JP4402927B2 - Water-based primer paint and coating film forming method using the same - Google Patents
Water-based primer paint and coating film forming method using the same Download PDFInfo
- Publication number
- JP4402927B2 JP4402927B2 JP2003326482A JP2003326482A JP4402927B2 JP 4402927 B2 JP4402927 B2 JP 4402927B2 JP 2003326482 A JP2003326482 A JP 2003326482A JP 2003326482 A JP2003326482 A JP 2003326482A JP 4402927 B2 JP4402927 B2 JP 4402927B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- water
- aqueous
- paint
- coating film
- 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.)
- Expired - Lifetime
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- 238000000576 coating method Methods 0.000 title claims description 84
- 239000011248 coating agent Substances 0.000 title claims description 83
- 238000000034 method Methods 0.000 title claims description 21
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- 239000003973 paint Substances 0.000 title description 74
- -1 primary amine compound Chemical class 0.000 claims description 96
- 229920005989 resin Polymers 0.000 claims description 68
- 239000011347 resin Substances 0.000 claims description 68
- 239000002987 primer (paints) Substances 0.000 claims description 54
- 229920000877 Melamine resin Polymers 0.000 claims description 47
- 239000000126 substance Substances 0.000 claims description 42
- 239000004640 Melamine resin Substances 0.000 claims description 40
- 239000000839 emulsion Substances 0.000 claims description 40
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- 239000000463 material Substances 0.000 claims description 34
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- 229920000180 alkyd Polymers 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 25
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- 229920000647 polyepoxide Polymers 0.000 claims description 21
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000000049 pigment Substances 0.000 description 36
- 239000004743 Polypropylene Substances 0.000 description 33
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- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
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- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 7
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- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Description
本発明は、ポリプロピレン素材に適した水性プライマー塗料およびこれを用いた塗膜形成方法に関する。 The present invention relates to an aqueous primer coating suitable for a polypropylene material and a coating film forming method using the same.
自動車バンパーなどには、その長期性能保持と美観・意匠性の向上を目的として、その素材上にプライマー塗料や上塗り塗料による塗装が施される。これらプライマー塗料や上塗り塗料などの塗料は、近年、環境を考慮して、有機溶剤型塗料から水性塗料に変換されつつある。
ところで、自動車バンパーなどの素材としては、リサイクルが容易なポリプロピレンが汎用されているが、ポリプロピレン素材は化学的に不活性であるために、塗料の密着性が極めて悪い。そこで、ポリプロピレン素材に対して良好な密着性を示す水性塗料として、例えば酸無水物や不飽和ポリカルボン酸などで変性された変性塩素化ポリオレフィンを含むプライマー塗料が提案されている（例えば、特許文献１、２参照）。特に、特許文献２においては、顔料分散性および耐水性を改善するために、水性エポキシ樹脂および水性アルキッド樹脂を配合することが開示されている。
By the way, as a material for an automobile bumper or the like, polypropylene that is easy to recycle is widely used. However, since the polypropylene material is chemically inert, the adhesion of the paint is extremely poor. Accordingly, as a water-based paint exhibiting good adhesion to a polypropylene material, for example, a primer paint containing a modified chlorinated polyolefin modified with an acid anhydride or an unsaturated polycarboxylic acid has been proposed (for example, patent document). 1 and 2). In particular, Patent Document 2 discloses blending an aqueous epoxy resin and an aqueous alkyd resin in order to improve pigment dispersibility and water resistance.
しかしながら、前記特許文献１および２で開示されているような塗料により形成される塗膜は、いずれも熱可塑性樹脂塗膜に近いものであり、いわゆる架橋された塗膜ではないので、塗膜強度が低く、耐水性も未だ不充分であった。
一般に、水性塗料より形成される塗膜に施しうる架橋としては、ポリカルボジイミドによる架橋、水性エポキシ樹脂−アミンによる架橋、水性イソシアネート−ポリオール含有樹脂による架橋、メラミン樹脂による架橋などが考えられる。これらのなかで、ポリカルボジイミドによる架橋は貯蔵安定性が悪くなるという欠点があり、水性エポキシ樹脂−アミンによる架橋および水性イソシアネート−ポリオール含有樹脂による架橋は２液型であるため利便性を損なうという欠点があるため、１液型で貯蔵安定性が良好なメラミン樹脂による架橋が望ましい。このメラミン樹脂による架橋においては、触媒として酸性物質が有効であり、塗料のｐＨが低いほど、すなわち酸性度が高いほど、反応が進行しやすいことが知られている。
However, since the coating film formed by the paint as disclosed in Patent Documents 1 and 2 is close to the thermoplastic resin coating film and is not a so-called crosslinked coating film, the coating film strength The water resistance was still insufficient.
In general, examples of crosslinking that can be applied to a coating film formed from an aqueous paint include crosslinking with polycarbodiimide, crosslinking with an aqueous epoxy resin-amine, crosslinking with an aqueous isocyanate-polyol-containing resin, and crosslinking with a melamine resin. Among these, cross-linking with polycarbodiimide has the disadvantage that storage stability is poor, and cross-linking with aqueous epoxy resin-amine and cross-linking with aqueous isocyanate-polyol-containing resin is a two-component type, which impairs convenience. Therefore, cross-linking with a melamine resin that is one-pack type and has good storage stability is desirable. In this melamine resin crosslinking, it is known that an acidic substance is effective as a catalyst, and the reaction proceeds more easily as the pH of the paint is lower, that is, the acidity is higher.
ところが、水性塗料においては、通常、水中安定性を保つために、樹脂等の中和剤やｐＨ調整剤として塩基性物質が配合されており、この塩基性物質としては、解離定数が大きく比較的少量で中和することができるという理由から、一般に第２級アミン化合物や第３級アミン化合物が用いられている。この第２級アミン化合物や第３級アミン化合物は、塗料中の酸性物質と塩を形成して酸性度を低下させ、酸性物質の触媒としての作用を阻害してメラミン樹脂による架橋を妨げることになる。このように第２級アミン化合物や第３級アミン化合物がメラミン樹脂による架橋を妨げるという現象は、高温での焼付けが可能な用途においては、高温で焼付けする際に第２級アミン化合物や第３級アミン化合物を解離・揮散させ、その後、酸性度が高い状態になったところで架橋反応を進行させることが可能であるので、問題になることはないが、ポリプロピレン素材に塗装する場合など、高温焼付けができない用途においては、致命的な問題となる。したがって、ポリプロピレン素材用の水性塗料においては、メラミン樹脂による架橋は適さないと考えられていた。 However, in water-based paints, a basic substance is usually blended as a neutralizing agent such as a resin or a pH adjuster in order to maintain stability in water. As this basic substance, the dissociation constant is relatively large. Secondary amine compounds and tertiary amine compounds are generally used because they can be neutralized in a small amount. This secondary amine compound or tertiary amine compound forms a salt with the acidic substance in the paint to reduce the acidity, inhibits the action of the acidic substance as a catalyst, and prevents the crosslinking by the melamine resin. Become. As described above, the phenomenon that the secondary amine compound or the tertiary amine compound prevents the crosslinking by the melamine resin is used in applications where baking at a high temperature is possible. Since the secondary amine can be dissociated and volatilized, and then the crosslinking reaction can proceed when the acidity is high, there is no problem. In applications where this is not possible, this is a fatal problem. Accordingly, it has been considered that crosslinking with a melamine resin is not suitable for water-based paints for polypropylene materials.
また、第２級アミン化合物や第３級アミン化合物がメラミン樹脂による架橋を妨げるという現象は、メラミン樹脂による架橋やこれ以外の架橋を利用した水性プライマー塗料で形成されたプライマー塗膜に、上塗り塗料としてメラミン樹脂硬化型塗料を塗装する場合にも問題となる。すなわち、中和剤やｐＨ調整剤に由来してプライマー塗膜に存在する第２級アミン化合物や第３級アミン化合物が揮散して上塗りしたメラミン樹脂硬化型塗料中に移行し、メラミン樹脂硬化型塗料の架橋反応を妨げることになるのである。この場合も、高温焼付けが可能であれば、プライマー塗料の塗装後に高温で焼付けすることにより第２級アミン化合物や第３級アミン化合物を解離・揮散させて、架橋反応の阻害を防ぐことができるが、高温焼付けができない用途においては、上塗り塗膜の架橋を妨げ、その膜性能を損なうという問題を招くことになる。 In addition, the phenomenon that the secondary amine compound or the tertiary amine compound hinders the crosslinking with the melamine resin is caused by the fact that the primer coating formed by the aqueous primer coating using the crosslinking by the melamine resin or other crosslinking is applied to the top coating. As a problem, it also becomes a problem when a melamine resin curable coating is applied. That is, the secondary amine compound and tertiary amine compound present in the primer coating derived from the neutralizing agent and the pH adjusting agent are volatilized and transferred to the overcoated melamine resin curable paint, and the melamine resin curable type This hinders the crosslinking reaction of the paint. Also in this case, if high-temperature baking is possible, secondary amine compounds and tertiary amine compounds can be dissociated and volatilized by baking at a high temperature after application of the primer paint, thereby preventing the crosslinking reaction from being inhibited. However, in applications where high-temperature baking is not possible, crosslinking of the top coat film is hindered and the film performance is impaired.
そこで、本発明が解決しようとする課題は、１液型で貯蔵安定性にも優れ、高温での焼付けを要することなく、耐水性等の膜性能が良好な塗膜を形成することができ、しかも、メラミン樹脂硬化型塗料を上塗りした場合にも該上塗り塗膜の膜性能を損なうことのない、水性プライマー塗料およびこれを用いた塗膜形成方法を提供することにある。 Therefore, the problem to be solved by the present invention is a one-component type that is excellent in storage stability, can form a coating film with good film performance such as water resistance without requiring baking at a high temperature, Moreover, it is an object of the present invention to provide a water-based primer coating and a coating film forming method using the same without impairing the film performance of the top coating film even when the melamine resin curable coating is overcoated.
本発明者は、上記課題を解決するべく鋭意検討を行った。その結果、第１級アミン化合物もしくはアンモニアであれば、水性塗料中に存在していても、前述したようなメラミン樹脂による架橋を妨げるという現象を起こさないことを見出し、架橋剤として特定量のメラミン樹脂を配合するとともに、水性塗料において樹脂等の中和剤やｐＨ調整剤などとして用いる塩基性物質として第１級アミン化合物もしくはアンモニアを選択するようにし、当該水性塗料中の第１級アミン化合物およびアンモニア以外の塩基性物質の含有量を特定量以下に抑えることによって、前記課題を一挙に解決できることを確認して、本発明を完成した。 The present inventor has intensively studied to solve the above problems. As a result, if it is a primary amine compound or ammonia, it has been found that even if it is present in an aqueous coating, it does not cause the phenomenon of preventing crosslinking by the melamine resin as described above, and a specific amount of melamine as a crosslinking agent is found. In addition to blending a resin, a primary amine compound or ammonia is selected as a basic substance to be used as a neutralizing agent or pH adjuster for a resin in a water-based paint, and the primary amine compound in the water-based paint and The present invention was completed by confirming that the above problems could be solved at once by suppressing the content of basic substances other than ammonia to a specific amount or less.
すなわち、本発明にかかる水性プライマー塗料は、酸無水物変性塩素化ポリオレフィンエマルション樹脂、水性エポキシ樹脂および水性アルキッド樹脂を必須ビヒクルとする水性プライマー塗料であって、固形分基準で前記必須ビヒクル１００質量部に対して１〜２０質量部のメラミン樹脂を含有するとともに、第１級アミン化合物およびアンモニア以外の塩基性物質の含有量が全塩基性物質の１０質量％以下である、ことを特徴とする。
本発明にかかる塗膜形成方法は、プライマー塗料により形成された塗膜に、上塗り塗料としてメラミン樹脂硬化型塗料を塗装する塗膜形成方法において、前記プライマー塗料として前記本発明の水性プライマー塗料を用いる、ことを特徴とする。
That is, the aqueous primer coating according to the present invention is an aqueous primer coating having an acid anhydride-modified chlorinated polyolefin emulsion resin, an aqueous epoxy resin and an aqueous alkyd resin as essential vehicles, and 100 parts by mass of the essential vehicle based on solid content 1 to 20 parts by mass of the melamine resin with respect to the primary amine compound and the content of the basic substance other than ammonia is 10% by mass or less of the total basic substance.
The method for forming a coating film according to the present invention uses the water-based primer coating of the present invention as the primer coating in the coating film forming method in which a melamine resin curable coating is applied as a top coating to a coating formed by a primer coating. It is characterized by that.
本発明によれば、１液型で貯蔵安定性にも優れ、高温での焼付けを要することなく、耐水性等の膜性能が良好な塗膜を形成することができ、しかも、メラミン樹脂硬化型塗料を上塗りした場合にも該上塗り塗膜の膜性能を損なうことのない、水性プライマー塗料およびこれを用いた塗膜形成方法を提供することができる。 According to the present invention, a one-pack type is excellent in storage stability, can be formed into a coating film with good film performance such as water resistance without requiring baking at high temperature, and further, a melamine resin curable type It is possible to provide a water-based primer coating and a method for forming a coating using the same without impairing the film performance of the top coating even when the coating is overcoated.
以下、本発明にかかる水性プライマー塗料および塗膜形成方法について詳しく説明するが、本発明の範囲はこれらの説明に拘束されることはなく、以下の例示以外についても、本発明の趣旨を損なわない範囲で適宜変更実施し得る。
〔水性プライマー塗料〕
本発明の水性プライマー塗料は、酸無水物変性塩素化ポリオレフィンエマルション樹脂、水性エポキシ樹脂および水性アルキッド樹脂を必須ビヒクルとする。
前記酸無水物変性塩素化ポリオレフィンエマルション樹脂は、酸無水物変性塩素化ポリオレフィン樹脂のエマルションである。酸無水物変性塩素化ポリオレフィン樹脂は、疎水性が高く、水に安定して分散させることが困難であるので、本発明においては、酸無水物変性塩素化ポリオレフィン樹脂を、乳化剤や塩基性物質を使用してエマルション化させ、エマルションとして用いるのである。
Hereinafter, although the water-based primer coating material and coating-film formation method concerning this invention are demonstrated in detail, the scope of this invention is not restrained by these description and does not impair the meaning of this invention except the following illustrations. Changes can be made as appropriate within the range.
[Water-based primer paint]
The water-based primer coating of the present invention uses an acid anhydride-modified chlorinated polyolefin emulsion resin, a water-based epoxy resin, and a water-based alkyd resin as essential vehicles.
The acid anhydride-modified chlorinated polyolefin emulsion resin is an emulsion of an acid anhydride-modified chlorinated polyolefin resin. An acid anhydride-modified chlorinated polyolefin resin is highly hydrophobic and difficult to disperse stably in water. Therefore, in the present invention, an acid anhydride-modified chlorinated polyolefin resin is used as an emulsifier or a basic substance. It is made into an emulsion and used as an emulsion.
前記酸無水物変性塩素化ポリオレフィン樹脂は、塩素化ポリオレフィン部分と、この塩素化ポリオレフィン部分に結合した酸無水物部分とを含むポリオレフィン誘導体である。詳しくは、塩素化ポリオレフィン部分は、塩素原子が置換したポリオレフィンからなる部分であり、酸無水物部分は、酸無水物に由来する基からなり、グラフトして得られる変性された部分である。
前記酸無水物変性塩素化ポリオレフィン樹脂は、例えば、ポリオレフィンに対して塩素および酸無水物を反応させて内部変性することにより得ることができる。ここで、塩素および酸無水物はどちらを先に反応させてもよい。塩素との反応は、例えば、ポリオレフィンを含む溶液に塩素ガスを導入することによって行うことができる。また、酸無水物との反応は、例えば、過酸化物の存在下、ポリオレフィン（または塩素化ポリオレフィン）に酸無水物を反応させることによって行うことができる。
The acid anhydride-modified chlorinated polyolefin resin is a polyolefin derivative containing a chlorinated polyolefin portion and an acid anhydride portion bonded to the chlorinated polyolefin portion. Specifically, the chlorinated polyolefin portion is a portion made of polyolefin substituted with a chlorine atom, and the acid anhydride portion is a modified portion made of a group derived from an acid anhydride and obtained by grafting.
The acid anhydride-modified chlorinated polyolefin resin can be obtained, for example, by reacting a polyolefin with chlorine and an acid anhydride to internally modify the polyolefin. Here, either chlorine or acid anhydride may be reacted first. The reaction with chlorine can be performed, for example, by introducing chlorine gas into a solution containing polyolefin. Moreover, reaction with an acid anhydride can be performed by making an acid anhydride react with polyolefin (or chlorinated polyolefin) in presence of a peroxide, for example.
前記ポリオレフィンとしては、例えば、ポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体、エチレン−プロピレン−ジエン共重合体、ポリブテンや、スチレン−ブタジエン−イソプレンなどの共重合体の水添加物等が挙げられる。これらの中でも、ポリプロピレンが、入手のし易さと、プラスチック素材、とりわけポリプロピレン素材に対する密着性に優れる点から好ましい。前記ポリオレフィンは、１種のみであってもよいし、２種以上であってもよい。
前記酸無水物としては、例えば、無水マレイン酸、無水シトラコン酸、無水イタコン酸等が挙げられる。前記酸無水物は、１種のみであってもよいし、２種以上であってもよい。
Examples of the polyolefin include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, polybutene, and water additives of copolymers such as styrene-butadiene-isoprene. Among these, polypropylene is preferable because it is easily available and has excellent adhesion to plastic materials, particularly polypropylene materials. 1 type may be sufficient as the said polyolefin, and 2 or more types may be sufficient as it.
Examples of the acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride and the like. The acid anhydride may be only one kind or two or more kinds.
前記酸無水物変性塩素化ポリオレフィン樹脂は、その塩素含有率が１０〜３０質量％の範囲にあることが好ましく、１８〜２２質量％の範囲にあることがより好ましい。塩素含有率が１０質量％未満であると、溶剤溶解性が低く、エマルション化しにくくなる傾向があり、一方、３０質量％を超えると、プラスチック素材への密着性が低下する恐れがある。
前記酸無水物変性塩素化ポリオレフィン樹脂の酸無水物含有率は、１〜１０質量％の範囲にあることが好ましく、１．２〜５質量％の範囲にあることがより好ましい。酸無水物含有率が１質量％未満であると、エマルション化しにくくなるとともに、塗料の貯蔵安定性が悪くなる恐れがあり、一方、１０質量％を超えると、酸無水物基が多くなり、得られる塗膜の耐水性が低下する傾向がある。
The acid anhydride-modified chlorinated polyolefin resin preferably has a chlorine content in the range of 10 to 30% by mass, and more preferably in the range of 18 to 22% by mass. If the chlorine content is less than 10% by mass, the solvent solubility is low and the emulsion tends to be difficult to be emulsified. On the other hand, if it exceeds 30% by mass, the adhesion to the plastic material may be reduced.
The acid anhydride content of the acid anhydride-modified chlorinated polyolefin resin is preferably in the range of 1 to 10% by mass, and more preferably in the range of 1.2 to 5% by mass. If the acid anhydride content is less than 1% by mass, it may be difficult to emulsify and the storage stability of the paint may be deteriorated. On the other hand, if it exceeds 10% by mass, the number of acid anhydride groups increases. There is a tendency for the water resistance of the resulting coating film to decrease.
前記酸無水物変性塩素化ポリオレフィン樹脂は、その重量平均分子量が２００００〜２０００００の範囲にあることが好ましく、５００００〜１２００００の範囲にあることがより好ましい。重量平均分子量が２００００未満であると、得られる塗膜の膜強度が低下し、密着性も低くなる傾向があり、一方、２０００００を超えると、粘度が高くなり、エマルション化しにくくなるとともに、塗料の貯蔵安定性が低下する恐れがある。
前記酸無水物変性塩素化ポリオレフィン樹脂をエマルション化し、酸無水物変性塩素化ポリオレフィンエマルション樹脂とする方法としては、特に制限はなく、従来公知の方法で行うことができる。例えば、前記酸無水物変性塩素化ポリオレフィン樹脂に、乳化剤、中和剤としての塩基性物質、必要により溶剤を加えて加熱またはそのままで溶解させ、市販の乳化機にて水中に乳化させるか、あるいは、前記酸無水物変性塩素化ポリオレフィン樹脂に、乳化剤、必要により溶剤を加えて加熱またはそのままで溶解させ、市販の乳化機にて塩基性物質を添加した水中に乳化させるようにすればよい。また、逆に、前記酸無水物変性塩素化ポリオレフィン樹脂に、乳化剤、中和剤としての塩基性物質、必要により溶剤を加えて加熱またはそのままで溶解させた有機相に、水を攪拌下でゆっくりと添加して転相乳化させるか、あるいは、前記酸無水物変性塩素化ポリオレフィン樹脂に、乳化剤、必要により溶剤を加えて加熱またはそのままで溶解させた有機相に、塩基性物質を添加した水を攪拌下でゆっくりと添加して転相乳化させるようにしてもよい。
The acid anhydride-modified chlorinated polyolefin resin preferably has a weight average molecular weight in the range of 20,000 to 200,000, and more preferably in the range of 50,000 to 120,000. When the weight average molecular weight is less than 20000, the film strength of the resulting coating film tends to be low and the adhesion tends to be low. On the other hand, when it exceeds 200,000, the viscosity becomes high and it becomes difficult to emulsify. Storage stability may be reduced.
The method for emulsifying the acid anhydride-modified chlorinated polyolefin resin to obtain an acid anhydride-modified chlorinated polyolefin emulsion resin is not particularly limited, and can be performed by a conventionally known method. For example, to the acid anhydride-modified chlorinated polyolefin resin, an emulsifier, a basic substance as a neutralizing agent, if necessary, a solvent is added and dissolved by heating or as it is, and emulsified in water with a commercially available emulsifier, or The acid anhydride-modified chlorinated polyolefin resin may be added with an emulsifier and, if necessary, a solvent, heated or dissolved as it is, and emulsified in water containing a basic substance by a commercially available emulsifier. Conversely, water is slowly added to the organic phase obtained by adding an emulsifier, a basic substance as a neutralizing agent, and optionally adding a solvent to the acid anhydride-modified chlorinated polyolefin resin and dissolving it with heating or as it is, with stirring. To the organic phase obtained by adding an emulsifier and, if necessary, a solvent to the acid anhydride-modified chlorinated polyolefin resin and dissolving it by heating or as it is, water containing a basic substance is added. You may make it phase-emulsify by adding slowly under stirring.
前記エマルション化の際に用いる乳化剤としては、特に限定はないが、例えば、ポリオキシエチレンアルキルエーテル（例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテルなど）、ポリオキシエチレンアルキルフェノールエーテル（例えば、ポリオキシエチレンノニルフェノールエーテルなど）、ポリオキシエチレン脂肪族エステル、ポリオキシエチレン多価アルコール脂肪酸エステル、多価アルコール脂肪酸エステル、ポリオキシエチレンプロピレンポリオール、アルキロールアミド等のノニオン型乳化剤；アルキル硫酸エステル塩、ジアルキルスルホコハク酸塩、アルキルスルフォン酸塩、ポリオキシエチレンステアリルエーテル硫酸塩、ポリオキシエチレンノニルフェニルエーテル硫酸塩、アルキルリン酸塩等のアニオン型乳化剤；アルキルベタイン（例えば、ステアリルベタイン、ラウリルベタインなど）、アルキルイミダゾリン等の両性乳化剤；ポリオキシエチレン基含有ウレタン樹脂、カルボン酸塩基含有ウレタン樹脂等の樹脂型乳化剤；イミダゾリンラウレート、ラウリルトリメチルアンモニウムクロライド、ジステアリルジメチルアンモニウムクロライド等のカチオン型乳化剤；等を挙げることができる。これらの中でも、親水性の高いイオン性極性基を有さないノニオン型乳化剤が、得られる塗膜により良好な耐水性を付与しうる点から好ましい。 The emulsifier used for emulsification is not particularly limited. For example, polyoxyethylene alkyl ether (for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether), polyoxyethylene alkylphenol ether (for example, polyoxyethylene alkylphenol ether) Nonionic emulsifiers such as polyoxyethylene aliphatic ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyhydric alcohol fatty acid ester, polyoxyethylene propylene polyol, alkylolamide; alkyl sulfate ester salt, dialkyl Sulfosuccinate, alkyl sulfonate, polyoxyethylene stearyl ether sulfate, polyoxyethylene nonylphenyl ether sulfate, alkyl Anionic emulsifiers such as phosphates; amphoteric emulsifiers such as alkylbetaines (for example, stearylbetaine, laurylbetaine) and alkylimidazolines; resin-type emulsifiers such as polyoxyethylene group-containing urethane resins and carboxylate group-containing urethane resins; imidazolines And cationic emulsifiers such as laurate, lauryltrimethylammonium chloride, and distearyldimethylammonium chloride. Among these, nonionic emulsifiers that do not have a highly hydrophilic ionic polar group are preferable from the viewpoint that good water resistance can be imparted to the resulting coating film.
前記エマルション化で用いる前記乳化剤の使用量は、酸無水物変性塩素化ポリオレフィン樹脂の量、塩基性物質や水の配合割合によって適宜設定すればよいが、例えば、酸無水物変性塩素化ポリオレフィン樹脂１００質量部に対して５〜５０質量部とすることが好ましく、１０〜３０質量部とすることがより好ましい。５質量部未満であると、塗料の貯蔵安定性が低下するとともに、エマルション化の際に凝集や沈降が起こり易くなる恐れがあり、一方、５０質量部を超えると、得られる塗膜中に乳化剤が多量に残存することになり、耐水性が低下する傾向がある。
前記エマルション化の際に用いる塩基性物質は、酸無水物変性塩素化ポリオレフィン樹脂が有する酸無水物基および／またはカルボキシル基に付加するか、および／または、これらの基を中和して、酸無水物変性塩素化ポリオレフィン樹脂の親水性を高め、エマルションの貯蔵安定性を向上させる働きをするものである。後述するように、本発明においては、水性塗料中に存在する塩基性物質のうち、第１級アミンおよびアンモニア以外の塩基性物質の量が１０質量％以下であることが重要であるので、エマルション化の際に用いる塩基性物質の種類（１種でも２種以上でもよく、２種以上の場合はその比率も）は、第１級アミン化合物およびアンモニア以外の塩基性物質の含有量が全塩基性物質の１０質量％以下となるように選択する必要がある。エマルション化の際に用いる塩基性物質として選択しうるものの具体例は後述する。
The amount of the emulsifier used in the emulsification may be appropriately set depending on the amount of the acid anhydride-modified chlorinated polyolefin resin and the mixing ratio of the basic substance and water. For example, the acid anhydride-modified chlorinated polyolefin resin 100 It is preferable to set it as 5-50 mass parts with respect to a mass part, and it is more preferable to set it as 10-30 mass parts. If the amount is less than 5 parts by mass, the storage stability of the paint may be reduced, and aggregation or sedimentation may occur during emulsification. On the other hand, if the amount exceeds 50 parts by mass, an emulsifier is contained in the resulting coating film. Will remain in a large amount and the water resistance tends to decrease.
The basic substance used for emulsification is added to the acid anhydride group and / or carboxyl group of the acid anhydride-modified chlorinated polyolefin resin, and / or these groups are neutralized to produce an acid. It functions to increase the hydrophilicity of the anhydride-modified chlorinated polyolefin resin and to improve the storage stability of the emulsion. As will be described later, in the present invention, among the basic substances present in the aqueous paint, it is important that the amount of the basic substance other than the primary amine and ammonia is 10% by mass or less. The type of basic substance used in the conversion (one or two or more, and the ratio in the case of two or more) includes basic substances other than the primary amine compound and ammonia. It is necessary to select so that it may become 10 mass% or less of a sex substance. Specific examples of those that can be selected as the basic substance used in emulsification will be described later.
前記エマルション化で用いる塩基性物質の使用量は、酸無水物変性塩素化ポリオレフィン樹脂の量、乳化剤や水の配合割合に応じて、酸無水物変性塩素化ポリオレフィン樹脂や乳化剤等に含まれる酸性官能基を充分に中和しうるよう適宜設定すればよい。例えば、酸無水物変性塩素化ポリオレフィン樹脂に含まれる酸性官能基１当量に対し、好ましくは０．５〜４当量とするのがよい。０．５当量未満であると、エマルション化が不充分となる傾向があり、一方、４当量を超えると、残存する塩基性物質が得られる塗膜の耐水性を低下させたり、酸無水物変性塩素化ポリオレフィン樹脂の脱塩素化を促進する恐れがある。
前記エマルション化の際に用いる水の使用量は、得られるエマルション全体の５０〜９５質量％とすることが好ましく、６０〜８５質量％とすることがより好ましく、６５〜８０質量％とすることが最も好ましい。５０質量％未満であると、エマルション中の樹脂固形分が多くなりすぎ、凝集等が生じ易く、エマルションの貯蔵安定性が低下する傾向があり、一方、９５質量％を超えると、塗料中の樹脂固形分が低くなり、塗装作業性が低下する恐れがある。
The amount of the basic substance used in the emulsification is determined depending on the amount of the acid anhydride-modified chlorinated polyolefin resin, the mixing ratio of the emulsifier and water, and the acid functionality contained in the acid anhydride-modified chlorinated polyolefin resin and the emulsifier. What is necessary is just to set suitably so that group can fully be neutralized. For example, with respect to 1 equivalent of acidic functional group contained in the acid anhydride-modified chlorinated polyolefin resin, the amount is preferably 0.5 to 4 equivalents. If the amount is less than 0.5 equivalent, emulsification tends to be insufficient. On the other hand, if the amount exceeds 4 equivalents, the water resistance of the coating film from which the remaining basic substance is obtained is reduced or the acid anhydride is modified. There is a risk of promoting dechlorination of the chlorinated polyolefin resin.
The amount of water used for emulsification is preferably 50 to 95% by mass, more preferably 60 to 85% by mass, and 65 to 80% by mass of the total emulsion to be obtained. Most preferred. If it is less than 50% by mass, the solid content of the resin in the emulsion is excessively increased and aggregation or the like tends to occur, and the storage stability of the emulsion tends to decrease. On the other hand, if it exceeds 95% by mass, the resin in the paint There is a possibility that the solid content is lowered and the coating workability is lowered.
前記エマルション化の際に用いることのできる溶剤としては、特に限定はないが、例えば、トルエン、キシレン等の芳香族系溶剤（市販品では、例えば、エクソン社製のソルベッソ１００など）；ジエチレングリコールモノエチルエーテルアセテート、ブチルセロソルブ、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、プロピレングリコール−ｎ−プロピルエーテル等のエチレングリコール系またはプロピレングリコール系溶剤；等が挙げられる。
前記エマルション化で用いる溶剤の使用量は、特に制限されないが、例えば、酸無水物変性塩素化ポリオレフィン樹脂と乳化剤の合計１００質量部に対して１５〜５０質量部とすることが好ましい。１５質量部未満であると、エマルション化の際に粘度が高くなりすぎてうまくエマルション化できなくなることがあり、一方、５０質量部を超えると、エマルションが徐々に融着して安定性が悪くなる恐れがある。
The solvent that can be used in the emulsification is not particularly limited, and for example, aromatic solvents such as toluene and xylene (commercially available products such as Solvesso 100 manufactured by Exxon); diethylene glycol monoethyl And ethylene glycol-based or propylene glycol-based solvents such as ether acetate, butyl cellosolve, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and propylene glycol-n-propyl ether.
Although the usage-amount of the solvent used by the said emulsification is not restrict | limited in particular, For example, it is preferable to set it as 15-50 mass parts with respect to 100 mass parts in total of an acid anhydride modified chlorinated polyolefin resin and an emulsifier. If the amount is less than 15 parts by mass, the viscosity may become too high when emulsifying, making it impossible to emulsify well. On the other hand, if the amount exceeds 50 parts by mass, the emulsion gradually melts and the stability deteriorates. There is a fear.
前記酸無水物変性塩素化ポリオレフィンエマルション樹脂のｐＨは、エマルション化の際に用いる塩基性物質によって決まるのであるが、好ましくは７〜１０．５、さらに好ましくは８〜１０であるのがよい。ｐＨが７未満であると、中和が不充分で、エマルションの貯蔵安定性が低下することがあり、一方、ｐＨが１０．５を超えると、得られる塗膜の耐水性が低下したり、遊離の塩基性物質が過剰に存在することとなり、臭気が強くて使用しにくくなることがある。
前記酸無水物変性塩素化ポリオレフィンエマルション樹脂中の粒子（前記酸無水物変性塩素化ポリオレフィン樹脂）の粒径は、特に限定されないが、０．０３〜５μｍが好ましく、０．０５〜１μｍがより好ましい。ポリマー粒子の平均粒径が０．０３μｍ未満であると、乳化剤が多量に必要となり、得られる塗膜の耐水性が低下する恐れがあり、一方、５μｍを超えると、塗料の貯蔵安定性が悪くなる傾向があるとともに、膜の形成性が悪化して塗膜の平滑性が得られなくなる恐れがある。
The pH of the acid anhydride-modified chlorinated polyolefin emulsion resin is determined by the basic substance used for emulsification, but it is preferably 7 to 10.5, more preferably 8 to 10. When the pH is less than 7, neutralization is insufficient, and the storage stability of the emulsion may be lowered. On the other hand, when the pH is more than 10.5, the water resistance of the obtained coating film is lowered, Excessive basic substances will be present in excess, and the odor may be strong and difficult to use.
The particle size of the particles in the acid anhydride-modified chlorinated polyolefin emulsion resin (the acid anhydride-modified chlorinated polyolefin resin) is not particularly limited, but is preferably 0.03 to 5 μm, more preferably 0.05 to 1 μm. . If the average particle size of the polymer particles is less than 0.03 μm, a large amount of emulsifier is required, and the water resistance of the resulting coating film may be lowered. On the other hand, if it exceeds 5 μm, the storage stability of the paint is poor. In addition, the film formability may be deteriorated and the smoothness of the coating film may not be obtained.
前記水性エポキシ樹脂は、エポキシ基を１分子中に１個以上有する水性樹脂であれば、特に制限されるものではなく、通常、塗料に用いられる従来公知の水性エポキシ樹脂を用いることができる。具体的には、ビスフェノールにエピクロロヒドリンを付加させて得られるビスフェノール型エポキシ樹脂を乳化剤を用いて強制乳化させたもの、市販品では、例えば、シェルケミカル（株）製のエピレッツ３５１０Ｗ６０、３５１５Ｗ６、３５２２Ｗ６０、３５４０ＷＹ５５、８８０ＳＡＷ−６５等；フェノールノボラック樹脂にエピクロロヒドリンを付加させて得られるノボラック型エポキシ樹脂を乳化剤を用いて強制乳化させたもの、市販品では、例えば、長瀬ケムテック（株）製のデナコールＥＭ１５０や、シェルケミカル（株）製のエピレッツ６００６Ｗ７０、５００３Ｗ５５や、東都化成（株）製のＷＥＸ−５１００等；ペンタエリスリトール、ソルビトール、グリセリン等のポリオールにエピクロロヒドリンを付加させたもの、市販品では、例えば、長瀬ケムテック（株）製のデナコールＥＸ６１１、ＥＸ６１４、ＥＸ４１１、ＥＸ３１３等；等が挙げられる。 The aqueous epoxy resin is not particularly limited as long as it is an aqueous resin having one or more epoxy groups in one molecule, and conventionally known aqueous epoxy resins that are usually used in paints can be used. Specifically, bisphenol-type epoxy resin obtained by adding epichlorohydrin to bisphenol is forcibly emulsified using an emulsifier, and commercially available products such as Epiletts 3510W60 and 3515W6 manufactured by Shell Chemical Co., Ltd. 3522W60, 3540WY55, 880SAW-65, etc .; forcibly emulsified novolac epoxy resin obtained by adding epichlorohydrin to phenol novolac resin using an emulsifier, commercially available products, for example, manufactured by Nagase Chemtech Co., Ltd. Denacol EM150, Shell Chemical Co., Ltd. Epiletts 6006W70, 5003W55, Toto Kasei Co., Ltd. WEX-5100, etc .; those obtained by adding epichlorohydrin to polyols such as pentaerythritol, sorbitol, glycerin, In Commercially available products, for example, Nagase Chemtech Co. Denacol EX611, EX614, EX411, EX313 and the like; and the like.
前記水性アルキッド樹脂は、多価アルコールと、酸成分の一部が植物油の長鎖脂肪酸であってもよい多官能カルボン酸とのポリエステル化反応生成物である。
前記多価アルコールとしては、例えば、グリセロール、トリメチロールエタン、トリメチロールプロパン、ジエチレングリコール、ネオペンチルグリコール、１，４−シクロヘキサンジメタノール、２，２，４−トリメチル−１，３−ペンタンジオール、１，６−ヘキサンジオール、１，２−プロピレングリコール、１，２−プロパンジオール、エチレングリコール、ブチレングリコール、ジプロピレングリコール、ペンタエリスリトール等が挙げられる。
The aqueous alkyd resin is a polyesterification reaction product of a polyhydric alcohol and a polyfunctional carboxylic acid in which a part of the acid component may be a long-chain fatty acid of vegetable oil.
Examples of the polyhydric alcohol include glycerol, trimethylolethane, trimethylolpropane, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, 1, Examples include 6-hexanediol, 1,2-propylene glycol, 1,2-propanediol, ethylene glycol, butylene glycol, dipropylene glycol, and pentaerythritol.
前記多官能カルボン酸としては、例えば、フタル酸無水物、アジピン酸、マレイン酸無水物、イソフタル酸、セバチン酸、アゼライン酸、テレフタル酸、トリメリット酸無水物、リノール酸、リノレイン酸、安息香酸、ヘキサヒドロフタル酸無水物、テトラヒドロフタル酸無水物、１，４−シクロヘキサンジカルボン酸、フマル酸等が挙げられる。
前記水性アルキッド樹脂は、各種オイルで変性することにより改質されたものであってもよい。変性に用いることのできるオイルとしては、例えば、桐油、アマニ油、大豆油、べにばな油、ヒマシ油、コーン油、綿種油、ペララ油、ゴマ油、ココナツ油、脱水ヒマシ油、トール油等が挙げられる。
Examples of the polyfunctional carboxylic acid include phthalic anhydride, adipic acid, maleic anhydride, isophthalic acid, sebacic acid, azelaic acid, terephthalic acid, trimellitic anhydride, linoleic acid, linolenic acid, benzoic acid, Examples include hexahydrophthalic anhydride, tetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, and fumaric acid.
The aqueous alkyd resin may be modified by modification with various oils. Examples of oils that can be used for modification include paulownia oil, linseed oil, soybean oil, safflower oil, castor oil, corn oil, cotton seed oil, pella oil, sesame oil, coconut oil, dehydrated castor oil, and tall oil. Etc.
前記水性アルキッド樹脂の樹脂固形分酸価は、５〜１００ｍｇＫＯＨ／ｇであることが好ましく、１０〜４０ｍｇＫＯＨ／ｇであることがより好ましい。樹脂固形分酸価が５ｍｇＫＯＨ／ｇ未満であると、アルキッド樹脂の水への分散性が不充分で、安定な水溶性樹脂になりにくく、一方、１００ｍｇＫＯＨ／ｇを超えると、本発明の水性プライマー塗料により形成される塗膜の耐水性や耐候性が低下する恐れがある。
前記水性アルキッド樹脂の具体例としては、市販品では、例えば、大日本インキ（株）製ウォーターゾルシリーズのＳ１１８、Ｓ１２６、Ｓ３４６や、日本触媒（株）製アロロンシリーズの３７６、５８０や、日本触媒（株）製アクリセットシリーズのＡＲＬ５８１、ＡＲＬ５８０等が挙げられる。
The resin solid content acid value of the aqueous alkyd resin is preferably 5 to 100 mgKOH / g, and more preferably 10 to 40 mgKOH / g. When the resin solid acid value is less than 5 mgKOH / g, the dispersibility of the alkyd resin in water is insufficient, and it is difficult to become a stable water-soluble resin. There is a risk that the water resistance and weather resistance of the coating film formed by the paint may be lowered.
Specific examples of the water-based alkyd resin include commercially available products such as S118, S126, and S346 from Dainippon Ink Co., Ltd., Allolon series 376 and 580 from Nippon Shokubai Co., Ltd. Examples include ARL581 and ARL580 of the Acryset series manufactured by Catalyst Co., Ltd.
必須ビヒクルとなる前記酸無水物変性塩素化ポリオレフィンエマルション樹脂、前記水性エポキシ樹脂および前記水性アルキッド樹脂の各割合は、特に制限されないが、好ましくは、塗料中の全樹脂固形分に対して、固形分基準で、前記酸無水物変性塩素化ポリオレフィンエマルション樹脂が２０〜６０重量％、より好ましくは３０〜５０重量％であり、前記水性エポキシ樹脂が１０〜６０重量％、より好ましくは２０〜５０重量％であり、前記水性アルキッド樹脂が１０〜６０重量％、より好ましくは２０〜５０重量％であるのがよい。酸無水物変性塩素化ポリオレフィンエマルション樹脂が少ないと、プラスチクック素材、とりわけポリプロピレン素材に対する充分な密着性が得られにくくなり、一方、多すぎると、上塗り塗料との相関付着が不良となったり、顔料分散性が悪くなったりする傾向がある。水性エポキシ樹脂が少ないと、得られる塗膜の耐水性が低下する傾向があり、一方、多すぎると、造膜性が悪くなり、造膜できたとしても硬く脆い塗膜となる恐れがある。水性アルキッド樹脂が少ないと、顔料分散性が悪くなる傾向があり、一方、多すぎると、得られる塗膜の耐水性が低下する恐れがある。 The proportions of the acid anhydride-modified chlorinated polyolefin emulsion resin, the aqueous epoxy resin, and the aqueous alkyd resin, which are essential vehicles, are not particularly limited, but preferably, the solid content relative to the total resin solid content in the paint On a standard basis, the acid anhydride-modified chlorinated polyolefin emulsion resin is 20 to 60% by weight, more preferably 30 to 50% by weight, and the aqueous epoxy resin is 10 to 60% by weight, more preferably 20 to 50% by weight. The aqueous alkyd resin is preferably 10 to 60% by weight, more preferably 20 to 50% by weight. If there are few acid anhydride-modified chlorinated polyolefin emulsion resins, it will be difficult to obtain sufficient adhesion to plastic materials, especially polypropylene materials. There is a tendency for dispersibility to deteriorate. When the amount of the water-based epoxy resin is small, the water resistance of the resulting coating film tends to be lowered. On the other hand, when the amount is too large, the film-forming property is deteriorated, and even if the film can be formed, there is a fear that the coating film is hard and brittle. If the amount of the aqueous alkyd resin is small, the pigment dispersibility tends to be poor. On the other hand, if the amount is too large, the water resistance of the resulting coating film may be lowered.
本発明の水性プライマー塗料は、メラミン樹脂を含有するものであることが重要である。メラミン樹脂は架橋剤として作用するものであり、これにより、１液型で良好な貯蔵安定性を保持しつつ、耐水性等の膜性能が良好な塗膜を形成することができるのである。
前記メラミン樹脂としては、トリアジン環を１分子中に１個以上有するメラミン樹脂であれば、特に制限されるものではない。例えば、メトキシメチロールメラミン、ｎ−ブトキシメチロールメラミン、イソブトキシメチロールメラミン、メトキシブトキシメチロールメラミン、メトキシ／ｎ−ブトキシ混合メチロールメラミン（メラミン骨格にメトキシ基およびｎ−ブトキシ基がエーテル化されたもの）、およびこれらの縮合物等のようなアルコキシメチロールメラミン類が挙げられる。これらの中でも、平均縮合度が１〜４であるメトキシメチロールメラミン、ｎ−ブトキシメチロールメラミン、メトキシ／ｎ−ブトキシ混合メチロールメラミンが好ましい。
It is important that the aqueous primer paint of the present invention contains a melamine resin. The melamine resin acts as a cross-linking agent, whereby a coating film with good film performance such as water resistance can be formed while maintaining good storage stability in a one-pack type.
The melamine resin is not particularly limited as long as it is a melamine resin having one or more triazine rings in one molecule. For example, methoxymethylol melamine, n-butoxymethylol melamine, isobutoxymethylol melamine, methoxybutoxymethylol melamine, methoxy / n-butoxy mixed methylol melamine (melamine skeleton with methoxy and n-butoxy groups etherified), and Examples include alkoxymethylol melamines such as these condensates. Among these, methoxymethylol melamine, n-butoxymethylol melamine, and methoxy / n-butoxy mixed methylol melamine having an average degree of condensation of 1 to 4 are preferable.
前記メラミン樹脂の含有量は、固形分基準で前記必須ビヒクル（酸無水物変性塩素化ポリオレフィンエマルション樹脂、水性エポキシ樹脂および水性アルキッド樹脂）１００質量部に対して１〜２０質量部であることが重要である。１質量部未満であると、得られる塗膜の耐水性が不充分となり、一方、２０質量部を超えると、塗料の貯蔵安定性が悪化するとともに、得られる塗膜も硬くて脆いものとなる傾向がある。
本発明の水性プライマー塗料は、第１級アミン化合物およびアンモニア以外の塩基性物質の含有量が全塩基性物質の１０質量％以下であることが重要である。詳しくは、通常、水性塗料を得る際には、塗料の安定性を保つため、各ビヒクル（樹脂成分）の調製時もしくは塗料のｐＨを調整する時などに塩基性物質が使用されるのであるが、これら塗料を得る際に使用される全塩基性物質のうち、第１級アミン化合物およびアンモニア以外の塩基性物質の使用量を全塩基性物質の１０質量％以下とすることが重要となるのである。好ましくは、第１級アミン化合物およびアンモニア以外の塩基性物質は全く含有していない態様、すなわち、水性塗料を得るのに使用する塩基性物質として第１級アミン化合物および／またはアンモニアのみを使用する態様が望ましい。第１級アミン化合物もしくはアンモニアであれば、水性塗料中に存在していても、メラミン樹脂による架橋を妨げることがなく、高温で焼付けできない用途においても耐水性などの膜物性が良好な塗膜を形成することができる。
It is important that the content of the melamine resin is 1 to 20 parts by mass with respect to 100 parts by mass of the essential vehicle (acid anhydride-modified chlorinated polyolefin emulsion resin, aqueous epoxy resin and aqueous alkyd resin) on a solid basis. It is. When the amount is less than 1 part by mass, the resulting coating film has insufficient water resistance. On the other hand, when it exceeds 20 parts by mass, the storage stability of the paint deteriorates and the resulting coating film is also hard and brittle. Tend.
In the aqueous primer coating material of the present invention, it is important that the content of basic substances other than the primary amine compound and ammonia is 10% by mass or less of the total basic substances. Specifically, when obtaining a water-based paint, a basic substance is usually used when preparing each vehicle (resin component) or adjusting the pH of the paint in order to maintain the stability of the paint. Of the total basic substances used in obtaining these paints, it is important that the amount of basic substances other than primary amine compounds and ammonia be 10% by mass or less of the total basic substances. is there. Preferably, an embodiment containing no basic substance other than the primary amine compound and ammonia, that is, only the primary amine compound and / or ammonia is used as the basic substance used to obtain the water-based paint. Embodiments are desirable. If it is a primary amine compound or ammonia, even if it is present in a water-based paint, it will not interfere with crosslinking by the melamine resin, and a coating film with good film properties such as water resistance even in applications where it cannot be baked at high temperatures. Can be formed.
前記第１級アミン化合物としては、例えば、２−アミノ−２−メチルプロパノール、アリルアミン、イソプロピルアミン、エチルアミン、２−エチルヘキシルアミン、３−（２−エチルヘキシル）オキシプロピルアミン、３−エトキシプロピルアミン、ｔ−ブチルアミン、ｓｅｃ−ブチルアミン、プロピルアミン、３−メトキシプロピルアミン、イソプロパノールアミン、エタノールアミン等が挙げられる。
前記第１級アミン化合物およびアンモニア以外の塩基性物質とは、通常、水性塗料において樹脂等の中和剤やｐＨ調整剤などとして汎用されている第２級アミン化合物や第３級アミン化合物などのことである。具体的には、例えば、ジエチルアミン、ジイソブチルアミン、ジ−２−エチルヘキシルアミン等の第２級アミン化合物；トリエチルアミン、Ｎ，Ｎ−ジメチルエタノールアミン等の第３級アミン化合物；等が挙げられる。
Examples of the primary amine compound include 2-amino-2-methylpropanol, allylamine, isopropylamine, ethylamine, 2-ethylhexylamine, 3- (2-ethylhexyl) oxypropylamine, 3-ethoxypropylamine, t -Butylamine, sec-butylamine, propylamine, 3-methoxypropylamine, isopropanolamine, ethanolamine and the like.
The primary amine compound and the basic substance other than ammonia are usually secondary amine compounds and tertiary amine compounds that are widely used as neutralizing agents such as resins and pH adjusters in aqueous paints. That is. Specific examples include secondary amine compounds such as diethylamine, diisobutylamine and di-2-ethylhexylamine; tertiary amine compounds such as triethylamine and N, N-dimethylethanolamine; and the like.
本発明の水性プライマー塗料を得る際に用いる塩基性物質としては、特に、２−アミノ−２−メチルプロパノール、アンモニアが、メラミン樹脂の硬化を阻害しにくいことから好ましい。
本発明の水性プライマー塗料は、前記酸無水物変性塩素化ポリオレフィンエマルション樹脂、前記水性エポキシ樹脂および前記水性アルキッド樹脂を必須のビヒクルとし、前記メラミン樹脂を架橋剤とするものであるが、必要に応じて、これら樹脂以外の他の水性樹脂を、本発明の効果を損なわない範囲で適宜配合することもできる。他の水性樹脂としては、例えば、水性アクリル系樹脂、アクリル系エマルション樹脂、水性ウレタンディスパージョン等が挙げられる。
As a basic substance used when obtaining the water-based primer coating material of this invention, especially 2-amino-2-methylpropanol and ammonia are preferable since it is hard to inhibit hardening of a melamine resin.
The water-based primer coating of the present invention comprises the acid anhydride-modified chlorinated polyolefin emulsion resin, the water-based epoxy resin and the water-based alkyd resin as essential vehicles, and the melamine resin as a cross-linking agent. In addition, other aqueous resins other than these resins can be appropriately blended within a range not impairing the effects of the present invention. Examples of other aqueous resins include aqueous acrylic resins, acrylic emulsion resins, aqueous urethane dispersions, and the like.
本発明の水性プライマー塗料には、顔料を配合することができる。顔料としては、例えば、酸化チタン、カーボンブラック、酸化鉄系顔料、酸化クロム等の無機顔料；アゾ系顔料、アントラセン系顔料、ペリレン系顔料、キナクリドン系顔料、インジゴ系顔料、フタロシアニン系顔料、イソインドリノン系顔料、ペンツイミダゾロン系顔料等の有機顔料；アルミニウム系顔料（例えば、コーティングアルミなど）等の金属系顔料；マイカ系顔料；等が挙げられる。顔料は１種のみであってもよいし、２種以上であってもよい。顔料を配合する場合には、用いる全樹脂（塗料中の全樹脂固形分）に対して５〜７０質量％とすることが好ましい。５質量％未満であると、着色力が低く、隠蔽性が不充分となり、一方、７０質量％を超えると、得られる塗膜の平滑性や密着性が低下する恐れがある。なお、前記顔料としてアルミニウム系顔料のような金属系顔料を用いる場合には、金属（アルミニウム等）が酸化腐食して沈降凝集したり、塗膜としたときに金属光沢を発しなくなったりするのを防止するため、当該金属系顔料にあらかじめクロメート処理や酸化防止剤（例えば、有機燐化合物など）による処理を施しておいたり、塗料中に金属酸化防止剤を別途配合するなどの措置を講ずることが好ましい。 A pigment can be mix | blended with the water-based primer coating material of this invention. Examples of the pigment include inorganic pigments such as titanium oxide, carbon black, iron oxide pigment, chromium oxide; azo pigment, anthracene pigment, perylene pigment, quinacridone pigment, indigo pigment, phthalocyanine pigment, isoindo Organic pigments such as linone pigments and pentimidazolone pigments; metal pigments such as aluminum pigments (for example, coating aluminum); mica pigments; and the like. Only one kind of pigment may be used, or two or more kinds of pigments may be used. When a pigment is blended, the content is preferably 5 to 70% by mass with respect to the total resin used (total resin solid content in the paint). If it is less than 5% by mass, the coloring power is low and the concealability becomes insufficient. On the other hand, if it exceeds 70% by mass, the smoothness and adhesion of the resulting coating film may be lowered. When a metal pigment such as an aluminum pigment is used as the pigment, the metal (aluminum, etc.) may oxidize and corrode to precipitate and agglomerate. In order to prevent this, the metal pigment may be treated with chromate treatment or antioxidant (for example, organic phosphorus compound) in advance, or a metal antioxidant may be added separately in the paint. preferable.
本発明の水性プライマー塗料には、必要に応じて、塗料として通常添加される他の添加剤、例えば、安定剤、増粘剤、消泡剤、表面調整剤、レベリング剤、顔料分散剤、紫外線吸収剤、酸化防止剤、無機充填剤（例えば、シリカなど）、導電性充填剤（例えば、導電性カーボン、導電性フィラー、金属粉など）、有機改質剤、可塑剤、防腐・防徹剤等を、本発明の効果を損なわない範囲で配合することができる。また、膜乾燥性等を向上させるために、セルロースアセテートブチレート等を本発明の効果を損なわない範囲で配合することもできる。
本発明の水性プライマー塗料は、前述した各成分を通常の方法によって均一に混合することにより得ることができる。例えば、顔料を配合する場合には、顔料をあらかじめ一部または全ビヒクルに必要なレベルまで分散させて顔料分散ペ−ストとしておき、この中に、残りの他の成分を順次もしくは一挙に添加し、均一に混合するようにすればよい。
If necessary, the water-based primer paint of the present invention may contain other additives usually added as a paint, such as stabilizers, thickeners, antifoaming agents, surface conditioners, leveling agents, pigment dispersants, ultraviolet rays. Absorbent, antioxidant, inorganic filler (for example, silica), conductive filler (for example, conductive carbon, conductive filler, metal powder, etc.), organic modifier, plasticizer, antiseptic / protective agent Etc. can be mix | blended in the range which does not impair the effect of this invention. In order to improve the film drying property and the like, cellulose acetate butyrate and the like can be blended within a range not impairing the effects of the present invention.
The water-based primer paint of the present invention can be obtained by uniformly mixing the above-described components by an ordinary method. For example, when blending a pigment, the pigment is dispersed in advance to a level necessary for a part or all of the vehicle to obtain a pigment dispersion paste, and the remaining other components are added sequentially or all at once. It is sufficient to mix them uniformly.
本発明の水性プライマー塗料を塗布する方法については、特に限定はなく、エアースプレー塗装、エアレススプレー塗装、回転ディスク塗装、浸漬塗装、ハケ塗り塗装などの公知の方法を採用することができる。また、塗装時に静電をかけて、塗着効率を上げるようにしてもよい。
前記水性プライマー塗料の塗布量は、特に制限されないが、例えば、乾燥膜厚が２〜３０μｍ、好ましくは５〜２０μμｍなるようにするのがよい。乾燥膜厚が２μｍ未満であると、薄すぎて連続な均一膜を得られにくく、一方、３０μｍを超えると、耐水性等の膜性能が低下したり、塗布時にタレが生じたりすることがある。
The method for applying the aqueous primer coating of the present invention is not particularly limited, and known methods such as air spray coating, airless spray coating, rotating disk coating, dip coating, and brush coating can be employed. Alternatively, electrostatic application may be applied to increase the coating efficiency.
The application amount of the water-based primer coating is not particularly limited, but for example, the dry film thickness is 2 to 30 μm, preferably 5 to 20 μm. If the dry film thickness is less than 2 μm, it is difficult to obtain a continuous uniform film because it is too thin. On the other hand, if it exceeds 30 μm, the film performance such as water resistance may be deteriorated or sagging may occur during application. .
本発明の水性プライマー塗料は、塗布したのち焼付け（乾燥）を施す際の温度が制限されるものではない。すなわち、従来は、水性塗料をメラミン樹脂で硬化させようとする場合には、１４０℃以上の高温で焼付けを行なう必要があったが、本発明の水性プライマー塗料は、例えば４０℃程度の低温であっても、１４０℃程度の高温であっても、架橋反応は速やかに進行し、良好な膜物性の塗膜を形成することができる。
本発明の水性プライマー塗料が対象とする素材としては、特に限定されないが、例えば、ポリプロピレン（ＰＰ）、ポリエチレン（ＰＥ）等のポリオレフィンのほか、アクリロニトリルスチレン（ＡＳ）、アクリロニトリルブタジエンスチレン（ＡＢＳ）、ポリフェニレンオキサイド（ＰＰＯ）、塩化ビニル（ＰＶＣ）、ポリウレタン（ＰＵ）、ポリカーボネート（ＰＣ）等のプラスチック素材が挙げられる。これらの中でも特に、ポリプロピレンが密着性の点から好適である。
The temperature at the time of performing the baking (drying) after apply | coating the water-based primer coating material of this invention is not restrict | limited. That is, conventionally, when it is intended to cure a water-based paint with a melamine resin, it has been necessary to perform baking at a high temperature of 140 ° C. or higher. However, the water-based primer paint of the present invention has a low temperature of about 40 ° C. Even at a high temperature of about 140 ° C., the crosslinking reaction proceeds rapidly, and a coating film having good film properties can be formed.
The material targeted by the aqueous primer coating of the present invention is not particularly limited. For example, in addition to polyolefins such as polypropylene (PP) and polyethylene (PE), acrylonitrile styrene (AS), acrylonitrile butadiene styrene (ABS), polyphenylene, and the like. Examples thereof include plastic materials such as oxide (PPO), vinyl chloride (PVC), polyurethane (PU), and polycarbonate (PC). Among these, polypropylene is particularly preferable from the viewpoint of adhesion.
〔塗膜形成方法〕
本発明の塗膜形成方法は、プライマー塗料により形成された塗膜に、上塗り塗料としてメラミン樹脂硬化型塗料を塗装するものであり、前記プライマー塗料として前記本発明の水性プライマー塗料を用いるものである。プライマー塗料として前記本発明の水性プライマー塗料を用いることにより、メラミン樹脂硬化型塗料を上塗りした場合にも、焼付けの温度に関わらず、該メラミン樹脂硬化型塗料の架橋反応が阻害されることなく、良好な膜性能の上塗り塗膜を形成することができる。
前記メラミン樹脂硬化型塗料は、水性塗料であっても溶剤型塗料であってもよい。例えば、アクリルメラミン水性ベース塗料、アルキッドメラミン溶剤型塗料等が挙げられる。
[Coating film forming method]
The coating film forming method of the present invention is a method in which a melamine resin curable coating is applied as a top coating to a coating formed by a primer coating, and the aqueous primer coating of the present invention is used as the primer coating. . By using the water-based primer paint of the present invention as a primer paint, even when the melamine resin curable paint is overcoated, regardless of the baking temperature, the crosslinking reaction of the melamine resin curable paint is not inhibited, An overcoat film having good film performance can be formed.
The melamine resin curable paint may be an aqueous paint or a solvent paint. For example, acrylic melamine aqueous base paint, alkyd melamine solvent-type paint, and the like can be mentioned.
プライマー塗膜の上に塗装する上塗り塗料は、いわゆるベース塗料であってもよいし、クリヤー塗料であってもよい。言い換えれば、本発明の塗膜形成方法で形成される塗膜は、プライマー塗膜とベース塗膜とクリヤー塗膜からなる３層塗膜であってもよいし、プライマー塗膜とクリヤー塗膜からなる２層塗膜であってもよい。
各塗料の塗布量については、特に制限はない。例えば、前記水性プライマー塗料の塗布量は、本発明の水性プライマー塗料の項で前述した通りとすればよい。３層塗膜を形成する場合には、ベース塗料は、乾燥膜厚が８〜３０μｍ、好ましくは１０〜２０μμｍなるようにするのがよく、クリヤー塗料は、乾燥膜厚が１５〜８０μｍ、好ましくは２０〜５０μμｍなるようにするのがよい。なお、各塗料の塗布方法については、本発明の水性プライマー塗料の項で前述した通りとすればよい。
The top coating material applied on the primer coating film may be a so-called base coating material or a clear coating material. In other words, the coating film formed by the coating film forming method of the present invention may be a three-layer coating film composed of a primer coating film, a base coating film, and a clear coating film, or from a primer coating film and a clear coating film. It may be a two-layer coating film.
There is no restriction | limiting in particular about the application quantity of each coating material. For example, the application amount of the water-based primer paint may be as described above in the section of the water-based primer paint of the present invention. When forming a three-layer coating film, the base paint should have a dry film thickness of 8 to 30 μm, preferably 10 to 20 μm, and the clear paint has a dry film thickness of 15 to 80 μm, preferably It is good to make it 20-50 micrometers. In addition, about the coating method of each coating material, what is necessary is just as having mentioned above by the term of the aqueous primer coating material of this invention.
各塗料を塗布したのちの焼付け（乾燥）については、特に制限はなく、通常の方法に従って行なえばよい。例えば、３層塗膜を形成する場合には、水性プライマー塗料の塗布後には４０〜１４０℃、好ましくは５０〜１００℃で乾燥し、ベース塗料の塗布後には乾燥せずに常温で放置し、クリヤー塗料を塗布後に、３層になった塗膜を７０〜１４０℃で乾燥するようにすればよい。また、必要に応じて、各乾燥の前後に、常温で放置したり、予備乾燥を行なったり、冷却したりする工程を含めてもよい。 Baking (drying) after applying each paint is not particularly limited, and may be performed according to a normal method. For example, in the case of forming a three-layer coating film, it is dried at 40 to 140 ° C., preferably 50 to 100 ° C. after application of the aqueous primer coating, and is left at room temperature without being dried after application of the base coating, What is necessary is just to make it dry the 70-140 degreeC coating film which became three layers after apply | coating a clear coating material. Moreover, you may include the process of leaving at normal temperature, performing preliminary drying, and cooling before and after each drying as needed.
以下に、実施例および比較例によって本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。以下では、特に断りのない限り、「質量部」を単に「部」と、「質量％」を単に「％」と、記す。
〔製造例１−１：無水マレイン酸変性塩素化ポリプロピレンエマルション樹脂の製造〕
攪拌羽根、温度計、温度制御サーミスター装置、および冷却管を備えた反応装置に、無水マレイン酸変性塩素化ポリプロピレン樹脂（「スーパークロン８９２ＬＳ」日本製紙（株）製：塩素含有率２２％、重量平均分子量７００００〜８００００）２４０部、ノニルフェニルポリオキシエチレンエーテル（「エマルゲン９２０」花王（株）製）５２部、芳香族炭化水素溶剤（「ソルベッソ１００」エクソン社製）６２部、酢酸カービトール２７部を仕込み、１１０℃で１時間加熱し溶解させた後、１００℃以下に冷却した。次いで、イソプロパノールアミン（第１級アミン化合物）５部を溶解させた脱イオン水６１４部を１時間で滴下して転相乳化した。その後、室温まで冷却し、４００メッシュの網で濾過して、無水マレイン酸変性塩素化ポリプロピレンエマルション樹脂（１）を得た。得られた無水マレイン酸変性塩素化ポリプロピレンエマルション樹脂（１）の樹脂固形分は２９．２％であり、塩基性物質（イソプロパノールアミン（第１級アミン化合物））の含有量は０．５％であった。
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these. Hereinafter, unless otherwise specified, “part by mass” is simply referred to as “part”, and “mass%” is simply referred to as “%”.
[Production Example 1-1: Production of maleic anhydride-modified chlorinated polypropylene emulsion resin]
In a reactor equipped with a stirring blade, a thermometer, a temperature control thermistor device, and a cooling pipe, maleic anhydride-modified chlorinated polypropylene resin ("Supercron 892LS" manufactured by Nippon Paper Industries Co., Ltd .: chlorine content 22%, weight 240 parts of average molecular weight 70000-80000), 52 parts of nonylphenyl polyoxyethylene ether ("Emulgen 920" manufactured by Kao Corporation), 62 parts of aromatic hydrocarbon solvent ("Sorvesso 100" manufactured by Exxon), 27 parts of carbitol acetate Was heated at 110 ° C. for 1 hour to dissolve, and then cooled to 100 ° C. or lower. Subsequently, 614 parts of deionized water in which 5 parts of isopropanolamine (primary amine compound) was dissolved was added dropwise over 1 hour to perform phase inversion emulsification. Then, it cooled to room temperature and filtered with a 400 mesh net | network, and the maleic anhydride modified chlorinated polypropylene emulsion resin (1) was obtained. The obtained maleic anhydride-modified chlorinated polypropylene emulsion resin (1) has a resin solid content of 29.2% and a basic substance (isopropanolamine (primary amine compound)) content of 0.5%. there were.
〔製造例１−２：無水マレイン酸変性塩素化ポリプロピレンエマルション樹脂の製造〕
無水マレイン酸変性塩素化ポリプロピレン樹脂（「スーパークロン８９２ＬＳ」日本製紙（株）製：塩素含有率２２％、重量平均分子量７００００〜８００００）を、無水マレイン酸変性塩素化ポリプロピレン樹脂（「ハードレンＭ１２８Ｐ」東洋化成工業（株）製：塩素含有率２１％、重量平均分子量４００００）に変更し、イソプロパノールアミン（第１級アミン化合物）を２−アミノ−２−メチルプロパノール（第１級アミン化合物）に変更したこと以外は、製造例１−１と同様にして、無水マレイン酸変性塩素化ポリプロピレンエマルション樹脂（２）を得た。得られた無水マレイン酸変性塩素化ポリプロピレンエマルション樹脂（２）の樹脂固形分は２９．２％であり、塩基性物質（２−アミノ−２−メチルプロパノール（第１級アミン化合物））の含有量は０．５％であった。
[Production Example 1-2: Production of maleic anhydride-modified chlorinated polypropylene emulsion resin]
Maleic anhydride-modified chlorinated polypropylene resin ("Superclon 892LS" manufactured by Nippon Paper Industries Co., Ltd .: chlorine content 22%, weight average molecular weight 70000-80000) and maleic anhydride-modified chlorinated polypropylene resin ("Hardlen M128P" Toyo Made by Kasei Kogyo Co., Ltd .: Chlorine content 21%, weight average molecular weight 40000), isopropanolamine (primary amine compound) changed to 2-amino-2-methylpropanol (primary amine compound) Except for this, a maleic anhydride-modified chlorinated polypropylene emulsion resin (2) was obtained in the same manner as in Production Example 1-1. Resin solid content of the obtained maleic anhydride-modified chlorinated polypropylene emulsion resin (2) is 29.2%, and content of basic substance (2-amino-2-methylpropanol (primary amine compound)) Was 0.5%.
〔製造例１−３：無水マレイン酸変性塩素化ポリプロピレンエマルション樹脂の製造〕
イソプロパノールアミン（第１級アミン化合物）５部を２６％アンモニア水７部に変更し、脱イオン水の量を６１４部から６１２部に変更したこと以外は、製造例１−１と同様にして、無水マレイン酸変性塩素化ポリプロピレンエマルション樹脂（３）を得た。得られた無水マレイン酸変性塩素化ポリプロピレンエマルション樹脂（３）の樹脂固形分は２９．２％であり、塩基性物質（アンモニア）の含有量は０．１８２％であった。
〔比較製造例１−１：無水マレイン酸変性塩素化ポリプロピレンエマルション樹脂の製造〕
２６％アンモニア水７部をＮ，Ｎ−ジメチルエタノールアミン（第３級アミン化合物）７部に変更したこと以外は、製造例１−３と同様にして、比較用の無水マレイン酸変性塩素化ポリプロピレンエマルション樹脂（Ｃ１）を得た。得られた無水マレイン酸変性塩素化ポリプロピレンエマルション樹脂（Ｃ１）の樹脂固形分は２９．２％であり、塩基性物質（Ｎ，Ｎ−ジメチルエタノールアミン（第３級アミン化合物））の含有量は０．７％であった。
[Production Example 1-3: Production of maleic anhydride-modified chlorinated polypropylene emulsion resin]
Except for changing 5 parts of isopropanolamine (primary amine compound) to 7 parts of 26% ammonia water and changing the amount of deionized water from 614 parts to 612 parts, the same as in Production Example 1-1, A maleic anhydride-modified chlorinated polypropylene emulsion resin (3) was obtained. The obtained maleic anhydride-modified chlorinated polypropylene emulsion resin (3) had a resin solid content of 29.2% and a basic substance (ammonia) content of 0.182%.
[Comparative Production Example 1-1: Production of maleic anhydride-modified chlorinated polypropylene emulsion resin]
Maleic anhydride-modified chlorinated polypropylene for comparison in the same manner as in Production Example 1-3, except that 7 parts of 26% ammonia water was changed to 7 parts of N, N-dimethylethanolamine (tertiary amine compound). An emulsion resin (C1) was obtained. The obtained maleic anhydride-modified chlorinated polypropylene emulsion resin (C1) has a resin solid content of 29.2%, and the content of basic substance (N, N-dimethylethanolamine (tertiary amine compound)) is It was 0.7%.
〔製造例２−１：水性エポキシ樹脂溶液の調製〕
攪拌機を備えた容器に、水性エポキシ樹脂（「エピレッツ８８０ＳＡＷ−６５」シェルケミカル（株）製：樹脂固形分６５％）１００部を仕込み、攪拌しながら脱イオン水３０部を加えたのち、さらに３０分間攪拌して、水性エポキシ樹脂溶液（１）を得た。
〔製造例２−２：水性エポキシ樹脂溶液の調製〕
攪拌機を備えた容器に、水性エポキシ樹脂（「エピレッツ６００６Ｗ−７０」シェルケミカル（株）製：樹脂固形分７０％）１００部を仕込み、攪拌しながら脱イオン水４０部を加えたのち、さらに３０分間攪拌して、水性エポキシ樹脂溶液（２）を得た。
[Production Example 2-1: Preparation of aqueous epoxy resin solution]
A container equipped with a stirrer was charged with 100 parts of an aqueous epoxy resin (“Epilets 880SAW-65” manufactured by Shell Chemical Co., Ltd .: resin solid content 65%), 30 parts of deionized water was added while stirring, and then 30 parts. Stirring for a minute gave an aqueous epoxy resin solution (1).
[Production Example 2-2: Preparation of aqueous epoxy resin solution]
A container equipped with a stirrer was charged with 100 parts of an aqueous epoxy resin ("Epiletz 6006W-70" manufactured by Shell Chemical Co., Ltd .: resin solid content 70%), and after adding 40 parts of deionized water with stirring, an additional 30 parts were added. Stirring for a minute gave an aqueous epoxy resin solution (2).
〔製造例２−３：水性エポキシ樹脂溶液の調製〕
攪拌機を備えた容器に、水性エポキシ樹脂（「エピレッツ５００３Ｗ−５５」シェルケミカル（株）製：樹脂固形分５８％）１００部を仕込み、攪拌しながら脱イオン水１６部を加えたのち、さらに３０分間攪拌して、水性エポキシ樹脂溶液（３）を得た。
〔製造例３−１：水性アルキッド樹脂の顔料分散ペーストの調製〕
攪拌機を備えた容器に、水性アルキッド樹脂（「アクリセットＡＲＬ５８１」日本触媒（株）製：樹脂固形分３８％、２−アミノ−２−メチルプロパノール（第１級アミン化合物）理論含有量０．６７％）２８７部、脱イオン水３６８部、アセチレン系顔料湿潤剤（「サーフィノールＣＴ３２４」エアープロダクト社製）３０部、消泡剤（「フォーマスターＳ」ヘンケル社製）５部、導電カーボン（「カーボンＥＣＰ６００ＪＤ」ライオン社製）２０部、酸化チタン顔料（「タイピュアーＲ９６０」デュポン社製）２７０部、体質顔料（「ニップシールＳＳ５０Ｂ」日本シリカ社製）２０部を、順に攪拌下で添加し、１時間攪拌後、ラボ用１．４リットルのダイノミル分散機にてグラインドゲージで顔料粒子が２０μｍ以下になるまで分散を行い、水性アルキッド樹脂の顔料分散ペースト（１）を得た。得られた顔料分散ペースト（１）の不揮発分は４４．２％であり、樹脂固形分（水性アルキッド樹脂の含有量）は１０．９％であった。
[Production Example 2-3: Preparation of aqueous epoxy resin solution]
A container equipped with a stirrer was charged with 100 parts of an aqueous epoxy resin ("Epilettsu 5003W-55" manufactured by Shell Chemical Co., Ltd .: resin solid content 58%), and after adding 16 parts of deionized water with stirring, an additional 30 parts were added. Stirring for minutes gave an aqueous epoxy resin solution (3).
[Production Example 3-1: Preparation of pigment dispersion paste of aqueous alkyd resin]
In a container equipped with a stirrer, an aqueous alkyd resin (“Acryset ARL581” manufactured by Nippon Shokubai Co., Ltd .: resin solid content 38%, 2-amino-2-methylpropanol (primary amine compound) theoretical content 0.67 %) 287 parts, deionized water 368 parts, acetylene pigment wetting agent ("Surfinol CT324" manufactured by Air Product) 30 parts, antifoaming agent ("Formaster S" manufactured by Henkel) 5 parts, conductive carbon (" 20 parts of carbon ECP600JD “Lion Corporation”, 270 parts of titanium oxide pigment (“Typure R960” manufactured by DuPont) and 20 parts of extender pigment (“Nip Seal SS50B” manufactured by Nippon Silica Co., Ltd.) were added in this order. After stirring for a while, disperse with a 1.4-liter dynomill disperser for the lab until the pigment particles are 20 μm or less with a grind gauge There was obtained a water-based alkyd resin pigment-dispersed paste (1). The pigment dispersion paste (1) obtained had a nonvolatile content of 44.2% and a resin solid content (content of aqueous alkyd resin) of 10.9%.
〔比較製造例３−１：水性アルキッド樹脂の顔料分散ペーストの調製〕
水性アルキッド樹脂（「アクリセットＡＲＬ５８１」日本触媒（株）製：樹脂固形分３８％、２−アミノ−２−メチルプロパノール（第１級アミン化合物）理論含有量０．６７％）２８７部を、水性アルキッド樹脂（「アクリセットＡＲＬ５８０」日本触媒（株）製：樹脂固形分４２％、トリエチルアミン（第３級アミン化合物）理論含有量１．１％）２６０部に変更し、脱イオン水の量を３６８部から３９５部に変更したこと以外は、製造例３−１と同様にして、水性アルキッド樹脂の顔料分散ペースト（Ｃ１）を得た。得られた顔料分散ペースト（Ｃ１）の不揮発分は４４．２％であり、樹脂固形分（水性アルキッド樹脂の含有量）は１０．９％であった。
[Comparative Production Example 3-1: Preparation of pigment dispersion paste of aqueous alkyd resin]
287 parts of an aqueous alkyd resin (“Acryset ARL581” manufactured by Nippon Shokubai Co., Ltd .: resin solid content 38%, 2-amino-2-methylpropanol (primary amine compound) theoretical content 0.67%) Changed to 260 parts of alkyd resin (“Acryset ARL580” manufactured by Nippon Shokubai Co., Ltd .: resin solid content 42%, triethylamine (tertiary amine compound) theoretical content 1.1%), and the amount of deionized water was 368 A pigment dispersion paste (C1) of an aqueous alkyd resin was obtained in the same manner as in Production Example 3-1, except that the amount was changed from 395 parts to 395 parts. The obtained pigment dispersion paste (C1) had a non-volatile content of 44.2% and a resin solid content (content of aqueous alkyd resin) of 10.9%.
〔実施例１〕
攪拌機を備えた容器に、無水マレイン酸変性塩素化ポリプロピレンエマルション樹脂（１）２５４部を仕込んだ。次いで、攪拌しながら、水性エポキシ溶液（１）を８２部、水性アルキッド樹脂の顔料分散ペースト（１）を３６７部、ｐＨ調製剤としてイソプロパノールアミン（第１級アミン化合物）２．７部、メラミン樹脂（メトキシメチロールメラミン「サイメル３２７」三井サイテック（株）製：樹脂固形分９０％）１０．３部、脱イオン水２７５部、増粘剤（「アクリゾールＡＳＥ６０」ローム＆ハース社製）１１部を添加し、１時間攪拌して、水性プライマー塗料（１）を得た。
[Example 1]
A container equipped with a stirrer was charged with 254 parts of maleic anhydride-modified chlorinated polypropylene emulsion resin (1). Next, with stirring, 82 parts of the aqueous epoxy solution (1), 367 parts of the pigment dispersion paste (1) of the aqueous alkyd resin, 2.7 parts of isopropanolamine (primary amine compound) as a pH adjuster, melamine resin (Methoxymethylol melamine “Cymel 327” manufactured by Mitsui Cytec Co., Ltd .: resin solid content 90%) 10.3 parts, 275 parts deionized water, 11 parts thickener (“Acrysol ASE60” manufactured by Rohm & Haas) The mixture was stirred for 1 hour to obtain an aqueous primer paint (1).
〔実施例２〜８および比較例１〜６〕
各成分の種類と量を表１および表２に示すように変更したこと以外は、実施例１と同様にして、水性プライマー塗料（２）〜（８）および比較用の水性プライマー塗料（Ｃ１）〜（Ｃ６）を得た。
表１および表２においては、下記の略号を用いた。
・ＣＰＯＥｍ（１）：無水マレイン酸変性塩素化ポリプロピレンエマルション樹脂（１）
・ＣＰＯＥｍ（２）：無水マレイン酸変性塩素化ポリプロピレンエマルション樹脂（２）
・ＣＰＯＥｍ（３）：無水マレイン酸変性塩素化ポリプロピレンエマルション樹脂（３）
・ＣＰＯＥｍ（Ｃ１）：比較用の無水マレイン酸変性塩素化ポリプロピレンエマルション樹脂（Ｃ１）
・メラミン樹脂（１）：メトキシメチロールメラミン「サイメル３２７」三井サイテック（株）製、樹脂固形分９０％
・メラミン樹脂（２）：メトキシメチロールメラミン「レジメン７１７」ソリューシャ社製、樹脂固形分８４％
・メラミン樹脂（３）：メトキシ／ｎ−ブトキシ混合メチロールメラミン「サイメル２０４」三井サイテック（株）製、樹脂固形分８０％
・ｐＨ調整剤（１）：イソプロパノールアミン（第１級アミン化合物）
・ｐＨ調整剤（２）：２−アミノ−２−メチルプロパノール（第１級アミン化合物）
・ｐＨ調整剤（Ｃ１）：Ｎ，Ｎ−ジメチルエタノールアミン（第３級アミン化合物）
・ＣＡＢ：セルロースアセテートブチレート「ＣＭＣＡ６４１−０．５」イーストマンケミカル社製
実施例１〜８および比較例１〜６で得られた各水性プライマー塗料について、下記の評価を行なった。結果を表１および表２に示す。
[Examples 2 to 8 and Comparative Examples 1 to 6]
Aqueous primer paints (2) to (8) and a comparative aqueous primer paint (C1) in the same manner as in Example 1 except that the types and amounts of the respective components were changed as shown in Tables 1 and 2. To (C6).
In Tables 1 and 2, the following abbreviations were used.
CPOEm (1): Maleic anhydride modified chlorinated polypropylene emulsion resin (1)
CPOEm (2): Maleic anhydride modified chlorinated polypropylene emulsion resin (2)
CPOEm (3): Maleic anhydride modified chlorinated polypropylene emulsion resin (3)
CPOEm (C1): Maleic anhydride-modified chlorinated polypropylene emulsion resin (C1) for comparison
Melamine resin (1): Methoxymethylol melamine “Cymel 327” manufactured by Mitsui Cytec Co., Ltd., resin solid content 90%
Melamine resin (2): Methoxymethylol melamine “Regimen 717” manufactured by Solusha, 84% resin solids
Melamine resin (3): Methoxy / n-butoxy mixed methylolmelamine “Cymel 204” manufactured by Mitsui Cytec Co., Ltd., resin solid content 80%
PH adjuster (1): Isopropanolamine (primary amine compound)
PH adjuster (2): 2-amino-2-methylpropanol (primary amine compound)
PH adjuster (C1): N, N-dimethylethanolamine (tertiary amine compound)
CAB: cellulose acetate butyrate “CMCA641-0.5” manufactured by Eastman Chemical Co., Ltd. The following evaluations were performed on each aqueous primer coating obtained in Examples 1-8 and Comparative Examples 1-6. The results are shown in Tables 1 and 2.
＜貯蔵安定性＞
得られた水性プライマー塗料を４０℃で７日間放置したのち、塗料の状態を目視にて観察し、以下の基準で判定した。
○：粘度上昇が殆ど認められない、×：著しい粘度上昇またはゲル化が認められる
＜塗膜の外観＞
得られた水性プライマー塗料を、中性洗剤で洗浄したポリプロピレン素材（７０ｍｍ×２６０ｍｍ×３ｍｍ）に乾燥膜厚１０μｍとなるようにスプレー塗装し、８０℃で５分間乾燥したのち、室温で５分間放置した。次いで、上塗りベース塗料として、溶剤型メラミン樹脂硬化型塗料（１液アクリルメラミン塗料「Ｒ６３３１−１」日本ビー・ケミカル（株）製；表中「溶剤型」と略す）と水性メラミン樹脂硬化型塗料（１液アクリルメラミン塗料「アクアレックスＡＲ−２０００」日本ペイント（株）製；表中「水性」と略す）のうち表１および表２に示す方を乾燥膜厚１５μｍとなるように塗装し、室温で１分間放置した。溶剤型メラミン樹脂硬化型塗料を塗装した場合には、引き続き、上塗りクリヤー塗料として、溶剤型メラミン樹脂硬化型塗料（１液アクリルメラミン塗料「Ｒ６３４１−１クリヤー塗料」日本ビー・ケミカル（株）製）を乾燥膜厚３０μｍとなるように塗装し、室温で５分間放置したのち、１２０℃で２０分間乾燥して、試験片を作製した。他方、水性メラミン樹脂硬化型塗料を塗装した場合には、引き続き、８０℃で５分間乾燥したのち、室温で５分間放置し、その後、上塗りクリヤー塗料として、２液型クリヤー塗料（「Ｒ２５００クリヤー塗料」日本ビー・ケミカル（株）製）とイソシアネート硬化剤（「Ｈ２５００」日本ビー・ケミカル（株）製）とを１００／４０（質量比）で混合した２液型クリヤー塗料を乾燥膜厚３０μｍとなるように塗装し、室温で５分間放置したのち、１２０℃で２０分間乾燥して、試験片を作製した。そして、得られた試験片の外観を目視にて観察し、以下の基準で判定した。
○：光沢、平滑性、チジミ等の異常が認められない、×：光沢、平滑性、チジミ等の異常が認められる
＜塗膜の耐水性＞
塗膜の外観の評価で得た試験片を４０℃の温水中に１０日間全没浸漬したのち、取り出して室温で１時間放置した。その後、カッターで試験片の塗膜上からポリピロピレン素材表面に達するように、２ｍｍ角の１００個の碁盤目状に切り込みを入れ、その上に粘着テープを貼ったのちに強制的に剥離したときの塗膜の剥がれ具合を以下の基準で判定した。
○：塗膜の剥離が全く認められない、×：一部でも剥離が認められる
<Storage stability>
The obtained water-based primer coating was allowed to stand at 40 ° C. for 7 days, and then the state of the coating was visually observed and judged according to the following criteria.
○: Almost no increase in viscosity is observed, ×: Remarkable increase in viscosity or gelation is observed <Appearance of coating film>
The obtained water-based primer paint is spray-coated on a polypropylene material (70 mm × 260 mm × 3 mm) washed with a neutral detergent so as to have a dry film thickness of 10 μm, dried at 80 ° C. for 5 minutes, and then allowed to stand at room temperature for 5 minutes. did. Next, solvent-based melamine resin curable paint (one-component acrylic melamine paint “R63331-1” manufactured by Nippon Bee Chemical Co., Ltd .; abbreviated as “solvent type” in the table) and water-based melamine resin curable paint Of the one-pack acrylic melamine paint “AQUAREX AR-2000” manufactured by Nippon Paint Co., Ltd .; abbreviated as “water-based” in the table, the one shown in Tables 1 and 2 was applied to a dry film thickness of 15 μm Left at room temperature for 1 minute. When a solvent-type melamine resin curable paint is applied, the solvent-type melamine resin curable paint (one-part acrylic melamine paint "R6341-1 clear paint" manufactured by Nippon Bee Chemical Co., Ltd.) Was coated to a dry film thickness of 30 μm, allowed to stand at room temperature for 5 minutes, and then dried at 120 ° C. for 20 minutes to prepare a test piece. On the other hand, when a water-based melamine resin curable paint is applied, it is subsequently dried at 80 ° C. for 5 minutes and then left at room temperature for 5 minutes. Thereafter, a two-part clear paint (“R2500 clear paint” “Nippon Bee Chemical Co., Ltd.” and an isocyanate curing agent (“H2500” Nihon Bee Chemical Co., Ltd.) mixed at 100/40 (mass ratio) with a two-component clear paint having a dry film thickness of 30 μm Then, after leaving it to stand at room temperature for 5 minutes, it was dried at 120 ° C. for 20 minutes to prepare a test piece. And the external appearance of the obtained test piece was observed visually, and the following references | standards determined.
○: Abnormalities such as gloss, smoothness, and blemishes are not observed, X: Abnormalities such as gloss, smoothness, and blemishes are observed <Water resistance of coating film>
The test piece obtained by evaluating the appearance of the coating film was immersed in warm water at 40 ° C. for 10 days, and then taken out and left at room temperature for 1 hour. After that, with a cutter, cut into 100 square grids of 2 mm square so as to reach the surface of the polypyropylene material from the coating film of the test piece, and after forcibly peeling off after sticking an adhesive tape on it The degree of peeling of the coating film was determined according to the following criteria.
○: No peeling of the coating film is observed
本発明にかかる水性プライマー塗料および塗膜形成方法は、高温焼付けができないプラスチック素材、とりわけポリプロピレン素材に対して好適に使用することができ、例えば、自動車バンパー等の用途に有用なものである。 The water-based primer coating and the method for forming a coating film according to the present invention can be suitably used for plastic materials that cannot be baked at high temperatures, particularly polypropylene materials, and are useful for applications such as automobile bumpers.
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