JP6891702B2 - Anti-fog paint resin and anti-fog paint - Google Patents
Anti-fog paint resin and anti-fog paint Download PDFInfo
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Description
本発明は、防曇塗料用樹脂及び防曇塗料に関する。 The present invention relates to a resin for anti-fog coating and an anti-fog coating.
自動車のヘッドランプ等の車両灯具には一般に、透明素材からなるレンズが設けられている。かかる車両灯具においては、灯室内に高湿度の空気が入り込み、外気や降雨等によってレンズが冷やされ、内面に水分が結露することによって曇りが生じることがある。特に透明素材としてポリカーボネート等の透明樹脂が用いられている場合、表面の疎水性の高さから、上記のような曇りが生じやすい。レンズの曇りは、車両灯の輝度を低下させたり美観を損なう。そこで、このような曇りの発生を抑制するために、曇りが発生する部位に防曇塗料を塗布し、塗膜を設ける方法が知られている。
特許文献１には、アクリルアミド単量体等を含む単量体混合物から形成される親水性重合体部分と、（メタ）アクリル酸アルキルエステル単量体等を含む単量体混合物から形成される疎水性重合体部分とを有するブロックまたはグラフト共重合体を含む防曇塗料が開示されている。
Vehicle lighting fixtures such as automobile headlamps are generally provided with a lens made of a transparent material. In such vehicle lighting equipment, high-humidity air may enter the lighting chamber, the lens may be cooled by outside air, rainfall, or the like, and moisture may condense on the inner surface to cause fogging. In particular, when a transparent resin such as polycarbonate is used as the transparent material, the above-mentioned fogging is likely to occur due to the high hydrophobicity of the surface. Fogging of the lens reduces the brightness of the vehicle light and spoils the appearance. Therefore, in order to suppress the occurrence of such fogging, a method is known in which an antifogging paint is applied to a portion where fogging occurs and a coating film is provided.
Patent Document 1 describes a hydrophobic polymer moiety formed from a monomer mixture containing an acrylamide monomer and the like and a hydrophobic polymer formed from a monomer mixture containing a (meth) acrylic acid alkyl ester monomer and the like. An antifogging coating containing a block or graft copolymer having a sex polymer moiety is disclosed.
しかし、特許文献１で用いられている共重合体は、製造に際して多段階の重合を行う必要があり、手間がかかる。単にアクリルアミド単量体等を共重合させた樹脂を用いた防曇塗料は、形成された塗膜の膜面上で一旦水分が水滴として凝結し流れ落ちると、乾燥後の塗膜に筋状の跡（以下、水垂れ跡という。）が残ってしまうという問題がある。 However, the copolymer used in Patent Document 1 needs to be polymerized in multiple stages at the time of production, which is troublesome. An antifogging paint that uses a resin obtained by simply copolymerizing an acrylamide monomer or the like has streaky marks on the dried coating film once water has condensed as water droplets and flows down on the film surface of the formed coating film. There is a problem that (hereinafter referred to as "water dripping marks") remains.
本発明は、上記事情に鑑みてなされたものであり、防曇性に優れ、かつ水垂れ跡が残りにくい塗膜を形成できる防曇塗料用樹脂及び防曇塗料を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resin for an antifogging paint and an antifogging paint capable of forming a coating film having excellent antifogging properties and less likely to leave traces of water dripping. ..
本発明は、以下の態様を有する。
〔１〕水酸基及びアルコキシ基を有さないアクリルアミド単量体を１５〜４５質量％、水酸基及びアルコキシ基のいずれか一方又は両方を有するアクリルアミド単量体を５〜８５質量％含む重合性単量体混合物をリビングラジカル重合した防曇塗料用樹脂。
〔２〕前記〔１〕の防曇塗料用樹脂を含む防曇塗料。
The present invention has the following aspects.
[1] A polymerizable monomer containing 15 to 45% by mass of an acrylamide monomer having no hydroxyl group and an alkoxy group, and 5 to 85% by mass of an acrylamide monomer having one or both of a hydroxyl group and an alkoxy group. Resin for anti-fog coating, which is a mixture radically polymerized in the living.
[2] An anti-fog paint containing the resin for the anti-fog paint according to the above [1].
本発明の防曇塗料用樹脂によれば、防曇性に優れ、かつ水垂れ跡が残りにくい塗膜を形成できる防曇塗料を提供できる。
本発明の防曇塗料によれば、防曇性に優れ、かつ水垂れ跡が残りにくい塗膜を形成できる。
According to the anti-fog coating resin of the present invention, it is possible to provide an anti-fog coating that is excellent in anti-fog property and can form a coating film in which water dripping marks are less likely to remain.
According to the anti-fog coating material of the present invention, it is possible to form a coating film having excellent anti-fog properties and less likely to leave dripping marks.
〔防曇塗料用樹脂〕
本発明の防曇塗料用樹脂は、水酸基及びアルコキシ基を有さないアクリルアミド単量体（以下、単量体（ａ）ともいう。）を１５〜４５質量％、水酸基及びアルコキシ基のいずれか一方又は両方を有するアクリルアミド単量体（以下、単量体（ｂ）ともいう。）を５〜８５質量％含む重合性単量体混合物をリビングラジカル重合した共重合物である。
前記重合性単量体混合物は、単量体（ａ）及び単量体（ｂ）以外の他の重合性単量体をさらに含んでもよい。
[Resin for anti-fog paint]
The antifogging coating resin of the present invention contains 15 to 45% by mass of an acrylamide monomer (hereinafter, also referred to as monomer (a)) having no hydroxyl group and an alkoxy group, and either a hydroxyl group or an alkoxy group. Alternatively, it is a copolymer obtained by living radical polymerization of a polymerizable monomer mixture containing 5 to 85% by mass of an acrylamide monomer having both (hereinafter, also referred to as monomer (b)).
The polymerizable monomer mixture may further contain a polymerizable monomer other than the monomer (a) and the monomer (b).
単量体（ａ）は、防曇塗料用樹脂に親水性を付与する。防曇塗料用樹脂が親水性を有することで、形成される塗膜が防曇性を示す。
単量体（ａ）としては、例えば、下記式（ａ１）で表される単量体が挙げられる。
ＣＨ２＝ＣＨ−ＣＯ−ＮＲ１Ｒ２ ・・・（ａ１）
ここで、Ｒ１及びＲ２はそれぞれ独立に水素原子又はアルキル基であるか、又はＲ１とＲ２とが結合してＮとともに環式基を形成している。
アルキル基の炭素数は、防曇性の点から、１〜６が好ましく、１〜４がより好ましい。環式基としては、例えばモルホリノ基、ピロリジノ等が挙げられる。
The monomer (a) imparts hydrophilicity to the antifogging paint resin. Since the resin for anti-fog coating has hydrophilicity, the formed coating film exhibits anti-fog property.
Examples of the monomer (a) include a monomer represented by the following formula (a1).
CH 2 = CH-CO-NR 1 R 2 ... (a1)
Here, R 1 and R 2 are independent hydrogen atoms or alkyl groups, respectively, or R 1 and R 2 are bonded to form a cyclic group together with N.
The number of carbon atoms of the alkyl group is preferably 1 to 6 and more preferably 1 to 4 from the viewpoint of antifogging property. Examples of the cyclic group include a morpholino group, pyrrolidino and the like.
単量体（ａ）の例としては、アクリルアミド、ジメチルアクリルアミド、イソプロピルアクリルアミド、ジエチルアクリルアミド、アクリロイルモルホリン、Ｎ−ドデシルアクリルアミド等が挙げられる。これらのアクリルアミド単量体はいずれか１種を単独で用いてもよく２種以上を併用してもよい。 Examples of the monomer (a) include acrylamide, dimethylacrylamide, isopropylacrylamide, diethylacrylamide, acryloylmorpholine, N-dodecylacrylamide and the like. Any one of these acrylamide monomers may be used alone, or two or more thereof may be used in combination.
単量体（ｂ）は、防曇塗料用樹脂に架橋点を導入するための架橋性単量体である。塗膜中で水酸基（アルコキシ基の加水分解によって生成した水酸基であってもよい。）同士の縮合反応によって防曇塗料用樹脂が架橋することで、塗膜に疎水性が付与され、耐湿性が高まる。また、架橋性官能基がアルコキシ基又は水酸基であることで、架橋構造によって付与される疎水性が過度なものにならず、防曇性が損なわれにくい。
アルコキシ基としては、炭素数１〜４のアルコキシ基が好ましく、例えばメトキシ基、エトキシ基、ｎ−プロポキシ基、ｎ−ブトキシ基、ｉｓｏ−ブトキシ等が挙げられる。
The monomer (b) is a crosslinkable monomer for introducing a crosslink point into the antifogging paint resin. Hydroxylity is imparted to the coating film by cross-linking the anti-fog coating resin by the condensation reaction between hydroxyl groups (which may be hydroxyl groups generated by hydrolysis of alkoxy groups) in the coating film, and moisture resistance is improved. Increase. Further, since the crosslinkable functional group is an alkoxy group or a hydroxyl group, the hydrophobicity imparted by the crosslinked structure does not become excessive, and the antifogging property is not easily impaired.
The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group and an iso-butoxy.
単量体（ｂ）としては、例えば、下記式（ｂ１）で表される単量体が挙げられる。
ＣＨ２＝ＣＨ−ＣＯ−ＮＲ３Ｒ４ ・・・（ｂ１）
ここで、Ｒ３はアルコキシアルキル基又はヒドロキシアルキル基であり、Ｒ４は水素原子又はアルキル基である。
アルコキシアルキル基及びヒドロキシアルキル基それぞれにおけるアルキル基の炭素数は、例えば１〜４であってよい。
Ｒ４のアルキル基の炭素数は、例えば１〜１２であってよい。
Examples of the monomer (b) include a monomer represented by the following formula (b1).
CH 2 = CH-CO-NR 3 R 4 ... (b1)
Here, R 3 is an alkoxyalkyl group or a hydroxyalkyl group, and R 4 is a hydrogen atom or an alkyl group.
The number of carbon atoms of the alkyl group in each of the alkoxyalkyl group and the hydroxyalkyl group may be, for example, 1 to 4.
The alkyl group of R 4 may have, for example, 1 to 12 carbon atoms.
単量体（ｂ）の例としては、Ｎ−（メトキシメチル）アクリルアミド、Ｎ−（ヒドロキシメチル）アクリルアミド、Ｎ−（２−ヒドロキシエチル）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、Ｎ−（イソブトキシメチル）アクリルアミド等が挙げられる。これらのアクリルアミド単量体はいずれか１種を単独で用いてもよく２種以上を併用してもよい。 Examples of the monomer (b) are N- (methoxymethyl) acrylamide, N- (hydroxymethyl) acrylamide, N- (2-hydroxyethyl) acrylamide, N- (ethoxymethyl) acrylamide, N- (butoxymethyl). ) Acrylamide, N- (isobutoxymethyl) acrylamide and the like. Any one of these acrylamide monomers may be used alone, or two or more thereof may be used in combination.
他の重合性単量体としては、単量体（ａ）及び単量体（ｂ）と共重合可能であればよく、例えば非親水性単量体が挙げられる。非親水性単量体としては、例えば、メチル（メタ）アクリレート、エチル（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、２−エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート等の、炭化水素基を有する（メタ）アクリル酸エステル；スチレン、メチルスチレン、ジメチルスチレン、エチルスチレン、α−メチルスチレン、α−エチルスチレン等の芳香族ビニル単量体等が挙げられる。「（メタ）アクリレート」はアクリレート又はメタクリレートを示す。（メタ）アクリル酸エステルが有する炭化水素基の炭素数は１〜６が好ましい。これらの重合性単量体はいずれか１種を単独で用いてもよく２種以上を併用してもよい。
他の重合性単量体は、塗膜の耐湿性の点から、非親水性単量体を含むことが好ましい。
The other polymerizable monomer may be copolymerizable with the monomer (a) and the monomer (b), and examples thereof include a non-hydrophilic monomer. Examples of the non-hydrophilic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl. (Meta) acrylic acid ester having a hydrocarbon group such as (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate; styrene, methylstyrene, dimethylstyrene , Aromatic vinyl monomers such as ethyl styrene, α-methyl styrene, α-ethyl styrene and the like. "(Meta) acrylate" indicates acrylate or methacrylate. The hydrocarbon group of the (meth) acrylic acid ester preferably has 1 to 6 carbon atoms. Any one of these polymerizable monomers may be used alone, or two or more thereof may be used in combination.
The other polymerizable monomer preferably contains a non-hydrophilic monomer from the viewpoint of moisture resistance of the coating film.
重合性単量体混合物中の単量体（ａ）の含有量は、重合性単量体混合物の総質量に対し、１５〜４５質量％であり、２０〜４５質量％が好ましく、２５〜４５質量％がより好ましい。単量体（ａ）の含有量が１５質量％以上であれば、塗膜の防曇性が優れる。単量体（ａ）の含有量が４５質量％以下であれば、塗膜の耐湿性が優れ、耐湿性試験後の塗膜の外観が良好である。 The content of the monomer (a) in the polymerizable monomer mixture is 15 to 45% by mass, preferably 20 to 45% by mass, and 25 to 45% by mass, based on the total mass of the polymerizable monomer mixture. More preferably by mass. When the content of the monomer (a) is 15% by mass or more, the antifogging property of the coating film is excellent. When the content of the monomer (a) is 45% by mass or less, the moisture resistance of the coating film is excellent, and the appearance of the coating film after the moisture resistance test is good.
重合性単量体混合物中の単量体（ｂ）の含有量は、重合性単量体混合物の総質量に対し、５〜８５質量％であり、５〜４０質量％が好ましく、５〜２０質量％がより好ましい。単量体（ｂ）の含有量が５質量％以上であれば、耐湿性試験の際に塗膜が融解しない。単量体（ｂ）の含有量が８５質量％以下であれば、架橋構造による疎水性の付与が過度にならず、塗膜の防曇性が優れる。特に２０質量％以下であれば、ポリカーボネート等の透明樹脂に対する密着性が優れる。 The content of the monomer (b) in the polymerizable monomer mixture is 5 to 85% by mass, preferably 5 to 40% by mass, and 5 to 20% by mass, based on the total mass of the polymerizable monomer mixture. More preferably by mass. If the content of the monomer (b) is 5% by mass or more, the coating film does not melt during the moisture resistance test. When the content of the monomer (b) is 85% by mass or less, the hydrophobicity is not excessively imparted by the crosslinked structure, and the antifogging property of the coating film is excellent. In particular, when it is 20% by mass or less, the adhesion to a transparent resin such as polycarbonate is excellent.
重合性単量体混合物が非親水性単量体を含む場合、重合性単量体混合物中の非親水性単量体の含有量は、重合性単量体混合物の総質量に対し、１５〜７５質量％が好ましく、３５〜７０質量％がより好ましい。非親水性単量体の含有量が１５質量％以上であれば、塗膜の耐湿性がより優れる。非親水性単量体の含有量が７５質量％以下であれば、塗膜の防曇性がより優れる。 When the polymerizable monomer mixture contains a non-hydrophilic monomer, the content of the non-hydrophilic monomer in the polymerizable monomer mixture is 15 to 15 to the total mass of the polymerizable monomer mixture. 75% by mass is preferable, and 35 to 70% by mass is more preferable. When the content of the non-hydrophilic monomer is 15% by mass or more, the moisture resistance of the coating film is more excellent. When the content of the non-hydrophilic monomer is 75% by mass or less, the antifogging property of the coating film is more excellent.
本発明の防曇塗料用樹脂は、上述の重合性単量体混合物をリビングラジカル重合することにより得られる。
リビングラジカル重合としては、可逆的付加開裂連鎖移動重合（以下、ＲＡＦＴ重合ともいう。）、原子移動ラジカル重合（ＡＴＲＰ重合）、ニトロキシドによるラジカル重合（ＮＭＰ重合）等が挙げられる。これらの重合は公知の方法により実施できる。
The resin for antifogging coating material of the present invention is obtained by subjecting the above-mentioned polymerizable monomer mixture to living radical polymerization.
Examples of the living radical polymerization include reversible addition cleavage chain transfer polymerization (hereinafter, also referred to as RAFT polymerization), atom transfer radical polymerization (ATRP polymerization), radical polymerization by nitroxide (NMP polymerization) and the like. These polymerizations can be carried out by known methods.
以下、重合性単量体混合物をＲＡＦＴ重合する場合について、より詳細に説明する。
ＲＡＦＴ重合では、重合開始剤の存在下、連鎖移動剤（以下、ＲＡＦＴ重合に用いる連鎖移動剤を「ＲＡＦＴ剤」ともいう。）を用いて、重合性単量体混合物を重合させる。
Hereinafter, the case where the polymerizable monomer mixture is RAFT polymerized will be described in more detail.
In RAFT polymerization, a polymerizable monomer mixture is polymerized in the presence of a polymerization initiator using a chain transfer agent (hereinafter, the chain transfer agent used for RAFT polymerization is also referred to as “RAFT agent”).
ＲＡＦＴ重合に用いられる重合開始剤としては、特に限定されず、ラジカル重合を開始できるものであれば如何なるものを用いてもよい。このような重合開始剤としては、一般的には、過酸化物系重合開始剤、アゾ系重合開始剤等が用いられており、例えば２，２’−アゾビス（２−メチルブチロニトリル）、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２，４−ジメチルバレロニトリル）等が挙げられる。これらの重合開始剤はいずれか１種を単独で用いてもよく２種以上を併用してもよい。 The polymerization initiator used for RAFT polymerization is not particularly limited, and any polymerization initiator may be used as long as it can initiate radical polymerization. As such a polymerization initiator, a peroxide-based polymerization initiator, an azo-based polymerization initiator and the like are generally used, and for example, 2,2'-azobis (2-methylbutyronitrile), Examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile). Any one of these polymerization initiators may be used alone, or two or more thereof may be used in combination.
ＲＡＦＴ剤としては、特に限定されず、公知のＲＡＦＴ剤を用いることができる。例えばジチオエステル、トリチオカルボナート、ジチオカルバメート、キサンタート等のチオカルボニルチオ化合物が挙げられる。中でもジチオエステル、トリチオカルボナートが好ましい。具体例としては、４−シアノ−４−［（ドデシルスルファニルチオカルボニル）スルファニル］ペンタン酸、２−［（ドデシルスルファニルチオカルボニル）スルファニル］プロパン酸等が挙げられる。これらのＲＡＦＴ剤はいずれか１種を単独で用いてもよく２種以上を併用してもよい。 The RAFT agent is not particularly limited, and a known RAFT agent can be used. Examples thereof include thiocarbonylthio compounds such as dithioester, trithiocarbonate, dithiocarbamate and xanthate. Of these, dithioesters and trithiocarbonates are preferable. Specific examples include 4-cyano-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid, 2-[(dodecylsulfanylthiocarbonyl) sulfanyl] propanoic acid and the like. Any one of these RAFT agents may be used alone, or two or more thereof may be used in combination.
ＲＡＦＴ重合における重合方法としては、特に限定されず、公知の方法を採用でき、例えば、溶液重合法、乳化重合法、塊状重合法、懸濁重合法等が挙げられる。重合の際に用いる溶媒（重合溶媒）等についても特に限定されず、公知の溶媒等を用いることができる。重合条件も特に限定されず、例えば４０〜１００℃で２〜２４時間の条件が挙げられる。その後、冷却等によって反応を停止し、本発明の防曇塗料用樹脂が得られる。
なお、ＲＡＦＴ重合において、得られる樹脂の分子量は、重合開始剤の濃度ではなく、ＲＡＦＴ剤の濃度に依存する。
The polymerization method in RAFT polymerization is not particularly limited, and known methods can be adopted, and examples thereof include a solution polymerization method, an emulsion polymerization method, a massive polymerization method, and a suspension polymerization method. The solvent (polymerization solvent) or the like used in the polymerization is not particularly limited, and a known solvent or the like can be used. The polymerization conditions are also not particularly limited, and examples thereof include conditions of 40 to 100 ° C. for 2 to 24 hours. After that, the reaction is stopped by cooling or the like to obtain the antifogging coating resin of the present invention.
In RAFT polymerization, the molecular weight of the obtained resin depends on the concentration of the RAFT agent, not the concentration of the polymerization initiator.
本発明の防曇塗料用樹脂の分子量分布（Ｍｗ／Ｍｎ）は、１．１〜２．５が好ましく、１．１〜２．０がより好ましい。Ｍｗは重量平均分子量であり、Ｍｎは数平均分子量である。分子量分布が前記上限値以下であれば、水垂れ跡が残りにくい。
本発明の防曇塗料用樹脂の重量平均分子量（Ｍｗ）は、１万〜２０万が好ましく、２万〜１５万がより好ましい。Ｍｗが前記下限値以上であれば、耐湿性がより優れる傾向があり、前記上限値以下であれば、塗装性がより優れる傾向がある。
Ｍｗ及びＭｎはそれぞれ、ゲルパーミエーションクロマトグラフ法（ＧＰＣ）によって測定されるポリスチレン換算の値である。
The molecular weight distribution (Mw / Mn) of the antifogging coating resin of the present invention is preferably 1.1 to 2.5, more preferably 1.1 to 2.0. Mw is the weight average molecular weight and Mn is the number average molecular weight. When the molecular weight distribution is equal to or less than the upper limit value, it is difficult for water dripping marks to remain.
The weight average molecular weight (Mw) of the antifogging coating resin of the present invention is preferably 10,000 to 200,000, more preferably 20,000 to 150,000. When Mw is not less than the lower limit value, the moisture resistance tends to be more excellent, and when it is not more than the upper limit value, the coatability tends to be more excellent.
Mw and Mn are polystyrene-equivalent values measured by gel permeation chromatography (GPC), respectively.
本発明の防曇塗料用樹脂にあっては、単量体（ａ）及び単量体（ｂ）を特定の割合で含む重合性単量体混合物をリビングラジカル重合したものであるため、防曇塗料に用いたときに、防曇性に優れ、かつ水垂れ跡が残りにくい塗膜を形成できる。
特に、重合性単量体混合物中の単量体（ｂ）の含有量が２０質量％以下であれば、形成される塗膜は、ポリカーボネート等の透明樹脂基材に対する密着性にも優れる。
Since the resin for antifogging coating material of the present invention is a living radical polymerization of a polymerizable monomer mixture containing the monomer (a) and the monomer (b) in a specific ratio, it is antifogging. When used as a paint, it can form a coating film that has excellent antifogging properties and does not leave dripping marks.
In particular, when the content of the monomer (b) in the polymerizable monomer mixture is 20% by mass or less, the formed coating film is also excellent in adhesion to a transparent resin base material such as polycarbonate.
単量体（ａ）は、塗膜の親水性を高めて防曇性を付与する。重合性単量体混合物中の単量体（ａ）の割合が、充分な防曇性を付与できる程度に高い場合、リビングラジカル重合ではない通常のラジカル重合では、分子量分布が広く、また高分子鎖中での単量体（ａ）由来の構成単位の配置に偏りが生じる。このような分子量の偏りや構成単位の配置の偏りから、樹脂中に局所的に過度に親水性の高い部分が存在し、形成された塗膜に水滴が接した際、この親水性の高い部分が溶解し、水垂れ跡になっていたと考えられる。
本発明の防曇塗料用樹脂は、重合性単量体混合物の重合手法としてリビングラジカル重合を用いているため、通常のラジカル重合を用いた場合に比べて、上記のような分子量の偏りと構成単位の配置の偏りが抑制されている。そのため、防曇性と水垂れ跡の残りにくさとを高いレベルで両立できると考えられる。
The monomer (a) enhances the hydrophilicity of the coating film and imparts antifogging property. When the ratio of the monomer (a) in the polymerizable monomer mixture is high enough to impart sufficient antifogging property, the normal radical polymerization other than the living radical polymerization has a wide molecular weight distribution and a polymer. The arrangement of the structural units derived from the monomer (a) in the chain is biased. Due to such a bias in molecular weight and a bias in the arrangement of structural units, there is a locally excessively hydrophilic portion in the resin, and when water droplets come into contact with the formed coating film, this highly hydrophilic portion is present. It is probable that was dissolved and became a trace of water dripping.
Since the resin for antifogging coating of the present invention uses living radical polymerization as a polymerization method for the polymerizable monomer mixture, the molecular weight is biased and configured as described above as compared with the case where ordinary radical polymerization is used. The bias of the unit arrangement is suppressed. Therefore, it is considered that anti-fog property and resistance to remaining water dripping marks can be achieved at a high level.
なお、本発明の防曇塗料用樹脂において、単量体（ａ）、単量体（ｂ）等がどのように重合しているのか、詳細に特定することは困難である。例えば高分子鎖中で単量体（ａ）由来の構成単位がどのように配置されているかを特定することは困難である。即ち、本発明の防曇塗料用樹脂には、その構造又は特性によって直接特定することが不可能であるか、又はおよそ実際的ではないという事情（不可能・非実際的事情）が存在する。したがって、本発明の防曇塗料用樹脂は「重合性単量体混合物をリビングラジカル重合した」と規定することがより適切とされる。 In the anti-fog coating resin of the present invention, it is difficult to specify in detail how the monomer (a), the monomer (b) and the like are polymerized. For example, it is difficult to specify how the structural units derived from the monomer (a) are arranged in the polymer chain. That is, the antifogging coating resin of the present invention has a situation (impossible / impractical situation) that cannot be directly specified by its structure or characteristics, or is almost impractical. Therefore, it is more appropriate to define that the resin for antifogging coating material of the present invention is "living radical polymerization of a polymerizable monomer mixture".
〔防曇塗料〕
本発明の防曇塗料は、上述の本発明の防曇塗料用樹脂を含む。防曇塗料に含まれる防曇塗料用樹脂は１種でもよく２種以上でもよい。
[Anti-fog paint]
The antifogging coating material of the present invention includes the above-mentioned resin for antifogging coating material of the present invention. The antifogging paint resin contained in the antifogging paint may be one kind or two or more kinds.
本発明の防曇塗料は、典型的には、酸触媒をさらに含む。酸触媒は、防曇塗料用樹脂の架橋（硬化）反応を促進する。具体的には、水酸基同士の縮合反応、必要に応じてアルコキシ基の加水分解反応を促進する。
酸触媒としては、スルホン酸系触媒、リン酸系触媒等が挙げられる。スルホン酸系触媒としては、例えばｐ−トルエンスルホン酸、ドデシルベンゼンスルホン酸等のアルキルベンゼンスルホン酸が挙げられる。リン酸系触媒としては、例えばトリイソデシルホスフェイト、エチルアシッドホスフェイト、イソプロピルアシッドホスフェイト等が挙げられる。これらの酸触媒はいずれか１種を単独で用いてもよく２種以上を併用してもよい。上記の中でも、スルホン酸系触媒が好ましい。スルホン酸系触媒を用いることで、塗膜の硬化性 がより優れる。
The antifogging coating of the present invention typically further comprises an acid catalyst. The acid catalyst promotes the cross-linking (curing) reaction of the anti-fog coating resin. Specifically, it promotes a condensation reaction between hydroxyl groups and, if necessary, a hydrolysis reaction of an alkoxy group.
Examples of the acid catalyst include a sulfonic acid-based catalyst and a phosphoric acid-based catalyst. Examples of the sulfonic acid-based catalyst include alkylbenzene sulfonic acids such as p-toluene sulfonic acid and dodecylbenzene sulfonic acid. Examples of the phosphoric acid-based catalyst include triisodecyl phosphate, ethyl acid phosphate, isopropyl acid phosphate and the like. Any one of these acid catalysts may be used alone, or two or more thereof may be used in combination. Among the above, a sulfonic acid-based catalyst is preferable. By using a sulfonic acid-based catalyst, the curability of the coating film is more excellent.
本発明の防曇塗料は、有機溶剤をさらに含んでもよい。有機溶剤としては、例えばメタノール、エタノール、プロパノール、ブタノール等の低級アルコール系溶剤、ブチルセロソルブ等のセロソルブ系溶剤、酢酸エチル、酢酸ブチル等のエステル系溶剤、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤、ダイアセトンアルコール等が挙げられる。これらの有機溶剤はいずれか１種を単独で用いてもよく２種以上を併用してもよい。 The antifogging coating material of the present invention may further contain an organic solvent. Examples of the organic solvent include lower alcohol solvents such as methanol, ethanol, propanol and butanol, cellosolvent solvents such as butyl cellosolve, ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and dies. Examples include acetone alcohol. Any one of these organic solvents may be used alone, or two or more thereof may be used in combination.
本発明の防曇塗料は、必要に応じて、本発明の防曇塗料用樹脂、酸触媒及び有機溶剤以外の他の成分をさらに含んでもよい。他の成分としては、例えば、界面活性剤、シリコン系やフッ素系のレベリング剤、紫外線吸収剤、酸化防止剤、光安定剤（ＨＡＬＳ）等の各種の添加剤が挙げられる。 The antifogging coating material of the present invention may further contain components other than the resin for the antifogging coating material of the present invention, the acid catalyst and the organic solvent, if necessary. Examples of other components include various additives such as surfactants, silicon-based and fluorine-based leveling agents, ultraviolet absorbers, antioxidants, and light stabilizers (HALS).
本発明の防曇塗料において、本発明の防曇塗料用樹脂の含有量は、有機溶剤以外の成分の合計質量に対し、８０質量％以上が好ましく、８５〜９９質量％がより好ましい。防曇塗料用樹脂の含有量が前記下限値以上であれば、形成される塗膜の防曇性、基材に対する密着性がより優れる。 In the antifogging coating material of the present invention, the content of the antifogging coating resin of the present invention is preferably 80% by mass or more, more preferably 85 to 99% by mass, based on the total mass of the components other than the organic solvent. When the content of the anti-fog coating resin is at least the above lower limit value, the anti-fog property of the formed coating film and the adhesion to the base material are more excellent.
酸触媒の含有量は、本発明の防曇塗料用樹脂１００質量部に対して、３．０〜１０．０質量部が好ましく、３．０〜５．５質量部がより好ましい。酸触媒の含有量が前記下限値以上であれば、塗膜が充分に硬化しやすい。酸触媒の含有量が前記上限値以下であれば、ポリカーボネート等の基材に対する塗膜の付着性がより優れる。 The content of the acid catalyst is preferably 3.0 to 10.0 parts by mass, more preferably 3.0 to 5.5 parts by mass, based on 100 parts by mass of the antifogging coating resin of the present invention. When the content of the acid catalyst is at least the above lower limit value, the coating film is easily sufficiently cured. When the content of the acid catalyst is not more than the above upper limit value, the adhesion of the coating film to a substrate such as polycarbonate is more excellent.
防曇塗料が有機溶剤を含む場合、防曇塗料中の固形分濃度（有機溶剤以外の成分の含有量）は、防曇塗料の塗装方法を勘案して適宜設定でき、例えば５〜３０質量％であってよい。 When the antifogging paint contains an organic solvent, the solid content concentration (content of components other than the organic solvent) in the antifogging paint can be appropriately set in consideration of the coating method of the antifogging paint, for example, 5 to 30% by mass. It may be.
本発明の防曇塗料は、任意の基材に防曇性を付与するために用いられる。基材の表面に本発明の防曇塗料を塗装し、塗膜（防曇塗膜）を形成することで、防曇性が付与される。
基材の材質としては、特に制限はなく、例えばポリカードネート、ポリメチルメタクリレート等の樹脂、ガラス等が挙げられる。疎水性が高いために結露により曇りやすく、防曇性を付与することの有効性が高い点で、ポリカーボネート、ポリメチルメタクリレート等の透明樹脂が好適である。
防曇塗料の塗装方法としては、ディッピング法、スプレー法、ローラー法、フローコート法等の公知の塗装方法が採用できる。
塗装した防曇塗料を熱硬化させることにより、塗膜が形成される。熱硬化条件は、例えば、８０〜１２５℃で５〜３０分間であってよい。
形成される塗膜の厚さは、特に制限はない。例えば硬化後の厚さとして１〜８μｍであってよい。
本発明の防曇塗料が塗装された基材は、例えば自動車のヘッドランプ等の車両灯具、オートバイ等のメーターカバーやヘルメット等のバイザーカバー等に用いることができる。
The antifogging coating material of the present invention is used to impart antifogging properties to any base material. Anti-fog property is imparted by coating the surface of the base material with the anti-fog coating material of the present invention to form a coating film (anti-fog coating film).
The material of the base material is not particularly limited, and examples thereof include resins such as polycardate and polymethylmethacrylate, and glass. A transparent resin such as polycarbonate or polymethylmethacrylate is preferable because it is easily fogged by dew condensation due to its high hydrophobicity and is highly effective in imparting antifogging properties.
As a method for applying the antifogging paint, a known coating method such as a dipping method, a spray method, a roller method, or a flow coating method can be adopted.
A coating film is formed by thermosetting the applied antifogging paint. The thermosetting conditions may be, for example, 80 to 125 ° C. for 5 to 30 minutes.
The thickness of the coating film formed is not particularly limited. For example, the thickness after curing may be 1 to 8 μm.
The base material coated with the antifogging paint of the present invention can be used, for example, for vehicle lighting equipment such as automobile headlamps, meter covers for motorcycles, and visor covers such as helmets.
以上説明した本発明の防曇塗料は、本発明の防曇塗料用樹脂を含むため、防曇性に優れ、かつ水垂れ跡が残りにくい塗膜を形成できる。
特に、本発明の防曇塗料用樹脂を形成する重合性単量体混合物中の単量体（ｂ）の含有量が２０質量％以下であれば、形成される塗膜は、ポリカーボネート等の透明樹脂基材に対する密着性にも優れる。
Since the antifogging coating material of the present invention described above contains the resin for the antifogging coating material of the present invention, it is possible to form a coating film having excellent antifogging properties and less likely to leave water dripping marks.
In particular, when the content of the monomer (b) in the polymerizable monomer mixture forming the resin for antifogging coating of the present invention is 20% by mass or less, the coating film formed is transparent such as polycarbonate. It also has excellent adhesion to the resin substrate.
以下、実施例により本発明をさらに詳しく説明するが、本発明はこれらに限定されるものではない。以下において、「部」は「質量部」である。
以下において用いる各記号は、以下の各化合物を表すものとする。
ａ−１：ジエチルアクリルアミド。
ａ−２：アクリロイルモルホリン。
ａ−３：ジメチルアクリルアミド。
ａ−４：イソプロピルアクリルアミド。
ａ−５：Ｎ−ドデシルアクリルアミド。
ｂ−１：Ｎ−（メトキシメチル）アクリルアミド。
ｂ−２：Ｎ−（ヒドロキシメチル）アクリルアミド。
ｂ−３：Ｎ−（２−ヒドロキシメチル）アクリルアミド。
ＭＭＡ：メチルメタクリレート。
ＥＭＡ：エチルメタクリレート。
ＣＨＭＡ：シクロヘキシルメタクリレート。
ＡＢＮ−Ｅ：２，２’−アゾビス（２−メチルブチロニトリル）、株式会社日本ファインケム製。
Ｖ６５：２，２’−アゾビス（２，４−ジメチルバレロニトリル）、和光純薬工業株式会社製。
ＲＡＦＴ−１：下式（１）で表される化合物。
ＲＡＦＴ−２：下式（２）で表される化合物。
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the following, "part" is "part by mass".
Each symbol used below shall represent each of the following compounds.
a-1: Diethyl acrylamide.
a-2: Acryloyl morpholine.
a-3: Dimethyl acrylamide.
a-4: Isopropylacrylamide.
a-5: N-dodecylacrylamide.
b-1: N- (methoxymethyl) acrylamide.
b-2: N- (hydroxymethyl) acrylamide.
b-3: N- (2-hydroxymethyl) acrylamide.
MMA: Methyl methacrylate.
EMA: Ethyl methacrylate.
CHMA: Cyclohexyl methacrylate.
ABN-E: 2,2'-azobis (2-methylbutyronitrile), manufactured by Japan Finechem Company, Inc.
V65: 2,2'-azobis (2,4-dimethylvaleronitrile), manufactured by Wako Pure Chemical Industries, Ltd.
RAFT-1: A compound represented by the following formula (1).
RAFT-2: A compound represented by the following formula (2).
＜実施例１〜１７、比較例１〜４＞
表１〜３に示す配合に従って単量体、ＲＡＦＴ剤、重合開始剤及び重合溶媒を２口フラスコに投入し、フラスコ内を窒素ガスで置換しながら昇温し、表１〜３に示す重合条件（温度及び時間）にて撹拌下で重合反応を行い、不揮発分約４０質量％の樹脂溶液を得た。
各例における重合率（％）（得られた樹脂溶液の不揮発分／樹脂溶液の理論不揮発分×１００）を表１〜３に示す。得られた樹脂溶液の不揮発分（％、実測値）は、樹脂溶液約１ｇを分取し１３５℃×６０分で加熱したときの、加熱前の質量に対する加熱後の質量の比率として求めた。樹脂溶液の理論不揮発分（％）は、（単量体総量（部）＋ＲＡＦＴ剤量（部）＋重合開始剤量（部））／総仕込量（部）×１００により算出した。また、樹脂溶液に含まれる樹脂について、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によりポリスチレン換算の数平均分子量（Ｍｎ）、重量平均分子量（Ｍｗ）及び分子量分布（Ｍｗ／Ｍｎ）を求めた。ＧＰＣの測定条件は、以下の通りとした。結果を表１〜３に示す。
ＧＰＣ装置：ＧＰＣ−１０１（昭光通商株式会社製）。
カラム：Ｓｈｏｄｅｘ Ａ−８０６Ｍ×２本直列つなぎ（昭和電工株式会社製）。
検出器：Ｓｈｏｄｅｘ ＲＩ−７１（昭和電工株式会社製）。
移動相：テトラヒドロフラン。
流速：１ｍＬ／分。
<Examples 1 to 17, Comparative Examples 1 to 4>
The monomer, RAFT agent, polymerization initiator and polymerization solvent were put into a two-necked flask according to the formulations shown in Tables 1 to 3, and the temperature was raised while replacing the inside of the flask with nitrogen gas, and the polymerization conditions shown in Tables 1 to 3 were obtained. The polymerization reaction was carried out under stirring at (temperature and time) to obtain a resin solution having a non-volatile content of about 40% by mass.
The polymerization rate (%) (nonvolatile content of the obtained resin solution / theoretical non-volatile content of the resin solution × 100) in each example is shown in Tables 1 to 3. The non-volatile content (%, measured value) of the obtained resin solution was determined as the ratio of the mass after heating to the mass before heating when about 1 g of the resin solution was separated and heated at 135 ° C. × 60 minutes. The theoretical non-volatile content (%) of the resin solution was calculated by (total amount of monomer (parts) + amount of RAFT agent (parts) + amount of polymerization initiator (parts)) / total amount charged (parts) × 100. Further, regarding the resin contained in the resin solution, the polystyrene-equivalent number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC). The measurement conditions of GPC were as follows. The results are shown in Tables 1-3.
GPC device: GPC-101 (manufactured by Shoko Co., Ltd.).
Column: Shodex A-806M x 2 series connection (manufactured by Showa Denko KK).
Detector: Shodex RI-71 (manufactured by Showa Denko KK).
Mobile phase: tetrahydrofuran.
Flow velocity: 1 mL / min.
得られた樹脂溶液に、表１〜３に示す配合に従って、有機溶剤及び酸触媒を加え、防曇塗料とした。
得られた防曇塗料をポリカーボネート板の表面に、乾燥後の厚さが２〜３μｍとなるようにスプレー法にて塗装し、１２０℃で１５分間加熱乾燥して塗膜を形成した。得られた塗膜付きポリカーボネート板を試験材として、以下の手順で、初期防曇性の評価、水垂れ跡試験、初期付着性の評価、耐湿試験後外観の評価を行った。結果を表１〜３に示す。
An organic solvent and an acid catalyst were added to the obtained resin solution according to the formulations shown in Tables 1 to 3 to prepare an antifogging coating material.
The obtained antifogging paint was applied to the surface of the polycarbonate plate by a spray method so that the thickness after drying was 2 to 3 μm, and the coating film was formed by heating and drying at 120 ° C. for 15 minutes. Using the obtained polycarbonate plate with a coating film as a test material, the initial anti-fog property, the water dripping mark test, the initial adhesion evaluation, and the appearance after the moisture resistance test were evaluated by the following procedure. The results are shown in Tables 1-3.
（初期防曇性）
試験材を、塗膜表面を水滴が流れ落ちるように立て掛け、塗膜に対し４０℃のスチームを３分間当て、塗膜の外観を目視で観察し、以下の基準で初期防曇性を評価した。なお、スチーム中に塗膜が白化または溶解した場合は、初期防曇性の評価は中止した。
○：スチーム中に塗膜が曇らない。
△：スチーム中は塗膜が曇るが、スチームを止めてから５秒以内に曇りが取れる。
×：スチーム中に塗膜が曇り、スチームを止めてから５秒経過しても曇りが取れない。
(Initial anti-fog property)
The test material was leaned against the surface of the coating film so that water droplets flowed down, steam was applied to the coating film at 40 ° C. for 3 minutes, the appearance of the coating film was visually observed, and the initial antifogging property was evaluated according to the following criteria. When the coating film was whitened or dissolved during steam, the evaluation of the initial antifogging property was stopped.
◯: The coating film does not become cloudy during steam.
Δ: The coating film becomes cloudy during steam, but the cloudiness can be removed within 5 seconds after the steam is stopped.
X: The coating film becomes cloudy during steam, and the cloudiness cannot be removed even after 5 seconds have passed since the steam was stopped.
（水垂れ跡試験）
初期防曇性の評価でスチームを当てた後の試験材を、温度２５±２℃、湿度５５±５％ＲＨの環境下で１２時間放置した。これにより塗膜を乾燥させた。放置後の塗膜の外観を目視で観察し、以下の基準で水垂れ跡の残りにくさを評価した。
○：塗膜に水垂れ跡が無い。
×：塗膜に水垂れ跡が有る。
(Water dripping mark test)
The test material after being steamed in the evaluation of the initial antifogging property was left for 12 hours in an environment of a temperature of 25 ± 2 ° C. and a humidity of 55 ± 5% RH. This dried the coating film. The appearance of the coating film after being left to stand was visually observed, and the resistance to residual water dripping marks was evaluated according to the following criteria.
◯: There is no trace of water dripping on the coating film.
X: There is a water dripping mark on the coating film.
（初期付着性）
試験材の塗膜に１ｍｍ幅で１０×１０の碁盤目状にカッターで切れ目を入れ、碁盤目状の部分にセロハンテープ（ニチバン社製「ＣＴ−２４」）を貼着し剥がす操作を実施した。
○：セロハンテープへの塗膜の付着が無い。
△：セロハンテープへ１個以上２０個未満の碁盤目の付着が有る。
×：セロハンテープへ２０個以上の碁盤目の付着が有る。
(Initial adhesion)
A 1 mm wide 10 × 10 grid-shaped cut was made in the coating film of the test material, and cellophane tape (“CT-24” manufactured by Nichiban Co., Ltd.) was attached to the grid-shaped portion and peeled off. ..
◯: There is no adhesion of the coating film to the cellophane tape.
Δ: 1 or more and less than 20 grids are attached to the cellophane tape.
X: There are 20 or more grids attached to the cellophane tape.
（耐湿試験後外観）
試験材を６５℃、９５％ＲＨの環境下に１０日間放置した。その後、塗膜の外観を目視で観察し、以下の基準で評価した。
○：塗膜の外観に変化が無い。
△：塗膜に僅かな白化等の変化が見られる。
×：塗膜が白化又は溶解した。
(Appearance after moisture resistance test)
The test material was left in an environment of 65 ° C. and 95% RH for 10 days. Then, the appearance of the coating film was visually observed and evaluated according to the following criteria.
◯: There is no change in the appearance of the coating film.
Δ: A slight change such as whitening is observed in the coating film.
X: The coating film was whitened or dissolved.
各実施例によれば、防曇性に優れ、かつ水垂れ跡が残りにくい塗膜を形成できた。
一方、単量体（ａ）の含有量が１５質量％未満の比較例１では、塗膜の防曇性が劣っていた。単量体（ａ）の含有量が４５質量％超の比較例２では、塗膜がスチームによって白化し、防曇塗膜として機能しなかった。単量体（ｂ）の含有量が５質量％未満の比較例３では、塗膜がスチームによって溶解し、防曇塗膜として機能しなかった。重合性単量体混合物を通常のラジカル重合（ランダム重合）で重合した比較例４では、塗膜に水垂れ跡が残っていた。
According to each example, it was possible to form a coating film having excellent anti-fog properties and less likely to leave traces of water dripping.
On the other hand, in Comparative Example 1 in which the content of the monomer (a) was less than 15% by mass, the antifogging property of the coating film was inferior. In Comparative Example 2 in which the content of the monomer (a) was more than 45% by mass, the coating film was whitened by steam and did not function as an anti-fog coating film. In Comparative Example 3 in which the content of the monomer (b) was less than 5% by mass, the coating film was dissolved by steam and did not function as an anti-fog coating film. In Comparative Example 4 in which the polymerizable monomer mixture was polymerized by ordinary radical polymerization (random polymerization), water dripping marks remained on the coating film.
実施例３及び比較例４において、重合中の複数の時点で反応系の重合率及び重合物の重量平均分子量（Ｍｗ）を測定した。測定結果から、横軸に重合率、縦軸にＭｗをとったグラフを作成し、図１に示した。
図１から、比較例４（通常のラジカル重合）では、最初に高分子量の重合体が生成し、次第に低分子量の重合体が増えてＭｗが低下していること、対して実施例３（リビングラジカル重合）では、最初に低分子量の重合体が生成し、その分子鎖が次第に伸長してＭｗが増大していること、がわかる。
In Example 3 and Comparative Example 4, the polymerization rate of the reaction system and the weight average molecular weight (Mw) of the polymer were measured at a plurality of time points during the polymerization. From the measurement results, a graph with the polymerization rate on the horizontal axis and Mw on the vertical axis was created and shown in FIG.
From FIG. 1, in Comparative Example 4 (ordinary radical polymerization), a high molecular weight polymer was first produced, and then the low molecular weight polymer gradually increased and Mw decreased, whereas in Example 3 (living room). In radical polymerization), it can be seen that a polymer having a low molecular weight is first produced, and the molecular chain is gradually extended to increase Mw.
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