JP5046774B2 - Water-based primer coating composition and coating film forming method - Google Patents
Water-based primer coating composition and coating film forming method Download PDFInfo
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- JP5046774B2 JP5046774B2 JP2007196263A JP2007196263A JP5046774B2 JP 5046774 B2 JP5046774 B2 JP 5046774B2 JP 2007196263 A JP2007196263 A JP 2007196263A JP 2007196263 A JP2007196263 A JP 2007196263A JP 5046774 B2 JP5046774 B2 JP 5046774B2
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- resin
- aqueous
- mass
- water
- coating composition
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- 150000002739 metals Chemical class 0.000 description 1
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- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
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- 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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- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000007601 warm air drying Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
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- Paints Or Removers (AREA)
Description
本発明は、水性プライマー塗料組成物及び塗膜形成方法に関する。 The present invention relates to an aqueous primer coating composition and a coating film forming method.
自動車バンパーやモール等に用いられるプラスチック素材は、一般に塗料の濡れ性が悪く、密着性等に劣る。特に、プラスチック素材がポリプロピレン樹脂等である場合には、これらの樹脂が化学的に不活性であるために、上塗り塗料と素材の密着性が悪い。このため、上塗り塗料の塗装前にプライマーを塗装することが従来から一般的になされている。それらのプライマーとしては種々の溶剤型プライマーが検討、使用され、ここ数年は、環境配慮から有機溶剤を用いない水性プライマーが提案され、一部使用されつつある。 Plastic materials used for automobile bumpers and moldings generally have poor paint wettability and poor adhesion. In particular, when the plastic material is a polypropylene resin or the like, the adhesiveness between the top coating material and the material is poor because these resins are chemically inert. For this reason, conventionally, the primer is generally applied before the top coating is applied. As these primers, various solvent-type primers have been studied and used. In recent years, an aqueous primer that does not use an organic solvent has been proposed and partially used for environmental considerations.
プライマーには、上塗り塗膜と素材との間に優れた密着性が得られることや形成した複層塗膜に優れた耐ガソホール性を付与することが要求されるが、従来の水性プライマーでは、これらの性能を両立することは一般的に困難であった。また、近年、高圧洗浄による洗車がなされる場合があるが、従来の水性プライマーを適用した自動車を高圧洗車した場合、バンパー等のプラスチック素材において、プライマーとプラスチック素材の間から複層塗膜が剥離するという問題が生じていた。更に、耐湿性も必要とされているが、高圧洗車時の複層塗膜の剥離抑制と耐湿性を両立することも困難であった。 The primer is required to provide excellent adhesion between the top coat film and the material and to provide excellent gasohol resistance to the formed multilayer coating film. It has been generally difficult to achieve both of these performances. Also, in recent years, car washing by high-pressure washing may be performed, but when a car using a conventional water-based primer is subjected to high-pressure washing, the multilayer coating film peels off between the primer and the plastic material in a plastic material such as a bumper. There was a problem of doing. Furthermore, although moisture resistance is also required, it has been difficult to achieve both suppression of peeling of the multilayer coating film and moisture resistance during high-pressure car washing.
従来の水性プライマーとして、水性塩素化ポリオレフィン樹脂、水性アルキッド樹脂及び水性ノボラック型エポキシ樹脂を含むもの(特許文献1)、水性塩素化ポリオレフィン樹脂、水性ポリウレタン樹脂、水性エポキシ樹脂及び有機強塩基及び/又はその塩を含むもの(特許文献2)が開示されている。 Examples of conventional water-based primers include water-based chlorinated polyolefin resins, water-based alkyd resins, and water-based novolak-type epoxy resins (Patent Document 1), water-based chlorinated polyolefin resins, water-based polyurethane resins, water-based epoxy resins and organic strong bases and / or The thing containing the salt (patent document 2) is disclosed.
しかし、耐湿性や耐ガソホール性の更なる性能向上が必要であり、高圧洗車時の複層塗膜の剥離という問題もあった。また、塩素化ポリオレフィンを使用するものであるため、塩素化された樹脂の燃焼処理時の発生ガスヘの懸念から非塩素系樹脂への転換も近年では要請されてきた。 However, further improvement in moisture resistance and gasohol resistance is necessary, and there is also a problem of peeling of the multilayer coating film during high-pressure car washing. In addition, since chlorinated polyolefin is used, conversion to non-chlorine resin has been requested in recent years due to concerns about gas generated during combustion treatment of chlorinated resin.
特許文献3には、水性ポリオレフィン樹脂、水性アクリル樹脂、水性ポリウレタン樹脂に、オキサゾリン系硬化剤、エポキシ系硬化剤等の硬化剤を添加した水性プライマーが開示され、水性非塩素化ポリオレフィン系樹脂を用いた具体例として、無水マレイン酸変性エチレン・プロピレン共重合体と無水マレイン酸変性ポリプロピレン樹脂を併用して水性樹脂化した例が挙げられている。 Patent Document 3 discloses an aqueous primer obtained by adding a curing agent such as an oxazoline-based curing agent or an epoxy-based curing agent to an aqueous polyolefin resin, an aqueous acrylic resin, or an aqueous polyurethane resin, and uses an aqueous non-chlorinated polyolefin resin. As a specific example, an example in which a maleic anhydride-modified ethylene / propylene copolymer and a maleic anhydride-modified polypropylene resin are used in combination to form an aqueous resin is given.
しかし、ここで記載されているプライマーを用いてプラスチック素材に複層塗膜を形成した場合、素材に対する密着性及び耐ガソホール性の両立や高圧洗車時の複層塗膜の剥離抑制及び耐湿性の両立が困難であった。
本発明は、上記現状に鑑み、素材に対する密着性及び耐ガソホール性を両立できるとともに、高圧洗浄による洗車時における複層塗膜の剥離抑制及び耐湿性も両立でき、塩素を含まないポリオレフィン系樹脂を用いた水性プライマー塗料組成物を提供することを目的とするものである。 In view of the above-mentioned present situation, the present invention can achieve both adhesion to a material and gasohol resistance, and also can suppress peeling of a multilayer coating film and moisture resistance at the time of car washing by high-pressure washing. The object is to provide a water-based primer coating composition used.
本発明は、水性非塩素化ポリオレフィン系樹脂(A)、水性ポリウレタン樹脂(B)、水性エポキシ樹脂(C)及び内部架橋アクリル粒子エマルション(D)を含む水性プライマー塗料組成物であって、上記(A)、(B)、(C)及び(D)の合計量100質量%中、固形分換算で、上記(A)の含有量が15〜60質量%、上記(B)の含有量が10〜50質量%、上記(C)の含有量が20〜50質量%、上記(D)の含有量が5〜20質量%であり、上記(A)は、その結晶化度が35〜55%で、かつ、重量平均分子量が50000〜200000である水性ポリプロピレン系樹脂であることを特徴とする水性プライマー塗料組成物である。 The present invention is an aqueous primer coating composition comprising an aqueous non-chlorinated polyolefin resin (A), an aqueous polyurethane resin (B), an aqueous epoxy resin (C) and an internally crosslinked acrylic particle emulsion (D), In 100% by mass of the total amount of A), (B), (C) and (D), the content of (A) is 15 to 60% by mass and the content of (B) is 10 in terms of solid content. -50 mass%, the content of (C) is 20-50 mass%, the content of (D) is 5-20 mass%, and (A) has a crystallinity of 35-55%. The aqueous primer coating composition is an aqueous polypropylene resin having a weight average molecular weight of 50,000 to 200,000.
上記樹脂(A)は、メタロセン触媒を用いて得られたものであることが好ましい。
上記樹脂(A)は、乳化剤を使用することなく水性化させた水性ポリプロピレン系樹脂であることが好ましい。
The resin (A) is preferably obtained using a metallocene catalyst.
The resin (A) is preferably an aqueous polypropylene resin that has been made aqueous without using an emulsifier.
上記エマルション(D)は、エチレン性不飽和単量体及び架橋性単量体からなるモノマー組成物を乳化重合することによって得られるものであり、上記エチレン性不飽和単量体を重合して得られる非架橋ポリマーのガラス転移温度が50〜140℃で、かつ、上記架橋性単量体の含有量が上記モノマー組成物100質量%中0.1〜50質量%であること好ましい。 The emulsion (D) is obtained by emulsion polymerization of a monomer composition comprising an ethylenically unsaturated monomer and a crosslinkable monomer, and is obtained by polymerizing the ethylenically unsaturated monomer. It is preferable that the non-crosslinked polymer has a glass transition temperature of 50 to 140 ° C. and the content of the crosslinkable monomer is 0.1 to 50% by mass in 100% by mass of the monomer composition.
本発明はまた、上述の水性プライマー塗料組成物を基材に塗装する工程及び上塗り塗料を塗装する工程を含むことを特徴とする塗膜形成方法でもある。
以下、本発明を詳細に説明する。
The present invention is also a coating film forming method characterized by including a step of coating the above-mentioned aqueous primer coating composition on a substrate and a step of applying a top coating.
Hereinafter, the present invention will be described in detail.
本発明の水性プライマー塗料組成物は、水性非塩素化ポリオレフィン系樹脂(A)、水性ポリウレタン樹脂(B)、水性エポキシ樹脂(C)及び内部架橋アクリル粒子エマルション(D)を特定配合で含むもので、かつ、上記樹脂(A)が結晶化度35〜55%、重量平均分子量50000〜200000の水性ポリプロピレン系樹脂である。非塩素化ポリオレフィンを使用した場合、得られた複層塗膜において、密着性と耐ガソホール性を両立することは極めて困難であったが、本発明は上記構成を有しているため、これらの性能を両立することができる。また、高圧洗浄による洗車時において、得られた複層塗膜の剥離を抑制することと、耐湿性を両立することも可能である。上記水性プライマー塗料組成物は、樹脂成分として塩素を含まない樹脂のみを用いたものであることが好ましい。 The aqueous primer coating composition of the present invention comprises an aqueous non-chlorinated polyolefin resin (A), an aqueous polyurethane resin (B), an aqueous epoxy resin (C) and an internally crosslinked acrylic particle emulsion (D) in a specific formulation. The resin (A) is an aqueous polypropylene resin having a crystallinity of 35 to 55% and a weight average molecular weight of 50,000 to 200,000. In the case of using a non-chlorinated polyolefin, it was extremely difficult to achieve both adhesion and gasohol resistance in the obtained multilayer coating film. Both performances can be achieved. Moreover, it is possible to achieve both moisture resistance and suppression of peeling of the obtained multilayer coating film during car washing by high-pressure washing. The aqueous primer coating composition preferably uses only a resin not containing chlorine as a resin component.
本発明の水性プライマー塗料組成物は、水性非塩素化ポリオレフィン系樹脂(A)を含むものである。上記樹脂(A)の骨格は結晶部分と非晶部分が適度に存在しているため、結晶部位を残したまま融点の制御を可能とし、素材への密着性と耐ガソホール性を高い次元で両立させることができる。上記樹脂(A)は、塗膜のマトリックスを形成する成分であり、熱によって溶融させることができる。 The aqueous primer coating composition of the present invention contains an aqueous non-chlorinated polyolefin resin (A). The resin (A) skeleton has moderately crystalline and amorphous parts, so the melting point can be controlled while leaving the crystalline part, and the adhesion to the material and the resistance to gasohol are highly compatible. Can be made. The resin (A) is a component that forms a matrix of the coating film, and can be melted by heat.
上記樹脂(A)の含有量は、上記樹脂(A)、(B)、(C)及び(D)の合計量100質量%中、固形分換算で、15〜60質量%であり、20〜40質量%であることが好ましい。15質量%未満であると、付着点の不足による基材との付着性不良が生じるおそれがある。60質量%を超えると、極性差による上塗り(ベース)との付着不良が生じるおそれがある。 Content of the said resin (A) is 15-60 mass% in conversion of solid content in the total amount of 100 mass% of the said resin (A), (B), (C), and (D), and is 20-20. It is preferable that it is 40 mass%. If it is less than 15% by mass, adhesion failure with the substrate due to insufficient adhesion points may occur. If it exceeds 60% by mass, there is a risk of poor adhesion with the topcoat (base) due to the difference in polarity.
上記樹脂(A)は、結晶化度が35〜55%である。上記結晶化度が35%未満であると、耐ガソホール性、高圧洗車性に劣り、密着性も不充分となるおそれがある。55%を超えると、溶融性が低下し、素材との密着性が劣るおそれがある。
本明細書において、上記結晶化度の測定方法は、以下のとおりである。
The resin (A) has a crystallinity of 35 to 55%. If the crystallinity is less than 35%, gasohol resistance and high-pressure car washability are inferior, and adhesion may be insufficient. If it exceeds 55%, the meltability is lowered and the adhesion to the material may be inferior.
In the present specification, the method for measuring the crystallinity is as follows.
(結晶化度)
ポリプロピレンの立体規則性[mmmm]は、NMR装置(日本電子(株)製、400MHz)にて13C−NMRスペクトル測定法により測定した。試料350〜500mgを、10mmφのNMR用サンプル管中で、約2.2mlのオルトジクロロベンゼンを用いて完全に溶解させた。次いで、ロック溶媒として約0.2mlの重水素化ベンゼンを加え、均一化させた後、130℃でプロトン完全デカップリング法により測定を行った。測定条件は、フリップアングル90°、パルス間隔5T1以上(T1は、メチル基のスピン格子緩和時間のうち最長の値)とした。プロピレン系重合体において、メチレン基及びメチン基のスピン格子緩和時間はメチル基のそれよりも短いので、この測定条件では、すべての炭素の磁化の回復は99%以上である。20時間以上の積算を行い測定した。
(Crystallinity)
The stereoregularity [mmmm] of polypropylene was measured by a 13 C-NMR spectrum measurement method using an NMR apparatus (manufactured by JEOL Ltd., 400 MHz). 350-500 mg of sample was completely dissolved in about 10 ml of a sample tube for NMR using about 2.2 ml of orthodichlorobenzene. Next, about 0.2 ml of deuterated benzene was added as a lock solvent, and the mixture was homogenized. Then, measurement was performed at 130 ° C. by a complete proton decoupling method. The measurement conditions were a flip angle of 90 ° and a pulse interval of 5T 1 or more (T 1 is the longest value of the spin lattice relaxation time of the methyl group). In the propylene-based polymer, since the spin lattice relaxation time of the methylene group and methine group is shorter than that of the methyl group, the recovery of the magnetization of all the carbons is 99% or more under this measurement condition. Measurement was carried out by integrating over 20 hours.
ケミカルシフトは、頭−尾(head to tail)結合からなるプロピレン単位連鎖部の10種類のペンタッド(mmmm,mmmr,rmmr,mmrr,mmrm,rmrr,rmrm,rrrr,rrrm,mrrm)のうち、メチル分岐の絶対配置がすべて同一である、すなわち、mmmmで表されるプロピレン単位5連鎖の第3単位目のメチル基にもとづくピークのケミカルシフトを21.8ppmとして設定し、これを基準として他の炭素ピークのケミカルシフトを決定する。この基準では、例えば、その他のプロピレン単位5連鎖の場合、第3単位目のメチル基にもとづくピークのケミカルシフトはおおむね次のようになる。すなわち、mmmr:21.5〜21.7ppm、rmmr:21.3〜21.5ppm、mmrr:21.0〜21.1ppm、mmrm及びrmrr:20.8〜21.0ppm、rmrm:20.6〜20.8ppm、rrrr:20.3〜20.5ppm、rrrm:20.1〜20.3ppm、mrrm:19.9〜20.1ppmである。 The chemical shift is a methyl branch of 10 types of pentads (mmmm, mmr, rmmr, mmrr, mmrm, rmrr, rmrm, rrrr, rrrr, mrrm) of propylene unit chains composed of head-to-tail bonds. The absolute chemical configuration of all is the same, that is, the chemical shift of the peak based on the methyl group of the third unit of 5 units of propylene units expressed in mmmm is set as 21.8 ppm, and other carbon peaks are based on this. Determine the chemical shift. In this standard, for example, in the case of other five propylene units, the chemical shift of the peak based on the methyl group of the third unit is generally as follows. That is, mmmr: 21.5 to 21.7 ppm, rmmr: 21.3 to 21.5 ppm, mmrr: 21.0 to 21.1 ppm, mmrm and rmrr: 20.8 to 21.0 ppm, rmrm: 20.6 to 20.8 ppm, rrrr: 20.3-20.5 ppm, rrrm: 20.1-20.3 ppm, mrrm: 19.9-20.1 ppm.
このポリプロピレン主鎖は、上記mmmmで表されるペンタッドに帰属されるピークのピークトップのケミカルシフトを21.8ppmとした際に、19.8ppmから22.2ppmの範囲に現れる上記のペンタッド、すなわち、mmmm,mmmr,rmmr,mmrr,mmrm,rmrr,rmrm,rrrr,rrrm,mrrmのすべてのペンタッドに属するピークの総面積Sに対する、21.8ppmをピークトップとするピークの面積S1の比率(S1/S)を結晶化度と定義した。
なお、本願明細書では上記で述べた方法で結晶化度を測定するため、プロピレンと他のモノマーとの共重合体の結晶化度は、樹脂中のポリプロピレン部分の結晶化度を意味する。
This polypropylene main chain has the above pentad appearing in the range of 19.8 ppm to 22.2 ppm when the chemical shift of the peak top of the peak attributed to the pentad represented by mmmm is 21.8 ppm. Ratio of peak area S 1 having a peak top of 21.8 ppm to the total area S of peaks belonging to all pentads of mmmm, mmmr, rmr, mmrr, mmrm, rmrr, rmrm, rrrr, rrrm, mrrm (S 1 / S) was defined as the crystallinity.
In the present specification, since the crystallinity is measured by the method described above, the crystallinity of the copolymer of propylene and other monomers means the crystallinity of the polypropylene portion in the resin.
上記樹脂(A)の重量平均分子量は50000〜200000である。重量平均分子量が50000未満であると、塗膜の凝集力低下により密着性が低下し、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200000を超えると、樹脂の水性化が困難となり、水性樹脂製造に支障をきたすこととなる。
本明細書において、上記重量平均分子量の測定方法は、以下のとおりである。
The weight average molecular weight of the resin (A) is 50,000 to 200,000. When the weight average molecular weight is less than 50000, the adhesion is lowered due to the decrease in cohesive strength of the coating film, and there is a risk that gasohol resistance, moisture resistance, and high-pressure car wash properties are lowered. If the weight average molecular weight exceeds 200,000, it will be difficult to make the resin water-based, which will hinder the production of the water-based resin.
In the present specification, the method for measuring the weight average molecular weight is as follows.
(重量平均分子量)
はじめに試料20mgを30mlのバイアル瓶に採取し、安定剤としてBHTを0.04質量%含有するオルトジクロロベンゼン20gを添加した。135℃に加熱したオイルバスを用いて試料を溶解させた後、孔径3μmのPTFE(ポリテトラフルオロエチレン)フィルターにて熱濾過を行い、ポリマー濃度0.1質量%の試料溶液を調製した。次に、カラムとしてTSKgel GM H−HT(30cm×4本)及びRI検出器を装着したウォーターズ(Waters)社製GPC150CVを使用し、GPC測定を行った。測定条件としては、試料溶液のインジェクション量:500μl、カラム温度:135℃、溶媒:オルトジクロロベンゼン、流量:1.0ml/minを採用した。
分子量の算出に際しては、標準試料として市販の単分散のポリスチレンを使用し、該ポリスチレン標準試料に換算した分子量とした。
(Weight average molecular weight)
First, 20 mg of a sample was collected in a 30 ml vial, and 20 g of orthodichlorobenzene containing 0.04% by mass of BHT was added as a stabilizer. After dissolving the sample using an oil bath heated to 135 ° C., it was filtered hot with a PTFE (polytetrafluoroethylene) filter having a pore diameter of 3 μm to prepare a sample solution having a polymer concentration of 0.1% by mass. Next, GPC measurement was performed by using TSKgel GM H-HT (30 cm × 4) as a column and Waters GPC150CV equipped with an RI detector. As measurement conditions, a sample solution injection amount: 500 μl, a column temperature: 135 ° C., a solvent: orthodichlorobenzene, and a flow rate: 1.0 ml / min were employed.
In calculating the molecular weight, a commercially available monodisperse polystyrene was used as a standard sample, and the molecular weight was converted to the polystyrene standard sample.
上記樹脂(A)は、水性非塩素化ポリプロピレン系樹脂である。上記水性非塩素化ポリプロピレン系樹脂とは、塩素化されていない水性ポリプロピレン系樹脂である。本発明は水性非塩素化ポリプロピレン系樹脂を使用したものであるが、低温焼付け乾燥での密着性に優れている。上記水性非塩素化ポリプロピレン系樹脂としては、例えば、プロピレンの単独重合体、プロピレンとプロピレンと共重合可能な塩素不含の単量体(エチレン等)との共重合体が挙げられる。 The resin (A) is an aqueous non-chlorinated polypropylene resin. The aqueous non-chlorinated polypropylene resin is an aqueous polypropylene resin that is not chlorinated. The present invention uses an aqueous non-chlorinated polypropylene resin, and is excellent in adhesion at low temperature baking and drying. Examples of the aqueous non-chlorinated polypropylene resin include a propylene homopolymer and a copolymer of propylene and a chlorine-free monomer (such as ethylene) copolymerizable with propylene.
上記樹脂(A)は、構成モノマーの90質量%以上がプロピレンであるポリプロピレン系樹脂であることが好ましい。上記ポリプロピレン系樹脂において、プロピレンが90質量%未満であると、樹脂の結晶化度部分が少なくなり、耐ガソホール性、高圧洗車性が劣るおそれがある。 The resin (A) is preferably a polypropylene resin in which 90% by mass or more of the constituent monomer is propylene. In the polypropylene resin, if the propylene content is less than 90% by mass, the crystallinity portion of the resin decreases, and the gasohol resistance and high-pressure car wash properties may be inferior.
上記ポリプロピレン系樹脂において、プロピレン以外の構成モノマーとしては、例えば、炭素原子数2又は4〜20のモノ又はジオレフィン類、例えば、ブテン、ペンテン、ヘキセン、オクテン、デセン、ブタジエン、ヘキサジエン、オクタジエン、シクロブテン、シクロペンテン、シクロヘキセン、ノルボルネン、ノルボルナジエン、スチレン及びこれらの誘導体が挙げられる。本明細書において、樹脂を構成するモノマー含有量は、樹脂の製造に用いる各モノマー量により求めることができる。 In the polypropylene resin, examples of the constituent monomer other than propylene include mono- or diolefins having 2 or 4 to 20 carbon atoms, such as butene, pentene, hexene, octene, decene, butadiene, hexadiene, octadiene, and cyclobutene. , Cyclopentene, cyclohexene, norbornene, norbornadiene, styrene and derivatives thereof. In this specification, monomer content which comprises resin can be calculated | required by the amount of each monomer used for manufacture of resin.
上記樹脂(A)は、メタロセン触媒を用いて得られるものであることが好ましい。これは一般にメタロセン触媒が、リガンドのデサインによりミクロタクティシティーを制御できること、すなわち得られたポリプロピレン主鎖が、アタクチックポリプロピレンとは異なり、結晶化可能な連鎖長のアイソタクチックブロックを含有することを意味し、アイソタクチックブロックが存在するということは、言い換えれば、立体特異性(stereospecificity)が乱れたシークエンスからなるブロックも同時に主鎖に存在することを意味する。即ち、メタロセン触媒を用いて重合されたポリプロピレン主鎖中には、結晶性を有するブロックと非晶性のブロックとが共存し、かつ結晶性を有するブロックが、比較的長い平均連鎖長を有するアイソタクチックブロックから形成され、アイソタクチック性に富む構造になっているという特異な構造となったものである。このような特長から、メタロセン触媒を用いて重合されたポリオレフィンを用いた塗料は、100℃以下であっても得られる塗膜において、本発明の効果を良好に得ることが可能となるためである。
上記メタロセン触媒としては、従来公知のものを使用することができ、例えば、特開2004−115712号公報([0021]〜[0052])記載のもの等が挙げられる。
The resin (A) is preferably obtained using a metallocene catalyst. This generally indicates that metallocene catalysts can control microtacticity by ligand design, that is, the resulting polypropylene backbone contains crystallizable chain length isotactic blocks, unlike atactic polypropylene. In other words, the presence of an isotactic block means that a block composed of a sequence having a disordered stereospecificity is also present in the main chain at the same time. That is, in a polypropylene main chain polymerized using a metallocene catalyst, a crystalline block and an amorphous block coexist, and the crystalline block has an isochron having a relatively long average chain length. It is formed from a tactic block and has a unique structure that is rich in isotacticity. From such a feature, a coating using a polyolefin polymerized using a metallocene catalyst can obtain the effect of the present invention in a coating film obtained even at 100 ° C. or lower. .
As the metallocene catalyst, conventionally known ones can be used, and examples include those described in JP-A No. 2004-115712 ([0021] to [0052]).
上記樹脂(A)は、不飽和有機酸又はその酸無水物によって変性されたもの(以下、変性ポリプロピレン系樹脂ということがある。)であることが好ましい。上記不飽和有機酸又はその酸無水物によって変性されたものとしては、例えば、上記ポリプロピレン系樹脂の主鎖に、炭素原子数3〜25の不飽和カルボン酸又はその酸無水物をグラフト反応させて変性したものを挙げることができる。このグラフト反応は常法によりラジカル発生剤を用いて行うことができる。 The resin (A) is preferably a resin modified with an unsaturated organic acid or an acid anhydride thereof (hereinafter sometimes referred to as a modified polypropylene resin). As what was modified | denatured by the said unsaturated organic acid or its acid anhydride, for example, the main chain of the said polypropylene resin is made to graft-react the unsaturated carboxylic acid of 3-25 carbon atoms or its acid anhydride. Denatured ones can be mentioned. This grafting reaction can be carried out by a conventional method using a radical generator.
グラフトさせる不飽和カルボン酸又はその酸無水物としては、マレイン酸、フマル酸、イタコン酸、テトラヒドロフタル酸、シトラコン酸、クロトン酸、アリルコハク酸、メサコン酸、アコニット酸、及びこれらの無水物等が挙げられ、なかでも、マレイン酸及びこの無水物等が好ましい。 Examples of unsaturated carboxylic acids or acid anhydrides to be grafted include maleic acid, fumaric acid, itaconic acid, tetrahydrophthalic acid, citraconic acid, crotonic acid, allyl succinic acid, mesaconic acid, aconitic acid, and anhydrides thereof. Of these, maleic acid and its anhydride are preferred.
本発明に用いることができる変性ポリプロピレン系樹脂の不飽和カルボン酸又はその酸無水物の付加率(変性ポリプロピレン系樹脂中の不飽和カルボン酸又はその酸無水物の含有割合)は1〜10質量%、好ましくは1.5〜5質量%である。付加率が1質量%未満であると、得られる水性プライマー塗料組成物の分散粒子の粒子径が大きく分散安定性が不良となりやすく、10質量%を超えると、塗膜の耐水性が悪化する傾向となる。この付加率は、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、付加率(含有量)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。 The addition ratio of unsaturated carboxylic acid or acid anhydride thereof in the modified polypropylene resin that can be used in the present invention (content ratio of unsaturated carboxylic acid or acid anhydride in the modified polypropylene resin) is 1 to 10% by mass. , Preferably it is 1.5-5 mass%. When the addition rate is less than 1% by mass, the dispersed particles of the resulting aqueous primer coating composition have a large particle size and the dispersion stability tends to be poor, and when it exceeds 10% by mass, the water resistance of the coating tends to deteriorate. It becomes. This addition rate can be measured by comparing the absorption intensity of the carbonyl group with a calibration curve prepared on the basis of a sample having a known addition rate (content) by infrared spectroscopy.
不飽和カルボン酸又はその酸無水物を付加する方法としては、ラジカル発生剤の存在下で、ラジカル発生剤の分解条件に付すことによりグラフト反応させる方法が一般的であり、例えば、ポリプロピレン主鎖を有機溶媒に溶解し、不飽和カルボン酸又はその酸無水物とラジカル発生剤を添加し、撹拌下で加熱することにより付加を行う方法、各成分を押出機に供給して加熱混練しながら付加を行う方法等が挙げられる。 As a method for adding an unsaturated carboxylic acid or an acid anhydride thereof, there is a general method in which a graft reaction is performed by subjecting to a decomposition condition of the radical generator in the presence of the radical generator. A method of adding by dissolving in an organic solvent, adding an unsaturated carboxylic acid or its acid anhydride and a radical generator, and heating with stirring, supplying each component to an extruder and adding while heating and kneading. The method of performing etc. are mentioned.
使用されるラジカル発生剤と不飽和カルボン酸又はその酸無水物とのモル比(ラジカル発生剤と不飽和カルボン酸又はその酸無水物との比率)は、通常1/100〜3/5、好ましくは1/20〜1/2であり、反応温度は、特に制限はないが、通常50℃以上、好ましくは80〜200℃である。反応時間は、通常2〜10時間である。 The molar ratio of the radical generator to be used and the unsaturated carboxylic acid or acid anhydride thereof (ratio of the radical generator to the unsaturated carboxylic acid or acid anhydride thereof) is usually 1/100 to 3/5, preferably Is 1/20 to 1/2, and the reaction temperature is not particularly limited, but is usually 50 ° C. or higher, preferably 80 to 200 ° C. The reaction time is usually 2 to 10 hours.
グラフト反応に用いられるラジカル発生剤としては、通常のラジカル発生剤から適宜選択して使用することができ、例えば有機過酸化物等が挙げられる。有機過酸化物としては、ジイソプロピルパーオキシド、ジ(t−ブチル)パーオキシド、t−ブチルヒドロパーオキシド、ベンゾイルパーオキシド、ジクミルパーオキシド、クミルヒドロパーオキシド、ジラウロイルパーオキシド、ジベンゾイルパーオキシド、メチルエチルケトンパーオキシド、シクロヘキサノンパーオキシド、クメンヒドロパーオキシド、ジイソプロピルパーオキシカルボナート、ジシクロヘキシルパーオキシカルボナート、t−ブチルパーオキシイソプロピルモノカルボナート等が挙げられる。これらの中でも、ジ(t−ブチル)パーオキシド、ジクミルパーオキシド、t−ブチルパーオキシイソプロピルモノカルボナートが好ましい。 The radical generator used for the graft reaction can be appropriately selected from ordinary radical generators, and examples thereof include organic peroxides. Organic peroxides include diisopropyl peroxide, di (t-butyl) peroxide, t-butyl hydroperoxide, benzoyl peroxide, dicumyl peroxide, cumyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide Methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, diisopropyl peroxycarbonate, dicyclohexyl peroxycarbonate, t-butylperoxyisopropyl monocarbonate and the like. Among these, di (t-butyl) peroxide, dicumyl peroxide, and t-butyl peroxyisopropyl monocarbonate are preferable.
グラフト反応を溶解又は含浸状態で行う場合に用いられる有機溶媒としては、ベンゼン、トルエン、キシレン等の芳香族系炭化水素、ヘキサン、ヘプタン、オクタン、デカン等の脂肪族系炭化水素、トリクロロエチレン、パークロルエチレン、クロルベンゼン、o−ジクロロベンゼン等のハロゲン化炭化水素等が挙げられ、これらの中でも芳香族系炭化水素及びハロゲン化炭化水素が好ましく、特にトルエン、キシレン、クロルベンゼンが好ましい。 Organic solvents used when the grafting reaction is carried out in a dissolved or impregnated state include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane, octane and decane, trichlorethylene, and perchlor. Halogenated hydrocarbons such as ethylene, chlorobenzene, o-dichlorobenzene and the like can be mentioned. Among these, aromatic hydrocarbons and halogenated hydrocarbons are preferable, and toluene, xylene and chlorobenzene are particularly preferable.
また、不飽和ジカルボン酸モノエステルを変性成分として有する変性ポリプロピレン系樹脂を製造する場合は、不飽和ジカルボン酸モノエステルをポリプロピレン主鎖に上記のようにグラフト反応させる方法の他、不飽和ジカルボン酸又はその無水物を、ポリプロピレン主鎖にグラフト反応させた後、脂肪族アルコールを用いてカルボキシル基の1つをエステル化したり、酸無水物基をモノエステル化したりする方法によって製造することもできる。 In the case of producing a modified polypropylene-based resin having an unsaturated dicarboxylic acid monoester as a modifying component, in addition to the method of grafting the unsaturated dicarboxylic acid monoester to the polypropylene main chain as described above, the unsaturated dicarboxylic acid or The anhydride can also be produced by a method in which one of the carboxyl groups is esterified with an aliphatic alcohol and the acid anhydride group is monoesterified using a graft alcohol after grafting to the polypropylene main chain.
上記樹脂(A)は、融点が50〜100℃であることが好ましい。上記融点が50℃未満であると、非晶成分が多くなり、耐ガソホール性、耐湿性、高圧洗車性等が低下するおそれがある。100℃を超えると、溶融性が低下し、素材との密着性が劣るおそれがある。本明細書において、樹脂(A)の融点(℃)の測定方法は、以下のとおりである。 The resin (A) preferably has a melting point of 50 to 100 ° C. If the melting point is less than 50 ° C., the amount of amorphous components increases, and gasohol resistance, moisture resistance, high-pressure car washability, etc. may be reduced. When it exceeds 100 degreeC, a meltability will fall and there exists a possibility that adhesiveness with a raw material may be inferior. In this specification, the measuring method of melting | fusing point (degreeC) of resin (A) is as follows.
(融点測定方法)
示差走査熱量計(DSC)(熱分析装置SSC5200(セイコー電子製)にて以下の工程により測定した値を用いた。すなわち、昇温速度10℃/minにて20℃から150℃に昇温する工程(工程1)、降温速度10℃/minにて150℃から−50℃に降温する工程(工程2)、昇温速度10℃/minにて−50℃から150℃に昇温する工程(工程3)において、工程3の昇温時の図1のチャートの矢印で示される温度を融点とした。
(Measuring method of melting point)
A differential scanning calorimeter (DSC) (thermal analyzer SSC5200 (manufactured by Seiko Denshi)) was used as measured by the following steps: That is, the temperature was raised from 20 ° C. to 150 ° C. at a temperature rising rate of 10 ° C./min. Step (step 1), step of decreasing the temperature from 150 ° C. to −50 ° C. at a temperature decrease rate of 10 ° C./min (step 2), step of increasing the temperature from −50 ° C. to 150 ° C. at a temperature increase rate of 10 ° C./min ( In step 3), the temperature indicated by the arrow in the chart of FIG.
樹脂(A)の水性化方法としては、特に限定されず、従来公知の方法で製造することができる。例えば、上記で製造された酸無水物変性ポリプロピレンにトルエンを加えて100℃くらいで溶かした樹脂溶液とし、その後界面活性剤を加えて、50〜60℃くらいの状態で強制攪拌しながら、50℃くらいのイオン交換水を滴下して転相乳化し、トルエンについては、その後減圧除去する方法が挙げられる。また、テトラヒドロフラン等の溶剤で60℃くらいで上記酸無水物変性ポリプロピレン樹脂を加熱して溶解し、上記樹脂のカルボキシル基を過剰のアミンで中和した後、60℃くらいのイオン交換水を、強制攪拌しながらこの樹脂溶液に滴下し、相転移して乳化し、その後、減圧にて溶剤を除去する方法が挙げられる。更に、上記溶解溶液に乳化剤及びアミンを併用して混合し、60℃くらいのイオン交換水を強制攪拌しながら滴下して乳化し、その後溶媒を減圧除去する方法もある。上記手順とは逆に、アミン等の中和剤及び/又は界面活性剤等が溶解した温水中に上記加熱溶媒で溶かした酸無水物変性ポリオレフィン溶液を水中で強制攪拌しながら滴下し乳化後、溶媒を減圧除去する方法等も挙げられる。 It does not specifically limit as an aqueous-ized method of resin (A), It can manufacture by a conventionally well-known method. For example, a resin solution in which toluene is added to the acid anhydride-modified polypropylene produced above and dissolved at about 100 ° C., and then a surfactant is added, while forcibly stirring at about 50 to 60 ° C., 50 ° C. About ion-exchanged water is dripped and phase-inversion emulsified, and about toluene, the method of removing under reduced pressure after that is mentioned. In addition, the acid anhydride-modified polypropylene resin is heated and dissolved in a solvent such as tetrahydrofuran at about 60 ° C., and after neutralizing the carboxyl group of the resin with an excess of amine, ion-exchanged water at about 60 ° C. is forced. A method may be mentioned in which the solution is added dropwise to the resin solution with stirring, phase transition is performed, and then the solvent is removed under reduced pressure. Furthermore, there is also a method in which an emulsifier and an amine are used in combination with the dissolved solution, and ion-exchanged water at about 60 ° C. is added dropwise with emulsification while emulsifying, and the solvent is removed under reduced pressure. Contrary to the above procedure, an acid anhydride-modified polyolefin solution dissolved with the above heating solvent was added dropwise in warm water in which a neutralizing agent such as amine and / or a surfactant was dissolved in water while forcibly stirring, followed by emulsification. A method of removing the solvent under reduced pressure and the like are also included.
上記樹脂(A)は、乳化剤を使用することなく水性化させた水性ポリプロピレン系樹脂であることが好ましい。乳化剤を使用しないことにより、得られる複層塗膜の耐湿性をより向上させることができる。 The resin (A) is preferably an aqueous polypropylene resin that has been made aqueous without using an emulsifier. By not using an emulsifier, the moisture resistance of the resulting multilayer coating film can be further improved.
本発明の水性プライマー塗料組成物は、水性ポリウレタン樹脂(B)を含むものである。上記(B)を使用することにより、得られる複層塗膜において、優れた耐溶剤性及び耐ガソホール性を得ることができる。上記樹脂(B)は、塗膜のマトリックスを形成する成分である。 The aqueous primer coating composition of the present invention contains an aqueous polyurethane resin (B). By using the above (B), excellent solvent resistance and gasohol resistance can be obtained in the resulting multilayer coating film. The resin (B) is a component that forms a matrix of the coating film.
上記樹脂(B)の含有量は、上記樹脂(A)、(B)、(C)及び(D)の合計量100質量%中、固形分換算で、10〜50質量%である。10質量%未満であると、耐ガソホール性不良が生じるおそれがある。50質量%を超えると、高圧洗車性不良が生じるおそれがある。 Content of the said resin (B) is 10-50 mass% in conversion of solid content in 100 mass% of total amounts of the said resin (A), (B), (C), and (D). If it is less than 10% by mass, gasohol resistance may be poor. If it exceeds 50% by mass, high-pressure car washability may be deteriorated.
上記樹脂(B)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、ジメチロールプロパンジオール又はジメチロールブタンジオール等の水酸基とカルボン酸基を共に有する親水化剤をジブチル錫ジラウレート等の触媒の存在下、イソシアナート基過剰の状態で反応させて得られたウレタンプレポリマーに、アミン類等の有機塩基又は水酸化カリウム、水酸化ナトリウム等の無機塩基によりカルボン酸を中和した後、イオン交換水を加えて水性化した後、更に鎖伸長剤により高分子量化したウレタンディスパージョン;カルボン酸を含有しないウレタンプレポリマーを合成した後、カルボン酸、スルホン酸、エチレングリコール等の親水基を有したジオール又はジアミンを用いて鎖伸長した後、上記塩基性物質で中和して水性化し、必要により更に鎖伸長剤を用いて高分子量化したウレタンディスパージョン;必要により乳化剤も併用して得られたウレタンディスパージョンを挙げることができる。 Examples of the resin (B) include a polyfunctional isocyanate compound, a polyol having two or more hydroxyl groups in one molecule, and a hydrophilizing agent having both a hydroxyl group and a carboxylic acid group, such as dimethylolpropanediol or dimethylolbutanediol. In the presence of a catalyst such as dibutyltin dilaurate, and a urethane prepolymer obtained by reacting in an excess of isocyanate group with an organic base such as amines or an inorganic base such as potassium hydroxide or sodium hydroxide. After neutralizing the water, it was made aqueous by adding ion-exchanged water, and further urethane dispersion increased in molecular weight by a chain extender; after synthesizing a urethane prepolymer not containing carboxylic acid, carboxylic acid, sulfonic acid, ethylene After chain extension using a diol or diamine having a hydrophilic group such as glycol, And urethane dispersions emulsifier obtained in combination if necessary; serial neutralized with a basic substance and water-further urethane dispersion was high molecular weight using a chain extender as needed.
上記多官能イソシアネート化合物としては1,6−ヘキサンジイソシアネート、リジンジイソシアネート、イソホロンジイソシアネート、シクロヘキサン−1,4−ジイソシアネート、キシリレンジイソシアネート、2,4−トリレンジイソシアネート、2,6−トリレンジイソシアネート等のジイソシアネート化合物及びこれらのアダクト体、ビュウレット体、イソシアヌレート体等の多官能イソシアネート化合物等を挙げることができる。
また、上記ポリオールとして、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボナートポリオール等を挙げることができる。
Examples of the polyfunctional isocyanate compound include 1,6-hexane diisocyanate, lysine diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate. Examples thereof include polyfunctional isocyanate compounds such as compounds and adducts, burettes, and isocyanurates.
Examples of the polyol include polyester polyol, polyether polyol, polycarbonate polyol, and the like.
上記鎖長延長剤としては、エチレングリコール、プロピレングリコール、1,4−ブタンジオール、ネオペンチルグリコール、フランジメタノール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール等の低分子量ジオール化合物及びこれらにエチレンオキサイド、プロピレンオキサイド、テトラヒドロフラン等を付加重合させたポリエーテルジオール化合物;上記低分子量ジオール化合物と(無水)コハク酸、アジピン酸、(無水)フタル酸等のジカルボン酸及びこれらの無水物から得られる末端に水酸基を有するポリエステルジオール;トリメチロールエタン、トリメチロールプロパン等の多価アルコール;モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアミノアルコール;エチレンジアミン、プロピレンジアミン、ブチレンジアミン、ヘキサメチレンジアミン、フェニレンジアミン、トルエンジアミン、キシレンジアミン、イソホロンジアミン等のジアミン化合物;水、アンモニア、ヒドラジン、二塩基酸ヒドラジド等を挙げることができる。 Examples of the chain extender include low molecular weight diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, flange methanol, diethylene glycol, triethylene glycol, and tetraethylene glycol, and ethylene oxide and propylene. A polyether diol compound obtained by addition polymerization of oxide, tetrahydrofuran or the like; a hydroxyl group at the terminal obtained from the above low molecular weight diol compound and a dicarboxylic acid such as (anhydrous) succinic acid, adipic acid, (anhydrous) phthalic acid or the like, or an anhydride thereof. Polyester diol having; polyhydric alcohol such as trimethylolethane and trimethylolpropane; amino alcohol such as monoethanolamine, diethanolamine and triethanolamine; ethylene Amine, propylene diamine, butylene diamine, hexamethylene diamine, phenylene diamine, toluene diamine, xylene diamine, diamine compounds such as isophoronediamine; water, ammonia, hydrazine, may be mentioned dibasic acid hydrazide and the like.
上記樹脂(B)は、市販のウレタンディスパージョンを使用することもできる。上記市販のウレタンディスパージョンとしては特に限定されず、スーパーフレックス150、スーパーフレックス420、スーパーフレックス460(以上、第一工業製薬社製)、バイヒドロールVP LS2952(住化バイエルウレタン社製)、VONDIC 2260、VONDIC 2220、ハイドランWLS210、ハイドランWLS213(以上、大日本インキ化学工業社製)、NeoRez R9603(アビシア社製)等を挙げることができる。 Commercially available urethane dispersion can also be used for the resin (B). The commercially available urethane dispersion is not particularly limited. Superflex 150, Superflex 420, Superflex 460 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Bihydrol VP LS2952 (manufactured by Sumika Bayer Urethane Co., Ltd.), VONDIC 2260, VONDIC 2220, Hydran WLS210, Hydran WLS213 (manufactured by Dainippon Ink & Chemicals, Inc.), NeoRez R9603 (Avicia) and the like can be mentioned.
本発明の水性プライマー塗料組成物は、水性エポキシ樹脂(C)を含むものである。上記樹脂(C)を使用することにより、耐水性、耐湿性を向上させることができる。
上記樹脂(C)の含有量は、上記樹脂(A)、(B)、(C)及び(D)の合計量100質量%中、固形分換算で、20〜50質量%である。20質量%未満であると、ゲル分率低下による耐水、耐湿性不良が生じるおそれがある。50質量%を超えると、造膜不良による耐水、耐湿性不良が生じるおそれがある。
The aqueous primer coating composition of the present invention contains an aqueous epoxy resin (C). By using the resin (C), water resistance and moisture resistance can be improved.
Content of the said resin (C) is 20-50 mass% in conversion of solid content in 100 mass% of total amounts of the said resin (A), (B), (C), and (D). If it is less than 20% by mass, water resistance and moisture resistance may be deteriorated due to a decrease in gel fraction. If it exceeds 50% by mass, water resistance and moisture resistance may be poor due to poor film formation.
上記水性エポキシ樹脂(C)は、エポキシ基を分子中に1個以上有する水性樹脂で当該技術分野で公知のものを使用することができる。例えば、フェノールノボラック樹脂にエピクロヒドリンを付加して得られるノボラック型エポキシ樹脂を乳化剤で強制的にエマルション化した、長瀬ケムテック株式会社製デナコールEM150やジャパンエポキシレジン株式会社製エピレッツ6006W70や5003W55や東都化成株式会社のWEX−5100等を挙げることができる。また、ビスフェノールに同様にエピクロヒドリンを付加して得られるビスフェノール型エポキシ樹脂を乳化剤で強制乳化した長瀬ケムテック株式会社製デナコールEM101、EM103やジャパンエポキシレジン株式会社製エピレッツ3510W60、3515W6、3522W60、3540WY55等が挙げられる。更に、ソルビトールやペンタエリスリトールやグリセリン等のポリオールにエピクロヒドリンを付加したアルキルタイプのエポキシ樹脂として長瀬ケムテック株式会社製デナコールEX−611、EX−614、EX−411、EX−313等が挙げられる。 As the aqueous epoxy resin (C), an aqueous resin having at least one epoxy group in the molecule and known in the art can be used. For example, Nagano Chemtech Co., Ltd. Denacol EM150, Japan Epoxy Resins Co., Ltd. Epiletts 6006W70 and 5003W55, and Toto Kasei Co., Ltd., forcibly emulsified with an emulsifier, a novolak type epoxy resin obtained by adding epichlorohydrin to a phenol novolac resin. WEX-5100 and the like. Moreover, Nagase Chemtech Co., Ltd. Denacol EM101, EM103, Japan Epoxy Resins Co., Ltd. Epiletts 3510W60, 3515W6, 3522W60, 3540WY55 etc. which forcedly emulsified the bisphenol type epoxy resin obtained by adding epichlorohydrin similarly to bisphenol with an emulsifier are mentioned. It is done. Furthermore, Nagase Chemtech Co., Ltd. Denacol EX-611, EX-614, EX-411, EX-313 etc. are mentioned as an alkyl-type epoxy resin which added epichlorohydrin to polyols, such as sorbitol, pentaerythritol, and glycerol.
本発明の水性プライマー塗料組成物は、内部架橋アクリル粒子エマルション(D)を含むものである。上記エマルション(D)を使用することにより、高圧洗浄による洗車時において、複層塗膜の剥離を良好に抑制することができる。 The aqueous primer coating composition of the present invention contains an internally crosslinked acrylic particle emulsion (D). By using the emulsion (D), peeling of the multilayer coating film can be satisfactorily suppressed during car washing by high-pressure washing.
上記エマルション(D)の含有量は、上記樹脂(A)、(B)、(C)及び(D)の合計量100質量%中、固形分換算で、5〜20質量%である。5質量%未満であると、硬度不足による高圧洗車性不良が生じるおそれがある。20質量%を超えると、造膜不良による耐水、耐湿性不良が生じるおそれがある。 Content of the said emulsion (D) is 5-20 mass% in conversion of solid content in the total amount of 100 mass% of the said resin (A), (B), (C), and (D). If it is less than 5% by mass, a high-pressure car washability may be caused due to insufficient hardness. If it exceeds 20% by mass, water resistance and moisture resistance may be deteriorated due to defective film formation.
上記エマルション(D)は、架橋構造を有するアクリル樹脂からなるエマルションである。上記エマルション(D)としては、特に限定されず、例えば、エチレン性不飽和単量体及び架橋性単量体を用いて得られる架橋構造を有するアクリル樹脂からなるエマルションを挙げることができる。上記エマルション(D)の平均粒子径は、0.1〜1.0μmであることが好ましい。 The emulsion (D) is an emulsion made of an acrylic resin having a crosslinked structure. The emulsion (D) is not particularly limited, and examples thereof include an emulsion made of an acrylic resin having a crosslinked structure obtained using an ethylenically unsaturated monomer and a crosslinkable monomer. The average particle size of the emulsion (D) is preferably 0.1 to 1.0 μm.
上記エチレン性不飽和単量体としては特に限定されず、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アルリル酸n−ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸2−エチルヘキシル等のアクリル酸又はメタクリル酸のアルキルエステル;スチレン、α−メチルスチレン、ビニルトルエン、t−ブチルスチレン、エチレン、プロピレン、酢酸ビニル、プロピオン酸ビニル、アクリロニトリル、メタクリロニトリル、(メタ)アクリル酸ジメチルアミノエチル等を挙げることができる。これらは、単独で用いてもよく、2種以上を併用してもよい。 The ethylenically unsaturated monomer is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) allyllate, isobutyl (meth) acrylate, (meth) Alkyl esters of acrylic acid or methacrylic acid such as 2-ethylhexyl acrylate; styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, ethylene, propylene, vinyl acetate, vinyl propionate, acrylonitrile, methacrylonitrile, (meta ) Dimethylaminoethyl acrylate and the like. These may be used alone or in combination of two or more.
上記架橋性単量体としては特に限定されず、例えば、分子内に2個以上のラジカル重合可能なエチレン性不飽和結合を有する単量体、相互に反応し得る基をそれぞれ担持する2種のエチレン性不飽和基含有単量体等を挙げることができる。 The crosslinkable monomer is not particularly limited. For example, two or more monomers having an ethylenically unsaturated bond capable of radical polymerization in the molecule and two kinds of groups each carrying a group capable of reacting with each other can be used. Examples thereof include an ethylenically unsaturated group-containing monomer.
上記エマルション(D)の製造に使用することができる分子内に2個以上のラジカル重合可能なエチレン性不飽和結合を有する単量体としては特に限定されず、例えば、エチレングリコールジアクリレート、エチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、1,3−ブチレングリコールジメタクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリメタクリレート、1,4−ブタンジオールジアクリレート、ネオペンチルグリコールジアクリレート、ネオペンチルグリコールジメタクリレート、1,6−ヘキサンジオールジアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールジメタクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラメタクリレート、グリセロールジメタクリレート、グリセロールジアクリレート、グリセロールアリロキシジメタクリレート、1,1,1−トリスヒドロキシメチルエタンジアクリレート、1,1,1−トリスヒドロキシメチルエタントリアクリレート、1,1,1−トリスヒドロキシメチルエタンジメタクリレート、1,1,1−トリスヒドロキシメチルエタントリメタクリレート、1,1,1−トリスヒドロキシメチルプロパンジアクリレート、1,1,1−トリスヒドロキシメチルプロパントリアクリレート、1,1−トリスヒドロキシメチルプロパンジメタクリレート、1,1,1−トリスヒドロキシメチルプロパントリメタクリレート等の多価アルコールの重合性不飽和モノカルボン酸エステル;トリアリルシアヌレート、トリアリルイソシアヌレート、トリアリルトリメリテート、ジアリルテレフタレート、ジアリルフタレート等の多塩基酸の重合性不飽和アルコールエステル;ジビニルベンゼン等の2個以上のビニル基で置換された芳香族化合物等を挙げることができる。これらは、単独で用いてもよく、2種以上を併用してもよい。 The monomer having two or more radically polymerizable ethylenically unsaturated bonds that can be used in the production of the emulsion (D) is not particularly limited, and examples thereof include ethylene glycol diacrylate and ethylene glycol. Dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate , Neopentyl glycol dimethacrylate, 1,6-hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, penta Lithritol tetraacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol dimethacrylate, glycerol diacrylate, glycerol allyloxydimethacrylate, 1,1,1-trishydroxymethylethanediacrylate, 1,1 1,1-trishydroxymethylethane triacrylate, 1,1,1-trishydroxymethylethane dimethacrylate, 1,1,1-trishydroxymethylethane trimethacrylate, 1,1,1-trishydroxymethylpropane diacrylate, , 1,1-Trishydroxymethylpropane triacrylate, 1,1-trishydroxymethylpropane dimethacrylate, 1,1, Polymerizable unsaturated monocarboxylic esters of polyhydric alcohols such as trishydroxymethylpropanetrimethacrylate; polymerization of polybasic acids such as triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate Unsaturated aromatic ester; aromatic compounds substituted with two or more vinyl groups such as divinylbenzene. These may be used alone or in combination of two or more.
上記相互に反応し得る基をそれぞれ担持する2種のエチレン性不飽和基を有する単量体に存在する相互に反応する官能基の組合せとしては特に限定されず、例えば、エポキシ基とカルボキシル基、アミン基とカルボニル基、エポキシ基とカルボン酸無水物基、アミン基とカルボン酸塩化物基、アルキレンイミン基とカルボニル基、オルガノアルコキシシラン基とカルボキシル基、ヒドロキシル基とイソシアネートグリシジルアクリレート基等の組合せを挙げることができる。なかでも、エポキシ基とカルボキシル基の組合せがより好ましい。 The combination of the functional groups that react with each other present in the monomer having two types of ethylenically unsaturated groups that respectively carry the mutually reactive groups is not particularly limited. For example, an epoxy group and a carboxyl group, Combinations of amine groups and carbonyl groups, epoxy groups and carboxylic anhydride groups, amine groups and carboxylic acid chloride groups, alkyleneimine groups and carbonyl groups, organoalkoxysilane groups and carboxyl groups, hydroxyl groups and isocyanate glycidyl acrylate groups, etc. Can be mentioned. Of these, a combination of an epoxy group and a carboxyl group is more preferable.
上記エポキシ基とカルボキシル基の組合せによる2種のエチレン性不飽和基を有する単量体としては、グリシジルメタクリレート等のエポキシ基含有エチレン性不飽和単量体と、アクリル酸、メタクリル酸、クロトン酸等カルボキシル基含有エチレン性不飽和単量体の組合せ等を挙げることができる。 As monomers having two types of ethylenically unsaturated groups by the combination of the epoxy group and the carboxyl group, epoxy group-containing ethylenically unsaturated monomers such as glycidyl methacrylate, acrylic acid, methacrylic acid, crotonic acid, etc. Examples include combinations of carboxyl group-containing ethylenically unsaturated monomers.
上記エマルション(D)は、エチレン性不飽和単量体及び架橋性単量体からなるモノマー組成物を乳化重合することによって得られるものであり、上記エチレン性不飽和単量体を重合して得られる非架橋ポリマーのガラス転移温度が50〜140℃で、かつ、上記架橋性単量体の含有量が上記モノマー組成物100質量%中(上記エチレン性不飽和単量体及び架橋性単量体の合計量100質量%中)0.1〜50質量%であることが好ましい。この場合、本発明の効果を良好に得ることができる。 The emulsion (D) is obtained by emulsion polymerization of a monomer composition comprising an ethylenically unsaturated monomer and a crosslinkable monomer, and is obtained by polymerizing the ethylenically unsaturated monomer. The non-crosslinked polymer has a glass transition temperature of 50 to 140 ° C., and the content of the crosslinkable monomer is 100% by mass of the monomer composition (the ethylenically unsaturated monomer and the crosslinkable monomer). It is preferable that it is 0.1-50 mass%. In this case, the effect of the present invention can be obtained satisfactorily.
上記において、非架橋ポリマーのTgが50℃未満であると、粒子の硬さが低く、塗膜を硬くする効果が小さく、その結果、高圧洗車性が低下するおそれがある。また、架橋性単量体の含有量が0.1質量%未満であると、粒子架橋度が低く、結果的に粒子の強度と硬さが低く、塗膜を硬くする効果が小さくなり、その結果、高圧洗車性が低下するおそれがある。
上記において、非架橋ポリマーのTgが140℃を超えると、架橋粒子が石のように硬くなりすぎ、結果として、塗膜が硬くなりすぎ、凝集破壊しやすくなる。
In the above, when the Tg of the non-crosslinked polymer is less than 50 ° C., the hardness of the particles is low and the effect of hardening the coating film is small, and as a result, the high-pressure car washability may be reduced. In addition, when the content of the crosslinkable monomer is less than 0.1% by mass, the degree of particle crosslinking is low, and as a result, the strength and hardness of the particles are low, and the effect of hardening the coating film is reduced. As a result, the high-pressure car washability may be reduced.
In the above, when the Tg of the non-crosslinked polymer exceeds 140 ° C., the crosslinked particles become too hard like a stone, and as a result, the coating film becomes too hard and is liable to cohesive failure.
本明細書において、ガラス転移温度(Tg)は、上記融点測定方法と同一の方法により得られる工程3の昇温時のチャートから得られる値である。即ち、図2で示されるチャートの矢印で示される温度をTgとした。 In the present specification, the glass transition temperature (Tg) is a value obtained from the chart at the time of temperature increase in Step 3 obtained by the same method as the melting point measuring method. That is, the temperature indicated by the arrow in the chart shown in FIG.
本発明の水性プライマー塗料組成物は、上記必須の各成分(A)、(B)、(C)、(D)に加え、必要に応じ、他の水性樹脂を適宜配合することもできる。他の水性樹脂としては水性アクリル系樹脂、アクリル系エマルション、アミノ樹脂エマルション等が挙げられる。なお、これらの水性樹脂は、後述の顔料分散剤として用いられることがある。 In addition to the essential components (A), (B), (C), and (D), the water-based primer coating composition of the present invention can appropriately contain other water-based resins as necessary. Examples of other aqueous resins include aqueous acrylic resins, acrylic emulsions, amino resin emulsions, and the like. In addition, these aqueous resins may be used as a pigment dispersant described later.
本発明の水性プライマー塗料組成物は、塗料として通常添加される他の配合物、例えば、顔料、界面活性剤、中和剤、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、シリカ等の無機充填剤、導電性カーボン、導電性フィラー、金属粉等の導電性充填剤、有機改質剤、可塑剤等を必要に応じて配合することができる。 The water-based primer coating composition of the present invention can be used in other formulations usually added as coatings, such as pigments, surfactants, neutralizers, stabilizers, thickeners, antifoaming agents, surface conditioners, and leveling agents. , Pigment dispersants, UV absorbers, antioxidants, inorganic fillers such as silica, conductive carbon, conductive fillers, conductive fillers such as metal powders, organic modifiers, plasticizers, etc. as needed Can be blended.
上記増粘剤としては、例えば、会合型ノニオン系ウレタン増粘剤やアルカリ膨潤型増粘剤や無機系の層間化合物であるベントナイト等が挙げられる。
上記顔料としては、酸化チタン、カーボンブラック、酸化鉄、酸化クロム、紺青等の無機顔料やアゾ系顔料、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等の有機顔料等の着色顔料;タルク、沈降性硫酸バリウム等の体質顔料;導電カーボン、アンチモンドープの酸化スズをコートしたウイスカー等の導電顔料;アルミニウム、銅、亜鉛、ニッケル、スズ、酸化アルミニウム等の金属又は合金等の無着色あるいは着色された金属製光輝材等を挙げることができる。
Examples of the thickener include associative nonionic urethane thickener, alkali swelling thickener, bentonite which is an inorganic intercalation compound, and the like.
Examples of the pigment include inorganic pigments such as titanium oxide, carbon black, iron oxide, chromium oxide, and bitumen, and organic pigments such as azo pigments, anthracene pigments, perylene pigments, quinacridone pigments, indigo pigments, and phthalocyanine pigments. Color pigments such as talc, body pigments such as precipitated barium sulfate; conductive pigments such as whiskers coated with conductive carbon and antimony-doped tin oxide; metals or alloys such as aluminum, copper, zinc, nickel, tin, and aluminum oxide Examples thereof include non-colored or colored metallic luster materials.
上記顔料分散剤としては、水性アクリル系樹脂;ビックケミー社製のBYK−190等の酸性ブロック共重合体;スチレン−マレイン酸共重合体;エアプロダクツ社製のサーフィノールGA、サーフィノールT324等のアセチレンジオール誘導体;イーストマンカミカル社製のCMCAB−641−0.5等の水溶性カルボキシメチルセルロースアセテートブチレート等を挙げることができる。これらの顔料分散剤を用いることで、安定な顔料ペーストを調製することができる。上記消泡剤としては、例えば、エアープロダクト社製のサーフィノール104PA及びサーフィノール440等が挙げられる。 Examples of the pigment dispersant include aqueous acrylic resins; acidic block copolymers such as BYK-190 manufactured by Big Chemie; styrene-maleic acid copolymers; acetylenes such as Surfynol GA and Surfynol T324 manufactured by Air Products. Diol derivatives; water-soluble carboxymethylcellulose acetate butyrate such as CMCAB-641-0.5 manufactured by Eastman Comical, and the like can be mentioned. By using these pigment dispersants, a stable pigment paste can be prepared. Examples of the antifoaming agent include Surfynol 104PA and Surfynol 440 manufactured by Air Products.
本発明の水性プライマー塗料組成物は、上記で説明した(A)〜(D)と必要に応じて用いられる他の成分を混合して製造される。特に、顔料を含む水性プライマー塗料組成物を製造する場合、顔料及び顔料分散剤を含む顔料分散ペーストを予め調製しておいて水性プライマー塗料組成物を製造する方法は、製造効率が高い。 The aqueous primer coating composition of the present invention is produced by mixing (A) to (D) described above and other components used as necessary. In particular, when producing an aqueous primer coating composition containing a pigment, the method of producing an aqueous primer coating composition by preparing a pigment dispersion paste containing a pigment and a pigment dispersant in advance has high production efficiency.
本発明の塗膜形成方法は、上述した水性プライマー塗料組成物を基材に塗装する工程及び上塗り塗料を塗装する工程を含む方法である。
上記基材としては、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及びこれらの成形品を挙げることができる。
The coating film forming method of the present invention is a method including a step of coating the above-described aqueous primer coating composition on a substrate and a step of applying a top coating.
Examples of the substrate include polyolefins such as polypropylene (PP) and polyethylene (PE), acrylonitrile styrene (AS), acrylonitrile butadiene styrene (ABS), polyphenylene oxide (PPO), vinyl chloride (PVC), polyurethane ( Examples thereof include plastic materials such as PU) and polycarbonate (PC), and molded products thereof.
上記水性プライマー塗料組成物を基材に塗装する方法は、特に限定されず、エアースプレーやエアレススプレー等のスプレー塗装、ベル塗装、ディスク塗装、カーテンコート、シャワーコート、刷毛塗り等で塗布し、その後、得られたプライマー塗膜の乾燥を行う方法等を挙げることができる。上記乾燥は、自然乾燥及び強制乾燥のいずれで行ってもよいが、塗装効率の面からは強制乾燥を行うことが好ましい。強制乾燥としては、例えば、温風乾燥、近赤外線乾燥、電磁波乾燥等のいずれで行ってもよい。乾燥温度は、基材の熱変形が起こらない温度範囲で選択され、素材温度が100℃以下であることが好ましく、90℃以下であることがより好ましい。なお、乾燥時間は、通常、乾燥温度及び乾燥炉内の風速に依存し、エネルギー効率を考慮して適宜設定される。 The method of applying the water-based primer coating composition to the substrate is not particularly limited, and is applied by spray coating such as air spray or airless spray, bell coating, disk coating, curtain coating, shower coating, brush coating, etc. The method of drying the obtained primer coating film etc. can be mentioned. The drying may be performed by either natural drying or forced drying, but it is preferable to perform forced drying from the viewpoint of coating efficiency. As forced drying, you may carry out by any of warm air drying, near-infrared drying, electromagnetic wave drying, etc., for example. The drying temperature is selected within a temperature range in which the base material is not thermally deformed, and the material temperature is preferably 100 ° C. or lower, and more preferably 90 ° C. or lower. The drying time usually depends on the drying temperature and the wind speed in the drying furnace, and is appropriately set in consideration of energy efficiency.
上記水性プライマー塗料組成物の乾燥膜厚は、好ましくは5〜30μmである。乾燥膜厚が5μm未満であると、薄すぎて連続な均一膜を得られない傾向がある。30μmを超えると、耐水性等が低下する傾向がある。 The dry film thickness of the aqueous primer coating composition is preferably 5 to 30 μm. If the dry film thickness is less than 5 μm, it tends to be too thin to obtain a continuous uniform film. When it exceeds 30 μm, water resistance and the like tend to decrease.
上記水性プライマー塗料組成物の塗装工程で得られたプライマー塗膜上に、上塗り塗料を塗装する工程を行う。上塗り塗料としては特に限定されず、例えば、一液メラミン焼付塗料、二液ウレタン塗料、一液ラッカー塗料等が挙げられる。上記上塗り塗料の塗装方法は特に限定されず、水性プライマー塗料組成物と同様の方法で塗装することができる。 A step of applying a top coating on the primer coating obtained in the coating step of the aqueous primer coating composition is performed. The top coating is not particularly limited, and examples thereof include one-pack melamine baking paint, two-pack urethane paint, and one-pack lacquer paint. The method for applying the top coating is not particularly limited, and it can be applied by the same method as that for the aqueous primer coating composition.
本発明の水性プライマー塗料組成物は、上述した構成を有しているため、得られた複層塗膜において、密着性と耐ガソホール性を両立すること、高圧洗浄による洗車時において、得られた複層塗膜の剥離を抑制すること及び耐湿性を両立すること、が可能である。 Since the water-based primer coating composition of the present invention has the above-described configuration, the obtained multilayer coating film has both adhesion and gasohol resistance, and is obtained at the time of car washing by high-pressure washing. It is possible to suppress peeling of the multilayer coating film and achieve both moisture resistance.
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, 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 ポリプロピレンAP−1の製造
1000ml丸底フラスコに、脱塩水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1000ml丸底フラスコにて、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。
Production Example 1 Production of Polypropylene AP-1 In a 1000 ml round bottom flask, 110 ml of demineralized water, 22.2 g of magnesium sulfate heptahydrate and 18.2 g of sulfuric acid were collected and dissolved with stirring. 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 1000 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.
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。 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分間攪拌し、触媒スラリーを得た。 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.
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、67℃まで昇温し重合時の全圧を0.65MPa、水素濃度を400ppm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、溶媒並びに粘土残渣を除去したところ10.9質量%のポリプロピレントルエン溶液を11kg(1.20kgポリプロピレン)得た。得られたポリプロピレンAP−1の重量平均分子量Mwは300000(Pst換算値)、PP部の結晶化度は45%であった。 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 67 ° C., and the stirring was continued at the same temperature for 2 hours while keeping the total pressure during polymerization at 0.65 MPa and the hydrogen concentration at 400 ppm. 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 the clay residue were removed. As a result, 11 kg (1.20 kg polypropylene) of a 10.9% by mass polypropylene toluene solution was obtained. The resulting polypropylene AP-1 had a weight average molecular weight Mw of 300,000 (Pst equivalent) and a crystallinity of the PP part of 45%.
製造例2 ポリプロピレンAP−2〜AP−6の製造
重合条件を表1に示したように変更した以外は、製造例1と同様にしてポリプロピレンAP−2〜6を製造した。
Production Example 2 Production of polypropylene AP-2 to AP-6 Polypropylene AP-2 to 6 were produced in the same manner as in Production Example 1 except that the polymerization conditions were changed as shown in Table 1.
製造例3 無水マレイン酸変性ポリプロピレンAPM−1の製造
還流冷却管、温度計、攪拌機の付いたガラスフラスコ中に、製造例1で得られたポリプロピレンAP−1400gとトルエン600gとを入れ、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100g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(日本油脂社製、パーブチルI(PBI))30g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。更に、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APM−1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、3.7質量%(0.37mmol/g)であった。また重量平均分子量は140000であった。
Production Example 3 Production of maleic anhydride-modified polypropylene APM-1 Into a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, 400 g of polypropylene AP-1 obtained in Production Example 1 and 600 g of toluene were placed. The inside of the container was replaced with nitrogen gas, and the temperature was raised to 110 ° C. After heating, 100 g of maleic anhydride was added, 30 g of t-butyl peroxyisopropyl monocarbonate (manufactured by NOF Corporation, Perbutyl I (PBI)) 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 white powdery maleic anhydride-modified polymer APM-1. As a result of measuring the infrared absorption spectrum of this modified polymer, the content (graft ratio) of maleic anhydride groups was 3.7% by mass (0.37 mmol / g). The weight average molecular weight was 140,000.
製造例4 無水マレイン酸変性ポリプロピレンAPM−2〜APM−7の製造
使用するポリプロピレン、配合を表2に示したように変更した以外は、製造例3と同様にして無水マレイン酸変性ポリプロピレンAPM−2〜APM−7を製造した。
Production Example 4 Production of maleic anhydride-modified polypropylene APM-2 to APM-7 Maleic anhydride modification in the same manner as in Production Example 3 except that the polypropylene used and the blending were changed as shown in Table 2. Polypropylene APM-2 to APM-7 were produced.
製造例5 水性無水マレイン酸変性ポリプロピレンAPMW−1の製造
還流冷却管、温度計、攪拌機の付いたガラスフラスコ中に、製造例3で得られた無水マレイン酸変性ポリプロピレンAPM−1(重量平均分子量140000、無水マレイン酸グラフト率3.7%)100g及びテトラヒドロフラン150gとを入れ、65℃に加熱して溶解させた。次いでジメチルエタノールアミン5.8g(2化学当量)加え、温度を65℃に保ちながら、60℃のイオン交換水400gを滴下し、転相させた後、酸化防止剤としてハイドロキノン0.1gを加え、ゆっくり温度を上げてテトラヒドロフランを留去し、乳白色の分散体を得た。この分散体の固形分をイオン交換水を加えて20質量%に調整した。この水分散体の粒径は0.1μm以下であった。
Production Example 5 Production of aqueous maleic anhydride-modified polypropylene APMW-1 In a glass flask equipped with a reflux condenser, a thermometer, and a stirrer, the maleic anhydride-modified polypropylene APM-1 obtained in Production Example 3 ( 100 g of a weight average molecular weight of 140,000 and a maleic anhydride graft ratio of 3.7%) and 150 g of tetrahydrofuran were added and dissolved by heating to 65 ° C. Next, 5.8 g (2 chemical equivalents) of dimethylethanolamine was added, and while maintaining the temperature at 65 ° C., 400 g of ion-exchanged water at 60 ° C. was dropped and phase-inverted, and then 0.1 g of hydroquinone was added as an antioxidant, The temperature was slowly raised and the tetrahydrofuran was distilled off to obtain a milky white dispersion. The solid content of this dispersion was adjusted to 20% by mass by adding ion exchange water. The particle size of this aqueous dispersion was 0.1 μm or less.
製造例6 水性無水マレイン酸変性ポリプロピレンAPMW−2〜7の製造
配合量を表3に示したように変更した以外は、製造例5と同様にして水性無水マレイン酸変性ポリプロピレンAPMW−2〜7を製造した。
Production Example 6 Production of Aqueous Maleic Anhydride Modified Polypropylene APMW-2-7 Aqueous maleic anhydride modified polypropylene APMW- in the same manner as in Production Example 5 except that the blending amount was changed as shown in Table 3. 2-7 were produced.
製造例7 水性無水マレイン酸変性ポリプロピレンAPMW−8の製造
攪拌羽根、温度計、滴下装置、温度制御装置及び冷却管を付けた反応装置に、製造例3で得られた無水マレイン酸変性ポリプロピレンAPM−1 100g、トルエン250gを加え、100℃に昇温して溶解し、70℃まで冷却した。その後、ノニオン性界面活性剤エマルゲン220(花王社製、HLB=14.2、固形分100%)15g及びノニオン性界面活性剤エマルゲン147(花王社製、HLB=16.3、固形分100%)15gを加えて溶解し、50℃まで冷却した。温度を50℃に保ったまま、イオン交換水520gを少しずつ加えて、転相乳化した。その後、室温まで冷却して2−アミノ−2−メチル−1−プロパノールを加えてpH=8に調整した後、減圧下で脱トルエン操作を行い、若干のイオン交換水で調整し、固形分20%(AMP固形分15.4%、乳化剤固形分4.6%)のポリプロピレン水分散体を得た。ポリプロピレン水分散体の平均粒径は0.38μmであった。
Production Example 7 Production of aqueous maleic anhydride-modified polypropylene APMW-8 Maleic anhydride obtained in Production Example 3 was added to a reactor equipped with a stirring blade, a thermometer, a dropping device, a temperature control device, and a cooling pipe. 100 g of modified polypropylene APM-1 and 250 g of toluene were added, and the mixture was heated to 100 ° C. to dissolve, and cooled to 70 ° C. Thereafter, 15 g of nonionic surfactant Emulgen 220 (manufactured by Kao Corporation, HLB = 14.2, solid content 100%) and nonionic surfactant Emulgen 147 (manufactured by Kao Corporation, HLB = 16.3, solid content 100%) 15g was added and melt | dissolved, and it cooled to 50 degreeC. While maintaining the temperature at 50 ° C., 520 g of ion-exchanged water was added little by little to carry out phase inversion emulsification. Then, after cooling to room temperature and adding 2-amino-2-methyl-1-propanol to adjust to pH = 8, detoluene operation was performed under reduced pressure, adjusting with some ion-exchanged water, solid content 20 % (AMP solid content 15.4%, emulsifier solid content 4.6%) was obtained as a polypropylene aqueous dispersion. The average particle size of the polypropylene aqueous dispersion was 0.38 μm.
実施例1 塗料の製造
攪拌機の付いた適当な容器に、スーパーフレックス150(第一工業製薬社製、水性ポリウレタン樹脂)12.03部、エピレッツ5003W55(ジャパンエポキシレジン社製、水性エポキシ樹脂)7.47部、上記で得られたAPMW−1 25.27部、内部架橋アクリル粒子エマルション6.02部、顔料ペースト27.77部、脱イオン水19.28部、消泡剤のダイノール604(エアプロダクツ社製)0.72部、増粘剤のASE−60(ロームアンドハース社製)1.44部、ジメチルエタノールアミン(キシダ化学社製)0.01部を順に滴下し、1時間攪拌後目的の塗料を得た。
Example 1 Production of paint In a suitable container equipped with a stirrer, 12.03 parts of Superflex 150 (Daiichi Kogyo Seiyaku Co., Ltd., aqueous polyurethane resin), Epiletts 5003W55 (Japan Epoxy Resin Co., Ltd., aqueous epoxy) Resin) 7.47 parts, 25.27 parts of APMW-1 obtained above, 6.02 parts of internally cross-linked acrylic particle emulsion, 27.77 parts of pigment paste, 19.28 parts of deionized water, Dinol as antifoaming agent 604 (manufactured by Air Products) 0.72 part, 1.44 parts of thickener ASE-60 (manufactured by Rohm and Haas), 0.01 part of dimethylethanolamine (manufactured by Kishida Chemical Co., Ltd.) were added dropwise in this order. The desired paint was obtained after stirring for a period of time.
実施例2〜13及び比較例1〜10
表4〜5に示した塗料配合で原料を配合した以外は、実施例1と同様にして塗料を製造した。
Examples 2 to 13 and Comparative Examples 1 to 10
A paint was produced in the same manner as in Example 1 except that the raw materials were blended in the paint blends shown in Tables 4-5.
なお、上記で使用した顔料分散ペースト、内部架橋アクリル粒子エマルションは、以下の方法で製造した。
(顔料分散ペーストの製造)
攪拌機の付いた適当な容器に、水性アクリル樹脂(固形分酸価:50mgKOH/g、重量平均分子量:30000、不揮発分:30質量%)11.75部、サーフィノールT324(エアープロダクツ社製顔料分散剤)2.07部、サーフォノール440(エアープロダクツ社製消泡剤)1.61部、脱イオン水38.5部、カーボンブラックECP600JD(ライオン社製導電カーボン)2.54部、タイピュア−R960(デュポン社製酸化チタン顔料)37.64部、ニプシール50B(ニホンシリカ社製のシリカ)5.89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にてグライドゲージで20μ以下になるまで分散を行い、顔料分散ペーストを得た。
この顔料分散ペーストは不揮発分52質量%で粘度は60KU(20℃)であった。
The pigment dispersion paste and the internally crosslinked acrylic particle emulsion used above were produced by the following method.
(Manufacture of pigment dispersion paste)
In an appropriate container equipped with a stirrer, 11.75 parts of an aqueous acrylic resin (solid content acid value: 50 mgKOH / g, weight average molecular weight: 30000, nonvolatile content: 30% by mass), Surfynol T324 (pigment dispersion manufactured by Air Products) Agent) 2.07 parts, Surfonol 440 (air products manufactured antifoaming agent) 1.61 parts, deionized water 38.5 parts, carbon black ECP600JD (Lion Corporation conductive carbon) 2.54 parts, Taipure-R960 ( 37.64 parts of DuPont Titanium Oxide Pigment) and 5.89 parts of Nipsil 50B (Nihon Silica Silica) were added in order under stirring, and after stirring for 1 hour, glide with a 1.4-liter dynomill for laboratory use. Dispersion was performed with a gauge until the thickness became 20 μm or less to obtain a pigment dispersion paste.
This pigment dispersion paste had a nonvolatile content of 52% by mass and a viscosity of 60 KU (20 ° C.).
(内部架橋アクリル粒子エマルションAC−1〜6の製造)
脱イオン水220部にペレックス−SSH(花王社製、アルキルジフェニルエーテルジスルホン酸ナトリウム)5.0部を加えた溶液に、表6に示した配合のエチレン不飽和単量体混合物100部をゆっくり加え、乳化物を作成した。
次に、冷却器、温度計及び攪拌器を備えたガラスフラスコに、脱イオン水100部を入れ、80℃に加熱した。その後、上記乳化物及び脱イオン水15.0部と過硫酸アンモニウム0.03部からなる開始剤水溶液を3時間かけて滴下し目的の架橋アクリル粒子エマルションを得た。また、各エマルションの架橋性単量体を除いたアクリルのガラス転移温度(Tg)は表6に示した通りであった。
(Production of internally crosslinked acrylic particle emulsion AC-1 to 6)
To a solution obtained by adding 5.0 parts of Perex-SSH (manufactured by Kao Corporation, sodium alkyldiphenyl ether disulfonate) to 220 parts of deionized water, 100 parts of an ethylenically unsaturated monomer mixture having the composition shown in Table 6 was slowly added. An emulsion was made.
Next, 100 parts of deionized water was put into a glass flask equipped with a cooler, a thermometer and a stirrer, and heated to 80 ° C. Thereafter, an initiator aqueous solution composed of the above emulsion and 15.0 parts of deionized water and 0.03 part of ammonium persulfate was dropped over 3 hours to obtain a target crosslinked acrylic particle emulsion. Further, the glass transition temperature (Tg) of the acrylic excluding the crosslinkable monomer in each emulsion was as shown in Table 6.
〔評価〕
得られた塗料を、中性洗剤で洗浄したポリプロピレン素材(大きさ:70mm×260mm×3mm)にスプレー塗装(乾燥膜厚10μm)し、80℃で10分乾燥した。冷却後、溶剤系2液メタリックベース塗料(日本ビー・ケミカル株式会社製)を乾燥膜厚15μm、続いて、溶剤系2液クリアー(日本ビー・ケミカル株式会社製)を乾燥膜厚30μmになるようにスプレー塗装し、80℃で30分乾燥してテストピースを作製した。
得られたテストピースについて、以下の方法により、碁盤目剥離試験、耐湿試験、耐ガソホール試験、高圧洗車性試験を行った。結果を表4〜5に示した。
[Evaluation]
The obtained paint was spray-coated (dry film thickness 10 μm) on a polypropylene material (size: 70 mm × 260 mm × 3 mm) washed with a neutral detergent, and dried at 80 ° C. for 10 minutes. After cooling, solvent-based two-component metallic base paint (manufactured by Nippon Bee Chemical Co., Ltd.) has a dry film thickness of 15 μm, and solvent-based two-component clear (manufactured by Nippon Bee Chemical Co., Ltd.) has a dry film thickness of 30 μm. A test piece was prepared by spray coating and drying at 80 ° C. for 30 minutes.
The obtained test piece was subjected to a cross-cut peel test, a moisture resistance test, a gasohol resistance test, and a high-pressure car wash test by the following methods. The results are shown in Tables 4-5.
(碁盤目剥離試験)
JIS K5400に準拠して、碁盤目セロテープ(登録商標)剥離試験を行った。2mm角の100個の碁盤目を用意し、セロハンテープ剥離試験を行い、剥がれなかった碁盤目数を数えた。評価基準は以下の通りである。
○:0/100(剥離なし)
△:1/100〜50/100(50%以下剥離)
×:51/100〜100/100(51%以上剥離)
(Cross-cut peel test)
In accordance with JIS K5400, a cross-cut cello tape (registered trademark) peel test was performed. 100 grids of 2 mm square were prepared, and a cellophane tape peeling test was performed to count the number of grids that were not peeled off. The evaluation criteria are as follows.
○: 0/100 (no peeling)
Δ: 1/100 to 50/100 (50% or less peeling)
X: 51 / 100-100 / 100 (51% or more peeling)
(耐ガソホール性試験)
塗装後のポリオレフィン基材片(3cm×3cm)を、レギュラーガソリンにエタノールを10容量%添加して得られるガソホールに浸漬した後、塗膜の剥離が端部が2mmに達するまでの時間を測定し、30分以上を○、それ未満を×とした。
(Gasohol resistance test)
After immersing the polyolefin substrate piece (3cm x 3cm) after coating in gasohol obtained by adding 10% by volume of ethanol to regular gasoline, measure the time until the peeling of the coating reaches 2mm. , 30 minutes or more was marked with ◯, less than that was marked with ×.
(耐湿性試験)
塗装後のポリオレフィン基材を50℃、湿度98%の雰囲気下で10日間放置した後、上記碁盤目剥離試験及び外観評価を行った。上記耐湿試験で行った外観評価の評価基準は以下の通りである。
○:初期(耐湿試験前)と比較して異常がない場合
△:初期(耐湿試験前)と比較して塗膜に少しの膨れや艶引けが見られる場合
×:初期(耐湿試験前)と比較して塗膜に膨れや艶引けがある場合
(Moisture resistance test)
The polyolefin substrate after coating was allowed to stand for 10 days in an atmosphere of 50 ° C. and 98% humidity, and then subjected to the cross-cut peel test and appearance evaluation. The evaluation criteria of the appearance evaluation performed in the moisture resistance test are as follows.
○: When there is no abnormality compared with the initial stage (before the moisture resistance test) Δ: When the coating film is slightly swollen or glossy compared with the initial stage (before the moisture resistance test) ×: Initial stage (before the moisture resistance test) If the coating has swelling or gloss
(高圧洗車性試験)
塗装後のポリオレフィン素材において、カッターナイフにより素材に達する切れ目を7cmの長さで入れ、このポリオレフィン素材を水平に置いて固定し、20℃、水圧70kg/cm2の高圧水を、プライマー塗膜面から30度の角度で、20cmの距離から30秒間噴射した。ポリオレフィン素材からプライマー塗膜が浮き上がった長さを測定し、浮き上がりが全く生じなかったものを○、極小の浮き上がりが生じたもの(1mm以上2mm未満)を〇△、少し浮き上がりが生じたもの(2mm以上5mm未満)を△、浮き上がりが5mm以上生じたものを×とした。
(High pressure car wash test)
In the polyolefin material after painting, a cut to reach the material with a cutter knife is made with a length of 7 cm, this polyolefin material is placed horizontally and fixed, and high-pressure water at 20 ° C. and a water pressure of 70 kg / cm 2 is applied to the primer coating surface. 30 seconds from a distance of 20 cm at an angle of 30 degrees. Measure the length of the primer coating lifted from the polyolefin material, ○ if there was no lift, ○ △ if there was a minimal lift (1 mm or more and less than 2 mm), slightly lifted (2 mm) △ is less than 5 mm), and x is the one where the lift is 5 mm or more.
表4から、実施例で得られたテストピースは、すべての性能に優れていた。よって、密着性及び耐ガソホール性の両立、高圧洗車性及び耐湿性の両立が可能であることが明らかとなった。一方、表5から、比較例では、すべての性能を満たすものは得られなかった。 From Table 4, the test pieces obtained in the examples were excellent in all performances. Therefore, it became clear that it was possible to achieve both cohesion and gasohol resistance, and high-pressure car wash and moisture resistance. On the other hand, from Table 5, in the comparative example, what satisfy | filled all performance was not obtained.
本発明の水性プライマー塗料組成物は、種々のプラスチック基材及びこれらの成形品等に好適に用いることができる。 The aqueous primer coating composition of the present invention can be suitably used for various plastic substrates and molded articles thereof.
Claims (5)
前記(A)、(B)、(C)及び(D)の合計量100質量%中、固形分換算で、
前記(A)の含有量が15〜60質量%、
前記(B)の含有量が10〜50質量%、
前記(C)の含有量が20〜50質量%、
前記(D)の含有量が5〜20質量%であり、
前記(A)は、その結晶化度が35〜55%で、かつ、重量平均分子量が50000〜200000である水性ポリプロピレン系樹脂である
ことを特徴とする水性プライマー塗料組成物。 An aqueous primer coating composition comprising an aqueous non-chlorinated polyolefin resin (A), an aqueous polyurethane resin (B), an aqueous epoxy resin (C) and an internally crosslinked acrylic particle emulsion (D),
In the total amount of 100% by mass of (A), (B), (C) and (D), in terms of solid content,
The content of (A) is 15 to 60% by mass,
The content of (B) is 10 to 50% by mass,
The content of (C) is 20 to 50% by mass,
The content of (D) is 5 to 20% by mass,
The aqueous primer coating composition characterized in that (A) is an aqueous polypropylene resin having a crystallinity of 35 to 55% and a weight average molecular weight of 50,000 to 200,000.
前記エチレン性不飽和単量体を重合して得られる非架橋ポリマーのガラス転移温度が50〜140℃で、かつ、
前記架橋性単量体の含有量が前記モノマー組成物100質量%中0.1〜50質量%である請求項1、2又は3記載の水性プライマー塗料組成物。 The emulsion (D) is obtained by emulsion polymerization of a monomer composition comprising an ethylenically unsaturated monomer and a crosslinkable monomer,
The glass transition temperature of the non-crosslinked polymer obtained by polymerizing the ethylenically unsaturated monomer is 50 to 140 ° C., and
The water-based primer coating composition according to claim 1, 2, or 3, wherein the content of the crosslinkable monomer is 0.1 to 50% by mass in 100% by mass of the monomer composition.
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