JP2001279185A - Glass container covering material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a covering material for beer bottles, or the like, which excels in flaw opacifying properties, water resistance, alkali peelability, light blocking properties, and label adhesion, and a glass container covered with the covering material. SOLUTION: This glass container covering material comprises a resin composition having film-formability and a pigment for blocking rays having a wavelength of 450-550 nm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating material for a glass container and a glass container coated with the coating material. More specifically, the present invention relates to a coating material for a glass container excellent in wound concealing property, alkali peeling property, water resistance, light shielding property and label adhesiveness, and a glass container coated with the coating material.

[0002]

2. Description of the Related Art A coating agent for glass containers, such as beer and soft drinks, requires the following properties: a wound concealing property capable of concealing scratches generated on the surface; washing with an aqueous alkali solution to reuse the glass container. Then, alkali peeling property that the coating material can be easily peeled off; water resistance that the coating material does not peel off from the glass container even when the coating material is immersed in water can be mentioned. As a coating material with these characteristics,
Silicone resin is used. In addition, a label is usually adhered to the glass container in order to display the contents, product name, and the like. Here, after the label is adhered to the surface of the glass container coated with the silicone resin via a casein adhesive, and then immersed in water together with the glass container, the label partially peels off the surface of the coating material, that is, the silicone resin Has a problem that the label adhesion is low. For this reason, the label must be adhered to the surface of the glass container and then coated with a silicone resin.

[0003] On the other hand, a brown glass container coated with a silicone resin is used for filling contents such as beer. However, when exposed to sunlight, the contents are deteriorated, resulting in a so-called "sun odor". It is known that the so-called odor is generated in beer. For this reason, the glass container coated with the silicone resin could not prevent this odor.

[0004]

Accordingly, the present inventors coated a glass container to which a label was adhered with a coating material comprising a silicone resin and a pigment which shields sunlight, and applied the colored silicone resin to the label. The problem that the label was colored because it was covered from above, making the label description difficult to read, was found. An object of the present invention is to have a wound concealing property, an alkali peeling property and a water resistance, a light shielding property for suppressing deterioration of contents by sunlight, and a label capable of adhering a label to a surface of a coating material. An object of the present invention is to provide a coating material for a glass container having label adhesiveness.

[0005]

Means for Solving the Problems As a result of intensive studies on the coating material for glass containers, the present inventors have found that a coating material comprising a resin composition having a specific film forming property and a pigment for shielding light of a specific wavelength. However, they have found that they have properties required for a glass container covering material such as scratch concealing properties, alkali peeling properties, and water resistance, and also have a light-shielding property and a high label adhesiveness, and have completed the present invention. That is, the present invention provides a coating material for a glass container, comprising a resin composition having a film-forming property and a pigment that blocks light having a wavelength of 450 to 550 nm, and a practical material obtained by coating the coating material. A glass container is provided.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
As the resin composition having a film forming property in the present invention, for example, a photocurable resin, a composition comprising a resin having a film forming property such as a synthetic resin emulsion and a silane coupling agent, such as a fluid before coating. It is a resin composition having a flaw concealing property, alkali peeling property, water resistance and label adhesiveness, which can form a continuous film after coating and curing.

The photocurable resin used as the resin having a film-forming property is usually a photocurable resin comprising (A) a photocurable oligomer and / or monomer and (B) a photopolymerization initiator. And the like.

The oligomer and / or monomer having photocurability of the component (A) include, for example, oligomers and / or monomers having at least one unsaturated carbon-carbon bond capable of photoradical polymerization, and Michael addition. Examples thereof include a combination of an oligomer having a double bond at a molecular terminal capable of being polymerized with a polythiol, and an alicyclic epoxy compound capable of performing cationic photopolymerization. Among them, it is preferable to use an oligomer and / or a monomer having at least one unsaturated carbon-carbon bond.

As the oligomer having an unsaturated carbon-carbon bond, an oligomer having at least one kind of unsaturated group selected from acryloyl, methacryloyl and vinyl groups is usually used. Specifically, urethane acrylates, urethane acrylates such as urethane methacrylate, epoxy acrylates, epoxy acrylates such as epoxy methacrylate, polyester acrylates, polyester acrylates such as polyester methacrylate, melamine acrylate, melamine acrylates such as melamine methacrylate, Acrylic resin acrylates, unsaturated polyesters and polyenes are exemplified.

As urethane acrylates, for example, those obtained by reacting an organic polyisocyanate, a polyol and a hydroxy acrylate compound, etc., are also obtained by reacting an organic polyisocyanate and a hydroxy acrylate compound. It may be something. Examples of epoxy acrylates include those obtained by reacting acrylic resin and / or methacrylic acid with an epoxy resin such as a bisphenol A epoxy resin and a novolak type epoxy resin. As polyester acrylates, for example,
Examples thereof include those obtained by reacting acrylic acid and / or methacrylic acid with a polyester polyol synthesized from a polyhydric alcohol and a polycarboxylic acid.
As melamine acrylates, for example, melamine,
Examples thereof include those obtained by subjecting melamine resin obtained by condensation polymerization of urea, benzogamine and the like with formalin and the like to a dealcoholation reaction with β-hydroxyethyl acrylate and the like, and the like. As acrylic resin acrylates, for example, carboxylic acid group, hydroxyl group, contained in acrylic resin,
Examples include those obtained by reacting acrylic acid and / or methacrylic acid with a functional group such as a glycidoxy group. Examples of unsaturated polyesters include those obtained by reacting a polyol with an α, β-unsaturated dicarboxylic acid such as fumaric acid and maleic anhydride. Examples of the polyenes include those obtained by reacting an organic polyisocyanate with allyl alcohol and / or vinyl alcohol.

On the other hand, the monomer having an unsaturated carbon-carbon bond is usually at least one kind of unsaturated group-containing monomer selected from monofunctional acrylic monomers, polyfunctional acrylic monomers and vinyl group-containing monomers. Monomers and the like are used.

As the monofunctional acrylic monomer, a compound containing one acrylate group or methacrylate group in the molecule is usually used, and specific examples thereof include isobornyl acrylate, isobornyl methacrylate, and dicycloalkyl methacrylate. Monomers having a ring structure such as pentenyl acrylate, dicyclopentenyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, phenyl acrylate, phenyl methacrylate, benzyl acrylate and benzyl methacrylate, and 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate , 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate,
-Hydroxybutyl methacrylate, 2-hydroxy-
Examples include monomers having a hydroxyl group such as 3-phenoxypropyl acrylate and 2-hydroxy-3-phenoxypropyl methacrylate. Further, monofunctional acrylic monomers in which the raw material alcohol or phenol in the above-mentioned monomers having a ring structure is modified with an alkylene oxide in advance can also be used.
Particularly, a modified product of alkylene oxide having 2 to 3 carbon atoms is preferable, and examples thereof include dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, phenyloxyethyl acrylate, and phenyloxyethyl acrylate.

As the polyfunctional acrylic monomers, compounds containing two or more acrylate groups or methacrylate groups in the molecule are usually used.
Examples of the acrylate group-containing compound include diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, neopentyl glycol hydroxypivalic acid diacrylate, caprolactone-modified neopentyl glycol hydroxypivalic acid diacrylate, and trimethylolpropane. Triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, tris [acryloxyethyl]
And isocyanate.

Examples of vinyl group-containing monomers include vinyl esters such as vinyl acetate, vinyl propionate and branched fatty acid vinyl; aromatic vinyls such as styrene, chlorostyrene, alkylstyrene, and divinylbenzene;
Nitrogen-containing vinyls such as N-vinylpyrrolidone and N-vinylcaprolactam.

As the component (A) of the present invention, the above-mentioned monomers and oligomers may be used alone or in combination. However, the viscosity, mechanical strength, It is preferable to use a mixture of a monomer and an oligomer from the viewpoint of adhesiveness and the like.

Examples of the photopolymerization initiator of the component (B) include carbonyl compounds, sulfur compounds, azo compounds, peroxides and the like. Among them, carbonyl compounds are preferred, and specific examples thereof include benzophenone, benzyl, Michler's ketone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, benzoin ethyl ether, diethoxyacetophenone, benzyldimethylketal,
-Hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholinopropan-1-one, and 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,
Examples thereof include carbonyl compounds that absorb ultraviolet light such as 3,5-triazine and carbonyl compounds that absorb visible light such as camphorquinone and 3-ketocoumarin. These may be used alone or in combination of two or more. If necessary, a photopolymerization initiation aid such as N, N-dimethylaminoacetophenone and pN, N-dimethylethyl benzoate or a photosensitizer may be used in combination.

In the film-forming resin composition of the present invention, examples of the synthetic resin emulsion used as the film-forming resin include vinyl acetate resin emulsion, vinyl chloride resin emulsion, and acrylic resin emulsion. And the like. Among them, an acrylic resin emulsion is preferable.

Examples of the acrylic resin emulsion include copolymer emulsions of α, β-unsaturated carboxylic acid and its derivatives, α, β-unsaturated carboxylic acid and / or
Or a copolymer emulsion of a derivative thereof and an unsaturated monomer.

Specific examples of α, β-unsaturated carboxylic acids and derivatives thereof include (meth) acrylic acid monomers such as acrylic acid and methacrylic acid; maleic acid, itaconic acid, citraconic acid, crotonic acid, fumaric acid and the like. α, β
-Unsaturated dicarboxylic acids; (meth) acrylic acid monomers,
α, β-unsaturated dicarboxylic acid or the like and an ester such as methyl group, ethyl group, allyl group or 2-ethylhexyl group; α, β-unsaturated dicarboxylic anhydride such as maleic anhydride, fumaric anhydride or trimellitic acid Things. Among them, (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate and ethylhexyl (meth) acrylate, and (meth) acrylate monomers are preferred.

Examples of the unsaturated monomer include olefin monomers such as ethylene, propylene, butadiene, propylene, and styrene, and vinyl group-containing monomers such as acrylonitrile, acrylamide, vinyl acetate, and vinyl chloride. Among them, ethylene, styrene and vinyl acetate are preferred.

As the acrylic resin emulsion,
An emulsion obtained by copolymerizing a (meth) acrylic acid monomer is preferable. The amount of the (meth) acrylic acid monomer used in the acrylic resin emulsion is usually about 0.1 to 50 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the solid content of the emulsion.
It is about parts by weight. If the amount of the (meth) acrylic acid monomer is more than 50 parts by weight, the water resistance of the obtained coating material tends to decrease, which is not preferable.

Specific examples of the acrylic resin emulsion include (meth) acrylic acid- (meth) acrylic acid ester copolymer emulsion, styrene- (meth) acrylic acid copolymer emulsion, and styrene- (meth) acrylic acid- (Meth) acrylic acid ester copolymer emulsion, ethylene-vinyl acetate- (meth) acrylic acid copolymer emulsion, ethylene-vinyl acetate- (meth) acrylic acid- (meth) acrylic acid ester copolymer emulsion, and the like. And (meth) acrylic acid-
(Meth) acrylic acid ester copolymer emulsion, styrene- (meth) acrylic acid copolymer emulsion, and styrene- (meth) acrylic acid- (meth) acrylic acid ester copolymer emulsion are preferable.

Examples of the silane coupling agent used in the resin composition having a film forming property of the present invention include amino group-containing alkoxysilane, vinyl group-containing alkoxysilane, methacryl group-containing alkoxysilane, and mercapto group-containing alkoxysilane. And silane coupling agents such as glycidoxy group-containing alkoxysilanes and their partial hydrolysates.

Examples of the silane coupling agent (C) used in combination with the photocurable resin include amino group-containing alkoxysilanes and partial hydrolysates thereof. Among them, the following general formula (1) R ₁ NH _{(CH 2) 3 SiX p (} OR
₂ ) _3-p (1) (wherein, X represents a monovalent hydrocarbon group which may be substituted with a halogen atom, R ₁ represents hydrogen or a β-aminoethyl group, and R ₂ has 1 to 4 carbon atoms. The amino group-containing alkoxysilane represented by the following formula (1) and / or p represents 0 or 1) and / or a partial hydrolyzate thereof are preferable because they provide a coating material having high water resistance.

X in the general formula (1) is, for example, a group having about 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, an octyl group, a decyl group and a dodecyl group. Alkyl group; alkenyl group such as vinyl group and allyl group; aryl group such as phenyl group, tolyl group and xylyl group; aralkyl group such as β-phenylethyl group and β-phenylpropyl group; γ-chloropropyl group; Fluorine such as 3,3-trifluoropropyl group,
Examples include a hydrocarbon group in which a halogen atom such as chlorine is substituted. Among them, a methyl group is preferred. Examples of R ₁ include a hydrogen atom and a β-aminomethyl group, with a hydrogen atom being preferred. Examples of R ₂ include an alkyl group having about 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group. Among them, a methyl group is preferable. In addition, p is 0 or 1, and 0 is particularly preferable.

Specific examples of the silane coupling agent (C) represented by the general formula (1) include N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane,
-Β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc. And / or partial hydrolysates thereof. Among them, γ-aminopropyltriethoxysilane and / or a partial hydrolyzate thereof are preferable. In addition, two or more amino group-containing alkoxysilanes or partial hydrolysates thereof may be used in combination as the silane coupling agent (C), and a silane coupling agent other than the amino group-containing alkoxysilane may be used as long as the performance is not impaired. You may use together.

Examples of the silane coupling agent used in combination with the synthetic resin emulsion include glycidoxy group-containing alkoxysilanes. Among them, the following general formula (2) (Wherein, Y is a monovalent hydrocarbon group which may be substituted with a halogen atom, R is an alkyl group having 1 to 4 carbon atoms, and q is 0 or 1). The contained alkoxysilane and / or its partial hydrolyzate is preferable because it gives a coating material having high water resistance.

As Y in the general formula (2), for example, alkyl having 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, decyl, dodecyl and the like can be used. Alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group, tolyl group and xylyl group; aralkyl groups such as β-phenylethyl group and β-phenylpropyl group; γ-chloropropyl group; Fluorine such as 3,3-trifluoropropyl group,
Examples include a hydrocarbon group in which a halogen atom such as chlorine is substituted. Among them, a methyl group is preferred. As R, for example, an alkyl group having about 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group is used, and among them, a methyl group is preferable. Q is 0 or 1,
Among them, 0 is preferable.

Specific examples of the glycidoxy group-containing alkoxysilane represented by the general formula (2) include γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane. Ethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyltrimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropyl Ethyltriethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropylmethyldiisopropoxysilane, γ-glycidoxypropyltriisopropoxysilane, etc. as well as, It is like those of the partial hydrolyzate, among others, .gamma.-glycidoxypropyltrimethoxysilane, and / or its partial hydrolyzate are preferred. Further, as the silane coupling agent represented by the general formula (2), two or more glycidoxy group-containing alkoxysilanes or partial hydrolysates thereof may be used in combination, and other than the glycidoxy group-containing alkoxysilane as long as the performance is not impaired. May be used in combination.

The resin composition having a film forming property is (A)
In the case of a composition comprising the photocurable resin comprising (A) and (B) and the silane coupling agent (C), the ratio thereof is usually 100 parts by weight of the total of the components (A) to (C). (A) about 99.4 to 75 parts by weight of the component,
The component (B) is about 0.5 to 20 parts by weight, and the component (C) is about 0.1 to 5 parts by weight. When the amount of the component (B) does not reach 0.5 part by weight, the mechanical properties of the coating material tend to decrease, and when the amount of the component (B) exceeds 20 parts by weight, the processability during coating decreases. Tend to. When the amount of the component (C) does not reach 0.5 parts by weight, the water resistance of the coating material and the adhesiveness between the coating material and the container tend to decrease.
If the component (C) is used in excess of parts by weight, the photocurable resin composition is repelled on the surface of the glass container, and the homogeneity of the film tends to decrease, and the mechanical properties of the coating material tend to decrease.

When the resin composition having film-forming properties is a composition comprising a synthetic resin emulsion and a silane coupling agent, the ratio thereof is usually 100 parts by weight of the solid content of the synthetic resin emulsion, The ring agent is about 1 to 20 parts by weight, preferably about 2 to 1 part.
It is about 5 parts by weight, particularly preferably about 3 to 12 parts by weight. If the ratio of the silane coupling agent does not reach 1 part by weight, the adhesiveness between the coating material and the glass container tends to decrease, which is not preferable. The composition is repelled and the uniformity of the film is lowered, and the storage stability of the composition tends to be lowered, which is not preferable.

The coating material of the present invention has a wavelength of 45 to prevent light from penetrating the glass container and altering the contents thereof.
It is obtained by blending a pigment that reduces the light transmittance of 0 to 550 nm. The amount of the pigment used is appropriately set in accordance with the degree of coloring of the glass container, the thickness of the coating material, and the extinction coefficient of the pigment. Usually, the light transmittance of 500 nm transmitted through the coated glass container is 5%. An amount that shields light to about 1% or less, preferably about 1% or less is used. In order for the coating material of the brown glass container to maintain a brown appearance, about 6% of the coating material penetrating into the coated glass container is required.
It is preferable that the light transmittance of 00 nm or more is about 25% or more.

Examples of the pigment used in the present invention include azo, anthraquinone, naphthoquinone, isoindolinone, perylene, indigo, fluorenone, phenazine, phenothiazine, and polymethine.
Organic pigments such as polyene, difernylmethane, triphenylmethane, quinacdrine, acridine, phthalocyanine, quinophthalone, etc., having a wavelength of 450 to 5
Pigments that block light of 50 nm are exemplified. Specifically, SUMIPLAST RED AS (manufactured by Sumika Finechem), SUMI
PLAST RED FB (manufactured by Sumika Finechem), SYMULER FAST
RED 4134S (Dai Nippon Ink Co., Ltd.), FASTOGEN SUPER RED
7100Y (manufactured by Dainippon Ink and Chemicals), FASTOGEN SUPER RED 710
0Y-E (manufactured by Dainippon Ink), FASTOGEN SUPER RED 500RS
(Dai Nippon Ink Co., Ltd.), FASTOGEN SUPER VIOLET RVS
(Dai Nippon Ink Co., Ltd.), FASTOGEN SUPER VIOLET RXS
(Manufactured by Dainippon Ink), SYMULER FAST ORANGE K (manufactured by Dainippon Ink), and SYMULER FAST ORANGE 4183H (manufactured by Dainippon Ink).

The coating material of the present invention may contain butyl carbitol, triethoxy carbitol, 2,2,
4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, diethylene glycol mono-2-ethylhexyl ether, dibutyl sebacate,
Dibutyl citrate, acetyl tributyl citrate, diethylene glycol monobutyl ether acetate, 4-
Methyl-2-oxo-1,3-dioxolane, 3-methyl-3-methoxybutyl acetate, dipropylene glycol-n-butyl ether, dimethyl succinate, dimethyl glutarate, dimethyl adipate, tributyl phosphate, tributoxy Film-forming aids such as ethyl phosphate, dioctyl adipate, dibutyl diglycol adipate, bis (2-ethylhexyl) azelate, dioctyl sebacate, etc .; pH adjusters such as ammonia water and sodium hydroxide; leveling agents; viscosity adjusters; An activator, a water releasing agent, an antifoaming agent, a plasticizer, an ultraviolet absorber, a penetrant, a crosslinking agent, an antistatic agent, a polymerization inhibitor, an adhesion promoter, a surface conditioner, and an antioxidant may be added. . Further, a silicone resin may be added as long as the adhesiveness between the label and the coating material by the casein adhesive is not significantly reduced.

Examples of the glass container of the present invention include glass containers such as brown glass bottles, transparent glass bottles, and colored glass bottles. Among them, brown glass containers such as beer bottles are preferable.

As a method of coating the coating material on a glass container, for example, when the resin composition having film forming properties is a composition comprising a photocurable resin and a silane coupling agent, a roller type coating apparatus may be used. The composition is coated on a glass container by a method using a coating belt type coating apparatus or a spray type coating apparatus, brush coating, puff coating, transfer method, etc., and then cured by irradiating light such as ultraviolet ray, visible light laser or the like. And the like. Examples of the light source of the light beam include a low-pressure or high-pressure mercury lamp, a metal halide lamp, a xenon lamp, and the like. Further, when the resin composition having a film forming property is a composition comprising a synthetic resin emulsion and a silane coupling agent, in addition to the above method,
After the composition is coated on a glass container by a method such as an immersion method or a flow coater method, the composition is usually dried for about 0 to 48 hours to produce a target glass container. After coating the synthetic resin emulsion composition on the glass container, air blowing, heat treatment, or the like may be performed as necessary to shorten the drying time.

The thickness of the coating material of the present invention is usually about 0.5
The thickness is about 30 μm, preferably 1 to 20 μm, particularly preferably 2 to 15 μm.

[0038]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

(Resin Composition Having Film Forming Properties) As a resin composition having film forming properties, the following components were mixed in the parts by weight shown in Table 1. (1) Photocurable resin: Photocurable resin composed of epoxy acrylate, polyfunctional acrylic monomer and carbonyl compound (Sumiflash XR-98, manufactured by Sumitomo Chemical Co., Ltd.) (2) Synthetic resin emulsion: Acrylic resin Emulsion (Sumikaflex S-3550, manufactured by Sumitomo Chemical Co., Ltd.) (3) Synthetic resin emulsion: vinyl acetate resin emulsion (Sumikaflex S-752, manufactured by Sumitomo Chemical Co., Ltd.) (4) γ-aminopropyl Triethoxysilane (5) γ-glycidoxypropyltrimethoxysilane (6) γ-methacryloxypropyltrimethoxysilane (7) butyl carbitol (8) triethoxybutyl phosphate

(Pigment) The following pigments were mixed with the resin composition having film forming properties in parts by weight shown in Table 1. (9) SUMIPLAST RED AS (manufactured by Sumika Finechem Co., Ltd.) (10) SUMIPLAST RED FB (manufactured by Sumika Finechem Co., Ltd.) (11) SYMULER FAST RED 4134S (manufactured by Dainippon Ink and Chemicals, Inc.) (12) ) FASTOGEN SUPER RED 7100Y (Dai Nippon Ink Chemical Industry Co., Ltd.)

(Preparation of Glass Container Coated with Coating Material) (a) Photo-curable resin composition A photo-curable resin composition was placed in a large brown bottle (633 ml) for beer bottles which was used as a returnable and had scratches on the entire surface. (1), a silane coupling agent ((4), (5)) and a pigment ((9), (10)) were mixed in the weight ratio shown in Table 1, and the obtained coating material was mixed per bottle. It coated so that it might become 0.5 g. After coating, ultraviolet light was irradiated using a high-pressure mercury lamp to cure the resin, thereby obtaining a glass container. (A) Composition comprising synthetic resin emulsion and silane coupling agent Synthetic resin emulsion ((2), (3)), silane coupling agent ((5), (6)), additive ((7),
(8)) and the pigments ((11), (12)) were mixed at the weight ratios shown in Table 1, and the resulting coating material was flow-coated from the top of the glass container. After coating, it was dried at room temperature for 48 hours.

(Method of Evaluating Coating Material) (a) Flaw Concealing Property The appearance of the coating material after coating and curing was visually observed and evaluated according to the following criteria. ：: The entire glass container is glossy, and the scratches are hidden. ×: The entire glass container is not glossy and scratches are not concealed.

(A) Water resistance The appearance of the coated and cured glass container after immersion in water at 20 ° C. was observed and evaluated according to the following criteria. ：: Even if the glass container was immersed in water for one day, there was no change in the overall appearance. ：: Even if the glass container was immersed in water for 1 hour, there was no change in the overall appearance. ×: When the glass container was immersed in water for 1 hour,
Whitening, peeling or lifting occurred.

(C) Alkali peeling property A glass container coated with a 4% aqueous NaOH solution was placed at 80 ° C. ×
The appearance after immersion for 10 minutes was observed and evaluated according to the following criteria. ：: The coating material of the entire glass container was peeled off. ×: There is a portion where the coating material of the glass container is not peeled off.

(D) Light-shielding property The coated glass container was cut into a size of 1 cm × 3 cm, and cut with a spectrophotometer V-560 (manufactured by JASCO Corporation).
The transmittance at 00 nm was measured and evaluated according to the following criteria. ：: transmittance is 5% or less. X: The transmittance is larger than 5%.

(E) Label Adhesion Label paper was adhered to the surface of the coated glass container via a casein adhesive, dried for 4 days, and it was confirmed that the label was not peeled off at all. Next, it was immersed in water at 30 ° C. for one day and evaluated according to the following criteria. ：: The label was not peeled off from the coating material at all. ×: There is a part where the label is peeled off from the coating material.

(Examples 1 to 8, Comparative Example) Table 1 shows the weight ratio of the resin composition having a film forming property and the pigment and the evaluation results of the obtained coating material. The evaluation results of commercially available beer bottles are shown in Comparative Examples in Table 1.

[0048]

[Table 1]

[0049]

The glass container coated with the coating material of the present invention is excellent in wound concealing property, alkali peeling property, water resistance, light-shielding property and label adhesiveness. Can be used for

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C09D 5/00 C09D 5/02 5/02 127/06 127/06 131/04 Z 131/04 133/00 133/00 183/08 183/08 B65D 1/00 B (72) Inventor Shigeki Naito 3-1-198 Kasuganaka, Konohana-ku, Osaka City F-term in Sumitomo Chemical Co., Ltd. 3E033 BA01 BB08 CA20 EA10 4G059 AA04 AC30 FA09 FA12 FA13 FA15 FA22 4J038 CD021 CF021 CG141 CR071 DB261 DD181 DG211 FA011 FA041 FA061 FA111 FA231 FA241 FA261 FA281 GA01 GA06 JA29 JA33 JA34 JB36 JC18 JC34 JC35 KA03 NA10 NA10 NA10

Claims (18)

[Claims] 1. A resin composition having a film forming property and a wavelength of 45.
A coating material for a glass container, comprising a pigment that blocks light of 0 to 550 nm. 2. The resin composition having a film forming property is a composition comprising at least one kind of a resin having a film forming property selected from a photocurable resin and a synthetic resin emulsion, and a silane coupling agent. Claim 1.
A coating material according to claim 1. 3. The coating material according to claim 2, wherein the resin having a film forming property is a photocurable resin. 4. The coating according to claim 3, wherein the photocurable resin is a resin comprising (A) a photocurable oligomer and / or monomer and (B) a photopolymerization initiator. Wood. 5. The coating material according to claim 4, wherein the component (A) is an oligomer and / or a monomer having at least one unsaturated carbon-carbon bond. 6. The oligomer according to claim 5, wherein the oligomer having an unsaturated carbon-carbon bond is an oligomer having at least one unsaturated group selected from an acryloyl group, a methacryloyl group and a vinyl group. Covering material. 7. The monomer having an unsaturated carbon-carbon bond is at least one kind of unsaturated group-containing monomer selected from monofunctional acrylic monomers, polyfunctional acrylic monomers, and vinyl group-containing monomers. The coating material according to claim 5, characterized in that: 8. The coating material according to claim 2, wherein the resin having a film forming property is a synthetic resin emulsion. 9. The synthetic resin emulsion is at least one selected from a vinyl acetate resin emulsion, a vinyl chloride resin emulsion and an acrylic resin emulsion.
The coating material according to claim 8, wherein the coating material is a type of emulsion. 10. An acrylic resin emulsion is used in an amount of 0.1 to 50 parts by weight per 100 parts by weight of the solid content of the emulsion.
10. An emulsion obtained by copolymerizing parts by weight of (meth) acrylic acid monomer.
A coating material according to claim 1. 11. The silane coupling agent is represented by the following general formula (1) R ₁ NH (CH ₂ ) ₃ SiX _p (OR ₂ ) _3-p (1) (wherein X is substituted with a halogen atom) A good monovalent hydrocarbon group; R ₁ represents hydrogen or a β-aminoethyl group; R ₂ is an alkyl group having 1 to 4 carbon atoms;
Represents The coating material according to any one of claims 2 to 7, which is an amino group-containing alkoxysilane represented by the formula (1) and / or a partial hydrolyzate thereof. 12. The silane coupling agent according to the following general formula (2) (Wherein, Y is a monovalent hydrocarbon group optionally substituted with a halogen atom, R is an alkyl group having 1 to 4 carbon atoms,
q is 0 or 1. The composition comprising a glycidoxy group-containing alkoxysilane represented by the formula (1) and / or a partial hydrolyzate thereof.
The coating material according to any one of 9 and 10. 13. A film-forming resin composition comprising a photocurable resin comprising (A) and (B) and a coupling agent (C) having the following proportions, respectively. The coating material according to any one of claims 4 to 7 or 11, wherein (A): 99.4 to 75 parts by weight (B): 0.5 to 20 parts by weight (C): 0.1 to 5 parts by weight 14. The ratio of the film-forming resin composition comprising the synthetic resin emulsion and the silane coupling agent is 1 to 20 parts by weight of the silane coupling agent per 100 parts by weight of the solid content of the synthetic resin emulsion. The coating material according to any one of claims 2, 8, 9, 10 and 12, wherein the coating material is provided. 15. A glass container comprising the coating material according to any one of claims 1 to 14. 16. A wavelength of 500 nm transmitted through a glass container.
The glass container according to claim 15, wherein the light transmittance of the glass container is 5% or less. 17. A method for improving the label adhesion of a coating material, comprising using the coating material according to claim 1. Description: 18. A method for shading a glass container, comprising using the coating material according to claim 1. Description: