JP2014055224A - Coating material for glass scattering prevention - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating material for glass scattering prevention for forming a resin film having performance which prevents debris of glass from scattering when the glass material is broken by fall and the like and having high transparency on a surface of a glass material, and to provide a scattering prevented glass material using the coating material for glass scattering prevention.SOLUTION: The coating for glass scattering prevention contains an acryl resin and a silica fine particle, and the silica fine particle is 10 to 150 pts.mass based on 100 pts.mass of the acryl resin. Performance which prevents debris of glass form scattering is improved when the coating material for glass scattering prevention contains 0.5 to 10 pts.mass of a silane coupling agent based on 100 pts.mass of the acryl resin. A scattering prevented glass material is obtained by forming a resin film on a surface of the glass material by using the coating for glass scattering prevention.

Description

  The present invention relates to a glass scattering prevention coating material used for forming a resin film on the surface of a glass material for the purpose of preventing the scattering of the glass material, and a scattering prevention glass material using the coating material.

  In this specification, “silica fine particles” refers to silica particles having a primary particle diameter of 1 to 500 nm. The primary particle diameter can be measured by an observation method using a transmission electron microscope (SEM), a transmission electron microscope (TEM), or the like, or a BET method.

  In the present specification, “glass scattering prevention coating” refers to a resin film having a performance (hereinafter referred to as “scattering prevention performance”) that suppresses glass fragments from scattering when the glass material breaks due to dropping or the like. A paint for forming on the surface of a material.

In the following explanation, in the explanation regarding the content and content of the components contained in the glass scattering prevention paint, it is described in terms of nonvolatile content unless otherwise specified.

As a method for preventing glass fragments from being scattered when the glass material is broken, there is a method of providing a resin film on the surface of the glass material. As a method of providing a resin film, a method of attaching a resin film is well known. This method is often used for building window glass and the like, and JIS A5759 “film for architectural window glass” is available as a standard for films.

However, the method of pasting a film is easy to apply to a glass material with a smooth surface and a simple shape like a window glass, but it is difficult to apply to a glass material with a complicated shape having a non-planar part. there were.

  Therefore, a method has been proposed in which a resin film is formed by painting a surface of a glass material without using a film. Examples of paints used in such applications include the following.

  Patent Document 1 includes “a glass having a coating layer made of a composition containing a silane coupling agent, polycaprolactone, polydimethylsiloxane, and an isocyanate resin or a melamine resin” and “silane coupling agent, polycaprolactone, polydimethylsiloxane”. A coating agent comprising a composition containing siloxane and an isocyanate resin or a melamine resin is disclosed.

  Patent Document 2 discloses an aqueous polyurethane composition produced from a polyol compound, an organic polyisocyanate, another polyol having a carboxyl group or a sulfonic acid group, or another polyol having a basic group in the molecule and a chain extender. In the glass protective coating composition used, a glass protective coating composition characterized in that the polyol compound contains 50 to 100% by weight of polytetramethylene ether glycol having a molecular weight of 160 to 10,000 is disclosed.

In addition to the above-mentioned patent documents, patent document 3, patent document 4, and the like disclose urethane resin paints having an effect of preventing glass scattering.

JP 2006-290696 A (claims, etc.) JP-A-8-283660 (Claims etc.) JP 05-163460 A Japanese Patent Laid-Open No. 05-161876

As described above, the resin film formed on the surface of the glass material may be required to have high transparency so as not to impair the transparency of the glass. The resin film was not sufficiently transparent. Therefore, for example, when characters, scales, figures, patterns, and the like are drawn on a glass material, the visibility may be reduced by forming a resin film.
The present inventor has studied to obtain a coating material for preventing glass scattering using a highly transparent acrylic resin, unlike the one disclosed in the above-mentioned prior art, and has reached the present invention.

An object of this invention is to provide the coating material for glass scattering prevention with high transparency. Another object of the present invention is to provide an anti-scattering glass material using the glass anti-scattering paint.

The invention according to claim 1 is a glass scattering prevention paint for forming a resin film on the surface of a glass material, the paint contains an acrylic resin and silica fine particles, and 100 parts by mass of the acrylic resin. On the other hand, it is a coating material for preventing glass scattering, characterized in that the silica fine particles are 10 to 150 parts by mass.

The invention described in claim 2 is characterized in that, in the invention described in claim 1, the glass scattering preventing paint contains a silane coupling agent.

The invention according to claim 3 is the invention according to claim 2, wherein the coating material for preventing glass scattering contains 0.5 to 10 parts by mass of a silane coupling agent with respect to 100 parts by mass of the acrylic resin. It is characterized by.

  The invention according to claim 4 is the invention according to any one of claims 1 to 3, wherein the coating material for preventing glass scattering comprises at least one crosslinking agent selected from an isocyanate compound, an oxazoline compound, and a carbodiimide compound. It is characterized by containing.

The invention according to claim 5 is the invention according to any one of claims 1 to 4, wherein the surface of the glass material has a non-planar portion.

Invention of Claim 6 is a manufacturing method of the coating material for glass scattering prevention of Claim 2, Comprising: An acrylic resin, 10-150 mass parts silica fine particle with respect to 100 mass parts of acrylic resins, and silane It is characterized by mixing with a coupling agent.

The invention according to claim 7 is characterized in that a resin film having a thickness of 50 to 1000 μm is formed on the surface of the glass material by the paint for preventing glass scattering according to any one of claims 1 to 5. It is a shatterproof glass material.

  According to the first aspect of the present invention, a highly transparent paint for preventing glass scattering can be obtained.

According to the second aspect of the present invention, in addition to the effect of the first aspect of the invention, the coating film becomes tough, whereby a glass scattering prevention coating material having further excellent scattering prevention performance can be obtained.

  According to invention of Claim 3, in addition to the effect of invention of Claim 2, a coating film becomes especially tough.

  According to the invention described in claim 4, in addition to the effect of the invention described in any one of claims 1-3, a uniform resin film is easily formed even when the surface of the glass material has a non-planar portion. The coating material for preventing glass scattering can be obtained.

According to invention of Claim 5, the effect of the invention in any one of Claims 1-4 can be exhibited more effectively. In particular, the effect of the invention of claim 4 can be more effectively exhibited.

According to invention of Claim 6, the coating material for glass scattering prevention of Claim 2 can be manufactured easily just before coating. Thereby, it is possible to prevent the reaction between the acrylic resin and the silane coupling agent from proceeding before coating, and the effect of the invention according to claim 2 can be sufficiently obtained.

According to the seventh aspect of the present invention, it is possible to obtain an anti-scattering glass material that makes it difficult for the glass to scatter when the glass is broken.

  The coating material for preventing glass scattering according to the present invention is a coating material for forming a resin film on the surface of a glass material, contains an acrylic resin and silica fine particles, and 10 silica fine particles per 100 parts by mass of the acrylic resin. -150 parts by mass.

  The glass material is not particularly limited. For example, architectural glass materials such as window glass, glass materials for electrical appliances such as glass substrates for liquid crystal displays and plasma substrates, and lighting equipment such as fluorescent lamps and light bulbs. Used glass materials, beakers, flasks, graduated cylinders, desiccators, glass rods, glass tubes, funnels and other glassware for chemical experiments, glass containers such as cups and bottles (other than glassware for chemical experiments), etc. Can be mentioned.

  The glass scattering prevention paint is suitable for use in glass containers among these glass materials, and is suitable for use in glass containers used as glassware for chemical experiments. Glass containers (especially glass containers used as glassware for chemical experiments) may be required to be transparent so that the contents can be easily seen. A highly reliable resin film can be easily formed.

The glass scattering prevention coating material is suitable for use on a glass material having a non-planar portion on the surface. Normally, if there is such a shape, it is difficult to form a uniform resin film because the thickness of the resin film varies. However, if the coating material for preventing glass scattering is used, a uniform resin film can be formed even if there is such a shape. It is easy to obtain sufficient anti-scattering performance. If the resin film is not uniform, sufficient scattering prevention performance may not be obtained.
The non-planar portion specifically refers to a portion that is not a flat surface, such as a curved surface, a surface having irregularities, an entrance corner, and an exit corner. The entrance corner includes not only the inner corner where the two planes meet, but also the inner corner where the two curved surfaces meet and the inner corner where the plane and the curved surface meet. Similarly, the protruding corner includes not only the outer corner where the two planes meet but also the outer corner where the two curved surfaces meet and the outer corner where the plane and the curved surface meet. .

  The glass material preferably has a glass thickness of 0.5 to 10 mm (more preferably 0.8 to 6 mm, particularly preferably 1 to 5 mm). When the thickness is within this range, the glass material is easily broken, and fragments are easily scattered by the impact when broken, so that the effect of the glass scattering preventing paint can be further exhibited. When the thickness is less than 0.5 mm, the size of the glass material is generally small, so that the impact when broken is small and there is little risk of debris scattering over a wide area. On the contrary, if the thickness exceeds 10 mm, the impact when cracked is large, and thus there is a possibility that scattering cannot be sufficiently suppressed.

  The resin film is obtained by drying or curing a glass scattering prevention paint. The dry film thickness of the resin film is preferably 50 to 1000 μm (more preferably 80 to 800 μm, particularly preferably 100 to 500 μm). If the dry film thickness is within this range, sufficient scattering prevention performance can be obtained. When the dry film thickness is less than 50 μm, it is difficult to obtain sufficient scattering prevention performance. On the contrary, when the dry film thickness exceeds 1000 μm, depending on the use of the glass material for forming the resin film, the thermal conductivity of the resin film is smaller than the thermal conductivity of the glass. On the other hand, problems such as difficulty in cooling may occur.

  Below, the detail of each component which comprises the said glass scattering prevention coating material is demonstrated.

(acrylic resin)
The acrylic resin is a resin having (meth) acrylic acid ester and / or (meth) acrylic acid as a main monomer. In the present specification, (meth) acrylic acid means acrylic acid or methacrylic acid. As for the acrylic resin used for the said glass scattering prevention coating material, it is preferable that the content rate of (meth) acrylic acid ester and (meth) acrylic acid in an acrylic resin is 80 mass% or more (more preferably 95 mass% or more). . When the content ratio is within this range, it is easy to obtain a glass anti-scattering paint excellent in anti-scattering performance, and it is easy to ensure transparency of the resin film.

Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, (n-propyl) (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid-n. -Butyl, (meth) acrylate isobutyl, (meth) acrylate-t-butyl, (meth) acrylate-2-ethylhexyl, lauryl methacrylate, phenyl acrylate, isobornyl (meth) acrylate, cyclohexyl methacrylate, (Meth) acrylic acid-t-butylcyclohexyl, (meth) acrylic acid dicyclopentadienyl, (meth) acrylic acid dihydrodicyclopentadienyl, (meth) acrylic acid-1-hydroxyethyl, (meth) acrylic acid- 2-hydroxyethyl, 1-hydroxypropyl (meth) acrylate (Meth) acrylic acid 1-hydroxybutyl, and the like glycidyl methacrylate.

The acrylic resin may contain a compound copolymerizable with (meth) acrylic acid ester as required. Such a compound is not particularly limited. For example, aromatic vinyl monomers such as styrene, vinyl toluene, α-methyl styrene, vinyl naphthalene, and halogenated styrene, vinyl ester monomers such as vinyl acetate, vinyl chloride, Vinyl halide monomers such as vinylidene chloride, (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethylacrylamide, etc. Examples thereof include amide group-containing vinyl monomers, nitrile group-containing monomers such as acrylonitrile, vinyl ether monomers, itaconic acid, maleic acid, crotonic acid, tiglic acid, and cinnamic acid.
For example, for the purpose of improving the water resistance of a resin film with a glass scattering prevention coating material, the content of styrene in the acrylic resin is 1 to 20% by mass (more preferably 3 to 15% by mass, particularly preferably 5 to 10% by mass). ). If the said content rate exists in this range, the water resistance of a resin film will improve. When the content is less than 1% by mass, the water resistance of the resin film is not sufficiently improved. On the other hand, when the content exceeds 20% by mass, the resin film is easily discolored when affected by ultraviolet rays or the like.

The form of the acrylic resin is not particularly limited. For example, an emulsion or a water-soluble resin can be used. Two or more kinds of acrylic resins may be mixed and used.

The acrylic resin preferably has a glass transition point (Tg) of −50 to 40 ° C. (more preferably −40 to 10 ° C., particularly preferably −30 to −10 ° C.). If the Tg is within this range, it is easy to obtain a glass scattering preventing paint having excellent scattering preventing performance. When the Tg is less than −50 ° C., since the tensile strength of the resin film is small, the resin film is easily broken by an impact when the glass material is broken, and the resin film is broken at the edge of the glass piece. Since it becomes easy, there exists a possibility that scattering prevention performance may fall. On the other hand, when the Tg exceeds 40 ° C., the flexibility of the resin film is reduced, so that when the glass material is broken, the resin film is broken together, so that the scattering prevention performance may be lowered.
In addition, Tg of an acrylic resin can be measured by the method shown by JISK7121-1987 "Plastic transition temperature measuring method", for example.

  The content of the acrylic resin contained in the glass scattering prevention coating is 35 to 90% by mass (more preferably 45 to 85% by mass, particularly preferably 50 to 75% by mass) in the nonvolatile content of the glass scattering prevention coating. %). If the said content rate exists in this range, while being easy to obtain the coating material for glass scattering prevention excellent in scattering prevention performance, it is easy to ensure the transparency of a resin film. When the content is less than 35% by mass, sufficient transparency may not be obtained. On the contrary, when the content exceeds 90% by mass, the scattering prevention performance may be deteriorated.

(Silica fine particles)
As described above, the silica fine particles are silica particles having a primary particle diameter of 1 to 500 nm, and are contained in the glass scattering prevention coating material in an amount of 10 to 150 parts by mass with respect to 100 parts by mass of the acrylic resin. The When the silica fine particles are contained in an amount in this range with respect to the acrylic resin, sufficient scattering prevention performance can be obtained.
The anti-scattering performance is improved by the silica fine particles because the adhesion between the resin film and the glass material is moderately improved, and the balance between the tensile strength and flexibility of the resin film is suitable for preventing scattering. I guess that. Note that if the resin film and the glass material are not sufficiently adhered, the glass may be scattered due to separation of the resin film and the glass material when the glass material is broken. On the other hand, even if the glass material is broken, the resin film may be broken together when the glass material is broken, so that the glass at the portion where the resin film is broken may be scattered. Further, when the glass material is a glass container, there is a risk that the liquid or the like contained in the glass container may leak due to the resin film breaking.

The primary particle diameter of the silica fine particles is 1 to 500 nm (more preferably 2 to 250 nm, particularly preferably 5 to 150 nm). When the primary particle diameter is within this range, a glass scattering preventing paint excellent in scattering preventing performance can be obtained. When the primary particle diameter exceeds 500 nm, the resin film and the glass material are not sufficiently adhered to each other, so that sufficient scattering prevention performance may not be obtained. On the other hand, when the average primary particle size is less than 1 nm, the stability of the coating material for preventing glass scattering tends to decrease, so that the volatile content is increased to lower the concentration of the coating material in order to obtain sufficient stability. There is a need. It is difficult to obtain a uniform resin film with a glass scattering prevention paint with reduced stability, and it is difficult to obtain a resin film with a sufficient thickness to exhibit scattering prevention performance with a paint with a reduced concentration.

  The content of the silica fine particles contained in the glass scattering prevention coating is 10 to 150 parts by mass (more preferably 20 to 100 parts by mass, particularly preferably 30 to 80 parts by mass) with respect to 100 parts by mass of the acrylic resin. It is. When the content is within this range, a glass scattering preventing paint excellent in scattering preventing performance can be obtained. When the content exceeds 150 parts by mass with respect to 100 parts by mass of the acrylic resin, the resin film becomes hard and the resin film and the glass material are in close contact with each other, thereby obtaining sufficient scattering prevention performance. There is no fear. There is a fear. On the other hand, when the content is less than 10 parts by mass with respect to 100 parts by mass of the acrylic resin, the resin film and the glass material are not sufficiently adhered to each other, so that sufficient scattering prevention performance cannot be obtained. There is a fear.

When silica fine particles are contained in the glass scattering prevention coating material, it is preferable to use those in the form of colloidal silica, silica sol or silica gel. When the silica fine particles having such a form are used, the coating can be easily manufactured. In addition, when using the thing of an emulsion form as an acrylic resin, it is preferable to use colloidal silica. Colloidal silica can be easily mixed in the emulsion, and the adhesion between the resin film and the glass material is appropriately improved, so that the scattering prevention performance can be particularly improved.

(Crosslinking agent)
The glass scattering prevention coating material preferably contains a crosslinking agent in addition to the acrylic resin and the silica fine particles. In addition, when making a glass scattering prevention coating contain a crosslinking agent, you may mix a crosslinking agent with acrylic resin etc. previously, and you may mix just before coating.

As the crosslinking agent contained in the glass scattering prevention coating material, a silane coupling agent is preferable. By using a silane cup agent, the resin film formed with the glass scattering prevention coating material becomes tough, and the scattering prevention performance can be improved. The reason why the resin film becomes tough is presumed to be that the adhesion between the acrylic resin and the silica fine particles is improved by the silane coupling agent.
Further, by using the silane cup agent, it is possible to prevent the resin film from being discolored when the glass material reaches a high temperature of 160 ° C. or higher, and to improve the chemical resistance of the resin film. When the glass material is heated to a high temperature of 160 ° C. or higher, the resin film may be discolored, but such discoloration can be suppressed by containing a silane coupling agent. In addition, if the glass material is washed with a cleaner, detergent, etc., the resin film may suffer from problems such as discoloration or alteration. However, by improving the chemical resistance of the resin film, Problems can be made difficult to occur.

The silane coupling agent generally has a structure represented by R—Si (OR ′) ₃ (a plurality of R ′ may be the same or different. R ′ is usually an alkyl group). , R is a silane compound having a reactive group such as an epoxy group, a carboxyl group, a (meth) acryloyl group, an isocyanate group or an amino group. For example, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxy Silane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ -Acryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -Γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltri Examples thereof include methoxysilane and γ-ureidopropyltriethoxysilane.

The content of the silane coupling agent contained in the glass scattering prevention coating is 0.5 to 10 parts by mass (more preferably 1 to 8, particularly preferably 2 to 6 parts by mass with respect to 100 parts by mass of the acrylic resin. Part). If the content is within this range, chemical resistance can be improved without reducing the scattering prevention performance of the glass scattering prevention coating material. When the content is less than 0.5 parts by mass with respect to 100 parts by mass of the acrylic resin, the scattering prevention performance is not sufficiently improved, and the effect of suppressing discoloration and improving chemical resistance is sufficiently obtained. Absent. On the contrary, when the content exceeds 10 parts by mass with respect to 100 parts by mass of the acrylic resin, the flexibility of the resin film is reduced, and therefore the resin film is broken together when the glass material is broken. As a result, the glass at the portion where the resin film is broken may be scattered.

  As the crosslinking agent contained in the glass scattering prevention coating material, one or more types of crosslinking agents selected from isocyanate compounds, oxazoline compounds, and carbodiimide compounds are preferable. By using such a crosslinking agent, scattering prevention performance can be improved, and a uniform resin film can be formed even when the surface of the glass material has a non-planar portion. In addition, when the resin film is not uniform, there is a possibility that the anti-scattering performance of the resin film is deteriorated.

  The isocyanate compound is a compound having two or more isocyanate groups in the molecule. For example, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphite, P-phenylene diisocyanate, xylylene diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, Examples include monomers such as hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, trimethylolpropane adducts, isocyanurate modified products, biuret modified products, carbodiimide modified products, urethane modified products, and allophanate modified products of these monomers. be able to.

  The oxazoline compound is a compound having two or more oxazoline groups in the molecule. For example, 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4,4-oxazoline, 4,4-dimethyl-2-vinyl-5,6-dihydro-4H-1, -oxazine 4,4,6-trimethyl-2-vinyl-5,6-dihydro-4H-1,3-oxazine, 2-isopropenyl-2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline , 4-acryloyl-oxymethyl-2,4-dimethyl-2-oxazoline, 4-methacryloyl-oxymethyl-2,4-dimethyl-2-oxazoline, 4-methacryloyl-oxymethyl-2-phenyl-4-methyl-2 -Oxazoline, 2- (4-vinylphenyl) -4,4-dimethyl-2-oxazoline, 4-ethyl-4-hydroxymethyl-2-yl Propenyl-2-oxazoline, 4-ethyl-4-ethoxymethyl-2-isopropenyl-2-oxazoline, and the like.

  The carbodiimide compound is a compound containing two or more carbodiimide groups in the molecule. For example, 4,4'-diphenylmethanecarbodiimide, p-phenylenecarbodiimide, m-phenylenecarbodiimide, diisopropylphenylcarbodiimide, triisopropylphenylcarbodiimide, dicyclohexylmethanecarbodiimide, diisopropylcarbodiimide and the like can be mentioned.

  The content of the one or more crosslinking agents selected from the isocyanate compound, oxazoline compound, and carbodiimide compound is 1 to 55 parts by mass (more preferably 2 to 40 parts by mass, particularly 100 parts by mass of the acrylic resin). It is preferably 5 to 20 parts by mass). When the content is within this range, a glass scattering prevention paint having particularly excellent scattering prevention performance can be obtained, and a uniform resin film can be easily formed even when the surface of the glass material has a non-planar portion. Can do. When the content exceeds 55 parts by mass with respect to 100 parts by mass of the acrylic resin, the resin film and the glass material are not sufficiently adhered to each other, and thus the scattering prevention performance may be deteriorated. On the contrary, when the content is less than 1 part by mass with respect to 100 parts by mass of the acrylic resin, the effect of improving the scattering prevention performance cannot be sufficiently obtained.

(Other ingredients)
The glass scattering prevention coating material may contain components other than those described above as necessary. For example, the additive used for a general coating material can be contained. Examples of the additives include viscosity modifiers, dispersants, wetting agents, antifoaming agents, film-forming aids, antifreezing agents, antioxidants, ultraviolet absorbers, light stabilizers, and preservatives. .

  The glass scattering prevention paint may be colored with a pigment as necessary. What is necessary is just to use what is generally used for a paint as the pigment, for example, titanium oxide, zinc oxide, chrome lead, zinc white, yellow iron oxide, bengara, carbon black, cadmium red, molybdenum red, chromium yellow, Inorganic color pigments such as chromium oxide, Prussian blue, cobalt blue, azo pigment, diketopyrrolopyrrole pigment, benzimidazolone pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, isoindolinone pigment, selenium pigment, perylene pigment, Examples thereof include organic color pigments such as perinone pigments and dioxane pigments.

(Manufacturing method and resin film forming method)
There is no particular limitation on the method for producing the glass scattering preventing paint. For example, it can be produced by mixing acrylic resin and silica fine particles. Or it can manufacture by adding a silica particle during the copolymerization of an acrylic resin monomer, or copolymerizing while mixing an acrylic resin monomer and a silica particle. Examples of such a material include silica fine particle-containing emulsions obtained by emulsion polymerization in the presence of silica fine particles as described in paragraph 0017 of JP-A-07-325390.
Moreover, when it contains components other than an acrylic resin and a silica particle, it can manufacture by mixing an acrylic resin, a silica particle, and components other than those. In addition, when manufacturing the coating material for glass scattering prevention in this way, each component may be mixed previously and may be mixed just before coating. As a method of mixing immediately before painting, a method in which some components are mixed in advance and the remaining components are mixed, a method in which components are mixed in advance and mixed in advance. Can be mentioned.

  When the glass scattering prevention paint contains a crosslinking agent, it is preferable to mix the crosslinking agent immediately before coating. If the acrylic resin and the crosslinking agent are mixed in advance, the reaction between the acrylic resin and the crosslinking agent may proceed before coating. When mixing the crosslinking agent immediately before coating, the acrylic resin and the crosslinking agent may be mixed by any method as long as the acrylic resin and the crosslinking agent are not mixed in advance. For example, the acrylic resin, silica fine particles, and other components are mixed in advance. For example, a method of mixing a crosslinking agent immediately before coating may be used.

If it manufactures by the said method, the coating material for glass scattering prevention can be manufactured easily just before coating. If it manufactures immediately before coating, it can prevent that reaction with an acrylic resin and a crosslinking agent advances before coating, and can fully acquire the effect acquired by containing a crosslinking agent.

  A method for forming a resin film on the surface of the glass material with the glass scattering prevention coating is not particularly limited. For example, glass spraying by a spray coating method using a coating machine such as airless spray or air spray, a coating method using a coating device such as a roller or a brush, or a dipping method without using a coating device or a coating device. A resin film can be formed by applying a coating for prevention and drying.

The method for drying the glass scattering preventing coating is not particularly limited. Not only a method of drying in an environment of normal temperature and humidity, but also a method of drying in a high temperature environment or a low humidity environment using a drying furnace or the like can be employed.

(Test 1)
A drop test was performed by preparing a resin film made of the paint shown in Tables 1 and 2 on the entire outer surface of a glass eggplant-shaped flask as a glass material.
In Tables 1 and 2, the materials used for the paint and their blending amounts are described in parts by mass.

An eggplant type flask with a capacity of 1000 ml and a glass thickness of 2.8 mm was used.

  Details of the materials used for the paints shown in Tables 1 and 2 are described below.

The silica fine particle-containing acrylic resin emulsion is an emulsion produced by copolymerizing an acrylic resin monomer and silica fine particles while mixing. In the total amount of the emulsion, 28% by mass of acrylic resin and 15% by mass of silica fine particles are contained as nonvolatile components, 52% by mass of water and 5% by mass of additives are contained as volatile components. Moreover, the content rate of the (meth) acrylic acid ester and (meth) acrylic acid in an acrylic resin is 98 mass% or more, and the average primary particle diameter of the silica fine particle measured by BET method is 40 nm. The Tg of the acrylic resin is -18 ° C.

  The acrylic resin emulsion contains 50% by mass of an acrylic resin as a non-volatile component, 45% by mass of water, and 5% by mass of an additive as a volatile component in the total amount of the emulsion. Moreover, the content rate of the (meth) acrylic acid ester and (meth) acrylic acid in an acrylic resin is 98 mass% or more. The Tg of the acrylic resin is -20 ° C.

  In colloidal silica, the average primary particle diameter of silica fine particles measured by the BET method is 50 nm, and the non-volatile content is 40 mass%.

  The isocyanate compound is a mixture of HDI (hexamethylene diisocyanate) trimer type polyisocyanate and HDI allophanate type polyisocyanate, and the mixing ratio thereof is 1: 1 by mass ratio. The non-volatile content is 100% by mass.

  The oxazoline compound is an oxazoline group-containing polymer, and its nonvolatile content is 40% by mass.

  The carbodiimide compound is a carbodiimide group-containing polymer (polycarbodiimide), and its non-volatile content is 40% by mass.

  The silane coupling agent is 3-glycidoxypropyltrimethoxysilane, and the non-volatile content is 100% by mass.

  As other additives, viscosity modifiers, wetting agents, antifoaming agents, and film-forming aids were used.

  Each paint was applied with an air spray and then dried in an environment at a temperature of 40 ° C. When it was difficult to obtain a predetermined film thickness by a single coating, the paint was applied repeatedly until a predetermined film thickness was obtained after drying. The thickness of the formed resin film is shown in Tables 1 and 2.

  Tables 1 and 2 also describe the acrylic resin content in the non-volatile content of the paint, and the colloidal silica content relative to 100 parts by mass of the acrylic resin.

Using the eggplant-shaped flask on which the resin film was formed as described above, the scattering prevention performance was evaluated by the following test.
With the mouth of the eggplant-shaped flask facing upward, it was dropped onto the concrete and the presence or absence of glass pieces was confirmed. In addition, the height of dropping was 50 cm and 30 cm from the concrete.

The presence or absence of scattering of glass pieces was evaluated according to the following criteria.
○: No scattering of glass.
(Triangle | delta): The thing where the scattering of glass is settled within the radius 50cm of a fall point.
X: Glass scattered over a radius of 50 cm at the point of drop.

  Moreover, the same test was done also about the eggplant type flask in which the resin film is not formed as the comparative example 4. Tables 3 and 4 show the results of the test.

When a coating material containing an appropriate amount of colloidal silica, which is silica fine particles, was used, a resin film having sufficient scattering prevention performance was obtained. If the amount of colloidal silica is too small or too large, a resin film having sufficient anti-scattering performance could not be obtained.
When a cross-linking agent was used, a resin film having better scattering prevention performance was obtained.

  In addition to colloidal silica, a paint containing a crosslinking agent of any one of a silane coupling agent, an isocyanate compound, an oxazoline compound, and a carbodiimide compound is used compared to a paint containing no crosslinking agent. Improved scattering prevention performance.

(Test 2)
A drop test was performed using the paint produced in the Example of Test 1 or the Comparative Example.
In Test 2, a test piece was prepared by forming a resin film with a paint on the entire outer surface of a glass cup as a glass material in the same manner as in Test 1.

A cup with a capacity of 250 ml and a glass thickness of 3.4 mm was used.

Table 5 shows the paint used and the film thickness of the formed resin film.
In addition, about the used coating material, it is described by the number of the Example or the comparative example which Example of the test 1 or the coating material of the comparative example was used.

In the state where the mouth of the cup on which the resin film was formed as described above was faced up, it was dropped on the concrete to confirm the presence or absence of scattering of the glass pieces. In addition, the height of dropping was 50 cm and 30 cm from the concrete.

The presence or absence of scattering of glass pieces was evaluated according to the following criteria.
○: No scattering of glass.
(Triangle | delta): The thing where the scattering of glass is settled within the radius 50cm of a fall point.
X: Glass scattered over a radius of 50 cm at the point of drop.

  Moreover, the same test was done also about the cup in which the resin film is not formed as the comparative example 8. The results of the test are shown in Table 6.

When a paint containing an appropriate amount of colloidal silica, which is a silica fine particle, was used, a resin film having sufficient scattering prevention performance was obtained. If the amount of colloidal silica is too small or too large, a resin film having sufficient anti-scattering performance could not be obtained.

Claims (7)

A glass scattering prevention paint for forming a resin film on the surface of a glass material, the paint containing an acrylic resin and silica fine particles, and silica fine particles of 10 to 150 masses per 100 parts by mass of the acrylic resin. A paint for preventing glass scattering, characterized by being a part.   The silane coupling agent is contained, The glass scattering prevention coating material of Claim 1 characterized by the above-mentioned.   The paint for preventing glass scattering according to claim 2, wherein 0.5 to 10 parts by mass of a silane coupling agent is contained with respect to 100 parts by mass of the acrylic resin. The paint for preventing glass scattering according to any one of claims 1 to 3, comprising at least one crosslinking agent selected from an isocyanate compound, an oxazoline compound, and a carbodiimide compound.   The glass scattering prevention paint according to any one of claims 1 to 4, wherein the surface of the glass material has a non-planar portion.   It is a manufacturing method of the coating material for glass scattering prevention of Claim 2, Comprising: 10-150 mass parts silica particulates with respect to 100 mass parts of acrylic resins, and a silane coupling agent are mixed. A method for producing a coating material for preventing glass scattering. An anti-scattering glass material, wherein a resin film having a thickness of 50 to 1000 μm is formed on the surface of the glass material by the glass anti-scattering paint according to claim 1.