JPH0241378A - Fluoring-containing coating composition - Google Patents

Fluoring-containing coating composition

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Publication number
JPH0241378A
JPH0241378A JP19221088A JP19221088A JPH0241378A JP H0241378 A JPH0241378 A JP H0241378A JP 19221088 A JP19221088 A JP 19221088A JP 19221088 A JP19221088 A JP 19221088A JP H0241378 A JPH0241378 A JP H0241378A
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JP
Japan
Prior art keywords
fluorine
meth
group
parts
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP19221088A
Other languages
Japanese (ja)
Other versions
JP2869071B2 (en
Inventor
Itaru Ozaki
尾崎　格
Mikio Shin
新　幹雄
Tadanori Fukuda
福田　忠則
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
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Filing date
Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Priority to JP63192210A priority Critical patent/JP2869071B2/en
Publication of JPH0241378A publication Critical patent/JPH0241378A/en
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Publication of JP2869071B2 publication Critical patent/JP2869071B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Abstract

PURPOSE:To obtain the title composition having excellent weather resistance, water repellency, stain resistance and low frictional properties consisting essentially of a copolymer comprising specific two kinds of (meth)acrylic acid esters and a vinyl monomer containing an unsaturated group at the end. CONSTITUTION:The aimed composition consisting essentially of a copolymer comprising (A) 3-30wt.% (meth)acrylic acid esters shown by the formula (Rf is >=10F fluoroalkyl or perfluoroalkyl-containing substituent group; n is 1 or 2; R is H or methyl), (B) 20-60wt.% 5-25C alicyclic alkyl group-containing (meth) acrylic acid esters and (C) 10-77wt.% vinyl monomer (e.g., styrene or vinyl acetate) containing an unsaturated group at the end. Further the composition preferably comprises (D) 3-30wt.% functional group-containing vinyl monomer in the copolymer and a crosslinking agent capable of being reacted with the functional group.

Description

【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、耐候性、撥水性、耐汚染性、低摩擦性に優れ
た被膜を形成する被覆組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a coating composition that forms a film with excellent weather resistance, water repellency, stain resistance, and low friction.

［従来の技術］ 従来、耐候性、撥水性、耐汚染性に優れ、有機溶剤に可
溶な塗料用樹脂として、フッ素含有樹脂が用いられ、特
公昭５０−２９７３０号公報や特開昭５８−３４８６６
号公報などに示されている。また、特開昭６０−１８７
９２１号にはマクロモノマを使用したフッ素系グラフト
ポリマが明示されている。[Prior Art] Conventionally, fluorine-containing resins have been used as resins for coatings that have excellent weather resistance, water repellency, and stain resistance and are soluble in organic solvents, and are disclosed in Japanese Patent Publication No. 50-29730 and Japanese Patent Application Laid-open No. 1983-1989. 34866
This is shown in the issue of the publication, etc. Also, JP-A-60-187
No. 921 clearly discloses a fluorine-based graft polymer using a macromonomer.

［発明が解決しようとする課題］ しかしながら、かかる従来の技術においては、水分を吸
収することによって加水分解が起こり、耐久性が不充分
であるといった問題点を有していた。[Problems to be Solved by the Invention] However, in this conventional technique, hydrolysis occurs due to the absorption of moisture, resulting in insufficient durability.

本発明は、吸水率が低く、耐水性に優れるために、長期
に渡って耐候性などを維持することができる、耐久性に
優れたフッ素含有被覆組成物を提供することを目的とす
る。An object of the present invention is to provide a highly durable fluorine-containing coating composition that has low water absorption and excellent water resistance, and thus can maintain weather resistance over a long period of time.

［課題を解決するための手段］ 本発明は、上記目的を達成するために下記の構成を有す
る。[Means for Solving the Problems] The present invention has the following configuration to achieve the above object.

「下記（ａ＞、（ｂ）、（ｃ）の単量体成分から構成さ
れる共重合体を主成分としてなるフッ素含有被覆組成物
。"A fluorine-containing coating composition comprising a copolymer composed of the following monomer components (a>, (b), and (c)) as a main component.

（ａ）一般式Ｒｆ　（ＣＨ２）　ｎ　ＯＣＯＣＲ＝ＣＦ
＋２で表される（メタ）アクリル酸エステル３〜３０重
量％ （Ｒｆはフッ素原子の数が１０以上のフルオロアルキル
基またはパーフルオロアルキル基含有の置換基であり、
ｎは１または２．Ｒは水素またはメチル基を示す。）（
ｂ）炭素数５〜２５の脂環族アルキル基を有する（メタ
）アクリル酸エステル ２０〜６０重量％ （Ｃ）末端に不飽和基を有するビニル単量体１０〜７７
重量％」 本発明において（ａ）成分として使用されるフッ素含有
共重合体の単量体成分は、一般式Ｒｆ（ＣＨ２＞　ｎ０
ＣＯＣＲ＝ＣＨ２で表され、Ｒｆはフッ素原子の数が１
０以上のフルオロアルキル基またはパーフルオロアルキ
ル基、ｎは１または２゜Ｒは水素またはメチル基である
ことが必要である。(a) General formula Rf (CH2) n OCOCR=CF
3 to 30% by weight of (meth)acrylic acid ester represented by +2 (Rf is a substituent containing a fluoroalkyl group or perfluoroalkyl group having 10 or more fluorine atoms,
n is 1 or 2. R represents hydrogen or a methyl group. )(
b) 20 to 60% by weight (meth)acrylic acid ester having an alicyclic alkyl group having 5 to 25 carbon atoms (C) Vinyl monomer having an unsaturated group at the terminal 10 to 77
% by weight" The monomer component of the fluorine-containing copolymer used as component (a) in the present invention has the general formula Rf(CH2>n0
It is expressed as COCR=CH2, and Rf has 1 fluorine atom.
It is necessary that there are 0 or more fluoroalkyl groups or perfluoroalkyl groups, n is 1 or 2°, and R is hydrogen or methyl group.

具体的には次のような高級フルオロアルキル（メタ）ア
クリレートである。Specifically, the following higher fluoroalkyl (meth)acrylates are used.

Ｃｌ−１２＝ＣＲＣ０２（Ｃ）（２）　ｌ１ＩＣ，Ｆ２
．＋１（ｍは１または２、ｎは５〜１２の整数を示す）
ＣＨ２＝ＣＲＣＯ２ＣＨ２０（ＣＦ２）２　ＱＣ，Ｆ２
ｎ＋１（ｎは３〜４の整数を示す） ＣＨ２＝　ＣＲＣＯ２ＣＨ２（ＣＦ２　）　ｍ　Ｈ（ｍ
は６〜１４の偶数を示す。） ＣＨ２＝ＣＲＣＯ２（ＣＨ２）　２０ＧＯ８００９Ｆ１
□ＣＨ２＝ＣＲＣＯ２（ＣＨ２）　　ＮＲ”５０２Ｃｓ
Ｆ１７（ｍは１〜１０の整数を示す。Ｒｏは炭素数１〜
４のアルキル基を示す。） ＣＨ２＝ＣＲＣＯ２（ＣＨ２）　２　ＮＲ’Ｃ０Ｃ７Ｆ
１５（Ｒ’はＣ１〜Ｃ９のアルキル基を示す）ＣＨｐ＝
ＣＲＣＯ２（ＣＨ２）２　Ｒ（（Ｒｆは、Ｃ３Ｆ１３〜
Ｃｌ２Ｆ２５を示す）ＣＨ２＝ＣＲＣＯ２（ＣＨ２）２
　ＮＣＨＩＳＯ２ＣＨｐ＝ＣＲＣＯ２ＣＨ２ＣＨＯＨＣ
Ｈ２ＣｓＦ１７ＣＨ２＝ＣＲＣＯ２（ＣＨり）　　２　
Ｎ　ＣＨｓＣＯ（ＣＦ２０Ｆ２０）　３　Ｃ２Ｆ　ｓ ここでＲｆのフルオロアルキル基またはパーフルオロア
ルキル基においてフッ素原子の数が１０以上のものを用
いることによって、膜厚方向にフッ素の濃度分布をもっ
た被膜を形成し、被膜表面のフッ素濃度は高く、内部の
方はフッ素濃度が低くなるという効果を有する。特にＲ
ｆのフッ素原子の数が１２〜３０の範囲において、きわ
めて優れた効果を発揮する。Cl-12=CRC02(C)(2) l1IC,F2
．． +1 (m is 1 or 2, n is an integer from 5 to 12)
CH2=CRCO2CH20(CF2)2 QC,F2
n+1 (n represents an integer of 3 to 4) CH2= CRCO2CH2(CF2) m H(m
represents an even number from 6 to 14. ) CH2=CRCO2(CH2) 20GO8009F1
□CH2=CRCO2(CH2) NR”502Cs
F17 (m represents an integer of 1 to 10. Ro represents carbon number 1 to
4 shows the alkyl group. ) CH2=CRCO2(CH2) 2 NR'C0C7F
15 (R' represents a C1 to C9 alkyl group) CHp=
CRCO2(CH2)2 R((Rf is C3F13~
Cl2F25) CH2=CRCO2(CH2)2
NCHISO2CHp=CRCO2CH2CHOHC
H2CsF17CH2=CRCO2(CHri) 2
N CHsCO(CF20F20) 3 C2F s Here, by using a fluoroalkyl group or perfluoroalkyl group of Rf having 10 or more fluorine atoms, a film having a fluorine concentration distribution in the film thickness direction is formed. This has the effect that the fluorine concentration on the surface of the coating is high and the fluorine concentration inside is low. Especially R
Extremely excellent effects are exhibited when the number of fluorine atoms in f is in the range of 12 to 30.

フッ素濃度を知る手段としては、同一条件で接触角を測
定した場合、フッ素濃度が高いと被膜表面の接触角は大
きくなり、被膜表面の接触角を測定することによって簡
便に知ることができる。また２次イオン質量分析装置を
用いて被膜表面（〜１０００人）のフッ素濃度を直接に
測定することもできる。この装置は、５〜１５ｋｅｖ程
度のエネルギーを被膜表面に当て、スパッタリングによ
って試料から発生する２次イオンを質量分析する方法で
ある。As a means of knowing the fluorine concentration, when the contact angle is measured under the same conditions, the higher the fluorine concentration, the larger the contact angle on the coating surface, and it can be easily determined by measuring the contact angle on the coating surface. It is also possible to directly measure the fluorine concentration on the coating surface (~1000 people) using a secondary ion mass spectrometer. This device applies energy of about 5 to 15 keV to the surface of the coating and performs mass spectrometry on secondary ions generated from the sample by sputtering.

また、塗膜表面の元素組成分析については、防錆管理−
８６年１１月号３４０〜３４５頁にＥＳＣＡを用いて報
告されている。In addition, regarding the elemental composition analysis of the paint film surface, rust prevention management
It is reported using ESCA in the November 1986 issue, pages 340-345.

したがって、フッ素含有の該モノマを少量使用すること
によって被膜中のフッ素含有による効果を最大限に発揮
できる特徴がある。このように、被膜表面のフッ素濃度
がきわめて高くなることから、フッ素による優れた特性
が付与され、被膜表層の耐候性、撥水性、耐汚染性、耐
食性、低摩擦性を著しく向上させることができる。例え
ば、塗料用被膜は、酸化チタンなどの顔料によって着色
して使用する場合、屋外に暴露されても、太陽光線はそ
の大部分が被膜表面で反射され、内部にまでは浸入して
行きにくく、耐久性が求められる場合などにおいて、本
発明の組成物が効果的に使用される。Therefore, by using a small amount of the fluorine-containing monomer, the effect of the fluorine content in the coating can be maximized. In this way, the fluorine concentration on the surface of the coating becomes extremely high, giving it excellent properties due to fluorine, and making it possible to significantly improve the weather resistance, water repellency, stain resistance, corrosion resistance, and low friction properties of the coating surface layer. . For example, when a paint film is colored with a pigment such as titanium oxide, even if it is exposed outdoors, most of the sunlight is reflected on the surface of the film, making it difficult for it to penetrate inside. The composition of the present invention is effectively used in cases where durability is required.

一方、基板に接触する面（裏面）はフッ素濃度がほとん
ど無いために、被膜と基板との密着性が優れる特徴があ
り、通常のフッ素系塗料の密着性の悪さの問題点が解決
されている。このように本発明組成物から、被膜中のフ
ッ素含量を必要度の高いところに多く配置させ、一方必
要度の低いところにはフッ素を分布させない塗膜が得ら
れる。On the other hand, since the surface that contacts the substrate (back surface) has almost no fluorine concentration, it has excellent adhesion between the coating and the substrate, solving the problem of poor adhesion with ordinary fluorine-based paints. . As described above, from the composition of the present invention, a coating film can be obtained in which a large amount of fluorine is distributed in areas where the fluorine content is highly required, while not being distributed in areas where the fluorine content is low.

また、かかる（ａ）の単量体の使用量は共重合体中にお
いて３〜３０重量％であることが必要である。３重量％
未満ではフッ素含有による効果が小ざい。また、３０重
量％を越えると次のような理由から良好な被膜を作製す
ることができない。Further, the amount of the monomer (a) used in the copolymer must be 3 to 30% by weight. 3% by weight
If it is less than that, the effect of fluorine content will be small. Moreover, if it exceeds 30% by weight, a good film cannot be produced for the following reasons.

（イ）　フッ素含有共重合体は固体であるので、通常、
溶剤に溶かし溶液として取り扱う。該単量体の使用量が
３０重量％を越えると、フッ素含有共重合体の溶液は撹
拌時に石鹸のように泡立ち、塗装（コーテング）するこ
とが困難となる。(b) Since fluorine-containing copolymers are solid, they usually
Dissolve in solvent and treat as a solution. If the amount of the monomer used exceeds 30% by weight, the solution of the fluorine-containing copolymer foams like soap when stirred, making it difficult to coat.

消泡剤を用いることで改善はできるが、消泡剤使用によ
って耐水性、耐薬品性、耐候性などに悪影響をおよぼす
問題が生じやすい。Although it can be improved by using an antifoaming agent, the use of an antifoaming agent tends to cause problems that adversely affect water resistance, chemical resistance, weather resistance, etc.

（ロ）　被膜の機械的強度および硬度が低下しやすい。(b) Mechanical strength and hardness of the coating tend to decrease.

これは本発明で用いる高級フルオロアルキル（メタ）ア
クリレートのホモポリマのＴｇ（ガラス転移温度）が低
いために、その使用量が増えると被膜の引っ張り強度、
剛性および硬度が低下する。This is because the Tg (glass transition temperature) of the higher fluoroalkyl (meth)acrylate homopolymer used in the present invention is low, and as the amount used increases, the tensile strength of the coating increases.
Stiffness and hardness are reduced.

（ハ）　被膜の摩擦係数が増大し、目的とする低摩擦化
を達成できない。(c) The coefficient of friction of the coating increases, making it impossible to achieve the desired low friction.

（ニ）　下地基板との接着性が悪くなる。該モノマ量の
使用量が多くなるとフッ素含有の被膜が下地基板面にも
存在しやすくなり、そのために接着性がわる（なるもの
と思われる。(d) Adhesion to the underlying substrate deteriorates. When the amount of the monomer used increases, the fluorine-containing film tends to exist on the surface of the base substrate, which leads to a decrease in adhesion.

つぎに（ｂ）成分の脂環族アルキル基を有する（メタ）
アクリル酸エステルとしては、（メタ）アクリル酸アル
キルエステルのアルキル基が次に例示する脂環族アルキ
ル基によって置換されている化合物を挙げることができ
る。脂環族アルキル基としては、シクロペンチル、シク
ロヘキシル、メチルシクロヘキシル、２，２．５−トリ
メチルシクロヘキサン、ｎ−ボルニル、ｌ５Ｏ−ボルニ
ル、ノルボルニル、ノルボルニルメチル、α−メンチル
、α−フェンチル、１−７ダマンチル、２−アダマンチ
ル、３．５−ジメチル−１−アダマンチル、ｐ−メンタ
ン、２−メチルカンファン、ａ−メンチール、シクロド
デシル、トリシクロ［５，２，１，０２・６］デカ−８
−イル、トリシクロ［５，２，１，０２・６］デカ−４
−メチル、３−メチル−１−アダマンチル、８−エチル
アダマンチル、８−メチル−５−エチル−１−アダマン
チル、３，５．８−トリエチル−１−アダマンチル、３
．５−ジメチル−８−エチル−１−アダマンチル、ノル
ボルネン、オクタヒドロ−４，７−メンタノインデニル
、オクタヒドロ−４，７−メンツノインデン−１−イル
メチル、ｐ−メンチル−８、ｐ−メンチル−２，８−ヒ
ドロキシ−２，６，６−ドリメチルービシクロ［８，１
，１］ヘプタン、８．７．７−ドリメチルー４−ヒドロ
キシ−ビシクロ［４，１，Ｏｌヘプタン−４−イルなど
が代表的なものとして例示される。Next, component (b) having an alicyclic alkyl group (meth)
Examples of acrylic esters include compounds in which the alkyl group of (meth)acrylic acid alkyl ester is substituted with an alicyclic alkyl group exemplified below. Alicyclic alkyl groups include cyclopentyl, cyclohexyl, methylcyclohexyl, 2,2.5-trimethylcyclohexane, n-bornyl, l5O-bornyl, norbornyl, norbornylmethyl, α-menthyl, α-fenthyl, 1-7 Damantyl, 2-adamantyl, 3.5-dimethyl-1-adamantyl, p-menthane, 2-methylcamphane, a-menthyl, cyclododecyl, tricyclo[5,2,1,02.6]deca-8
-yl, tricyclo[5,2,1,02.6]deca-4
-Methyl, 3-methyl-1-adamantyl, 8-ethyladamantyl, 8-methyl-5-ethyl-1-adamantyl, 3,5.8-triethyl-1-adamantyl, 3
．． 5-dimethyl-8-ethyl-1-adamantyl, norbornene, octahydro-4,7-menthanoindenyl, octahydro-4,7-menthanoinden-1-ylmethyl, p-menthyl-8, p-menthyl-2 ,8-hydroxy-2,6,6-drimethyl-bicyclo[8,1
.

これらの脂環族アルキル基を有する（メタ）アクリル酸
エステルは本発明の被膜の吸水性を低下せしめる効果を
もたらすものである。共重合体中にこれを導入すること
によって被膜中のエステル結合、ウレタン結合等の加水
分解性を大幅に低減できる。また、前記（ａ）成分にお
けるフッ素を含有することによる効果に影響を与えるこ
とはない。すなわち、本発明からなる被膜は低吸水性を
有し、長期にわたって、耐候性、撥水性、対汚染性、低
摩擦性などの性能を維持するものである。These (meth)acrylic acid esters having an alicyclic alkyl group have the effect of reducing the water absorption of the coating of the present invention. By introducing this into the copolymer, the hydrolyzability of ester bonds, urethane bonds, etc. in the coating can be significantly reduced. Further, the effect of containing fluorine in the component (a) is not affected. In other words, the coating of the present invention has low water absorption and maintains properties such as weather resistance, water repellency, stain resistance, and low friction properties over a long period of time.

かかる（ｂ）成分の使用量は、２０〜６０重量％の範囲
が必要である。２００重量％未満場合には、本発明の特
徴とする低い吸水性において効果がなく、逆に６０重量
％を越えると疎水性の大きな分子によって脆くなり、密
着性や撥水性および耐候性などが低下する。ざらに好ま
しい範囲は３０〜５０重量％である。The amount of component (b) used must be in the range of 20 to 60% by weight. If it is less than 200% by weight, it will not be effective in achieving the low water absorption characteristic of the present invention, and if it exceeds 60% by weight, it will become brittle due to large hydrophobic molecules, resulting in decreased adhesion, water repellency, weather resistance, etc. do. A generally preferred range is 30 to 50% by weight.

次に（Ｃ）成分の末端に不飽和基を有するビニル単量体
の代表的なものとしては、スチレン、ビニルトルエン、
もしくはα−メチルスチレンの如き芳香族系ビニル化合
物；酢酸ビニル、塩化ビニル、塩化ビニリデンの如きビ
ニルエーテル類；メチル（メタ）アクリレート、エチル
（メタ）アクリレート、ｎ（またはｔ）−ブチル（メタ
）アクリレートの如き（メタ）アクリル酸エステル類：
マレイン酸、フマール酸、もしくはイタコン酸などの不
飽和ジカルボン酸類と０１〜ＣＩＯなる一価のアルコー
ルとのジエステル類：（メタ）アクリルアミド、ジメチ
ル（メタ）アクリルアミドもしくはＮ−アルコキシメチ
ル化（メタ）アクリルアミドの如き（メタ）アクリルア
ミド類；ジメチルアミノエチル（メタ）アクリレートの
如きＮ、Ｎ−ジアルキルアミノアルキル（メタ）アクリ
レート類；βアシッドホスホキシ（メタ）アクリレート
の如き燐酸基含有（メタ）アクリレート類；（メタ）ア
クリル酸、マレイン酸、フマール酸もしくはイタコン酸
あるいは水酸基含有ビニル単量体と飽和ポリカルボン酸
との等モル付加反応生成物の如き不飽和カルボン酸類；
グリシジル（メタ）アクリレート、メチルグリシジル（
メタ）アクリレートもしくは（メタ）アリルグリシジル
エーテルあるいは（メタ）アクリル酸、マレイン酸、フ
マール酸、イタコン酸などの不飽和カルボン酸と「エピ
コート１００１もしくは１００４Ｊ　　（シェル社製　
エポキシ樹脂）、「エピクロン２００．４００．４４１
．８５０もしくは１０５０Ｊ　（大日本インキ社製　エ
ポキシ樹脂）、「アラルダイト６０７１ｊ　　（チバガ
イギー社製　エポキシ樹脂）、または「チッソノックス
　２２１ｊ　　（チッソ社製　エポキシ樹脂）の如き１
分子中に少なくとも２個のエポキシ基を有するポリエポ
キシ化合物とを等モルで付加反応させて得られるエポキ
シ基含有重合性付加物二重合性不飽和結合およびエポキ
シ基を有する低分子量のポリエステル樹脂（例えばシェ
ル社の「ペオパ」）などが代表的なものとして挙げられ
る。Next, typical vinyl monomers having an unsaturated group at the terminal of component (C) include styrene, vinyltoluene,
or aromatic vinyl compounds such as α-methylstyrene; vinyl ethers such as vinyl acetate, vinyl chloride, vinylidene chloride; methyl (meth)acrylate, ethyl (meth)acrylate, n (or t)-butyl (meth)acrylate; (meth)acrylic acid esters:
Diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid, or itaconic acid and monohydric alcohols 01 to CIO: (meth)acrylamide, dimethyl (meth)acrylamide, or N-alkoxymethylated (meth)acrylamide. (meth)acrylamides such as; N,N-dialkylaminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate; phosphoric acid group-containing (meth)acrylates such as β-acid phosphoxy(meth)acrylate; ) unsaturated carboxylic acids such as acrylic acid, maleic acid, fumaric acid or itaconic acid or equimolar addition reaction products of hydroxyl group-containing vinyl monomers and saturated polycarboxylic acids;
Glycidyl (meth)acrylate, methylglycidyl (
Meth)acrylate or (meth)allyl glycidyl ether or unsaturated carboxylic acid such as (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid and "Epicote 1001 or 1004J (manufactured by Shell)
epoxy resin), “Epicron 200.400.441
．． 1 such as 850 or 1050J (epoxy resin manufactured by Dainippon Ink Co., Ltd.), Araldite 6071j (epoxy resin manufactured by Ciba Geigy), or Chissonox 221j (epoxy resin manufactured by Chisso Corporation).
An epoxy group-containing polymerizable adduct obtained by adding equimolar amounts of a polyepoxy compound having at least two epoxy groups in the molecule.A low molecular weight polyester resin having a polymerizable unsaturated bond and an epoxy group (e.g. A typical example is Shell's Peopa.

これらの使用量は、（ａ）成分や、（ｂ）成分の使用量
の関係から、１０〜７０重量％の範囲で使用することが
必要である。It is necessary to use these in an amount of 10 to 70% by weight, depending on the amount of component (a) and component (b) used.

本発明の以上に挙げた（ａ）〜（Ｃ）のビニル単量体か
らなるフッ素含有共重合体は、ガラス転移温度下ｑが３
０〜８０℃の範囲であることが好ましい。ＴＯが３０℃
未満の場合には硬化被膜の硬度が低く、一方、８０℃を
越えると硬化被膜が脆くなりすぎるので所望とする性□
能が得られない。The fluorine-containing copolymer of the present invention consisting of the vinyl monomers (a) to (C) listed above has a q value of 3 at the glass transition temperature.
The temperature is preferably in the range of 0 to 80°C. TO is 30℃
If the temperature is less than 80°C, the hardness of the cured film will be low, while if it exceeds 80°C, the cured film will become too brittle.
ability is not obtained.

特に好ましくは４０〜７０℃の範囲である。Particularly preferably, the temperature is in the range of 40 to 70°C.

本発明のフッ素含有共重合体は、以上にあげた（ａ）〜
（Ｃ）のビニル単量体を用いて公知の重合方法、例えば
ラジカル発生剤を用いて溶液重合法、塊状重合法、懸濁
重合法などによって行うことができる。これらのなかで
は溶液重合法が好ましく用いられ、ラジカル発生剤とし
てはアクリル系モノマの重合に用いられているものであ
ればいずれも使用しうる。代表的なものを挙げれば、ア
ゾビスイソブチロニトリル（ＡＩＢＮ＞、ジ−ｔ−ブチ
ルパーオキサイド（ＤＴＢＰＯ＞　、ベンゾイルパーオ
キサイド（ＢＰＯ）　、ｔ−ブチルパーベンゾエート（
ＴＢＰＢ＞、ｔ−ブチルパーオクトエート（ＴＢＰＯ＞
　、またはクメンハイドロパーオキサイド（ＣＨＰ）な
どが例示される。また使用できる有機溶剤としては、ト
ルエン、キシレン、の如き芳香族系炭化水素類：酢酸エ
チル、酢酸ブチルもしくは酢酸セロソルブの如き酢酸エ
ステル類；メチルエチルケトン、メチルイソブチルケト
ンの如きケトン類などのアクリル系塗料に通常使用され
ているような溶剤でおればそのまま使用可能である。ま
た、必要により、ｎ−ドデシルメルカプタン、オクチル
メルカプタン、またはｔ−ブチルメルカプタンの如きメ
ルカプタン類；「ジペンテン−ＴＪ　　（日本テルペン
化学社製）などの連鎖移動剤を使用することもできる。The fluorine-containing copolymer of the present invention has the above-mentioned (a) to
The polymerization can be carried out using the vinyl monomer (C) by a known polymerization method, for example, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, etc. using a radical generator. Among these, the solution polymerization method is preferably used, and any radical generator used in the polymerization of acrylic monomers can be used. Representative examples include azobisisobutyronitrile (AIBN), di-t-butyl peroxide (DTBPO), benzoyl peroxide (BPO), and t-butyl perbenzoate (
TBPB>, t-butyl peroctoate (TBPO>
, or cumene hydroperoxide (CHP). Organic solvents that can be used include aromatic hydrocarbons such as toluene and xylene; acetate esters such as ethyl acetate, butyl acetate, or cellosolve acetate; and ketones such as methyl ethyl ketone and methyl isobutyl ketone. Any commonly used solvent can be used as is. Furthermore, if necessary, mercaptans such as n-dodecyl mercaptan, octyl mercaptan, or t-butyl mercaptan; chain transfer agents such as Dipentene-TJ (manufactured by Nippon Terpene Kagaku Co., Ltd.) can also be used.

また本発明において、前記（ａ）〜（Ｃ）の単量体成分
から構成される共重合体中に、官能基含有ビニル単量体
を３〜３０重量％の割合で含有することにより、硬化系
被覆組成物を得ることができる。３重量％未溝の場合に
は架橋が不十分なために耐久性における効果が充分では
なく、また、逆に３０重量％を越える場合には架橋密度
が高くなりすぎて′被膜が脆くなるという問題や、また
、ワニスの安定性が低下したり、塗膜物性の低下などの
問題を生じるため好ましくない。この中でざらに好まし
い範囲は７〜１５重伍％である。Further, in the present invention, by containing a functional group-containing vinyl monomer in a proportion of 3 to 30% by weight in the copolymer composed of the monomer components (a) to (C), curing can be achieved. based coating compositions can be obtained. If 3% by weight is ungrooved, crosslinking is insufficient and the effect on durability is not sufficient, while if it exceeds 30% by weight, the crosslinking density becomes too high and the film becomes brittle. This is not preferable because it also causes problems such as a decrease in the stability of the varnish and a decrease in the physical properties of the coating film. Among these, the most preferable range is 7 to 15% by weight.

官能基含有ビニル単量体としては、β−ヒドロキシエチ
ル（メタ）アクリレート、β−ヒドロキシプロピル（メ
タ）アクリレート、４−ヒドロキシブチル（メタ）アク
リレート、の如きヒドロキシアルキル（メタ）アクリレ
ート類：（メタ）アクリル酸、イタコン酸、フマール酸
、マレイン酸、クロトン酸の如き不飽和カルボン酸類；
オクチル酸グリシジルエステルもしくはヤシ油脂肪酸グ
リシジルエステルの如き一価カルボン酸のモノグリシジ
ルエステル類、またはブチルグリシジルエーテル類など
で代表されるモノエポキシ化合物との付加物：不飽和カ
ルボン酸のアルキレノキサイド付加物；不飽和カルボン
酸アミドおよびそのメチロール化物；重合性不飽和結合
を有する低分子量のポリエステル系樹脂などが代表的な
ものとして例示される。Examples of functional group-containing vinyl monomers include hydroxyalkyl (meth)acrylates such as β-hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate: (meth) Unsaturated carboxylic acids such as acrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid;
Adducts with monoglycidyl esters of monovalent carboxylic acids such as octylic acid glycidyl ester or coconut oil fatty acid glycidyl ester, or monoepoxy compounds represented by butyl glycidyl ethers: alkylenoxide addition of unsaturated carboxylic acids Typical examples include unsaturated carboxylic acid amides and methylolated products thereof; low molecular weight polyester resins having polymerizable unsaturated bonds;

また、架橋剤を使用することによって、被膜の耐候性が
向上し、本発明の特性を安定して発現することができる
。架橋剤は、前記（Ｃ）成分中の官能基含有ビニル単量
体と反応し架橋構造を構築する。架橋剤としては、共重
合体中に含有される前記（Ｃ）成分中の官能基含有ビニ
ル単口体と反応しうる官能基を有するものであればどの
ようなものでもよいが、代表的なものは例え、ば通常ア
ミノ樹脂と称されるものが挙げられ、それには尿素、チ
オ尿素、エチレン尿素、メラミンベンゾグアナミンなど
とホルムアルデヒドとの共縮合物やそれらの低級アルコ
ール処理物：脂肪族、脂環族ジイソシアネート類やこれ
らのビューレットタイプ、アダクト体それにトリマ体な
どのポリイソシアネート類例えば、「バーノックＤ−７
５０，ＤＮ−９５０、−９７０またはＤ−８００Ｊ　　
（以上大日本インキ社製）、「タケネートＢ−８２ＯＮ
Ｓ。Further, by using a crosslinking agent, the weather resistance of the film can be improved, and the characteristics of the present invention can be stably expressed. The crosslinking agent reacts with the functional group-containing vinyl monomer in component (C) to form a crosslinked structure. Any crosslinking agent may be used as long as it has a functional group that can react with the functional group-containing vinyl monomer in the component (C) contained in the copolymer. Examples of such resins include those commonly referred to as amino resins, including cocondensates of urea, thiourea, ethylene urea, melamine benzoguanamine, etc., and formaldehyde, and their lower alcohol-treated products: aliphatic and alicyclic resins. Group diisocyanates and polyisocyanates such as biuret type, adduct type and trimer type, such as "Burnock D-7".
50, DN-950, -970 or D-800J
(manufactured by Dainippon Ink Co., Ltd.), “Takenate B-82ON”
S.

Ｄ−１１ＯＮ、Ｄ−１２３ＮまたはＤ−１４ＯＮＪ（以
上成田薬品社製）、「コロネートＬ、ＥＨまたは２０３
１Ｊ　　（以上日本ポリウレタン社製）「デスモジュー
ルＬＳＮまたはＨＬＪ　　（以上バイエル社製）などが
好適に使用される。また（ポリ）アミン類、酸無水物類
１．エポキシ樹脂類、熱反応性フェノール樹脂などが挙
げられる。被膜硬化反応には、−船釣な触媒、例えばジ
ブチルチンジラウレートなどの反応促進剤も併用できる
。架橋剤の配合量としては、前記（ａ）成分に対して、
０゜１〜５０重量％でおることが好ましい。０．１重量
％未満である場合は、硬化が十分に進んだ被膜が得られ
ず、５０重量％を越えると、硬化被膜中のフッ素濃度の
低下や、残存する架橋剤によって被膜が可塑化するなど
といった傾向がある。そしてこれら架橋剤のうち、ポリ
イソシアネートを使用する場合は、前記共重合体との配
合比としてＯＨ／ＮＧＯ＝１１０．２〜１／１．５（当
量比）となる範囲で使用するか、あるいは、共重合体に
対し、０．１〜４０重量％の範囲が好ましく用いられ、
硬化条件も常温から加熱まで任意の条件を選ぶことがで
きる。D-11ON, D-123N or D-14ONJ (manufactured by Narita Pharmaceutical Co., Ltd.), “Coronate L, EH or 203
1J (manufactured by Nippon Polyurethane Co., Ltd.), Desmodur LSN or HLJ (manufactured by Bayer Co., Ltd.), etc. are also preferably used. Also, (poly)amines, acid anhydrides, 1. Epoxy resins, heat-reactive phenolic resins, etc. For the film curing reaction, a catalyst such as a reaction accelerator such as dibutyl tin dilaurate can also be used in combination.
It is preferably 0.1 to 50% by weight. If it is less than 0.1% by weight, a sufficiently cured film will not be obtained, and if it exceeds 50% by weight, the fluorine concentration in the cured film will decrease and the film will become plasticized by the remaining crosslinking agent. There is a tendency to do so. Among these crosslinking agents, when polyisocyanate is used, it is used in a blending ratio with the copolymer of OH/NGO=110.2 to 1/1.5 (equivalent ratio), or , is preferably used in a range of 0.1 to 40% by weight based on the copolymer,
Any curing conditions can be selected from room temperature to heating.

基板への被覆組成物のコーティング方法としては、スプ
レー塗装が一般的であるが、へケ塗り、ローラー塗りな
どいずれの方法でもよい。As a method for coating the substrate with the coating composition, spray coating is generally used, but any method such as brush coating or roller coating may be used.

このようにして得られた本発明の共重合体およびその硬
化系被覆組成物は、そのままクリヤーとして使用するこ
ともできるし、あるいは顔料を混ぜてエナメル塗料とし
て使用することもできる。The thus obtained copolymer of the present invention and its curable coating composition can be used as it is as a clear coating, or can be mixed with a pigment and used as an enamel paint.

また、必要に応じて、各種の添加剤などを使用すること
もできる。このような添加剤としては例えば紫外線吸収
剤、酸化防止剤、滑剤、レベリング剤などがある。Moreover, various additives and the like can be used as necessary. Examples of such additives include ultraviolet absorbers, antioxidants, lubricants, and leveling agents.

〔実施例〕〔Example〕

次に本発明を実施例および比較例により更に詳細に説明
する。実施例および比較例中の「部」・は特に誤りのな
い限り「重量部」を示す。なお、被膜の評価項目と評価
方法は次のとおり。Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. "Parts" in Examples and Comparative Examples indicate "parts by weight" unless otherwise specified. The evaluation items and evaluation methods for the film are as follows.

塗装時固形分：フオードカツプ１５秒設定での固形分（
ｗｔ％）。希釈溶剤−ＭＩＢＫ耐水性（吸水率）ニガラ
ス基板上に塗装した被膜を１４０ｍＸ１４０ｍの大きざ
に剥がしとり、２５℃の水に浸積した後、重量を測定。Solid content during painting: Solid content at a food cup setting of 15 seconds (
wt%). Diluent Solvent - MIBK Water Resistance (Water Absorption Rate) A coating coated on a Niglass substrate was peeled off into a 140m x 140m piece, immersed in water at 25°C, and the weight was measured.

光沢値　　　　　　＝６０度鏡面皮射率を計測。Gloss value = Measure the specular skin emissivity at 60 degrees.

グロスメータＧＭ−３Ｍ型（村上色彩技術研究所社）。Gloss meter GM-3M type (Murakami Color Research Institute).

ゴバン目密着性テスト：１ｍｍ角のます目１００個をカ
ッターで作成。ニチバンセロテープによる剥離テスト。Goban adhesion test: Create 100 squares of 1 mm square using a cutter. Peeling test using Nichiban cello tape.

エリクセン値　　　：エリクセン測定機（東洋精機製作
新製）により１インチ硬球の押出し深度（ｍｍ）をみる
。Erichsen value: Check the extrusion depth (mm) of a 1-inch hard ball using an Erichsen measuring machine (newly manufactured by Toyo Seiki).

ＱＵＶテスト　　：紫外線／結露サイクル促進耐候性試
験機（米国Ｑ−パネル社製）を使用。QUV test: Using an ultraviolet ray/condensation cycle accelerated weather resistance tester (manufactured by Q-Panel, Inc., USA).

テスト条件ＬＪＶ　　７０℃×８時間　結露　５０℃×
４時問 屋外暴露　　　　：建屋屋上に３年間放置した。Test conditions LJV 70℃×8 hours Condensation 50℃×
4-hour outdoor exposure: Left on the roof of a building for 3 years.

実施例　１ 攪拌機、コンデンサー、滴下ロート、温度計および窒素
ガス吹込み管を備えた２ンルのガラス顎間つ目フラスコ
に、酢酸ｎ−ブチル（以下ＢＡＣと略記する）２５０部
、キシレン（以下ＸｙＬと略記する）２５０部を仕込み
、窒素ガスで系内を置換した後８０±２℃に昇温した。Example 1 250 parts of n-butyl acetate (hereinafter abbreviated as BAC) and xylene (hereinafter referred to as (abbreviated as )) was charged, and after replacing the inside of the system with nitrogen gas, the temperature was raised to 80±2°C.

同温度で攪拌を続けながら、ＩＨ，１Ｈ，２Ｈ，２Ｈ−
へブタデカフロロデシルメタクリレート（ＣＨ２＝　Ｃ
ＣＨ！　Ｃ００（ＣＨ２＞　２　（ＣＦ２　）　ａ　Ｆ
　（以下１７ＦＭと略記する）〕５５０部ｎ−ブチルア
クリレート（以下ＢＡと略記する＞８８．５部、メチル
メタアクリレート（以下ＭＭＡと略記する）１５９部、
アクリル酸（以下ＡＡと略記する）２．５部、メタアク
リル酸トリシクロ（５，２，１，０２・６）デカ−８−
イル（以下ＴＣＤＭＡと略記する）２００部および重合
開始剤としてアゾビスインブチロニトリル（以下ＡＩＢ
Ｎと略記する）５部からなる混合物を３時間所要して滴
下した。滴下終了俊１時間攪拌を続け、その後ＡＩＢＮ
１部を１時間毎に５回添加した。その後さらに１時間攪
拌を続は反応を終了し、不揮発分５０ｗｔ％、ガードナ
ーホルト粘度ＱＳＭｎ＝２０，０００部ＭＷ／Ｍｎ＝２
．５０の含フツ素共重合体溶液を得た。While stirring at the same temperature, IH, 1H, 2H, 2H-
Hebutadecafluorodecyl methacrylate (CH2=C
CH! C00(CH2>2 (CF2) a F
(hereinafter abbreviated as 17FM)] 550 parts n-butyl acrylate (hereinafter abbreviated as BA)>88.5 parts, methyl methacrylate (hereinafter abbreviated as MMA) 159 parts,
2.5 parts of acrylic acid (hereinafter abbreviated as AA), tricyclo(5,2,1,02·6)deca-8-methacrylate
(hereinafter abbreviated as TCDMA) and 200 parts of azobisinbutyronitrile (hereinafter referred to as AIB) as a polymerization initiator.
A mixture of 5 parts (abbreviated as N) was added dropwise over a period of 3 hours. After dropping, continue stirring for 1 hour, then add AIBN.
1 part was added every hour for 5 times. After that, the reaction was continued for another 1 hour, and the reaction was completed.
．． A fluorine-containing copolymer solution of No. 50 was obtained.

この含フツ素共重合体溶液１２０部に対し、酸化チタン
（Ｒ−５５０５原産業社製＞４０部、メチルインブチル
ケトン（ＩＸ下ＭＩＢＫと略記する＞４０部を加えて混
合し、フォードカップで１５秒になるようにざらにＭＩ
ＢＫで希釈した後、ガラス板およびリン酸亜鉛鋼板の基
盤上にスプレー塗装し、含フツ素アクリルの被膜を得た
。乾燥は１０分間セツティングした（麦、オーブン中で
８０℃で３０分間加熱し、さらに室温（２５℃）で１週
間とした。この含フツ素アクリルの被膜は表１に示すと
おり耐水性、耐候性などに優れ、ＱＬＪＶ２００Ｏｈｒ
後も劣化は見られなかった。To 120 parts of this fluorine-containing copolymer solution, titanium oxide (R-5505 manufactured by Hara Sangyo Co., Ltd. >40 parts and methyl inbutyl ketone (abbreviated as MIBK under IX) >40 parts were added and mixed, and mixed in a Ford cup. Roughly MI so that it is 15 seconds
After diluting with BK, the mixture was spray-painted onto glass plates and zinc phosphate steel plates to obtain fluorine-containing acrylic coatings. Drying was carried out for 10 minutes (heated in an oven at 80°C for 30 minutes, and then left at room temperature (25°C) for 1 week. As shown in Table 1, this fluorine-containing acrylic film has water resistance and weather resistance. Excellent performance, QLJV200Ohr
No deterioration was observed after that.

実施例　２ 実施例１における含フツ素共重合体溶液を得るに際し、
ＴＣＤＭＡの代わりにメタアクリル酸ｎ−ボルニル４０
部、ＢＡ１０１部、ＭＭＡ１４６゜５部を使用し、以下
実施例１と同様にして不揮発分５Ｑｗｔ％、ガードナー
ホルト粘度ＱＳＭｎ＝２０．０００．Ｍｗ／Ｍｎ＝２．
３０の含フツ素共重合体溶液を得た。ざらに実施例１と
同様に塗料化、塗装、乾燥を行い含フツ素アクリルの被
膜を得た。この含フツ素アクリルの被膜は表１に示すと
おり耐水性、耐候性などに優れ、ＱＬＪＶ２ＯＱＱｈｒ
後も劣化は見られなかった。Example 2 When obtaining the fluorine-containing copolymer solution in Example 1,
n-bornyl methacrylate 40 instead of TCDMA
In the same manner as in Example 1, using 101 parts of BA, 5 parts of MMA 146°, the non-volatile content was 5Qwt%, and the Gardner-Holdt viscosity QSMn was 20.000. Mw/Mn=2.
A fluorine-containing copolymer solution of No. 30 was obtained. The coating was formed into a paint, painted, and dried in the same manner as in Example 1 to obtain a fluorine-containing acrylic coating. This fluorine-containing acrylic coating has excellent water resistance and weather resistance as shown in Table 1, and has excellent water resistance and weather resistance.
No deterioration was observed after that.

実施例　３ 実施例１の含フツ素共重合体溶液を得るに際して使用し
た四ツロフラスコに、ＸｙＬ２５０部、ＢＡ０２５０部
を仕込み、窒素ガスで系内を置換した後９５±２℃に昇
温した。Example 3 250 parts of XyL and 250 parts of BA0 were charged into the four-tube flask used to obtain the fluorine-containing copolymer solution of Example 1, and after purging the inside of the system with nitrogen gas, the temperature was raised to 95±2°C.

同温度で攪拌を続けながら七ツマ組成として１７ＦＭ５
０部、ＢＡ１５１．５部、ＭＭＡ３８部、ＡＡ２．５部
、ＴＣＤＭＡ２００部、２−ヒドロキシエチルメタアク
リレート（以下ＨＥＭＡと略記する）５８部を使用し、
以下実施例１と同様に重合開始剤を添加して不揮発分５
０ｗｔ％、ガードナーホルト粘度Ｈ，Ｍｎ＝１１，００
０．ＭＷ／Ｍｎ−２，５の含フツ素共重合体溶液を得た
。17FM5 as Nanatsuma composition while continuing to stir at the same temperature.
Using 0 parts, 151.5 parts of BA, 38 parts of MMA, 2.5 parts of AA, 200 parts of TCDMA, and 58 parts of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA),
Thereafter, a polymerization initiator was added in the same manner as in Example 1, and the nonvolatile content was 5
0wt%, Gardner-Holdt viscosity H, Mn=11,00
0. A fluorine-containing copolymer solution with MW/Mn-2,5 was obtained.

この含フツ素共重合体溶液８０部に、ｎ−ブチル化メラ
ミン樹脂“スーパーベッカミンＧ−８２１”（大日本イ
ンキ化学工業社製）２０部を混合し、ざらに酸化チタン
をＰＷＣ＝４０ｗｔ％になるように配合し、以下実施例
１と同様に希釈、塗装、乾燥を行い含フツ素アクリルの
硬化被膜を得た。この含フツ素アクリルの硬化被膜は表
１に示すように耐水性、密着性、耐候性などに優れてい
た。To 80 parts of this fluorine-containing copolymer solution, 20 parts of n-butylated melamine resin "Super Beckamine G-821" (manufactured by Dainippon Ink Chemical Industries, Ltd.) was mixed, and titanium oxide was added to PWC = 40 wt%. After diluting, painting and drying in the same manner as in Example 1, a cured film of fluorine-containing acrylic was obtained. As shown in Table 1, this cured fluorine-containing acrylic film was excellent in water resistance, adhesion, weather resistance, etc.

実施例　４ 実施例３で得られた含フツ素共重合体溶液５０部、酸化
チタン２０．５部、イソシアネート化合物としてスミジ
ュールＮ−７５（住友バイエルウレタン社製）５．７部
、ＭＩＢＫ２３．４部を混合し、以下実施例１と同様に
希釈、塗装、乾燥を行い含フツ素アクリルの硬化被膜を
得た。この含フツ素アクリルの硬化被膜は表１に示すよ
うに耐水性、密着性、耐候性などに優れていた。Example 4 50 parts of the fluorine-containing copolymer solution obtained in Example 3, 20.5 parts of titanium oxide, 5.7 parts of Sumidur N-75 (manufactured by Sumitomo Bayer Urethane) as an isocyanate compound, and 23.4 parts of MIBK. The mixture was diluted, painted and dried in the same manner as in Example 1 to obtain a cured fluorine-containing acrylic film. As shown in Table 1, this cured fluorine-containing acrylic film was excellent in water resistance, adhesion, weather resistance, etc.

実施例　５ 実施例３の含フツ素共重合体溶液を得るに際し、ＢＡ１
１９部、ＭＭＡ７０．５部、アクリル酸トリシクロ（５
，２，１，０２・６）デカ−８−イル（以下ＴＣＤＡと
略記する＞４０部を使用する以外は実施例３と同様にし
て不揮発分５０Ｗ↑％、ガードナーホルト粘度Ｈ，Ｍｎ
＝１０．８００、Ｍｗ／Ｍｎ＝２．２の含フツ素共重合
体溶液を得た。この後、実施例３と同様に塗料化、塗装
、乾燥を行い硬化被膜を得た。Example 5 When obtaining the fluorine-containing copolymer solution of Example 3, BA1
19 parts, 70.5 parts of MMA, tricycloacrylate (5
, 2,1,02・6) dec-8-yl (hereinafter abbreviated as TCDA) was prepared in the same manner as in Example 3 except that >40 parts was used, non-volatile content 50W↑%, Gardner-Holdt viscosity H, Mn
A fluorine-containing copolymer solution with Mw/Mn=10.800 and Mw/Mn=2.2 was obtained. Thereafter, coating, painting, and drying were carried out in the same manner as in Example 3 to obtain a cured film.

評価結果を表１に示したが、実施例３の硬化被膜と同様
に耐水性、密着性、耐候性などに優れていた。The evaluation results are shown in Table 1, and like the cured film of Example 3, it was excellent in water resistance, adhesion, weather resistance, etc.

実施例　６ 実施例５で得られる含フツ素共重合体溶液５０部を用い
るほかは実施例４と同様の塗料化を行い、以下実施例１
と同様に塗装、乾燥を行い含フツ素アクリルの硬化被膜
を得た。この含フツ素アクリルの硬化被膜は表１に示す
ように耐水性、密着性、耐候性などに優れていた。Example 6 A coating was prepared in the same manner as in Example 4 except that 50 parts of the fluorine-containing copolymer solution obtained in Example 5 was used.
Painting and drying were performed in the same manner as above to obtain a cured film of fluorine-containing acrylic. As shown in Table 1, this cured fluorine-containing acrylic film was excellent in water resistance, adhesion, weather resistance, etc.

比較例　１ 実施例１の含フツ素共重合体溶液を得るに際して１７Ｆ
Ｍ５０部、ＢＡ１０８．５部、ＭＭＡ　２８１部、ＡＡ
２．５部、ＨＥＭＡ５８部を使用し、重合温度を９５±
２℃にする他は実施例１と同様にして不揮発分５０Ｗ↑
％、ガードナーホルト粘度Ｔ％Ｍｎ＝１０，０００．Ｍ
ｗ／Ｍｎ＝２．０の含フツ素共重合体溶液を得た。ざら
に実施例４と同様にして硬化被膜を得た。この硬化被膜
は本発明の組成物に比べ吸水性が高く、ＱＵＶテスト２
０００ｈｒにおいて光沢の劣化が見られた。Comparative Example 1 When obtaining the fluorine-containing copolymer solution of Example 1, 17F
M50 parts, BA108.5 parts, MMA 281 parts, AA
Using 2.5 parts and 58 parts of HEMA, the polymerization temperature was set at 95±
Same as Example 1 except that the temperature was 2℃, non-volatile content 50W↑
%, Gardner-Holdt viscosity T%Mn=10,000. M
A fluorine-containing copolymer solution with w/Mn=2.0 was obtained. A cured film was obtained in roughly the same manner as in Example 4. This cured film has higher water absorption than the composition of the present invention, and has a QUV test 2
Deterioration of gloss was observed after 000 hours.

比較例　２ 実施例１の含フツ素共重合体溶液を得るに際して１７Ｆ
Ｍ２００部、８Ａ７０．５部、ＡＡ２゜５部、ＴＣＤＭ
Ａ１６９部、ＨＥＭＡ５８部を使用し、重合温度を９５
±２℃にする他は実施例１と同様にして不揮発分５０ｗ
ｔ％、ガードナーホルト粘度ＱＳＭｎ＝９，１００部Ｍ
Ｗ／Ｍｎ＝１゜８の含フツ素共重合体溶液を得た。ざら
に実施例４と同様に塗料化、塗装、乾燥を行なって硬化
被膜を得たが、乾燥被膜にハジキやヘコミが多数あり、
平滑な被膜が得られず評価するに至らなかった。Comparative Example 2 When obtaining the fluorine-containing copolymer solution of Example 1, 17F
M200 parts, 8A70.5 parts, AA2°5 parts, TCDM
Using 169 parts of A and 58 parts of HEMA, the polymerization temperature was set at 95%.
The non-volatile content was 50w in the same manner as in Example 1 except that the temperature was ±2°C.
t%, Gardner-Holdt viscosity QSMn=9,100 parts M
A fluorine-containing copolymer solution with W/Mn=1°8 was obtained. A cured film was obtained by coating, painting, and drying in the same manner as in Example 4, but there were many cracks and dents in the dried film.
A smooth film could not be obtained and could not be evaluated.

比較例　３ 実施例１の含フツ素共重合体溶液を得るに際して１７Ｆ
Ｍ５０部、ＢＡ３９．５部、ＡＡ２．５部、ＴＯＤＭＡ
３５０部、ＨＥＭＡ５Ｂ部を使用し、重合温度を９５±
２℃にする他は実施例１と同様にして不揮発分５０ｗｔ
％、ガードナーホルト粘度Ｎ、Ｍｎ＝１３，０００．Ｍ
ｗ／Ｍｎ＝２゜２、樹脂Ｔｇ＝１０１℃の含フツ素共重
合体溶液を得た。ざらに実施例４と同様に塗料化、塗装
。Comparative Example 3 When obtaining the fluorine-containing copolymer solution of Example 1, 17F
M50 part, BA39.5 part, AA2.5 part, TODMA
Using 350 parts and 5B parts of HEMA, the polymerization temperature was set at 95±
The non-volatile content was 50 wt in the same manner as in Example 1 except that the temperature was 2°C.
%, Gardner-Holdt viscosity N, Mn=13,000. M
A fluorine-containing copolymer solution with w/Mn=2°2 and resin Tg=101°C was obtained. Roughly made into paint and painted in the same manner as in Example 4.

乾燥を行って硬化被膜を得たが、この硬化被膜は表１に
示したように密着性が大幅に低下した。Although a cured film was obtained by drying, the adhesion of this cured film was significantly reduced as shown in Table 1.

４〔発明の効果］ 本発明のフッ素含有被覆組成物は、優れた溌水性、耐汚
染性、耐食性に加えて、脂環族アルキル基を有する（メ
タ）アクリル酸エステルを用いるために、吸水率が低く
、耐候性、耐久性に優れる。4 [Effects of the Invention] In addition to excellent water repellency, stain resistance, and corrosion resistance, the fluorine-containing coating composition of the present invention has a high water absorption rate due to the use of (meth)acrylic ester having an alicyclic alkyl group. It has low corrosion resistance, excellent weather resistance, and durability.

Claims (2)

【特許請求の範囲】[Claims] （１）下記（ａ）、（ｂ）、（ｃ）の単量体成分から構
成される共重合体を主成分としてなるフッ素含有被覆組
成物。 （ａ）一般式Ｒｆ（ＣＨ＿２）＿ｎＯＣＯＣＲ＝ＣＨ＿
２で表される（メタ）アクリル酸エステル ３〜３０重量％ （Ｒｆはフッ素原子の数が１０以上のフル オロアルキル基またはパーフルオロアル キル基含有の置換基であり、ｎは１また は２、Ｒは水素またはメチル基を示す。） （ｂ）炭素数５〜２５の脂環族アルキル基を有する（メ
タ）アクリル酸エステル ２０〜６０重量％ （ｃ）末端に不飽和基を有するビニル単量体１０〜７７
重量％(1) A fluorine-containing coating composition whose main component is a copolymer composed of the following monomer components (a), (b), and (c). (a) General formula Rf(CH_2)_nOCOCR=CH_
3 to 30% by weight of (meth)acrylic acid ester represented by 2 (Rf is a substituent containing a fluoroalkyl group or perfluoroalkyl group having 10 or more fluorine atoms, n is 1 or 2, and R is (represents hydrogen or methyl group) (b) 20 to 60% by weight of (meth)acrylic acid ester having an alicyclic alkyl group having 5 to 25 carbon atoms (c) Vinyl monomer 10 having an unsaturated group at the terminal ~77
weight% （２）請求項（１）において、官能基含有ビニル単量体
を共重合体中３〜３０重量％の割合で含有し、かつ該官
能基と反応し得る架橋剤とを含有してなることを特徴と
するフッ素含有被覆組成物。(2) According to claim (1), the copolymer contains a functional group-containing vinyl monomer in an amount of 3 to 30% by weight, and also contains a crosslinking agent capable of reacting with the functional group. A fluorine-containing coating composition characterized by:
JP63192210A 1988-08-01 1988-08-01 Fluorine-containing coating composition Expired - Fee Related JP2869071B2 (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0251571A (en) * 1988-08-12 1990-02-21 Dainippon Ink & Chem Inc Coating resin composition
US5157091A (en) * 1987-10-07 1992-10-20 Murahara Masataka Ultraviolet-absorbing polymer material and photoetching process
US5707245A (en) * 1994-06-07 1998-01-13 The Whitaker Corporation Card connector with an ejection mechanism and a flexible printed circuit harness therefor
WO2003016412A1 (en) * 2001-08-14 2003-02-27 Avecia Bv Aqueous crosslinkable coating compositions based on vinyl fluoropolymer
JP2007138027A (en) * 2005-11-18 2007-06-07 Dainippon Ink & Chem Inc Polyimide-based coating composition
US7645502B2 (en) 2003-10-06 2010-01-12 Dai Nippon Printing Co., Ltd. Anti-dazzling film
CN113651700A (en) * 2021-08-06 2021-11-16 安徽东至广信农化有限公司 Deamination process of o-phenylenediamine mother liquor

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62577A (en) * 1985-03-18 1987-01-06 Daikin Ind Ltd Water and oil repellent material
JPH01271406A (en) * 1988-03-23 1989-10-30 Hoechst Celanese Corp Autooxidative fluorocarbon polymer and composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62577A (en) * 1985-03-18 1987-01-06 Daikin Ind Ltd Water and oil repellent material
JPH01271406A (en) * 1988-03-23 1989-10-30 Hoechst Celanese Corp Autooxidative fluorocarbon polymer and composition

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5157091A (en) * 1987-10-07 1992-10-20 Murahara Masataka Ultraviolet-absorbing polymer material and photoetching process
JPH0251571A (en) * 1988-08-12 1990-02-21 Dainippon Ink & Chem Inc Coating resin composition
US5707245A (en) * 1994-06-07 1998-01-13 The Whitaker Corporation Card connector with an ejection mechanism and a flexible printed circuit harness therefor
US5899758A (en) * 1994-06-07 1999-05-04 The Whitaker Corporation Flexible printed circuit harness
WO2003016412A1 (en) * 2001-08-14 2003-02-27 Avecia Bv Aqueous crosslinkable coating compositions based on vinyl fluoropolymer
US7247671B2 (en) 2001-08-14 2007-07-24 Dsm Ip Assets B.V. Aqueous crosslinkable coating compositions based on vinyl fluoropolymer
US7645502B2 (en) 2003-10-06 2010-01-12 Dai Nippon Printing Co., Ltd. Anti-dazzling film
JP2007138027A (en) * 2005-11-18 2007-06-07 Dainippon Ink & Chem Inc Polyimide-based coating composition
CN113651700A (en) * 2021-08-06 2021-11-16 安徽东至广信农化有限公司 Deamination process of o-phenylenediamine mother liquor

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