JP2017206662A - Quick-drying thick coating water paint and production method thereof - Google Patents
Quick-drying thick coating water paint and production method thereof Download PDFInfo
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- JP2017206662A JP2017206662A JP2016101819A JP2016101819A JP2017206662A JP 2017206662 A JP2017206662 A JP 2017206662A JP 2016101819 A JP2016101819 A JP 2016101819A JP 2016101819 A JP2016101819 A JP 2016101819A JP 2017206662 A JP2017206662 A JP 2017206662A
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- 239000003973 paint Substances 0.000 title claims abstract description 92
- 238000000576 coating method Methods 0.000 title claims abstract description 84
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
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- 239000000843 powder Substances 0.000 claims abstract description 63
- 229920005989 resin Polymers 0.000 claims abstract description 60
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- 238000006116 polymerization reaction Methods 0.000 claims abstract description 44
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- 229920002050 silicone resin Polymers 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- -1 acrylic ester Chemical class 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
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- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 229920006026 co-polymeric resin Polymers 0.000 claims description 5
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- 239000002562 thickening agent Substances 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
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- 239000005062 Polybutadiene Substances 0.000 claims description 4
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
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- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000000034 method Methods 0.000 description 3
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- 229920001296 polysiloxane Polymers 0.000 description 3
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
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- TUZBYYLVVXPEMA-UHFFFAOYSA-N butyl prop-2-enoate;styrene Chemical compound C=CC1=CC=CC=C1.CCCCOC(=O)C=C TUZBYYLVVXPEMA-UHFFFAOYSA-N 0.000 description 2
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- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 2
- 229920005651 polypropylene glycol dimethacrylate Polymers 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
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- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
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- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical compound OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、速乾性厚塗り水性塗料及びその製造方法に係り、より詳しくは、塗膜が厚く形成されているにもかかわらず乾燥が早い、速乾性厚塗り水性塗料及びその製造方法に関する。 The present invention relates to a quick-drying thick-coating water-based paint and a method for producing the same, and more particularly to a quick-drying thick-coating water-based paint and a method for producing the same that are quick to dry even though the coating film is formed thick.
塗料は、基材の上に薄く強固で美麗な塗膜を形成して基材を保護する目的で使用されることが多い。しかし、例えば道路面、横断歩道等を示す道路面の標識、家屋の周囲や車庫、及びコンクリート構造物等の、打放しのコンクリート表面やアスファルトの表面、鋼鉄製の橋や高架道路、鉄筋のした塗り等の鉄の防錆、或は木造家屋の外壁や塀などは、１回の塗装で厚い塗膜を形成することが要求される。 The paint is often used for the purpose of forming a thin, strong and beautiful coating film on the substrate to protect the substrate. However, for example, road surface signs indicating road surfaces, pedestrian crossings, surrounding concrete, garages, and concrete structures, such as bare concrete surfaces, asphalt surfaces, steel bridges, elevated roads, rebar coating It is required to form a thick coating film by coating once, such as rust prevention of iron or the like, or the outer wall or fence of a wooden house.
一方、塗料を厚く塗ると、塗料が乾燥・固化するまでの時間がかかるという必然的な問題点がある。道路面などを塗装する場合は、乾燥するまでの間は交通を遮断しなければならないし、特に油性の塗料は、乾燥するまで悪臭が漂い、火災の危険もあるので、塗料が乾燥・固化する速さは重大な問題である。また、傾斜面や垂直面に塗料を厚く塗ると液だれするので、塗料の粘性を高くしなければならない。このために、従来から、バインダー樹脂に増粘剤やケイ酸アルミニウム等の固体を配合して塗布することが行われてきた（例えば特許文献１を参照）。 On the other hand, when the paint is applied thickly, there is an inevitable problem that it takes time until the paint is dried and solidified. When painting road surfaces, it is necessary to block traffic until it dries. Especially, oil-based paint has a bad odor until it dries and there is a risk of fire, so the paint dries and solidifies. Speed is a serious problem. In addition, if the paint is applied thickly on an inclined surface or a vertical surface, it will drip and the viscosity of the paint must be increased. For this reason, conventionally, a binder resin and a solid such as a thickener and aluminum silicate are blended and applied (see, for example, Patent Document 1).
また、道路面の標識を塗装する場合に、水性のバインダー樹脂に固体粉末を加えてガラス転移点が−１０〜５０℃になるまで重合させて水性バインダー組成物として使用することが行われてきた。水性バインダー組成物は、固体粒子の表面をアンモニア水などで活性化し、ケイ酸ナトリウム等を配合して使用される（例えば特許文献２を参照）。特許文献２に記載の塗料は、路面に付着した後に、路面においてガラス転移点以上に加熱されて重合が進み、更に固化されるが、塗装とは言い難い。 In addition, when painting road surface signs, it has been practiced to add a solid powder to an aqueous binder resin and polymerize it until the glass transition point becomes -10 to 50 ° C. to use it as an aqueous binder composition. . The aqueous binder composition is used by activating the surface of solid particles with ammonia water or the like and blending sodium silicate or the like (see, for example, Patent Document 2). The paint described in Patent Document 2 is heated to a glass transition point or higher on the road surface after being attached to the road surface, polymerization proceeds and further solidifies, but it is difficult to say that it is a paint.
道路面の塗装方法として、アクリル酸エステル及び１分子中に少なくとも２個の架橋性二重結合を有する化合物を、２重ノズルを用いて使用時に混合しながら反応させて道路面に塗布する方法が実用化されている、（例えば特許文献３を参照）。しかし、この方法は、２重ノズルを使用する大型の噴射装置が必要であり、住宅などの比較的小規模な塗装に使用するのは困難であるという問題点を有する。 As a road surface coating method, there is a method in which an acrylic ester and a compound having at least two crosslinkable double bonds in one molecule are reacted while being mixed at the time of use using a double nozzle and applied to the road surface. It has been put into practical use (see, for example, Patent Document 3). However, this method has a problem that it requires a large-sized injection device using a double nozzle and is difficult to use for relatively small-scale painting such as a house.
かかる課題を解決するための本発明は、大型の塗布装置を使用とせず、住宅などの比較的小規模な作業場でも、一度の塗装で厚い塗膜の形成適用が可能であり、且つ速乾性の高い塗料を提供することを課題とする。
また、普通の塗装では剥離してしまうような基材、例えば鉄製の屋外構造物の上に塗装されることが多いので、本発明は、基材との接着性の強い厚塗り塗膜を形成する塗料を提供することを課題とする。
The present invention for solving such a problem does not use a large coating apparatus, can be applied to form a thick coating with a single coating even in a relatively small workplace such as a house, and has a quick drying property. It is an object to provide a high paint.
In addition, since it is often painted on a base material that is peeled off by ordinary coating, such as an iron outdoor structure, the present invention forms a thick coating film with strong adhesion to the base material. It is an object of the present invention to provide a paint that can be applied.
更に通常の塗装では摩耗されるような場所に塗装されることが多いので、耐摩耗性の強い塗膜を形成する塗料を提供することを課題とする。
また、例えばコンクリートのような粗面の上に直接塗布することがあるので、小さい凹凸を修復して、平滑で美麗な表面を有する塗料を提供することを課題とする。
また、塗装される場所に応じた機能を付加することができる塗料を提供することを課題とする。
Furthermore, since it is often applied to a place where it is worn by ordinary coating, it is an object to provide a coating material that forms a highly wear-resistant coating film.
Moreover, since it may apply | coat directly on rough surfaces, such as concrete, for example, it corrects a small unevenness | corrugation and makes it a subject to provide the coating material which has a smooth and beautiful surface.
It is another object of the present invention to provide a paint capable of adding a function corresponding to a place to be painted.
本発明は、かかる課題を解決するためになされたものであって、本発明の速乾性厚塗り塗料は、常温で重合して塗膜を形成する高分子樹脂のモノマー、オリゴマー、プレポリマー、又はプレコポリマーの中の１以上を、２．４０乃至５５．４重量部〈有効数字４桁目を四捨五入〉と、前記高分子樹脂の重合促進剤又は／及び硬化剤を、０．０６００乃至２２．４重量部と、平均粒径が２０μｍ以下であり、標準偏差が０．３５以下である大豆粉末を、０．０１３５乃至２．２４重量部と、水を、８．６９乃至６３．０重量部と、吸水性を有する粉末を、２０．０乃至７０．０重量部と、を含み、全体の重量を１００重量部としたことを特徴とする。
前記高分子樹脂と、前記重合促進剤又は／及び硬化剤と、の何れか一方が、重合開始剤を更に含むことができる。
The present invention has been made in order to solve such problems, and the quick-drying thick coating paint of the present invention is a monomer, oligomer, prepolymer, or polymer resin that forms a coating film by polymerization at room temperature. One or more of the precopolymers are added in an amount of 2.40 to 55.4 parts by weight (rounded off to the fourth significant digit), 0.0600 to 22.5 of the polymer resin polymerization accelerator or / and curing agent. 4 parts by weight, soybean powder having an average particle size of 20 μm or less and a standard deviation of 0.35 or less, 0.0135 to 2.24 parts by weight, and water, 8.69 to 63.0 parts by weight And 20.0 to 70.0 parts by weight of water-absorbing powder, and the total weight is 100 parts by weight.
Any one of the polymer resin and the polymerization accelerator or / and curing agent may further contain a polymerization initiator.
前記高分子樹脂は、エポキシ樹脂、ポリエステル樹脂、シリコーン樹脂、アクリル樹脂、ポリアクリロニトリル樹脂、ポリブタジエン樹脂、ポリスチレン樹脂の中の１以上であることができる。
前記高分子樹脂は、アクリル酸エステル樹脂、又はアクリル酸エステル‐スチレン共重合樹脂の中の１以上であることを特徴とする。
The polymer resin may be one or more of epoxy resin, polyester resin, silicone resin, acrylic resin, polyacrylonitrile resin, polybutadiene resin, and polystyrene resin.
The polymer resin is one or more of acrylic ester resin or acrylic ester-styrene copolymer resin.
前記吸水性を有する粉末が、珪藻土、活性白土、ゼオライト、セメント、炭酸カルシウム、リン酸アルミニウム、酸化チタン、シラスバルーンを含む中空微粒子、フライアッシュ、及び灰の中の１以上を含むことができる。
前記吸水性を有する粉末が、更に、顔料、ポリビニルアルコール繊維を含むセメント強化繊維、セメント強化剤、増粘剤、減水材、防錆剤、防虫剤、及び防腐剤の中の１以上を含むことを特徴とする。
The water-absorbing powder may include one or more of diatomaceous earth, activated clay, zeolite, cement, calcium carbonate, aluminum phosphate, titanium oxide, hollow fine particles including shirasu balloon, fly ash, and ash.
The water-absorbing powder further contains at least one of a pigment, a cement reinforced fiber containing polyvinyl alcohol fiber, a cement reinforced agent, a thickener, a water reducing material, a rust inhibitor, an insecticide, and an antiseptic. It is characterized by.
また、本発明の速乾性厚塗り水性塗料の製造方法は、請求項１乃至６の何れか１項に記載の塗料の製造方法であって、平均粒径が２０μｍ以下であり、標準偏差が０．３５以下である大豆粉末０．１５乃至３．５重量部を水に懸濁して１００重量部の大豆懸濁液とする大豆懸濁液製造段階と、重量比が９９：１乃至６０：４０の範囲であり、合計重量が２０乃至７０重量部の範囲である高分子樹脂のモノマー、オリゴマー、プレポリマー、又はプレコポリマーの中の１以上と、前記高分子の重合促進剤又は／及び硬化剤と、を別途に前記大豆懸濁液に懸濁して前記分子樹脂のモノマー、オリゴマー、プレポリマー、又はプレコポリマーの中の１以上のエマルジョンと、高分子モノマーの重合促進剤又は／及び硬化剤のエマルジョンと、を製造後に、それぞれを混合・撹拌して１００重量部の塗料用バインダー樹脂液とする塗料用バインダー樹脂液製造段階と、前記塗料用バインダー樹脂液３０乃至９０重量部と、前記粉末２０〜７０重量部とを混合して１００重量部の速乾性厚塗り塗料とする（重合開始剤の重量は除く）速乾性厚塗り塗料製造段階と、を有することを特徴とする。 Moreover, the manufacturing method of the quick-drying thick coating water-based paint of this invention is a manufacturing method of the coating material of any one of Claim 1 thru | or 6, Comprising: An average particle diameter is 20 micrometers or less, and a standard deviation is 0. A soybean suspension production stage in which 0.15 to 3.5 parts by weight of soybean powder having a particle size of 35 or less is suspended in water to obtain a soybean suspension of 100 parts by weight, and a weight ratio of 99: 1 to 60:40 At least one of the monomers, oligomers, prepolymers or precopolymers of the polymer resin having a total weight in the range of 20 to 70 parts by weight, and the polymerization accelerator or / and curing agent of the polymer And one or more emulsions in the molecular resin monomer, oligomer, prepolymer, or precopolymer, and a polymer monomer polymerization accelerator or / and hardener. With emulsion In addition, a binder resin solution for coating is prepared by mixing and stirring each to make 100 parts by weight of a binder resin solution for coating, 30 to 90 parts by weight of the binder resin solution for coating, and 20 to 70 parts by weight of the powder. To prepare a quick-drying thick coating material of 100 parts by weight (excluding the weight of the polymerization initiator).
本願の請求項１に係る速乾性厚塗り塗料は、本願発明の常温で重合して塗膜を形成する高分子樹脂原料の主剤を、２．４０乃至５５．４重量部と、前記高分子樹脂の補助剤を、０．０６００乃至２２．４重量部と、平均粒径が２０μｍ以下であり、標準偏差が０．３５以下である大豆粉末を、０．０１３５乃至２．２４重量部と、水を、８．６９乃至６３．０重量部と、吸水性を有する粉末を、２０．０乃至７０．０重量部と、を含み全体の重量を１００重量部とした塗料は、厚い塗膜を形成するにもかかわらず高い速乾性を有するという特徴を有する。 The quick-drying thick coating paint according to claim 1 of the present application is composed of 2.40 to 55.4 parts by weight of the main component of the polymer resin raw material that forms a coating film by polymerization at room temperature according to the present invention, Of soy powder having an average particle size of 20 μm or less and a standard deviation of 0.35 or less, 0.0135 to 2.24 parts by weight, and water. The coating composition comprising 8.69 to 63.0 parts by weight and 20.0 to 70.0 parts by weight of water-absorbing powder with a total weight of 100 parts by weight forms a thick coating film. In spite of this, it has a feature of having a high quick-drying property.
本願の請求項２に係る発明によれば、前記高分子樹脂原料の主剤又は補助剤の何れか一方に重合開始剤を加えることができる。これによって重合開始時期を制御できるので、反応速度の高い高分子樹脂原料の反応開始時期を制御できるという特徴を有する。
本願の請求項３に係る発明によれば、エポキシ樹脂、ポリエステル樹脂、シリコーン樹脂、アクリル樹脂、ポリアクリロニトリル樹脂、ポリブタジエン樹脂、ポリスチレン樹脂の中の１以上の高分子樹脂を用いることによって、基材との接着性が高く、耐摩耗性が高い速乾性厚塗り塗料を提供することができる。
According to the invention of claim 2 of the present application, a polymerization initiator can be added to either the main component or the auxiliary agent of the polymer resin raw material. As a result, the polymerization start time can be controlled, so that the reaction start time of the polymer resin raw material having a high reaction rate can be controlled.
According to the invention of claim 3 of the present application, by using one or more polymer resins among epoxy resin, polyester resin, silicone resin, acrylic resin, polyacrylonitrile resin, polybutadiene resin, polystyrene resin, It is possible to provide a quick-drying thick paint having high adhesion and high wear resistance.
本願の請求項４に係る発明によれば、アクリル酸エステル樹脂、又は／及びアクリル酸エステル‐スチレン共重合樹脂を用いることによって、基材との接着性が高く、耐摩耗性が高く、小さな凹凸には関係なく平坦な表面ヲ形成する速乾性厚塗り塗料を提供することができる。 According to the invention according to claim 4 of the present application, by using an acrylate resin or / and an acrylate-styrene copolymer resin, the adhesiveness to the base material is high, the wear resistance is high, and small unevenness. It is possible to provide a quick-drying thick coating that forms a flat surface regardless of the above.
本願の請求項５に係る発明によれば、吸水性粉末として、珪藻土、活性白土、ゼオライト、セメント、炭酸カルシウム、リン酸アルミニウム、酸化チタン、シラスバルーンを含む中空微粒子、フライアッシュ、及び灰の中の１以上を加えることによって、塗料用バインダー樹脂液のエマルジョンを解膠してバインダー樹脂の重合を開始させて固化・乾燥をさせると共に、吸水性粉末成分が速乾性厚塗り塗料の粘性を増加させて液だれを防ぐ効果及び増量剤として塗膜の厚さを増大させる効果を有する。 According to the invention of claim 5 of the present application, as the water-absorbing powder, diatomaceous earth, activated clay, zeolite, cement, calcium carbonate, aluminum phosphate, titanium oxide, hollow fine particles including shirasu balloon, fly ash, and ash By adding one or more of the above, the emulsion of the binder resin liquid for paint is peptized to initiate the polymerization of the binder resin to solidify and dry, and the water-absorbing powder component increases the viscosity of the quick-drying thick paint. The effect of preventing dripping and the effect of increasing the thickness of the coating film as an extender.
本願の請求項６に係る発明によれば、塗布する場所の必要性に応じて、顔料、ポリビニルアルコール繊維を含むセメント強化繊維、セメント強化剤、増粘剤、減水材、金属亜鉛や金属マグネシウムのような防錆剤、防虫剤、及び防腐剤の中の１以上を更に加えることによって、速乾性厚塗り塗料に、塗布する場所の必要に応じた機能を付加できるという特徴を有する。 According to the invention according to claim 6 of the present application, according to the necessity of the place to apply, pigment, cement reinforced fiber including polyvinyl alcohol fiber, cement reinforcing agent, thickener, water reducing material, metallic zinc and metallic magnesium By adding one or more of such rust preventives, insect repellents, and preservatives, the quick-drying thick paint can be provided with a function according to the necessity of the place to be applied.
本願の請求項７に係る発明によれば、大豆懸濁液を用い、高分子樹脂合成の主剤である高分子樹脂モノマーと、補助剤である重合促進剤又は／及び硬化剤と、を別個のエマルジョンを形成した後、混合して製造した塗料用バインダー樹脂液は、高分子樹脂合成の主剤である高分子樹脂モノマーの重合が防止された安定なエマルジョンを形成した。この塗料用バインダー樹脂液に吸水性粉末を加えることによって、エマルジョンが解膠されてバインダー樹脂の重合が開始され、速乾性厚塗り塗料が製造できる。これによって、バインダー樹脂の重合開始時期を制御できるので、容易に速乾性厚塗り塗料が製造できるという特徴を有する。 According to the invention according to claim 7 of the present application, a soybean suspension is used, and a polymer resin monomer that is a main component of polymer resin synthesis and a polymerization accelerator or / and a curing agent that is an auxiliary agent are separately provided. After the emulsion was formed, the coating binder resin liquid produced by mixing formed a stable emulsion in which polymerization of the polymer resin monomer, which is the main component of polymer resin synthesis, was prevented. By adding a water-absorbing powder to the binder resin liquid for paint, the emulsion is peptized to start the polymerization of the binder resin, and a quick-drying thick paint can be produced. As a result, the polymerization initiation timing of the binder resin can be controlled, so that a quick-drying thick paint can be easily produced.
本発明者は、豆乳として開示された特許文献４に記載の、平均粒径が２０μｍ以下であり、標準偏差が０．３５以下である大豆粉末（以下「大豆粉末」と略記する）と水との懸濁液（以下「大豆粉末懸濁液」と略記する）に含まれる大豆ケラチンが、塗料用の乳化剤として優れた作用を有することを見出して、本発明に着手した。 The present inventor has disclosed a soybean powder (hereinafter abbreviated as “soybean powder”) having an average particle size of 20 μm or less and a standard deviation of 0.35 or less described in Patent Document 4 disclosed as soy milk, water, It was found that soybean keratin contained in this suspension (hereinafter abbreviated as “soybean powder suspension”) has an excellent action as an emulsifier for paints, and the present invention was started.
本発明の速乾性厚塗り塗料は、塗膜形成の主剤である、常温で重合して塗膜を形成する高分子樹脂のモノマー、オリゴマー、プレポリマー、又はプレコポリマー（以下「高分子樹脂モノマー」と略記する）２．４０〜５５．４重量部と、塗膜形成の補助剤である高分子樹脂用の重合促進剤又は／及び硬化剤（以下「重合促進剤／硬化剤」と略記する）０．０６００〜２２．４重量部と、大豆粉末０．０１３５〜２．２４重量部と、吸水性を有する粉末（以下「吸水性粉末」と略記する）２０．０〜７０．０重量部と、水、８．６９〜６３．０重量部と、を含み、全体の重量を１００重量部とした（有効数字４桁目を四捨五入）。 The quick-drying thick paint of the present invention is a polymer resin monomer, oligomer, prepolymer, or precopolymer (hereinafter referred to as “polymer resin monomer”) that forms a coating film by polymerization at room temperature, which is the main component of coating film formation. 2.40 to 55.4 parts by weight) and a polymerization accelerator or / and curing agent for a polymer resin that is an auxiliary agent for coating film formation (hereinafter abbreviated as “polymerization accelerator / curing agent”). 0.0600 to 22.4 parts by weight, 0.0135 to 2.24 parts by weight of soybean powder, and 20.0 to 70.0 parts by weight of powder having water absorption (hereinafter abbreviated as “water absorbent powder”) , Water, 8.69 to 63.0 parts by weight, and the total weight was 100 parts by weight (the fourth significant digit was rounded off).
本発明の高分子樹脂モノマーは、本発明に適うものであれば特に限定されないが、エポキシ樹脂、ポリエステル樹脂、シリコーン樹脂、アクリル樹脂、ポリアクリロニトリル、ポリブタジエン、及びポリスチレンのモノマーを好ましい例として挙げることができる。
より好ましい実例として、アクリル樹脂の範疇に含まれるアクリル酸エステル重合体及びアクリル酸エステル‐スチレンと共重合体を挙げることができる。
高分子樹脂モノマーの重量が２．４０重量部未満では、充分な塗膜を形成できない場合があり、２２．４重量部を超えると、経済的に好ましくないだけでなく、速乾性、粘度低下による液だれ発生と塗膜の薄膜化等の速乾性厚塗り塗料としての特徴を示さない場合があった。
The polymer resin monomer of the present invention is not particularly limited as long as it is suitable for the present invention, but preferable examples include monomers of epoxy resin, polyester resin, silicone resin, acrylic resin, polyacrylonitrile, polybutadiene, and polystyrene. it can.
More preferable examples include acrylic acid ester polymers and acrylic acid ester-styrene copolymers that are included in the category of acrylic resins.
If the weight of the polymer resin monomer is less than 2.40 parts by weight, a sufficient coating film may not be formed, and if it exceeds 22.4 parts by weight, it is not only economically unfavorable, but also due to quick drying and reduced viscosity. In some cases, it did not show characteristics as a quick-drying thick paint such as dripping and thinning of the coating film.
重合促進剤又は／及び硬化剤の高分子樹脂モノマーに対する比率及び重量は、高分子樹脂モノマーの種類、及び用いる重合促進剤又は／及び硬化剤の種類によって使用説明書等に記載されているのでそれに従うこととし、重複した説明を省略する。
また、必要な場合には、高分子樹脂原料、又は重合促進剤又は／及び硬化剤の何れか一方に、前記高分子樹脂の重合開始剤を添加した。
The ratio and weight of the polymerization accelerator or / and curing agent to the polymer resin monomer are described in the instruction manual depending on the type of polymer resin monomer and the type of polymerization accelerator or / and curing agent used. And redundant description will be omitted.
Further, when necessary, a polymerization initiator for the polymer resin was added to either the polymer resin raw material, the polymerization accelerator or / and the curing agent.
大豆粉末は、平均粒径が２０μｍ以下であり、標準偏差が０．３５以下であり、含有量が、０．０１３５〜２．２４重量部の範囲であることが好ましい。平均粒径が２０μｍを超えるか、標準偏差が０．３５を超えるか、又は含有量が０．０１３５重量部未満であると、滲出する大豆ケラチンの量が不足して必要な乳化力が不足し、充分なエマルジョンを形成できず、エマルジョンが不安定になるか、高分子樹脂モノマーが重合を開始してしまう場合があった。大豆粉の含有量が２．２４重量部を超えても、乳化力の増加はわずかであり、エマルジョンの粘度が大きくなりすぎて操作が困難になる場合があった。 The soybean powder preferably has an average particle size of 20 μm or less, a standard deviation of 0.35 or less, and a content in the range of 0.0135 to 2.24 parts by weight. If the average particle size exceeds 20 μm, the standard deviation exceeds 0.35, or the content is less than 0.0135 parts by weight, the amount of soybean keratin that oozes out is insufficient and the necessary emulsifying power is insufficient. In some cases, a sufficient emulsion cannot be formed and the emulsion becomes unstable or the polymer resin monomer starts to polymerize. Even if the content of soybean powder exceeds 2.24 parts by weight, the increase in emulsifying power is slight, and the viscosity of the emulsion becomes too large, which sometimes makes operation difficult.
水の含有量は、８．６９〜６３．０重量部であることが好ましい。水が８．６９重量部未満では、適切な粘度を有する塗料が形成できない場合があり、６３．０重量部を超えると、高分子樹脂成分及び固形成分が不足する場合があった。 The water content is preferably 8.69 to 63.0 parts by weight. If water is less than 8.69 parts by weight, a paint having an appropriate viscosity may not be formed. If it exceeds 63.0 parts by weight, the polymer resin component and the solid component may be insufficient.
吸水性粉末は、エマルジョンの水分を吸収してエマルジョンを解膠できるものであれば特に制限されないが、珪藻土、活性白土、ゼオライト、セメント、炭酸カルシウム、リン酸アルミニウム、酸化チタン、シラスバルーンを含む中空粒子、フライアッシュ、及び灰の中の１以上から選ばれることが好ましい。 The water-absorbing powder is not particularly limited as long as it can absorb the moisture of the emulsion and peptize the emulsion, but it is hollow including diatomaceous earth, activated clay, zeolite, cement, calcium carbonate, aluminum phosphate, titanium oxide, and shirasu balloon. It is preferably selected from one or more of particles, fly ash, and ash.
特に、中空粒子であるシラスバルーンは開口部を有し、中空部分に水分を保留できるので好ましい。
吸水性粉末は、更に、顔料、セメント強化剤、ポリビニルアルコール繊維を含むセメント強化繊維、増粘剤、減水材、防錆剤、防虫剤、及び防腐剤の中の以上を含むことができる。
In particular, the shirasu balloon, which is a hollow particle, is preferable because it has an opening and can retain moisture in the hollow portion.
The water-absorbing powder may further include the above among pigments, cement reinforcing agents, cement reinforcing fibers including polyvinyl alcohol fibers, thickeners, water reducing materials, rust preventives, insect repellents, and preservatives.
吸水性粉末の量は、２０．０乃至７０．０重量部であることが好ましい。含有量が２０重量部未満では、充分な厚さの塗膜が形成できない、塗料用バインダー樹脂液の粘度が低すぎて液だれする、及び吸水性粉末の量が少なすぎて塗料用バインダー樹脂液のエマルジョンを充分に解膠することができず硬化時間が長くなる場合があるという問題がある。また、前記吸水性粉末の量が７０重量部を超えると、吸水性粉末の量に対するバインダー樹脂液の量が不足で形成される塗膜の性能が不十分になる、及び塗料の粘性が大きくなりすぎて塗布が困難になるという問題がある。 The amount of the water-absorbing powder is preferably 20.0 to 70.0 parts by weight. If the content is less than 20 parts by weight, a coating film having a sufficient thickness cannot be formed, the viscosity of the coating binder resin liquid is too low, and the amount of the water-absorbing powder is too small, so that the coating binder resin liquid is too small. There is a problem in that the emulsion cannot be sufficiently peptized and the curing time becomes long. On the other hand, if the amount of the water-absorbing powder exceeds 70 parts by weight, the performance of the coating film formed due to the insufficient amount of the binder resin liquid relative to the amount of the water-absorbing powder becomes insufficient, and the viscosity of the paint increases. There is a problem that it becomes too difficult to apply.
図１は、本発明の速乾性厚塗り水性塗料の製造工程を示すブロック図である。
以下に、図１を参照しながら、発明の速乾性厚塗り水性塗料の製造工程を説明する。
［大豆懸濁液製造工程］
本発明の大豆懸濁液は、特許文献４に従って製造したものを使用した。
本発明の大豆懸濁液は、大豆粉末０．１５〜３．５重量部と水とを混合して１００重量部とした大豆混合液を、６０ＭＰａ以上の圧力及び／又は１３０ｍ／秒以上の流速で細管内を通過させることにより破砕して製造した（Ｓ−１０）。
FIG. 1 is a block diagram showing the manufacturing process of the quick-drying thick-coating water-based paint of the present invention.
Below, the manufacturing process of the quick-drying thick coating water-based paint of the invention will be described with reference to FIG.
[Soybean suspension manufacturing process]
What was manufactured according to patent document 4 was used for the soybean suspension of this invention.
In the soybean suspension of the present invention, a soybean mixture obtained by mixing 0.15 to 3.5 parts by weight of soybean powder and water to 100 parts by weight is used at a pressure of 60 MPa or higher and / or a flow rate of 130 m / second or higher. The product was crushed and manufactured by passing through a thin tube (S-10).
大豆粉末の平均粒径が２０μｍを超えると、大豆懸濁液が解膠され易くなり不安定となり、また本発明で必要とする乳化力を発揮できなくなった。
また、大豆粉末の重量が０．１５重量部未満では、滲出される大豆ケラチンの量が少なすぎてエマルジョンの形成が不十分で、高分子樹脂のモノマーの重合が起こる場合があり、３．５重量部を超える大豆懸濁液の製造は追加の労力を有するが乳化力の増加はわずかであり、エマルジョンの粘度が大きくなりすぎて操作が困難になる場合があるという問題点を有する。
When the average particle size of the soybean powder exceeds 20 μm, the soybean suspension is easily peptized and becomes unstable, and the emulsifying power required in the present invention cannot be exhibited.
On the other hand, if the weight of the soybean powder is less than 0.15 parts by weight, the amount of soybean keratin that is exuded is too small to form an emulsion and polymerization of the monomer of the polymer resin may occur. The production of soy suspensions in excess of parts by weight has the additional labor, but the increase in emulsifying power is slight and has the problem that the viscosity of the emulsion becomes too high and the operation may be difficult.
［塗料用バインダー樹脂エマルジョン製造工程］
高分子樹脂モノマーと、重合促進剤又は／及び硬化剤と、を別途に前記大豆懸濁液に懸濁してエマルジョンとした後に、２つのエマルジョンを合わせ、混合して塗料用バインダー樹脂液を製造した（Ｓ−２０）。エマルジョンの製造方法及び混合方法は、通常の水性エマルジョン塗料を製造する撹拌装置やホモジナイザーであれば特に制限されない。
[Binder resin emulsion manufacturing process for paints]
A polymer resin monomer and a polymerization accelerator or / and a curing agent were separately suspended in the soybean suspension to form an emulsion, and then the two emulsions were combined and mixed to produce a binder resin solution for paint. (S-20). The emulsion production method and mixing method are not particularly limited as long as they are a stirrer or a homogenizer for producing a normal aqueous emulsion paint.
塗料用バインダー樹脂エマルジョンの重量を１００重量部としたときに、高分子樹脂モノマー及と、重合促進剤又は／及び硬化剤と、の合計重量は、２０乃至７０重量部の範囲であることが好ましく、３０乃至６０重量部の範囲であることがより好ましく、４０乃至５０重量部の範囲であることが最も好ましい。また、高分子モノマーと、重合促進剤又は／及び硬化剤と、の重量の比率は、６０：４０〜９９：１の範囲であることができる。 When the weight of the binder resin emulsion for paint is 100 parts by weight, the total weight of the polymer resin monomer and the polymerization accelerator or / and curing agent is preferably in the range of 20 to 70 parts by weight. 30 to 60 parts by weight is more preferable, and 40 to 50 parts by weight is most preferable. The weight ratio of the polymer monomer and the polymerization accelerator or / and the curing agent can be in the range of 60:40 to 99: 1.
高分子樹脂モノマーと、重合促進剤又は／及び硬化剤と、の合計重量が７０重量部を超えると、良好なエマルジョンを形成しにくい場合があり、２０重量部未満では、高分子樹脂成分が少なくなりすぎて、良好な塗膜を形成できない場合がある。
重合促進剤又は／及び硬化剤の高分子樹脂モノマーに対する比率及び重量は、高分子樹脂モノマーの種類、及び用いる重合促進剤又は／及び硬化剤の種類によって使用説明書等に記載されているのでそれに従うこととし、重複した説明を省略する。
If the total weight of the polymer resin monomer and the polymerization accelerator or / and curing agent exceeds 70 parts by weight, it may be difficult to form a good emulsion. If it is less than 20 parts by weight, the polymer resin component is small. It may become too much to form a good coating film.
The ratio and weight of the polymerization accelerator or / and curing agent to the polymer resin monomer are described in the instruction manual depending on the type of polymer resin monomer and the type of polymerization accelerator or / and curing agent used. And redundant description will be omitted.
［速乾性厚塗り塗料製造工程］
前記塗料用バインダー樹脂液と、前記吸水性粉末２０〜７０重量部と、を混合して製造した。
吸水性粉末の量は２０〜７０重量部の範囲であることが好ましく、３０〜７０重量部の範囲であることがより好ましく、最も好ましい例として、４０〜６０重量部の範囲を挙げることができる。
[Quick-drying paint manufacturing process]
The paint binder resin liquid was mixed with 20 to 70 parts by weight of the water-absorbing powder.
The amount of the water-absorbing powder is preferably in the range of 20 to 70 parts by weight, more preferably in the range of 30 to 70 parts by weight, and most preferable examples include the range of 40 to 60 parts by weight. .
塗料の硬化時間に対する要望は、その使用場面の状況に要求にされるが、本発明の塗料は速乾性であって、一般的にいえば１５〜３０分で指触乾燥し、３０〜１２０分で硬化乾燥することが好ましい。指触硬化時間が１５分未満では、塗料を調整してから塗布し終わるまでの時間が足りないことがあり、硬化時間が１２０分以上では、「速乾性」のとは言えないことがあるが、前記乾燥時間は塗料の種類や塗膜の厚さによっては許容される場合もある。
また、好ましくは、０．２ｍｍ以上、場合によっては１ｍｍ以上の塗膜を形成することが要求される場合もある。
Although the demand for the curing time of the paint is required depending on the situation of use, the paint of the present invention is quick-drying, and generally speaking, it is dry to the touch in 15 to 30 minutes, and 30 to 120 minutes. It is preferable to dry by curing. If the finger-curing time is less than 15 minutes, there may be insufficient time until the application is finished after the coating is adjusted. If the curing time is 120 minutes or more, it may not be said to be “quick-drying”. The drying time may be allowed depending on the type of paint and the thickness of the coating film.
Further, preferably, it may be required to form a coating film of 0.2 mm or more, and in some cases, 1 mm or more.
前記吸水性粉末の量が２０重量部未満では、充分な厚さの塗膜が形成できない、塗料用バインダー樹脂液の粘度が低すぎて液だれする、及び吸水性粉末の量が少なすぎて塗料用バインダー樹脂液のエマルジョンを充分に解膠することができず硬化時間が長くなる場合があるという問題がある。
前記吸水性粉末の量が７０重量部を超えると、吸水性粉末の量に対するバインダー樹脂液の量が不足で形成される塗膜の性能が不十分になる、及び塗料の粘性が大きくなりすぎて塗布が困難になるという問題がある。
When the amount of the water-absorbing powder is less than 20 parts by weight, a coating film having a sufficient thickness cannot be formed, the viscosity of the binder resin solution for coating is too low, and the amount of the water-absorbing powder is too small. There is a problem in that the binder resin liquid emulsion may not be sufficiently peptized and the curing time may be long.
If the amount of the water-absorbing powder exceeds 70 parts by weight, the performance of the coating film formed due to the insufficient amount of the binder resin liquid relative to the amount of the water-absorbing powder becomes insufficient, and the viscosity of the paint becomes too large. There is a problem that application becomes difficult.
ここで、速乾性厚塗り塗料工程（Ｓ−３０）において、塗料の重量を１００重量部とした場合に、吸水性粉末の重量は、２０〜７０重量部であり、塗料用バインダー樹脂液の重量は３０〜８０重量部である。
塗料用バインダー樹脂液製造工程（Ｓ−２０）における高分子樹脂モノマーと重合促進剤又は／及び硬化剤との合計重量は、塗料用バインダー樹脂液を１００重量部とした場合に２０乃至７０重量部であるから、塗料の重量を１００重量部とした場合に換算すると、硬化剤の合計重量は６〜５６重量部であり、大豆懸濁液の重量は、９〜６４重量部である。
Here, in the quick-drying thick paint step (S-30), when the weight of the paint is 100 parts by weight, the weight of the water-absorbing powder is 20 to 70 parts by weight, and the weight of the binder resin liquid for paints Is 30 to 80 parts by weight.
The total weight of the polymer resin monomer and the polymerization accelerator or / and the curing agent in the coating binder resin liquid production step (S-20) is 20 to 70 parts by weight when the coating binder resin liquid is 100 parts by weight. Therefore, when converted to 100 parts by weight of the coating material, the total weight of the curing agent is 6 to 56 parts by weight, and the weight of the soybean suspension is 9 to 64 parts by weight.
塗料用バインダー樹脂液製造工程（Ｓ−２０）におけるモノマーと重合促進剤又は／及び硬化剤の重量比は９９：１〜６０：４０であるから、塗料の重量を１００重量部とした場合に換算すると、高分子樹脂モノマーの量は、２．４０〜５５・４（有効数字４桁目四捨五入、以下同じ）であり、重合促進剤又は／及び硬化剤の重量は、０．０６００〜２２．４重量部である。 Since the weight ratio of the monomer and the polymerization accelerator or / and the curing agent in the binder resin liquid production process (S-20) for paint is 99: 1 to 60:40, it is converted when the weight of the paint is 100 parts by weight. Then, the amount of the polymer resin monomer is 2.40 to 55.4 (rounded to the fourth significant digit, the same shall apply hereinafter), and the weight of the polymerization accelerator or / and the curing agent is 0.0600 to 22.4. Parts by weight.
塗料用バインダー樹脂液製造工程（Ｓ−２０）における大豆懸濁液の重量は、塗料用バインダー樹脂液を１００重量部とした場合に３０〜８０重量部であるから、塗料の重量を１００重量部とした場合に換算すると、９．００〜６４．０重量部である。大豆懸濁液製造工程（Ｓ−１０）における大豆の量は、大豆懸濁液を１００重量部とした場合に１．５〜３．５重量部であるから、塗料の重量を１００重量部とした場合に換算すると、大豆の量は、０．０１３５〜２．２４重量部であり、水の量は、８．６９〜６３．０重量部の範囲である。 Since the weight of the soybean suspension in the paint binder resin liquid production step (S-20) is 30 to 80 parts by weight when the paint binder resin liquid is 100 parts by weight, the weight of the paint is 100 parts by weight. In other words, it is 9.00 to 64.0 parts by weight. Since the amount of soybean in the soybean suspension production step (S-10) is 1.5 to 3.5 parts by weight when the soybean suspension is 100 parts by weight, the weight of the coating is 100 parts by weight. When converted, the amount of soybean is 0.0135 to 2.24 parts by weight, and the amount of water is in the range of 8.69 to 63.0 parts by weight.
以下に、実施例を示し、本発明を詳細に説明する。
［大豆懸濁液製造工程］
（製造例１）
平均粒径が２０μｍ以下である大豆粉末０．２５重量部と水とを混合して１００重量部とした大豆混合液を、６０ＭＰａ以上の圧力及び／又は１３０ｍ／秒以上の流速で細管内を通過させることにより破砕して大豆懸濁液を製造した。
なお、本発明における「粒径」は、ＪＩＳ Ｚ８８２５−１：２００１（粒子径解析−レーザー回折法／ＩＳＯ９２７６−１：１９９８に対応）に従って屈折率：１．７０−０．２０ｉ（ｉは虚数単位）の条件で測定されたデータ（散乱光強度）をＷｉｎｇＳＡＬＤｗｏ用いて変換することにより得られる粒径値を意味する。下記表１に、測定結果を示す。
Hereinafter, the present invention will be described in detail with reference to examples.
[Soybean suspension manufacturing process]
(Production Example 1)
A soy mixed liquid in which 0.25 parts by weight of soybean powder having an average particle size of 20 μm or less and water are mixed to make 100 parts by weight passes through a narrow tube at a pressure of 60 MPa or more and / or a flow rate of 130 m / second or more. To produce a soybean suspension.
The “particle diameter” in the present invention is a refractive index of 1.70-0.20i (i is an imaginary unit) according to JIS Z8825-1: 2001 (corresponding to particle diameter analysis—laser diffraction method / ISO9276-1: 1998). ) Means a particle size value obtained by converting data (scattered light intensity) measured under the conditions of (2) using WingSALDwo. Table 1 below shows the measurement results.
（比較例１）
平均粒径が５０μｍ以下である大豆粉末を用いて、実施例１と同様の方法で大豆懸濁液
を製造した。
(Comparative Example 1)
A soybean suspension was produced in the same manner as in Example 1 using soybean powder having an average particle size of 50 μm or less.
［塗料用バインダー樹脂液製造工程］
（実施例１）
＜アクリル酸ブチル‐スチレン共重合体バインダー樹脂液の製造＞
塗料用バインダー樹脂液を１００重量部として、アクリル酸ブチル‐スチレン共重合体オリゴマー４．０重量部、重合促進剤であるジメチル−ｐ−トルイジン０．５重量部、及び実施例１で製造した大豆懸濁液４９．５重量部を、高速撹拌機を用い１時間撹拌してエマルジョンとした。この場合、アクリル酸ブチル‐スチレン共重合体オリゴマーは、重合促進剤であるジメチル−ｐ−トルイジンを含んでいても、重合が僅かしか進まない。
[Binder resin liquid manufacturing process for paint]
Example 1
<Production of butyl acrylate-styrene copolymer binder resin solution>
100 parts by weight of the binder resin solution for paint, 4.0 parts by weight of butyl acrylate-styrene copolymer oligomer, 0.5 parts by weight of dimethyl-p-toluidine as a polymerization accelerator, and soybean produced in Example 1 49.5 parts by weight of the suspension was stirred for 1 hour using a high-speed stirrer to obtain an emulsion. In this case, even if the butyl acrylate-styrene copolymer oligomer contains dimethyl-p-toluidine which is a polymerization accelerator, the polymerization proceeds only slightly.
同様に、アクリル酸ブチル‐スチレン共重合体の架橋剤であるポリプロピレングリコールジメタクリレート２．０重量部と実施例１で製造した大豆懸濁液８．０重量部を、高速撹拌機を用い１時間撹拌してエマルジョンとした。
次いで、アクリル酸ブチル‐スチレン共重合体オリゴマーのエマルジョン及びポリプロピレングリコールジメタクリレートのエマルジョンを合わせ、高速撹拌機を用い１０分間撹拌してアクリル酸ブチル‐スチレン共重合体バインダー樹脂液を製造した。
Similarly, 2.0 parts by weight of polypropylene glycol dimethacrylate, which is a crosslinking agent of butyl acrylate-styrene copolymer, and 8.0 parts by weight of the soybean suspension prepared in Example 1 were used for 1 hour using a high-speed stirrer. Stir to make an emulsion.
Subsequently, the emulsion of butyl acrylate-styrene copolymer oligomer and the emulsion of polypropylene glycol dimethacrylate were combined and stirred for 10 minutes using a high-speed stirrer to produce a butyl acrylate-styrene copolymer binder resin solution.
（実施例２）
＜エポキシ樹脂バインダー樹脂液の製造＞
塗料用バインダー樹脂液を１００重量部として、ビスフェノールＡ型エポキシモノマー３５重量部と請求項１で製造した大豆懸濁液３５重量部を、高速撹拌機を用い１時間撹拌してエマルジョンとした。
(Example 2)
<Manufacture of epoxy resin binder resin solution>
100 parts by weight of the binder resin solution for coating was used, and 35 parts by weight of the bisphenol A type epoxy monomer and 35 parts by weight of the soybean suspension prepared in claim 1 were stirred for 1 hour using a high-speed stirrer to obtain an emulsion.
同様に、エポキシ硬化剤１５重量部、請求項１で製造した大豆懸濁液１４．５重量部、及び重合開始剤であるＤＢＵ（ジアザビシクロウンデセン）０．５重量部を、高速撹拌機を用い１時間撹拌してエマルジョンとした。
次いで、ビスフェノールＡ型エポキシモノマーのエマルジョン及びエポキシ硬化剤−ＤＢＵのエマルジョンを合わせ、高速撹拌機を用い１０分間撹拌してエポキシ樹脂バインダー樹脂液を製造した。
Similarly, 15 parts by weight of an epoxy curing agent, 14.5 parts by weight of the soybean suspension produced in claim 1, and 0.5 parts by weight of DBU (diazabicycloundecene) as a polymerization initiator were added to a high-speed stirrer. And stirred for 1 hour to make an emulsion.
Next, the emulsion of bisphenol A type epoxy monomer and the emulsion of epoxy curing agent-DBU were combined and stirred for 10 minutes using a high speed stirrer to produce an epoxy resin binder resin solution.
（実施例３）
＜シリコーン樹脂バインダー樹脂液の製造＞
塗料用バインダー樹脂液を１００重量部として、オルガノハイドロゲンポリシロキサン４１重量部、重合触媒であるＭ，Ｍ−ヒドロキシジエチルアミン２重量部、及び請求項１で製造した大豆懸濁液４３重量部を、高速撹拌機を用い１時間撹拌してオルガノハイドロゲンポリシロキサン−重合触媒エマルジョンとした。
同様に、両末端水酸基含有ポリシロキサン７重量部と請求項１で製造した大豆懸濁液７重量部を、高速撹拌機を用い１時間撹拌して両末端水酸基含有ポリシロキサンエマルジョンとした。
(Example 3)
<Manufacture of silicone resin binder resin liquid>
100 parts by weight of the binder resin solution for paint, 41 parts by weight of organohydrogenpolysiloxane, 2 parts by weight of M, M-hydroxydiethylamine as a polymerization catalyst, and 43 parts by weight of the soybean suspension produced in claim 1 The mixture was stirred for 1 hour using a stirrer to prepare an organohydrogenpolysiloxane-polymerization catalyst emulsion.
Similarly, 7 parts by weight of both-end hydroxyl group-containing polysiloxane and 7 parts by weight of the soybean suspension prepared in claim 1 were stirred for 1 hour using a high-speed stirrer to obtain a both-end hydroxyl group-containing polysiloxane emulsion.
次いで、オルガノハイドロゲンポリシロキサン−重合触媒エマルジョン及び両末端水酸基含有ポリシロキサンエマルジョンを合わせ、高速撹拌機を用い１０分間撹拌してシリコーン樹脂塗料用バインダー液を製造した。 Next, the organohydrogenpolysiloxane-polymerization catalyst emulsion and the polysiloxane emulsion containing hydroxyl groups at both terminals were combined and stirred for 10 minutes using a high-speed stirrer to produce a binder liquid for silicone resin paint.
（比較例１）
実施例１と同様に、但し均粒径が２０μｍ以下である大豆粉末の代わりに、平均粒径が５０μｍ以下である大豆粉末を用いてエポキシ樹脂塗料用バインダー樹脂液を製造した。
(Comparative Example 1)
As in Example 1, a binder resin solution for epoxy resin coatings was produced using soybean powder having an average particle size of 50 μm or less instead of soybean powder having an average particle size of 20 μm or less.
（比較例２）
実施例１と同様に、但し大豆懸濁液の代わりに脱イオン水を用いてエポキシ樹脂塗料用バインダー樹脂液を製造した。
(Comparative Example 2)
In the same manner as in Example 1, except that a deionized water was used instead of the soybean suspension to prepare a binder resin solution for an epoxy resin paint.
（比較例３）
実施例１と同様に、但し大豆懸濁液の代わりに脱イオン水に乳化剤として２．５重量％のグリシジルエーテル系乳化剤を添加してエポキシ樹脂塗料用バインダー樹脂液を製造した。
実施例１〜３、及び比較例１〜３の塗料用バインダー樹脂液の安定性を１カ月関観察し、その結果を表２に示す
安定性評価基準 ◎：安定性に優れ評価期間中変化は見られなかった。
○：安定であったが、１ヶ月後に僅かなエマルジョンの解膠又は高
分子樹脂の重合が観察された。
△：やや不安定で、解膠又は重合が進行した。
×：混合後直ちに解膠又は重合が進行した。
(Comparative Example 3)
In the same manner as in Example 1, except that 2.5% by weight of a glycidyl ether emulsifier was added as an emulsifier to deionized water instead of the soybean suspension to prepare a binder resin liquid for epoxy resin coatings.
The stability of the binder resin liquids for paints of Examples 1 to 3 and Comparative Examples 1 to 3 was observed for one month, and the results are shown in Table 2. Stability evaluation criteria ◎: Excellent stability and change during the evaluation period I couldn't see it.
○: Stable, but slight emulsion peptization or high after 1 month
Polymerization of the molecular resin was observed.
Δ: Slightly unstable and peptization or polymerization progressed.
X: Peptization or polymerization proceeded immediately after mixing.
表２に示すように、本発明の実施例１〜３の塗料用バインダー樹脂液は、安定性に優れ評価期間中変化は見られなかったが、大豆懸濁液の代わりに脱イオン水を用いてエポキシ樹脂塗料用バインダー樹脂液を製造した比較例２は、直ちに高分子樹脂の重合が進行し、樹脂成分が分離した。一方、平均粒径が５０μｍ以下である大豆粉末を用板比較例１及び２．５重量％のグリシジルエーテル系乳化剤を添加した比較例３の試料は、２〜３日でエマルジョンが解膠され、その時点では重合が完了していた As shown in Table 2, the binder resin solutions for paints of Examples 1 to 3 of the present invention were excellent in stability and did not change during the evaluation period, but deionized water was used instead of the soybean suspension. In Comparative Example 2 in which the binder resin liquid for epoxy resin coating was produced, the polymerization of the polymer resin proceeded immediately and the resin component was separated. On the other hand, the soybean powder having an average particle size of 50 μm or less, the sample of Comparative Example 3 to which the glycidyl ether emulsifier of 2.5% by weight was added to the soybean plate comparative example, the emulsion was peptized in 2 to 3 days, At that time the polymerization was complete
［速乾性厚塗り塗料製造工程］
（実施例４〜７）
白セメント３６．７重量％、珪砂１８．０重量％、炭酸カルシウム３３．３重量％、シラスバルーン１０．０重量％、及び酸化チタン２，０重量％から成る吸水性粉末を混合して吸水性粉末を製造した。
実施例１で製造したアクリル酸ブチル‐スチレン共重合体バインダー樹脂液に、上記で製造した吸水性粉末を表２に示す割合で投入し、直ちに撹拌機で撹拌して実施例４〜７の速乾性厚塗りシリコーン樹脂塗料を製造した。
製造した塗料を、塗布し、形成された塗料の粘度及び塗膜の外観を観察、評価すると共に、触指乾燥時間と、硬化時間を測定した。それらの評価結果を、表３に示す。
[Quick-drying paint manufacturing process]
(Examples 4 to 7)
Mixing water-absorbing powder composed of 36.7% by weight of white cement, 18.0% by weight of silica sand, 33.3% by weight of calcium carbonate, 10.0% by weight of shirasu balloon, and 2.0% by weight of titanium oxide A powder was produced.
Into the butyl acrylate-styrene copolymer binder resin solution produced in Example 1, the water-absorbing powder produced above was added in the ratio shown in Table 2, and immediately stirred with a stirrer to speed up Examples 4-7. A dry thick silicone resin paint was produced.
The produced paint was applied, the viscosity of the formed paint and the appearance of the coating film were observed and evaluated, and the dry time of the finger and the curing time were measured. The evaluation results are shown in Table 3.
（比較例４、５）
実施例３と同じ方法で、但し塗料用バインダー樹脂液と吸水性粉末の添加量を変化させて表２に示す速乾性厚塗り塗料を製造し、直ちに塗膜を形成するように塗布した。それらの評価結果を、表３に示す。
(Comparative Examples 4 and 5)
A quick-drying thick paint shown in Table 2 was produced in the same manner as in Example 3 except that the addition amount of the binder resin liquid for paint and the water-absorbing powder was changed, and immediately applied to form a coating film. The evaluation results are shown in Table 3.
（実施例８、９）
＜速乾性厚塗りエポキシ樹脂塗料及びシリコーン樹脂塗料＞
ポルトランドセメント６３．４重量部、リン酸アルミニウム１０重量部、亜鉛末２６，６重量部を混合して吸水性粉末を製造した。この吸水性粉末各５０重量部を、実施例２，３で製造したエポキシ樹脂バインダー樹脂液と、シリコーン樹脂バインダー樹脂液各５０重量部に投入し、直ちに撹拌機で撹拌して実施例８、９の速乾性厚塗りシリコーン樹脂塗料を製造した。
(Examples 8 and 9)
<Quick-drying thick epoxy resin paint and silicone resin paint>
A water-absorbing powder was produced by mixing 63.4 parts by weight of Portland cement, 10 parts by weight of aluminum phosphate, and 26,6 parts by weight of zinc powder. 50 parts by weight of each of the water-absorbing powders were put into 50 parts by weight of the epoxy resin binder resin liquid prepared in Examples 2 and 3 and each of the silicone resin binder resin liquids, and immediately stirred with a stirrer. A quick-drying thick-coating silicone resin paint was produced.
製造した塗料を、直ちに塗布し、形成された塗料の粘度及び塗膜の外観を観察、評価すると共に、触指乾燥時間と、硬化時間を測定した。それらの評価結果を、表３に示す。
実施例８、９で製造した塗料は、吸水性粉末に、還元剤として金属亜鉛が加えられているので、例えばコンクリート用鉄筋のした塗り剤として好ましく用いることができる。
実施例８、９で製造した塗料の評価結果を、表３に示す。
The prepared paint was applied immediately, and the viscosity of the formed paint and the appearance of the coating film were observed and evaluated, and the dry time of the finger and the curing time were measured. The evaluation results are shown in Table 3.
The coating materials produced in Examples 8 and 9 can be preferably used as, for example, a coating with a reinforcing bar for concrete, since metallic zinc is added as a reducing agent to the water-absorbing powder.
Table 3 shows the evaluation results of the paints produced in Examples 8 and 9.
評価基準
・粘度 厚塗り塗料としての使用感を官能評価した。
◎：優秀
○：良好
△：やや不良
×：不良
・外観 外観を総合的に官能評価した。
◎：優秀
○：良好
△：やや不良
×：不良
但し、触指乾燥時間は、指で塗面に触れても指が汚れなくなる時間であり、硬化時間は、塗面の中央を親指と人差指とで強くはさんでみて、塗面に指紋によるへこみがつかず、塗膜の動きが感じられず、また塗面の中央を指先で急速に繰り返しこすってみて塗面にすりあとがつかなくなる時間である
Evaluation criteria
-Viscosity Sensory evaluation of the feeling of use as a thick paint.
A: Excellent
○: Good
Δ: Somewhat bad
X: Defect ・ Appearance The appearance was comprehensively sensory evaluated.
A: Excellent
○: Good
Δ: Somewhat bad
×: Defect However, the finger drying time is the time when the finger does not get dirty even if it touches the paint surface with the finger, and the curing time is determined by strongly sandwiching the center of the paint surface with the thumb and index finger, It is the time when the dent due to the fingerprint does not stick, the movement of the coating film is not felt, and the center of the coating surface is repeatedly rubbed with the tip of the finger and the coating surface is not rubbed.
表３に示すように、実施例４の試料は、吸水性粉末の含量が多めなので、速乾性厚塗り塗料の粘度が高すぎて若干扱いにくい面があり、外観も光沢に乏しいが、安価な吸収性粉末を多く含み経済的に有利である。
実施例５の試料は、速乾性厚塗り塗料の粘度も、塗装体の外観も良好であった。
実施例６の試料は、吸水性粉末の含有量が少なめなので粘度が低く、垂直面に塗ると液だれする心配がある。
As shown in Table 3, since the sample of Example 4 has a high water-absorbing powder content, the viscosity of the quick-drying thick paint is too high to be a little difficult to handle, and the appearance is poor in gloss, but is inexpensive. It contains a lot of absorbent powder and is economically advantageous.
In the sample of Example 5, the viscosity of the quick-drying thick paint and the appearance of the coated body were good.
The sample of Example 6 has a low viscosity because the content of the water-absorbing powder is small, and there is a concern that the liquid may drip when applied to a vertical surface.
実施例７の試料は、吸水性粉末の含有量が少ないので、粘度が低いという問題点はあるが、吸水性粉末が比重が約０．２ｇ／ｃｍ２と軽量のシラスバルーンの比率を多くすれば、使用可能であると判断した。 The sample of Example 7 has a problem that the viscosity is low because the content of the water-absorbing powder is small, but the water-absorbing powder has a specific gravity of about 0.2 g / cm 2 and increases the ratio of the light-weight shirasu balloon. It was judged that it was usable.
比較例４の試料は、塗料用バインダー樹脂液の量が少なすぎて、強くこすると粉体が剥がれ落ち、比較例５のサンプルは、吸水性粉末の量が少なすぎて粘度が低くなりすぎると共に、エマルジョンの解膠の進行が遅く、速乾性厚塗り塗料としては性能が不十分であった。 In the sample of Comparative Example 4, the amount of the binder resin liquid for paint is too small, and when rubbed strongly, the powder peels off. In the sample of Comparative Example 5, the amount of the water-absorbing powder is too small and the viscosity becomes too low. The progress of peptization of the emulsion was slow, and the performance as a quick-drying thick coating was insufficient.
実施例８のエポキシ樹脂塗料及び実施例９乃シリコーン樹脂塗料も優秀な粘度及び塗膜の外観を有する。しかし、これらの塗料は、通常の塗布方法よりは乾燥時間は短縮されているが、常温ではアクリル酸ブチル‐スチレン共重合体樹脂よりも重合速度が遅いので、アクリル酸ブチル‐スチレン共重合体樹脂よりは長くかかる。 The epoxy resin paint of Example 8 and the silicone resin paint of Example 9 also have excellent viscosity and coating appearance. However, these paints have a shorter drying time than the usual coating method, but the polymerization rate is slower than butyl acrylate-styrene copolymer resin at room temperature, so butyl acrylate-styrene copolymer resin It takes longer.
Claims (7)
平均粒径が２０μｍ以下であり、標準偏差が０．３５以下である大豆粉末０．１５乃至３．５重量部を水に懸濁して１００重量部の大豆懸濁液とする大豆懸濁液製造段階と、
重量比が９９：１乃至６０：４０の範囲であり、合計重量が２０乃至７０重量部の範囲である高分子樹脂のモノマー、オリゴマー、プレポリマー、又はプレコポリマーの中の１以上と、高分子の重合促進剤又は／及び硬化剤と、を別途に前記大豆懸濁液に懸濁して前記分子樹脂のモノマー、オリゴマー、プレポリマー、又はプレコポリマーの中の１以上のエマルジョンと、前記重合促進剤又は／及び硬化剤のエマルジョンと、を製造後に、それぞれを混合・撹拌して１００重量部の塗料用バインダー樹脂液とする塗料用バインダー樹脂液製造段階と、
前記塗料用バインダー樹脂液３０乃至９０重量部と、吸水性を有する粉末２０〜７０重量部とを混合して１００重量部の速乾性厚塗り塗料とする（重合開始剤の重量は除く）速乾性厚塗り塗料製造段階と、
を有することを特徴とする速乾性厚塗り塗料の製造方法。 A method for producing a paint according to any one of claims 1 to 5,
Production of soybean suspension by suspending 0.15 to 3.5 parts by weight of soybean powder having an average particle size of 20 μm or less and a standard deviation of 0.35 or less in water to give 100 parts by weight of soybean suspension Stages,
One or more of the monomers, oligomers, prepolymers or precopolymers of the polymer resin having a weight ratio in the range of 99: 1 to 60:40 and a total weight in the range of 20 to 70 parts by weight; A polymerization accelerator or / and a curing agent, and separately suspended in the soybean suspension and one or more emulsions in the monomer, oligomer, prepolymer, or precopolymer of the molecular resin, and the polymerization accelerator Or / and an emulsion of a curing agent, and after the production, mixing and stirring each to produce 100 parts by weight of the binder resin liquid for paint,
30 to 90 parts by weight of the binder resin solution for paint and 20 to 70 parts by weight of water-absorbing powder are mixed to form a quick-drying thick paint of 100 parts by weight (excluding the weight of the polymerization initiator). Thick paint production stage,
A method for producing a quick-drying thick paint, characterized by comprising:
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| JP2021193155A (en) * | 2020-06-08 | 2021-12-23 | 株式会社まつえペイント | Coating composition and method for forming coated film |
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