meth)acrylates such as glycol, 1.3- or 1,4-butanediol, and neopentyl glycol, and di- or tri(meth)acrylates of trimethylolpropane.
これらの重合性単量体は１種または２種以上混合して用
いられる。These polymerizable monomers may be used alone or in combination of two or more.
本発明に於ける（Ｃ）其の他添加剤としては促進剤、発
熱抑制剤、硬化剤、揺変剤、揺変助剤、減粘剤、増粘剤
、着色剤、脱泡剤、空乾剤等の様な物であり必要により
適宜添加する物である。(C) Other additives in the present invention include accelerators, heat generation suppressants, curing agents, thixotropic agents, thixotropic aids, thinners, thickeners, colorants, defoaming agents, and It is something like a drying agent and is added as needed.
本発明の不飽和ポリエステル樹脂中の不飽和ポリエステ
ルと重合性単量体との混合割合は前者４０−８０重量％
に対して、後者２０−６０重量％の範囲で其の他添加剤
とあわせて総量が１００重量部として用いられる。The mixing ratio of the unsaturated polyester and the polymerizable monomer in the unsaturated polyester resin of the present invention is 40-80% by weight of the former.
On the other hand, the latter is used in a range of 20-60% by weight together with other additives for a total of 100 parts by weight.
不飽和ポリエステルの量が４０重量部未満の時は構造物
として十分な強度かえられず、又８０重量部を越る場合
は、粘度が高くなったり、作業性が悪化する。If the amount of unsaturated polyester is less than 40 parts by weight, the structure will not have sufficient strength, and if it exceeds 80 parts by weight, the viscosity will increase and workability will deteriorate.
不飽和ポリエステル樹脂に対するグリシジルメタクリレ
ートの添加量は不飽和多塩基酸と飽和多塩基酸と多価ア
ルコールとをエステル化して得られる不飽和ポリエステ
ルのスチレンモノマー溶液１００部に対して、グリシジ
ルメタクリレートは０．１−１０ 重量部添加するが、
好ましくは１〜５重量部である。The amount of glycidyl methacrylate added to the unsaturated polyester resin is 0.0 parts per 100 parts of the styrene monomer solution of the unsaturated polyester obtained by esterifying an unsaturated polybasic acid, a saturated polybasic acid, and a polyhydric alcohol. Add 1-10 parts by weight,
Preferably it is 1 to 5 parts by weight.
グリシジルメタクリレートの添加方法は、不飽和ポリエ
ステルを製造する時点で添加しておき樹脂組成物として
使用してもよいが、グリシジルメタクリレートを添加し
ない不飽和ポリエステルを製造しておき実際に使用時に
グリシジルメタクリレートをこれに添加して使用しても
よい。この場合も多大の効果がある事も実験の結果判明
している。Glycidyl methacrylate can be added at the time of manufacturing unsaturated polyester and used as a resin composition, but unsaturated polyester without glycidyl methacrylate is manufactured and glycidyl methacrylate is added at the time of actual use. It may be used by adding it to this. Experiments have also shown that this method has a great effect.
本発明で、不飽和ポリエステル樹脂を製造する時点に於
いて添加剤としてグリシジルメタクリレートを使用する
のであるが、このグリシジルメタクリレートを不飽和ポ
リエステル樹脂に添加することによって、繊維強化不飽
和ポリエステル樹脂の耐水性、耐熱水性、耐煮沸性、耐
薬品性が改良される事を見出したのである。In the present invention, glycidyl methacrylate is used as an additive at the time of manufacturing the unsaturated polyester resin, and by adding this glycidyl methacrylate to the unsaturated polyester resin, the water resistance of the fiber-reinforced unsaturated polyester resin can be improved. They found that hot water resistance, boiling resistance, and chemical resistance were improved.
次に本発明に於いて使用する繊維強化材の一部について
説明する。Next, some of the fiber reinforcement materials used in the present invention will be explained.
ａ、ガラス繊維
一般にガラスと呼ばれている物はシリカ（Ｓｉｎ、）を
主成分としてこれに各種の金属酸化物、炭酸塩を加えて
溶融、急冷した無定形物であるが、不飽和ポリエステル
複合材に用いられるガラス繊維は、Ｎａ２Ｏやに２０
のアルカリ分を含まない無アルカリガラスを繊維化した
ものがほとんどである。形態としてはチョツプドストラ
ンド、チョツプドストランドマット、ロービング、クロ
ス等があり各種ガラスメーカーから発売されている。a.Glass fiber What is generally called glass is an amorphous material made by adding various metal oxides and carbonates to silica (Sin) as its main component, melting and quenching it, but unsaturated polyester composite The glass fiber used for the material is Na2O20
Most of the fibers are made from alkali-free glass that does not contain any alkaline content. It comes in various forms such as chopped strand, chopped strand mat, roving, and cloth, and is sold by various glass manufacturers.
ｂ、カーボン繊維
レーヨン、ポリアクリロニトリル等の有機繊維を数段階
の温度で炭化焼成して製造する。例えばポリアクリロニ
トリル系繊維の場合、２００３００℃で１０−２０時間
、空気中で耐炎化した後７００−１８００℃で炭素化し
、更に２５００−３０００℃で処理して黒鉛化する。途
中耐炎化工程で繊維を延伸することにより黒鉛結晶の軸
方向への配向が達成される。カーボン繊維は国内ではト
ーレ、県別化学、東邦レーヨン等各社で発売されている
。b. Manufactured by carbonizing and firing organic fibers such as carbon fiber rayon and polyacrylonitrile at several temperatures. For example, in the case of polyacrylonitrile fibers, it is flame-resistant at 200-300°C for 10-20 hours in air, carbonized at 700-1800°C, and further treated at 2500-3000°C to graphitize. The graphite crystals are oriented in the axial direction by stretching the fibers during the flameproofing step. Carbon fiber is sold domestically by Toray, Kenbetsu Kagaku, Toho Rayon, and other companies.
Ｃ，アラミド繊維
ポリ−ｐ−フェニレンテレフタルアミド、 ポリベンズ
アミド等を主成分とした芳香族ポリアミド系繊維であり
引張り特性と耐熱性が優れ、又比重も小さい。C, aramid fiber This is an aromatic polyamide fiber mainly composed of poly-p-phenylene terephthalamide, polybenzamide, etc., and has excellent tensile properties and heat resistance, and also has a small specific gravity.
デュポン、加化成、帝人等各社で発売されている。It is sold by companies such as DuPont, Kakasei, and Teijin.
本発明に於いて使用する強化材はガラス繊維、カーボン
繊維、アラミド繊維、ボロン繊維、金属繊維、有機繊維
等の１種以上でありこれによって繊維強化不飽和ポリエ
ステル複合材としての効果をあげられる。この際不飽和
ポリエステル樹脂と強化材の混合比は重量比で不飽和ポ
リエステル樹脂１００に対して強化材５−２００である
。The reinforcing material used in the present invention is one or more of glass fibers, carbon fibers, aramid fibers, boron fibers, metal fibers, organic fibers, etc., and this can provide an effect as a fiber-reinforced unsaturated polyester composite material. At this time, the mixing ratio of the unsaturated polyester resin and the reinforcing material is 100 parts of the unsaturated polyester resin to 5 to 200 parts of the reinforcing material by weight.
（実施例）
イソフタル酸 １７．７重量部フマル酸
８．３重量部無水マレイン酸
５．８重量部ネオペンチルグリコール ２０
．３重量部水素添加ビスフェノールＡ ４７．９重量
部からなる配合組成物を不活性ガス下で通常の反応でエ
ステル化して得られた不飽和ポリエステルを６０重量部
とし、これをスチレンモノマー４０重量部に溶解し、そ
の際に添加剤として促進剤０．５重量部、 グリシジル
メタクリレート３重量部を添加した。(Example) Isophthalic acid 17.7 parts by weight Fumaric acid
8.3 parts by weight maleic anhydride
5.8 parts by weight neopentyl glycol 20
．． A blended composition consisting of 3 parts by weight of hydrogenated bisphenol A and 47.9 parts by weight was esterified in a normal reaction under an inert gas to obtain 60 parts by weight of unsaturated polyester, and this was added to 40 parts by weight of styrene monomer. The mixture was dissolved, and at that time, 0.5 parts by weight of accelerator and 3 parts by weight of glycidyl methacrylate were added as additives.
このようにして得られた不飽和ポリエステルの１００重
量部に対して有機過酸化物Ｑ、５−２．０重量部を添加
し不飽和ポリエステル樹脂組成物として４５０番手のチ
ョツプドストランドマットを３層、厚さ３ｍｎにハンド
レイアップ法で積層した。5 to 2.0 parts by weight of organic peroxide Q was added to 100 parts by weight of the unsaturated polyester thus obtained, and 3 parts of chopped strand mat of #450 was prepared as an unsaturated polyester resin composition. The layers were laminated to a thickness of 3 mm using a hand lay-up method.
この積層板を常温で十分硬化させたのち、１０５℃の電
気式熱処理雰囲気炉に２時間入れて後硬化とした。After this laminate was sufficiently cured at room temperature, it was placed in an electric heat treatment atmosphere furnace at 105° C. for 2 hours for post-curing.
こうしてできた積層板は９８℃の熱湯中での３００時間
に渡る片面浸漬煮沸試験をしたあとも、又１００℃の熱
湯中での３００時間に渡る全面浸漬煮沸試験をした後も
いずれもふくれ、クラックは認められずガラス白化もわ
ずかな白化にとどまった・
（比較例）
イソフタル酸 １７．７重量部フマル酸
８．３重量部無水マレイン酸
５．８重量部ネオペンチルグリコール ２０．
３重量部水素添加ビスフェノールＡ ４７．９重量部
からなる配合組成物を不活性ガス下で通常の反応でエス
テル化して得られた不飽和ポリエステルを６０重量部と
し、これをスチレンモノマー４０重量部に溶解し、その
際に添加材として促進剤０．５重量部を添加した。The laminates made in this way did not swell even after a single side immersion boiling test in 98°C hot water for 300 hours and a full 300 hour full immersion boiling test in 100°C boiling water. No cracks were observed and glass whitening was only slight (comparative example) Isophthalic acid 17.7 parts by weight Fumaric acid
8.3 parts by weight maleic anhydride
5.8 parts by weight neopentyl glycol 20.
A blended composition consisting of 3 parts by weight of hydrogenated bisphenol A and 47.9 parts by weight was esterified in a normal reaction under an inert gas to obtain 60 parts by weight of unsaturated polyester, and this was added to 40 parts by weight of styrene monomer. The mixture was dissolved, and at that time, 0.5 parts by weight of accelerator was added as an additive.
このようにして得られた不飽和ポリエステルの１００重
量部に対して有機過酸化物Ｑ、５−２．０重量部を添加
し不飽和ポリエステル樹脂組成物として４５０番手のチ
ョツプドストランドマットを３層、厚さ３■にハンドレ
イアップ法で積層した。5 to 2.0 parts by weight of organic peroxide Q was added to 100 parts by weight of the unsaturated polyester thus obtained, and 3 parts of chopped strand mat of #450 was prepared as an unsaturated polyester resin composition. The layers were laminated to a thickness of 3 cm using the hand lay-up method.
この積層板を常温で十分硬化させたのち、１０５℃の電
気式熱処理雰囲気炉に２時間入れて後硬化とした。After this laminate was sufficiently cured at room temperature, it was placed in an electric heat treatment atmosphere furnace at 105° C. for 2 hours for post-curing.
こうしてできた積層板を９８℃の熱湯中での３００時間
に渡る片面浸漬煮沸試験又は１００℃の熱湯中での３０
０時間に渡る全面浸漬煮沸試験をしたところ全面浸漬煮
沸試験では１００時間で一部ガラス白化とふくれが現わ
れ始め、３００時間では更にその程度が進んだ。又片面
浸漬煮沸試験でも３００時間ではガラス白化やふくれが
全面に強く現われた。The thus-produced laminate was subjected to a one-sided immersion boiling test for 300 hours in boiling water at 98°C or a boiling test for 300 hours in boiling water at 100°C.
When the entire surface was immersed in a boiling test for 0 hours, some glass whitening and blistering started to appear after 100 hours, and the degree of blistering had further progressed after 300 hours. Also, in the single-sided immersion and boiling test, glass whitening and blistering appeared strongly on the entire surface after 300 hours.
（発明の効果）
本発明による不飽和ポリエステル樹脂組成物は減粘性が
良く高含浸性でもあるので機械部品、電気器具、輸送機
器、建材、家具、食器、玩具、スポーツ用品、タンク、
容器等広範囲に用いる事により従来の繊維強化不飽和ポ
リエステル複合材では果たせなかった高強度に加え耐水
性、耐熱水性、耐煮沸性、耐薬品性の優れた性質を付与
する事が可能になり更に表面の透明ゲルコート、中間の
透明積層用樹脂を用いた成形物の外観上の価値の保持を
可能とした。(Effects of the Invention) The unsaturated polyester resin composition according to the present invention has good viscosity reducing properties and high impregnation properties, so it can be used in mechanical parts, electrical appliances, transportation equipment, building materials, furniture, tableware, toys, sporting goods, tanks, etc.
By using it in a wide range of applications such as containers, it is possible to provide excellent properties such as water resistance, hot water resistance, boiling resistance, and chemical resistance in addition to high strength that was not possible with conventional fiber-reinforced unsaturated polyester composites. By using a transparent gel coat on the surface and a transparent laminating resin in the middle, it is possible to maintain the appearance value of the molded product.
Claims (3)
００重量部に （Ｄ）グリシジルメタクリレート０．１−１０重量部を
配合してなる繊維強化プラスチ ック用不飽和ポリエステル樹脂組成物(1) Unsaturated polyester resin 1 consisting of (A) 40-80% by weight of unsaturated polyester, (B) 20-60% by weight of polymerizable monomer, and (C) other additives
An unsaturated polyester resin composition for fiber-reinforced plastics comprising 0.1-10 parts by weight of (D) glycidyl methacrylate in 0.00 parts by weight.
酸、フマル酸のいずれか１種以上の不飽和多塩基酸と又
は更にこれに無水フタル酸、イソフタル酸、テレフタル
酸、アジピン酸、コハク酸、テトラクロル無水フタル酸
、ヘット酸等の様ないずれか１種以上の飽和多塩基酸と
プロピレングリコール、エチレングリコール、ブタンジ
オール、ジプロピレングリコール、ジエチレングリコー
ル、グリセリン、ネオペンチルグリコール、ビスフェノ
ールＡのアルキレンオキシド付加体、水素化ビスフェノ
ール等の様な多価アルコールのいずれか１種以上とをエ
ステル化して得られる特許請求の範囲第１項記載の繊維
強化プラスチック用不飽和ポリエステル樹脂組成物(2) The unsaturated polyester is composed of one or more unsaturated polybasic acids such as maleic acid, maleic anhydride, and fumaric acid, or further combined with phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, succinic acid, and tetrachloride. alkylene oxide adducts of any one or more saturated polybasic acids such as phthalic anhydride, het acid, etc. and propylene glycol, ethylene glycol, butanediol, dipropylene glycol, diethylene glycol, glycerin, neopentyl glycol, bisphenol A; The unsaturated polyester resin composition for fiber-reinforced plastics according to claim 1 obtained by esterifying any one or more polyhydric alcohols such as hydrogenated bisphenol.
維、カーボン繊維、アラミド繊維、ボロン繊維、金属繊
維、有機繊維の様な強化材のいずれか１種以上を含浸し
て得られる繊維強化不飽和ポリエステル複合材(3) Fiber obtained by impregnating any one or more of reinforcing materials such as glass fiber, carbon fiber, aramid fiber, boron fiber, metal fiber, and organic fiber with the resin described in (1) and (2) above. Reinforced unsaturated polyester composite
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29368788A JPH02142847A (en) | 1988-11-22 | 1988-11-22 | Unsaturated polyester resin composition for fiber-reinforced plastic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29368788A JPH02142847A (en) | 1988-11-22 | 1988-11-22 | Unsaturated polyester resin composition for fiber-reinforced plastic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02142847A true JPH02142847A (en) | 1990-05-31 |
Family
ID=17797934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29368788A Pending JPH02142847A (en) | 1988-11-22 | 1988-11-22 | Unsaturated polyester resin composition for fiber-reinforced plastic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02142847A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100433339B1 (en) * | 2001-08-22 | 2004-05-28 | 애경화학 주식회사 | Epoxy Modified unsaturated polyester resin for lining adhesive of iron plate and steel and process for preparing the same |
-
1988
- 1988-11-22 JP JP29368788A patent/JPH02142847A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100433339B1 (en) * | 2001-08-22 | 2004-05-28 | 애경화학 주식회사 | Epoxy Modified unsaturated polyester resin for lining adhesive of iron plate and steel and process for preparing the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5900311A (en) | Thermosetting polyester composites prepared via vacuum-assisted technique with smooth surface appearance | |
| JPH09241496A (en) | Unsaturated polyester resin composition and sheet-like molding material | |
| JPH09227665A (en) | Heat-resistant unsaturated polyester resin composition, heat-resistant fiber reinforced composite material, and heat-resistant molding comprising the same | |
| JPH02142847A (en) | Unsaturated polyester resin composition for fiber-reinforced plastic | |
| US3432458A (en) | Thickened polymerizable unsaturated polyester resin compositions and fibrous substances impregnated therewith | |
| Cassis et al. | Polyester and vinyl ester resins | |
| JPH0940727A (en) | Cured thermosetting resin obtained from unsaturated polyether ester resin and glass-reinforced composite material | |
| JP2005054068A (en) | Unsaturated polyester resin, unsaturated polyester resin composite, and cured product of the resin composite | |
| JPS6099158A (en) | Resin composition | |
| JPH01234434A (en) | Bulk molding compound composition and molded article produced therefrom | |
| JP3294809B2 (en) | Lightweight laminate | |
| Mohammad | Synthesis, characterization and properties of the new unsaturated polyester resins for composite applications | |
| KR101155073B1 (en) | Manufacturing method of fiber glass reinforced plastics material using the unsaturated polyester resin comprising carbon nanotube | |
| JPS59176313A (en) | Composite reinforced unsaturated polyester resin molding | |
| JPH1036459A (en) | Unsaturated polyester resin composition | |
| US3011994A (en) | Polyesters with improved adhesion to glass | |
| KR20010051002A (en) | Sheet molding materials for obtaining molded articles having a high degree of transparency and molded articles obtained therefrom | |
| JP2000143958A (en) | Unsaturated polyester resin for flexible frp sheet and its use | |
| JP2003212979A (en) | Unsaturated polyester resin, unsaturated polyester resin composition, and thermosetting molding material using the composition | |
| JPS6351451A (en) | Unsaturated polyester resin composition | |
| JPS61166850A (en) | Unsaturated polyester resin composition | |
| JPH04198209A (en) | Dicyclopentadiene-modified unsaturated polyester composition and its use | |
| JPS6227103B2 (en) | ||
| JPS6311136B2 (en) | ||
| JP3857224B2 (en) | Mat binder |