JP2007284597A - Coating composition and glass container - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy beam-curable type water-based coating composition having small environmental load because of water-based composition and forming a coating film excellent in alkaline resistance and adhesiveness on the surface of glass container by active energy beam curing. <P>SOLUTION: The coating composition comprises (A) an active energy beam-curable composition, (B) a nonionic surfactant, (C) an alkoxysilane compound and water as essential components. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a coating composition. More specifically, the present invention relates to a coating composition that forms a coating film excellent in alkali-cleaning resistance on a glass container.

  Glass containers coated on the surface are widely used as containers for foods, soft drinks, alcoholic beverages, cosmetics and the like for the purpose of preventing the transmission of ultraviolet rays and enhancing the design to give a high-class feeling. The coating agent or coating method for the glass container is, for example, selected from the group consisting of two or more fluoroacryloyl groups, methacryloyl groups, and acryloyl groups in the molecule in a glass container that has been previously treated with a silane coupling agent. A method of applying a curable composition containing at least one curable compound having an acryloyl group and irradiating with an active energy ray, and a curable composition obtained by adding a silane coupling agent to the curable compound A method is known in which an object is applied to a glass container and cured by irradiation with an active energy ray (see, for example, Patent Document 1).

  However, in the above method, since the viscosity of the active energy ray-curable resin is high, it is necessary to dilute with a solvent or with a large amount of monomer. In the case of diluting with the above monomer, there is a problem that a product satisfying the alkali cleaning resistance and impact resistance cannot be obtained.

  Furthermore, as a thing which does not use a solvent etc., aqueous | water-based active energy ray hardening-type resin, such as active energy ray hardening-type polyurethane aqueous resin dispersion liquid, may be used. However, since the coating film obtained by this method is inferior in alkali resistance, when the glass container is immersed in a cleaning solution such as an aqueous solution of caustic soda in the alkali cleaning step, the coating film is whitened or the film is peeled off from the glass container. There was a big problem in practical use.

JP-A-1-201047

  An object of the present invention is to provide an active energy ray-curable coating composition that is water-based and has a low environmental impact, and that forms a coating film with excellent alkali resistance on a glass container.

  The inventors of the present invention have a conventional aqueous active energy ray-curable resin such as an active energy ray-curable polyurethane aqueous resin dispersion having an ionic functional group such as an amino group or a carboxyl group in the molecule. It is dispersed in water by neutralization, and it is thought that the alkali resistance is reduced due to this, and as a result of intensive studies, it uses a water-based active energy ray curable resin dispersed with a nonionic emulsifier It has been found that the alkali resistance of the coating film can be greatly improved by doing so. Furthermore, it discovered that the adhesiveness to glass of the water-system active energy ray hardening-type resin disperse | distributed with the nonionic surfactant improved by using together an alkoxysilane compound, and completed this invention.

  That is, the present invention provides a coating composition comprising an active energy ray-curable compound (A), a nonionic surfactant (B), an alkoxysilane compound (C) and water as essential components. provide.

  Furthermore, the present invention provides the coating composition, wherein the active energy ray-curable compound (A) is dispersed in water with the nonionic surfactant (B).

  Furthermore, in the present invention, the active energy ray-curable compound (A) is selected from the group consisting of a polyvalent (meth) acrylate, a polyester (meth) acrylate, an epoxy-modified (meth) acrylate, and a polyurethane (meth) acrylate. A coating composition as described above is provided which is at least one compound.

  Furthermore, this invention provides the said coating composition containing 1-35 weight part of said alkoxysilane compounds (C) with respect to 100 weight part of said active energy ray hardening-type compounds (A).

  Furthermore, this invention provides the glass container formed by apply | coating the said coating composition and hardening | curing with an active energy ray.

  According to the present invention, a coating film excellent in alkali detergency can be obtained using an aqueous coating composition. Since the present invention has higher safety than conventional methods, and is excellent in environmental suitability and economic efficiency, it can be practically widely used for glass containers such as alcoholic beverages and soft drinks.

Hereinafter, the present invention will be described more specifically.
The coating composition of the present invention comprises an active energy ray-curable compound (hereinafter referred to as component (A)), a nonionic surfactant (hereinafter referred to as component (B)), an alkoxysilane compound (hereinafter referred to as component (C). )) And water as essential components.

  The active energy ray-curable resin used in the component (A) of the present invention is a resin that is cured by irradiation with active energy rays such as visible light and ultraviolet rays to give a normal resin used for plastic coating of glass containers. If it is, it will not specifically limit. As the component (A), for example, a reactive compound mainly having two or more (meth) acryloyl groups in the molecule and a monofunctional monomer having one (meth) acryloyl group in the molecule as necessary (dilution) And those containing a monomer). In the present specification, “(meth) acryl” means “acryl” and / or “methacryl”.

  Examples of the component (A) include (1) polyhydric (meth) acrylate in which two or more (meth) acrylic acids are bonded to polyhydric alcohol, and (2) reaction of polyhydric alcohol and polybasic acid. Polyester (meth) acrylate in which two or more (meth) acrylic acids are bonded to the polyester polyol, and (3) the epoxy group of an epoxy compound having at least two epoxy groups in the molecule is esterified with (meth) acrylic acid. Examples include epoxy-modified (meth) acrylates having (meth) acryloyl groups as functional groups, and (4) polyurethane (meth) acrylates obtained by reacting polyvalent isocyanate compounds with hydroxyl group-containing (meth) acrylates. Among these, from the viewpoint of the strength of the cured resin film, polyvalent (meth) acrylate, epoxy-modified (meth) acrylate and polyurethane (meth) acrylate are preferably used.

  Examples of the polyvalent (meth) acrylate include diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and bisphenol. A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like can be mentioned, but are not limited thereto. These are also available as commercial products, and examples thereof include “DPGDA”, “TPGDA”, “PETIA”, “TMPEOTA”, “DPHA”, etc. manufactured by Cytec Surface Specialties.

  Examples of the polyester (meth) acrylate include phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid as polybasic acids. Aliphatic dicarboxylic acids such as 1,2-hexahydrophthalic acid, 1,3-hexahydrophthalic acid, 1,4-hexahydrophthalic acid, perhydronaphthalenedicarboxylic acid and the like, fumaric acid, Unsaturated dicarboxylic acids such as maleic acid and itaconic acid, unsaturated alicyclic dicarboxylic acids such as tetrahydrophthalic acid and cyclobutene dicarboxylic acid, oxyacids such as p-hydroxyethyloxybenzoic acid and ε-caprolactone, and polyhydric alcohols As ethylene glycol, propylene glycol, 1,3-propane All, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,3-propanediol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1, 3-pentanediol, 1,4-cyclohexanedimethanol, spiroglycol, 1,4-phenylene glycol, ethylene oxide adduct of 1,4-phenylene glycol, ethylene oxide adduct and propylene oxide adduct of bisphenol A, hydrogenation The polyester polyol synthesized by the condensation half-reaction of bisphenol A ethylene oxide adduct and propylene oxide adduct, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. Examples include those obtained by reacting phosphoric acid. These are also available as commercial products, for example, “Ebecryl 657”, “Ebecryl 800”, “Ebecryl 870” manufactured by Cytec Surface Specialties.

  Examples of the epoxy-modified (meth) acrylate include bisphenol A epoxy-modified (meth) acrylate, glycerol diglycidyl ether-modified (meth) acrylate, neopentyl glycol diglycidyl ether-modified (meth) acrylate, and ethylene glycol diglycidyl ether-modified ( Examples thereof include, but are not limited to, (meth) acrylate. These are also available as commercial products, for example, “Ebecryl 3700”, “Ebecryl 3708”, “Ebecryl 600” manufactured by Cytec Surface Specialties, and the like.

  The polyurethane (meth) acrylate is obtained by a reaction between a polyisocyanate compound and a (meth) acrylic monomer having active hydrogen.

  Examples of the polyisocyanate compound used include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dibenzyl diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexamethylene Of these diisocyanate compounds, diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Divalent compounds such as diisocyanate compounds obtained by hydrogenating aromatic isocyanates (for example, diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate), triphenylmethane triisocyanate, and dimethylenetriphenyl triisocyanate. Or the isocyanate group containing compounds, such as a trivalent diisocyanate compound or a polyisocyanate compound, and the multimerization polyisocyanate compound obtained by multiplying these, are mentioned.

  Furthermore, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 1,4-butanediol, 1,2 before reacting diisocyanate and acrylate for the purpose of adjusting molecular weight and molecular flexibility. , 6-hexanediol, 3-methyl-1,5-pentanediol, ethylene oxide / propylene oxide of bisphenyl A, polyester polyol having two or more hydroxyl groups in one molecule, oxyethylene / oxypropylene copolymer, etc. The reaction product of a known general-purpose product and diisocyanate can be used.

  A polyester polyol having two or more hydroxyl groups in one molecule can be obtained by an esterification reaction of a polycarboxylic acid and a polyhydric alcohol. The polyvalent carboxylic acid is not particularly limited, but adipic acid, sebacic acid, succinic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, fumaric acid, maleic acid, Examples include maleic anhydride, itaconic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, and the like. Further, the polyhydric alcohol is not particularly limited, but ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl 1,5- Examples thereof include pentanediol, bisphenol A ethylene oxide or propylene oxide adduct, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, dimethylolpropionic acid, dimethylolbutanoic acid, and the like.

  The polyisocyanate compound may be limited in kind, or two or more kinds of polyisocyanate compounds may be used in combination.

  Examples of the (meth) acrylic monomer having active hydrogen include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, 2 -Hydroxy-3-methoxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) acrylamide and the like. These lactone adducts (for example, “Placcel FA” or “Placcel FM” series manufactured by Daicel Chemical Industries, Ltd.) can also be used.

  The polyurethane (meth) acrylate is also available as a commercial product, and examples thereof include “Ebecryl 230”, “Ebecryl 8402”, “Ebecryl 4858”, “Ebecryl 1290” manufactured by Cytec Surface Specialties.

  As the nonionic surfactant used in the component (B) of the present invention, known nonionic surfactants such as sugar ester type, alcohol type and alkylphenol type can be used. For example, polyoxyethylene Examples include alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene acyl ester, sorbitan fatty acid ester, glycerol fatty acid ester and the like. These nonionic surfactants may be used alone or in admixture of two or more.

  The amount of component (B) is preferably 0.1 to 25 parts by weight, more preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the solid content of the active energy ray-curable compound (component (A)). Used in part range. If the amount is less than 0.1 parts by weight, it is difficult to obtain an emulsion having excellent storage stability. Even if it is used in an amount of more than 25 parts by weight, the storage stability of the emulsion is not improved so much. This is not preferable because the water resistance of the coating film and the adhesion to the substrate are lowered.

  In the present invention, an active energy ray-curable compound (component (A)) dispersed in water using a nonionic surfactant (component (B)) is used. A typical emulsification method of this dispersion is a method in which a nonionic surfactant is mixed in water and an active energy ray-curable compound is gradually added to the mixture with stirring. In addition, when the viscosity of an active energy ray hardening-type compound is high, it is preferable to emulsify, after heating to about 50-100 degreeC and reducing a viscosity.

  As described above, the coating composition of the present invention is characterized in that the component (A) is dispersed in water by a nonionic emulsifier, not by neutralization of ionic functional groups. Thereby, the alkali resistance of the composition of the present invention is dramatically improved while maintaining water dispersibility. In the case of a type that has an ionic functional group in the molecule and is dispersed in water by neutralizing these with an ionic surfactant such as an anionic surfactant or a cationic surfactant, Since it swells or elutes into water, it is considered that the alkali resistance of the coating film decreases.

  The alkoxysilane compound used as the component (C) of the present invention is not particularly limited, but (meth) acryloylalkoxysilane accompanied by a reaction during active energy ray curing is preferable. Examples of such alkoxysilane compounds include γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- ( (Meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) ) Acryloxypropyldimethylethoxysilane, γ- (meth) acryloxypropyltrichlorosilane, γ- (meth) acryloxypropylmethyldichlorosilane, γ- (meth) acryloxypropyldimethylchlorosilane, γ- (meth) acryloxypropyl Tripro Oxysilane, γ- (meth) acryloxypropylmethyldipropoxyoxysilane, γ- (meth) acryloxypropyltributoxysilane, γ- (meth) acryloxybutyltrimethoxysilane, γ- (meth) acryloxypentyltrimethoxy Silane, γ- (meth) acryloxyhexyltrimethoxysilane, γ- (meth) acryloxyhexyltriethoxysilane, γ- (meth) acryloxyoctyltrimethoxysilane, γ- (meth) acryloxydecyltrimethoxysilane, γ- (meth) acryloxydodecyltrimethoxysilane, γ- (meth) acryloxyoctadecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripyropoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxy Examples include silane, vinylmethyldipropoxysilane, and the like.

  The compounding amount of the component (C) of the present invention is preferably 1 to 35 parts by weight, more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the solid content of the active energy ray-curable compound (component (A)). is there. If it is less than 1 part by weight, sufficient adhesion to glass may not be obtained, and if it exceeds 35 parts by weight, storage stability may be reduced.

  The component (C) of the present invention plays a role of improving the adhesion of the active energy ray-curable compound (component (A)) to glass.

  The coating composition of the present invention is an aqueous composition in which the above components (A) to (C) are dispersed in water. By using an aqueous system, the environmental load is small, and the viscosity can be controlled to an appropriate viscosity, so that workability such as coating properties is improved. Although the water used for this invention is not specifically limited, Purified water, such as distilled water and ion-exchange water, is preferable. In the coating composition of the present invention, the water content is preferably 80 to 20% by weight, more preferably 70 to 30% by weight.

  The coating composition of the present invention is used by coating an article to be coated and curing the active energy ray to form a cured layer (coating layer). The object to be coated is a glass container from the viewpoint of adhesion. Examples of the glass container include, but are not limited to, glass bottles for soft drinks, alcoholic beverages, medicines, seasonings and the like, glass tableware such as cups and dishes, and vases.

  The coating method used when coating the coating composition of the present invention on the object to be coated varies depending on the object to be coated, and is not particularly limited. For example, spin coating, brush coating, spray coating (spraying), immersion Known methods such as a method (dip coating method), a blade coating method, a roll coating method, ink jet printing, gravure printing, screen printing, flexographic printing, bar coating method, and die coating method can be used. Of these, spray coating, dipping, and the like are preferably used when coating a glass container. The coating film thickness is usually in the range of 1 to 50 μm, but it is preferably in the range of 3 to 25 μm in view of economic efficiency, film properties and the like.

  The curing method for the coating composition of the present invention is based on irradiation with active energy rays from the viewpoints of workability, productivity, and a wide range of applicable objects. Crosslinking and curing according to the present invention can be performed by irradiating active energy rays after evaporating a part or all of water as a dispersion medium. Visible light, infrared rays, ultraviolet rays, X-rays, α-rays, β-rays, γ-rays, electron beams, and the like can be used as the active energy rays to be irradiated. Among these, visible light and ultraviolet light are preferably used from the viewpoint of industrial properties such as safety and reaction efficiency. As an active energy ray irradiation device, for example, a xenon lamp, a low-pressure, medium-pressure or high-pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, or a tungsten lamp can be used.

  By curing the resin in the glass container coated with the composition of the present invention by the above method, a frosted glass container excellent in alkali resistance or further excellent in impact resistance can be obtained.

  When the cross-linking means is ionizing radiation or electron beam, it cross-links quickly without adding a polymerization initiator, but when the cross-linking means is ultraviolet light, the coating composition of the present invention contains: Usually, a photopolymerization initiator is used. Examples of the photopolymerization initiator include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-acetophenone, 2,2- Acetophenones such as diethoxy-2-acetophenone, 1,1-dichloroacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1-chloroanthraquinone, anthraquinones such as 2-amylanthraquinone, 2, Thioxanthones such as 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 1-chlorothioxanthone, 2,4-diisopropylpropylthioxanthone, acetophenone dimethyl ketal, benzi There are ketals such as dimethyl ketal, benzophenones such as benzophenone, and xanthones, and the photopolymerization initiator is one or two of known and commonly used photopolymerization accelerators such as benzoic acid type or tertiary amine type. A combination of the above and conventional methods can also be used. The amount of the photopolymerization initiator is preferably 0.001 to 20% by weight, more preferably 0.1 to 5% by weight, based on the coating composition.

  If necessary, an ultraviolet absorber may be added to the coating composition of the present invention for the purpose of imparting an ultraviolet absorption effect to the coating film. As the ultraviolet absorber, those having good compatibility with the resin are preferable. For example, 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2- Benzophenone ultraviolet absorbers such as hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone; 2- (2-hydroxy-5-methylphenyl) Benzotriazole, 2- (2-hydroxy-3-t-butyl-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2- Hydroxy-5-t-octylphenyl) benzoto Benzotriazole ultraviolet absorbers such as azole and 2- (2-hydroxy-3,5-di-t-amylphenyl) benzotriazole; 2,4-di-t-butylphenyl-3,5-di-t- A benzoate-based ultraviolet absorber such as butyl-4-hydroxybenzoate; a salicylic acid-based ultraviolet absorber; a cyanoacrylate-based ultraviolet absorber or the like may be selected as necessary.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the examples. In addition, the compound used in the Example is as follows.

<Component A>
DPHA: manufactured by Cytec Surface Specialties, dipentaerythritol hexaacrylate, trade name “DPHA”
EB1290: Cytec Surface Specialties, urethane acrylate, trade name “Ebecry 1290”
EB8402: Cytec Surface Specialties, urethane acrylate, trade name “Ebecryl 8402”
EB3700: Cytec Surface Specialties, epoxy acrylate, trade name “Ebecryl 3700”
<Active energy ray-curable compound other than Component A>
Ucecoat 7773: manufactured by Cytec Surface Specialties, carboxyl group-containing polyurethane acrylate aqueous dispersion, trade name “Ucecoat 7773”
<Component B>
Emulgen 935: manufactured by Kao Atlas Co., Ltd., polyoxyethylene nonyl phenyl ether nonionic surfactant, trade name “Emulgen 935”, HLB = 17.5
<Component C>
A-174: GE Toshiba Silicone Co., Ltd., γ-methacryloxypropyltrimethoxysilane, trade name “A-174”
<Others (photopolymerization initiator)>
DAROCUR1173: manufactured by Ciba Specialty Chemicals Co., Ltd., 2-hydroxy-2-methyl-1-phenyl-propan-1-one, trade name “DAROCUR 1173”
Irgacure 2959: manufactured by Ciba Specialty Chemicals Co., Ltd., 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, trade name “Irgacure 2959”

  The measurement methods and evaluation methods used in the examples are as follows.

(1) Alkali resistance A glass container with a coating layer obtained in Examples and Comparative Examples was used as a sample.
The glass container was immersed in a 2.5% NaOH aqueous solution at 60 ° C. for 15 minutes, and the peeling state of the coating layer was observed. A coating layer with no whitening and peeling is judged as having good alkali resistance (○), a portion with peeling is insufficient (△), and a whitening and peeling being judged as poor alkali resistance (×) did.

(2) Adhesiveness The glass container with a coating layer obtained in Examples and Comparative Examples was used as a sample.
In accordance with JIS K 5600, a cellophane tape peeling test (without cross-cutting) is performed. When peeling is not observed, adhesion is good (◯), and when partial peeling is seen, adhesion is insufficient (Δ), When peeling was seen on the entire surface, it was judged as poor adhesion (x).

(3) Stability after 1 day After the coating compositions (aqueous dispersions) obtained in Examples and Comparative Examples were allowed to stand for 1 day, the dispersion state was visually observed. If no sedimentation or aggregation is observed, the stability is good (○). If the aggregation is slightly observed, the stability is insufficient (△). If the aggregation or precipitation is observed, the stability is poor (x). did.

(4) Appearance of coating film The glass container with a coating layer obtained in Examples and Comparative Examples is visually observed. If the coating film is clear and free of aggregates, good appearance (◯), aggregates, etc. are observed. In this case, it was determined that the appearance was poor (x).

(5) Viscosity The viscosity was measured at 25 ° C. using an E-type viscometer.

  Below, the synthesis example of the emulsion of the active energy ray hardening-type compound used in the Example is shown. Table 1 shows the physical properties of the emulsions obtained in Synthesis Examples 1 to 4.

Synthesis example 1
In a 300 ml beaker, 75 g of dipentaerythritol hexaacrylate (“DPHA” manufactured by Cytec Surface Specialties) was added and stirred with a homomixer. While stirring, 16 g (active ingredient 8 g) of a 50% aqueous solution of a nonionic surfactant (“Emulgen 935” manufactured by Kao Atlas Co., Ltd.) was added. After thoroughly stirring, 42 g of deionized water was gradually added to obtain an emulsion having a nonvolatile content (component (A) + component (B)) of about 60%. The viscosity of the obtained aqueous dispersion was 95 mPa · s at 25 ° C.

Synthesis Examples 2-4
As shown in Table 1, an active energy ray-curable compound was changed, and an emulsion was obtained in the same manner as in Synthesis Example 1. The results are shown in Table 1.

  Below, as an Example and a comparative example, the coating composition of this invention, the coating composition other than this invention, and the manufacture example of the glass container with the coating layer which apply | coated and hardened this to the glass container are shown. Table 2 shows the blending amount of each component and the physical properties of the coating composition (including the cured coating layer) in each of the examples and comparative examples.

Example 1
20 parts by weight of γ-methacryloxypropyltrimethoxysilane (“A-174” manufactured by GE Toshiba Silicones Co., Ltd.), 2-hydroxy-2-methyl-1-based on 100 parts by weight of the emulsion obtained in Synthesis Example 1 4 parts by weight of phenyl-propan-1-one (“DAROCUR 1173” manufactured by Ciba Specialty Chemicals), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1- 1 part by weight of propan-1-one (“Irgacure 2959” manufactured by Ciba Specialty Chemicals Co., Ltd.) was added and mixed by stirring to obtain a coating composition of the present invention.
A glass container washed with an alkaline aqueous solution was immersed in the coating composition, and then heated and dried at 80 ° C. for 15 minutes. Next, the coating film was cured by irradiating ultraviolet rays having an energy amount of 624 mJ / cm ² twice to obtain a glass container (a glass container with a coating layer) having a coating layer.
As shown in Table 2, the glass container coated with the coating composition thus obtained was excellent in alkali resistance without whitening of the coating layer and peeling from the glass container even after being immersed in NaOH for 15 minutes. there were. Moreover, it was excellent also in adhesiveness.

Example 2
The coating composition of the present invention was carried out in the same manner as in Example 1 except that the amount of γ-methacryloxypropyltrimethoxysilane (“A-174” manufactured by GE Toshiba Silicone Co., Ltd.) was 1 part by weight. Got. Moreover, it carried out similarly to Example 1, and obtained the glass container with a coating layer.
As shown in Table 2, the glass container coated with the obtained coating composition was excellent in alkali resistance and adhesion.

Examples 3-5
A coating composition of the present invention and a glass container with a coating layer were obtained in the same manner as in Example 1 except that the emulsions obtained in Synthesis Example 2, Synthesis Example 3, and Synthesis Example 4 were used as emulsions. It was.
As shown in Table 2, the glass container coated with the obtained coating composition was excellent in alkali resistance and adhesion.

Comparative Example 1
For coating, in the same manner as in Example 1, except that the emulsion of Synthesis Example 1 was used instead of the active energy ray-curable urethane dispersion (Cytec Surface Specialties "Ucecoat 7773") instead of the emulsion of Synthesis Example 1. A composition was obtained.
A glass container washed with an alkaline aqueous solution was immersed in the composition, and then heated and dried at 80 ° C. for 15 minutes. Next, the coating film was cured by irradiating twice with ultraviolet rays having an energy amount of 624 mJ / cm ² to obtain a coated glass container. Moreover, it carried out similarly to Example 1, and obtained the glass container with a coating layer.
As shown in Table 2, the glass container coated with the obtained coating composition was inferior in alkali resistance because whitening and peeling from the glass container were observed after immersion in NaOH for 15 minutes. Also, the adhesion was insufficient.

Comparative Example 2
A coating composition was obtained in the same manner as in Example 1, except that γ-methacryloxypropyltrimethoxysilane (“A-174” manufactured by GE Toshiba Silicone Co., Ltd.) was not used.
A glass container washed with an alkaline aqueous solution was immersed in the composition, and then heated and dried at 80 ° C. for 15 minutes. Next, the coating film was cured by irradiating twice with ultraviolet rays having an energy amount of 624 mJ / cm ² to obtain a coated glass container. Moreover, it carried out similarly to Example 1, and obtained the glass container with a coating layer.
As shown in Table 2, the glass container coated with the obtained coating composition was inferior in alkali resistance because whitening and peeling from the glass container were observed after immersion in NaOH for 15 minutes. Also, the adhesion was insufficient.

Claims (5)

  A coating composition comprising an active energy ray-curable compound (A), a nonionic surfactant (B), an alkoxysilane compound (C) and water as essential components.   The coating composition according to claim 1, wherein the active energy ray-curable compound (A) is dispersed in water with the nonionic surfactant (B).   The active energy ray-curable compound (A) is at least one compound selected from the group consisting of polyvalent (meth) acrylates, polyester (meth) acrylates, epoxy-modified (meth) acrylates and polyurethane (meth) acrylates. The coating composition according to claim 1 or 2.   The coating composition according to any one of claims 1 to 3, comprising 1-35 parts by weight of the alkoxysilane compound (C) with respect to 100 parts by weight of the active energy ray-curable compound (A).   The glass container formed by apply | coating the coating composition in any one of Claims 1-4, and hardening | curing with an active energy ray.