JP5604870B2 - Thermosetting coating resin composition - Google Patents
Thermosetting coating resin composition Download PDFInfo
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- JP5604870B2 JP5604870B2 JP2009514568A JP2009514568A JP5604870B2 JP 5604870 B2 JP5604870 B2 JP 5604870B2 JP 2009514568 A JP2009514568 A JP 2009514568A JP 2009514568 A JP2009514568 A JP 2009514568A JP 5604870 B2 JP5604870 B2 JP 5604870B2
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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Description
本発明は、自動車ボディの塗膜のように高度の美粧性と優れた塗膜性能、例えば、塗膜の耐擦り傷性、耐亜硫酸性および屋外暴露時における優れた光沢特性が要求される分野で用いられ、また熱変形温度の低いプラスチックへの応用の展開も可能な熱硬化型被膜用組成物に関するものである。
本願は、２００８年３月６日に、日本に出願された特願２００８−５６５４５号に基づき優先権を主張し、その内容をここに援用する。The present invention is used in fields where a high degree of cosmetics and excellent coating performance such as a coating film of an automobile body are required, such as scratch resistance, sulfite resistance, and excellent gloss characteristics during outdoor exposure. The present invention relates to a thermosetting coating composition that can be used and can be applied to plastics having a low heat distortion temperature.
This application claims priority on March 6, 2008 based on Japanese Patent Application No. 2008-56545 for which it applied to Japan, and uses the content for it here.
これまで自動車用トップコート等に有用な塗料としては、耐候性および美粧性に優れた性能を有することから、アクリル−メラミン系樹脂が多く使用されている。しかし、アクリル−メラミン系樹脂はメラミン樹脂を硬化剤として使用するために耐亜硫酸性に劣り、これを塗料に適用した場合、酸性雨により塗膜に雨ジミが発生し、外観が低下するという欠点を有する。 Until now, acrylic-melamine-based resins have been widely used as paints useful for automobile top coats and the like because they have excellent weather resistance and cosmetic properties. However, acrylic-melamine resins are inferior in sulfite resistance due to the use of melamine resin as a curing agent, and when this is applied to paints, the appearance of rain stains on the coating film due to acid rain and the appearance is reduced. Have
この問題を解決するために、メラミン重合体を使用せずに、酸・エポキシ硬化系を用いる熱硬化性組成物が提案されている。 In order to solve this problem, a thermosetting composition using an acid / epoxy curing system without using a melamine polymer has been proposed.
しかし近年、自動車産業分野では塗膜の耐久性の問題、特にスリキズによる塗膜外観の低位が問題となっている。酸・エポキシ硬化系を用いる熱硬化性組成物を塗布して得られる塗膜表面では、洗車ブラシ、コンパウンドやワックス等の研磨剤、走行中に舞い上がる砂粒、異物との接触などによって、生じるスリキズが目立ちやすく、特に、自動洗車機の洗車ブラシによって発生するスリキズの問題は、国内外を問わずその解決が強く望まれている。このような問題点の解決策として、これまで、ＵＶ硬化系やシリコン系塗料などを用いるハードコート技術が提案され、また、その他、特開２００２−１７９９８７公報には熱硬化系であるポリイソシアネートを用いて架橋されるヒドロキシ官能性（メタ）アクリレート共重合体に基づく塗料が提案されている。しかし、この塗料は硬度、耐候性および耐汚染性が不十分であった。
本発明の目的は、塗膜を構成する塗料中の樹脂成分として特定のアクリル熱硬化塗膜を形成し得るものを使用することにより、従来のハーフエステル化した共重合体、エポキシ基および水酸基を有する化合物を含有する熱硬化性組成物の有する耐亜硫酸性、耐候性を維持しつつ、従来のＵＶ硬化系やシリコン系塗料、ウレタン系アクリル熱硬化塗膜より耐擦り傷性および美粧性、特に耐候性試験後の擦り傷性、耐汚染性に優れた塗膜を形成する熱硬化性被覆用樹脂組成物を提供することにある。 The object of the present invention is to use a conventional half-esterified copolymer, epoxy group and hydroxyl group by using what can form a specific acrylic thermosetting coating film as a resin component in the coating material constituting the coating film. While maintaining the sulfite resistance and weather resistance of the thermosetting composition containing the compound having the above, it is more resistant to scratches and cosmetics, particularly weather resistance than conventional UV curing systems, silicone coatings, and urethane acrylic thermosetting coatings. Another object of the present invention is to provide a thermosetting coating resin composition that forms a coating film having excellent scratch resistance and stain resistance after a property test.
[１] 本発明の第１の要旨は、下記式（１）で表される単量体（ａ）単位、
第２級水酸基含有ポリオキシアルキレンモノ(メタ)アクリレート単量体（ｂ）単位、及びイソボルニル(メタ)アクリレート単量体（ｃ）単位を含有し、前記単量体（ａ）単位の含有量（質量）が前記単量体（ｂ）単位の含有量よりも大きい熱硬化性被覆用樹脂組成物用アクリル系共重合体（Ａ）
[２] 本発明の第２の要旨は、前記アクリル系共重合体（Ａ）と、ポリイソシアネート硬化剤（Ｂ）とを含有する熱硬化性被覆用樹脂組成物である。
[３] 本発明の第３の要旨は、[２]に記載の熱硬化性被膜用樹脂組成物を硬化させて得られる塗膜。
[４] 本発明の第４の要旨は、[３]に記載の塗膜を有する物品。[1] The first gist of the present invention is a monomer (a) unit represented by the following formula (1):
A secondary hydroxyl group-containing polyoxyalkylene mono (meth) acrylate monomer (b) unit and an isobornyl (meth) acrylate monomer (c) unit, and the content of the monomer (a) unit ( Acrylic copolymer for thermosetting coating resin composition (A) having a mass) greater than the content of the monomer (b) unit
[2] A second gist of the present invention is a thermosetting coating resin composition containing the acrylic copolymer (A) and a polyisocyanate curing agent (B).
[3] A third aspect of the present invention is a coating film obtained by curing the thermosetting film resin composition according to [2].
[4] A fourth aspect of the present invention is an article having the coating film according to [3].
なお、本発明においては、（メタ）アクリルとはアクリルとメタクリルの総称である。 In the present invention, (meth) acryl is a general term for acrylic and methacrylic.
本発明の熱硬化性被膜用樹脂組成物を用いると、外観、（初期、耐候後）耐擦り傷性、外観仕上がり性、耐候性、貯蔵安定性、耐汚染性、硬化性、硬度、耐亜硫酸性の優れた塗膜の提供が可能であり、工業上非常に有益なものである。 When the resin composition for thermosetting coatings of the present invention is used, appearance, (initial, after weather resistance) scratch resistance, appearance finish, weather resistance, storage stability, stain resistance, curability, hardness, sulfite resistance It is possible to provide an excellent coating film, which is very useful industrially.
重合して(メタ)アクリル酸エステル単量体（ａ）単位（以下、単量体（ａ）単位ともいう）を与える単量体としては、例えば、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレートなどが挙げられ、これらを単独であるいは二種以上を併用して使用することができる。単量体（ａ）単位のエステル部位のアルキル基の炭素数は２〜４であり、第２級水酸基を有することが重要である。これは、前記アルキル基の炭素数が５以上になると塗膜外観、ポットライフが低くなるためである。また、前記アルキル基に結合する水酸基が第１級である場合、または前記アルキル基の炭素数が１である場合は仕上がり外観が低下するためである。この理由は、第１級水酸基と第２級水酸基との硬化速度の違いにあると考えている。すなわち、ベースコート用塗料を塗装し、次いでクリヤーコート用塗料を重ね塗りした後、加熱硬化させて積層被覆を得る、いわゆる２コート・１ベーク塗装方式においては、ベースコート層が固まる前にクリヤーコート層が固まると外観が低下してしまうが、単量体（ａ）単位に含まれる水酸基が第１級であると硬化速度が速く、第２級だと遅いからであると推測している。 Examples of the monomer that polymerizes to give a (meth) acrylic acid ester monomer (a) unit (hereinafter also referred to as a monomer (a) unit) include 2-hydroxypropyl (meth) acrylate, 2- Hydroxybutyl (meth) acrylate etc. are mentioned, These can be used individually or in combination of 2 or more types. It is important that the alkyl group in the ester moiety of the monomer (a) unit has 2 to 4 carbon atoms and has a secondary hydroxyl group. This is because when the carbon number of the alkyl group is 5 or more, the coating film appearance and pot life are lowered. Moreover, when the hydroxyl group couple | bonded with the said alkyl group is primary, or when the carbon number of the said alkyl group is 1, it is because a finished external appearance will fall. The reason for this is considered to be the difference in curing rate between the primary hydroxyl group and the secondary hydroxyl group. In other words, in the so-called two-coat / one-bake coating method in which a base coat paint is applied and then a clear coat paint is repeatedly applied and then cured by heating, a clear coat layer is formed before the base coat layer is solidified. When it hardens, the appearance deteriorates, but it is presumed that the curing rate is fast when the hydroxyl group contained in the monomer (a) unit is primary, and it is slow when it is secondary.
また、本発明では単量体（ａ）単位の含有量（質量）が第２級水酸基含有ポリオキシアルキレンモノ(メタ)アクリレート単量体（ｂ）単位（以下、単量体（ｂ）単位ともいう）の含有量よりも大きいことが重要である。これは、単量体（ｂ）単位は耐擦り傷性を付与する効果があるが、親水性が高いため、単量体（ａ）単位より多いと耐汚染性が不十分となるためである。また、単量体（ｂ）単位の含有量が多いと重合体の架橋間分子量が大きくなり、それに起因して硬度、耐候性、が低下するおそれがあり好ましくない。 In the present invention, the content (mass) of the monomer (a) unit is the secondary hydroxyl group-containing polyoxyalkylene mono (meth) acrylate monomer (b) unit (hereinafter referred to as the monomer (b) unit). It is important that the content is greater than This is because the monomer (b) unit has an effect of imparting scratch resistance, but has high hydrophilicity, and if it is more than the monomer (a) unit, the stain resistance becomes insufficient. Moreover, when there is much content of a monomer (b) unit, the molecular weight between bridge | crosslinking of a polymer becomes large, and there exists a possibility that hardness and a weather resistance may fall resulting from it, and it is unpreferable.
単量体（ａ）単位の含有量はアクリル系共重合体（Ａ）に対し、１０〜５０質量％が好ましく、１０〜３５質量％がより好ましい。これは、１０質量％未満では硬化性、硬度が不十分になり、５０質量％を越えると、初期耐擦り傷性、耐候性試験後耐擦り傷性が不十分となるためである。単量体（ａ）単位と第１級水酸基含有（メタ）アクリレートを併用してもよいが、外観の悪化を抑制するために、第１級水酸基含有（メタ）アクリレートの使用量はアクリル系共重合体（Ａ）に対し１５質量％未満が好ましい。 The content of the monomer (a) unit is preferably 10 to 50% by mass and more preferably 10 to 35% by mass with respect to the acrylic copolymer (A). This is because if it is less than 10% by mass, the curability and hardness are insufficient, and if it exceeds 50% by mass, the initial scratch resistance and the scratch resistance after the weather resistance test are insufficient. Although the monomer (a) unit and primary hydroxyl group-containing (meth) acrylate may be used in combination, the amount of primary hydroxyl group-containing (meth) acrylate used is an acrylic copolymer in order to suppress deterioration of the appearance. Less than 15 mass% is preferable with respect to a polymer (A).
なお、アクリル系共重合体（Ａ）中の各単量体単位の含有量はＮＭＲやガスクロマトグラフ等により定量することができる。 The content of each monomer unit in the acrylic copolymer (A) can be quantified by NMR, gas chromatograph or the like.
重合して単量体（ｂ）単位を与える第２級水酸基含有ポリオキシアルキレンモノ(メタ)アクリレートとしては、ポリアルキレングリコールと(メタ)アクリレートの反応生成物が挙げられる。詳しくは、以下の一般式を有する。
(式（２）中、Ｒ１は水素原子又はメチル基であり、ｎ、ｍ、ｌはそれぞれ独立して０〜１０の整数であり、ｎ、ｍ、ｌの少なくとも１つが１以上である。ポリオキシアルキレン構造はブロック共重合体だけでなく、ランダム共重合体も含む。)
上記式（２）で表されるポリアルキレングリコール(メタ)アクリレートのうち、好ましくはｍが１以上のポリプロピレングリコール部位を持つものである。具体的には以下に示す日本油脂製「ブレンマー」が挙げられる。なお、括弧内は式（２）との対応を示す。(In Formula (2), R1 is a hydrogen atom or a methyl group, n, m, and l are each independently an integer of 0 to 10, and at least one of n, m, and l is 1 or more. (Oxyalkylene structures include not only block copolymers but also random copolymers.)
Of the polyalkylene glycol (meth) acrylates represented by the above formula (2), those having a polypropylene glycol moiety where m is preferably 1 or more are preferred. Specific examples include “Blemmer” made by Nippon Oils and Fats shown below. The parentheses indicate the correspondence with the formula (2).
ブレンマーＰＰ−１０００（Ｒ１＝メチル基、ｎ＝０、ｍ＝４〜６、ｌ＝０の化合物）、ブレンマーＰＰ−５００（Ｒ１＝メチル基、ｎ＝０、ｍ＝９、ｌ＝０の化合物）、ブレンマーＰＰ−８００（Ｒ１＝メチル基、ｎ＝０、ｍ＝１３、ｌ＝０の化合物）、ブレンマーＡＰ−１５０（Ｒ１＝水素原子、ｎ＝０、ｍ＝３、ｌ＝０の化合物）、ブレンマーＡＰ−４００（Ｒ１＝水素原子、ｎ＝０、ｍ＝６、ｌ＝０の化合物）、ブレンマーＡＰ−５５０（Ｒ１＝水素原子、ｎ＝０、ｍ＝９、ｌ＝０の化合物）、ブレンマーＡＰ−８００（Ｒ１＝水素原子、ｎ＝０、ｍ＝１３、ｌ＝０の化合物）、ブレンマー５０ＰＥＰ−３００（Ｒ１＝メチル基、ｎ＝３．５、ｍ＝２．５、ｌ＝０の化合物）、ブレンマー７０ＰＥＰ−３５０（Ｒ１＝メチル基、ｎ＝５、ｍ＝２、ｌ＝０の化合物）、ブレンマーＡＥＰ、ブレンマー５５ＰＥＴ−４００（Ｒ１＝メチル基、ｎ＝５、ｍ＝０、ｌ＝２の化合物）、ブレンマー３０ＰＥＴ−８００（Ｒ１＝メチル基、ｎ＝６、ｍ＝０、ｌ＝１０の化合物）、ブレンマー５５ＰＥＴ−８００（Ｒ１＝メチル基、ｎ＝１０、ｍ＝０、ｌ＝５の化合物）、ブレンマー３０ＰＰＴ−８００（Ｒ１＝メチル基、ｎ＝０、ｍ＝４、ｌ＝８の化合物）、ブレンマー５０ＰＰＴ−８００（Ｒ１＝メチル基、ｎ＝０、ｍ＝７、ｌ＝６の化合物）、ブレンマー７０ＰＰＴ−８００（Ｒ１＝メチル基、ｎ＝０、ｍ＝１０、ｌ＝３の化合物）、ブレンマーＡＰＴ、ブレンマー１０ＰＰＢ−５００Ｂ（Ｒ１＝メチル基、ｎ＝０、ｍ＝１、ｌ＝６の化合物）、ブレンマー１０ＡＰＢ−５００Ｂ（Ｒ１＝水素原子、ｎ＝０、ｍ＝１、ｌ＝６の化合物）。 Blemmer PP-1000 (R1 = methyl group, n = 0, m = 4-6, l = 0 compound), Blemmer PP-500 (R1 = methyl group, n = 0, m = 9, l = 0 compound) ), Blemmer PP-800 (R1 = methyl group, n = 0, m = 13, l = 0 compound), Blemmer AP-150 (R1 = hydrogen atom, n = 0, m = 3, l = 0 compound) ), Blemmer AP-400 (compound with R1 = hydrogen atom, n = 0, m = 6, l = 0), Blemmer AP-550 (compound with R1 = hydrogen atom, n = 0, m = 9, l = 0) ), Blemmer AP-800 (R1 = hydrogen atom, n = 0, m = 13, l = 0 compound), Blemmer 50PEP-300 (R1 = methyl group, n = 3.5, m = 2.5, l) = 0 compound), Blemmer 70PEP-350 (R1 = methyl group, n = , M = 2, l = 0 compound), Blemmer AEP, Blemmer 55PET-400 (R1 = methyl group, n = 5, m = 0, l = 2 compound), Blemmer 30PET-800 (R1 = methyl group, n = 6, m = 0, l = 10 compound), Blemmer 55PET-800 (R1 = methyl group, n = 10, m = 0, l = 5 compound), Blemmer 30PPT-800 (R1 = methyl group, n = 0, m = 4, l = 8 compound), Blemmer 50PPT-800 (R1 = methyl group, n = 0, m = 7, l = 6 compound), Blemmer 70PPT-800 (R1 = methyl group, n = 0, m = 10, l = 3 compound), Blemmer APT, Blemmer 10PPB-500B (R1 = methyl group, n = 0, m = 1, l = 6 compound), Blemmer 10APB-500B ( 1 = hydrogen atom, n = 0, m = 1, the compounds of the l = 6).
これらは単独であるいは二種以上を併用して使用することができる。本発明においては、硬化速度を適切に制御して塗膜外観を良好にするために、単量体（ｂ）単位が第２級水酸基を有することが重要である。
単量体（ｂ）単位の含有量はアクリル系共重合体（Ａ）に対し、５〜３５質量％が好ましく、５〜２５質量％がより好ましい。これは５質量％未満では初期耐擦り傷性、耐候性試験後耐擦り傷性が不十分になり、３５質量％を超えると、硬化性、耐汚染性が不十分となるためである。These can be used alone or in combination of two or more. In the present invention, it is important that the monomer (b) unit has a secondary hydroxyl group in order to appropriately control the curing rate to improve the appearance of the coating film.
The content of the monomer (b) unit is preferably 5 to 35% by mass and more preferably 5 to 25% by mass with respect to the acrylic copolymer (A). This is because if it is less than 5% by mass, the initial scratch resistance and scratch resistance after the weather resistance test will be insufficient, and if it exceeds 35% by mass, the curability and stain resistance will be insufficient.
さらにアクリル系共重合体（Ａ）はイソボルニル(メタ)アクリレート単量体（ｃ）単位（以下、単量体（ｃ）単位ともいう）を含むことにより、初期擦り傷性が良好となり、また、特に耐候性試験後の耐擦り傷性の低下を防ぐことができる。単量体（ｃ）単位の含有量は、アクリル系共重合体（Ａ）に対し、１０〜５０質量%が好ましい。１０質量％未満では硬度、耐汚染性が低くなり、５０質量％を超えると塗膜硬度が上がりすぎて耐擦り傷性が低下してしまう。 Further, the acrylic copolymer (A) contains an isobornyl (meth) acrylate monomer (c) unit (hereinafter also referred to as a monomer (c) unit), thereby improving initial scratch resistance, A reduction in scratch resistance after the weather resistance test can be prevented. The content of the monomer (c) unit is preferably 10 to 50% by mass with respect to the acrylic copolymer (A). If it is less than 10% by mass, the hardness and stain resistance will be low, and if it exceeds 50% by mass, the coating film hardness will be too high and the scratch resistance will be reduced.
さらにアクリル系共重合体（Ａ）には、上記単量体（ａ）単位〜（ｃ）単位以外のエチレン性不飽和単量体に由来する単量体単位（ｄ）（以下、単量体（ｄ）単位ともいう）が含有されていてもよい。重合して単量体（ｄ）単位を与えるエチレン性不飽和単量体としては、特に限定されるものではないが、先ず、カルボキシル基を有するエチレン性不飽和モノマーを挙げることができる。例えば、メタクリル酸、アクリル酸、フマール酸、イタコン酸、マレイン酸、クロトン酸、ビニル安息香酸、マレイン酸モノブチルエステル、イタコン酸モノメチルエステル、イタコン酸ブチルエステル等が挙げられ、これらを単独であるいは二種以上を併用して使用することもできる。 Furthermore, the acrylic copolymer (A) includes a monomer unit (d) derived from an ethylenically unsaturated monomer other than the above-mentioned monomer (a) unit to (c) unit (hereinafter referred to as a monomer). (D) (also referred to as a unit) may be contained. Although it does not specifically limit as an ethylenically unsaturated monomer which superposes | polymerizes and gives a monomer (d) unit, First, the ethylenically unsaturated monomer which has a carboxyl group can be mentioned. Examples include methacrylic acid, acrylic acid, fumaric acid, itaconic acid, maleic acid, crotonic acid, vinyl benzoic acid, maleic acid monobutyl ester, itaconic acid monomethyl ester, and itaconic acid butyl ester. It can also be used in combination of more than one species.
また、カルボキシル基を有するもの以外のエチレン性不飽和単量体の例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ｓｅｃ−ブチル（メタ）アクリレート、ｎ−ペンチル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、シクロヘプチル（メタ）アクリレート、アダマンチル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジヒドロジシクロペンタジエニル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート等の（メタ）アクリレート類、スチレン、ビニルトルエン、α−メチルスチレン等のスチレン誘導体、アクリロニトリル、メタクリロニトリル等のエチレン性不飽和ニトリル類、Ｎ−メトキシメチルアクリルアミド、Ｎ−エトキシメチルアクリルアミド、Ｎ−ブトキシメチルアクリルアミド等のＮ−アルコキシ置換アミド類、グリシジル（メタ）アクリレート、メタリルグリシジルエーテル等のエポキシ基含有エチレン性不飽和単量体類、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート等のエチレン性不飽和塩基性単量体類等が挙げられ、これらを単独であるいは二種以上を併用して使用することができる。 Examples of ethylenically unsaturated monomers other than those having a carboxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, i -Butyl (meth) acrylate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, nonyl (meth) ) Acrylate, isononyl (meth) acrylate, cycloheptyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dihydrodicyclopentadienyl (meth) acrylate, tricyclodecanyl (meth) (Meth) acrylates such as acrylate, styrene derivatives such as styrene, vinyltoluene and α-methylstyrene, ethylenically unsaturated nitriles such as acrylonitrile and methacrylonitrile, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N -N-alkoxy-substituted amides such as butoxymethylacrylamide, epoxy group-containing ethylenically unsaturated monomers such as glycidyl (meth) acrylate and methallyl glycidyl ether, dimethylamino Examples include ethylenically unsaturated basic monomers such as noethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, and these can be used alone or in combination of two or more.
単量体（ｄ）単位の含有量はアクリル系共重合体（Ａ）から単量体（ａ）単位〜（ｃ）単位の含有量の合計を引いた値であり、５〜５０質量％が好ましい。 The content of the monomer (d) unit is a value obtained by subtracting the total content of the monomer (a) unit to the (c) unit from the acrylic copolymer (A), and 5 to 50% by mass. preferable.
アクリル系共重合体（Ａ）は、水酸基価は１３０〜１８０ｍｇＫＯＨ／ｇの範囲が好ましく、より好ましくは、１３５〜１７５ｍｇＫＯＨ／ｇの範囲である。これは、アクリル系共重合体（Ａ）の水酸基価が１３０ｍｇＫＯＨ／ｇ未満であると、硬化塗膜の硬度、耐擦り傷性が低下する傾向にあり、１８０ｍｇＫＯＨ／ｇを越えると、硬化塗膜の耐水性、耐衝撃性が低下する傾向にあるためである。 The acrylic copolymer (A) preferably has a hydroxyl value in the range of 130 to 180 mgKOH / g, and more preferably in the range of 135 to 175 mgKOH / g. This is because when the hydroxyl value of the acrylic copolymer (A) is less than 130 mgKOH / g, the hardness and scratch resistance of the cured coating film tend to decrease, and when it exceeds 180 mgKOH / g, This is because the water resistance and impact resistance tend to decrease.
アクリル系共重合体（Ａ）の酸価は１〜３０ｍｇＫＯＨ／ｇの範囲が好ましい。酸価が１ｍｇＫＯＨ／ｇより小さいと硬化性、硬度が低くなり、３０ｍｇＫＯＨ／ｇより大きいと外観が低下する傾向にあるためである。 The acid value of the acrylic copolymer (A) is preferably in the range of 1 to 30 mgKOH / g. This is because if the acid value is less than 1 mgKOH / g, the curability and hardness are lowered, and if it is greater than 30 mgKOH / g, the appearance tends to be lowered.
アクリル系共重合体（Ａ）の質量平均分子量は、２０００〜５００００であることが好ましい。これは、質量平均分子量が２０００未満であると、形成した塗膜の耐溶剤性、硬度、耐候性が低下する傾向にあり、５００００を越えると、美粧性や塗装時の溶剤揮発性が低下する傾向にあるためである。 The mass average molecular weight of the acrylic copolymer (A) is preferably 2000 to 50000. If the mass average molecular weight is less than 2000, the solvent resistance, hardness, and weather resistance of the formed coating film tend to decrease, and if it exceeds 50,000, the cosmetic properties and solvent volatility during coating decrease. It is because it is in a tendency.
本発明のアクリル系共重合体（Ａ）は、重合して単量体（ａ）単位〜（ｄ）単位を与える単量体を溶液重合法、塊状重合法、懸濁重合、乳化重合法等の既知の重合法により製造することができる。例えば、溶液重合法により上記アクリル系共重合体（Ａ）を製造する場合には、有機溶剤および重合開始剤の存在下に上記単量体を共重合させる。 The acrylic copolymer (A) of the present invention is obtained by polymerizing monomers that give monomers (a) to (d) units by solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, etc. These can be produced by known polymerization methods. For example, when the acrylic copolymer (A) is produced by a solution polymerization method, the monomer is copolymerized in the presence of an organic solvent and a polymerization initiator.
有機溶剤としては、イソプロパノール、ｎ−ブタノール、トルエン、キシレン、ソルベッソ１００、ソルベッソ１５０（エッソ社製の芳香族石油誘導体）、プロピレングリコールモノメチルエーテルアセテート、ＥＥＰソルベント（イーストマン製エステル溶剤）等の一般的なものを選択できる。重合開始剤としては、アゾビスイソブチロニトリル、過酸化ベンゾイル、クメンヒドロペルオキシド等の通常用いられる重合開始剤から選択できる。また、必要に応じて２−メルカプトエタノール、ｎ−オクチルメルカプタン等の連鎖移動剤を使用することができる。 Common organic solvents such as isopropanol, n-butanol, toluene, xylene, Solvesso 100, Solvesso 150 (aromatic petroleum derivative made by Esso), propylene glycol monomethyl ether acetate, EEP solvent (Eastman ester solvent) You can choose anything. The polymerization initiator can be selected from commonly used polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide and the like. Moreover, chain transfer agents, such as 2-mercaptoethanol and n-octyl mercaptan, can be used as needed.
本発明のアクリル系共重合体（Ａ）は、ポリイソシアネート硬化剤（Ｂ）と共に熱硬化性被覆用樹脂組成物として使用することができる。ポリイソシアネート硬化剤（Ｂ）は、特に限定されるものではなく、用途に合わせて適宜選択することができるが、例えば、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサンジイソシアネート等の脂肪族ジイソシアネート類、イソホロンジイソシアネート、４，４’−メチレンビス（シクロヘキシルイソシアネート）等の脂環族ジイソシアネート類、キシリレンジイソシアネート、トリレンジイソシアネート等の芳香族ジイソシアネート類等が挙げられる。 The acrylic copolymer (A) of the present invention can be used as a thermosetting coating resin composition together with the polyisocyanate curing agent (B). The polyisocyanate curing agent (B) is not particularly limited and can be appropriately selected according to the use. For example, aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate, isophorone Examples thereof include alicyclic diisocyanates such as diisocyanate and 4,4′-methylenebis (cyclohexyl isocyanate), and aromatic diisocyanates such as xylylene diisocyanate and tolylene diisocyanate.
ポリイソシアネート硬化剤（Ｂ）と共に、エチレングリコール、プロピレングリコール、ネオペンチルグリコール、トリメチロールプロパン等の多価アルコールやイソシアネート基と反応する官能基を有する低分子量のポリエステル樹脂、イソシアネート基と水などの付加物、またはビュレット体もしくはジイソシアネート同士の重合体、さらにポリイソシアネート硬化剤（Ｂ）と低級一価アルコールまたはメチルエチルケトオキシムなど公知のブロック化剤でブロックしたもの等を併用することができる。 Addition of polyisocyanate curing agent (B), low molecular weight polyester resins having functional groups that react with polyhydric alcohols such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and isocyanate groups, and isocyanate groups and water Or a polymer of a buret body or a diisocyanate, and a polyisocyanate curing agent (B) and a blocked with a known blocking agent such as a lower monohydric alcohol or methyl ethyl ketoxime can be used in combination.
ポリイソシアネート硬化剤（Ｂ）は、好ましくは熱硬化性被覆用樹脂組成物の１０〜６０質量％の範囲で使用される。硬化剤が１０質量％未満では、硬化塗膜の耐溶剤性、硬度が低下する傾向にあり、６０質量％を越えると硬化塗膜が脆くなり、塗膜の耐衝撃性や耐候性が低下する傾向にある。より好ましくは、１５〜５０質量％である。また、これらポリイソシアネート硬化剤（Ｂ）は、本発明のアクリル系共重合体（Ａ）に含まれる水酸基当量とポリイソシアネート硬化剤（Ｂ）に含まれるイソシアネート基当量の比がＯＨ／ＮＣＯ＝１／０．５〜１／２となる範囲で使用することが好ましく、より好ましくは、ＯＨ／ＮＣＯ＝１／０．８〜１／１．３の範囲である。 The polyisocyanate curing agent (B) is preferably used in the range of 10 to 60% by mass of the thermosetting coating resin composition. If the curing agent is less than 10% by mass, the solvent resistance and hardness of the cured coating film tend to decrease, and if it exceeds 60% by mass, the cured coating film becomes brittle and the impact resistance and weather resistance of the coating film decrease. There is a tendency. More preferably, it is 15-50 mass%. Further, these polyisocyanate curing agents (B) have a ratio of hydroxyl group equivalent contained in the acrylic copolymer (A) of the present invention to isocyanate group equivalent contained in the polyisocyanate curing agent (B) of OH / NCO = 1. It is preferable to use in the range which becomes /0.5-1/2, More preferably, it is the range of OH / NCO = 1 / 0.8-1 / 1.3.
熱硬化性被覆用樹脂組成物を調製する際には、必要に応じて、ジブチル錫ジラウレート等に代表される硬化促進剤や、硬化触媒（アミン系等）を使用することができる。 When preparing the thermosetting coating resin composition, a curing accelerator represented by dibutyltin dilaurate or the like, or a curing catalyst (amine system or the like) can be used as necessary.
また、本発明の熱硬化性被覆用樹脂組成物を塗料化する際には、酸化チタンなどの無機系顔料やシアニンブルー等の有機系顔料、表面調製剤、紫外線吸収剤、光安定剤、酸化防止剤、垂れ止め剤等の添加剤を必要に応じて公知の手段を用いて配合し、最後に希釈用有機溶剤で適当な粘度となるように希釈調整する。希釈用有機溶剤の具体例としては、キシレン、ソルベッソ＃１００、ソルベッソ＃１５０（エッソ社製芳香族石油誘導体）、ケトンの２−ヘプタノン（イーストマン社製）、エステル系溶剤のＥＥＰ（イーストマン社製）、プロピレングリコールモノメチルエーテルアセテートなどが挙げられる。 Further, when the thermosetting coating resin composition of the present invention is made into a paint, inorganic pigments such as titanium oxide, organic pigments such as cyanine blue, surface preparation agents, ultraviolet absorbers, light stabilizers, oxidation agents Additives such as an inhibitor and an anti-sagging agent are blended as necessary using known means, and finally diluted with an organic solvent for dilution so as to have an appropriate viscosity. Specific examples of the organic solvent for dilution include xylene, Solvesso # 100, Solvesso # 150 (Esso aromatic petroleum derivative), ketone 2-heptanone (Eastman), ester solvent EEP (Eastman) And propylene glycol monomethyl ether acetate.
特に本発明の熱硬化性被膜用樹脂組成物は、多層塗膜のクリヤーコート層として使用することができる。該クリヤーコート層は、本発明の熱硬化性被膜用樹脂組成物のみからなる単層クリヤーコート層または公知の熱硬化性被膜用樹脂組成物、好ましくは熱硬化アクリル樹脂からなるクリヤーコート層を含んだ多層クリヤーコート層のどちらでもよく、これらは用途に応じて適宜選択することができる。 In particular, the resin composition for thermosetting coatings of the present invention can be used as a clear coat layer of a multilayer coating film. The clear coat layer includes a single-layer clear coat layer made of only the thermosetting coating resin composition of the present invention or a known thermosetting coating resin composition, preferably a clear coating layer made of a thermosetting acrylic resin. Any of the multi-layer clear coat layers may be used, and these can be appropriately selected depending on the application.
本発明の熱硬化性被覆用樹脂組成物を含む塗料は、スプレー塗装、刷毛塗り塗装、浸漬塗装、ロール塗装、流し塗装等により塗装することができる。また、発明のクリヤー塗料組成物は、木、金属、ガラス、布、プラスチック、発砲体等、特にプラスチック及び金属表面（例えば、スチール、アルミニウムおよびこれら合金）に有利に用いることができ、自動車用クリヤー塗料として好適に使用することができる。 The coating material containing the thermosetting coating resin composition of the present invention can be applied by spray coating, brush coating, dip coating, roll coating, flow coating, or the like. The clear coating composition of the invention can be advantageously used for wood, metal, glass, cloth, plastic, foam, etc., particularly plastic and metal surfaces (for example, steel, aluminum and alloys thereof). It can be suitably used as a paint.
以下、本発明を実施例・比較例により具体的に説明する。なお実施例中の「部」は質量部を意味する。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In the examples, “part” means part by mass.
＜アクリル系共重合体溶液（Ａ−１）〜（Ａ−１１）の合成＞
攪拌翼、原料供給ライン、窒素加圧ライン、温調装置を備えた攪拌槽型反応装置に溶剤としてソルベッソ＃１５０（エッソ社製、芳香族炭化水素）を４５部仕込み、系内に窒素を１００ｍｌ/分で吹き込みながら釜内温を１５０℃まで加熱した。<Synthesis of Acrylic Copolymer Solutions (A-1) to (A-11)>
A stirring vessel reactor equipped with a stirring blade, raw material supply line, nitrogen pressure line, and temperature control device was charged with 45 parts of Solvesso # 150 (Esso, aromatic hydrocarbon) as a solvent, and 100 ml of nitrogen was added to the system. The temperature inside the kettle was heated to 150 ° C. while blowing at / min.
次にイソボルニルメタクリレート２０部、メチルメタクリレート１８部、ラウリルメタクリレート５部、２−ヒドロキシプロピルアクリレート３０部、ブレンマーＰＰ１０００を１０部、メタクリル酸２部およびジ−ｔ−ヘキシルパーオキサイド５部からなる単量体と重合開始剤の混合物を準備し、滴下ポンプにて容器上部より３時間かけて連続的に滴下した。滴下終了後、内温を１２０℃まで下げ、追加触媒としてｔ−ブチルパーオキシ−２−エチルヘキサノエート２部を３０分かけて連続的に滴下し、更に１２０℃で３０分保持して樹脂への転化率を充分に高めた。得られたアクリル系共重合体溶液（Ａ−１）をＧＰＣで測定した結果、質量平均分子量は６０００であった。 Next, 20 parts of isobornyl methacrylate, 18 parts of methyl methacrylate, 5 parts of lauryl methacrylate, 30 parts of 2-hydroxypropyl acrylate, 10 parts of Bremer PP1000, 2 parts of methacrylic acid and 5 parts of di-t-hexyl peroxide. A mixture of a monomer and a polymerization initiator was prepared, and the mixture was continuously dropped from the upper part of the container with a dropping pump over 3 hours. After completion of the dropping, the internal temperature is lowered to 120 ° C., 2 parts of t-butylperoxy-2-ethylhexanoate is continuously added dropwise over 30 minutes as an additional catalyst, and the resin is further maintained at 120 ° C. for 30 minutes. The conversion rate to was sufficiently increased. As a result of measuring the obtained acrylic copolymer solution (A-1) by GPC, the mass average molecular weight was 6000.
以下、表１に示されるアクリル系共重合体溶液（Ａ−２）〜（Ａ−１１）についても（Ａ−１）に準じて重合反応を行った。 Hereinafter, the acrylic copolymer solutions (A-2) to (A-11) shown in Table 1 were also subjected to the polymerization reaction according to (A-1).
＜クリヤーコート塗料（Ｂ−１）〜（Ｂ−１１）の調整＞
アクリル系共重合体溶液（Ａ−１）に、ポリイソシアネート硬化剤として、ＮＣＯ基当量の比がＯＨ／ＮＣＯ＝１／１になるようにソルベッソ＃１００にて５０％まで希釈したデュラネートＴＰＡ−１００（旭化成製、ＮＣＯ比率２３．１質量％）を所定量加え、モダフロー（モンサット社製、表面調整剤）０．０８部、チヌビン９００（チバガイギー社製、紫外線吸収剤）１部、サノール２９２（三共(株)製、光安定剤）１部を加え、希釈シンナー（ソルベッソ＃１００/ソルベッソ＃１５０＝１／１）によって、フォードカップＮｏ．４にて２０秒の粘度になるまで希釈調整してクリヤーコート塗料（Ｂ−１）を得た。<Adjustment of clear coat paints (B-1) to (B-11)>
In the acrylic copolymer solution (A-1), as a polyisocyanate curing agent, Duranate TPA-100 diluted to 50% with Solvesso # 100 so that the ratio of NCO group equivalent is OH / NCO = 1/1 (Asahi Kasei, NCO ratio 23.1% by mass) is added in a predetermined amount, Modaflow (Monsat, surface conditioner) 0.08 parts, Tinuvin 900 (Ciba Geigy, UV absorber) 1 part, Sanol 292 (Sankyo) 1 part of a light stabilizer (manufactured by Co., Ltd.) was added, and a Ford Cup No. 1 was diluted with a diluted thinner (Solvesso # 100 / Solvesso # 150 = 1/1). The clear coating composition (B-1) was obtained by adjusting the dilution at 4 until the viscosity reached 20 seconds.
以下、同様にしてアクリル系共重合体（Ａ−２）〜（Ａ−１１）についても、対応するクリヤーコート塗料（Ｂ−２）〜（Ｂ−１１）をそれぞれ得た。 Hereinafter, corresponding clear coat paints (B-2) to (B-11) were obtained in the same manner for the acrylic copolymers (A-2) to (A-11).
＜ベースコート塗料用系共重合体水溶液（Ｃ−１）の合成＞
攪拌翼、原料供給ライン、窒素加圧ライン、温調装置を備えた攪拌槽型反応装置に溶剤としてブチセロソルブを４５部仕込み、系内に窒素を１００ｍｌ／分で吹き込みながら釜内温を１００℃まで加熱した。次に、
スチレン ３０部
メチルメタクリレート １５部
ｎ−ブチルアクリレート ３４部
２−エチルヘキシルメタクリレート ６部
２−ヒドロキシメタクリレート １２部
メタクリル酸 ３部
アゾビスイソブチロニトリル １部
からなる単量体と重合開始剤の混合物を準備し、滴下ポンプにて容器上部より４時間かけて連続的に滴下した。滴下終了後、内温を９０℃まで下げ、追加触媒としてアゾビスイソブチロニトリル０．５部をブチルセロソルブ５部に溶解させたものを３０分かけて連続的に滴下し、同温度にて３０分保持した後、更に８０℃まで降温し、ジメチルアミノエタノールを加えることで全カルボキシル基の８０モル％を中和してベースコート塗料用系共重合体水溶液（Ｃ−１）を得た。<Synthesis of Base Coat Coating System Copolymer Aqueous Solution (C-1)>
A stirring vessel reactor equipped with a stirring blade, raw material supply line, nitrogen pressure line, and temperature controller was charged with 45 parts of buticellosolve as a solvent, and the temperature inside the kettle was 100 ° C. while blowing nitrogen into the system at 100 ml / min. Until heated. next,
Styrene 30 parts Methyl methacrylate 15 parts n-Butyl acrylate 34 parts 2-Ethylhexyl methacrylate 6 parts 2-hydroxy methacrylate 12 parts Methacrylic acid 3 parts Azobisisobutyronitrile 1 part A monomer and polymerization initiator mixture is prepared And it was dripped continuously over 4 hours from the container upper part with the dripping pump. After completion of the dropwise addition, the internal temperature was lowered to 90 ° C., and 0.5 parts of azobisisobutyronitrile dissolved in 5 parts of butyl cellosolve was continuously added dropwise over 30 minutes as an additional catalyst. Then, the temperature was further lowered to 80 ° C., and dimethylaminoethanol was added to neutralize 80 mol% of all carboxyl groups to obtain a base coat paint aqueous solution (C-1).
＜ベースコート塗料（Ｄ−１）の調整＞
ベースコート塗料用系共重合体水溶液（Ｃ−１）に、メラミン硬化剤のサイメル７０３（日本サイテックインダストリーズ製、メチル化メラミン樹脂、８０％）４５部、アルミペースト＃９６７０（東洋アルミニウム製）２０部、リン酸含有樹脂１０部およびイソプロピルアルコール３０部を混合し、さらにフォードカップＮｏ．４にて４０秒の粘度になるまで水を加えて希釈した。<Adjustment of base coat paint (D-1)>
To base coat paint aqueous solution (C-1), melamine curing agent Cymel 703 (manufactured by Nippon Cytec Industries, methylated melamine resin, 80%), 45 parts, aluminum paste # 9660 (manufactured by Toyo Aluminum), 10 parts of a phosphoric acid-containing resin and 30 parts of isopropyl alcohol were mixed. 4 was diluted with water until the viscosity reached 40 seconds.
なお、アクリル系共重合体の物性は、下記により評価した。 The physical properties of the acrylic copolymer were evaluated as follows.
＜加熱残分＞
１ｇのアクリル系共重合体溶液をアルミ皿上にサンプリングし、１５０℃で１時間乾燥させたときの不揮発分の比率（質量％）を求めた。<Remaining heating>
1 g of the acrylic copolymer solution was sampled on an aluminum dish and the ratio of non-volatile content (mass%) when dried at 150 ° C. for 1 hour was determined.
＜質量平均分子量＞
アクリル系共重合体溶液のテトラヒドロフラン溶液（０．４質量％）を調整後、ＴＯＳＯ社製カラム（ＧＥ４０００ＨＸＬ及びＧ２０００ＨＸＬ）が装着されたＴＯＳＯ社製ゲルパーミエーションクロマトグラフィー装置に上記の溶液１００μｌを注入し、流量：１ｍｌ／分、溶離液：テトラヒドロフラン、カラム温度：４０℃の条件でゲルパーミエーションクロマトグラフィー法を用いて測定され、標準ポリスチレンで換算された値を求めた。<Mass average molecular weight>
After preparing a tetrahydrofuran solution (0.4% by mass) of an acrylic copolymer solution, 100 μl of the above solution was injected into a TOSO gel permeation chromatography apparatus equipped with a TOSO column (GE4000HXL and G2000HXL). , Flow rate: 1 ml / min, eluent: tetrahydrofuran, column temperature: measured by gel permeation chromatography under conditions of 40 ° C., and a value converted to standard polystyrene was obtained.
＜硬化性試験＞
硬化性は架橋間分子量により判断した。架橋間分子量は以下の方法で求めた。<Curing test>
Curability was judged by molecular weight between crosslinks. The molecular weight between crosslinks was determined by the following method.
粘弾性アナライザーＲＳＡＩＩ（レオメトリックス社製）を用いて、後述する試験板から塗膜を剥離させて裁断することによって作製した測定用サンプルに、室温から２００℃の範囲において、１分間に２℃の昇温速度にて、周波数１１Ｈｚで振動を与えてそのときのＥ´（貯蔵弾性率）とＥ´が最小になるときの温度から下式を用いて算出した。 Using a viscoelasticity analyzer RSAII (manufactured by Rheometrics), a measurement sample prepared by peeling and cutting a coating film from a test plate described later was applied at a temperature of 2 ° C. per minute in the range of room temperature to 200 ° C. It calculated using the following formula from the temperature at which E ′ (storage elastic modulus) and E ′ at that time were minimized by applying vibration at a frequency of 11 Hz at the rate of temperature rise.
Ｍｃ（架橋間分子量）＝３ｆＲＴ／Ｅ´
Ｒ：気体定数 ｆ：試料塗膜の密度
＜硬度＞
リン酸亜鉛処理された鋼板（３０ｃｍ×４５ｃｍ）に自動車用カチオン電着塗料を塗装し、１８０℃で３０分間焼き付けた。さらにアミノアルキッド樹脂系の中塗り塗料を塗装し、１６０℃で３０分間焼き付けた後、塗膜を水研し、乾燥させた。この塗膜上にまず、ベースコート塗料（Ｄ−１）を乾燥膜厚が１０〜５０μｍとなるようにスプレー塗装し、５分間放置した後、８０℃で１０分間プレヒートした。次に塗板を冷却した後、クリヤーコート塗料（Ｂ−１）〜（Ｂ−５）を乾燥膜厚が３０〜４０μｍとなるようにウェットオンウエット方式で重ね塗り、１０分間放置後、１４０℃の熱風乾燥機で３０分間焼き付けて塗膜が形成された試験板を作製した。この試験板により、三菱鉛筆「ユニ」を用いて４５度の角度で塗膜を引っかいて傷のつかない最も硬い硬度を判定した。Mc (molecular weight between crosslinks) = 3 fRT / E ′
R: gas constant f: density of sample coating film <hardness>
An automotive cationic electrodeposition coating was applied to a zinc phosphate-treated steel plate (30 cm × 45 cm) and baked at 180 ° C. for 30 minutes. Further, an aminoalkyd resin-based intermediate coating was applied and baked at 160 ° C. for 30 minutes, and then the coating film was wet-polished and dried. First, the base coat paint (D-1) was spray-coated on this coating film so as to have a dry film thickness of 10 to 50 μm, left for 5 minutes, and preheated at 80 ° C. for 10 minutes. Next, after the coated plate is cooled, the clear coat paints (B-1) to (B-5) are repeatedly applied by a wet on wet method so that the dry film thickness becomes 30 to 40 μm, and left to stand for 140 minutes. A test plate on which a coating film was formed was baked for 30 minutes with a hot air dryer. Using this test plate, the hardest hardness without scratches was determined by scratching the coating film at an angle of 45 degrees using a Mitsubishi pencil “Uni”.
＜外観＞
硬度測定と同様に塗膜を形成し、Ｗａｖｅ−ｓｃａｎ−ＤＯＩ（ＢＹＫ−Ｇａｒｄｎｅｒ社製）を用いて仕上がり外観を測定した。測定値のうちＷｃ値は塗膜外観のチリ、ムジの項目に該当し、Ｗｄは外観の肌、チリの項目に相関する。外観評価はＷｃ、Ｗｄ値を用いて行った。これらの値は、数値が小さいほど良好である。<Appearance>
A coating film was formed in the same manner as the hardness measurement, and the finished appearance was measured using Wave-scan-DOI (manufactured by BYK-Gardner). Of the measured values, the Wc value corresponds to the items of dust and muzzle on the appearance of the coating film, and Wd correlates with the items of skin and dust on the appearance. Appearance evaluation was performed using Wc and Wd values. These values are better as the numerical value is smaller.
＜耐擦り傷性＞
硬度測定と同様に試験板を作製した。大栄科学精器（株）製の摩擦堅牢度試験機を用い、マケン石鹸（株）製マケンクレンザーの５０％水溶液を塗りつけたガーゼを塗面と接触する箇所に当て、荷重１ｋｇで５０往復摩擦試験を行い、傷跡を目視判定した。<Abrasion resistance>
A test plate was prepared in the same manner as the hardness measurement. Using a friction fastness tester manufactured by Daiei Kagaku Seiki Co., Ltd., apply gauze coated with a 50% aqueous solution of Maken Cleanser manufactured by Maken Soap Co., Ltd. to the part that comes into contact with the coated surface, and perform 50 reciprocating friction tests at a load of 1 kg. The scar was visually determined.
○：ほとんど傷は視認できない
△：若干傷はあるが使用可能
×：傷が多く、不良
＜耐候性＞
硬度測定と同様に試験板を作製し、サンシャインウェザオメーター（スガ試験機製）を用い、初期光沢値に対する２０００時間後の光沢値を基に以下の基準で評価した。○: Scratches are hardly visible
Δ: Slightly scratched but usable
×: Many scratches, poor <weather resistance>
A test plate was prepared in the same manner as the hardness measurement, and evaluated using the sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.) on the basis of the gloss value after 2000 hours with respect to the initial gloss value.
○：光沢良好
△：光沢不良
×：光沢不良、マイクロクラック有
＜耐候性試験後耐擦り傷性＞
上記耐候性試験を実施した塗膜にて、大栄科学精器（株）製の摩擦堅牢度試験機を用い、マケン石鹸（株）製マケンクレンザーの５０％水溶液を塗りつけたガーゼを塗面と接触する箇所に当て、荷重１ｋｇで５０往復摩擦試験を行い、傷跡を目視判定した。○: Good gloss
Δ: Poor gloss
X: Poor gloss, with micro crack
<Abrasion resistance after weather resistance test>
In the coating film subjected to the weather resistance test, using a friction fastness tester manufactured by Daiei Kagaku Seiki Co., Ltd., contact the coated surface with gauze coated with 50% aqueous solution of Macken Cleanser manufactured by Makken Soap Co., Ltd. A 50 reciprocating friction test was performed at a load of 1 kg, and the scar was visually determined.
○：ほとんど傷は視認できない
△：若干傷はあるが使用可能
＜耐汚染性＞
硬度測定と同様に試験板を作製し、屋外に設置し３ヶ月経過後における水シミの有無を目視判定した。○: Scratches are hardly visible
Δ: Slightly scratched but usable <Contamination resistance>
A test plate was prepared in the same manner as the hardness measurement, installed outdoors, and visually checked for the presence of water spots after 3 months.
○：水シミなし
×：水シミあり
以上の実施例からも明らかなように、本発明の熱硬化性被膜用樹脂組成物を用いると、外観、（初期、耐候後）耐擦り傷性、外観仕上がり性、耐候性、貯蔵安定性、耐汚染性、硬化性、硬度、耐亜硫酸性の優れた塗膜の提供が可能であり、工業上非常に有益なものである。○: No water stain
X: Water stains As is apparent from the above examples, when the thermosetting coating resin composition of the present invention is used, the appearance, (initial, after weathering) scratch resistance, appearance finish, weather resistance, It is possible to provide a coating film having excellent storage stability, stain resistance, curability, hardness, and sulfite resistance, which is very useful industrially.
これに対し、比較例１では単量体（ａ）単位に換えて２−ヒドロキシエチルメタクリレート単位を用いた例であり、外観が悪化していた。また、比較例２では単量体（ａ）単位の含有量より単量体（ｂ）単位の含有量の方が多い例であり、外観、硬度、耐汚染性が悪化した。比較例３では単量体（ｃ）単位に換えてシクロヘキシルメタクリレート単位を用いた例であり、初期及び耐候性試験後の耐擦り傷並びに耐汚染性が悪化した。
本発明の熱硬化性被膜用樹脂組成物を用いると、外観、（初期、耐候後）耐擦り傷性、外観仕上がり性、耐候性、貯蔵安定性、耐汚染性、硬化性、硬度、耐亜硫酸性の優れた塗膜が利用可能であり、工業上非常に有益なものである。
When the resin composition for thermosetting coatings of the present invention is used, appearance, (initial, after weather resistance) scratch resistance, appearance finish, weather resistance, storage stability, stain resistance, curability, hardness, sulfite resistance Excellent coatings are available and are very useful industrially.
Claims (4)
該アクリル系共重合体の水酸基価が１３０〜１８０ｍｇＫＯＨ／ｇである熱硬化性被覆用樹脂組成物用アクリル系共重合体（Ａ）。
An acrylic copolymer (A) for a thermosetting coating resin composition, wherein the acrylic copolymer has a hydroxyl value of 130 to 180 mgKOH / g .
An article having the coating film according to claim 3.
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| JPH06212120A (en) * | 1993-01-20 | 1994-08-02 | Mitsubishi Rayon Co Ltd | Thermosetting coating composition and formation of coating film |
| JPH08188626A (en) * | 1994-10-07 | 1996-07-23 | Hoechst Ag | Copolymer comprising structural unit derived from cyclic or polycyclic monomer having special isomer distribution and coating material containing same |
| JP2006124414A (en) * | 2004-10-26 | 2006-05-18 | Cemedine Co Ltd | Two pack type acrylic adhesive for casting model preparation and adhesive technique using the same adhesive |
| JP2006348172A (en) * | 2005-06-16 | 2006-12-28 | Basf Coatings Japan Ltd | Thermosetting coating composition |
| JP2007238643A (en) * | 2006-03-03 | 2007-09-20 | Harima Chem Inc | Resin for dispersing pigment and ink or coating material composition containing the same |
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| JPH01156387A (en) * | 1987-12-14 | 1989-06-19 | Cemedine Co Ltd | Photocurable adhesive composition having water resistance |
| JPH0859749A (en) * | 1994-08-23 | 1996-03-05 | Nippon Paint Co Ltd | Curable resin composition, coating compound composition, method for coating and coated material |
| JP3532976B2 (en) * | 1994-10-07 | 2004-05-31 | 三菱レイヨン株式会社 | Base resin for toning |
| JP4370668B2 (en) * | 2000-03-29 | 2009-11-25 | Ｊｓｒ株式会社 | Positive-type radiation-sensitive resin composition for plating model production and method for producing plating model |
| JP4403627B2 (en) * | 2000-03-29 | 2010-01-27 | Ｊｓｒ株式会社 | Positive-type radiation-sensitive resin composition and method for producing plated molded article |
| JP4268316B2 (en) * | 2000-06-07 | 2009-05-27 | 大日本印刷株式会社 | Protective layer transfer sheet and printed matter |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06212120A (en) * | 1993-01-20 | 1994-08-02 | Mitsubishi Rayon Co Ltd | Thermosetting coating composition and formation of coating film |
| JPH08188626A (en) * | 1994-10-07 | 1996-07-23 | Hoechst Ag | Copolymer comprising structural unit derived from cyclic or polycyclic monomer having special isomer distribution and coating material containing same |
| JP2006124414A (en) * | 2004-10-26 | 2006-05-18 | Cemedine Co Ltd | Two pack type acrylic adhesive for casting model preparation and adhesive technique using the same adhesive |
| JP2006348172A (en) * | 2005-06-16 | 2006-12-28 | Basf Coatings Japan Ltd | Thermosetting coating composition |
| JP2007238643A (en) * | 2006-03-03 | 2007-09-20 | Harima Chem Inc | Resin for dispersing pigment and ink or coating material composition containing the same |
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