JPS62267376A - Paint composition - Google Patents
Paint compositionInfo
- Publication number
- JPS62267376A JPS62267376A JP10937586A JP10937586A JPS62267376A JP S62267376 A JPS62267376 A JP S62267376A JP 10937586 A JP10937586 A JP 10937586A JP 10937586 A JP10937586 A JP 10937586A JP S62267376 A JPS62267376 A JP S62267376A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- monomer
- epoxy equivalent
- acrylic acid
- acid ester
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 239000003973 paint Substances 0.000 title abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 229920001577 copolymer Polymers 0.000 claims abstract description 21
- 239000004593 Epoxy Substances 0.000 claims abstract description 19
- -1 disulfide compound Chemical class 0.000 claims abstract description 11
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 10
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 239000008199 coating composition Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229920000768 polyamine Polymers 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 abstract 1
- 125000005641 methacryl group Chemical group 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 10
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000005856 abnormality Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- VBHXIMACZBQHPX-UHFFFAOYSA-N 2,2,2-trifluoroethyl prop-2-enoate Chemical compound FC(F)(F)COC(=O)C=C VBHXIMACZBQHPX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は耐候性、耐薬品性、撥水性、熱的性質、機械的
性質てすぐれた性能を有する塗料に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a paint having excellent weather resistance, chemical resistance, water repellency, thermal properties, and mechanical properties.
（メタ）アクリル酸エステル単量体てはメタクリル酸メ
チル、メタクリル酸エチル、メタクリル酸ｎ−ブチル、
メタクリル酸シクロヘキシル、アクリル酸メチル、アク
リル酸エチル、アクリル酸ｎ−ゾチル、アクリル酸２−
エチルヘキシル、メタクリル酸グリンジル、アクリルｈ
’）グリンジル、メタクリル酸２−ヒドロキシエチル、
メタクリル酸２−ヒドロキシゾロピル、アクリル酸２−
ヒドロキシエチル、アクリル酸２−ヒＰ口キシプ口ビル
などがあり、本発明に使用される（メタ）アクリル酸エ
ステル単量体はこれらの群から選ばれるものである。該
単量体は単独で用いても、２種以上の混合物として用い
てもよい、本発明では、メタクリル酸エチル、メタクリ
ル酸ｎ−ブチル、メタクリル酸シクロヘキシル、アクリ
ル酸ｎ−ブチル、メタクリル酸グリシジルが特に好適に
利用できる。これらの単量体は被膜に可どう性、硬度、
基材への密着性を付与するのに有用である。また、アク
リル樹脂（人）にエポキシ基を付与する目的でも使用さ
れる。アクリル樹脂（Ａ）のエポキシ当量は、メタクリ
ルＷ１．／リシジル、アクリル酸グリシジルのように分
子内にグリシジル基な有する単量体を用い、その使用量
を調整することで決定される。アクリル樹脂（Ａ）のエ
ポキシ当量は３００以上が適切であり、これ以外では良
好な密着性、可と５性、耐薬品性が得られない。(Meth)acrylic acid ester monomers include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate,
Cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, n-zotyl acrylate, 2-acrylate
Ethylhexyl, Grindyl methacrylate, Acrylic h
') Grindyl, 2-hydroxyethyl methacrylate,
2-hydroxyzolopyl methacrylate, 2-acrylic acid
Examples include hydroxyethyl, 2-hyperacrylate, and the like, and the (meth)acrylic acid ester monomer used in the present invention is selected from these groups. The monomers may be used alone or as a mixture of two or more. In the present invention, ethyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, n-butyl acrylate, and glycidyl methacrylate are used. It can be used particularly suitably. These monomers add flexibility, hardness,
It is useful for imparting adhesion to substrates. It is also used to add epoxy groups to acrylic resins. The epoxy equivalent of the acrylic resin (A) is methacrylic W1. It is determined by using a monomer having a glycidyl group in the molecule, such as /lycidyl or glycidyl acrylate, and adjusting the amount used. The epoxy equivalent of the acrylic resin (A) is suitably 300 or more; otherwise, good adhesion, abrasion resistance, and chemical resistance cannot be obtained.
ジスルフィド化合物には粁々のものがあるが、本発明で
は、テトラメチルチウラムノスルフィド、テトラエチル
チウラムジスルフィド、テトラブチルチウラムジスルフ
ィドが好適に用いられ、本発明の主旨をもつとも効果的
に発現する。該化合物は前記単量体に対し０．０５〜１
４５重量％用いればよい。０．０５重量％以下では十分
な効果が得られず、１．５重量％以上では重合率が上が
り難く、また分子量が小さくなり過ぎて好ましくない。Although there are many types of disulfide compounds, tetramethylthiuramnosulfide, tetraethylthiuram disulfide, and tetrabutylthiuram disulfide are preferably used in the present invention, and the gist of the present invention is effectively expressed. The compound has a ratio of 0.05 to 1 to the monomer.
It is sufficient to use 45% by weight. If it is less than 0.05% by weight, a sufficient effect cannot be obtained, and if it is more than 1.5% by weight, it is difficult to increase the polymerization rate and the molecular weight becomes too small, which is not preferable.
アクリル樹脂（Ａ）はジスルフィド化合物の存在下に、
１００〜１３０℃の重合温度で、（メタ）アクリル酸エ
ステル単量体をラジカル重合することにより容易に調整
できる。Acrylic resin (A) in the presence of a disulfide compound,
It can be easily adjusted by radical polymerizing a (meth)acrylic acid ester monomer at a polymerization temperature of 100 to 130°C.
（メタ）アクリル酸フルオロアルキルエステル単量体に
は、メタクリル酸トリフルオロエチル、メタクリル酸ペ
ンタフルオロゾロ・ξノ、アクリル酸トリフルオロエチ
ル、アクリル酸ペンタフルオロプロ・ぞンなどがあり、
該単量体は単独で用いても、２種以上の混合物として用
℃・てもよし・。該単量体は単独でまたは（メタ）アク
リル酸エステル単量体と混合してエポキシ当Ｊｉ’；
１ｏ以上の単量体混合物として使用される。エポキシ当
量は既述アクリル樹脂（Ａ’）と同様の方法で決定され
る。該Ａｉｔ体混体物合物）は５〜６０重量％使用すれ
ばよい。５重量％以下では、フッ素原子による耐候性、
撥水性などの効果が全く得られず、６０重量％以上では
、被膜が脆（なったり、基材への密着性が低下して塗料
として好ましくない。８〜４０重量％用いるのがもつと
も好適で、フッ素原子による性能を余すところなく引出
すことができ、被膜も強靭で基材への密着性にもすぐれ
ている。Examples of (meth)acrylic acid fluoroalkyl ester monomers include trifluoroethyl methacrylate, pentafluorozolo methacrylate, trifluoroethyl acrylate, and pentafluoroprozone acrylate.
The monomers may be used alone or as a mixture of two or more. The monomer is used alone or in combination with a (meth)acrylic acid ester monomer to form an epoxy compound;
It is used as a monomer mixture of 10 or more. The epoxy equivalent is determined in the same manner as for the acrylic resin (A') described above. The Ait mixture compound) may be used in an amount of 5 to 60% by weight. At 5% by weight or less, weather resistance due to fluorine atoms,
No effect such as water repellency can be obtained, and if it exceeds 60% by weight, the coating becomes brittle and the adhesion to the substrate decreases, making it undesirable as a paint. It is most suitable to use it in an amount of 8 to 40% by weight. , the performance of fluorine atoms can be brought out to the fullest, and the coating is strong and has excellent adhesion to the base material.
本発明に係る共重合体は、アクリル樹脂（Ａ）の存在下
に、重合温度１００〜１３０℃で、単量体混合物（Ｂ）
のラジカル重合を実施することにより容易に得られ、何
等の特別な方法は必要としない。The copolymer according to the present invention is produced by forming a monomer mixture (B) in the presence of an acrylic resin (A) at a polymerization temperature of 100 to 130°C.
It can be easily obtained by carrying out radical polymerization, and no special method is required.
この際、ｔ・−ブチルノぞ一オキシー２−エチルヘキサ
ノエート、ｔ−プチルノゼーオキシベンゾエートなどの
有機過酸化物を、単量体混合物（Ｂ）に対し０．０２〜
１．５重量％用いれば、より迅速に発明の主旨にそった
共重合体を得ろことができる。At this time, an organic peroxide such as t-butylno-oxy-2-ethylhexanoate or t-butylno-oxybenzoate is added in an amount of 0.02 to
If 1.5% by weight is used, a copolymer meeting the gist of the invention can be obtained more quickly.
得られた共重合体は３５０〜４７５０のエポキシ当量！
有することが望ましい。エポキシ当量３５０以下では共
重合体が高粘度シてなり過ぎ、塗料用としての適正に欠
ける。エポキシ当量が４７５０以上ではエポキシ基を導
入する意味合いが薄く、密着性、耐溶剤性などが不良で
ある。エポキシ当−量は５００〜３２００がもつとも好
ましく、均衡のとれた性能を発揮するばかりでなく、水
筒２の発明を実施するうえでも好まし−・。The resulting copolymer has an epoxy equivalent weight of 350-4750!
It is desirable to have one. If the epoxy equivalent is less than 350, the copolymer will have too high a viscosity and will be unsuitable for use in paints. If the epoxy equivalent is 4,750 or more, the meaning of introducing epoxy groups is weak, and adhesion, solvent resistance, etc. are poor. It is preferable that the epoxy equivalent is between 500 and 3200, which not only provides balanced performance but also is preferable for carrying out the invention of the water bottle 2.
得られた共重合体はブロック状に共重合していることが
推定され、通常のランダム共重合物に比べ、単量体混合
物（Ｂ） Ｋ含有されているフッ素原子のすぐれて特徴
ある効果がより顕著に発現され、既述のとうり耐候性、
耐薬品性、撥水性、熱的性質、機械的性質なとて均衡が
とれて優秀な性能を発揮する。It is presumed that the obtained copolymer is copolymerized in a block form, and compared to a normal random copolymer, the monomer mixture (B) has a unique effect of the fluorine atoms contained in K. Weather resistance is more prominent than that mentioned above.
It exhibits excellent performance with a good balance of chemical resistance, water repellency, thermal properties, and mechanical properties.
本発明に係る第２の発明は、既述のとうり得られたエポ
キシ基を有する共重合体と、該共重合体に対し０．６〜
１．４ｐ＋＋ｒで配合されるポリアミン化合物とから得
られるＪｒ薬品性、撥水性、耐候性、熱的性質、機械的
性質にきわめてすぐれた性能を発揮する塗料組成物に関
するものである。The second invention according to the present invention provides a copolymer having an epoxy group obtained as described above, and a copolymer having an epoxy group of 0.6 to
The present invention relates to a coating composition that exhibits extremely excellent performance in chemical properties, water repellency, weather resistance, thermal properties, and mechanical properties obtained from a polyamine compound blended with 1.4p++r.
ポリアミン化合物は既に工業化、上布されているものの
群から自由に選択することができ、何らの限定は必要と
しない。具体的に例を挙げれば、工ぎキュア１００、エ
ビキュア１０１、エビキュア１０３、エビキュア１０４
（以上シェル化学の商品）などがある。該化合物は共重
合体に対し、０．６〜１．４ ｐｈｒの範囲で配合すれ
ばよい。このとき共重合体のすぐれた性能は、より一段
と強調され確固たるものとなる。The polyamine compound can be freely selected from the group of those already industrialized and commercially available, and no limitations are required. Specific examples include Kogi Cure 100, Ebicure 101, Ebicure 103, and Ebicure 104.
(The above are Shell Chemical products). The compound may be added to the copolymer in an amount of 0.6 to 1.4 phr. At this time, the excellent performance of the copolymer is further emphasized and solidified.
以下に、実施例、比較例をもって本発明を更に詳しく説
明するが、本発明がこれだけに限定されるものでないこ
とはもちろんである。The present invention will be explained in more detail below with reference to Examples and Comparative Examples, but it goes without saying that the present invention is not limited thereto.
〔実施例および比較り１〕
実施例１゜
窒素導入管、逆流冷却器、撹拌装置のついた１を四つロ
フラスコに、メタクリル酔ｎ−ブチル２６４ｆ、アクリ
ル酸ｎ−ブチル４０９．メタクリル酸グリシジル３２１
、テトラエチルチウラムジチオスルフィド１．２２、キ
シレン２００？を仕込み、１１０℃に昇温して２０時間
重合を行なった。次いで、酢酸セロソルブ５０？、ｔ−
ジチルノミ−オキシベンゾニー）０．２Ｆを仕込み、更
にメタクリル酸トリフルオロエチル６４ｆ’に１時間か
げてフラスコ内に滴下した。３時間重合の後、酢酸セロ
ソルブ１０（１、ｔ−ブチルパーオキシベンゾニー）０
．１Ｆを３回に分け、１時間毎に添加した。更に３時間
１１０℃で重合の後、キシレン５０２を加え常温まで冷
却してエイキシ当ｊｋ １７７５（固型分換算）の共重
合体を得た。[Example and Comparison 1] Example 1 In a four-bottle flask equipped with a nitrogen inlet tube, a backflow condenser, and a stirring device, 264 f of n-butyl methacrylate and 409 g of n-butyl acrylate were added. Glycidyl methacrylate 321
, tetraethylthiuram dithiosulfide 1.22, xylene 200? was charged, the temperature was raised to 110°C, and polymerization was carried out for 20 hours. Next, cellosolve acetate 50? , t-
0.2F of dithyloxybenzonylic acid was added thereto, and then added dropwise to the flask over 64f' of trifluoroethyl methacrylate for 1 hour. After 3 hours of polymerization, cellosolve acetate 10 (1, t-butylperoxybenzony) 0
．． 1F was divided into three portions and added every hour. After further polymerization at 110° C. for 3 hours, xylene 502 was added and the mixture was cooled to room temperature to obtain a copolymer with a xylene weight of 1775 (in terms of solid content).
実施例２゜
実施例１．と同様の装置にメタクリル酸エチル２６４ｔ
、メタクリル酸ｎ−ブチル４０Ｐ１メタクリル酸グリシ
ジル２８．８Ｆ％テトラエチルチウラムジスルフィド１
．５ｆ、キシレン２５０１を仕込み、１１０℃に昇温し
て２０時間重合を行なった。次いで、酢酸セロソルブ５
０ｆｔｔ−ブチル・ぞ−オキシベンゾエート０．２２を
仕込み、更にメタクリル酸トリフルオロエチル６４？、
メタクリル酸グリシジル３，２２の単量体混合物を１時
間かけてフラスコ内に滴下した。３時間重合の後酢酸セ
ロソルゾ１００Ｆ、ｔ−ブチルパーオキシベンゾエート
ｏ、１ｆを３回に分け、１時間毎に添加した。更に３時
間１１０℃で重合を行なった後、常温まで冷却してエポ
キシ当′ｊＬ１７７５（固型分換算）の共重合体を得た
、
実施例３゜
実施例１．で得た共重合体１００？とエビキュア１０４
２．７ｆを均一に攪拌混合し、塗料組成物を得た。Example 2゜Example 1. 264 tons of ethyl methacrylate in the same equipment as
, n-butyl methacrylate 40P1 glycidyl methacrylate 28.8F% tetraethylthiuram disulfide 1
．． 5f and xylene 2501 were charged, the temperature was raised to 110°C, and polymerization was carried out for 20 hours. Then cellosolve acetate 5
0ftt-butyl zo-oxybenzoate 0.22 was charged, and trifluoroethyl methacrylate 64? ,
A monomer mixture of 3,22 glycidyl methacrylate was added dropwise into the flask over 1 hour. After polymerization for 3 hours, cellosolzo acetate 100F, t-butylperoxybenzoate o, and 1f were divided into three portions and added every hour. After polymerization was further carried out at 110° C. for 3 hours, the mixture was cooled to room temperature to obtain a copolymer with an epoxy equivalent of 1775 (solid content). Example 3 Example 1. Copolymer 100? and Ebicure 104
2.7f were uniformly stirred and mixed to obtain a coating composition.
実施例４゜
実施例２．で得た共重合体組成物１００２とエビキュア
１０４ ２．７９を均一に攪拌混合し、塗料組成物を得
た。Example 4゜Example 2. Copolymer composition 1002 obtained in step 1 and Ebicure 104 2.79% were uniformly stirred and mixed to obtain a coating composition.
比較例１゜
実施例１．と同様の装置にキシレン２４０ｆ％ を−ブ
チルパーオキシベンゾエート４．８ｆ’ｇ仕込み、１１
０℃に昇温する。メタクリルｊｊ２ｎ−ブチル４０２、
メタクリル酸グリシジル３２２、メタクリル酸トリフル
オロエチル６４２の単量体混合物を３時間でフラスコ内
に滴下し、更に２時間重合する。Comparative example 1゜Example 1. 240 f% of xylene and 4.8 f'g of -butyl peroxybenzoate were charged into the same apparatus as above, and 11
Raise the temperature to 0°C. methacryljj2n-butyl 402,
A monomer mixture of 322 glycidyl methacrylate and 642 trifluoroethyl methacrylate was added dropwise into the flask over a period of 3 hours, and the mixture was further polymerized for 2 hours.
トルエン４０ｆ、ｔ−プチルノソーオキシベンゾエ−）
０．４ｆの混合物を１時間毎４回添加し、更に３時間重
合した後常温まで冷却して、工４キシ当量１７７５（固
型分換算）の共重合体を得た。Toluene 40f, t-butylnosoxybenzoate)
A mixture of 0.4 f was added four times every hour, and after further polymerization for 3 hours, the mixture was cooled to room temperature to obtain a copolymer with a polyethylene equivalent of 1775 (in terms of solid content).
比較例２゜
比較例１．で得た共重合体１００２とエビキュア１０４
２．７ｆを均一に攪拌混合し、塗料組成物を得た。Comparative example 2゜Comparative example 1. Copolymer 1002 and Ebicure 104 obtained in
2.7f were uniformly stirred and mixed to obtain a coating composition.
実施例、比較例の生成物な用いて行った各種試験および
その結果は次の通りである。Various tests conducted using the products of Examples and Comparative Examples and their results are as follows.
各々の生成物を用い、ガラス板上［３０〜５０μｍの被
膜を作り、２０℃、７０％ＲＨの条件下で２週間乾鰯し
た。この被膜（フィルム）を用いて各種試験を行なった
。下表に試験結果を示す。Using each product, a film of 30 to 50 μm was formed on a glass plate and dried under conditions of 20° C. and 70% RH for 2 weeks. Various tests were conducted using this coating (film). The test results are shown in the table below.
＊）試験項目の説明
１）硫酸：５０％硫酸水中に１週間浸漬ｔ７、被膜の変
化を調べた。◎異常なし、○はと
んど異常なし、Δ変色、ブリスター発
生、×被膜破壊
２）揃酸：３０％硝酸水中に１週間浸漬し、被膜の変化
を調べた。◎異常なし、○はと
んど異常なし、△変色、ブリスター発
生、×被膜破壊
３）苛性ソーダ：１０％苛性ソーダ水中に１週間浸漬し
、被膜の変化を調べた。◎異常
なし、○はとんど異常なし、Δブリス
ター発生
４）耐候性：サンシャインウェザ−メーター（サンシャ
インカーボンアーク型促進耐候
性試験機）で１０００時間試験の後、
被膜の変化を調べた。*) Explanation of test items 1) Sulfuric acid: The film was immersed in 50% sulfuric acid water for one week at t7, and changes in the film were examined. ◎ No abnormality, ○ means almost no abnormality, Δ discoloration, blister generation, × film destruction 2) All acids: immersed in 30% nitric acid water for one week, and changes in the film were examined. ◎ No abnormality, ○ means almost no abnormality, △ discoloration, blister generation, × film destruction 3) Caustic soda: The film was immersed in 10% caustic soda water for one week, and changes in the film were examined. ◎No abnormality, ○: almost no abnormality, ∆blister occurrence 4) Weather resistance: Changes in the film were examined after a 1000 hour test using a Sunshine Weathermeter (Sunshine Carbon Arc Type Accelerated Weathering Tester).
５）ＴＢ： ２００ｗ−の引張り速度でテンシロンによ
り破断強度を求めた。値が大で
ある程すぐれている。5) TB: The breaking strength was determined using Tensilon at a tensile speed of 200 W-. The higher the value, the better.
６）ＥＢ： ２００卿／＝の引張り速度でテンシロン
により破断伸びを求めた。値が大で
ある程すぐれている。6) EB: The elongation at break was determined using a tensilon at a tensile rate of 200 m/=. The higher the value, the better.
以上のように、本発明に係る共重合体を含む塗料組成物
は種々の点においてきわめてすぐれた性能を有している
。As described above, the coating composition containing the copolymer according to the present invention has extremely excellent performance in various respects.
Claims (1)
し０．０５〜１．５重量％のジスルフィド化合物とから
成るエポキシ当量３００以上のアクリル樹脂（Ａ）４０
〜９５重量％と、（メタ）アクリル酸フルオロアルキル
エステル単量体およびその他の（メタ）アクリル酸エス
テル単量体（本単量体は（メタ）アクリル酸フルオロア
ルキルエステルに対し０〜２０重量％使用する）から成
るエポキシ当量７１０以上の単量体混合物（Ｂ）６０〜
５重量％とを重合させて得たエポキシ当量３５０〜４７
５０のエポキシ基含有共重合体を含む塗料組成物。 ２）（メタ）アクリル酸エステル単量体と該単量体に対
し０．０５〜１．５重量％のジスルフィド化合物とから
成るエポキシ当量３００以上のアクリル樹脂（Ａ）４０
〜９５重量％と、（メタ）アクリル酸フルオロアルキル
エステル単量体およびその他の（メタ）アクリル酸エス
テル単量体（本単量体は（メタ）アクリル酸フルオロア
ルキルエステルに対し０〜２０重量％使用する）から成
るエポキシ当量７１０以上の単量体混合物６０〜５重量
％とを重合させて得たエポキシ当量３５０〜４７５０の
エポキシ基含有共重合体と、該共重合体に対し０．６〜
１．４ｐｈｒで配合したポリアミン化合物とを含む塗料
組成物。[Claims] 1) Acrylic resin (A) 40 having an epoxy equivalent of 300 or more and consisting of a (meth)acrylic acid ester monomer and a disulfide compound in an amount of 0.05 to 1.5% by weight based on the monomer.
~95% by weight, and fluoroalkyl (meth)acrylic acid ester monomer and other (meth)acrylic acid ester monomers (this monomer is 0 to 20% by weight based on the fluoroalkyl (meth)acrylic acid ester) Monomer mixture (B) with an epoxy equivalent of 710 or more consisting of (used) 60 to
Epoxy equivalent obtained by polymerizing 5% by weight of 350 to 47
A coating composition containing an epoxy group-containing copolymer of 50. 2) Acrylic resin (A) 40 with an epoxy equivalent of 300 or more, consisting of a (meth)acrylic acid ester monomer and a disulfide compound in an amount of 0.05 to 1.5% by weight based on the monomer
~95% by weight, and fluoroalkyl (meth)acrylic acid ester monomer and other (meth)acrylic acid ester monomers (this monomer is 0 to 20% by weight based on the fluoroalkyl (meth)acrylic acid ester) An epoxy group-containing copolymer having an epoxy equivalent of 350 to 4,750 obtained by polymerizing 60 to 5% by weight of a monomer mixture having an epoxy equivalent of 710 or more consisting of
A coating composition containing a polyamine compound blended at 1.4 phr.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10937586A JPS62267376A (en) | 1986-05-15 | 1986-05-15 | Paint composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10937586A JPS62267376A (en) | 1986-05-15 | 1986-05-15 | Paint composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62267376A true JPS62267376A (en) | 1987-11-20 |
Family
ID=14508643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10937586A Pending JPS62267376A (en) | 1986-05-15 | 1986-05-15 | Paint composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62267376A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5597874A (en) * | 1995-10-16 | 1997-01-28 | E. I. Du Pont De Nemours And Company | Coating compositions of an acrylic fluorocarbon polymer and a fluorinated polyisocyanate |
| US5629372A (en) * | 1994-11-22 | 1997-05-13 | E. I. Du Pont De Nemours And Company | Acrylic fluorocarbon polymer containing coating |
| US5948851A (en) * | 1997-11-21 | 1999-09-07 | E. I. Du Pont De Nemours And Company | Coating compositions containing a highly fluorinated polymeric additive |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60238311A (en) * | 1984-05-10 | 1985-11-27 | Sunstar Giken Kk | Fluorine-containing acrylic resin and elastic finish structure of exterior wall having said resin as top layer |
-
1986
- 1986-05-15 JP JP10937586A patent/JPS62267376A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60238311A (en) * | 1984-05-10 | 1985-11-27 | Sunstar Giken Kk | Fluorine-containing acrylic resin and elastic finish structure of exterior wall having said resin as top layer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5629372A (en) * | 1994-11-22 | 1997-05-13 | E. I. Du Pont De Nemours And Company | Acrylic fluorocarbon polymer containing coating |
| US5597874A (en) * | 1995-10-16 | 1997-01-28 | E. I. Du Pont De Nemours And Company | Coating compositions of an acrylic fluorocarbon polymer and a fluorinated polyisocyanate |
| US5948851A (en) * | 1997-11-21 | 1999-09-07 | E. I. Du Pont De Nemours And Company | Coating compositions containing a highly fluorinated polymeric additive |
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