JPH0673308A - One-pack water-based primer composition - Google Patents
One-pack water-based primer compositionInfo
- Publication number
- JPH0673308A JPH0673308A JP23039892A JP23039892A JPH0673308A JP H0673308 A JPH0673308 A JP H0673308A JP 23039892 A JP23039892 A JP 23039892A JP 23039892 A JP23039892 A JP 23039892A JP H0673308 A JPH0673308 A JP H0673308A
- Authority
- JP
- Japan
- Prior art keywords
- component
- primer composition
- emulsion
- aqueous primer
- molecular weight
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 74
- 229920001577 copolymer Polymers 0.000 claims abstract description 30
- 239000010419 fine particle Substances 0.000 claims abstract description 30
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 19
- 239000012736 aqueous medium Substances 0.000 claims abstract description 13
- 239000000839 emulsion Substances 0.000 claims description 51
- 125000003277 amino group Chemical group 0.000 claims description 18
- 229920006158 high molecular weight polymer Polymers 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- -1 reinforcing property Substances 0.000 abstract description 10
- 230000003014 reinforcing effect Effects 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 23
- 229920000642 polymer Polymers 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000012986 chain transfer agent Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000003973 paint Substances 0.000 description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 7
- 230000002787 reinforcement Effects 0.000 description 7
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 6
- 230000035699 permeability Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 150000002168 ethanoic acid esters Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000012874 anionic emulsifier Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000012875 nonionic emulsifier Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- CBOSJQAECKBKFZ-UHFFFAOYSA-N (1-chloro-2-hydroxypropyl) prop-2-enoate Chemical compound CC(O)C(Cl)OC(=O)C=C CBOSJQAECKBKFZ-UHFFFAOYSA-N 0.000 description 1
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- DEGZUQBZHACZKW-UHFFFAOYSA-N 2-(methylamino)ethyl 2-methylprop-2-enoate Chemical compound CNCCOC(=O)C(C)=C DEGZUQBZHACZKW-UHFFFAOYSA-N 0.000 description 1
- ULEVTQHCVWIDPC-UHFFFAOYSA-N 2-(methylamino)ethyl prop-2-enoate Chemical compound CNCCOC(=O)C=C ULEVTQHCVWIDPC-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- XJELOQYISYPGDX-UHFFFAOYSA-N ethenyl 2-chloroacetate Chemical compound ClCC(=O)OC=C XJELOQYISYPGDX-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、各種基材に対して優れ
た浸透性，補強性，密着性および耐水性を発揮し、各種
上塗り塗料との密着性に優れた一成分系水性プライマー
組成物に関するものである。The present invention relates to a one-component water-based primer composition which exhibits excellent penetration, reinforcement, adhesion and water resistance to various base materials and excellent adhesion to various top coats. It is about things.
【０００２】[0002]
【従来の技術】近年、無機建材は、アスベスト規制等に
より、基材の脆弱化が著しく、従来のエマルジョンでは
基材表面層の補強が非常に困難になってきた。そこで、
エマルジョンの粒子径を小さくしたもの、密着性を向上
させる官能基を共重合したエマルジョンが市場に出ては
いるが、いずれも基材補強性に関して未だ不充分であ
る。2. Description of the Related Art In recent years, as for inorganic building materials, the base material has been remarkably weakened due to asbestos regulations, and it has become very difficult to reinforce the base material surface layer with conventional emulsions. Therefore,
Although there are on the market, emulsions having a smaller particle size and copolymers having a functional group for improving adhesiveness are on the market, both of which are still insufficient in terms of reinforcing the base material.
【０００３】[0003]
【発明が解決しようとする課題】一方、浸透性に優れた
特徴から水溶性樹脂を利用したシーラーが用いられてい
る場合があるか、水溶性樹脂単独では、浸透性および補
強性は優れてはいるものもあるが、耐水性に関しては、
硬化剤の併用を除いては耐水性の発現はなく、シーラー
として不適当である。そして、近年、水溶性樹脂を保護
コロイドとしたエマルジョンが種々出回っているが、充
分な基材補強性が得られず、耐水性等もシーラーとして
使用可能な範囲のものではなく、これら水系１液型シー
ラーで溶剤系と同等の性能を発揮するのは現状では困難
である。On the other hand, there are cases where a sealer using a water-soluble resin is used because of its excellent permeability, or the water-soluble resin alone does not have excellent permeability and reinforcement. There are some, but regarding water resistance,
Except for the combined use of a curing agent, it does not exhibit water resistance and is unsuitable as a sealer. In recent years, various emulsions in which a water-soluble resin is used as a protective colloid have been available on the market. However, sufficient base material reinforcement cannot be obtained, and water resistance is not within the range usable as a sealer. At present, it is difficult to achieve the same performance as a solvent-based type sealer.
【０００４】また、鋼板，プラスチック素材に関しても
溶剤規制，公害，衛生面等の問題から、水系塗料への移
行が、近年、急速に目立っている。しかし、プラスチッ
ク等の表面の極性が著しく小さい素材は、塗膜の密着性
が非常に悪く、一部の溶剤系塗料しか使用できないのが
現状であり、水系１液型プライマーでは溶剤系の代替は
困難である。Also, with respect to steel sheets and plastic materials, the shift to water-based paints has been rapidly conspicuous in recent years due to problems such as solvent regulation, pollution, and hygiene. However, for materials such as plastics whose surface polarity is extremely low, the adhesion of the coating film is very poor, and at present, only some solvent-based paints can be used. Have difficulty.
【０００５】本発明は、このような事情に鑑みなされた
もので、各種基材への浸透性，密着性，補強性，耐水
性，上塗り塗膜との密着性の全てに優れた一成分系水性
プライマー組成物の提供を目的とする。The present invention has been made in view of the above circumstances, and is a one-component system excellent in penetration into various substrates, adhesion, reinforcement, water resistance, and adhesion to a top coating film. It is intended to provide an aqueous primer composition.
【０００６】[0006]
【課題を解決するための手段】上記の目的を達成するた
め、本発明は、下記の（Ａ）成分が下記の（Ｂ）成分に
よって被覆保護されている二重構造の微粒子が、水性媒
体中に含有され、上記（Ａ）成分および（Ｂ）成分の双
方とも数平均分子量が１０００〜１００００の範囲に設
定されている一成分系水性プライマー組成物を第１の要
旨とし、 （Ａ）グリシジル基含有単量体とエチレン性不飽和単量
体とからなる共重合体。 （Ｂ）アミノ基含有単量体とエチレン性不飽和単量体と
からなる共重合体。 下記の（Ｃ）成分が、下記の（Ｅ）成分を介して下記の
（Ｄ）成分によって被覆保護されている三重構造の微粒
子が、水性媒体中に含有され、上記（Ｃ）〜（Ｅ）成分
の全ての数平均分子量が１０００〜１００００の範囲に
設定されている一成分系水性プライマー組成物を第２の
要旨とする。 （Ｃ）グリシジル基含有単量体からなる共重合体。 （Ｄ）アミノ基含有単量体からなる共重合体。 （Ｅ）エチレン性不飽和単量体からなる共重合体。In order to achieve the above object, the present invention provides a fine particle having a double structure in which the following component (A) is covered and protected by the following component (B) in an aqueous medium. And the number-average molecular weight of both the component (A) and the component (B) is set in the range of 1,000 to 10,000 as the first gist, and the (A) glycidyl group A copolymer comprising a contained monomer and an ethylenically unsaturated monomer. (B) A copolymer composed of an amino group-containing monomer and an ethylenically unsaturated monomer. Fine particles having a triple structure in which the following component (C) is covered and protected by the following component (D) via the following component (E) are contained in an aqueous medium, and the above (C) to (E) are included. The second gist is a one-component aqueous primer composition in which all the number average molecular weights of the components are set in the range of 1,000 to 10,000. (C) A copolymer composed of a glycidyl group-containing monomer. (D) A copolymer composed of an amino group-containing monomer. (E) A copolymer composed of an ethylenically unsaturated monomer.
【０００７】[0007]
【作用】すなわち、本発明者らは、各種基材への浸透
性，密着性，補強性，耐水性および上塗り塗膜との密着
性の全てに優れた水性プライマー組成物を得るために一
連の研究を重ねた。その結果、グリシジル基含有単量体
とエチレン性不飽和単量体からなる共重合体（Ａ成分）
がアミノ基含有単量体とエチレン性不飽和単量体からな
る共重合体（Ｂ成分）によって被覆保護され、かつ上記
ＡおよびＢ成分とも特定の数平均分子量に設定された二
重構造の微粒子を含有する一成分系水性プライマー組成
物を用いると、所期の目的を達成できることを見出し
た。また、グリシジル基含有単量体からなる共重合体
（Ｃ成分）が、エチレン性不飽和単量体からなる共重合
体（Ｅ成分）を介してアミノ基含有単量体からなる共重
合体（Ｄ成分）によって被覆され、かつ上記Ｃ〜Ｅ成分
が特定の数平均分子量に設定された三重構造の微粒子を
含有する一成分系水性プライマー組成物を用いると、上
記二重構造の微粒子含有一成分系水性プライマー組成物
と同様、所期の目的を達成できることを見出し本発明に
到達した。In other words, the present inventors have made a series of preparations for obtaining an aqueous primer composition which is excellent in permeability to various substrates, adhesion, reinforcement, water resistance and adhesion to a top coating film. Repeated research. As a result, a copolymer composed of a glycidyl group-containing monomer and an ethylenically unsaturated monomer (component A)
Is a fine particle having a double structure in which is protected by coating with a copolymer (component B) composed of an amino group-containing monomer and an ethylenically unsaturated monomer, and both the components A and B are set to have a specific number average molecular weight. It was found that the intended purpose can be achieved by using a one-component aqueous primer composition containing Further, a copolymer (C component) composed of a glycidyl group-containing monomer is a copolymer (A component) composed of an amino group-containing monomer via a copolymer (E component) composed of an ethylenically unsaturated monomer. When using a one-component aqueous primer composition containing fine particles of triple structure in which the above-mentioned components C to E are set to a specific number average molecular weight, As with the water-based aqueous primer composition, the inventors have found that the intended purpose can be achieved, and arrived at the present invention.
【０００８】つぎに、本発明について詳しく説明する。Next, the present invention will be described in detail.
【０００９】本発明に用いられる水性媒体としては、水
が最適である。しかし、基材に対する浸透性を高めたり
することを目的として、水に易溶性の有機溶剤を併用し
ても差し支えない。このような有機溶剤としては、イソ
プロピルアルコール，メタノール，エタノール，プロパ
ノール，アセトン，メチルエチルケトン，ジオキサン，
エチレングリコール，プロピレングリコール，グリセリ
ン，メチルカルビトール，エチルカルビトール，ブチル
カルビトール，メチルセロソルブ，エチルセロソルブ，
酢酸，上記アルコールの酢酸エステル類，上記カルビト
ールの酢酸エステル類および上記セロソルブの酢酸エス
テル類等があげられる。このような有機溶剤を併用する
場合には、得られる一成分系水性プライマー組成物の安
全性の観点から、媒体全体の５０重量％（以下「％」と
略す）以下の範囲で使用することが好ましく、特に２０
％以下の範囲で使用することが好ましい。Water is the most suitable as the aqueous medium used in the present invention. However, an easily soluble organic solvent may be used in combination with water for the purpose of increasing the permeability to the substrate. Such organic solvents include isopropyl alcohol, methanol, ethanol, propanol, acetone, methyl ethyl ketone, dioxane,
Ethylene glycol, propylene glycol, glycerin, methyl carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve,
Examples thereof include acetic acid, acetic acid esters of the above alcohols, acetic acid esters of the above carbitol, and acetic acid esters of the above cellosolve. When such an organic solvent is used in combination, from the viewpoint of the safety of the obtained one-component aqueous primer composition, it may be used within the range of 50% by weight (hereinafter abbreviated as “%”) of the entire medium. Preferably 20 in particular
It is preferably used in the range of not more than%.
【００１０】本発明の一成分系水性プライマー組成物
は、２通りの形態に分けられる。一つは、上記水性媒体
中に、図１に示すように、下記の（Ａ）成分１が（Ｂ）
成分２によって被覆保護されている二重構造の微粒子が
含有されたものである。The one-component aqueous primer composition of the present invention can be divided into two forms. One is the following (A) component 1 (B) in the aqueous medium as shown in FIG.
It contains fine particles of a double structure which are covered and protected by the component 2.
【００１１】（Ａ）グリシジル基含有単量体およびエチ
レン性不飽和単量体とから共重合体。 （Ｂ）アミノ基含有単量体およびエチレン性不飽和単量
体とから共重合体。(A) A copolymer comprising a glycidyl group-containing monomer and an ethylenically unsaturated monomer. (B) A copolymer comprising an amino group-containing monomer and an ethylenically unsaturated monomer.
【００１２】もう一つは、上記水性媒体中に、図２に示
すように、下記の（Ｃ）成分３が、下記の（Ｅ）成分５
を介して下記の（Ｄ）成分４によって被覆保護されてい
る三重構造の微粒子が含有されたものである。Second, as shown in FIG. 2, the following (C) component 3 and the following (E) component 5 are added to the above aqueous medium.
The fine particles having a triple structure, which are covered with and protected by the following (D) component 4, are contained.
【００１３】（Ｃ）グリシジル基含有単量体を主成分と
する共重合体。 （Ｄ）アミノ基含有単量体を主成分とする共重合体。 （Ｅ）エチレン性不飽和単量体を主成分とする共重合
体。(C) A copolymer whose main component is a glycidyl group-containing monomer. (D) A copolymer containing an amino group-containing monomer as a main component. (E) A copolymer containing an ethylenically unsaturated monomer as a main component.
【００１４】上記（Ａ）成分に用いられるグリシジル基
含有単量体としては、グリシジルアクリレート，グリシ
ジルメタクリレート等があげられる。これらは単独でも
しくは併せて用いられる。Examples of the glycidyl group-containing monomer used as the component (A) include glycidyl acrylate and glycidyl methacrylate. These may be used alone or in combination.
【００１５】また、上記グリシジル基含有単量体ととも
に用いられるエチレン性不飽和単量体としては、通常の
エマルジョン重合に用いられる単量体があげられ、例え
ば酢酸ビニル，アクリル酸アルキルエステル，メタクリ
ル酸アルキルエステル，スチレン，アクリロニトリル，
メタクリロニトリル等の疎水性単量体があげられる。こ
れらは単独でもしくは併せて用いられる。なお、上記エ
チレン性不飽和単量体を用いて本発明の一成分系水性プ
ライマー組成物を作製する場合には、上記疎水性単量体
とともにアクリル酸，メタクリル酸，アクリル酸もしく
はメタクリル酸のアミド類，メチロール化アミド類，ア
ルコキシメチル化アミド類，アルキルアミノエステル
類，モノクロル酢酸ビニル，１−クロロ−２−ヒドロキ
シプロピルアクリレート等の親水性単量体を併用するこ
ともできる。Examples of the ethylenically unsaturated monomer used together with the glycidyl group-containing monomer include monomers used in ordinary emulsion polymerization, such as vinyl acetate, acrylic acid alkyl ester, and methacrylic acid. Alkyl ester, styrene, acrylonitrile,
Hydrophobic monomers such as methacrylonitrile may be mentioned. These may be used alone or in combination. When the one-component aqueous primer composition of the present invention is prepared using the above ethylenically unsaturated monomer, acrylic acid, methacrylic acid, amide of acrylic acid or methacrylic acid is used together with the above hydrophobic monomer. Hydrophilic monomers such as compounds, methylolated amides, alkoxymethylated amides, alkylaminoesters, vinyl monochloroacetate, and 1-chloro-2-hydroxypropyl acrylate can be used in combination.
【００１６】上記（Ｂ）成分に用いられるアミノ基含有
単量体としては、一級，二級または三級アミノ基含有単
量体が用いられ、具体的には、アクリル酸モノメチルア
ミノエチル，アクリル酸ジメチルアミノエチル，アクリ
ル酸ジエチルアミノエチル，メタクリル酸モノメチルア
ミノエチル，メタクリル酸ジメチルアミノエチル，メタ
クリル酸ジエチルアミノエチル，ジメチルアミノプロピ
ルアクリルアミド，ジメチルアミノプロピルメタクリル
アミド，アリルアミン等があげられる。これらは単独で
もしくは併せて用いられる。As the amino group-containing monomer used in the component (B), a primary, secondary or tertiary amino group-containing monomer is used. Specifically, monomethylaminoethyl acrylate, acrylic acid Examples thereof include dimethylaminoethyl, diethylaminoethyl acrylate, monomethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, and allylamine. These may be used alone or in combination.
【００１７】また、上記アミノ基含有単量体とともに用
いられるエチレン性不飽和単量体としては、上記Ａ成分
に用いられるものと同様のものがあげられる。As the ethylenically unsaturated monomer used together with the amino group-containing monomer, the same ones as those used for the component A can be mentioned.
【００１８】一方、前記三重構造の微粒子を構成する
（Ｃ）〜（Ｅ）成分中のグリシジル基含有単量体，アミ
ノ基含有単量体，エチレン性不飽和単量体としては、そ
れぞれ上記二重構造の微粒子を構成する各単量体と同様
のものがあげられる。On the other hand, the glycidyl group-containing monomer, the amino group-containing monomer, and the ethylenically unsaturated monomer in the components (C) to (E) constituting the fine particles having the above-mentioned triple structure are respectively the above-mentioned two. Examples thereof include the same monomers as those constituting the fine particles having a heavy structure.
【００１９】本発明の一成分系水性プライマー組成物に
は、上記（Ａ）および（Ｂ）成分または（Ｃ）〜（Ｅ）
成分以外に、これを希釈して使用する際の用いる水、あ
るいは必要に応じて可塑剤，充填剤，顔料，分散剤，増
粘剤，溶剤，消泡剤，防腐剤等の通常の塗料に用いられ
る添加剤を適宜に配合することができる。The one-component aqueous primer composition of the present invention comprises the above-mentioned components (A) and (B) or (C) to (E).
In addition to the components, it can be used for water used when diluting it, or for ordinary paints such as plasticizers, fillers, pigments, dispersants, thickeners, solvents, defoamers, preservatives, etc. The additives used can be blended appropriately.
【００２０】本発明の一成分系水性プライマー組成物
は、つぎの二通りの方法によって得られる。まず、二
重構造の微粒子を含有する水性プライマー組成物は、例
えばつぎのようにして得られる。すなわち、水性媒体と
乳化液との配合物に、グリシジル基含有単量体，エチレ
ン性不飽和単量体および連鎖移動剤が含有された乳化液
の一部と、重合開始剤を水に溶解したものを滴下する。
つぎに、残りの乳化液を滴下して滴下反応し、完結反応
を行う。これに、アミノ基含有単量体，エチレン性不飽
和単量体および連鎖移動剤を含む乳化液を滴下し反応さ
せることにより、水性媒体中に、二重構造の微粒子（図
１参照）を含む水性プライマー組成物が得られる。The one-component aqueous primer composition of the present invention can be obtained by the following two methods. First, an aqueous primer composition containing fine particles having a double structure is obtained, for example, as follows. That is, in a mixture of an aqueous medium and an emulsion, a part of the emulsion containing a glycidyl group-containing monomer, an ethylenically unsaturated monomer and a chain transfer agent, and a polymerization initiator were dissolved in water. Drop things.
Next, the rest of the emulsion is dropped to carry out a dropping reaction to complete the reaction. An emulsion containing a monomer containing an amino group, an ethylenically unsaturated monomer, and a chain transfer agent is added dropwise to the mixture to react with each other, whereby fine particles having a double structure (see FIG. 1) are contained in the aqueous medium. An aqueous primer composition is obtained.
【００２１】つぎに、三重構造の微粒子を含有する水
性プライマー組成物は、例えばつぎのようにして得られ
る。すなわち、水性媒体と乳化液との配合物に、グリシ
ジル基含有単量体，エチレン性不飽和単量体および連鎖
移動剤が含有された乳化液の一部と重合開始剤を水に溶
解したものを滴下する。つぎに、残りの乳化液を滴下し
て滴下反応させ、完結反応を行う。これに、エチレン性
不飽和単量体，連鎖移動剤を含む乳化液を滴下し反応さ
せる。完結反応を行った後、さらにアミノ基含有単量
体，エチレン性不飽和単量体および連鎖移動剤を含む乳
化液を滴下し反応させることにより、水性媒体中に、三
重構造の微粒子（図２参照）を含む水性プライマー組成
物が得られる。Next, an aqueous primer composition containing fine particles having a triple structure is obtained, for example, as follows. That is, a mixture of an aqueous medium and an emulsion, a part of an emulsion containing a glycidyl group-containing monomer, an ethylenically unsaturated monomer and a chain transfer agent and a polymerization initiator dissolved in water Is dripped. Next, the rest of the emulsion is added dropwise to cause a drop reaction to complete the reaction. An emulsified liquid containing an ethylenically unsaturated monomer and a chain transfer agent is added dropwise to this and reacted. After the completion reaction is completed, an emulsion containing an amino group-containing monomer, an ethylenically unsaturated monomer and a chain transfer agent is further added dropwise to cause a reaction, whereby fine particles having a triple structure (see FIG. An aqueous primer composition is obtained which comprises (cf.
【００２２】このようにして得られる一成分系水性プラ
イマー組成物の各微粒子は、コア部およびシェル部とも
数平均分子量が１０００〜１００００の低分子量の範囲
に設定する必要がある。さらに、三重構造の微粒子の場
合は、コア部とシェル部との間に形成される中間部であ
るエチレン性不飽和単量体の共重合体の数平均分子量も
上記と同様１０００〜１００００の低分子量の範囲に設
定する必要がある。すなわち、上記数平均分子量が１０
００未満では、ポリマーの凝集力が著しく低下するた
め、基材の補強効果も大幅に劣化する。また、ポリマー
の架橋が不充分な場合も同様である。そして、数平均分
子量が１００００を超えると、基材への浸透性が著しく
低下するため、含浸補強効果が不充分となるからであ
る。The fine particles of the one-component aqueous primer composition thus obtained need to have a low molecular weight range of 1,000 to 10,000 in both the core and shell. Further, in the case of fine particles having a triple structure, the number average molecular weight of the copolymer of the ethylenically unsaturated monomer, which is the intermediate portion formed between the core portion and the shell portion, is as low as 1,000 to 10,000 as in the above. It is necessary to set it in the molecular weight range. That is, the number average molecular weight is 10
When it is less than 00, the cohesive force of the polymer is remarkably reduced, and the reinforcing effect of the base material is significantly deteriorated. The same applies when the crosslinking of the polymer is insufficient. If the number average molecular weight exceeds 10,000, the permeability into the base material is significantly reduced, and the impregnation reinforcement effect becomes insufficient.
【００２３】上記分子量調整のために連鎖移動剤が用い
られ、例えば連鎖移動効果のあるアルキルメルカプタン
類，長鎖アルキルメルカプタン類，チオール基含有の酸
化合物，芳香族系のメルカプタン類，アルコール類，ハ
ロゲン化炭化水素類等があげられる。A chain transfer agent is used to adjust the molecular weight, and examples thereof include alkyl mercaptans having a chain transfer effect, long-chain alkyl mercaptans, thiol group-containing acid compounds, aromatic mercaptans, alcohols and halogens. Chemical hydrocarbons and the like can be mentioned.
【００２４】上記製法において、乳化重合する際に用い
られる乳化剤としては、アルキル硫酸ナトリウム，アル
キルベンゼンスルホン酸ナトリウム，アルキルスルホコ
ハク酸ナトリウム，アルキルエーテル硫酸ナトリウム，
ポリオキシエチレンアルキルエーテル，ポリオキシエチ
レンアルキルフェノールエーテル等の通常の乳化剤があ
げられる。In the above-mentioned production method, as the emulsifying agent used for emulsion polymerization, sodium alkylsulfate, sodium alkylbenzenesulfonate, sodium alkylsulfosuccinate, sodium alkylethersulfate,
Usual emulsifiers such as polyoxyethylene alkyl ether and polyoxyethylene alkylphenol ether are included.
【００２５】また、共重合を行う際に用いる重合開始剤
としては、過酸化ベンゾイル、アゾビスイソブチロニト
リル、２，２′−アゾビスアミノジプロパン塩酸塩、過
硫酸アンモン、過硫酸カリウム等があげられる。The polymerization initiator used for the copolymerization is benzoyl peroxide, azobisisobutyronitrile, 2,2'-azobisaminodipropane hydrochloride, ammonium persulfate, potassium persulfate, etc. Can be given.
【００２６】このようにして得られる一成分系水性プラ
イマー組成物は、グリシジル基，アミノ基が反応性を有
するために、接触の度合いが高いとゲル化が生じる。こ
のため、ある程度は接触していても差し支えないが、可
能な限りグリシジル基とアミノ基とがエマルジョン形態
では接触していないことが好ましく、エマルジョンの造
膜が開始して始めて両者の官能基が接触し架橋が生じる
ことが望ましい。Since the glycidyl group and the amino group have reactivity in the one-component aqueous primer composition thus obtained, gelation occurs when the degree of contact is high. For this reason, it may be contacted to some extent, but it is preferable that the glycidyl group and the amino group are not in contact with each other in the emulsion form as much as possible, and the functional groups of both are contacted only after the emulsion film formation is started. It is desirable that crosslinking occur.
【００２７】なお、本発明の一成分系水性プライマー組
成物では、これを単独ではもちろん、通常の乳化重合で
得られる高分子量ポリマーで構成されるエマルジョンと
の混合物を用いてもよい。この際の本発明の一成分系水
性プライマー組成物（Ｍ）と高分子量ポリマーで構成さ
れるエマルジョン（Ｎ）の混合比（固形分）は、重量比
で、Ｍ／Ｎ＝１００／０〜９０／１０に設定することが
好ましい。In the one-component aqueous primer composition of the present invention, it may be used alone or as a mixture with an emulsion composed of a high molecular weight polymer obtained by ordinary emulsion polymerization. At this time, the mixing ratio (solid content) of the one-component aqueous primer composition (M) of the present invention and the emulsion (N) composed of a high molecular weight polymer is M / N = 100/0 to 90 by weight. It is preferably set to / 10.
【００２８】上記のようにして得られた本発明の一成分
系水性プライマー組成物は、コンクリート，スレート，
ケイカル板，軽量気泡コンクリート（ＡＬＣ）板等の無
機建材，金属，木材，紙，織物，ガラス，合成樹脂，陶
磁器，皮革等のあらゆる基材の補強材として塗布するこ
とができ、耐水性，補強性および密着性に優れた性能を
有する。The one-component water-based primer composition of the present invention obtained as described above comprises concrete, slate,
It can be applied as a reinforcing material for all kinds of base materials such as inorganic building materials such as calcareous board and lightweight aerated concrete (ALC) board, metal, wood, paper, fabric, glass, synthetic resin, ceramics, leather, etc. It has excellent properties and adhesiveness.
【００２９】そして、本発明の一成分系水性プライマー
組成物である塗布液は、基材の表面層で乾燥過程におい
て、数平均分子量１０００〜１００００の範囲内の低分
子量ポリマーで構成されるエマルジョン粒子から、低分
子量ポリマーが脆弱層に速やかに溶融拡散し、層が均一
に上記ポリマーで満たされた状態となる。ついで、ポリ
マー鎖に共重合されているグリシジル基とアミノ基はエ
マルジョン形態では、互いに完全に隔離されているが、
エマルジョン粒子の融着により接触して架橋が生じ、三
次元網目構造となる。そして、低分子量ポリマーが、即
座に強靱な皮膜へと変わることにより、従来にない極め
て優れた基材補強性，耐水性が発現する。The coating solution, which is the one-component aqueous primer composition of the present invention, is an emulsion particle composed of a low molecular weight polymer having a number average molecular weight of 1,000 to 10,000 in the drying process on the surface layer of the substrate. Therefore, the low molecular weight polymer is rapidly melt-diffused into the brittle layer, and the layer is uniformly filled with the polymer. Then, the glycidyl group and the amino group copolymerized to the polymer chain are completely separated from each other in the emulsion form,
Due to the fusion of the emulsion particles, they are brought into contact with each other to cause cross-linking to form a three-dimensional network structure. Then, the low-molecular weight polymer is immediately changed into a tough film, whereby extremely excellent base material reinforcing properties and water resistance, which have never existed before, are exhibited.
【００３０】[0030]
【発明の効果】以上のように、本発明は、グリシジル基
含有単量体とエチレン性不飽和単量体からなる共重合体
（Ａ成分）がアミノ基含有単量体とエチレン性不飽和単
量体からなる共重合体（Ｂ成分）によって被覆保護さ
れ、かつ上記ＡおよびＢ成分とも特定の数平均分子量に
設定された二重構造の微粒子を、水性媒体中に含有する
一成分系水性プライマー組成物である。また、グリシジ
ル基含有単量体からなる共重合体（Ｃ成分）が、エチレ
ン性不飽和単量体からなる共重合体（Ｅ成分）を介して
アミノ基含有単量体からなる共重合体（Ｄ成分）によっ
て被覆され、かつ上記Ｃ〜Ｅ成分が特定の数平均分子量
に設定された三重構造の微粒子を、水性媒体中に含有す
る一成分系水性プライマー組成物である。このため、優
れた浸透性を有し、しかもこれを用いて得られる塗膜
は、優れた密着性，補強性，耐水性および上塗り塗膜と
の密着性を備えている。したがって、水性でありなが
ら、従来の溶剤系塗料と同等以上の優れた基材補強効果
を有し、しかも安全で公害源にもならない。さらに、上
塗り塗料等に対する親和性を発揮し、これからなる仕上
げ剤層を、基材表面に強固に一体化させるという優れた
効果をも有する。As described above, according to the present invention, the copolymer (component (A)) comprising a glycidyl group-containing monomer and an ethylenically unsaturated monomer is used as an amino group-containing monomer and an ethylenically unsaturated monomer. One-component aqueous primer containing fine particles having a double structure, which are coated and protected by a copolymer (component B) composed of a monomer, and in which both the components A and B have a specific number average molecular weight, in an aqueous medium. It is a composition. Further, a copolymer (C component) composed of a glycidyl group-containing monomer is a copolymer (A component) composed of an amino group-containing monomer via a copolymer (E component) composed of an ethylenically unsaturated monomer. A one-component aqueous primer composition containing fine particles having a triple structure in which the above-mentioned C to E components are set to have a specific number average molecular weight in an aqueous medium. Therefore, it has excellent penetrability, and the coating film obtained by using it has excellent adhesion, reinforcement, water resistance and adhesion to the top coat film. Therefore, even though it is water-based, it has an excellent base material reinforcing effect equivalent to or better than that of conventional solvent-based paints, and is safe and does not become a pollution source. Further, it also has an excellent effect of exhibiting an affinity for a top coat and the like and firmly integrating a finishing agent layer made of the same onto the surface of the base material.
【００３１】つぎに、実施例について比較例と併せて説
明する。Next, examples will be described together with comparative examples.
【００３２】[0032]
【実施例１】攪拌翼，温度計および還流冷却器を取り付
けた４つ口フラスコに、水７０重量部（以下「部」と略
す）、エマルゲン９５０（花王社製，ノニオン系乳化
剤）２部を添加した後加温して内温度７０℃とした。そ
して、この状態で、下記の表１に示す乳化液Ａ用の各モ
ノマーと連鎖移動剤が含有された乳化液の５％、過硫酸
カリウム０．２部を水４部に溶解したものを添加した。
つぎに、残りの乳化液を２時間かけて滴下ロートを用い
て滴下反応させ、０．５時間の完結反応を行った。さら
に、下記の表１に示す乳化液Ｂ用の各モノマーからなる
乳化液Ｂおよび過硫酸カリウム０．３部を水１０部に溶
解した液を２時間かけて滴下ロートを用いて滴下反応さ
せ、１時間の完結反応を行った。そして、冷却後、これ
にアンモニア水２部を添加した。このようにして目的と
する二重構造の微粒子が含有された水性プライマー組成
物を得た。Example 1 A four-necked flask equipped with a stirring blade, a thermometer and a reflux condenser was charged with 70 parts by weight of water (hereinafter abbreviated as “part”) and 2 parts of Emulgen 950 (Kao Corporation, nonionic emulsifier). After the addition, the temperature was raised to 70 ° C. Then, in this state, 5% of the emulsion containing each monomer for emulsion A and the chain transfer agent shown in Table 1 below, and 0.2 parts of potassium persulfate dissolved in 4 parts of water were added. did.
Next, the rest of the emulsion was added dropwise using a dropping funnel over 2 hours to complete the reaction for 0.5 hours. Further, an emulsion B composed of each monomer for the emulsion B shown in Table 1 below and a solution prepared by dissolving 0.3 part of potassium persulfate in 10 parts of water are reacted dropwise using a dropping funnel for 2 hours. A complete reaction was carried out for 1 hour. Then, after cooling, 2 parts of ammonia water was added thereto. In this way, an aqueous primer composition containing the target double-structured fine particles was obtained.
【００３３】[0033]
【表１】 [Table 1]
【００３４】上記のようにして得られたエマルジョンの
濃度は、５０％で、ｐＨ＝８．７であった。また、この
微粒子のコア部とシェル部のポリマーの各数平均分子量
は１００００であった。なお、上記分子量の測定は、ウ
ォーターズ社製のモデル６６Ｋに、カラムとしてウルト
ラスタイラジェル５００Å，１０3 Å，１０4 Å，１０
5 Åの４カラムを直列に連結し、テトラヒドロフランを
移動剤として用いた。また、検量線の作成には、ポリス
チレン（重量平均分子量と数平均分子量の比が１．０４
のもの）を標準試料とした。The emulsion thus obtained had a concentration of 50% and a pH of 8.7. The number average molecular weight of each of the polymer in the core portion and the shell portion of the fine particles was 10,000. In addition, the measurement of the above-mentioned molecular weight was carried out on a model 66K manufactured by Waters Co., Ltd., using Ultrastyra Gel 500Å, 10 3 Å, 10 4 Å, 10 as a column.
The four columns of 5 Å connected in series, tetrahydrofuran was used as a transfer agent. In addition, polystyrene was used for preparing the calibration curve (the ratio of the weight average molecular weight to the number average molecular weight was 1.04).
) Was used as a standard sample.
【００３５】[0035]
【実施例２】連鎖移動剤（ｎ−ドデシルメルカプタン）
を乳化液Ａ，Ｂともに４部に変えた。それ以外は実施例
１と同様にして目的とする水性プライマー組成物を得
た。この微粒子のコア部とシェル部のポリマーの各数平
均分子量は１０００であった。Example 2 Chain transfer agent (n-dodecyl mercaptan)
Was changed to 4 parts for both emulsions A and B. Except for this, the same procedure as in Example 1 was carried out to obtain a desired aqueous primer composition. The number average molecular weight of each of the polymer in the core portion and the shell portion of the fine particles was 1,000.
【００３６】[0036]
【実施例３】攪拌翼，温度計および還流冷却器を取り付
けた４つ口フラスコに、水８０部、レベノールＷＺ（花
王社製，アニオン系乳化剤）２部を添加した後加温して
内温度７０℃とした。そして、この状態で、下記の表２
に示す各モノマーからなる乳化液の５％と、過硫酸カリ
ウム０．５部を水４部に溶解したものを添加した。つぎ
に、残りのモノマー乳化液を４時間かけて滴下ロートを
用いて滴下反応させ、２時間の完結反応を行った。そし
て、冷却後、これにアンモニア水２部を添加した。この
ようにしてエマルジョンを作成した。Example 3 To a four-necked flask equipped with a stirring blade, a thermometer, and a reflux condenser, 80 parts of water and 2 parts of Rebenol WZ (Kao Corporation, anionic emulsifier) were added, and then heated to an internal temperature. The temperature was 70 ° C. And in this state, Table 2 below
5% of the emulsified liquid consisting of the monomers shown in Table 1 and 0.5 parts of potassium persulfate dissolved in 4 parts of water were added. Next, the remaining monomer emulsion was added dropwise using a dropping funnel for 4 hours to complete the reaction for 2 hours. Then, after cooling, 2 parts of ammonia water was added thereto. An emulsion was prepared in this way.
【００３７】[0037]
【表２】 [Table 2]
【００３８】上記のようにして得られたエマルジョンの
濃度は、５０％で、ｐＨ＝８．７であった。また、この
ポリマーの数平均分子量は１０万以上であった。The emulsion thus obtained had a concentration of 50% and a pH of 8.7. The number average molecular weight of this polymer was 100,000 or more.
【００３９】そして、前記実施例１で得られたエマルジ
ョン（Ｘ）と上記エマルジョン（Ｙ）とを、重量比で
Ｘ：Ｙ＝９：１の割合で混合することにより水性プライ
マー組成物を得た。この組成物において、数平均分子量
１００００のポリマー成分を９０％含有している。Then, the emulsion (X) obtained in Example 1 and the emulsion (Y) were mixed in a weight ratio of X: Y = 9: 1 to obtain an aqueous primer composition. . This composition contains 90% of a polymer component having a number average molecular weight of 10,000.
【００４０】[0040]
【実施例４】攪拌翼，温度計および還流冷却器を取り付
けた４つ口フラスコに、水７０部、エマルゲン９５０
（花王社製，ノニオン系乳化剤）２部を添加した後加温
して内温度７０℃とした。そして、この状態で、下記の
表３に示す乳化液Ｃ用の各モノマーと連鎖移動剤が含有
された乳化液の５％、過硫酸カリウム０．２部を水４部
に溶解したものを添加した。つぎに、残りのモノマー乳
化液を１．５時間かけて滴下ロートを用いて滴下反応さ
せ、０．５時間の完結反応を行った。さらに、下記の表
３に示す乳化液Ｄを１時間かけて滴下反応させ、０．５
時間の完結反応の後、乳化液Ｅを１．５時間かけて滴下
反応させ、さらに１時間の完結反応を行った。なお、乳
化液Ｄ，Ｅの滴下と並行して、過硫酸カリウム０．３部
を水１０部に溶解した液も滴下した。そして、冷却後、
これにアンモニア水２部を添加した。このようにして目
的とする水性プライマー組成物を得た。Example 4 A four-necked flask equipped with a stirring blade, a thermometer and a reflux condenser was charged with 70 parts of water and 950 Emulgen.
2 parts (manufactured by Kao Corporation, nonionic emulsifier) were added and then heated to an internal temperature of 70 ° C. Then, in this state, 5% of the emulsion containing each monomer for Emulsion C shown in Table 3 below and the chain transfer agent, and 0.2 parts of potassium persulfate dissolved in 4 parts of water were added. did. Next, the remaining monomer emulsion was subjected to a dropwise reaction using a dropping funnel over 1.5 hours to complete the reaction for 0.5 hours. Furthermore, the emulsion D shown in Table 3 below was reacted dropwise over 1 hour to give 0.5
After the completion reaction of time, the emulsion E was added dropwise for 1.5 hours to carry out the reaction, and the completion reaction was further carried out for 1 hour. In addition, in parallel with the dropping of the emulsions D and E, a solution prepared by dissolving 0.3 part of potassium persulfate in 10 parts of water was also dropped. And after cooling,
To this, 2 parts of aqueous ammonia was added. Thus, the desired aqueous primer composition was obtained.
【００４１】[0041]
【表３】 [Table 3]
【００４２】上記のようにして得られたエマルジョンの
濃度は、５０％で、ｐＨ＝８．７であった。また、この
微粒子のコア部とシェル部および両者の間に位置する部
分のポリマーの各数平均分子量は１００００であった。
なお、上記分子量は上記実施例１と同様にして測定し
た。The concentration of the emulsion obtained as described above was 50% and the pH was 8.7. The number average molecular weight of the polymer in the core portion and shell portion of the fine particles and in the portion located between the core portion and the shell portion was 10,000.
The molecular weight was measured in the same manner as in Example 1 above.
【００４３】[0043]
【実施例５】連鎖移動剤（ｎ−ドデシルメルカプタン）
を乳化液Ｃ，Ｄ，Ｅともに３部に変えた。それ以外は実
施例４と同様にして目的とする水性プライマー組成物を
得た。この組成物中の微粒子のコア部とシェル部および
両者の間に位置する部分のポリマーの各数平均分子量
は、数平均分子量は１０００であった。Example 5 Chain Transfer Agent (n-dodecyl mercaptan)
Was changed to 3 parts for each of emulsions C, D and E. Except for this, the same procedure as in Example 4 was carried out to obtain a desired aqueous primer composition. The number average molecular weight of the polymer in the core portion and the shell portion of the fine particles in this composition, and the portion located between the both portions was 1,000.
【００４４】[0044]
【実施例６】攪拌翼，温度計および還流冷却器を取り付
けた４つ口フラスコに、水８０部、レベノールＷＺ（花
王社製，アニオン系乳化剤）２部を添加した後加温して
内温度７０℃とした。そして、この状態で、下記の表４
に示す各モノマーからなる乳化液の５％と、過硫酸カリ
ウム０．５部を水４部に溶解したものを添加した。つぎ
に、残りのモノマー乳化液を４時間かけて滴下ロートを
用いて滴下反応させ、２時間の完結反応を行った。そし
て、冷却後、これにアンモニア水２部を添加した。この
ようにしてエマルジョンを作成した。Example 6 To a four-necked flask equipped with a stirring blade, a thermometer and a reflux condenser, 80 parts of water and 2 parts of Rebenol WZ (Kao Corporation, anionic emulsifier) were added and then heated to an internal temperature. The temperature was 70 ° C. And in this state, Table 4 below
5% of the emulsified liquid consisting of the monomers shown in Table 1 and 0.5 parts of potassium persulfate dissolved in 4 parts of water were added. Next, the remaining monomer emulsion was added dropwise using a dropping funnel for 4 hours to complete the reaction for 2 hours. Then, after cooling, 2 parts of ammonia water was added thereto. An emulsion was prepared in this way.
【００４５】[0045]
【表４】 [Table 4]
【００４６】上記のようにして得られたエマルジョンの
濃度は、５０％で、ｐＨ＝８．７であった。また、この
ポリマーの数平均分子量は１０万以上であった。The concentration of the emulsion thus obtained was 50% and the pH was 8.7. The number average molecular weight of this polymer was 100,000 or more.
【００４７】そして、前記実施例４で得られたエマルジ
ョン（Ｘ）と上記エマルジョン（Ｙ）とを、重量比で
Ｘ：Ｙ＝９：１の割合で混合することにより目的とする
水性プライマー組成物を得た。この組成物において、数
平均分子量１００００のポリマー成分を９０％含有して
いる。Then, the emulsion (X) obtained in Example 4 and the above emulsion (Y) are mixed in a weight ratio of X: Y = 9: 1 to obtain a desired aqueous primer composition. Got This composition contains 90% of a polymer component having a number average molecular weight of 10,000.
【００４８】[0048]
【比較例１】連鎖移動剤（ｎ−ドデシルメルカプタン）
を乳化液Ａ，Ｂともに０．５部に変えた。それ以外は実
施例１と同様にして水性プライマー組成物を得た。この
組成物中の微粒子のコア部およびシェル部の数平均分子
量は２００００であった。Comparative Example 1 Chain transfer agent (n-dodecyl mercaptan)
Was changed to 0.5 parts for both emulsions A and B. An aqueous primer composition was obtained in the same manner as in Example 1 except for the above. The number average molecular weight of the core portion and shell portion of the fine particles in this composition was 20,000.
【００４９】[0049]
【比較例２】連鎖移動剤（ｎ−ドデシルメルカプタン）
を乳化液Ａ，Ｂともに６部に変えた。それ以外は実施例
１と同様にして水性プライマー組成物を得た。この組成
物中の微粒子のコア部およびシェル部の数平均分子量は
７００であった。Comparative Example 2 Chain transfer agent (n-dodecyl mercaptan)
Was changed to 6 parts for both emulsions A and B. An aqueous primer composition was obtained in the same manner as in Example 1 except for the above. The number average molecular weight of the core portion and shell portion of the fine particles in this composition was 700.
【００５０】[0050]
【比較例３】グリシジルメタクリレートを用いなかっ
た。それ以外は実施例１と同様にして水性プライマー組
成物を得た。Comparative Example 3 Glycidyl methacrylate was not used. An aqueous primer composition was obtained in the same manner as in Example 1 except for the above.
【００５１】[0051]
【比較例４】ジメチルアミノエチルメタクリレートを用
いなかった。それ以外は実施例１と同様にして水性プラ
イマー組成物を得た。Comparative Example 4 Dimethylaminoethyl methacrylate was not used. An aqueous primer composition was obtained in the same manner as in Example 1 except for the above.
【００５２】[0052]
【比較例５】連鎖移動剤（ｎ−ドデシルメルカプタン）
を乳化液Ｃ，Ｄ，Ｅともに０．５部に変えた。それ以外
は実施例４と同様にして水性プライマー組成物を得た。
この組成物中の微粒子のコア部とシェル部および両者の
間に位置する部分のポリマーの各数平均分子量は２００
００であった。[Comparative Example 5] Chain transfer agent (n-dodecyl mercaptan)
Was changed to 0.5 parts for each of Emulsions C, D and E. An aqueous primer composition was obtained in the same manner as in Example 4 except for the above.
The number average molecular weight of each polymer of the core portion and the shell portion of the fine particles in this composition and the portion located between them is 200.
It was 00.
【００５３】[0053]
【比較例６】連鎖移動剤（ｎ−ドデシルメルカプタン）
を乳化液Ｃ，Ｄ，Ｅともに４部に変えた。それ以外は実
施例４と同様にして水性プライマー組成物を得た。この
組成物中の微粒子のコア部とシェル部および両者の間に
位置する部分のポリマーの各数平均分子量は７００であ
った。Comparative Example 6 Chain transfer agent (n-dodecyl mercaptan)
Was changed to 4 parts for each of Emulsions C, D and E. An aqueous primer composition was obtained in the same manner as in Example 4 except for the above. The number average molecular weight of the polymer in the core portion and the shell portion of the fine particles in this composition and in the portion located between them was 700.
【００５４】[0054]
【比較例７】グリシジルメタクリレートを用いなかっ
た。それ以外は実施例４と同様にして水性プライマー組
成物を得た。Comparative Example 7 Glycidyl methacrylate was not used. An aqueous primer composition was obtained in the same manner as in Example 4 except for the above.
【００５５】[0055]
【比較例８】ジメチルアミノエチルメタクリレートを用
いなかった。それ以外は実施例４と同様にして水性プラ
イマー組成物を得た。Comparative Example 8 Dimethylaminoethyl methacrylate was not used. An aqueous primer composition was obtained in the same manner as in Example 4 except for the above.
【００５６】このようにして得られた実施例品および比
較例品９４．５部に、水６０．４部、分散剤（プライマ
ール８５０、ロームアンドハース社製）２部、増粘剤
（１５％ヨドゾール ＫＡ−１０、カネボウ・エヌエス
シー社製）０．５部、酸化チタン（Ｒ−６５０、堺化学
社製）１２．６部、クレー（ＡＳＰ４００Ｐ、エンゲル
ハート社製）５０部、造膜助剤（テキサノール、チッソ
社製）７部を加え塗料化した。作製した塗料の濃度は４
５％、粘度２００ｃｐｓ、顔料体積濃度（ＰＶＣ）３７
％であった。塗料化したサンプルを市販のケイカル板
（比重０．７ｇ／ｃｍ3 ）に刷毛で１２０ｇ／ｍ2 塗布
し、１２０℃×５分乾燥した後、適当な大きさに切断
し、密着性試験，耐水性試験，耐温水試験，耐アルカリ
試験，凍結融解サイクル試験および耐候性の各種試験を
行った。その結果を下記の表５および表６に示した。な
お、上記各種試験方法は下記に従った。In addition to 94.5 parts of the example product and comparative product thus obtained, 60.4 parts of water, 2 parts of a dispersant (Primal 850, manufactured by Rohm and Haas), and a thickener (15 % Iodozol KA-10, Kanebo NSC Co., Ltd. 0.5 part, titanium oxide (R-650, Sakai Chemical Co., Ltd.) 12.6 parts, clay (ASP400P, Engelhart Co., Ltd.) 50 parts, film formation aid 7 parts of an agent (Texanol, manufactured by Chisso Co.) was added to form a paint. The concentration of the prepared paint is 4
5%, viscosity 200 cps, pigment volume concentration (PVC) 37
%Met. A paint sample is applied to a commercially available silica sheet (specific gravity 0.7 g / cm 3 ) with a brush at 120 g / m 2, dried at 120 ° C for 5 minutes, and then cut to an appropriate size for adhesion test and water resistance. A variety of tests were conducted, including a heat resistance test, hot water resistance test, alkali resistance test, freeze-thaw cycle test, and weather resistance. The results are shown in Tables 5 and 6 below. The above-mentioned various test methods were as follows.
【００５７】〔密着性試験〕塗膜に市販カッターで４ｍ
ｍ間隔で傷をつけ、２５個の枡目を作製した。ついで、
セロハンテープで強く張り付け、急激に剥がした。そし
て、残存した塗膜の枡目をカウントした（碁盤目試
験）。その結果、枡目２５個全てが残存したものを○、
１１〜２４個残存したものを△、残存個数が１０個以下
のものを×として評価した。[Adhesion test] 4 m with a commercially available cutter on the coating film
Twenty-five squares were produced by making scratches at m intervals. Then,
It was strongly adhered with cellophane tape and then rapidly peeled off. Then, the squares of the remaining coating film were counted (cross-cut test). As a result, if all 25 cells remained, ○,
When 11 to 24 pieces remained, it was evaluated as Δ, and when the remaining number was 10 pieces or less, it was evaluated as x.
【００５８】〔耐水性試験〕上記塗装板を１０ｃｍ×５
ｃｍの大きさに切断し、水中（２０℃）に１週間浸漬し
た後、５０℃で４時間乾燥して上記と同様の碁盤目試験
を行った。[Water resistance test] The coated plate was 10 cm × 5
It was cut into a size of cm, immersed in water (20 ° C.) for 1 week, dried at 50 ° C. for 4 hours, and subjected to the same cross-cut test as above.
【００５９】〔耐温水試験〕上記塗装板を１０ｃｍ×５
ｃｍの大きさに切断し、温水（５０℃）に１週間浸漬し
た後、５０℃で４時間乾燥して上記と同様の碁盤目試験
を行った。[Hot Water Resistance Test] The above coated plate was 10 cm × 5
The sample was cut into a size of cm, immersed in warm water (50 ° C.) for 1 week, dried at 50 ° C. for 4 hours, and subjected to the same cross-cut test as above.
【００６０】〔耐アルカリ試験〕上記塗装板を１０ｃｍ
×５ｃｍの大きさに切断し、飽和Ｃａ（ＯＨ）2 水溶液
に２日間浸漬した後、５０℃で４時間乾燥して上記と同
様の碁盤目試験を行った。[Alkali resistance test] 10 cm of the above coated plate
After being cut into a size of 5 cm and immersed in a saturated Ca (OH) 2 aqueous solution for 2 days, it was dried at 50 ° C. for 4 hours and the same cross-cut test was performed.
【００６１】〔凍結融解サイクル試験〕上記塗装板を１
０ｃｍ×５ｃｍの大きさに切断し、裏面と側面をエポキ
シ樹脂でシールした。そして、１日放置した後、水中
に１６時間浸漬、−２５℃で４時間、５０℃で４時
間の〜を１サイクルとして１０サイクルの試験を行
った。そして、その後の塗膜の状態を観察した。その結
果、塗膜に剥がれの生じなかったものを○、１０〜４０
％の剥がれの生じたものを△、５０〜１００％の剥がれ
の生じたものを×として評価した。[Freeze-thaw cycle test]
It was cut into a size of 0 cm × 5 cm, and the back and side surfaces were sealed with epoxy resin. Then, after leaving it for 1 day, it was immersed in water for 16 hours, and was subjected to 10 cycles of tests, with one cycle consisting of -25 ° C. for 4 hours and 50 ° C. for 4 hours. And the state of the coating film after that was observed. As a result, the film which did not peel off was rated as ◯, 10 to 40
% Peeling was evaluated as Δ, and 50-100% peeling was evaluated as x.
【００６２】〔耐候性〕上記塗装板を１０ｃｍ×５ｃｍ
の大きさに切断し、裏面と側面をエポキシ樹脂でシール
した。そして、ウェザーメーターに５００時間放置し、
塗膜の状態を観察した。その結果、塗膜に剥がれの生じ
なかったものを○、１０〜４０％の剥がれの生じたもの
を△、５０〜１００％の剥がれの生じたものを×として
評価した。[Weather resistance] 10 cm × 5 cm of the above coated plate
It was cut to the size of, and the back and side were sealed with epoxy resin. Then leave it on the weather meter for 500 hours,
The state of the coating film was observed. As a result, the film having no peeling was evaluated as ◯, the film having 10 to 40% peeling was evaluated as Δ, and the film having 50 to 100% peeling was evaluated as ×.
【００６３】[0063]
【表５】 [Table 5]
【００６４】[0064]
【表６】 [Table 6]
【００６５】上記表５および表６の結果から、実施例品
は、密着性試験，耐水性試験，耐温水試験，耐アルカリ
試験，凍結融解サイクル試験および耐候性試験の全てに
優れた評価が得られた。From the results of Table 5 and Table 6 above, the Example products were evaluated excellent in all of the adhesion test, water resistance test, hot water resistance test, alkali resistance test, freeze-thaw cycle test and weather resistance test. Was given.
【００６６】さらに、上記実施例および比較例で得られ
たプライマー組成物を水で２倍に希釈した。そして、こ
れを、ポリエチレンテレフタレート（ＰＥＴ）フィル
ム，鋼板およびガラス板に２５０μｍのアプリケーター
で塗布する。ついで、８０℃で１０分間乾燥させた後、
塗膜に市販カッターで２ｍｍ間隔で傷をつけ、１００個
の枡目を作製した。ついで、セロハンテープで強く張り
付け、急激に剥がした。そして、残存した塗膜の枡目を
カウントした（碁盤目試験）。その結果、枡目１００個
全てが残存したものを○、８１〜９９個残存したものを
△、残存個数が８０個以下のものを×として評価した。
この評価結果を下記の表７および表８に示す。Furthermore, the primer compositions obtained in the above Examples and Comparative Examples were diluted with water by a factor of 2. Then, this is applied to a polyethylene terephthalate (PET) film, a steel plate and a glass plate with a 250 μm applicator. Then, after drying at 80 ° C. for 10 minutes,
The coating film was scratched with a commercially available cutter at 2 mm intervals to make 100 squares. Then, it was strongly attached with cellophane tape and peeled off rapidly. Then, the squares of the remaining coating film were counted (cross-cut test). As a result, the case where all 100 meshes remained was evaluated as ◯, the case where 81 to 99 pieces remained was evaluated as Δ, and the case where the remaining number was 80 or less was evaluated as x.
The evaluation results are shown in Tables 7 and 8 below.
【００６７】[0067]
【表７】 [Table 7]
【００６８】[0068]
【表８】 [Table 8]
【００６９】上記表７および表８の結果から、実施例品
はＰＥＴフィルム，鋼板およびガラス板の全てに対して
強固に密着していることがわかる。From the results shown in Tables 7 and 8 above, it can be seen that the product of Example is firmly adhered to all of the PET film, steel plate and glass plate.
【図１】本発明の水性プライマー組成物中に含有される
二重構造の微粒子の構造を示す模式図である。FIG. 1 is a schematic diagram showing the structure of fine particles having a double structure contained in the aqueous primer composition of the present invention.
【図２】本発明の水性プライマー組成物中に含有される
三重構造の微粒子の構造を示す模式図である。FIG. 2 is a schematic view showing the structure of fine particles having a triple structure contained in the aqueous primer composition of the present invention.
１ （Ａ）成分 ２ （Ｂ）成分 ３ （Ｃ）成分 ４ （Ｄ）成分 ５ （Ｅ）成分 1 (A) component 2 (B) component 3 (C) component 4 (D) component 5 (E) component
Claims (4)
よって被覆保護されている二重構造の微粒子が、水性媒
体中に含有され、上記（Ａ）成分および（Ｂ）成分の双
方とも数平均分子量が１０００〜１００００の範囲に設
定されていることを特徴とする一成分系水性プライマー
組成物。 （Ａ）グリシジル基含有単量体とエチレン性不飽和単量
体とからなる共重合体。 （Ｂ）アミノ基含有単量体とエチレン性不飽和単量体と
からなる共重合体。1. A double-structured fine particle in which the following component (A) is coated and protected by the following component (B) is contained in an aqueous medium, and both the component (A) and the component (B) are contained. Both have a number-average molecular weight in the range of 1,000 to 10,000, and a one-component aqueous primer composition. (A) A copolymer composed of a glycidyl group-containing monomer and an ethylenically unsaturated monomer. (B) A copolymer composed of an amino group-containing monomer and an ethylenically unsaturated monomer.
組成物と、任意の高分子量ポリマーで構成されるエマル
ジョンとからなる水性プライマー組成物であって、上記
一成分系水性プライマー組成物（Ｍ）と任意の高分子量
ポリマーで構成されるエマルジョン（Ｎ）との混合割合
が、重量比で、Ｍ／Ｎ＝１００／０〜９０／１０の範囲
に設定されている請求項１記載の一成分系水性プライマ
ー組成物。2. An aqueous primer composition comprising the one-component aqueous primer composition according to claim 1 and an emulsion composed of an arbitrary high molecular weight polymer, wherein the one-component aqueous primer composition (M 2.) One component according to claim 1, wherein the mixing ratio of the emulsion (N) composed of a high molecular weight polymer is set in the range of M / N = 100/0 to 90/10 by weight. -Based aqueous primer composition.
を介して下記の（Ｄ）成分によって被覆保護されている
三重構造の微粒子が、水性媒体中に含有され、上記
（Ｃ）〜（Ｅ）成分の全ての数平均分子量が１０００〜
１００００の範囲に設定されていることを特徴とする一
成分系水性プライマー組成物。 （Ｃ）グリシジル基含有単量体からなる共重合体。 （Ｄ）アミノ基含有単量体からなる共重合体。 （Ｅ）エチレン性不飽和単量体からなる共重合体。3. A fine particle having a triple structure in which the following component (C) is covered and protected by the following component (D) via the following component (E) is contained in an aqueous medium, and the above (C )-(E) all number average molecular weights of 1000-
A one-component water-based primer composition, which is set in a range of 10,000. (C) A copolymer composed of a glycidyl group-containing monomer. (D) A copolymer composed of an amino group-containing monomer. (E) A copolymer composed of an ethylenically unsaturated monomer.
組成物と、任意の高分子量ポリマーで構成されるエマル
ジョンとからなる水性プライマー組成物であって、上記
一成分系水性プライマー組成物（Ｍ）と任意の高分子量
ポリマーで構成されるエマルジョン（Ｎ）との混合割合
が、重量比で、Ｍ／Ｎ＝１００／０〜９０／１０の範囲
に設定されている請求項３記載の一成分系水性プライマ
ー組成物。4. An aqueous primer composition comprising the one-component aqueous primer composition according to claim 3 and an emulsion composed of an arbitrary high molecular weight polymer, wherein the one-component aqueous primer composition (M 4.) One component according to claim 3, wherein the mixing ratio of the emulsion (N) composed of an arbitrary high molecular weight polymer is set to a weight ratio of M / N = 100/0 to 90/10. -Based aqueous primer composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23039892A JP2752862B2 (en) | 1992-08-28 | 1992-08-28 | One-component aqueous primer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23039892A JP2752862B2 (en) | 1992-08-28 | 1992-08-28 | One-component aqueous primer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0673308A true JPH0673308A (en) | 1994-03-15 |
| JP2752862B2 JP2752862B2 (en) | 1998-05-18 |
Family
ID=16907258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23039892A Expired - Fee Related JP2752862B2 (en) | 1992-08-28 | 1992-08-28 | One-component aqueous primer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2752862B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5869568A (en) * | 1996-12-05 | 1999-02-09 | National Starch And Chemical Investment Holding Corporation | One-part cold crosslinking emulsion composition and method of manufacturing the same |
| JP2004115678A (en) * | 2002-09-26 | 2004-04-15 | Sk Kaken Co Ltd | Aqueous undercoat composition |
| US9862854B2 (en) | 2004-10-20 | 2018-01-09 | Valspar Sourcing, Inc. | Coating compositions for aluminum beverage cans and methods of coating same |
| US10563010B2 (en) | 2009-04-09 | 2020-02-18 | The Sherwin-Williams Company | Polymer having unsaturated cycloaliphatic functionality and coating compositions therefrom |
-
1992
- 1992-08-28 JP JP23039892A patent/JP2752862B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5869568A (en) * | 1996-12-05 | 1999-02-09 | National Starch And Chemical Investment Holding Corporation | One-part cold crosslinking emulsion composition and method of manufacturing the same |
| JP2004115678A (en) * | 2002-09-26 | 2004-04-15 | Sk Kaken Co Ltd | Aqueous undercoat composition |
| US9862854B2 (en) | 2004-10-20 | 2018-01-09 | Valspar Sourcing, Inc. | Coating compositions for aluminum beverage cans and methods of coating same |
| US10336909B2 (en) | 2004-10-20 | 2019-07-02 | The Sherwin-Williams Company | Coating compositions for aluminum beverage cans and methods of coating same |
| US10563010B2 (en) | 2009-04-09 | 2020-02-18 | The Sherwin-Williams Company | Polymer having unsaturated cycloaliphatic functionality and coating compositions therefrom |
| US10961344B2 (en) | 2009-04-09 | 2021-03-30 | The Sherwin-Williams Company | Polymer having unsaturated cycloaliphatic functionality and coating compositions therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2752862B2 (en) | 1998-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6372781A (en) | Mastic and coking composition and composite article | |
| JP2002502449A (en) | Fast curing latex coatings and formulations | |
| CN109153739B (en) | Amine functional anionic polymer dispersion and coating composition therefor | |
| CA1067236A (en) | Aqueous acrylic-carboxylated polyether compositions | |
| JP3624274B2 (en) | Coating composition | |
| EP0521997B1 (en) | Crosslinkable surface coatings and methods for producing same | |
| JPH07196974A (en) | Ambient and elevated temperature curable polymer compositions useful in waterborne and wood coatings | |
| JP3155480B2 (en) | One-part cold crosslinking emulsion composition and production method thereof | |
| JP3358873B2 (en) | Aqueous solution for primer | |
| JPH0673334A (en) | Two-component water-based primer composition | |
| JP3358872B2 (en) | Aqueous liquid for primer | |
| JP2655783B2 (en) | Aqueous liquid for primer | |
| JP2769068B2 (en) | Cationic microemulsion composition and method for producing the same | |
| JPH0673308A (en) | One-pack water-based primer composition | |
| JPH02308887A (en) | Water resin composition for sealer | |
| JPS624075B2 (en) | ||
| JPH04154874A (en) | Aqueous primer composition | |
| CN121135965A (en) | Environmentally friendly water-based coating compositions | |
| JP2557581B2 (en) | Coating film structure and manufacturing method thereof | |
| NZ260296A (en) | Use of a coating composition comprising acid-functional polymer and an organosilane to impart stain resistance, adhesive improvement, fire and smoke block and/or various other uses | |
| JPH03229766A (en) | Aqueous primer solution | |
| JPS62277474A (en) | Coating material composition | |
| JPS59155413A (en) | Resin dispersion and its production | |
| JPH09309933A (en) | Cold curing aqueous resin and preparation thereof | |
| JPH07305019A (en) | Water-based coating composition and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080227 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090227 Year of fee payment: 11 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090227 Year of fee payment: 11 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090227 Year of fee payment: 11 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 11 Free format text: PAYMENT UNTIL: 20090227 |
|
| R371 | Transfer withdrawn |
Free format text: JAPANESE INTERMEDIATE CODE: R371 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090227 Year of fee payment: 11 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 11 Free format text: PAYMENT UNTIL: 20090227 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100227 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100227 Year of fee payment: 12 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 12 Free format text: PAYMENT UNTIL: 20100227 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 12 Free format text: PAYMENT UNTIL: 20100227 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 13 Free format text: PAYMENT UNTIL: 20110227 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110227 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 14 Free format text: PAYMENT UNTIL: 20120227 |
|
| LAPS | Cancellation because of no payment of annual fees |