JPH036941B2 - - Google Patents
Info
- Publication number
- JPH036941B2 JPH036941B2 JP57224592A JP22459282A JPH036941B2 JP H036941 B2 JPH036941 B2 JP H036941B2 JP 57224592 A JP57224592 A JP 57224592A JP 22459282 A JP22459282 A JP 22459282A JP H036941 B2 JPH036941 B2 JP H036941B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- zeolite
- formula
- groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 claims description 16
- 229910021536 Zeolite Inorganic materials 0.000 claims description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000010457 zeolite Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 8
- -1 polyoxypropylene Polymers 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 125000005370 alkoxysilyl group Chemical group 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 125000003302 alkenyloxy group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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 1
- VYVFQBFOMKEKBG-UHFFFAOYSA-L 3,3-dibutyl-2,4,3-benzodioxastannepine-1,5-dione Chemical compound O=C1O[Sn](CCCC)(CCCC)OC(=O)C2=CC=CC=C21 VYVFQBFOMKEKBG-UHFFFAOYSA-L 0.000 description 1
- NGKNMHFWZMHABQ-UHFFFAOYSA-N 4-chloro-2h-benzotriazole Chemical compound ClC1=CC=CC2=NNN=C12 NGKNMHFWZMHABQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- XLIDPNGFCHXNGX-UHFFFAOYSA-N dialuminum;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Si+4] XLIDPNGFCHXNGX-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920002601 oligoester Polymers 0.000 description 1
- 125000005386 organosiloxy group Chemical group 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- 150000002923 oximes Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003606 tin compounds Chemical group 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
Description
本発明は、室温硬化性組成物に係り、特に硬化
触媒の安定性が改善されたシリコーン変成ポリエ
ーテル組成物を提供することに関する。
加水分解性シリコーン官能基を有し、主鎖が本
質的にポリエーテルである重合体をベースにした
室温硬化性組成物としては１例として、主剤と硬
化剤からなる２液型が知られている。２液型の場
合に使用される硬化触媒の中で、最も一般的な２
価の錫化合物は、水分、熱、水などに対して不安
定であるという欠点をもつている。そのため該組
成物を、例えばシーラントに応用した場合、表面
の薄層部分の硬化不良を起こすことがあつた。
本発明者らは、この点を改良すべき鋭意検討を
重ねた結果、硬化触媒を含む硬化剤にケイ酸化合
物を添加することにより目的が達せられることを
見出し、本発明に到達した。
すなわち本発明は、
(a) 架橋可能な加水分解性シリコーン官能基を有
し、主鎖が本質的にポリエーテルである重合体
100重量部、
(b) ゼオライト0.01〜30重量部、
(c) 硬化触媒0.001〜10重量部
を配合してなる室温硬化性組成物である。
本発明で使用する架橋可能な加水分解性シリコ
ーン官能基を有し、主鎖が本質的にポリエーテル
である重合体とは、主鎖が本質的に、式
−R1−Ｏ− (1)
（式中、R1は炭素数が１〜４である２価のアル
キレン基）
で示される化学的に結合された繰り返し単位を含
み、かつ加水分解性性と結合したシリコーン原子
を有することにより、湿分の存在下で架橋可能な
重合体である。代表的には末端官能基が、式
〔式中、Ｚは−Ｒ−、−ROR−、
The present invention relates to room temperature curable compositions, and more particularly to providing silicone-modified polyether compositions with improved curing catalyst stability. As an example of a room temperature curable composition based on a polymer having a hydrolyzable silicone functional group and whose main chain is essentially polyether, a two-component type consisting of a base agent and a curing agent is known. There is. Among the curing catalysts used in the two-component type, the most common curing catalyst is
Tin compounds have the disadvantage of being unstable to moisture, heat, water, and the like. Therefore, when the composition is applied to a sealant, for example, curing failure may occur in the thin layer on the surface. As a result of intensive studies to improve this point, the present inventors discovered that the objective could be achieved by adding a silicic acid compound to a curing agent containing a curing catalyst, and arrived at the present invention. That is, the present invention provides (a) a polymer having a crosslinkable hydrolyzable silicone functional group and whose main chain is essentially a polyether;
(b) 0.01 to 30 parts by weight of zeolite, and (c) 0.001 to 10 parts by weight of curing catalyst. Polymers having crosslinkable hydrolyzable silicone functional groups and whose main chain is essentially a polyether for use in the present invention are those whose main chain is essentially of the formula -R 1 -O- (1) (In the formula, R 1 is a divalent alkylene group having 1 to 4 carbon atoms) By containing a chemically bonded repeating unit represented by and having a silicone atom bonded with hydrolyzability, It is a polymer that can be crosslinked in the presence of moisture. Typically, the terminal functional group is of the formula [In the formula, Z is -R-, -ROR-,
【式】【formula】
【式】及び[Formula] and
【式】（式中、
Ｒは同種又は異種の炭素数１〜20の２価の炭化水
素基）、R2は水素又は炭素数１〜20の置換もしく
は非置換の１価の有機基、R3は炭素数１〜20の
置換もしくは非置換の１価の有機基又はオルガノ
シロキシ基、R4は炭素数１〜20の飽和又は不飽
和の１価の炭化水素基、ａは０又は１の整数、ｂ
は０、１又は２の整数、ｃは０、１又は２の整
数、ｍは０〜18の整数、Ｘはハロゲン基、アルコ
キシ基、アルケニルオキシ基、アシロキシ基、ア
ミノ基、アミノオキシ基、オキシム基、ケトオキ
シム基、アミド基等の加水分解性基又は原子〕で
示される重合体をさす。
これらの重合体はたとえば、末端に、式
（式中、Ｚ、R2、ａは前記に同じ）
を有するポリエーテルに、式
（式中、R3，R4，ｂ，ｃ，ｍ，Ｘは前記に同じ）
で示される化合物を塩化白金酸のような公知のヒ
ドロシリル化触媒を用いて室温ないし200℃で反
応させることにより容易に得ることが出来る。
−Ｒ−Ｏ−（式(1)）で示される化学的に結合さ
れた繰り返し単位には、例えば−CH2O−、−
CH2CH2O−、[Formula] (wherein R is the same or different divalent hydrocarbon group having 1 to 20 carbon atoms), R 2 is hydrogen or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, R 3 is a substituted or unsubstituted monovalent organic group or organosiloxy group having 1 to 20 carbon atoms, R 4 is a saturated or unsaturated monovalent hydrocarbon group having 1 to 20 carbon atoms, and a is 0 or 1. integer, b
is an integer of 0, 1 or 2, c is an integer of 0, 1 or 2, m is an integer of 0 to 18, X is a halogen group, alkoxy group, alkenyloxy group, acyloxy group, amino group, aminooxy group, oxime [hydrolyzable groups or atoms] such as hydrolyzable groups, ketoxime groups, and amide groups]. These polymers may have, for example, terminals with the formula (In the formula, Z, R 2 and a are the same as above) to a polyether having the formula (In the formula, R 3 , R 4 , b, c, m, and X are the same as above)
It can be easily obtained by reacting the compound shown by using a known hydrosilylation catalyst such as chloroplatinic acid at room temperature to 200°C. The chemically bonded repeating unit represented by -R-O- (formula (1)) includes, for example, -CH 2 O-, -
CH 2 CH 2 O−,
【式】【formula】
【式】−CH2CH2CH2CH2O−など
が具体的に挙げられる。これらは単独及び混合の
形で用いられるが、特にポリオキシプロピレンが
よい。加水分解性シリコーン官能基は好ましくは
ポリエーテル重合体の末端に存在し、その加水分
解性基としてはアルコキシ基、アシロキシ基、ア
ミノ基、アミノオキシ基、オキシム基、ケトオキ
シム基、アミド基、アルケニルオキシ基、ハロゲ
ン基が例示される。
本発明で使用されるケイ酸含有化合物は、ゼオ
ライトが最も優れている。他のケイ酸含有化合物
には、例えばカオリン、焼成クレー、パイロフイ
ライト、ベントナイト、セリサイト、ゼオライ
ト、ネフエリン・シナイト、タルク、アタパルジ
ヤイト、ワラストナイト、合成ケイ酸アルミ、合
成ケイ酸カルシウム、ケイソウ土、ケイ石粉、含
水微粉ケイ酸、及び無水微粉ケイ酸があるが特に
ゼオライトが有効である。
これらを含む硬化剤は次のようにして作製する
ことが最も代表的である。硬化触媒、ゼオライ
ト、可塑剤および充填剤を硬化剤となし、これを
主剤に対し概ね、重量で10：１になるように添加
し、ロール又は高速撹拌装置で混合する。この場
合、充填剤は入れなくてもよく、また必要に応じ
て水添ヒマシ油等のタレ防止剤を添加してもよ
い。添加方法は、触媒とゼオライトを最初に混ぜ
た後、残りの可塑剤、充填剤等を加えても、最初
から硬化剤成分を全て入れて作製してもよいが、
前者の方が好ましい。
シリコーン官能基含有ポリエーテル100重量部
に対して、ゼオライトは0.01〜30重量部の範囲で
使用されるが、好ましくは0.1〜10重量部の範囲
で使用するのがよい。0.01重量部未満では効果が
小さく、また30重量部を越えるとモジユラスが高
くなるなどの物性への悪影響が出ることがある。
本発明で使用する硬化触媒としては、オクチル
酸錫、ジブチル錫ジラウレート、ジブチル錫マレ
エート、ジブチル錫フタレート等のカルボン酸金
属塩；有機錫酸化物とエステルとの反応物；テト
ラブチルチタネート、オルガノシロキシチタン等
の有機チタン酸エステル；アミン類、アミン塩、
４級アンモニウム塩、グアニジン化合物等が挙げ
られる。この中で、本発明の効果は、錫系の化合
物、特にオクチル酸錫等の２価の錫系の化合物を
硬化触媒として採用したとき顕著である。これら
は単独もしくは混合して使用できる。これらの硬
化触媒は、シリコーン官能基含有ポリエーテル
100重量部に対し、0.001〜10重量部使用するのが
好ましい。
本発明を採用したとき、硬化触媒の水分、熱、
光に対する不安定性は大きく改善され、表面にお
ける硬化不良というような現象はなくなる。
以下実施例を挙げて具体的に説明する。
比較例 １
平均分子量8000、末端基として、Specific examples include [Formula] -CH 2 CH 2 CH 2 CH 2 O-. These may be used alone or in a mixed form, but polyoxypropylene is particularly preferred. Hydrolyzable silicone functional groups are preferably present at the ends of the polyether polymer, and the hydrolyzable groups include alkoxy groups, acyloxy groups, amino groups, aminooxy groups, oxime groups, ketoxime groups, amide groups, and alkenyloxy groups. and halogen groups. The best silicic acid-containing compound used in the present invention is zeolite. Other silicic acid-containing compounds include, for example, kaolin, calcined clay, pyrophyllite, bentonite, sericite, zeolite, nephelin sinite, talc, attapulgite, wollastonite, synthetic aluminum silicate, synthetic calcium silicate, diatomaceous earth. , silica powder, hydrous fine silicic acid, and anhydrous fine silicic acid, and zeolite is particularly effective. Curing agents containing these are most typically produced as follows. A curing catalyst, a zeolite, a plasticizer, and a filler are used as a curing agent, which are added to the base material in a ratio of approximately 10:1 by weight, and mixed using a roll or a high-speed stirring device. In this case, the filler may not be added, and an anti-sagging agent such as hydrogenated castor oil may be added if necessary. The addition method can be either by first mixing the catalyst and zeolite and then adding the remaining plasticizer, filler, etc., or by adding all the curing agent components from the beginning.
The former is preferable. The zeolite is used in an amount of 0.01 to 30 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the silicone functional group-containing polyether. If the amount is less than 0.01 parts by weight, the effect will be small, and if it exceeds 30 parts by weight, there may be adverse effects on physical properties such as increased modulus. Curing catalysts used in the present invention include carboxylic acid metal salts such as tin octylate, dibutyltin dilaurate, dibutyltin maleate, and dibutyltin phthalate; reaction products of organic tin oxides and esters; tetrabutyl titanate, organosiloxy titanium. Organic titanate esters such as; amines, amine salts,
Examples include quaternary ammonium salts and guanidine compounds. Among these, the effects of the present invention are remarkable when a tin-based compound, particularly a divalent tin-based compound such as tin octylate, is employed as a curing catalyst. These can be used alone or in combination. These curing catalysts are silicone-functionalized polyethers.
It is preferable to use 0.001 to 10 parts by weight per 100 parts by weight. When the present invention is adopted, moisture in the curing catalyst, heat,
The instability to light is greatly improved, and phenomena such as poor curing on the surface are eliminated. This will be specifically explained below by giving examples. Comparative Example 1 Average molecular weight 8000, as a terminal group,
【式】基を全末端基
のうち80％有するポリプロピレンオキシド100重
量部に対し、脂肪酸処理炭酸カルシウム（白石カ
ルシウム製、商品名CCR）100重量部、ルチル型
酸化チタン28重量部、エポキシヘキサヒドロフタ
ル酸ジオクチル35重量部、ジオクチルフタレート
20重量部、水添化ヒマシ油６重量部、カーボンブ
ラツク0.5重量部、オリゴエステルアクリレート
（東亜合成化学製、商品名Ｍ−8060）５重量部、
２，2′−メチレン−ビス−（４−メチル−６−ter
−ブチルフエノール）１重量部、２（2′−ヒドロ
キシ−3′，5′−ジ−ter−ブチルフエニル）−５−
クロロベンゾトリアゾール１重量部を加え、３本
ペイントロールにてよく混合した配合物を作製
し、これを主剤とした。
オクチル酸錫３重量部、ラウリルアミン0.5重
量部、ジオクチルフタレート6.5重量部、重質炭
酸カルシウム20重量部、水添化ヒマシ油0.2重量
部を加え、ホモジナイザー（日本精機製作所）で
10000回／分で15分間撹拌し、よく混合、分散し
た配合物を作製した。これを硬化剤とした。
このようにして得られた主剤と硬化剤を10：１
の重量比で混合し、0.075mm厚のシートを作製し、
35℃80％湿度下におき、タツクフリー時間（JIS
−A5758に従う）を測定した。
比較例 ２
比較例１において、硬化触媒中、ラウリルアミ
ン0.5重量部の代わりにステアリルアミン1.0重量
部添加すること以外は同様にして硬化シートを作
製し、タツクフリー時間を測定した。
実施例 １〜４
比較例１に対し、表１に示すようなゼオライト
を硬化剤に添加する以外は同様にして硬化シート
を作製し、タツクフリー時間を測定した（実施例
１，２，３，４）。ゼオライトの添加方法は、手
順としてオクチル酸錫３重量部、ラウリルアミ
ン0.5重量部及びゼオライト２重量部を添加し、
スパチユラでよく撹拌する、残りの添加物を加
えホモジナイザーで作製する。測定結果を表１に
記す。
実施例 ５〜８
比較例２に対し、表１に示すようなゼオライト
を硬化剤に添加する以外は同様にして硬化シート
を作製し、タツクフリー時間を測定した（実施例
５，６，７，８）。ゼオライトの添加方法は実施
例１〜４と同じである。[Formula] 100 parts by weight of polypropylene oxide having 80% of all end groups, 100 parts by weight of fatty acid-treated calcium carbonate (manufactured by Shiraishi Calcium, trade name: CCR), 28 parts by weight of rutile titanium oxide, epoxyhexahydrophthal 35 parts by weight of dioctyl acid, dioctyl phthalate
20 parts by weight, 6 parts by weight of hydrogenated castor oil, 0.5 parts by weight of carbon black, 5 parts by weight of oligoester acrylate (manufactured by Toagosei Chemical Co., Ltd., trade name M-8060),
2,2'-methylene-bis-(4-methyl-6-ter
-butylphenol) 1 part by weight, 2(2'-hydroxy-3',5'-di-ter-butylphenyl)-5-
One part by weight of chlorobenzotriazole was added and thoroughly mixed using three paint rolls to prepare a formulation, which was used as the main ingredient. Add 3 parts by weight of tin octylate, 0.5 parts by weight of laurylamine, 6.5 parts by weight of dioctyl phthalate, 20 parts by weight of heavy calcium carbonate, and 0.2 parts by weight of hydrogenated castor oil, and use a homogenizer (Nippon Seiki Seisakusho) to
The mixture was stirred at 10,000 times/min for 15 minutes to produce a well-mixed and dispersed formulation. This was used as a hardening agent. The base resin and curing agent obtained in this way were mixed in a ratio of 10:1.
A 0.075mm thick sheet was prepared by mixing at a weight ratio of
Tack-free time (JIS
−A5758) was measured. Comparative Example 2 A cured sheet was prepared in the same manner as in Comparative Example 1 except that 1.0 part by weight of stearylamine was added instead of 0.5 part by weight of laurylamine in the curing catalyst, and the tack-free time was measured. Examples 1 to 4 Cured sheets were prepared in the same manner as in Comparative Example 1 except that zeolite as shown in Table 1 was added to the curing agent, and the tack-free time was measured (Examples 1, 2, 3, and 4). ). The method for adding zeolite is to add 3 parts by weight of tin octylate, 0.5 parts by weight of laurylamine, and 2 parts by weight of zeolite.
Stir well with a spatula, add the remaining additives, and prepare with a homogenizer. The measurement results are shown in Table 1. Examples 5 to 8 Cured sheets were prepared in the same manner as in Comparative Example 2 except that zeolite as shown in Table 1 was added to the curing agent, and the tack-free time was measured (Examples 5, 6, 7, and 8). ). The method of adding zeolite is the same as in Examples 1-4.
【表】【table】
【表】
＊ ユニオン昭和(株)製 結晶性ゼオライ
ト
比較例 ３−７
比較例１に対して、表２に示すようなケイ酸含
有化合物２重量部を硬化剤に添加する以外は同様
にして硬化シートを作製し、タツクフリー時間を
測定した（比較例３、４、５、６、７）。
ケイ酸含有化合物の添加方法は、次の手順によ
る。
触媒を添加、ケイ酸含有化合物を添加して
スパチユラでよく混合する、残りの組成物を添
加してホモジナイザーで10000回／分で15分間撹
拌、混合する。測定結果を表２に記す。
比較例 ８〜12
比較例２に対して、表２に示すようなケイ酸含
有化合物を硬化剤に添加する以外は同様にしてタ
ツクフリー時間を測定した（比較例８、９、10、
11、12）。作製手順は比較例３〜７と同じである。
結果を表２に記す。[Table] * Crystalline zeolite Comparative Example 3-7 manufactured by Union Showa Co., Ltd. Cured in the same manner as Comparative Example 1 except that 2 parts by weight of the silicic acid-containing compound shown in Table 2 was added to the curing agent. A sheet was produced and the tack-free time was measured (Comparative Examples 3, 4, 5, 6, 7). The method for adding the silicic acid-containing compound is as follows. Add the catalyst, add the silicic acid-containing compound and mix well with a spatula, add the remaining composition and stir and mix with a homogenizer at 10,000 times/min for 15 minutes. The measurement results are shown in Table 2. Comparative Examples 8 to 12 The tack-free time was measured in the same manner as in Comparative Example 2 except that the silicic acid-containing compound shown in Table 2 was added to the curing agent (Comparative Examples 8, 9, 10,
11, 12). The manufacturing procedure is the same as Comparative Examples 3-7.
The results are shown in Table 2.
【表】【table】
【表】
＊１ 徳山曹達(株)製
＊２ 土屋カオリン工業(株)製
[Table] *1 Manufactured by Tokuyama Soda Co., Ltd.
*2 Manufactured by Tsuchiya Kaolin Kogyo Co., Ltd.
Claims (1)
を有し、主鎖が主鎖が本質的にポリエーテル
である重合体100重量部、 (b) ゼオライト0.01〜30重量部、 (c) 硬化触媒0.001〜10重量部 を含有する室温硬化性組成物。 ２ (a)の加水分解性シリコーン官能基がアルコキ
シシリル基である特許請求の範囲第１項記載の室
温硬化性組成物。 ３ (a)の主鎖が本質的にポリオキシプロピレンで
ある特許請求の範囲第１項記載の室温硬化性組成
物。 ４ (c)の硬化触媒が錫系の化合物である特許請求
の範囲第１項、第２項又は第３項記載の室温硬化
性組成物。[Scope of Claims] 1 (a) 100 parts by weight of a polymer having crosslinkable hydrolyzable silicone functional groups and whose main chain is essentially a polyether; (b) 0.01 to 30 parts by weight of zeolite. (c) a room temperature curable composition containing from 0.001 to 10 parts by weight of a curing catalyst. 2. The room temperature curable composition according to claim 1, wherein the hydrolyzable silicone functional group in (a) is an alkoxysilyl group. 3. A room temperature curable composition according to claim 1, wherein the main chain of (a) is essentially polyoxypropylene. 4. The room temperature curable composition according to claim 1, 2 or 3, wherein the curing catalyst (c) is a tin-based compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22459282A JPS59113051A (en) | 1982-12-20 | 1982-12-20 | Room temperature curable composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22459282A JPS59113051A (en) | 1982-12-20 | 1982-12-20 | Room temperature curable composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59113051A JPS59113051A (en) | 1984-06-29 |
| JPH036941B2 true JPH036941B2 (en) | 1991-01-31 |
Family
ID=16816139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22459282A Granted JPS59113051A (en) | 1982-12-20 | 1982-12-20 | Room temperature curable composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59113051A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6346282A (en) * | 1987-08-07 | 1988-02-27 | Semedain Kk | Adhesive |
| JP3183171B2 (en) * | 1996-05-31 | 2001-07-03 | トヨタ自動車株式会社 | Thermal insulation ceramic layer and method of forming the same |
| JP5048464B2 (en) * | 2001-05-17 | 2012-10-17 | 株式会社カネカ | Curable composition with improved thin layer curability and method for improving thin layer curability |
| JP2005281404A (en) * | 2004-03-29 | 2005-10-13 | Aica Kogyo Co Ltd | Moisture curable resin composition and its curing acceleration method |
| JP2008120859A (en) * | 2006-11-08 | 2008-05-29 | Toyota Motor Corp | Curing method of sealing material and assembling method of electronic equipment |
| AU2010285732A1 (en) * | 2009-08-17 | 2012-02-16 | Asahi Glass Company, Limited | Curable composition |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51107399A (en) * | 1975-03-14 | 1976-09-22 | Furuuitsudomasutaa Inc | |
| JPS5212218A (en) * | 1975-07-19 | 1977-01-29 | Nippon Chemical Ind | Method of manufacturing hydrated alkali silicate glass |
| JPS5273998A (en) * | 1975-12-16 | 1977-06-21 | Kanegafuchi Chem Ind Co Ltd | Room temperature curing compositions |
| JPS5556154A (en) * | 1978-10-23 | 1980-04-24 | Kanegafuchi Chem Ind Co Ltd | Clear curable composition |
| JPS57155250A (en) * | 1981-03-20 | 1982-09-25 | Kanegafuchi Chem Ind Co Ltd | Curable composition |
-
1982
- 1982-12-20 JP JP22459282A patent/JPS59113051A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51107399A (en) * | 1975-03-14 | 1976-09-22 | Furuuitsudomasutaa Inc | |
| JPS5212218A (en) * | 1975-07-19 | 1977-01-29 | Nippon Chemical Ind | Method of manufacturing hydrated alkali silicate glass |
| JPS5273998A (en) * | 1975-12-16 | 1977-06-21 | Kanegafuchi Chem Ind Co Ltd | Room temperature curing compositions |
| JPS5556154A (en) * | 1978-10-23 | 1980-04-24 | Kanegafuchi Chem Ind Co Ltd | Clear curable composition |
| JPS57155250A (en) * | 1981-03-20 | 1982-09-25 | Kanegafuchi Chem Ind Co Ltd | Curable composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59113051A (en) | 1984-06-29 |
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