JP4796326B2 - Synthetic resin coating, method for producing the same, and synthetic resin molding having the coating film - Google Patents
Synthetic resin coating, method for producing the same, and synthetic resin molding having the coating film Download PDFInfo
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- JP4796326B2 JP4796326B2 JP2005128726A JP2005128726A JP4796326B2 JP 4796326 B2 JP4796326 B2 JP 4796326B2 JP 2005128726 A JP2005128726 A JP 2005128726A JP 2005128726 A JP2005128726 A JP 2005128726A JP 4796326 B2 JP4796326 B2 JP 4796326B2
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- 239000011248 coating agent Substances 0.000 title claims description 46
- 238000000576 coating method Methods 0.000 title claims description 46
- 229920003002 synthetic resin Polymers 0.000 title claims description 45
- 239000000057 synthetic resin Substances 0.000 title claims description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000000465 moulding Methods 0.000 title claims description 6
- 239000003973 paint Substances 0.000 claims description 37
- -1 polypropylene Polymers 0.000 claims description 28
- 239000004743 Polypropylene Substances 0.000 claims description 21
- 229920001155 polypropylene Polymers 0.000 claims description 21
- 239000012188 paraffin wax Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 18
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 12
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 11
- 239000008158 vegetable oil Substances 0.000 claims description 11
- 239000002990 reinforced plastic Substances 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 4
- 229920006337 unsaturated polyester resin Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000195493 Cryptophyta Species 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002987 primer (paints) Substances 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
本発明は、バインダー成分として塩素化ポリエチレンおよび／または塩素化ポリプロピレンを用いた新規な合成樹脂用塗料、その製造方法およびその塗膜を有する合成樹脂成形体に関する。 The present invention relates to a novel synthetic resin coating material using chlorinated polyethylene and / or chlorinated polypropylene as a binder component, a method for producing the same, and a synthetic resin molded article having the coating film.
ポリエチレンやポリプロピレンのような合成樹脂や強化プラスチック（たとえば、ガラス繊維に不飽和ポリエステル系樹脂を含浸、硬化したもの）などの表面に塗料を塗装しても、密着性の優れた塗膜を得ることはできない。
そのため、各種合成樹脂と塗料や印刷インキとの接着性を向上させる技術がいろいろ提案されている。このような従来技術としては、（ａ）コロナ放電処理、（ｂ）フレーム処理、（ｃ）オゾン処理、（ｄ）プラズマ処理、（ｅ）電子線照射処理、（ｆ）紫外線照射処理、（ｇ）プライマー処理、（ｈ）薬品処理、（ｉ）表面微細凹凸化処理などの表面処理技術が挙げられる（非特許文献１）。
しかしながら、合成樹脂や強化プラスチックに塗装や印刷を行うためにこのような表面処理が必要であるということは、そのために余分のコストがかかることを意味している。
Even if a paint is applied to the surface of a synthetic resin such as polyethylene or polypropylene or a reinforced plastic (for example, a glass fiber impregnated and cured with an unsaturated polyester resin), a coating film with excellent adhesion can be obtained. I can't.
Therefore, various techniques for improving the adhesion between various synthetic resins and paints or printing inks have been proposed. Such conventional techniques include (a) corona discharge treatment, (b) flame treatment, (c) ozone treatment, (d) plasma treatment, (e) electron beam irradiation treatment, (f) ultraviolet irradiation treatment, (g And surface treatment techniques such as primer treatment, (h) chemical treatment, and (i) surface fine unevenness treatment (Non-Patent Document 1).
However, the fact that such a surface treatment is necessary for painting or printing on a synthetic resin or reinforced plastic means that extra costs are required.
本発明の目的は、合成樹脂製成形体や強化プラスチックなどの合成樹脂表面に何んらかの前処理も施すことなく、また下塗り塗料をあらかじめ塗布（プライマー処理）することなく、直接塗装しても、その塗膜の密着力が極めて高い新規な合成樹脂用塗料、その製造方法およびその塗膜を有する合成樹脂成形体を提供する点にある。 The object of the present invention is to directly coat the surface of a synthetic resin such as a synthetic resin molding or a reinforced plastic without any pre-treatment and without applying a primer coating (primer treatment) in advance. Another object of the present invention is to provide a novel coating material for a synthetic resin having a very high adhesion of the coating film, a method for producing the coating material, and a synthetic resin molding having the coating film.
本発明の第１は、
（Ａ）塩素化ポリエチレンおよび／または塩素化ポリプロピレン１５〜４５重量％
（Ｂ）塩素化パラフィン５〜２５重量％
（Ｃ）エポキシ化植物油０．５〜５重量％
を含有する合成樹脂用塗料に関する。
本発明の第２は、
（Ａ）塩素化ポリエチレンおよび／または塩素化ポリプロピレン１５〜４５重量％
（Ｂ）塩素化パラフィン５〜２５重量％
（Ｃ）エポキシ化植物油０．５〜５重量％
（Ｄ）エチレン／酢酸ビニル共重合体２．５〜５．５重量％
を含有するものである合成樹脂用塗料に関する。
本発明の第３は、合成樹脂が非極性の合成樹脂である請求項１又は２記載の合成樹脂用塗料に関する。
本発明の第４は、合成樹脂が強化プラスチックである請求項１又は２記載の合成樹脂用塗料に関する。
本発明の第５は、溶剤にまず（Ｃ）成分であるエポキシ化植物油を溶解し、その後（Ｂ）成分である塩素化パラフィンを溶解してから、（Ａ）成分である塩素化ポリエチレンおよび／または塩素化ポリプロピレンを溶解することを特徴とする請求項１記載の合成樹脂用塗料の製造方法に関する。
本発明の第６は、溶剤にまず（Ｃ）成分であるエポキシ化植物油を溶解し、その後（Ｂ）成分である塩素化パラフィンを溶解してから、（Ｄ）成分であるエチレン／酢酸ビニル共重合体を溶解し、ひきつづいて（Ａ）成分である塩素化ポリエチレンおよび／または塩素化ポリプロピレンを溶解することを特徴とする請求項２記載の合成樹脂用塗料の製造方法に関する。
本発明の第７は、請求項１〜４いずれか記載の合成樹脂用塗料の塗膜を有することを特徴とする合成樹脂成形体に関する。
本発明の第８は、合成樹脂が強化プラスチックである請求項７記載の合成樹脂成形体に関する。
The first of the present invention is
(A) 15 to 45% by weight of chlorinated polyethylene and / or chlorinated polypropylene
(B) 5-25% by weight of chlorinated paraffin
(C) Epoxidized vegetable oil 0.5 to 5% by weight
The present invention relates to a coating material for synthetic resin.
The second of the present invention is
(A) 15 to 45% by weight of chlorinated polyethylene and / or chlorinated polypropylene
(B) 5-25% by weight of chlorinated paraffin
(C) Epoxidized vegetable oil 0.5 to 5% by weight
(D) Ethylene / vinyl acetate copolymer 2.5 to 5.5% by weight
It is related with the coating material for synthetic resins which contains this.
A third aspect of the present invention relates to the synthetic resin coating material according to claim 1 or 2 , wherein the synthetic resin is a nonpolar synthetic resin.
A fourth aspect of the present invention relates to the synthetic resin coating material according to claim 1 or 2 , wherein the synthetic resin is a reinforced plastic.
In the fifth aspect of the present invention, the epoxidized vegetable oil as the component (C) is first dissolved in the solvent, and then the chlorinated paraffin as the component (B) is dissolved, and then the chlorinated polyethylene as the component (A) and / or or a method of manufacturing a synthetic resin paint according to claim 1 Symbol mounting, characterized in that dissolving the chlorinated polypropylene.
In the sixth aspect of the present invention, the epoxidized vegetable oil as the component (C) is first dissolved in the solvent, and then the chlorinated paraffin as the component (B) is dissolved, and then the ethylene / vinyl acetate copolymer as the component (D) is dissolved. It was dissolved polymer, a method for manufacturing a synthetic resin paint according to claim 2 Symbol mounting, characterized in that dissolving subsequently with a chlorinated polyethylene and / or chlorinated polypropylene as component (a).
7th of this invention is related with the synthetic resin molding which has a coating film of the coating material for synthetic resins in any one of Claims 1-4.
Eighth invention relates to a synthetic resin molded article according to claim 7, wherein the synthetic resins are reinforced plastic.
本発明で用いる（Ａ）成分の塩素化ポリエチレンや塩素化ポリプロピレンは、塩素含有量が５０〜８０重量％、好ましくは５５〜７０重量％のものを用いることができる。また、これらのポリマーの分子量は５０００以上、好ましくは５０００〜５００００のものを用いることができる。
本発明で用いる（Ａ）成分の塩素化ポリエチレンや塩素化ポリプロピレンは、従来の塗料用樹脂組成物に用いられているものが、塩素含有量２０〜４０重量％のものであるのに対して２割以上塩素含有量が高い点が１つの特徴点である。また、固形分を高くすることができる点も本発明の特徴点であり、とくに後記表１〜２に示すように密着性が１００／１００を示すケースにおいては固形分は３４〜５５．１重量％と高いことが判る。
The chlorinated polyethylene or the chlorinated polypropylene as the component (A) used in the present invention may have a chlorine content of 50 to 80% by weight, preferably 55 to 70% by weight. Moreover, the molecular weight of these polymers is 5000 or more, Preferably the thing of 5000-50000 can be used.
The component (A) chlorinated polyethylene and chlorinated polypropylene used in the present invention are those used in conventional coating resin compositions, whereas the chlorine content is 20 to 40% by weight. One of the features is that the chlorine content is higher than that. Moreover, the point which can make solid content high is also the feature point of this invention, especially in the case where adhesiveness shows 100/100 as shown in Tables 1-2 below, solid content is 34-55.1 weight. % Is high.
本発明においては、（Ａ）成分の塩素化ポリエチレンや塩素化ポリプロピレンを塗料全量に対し１５〜４５重量％、好ましくは２０〜３５重量％配合することが必要である。 In the present invention, it is necessary to blend 15 to 45% by weight, preferably 20 to 35% by weight, of chlorinated polyethylene or chlorinated polypropylene as the component (A) with respect to the total amount of the paint.
また、本発明において塩素化ポリエチレンと塩素化ポリプロピレンの混合物を用いる場合はその合計量で（Ａ）成分が少なくとも１５重量％以上含有されていることが必要である。これにより本発明塗料の基本的な接着力が得られる。 In the present invention, when a mixture of chlorinated polyethylene and chlorinated polypropylene is used, the total amount of component (A) must be at least 15% by weight or more. Thereby, the basic adhesive force of the paint of the present invention can be obtained.
（Ｂ）の塩素化パラフィンの使用量は、塗料全量に対し５〜２５重量％、好ましくは
８〜１５重量％であり、塩素化パラフィンにおける塩素含有量は平均値で３０〜６０重量％、好ましくは４０〜５０重量％である。
（Ｂ）の塩素化パラフィンは、本発明の塗料において、塗膜に柔軟性を与える可塑剤としての機能を有し、塗膜形成性を高める。その役割を果たすためにも、前記使用量が必要である。
とくに（Ｂ）の塩素化パラフィンは、塩素含有量が４０重量％以上と高いもの（以下塩素化パラフィンIという）と塩素含有量が３０重量％以下と低いもの（以下塩素化パラフィンIIという）を併用することが好ましい。塩素化パラフィンＩは塩素化パラフィンの全量に対し７０重量％以上、塩素化パラフィンIIは塩素化パラフィンの全量に対し３０重量％以下の割合で使用することが好ましい。塩素化パラフィンＩとIIの併用は、塩素化パラフィンの使用量をある一定の範囲に抑えながら、塗膜の柔軟性や塗膜形成性を調整するのに極めて便利である。
The amount of the chlorinated paraffin used in (B) is 5 to 25% by weight, preferably 8 to 15% by weight, based on the total amount of the paint, and the chlorine content in the chlorinated paraffin is 30 to 60% by weight, preferably Is 40 to 50% by weight.
The chlorinated paraffin (B) has a function as a plasticizer for imparting flexibility to the coating film in the coating material of the present invention, and improves the coating film forming property. In order to fulfill this role, the amount used is necessary.
In particular, the chlorinated paraffin (B) has a high chlorine content of 40% by weight or more (hereinafter referred to as chlorinated paraffin I) and a low chlorine content of 30% by weight or less (hereinafter referred to as chlorinated paraffin II). It is preferable to use together. It is preferable to use chlorinated paraffin I in a proportion of 70% by weight or more with respect to the total amount of chlorinated paraffin, and chlorinated paraffin II in a proportion of 30% by weight or less with respect to the total amount of chlorinated paraffin. The combined use of chlorinated paraffins I and II is extremely convenient for adjusting the flexibility and film formability of the coating film while keeping the amount of chlorinated paraffin used within a certain range.
本発明における（Ｃ）のエポキシ化植物油は、大豆油や亜麻仁油などの不飽和エステルよりなる植物油をエポキシ化したものである。その代表的なものとしては、エポキシ化大豆油、エボキシ化亜麻仁油などがある。
これらの（Ｃ）成分は、（Ａ）成分の塩素化ポリエチレンや塩素化ポリプロピレンが加工される際に安定剤として機能する。
エポキシ化植物油の使用量は、通常、塗料全量に対し０．５〜５重量％、好ましくは
０．７〜３重量％である。
The epoxidized vegetable oil (C) in the present invention is obtained by epoxidizing a vegetable oil made of an unsaturated ester such as soybean oil or linseed oil. Typical examples include epoxidized soybean oil and epoxidized linseed oil.
These components (C) function as stabilizers when the chlorinated polyethylene or chlorinated polypropylene of component (A) is processed.
The amount of epoxidized vegetable oil used is usually 0.5 to 5% by weight, preferably 0.7 to 3% by weight, based on the total amount of paint.
本発明における（Ｄ）のエチレン／酢酸ビニル共重合体は、エチレン対酢酸ビニルの重量割合が、エチレン５０〜１０重量％、酢酸ビニル５０〜９０重量％、好ましくはエチレン４５〜３０重量％、酢酸ビニル５５〜７０重量％であり、（Ｄ）のエチレン／酢酸ビニル共重合体の使用量は、通常、塗料全量に対し２．５〜５．５重量％である。
（Ｄ）のエチレン／酢酸ビニル共重合体は、本発明の塗料において、塗膜の密着性および柔軟性を向上させる役割を果たすものであり、その役割を果たすためにも、前記使用量が好適である。
In the ethylene / vinyl acetate copolymer (D) in the present invention, the weight ratio of ethylene to vinyl acetate is 50 to 10% by weight of ethylene, 50 to 90% by weight of vinyl acetate, preferably 45 to 30% by weight of ethylene, and acetic acid. Vinyl is 55 to 70% by weight, and the amount of the (D) ethylene / vinyl acetate copolymer used is usually 2.5 to 5.5% by weight based on the total amount of the coating material.
The ethylene / vinyl acetate copolymer (D) plays a role of improving the adhesion and flexibility of the coating film in the paint of the present invention, and the amount used is also suitable for this role. It is.
本発明においては、必要に応じてウレタン変性エポキシ樹脂を可塑剤として併用することができる。このものは樹脂としての塗膜形成能を期待して使用するものではないから、エポキシ用硬化剤を添加する必要はない。前記ウレタン変性エポキシ樹脂はたとえば特開平８−１４３６３９号公報記載の方法により製造することができる。ウレタン変性エポキシ樹脂の使用量は、通常、塗料全量に対し３〜２５重量％、好ましくは５〜１０重量％である。本発明組成物中には、エポキシ基と反応する成分は含まれていないので、この塗料は通常のラッカータイプの塗料と同様の使用方法を採用する。 In the present invention, a urethane-modified epoxy resin can be used as a plasticizer if necessary. Since this product is not used in anticipation of the ability to form a coating film as a resin, it is not necessary to add an epoxy curing agent. The urethane-modified epoxy resin can be produced, for example, by the method described in JP-A-8-143939. The amount of the urethane-modified epoxy resin used is usually 3 to 25% by weight, preferably 5 to 10% by weight, based on the total amount of the paint. Since the composition which reacts with an epoxy group is not contained in the composition of the present invention, this paint adopts the same method of use as a normal lacquer type paint.
本発明における溶剤は、（Ａ）成分の塩素化ポリエチレンおよび／または塩素化ポリプロピレンを主成分とする本発明の（Ａ）〜（Ｄ）成分を溶解するものであれば、とくに制限はないが、通常、炭化水素系溶媒、とくに芳香族炭化水素系溶媒、例えば、トルエン、キシレンなどを使用することができる。 The solvent in the present invention is not particularly limited as long as it dissolves the components (A) to (D) of the present invention mainly composed of the chlorinated polyethylene and / or chlorinated polypropylene as the component (A). Usually, hydrocarbon solvents, particularly aromatic hydrocarbon solvents such as toluene and xylene can be used.
本発明の塗料を製造するには、各成分の配合順序が重要であり、請求項５および６記載の添加順序に従う必要がある。この順序で配合した場合に限り、均一で塗装性のよい塗料を得ることができる。 In order to produce the paint of the present invention, the blending order of each component is important, and it is necessary to follow the order of addition described in claims 5 and 6 . Only when blended in this order, a uniform and good paint can be obtained.
本発明塗料の塗布対象物は合成樹脂成形体である。成形体を構成する合成樹脂としては、非極性のポリエチレン、ポリプロピレン；ナイロン６、ナイロン６６などのポリアミド；ポリエチレンテレフタレートなどの飽和ポリエステル；アクリル系樹脂；不飽和ポリエステル樹脂、エポキシ樹脂、フェノール樹脂、メラミン樹脂、尿素樹脂などの熱硬化性樹脂を挙げることができる。なお、合成樹脂成形体がポリエチレンである場合には、前記（Ａ）としては塩素化ポリエチレンであることが好ましく、合成樹脂成形体がポリプロピレンである場合には、前記（Ａ）としては塩素化ポリプロピレンであることが好ましい。
また、ガラス繊維、炭素繊維、天然繊維、合成繊維などの繊維よりなるマット、不織布、織布などの繊維材に合成樹脂を含浸した強化プラスチックなどをあげることができる。強化プラスチックとしてもっとも代表的なものとしては、ガラス繊維に不飽和ポリエステルを含浸、硬化して得られたものであるが、含浸用の硬化性樹脂としては不飽和ポリエステル樹脂に限らず、エポキシ樹脂などの熱硬化性樹脂を用いたものであってもよい。
The application object of the paint of the present invention is a synthetic resin molding. Synthetic resins constituting the molded body include nonpolar polyethylene, polypropylene; polyamides such as nylon 6 and nylon 66; saturated polyesters such as polyethylene terephthalate; acrylic resins; unsaturated polyester resins, epoxy resins, phenol resins, and melamine resins. And thermosetting resins such as urea resins. When the synthetic resin molded body is polyethylene, the (A) is preferably chlorinated polyethylene. When the synthetic resin molded body is polypropylene, the (A) is chlorinated polypropylene. It is preferable that
Further, examples thereof include reinforced plastics in which fiber materials such as mats, nonwoven fabrics, and woven fabrics made of fibers such as glass fibers, carbon fibers, natural fibers, and synthetic fibers are impregnated with synthetic resins. The most typical reinforced plastic is obtained by impregnating and curing glass fiber with unsaturated polyester, but the curable resin for impregnation is not limited to unsaturated polyester resin, epoxy resin, etc. The thermosetting resin may be used.
本発明の塗料は、ガラス繊維に不飽和ポリエステル樹脂を含浸、硬化させたいわゆるＦＲＰ成形体、とくにＦＲＰ製高架水槽や受水槽の塗装に用いるのに好適である。
従来の塗料による塗装では、まずＦＲＰ表面を、たとえばサンドペーパーなどで微細な凹凸を設け、その上に塗装を行っていたが、本発明の塗料を用いる場合は、前述の表面微細凹凸化は必要でなく、ただ表面が脱脂された状態であればよい。
このような表面に本発明の塗料を塗布することにより得られた塗膜は、前処理をした後に形成された従来の塗膜に較べて、何の前処理も施されていないにもかかわらず、ＦＲＰ表面に強固に接着し、耐剥離性、耐候性に優れている。
The coating material of the present invention is suitable for use in the coating of so-called FRP molded products obtained by impregnating and curing an unsaturated polyester resin in glass fibers, particularly for FRP elevated water tanks and water receiving tanks.
In the conventional coating with paint, the FRP surface was first provided with fine irregularities with, for example, sandpaper, and then painted thereon. However, when using the paint of the present invention, the above-mentioned surface fine irregularities are necessary. Instead, it is only necessary that the surface is degreased.
The coating film obtained by applying the paint of the present invention to such a surface is not subjected to any pretreatment as compared with the conventional coating film formed after the pretreatment. It adheres firmly to the FRP surface and has excellent peel resistance and weather resistance.
とくにＦＲＰ製の水槽は、そのままでは太陽光がある程度水槽内部まで透過してしまうため、水槽内に藻類が発生する。これを防止するためには遮光性塗料を塗布する必要があるが、この場合も従来の塗料では表面の微細凹凸化が不可欠である。従来の遮光性塗料、とくに水槽内の藻類発生を防止するための塗料には、光を完全に遮断するため金属フレーク、例えば幅２０ミクロン、厚さ０.３ミクロンのステンレスフレークが配合されている。
本発明の塗料にこの金属フレークを配合した塗料を用いれば、何の前処理もなく、耐剥離性、耐候性に優れた塗膜を形成することができる。
In particular, in an aquarium tank made of FRP, sunlight passes through to some extent inside the aquarium, and algae are generated in the aquarium. In order to prevent this, it is necessary to apply a light-shielding paint, but in this case as well, it is indispensable to make fine irregularities on the surface of the conventional paint. Conventional light-shielding paints, especially paints for preventing the generation of algae in the aquarium, are mixed with metal flakes such as stainless steel flakes having a width of 20 microns and a thickness of 0.3 microns in order to completely block light. .
If the coating material which mix | blended this metal flake with the coating material of this invention is used, the coating film excellent in peeling resistance and a weather resistance can be formed without any pretreatment.
（１）本発明の塗料は、合成樹脂表面に対して何の前処理も必要とせず、脱脂が必要でない程表面が清潔であれば、直接そこに塗装するだけで剥離しない耐久性のある塗膜を形成することができる。
（２）本発明の塗料は、硬化剤なしで、常温で、５分間程度で指触乾燥の状態となる。
（３）本発明の塗料は、プルオフ法による測定結果で、ポリプロピレン表面に対しては１ｋｇ／ｃｍ２程度の密着力が得られ、ポリエチレン表面に対しては０．６ｋｇ／ｃｍ２程度の密着力が得られた。また剥離強さ試験を幅１０ｍｍ、剥離速度１ｍｍ／ｍｉｎでおこなった結果、ポリプロピレンに対しては１０００Ｇ／ｃｍ程度の剥離強さを、ポリエチレンに対しては３００〜５００Ｇ／ｃｍ程度の剥離強さを示した。
（４）本発明の塗料は、樹脂に対する密着性が優れているほか、金属に対しても優れた密着性を有しているので、合成樹脂用および金属用の塗料として極めて有用である。そのため合成樹脂と金属が組み合わさった物品への塗装に有用である。
(1) The paint of the present invention does not require any pre-treatment on the surface of the synthetic resin, and if the surface is clean enough not to be degreased, it is a durable coating that does not peel off simply by painting directly on it. A film can be formed.
(2) The coating material of the present invention is dry to the touch in about 5 minutes at room temperature without a curing agent.
(3) The coating material of the present invention is a measurement result by a pull-off method, and an adhesive force of about 1 kg / cm 2 is obtained on the polypropylene surface, and an adhesive force of about 0.6 kg / cm 2 is applied to the polyethylene surface. was gotten. In addition, as a result of performing a peel strength test at a width of 10 mm and a peel speed of 1 mm / min, a peel strength of about 1000 G / cm for polypropylene and a peel strength of about 300 to 500 G / cm for polyethylene are obtained. Indicated.
(4) The coating material of the present invention is extremely useful as a coating material for synthetic resin and metal because it has excellent adhesion to resin and also has excellent adhesion to metal. Therefore, it is useful for coating on articles in which synthetic resin and metal are combined.
以下に実施例及び参考例を挙げて本発明を説明するが、本発明はこれにより何ら限定されるものではない。なお、塗料成分の配合順序は請求項５及び６に従った。 Hereinafter, the present invention will be described with reference to examples and reference examples , but the present invention is not limited thereto. The blending order of the paint components complies with claims 5 and 6 .
実施例１〜８、参考例１〜８ Examples 1-8, Reference Examples 1-8
前記表中のＡ〜Ｅは下記の成分に相当する。
Ａ：塩素化ポリエチレン（塩素化率６６重量％）
Ｂ：塩素化パラフィン（塩素化率４５．５重量％）
Ｃ：エポキシ化大豆油
Ｄ：エチレン／酢酸ビニル共重合体（エチレン含有量３０重量％）の３５重量％を
トルエン／酢酸エチル溶媒に溶解した溶液として使用。
Ｅ：トルエン
表中の数字は塗料全量に対する重量％である。
A to E in the table correspond to the following components.
A: Chlorinated polyethylene (chlorination rate 66% by weight)
B: Chlorinated paraffin (chlorination rate: 45.5% by weight)
C: Epoxidized soybean oil D: Used as a solution in which 35% by weight of an ethylene / vinyl acetate copolymer (ethylene content 30% by weight) is dissolved in a toluene / ethyl acetate solvent.
E: Toluene The numbers in the table are% by weight relative to the total amount of paint.
表１および表２にその組成を示した請求項１にかかる実施例１〜４、参考例１〜４および請求項２にかかる実施例５〜８、参考例５〜８のそれぞれの塗料を脱脂処理されただけのポリエチレン板上に膜厚２０ミクロンになるように塗付し、乾燥後の塗膜の剥離性を基板目テープ剥離試験によりチェックした。その試験方法は下記に示す。表中の含有塩素量は、（Ａ）、（Ｂ）、（Ｃ）または（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）の全量に対する重量％である。
密着性の試験はＪＩＳ Ｋ ５４００の碁盤目テープ剥離試験によるものである。碁盤に相当する塗膜面の大きさは１０ｍｍ×１０ｍｍであり、そこに縦および横にそれぞれ１ｍｍ間隔でカッターによる切断線を引き、この面にセロハンテープを貼り付けた後、これを引き剥がして碁盤の目１００個のうち何個がセロハンテープ側に塗膜が付着したかを調べ、１００個の基板目（分母）のなかから、剥離しなかった基板目（分子）の数を表示した。
Table 1 and Table 2 show the compositions of Examples 1-4 according to Claim 1, Reference Examples 1-4 , Examples 5-8 according to Claim 2, and Reference Examples 5-8. The film was coated on a polyethylene plate that had been treated so as to have a film thickness of 20 microns, and the peelability of the coating film after drying was checked by a substrate tape peeling test. The test method is shown below. The chlorine content in the table is (%) with respect to the total amount of (A), (B), (C) or (A), (B), (C), (D).
The adhesion test is based on a cross-cut tape peeling test of JIS K 5400. The size of the coating surface corresponding to the grid is 10 mm x 10 mm, and a cutting line with a cutter is drawn vertically and horizontally at intervals of 1 mm, and cellophane tape is attached to this surface, and then peeled off. It was examined how many of the 100 grids of the grid had the coating film attached to the cellophane tape side, and the number of substrates (numerators) that did not peel from the 100 substrates (denominator) was displayed.
実施例９
不飽和ポリエステルを用いたガラス繊維強化プラスチックの水槽の外表面に、アセトンを用いた脱脂処理のみで、表面凹凸化処理を施すことなく、下記組成の塗料に、必要に応じてトルエンを加えて（１０％以下）粘度を調整し塗膜の膜厚が１００μｍになるよう塗布した。
実施例６の基本塗料組成物 ８３重量％
ステンレスフレーク（商品名ＳＵＳ３１６−Ｌ） １５重量％
分散剤 １重量％
湿潤剤 ０．５重量％
沈澱防止剤 ０．５重量％
このようにして得られた塗膜に対して、前記基板目テープ剥離試験を行なったところ、１００個中ただの１個も剥離する部分は認められなかった。
また、この塗膜の遮光効果は完璧であり、藻の発生（光合成）を完全に食い止めることができた。
従来、ＦＲＰの表面に水分がついて、４０℃前後で樹脂とガラス繊維がハクリする現象がおこることが知られているが、本発明の塗料によりこの現象も抑制することができる。
なお、比較のために、ＦＲＰの表面凹凸化処理を前提として市販されている塗料成分（アクリル樹脂塗料、ウレタン樹脂塗料、エポキシ樹脂塗料）を用いるほかは、実施例９と同様の塗料をつくり、これを実施例９と同様に塗布（ＦＲＰの表面凹凸化処理なし）し、その塗膜の剥離性を調べたところ、合格にはほど遠い結果を示した。
Example 9
Toluene is added to the coating composition of the following composition as needed on the outer surface of the water tank of glass fiber reinforced plastic using unsaturated polyester only by degreasing treatment using acetone, without subjecting the surface unevenness treatment ( (10% or less) The viscosity was adjusted and the coating film was applied to a thickness of 100 μm.
83% by weight of basic coating composition of Example 6
Stainless steel flake (trade name SUS316-L) 15% by weight
Dispersant 1% by weight
Wetting agent 0.5% by weight
Anti-precipitation agent 0.5% by weight
When the above-mentioned substrate tape peeling test was performed on the coating film thus obtained, only one of 100 pieces was peeled off.
Moreover, the light shielding effect of this coating film was perfect, and the generation of algae (photosynthesis) could be completely stopped.
Conventionally, it has been known that the surface of the FRP has moisture and the resin and the glass fiber are peeled off at around 40 ° C., but this phenomenon can also be suppressed by the paint of the present invention.
For comparison, a paint similar to that in Example 9 was prepared except that a commercially available paint component (acrylic resin paint, urethane resin paint, epoxy resin paint) was used on the premise of the surface roughening treatment of FRP, When this was applied in the same manner as in Example 9 (without FRP surface unevenness treatment) and the peelability of the coating film was examined, a result far from passing was shown.
Claims (8)
（Ｂ）塩素化パラフィン５〜２５重量％
（Ｃ）エポキシ化植物油０．５〜５重量％
を含有する合成樹脂用塗料。 (A) 15 to 45% by weight of chlorinated polyethylene and / or chlorinated polypropylene
(B) 5-25% by weight of chlorinated paraffin
(C) Epoxidized vegetable oil 0.5 to 5% by weight
A paint for synthetic resin.
（Ｂ）塩素化パラフィン５〜２５重量％
（Ｃ）エポキシ化植物油０．５〜５重量％
（Ｄ）エチレン／酢酸ビニル共重合体２．５〜５．５重量％
を含有するものである合成樹脂用塗料。 (A) 15 to 45% by weight of chlorinated polyethylene and / or chlorinated polypropylene
(B) 5-25% by weight of chlorinated paraffin
(C) Epoxidized vegetable oil 0.5 to 5% by weight
(D) Ethylene / vinyl acetate copolymer 2.5 to 5.5% by weight
A paint for synthetic resins which contains
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