TW202300544A - 丙烯酸樹脂乳液及其製造方法以及塗料組成物 - Google Patents
丙烯酸樹脂乳液及其製造方法以及塗料組成物 Download PDFInfo
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- TW202300544A TW202300544A TW111111119A TW111111119A TW202300544A TW 202300544 A TW202300544 A TW 202300544A TW 111111119 A TW111111119 A TW 111111119A TW 111111119 A TW111111119 A TW 111111119A TW 202300544 A TW202300544 A TW 202300544A
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- acrylic resin
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- acrylate
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- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 45
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
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Classifications
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/022—Emulsions, e.g. oil in water
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- 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
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- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- 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
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- C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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- C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/027—Dispersing agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/45—Anti-settling agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
[課題] 本發明之目的在於提供一種賦予具有透明性、耐水性、耐鹽水性、及撥水性之塗膜之丙烯酸樹脂乳液、及其製造方法、以及塗料組成物。
[解決手段] 一種丙烯酸樹脂乳液,其包含:丙烯酸樹脂、高分子乳化劑及水;該丙烯酸樹脂為(A)含聚合性基之三有機矽基酯單體20~80質量份、(B)不具有官能基之(甲基)丙烯酸烷基酯單體20~80質量份,及(C)(A)成分及(B)成分以外之含聚合性基及官能基之單體0~60質量份(但,(A)~(C)之合計為100質量份)之聚合物;該高分子乳化劑為(D)具有數平均分子量1,000以上之高分子乳化劑,相對於前述(A)~(C)成分之合計100質量份為5~70質量份。
Description
本發明係關於丙烯酸樹脂乳液者,更詳言之,關於能形成透明性、耐水性、耐鹽水性、撥水性優異之皮膜之丙烯酸樹脂乳液及其製造方法。並且本發明係關於包含該乳液之塗料組成物。
以往,在水中及海水中所使用之物品之作為塗料之黏合劑,至今諸多使用油性系樹脂、松香系樹脂、乙烯系樹脂、丙烯酸系樹脂、氯化橡膠系樹脂等,該等皆為溶劑稀釋型。
然而,近年來由於環境之問題點,故分散媒體從有機溶劑系逐漸朝向轉往水系。丙烯酸系樹脂乳液具有多種之單體,由於其設計之容易性,故經常被一般性使用。但,使用界面活性劑之丙烯酸樹脂乳液雖然為高透明性,但耐水性明顯較差的情況為多。
為了解決該問題點,進行開發提高耐水性之丙烯酸系樹脂乳液。日本特開平7-268022號公報揭示將變性苯乙烯‐(甲基)丙烯酸酯‐不飽和羧酸共聚物之水溶性鹽作為保護膠質進行乳化聚合而成之丙烯酸樹脂乳液。又,日本特開2008-280469號公報揭示使用PVA作為分散劑之丙烯酸系之水性乳液組成物之耐水性為高。
然而該等方法雖可取得耐水性,但會有損及皮膜透明性的情況。在使用作為塗料之情況,若損及透明性,則由於塗料之色彩會變得不鮮艷,故期望開發具備透明性與耐水性之丙烯酸樹脂乳液。
另一方面,含三有機矽基之單體係自以往即已知作為具有耐水性之單體。例如,日本特開2005-82725號公報或WO2017/164283揭示一種塗料組成物,其係含有甲基丙烯酸三異丙基矽基酯與丙烯酸單體之共聚物。但,由於皆為有機溶劑系之組成物,故從規制VOC之觀點,或有因塗裝作業者暴露於有機溶劑所造成之健康受損之憂慮,故期望開發考量到環境之水系之乳液。
日本特開2006-052284號公報揭示一種水分散體,其係使包含甲基丙烯酸三異丙基矽基酯與其他聚合性不飽和單體之混合物進行乳化聚合而成。
[先前技術文獻]
[專利文獻]
[專利文獻1] 日本特開平7-268022號公報
[專利文獻2] 日本特開2008-280469號公報
[專利文獻3] 日本特開2005-82725號公報
[專利文獻4] WO2017/164283
[專利文獻5] 日本特開2006-052284號公報
[發明所欲解決之課題]
但,上述專利文獻5記載之水分散體在透明性及耐鹽水性之面上仍尚有改良之餘地。
本發明係有鑑於上述情況所完成者,其目的在於提供會賦予具有透明性、耐水性、耐鹽水性、及撥水性之塗膜之丙烯酸樹脂乳液、及其製造方法、以及塗料組成物。
[用以解決課題之手段]
本發明者為了達成上述目的經過精心研討之結果,發現使(A)含聚合性基之三有機矽基酯單體、(B)(甲基)丙烯酸烷基酯單體、及(C)任意之其他含聚合性基之單體,在(D)特定之高分子乳化劑之存在下進行乳化並聚合而得之丙烯酸樹脂乳液會賦予具有透明性、耐水性、耐鹽水性、及撥水性之塗膜,進而完成本發明。
因此,本發明提供下述之丙烯酸樹脂乳液及其製造方法,以及塗料組成物。
一種丙烯酸樹脂乳液,其包含:丙烯酸樹脂、高分子乳化劑及水;該丙烯酸樹脂為(A)含聚合性基之三有機矽基酯單體20~80質量份、(B)不具有官能基之(甲基)丙烯酸烷基酯單體20~80質量份,及(C) (A)成分及(B)成分以外之含聚合性基及官能基之單體0~60質量份(但,(A)~(C)之合計為100質量份)之聚合物;該高分子乳化劑為(D)具有數平均分子量1,000以上之高分子乳化劑,相對於前述(A)~(C)成分之合計100質量份為5~70質量份。
尚且,本發明中,「(甲基)丙烯酸烷基酯單體」係意指丙烯酸烷基酯單體及甲基丙烯酸烷基酯單體之至少一種。又「高分子乳化劑」係意指具有高分子量之乳化劑。更詳細而言,具有乳化劑能力之高分子化合物。
[發明效果]
本發明之丙烯酸樹脂乳液可賦予具有透明性、耐水性、耐鹽水性、及撥水性之塗膜。由含有該乳液之塗料組成物所得之塗膜具有優異之耐水性及產色性。又,本發明之乳液由於為水系,故在作業面及環境面上之益處顯著。並且本發明之乳液之長期間保存安定性亦為優異。
本發明之丙烯酸樹脂乳液係能使(A)含聚合性基之三有機矽基酯單體、(B)丙烯酸烷基酯單體及/或甲基丙烯酸烷基酯單體、(C)因應必要之能與(A)成分及(B)成分進行共聚合之其他之含官能基單體,在(D)特定之高分子乳化劑之存在下進行乳化聚合來製造。
以下,詳述關於各成分。
(A)含聚合性基之三有機矽基酯單體
含聚合性基之三有機矽基酯單體為具有三有機矽基與聚合性基之單體。聚合性基為例如,具有聚合性不飽和雙鍵之碳數2~24之可具有雜原子之一價烴基,可舉出例如,源自(甲基)丙烯酸、源自4-戊烯酸、源自馬來酸、及源自富馬酸之基。
(A)成分較佳為下述一般式(I)所示者。
R
1為具有聚合性不飽和雙鍵之碳數2~24之可具有雜原子之一價有機基,R
2~R
4係互相獨立為碳數3~10之1價之直鏈或分支狀烴基,或碳數3~10之1價之環狀烴基。
上述式(I)中,R
1為具有聚合性不飽和雙鍵之碳數2~24,較佳為碳數2~15,更佳為碳數2~10之可具有雜原子之一價有機基。例如,具有聚合性不飽和雙鍵之碳數2~10,較佳為碳數2~6之一價烴基,更佳可舉出如下述所示之基。
上述中,作為R
5,可舉出如碳數1~8之直鏈狀、支鏈狀、或環狀之烷基、不飽和烷基、及芳烷基等。作為碳數1~8之直鏈或支鏈狀之烷基,可舉出例如,甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、s-丁基、t-丁基、2-甲基丁基、2-乙基丁基、n-戊基、3-甲基戊基、己基、庚基、辛基等。作為環狀烷基,可舉出例如,環丙基、環丁基、環戊基、環己基、環庚基、環辛基等。作為不飽和烷基,可舉出如2-丙烯基、2-丁烯基、3-丁烯基、2-戊烯基、3-戊烯基、4-戊烯基等。作為芳烷基,可舉出例如,苄基、苯乙基、苯基丙基等。尚且,前述烷基、環烷基、不飽和烷基、芳烷基等亦可具有取代基。作為取代基,可舉出如烷氧基、醯基等。關於取代基之數量及取代位置等,只要在不妨礙本發明效果之範圍即可,而並非係受到特別限定者。以碳數1~8之直鏈狀、支鏈狀、或環狀之烷基為佳。
R
6~R
8係互相獨立表示碳數3~8之分支烷基或苯基。作為碳數3~8之分支烷基,可舉出例如,異丙基、異丁基、s-丁基、t-丁基、2-甲基丁基、異戊基、2-乙基丁基、3-甲基戊基等。尤其,作為R
6~R
8,以異丙基、s-丁基、t-丁基、及苯基為佳,以異丙基為較佳。
(A)成分較佳為下述一般式(I’)或(II)所示者。
上述式(I’)中,R
1’為具有聚合性不飽和雙鍵之碳數2~10之一價烴基。R
1’係以碳數2~6之一價烴基為佳,較佳為下述所示之基。
特佳係R
1’為CH
2=C(CH
3)-或CH
2=CH-。
上述式(II)中,R
9為上述R
5所示之基,或上述
R
6R
7R
8Si-所示之三有機矽基。即,碳數1~8之直鏈狀、支鏈狀、或環狀之烷基、不飽和烷基、芳烷基、或R
6R
7R
8Si-所示之基,R
6~R
8係互相獨立為碳數3~8之分支烷基或苯基。
上述(I)、(I’)及(II)中,R
2~R
4係互相獨立為碳數3~10,較佳為碳數3~8之直鏈或分支狀之一價烴基,或碳數3~10,較佳為碳數3~8之一價環狀烴基。作為直鏈狀之一價烴基,可舉出例如,n-丙基、n-丁基、n-戊基、己基、庚基、辛基等之烷基。作為分支狀之一價烴基,以在α位或β位之碳原子具有1價烴基之第2級或第3級烷基為佳。在此,α位之碳原子係指上述式中與矽原子鍵結之碳原子,β位之碳原子係指位於該α位之碳原子近鄰之碳原子。在α位或β位之碳原子上鍵結之1價烴基為甲基、乙基等即可。作為分支狀之一價烴基,可舉出例如,異丙基、異丁基、s-丁基、t-丁基、2-甲基丁基、異戊基、2-乙基丁基、及3-甲基戊基等。作為碳數3~10之1價之環狀烴基,可舉出如苯基、苄基、環己基等。尤其,作為R
2~R
4,以異丙基、s-丁基、t-丁基、及苯基為佳,以異丙基為較佳。
可舉出例如,含三異丙基矽基之單體、含三異丁基矽基之單體、含三s-丁基矽基之單體、含三異戊基矽基之單體、含三苯基矽基之單體、含二異丙基異丁基矽基之單體、含二異丙基s-丁基矽基之單體、含二異丙基異戊基矽基之單體、含二異丙基苯基矽基之單體、含異丙基二異丁基矽基之單體、含異丙基二s-丁基矽基之單體、含t-丁基二異丁基矽基之單體、含t-丁基二異戊基矽基之單體,及,含t-丁基二苯基矽基之單體等之含三有機矽基之單體。該等含三有機矽基之單體係可單獨使用或可組合使用2種以上。其中,尤其係以含三異丙基矽基之單體、含三s-丁基矽基之單體及含t-丁基二苯基矽基之單體為佳,以含三異丙基矽基之單體為較佳。尤其,從製造步驟、製造成本、原料取得容易性及環境安全性之觀點,作為含三有機矽基之單體,以R
2~R
4皆為異丙基之含三異丙基矽基之單體為佳。
作為(A)成分,可舉出例如,(甲基)丙烯酸三異丙基矽基酯、4-戊烯酸三異丙基矽基酯、馬來酸雙(三異丙基矽基)酯、馬來酸甲基三異丙基矽基酯、馬來酸乙基三異丙基矽基酯、馬來酸n-丁基三異丙基矽基酯、馬來酸異丁基三異丙基矽基酯、馬來酸t-丁基三異丙基矽基酯、馬來酸n-戊基三異丙基矽基酯、馬來酸異戊基三丙基矽基酯、馬來酸2-乙基己基三異丙基矽基酯、馬來酸環己基三異丙基矽基酯、富馬酸雙(三異丙基矽基)酯、富馬酸甲基三異丙基矽基酯、富馬酸乙基三異丙基矽基酯、富馬酸n-丁基三異丙基矽基酯、富馬酸異丁基三異丙基矽基酯、富馬酸n-戊基三異丙基矽基酯、富馬酸異戊基三異丙基矽基酯、富馬酸2-乙基己基三異丙基矽基酯、富馬酸環己基三異丙基矽基酯等。該等係可單獨使用或可使用兩種以上。尤其,以(甲基)丙烯酸三異丙基矽基酯為佳。尚且,(甲基)丙烯酸三異丙基矽基係指丙烯酸三異丙基矽基酯或甲基丙烯酸三異丙基矽基酯。
相對於(A)~(C)成分之合計100質量份,(A)成分之量為20~80質量份,以40~75質量份為佳。若未滿20質量份,則有取得之皮膜不具有充分耐水性及耐鹽水性之憂慮,若超過80質量份,則有丙烯酸樹脂乳液之MFT超過50℃之憂慮。
(B)不具有官能基之(甲基)丙烯酸烷基酯單體
(B)成分為丙烯酸烷基酯單體及/或甲基丙烯酸烷基酯單體(以下,有稱為丙烯酸成分的情況)。不具有羥基、烷氧基、醯胺基、羧基等之官能基之丙烯酸烷基酯單體或甲基丙烯酸烷基酯單體。以在酯末端具有碳數1~10之烷基為佳。以丙烯酸成分之聚合物之玻璃轉移溫度(以下,有稱為Tg的情況)在40℃以上為佳,較佳在60℃以上之單體為佳。作為該單體,可舉出例如甲基丙烯酸甲酯、甲基丙烯酸異丙基酯、甲基丙烯酸乙基酯、甲基丙烯酸環己基酯、丙烯酸2-乙基己基酯、及丙烯酸丁基酯等。尚且,Tg之上限係以200℃以下為佳,更佳為150℃以下。該玻璃轉移溫度係能依據JIS K7121進行測量。
相對於(A)~(C)成分之合計100質量份,(B)成分之量為20~80質量份,以25~75質量份為佳。若未滿20質量份,則有乳化聚合反應不會進行的憂慮,若超過80質量份,則有取得之皮膜不具有耐水性的憂慮。
又,也可使能與上述(A)成分及(B)成分共聚合之含有官能基之其他單體(C)進行共聚合。該(C)成分只要係可具有羧基、醯胺基、羥基、烷氧基、乙烯基或烯丙基等之官能基之具有不飽和鍵之單體即可。可舉出例如,甲基丙烯酸、丙烯酸、丙烯醯胺、甲基丙烯酸烯丙基酯、甲基丙烯酸乙烯酯、丙烯酸2-甲氧基乙酯(甲氧基乙基丙烯酸酯)、甲基丙烯酸2-羥基乙基酯、及甲基丙烯酸2-羥基丙基酯。藉由使該等進行共聚合,變得能使核殼樹脂與熱可塑性樹脂之相容性提升。以甲基丙烯酸、丙烯酸、丙烯酸2-甲氧基乙基酯、及甲基丙烯酸2-羥基乙基酯為佳。
相對於上述(A)~(C)之合計100質量份,(C)成分之量為0~60質量份,較佳為0.5~30質量份,或1~25質量份,以及5~20質量份。若超過60質量份,則有乳液變得不安定而無法聚合的不良情況。
(D)高分子乳化劑
(D)成分只要係公知之高分子乳化劑即可。高分子乳化劑係指如上述般具有高分子量之乳化劑,更詳細而言,具有乳化劑能力之高分子化合物。高分子量係指數(或重量)平均分子量1,000以上,以1,000~200,000為佳。該數平均分子量之下限值較佳為3,000以上,更佳宜為5,000以上。上限值係以100,000以下為佳,較佳為80,000以下,更佳宜為50,000以下。乳化劑之分子量若未滿上述下限值,則有會產生凝聚物之不良情況的憂慮,若超出上述上限值,則會大量產生凝聚物,最差的情況會有產生膠化之不良情況的憂慮。數平均分子量係以GPC來測量之聚苯乙烯換算值。又,本發明中將具有分子量50,000以下之化合物稱為寡聚物。
作為高分子乳化劑,可舉出例如,選自含羧基之(共)聚合物或其鹽、含羧酸酯之(共)聚合物、及胺基甲酸酯樹脂之1種以上之高分子乳化劑。較佳可舉出如,選自聚(甲基)丙烯酸、聚(甲基)丙烯酸鹽、聚(甲基)丙烯酸酯、苯乙烯・(甲基)丙烯酸共聚物、苯乙烯・(甲基)丙烯酸鹽共聚物、苯乙烯・(甲基)丙烯酸酯共聚物、及聚胺基甲酸酯樹脂之1種以上之高分子化合物。
作為包含聚(甲基)丙烯酸鹽、聚(甲基)丙烯酸酯、苯乙烯・(甲基)丙烯酸共聚物、苯乙烯・(甲基)丙烯酸鹽共聚物、及苯乙烯・(甲基)丙烯酸酯共聚物之乳化劑,可舉出如JONCRYL JDX-6500(不揮發分30%)、JONCRYL JDX-6102B(不揮發分24.5%)、JONCRYL HPD-96J(不揮發分34%)、及JONCRYL 52J(不揮發分60%)(皆為BASF公司製)、E-1048、及HE-1335(不揮發分45.5%)(星光PMC公司等)。
作為聚(甲基)丙烯酸,可舉出如Aron(東亞合成公司製,聚丙烯酸系)聚丙烯酸酯。
作為聚胺基甲酸酯樹脂,可舉出如Hydran WLS-213(DIC公司製,不揮發分34%~36%)等。
相對於上述(A)~(C)成分之合計100質量份,該(D)高分子乳化劑之量為5~70質量份,以20~60質量份為佳。如上述市售品般,在包含高分子乳化劑與溶劑之情況,相對於上述(A)~(C)成分之合計100質量份,以固體成分量計為5~70質量份,以20~60質量份為佳。若未滿5質量份,則有因不與丙烯酸單體而導致大量殘留的不良情況。
本發明之丙烯酸樹脂乳液係藉由使上述(A)成分及(B)成分,與因應必要之(C)成分,在(D)高分子乳化劑之存在下進行乳化使其聚合之方法來取得。詳細而言,使(A)及(B)成分與因應必要(C)成分之混合物,在自由基起始劑存在下,在50~90℃之條件下,在指定時間內(3小時~)追加2~10次,或連續性地滴下(D)高分子乳化劑來使其反應。
作為自由基起始劑,可舉出例如過硫酸鉀、過硫酸銨等之過硫酸鹽、過硫酸氫水、t-丁基氫過氧化物、過氧化氫、過氧化苯甲醯、及AIBN等。因應必要,也可使用併用有酸性亞硫酸鈉、甲醛次硫酸氫鈉、L-抗壞血酸、酒石酸、糖類、及胺類等之還原劑的氧化還原系統。
並且為了調整聚合物之分子量,而可添加鏈轉移劑。
聚合溫度係以50~90℃為佳,以50~70℃為更佳。
本發明之丙烯酸樹脂乳液具有平均粒子徑300nm以下,較佳具有50~250nm,更佳具有50~200nm。在平均粒徑過大的情況,會無法取得透明塗覆材料,在過小的情況,則有分散性降低的問題。也能使用濕式微粒化裝置(Star Burst)、高壓均質機、連續式乳化機、膠體磨機,及捏合機等公知方法進行微粒化。乳液之平均粒子徑係可使用例如大塚電子公司製FPAR-1000,以動態光散射法進行測量。
本發明之丙烯酸樹脂乳液係以具有最低成膜溫度(MFT)50℃以下為佳。以0~50℃為佳,較佳為0~20℃,更佳為0~15℃。藉此,即使在室溫、低氣溫之環境下,也可良好地形成皮膜。MFT若超過上述上限值,則有在室溫進行乾燥之情況導致塗膜產生龜裂的憂慮。前述最低成膜溫度係使塗膜組成物進行乾燥時,會形成無龜裂且均勻皮膜之最低溫度,可藉由JIS K 6828-2:2003記載之方法進行測量。
丙烯酸樹脂乳液之固體成分係以25~50質量%為佳。又,黏度(25℃)係以500mPa・s以下為佳,以20~ 300mPa・s為更佳。黏度係能以旋轉黏度計進行測量。尚且,乳液之剩餘部分為水,因應必要亦可含有有機溶劑。水之量並無特別限制,較佳係乳液之固體成分成為25~50質量%之量。
本發明之丙烯酸樹脂乳液之長期保存安定性為良好,且由於能形成透明性、耐水性、耐鹽水性、及撥水性優異之塗膜,故適宜使用作為塗料組成物。
本發明之塗料組成物除了前述丙烯酸樹脂乳液之外,亦可使用其他有機樹脂、防污劑、顏料、塑化劑、其他添加物等。
作為前述其他有機樹脂,並非係受到特別限定者,可舉出例如,氯化橡膠、氯乙烯-乙酸乙烯酯共聚合物、氯乙烯-異丁基乙烯基醚共聚合物等之合成樹脂或松香、松香金屬鹽或變性松香等之天然樹脂,該等係可單獨使用或可組合使用2種以上。
作為前述防污劑,可舉出例如,氧化亞銅、硫氰化銅(copper rhodanide)、銅粉、2-巰基吡啶-N-氧化銅等之銅化合物、2-巰基吡啶-N-氧化鋅、雙二甲基二硫代胺甲醯基鋅伸乙基雙二硫代胺甲酸酯
(bisdimethyldithiocarbamoylzinc ethylenebisdithiocarbamate)、鋅二甲基二硫代胺甲酸酯等之鋅化合物,2,4,5,6-四氯間苯二甲腈、3,4-二氯苯基二甲基脲、4,5-二氯-2-N-辛基-3-(2H)-異噻唑啉、N,N-二甲基-N’-苯基(N-氟二氯甲硫基)磺醯胺、四甲基秋蘭姆二硫醚、四乙基秋蘭姆二硫醚、3-碘-2-丙炔基丁基胺甲酸酯、吡啶三苯基硼烷、2-(甲氧基羰基胺基)苯並咪唑等之不包含金屬之化合物等,該等係可單獨使用或可組合使用2種以上。
作為前述顏料,並非係受到特別限定者,可舉出例如,氧化鐵紅(Bengala)、滑石、氧化鈦、二氧化矽、碳酸鈣、硫酸鋇、氧化鈣、氧化鋅等,該等係可單獨使用或可組合使用2種以上。
作為前述塑化劑、其他添加物,並非係受到特別限定者,可舉出例如,磷酸三甲苯酚基酯、鄰苯二甲酸二辛基酯、氯化石蠟、流動石蠟、聚丁烯等之塑化劑、皂土、氧化聚乙烯、各種之醯胺化合物等之觸變劑、染料、消泡劑、水結合劑、有機溶劑等,該等係可單獨使用或可組合使用2種以上。
在基材,例如,塑膠(PET、PI、合成皮革等)、玻璃(泛用玻璃、SiO
2等)、金屬(Si、Cu、Fe、Ni、Co、Au、Ag、Ti、Al、Zn、Sn、Zr、該等之合金等)、木材、紙、陶瓷(氧化物、碳化物、氮化物等之燒成物等)等之基材之單面或兩面塗布或浸漬本發明之塗料組成物並進行乾燥(室溫~150℃)時,即能維持基材之長處,並同時長期地賦予本樹脂之耐水性之益處。
在此作為金屬素材,可舉出如SUS或SPHC等。作為金屬素材之塗覆用途,可舉出如船底、船體、車裝、車體、建築資材等。
作為塑膠基材,使用如聚甲基丙烯酸甲酯等之聚(甲基)丙烯酸酯、聚碳酸酯、聚苯乙烯、聚對酞酸乙二酯、聚氯乙烯、聚酯、纖維素、二乙二醇雙烯丙基碳酸酯聚合物、丙烯腈-丁二烯-苯乙烯聚合物、聚胺基甲酸酯、及環氧樹脂等。作為塑膠加工品,如有汽車內裝材或有機玻璃、電材或建材、建築物之外裝材、使用液晶顯示器等之光學薄膜、光擴散薄膜、行動電話、家電製品等。
作為玻璃基材,使用如鈉鈣玻璃、石英玻璃、鉛玻璃、硼矽酸玻璃、無鹼玻璃等。作為玻璃加工品,如有建築用板玻璃、汽車等車輛用玻璃、透鏡用玻璃、鏡用玻璃、顯示器面板用玻璃、太陽能電池模組用玻璃等。
作為木材基材,使用如槭樹科、樺木科、樟科、栗科、玄參科、南洋杉科、榆科、紫葳科、薔薇科、柏科、龍腦香科、桃金孃科、殼斗科、松科、豆科、木犀科等之木材。作為木材加工品,也可為選自將木本身作為原料之加工及成形品、合板及集成材及該等之加工及成形品、及該等之組合者,例如,有包含建築物之外裝及內裝用資材之住宅建築用資材、桌子等之家具類、木頭玩具、樂器等。
將本發明之塗料組成物塗覆於基材之方法並無特別限定,可舉出例如,凹版塗佈機、棒塗機、刮刀塗佈機、輥塗機、氣刀塗佈機、絲網塗佈機、簾式塗佈機、毛刷塗佈等之利用各種塗佈機之塗布方法、噴霧塗布、浸漬等。
本發明之塗料組成物對基材之塗布量並無特別限定。從施工作業性等之觀點,以固體成分換算通常係以1~300g/m
2,較佳係5~100g/m
2之範圍或以厚度1~500 μm,較佳以5~100μm來形成。成膜係可使用室溫乾燥,又,加熱100~200℃進行乾燥使其成膜。
本發明之塗料組成物尤其係適宜使用作為在水中及海水中所使用之物品之塗料,適宜作為水中塗料及海中塗料。尤其,由本發明之塗料組成物所得之塗膜之耐鹽水性為良好,故適宜使用作為塗佈在船舶之船底、海中構築物、發電所導水管、養殖用或定置用之漁網或該等所使用之浮子、繩索等之漁網附屬工具等之海中物品類表面之海中防污塗料。
[實施例]
以下,展示實施例及比較例,更加詳細說明本發明,但本發明並非係受到下述實施例所限制者。尚且,下述之例中,份及%係分別表示質量份、質量%。
[丙烯酸樹脂乳液]
[實施例1]
在附有攪拌裝置、溫度計、迴流冷卻器之2L玻璃燒瓶中,將裝有離子交換水770g、碳酸鈉2g、JDX-6500(聚丙烯酸寡聚物,數平均分子量10000,不揮發分30%)630g之容器以氮取代,以攪拌機進行攪拌,並進行加熱使內溶液之溫度成為60℃為止。將內溶液之溫度維持在60℃±1℃並同時在氮氣流下,使用滴下漏斗花費3小時滴下丙烯酸2-乙基己酯(2-EHA)70g、甲氧基乙基丙烯酸酯(MEA)87.5g、及甲基丙烯酸三異丙基矽基酯(TIPSMA)192.5g之混合物,並同時花費4小時滴下溶解於離子交換水45g中之過硫酸銨(APS)1g,而使上述混合物進行乳化聚合。反應結束後,冷卻至40℃以下,而取得具有在105℃下乾燥1小時後之不揮發分(固體成分)31%之乳白色之丙烯酸樹脂乳液。
[實施例2]
在附有攪拌裝置、溫度計、迴流冷卻器之2L玻璃燒瓶中,將裝有離子交換水770g、碳酸鈉2g、JDX-6500(聚丙烯酸寡聚物,數平均分子量10000,不揮發分30%)291.5g之容器以氮取代,以攪拌機進行攪拌,並進行加熱使內溶液之溫度成為60℃為止。將內溶液之溫度維持在60℃±1℃並同時在氮氣流下,使用滴下漏斗花費3小時滴下丙烯酸甲基丁酯(BA)87.5g、丙烯酸甲氧基乙酯(MEA)70g、及甲基丙烯酸三異丙基矽基酯(TIPSMA)192.5g之混合物,並同時花費4小時滴下溶解於離子交換水45g中之過硫酸銨(APS)1g,而使上述混合物進行乳化聚合。反應結束後,冷卻至40℃以下,而取得具有在105℃下乾燥1小時後之不揮發分(固體成分)29%之乳白色之丙烯酸樹脂乳液。
[實施例3]
在附有攪拌裝置、溫度計、迴流冷卻器之2L玻璃燒瓶中,將裝有離子交換水770g、碳酸鈉2g、JDX-6500(聚丙烯酸寡聚物,數平均分子量10000,不揮發分30%)630g之容器以氮取代,以攪拌機進行攪拌,並進行加熱使內溶液之溫度成為60℃為止。將內溶液之溫度維持在60℃±1℃並同時在氮氣流下,使用滴下漏斗花費3小時滴下丙烯酸2-乙基己酯(2-EHA)87.5g、及甲基丙烯酸三異丙基矽基酯(TIPSMA)262.5g之混合物,並同時花費4小時滴下溶解於離子交換水45g中之過硫酸銨(APS)1g,而使上述混合物進行乳化聚合。反應結束後,冷卻至40℃以下,而取得具有在105℃下乾燥1小時後之不揮發分(固體成分)30%之乳白色之丙烯酸樹脂乳液。
[實施例4]
在附有攪拌裝置、溫度計、迴流冷卻器之2L玻璃燒瓶中,將裝有離子交換水770g、碳酸鈉2g、JDX-6500(聚丙烯酸寡聚物,數平均分子量10000,不揮發分30%) 630g之容器以氮取代,以攪拌機進行攪拌,並進行加熱使內溶液之溫度成為60℃為止。將內溶液之溫度維持在60℃±1℃並同時在氮氣流下,使用滴下漏斗花費3小時滴下丙烯酸2-乙基己酯(2-EHA)262.5g、及甲基丙烯酸三異丙基矽基酯(TIPSMA)87.5g之混合物,並同時花費4小時滴下溶解於離子交換水45g中之過硫酸銨(APS)1g,而使上述混合物進行乳化聚合。反應結束後,冷卻至40℃以下,取得具有在105℃下乾燥1小時後之不揮發分(固體成分)30%之乳白色之乳液。
[實施例5]
在附有攪拌裝置、溫度計、迴流冷卻器之2L玻璃燒瓶中,將裝有離子交換水770g、碳酸鈉2g、WLS-213(胺基甲酸酯樹脂、數平均分子量25000、不揮發分30%)630g之容器以氮取代,以攪拌機進行攪拌,並進行加熱使內溶液之溫度成為60℃為止。將內溶液之溫度維持在60℃±1℃並同時在氮氣流下,使用滴下漏斗花費3小時滴下丙烯酸2-乙基己酯(2-EHA)70g、丙烯酸甲氧基乙酯(MEA)87.5g、及甲基丙烯酸三異丙基矽基酯(TIPSMA)192.5g之混合物,並同時花費4小時滴下溶解於離子交換水45g中之過硫酸銨(APS)1g,而使上述混合物進行乳化聚合。反應結束後,冷卻至40℃以下,而取得具有在105℃下乾燥1小時後之不揮發分(固體成分)30%之乳白色之乳液。
[比較例1]
在附有攪拌裝置、溫度計、迴流冷卻器之2L玻璃燒瓶中,將裝有離子交換水770g、碳酸鈉2g、JDX-6500(聚丙烯酸寡聚物,數平均分子量10000,不揮發分30%) 630g之容器以氮取代,以攪拌機進行攪拌,並進行加熱使內溶液之溫度成為60℃為止。將內溶液之溫度維持在60℃±1℃並同時在氮氣流下,使用滴下漏斗花費3時間滴下甲基丙烯酸甲酯350g,並同時花費4小時滴下溶解於離子交換水45g中之過硫酸銨(APS)1g,而使上述混合物進行乳化聚合。反應結束後,冷卻至40℃以下,而取得具有在105℃下乾燥1小時後之不揮發分(固體成分)30%之乳白色之乳液。
[比較例2]
對具備攪拌機、冷凝器、溫度計及氮氣導入口之3L聚合容器放入離子交換水500g,進行15分鐘氮氣取代後,升溫至70℃。其次,在另一容器中,以均質機使丙烯酸2-乙基己酯(2-EHA)70g、丙烯酸甲氧基乙酯(MEA)87.5g、甲基丙烯酸三異丙基矽基酯(TIPSMA)192.5g、Sanmorin OT-70(花王(股)製)3g、Neugen XL-41(第一工業製藥公司製)16g、Neugen XL-400(第一工業製藥公司製)28g、及離子交換水400g進行混合乳化而取得乳化液。將該乳化液與過硫酸鉀3g及離子交換水100g之混合物個別地進行攪拌並同時花費4小時均勻地滴下至上述聚合容器。並且,在70℃下反應2小時而結束聚合。冷卻後,添加25%氨水將pH調整成7。取得之合成樹脂乳液之固體成分為40.4%。
[比較例3]
在附有攪拌裝置、溫度計、迴流冷卻器之2L玻璃燒瓶中,將裝有離子交換水770g、碳酸鈉2g、JDX-6500(聚丙烯酸寡聚物,數平均分子量10000,不揮發分30%)630g之容器以氮取代,以攪拌機進行攪拌,並進行加熱使內溶液之溫度成為60℃為止。將內溶液之溫度維持在60℃±1℃並同時在氮氣流下,使用滴下漏斗花費3小時滴下甲基丙烯酸甲酯192.5g、丙烯酸甲氧基乙酯(MEA)140g、及甲基丙烯酸三異丙基矽基酯(TIPSMA)17.5g之混合物,並同時花費4小時滴下溶解於離子交換水45g中之過硫酸銨(APS)1g,而使上述混合物進行乳化聚合。反應結束後,冷卻至40℃以下,而取得具有在105℃下乾燥1小時後之不揮發分(固體成分)29%之乳白色之乳液。
[比較例4]
在附有攪拌裝置、溫度計、迴流冷卻器之2L玻璃燒瓶中,將裝有離子交換水770g、碳酸鈉2g、JDX-6500(聚丙烯酸寡聚物,數平均分子量10000,不揮發分30%)933g之容器以氮取代,以攪拌機進行攪拌,並進行加熱使內溶液之溫度成為60℃為止。將內溶液之溫度維持在60℃±1℃並同時在氮氣流下,使用滴下漏斗花費3小時滴下甲基丙烯酸三異丙基矽基酯(TIPSMA)350g,並同時花費4小時滴下溶解於離子交換水45g中之過硫酸銨(APS)1g,使甲基丙烯酸三異丙基矽基酯進行乳化聚合。反應結束後,冷卻至40℃以下,而取具有在105℃下乾燥1小時後之不揮發分(固體成分)29%之乳白色之乳液。
<固體成分之測量方法>
在鋁箔製之皿中正確地量取各例之樹脂乳液(試料)約1g,並放入保持在約105℃之乾燥器,加熱1小時後,從乾燥器取出並在乾燥器之中放置冷卻,測量試料之乾燥後之重量,藉由下述式來算出蒸發殘留分。
R:蒸發殘留分(%)
W:裝有乾燥前之試料之鋁箔皿之質量(g)
L:鋁箔皿之質量(g)
T:裝有乾燥後之試料之鋁箔皿之質量(g)
鋁箔皿之尺寸:70ϕ×12h(mm)
<pH之測量方法>
藉由JIS Z8802(pH測量方法),使用pH計在25℃下測量各乳液之pH。
<最低成膜溫度(MFT)之測量方法>
使用依據JIS K-6828-2之方法來測量乳液之最低成膜溫度(MFT)。詳細而言,使用加熱源與冷卻源經由固定距離來設置之簡易成膜溫度測量裝置(井元製作所製)。在鋁箔上塗佈乳液1mil,使用該裝置觀察2h後之塗膜狀態。基於溫度梯度來乾燥乳液,進行成膜並測量透明部分與未成膜之部分之境界溫度,而作為最低成膜溫度(MFT,℃)。
<乳液粒子之平均粒子徑之測量方法>
再以離子交換水來稀釋上述取得之乳液而作成固體成分:0.5~2%之溶液,使用大塚電子公司製FPAR-1000,以動態光散射法來測量乳液粒子徑。
<經時安定性之評價>
在室溫(25℃)下保管乳液3個月。使用上述方法來測量保管後之乳液之平均粒子徑。將相對於剛製造後之乳液而粒徑不會增加超過20%之範圍者評價為○。
<成膜方法>
在鋼板(日本TestPanel公司製,SPHC兩面噴砂處理)上以乾燥膜厚成為100μm之方式毛刷塗佈環氧樹脂系防鏽塗料(Bannoh 500S,中國塗料製)。乾燥後,在該膜上以乾燥膜厚成為100μm之方式毛刷塗佈乳液,在室溫下乾燥而作成塗膜試樣。
<霧度值之測量>
在載玻片(霧度值0.70%)上以乾燥膜厚成為約7μm之方式塗布乳液,使用棒塗機No.10在室溫下乾燥而形成塗膜。使用製品名「霧度計NDH7000」(日本電色工業公司製)測量具有上述塗膜之載玻片之霧度值。
<對水接觸角之測量>
對上述塗膜試樣滴下0.2μL之水滴後,使用協和界面化學公司製自動接觸角計DCA-VZ來測量30秒後之接觸角。
<耐鹽水性>
將氯化鈉溶解於離子交換水3.5%者設想作為海水,浸漬上述塗膜試樣數天,藉由目視來觀察塗膜之狀態。若無白化、剝離、及龜裂則視為沒有問題,從而進行追蹤觀察。在確認到有白化、剝離、或龜裂等皮膜異常之階段,停止觀察並當作終點。將到終點為止之天數展示於表1。
TIPSMA:甲基丙烯酸三異丙基矽基酯(信越化學工業公司製)
MMA:甲基丙烯酸甲酯
BA:丙烯酸丁酯
2-EHA:丙烯酸2-乙基己酯
MEA:丙烯酸甲氧基乙酯
JDX-6500:BASF公司製 聚丙烯酸鹽系寡聚物(數平均分子量10000)
WLS-213:DIC公司製Hydran WLS-213水性聚胺基甲酸酯樹脂(數平均分子量25000)
[實施例6]
使用均質分散機以旋轉速度3000rpm使離子交換水25份、BYK-190(濕潤分散劑,Byk-Chemie公司製)2份、氧化鈦(Tipaque CR-95(石原產業公司製)平均粒子徑0.28μm、金紅石型氧化鈦)20份、滑石MS(日本滑石公司製)及玻璃珠(直徑:1mm)100份進行分散60分鐘後,藉由使用100篩目之金屬網進行過濾,而調製出白色糊料。對其中添加實施例1取得之乳液371份而取得塗料組成物。
[實施例7~10、比較例6~9]
除了將乳液變更成下述表2之摻合之外,其他係重複上述實施例6而取得塗料組成物。
<成膜方法>
在鋼板(日本TestPanel公司製,SPHC兩面噴砂處理)上以乾燥膜厚成為100μm之方式毛刷塗佈環氧樹脂系防鏽塗料(Bannoh 500S,中國塗料製)。乾燥後,在該塗膜上以乾燥膜厚成為100μm之方式毛刷塗佈上述塗料組成物,在室溫下乾燥而取得塗膜試樣。
使用上述方法來評價各塗膜試樣之對水接觸角及耐鹽水性。將結果展示於表2。
如表1及2所示般,本發明之丙烯酸樹脂乳液能賦予具有透明性、耐水性、耐鹽水性、及撥水性之塗膜,並且長期間之保存安定性亦優。又,本發明之丙烯酸樹脂乳液由於具有50℃以下之最低成膜溫度(MFT),故在室溫下也能良好地形成皮膜。
Claims (15)
- 一種丙烯酸樹脂乳液,其包含:丙烯酸樹脂、高分子乳化劑及水; 該丙烯酸樹脂為(A)含聚合性基之三有機矽基酯單體20~80質量份、(B)不具有官能基之(甲基)丙烯酸烷基酯單體20~80質量份,及(C)(A)成分及(B)成分以外之含聚合性基及官能基之單體0~60質量份(但,(A)~(C)之合計為100質量份)之聚合物; 該高分子乳化劑為(D)具有數平均分子量1,000以上之高分子乳化劑,相對於前述(A)~(C)成分之合計100質量份為5~70質量份。
- 如請求項1或2之丙烯酸樹脂乳液,其中前述(D)成分具有數平均分子量3,000以上200,000以下。
- 如請求項1~3中任一項之丙烯酸樹脂乳液,其中前述(D)成分為選自含羧基之(共)聚合物或其鹽、含羧酸酯之(共)聚合物,及胺基甲酸酯樹脂之1種以上之高分子乳化劑。
- 如請求項4之丙烯酸樹脂乳液,其中前述(D)成分為選自聚(甲基)丙烯酸、聚(甲基)丙烯酸鹽、聚(甲基)丙烯酸酯、苯乙烯・(甲基)丙烯酸共聚物、苯乙烯・(甲基)丙烯酸鹽共聚物、苯乙烯・(甲基)丙烯酸酯共聚物,及聚胺基甲酸酯樹脂之1種以上之高分子乳化劑。
- 如請求項1~5中任一項之丙烯酸樹脂乳液,其具有最低成膜溫度(MFT)0~50℃。
- 如請求項1~6中任一項之丙烯酸樹脂乳液,其中前述(B)成分為具有碳數1~10之烷基之(甲基)丙烯酸烷基酯。
- 一種塗料組成物,其包含如請求項1~7中任一項之丙烯酸樹脂乳液。
- 一種丙烯酸樹脂乳液之製造方法,其特徵為使(A)含聚合性基之三有機矽基酯單體、(B)不具有官能基之(甲基)丙烯酸烷基酯單體,及(C)上述(A)成分及(B)成分以外之任意之含聚合性基及官能基之單體,在(D)高分子乳化劑之存在下進行乳化並使其聚合而取得丙烯酸樹脂之乳液; 其中,該(D)高分子乳化劑為以相對於(A)成分、(B)成分、及(C)成分100質量份而成為5~70質量份之量之(D)具有數平均分子量1000以上之高分子乳化劑。
- 如請求項9記載之製造方法,其中前述(D)成分具有數平均分子量3,000以上200,000以下。
- 如請求項9~10中任一項之製造方法,其中前述(D)成分為選自含羧基之(共)聚合物或其鹽、含羧酸酯之(共)聚合物,及胺基甲酸酯樹脂之1種以上之高分子乳化劑。
- 如請求項11之製造方法,其中前述(D)成分為選自聚(甲基)丙烯酸、聚(甲基)丙烯酸鹽、聚(甲基)丙烯酸酯、苯乙烯・(甲基)丙烯酸共聚物、苯乙烯・(甲基)丙烯酸鹽共聚物、苯乙烯・(甲基)丙烯酸酯共聚物,及聚胺基甲酸酯之1種以上之高分子乳化劑。
- 如請求項9~13中任一項之製造方法,其中前述丙烯酸樹脂乳液具有最低成膜溫度(MFT)0~50℃。
- 如請求項9~14中任一項之製造方法,其中(B)成分為具有碳數1~10之烷基之(甲基)丙烯酸烷基酯。
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JPH07268022A (ja) | 1994-03-29 | 1995-10-17 | Showa Highpolymer Co Ltd | 耐水性を有する水性エマルジョン組成物およびその製造方法 |
JP3681216B2 (ja) * | 1995-06-01 | 2005-08-10 | 中国塗料株式会社 | 防汚塗料組成物、この防汚塗料組成物から形成されている塗膜および該防汚塗料組成物を用いた防汚方法並びに該塗膜で被覆された船体または水中構造物 |
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