JPH1036752A - Curable coating composition - Google Patents
Curable coating compositionInfo
- Publication number
- JPH1036752A JPH1036752A JP8486497A JP8486497A JPH1036752A JP H1036752 A JPH1036752 A JP H1036752A JP 8486497 A JP8486497 A JP 8486497A JP 8486497 A JP8486497 A JP 8486497A JP H1036752 A JPH1036752 A JP H1036752A
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- coating composition
- curable coating
- component
- 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.)
- Granted
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 16
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000004641 Diallyl-phthalate Substances 0.000 claims abstract description 6
- 239000004593 Epoxy Substances 0.000 claims abstract description 6
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 229920001400 block copolymer Polymers 0.000 claims abstract description 3
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 229920000728 polyester Polymers 0.000 claims abstract description 3
- -1 ether ester Chemical class 0.000 claims description 14
- 229940126062 Compound A Drugs 0.000 claims description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical group NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229940126214 compound 3 Drugs 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 239000004480 active ingredient Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 3
- 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 abstract 2
- 239000003973 paint Substances 0.000 description 14
- 238000001723 curing Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000004922 lacquer Substances 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
- 239000008096 xylene Substances 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
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 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 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-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
- KHLRJDNGHBXOSV-UHFFFAOYSA-N 5-trimethoxysilylpentane-1,3-diamine Chemical compound CO[Si](OC)(OC)CCC(N)CCN KHLRJDNGHBXOSV-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004923 Acrylic lacquer Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-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
- 239000006096 absorbing agent Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- UIJGNTRUPZPVNG-UHFFFAOYSA-N benzenecarbothioic s-acid Chemical compound SC(=O)C1=CC=CC=C1 UIJGNTRUPZPVNG-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- FAXZWVLVYZJMPC-UHFFFAOYSA-N butyl(sulfanylidene)tin Chemical compound CCCC[Sn]=S FAXZWVLVYZJMPC-UHFFFAOYSA-N 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- NCEXYHBECQHGNR-UHFFFAOYSA-N chembl421 Chemical compound C1=C(O)C(C(=O)O)=CC(N=NC=2C=CC(=CC=2)S(=O)(=O)NC=2N=CC=CC=2)=C1 NCEXYHBECQHGNR-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- WNEDOMBPJDUQPS-BFIADXHOSA-L dioctyltin(2+);(z)-4-hydroxy-4-oxobut-2-enoate Chemical compound CCCCCCCC[Sn](OC(=O)\C=C/C(O)=O)(OC(=O)\C=C/C(O)=O)CCCCCCCC WNEDOMBPJDUQPS-BFIADXHOSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000013615 primer Substances 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 229940103494 thiosalicylic acid Drugs 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水分により室温硬
化しうるシリル基末端化合物と、シラノール縮合触媒で
ある有機錫化合物及びポットライフ調節剤としてメルカ
プト基含有化合物を有効成分として含有する新規な硬化
性塗料用組成物に関する。The present invention relates to a novel curing method comprising a silyl group-terminated compound capable of curing at room temperature with moisture, an organotin compound as a silanol condensation catalyst, and a mercapto group-containing compound as a pot life regulator as active ingredients. The present invention relates to a composition for a functional paint.
【０００２】湿分硬化性シリル官能基を末端に有する化
合物は、塗料、コーティング材、接着剤、密封剤などと
して有用な材料である。[0002] Moisture-curable compounds having silyl functional groups at the terminals are useful materials as paints, coatings, adhesives, sealants and the like.
【０００３】[0003]
【従来の技術と発明が解決しようとする課題】シリル基
含有化合物の硬化特性については、硬化剤の種類により
大きく影響を受けるため、用途にあった硬化剤の選択が
不可欠であった。例えばシリル基含有化合物−有機錫化
合物を自動車補修用塗料として用いた場合、ポットライ
フ、外観性と硬化性のバランスが悪く、実用上使用する
には問題が多い。すなわち有機錫化合物の使用量を少な
くすればポットライフ、外観性は向上するが、硬化性が
悪くなり、一方、有機錫化合物の使用量を多くすると硬
化性は実用上問題ないが、ポットライフと外観性は極端
に低下するので、実用上の大きな障壁となっていた。2. Description of the Related Art Since the curing characteristics of a silyl group-containing compound are greatly affected by the type of curing agent, it is essential to select a curing agent suitable for the intended use. For example, when a silyl group-containing compound-organotin compound is used as a paint for repairing automobiles, the pot life, appearance, and curability are poorly balanced, and there are many problems in practical use. That is, if the amount of the organotin compound is reduced, the pot life and the appearance are improved, but the curability is deteriorated. On the other hand, if the amount of the organotin compound is increased, the curability is practically no problem, but the pot life and Since the appearance was extremely reduced, it was a large barrier in practical use.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、この問題
に対し鋭意研究した結果、有機錫化合物にメルカプト基
含有化合物を添加すると殆んど触媒活性は低下せず、そ
の一方で、ポットライフ及び外観性が向上するという実
用上極めて重要な硬化剤となり得ることを見出した。す
なわち、本発明は、 （Ａ）下記一般式Means for Solving the Problems The present inventors have conducted intensive studies on this problem, and as a result, it has been found that when a mercapto group-containing compound is added to an organotin compound, the catalyst activity hardly decreases, while a pot It has been found that it can be a very important hardening agent for practical use that improves the life and appearance. That is, the present invention provides:
【化２】 ［式中、Ｒ１，Ｒ２は水素又は炭素数１〜１０までのア
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、Ｘはハロゲン、アルコキシ基、アシルオ
キシ基、ケトキシメート基、アミド基、酸アミド基、ア
ミノオキシ基およびメルカプト基より選ばれる基、ａ＝
０，１又は２の整数］で示されるシリル基を分子中に少
なくとも１つ有するポリエステル、エーテルエステルブ
ロック共重合体、ビニル系重合体、ジアリルフタレート
系化合物、ジアリルフタレート系共重合体、エポキシ系
化合物の１種又は２種以上の混合物 （Ｂ）有機錫化合物 （Ｃ）メルカプト基含有化合物 上記成分（Ａ）（Ｂ）（Ｃ）を有効成分として含有する
硬化性塗料用組成物であって、成分（Ａ）１００重量部
に対して成分（Ｂ）が０．０００１〜５０重量部含有し
てなり、成分（Ｃ）が成分（Ｂ）に対して重量比で０．
０５〜２０含有してなるものである。Embedded image [Wherein, R 1 and R 2 are hydrogen or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group, X is a halogen, an alkoxy group, an acyloxy group, a ketoximate group, A group selected from an amide group, an acid amide group, an aminooxy group and a mercapto group, a =
Polyester, ether ester block copolymer, vinyl polymer, diallyl phthalate compound, diallyl phthalate copolymer, epoxy compound having at least one silyl group in the molecule represented by an integer of 0, 1 or 2] (B) Organotin compound (C) Mercapto group-containing compound A curable coating composition containing the above components (A), (B), and (C) as an active component, The component (B) is contained in an amount of 0.0001 to 50 parts by weight based on 100 parts by weight of the component (A), and the component (C) is added in a weight ratio of 0.1 to 50 parts by weight of the component (B).
It contains 0.5-20.
【０００５】[0005]
【発明の実施の形態】本発明のシリル基含有化合物
（Ａ）の製造は種々の方法で可能である。例えば炭素
−炭素二重結合を有するビニル系樹脂とヒドロシランと
によるヒドロシリル化反応、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共重合、エポキシ
基を有する化合物とアミノシラン又はメルカプトシラン
等との反応がある。，の詳細な合成方法については
特開昭５４−３６３９５、特開昭５７−６３３５１、特
公昭５９−１４２３等に示されている。の方法におけ
るエポキシ系化合物は、例えばビスフェノールＡタイ
プ、エポキシウレタンタイプ、ノボラックタイプ等のエ
ポキシ樹脂とγ−アミノプロピルトリメトキシシラン、
γ（２−アミノエチル）−アミノプロピルトリメトキシ
シラン等アミノシラン化合物又はγ−メルカプトプロピ
ルトリメトキシシラン等メルカプトシラン化合物を反応
させることにより得られる。反応条件は、溶媒として例
えばトルエン、キシレンなどを用い、無水の状態で７０
〜８０℃でこれらを数時間撹拌混合すればよい。BEST MODE FOR CARRYING OUT THE INVENTION The silyl group-containing compound (A) of the present invention can be produced by various methods. For example, a hydrosilylation reaction between a vinyl resin having a carbon-carbon double bond and a hydrosilane, a copolymerization of a vinyl compound and a silyl compound having a polymerizable double bond, a compound having an epoxy group and an aminosilane or mercaptosilane, etc. There is a reaction. Are disclosed in JP-A-54-36395, JP-A-57-63351, JP-B-59-1423 and the like. The epoxy compound in the method of, for example, bisphenol A type, epoxy urethane type, epoxy resin such as novolak type and γ-aminopropyltrimethoxysilane,
It is obtained by reacting an aminosilane compound such as γ (2-aminoethyl) -aminopropyltrimethoxysilane or a mercaptosilane compound such as γ-mercaptopropyltrimethoxysilane. The reaction conditions are as follows.
What is necessary is just to stir and mix these at -80 degreeC for several hours.
【０００６】本発明に用いられる有機錫化合物（Ｂ）
は、オクチル酸錫、ジブチル錫ジラウレート、ジオクチ
ル錫マレート、等のカルボン酸型有機錫化合物；モノブ
チル錫サルファイド、ジオクチル錫メルカプタイド等の
スルフィド型、メルカプチド型有機錫化合物；ジオクチ
ル錫オキサイド等の有機錫オキサイド；有機錫オキサイ
ドとエチルシリケート、エチルシリケート４０、マレイ
ン酸ジメチル、フタル酸ジオクチル等のエステル化合物
との反応による化合物が有効である。これら触媒は、シ
リル基含有化合物１００重量部に対し０．０００１〜５
０重量部、好ましくは０．００１〜３０重量部用いられ
る。The organotin compound (B) used in the present invention
Are carboxylic acid-type organic tin compounds such as tin octylate, dibutyltin dilaurate, and dioctyltin malate; sulfide-type and mercaptide-type organic tin compounds such as monobutyltin sulfide and dioctyltin mercaptide; organic tin oxides such as dioctyltin oxide; A compound obtained by reacting an organic tin oxide with an ester compound such as ethyl silicate, ethyl silicate 40, dimethyl maleate, or dioctyl phthalate is effective. These catalysts are used in an amount of 0.0001 to 5 per 100 parts by weight of the silyl group-containing compound.
0 parts by weight, preferably 0.001 to 30 parts by weight.
【０００７】本発明に用いられるメルカプト基含有化合
物（Ｃ）としては、ｎ−ドデシルメルカプタン、ｔｅｒ
ｔ−ブチルメルカプタン等アルキルメルカプタン；γ−
メルカプトプロピルトリメトキシシラン等メルカプトシ
ラン；２−メルカプトプロピオン酸、チオサリチル酸等
カルボン酸；チオグリコール酸２−エチルヘキシル等エ
ステル化合物；カプキュア３−８００（ダイヤモンドシ
ヤムロツクケミカルズ社製、両末端がメルカプト基であ
るポリエーテル）等のポリマー、やチオフェノール、チ
オ安息香酸等が使用される。これらメルカプト基含有化
合物は、有機錫化合物に対して重量比で０．０５〜２
０、好ましくは０．１〜１０の範囲である。The compound (C) containing a mercapto group used in the present invention includes n-dodecyl mercaptan, ter
alkyl mercaptans such as t-butyl mercaptan; γ-
Mercaptosilanes such as mercaptopropyltrimethoxysilane; carboxylic acids such as 2-mercaptopropionic acid and thiosalicylic acid; ester compounds such as 2-ethylhexyl thioglycolate; Polymers such as certain polyethers), thiophenol, and thiobenzoic acid are used. These mercapto group-containing compounds are used in a weight ratio of 0.05 to 2 with respect to the organotin compound.
0, preferably in the range of 0.1 to 10.
【０００８】有機錫化合物とメルカプト基含有化合物
は、あらかじめ所定量混合した状態でシリル基含有化合
物に加えても、また別々に添加してもよい。The organotin compound and the mercapto group-containing compound may be added to the silyl group-containing compound in a predetermined mixture, or may be added separately.
【０００９】本発明に係る硬化性塗料用組成物は、使用
前にシリル基含有化合物と有機錫化合物、メルカプト基
含有化合物を混合する方法（２液型）でも、あらかじめ
混合物に安定剤を加え、水分の混入のない状態で保存
し、そのまま用いる方法（１液型）でも、どちらでもよ
い。本発明の硬化性塗料用組成物には、成分（Ａ）、
（Ｂ）及び（Ｃ）に加えて、その他各種の充填剤、顔
料、紫外線吸収剤、酸化防止剤、艶消し剤、レベリング
剤等の通常の添加剤を公知有効濃度で含ませることがで
きる。[0009] The curable coating composition according to the present invention can also be prepared by adding a stabilizer to a mixture in advance by a method of mixing a silyl group-containing compound with an organotin compound and a mercapto group-containing compound before use (two-pack type). A method (one-pack type) of preserving in a state free of water and using as it is may be used. The composition for a curable coating composition of the present invention includes component (A),
In addition to (B) and (C), conventional additives such as various other fillers, pigments, ultraviolet absorbers, antioxidants, matting agents, leveling agents, and the like can be contained at known effective concentrations.
【００１０】[0010]
【発明の効果】本発明の硬化性塗料用組成物は、常温〜
高温の温度範囲で短時間で硬化可能であること、及び硬
化物の密着性、耐候性等の物性が優れていることから無
機物及び有機物表面に対する塗料、コーティング剤、プ
ライマー、接着剤等として有用である。特に低温硬化可
能ということから、橋りょう等の防蝕用、上塗り用、自
動車補修用塗料、有機物表面に対する塗料等としても有
効である。また現在、塗料、コーティング剤、プライマ
ー、接着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、例えばラッカー系塗料、アクリ
ルラッカー系塗料、熱硬化型アクリル塗料、アルキッド
塗料、メラミン塗料、エポキシ系塗料等と適切な割合で
混合し使用することができ、これら塗料、コーティング
剤の密着性、耐候性等の物性を向上させることができ
る。The composition for a curable coating composition of the present invention can be used at room temperature to
It can be cured in a short time in a high temperature range, and has excellent physical properties such as adhesion and weather resistance of the cured product, so it is useful as a paint, coating agent, primer, adhesive, etc. for inorganic and organic surfaces. is there. In particular, since it can be cured at a low temperature, it is also effective as a coating for corrosion protection of bridges and the like, a top coating, a repair coating for automobiles, a coating for organic material surfaces, and the like. It can be blended with various resins currently used as paints, coatings, primers and adhesives. For example, lacquer paints, acrylic lacquer paints, thermosetting acrylic paints, alkyd paints, melamine paints It can be used by mixing it with an epoxy paint or the like at an appropriate ratio, and the physical properties such as adhesion and weather resistance of these paints and coating agents can be improved.
【００１１】[0011]
【実施例】以下、本発明を実施例によって説明する。The present invention will be described below with reference to examples.
【００１２】合成例１ １１０℃に加熱した４５０ｇのキシレンに、スチレン１
５０ｇ、ブチルアクリレート３００ｇ、メチルメタクリ
レート４３０ｇ、γ−メタクリロキシプロピルトリメト
キシシラン１００ｇ、アクリルアミド２０ｇ、アゾビス
イソブチロニトリル１８ｇからなる混合液を、リフラッ
クス下、５時間にわたって滴下し、更にアゾビスイソブ
チロニトリル１ｇとキシレン９０ｇからなる混合液を１
時間滴下し、後重合２時間行い、固形分濃度６４％の溶
液を得た。溶液粘度は２５℃で１２０ポイズであった。
得られたシリル基含有化合物のＧＰＣ法による数平均分
子量は１０，０００であった。 Synthesis Example 1 Styrene 1 was added to 450 g of xylene heated to 110 ° C.
A mixture of 50 g, 300 g of butyl acrylate, 430 g of methyl methacrylate, 100 g of γ-methacryloxypropyltrimethoxysilane, 20 g of acrylamide, and 18 g of azobisisobutyronitrile was added dropwise under reflux for 5 hours. A mixed solution consisting of 1 g of butyronitrile and 90 g of xylene was added to 1
The mixture was added dropwise for 2 hours, followed by polymerization for 2 hours to obtain a solution having a solid content of 64%. The solution viscosity was 120 poise at 25 ° C.
The number average molecular weight of the obtained silyl group-containing compound measured by GPC was 10,000.
【００１３】実施例１〜５および比較例１ 合成例１で得られたシリル基含有化合物１００重量部
（固形分換算）を、キシレンにて固形分濃度３５％に希
釈した後、ジオクチル錫ジマレート２重量部、メルカプ
ト基含有化合物１重量部加えた。得られた硬化性塗料用
組成物を予めラッカープラサフを塗装しておいた磨き軟
鋼板上にスプレー塗装し、２０℃、３０分セッティング
をした後、６０℃での硬化性及び２０℃でのポットライ
フ等物性測定を行った。結果を［表１］に示した。比較
例として、メルカプト基含有化合物を使用しない場合も
併記した。 Examples 1 to 5 and Comparative Example 1 100 parts by weight (in terms of solid content) of the silyl group-containing compound obtained in Synthesis Example 1 was diluted with xylene to a solid concentration of 35%, and then dioctyltin dimaleate 2 was added. 1 part by weight of a mercapto group-containing compound was added. The obtained curable coating composition is spray-coated on a polished mild steel sheet which has been coated with lacquer plastic beforehand, set at 20 ° C. for 30 minutes, and then cured at 60 ° C. and a pot at 20 ° C. Physical properties such as life were measured. The results are shown in [Table 1]. As a comparative example, the case where no mercapto group-containing compound was used was also described.
【００１４】なお、物性測定は以下の方法に従った。The physical properties were measured according to the following methods.
【００１５】ａ）外観性：ラッカープラサフ上のクリヤ
ー塗膜の塗面状態の良否で判定した。○…塗面状態良
好、×…塗面状態不良。A) Appearance: Judgment was made based on the state of the coated surface of the clear coating film on the lacquer plastic. …: Good paint surface condition, x: poor paint surface condition.
【００１６】ｂ）硬化性（マスキング性）：セッティン
グ後、６０℃で塗膜上にマスキングテープ（日東電気工
業（株）製紙粘着テープＮｏ．７２０）を所定時間毎に
はってゆき、テープ跡の状態、またはテープ跡が残らな
くなるまでの時間で判定した。B) Curability (masking property): After setting, a masking tape (paper adhesive tape No. 720 manufactured by Nitto Electric Industry Co., Ltd.) is applied to the coating at 60 ° C. every predetermined time, and the tape mark is formed. , Or the time until no tape traces remained.
【００１７】ｃ）ポットライフ：調整した組成物７０ｇ
を１００ｃｃデスカップ（テラオカ製）にとり、２０℃
の開放状態で静置し、イワタカップで調整後、２時間の
粘度変化を調べた。C) Pot life: 70 g of the prepared composition
In a 100cc Death Cup (Terraoka), 20 ℃
Was left standing in an open state, and adjusted with an Iwata cup, and the viscosity change for 2 hours was examined.
【００１８】ｄ）鉛筆硬度：ＪＩＳ−５４００に基づき
測定した。D) Pencil hardness: Measured according to JIS-5400.
【００１９】[0019]
【表１】 [Table 1]
Claims (4)
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、Ｘはハロゲン、アルコキシ基、アシルオ
キシ基、ケトキシメート基、アミド基、酸アミド基、ア
ミノオキシ基およびメルカプト基より選ばれる基、ａ＝
０，１又は２の整数］で示されるシリル基を分子中に少
なくとも１つ有するポリエステル、エーテルエステルブ
ロック共重合体、ビニル系重合体、ジアリルフタレート
系化合物、ジアリルフタレート系共重合体、エポキシ系
化合物の１種又は２種以上の混合物 （Ｂ）有機錫化合物 （Ｃ）メルカプト基含有化合物 上記成分（Ａ）（Ｂ）（Ｃ）を有効成分として含有する
硬化性塗料用組成物であって、成分（Ａ）１００重量部
に対して成分（Ｂ）が０．０００１〜５０重量部含有し
てなり、成分（Ｃ）が成分（Ｂ）に対して重量比で０．
０５〜２０含有してなることを特徴とする硬化性塗料用
組成物。(A) The following general formula: [Wherein, R 1 and R 2 are hydrogen or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group, X is a halogen, an alkoxy group, an acyloxy group, a ketoximate group, A group selected from an amide group, an acid amide group, an aminooxy group and a mercapto group, a =
Polyester, ether ester block copolymer, vinyl polymer, diallyl phthalate compound, diallyl phthalate copolymer, epoxy compound having at least one silyl group in the molecule represented by the following formula: (B) Organotin compound (C) Mercapto group-containing compound A curable coating composition containing the above components (A), (B), and (C) as an active component, The component (B) is contained in an amount of 0.0001 to 50 parts by weight based on 100 parts by weight of the component (A), and the component (C) is added in a weight ratio of 0.1 to 50 parts by weight of the component (B).
A composition for a curable coating, comprising from 0.5 to 20.
のビニル系重合体である請求項１記載の硬化性塗料用組
成物。2. Component (A) having a molecular weight of 300 to 20,000.
The curable coating composition according to claim 1, wherein the composition is a vinyl polymer.
−ドデシルメルカプタンである請求項１または２記載の
硬化性塗料用組成物。3. A compound (C) containing a mercapto group-containing compound
3. The curable coating composition according to claim 1, which is dodecyl mercaptan.
−メルカプトプロピルトリメトキシシランである請求項
１〜３のいずれか１項記載の硬化性塗料用組成物。4. The compound (C) containing a mercapto group is γ
The curable coating composition according to any one of claims 1 to 3, which is -mercaptopropyltrimethoxysilane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8486497A JP2926326B2 (en) | 1997-04-03 | 1997-04-03 | Composition for curable paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8486497A JP2926326B2 (en) | 1997-04-03 | 1997-04-03 | Composition for curable paint |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21841385A Division JPS6274959A (en) | 1985-09-30 | 1985-09-30 | Curable composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1036752A true JPH1036752A (en) | 1998-02-10 |
| JP2926326B2 JP2926326B2 (en) | 1999-07-28 |
Family
ID=13842684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8486497A Expired - Lifetime JP2926326B2 (en) | 1997-04-03 | 1997-04-03 | Composition for curable paint |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2926326B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008019362A (en) * | 2006-07-14 | 2008-01-31 | Momentive Performance Materials Japan Kk | Method for preparing reactive silicon group-containing polymer composition and room temperature curable silicon group-containing polymer composition |
-
1997
- 1997-04-03 JP JP8486497A patent/JP2926326B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008019362A (en) * | 2006-07-14 | 2008-01-31 | Momentive Performance Materials Japan Kk | Method for preparing reactive silicon group-containing polymer composition and room temperature curable silicon group-containing polymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2926326B2 (en) | 1999-07-28 |
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