JPS63277264A - Curable resin composition - Google Patents
Curable resin compositionInfo
- Publication number
- JPS63277264A JPS63277264A JP11076387A JP11076387A JPS63277264A JP S63277264 A JPS63277264 A JP S63277264A JP 11076387 A JP11076387 A JP 11076387A JP 11076387 A JP11076387 A JP 11076387A JP S63277264 A JPS63277264 A JP S63277264A
- Authority
- JP
- Japan
- Prior art keywords
- side chain
- meth
- parts
- polymer
- acryloyl group
- 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 11
- 229920000642 polymer Polymers 0.000 claims abstract description 58
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 34
- 238000009835 boiling Methods 0.000 abstract description 17
- 239000000203 mixture Substances 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004342 Benzoyl peroxide Substances 0.000 abstract description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 abstract description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 abstract description 2
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- 239000011521 glass Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- -1 2-hydroxylethyl Chemical group 0.000 description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- 238000005266 casting Methods 0.000 description 10
- 239000003822 epoxy resin Substances 0.000 description 10
- 229920000647 polyepoxide Polymers 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000010526 radical polymerization reaction Methods 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ALYFAKDWRRJJOJ-UHFFFAOYSA-N 2,2-dimethyltetradecane-3-thiol Chemical compound CCCCCCCCCCCC(S)C(C)(C)C ALYFAKDWRRJJOJ-UHFFFAOYSA-N 0.000 description 3
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 230000002087 whitening effect 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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003112 inhibitor Substances 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- PVCVRLMCLUQGBT-UHFFFAOYSA-N (1-tert-butylcyclohexyl) (1-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CCCCC1(C(C)(C)C)OC(=O)OOC(=O)OC1(C(C)(C)C)CCCCC1 PVCVRLMCLUQGBT-UHFFFAOYSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000002928 artificial marble Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 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 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IIQWTZQWBGDRQG-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;isocyanic acid Chemical compound N=C=O.CCOC(=O)C(C)=C IIQWTZQWBGDRQG-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- XEBWQGVWTUSTLN-UHFFFAOYSA-M phenylmercury acetate Chemical compound CC(=O)O[Hg]C1=CC=CC=C1 XEBWQGVWTUSTLN-UHFFFAOYSA-M 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000002360 preparation method 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
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明は、浴槽、洗面化粧台、タイルといった美感と耐
水性とを兼ね備えて要求される成形品とくに人造大理石
に有用な硬化性樹脂組成物に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a curable resin composition useful for molded products such as bathtubs, washstands, and tiles that are required to have both aesthetic appearance and water resistance, especially for artificial marble. Regarding.
[従来の技術]
浴槽を例にとってみると、着色ゲルコート施工後、ポリ
エステル樹脂とガラス繊維で裏打ちを行い、単一の透明
感のない浴槽を製造していたのが従来から行われていた
方法であった。[Conventional technology] Taking a bathtub as an example, the conventional method was to apply a colored gel coat and then line it with polyester resin and glass fiber to produce a single, non-transparent bathtub. there were.
然し、要求される外観、並びに性能が高度化されるにつ
れて、その製造方法にも変化が生じてきた。However, as the required appearance and performance have become more sophisticated, the manufacturing method has also changed.
例えば、透明なゲルコートを施してからガラス繊維と樹
脂で裏打ち積層し、更にフィラーを混合した樹脂で注型
を行うことによって、透明感のある天理石調の浴槽が製
造されており、増加の傾向がみられる。For example, transparent celestial stone-like bathtubs are manufactured by applying a transparent gel coat, then lining and laminating with glass fiber and resin, and then casting with resin mixed with fillers, and this trend is increasing. can be seen.
ガラス繊維を用いずに、ゲルコートに続いて注型を行う
場合もあり、製品の多様化に拍車がかけられている。In some cases, gel coating is followed by casting without using glass fiber, spurring product diversification.
問題は、このような成形品にあっては、硬化樹脂の色調
が良(、フィラー混合、硬化させた時の透明感、美麗感
があり、しかもこれらの外観が連続の煮沸テストによっ
て、黄変、白濁などの変化があってはならないことであ
る。The problem with such molded products is that the cured resin has a good color tone (filler mixture, transparency and beauty when cured, but the appearance of these products does not turn yellow in continuous boiling tests). There should be no changes such as cloudiness.
〔発明が解決しようとする問題点]
本発明は、前述した諸欠点を除き、試験で最も厳しいと
される片面煮沸テスト、即ちゲルコート面のみを沸騰水
に接触させる連続煮沸テストでも十分に満足できる物性
を示す成形品に有用な硬化性樹脂組成物の提供を目的と
するものである。[Problems to be Solved by the Invention] Other than the above-mentioned drawbacks, the present invention is sufficiently satisfactory even in a single-sided boiling test, which is considered to be the most severe test, that is, a continuous boiling test in which only the gel coated surface is brought into contact with boiling water. The object of the present invention is to provide a curable resin composition useful for molded articles exhibiting physical properties.
[問題点を解決するための手段]
即ち本発明の硬化性樹脂組成物は、前記目的を達成する
ために、型にゲルコートを施し、これにガラス質フィラ
ーを混入した樹脂組成物を用いて裏打ち成形するに際し
て、樹脂組成物として(A) 側鎖にウレタン結合又
はエステル結合を介して(メタ)アクリロイル基を有し
主鎖が炭素−炭素結合である側鎖不飽和ポリマー及び(
B)(メタ)アクリロイル基と共重合可能なモノマー、
(C) ガラス質フィラー及び
(D) ラジカル発生触媒からなることを特徴とし、
それによって前記諸欠点を解消することを可能とした。[Means for Solving the Problems] That is, in order to achieve the above-mentioned object, the curable resin composition of the present invention applies gel coating to a mold, and lines the mold with a resin composition mixed with a glass filler. When molding, as a resin composition (A) a side chain unsaturated polymer having a (meth)acryloyl group in the side chain via a urethane bond or an ester bond and whose main chain is a carbon-carbon bond;
B) a monomer copolymerizable with a (meth)acryloyl group, (C) a glassy filler, and (D) a radical generating catalyst,
This made it possible to eliminate the various drawbacks mentioned above.
[作 用コ
側鎖に(メタ)アクリロイル基を有し主鎖が炭素−炭素
結合である側鎖不飽和ポリマーは、構成分子の主鎖が炭
素−炭素結合であるために耐加水分解性に優れており、
ガラス質フィラーを充てんして注型層を形成、硬化させ
たものは、ゲルコート樹脂層に成程度の耐水性があれば
、煮沸テストによって、ブリスターの発生、或は劣化に
よる外観不良、黄変、白化、などが無く、煮沸テスト後
も頗る良好な透明性、色調、を有するものが得られると
考えられる。[Function] Side-chain unsaturated polymers with a (meth)acryloyl group in the side chain and a carbon-carbon bond in the main chain have poor hydrolysis resistance because the main chain of the constituent molecules is a carbon-carbon bond. Excellent,
For products filled with glass filler to form a cast layer and cured, if the gel coat resin layer has a certain degree of water resistance, a boiling test will show that blistering or poor appearance due to deterioration, yellowing, or It is thought that a product that is free from whitening and has excellent transparency and color tone even after the boiling test can be obtained.
本発明で用いられる側鎖不飽和ポリマーとしては、側鎖
にウレタン結合又はエステル結合を介して(メタ)アク
リロイル基を有し主鎖が炭素−炭素結合である硬化可能
なポリマーであり、側鎖にヒドロキシル基、カルボキシ
ル基、グリシジル基などの官能基を有するビニル系ポリ
マーを製造し、次いで該官能基とウレタン化又はエステ
ル化反応を行う反応基及び(メタ)アクリロイル基を共
有する化合物を反応させて製造される。その代表的な製
造方法及び具体例として以下のものが挙げられる。The side chain unsaturated polymer used in the present invention is a curable polymer having a (meth)acryloyl group in the side chain via a urethane bond or an ester bond, and the main chain is a carbon-carbon bond. A vinyl polymer having a functional group such as a hydroxyl group, a carboxyl group, or a glycidyl group is produced, and then the functional group is reacted with a compound that shares a reactive group that performs a urethanization or esterification reaction and a (meth)acryloyl group. Manufactured by Typical manufacturing methods and specific examples include the following.
(1)側鎖にウレタン結合を介して(メタ)アクリロイ
ル基を有する側鎖不飽和ポリマー
0)特開昭59−230019号公報、同80−384
03号公報に記載と同様の、
[A] 側鎖にヒドロキシル基を含むポリマーと、C
B] 多価イソシアナートと(メタ)アクリロイル基
を有する不飽和モノアルコールとの付加物で遊離のイソ
シアナート基を有する不飽和イソシアナートとを重合性
単量体中で[A]のヒドロキシル基とCB]のイソシア
ナート基とを反応させることよりなる硬化可能な側鎖不
飽和ポリマーが挙げられる。(1) Side chain unsaturated polymer having a (meth)acryloyl group in the side chain via a urethane bond 0) JP-A-59-230019, JP-A-80-384
[A] A polymer containing a hydroxyl group in the side chain, similar to that described in Publication No. 03, and C
B] An adduct of a polyvalent isocyanate and an unsaturated monoalcohol having a (meth)acryloyl group, in which an unsaturated isocyanate having a free isocyanate group is combined with the hydroxyl group of [A] in a polymerizable monomer. Examples include curable side-chain unsaturated polymers obtained by reacting CB] with isocyanate groups.
そのなかで、下記一般式[I]で示されるポリマーが本
発明において好適に使用される。Among them, polymers represented by the following general formula [I] are preferably used in the present invention.
〔但し、Ri 、R2は水素又はメチル基であり、Gは
ジイソシアナートの残基を表わし、Mは50〜300、
nは70〜99、mは1〜30゜gは2又は3の整数で
ある。〕
具体的には、側鎖にヒドロキシル基を含むポリマーとし
て2−ヒドロキシルエチル(メタ)アクリレート又は2
−ヒドロキシプロピル(メタ)アクリレートとスチレン
との共重合体を用い、それに不飽和イソシアナートとし
てトリレンジイソシアナートと2−ヒドロキシエチル(
メタ)アクリレート又は2−ヒドロキシプロピル(メタ
)アクリレートの1:1モル付加物を反応させて得られ
るものが最適である。[However, Ri and R2 are hydrogen or a methyl group, G represents a diisocyanate residue, M is 50 to 300,
n is 70-99, m is 1-30°g, and is an integer of 2 or 3. ] Specifically, 2-hydroxylethyl (meth)acrylate or 2-hydroxylethyl (meth)acrylate is used as a polymer containing a hydroxyl group in the side chain.
- Using a copolymer of hydroxypropyl (meth)acrylate and styrene, tolylene diisocyanate and 2-hydroxyethyl (
Most suitable are those obtained by reacting 1:1 molar adducts of meth)acrylate or 2-hydroxypropyl (meth)acrylate.
(ロ)前記の側鎖にヒドロキシル基を含むポリマーと、
(メタ)アクリロイルオキシエチルイソシアナート也を
反応させることよりなる硬化可能な側鎖不飽和ポリマー
が挙げられる。(b) the polymer containing a hydroxyl group in the side chain;
Examples include curable side-chain unsaturated polymers formed by reacting (meth)acryloyloxyethyl isocyanate.
(ハ) (メタ)アクリロイルオキシエチルイソシアナ
ートと、他のスチレン、メチルメタクリレート等ビニル
モノマーとの共重合によって得られる側鎖にイソシアナ
ートを含むポリマーと、(メタ)アクリロイル基を有す
る不飽和アルコールとを反応させることより得られる側
鎖不飽和ポリマーがあげられる。(c) A polymer containing isocyanate in the side chain obtained by copolymerizing (meth)acryloyloxyethyl isocyanate with other vinyl monomers such as styrene and methyl methacrylate, and an unsaturated alcohol having a (meth)acryloyl group. Examples include side-chain unsaturated polymers obtained by reacting.
(2)側鎖にエステル結合を介して(メタ)アクリロイ
ル基を有する側鎖不飽和ポリマー、仁)側鎖にグリシジ
ル基を含むポリマーと、(メタ)アクリル酸とを反応さ
せることよりなる得られる側鎖不飽和ポリマーであり下
記一般式[n]で示されるポリマーが代表的である。(2) A side chain unsaturated polymer having a (meth)acryloyl group in the side chain via an ester bond; A typical example is a side chain unsaturated polymer represented by the following general formula [n].
〔但し、R1,R2,M、n及びmの定義は前記と同じ
〕。[However, the definitions of R1, R2, M, n and m are the same as above].
具体的には、スチレンとグリシジル(メタ)アクリレー
トとの共重合体に、(メタ)アクリル酸をエステル化反
応させて得られるものが好適である。また、グリシジル
(メタ)アクリレ−!・の1部に代えてアリルグリシジ
ルエーテルを用いたものも好適に使用される。Specifically, a material obtained by subjecting a copolymer of styrene and glycidyl (meth)acrylate to an esterification reaction with (meth)acrylic acid is suitable. Also, glycidyl (meth)acrylate! It is also preferable to use allyl glycidyl ether in place of a part of .
(ホ)側鎖にカルボキシル基を含むポリマーと、不飽和
エポキシ化合物とを反応させて得られる上記一般式[I
I]で示されるポリマーが挙げられる。(e) The above general formula [I
Examples include polymers represented by I].
具体的には、スチレンと(メタ)アクリル酸との共重合
体に、グリシジル(メタ)アクリレートを反応させて得
られるものが好適である。Specifically, a material obtained by reacting a copolymer of styrene and (meth)acrylic acid with glycidyl (meth)acrylate is suitable.
(〜 特開昭61−258817号「硬化可能な樹脂及
びその製造方法」に代表される、
[A](メタ)アクリル酸1モルに対して、エポキシ樹
脂1モル以上とを反応させて得られる分子中に(メタ)
アクリロイル基とエポキシ基とを有する不飽和エポキシ
樹脂を少なくとも一成分として含む成分と、ビニルモノ
マー、とをラジカル重合触媒を用いて共重合させること
により、生成ポリマーの側鎖にエポキシ基を有するポリ
マー含有反応混合物を造り、次いで、
[B] 工程[A]から得られた反応混合物中に残存
するエポキシ基と実質的に等モルの(メタ)アクリル酸
を加えて、エポキシ基とカルボキシル基の反応を行わせ
ることによって得られる側鎖不飽和ポリマーが挙げられ
る。(~ JP-A No. 61-258817 "Curable resin and method for producing the same") [A] Obtained by reacting 1 mole of (meth)acrylic acid with 1 mole or more of epoxy resin in the molecule (meta)
By copolymerizing a component containing an unsaturated epoxy resin having an acryloyl group and an epoxy group as at least one component and a vinyl monomer using a radical polymerization catalyst, the resulting polymer contains a polymer having an epoxy group in the side chain. A reaction mixture is prepared, and then [B] substantially equimolar (meth)acrylic acid is added to the epoxy groups remaining in the reaction mixture obtained from step [A] to cause the reaction between the epoxy groups and the carboxyl groups. Examples include side-chain unsaturated polymers obtained by carrying out this process.
そのなかで、下記一般式[m]で示されるポリマーが好
適である。Among these, polymers represented by the following general formula [m] are preferred.
(以下余白)
同様に、上記ビスフェノール型エポキシ樹脂に代えて、
ノボラック型エポキシ樹脂、脂環式エポキシ樹脂を用い
たものも好適に使用される。(Left below) Similarly, instead of the above bisphenol type epoxy resin,
Those using novolac type epoxy resin and alicyclic epoxy resin are also preferably used.
0→ 側鎖にカルボキシル基を含むポリマーに、上記不
飽和エポキシ樹脂を反応させて得られる一般式[I[I
]で表わされる側鎖不飽和ポリマーが挙げられる。0→ The general formula [I [I
] Examples include side chain unsaturated polymers represented by the following.
使用されるエポキシ樹脂は」二足と同様である。The epoxy resin used is similar to 'Biped'.
(→ 側鎖に酸無水物基を含むポリマーに、(メタ)ア
クリロイル基を有する不飽和アルコールを反応させて得
られる側鎖不飽和ポリマーが挙げられる。(→ Examples include side chain unsaturated polymers obtained by reacting a polymer containing an acid anhydride group in the side chain with an unsaturated alcohol having a (meth)acryloyl group.
そのなかで、下記一般式[IV]で示されるポリマーが
好適に使用される。Among them, a polymer represented by the following general formula [IV] is preferably used.
(以下余白)
〔但し、R、R2、n、m及びMは前記した通りである
〕。(The following is a blank space) [However, R, R2, n, m and M are as described above].
具体的には、酸無水物基を有するポリマーとしてスチレ
ンと無水マイレン酸との共重合体を用い、それに2−ヒ
ドロキシエチル(メタ)アクリレート又は2−ヒドロキ
シプロピル(メタ)アクリレートを反応させて得られる
ものが最適である。Specifically, it is obtained by using a copolymer of styrene and maleic anhydride as a polymer having an acid anhydride group, and reacting it with 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate. The one that is the best.
更に、エステル化の結果生じた遊離カルボキシル基をエ
ポキシ基またはヒドロキシル基及び(メタ)アクリロイ
ル基とを共有しているモノマーと反応させることによっ
て得られる遊離のカルボキシル基の無いポリマーも本発
明において使用可能である。Furthermore, polymers free of free carboxyl groups obtained by reacting the free carboxyl groups resulting from esterification with epoxy groups or monomers sharing hydroxyl groups and (meth)acryloyl groups can also be used in the present invention. It is.
以上の側鎖不飽和ポリマーは分子1m5000以上、望
ましくは1万以上10万以下が望ましい。The above-mentioned side chain unsaturated polymer has a molecular size of 1 m2 or more, preferably 10,000 or more and 100,000 or less.
5000以下の分子量では硬化性、物性が必ずしも十分
ではなく、10万以上では粘度が高くなって作業性が劣
るようになる。If the molecular weight is less than 5,000, the curability and physical properties are not necessarily sufficient, and if it is more than 100,000, the viscosity becomes high and workability becomes poor.
側鎖不飽和ポリマー中の(メタ)アクリロイル基の比率
は、1モル%以上30モル%以下が望ま17い。The ratio of (meth)acryloyl groups in the side chain unsaturated polymer is desirably 1 mol% or more and 30 mol% or less.
最も適当な範囲は5モル%以上20モル%以下である。The most suitable range is 5 mol% or more and 20 mol% or less.
本発明に使用されるガラス質フィラーは、例えば日本フ
ェロ−■から“フリット”なる商品名で発売されている
もの或はガラスピーズとして東芸バロティー二社のもの
を使用できる。さらに、大きさ約50〜400 ミクロ
ン、厚さ2〜10ミクロンの偏平状のものであり、例え
ば日本硝子繊維■のガラスフレークCFも使用可能であ
る。As the vitreous filler used in the present invention, for example, there can be used one sold under the trade name "Frit" by Nippon Ferro-■, or one manufactured by Togei Baroty Nisha as Glass Peas. Further, it is a flat material having a size of about 50 to 400 microns and a thickness of 2 to 10 microns, and for example, glass flakes CF manufactured by Nippon Glass Fiber (■) can also be used.
樹脂(側鎖不飽和ポリマーと共重合可能なモノマーとの
混合物)とガラス質フィラーとの混合割合は特に制限を
加える必要はないが、樹脂100部に対して、ガラス質
フィラー50部以上250部以下が望まし−い。There is no particular restriction on the mixing ratio of the resin (a mixture of a side chain unsaturated polymer and a copolymerizable monomer) and the glass filler, but the glass filler should be 50 parts or more and 250 parts or more per 100 parts of the resin. The following is desirable.
50部以下ではフィラーを併用する意味が薄れ、250
部以コニでは混合物の粘度が高くなって作業が困難どな
る傾向がある。If it is less than 50 parts, the meaning of using filler will be diminished, and 250 parts
When the mixture is mixed, the viscosity of the mixture tends to increase, making it difficult to work with.
フィラーの粒径は500μ以下で、現在市販されている
10g以上]、00μ以下程度のもので十分である。The particle size of the filler is 500μ or less, and currently commercially available fillers of 10g or more and 00μ or less are sufficient.
側鎖不飽和ポリマーは、通常それ自体は固体であること
から、(メタ)アクリロイル基と共重合可能なモノマー
に溶解した形で使用される。モノマーの配合はいつでも
よいが、エステル化反応前に反応系に存在させて反応溶
媒として作用させる方法を採用するのが便利である。Since the side chain unsaturated polymer is usually solid itself, it is used in a form dissolved in a monomer copolymerizable with a (meth)acryloyl group. The monomers may be added at any time, but it is convenient to have them present in the reaction system before the esterification reaction to act as a reaction solvent.
このために利用し得るモノマーとしてはコスト、硬化性
などの点からスチレン、ビニルトルエンが一般的である
が、ジビニルベンゼンを併用することもできる。その他
にも、例えば(メタ)アクリル酸のモノ或はジエステル
類、代表的にはメタクリル酸メチルが用いられる・
他のモノマー類を併用することは自由である。As monomers that can be used for this purpose, styrene and vinyltoluene are generally used in terms of cost and curability, but divinylbenzene can also be used in combination. In addition, for example, mono- or diesters of (meth)acrylic acid, typically methyl methacrylate, may be used.Other monomers may be used in combination.
モノマーと側鎖不飽和ポリマーの比率は特に制限される
わけではなく、主として作業性の点から決められるが、
普通側鎖不飽和ポリマー100重世部に対してモノマー
50部具−1=150部以下が適当であり、最も良い比
率は100〜120部である。The ratio of monomer to side chain unsaturated polymer is not particularly limited and is determined mainly from the viewpoint of workability, but
Generally, it is appropriate to use 50 parts of monomer to 100 parts of side chain unsaturated polymer = 150 parts or less, and the best ratio is 100 to 120 parts.
側鎖不飽和ポリマーとモノマーが混合された樹脂には、
一般に用いられている重合防止剤を加える必要がある。The resin, which is a mixture of side chain unsaturated polymer and monomer, has
It is necessary to add a commonly used polymerization inhibitor.
本発明で用いられるラジカル発生触媒としては、市販の
有機過酸化物が使用され、例えばベンゾイルパーキシド
、ジt−ブチルバーオキシド、1−ブチルパーオキシビ
バレート、t−ブチルパーオキシ 2エチルヘキザネー
ト、シミリスチルパーオキシジカーボネート、ビス(t
−ブチルシクロヘキシル)パーオキシジカーボネートな
どがあげられ、更に促進剤と併用する場合、例えば、パ
ーオキシケタールと第4級アンモニウム塩との組合せ、
ケトンパーオキサイド類とコバルトの有機酸塩との組合
せ、ハイドロパーオキサイド類と銅塩又はバナジウム塩
との組合せなどがあげられる。As the radical generating catalyst used in the present invention, commercially available organic peroxides are used, such as benzoyl peroxide, di-t-butyl peroxide, 1-butyl peroxyvivalate, t-butyl peroxy, 2-ethyl hexa ester, cimilistyl peroxydicarbonate, bis(t
-butylcyclohexyl) peroxydicarbonate, and when used in combination with an accelerator, for example, a combination of peroxyketal and quaternary ammonium salt,
Examples include combinations of ketone peroxides and organic acid salts of cobalt, and combinations of hydroperoxides and copper salts or vanadium salts.
その使用曾は通常、樹脂100重量部当り0.01〜5
重全部である。Its usage is usually 0.01 to 5 parts per 100 parts by weight of resin.
It is a heavy part.
本発明の硬化性樹脂組成物には必要に応じて着色剤、熱
可塑性ポリマー、或は他のフィラーを加えることは自由
である。Colorants, thermoplastic polymers, or other fillers may be added to the curable resin composition of the present invention as needed.
また物性を変えない範囲で不飽和ポリエステル樹脂、ビ
ニルエステル樹脂等の汎用の硬化性樹脂を併用すること
も出来ることは勿論である。It goes without saying that general-purpose curable resins such as unsaturated polyester resins and vinyl ester resins can also be used in combination without changing the physical properties.
本発明の硬化性樹脂組成物は、前記硬化可能なポリマー
、共重合可能なモノマー、ガラス質フィラー及びラジカ
ル発生触媒を通常の方法で、混合し、成形し、硬化して
種々な成形品に製造される。The curable resin composition of the present invention can be manufactured into various molded products by mixing, molding, and curing the curable polymer, copolymerizable monomer, glassy filler, and radical generating catalyst using a conventional method. be done.
[実 施 例]
次に本発明の理解を助けるために、以下に実施例を示す
。[Example] Next, in order to help the understanding of the present invention, examples are shown below.
実施例 1
側鎖にウレタン結合を介してメタアクリロイル基を有す
る側鎖不飽和ポリマー[A]の合成。Example 1 Synthesis of side chain unsaturated polymer [A] having a methacryloyl group in the side chain via a urethane bond.
攪拌器、還流コンデンサー、ガスの導入管、温度計を付
した1gセパラブルフラスコに、スチレン312 g、
2−ヒドロキシプロピルメタクリレ−。In a 1 g separable flask equipped with a stirrer, reflux condenser, gas inlet tube, and thermometer, 312 g of styrene was added.
2-Hydroxypropyl methacrylate.
ト43g5 t−ブチルドデシルメルカプタン3.5g
を仕込み、窒素ガス気流中で120〜125℃に加熱重
合すると、5時間で重合率62%に達した。GPC14
11定によると分子量2万7千の所にピークのあるポリ
マーであった。ハイドロキノン0゜2g加えた後、スチ
レン155gを追加し、温度を60℃に下げ、更に不飽
和イソシアナートとしてダウケミカル社製イソシアナー
トエチルメタクリレート(下式)
を40g、ジブチル錫ジラウレLトを0.5g加え、6
0°Cで5時間、乾燥空気系流中で反応すると、赤外分
析の結果、遊離のイソシアナ−1・基は完全に消失した
ことが認められた。t-43g5 t-butyldodecylmercaptan 3.5g
was charged and polymerized by heating at 120 to 125° C. in a nitrogen gas stream, and the polymerization rate reached 62% in 5 hours. GPC14
According to the 11th constant, it was a polymer with a peak at a molecular weight of 27,000. After adding 0.2 g of hydroquinone, 155 g of styrene was added, the temperature was lowered to 60°C, and 40 g of isocyanate ethyl methacrylate (formula below) manufactured by Dow Chemical Company as an unsaturated isocyanate and 0.2 g of dibutyltin dilaure L were added. Add 5g, 6
After reacting at 0°C for 5 hours in a dry air stream, infrared analysis showed that the free isocyanate-1 groups had completely disappeared.
はとんど無色で、粘度6.7ポイズの側鎖不飽和ポリマ
ー〔A]が得られた。A side chain unsaturated polymer [A] which was almost colorless and had a viscosity of 6.7 poise was obtained.
注型品の成形と煮沸テスト。Molding and boiling test of cast products.
380m/mX 360m/mのガラス板上に離型剤を
塗布した後、ゲルコートとして昭和高分子社製ポリエス
テル樹脂である“G −400″ (エロジル4%を含
む)を100部に、化薬ヌーリー社製“パー力ドックス
#16“ 〔ビス(4−tブチルシクロヘキシル)パー
オキシジカーボネート〕を1.5部加え、0.5〜0.
[3m/m厚になるようにスプレー塗布した後、60°
C1時間の加温でゲル化させた。After applying a mold release agent on a glass plate of 380 m/m x 360 m/m, 100 parts of "G-400" (containing 4% Erosil), a polyester resin manufactured by Showa Kobunshi Co., Ltd., was added as a gel coat, and Kayaku Nouri was applied as a gel coat. Add 1.5 parts of "Parriki Dox #16" [bis(4-t-butylcyclohexyl) peroxydicarbonate] manufactured by Co., Ltd., and add 0.5 to 0.
[After spraying to a thickness of 3m/m, 60°
It was gelled by heating for C1 hour.
これを一方の側とし、別の側を厚さ1.2m/mのガラ
スマット、ポリエステル樹脂使用のFRP板とし、厚さ
lOm/+nのスペーサーをはさんで固定し、このゲル
コート鋳型ガラス板とFRP板との間に、注型用樹脂と
して、ポリマー[A]を100部、日本フェロ−社製フ
リット、M−10−8を200部、バー力ドックス#1
6を2部添加し、均一に混練、脱泡した混合樹脂を用い
、注型した。This is used as one side, and the other side is a glass mat with a thickness of 1.2 m/m and an FRP plate using polyester resin, and fixed with a spacer of 10m/+n in thickness, and this gel coat molded glass plate and Between the FRP board and the resin for casting, 100 parts of polymer [A], 200 parts of frit M-10-8 manufactured by Nippon Ferro Co., Ltd., and Bariki Dox #1 were added.
6 was added, and the mixed resin was uniformly kneaded and defoamed, and cast.
注型後60℃1時間、70°C4時間加熱して硬化させ
た。After casting, it was cured by heating at 60°C for 1 hour and then at 70°C for 4 hours.
硬化終了後、150m/mX 150rfi/mに切断
し、ケルコートを施した面を直径12On+/mの円形
に穴あけした耐煮沸性テスト容器に、シリコンゴムバッ
キングを介して密着させ、連続煮沸テストを行った。After curing, it was cut to 150m/m x 150rfi/m, and the surface coated with Kelcoat was brought into close contact with a boiling resistance test container with a circular hole of 12On+/m in diameter via a silicone rubber backing, and a continuous boiling test was performed. Ta.
比較のために、側鎖不飽和ポリマー[A]に替えてポリ
エステル樹脂[:B] (ネオペンチルグリコール1
0,7モル−イソフタル酸4モル〜フマル酸6モル、2
段法、最終酸価34.4、スチレン45%)使用し、他
はすべて同−條件とした注型板を作成した。For comparison, polyester resin [:B] (neopentyl glycol 1
0,7 mol - 4 mol of isophthalic acid to 6 mol of fumaric acid, 2
A cast plate was prepared using the step method, final acid value 34.4, styrene 45%), with all other conditions being the same.
連続煮沸テストの結果は第1表にみられるように、側鎖
不飽和ポリマー[A]を用いた注型板が明らかに優れて
いた。As shown in Table 1, the results of the continuous boiling test clearly showed that the casting plate using the side chain unsaturated polymer [A] was superior.
(以下余白)
第 1 表
実施例 2
側鎖にエステル結合を介してアクリロイル基を有する側
鎖不飽和ポリマー[C]の合成。(Left below) Table 1 Example 2 Synthesis of side chain unsaturated polymer [C] having an acryloyl group in the side chain via an ester bond.
攪拌器、還流コンデンサー、温度計、ガス導入管を付し
た2gセパラブルフラスコに、スチレン936g、グリ
シデルメタクリレート140 g、 t −ブチルド
デシルメルカプタンlOgを仕込み、120〜125℃
に6時間窒素気流中で攪拌すると、GPC測定による分
子全3万6千にピークを有し反応率は46%となっての
で、ハイドロキノン0.3gを加え、温度を110℃に
下げ、空気系流中でアクリル酸87g、 トリメチル
ベンジルアンモニウムクロライド2gを加え3時間反応
した。酸価13.4、赤外吸収スペクトルでエポキシ基
の吸収は完全に消失したことが確;召された。A 2g separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a gas inlet tube was charged with 936g of styrene, 140g of glycidel methacrylate, and 10g of t-butyldodecylmercaptan, and heated to 120-125°C.
When stirred in a nitrogen stream for 6 hours, GPC measurement showed a peak for all 36,000 molecules and the reaction rate was 46%, so 0.3 g of hydroquinone was added, the temperature was lowered to 110°C, and the air system was stirred. 87 g of acrylic acid and 2 g of trimethylbenzylammonium chloride were added in a flowing stream and reacted for 3 hours. It was confirmed that the acid value was 13.4 and that the absorption of epoxy groups had completely disappeared from the infrared absorption spectrum.
ハーゼン色数75、粘度5.9ポイズの側鎖不飽和ポリ
マー[Cコが得られた。A side chain unsaturated polymer [C] having a Hazen color number of 75 and a viscosity of 5.9 poise was obtained.
注型品の製造
離型剤を塗布した360 X360111/Inガラス
板ヒに、ゲルコートとして側鎖不飽和結合型ポリマー[
Cコを100部、アエロジル#200を4部、t−ブチ
ルパーオキシビバレート2部を均一に混合し、0.5〜
0.6+a/m厚になるようにバーコーターで塗装した
。Production of cast products A side chain unsaturated bond type polymer [[
Uniformly mix 100 parts of C, 4 parts of Aerosil #200, and 2 parts of t-butyl peroxyvivalate,
It was coated with a bar coater to a thickness of 0.6+a/m.
70°C30分放置して表面が非粘着になった段階で、
実施例1と同様に片側をFRP、片側をゲルコート塗装
したガラス板で厚さ10+11/II+のスペーサーで
注型用型とした中に不飽和ポリマー[C3100部に東
芸バロティー二社製平均粒径約30μのガラス球(商品
名EGBの31)を150部、シランカップリング剤と
してユニザン・カーバイト社製A−174を1部、更に
t−プチルパーオキシビパレート1.5部を加え注入し
た後、60℃1時間、70℃3時間加熱して硬化を完了
させた。Leave it at 70°C for 30 minutes and when the surface becomes non-adhesive,
As in Example 1, a glass plate coated with FRP on one side and gel coated on the other side was used as a casting mold with a spacer of thickness 10+11/II+, and the inside was filled with unsaturated polymer [C3100 parts manufactured by Togei Barotii Co., Ltd. with average particle size] 150 parts of approximately 30μ glass bulbs (trade name: EGB 31), 1 part of A-174 manufactured by Unisan Carbide as a silane coupling agent, and 1.5 parts of t-butyl peroxybiparate were added and injected. Thereafter, the film was heated at 60° C. for 1 hour and at 70° C. for 3 hours to complete curing.
や\透明感のある注型板が得られた。これを実施例1と
同様に片面煮沸のテストを行った。A casting plate with a sense of transparency was obtained. This was subjected to a single-sided boiling test in the same manner as in Example 1.
結果は第2表にみられるように、良好であった。The results were good, as seen in Table 2.
第 2 表
実施例 3
側鎖にエステル結合を介してメタクリロイル基を有する
側鎖不飽和ポリマー[D]の合成、攪拌器、還流コンデ
ンサー、温度計付ガス導入管、滴下ロートを付した2g
セパラブルフラスコに、スチレン728g、かt−ブチ
ルドデシルメルカプタンlog、を仕込み、窒素気流中
温度100℃でメチルメタクリレート200g、無水マ
レイン酸98gの混合物を滴下した。Table 2 Example 3 Synthesis of side chain unsaturated polymer [D] having a methacryloyl group via an ester bond in the side chain, 2 g equipped with a stirrer, reflux condenser, gas inlet tube with thermometer, and dropping funnel
A separable flask was charged with 728 g of styrene and log of t-butyldodecyl mercaptan, and a mixture of 200 g of methyl methacrylate and 98 g of maleic anhydride was added dropwise at a temperature of 100° C. in a nitrogen stream.
滴下開始後温度を120℃に上昇させ、同温度で5時間
を要して滴下を終了させた。After the dropwise addition was started, the temperature was raised to 120°C, and the dropwise addition was completed at the same temperature for 5 hours.
滴下終了後、更に1時間同温度で加熱を続けると固型分
は45(%)となった。GPCによる分子量測定では2
万8千の所にピークがあった。温度を100℃に下げ、
ハイドロキノン0.2g、2−ヒドロキシエチルメタク
リレート130g、パラトルエンスルホン酸2gを加え
、同温度で6時間反応すると、赤外分析の結果ポリマー
中の酸無水物の吸収は約70(%)程度消失したものと
判断された。After the dropwise addition was completed, heating was continued at the same temperature for an additional hour, and the solid content became 45 (%). In molecular weight measurement by GPC, 2
The peak was at 8,000. Lower the temperature to 100℃,
After adding 0.2 g of hydroquinone, 130 g of 2-hydroxyethyl methacrylate, and 2 g of para-toluenesulfonic acid and reacting at the same temperature for 6 hours, infrared analysis showed that approximately 70 (%) of the acid anhydride absorption in the polymer disappeared. It was determined that
側鎖にメタクリロイル基を有する側鎖不飽和ポリマー[
D]が粘度9.4ボイズ、ハーゼン色数200で得られ
た。Side chain unsaturated polymer with methacryloyl group in the side chain [
D] was obtained with a viscosity of 9.4 voids and a Hazen color number of 200.
注型板の製造とテスト。Production and testing of casting plates.
実施例1と同様にゲルコート塗装したガラス板と、FR
P板の間に、Low/m厚になるように、側鎖不飽和ポ
リマーCD1100部、フリットS−10−8200部
、t−プチルパーオキシビパレート1.5部、シランカ
ップリング剤A−1741部の混合樹脂を脱泡、注型し
、た。A glass plate coated with gel coat as in Example 1 and FR
Between the P plates, 1100 parts of side chain unsaturated polymer CD, 8200 parts of frit S-10-8, 1.5 parts of t-butyl peroxybiparate, and 1741 parts of silane coupling agent A- were placed so that the thickness was Low/m. The mixed resin was defoamed and cast.
60℃1時間、70℃3時間加熱硬化すると硬化したの
で、実施例1と同様の寸法に切断煮沸テストを行った。It was cured by heating at 60° C. for 1 hour and at 70° C. for 3 hours, so a cutting and boiling test was conducted to the same dimensions as in Example 1.
300時間片面連続煮沸テストの結果、ブリスターの発
生は認められなかった。As a result of a 300-hour continuous boiling test on one side, no blisters were observed.
実施例′4
側鎖にエステル結合を介して(メタ)アクリロイル基を
有する側鎖不飽和ポリマー[E]の合成、攪拌機、還流
コンデンサー、ガス導入管、温度計を付した2gセパラ
ブルフラスコに、エポキシ樹脂として、エボキト価18
7のジグリシヂルエーテル型エポキシ樹脂を1125g
、メタクリル酸86g1トリメチルベンジルアンモニウ
ムクロライド3g1ハイドロキノン0.3gを仕込み、
空気気流中130〜135℃に加熱攪拌すると、約1.
5時間で酸価は実質上ゼロとなったので、スチレン29
0 g加え不飽和エポキシ樹脂[I]を得た。Example '4 Synthesis of side chain unsaturated polymer [E] having a (meth)acryloyl group via an ester bond in the side chain. As an epoxy resin, ebokite value 18
1125g of diglycidyl ether type epoxy resin No.7
, 86 g of methacrylic acid, 3 g of trimethylbenzylammonium chloride, and 0.3 g of hydroquinone were charged.
When heated and stirred at 130-135°C in an air stream, about 1.
After 5 hours, the acid value became practically zero, so styrene 29
0 g was added to obtain unsaturated epoxy resin [I].
別に用意した同様の装置に、不飽和エポキシ樹脂[I]
を300g、スチレン1000g、を仕込み、窒素ガス
気流中、120℃で6時間加熱し、固形公約46%とし
た後、メタクリル酸88g、 トリメチルベンジルアン
モニウムクロライド2.7g、ハイドロキノン0.5g
、を追加し、空気気流中で110〜115℃で3時間反
応すると、酸価は11.4となったので、更にスチレン
114gを追加し、側鎖不飽和ポリマー[E]が、ハー
ゼン色数250粘度3.7ポイズで得られた。In a similar device prepared separately, unsaturated epoxy resin [I]
300g of methacrylic acid, 1000g of styrene were heated at 120°C for 6 hours in a nitrogen gas stream to make the solids approximately 46%, and then 88g of methacrylic acid, 2.7g of trimethylbenzylammonium chloride, and 0.5g of hydroquinone were added.
, and reacted for 3 hours at 110 to 115°C in an air stream, the acid value was 11.4, so 114 g of styrene was added, and the side chain unsaturated polymer [E] was converted to Hazen color number. 250 with a viscosity of 3.7 poise.
側鎖不飽和ポリマー[E]を100部に、化薬ヌーリー
社■の商品名パー力ドックス#16を1.5部加え、更
にガラスフレークとしてCF−150(日本硝子繊維■
製を70部、シランカップリング剤A−1742部加え
、減圧脱泡した後、実施例1で調整したと同様のゲルコ
ート、FRP板の間に注入、60°C1一時間、次いで
70℃4時間硬化させて注型板とした。To 100 parts of side chain unsaturated polymer [E], 1.5 parts of Perryoku Dox #16 (trade name, manufactured by Kayaku Nouri Co., Ltd.) was added, and glass flakes such as CF-150 (Nippon Glass Fibers) were added.
After adding 70 parts of Silane Coupling Agent A-1742 parts and defoaming under reduced pressure, the same gel coat as prepared in Example 1 was injected between FRP plates and cured at 60°C for 1 hour, then at 70°C for 4 hours. It was made into a casting board.
片面連続煮沸では、1000時間に至ってもふくれ、ク
ラックの発生はみられず、注型層の白化もみられなかっ
た。In continuous boiling on one side, no blistering or cracking was observed even after 1000 hours, and no whitening of the cast layer was observed.
実施例 5
側鎖にウレタン結合を介して(メタ)アクリロイル基を
有する側鎖不飽和ポリマー[F]の製造加熱及び冷却可
能な3!:lのオートクレーブに、スチレン、ヒドロキ
シエチルメタクリレート、t−ドデシルメルカプタン及
びn−ドデシルメルカプタンの所定量を仕込み、所定温
度で共重合を行った。定期的にサンプルを採取し、分子
量を測定した。Example 5 Production of side chain unsaturated polymer [F] having (meth)acryloyl group in side chain via urethane bond 3! Predetermined amounts of styrene, hydroxyethyl methacrylate, t-dodecyl mercaptan, and n-dodecyl mercaptan were charged into a :1 autoclave, and copolymerization was carried out at a predetermined temperature. Samples were taken periodically and the molecular weight was determined.
所定の分子量に達した時点で、希釈モノマーとしてスチ
レン、重合禁止剤としてハイドロキノン、触媒としてジ
ブチル錫ジラウレートからなる希釈液の所定量をオート
クレーブに注入し、60℃に保ちながら0.5時間攪拌
し7た。When a predetermined molecular weight was reached, a predetermined amount of a diluent consisting of styrene as a diluent monomer, hydroquinone as a polymerization inhibitor, and dibutyltin dilaurate as a catalyst was poured into an autoclave, and the mixture was stirred for 0.5 hours while maintaining the temperature at 60°C. Ta.
次いで、トリレンジイソシアナートの130部と2−ヒ
ドロキシプロピルメタクリレートの150部とを反応し
て得られた分子中にメタクリロイル基とイソシアナート
基を共有する不飽和イソシアナートの当量を加え、60
°Cにてイソシアナート基が消失するまでつlノタン化
を行った。反応時間は約6時間であった。Next, 130 parts of tolylene diisocyanate and 150 parts of 2-hydroxypropyl methacrylate were reacted, and an equivalent amount of an unsaturated isocyanate sharing a methacryloyl group and an isocyanate group was added to the molecule obtained by reacting 130 parts of tolylene diisocyanate with 150 parts of 2-hydroxypropyl methacrylate.
The notanization was carried out at °C until the isocyanate groups disappeared. The reaction time was approximately 6 hours.
得られた側鎖不飽和ポリマー[F] ioo部に過酸化
物触媒(日本油脂蛛製、バーギュア5A)l。5部及び
ナフテン酸コバルト(6%コバルト含有)0.5部を配
合して常温で硬化させて物性を測定した。A peroxide catalyst (manufactured by NOF HOME CO., LTD., VIRGURE 5A) was added to the ioo portion of the obtained side chain unsaturated polymer [F]. 5 parts and 0.5 parts of cobalt naphthenate (containing 6% cobalt) were blended and cured at room temperature, and the physical properties were measured.
(以下余白)
第 3 表
ゲルコートの製造
側鎖不飽和ポリマー[P] 100部に、エロジルRx
−200を4部、フタロシアニンブルー0.02部をロ
ール混練してゲルコートとじた。(Margins below) Table 3 Production of gel coat 100 parts of side chain unsaturated polymer [P], Erosil Rx
4 parts of -200 and 0.02 part of phthalocyanine blue were roll-kneaded and gel coated.
テストピースの作成
離型剤処理をしたガラス板上に、ゲルコート100部に
パー力ドックス+16を1.5部加え0.6m/m 、
になるようにバーコータで塗装し、60℃30分加熱し
てゲル化させた後、側鎖不飽和ポリマー[F] 100
部に、エロジルRx −2001,5部、バーカドック
ス#161部加えて調製した樹脂液によって、ガラスサ
ーフェスマット30pを含浸、ゲルコート層の次に塗着
し、60℃で30分加熱してゲル化させた。中間層の厚
さは約0.8mmであった。Preparation of test piece On a glass plate treated with a mold release agent, add 1.5 parts of Parriki Dox +16 to 100 parts of gel coat at 0.6 m/m.
After coating with a bar coater so that
Glass Surface Mat 30p was impregnated with a resin solution prepared by adding 5 parts of Erosil Rx-2001 and 161 parts of Verkadox #1, and applied next to the gel coat layer, and heated at 60°C for 30 minutes to gel. I let it happen. The thickness of the intermediate layer was approximately 0.8 mm.
これを一方の面とし、他面を厚さ1〜1.5m/a+の
ガラスマット使用FRP板とし、厚さ約8 m/rnと
なるように、側鎖不飽和ポリマー[F] 100部にフ
リットMIO−8を200部、パーカドックス#16を
1部、を加えた注型組成物を注型、当初60℃1時間、
70℃4時間加熱して硬化させた。This was used as one side, and the other side was an FRP plate using glass mat with a thickness of 1 to 1.5 m/a+, and 100 parts of side chain unsaturated polymer [F] was added to the plate so that the thickness was about 8 m/rn. A casting composition containing 200 parts of Frit MIO-8 and 1 part of Parkadox #16 was cast, initially at 60°C for 1 hour.
It was cured by heating at 70°C for 4 hours.
実施例1と同様に片面煮沸を実施した所、500時間経
過後もブリスター、白化の発生はみられなかった。When one-sided boiling was carried out in the same manner as in Example 1, no blistering or whitening was observed even after 500 hours.
[発明の効果コ
本発明の硬化性樹脂組成物は、低コストで、極めて優れ
た耐煮沸性を有する種々の成形品を製造することができ
、浴槽、洗面化粧台、タイルなどの耐水性と美感を要求
される用途に非常に有用である。[Effects of the Invention] The curable resin composition of the present invention can be used to produce various molded products with extremely excellent boiling resistance at low cost, and can be used to improve the water resistance of bathtubs, bathroom vanities, tiles, etc. Very useful for applications that require aesthetic appearance.
Claims (1)
メタ)アクリロイル基を有し主鎖が炭素−炭素結合であ
る側鎖不飽和ポリマー、 (B)(メタ)アクリロイル基と共重合可能なモノマー
、 (C)ガラス質フィラー及び (D)ラジカル発生触媒からなる硬化性樹脂組成物。[Claims] (A) Through a urethane bond or an ester bond in the side chain (
(meth) A side chain unsaturated polymer having an acryloyl group and whose main chain is a carbon-carbon bond, (B) A monomer copolymerizable with the (meth)acryloyl group, (C) A glassy filler, and (D) A radical generating catalyst. A curable resin composition consisting of:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11076387A JPS63277264A (en) | 1987-05-08 | 1987-05-08 | Curable resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11076387A JPS63277264A (en) | 1987-05-08 | 1987-05-08 | Curable resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS63277264A true JPS63277264A (en) | 1988-11-15 |
Family
ID=14543951
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11076387A Pending JPS63277264A (en) | 1987-05-08 | 1987-05-08 | Curable resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63277264A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008123358A1 (en) * | 2007-03-29 | 2008-10-16 | Dic Corporation | Active energy ray-curable resin composition for cast polymerization and cured product |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4957056A (en) * | 1972-10-04 | 1974-06-03 | ||
JPS61197618A (en) * | 1984-12-28 | 1986-09-01 | アトランテイツク・リツチフイ−ルド・カンパニ− | Radiation curable macromolecular monomer composition and polymerization |
-
1987
- 1987-05-08 JP JP11076387A patent/JPS63277264A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4957056A (en) * | 1972-10-04 | 1974-06-03 | ||
JPS61197618A (en) * | 1984-12-28 | 1986-09-01 | アトランテイツク・リツチフイ−ルド・カンパニ− | Radiation curable macromolecular monomer composition and polymerization |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008123358A1 (en) * | 2007-03-29 | 2008-10-16 | Dic Corporation | Active energy ray-curable resin composition for cast polymerization and cured product |
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