JP4535764B2 - Primer composition for glass surface - Google Patents
Primer composition for glass surface Download PDFInfo
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- JP4535764B2 JP4535764B2 JP2004115464A JP2004115464A JP4535764B2 JP 4535764 B2 JP4535764 B2 JP 4535764B2 JP 2004115464 A JP2004115464 A JP 2004115464A JP 2004115464 A JP2004115464 A JP 2004115464A JP 4535764 B2 JP4535764 B2 JP 4535764B2
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- primer
- primer composition
- composition
- glass surface
- polyisocyanate
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- 239000000203 mixture Substances 0.000 title claims description 29
- 239000011521 glass Substances 0.000 title claims description 10
- 239000005056 polyisocyanate Substances 0.000 claims description 14
- 229920001228 polyisocyanate Polymers 0.000 claims description 14
- 229910052797 bismuth Inorganic materials 0.000 claims description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 9
- -1 silane compound Chemical class 0.000 claims description 8
- 239000007983 Tris buffer Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 125000005474 octanoate group Chemical group 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-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
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-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
- 241001505456 Aloysia gratissima Species 0.000 description 1
- 235000018078 Aloysia gratissima var schulziae Nutrition 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 241000272194 Ciconiiformes Species 0.000 description 1
- 241000178435 Eliokarmos dubius Species 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 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
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 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
- BSJLEDBWSQNUBG-UHFFFAOYSA-N diethoxysilylmethanamine Chemical compound CCO[SiH](CN)OCC BSJLEDBWSQNUBG-UHFFFAOYSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- GDKZYUIRADWUBI-UHFFFAOYSA-N n'-(2-methyl-3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CC(C)CNCCN GDKZYUIRADWUBI-UHFFFAOYSA-N 0.000 description 1
- CSNJSTXFSLBBPX-UHFFFAOYSA-N n'-(trimethoxysilylmethyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CNCCN CSNJSTXFSLBBPX-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 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 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- ROWWCTUMLAVVQB-UHFFFAOYSA-N triethoxysilylmethanamine Chemical compound CCO[Si](CN)(OCC)OCC ROWWCTUMLAVVQB-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 235000002894 whitebrush Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
本発明はガラス面用プライマー組成物、更に詳しくは、自動車のフロントガラスやリヤーガラスを車体に直接接着するのに適用され、特に該プライマー塗布後のオープンタイムを長期（概して３ヶ月以上）にわたって設定しても、十分プライマー性能を保持できるプライマー組成物に関する。 The present invention is applied to a glass surface primer composition, more specifically, for directly bonding an automobile windshield or rear glass to a vehicle body, and in particular, an open time after application of the primer is set over a long period (generally 3 months or more). Even so, the present invention relates to a primer composition that can maintain sufficient primer performance.
この種自動車窓ガラスの車体への接着には、一般に湿気硬化性ポリウレタン系接着剤が汎用されているが、接着性向上のため、従来より、たとえばポリエステルポリウレタン；アクリル樹脂などの皮膜形成用バインダー；シランカップリング剤；ポリイソシアネート；紫外線や可視光線を遮蔽または吸収するカーボンブラック等を有機溶剤に配合して成るプライマー組成物が使用されていた。
しかし、該プライマー塗布後接着剤塗布までのオープンタイム中に、ポリエステルポリウレタンやポリイソシアネートに含まれるイソシアネート基が大気中の水分と反応を起す結果、接着促進に有効なイソシアネート基数の減少、いわゆるプライマー表面の失活により、十分なプライマー性能が発揮できなくなるという事態を招く。なお、このようなプライマー表面の失活は概して、オープンタイム２４時間以内で見られる現状にあった。
In general, moisture curable polyurethane adhesives are commonly used for bonding this type of automobile window glass to the vehicle body. However, conventionally, for example, polyester polyurethane; a binder for film formation such as acrylic resin; A primer composition comprising a silane coupling agent; a polyisocyanate; a carbon black that shields or absorbs ultraviolet rays and visible rays, and the like in an organic solvent has been used.
However, during the open time from primer application to adhesive application, the isocyanate groups contained in the polyester polyurethane or polyisocyanate react with moisture in the atmosphere, resulting in a decrease in the number of isocyanate groups effective for promoting adhesion, so-called primer surface This will cause a situation in which sufficient primer performance cannot be exhibited due to the inactivation of. Such inactivation of the primer surface was generally observed within an open time of 24 hours.
このため、オープンタイムの長期化が望まれ、たとえば別ラインで予めプライマーを塗布した状態で７日間以上の保管後でも、十分にプライマー性能を発揮できることが望まれつつあった。こうした状況下、かかる要望に適するプライマーとして、たとえば「側鎖にアルコキシシリル基と水酸基を持った、メチルメタクリレートおよびブチルメタクリレート含有のアクリル重合体を主成分とし、これにシランカップリング剤やカーボンブラック等を加え、有機溶剤に溶解もしくは分散したプライマー組成物」（特許文献１参照）や、「１次プライマーとして、たとえば水添ポリブタジエン樹脂とポリイソシアネートを反応させて得られる末端イソシアネート基含有ウレタンプレポリマーに、アクリル樹脂溶液を加えたものと；２次プライマーとして、たとえばポリイソシアネート溶液にポリエステル樹脂溶液を加えたものとを併用するプライマー組成物」（特許文献２参照）が提案されている。 For this reason, it has been desired to extend the open time. For example, it has been desired that the primer performance can be sufficiently exhibited even after storage for 7 days or more in a state where the primer is previously applied in another line. Under such circumstances, as a primer suitable for such a request, for example, “the main component is an acrylic polymer containing methyl methacrylate and butyl methacrylate having an alkoxysilyl group and a hydroxyl group in the side chain, and a silane coupling agent, carbon black, etc. To the end isocyanate group-containing urethane prepolymer obtained by reacting, for example, a hydrogenated polybutadiene resin and a polyisocyanate as a primary primer. A primer composition in which an acrylic resin solution is added and a secondary primer in which a polyester resin solution is added to a polyisocyanate solution, for example (see Patent Document 2) has been proposed.
本発明者らは、上述の要望を満足すべきため、また上記提案プライマー組成物に優るとも劣らない、より長期にわたるオープンタイムを設定しても十分なプライマー性能を発揮でき、特に実用面で極めて重要な接着耐久性にも寄与しうるガラス面用プライマー組成物を提供するため鋭意研究を進めたところ、上記特許文献１および２並びに他の特許文献、たとえば特公昭５７−３３３１８号公報などに記載される、各種のプライマー成分や皮膜形成用バインダー、その他の配合成分の中から、以下に示す適当に採択した成分の配合物に、一般にイソシアネート基の熱によるブロック解除の触媒として、あるいはオルガノシロキサンの硬化触媒として公知の“ビスマストリスオクトエート”を特定量添加すれば、貯蔵安定性に何ら支障なく、所期目的のガラス面用プライマー組成物が得られることを見出し、本発明を完成させるに至った。 In order to satisfy the above-mentioned demands, the present inventors can exhibit sufficient primer performance even if a longer open time is set, which is not inferior to the proposed primer composition, and is extremely practical. As a result of diligent research to provide a glass surface primer composition that can also contribute to important adhesion durability, it is described in Patent Documents 1 and 2 and other patent documents such as JP-B-57-33318. Among the various primer components, film-forming binders, and other compounding components, the following composition of appropriately selected components is generally used as a catalyst for deblocking by heat of isocyanate groups, or organosiloxane Addition of a specific amount of “bismuth tris octoate”, which is known as a curing catalyst, has no effect on storage stability. It found that the glass surface for primer composition of the present invention can be obtained, and have completed the present invention.
すなわち、本発明は、シランカップリング剤、ポリイソシアネートとシラン化合物の反応生成物（以下、シラン変性ポリイソシアネートと称す）、皮膜形成用バインダーおよびカーボンブラックを有機溶剤に溶解もしくは分散せしめて成るプライマー組成物において、組成物全量中０．００１〜２％（重量％、以下同様）のビスマストリスオクトエートを添加したことを特徴とするガラス面用プライマー組成物を提供するものである。 That is, the present invention provides a primer composition comprising a silane coupling agent, a reaction product of a polyisocyanate and a silane compound (hereinafter referred to as silane-modified polyisocyanate), a film-forming binder, and carbon black dissolved or dispersed in an organic solvent. The glass surface primer composition is characterized by adding 0.001 to 2% (% by weight, hereinafter the same) of bismuth tris octoate in the total amount of the composition.
本発明のガラス面用プライマー組成物によれば、塗布後接着剤塗布までの長期にわたる、概して３ヶ月以上ものオープンタイムを設定しても、プライマーとしての接着促進機能が低下せず、しかも接着耐久性にも十分寄与することができる。このように、フロントガラスやリヤーガラスに予め塗布しておき、所定の期間内で保管すれば、従来必要であったオープンタイムの管理が不要となり、かついわゆるウインド工程でのプライマー塗布工程およびその装置やスペースを削除でき、ウインド工程の簡素化を図ることができる。 According to the primer composition for a glass surface of the present invention, even when an open time of 3 months or more is set for a long time from application to adhesive application, the adhesion promoting function as a primer does not deteriorate, and adhesion durability It can also contribute to sex. In this way, if it is applied in advance to the windshield and rear glass and stored within a predetermined period, the management of the open time, which has been necessary in the past, becomes unnecessary, and the primer application process in the so-called window process and its apparatus And space can be deleted, and the window process can be simplified.
本発明で用いるシランカップリング剤としては、たとえばγ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−イソシアネートプロピルトリメトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−（β−アミノエチル）−γ−アミノプロピルトリメトキシシラン、ビニルトリメトキシシラン等が挙げられる。使用量は通常、組成物全量中２〜１５％の範囲で選定すればよい。 Examples of the silane coupling agent used in the present invention include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-mercapto. Propyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, vinyltrimethoxysilane Etc. What is necessary is just to select the usage-amount in the range of 2-15% normally in the composition whole quantity.
本発明で用いるシラン変性ポリイソシアネートは、ポリイソシアネート（たとえばトリメチルヘキサメチレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、リジンジイソシアネートメチルエステル、トリレンジイソシアネート、デスモジュールＮ、コロネートＨＬ等）とシラン化合物［たとえばアミノメチルトリエトキシシラン、Ｎ−（β−アミノエチル）アミノメチルトリメトキシシラン、アミノメチルジエトキシシラン、Ｎ−（β−アミノエチル）メチルトリブトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルメチルジエトキシシラン、γ−アミノイソブチルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、Ｎ−ビス（β−ヒドロキシエチル）−γ−アミノプロピルトリエトキシシラン、Ｎ−（β−アミノエチル）−γ−アミノプロピルトリメトキシシラン、Ｎ−（β−アミノエチル）−γ−アミノプロピルメチルジメトキシシラン、Ｎ−（β−アミノエチル）−γ−アミノ−β−メチルプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、３，４−エポキシシクロヘキシルエチルトリメトキシシラン、３，４−エポキシシクロヘキシルエチルメチルジメトキシシラン等の反応によって製造され、使用量は通常、組成物全量中２〜１０％の範囲で選定すればよい。 The silane-modified polyisocyanate used in the present invention includes polyisocyanate (for example, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate methyl ester, tolylene diisocyanate, Desmodur N, coronate HL, etc.) and a silane compound [for example, aminomethyl Triethoxysilane, N- (β-aminoethyl) aminomethyltrimethoxysilane, aminomethyldiethoxysilane, N- (β-aminoethyl) methyltributoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyl Diethoxysilane, γ-aminoisobutyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, N-bis (β-hydroxyethyl) -γ-ami Nopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ -Amino-β-methylpropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethylmethyl Manufactured by a reaction such as dimethoxysilane, and the amount used is usually selected in a range of 2 to 10% in the total amount of the composition.
本発明で用いる皮膜形成用バインダーとしてはポリエステル、ポリエステルウレタン、アクリル樹脂、シリコーン樹脂、エチレン酢酸ビニル共重合体、ポリオレフィン、ポリカーボネート、ポリアミド等が挙げられる。特にアクリル樹脂が耐候性に優れるので望ましい。バインダーの使用量は通常、組成物全量中２〜１０％の範囲で選定すればよい。
本発明で用いるカーボンブラックの使用量は通常、組成物全量中２〜１５％の範囲で選定すればよい。
Examples of the film forming binder used in the present invention include polyester, polyester urethane, acrylic resin, silicone resin, ethylene vinyl acetate copolymer, polyolefin, polycarbonate, polyamide and the like. In particular, an acrylic resin is preferable because it has excellent weather resistance. What is necessary is just to select the usage-amount of a binder in the range of 2 to 10% normally in the composition whole quantity.
The amount of carbon black used in the present invention is usually selected within a range of 2 to 15% of the total composition.
本発明で用いる有機溶剤としては、たとえば酢酸エチル、酢酸ブチル、セロソルブアセテート、ミネラルスピリット、トルエン、キシレン、ジメチルアセトアミド、メチルエチルケトン、アセトン、ｎ−ヘキサン、テトラヒドロフラン、エチルエーテル、ジオキサン等が挙げられる。 Examples of the organic solvent used in the present invention include ethyl acetate, butyl acetate, cellosolve acetate, mineral spirit, toluene, xylene, dimethylacetamide, methyl ethyl ketone, acetone, n-hexane, tetrahydrofuran, ethyl ether, dioxane and the like.
本発明で用いるビスマストリスオクトエートの使用量は、組成物全量中０．００１〜２％、好ましくは０．０１〜１．０％の範囲で選定する。０．００１％未満では、プライマーのオープンタイムを延長する効果が得られず、また２％を超えると、貯蔵安定性が損なわれる傾向となる。 The amount of bismuth tris octoate used in the present invention is selected in the range of 0.001 to 2%, preferably 0.01 to 1.0% in the total amount of the composition. If it is less than 0.001%, the effect of extending the open time of the primer cannot be obtained, and if it exceeds 2%, the storage stability tends to be impaired.
本発明に係るガラス面用プライマー組成物は、上記所定量のシランカップリング剤、シラン変性ポリイソシアネート、皮膜形成用バインダー、カーボンブラックおよびビスマストリスオクトエートを有機溶剤に溶解もしくは分散した系で構成され、さらに必要に応じて、無機顔料、有機染顔料、紫外線吸収剤、充填剤、増粘剤、可塑剤、ポリエステル、ポリエステルウレタン、エポキシ樹脂等を適量加えてもよい。 The primer composition for a glass surface according to the present invention comprises a system in which the predetermined amount of a silane coupling agent, a silane-modified polyisocyanate, a film-forming binder, carbon black, and bismuth trisoctate are dissolved or dispersed in an organic solvent. Further, if necessary, an appropriate amount of inorganic pigment, organic dye / pigment, ultraviolet absorber, filler, thickener, plasticizer, polyester, polyester urethane, epoxy resin, etc. may be added.
次に実施例および比較例を挙げて、本発明をより具体的に説明する。
実施例１〜４
（１）シラン変性ポリイソシアネートの製造
末端にイソシアネート基（ＮＣＯ）を３個有する分子量約６９０のポリイソシアネート（武田薬品（株）製「タケネートＤ−１２０Ｎ」）２７０ｇを、メチルエチルケトン（ＭＥＫ）３３０ｇ中ジブチル錫ジラウレート１ｇの存在下、γ−メルカプトプロピルトリメトキシシラン１６０ｇと、７０℃で２０時間反応させて、遊離ＮＣＯ含有量０．７％のシラン変性ポリイソシアネートを得る。
Next, an Example and a comparative example are given and this invention is demonstrated more concretely.
Examples 1-4
(1) Production of silane-modified polyisocyanate 270 g of polyisocyanate having three isocyanate groups (NCO) at the end and a molecular weight of about 690 (“Takenate D-120N” manufactured by Takeda Pharmaceutical Co., Ltd.) in dibutyl in 330 g of methyl ethyl ketone (MEK) In the presence of 1 g of tin dilaurate, 160 g of γ-mercaptopropyltrimethoxysilane is reacted at 70 ° C. for 20 hours to obtain a silane-modified polyisocyanate having a free NCO content of 0.7%.
（２）プライマー組成物の調製
上記（１）のシラン変性ポリイソシアネート７部（重量部、以下同様）、γ−グリシドキシプロピルトリメトキシシラン３部、Ｎ−（β−アミノエチル）−γ−アミノプロピルメチルジメトキシシラン２部、ビニルトリメトキシシラン２部、カーボンブラック１０部、アクリル樹脂７部およびエポキシ樹脂２部を、ＭＥＫ７２部に溶解もしくは分散せしめた系に、下記部数（含有量）のビスマストリスオクトエートを加える。
実施例 ビスマストリスオクトエート
１ ０．１部 （約０．０９５％）
２ ０．２部 （約０．１９％）
３ ０．０１部（約０．００９５％）
４ １部 （約０．９４％）
(2) Preparation of primer composition 7 parts of silane-modified polyisocyanate (1 part by weight), 3 parts of γ-glycidoxypropyltrimethoxysilane, N- (β-aminoethyl) -γ- In a system in which 2 parts of aminopropylmethyldimethoxysilane, 2 parts of vinyltrimethoxysilane, 10 parts of carbon black, 7 parts of acrylic resin and 2 parts of epoxy resin are dissolved or dispersed in 72 parts of MEK, the following parts (content) of bismuth Add tris octoate.
Example Bismuth Tris Octoate
1 0.1 part (about 0.095%)
2 0.2 parts (about 0.19%)
3 0.01 parts (about 0.0095%)
4 1 copy (approx. 0.94%)
比較例１
実施例１〜４／（２）において、ビスマストリスオクトエートを省略する以外は、同様にしてプライマー組成物を得る。
比較例２
実施例１〜４／（２）において、ビスマストリスオクトエートの代わりにジブチル錫ジラウレート０．１部を用いる以外は、同様にしてプラマー組成物を得る。
比較例３
実施例１〜４／（２）において、ビスマストリスオクトエートの代わりにジブチル錫ビスアセチルアセトネート０．１部を用いる以外は、同様にしてプライマー組成物を得る。
Comparative Example 1
In Examples 1-4 / (2), a primer composition is obtained in the same manner except that bismuth tris octoate is omitted.
Comparative Example 2
In Examples 1 to 4 / (2), a plummer composition is obtained in the same manner except that 0.1 part of dibutyltin dilaurate is used instead of bismuth trisoctoate.
Comparative Example 3
In Examples 1 to 4 / (2), a primer composition is obtained in the same manner except that 0.1 part of dibutyltin bisacetylacetonate is used instead of bismuth trisoctoate.
性能試験
実施例１〜４および比較例１〜３のプライマー組成物について、下記の性能試験を行い、結果を表１に示す。
（１）手剥離接着性（オープンタイム性能）
フロート板ガラス上に各プライマー組成物を白刷毛にて約２０ｇ／ｍ２の量で塗布し、直ちに３５℃、９０％ＲＨの雰囲気下で９０日間放置（オープンタイム設置）した後、さらに湿気硬化性ポリウレタン系接着剤（サンスター技研（株）製「ペンギンシール＃５６０」）を３ｍｍ厚となるように塗布し、２０℃、６５％ＲＨ×３日間の養生硬化後、下記の条件を経て手剥離接着性試験を行なう。
Performance test The following performance test was done about the primer composition of Examples 1-4 and Comparative Examples 1-3, and a result is shown in Table 1.
(1) Hand peel adhesion (open time performance)
Each primer composition was coated on a float plate glass with a white brush in an amount of about 20 g / m 2 and immediately left in an atmosphere of 35 ° C. and 90% RH for 90 days (open time setting). A polyurethane adhesive ("Penguin Seal # 560" manufactured by Sunstar Giken Co., Ltd.) was applied to a thickness of 3 mm, cured after curing at 20 ° C and 65% RH x 3 days, and then manually peeled off under the following conditions Perform adhesion test.
条件
室温硬化：２０℃、６５％ＲＨ×６日
加熱老化：８０℃×１０日
水浸漬老化：４０℃水×１０日
ウインドウォッシャ液老化：５０％水希釈品、２０℃×１０日
短時間水浸漬老化：２０℃、６５％ＲＨ×３時間＋４０℃水×３日
促進耐候性：サンシャインウエザオメータ１０００時間
Condition Room temperature curing: 20 ° C., 65% RH × 6 days Heat aging: 80 ° C. × 10 days Water immersion aging: 40 ° C. water × 10 days Window washer fluid aging: 50% water diluted product, 20 ° C. × 10 days Short time water Immersion aging: 20 ° C., 65% RH × 3 hours + 40 ° C. water × 3 days Accelerated weather resistance: 1000 hours of sunshine weatherometer
（２）貯蔵安定性
各プライマー組成物を１５０ｍＬ用金属缶に密封し、４０℃×２０日間放置した後、プライマーの粘度変化をフォードカップＮｏ．４にて測定する。
(2) Storage stability Each primer composition was sealed in a 150 mL metal can and allowed to stand at 40 ° C. for 20 days. Measure at 4.
ＣＦ１００：接着剤の凝集破壊１００％
ＰＳ：プライマー／接着剤の界面破壊で、ＰＳ８０は界面破壊８０％、凝集破壊２０％ を意味する。
CF100: 100% cohesive failure of adhesive
PS: Primer / adhesive interface failure. PS80 means 80% interface failure and 20% cohesive failure.
Claims (1)
A primer composition comprising a silane coupling agent, a reaction product of a polyisocyanate and a silane compound, a film-forming binder, and carbon black dissolved or dispersed in an organic solvent, and 0.001 to 2% by weight of bismuth in the total amount of the composition A primer composition for glass surface, characterized in that tris octoate is added.
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| US8232362B2 (en) * | 2005-09-15 | 2012-07-31 | Momentive Performance Materials Inc. | Preparation of amino-silane terminated polymer by using organic bismuth catalyst and cured polymer therefrom by using non-tin catalyst |
| US20090011256A1 (en) * | 2006-02-24 | 2009-01-08 | Idemitsu Kosan Co., Ltd. | Coating composition, hardened film and resin laminate |
| BRPI0715322A2 (en) * | 2006-10-05 | 2013-07-16 | Dow Global Technologies Inc | improved binder composition, bonded structure and method of attaching a glass panel to the structure of a vehicle |
| JP5154187B2 (en) * | 2007-10-03 | 2013-02-27 | アイカ工業株式会社 | Surface urethane resin composition for waterworks |
| JP5933927B2 (en) * | 2011-03-08 | 2016-06-15 | 帝人株式会社 | Adhesive structure |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02145661A (en) * | 1988-11-28 | 1990-06-05 | Sunstar Eng Inc | Primer composition for glass |
| JPH036274A (en) * | 1989-05-31 | 1991-01-11 | Sunstar Eng Inc | Primer composition |
| JPH0465417A (en) * | 1990-07-04 | 1992-03-02 | Yokohama Rubber Co Ltd:The | Polyurethane composition |
| US5792811A (en) * | 1996-12-30 | 1998-08-11 | The Dow Chemical Company | Primer composition for improving the bonding of a urethane adhesive |
| JP2001342235A (en) * | 2000-05-31 | 2001-12-11 | Nitto Kasei Co Ltd | Curing type composition |
| JP2002524592A (en) * | 1998-09-04 | 2002-08-06 | バイエル アクチェンゲゼルシャフト | Reactive binder with extended pot life |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02145661A (en) * | 1988-11-28 | 1990-06-05 | Sunstar Eng Inc | Primer composition for glass |
| JPH036274A (en) * | 1989-05-31 | 1991-01-11 | Sunstar Eng Inc | Primer composition |
| JPH0465417A (en) * | 1990-07-04 | 1992-03-02 | Yokohama Rubber Co Ltd:The | Polyurethane composition |
| US5792811A (en) * | 1996-12-30 | 1998-08-11 | The Dow Chemical Company | Primer composition for improving the bonding of a urethane adhesive |
| JP2002524592A (en) * | 1998-09-04 | 2002-08-06 | バイエル アクチェンゲゼルシャフト | Reactive binder with extended pot life |
| JP2001342235A (en) * | 2000-05-31 | 2001-12-11 | Nitto Kasei Co Ltd | Curing type composition |
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| R250 | Receipt of annual fees |
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