JP2632696B2 - How to improve the mechanical strength of glass containers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] <Field of Industrial Application> The present invention relates to a method for improving the mechanical strength of a glass container, and more particularly, to a method for curing a reactive composition which is cured by irradiation with active energy rays. The present invention relates to a method for improving the pressure resistance and impact strength of a glass container by coating the surface.

<Conventional technology> In general, glass takes advantage of its transparency, glossiness, high light resistance, chemical resistance and the like, and is used for containers for food dissolving and chemicals such as bottles and cups, decorative articles, instruments for scientific experiments, and the like. It is used in various fields. However, glass, on the other hand, is inherently heavy as compared to plastics and the like, and is inferior in flexibility and impact resistance, and is also brittle and inferior in impact resistance as compared to metals. In particular, in the case of glass bottles, the use of glass bottles has been limited compared to plastic containers and metal containers due to the problem of damage and scattering of glass due to external impact, and particularly to personal injury at the time of breakage and scattering due to internal pressure of pressurized sealed bottles. .

From these facts, a resin protective film is formed on a glass molded body such as a glass bottle, or a protective support is attached to the glass to improve the impact resistance and the effect of preventing scattering at the time of breakage. Means for doing so have already been proposed.

For example, 1) a method of coating a photocurable resin on the outer surface of a glass molded body such as a glass bottle to prevent the glass from being scratched or scattered when broken (Japanese Patent Application Laid-Open Nos. 49-102711 and 59-1402)
No. 67, GB2073050, etc.), 2) Apply a synthetic resin with excellent adhesion to the glass surface,
Methods to prevent scattering and improve impact resistance (Japanese Patent Publication No. 50-20964)
3) A method of improving scattering resistance and improving impact resistance by forming a laminated glass using a photocurable resin composition (Japanese Patent Laid-Open No. 59-223257, JP-A-61-7352, etc.) and others have been proposed.

<Problems to be Solved by the Invention> However, these proposals suggest that, although there is hardening to prevent scattering of glass, the impact force is reduced by forming a coating on the glass surface, and the glass is prevented from being damaged. However, it does not improve the pressure resistance and impact strength of a glass formed body such as a glass bottle. Therefore, with the methods according to these proposals, it is not possible to reduce the wall pressure of the glass while maintaining the pressure resistance and the impact strength, and to reduce the weight of the glass bottle.

As described above, by applying resin to the glass bottle,
An economically excellent dynamics of a glass bottle which can improve the pressure resistance and impact strength of the glass bottle and reduce the weight by reducing the thickness of the glass bottle without reducing the mechanical strength. At present, no method has been found to improve the mechanical strength.

[Structure of the Invention] <Means for Solving the Problems> The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems of the prior art, and as a result, performed a treatment with a silane coupling agent on a glass container in advance. After applying a specific reactive composition, or applying a specific reactive composition premixed with a silane coupling agent to a glass container, and then irradiating with an active energy ray, it adheres. The present invention was completed by finding that a coating film excellent in the thickness of the glass container could be formed, and that the pressure resistance and the impact strength of the glass container could be remarkably improved at the same time even when the coating film thickness was on the order of microns.

That is, the present invention provides [1] a reactive compound (II) in which a glass surface is preliminarily treated with a silane coupling agent (I) and then has two or more fluoroacryloyl groups or (meth) acryloyl groups in the molecule. Is applied to a glass container and cured by irradiating with an active energy ray, or [2] the reactive composition containing the silane coupling agent (I) is made of glass. The present invention relates to a method for improving the pressure resistance and the impact strength of a glass container, which is characterized by irradiating with an active energy ray after being applied to the container and curing.

 Hereinafter, the configuration of the present invention will be described in detail.

The present invention can be achieved by any of the methods [1] and [2].

The silane coupling agent treatment according to the method of the present invention [1] is a method of applying the silane coupling agent to a glass container as it is or a purified water such as distilled water or ion-exchanged water and / or an organic solvent. After dissolving in
It is usually carried out by applying the silane coupling agent solution to a glass container.

In the latter method, the concentration of the silane coupling agent in the silane coupling agent solution may be 0.01% by weight or more. In preparing this solution, it is preferable to dissolve the silane coupling agent in purified water and / or an organic solvent and then stir at room temperature for 5 minutes or more before applying the solution.

The solvent used here is used for controlling the viscosity, coatability and film thickness of the reactive composition described below, and is not particularly limited as long as it dissolves the silane coupling agent, but is compatible with purified water. Are preferred.

When the silane coupling agent solution treatment is performed on the glass container by the latter method, it is preferable to adjust the pH of the solution. According to the findings of the present inventors, the pH value after adjustment is 3 to
It is particularly preferable that the ratio be in the range of 5 from the viewpoint of improving the adhesion of the applied resin to glass, the pressure resistance, and the impact strength.

The applied amount of the silane coupling agent solution may be any amount as long as it is 1 mg or more per 1 m ² of surface area of the glass container as the silane coupling agent, but is preferably 1 mg to 100 mg per 1 m ² .

On the other hand, in the method [2], the silane coupling agent of the method [1] is previously abbreviated as two or more fluoroacryloyl groups or (meth) acryloyl groups [hereinafter simply referred to as (meth) acryloyl groups] in the molecule. Is mixed with a reactive composition containing at least one reactive compound having the formula (1) and applied to a glass container.

The content of the silane coupling agent in the reactive composition in which the silane coupling agent is preliminarily mixed in this method is 0.01 to 30% by weight, and is preferably 0.01 to 10% by weight from the viewpoint of strength development and economy.

According to the findings of the present inventors, it is obvious that the glass container coated with the reactive composition in which the silane coupling agent according to the method [2] is previously mixed has improved pressure resistance and impact strength. However, when it is used under severe conditions such as exposure to hot water and / or alkaline hot water, it is necessary to improve the adhesion, pressure resistance and impact strength to the glass of the resin to be coated. It is preferred that the reactive composition has an acid value of from 0.01 to 100.

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 reactive composition.

In the methods [1] and [2], the components for adjusting the pH or the acid value may be any available acids, bases and buffers without any limitation. For example, the reactive compound (II)
Or acid groups bonded in the diluent monomer (III) or (meth) acrylic acid generated by decomposition from them,
Further, a newly added organic acid or mineral acid may be used.

Examples of the acid component according to the present invention include a compound formed by adding succinic anhydride or phthalic anhydride to the hydroxyl group of the reactive compound having a hydroxyl group in the molecule (g)-(i). A compound shown below in III-1, III-37, In addition to CH ₂ = CHCONHC (CH ₃ ) ₂ CH ₂ SO ₃ H, the following specific examples can be given.

Acetic acid, fatty acid having an alkyl group having 2 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. still,
Examples of the base include various amines, lithium hydroxide, potassium hydroxide, and sodium hydroxide.

The silane coupling agent according to the present invention, a reactive composition,
As a method for applying these mixtures to a glass container, various methods known in the art, for example, brush coating,
Coating method using applicator, bar coater, roller brush, roll coater, etc., spray coating method using air spray or airless spray coating machine, flow coating method using shower coater or curtain flow coater (flow coating), dipping method, and 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 container.

Further, when the silane coupling agent according to the present invention, the reactive composition and a mixture thereof are applied or impregnated in a glass container as a solution obtained by dissolving the mixture in a solvent, the solvent is dried at room temperature, under heating or under reduced pressure. Performing a process is required.

According to the findings of the present inventors, irrespective of the presence or absence of the solvent in the silane coupling agent (solution), the reactive composition, and the mixture thereof according to the present invention, it is applied to a glass container and then heated and held. The glass adhesion of the cured resin is improved, and the effect of improving mechanical strength such as pressure resistance and impact strength is stabilized. Heating of the applied silane coupling agent (solution), the reactive composition and the mixture thereof,
The residual heat of the pre-heated glass container or glass substrate may be used, or it may be newly exposed to hot air or introduced into an oven, or may be carried out by irradiating a far infrared heater or microwave. Is also good. The heating temperature is preferably 40 to 120 ° C., and the heating time is preferably 10 seconds to 1 hour. However, when the solvent is removed by heating from the reactive composition and the mixture of the silane coupling agent solution and the reactive composition, the heating of the monomer is performed. More preferably, the solvent is removed at 50 to 80 ° C. for 10 seconds to 1 hour to prevent polymerization.

When polymerizing and curing the reactive composition according to the present invention and a mixture of the silane coupling agent with the reactive composition, known in the art, a germicidal lamp, a fluorescent lamp for ultraviolet rays, a carbon arc, a xenon lamp, a high-pressure mercury lamp for copying, Medium- or high-pressure mercury lamps, ultra-high-temperature mercury lamps, electrodeless lamps, metal halide lamps, ultraviolet rays using natural light as a light source, or electron beams using a scanning or curtain electron beam accelerating path can be used, and the thickness is 1 μm or less. In the case of ultraviolet curing of the coating layer, it is preferable to irradiate under an inert gas atmosphere such as nitrogen gas from the viewpoint of increasing the efficiency of polymerization.

In the method for improving the mechanical strength such as the pressure resistance of the glass container according to the present invention, the thickness of the cured resin film including the coating layer of the silane coupling agent required for effectively exhibiting the strength improving effect, As long as it is 0.5 μm or more, there is no problem. However, even after washing with alkaline hot water and / or hot water, a tough and excellently adhered cured film is formed. Is preferably 2 to 200 μm, and 2 to 30 μm
Is more preferable.

The silane coupling agent (I) according to the present invention is an organosilicon monomer having two or more different reactive groups in a molecule, and one of the reactive groups is a group capable of reacting with glass. A certain methoxy group, an ethoxy group, a silanol group, etc., and another reactive group capable of reacting with a (meth) acryloyl group, such as a vinyl group, a methacryloyl group, an acryloyl group, an epoxy group, an amino group, and a mercapto group. Etc.

Specific examples of the silane coupling agent (I) include the following compounds.

_{(I) -1 CH 2 = CHSiCl} 3 (I) -2 CH 2 = CHSi (OCH 3) 3 (I) -3 CH 2 = CHSi (OC 2 H 5) 3 _{(I) -5 CH 2 = CHSi} (OCH 2 CH 2 OCH 3) 3 _{(I) -7 H 2 NCH 2} CH 2 NHCH 2 CH 2 CH 2 Si (OCH 3) 3 (I) -8 H 2 NCH 2 CH 2 CH 2 Si (OC 2 H 5) 3 (I) -9 CH _{2 = CHCH 2 NHC 2 H 4} NHC 3 H 6 Si (OCH 3) 3 (I) -10 CH 2 = CHCH 2 NHC 2 H 6 Si (OCH 3) 3 _{(I) -15 CH 2 = CHCOOC} 3 H 6 Si (OCH 3) 3 (I) -21 ClCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (I) -22 HSCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ Further, these specific compounds are hydrolyzed by a method known in the art, A compound having a structure in which part or all of an alkoxy group is changed to a silanol group can also be included as the silane coupling agent according to the present invention.

Among these silane coupling agents (I), those having an unsaturated double bond are preferable, and among them, (I) -13 to
Those having a (meth) acryloyl group as exemplified in (I) -16 are particularly preferred.

It should be noted that the silane coupling agent according to the present invention is not limited to the specific examples described above.

The reactive compound (II) having two or more (meth) acryloyl groups in the molecule according to the present invention is an essential component for the purpose of expressing its strength in a resin obtained by curing after irradiation with active energy rays. As long as it contains two or more (meth) acryloyl groups in the molecule, those known in the art can be used without any limitation.

The weight ratio of the reactive compound (II) in the reactive composition according to the present invention may be 100% except for the photoinitiator in any of the methods [1] and [2], but is usually 5 to 95%. Yes, from the viewpoint of the toughness and curability of the cured resin film
90% is preferred.

The reactive compound (II) according to the present invention includes those commonly referred to in the art as polyfunctional (meth) acrylates and those referred to as prepolymers, base resins, oligomers or acrylic oligomers. Specifically, the following are exemplified.

(II)-(i) Polyhydric (meth) acrylate in which two or more (meth) acrylic acids are bonded to a polyhydric alcohol.

(II)-(ii) Polyhydric acrylate in which two or more fluoroacrylic acids are bonded to a polyhydric alcohol.

(II)-(iii) A polyester acrylate in which two or more (meth) acrylic acids are bonded to a polyester polyol obtained by a reaction between a polyhydric alcohol and a polybasic acid.

Examples of the polyhydric alcohol in the above (i), (ii) and (iii) include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol,
Trimethylolpropane, dipropylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, dipentaerythritol, bisphenol A, And the like.

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. Examples of polybasic acids include phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid, succinic acid, terephthalic acid, alkenyl succinic acid, and the like.

(II)-(iv) An epoxy-modified (meth) acrylate in which an epoxy group of an epoxy compound having at least two epoxy groups in a molecule is esterified with (meth) acrylic acid to form a (meth) acryloyl group as a functional group.

(II)-(v) An epoxy-modified fluoroacrylate in which an epoxy group of an epoxy compound having at least two epoxy groups in a molecule is esterified with fluoroacrylic acid to obtain a fluoroacryloyl group as a functional group.

Examples of the epoxy compound having at least two epoxy groups in a molecule include bisphenol A-epichlorohydrin type resin, phenol novolak-epichlorohydrin type resin, and polyhydric alcohol epichlorohydrin type alicyclic resin.

(II)-(vi) A polyurethane acrylate obtained by reacting 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 molecular center and containing isocyanate groups at both ends.

(II)-(vii) Other examples include polyether (meth) acrylate, melamine (meth) acrylate, alkyd (meth) acrylate, isocyanurate (meth) acrylate, and silicon (meth) acrylate.

Among the above-mentioned reactive compounds (II) having two or more (meth) acryloyl groups in the molecule, in order to effectively improve the pressure resistance and impact strength of the glass container, the following reactive compounds are preferred. Compounds.

Equation (a) Wherein R is H, F or CH ₃ , and n and m are 2n
+ M10 and may be the same or different,
X is H or F], a compound represented by the formula (b): Wherein l is an integer of 1 to 10, and R is as defined above. A reactive compound represented by the formula (c): A compound represented by the formula: (d) A compound represented by the formula: A compound represented by the formula: (f) A compound represented by Equation (g) A compound represented by the formula: (h) A compound represented by the formula: A compound represented by the formula: (j) [R, p and R ₁ are all the same as defined above. In the reactive compound having two or more (meth) acryloyl groups in the molecule according to the present invention, the compounds represented by the general formulas (a) to (a)
The weight ratio of the compound of (i) may be 100%, and usually 5 to 95% is appropriate. However, in order to improve the adhesion of the coated resin to glass and obtain higher hot water resistance, the formula (b) is used. The compound of (i) is preferably 5 to 50%.

More specific examples of these (II) include the following.

(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 (II) -5 propylene glycol di (meth) acrylate (II) -6 dipropylene glycol di (meth) acrylate (II) -7 tripropylene glycol di (meth) acrylate (II) -8 polypropylene Glycol di (meth) acrylate (number average molecular weight 250-1000) (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 hydroxypivalic acid ester neopentyl glycol di (meth) acrylate (R is H or CH ₃ ) (R is H or CH ₃ ) (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 dipentaerythritol hexaacrylate (II) -28-tolyl (2-acryloxy) isocyanurate (N and x are integers from 1 to 10) (N, x is an integer of from 1 to 10) (however, R is H or -CH _3.) (II) -32 polyethyleneglycol 400 di (meth) acrylate (II) -33 1,3-bis (3 '-Acryloxyethoxy-2'-hydroxypropyl) 5,5-dimethylhydantoin _{(II) -35 (CH 2 =} (C) RCOOCH 2 CH 2 O 3 P = 0 ( where, R is H or -CH _3.) (II) -65 dipentaerythritol diacrylate (II) -66 dipentaerythritol triacrylate (II) -67 dipentaerythritol tetraacrylate (II) -68 dipentaerythritol pentaacrylate (Q is an integer of 1 to 10) (Q is an integer of 1 to 10) (Q is an integer of 2 to 9) (Or R is H, F or CH _3.) (II) Specific examples shown in -69~ (II) -87 but is an epoxy-modified (meth) acrylate of all α adduct, also β-adduct And the reactive compounds (II) to (iii) according to the present invention. In addition, the reactive compound (II)
-(Iii) is, of course, not limited to the above specific examples.

The reactive compound according to the present invention contains a reactive compound (I
In addition to I), for the purpose of controlling the viscosity, reactivity, and post-effect hardness of the composition, a monofunctional monomer having one (meth) acryloyl group in the molecule, that is, generally referred to as a diluent monomer in the art. Compound (III) to be used.

Specific examples thereof include: III-1 (meth) acrylic acid 〃2 alkyl (meth) acrylate (C ₁ -C ₁₈ ) III-3 phenoxyethyl (meth) acrylate ４4 ethoxyethyl (meth) acrylate ５5 methoxy Ethyl (meth) acrylate 6 Butoxyethyl (meth) acrylate 7 N, N-diethylaminoethyl (meth) acrylate 8 N, N-dimethylaminoethyl (meth) acrylate 9 Glycidyl (meth) acrylate 10 Allyl (meth) ) Acrylate 〃 11 2-hydroxyethyl (meth) acrylate 〃 12 2-hydroxypropyl (meth) acrylate 〃 13 2-methoxyethoxyethyl (meth) acrylate 〃 14 2-ethoxyethoxyethyl (meth) acrylate 〃 15 benzyl (meth) Acrylate 〃 16 cyclo Sil (meth) acrylate III-17 dicyclopentenyl (meth) acrylate 〃18 dicyclopentenyloxyethyl (meth) acrylate 〃19 2-hydroxyethyl (meth) acryloyl phosphate 〃20 tetrahydrofurfuryl (meth) acrylate 〃21 dicyclo Pentadienyl (meth) acrylate 〃22 Dicyclopentadieneethoxy (meth) acrylate 〃23 p-Penzylphenoxyethyl (meth) acrylate 〃24 1,6-Hexanediol mono (meth) acrylate 〃25 Neopentyl glycol mono (meth) ) Acrylate 〃26 Glycerin mono (meth) acrylate 〃27 Trimethylolpropane mono (meth) acrylate III-28 Pentaerythritol mono (meth) acrylate 〃29 2-Hydroxy-3-phenyloxy Ropyr (meth) acrylate 〃 30 2-hydroxy-3-octyloxypropyl (meth) acrylate 〃 33 diethylene glycol mono (meth) acrylate 〃 32 polyethylene glycol (400) mono (meth) acrylate 〃 33 2- (perfluorooctyl) ethyl (Meta)
Acrylate 〃 34 Isobornyl (meth) acrylate 〃 35 Dicyclopetanyl (meth) acrylate 〃 36 Phenyl (meth) acrylate And the like.

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

The above-mentioned oil-soluble fluorine-containing surfactant (IV) has at least one or more fluorinated aliphatic groups having 1 to 20 carbon atoms in a molecule, and has a concentration of 0.1 to 25 ° C with respect to an organic solvent. weight%
It is a compound having the above solubility. Examples of the organic solvent used herein include those used for controlling the viscosity, coatability and film thickness of the reactive composition as described later.

Representative specific 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, and specific examples of these compounds include the following.

_{(IV) -3 C 8 F 17} CH 2 CH 2 OCHCHO 15 H (IV) -4 C 8 F 17 CH 2 CH 2 SCH 2 CH 2 OCH 2 CH 2 O 10 H (2) a fluorinated aliphatic group is heavy It is introduced as a side chain of the coalesced skeleton, and some of such fluoropolymers can be obtained from commercial products. For example, a fluorine-based surfactant Megafac F-177, F-173, F-172, F-171, F-184 manufactured by Dainippon Ink and Chemicals, a surface modifier Defensor MCF-300, MCF-312, MCF-323, solvent-type water / oil repellents 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 fluorinated (meth) acrylate containing a fluorinated aliphatic group having 1 to 20 carbon atoms, and (meth)
It is a copolymer with a monofunctional monomer having one acryloyl group, and more specific examples thereof include the following.

(IV) -5 The molar ratio of methyl methacrylate 1: copolymer of 5 (average molecular weight _{20,000) (IV) -6 C n} F 2n + 1 CH 2 CH 2 OCOCH = CH 2 (n: a mixture of 1 to 16, average molecular weight 520 ) And a methyl methacrylate macromer having an average molecular weight of about 5,000 at a molar ratio of 3: 1 (average molecular weight of 40,000) (IV) -7 C ₁₀ F ₂₁ CH ₂ CH ₂ OH, polypropylene glycol having a molecular weight of 5,000, and tolylene the molar ratio of isocyanate 2: 1: 2 of polyurethane (average molecular weight _{5,900) (IV) -8 C 8} F 17 SO 2 N (CH 2 CH 2 OH) 2, the molar ratio of polyethylene glycol and adipic acid of 1: 3 : 4 polyester (average molecular weight of 4,700) The reactive composition according to the present invention is applied or impregnated in a glass container which has been previously treated with a silane coupling agent or which has not been treated, and is then subjected to light, electron beam, radiation energy, Is polymerized and cured by applying heat to form the desired coating film. It can be formed. When light such as ultraviolet light is used as the polymerization initiation energy, 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,
(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: 2-hydroxy-2-methyl-1-phenylpropan-1-one and the like, and optionally an amine compound or a phosphorus compound. Photosensitizers can be added to speed up the polymerization. When polymerizing and curing with an electron beam or radiation, addition of a polymerization initiator or the like is not particularly required.

In addition, when heat is used as the polymerization initiator, the polymerization can be cured in the absence of a catalyst or in the presence of a polymerization initiator such as azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide-cobalt naphthenate. It is possible.

In the reactive composition of the present invention, in addition to the polymerization initiator and the like, a solvent, a light stabilizer, an ultraviolet absorber, a pigment, a dye,
Various additives such as an antifoaming agent, a leveling agent, a silane coupling agent, and a surfactant can be added.

The solvent can be blended to control the viscosity, coatability, and film thickness of the reactive composition of the present invention and the silane coupling agent. Such a solvent is not particularly limited as long as it does not adversely affect the polymerization reactivity of the reactive composition according to the present invention and the silane coupling agent treatment, but methanol, ethanol, isopropyl alcohol, butanol, acetone, methyl ethyl ketone, Methyl isobutyl ketone, diethyl ether, tetrahydrofuran, methyl acetate, ethyl acetate, butyl acetate, n-
Hexane, toluene, chloroform, dichloroethane,
Low boiling solvents such as carbon tetrachloride and 1-fluoro-1-dichloro-2-difluoro-2-chloroethane are preferred from the viewpoint of workability.

[Examples] Next, specific examples of the method of the present inventions [1] and [2] will be described, but it is needless to say that the present invention is not limited by the related description. "Part" in the text
Is based on weight.

Examples 1-31 and Comparative Examples 1-4 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 an oven. And dried for 5 minutes. Next, the glass plate is cut and inserted with a diamond cutter (cut grooves are formed), and in the embodiment of the method [1], after a silane coupling agent treatment described below is performed, the mixture is treated with methyl ethyl ketone using a No. 3 bar coater. After coating various reactive compositions in which the active ingredient was adjusted to 40% by weight, drying in an oven at 60 ° C. for 1 minute, and using a high-pressure mercury lamp of 80 W / cm1 for 30 minutes
Irradiated with ultraviolet light for 2 seconds and cured. The cured film pressure was 3 μm.

The three-point bending rupture test result of the obtained glass plate sample,
And the results of the hot water test are summarized in Table 1.

 Various experimental conditions are as follows.

Treatment with silane coupling agent (a) 0.5% by weight solution of silane coupling agent in water / isopropyl alcohol (1/2% by weight) or (b) 0.5% by weight of silane coupling agent in water / isopropyl alcohol (1/2% by weight) Ratio) was adjusted to pH 4.5 with acetic acid, and after mixing, the mixture was stirred at room temperature for 15 minutes, and then subjected to dip coating of a glass plate into which a cut was inserted. The coated glass plate was dried at 60 ° C. for 2 minutes and treated with a silane coupling agent. The coating thickness of the silane coupling agent is 3 mg / m ² . In the table, (a) and (b) show the above silane coupling agent solutions, respectively.

3-point bending rupture strength test Glass plate sample coated with reactive composition (n = 20)
Bending strength tester (Shimadzu Autograph AG-5000)
C) Using, span distance 50mm, head speed 0.5mm
At / min, the three-point bending breaking strength was measured. The obtained results are shown in the table as relative values to blanks where neither the silane coupling agent treatment nor the reactive composition was applied.

Hot water resistance test The glass plate coated with the reactive composition was immersed in hot water at 80 ° C and rubbed with a cotton cloth. The results of a three-point bending strength test (n = 20) after immersion in hot water at 80 ° C. for one hour are shown.

In addition, the number in a table | surface shows the compound in the main part, the code | symbol M described after shows a methacrylate compound, and the code | symbol A shows an acrylate compound.

Example 32 A glass bottle (weight 170 gr, volume 300 ml) manufactured by the applicant of the present invention, Yamamura Glass, was externally wounded as follows, treated with a silane coupling agent, and then treated with methyl ethyl ketone. The reactive compositions of Examples 1 to 31 in which the active ingredient was adjusted to 40% by weight were applied by a dipping method, immediately dried at 60 ° C. for 1 minute in an open state, and then placed in an ultraviolet curing furnace (160 W / cm high pressure). (2 mercury lamps). With respect to the sample bottle having a 3 μm cured film formed on the outer surface in this manner, a pressure resistance test (internal pressure test method for glass bottles for carbonated beverages)
JIS-S-2322 However, for those which did not burst at a water injection pressure of 700 pounds, the pressure resistance was calculated as 700 pounds. ) And an impact strength test (mechanical impact test method for glass bottles for carbonated beverages, JIS-S-2303). The results of the obtained strength are shown in Table 2 as the average value and the minimum value improvement ratio of the average value and the minimum value of the glass container (control bottle) not coated with the reactive composition according to the present invention. For reference, Table 3 shows the measurement results of the pressure resistance and impact strength of the control bottle. In addition, various injury conditions were performed as follows.

1) Internal wounding: Put carborundum # 24,11gr into a glass bottle, hold the bottle horizontally and rotate for 30 seconds to evenly scratch the inner surface.

2) External injury: ALS LS (Line Simulator)
Scratches for 5 minutes to evenly scratch the outer surface of the bottle.

At the same time, the same test was conducted for the compositions used in Comparative Examples 1 to 4, and the results are shown in Table 2.

From the results in Table 2, it can be seen that the reactive composition according to the present invention significantly improves the pressure resistance and impact strength of the bottle. In particular, the result of the improvement in the pressure resistance is a remarkable effect that cannot be obtained conventionally.

Examples 33 to 71 and Comparative Examples 5 to 12 The following various reactive compositions were prepared by washing the cut and inserted glass plates in the same manner as in Examples 1 to 31 and adjusting the active ingredient to 40% by weight with methyl ethyl ketone. The composition was applied with a bar coater and cured in the same manner as in Examples 1 to 32. The cured film thickness
3.0 μm.

The obtained sample (n = 20) was subjected to three-point bending rupture strength under the same conditions as in Examples 1 to 31.
Each test of the point bending rupture strength was performed. The results are shown in Table 4.

Example 72 A glass bottle subjected to various injuries under the above conditions,
The reactive composition of Example 33, in which the active ingredient was adjusted to 40% by weight with methyl ethyl ketone and previously mixed with a silane coupling agent, was applied to the outer surface, the inner surface, or both the inner and outer surfaces, and dried and cured. These bottles (24 samples) were subjected to each of the tests of pressure resistance and impact strength under the same conditions as described above. The obtained results are shown in Table 5 as the improvement ratio of the strength of each of the control bottles which were not damaged or variously damaged. The injury conditions are the same as described above.

Next, Table 6 shows the results of tests performed in the same manner as in Example 72 using the reactive compositions shown in Examples 34 to 71 and Comparative Examples 5 to 12. The numerical values in the table are all improvement rates (%) of the average value and the minimum value (lower value) of the pressure resistance and the impact strength of the outer coated bottle with respect to the uninjured control bottle.

Example 73 Using a silane coupling agent I-13, a silane coupling agent-treated solution was prepared by the method (b) of the above method [1], and the same procedure as in Examples 1 to 31 was performed for a glass plate and a glass bottle. Was treated with a silane coupling agent. Thereafter, the reactive compositions shown in Table 7 were prepared in an amount of 40% by weight of the active ingredient, applied to glass plates and glass bottles in the same manner as in Examples 33 to 71, and physical properties were measured. Table 7 shows the measurement results of the three-point bending rupture strength of the glass plate coated with the resin, and Table 8 shows the improvement ratio of the pressure resistance and the impact strength of the glass bottle coated with the reactive composition on the outer surface.

Example 74 The reactive composition according to the present invention used in Examples 1 to 31 and 33 to 71 and 73 was treated in the same manner as in Example 31 to a thickness of 3
The coating was applied to the outer surface of a 300 ml glass bottle with a μm, loaded into a vending machine, and the breakage rate was examined. 50 μm thick in glass bottle
When the resin composition according to the present invention was applied to both the case where the heat-shrinkable film was attached and the case where the heat-shrinkable film was not attached, the breakage rate was extremely small as compared with the control bottle. On the other hand, when the compositions of Comparative Examples 1 to 4 and Comparative Examples 6 to 12 were applied, almost no improvement in the decrease in the breakage rate was obtained.

Comparative Example 13 On the same glass plate as used in the example, a solvent-based urethane resin or an aqueous latex, which is generally used for shatter prevention in the glass bottle industry, is applied and dried at 70 ° C. to form a film. However, when the same bending test was performed, the relative value was 1.0 in all cases, and no improvement in mechanical strength was observed.

Comparative Example 14 A glass bottle for carbonated beverages (weight 580 gr, capacity 1000 ml) manufactured by the applicant of the present invention, Yamamura Glass, coated with a 200 μm solvent-free, non-yellowing urethane resin on the outer surface for the purpose of preventing fragments from scattering. It has been submitted to users as a glass bottle for carbonated drinks.

A pressure resistance test was similarly performed using this bottle. The results obtained are shown in Table 9 as an improvement ratio with respect to the control bottle.

 The test was performed on 2 Lots.

From the results in Table 11, it can be seen that the reactive composition according to the present invention significantly improves the pressure resistance and impact strength of the bottle. In particular, the result of the improvement in the pressure resistance is a remarkable effect that cannot be obtained conventionally.

〔The invention's effect〕

According to the method for improving the strength of the glass container according to the present invention,
Since the pressure resistance and impact strength of the glass container are significantly improved, the thickness of the glass can be reduced while maintaining the mechanical strength of the glass at the same level or higher. 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 molding, and the mechanical strength decreases even after slow cooling. For the purpose of preventing the occurrence of scratches on the surface due to the impact or friction that also triggers, a surfactant application step or the like is provided, but if a reactive composition coating step according to the present invention is introduced, The step of strengthening the mechanical strength of the glass container and the step of preventing the glass container from being damaged can be omitted, and the productivity of the glass container can be improved and the production cost can be reduced. In addition, conventionally, in the production site of glass containers, defective products have been generated in terms of mechanical strength, but when used in the method for improving the strength of glass containers according to the present invention, the pressure resistance and impact strength of these containers are kept at a certain level. Since the improvement can be achieved as described above, it is possible to obtain economic advantages such as high quality of the method for improving the glass container and improvement in the yield. Still further, the method for improving the strength of a glass container according to the present invention enables recycling of a returnable glass bottle having reduced mechanical strength.

Furthermore, since the reactive composition according to the present invention is usually in a liquid state and can be arbitrarily adjusted in viscosity by being diluted with a solvent, it can be applied not only to glass bottles but also to other complicated shaped glass molded articles. In addition, since active energy rays such as ultraviolet rays penetrate to the inside regardless of the shape of the glass, it is possible to cure and coat various forms. Therefore, if the reactive resin composition according to the present invention is used, the size of the glass molded body,
It is possible to improve the thickness resistance and impact strength of various glass molded articles regardless of their shapes, such as the thickness of glass, and film, plate, rod, sphere, and linear shapes, and combinations thereof. It is possible.

Further, since the reactive composition according to the present invention can introduce a pigment or a dye, according to the method for improving the pressure resistance and impact strength of the glass container 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.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tsukasa Matsubara 3-25-402, Tonoyamacho, Nishinomiya-shi, Hyogo (72) Inventor Shigeo Kawaguchi 2-2-8-410 Tanaka, Minato-ku, Osaka-shi, Osaka

Claims (7)

(57) [Claims] A glass surface is treated with a silane coupling agent, and then a reactive composition containing a reactive compound having two or more fluoroacryloyl groups or (meth) acryloyl groups in a molecule is applied. And a method for improving pressure resistance and impact strength of a glass container, wherein the glass container is cured by irradiation with an active energy ray. 2. A reactive composition comprising a silane coupling agent and a reactive compound having two or more fluoroacryloyl groups or (meth) acryloyl groups in a molecule is applied to a glass surface, and then the active energy is applied. A method for improving the pressure resistance and impact strength of a glass container, which comprises curing the glass container by irradiation with radiation. 3. The method according to claim 1, wherein the reactive compound is a polyhydric alcohol (meth)
Epoxy compound in which two or more (meth) acrylic acids are bonded to the epoxy group of a polyvalent (meth) acrylate in which two or more acrylic acids are bonded and / or an epoxy compound having an epoxy group having at least two epoxy groups in a molecule 3. The method according to claim 1, which is a modified (meth) acrylate. 4. The reactive compound is a polyhydric fluoroacrylate in which two or more fluoroacrylic acids are bonded to a polyhydric alcohol and / or an epoxy group of an epoxy compound having an epoxy group having at least two epoxy groups in a molecule. 3. The method according to claim 1, wherein the fluoroacrylic acid is an epoxy-modified fluoroacrylate having two or more fluoroacrylic acids bonded thereto. 5. The silane coupling agent solution in the silane coupling agent treatment has a pH of 3-5.
The described method. 6. The method according to claim 2, wherein the acid value of the reactive composition is 0.01 to 100. 7. The method according to claim 1, wherein the reactive composition contains an oil-soluble fluorinated surfactant.