JP2003096377A - Thermosetting fluoroplastic powder coating material composition - Google Patents
Thermosetting fluoroplastic powder coating material compositionInfo
- Publication number
- JP2003096377A JP2003096377A JP2001290905A JP2001290905A JP2003096377A JP 2003096377 A JP2003096377 A JP 2003096377A JP 2001290905 A JP2001290905 A JP 2001290905A JP 2001290905 A JP2001290905 A JP 2001290905A JP 2003096377 A JP2003096377 A JP 2003096377A
- Authority
- JP
- Japan
- Prior art keywords
- curing agent
- fluorine
- thermosetting
- acid
- powder coating
- 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.)
- Withdrawn
Links
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、含フッ素共重合体
と硬化剤からなる熱硬化性フッ素樹脂粉体塗料組成物に
関し、より詳しくは、ブロックイソシアネートを硬化剤
としたときのようなヤニの発生がなく、低温で硬化で
き、耐ブロッキング性に優れ、しかも含フッ素共重合体
と硬化剤との相溶性が良い熱硬化性フッ素樹脂粉体塗料
組成物に関する。TECHNICAL FIELD The present invention relates to a thermosetting fluororesin powder coating composition comprising a fluorine-containing copolymer and a curing agent, and more particularly to a resin composition containing a blocked isocyanate as a curing agent. The present invention relates to a thermosetting fluororesin powder coating composition that does not generate, can be cured at low temperature, has excellent blocking resistance, and has good compatibility between a fluorocopolymer and a curing agent.
【0002】[0002]
【従来の技術】従来、ポリフッ化ビニリデンを主成分と
する熱可塑性のディスパーション型フッ素樹脂塗料やフ
ルオロオレフィンとビニルエーテルまたはビニルエステ
ルとの共重合体を主成分とする溶剤可溶型熱硬化性フッ
素樹脂塗料は、塗膜の耐食性や耐久性、汚れの落ちやす
さなどの理由から重防食用、建築用、工業用などの塗料
分野で近年広く使用されるようになってきた(例えば、
特公昭60−21667、特開昭59−102962、
特開昭61−57609等を参照。)。2. Description of the Related Art Conventionally, a thermoplastic dispersion type fluororesin coating containing polyvinylidene fluoride as a main component and a solvent-soluble thermosetting fluorine containing a copolymer of fluoroolefin and vinyl ether or vinyl ester as a main component. Resin paints have come to be widely used in recent years in the field of paints such as heavy-duty anticorrosion, construction, and industrial use because of the corrosion resistance and durability of coating films and the ease with which stains can be removed (for example,
JP-B-60-21667, JP-A-59-102962,
See JP-A-61-57609. ).
【0003】また、年々深刻化する環境問題に対して有
機溶剤(VOC)の排出量を削減した非溶剤系塗料であ
る粉体フッ素樹脂塗料が提案されている(例えば、特開
平1−103670、特開平2−60968、特開平6
−345822、特開平7−145332等を参
照。)。In addition, a powder fluororesin paint which is a non-solvent paint in which the emission amount of an organic solvent (VOC) is reduced in response to an environmental problem which becomes serious year by year has been proposed (for example, JP-A-1-103670, JP-A-2-60968, JP-A-6
See -345822, JP-A-7-145332 and the like. ).
【0004】ポリフッ化ビニリデン等を主体とする熱可
塑性フッ素樹脂塗料は、融点が高いために200℃以上
の高温での焼き付けが必要であり、かつ結晶性の樹脂で
あることから塗膜の光沢が不充分なものしか得られず、
用途が制限される問題点がある。またフッ化ビニリデン
にテトラフルオロエチレンやヘキサフルオロプロピレン
を共重合させて得られる熱可塑性の低融点フッ素樹脂塗
料も提案されている(例えば、特開平3−220272
を参照。)が、この場合にはコストのかかる低温粉砕を
あらかじめ行う必要がある。Thermoplastic fluororesin paints mainly composed of polyvinylidene fluoride require a baking at a high temperature of 200 ° C. or more because of their high melting points, and since they are crystalline resins, the coating film has a gloss. You can only get enough,
There is a problem that the application is limited. A thermoplastic low-melting-point fluororesin paint obtained by copolymerizing vinylidene fluoride with tetrafluoroethylene or hexafluoropropylene has also been proposed (for example, JP-A-3-220272).
See. However, in this case, it is necessary to perform costly low temperature pulverization in advance.
【0005】他方、熱硬化性フッ素樹脂塗料は、硬化部
位を有するので比較的低い温度で粉体塗装でき、光沢、
透明性、耐溶剤性、機械的強度に優れた塗膜を得ること
ができる。しかしながら、従来の熱硬化性フッ素樹脂粉
体塗料としては、硬化部位を有する単量体として、架橋
性官能基である水酸基を有するビニルエーテル単量体、
アリルエーテル単量体またはクロトン酸アルキル単量体
を共重合させ、ブロックイソシアネートを硬化剤とする
ものが実用化されているのみであった。ブロックイソシ
アネート系硬化剤は、焼き付け塗装時に外れて揮散する
ブロック化剤が乾燥炉に付着し、ヤニ汚染や臭気の原因
の一つとなっている。また少量といえども数パーセント
の揮発物が発生するのは環境面からも好ましくない。更
に低温で硬化させることができないため基材が限定され
るなどの不都合が生じる。On the other hand, since the thermosetting fluororesin coating material has a curing site, it can be powder coated at a relatively low temperature, and has a gloss,
It is possible to obtain a coating film having excellent transparency, solvent resistance and mechanical strength. However, as a conventional thermosetting fluororesin powder coating, as a monomer having a curing site, a vinyl ether monomer having a hydroxyl group which is a crosslinkable functional group,
Only those in which an allyl ether monomer or an alkyl crotonic acid monomer is copolymerized and a blocked isocyanate is used as a curing agent have been put into practical use. The blocked isocyanate curing agent is one of the causes of tar contamination and odor due to the blocking agent that comes off and volatilizes during baking and coating adheres to the drying furnace. In addition, it is not preferable from the environmental point of view that even a small amount of volatile matter is generated in a few percent. Further, since it cannot be cured at a low temperature, disadvantages such as limitation of the base material occur.
【0006】一方、架橋性官能基であるカルボキシル基
を硬化部位として架橋する熱硬化性塗料としては、トリ
グリシジルイソシアヌレート(TGIC)硬化系がある
が、皮膚かぶれなどの問題点が指摘されている。On the other hand, there is a triglycidyl isocyanurate (TGIC) curing system as a thermosetting coating composition that crosslinks a carboxyl group which is a crosslinkable functional group as a curing site, but problems such as skin irritation have been pointed out. .
【0007】一方、架橋性官能基としてカルボキシル基
を含有する熱硬化性ポリエステル樹脂粉体塗料の硬化剤
として、ブロック化剤を使用しないβ−ヒドロキシアク
リルアミド系硬化剤が提案されている。この場合は、た
しかに、ブロック化剤によるごとき臭気やヤニは発生し
ないが、酸と水酸基の反応により水が必然的に離脱する
ので、塗膜にピンホールが生じたり、塗膜のふくれやへ
こみのごとき塗膜欠陥が生じやすいという大きな問題が
ある。On the other hand, a β-hydroxyacrylamide type curing agent which does not use a blocking agent has been proposed as a curing agent for thermosetting polyester resin powder coatings containing a carboxyl group as a crosslinkable functional group. In this case, it is true that no odor or tar is generated by the blocking agent, but water is inevitably released due to the reaction between the acid and the hydroxyl group, so that pinholes are generated in the coating film, or swelling or denting of the coating film occurs. There is a big problem that coating film defects are likely to occur.
【0008】[0008]
【発明が解決しようとする課題】本発明は、前述の従来
技術の有する問題点を解決しようとするものであり、ブ
ロックイソシアネートを硬化剤としたときのようなヤニ
の発生がなく、低温で硬化でき、また熱硬化性ポリエス
テル樹脂塗料において問題となっているピンホール、ふ
くれ、へこみ等の塗膜欠陥が生じない熱硬化性フッ素樹
脂粉体塗料組成物を提供することである。DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned problems of the prior art, and does not cause tarring as in the case of using blocked isocyanate as a curing agent, and cures at a low temperature. Another object of the present invention is to provide a thermosetting fluororesin powder coating composition which can be formed and does not cause coating film defects such as pinholes, blisters and dents, which are problems in thermosetting polyester resin coatings.
【0009】[0009]
【課題を解決するための手段】本発明は上記課題を解決
するためになされたものであり、本発明に従えば、含フ
ッ素共重合体(A)と硬化剤(B)とを含み、当該含フ
ッ素共重合体(A)は、カルボキシル基を含有し、か
つ、フッ素原子の含有量が10〜64質量%の範囲内の
ものであり、また当該硬化剤(B)は、β−ヒドロキシ
アルキルアミド基を有する硬化剤であることを特徴とす
る熱硬化性フッ素樹脂粉体塗料組成物、が提供される。The present invention has been made to solve the above-mentioned problems, and according to the present invention, it comprises a fluorine-containing copolymer (A) and a curing agent (B). The fluorinated copolymer (A) contains a carboxyl group and has a fluorine atom content within a range of 10 to 64% by mass, and the curing agent (B) is a β-hydroxyalkyl. Provided is a thermosetting fluororesin powder coating composition, which is a curing agent having an amide group.
【0010】[0010]
【発明の実施の形態】以下、本発明の好ましい実施の形
態を詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be described in detail.
【0011】本発明におけるカルボキシル基を含有し、
フッ素原子の含有量が10〜64質量%の範囲内である
含フッ素共重合体(A)は、基本的に、以下の(a)、
(b)、(c)の重合単位で構成される。
(a)フルオロオレフィン
(b)カルボキシル基を含有する単量体
(c)その他共重合可能な単量体Containing a carboxyl group in the present invention,
The fluorine-containing copolymer (A) having a fluorine atom content in the range of 10 to 64% by mass basically has the following (a):
It is composed of polymerized units of (b) and (c). (A) Fluoroolefin (b) Monomer containing carboxyl group (c) Other copolymerizable monomer
【0012】または、以下の(a)、(d)、(c)の
重合単位から構成される水酸基を含有する含フッ素共重
合体(A′)に、酸無水物を反応させてカルボキシル基
を付与させて得ることができる。Alternatively, a fluorine-containing copolymer (A ') containing a hydroxyl group composed of the following polymer units (a), (d) and (c) is reacted with an acid anhydride to form a carboxyl group. It can be obtained by giving.
【0013】ただし、フッ素原子の含有量は10〜64
質量%の範囲内にある。水酸基を含有する含フッ素共重
合体(A′)
(a)フルオロオレフィン
(d)水酸基を含有する単量体
(c)その他共重合可能な単量体However, the content of fluorine atoms is 10 to 64.
It is in the range of mass%. Fluorine-containing copolymer having hydroxyl group (A ′) (a) Fluoroolefin (d) Monomer having hydroxyl group (c) Other copolymerizable monomer
【0014】本発明における含フッ素共重合体(A)を
粉体塗料組成物とする場合、フッ素原子の含有量は、1
0〜64質量%の範囲内にあることが要請される。When the fluorine-containing copolymer (A) in the present invention is used as a powder coating composition, the content of fluorine atoms is 1
It is required to be in the range of 0 to 64% by mass.
【0015】フッ素原子の含有量がこれより少ないと、
塗膜の耐候性が低下するだけでなく、塗膜表面の欠陥が
増大する。逆にこれより多いと、β−ヒドロキシアルキ
ルアミド基を含有する硬化剤(B)との相溶性が低下
し、十分に架橋が進行せず、塗膜性能が低下する。好ま
しいフッ素原子の含有量は15〜60質量%である。When the content of fluorine atoms is less than this,
Not only the weather resistance of the coating film decreases, but also the defects on the coating surface increase. On the other hand, if the amount is larger than this, the compatibility with the curing agent (B) containing a β-hydroxyalkylamide group decreases, the crosslinking does not proceed sufficiently, and the coating film performance deteriorates. A preferable content of fluorine atoms is 15 to 60% by mass.
【0016】本発明における含フッ素共重合体(A)の
酸価は、1〜120(mgKOH/g-共重合体)の範囲内であ
ることが好ましい。これより酸価が小さいと、架橋が困
難となり、またβ−ヒドロキシアルキルアミド基を含有
する硬化剤(B)との相溶性も低下する。逆に多すぎる
と、塗膜の耐候性の低下や塗膜欠陥が増大する。より好
ましい酸価の範囲は、5〜100(mgKOH/g-共重合体)
である。なお、後記するように重合単位(c)は、硬化
剤との相溶性や塗膜の柔軟性の向上に貢献する。The acid value of the fluorocopolymer (A) in the present invention is preferably in the range of 1 to 120 (mgKOH / g-copolymer). If the acid value is smaller than this, crosslinking becomes difficult and the compatibility with the curing agent (B) containing a β-hydroxyalkylamide group also decreases. On the other hand, if the amount is too large, the weather resistance of the coating film decreases and the coating film defects increase. A more preferable acid value range is 5 to 100 (mgKOH / g-copolymer)
Is. As will be described later, the polymerized unit (c) contributes to the compatibility with the curing agent and the flexibility of the coating film.
【0017】以上のごとく含フッ素共重合体(A)の組
成は、上記に述べたフッ素原子の含有量の条件や好まし
い酸価の条件を満たす組成であればよく、また、水酸基
を有する含フッ素共重合体(A′)の場合は、酸無水物
等を反応させてカルボキシル基を付与させた後に、同様
の条件を満たすような組成であればよい。As described above, the composition of the fluorine-containing copolymer (A) may be any composition as long as it satisfies the above-mentioned conditions of the content of fluorine atoms and the preferable acid value, and the fluorine-containing copolymer having a hydroxyl group. In the case of the copolymer (A ′), the composition may be one that satisfies the same conditions after reacting an acid anhydride or the like to give a carboxyl group.
【0018】本発明において、(a)のフルオロオレフ
ィンとしては、トリフルオロエチレン、クロロトリフル
オロエチレン、テトラフルオロエチレン、トリフルオロ
プロピレン、テトラフルオロプロピレン、フッ化ビニリ
デン、ペンタフルオロプロピレン、ヘキサフルオロプロ
ピレン、テトラフルオロブチレン、ペンタフルオロブチ
レン等のフッ素原子を含む炭素数2〜4程度のフルオロ
オレフィンが好ましく、中でもトリフルオロエチレン、
クロロトリフルオロエチレン、テトラフルオロエチレ
ン、フッ化ビニリデン、ヘキサフルオロプロピレンが好
ましい。なお、フッ素原子とともに、塩素原子等の他の
ハロゲン原子を含んでいてもよい。In the present invention, examples of the fluoroolefin (a) include trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, trifluoropropylene, tetrafluoropropylene, vinylidene fluoride, pentafluoropropylene, hexafluoropropylene and tetra. Fluoroolefins having a carbon atom number of about 2 to 4 such as fluorobutylene and pentafluorobutylene are preferable, and among them, trifluoroethylene,
Chlorotrifluoroethylene, tetrafluoroethylene, vinylidene fluoride and hexafluoropropylene are preferred. In addition to the fluorine atom, other halogen atom such as chlorine atom may be contained.
【0019】また、(b)のカルボキシル基を含有する
単量体としては、アクリル酸、メタクリル酸、クロトン
酸、イソクロトン酸、10―ウンデシレン(ウンデセ
ン)酸、9−オクタデセン酸(オレイン酸)、フマール
酸、マレイン酸のごとき不飽和脂肪酸等のカルボキシル
基を有する単量体や、式(1)、(2)で表されるカル
ボン酸基含有単量体などが例示される。Examples of the monomer containing a carboxyl group (b) include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, 10-undecylene (undecene) acid, 9-octadecenoic acid (oleic acid) and fumar. Examples thereof include monomers having a carboxyl group such as unsaturated fatty acids such as acids and maleic acids, and carboxylic acid group-containing monomers represented by the formulas (1) and (2).
【0020】(1) CH2=CHOR1OCOR2COO
M
(2) CH2=CHCH2OR3OCOR4COOM
(式中、R1、R3は、炭素数2〜15の二価の炭化水素
基、R2、R4は、飽和あるいは不飽和の直鎖状または環
状の二価の炭化水素基、Mは水素原子、炭化水素基、ア
ルカリ金属または窒素原子を含む化合物である。)(1) CH 2 = CHOR 1 OCOR 2 COO
M (2) CH 2 = CHCH in 2 OR 3 OCOR 4 COOM (formula, R 1, R 3 is a divalent hydrocarbon group having 2 to 15 carbon atoms, R 2, R 4 is a saturated or unsaturated (A linear or cyclic divalent hydrocarbon group, M is a compound containing a hydrogen atom, a hydrocarbon group, an alkali metal or a nitrogen atom.)
【0021】中でも10−ウンデシレン酸がフルオロオ
レフィンとの共重合性が良く、好ましい。Among them, 10-undecylenic acid is preferable because it has good copolymerizability with fluoroolefin.
【0022】これらのカルボキシル基を含有する単量体
は、そのまま共重合することも可能であるが、ビニルエ
ーテルなどのように酸性雰囲気下では共重合しにくい単
量体を共重合させる場合には、重合時にカルボキシル基
をアルカリ塩などの形でブロックしておき、重合後に酸
洗浄を行ってカルボキシル基に戻せば良い。These carboxyl group-containing monomers can be copolymerized as they are, but when copolymerizing a monomer which is difficult to copolymerize in an acidic atmosphere such as vinyl ether, At the time of polymerization, the carboxyl group may be blocked in the form of an alkali salt or the like, and after the polymerization, acid washing may be performed to restore the carboxyl group.
【0023】さらにまた、(c)のその他共重合可能な
単量体としては、酢酸ビニル、プロピオン酸ビニル、酪
酸ビニル、ピバリン酸ビニル、カプロン酸ビニル、カプ
リル酸ビニル、ステアリン酸ビニルなどのビニルエステ
ル類;メチルビニルエーテル、エチルビニルエーテル、
プロピルビニルエーテル、ブチルビニルエーテル、シク
ロヘキシルビニルエーテルなどのビニルエーテル類;メ
チルイソプロペニルエーテル、エチルイソプロペニルエ
ーテル、プロピルイソプロペニルエーテル、ブチルイソ
プロペニルエーテル、シクロヘキシルイソプロペニルエ
ーテルなどのイソプロペニルエーテル類;(メタ)アク
リル酸メチル、(メタ)アクリル酸エチル、(メタ)ア
クリル酸n−プロピル、(メタ)アクリル酸イソプロピ
ル、(メタ)アクリル酸n−ブチル、(メタ)アクリル
酸イソブチル、(メタ)アクリル酸t−ブチル、(メ
タ)アクリル酸n−アミル、(メタ)アクリル酸イソア
ミル、(メタ)アクリル酸n−ヘキシル、(メタ)アク
リル酸イソヘキシル、(メタ)アクリル酸2―エチルヘ
キシル、(メタ)アクリル酸ラウリルなどの(メタ)ア
クリル酸エステル類;クロトン酸メチル、イソクロトン
酸メチル、クロトン酸エチル、イソクロトン酸エチル、
クロトン酸n−プロピル、クロトン酸イソプロピル、ク
ロトン酸n−ブチル、クロトン酸イソブチル、クロトン
酸t−ブチル、クロトン酸n−ヘキシル、クロトン酸イ
ソヘキシルなどのクロトン酸エステル類;エチルアリル
エーテル、プロピルアリルエーテル、ブチルアリルエー
テル、イソブチルアリルエーテルなどのアリルエーテル
類;エチレン、プロピレン、ブチレン、ヘキセン、シク
ロヘキセンなどのオレフィン類などが挙げられる。これ
らを適宜使用することにより、硬化剤との相溶性や塗膜
の柔軟性等を向上させることができる。Further, as the other copolymerizable monomer (c), vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl stearate, etc. Kinds; methyl vinyl ether, ethyl vinyl ether,
Vinyl ethers such as propyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether; isopropenyl ethers such as methyl isopropenyl ether, ethyl isopropenyl ether, propyl isopropenyl ether, butyl isopropenyl ether, cyclohexyl isopropenyl ether; methyl (meth) acrylate , Ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, ( (Meth) acrylic acid n-amyl, (meth) acrylic acid isoamyl, (meth) acrylic acid n-hexyl, (meth) acrylic acid isohexyl, (meth) acrylic acid 2-ethylhexyl, (meth) amyl (Meth) acrylic acid esters such as acrylic acid lauryl, methyl crotonate, methyl isocrotonic acid, ethyl crotonate, ethyl isocrotonic acid,
Crotonic acid esters such as n-propyl crotonic acid, isopropyl crotonic acid, n-butyl crotonic acid, isobutyl crotonic acid, t-butyl crotonic acid, n-hexyl crotonic acid, isohexyl crotonic acid; ethyl allyl ether, propyl allyl ether, Allyl ethers such as butyl allyl ether and isobutyl allyl ether; olefins such as ethylene, propylene, butylene, hexene and cyclohexene. By using these appropriately, the compatibility with the curing agent and the flexibility of the coating film can be improved.
【0024】また、(d)の水酸基を含有する単量体と
しては、2−ヒドロキシエチルビニルエーテル、4−ヒ
ドロキシブチルビニルエーテル、1−ヒドロキシメチル
−4−ビニロキシメチルシクロヘキサン、クロトン酸2
−ヒドロキシエチル、2−ヒドロキシエチルアリルエー
テル、アリルアルコール、(メタ)アクリル酸2−ヒド
ロキシエチル、(メタ)アクリル酸3−ヒドロキシプロ
ピル、(メタ)アクリル酸2−ヒドロキシプロピル、
(メタ)アクリル酸4−ヒドロキシブチル等が挙げられ
る。The hydroxyl group-containing monomer (d) includes 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1-hydroxymethyl-4-vinyloxymethylcyclohexane, and crotonic acid 2
-Hydroxyethyl, 2-hydroxyethyl allyl ether, allyl alcohol, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
4-hydroxybutyl (meth) acrylate etc. are mentioned.
【0025】なお、水酸基を含有する含フッ素共重合体
(A’)は、無水コハク酸や無水グルタル酸のような多
塩基酸無水物を反応せしめてカルボキシル基を有する共
重合体に変性することができる。The fluorine-containing copolymer (A ') containing a hydroxyl group should be modified into a copolymer having a carboxyl group by reacting a polybasic acid anhydride such as succinic anhydride or glutaric anhydride. You can
【0026】本発明のフッ素樹脂粉体塗料組成物におけ
る硬化剤(B)は、β−ヒドロキシアルキルアミド基を
有する硬化剤である。The curing agent (B) in the fluororesin powder coating composition of the present invention is a curing agent having a β-hydroxyalkylamide group.
【0027】β−ヒドロキシアルキルアミド基を有する
硬化剤としては、例えば式(3)で表される化合物があ
げられる。Examples of the curing agent having a β-hydroxyalkylamide group include compounds represented by the formula (3).
【0028】(3) 〔HOCHR5CH2〕2NCOR6
CON〔CH2CHR5OH〕2
(式中、R5は水素原子又は炭素数1〜5のアルキル基
であり、R6はメチレン基、エチレン基、トリメチレン
基、テトラメチレン基又はプロピレン基である。)(3) [HOCHR 5 CH 2 ] 2 NCOR 6
CON [CH 2 CHR 5 OH] 2 (In the formula, R 5 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 6 is a methylene group, an ethylene group, a trimethylene group, a tetramethylene group or a propylene group. .)
【0029】かかるβ−ヒドロキシアルキルアミド基を
含有する硬化剤(B)としては、例えばPrimid XL-552
(商標名:エムス昭和電工社製、式(3)において、R
5はH、R6 は−(CH2)4 −に相当する。)などが挙
げられる。As the curing agent (B) containing such a β-hydroxyalkylamide group, for example, Primid XL-552
(Trademark: EMS Showa Denko KK, in the formula (3), R
5 corresponds to H and R 6 corresponds to — (CH 2 ) 4 —. ) And the like.
【0030】硬化剤(B)は、含フッ素共重合体(A)
に含まれるカルボキシル基に対し、0.2〜3.0倍当
量、好ましくは0.5〜2.0当量使用する。The curing agent (B) is the fluorine-containing copolymer (A).
It is used in an amount of 0.2 to 3.0 times equivalent, preferably 0.5 to 2.0 equivalents, relative to the carboxyl group contained in.
【0031】一般的にβ−ヒドロキシアルキルアミド基
を含有する硬化剤は、すでに述べたように、ブロックイ
ソシアネート硬化剤のように焼付け時にブロック化剤が
煙となって発生することがなく、乾燥炉を汚染せず、ま
た反応による副生成物は微量の水分のみであり、環境保
全の面からも好適である。ただし、これをポリエステル
樹脂の硬化剤として使用した場合は、水酸基との反応に
より生ずる水等のため、塗膜にピンホールが生じたり、
塗膜のふくれやへこみのごとき塗膜欠陥が生じやすいと
いう問題があった。Generally, the curing agent containing a β-hydroxyalkylamide group does not generate smoke as a blocking agent during baking, unlike the blocked isocyanate curing agent, as described above. Is not polluted, and the by-product of the reaction is only a trace amount of water, which is suitable from the viewpoint of environmental protection. However, when it is used as a curing agent for polyester resin, it may have pinholes in the coating film due to water or the like generated by the reaction with hydroxyl groups,
There is a problem that coating film defects such as swelling and dents of the coating film are likely to occur.
【0032】これに対して、β−ヒドロキシアルキルア
ミド基を含有する硬化剤を、本発明で規定する特定のフ
ッ素原子含有量の含フッ素共重合体(A)の硬化剤とし
て使用した場合は、ピンホールや、塗膜のふくれやへこ
みが実質的に生じないという予想外の効果が奏される。
しかも、β−ヒドロキシアルキルアミド基を含有する硬
化剤は、他の硬化剤と比較して、カルボキシル基を含有
する当該含フッ素共重合体との相溶性に優れるという効
果も奏される。なお、その他、低温硬化も可能になる。On the other hand, when a curing agent containing a β-hydroxyalkylamide group is used as a curing agent for the fluorocopolymer (A) having a specific fluorine atom content specified in the present invention, It has an unexpected effect that pinholes, swelling and dents in the coating film do not substantially occur.
In addition, the curing agent containing a β-hydroxyalkylamide group has the effect of being more compatible with the fluorine-containing copolymer containing a carboxyl group than other curing agents. In addition, low temperature curing is also possible.
【0033】本発明における含フッ素共重合体(A)
は、(a)〜(c)等の単量体を乳化重合、溶液重合、
懸濁重合などの適宜な方法で重合し、含フッ素共重合体
の水性分散液や溶液、またはスラリーを得、これを分離
乾燥することにより得られる。Fluorine-containing copolymer (A) in the present invention
Are emulsion polymerization, solution polymerization, and the like of the monomers (a) to (c).
Polymerization is carried out by an appropriate method such as suspension polymerization to obtain an aqueous dispersion, solution or slurry of the fluorocopolymer, which is obtained by separating and drying.
【0034】例えば乳化重合の場合、重合開始剤として
は、通常のラジカル開始剤、特に水溶性開始剤が好まし
く採用され、具体的には、過硫酸アンモニウムなどの過
硫酸塩、過酸化水素あるいはこれらと亜硫酸水素ナトリ
ウム、チオ硫酸ナトリウムなどの還元剤との組み合わせ
からなるレドックス開始剤等が使用される。For example, in the case of emulsion polymerization, as a polymerization initiator, an ordinary radical initiator, particularly a water-soluble initiator is preferably adopted, and specifically, a persulfate such as ammonium persulfate, hydrogen peroxide or a combination thereof is used. A redox initiator or the like composed of a combination with a reducing agent such as sodium hydrogen sulfite or sodium thiosulfate is used.
【0035】重合開始剤の使用量は、その種類、乳化重
合条件などに応じて適宜変更可能であるが、通常は乳化
重合させるべき単量体100質量部あたり0.005〜
0.5質量部程度が好ましい。また、これらの重合開始
剤は、一括添加しても分割添加してもよい。The amount of the polymerization initiator to be used can be appropriately changed depending on the type, emulsion polymerization conditions and the like, but usually 0.005 to 100 parts by mass of the monomer to be emulsion polymerized.
About 0.5 parts by mass is preferable. Further, these polymerization initiators may be added all at once or in portions.
【0036】乳化物のpHを上昇させる目的で、pH調
整剤を用いてもよい。pH調整剤としては、炭酸ナトリ
ウム、炭酸カリウム、オルトリン酸水素ナトリウム、チ
オ硫酸ナトリウムなどの無機塩基及びトリエチルアミ
ン、トリエタノールアミン、ジメチルエタノールアミ
ン、ジエチルエタノールアミンなどの有機塩基類などが
例示される。A pH adjusting agent may be used for the purpose of increasing the pH of the emulsion. Examples of the pH adjuster include inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen orthophosphate, and sodium thiosulfate, and organic bases such as triethylamine, triethanolamine, dimethylethanolamine, and diethylethanolamine.
【0037】乳化重合開始温度は、重合開始剤の種類に
応じて適宜選定されるが、通常は0〜100℃、特に1
0〜90℃程度が好ましく採用され、また重合温度は、
20〜120℃程度である。反応圧力は、適宜選定可能
であるが、通常は0.1〜10MPa、特に0.2〜5
MPa程度を採用する。The emulsion polymerization initiation temperature is appropriately selected according to the kind of the polymerization initiator, but is usually 0 to 100 ° C., and particularly 1
About 0 to 90 ° C is preferably adopted, and the polymerization temperature is
It is about 20 to 120 ° C. The reaction pressure can be appropriately selected, but is usually 0.1 to 10 MPa, particularly 0.2 to 5 MPa.
Adopt about MPa.
【0038】なお単量体はその全量を一括して反応器に
装入する方法、全量を連続して装入する方法、全量を分
割して装入する方法、その一部を仕込んで先ず反応させ
た後、残りを分割してあるいは連続して装入する方法等
種々の方法が採用できる。The monomer is charged all at once into the reactor, all of the monomers are continuously charged, all of the monomers are dividedly charged, and a part of them is charged to start the reaction. After this, various methods such as a method in which the rest is divided or continuously charged can be adopted.
【0039】本発明の粉体塗料組成物は、基本的に、含
フッ素共重合体(A)と硬化剤(B)とからなるが、必
要に応じて、本発明の目的を阻害しない範囲において、
表面平滑剤、発泡抑制剤、シランカップリング剤、紫外
線吸収剤、光安定剤、酸化防止剤、着色顔料、メタリッ
ク顔料、体質顔料などを配合できる。また、含フッ素共
重合体(A)とともに、一般の塗料用組成物に用いる公
知のアクリル樹脂、ポリエステル樹脂、アルキド樹脂、
アミノ樹脂、エポキシ樹脂、ポリウレタン樹脂などの樹
脂を併用してもよい。The powder coating composition of the present invention basically comprises a fluorinated copolymer (A) and a curing agent (B), but, if necessary, within a range not impairing the object of the present invention. ,
Surface smoothing agents, foaming inhibitors, silane coupling agents, ultraviolet absorbers, light stabilizers, antioxidants, color pigments, metallic pigments, extender pigments and the like can be added. Further, together with the fluorinated copolymer (A), known acrylic resins, polyester resins, alkyd resins used in general coating compositions,
Resins such as amino resins, epoxy resins and polyurethane resins may be used in combination.
【0040】含フッ素共重合体(A)、硬化剤(B)と
共にこれらの各成分を、粉末の状態でヘンシェルミキサ
ー等により混合(ドライブレンド)した後、一軸又は二
軸の押出混練機等で溶融混練する。押出機内の温度は、
通常100〜160℃程度とする。充分に溶融混練され
た混練物をシート状等に押出し、当該押出物を冷却し室
温で粉砕する。粉砕後の粒度分布は、吹き付け塗装用に
は20〜50μm程度、流動浸漬塗装用には70〜12
0μm程度とすることが好ましい。The respective components together with the fluorine-containing copolymer (A) and the curing agent (B) are mixed (dry blended) in a powder state with a Henschel mixer or the like, and then, with a uniaxial or biaxial extrusion kneader or the like. Melt and knead. The temperature inside the extruder is
It is usually about 100 to 160 ° C. The kneaded product that has been sufficiently melt-kneaded is extruded into a sheet or the like, and the extruded product is cooled and ground at room temperature. The particle size distribution after crushing is about 20 to 50 μm for spray coating and 70 to 12 for fluidized immersion coating.
It is preferably about 0 μm.
【0041】また塗料組成物の粉体粒子のブロッキング
防止や流動性向上の目的で、粒子表面を有機及び/又は
無機の微粒子で被覆してもよい。このような無機微粒子
としては、硫酸バリウム、炭酸カルシウム、酸化アルミ
ニウム、ケイ酸カルシウム、ケイ酸マグネシウム、酸化
アンチモン、二酸化チタン、酸化鉄、微粉末シリカなど
が挙げられ、有機微粒子としては、ポリオレフィン、ア
クリル系共重合体などが挙げられる。For the purpose of preventing blocking of powder particles of the coating composition and improving fluidity, the surface of the particles may be coated with organic and / or inorganic fine particles. Examples of such inorganic fine particles include barium sulfate, calcium carbonate, aluminum oxide, calcium silicate, magnesium silicate, antimony oxide, titanium dioxide, iron oxide, and fine powder silica. Organic fine particles include polyolefin and acrylic. Examples include system copolymers.
【0042】本発明の熱硬化性フッ素樹脂粉体組成物
は、対象とする基材に塗装後、加熱処理して焼付け硬化
させて塗装塗膜を形成するものである。The thermosetting fluororesin powder composition of the present invention is for coating a target substrate, followed by heat treatment and baking to cure to form a coating film.
【0043】塗装方法としては、特に限定するものでは
なく、従来公知の方法、例えば静電スプレー塗装(吹き
付け塗装)、流動浸漬塗装等が採用できる。塗膜厚みは
特に限定するものではないが、通常乾燥厚みで、30〜
120μmである。加熱処理温度は140〜200℃、
好ましくは150〜180℃程度であり、加熱処理時間
は10〜60分、好ましくは15〜30分程度である。The coating method is not particularly limited, and conventionally known methods such as electrostatic spray coating (spray coating) and fluidized immersion coating can be adopted. The thickness of the coating film is not particularly limited, but is usually a dry thickness of 30 to
It is 120 μm. The heat treatment temperature is 140 to 200 ° C,
It is preferably about 150 to 180 ° C., and the heat treatment time is about 10 to 60 minutes, preferably about 15 to 30 minutes.
【0044】本発明の塗料組成物が対象とする基材は、
例えば、鉄板、ステンレス鋼、アルミニウム、亜鉛処理
鋼板等があげられ、これらの表面は、あらかじめリン酸
クロム処理、リン酸亜鉛処理、クロメート処理等を行っ
てもよい。The base material targeted by the coating composition of the present invention is
Examples thereof include iron plates, stainless steel, aluminum, and zinc-treated steel plates, and the surfaces thereof may be previously subjected to chromium phosphate treatment, zinc phosphate treatment, chromate treatment, and the like.
【0045】[0045]
【実施例】以下に合成例、実施例を掲げて本発明を具体
的に説明するが、かかる実施例などにより本発明は何ら
限定されるものではない。なお、以下の実施例中の部数
は、とくに断りのない限り質量部を示すものであり、%
とあるのは、質量%を示す。EXAMPLES The present invention will be specifically described below with reference to synthesis examples and examples, but the present invention is not limited to the examples. In addition, the number of parts in the following examples indicates parts by mass unless otherwise specified.
"%" Means "% by mass".
【0046】(合成例1)
(1)内容積2.5Lのステンレス鋼製撹拌機付きオー
トクレーブに、イオン交換水860g、10−ウンデシ
レン酸35g、tert―ブタノール46.6g及び炭
酸カリウム26.2gを仕込み、真空ポンプによる脱
気、窒素ガスによる加圧を繰り返して空気を除去した。(Synthesis Example 1) (1) 860 g of ion-exchanged water, 35 g of 10-undecylenic acid, 46.6 g of tert-butanol and 26.2 g of potassium carbonate were placed in an autoclave with a stirrer made of stainless steel and having an internal volume of 2.5 L. Air was removed by repeating charging, deaeration with a vacuum pump, and pressurization with nitrogen gas.
【0047】次に、テトラフルオロエチレン72g、プ
ロピレン1.1g及びエチレン1.4gをオートクレー
ブ中に導入した。Next, 72 g of tetrafluoroethylene, 1.1 g of propylene and 1.4 g of ethylene were introduced into the autoclave.
【0048】(2)オートクレーブ内の温度が70℃に
達した時点で、圧力1.34MPaを示した。その後、
過硫酸アンモニウムの25%水溶液2mLを添加し、反
応を開始させた。圧力の低下に伴い加圧して圧力を維持
しつつ、テトラフルオロエチレン50モル%、プロピレ
ン25モル%、エチレン25モル%の混合ガス250.
5gを連続的に加え反応を続行させた。なお、反応進行
中、過硫酸アンモニウム25%水溶液30ccを連続的
に加えた。(2) When the temperature inside the autoclave reached 70 ° C., the pressure was 1.34 MPa. afterwards,
2 mL of a 25% aqueous solution of ammonium persulfate was added to start the reaction. A mixed gas of 50 mol% tetrafluoroethylene, 25 mol% propylene, and 25 mol% ethylene was added while maintaining the pressure by increasing the pressure as the pressure decreased.
The reaction was continued by continuously adding 5 g. During the progress of the reaction, 30 cc of 25% ammonium persulfate aqueous solution was continuously added.
【0049】8時間後、混合ガスの供給を停止し、オー
トクレーブを水冷して室温に達した後、未反応モノマを
パージし、オートクレーブを開放して固形分濃度30.
1質量%の水性分散液を得た。After 8 hours, the supply of the mixed gas was stopped, the autoclave was cooled with water to reach room temperature, unreacted monomers were purged, and the autoclave was opened to a solid content concentration of 30.
A 1% by weight aqueous dispersion was obtained.
【0050】(3)次いで1N塩酸をpHが3に達する
まで添加し、凝集させ、イオン交換水で洗浄を繰り返し
た後、60℃で乾燥して粉末状の共重合体を得た。(3) Next, 1N hydrochloric acid was added until the pH reached 3, aggregated, washed repeatedly with ion-exchanged water, and dried at 60 ° C. to obtain a powdery copolymer.
【0051】当該共重合体の13C−NMRによる組成分
析の結果は、テトラフルオロエチレンに基づく重合単位
52モル%、プロピレンに基づく重合単位26モル%、
エチレンに基づく重合単位18モル%及び10−ウンデ
シレン酸に基づく重合単位4モル%であった。またフッ
素原子の含有量は、52.5%、酸価は、30.1(mg
KOH/g-共重合体)であった。結果を表1に示す。The results of composition analysis by 13 C-NMR of the copolymer were as follows: 52 mol% of polymer units based on tetrafluoroethylene, 26 mol% of polymer units based on propylene,
Polymerization units were 18 mol% based on ethylene and 4 mol% based on 10-undecylenic acid. The content of fluorine atoms is 52.5% and the acid value is 30.1 (mg
KOH / g-copolymer). The results are shown in Table 1.
【0052】なお、表1の分数で表示された数値のう
ち、分子は供給単量体の組成(モル%)、分母は得られ
た共重合体の組成(モル%)を示す。In the numerical values represented by the fractions in Table 1, the numerator represents the composition (mol%) of the feed monomer, and the denominator represents the composition (mol%) of the obtained copolymer.
【0053】(合成例2〜5)単量体組成を表1に示す
ように変更する他は、合成例1と同様にして重合し、共
重合体を得た。結果を表1に示す。(Synthesis Examples 2 to 5) Polymerization was carried out in the same manner as in Synthesis Example 1 except that the monomer composition was changed as shown in Table 1 to obtain a copolymer. The results are shown in Table 1.
【0054】(合成例6)
(1)内容積300mLのステンレス鋼製撹拌機付き反
応器に、キシレン117g、エタノール21g、シクロ
ヘキシルビニルエーテル(CHVE)42g、4−ヒド
ロキシブチルビニルエーテル(HBVE)14g、炭酸
カリウム1g及びパーブチルPV(PBPV)(商品
名:日本油脂社製過酸化物開始剤)0.07gを仕込
み、液体窒素による固化脱気により溶存酸素を除去し
た。しかる後、クロロトリフルオロエチレン(CTF
E)58gを導入し徐々に昇温した。そして、温度65
℃に維持して、撹拌下で反応を続け、10時間後に反応
器を水冷して反応を停止した。室温まで冷却した後、未
反応単量体を抜出し、反応器を開放した。Synthesis Example 6 (1) In a reactor having a stirrer made of stainless steel and having an internal volume of 300 mL, 117 g of xylene, 21 g of ethanol, 42 g of cyclohexyl vinyl ether (CHVE), 14 g of 4-hydroxybutyl vinyl ether (HBVE), and potassium carbonate. 1 g and 0.07 g of perbutyl PV (PBPV) (trade name: peroxide initiator manufactured by NOF CORPORATION) were charged, and dissolved oxygen was removed by solidification degassing with liquid nitrogen. After that, chlorotrifluoroethylene (CTF
E) 58 g was introduced and the temperature was gradually raised. And the temperature 65
The temperature was maintained at 0 ° C., the reaction was continued under stirring, and after 10 hours, the reaction was stopped by cooling the reactor with water. After cooling to room temperature, unreacted monomers were extracted and the reactor was opened.
【0055】(2)ケイソウ土で固形物をろ過した後、
80℃に加熱し、真空乾燥機で24時間かけて分散媒を
除去したのち、衝撃式ハンマーミルで粉砕し、粉末状の
共重合体(水酸基含有含フッ素共重合体(A′))を得
た。当該共重合体の13C−NMRによる組成分析の結果
は、CTFEに基づく重合単位51モル%、CHVEに
基づく重合単位37モル%、HBVEに基づく重合単位
12モル%であった。(2) After filtering the solid matter with diatomaceous earth,
After heating to 80 ° C and removing the dispersion medium for 24 hours with a vacuum dryer, the powder was pulverized with an impact hammer mill to obtain a powdery copolymer (hydroxyl group-containing fluorocopolymer (A ')). It was The result of composition analysis by 13 C-NMR of the copolymer was 51 mol% of polymer units based on CTFE, 37 mol% of polymer units based on CHVE, and 12 mol% of polymer units based on HBVE.
【0056】(3)次に、得られた水酸基含有含フッ素
共重合体(A′)をアセトンに溶解し、無水コハク酸の
付加反応を60℃で5時間行った。真空乾燥機で24時
間かけて分散媒を除去した後、衝撃式ハンマーミルで粉
砕し、3モル%のカルボキシル基を導入した粉末状の含
フッ素共重合体を得た。フッ素原子の含有量は23.6
%、酸価は13.7(mgKOH/g-共重合体)であった。(3) Next, the obtained hydroxyl group-containing fluorinated copolymer (A ') was dissolved in acetone, and the addition reaction of succinic anhydride was carried out at 60 ° C for 5 hours. After the dispersion medium was removed by a vacuum dryer for 24 hours, it was crushed by an impact hammer mill to obtain a powdery fluorine-containing copolymer having 3 mol% of carboxyl groups introduced. The content of fluorine atoms is 23.6.
%, And the acid value was 13.7 (mgKOH / g-copolymer).
【0057】(合成例7)単量体組成を表1に示すよう
に変更する他は、合成例6と同様にして重合し、共重合
体を得た。結果を表1に示す。(Synthesis Example 7) A copolymer was obtained by polymerizing in the same manner as in Synthesis Example 6 except that the monomer composition was changed as shown in Table 1. The results are shown in Table 1.
【0058】(合成例8)
(1)撹拌機、温度計、精留塔及び窒素ガス導入口を備
えた反応器に、エチレングリコール150g、ネオペン
チルグリコール840gおよびシクロヘキサンジメタノ
ール165gを仕込んで、窒素雰囲気下で撹拌を続けな
がら150℃まで昇温し、次いで、イソフタル酸345
g、テレフタル酸1500gおよびジブチル錫オキサイ
ド2gを仕込んで、撹拌を続けながら240℃にまで昇
温した。Synthesis Example 8 (1) 150 g of ethylene glycol, 840 g of neopentyl glycol and 165 g of cyclohexanedimethanol were charged into a reactor equipped with a stirrer, a thermometer, a rectification column and a nitrogen gas inlet, and nitrogen was charged. The temperature was raised to 150 ° C. under continuous stirring and the isophthalic acid 345 was then added.
g, 1500 g of terephthalic acid and 2 g of dibutyltin oxide were charged, and the temperature was raised to 240 ° C. while continuing stirring.
【0059】(2)さらに、同温度で、樹脂の酸価が1
2(mgKOH/g-樹脂)、水酸基価が26(mgKOH/g-樹脂)
になるまで脱水縮合反応を続行せしめた後、冷却し、真
空乾燥機で24時間かけて分散媒を除去した後、衝撃式
ハンマーミルで粉砕し、粉末状のポリエステル樹脂を得
た。(2) Further, at the same temperature, the acid value of the resin is 1
2 (mgKOH / g-resin), hydroxyl value is 26 (mgKOH / g-resin)
The dehydration condensation reaction was allowed to continue until it became, and the mixture was cooled, the dispersion medium was removed by a vacuum dryer for 24 hours, and the powder was crushed with an impact hammer mill to obtain a powdery polyester resin.
【0060】(実施例1)
(1)合成例1で得たフッ素系共重合体の粉末47g、
Primid XL-552(商品名:エムス昭和電工社製β−ヒド
ロキシアルキルアミド基含有硬化剤)15g、モダフロ
ー2000(商品名:モンサント社製アクリル系重合体
のレベリング剤)0.5g、チヌビン900(商品名:
チバガイギー社製ベンゾトリアゾール系紫外線吸収剤)
2g、チヌビン144(商品名:チバガイギー社製ヒン
ダードアミン系光安定剤)0.7gをドライブレンダー
(三井化工機社製のヘンシェルミキサー型ブレンダー)
により約1分間混合し、ついで90〜130℃の温度条
件で押し出し混練機(プスコニーダーPR−46、プス
社製)を用いて溶融混合した。Example 1 (1) 47 g of the fluorocopolymer powder obtained in Synthesis Example 1,
Primid XL-552 (trade name: β-hydroxyalkylamide group-containing curing agent manufactured by Ems Showa Denko) 15 g, Modaflow 2000 (trade name: acrylic polymer leveling agent manufactured by Monsanto) 0.5 g, Tinuvin 900 (product) Name:
Benzotriazole type UV absorber manufactured by Ciba Geigy)
2g, Tinubin 144 (trade name: Ciba-Geigy hindered amine light stabilizer) 0.7g drive blender (Mitsui Kakohki Henschel mixer type blender)
For about 1 minute, and then melt-mixed using an extrusion kneader (Puskone Kneader PR-46, manufactured by Puss) under a temperature condition of 90 to 130 ° C.
【0061】(2)この溶融混合物を20℃に冷却した
後、衝撃式ハンマーミルで粉砕し、180メッシュの金
網でふるいにかけ熱硬化性フッ素樹脂粉体塗料組成物を
得た。(2) This molten mixture was cooled to 20 ° C., crushed with an impact hammer mill, and sieved with a 180-mesh wire net to obtain a thermosetting fluororesin powder coating composition.
【0062】(3) 次にリン酸亜鉛処理を施した厚さ
1.8mmの鉄板上に、上記粉体塗料組成物を乾燥膜厚
が50μmになるように静電スプレー塗装し、160℃
で20分間加熱処理して硬化させて塗装物を得た。当該
塗膜について以下の項目について塗膜性能試験を行っ
た。結果を表3に示す。(3) Next, the above powder coating composition was electrostatically spray-coated to a dry film thickness of 50 μm on an iron plate having a thickness of 1.8 mm which had been treated with zinc phosphate, and the temperature was adjusted to 160 ° C.
It was heat-treated for 20 minutes and cured to obtain a coated article. With respect to the coating film, a coating film performance test was conducted on the following items. The results are shown in Table 3.
【0063】(a)ヤニの発生: 塗装板からの発煙が
認められるものを不良、認められないものを良好とし
た。(A) Generation of tars: Those in which smoke was observed from the coated plate were evaluated as bad, and those in which smoke was not observed were evaluated as good.
【0064】(b)塗料組成物の貯蔵安定性: 塗料組
成物の15gを内径40mmの試験管に採取し、20
g/cm2の荷重をかけて40℃に240時間放置して
から試料を取り出し、元の粉末状態に戻る場合には、良
好とし、塊状物が見られる場合には不良とした。(B) Storage stability of coating composition: 15 g of the coating composition was sampled in a test tube having an inner diameter of 40 mm, and 20
The sample was taken out after being left at 40 ° C. for 240 hours under a load of g / cm 2 and returned to the original powder state, and it was evaluated as good when lumps were observed, and evaluated as defective.
【0065】(c)耐水性: 塗装サンプルを2時間煮
沸し、異常がないものを○、やや塗膜のフクレやハガレ
が見られるものを△、著しいものを×とした。(C) Water resistance: The coated samples were boiled for 2 hours, and those having no abnormality were evaluated as ◯, those with slight swelling or peeling of the coating film were evaluated as Δ, and marked ones as ×.
【0066】(d)耐溶剤性: キシレンに浸漬した脱
脂綿に、500g/cm2 の荷重をかけて塗膜を往復1
00回ラビングし、傷の有無やはがれを見る。傷やはが
れのいずれもないものを合格とした。(D) Solvent resistance: An absorbent cotton dipped in xylene was applied with a load of 500 g / cm 2 to reciprocate the coating film 1
Rub 00 times to see if there are any scratches or peeling. Those without any scratches or peeling were accepted.
【0067】(e)耐酸性: 塗膜上に10%硫酸を直
径1cmとなるようにスポットし、60℃で1時間加熱
して目視で異常を確認する。○は異常なし、△はややし
み痕のあるものである。(E) Acid resistance: 10% sulfuric acid was spotted on the coating film so that the diameter was 1 cm and heated at 60 ° C. for 1 hour to visually confirm abnormality. ○: No abnormality, △: Slightly scratched mark.
【0068】(f)耐候性: サンシャインウエザオメ
ーターで6,000時間曝露した後の60゜−60゜で
の光沢保持率(%)で表示する。(F) Weather resistance: The gloss retention (%) at 60 ° -60 ° after exposure for 6,000 hours with a sunshine weatherometer is displayed.
【0069】(g)塗膜欠陥: 目視により塗膜のピン
ホール、ふくれ、へこみの有無を確認する。ピンホー
ル、ふくれ、へこみ等の無いものを○、ピンホール、ふ
くれ、へこみが認められるものを×とする。(G) Coating film defect: Visually confirm the presence or absence of pinholes, blisters and dents in the coating film. O: No pinholes, blister, dents, etc., x: Pinholes, blisters, or dents.
【0070】(実施例2〜5)合成例2〜4及び合成例
6で得た含フッ素系共重合体の粉末から、表2に示す質
量比の粉体塗料組成物を、それぞれ実施例1と同様に調
製し、同様に静電スプレー塗装して塗装物を得た。当該
塗膜について実施例1と同様な塗膜性能試験を行った結
果を表3に示す。(Examples 2 to 5) Powder coating compositions having the mass ratios shown in Table 2 were prepared from the powders of the fluorine-containing copolymers obtained in Synthesis Examples 2 to 4 and Synthesis Example 6, respectively. Was prepared in the same manner as above and electrostatically spray-coated in the same manner to obtain a coated product. Table 3 shows the results of conducting the same coating film performance test as in Example 1 on the coating film.
【0071】(比較例1〜3)合成例5および合成例7
で得た含フッ素系共重合体、および合成例8のポリエス
テル樹脂の粉末から、表2に示す質量比の粉体塗料組成
物を、それぞれ実施例1と同様に調製し、同様に静電ス
プレー塗装して塗装物を得た。当該塗膜について実施例
1と同様な塗膜性能試験を行った結果を表3に示す。Comparative Examples 1 to 3 Synthesis Example 5 and Synthesis Example 7
A powder coating composition having a mass ratio shown in Table 2 was prepared in the same manner as in Example 1 from the fluorine-containing copolymer obtained in Example 1 and the powder of the polyester resin of Synthesis Example 8, and electrostatic spraying was performed in the same manner. The paint was obtained by painting. Table 3 shows the results of conducting the same coating film performance test as in Example 1 on the coating film.
【0072】[0072]
【表1】 [Table 1]
【0073】[0073]
【表2】 [Table 2]
【0074】[0074]
【表3】 [Table 3]
【0075】[0075]
【発明の効果】本発明の熱硬化性フッ素樹脂粉体塗料組
成物においては、硬化剤として、β−ヒドロキシアルキ
ルアミド基を有する硬化剤を使用しているので、ブロッ
クイソシアネートを硬化剤としたときのようなヤニの発
生がなく、低温で硬化でき、耐ブロッキング性に優れ、
含フッ素共重合体と硬化剤との相溶性が良いという優れ
た作用効果が奏される。In the thermosetting fluororesin powder coating composition of the present invention, since a curing agent having a β-hydroxyalkylamide group is used as the curing agent, when a blocked isocyanate is used as the curing agent. It can be cured at low temperature and has excellent blocking resistance,
The excellent effect that the compatibility between the fluorine-containing copolymer and the curing agent is good is exhibited.
【0076】また、含フッ素共重合体は、熱硬化性ポリ
エステル樹脂塗料において問題となっているピンホー
ル、ふくれ、へこみ等の塗膜欠陥が生じないという大き
な効果が得られる。Further, the fluorine-containing copolymer has a great effect that coating defects such as pinholes, blisters, and dents, which are problems in thermosetting polyester resin coatings, do not occur.
Claims (3)
とを含み、当該含フッ素共重合体(A)は、カルボキシ
ル基を含有し、かつ、フッ素原子の含有量が10〜64
質量%の範囲内のものであり、また当該硬化剤(B)
は、β−ヒドロキシアルキルアミド基を有する硬化剤で
あることを特徴とする熱硬化性フッ素樹脂粉体塗料組成
物。1. A fluorocopolymer (A) and a curing agent (B)
And the fluorine-containing copolymer (A) contains a carboxyl group and has a fluorine atom content of 10 to 64.
Within the range of% by mass, and the curing agent (B)
Is a curing agent having a β-hydroxyalkylamide group, which is a thermosetting fluororesin powder coating composition.
合体(A)の酸価が、1〜120(mgKOH/g-共重合体)
の範囲内である請求項1に記載の熱硬化性フッ素樹脂粉
体塗料組成物。2. The acid value of the fluorine-containing copolymer (A) having a carboxyl group is 1 to 120 (mgKOH / g-copolymer).
The thermosetting fluororesin powder coating composition according to claim 1, which is within the range.
デシレン酸を単量体単位として含有する請求項1又は2
に記載の熱硬化性フッ素樹脂粉体塗料組成物。3. The fluorine-containing copolymer (A) contains 10-undecylenic acid as a monomer unit.
The thermosetting fluororesin powder coating composition according to.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001290905A JP2003096377A (en) | 2001-09-25 | 2001-09-25 | Thermosetting fluoroplastic powder coating material composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001290905A JP2003096377A (en) | 2001-09-25 | 2001-09-25 | Thermosetting fluoroplastic powder coating material composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2003096377A true JP2003096377A (en) | 2003-04-03 |
Family
ID=19113136
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2001290905A Withdrawn JP2003096377A (en) | 2001-09-25 | 2001-09-25 | Thermosetting fluoroplastic powder coating material composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2003096377A (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012107249A (en) * | 2004-01-22 | 2012-06-07 | Dow Corning Corp | Composition improved in adherence with addition-curable material and composite article incorporating the composition |
WO2013186832A1 (en) * | 2012-06-11 | 2013-12-19 | 大日本塗料株式会社 | Powder coating material composition and method for producing same |
WO2015020107A1 (en) | 2013-08-09 | 2015-02-12 | 旭硝子株式会社 | Method for manufacturing powder coating material, coated article and method for manufacturing same, and method for manufacturing carboxyl-group-containing fluororesin |
WO2015159890A1 (en) * | 2014-04-18 | 2015-10-22 | 旭硝子株式会社 | Powder paint and painted article |
WO2018008421A1 (en) * | 2016-07-08 | 2018-01-11 | ダイキン工業株式会社 | Powder coating composition, coating film, and coated article |
WO2018131655A1 (en) | 2017-01-12 | 2018-07-19 | 旭硝子株式会社 | Powder coating material, method for producing substrate with coating film, coated article and fluorine-containing polymer |
JPWO2018216348A1 (en) * | 2017-05-26 | 2019-11-21 | ダイキン工業株式会社 | Secondary battery separator and secondary battery |
WO2021261401A1 (en) * | 2020-06-22 | 2021-12-30 | Agc株式会社 | Powder coating material composition and laminated body |
-
2001
- 2001-09-25 JP JP2001290905A patent/JP2003096377A/en not_active Withdrawn
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012107249A (en) * | 2004-01-22 | 2012-06-07 | Dow Corning Corp | Composition improved in adherence with addition-curable material and composite article incorporating the composition |
WO2013186832A1 (en) * | 2012-06-11 | 2013-12-19 | 大日本塗料株式会社 | Powder coating material composition and method for producing same |
CN104520395A (en) * | 2012-06-11 | 2015-04-15 | 大日本涂料株式会社 | Powder coating material composition and method for producing same |
JPWO2013186832A1 (en) * | 2012-06-11 | 2016-02-01 | 大日本塗料株式会社 | Powder coating composition and method for producing the same |
JPWO2015020107A1 (en) * | 2013-08-09 | 2017-03-02 | 旭硝子株式会社 | Manufacturing method of powder coating material, coated article and manufacturing method thereof, and manufacturing method of carboxy group-containing fluororesin |
WO2015020107A1 (en) | 2013-08-09 | 2015-02-12 | 旭硝子株式会社 | Method for manufacturing powder coating material, coated article and method for manufacturing same, and method for manufacturing carboxyl-group-containing fluororesin |
CN105452405A (en) * | 2013-08-09 | 2016-03-30 | 旭硝子株式会社 | Method for manufacturing powder coating material, coated article and method for manufacturing same, and method for manufacturing carboxyl-group-containing fluororesin |
WO2015159890A1 (en) * | 2014-04-18 | 2015-10-22 | 旭硝子株式会社 | Powder paint and painted article |
CN106232751A (en) * | 2014-04-18 | 2016-12-14 | 旭硝子株式会社 | powder coating and coated article |
JPWO2015159890A1 (en) * | 2014-04-18 | 2017-04-13 | 旭硝子株式会社 | Powder paint and painted articles |
US10246592B2 (en) | 2014-04-18 | 2019-04-02 | AGC Inc. | Powder paint and painted article |
WO2018008421A1 (en) * | 2016-07-08 | 2018-01-11 | ダイキン工業株式会社 | Powder coating composition, coating film, and coated article |
WO2018131655A1 (en) | 2017-01-12 | 2018-07-19 | 旭硝子株式会社 | Powder coating material, method for producing substrate with coating film, coated article and fluorine-containing polymer |
US11130870B2 (en) | 2017-01-12 | 2021-09-28 | AGC Inc. | Powder coating material, method for producing substrate provided with coating film, coated article and fluorinated polymer |
JPWO2018216348A1 (en) * | 2017-05-26 | 2019-11-21 | ダイキン工業株式会社 | Secondary battery separator and secondary battery |
WO2021261401A1 (en) * | 2020-06-22 | 2021-12-30 | Agc株式会社 | Powder coating material composition and laminated body |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6597806B2 (en) | Powder coating composition, method for producing cured film, and coated article | |
JP6447498B2 (en) | Powder coating material, coated article, and manufacturing method thereof | |
WO2015159890A1 (en) | Powder paint and painted article | |
JPH05247380A (en) | Thermosetting powder coating composition | |
AU775474B2 (en) | Highly weathering-resistant powder coating composition | |
US10655022B2 (en) | Powder coating material, method for producing powder coating material, and coated article | |
JPH01103670A (en) | Thermosetting powder coating composition | |
TW201833248A (en) | Powder coating material, method for producing substrate with coating film, coated article and fluorine-containing polymer | |
JP4232633B2 (en) | Fluorine-containing resin powder having curable functional group and method for producing coating composition thereof | |
JP2003096377A (en) | Thermosetting fluoroplastic powder coating material composition | |
JP3489690B2 (en) | Thermosetting powder coating composition | |
JPH0395276A (en) | Thermosetting powder coating composition | |
JP3716946B2 (en) | Thermosetting powder coating resin composition | |
JPH09302271A (en) | Resin composition for thermosetting powder coating | |
WO1999057208A1 (en) | Thermosetting powder coating composition | |
JP2003105266A (en) | Powder coating material and method for forming coated film | |
WO2017204085A1 (en) | Powder coating composition, process for producing powder coating composition, and coated article | |
JP2022169114A (en) | Powder coating, method for producing coated article, and coated article | |
JP2003105252A (en) | Fluororesin powder coating material composition and production method therefor | |
JP2003105253A (en) | Fluororesin-based coating material composition | |
EP3559126B1 (en) | Fluoropolymer based powder coating | |
JP2000154219A (en) | Powder coating material | |
JP2003105251A (en) | Fluororesin powder coating material composition | |
JP4296765B2 (en) | Fluorine-containing powder coating composition | |
JP2003096378A (en) | Fluoroplastic powder coating material composition and coated product |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20081202 |