WO2009104779A1

WO2009104779A1 - Active energy ray-curable coating composition, method for formation of coating film, and coated article

Info

Publication number: WO2009104779A1
Application number: PCT/JP2009/053119
Authority: WO
Inventors: 稲田祐一; 増田秀樹
Original assignee: 関西ペイント株式会社
Priority date: 2008-02-18
Filing date: 2009-02-17
Publication date: 2009-08-27

Abstract

Disclosed is an active energy ray-curable coating composition which is characterized by comprising: (a1) an acrylic acid ester of a non-cyclic oligosaccharide or a derivative thereof, which has an weight average molecular weight of 400 to 2,000 and contains 3.0 to 12.0 acryloyl groups on average per molecule; and (a2) a photopolymerization initiator. The active energy ray-curable coating composition is a bio-derived active energy ray-curable coating composition, and can form a coating film having excellent finished appearance, pencil hardness, scratch resistance, weather resistance and solvent resistance.

Description

Description Active energy ray curable coating composition, coating film forming method, and coated article Technical Field

The present invention relates to an active energy ray-curable coating composition containing an acrylic ester of a specific acyclic oligosaccharide having an acryloyl group or a derivative thereof. Furthermore, the present invention provides a method of laminating a base coating film using a starch-based base coating composition using starch and a coating film using an active energy ray-curable aqueous coating composition using saccharides on the base coating film. Coating film forming method and a coated article obtained by the coating film forming method. Background art

In recent years, from the perspective of reducing the impact on global warming,

C_〇 has been required to reduce the ₂ emissions, a renewable resources to replace petroleum, positively utilizing biological components not to increase the amount of released C_〇 ₂ in carbon dioxide circulating on earth It is demanded. Typical materials for such renewable resources include polysaccharide starch, modified starch such as acetylated starch. These starches or modified starches have been conventionally used in the food industry and paper industry, but in recent years, they have also been used in fields such as food containers, packaging materials, cushioning sheets, agricultural films, and disposable ommu. It is becoming possible. In order to use starch as a raw material for industrial products, various improvements related to modified starch have been accumulated along with the modification of starch. The basic structure of starch is a mixture of amylose with 0! —D—glucose linearly linked by one or four single bonds and amycin bectin with a branched structure. Modifications by esterification, etherification, etc. have been made in the 1960's by utilizing the hydroxyl group in the structure.

Japanese Laid-Open Patent Publication No. 54-126096, Japanese Laid-Open Patent Publication No. 5-5900-5, Japanese Laid-Open Patent Publication No. Sho 56-16-27746, and Japanese Laid-Open Patent Publication No. 8-2-2. No. 3 9 4 0 2 discloses a graph in which a starch resin and an acrylic resin are indirectly grafted via polyisocyanate, as well as a radical graft polymerization of unsaturated monomers in starch or modified starch. An invention related to the grafted starch is disclosed.

In addition, Japanese Patent Laid-Open Nos. 6-2 0 7 0 47, 8-2 3 1 7 6 2 and 2 0 0 2 — 1 6 7 5 2 0 disclose starch and other As an example of combining plant-derived resins, an invention using a polymer blend in which starch or modified starch and cellulose derivatives are combined is disclosed as a molding material. In addition, an invention relating to a resin composition using a starch-based resin as a water-absorbing resin is disclosed.

As is clear from these prior patent documents, a starch-based resin itself obtained by combining or grafting various polymers is a known technique. However, all of these technologies assume adhesives, structural materials, injection molding materials, sheets, etc. as the applications of starch resins, and few have been disclosed for use as paints.

Regarding a paint using a starch-based resin, Japanese Patent Application Laid-Open No. 2000-087-2 has a function of reacting complementarily with starch and at least one hydroxyl group contained in the starch molecule. An invention relating to a curable starch composition, which is a mixture of curing agents having groups, is disclosed. It is also disclosed that curable types such as an oxidation polymerization curable type, a room temperature curable type, and an active energy ray curable type are possible.

Japanese Patent Application Laid-Open No. 2 0 0 6 — 2 8 2 9 60 describes starch, polyisocyanate curing agent, plant-derived resin excluding starch, metal complex and Curing containing a blocking agent selected from diketones, acetoacetic esters, malonic esters, ketones having a hydroxyl group at the iS position, aldehydes having a hydroxyl group at the iS position, and esters having a hydroxyl group at the / 3 position An invention relating to a modified starch composition is disclosed.

However, with respect to these starch-based paints, a coating film forming method capable of forming a coating film excellent in finish, pencil hardness, scratch resistance, adhesion, weather resistance, alkali resistance, and solvent resistance on an object to be coated. There was no. In addition, the use of organic solvent-based paints in all paints used has a problem of increasing the amount of solvent used.

In addition, Japanese Patent Application Laid-Open No. 10-258582 discloses a (meth) acrylic acid ester of cyclodextrin and an active energy linear curing resin composition containing the same. The energy ray curable resin composition has a structure in which glucose is cyclically linked by a glycosidic bond, and its steric freedom is low, so that photocurability is not sufficient. Disclosure of the invention

The present invention has been made in view of the above circumstances, an object of the present invention has less emissions of total C_〇 ₂ involved in the life cycle of the product, it is possible to reduce environmental pollution, finished appearance, pencil hardness, resistance to An object of the present invention is to provide a bioactive active energy ray-curable coating composition capable of forming a coating film having excellent scratch resistance, weather resistance, solvent resistance and photocurability.

Furthermore, another object of the present invention is to use a saccharide or a derivative thereof, or starch or modified starch as a raw material for a coating composition, and finish, pencil hardness, scratch resistance, interlayer adhesion, weather resistance, resistance An object of the present invention is to provide a method for forming a coating film, which is excellent in alkalinity and solvent resistance, and can obtain a multilayer coating film capable of reducing the amount of organic solvent used. As a result of intensive studies to solve the above-described problems of the prior art, the present inventors have found that an acyclic oligosaccharide having a specific molecular weight and a specific number of acryloyl groups or an acrylate ester thereof. The inventors have found that the above object can be achieved by an active energy ray-curable coating composition containing (a 1) and a photopolymerization initiator (a 2), and have completed the present invention.

Furthermore, the present inventors apply a starch-based coating composition containing a starch-based resin and a coloring pigment and / or a luster pigment on a substrate to form a base coating film, A step of coating an active energy ray-curable aqueous coating composition containing an aqueous dispersion of a saccharide or a derivative thereof (b 1) and a photopolymerization initiator (b 2) on the base coating film. And it discovered that said another objective could be achieved by the coating-film formation method characterized by the step of irradiating an active energy ray, and came to complete this invention.

That is, the present invention relates to the following aspects.

[Aspect 1]

Acrylic esters of non-cyclic oligosaccharides or derivatives thereof having a weight average molecular weight of 400 to 2,00,000 and an average of 3.0 to 12.0 acryloyl groups per molecule (al ) And a photopolymerization initiator (a 2). An active energy ray-curable coating composition comprising:

[Aspect 2]

The active energy ray-curable coating composition according to embodiment 1, wherein the acyclic oligosaccharide or derivative thereof is dextrin or modified dextrin.

[Aspect 3]

The acyclic oligosaccharide or derivative thereof is sucrose or treha The active energy ray-curable coating composition according to embodiment 1, which is a loin.

[Aspect 4]

The active energy ray-curable coating composition according to aspect 1, further comprising an active energy ray-curable compound (a 3).

[Aspect 5]

The active energy ray-curable coating composition according to embodiment 1, wherein the acrylic ester (a 1) of the acyclic oligosaccharide or derivative thereof is an aqueous dispersion.

[Aspect 6]

A coated article obtained by coating the active energy ray-curable coating composition according to aspect 1.

[Aspect 7]

A step of forming a base coating film by coating a starch-based base coating composition containing a starch-based resin, a color pigment, and Z or a luster pigment on an object to be coated;

Coating an active energy one-line curable aqueous coating composition containing an aqueous dispersion of an acrylic ester (b 1) of a saccharide or a derivative thereof and a photopolymerization initiator (b 2) on the base coating film; And

Irradiating active energy rays;

A method of forming a coating film characterized by

[Aspect 8]

An embodiment wherein the acrylate ester (bl) of a saccharide or a derivative thereof has a weight average molecular weight of 400 to 2,00,000 and an average of 3.0 to 12.0 acryloyl groups per molecule Method for forming a coating film according to 7

[Aspect 9]

The saccharide or derivative thereof is an acyclic oligosaccharide or derivative thereof. The coating film forming method according to embodiment 7, wherein

[Aspect 1 0]

The coating film forming method according to embodiment 9, wherein the acyclic oligosaccharide or derivative thereof is dextrin or modified dextrin.

[Aspect 1 1]

The coating film forming method according to embodiment 9, wherein the acyclic oligosaccharide or derivative thereof is sucrose or coconut rehalose.

[Aspect 1 2]

A coated article obtained by the coating film forming method according to aspect 7.

The active energy ray curable coating composition of the present invention has less emissions of total C_〇 ₂ involved in the life cycle of the product, both when possible to reduce the environmental pollution, finished appearance, pencil hardness, mar resistance, weather resistance, A coating film excellent in solvent resistance and photocurability can be formed.

Furthermore, the coating film forming method of the present invention reduces the amount of petroleum resources used, reduces the total carbon dioxide emissions related to the product life cycle, reduces environmental pollution, and also provides finish, pencil hardness, and scratch resistance. A multilayer coating film excellent in interlayer adhesion, weather resistance, alkali resistance and solvent resistance can be obtained. In addition, since the aqueous coating composition is used as a part of the coating composition to be used, the amount of the organic solvent used can be reduced. BEST MODE FOR CARRYING OUT THE INVENTION

Subsequently, a preferred embodiment of the present invention will be described. It should be understood that the present invention is not limited to the specific embodiments described below.

<<A. Active energy ray curable coating composition>>

The active energy ray-curable coating composition of the present invention contains an acrylic acid ester (a 1) and a photopolymerization initiator (a 2). Below in detail explain.

[Acrylic acid ester (a 1)]

The acrylic acid ester (a 1) used in the present invention is an acrylic acid ester of an acyclic oligosaccharide or a derivative thereof, and has a weight average molecular weight of 400 to 2, 2,000, and 1 It has an average of 3.0 to 12.0 acryloyl groups per molecule.

In the present specification, an acyclic oligosaccharide is an oligosaccharide having a structure in which a plurality of monosaccharides are cyclically linked by glycosidic bonds (cyclic oligosaccharide), specifically, for example, unlike cyclodextrins, This refers to an oligosaccharide having a structure in which a plurality of monosaccharides are linked in a chain by daricoside bonds. In the present specification, oligosaccharide means a saccharide from disaccharide to decasaccharide. Specific examples of non-cyclic oligosaccharides include disaccharides such as reducing disaccharides (maltose, cellobiose, lactose, etc.), non-reducing disaccharides (sucrose, trehalose, etc.); Examples thereof include oligosaccharides having three or more sugars such as monosaccharide, notose, stachyose and dextrin. Among these, dextrin is preferable because it can be obtained with any molecular weight by hydrolyzing starch. Non-reducing sucrose and trehalose do not cause browning due to the mailer reaction (browning reaction). Therefore, it is preferable from the viewpoint of durability of the coating film. As a derivative of acyclic oligosaccharide, for example, a part of the hydroxyl group in acyclic oligosaccharide is a saturated carboxylic acid having 2 to 22 carbon atoms (saturated carboxylic acid, saturated carboxylic acid ester, saturated force sulfonic acid halai A compound that has been converted to a carboxylic acid ester by at least one selected from (ii) can be suitably used. Specific examples include acetate esters and laurate esters.

Acrylic acid esters (a 1) of acyclic oligosaccharides or their derivatives usually have better photocurability than acrylic acid esters of cyclic oligosaccharides. It is. This is because the acyclic oligosaccharide or its derivative has a chain structure in which a plurality of monosaccharides are linked in a chain form by glycosidic bonds, and thus has a higher degree of steric freedom than the cyclic oligosaccharide. Presumed. And as a result of being excellent in photocurability, the coating film obtained by photocuring the active energy ray-curable coating composition of the present invention is usually more pencil-hardened than the coating film obtained by photocuring a cyclic oligosaccharide. The acrylic ester (a 1) used in the present invention having excellent scratch resistance can be produced according to a conventional method and is not particularly limited. For example, the acrylic ester (a 1) used in the present invention can be obtained by reacting an acyclic oligosaccharide or a derivative thereof with an acrylic ester such as acrylic acid or methyl acrylate. Specifically, for example, after dissolving an acyclic oligosaccharide or a derivative thereof in an organic solvent, the total mass of the acyclic oligosaccharide or the derivative thereof and an acrylate ester such as acrylic acid or methyl acrylate is used as a reference. The non-cyclic oligosaccharide or derivative thereof is 50 to 99% by mass, preferably 60 to 98% by mass, and acrylic acid or acrylic acid ester such as methyl acrylate is 1 to 50% by mass, preferably An organic solvent, for example, a hydrocarbon solvent such as toluene, xylene, cyclohexane, n-hexane, etc .; acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl in an amount ranging from 2 to 40% by mass Ketone-based solvents such as ketones; or a mixture of these in a mixture, etc., adding a basic compound as appropriate, and stirring at 60 ° C. to 100 ° C. Properly at temperatures of 7 0-9 0, 3 0 minutes to 1 0 hours, more preferably, to manufacture by 1 hour to about 5 hours, to esterification or transesterification.

In the production of the acrylic ester (a 1) used in the present invention The amount of acryloyl group introduced can be adjusted by the reaction temperature and reaction time during production. In addition, the average number of acryloyl groups per molecule of the acrylate ester (al) used in the present invention is determined, for example, by quantifying the generated alcohol by gas chromatography or the like in the case of production by transesterification. be able to.

The acrylic ester (a 1) used in the present invention is produced by dissolving the above acyclic oligosaccharide or a derivative thereof in an organic solvent and adding acrylic acid halide (for example, acrylic acid chloride). It can also be obtained by neutralizing the acid and washing with water (dehydrochlorination method) The weight average molecular weight of the acrylic acid ester (al) used in the present invention thus obtained is 400 to 2 , 0 00, preferably 5 0 0 to 1, 8 0 0, from the viewpoint of easy production, paint viscosity, and finish.

In this specification, the number average molecular weight and the weight average molecular weight are in accordance with the method described in JISK 0 1 2 4-8 3 as “TSKGEL 4 0 00 HX L”, “TSKG 3 0 0 0 HX L” as separation columns. L ”,“ TSKG 2 500 HX L ”,“ TSKG 2 00 HX L ”(manufactured by Tosohichi Co., Ltd.), and 4 using GPC tetrahydrofuran as eluent, It was obtained from the chromatogram obtained with the RI refractometer and the calibration curve of polystyrene at 0, a flow rate of 1 and O mLZ.

The acrylate (a1) used in the present invention has an average of 3.0 to 12.0, preferably 4.0 to 9.0, acryloyl groups per molecule. This increases the reactivity during irradiation with active energy rays and improves the scratch resistance and adhesion of the resulting coating film. Can be made.

When making the active energy ray-curable coating composition of the present invention aqueous

The acrylic ester (al) used in the present invention is preferably dispersed in water from the viewpoint of water resistance and storage stability.

The method for dispersing the acrylic ester (al) used in the present invention in water is not particularly limited. Specific examples of the water dispersion method include a method of forced emulsification using an emulsifier.

As a method of forced emulsification using an emulsifier, specifically, for example, an acrylic ester (al) used in the present invention or an organic solvent solution thereof and an emulsifier are mixed, and then water is gradually added while stirring. There is a method of dispersing in water by adding. When the acrylic ester (al) or the organic solvent solution thereof used in the present invention and the emulsifier are mixed, a photopolymerization initiator (a2) described later may be further mixed. In order to reduce the particle size of the water dispersion obtained by water dispersion, the water dispersion obtained by the above method may be further treated with a homogenizer, a high-pressure emulsifier or the like. In the case of using an organic solvent solution of acrylate (al) used in the present invention, the organic solvent may be completely or partially removed and then dispersed in water, or after obtaining an aqueous dispersion. All or part of the organic solvent may be removed. This can reduce the amount of organic solvent in the aqueous dispersion.

The emulsifier is not particularly limited. Examples of emulsifiers include reactive emulsifiers and non-reactive emulsifiers. Examples of the reactive emulsifier include nonionic reactive emulsifiers such as polyethylene glycol mono (meth) acrylate, polyethylene glycol di (meth) acrylate, and polyoxyethylene nonylphenyl ether acrylate; 1 0 (Product name, made by Daiichi Industry New Frontier A— 2 29 E (trade name, manufactured by Daiichi Kogyo Co., Ltd.), Ade force rear soap SE—10 N (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), Sulfoethyl methacrylate Anionic reactive emulsifiers having an anionic group such as sodium salt and α, β monoethylenic double bond; polyoxyethylene-1 mono (aryloxymethyl) alkyl ether sulfate ammonium salt, a — Sulfo_ ω— (1 — (alkoxy) methyl-2 — (2-propenyloxy) ethoxy) monopoly (oxyl 1, 2 — ethanedyl) ammonium salts and other anions • Nonionic reactive emulsifiers; quaternary ammonia And a cationic reactive emulsifier having a base and an a, -ethylenic double bond; a reactive high molecular emulsifier, and the like.

Examples of the reactive polymer emulsifier include a copolymer of a monofunctional acrylic monomer having a hydrophilic group such as sulfate ester, phosphate ester, carboxylic acid, amino group, and polyethylene glycol chain, and other copolymerizable monomers. Then, a reactive polymer emulsifier in which a double bond is introduced into the terminal or side chain is exemplified. Specifically, for example, a monomer mixture containing an epoxy group-containing unsaturated monomer, a hydroxyl group-containing unsaturated monomer, and a hydrophobic unsaturated monomer is polymerized to obtain an acryl polymer. After

In the presence of the acrylic polymer, a graft acrylic polymer is obtained by polymerizing a monomer mixture containing a carboxyl group-containing unsaturated monomer, a hydroxyl group-containing unsaturated monomer, and a hydrophilic unsaturated monomer. And reactive polymer emulsifiers produced by adding an unsaturated monomer having an isocyanate group to the hydroxyl group of the graft acrylic polymer.

Examples of the non-reactive emulsifier include sodium alkylbenzene sulfonate, sodium lauryl sulfate, sodium dioctyl sulfosuccinate, and alkylphenyl polyoxyethylene sulfate. —Anionic emulsifiers such as Da salt or ammonium salt, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene monopolyoxypropylene block copolymer, and the like.

Among these emulsifiers, it is preferable from the viewpoint of water resistance to use reactive emulsifiers.

The amount of the emulsifier is not particularly limited. Preferably, it is 0.2 to 20 parts by mass, and more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the acrylic acid ester (a 1) used in the present invention. The lower limit of these ranges is significant in that a stable aqueous dispersion can be obtained. The upper limit of these ranges is significant in terms of water resistance.

[Photoinitiator (a 2)]

The photopolymerization initiator (a 2) generates radicals by being excited by the light energy of the active energy ray, and the radical polymerizable unsaturated group (specifically, the acrylate ester (al) used in the present invention has Initiates a radical polymerization reaction of (acryloyl group).

Specific examples of the photopolymerization initiator (a 2) include, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, ketoxiacephenone, 2-hydroxyl 2-methyl-1 1 1 Phenylpropane 1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl roofyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propane 1-one, 2-benzyl-2-dimethyla Minnow 1 — (4 -Morpholinophenyl) -Evenone, 2, 4, 6 — Trimethylbenzoylphenylphosphine oxide, 2, 4, 6 — Trimethylbenzoylphenyloxyphosphine oxide, benzophenone O-Benzyl methyl benzoate, Hydroxybenzophenone, 2-Isopropylthioxanthone, 2,4-Dimethylthioxanthone, 2,4-Diethylthioxanthone, 2,4-Dichlorothixanthone, 2, 4, 6 — Tris (trichloromethyl) 1 S— Triazine, 2 — Methyl-4, 6 — Bis (Trichloromethyl) 1 S— Triazine, 2 – (4 -Methoxyphenyl) 1 4, 6 — Bis (Trichloromethyl) 1 S — Some examples include lyazine. These photopolymerization initiators (b 2) can be used alone or in combination of two or more. The content of the photopolymerization initiator (a 2) is 0 with respect to 100 parts by mass of the total amount of the saccharide or its derivative acrylic acid ester (a 1) and the active energy ray-curable compound (a 3) described later. 1 to: L 0 parts by mass, preferably 0.2 to 5 parts by mass.

In the active energy ray-curable coating composition of the present invention, in order to promote radical polymerization reaction by irradiation with active energy rays, in addition to the photopolymerization initiator (a 2), the sensitivity of radical generation is improved and the Z or wavelength region A photosensitizer may be used in combination for the purpose of expansion.

Examples of photosensitizers that can be used in combination include triethylamine, triethanolamine, methyljetanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminoaminobenzoate, benzoic acid (2-dimethylamino) ) Tertiary amines such as ethyl, Michler's ketone, 4,4, -jetylaminobenzenphenone, alkyl phosphines such as triphenylphosphine, and thioethers such as 6-thiodiglycol. These photosensitizers are acrylic acid esters used in the present invention.

A range of 0.1 to 5 parts by mass is preferable with respect to 100 parts by mass of (a 1) and the total amount of the active energy ray-curable compound (a 3) described later.

[Active energy ray curable compound (a 3)] The active energy ray-curable coating composition of the present invention can be blended with an active energy ray-curable compound (a 3) as necessary. The active energy ray-curable compound (a 3) to be combined is a radical polymerizable unsaturated monomer other than the acrylate ester (a 1) used in the present invention, a radical polymerizable unsaturated group-containing resin, and a radical. It is preferably at least one monomer and / or resin selected from the group consisting of resins having both a polymerizable unsaturated group and a thermosetting functional group. Examples of the radical polymerizable unsaturated monomer include a monofunctional polymerizable monomer, a bifunctional polymerizable monomer, and a trifunctional or higher functional polymerizable monomer.

Monofunctional polymerizable monomers include styrene, methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate.

― 卜, 2-ethyl hexyl (meth) acrylic acid, lauryl (meta)

) Acrylate 卜, Cyclohexyl (meth) acrylate, Cyclohexenyl (meth) acrylate — 卜, 2-Hydroxyl (meth) acrylate, Hydroxypropyl (Meth) Arc U, I. Tetrahydro Furfuryl (Meth) Acrylate, ε-Force Pactone Modified Tetrahydr d Furfuryl (Meth) Acrylate, F X

) Acrylate 卜, Phenoxypolyethylene U-Cole (Meth) Acrylate 卜, Dicyclopentenyl (Meth) Acrylate U-Rate, Dicyclopentenyloxetyl (Meyu) Acrylateイソ, Isoponil (meta

) Acrylate 卜, benzyl (meth) acrylate, ε-force prolacton-modified hydroxychetyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyp Methyl pyrene glycol mono (methyl), 2--hydroxy 3—phenoxypropyl (methyl), 2--hydroxy—3--butoxypropyl

(Meta) acrylate, phthalate monohydride □ Kichetil (Meta) Clear clay, paracylphenol enylene oxide modification (meta

) Acrylates, N-methylol (meth) acrylic acid S, N-methylol (meth) acrylamidobutyl ether, acryloylmorpholine, dimethylaminoethyl (meth) acrylic acid, N vinyl roux 2 — Pichi Lidon Can be mentioned.

In this specification, “(meta) acrylate” means “medium” and / or “acrylate”.

Examples of the bifunctional polymerizable monomer include, for example, ethylene glycol

(Meth) acrylate, diethylene glycol (meth) acrylic acid, polyethylene dairy glycol (meth) acrylate, propylene glycol (meth) acrylate, dipropylene alcohol

(Meth) acrylate, Polypropylene glycol di (meth) Acrylate, neopentyl alcoholic acid (Meth) acrylate, 1 4 Butanediol (meth) acrylic, 1, 6 _Hexanediorn ( (Meta) alkyl 'J ret bisphenol-A ethylenic acid-modified di (meth) acrylic, bisphenol-A propylene oxide modified di (me) Acryl, 2-hydroxyl-oxyloxy 3 -Metal U mouth xip mouth mouth, シクロ U cyclodecane dimethanol (meta), u re ret (meyu), acryloyloxy tyrosid phosphate, etc. HX-2 2 0 ”,“ Carrad 6 ”

Monomers marketed by Nippon Kayaku Co., Ltd. under product names such as “20”, “Riyadh R-6400” and “MANDA” can also be used.

Examples of the tri- or higher functional polymerizable monomers include trimethylol propane bread U (metha) ack U les, 卜 methylolpropane ethylene oxide modified tri (meth) acrylate, trimethylol propane pan Propylene oxide modified tri (meth) acrylate, Dali Serine tri (meth) acrylate, glycerin ethylene oxide modified tri (meth) acrylate, glycerin propylene oxide modified tri (meth) acrylate, pen erythritol tri (meth) acrylate, pen erythritol tetra Preferred examples of the radically polymerizable unsaturated monomer include (meth) acrylic acid 卜, isocyanuric acid ethylene oxide-modified triacrylate, dipentaerythritol hexa (meth) acrylate, and the like. Photo-curing property, adhesion property From the viewpoint of scratch resistance, etc., it is a bifunctional polymerizable monomer and / or a trifunctional or higher functional monomer.

Examples of the radical polymerizable unsaturated group-containing resin include unsaturated acrylic resin, unsaturated urethane resin, unsaturated epoxy resin, polyester (meth) acrylate, unsaturated silicone resin, and the like. 1 type, or 2 or more types selected from can be used. Among these, a resin having at least one radical polymerizable unsaturated group and one thermosetting functional group in each molecule can be used. From the viewpoint of the curability of the coating film, the unsaturated group and the thermosetting It is preferable to use a resin having a plurality of functional groups.

Examples of the thermosetting performance group include functional groups such as a hydroxyl group, an acid group, an epoxy group, and an isocyanate group. Examples of the acid group include a strong lpoxyl group and a phosphoric acid group.

Specific examples of the resin having one or more radically polymerizable unsaturated groups and one or more thermosetting functional groups in one molecule include, for example, a radically polymerizable unsaturated group and epoxy group-containing acryl resin, Examples thereof include saturated group and isocyanate group-containing acryl resins.

Further, when the active energy ray curable compound (a 3) has a thermosetting functional group, for example, an amino resin or a polyisocyanate compound is used. It is preferable from the viewpoint of improving the hardness of the coating film that the product and the epoxy group-containing compound are used in combination. As said amino resin, a melamine resin, a guanamine resin, a urea resin etc. can be used, for example.

The blending ratio of the active energy line curable compound (a 3) to the acrylic acid ester (a 1) used in the present invention is as follows. The acrylic acid ester (a 1) used in the present invention is 100 parts by mass. The active energy ray-curable compound (a 3) is preferably 0 to 90 parts by mass, more preferably 30 to 400 parts by mass, from the viewpoint of finish and scratch resistance.

Furthermore, the active energy ray-curable coating composition of the present invention includes, if necessary, an anti-fogging agent, a surface conditioner, an ultraviolet absorber, a light stabilizer, an antifoaming agent, an organic colorant, a natural dye and an inorganic pigment Can be used.

Examples of the organic colorant include those specified by Ministry of Health and Welfare Ordinance No. 37. Specifically, for example, Red No. 20 (Resolu Rubin BCA), Red No. 203 (Lake Red C), Red No. 20 (Lake Red CBA), Red No. 20 (Riso Red Red) , Red No. 2 06 (Reso Red Red CA), Red No. 2 07 (Reso Red Red BA), Red No. 2 08 (Reso Red Red SR), Red No. 2 1 9 (Brilliant Red Killed) R), red 2 220 (Deep Marin), red 2 2 1 (Dark Louis Red), red 2 2 8 (Parton Mutton Red), orange 20 3 (Permanen Orange) , Orange 2 0 4 (bench jin orange G), yellow 2 0 5 (bench jinero 1 G), red 4 0 4 (brilliant fast skalet), red 4 0 5 (permanent treasure) De F 5 R), Orange 4 0 1 (Hansa Orange), Yellow 4 0 1 Eight Nzaero), blue 4 0 4 issue (phthalocyanine blue), and the like.

Specific examples of natural pigments include carotenoids, Carotene, forceful chinal, capsanthin, lycopene, bixin, sucrose cin, canthaxanthin, anato, etc., flavonoids,

,,,

Antophanenins such as sonin, raphanin, enosyanin, saffs, loueroles, chalcones such as safflowers, flavonols such as rutin and quercetin, furans such as cacao pigments, flavin, riboflavin, etc. In chloroquine, anthraquinones such as lacaic acid, carminic acid (cochineal), kermesic acid, alizarin

, Naphthoquinones such as shikonin, alginine, echinochrome, etc., chlorophyll, hemoglobin, etc. for polyphyllin, curcumin (turmeric), etc. for diken, etc. Then, there are benin and the like.

Examples of inorganic pigments include caustic anhydride, magnesium silicate, talc, kaolin, bentonite, my strength, titanium mica, bismuth oxychloride, zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, and light carbonic acid. Calcium, heavy calcium carbonate, light magnesium carbonate, heavy magnesium carbonate, barium sulfate, yellow iron oxide, bengara, black iron oxide, gunjio, chromium oxide, chromium hydroxide, Kiichi pump rack, calamin, etc. Is mentioned. The blending ratio of the organic colorant, natural colorant and inorganic pigment may be appropriately determined according to the intended use and / or required performance.

The active energy ray-curable coating composition of the present invention may be any of an organic solvent type, an insoluble type, and an aqueous type coating composition. Making the active energy ray-curable coating composition of the present invention water-based is preferable because the amount of solvent used can be reduced without impairing the coating workability.

In the case of the organic solvent type, examples of the organic solvent to be used include acetonitrile, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone, ethyl isoamyl ketone, and diisopetite. Ketones such as ruketone and methylhexylketone; esters such as ethyl acetate, ethyl acetate, methyl benzoate and methyl propionate; ethers such as tetrahydrofuran, dioxane and dimethoxetane; ethylene glycol monomethyl ether, ethylene glycol No-ethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, darlicol ethers such as 3-methyl butyl acetate; alcohols such as ethyl alcohol and benzyl alcohol; aromatic hydrocarbons, aliphatic carbonization Hydrogen etc. are mentioned.

The method of making the active energy ray-curable coating composition of the present invention aqueous is not particularly limited. As a method for making the aqueous solution, for example, the acrylic acid ester (a 1) or the organic solvent solution, the photopolymerization initiator (a 2) and the emulsifier used in the present invention are mixed, and then gradually stirred. An example is a method in which water is dispersed to form an aqueous solution by adding water. As another method, an aqueous dispersion obtained by making the acrylic ester (al) used in the present invention aqueous and other components such as a photopolymerization initiator (a 2) in an aqueous medium. A method of mixing and making it aqueous according to a conventional method can be mentioned. When the active energy ray-curable compound (a 3) is used, it is preferable from the viewpoint of mixing stability that an aqueous dispersion obtained by previously dispersing the compound in water is used. The method for dispersing the active energy line curable compound (a3) in water can be the same as the method for dispersing the acrylic ester (al) used in the present invention. In addition, when the photopolymerization initiator (a 2) is a solid photopolymerization initiator having low solubility in water, it can be uniformly added and dissolved in the active energy ray-curable compound (a 3). It is preferable from the viewpoints of photocuring, finish, and scratch resistance. In addition, when the active energy ray-curable coating composition of the present invention is made aqueous, a photopolymerization initiator (a 2) is Irgacure 500 (trade name, Ciba's Specialty • Chemicals, 1—Hydroxyshiki Hexroof Elulu ketone and benzofuenone 1: 1 (mass ratio) mixture), Darocur 1 1 7 3 (Product name, Ciba 'Specialty' manufactured by Chemicals, 2 Hydroxyl-2-Methyl-1, 1-Propane 1-On), etc. From the viewpoint of sex.

[Coated article]

The object to be coated with the active energy ray-curable coating composition of the present invention is not particularly limited, such as metal, plastic, and wood. Examples of the metal include a cold-rolled steel plate, a tin-plated steel plate, a zinc-plated steel plate, a chrome-plated steel plate, and an aluminum plate. These metal plates can be used after being subjected to surface treatment such as power phosphate treatment, zirconium salt treatment, chromate treatment, etc., which can be used without treatment. Examples of the plastic include acrylic resin, polyester resin, polyamide resin, polycarbonate resin, ABS resin, polypropylene resin, and polyethylene resin.

These coated materials may be coated with a base coat paint containing an undercoat and / or a brightening agent, if necessary.

The coating is formed by coating the active energy ray curable coating composition with a dry film thickness of 0.1 to 30 m, preferably l to 25 m, more preferably 5 to 20 ^ m, and A cured coating film can be obtained by combining irradiation, or heating and irradiation of active energy rays.

Examples of the coating means include roller coating, brush coating, dip coating, spray coating (non-electrostatic coating, electrostatic coating, etc.), curtain flow coating, screen printing, letterpress printing, and the like. The non-volatile concentration of the active energy ray-curable coating composition is not particularly limited as long as it can be applied, but is preferably in the range of 10 to 50% by mass when spray coating is performed.

When applying an active energy ray-curable coating composition containing an organic solvent or water, it is desirable to volatilize the organic solvent or water by heating or setting after coating, and then irradiate the active energy ray. The means for heating is not particularly limited, and for example, a drying facility such as a hot air furnace, an electric furnace, or infrared induction heating can be applied. The heating temperature is not particularly limited, but is usually in the range of 35 to 100 ° C., preferably 40 to 90 ° C. The heating time is not particularly limited, but usually a range of 1 to 30 minutes is preferable.

The active energy ray used for the curing is not particularly limited, and may be any of electron beam, ultraviolet ray, visible light, and infrared ray. An active energy ray having a wavelength of 200 to 60 nm, preferably a wavelength of 300 to 45 nm is preferable from the viewpoint of finish.

Depending on the type of the photopolymerization initiator (a 2), an irradiation source having a highly sensitive wavelength can be appropriately selected and used. Examples of the active energy ray irradiation source include a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, and sunlight.

The conditions for irradiating the coating with active energy rays are usually in the range where the integrated light quantity is 1, 0 00 to ²⁰ , OOOJ Zm ² , preferably 2, 0 0 0 to 1 5, 0 0 0 J Zm ² Is suitable. The coating film can be cured with an irradiation time of about 1 second to about 5 minutes. It is preferable that it is in the above range from the viewpoint of photocurability of the coating film, yellowing resistance and the like.

The active energy ray-curable coating composition of the present invention is water or organic. Regardless of the presence or absence of a solvent, heating can also be performed as an auxiliary crosslinking means after irradiation with active energy rays.

The coated article obtained by applying the active energy ray-curable coating composition of the present invention can be used, for example, as a material or a part of an electrical component, a mobile phone, lighting, an electrical element, a semiconductor, a vending machine, or the like. it can.

<< B. Method for forming coating film>

[Coating]

The coated material used in the coating film forming method of the present invention can be the same as the coated material described in the section “A. Active energy ray-curable coating composition”. Further, for example, a primer layer and / or an electrodeposition coating layer may be formed in advance by applying a primer coating, a cationic electrodeposition coating, or the like to the object to be coated.

[Starch-based paint composition]

In the coating film forming method of the present invention, the starch-based base coating composition to be coated on the article to be coated contains a starch-based resin and a coloring pigment and / or a luster pigment.

[Starch resin]

In the present specification, the starch-based resin means starch, modified starch, and a resin having a structure derived from starch or modified starch. Specifically, for example, the following starch-based resin;

Starch-based resin (I): Starch and Z or modified starch;

Starch Resin (II): Reaction of Starch Resin (I) with Product (X) with Isocyanate Group Obtained by Reaction of Polyisocyanate Compound (xl) and Polyhydric Alcohol (x2) Starch-based resin obtained by allowing

Starch resin (III): obtained by reacting starch resin (I) with polyisocyanate compound (xl) and polyhydric alcohol (x2). A starch-based resin obtained by reacting a product (X) having an isocyanate group with a vinyl copolymer resin (Y);

Starch-based resin (IV): starch-based resin obtained by subjecting starch-based resin (I) to radical-polymerizable unsaturated monomer graph polymerization; and

Starch Resin (V): Resin (Z) obtained by graph-polymerizing a radical polymerizable unsaturated monomer to starch resin (I), polyisocyanate compound (xl) and polyhydric alcohol (x 2 ) Is a starch-based resin obtained by reacting with a product (X) having an isocyanate group obtained by reacting:

Can be mentioned.

[Starch resin (I)]

Examples of starch in the starch-based resin (I) include corn starch, high amylose starch, wheat starch, unmodified starch of cereals such as rice starch, potato unmodified starch such as potato starch, evening pio force starch, etc. It is done. As starch modified with starch resin (I), starch is esterified.

And starch-substituted derivatives etherified, oxidized, acid-treated or dextrinized. Specifically, for example, an organic functional group such as an aliphatic saturated hydrocarbon group, an aliphatic unsaturated hydrocarbon group, or an aromatic hydrocarbon group is added to the starch or starch degradation product via an ester bond and / or an ether bond. And modified starches bound together. Here, examples of the starch degradation product include those obtained by subjecting starch to a low molecular weight treatment with an enzyme, an acid, or an oxidizing agent.

The starch or starch degradation product has a number average molecular weight of 1, 0 0 0 to 2, 0 0 0, 0 0 0, more preferably 3, 0 0 0 to 5 0 0, 0 0 0, particularly 5, 0 0 0 It is preferable from the viewpoint of force, film-forming property, etc. to be in the range of ˜100,000.

Examples of the modification method of the modified starch include esterification modification. A preferred modifying group is an acyl group having 2 to 18 carbon atoms. The modification can be performed by using organic acids having 2 to 18 carbon atoms alone or in combination of two or more.

The degree of modification of the modified starch is preferably in the range of 0.1 to 2.8 in terms of the degree of substitution, particularly preferably in the range of 1.0 to 2.5. If the degree of substitution exceeds 2.8, biodegradability may be reduced.

Modified starch has a glass transition point below the starch decomposition temperature (about 3500 ° C), and has a glass transition point, and the degree of change is adjusted to have thermoplasticity and biodegradability. It is desirable that Therefore, when the number of carbon atoms of the substituent used for modification is large, the level of modification is low. For example, when the substituent is a stearoyl group having 18 carbon atoms, the degree of ester substitution is 0.:! To 1.8. It is preferably within the range, and when the number of carbon atoms of the substituent is small, it is highly modified.For example, when the substituent is a acetyl group having 2 carbon atoms, the degree of ester substitution is 1, 5 to 2. It is preferably within the range of 8.

The degree of substitution is the average number of hydroxyl groups substituted by a denaturing agent per monosaccharide unit constituting the starch. For example, the degree of substitution 3 is in one monosaccharide unit constituting the starch. This means that all three hydroxyl groups present are substituted by a modifier, and a substitution degree of 1 means that only one of the three hydroxyl groups present in one monosaccharide unit constituting the starch is a modifier. It means that it is replaced by.

An example of a modified starch is obtained by mixing anhydrous starch having an amylose content of 50% or more with an esterification reagent in a non-protonic solvent and reacting between the starch and the esterification reagent. Hydrophobic biodegradable starch ester product (see Japanese Patent Publication No. Hei 8-500 25 2), starch ester modified with vinyl ester as an esterifying reagent, Carbon number of the group Is a starch ester obtained by reacting with starch using an esterification catalyst in a non-aqueous organic solvent (refer to Japanese Patent Laid-Open No. Hei 8- 186060), esterification In addition, starch in which the polyvinyl ester is made into a dull (see Japanese Patent Laid-Open Nos. 8-239204 and JP-A-8-3010994), polyester graft chains with starch molecules A polyester-draft polymerized starch having a part of or all of hydroxyl groups directly connected to starch and blocked by ester groups, and having the same components as the polyester graft chain. And a polyester graph formed by uniformly mixing with an independent polyester in which some or all of the terminal hydroxyl groups are blocked with ester groups (see Japanese Patent Application Laid-open No. Hei 9 3 1 3 0 8), etc. Can mention .

Furthermore, a short-chain single-long-chain mixed starch ester obtained by substituting hydrogen of the reactive hydroxyl group of the same starch molecule with a short-chain acyl group having 2 to 4 carbon atoms and a long-chain acyl group having 6 to 18 carbon atoms. 0 0 0 — 1 5 9 8 0 1), the reactive hydroxyl group of the same starch molecule is a short chain hydrocarbon-containing group having 2 to 4 carbon atoms and a long chain hydrocarbon-containing group having 6 to 24 carbon atoms. Substituted short chain and long chain mixed starch substituted derivatives (see Japanese Patent Laid-Open No. 2 0 0 0-1 5 9 8 0 2) and the like. These modified starches are biodegradable because they are based on starch, and are particularly excellent in solubility in solvents and Z or compatibility.

These starches and / or modified starches can be used alone or in combination.

[Starch resin (I I)]

[Products having isocyanate groups (X)]

The product (X) having an isocyanate group can be obtained by reacting the polyisocyanate compound (xl) with a polyhydric alcohol (x 2). Polyisocyanate compounds (X 1) include, for example, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, lysine diisocyanate, naphthenic diisocyanate, triphenylmethane triisocyanate. Nate, Tris (Phenol Isocyanate) Thiophosphate, Phenyl Diisocyanate, Hexamethylene Diisocyanate, Trimethyl Hexamethylene Diisocyanate, Lysine Diisocyanate, Xylylene Diisocyanate, Bis (Isocyanatomethyl) □ □ hexane, dicyclohexylhexane diisocyanate, isopropylidenebis (cyclohexylisocyanate), 3— (2′-isocyanatocyclohexyl) propylisocyanate, dianicidindi Shiane one Bok include diphenyl ether disulfonate iso Xia sulfonate, and the like. Of these, the use of isophosphonate diisocyanate and hexamethylene diisocyanate is particularly preferred from the viewpoint of hardness, adhesion, and impact resistance.

Commercial α of polyisocyanate compound (X1)

For example, “Barnock D 1750, D—800, DN-9500, DN 9700 or 1 5 1 4 5 5” (Dai Nippon Chemical Industries, Ltd.) Products), "

❖

Desmonle, N, H L or N 3 3 90 J (product of Bayer, Germany), “Takenai D_ 1 0 2, D-1 700 H N, D-2 0 2

, D 1 110 or D _ 1 2 3 N "(Mitsui Chemicals Polyurethane Co., Ltd. product)," 3 Roneichi EH, L, HL or 20 3 "(Nihon Polyuretan Kogyo Co., Ltd.) Product) or “deyuranate 2 4 A 1 90 CX” (product of Asahi Kasei Chemicals Corporation).

Examples of the polyhydric alcohol (x2) include alkylene diols, trivalent or higher valent alkane polyols, ether polyols, polyester polyols, and other polyols.

Examples of the alkylene diol include ethylene glycol, plastic Lopylene glycol, 1,3-butylene glycol, 1,4-butylenediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, cyclohexane-1,4 Examples include dimethylol, 2-methyl-2,4 monopentanediol, and hydrogenated bisphenol A.

Examples of the trivalent or higher-valent alkane polyols include triols such as glycerin, trimethylolethane, trimethylolpropane; and higher-valent alkane polyols such as pen erythritol, α-methyldaricoside, and sorbitol.

Examples of the ether polyol include those produced by ring-opening addition reaction of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, diethylene glycol, dipropylene glycol, polyethylene glycol, Polypropylene glycol, polytetramethylene glycol, triethylene glycol, poly (oxyethylene oxypropylene) glycol, bisphenol ノール polyethylene glycol ether, bisphenol A polypropylene glycol ether, sucrose, dipentyl erythritol, and the like.

Examples of the polyester polyol include those obtained by subjecting an organic dicarboxylic acid or an anhydride thereof to a polycondensation reaction with an organic diol component under conditions of excess organic diol. Specifically, a polyester polyol which is a condensate of adipic acid and ethylene glycol and a condensate of adipic acid and neopentyl dallicol can be mentioned.

Examples of the organic dicarboxylic acid include aliphatic, alicyclic or aromatic dicarboxylic acids having 2 to 4 carbon atoms, particularly 4 to 36 carbon atoms, such as succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid. Acid, fumar Acid, glutaric acid, hexaclonal heptane dicarboxylic acid, cyclohexane dicarboxylic acid, O-phthalic acid, isophthalic acid, terephthalic acid, tetrahydrobutyric acid, and tetraclofuuric acid. In addition to these dicarboxylic acids, a small amount of polycarboxylic acid anhydrides and / or unsaturated fatty acid adducts having three or more carboxyl groups can be used in combination. Examples of the organic diol component include alkylene glycols such as ethylene glycol, propylene glycol, 1,4 monobutanediol, 1,5-pentanediol, 1,6-hexanediol, and neopentyldarlicol. 1,4-cyclohexanedimethanol, 2-butyl-2-ethyl-1,3-propanediol, 3_methyl_1,5 monopentanediol, 2-methyl-2,4 monopentanediol, etc. In some cases, these may be used in combination with a small amount of a trivalent or higher valent polyol such as trimethylolpropane, glycerin, or penicillin erythritol. Among the polyhydric alcohols (x2) mentioned above, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, bishydride Phenolic A, Glycerin, Trimethyl Mouth Lutane, Limethylolpropane, Pentaerythritol, Dipentaerythritol, Polyethylene Glycol, Polypropylene Glycol, Polytetramethylene Glycol, Poly (oxyethyleneoxypropylene) glycol, Bisphenol A Ethylene A material selected from the group consisting of glycol ether and bisphenol A polypropylene glycol ether is preferred from the viewpoint of impact resistance and flex resistance.

The reaction of the polyisocyanate compound (xl) and the polyhydric alcohol (X 2) is performed by an organic solvent such as toluene, xylene, cyclohexane. Hydrocarbon solvents such as xane and n-hexane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isoptyl ketone, and methyl amyl ketone; or It can be carried out in a mixture of these. Here, the reaction ratio of the polyisocyanate compound (xl) and the polyhydric alcohol (x 2) is not particularly limited as long as the reaction ratio is such that free isocyanate is left. As the reaction rate, for example, the number of moles of NC group based on polyisocyanate compound (X 1) and the number of moles of H group based on polyhydric alcohol (x 2) is OH group ZN CO Group = 0.4 / 1.0 to 0.95 / 1.0, preferably 0.5 / 1.0 to 0.9 / 1.0. In the above reaction, a catalyst such as monobutyltin oxide or dibutyltin oxide can be used as appropriate. The temperature and time of the above reaction are not particularly limited. For example, at a temperature of 50 ° C. to 200 ° C., preferably 60 ° C. to 150 ° C., 30 minutes to 1 0 hours, preferably; ~ 5 hours. The NCO value of the product (X) having an isocyanate group obtained by the above reaction is preferably in the range of SSSO mg NCO / g, particularly 7 to 200 mg NC OZ g.

The reaction between the starch-based resin (I) and the product (X) having an isocyanate group is an organic solvent, for example, a hydrocarbon solvent such as toluene, xylene, cyclohexane, n-hexane, methyl acetate, It can be carried out in ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isoptyl ketone and methyl amyl ketone; or a mixture thereof. The blending ratio of the starch-based resin (I) and the product (X) having an isocyanate group can be appropriately adjusted according to the required coating film performance. For example, the blending ratio is determined based on the starch-based resin (I) and the product having isocyanate group ( X) is a product having an isocyanate group in which the starch-based resin (I) is in an amount ranging from 50 to 99% by mass, preferably from 60 to 98% by mass, based on the total non-volatile content of X (X) is an amount in the range of 1 to 50 mass%, preferably 2 to 40 mass%. In the above reaction, a catalyst such as monobutyltin oxide or dibutyltin oxide can be appropriately used. The temperature and time of the above reaction are not particularly limited. For example, at a temperature of 50 to -20 ° C, preferably 60 to 1550 ° C, 30 minutes to 10 hours. It is preferably 1 to 5 hours. The number average molecular weight of the starch-based resin (II) obtained by the above reaction is preferably in the range of 3, 0 00 to 2 0 0, 0 0 0, more preferably 5, 0 0 0 to 1 0 0, 0 0 The range is 0. The starch-based resin (II) produced in this manner is suitable as a binder for a starch-based base coating composition formed by dissolving or dispersing the starch-based resin (II) in an organic solvent solvent. Can be used for Here, when the amount of the starch-based resin (I) is less than 50% by mass, the bio-derived components are decreased, whereas when it exceeds 99% by mass, the chemical resistance of the coating film may be lowered.

[Starch Resin (I I I)]

The starch-based resin (III) comprises a starch-based resin (I), a product (X) having an isocyanate group obtained by reacting a polyisocyanate compound (xl) and a polyhydric alcohol (x2), It is obtained by reacting with vinyl copolymer resin (Y).

[Vinyl copolymer resin (Y)]

The vinyl copolymer resin (Y) can be obtained by subjecting a mixture of radically polymerizable unsaturated monomers to a radical polymerization reaction in the presence of an organic solvent and a polymerization initiator.

The mixture of the radical polymerizable unsaturated monomer is 1 to 90% by mass of the aromatic radical polymerizable unsaturated monomer based on the total mass of the mixture, Preferably 5 to 80 mass%, more preferably 1.0 to 85 mass%, hydroxyl-containing radically polymerizable unsaturated monomer 1 to 50 mass%, preferably 2 to 40 mass%, More preferably 5 to 30% by mass and other radical polymerizable unsaturated monomers 0 to 98% by mass, preferably 2 to 93% by mass, and more preferably 5 to 85% by mass. Radical polymerizability When it is a mixture of unsaturated monomers, it is possible to form a coating film excellent in finish, adhesion, solvent resistance, alkali resistance, impact resistance and flex resistance.

Examples of the aromatic radical polymerizable unsaturated monomer include styrene, vinyltoluene, 2-methylstyrene, t_butylstyrene, chlorostyrene, vinylnaphthalene, and the like.

The hydroxyl group-containing radically polymerizable unsaturated monomers include 2 —hydroxychetyl (meth) acrylate, 2 —hydroxypropyl (methyl) acrylate, and 3 —hydroxypropyl. (Meth) acrylic acid, 4-hydroxybutyl (meth) acrylic acid, etc., an alkyl group having 2 to 8 carbon atoms or a hydroxyalkyl ester of maleic acid; ) Hydroxy hydroxy ester ester modified with acrylic acid (for example, Daicel Chemical Co., Ltd., trade name “Braxel F” series) and the like. Among them, 2—Hydroxyl Chlorate, 2—Hydroxyshemethyl Acrylate, 2—Hydroxypropyl Acrylate, 2—Hydroxypropyl Metaacrylate and 4— At least one selected from hydroxybutyl acrylate has improved compatibility with starch-based resins (I) and / or products having isocyanate groups (X) to improve paint stability. This is particularly preferable from the viewpoint of ensuring the above.

Examples of other radical polymerizable unsaturated monomers include (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid and the like. Of radical polymerizable unsaturated monomer containing lpoxyl group; methyl (meta

) Acrylate, ethyl (meth) acrylate, n-propyl (methyl) acrylate, isopropyl (meth) acrylate, n —, i or t — ptyl ( (Meta) acrylate, Hexyl (meta) acrylate, 2—ethylhexyl (meta) acrylate, n—Yetyl hexyl (meta) acrylate, Decyl (meta) alkyl C1-C18 alkyl ester or cycloalkyl ester of acrylic acid or methacrylic acid such as relate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, etc. N—Methylol acrylamide, N—Butoxymethyl acrylamide, N—Methyl oxymethyl amide, N—Methylol methyl amide, N—Butoxymethyl methacrylamide, N — Conversion accession Riruami de type or N - it can be exemplified substituted Metaku Lil Ami de monomer.

In addition, other examples of the radical polymerizable unsaturated monomer include fatty acid-modified radical polymerizable unsaturated monomers.

The fatty acid-modified radically polymerizable unsaturated monomer includes a radically polymerizable unsaturated monomer having a radically polymerizable unsaturated group at the terminal of a fatty acid-derived hydrocarbon chain. Examples of the fatty acid-modified radical polymerizable unsaturated monomer include those obtained by reacting a fatty acid with an epoxy group-containing radical polymerizable unsaturated monomer or a hydroxyl group-containing radical polymerizable unsaturated monomer. be able to.

Examples of the fatty acid include dry oil fatty acid, semi-dry oil fatty acid and non-dry oil fatty acid. Examples of the dry oil fatty acid and semi-dry oil fatty acid include fish oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, poppy oil fatty acid, eno oil fatty acid, grape oil fatty acid, grape Nuclear oil fatty acid, corn oil fatty acid, tall oil fatty acid, castor oil fatty acid, cottonseed oil fatty acid, curd Examples include coconut oil fatty acid, rubber seed oil fatty acid, and hyogen acid fatty acid. Examples of the non-drying oil fatty acid include coconut oil fatty acid, hydrogenated coconut oil fatty acid, and palm oil fatty acid. Each of these can be used alone or in combination of two or more. Furthermore, these fatty acids can be used in combination with cabronic acid, strong puric acid, lauric acid, myristic acid, palmitic acid, stearic acid and the like. In order to produce the fatty acid-modified radical polymerizable unsaturated monomer, the monomer that can be reacted with the fatty acid is preferably a radical polymerizable unsaturated monomer containing an epoxy group, for example , Glycidyl (meth) acrylate, jS —Methyldaricidyl (meth) 7 acrylate, 3,4_epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate Examples thereof include 3,4_epoxycyclohexylpropyl (meth) acrylate, allylglycidyl ether, and the like.

The vinyl copolymer resin (Y) can be easily prepared, for example, by subjecting a mixture of the above-mentioned radical polymerizable unsaturated monomers to a radical polymerization reaction in an organic solvent in the presence of a polymerization initiator. Can do. In the above reaction, for example, a mixture of a radical polymerizable unsaturated monomer and a mixture of a polymerization initiator are uniformly dropped to 60 to 200 ° C., preferably 80 to 180. At a reaction temperature of 30 minutes to 6 hours, preferably 1 to 5 hours.

Examples of the organic solvent include hydrocarbon solvents such as toluene, xylene, cyclohexane, and n-hexane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; acetone, methyl ethyl ketone, and methyl isoform. Ketone solvents such as butyl ketone and methyl amyl ketone; or a mixture thereof.

Vinyl copolymer resin (Y) has a hydroxyl value of 5 to 40 O mg KOH / g, and the weight average molecular weight is preferably in the range of 3, 0 00 to 1 0 0, 0 0 0, particularly 5, 0 0 0 to 2 0, 0 0 0.

The reaction between the starch-based resin (I) and the product (X) having an isocyanate group can be carried out in an organic solvent similar to that described in the production of the starch-based resin (I I). The blending ratio of the starch-based resin (I), the product having an isocyanate group (X), and the vinyl copolymer resin (Y) can be appropriately adjusted according to the required coating film performance. . For example, the blending ratio of starch-based resin (I), starch-based resin (I) is 50% based on the total non-volatile content of product (X) and vinyl copolymer resin (Y) having isocyanate group. ˜98% by mass, preferably 65 to 95% by mass, and the product (X) having an isocyanate group is 1 to 49% by mass, preferably 2 to 33% by mass. %, And the vinyl copolymer resin (Y) is in the range of 1 to 49% by mass, preferably 2 to 33% by mass. In the above reaction, a tin catalyst such as monobutyltin oxide or dibutyltin oxide can be appropriately used. The temperature and time of the above reaction are not particularly limited. For example, the reaction is performed at a temperature of 50 ° C. to 200 ° C., preferably 60 ° C. to 150 ° C., for 30 minutes to 10 ° C. Time, preferably 1 to 5 hours.

The number average molecular weight of the starch-based resin (III) obtained by the above reaction is preferably in the range of 3, 0 00 to 2 0 0, 0 0 0, more preferably 5, 0 0 0 to 1 0 0, The range is 0 0 0. The starch-based resin (III) thus produced can be suitably used as a binder for a starch-based base coating composition dissolved or dispersed in an organic solvent-based solvent. Here, when the amount of the starch-based resin (I) is less than 50% by mass, the biological component is decreased, and when it exceeds 98% by mass, the chemical resistance and / or adhesion of the coating film is lowered. There are things to do. Raw materials with isocyanate groups If the amount of the composition (X) is less than 1% by mass, the storage stability of the varnish and the chemical resistance of Z or the coating film may be inferior. In addition, the solvent solubility of the resin may be reduced. In addition, when the amount of the vinyl copolymer resin (Y) is less than 1% by mass, the adhesion and / or chemical resistance of the coating film may be reduced. There are fewer ingredients.

[Starch Resin (IV)]

The starch-based resin (IV) is obtained by graph-polymerizing a radical polymerizable unsaturated monomer with the starch-based resin (I).

For example, U.S. Pat. Nos. 3 4 2 5 9 7 1, 3 9 8 1 1 0 0 and JP 5 6-1 6 7 7 4 6 disclose an aqueous dispersion or Discloses a graft polymerization of vinyl monomers using a cerium salt as a radical polymerization initiation catalyst in slurry-like starch or modified starch. In addition, Japanese Patent Application Laid-Open Nos. 54-102086 and 55-1900-5 disclose styrene for starch modified with maleic acid, which is a compound containing an unsaturated group, and Graft polymerization of acrylic monomers has been disclosed. Japanese Patent Application Laid-Open No. 8-213940 discloses the graft polymerization of (vinyl) esterified starch and vinyl monomer in an organic solvent. In addition, Japanese Patent Application Laid-Open Nos. 55-13 3 4 72 and 5 6-1 5 7 4 6 3 disclose a cellulose acetate in a solution using a radical initiator. A graph of vinyl monomers to 卜 polymerization is disclosed. If nitrocellulose acetate is replaced with starch and / or modified starch, it is easy to graft polymerize vinyl monomers to starch and / or modified starch.

As described above, some known examples of graft polymerization have been described. The target starch resin (IV) can be produced by these known methods. Alternatively, it can be produced by other known methods. Can.

There are no particular limitations on the ratio of the starch-based resin (I) and the radically polymerizable unsaturated monomer. As the radical polymerizable unsaturated monomer, it is preferable to use a mixture of monomers having different properties. The above-mentioned mixture of radically polymerizable unsaturated monomers is, for example, radically polymerizable from the viewpoint of forming a coating film excellent in finish, adhesion, solvent resistance, alkali resistance, impact resistance and flex resistance. Aromatic radical polymerizable unsaturated monomer 1 to 90% by mass, preferably 5 to 80% by mass, based on the total mass of the mixture of unsaturated monomers, hydroxyl group-containing radical polymerizable unsaturated monomer 1 to 50 mass%, preferably 2 to 40 mass%, and other radical polymerizable unsaturated monomers 0 to 98 mass%, preferably 18 to 93 mass% A mixture of polymerizable unsaturated monomers is desirable.

Examples of the aromatic radically polymerizable unsaturated monomer include aromatic radically polymerizable unsaturated monomers exemplified in the above-mentioned vinyl copolymer resin (Y) section.

Examples of the hydroxyl group-containing radical polymerizable unsaturated monomer include the hydroxyl group-containing radical polymerizable unsaturated monomer exemplified in the above-mentioned section of the pinyl copolymer resin (Y).

Examples of the other radically polymerizable unsaturated monomer include other radically polymerizable unsaturated monomers exemplified in the above-mentioned section of the vinyl copolymer resin (Y).

As a method for graft polymerization of a radically polymerizable unsaturated monomer to starch and / or modified starch, specifically, for example, a mixture of a radically polymerizable unsaturated monomer and a polymerization initiator are mixed with a starch-based resin. A method of radical polymerization reaction by dropping it into the organic solvent solution (I) is simple. The above reaction may be carried out, for example, by adding dropwise a mixture of radically polymerizable unsaturated monomers and a mixture of polymerization initiators to 60 to 200, preferably 8 The reaction is carried out at a reaction temperature of 0 to 180 ° C. for 30 minutes to 6 hours, preferably 1 to 5 hours.

Here, as the polymerization initiator, a known radical polymerization initiator can be used, but the radical polymerizable unsaturated monomer mixture and the polymerization initiator are dropped into the organic solvent solution of the starch resin (I). In the case of adopting the graph polymerization method, it is preferable to use a peroxide-based initiator. Examples of such peroxide-based initiators include t-butyl didropoxide, p-men drip drop oxide, cumene high drop oxide, diisopropylbenzene drop drop oxide, and the like. 8-hydroxyperoxides; peroxyesters such as t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butylyloxydecanoate, etc .; 1, 5 — di-t-perylperoxy-3, 3 , 5-Peroxy ketones such as trimethylcyclohexane; Ketone peroxides such as acetoacetate acetate; Diacyl peroxides such as benzoyl peroxide.

The number average molecular weight of the starch-based resin (IV) obtained by the above reaction is preferably in the range of 3,000 to 200,000, more preferably 5,0, from the viewpoint of film forming property and the like. The range is from 0 0 to 1 0 0, 0 0 0.

[Starch resin (V)]

The starch resin (V) comprises a resin (Z) obtained by graft polymerization of a radically polymerizable unsaturated monomer to the starch resin (I), and a polyisocyanate. It is obtained by reacting a product (X) having an isocyanate group obtained by reacting an nate compound (xl) and a polyhydric alcohol (x 2).

The resin (Ζ) obtained by graft polymerizing a radical polymerizable unsaturated monomer to the starch resin (I) can be the same as the starch resin (IV). Specific methods for obtaining the resin (（) include the same methods as those for obtaining the starch-based resin (IV) described in the production of the starch-based resin (IV).

The reaction between the resin (Ζ) and the product (X) having an isocyanine group is

It can be carried out in an organic solvent. Examples of the organic solvent include the same organic solvents as those described in the production of the above starch-based resin (I I). The blending ratio of the resin (（) and the product (X) having an isocyanate group can be appropriately adjusted according to the required coating film performance. For example, the blending ratio is 50 to 99% by mass, preferably 60 to 99% by mass of the resin (Ζ) based on the total nonvolatile mass of the resin (Ζ) and the product (X) having an isocyanate group. The amount of the product (X) having an isocyanate group is 1 to 50% by mass, preferably 2 to 40% by mass. In the above reaction, a catalyst such as monobutyltin oxide or dibutyltin oxide can be appropriately used. The temperature and time of the above reaction are not particularly limited. For example, the reaction is carried out at a temperature of 50 ° C. to 200 ° C., preferably 60 ° C. to 150 ° C. for 30 minutes to 10 ° C. The time is preferably 1 to 5 hours.

The number average molecular weight of the starch-based resin (V) obtained by the above reaction is preferably in the range of 3, 0 00 to 2 0 0, 0 0 0, more preferably 5 0 0 0, from the viewpoint of film forming property and the like. The range is 0 to 1 0 0, 0 0 0.

[Colored pigments and / or bright pigments] Coloring pigments include white pigments such as titanium oxide, zinc white, lead white, basic lead sulfate, lead sulfate, lithobon, zinc sulfide, antimony white, etc .; Power Pon Black, Acetylene Black, Lamp Black, Pon Black Black pigments such as black, graphite, iron black, and aniline black;

— Yellow pigments such as S, Hansaero I, Pigment Yellow L, Benzidine Yellow, Permanent Yellow, etc .; Orange pigments such as chrome orange, chrome virion, and permanent orange; Brown pigments such as iron oxide and amber; Bengala, lead Red pigments such as red, permanent red and quinacridone red pigments; purple pigments such as cobalt violet, fast violet, methyl violet lake, blue pigments such as ultramarine, bitumen, cobalt blue, phthalocyanine blue, indigo; chrome green And green pigments such as pigment green B and phthalocyanine green.

Examples of the luster pigment include aluminum powder, bronze powder, copper powder, tin powder, lead powder, zinc powder, iron phosphate, pearl metal coating mica powder, and micaceous iron oxide.

The blending ratio of the color pigment and / or the luster pigment may be appropriately determined according to the intended use and / or required performance, but it is generally 0. The range is from 0 to 1 to 400 parts by mass, and preferably from 0.01 to 200 parts by mass.

The starch-based base coating composition used in the present invention may be blended with other plant-derived resins as necessary. Examples of plant-derived resins other than starch-based resins include plant fiber or cellulose resin, polyhydroxycarboxylic acid typified by polylactic acid, polystrength prolactam, and modified polyvinyl alcohol.

The starch-based base coating composition used in the present invention can contain a cross-linking agent as required. Specific examples of cross-linking agents include A lysocyanine monovalent compound is mentioned. Specifically, as the polyisocyanate compound, for example, the above-mentioned polyisocyanate compound

Examples of the starch-based coating composition used in the present invention include the polyisocyanate compounds exemplified in the section (X 1), as necessary, known plasticizers, UV stabilizers, metal dryers, fluids It is possible to add property modifiers, anti-repellent agents, anti-sagging agents, antioxidants, anti-fogging agents, anti-fogging agents, antiseptics, curing accelerators, scratch-proofing agents, antifoaming agents, and the like.

The starch-based coating composition used in the present invention can be used in known liquid coating systems such as water-based coatings and organic solvent-based coatings. Among these, organic solvent-type paints include, for example, hydrocarbon organic solvents such as toluene, xylene, cyclohexane and n-hexane, ester organic solvents such as methyl acetate, ethyl acetate and butyl acetate, acetone , Methylethylketone, Methylisoptylketone, Methylamylketone and other ketone-based organic solvents used alone or in combination as a dilution solvent are easy to paint as a lacquer, dry It can be made into a very easy-to-use paint with excellent speed.

[Formation of base coating film]

The base coating film in the present invention is formed by coating the starch-based base coating composition on an object to be coated. A known coating method can be applied as a coating method for forming the base coating film. For example, roller coating, brush coating, immersion coating, spray coating (non-electrostatic coating, electrostatic coating, etc.), curtain flow coating, screen printing, letterpress printing, and the like. Of these, spray coating is preferred.

After painting, dry or set. The drying conditions are not particularly limited, but usually the drying is less than 100 ° C, preferably Perform for 1 to 40 minutes at a temperature between 40 ° C and 90 ° C. Alternatively, it can be performed by leaving it set for 10 minutes or more at a temperature of less than 40 ° C.

The film thickness of the base coating film is not particularly limited, but the dry film thickness is generally 0.1 to 30 m, preferably 0.5 to 20 rn, more preferably 1 to 1. 0 m.

[Active energy ray-curable water-based coating composition]

The active energy ray-curable aqueous coating composition used in the present invention contains an aqueous dispersion of an acrylic ester (bl) of a saccharide or a derivative thereof and a photopolymerization initiator (b2).

[Aqueous dispersion of saccharide or its derivative acrylic ester (bl)] An aqueous dispersion of saccharide or its derivative acrylic ester (bl) is a sugar or its derivative, acrylic acid, acrylic acid such as methyl acrylate, etc. Ester (bl) or acrylic acid halide such as acrylic acid chloride is reacted to form acrylic acid ester (bl), and then acrylic acid ester (b 1) is dispersed in water. It is. Examples of the saccharides or derivatives thereof include monosaccharides, sugar alcohols, cyclic alcohols, oligosaccharides, polysaccharides and derivatives thereof. Specific examples of the sugar alcohol include sorbitol, dulci-zyl, and xylitol. Specific examples of the cyclic alcohol include inositol. In the present specification, oligosaccharide means a saccharide from disaccharide to decasaccharide. Examples of the oligosaccharide include a cyclic oligosaccharide and a non-cyclic oligosaccharide. In the present specification, the cyclic oligosaccharide means an oligosaccharide having a structure in which a plurality of monosaccharides are linked in a cyclic form by glycosidic bonds. In addition, the non-cyclic oligosaccharide means an oligosaccharide having a structure in which a plurality of monosaccharides are linked in a chain and non-cyclic manner by glycosidic bonds, unlike the above-mentioned cyclic oligosaccharide. Ring Specific examples of the oligosaccharide include cyclodextrins. Specific examples of non-cyclic oligosaccharides include disaccharides such as reducing disaccharides (maltose, cellobiose, lactose, etc.) and non-reducing disaccharides (sucrose, trehalose, etc.); Examples thereof include oligosaccharides having three or more sugars such as pathose, swath, dextrin and the like. Of these, dextrin is preferred because starch can be obtained by hydrolyzing starch. Non-reducing sucrose and trehalose are not browned by the Maillard reaction (browning reaction). Therefore, it is preferable from the viewpoint of durability of the coating film. In the present specification, the polysaccharide means a saccharide in which a plurality of monosaccharides are linked by glycosidic bonds, and the number of monosaccharides to be bonded is larger than that of oligosaccharides. Specific examples of the polysaccharide include cellulose, chitin, starch, glycogen, agarose, pectin and the like.

As the derivative, for example, a small part of the hydroxyl group in the saccharide is selected from saturated carboxylic acids having 2 to 22 carbon atoms (saturated carboxylic acid, saturated sulfonate ester and / or saturated sulfonate sulfonate). A carboxylic acid ester can be suitably used by at least one kind. Specifically, for example, acetate ester, laurate ester and the like can be mentioned.

The method for producing the acrylate ester (bl) used in the present invention is the same as that for the acrylate ester (al).

The method for adjusting the amount of acryloyl group introduced in the production of the acrylic acid ester (b 1) used in the present invention is the same as in the case of the acrylic acid ester (al).

In addition, the acrylic ester (b 1) of a saccharide or its derivative is obtained by dissolving the saccharide or its derivative in an organic solvent and adding acrylic acid halide (for example, acrylic acid chloride) to produce the acid produced. Neutralize and wash Can also be obtained (dehydrochlorination method).

The weight average molecular weight of the acrylic acid ester (b 1) of the saccharide or derivative thereof thus obtained may have a range of 400 to 2, 2,000, preferably 5,000 to 1,800. From the viewpoint of ease of production, paint viscosity, and finish.

The acrylic ester (bl) of the saccharide or its derivative preferably has an average of 3.0 to 12.0, more preferably an average of 4.0 to 9.0 acryloyl groups per molecule. As a result, the reactivity during irradiation with the active energy line can be increased, and the scratch resistance and Z or adhesion of the obtained coating film can be improved.

The method and emulsifier of the saccharide or its derivative acrylic ester (bl) dispersed in water to form an aqueous dispersion are the same as in the case of the acrylic ester (a1).

[Photoinitiator (b 2)]

The photopolymerization initiator (b 2) generates a radical by being excited by the light energy of the active energy ray, and the radical polymerizable unsaturated group (specifically, the acrylic ester (bl) of the present invention (specifically, Acryloyl group) radical polymerization reaction.

Specific examples of the photopolymerization initiator (b 2) include the same ones as the photopolymerization initiator (a 2).

These photopolymerization initiators (b 2) can be used alone or in combination of two or more. Photopolymerization initiator (b 2) is Irgacure 500 [trade name, manufactured by Ciba Specialty Chemicals Co., Ltd .: 1—Hydroxy-cyclohexyl monophenyl ketone and benzophenone 1: 1 mixture by mass] , Darocur 1 1 7 3 (trade name, Ciba ♦ Specialties Chemicals, 2-Hydroxy-2-methyl-1-phenyl-1-propane) b 2) is preferred from the viewpoint of mixing stability. The content of the photopolymerization initiator (b 2) is 0 with respect to the total amount of acrylic ester (b 1) of the saccharide or its derivative and the active energy ray-curable compound (b 3) described later, 100 parts by mass. Within the range of 1 to 10 parts by weight, preferably 0.2 to 5 parts by weight.

The active energy ray-curable aqueous coating composition used in the coating film forming method of the present invention contains a radical in addition to the photopolymerization initiator (b 2) in order to accelerate the radical polymerization reaction by irradiation with active energy rays. A photosensitizer may be used in combination for the purpose of improving the generation sensitivity and extending the Z or wavelength region.

Specific examples of the photosensitizer that can be used in combination are the same as those of the photosensitizer in the photopolymerization initiator (a 2).

These photosensitizers are acrylic acid esters of sugars or their derivatives.

The range of 0.1 to 5 parts by mass is preferable with respect to 100 parts by mass of (b 1) and the total amount of the active energy ray-curable compound (b 3) described later.

[Active energy ray-curable compound (b 3)]

The active energy ray-curable aqueous coating composition of the present invention may contain an active energy ray-curable compound (b 3) other than the acrylate ester (bl) of the saccharide or a derivative thereof as necessary. . The active energy ray-curable compound (b3) to be blended is a radically polymerizable unsaturated monomer, a radically polymerizable unsaturated group-containing resin, or a radical polymer other than an acrylic ester (b1) of a saccharide or its derivative. It is preferably at least one monomer and / or resin selected from the group consisting of polymerizable unsaturated group- and thermosetting functional group-containing resins. Examples of the radical polymerizable unsaturated monomer include a monofunctional polymerizable monomer, a bifunctional polymerizable monomer, and a trifunctional or higher functional polymerizable monomer. As the monofunctional polymerizable monomer, bifunctional polymerizable monomer, and trifunctional or higher polymerizable monomer, those described in the section of the active energy ray-curable compound (a 3) can be used.

Preferred radical polymerizable unsaturated monomers are bifunctional polymerizable monomers and Z or trifunctional or higher polymerizable monomers from the viewpoint of photocurability, adhesion, and scratch resistance.

As the radical polymerizable unsaturated group-containing resin, those described in the section of the active energy ray-curable compound (a 3) can be used.

Activity of saccharide or its derivative with respect to acrylic ester (bl) As a blending ratio of the energy ray curable compound (b 3), saccharide or its derivative with acrylic ester (b 1) 100 parts by mass is active. The energy ray-curable compound (b 3) is preferably 0 to 90 parts by mass, and more preferably 30 to 400 parts by mass, from the viewpoint of finish and scratch resistance.

Further, the active energy ray-curable water-based coating composition used in the present invention includes, as necessary, a defoaming agent, a surface conditioner, an ultraviolet absorber, a light stabilizer, an antifoaming agent, an organic colorant, a natural colorant, Dyes and inorganic pigments can be used. Examples thereof include those described in the section “A. Active energy ray-curable coating composition”.

There is no particular limitation on the method of making the aqueous composition when producing the active energy ray-curable aqueous coating composition used in the coating film forming method of the present invention. As a method of making it aqueous, for example, after mixing an acrylic ester (bl) of a saccharide or a derivative thereof or an organic solvent solution thereof, a photopolymerization initiator (b 2) and an emulsifier, water is gradually added while stirring. The method of making it water-dispersed by making it water-based is mentioned. As another method, an aqueous dispersion obtained by dispersing an acrylic ester (bl) of a saccharide or a derivative thereof in water, and a photopolymerization initiator (b 2) And other components in an aqueous medium according to a conventional method. When the active energy ray-curable compound (b 3) is used, it is preferable from the viewpoint of mixing stability to use an aqueous dispersion obtained by previously dispersing the compound in water. The method for dispersing the active energy ray-curable compound (b 3) in water can be the same as the method for dispersing the acrylate or acrylate ester (b 1) in water. Further, when the photopolymerization initiator (b 2) is a solid photopolymerization initiator (b 2) having a low water solubility, it can be uniformly added and dissolved in the active energy ray-curable compound (b 3). It is preferable from the viewpoint of photocuring, finish, and scratch resistance.

[Method of coating active energy ray-curable aqueous coating composition]

A known coating method can be applied as a coating method when the active energy ray-curable aqueous coating composition used in the present invention is applied. For example, roller coating, brush coating, immersion coating, spray coating (non-electrostatic coating, electrostatic coating, etc.), curtain flow coating, screen printing, letterpress printing, and the like. Of these, spray coating is preferred.

The film thickness of the coating film formed by the above coating is not particularly limited, but the dry film thickness is 0.1 to 30 m, preferably 1 to 25 im, more preferably 5 to 2 0 m.

The concentration of the non-volatile content of the active energy ray-curable aqueous coating composition is not particularly limited as long as it can be applied. However, when spray coating is performed, it is preferably in the range of 10 to 50% by mass. is there.

[Step of irradiating active energy rays]

After applying the active energy ray-curable aqueous coating composition, it is desirable to volatilize a solvent such as water by heating or setting and then irradiate the active energy ray. The means for heating is not particularly limited. For example, a hot air furnace, an electric furnace ・ Drying equipment such as infrared induction heating can be applied. The heating temperature is not particularly limited, but is usually in the range of 35 to 100 ° C., preferably 40 to 90 ° C. The heating time is not particularly limited, but usually a range of 1 to 30 minutes is preferable.

The active energy ray to be irradiated is not particularly limited, and may be any of electron beam, ultraviolet ray, visible light, and infrared ray. An active energy ray having a wavelength of 200 to 600 nm, preferably a wavelength of 300 to 45 nm is preferable from the viewpoint of finish.

As the active energy ray irradiation source, an irradiation source having a wavelength with high sensitivity can be appropriately selected and used according to the type of the photopolymerization initiator (b 2). Examples of the active energy ray irradiation source include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, and sunlight.

The conditions for irradiating active energy rays are usually in the range where the integrated light quantity is 1, 0 0 0 to 2 0, OOOJ Zm ² , preferably 2, 0 0 0 to 1 5, 0 0 0 J / m ² ing. As the irradiation time, the coating film can be cured in about 1 second to 5 minutes. The above range is preferable from the viewpoints of the photocurability of the coating film and resistance to yellowing.

In addition, the active energy ray-curable water-based coating composition can be heated as an auxiliary crosslinking means after or simultaneously with irradiation of the active energy line.

The coated article obtained by the coating film forming method of the present invention can be used as a material or a part of, for example, an electric part, a mobile phone, lighting, an electric element, a semiconductor, a vending machine or the like. Example

Hereinafter, the present invention will be described more specifically with reference to examples. Akira is not limited to this. “Parts” and “%” mean “parts by mass” and “% by mass” unless otherwise specified.

<< A. Examples of active energy ray curable coating compositions >> <Production example A— 1>

Example of production of acrylic ester N o. A_ l solution (for examples)

In a reaction vessel equipped with a distillation apparatus, thermometer, and stirrer, dextrin (I) (glucose polymer having an average polymerization number of 4 and having an average of 14 hydroxyl groups per molecule) 80 parts, methylisoptyl ketone 1 100 parts, 0.16 parts of methylhydroquinone, 5.9 parts of lithium hydroxide monohydrate, and 50.6.2 parts of methyl acrylate were charged.

Next, nitrogen was blown into this solution and heated to 90 ° C. with stirring, and methyl acrylate, methanol, and methyl isoptyl ketone were gradually distilled out of the system. Methyl acrylate and methyl isobutyl ketone, which decrease with distillation, are added to the reaction vessel, and then the reaction is traced by measuring the amount of methanol in the reaction vessel and the distilled methanol by gas chromatography. Then, the mixture was cooled when 6.0 hydroxyl groups per molecule of the above dextrin (I) were converted to acrylate. Furthermore, the reaction solution is concentrated under reduced pressure, and ethyl acetate is added to the residue to obtain a nonvolatile content concentration of 25%, a weight average molecular weight of 1,100, and an average of 6.0 acryloyl groups per molecule. An acrylic ester No. A-1 solution of the present invention was obtained.

Example of production of acrylic ester No. A-2 solution (for examples)

In Production Example A-1, 1 molecule per dextrin (I) The reaction was traced by quantifying the methanol and distilled methanol in the reaction vessel by gas chromatography until an average of 10.0 hydroxyl groups out of an average of 14 hydroxyl groups was converted to acrylate ester. The acrylic acid of the present invention having a weight average molecular weight of 1,400 and an average of 10.0 acryloyl groups per molecule was the same as in Production Example A-1 except that the reaction time was extended. An ester No. A-2 solution was obtained.

Example of production of acrylic ester No. A-3 solution (for examples)

In Production Example A-1, dextrin (I) is a glucose polymer having an average polymerization number of 3 and having an average of 11 hydroxyl groups per molecule.

In the same manner as in Production Example A-1 except that I) is used, an average of 6 hydroxyl groups per molecule of the dextrin (I I) is 6.

The reaction was traced by measuring the methanol and distilled methanol in the reaction vessel by gas chromatography until 0 hydroxyl groups were converted to acrylate, and the weight average molecular weight was 9500 and 1 molecule. An acrylic acid ester No. A-3 solution of the present invention having an average of 6.0 acryloyl groups per unit was obtained.

Example of production of acrylic ester No 4 A-4 solution (for examples)

In Production Example A-1, the same procedure as in Production Example A-1 except that dextrin (III), which is a glucose polymer having an average polymerization number of 6 and has an average of 20 hydroxyl groups per molecule, was used. The methanol and distilled methanol in the reaction vessel were measured by gas chromatography until an average of 6.0 hydroxyl groups per molecule of dextrin (III) was converted to acrylate. The reaction is followed by quantifying the weight average molecular weight of 1,500 and An acrylate ester No. A-4 solution of the present invention having an average of 6.0 acryloyl groups per molecule was obtained.

Example of production of acrylic ester No. A-5 solution (for comparison)

In Production Example A-1, the reaction was traced by quantifying methanol and distilled methanol in the reaction vessel by gas chromatography, and an average of 2.0 per molecule of dextrin (I) Acrylic acid ester having a weight average molecular weight of 800 and an average of 2.0 acryloyl groups per molecule in the same manner as in Production Example A-1 except that cooling is performed when the hydroxyl group is converted to an acrylic ester. A No. A 15 solution was obtained.

Acrylic ester No. A-6 production example (for comparative example)

In Production Example A-1, the reaction was traced by quantifying methanol and distilled methanol in the reaction vessel by gas chromatography, and an average of 13.0 molecules per molecule of dextrin (I). Except for cooling when the hydroxyl group is converted to acrylic acid ester, it has a weight average molecular weight of 1,600 and an average of 13.0 acryloyl groups per molecule in the same manner as in Production Example A_ l An acrylic ester No. A-6 solution was obtained.

Acrylic acid ester N o. A—Production example of 7 solution (for comparative example)

In Production Example A-1, the same procedure as in Production Example A-1 except that dextrin (IV), which is a glucose polymer having an average polymerization number of 8 and has an average of 26 hydroxyl groups per molecule, is used. Among the 26 hydroxyl groups averaged per molecule possessed by the dextrin (IV), an average of 10.0 hydroxyl groups is converted into acrylic acid ester until the methacrylic acid in the reaction vessel. The reaction was traced by determining the amount of methanol and distilled methanol by gas chromatography, and acrylic acid having a weight average molecular weight of 2,100 and an average of 10.0 acryloyl groups per molecule. An ester No. A-7 solution was obtained.

Example of production of acrylic ester No. A-8 solution (for examples)

In Production Example A-1, trehalo was substituted for dextrin (I).

-The reaction was traced by measuring the amount of methanol in the reaction vessel and the distilled methanol by gas chromatography, and an average of 6.0 hydroxyl groups per molecule of trehalose was converted to an acrylate ester. Acrylate ester No. A-8 solution having a weight average molecular weight of 780 and an average of 6.0 acryloyl groups per molecule was obtained in the same manner as in Production Example A-1 except that the sample was cooled in the middle. The

Example of production of acrylic ester No. A-9 solution (for examples)

In Production Example A-1, the reaction was traced by using trehalose instead of dextrin (I), and quantifying the methanol in the reaction vessel and the distilled methanol by gas chromatography. The average weight per molecule of 3. In the same manner as in Production Example A-1 except that cooling is performed when two hydroxyl groups have been converted to acrylates, the weight average molecular weight is 5 60 and the average is 3.2 per molecule. Acrylic acid ester N o .A-9 solution containing acryloyl group was obtained

Acrylic ester No. A—10 Example of production of solution (for comparative example)

Instead of dextrin (I) in Production Example A-1 Trehalo The reaction was followed by quantifying the methanol in the reaction vessel and the distilled methanol by gas chromatography, and an average of 2.0 hydroxyl groups per molecule of trehalose was esterified with acrylic acid. By the way, except for cooling, in the same manner as in Production Example A-1, an acrylate ester having a weight average molecular weight of 4900 and an average of 2.0 acryloyl groups per molecule No. A-10 Production Example A-1 1 1>

Acrylic acid ester No. A— 1 1 Example of production of solution (for examples)

In Production Example A-1, maltose was used in place of dextrin (I), and the reaction was traced by quantifying the methanol in the reaction vessel and the distilled methanol by gas chromatography. Except for cooling when an average of 6.0 hydroxyl groups per molecule was esterified with acrylic acid, in the same manner as in Production Example A-1, the weight average molecular weight was 780 and an average of 6.0 per molecule. An acrylic ester N o, A-11 solution having an acryloyl group was obtained. <Production example A— 1 2>

Example of production of acrylic acid ester N o. A— 1 2 solution (for Examples)

In Production Example A-1, sucrose was used instead of dextrin (I), and the reaction was traced by quantifying the methanol in the reaction vessel and the distilled methanol by gas chromatography, and per molecule of the sucrose. Except for cooling when an average of 6.0 hydroxyl groups was esterified with acrylic acid, the same as in Production Example A-1, the weight average molecular weight was 7800 and the average of 6.0 acryloyl per molecule. An acrylic ester N 0 .A-12 solution containing a thio group was obtained. <Production example A— 1 3>

Acrylic ester N o. A— 1 3 Example of making solution (for comparison) In a 1-liter glass round bottom four-necked flask equipped with a distillation apparatus, thermometer and stirrer, add 79.5 parts of j6-cyclodextrin, 400 parts of dimethylformamide, and 0 part of methylhydroquinone. 1 Prepared 6 copies. Next, after stirring this mixed liquid to a uniform state, 17.4 parts of dibutyltinoxide (corresponding to 2 parts relative to 100 parts of 3-cyclodextrin) was added, and air was added to the mixed liquid. Was heated to 110 ° C. while blowing the solution at 10 ml LZ and stirring the solution. Next, while maintaining the temperature of the reaction solution at 110 ° C., 1,000 parts of methyl acrylate were dropped into the reaction solution at a rate of about 40 parts Z over 25 hours. Twenty-five hours after the start of distillation, the amount of methanol contained in the distillate was 9.27 parts. From the amount of methanol removed, an average of 4.0 per molecule of ^ -cyclodextrin was obtained. It was confirmed that each hydroxyl group was esterified with acrylic acid.

The catalyst in the reaction solution was filtered off, and the filtrate was concentrated under reduced pressure. Then, isopropanol was added to the residue to crystallize the desired product, and the crystal was separated. The obtained crystals were washed with isopropanol and dried to obtain 72.6 parts of 4.0-functional acrylic acid ester of / 3-cyclodextrin. The obtained acrylic acid ester was dissolved in butyl acetate, and the acrylic acid ester having a nonvolatile content concentration of 25%, a weight average molecular weight of 1520 and an average of 4.0 acryloyl groups per molecule No. A-1 3 A solution was obtained.

Photo curable resin solution No. A— 1 production example (equivalent to active energy ray curable compound (a 3))

In a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser, and air blowing device, isophorone diisocyanate 8 8 8 parts, 2 — Hydroxy sheryl acrylate 4 6 4 parts and a feed port Kinonmo Charge 0.7 parts of nomethyl ether, blow the air into the reaction vessel, raise the temperature to 80 X and keep at that temperature for 5 hours, and the added hydroxyl group of 2-hydroxychetyl acrylate is substantially After confirming that all of the reaction had occurred, 13.6 parts of pentaerythritol, 37.2 parts of butyl acetate and 0.2 part of dibutyltin dilaurate were added, and the temperature was further maintained at 80 ° C. After confirming that substantially all of the isocyanate groups of the isocyanate had reacted, the mixture was cooled to obtain a photocurable resin solution No. A-1 having a resin non-volatile content of 80%. The number average molecular weight of this resin was about 1,500.

Reactive polymer emulsifiers No. A-1 Production of solutions

Add 1 part of propylene glycol monomethyl ether acetate to a four-necked flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen inlet, and stir while introducing nitrogen gas. Heated to 20 ° C. Next, styrene 1 30 parts, n-butyl methacrylate 5 90 parts, 2-hydroxychestyl methacrylate 8 parts, glycidyl methacrylate 5 parts, methyl methacrylate 40 parts, 2, 2 '—azobis — A mixture of 20 parts of 2_methylbutylonitrile was added dropwise from the dropping tank over 3 hours. After completion of the dropwise addition, a copolymer was obtained by maintaining at the same temperature for 0.5 hours, and then 20 parts of styrene, 4 parts of n-butyl methacrylate, 2 parts of 2-hydroxychetyl methacrylate. A mixture of 15 parts of 1 part, 60 parts of acrylic acid, 10 parts of methyl methacrylate, and 10 parts of t-methyl paroxyl-2-ethylhexanoate was added dropwise from a dropping tank over 1 hour. After completion of the dropwise addition, the mixture was kept at the same temperature for 0.5 hours, and further, 3 parts of 50 parts of a solution of 10 parts of 1-butyl peroxy-2-ethyl hexanoate dissolved in 40 parts of propylene glycol monomethyl ether acetate. It was added dropwise over 0 minutes. 1 hour Aged. After cooling to 80 ° C., 50 parts of 2-acryloyloxychetyl isocyanate and 0.1 part of neostane U—100 (tin-based catalyst) were added and stirred for 2 hours. The solvent was distilled off to a non-volatile content concentration of 70% to obtain a reactive polymer emulsifier No. A-1 solution.

Production of active energy ray curable coating composition No. A-1

Production Example A— Irgacure 1 8 4 (Product Name) against acryloyl ester No. A-1 solution 4 0 0 parts (nonvolatile content 1 0 0 parts) obtained in A-1

5 5

Ciba Specialty Chemicals Co., Ltd., photopolymerization initiator) 3 parts added and dissolved, diluted with butyl acetate to a non-volatile content concentration of 20%, organic solvent type active energy ray curable coating composition N o. A-1 was obtained.

Production of active energy ray curable coating composition No. A— 2 to No. A— 1 1

Except for the contents shown in Table A-1 below, the organic solvent type active energy ray curable coating compositions No. A-2 to No. A_11 were obtained in the same manner as Example A-1. It was.

Table A— 1

The numerical value in a mixing | blending shows a non volatile matter.

Production of active energy ray-curable coating composition No. A— 1 2

The solvent was distilled off from the acrylic acid ester No. A-1 solution obtained in Production Example A-1 to obtain a solution having a nonvolatile content of 70%. 1 4 2. 9 parts of this solution (non-volatile content: 100 parts) were added to Darocur 1 1 7 3 (trade name, manufactured by Ciba 'Specialty' Chemicals, 2 — Hydroxy 2 — Methyl 1 1_ON, photopolymerization initiator) 3 parts, and RMA-5 0 6 (trade name, manufactured by Nippon Emulsifier Co., Ltd., polyoxyethylene nonyl phenyl ether acrylate, nonionic reactive emulsifier) 6 parts While stirring, 20.4 parts of deionized water was gradually added to disperse in water. In addition, 1 part of B YK-3 4 8 (trade name, manufactured by Bicchemi Co., Ltd., surface conditioner) was added, and 30% non-volatile water-based active energy-line curable coating composition No. A-1 2 was added. Obtained.

Production of active energy ray curable coating compositions No. A— 1 3 and No. A— 14

Examples according to the formulation in Table A-2 except that the acrylic ester No. A-1 solution was changed to an acrylic ester No. A-8 solution and an acrylic ester No. A-12 solution. In the same manner as A-1 2, aqueous type active energy ray curable coating compositions having a non-volatile content of 30% were obtained.

Production of active energy ray-curable coating composition No. A—15

The solvent was distilled off from the acrylic ester No. A-1 solution obtained in Production Example A-1 to obtain a solution having a nonvolatile content of 70%. 1 4 2. 9 parts of this solution (non-volatile content 100 parts), Darocur 1 1 7 3 3 parts, and the reactive polymer emulsifier obtained in Production Example A-1 5 No. A-1 1 4 3 parts (10 parts of non-volatile content) was added, and 2 18.8 parts of deionized water was gradually added while stirring to disperse in water. Furthermore, 1 part of B YK-3 4 8 was added to obtain an aqueous active energy ray-curable coating composition No. A-15 having a nonvolatile content of 30%.

Production of active energy ray curable coating composition No. A—16

To the photocurable resin solution No. A-1 obtained in Production Example A-14, butyl acetate was added to obtain a solution having a nonvolatile content of 70%. Darocur 1 1 7 3 3 parts and RMA — 5 0 6 6 parts are added to 1 4 2.9 parts of this solution (non-volatile content 1 100 parts), and 2 1 0. 4 parts of deionized water are gradually added while stirring. In addition, an aqueous dispersion was obtained. Further, 1 part of BYK-3 4 8 was added to obtain a composition having a nonvolatile content of 30%. 30 parts of this composition was mixed with 30 parts of an aqueous active energy ray-curable coating composition of 30% non-volatile content obtained in Example A-1 2 with stirring. As a result, an aqueous active energy ray-curable coating composition No. A_l 6 having a nonvolatile content of 30% was obtained.

Table A-2

The numerical value in a mixing | blending shows a non volatile matter.

Production of active energy ray curable coating compositions No. A—17 to No. A—23

Except for the contents shown in Table A-3, the organic solvent-type active energy ray-curable coating composition No. A—17 to No. A — 23 was obtained in the same manner as in Example A-1. It was.

Table A-3

The numerical value in a mixing | blending shows a non volatile matter.

Production of active energy ray curable coating compositions No. A—24-No.A-26

Aqueous active energy ray-curable coating compositions No. A—24 to No. A—26 were obtained in the same manner as in Example A—12 except that the content of Table A-4 was used. It was.

Production of active energy ray curable coating composition No. A-2 7

A water-based active energy ray-curable coating composition No. A-2 7 was obtained in the same manner as in Example A-1-6 except that the content of Table A-4 was changed.

Table A— 4

The numerical value in a mixing | blending shows a non volatile matter.

[Preparation of test paint plate]

A polycarbonate resin plate (trade name, Dialite P, manufactured by Mitsubishi Rayon Co., Ltd., 70 mmXl 50 mmX2 mm) was used as an object to be coated. Each of the active energy ray-curing coating compositions obtained in Examples and Comparative Examples No. A 1 l to No. A-2 7 is applied by air spray so that the dry coating film becomes 12 m. Example A— 1 to A— 1 1 and Comparative Example A— 1 to A_ 7 at 60 at 5 minutes, Example A— 1 2 to A— 1 6 and Comparative Example A— 8 to A— 1 1 was dried at 60 ° C. for 10 minutes. Furthermore, the test plate corresponding to No of each active energy ray-curing coating composition is cured by irradiating with UV light of 6,00 0 J Zm ² with a high-pressure mercury lamp and photocuring. ~ No o A-2 7 was obtained.

Test plates No. A—l to No. A—27 were subjected to the test according to the following test method. The results of the examples are shown in Table A-5, and the results of the comparative examples are shown in Table A-6.

Table A-5

Table A—5 (continued)

Table A—6

Table A—6 (continued)

[Test method]

(Note A— 1) Finishability

The coated surface appearance of each coating film was visually evaluated.

VeryGood (VG): No waviness, glossy pickle, or chilli skin, and a good finish (passed as a product)

Good (G): Slightly at least one of swell, glossy pickle, and chilli skin but good finish (pass as product)

F i r (F): At least one of swell, glossy pickle, and chilli skin is seen (failed as a product)

P o o r (P): At least one of swell, glossy pickle, and chilli skin is noticeable and the finish is poor (failed as a product)

(Note A—2) Pencil hardness

In accordance with JISK 5 6 0 0— 5— 4 (1 9 9 9), apply a pencil lead at an angle of approximately 45 ° to each coating surface, and press against the test coating surface to the extent that the lead does not break. However, it moved about 10 mm forward at a uniform speed. This operation was repeated 5 times with different test locations, and the hardness symbol of the hardest pencil when the coating did not break was designated as pencil hardness.

(Note A-3) Scratch resistance (1)

A commercially available business card was pressed against the coating film on each coating film and rubbed back and forth 20 times.

V er y Go o d (V G): Not scratched at all.

G o o d (G): Scratches are scarce and must be approached (5 cm). Scratches not visible (pass as product)

F a i r (F): Slightly scratched (not acceptable as a product)

P o o r (P): Scratch is severe (failed as a product)

_11 Main A — 4) Scratch resistance (2) Each coated plate for test was subjected to a Taber abrasion test (abrasion wheel CF—10 P, load: 500 g, 100 rpm) in accordance with AS TM D 10 4 4. With respect to the coating film before and after the test, the luminosity of each coating surface was measured according to the specular glossiness (60 degrees) of JISK 5600-0-7 (199). The glossiness after the test relative to the glossiness before the test was determined as the gloss retention (%) and evaluated according to the following criteria.

VeryGood (VG): Gloss retention 90% or more

G o o d (G): Gloss retention 80% or more and less than 90%

F a i r (F): Gloss retention 60% or more and less than 80%

P o o r (P): Gloss retention less than 60%

(Note A-5) Weather resistance

Each test plate was subjected to a 500-hour weather resistance test using Sunshine Weathering according to JISK 5600-0-7-8 (1 9 9 9), according to the following criteria: evaluated.

Very Good (VG): No abnormalities were observed on the paint film surface, and the color difference ΔΕ conforming to JISZ 87 30 was less than 0.3 in the test plate at the initial stage and after the test. )

G ood (G): Slight yellowing is observed, and the color difference Δ 準拠 in accordance with JISZ 8 7 3 0 is 0.3 or more and less than 0.5 in the initial and post-test test plates. )

F air (F): Yellowing is observed in the paint film, and the color difference △ E based on JISZ 8 7 30 is between 0.5 and less than 0.8 in the test plate in the initial stage and after the test. failure)

P o o r (P): The yellowing of the paint film is remarkable, and the color difference Δ 準拠 in accordance with JISZ 8 7 3 0 is 0.8 or more in the initial and post-test test plates.

(Note Α-6) Solvent resistance Two filter papers were placed side by side on each coating surface, and 78% ethanol and 2% formalin were separately dropped on each filter paper with a spot to wet the filter paper. Dropping with this spot was performed 5 times at 1 hour intervals, and after 2 hours, the surface of the coating film with the filter paper removed was visually evaluated.

G o o d (G): No abnormalities such as bulge and Z or peeling

F a i r (F): At least one of the coating films has a slight bulge and / or abnormalities such as galling.

P o o r (P): At least one of the coatings dissolves

<< B. Examples of coating film formation method >>

Manufacture of starch-based resin (I)

Starch-based resin (I 1 1)

High amylose corn starch (manufactured by Nippon Corn Starch Co., Ltd., hydroxy group value 500 mg KOHZ g) 2 5 parts are suspended in 20 parts of dimethyl sulfoxide (DMSO) and heated to 90 ° C while stirring. Warm and hold at that temperature for 20 minutes to gelatinize. To this solution, 20 parts of sodium bicarbonate was added as a catalyst, 17 parts of vinyl laurate was added while maintaining 90 ° C., and the mixture was reacted at that temperature for 1 hour. Next, another 7 parts of vinyl acetate 37 was added and reacted at 80 ° C for 1 hour. Thereafter, the reaction solution was poured into tap water, stirred at high speed, pulverized, filtered, dehydrated and dried to prepare a starch-based resin (I 1 1).

Production of a product (X) having an isocyanate group

Adult cattle with isocyanate groups (X— 1)

Charge a 1 L reaction vessel equipped with a thermometer, thermostat, stirrer, condenser, and dripping device. 1 25 5 parts of toluene and 7 7 parts of isophorone diisocyanate are stirred in a nitrogen atmosphere. Mix while The temperature was raised to 80 ° C. Subsequently, 1,3-butanediol 1 2 3 parts were added dropwise over 3 hours, and after completion of the addition, the mixture was aged for 30 minutes at 80 ° C., and a product having an isocyanate group with a non-volatile content of 80% ( X— 1) A solution was prepared. N of the obtained product (X-1) having an isocyanate group

The C 2 O value was 55 mg N C OZ g.

Products with isocyanate groups (X— 2)

A 1 L reaction vessel equipped with a thermometer, thermostat, stirrer, condenser, and dripping device was charged with 1 2 5 parts of toluene and 1 2 3 parts of isophorone diisocyanate and stirred in a nitrogen atmosphere. The mixture was mixed and heated to 80 ° C. Next, 7 parts of triethylene glycol 1 1 7 parts were added dropwise over 3 hours. After completion of the addition, the mixture was aged for 30 minutes at 80 ° C, and a product having an isocyanate group of 80% non-volatile content (X-2 ) The solution was prepared. The N C O value of the product (X-2) having an isocyanate group thus obtained was 57 mg N C O / g.

Manufacture of vinyl copolymer resin (Y)

Production Example B-4>

Vinyl copolymer resin (Y—1)

Charge 33.3 parts of toluene into a 1 L reaction vessel equipped with a thermometer, thermostat, stirrer, condenser and dripping device, mix under stirring in a nitrogen atmosphere, and rise to 100 ° C Warm up. Next, “Mixture B-1” having the following composition was added dropwise over 4 hours. After completion of the dropwise addition, the mixture was aged at 100 ° C. for 1 hour to obtain a vinyl copolymer resin (Y-1) having a nonvolatile content of 60%. A solution was obtained. The obtained vinyl copolymer resin (Y-1) had a hydroxyl value of 86 mg KOHZ g.

“Mixture B— 1”

Styrene 2 0 0 parts Methyl methacrylate 1 5 0 parts n-Butyl acrylate 5 0 parts Methacrylic acid 2-hydroxychetyl 1 0 0 parts

2, 2, —Azobis (2-methylpropylonitrile) 2 5 parts Manufacture of starch-based resin (I I)

Starch-based resin (I I 1 1)

Into a 1 L reaction vessel equipped with a thermometer, thermostat, stirrer and condenser, 5.95.0 parts of butyl acetate was charged, and the temperature was raised to 50 ° C. while stirring in a nitrogen atmosphere. Next, 1 80 parts of the starch-based resin (I 1 1) obtained in Production Example B 1-1 while being kept at 50 ° C was charged into a reaction vessel, and then heated to 100 ° C and charged. The starch-based resin (I-1) was stirred until all was dissolved. Next, after adding 25 parts of the product (X-1) solution having an isocyanate group having a non-volatile content of 80% obtained in Production Example B-2 and stirring until homogeneous, dibutyltin dilaurate was used as a catalyst. 0,02 parts were added, and the mixture was reacted at 100 ° C. for 6 hours with stirring under a nitrogen atmosphere to obtain a starch resin (II 1 1) solution having a nonvolatile content of 25%. The N C O value of the obtained starch-based resin (I I 1 1) was 0.4 mg N C OZ g.

Manufacturing Example B— 6 to B _ 8>

Starch-based resin (I 1-2) to (I 1-4)

A starch-based resin (II-12) to (II-4) solution was obtained in the same manner as in Production Example B-5 except that the composition shown in Table B_1 was used. Table B-1 shows the N C O values of the resins obtained.

Manufacture of starch-based resin (I I I)

Starch-based resin (III 1 1) A vinyl copolymer resin with a non-volatile content of 60% obtained in Production Example B-4 in a 1 L reaction vessel equipped with a thermometer, thermostat, stirrer, and condenser, in a 1 L capacity vessel. (Y-1) The solution was charged with 33.4 parts, and the temperature was raised to 50 ° C. with stirring in a nitrogen atmosphere. Next, the starch-based resin (I 1 1) 160 obtained in Production Example B-1 was maintained at 50 ° C. in a reaction vessel with stirring, and the temperature was raised to 100 ° C. Thus, all of the charged starch resin (I-1) was dissolved. Next, 25 parts of a product (X-1) solution having an isocyanate group having a nonvolatile content of 80% obtained in Production Example B-2 was charged and stirred until homogeneous, and then dipyltin dilaurate as a catalyst. 0.02 part was added, and the mixture was reacted at 100 ° C. for 6 hours with stirring under a nitrogen atmosphere to obtain a starch resin (III-11) solution having a nonvolatile content of 25%. The NCO value of the obtained starch-based resin (III-1) was 0.4 mg NC0 /.

Production Example B— 1 0 to B— 1 2>

Starch Resin (I I I 1 2)-(I I I 1 4)

A starch-based resin (III-12) to (III-14) solution was obtained in the same manner as in Production Example B-9 except that the composition shown in Table B-1 was used. Table B-1 shows the NC values of the resins obtained.

Table B— 1

The numerical value in a mixing | blending represents a mass part, The inside of () represents a non volatile matter.

Manufacture of starch-based resin (IV)

Starch resin (I V— 1)

Into a reaction vessel with a capacity of 1 L equipped with a thermometer, thermostat, stirrer, condenser, and dripping device, 46 6 parts of butyl acetate was charged, and the temperature was raised to 50 ° C. while stirring in a nitrogen atmosphere. Next, hold the starch-based resin (I 1 1) 160 obtained in Production Example B-1 at 50 ° C. in a reaction vessel, and then raise the temperature to 100 ° C. The starch-based resin (I 1 1) was stirred until completely dissolved. Next, “Mixture B-2” having the following composition was added dropwise over 1 hour. After completion of the addition, the mixture was aged at 100 ° C. for 1 hour to give a starch-based resin (IV-1) solution having a nonvolatile content of 30%. Got.

"Mixture B-2"

Styrene 3 2 parts Methyl methacrylate 4 parts Acrylic acid n —Butyl 4 parts Par force Dock C H— 50 L (Note B _ 1) 4 parts

(Note B-1) Polymerization initiator containing 50% disilver oxide: manufactured by Kayaku Akuzo Corporation

Starch-based resin (IV-2)

A starch-based resin (IV-2) solution with a nonvolatile content of 30% in the same manner as in Production Example B-13, except that "Mixture B-3" having the following composition was used instead of "Mixture B-2" Got.

“Mixture B-3”

Styrene 2 8 parts Methyl methacrylate 4 parts Acrylic acid n —Ptyl 4 parts Methacrylic acid 2 —Hydrochetil 4 parts Pour force CH— 5 0 L 4 parts

Starch-based resin (IV-3)

A starch-based resin (IV_3) solution with a nonvolatile content of 30% in the same manner as in Production Example B-13, except that "Mixture B-4" having the following composition was used instead of "Mixture B-2" Got.

“Mixture B—4”

Styrene 1 6 parts Methyl methacrylate 1 6 parts N-butyl acrylate 4 parts Methacrylic acid 2 —Hydroxychetyl 4 parts Parr force Dock C H— 50 L 4 parts Production Example B— 1 6>

Starch resin (I V _ 4)

The amount of starch-based resin (I 1 1) charged is 180 parts.

A starch-based resin (IV-4) with a nonvolatile content of 30% was prepared in the same manner as in Production Example B-13, except that "Mixture B-5" having the following composition was used instead of "2".

) A solution was obtained.

"Mixture B-5"

Styrene 1 4 parts Methyl methacrylate 2 parts N-butyl acrylate 2 parts Methyl methacrylate 2 —Hydroxychetyl 2 parts Power dox C H— 50 L 2 parts

Starch resin 1J V— 5) A starch-based resin (IV-5) with a non-volatile content of 30% was prepared in the same manner as in Production Example B_l3, except that “Mixture B — 6” having the following composition was used instead of “Mixture B-2”. A solution was obtained.

“Mixture B—6”

Methyl methacrylate 3 2 parts N-butyl acrylate 4 parts Parr force Dock C H— 50 L 4 parts Manufacture of starch-based resin (V)

Starch-based resin (V— 1)

Production of products with isocyanate groups (X— 3)

A 1 L reaction vessel equipped with a thermometer, thermostat, stirrer, condenser, and dripping device was charged with 12.5 parts of toluene and 2 parts of hexamethylene diisocyanate, and stirred under a nitrogen atmosphere. While mixing, the temperature was raised to 80. Next, 20 parts of triethylene glycol was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was aged for 30 minutes at 80 ° C. to obtain a product having an isocyanate group having a nonvolatile content of 80% (X-3 ) A solution was obtained. The obtained product (X-3) having an isocyanate group had an N 2 C 3 O value of 58 mg N C0 / g.

Manufacture of starch-based resin (V-1)

In a 1 L reaction vessel equipped with a thermometer, thermostat, stirrer and cooling tube, 4 parts of Ptyl acetate, 30% non-volatile starch resin (IV-2) solution obtained in Production Example B-14 Was heated to 100 ° C. with stirring in a nitrogen atmosphere. Next, 25 parts of the product (X-3) solution having an isocyanate r "to group having a non-volatile content of 80% obtained above was charged and stirred until homogeneous, and then dibutyltin dilaurate as a catalyst. 0, 0 4 parts are added and stirred in a nitrogen atmosphere with 1 0 0 at 6 By reacting for a period of time, a starch resin (V-1) solution having a nonvolatile content of 30% was obtained. The NC value of the obtained starch-based resin (V-1) was 0.4 mg NCO / g.

Starch resin (V— 2)

Production of products with isocyanate groups (X— 4)

Into a 1 L reaction vessel equipped with a thermometer, thermostat, stirrer, condenser and dripping device, charge 12.5 parts of toluene and 37.8 parts of isophorone diisocyanate and mix in a nitrogen atmosphere while stirring. The temperature was raised to 80 ° C. Next, 1,2-butanediol 1 2 2 parts were added dropwise over 3 hours. After completion of the addition, the product was aged at 80 ° C. for 30 minutes to give a product having an isocyanate group having a nonvolatile content of 80% ( X— 4) A solution was obtained. The N C O value of the product (X-4) having an isocyanate group thus obtained was 57 mg N C O / g.

Manufacture of starch-based resin (V-2)

Starch resin (IV-5) solution with a non-volatile content of 30% obtained in Production Example B-17 in a 1 L reaction vessel equipped with a thermometer, thermostat, stirrer, and condenser. Was heated to 100 ° C. with stirring under a nitrogen atmosphere. Next, 25 parts of the product (X-4) solution having an isocyanate group having a non-volatile content of 80% obtained above was charged, stirred until uniform, and dibutyltin dilaurate as a catalyst. 4 parts were added and reacted for 6 hours at 100 ° C. with stirring in a nitrogen atmosphere to obtain a starch-based resin (V-2) solution having a nonvolatile content of 30%. The N C0 value of the obtained starch-based resin (V-2) was 0.4 mg N C O Z g.

Manufacture of starch-based base coating composition

<Production example B-2 0> Starch-based paint composition No. B— 1

100 parts of starch-based resin (I 1 1) obtained in Production Example B-1 (100 parts of non-volatile content), aluminum paste F. X 1 4 4 0 (Note B— 2) 4 1. 8 Parts (non-volatile content 2 3 parts), high-conc black (Note B-3) 3 parts, and methyl ethyl ketone 3 5 9. Add 2 parts and mix well with a stirrer. A starch-based base coating composition No. B-1 was obtained.

Starch-based base coating composition N o. B— 2 to N o. B— 2 0

Except for the blending composition shown in Table B-2, a starch-based base coating composition having a nonvolatile content of 25% No. B-2 to No. B-2 as in Production Example B-20 Got 0.

Table B-2

Numerical values in the formulation represent parts by mass, and () represents the nonvolatile content.

Table B-2 (continued)

(Note B—2) Aluminum paste F. X 1 4 40: Product name, manufactured by Toyo Aluminum Co., Ltd. Aluminum pace 卜

(Note B-3) High-conc black: Product name, manufactured by Yokohama Kasei Co., Ltd., black colorant for solvent-borne paints

(Note B-4) Nitrified cotton for industrial use BNC-HIGG-2: Product name, manufactured by Bergerac N.C. France, dissolved in 2-ethylcellulose cellulose in ethyl acetate

(Note B-5) C AB 5 5 1-0.2: Product name, manufactured by Yeast Man Chemical Products, cellulose acetate petitate dissolved in ethyl acetate

(Note B—6) Takenate D—170 HN: Trade name, manufactured by Mitsui Chemicals Polyurethane, Inc. Isocyanurate of hexamethylene diisocyanate

Manufacture of base coating composition (for comparative example)

Base paint composition N o. B— 2 1

Manufacture of acrylic resin solution

Into a 1 L reaction vessel equipped with a thermometer, thermostat, stirrer, condenser and dripping device, charge 33 3 parts of toluene, mix under stirring in a nitrogen atmosphere, and rise to 100 ° C. Warm up. Next, “Mixture B — 6” having the following composition was added dropwise over 4 hours. After completion of the addition, the mixture was aged at 100 ° C. for 1 hour to obtain an acrylic resin solution having a nonvolatile content of 60%. The resulting acryl resin solution had a hydroxyl value of 86 mg KOH / g.

“Mixture B—6”

Methyl methacrylate 3 5 0 parts n-Ptyl acrylate 5 0 parts Methacrylic acid 2-hydroxetyl 1 0 0 parts 2, 2, -azobis (2-methyl ptyronitrile) 2 5 parts Manufacture of base coating composition No. B-2 1

16.7 parts of the acrylic resin solution obtained above (non-volatile content 100 parts), aluminum paste F.X 1 4 4 0 4 1.8 parts (non-volatile content 23 parts), high-conc black 3 parts (non-volatile material) 3 parts) and 29.2 parts of methylethylketone and mixed well with a stirrer to obtain a base coating composition No. B-21 with a nonvolatile content of 25%.

Manufacture of acrylic ester (b l) of saccharides or derivatives

Acrylic esters of sugars or their derivatives No B. 1

In a reaction vessel equipped with a distillation apparatus, a thermometer, and a stirrer, dex 卜 phosphorus (I) (glucose polymer having an average polymerization number of 4 and having an average of 14 hydroxyl groups per molecule) 80 parts, methyl isobutyl ketone 100 parts, 0.16 parts of methylhydroquinone, 5.9 parts of lithium hydroxide monohydrate and 50.6.2 parts of methyl acrylate were charged. Next, nitrogen was blown into the solution and heated to 90 ° C. with stirring, and methyl acrylate, methanol, and methyl isobutyl ketone were gradually distilled out of the system. Methyl acrylate and methyl isopropyl ketone, which decrease with distillation, were added to the reaction vessel. Next, the reaction was traced by quantifying the methanol in the reaction vessel and the distilled methanol by gas chromatography, and an average of 6.0 hydroxyl groups per molecule of the above dexterin (I) was acrylic acid. Cooled where esterified. Furthermore, the reaction solution is concentrated under reduced pressure, and ethyl acetate is added to the residue to have a nonvolatile content of 25%, a weight average molecular weight of 1,100, and an average of 6.0 acryloyl groups per molecule. An acrylate ester N o .B-1 solution was obtained.

<Production example B-4 4> Bester of sugar or its derivative No. B-2 Production Example B-41 In dextrin (I), an average of 10.0 hydroxyl groups out of an average of 14 hydroxyl groups per molecule Production Example B- 4 1 Except that the reaction was traced by quantifying the methanol and distilled methanol in the reaction vessel by gas chromatography until the reaction time was extended until the esterification was achieved. In the same manner, an acrylic acid ester No. B-2 solution having a weight average molecular weight of 1,400 and an average of 10.0 acryloyl groups per molecule was obtained.

Acrylic esters of sugars or their derivatives No. B-3

In Production Example B-41, the same as Production Example B-41 except that dextrin (II), which is a glucose polymer with an average polymerization number of 3 and has an average of 11 hydroxyl groups per molecule, is used. The methanol in the reaction vessel and the distilled methanol were used until an average of 6.0 hydroxyl groups out of an average of 11 hydroxyl groups per molecule of the dextrin (II) was converted to an acrylate ester. The reaction was traced by quantification by gas chromatography, and an acrylic acid ester No. B-3 solution having a weight average molecular weight of 950 and an average of 6.0 acryloyl groups per molecule was obtained. .

Acrylic esters of sugars or their derivatives N o. B-4

In Production Example B-41, Production Example B-41, except that dextrin (III), which is a glucose polymer with an average polymerization number of 6 and has an average of 20 hydroxyl groups per molecule, is used. Similarly, until an average of 6.0 hydroxyl groups out of an average of 20 hydroxyl groups per molecule of dextrin (III) is acrylated, The reaction was traced by quantifying the methanol in it and the distilled methanol by gas chromatography, and a carboxylic acid ester having a weight average molecular weight of 1,500 and an average of 6.0 acryloyl groups per molecule. A No. B-4 solution was obtained.

Acrylic esters of sugars or their derivatives N o. B-5

In Production Example B-41, the reaction was followed by using trehalose instead of dextrin (I) and quantifying the methanol in the reaction vessel and the distilled methanol by gas chromatography.

In the same manner as in Production Example B—41, except that an average of 6.0 hydroxyl groups per molecule of the above-mentioned rehalose was cooled, the weight average molecular weight was 7800 and per molecule. An acrylic ester No. B-5 solution having an average of 6.0 acryloyl groups was obtained.

Acrylic esters of sugars or their derivatives No. B-6

In Production Example B-41, sucrose was used instead of dextrin (I), and the reaction was traced by quantifying the methanol in the reaction vessel and the distilled methanol by gas chromatography. Except for cooling when 6.0 hydroxyl groups on average per molecule of acryloyl ester were converted to acrylic acid ester, the same as in Production Example B-41, the weight average molecular weight was 7 80 and the average was 6.0 per molecule. Acrylic acid ester N o .B-6 solution having an acryloyl group was obtained.

Active energy ray-curable compound N o. B— 1

Thermometer, thermostat, stirrer, reflux condenser and air blowing device Into a reaction vessel equipped with 8 8 parts of isophorone diisocyanate, 2 6 parts of hydroxetyl acrylate and 0.7 part of hydroquinone monomethyl ether, and blow air into the reaction vessel. However, after raising the temperature to 80 ° C. and maintaining that temperature for 5 hours, it was confirmed that substantially all of the hydroxyl groups of the added 2-hydroxyxetyl acrylate had reacted. 1 3 6 parts, butyl acetate 3 7 2 parts and dibutyl tin dilaurate 0.2 part were added and kept at 80 ° C., and the isocyanate group of isophorone diisocyanate was substantially completely reacted. After confirmation, the mixture was cooled to obtain an active energy linear curing compound No. B-1 having a nonvolatile content of 80%. The number average molecular weight of this resin was about 1,500.

Manufacturing Example B— 4 8>

Reactive polymer emulsifier N o. B— 1

Add 100 parts of propylene glycol monomethyl ether acetate to a four-necked flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and nitrogen inlet, and stir while introducing nitrogen gas. And heated to 120 ° C. Next, styrene 13.0 parts, n-butyl methacrylate 590 parts, 2—hydroxylshethyl methacrylate 8 5 parts, glycidyl methacrylate 5 parts, methyl methacrylate 40 parts, 2, 2'-azobis — 2 —Methylptyronitrile 20 part of the mixture was added dropwise from the dropping tank over 3 hours. After completion of the dropwise addition, the copolymer was obtained by maintaining at the same temperature for 0.5 hours, and in this, 20 parts of styrene, 45 parts of n_methyl methacrylate, 2-hydroxychetyl methacrylate A mixture of 15 parts, 60 parts of acrylic acid, 10 parts of methyl methacrylate, and 10 parts of t-butylperoxy-2-ethylhexanoe was added dropwise from a dropping tank over 1 hour. After completion of dropping, after maintaining at the same temperature for 0.5 hour, further propylene glycol monomethyl ether acetate 50 parts of a solution in which 10 parts of 1-butyl methoxyl-2-ethylhexanoe was dissolved in 40 parts of the solution was added dropwise over 30 minutes. Then it was aged for 1 hour. After cooling to 80 ° C., 50 parts of 2-acryloyloxychetyl isocyanate and 0.1 part of neostane U—100 (tin-based catalyst) were added and stirred for 2 hours. The solvent was distilled off until the nonvolatile content became 70% to obtain a reactive polymer emulsifier No. B-1 solution.

Production of active energy ray-curable aqueous coating composition No. B-1

Active energy ray-curable aqueous coating composition No. B— 1

The solvent was distilled off from the acrylic ester No. B-1 solution obtained in Production Example B-41 to obtain a solution having a nonvolatile content of 70%. Darocur 1 1 7 3 (trade name, manufactured by Ciba 'Specialty' Chemicals Co., Ltd., 2-hydroxy-2-methyl 1-phenyl-propane) 1—one, photopolymerization initiator) 3 parts, and RMA—500 6 (trade name, manufactured by Nippon Emulsifier Co., Ltd., polyoxyethylene nonyl phenyl ether acrylate, nonionic reactive emulsifier) 6 parts While stirring, 20.4 parts of deionized water was gradually added to disperse in water. Further, 1 part of B YK-3 4 8 (trade name, manufactured by Bicchemi Co., Ltd., surface conditioner) was added to obtain an active energy ray-curable aqueous coating composition No. B-1 having a nonvolatile content of 30%. .

Active energy ray-curable water-based paint composition No. B— 2 to No. B— 3_

Except that the acrylic acid ester No. B-1 solution was changed to the acrylic acid ester No. B-2 to No. B_6 solution, according to the formulation in Table B-3, production example B-4 9 In the same manner, active energy one-line curable water-based coating compositions No. B-2 to No. B-6 having a nonvolatile content of 30% were obtained. Table B— 3

The numerical value in a mixing | blending shows a non volatile matter.

Active energy ray-curable water-based coating composition No. B— 7

The solvent was distilled off from the acrylic ester No. B-1 solution obtained in Production Example B_41 to obtain a solution having a nonvolatile content of 70%. To this solution, 12.9 parts (non-volatile content, 100 parts), Darocur 1 1 7 3 3 parts, and the reactive polymer emulsifier No. B-1 1 4. obtained in Production Example B-4 8 3 parts (10 parts of non-volatile content) was added, and 2 18.8 parts of deionized water was gradually added while stirring to disperse in water. Further, 1 part of B YK-3 4 8 was added to obtain an active energy ray-curable aqueous coating composition No. B-7 having a nonvolatile content of 30%.

Active energy ray-curable aqueous coating composition No. B— 8

Butyl acetate was added to the active energy ray-curable compound (b 3) No. B-1 obtained in Production Example B-47 to obtain a solution having a nonvolatile content of 70%. Darocur 1 1 7 3 3 parts and RMA — 5 0 6 6 parts are added to 1 2.29 parts (non-volatile content 1 100 parts) of this solution, and 2 1 0. 4 parts of deionized water are gradually added while stirring. In addition, an aqueous dispersion was obtained. Further, 1 part of BYK-3 4 8 was added to obtain a composition having a nonvolatile content of 30%. 30 parts of this composition and 30% of the active energy ray-curable aqueous coating composition having a non-volatile content of 30% obtained in Production Example B-49 were mixed and stirred to obtain a non-volatile content of 3 0% active energy ray-curable aqueous coating composition No. B-8 was obtained.

Active energy ray-curable coating composition No. B-9 (for comparative example)

Production example B-47 Active energy ray-curable compound (b 3) No. B-1 1 2 5 parts (non-volatile content 100 parts) and Irgacure 1 8 4 (trade name, Ciba · Specialty Chemicals, photopolymerization Initiator) 3 parts were added and dissolved, and then diluted to 30% non-volatile content with butyl acetate to obtain active energy ray-curable coating composition No. B-9.

Active energy ray-curable water-based paint composition No. B— 1 0 (for comparative example 1_

Butyl acetate was added to the active energy ray-curable compound (b 3) No. B-1 obtained in Production Example B-47 to obtain a solution having a nonvolatile content of 70%. Darocur 1 1 7 3 3 parts and RMA — 5 0 6 6 parts are added to 1 2.29 parts (non-volatile content 1 100 parts) of this solution, and 2 1 0. 4 parts of deionized water are gradually added while stirring. In addition, an aqueous dispersion was obtained. Further, 1 part of BYK-3 4 8 was added to obtain an active energy ray-curable aqueous coating composition No. B-10 having a nonvolatile content of 30%.

Example B— 1>

Formation of coating film

A multilayer coating film No. B-1 was prepared by the following steps.

Step 1: A polycarbonate resin plate (trade name, Dialite P, manufactured by Mitsubishi Rayon Co., Ltd., 70 mmX 150 mmX 2 mm) was used as an object to be coated. Apply the starch-based paint composition No. B-1 obtained in Production Example B- 20 to the coating material degreased with isopropanol by air spray so that the dry coating film is 8 m. The base coating film was prepared by heating and drying at 60 ° C. for 15 minutes.

Step 2: On the base coating film prepared in Step 1, the active energy ray-curable aqueous coating composition N 0. B— 1 obtained in Production Example B—4 9 is air sprayed to form a dry coating 1 2 im And dried by heating at 60 for 5 minutes.

Process 3: Apply the high-pressure mercury lamp to the coating film dried in Process 2, By ultraviolet irradiation of OOOJ / m ^2, it was created Fukusonurimaku N o. B- 1.

About the coating board which has the obtained multilayer coating film, it used for the following test. The test results are shown in Table B-4.

A multilayer coating film No. B according to the same procedure as Example B-1 except that each starch-based base coating composition and each active energy ray-curable aqueous coating composition shown in Table B-4 are used. — 2 to B— 2 9 were created. About the coating board which has the obtained multilayer coating film, it used for the following test. The test results are shown in Table B-4.

Table B— 4

Table B—4 (continued)

Table B-5 (starch-based) base coating composition, active energy ray curable (aqueous) Multi-layer coating film by the same process as Example B-1 except that the coating composition is used. 3 0 to B— 3 3 were created. The obtained coated plate having a multilayer coating film was subjected to the following test. The test results are shown in Table B-5.

Table B— 5

[Test method]

(Note B—7) Contains bio-derived ingredients

Each (starch-based) base coating composition and active energy ray-curable (aqueous) coating composition were evaluated for the presence or absence of blending of biologically derived components according to the following criteria.

Y e s (Y): Starch-based resin, or carboxylic acid ester (bl) (biological component) of saccharide or its derivative is included in the paint.

N o (N): Starch-based resin or acrylate or derivative of saccharide or its derivative (bl) (component derived from living body) is not included in paint.

(Note B_8) Finishability, (Note B—9) Pencil hardness, (Note B—10) Scratch resistance (1) and (Note B—1 1) Scratch resistance (2)

The tests and evaluation methods for finish, pencil hardness, scratch resistance (1) and scratch resistance (2) are (Note A—1), (Note A—2), (Note A_3) and (Note), respectively. Note A— It is the same as the method described in 4).

(Note B— 1 2) Adhesion to substrate and adhesion to interlayer

In accordance with JISK 5 6 0 0-5-6 (1 9 9 0), make 100 mm l mm x l mm gobangs on each multi-layer coating film, and apply adhesive tape on the surface, and quickly After peeling, the number of remaining gobang eyes was evaluated. The case where the peeled portion was between the object to be coated and the base coating film was evaluated as having not remained in the substrate adhesion. An evaluation was made on the assumption that the peeled portion remained between the layers of the multilayer coating film remained in the substrate adhesion but did not remain in the interlayer adhesion.

G o o d (G) ： Remaining number Total number = 1 0 0/1 0 0

F air (F): Remaining number Z Total number of pieces = 90 to 99/9 pieces / ^ 1 0 0 pieces P oor (P): Remaining number of pieces = Total number of pieces = 8 9 pieces or less / 100 pieces (Note B— 1 3) Weather resistance

The weather resistance test and evaluation method are the same as those described in (Note A-5).

(Note B— 1 4) Alkali resistance

Drop 0.5 mL of 1% aqueous sodium hydroxide on each multilayer coating surface and leave it in an atmosphere at a temperature of 20 and a relative humidity of 65% for 24 hours, and then wipe the coated surface with gauze. The appearance was visually evaluated.

G o o d (G): There is no abnormality on the coating surface.

F a i r (F): Discoloration (whitening) of the coating surface is observed.

P o o r (P): Discoloration (whitening) of the coating surface is remarkable.

(Note B— 1 5) Solvent resistance

The test and evaluation method for solvent resistance is the same as the method described in (Note A-6). Industrial applicability

The active energy ray-curable coating composition of the present invention has a low total CO ₂ emission related to the product life cycle and can reduce environmental pollution, as well as finish, pencil hardness, scratch resistance, weather resistance and resistance. Since it is possible to form a coating film having excellent solvent and photocuring properties, it is industrially useful.

Furthermore, the coating film forming method of the present invention reduces the amount of petroleum resources used, reduces the total carbon dioxide emissions related to the product life cycle, reduces environmental pollution, and also provides finish, pencil hardness, and scratch resistance. It is possible to obtain a multi-layer coating film having excellent interlayer adhesion, weather resistance, alkali resistance and solvent resistance, and since an aqueous coating composition is used as a part of the coating composition to be used, Since the amount used can be reduced, Industrially useful

Claims

1. Acrylic acid ester of an acyclic oligosaccharide or a derivative thereof having a weight average molecular weight of 400 to 2,000 and an average of 3.0 to 1 2.0 acryloyl groups per molecule An active energy ray-curable coating composition comprising (a 1) and a photopolymerization initiator (a 2).

2. The active energy ray-curable coating composition according to claim 1, wherein the acyclic oligosaccharide or a derivative thereof is dextrin or modified dextrin.

3. The active energy ray-curable coating composition according to claim 1, wherein the acyclic oligosaccharide or a derivative enclosure thereof is sucrose or trehalose.

4. The active energy ray-curable coating composition according to claim 1, further comprising an active energy ray-curable compound (a 3).

5. The active energy ray-curable coating composition according to claim 1, wherein the acrylic ester (a 1) of an acyclic oligosaccharide or a derivative thereof is an aqueous dispersion.

6. A coated article obtained by coating the active energy ray-curable coating composition according to claim 1.

7. A step of coating a starch-based base coating composition containing a starch-based resin and a color pigment and / or a luster pigment on an object to form a base coating film;

Coating an active energy one-line curable aqueous coating composition containing an aqueous dispersion of acrylic acid ester (b 1) of a saccharide or a derivative thereof and a photopolymerization initiator (b 2) on the base coating film; And

A step of irradiating active energy rays, A method of forming a coating film characterized by

8. Acrylic ester (bl) of a saccharide or a derivative thereof has a weight average molecular weight of 400 to 2,000 and an average of 3.0 to 12.0 acryloyl groups per molecule. The method for forming a coating film according to claim 7.

9. The method for forming a coating film according to claim 7, wherein the saccharide or a derivative thereof is an acyclic oligosaccharide or a derivative thereof.

10. The method for forming a coating film according to claim 9, wherein the acyclic oligosaccharide or a derivative thereof is dextrin or modified dextrin.

1 1. The coating film forming method according to claim 9, wherein the acyclic oligosaccharide or a derivative thereof is sucrose or trehalose.

1 2. A coated article obtained by the coating film forming method according to claim 7.