JPH0347669B2 - - Google Patents
Info
- Publication number
- JPH0347669B2 JPH0347669B2 JP58027989A JP2798983A JPH0347669B2 JP H0347669 B2 JPH0347669 B2 JP H0347669B2 JP 58027989 A JP58027989 A JP 58027989A JP 2798983 A JP2798983 A JP 2798983A JP H0347669 B2 JPH0347669 B2 JP H0347669B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- monomer
- emulsion
- copolymer
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 16
- 239000003995 emulsifying agent Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000008199 coating composition Substances 0.000 claims description 10
- 239000008119 colloidal silica Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- 229920003002 synthetic resin Polymers 0.000 description 8
- 239000000057 synthetic resin Substances 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- -1 alkylaryl sulfosuccinate Chemical compound 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- WCRQPXHVVCBDDT-PLNGDYQASA-N (z)-2-(3-sulfopropyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\CCCS(O)(=O)=O WCRQPXHVVCBDDT-PLNGDYQASA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 2
- 159000000011 group IA salts Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- DMZPTAFGSRVFIA-UHFFFAOYSA-N 3-[tris(2-methoxyethoxy)silyl]propyl 2-methylprop-2-enoate Chemical compound COCCO[Si](OCCOC)(OCCOC)CCCOC(=O)C(C)=C DMZPTAFGSRVFIA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- BYOIQYHAYWYSCZ-UHFFFAOYSA-N prop-2-enoxysilane Chemical compound [SiH3]OCC=C BYOIQYHAYWYSCZ-UHFFFAOYSA-N 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Description
本発明は耐水性のきわめてすぐれたシラン系合
成樹脂エマルジヨンコーテイング組成物に関す
る。
合成樹脂水性エマルジヨンは、水系であるた
め、溶剤系のものに比べて、無公害、無火災、省
エネルギーであり、また各種単量体を容易に共重
合させて性能アツプができること、溶剤系では重
合体によつて溶剤を選ぶので難しいとされている
重合体同志のブレンドが容易にできること、また
乳化剤を選ぶことによつて、例えばイオン性を変
えるなど、エマルジヨンや重合体そのものの性能
に容易に変化をつけることができるなどの利点が
あり、塗料バインダー、接着剤、繊維加工、紙加
工、フイルム加工、建築仕上げ、土木関係などの
分野に大量に使用されている。
しかし乍ら、乳化重合で製造するため、多かれ
少なかれ乳化剤を含有しており、皮膜の耐水性に
はつねに問題が残されてきた。
耐水性のきわめてすぐれた合成樹脂エマルジヨ
ンがえられると、とくにコーテイング剤として有
利に使用することができるので、その出現が望ま
れていた。
本発明者らは、最近開発されてきたシラン系合
成樹脂エマルジヨンのすぐれた耐水性、耐薬品
性、金属などへの密着性、耐摩耗性、耐熱性など
に着目し、これの耐水性をより一層高めた耐水性
コーテイング組成物を開発するべく、種々検討を
行なつた結果、単量体組成、乳化剤、および添加
剤を特定することにより、きわめて耐水性のすぐ
れた皮膜を形成するエマルジヨン組成物を見出
し、本発明を完成した。
すなわち本発明は、ビニルシランとアクリル系
単量体を、重合性乳化剤を用いて乳化重合してえ
たガラス転移温度70℃以下の共重合体を含有する
水性エマルジヨンに、その固形分100重量部に対
し、コロイダルシリカ20〜400重量部を配合して
なる耐水性コーテイング組成物である。
本発明で用いるビニルシランとしては加水分解
型のものが好適であり、たとえばビニルトリメト
オキシシラン、ビニルトリエトオキシシラン、ビ
ニルトリス（２−メトオキシ−エトオキシ）シラ
ン、ビニルトリアセトオキシシラン、γ−メタク
リロオキシプロピルトリメトオキシシラン、ビニ
ルトリクロロシラン、γ−メタクリロオキシプロ
ピルトリス（メトオキシ−エトオキシ）シランな
どであるが、共重合性の点からγ−メタクリロオ
キシプロピルトリメトオキシシランが最も好まし
い。
本発明で用いるアクリル系単量体としては、ア
ルキル基の炭素原子が１〜12個のアクリル酸アル
キルエステルおよびアルキル基の炭素原子が１〜
12個のメタクリル酸アルキルエステルである。そ
して、これらと共重合させる単量体としてはスチ
レンがある。その他の単量体としては、少量のＮ
−メチロールアクリルアミド、アクリル酸、メタ
クリル酸、イタコン酸、アクリルアマイド、アク
リルニトリル、酢酸ビニル、α−位で分岐した飽
和カルボン酸のビニルエステルなどがある。
ビニルシランの共重合割合は、アクリル系単量
体および共重合用単量体の合計100重量部に対し
て、0.5〜15重量部、好ましくは１〜10重量部で
ある。
共重合体のガラス転移温度は70℃以下でなけれ
ばならない。それは、70℃を超えると透明性のあ
る均一な塗膜がえられにくいからである。
好適な共重合体の組合せは、ビニルトリメトオ
キシシラン・アクリル酸ブチル・メタクリル酸メ
チル；ビニルトリエトオキシシラン・アクリル酸
２−エチルヘキシル・メタクリル酸メチル・アク
リル酸；ビニルメトオキシシラン・アクリル酸ブ
チル・スチレン；ビニルトリアセトオキシシラ
ン・アクリル酸ブチル・メタクリル酸メチル；ビ
ニルトリス（２−メトオキシ−エトオキシ）シラ
ン・アクリル酸２−エチルヘキシル・スチレン；
γ−メタアクリルオキシプロピルトリメトオキシ
シラン・アクリル酸オクチル・メタクリル酸メチ
ルなどのうちでガラス転移温度が70℃以下の組成
割合のものが挙げられる。
乳化剤としては、耐水性を向上させるために、
次に挙げるごとき重合性乳化剤が用いられる。
すなわち、
(1) アルキルアリルスルホサクシネートのアルカ
リ塩
（式中、R1は炭素数８〜20個のアルキル基）
(2) ソジウム（グリセリンｎ−アルケニルサクシ
ノイルグリセリン）ボラート
（式中、R2は炭素数12〜20個のアルキル基）
(3) スルホプロピルマレイン酸モノアルキルエス
テルのアルカリ塩
（式中、R3は炭素数８〜20個のアルキル基）
(4) アクリル酸又はメタクリル酸のポリオキシエ
チレンアルキルエステル
（式中、R4はＨ又はCH3、R5は炭素数８〜20
個のアルキル基、ｎは１〜20の整数）
などである。
これらの重合性乳化剤は、単量体とともに共重
合してしまい、乳化剤のままで残らないので、皮
膜の耐水性向上に大きく寄与するのである。
重合方法としては、単量体の仕込方法が回分方
式でも、連続送入方式でもよい。また一部を先に
重合したのち、残部を連続的に送入する方式でも
よい。
連続的に送入する単量体は、そのままでもよい
が、水と乳化剤を用いて単量体乳化液として送入
する方式は、きわめて好適である。又、高温重合
でも、レドツクス重合でもよい。
次に、えられたシラン系合成樹脂エマルジヨン
にコロイダルシリカを添加混合するのであるが、
用いるコロイダルシリカとしては、コロイド状に
水に分散させた超微粒子シリカゾル、又は超微粒
子粉末シリカで、いずれも一次粒子の粒子径は７
〜50ｍμで球状を示すものである。しかして表面
活性の点から水中にコロイド状に分散させたもの
が好ましい。コロイダルシリカの添加量は、シラ
ン系合成樹脂エマルジヨンの固形分100重量部に
対して、固形分で20〜400重量部が好適である。
シラン系合成樹脂エマルジヨンの皮膜は、常温
で自己架橋するが、このときコロイダルシリカが
存在するとより強固に架橋反応が進み、皮膜にき
わめてすぐれた耐水性が付与されるのである。
このようにきわめて耐水性のすぐれた皮膜を形
成するコーテイング組成物は、単量体組成を変え
ることにより、硬い皮膜を形成するものから、軟
い皮膜を形成するものや、接着性のよいものや、
粘着性のあるものなどを作ることができるので、
コンクリート、あるいはALCのような軽量コン
クリートの吸水性防止用シーラーにも、また顔料
やフイラーを混合して耐水性のよいエマルジヨン
塗料にも、プラスチツクフイルムのコーテイング
にも、紙のコーテイングにも使用できる。
次に実施例と比較例をあげて本発明を説明す
る。
実施例 １
アルキルアリルスルホサクシネートのナトリウ
ム塩２重量部の存在下にアクリル酸ブチル50重量
部、メタクリル酸メチル44重量部、ビニルトリメ
トオキシシラン６重量部から成る混合単量体を乳
化重合してえた固形分含有量40重量％、粘度100
センチポイズの水性分散液100重量部に粒子径10
〜20ｍμ、固形分含有量30重量％のコロイダルシ
リカ水溶液100重量部を加えて、固形分濃度35重
量％、粘液50センチポイズ、PH8.5のコーテイン
グ組成物をえた。
実施例 ２
実施例１で用いた乳化剤、アルキルアリルスル
ホサクシネートのナトリウム塩の代りに、スルホ
プロピルマレイン酸モノアルキルエステルのナト
リウム塩を使用した以外は、実施例１と同様にし
て、コーテイング組成物をえた。
実施例 ３
実施例１のビニルトリメトオキシシランの代り
にγ−メタクリロオキシプロピルトリメトオキシ
シランを用いた以外は、実施例１と同様にしてコ
ーテイング組成物をえた。
比較例 １
実施例１においてえた合成樹脂エマルジヨン
で、コロイダルシリカ水溶液を添加しないもの。
比較例 ２
実施例１において、ビニルトリメトオキシシラ
ンを用いずに重合した以外は、実施例１と全く同
様にして、コーテイング組成物をえた。
比較例 ３
実施例１において、アルキルアリルスルホサク
シネートのナトリウム塩の代りに、非イオン性界
面活性剤を用いた以外は実施例１と全く同様にし
て、コーテイング組成物をえた。
（試験結果）
実施例および比較例でえた組成物を、ガラス板
に0.2mmの厚さになるように塗布し、40℃で乾燥
したものについて、室温水７日浸漬放置した後、
塗工皮膜の白化の有無と密着性を測定した。
その結果は第１表のとおりであつた。
The present invention relates to a silane-based synthetic resin emulsion coating composition that has excellent water resistance. Since synthetic resin aqueous emulsions are water-based, they are pollution-free, fire-free, and energy-saving compared to solvent-based ones.In addition, various monomers can be easily copolymerized to improve performance; It is possible to easily blend polymers together, which is considered difficult because the solvent is selected depending on the coalescence, and the performance of the emulsion or polymer itself can be easily changed, for example by changing the ionicity, by selecting the emulsifier. It has the advantage of being able to be used with paint binders, adhesives, textile processing, paper processing, film processing, architectural finishing, civil engineering, and other fields. However, since it is manufactured by emulsion polymerization, it contains more or less emulsifier, and there has always been a problem with the water resistance of the film. If a synthetic resin emulsion with extremely good water resistance could be obtained, it would be particularly advantageous to use it as a coating agent, so it has been desired to produce it. The present inventors have focused on the excellent water resistance, chemical resistance, adhesion to metals, abrasion resistance, heat resistance, etc. of the recently developed silane-based synthetic resin emulsion, and have improved the water resistance of this emulsion. As a result of various studies in order to develop a coating composition with even higher water resistance, by specifying the monomer composition, emulsifier, and additives, an emulsion composition that forms a coating with extremely excellent water resistance was developed. They discovered this and completed the present invention. In other words, the present invention provides an aqueous emulsion containing a copolymer having a glass transition temperature of 70°C or less obtained by emulsion polymerization of vinyl silane and an acrylic monomer using a polymerizable emulsifier, based on 100 parts by weight of the solid content. , a water-resistant coating composition containing 20 to 400 parts by weight of colloidal silica. Hydrolyzable vinylsilanes are suitable for use in the present invention, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxy-ethoxy)silane, vinyltriacetoxysilane, and γ-methacrylosilane. Examples include oxypropyltrimethoxysilane, vinyltrichlorosilane, and γ-methacrylooxypropyltris(methoxy-ethoxy)silane, but γ-methacrylooxypropyltrimethoxysilane is most preferred from the viewpoint of copolymerizability. Acrylic monomers used in the present invention include acrylic acid alkyl esters in which the alkyl group has 1 to 12 carbon atoms, and acrylic acid alkyl esters in which the alkyl group has 1 to 12 carbon atoms;
12 methacrylic acid alkyl esters. Styrene is a monomer copolymerized with these. Other monomers include a small amount of N
Examples include methylol acrylamide, acrylic acid, methacrylic acid, itaconic acid, acrylamide, acrylonitrile, vinyl acetate, and vinyl esters of saturated carboxylic acids branched at the α-position. The copolymerization ratio of vinyl silane is 0.5 to 15 parts by weight, preferably 1 to 10 parts by weight, based on a total of 100 parts by weight of the acrylic monomer and the monomer for copolymerization. The glass transition temperature of the copolymer must be below 70°C. This is because if the temperature exceeds 70°C, it is difficult to obtain a transparent and uniform coating film. Suitable copolymer combinations include vinyltrimethoxysilane/butyl acrylate/methyl methacrylate; vinyltriethoxysilane/2-ethylhexyl acrylate/methyl methacrylate/acrylic acid; vinylmethoxysilane/butyl acrylate.・Styrene; vinyltriacetoxysilane, butyl acrylate, methyl methacrylate; vinyltris(2-methoxy-ethoxy)silane, 2-ethylhexyl acrylate, styrene;
Among γ-methacryloxypropyltrimethoxysilane, octyl acrylate, methyl methacrylate, etc., those having a glass transition temperature of 70° C. or lower can be mentioned. As an emulsifier, to improve water resistance,
The following polymerizable emulsifiers are used. (1) Alkaline salt of alkylaryl sulfosuccinate; (In the formula, R 1 is an alkyl group having 8 to 20 carbon atoms) (2) Sodium (glycerin n-alkenylsuccinoylglycerin) borate (In the formula, R 2 is an alkyl group having 12 to 20 carbon atoms) (3) Alkaline salt of sulfopropyl maleic acid monoalkyl ester (In the formula, R 3 is an alkyl group having 8 to 20 carbon atoms) (4) Polyoxyethylene alkyl ester of acrylic acid or methacrylic acid (In the formula, R 4 is H or CH 3 , R 5 has a carbon number of 8 to 20
alkyl groups, n is an integer from 1 to 20). These polymerizable emulsifiers copolymerize with the monomer and do not remain as emulsifiers, so they greatly contribute to improving the water resistance of the film. As for the polymerization method, the monomer may be charged in a batch manner or in a continuous feeding manner. Alternatively, a method may be adopted in which a portion is first polymerized and then the remaining portion is continuously fed. Although the monomers that are continuously fed may be fed as they are, it is extremely suitable to feed the monomers as a monomer emulsion using water and an emulsifier. Further, high temperature polymerization or redox polymerization may be used. Next, colloidal silica is added and mixed into the resulting silane-based synthetic resin emulsion.
The colloidal silica used is ultrafine silica sol dispersed in colloidal water or ultrafine powder silica, both of which have a primary particle diameter of 7.
It exhibits a spherical shape with a diameter of ~50 mμ. Therefore, from the viewpoint of surface activity, it is preferable to use a colloidal dispersion in water. The amount of colloidal silica added is preferably 20 to 400 parts by weight based on 100 parts by weight of the solid content of the silane-based synthetic resin emulsion. Silane-based synthetic resin emulsion films self-crosslink at room temperature, and the presence of colloidal silica at this time allows the crosslinking reaction to proceed more strongly, giving the film excellent water resistance. Coating compositions that form highly water-resistant films can be made by changing the monomer composition, from those that form hard films to those that form soft films, and those that form highly adhesive films. ,
You can make things that are sticky, so
It can be used as a sealer to prevent water absorption of concrete or lightweight concrete such as ALC, as a water-resistant emulsion paint mixed with pigments and fillers, as a coating for plastic films, and as a coating for paper. Next, the present invention will be explained with reference to Examples and Comparative Examples. Example 1 A monomer mixture consisting of 50 parts by weight of butyl acrylate, 44 parts by weight of methyl methacrylate, and 6 parts by weight of vinyltrimethoxysilane was emulsion polymerized in the presence of 2 parts by weight of sodium salt of alkylaryl sulfosuccinate. Solid content 40% by weight, viscosity 100
Particle size 10 in 100 parts by weight of centipoise aqueous dispersion
100 parts by weight of an aqueous colloidal silica solution having a solid content of ~20 mμ and a solid content of 30% by weight were added to obtain a coating composition having a solid content of 35% by weight, a mucus of 50 centipoise, and a pH of 8.5. Example 2 A coating composition was prepared in the same manner as in Example 1, except that a sodium salt of sulfopropyl maleic acid monoalkyl ester was used instead of the emulsifier used in Example 1, the sodium salt of alkylaryl sulfosuccinate. I got it. Example 3 A coating composition was obtained in the same manner as in Example 1, except that γ-methacrylooxypropyltrimethoxysilane was used instead of vinyltrimethoxysilane. Comparative Example 1 A synthetic resin emulsion obtained in Example 1 to which no aqueous colloidal silica solution was added. Comparative Example 2 A coating composition was obtained in exactly the same manner as in Example 1, except that the polymerization was performed without using vinyltrimethoxysilane. Comparative Example 3 A coating composition was obtained in exactly the same manner as in Example 1, except that a nonionic surfactant was used instead of the sodium salt of alkylaryl sulfosuccinate. (Test results) The compositions obtained in the Examples and Comparative Examples were applied to a glass plate to a thickness of 0.2 mm, dried at 40°C, and then left immersed in room temperature water for 7 days.
The presence or absence of whitening of the coating film and its adhesion were measured. The results were as shown in Table 1.
【表】【table】
Claims (1)
乳化剤を用いて乳化重合してえたガラス転移温度
70℃以下の共重合体を含有する水性エマルジヨン
に、その固形分100重量部に対し、コロイダルシ
リカ20〜400重量部を配合してなる耐水性コーテ
イング組成物。 ２ 前記共重合体が、ビニルシランとアクリル系
単量体と他の共重合性単量体とを乳化重合してえ
られた共重合体である特許請求の範囲第１項記載
の組成物。[Claims] 1. Glass transition temperature obtained by emulsion polymerization of vinyl silane and acrylic monomer using a polymerizable emulsifier.
A water-resistant coating composition comprising 20 to 400 parts by weight of colloidal silica per 100 parts by weight of the solid content of an aqueous emulsion containing a copolymer having a temperature of 70°C or less. 2. The composition according to claim 1, wherein the copolymer is a copolymer obtained by emulsion polymerization of vinylsilane, an acrylic monomer, and another copolymerizable monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58027989A JPS59152972A (en) | 1983-02-21 | 1983-02-21 | Water-resistant coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58027989A JPS59152972A (en) | 1983-02-21 | 1983-02-21 | Water-resistant coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59152972A JPS59152972A (en) | 1984-08-31 |
| JPH0347669B2 true JPH0347669B2 (en) | 1991-07-22 |
Family
ID=12236235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58027989A Granted JPS59152972A (en) | 1983-02-21 | 1983-02-21 | Water-resistant coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59152972A (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2303632B (en) * | 1995-07-24 | 1999-03-10 | Toagosei Co Limited | Curable emulsion and coating material comprising the same |
| JP4804633B2 (en) * | 2001-02-15 | 2011-11-02 | 日東電工株式会社 | Water-dispersed pressure-sensitive adhesive composition and pressure-sensitive adhesive sheets |
| KR100731563B1 (en) * | 2002-02-04 | 2007-06-22 | 아사히 가세이 케미칼즈 가부시키가이샤 | Antifouling water-based coating composition |
| TWI294361B (en) * | 2003-03-31 | 2008-03-11 | Jujo Paper Co Ltd | Thermally sensitive recording medium |
| JP4971651B2 (en) * | 2006-03-01 | 2012-07-11 | 関西ペイント株式会社 | Water-based colorful pattern paint and painting method |
| KR101664816B1 (en) | 2009-03-10 | 2016-10-11 | 다우 코닝 도레이 캄파니 리미티드 | Oil-in-water silicone emulsion composition |
| EP2406322A2 (en) | 2009-03-10 | 2012-01-18 | Dow Corning Toray Co., Ltd. | Oil-in-water silicone emulsion composition |
| CN102470680A (en) | 2009-07-17 | 2012-05-23 | 三菱制纸株式会社 | Coated printing paper |
| JP5848704B2 (en) | 2010-07-02 | 2016-01-27 | 東レ・ダウコーニング株式会社 | Oil-in-water silicone emulsion composition |
| US10947407B2 (en) | 2017-12-01 | 2021-03-16 | Essential Industries, Inc. | Coating compositions |
| CN108192469A (en) * | 2018-01-22 | 2018-06-22 | 成都今天化工有限公司 | It is a kind of to prepare a nanometer method for osmosis type water-repellent paint |
| CN109628028B (en) * | 2018-12-19 | 2020-10-27 | 常熟巴德富科技有限公司 | Ceramic tile back glue emulsion and preparation method thereof |
| WO2020255895A1 (en) | 2019-06-21 | 2020-12-24 | ダウ・東レ株式会社 | Oil-in-water silicone emulsion composition and use thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5289132A (en) * | 1976-01-22 | 1977-07-26 | Kansai Paint Co Ltd | Paint composition |
| JPS5657860A (en) * | 1979-10-18 | 1981-05-20 | Kansai Paint Co Ltd | Coating composition for building material |
-
1983
- 1983-02-21 JP JP58027989A patent/JPS59152972A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5289132A (en) * | 1976-01-22 | 1977-07-26 | Kansai Paint Co Ltd | Paint composition |
| JPS5657860A (en) * | 1979-10-18 | 1981-05-20 | Kansai Paint Co Ltd | Coating composition for building material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59152972A (en) | 1984-08-31 |
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