JP2001123104A - Powder coating for uneven pattern formation, production thereof, formation of coating film and coated article - Google Patents
Powder coating for uneven pattern formation, production thereof, formation of coating film and coated articleInfo
- Publication number
- JP2001123104A JP2001123104A JP30245499A JP30245499A JP2001123104A JP 2001123104 A JP2001123104 A JP 2001123104A JP 30245499 A JP30245499 A JP 30245499A JP 30245499 A JP30245499 A JP 30245499A JP 2001123104 A JP2001123104 A JP 2001123104A
- Authority
- JP
- Japan
- Prior art keywords
- coating film
- forming
- fluororesin
- resin
- 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.)
- Granted
Links
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明はフッ素樹脂を含む凹
凸模様形成性粉体塗料、さらに詳しくは優れた意匠性を
有する凹凸模様、特にテクスチュア調の模様を形成する
ことができる凹凸模様形成性粉体塗料、この粉体塗料の
製造方法、塗膜の形成方法および塗装物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an irregular pattern-forming powder coating containing a fluororesin, and more particularly, to an irregular pattern having excellent design properties, especially a texture-forming powder capable of forming a texture-like pattern. The present invention relates to a body paint, a method for producing the powder paint, a method for forming a coating film, and a painted object.
【0002】[0002]
【従来の技術】近年、家電製品を始めパソコン、プリン
ターなどのOA機器、さらには鋼製家具などの被塗物へ
の装飾表現の多様化が進んでいる。また地球環境保護対
応型塗料として粉体塗料への期待が高まる中、従来の粉
体塗料では表現できなかった意匠性、特に凹凸模様を形
成させて意匠性を付与する粉体塗料が要求されている。2. Description of the Related Art In recent years, OA equipment such as home appliances, personal computers, and printers, as well as decorative expressions on objects to be coated such as steel furniture have been diversified. In addition, as powder paints are expected to become more environmentally friendly paints, there is a demand for powder paints that cannot be expressed with conventional powder paints, especially those that form concavo-convex patterns to impart design properties. I have.
【0003】凹凸模様を形成させる従来の方法として、
特定の樹脂を粉体塗料の主体樹脂に分散して塗料化する
方法が知られている。例えば特開昭60−258270
号には、常温で固体の熱硬化性樹脂と熱可塑性セルロー
スエーテル系樹脂粉末とを含有する混合物を、熱硬化性
樹脂は溶融するが熱可塑性セルロース系樹脂は溶融しな
い温度で混練し、冷却後、微粉砕化した粉体塗料が開示
されている。しかし、この粉体塗料では熱硬化性樹脂と
熱可塑性セルロースエーテル系樹脂とを同一温度で混練
するため、熱可塑性セルロースエーテル系樹脂の十分な
分散が得られず、塗膜の模様の均一性が得られないばか
りでなく、塗膜の一部は素地にまで達する現象を起こ
し、耐食性に欠けるという問題点を有している。[0003] As a conventional method of forming an uneven pattern,
There is known a method in which a specific resin is dispersed in a main resin of a powder coating to form a coating. For example, JP-A-60-258270
No. 2, a mixture containing a thermosetting resin that is solid at room temperature and a thermoplastic cellulose ether-based resin powder, kneaded at a temperature at which the thermosetting resin melts but the thermoplastic cellulose-based resin does not melt, and after cooling And pulverized powder coatings are disclosed. However, in this powder coating, since the thermosetting resin and the thermoplastic cellulose ether-based resin are kneaded at the same temperature, sufficient dispersion of the thermoplastic cellulose ether-based resin cannot be obtained, and the uniformity of the pattern of the coating film is reduced. Not only cannot it be obtained, but also a part of the coating film has a problem that it reaches the base material and lacks corrosion resistance.
【0004】別の方法として、加熱硬化温度において形
状の安定な樹脂ビーズによりサテン調の凹凸模様を形成
させる方法が提案されている。例えば特開平9−302
272号には、平均粒径が10〜200μmの樹脂ビー
ズ0.1〜40重量%を含有する粉体塗料を塗装する方
法が開示されている。しかし上記方法では、ちぢみ模様
に近い微細な凹凸模様を得るには樹脂ビーズの粒径を小
さくし、塗装膜厚を樹脂ビーズの粒径以下で塗装する必
要があるので、粉体塗料の持つ防食性が十分発揮されな
い。As another method, there has been proposed a method of forming a satin-like uneven pattern using resin beads having a stable shape at a heat curing temperature. For example, JP-A-9-302
No. 272 discloses a method of applying a powder coating containing 0.1 to 40% by weight of resin beads having an average particle size of 10 to 200 μm. However, in the above method, it is necessary to reduce the particle size of the resin beads and apply the coating with a film thickness equal to or less than the particle size of the resin beads in order to obtain a fine uneven pattern close to a fine pattern, so that the corrosion prevention of powder coating is required. Not enough.
【0005】さらに別の方法として、特定の樹脂、硬化
剤、硬化触媒を用いることにより亀甲状の不特定網目模
様を形成させる方法が提案されている。例えば特開平7
−62269号には、水酸基価が10〜320mgKO
H/gの常温で固体の粉体塗料用樹脂60〜95重量
部、ガラス転移温度が30〜70℃のトルエンスルホン
アミド変性メラミン樹脂5〜40重量部、沸点が80〜
250℃のアミン化合物でブロックしたスルホン酸化合
物0.1〜3重量部を配合した粉体塗料が開示されてい
る。しかしこの方法では、特定の樹脂を用いるため、コ
ストが高くなるほか、塗膜の性能も限られたものとなっ
てしまう。[0005] As another method, there has been proposed a method of forming an irregular mesh-like mesh pattern by using a specific resin, a curing agent, and a curing catalyst. For example, JP-A-7
-62269 has a hydroxyl value of 10 to 320 mg KO.
60/95 parts by weight of a resin for powder coating which is solid at room temperature of H / g, 5-40 parts by weight of a toluenesulfonamide-modified melamine resin having a glass transition temperature of 30-70 ° C, and a boiling point of 80-
A powder coating is disclosed which contains 0.1 to 3 parts by weight of a sulfonic acid compound blocked with an amine compound at 250 ° C. However, in this method, since a specific resin is used, the cost is increased, and the performance of the coating film is also limited.
【0006】[0006]
【発明を解決しようとする課題】これら従来の方法によ
る意匠性塗膜は、塗膜表面に比較的大きな凹凸差の形成
による意匠性表現に限られており、異なるトーンや、ソ
フトな手触り感を有した模様は得られていない。また近
年、パソコンやプリンターのようなOA機器、携帯電
話、オフィス家具、計測機器等を中心にデザイン傾向が
高まり、より均一かつ緻密かつ微細な凹凸模様の形成に
よる優れた意匠性とソフトな手触り感を有する模様(以
下、織物調の手触り感という意味でテクスチュアー調模
様という場合がある)を与える塗膜が求められている。However, these conventional coating films are limited to a design expression by forming a relatively large unevenness on the coating film surface, and have different tones and a soft touch feeling. No pattern was obtained. In recent years, the design trend has been increasing mainly in OA equipment such as personal computers and printers, mobile phones, office furniture, measuring equipment, and the like, and excellent design and soft touch due to the formation of more uniform, dense and fine uneven patterns. (Hereinafter, may be referred to as a texture-like pattern in the sense of a fabric-like touch) is required.
【0007】本発明の課題は、このような要望に応える
ため、均一かつ緻密かつ微細で優れた意匠性とソフトな
手触り感を有する凹凸模様を形成することができるとと
もに、塗膜硬度が硬く、しかも塗膜性能に優れた塗膜を
形成することができる凹凸模様形成性粉体塗料を提供す
ることである。本発明の他の課題は、上記凹凸模様形成
性粉体塗料を簡単に効率よく製造することができる凹凸
模様形成性粉体塗料の製造方法を提案することである。
本発明のさらに他の課題は、上記凹凸模様形成性粉体塗
料を用いて凹凸模様の塗膜を形成する塗膜の形成方法、
およびそれによって得られる塗装物を提供することであ
る。[0007] The object of the present invention is to meet such demands by forming a uniform, dense and fine uneven pattern having excellent designability and soft touch feeling, and at the same time, the coating film hardness is high. Moreover, it is an object of the present invention to provide an uneven pattern-forming powder coating material capable of forming a coating film having excellent coating film performance. Another object of the present invention is to propose a method for producing a concavo-convex pattern-forming powder coating which can easily and efficiently produce the concavo-convex pattern-forming powder coating.
Still another object of the present invention is a method for forming a coating film having a concavo-convex pattern using the concavo-convex pattern-forming powder coating,
And to provide a coating obtained thereby.
【0008】[0008]
【課題を解決するための手段】本発明は次の凹凸模様形
成性粉体塗料、その製造方法、塗膜の形成方法および塗
装物である。 (1) 常温で固体の熱硬化型の塗膜形成樹脂(A)1
00重量部に対して、フッ素樹脂(B)を0.01〜2
0重量部の割合で含む粉体塗料であり、フッ素樹脂
(B)は塗膜形成樹脂(A)の溶融温度および硬化温度
において溶融せず、フッ素含有量が10〜85重量%の
フッ素樹脂であり、塗膜形成樹脂(A)がフッ素樹脂
(B)に融着している凹凸模様形成性粉体塗料。 (2) フッ素樹脂(B)は溶融温度が150〜340
℃のフッ素樹脂である上記(1)記載の凹凸模様形成性
粉体塗料。 (3) フッ素樹脂(B)がポリテトラフルオロエチレ
ン、ポリクロロトリフルオロエチレン、ポリフッ化ビニ
リデン、テトラフルオロエチレン・ペルフルオロアルキ
ルビニルエーテル共重合体、テトラフルオロエチレン・
ペルフルオロプロピレン共重合体、またはエチレン・テ
トラフルオロエチレン共重合体である上記(1)または
(2)記載の凹凸模様形成性粉体塗料。 (4) フッ素樹脂(B)の溶融温度未満の温度で塗膜
形成樹脂(A)を加熱硬化させて形成される塗膜が、中
心線平均粗さ(Ra)が2〜20μm、10点平均粗さ
(Rz)が10〜100μm、1cmあたりのピーク数
(Pc)が10〜40個の凹凸模様の塗膜である上記
(1)ないし(3)のいずれかに記載の凹凸模様形成性
粉体塗料。 (5) 塗膜形成樹脂(A)100重量部に対してフッ
素樹脂(B)を0.01〜20重量部の割合で添加した
後、塗膜形成樹脂(A)をその硬化温度未満の温度で加
熱溶融させて混合し、次に冷却したのち粉砕する上記
(1)ないし(4)のいずれかに記載の凹凸模様形成性
粉体塗料の製造方法。 (6) 上記(1)ないし(4)のいずれかに記載の凹
凸模様形成性粉体塗料の塗膜の形成方法であって、フッ
素樹脂(B)の溶融温度未満の温度で塗膜形成樹脂
(A)を加熱硬化させて塗膜を形成する塗膜の形成方
法。 (7) 上記(1)ないし(4)のいずれかに記載の凹
凸模様形成性粉体塗料を被塗物に塗布し、フッ素樹脂
(B)の溶融温度未満の温度で塗膜形成樹脂(A)を加
熱硬化させて塗膜を形成した塗装物。SUMMARY OF THE INVENTION The present invention relates to the following powder coating material having a concavo-convex pattern, a method for producing the same, a method for forming a coating film, and a coated article. (1) Thermosetting film-forming resin (A) 1 which is solid at room temperature
0.01 to 2 parts by weight of the fluororesin (B)
It is a powder coating containing 0 parts by weight. The fluororesin (B) does not melt at the melting temperature and the curing temperature of the coating film forming resin (A), and has a fluorine content of 10 to 85% by weight. An uneven pattern-forming powder coating in which a coating film forming resin (A) is fused to a fluororesin (B). (2) The melting temperature of the fluororesin (B) is 150 to 340
The uneven pattern-forming powder coating according to the above (1), which is a fluororesin at a temperature of ° C. (3) When the fluororesin (B) is polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / perfluoroalkylvinyl ether copolymer, tetrafluoroethylene
The uneven pattern-forming powder coating according to the above (1) or (2), which is a perfluoropropylene copolymer or an ethylene / tetrafluoroethylene copolymer. (4) A coating film formed by heating and curing the coating film forming resin (A) at a temperature lower than the melting temperature of the fluororesin (B) has a center line average roughness (Ra) of 2 to 20 μm and a 10-point average. The uneven pattern-forming powder according to any one of the above (1) to (3), which is a coating film having an uneven pattern having a roughness (Rz) of 10 to 100 μm and a peak number (Pc) of 1 to 40 per cm. Body paint. (5) After adding the fluororesin (B) at a ratio of 0.01 to 20 parts by weight with respect to 100 parts by weight of the film-forming resin (A), the film-forming resin (A) is heated to a temperature lower than its curing temperature. The method according to any one of the above (1) to (4), wherein the powder coating is heated and melted, mixed, cooled, and then pulverized. (6) A method for forming a coating film of the uneven pattern forming powder coating material according to any one of (1) to (4) above, wherein the coating film forming resin is formed at a temperature lower than the melting temperature of the fluororesin (B). A method for forming a coating film in which (A) is cured by heating to form a coating film. (7) The uneven pattern-forming powder coating material according to any one of (1) to (4) is applied to an object to be coated, and the film-forming resin (A) is applied at a temperature lower than the melting temperature of the fluororesin (B). ) Is heat-cured to form a coating.
【0009】[0009]
【発明の実施の形態】本発明で使用される塗膜形成樹脂
(A)は常温で固体であり、加熱溶融することにより硬
化する熱硬化型の樹脂が制限なく使用できる。塗膜形成
樹脂(A)としては、従来から粉体塗料用として用いら
れている公知の熱硬化型樹脂を用いることができる。例
えば、主体樹脂と硬化剤とを含む硬化剤既含有型の樹
脂、硬化剤後添加型の樹脂、および加熱により架橋が形
成される2種以上の架橋反応基を1分子内に有する自己
架橋型樹脂のいずれのものでも使用できる。なお本明細
書においては、塗膜形成に硬化剤が用いられる場合、塗
膜形成樹脂(A)は主体樹脂および硬化剤の両者を合せ
たものを意味する。BEST MODE FOR CARRYING OUT THE INVENTION The film-forming resin (A) used in the present invention is a solid at ordinary temperature, and a thermosetting resin which cures by heating and melting can be used without limitation. As the coating film forming resin (A), a known thermosetting resin conventionally used for powder coatings can be used. For example, a curing agent-containing resin containing a main resin and a curing agent, a curing agent post-addition type resin, and a self-crosslinking type having two or more types of crosslinking reactive groups in one molecule which are crosslinked by heating. Any resin can be used. In the present specification, when a curing agent is used for forming a coating film, the coating film forming resin (A) means a combination of both the main resin and the curing agent.
【0010】塗膜形成樹脂(A)を構成する主体樹脂と
してはエポキシ樹脂、ポリエステル樹脂、アクリル樹
脂、フッ素樹脂などがあげられる。また硬化剤としては
メラミン樹脂、グリシジル化合物、ブロックイソシアネ
ート化合物、イソシアネート化合物、ウレトジオン化合
物、ヒドロキシアルキルアミド化合物、アルキルアミド
化合物、アミド化合物、アミン化合物、多塩基酸化合
物、酸無水化合物、ヒドラジン化合物、フェノール化合
物、およびそれらの重合体などがあげられる。これらの
主体樹脂と硬化剤とは、塗膜に要求される性質に応じて
任意に組み合せて使用される。As the main resin constituting the coating film forming resin (A), there are an epoxy resin, a polyester resin, an acrylic resin, a fluororesin and the like. As the curing agent, melamine resin, glycidyl compound, blocked isocyanate compound, isocyanate compound, uretdione compound, hydroxyalkylamide compound, alkylamide compound, amide compound, amine compound, polybasic acid compound, acid anhydride compound, hydrazine compound, phenol compound And polymers thereof. These main resin and curing agent are used in any combination depending on the properties required for the coating film.
【0011】塗膜形成樹脂(A)として用いられる主体
樹脂と硬化剤との具体的な組合せとしては、主体樹脂が
ポリエステル樹脂の場合、硬化剤としてはメラミン樹
脂、グリシジル化合物、ブロックイソシアネート化合
物、ウレトジオン化合物およびヒドロキシアルキルアミ
ド化合物などからなる群から選ばれる少なくとも一種の
硬化剤が用いられる。また主体樹脂がエポキシ樹脂の場
合、硬化剤としてはアミン化合物、多塩基酸化合物、酸
無水化合物、ヒドラジン化合物およびフェノール化合物
などからなる群から選ばれる少なくとも一種の硬化剤が
用いられる。As a specific combination of the main resin used as the coating film forming resin (A) and the curing agent, when the main resin is a polyester resin, the curing agent may be a melamine resin, a glycidyl compound, a blocked isocyanate compound, a uretdione. At least one curing agent selected from the group consisting of a compound and a hydroxyalkylamide compound is used. When the main resin is an epoxy resin, at least one curing agent selected from the group consisting of an amine compound, a polybasic acid compound, an acid anhydride compound, a hydrazine compound and a phenol compound is used as the curing agent.
【0012】また主体樹脂がアクリル樹脂の場合、硬化
剤としてはグリシジル化合物、ブロックイソシアネート
化合物、ウレトジオン化合物、ヒドロキシアルキルアミ
ド化合物、多塩基酸化合物および酸無水化合物などから
なる群から選ばれる少なくとも一種の硬化剤が用いられ
る。また主体樹脂がフッ素樹脂の場合、硬化剤としては
メラミン樹脂、グリシジル化合物、ブロックイソシアネ
ート化合物、ウレトジオン化合物、ヒドロキシアルキル
アミド化合物、多塩基酸化合物および酸無水化合物など
からなる群から選ばれる少なくとも一種の硬化剤が用い
られる。塗膜形成樹脂(A)は一種単独で使用すること
もできる、二種以上を組み合せて使用することもでき
る。When the main resin is an acrylic resin, the curing agent may be at least one curing agent selected from the group consisting of glycidyl compounds, blocked isocyanate compounds, uretdione compounds, hydroxyalkylamide compounds, polybasic acid compounds and acid anhydride compounds. Agent is used. When the main resin is a fluororesin, as a curing agent, at least one type of curing selected from the group consisting of melamine resins, glycidyl compounds, blocked isocyanate compounds, uretdione compounds, hydroxyalkylamide compounds, polybasic acid compounds and acid anhydride compounds. Agent is used. The film-forming resin (A) may be used alone, or two or more kinds may be used in combination.
【0013】本発明で用いられるフッ素樹脂(B)とし
ては、フッ素樹脂(B)中にフッ素原子を10〜85重
量%、好ましくは40〜80重量%含有するものが制限
なく用いられるが、塗膜形成樹脂(A)の溶融温度およ
び塗膜形成樹脂(A)の硬化温度において溶融しないフ
ッ素樹脂が選択される。塗膜形成樹脂(A)の溶融温度
とは塗膜形成樹脂(A)が軟化して流動化する温度であ
る。上記塗膜形成樹脂(A)の硬化温度とは、塗膜形成
樹脂(A)の硬化反応が行われる温度であり、焼付け温
度に相当する。フッ素樹脂(B)は溶融温度が150〜
340℃、好ましくは170〜330℃であるのが望ま
しい。As the fluororesin (B) used in the present invention, those containing 10 to 85% by weight, preferably 40 to 80% by weight, of fluorine atoms in the fluororesin (B) are used without limitation. A fluororesin that does not melt at the melting temperature of the film-forming resin (A) and the curing temperature of the film-forming resin (A) is selected. The melting temperature of the coating film forming resin (A) is a temperature at which the coating film forming resin (A) softens and flows. The curing temperature of the film-forming resin (A) is a temperature at which a curing reaction of the film-forming resin (A) is performed, and corresponds to a baking temperature. The melting temperature of the fluororesin (B) is 150-
It is desirably 340 ° C, preferably 170-330 ° C.
【0014】なおフッ素樹脂(B)に融点が存在しな
い、すなわち溶融しないものも使用することができ、こ
の場合は塗膜形成樹脂(A)の硬化温度では分解しない
ものが選択される。また塗膜形成樹脂(A)を2種以上
使用する場合は、その中で最も高い硬化温度において溶
融しないフッ素樹脂(B)を組み合せて用いる。フッ素
樹脂(B)は本発明の凹凸模様形成性粉体塗料中におい
て骨材として用いられ、凹凸模様の形成をなすものであ
る。A fluororesin (B) having no melting point, that is, a resin that does not melt can be used. In this case, a resin that does not decompose at the curing temperature of the coating film forming resin (A) is selected. When two or more coating film forming resins (A) are used, a fluororesin (B) which does not melt at the highest curing temperature is used in combination. The fluororesin (B) is used as an aggregate in the concavo-convex pattern-forming powder coating material of the present invention to form a concavo-convex pattern.
【0015】フッ素樹脂(B)を構成するフッ素含有単
量体の種類は特に限定されるものではない。またフッ素
含有単量体の単独重合体であってもよく、2種以上のフ
ッ素含有単量体の共重合体であってもよく、またはフッ
素含有単量体とフッ素を含有しない他の単量体との共重
合体であってもよい。The type of the fluorine-containing monomer constituting the fluororesin (B) is not particularly limited. Further, it may be a homopolymer of a fluorine-containing monomer, a copolymer of two or more types of fluorine-containing monomers, or another monomer containing no fluorine-containing monomer and fluorine. It may be a copolymer with a body.
【0016】フッ素含有単量体の例としてはテトラフル
オロエチレン、クロロトリフルオロエチレン、フッ化ビ
ニリデン、ペルフルオロプロピレン、ペルフルオロアル
キルビニルエーテルなどがあげられる。フッ素を含有し
ない他の単量体としては、エチレン、プロピレンなどの
α−オレフィンなどがあげられる。Examples of the fluorine-containing monomer include tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, perfluoropropylene, perfluoroalkyl vinyl ether and the like. Examples of other monomers containing no fluorine include α-olefins such as ethylene and propylene.
【0017】フッ素樹脂(B)の具体的なものとして
は、ポリテトラフルオロエチレン(フッ素含有量=76
重量%、融点=327℃)、ポリクロロトリフルオロエ
チレン(フッ素含有量=49重量%、融点=220
℃)、ポリフッ化ビニリデン(フッ素含有量=59重量
%、融点=156〜178℃)、テトラフルオロエチレ
ン・ペルフルオロアルキルビニルエーテル共重合体、テ
トラフルオロエチレン・ペルフルオロプロピレン共重合
体(フッ素含有量=76重量%、融点=275℃)、ま
たはエチレン・テトラフルオロエチレン共重合体(エチ
レン/テトラフルオロエチレンのモル比が1/1の場合
のフッ素含有量=59重量%、融点=270℃)などが
あげられる。なお上記フッ素樹脂(B)のフッ素含有量
は構造式から算出される値であり、融点は公知の方法で
重合された重合体の一例である。Specific examples of the fluororesin (B) include polytetrafluoroethylene (fluorine content = 76
% By weight, melting point = 327 ° C.), polychlorotrifluoroethylene (fluorine content = 49% by weight, melting point = 220)
° C), polyvinylidene fluoride (fluorine content = 59% by weight, melting point = 156 to 178 ° C), tetrafluoroethylene / perfluoroalkylvinyl ether copolymer, tetrafluoroethylene / perfluoropropylene copolymer (fluorine content = 76% by weight) %, Melting point = 275 ° C.) or an ethylene / tetrafluoroethylene copolymer (fluorine content = 59% by weight, melting point = 270 ° C. when the molar ratio of ethylene / tetrafluoroethylene is 1/1). . The fluorine content of the fluororesin (B) is a value calculated from the structural formula, and the melting point is an example of a polymer polymerized by a known method.
【0018】フッ素樹脂(B)としては市販品を使用す
ることもできる。市販品の代表的なものとしては、例え
ばDYNEON TFシリーズ(商品名:DYNEON
社製)、DYNEON TFMシリーズ(商品名:DY
NEON社製)、FLUOシリーズ(商品名:MICR
O POWDERS,INC.製)などをあげることが
できる。Commercial products can be used as the fluororesin (B). Representative examples of commercially available products include, for example, DYNEON TF series (trade name: DYNEON
DYNEON TFM series (trade name: DY)
NEON), FLUO series (product name: MICR)
O POWDERS, INC. Manufactured).
【0019】フッ素樹脂(B)は有色、無色問わず所望
とする色調に応じて、任意のものをを使用することがで
きる。また1種類単独で用いてもよいし、2種類以上を
組み合せて用いてもよい。また従来の凹凸模様を与える
組成物やメタリック調を与える組成物と組み合せてもよ
い。As the fluororesin (B), any one can be used according to a desired color tone regardless of color or colorless. One type may be used alone, or two or more types may be used in combination. Moreover, you may combine with the composition which gives the conventional uneven | corrugated pattern, or the composition which gives a metallic tone.
【0020】本発明の凹凸模様形成性粉体塗料における
フッ素樹脂(B)の含有量は、塗膜形成樹脂(A)10
0重量部に対して0.01〜20重量部、好ましくは
0.1〜10重量部の割合である。フッ素樹脂(B)の
含有量が15重量部の割合を越えてもテクスチュア調の
模様が得られる場合もあるが、加工性および塗膜の物性
低下が生じる。一方、0.01重量部未満では模様の均
一性に乏しい塗膜となる。The content of the fluororesin (B) in the concavo-convex pattern-forming powder coating composition of the present invention is determined based on the coating film forming resin (A) 10
The ratio is 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight with respect to 0 parts by weight. Even when the content of the fluororesin (B) exceeds 15 parts by weight, a texture-like pattern may be obtained, but processability and physical properties of the coating film are deteriorated. On the other hand, if the amount is less than 0.01 part by weight, a coating film having poor pattern uniformity is obtained.
【0021】本発明の凹凸模様形成性粉体塗料では塗膜
形成樹脂(A)がフッ素樹脂(B)に融着した粉体塗料
である。このような粉体塗料は、塗膜形成樹脂(A)が
その硬化温度より低い温度で溶融し、フッ素樹脂(B)
は溶融しない状態で両者を混合し、冷却により固化させ
粉砕して得られる粉体塗料であり、塗膜形成樹脂(A)
とフッ素樹脂(B)とが融着した状態の粉体から構成さ
れる。The uneven pattern-forming powder coating material of the present invention is a powder coating material in which the coating film forming resin (A) is fused to the fluororesin (B). In such a powder coating, the film-forming resin (A) melts at a temperature lower than its curing temperature, and the fluororesin (B)
Is a powder coating obtained by mixing the two in a state where they are not melted, solidifying by cooling, and pulverizing.
And a fluororesin (B) fused together.
【0022】塗膜形成樹脂(A)とフッ素樹脂(B)と
が融着していない場合、例えば塗膜形成樹脂(A)の粒
子とフッ素樹脂(B)の粒子との単純な粉体の混合物の
場合、テクスチュアー調模様を形成することはできな
い。また保存、運搬または塗装作業中に塗膜形成樹脂
(A)とフッ素樹脂(B)とが分離することもない。When the film-forming resin (A) and the fluororesin (B) are not fused, for example, a simple powder of particles of the film-forming resin (A) and particles of the fluororesin (B) may be used. In the case of a mixture, a textured pattern cannot be formed. In addition, the film-forming resin (A) and the fluororesin (B) do not separate during storage, transportation or painting.
【0023】本発明の凹凸模様形成性粉体塗料は塗膜形
成樹脂(A)およびフッ素樹脂(B)の他に、必要に応
じて塗膜形成樹脂(A)100重量部に対して0.01
〜100重量部の割合で顔料を配合することができる。
顔料としては二酸化チタン、カーボンブラック、酸化鉄
等の無機顔料;タルク、硫酸バリウム、シリカ、炭酸カ
ルシウム等の体質顔料;シアニンブルー、アゾ顔料等の
有機顔料;メタリックやパール顔料などがあげられる。The uneven pattern-forming powder coating material of the present invention may be used, if necessary, in addition to the film-forming resin (A) and the fluororesin (B) in an amount of 0.1 to 100 parts by weight of the film-forming resin (A). 01
The pigment can be blended at a ratio of 100100 parts by weight.
Examples of the pigment include inorganic pigments such as titanium dioxide, carbon black, and iron oxide; extender pigments such as talc, barium sulfate, silica, and calcium carbonate; organic pigments such as cyanine blue and azo pigments; and metallic and pearl pigments.
【0024】また本発明の凹凸模様形成性粉体塗料に
は、本発明の目的を損なわない範囲で、従来の粉体塗料
に配合されている公知の硬化促進剤、レベリング剤、消
泡剤、酸化防止剤、紫外線吸収剤等の改質剤、または他
の添加剤、あるいは従来の凹凸模様を与える組成物やメ
タリック調を与える組成物などを他の成分として配合す
ることもできる。他の成分の配合量は顔料を除く合計の
配合量として、塗膜形成樹脂(A)100重量部に対し
て0.01〜30重量部の割合とするのが好ましい。[0024] In addition, as long as the object of the present invention is not impaired, the powdery paint for forming a concavo-convex pattern of the present invention may contain a known curing accelerator, leveling agent, defoaming agent, and the like, which are blended in a conventional powdery paint. A modifier such as an antioxidant or an ultraviolet absorber, or another additive, or a conventional composition for providing a concavo-convex pattern or a composition for giving a metallic tone can be blended as another component. The amount of the other components is preferably 0.01 to 30 parts by weight based on 100 parts by weight of the film-forming resin (A), as the total amount excluding the pigment.
【0025】本発明の凹凸模様形成性粉体塗料は、塗膜
形成樹脂(A)100重量部に対してフッ素樹脂(B)
を0.01〜20重量部の割合で添加し、さらに必要に
より添加する他の成分を添加した後、塗膜形成樹脂
(A)をその硬化温度未満の温度、好ましくは硬化温度
より20℃以上低い温度で加熱溶融させて混合し、次に
冷却したのち粉砕することにより製造することができ
る。塗膜形成樹脂(A)を加熱溶融させて混合する前
に、ドライブレンダーなどで各成分を混合することもで
きる。このような製造方法により、塗膜形成樹脂(A)
がフッ素樹脂(B)に融着している本発明の凹凸模様形
成性粉体塗料を容易に効率よく得ることができる。The uneven pattern-forming powder coating material of the present invention comprises a fluororesin (B) based on 100 parts by weight of a film-forming resin (A).
Is added at a ratio of 0.01 to 20 parts by weight, and further, if necessary, other components are added. Then, the coating film-forming resin (A) is heated to a temperature lower than its curing temperature, preferably 20 ° C. or higher than the curing temperature. It can be manufactured by heating and melting at a low temperature, mixing, cooling, and then pulverizing. Each component can be mixed by a drive render or the like before the film-forming resin (A) is melted by heating. By such a production method, the film-forming resin (A)
Can easily and efficiently obtain a powder coating having a concavo-convex pattern of the present invention in which is fused to a fluororesin (B).
【0026】本発明の凹凸模様形成性粉体塗料の好まし
い製造は、塗膜形成樹脂(A)、ならびに必要により配
合される顔料および添加剤等の混合物中にフッ素樹脂
(B)を所定量添加してドライブレンダーで混合した
後、押出混練機、一軸または二軸エクストルーダー等を
用いて塗膜形成樹脂(A)の溶融する温度範囲であって
硬化しない温度範囲、通常80〜120℃で溶融混練を
行い、ペレット状とした後冷却する。冷却後に得られる
固体を衝撃粉砕機、気流式粉砕機等により粉砕、好まし
くは微粉砕することにより凹凸模様形成性粉体塗料を製
造することができる。また粉砕後に、分級することもで
きる。[0026] A preferable production of the powder coating having a concavo-convex pattern of the present invention is to add a predetermined amount of a fluororesin (B) to a mixture of a film-forming resin (A) and, if necessary, a pigment and an additive. And then mixed with a drive render, using an extrusion kneader, a single-screw or twin-screw extruder, etc., and melt at a temperature range where the coating film forming resin (A) melts but does not cure, usually 80 to 120 ° C. The mixture is kneaded, pelletized, and cooled. The solid obtained after cooling can be pulverized, preferably finely pulverized by an impact pulverizer, an air-flow pulverizer, or the like, to produce a powder coating having a concavo-convex pattern. After pulverization, classification can also be performed.
【0027】ここでフッ素樹脂(B)を塗膜形成樹脂
(A)の溶融状態で混合することなく、例えば粉砕時、
または分級時にフッ素樹脂(B)を添加して粉体状態で
混合しても、塗膜形成樹脂(A)がフッ素樹脂(B)に
融着した本発明の凹凸模様形成性の粉体塗料を得ること
はできない。Here, without mixing the fluororesin (B) in the molten state of the coating film forming resin (A), for example,
Alternatively, even if the fluororesin (B) is added at the time of classification and mixed in a powder state, the powder coating material having the concavo-convex pattern of the present invention in which the film-forming resin (A) is fused to the fluororesin (B) is used. You can't get it.
【0028】本発明の凹凸模様形成性粉体塗料を用いた
塗膜の形成方法は、前記本発明の凹凸模様形成性粉体塗
料を静電吹付法、摩擦帯電吹付法、流動浸漬法または静
電流動浸漬法などの公知の粉体塗料における塗装方法に
より被塗物に塗布し、その後フッ素樹脂(B)の溶融温
度未満の温度で、塗膜形成樹脂(A)を加熱溶融させて
硬化させることにより、塗膜を形成する方法である。こ
のような方法により、均一かつ緻密かつ微細な凹凸模様
を有する塗膜を形成させることができ、これにより優れ
た意匠性とソフトな手触り感を有する凹凸模様を有する
塗膜を形成することができる。本発明の凹凸模様形成性
粉体塗料から形成される塗膜は、従来の凹凸模様粉体塗
料では得られない均一かつ緻密かつ微細な凹凸模様を有
する塗膜である。The method for forming a coating film using the concavo-convex pattern-forming powder coating material of the present invention comprises the step of applying the concavo-convex pattern-forming powder coating material of the present invention to an electrostatic spraying method, a triboelectric spraying method, a fluid immersion method or a static immersion method. It is applied to an object to be coated by a known powder coating method such as a current dynamic immersion method, and then the film-forming resin (A) is heated and melted at a temperature lower than the melting temperature of the fluororesin (B) to be cured. This is a method for forming a coating film. By such a method, a coating film having a uniform, dense and fine uneven pattern can be formed, and thereby a coating film having an uneven pattern having excellent design properties and a soft touch can be formed. . The coating film formed from the concavo-convex pattern-forming powder coating material of the present invention is a coating film having a uniform, dense and fine concavo-convex pattern, which cannot be obtained by the conventional concavo-convex pattern powder coating material.
【0029】被塗物としては塗膜形成時における加熱硬
化条件に耐え得るものであれば、材質および形状は特に
制限はなく、任意の被塗物に塗装を行うことができる。
このような被塗物の材質としては、例えば0.2〜2m
m厚程度の鋼板、亜鉛メッキ鋼板、アルミニウム板、マ
グネシウム合金、ステンレス鋼板等の金属板、硝子、セ
ラミック、それらの成形品などをあげることができる。The material and shape of the object to be coated are not particularly limited as long as it can withstand the heat-curing conditions at the time of forming the coating film, and any object can be coated.
As a material of such an object to be coated, for example, 0.2 to 2 m
Examples include a steel plate having a thickness of about m, a galvanized steel plate, an aluminum plate, a magnesium alloy, a metal plate such as a stainless steel plate, glass, ceramic, and a molded product thereof.
【0030】本発明の凹凸模様形成性粉体塗料の硬化温
度(焼付温度)は、塗膜形成樹脂(A)の硬化反応温度
以上の温度であって、かつフッ素樹脂(B)の溶融温度
未満の温度で行う。通常、熱硬化型の粉体塗料の硬化反
応温度(架橋温度)は120〜280℃であるので、こ
の温度で硬化が行われる。この場合、硬化温度はフッ素
樹脂(B)の溶融温度よりも5℃以上、好ましくは10
℃以上低いのが望ましい。フッ素樹脂(B)を2種類以
上使用している場合は、上記フッ素樹脂(B)の溶融温
度は最も溶融温度が低いフッ素樹脂(B)の溶融温度で
ある。またフッ素樹脂(B)の溶融温度に幅がある場合
は低い側の溶融温度である。このような硬化温度を選択
することにより、容易にテクスチュアー調模様の塗膜を
得ることができる。硬化温度を高くすると硬化処理の時
間を短縮することができるので、硬化温度を高くする場
合には溶融温度のより高いフッ素樹脂(B)を塗膜形成
樹脂(A)と組合せて使用する。The curing temperature (baking temperature) of the uneven pattern-forming powder coating material of the present invention is a temperature not lower than the curing reaction temperature of the film-forming resin (A) and lower than the melting temperature of the fluororesin (B). At a temperature of Usually, the curing reaction temperature (crosslinking temperature) of the thermosetting powder coating is 120 to 280 ° C., and the curing is performed at this temperature. In this case, the curing temperature is 5 ° C. or higher, preferably 10 ° C., higher than the melting temperature of the fluororesin (B).
It is desirable that the temperature be lower by at least C. When two or more fluororesins (B) are used, the melting temperature of the fluororesin (B) is the melting temperature of the fluororesin (B) having the lowest melting temperature. When there is a range in the melting temperature of the fluororesin (B), the melting temperature is on the lower side. By selecting such a curing temperature, a textured coating film can be easily obtained. When the curing temperature is increased, the curing time can be shortened. Therefore, when the curing temperature is increased, a fluororesin (B) having a higher melting temperature is used in combination with the film-forming resin (A).
【0031】本発明の凹凸模様形成性粉体塗料を被塗物
へ塗装するには、市販の静電塗装機(荷電圧:−50〜
−100kV)やその他粉体塗装法により均一に塗装し
た後、熱風焼付炉、赤外炉、誘導加熱炉等で加熱溶融し
硬化させて塗膜を形成する。加熱硬化の条件としては、
塗膜形成樹脂(A)の種類や塗料の配合組成にもよる
が、通常、被塗物の温度が120〜280℃で1〜30
分間、好ましくは150〜250℃で3〜20分間が適
当である。In order to apply the concavo-convex pattern-forming powder coating material of the present invention to an object to be coated, a commercially available electrostatic coating machine (charge voltage: -50 to
-100 kV) or other powder coating method, and then heat-melt and harden in a hot air baking furnace, infrared furnace, induction heating furnace or the like to form a coating film. Heat curing conditions include:
Usually, the temperature of the object to be coated is 120 to 280 ° C. and 1 to 30 depending on the type of the film-forming resin (A) and the composition of the paint.
Minutes, preferably 3 to 20 minutes at 150 to 250 ° C.
【0032】塗装膜厚としては特に制限にはないが、通
常、平均膜厚で20〜100μm、好ましくは30〜8
0μmの塗膜厚とする。このようにして塗装することに
より、塗膜硬度が硬く、しかも耐食性等の塗膜性能に優
れ、かつ均一かつ緻密かつ微細な凹凸模様を有し、優れ
た意匠性を有するテクスチュア調模様の塗膜が形成され
る。The coating thickness is not particularly limited, but is usually 20 to 100 μm, preferably 30 to 8 μm in average thickness.
The coating thickness is 0 μm. By coating in this manner, the coating film hardness is high, and furthermore, it has excellent coating performance such as corrosion resistance, and has a uniform, dense and fine uneven pattern, and a textured coating film having excellent design properties. Is formed.
【0033】本発明の凹凸模様形成性粉体塗料の塗装に
よりテクスチュア調模様の塗膜が形成される理由は明ら
かではないが、塗膜形成樹脂(A)の硬化温度において
溶融しないフッ素樹脂(B)が表面張力の関係で塗膜表
面に集まり、そのため塗料の溶融粘度が高い状態で硬化
するため膜厚に大きく左右されることなく、微細な凹凸
模様を形成するためであると推測される。Although it is not clear why the textured coating film is formed by applying the concavo-convex pattern-forming powder coating material of the present invention, a fluorine resin (B) which does not melt at the curing temperature of the coating film forming resin (A) is used. ) Gather on the surface of the coating film due to the relationship of surface tension, and therefore the coating material is cured in a state where the melt viscosity of the coating material is high.
【0034】このようにして形成される塗膜が均一かつ
緻密かつ微細な凹凸模様を有していることは、中心線平
均粗さ(Ra)、10点平均粗さ(Rz)および1cm
あたりのピーク数(Pc)を指標にして示すことができ
る。すなわち、本発明の凹凸模様形成性粉体塗料を用い
て前記方法により硬化塗膜を形成することにより、中心
線平均粗さ(Ra)が2〜20μm、好ましくは3〜9
μm、10点平均粗さ(Rz)が10〜100μm、好
ましくは15〜55μm、1cmあたりのピーク数(P
c)が5〜40個、好ましくは10〜35個の均一かつ
緻密かつ微細な凹凸模様を有している塗膜を容易に形成
することができる。The uniformity, fineness, and fine unevenness of the coating film formed in this manner are based on the center line average roughness (Ra), the 10-point average roughness (Rz) and the 1 cm average roughness.
The peak number per unit (Pc) can be shown as an index. That is, by forming a cured coating film by the above method using the uneven pattern-forming powder coating material of the present invention, the center line average roughness (Ra) is 2 to 20 μm, preferably 3 to 9 μm.
μm, 10-point average roughness (Rz) is 10 to 100 μm, preferably 15 to 55 μm, and the number of peaks per cm (P
c) 5 to 40, preferably 10 to 35, coating films having a uniform, dense and fine concavo-convex pattern can be easily formed.
【0035】上記中心線平均粗さ(Ra)および10点
平均粗さ(Rz)は模様の高さを表現するもので次の値
である。また1cmあたりのピーク数(Pc)は凹凸の
緻密さを表現するもので次の値である。 Ra:平均線からの絶対値偏差の平均値。 Rz:基準長さ毎の凸部の高い方から5点の絶対値の平
均値と、凹部の低い方から5点の絶対値の平均値との
和。 Pc:中心線に平行な二本のカウントレベルを設け、下
側のカウントレベルと曲線の交差する2点間において、
上側のカウントレベルと曲線が交差する点が1点以上あ
る場合に1山(ピーク)とし、1cm当たりの山(ピー
ク)の数。The center line average roughness (Ra) and the 10-point average roughness (Rz) express the height of the pattern and are as follows. The number of peaks per cm (Pc) expresses the fineness of the unevenness and is the following value. Ra: Average value of absolute value deviation from the average line. Rz: the sum of the average value of the absolute values of the five points from the higher side of the convex portion and the average value of the absolute values of the five points from the lower side of the concave portion for each reference length. Pc: Two count levels parallel to the center line are provided, and between the lower count level and two points where the curve intersects,
When there is one or more points where the upper count level and the curve intersect, one peak (peak) is defined as the number of peaks (peaks) per cm.
【0036】上記中心線平均粗さ(Ra)は表面粗度
計、例えば(株)ミツトヨ製サーフテスト301(商
標)により測定することができる。また10点平均粗さ
(Rz)は表面粗度計、例えば(株)ミツトヨ製サーフ
テスト301(商標)により測定することができる。ま
た1cmあたりのピーク数(Pc)は表面粗度計、例え
ば(株)ミツトヨ製サーフテスト301(商標)により
測定することができる。The center line average roughness (Ra) can be measured by a surface roughness meter, for example, Surf Test 301 (trademark) manufactured by Mitutoyo Corporation. The 10-point average roughness (Rz) can be measured by a surface roughness meter, for example, Surf Test 301 (trademark) manufactured by Mitutoyo Corporation. The number of peaks per 1 cm (Pc) can be measured by a surface roughness meter, for example, Surf Test 301 (trademark) manufactured by Mitutoyo Corporation.
【0037】このようなテクスチュア模様が形成された
塗膜を有する被塗物は、優れた意匠性を有するとともに
ソフトな手触り感を有し、しかも塗膜硬度が硬く、かつ
耐食性などの塗膜性能にも優れているので、自動車のボ
ディおよび部品;テレビ、オーディオ等の家電製品;パ
ソコン、プリンター等のOA機器;電話機、携帯電話等
の電気、通信機器;ポール、防音壁等の道路資材;建物
の内壁、柱巻、ルーフ、間仕切り板等の建材;パイプ、
継手、金属機械、ゴミ入れ、小物入れ、スチール家具、
スチール机、飲料缶といった鉄、亜鉛メッキ鋼、ステン
レス、アルミニウム、マグネシウムおよびそれらの合金
等の金属製品;ガラス、木材、石こうボート、ガラス繊
維等を原料とする織物、耐熱紙、150℃以上の耐熱を
有するプラスチックス、これらの印刷物または着色物な
どの分野で使用することができる。An object to be coated having a coating film on which such a texture pattern is formed has excellent design properties, has a soft touch feeling, and has a high coating film hardness and a coating film property such as corrosion resistance. Car body and parts; Home appliances such as TVs and audios; OA equipment such as personal computers and printers; Electricity and communication equipment such as telephones and mobile phones; Road materials such as poles and sound barriers; Building materials such as inner walls, pillars, roofs, partition boards; pipes,
Fittings, metal machinery, trash bins, accessory bins, steel furniture,
Metal products such as iron, galvanized steel, stainless steel, aluminum, magnesium and their alloys such as steel desks and beverage cans; fabrics made of glass, wood, gypsum boats, glass fibers, etc., heat-resistant paper, heat resistant to 150 ° C or more Can be used in the field of plastics having these, printed matter or colored matter thereof.
【0038】[0038]
【発明の効果】本発明の凹凸模様形成性粉体塗料は、塗
膜形成樹脂および特定のフッ素樹脂を特定量含有し、し
かも両成分は融着しているので、均一かつ緻密かつ微細
で優れた意匠性とソフトな手触り感を有する凹凸模様が
形成されるとともに、塗膜硬度が硬く、しかも塗膜性能
に優れた塗膜が形成される。本発明の凹凸模様形成性粉
体塗料の製造方法は、塗膜形成樹脂にフッ素樹脂を添加
した後、塗膜形成樹脂をその硬化温度未満の温度で加熱
溶融させて混合し、次に冷却したのち粉砕しているの
で、上記凹凸模様形成性粉体塗料を簡単に効率よく製造
することができる。According to the present invention, since the powder coating material having a concavo-convex pattern of the present invention contains a specific amount of a resin for forming a coating film and a specific fluororesin, and both components are fused, it is excellent in uniformity, denseness and fineness. In addition to forming a concavo-convex pattern having a good design and soft touch, a coating film having a high coating film hardness and excellent coating film performance is formed. The method for producing the concavo-convex pattern-forming powder coating material of the present invention is such that after adding a fluororesin to the film-forming resin, the film-forming resin is heated and melted at a temperature lower than its curing temperature, mixed, and then cooled. Since the powder is subsequently pulverized, the above-mentioned uneven pattern-forming powder coating material can be easily and efficiently produced.
【0039】本発明の塗膜の形成方法は、上記凹凸模様
形成性粉体塗料から塗膜を形成するに際して、フッ素樹
脂の溶融温度未満の温度で塗膜形成樹脂を硬化させて塗
膜を形成しているので、均一かつ緻密かつ微細で優れた
意匠性とソフトな手触り感を有する凹凸模様を形成する
ことができるとともに、塗膜硬度が硬く、しかも塗膜性
能に優れた塗膜を形成することができる。本発明の塗装
物は上記塗膜が形成されているので、意匠性に優れ、ソ
フトな手触り感および織物調の手触り感を有している。In the method for forming a coating film of the present invention, the coating film is formed by curing the coating film forming resin at a temperature lower than the melting temperature of the fluororesin when forming the coating film from the above-mentioned powdery coating material having an uneven pattern. As a result, it is possible to form a uniform, dense, fine, uneven design having excellent design properties and a soft touch feeling, and to form a coating film having a high coating film hardness and excellent coating performance. be able to. Since the coated material of the present invention has the above-mentioned coating film formed thereon, it has excellent design properties, and has a soft touch feeling and a fabric-like touch feeling.
【0040】[0040]
【実施例】次に、本発明を実施例によりさらに具体的に
説明するが本発明はこれらの実施例によって何ら制限さ
れるものではない。EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
【0041】実施例1〜4 表1に示した成分を、ドライブレンダー(商品名;ヘン
シェルミキサー、三井三池化工機株式会社製)により約
1分間均一に混合し、次に80〜100℃の温度条件で
押出混練機(商品名;ブスコニーダーPR46、ブス社
製)を用いて溶融混練し、塗膜形成樹脂(A)をフッ素
樹脂(B)に融着させた。冷却後ハンマー式衝撃粉砕機
で微粉砕した後、100メッシュの金網で分級すること
により凹凸模様形成性粉体塗料を製造した。Examples 1 to 4 The components shown in Table 1 were uniformly mixed by a drive render (trade name: Henschel mixer, manufactured by Mitsui Miike Kakoki Co., Ltd.) for about 1 minute, and then a temperature of 80 to 100 ° C. Under the conditions, the mixture was melt-kneaded using an extrusion kneader (trade name: Buscon Kneader PR46, manufactured by Bus) to fuse the film-forming resin (A) to the fluororesin (B). After cooling, the resultant was finely pulverized with a hammer-type impact pulverizer, and then classified with a 100-mesh wire net, thereby producing a powder coating having a concavo-convex pattern.
【0042】得られた粉体塗料を、−80kV荷電で静
電吹付法によりマグネシウム合金製の金属板に塗装し
た。次いで表2に示した焼付条件において加熱硬化させ
た後、塗膜外観および塗膜物性について評価を行った。
結果を表2に示す。また得られた塗膜について、(株)
ミツトヨ製サーフテスト301(商標)を用いて表面粗
さ曲線を下記測定条件で求めた。図1〜図4に示す。 縦軸:1目盛り10μm 横軸:1区間2.5mm 基準長さカットオフ:2.5mm ピークカウントレベル:2.5μmThe obtained powder coating was applied to a metal plate made of a magnesium alloy by electrostatic spraying at a charge of -80 kV. Next, after curing by heating under the baking conditions shown in Table 2, the appearance and physical properties of the coating film were evaluated.
Table 2 shows the results. About the obtained coating film,
The surface roughness curve was determined using Surf Test 301 (trademark) manufactured by Mitutoyo under the following measurement conditions. 1 to 4. Vertical axis: 1 scale 10 μm Horizontal axis: 1 section 2.5 mm Reference length cutoff: 2.5 mm Peak count level: 2.5 μm
【0043】[0043]
【表1】 [Table 1]
【0044】表1の注 *1 P−3450:ポリエステル樹脂、酸価=35m
gKOH/g、DSMResins社製、商標 *2 M−8120:ポリエステル樹脂、水酸基価=3
0mgKOH/g、大日本インキ化学工業(株)製、商
標 *3 EP1002:エポキシ樹脂、エポキシ当量=6
50g/eq.、SHELL Chemicals社
製、商標 *4 B1530:アダクト体イソシアネート硬化剤、
イソシアネート当量=280g/eq.、CREANO
VA社製、商標 *5 モダフロー:レベリング剤、MONSANT社
製、商標 *6 ブタフロー:硬化促進剤、ESTRON Che
mical Inc.製、商標 *7 TF1645:DYNEON TF1645、ポ
リテトラフルオロエチレン、フッ素含量=76重量%、
融点=320℃、DYNEON社製、商標 *8 TF1750:DYNEON TF1750、ポ
リテトラフルオロエチレン、フッ素含量=76重量%、
融点=320℃、DYNEON社製、商標 *9 FLUO 625F :ポリテトラフルオロエチレン、フッ
素含量=74重量%、融点=316℃、MICRO P
OWDERS INC.製、商標Notes on Table 1 * 1 P-3450: polyester resin, acid value = 35 m
gKOH / g, manufactured by DSM Resins, trademark * 2 M-8120: polyester resin, hydroxyl value = 3
0 mgKOH / g, manufactured by Dainippon Ink and Chemicals, Inc., trademark * 3 EP1002: epoxy resin, epoxy equivalent = 6
50 g / eq. Manufactured by SHELL Chemicals, Inc., trademark * 4 B1530: adduct isocyanate curing agent,
Isocyanate equivalent = 280 g / eq. , CREANO
VA, trademark * 5 Modaflow: leveling agent, MONSANT, trademark * 6 Butaflow: curing accelerator, ESTRON Che
medical Inc. * 7 TF1645: DYNEON TF1645, polytetrafluoroethylene, fluorine content = 76% by weight,
Melting point = 320 ° C., manufactured by DYNEON, trademark * 8 TF1750: DYNEON TF1750, polytetrafluoroethylene, fluorine content = 76% by weight,
Melting point = 320 ° C., manufactured by DYNEON, trademark * 9 FLUO 625F: polytetrafluoroethylene, fluorine content = 74% by weight, melting point = 316 ° C., MICRO P
OWDERS INC. Made, trademark
【0045】[0045]
【表2】 [Table 2]
【0046】表2の注 *1 B成分の配合割合:A成分100重量部に対する
B成分の重量部。 *2 塗膜模様:均一かつ緻密かつ微細な凹凸模様が形
成されることにより、意匠性とソフトな手触り感を有す
る塗膜(すなわちテクスチュアー調模様)が形成された
か否かを、肉眼観察により判定した。 良好:テクスチュアー調模様が形成された。 不均一:凸部が独立し、不均一な模様が形成された。 *3 Ra(中心線平均粗さ):(株)ミツトヨ製サー
フテスト301(商標)により求めた。 *4 Rz(10点平均粗さ):(株)ミツトヨ製サー
フテスト301(商標)により求めた。 *5 Pc(ピークカウント):(株)ミツトヨ製サー
フテスト301(商標)により求めた。 *6 エリクセン値: JIS K5400 8.2.
2破断距離法に準じて行った。 *7 耐衝撃性:JIS K5400 8.3.2デュ
ポン式に準じて行った。 *8 屈曲性試験:JIS K5400 8.1に準じ
て行った。 *9 耐塩水噴霧性:JIS K5400 9.2に準
じて、塗膜表面にクロスカットを行った後、300時間
連続で試験を行った。カット面上でテープはく離を行
い、カット中心線からはく離した幅の最大値をはく離距
離として測定し、耐塩水噴霧性の指標とした。 *10 鉛筆硬度:JIS K5400 8.4.2に
準じて行った。Notes to Table 2 * 1 B component blending ratio: 100 parts by weight of component A, parts by weight of component B. * 2 Coating film pattern: Determined by visual observation whether or not a coating film having a design property and a soft touch (that is, a texture-like pattern) was formed by forming a uniform, dense and fine uneven pattern. did. Good: A texture pattern was formed. Non-uniform: The convex portions are independent, and a non-uniform pattern is formed. * 3 Ra (center line average roughness): determined by Surftest 301 (trademark) manufactured by Mitutoyo Corporation. * 4 Rz (10-point average roughness): determined by Surftest 301 (trademark) manufactured by Mitutoyo Corporation. * 5 Pc (peak count): determined by Surftest 301 (trademark) manufactured by Mitutoyo Corporation. * 6 Erichsen value: JIS K5400 8.2.
The measurement was performed according to the 2 breaking distance method. * 7 Impact resistance: Performed according to JIS K5400 8.3.2 Dupont method. * 8 Flexibility test: Conducted according to JIS K5400 8.1. * 9 Salt water spray resistance: After performing a cross cut on the coating film surface according to JIS K5400 9.2, a test was performed continuously for 300 hours. The tape was peeled off on the cut surface, and the maximum value of the width peeled from the cut center line was measured as a peel distance, which was used as an index of salt spray resistance. * 10 Pencil hardness: Performed according to JIS K5400 8.4.2.
【0047】実施例1および2はフッ素樹脂(B)とし
て融点が320℃のポリテトラフルオロエチレンを異な
る重量部用いたハイブリッド系粉体塗料、実施例3はフ
ッ素樹脂(B)として融点が316℃以上のポリテトラ
フルオロエチレンを用いたウレタン系粉体塗料、実施例
4は融点が異なるポリテトラフルオロエチレンを2種用
いたウレタン系粉体塗料である。Examples 1 and 2 are hybrid powder coatings using different parts by weight of polytetrafluoroethylene having a melting point of 320 ° C. as the fluororesin (B), and Example 3 is a fluororesin (B) having a melting point of 316 ° C. The urethane-based powder coating using polytetrafluoroethylene described above, and Example 4 is a urethane-based powder coating using two types of polytetrafluoroethylene having different melting points.
【0048】表2からわかるように、実施例1〜4のい
ずれの凹凸模様形成性粉体塗料においても、塗装された
塗膜はテクスチュア調の模様が被塗物上に形成され、優
れた意匠性と共に良好な塗膜物性を示す塗膜が得られ
た。As can be seen from Table 2, in any of the irregular-pattern-forming powder coatings of Examples 1 to 4, the applied coating had a texture-like pattern formed on the object to be coated. A coating film showing good coating film properties together with the properties was obtained.
【0049】比較例1〜2 表3に示した成分を用いて、実施例1〜4と同じ方法に
より粉体塗料を製造し、実施例1〜4と同じ方法により
塗装を行った。次いで表4に示した焼付条件において加
熱硬化させた後、塗膜外観および塗膜物性について評価
を行った。結果を表4、図12および図13に示す。Comparative Examples 1-2 Using the components shown in Table 3, powder coatings were produced in the same manner as in Examples 1-4, and coating was carried out in the same manner as in Examples 1-4. Next, after curing by heating under the baking conditions shown in Table 4, the appearance and physical properties of the coating film were evaluated. The results are shown in Table 4, FIG. 12 and FIG.
【0050】比較例3 表3に示したフッ素樹脂以外の成分をドライブレンダー
(商品名;ヘンシェルミキサー、三井三池化工機株式会
社製)により約1分間均一に混合し、次に80〜100
℃の温度条件で押出混練機(商品名;ブスコニーダーP
R46、ブス社製)を用いて溶融混練を行い、冷却後表
3に示したフッ素樹脂を添加してハンマー式衝撃粉砕機
で微粉砕した後、100メッシュの金網で分級すること
により粉体塗料を製造した。得られた粉体塗料は、実施
例1〜4と同じ方法により塗装を行った。次いで表4に
示した焼付条件において加熱硬化させた後、塗膜外観お
よび塗膜物性について評価を行った。結果を表4に示
す。Comparative Example 3 Components other than the fluororesins shown in Table 3 were uniformly mixed for about 1 minute by a drive render (trade name: Henschel mixer, manufactured by Mitsui Miike Kakoki Co., Ltd.), and then 80 to 100
Extrusion kneader (Trade name; Buscon Kneader P)
R46, manufactured by Bus Co., Ltd.), cooled, added with the fluororesin shown in Table 3, finely pulverized with a hammer-type impact pulverizer, and then classified with a 100-mesh wire mesh to obtain a powder coating. Was manufactured. The obtained powder coating was applied by the same method as in Examples 1 to 4. Next, after curing by heating under the baking conditions shown in Table 4, the appearance and physical properties of the coating film were evaluated. Table 4 shows the results.
【0051】比較例4 比較例3と同様にフッ素樹脂以外の成分を溶融混練を行
い、冷却後にハンマー式衝撃粉砕機で微粉砕した。その
後、フッ素樹脂を添加してから100メッシュの金網で
分級することにより粉体塗料を製造した。得られた粉体
塗料は、実施例1〜4と同じ方法により塗装を行った。
次いで表4に示した焼付条件において加熱硬化させた
後、塗膜外観および塗膜物性について評価を行った。結
果を表4に示す。Comparative Example 4 Components other than the fluororesin were melt-kneaded in the same manner as in Comparative Example 3, and after cooling, were finely pulverized with a hammer impact pulverizer. Thereafter, a powder coating was manufactured by adding a fluororesin and then classifying it with a 100-mesh wire net. The obtained powder coating was applied by the same method as in Examples 1 to 4.
Next, after curing by heating under the baking conditions shown in Table 4, the appearance and physical properties of the coating film were evaluated. Table 4 shows the results.
【0052】[0052]
【表3】 *1 表1参照 *3 表1参照 *5 表1参照 *7 表1参照 *10 SYNFLUO 180VF :ポリテトラフルオロエチレン樹脂、フッ素含量=7 6重量%、融点=104〜110℃、MICRO POWDERS INC.製 、商標[Table 3] * 1 See Table 1 * 3 See Table 1 * 5 See Table 1 * 7 See Table 1 * 10 SYNFLUO 180VF: Polytetrafluoroethylene resin, fluorine content = 76% by weight, melting point = 104-110 ° C., MICRO POWDERS INC. Made, trademark
【0053】[0053]
【表4】 *1〜*10 表2参照[Table 4] * 1 to * 10 See Table 2
【0054】比較例1、2はフッ素樹脂として硬化温度
より融点が低いポリテトラフルオロエチレンを異なる重
量部用いた粉体塗料である。表4からわかるように、比
較例1、2の粉体塗料ではいずれの塗膜も目的とするテ
クスチュア調模様は得られなかった。また比較例3、4
の粉体塗料では、いずれも塗装中に吹きムラを生じ、目
的とするテクスチュア調模様は得られず、塗膜物性の低
下も認められた。Comparative Examples 1 and 2 are powder coatings using different parts by weight of polytetrafluoroethylene having a melting point lower than the curing temperature as a fluororesin. As can be seen from Table 4, with the powder coatings of Comparative Examples 1 and 2, the desired texture pattern was not obtained in any of the coating films. Comparative Examples 3 and 4
In any of the powder coatings, blow unevenness occurred during coating, the desired textured pattern could not be obtained, and a decrease in coating film physical properties was also observed.
【0055】実施例5〜11 表5または表7に示した成分を用いて、実施例1〜4と
同じ方法により凹凸模様形成性粉体塗料を製造し、実施
例1〜4と同じ方法により塗装を行った。次いで表6ま
たは表8に示した焼付条件において加熱硬化させた後、
塗膜外観および塗膜物性について評価を行った。結果を
表6、表8、図5〜図11に示す。Examples 5 to 11 By using the components shown in Table 5 or Table 7, powder coatings having an uneven pattern were produced in the same manner as in Examples 1 to 4, and were prepared in the same manner as in Examples 1 to 4. Painted. Then, after heating and curing under the baking conditions shown in Table 6 or Table 8,
The coating film appearance and physical properties were evaluated. The results are shown in Tables 6 and 8, and FIGS.
【0056】[0056]
【表5】 [Table 5]
【0057】表5の注 *1 AN720:ポリエステル樹脂、酸価=60mg
KOH/g、Vianova Resins社製、商標 *2 GV150:ポリエステル樹脂、水酸基価=34
mgKOH/g、日本ユピカ(株)製、商標 *3 DER663U:エポキシ樹脂、エポキシ当量=
775g/eq.、Dow Chemicals社製、
商標 *4 B1530:アダクト体イソシアネート硬化剤、
イソシアネート当量=280g/eq.、CREANO
VA社製、商標 *5 モダフロー:レベリング剤、MONSANT社
製、商標 *6 ブタフロー:硬化促進剤、ESTRON Che
mical Inc.製、商標 *7 PTFE:DYNEON PTFE、ポリテトラ
フルオロエチレン、フッ素含量=76重量%、融点=3
20℃、DYNEON社製、商標 *8 PVdF:ポリフッ化ビニリデン、フッ素含量=
59重量%、融点=156〜178℃、elf ato
chem社製、商標Notes to Table 5 * 1 AN720: polyester resin, acid value = 60 mg
KOH / g, manufactured by Vianova Resins, trademark * 2 GV150: polyester resin, hydroxyl value = 34
mgKOH / g, manufactured by Nippon Yupika Co., Ltd., trademark * 3 DER663U: epoxy resin, epoxy equivalent =
775 g / eq. Manufactured by Dow Chemicals,
Trademark * 4 B1530: Adduct isocyanate curing agent,
Isocyanate equivalent = 280 g / eq. , CREANO
VA, trademark * 5 Modaflow: leveling agent, MONSANT, trademark * 6 Butaflow: curing accelerator, ESTRON Che
medical Inc. * 7 PTFE: DYNEON PTFE, polytetrafluoroethylene, fluorine content = 76% by weight, melting point = 3
20 ° C., manufactured by DYNEON, trademark * 8 PVdF: polyvinylidene fluoride, fluorine content =
59% by weight, melting point = 156-178 ° C., elf ato
Chem, trademark
【0058】[0058]
【表6】 *1〜*10 表2参照[Table 6] * 1 to * 10 See Table 2
【0059】[0059]
【表7】 *1〜*8 表5参照[Table 7] * 1 to * 8 See Table 5
【0060】[0060]
【表8】 *1〜*10 表2参照[Table 8] * 1 to * 10 See Table 2
【0061】実施例5〜8はフッ素樹脂(B)として融
点が320℃のポリテトラフルオロエチレンを異なる重
量部用いたハイブリッド系粉体塗料またはウレタン系粉
体塗料、実施例9は実施例6のウレタン系粉体塗料の塗
膜厚を変えた例、実施例10は実施例6のウレタン系粉
体塗料の焼付条件を変えた例、実施例11はフッ素樹脂
(B)として融点が156〜178℃のポリフッ化ビニ
リデンを用いたハイブリッド系粉体塗料である。Examples 5 to 8 are hybrid powder coatings or urethane powder coatings using different parts by weight of polytetrafluoroethylene having a melting point of 320 ° C. as the fluororesin (B). Example 10 in which the coating thickness of the urethane-based powder coating was changed, Example 10 in which the baking conditions of the urethane-based powder coating in Example 6 were changed, and Example 11 in which the melting point was 156 to 178 as the fluororesin (B). This is a hybrid powder coating material using polyvinylidene fluoride at a temperature of ° C.
【0062】表6および表8からわかるように、実施例
5〜11のいずれの凹凸模様形成性粉体塗料において
も、塗装された塗膜はテクスチュア調の模様が被塗物上
に形成され、優れた意匠性と共に良好な塗膜物性を示す
塗膜が得られた。As can be seen from Tables 6 and 8, in any of the uneven pattern-forming powder coatings of Examples 5 to 11, the applied coating film had a textured pattern formed on the substrate. A coating film exhibiting good design properties together with excellent design properties was obtained.
【0063】比較例5、6 表9に示した成分を用いて、実施例1〜4と同じ方法に
より粉体塗料を製造し、実施例1〜4と同じ方法により
塗装を行った。次いで表9に示した焼付条件において加
熱硬化させた後、塗膜外観および塗膜物性について評価
を行った。結果を表10および図14に示す。Comparative Examples 5 and 6 Using the components shown in Table 9, powder coatings were produced in the same manner as in Examples 1 to 4, and coating was carried out in the same manner as in Examples 1 to 4. Next, after curing by heating under the baking conditions shown in Table 9, the appearance and physical properties of the coating film were evaluated. The results are shown in Table 10 and FIG.
【0064】[0064]
【表9】 *1〜*8 表5参照[Table 9] * 1 to * 8 See Table 5
【0065】[0065]
【表10】 *1〜*10 表2参照 *11 粉体塗料を得ることができず、試験できなかった。[Table 10] * 1 to * 10 See Table 2. * 11 A powder coating could not be obtained and could not be tested.
【0066】比較例5はポリテトラフルオロエチレンを
多量に配合したポリエステル/ウレタン系粉体塗料、比
較例6はフッ素樹脂として硬化温度より融点が低いポリ
フッ素ビニリデンを用いた粉体塗料である。表10から
わかるように、比較例5では熱可塑性を示すフッ素樹脂
成分(B)の比率が高くなるため溶融混練後のハンマー
式衝撃粉砕機で粉砕が困難となり、粉体塗料を製造する
ことができなかった。また比較例6では塗膜形成樹脂が
硬化するときにフッ素樹脂が溶融してしまい、目的とす
るテクスチュア調模様は得られなかった。Comparative Example 5 is a polyester / urethane-based powder coating containing a large amount of polytetrafluoroethylene, and Comparative Example 6 is a powder coating using polyvinylidene fluoride having a melting point lower than the curing temperature as a fluororesin. As can be seen from Table 10, in Comparative Example 5, since the ratio of the fluororesin component (B) exhibiting thermoplasticity was high, pulverization was difficult with a hammer-type impact pulverizer after melt-kneading, and powder coatings could be produced. could not. Further, in Comparative Example 6, the fluororesin melted when the coating film forming resin was cured, so that the desired textured pattern could not be obtained.
【0067】図1〜図11からわかるように、実施例1
〜11のいずれの硬化塗膜も凹凸の大小は異なるもの
の、テクスチュア調凹凸模様が観測された。これに対し
て、図12〜14(比較例1、2、6)では凹凸模様が
観測されなかった。図1〜3(実施例1〜3)はフッ素
樹脂(B)の配合割合の違いによる表面粗さ曲線を示し
ており、フッ素樹脂(B)の配合割合が多くなるほど凹
凸は大きくなる傾向が認められる。また図6〜8(実施
例6〜8)についても図1〜3と同じ傾向が認められ
る。As can be seen from FIGS. 1 to 11, the first embodiment
In any of the cured coating films of Nos. 1 to 11, the texture-like uneven pattern was observed, though the size of the unevenness was different. In contrast, in FIGS. 12 to 14 (Comparative Examples 1, 2, and 6), no uneven pattern was observed. FIGS. 1 to 3 (Examples 1 to 3) show surface roughness curves depending on the mixing ratio of the fluororesin (B), and the unevenness tends to increase as the mixing ratio of the fluororesin (B) increases. Can be 6 to 8 (Examples 6 to 8) show the same tendency as in FIGS.
【図1】実施例1で得られた硬化塗膜の表面粗さ曲線を
示すグラフである。FIG. 1 is a graph showing a surface roughness curve of a cured coating film obtained in Example 1.
【図2】実施例2で得られた硬化塗膜の表面粗さ曲線を
示すグラフである。FIG. 2 is a graph showing a surface roughness curve of a cured coating film obtained in Example 2.
【図3】実施例3で得られた硬化塗膜の表面粗さ曲線を
示すグラフである。FIG. 3 is a graph showing a surface roughness curve of a cured coating film obtained in Example 3.
【図4】実施例4で得られた硬化塗膜の表面粗さ曲線を
示すグラフである。FIG. 4 is a graph showing a surface roughness curve of a cured coating film obtained in Example 4.
【図5】実施例5で得られた硬化塗膜の表面粗さ曲線を
示すグラフである。FIG. 5 is a graph showing a surface roughness curve of a cured coating film obtained in Example 5.
【図6】実施例6で得られた硬化塗膜の表面粗さ曲線を
示すグラフである。FIG. 6 is a graph showing a surface roughness curve of a cured coating film obtained in Example 6.
【図7】実施例7で得られた硬化塗膜の表面粗さ曲線を
示すグラフである。FIG. 7 is a graph showing a surface roughness curve of a cured coating film obtained in Example 7.
【図8】実施例8で得られた硬化塗膜の表面粗さ曲線を
示すグラフである。FIG. 8 is a graph showing a surface roughness curve of a cured coating film obtained in Example 8.
【図9】実施例9で得られた硬化塗膜の表面粗さ曲線を
示すグラフである。FIG. 9 is a graph showing a surface roughness curve of a cured coating film obtained in Example 9.
【図10】実施例10で得られた硬化塗膜の表面粗さ曲
線を示すグラフである。FIG. 10 is a graph showing a surface roughness curve of a cured coating film obtained in Example 10.
【図11】実施例11で得られた硬化塗膜の表面粗さ曲
線を示すグラフである。FIG. 11 is a graph showing a surface roughness curve of a cured coating film obtained in Example 11.
【図12】比較例1で得られた硬化塗膜の表面粗さ曲線
を示すグラフである。FIG. 12 is a graph showing a surface roughness curve of a cured coating film obtained in Comparative Example 1.
【図13】比較例2で得られた硬化塗膜の表面粗さ曲線
を示すグラフである。FIG. 13 is a graph showing a surface roughness curve of a cured coating film obtained in Comparative Example 2.
【図14】比較例6で得られた硬化塗膜の表面粗さ曲線
を示すグラフである。FIG. 14 is a graph showing a surface roughness curve of a cured coating film obtained in Comparative Example 6.
───────────────────────────────────────────────────── フロントページの続き Fターム(参考) 4J038 CD091 CD092 CD112 CD122 CE052 CG001 DA162 DB001 DB002 DD001 DG262 DG302 GA12 JA35 JA64 JB01 JB12 JB17 KA03 MA02 NA01 PA02 PB05 PB09 PC02 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J038 CD091 CD092 CD112 CD122 CE052 CG001 DA162 DB001 DB002 DD001 DG262 DG302 GA12 JA35 JA64 JB01 JB12 JB17 KA03 MA02 NA01 PA02 PB05 PB09 PC02
Claims (7)
(A)100重量部に対して、フッ素樹脂(B)を0.
01〜20重量部の割合で含む粉体塗料であり、 フッ素樹脂(B)は塗膜形成樹脂(A)の溶融温度およ
び硬化温度において溶融せず、フッ素含有量が10〜8
5重量%のフッ素樹脂であり、 塗膜形成樹脂(A)がフッ素樹脂(B)に融着している
凹凸模様形成性粉体塗料。1. A fluororesin (B) is added in an amount of 100 parts by weight of a thermosetting film-forming resin (A) which is solid at room temperature.
A fluorine-containing resin (B) that does not melt at the melting and curing temperatures of the film-forming resin (A) and has a fluorine content of 10 to 8 parts by weight.
An uneven pattern-forming powder coating material comprising 5% by weight of a fluororesin, wherein the coating film forming resin (A) is fused to the fluororesin (B).
340℃のフッ素樹脂である請求項1記載の凹凸模様形
成性粉体塗料。2. The fluororesin (B) has a melting temperature of 150 to
2. The powdery coating material having an uneven pattern according to claim 1, which is a fluororesin at 340.degree.
エチレン、ポリクロロトリフルオロエチレン、ポリフッ
化ビニリデン、テトラフルオロエチレン・ペルフルオロ
アルキルビニルエーテル共重合体、テトラフルオロエチ
レン・ペルフルオロプロピレン共重合体、またはエチレ
ン・テトラフルオロエチレン共重合体である請求項1ま
たは2記載の凹凸模様形成性粉体塗料。3. The method according to claim 1, wherein the fluororesin (B) is polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / perfluoroalkylvinyl ether copolymer, tetrafluoroethylene / perfluoropropylene copolymer, or ethylene. The uneven pattern-forming powder coating according to claim 1 or 2, which is a tetrafluoroethylene copolymer.
で塗膜形成樹脂(A)を加熱硬化させて形成される塗膜
が、中心線平均粗さ(Ra)が2〜20μm、10点平
均粗さ(Rz)が10〜100μm、1cmあたりのピ
ーク数(Pc)が10〜40個の凹凸模様の塗膜である
請求項1ないし3のいずれかに記載の凹凸模様形成性粉
体塗料。4. A coating film formed by heating and curing the coating film forming resin (A) at a temperature lower than the melting temperature of the fluororesin (B) has a center line average roughness (Ra) of 2 to 20 μm, The uneven pattern-forming powder according to any one of claims 1 to 3, which is a coating film having an uneven pattern having a point average roughness (Rz) of 10 to 100 µm and a peak number (Pc) of 1 to 40 per cm. paint.
てフッ素樹脂(B)を0.01〜20重量部の割合で添
加した後、塗膜形成樹脂(A)をその硬化温度未満の温
度で加熱溶融させて混合し、次に冷却したのち粉砕する
請求項1ないし4のいずれかに記載の凹凸模様形成性粉
体塗料の製造方法。5. After adding the fluororesin (B) at a ratio of 0.01 to 20 parts by weight to 100 parts by weight of the film-forming resin (A), the film-forming resin (A) is cooled below its curing temperature. 5. The method for producing an uneven pattern-forming powder coating according to claim 1, wherein the powder coating is heated and melted at a temperature of, mixed, cooled, and then pulverized.
凸模様形成性粉体塗料の塗膜の形成方法であって、フッ
素樹脂(B)の溶融温度未満の温度で塗膜形成樹脂
(A)を加熱硬化させて塗膜を形成する塗膜の形成方
法。6. The method for forming a coating film of a powder coating having a concavo-convex pattern according to any one of claims 1 to 4, wherein the coating film-forming resin is formed at a temperature lower than the melting temperature of the fluororesin (B). A method for forming a coating film in which A) is cured by heating to form a coating film.
凸模様形成性粉体塗料を被塗物に塗布し、フッ素樹脂
(B)の溶融温度未満の温度で塗膜形成樹脂(A)を加
熱硬化させて塗膜を形成した塗装物。7. A coating film forming resin (A) which is obtained by applying the concavo-convex pattern forming powder coating material according to any one of claims 1 to 4 to an object to be coated at a temperature lower than the melting temperature of the fluororesin (B). A coated object formed by heating to cure a film.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30245499A JP3876575B2 (en) | 1999-10-25 | 1999-10-25 | Irregular pattern-forming powder coating, method for producing the same, method for forming a coating film, and painted product |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP30245499A JP3876575B2 (en) | 1999-10-25 | 1999-10-25 | Irregular pattern-forming powder coating, method for producing the same, method for forming a coating film, and painted product |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2001123104A true JP2001123104A (en) | 2001-05-08 |
JP3876575B2 JP3876575B2 (en) | 2007-01-31 |
Family
ID=17909142
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP30245499A Expired - Fee Related JP3876575B2 (en) | 1999-10-25 | 1999-10-25 | Irregular pattern-forming powder coating, method for producing the same, method for forming a coating film, and painted product |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3876575B2 (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003029369A1 (en) * | 2001-09-27 | 2003-04-10 | Asahi Glass Company, Limited | Composition for fluororesin powder coating material |
US20110287271A1 (en) * | 2009-01-06 | 2011-11-24 | Ewald Doerken Ag | Method for producing a coating powder |
JP2012121323A (en) * | 2010-11-17 | 2012-06-28 | Nippon Steel Corp | Chromate-free colored coated metal sheet |
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 |
JP2018525240A (en) * | 2015-05-01 | 2018-09-06 | ヴァルスパー・ソーシング・インコーポレーテッド | High performance texture coating |
JP2019044098A (en) * | 2017-09-04 | 2019-03-22 | ソマール株式会社 | Epoxy resin powder coating composition |
CN111359860A (en) * | 2020-03-30 | 2020-07-03 | 北京***汇技术有限公司 | Clamp spring polyester resin coating processing method and production line |
JP2021038323A (en) * | 2019-09-04 | 2021-03-11 | 株式会社デンソー | Powdered paint, lubricant film, and component |
-
1999
- 1999-10-25 JP JP30245499A patent/JP3876575B2/en not_active Expired - Fee Related
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003029369A1 (en) * | 2001-09-27 | 2003-04-10 | Asahi Glass Company, Limited | Composition for fluororesin powder coating material |
US7153907B2 (en) | 2001-09-27 | 2006-12-26 | Asahi Glass Company, Limited | Composition for fluororesin powder coating material |
US20110287271A1 (en) * | 2009-01-06 | 2011-11-24 | Ewald Doerken Ag | Method for producing a coating powder |
CN102272242A (en) * | 2009-01-06 | 2011-12-07 | 艾华德·多肯股份公司 | Method for producing a powder coating |
JP2012514662A (en) * | 2009-01-06 | 2012-06-28 | エーヴァルト デルケン アーゲー | Method for producing coated powder and coated powder |
JP2012121323A (en) * | 2010-11-17 | 2012-06-28 | Nippon Steel Corp | Chromate-free colored coated metal sheet |
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 |
JP2018525240A (en) * | 2015-05-01 | 2018-09-06 | ヴァルスパー・ソーシング・インコーポレーテッド | High performance texture coating |
JP2019044098A (en) * | 2017-09-04 | 2019-03-22 | ソマール株式会社 | Epoxy resin powder coating composition |
JP7020825B2 (en) | 2017-09-04 | 2022-02-16 | ソマール株式会社 | Epoxy resin powder coating composition |
JP2021038323A (en) * | 2019-09-04 | 2021-03-11 | 株式会社デンソー | Powdered paint, lubricant film, and component |
JP7259652B2 (en) | 2019-09-04 | 2023-04-18 | 株式会社デンソー | Powder coatings, lubricating films, and parts |
CN111359860A (en) * | 2020-03-30 | 2020-07-03 | 北京***汇技术有限公司 | Clamp spring polyester resin coating processing method and production line |
Also Published As
Publication number | Publication date |
---|---|
JP3876575B2 (en) | 2007-01-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7122585B2 (en) | Coating powders, methods of manufacture thereof, and articles formed therefrom | |
CA2206481C (en) | Cathodic disbondment resistant epoxy powder coating composition and reinforcing steel bar coated therewith | |
CN110408311B (en) | Weather-resistant powder coating and preparation method thereof | |
JPH06293867A (en) | Matte powdery coating composition, method for coating and film made therefrom | |
JP3876575B2 (en) | Irregular pattern-forming powder coating, method for producing the same, method for forming a coating film, and painted product | |
US20040102561A1 (en) | Powder coating composition | |
US20040157961A1 (en) | Curable coating powders and powder coatings formed therefrom | |
WO2002051922A2 (en) | Powder coating compositions containing reactive nanoparticles | |
CA2426916C (en) | Coating powders, methods of manufacture thereof and articles formed therefrom | |
JP2000273390A (en) | Powder coating composition | |
JP2007091802A (en) | Uneven pattern-forming powder coating composition | |
JP4894096B2 (en) | Fluoropolymer powder manufacturing method | |
WO2017204085A1 (en) | Powder coating composition, process for producing powder coating composition, and coated article | |
JP3605940B2 (en) | Irregular pattern-forming powder coating, method for producing the same, and coated object | |
JP2591664B2 (en) | Powder coating composition | |
CN112480794A (en) | Mixed extinction powder coating and preparation method thereof | |
JP2002194297A (en) | Designing powder coating composition for precoat material, method for forming designing coating film and precoat material with designing coating | |
JPH0762269A (en) | Powder coating composition giving honeycomb pattern, its coating method, coating film and coated product | |
JPH05271577A (en) | Powder coating composition capable of providing hexagonal pattern, method for coating the same, film and coated product produced therefrom | |
JP2001139887A (en) | Metallic powder coating composition | |
JP2001311045A (en) | Designable powder coating composition, method for forming designed coating film and coated article having design | |
JP2000204289A (en) | Powder paint composition | |
JP2000345076A (en) | Thermosetting flat powder coating composition | |
JP2008063581A (en) | Method for manufacturing silver-metallic powder coating for tribocharging spray gun | |
JPH0586821B2 (en) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040405 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20060706 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060711 |
|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060908 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20061010 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20061023 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
LAPS | Cancellation because of no payment of annual fees |