JPH0733404B2 - Molding composition and method for producing molded article - Google Patents
Molding composition and method for producing molded articleInfo
- Publication number
- JPH0733404B2 JPH0733404B2 JP1264322A JP26432289A JPH0733404B2 JP H0733404 B2 JPH0733404 B2 JP H0733404B2 JP 1264322 A JP1264322 A JP 1264322A JP 26432289 A JP26432289 A JP 26432289A JP H0733404 B2 JPH0733404 B2 JP H0733404B2
- Authority
- JP
- Japan
- Prior art keywords
- composition
- present
- meth
- integers
- parts
- 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 - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 32
- 238000000465 moulding Methods 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000000178 monomer Substances 0.000 claims description 17
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 125000002723 alicyclic group Chemical group 0.000 claims description 9
- 239000003505 polymerization initiator Substances 0.000 claims description 5
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 238000013007 heat curing Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- -1 vinyl propio Chemical class 0.000 description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- 238000001723 curing Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000005251 gamma ray Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- MXWDONCKZRKQMP-UHFFFAOYSA-J sulfanide triacetyloxystannanylium Chemical compound C(C)(=O)[O-].S[Sn+3].C(C)(=O)[O-].C(C)(=O)[O-] MXWDONCKZRKQMP-UHFFFAOYSA-J 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-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
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical class C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 210000001217 buttock Anatomy 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 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 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、成形用組成物および成形体の製造法に関す
る。TECHNICAL FIELD The present invention relates to a molding composition and a method for producing a molded product.
［従来の技術］ 従来、塩化ビニル系樹脂とトリメチロールプロパントリ
メタクリレート、ネオペンチルジメタクリレートなどの
メタクリル酸エステル系単量体とからなる組成物が知ら
れている。[Prior Art] Conventionally, a composition comprising a vinyl chloride resin and a methacrylic ester monomer such as trimethylolpropane trimethacrylate or neopentyl dimethacrylate has been known.
［発明が解決しようとする課題］ しかし、従来のものでは、高弾性率、高強度を有する硬
化物は得られなっかた。[Problems to be Solved by the Invention] However, in the conventional case, a cured product having a high elastic modulus and a high strength has not been obtained.
［課題を解決するための手段］ 本発明者らは、高弾性率、高強度を有する硬化物が得ら
れる組成物および製造法を鋭意検討した結果、本発明に
到達した。[Means for Solving the Problems] The present inventors have arrived at the present invention as a result of earnestly examining a composition and a production method capable of obtaining a cured product having a high elastic modulus and a high strength.
すなわち、本発明は、塩化ビニル系樹脂（Ａ）、脂環構
造を有する多官能重合性単量体を含む重合性単量体
（Ｂ）および必要により重合開始剤（Ｃ）からなる成形
用組成物および流動性をなくした組成物、熱および／ま
たは放射線照射により硬化した成形体の製造法である。That is, the present invention is a molding composition comprising a vinyl chloride resin (A), a polymerizable monomer (B) containing a polyfunctional polymerizable monomer having an alicyclic structure, and optionally a polymerization initiator (C). It is a method for producing a molded article which is cured by irradiation with heat and / or radiation, and a composition having a fluidity and a fluidity.
塩化ビニル系樹脂（Ａ）としては塩化ビニル単独重合
体、または塩化ビニルと他のビニルモノマー、たとえ
ば、酢酸ビニル、塩化ビニリデン、アクリル酸、メタア
クリル酸、メタクリル酸メチル、アクリル酸ブチルおよ
びビニルプロピオネートなどの不飽和単量体との共重合
体およびそれらの重合体の後塩素化物などがあげられ
る。特に好ましくは、塩化ビニル単独重合体および塩化
ビニルの含量が70重量％以上の共重合体である。The vinyl chloride resin (A) is a vinyl chloride homopolymer, or vinyl chloride and other vinyl monomers such as vinyl acetate, vinylidene chloride, acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate and vinyl propio. Examples thereof include copolymers with unsaturated monomers such as nates and post-chlorinated products of those polymers. Particularly preferred are vinyl chloride homopolymers and copolymers having a vinyl chloride content of 70% by weight or more.
塩化ビニル系樹脂の重合度は、特に限定されないが、通
常300〜10000、こましくは500〜6000である。The degree of polymerization of the vinyl chloride resin is not particularly limited, but is usually 300 to 10000, preferably 500 to 6000.
本発明における脂環構造を有する多官能重合性単量体は
特に限定されないが、たとえば、一般式（１）、（２）
および（３）に示される単量体があげられる。The polyfunctional polymerizable monomer having an alicyclic structure in the present invention is not particularly limited, but for example, general formulas (1) and (2)
And the monomers shown in (3).
（式中、R1,R2,R3は、水素原子またはメチル基、Ａはエ
チレン基またはプロピレン基であり、ｐ、ｑは０〜10の
整数、ｍ、ｎは０〜２の整数、ｘ、ｙは０〜３の整数で
ある。） 一般式（１）、（２）および（３）において、ｐ、ｑは
好ましくは０〜５の整数、ｍ、ｎは好ましくは０〜１の
整数、ｘ、ｙは好ましくは０〜２の整数である。 (In the formula, R 1 , R 2 and R 3 are a hydrogen atom or a methyl group, A is an ethylene group or a propylene group, p and q are integers of 0 to 10, m and n are integers of 0 to 2, and x and y are integers of 0 to 3.) In the general formulas (1), (2) and (3), p and q are preferably integers of 0 to 5 and m and n are preferably 0 to 1. Integers, x and y are preferably integers of 0-2.
また、イソホロンジイソシアネート、ジシクロヘキシル
ジイソシアネートなどの脂環式ポリイソシアネートと水
酸基含有（メタ）アクリレート［たとえば、（メタ）ア
クリル酸２−ヒドロキシエチルなど］または（メタ）ア
クリル酸との反応物、イソホロンジアミン、ジシクロヘ
キシルジアミンなどの脂環式ポリアンと（メタ）アクリ
ル酸クロライドとの反応物も使用できる。Further, a reaction product of an alicyclic polyisocyanate such as isophorone diisocyanate or dicyclohexyl diisocyanate and a hydroxyl group-containing (meth) acrylate [for example, 2-hydroxyethyl (meth) acrylate] or (meth) acrylic acid, isophorone diamine, dicyclohexyl. A reaction product of an alicyclic polyan such as diamine and (meth) acrylic acid chloride can also be used.
特に好ましくは、一般式（１）で示される化合物とし
て、ビス［（メタ）アクリロイルオキシ］トリシクロ
［5,2,02.6］デカン（ｐ、ｍ、ｎ、ｑ、ｘ、ｙが０のも
の）、ビス［（メタ）アクリロイルオキシメチル］トリ
シクロ［5,2,02.6］デカン（ｐ、ｑ、ｘ、ｙが０で、
ｍ、ｎが１のもの）、一般式（２）で示される化合物と
して、ビス［（メタ）アクリロイルオキシ］テトラシク
ロ［4,4,0,12.5,17.10］ドデカン（ｐ、ｍ、ｎ、ｑが０
で、ｘが１のもの）、ビス［（メタ）アクリロイルオキ
シメチル］テトラシクロ［4,4,0,12.5,1,7.10］ドデカ
ン（ｐ、ｑが０で、ｍ、ｎ、ｘが１のもの）、一般式
（３）で示される化合物として、水素化ビスフェノール
Ａのエチレンオキサイドおよび／またはプロピレンオキ
サイド付加物（ｐ、ｑは１〜３）の（メタ）アクリル酸
エステルである。Particularly preferably, as the compound represented by the general formula (1), bis [(meth) acryloyloxy] tricyclo [5,2,0 2.6 ] decane (p, m, n, q, x, y are 0) , Bis [(meth) acryloyloxymethyl] tricyclo [5,2,0 2.6 ] decane (p, q, x, y are 0,
m and n are 1) and the compound represented by the general formula (2) is bis [(meth) acryloyloxy] tetracyclo [4,4,0,1 2.5 , 1 7.10 ] dodecane (p, m, n, q is 0
And x is 1), bis [(meth) acryloyloxymethyl] tetracyclo [4,4,0,1 2.5 , 1, 7.10 ] dodecane (p and q are 0, m, n and x are 1) And a compound represented by the general formula (3) is a (meth) acrylic acid ester of hydrogenated bisphenol A ethylene oxide and / or propylene oxide adduct (p and q are 1 to 3).
本発明において、必要により脂環構造を有する多官能重
合性単量体以外に公知の重合性単量体たとえば単官能お
よび／または多官能（メタ）アクリル酸エステルを併用
することができる。なお、（メタ）アクリル酸エステル
とは、アクリル酸エステルおよび／またはメタクリル酸
エステルのことを表す（以下も同様）。In the present invention, a known polymerizable monomer such as a monofunctional and / or polyfunctional (meth) acrylic acid ester can be used in combination with the polyfunctional polymerizable monomer having an alicyclic structure, if necessary. In addition, a (meth) acrylic acid ester represents an acrylic acid ester and / or a methacrylic acid ester (same below).
単官能（メタ）アクリル酸エステルとしては、たとえ
ば、（メタ）アクリル酸２−エチルヘキシルおよび２−
エチルヘキサノール、フェノール、アルキル（アルキル
基の炭素数は通常１〜20）フェノールなどのアルキレン
オキサイド（たとえば、エチレンオキサイド、プロピレ
ンオキサイドなど）付加物（以下、AOAと略す）の（メ
タ）アクリル酸エステルなどがあげられる。多官能（メ
タ）アクリル酸エステルとしては、たとえば、1,4−ブ
チレングリコール、ネオペンチルグリコール、1,6−ヘ
キサングリコール、トリメチロールプロパン、ペンタエ
リスリトール、ジペンタエリスリトールおよびこれらの
AOAの多官能（メタ）アクリル酸エステルがあげられ
る。Examples of monofunctional (meth) acrylic acid esters include 2-ethylhexyl (meth) acrylic acid and 2-ethylhexyl (meth) acrylic acid.
(Meth) acrylic acid ester of alkylene oxide (for example, ethylene oxide, propylene oxide, etc.) adduct (hereinafter abbreviated as AOA) such as ethylhexanol, phenol, and alkyl (the carbon number of the alkyl group is usually 1 to 20) Can be given. Examples of the polyfunctional (meth) acrylic acid ester include 1,4-butylene glycol, neopentyl glycol, 1,6-hexane glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and their derivatives.
A polyfunctional (meth) acrylic acid ester of AOA can be mentioned.
（Ｂ）中の脂環構造を有する多官能重合性単量体の量は
通常10重量％以上、好ましくは20重量％以上である。The amount of the polyfunctional polymerizable monomer having an alicyclic structure in (B) is usually 10% by weight or more, preferably 20% by weight or more.
本発明において、必要により重合開始剤（Ｃ）たとえ
ば、公知の熱および／または光重合開始剤を添加するこ
とができる。In the present invention, a polymerization initiator (C), for example, a known heat and / or photopolymerization initiator can be added, if necessary.
熱重合開始剤としては、たとえば、ベンゾイルパーオキ
サイド、ジクミルパーオキサイド、ｔ−ブチルパーオキ
シベンゾエート、メチルエチルケトンパーオキサイドお
よびアゾビスイソブチロニトリルなどがあげられる。ま
た、光重合開始剤としては、たとえば、ベンゾインアル
キルエーテル、ベンジルケタール、１−ヒドキシシクロ
ヘキシルフェニルケトン、２−ヒドロキシ−２−メチル
−１−フェニルプロパン−１−オン、ベンゾフェノンな
どがあげられる。Examples of the thermal polymerization initiator include benzoyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, methyl ethyl ketone peroxide and azobisisobutyronitrile. Examples of the photopolymerization initiator include benzoin alkyl ether, benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzophenone.
なお、熱重合開始剤を使用する場合は、必要によりナフ
テン酸コバルトなどの金属石鹸、ジメチルアニリンなど
の第３級アミンなどの公知の促進剤を併用することがで
きる。When a thermal polymerization initiator is used, a known accelerator such as a metal soap such as cobalt naphthenate or a tertiary amine such as dimethylaniline can be used if necessary.
本発明において、（Ａ）と（Ｂ）の重量割合は、通常2
0:80〜80:20、好ましくは、30:70〜70:30である。In the present invention, the weight ratio of (A) and (B) is usually 2
It is 0:80 to 80:20, preferably 30:70 to 70:30.
（Ａ）が20未満では、硬化して得られた成形体が脆くな
り、80を越えると得られた成形体の弾性率および強度が
低下する。If (A) is less than 20, the molded product obtained by curing will become brittle, and if it exceeds 80, the elastic modulus and strength of the resulting molded product will decrease.
（Ｃ）の添加量は、（Ａ）と（Ｂ）の合計重量100部に
対して通常０〜10部、好ましくは、0.05〜５部である。
ただし、紫外線を除く放射線（たとえば、電子線、中性
子線、γ線など）照射により硬化させる場合は、開始剤
の添加は通常不要である。The amount of (C) added is usually 0 to 10 parts, preferably 0.05 to 5 parts, based on 100 parts by weight of the total of (A) and (B).
However, in the case of curing by irradiation with radiation other than ultraviolet rays (for example, electron beam, neutron beam, γ ray, etc.), addition of an initiator is usually unnecessary.
また、熱可塑性樹脂たとえば塩化ビニル系樹脂の公知の
添加剤たとえば安定剤、充填剤、着色剤、界面活性剤、
増粘剤、発泡剤などを添加することができる。塩化ビニ
ル系樹脂用の通常の可塑剤も添加できるが添加量が多く
なると高弾性率の硬化体が得られにくくなるため、添加
量は熱可塑性樹脂たとえばポリ塩化ビニル系樹脂100重
量部に対して通常20重量部以下、好ましくは10重量部以
下である。Further, known additives such as stabilizers, fillers, colorants, surfactants for thermoplastic resins such as vinyl chloride resins,
Thickeners, foaming agents and the like can be added. Ordinary plasticizers for vinyl chloride resins can also be added, but if the amount added is too large, it becomes difficult to obtain a cured product with a high elastic modulus, so the amount added is based on 100 parts by weight of a thermoplastic resin such as polyvinyl chloride resin. It is usually 20 parts by weight or less, preferably 10 parts by weight or less.
本発明の組成物は、実質的に重合を起こさせずに加熱す
ることにより可塑化して常温で流動性をなくした組成物
を得ることができる。加熱の条件は、通常40〜120℃、
好ましくは50〜90℃である。The composition of the present invention can be plasticized by heating without causing polymerization substantially to obtain a composition having no fluidity at room temperature. Heating conditions are usually 40-120 ℃,
It is preferably 50 to 90 ° C.
流動性をなくした組成物は、真空成形、プレス成形など
で成形することができる。The composition having no fluidity can be molded by vacuum molding, press molding or the like.
本発明の組成物は、熱および／または放射線照射により
硬化し成形体とすることができる。なお、本発明におけ
る放射線とは、電子線、中性子線、γ線、紫外線などを
表す。The composition of the present invention can be cured by heat and / or irradiation to give a molded product. In addition, the radiation in the present invention represents an electron beam, a neutron beam, a γ ray, an ultraviolet ray and the like.
本発明の組成物を用いて成形体を製造する方法は特に限
定されない。たとえば、組成物を型内に常圧で、または
必要により加圧して、または型内を減圧にして注入し硬
化させる方法、組成物を所望の形状（たとえばシート
状）にした後、または同時に加熱により可塑化して流動
性をなくした組成物を金型などで成形した後、硬化させ
る方法などがあげられる。具体例としては、注型成形、
射出成形、リアクション・インジェクション・モールデ
ィング、レジン・インジェクション、圧縮成形、押出成
形、トランスファー成形などがあげられる。The method for producing a molded product using the composition of the present invention is not particularly limited. For example, a method of injecting the composition into the mold at normal pressure, or optionally under pressure, or reducing the pressure in the mold to cure the composition, heating the composition into a desired shape (for example, a sheet), or simultaneously heating the composition. Examples of the method include a method of molding a composition which has been plasticized to lose fluidity by a mold or the like and then cured. As a specific example, cast molding,
Examples include injection molding, reaction injection molding, resin injection, compression molding, extrusion molding and transfer molding.
加熱硬化する場合の温度は、通常40〜180℃、好ましく
は50〜160℃であるが、組成物を可塑化したのち硬化す
る場合は、80〜180℃、好ましくは100〜160℃である。
放射線たとえば電子線照射により硬化する場合の照射線
量は、通常0.1〜50Mrad、好ましくは0.5〜20Mradであ
る。The temperature in the case of heat curing is usually 40 to 180 ° C, preferably 50 to 160 ° C, but is 80 to 180 ° C, preferably 100 to 160 ° C in the case of curing after plasticizing the composition.
The irradiation dose for curing by radiation such as electron beam irradiation is usually 0.1 to 50 Mrad, preferably 0.5 to 20 Mrad.
［実施例］ 以下に本発明を実施例により説明するが、本発明はこれ
に限定されるものではない。実施例中の部は重量部を示
す。[Examples] The present invention is described below by referring to Examples, but the present invention is not limited thereto. Parts in the examples indicate parts by weight.
実施例１ 塩化ビニル樹脂（重合度1650） 60部 ビス（メタクリロイルオキシメチル）トリシクロ［5,2,
02.6］デカン 40部 ｔ−ブチルパーオキシベゾエート 0.4部 メルカプト錫アセテート（安定剤） 0.6部 を配合し、減圧脱泡し本発明の組成物を得た。２枚のガ
ラス板で作った3mmの間隙を有する型に注入し、130℃、
５分間加熱硬化させ本発明の成形体を得た。Example 1 Vinyl chloride resin (degree of polymerization: 1650) 60 parts Bis (methacryloyloxymethyl) tricyclo [5,2,
[ 2.6 ] Decane 40 parts t-butyl peroxybezoate 0.4 part Mercaptotin acetate (stabilizer) 0.6 part was mixed and defoamed under reduced pressure to obtain a composition of the present invention. Pour into a mold made of two glass plates with a gap of 3mm, 130 ℃,
It was heated and cured for 5 minutes to obtain the molded product of the present invention.
実施例２ 塩化ビニル樹脂（重合体3500） 50部 ビス（アクリロイルオキシメチル）トリシクロ［5,2,0
2.6］デカン 50部 ｔ−ブチルパーオキシベンゾエート 0.5部 メルカプト錫アセテート 0.5部 を実施例１と同様にして本発明の組成物を得た。この組
成物を２枚のガラス板で作った3mmの間隙を有する型に
注入し、80℃、10分間加熱し流動性のない組成物を得
た。この組成物を130℃、５分間プレス成形して本発明
の成形体を得た。Example 2 Vinyl chloride resin (polymer 3500) 50 parts Bis (acryloyloxymethyl) tricyclo [5,2,0
2.6 ] Decane 50 parts t-Butylperoxybenzoate 0.5 parts Mercaptotin acetate 0.5 parts was treated in the same manner as in Example 1 to obtain a composition of the present invention. This composition was poured into a mold made of two glass plates and having a gap of 3 mm, and heated at 80 ° C. for 10 minutes to obtain a composition having no fluidity. This composition was press-molded at 130 ° C. for 5 minutes to obtain a molded product of the present invention.
実施例３ 実施例１のビス（メタクリロイルオキシメチル）トリシ
クロ［5,2,02.6］デカンのかわりにビス［（メタ）アク
リロイルオキシメチル］テトラシクロ［4,4,0,12.5,1,
7.10］ドデカンを用いて実施例１と同様にして本発明の
組成物および成形体を得た。Example 3 Instead of bis (methacryloyloxymethyl) tricyclo [5,2,0 2.6 ] decane of Example 1, bis [(meth) acryloyloxymethyl] tetracyclo [4,4,0,1 2.5 , 1,
7.10 ] Dodecane was used in the same manner as in Example 1 to obtain a composition and a molded product of the present invention.
実施例４ 実施例２のビス（アクリロイルオキシメチル）トリシク
ロ［5,2,02.6］デカンのかわりにビス（アクリロイルオ
キシメチル）トリシクロ［5,2,02,6］デカン35部、トリ
メチロールプロパントリメタクリレート15部を用いて実
施例１と同様にして本発明の組成物および成形体を得
た。Example 4 Instead of bis (acryloyloxymethyl) tricyclo [5,2,0 2.6 ] decane of Example 2, 35 parts of bis (acryloyloxymethyl) tricyclo [5,2,0 2,6 ] decane, trimethylolpropane Using 15 parts of trimethacrylate, the composition of the present invention and a molded product were obtained in the same manner as in Example 1.
参考例１ 実施例１のビス（メタクリロイルオキシメチル）トリシ
クロ［5,2,02.6］デカンのかわりにネオペンチルグリコ
ールジメタクリレートを用いて実施例１と同様にして参
考用の組成物および成形体を得た。Reference Example 1 A reference composition and molded article were prepared in the same manner as in Example 1 except that neopentyl glycol dimethacrylate was used instead of bis (methacryloyloxymethyl) tricyclo [5,2,0 2.6 ] decane of Example 1. Obtained.
参考例２ 実施例２のビス（アクリロイルオキシメチル）トリシク
ロ［5,2,02.6］デカンのかわりにトリメチロールプロパ
ントリメタクリレートを用いて実施例１と同様にして参
考用の組成物および成形体を得た。Reference Example 2 Using trimethylolpropane trimethacrylate instead of bis (acryloyloxymethyl) tricyclo [5,2,0 2.6 ] decane of Example 2, a reference composition and molded article were prepared in the same manner as in Example 1. Obtained.
試験例１ 実施例１〜４および参考例１、２で得られた成形体の曲
げ弾性率および曲げ強度を測定した。測定結果を表１に
示す。Test Example 1 The flexural modulus and flexural strength of the molded bodies obtained in Examples 1 to 4 and Reference Examples 1 and 2 were measured. The measurement results are shown in Table 1.
［発明の効果］ 本発明の組成物を用いて製造した成形体は、従来のもの
と比べて高弾性率および高強度を有する。具体的には、
曲げ弾性率、曲げ強度が優れている。 [Effect of the Invention] The molded product produced by using the composition of the present invention has a higher elastic modulus and a higher strength than the conventional one. In particular,
Excellent flexural modulus and flexural strength.
本発明の組成物から得られる成形体は高弾性率および高
強度を有しているため、事務用機器（タイプライター、
プリンター、複写機など）、家電機器（テレビ、ステレ
オ、VTRなど）などの部品、ハウジングなど、電機機器
（各種絶縁用パネル、スイッチボックス、支持具類な
ど）、耐蝕機器（ポンプハウジング、タンク、防水パン
など）、輸送機器（フロントパネル、フェンダー、バン
パーなど）、農業機器などの部品他建材などに使用する
ことができる。Since the molded product obtained from the composition of the present invention has high elastic modulus and high strength, it can be used for office equipment (typewriter,
Printers, copiers, etc., parts for home appliances (TVs, stereos, VTRs, etc.), housings, electrical equipment (various insulation panels, switch boxes, supports, etc.), corrosion-resistant equipment (pump housings, tanks, waterproofing) It can be used for parts such as bread), transportation equipment (front panel, fender, bumper, etc.), agricultural equipment, and other building materials.
なお、本発明における脂環構造を有する多官能重合性単
量体は、塩化ビニル系樹脂の改質剤として用いれば、耐
熱性、強度などを向上させることができる。The polyfunctional polymerizable monomer having an alicyclic structure in the present invention can improve heat resistance, strength and the like when used as a modifier of a vinyl chloride resin.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭53−130896（ＪＰ，Ａ) 特開 平２−105155（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-53-130896 (JP, A) JP-A-2-105155 (JP, A)
Claims (4)
る多官能重合性単量体を含む重合性単量体（Ｂ）および
必要により重合開始剤（Ｃ）からなる成形用組成物。1. A molding composition comprising a vinyl chloride resin (A), a polymerizable monomer (B) containing a polyfunctional polymerizable monomer having an alicyclic structure, and optionally a polymerization initiator (C). .
項１記載の組成物。 ［ただし、一般式（１）、（２）および（３）におい
て、R1、R2およびR3は水素原子またはメチル基、Ａはエ
チレン基またはプロピレン基、ｐとｑは０〜10の整数、
ｍとｎは０〜２の整数、ｘとｙは０〜３の整数であ
る。］2. A polyfunctional polymerizable monomer having an alicyclic structure is represented by the general formula (1). A monomer represented by the general formula (2) A monomer represented by the general formula (3) The composition according to claim 1, which is at least one monomer selected from the group consisting of: [However, in the general formulas (1), (2) and (3), R 1 , R 2 and R 3 are hydrogen atoms or methyl groups, A is an ethylene group or a propylene group, p and q are integers from 0 to 10] ,
m and n are integers of 0 to 2, and x and y are integers of 0 to 3. ]
１または２記載の組成物。3. The composition according to claim 1, which is made to lose fluidity by plasticizing.
熱硬化する成形体の製法。4. A method for producing a molded article, which comprises heat-curing the composition according to claim 1.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1264322A JPH0733404B2 (en) | 1989-10-11 | 1989-10-11 | Molding composition and method for producing molded article |
| US07/593,873 US5369183A (en) | 1989-10-09 | 1990-10-05 | Composite and molding from the composite |
| EP19900310996 EP0423998A3 (en) | 1989-10-09 | 1990-10-08 | Composite and moulded articles therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1264322A JPH0733404B2 (en) | 1989-10-11 | 1989-10-11 | Molding composition and method for producing molded article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03124702A JPH03124702A (en) | 1991-05-28 |
| JPH0733404B2 true JPH0733404B2 (en) | 1995-04-12 |
Family
ID=17401573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1264322A Expired - Lifetime JPH0733404B2 (en) | 1989-10-09 | 1989-10-11 | Molding composition and method for producing molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0733404B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH629664A5 (en) * | 1977-04-19 | 1982-05-14 | Espe Pharm Praep | Polymerisable composition for dental purposes |
| JP2719799B2 (en) * | 1988-10-14 | 1998-02-25 | 日本合成化学工業株式会社 | Photosensitive resin composition |
-
1989
- 1989-10-11 JP JP1264322A patent/JPH0733404B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03124702A (en) | 1991-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| GB1575698A (en) | Radiation shielding composition and a process for producing the same | |
| EP0504528A1 (en) | In-mould coating compositions and use thereof | |
| JP3718295B2 (en) | Vinyl ester resin composition and cured product | |
| EP0390207A1 (en) | Vibration-proof damping polymer material | |
| US5369183A (en) | Composite and molding from the composite | |
| JP3139685B2 (en) | Method for producing acrylic resin premix and acrylic artificial marble | |
| JPH0733404B2 (en) | Molding composition and method for producing molded article | |
| US3557256A (en) | Powder thermosetting compositions based on bulk polymerized polyvinyl chloride and polyacrylate plasticizer | |
| JP3198133B2 (en) | Molding resin composition | |
| JPH0513899B2 (en) | ||
| JP2884095B2 (en) | Molded article composition and molded article | |
| JP3906122B2 (en) | Vinyl ester resin composition for artificial marble with excellent storage stability | |
| JPH03217410A (en) | Molding composition and preparation of molded product | |
| JPH05171023A (en) | Resin composition for heat compression molding | |
| US3275714A (en) | Method and catalysts for converting vinyl chloride polymer-monomer compositions to polymeric products | |
| JPH03126702A (en) | Composition for molding and production of molded material thereof | |
| JPH03124703A (en) | Production of molding composition and molding | |
| JP2908528B2 (en) | Composition for artificial stone | |
| JPH0155650B2 (en) | ||
| JPH03124707A (en) | Production of molding composition and molding | |
| JP2873346B2 (en) | Process for producing putty-like composition and jig | |
| JPH0149181B2 (en) | ||
| JPH0453858A (en) | Molding composition and production of molding | |
| CA1265281A (en) | Impact modified methyl methacrylate polymer | |
| JP2850234B2 (en) | Resin composition |