JPS6360046B2 - - Google Patents
Info
- Publication number
- JPS6360046B2 JPS6360046B2 JP54037846A JP3784679A JPS6360046B2 JP S6360046 B2 JPS6360046 B2 JP S6360046B2 JP 54037846 A JP54037846 A JP 54037846A JP 3784679 A JP3784679 A JP 3784679A JP S6360046 B2 JPS6360046 B2 JP S6360046B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- silyl group
- formula
- resin
- containing vinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920005989 resin Polymers 0.000 claims description 37
- 239000011347 resin Substances 0.000 claims description 37
- 229920002554 vinyl polymer Polymers 0.000 claims description 33
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 31
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 29
- -1 aminoxy, phenoxy Chemical group 0.000 claims description 21
- 229910000077 silane Inorganic materials 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004423 acyloxy group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000005309 thioalkoxy group Chemical group 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000001475 halogen functional group Chemical group 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 150000002443 hydroxylamines Chemical class 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- CWLUFVAFWWNXJZ-UHFFFAOYSA-N 1-hydroxypyrrolidine Chemical compound ON1CCCC1 CWLUFVAFWWNXJZ-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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005048 methyldichlorosilane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- VMESOKCXSYNAKD-UHFFFAOYSA-N n,n-dimethylhydroxylamine Chemical compound CN(C)O VMESOKCXSYNAKD-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明はシリル基含有ビニル系樹脂に関する。
本発明の樹脂は、式
（式中、R1は炭素数１〜10のアルキル基、ア
リール基、アラルキル基より選ばれる１価の炭化
水素基、R3は重合性二重結合を有する有機基、
Ｘはハロゲン、アルコキシ、アシロキシ、アミノ
キシ、フエノキシ、チオアルコキシ、アミノ基よ
り選ばれる基である。）
で示されるシラン化合物とビニル系化合物とをラ
ジカル共重合させることにより、主鎖が実質的に
ビニル系重合体からなり、２個の加水分解性基と
結合した珪素基を１分子中に少くとも１個有し、
かつそのシリル基当量が300〜2500である数平均
分子量300〜30000の塗料として好適なシリル基含
有ビニル系樹脂である。
本発明は、末端あるいは側鎖に加水分解性基を
有するシリル基を含有する化合物であり、そのた
めビニル樹脂の特徴だけでなく密着性が改善さ
れ、更に水分特に大気中の水分による常温架橋
で、ち密な網状構造を形成し、耐溶剤性、耐水
性、耐熱性、硬度、耐候性の優れた樹脂となる。
この様に常温又は低温で架橋し優れた物性の樹脂
となるため、現在無公害化、省資源化が大きく注
目されている塗料、コーテイング用樹脂として非
常に好都合なものである。特に本発明の樹脂は、
これまでのビニル系樹脂に比べ分子量が低くても
よい物性を得ることができ高固形分型塗料への応
用が容易となるのも大きな利点である。
これまで各種ビニル系樹脂は既によく知られて
いて熱可塑性樹脂として多量に用いられている。
又、シリル基含有ビニル系樹脂としては、特開昭
49−45130等に見られる様に種々のものが知られ
ている。しかしこれ等は硬化化の樹脂として知ら
れていたにも拘らず、本発明のような塗料の成分
としては全く用いられていないのが実情である。
そこで本発明者等は鋭意研究の結果、特定の分
子量を有し、且つ１個のシリル基において２個の
加水分解性官能基を有するシリル基含有ビニル系
樹脂のみが優れた塗膜を形成することを見出し
た。
本発明においては、分子量とともに１個の珪素
原子に結合した加水分解性基の数が重要である。
加水分解性基を３個有するシリル基含有のビニル
系樹脂が知られているが、本発明の様な加水分解
性基を２個有するシリル基含有のビニル系樹脂は
知られていない。例えば、特開昭49−45130によ
るとビニル系単量体とγ−メタクリロキシプロピ
ルトリメトキシシランとをラジカル開始剤とで共
重合し加水分解基を３個有するシリル基含有のビ
ニル系樹脂を合成している。この様にして得られ
たビニル系樹脂は本発明によるビニル系樹脂と同
様に常温架橋することができる。しかし、加水分
解性基を３個有するシリル基含有ビニル系樹脂に
おいては加水分解性基を３個有するということか
らくるいくつかの欠点を有している。その理由は
明らかではないが、次のように推定される。即
ち、加水分解性基が多くなるに従い、シランの加
水分解、縮合の反応速度は大きくなり加水分解性
基を３個有するシリル基含有ビニル系樹脂におい
ては共重合時及び架橋前の保存時の水分量を極め
て少なく抑える必要があり作業性の点で大きな問
題である。又、架橋反応時、アルコールの様なカ
サの大きな分子が樹脂中から抜けるため、加水分
解性基を３個有するシリル基含有ビニル系樹脂に
おいては、部分的に大きな歪がかかり、また部分
的に架橋密度が高くなり、例えば塗料として使用
した場合、塗膜の亀裂及び屈曲性の欠除等の欠点
がみられる。これに対し本発明の加水分解性基を
２個有するシリル基含有ビニル系樹脂において
は、以上の様な欠点はなく、また縮合触媒を用い
ることにより架橋速度は加水分解性基を３個有す
るシリル基含有ビニル系樹脂に劣らない状態とす
ることができることが判かり本発明に至つた。
本発明の樹脂においては、１分子中に少くとも
１個好ましくは２個以上の２官能性シリル基を有
するものであり、該シリル基の多くは
The present invention relates to a silyl group-containing vinyl resin. The resin of the present invention has the formula (In the formula, R 1 is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group, R 3 is an organic group having a polymerizable double bond,
X is a group selected from halogen, alkoxy, acyloxy, aminoxy, phenoxy, thioalkoxy, and amino groups. ) By radically copolymerizing the silane compound represented by the formula with a vinyl compound, the main chain is substantially composed of a vinyl polymer, and a small number of silicon groups bonded to two hydrolyzable groups is contained in one molecule. Both have one,
It is a silyl group-containing vinyl resin having a silyl group equivalent weight of 300 to 2,500 and a number average molecular weight of 300 to 30,000, which is suitable as a coating material. The present invention is a compound containing a silyl group having a hydrolyzable group at the terminal or side chain, and therefore not only has the characteristics of a vinyl resin but also improves adhesion. It forms a dense network structure and becomes a resin with excellent solvent resistance, water resistance, heat resistance, hardness, and weather resistance.
Since it crosslinks at room temperature or low temperature and becomes a resin with excellent physical properties, it is very suitable as a resin for paints and coatings, where pollution-free and resource-saving are currently attracting great attention. In particular, the resin of the present invention
Another major advantage is that it can obtain physical properties that require a lower molecular weight than conventional vinyl resins, making it easier to apply to high solid content type paints. Various vinyl resins are already well known and have been used in large quantities as thermoplastic resins.
In addition, as a silyl group-containing vinyl resin, JP-A-Sho
Various types are known, such as No. 49-45130. However, although these are known as curing resins, the reality is that they are not used at all as components of paints such as those used in the present invention. As a result of intensive research, the present inventors have found that only silyl group-containing vinyl resins that have a specific molecular weight and have two hydrolyzable functional groups in one silyl group form an excellent coating film. I discovered that. In the present invention, the number of hydrolyzable groups bonded to one silicon atom is important as well as the molecular weight.
Silyl group-containing vinyl resins having three hydrolyzable groups are known, but silyl group-containing vinyl resins having two hydrolyzable groups as in the present invention are not known. For example, according to JP-A-49-45130, a vinyl monomer and γ-methacryloxypropyltrimethoxysilane are copolymerized with a radical initiator to synthesize a silyl group-containing vinyl resin having three hydrolyzable groups. are doing. The vinyl resin thus obtained can be crosslinked at room temperature in the same way as the vinyl resin according to the present invention. However, silyl group-containing vinyl resins having three hydrolyzable groups have several drawbacks due to the fact that they have three hydrolyzable groups. Although the reason is not clear, it is presumed as follows. In other words, as the number of hydrolyzable groups increases, the reaction rate of hydrolysis and condensation of silane increases. It is necessary to keep the amount extremely small, which is a big problem in terms of workability. In addition, during the crosslinking reaction, large bulk molecules such as alcohol escape from the resin, so silyl group-containing vinyl resins that have three hydrolyzable groups are partially strained, and partially The crosslinking density increases and, for example, when used as a paint, disadvantages such as cracks in the coating and lack of flexibility are observed. On the other hand, the silyl group-containing vinyl resin having two hydrolyzable groups of the present invention does not have the above drawbacks, and by using a condensation catalyst, the crosslinking rate is lower than that of the silyl group having three hydrolyzable groups. It has been found that it is possible to achieve conditions comparable to group-containing vinyl resins, leading to the present invention. The resin of the present invention has at least one, preferably two or more, difunctional silyl groups in one molecule, and most of the silyl groups are
【式】（Ｘは加水分解性基、R1，R2は
水素または炭素数１〜10までのアルキル基、アリ
ール基またはアラルキル基を示す。）で示される。
以上の様に本発明の加水分解性基を２個有する
シリル基含有ビニル系樹脂は新規な物質である。
本発明のシリル基含有ビニル系樹脂の製造は、
ビニル系化合物と重合性二重結合を有するシリル
化合物とのラジカル共重合法による。以下に詳細
に説明する。
本発明の樹脂は、式
（式中、R1、R3、Ｘは前記に同じ）
で示されるシラン化合物と各種ビニル系化合物を
ラジカル重合することにより製造される。
本発明に使用されるシラン化合物としては、例
えば、It is represented by the formula: (X is a hydrolyzable group, R 1 and R 2 are hydrogen or an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group). As described above, the silyl group-containing vinyl resin having two hydrolyzable groups of the present invention is a novel substance. The production of the silyl group-containing vinyl resin of the present invention includes:
Based on a radical copolymerization method of a vinyl compound and a silyl compound having a polymerizable double bond. This will be explained in detail below. The resin of the present invention has the formula (In the formula, R 1 , R 3 , and X are the same as described above.) It is produced by radical polymerizing a silane compound represented by the following formula and various vinyl compounds. Examples of the silane compounds used in the present invention include:
【式】【formula】
等が挙げられる。
これらのシラン化合物は種々の方法により合成
されるが、例えばアセチレン、アリルアクリレー
ト、アリルメタクリレート、ジアリルフタレート
とメチルジメトキシシラン、メチルジクロルシラ
ンとを族遷移金属の触媒下で反応させることに
より製造することができる。
本発明に使用されるビニル系化合物としてはス
チレン、α−メチルスチレン、アクリル酸及びそ
のエステル、メタクリル酸及びそのエステル、ア
クリルアミド、酢酸ビニル、エチレン、無水マレ
イン酸等がある。これらビニル系化合物とシラン
化合物の共重合体の合成は通常の溶液重合法でお
こなわれる。ビニル系化合物、シラン化合物、ラ
ジカル開始剤、または分子量300〜30000の共重合
体を得るために必要に応じてｎ−ドデシルメルカ
プタン、ｔ−ドデシルメルカプタンの如き連鎖移
動剤を加え、50〜150℃で反応させる。溶剤は使
用しても、しなくてもよいが、使用する場合はエ
ーテル類、炭化水素類、酢酸エステル類の如き非
反応性の溶剤の使用が好ましい。またシリル基１
個当りの分子量（シリル基当量）が300〜2500に
なるよう前記のシラン化合物の使用量を選択して
決める。シリル基当量が300末満では重合体分子
間の架橋密度が高くなり過ぎて塗装後の塗膜の亀
裂が生じ易くなり、2500をこえると逆に架橋密度
が低くなり塗膜の耐溶剤性が低下する傾向があ
る。
この様にして得られたシリル基含有ビニル系樹
脂の加水分解性官能基としては、ハロゲン基、ア
ルコキシ基、アシロキシ基、アミノキシ基、フエ
ノキシ基、チオアルコキシ基、アミノ基が挙げら
れる。これらの中でハロゲン官能基を他の加水分
解性官能基に変換する方法としては次の方法があ
る。(1)アルコキシ基に変換する方法としては、
メタノール、エタノール、２−メトキシエタノー
ル、sec−ブタノール、tert−ブタノールおよび
フエノールの如きアルコール類及びフエノール
類、アルコール類およびフエノール類のアルカ
リ金属塩、オルトギ酸メチル、オルトギ酸エチ
ルの如きアルトギ酸アルキル類、などをハロゲン
官能基と反応させる方法が具体的に挙げられる。
(2)アシロキシ基に変換する方法としては、酢
酸、プロピオン酸、安息香酸の如きカルボン酸
類、カルボン酸類のアルカリ金属塩、などをハ
ロゲン官能基と反応させる方法が具体的に挙げら
れる。(3)アミノキシ基に変換する方法としては、
Ｎ，Ｎ−ジメチルヒドロキシルアミン、Ｎ，Ｎ
−ジエチルヒドロキシアミン、Ｎ，Ｎ−メチルフ
エニルヒドロキシルアミンおよびＮ−ヒドロキシ
ピロリジンの如きヒドロキシルアミン類、ヒド
ロキシルアミン類のアルカリ金属塩、などをハロ
ゲン官能基と反応させる方法が具体的に挙げられ
る。(4)アミノ基に変換する方法としては、Ｎ，
Ｎ−ジメチルアミン、Ｎ，Ｎ−メチルフエニルア
ミンおよびピロリジンの如き１級および２級アミ
ン類、１級および２級アミン類のアルカリ金属
塩、などをハロゲン官能基と反応させる方法が具
体的に挙げられる。(5)チオアルコキシ基に変換す
る方法としては、エチルメルカプタン、チオフ
エノールの如きチオアルコールおよびチオフエノ
ール類、チオアルコールおよびチオフエノール
類のアルカリ金属塩、などをハロゲン官能基と反
応させる方法が具体的に挙げられる。
本発明のシリル基含有ビニル樹脂は、大気中に
暴露されると常温で網状組織を形成し硬化する。
この場合の硬化速度は大気温度、相対湿度および
加水分解性基の種類により変化するので使用にあ
たつては特に加水分解性基の種類を充分考慮する
必要がある。
本発明のシリル基含有ビニル系樹脂を硬化させ
るにあたつては、硬化促進剤を使用してもしなく
てもよい。硬化促進剤を使用する場合はアルキル
チタン酸塩、オクチル酸錫およびジブチル錫ラウ
レート等の如きカルボン酸の金属塩、ジブチルア
ミン−２−ヘキソエート等の如きアミン塩ならび
に他の酸性触媒および塩基性触媒が有効である。
これら硬化速進剤の添加量は、該樹脂に対し
0.001〜10重量％で使用するのが好ましい。
本発明のシリル基含有ビニル系樹脂は、常温又
は低温でも硬化が可能である。実際、実施例で示
す様に常温で速かに硬化し表面光沢の優れた塗膜
を与える。エチルシリケート等の本発明のシリル
基含有ビニル系樹脂と共縮合可能な化合物を添加
することにより表面硬度等の物性向上を計ること
も可能である。又、現在塗料、コーテイング剤と
して用いられている種々の樹脂とブレンドするこ
とが可能であり、密着性、耐候性等の物性を向上
させることができる。
本発明のシリル基含有ビニル系樹脂は種々の充
てん剤、顔料等を混入することが可能である。充
てん剤、顔料としては、各種シリカ類、炭酸カル
シウム、炭酸マグネシウム、酸化チタン、酸化
鉄、ガラス繊維等種々のものが使用可能である。
このようにして前記の用途だけでなく、航空機、
建造物、自動車、ガラス等の被覆組成物、密封組
成物及び各種無機物の表面処理剤としても有用で
ある。
次に、実施例を記載する。
実施例 １
メタクリル酸アリル126ｇ、ヒドロキノン１ｇ、
トルエン200mlに塩化白金酸0.05ｇをイソプロパ
ノールに溶かした溶液を加え90℃に加熱し、メチ
ルジメトキシシラン127ｇを滴下し、４時間反応
させ減圧蒸留により
を得た。
次に、90℃に加熱した100ｇのトルエン中にス
チレン30ｇ、得られた
29ｇ、メタクリル酸メチル20ｇ、メタクリル酸ｎ
−ブチル19ｇ、アクリル酸ブチル14ｇ、アクリル
酸１ｇ、ｎ−ドデシルメルカプタン２ｇにアゾビ
スイソブチロニトリル２ｇを溶かした溶液を滴下
し10時間反応させ、分子量9000でシリル基当量
904のシリル基含有ビニル系重合体を得た。
比較例
実施例１の
の代りにシランカツプリング剤のCH2＝Ｃ（CH3）
COO（CH2）3Si（OCH3）327ｇを用いて重合をおこ
なつた。
以上の実施例１及び比較例で得られた重合体溶
液に固形分に対し２部のジブチル錫ラウレートを
加え、軟鋼板に塗布し、１週間室温で放置し物性
を測定した。下表に物性及び固形分50％溶液の保
存性の結果を示す。 etc. These silane compounds can be synthesized by various methods, such as by reacting acetylene, allyl acrylate, allyl methacrylate, diallyl phthalate with methyldimethoxysilane or methyldichlorosilane under a group transition metal catalyst. Can be done. Vinyl compounds used in the present invention include styrene, α-methylstyrene, acrylic acid and its esters, methacrylic acid and its esters, acrylamide, vinyl acetate, ethylene, maleic anhydride, and the like. These copolymers of vinyl compounds and silane compounds are synthesized by conventional solution polymerization methods. Add a vinyl compound, a silane compound, a radical initiator, or a chain transfer agent such as n-dodecyl mercaptan or t-dodecyl mercaptan as necessary to obtain a copolymer with a molecular weight of 300 to 30,000, and heat at 50 to 150°C. Make it react. A solvent may or may not be used, but when used, it is preferable to use a non-reactive solvent such as ethers, hydrocarbons, and acetic esters. Also, silyl group 1
The amount of the silane compound to be used is selected so that the molecular weight (silyl group equivalent) per silane compound is 300 to 2,500. If the silyl group equivalent is less than 300, the crosslinking density between polymer molecules becomes too high and the coating film tends to crack after painting.If it exceeds 2500, the crosslinking density decreases and the solvent resistance of the coating film decreases. There is a tendency to decrease. Examples of the hydrolyzable functional group of the silyl group-containing vinyl resin thus obtained include a halogen group, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group, and an amino group. Among these methods, the following methods are available for converting halogen functional groups into other hydrolyzable functional groups. (1) The method of converting to an alkoxy group is as follows:
Alcohols and phenols such as methanol, ethanol, 2-methoxyethanol, sec-butanol, tert-butanol and phenol; alkali metal salts of alcohols and phenols; alkyl altoformates such as methyl orthoformate and ethyl orthoformate; A specific example is a method of reacting the like with a halogen functional group.
(2) Specific examples of the method for converting into an acyloxy group include a method in which carboxylic acids such as acetic acid, propionic acid, and benzoic acid, alkali metal salts of carboxylic acids, and the like are reacted with a halogen functional group. (3) As a method for converting into an aminoxy group,
N,N-dimethylhydroxylamine, N,N
Specific examples include a method in which hydroxylamines such as -diethylhydroxyamine, N,N-methylphenylhydroxylamine and N-hydroxypyrrolidine, alkali metal salts of hydroxylamines, and the like are reacted with a halogen functional group. (4) As a method for converting into an amino group, N,
Specifically, there is a method of reacting primary and secondary amines such as N-dimethylamine, N,N-methylphenylamine and pyrrolidine, alkali metal salts of primary and secondary amines, etc. with a halogen functional group. Can be mentioned. (5) Specific methods for converting into thioalkoxy groups include a method in which ethyl mercaptan, thioalcohols such as thiophenol, thiophenols, alkali metal salts of thioalcohols and thiophenols, etc. are reacted with a halogen functional group. It is mentioned in When the silyl group-containing vinyl resin of the present invention is exposed to the atmosphere, it forms a network structure and hardens at room temperature.
In this case, the curing rate varies depending on atmospheric temperature, relative humidity, and the type of hydrolyzable group, so the type of hydrolyzable group must be carefully considered when using the resin. When curing the silyl group-containing vinyl resin of the present invention, a curing accelerator may or may not be used. When curing accelerators are used, alkyl titanates, metal salts of carboxylic acids such as tin octylate and dibutyltin laurate, amine salts such as dibutylamine-2-hexoate, and other acidic and basic catalysts are used. It is valid.
The amount of these curing accelerators added is determined based on the resin.
Preferably, it is used in an amount of 0.001 to 10% by weight. The silyl group-containing vinyl resin of the present invention can be cured at room temperature or low temperature. In fact, as shown in the examples, it cures quickly at room temperature and provides a coating film with excellent surface gloss. It is also possible to improve physical properties such as surface hardness by adding a compound such as ethyl silicate that can be co-condensed with the silyl group-containing vinyl resin of the present invention. Furthermore, it can be blended with various resins currently used as paints and coating agents, and physical properties such as adhesion and weather resistance can be improved. The silyl group-containing vinyl resin of the present invention can be mixed with various fillers, pigments, etc. As fillers and pigments, various kinds of silicas, calcium carbonate, magnesium carbonate, titanium oxide, iron oxide, glass fiber, etc. can be used.
In this way, not only the above-mentioned applications, but also aircraft,
It is also useful as a coating composition for buildings, automobiles, glass, etc., as a sealing composition, and as a surface treatment agent for various inorganic materials. Next, examples will be described. Example 1 Allyl methacrylate 126g, hydroquinone 1g,
A solution of 0.05 g of chloroplatinic acid dissolved in isopropanol was added to 200 ml of toluene, heated to 90°C, and 127 g of methyldimethoxysilane was added dropwise, allowed to react for 4 hours, and then distilled under reduced pressure. I got it. Next, 30g of styrene was obtained in 100g of toluene heated to 90℃. 29g, methyl methacrylate 20g, methacrylic acid n
- A solution of 2 g of azobisisobutyronitrile dissolved in 19 g of butyl, 14 g of butyl acrylate, 1 g of acrylic acid, and 2 g of n-dodecyl mercaptan was added dropwise and reacted for 10 hours, and the molecular weight was 9000 and the silyl group equivalent was
A silyl group-containing vinyl polymer of No. 904 was obtained. Comparative example Example 1 CH 2 =C(CH 3 ) of silane coupling agent instead of
Polymerization was carried out using 27 g of COO(CH 2 ) 3 Si(OCH 3 ) 3 . 2 parts of dibutyltin laurate based on the solid content was added to the polymer solutions obtained in Example 1 and Comparative Example above, and the solution was applied onto a mild steel plate, left at room temperature for one week, and its physical properties were measured. The table below shows the results of physical properties and storage stability of 50% solids solution.
【表】
以上の様に三官能性シリコンを含有するポリマ
ーに比べ、二官能性シリコンを含有するポリマー
が、屈曲性、保存性の点で優れていることが判か
る。[Table] As shown above, it can be seen that the polymer containing difunctional silicone is superior to the polymer containing trifunctional silicone in terms of flexibility and storage stability.
Claims (1)
リール基、アラルキル基より選ばれる１価の炭化
水素基、R3は重合性二重結合を有する有機基、
Ｘはハロゲン、アルコキシ、アシロキシ、アミノ
キシ、フエノキシ、チオアルコキシ、アミノ基よ
り選ばれる基である。） で示されるシラン化合物とビニル系化合物とをラ
ジカル共重合させることにより、主鎖が実質的に
ビニル系重合体からなり、２個の加水分解性基と
結合した珪素基を１分子中に少くとも１個有し、
かつそのシリル基当量が300〜2500である数平均
分子量300〜30000のシリル基含有ビニル系樹脂。[Claims] 1 Formula: (In the formula, R 1 is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group, R 3 is an organic group having a polymerizable double bond,
X is a group selected from halogen, alkoxy, acyloxy, aminoxy, phenoxy, thioalkoxy, and amino groups. ) By radically copolymerizing the silane compound represented by the formula with a vinyl compound, the main chain is substantially composed of a vinyl polymer, and a small number of silicon groups bonded to two hydrolyzable groups is contained in one molecule. Both have one,
A silyl group-containing vinyl resin having a number average molecular weight of 300 to 30,000 and a silyl group equivalent of 300 to 2,500.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3784679A JPS55129405A (en) | 1979-03-29 | 1979-03-29 | Silyl group-containing vinyl resin and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3784679A JPS55129405A (en) | 1979-03-29 | 1979-03-29 | Silyl group-containing vinyl resin and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55129405A JPS55129405A (en) | 1980-10-07 |
| JPS6360046B2 true JPS6360046B2 (en) | 1988-11-22 |
Family
ID=12508891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3784679A Granted JPS55129405A (en) | 1979-03-29 | 1979-03-29 | Silyl group-containing vinyl resin and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55129405A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57167359A (en) * | 1981-04-08 | 1982-10-15 | Dainippon Ink & Chem Inc | Cold curing resin composition for paint |
| US4598116A (en) * | 1984-11-09 | 1986-07-01 | Union Carbide Corporation | Scorch resistant compositions based on water-curable thermoplastic polymers having hydrolyzable, pendant silane moieties, and organo titanates |
| US4714738A (en) * | 1985-04-30 | 1987-12-22 | Ppg Industries, Inc. | Acrylic polymers containing hydrolyzable moieties from organosilane compounds |
| JPS6274959A (en) * | 1985-09-30 | 1987-04-06 | Kanegafuchi Chem Ind Co Ltd | Curable composition |
| JP2525238B2 (en) * | 1989-02-23 | 1996-08-14 | 三洋化成工業株式会社 | Method for producing highly weather-resistant coated base material |
| US5840800A (en) | 1995-11-02 | 1998-11-24 | Dow Corning Corporation | Crosslinked emulsions of pre-formed silicon modified organic polymers |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50123189A (en) * | 1974-03-14 | 1975-09-27 | ||
| JPS5436395A (en) * | 1977-08-25 | 1979-03-17 | Kanegafuchi Chem Ind Co Ltd | Novel vinyl type resins, their preparation, and coatings containing the same |
| JPS5437184A (en) * | 1977-08-29 | 1979-03-19 | Kanegafuchi Chem Ind Co Ltd | Novel diallylphthalate curable compound, its preparation, and adhesive and paint containing resin therefrom |
-
1979
- 1979-03-29 JP JP3784679A patent/JPS55129405A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50123189A (en) * | 1974-03-14 | 1975-09-27 | ||
| JPS5436395A (en) * | 1977-08-25 | 1979-03-17 | Kanegafuchi Chem Ind Co Ltd | Novel vinyl type resins, their preparation, and coatings containing the same |
| JPS5437184A (en) * | 1977-08-29 | 1979-03-19 | Kanegafuchi Chem Ind Co Ltd | Novel diallylphthalate curable compound, its preparation, and adhesive and paint containing resin therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55129405A (en) | 1980-10-07 |
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