JP5483328B2 - Aqueous primer composition - Google Patents
Aqueous primer composition Download PDFInfo
- Publication number
- JP5483328B2 JP5483328B2 JP2009291935A JP2009291935A JP5483328B2 JP 5483328 B2 JP5483328 B2 JP 5483328B2 JP 2009291935 A JP2009291935 A JP 2009291935A JP 2009291935 A JP2009291935 A JP 2009291935A JP 5483328 B2 JP5483328 B2 JP 5483328B2
- Authority
- JP
- Japan
- Prior art keywords
- solid content
- primer composition
- aqueous
- mgkoh
- mass
- 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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- 239000000203 mixture Substances 0.000 title claims description 46
- 239000007787 solid Substances 0.000 claims description 57
- 239000006185 dispersion Substances 0.000 claims description 50
- 229920005672 polyolefin resin Polymers 0.000 claims description 34
- 239000000049 pigment Substances 0.000 claims description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 27
- 229920005749 polyurethane resin Polymers 0.000 claims description 27
- 150000001412 amines Chemical class 0.000 claims description 25
- 239000002270 dispersing agent Substances 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- 150000008065 acid anhydrides Chemical class 0.000 claims description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000002987 primer (paints) Substances 0.000 description 38
- 238000000576 coating method Methods 0.000 description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 239000011248 coating agent Substances 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- -1 polypropylene Polymers 0.000 description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
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- 229910052782 aluminium Inorganic materials 0.000 description 5
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- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
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- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
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- 239000006229 carbon black Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
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- 150000002513 isocyanates Chemical class 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000006353 oxyethylene group Chemical group 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical group COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical group CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
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- DEDUBNVYPMOFDR-UHFFFAOYSA-N 2-ethoxypropan-1-ol Chemical group CCOC(C)CO DEDUBNVYPMOFDR-UHFFFAOYSA-N 0.000 description 2
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical group COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 description 2
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 125000002877 alkyl aryl group Chemical group 0.000 description 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
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- 229920006122 polyamide resin Polymers 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
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- 239000006228 supernatant Substances 0.000 description 1
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Landscapes
- Paints Or Removers (AREA)
Description
本発明は、プラスチック素材、特にポリオレフィン系素材に適した非塩素系水性プライマー組成物に関する。 The present invention relates to a non-chlorine aqueous primer composition suitable for plastic materials, particularly polyolefin-based materials.
プラスチック素材への付着性及び上塗り塗膜への付着性に優れた水性プライマー組成物として、例えば、塩素化ポリオレフィン（Ａ）、ポリウレタン水分散体（Ｂ）及び活性メチレンブロックポリイソシアネート化合物（Ｃ）の固形分合計に基いて、塩素化ポリオレフィン（Ａ）を固形分で１０〜８０重量％、ポリウレタン水分散体（Ｂ）を固形分で５〜５０重量％、及び活性メチレンブロックポリイソシアネート化合物（Ｃ）を５〜４０重量％の範囲内で含有してなることを特徴とするプラスチック成形品用水性プライマー組成物が知られている（特許文献１参照）。しかしながら、該水性プライマー組成物は、過酷な耐湿性試験（例えば、５０℃／９８％×３００時間）において塗膜性能が十分ではなく、ブリスターを生ずるという欠点があった。 Examples of aqueous primer compositions having excellent adhesion to plastic materials and adhesion to top coat films include, for example, chlorinated polyolefin (A), polyurethane water dispersion (B), and active methylene block polyisocyanate compound (C). Based on the total solid content, the chlorinated polyolefin (A) is 10 to 80 wt% in solid content, the polyurethane water dispersion (B) is 5 to 50 wt% in solid content, and the active methylene block polyisocyanate compound (C). There is known an aqueous primer composition for plastic molded products characterized by containing 5 to 40% by weight of the resin (see Patent Document 1). However, the water-based primer composition has a drawback in that the coating performance is not sufficient in a severe moisture resistance test (for example, 50 ° C./98%×300 hours) and blisters are formed.
また、自動車用バンパーなどのプラスチック成形品に高明度或いは高彩度の塗色を形成可能で、十分な導電性を有し、耐水性、耐湿性等に優れたプライマー塗膜を形成できる水性プライマー組成物として、（Ａ）変性ポリオレフィンの水性分散体、（Ｂ）水性ウレタン樹脂及び／又は水性アクリル樹脂、（Ｃ）導電性金属酸化物、及び（Ｄ）アルミニウム片を含んでなり、成分（Ａ）／成分（Ｂ）の固形分質量比が１５／８５〜８０／２０の範囲内にあり、且つ成分（Ｃ）を組成物中の全樹脂固形分１００質量部に対して５０〜３００質量部の範囲内で含有し、成分（Ｄ）を組成物中の全樹脂固形分１００質量部に対して１〜３０質量部の範囲内で含有することを特徴とする水性プライマー組成物が知られている（特許文献２参照）。しかしながら、該水性プライマー組成物は、耐水性を低下させるアルミニウム片を含むため、過酷な耐湿性試験（例えば、５０℃／９８％×３００時間）において塗膜性能が十分ではなく、ブリスターを生ずるという欠点があった。 Also, an aqueous primer composition capable of forming a paint film with high brightness or high saturation on a plastic molded article such as an automobile bumper, having sufficient conductivity, and capable of forming a primer coating having excellent water resistance and moisture resistance. Comprising (A) an aqueous dispersion of a modified polyolefin, (B) an aqueous urethane resin and / or an aqueous acrylic resin, (C) a conductive metal oxide, and (D) an aluminum piece. The solid content mass ratio of the component (B) is in the range of 15/85 to 80/20, and the component (C) is in the range of 50 to 300 parts by mass with respect to 100 parts by mass of the total resin solid content in the composition. An aqueous primer composition is known which contains 1 to 30 parts by mass of the component (D) in an amount of 1 to 30 parts by mass with respect to 100 parts by mass of the total resin solid content in the composition ( Patent Document 2). However, since the water-based primer composition contains aluminum pieces that reduce water resistance, the coating performance is not sufficient in a severe moisture resistance test (for example, 50 ° C./98%×300 hours), and blisters are generated. There were drawbacks.
また、（Ａ）融点が１２０℃以下で且つ重量平均分子量が３０，０００〜１８０，０００の範囲内にある不飽和カルボン酸−又は酸無水物−変性ポリオレフィン（ａ）を水性媒体中に分散せしめてなる変性ポリオレフィンの水性分散体、（Ｂ）イオン性官能基を含有するアクリル樹脂、及び（Ｃ）導電性カーボンを含む顔料を含んでなり、Ｌ値が３５以上で且つ表面抵抗率が１×１０８Ω／□以下の塗膜を形成する水性プライマー組成物が、明度を確保しつつ、塗膜に導電性を付与することができ、しかも耐水性、付着性などに優れた塗膜を形成することができる水性プライマー組成物として、知られている（特許文献３参照）。しかしながら、該水性プライマー組成物は、イオン性官能基を含有するアクリル樹脂が含有されるため、過酷な耐湿性試験（例えば、５０℃／９８％×３００時間）において塗膜性能が十分ではなく、ブリスターを生ずるという欠点があった。また、同組成物では分散が困難なため、長期保管すると顔料が沈降し、ブツなどの問題を引き起こすことがあった。 Further, (A) an unsaturated carboxylic acid- or acid anhydride-modified polyolefin (a) having a melting point of 120 ° C. or less and a weight average molecular weight in the range of 30,000 to 180,000 is dispersed in an aqueous medium. A modified polyolefin aqueous dispersion, (B) an acrylic resin containing an ionic functional group, and (C) a pigment containing conductive carbon, having an L value of 35 or more and a surface resistivity of 1 × An aqueous primer composition that forms a coating film of 10 8 Ω / □ or less can provide conductivity to the coating film while ensuring lightness, and forms a coating film that is excellent in water resistance and adhesion. It is known as an aqueous primer composition that can be used (see Patent Document 3). However, since the aqueous primer composition contains an acrylic resin containing an ionic functional group, the coating performance is not sufficient in a severe moisture resistance test (for example, 50 ° C./98%×300 hours), There was the disadvantage of producing blisters. In addition, since the composition is difficult to disperse, the pigment may settle out when stored for a long time, which may cause problems such as blistering.
さらに、（Ａ）融点が１２０℃以下で且つ重量平均分子量が５００００〜１５００００の範囲内にある不飽和カルボン酸もしくは酸無水物変性ポリオレフィン（ａ）を水性媒体中に分散せしめてなる非塩素系変性ポリオレフィンの水性分散体、（Ｂ）水溶性もしくは水分散性のポリオール樹脂、及び（Ｃ）顔料を含んでなり、成分（Ａ）／成分（Ｂ）の固形分重量比が２０／８０〜８５／１５の範囲内にあり、且つ成分（Ｃ）を組成物中の全樹脂固形分１００重量部に対して０．５〜２００重量部の範囲内で含有することを特徴とする水性プライマー組成物が、付着性、耐水性、耐溶剤性などに優れた塗膜を形成し得る非塩素系水性プライマー組成物として、知られている（特許文献４参照）。しかしながら、該水性プライマー組成物は、過酷な耐湿性試験（例えば、５０℃／９８％×３００時間）において塗膜性能が十分ではなく、ブリスターを生ずるという欠点があった。 Further, (A) a non-chlorine-based modification in which an unsaturated carboxylic acid or acid anhydride-modified polyolefin (a) having a melting point of 120 ° C. or lower and a weight average molecular weight in the range of 50,000 to 150,000 is dispersed in an aqueous medium. An aqueous dispersion of polyolefin, (B) a water-soluble or water-dispersible polyol resin, and (C) a pigment, wherein the solid content weight ratio of component (A) / component (B) is 20/80 to 85 / An aqueous primer composition comprising 15 parts and containing component (C) in a range of 0.5 to 200 parts by weight with respect to 100 parts by weight of the total resin solids in the composition. It is known as a non-chlorine aqueous primer composition capable of forming a coating film excellent in adhesion, water resistance, solvent resistance and the like (see Patent Document 4). However, the water-based primer composition has a drawback in that the coating performance is not sufficient in a severe moisture resistance test (for example, 50 ° C./98%×300 hours) and blisters are formed.
本発明は、ダイオキシンを発生する可能性がある塩素原子を含有しない、非塩素系ポリオレフィン樹脂系プライマー組成物であって、特に８０℃程度の低温焼付け時におけるポリオレフィン素材への付着性に優れ、過酷な条件下での耐湿性試験を満足させる塗膜を形成することができ、かつ、貯蔵安定性が良好な水性プライマー組成物を提供することにある。 The present invention is a non-chlorine polyolefin resin-based primer composition that does not contain chlorine atoms that may generate dioxins, and is particularly excellent in adhesion to polyolefin materials during baking at a low temperature of about 80 ° C. Another object of the present invention is to provide an aqueous primer composition that can form a coating film that satisfies a moisture resistance test under various conditions and that has good storage stability.
本発明者らは、前記課題を解決するべく、鋭意研究を重ねた結果、今回、特定の非塩素化ポリオレフィン樹脂の水分散体、特定のポリウレタン樹脂水分散体、導電性カーボン及び特定の顔料分散剤を特定の割合で配合することで、上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive research to solve the above problems, the present inventors have now obtained a specific non-chlorinated polyolefin resin aqueous dispersion, a specific polyurethane resin aqueous dispersion, conductive carbon, and a specific pigment dispersion. It has been found that the above problems can be solved by blending the agent at a specific ratio, and the present invention has been completed.
すなわち、本発明は、（Ａ）融点が６０℃〜１００℃であり、重量平均分子量が５０，０００〜２５０，０００である、不飽和カルボン酸及び／又は酸無水物によって変性された非塩素化ポリオレフィン樹脂の水分散体、（Ｂ）水酸基を含有しないポリウレタン樹脂水分散体、（Ｃ）導電性カーボン、及び（Ｄ）アミン価又は酸価の少なくとも一方が０ｍｇＫＯＨ／ｇ超であり、分散剤の固形分あたりアミン価が６５ｍｇＫＯＨ／ｇ以下であり、酸価が３５ｍｇＫＯＨ／ｇ以下である顔料分散剤、を含有し、（Ａ）／（Ｂ）の含有質量比率が、固形分換算で２０／８０〜８０／２０の範囲内であり、かつ、（Ｃ）／｛（Ａ）＋（Ｂ）｝の含有質量比率が、固形分換算で２／９８〜２０／８０の範囲内であり、かつ、（Ｄ）／（Ｃ）の含有質量比率が、固形分換算で１０／９０〜５０／５０の範囲内であることを特徴とする水性プライマー組成物を提供するものである。
また、本発明は、上記水性プライマー組成物において、前記（Ｄ）成分の顔料分散剤のアミン価が４５ｍｇＫＯＨ／ｇ以下である水性プライマー組成物を提供するものである。
また、本発明は、上記水性プライマー組成物において、前記水酸基を含有しないポリウレタン樹脂水分散体の平均粒径が５ｎｍ以上、かつ１３０ｎｍ以下である水性プライマー組成物を提供するものである。
また、本発明は、上記水性プライマー組成物において、前記（Ｃ）／｛（Ａ）＋（Ｂ）｝の含有質量比率が、固形分換算で４／９６〜１７／８３の範囲内であり、かつ、（Ｄ）／（Ｃ）の含有質量比率が、固形分換算で１５／８５〜４５／５５の範囲内である水性プライマー組成を提供するものである。
That is, the present invention provides (A) a non-chlorinated modified with an unsaturated carboxylic acid and / or acid anhydride having a melting point of 60 ° C. to 100 ° C. and a weight average molecular weight of 50,000 to 250,000. An aqueous dispersion of a polyolefin resin, (B) a polyurethane resin aqueous dispersion containing no hydroxyl group, (C) conductive carbon, and (D) at least one of an amine value or an acid value is greater than 0 mgKOH / g , A pigment dispersant having an amine value of 65 mgKOH / g or less and an acid value of 35 mgKOH / g or less per solid content, and the mass ratio of (A) / (B) is 20/80 in terms of solid content. And the content mass ratio of (C) / {(A) + (B)} is in the range of 2/98 to 20/80 in terms of solid content, and Content mass of (D) / (C) Rate is intended to provide an aqueous primer composition characterized in that is in the range of 10 / 90-50 / 50 in terms of solid content.
The present invention also provides an aqueous primer composition in which the amine value of the pigment dispersant as the component (D) is 45 mgKOH / g or less.
The present invention also provides an aqueous primer composition having an average particle diameter of 5 nm or more and 130 nm or less of the polyurethane resin aqueous dispersion containing no hydroxyl group in the aqueous primer composition.
Further, in the aqueous primer composition according to the present invention, the content mass ratio of (C) / {(A) + (B)} is within a range of 4/96 to 17/83 in terms of solid content, And the content ratio of (D) / (C) provides the aqueous primer composition which exists in the range of 15 / 85-45 / 55 in conversion of solid content.
本発明の水性プライマー組成物は、特に８０℃程度の低温焼付け時におけるポリオレフィン素材への付着性に優れ、過酷な条件下での耐湿性試験を満足させる塗膜を形成することができ、かつ、貯蔵安定性が良好である。 The aqueous primer composition of the present invention is particularly excellent in adhesion to a polyolefin material during baking at a low temperature of about 80 ° C., can form a coating film that satisfies a moisture resistance test under severe conditions, and Storage stability is good.
本発明の水性プライマー組成物は、非塩素化ポリオレフィン樹脂の水分散体（Ａ）、特定のポリウレタン樹脂水分散体（Ｂ）、導電性カーボン（Ｃ）、及び顔料分散剤（Ｄ）を主成分として構成される。
本発明の（Ａ）成分は、塩素を含有しないポリオレフィン樹脂の水分散体であるが、塩素を含有しないポリオレフィン樹脂は、不飽和カルボン酸及び／又は酸無水物によって変性されたものである。
The aqueous primer composition of the present invention is mainly composed of an aqueous dispersion (A) of a non-chlorinated polyolefin resin, a specific polyurethane resin aqueous dispersion (B), conductive carbon (C), and a pigment dispersant (D). Configured as
The component (A) of the present invention is an aqueous dispersion of a polyolefin resin that does not contain chlorine. The polyolefin resin that does not contain chlorine is modified with an unsaturated carboxylic acid and / or an acid anhydride.
塩素を含有しないポリオレフィン樹脂は、ポリエチレン樹脂、ポリプロピレン樹脂、ポリブテン樹脂などが挙げられるが、ポリプロピレン樹脂が好ましい。ポリプロピレン樹脂としては、プロピレン単独重合体樹脂、プロピレンと他のαオレフィンとの共重合体樹脂などが挙げられる。プロピレンと他のαオレフィンとの共重合体樹脂としては、エチレン−プロピレン共重合体樹脂、プロピレン−ブテン共重合体樹脂、エチレン−プロピレン−ブテン共重合体樹脂、プロピレン−ヘキセン共重合体樹脂などが好ましく挙げられる。これらのうち、プロピレンの含有量が５０ｍｏｌ％以上のプロピレン系重合体樹脂がより好ましく、プロピレンの含有量が６０ｍｏｌ％以上のプロピレン系重合体樹脂が特に好ましい。 Examples of the polyolefin resin not containing chlorine include polyethylene resin, polypropylene resin, and polybutene resin, and polypropylene resin is preferable. Examples of the polypropylene resin include a propylene homopolymer resin and a copolymer resin of propylene and another α-olefin. Examples of copolymer resins of propylene and other α-olefins include ethylene-propylene copolymer resins, propylene-butene copolymer resins, ethylene-propylene-butene copolymer resins, propylene-hexene copolymer resins, and the like. Preferably mentioned. Among these, a propylene-based polymer resin having a propylene content of 50 mol% or more is more preferable, and a propylene-based polymer resin having a propylene content of 60 mol% or more is particularly preferable.
変性に用いられる不飽和カルボン酸又は酸無水物は、α，β―不飽和カルボン酸及び／又はその酸無水物が好ましく、具体的な例としては、マレイン酸及びその酸無水物、イタコン酸及びその酸無水物、シトラコン酸及びその酸無水物などが挙げられ、これらから選ばれた１種以上を好適に使用することができる。不飽和カルボン酸及び／又は酸無水物による変性量は、塩素を含有しないポリオレフィン樹脂１ｇ当たりに対して、０．０５〜０．８ｍｍｏｌが好ましく、より好ましくは、０．０７〜０．５ｍｍｏｌであり、特に好ましくは、０．１〜０．３５ｍｍｏｌである。この変性量（付加率）は、赤外分光スペクトル分析法により、カルボニル基の吸収強度を、この変性量（付加率）既知のサンプルに基づいて作成した検量線と対比することにより測定できる。この変性量が、０．０５ｍｍｏｌ未満では、乳化が困難であり、０．８ｍｍｏｌを超えると耐湿性が低下する。 The unsaturated carboxylic acid or acid anhydride used for modification is preferably α, β-unsaturated carboxylic acid and / or acid anhydride thereof. Specific examples include maleic acid and acid anhydrides, itaconic acid and Examples thereof include acid anhydrides, citraconic acid and acid anhydrides thereof, and one or more selected from these can be suitably used. The amount of modification with unsaturated carboxylic acid and / or acid anhydride is preferably 0.05 to 0.8 mmol, more preferably 0.07 to 0.5 mmol, per 1 g of polyolefin resin not containing chlorine. Particularly preferred is 0.1 to 0.35 mmol. This amount of modification (addition rate) can be measured by comparing the absorption intensity of the carbonyl group with a calibration curve prepared based on a sample having this modification amount (addition rate) known by infrared spectroscopy. If the amount of modification is less than 0.05 mmol, emulsification is difficult, and if it exceeds 0.8 mmol, the moisture resistance decreases.
本発明に用いる不飽和カルボン酸及び／又は酸無水物によって変性された非塩素化ポリオレフィン樹脂の融点は６０℃〜１００℃であり、好ましくは７０℃〜９５℃である。融点が６０℃未満の場合、耐湿性が低下し、また、１００℃を超えると付着性、低温衝撃性、低温屈曲性が低下する。なお、非塩素化ポリオレフィン樹脂の融点は、示差走査熱量測定器「ＤＳＣ−５０」（島津製作所）を使用し、−８０℃から１２０℃まで昇温速度５℃／分にて熱量を測定して得ることができる。 The melting point of the non-chlorinated polyolefin resin modified with the unsaturated carboxylic acid and / or acid anhydride used in the present invention is 60 ° C to 100 ° C, preferably 70 ° C to 95 ° C. When the melting point is less than 60 ° C., the moisture resistance is lowered, and when it exceeds 100 ° C., the adhesion, the low temperature impact property, and the low temperature flexibility are lowered. The melting point of the non-chlorinated polyolefin resin was measured by using a differential scanning calorimeter “DSC-50” (Shimadzu Corporation) and measuring the calorie from −80 ° C. to 120 ° C. at a heating rate of 5 ° C./min. Can be obtained.
また、本発明に用いる不飽和カルボン酸及び／又は酸無水物によって変性された非塩素化ポリオレフィン樹脂の重量平均分子量は、５０，０００〜２５０，０００であり、好ましくは７０，０００〜２１０，０００である。重量平均分子量が５０，０００未満であると、塗膜の凝集力低下により付着性が低下し、耐ガソホール性、耐湿性、高圧洗車性が低下するおそれがある。重量平均分子量が２５０，０００を超えると、水性樹脂製造に支障をきたすこととなる。なお、本発明において、重量平均分子量とは、ゲルパーミュエーションクロマトグラフィ（ＧＰＣ）により測定した重量平均分子量を、ポリスチレンの重量平均分子量を基準にして換算したときの値である。 The weight average molecular weight of the non-chlorinated polyolefin resin modified with the unsaturated carboxylic acid and / or acid anhydride used in the present invention is 50,000 to 250,000, preferably 70,000 to 210,000. It is. When the weight average molecular weight is less than 50,000, the adhesiveness is lowered due to a decrease in the cohesive strength of the coating film, and the gasohol resistance, moisture resistance, and high-pressure car washability may be reduced. When the weight average molecular weight exceeds 250,000, the aqueous resin production is hindered. In the present invention, the weight average molecular weight is a value obtained by converting the weight average molecular weight measured by gel permeation chromatography (GPC) on the basis of the weight average molecular weight of polystyrene.
また、本発明に用いる不飽和カルボン酸及び／又は酸無水物によって変性された非塩素化ポリオレフィン樹脂は、水性媒体に分散させるに当たって、水性化されていることが好ましい。
不飽和カルボン酸及び／又は酸無水物によって変性された非塩素化ポリオレフィン樹脂を水性化するには、アンモニアまたは１級〜３級の有機アミン類等のアミン系化合物を反応させて塩を形成することにより行うことができる。アミン系化合物としてはトリエチルアミン、トリプロピルアミン、トリブチルアミン、ジメチルエタノールアミン、トリエタノールアミン、ピリジン等の３級アミン類；ジプロピルアミン、ジブチルアミン、ジエタノールアミン、ピペリジン等の２級アミン類；プロピルアミン、ブチルアミン、エタノールアミン、アニリン等の１級アミン類などが使用できるが、特に３級アミンが好適である。アンモニアまたはアミン系化合物の使用量は、水性化する非塩素化ポリオレフィン系樹脂のカルボキシル基１モルに対して０．５〜３．０モル、好ましくは０．８〜２．５モルの範囲内とするのが望ましい。
In addition, the non-chlorinated polyolefin resin modified with the unsaturated carboxylic acid and / or acid anhydride used in the present invention is preferably made aqueous when dispersed in an aqueous medium.
In order to make a non-chlorinated polyolefin resin modified with an unsaturated carboxylic acid and / or acid anhydride aqueous, a salt is formed by reacting ammonia or an amine-based compound such as primary to tertiary organic amines. Can be done. Examples of amine compounds include tertiary amines such as triethylamine, tripropylamine, tributylamine, dimethylethanolamine, triethanolamine, and pyridine; secondary amines such as dipropylamine, dibutylamine, diethanolamine, and piperidine; propylamine, Primary amines such as butylamine, ethanolamine and aniline can be used, and tertiary amines are particularly preferred. The amount of ammonia or amine compound used is 0.5 to 3.0 moles, preferably 0.8 to 2.5 moles per mole of carboxyl groups of the non-chlorinated polyolefin resin to be water-based. It is desirable to do.
また、該非塩素化ポリオレフィン系樹脂の水性化には、必要に応じて界面活性剤を使用しても良い。界面活性剤としてはポリオキシエチレンモノアルキルエーテル、ポリオキシエチレンモノアルキルアリールエーテル、ポリオキシエチレンモノアルキルエステル等のノニオン系界面活性剤；ポリオキシエチレンアルキルアリールサルフェート塩、アルキルアリールサルフェート塩、アルキルサルフェート塩等のアニオン系界面活性剤などが使用できる。界面活性剤の使用量は該非塩素化ポリオレフィン樹脂樹固形分に対して通常１０質量％以下が好ましい。 In addition, a surfactant may be used as necessary for making the non-chlorinated polyolefin resin aqueous. Nonionic surfactants such as polyoxyethylene monoalkyl ether, polyoxyethylene monoalkyl aryl ether, polyoxyethylene monoalkyl ester, etc. as surfactants; polyoxyethylene alkyl aryl sulfate salts, alkyl aryl sulfate salts, alkyl sulfate salts Anionic surfactants such as can be used. As for the usage-amount of surfactant, 10 mass% or less is preferable normally with respect to this non-chlorinated polyolefin resin tree solid content.
また、該非塩素化ポリオレフィン系樹脂の水性化は、不飽和カルボン酸及び／又は酸無水物によって変性された非塩素化ポリオレフィン樹脂をポリ（オキシエチレン／オキシプロピレン）ブロック共重合体などの親水性高分子と結合させる方法により行ってもよい。親水性高分子は、重量平均分子量が２００〜１００，０００であることが好ましく、３００〜５０，０００がより好ましく、５００〜１０，０００が更に好ましい。また、不飽和カルボン酸及び／又は酸無水物によって変性された非塩素化ポリオレフィン樹脂への親水性高分子の結合量は、該変性された非塩素化ポリオレフィン樹脂１ｇ当たり０．０５〜１．０ｍｍｏｌが好ましく、０．１〜０．６ｍｍｏｌが特に好ましい。この方法としては、特開２００８−０３１３６０号公報などの公知の方法が挙げられる。 In addition, the non-chlorinated polyolefin resin can be made water-based by using a non-chlorinated polyolefin resin modified with an unsaturated carboxylic acid and / or an acid anhydride, such as a poly (oxyethylene / oxypropylene) block copolymer, which is highly hydrophilic. You may carry out by the method combined with a molecule | numerator. The hydrophilic polymer preferably has a weight average molecular weight of 200 to 100,000, more preferably 300 to 50,000, and still more preferably 500 to 10,000. Further, the binding amount of the hydrophilic polymer to the non-chlorinated polyolefin resin modified with the unsaturated carboxylic acid and / or acid anhydride is 0.05 to 1.0 mmol per 1 g of the modified non-chlorinated polyolefin resin. Is preferable, and 0.1 to 0.6 mmol is particularly preferable. Examples of this method include known methods such as JP-A-2008-031360.
（Ａ）成分の非塩素化ポリオレフィン樹脂の水分散体は、非塩素化ポリオレフィン樹脂、好ましくは水性化された非塩素化ポリオレフィン樹脂が水性媒体中に分散されたものである。非塩素化ポリオレフィン樹脂の水分散体における、分散された非塩素化ポリオレフィン樹脂の濃度は、通常５〜５０質量％が好ましく、１０〜４０質量％がより好ましい。
なお、水性媒体には、水以外の他の溶媒を配合してもよい。他の溶媒としては、例えば、トルエン、キシレン等の芳香族系炭化水素、ヘキサン、オクタン、デカン等の脂肪族系炭化水素、シクロヘキサン、メチルシクロヘキサン等の脂環式脂肪族系炭化水素、塩化メチレン、四塩化炭素、クロルベンゼン等のハロゲン化炭化水素、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル等のエステル類、アセトン、メチルエチルケトン、メチルプロピルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類、メタノール、エタノール、ｎ−プロピル、イソプロパノール、ｎ−ブタノール、２−ブタノール、イソブタノール、ｔ−ブタノール、シクロヘキサノール、エチレングリコール、プロピレングリコール、ブタンジオール等のアルコール類、ジプロピルエーテル、ジブチルエーテル、テトラヒドロフラン等のエーテル類、２−メトキシエタノール、２−エトキシエタノール、２−ブトキシエタノール、２−メトキシプロパノール、２−エトキシプロパノール、ジアセトンアルコール等の２以上の官能基を持つ有機溶媒、ジメチルホルムアミド、ジメチルスルホキシド等の極性溶媒などが挙げられる。
The aqueous dispersion of the non-chlorinated polyolefin resin (A) is a non-chlorinated polyolefin resin, preferably an aqueous non-chlorinated polyolefin resin dispersed in an aqueous medium. The concentration of the dispersed non-chlorinated polyolefin resin in the aqueous dispersion of the non-chlorinated polyolefin resin is usually preferably 5 to 50% by mass, and more preferably 10 to 40% by mass.
In addition, you may mix | blend other solvents other than water with an aqueous medium. Other solvents include, for example, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, octane and decane, alicyclic aliphatic hydrocarbons such as cyclohexane and methylcyclohexane, methylene chloride, Halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene, esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone and cyclohexanone, methanol, ethanol , N-propyl, isopropanol, n-butanol, 2-butanol, isobutanol, t-butanol, cyclohexanol, alcohols such as ethylene glycol, propylene glycol, butanediol, dipropyl ether, dibutyl ether, Ethers such as lahydrofuran, organic solvents having two or more functional groups such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol, diacetone alcohol, dimethylformamide, dimethyl Examples include polar solvents such as sulfoxide.
中でも、水に１質量％以上溶解する溶媒が好ましく、更に好ましくは５質量％以上溶解するものであり、例えば、メチルエチルケトン、メチルプロピルケトン、シクロヘキサノン、ｎ−プロピル、イソプロパノール、ｎ−ブタノール、２−ブタノール、イソブタノール、ｔ−ブタノール、シクロヘキサノール、テトラヒドロフラン、２−メトキシエタノール、２−エトキシエタノール、２−ブトキシエタノール、２−メトキシプロパノール、２−エトキシプロパノール、ジアセトンアルコールが好ましい。 Among them, a solvent that dissolves 1% by mass or more in water is preferable, and more preferably 5% by mass or more. For example, methyl ethyl ketone, methyl propyl ketone, cyclohexanone, n-propyl, isopropanol, n-butanol, 2-butanol , Isobutanol, t-butanol, cyclohexanol, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-ethoxypropanol and diacetone alcohol are preferred.
本発明の（Ｂ）成分である水酸基を含有しないポリウレタン樹脂水分散体としては、多官能イソシアネート化合物、一分子中に２個以上の水酸基を有するポリオール及び、アニオン性基を有する水酸基含有化合物を反応させて得られたウレタンプレポリマーをアンモニア、又は有機アミン類、又は水酸化カリウム、水酸化ナトリウム等の無機塩基類により中和し親水化したものを挙げることができる。さらに、同水分散体を、水、水溶性ポリアミン、グリコール類などの鎖伸長剤により高分子量化したものを用いても良い。また、必要に応じてアクリル等の変性をしても良い。 As the polyurethane resin aqueous dispersion which does not contain a hydroxyl group as the component (B) of the present invention, a polyfunctional isocyanate compound, a polyol having two or more hydroxyl groups in one molecule, and a hydroxyl group-containing compound having an anionic group are reacted. Examples thereof include those obtained by neutralizing the urethane prepolymer thus obtained with ammonia, organic amines, or inorganic bases such as potassium hydroxide and sodium hydroxide to make them hydrophilic. Further, the water dispersion may have a high molecular weight with a chain extender such as water, water-soluble polyamine, or glycols. Moreover, you may modify | denature acrylic etc. as needed.
この水酸基を含有しないポリウレタン樹脂水分散体に用いられるポリオールの種類としては特に限定されるものではなく、ポリエステルポリーオール、ポリエーテルポリオール、ポリカーボネートポリオール等を用いることができ、これらポリオールを用いて得られたウレタンプレポリマーはアクリル樹脂で一部変性されていても良い。また、ウレタンプレポリマーの親水化には、上述の水酸化カリウム、水酸化ナトリウム等の無機塩基類を用いても良いが、耐湿性の観点から、沸点が低く蒸発しやすいアンモニア、又は有機アミン類が好ましい。 The type of polyol used in the polyurethane resin aqueous dispersion containing no hydroxyl group is not particularly limited, and polyester polyols, polyether polyols, polycarbonate polyols, and the like can be used and are obtained using these polyols. The urethane prepolymer may be partially modified with an acrylic resin. In addition, for the hydrophilization of the urethane prepolymer, inorganic bases such as the above-mentioned potassium hydroxide and sodium hydroxide may be used. From the viewpoint of moisture resistance, ammonia or organic amines having a low boiling point and easily evaporated. Is preferred.
ポリウレタン樹脂水分散体が水酸基を含有する場合、未反応のまま塗膜中に残存し、耐湿性が低下するので好ましくない。
また、水酸基を含有しないポリウレタン樹脂水分散体は、測定可能な粒径を有し、かつ、平均粒径が１３０ｎｍ以下であることが好ましい。水に溶解してしまい、粒径が測定できない水溶性ポリウレタン樹脂の場合、塗装時にタレを生じやすく、塗膜外観が低下するため好ましくない。
When the polyurethane resin aqueous dispersion contains a hydroxyl group, it remains unreacted in the coating film, which is not preferable because moisture resistance is lowered.
Moreover, it is preferable that the polyurethane resin aqueous dispersion which does not contain a hydroxyl group has a measurable particle diameter, and an average particle diameter is 130 nm or less. A water-soluble polyurethane resin that dissolves in water and whose particle size cannot be measured is not preferable because it tends to cause sagging during coating and the appearance of the coating film decreases.
また、水酸基を含有しないポリウレタン樹脂水分散体の平均粒径が１３０ｎｍを超える場合は、粒子が大きいため沈降し、ブツや増粘を生じやすいので好ましくない。水酸基を含有しないポリウレタン樹脂水分散体の平均粒径の上限値は、１２０ｎｍ以下が好ましく、１００ｎｍ以下がより好ましい。水酸基を含有しないポリウレタン樹脂水分散体の平均粒径の下限値は、特に制限ないが、５ｎｍ以上が好ましく、１０ｎｍ以上がより好ましい。なお、水酸基を含有しないポリウレタン樹脂水分散体の粒径は、Ｎｉｃｏｍｐ社のＮｉｃｏｍｐ３８０ＺＬＳ粒度分布・ゼータ電位測定器で測定し、Ｇａｕｓｓｉａｎ分布／Ｖｏｌｕｍｅ Ｗｅｉｇｈｔｉｎｇの値を用いた。 Moreover, when the average particle diameter of the polyurethane resin aqueous dispersion which does not contain a hydroxyl group exceeds 130 nm, it is not preferable because the particles are so large that they are settled and easily cause blistering and thickening. The upper limit of the average particle size of the polyurethane resin aqueous dispersion containing no hydroxyl group, preferably at most 120 n m, and more preferably not more than 100 n m. The lower limit of the average particle diameter of the polyurethane resin water dispersion having no hydroxyl group is not particularly limited, preferably at least 5 n m, more preferably not less than 10 n m. In addition, the particle size of the polyurethane resin aqueous dispersion containing no hydroxyl group was measured with a Nicomp 380ZLS particle size distribution / zeta potential measuring instrument manufactured by Nicomp, and the value of Gaussian distribution / Volume Weighting was used.
水酸基を含有しないポリウレタン樹脂水分散体における、分散された水酸基を含有しないポリウレタン樹脂の濃度は、通常５〜５０質量％が好ましく、１０〜４０質量％がより好ましい。
また、水酸基を含有しないポリウレタン樹脂水分散体の水性媒体には、必要に応じて、Ｎ−メチル−２−ピロリドン、Ｎ−エチル−２−ピロリドン、２−ブトキシエタノールを含有させてもよい。
本発明の（Ｂ）成分である水酸基を含有しないポリウレタン樹脂水分散体の製造方法の具体例としては、特開２００８−０５６９１４号公報などが公知の方法として知られている。市販されている水酸基を含有しないポリウレタン樹脂水分散体としては、例えば、バイヒドロールＶＰ ＬＳ２９５２／１、バイヒドロール２３４２（住化バイエルウレタン社製）等を挙げることができる。
The concentration of the polyurethane resin containing no dispersed hydroxyl group in the polyurethane resin aqueous dispersion containing no hydroxyl group is usually preferably 5 to 50% by mass, more preferably 10 to 40% by mass.
Further, the aqueous medium of the polyurethane resin aqueous dispersion not containing a hydroxyl group may contain N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and 2-butoxyethanol as necessary.
As a specific example of a method for producing a polyurethane resin aqueous dispersion which does not contain a hydroxyl group as the component (B) of the present invention, JP-A-2008-056914 is known as a known method. Examples of commercially available polyurethane resin aqueous dispersions not containing a hydroxyl group include Bihydrol VP LS2952 / 1, Bihydrol 2342 (manufactured by Sumika Bayer Urethane Co., Ltd.), and the like.
本発明の（Ｃ）成分である導電性カーボンとしては、カーボンブラックなどが挙げられる。導電性カーボンは、例えば、２００ｍ２／ｇ以上、好ましくは８００ｍ２／ｇ以上の比表面積を有することが好ましい。比表面積が２００ｍ２／ｇ未満の場合、カーボンブラックの単位重量あたりの粒子個数が少なくなり、導電性が低下するため好ましくない。
導電性カーボンの平均粒径は、１０〜５０ｎｍが好ましい。
Examples of the conductive carbon that is the component (C) of the present invention include carbon black. The conductive carbon preferably has a specific surface area of, for example, 200 m 2 / g or more, preferably 800 m 2 / g or more. A specific surface area of less than 200 m 2 / g is not preferable because the number of particles per unit weight of carbon black decreases and the conductivity decreases.
The average particle size of the conductive carbon is preferably 10 to 50 nm.
本発明の（Ｄ）成分は、アミン価又は酸価の少なくとも一方が０ｍｇＫＯＨ／ｇ超である顔料分散剤であって、アミン価が分散剤の固形分あたり６５ｍｇＫＯＨ／ｇ以下であり、酸価が分散剤の固形分あたり３５ｍｇＫＯＨ／ｇ以下である顔料分散剤である。アミン価又は酸価のうち、アミン価は０ｍｇＫＯＨ／ｇ超であることが好ましい。アミン価は、分散剤の固形分あたり好ましくは４５ｍｇＫＯＨ／ｇ以下である。（Ｄ）成分である顔料分散剤のアミン価が６５ｍｇＫＯＨ／ｇを超える場合には、耐湿性が低下し、酸価が３５ｍｇＫＯＨ／ｇを超える場合には、塗料が凝集し増粘などの問題を生ずる。
顔料分散剤のアミン価の下限値は、１０ｍｇＫＯＨ／ｇ以上が好ましく、１５ｍｇＫＯＨ／ｇ以上がより好ましい。顔料分散剤の酸価の下限値は、１０ｍｇＫＯＨ／ｇ以上が好ましく、２０ｍｇＫＯＨ／ｇ以上がより好ましい。
The component (D) of the present invention is a pigment dispersant in which at least one of an amine value or an acid value is more than 0 mgKOH / g, the amine value is 65 mgKOH / g or less per solid content of the dispersant, and the acid value is It is a pigment dispersant which is 35 mgKOH / g or less per solid content of the dispersant. Of the amine value or acid value, the amine value is preferably more than 0 mgKOH / g. Amine value is preferably per solid content of the dispersant is Ru Der below 45 mg KOH / g. When the amine value of the pigment dispersant as component (D) exceeds 65 mgKOH / g, the moisture resistance decreases, and when the acid value exceeds 35 mgKOH / g, the paint aggregates and causes problems such as thickening. Is produced.
The lower limit of the amine value of the pigment dispersant is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more. The lower limit of the acid value of the pigment dispersant is preferably 10 mgKOH / g or more, and more preferably 20 mgKOH / g or more.
（Ｄ）成分の顔料分散剤の樹脂骨格としては、特に制限はなく、スチレン−マレイン酸共重合体樹脂、ポリウレタン樹脂、ポリエステル樹脂、アクリル樹脂などを用いることができる。
（Ｄ）成分の市販品としては、例えば、ＥＦＫＡ４５５０、ＥＦＫＡ４５８０（以上、Ｃｉｂａ社製品名）、ソルスパース４３０００、ソルスパース４４０００、ソルスパース４６０００、ソルスパース４７０００（以上、ルブリゾール社製品名）、Ｄｉｓｐｅｒｂｙｋ１８３、Ｄｉｓｐｅｒｂｙｋ１８５、Ｄｉｓｐｅｒｂｙｋ１８４、Ｄｉｓｐｅｒｂｙｋ１９０、Ｄｉｓｐｅｒｂｙｋ１９１、Ｄｉｓｐｅｒｂｙｋ２０１０、Ｄｉｓｐｅｒｂｙｋ２０９１（以上、ＢＹＫ
Ｃｈｅｍｉｅ社製品名）などが挙げられる。
There is no restriction | limiting in particular as resin skeleton of the pigment dispersant of (D) component, A styrene-maleic acid copolymer resin, a polyurethane resin, a polyester resin, an acrylic resin etc. can be used.
Examples of commercially available products of the component (D) include EFKA4550, EFKA4580 (above, product name of Ciba), Solsperse 43000, Solsperse 44000, Solsperse 46000, Solsperse 47000 (above, product name of Lubrizol), Disperbyk183, Disperbyk185, Disperk, 185 Disperbyk190, Disperbyk191, Disperbyk2010, Disperbyk2091 (above, BYK
Chemie product name).
本発明の水性プライマー組成物において、（Ａ）成分であるポリオレフィン水分散体の（Ｂ）成分の水酸基を含有しないポリウレタン樹脂水分散体に対する含有質量比率、すなわち（Ａ）／（Ｂ）で表される含有質量比率は、固形分換算で、２０／８０〜８０／２０の範囲内であり、好ましくは、３０／７０〜７０／３０の範囲内であり、特に好ましくは、４０／６０〜６０／４０の範囲内である。
（Ａ）成分の（Ｂ）成分に対する含有質量比率が２０／８０よりも少ない場合には、ポリプロピレン素材への付着性が低下する。また、（Ａ）成分の（Ｂ）成分に対する含有質量比率が８０／２０よりも多い場合には、極性差による上塗り（ベースコート）との付着不良が生じる。
In the aqueous primer composition of the present invention, the content ratio by mass of the aqueous polyolefin resin dispersion (A) to the aqueous polyurethane resin dispersion containing no hydroxyl group of the (B) component, that is, (A) / (B) The contained mass ratio is in the range of 20/80 to 80/20 in terms of solid content, preferably in the range of 30/70 to 70/30, particularly preferably 40/60 to 60 /. Within the range of 40.
When the content ratio of the component (A) to the component (B) is less than 20/80, the adhesion to the polypropylene material is lowered. Further, when the content ratio of the component (A) to the component (B) is more than 80/20, poor adhesion with the top coat (base coat) due to the polarity difference occurs.
また、（Ｃ）成分の導電性カーボンの（Ａ）成分と（Ｂ）成分とを合計した量に対する含有質量比率、すなわち（Ｃ）／｛（Ａ）＋（Ｂ）｝で表される含有質量比率は、固形分換算で２／９８〜２０／８０の範囲内であり、好ましくは４／９６〜１７／８３の範囲内であり、特に好ましくは６／９４〜１５／８５の範囲内である。
（Ｃ）成分の（Ａ）成分と（Ｂ）成分との合計量に対する含有質量比率が２／９８よりも少ない場合には、導電性が低下し、（Ｃ）成分の（Ａ）成分と（Ｂ）成分との合計量に対する含有質量比率が２０／８０よりも多い場合には、分散不良となり、ブツや沈降を生ずる可能性がある。
Moreover, the content mass ratio with respect to the total amount of the component (A) and the component (B) of the conductive carbon of the component (C), that is, the content mass represented by (C) / {(A) + (B)} The ratio is in the range of 2/98 to 20/80 in terms of solid content, preferably in the range of 4/96 to 17/83, and particularly preferably in the range of 6/94 to 15/85. .
When the content ratio of the (C) component to the total amount of the (A) component and the (B) component is less than 2/98, the conductivity decreases, and the (A) component (C) and ( When the content mass ratio with respect to the total amount with B) component is more than 20/80, it becomes a dispersion | distribution defect and may produce a fuzz and sedimentation.
さらに、（Ｄ）成分の顔料分散剤の（Ｃ）成分に対する含有質量比率は、固形分換算で、１０／９０〜５０／５０の範囲内であり、好ましくは、１５／８５〜４５／５５の範囲内であり、特に好ましくは、２０／８０〜４０／６０の範囲内である。
（Ｄ）成分の（Ｃ）成分に対する含有質量比率が１０／９０よりも少ない場合には、分散不良となり、ブツや沈降を生じやすく、（Ｄ）成分の（Ｃ）成分に対する含有質量比率が５０／５０よりも多い場合には、過分散となり再凝集によるブツ、沈降などが生じ、安定性の問題を生ずる可能性がある。
Furthermore, the mass ratio of the component (D) to the component (C) of the pigment dispersant is in the range of 10/90 to 50/50, preferably 15/85 to 45/55, in terms of solid content. It is in the range, and particularly preferably in the range of 20/80 to 40/60.
When the content ratio of the component (D) with respect to the component (C) is less than 10/90, dispersion is poor, and it is easy to cause unevenness and sedimentation. The content ratio of the component (D) with respect to the component (C) is 50. When the ratio is more than / 50, overdispersion occurs, causing reagglomeration, precipitation, sedimentation, and the like, which may cause stability problems.
本発明の水性プライマー組成物には、必要に応じて塗料分野で通常使用される着色顔料、体質顔料、消泡剤、レオロジーコントロール剤、硬化触媒、有機溶剤などを適宜使用することができる。着色顔料としては、例えば、二酸化チタン、ベンガラ、アゾ系顔料、フタロシアニン系顔料などが挙げられ、体質顔料としては、例えば、タルク、シリカ、炭酸カルシウム、硫酸バリウム、亜鉛華（酸化亜鉛）などが挙げられる。
本発明の水性プライマー組成物は、上記各成分と水性媒体とを含有するが、上記各成分の合計含有量は、固形分換算で１５〜４５質量％が好ましく、２５〜４０質量％がより好ましい。
In the aqueous primer composition of the present invention, coloring pigments, extender pigments, antifoaming agents, rheology control agents, curing catalysts, organic solvents and the like that are usually used in the paint field can be appropriately used as necessary. Examples of the color pigment include titanium dioxide, bengara, azo pigment, and phthalocyanine pigment, and examples of the extender pigment include talc, silica, calcium carbonate, barium sulfate, and zinc white (zinc oxide). It is done.
Although the aqueous | water-based primer composition of this invention contains said each component and aqueous medium, 15-45 mass% is preferable in conversion of solid content, and, as for the total content of said each component, 25-40 mass% is more preferable. .
本発明の水性プライマー組成物を塗装できるプラスチック素材としては、ポリプロピレン系樹脂、ポリアミド系樹脂、ポリブチレンテレフタレート系樹脂、不飽和ポリエステル系樹脂、ポリウレタン系樹脂、ポリカーボネート系樹脂、アクリル系樹脂、ポリフェニレンオキサイド系樹脂、ポリプロピレン系以外のポリオレフィン系樹脂など、幅広い樹脂が挙げられるが、これらの中ではポリプロピレン系樹脂が好ましい。
これらのプラスチック素材は、水性プライマー組成物の塗装に先立ち、既知の方法で、脱脂処理、水洗処理などを適宜行なっておくことができる。
Examples of plastic materials that can be coated with the aqueous primer composition of the present invention include polypropylene resins, polyamide resins, polybutylene terephthalate resins, unsaturated polyester resins, polyurethane resins, polycarbonate resins, acrylic resins, polyphenylene oxides A wide range of resins such as resins and polyolefin resins other than polypropylene are exemplified, and among these, polypropylene resins are preferable.
Prior to the application of the aqueous primer composition, these plastic materials can be appropriately subjected to degreasing treatment, washing treatment, and the like by a known method.
本発明の水性プライマー組成物の塗装は、プラスチック素材に対し、通常、乾燥膜厚で１〜４０μｍ、好ましくは５〜３０μｍの範囲内となるように行い、塗装方法としては特に限定はないが、スプレー方式または回転霧化方式が好ましい。
本発明の水性プライマー組成物の塗装後、必要に応じて室温で１０秒〜６０分間のセッティング、又は４０〜８０℃の温度で１〜６０分間予備加熱し、次に、上塗り塗料を塗装することが好ましい。
本発明の水性プライマー組成物とセットで用いる上塗り塗料としては、素材を変形させない温度で硬化が可能なものであれば特に限定されず、１液メラミン架橋塗料、１液イソシアネート架橋塗料、２液イソシアネート架橋などを上げることができる。ベースコート塗料は水性型、溶剤型のどちらを用いても良いが、クリヤーコート塗料は溶剤型の２液イソシアネート架橋塗料が好ましい。
The coating of the aqueous primer composition of the present invention is usually performed on a plastic material so that the dry film thickness is 1 to 40 μm, preferably 5 to 30 μm, and the coating method is not particularly limited, A spray method or a rotary atomization method is preferred.
After the application of the aqueous primer composition of the present invention, if necessary, setting at room temperature for 10 seconds to 60 minutes, or preheating at a temperature of 40 to 80 ° C. for 1 to 60 minutes, and then applying a top coating. Is preferred.
The top coat used in combination with the aqueous primer composition of the present invention is not particularly limited as long as it can be cured at a temperature that does not deform the material. One-part melamine crosslinked paint, one-part isocyanate crosslinked paint, two-part isocyanate Crosslinking can be raised. The base coat paint may be either an aqueous type or a solvent type, but the clear coat paint is preferably a solvent type two-component isocyanate cross-linked paint.
上塗塗料がメタリック塗料である場合、通常、ベースコート塗料とクリヤーコート塗料とは、ウェットオンウェットにて塗装される。ベースコート塗料の塗膜厚は、乾燥膜厚で１０〜２５μｍが好ましく、クリヤー塗料の塗膜厚は、２０〜５０μｍが好ましい。
上塗塗料がソリッド塗料である場合、乾燥膜厚で２０〜５０μｍが好ましい。
加熱硬化条件は、例えば、熱風加熱、赤外線加熱、高周波加熱等を用いて８０℃程度で２０〜４０分間加熱して硬化させることが好ましい。
上塗り塗料の塗装方法としてはスプレー塗装、または、回転霧化塗装が一般的であり、本発明の水性プライマー組成物が導電性を有しているため、ベース塗料及びクリヤ塗料の塗装は静電塗装を用いることができる。
When the top coat is a metallic paint, the base coat paint and the clear coat paint are usually applied wet-on-wet. The film thickness of the base coat paint is preferably 10 to 25 μm in terms of dry film thickness, and the film thickness of the clear paint is preferably 20 to 50 μm.
When the top coat is a solid paint, the dry film thickness is preferably 20 to 50 μm.
The heat curing conditions are preferably set by heating at about 80 ° C. for 20 to 40 minutes using hot air heating, infrared heating, high frequency heating or the like, for example.
Spray coating or rotary atomization coating is generally used as the top coating method. Since the aqueous primer composition of the present invention has conductivity, the base coating and the clear coating are applied electrostatically. Can be used.
以下、本発明について実施例を掲げて更に詳しく説明するが、本発明はこれらの実施例のみに限定されるものではない。また実施例中、「部」、「％」は特に断りのない限り「質量部」、「質量％」を意味する。 EXAMPLES Hereinafter, although an Example is hung up and demonstrated in more detail about this invention, this invention is not limited only to these Examples. In the examples, “parts” and “%” mean “parts by mass” and “% by mass” unless otherwise specified.
［製造例１：非塩素化ポリオレフィン樹脂の水分散体Ｐ−１の製造］
本発明に用いる非塩素化ポリオレフィン樹脂の水分散体は、次の３段階のプロセスを経て製造される。
（ｉ）第１段階：非塩素化ポリオレフィン樹脂の製造
１，０００ｍｌ丸底フラスコに、脱イオン水１１０ｍｌ、硫酸マグネシウム・７水和物２２．２ｇ及び硫酸１８．２ｇを採取し、攪拌下に溶解させた。この溶液に、市販の造粒モンモリロナイト１６．７ｇを分散させ、１００℃まで昇温し、２時間攪拌を行った。その後、室温まで冷却し、得られたスラリーを濾過してウェットケーキを回収した。回収したケーキを１，０００ｍｌ丸底フラスコ内で脱塩水５００ｍｌにて再度スラリー化し、濾過を行った。この操作を２回繰り返した。最終的に得られたケーキを、窒素雰囲気下１１０℃で終夜乾燥し、化学処理モンモリロナイト１３．３ｇを得た。得られた化学処理モンモリロナイト４．４ｇに、トリエチルアルミニウムのトルエン溶液（０．４ｍｍｏｌ／ｍｌ）２０ｍｌを加え、室温で１時間攪拌した。この懸濁液にトルエン８０ｍｌを加え、攪拌後、上澄みを除いた。この操作を２回繰り返した後、トルエンを加えて、粘土スラリー（スラリー濃度＝９９ｍｇ粘土／ｍｌ）を得た。
[Production Example 1: Production of water dispersion P-1 of non-chlorinated polyolefin resin]
The aqueous dispersion of non-chlorinated polyolefin resin used in the present invention is produced through the following three-stage process.
(I) First stage: Production of non-chlorinated polyolefin resin In a 1,000 ml round bottom flask, 110 ml of deionized water, 22.2 g of magnesium sulfate heptahydrate and 18.2 g of sulfuric acid were collected and dissolved under stirring. I let you. In this solution, 16.7 g of commercially available granulated montmorillonite was dispersed, heated to 100 ° C., and stirred for 2 hours. Then, it cooled to room temperature and filtered the obtained slurry, and collect | recovered the wet cake. The recovered cake was slurried again with 500 ml of demineralized water in a 1,000 ml round bottom flask and filtered. This operation was repeated twice. The finally obtained cake was dried at 110 ° C. overnight under a nitrogen atmosphere to obtain 13.3 g of chemically treated montmorillonite. To 4.4 g of the obtained chemically treated montmorillonite, 20 ml of a toluene solution of triethylaluminum (0.4 mmol / ml) was added and stirred at room temperature for 1 hour. To this suspension was added 80 ml of toluene, and after stirring, the supernatant was removed. After repeating this operation twice, toluene was added to obtain a clay slurry (slurry concentration = 99 mg clay / ml).
別のフラスコに、トリイソブチルアルミニウム０．２ｍｍｏｌを採取し、ここで得られた粘土スラリー１９ｍｌ及びジクロロ［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチル−４Ｈ−５，６，７，８−テトラヒドロ−１−アズレニル）ハフニウム１３１ｍｇ（５７μｍｏｌ）のトルエン希釈液を加え、室温で１０分間撹拌し、触媒スラリーを得た。
次いで、内容積２４リッターの誘導攪拌式オートクレーブ内に、トルエン１１Ｌ、トリイソブチルアルミニウム３．５ｍｍｏｌ及び液体プロピレン２．６４Ｌを導入した。室温で、上記触媒スラリーを全量導入し、６２℃まで昇温し重合時の全圧を０．６５ＭＰａで一定に保持しながら、同温度で２時間攪拌を継続した。攪拌終了後、未反応プロピレンをパージして重合を停止した。オートクレーブを開放してポリマーのトルエン溶液を全量回収し、溶媒ならびに粘土残渣を除去したところ、１１．０質量％のプロピレン系重合体のトルエン溶液を１１ｋｇ得た。得られたプロピレン系重合体の重量平均分子量Ｍｗは２１０，０００であった。
In a separate flask, 0.2 mmol of triisobutylaluminum was collected, and 19 ml of the clay slurry obtained here and dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-5,6,7,8 -Tetrahydro-1-azulenyl) Hafnium 131 mg (57 μmol) in toluene was added and stirred at room temperature for 10 minutes to obtain a catalyst slurry.
Next, 11 L of toluene, 3.5 mmol of triisobutylaluminum and 2.64 L of liquid propylene were introduced into an induction stirring autoclave having an internal volume of 24 liters. The whole amount of the catalyst slurry was introduced at room temperature, the temperature was raised to 62 ° C., and the stirring was continued at the same temperature for 2 hours while keeping the total pressure during polymerization at 0.65 MPa. After completion of the stirring, unreacted propylene was purged to terminate the polymerization. The autoclave was opened and the whole toluene solution of the polymer was recovered, and the solvent and clay residue were removed. As a result, 11 kg of a 11.0% by mass propylene polymer toluene solution was obtained. The weight average molecular weight Mw of the obtained propylene polymer was 210,000.
（ｉｉ）第２段階：非塩素化ポリオレフィン樹脂の無水マレイン酸変性品の製造
還流冷却管、温度計、攪拌機のついたガラスフラスコ中に、上記（ｉ）で示した第１段階で得られたプロピレン系重合体２００ｇ、及びトルエン３００ｇを入れ、容器内を窒素ガスで置換し、１１０℃に昇温した。昇温後、無水マレイン酸１２ｇを加え、ｔ−ブチルパーオキシイソプロピルモノカルボナート（日油（株）製、パーブチルＩ）６ｇを加え、７時間同温度で攪拌を続けて反応を行った。反応終了後、系を室温付近まで冷却し、アセトンを加えて、沈殿したポリマーを濾別した。さらにアセトンで沈殿・濾別を繰り返し、最終的に得られたポリマーをアセトンで洗浄した。洗浄後に得られたポリマーを減圧乾燥することにより、白色粉末状の無水マレイン酸変性ポリマーが得られた。この変性ポリマーの赤外線吸収スペクトル測定を行った結果、無水マレイン酸基の含量（グラフト率）は、１．３質量％（無水マレイン酸基として０．１３ｍｍｏｌ／プロピレン系重合体１ｇ）、重量平均分子量は１２０，０００であり、示差走査熱量測定器「ＤＳ−５０」で測定した融点は ８０℃であった。
(Ii) Second stage: Production of maleic anhydride modified product of non-chlorinated polyolefin resin Obtained in the first stage shown in (i) above in a glass flask equipped with a reflux condenser, thermometer and stirrer. 200 g of a propylene polymer and 300 g of toluene were added, the inside of the container was replaced with nitrogen gas, and the temperature was raised to 110 ° C. After raising the temperature, 12 g of maleic anhydride was added, 6 g of t-butyl peroxyisopropyl monocarbonate (manufactured by NOF Corporation, Perbutyl I) was added, and the reaction was continued for 7 hours at the same temperature. After completion of the reaction, the system was cooled to around room temperature, acetone was added, and the precipitated polymer was filtered off. Further, precipitation and filtration were repeated with acetone, and the finally obtained polymer was washed with acetone. The polymer obtained after washing was dried under reduced pressure to obtain a maleic anhydride-modified polymer in the form of a white powder. As a result of measuring the infrared absorption spectrum of this modified polymer, the content (graft ratio) of maleic anhydride groups was 1.3% by mass (0.13 mmol as maleic anhydride groups / 1 g of propylene polymer), and the weight average molecular weight. The melting point measured by a differential scanning calorimeter “DS-50” was 80 ° C.
（ｉｉｉ）第３段階：無水マレイン酸で変性された非塩素化ポリオレフィン樹脂の水分散体の製造
還流冷却管、温度計、攪拌機のついたガラスフラスコ中に、上記（ｉｉ）の第２段階で得られた無水マレイン酸変性プロピレン系重合体１００ｇ（無水マレイン酸基の含量１３ｍｍｏｌ）及びトルエン２５０ｇを加え、１１０℃に昇温し、完全に溶解した。次いで、ポリ（オキシエチレン／オキシプロピレン）ブロック共重合体（分子量１０００）３０ｇ（３０．０ｍｍｏｌ、プロピレン系重合体１００質量部に対し３０質量部に相当）をトルエン２２．５ｇに溶解した溶液を加え、１１０℃で３時間反応させた。
冷却後トルエンを減圧留去し、黄色のポリマー１１５ｇを得た。得られた生成物の赤外吸収スペクトル分析を行った結果、１７８４ｃｍ−１付近の無水マレイン酸に相当するピークは消滅し、無水マレイン酸変性プロピレン系重合体とポリエーテルが結合していることが確認された。無水マレイン酸変性プロピレン系重合体にポリエーテルがグラフト結合したグラフト共重合体を形成している。得られた変性ポリマー４０ｇにテトラヒドロフラン（ＴＨＦ）１６０ｇを加え６５℃で完全に溶解させた。純水２００ｇを同温度で１時間かけて滴下し、半透明の淡黄色溶液を得た。これを５０℃に冷却し、減圧度０．０３ＭＰａから０．００４５ＭＰａまで徐々に圧力を下げて樹脂固形分濃度が２５質量％になるまでＴＨＦ及び水を減圧留去し、半透明淡黄色の水性樹脂分散体Ｐ−１を得た。
なお、本実施例で用いたポリ（オキシエチレン／オキシプロピレン）ブロック共重合体は、２５℃の水に１０質量％の濃度で溶解させたときに不溶分が１質量％以下であり、親水性高分子であった。
(Iii) Third stage: Preparation of aqueous dispersion of non-chlorinated polyolefin resin modified with maleic anhydride In a glass flask equipped with a reflux condenser, a thermometer and a stirrer, the above (ii) 100 g of maleic anhydride-modified propylene polymer obtained in the second stage (maleic anhydride group content 13 mmol) and 250 g of toluene were added, and the temperature was raised to 110 ° C. to completely dissolve. Next, a solution of 30 g of poly (oxyethylene / oxypropylene) block copolymer (molecular weight 1000) (30.0 mmol, corresponding to 30 parts by mass with respect to 100 parts by mass of the propylene polymer) dissolved in 22.5 g of toluene was added. , Reacted at 110 ° C. for 3 hours.
After cooling, toluene was distilled off under reduced pressure to obtain 115 g of a yellow polymer. As a result of infrared absorption spectrum analysis of the obtained product, the peak corresponding to maleic anhydride in the vicinity of 1784 cm −1 disappears, and the maleic anhydride-modified propylene polymer and the polyether are bonded. confirmed. A graft copolymer is formed by grafting a polyether to a maleic anhydride-modified propylene polymer. To 40 g of the resulting modified polymer, 160 g of tetrahydrofuran (THF) was added and completely dissolved at 65 ° C. 200 g of pure water was added dropwise at the same temperature over 1 hour to obtain a translucent pale yellow solution. This was cooled to 50 ° C., and the pressure was gradually reduced from 0.03 MPa to 0.0045 MPa, and THF and water were distilled off under reduced pressure until the resin solids concentration was 25% by mass. Resin dispersion P-1 was obtained.
The poly (oxyethylene / oxypropylene) block copolymer used in this example has an insoluble content of 1% by mass or less when dissolved in water at 25 ° C. at a concentration of 10% by mass, and is hydrophilic. It was a polymer.
〔実施例１〕
水酸基を含有しないポリウレタン樹脂水分散体「Ｄａｏｔａｎ ＴＷ１２３７／３２ＷＡＮＥＰ」（商品名、日本サイテックインダストリーズ社製、固形分３２質量％、平均粒子径６２ｎｍ、水酸基価 ０ｍｇＫＯＨ／ｇ）２７．６４部に、導電性カーボンブラック「プリンテックスＸＥ２Ｂ」（商品名、デグサ社製）１．５５部、二酸化チタン「ＪＲ６００−Ｅ」（商品名、テイカ社製）８．８４部、顔料分散剤「Ｄｉｓｐｅｒｂｙｋ１９１」（商品名、ＢＹＫ Ｃｈｅｍｉｅ社製、固形分９８質量％、酸価 ３１ｍｇＫＯＨ／ｇ、アミン価 ２０ｍｇＫＯＨ／ｇ）０．９３部を加えて、分散機にて分散後、非塩素化ポリオレフィン樹脂の水分散体Ｐ−１ ４３．２４部、脱イオン水 １５．８部、レベリング剤「ＢＹＫ―３４８」（商品名、ＢＹＫ Ｃｈｅｍｉｅ社製）０．８部、 増粘剤「ＡＳＥ−６０」（ローム・アンド・ハース社製、固形分２８質量％）１．１部を加えてディゾルバーで混合した後、ｐＨを７〜８になるように、ジメチルエタノールアミンにて調整し、水性プライマー組成物を製造した。
[Example 1]
Polyurethane resin water dispersion “Daotan TW1237 / 32WANEP” containing no hydroxyl group (trade name, manufactured by Nippon Cytec Industries, Inc., solid content 32% by mass, average particle size 62 nm, hydroxyl value 0 mg KOH / g) Carbon black “Printex XE2B” (trade name, manufactured by Degussa) 1.55 parts, titanium dioxide “JR600-E” (trade name, manufactured by Teika) 8.84 parts, pigment dispersant “Disperbyk191” (trade name, BYK Chemie, solid content 98% by mass, acid value 31 mgKOH / g, amine value 20 mgKOH / g) 0.93 part was added and dispersed with a disperser, then an aqueous dispersion P-1 of non-chlorinated polyolefin resin 43.24 parts, deionized water 15.8 parts, leveling agent “BYK-348” (trade name, BYK (Chemie) 0.8 parts, Thickener “ASE-60” (Rohm and Haas, solid content 28% by mass) 1.1 parts was added and mixed with a dissolver, and the pH was adjusted to 7-8. The aqueous primer composition was prepared by adjusting with dimethylethanolamine.
〔実施例２〜６、比較例１〜１０〕
表１〜表３に記載した原料に替えた以外は、実施例１と同様にして、実施例２〜６、比較例１〜１０を製造した。
Example 2-6, Comparative Examples 1-10]
Except for changing the raw materials described in Table 1 to Table 3, in the same manner as in Example 1, Example 2-6 was prepared in Comparative Example 1-10.
表１〜３の注記
・Ｄａｏｔａｎ ＴＷ１２３７／３２ＷＮＥＰ（水酸基を含有しないポリウレタン樹脂水分散体；商品名、日本サイテックインダストリーズ社製、固形分３２質量％、平均粒子径６２ｎｍ、水酸基価０ｍｇＫＯＨ／ｇ）
・Ｂａｙｈｙｄｒｏｌ ＰＲ６５０（水酸基を含有しないポリウレタン樹脂水分散体；商品名、住化バイエルウレタン社製、固形分５０質量％、平均粒子径１６９ｎｍ、水酸基価０ｍｇＫＯＨ／ｇ）
・Ｄａｏｔａｎ ＶＴＷ１２６５／３６ＷＡ
（ポリウレタン樹脂水分散体；商品名、日本サイテックインダストリーズ社製、固形分３６質量％、平均粒子径４０ｎｍ、水酸基価２４ｍｇＫＯＨ／ｇ）
Notes in Tables 1 to 3: Daotan TW1237 / 32WNEP (polyurethane resin aqueous dispersion containing no hydroxyl group; trade name, manufactured by Nippon Cytec Industries, solid content 32% by mass, average particle size 62 nm, hydroxyl value 0 mgKOH / g)
Bayhydrol PR650 (polyurethane resin aqueous dispersion containing no hydroxyl group; trade name, manufactured by Sumika Bayer Urethane Co., Ltd., solid content 50 mass%, average particle size 169 nm, hydroxyl value 0 mg KOH / g)
・ Daotan VTW1265 / 36WA
(Polyurethane resin aqueous dispersion; trade name, manufactured by Nippon Cytec Industries, Ltd., solid content 36% by mass, average particle size 40 nm, hydroxyl value 24 mgKOH / g)
・Ｄｉｓｐｅｒｂｙｋ １９１ （顔料分散剤；商品名、ＢＹＫ Ｃｈｅｍｉｅ社製、固形分９８質量％、固形分あたりの酸価３１ｍｇＫＯＨ／ｇ、固形分あたりのアミン価２０ｍｇＫＯＨ／ｇ）
・Ｄｉｓｐｅｒｂｙｋ １８３（顔料分散剤；商品名、ＢＹＫ Ｃｈｅｍｉｅ社製、固形分５２質量％、固形分あたりの酸価０ｍｇＫＯＨ／ｇ、固形分あたりのアミン価３３ｍｇＫＯＨ／ｇ）
・ＥＦＫＡ ４５５０（顔料分散剤；商品名、Ｃｉｂａ社製、固形分５０質量％ 固形分あたりの酸価０ｍｇＫＯＨ／ｇ、固形分あたりのアミン価５０〜６２ｍｇＫＯＨ／ｇ）
・ＥＦＫＡ ４５９０（顔料分散剤；商品名、Ｃｉｂａ社製、固形分４２質量％、固形分あたりの酸価９．５〜１９ｍｇＫＯＨ／ｇ、固形分あたりのアミン価８５．７〜１００ｍｇＫＯＨ／ｇ）
・Ｄｉｓｐｅｒｂｙｋ ２０９０（顔料分散剤；商品名、ＢＹＫ Ｃｈｅｍｉｅ社製、固形分８１質量％、固形分あたりの酸価７５ｍｇＫＯＨ／ｇ、固形分あたりのアミン価０ｍｇＫＯＨ／ｇ）
・Ｄｉｓｐｅｒｂｙｋ ２０１０（顔料分散剤；商品名、ＢＹＫ Ｃｈｅｍｉｅ社製、固形分４０質量％、固形分あたりの酸価５０ｍｇＫＯＨ／ｇ、固形分あたりのアミン価５０ｍｇＫＯＨ／ｇ）
・Ｄｉｓｐｅｒｂｙｋ １８０（顔料分散剤；商品名、ＢＹＫ Ｃｈｅｍｉｅ社製、固形分８１質量％、 固形分あたりの酸価１１６ｍｇＫＯＨ／ｇ、固形分あたりのアミン価１１６ｍｇＫＯＨ／ｇ）
Disperbyk 191 (pigment dispersant; trade name, manufactured by BYK Chemie, solid content 98% by mass, acid value 31 mgKOH / g per solid content, amine value 20 mgKOH / g per solid content)
Disperbyk 183 (pigment dispersant; trade name, manufactured by BYK Chemie, solid content 52% by mass, acid value 0 mgKOH / g per solid content, amine value 33 mgKOH / g per solid content)
EFKA 4550 (pigment dispersant; trade name, manufactured by Ciba, solid content 50% by mass, acid value 0 mgKOH / g per solid content, amine value 50-62 mgKOH / g per solid content)
EFKA 4590 (pigment dispersant; trade name, manufactured by Ciba, 42 mass% solid content, acid value 9.5 to 19 mg KOH / g per solid content, amine value 85.7 to 100 mg KOH / g per solid content)
Disperbyk 2090 (pigment dispersant; trade name, manufactured by BYK Chemie, solid content 81% by mass, acid value 75 mgKOH / g per solid content, amine value 0 mgKOH / g per solid content)
Disperbyk 2010 (pigment dispersant; trade name, manufactured by BYK Chemie, solid content 40% by mass, acid value 50 mgKOH / g per solid content, amine value 50 mgKOH / g per solid content)
Disperbyk 180 (pigment dispersant; trade name, manufactured by BYK Chemie, solid content 81% by mass, acid value 116 mgKOH / g per solid content, amine value 116 mgKOH / g per solid content)
＜試験方法及び評価＞
試験方法及び評価は、次に記載した方法で実施し、結果を表１〜表３に示した。
（試験板の作成）
イソプロピルアルコールを用いて表面をワイプしたポリプロピレン素材「ＳＰ−８５３」に各水性プライマー組成物をエアースプレーで乾燥塗膜が６〜８μｍになるように塗装を行い、６０℃雰囲気の乾燥機で４分間乾燥させた。乾燥後、試験板を室温まで冷却した。次いで、アクリル樹脂系ベースコート「プライマックＮｏ．８６５０シルバーメタリック」（ＢＡＳＦコーティングスジャパン社製）を塗装し、次に、アクリルウレタン系トップコート「プライマックＮｏ．８６５０クリヤーコート」（ＢＡＳＦコーティングスジャパン社製）を塗装した。室温で１０分間放置した後、８０℃で３０分間焼き付け乾燥させた。
<Test method and evaluation>
The test method and evaluation were carried out by the methods described below, and the results are shown in Tables 1 to 3.
(Creation of test plate)
Each water-based primer composition is applied to a polypropylene material “SP-853” whose surface is wiped with isopropyl alcohol so that the dry coating film becomes 6 to 8 μm by air spray, and is dried for 4 minutes in a dryer at 60 ° C. atmosphere. Dried. After drying, the test plate was cooled to room temperature. Next, an acrylic resin base coat “Primac No. 8650 Silver Metallic” (manufactured by BASF Coatings Japan) is applied, and then an acrylic urethane top coat “Primac No. 8650 clear coat” (manufactured by BASF Coatings Japan). ) Was painted. After leaving at room temperature for 10 minutes, it was baked and dried at 80 ° C. for 30 minutes.
（導電性）
長さが約１５ｃｍのプラスチック素材の両端を各々に、市販されているアルミニウムテープを巻き付け、測定器の端子間距離が、１０ｃｍになるように、端子の位置に予め印を付けておき、次に、アルミニウムテープの上から、素材との境を約３〜５ｍｍ残して、マスキングテープを巻き付けた後、導電性プライマー用塗料組成物をエアースプレーにて塗装した。塗装直後、マスキングテープを速やかに剥がし、６０℃で４分間乾燥させた後、両端のアルミニウムテープ部分に、共立電気計器（株）製「３レンジ絶縁抵抗計モデル３３０１」の端子を取り付け、導電性を測定した。測定値の単位は、「×１０６Ω」である。ＷＥＴ塗膜導電性の評価基準は、１，０００×１０６Ω未満であるものを「○」とし、１，０００×１０６Ω以上を「×」とした。
(Conductivity)
Wrap a commercially available aluminum tape around each end of a plastic material with a length of about 15 cm, and mark the terminal positions in advance so that the distance between terminals of the measuring device is 10 cm. From the top of the aluminum tape, the masking tape was wrapped around the boundary with the material, leaving about 3 to 5 mm, and then the conductive primer coating composition was applied by air spray. Immediately after painting, the masking tape is quickly peeled off and dried at 60 ° C for 4 minutes, and then the terminals of “3 range insulation resistance meter model 3301” manufactured by Kyoritsu Electric Instruments Co., Ltd. are attached to the aluminum tape portions at both ends. Was measured. The unit of the measured value is “× 10 6 Ω”. Evaluation criteria WET Nurimakushirube conductive are those less than 1,000 × 10 6 Omega as "○", and the above 1,000 × 10 6 Omega as "×".
（分散性）
分散したミルベースの分散度をＪＩＳ Ｋ−５６００−２−５（２００９年版）に従い測定した。
○・・・分散度が１５μ未満で、ブツなどの異常がない状態。
△・・・分散度が１５μ〜２０μで僅かにブツがある状態。
×・・・分散度２０μより大きく分散が進まず多数のブツがある状態。
(Dispersibility)
The degree of dispersion of the dispersed mill base was measured according to JIS K-5600-2-5 (2009 edition).
○ ... The degree of dispersion is less than 15μ and there is no abnormality such as bumps.
Δ: The degree of dispersion is 15 μm to 20 μm, and there are slight bumps.
X: Dispersion greater than 20μ, and dispersion does not proceed, and there are a large number of irregularities.
（塗料の凝集）
製造した塗料容器の中を目視で確認した。次いで、ガラス板に流し塗りし、塗膜に凝集ブツがないか目視で確認した。
○・・・塗料、塗膜ともに異常が無い状態。
△・・・塗料がややクリーム状、もしくは、塗膜に少量の凝集ブツが見られる状態。
×・・・塗装が不可能な状態。
(Coagulation of paint)
The inside of the manufactured paint container was visually confirmed. Subsequently, the glass plate was cast and coated, and the coating film was visually confirmed to be free from agglomeration.
○ ・ ・ ・ Neither paint nor coating film is abnormal.
Δ: The paint is a little creamy, or a small amount of cohesive spots are seen in the coating film.
X: State in which painting is impossible.
（付着性）
上塗り塗装された塗膜に、２ｍｍ間隔の１００マスが得られるように、カッターナイフで縦横１１本の切れ目を入れ、セロハンテープを密着させて一気にはがした時に塗膜が剥離せず残存したマス目数によって以下の基準で評価した。
付着性の評価は次のようにした。
○・・・塗膜のハガレがない状態（碁盤目表記では、１００／１００）。
△・・・塗膜の一部にハガレがある状態（碁盤目表記では、９５〜９９／１００）。
×・・・塗膜の大部分にハガレがある状態（碁盤目表記では、０〜９４／１００）。
なお、「付着性（素材）」とは、素材とプライマー塗膜との層間の付着性のことであり、「付着性（上塗り）」とは、プライマー塗膜と上塗り塗膜との層間の付着性を意味している。
(Adhesiveness)
In order to obtain 100 squares at 2 mm intervals on the top-coated film, cut the 11 vertical and horizontal cuts with a cutter knife, adhere the cellophane tape and remove the coating without peeling off at once. Evaluation was made according to the following criteria according to the number of eyes.
The evaluation of adhesion was as follows.
○: No peeling of the coating film (100/100 in crosscut notation).
Δ: A state in which there is peeling in a part of the coating film (95 to 99/100 in cross notation).
X: A state in which the majority of the coating film has peeling (0 to 94/100 in cross-cut notation).
“Adhesion (material)” refers to the adhesion between the material and the primer coating, and “Adhesion (overcoat)” refers to the adhesion between the primer and the top coating. It means sex.
（耐湿性）
上塗り塗装された塗装板を、５０℃、湿度９５％の恒温恒湿槽内に入れ、３００時間放置した。放置後、塗装板を取り出し、塗膜の外観異常や、ふくれの程度を調べた。また、取り出してから２時間後に上記付着性試験と同様の方法で、耐湿性試験後の付着性を評価した。耐湿性試験後の外観の評価は次のようにした。
○・・・塗膜に異常が無い状態。
△・・・塗膜にチカチカや、僅かに外観異常がある状態。
×・・・塗膜にふくれや著しい外観異常がある状態。
また、耐湿試験後の付着性試験は、上記の方法と同じである。
(Moisture resistance)
The coated plate coated with the top coat was placed in a constant temperature and humidity chamber at 50 ° C. and a humidity of 95% and left for 300 hours. After leaving, the painted plate was taken out, and the appearance abnormality of the coating film and the degree of blistering were examined. In addition, the adhesion after the moisture resistance test was evaluated by the same method as the above adhesion test 2 hours after the removal. The appearance after the moisture resistance test was evaluated as follows.
○ ・ ・ ・ No abnormality in the coating film.
Δ: The coating film is flickering or has a slight appearance abnormality.
X: A state where the coating film has blisters or significant appearance abnormality.
The adhesion test after the moisture resistance test is the same as the above method.
（安定性）
塗料を３０℃の恒温層に入れ３ヶ月静置した。室温に冷却した後、スプレー塗装し、外観を目視で確認した。
○・・・塗膜に異常が無い状態。
△・・・顔料凝集によるブツが僅かにあるが、塗装可能な状態。
×・・・ブツが多く塗装が不可能な状態。
(Stability)
The paint was placed in a constant temperature layer at 30 ° C. and allowed to stand for 3 months. After cooling to room temperature, spray coating was performed and the appearance was visually confirmed.
○ ・ ・ ・ No abnormality in the coating film.
Δ: There is a slight amount of pigment aggregation, but it can be painted.
× ・ ・ ・ There are so many things that can't be painted.
Claims (4)
（Ｂ）水酸基を含有しないポリウレタン樹脂水分散体、
（Ｃ）導電性カーボン、及び
（Ｄ）アミン価又は酸価の少なくとも一方が０ｍｇＫＯＨ／ｇ超であり、分散剤の固形分あたりアミン価が６５ｍｇＫＯＨ／ｇ以下であり、酸価が３５ｍｇＫＯＨ／ｇ以下である顔料分散剤、を含有し、（Ａ）／（Ｂ）の含有質量比率が、固形分換算で２０／８０〜８０／２０の範囲内であり、かつ、（Ｃ）／｛（Ａ）＋（Ｂ）｝の含有質量比率が、固形分換算で２／９８〜２０／８０の範囲内であり、かつ、（Ｄ）／（Ｃ）の含有質量比率が、固形分換算で１０／９０〜５０／５０の範囲内であることを特徴とする水性プライマー組成物。 (A) An aqueous dispersion of a non-chlorinated polyolefin resin modified with an unsaturated carboxylic acid and / or acid anhydride having a melting point of 60 ° C. to 100 ° C. and a weight average molecular weight of 50,000 to 250,000. ,
(B) a polyurethane resin aqueous dispersion containing no hydroxyl group,
(C) conductive carbon, and (D) at least one of amine value or acid value is more than 0 mgKOH / g, amine value is 65 mgKOH / g or less per solid content of the dispersant , and acid value is 35 mgKOH / g or less. And (A) / (B) containing mass ratio is in the range of 20/80 to 80/20 in terms of solid content, and (C) / {(A) + (B)} is in the range of 2/98 to 20/80 in terms of solid content, and the content ratio of (D) / (C) is 10/90 in terms of solid content. An aqueous primer composition characterized by being in the range of ~ 50/50.
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