JP2987402B2 - Active energy ray-curable composition and method for improving mechanical strength of glass using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable composition and a method for improving the mechanical strength of glass using the same.

[0002]

2. Description of the Related Art As a method for improving the mechanical strength of a glass container, Japanese Patent Application Laid-Open No. 1-201047 discloses [I] a method in which a glass surface is previously treated with a silane coupling agent. A curable composition containing at least one curable compound having an acryloyl group selected from the group consisting of the above fluoroacryloyl groups, methacryloyl groups, and acryloyl groups is applied to a glass container, and irradiated with an active energy ray. Cure or [I
I) a method for improving the mechanical strength of a glass container, which comprises applying the curable composition containing a silane coupling agent to a glass container, and thereafter irradiating with an active energy ray to cure the composition. Have been.

[0003]

However, the method of the above [I] has one additional step compared to the method of the above [II], so that the productivity is inferior, and the active energy ray used in the method of the above [II] is poor. An active energy ray-curable composition comprising a curable compound, a silane coupling agent, and an organic solvent has poor storage stability. Even if the composition after being left for a long time is applied to a glass container and cured, the The maximum value of the initial mechanical strength when the composition was applied and cured was not obtained, and the mechanical strength of the glass container hardly improved.

[0004]

Accordingly, the present inventors have found a curable composition which can obtain the maximum value of mechanical strength when the curable composition immediately after preparation is applied to glass and cured even after long-term storage. After intensive studies, surprisingly, the above [I
It has been found that a composition obtained by adding water to the curable composition used in the method of I) gives a mechanical strength that is completely equivalent to that of the composition immediately after preparation even after long-term storage. It was completed.

That is, the present invention relates to an active energy ray-curable composition comprising a coupling agent, an active energy ray-curable compound and water and having an acid value of 0.01 to 100, and a coupling agent and an active energy ray-curable composition. Applying an active energy ray-curable composition containing an energy ray-curable compound and water to a glass surface, and then irradiating with an active energy ray to cure the glass, It provides an improvement method.

Hereinafter, unless otherwise specified, the active energy ray-curable compound is referred to as “curable compound”, and the active energy ray-curable composition is referred to as “curable composition”. The curable composition according to the present invention is prepared by appropriately mixing a coupling agent (I), a curable compound (II), and water (III). The order of mixing is not particularly limited, and (II) may be added to the aqueous solution obtained by mixing (I) and (III), or (I) and (II) may be added in advance. To the mixture
(III) may be added. At that time, an organic solvent may be used together if necessary.

The mixing ratio of the above (I), (II) and (III) is not particularly limited. The content of (I) in the curable composition according to the present invention is usually 0.01 to 30 parts by weight per 100 parts by weight of the total of (I), (II), and (III), and the strength development and 0.01 to 10 from the viewpoint of economy
Parts by weight are preferred.

The content of (III) in the curable composition of the present invention is usually 0.5 to 80 parts by weight per 100 parts by weight of the total of (I), (II) and (III), 0.5 to 5
It is preferably 0% by weight.

[0009] The content of (II) in the cured composition according to the present invention is determined according to the amount of (I) and (III) used. The coupling agent (I) according to the present invention refers to an organic compound having two or more different reactive groups in a molecule, such as a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, and zirconium. Coupling agents and zirconium / aluminum coupling agents are exemplified, and among them, silane coupling agents are preferred.

As the coupling agent (I), two or more different coupling agents may be used in combination. The silane coupling agent used in the present invention includes 2
An organic silicon monomer having at least two different reactive groups, one of the reactive groups being a group capable of reacting with glass and the other reactive group being a group capable of reacting with a (meth) acryloyl group. Consisting of Examples of such a material include those represented by the following general formula.

[0011]

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Or

[0013]

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Specific examples of the silane coupling agent include the following compounds.

[0015]

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[0016]

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[0017]

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Further, compounds having a structure in which these specific compounds are hydrolyzed by a method in the art and part or all of the alkoxy groups are changed to silanol groups can be included as the silane coupling agent according to the present invention.

The titanium coupling agent is not particularly limited either, and examples thereof include the following compounds.

[0020]

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[0021]

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The coupling agent (I) according to the present invention is, of course, not limited by the above-mentioned specific examples. The active energy ray-curable compound (II) according to the present invention is a compound that cures to a resin after irradiation with active energy rays, and includes, for example, a fluoroacryloyl group,
Examples include those containing an acryloyl-based group selected from the group consisting of a methacryloyl group and an acryloyl group (hereinafter, simply referred to as acrylate), but those known in the art can be used without any limitation.

Hereinafter, unless otherwise specified, an acryloyl group, a methacryloyl group, and a fluoroacryloyl group are collectively referred to as an acryloyl group. The (meth) acryl group combines methacrylic acid and acrylic acid.

The curable compound (II) according to the present invention is generally classified in the art as a polyfunctional (meth) acrylate or a prepolymer, base range, oligomer or acrylic oligomer. The following are specifically included. (II)-(i) Polyhydric (meth) acrylate in which two or more α-fluoroacrylic acids or (meth) acrylic acids are bonded to a polyhydric alcohol. (II)-(ii) A polyester acrylate in which two or more α-fluoroacrylic acids or (meth) acrylic acids are bonded to a polyester polyol obtained by a reaction between a polyhydric alcohol and a polybasic acid.

The polyhydric alcohol in the above (i) and (ii) includes ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, trimethylolpropane, dipropylene glycol, polyethylene glycol, and polypropylene. Glycol, pentaerythritol, dipentaerythritol,
Bisphenol A,

[0026]

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The polyhydric alcohols include ethylene oxide-modified polyhydric alcohols and propylene oxide-modified polyhydric alcohols formed by adding ethylene oxide or propylene oxide to the above specific compounds. The polybasic acids include phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid, succinic acid, terephthalic acid,
Alkenyl succinic acid and the like can be mentioned. (II)-(iii) An epoxy-modified acrylate in which the epoxy group of an epoxy compound having at least two epoxy groups in the molecule is esterified with α-fluoroacrylic acid or (meth) acrylic acid to form an acryloyl group as a functional group.

Examples of the epoxy compound having at least two epoxy groups in the molecule include bisphenol A-epichlorohydrin type resin, phenol novolak-epichlorohydrin type resin, polyhydric alcohol epichlorohydrin type alicyclic resin and the like. (II)-(iv) A polyurethane acrylate obtained by reacting a hydroxyl group-containing α-fluoroacrylate or a hydroxyl group-containing (meth) acrylate with a polyvalent isocyanate compound.

Examples of the polyvalent isocyanate compound include compounds having a structure such as polyester, polyether, or polyurethane at the center of the molecule and containing isocyanate groups at both ends. (II)-(v) In addition, polyether (meth)
Acrylate, polyether α-fluoroacrylate, melamine (meth) acrylate, melamine α-fluoroacrylate, alkyd (meth) acrylate, alkyd α-fluoroacrylate, isocyanurate (meth) acrylate, isocyanurate α-fluoroacrylate, silicon (meth) ) Acrylate, silicon α-fluoroacrylate. (II)-(vi) A compound having one acryloyl group in the molecule.

Among the above-mentioned curable compounds having two or more acryloyl-based groups in the molecule, the following curable compounds are particularly preferable for effectively improving the pressure resistance and impact strength of the glass container. No.

[0031]

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Wherein R is H, F or CH3;
n and m are integers satisfying 2 ≦ n + m ≦ 10 and may be the same or different, and X is H or F].

[0033]

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Wherein 1 is an integer of 1 to 10, and R has the same meaning as described above. A reactive compound represented by

[0035]

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A compound represented by the formula:

[0037]

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A compound represented by the formula:

[0039]

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A compound represented by the formula:

[0041]

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A compound represented by the formula:

[0043]

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[0044]

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A compound represented by the formula:

[0046]

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A compound represented by the formula:

[0048]

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[0049]

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[R, p and R1 are all the same as defined above. More specifically, these (II) are exemplified as follows. (II) -1 Ethylene glycol di (meth) acrylate (II) -2 Diethylene glycol di (meth) acrylate (II) -3 Triethylene glycol di (meth) acrylate (II) -4 Polyethylene glycol di (meth) acrylate (number (Average molecular weight: 150 to 1000) (II) -5 Propylene glycol di (meth) acrylate (II) -6 Dipropylene glycol di (meth) acrylate (II) -7 Triprophylene glycol di (meth) acrylate (II) -8 Polypropylene glycol di (meth) acrylate (number average molecular weight 250 to 1000) (II) -9 Neopentyl glycol di (meth) acrylate (II) -10 1,3-butanediol di (meth) acrylate (II) -11 1 , 4-Butanediol di (meth) acrylate (II ) -12 1,6-Hexanediol di (meth) acrylate (II) -13 hydroxypivalate neopentyl glycol di (meth) acrylate

[0051]

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(II) -16 Bisphenol A di (meth)
Acrylate (II) -17 Trimethylolpropane tri (meth) acrylate (II) -18 Pentaerythritol tri (meth) acrylate (II) -19 Dipentaerythritol hexa (meth) acrylate (II) -20 Pentaerythritol tetra (meth) Acrylate (II) -21 Trimethylolpropane di (meth) acrylate (II) -22 Dipentaerythritol monohydroxypenta (meth) acrylate (II) -23 Polypropylene glycol-modified neopentyl glycol diacrylate (II) -24 Polyethylene glycol-modified Bisphenol A diacrylate (II) -25 Polypropylene glycol-modified trimethylolpropane triacrylate (II) -26 Polyethylene glycol-modified trimethylolpropane triacrylate (II) -27 dipe Data hexaacrylate (II) -28 tris (2-acryloxy) isocyanurate

[0053]

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(II) -32 Polyethylene glycol 40
O-di (meth) acrylate (II) -33 1,3-bis (3'-acryloxyethoxy-2'-hydroxypropyl) 5,5-dimethylhydantoin

[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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(II) -65 dipentaerythritol diacrylate (II) -66 dipentaerythritol triacrylate (II) -67 dipentaerythritol tetraacrylate (II) -68 dipentaerythritol pentaacrylate

[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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And the like. Examples of the curable compound having one acryloyl group in the molecule include (II) -88 (meth) acrylic acid (II) -89 alkyl (meth) acrylate (C1 to C1)
8) (II) -90 Phenoxyethyl (meth) acrylate (II) -91 Ethoxyethyl (meth) acrylate (II) -92 Methoxyethyl (meth) acrylate (II) -93 Butoxyethyl (meth) acrylate (II)- 94 N, N-Diethylaminoethyl (meth) acrylate (II) -95 N, N-Dimethylaminoethyl (meth) acrylate (II) -96 Glycidyl (meth) acrylate (II) -97 Allyl (meth) acrylate (II) -98 2-hydroxyethyl (meth) acrylate (II) -99 2-hydroxypropyl (meth) acrylate (II) -100 2-methoxyethoxyethyl (meth) acrylate (II) -101 2-ethoxyethoxyethyl (meth) Acrylate (II) -102 Benzyl (meth) acrylate (II) -103 Cyclohexyl (meth) acryl Over preparative (II) -104 dicyclopentenyl (meth) acrylate (II) -105 dicyclopentenyloxyethyl (meth)
Acrylate (II) -106 2-hydroxyethyl (meth) acryloyl phosphate (II) -107 tetrahydrofuryl (meth) acrylate (II) -108 dicyclopentadienyl (meth) acrylate (II) -109 dicyclopentadiene ethoxy ( (Meth) acrylate (II) -110 p-benzylphenoxyethyl (meth) acrylate (II) -111 1,6-hexanediol mono (meth) acrylate (II) -112 neopentyl glycol mono (meth) acrylate (II)- 113 glycerin mono (meth) acrylate (II) -114 trimethylolpropane mono (meth) acrylate (II) -115 pentaerythritol mono (meth) acrylate (II) -116 2-hydroxy-3-phenyloxypropyl (meth) acrylate (II) -117 2-Hydroxy-3 Octyloxypropyl (meth) acrylate (II) -118 diethylene glycol mono (meth) acrylate (II) -119 polyethylene glycol (400) mono (meth) acrylate (II) -120 2- (perfluorooctyl) ethyl (meth) acrylate (II) -121 Isobornyl (meth) acrylate (II) -122 Dicyclopetanyl (meth) acrylate (II) -123 Phenyl (meth) acrylate

[0071]

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(II) -125 Isooctyl (meth) acrylate and the like. The above (II) -69 to (II) -8
Although all the specific examples shown in 7 are epoxy-modified (meth) acrylates of α-adduct, β-adducts are also included in the curable compounds (II)-(iii) of the present invention. (II) -1
(II) -125 as (meth) acrylate
Although the acryloyl group and the methacryloyl group are shown, it is needless to say that they may be fluoroacryloyl groups. The curable compound (II) is, of course, not limited to the specific examples described above.

The composition ratio of the monofunctional monomer and the difunctional or higher functional monomer constituting the active energy ray-curable compound according to the present invention is not particularly limited, and the weight ratio is 100: 0 to 100: 0.
The ratio is 0: 100, but when ultraviolet rays are used as the active energy ray, 98: 2 to 0: 100 is preferable, and 95: 5 to 0 :, from the viewpoint of curability and toughness of the cured coating film.
100 is more preferred.

As described above, the curable compound according to the present invention may be composed of only a curable compound having one acryloyl group in a molecule such as (II) -88 to (II) -124. Although it is preferable, it is preferable to use a curable compound having two or more acryloyl-based groups in a molecule such as (II) -1 to (II) -87 as an essential component.

Usually, a composition finally obtained by using a curable compound having two or more acryloyl groups in a molecule as a main component and a curable compound having one acryloyl group in a molecule in combination. The viscosity, reactivity, and hardness after curing of the product can be controlled.

As the water (III), purified water such as distilled water or ion-exchanged water is preferable. An organic solvent can be added to the curable composition of the present invention in order to control viscosity, coatability, and film thickness. Such an organic solvent is not particularly limited as long as it does not adversely affect the polymerization reactivity of the curable composition according to the present invention, but includes methanol, ethanol, isopropyl alcohol, butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, and diethyl ether. Low boiling solvents such as ether, tetrahydrofuran, methyl acetate, ethyl acetate, butyl acetate, n-hexane, toluene, chloroform, dichloroethane, carbon tetrachloride, 1-fluoro-1-dichloro-2-difluoro-2-chloroethane, etc. It is preferable from the viewpoint of workability. Among them, an organic solvent which can dissolve the coupling agent (I) and is compatible with water (III) is particularly preferable.

According to the findings of the present inventors, (I) and (I
The glass container coated with the curable composition consisting of only I) and (III) not only has improved mechanical strength, but is exposed to hot water and / or alkaline hot water. When used under severe conditions, the curable composition may have an acid value of 0.01 to 100 in terms of improving the adhesion of the resin to be coated to glass, the pressure resistance and the impact strength. preferable.

The acid value as used herein means the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 gram of the curable composition. As the component for adjusting the acid value at this time, available acids, bases, and buffers can be used without any limitation. For example, acid groups bonded to the curable compound (II) or decomposed from them. Α-fluoroacrylic acid or (meth) acrylic acid generated by the reaction may be used, or a newly added organic acid or mineral acid may be used.

The acid component according to the present invention is formed by adding succinic anhydride or phthalic anhydride to the above-mentioned hydroxyl group of the curable compound formula (g)-(i) having a hydroxyl group in the molecule. A compound represented by the formula (II) -88 or (II) -124:

[0080]

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In addition to the above, the following specific examples are given.
Acetic acid, fatty acid having an alkyl group having 3 to 18 carbon atoms, methanesulfonic acid, alkylsulfonic acid having an alkyl group having 2 to 18 carbon atoms, trifluoromethanesulfonic acid, p
-Toluenesulfonic acid, benzoic acid, phthalic acid, formic acid, lactic acid, cinnamic acid, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid and the like.
In addition, examples of the base include various amines, lithium hydroxide, potassium hydroxide, and sodium hydroxide.

According to the findings of the present inventors, it is preferable to add a leveling agent or a surfactant to the curable composition according to the present invention in order to improve the uniformity of application to a glass container. . As such a leveling agent or a surfactant, any of a hydrocarbon type, a silicone type and a fluorine type can be used, and in particular, an oil-soluble fluorine type surfactant (IV)
, It is possible to more effectively improve the pressure resistance and impact strength of the glass container.

The above-mentioned oil-soluble fluorine-based surfactant (IV)
Means at least one or more carbon atoms in a molecule of 1 to 2
It has 0 fluorinated aliphatic groups and 25 ° C for organic solvents.
Is a compound having a solubility of 0.1% by weight or more. Examples of the organic solvent used herein include those used for controlling the viscosity, coatability and film thickness of the curable composition as described above.

Typical examples of the oil-soluble fluorine-based surfactant (IV) include the following two types. (1) A fluorinated aliphatic group is linked to a polar group via a divalent linking group. Specific examples of these compounds include the following.

[0085]

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(2) A fluorinated aliphatic group is introduced as a side chain of the polymer skeleton, and some such fluorinated polymers can be obtained from commercial products. For example, a fluorine-based surfactant Megafac F-177, F-173, F-172, F- manufactured by Dainippon Ink and Chemicals, Inc.
171, F-184, surface modifier Defensor MCF-
300, MCF-312, MCF-323, Dickguard F-320, F-327 and the like. In addition, fluorine-based polymers having various molecular structures can be synthesized and used according to the required characteristic level. For example, a copolymer of a fluorinated (meth) acrylate having a fluorinated aliphatic group having 1 to 20 carbon atoms and a monofunctional monomer having one (meth) acryloyl group in the molecule, More specific examples of these include the following.

[0087]

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The curable composition according to the present invention is applied or impregnated on glass which has been previously treated with a silane coupling agent or has not been treated, and then polymerized and cured by applying an active energy ray or heat to obtain a desired coating. A covering film can be formed.

The active energy rays in the present invention include, for example, microwaves, far infrared rays, infrared rays, visible rays,
Ultraviolet rays, electron beams, radiation (β-rays, γ-rays) and the like can be mentioned. The active energy ray-curable composition in the present invention is
When an electron beam curable compound is used as the curable compound (II), an electron beam curable composition is used, and when an ultraviolet curable compound is used, an ultraviolet curable composition is used.

When light such as ultraviolet light is used as the active energy ray, a so-called photopolymerization initiator known in the art can be used. Examples of such a photoinitiator (V) include (V) -1: benzophenone, (V) -2: acetophenone, (V) -3: benzoin, and (V) -4:
Benzoin ethyl ether, (V) -5: benzoin isobutyl ether, (V) -6: benzyl methyl ketal, (V) -7: azobisisobutyronitrile, (V)
-8: 1-hydroxycyclohexyl phenyl ketone,
(V) -9: Addition of 2-hydroxy-2-methyl-1-phenylpropan-1-one and a photosensitizer such as an amine compound or a phosphorus compound as needed to speed up the polymerization. can do. When polymerizing and curing with an electron beam or radiation, addition of a polymerization initiator or the like is not particularly required.

Further, in the curable composition of the present invention, an organic metal compound such as a salt, an organic zinc compound, an organic tin compound, an organic platinum compound or the like, which is a catalyst for the coupling agent (I), may be used, if necessary. You may. Examples of the salt include ammonium chloride, ammonium perchlorate, sodium carbonate, sodium hydrogen carbonate, sodium hydrogen phosphate, and the like.

[0092]

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[0093] Specific examples of the organometallic compound include, for example, zinc octylate, tin octylate,
Examples include dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate and the like.

The glass according to the present invention includes substances generally referred to as glass, such as general oxide glass, non-oxide glass, and functional glass called new glass, and is not limited in any way. However, oxide glass is important in terms of marketability and practicality of the film adhered to the glass and the glass strengthened by the film, and its shape is not limited at all. Thus, containers are of particular importance.

The method of applying the curable composition according to the present invention to glass includes various methods known in the art, for example,
Brush coating, coating method using an applicator, bar coater, roller brush, roll coater, etc., spray coating method using an air spray or airless spray coating machine, flow coating method using a shower coater or curtain flow coater, etc., dipping Method, a spinner coating method, or the like can be used, and it is desirable to appropriately use them according to the shape or use of the glass.

In the method of the present invention, for example, when the mechanical strength such as the pressure resistance of a glass container is to be improved, the thickness of the resin coating after curing is not particularly limited as long as the strength improving effect is effectively exhibited. The thickness of the subsequent resin film is 0.
The curable composition may be applied to a glass container and cured so that the thickness becomes 5 μm or more. However, alkaline hot water and / or
Alternatively, in order to form a tough cured film having excellent adhesion even after rinsing with hot water, and to maintain the initial mechanical strength such as pressure resistance, the thickness of the cured resin film is 2 μm.
It is preferable to apply and cure the curable composition so as to have a thickness of from 200 to 200 μm, especially from 2 to 30 μm.

When the curable composition according to the present invention is further applied or impregnated to glass as a solution obtained by further dissolving the curable composition in a solvent, drying of the water or the solvent may be performed at room temperature, under heating or under reduced pressure, if necessary. May be provided.

According to the findings of the present inventors, the curable composition according to the present invention can be used irrespective of whether water or a solvent is contained therein.
Although it may be cured with active energy rays immediately after application to glass, activation of the composition by heating and holding or irradiation with active energy rays before that improves the glass adhesion of the cured resin, The effect of improving mechanical strength such as impact strength is further improved.

The drying and activation of the water and the solvent can be performed simultaneously. Activation of the applied curable composition,
You may use the residual heat held by the glass itself in advance,
It may be newly exposed to hot air, introduced into an oven, or may be irradiated with the above-mentioned active energy ray.

If necessary, a thermopolymerization curing inhibitor may be added to the curable composition in advance to prevent curing of the curable compound in the curable composition during activation. . In the case of activation using hot air, the temperature of the hot air is a temperature at which the curable composition in the curable composition does not thermally polymerize, for example, 40 to
The temperature is 120 ° C., preferably 50 to 80 ° C., and the time is preferably 10 seconds to 1 hour.

Incidentally, when the conditions of the active energy ray curing step following the activation step are kept constant, the activation time (activation time) at 60 ° C. when hot air is applied to the curable composition is increased. Up to a time of 60 seconds, the mechanical strength of the finally obtained resin-coated glass tends to increase.

In activation using an active energy ray, it is preferable to use an active energy ray different from that used in the curing step, and it is particularly preferable to use far-infrared rays or microwaves.

If necessary, an inactivating agent for the active energy ray used in the activation step and the activation step may be used so that the curable compound is not cured. By the way, following the activation process,
When the condition of the active energy ray curing step is kept constant, the time for irradiating the curable composition with far-infrared rays from a far-infrared ray irradiator having a surface temperature of 400 ° C. to extend the activation time is 5 seconds in irradiation time. The maximum value of the mechanical strength of the finally obtained resin-coated glass is obtained, and even if the irradiation is performed for 5 seconds or more, the result tends to be unchanged.

In the activation by far-infrared rays, the conditions vary depending on three factors: the surface temperature of the irradiation surface of the far-infrared irradiation device, the distance between the irradiation object and the irradiation surface, and the irradiation time. It is preferable to perform several times to determine the optimum value of each element.

The activation method has a short activation time and is excellent in productivity, and it is difficult to volatilize the curable composition partially or make the composition nonuniform even in a three-dimensional glass. Is hard to rise, and the deterioration of the glass itself due to heat history does not easily occur.
Activation by an active energy ray is preferable because it has advantages such as the ability to use a compact device.

The above-mentioned activating method is not limited to the curable composition of the present invention, but includes compositions, paints, and fiber processing agents essentially containing a conventional silane coupling agent and an active energy ray-curable compound. , Adhesives, binders and the like.

For example, the curable composition for coating a glass container containing a silane coupling agent, an active energy ray-curable compound, and, if necessary, an organic solvent described in JP-A-1-201047 can also be used. Method can be applied.

When the curable composition of the present invention is activated or polymerized and cured, a germicidal lamp, a fluorescent lamp for ultraviolet rays, a carbon arc, a xenon lamp, a high-pressure mercury lamp for copying, a medium- or high-pressure mercury lamp, an ultra-high-pressure mercury lamp known in the art. , An electrodeless lamp, a metal halide lamp, ultraviolet light using natural light as a light source, or an electron beam using a scanning type, curtain type electron beam accelerating path, a far-infrared ray using an iron ferrite type generator, or a ceramic type generator. it can.

The curable composition according to the present invention can be easily cured by using the above-mentioned active energy ray and its generator. However, the thickness is 1μ
In the case of ultraviolet curing of a coating layer having a thickness of m or less, it is preferable to irradiate ultraviolet rays in an atmosphere of an inert gas such as nitrogen gas from the viewpoint of efficiency of polymerization.

The conditions of the active energy ray irradiation are not particularly limited, and may be any energy and irradiation time sufficient for curing the curable composition.
30 seconds is preferred.

When heat is used as a polymerization initiator, no catalyst or azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide,
It is possible to polymerize and cure in the presence of a polymerization initiator such as cobalt naphthenate.

The curable composition of the present invention may further comprise, if necessary, a thermal polymerization inhibitor, a synthetic resin,
Various additives such as light stabilizers, far infrared absorbers, infrared absorbers, ultraviolet absorbers, pigments, dyes, defoamers, leveling agents, and surfactants can be added.

According to the method for improving the mechanical strength of glass according to the present invention, the pressure resistance and impact strength of the glass container are remarkably improved. Can be reduced in thickness. Therefore, the cost of raw materials can be reduced and the weight of the glass container can be reduced. In addition, by increasing the mechanical strength of the glass container by the method according to the present invention, even for vending machines such as soft drinks that have been tended to be avoided in the past, it is possible to open up the use of the glass container, The demand can be expanded.

In general, in the production of glass containers, various chemical strengthening treatment steps are provided for the purpose of imparting mechanical strength to a high-temperature glass container immediately after formation.
Further, for the purpose of preventing the occurrence of surface scratches due to impact or friction that also triggers a decrease in mechanical strength even after slow cooling, a surfactant coating step or the like is provided, but the curing according to the present invention Introducing the coating process of the conductive composition can omit the step of strengthening the mechanical strength of the glass container and the step of preventing the glass container from being damaged, thereby improving the productivity of the glass container and reducing the production cost. can do. In addition, conventionally, in the production site of glass containers, defective products have been generated in terms of mechanical strength, but if the method for improving the mechanical strength of glass according to the present invention is used, the pressure resistance and impact strength of these containers are kept constant. Since the glass container can be improved to a level higher than the standard, it is possible to obtain economical advantages such as higher quality of the method for improving the glass container and improvement in yield. Still further, the method for improving the mechanical strength of glass according to the present invention makes it possible to reuse a returnable glass bottle having reduced mechanical strength.

Further, the curable composition of the present invention is usually in a liquid state, and its viscosity can be arbitrarily adjusted by diluting it with a solvent. It can be applied, and since active energy rays such as ultraviolet rays penetrate into the inside regardless of the shape of the glass, it is possible to cure and coat various forms. Therefore, if the curable composition according to the present invention is used, the size of the glass molded body, the thickness of the glass, and the shape of a film, a plate, a rod, a sphere,
It is possible to improve the pressure resistance and the impact strength of various glass molded articles regardless of their shapes, such as a linear shape and a combination thereof.

Further, since it is possible to introduce pigments and dyes into the curable composition according to the present invention, according to the method for improving the mechanical strength of glass according to the present invention, various types of flint glass containers can be used. Coloring can be provided. Therefore, in the conventional process, when changing colors, a considerable time is required for the color change time, and a product loss occurs during the time.However, the method according to the present invention can solve such a problem. It is possible.

[0117]

EXAMPLES Next, specific examples of the present invention will be described. However, it is needless to say that the present invention is not limited by the related description. In the description, “parts” are based on weight. Example 1 and Comparative Examples 1 to 3 A commercially available hard glass plate (70 × 150 × 2 mm) was immersed in a 5% by weight aqueous sodium hydroxide solution for 1 hour, washed with distilled water, and then heated to 60 ° C. in a hot-air circulation oven. For 5 minutes. Next, the glass plate was cut and inserted (formation of kerfs) with a diamond cutter, and various curable compositions shown in Table 1 were applied. Next, after drying in the oven at 60 ° C. for 1 minute and holding by heating, immediately the high pressure mercury lamp 80 W
UV light was irradiated for 30 seconds using a / cm1 lamp to cure.
The cured film thickness was 3 μm.

Table 1 shows the results of a three-point bending rupture test of the obtained glass plate sample (n = 20). The conditions of the three-point bending rupture test are as follows. 3-point bending rupture strength test A glass plate sample coated with the curable composition was subjected to a spa distance of 50 mm and a head speed of 0.5 mm / min using a bending strength tester (Autograph AG-5000C, Shimadzu Corporation).
, The coated surface was directed to the two-point support side, and the three-point bending strength was measured. The results obtained are shown in the table as relative values to a damaged blank glass plate sample on which the curable composition was not applied.

The numbers in the table indicate the compounds in the text.
The symbol (M) described thereafter indicates a methacrylate compound, the symbol (A) indicates an acrylate compound, and MEK indicates methyl ethyl ketone.

Hereinafter, “immediately after adjustment” in the column of the test in the table means:
The composition prepared under the conditions of 25 ° C. and 60% humidity was referred to as “4.
"After 8 hours" indicates a composition 48 hours after preparation under the above conditions.

[0121]

[Table 1]

Examples 2 to 4 and Comparative Examples 4 to 6 In the same manner as in Example 1, various curable compositions shown in Tables 2 to 4 were applied to glass plates to obtain samples of the glass plates. (Cured film thickness 30 microns).

The obtained glass plate sample (n = 20) was subjected to a three-point bending rupture test based on the method of Example 1 and a hot water resistance test. The results are summarized in Table 2. The conditions of the hot water test are as follows. Hot water test A glass plate coated with the curable composition was placed in hot water at 80 ° C for 6 hours.
After immersion for 2 minutes and rubbing with a 2H pencil, the time required for the coating to peel off (peeling time)
The results of a three-point bending strength test (n = 20) after immersion in hot water at 80 ° C. for a time are shown.

Hereinafter, “after 192 hours” in the table means 25
The composition was prepared under the conditions of a temperature of 60 ° C. and a humidity of 60%.
The composition after 2 hours is shown.

[0125]

[Table 2]

[0126]

[Table 3]

[0127]

[Table 4]

Examples 5 to 7 Using the curable compositions of Examples 2 to 4, drying in an oven at 60 ° C. for 1 minute and holding by heating was performed by adjusting the surface temperature of the irradiated surface to 400 ° C. Ceramic type coating type far-infrared irradiator [manufactured by Teikoku Piston Ring Co., Ltd., 1 irradiation surface 13 cm × 13 cm, 200 V, 0.4
The number of one irradiation surface was adjusted so that kW and the area of the irradiation surface became three times or more. Example 1 except that the distance between the glass plate and the composition-coated surface was adjusted to be 10 cm, and the operation of irradiating far infrared rays to the coated surface of the glass plate for 5 seconds was used. A glass plate sample was obtained in exactly the same manner as described above. Using this glass plate sample, the same tests as in Examples 1 and 2 were performed. Table 5 shows the results.

[0129]

[Table 5]

Example 8 A hot-end coating (hereinafter abbreviated as H / C) process and a cold-end coating (hereinafter abbreviated as C / C) process manufactured by the applicant of the present invention, Yamamura Glass Co., Ltd., were performed. The curable composition 192 hours after the preparation of Example 2 was applied to the outer surface of a glass bottle (weight: 150 gr, capacity: 300 ml) by a dipping method, and was immediately placed in the oven in the oven.
After drying, heating and holding at 0 ° C. for 1 minute, an ultraviolet curing oven (16
(0 W / cm 2 high-pressure mercury lamps) for 30 seconds. With respect to 50 sample bottles having a cured film of 3 μm formed on the outer surface in this manner, a pressure resistance test (internal pressure test method for glass bottles for carbonated beverages JIS-S-2302, provided that those which do not burst at a water injection pressure of 900 spi, , Pressure resistance was calculated as 900 psi), and impact strength test (mechanical impact test method for glass bottles for carbonated beverages, JIS-S-2).
303). Table 6 shows the minimum and average values of the pressure resistance and the impact strength of the 50 sample bottles. Comparative Example 7 Fifty bottles were obtained in the same manner as in Example 8 except that the curable composition immediately after preparation in Comparative Example 4 was used, and the same test was performed. Table 6 shows the results.

Glass bottle without H / C treatment, or C
/ C treated glass bottle, or H / C treated and C /
A test similar to that of Example 8 was performed on a glass bottle that was not subjected to the C treatment. In each case, a good improvement in pressure resistance and impact strength was observed. Comparative Example 8 The same test as in Example 7 was performed using 24 glass bottles (control bottles) that were not coated with anything. The results are shown in Table 3.

[0132]

[Table 6]

Example 9 The operation of drying and heating in an oven at 60 ° C. for 1 minute in Example 8 was repeated by using the far-infrared ray irradiator in which the surface temperature of the irradiated surface was adjusted to 400 ° C. The same test was carried out by obtaining 50 sample bottles in exactly the same manner except that the bottles were passed along the irradiated surface for 5 seconds in such a manner that the distance between the bottles was 10 cm. Table 7 shows the results.

[0134]

[Table 7]

Glass bottle without H / C treatment, or C
/ C treated glass bottle, and also H / C treated, C / C
The same tests as in Example 9 were performed on the glass bottles that were not subjected to any treatment, and in all cases, good improvements in pressure resistance and impact strength were recognized. Example 10 In the same manner as in Example 1, the curable composition shown in Table 8 was applied to a glass plate, dried in an oven at 60 ° C. for 1 minute, and heated and held. 300kV,
Current 25mA, dose rate 30Mrad / sec, oxygen concentration at irradiation 0.
(1%) was irradiated with 5 Mrad and cured. The cured film thickness was 3 μm.

A three-point bending rupture test of the obtained glass plate sample was performed using the method of Example 1. Table 8 shows the results.
Shown in

[0137]

[Table 8]

Example 11 H / H manufactured by the present applicant, Yamamura Glass Co., Ltd.
Glass bottle with only C treatment (weight 150g, capacity 300
ml) was kept at a temperature of 60 ° C. ± 10 ° C., immersed in the curable composition 192 hours after preparation in Example 2, applied to the outer surface of the bottle, and immediately after the application, an ultraviolet curing oven (160 W / cm)
(2 high-pressure mercury lamps) for 30 seconds to cure.
With respect to 50 sample bottles having a cured film of 3 μm formed on the outer surface in this way, a pressure resistance test (JIS-S-2302, internal pressure resistance test method for glass bottles for carbonated beverages, provided that those which do not break at a water injection pressure of 900 psi) , Pressure resistance 9
Calculated as 00 psi. ) And impact strength test (mechanical impact test method for glass bottles for carbonated beverages JIS-S-2303)
Was done. Table 9 shows the minimum and average values of the pressure resistance and the impact strength of the 50 sample bottles.

[0139]

[Table 9]

[0140]

The active energy ray-curable composition of the present invention has excellent storage stability. Even if the composition stored for a long time is applied to glass and cured, the composition immediately after preparation is applied to glass and cured. This has a particularly remarkable effect that the maximum value of the mechanical strength is obtained. Moreover, the mechanical strength of the glass obtained by coating and curing the composition of the present invention immediately after preparation is superior to that of the glass obtained using the conventional composition immediately after preparation.

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁶ Identification code FI C08F 220/30 C08F 220/30 230/08 230/08 (72) Inventor Shigeo Kawaguchi 2-8- Tanaka, Minato-ku, Osaka-shi, Osaka 21-410 (56) References JP-A-2-90973 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 299/00-299/08 C08F 290/00-290 / 14 B65D 23/08 B65D 25/34 C03C 17/34 C08F 220/00-220/70 C08F 230/00-230/10

Claims (15)

(57) [Claims] 1. An acid value comprising a coupling agent, an active energy ray-curable compound and water, wherein the acid value is from 0.01 to 10.
An active energy ray-curable composition which is 0. 2. An acid value comprising a silane coupling agent, an active energy ray-curable compound and water, having an acid value of 0.01.
An active energy ray-curable composition of from 100 to 100. 3. An active energy ray-curable composition having an acid value of 0.01 to 100, comprising a silane coupling agent, an active energy ray-curable compound, water and an organic solvent. 4. The composition according to claim 2, wherein the active energy ray-curable compound is a curable compound having an acryloyl group selected from the group consisting of a fluoroacryloyl group, a methacryloyl group, and an acryloyl group. 5. The active energy ray-curable compound is a curable compound having in its molecule an acryloyl group selected from the group consisting of two or more fluoroacryloyl groups, methacryloyl groups, and acryloyl groups. 3
A composition as described. 6. The active energy ray-curable compound is a polyhydric alcohol and two or more (meth) acrylic acids bonded to a polyhydric (meth) acrylate and / or at least 2 in the molecule.
The composition according to claim 2, wherein the composition is an epoxy-modified (meth) acrylate in which two or more (meth) acrylic acids are bonded to an epoxy group of an epoxy compound having two epoxy groups. 7. The composition according to claim 1, wherein the content of water is 0.5 to 80 parts by weight per 100 parts by weight of the total of the coupling agent, the active energy ray-curable compound and water. 8. The active energy ray-curable compound is a curable compound having an acryloyl group selected from the group consisting of a fluoroacryloyl group, a methacryloyl group, and an acroyl group, and the content of water is different from that of the coupling agent. 0.5 to 100 parts by weight in total of the curable compound and water
The composition according to claim 1, which is 80 parts by weight. 9. The active energy ray-curable compound is a curable compound having an acryloyl group selected from the group consisting of two or more fluoroacryloyl groups, methacryloyl groups and acryloyl groups in a molecule, and water The content is 10 in total of the coupling agent, the curable compound and water.
The amount is 0.5 to 50 parts by weight per 0 parts by weight.
A composition as described. 10. The method according to claim 1,2,3,4 for glass.
10. The composition according to 5, 6, 7, 8, or 9. 11. The active energy ray-reactive composition contains an oil-soluble fluorine-based surfactant.
The composition according to 5, 6, 7, 8, 9 or 10. 12. A method for improving the mechanical strength of glass, comprising applying the active energy ray-curable composition according to claim 1 to a glass surface and thereafter irradiating with an active energy ray to cure the composition. 13. A method for improving the mechanical strength of glass, comprising applying the active energy ray-curable composition according to claim 2 to a glass surface, and thereafter irradiating the active energy ray to cure the composition. 14. An ultraviolet-curable composition comprising a silane coupling agent, an ultraviolet-curable compound, and water is applied to a glass surface, irradiated with far-infrared rays, and then cured with ultraviolet rays. How to improve the mechanical strength of glass. 15. An electron beam-curable composition comprising a silane coupling agent, an electron beam-curable compound and water, applied to a glass surface, irradiated with far-infrared rays, and then cured with an electron beam. A characteristic method for improving the mechanical strength of glass.