JP2011127007A - Curable composition having improved heat-resistance - Google Patents
Curable composition having improved heat-resistance Download PDFInfo
- Publication number
- JP2011127007A JP2011127007A JP2009287285A JP2009287285A JP2011127007A JP 2011127007 A JP2011127007 A JP 2011127007A JP 2009287285 A JP2009287285 A JP 2009287285A JP 2009287285 A JP2009287285 A JP 2009287285A JP 2011127007 A JP2011127007 A JP 2011127007A
- Authority
- JP
- Japan
- Prior art keywords
- group
- crosslinkable silicon
- polymer
- curable composition
- weight
- 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
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- 239000000203 mixture Substances 0.000 title claims abstract description 79
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 124
- 229920000642 polymer Polymers 0.000 claims abstract description 120
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 65
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 32
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000292 calcium oxide Substances 0.000 claims abstract description 31
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 24
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 42
- 230000001070 adhesive effect Effects 0.000 abstract description 41
- 125000005702 oxyalkylene group Chemical group 0.000 abstract description 4
- -1 trimethoxysilyl group Chemical group 0.000 description 45
- 239000000047 product Substances 0.000 description 38
- 239000003054 catalyst Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 21
- 238000000034 method Methods 0.000 description 16
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- 239000003566 sealing material Substances 0.000 description 16
- 229920001451 polypropylene glycol Polymers 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
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- 230000015572 biosynthetic process Effects 0.000 description 10
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- 238000006116 polymerization reaction Methods 0.000 description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
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- 239000002904 solvent Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 7
- 239000004014 plasticizer Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical class C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003945 anionic surfactant Substances 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000013008 thixotropic agent Substances 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 150000004756 silanes Chemical class 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 5
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 4
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- 239000000654 additive Substances 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 4
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- NXMOWTFIUDDXIT-UHFFFAOYSA-L [7,7-dimethyloctanoyloxy(dioctyl)stannyl] 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCC(C)(C)C NXMOWTFIUDDXIT-UHFFFAOYSA-L 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000007665 sagging Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 3
- TYKCBTYOMAUNLH-MTOQALJVSA-J (z)-4-oxopent-2-en-2-olate;titanium(4+) Chemical compound [Ti+4].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O TYKCBTYOMAUNLH-MTOQALJVSA-J 0.000 description 2
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 2
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-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
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-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
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical group CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
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- 229920002367 Polyisobutene Polymers 0.000 description 2
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- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
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- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 2
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- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
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Abstract
Description
本発明は架橋性珪素基を有するポリオキシアルキレン系重合体を含有する硬化性組成物に関し、特に、硬化物が高温において基材に対する大きい接着強度を有する架橋性珪素基を有するポリオキシアルキレン系重合体を含有する硬化性組成物に関する。 The present invention relates to a curable composition containing a polyoxyalkylene polymer having a crosslinkable silicon group, and in particular, the cured product has a polyoxyalkylene polymer having a crosslinkable silicon group having a high adhesive strength to a substrate at a high temperature. The present invention relates to a curable composition containing a coalescence.
特許文献１や非特許文献１の１５６〜１６３ページにあるように、架橋性珪素基を有するポリオキシアルキレン系重合体は高粘度の液体で、室温で空気中の湿分等の作用によりシロキサン結合を形成することにより架橋し、硬化物としてゴム状物質を生成する。このため、架橋性珪素基を有するポリオキシアルキレン系重合体を含有する硬化性組成物は接着剤やシーリング材として使用されている。 As described on pages 156 to 163 of Patent Document 1 and Non-Patent Document 1, a polyoxyalkylene polymer having a crosslinkable silicon group is a highly viscous liquid and has a siloxane bond due to the action of moisture in the air at room temperature. To form a rubbery substance as a cured product. For this reason, the curable composition containing the polyoxyalkylene type polymer which has a crosslinkable silicon group is used as an adhesive agent or a sealing material.
接着剤やシーリング材は容器に保存され、使用時に容器から吐出されることが多い。この際、接着剤やシーリング材は粘度が低いことが望ましい。粘度が低いと吐出しやすいためである。 Adhesives and sealing materials are stored in containers and are often discharged from the containers during use. At this time, it is desirable that the adhesive and the sealing material have a low viscosity. This is because if the viscosity is low, it is easy to discharge.
また、接着剤を接着すべき基材に塗布する場合、ヘラやコーターを使用する場合がある。この場合、接着剤の塗布後に、基材に塗布された接着剤とヘラやコーターのブレード等に付着している接着剤が直ちに分離することが必要である。分離しないと接着剤が被着体とヘラやコーターのブレード等の間に糸状に残り（糸引き状態）、被着体等を汚染するからである。 Moreover, when applying an adhesive agent to the base material which should be adhere | attached, a spatula and a coater may be used. In this case, it is necessary to immediately separate the adhesive applied to the base material and the adhesive attached to the spatula, the blade of the coater, etc. after applying the adhesive. If not separated, the adhesive remains in the form of a thread between the adherend and the spatula or the blade of the coater (threaded state) and contaminates the adherend.
また、シーリング材を目地（壁材等の隙間）に施工する場合、目地に充填されたシーリング材表面をヘラで平滑にする。この場合にも、ヘラを目地のシーリング材から分離する際、ヘラと目地のシーリング材の間にシーリング材が糸状に残らないことが必要である。 Further, when the sealing material is applied to the joint (gap between the wall materials and the like), the surface of the sealing material filled in the joint is smoothed with a spatula. In this case as well, when the spatula is separated from the joint sealing material, it is necessary that the sealing material does not remain in the form of a thread between the spatula and the joint sealing material.
さらに、接着剤を垂直方向に塗布したり、シーリング材を垂直方向の目地に充填することがある。この場合、塗布後の接着剤や充填後のシーリング材が垂れないことが必要である。 Further, the adhesive may be applied in the vertical direction or the sealing material may be filled in the vertical joint. In this case, it is necessary that the adhesive after application and the sealing material after filling do not drip.
吐出性を与え、糸引きや垂れを防止するため、接着剤やシーリング材にはチクソ性を有することが望ましい。チクソ性とは流動しているときは低粘度で、静止しているときは高粘度になる性質をいう。チクソ性を有する接着剤やシーリング材は流動しているときは低粘度であるので、容器等から吐出させやすく、糸引き状態になることもない。また、これらは静止状態では高粘度であるので、垂直方向に塗布したり、垂直方向の目地に充填される場合に垂れることがない。 It is desirable that the adhesive and the sealing material have thixotropy in order to provide dischargeability and prevent stringing and sagging. The thixotropy refers to the property of having a low viscosity when flowing and a high viscosity when standing still. The thixotropic adhesive or sealing material has a low viscosity when it is flowing, so that it can be easily discharged from a container or the like and does not enter a stringing state. In addition, since these are highly viscous in a stationary state, they do not sag when applied in the vertical direction or filled in vertical joints.
接着剤やシーリング材等にチクソ性を付与するにはチクソ剤（チクソトロピック剤、レオロジーコントロール剤、揺変剤、粘弾性調整剤、垂れ防止剤とも呼ばれる）が添加される。チクソ剤には有機系のものと無機系のものがあり、無機系チクソ剤の例として、微粉末状の炭酸カルシウムやシリカを挙げることができる。特許文献２〜４や非特許文献１の１５８ページ、７〜１０行にあるように架橋性珪素基を有するポリオキシアルキレン系重合体を含有する硬化性組成物には無機系チクソ剤として微粉末状の炭酸カルシウムが使用されることが多い。チクソ性を付与するのが容易であり、組成物を保存する場合に特性の劣化を生じることがなく、充填剤としても使用でき、且つ安価だからである。 A thixotropic agent (also called a thixotropic agent, a rheology control agent, a thixotropic agent, a viscoelasticity adjusting agent, or an anti-sagging agent) is added to impart thixotropy to an adhesive or a sealing material. There are organic and inorganic thixotropic agents. Examples of inorganic thixotropic agents include finely powdered calcium carbonate and silica. Fine powder as an inorganic thixotropic agent for a curable composition containing a polyoxyalkylene polymer having a crosslinkable silicon group as described in Patent Documents 2 to 4 and Non-Patent Document 1, page 158, lines 7 to 10 Often, calcium carbonate is used. This is because it is easy to impart thixotropy, does not cause deterioration of properties when the composition is stored, can be used as a filler, and is inexpensive.
しかしながら、微粉末状の炭酸カルシウムが添加された架橋性珪素基を有するポリオキシアルキレン系重合体を含有する硬化性組成物の硬化物は基材に対する高温時の剥離強度に十分でない場合があることが判明した。自動車内部、特にエンジンルーム内部や建築物の外壁等はかなりの高温になるため、このような部分に使用される接着剤やシーリング材は高温時の大きい剥離強度が求められる。 However, a cured product of a curable composition containing a polyoxyalkylene polymer having a crosslinkable silicon group to which fine powdered calcium carbonate has been added may not be sufficient for the peel strength at high temperatures on the substrate. There was found. Since the inside of an automobile, particularly the inside of an engine room, the outer wall of a building, and the like are considerably hot, an adhesive and a sealing material used for such a part are required to have high peel strength at high temperatures.
本発明の目的は架橋性珪素基を有するポリオキシアルキレン系重合体及び膠質炭酸カルシウムを含有する硬化性組成物であって、硬化物が大きい接着強度、特に高温雰囲気下における大きい接着強度（熱間接着強度）を有する硬化性組成物を提供することにある。 An object of the present invention is a curable composition containing a polyoxyalkylene polymer having a crosslinkable silicon group and colloidal calcium carbonate, wherein the cured product has high adhesive strength, particularly high adhesive strength in a high temperature atmosphere (thermal indirect). The object of the present invention is to provide a curable composition having an adhesion strength.
本発明者等は、架橋性珪素基を分子末端に有するポリオキシアルキレン系重合体及び膠質炭酸カルシウムを含有する硬化性組成物にさらに酸化カルシウムや酸化マグネシウムを添加すると、硬化物が大きい熱間接着強度を有することを見出した。すなわち、本発明は次の硬化性組成物に関する。 When the present inventors further add calcium oxide or magnesium oxide to a curable composition containing a polyoxyalkylene polymer having a crosslinkable silicon group at the molecular end and colloidal calcium carbonate, the cured product has a large hot bond. It was found to have strength. That is, this invention relates to the following curable composition.
（１）珪素原子に結合した水酸基又は加水分解性基を有し、シロキサン結合を形成し架橋し得る架橋性珪素基を分子鎖末端に有するポリオキシアルキレン系重合体、膠質炭酸カルシウム及び酸化カルシウムと酸化マグネシウムからなる群から選択される少なくとも１種の酸化物を含有する硬化性組成物であって、架橋性珪素基を分子鎖末端に有するポリオキシアルキレン系重合体１００重量部、架橋性珪素基を分子鎖末端に有するポリオキシアルキレン系重合体以外の架橋性珪素基を有する重合体を含有する場合はすべての架橋性珪素基を有する重合体１００重量部、に対して膠質炭酸カルシウム２〜２００重量部、及び酸化カルシウムと酸化マグネシウムからなる群から選択される少なくとも１種の酸化物を２〜１００重量部含有する硬化性組成物。 (1) a polyoxyalkylene polymer having a hydroxyl group bonded to a silicon atom or a hydrolyzable group and having a crosslinkable silicon group capable of crosslinking by forming a siloxane bond at the molecular chain terminal, colloidal calcium carbonate and calcium oxide; A curable composition containing at least one oxide selected from the group consisting of magnesium oxide, 100 parts by weight of a polyoxyalkylene polymer having a crosslinkable silicon group at the molecular chain end, and a crosslinkable silicon group In the case of containing a polymer having a crosslinkable silicon group other than the polyoxyalkylene polymer having a molecular chain terminal, 100 to 100 parts by weight of the polymer having all the crosslinkable silicon groups, Curing containing 2 to 100 parts by weight of at least one oxide selected from the group consisting of parts by weight and calcium oxide and magnesium oxide Composition.
（２）前記架橋性珪素基が下記式（１）で示される基であることを特徴とする（１）記載の硬化性組成物。
（３）前記架橋性珪素基が下記式（３）で示される基であることを特徴とする（２）記載の硬化性組成物。
（４）前記架橋性珪素基においてａが２又は３であることを特徴とする（３）記載の硬化性組成物。 (4) The curable composition according to (3), wherein a is 2 or 3 in the crosslinkable silicon group.
（５）前記架橋性珪素基においてａが３であることを特徴とする（４）記載の硬化性組成物。
(5) The curable composition according to (4), wherein a is 3 in the crosslinkable silicon group.
（６）前記架橋性珪素基において加水分解性基がアルコキシ基であることを特徴とする（１）〜（５）記載の硬化性組成物。 (6) The curable composition according to any one of (1) to (5), wherein the hydrolyzable group in the crosslinkable silicon group is an alkoxy group.
（７）前記架橋性珪素基において加水分解性基がメトキシ基であることを特徴とする（６）記載の硬化性組成物。 (7) The curable composition according to (6), wherein the hydrolyzable group in the crosslinkable silicon group is a methoxy group.
（８）架橋性珪素基を分子鎖末端に有するポリオキシアルキレン系重合体１００重量部に対して、珪素原子に結合した水酸基又は加水分解性基を有し、湿分によりシロキサン結合を形成することによって架橋し得る架橋性珪素基を有する（メタ）アクリル酸エステル重合体１０〜２００重量部をさらに含有することを特徴とする（１）〜（７）記載の硬化性組成物。 (8) For 100 parts by weight of a polyoxyalkylene polymer having a crosslinkable silicon group at the molecular chain end, it has a hydroxyl group or hydrolyzable group bonded to a silicon atom and forms a siloxane bond by moisture. The curable composition according to any one of (1) to (7), further comprising 10 to 200 parts by weight of a (meth) acrylic acid ester polymer having a crosslinkable silicon group that can be crosslinked by the above.
（９）酸化カルシウムと酸化マグネシウムからなる群から選択される少なくとも１つの酸化物が表面処理されていない酸化物であることを特徴とする（１）〜（８）記載の硬化性組成物。 (9) The curable composition according to any one of (1) to (8), wherein at least one oxide selected from the group consisting of calcium oxide and magnesium oxide is an oxide that has not been surface-treated.
本発明の硬化性組成物は、硬化物が大きい熱間剥離強度を有する。 In the curable composition of the present invention, the cured product has a high hot peel strength.
本発明に用いる架橋性珪素基を有するポリオキシアルキレン系重合体の架橋性珪素基は珪素原子に結合した水酸基又は加水分解性基を有し、シロキサン結合を形成することにより架橋しうる基である。代表例としては、式（１）：
該加水分解性基や水酸基は１個の珪素原子に１〜３個の範囲で結合することができ、ａ＋（ｂの和）は１〜５の範囲が好ましい。加水分解性基や水酸基が架橋性珪素基中に２個以上結合する場合には、それらは同一であってもよく、異なっていてもよい。 The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and a + (sum of b) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different.
架橋性珪素基を形成する珪素原子は１個でもよく、２個以上であってもよいが、シロキサン結合等により連結された珪素原子の場合には、２０個程度あってもよい。
なお、式（３）：
Formula (3):
上記Ｒ１の具体例としては、たとえばメチル基、エチル基等のアルキル基、シクロヘキシル基等のシクロアルキル基、フェニル基等のアリール基、ベンジル基等のアラルキル基や、Ｒ１ ３ＳｉＯ−で示されるトリオルガノシロキシ基等があげられる。これらの中ではメチル基が好ましい。 Specific examples of R 1 include an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and R 1 3 SiO—. And triorganosiloxy group. Of these, a methyl group is preferred.
上記Ｘで示される加水分解性基としては、特に限定されず、従来公知の加水分解性基であればよい。具体的には、たとえば水素原子、ハロゲン原子、アルコキシ基、アシルオキシ基、ケトキシメート基、アミノ基、アミド基、酸アミド基、アミノオキシ基、メルカプト基、アルケニルオキシ基等があげられる。これらの中では、水素原子、アルコキシ基、アシルオキシ基、ケトキシメート基、アミノ基、アミド基、アミノオキシ基、メルカプト基およびアルケニルオキシ基が好ましく、アルコキシ基、アミド基、アミノオキシ基がさらに好ましい。加水分解性が穏やかで取扱やすいという観点からアルコキシ基が特に好ましい。アルコキシ基の中では炭素数の少ないものの方が反応性が高く、メトキシ基＞エトキシ基＞プロポキシ基の順のように炭素数が多くなるほどに反応性が低くなる。目的や用途に応じて選択できるが通常メトキシ基やエトキシ基が使用される。 It does not specifically limit as a hydrolysable group shown by said X, What is necessary is just a conventionally well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable, and an alkoxy group, an amide group, and an aminooxy group are more preferable. An alkoxy group is particularly preferred from the viewpoint of mild hydrolysis and easy handling. Among the alkoxy groups, those having a smaller number of carbon atoms have higher reactivity, and the reactivity increases as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group. Although it can be selected according to the purpose and use, a methoxy group or an ethoxy group is usually used.
式（３）で示される架橋性珪素基の場合、硬化性を考慮するとａは２以上が好ましい。通常、ａが３の場合、ａが２の場合に比較し、硬化物の硬度は大きくなるが熱間剥離強度は小さくなる。しかし本発明においては、ａが３の場合においても十分な熱間剥離強度を有しており、且つ、硬化物の硬度も大きくスピーカーの音質も優れている。 In the case of the crosslinkable silicon group represented by the formula (3), a is preferably 2 or more in consideration of curability. Usually, when a is 3, compared with the case where a is 2, the hardness of the cured product is increased, but the hot peel strength is decreased. However, in the present invention, even when a is 3, it has a sufficient hot peel strength, the hardness of the cured product is large, and the sound quality of the speaker is excellent.
架橋性珪素基の具体的な構造としては、トリメトキシシリル基、トリエトキシシリル基等のトリアルコキシシリル基、−Ｓｉ（ＯＲ）３、メチルジメトキシシリル基、メチルジエトキシシリル基等のジアルコキシシリル基、−ＳｉＲ１（ＯＲ）２、があげられる。ここでＲはメチル基やエチル基のようなアルキル基である。 Specific structures of the crosslinkable silicon group include trialkoxysilyl groups such as trimethoxysilyl group and triethoxysilyl group, dialkoxysilyl groups such as —Si (OR) 3 , methyldimethoxysilyl group, and methyldiethoxysilyl group. Group, —SiR 1 (OR) 2 . Here, R is an alkyl group such as a methyl group or an ethyl group.
また、架橋性珪素基は１種で使用しても良く、２種以上併用してもかまわない。架橋性珪素基は、主鎖または側鎖あるいはいずれにも存在しうる。本発明においては架橋性珪素基が分子鎖末端に存在するポリオキシアルキレン系重合体を使用する。架橋性珪素基が分子鎖末端に存在すると硬化物の引張特性や接着特性等の硬化物物性が優れる。ポリオキシアルキレン系重合体のすべての末端に架橋性珪素基が存在する必要はなく、分子末端の少なくとも１個、好ましくは１．１以上２個未満存在するのがよい。分子中に含まれる架橋性珪素基の数が１個未満になると、硬化性が不充分になり、また多すぎると網目構造があまりに密となるため良好な機械特性を示さなくなる。ポリオキシアルキレン系重合体の分子鎖末端に架橋性珪素基が存在すれば、分子鎖末端以外に存在してもよいが、架橋性珪素基が分子鎖末端以外に実質的に存在しないことが好ましい。 Further, the crosslinkable silicon group may be used alone or in combination of two or more. The crosslinkable silicon group can be present in the main chain, the side chain, or both. In the present invention, a polyoxyalkylene polymer having a crosslinkable silicon group at the molecular chain terminal is used. When a crosslinkable silicon group is present at the end of the molecular chain, the cured product properties such as tensile properties and adhesive properties of the cured product are excellent. It is not necessary that a crosslinkable silicon group is present at all terminals of the polyoxyalkylene polymer, and at least one of the molecular terminals, preferably 1.1 or more and less than 2, may be present. When the number of crosslinkable silicon groups contained in the molecule is less than one, the curability is insufficient, and when the number is too large, the network structure becomes too dense, and good mechanical properties are not exhibited. If a crosslinkable silicon group is present at the molecular chain end of the polyoxyalkylene polymer, it may be present other than at the molecular chain end, but it is preferable that the crosslinkable silicon group is substantially absent other than at the molecular chain end. .
本発明に用いるポリオキシアルキレン系重合体は本質的に式（４）で示される繰り返し単位を有する重合体である。
式（４）におけるＲ２は、炭素数１〜１４の、さらには２〜４の、直鎖状もしくは分岐状アルキレン基が好ましい。式（４）で示される繰り返し単位の具体例としては、例えば、 R 2 in Formula (4) is preferably a linear or branched alkylene group having 1 to 14 carbon atoms, and more preferably 2 to 4 carbon atoms. Specific examples of the repeating unit represented by the formula (4) include, for example,
架橋性珪素基を有するポリオキシアルキレン系重合体は、直鎖状でもよくまたは分岐を有してもよいが直鎖状であることが好ましい。本発明に用いるポリオキシアルキレン系重合体は数平均分子量で２０００〜５０，０００、さらには５０００〜３００００が好ましい。また分子量分布は、重量平均分子量／数平均分子量で１．０〜５．０の範囲のものを使用できるが、１．０〜２．０のように小さいほうが好ましい。 The polyoxyalkylene polymer having a crosslinkable silicon group may be linear or branched, but is preferably linear. The polyoxyalkylene polymer used in the present invention has a number average molecular weight of preferably 2000 to 50,000, more preferably 5000 to 30000. The molecular weight distribution may be 1.0 to 5.0 in terms of weight average molecular weight / number average molecular weight, but is preferably as small as 1.0 to 2.0.
架橋性珪素基を有する高分子量のポリオキシアルキレン系重合体を使用すると熱間剥離強度を含めた剥離強度に優れた硬化物を得ることができる。また、架橋性珪素基を有する低分子量のポリオキシアルキレン系重合体を使用すると剥離強度は低下するが、硬化物の硬度が大きくなる。これは分子鎖末端に架橋性珪素基を有し低分子量のポリオキシアルキレン系重合体の硬化物は架橋点間分子量が小さくため、脆い硬化物となるが硬度は大きくなるためであると考えられる。このように、分子量が異なる架橋性珪素基を有するポリオキシアルキレン系重合体を併用し、分子量や組成比を調整することにより所望の剥離強度や硬度を得ることができる。 When a high molecular weight polyoxyalkylene polymer having a crosslinkable silicon group is used, a cured product having excellent peel strength including hot peel strength can be obtained. When a low molecular weight polyoxyalkylene polymer having a crosslinkable silicon group is used, the peel strength decreases, but the hardness of the cured product increases. This is thought to be because a cured product of a polyoxyalkylene polymer having a crosslinkable silicon group at the molecular chain terminal is a brittle cured product but has a high hardness because the molecular weight between crosslinking points is small. . Thus, desired peel strength and hardness can be obtained by using together the polyoxyalkylene type polymer which has a crosslinkable silicon group from which molecular weight differs, and adjusting molecular weight and a composition ratio.
ポリオキシアルキレン系重合体の合成法としては、たとえばＫＯＨのようなアルカリ触媒による重合法、たとえば特開昭６１−１９７６３１号、同６１−２１５６２２号、同６１−２１５６２３号、同６１−２１５６２３号に示されるような有機アルミニウム化合物とポルフィリンとを反応させて得られる、有機アルミ−ポルフィリン錯体触媒による重合法、たとえば特公昭４６−２７２５０号および特公昭５９−１５３３６号などに示される複金属シアン化物錯体触媒による重合法等があげられるが、特に限定されるものではない。有機アルミ−ポルフィリン錯体触媒による重合法や複金属シアン化物錯体触媒による重合法によれば数平均分子量６，０００以上、Ｍｗ／Ｍｎが１．６以下の高分子量で分子量分布が狭いポリオキシアルキレン系重合体を得ることができる。 As a method for synthesizing a polyoxyalkylene polymer, for example, a polymerization method using an alkali catalyst such as KOH, for example, JP-A Nos. 61-197631, 61-215622, 61-215623, and 61-215623 can be used. Polymerization method using an organoaluminum-porphyrin complex catalyst obtained by reacting an organoaluminum compound and a porphyrin as shown, for example, a double metal cyanide complex shown in JP-B-46-27250 and JP-B-59-15336 Examples of the polymerization method using a catalyst include, but are not limited to, a polymerization method. A polyoxyalkylene system having a narrow molecular weight distribution with a high molecular weight having a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less according to a polymerization method using an organic aluminum-porphyrin complex catalyst or a polymerization method using a double metal cyanide complex catalyst A polymer can be obtained.
上記ポリオキシアルキレン系重合体の主鎖骨格中にはウレタン結合成分等の他の成分を含んでいてもよい。ウレタン結合成分としては、たとえばトルエン（トリレン）ジイソシアネート、ジフェニルメタンジイソシアネート、キシリレンジイソシアネート等の芳香族系ポリイソシアネート；イソフォロンジイソシアネート、ヘキサメチレンジイソシアネート等の脂肪族系ポリイソシアネートと水酸基を有するポリオキシアルキレン系重合体との反応から得られるものをあげることができる。 The main chain skeleton of the polyoxyalkylene polymer may contain other components such as a urethane bond component. Examples of the urethane bond component include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate; The thing obtained from reaction with coalescence can be mention | raise | lifted.
ポリオキシアルキレン系重合体への架橋性珪素基の導入は、分子中に不飽和基、水酸基、エポキシ基やイソシアネート基等の官能基を有するポリオキシアルキレン系重合体に、この官能基に対して反応性を示す官能基および架橋性珪素基を有する化合物を反応させることにより行うことができる（以下、高分子反応法という）。 The introduction of a crosslinkable silicon group into a polyoxyalkylene polymer can be performed on a polyoxyalkylene polymer having a functional group such as an unsaturated group, a hydroxyl group, an epoxy group or an isocyanate group in the molecule. The reaction can be carried out by reacting a compound having a reactive functional group and a crosslinkable silicon group (hereinafter referred to as a polymer reaction method).
高分子反応法の具体例として、不飽和基含有ポリオキシアルキレン系重合体に架橋性珪素基を有するヒドロシランや架橋性珪素基を有するメルカプト化合物を作用させてヒドロシリル化やメルカプト化し、架橋性珪素基を有するポリオキシアルキレン系重合体を得る方法をあげることができる。不飽和基含有ポリオキシアルキレン系重合体は水酸基等の官能基を有する有機重合体に、この官能基に対して反応性を示す活性基および不飽和基を有する有機化合物を反応させ、不飽和基を含有するポリオキシアルキレン系重合体を得ることができる。 As a specific example of the polymer reaction method, a hydrosilane or mercapto compound obtained by allowing a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to act on an unsaturated group-containing polyoxyalkylene polymer to form a crosslinkable silicon group The method of obtaining the polyoxyalkylene type polymer which has this can be mention | raise | lifted. An unsaturated group-containing polyoxyalkylene polymer is obtained by reacting an organic polymer having a functional group such as a hydroxyl group with an organic compound having an active group and an unsaturated group that are reactive with the functional group, A polyoxyalkylene polymer containing can be obtained.
また、高分子反応法の他の具体例として、末端に水酸基を有するポリオキシアルキレン系重合体とイソシアネート基および架橋性珪素基を有する化合物を反応させる方法や末端にイソシアネート基を有するポリオキシアルキレン系重合体と水酸基やアミノ基等の活性水素基および架橋性珪素基を有する化合物を反応させる方法をあげることができる。イソシアネート化合物を使用すると、容易に架橋性珪素基を有するポリオキシアルキレン系重合体を得ることができる。 Other specific examples of the polymer reaction method include a method of reacting a polyoxyalkylene polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a crosslinkable silicon group, or a polyoxyalkylene system having an isocyanate group at a terminal. Examples thereof include a method of reacting a polymer with a compound having an active hydrogen group such as a hydroxyl group or an amino group and a crosslinkable silicon group. When an isocyanate compound is used, a polyoxyalkylene polymer having a crosslinkable silicon group can be easily obtained.
架橋性珪素基を有するポリオキシアルキレン系重合体の具体例としては、特公昭４５−３６３１９号、同４６−１２１５４号、特開昭５０−１５６５９９号、同５４−６０９６号、同５５−１３７６７号、同５７−１６４１２３号、特公平３−２４５０号、特開２００５−２１３４４６号、同２００５−３０６８９１号、国際公開特許ＷＯ２００７−０４０１４３号、米国特許３，６３２，５５７、同４，３４５，０５３、同４，９６０，８４４等の各公報に提案されているものをあげることができる。 Specific examples of the polyoxyalkylene polymer having a crosslinkable silicon group include JP-B Nos. 45-36319, 46-12154, JP-A Nos. 50-156599, 54-6096, and 55-13767. No. 57-164123, JP-B No. 3-2450, JP-A No. 2005-213446, No. 2005-306891, International Publication No. WO2007-040143, US Pat. No. 3,632,557, No. 4,345,053, The ones proposed in the publications such as 4,960,844 can be listed.
本発明の硬化性組成物には架橋性珪素基を有するポリオキシアルキレン系重合体以外の重合体を併用してもよい。このような重合体の例として、架橋性珪素基を有する（メタ）アクリル酸エステル系重合体をあげることができる。架橋性珪素基を有する（メタ）アクリル酸アルキルエステル系重合体を併用すると硬化物が機械強度に優れ、且つ、耐熱性や基材との接着性にも優れる特性を有するため、この重合体を併用することは本発明に特に適している。 A polymer other than the polyoxyalkylene polymer having a crosslinkable silicon group may be used in combination with the curable composition of the present invention. As an example of such a polymer, a (meth) acrylic acid ester-based polymer having a crosslinkable silicon group can be given. When a (meth) acrylic acid alkyl ester-based polymer having a crosslinkable silicon group is used in combination, the cured product has excellent mechanical strength and also has excellent heat resistance and adhesion to a substrate. The combined use is particularly suitable for the present invention.
架橋性珪素基を有する（メタ）アクリル酸アルキルエステル系重合体は本質的に式（５）で示される繰り返し単位を有する重合体である。
式（５）におけるＲ４はアルキル基であり、炭素数１〜３０のアルキル基が好ましい。Ｒ４は直鎖状であってもよく、分岐状であってもよい。また、ハロゲン原子やフェニル基等を有する置換アルキル基でもよい。Ｒ４の例としては、メチル基、エチル基、プロピル基、ｎ−ブチル基、ｔ−ブチル基、２−エチルヘキシル基、ラウリル基、トリデシル基、セチル基、ステアリル基、ベヘニル基等をあげることができる。 R 4 in Formula (5) is an alkyl group, and an alkyl group having 1 to 30 carbon atoms is preferable. R 4 may be linear or branched. Moreover, the substituted alkyl group which has a halogen atom, a phenyl group, etc. may be sufficient. Examples of R 4 include methyl group, ethyl group, propyl group, n-butyl group, t-butyl group, 2-ethylhexyl group, lauryl group, tridecyl group, cetyl group, stearyl group, and behenyl group. it can.
（メタ）アクリル酸アルキルエステル系重合体の分子鎖は本質的に式（５）の単量体単位からなるが、ここでいう「本質的に」とは該重合体中に存在する式（５）の単量体単位の合計が５０重量％をこえることを意味する。式（５）の単量体単位の合計は好ましくは７０重量％以上である。 The molecular chain of the (meth) acrylic acid alkyl ester polymer essentially consists of the monomer unit of the formula (5). The term “essentially” as used herein refers to the formula (5) present in the polymer. ) Of the monomer units exceeds 50% by weight. The total of the monomer units of the formula (5) is preferably 70% by weight or more.
式（５）以外の単量体単位の例としては、アクリル酸、メタクリル酸等の（メタ）アクリル酸に起因する単量体単位；アクリルアミド、メタクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ−メチロールメタクリルアミド等のアミド基を含む単量体に起因する単量体単位；グリシジルアクリレート、グリシジルメタクリレート等のエポキシ基を含む単量体に起因する単量体単位；ジエチルアミノエチルアクリレート、ジエチルアミノエチルメタクリレート、アミノエチルビニルエーテル等のアミノ基を含む単量体に起因する単量体単位；その他アクリロニトリル、スチレン、α−メチルスチレン、アルキルビニルエーテル、塩化ビニル、酢酸ビニル、プロピオン酸ビニル、エチレン等に起因する単量体単位があげられる。 Examples of monomer units other than the formula (5) include monomer units derived from (meth) acrylic acid such as acrylic acid and methacrylic acid; acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide Monomer units derived from monomers containing amide groups such as: monomer units derived from monomers containing epoxy groups such as glycidyl acrylate and glycidyl methacrylate; diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether Monomer units derived from monomers containing amino groups such as acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, etc. can give.
架橋性珪素基を有する（メタ）アクリル酸アルキルエステル系重合体がポリオキシアルキレン系重合体と混合して使用される場合、架橋性珪素基を有するポリオキシアルキレン系重合体との相溶性が大きい点で、架橋性珪素基を有し分子鎖が、下記式（６）：
で表される（メタ）アクリル酸エステル単量体単位と、下記式（７）：
で表される（メタ）アクリル酸エステル単量体単位からなる共重合体であることが好ましい。
When a (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group is used by mixing with a polyoxyalkylene polymer, the compatibility with the polyoxyalkylene polymer having a crosslinkable silicon group is high. In that respect, the molecular chain having a crosslinkable silicon group has the following formula (6):
(Meth) acrylic acid ester monomer unit represented by the following formula (7):
It is preferable that it is a copolymer which consists of a (meth) acrylic acid ester monomer unit represented by these.
前記式（６）のＲ５としては、たとえばメチル基、エチル基、プロピル基、ｎ−ブチル基、ｔ−ブチル基等の炭素数１〜５、好ましくは１〜４、さらに好ましくは１〜２のアルキル基があげられる。なお、Ｒ５は一種でもよく、２種以上混合してもよい。 As R < 5 > of said Formula (6), C1-C5, such as a methyl group, an ethyl group, a propyl group, n-butyl group, t-butyl group, etc., Preferably it is 1-4, More preferably, it is 1-2. Of the alkyl group. Incidentally, R 5 may be a kind or as a mixture of two or more.
前記式（７）のＲ６としては、たとえば２−エチルヘキシル基、ラウリル基、トリデシル基、セチル基、ステアリル基、ベヘニル基等の炭素数６以上、通常は７〜３０、好ましくは８〜２０の長鎖のアルキル基があげられる。なお、Ｒ６は一種でもよく、２種以上混合したものであってもよい。また、式（６）の単量体単位と式（７）の単量体単位の存在比は、重量比で９５：５〜４０：６０が好ましく、９０：１０〜６０：４０がさらに好ましい。 R 6 in the formula (7) is, for example, 2-ethylhexyl group, lauryl group, tridecyl group, cetyl group, stearyl group, behenyl group and the like having 6 or more carbon atoms, usually 7-30, preferably 8-20. Long chain alkyl groups. R 6 may be a single type or a mixture of two or more types. Moreover, the weight ratio of the monomer unit of the formula (6) and the monomer unit of the formula (7) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40.
架橋性珪素基を有する（メタ）アクリル酸アルキルエステル系重合体は通常、（メタ）アクリル酸アルキルエステルと架橋性珪素基を有する（メタ）アクリル酸アルキルエステルをラジカル共重合して得ることができる。また、架橋性珪素基を有する開始剤や架橋性珪素基を有する連鎖移動剤を使用すると分子鎖末端に架橋性珪素基を導入することができる。 The (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group can usually be obtained by radical copolymerization of a (meth) acrylic acid alkyl ester and a (meth) acrylic acid alkyl ester having a crosslinkable silicon group. . Further, when an initiator having a crosslinkable silicon group or a chain transfer agent having a crosslinkable silicon group is used, the crosslinkable silicon group can be introduced into the molecular chain terminal.
特開２００１−０４００３７号公報、特開２００３−０４８９２３号公報および特開２００３−０４８９２４号公報には架橋性珪素基を有するメルカプタンおよびメタロセン化合物を使用して得られる架橋性珪素基を有する（メタ）アクリル酸アルキルエステル系重合体が記載されている。また、特開２００５−０８２６８１号公報には高温連続重合による架橋性珪素基を有する（メタ）アクリル酸アルキルエステル系重合体が記載されている。 JP 2001-040037 A, JP 2003-048923 A and JP 2003-048924 A have a crosslinkable silicon group (meth) obtained by using a mercaptan having a crosslinkable silicon group and a metallocene compound. Acrylic acid alkyl ester polymers are described. Japanese Patent Laid-Open No. 2005-082681 describes a (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group by continuous polymerization at high temperature.
架橋性珪素基を有する（メタ）アクリル酸アルキルエステル系重合体であって架橋性珪素基が分子鎖末端に高い割合で導入された重合体も特開２０００−０８６９９９号公報等に開示されている。このような重合体はリビングラジカル重合によって製造されているため、高い割合で架橋性珪素基を分子鎖末端に導入することができる。本発明では以上に述べたような（メタ）アクリル酸アルキルエステル系重合体を使用することができる。 A (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group, in which a crosslinkable silicon group is introduced at a high ratio at the molecular chain terminal, is also disclosed in JP-A-2000-086999. . Since such a polymer is produced by living radical polymerization, a crosslinkable silicon group can be introduced into the molecular chain terminal at a high rate. In the present invention, a (meth) acrylic acid alkyl ester polymer as described above can be used.
架橋性珪素基を有する（メタ）アクリル酸エステル系重合体やこの重合体と架橋性珪素基を有するポリオキシアルキレン系重合体の混合物の具体例は、特開昭５９−１２２５４１号、同６３−１１２６４２号、同特開平６−１７２６３１号等の各公報に記載されている。また、特開昭５９−７８２２３号、特開昭５９−１６８０１４号、特開昭６０−２２８５１６号、特開昭６０−２２８５１７号等の各公報には、架橋性珪素基を有するポリオキシアルキレン系重合体の存在下で（メタ）アクリル酸エステル系単量体の重合を行い、架橋性珪素基を有するポリオキシアルキレン系重合体と架橋性珪素基を有する（メタ）アクリル酸アルキルエステル系重合体の混合物を得る方法が記載されている。 Specific examples of the (meth) acrylic acid ester-based polymer having a crosslinkable silicon group and a mixture of this polymer and a polyoxyalkylene polymer having a crosslinkable silicon group are disclosed in JP-A-59-122541 and 63-. No. 112642, JP-A-6-172631, and the like. Further, JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, and the like disclose polyoxyalkylene series having a crosslinkable silicon group. Polymerization of a (meth) acrylic acid ester monomer in the presence of a polymer, a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group A method for obtaining a mixture of is described.
架橋性珪素基を有する（メタ）アクリル酸アルキルエステル系重合体を併用する場合、架橋性珪素基を有するポリオキシアルキレン系重合体１００重量部に対し、架橋性珪素基を有する（メタ）アクリル酸エステル系重合体を１０〜２００重量部使用することが好ましく、２０〜８０重量部使用することがさらに好ましい。 When a (meth) acrylic acid alkyl ester polymer having a crosslinkable silicon group is used in combination, the (meth) acrylic acid having a crosslinkable silicon group is used with respect to 100 parts by weight of the polyoxyalkylene polymer having a crosslinkable silicon group. The ester polymer is preferably used in an amount of 10 to 200 parts by weight, more preferably 20 to 80 parts by weight.
本発明の硬化性組成物には膠質炭酸カルシウムを使用する。本発明の膠質炭酸カルシウムは０．５μｍ以下、好ましくは０．０１〜０．１μｍの一次粒子径を有する炭酸カルシウムで、多くは立方体結晶である。膠質炭酸カルシウムは通常、カルシウム塩水溶液に二酸化炭素や炭酸塩化合物を添加し沈降炭酸カルシウムとして製造される。炭酸カルシウムは充填剤として用いられるが、このような粒径が小さい炭酸カルシウムを使用することにより、硬化性組成物にチキソ性を付与することができる。 Collagen calcium carbonate is used in the curable composition of the present invention. The colloidal calcium carbonate of the present invention is calcium carbonate having a primary particle size of 0.5 μm or less, preferably 0.01 to 0.1 μm, and many are cubic crystals. Colloidal calcium carbonate is usually produced as precipitated calcium carbonate by adding carbon dioxide or a carbonate compound to an aqueous calcium salt solution. Although calcium carbonate is used as a filler, thixotropy can be imparted to the curable composition by using calcium carbonate having such a small particle size.
膠質炭酸カルシウムは高級脂肪酸系化合物等によって表面処理されていることが好ましい。表面処理剤としては、たとえば高級脂肪酸系化合物、樹脂酸系化合物、芳香族カルボン酸エステル、陰イオン系界面活性剤、陽イオン系界面活性剤、ノニオン系界面活性剤などが挙げられる。 The colloidal calcium carbonate is preferably surface-treated with a higher fatty acid compound or the like. Examples of the surface treatment agent include higher fatty acid compounds, resin acid compounds, aromatic carboxylic acid esters, anionic surfactants, cationic surfactants, and nonionic surfactants.
高級脂肪酸系化合物としてたとえばステアリン酸ナトリウムのような炭素数が１０個以上の高級脂肪酸系のアルカリ金属塩；樹脂酸系化合物としてたとえばアビエチン酸、ネオアビエチン酸、ｄ−ピマル酸、ｉ−ｄ−ピマル酸、ボドカルプ酸、安息香酸、ケイ皮酸など；芳香族カルボン酸エステルとしてたとえばフタル酸のオクチルアルコール、ブチルアルコール、イソブチルアルコールなどとのエステル、ナフト酸の低級アルコールエステル、ロジン酸の低級アルコールエステルおよび芳香族ジカルボン酸またはロジン酸のマレイン酸付加物のような芳香族ポリカルボン酸の部分エステル化物または異種アルコールエステル化物など；また陰イオン界面活性剤としてたとえばドデシル硫酸ナトリウムのような硫酸エステル型またはドデシルベンゼンスルホン酸ナトリウム、ラウリルスルホン酸ナトリウム、ドデシルベンゼンスルホン酸などのスルホン酸型の陰イオン界面活性剤が挙げられる。 Higher fatty acid compounds such as sodium stearate and higher fatty acid alkali metal salts such as sodium stearate; Resin acid compounds such as abietic acid, neoabietic acid, d-pimaric acid, id-pimal Acids, bodocarbic acid, benzoic acid, cinnamic acid, etc .; aromatic carboxylic acid esters such as phthalic acid octyl alcohol, butyl alcohol, isobutyl alcohol, etc., naphthoic acid lower alcohol ester, rosin acid lower alcohol ester and Partially esterified aromatic polycarboxylic acid such as aromatic dicarboxylic acid or maleic acid adduct of rosin acid or heteroalcohol esterified product; and sulfate type or dodecyl such as sodium dodecyl sulfate as anionic surfactant Sodium Nzensuruhon acid, sodium lauryl sulfonate, anionic surfactant of the sulfonic acid type such as dodecylbenzene sulfonic acid.
これらの表面処理剤は単独で使用してもよく、２種以上併用してもよい。たとえば、高級脂肪酸系有機物と樹脂酸系有機物とを、それらの総量が炭酸カルシウム１００重量部に対し０．２〜４重量部の範囲となるように吸着させたもの、また、硫酸エステル型またはスルホン酸型の陰イオン界面活性剤と芳香族カルボン酸のエステルとを芳香族カルボン酸のエステル１０重量部に対し硫酸エステル型またはスルホン酸型の陰イオン界面活性剤を５〜２０重量部の割合で添加できる。本発明においては、特に陰イオン系界面活性剤を単独または他の表面処理剤と併用して使用するのが好ましい。 These surface treatment agents may be used alone or in combination of two or more. For example, a higher fatty acid organic material and a resin acid organic material adsorbed so that the total amount thereof is in the range of 0.2 to 4 parts by weight with respect to 100 parts by weight of calcium carbonate, or a sulfate ester type or sulfone An acid type anionic surfactant and an ester of an aromatic carboxylic acid in a ratio of 5 to 20 parts by weight of an anionic surfactant of sulfuric acid type or sulfonic acid type with respect to 10 parts by weight of the ester of aromatic carboxylic acid. Can be added. In the present invention, it is particularly preferable to use an anionic surfactant alone or in combination with another surface treatment agent.
膠質炭酸カルシウムの使用量は、架橋性珪素基を分子鎖末端に有するオキシアルキレン系重合体１００重量部に対し、２〜２００重量部が好ましく、５〜１００重量部がさらに好ましく、１０〜５０重量部が特に好ましい。２重量部未満では、得られる組成物のチクソ性が不充分であり、また硬化後の引張物性も不充分となる。１００重量部を超えると、引張物性が低下する傾向にある。また、架橋性珪素基を有する他の重合体を併用する場合、膠質炭酸カルシウムの使用量は、架橋性珪素基を分子鎖末端に有するオキシアルキレン系重合体を含めたすべての架橋性珪素基を有する重合体１００重量部に対し、２〜２００重量部が好ましく、５〜１００重量部がさらに好ましく、１０〜５０重量部が特に好ましい。 The amount of colloidal calcium carbonate used is preferably 2 to 200 parts by weight, more preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight based on 100 parts by weight of the oxyalkylene polymer having a crosslinkable silicon group at the molecular chain terminal. Part is particularly preferred. If it is less than 2 parts by weight, the thixotropy of the resulting composition is insufficient, and the tensile properties after curing are also insufficient. If it exceeds 100 parts by weight, the tensile properties tend to decrease. When other polymers having a crosslinkable silicon group are used in combination, the amount of colloidal calcium carbonate used is that all crosslinkable silicon groups including oxyalkylene polymers having a crosslinkable silicon group at the molecular chain terminal are used. The amount is preferably 2 to 200 parts by weight, more preferably 5 to 100 parts by weight, and particularly preferably 10 to 50 parts by weight with respect to 100 parts by weight of the polymer.
本発明に使用する酸化カルシウム及び酸化マグネシウムから選ばれる少なくとも一種の酸化物を使用する。これらの中では酸化カルシウムが硬化物の耐熱性をより改善できるため好ましい。酸化物は脂肪酸や界面活性剤等で表面処理されることがあるが本発明では表面処理されていない酸化物のほうが硬化物の耐熱性をより改善できるため好ましい。 At least one oxide selected from calcium oxide and magnesium oxide used in the present invention is used. Among these, calcium oxide is preferable because it can further improve the heat resistance of the cured product. The oxide may be surface-treated with a fatty acid, a surfactant, or the like, but in the present invention, an oxide that has not been surface-treated is preferred because the heat resistance of the cured product can be further improved.
酸化カルシウムは近江化学工業（株）からＣＭＬなどの商品名で販売されている。酸化マグネシウムは神島化学工業（株）からスターマグの商品名で、協和化学工業（株）からキスマの商品名で販売されている。 Calcium oxide is sold by Omi Chemical Industry Co., Ltd. under a trade name such as CML. Magnesium oxide is sold by Kamishima Chemical Industry Co., Ltd. under the trade name of Starmag and Kyowa Chemical Industry Co., Ltd. under the trade name of Kisuma.
酸化カルシウム及び酸化マグネシウムは本発明の硬化性組成物にチクソ性を付与する効果は小さい。しかし、酸化カルシウムや酸化マグネシウムを使用せず膠質炭酸カルシウムを使用した硬化性組成物に比較し、膠質炭酸カルシウムの一部を同重量の酸化カルシウム及び酸化マグネシウムで置換した硬化性組成物は使用上問題ないチクソ性を有する。また、酸化カルシウムや酸化マグネシウム、特に酸化カルシウムを使用すると硬化物の硬度や損失正接(tanδ)が小さくなり、本発明の組成物は、このような特性が必要な用途に好適に使用できる。 Calcium oxide and magnesium oxide have a small effect of imparting thixotropy to the curable composition of the present invention. However, compared with a curable composition using colloidal calcium carbonate without using calcium oxide or magnesium oxide, a curable composition in which a part of the colloidal calcium carbonate is replaced with the same weight of calcium oxide and magnesium oxide is used in use. Has no problem thixotropy. Further, when calcium oxide or magnesium oxide, particularly calcium oxide is used, the hardness and loss tangent (tan δ) of the cured product are reduced, and the composition of the present invention can be suitably used for applications requiring such characteristics.
酸化カルシウム及び酸化マグネシウムから選ばれる少なくとも一種の酸化物の使用量は、架橋性珪素基を有するポリオキシアルキレン系重合体１００重量部に対し２〜１００重量部が好ましく、５〜５０重量部がさらに好ましく、５〜３０重量部が特に好ましい。また、架橋性珪素基を有する他の重合体を併用する場合、酸化カルシウム及び酸化マグネシウムから選ばれる少なくとも一種の酸化物の使用量は、架橋性珪素基を分子鎖末端に有するオキシアルキレン系重合体を含めたすべての架橋性珪素基を有する重合体１００重量部に対し、２〜１００重量部が好ましく、５〜５０重量部がさらに好ましく、５〜３０重量部が特に好ましい。 The amount of at least one oxide selected from calcium oxide and magnesium oxide is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer having a crosslinkable silicon group. Preferably, 5 to 30 parts by weight is particularly preferable. In addition, when another polymer having a crosslinkable silicon group is used in combination, the amount of at least one oxide selected from calcium oxide and magnesium oxide is an oxyalkylene polymer having a crosslinkable silicon group at the molecular chain terminal. The amount is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, and particularly preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polymer having all crosslinkable silicon groups.
本発明の接着剤には必要に応じて膠質炭酸カルシウム、酸化カルシウムや酸化マグネシウム以外の充填剤、硬化触媒、可塑剤、接着性付与剤、溶剤、粘着付与剤等の各種添加剤を併用することができる。 The adhesive of the present invention may be used in combination with various additives such as colloidal calcium carbonate, fillers other than calcium oxide and magnesium oxide, curing catalysts, plasticizers, adhesion promoters, solvents, and tackifiers as necessary. Can do.
膠質炭酸カルシウム、酸化カルシウムや酸化マグネシウム以外の充填剤としては、ヒュームシリカ、沈降性シリカ、無水ケイ酸、含水ケイ酸およびカーボンブラックの如き補強性充填剤；重質炭酸カルシウム、炭酸マグネシウム、ケイソウ土、焼成クレー、クレー、タルク、カオリン、酸化チタン、ベントナイト、有機ベントナイト、酸化第二鉄、酸化亜鉛、ガラスバルーン、シラスバルーン、有機バルーン、有機繊維および無機繊維等の如き充填剤等が使用できる。 As fillers other than colloidal calcium carbonate, calcium oxide and magnesium oxide, reinforcing fillers such as fume silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black; heavy calcium carbonate, magnesium carbonate, diatomaceous earth A filler such as calcined clay, clay, talc, kaolin, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, glass balloon, shirasu balloon, organic balloon, organic fiber, and inorganic fiber can be used.
これら充填剤の使用により強度の高い硬化物を得たい場合には、主にヒュームシリカ、沈降性シリカ、無水ケイ酸、含水ケイ酸およびカーボンブラック、焼成クレーおよびクレー等から選ばれる充填剤をすべての架橋性珪素基を有する重合体１００重量部に対し、１〜２００重量部の範囲で使用すれば好ましい結果が得られる。また、低強度で伸びが大である硬化物を得たい場合には、主に酸化チタン、重質炭酸カルシウム、炭酸マグネシウム、タルク、酸化第二鉄、およびシラスバルーン等から選ばれる充填剤を同重合体１００重量部に対し５〜５００重量部の範囲で使用すれば好ましい結果が得られる。これら充填剤は１種類のみで使用してもよいし、２種類以上混合使用してもよい。 When you want to obtain a cured product with high strength by using these fillers, all fillers selected from fume silica, precipitated silica, silicic anhydride, hydrous silicic acid and carbon black, calcined clay, clay, etc. are all used. When 100 to 100 parts by weight of the polymer having a crosslinkable silicon group is used in the range of 1 to 200 parts by weight, preferable results are obtained. When it is desired to obtain a cured product having low strength and large elongation, a filler selected from titanium oxide, heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, shirasu balloon, etc. is used. Preferred results are obtained when used in the range of 5 to 500 parts by weight per 100 parts by weight of the polymer. These fillers may be used alone or in combination of two or more.
硬化触媒は架橋性珪素基を有するポリオキシアルキレン系重合体等の重合体を速やかに硬化させるため用いられる。 The curing catalyst is used for rapidly curing a polymer such as a polyoxyalkylene polymer having a crosslinkable silicon group.
硬化触媒の例としては、テトラブチルチタネート、テトラプロピルチタネート、テトライソプロピルチタネート、チタンテトラアセチルアセトナート等のチタン酸エステル類；ジブチル錫ジラウレート、ジブチル錫マレエート、ジブチル錫ジアセテート、ジブチル錫ジアセチルアセトナート、ジブチル錫オキサイド、ジオクチル錫ジラウレート、ジオクチル錫マレエート、ジオクチル錫ジアセテート、ジオクチル錫ジネオデカネート（ジオクチル錫ジバーサテート）、ジオクチル錫オキサイド、ジブチル錫オキサイドとフタル酸エステルとの反応物等の４価錫化合物、オクチル酸錫、ナフテン酸錫、ステアリン酸錫、ジネオデカン酸錫（バーサチック酸錫）等の２価錫化合物等の有機錫化合物類；アルミニウムトリスアセチルアセトナート、アルミニウムトリスエチルアセトアセテート、ジイソプロポキシアルミニウムエチルアセトアセテート等の有機アルミニウム化合物類；ビスマス−トリス（２−エチルヘキソエート）、ビスマス−トリス（ネオデカノエート）等のビスマス塩と有機カルボン酸または有機アミンとの反応物等；ジルコニウムテトラアセチルアセトナート、チタンテトラアセチルアセトナート等のキレート化合物類；オクチル酸鉛等の有機鉛化合物；ナフテン酸鉄等の有機鉄化合物；有機バナジウム化合物；ブチルアミン、オクチルアミン、ラウリルアミン、ジブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジエチレントリアミン、トリエチレンテトラミン、オレイルアミン、シクロヘキシルアミン、ベンジルアミン、ジエチルアミノプロピルアミン、キシリレンジアミン、トリエチレンジアミン、グアニジン、ジフェニルグアニジン、２，４，６−トリス（ジメチルアミノメチル）フェノール、モルホリン、Ｎ−メチルモルホリン、２−エチル−４−メチルイミダゾール、１，８−ジアザビシクロ（５，４，０）ウンデセン−７（ＤＢＵ）等のアミン系化合物あるいはそれらのカルボン酸等との塩；過剰のポリアミンと多塩基酸とから得られる低分子量ポリアミド樹脂；過剰のポリアミンとエポキシ化合物との反応生成物等が例示される。 Examples of curing catalysts include tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, titanates such as titanium tetraacetylacetonate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, Tetravalent tin compounds such as dibutyltin oxide, dioctyltin dilaurate, dioctyltin maleate, dioctyltin diacetate, dioctyltin dineodecanate (dioctyltin diversate), dioctyltin oxide, reaction product of dibutyltin oxide and phthalate, octyl acid Organotin compounds such as divalent tin compounds such as tin, tin naphthenate, tin stearate, tin neodecanoate (tin versatic acid); aluminum trisacetylacetonate, Organoaluminum compounds such as luminium trisethyl acetoacetate and diisopropoxyaluminum ethyl acetoacetate; bismuth salts such as bismuth-tris (2-ethylhexoate), bismuth-tris (neodecanoate) and an organic carboxylic acid or organic amine Reaction products, etc .; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; organic lead compounds such as lead octylate; organic iron compounds such as iron naphthenate; organic vanadium compounds; butylamine, octylamine, lauryl Amine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diamine Tylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8 -Amine compounds such as diazabicyclo (5,4,0) undecene-7 (DBU) or salts thereof with carboxylic acids, etc .; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; excess polyamines Examples include reaction products with epoxy compounds.
これらの硬化触媒は単独で使用してもよく、２種以上併用してもよい。これらの硬化触媒のうち、有機金属化合物類、または有機金属化合物類とアミン系化合物の併用系が硬化性の点から好ましい。さらには、硬化速度が大きい点からジブチル錫マレエート、ジブチル錫オキサイドとフタル酸エステルとの反応物、ジブチル錫ジアセチルアセトナート等のジブチル錫系化合物が好ましい。また、触媒活性は少し低下するが環境問題の点からジオクチル錫ジネオデカネート等のジオクチル錫化合物やジオクチル錫オキサイドが好ましい。ジオクチル錫オキサイドは触媒活性が小さいので接着剤製造時に硬化しにくいため、これを含有する接着剤の製造は容易であるが、硬化時間が長くなる。このため、国際公開ＷＯ２００５−０１２４２６号公報に開示されているように、接着剤製造後に触媒活性を向上させるため、接着剤の加熱処理を行うことができる。 These curing catalysts may be used alone or in combination of two or more. Of these curing catalysts, organometallic compounds or a combined system of organometallic compounds and an amine compound are preferred from the viewpoint of curability. Furthermore, dibutyltin-based compounds such as dibutyltin maleate, a reaction product of dibutyltin oxide and a phthalate ester, and dibutyltin diacetylacetonate are preferable from the viewpoint of a high curing rate. Further, although the catalytic activity is slightly lowered, dioctyltin compounds such as dioctyltin dineodecanate and dioctyltin oxide are preferred from the viewpoint of environmental problems. Since dioctyltin oxide has a low catalytic activity, it is difficult to cure at the time of production of the adhesive. Therefore, it is easy to produce an adhesive containing this, but the curing time becomes long. For this reason, as disclosed in International Publication No. WO2005-012426, the adhesive can be heat-treated in order to improve the catalytic activity after the production of the adhesive.
式（３）においてａが３である架橋性珪素基を有するポリオキシアルキレン系重合体は反応性が高く、大きい硬化速度を有する。この重合体に高活性な硬化触媒を使用すると硬化速度が大きくなりすぎ、接着剤製造時に硬化する、接着剤使用時に円滑な接着作業ができない、等に問題が発生する場合がある。このような場合、上記したジオクチル錫ジネオデカネート等のジオクチル錫化合物を使用したり、接着剤製造後加熱処理をしてジオクチル錫オキサイドを使用することが好ましい。 The polyoxyalkylene polymer having a crosslinkable silicon group in which a is 3 in the formula (3) has high reactivity and a high curing rate. When a highly active curing catalyst is used for this polymer, the curing rate becomes too high, and there are cases where problems such as curing during the production of the adhesive and smooth adhesion work during the use of the adhesive may occur. In such a case, it is preferable to use a dioctyltin compound such as the above-mentioned dioctyltin dineodecanate, or to use dioctyltin oxide by heat treatment after production of the adhesive.
硬化触媒はすべての架橋性珪素基を有する重合体１００重量部に対して０．５〜１０重量部用いるのが好ましい。 The curing catalyst is preferably used in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the polymer having all crosslinkable silicon groups.
可塑剤としては、ジイソデシルフタレート、ジウンデシルフタレート、ジイソウンデシルフタレート、ジオクチルフタレート、ジブチルフタレート、ブチルベンジルフタレート等の如きフタル酸エステル類；アジピン酸ジオクチル、コハク酸イソデシル、セバシン酸ジブチル等の如き脂肪族二塩基酸エステル類；ジエチレングリコールジベンゾエート、ペンタエリスリトールエステル等の如きグリコールエステル類；オレイン酸ブチル、アセチルリシノール酸メチルの如き脂肪族エステル類；エポキシ化大豆油、エポキシ化アマニ油、エポキシステアリン酸ベンジル等の如きエポキシ可塑剤類；２塩基酸と２価アルコールとのポリエステル類等のポリエステル系可塑剤；ポリプロピレングリコールやその誘導体等のポリエーテル類；ポリ−α−メチルスチレン、ポリスチレン等のポリスチレン類；ポリブタジエン、ブタジエン−アクリロニトリル共重合体、ポリクロロプレン、ポリイソプレン、ポリイソブテン、パラフィン系炭化水素、ナフテン系炭化水素、パラフィン−ナフテン系混合炭化水素、塩素化パラフィン類等の可塑剤が単独または２種類以上の混合物の形で任意に使用できる。とくに、耐候性の点から重合体主鎖内に不飽和結合を含有しないポリプロピレングリコールやその誘導体等のポリエーテル系可塑剤、ポリイソブテン、パラフィン等が好ましい。 Plasticizers include phthalates such as diisodecyl phthalate, diundecyl phthalate, diisoundecyl phthalate, dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate; aliphatics such as dioctyl adipate, isodecyl succinate, dibutyl sebacate, etc. Dibasic acid esters; Glycol esters such as diethylene glycol dibenzoate and pentaerythritol ester; Aliphatic esters such as butyl oleate and methyl acetyl ricinoleate; Epoxidized soybean oil, epoxidized linseed oil, epoxy benzyl stearate, etc. Epoxy plasticizers such as: polyester plasticizers such as polyesters of dibasic acids and dihydric alcohols; polyethers such as polypropylene glycol and derivatives thereof; poly-α Polystyrenes such as methylstyrene and polystyrene; polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polyisobutene, paraffin hydrocarbon, naphthene hydrocarbon, paraffin-naphthene mixed hydrocarbon, chlorinated paraffin, etc. The plasticizer can be optionally used alone or in the form of a mixture of two or more. In particular, polyether plasticizers such as polypropylene glycol and its derivatives, polyisobutene, paraffin and the like that do not contain an unsaturated bond in the polymer main chain are preferable from the viewpoint of weather resistance.
可塑剤は、すべての架橋性珪素基を有する重合体１００重量部に対して１から３００重量部添加することが好ましく、さらには５から２００重量部添加することが好ましい。 The plasticizer is preferably added in an amount of 1 to 300 parts by weight, more preferably 5 to 200 parts by weight, based on 100 parts by weight of the polymer having all crosslinkable silicon groups.
接着性付与剤としては、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、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−アミノプロピルメチルジメトキシシラン、１，３−ジアミノイソプロピルトリメトキシシラン等のアミノ基含有シラン類；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トリエトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、β−（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等のエポキシ基含有シラン類；γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルメチルジメトキシシラン等のメルカプト基含有シラン類；ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−メタクリロイルオキシプロピルトリメトキシシラン、γ−アクリロイルオキシプロピルメチルジメトキシシラン等のビニル型不飽和基含有シラン類；γ−クロロプロピルトリメトキシシラン等の塩素原子含有シラン類；γ−イソシアネートプロピルトリエトキシシラン、γ−イソシアネートプロピルメチルジメトキシシラン等のイソシアネート含有シラン類；メチルジメトキシシラン、トリメトキシシラン、メチルジエトキシシラン等のハイドロシラン類等が具体的に例示されうるが、これらに限定されるものではない。 Examples of the adhesion-imparting agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- Amino group-containing silanes such as (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane; Epoxy group-containing silanes such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Γ-mercaptopropyltrimethoxysilane, Mercapto group-containing silanes such as γ-mercaptopropylmethyldimethoxysilane; vinyl-type unsaturated groups such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-acryloyloxypropylmethyldimethoxysilane Silanes; Chlorine atom-containing silanes such as γ-chloropropyltrimethoxysilane; Isocyanate-containing silanes such as γ-isocyanatopropyltriethoxysilane and γ-isocyanatopropylmethyldimethoxysilane; methyldimethoxysilane, trimethoxysilane, methyldi Specific examples include hydrosilanes such as ethoxysilane, but are not limited thereto.
接着性付与剤は、あまりに多く添加すると、硬化物のモジュラスが高くなり、少なすぎると接着性が低下することから、すべての架橋性珪素基を有する重合体１００重量部に対して０．１〜１５重量部添加することが好ましく、さらには０．５〜１０重量部添加することが好ましい。 If the adhesiveness-imparting agent is added too much, the modulus of the cured product becomes high, and if it is too small, the adhesiveness is lowered. Therefore, 0.1 to 100 parts by weight of the polymer having all crosslinkable silicon groups. 15 parts by weight is preferably added, and more preferably 0.5 to 10 parts by weight.
作業性の改善、粘度の低下等のために溶剤や希釈剤を配合してもよい。溶剤の例としては、トルエン、キシレン等の芳香族炭化水素系溶剤；酢酸エチル、酢酸ブチル、酢酸アミル、酢酸セロソルブ等のエステル系溶剤；メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤等があげられる。希釈剤の例としてはノルマルパラフィン、イソパラフィン、等があげられる。 You may mix | blend a solvent and a diluent for the improvement of workability | operativity, the fall of a viscosity, etc. Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate and cellosolve; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Examples of the diluent include normal paraffin, isoparaffin, and the like.
溶剤や希釈剤は、すべての架橋性珪素基を有する重合体１００重量部に対して１から１００重量部添加することが好ましく、さらには５から５０重量部添加することが好ましい。 The solvent or diluent is preferably added in an amount of 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the polymer having all crosslinkable silicon groups.
粘着付与剤は被着体へのぬれ性の改善や、はく離強度を高める上で好ましい。石油樹脂系、ロジン・ロジンエステル系、アクリル樹脂系、テルペン樹脂、水添テルペン樹脂やそのフェノール樹脂共重合体、フェノール・フェノールノボラック樹脂系等の粘着付与樹脂が例示されうるが、これらに限定されるものではない。粘着付与剤は、すべての架橋性珪素基を有する重合体１００重量部に対して１〜１００重量部添加することが好ましく、さらには５〜５０重量部添加することが好ましい。 The tackifier is preferable for improving the wettability to the adherend and increasing the peel strength. Examples include, but are not limited to, petroleum resin-based, rosin / rosin ester-based, acrylic resin-based, terpene resin, hydrogenated terpene resin and its phenolic resin copolymer, phenol / phenol novolac resin-based tackifier resin, etc. It is not something. The tackifier is preferably added in an amount of 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the polymer having all crosslinkable silicon groups.
その他の添加剤としては、例えば、水添ヒマシ油、有機ベントナイト、ステアリン酸カルシウム等のタレ防止剤、着色剤、酸化防止剤、紫外線吸収剤、光安定剤等が挙げられる。さらに、必要に応じてエポキシ樹脂等の他の樹脂、エポキシ樹脂硬化剤等の硬化剤、物性調整剤、保存安定性改良剤、滑剤、発泡剤等の添加剤も適宜添加することが可能である。 Examples of other additives include sagging inhibitors such as hydrogenated castor oil, organic bentonite, and calcium stearate, colorants, antioxidants, ultraviolet absorbers, and light stabilizers. Furthermore, additives such as other resins such as epoxy resins, curing agents such as epoxy resin curing agents, physical property modifiers, storage stability improvers, lubricants, and foaming agents can be added as necessary. .
本発明の硬化性組成物は全成分を混合物とする一液型組成物としても、架橋性珪素基を有する樹脂成分と硬化触媒成分とを別の成分とする二液型組成物としても使用することができる。二液型組成物は一般に特性が優れた硬化物を得ることができるが、使用時に樹脂成分と硬化触媒成分を混合する操作が必要であるので、作業上からは一液型組成物が好ましい。 The curable composition of the present invention can be used as a one-component composition comprising all components as a mixture, or as a two-component composition comprising a resin component having a crosslinkable silicon group and a curing catalyst component as separate components. be able to. In general, a two-part composition can provide a cured product having excellent characteristics, but since it requires an operation of mixing a resin component and a curing catalyst component at the time of use, a one-part composition is preferred from the viewpoint of work.
本発明の接着剤の製造方法には特に限定はなく、例えば、前記した成分を配合し、ミキサーやロールやニーダーなどを用いて常温または加熱下で混練したり、適した溶剤を少量使用して成分を溶解させ、混合したりするなどの通常の方法が挙げられる。 The method for producing the adhesive of the present invention is not particularly limited. For example, the above-described components are blended and kneaded using a mixer, a roll, a kneader or the like at room temperature or under heating, or a small amount of a suitable solvent is used. The usual methods, such as melt | dissolving a component and mixing, are mentioned.
本発明の硬化性組成物は、接着剤、シーリング材、防水材、コーティング剤などに使用できる。特に、高温になる自動車部品の接着剤や、外壁材のシーリング材に好適に使用できる。 The curable composition of the present invention can be used for an adhesive, a sealing material, a waterproof material, a coating agent, and the like. In particular, it can be suitably used as an adhesive for automobile parts that become high temperature and a sealing material for outer wall materials.
（合成例１）
ポリオキシプロピレンジオールにナトリウムメトキシド（ＮａＯＭｅ）のメタノール溶液を添加してメタノールを留去し、更に塩化アリルを添加して末端の水酸基をアリル基に変換した。未反応の塩化アリルを減圧脱揮により除去し、さらに生成した金属塩を水により抽出除去して、末端にアリル基を有するポリオキシプロピレンを得た。得られたアリル基末端ポリオキシプロピレンに対し、白金ビニルシロキサン錯体のイソプロパノール溶液を添加し、トリメトキシシランを反応させ、ＰＰＧ（ポリプロピレングリコール）換算の重量平均分子量が約２５０００、１分子当たり１．５個の末端トリメトキシシリル基を有するポリオキシプロピレン系重合体を得た。
(Synthesis Example 1)
A methanol solution of sodium methoxide (NaOMe) was added to polyoxypropylene diol to distill off the methanol, and allyl chloride was further added to convert the terminal hydroxyl group to an allyl group. Unreacted allyl chloride was removed by devolatilization under reduced pressure, and the resulting metal salt was extracted and removed with water to obtain polyoxypropylene having an allyl group at the terminal. To the resulting allyl group-terminated polyoxypropylene, an isopropanol solution of a platinum vinylsiloxane complex is added, and trimethoxysilane is reacted. The weight average molecular weight in terms of PPG (polypropylene glycol) is about 25,000, and 1.5 per molecule. A polyoxypropylene-based polymer having a number of terminal trimethoxysilyl groups was obtained.
（合成例２）
合成例１で用いたポリオキシプロピレンジオールより分子量が小さいポリオキシプロピレンジオールにナトリウムメトキシド（ＮａＯＭｅ）のメタノール溶液を添加してメタノールを留去し、更に塩化アリルを添加して末端の水酸基をアリル基に変換した。未反応の塩化アリルを減圧脱揮により除去し、さらに生成した金属塩を水により抽出除去して、末端にアリル基を有するポリオキシプロピレンを得た。得られたアリル基末端ポリオキシプロピレンに対し、白金ビニルシロキサン錯体のイソプロパノール溶液を添加し、トリメトキシシランを反応させ、ＰＰＧ換算の重量平均分子量が約１５０００、１分子当たり１．５個の末端トリメトキシシリル基を有するポリオキシプロピレン系重合体を得た。
(Synthesis Example 2)
Add a methanol solution of sodium methoxide (NaOMe) to polyoxypropylene diol having a molecular weight smaller than that of the polyoxypropylene diol used in Synthesis Example 1 to distill off the methanol, and then add allyl chloride to remove the terminal hydroxyl group. Converted to the base. Unreacted allyl chloride was removed by devolatilization under reduced pressure, and the resulting metal salt was extracted and removed with water to obtain polyoxypropylene having an allyl group at the terminal. To the resulting allyl group-terminated polyoxypropylene, an isopropanol solution of a platinum vinylsiloxane complex is added and reacted with trimethoxysilane, and the weight average molecular weight in terms of PPG is about 15000, and 1.5 terminal trioxyls per molecule. A polyoxypropylene polymer having a methoxysilyl group was obtained.
（合成例３）
フラスコに溶剤である酢酸エチル４０重量部、メチルメタクリレート５９重量部、２−エチルヘキシルメタクリレート２５重量部、γ−メタクリロキシプロピルトリメトキシシラン２２重量部、及び金属触媒としてルテノセンジクロライド０．１重量部を仕込み窒素ガスを導入しながら８０℃に加熱した。ついで、３−メルカプトプロピルトリメトキシシラン８重量部をフラスコ内に添加し８０℃で６時間反応を行った。室温に冷却後、ベンゾキノン溶液（９５％ＴＨＦ溶液）を２０重量部添加して重合を停止した。溶剤および未反応物を留去し、ポリスチレン換算の重量平均分子量が約６０００であるトリメトキシシリル基を有するアクリル酸エステル系重合体を得た。
(Synthesis Example 3)
In a flask, 40 parts by weight of ethyl acetate as a solvent, 59 parts by weight of methyl methacrylate, 25 parts by weight of 2-ethylhexyl methacrylate, 22 parts by weight of γ-methacryloxypropyltrimethoxysilane, and 0.1 part by weight of ruthenocene dichloride as a metal catalyst were added. The mixture was heated to 80 ° C. while introducing charged nitrogen gas. Then, 8 parts by weight of 3-mercaptopropyltrimethoxysilane was added to the flask and reacted at 80 ° C. for 6 hours. After cooling to room temperature, 20 parts by weight of a benzoquinone solution (95% THF solution) was added to terminate the polymerization. The solvent and unreacted substances were distilled off to obtain an acrylate polymer having a trimethoxysilyl group having a polystyrene-equivalent weight average molecular weight of about 6000.
実施例における硬化速度、熱間剥離強度、硬度や損失正接（ｔａｎδ）の測定方法は次のとおりである。 The measuring method of the curing rate, hot peel strength, hardness and loss tangent (tan δ) in the examples is as follows.
（硬化速度）
硬化速度は皮張り時間によって評価した。内径６０ｍｍの円筒容器に５ｍｍ厚まで試料を充填し、直ちに２３℃、５０％ＲＨの恒温恒湿室に静置し、表面を指で触り、組成物が指に付着しなくなるまでの時間を測定する。
(Curing speed)
The curing rate was evaluated by the skinning time. Fill a cylindrical container with an inner diameter of 60 mm to a thickness of 5 mm, immediately place it in a constant temperature and humidity chamber at 23 ° C. and 50% RH, touch the surface with a finger, and measure the time until the composition does not adhere to the finger To do.
（熱間剥離強度）
幅２５ｍｍ、長さ１００ｍｍ、厚み１．６ｍｍのアルミ板に、接着剤組成物を一端から７５ｍｍの長さの部分に２００μｍの厚みに塗布する。一方、幅２５ｍｍ、長さ２００ｍｍの５号キャンパスに、接着剤組成物を一端から７５ｍｍの長さの部分に２００μｍの厚みに２回塗布する。塗布部分が重なるように貼り合わせ、ハンドローラーで３往復厚締する。これを２３℃５０％ＲＨで１週間養生したものを試験片とする。所定温度雰囲気下でキャンパスの１８０°剥離強度を測定する（引張りスピード２００ｍｍ／分）。
(Hot peel strength)
The adhesive composition is applied to an aluminum plate having a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm to a thickness of 200 μm on a portion having a length of 75 mm from one end. On the other hand, the adhesive composition is applied twice to a portion having a length of 75 mm from one end of the No. 5 campus having a width of 25 mm and a length of 200 mm twice. Laminate the coated parts so that they overlap, and tighten them 3 times with a hand roller. This was cured at 23 ° C. and 50% RH for 1 week as a test piece. The 180 ° peel strength of the campus is measured under a predetermined temperature atmosphere (tensile speed 200 mm / min).
（硬度）
ＪＩＳ Ｋ６２５３に準拠し、接着剤組成物の２３℃、５０％ＲＨで１週間養生したものを試験片とし、ＪＩＳ Ａ硬度を測定する。
(hardness)
In accordance with JIS K6253, the adhesive composition cured at 23 ° C. and 50% RH for 1 week is used as a test piece, and JIS A hardness is measured.
（損失正接（ｔａｎδ））
接着剤から厚み２ｍｍのシートを調製する。動的粘弾性試験は、セイコーインスツルメンツ（株）製ＤＭＳ６１００を用いて、測定温度２３℃、周波数１００Ｈｚ及び歪率０．１％の条件で、２ｍｍシートについて行い、次に損失正接（ｔａｎδ）を下式により求める。
ｔａｎδ＝Ｅ”／Ｅ’
（Ｅ’：貯蔵弾性率、Ｅ”：損失弾性率）
(Loss tangent (tan δ))
A sheet having a thickness of 2 mm is prepared from the adhesive. The dynamic viscoelasticity test was performed on a 2 mm sheet using a DMS6100 manufactured by Seiko Instruments Inc. at a measurement temperature of 23 ° C., a frequency of 100 Hz, and a distortion rate of 0.1%, and then the loss tangent (tan δ) was reduced. Obtained by the formula.
tan δ = E ″ / E ′
(E ': storage elastic modulus, E ": loss elastic modulus)
（糸切れ性）
内径６０ｍｍの円筒容器に５０ｍｍ厚まで試料を充填し、外径４ｍｍのガラス棒の先端４０ｍｍを試料に垂直に沈める。直ちにガラス棒を静かに引き上げ、試料の糸切れ性を確認した。評価基準は、○：糸切れする、△：少し糸引きする、×：糸引きする。
(Thread breakage)
A cylindrical container with an inner diameter of 60 mm is filled with a sample to a thickness of 50 mm, and the tip of a glass rod with an outer diameter of 4 mm is vertically submerged in the sample. Immediately after that, the glass rod was gently pulled up to confirm the thread breakage of the sample. Evaluation criteria are: ○: thread breakage, Δ: slightly threaded, x: threaded.
実施例の接着剤は表１及び２に示す組成で各配合物質を混合攪拌し接着剤を調製した。なお、表１及び２において実及び比はそれぞれ実施例、比較例を示す。また、各実施例、比較例、参考例及び参考比較例の接着剤において、表１に示した配合物に加え次の添加物を共通して加えている。
酸化防止剤：チバ・ジャパン（株）製、ヒンダードフェノール系酸化防止剤、商品名：イルガノックス２４５、１重量部。
脱水剤：コルコート（株）製、テトラエトキシシラン、商品名：エチルシリケート２８、１重量部。
希釈剤：ジャパンエナジー（株）製、パラフィン系希釈剤、商品名：カクタスノルマルパラフィンＮ−１１、１０重量部。
接着性付与剤：信越化学工業（株）製、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、商品名：信越シリコーンＫＢＭ６０３、６重量部。
The adhesives of the examples were prepared by mixing and agitating each compounding substance with the compositions shown in Tables 1 and 2. In Tables 1 and 2, the actual values and ratios indicate examples and comparative examples, respectively. In addition, in the adhesives of Examples, Comparative Examples, Reference Examples, and Reference Comparative Examples, the following additives are commonly added in addition to the formulations shown in Table 1.
Antioxidant: Ciba Japan Co., Ltd., hindered phenol antioxidant, trade name: Irganox 245, 1 part by weight.
Dehydrating agent: Colcoat Co., Ltd., tetraethoxysilane, trade name: ethyl silicate 28, 1 part by weight.
Diluent: manufactured by Japan Energy Co., Ltd., paraffinic diluent, trade name: Cactus normal paraffin N-11, 10 parts by weight.
Adhesiveness imparting agent: manufactured by Shin-Etsu Chemical Co., Ltd., N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, trade name: Shin-Etsu Silicone KBM603, 6 parts by weight.
（実施例１〜２、比較例１）
実施例３及び比較例２においては、架橋性珪素基としてトリアルコキシシリル基を有するポリオキシアルキレン系重合体を使用している。接着剤の硬化速度、熱間剥離強度、硬度、損失正接および糸切れ性を表１に示した。実施例１〜２と比較例１との比較から明らかなように、炭酸カルシウムに代えて酸化カルシウムを添加することにより、剥離強度、特に、高温時の剥離強度が改善されることがわかる。また、硬度が大きくなることがわかる。なお、実施例１〜２、比較例１においては酸化カルシウムと炭酸カルシウムの合計量が同一になるよう組成物を調製している。また、実施例１と、同様の組成で充填剤を配合していない組成物の糸切れ性を比較したところ、実施例１の糸切れ性は○であったが、充填剤を配合していない組成物の糸切れ性は×であった。
(Examples 1-2, Comparative Example 1)
In Example 3 and Comparative Example 2, a polyoxyalkylene polymer having a trialkoxysilyl group as a crosslinkable silicon group is used. Table 1 shows the curing rate, hot peel strength, hardness, loss tangent and thread breakage of the adhesive. As is clear from the comparison between Examples 1 and 2 and Comparative Example 1, it can be seen that the addition of calcium oxide instead of calcium carbonate improves the peel strength, particularly the peel strength at high temperatures. Moreover, it turns out that hardness becomes large. In Examples 1 and 2 and Comparative Example 1, the compositions were prepared so that the total amount of calcium oxide and calcium carbonate was the same. Moreover, when the thread breakage property of the composition which is the same composition as Example 1 and which did not mix | blend a filler was compared, the thread breakage property of Example 1 was (circle), but the filler was not mix | blended. The yarn breakability of the composition was x.
（実施例３、比較例２）
実施例３、比較例２においては、架橋性珪素基としてトリアルコキシシリル基に代えて市販されているジアルコキシシリル基を有する重合体を使用している。接着剤の硬化速度、熱間剥離強度、硬度および損失正接を表１に示した。実施例３と比較例２との比較から明らかなように、この重合体を使用した場合にも炭酸カルシウムに代えて酸化カルシウムを添加することにより、剥離強度、特に、高温時の剥離強度が改善されることがわかる。また、硬度が大きくなることがわかる。架橋性珪素基としてジアルコキシシリル基を有する重合体を用いた硬化性組成物はトリアルコキシシリル基を有する重合体を用いた硬化性組成物よりも硬化速度が小さいので活性が高い硬化触媒を使用している。また、ジアルコキシシリル基を有する重合体を用いた硬化性組成物はトリアルコキシシリル基を有する重合体を用いた硬化性組成物よりも剥離強度が大きくなる傾向にある。
(Example 3, Comparative Example 2)
In Example 3 and Comparative Example 2, a commercially available polymer having a dialkoxysilyl group instead of a trialkoxysilyl group as a crosslinkable silicon group is used. Table 1 shows the curing rate, hot peel strength, hardness, and loss tangent of the adhesive. As is clear from the comparison between Example 3 and Comparative Example 2, even when this polymer is used, the peel strength, particularly the peel strength at high temperatures, is improved by adding calcium oxide instead of calcium carbonate. You can see that Moreover, it turns out that hardness becomes large. A curable composition using a polymer having a dialkoxysilyl group as a crosslinkable silicon group has a lower curing rate than a curable composition using a polymer having a trialkoxysilyl group, so a highly active curing catalyst is used. is doing. Further, the curable composition using a polymer having a dialkoxysilyl group tends to have a higher peel strength than the curable composition using a polymer having a trialkoxysilyl group.
（実施例４〜１１、比較例３〜４）
実施例４〜１１及び比較例３〜４においては、架橋性珪素基を有するポリオキシアルキレン系重合体として合成例１で得られた重合体と合成例２で得られた重合体とを混合して使用している。また、実施例４〜８では酸化カルシウム（表面処理されたものを含む）を使用し、実施例９〜１１では酸化マグネシウム（表面処理されたものを含む）を使用している。比較例４では金属酸化物である酸化チタンを使用している。接着剤の硬化速度、熱間剥離強度、硬度および損失正接を表２に示した。
(Examples 4-11, Comparative Examples 3-4)
In Examples 4 to 11 and Comparative Examples 3 to 4, the polymer obtained in Synthesis Example 1 and the polymer obtained in Synthesis Example 2 were mixed as a polyoxyalkylene polymer having a crosslinkable silicon group. Are used. In Examples 4 to 8, calcium oxide (including a surface-treated product) is used, and in Examples 9 to 11, magnesium oxide (including a surface-treated product) is used. In Comparative Example 4, titanium oxide which is a metal oxide is used. Table 2 shows the curing rate, hot peel strength, hardness and loss tangent of the adhesive.
実施例４〜１１と比較例３との比較から明らかなように、炭酸カルシウムに代えて酸化カルシウムや酸化マグネシウムを添加することにより、剥離強度、特に、高温時の剥離強度が改善されることがわかる。 As is clear from the comparison between Examples 4 to 11 and Comparative Example 3, the peel strength, particularly the peel strength at high temperatures, can be improved by adding calcium oxide or magnesium oxide instead of calcium carbonate. Recognize.
また、実施例５（無処理酸化カルシウム）、実施例９（無処理酸化マグネシウム）と比較例３（酸化チタン）との比較から酸化カルシウムや酸化マグネシウムを使用すると高温時の剥離強度や硬化物の硬度が大きくなることがわかる。さらに、特に実施例５と実施例６との比較及び実施例９と実施例１１との比較から、表面処理されていない酸化物の場合、表面処理された酸化物の場合に比較し、高温時の剥離強度や硬化物の硬度が大きい場合が多いことがわかる。 Further, when calcium oxide or magnesium oxide is used in comparison with Example 5 (untreated calcium oxide), Example 9 (untreated magnesium oxide) and Comparative Example 3 (titanium oxide), the peel strength at high temperature and the cured product It can be seen that the hardness increases. Further, particularly from the comparison between Example 5 and Example 6 and the comparison between Example 9 and Example 11, in the case of an oxide that has not been surface-treated, compared to the case of an oxide that has been surface-treated, It can be seen that the peel strength and the hardness of the cured product are often large.
（実施例１２、比較例５）
実施例１２及び比較例５においては、架橋性珪素基を有するポリオキシアルキレン系重合体として合成例１で得られた重合体と合成例２で得られた重合体とを混合して使用しているが、合成例２で得られた分子量が小さい重合体を増量して使用している。接着剤の硬化速度、熱間剥離強度、硬度および損失正接を表３に示した。
(Example 12, Comparative Example 5)
In Example 12 and Comparative Example 5, the polymer obtained in Synthesis Example 1 and the polymer obtained in Synthesis Example 2 were mixed and used as a polyoxyalkylene polymer having a crosslinkable silicon group. However, the amount of the polymer having a small molecular weight obtained in Synthesis Example 2 is increased. Table 3 shows the curing rate, hot peel strength, hardness and loss tangent of the adhesive.
実施例１、実施例５及び実施例１２の硬度の値から明らかなように、分子量が小さい合成例２のポリオキシアルキレン重合体を使用することにより硬度が大きくなることがわかる。また、実施例１２と比較例５との比較から明らかなように、炭酸カルシウムに代えて酸化カルシウムを添加することにより、高温時の剥離強度や硬度が改善されることがわかる。 As is apparent from the hardness values of Examples 1, 5 and 12, it can be seen that the hardness is increased by using the polyoxyalkylene polymer of Synthesis Example 2 having a small molecular weight. Further, as is clear from the comparison between Example 12 and Comparative Example 5, it can be seen that the peel strength and hardness at high temperature are improved by adding calcium oxide instead of calcium carbonate.
（実施例１３〜１４、比較例６）
実施例１３〜１４、比較例６においては、硬化触媒としてジオクチル錫ジバーサテートにかえてジオクチル錫オキシドを使用した。但し、ジオクチル錫オキシドは触媒活性が低く、触媒活性を向上させるため接着剤組成物の製造後、接着剤組成物の加熱処理を行った。接着剤の硬化速度、熱間剥離強度、硬度および損失正接を表３に示した。実施例１３〜１４と比較例５との比較から明らかなように、他の触媒を用いても炭酸カルシウムに代えて酸化カルシウムを添加することにより、高温時の剥離強度や硬度が改善されることがわかる。
(Examples 13 to 14, Comparative Example 6)
In Examples 13 to 14 and Comparative Example 6, dioctyltin oxide was used as a curing catalyst instead of dioctyltin diversate. However, dioctyltin oxide has low catalytic activity, and the adhesive composition was heated after the production of the adhesive composition in order to improve the catalytic activity. Table 3 shows the curing rate, hot peel strength, hardness and loss tangent of the adhesive. As is clear from the comparison between Examples 13 to 14 and Comparative Example 5, the peel strength and hardness at high temperatures are improved by adding calcium oxide instead of calcium carbonate even when other catalysts are used. I understand.
表１、表２及び表３における配合物質の配合量は重量部で示され、＊１〜＊１１は次の通りである。
＊１：（株）カネカ製、主鎖がポリオキシプロピレンで分子末端にジメトキシ基を有するポリマーと、主鎖がポリメタクリル酸エステルの共重合体で分子中にジメトキシシリル基を有するポリマーとの混合物、商品名：サイリルＭＡ４４０
＊２：近江化学（株）製、表面処理されていない酸化カルシウム、商品名：ＣＭＬ−３５Ｓ
＊３：近江化学（株）製、脂肪酸処理酸化カルシウム、商品名：ＣＭＬ−３１
＊４：神島化学（株）製、表面処理されていない酸化マグネシウム、商品名：スターマグＭ
＊５：神島化学（株）製、脂肪酸処理酸化マグネシウム、商品名：スターマグＣＸ
＊６：堺化学工業（株）製、表面処理されていないルチル型酸化チタン、商品名：ＤＡＩＡＷＨＩＴＥ ＴＣＲ−１０
＊７：白石カルシウム（株）製、重質炭酸カルシウム、商品名：ホワイトンＳＢ
＊８：丸尾カルシウム（株）製、脂肪酸処理炭酸カルシウム、商品名：カルファイン２００
＊９：日東化成（株）製、ジオクチル錫ジバーサテート硬化触媒、商品名：ネオスタン Ｕ−８３０
＊１０：日東化成（株）製、ジオクチル錫オキシド硬化触媒、商品名：ネオスタン Ｕ−８００Ｐ
＊１１：日東化成（株）製、ジブチル錫ビスアセチルアセトナート硬化触媒、商品名：ネオスタン Ｕ−２２０Ｈ
The compounding amounts of the compounding substances in Tables 1, 2 and 3 are expressed in parts by weight, and * 1 to * 11 are as follows.
* 1: A mixture of Kaneka Co., Ltd. polymer with a main chain of polyoxypropylene and a dimethoxy group at the molecular end, and a polymer with a main chain of polymethacrylic acid ester and a dimethoxysilyl group in the molecule. Product name: Silyl MA440
* 2: Omi Chemical Co., Ltd., surface-treated calcium oxide, product name: CML-35S
* 3: Omi Chemical Co., Ltd., fatty acid-treated calcium oxide, product name: CML-31
* 4: Manufactured by Kamishima Chemical Co., Ltd., surface-treated magnesium oxide, product name: Starmag M
* 5: Manufactured by Kamishima Chemical Co., Ltd., fatty acid-treated magnesium oxide, product name: Starmag CX
* 6: Sakai Chemical Industry Co., Ltd., non-surface-treated rutile titanium oxide, product name: DAIAWHITE TCR-10
* 7: Heavy calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd., Product name: Whiten SB
* 8: Maruo Calcium Co., Ltd., fatty acid-treated calcium carbonate, product name: Calfine 200
* 9: Nitto Kasei Co., Ltd. dioctyl tin diversate curing catalyst, product name: Neostan U-830
* 10: Nitto Kasei Co., Ltd., dioctyl tin oxide curing catalyst, product name: Neostan U-800P
* 11: Nitto Kasei Co., Ltd., dibutyltin bisacetylacetonate curing catalyst, product name: Neostan U-220H
Claims (9)
A polyoxyalkylene polymer having a hydroxyl group bonded to a silicon atom or a hydrolyzable group and having a crosslinkable silicon group capable of crosslinking by forming a siloxane bond at the molecular chain end, from calcium carbonate and calcium oxide and magnesium oxide A curable composition containing at least one oxide selected from the group consisting of 100 parts by weight of a polyoxyalkylene polymer having a crosslinkable silicon group at a molecular chain terminal, and a crosslinkable silicon group having a molecular chain In the case of containing a polymer having a crosslinkable silicon group other than the polyoxyalkylene polymer at the terminal, 100 parts by weight of the polymer having all crosslinkable silicon groups, 2 to 200 parts by weight of calcium carbonate carbonate, And curable composition containing 2 to 100 parts by weight of at least one oxide selected from the group consisting of calcium oxide and magnesium oxide .
The curable composition according to claim 3, wherein a is 2 or 3 in the crosslinkable silicon group.
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| WO2013157486A1 (en) * | 2012-04-18 | 2013-10-24 | 旭硝子株式会社 | Method for producing polyether |
| WO2014017218A1 (en) * | 2012-07-25 | 2014-01-30 | セメダイン株式会社 | Two-component curable composition |
| CN104277647A (en) * | 2014-09-05 | 2015-01-14 | 安徽桑瑞斯环保新材料有限公司 | Water-resistant magnesite waterproof paint |
| JP2016172825A (en) * | 2015-03-17 | 2016-09-29 | セメダイン株式会社 | One-pack type normal temperature moisture-curable adhesive composition for woody floor material |
| CN109071934A (en) * | 2016-04-27 | 2018-12-21 | 株式会社钟化 | The solidification compound of heat-curing type |
| JP2020105463A (en) * | 2018-12-28 | 2020-07-09 | サンスター技研株式会社 | Curable composition |
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| CN109071934B (en) * | 2016-04-27 | 2021-07-20 | 株式会社钟化 | Heat-curable composition |
| JP2020105463A (en) * | 2018-12-28 | 2020-07-09 | サンスター技研株式会社 | Curable composition |
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