JPH07113062A - Composition for coating compound - Google Patents
Composition for coating compoundInfo
- Publication number
- JPH07113062A JPH07113062A JP28395593A JP28395593A JPH07113062A JP H07113062 A JPH07113062 A JP H07113062A JP 28395593 A JP28395593 A JP 28395593A JP 28395593 A JP28395593 A JP 28395593A JP H07113062 A JPH07113062 A JP H07113062A
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- JP
- Japan
- Prior art keywords
- weight
- parts
- resin
- monomer
- vinyl
- 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.)
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- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Silicon Polymers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、塗膜形成要素として耐
候性、防食性、耐クラック性、耐汚染性、密着性等の性
能の優れた塗料用樹脂組成物（ビヒクル固形分）に関
し、この樹脂組成物をビヒクル固形分として使用した塗
料は、金属、セラミックス、ガラス、プラスチック等に
塗装して自動車、産業用電気製品、家庭電化製品、建築
材、精密機械等に広く応用することができる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating resin composition (vehicle solid content) having excellent properties such as weather resistance, corrosion resistance, crack resistance, stain resistance, and adhesion as a film-forming element. A paint using this resin composition as a vehicle solid content can be applied to metals, ceramics, glass, plastics, etc., and can be widely applied to automobiles, industrial electric appliances, household appliances, building materials, precision machinery, etc. .
【０００２】[0002]
【従来の技術】耐水性、耐湿性、耐食性、耐候性、耐摩
耗性等の優れた塗膜を作ることのできるいわゆる耐久性
のある屋外用耐候性塗料は、メンテナンスフリーの塗料
として、紫外線、風雨等に対して耐久性を要望される建
物、構築物、車輛等に広く用いられている。この代表的
なものにフッ素系樹脂塗料があり、その抜群の耐候性を
生かして屋外での耐久性を要求される用途に使用されて
いる。2. Description of the Related Art A so-called durable outdoor weather-resistant paint capable of forming a coating film excellent in water resistance, moisture resistance, corrosion resistance, weather resistance, abrasion resistance, etc. It is widely used in buildings, structures, vehicles, etc. that require durability against wind and rain. A typical example of this is a fluorine-based resin paint, which is used for applications that require outdoor durability by taking advantage of its outstanding weather resistance.
【０００３】しかしながら、フッ素系樹脂塗料は、一般
に焼付温度での溶融粘度が高いため加工性が劣ってお
り、塗膜中に微細なボイド（空孔）を残し易い欠点を有
し、また表面硬度が小さく、更に粉塵、マジックイン
キ、食品などにより汚れ易く、取れにくいという欠点が
あった。However, the fluororesin coating material generally has a high melt viscosity at the baking temperature and thus is inferior in workability, and has the drawback that fine voids (pores) are likely to remain in the coating film, and the surface hardness is also high. However, it has a drawback that it is easily soiled with dust, magic ink, food, etc., and is difficult to remove.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、フッ素樹脂
系塗料の有する耐候性という長所を生かした上で、フッ
素樹脂系塗料の欠点である加工性の改良、塗膜形成能の
改善並びに硬度、耐汚染性を向上することを目的として
いる。DISCLOSURE OF THE INVENTION The present invention takes advantage of the weather resistance of fluororesin-based paints, and further improves workability, which is a drawback of fluororesin-based paints, and improves film-forming ability and hardness. , Is intended to improve the stain resistance.
【０００５】[0005]
【課題を解決するための手段】本発明は、側鎖に重合性
の不飽和基を有するオルガノシルセスキオキサンオリゴ
マーおよびビニルモノマー（１）との共重合体樹脂
（Ａ）および重合性の不飽和基を有するフッ素化炭化水
素モノマーの重合体、またはそれとビニルモノマー
（２）を共重合して得られるフッ素系樹脂（Ｂ）とを配
合した塗料用組成物を開発することにより前記の目的を
達成した。The present invention is directed to a copolymer resin (A) with an organosilsesquioxane oligomer having a polymerizable unsaturated group in its side chain and a vinyl monomer (1) and a polymerizable resin. By developing a polymer of a fluorinated hydrocarbon monomer having a saturated group or a fluorine-based resin (B) obtained by copolymerizing the same with a vinyl monomer (2), a coating composition is developed. Achieved
【０００６】本発明において重合性の不飽和基を有する
オルガノシルセスキオキサンオリゴマー（以下、単にシ
リコーンオリゴマーという。）は、一般式（１）In the present invention, the organosilsesquioxane oligomer having a polymerizable unsaturated group (hereinafter, simply referred to as a silicone oligomer) has the general formula (1).
【化３】 または一般式（２）[Chemical 3] Or general formula (2)
【化４】 で示される構造を有するオリゴマーである。[Chemical 4] It is an oligomer having a structure shown by.
【０００７】これらのシリコーンオリゴマーは種々の方
法で合成することができる。例えば一般式（１）のシリ
コーンオリゴマーは、モノアルキル［またはモノフェニ
ル（置換されていても良い。）］−トリアルコキシシラ
ン（または−トリクロルシラン）とヒドロキシアルキル
−トリアルコキシシラン（または−トリクロルシラン）
とを共縮合させ、得られたヒドロキシアルキル基を有す
るシリコーン化合物に（メタ）アクリル酸を反応させる
か、（メタ）アクリロキシアルキル−トリアルコキシシ
ラン（または−トリクロルシラン）を共縮合させれば良
い。この場合の（メタ）アクリロキシアルキル−トリア
ルコキシシランまたは（メタ）アクリロキシアルキル−
トリクロルシランとしては、（メタ）アクリロキシ−メ
チル−トリメトキシシラン、（メタ）アクリロキシ−エ
チル−トリエトキシシラン、（メタ）アクリロキシ−プ
ロピル−トリメトキシシラン、（メタ）アクリロキシ−
エチル−トリクロルシラン、（メタ）アクリロキシ−プ
ロピル−トリクロルシラン等を挙げることができる。These silicone oligomers can be synthesized by various methods. For example, the silicone oligomer represented by the general formula (1) includes a monoalkyl [or monophenyl (which may be substituted)]-trialkoxysilane (or -trichlorosilane) and a hydroxyalkyl-trialkoxysilane (or -trichlorosilane).
And (meth) acrylic acid are reacted with the obtained silicone compound having a hydroxyalkyl group, or (meth) acryloxyalkyl-trialkoxysilane (or -trichlorosilane) is co-condensed with . In this case, (meth) acryloxyalkyl-trialkoxysilane or (meth) acryloxyalkyl-
Examples of trichlorosilane include (meth) acryloxy-methyl-trimethoxysilane, (meth) acryloxy-ethyl-triethoxysilane, (meth) acryloxy-propyl-trimethoxysilane, (meth) acryloxy-
Examples thereof include ethyl-trichlorosilane and (meth) acryloxy-propyl-trichlorosilane.
【０００８】また、一般式（２）の場合においては、一
般式（１）の化合物の合成における（メタ）アクリロキ
シアルキル−トリアルコキシシラン（または−トリクロ
ルシラン）に代えて、末端にビニル基を有するアルケニ
ル−トリアルコキシシラン（または−トリクロルシラ
ン）を用いて共縮合させれば良い。これらの化合物とし
ては例えばビニル−トリアルコキシシラン（またはトリ
クロルシラン）、プロペニル−トリアルコキシシラン
（またはトリクロルシラン）を挙げることができる。Further, in the case of the general formula (2), instead of the (meth) acryloxyalkyl-trialkoxysilane (or -trichlorosilane) in the synthesis of the compound of the general formula (1), a vinyl group is added to the terminal. The alkenyl-trialkoxysilane (or -trichlorosilane) may be used for cocondensation. Examples of these compounds include vinyl-trialkoxysilane (or trichlorosilane) and propenyl-trialkoxysilane (or trichlorosilane).
【０００９】シリコーンオリゴマーと共縮合するビニル
モノマー（１）としては、アクリル酸メチル、アクリル
酸エチル、アクリル酸ブチル、アクリル酸−２−エチル
ヘキシル、メタクリル酸メチル、メタクリル酸エチル、
メタクリル酸ブチル、メタクリル酸−２−エチルヘキシ
ル、スチレン、アルファメチルスチレン、酢酸ビニル、
プロピオン酸ビニル、ステアリン酸ビニル、バーサチッ
ク酸ビニル、エポキシアクリレート、ウレタンアクリレ
ート、シリコーンアクリレート、ヒドロキシエチルアク
リレート、ヒドロキシエチルメタクリレート、ヒドロキ
シプロピルアクリレート、ヒドロキシプロピルメタクリ
レート、アミノエチルアクリレート、アミノエチルメタ
クリレート等が用いられる。The vinyl monomer (1) co-condensed with the silicone oligomer includes methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate,
Butyl methacrylate, 2-ethylhexyl methacrylate, styrene, alpha methyl styrene, vinyl acetate,
Vinyl propionate, vinyl stearate, vinyl versatate, epoxy acrylate, urethane acrylate, silicone acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, aminoethyl acrylate, aminoethyl methacrylate and the like are used.
【００１０】このシリコーンオリゴマーとビニルモノマ
ー（１）を、過酸化ベンゾイル、過酸化ラウリル、アゾ
イソブチロニトリル、過酸化水素、過硫酸アンモニウム
のような過酸、過酸化物、アゾ化合物等のラジカル反応
開始剤を用いて、溶液重合、懸濁重合、乳化重合などの
方法により共重合させ共重合体樹脂（Ａ）を得ることが
できる。Radical reaction of the silicone oligomer with the vinyl monomer (1) such as benzoyl peroxide, lauryl peroxide, azoisobutyronitrile, hydrogen peroxide, peroxides such as ammonium persulfate, peroxides and azo compounds. A copolymer resin (A) can be obtained by copolymerizing using an initiator by a method such as solution polymerization, suspension polymerization or emulsion polymerization.
【００１１】この場合、シリコーンオリゴマーとビニル
モノマー（１）の配合比は、１〜９９部：９９〜１部、
好ましくは１０〜６０部：９０〜４０部（合計１００部
とする。）と相当広範に変えることができる。In this case, the compounding ratio of the silicone oligomer and the vinyl monomer (1) is 1 to 99 parts: 99 to 1 part,
It can be widely changed to preferably 10 to 60 parts: 90 to 40 parts (total of 100 parts).
【００１２】シリコーンオリゴマーが１０部より少なく
なるに従い、シリコーンの特徴である硬度、耐食性、耐
汚染性が低下し始め１部より少なくなると、その効果が
全くなくなる。また６０部より多くなると重合過程でゲ
ル化の危険が増し、９９部を越えるとほとんどの場合ゲ
ル化が避けられなくなる。When the amount of silicone oligomer is less than 10 parts, the hardness, corrosion resistance, and stain resistance, which are the characteristics of silicone, start to deteriorate, and when the amount is less than 1 part, the effect is completely abolished. If it exceeds 60 parts, the risk of gelation increases during the polymerization process, and if it exceeds 99 parts, gelation is unavoidable in most cases.
【００１３】一方、フッ素系樹脂（Ｂ）は、フッ化ビニ
ル、フッ化ビニリデン、三フッ化エチレン、四フッ化エ
チレン、クロロトリフルオロエチレン等フッ素化合物モ
ノマーのホモポリマーもしくはそれらの共重合体または
前記フッ素化合物モノマー、一般式（３）On the other hand, the fluorine-based resin (B) is a homopolymer of a fluorine compound monomer such as vinyl fluoride, vinylidene fluoride, ethylene trifluoride, ethylene tetrafluoride, chlorotrifluoroethylene or a copolymer thereof or the above. Fluorine compound monomer, general formula (3)
【化５】 または一般式（４）[Chemical 5] Or general formula (4)
【化６】 で示されるフロロアルキル（メタ）アクリレートおよび
これらとビニルモノマー（２）の共重合体である。フロ
ロアルキル（メタ）アクリレートとしては、一般式
（３）で示される末端ＣＦ3 基含有化合物のほうが撥水
性が大であるが、一般式（４）の末端ＣＨ3 含有化合物
の方が合成が容易である。[Chemical 6] Are fluoroalkyl (meth) acrylates and copolymers of these with vinyl monomers (2). As the fluoroalkyl (meth) acrylate, the terminal CF 3 group-containing compound represented by the general formula (3) has higher water repellency, but the terminal CH 3 -containing compound of the general formula (4) is easier to synthesize. Is.
【００１４】このビニルモノマー（２）としては、エチ
レン、プロピレン、ビニルエーテル、ビニルエステル、
メタクリル酸エステル、アクリル酸エステル、更に水酸
基を含むモノマーとしてヒドロキシエチルアクリレー
ト、ヒドロキシエチルメタクリレート、ヒドロキシプロ
ピルアクリレート、ヒドロキシプロピルメタクリレー
ト、ヒドロキシブチルビニルエーテル等を挙げることが
できる。As the vinyl monomer (2), ethylene, propylene, vinyl ether, vinyl ester,
Examples of the methacrylic acid ester, the acrylic acid ester, and the hydroxyl group-containing monomer include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and hydroxybutyl vinyl ether.
【００１５】フッ素系樹脂（Ｂ）はフッ素化合物モノマ
ー単独であるときはラジカル反応開始剤を用いて懸濁重
合、乳化重合が、ビニルモノマー（２）との共重合であ
るときは溶液重合（溶解性が不十分なときは乳化重合）
を行って製造する。When the fluorine-based resin (B) is a fluorine compound monomer alone, suspension polymerization or emulsion polymerization is carried out by using a radical reaction initiator, and when it is copolymerization with the vinyl monomer (2), solution polymerization (dissolution). Emulsion polymerization when properties are insufficient)
To manufacture.
【００１６】共重合体樹脂（Ａ）とフッ素系樹脂（Ｂ）
の配合比は、固形分として１〜９９重量部：９９〜１重
量部、好ましくは１０〜９０重量部：９０〜１０重量
部、より好ましくは１５〜７０重量部：８５〜３０重量
部（合計１００重量部）である。Copolymer resin (A) and fluororesin (B)
1 to 99 parts by weight: 99 to 1 parts by weight, preferably 10 to 90 parts by weight: 90 to 10 parts by weight, and more preferably 15 to 70 parts by weight: 85 to 30 parts by weight (total). 100 parts by weight).
【００１７】共重合体樹脂（Ａ）の配合比が１０重量部
より少ないと加工性、硬度、耐汚染性の性能が配合比に
並行して低下し、不十分となる。また（Ａ）の配合比が
９０重量部を越えるに従い、塗膜の硬度が増し、割れを
生じ易くなる傾向がある。When the blending ratio of the copolymer resin (A) is less than 10 parts by weight, the workability, hardness and stain resistance performances are lowered in parallel with the blending ratio and are insufficient. Further, as the compounding ratio of (A) exceeds 90 parts by weight, the hardness of the coating film tends to increase and cracking tends to occur.
【００１８】共重合体樹脂（Ａ）とフッ素系樹脂（Ｂ）
との混合は、それぞれの溶媒または分散媒が共通であれ
ばもっとも好ましいが、異なっても両者の溶媒または分
散媒が相溶性があり、他の溶液と混合してもゲル化を生
じないことが必要であり、このようなものであれば両者
を混合し、撹拌または振盪し、均一に混合することによ
り塗料用組成物が得られる。Copolymer resin (A) and fluororesin (B)
Mixing with is most preferable if the respective solvents or dispersion media are common, but even if they are different, both solvents or dispersion media are compatible, and even if mixed with other solutions, gelation may not occur. It is necessary, and in such a case, the coating composition can be obtained by mixing both, stirring or shaking, and uniformly mixing.
【００１９】更に、共重合体樹脂（Ａ）およびフッ素系
樹脂（Ｂ）からなる樹脂組成物に含まれるＯＨ、ＣＯＯ
Ｈ、ＣＯＮＨ2 、ＮＨ2 等の官能基を対象にカップリン
グ剤を配合し、室温または加熱により架橋硬化すること
もできる。Further, OH and COO contained in the resin composition comprising the copolymer resin (A) and the fluororesin (B).
It is also possible to mix a coupling agent for functional groups such as H, CONH 2 , NH 2 and the like, and crosslink and cure at room temperature or by heating.
【００２０】カップリング剤としては、ポリイソシアネ
ート化合物、アミノ樹脂、エポキシ樹脂等、前記官能基
と反応し、常温または加熱により架橋ができる化合物が
挙げられる。Examples of the coupling agent include polyisocyanate compounds, amino resins, epoxy resins, and other compounds that react with the functional groups and can be crosslinked at room temperature or by heating.
【００２１】このようにして得られた塗料用組成物に紫
外線吸収剤、酸化防止剤、脱泡剤、チクソ付与剤、硬化
剤などを添加してクリヤーコート塗料とするか、または
更に顔料、メタルフレーク、分散安定剤等を添加して着
色塗料をつくることができる。An ultraviolet absorber, an antioxidant, a defoaming agent, a thixotropic agent, a curing agent or the like is added to the coating composition thus obtained to prepare a clear coat coating, or a pigment or metal is further added. Colored paints can be made by adding flakes, dispersion stabilizers and the like.
【００２２】また本発明組成物の性能を損なわぬ範囲
で、アクリル樹脂、ビニル樹脂、アルキッド樹脂、ウレ
タン樹脂、エポキシ樹脂、シリコーン樹脂、ポリイミド
樹脂、セルロース系樹脂などを例えば本組成物の５０重
量％以下添加することができる。Acrylic resin, vinyl resin, alkyd resin, urethane resin, epoxy resin, silicone resin, polyimide resin, cellulosic resin, etc., for example, 50% by weight of the present composition may be used within a range not impairing the performance of the composition of the present invention. The following can be added.
【００２３】本組成物から製造した塗料は作業性よく、
ロールコート、フローコート、スプレーコートなど各種
の塗装法に適し、塗膜は耐候性、耐水性、耐湿性、耐光
性等に優れ、硬度が高く、耐汚染性も良好であり、屋内
用塗料はもちろん特に屋外用塗料として有効である。The paint produced from this composition has good workability,
Suitable for various coating methods such as roll coating, flow coating, and spray coating.The coating film has excellent weather resistance, water resistance, moisture resistance, light resistance, etc., high hardness, and good stain resistance. Of course, it is particularly effective as an outdoor paint.
【００２４】[0024]
【作用】フッ素系樹脂塗料は、一般に非粘着性、耐熱
性、耐薬品性、電気特性、耐候性、耐水性、耐湿性に優
れ、耐久性のある屋外使用用塗料として極めて優れた塗
料である。[Function] Fluorine resin paints are generally excellent in non-adhesiveness, heat resistance, chemical resistance, electrical properties, weather resistance, water resistance and moisture resistance, and are extremely excellent as durable paints for outdoor use. .
【００２５】しかし、フッ素系樹脂は一般に焼付温度に
おいて溶融粘度が高いため、塗膜のボイド発生が頻発
し、また表面硬度が小さいために傷の発生が多く、上記
の耐水性、耐食性などの性能を充分に発揮できないこと
が多く、更に粉塵、油脂、マジックインキ等により汚れ
やすく、かつ取れにくいという問題があった。However, since the fluorine-based resin generally has a high melt viscosity at the baking temperature, voids in the coating film frequently occur, and the surface hardness is small, so that many scratches occur, and the above-mentioned performances such as water resistance and corrosion resistance. In many cases, it is not possible to sufficiently exhibit the above, and there is a problem that it is easily soiled by dust, oil and fat, magic ink, etc., and is difficult to remove.
【００２６】このような問題点をラダータイプシリコー
ンオリゴマーとビニルモノマー（１）を共重合させて得
られる共重合体樹脂（Ａ）を配合することによりラダー
タイプシリコーン樹脂の塗膜表面硬度および耐汚染性の
向上、共重合体による作業性（ボイド発生の防止）の改
善に成功した。These problems are solved by blending the copolymer resin (A) obtained by copolymerizing the ladder-type silicone oligomer and the vinyl monomer (1) with the coating surface hardness and stain resistance of the ladder-type silicone resin. We succeeded in improving the workability and the workability of the copolymer (preventing the occurrence of voids).
【００２７】[0027]
（実施例１）メタアクリル基含量が２０モル％であり、
分子量２１００のＲ1 がプロペニル基である一般式
（１）のシリコーンオリゴマー３０重量部と、メタクリ
ル酸メチル３０重量部、アクリル酸ブチル３０重量部、
ヒドロキシエチルメタクリレート７重量部、メタクリル
酸３重量部とをトルエン中で溶液重合して、固形分６０
重量％、分子量２３，０００の共重合体樹脂（Ａ）の溶
液（Ａ−１）を作った。別にフッ化ビニリデン樹脂（分
子量１８，０００、平均粒径０．３μｍ）の粉末６０重
量部をイソホロン４０重量部と混合し分散液（Ｂ−１）
を作った。（Ａ−１）２０重量部、（Ｂ−１）８０重量
部とを配合し、ベンゾトリアゾール系紫外線吸収剤１．
５重量部、ピペリジン系光安定剤１．０重量部を添加し
た。この塗料をロールコーターを用い、エポキシプライ
マーの処理を施した鋼板に３０μｍの厚さ（乾燥膜厚）
にコートし、８０℃で予備乾燥後、２２０℃にて３分焼
きつけて仕上げた。塗板の試験結果を表１に示した。(Example 1) The content of methacrylic group is 20 mol%,
30 parts by weight of a silicone oligomer of the general formula (1) in which R 1 having a molecular weight of 2100 is a propenyl group, 30 parts by weight of methyl methacrylate, 30 parts by weight of butyl acrylate,
Solution polymerization of 7 parts by weight of hydroxyethyl methacrylate and 3 parts by weight of methacrylic acid in toluene to give a solid content of 60
A solution (A-1) of a copolymer resin (A) having a weight percentage of 23,000 and a molecular weight of 23,000 was prepared. Separately, 60 parts by weight of a powder of vinylidene fluoride resin (molecular weight: 18,000, average particle size: 0.3 μm) was mixed with 40 parts by weight of isophorone to prepare a dispersion liquid (B-1).
made. 20 parts by weight of (A-1) and 80 parts by weight of (B-1) are blended to prepare a benzotriazole-based ultraviolet absorber 1.
5 parts by weight and 1.0 part by weight of piperidine-based light stabilizer were added. Using a roll coater, apply this paint to a steel plate that has been treated with an epoxy primer to a thickness of 30 μm (dry film thickness).
Was pre-dried at 80 ° C. and baked at 220 ° C. for 3 minutes to finish. The test results of the coated plate are shown in Table 1.
【００２８】（比較例１）実施例１の（Ａ−１）の製造
においてシリコーンオリゴマーを省略し、後は同様の操
作でアクリルポリマーの固形分６０重量％のトルエン溶
液を製造した。（Ａ−２）このものの分子量は２５，０
００であった。（Ａ−２）２０重量部と（Ｂ−１）８０
重量部とを実施例１と同様に配合し、同様の方法でエポ
キシプライマー処理した鋼板にコートした。塗板の試験
結果を表１に併記した。実施例１と比較例１とを比較す
ると、特に硬度、耐汚染性において実施例１が優れてい
ることが分かる。(Comparative Example 1) In the production of (A-1) in Example 1, the silicone oligomer was omitted, and the same procedure was followed to produce a toluene solution of acrylic polymer having a solid content of 60% by weight. (A-2) The molecular weight of this product is 25,0
It was 00. (A-2) 20 parts by weight and (B-1) 80
Parts by weight were mixed in the same manner as in Example 1, and the epoxy-primed steel sheet was coated in the same manner. The test results of the coated plate are also shown in Table 1. Comparing Example 1 with Comparative Example 1, it can be seen that Example 1 is excellent in hardness and stain resistance.
【００２９】[0029]
【表１】 ＊ ＪＩＳ Ｋ ５４００ ＊＊マジックインキ赤を塗り、２４ｈｒｓ後紙でふきと
る。全部消えたものが○、一部残ったものが△[Table 1] * JIS K 5400 ** Apply the magic ink red and wipe it off with paper after 24 hours. The ones that have all disappeared are ○, and the ones that partially remain are △
【００３０】（実施例２）一般式（１）において、Ｒ1
がプロペニル基、Ｒ2 の９０モル％がメチル基であり、
１０モル％がフェニル基であり、メタアクリル基含量が
１７モル％であり、分子量１９００のシリコーンオリゴ
マー３０重量部、スチレン１０重量部、メタクリル酸メ
チル２０重量部、アクリル酸−２−エチルヘキシル３０
重量部およびヒドロキシプロピルメタクリレート１０重
量部とを酢酸ブチル、トルエン混液（２：１重量比）中
で溶液重合して、固形分濃度６０％、分子量２５，００
０のポリマー溶液（Ａ−３）を作った。別に四フッ化エ
チレン４０モル％、イソブチルビニルエーテル４０モル
％、ヒドロキシエチルメタクリレート２０％の共重合体
（分子量１６，０００）の固形分濃度６０％のキシレン
溶液（Ｂ−２）を作った。（Ａ−３）３０重量部、（Ｂ
−２）７０重量部とを配合し、ベンゾトリアゾール系紫
外線吸収剤１．５重量部、ピペリジン系光安定剤１．０
重量部、フッ素系消泡剤０．３重量部を添加し、更にチ
タン白５０重量部を加えて混練し、良く分散させて白色
塗料を製造した。この塗料に使用前にヘキサメチレンジ
イソシアネート３量体５重量部を加え、［（Ａ−３）と
（Ｂ−２）の全ＯＨのモル数とＮＣＯのモル数との比
１：１］を加え、スプレーコートにより、ウレタンプラ
イマー処理を施した珪カル板にコートした。塗膜厚は乾
燥状態で５０μｍとした。５０℃で乾燥後、８０℃で６
０分加熱して硬化せしめた。塗装物の試験結果を表２に
示した。Example 2 In the general formula (1), R 1
Is a propenyl group, 90 mol% of R 2 is a methyl group,
10 mol% is a phenyl group, the methacrylic group content is 17 mol%, 30 parts by weight of a silicone oligomer having a molecular weight of 1900, 10 parts by weight of styrene, 20 parts by weight of methyl methacrylate, 30 parts of 2-ethylhexyl acrylate.
Parts by weight and 10 parts by weight of hydroxypropyl methacrylate are solution polymerized in a mixed solution of butyl acetate and toluene (2: 1 weight ratio) to obtain a solid content concentration of 60% and a molecular weight of 25,000.
0 polymer solution (A-3) was made. Separately, a xylene solution (B-2) having a solid content concentration of 60% of a copolymer (molecular weight 16,000) of 40 mol% of tetrafluoroethylene, 40 mol% of isobutyl vinyl ether and 20% of hydroxyethyl methacrylate was prepared. (A-3) 30 parts by weight, (B
-2) 70 parts by weight of benzotriazole-based UV absorber 1.5 parts by weight, piperidine-based light stabilizer 1.0
By weight, 0.3 part by weight of a fluorine-based defoaming agent was added, and further 50 parts by weight of titanium white was added, kneaded, and well dispersed to produce a white paint. To this coating, 5 parts by weight of hexamethylene diisocyanate trimer were added before use, and [(A-3) and (B-2) total OH mole ratio to NCO mole ratio 1: 1] was added. By spray coating, it was coated on a silica plate that had been subjected to urethane primer treatment. The coating thickness was 50 μm in the dry state. After drying at 50 ° C, 6 at 80 ° C
It was heated for 0 minutes to cure. The test results of the coated products are shown in Table 2.
【００３１】（比較例２）実施例１の（Ａ−３）の成分
を省略し、（Ｂ−２）ポリマー溶液に実施例２と同じ添
加剤を加えて塗料を作った。配合量は（Ｂ−２）ポリマ
ー１００重量部にベンゾトリアゾール系紫外線吸収剤
１．５重量部、ピペリジン系光安定剤１．０重量部、フ
ッ素系消泡剤０．３重量部、チタン白５０重量部であ
る。この塗料に使用前にヘキサメチレンジイソシアネー
ト３量体３．６重量部を加え、［（Ｂ−２）中のＯＨの
モル数とＮＣＯのモル数との比は１：１］、スプレーコ
ートによりウレタンプライマー処理を施した珪カル板に
コートし、膜厚は乾燥状態で５０μｍとした。５０℃で
乾燥後、８０℃で６０分加熱して硬化せしめた。塗装物
の試験結果は表２に示すとおりであり、ウェザーメータ
ーによる促進耐候性試験は実施例２、比較例２共に優れ
ていたが、硬度、耐汚染性において実施例のほうが格段
に優れていた。(Comparative Example 2) The component (A-3) of Example 1 was omitted, and the same additives as in Example 2 were added to the polymer solution (B-2) to prepare a coating composition. The blending amount is 100 parts by weight of the polymer (B-2), 1.5 parts by weight of a benzotriazole-based ultraviolet absorber, 1.0 part by weight of a piperidine-based light stabilizer, 0.3 part by weight of a fluorine-based antifoaming agent, and titanium white 50. Parts by weight. Before use, 3.6 parts by weight of hexamethylene diisocyanate trimer was added to this paint, and the ratio of the number of moles of OH and the number of NCO in ((B-2) was 1: 1). A primer-treated silica plate was coated, and the film thickness was 50 μm in a dry state. After drying at 50 ° C., it was heated at 80 ° C. for 60 minutes to be cured. The test results of the coated product are shown in Table 2, and the accelerated weather resistance test using a weather meter was excellent in both Example 2 and Comparative Example 2, but the example was far superior in hardness and stain resistance. .
【００３２】[0032]
【表２】 ＊ ＪＩＳ Ｋ ５４００ ＊＊ マジックインキ赤を塗り、２４ｈｒｓ後紙でふき
とる。全部消えたものが○、一部残ったものが△ ＊＊＊ ３０日間９５ＲＨ[Table 2] * JIS K 5400 ** Apply magic ink red and wipe off with paper after 24 hours. All disappeared ○, some remained △ ＊＊＊ 30 days 95RH
【００３３】（実施例３）一般式（３）のａが３、Ｒ3
がメチル基で示されるパーフルオロオクタアルキルアク
リレート３０重量部、メタクリル酸メチル４０重量部、
アクリル酸ブチル２０重量部、ヒドロキシエチルメタク
リレート６部、メタクリル酸４部をトルエン溶液中で重
合してフッ素系樹脂（Ｂ）の固形分濃度６０％であるト
ルエン溶液（Ｂ−３）を製造した。実施例１の共重合体
樹脂（Ａ−１）６０重量部、前記で製造したフッ素系樹
脂（Ｂ−３）４０重量部の混合物にベンゾトリアゾール
系紫外線吸収剤１．５重量部、ピペリジン系光安定剤
１．０重量部を加え、該混合物１００重量部に更にヘキ
サメチレンジイソシアネート３量体２．９重量部［（Ａ
−１）と（Ｂ−３）の含有全ＯＨ基のモル数とイソシア
ネート基のモル比は１：１］を加え、アミノシランカッ
プリング剤でプライマー処理したポリカーボネート板に
乾燥塗膜厚２μｍとなるようにスプレーコートした。５
０℃で乾燥後、７０℃で３０分加熱して仕上げた。コー
ティングした塗膜の性質を表３に示す。(Example 3) In the general formula (3), a is 3, R 3
Is a methyl group, 30 parts by weight of perfluorooctaalkyl acrylate, 40 parts by weight of methyl methacrylate,
20 parts by weight of butyl acrylate, 6 parts of hydroxyethyl methacrylate and 4 parts of methacrylic acid were polymerized in a toluene solution to prepare a toluene solution (B-3) having a solid content concentration of 60% of the fluororesin (B). A mixture of 60 parts by weight of the copolymer resin (A-1) of Example 1 and 40 parts by weight of the fluororesin (B-3) prepared above was added to 1.5 parts by weight of a benzotriazole-based ultraviolet absorber and piperidine-based light. 1.0 part by weight of a stabilizer was added, and 2.9 parts by weight of hexamethylene diisocyanate trimer was added to 100 parts by weight of the mixture [(A
-1) and (B-3) are added so that the molar ratio of the total OH groups to the isocyanate groups is 1: 1], and a dry coating film thickness of 2 μm is applied to a polycarbonate plate primed with an aminosilane coupling agent. It was spray coated on. 5
After drying at 0 ° C., it was heated at 70 ° C. for 30 minutes to finish. The properties of the coated film are shown in Table 3.
【００３４】（比較例３）実施例３の処方のうち、（Ａ
−１）を省略して、（Ｂ−３）にヘキサメチレンジイソ
シアネート３量体の添加量を２．６重量部（ＯＨとイソ
シアネート基のモル比は１：１）添加したほかは同様の
操作で、同様な処理をしたポリカーボネート板にコーテ
ィングした。結果を表３に示した。表３から分かるよう
に（Ａ−１）の添加によるウエザオメーターによる耐候
性試験結果が著しく向上し、硬度、耐汚染性も優れてい
ることが分かった。(Comparative Example 3) Of the formulations of Example 3, (A
-1) is omitted, and the same operation is performed except that 2.6 parts by weight of hexamethylene diisocyanate trimer is added to (B-3) (the molar ratio of OH and isocyanate groups is 1: 1). A polycarbonate plate which had been treated in the same manner was coated. The results are shown in Table 3. As can be seen from Table 3, the weather resistance test result by the weatherometer by the addition of (A-1) was remarkably improved, and the hardness and the stain resistance were also excellent.
【００３５】[0035]
【表３】 ＊ ＪＩＳ Ｋ ５４００ ＊＊ マジックインキ赤を塗り、２４ｈｒｓ後紙でふき
とる。全部消えたものが○、一部残ったものが△ ＊＊＊ ステンレスウール（＃００００）で表面を５０
回摩擦した後の傷つき性：Ａ全く変化なし、Ｂ＞Ｃ＞Ｄ
で傷つき程度判定[Table 3] * JIS K 5400 ** Apply magic ink red and wipe off with paper after 24 hours. All disappeared ○, some remained △ *** Stainless steel wool (# 0000) 50 on the surface
Scratchability after repeated rubbing: A no change, B>C> D
Judgment degree with
【００３６】（実施例４）実施例１においてメタアクリ
ル基含量２０モル％のかわりに、ビニル基含量２０モル
％である分子量２，６００の一般式（２）のシリコーン
オリゴマーを合成した。 ［一般式（２）においてＲ1 ＝０，Ｒ’＝Ｈ］ このオリゴマー２０重量部とメタクリル酸メチル２０重
量部、アクリル酸２−エチルヘキシル３０重量部、バー
サチック酸ビニル２０重量部、ヒドロキシプロピルメタ
クリレート７重量部、アクリル酸３重量部とをトルエン
中で溶液重合して、固形分６０重量％、分子量３４，０
００の共重合樹脂溶液（Ａ−４）を作った。実施例１と
同様に（Ａ−４）２０重量部、（Ｂ−１）８０重量部、
ベンゾトリアゾール系紫外線吸収剤１．５重量部、ピペ
リジン系光安定剤１．０重量部とを加えて塗料を作成
し、実施例１と同様の操作でエポキシプライマーを施し
た鋼板に塗布した。塗板の試験結果は次のようである。Example 4 Instead of the methacrylic group content of 20 mol% in Example 1, a silicone oligomer of the general formula (2) having a vinyl group content of 20 mol% and a molecular weight of 2,600 was synthesized. [R 1 = 0, R ′ = H in General Formula (2)] 20 parts by weight of this oligomer, 20 parts by weight of methyl methacrylate, 30 parts by weight of 2-ethylhexyl acrylate, 20 parts by weight of vinyl versatate, and 7 of hydroxypropyl methacrylate. Parts by weight and 3 parts by weight of acrylic acid are solution-polymerized in toluene to give a solid content of 60% by weight and a molecular weight of 34.0.
00 copolymer resin solution (A-4) was prepared. As in Example 1, (A-4) 20 parts by weight, (B-1) 80 parts by weight,
A coating material was prepared by adding 1.5 parts by weight of a benzotriazole-based ultraviolet absorber and 1.0 part by weight of a piperidine-based light stabilizer, and applied to a steel sheet provided with an epoxy primer by the same operation as in Example 1. The test results of the coated plate are as follows.
【００３７】[0037]
【表４】 ＊ ＪＩＳ Ｋ ５４００ ＊＊マジックインキ赤を塗り、２４ｈｒｓ後紙でふきと
る。全部消えたものが○、一部残ったものが△[Table 4] * JIS K 5400 ** Apply the magic ink red and wipe it off with paper after 24 hours. The ones that have all disappeared are ○, and the ones that partially remain are △
【００３８】[0038]
【発明の効果】本発明の塗料用組成物は、シリコーンオ
リゴマーとビニルモノマー（１）との共重合した共重合
体樹脂（Ａ）とフッ素樹脂またはフッ素化合物モノマー
とビニルモノマー（２）との共重合体からなるフッ素系
樹脂を配合することにより、フッ素系樹脂塗料の長所で
ある耐熱性、耐薬品性、耐水性、耐湿性、特に耐候性を
有し、かつフッ素樹脂塗料の問題点であるボイドの発生
が少なく、塗膜の硬度を向上させ、耐汚染性を大きく改
善した塗料組成物を開発できた。The coating composition of the present invention comprises a copolymer resin (A) obtained by copolymerizing a silicone oligomer and a vinyl monomer (1) and a fluororesin or a fluorine compound monomer and a vinyl monomer (2). By incorporating a fluororesin made of a polymer, it has the advantages of the fluororesin paint, such as heat resistance, chemical resistance, water resistance, moisture resistance, and particularly weather resistance, and is a problem of the fluororesin paint. It has been possible to develop a coating composition with few voids, improved coating hardness, and greatly improved stain resistance.
【００３９】この結果、屋内用塗料としてはもちろん、
日光、風雨にさらされる金属、コンクリート、セラミッ
クス、プラスチック、木材用塗料組成物として、建築、
土木、自動車等の車輛関係、エクステリア等の屋外塗装
物に対して耐久性の優れた塗料用組成物として有効に使
用できるものである。As a result, as an indoor paint, of course,
As a paint composition for metals, concrete, ceramics, plastics and wood exposed to sunlight and wind and rain, construction,
It can be effectively used as a coating composition having excellent durability for civil engineering, vehicle-related vehicles, and exterior coatings such as exteriors.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年２月２５日[Submission date] February 25, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項４[Name of item to be corrected] Claim 4
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【化１】 または一般式（２）[Chemical 1] Or general formula (2)
【化２】 で示されるオルガノシルセスキオキサンオリゴマーであ
る請求項１〜３記載の塗料用組成物。[Chemical 2] The coating composition according to any one of claims 1 to 3, which is an organosilsesquioxane oligomer represented by:
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００６[Correction target item name] 0006
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００６】本発明において重合性の不飽和基を有する
オルガノシルセスキオキサンオリゴマー（以下、単にシ
リコーンオリゴマーという。）は、一般式（１）In the present invention, the organosilsesquioxane oligomer having a polymerizable unsaturated group (hereinafter, simply referred to as a silicone oligomer) has the general formula (1).
【化３】 または一般式（２）[Chemical 3] Or general formula (2)
【化４】 で示される構造を有するオリゴマーである。[Chemical 4] It is an oligomer having a structure shown by.
Claims (5)
ノシルセスキオキサンオリゴマーおよびビニルモノマー
（１）との共重合体樹脂（Ａ）および重合性の不飽和基
を有するフッ素化炭化水素モノマーの重合体、またはそ
れとビニルモノマー（２）を共重合して得られるフッ素
系樹脂（Ｂ）とを配合したことを特徴とする塗料用組成
物。1. A copolymer resin (A) with an organosilsesquioxane oligomer having a polymerizable unsaturated group in its side chain and a vinyl monomer (1), and a fluorinated hydrocarbon having a polymerizable unsaturated group. A coating composition comprising a monomer polymer or a fluororesin (B) obtained by copolymerizing the polymer with a vinyl monomer (2).
（Ｂ）にポリイソシアネート化合物、アミノ樹脂、エポ
キシ樹脂等のカップリング剤を配合した請求項１記載の
塗料用樹脂組成物。2. The resin composition for coating composition according to claim 1, wherein the copolymer resin (A) and the fluororesin (B) are mixed with a coupling agent such as a polyisocyanate compound, an amino resin and an epoxy resin.
（Ａ）１５〜７０重量部およびフッ素系樹脂８５〜３０
重量部である請求項１〜２記載の塗料用組成物。3. A copolymer resin (A) in an amount of 15 to 70 parts by weight as a solid content and a fluorine resin 85 to 30.
The coating composition according to claim 1, which is part by weight.
る請求項１〜３記載の塗料用組成物。4. A compound represented by the general formula (1): Or general formula (2) The coating composition according to any one of claims 1 to 3, which is an organosilsesquioxane oligomer represented by:
水素モノマーが、フッ化ビニル、フッ化ビニリデン、三
フッ化エチレン、四フッ化エチレン、ヘキサフルオロプ
ロピレン、フロロアルキルアクリレート、フロロアルキ
ルメタクリレートである請求項１〜４記載の塗料用組成
物。5. The fluorinated hydrocarbon monomer having a polymerizable unsaturated group is vinyl fluoride, vinylidene fluoride, ethylene trifluoride, ethylene tetrafluoride, hexafluoropropylene, fluoroalkyl acrylate, fluoroalkyl methacrylate. The coating composition according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28395593A JPH07113062A (en) | 1993-10-18 | 1993-10-18 | Composition for coating compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28395593A JPH07113062A (en) | 1993-10-18 | 1993-10-18 | Composition for coating compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07113062A true JPH07113062A (en) | 1995-05-02 |
Family
ID=17672393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28395593A Pending JPH07113062A (en) | 1993-10-18 | 1993-10-18 | Composition for coating compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07113062A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003507522A (en) * | 1999-08-16 | 2003-02-25 | ビーエーエスエフ コーティングス アクチェンゲゼルシャフト | Coating material and its use for producing high scratch resistant multilayer transparent coatings |
| JP2004038143A (en) * | 2002-03-03 | 2004-02-05 | Shipley Co Llc | Method for preparing silane monomer and polymer, and photoresist composition containing same |
| US7125936B2 (en) | 2000-07-31 | 2006-10-24 | Nissan Motor Co., Ltd. | Clear coating composition, method of forming a coating film and multilayer coating film |
| JP2007112893A (en) * | 2005-10-20 | 2007-05-10 | Asahi Glass Coat & Resin Co Ltd | Composition for coating, coating, kit for coating and coated article |
| JP2009029986A (en) * | 2007-07-30 | 2009-02-12 | Hitachi Cable Ltd | Coating material and product with high water repellency and high sliding property |
| JP2009185107A (en) * | 2008-02-04 | 2009-08-20 | Pialex Technologies Corp | Hydrophilic coating material and hydrophilic coated object |
-
1993
- 1993-10-18 JP JP28395593A patent/JPH07113062A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003507522A (en) * | 1999-08-16 | 2003-02-25 | ビーエーエスエフ コーティングス アクチェンゲゼルシャフト | Coating material and its use for producing high scratch resistant multilayer transparent coatings |
| US7125936B2 (en) | 2000-07-31 | 2006-10-24 | Nissan Motor Co., Ltd. | Clear coating composition, method of forming a coating film and multilayer coating film |
| JP2004038143A (en) * | 2002-03-03 | 2004-02-05 | Shipley Co Llc | Method for preparing silane monomer and polymer, and photoresist composition containing same |
| JP4557497B2 (en) * | 2002-03-03 | 2010-10-06 | ローム・アンド・ハース・エレクトロニック・マテリアルズ，エル．エル．シー． | Method for producing silane monomer and polymer and photoresist composition comprising the same |
| JP2007112893A (en) * | 2005-10-20 | 2007-05-10 | Asahi Glass Coat & Resin Co Ltd | Composition for coating, coating, kit for coating and coated article |
| JP2009029986A (en) * | 2007-07-30 | 2009-02-12 | Hitachi Cable Ltd | Coating material and product with high water repellency and high sliding property |
| JP2009185107A (en) * | 2008-02-04 | 2009-08-20 | Pialex Technologies Corp | Hydrophilic coating material and hydrophilic coated object |
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