JP2002265238A - Automobile side glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an automobile side glass of thin thickness which is excellent in impact resistance, penetration resistance, scuffing resistance and durability. SOLUTION: In this automobile side glass which is made by laminating one sheet of glass and a film comprising an organic polymer via a transparent adhesive layer comprising an organic resin, the transparent adhesive layer consists of a triallyl isocyanurate crosslinked derivative of ethylene-vinyl acetate copolymer, and a hard coat layer consisting of a hardened coated film of a curable resin containing silica fine particles is disposed on the surface of the side which is not in contact with the transparent adhesive layer of the organic polymer film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to scratch resistance, impact resistance, penetration resistance, which is preferably used for automobile side glass.
Glass with excellent durability, etc.
The present invention relates to an automobile side glass having two glass plates and a method for manufacturing the same.

[0002]

2. Description of the Related Art In general, laminated glass having a structure in which a transparent adhesive layer (intermediate film) made of an organic resin is sandwiched between glass plates is used for glass used for automobiles, particularly for windshields. The transparent adhesive layer is formed of, for example, a PVB film or the like, and the presence of the transparent adhesive layer improves the penetration resistance and the like of the laminated glass. In addition, broken glass fragments remain stuck to the transparent adhesive layer in response to an external impact, thereby preventing the glass fragments from scattering. For this reason, for example, even if the laminated glass of an automobile is broken for theft, intrusion, or the like, the window cannot be freely opened, so that it is also useful as security glass.

On the other hand, for example, side glass such as automobile door glass and glazed glass is generally less likely to be broken in an accident, and does not require the same penetration resistance as the above-mentioned windshield. Low one
Two glass plates are used. However, when only such one glass plate is used, there are the following disadvantages. That is, (1) it is inferior to laminated glass in terms of impact resistance and penetration resistance, etc. (2) If it is broken for theft or intrusion, it breaks into many pieces and the windows can be freely opened. Cannot do it, etc. For this reason, it is desired to use glass having characteristics such as laminated glass also for the door glass and the fitted glass.

[0004] Such laminated glass, particularly for door glass of automobiles, is disclosed in, for example, JP-A-61-155.
No. 232 discloses a safety glass in which a plastic film is laminated on a glass surface via an ethylene / vinyl acetate copolymer (EVA) -based intermediate film, and a hardened surface film is formed on the plastic film. I have.

[0005] As described above, the door glass and the like are usually single-pane glass, and the thickness, strength, and the like of the above-mentioned laminated glass for windshield are not usually required.
Further, since the laminated glass of two glasses has a certain thickness, it may not be used for side glass and fitted glass, for example, for a small car having a relatively small size.

Accordingly, the laminated glass having a three-layer structure comprising the glass, the intermediate layer and the film disclosed in the above publication is
It is suitable for door glass and the like.

That is, it can be said that the film has a thin film reinforced glass which has the above-mentioned impact resistance and penetration resistance as well as security, and can be manufactured relatively easily.

However, the laminated glass having the three-layer structure is more easily scratched on the surface of the plastic film than on the surface of the glass. In the above publication, a surface cured film is provided, which is a cured organic polysiloxane film or a self-healing surface film such as polyurethane, and the former is complicated and expensive to manufacture, and the latter is inferior in hardness. Sufficient and easily damaged.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention, which has been made in view of the above points, is that it has good abrasion resistance, can be easily manufactured, has excellent penetration resistance, and has excellent security.
It is still another object of the present invention to provide a side glass for a vehicle made of a thin film-reinforced glass having excellent long-term transparency and excellent adhesion between a film and glass.

[0010]

Means for Solving the Problems The inventors of the present invention have made an effort to obtain a thin film reinforced glass having a good abrasion resistance, which can be easily manufactured, and which has excellent penetration resistance and a security property. As a result of intensive studies, one glass plate and a film made of an organic polymer are a film-reinforced glass laminated through a transparent adhesive layer made of an organic resin, and In order to obtain a film-reinforced glass, a hard coat layer composed of a cured film of a curable resin containing silica fine particles (generally, an ultraviolet curable resin) is provided on the surface not contacting the adhesive layer. It has arrived. The present applicant has already filed a patent application for this invention (Japanese Patent Application No. 2000-3873).
No. 91).

However, according to the study of the present inventors, when a film reinforced glass in which glass and an organic polymer film are sandwiched by an organic resin is used for a side glass for an automobile, it is subject to severe operating conditions in which windows are opened and closed. Exposure revealed that although the abrasion resistance was improved by the hard coat layer, whitening or peeling could occur from the edge of the glass. This is because, when used for a side glass, unlike the windshield, the transparent adhesive layer is exposed at the glass edge, and the moisture resistance is insufficient, so that the whitening and the decrease in the adhesiveness are found. Was. In order to solve this, as a result of repeated studies by the present inventors, the use of a crosslinked product of triallyl isocyanurate of an ethylene-vinyl acetate copolymer as the organic resin of the transparent adhesive layer has significantly improved moisture resistance, whitening,
It was found that the adhesion was improved. In addition, it is considered that the use of this cross-linked material for the transparent adhesive layer improves the adhesive strength, and also reduces the adhesive failure due to curing shrinkage observed during the formation of the hard coat. Further, it has been found that it is effective to use γ- (methacryloxypropyl) trimethoxysilane at that time.

Accordingly, the present invention provides an automobile side glass in which one glass plate and a film made of an organic polymer are laminated via a transparent adhesive layer made of an organic resin, wherein the transparent adhesive layer is made of A hard coat layer comprising a cured coating of a curable resin containing fine silica particles on the surface of the organic polymer film on the side not in contact with the transparent adhesive layer, comprising a crosslinked product of triallyl isocyanurate of ethylene vinyl acetate copolymer Is provided in the automobile side glass.

In the above-mentioned film-reinforced glass, the primary particle size of the silica fine particles is preferably in the range of 1 to 200 nm, and particularly preferably in the range of 10 to 100 nm. Further, the silica fine particles have a polymerizable unsaturated group, and in particular, those formed by a reaction between the silica fine particles and an alkoxysilane compound having a polymerizable unsaturated group (and preferably a urethane bond) are preferable.

Preferably, an antireflection layer is formed on the surface of the hard coat layer. The antireflection layer is preferably composed of a high-refractive-index conductive layer (preferably an ITO film) and a low-refractive-index layer thereon (preferably an SIO ₂ layer). Alternatively, a combination of an organic polymer film, a hard coat layer, and an antireflection layer preferably has a light transmittance at 365 nm of 40% or less.

Preferably, the organic polymer is polyethylene terephthalate.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION
One glass plate, an automobile of a film reinforced glass in which a film composed of an organic polymer and a transparent adhesive layer containing a triallyl isocyanurate crosslinked product of ethylene vinyl acetate copolymer (hereinafter also referred to as “EVAT”) as a main component and an organic polymer are laminated. A side-glass, film-reinforced glass in which a hardened layer of hardening resin containing silica fine particles as a hard coat layer (generally an ultraviolet-curing resin) is provided on the film, and is particularly excellent in scratch resistance, crime prevention, and durability. It is a thing. The EVAT can include additives such as a silane coupling agent, a plasticizer, and an organic peroxide. For the film made of an organic polymer, for example, polyethylene terephthalate (hereinafter, referred to as “PET”) is used.

The film-reinforced glass of the present invention is particularly excellent in abrasion resistance in spite of being easily manufactured by such a structure, has moderate performance in impact resistance, penetration resistance, and the like, and has moisture resistance. It is also excellent in durability due to. For this reason, it is suitable for use as an automobile side glass (that is, a door glass or a side-inserted glass). In other words, from the viewpoint of crime prevention, such glass is prevented from easily entering from the outside due to destruction or the like, but has impact resistance and penetration resistance that can be broken in an emergency such as an accident. Is also needed. Furthermore, since the automotive side glass of the present invention has improved moisture resistance, even when used in a door glass in which a window is opened and closed, there is no whitening of the glass edge or occurrence of peeling of the film, and a long term. It is possible to use.

Hereinafter, the automobile side glass of the present invention will be described in detail with reference to FIGS.

In FIG. 1, a transparent adhesive layer 2 and a film 3 made of an organic polymer are formed on the surface of one glass plate 1.
Are laminated, and a hard coat layer 4 is provided on the surface of the film 3. The transparent adhesive layer 2 has a slightly poor transparency, but from the viewpoint of durability such as water resistance and adhesiveness,
Triallyl isocyanurate crosslinked ethylene vinyl acetate copolymer is used. As the organic polymer of the film 3, for example, PET is preferably used. The specific hard coat layer 4 of the present invention is formed on the surface of the organic polymer film 3, thereby improving the scratch resistance. Since this layer usually faces the interior side of a vehicle or the like, it is provided to prevent scratches caused by touching or hitting an object.
Such concerns are unnecessary because the glass is directly exposed on the outside. The hard coat layer of the present invention can be easily formed, has a hardness close to that of a glass surface, and is excellent in transparency.

Since the automobile side glass having such a structure is used as an automobile side glass, it is exposed to severe operating conditions in which windows are opened and closed, and the abrasion resistance is improved by the hard coat layer. Then, whitening or peeling may occur from the glass edge. This is because, when used as a side glass, unlike the windshield, the transparent adhesive layer is exposed at the end of the glass, and its moisture resistance is insufficient, so that the whitening and the decrease in the adhesiveness occur. However, by using the crosslinked product of triallyl isocyanurate of the ethylene-vinyl acetate copolymer of the present invention as the organic resin of the transparent adhesive layer, the moisture resistance is greatly improved. Therefore, even if it is used for a door glass in which a window is opened and closed as described above, whitening of the glass edge,
The film can be used for a long time without peeling of the film.

Further, in the above automobile side glass, since the hard coat layer is provided on the organic polymer film, the adhesiveness between the organic polymer film and the glass may be reduced due to shrinkage of the hardening when the hard coat layer is formed. is there. However, by using the crosslinked product of triallyl isocyanurate of the ethylene-vinyl acetate copolymer of the present invention as the organic resin of the transparent adhesive layer, the adhesiveness is greatly improved. Therefore, even when used for a door glass in which a window is opened and closed as described above, it is considered that there is no occurrence of peeling of the film, and it can be used for a long time.

The organic polymer film 3 is provided to significantly prevent breakage of the glass. Therefore,
By using such a film and adopting the above-described configuration, the above-described performance can be obtained even with a single glass plate. Excellent film tempered glass can be used.

Further, it is preferable to provide an antireflection layer on the hard coat layer of the present invention. This allows
When you look out from the window, you can see the scenery without glare. Further, the hard coat layer containing the silica fine particles of the present invention has good adhesion to the antireflection layer, and the durability of the film-reinforced glass provided with the antireflection layer is improved.

FIG. 2 is a sectional view taken along the line AA 'of FIG. The transparent adhesive layer 2 sandwiched between a single glass plate 1 and a film 3 made of an organic polymer has a low penetration resistance when the thickness is small and a low transparency when the thickness is large. In the case of the side glass of the automobile of the present invention, the transparent adhesive layer does not need to be as thick as the windshield.
Generally within the range of 1 to 10 mm, 0.3 to 3 mm
Is preferably within the range. Similarly, the thickness of the film 3 made of an organic polymer is generally in the range of 0.1 to 2 mm, and preferably in the range of 0.5 to 1 mm.

To manufacture the automobile side glass of the present invention, first, a transparent adhesive layer 2 having the same shape as this glass plate is placed on the surface of one glass plate 1, and a film 3 made of an organic polymer having the same shape is formed. And press-bonding them. The pressure bonding is usually performed with a roll or the like under heating. The pressure bonding may be performed using an adhesive.
Next, a hard coat treatment is performed on the surface of the film 3 made of an organic polymer. Alternatively, a hard coat layer may be formed on the film 3 in advance, and a glass plate, a transparent adhesive layer and a film made of the organic polymer may be pressed.

Alternatively, when the transparent adhesive layer is EVA containing a photopolymerization initiator, the following simple method can be adopted. First, on the surface of one glass plate 1, a transparent adhesive layer 2 of EVA containing a photopolymerization initiator having the same shape as the glass plate is placed, and a film 3 made of an organic polymer having the same shape is placed. Then, a resin solution for forming a hard coat layer was applied, and the applied layer was dried or a release sheet was placed on the applied layer, and then the entire obtained laminate was vacuum degassed and pre-pressed. Thereafter, the coating layer or the transparent adhesive layer is cured by irradiating the coating layer or the release sheet with ultraviolet rays. As a result, a laminate in which four or five layers are firmly pressed can be obtained, thereby making it possible to manufacture an automobile side glass.

The release sheet may be placed after drying the coating layer. In particular, if the surface does not solidify even after drying the coating layer, it is preferable to provide the coating layer.

As described above, when the resin solution for forming a hard coat layer is cured by irradiation with ultraviolet rays, a photopolymerization initiator is contained in this solution and the organic resin film, and the coating layer and the organic resin film are irradiated with the ultraviolet rays. Curing (crosslinking) both simultaneously
Let it. Therefore, the crosslinking treatment of the organic resin film can be omitted.

The automobile side glass of the present invention has a structure in which a film 3 made of an organic polymer is laminated on the surface of one glass plate 1 via a transparent adhesive layer 2 and a hard coat layer is provided on the surface of the film 3. It is characterized by having. That is, EVAT used for the transparent adhesive layer 2 for bonding the film 3 to the glass 1 has excellent water resistance. Generally, since the door glass is freely moved up and down, the door glass frequently comes into contact with the window frame and is likely to be peeled off. However, since the automobile side glass of the present invention has improved adhesiveness and water resistance, peeling between one glass plate 1 and a film 3 made of an organic polymer can be significantly prevented. In addition, even if the glass plate is broken for the purpose of crime, the fragments remain adhered due to the presence of the transparent adhesive layer 2 and the windows are not easily opened, so that they can be used as security glass. Function.

One glass plate 1 of the present invention is usually a silicate glass. The thickness of the glass plate does not need to be as thick as a windshield, and is generally 1 to 10 mm.
3-5 mm is preferred. The one glass plate 1 is chemically or thermally strengthened.

The organic resin used for the transparent adhesive layer 2 of the present invention is an ethylene vinyl acetate copolymer crosslinked triallyl isocyanurate (EVAT). That is, a small amount of triallyl isocyanurate is added to the ethylene vinyl acetate copolymer, and the ethylene vinyl acetate copolymer is crosslinked with triallyl isocyanurate. Along with ethylene vinyl acetate copolymer (EVA), if desired, a polyvinyl acetal-based resin (eg, polyvinyl formal, polyvinyl butyral (PVB resin)),
Modified PVB) and vinyl chloride resin may be used.

The amount of triallyl isocyanurate is EV
In general, 0.1 to 20 parts by mass with respect to 100 parts by mass of A,
Preferably it is 0.5 to 10 parts by mass, especially 0.5 to 5 parts by mass. When the amount of triallyl isocyanurate is less than the above, transparency and adhesiveness decrease, and when it is too large, elongation decreases, which is not preferable.

EVA has a vinyl acetate content of 10 to 50.
It is preferable that the content be 15% by mass, particularly 15 to 40% by mass.
When the vinyl acetate content is less than 10% by mass, the transparency of the resin obtained when crosslinking and curing at a high temperature is not sufficient. On the contrary, when the content exceeds 50% by mass, the impact resistance in the case of making a security glass is obtained. , The penetration resistance tends to be insufficient.

In the present invention, in order to further increase the adhesive strength between the transparent adhesive layer 2 and one glass plate 1 and the film 3 made of an organic polymer, a silane coupling agent is added as an adhesion improver. Is preferred.

As an example of this silane coupling agent, γ
-Chloropropylmethoxysilane, vinylethoxysilane, vinyltris (β-methoxyethoxy) silane, γ
-(Methacryloxypropyl) trimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-
Examples include aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane. Among them, γ- (methacryloxypropyl) trimethoxysilane is particularly preferred. These silane coupling agents can be used alone or
It may be used in combination of more than one kind. The content of the compound is preferably 5 parts by mass or less, particularly preferably 0.1 to 3 parts by mass, based on 100 parts by mass of EVAT.

EVAT used for the transparent adhesive layer 2
The resin composition for use can contain various additives such as a plasticizer, an organic peroxide, and an adhesion improver.

The plasticizer is not particularly limited, but generally an ester of a polybasic acid or an ester of a polyhydric alcohol is used. Examples include dioctyl phthalate, dihexyl adipate, triethylene glycol-di-2-ethyl butyrate, butyl sebacate,
Examples thereof include tetraethylene glycol diheptanoate and triethylene glycol diperargonate. One plasticizer may be used, or two or more plasticizers may be used in combination. The content of the plasticizer is preferably 5 parts by mass or less based on 100 parts by mass of EVAT.

The above resin composition for EVAT generally contains an organic peroxide as an agent for controlling the adhesion to one glass plate 1 and a film 3 made of an organic polymer. Since the curability of the resin composition containing an organic peroxide is improved by heating, the film strength of the obtained transparent adhesive layer 2 is also improved.

As the organic peroxide, any organic peroxide can be used as long as it decomposes at a temperature of 100 ° C. or more to generate radicals. Organic peroxide is
In general, the temperature is selected in consideration of the film forming temperature, composition adjustment conditions, curing (bonding) temperature, heat resistance of the adherend, and storage stability. In particular, those having a decomposition temperature of 70 ° C. or more with a half-life of 10 hours are preferred.

Examples of the organic peroxide include 2,5-
Dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3-di-t-butylperoxide,
t-butylcumyl peroxide, 2,5-dimethyl-
2,5-di (t-butylperoxy) hexane, dicumyl peroxide, α, α′-bis (t-butylperoxyisopropyl) benzene, n-butyl-4,4-bis (t-butylperoxy) ) Valerate, 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-
Butylperoxy) cyclohexane, 1,1-bis (t
-Butylperoxy) -3,3,5-trimethylcyclohexane, t-butylperoxybenzoate, benzoyl peroxide, t-butylperoxyacetate, methylethylketone peroxide, 2,5-dimethyl-2,5-bis (t -Butylperoxy) -3,
3,5-trimethylcyclohexane, 1,1-bis (t
-Butylperoxy) cyclohexane, methyl ethyl ketone peroxide, 2,5-dimethylhexyl-2,
5-bisperoxybenzoate, t-butyl hydroperoxide, p-menthane hydroperoxide, p-chlorobenzoyl peroxide, hydroxyheptyl peroxide, chlorohexanone peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide Oxide, cumylperoxy octoate, succinic peroxide, acetyl peroxide, t-butylperoxy (2-ethylhexanoate), m-toluoyl peroxide, t-butylperoxyisobutyrate and 2,4 -Dichlorobenzoyl peroxide. One kind of the organic peroxide may be used, or two or more kinds may be used in combination. The content of organic peroxide is EVAT10
The range of 0.1 to 5 parts by mass relative to 0 parts by mass is preferred.

When the resin composition for EVAT is crosslinked by light, a photosensitizer (photopolymerization initiator) is used instead of the above peroxide.
Is usually 5 parts by mass or less, preferably 0.1 to 5.0 parts by mass, based on 100 parts by mass of EVAT.

Examples of the photopolymerization initiator include benzoin, benzophenone, benzoylmethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, dibenzyl,
Nitroacenaphthene, hexachlorocyclopentadiene, p-nitrodiphenyl, p-nitroaniline, 2,
Examples thereof include 4,6-trinitroaniline, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone and the like. These alone,
Alternatively, two or more kinds can be used in combination.

Transparent adhesive layer 2 comprising EVAT of the present invention
May further improve or adjust various physical properties (optical properties such as mechanical strength, adhesiveness, transparency, heat resistance, light resistance, cross-linking speed, etc.) of the film, if necessary, and particularly improve mechanical strength. Therefore, it may contain an acryloxy group-containing compound, a methacryloxy group-containing compound, and / or an epoxy group-containing compound other than triallyl isocyanurate.

The acryloxy group-containing compound and methacryloxy group-containing compound to be used are generally acrylic acid or methacrylic acid derivatives, for example, esters or amides of acrylic acid or methacrylic acid. Examples of ester residues include linear alkyl groups such as methyl, ethyl, dodecyl, stearyl, lauryl, etc., cyclohexyl, tetrahydrofurfuryl, aminoethyl, 2-hydroxyethyl, 3-hydroxypropyl And a 3-chloro-2-hydroxypropyl group. Further, esters of polyhydric alcohols such as ethylene glycol, triethylene glycol, polypropylene glycol, polyethylene glycol, trimethylolpropane, pentaerythritol and acrylic acid or methacrylic acid can also be mentioned.

Examples of the amide include diacetone acrylamide.

Examples of the polyfunctional compound include glycerin, trimethylolpropane, pentaerythritol and the like obtained by esterifying a plurality of acrylic acids or methacrylic acids, and triallyl cyanurate.

As the epoxy-containing compound, triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether,
1,6-hexanediol diglycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol (ethyleneoxy) ₅ glycidyl ether, pt-butylphenyl glycidyl ether, adipic acid diglycidyl ester, phthalic acid Examples thereof include diglycidyl ester, glycidyl methacrylate, and butyl glycidyl ether.

Transparent adhesive layer 2 comprising EVAT of the present invention
Can be produced, for example, by a method of obtaining a sheet-like material by ordinary extrusion molding, calendar molding, or the like. Further, the above-mentioned composition for EVAT is dissolved in a solvent, and this solution is coated on a suitable support with a suitable coating machine (coater).
By drying to form a coating film, a sheet-like material can be obtained.

Examples of the organic polymer used for the film 3 of the present invention include polyester, polycarbonate, acrylic resin, polyamide (eg, nylon) and the like. Polyester is preferable, and examples thereof include PET, polyethylene naphthalate, and polyethylene butyrate. PET is particularly preferable.

The hard coat layer 4 of the present invention is a layer composed of a cured film of a curable resin containing silica fine particles (generally, an ultraviolet curable resin). A hard coat layer having excellent scratch resistance can be provided on the film.

The silica fine particles have a primary particle size of 1 to 200.
It is preferably in the range of nm. Further, the silica fine particles have a polymerizable unsaturated group (preferably a polymerizable double bond group), and particularly a reaction between the silica fine particles and an alkoxysilane compound having a polymerizable unsaturated group (and preferably a urethane bond). Is preferably formed.

The silica fine particles are powdery silica or colloidal silica and have a primary particle size of 1 to 200 nm.
(Mμ), more preferably in the range of 10 to 100 nm. The shape of the silica fine particles is spherical, hollow, porous, rod-like, plate-like, fibrous, or indefinite,
Preferably it is spherical. The specific surface area of the silica fine particles is 0.1.
1 to 3000 m ² / g, preferably 10 to 150 m ² / g.
0 m ² / g. These silica fine particles can be used in the form of dry powder or in a state of being dispersed in water or an organic solvent, and a dispersion of fine silica particles known as colloidal silica can be directly used. In particular, in order to obtain transparency, it is preferable to use colloidal silica. When the colloidal silica dispersion solvent is water, its hydrogen ion concentration is 2 to 1 as a pH value.
In the range of 0, preferably, acidic colloidal silica having a pH of 3 to 7 is used. When the colloidal silica dispersion solvent is an organic solvent, the organic solvent may be methanol, isopropyl alcohol, ethylene glycol, or butanol.
May be used as a solvent such as toluene, ethylene glycol monopropyl ether, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, dimethylformamide, or a mixture thereof with an organic solvent or water compatible therewith. Preferred dispersing solvents are methanol, isopropyl alcohol, methyl ethyl ketone and xylene. Commercially available silica fine particles include, for example, colloidal silica such as methanol silica sol manufactured by Nissan Chemical Industries, Ltd., IPA-ST, MEK-ST, NBA-ST, and XB.
A-ST, DMAC-ST and ST-UP, ST-O
UP, ST-20, ST-40, ST-C, ST-N,
ST-O, ST-50, ST-OL and the like can be mentioned. Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600 and Aerosil OT600 manufactured by Nippon Aerosil Co., Ltd.
X50, Sildex H31, H3 manufactured by Asahi Glass Co., Ltd.
2, H51, H52, H121, H122, E220A, E220 manufactured by Nippon Silica Industry Co., Ltd. Sylysia 470 manufactured by Fuji Silysia K.K., S manufactured by Nippon Sheet Glass Co., Ltd.
G flake and the like can be mentioned.

As described above, the silica fine particles contained in the curable resin for forming a hard coat layer (generally, an ultraviolet curable resin) of the present invention include silica fine particles and a polymerizable unsaturated group (and preferably a urethane bond). It is preferably formed by reaction with an alkoxysilane compound having the same (hereinafter referred to as “modified silica fine particles”), and preferably has the following structure.

The above-mentioned modified silica fine particles of the present invention comprise a polymerizable unsaturated group and a urethane binding group, and a compound represented by the formula (I) -XC (= Y)
It is preferably a reaction product obtained by reacting an alkoxysilane compound having an organic group represented by —NH— with silica fine particles (in the above formula (I), X is —NH
-, -O- or -S-, and Y is an oxygen atom or a sulfur atom, provided that when X is -O-, Y is a sulfur atom).

The modified silica fine particles are produced by a method including an operation of mixing at least the alkoxysilane compound and the silica fine particles. The content of the alkoxysilane compound residue fixed on the silica fine particles is 0.01% by mass.
It is preferably at least 0.1% by mass, particularly preferably at least 1% by mass. When the content of the alkoxysilane compound residue fixed in the silica fine particles is less than 0.01% by mass, the dispersibility, transparency, and abrasion resistance of the silica fine particles or colloidal silica in the composition may not be sufficient. . Further, the ratio of the alkoxysilane compound in the raw material composition at the time of production is preferably at least 10% by mass, particularly preferably at least 30% by mass.
When the ratio of the alkoxysilane compound is less than 10% by mass, the film forming property of the ultraviolet curable resin may be poor. The ratio of the silica fine particles in the ultraviolet curable resin is preferably 50% by mass or less, and particularly preferably 20% by mass.
It is as follows. When the proportion of the silica fine particles in the ultraviolet curable resin is 50% by mass or more, the dispersibility, transparency, and abrasion resistance of the composition of the present invention may not be sufficient.

The alkoxysilane compound contains at least one polymerizable unsaturated group, a urethane bonding group, the organic group represented by the above formula (I), and at least one alkoxysilyl group in the molecule. An alkoxysilyl group is a component that binds to a silanol group present on the surface of silica fine particles by hydrolysis and condensation reactions, and a polymerizable unsaturated group is a compound that chemically reacts between molecules through addition polymerization by an active radical species. It is a component that crosslinks. In addition, the divalent organic group represented by the formula (I), i.e., the -X (C = Y) NH- group and the urethane bonding group, are a molecular piece having an alkoxysilyl group and a molecule having a polymerizable unsaturated group. It is a constituent unit that bonds directly to a piece or via another molecular piece, and at the same time, generates an appropriate cohesive force due to hydrogen bonding between molecules,
It is considered that the hard coat layer of the present invention generates performance such as excellent mechanical strength, adhesion to a substrate, and heat resistance. -X
As the (C = Y) NH- group, a -S (C = O) NH- group is preferable.

The structure of the alkoxysilane compound is, for example, a compound represented by the following general formula (II):

[0058]

Embedded image And an alkoxysilane compound represented by the following formula:

In the above general formula (II), R ¹ is a hydrogen atom and a C ₁ -C ₈ monovalent organic group.
And methyl, ethyl, propyl, butyl, phenyl, octyl and the like. R ² is a hydrogen atom and _one of C _{1 to} C ₃
Is a valent alkyl group. m is 1, 2 or 3;
Examples of the alkoxysilyl group represented by (R ¹ O) _m R ² Si _3-m include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. And preferably a trimethoxysilyl group and a triethoxysilyl group.

[0060] In the formula, - [(C = O) NH-R 4 -
The structural unit represented by NH (C = O) OXO] _p -is introduced for the purpose of extending the molecular chain in the structure represented by the formula (II). R ³ is a C ^{1 to} C ³ divalent organic group. R ⁴ is a divalent organic group, which may be the same or different from R ^3, and usually has a molecular weight of 14 to 10,000,
Preferably, it is selected from divalent organic groups having a molecular weight of 78 to 1000, and is, for example, a linear polyalkylene group such as methylene, ethylene, propylene, hexamethylene, octamethylene, and dodecamethylene; Cyclic or polycyclic divalent organic groups; divalent aromatic groups such as vinylene, phenylene, naphthylene, biphenylene, and polyphenylene; and the like.
Further, these alkyl group-substituted and aryl group-substituted products can also be used. These divalent organic structures may contain atomic groups composed of elements other than carbon and hydrogen atoms. In the formula, p is 0 or 1, X is a divalent organic group, and a divalent organic group derived from a compound having two or more active hydrogen atoms in the molecule capable of undergoing an addition reaction with an isocyanate group. A polyalkylene glycol, a polyalkylene thioglycol, a polyester, a polyamide, a polycarbonate, a polyalkylene diamine, a polyalkylene dicarboxylic acid, a polyalkylene diol And divalent organic groups derived by removing two active hydrogen atoms from polyalkylene dimercaptans. R ⁵ is an (n + 1) -valent organic group. Such organic groups are preferably selected from chain, branched or cyclic saturated hydrocarbon groups, unsaturated hydrocarbon groups, and alicyclic groups. Also, n
Is preferably a positive integer of 1 to 20, more preferably 1 to 10, and still more preferably 3 to 5. In the above formula, Y represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular cross-linking reaction in the presence of an active radical species, for example, an acryloxy group, a methacryloxy group, a vinyl group, a propenyl group, Butadienyl group, styryl group, ethynyl group, cinnamoyl group, maleate group, acrylamide group and the like. Among these, an acryloxy group is preferred.

For the formation of the molecular structure of the alkoxysilane compound, usually, an alkoxysilane having a mercapto group,
That is, it can be carried out by an addition reaction of a mercaptoalkoxysilane with a polyisocyanate compound and an active hydrogen group-containing polymerizable unsaturated compound having an active hydrogen causing an addition reaction with an isocyanate group.

As a method for producing an alkoxysilane compound, for example, the method (A); first, an adduct of a mercaptoalkoxysilane and a polyisocyanate compound is reacted to form an alkoxysilyl group, -S (C = O)
An intermediate containing an NH-bonding group and an isocyanate group is produced, and then the isocyanate remaining in the intermediate is reacted with an active hydrogen group-containing polymerizable unsaturated compound to bond via an urethane group. How to let. Method (B): An intermediate containing a polymerizable unsaturated group, a urethane bonding group, and an isocyanate group in the molecule by reacting an adduct of a polyisocyanate compound with a polymerizable unsaturated compound having an active hydrogen group. And a mercaptoalkoxysilane is reacted therewith to form -S (C = O) NH-
A method of bonding via a group and the like can be given. Further, in the above method (A) or (B), a chain, cyclic or branched compound having two or more active hydrogens which cause an addition reaction with isocyanate in the molecule as a chain extension unit may be further used as a polyisocyanate. It can also be extended through a urethane bond with the compound.

In the production of the compound represented by the formula (II), the compound is directly reacted with a polyisocyanate compound.
Examples of the alkoxysilane capable of forming an S (C ＝ O) NH— bond can be selected from compounds having at least one alkoxysilyl group and one or more mercapto group in the molecule as a reaction product. For example, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptopropylmethoxydimethylsilane, mercaptopropyltriethoxysilane, mercaptopropyltriphenoxysilane, mercaptopropyltriethoxysilane Examples include mercaptoalkoxysilanes such as butoxysilane, and preferred are mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane. Commercially available mercaptoalkoxysilanes include, for example, SH60 manufactured by Dow Corning Toray Co., Ltd.
62. These mercaptoalkoxysilanes may be used alone or as a mixture of two or more kinds. Further, examples of mercaptoalkoxysilanes include addition products of amino-substituted alkoxysilanes and epoxy-substituted mercaptans, epoxysilanes and α, ω -An addition product with a dimercapto compound can be used. Used when producing an alkoxysilane compound,
As the polyisocyanate compound, a chain saturated hydrocarbon,
It can be selected from polyisocyanate compounds composed of cyclic saturated hydrocarbons and aromatic hydrocarbons, and can be used alone or in combination of two or more. The number of isocyanate groups in one molecule is usually 2 or more and less than 30 and preferably 2 or more and less than 10. If it exceeds 30, the viscosity of the product will increase and the workability may decrease.

Examples of such polyisocyanate compounds include, for example, tetramethylene diisocyanate,
Chain hydrocarbon polyisocyanate compounds such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate; isophorone diisocyanate
, Dicyclohexylmethane diisocyanate, methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, 3
Cyclic saturated hydrocarbon polyisocyanate compounds such as -bis (isocyanatomethyl) cyclohexane; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate 1,4-
Xylylene diisocyanate, paraphenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, diphenylmethane-4,4'-
Diisocyanate, 4,4'-biphenylenediisocyanate, 6-isopropyl-1,3-phenyldiisocyanate, 4-diphenylpropanediisocyanate,
Lysine diisocyanate, 1,5-naphthalenediisocyanate, polyisocyanate of polydiphenylmethane
And aromatic hydrocarbon polyisocyanate compounds.

Of these, preferred are a cyclic saturated hydrocarbon polyisocyanate compound and an aromatic hydrocarbon polyisocyanate compound, more preferably a cyclic saturated hydrocarbon polyisocyanate compound. Preferred specific examples are isophorone diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated toluene diisocyanate. Examples of commercially available polyisocyanate compounds include TDI-80 / 20 and TDI-10 manufactured by Mitsui Nisso Urethane Co., Ltd.
0, MDI-CR100, MDI-CR300, MDI
-PH, NDI, Nippon Polyurethane Industry Co., Ltd., Coronate T, Millionate MT, Millionate MR, HD
I. Taketake 600 manufactured by Takeda Pharmaceutical Company Limited.

The amount of the polyisocyanate compound used in the production method described in the above method (A) is usually 0.1 to 1 equivalent of the isocyanate group per 1 equivalent of the mercapto group of the mercaptoalkoxysilane. It is added in the range of 100, preferably in the range of 0.5 to 10, more preferably in the range of 0.9 to 1.2. When the amount of the polyisocyanate compound group equivalent is less than 0.1 equivalent,
Unreacted mercaptosilane is present in an amount of 0.9 equivalent or more, and the abrasion of the coating film may not be sufficient. Also,
If the polyisocyanate compound is used in an amount exceeding 100 equivalents, the unreacted isocyanate group may be excessively present and the weather resistance may be reduced.

On the other hand, in the production method shown in the above method (B), the polyisocyanate compound is usually used in an amount of 0.1 to 100 as an isocyanate equivalent relative to 1 equivalent of the active hydrogen group in the active hydrogen group-containing polymerizable unsaturated compound. , Preferably in the range of 0.5 to 10 equivalents, more preferably in the range of 0.9 to 1.2.

In any of the above methods (A) and (B), a catalyst may be added for the purpose of shortening the reaction time. As such a catalyst, either a basic catalyst or an acidic catalyst is used. Examples of the basic catalyst include amines such as pyridine, pyrrol, triethylamine, diethylamine, dibutylamine, and ammonia;
Phosphines such as tributylphosphine and triphenylphosphine can be exemplified. Of these, tertiary amines such as pyridine and triethylamine are preferred. Examples of the acidic catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, 1,4-diazabicyclo [2.2.2] octane (DABCO), methyl DABC
Metal alkoxides such as O, tributoxyaluminum, trititanium tetrabutoxide and zirconium tetrabutoxide; Lewis acids such as boron trifluoride diethyl etherate and aluminum chloride; tin 2-ethylhexanoate, octyltin trilaurate; And tin compounds such as dibutyltin dilaurate and octyltin diacetate.
Among these catalysts, preferred are acidic catalysts, particularly preferred are tin compounds, and more preferred are octyltin trilaurate, dibutyltin dilaurate, octyltin diacetate and the like. These catalysts are added in an amount of 0.01 to 5 parts per 100 parts by mass of the polyisocyanate compound.
Parts by mass, preferably 0.1 to 1 part by mass. 0.
If the amount is less than 01 parts by mass, the effect of shortening the reaction time by adding a catalyst is small, while if it exceeds 5 parts by mass, the storage stability of the product may be reduced.

In the production of the alkoxysilyl compound,
Examples of the polymerizable unsaturated compound which can be bonded to the polyisocyanate compound through a urethane bond by an addition reaction include an active hydrogen atom capable of forming a urethane bond by an addition reaction with an isocyanate group in the molecule. And one or a mixture of two or more compounds having one or more polymerizable unsaturated groups in the molecule.

Examples of such a compound include a carboxylic acid-containing polymerizable unsaturated compound and a hydroxyl group-containing polymerizable unsaturated compound. For example, the polymerizable unsaturated compound containing a carboxylic acid includes (meth) acrylic acid, itaconic acid, cinnamic acid, maleic acid, fumaric acid, 2- (meth) acryloxypropylhexahydrogenphthalate, -(Meta)
Unsaturated aliphatic carboxylic acids such as acryloxyethyl hexahydrogen phthalate; unsaturated aromatics such as 2- (meth) acryloxypropyl phthalate and 2- (meth) acryloxypropyl ethyl phthalate Group carboxylic acids; Further, as a hydroxyl group-containing polymerizable unsaturated compound, 2-hydroxyethyl (meth) acryl
2-hydroxypropyl (meth) acrylate, 2
-Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate
1,4-butanediol mono (meth) acrylate,
2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, neopentylglycol mono (meth) acrylate, poly (pentamethyleneoxycarboxylate)
Ethoxy (meth) acrylate, hydroxystyrene,
Hydroxy alpha methyl styrene, hydroxyethyl styrene, hydroxy-terminated polyethylene glycol-styryl ether, hydroxy-terminated polypropylene glyco-
Rustyryl ether, hydroxy-terminated polytetramethylene glycol-styryl ether, hydroxy-terminated polyethylene polyethylene glycol (meth) acrylate, hydroxy-terminated polypropylene polypropylene (meth) acrylate, hydroxy-terminated polytetramethylene glycol ( (Meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane mono (meth) acrylate, EO-modified trimethylolpropanetri (meth) acrylate, PO-modified trimethylolpropanetri (meth) acrylate G, pentaerythritol tri (meta)
Acrylate, pentaerythritol di (meth) acrylate, pentaerythritol mono (meth) acrylate
G, dipentaerythritol penta (meth) acryle
G, dipentaerythritol tetra (meth) acryle
G, dipentaerythritol tri (meth) acryle
G, dipentaerythritol di (meth) acrylate,
Hydroxyl-containing acrylates such as dipentaerythritol mono (meth) acrylate, and hydroxyl-containing methacrylate
And hydroxyl group-containing styrenes.

Preferred among these are unsaturated aliphatic carboxylic acids and hydroxyl-containing acrylate compounds.
More preferably, it is a hydroxyl group-containing acrylate compound, for example, 2-hydroxyethyl acrylate,
-Hydroxypropyl acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate.

The amount of the polymerizable unsaturated compound used is the equivalent of the active hydrogen group, based on 1 equivalent of the residual isocyanate group in the intermediate obtained by the addition reaction of the mercaptoalkoxysilane with the polyisocyanate compound. Usually, it is 1 equivalent or more. When the amount is less than 1 equivalent, since an active isocyanate group remains in the alkoxysilyl compound, undesirable performances such as foaming, thickening, and coloring due to a reaction with moisture may be exhibited.

In the production of an alkoxysilyl compound, an addition reaction with a polyisocyanate compound is carried out between the alkoxysilyl group and the polymerizable unsaturated group for the purpose of improving the flexibility of the coating film and the adhesion to the substrate. A divalent organic group may be introduced. As a precursor of such a divalent organic compound unit, a chain, cyclic, or branched chain having two or more active hydrogens in the molecule that cause an addition reaction with an isocyanate group may be used. Organic compounds can be used. Here, examples of the group having active hydrogen include a hydroxyl group, a carboxyl group, a mercapto group,
Examples include an amino group, a sulfonic acid group, a phosphoric acid group, and a silanol group. These organic compounds have two or more active hydrogens, preferably two or more and less than ten, and more preferably two. The molecular weight of such a compound having active hydrogen is usually from 500,000 to 100,000, preferably from 100 to 50,000, more preferably from 500 to 10,000.
Examples of such a divalent organic compound include polyalkylene glycols, polyalkylene thioglycols, polyester diols, polyamides, and polycarbonates.
Bonneted diols, polyalkylenediamines, polyalkylenedicarboxylic acids, polyalkylenediols, and polyalkylenedimercaptans can be mentioned. Of these, polyalkylene glycol is preferred. Examples of commercially available polyalkylene glycols include, for example, polyethylene glycol, polypropylene glycol, polytetraethylene glycol, polyhexamethylene glycol, and two or more kinds of these polyalkylene glycols. Can be selected from among copolymers with
UNICEF DC1100, UNICEF manufactured by NOF Corporation
DC1800, UNICEF DCB1100, UNICEF
DCB1800, PPTG40 manufactured by Hodogaya Chemical Co., Ltd.
00, PPTG2000, PPTG1000, PTG2
000, PTG3000, PTG650, PTGL20
00, PTGL1000, EXENO manufactured by Asahi Glass Co., Ltd.
L1020, PBG3000 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
PBG2000, PBG1000, Z3001, etc. can be cited.

The production of the above-mentioned alkoxysilane containing a polymerizable unsaturated group containing a divalent organic group as a constituent component is described as the production methods (C) and (D) using polyalkylene glycol as an example. .

Production method (C): Active isocyanate at the terminal
A polyalkylene glycol is added to an adduct of a mercaptoalkoxysilane and a polysocyanate compound having a hydroxyl group to form a one-terminal hydroxy alkoxysilane, which is then separately synthesized and has a terminal hydroxyl group. A method in which an adduct of a polymerizable unsaturated compound and a polyisocyanate compound is reacted, and the two are connected by a urethane bond.

Production method (D): Active isocyanate at terminal
Addition of an adduct of a mercaptoalkoxysilane and a polyisocyanate compound having a hydroxyl group to a polyalkylene glycol polyisocyanate compound having an active hydroxyl group at a terminal, a hydroxyl group-containing polymerizable unsaturated compound, which is separately synthesized. A method of reacting the body and connecting the both by a urethane bond can be mentioned. The formation conditions of the urethane bond in the above-mentioned method (C) or (D) are the same as those in the above method (A) or (B), and the hydroxyl group is added to the compound having an active isocyanate group at the terminal. Is usually in the range of 1.0 to 1.2. If it is less than 1.0, coloring and thickening due to unreacted isocyanate groups are likely to occur.

In the production of the alkoxysilane compound, a hydrolyzate of a polymerizable unsaturated group-modified alkoxysilane with another organic alkoxysilane may be used. For example, tetramethoxysilane, tetraethoxysilane Alternatively, a condensate with an alkylalkoxysilane such as tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, or phenyltrimethoxysilane may be used. When producing a hydrolysis product, the amount of water used for the hydrolysis is usually 0.5 to 1.5 equivalents based on all alkoxy groups,
By heating and stirring at a temperature of from 0 ° C. to the boiling point of the component for 5 minutes to 24 hours in the presence or absence of a solvent, a hydrolysis and condensation polymerization product can be obtained. At that time, an acidic catalyst or a base catalyst can be used in combination for the purpose of shortening the reaction time.

As the silica fine particles used in the production of the modified silica fine particles, those described above can be used in the same manner.

The alkoxysilane compound fixed on the modified silica fine particles is usually expressed as a constant value of the mass loss% when the dry powder is completely burned in air, for example, from room temperature to 800 ° C. in air. It can be determined by thermal mass spectrometry.

The amount of water consumed in the hydrolysis of the alkoxysilane compound in the production of the modified silica fine particles may be such that at least one of the alkoxy groups on silicon in one molecule is hydrolyzed. Preferably, the amount of water added or present at the time of hydrolysis is at least one third of the number of moles of all alkoxy groups on silicon, more preferably one half of the number of moles of all alkoxy groups. More than three times. The product obtained by mixing the alkoxysilane compound represented by the formula (II) and the silica fine particles under completely free of water is a product obtained by physically adsorbing the alkoxysilane compound on the surface of the silica fine particles. In the composition composed of such components, the effect of developing abrasion resistance, which is one object of the composition of the present invention, is low.

In the production of the modified silica fine particles of the present invention, the alkoxysilane compound represented by the formula (II) is separately hydrolyzed, and then mixed with the powdered silica fine particles or colloidal silica. A method of performing a stirring operation; or a method of performing hydrolysis of the alkoxysilane compound represented by the above formula (II) in the presence of silica fine particles; and other components such as a polyfunctional unsaturated organic compound and a unit price In the presence of a saturated organic compound, a photopolymerization initiator, etc.
A method of performing a surface treatment of the silica fine particles can be selected, but a method of hydrolyzing the alkoxysilane compound represented by the formula (II) in the presence of the silica fine particles is preferable. When producing the component B, the temperature during the production is usually 2
0 ° C. to 150 ° C. and the treatment time ranges from 5 minutes to 24 hours.

It is known that the silica fine particles contain water as adsorbed water on the particle surface in a normal storage state.
For example, even colloidal silica dispersed in an organic solvent usually contains 0.5% of water as a product. Therefore, in the production of the modified silica fine particles, it is also possible to mix the alkoxysilane compound and the silica fine particles, and heat and stir the mixture to utilize the water contained in the raw material.

When powdery silica is used in the production of the modified silica fine particles of the present invention, the reaction with the alkoxysilane compound is carried out smoothly and uniformly.
An organic solvent compatible with water may be added. Preferred types of such organic solvents are alcohols, ketones, ethers, and amides, and the alcohols include methanol, ethanol, isopropyl alcohol, and butanol. , Ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, etc .; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; and amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, gamma-butyrolactone Can be. The amount of these solvents to be added is not particularly limited as long as it meets the purpose of making the reaction proceed smoothly and uniformly.

In the production of modified silica fine particles,
In order to promote the reaction, an acid or a base may be added as a catalyst, and as the acid, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid,
Inorganic acids such as methanesulfonic acid, toluenesulfonic acid, phthalic acid, malonic acid, formic acid, acetic acid, oxalic acid, etc., unsaturated organic acids such as methacrylic acid, acrylic acid, itaconic acid and tetramethylammonium hydrochloric acid And ammonium salts such as tetrabutylammonium hydrochloride. As the base, ammonia water,
Diethylamine, triethylamine, dibutylamine,
Primary, secondary or tertiary aliphatic amines such as cyclohexylamine, aromatic amines such as pyridine, quaternary ammonium hydroxides such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and tetrabutylammonium hydroxide Can be mentioned. Of these, preferred examples include organic acids and unsaturated organic acids as the acid, and tertiary amines or quaternary ammonium hydroxides as the base. The amount of the acid or base to be added is 0.001 to 1.0 parts by mass, preferably 0.01 to 0.1 parts by mass, per 100 parts by mass of the alkoxysilane compound.

The curable resin for forming the hard coat layer 4 of the present invention is generally an ultraviolet-curable resin, and the ultraviolet-curable resin is a known ultraviolet-curable resin except for containing the above-mentioned fine particle silica and / or modified fine particle silica. Functional resins (including polymerizable oligomers, polyfunctional monomers, monofunctional monomers, photopolymerization initiators, additives, etc.) can be used.

Such an ultraviolet curable resin is, for example, an oligomer such as a urethane oligomer, a polyester oligomer or an epoxy oligomer having a plurality of ethylenic double bonds, pentaerythritol tetraacrylate (P
ETA), pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate (DP
It is preferably composed of a polymerizable oligomer such as EHA) and / or a polyfunctional monomer as a main component. The functional polymerizable monomer used in the production of the modified silica fine particles can be used as appropriate.

As described above, the resin is generally composed of an oligomer, a reactive diluent (polyfunctional monomer, monofunctional monomer) if necessary, and a photopolymerization initiator. Examples of the photopolymerization initiator include benzoin, benzophenone, benzoylmethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, dibenzyl, 5-nitroacenaphthene, hexachlorocyclopentadiene, p-nitrodiphenyl, p-nitrodiphenyl, and p-nitrodiphenyl.
-Nitroaniline, 2,4,6-trinitroaniline,
1,2-benzanthraquinone, 3-methyl-1,3-
Diaza-1,9-benzanthrone; acetophenone,
Acetophenone benzyl ketal, anthraquinone, 1
-Hydroxycyclohexyl phenyl ketone, 2,2-
Dimethoxy-2-phenylacetophenone, xanthone compounds, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone,
4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1 −
On, carbazole, xanthone, 1,1-dimethoxydeoxybenzoin, 3,3′-dimethyl-4-methoxybenzophenone, thioxanthone compounds, diethylthioxanthone, 2-isopropylthioxanthone,
-Chlorothioxanthone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl]
-2-morpholino-propan-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, Bisacylphosphine oxide, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzaldehyde, Michler's ketone, 2-benzyl-2-
Dimethylamino-1- (4-morpholinophenyl)-
Butan-1-one, 3-methylacetophenone, 3,
3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone (BTTB) and the like. Further, BTTB and a dye sensitizer such as xanthene,
Combinations with thioxanthene, coumarin, ketocoumarin and the like can be mentioned. Among them, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide , 2-benzyl-2-dimethylamino-1- (4
-Morpholinophenyl) -butan-1-one is preferred.

These can be used alone or in combination of two or more. The oligomer, reactive diluent and initiator may be used alone or in combination of two or more. The content of the reactive diluent is generally 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, per 100 parts by mass of the ultraviolet curable resin. The content of the photopolymerization initiator is preferably 5 parts by mass or less based on 100 parts by mass of the ultraviolet curable resin.

The ultraviolet curable resin of the present invention may further contain a silicone polymer. Preferably, it is a graft copolymer having silicone in a side chain, and more preferably, an acrylic graft copolymer having silicone in a side chain. As the silicone-based graft copolymer obtained by radically polymerizing an acrylic-modified silicone polymer monomer and a radical-polymerizable monomer, the acrylic-modified silicone is a silicone represented by the following formula (III) and a silicone represented by the following formula (IV). Products obtained by condensing with the acrylic compound shown can be mentioned.

[0090]

Embedded image

(Wherein R ⁶ and R ⁷ represent a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a phenyl group or a monovalent halogenated hydrocarbon group, and q is one or more positive number) .)

[0092]

Embedded image

Wherein R ⁸ represents a hydrogen atom or a methyl group, R ⁹ represents a methyl group, an ethyl group or a phenyl group;
Two R ⁹ may be the same or different from each other;
Z represents a chlorine atom, a methoxy group or an ethoxy group. )

The silicone represented by the formula (III) can be obtained as a commercial product, and a product suitable for the purpose can be used. Wherein R ⁶ and R ⁷ in formula (III) is an aliphatic hydrocarbon group, a phenyl group or a monovalent halogenated hydrocarbon monovalent C1-10, C1-10
Examples of the monovalent aliphatic hydrocarbon group include a methyl group,
Examples of the monovalent halogenated hydrocarbon include an ethyl group and an acyl group. Examples of the monovalent halogenated hydrocarbon include a 3,3,3-trifluoropropyl group, a 4,4,4-trifluoro-3,3-difluorobutyl group, -Chloroethyl group and the like. Particularly preferred as R8 and R9 is a methyl group.

In the above formula (III), q is a positive number of 1 or more. Generally, a copolymer of an acrylic modified silicone derived from a high molecular weight silicone having q of 100 or more and a radical polymerizable monomer. From the tendency to obtain oily, from the copolymerization of acrylic-modified silicone derived from a low molecular weight silicone having a number of q of 100 or less and a radical polymerizable monomer, depending on the type of monomer used, Various types such as shape, jelly shape, and solid shape can be obtained.

Next, examples of the acrylsilane compound represented by the above formula (IV) include γ-methacryloxypropyldimethylchlorosilane, γ-methacryloxypropyldimethylethoxysilane, γ-methacryloxypropyldiphenylchlorosilane, γ-acryloxypropyl Examples include dimethylchlorosilane, γ-methacryloxypropyltriethoxysilane, and γ-methacryloxypropyltrichlorosilane. These acrylic silane compounds can be easily obtained by reacting a silicon compound with a compound having an aliphatic multiple bond in the presence of chloroplatinic acid according to the method of JP-B-33-9969.

For the radical copolymerization of the acrylic-modified silicone and the radical polymerizable monomer, a conventionally known method can be used, and a radiation irradiation method and a method using a radical polymerization initiator can be used. Furthermore, when copolymerizing by an ultraviolet irradiation method, a known sensitizer is used as a radical polymerization initiator, and when copolymerizing by electron beam irradiation, it is not necessary to use a radical polymerization initiator. The silicone copolymer thus obtained is a comb-shaped graft copolymer having a radical polymerizable monomer as a trunk and silicone as a branch.

Commercially available silicone copolymers include Cymac US-150, US-270, US-350,
US-450, Reseda GP-700 (all manufactured by Toagosei Co., Ltd.) and the like.

In the present invention, various additives can be added as needed.
For example, antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, antioxidants, thermal polymerization inhibitors, coloring agents, leveling agents, surfactants, storage stabilizers, plasticizers, lubricants,
Examples include a solvent, an inorganic filler, an organic filler, a filler, a wettability improver, and a coating surface improver.

The hard coat layer of the film-reinforced glass with a hard coat of the present invention (automotive side glass) contains the above-mentioned components as a main component, but is obtained by modifying the above oligomer or monomer or other functional resin. By further using an additive or the like, a hard coat layer having various functions can be obtained. For example, a high scratch-resistant hard coat layer having further improved scratch resistance, an anti-fogging hard coat layer provided with anti-fogging property, a conductive hard coating layer having conductivity, an anti-static property given with anti-static property Hard coat layers, high gloss hard coat layers with further improved gloss, solvent resistant hard coat layers with particularly excellent solvent resistance, and low moisture permeable hard coat layers that hardly transmit moisture. Depending on the application, at least two of these layers may be combined to form a hard coat layer. Of course, one layer may be used. Alternatively, the hard coat layer containing the specific silica fine particles of the present invention can be combined with the above-mentioned hard coat layer.

In the present invention, the high scratch-resistant hard coat refers to a hard coat having a pencil hardness of 8H or more, preferably 9H or more. The general hard coat layer is set to 5H or more. In order to further improve the abrasion resistance, it can be performed by further increasing the hardness as described above than the ordinary hard coat layer, but it is necessary to prevent the film crack by making the film thickness smaller than usual. . Examples of the scratch-resistant hard coat include UVCH1105 (trade name, manufactured by Toshiba Silicone Co., Ltd.).

The anti-fog hard coat layer is a layer that does not dew due to water vapor and does not decrease in transparency. In order to impart anti-fogging properties, it is necessary to form a hard coat layer using, for example, a hydrophilic oligomer or monomer, or a surfactant (particularly a wet penetrant). As the anti-fog hard coat, for example, trade name: Diabeam M
H-3263 (manufactured by Mitsubishi Rayon Co., Ltd.) can be mentioned.

The conductive hard coat layer is a highly conductive layer, and usually has an electric conductivity of 10 ² to 10 ⁴ s / s in the present invention.
cm refers to a layer. In order to provide conductivity for cutting electromagnetic waves, for example, a hard coat layer containing a conductive material (metal fine particles of carbon, silver, copper, nickel, etc.) or the like is formed. As the conductive hard coat, for example, trade name:
Conductive EJ-3 (manufactured by Dainippon Paint Co., Ltd.) can be mentioned.

The antistatic hard coat layer is a layer that does not easily generate static electricity due to friction. In the present invention, the antistatic hard coat layer generally has a volume resistivity value of 10 ¹² Ω · cm or less. In general, the antistatic property can be imparted by using various surfactants, oligomers and monomers having a group having a surface active function, and the like. Examples of the antistatic hard coat include Sunrad UXH601 (trade name, manufactured by Sanyo Chemical Industries, Ltd.).

The high gloss hard coat layer has a gloss (gloss)
In the present invention, the gloss is usually 95 or more (J
IS-K-7105). In order to improve gloss, it is generally performed by suitably combining an oligomer and a monomer component. Examples of the high gloss hard coat include trade name: ADEKA OPTOMER KR-567 (manufactured by Asahi Denka Kogyo KK).

Although the hard coat layer itself is excellent in solvent resistance, the solvent resistant hard coat layer of the present invention is a layer that is also excellent in high polar solvents (DMF and the like). In order to improve the solvent resistance, for example, a silicon-modified or fluorine-modified oligomer, monomer or resin is used. As the solvent-resistant hard coat, for example, trade name: silicone hard coat agent KP85
1 (manufactured by Shin-Etsu Chemical Co., Ltd.).

The low-moisture-permeable hard coat layer is a layer that hardly permeates water vapor.
5g ^/ m 2 · 24h or less refers to a layer of (JIS-Z-0208). In order to make the moisture hardly permeate, for example, silicon-modified, fluorine-modified oligomers, monomers or resins are used. Examples of the low moisture permeable hard coat include a trade name: low moisture permeable ultraviolet curing resin (manufactured by Nippon Kasei Co., Ltd.).

The layer thickness of the hard coat layer is 0.1 in the case of one layer.
The thickness is preferably 1 to 20 μm (particularly 1 to 15 μm), and in the case of a multilayer, the total is preferably in these ranges.

It is preferable to provide an antireflection layer on the surface of the hard coat layer of the film reinforced glass of the present invention.

As the antireflection layer, for example, the following can be used.

A) A single layer of a high refractive index transparent thin film is provided (b) A layer of a medium refractive index transparent thin film / a single layer of a high refractive index transparent thin film is stacked in a total of two layers (c) One layer each in the order of a refractive index transparent thin film / a low refractive index transparent thin film / a high refractive index transparent thin film, and a total of three layers (d) High refractive index transparent thin film / low refractive index transparent thin film / high refractive index transparent A thin film / low-refractive-index transparent thin film laminated in a total of four layers, one layer each (e) High-refractive-index transparent thin film / low-refractive-index transparent thin film / high-refractive-index transparent thin film / low-refractive-index transparent thin film / high One layer each in the order of the refractive index transparent thin film laminated in a total of 5 layers. Here, as the high refractive index or medium refractive index transparent thin film, ITO (tin indium oxide), ZnO, or Zn doped with Al is used.
A thin film having a refractive index of 1.8 or more, such as O, TiO ₂ , SnO ₂ , and ZrO, can be employed.

As the transparent film having a low refractive index or a medium refractive index, a thin film having a refractive index of 1.6 or less such as SiO ₂ , MgF ₂ , Al ₂ O ₃ , acrylic resin, urethane resin, silicone resin, and fluororesin can be used. Can be used.

The thicknesses of the high-refractive-index transparent thin film, the medium-refractive-index transparent thin film, and the low-refractive-index transparent thin film are determined so that the reflectance in the visible light region can be reduced by light interference. , The center wavelength and the like.

Such a transparent thin film can be formed by vapor deposition, sputtering, ion plating, CVD, microgravure coating, direct gravure coating, slot die coating, or the like.

Alternatively, the antireflection layer comprises a high refractive index conductive layer formed on the hard coat layer and a low refractive index layer formed on the high refractive index conductive layer. An ITO film (tin-indium oxide film) having a thickness of 100 to 600 °, wherein the low refractive index layer has a thickness of 900 to 150;
It is also preferable to use a 0 ° SiO ₂ film.

Since such an anti-reflection layer has a two-layer structure of a high-refractive-index conductive layer and a low-refractive-index layer, the anti-reflection layer has better anti-reflection performance than a single-layer anti-reflection layer. ,
In addition, the structure can be simplified and the cost can be reduced at a low cost as compared with the case where the antireflection layer having the multilayer structure is provided. Also,
Since it has a high refractive index conductive layer, it also has antistatic performance in addition to antireflective performance.

As described above, as the antireflection layer, the high refractive index conductive layer made of an ITO film having a thickness of 100 to 600 ° and the low refractive index layer 5 made of an SiO ₂ film having a thickness of 900 to 1500 ° are used. When forming an antireflection layer having a two-layer structure,
If the thickness of the ITO film is less than 100 °, a sufficient antistatic function cannot be obtained, and if it exceeds 600 °, the film formation cost rises. On the other hand, if the thickness of the ITO film is out of the range of 100 to 600 °, good antireflection performance cannot be obtained with a laminated structure of SiO ₂ having a thickness of 900 to 1500 °.

The thickness of the SiO ₂ film is 900 to 150.
Outside the range of 0 °, good antireflection performance cannot be obtained in a laminated structure with an ITO film having a thickness of 100 to 600 °.

The ITO film and the SiO ₂ film can be formed by vapor deposition, sputtering, ion plating, CVD or the like.

When an antireflection layer is provided on the hard coat layer of the present invention, the light transmittance at 365 nm of a laminate comprising an organic polymer film, a hard coat layer and an antireflection layer is 40% or less. Is preferred.

When the light transmittance at 365 nm is 40% or less, the film reinforced glass of the present invention is not largely affected by the surrounding environment such as ultraviolet rays and has good weather resistance,
Due to the excellent durability, problems of yellowing and film peeling are prevented.

The laminate may have, for example, the following structure.

An ultraviolet cut layer is provided between the organic polymer film and the hard coat layer. The hard coat layer is an ultraviolet cut layer. The antireflection layer is an ultraviolet cut layer.

The light transmittance at 365 nm of the laminate is preferably as low as possible. In the present invention, the light transmittance at 365 nm is preferably 30% or less.
It is desirable that the light transmittance for light having a wavelength of nm is 20% or less, particularly 10% or less, particularly 5% or less.

When the ultraviolet ray cut layer is formed as described above, the ultraviolet ray cut layer may be formed by coating a known coating material such as an acrylic resin, a urethane resin, a silicone resin, or an epoxy resin with a known ultraviolet absorbing material. 10
What is necessary is just to mix | blend about mass% and coat on the base film 1. FIG. It is preferable that the thickness of the ultraviolet cut layer 7 formed in this way is about 0.5 to 20 μm.

In the case where the hard coat layer itself is made to have an ultraviolet cut property, the ultraviolet cut hard coat layer is formed by adding a known ultraviolet absorber to the hard coat material (ultraviolet curable resin) in an amount of 0.05 to 5 mass%. % In the range and coated.

In order for the antireflection layer itself to have an ultraviolet-cutting property, a material having a high light transmittance near 400 nm and a high absorption of light near 350 nm or less is used as the material of the high refractive index transparent thin film. It is preferable to use ITO, ZnO, or the like as such a material.

On the surface of one glass plate 1, metal and / or
Alternatively, a transparent conductive layer made of a metal oxide may be provided.

Thus, the automobile side glass of the present invention is obtained. The obtained film-reinforced glass constitutes a glass having particularly excellent security such as durability, scratch resistance, impact resistance, penetration resistance and the like.

[0130]

The present invention will be described in more detail with reference to the following examples. [Production Example of Colloidal Silica with Added Polymerizable Unsaturated Group] In a dry air, a solution consisting of 7.8 parts by weight of mercaptopropyltrimethoxysilane and 0.2 parts by weight of dibutyltin dilaurate was added with isophorone diisocyanate 2
After dropping 0.6 parts by mass at 50 ° C. over 1 hour with stirring, the mixture was stirred at 60 ° C. for 3 hours. After 71.4 parts by mass of pentaerythritol triacrylate was added dropwise at 30 ° C. over 1 hour, the mixture was heated and stirred at 60 ° C. for 3 hours to obtain an alkoxysilane compound.

8.1 parts by mass of the obtained silane compound A, methanol silica sol MEK-ST (manufactured by Nissan Chemical Industries, Ltd.)
Methyl ethyl ketone dispersed colloidal silica (average particle size 5
0 nm), a mixture of 30% silica at 90.5 parts by mass and 0.1 part by mass of ion-exchanged water was stirred at 60 ° C. for 3 hours, and 1.3 parts by mass of methyl orthoformate was added.
By further heating and stirring at the same temperature for 1 hour, a dispersion liquid of colloidal silica having a polymerizable unsaturated group added thereto (dispersion liquid A,
(Mass% of silica: 27%).

[Examples 1 to 3 and Comparative Examples 1 and 2] <Preparation of automotive side glass> (Preparation of ultraviolet curable resin (coating solution)) 33 parts by mass of dispersion A obtained above, dipentaerythritol hexaacrylate The above coating liquid was obtained by stirring (DPHA) 15 parts by mass and 1-hydroxycyclohexylphenyl ketone (HCHPK) 2 parts by mass at room temperature for 30 minutes. In the same manner, coating solutions having the formulations shown in Table 1 were prepared.

(Preparation of Laminate) PET film (122)
μm thick;
10 and the solvent was evaporated at 60 ° C. for 5 minutes.
J / cm ² ) to obtain a 5 μm hard coat layer.

On the hard coat layer, a thickness of 25
An ITO film having a thickness of 0 ° and a SiO ₂ film having a thickness of 1200 ° were formed in this order by a reactive sputtering method, and an antireflection layer having a two-layer structure was provided.

Thus, a PET film having a hard coat layer and an antireflection layer was obtained.

A transparent adhesive layer was prepared as follows.

Separately, ethylene vinyl acetate copolymer (vinyl acetate content 25% by mass, melt index 4) 9
5 parts by mass, 5 parts by mass of triallyl isocyanurate, 1,
1 part by mass of 1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and γ-methacryloxypropyltrimethoxysilane were mixed by a roll mill heated to about 80 ° C. to prepare a composition for EVAT. did. The composition was sandwiched between PET films using a press to produce a 188 μm thick sheet.

Next, the sheet for the transparent adhesive layer of EVAT and the PET film (122 μm thick) obtained above were stacked on one glass plate having a thickness of 5 mm which had been washed and dried in advance.
Next, a PET release sheet was laminated on the coating layer.

This was put in a rubber bag and degassed under vacuum.
Pre-compression bonding at a temperature of Next, the pre-pressed glass was placed in an oven and subjected to a pressure treatment at a temperature of 150 ° C. for 30 minutes.

[0140]

[Table 1] Example 1 Comparative Example 1 Example 2 Example 3 Comparative Example 2 Comparative Example 3 DPHA 15 15 15 15 15 15 15 Dispersion A--66 66--Silica (MEK-ST) 60 60----HCHPK 2 222 2 2 MEK 23 17 23 23 60 60 EVA / TAIC of transparent adhesive layer Mass ratio 95/5 100/0 95/5 97/3 95/5 95/5 Anti-reflective layer Yes Yes Yes Yes No Yes

Abrasion resistance ○ ○ ◎ ◎ × × Scratch resistance ○ ○ ◎ ◎ × × Anti-reflective property ○ ○ ◎ ◎ × ○ Transparency ◎ ○ ◎ ◎ ○ ○ Adhesion ◎ ○ ◎ ◎ ◎ ◎ ◎

Remarks) PTA: pentaerythritol triacrylate MEK: methyl ethyl ketone

<Evaluation of Film-Tempered Glass> (1) The abrasion resistance was measured in accordance with JIS-R3221, using a Taber abrasion tester on the surface on the antireflection layer side (wear wheel: CS-10F; load). : 500 g; 1
000 times), and the haze after the test was measured.
A haze value of less than 10 was evaluated as ○ (especially low one), and a value of 10 or more was evaluated as x.

(2) The abrasion resistance of the surface on the antireflection layer side was 200 g / cm ² on steel wool # 0000.
, And reciprocate 10 times.
A mark with slight scratches was marked with "O", and a mark with marked scratches was marked with "X".

(3) Regarding the anti-reflection performance, x indicates that the glare was visually recognized, and ○ indicates that the glare was hardly observed.

(4) The transparency was measured after subjecting the obtained film-reinforced glass to a weatherometer test for 1000 hours.
The haze was measured. A haze value of less than 10 was evaluated as ○ (especially low one), and a value of 10 or more was evaluated as x.

(5) The adhesion was evaluated by subjecting the obtained film-reinforced glass to a weatherometer test for 1000 hours.
The state of peeling and whitening of the edge between the film and the glass was observed.も の indicates that no peeling or whitening was observed, ○ indicates slight peeling or whitening, and X indicates clearly peeling or whitening.

(6) The glass obtained in the examples had high transparency, had no optical distortion, and was excellent in impact resistance, penetration resistance, scratch resistance and antireflection properties. Therefore, it was suitable as a side or rear glass of an automobile.

[Embodiments 4 to 6] Embodiments 4 to 6 correspond to Embodiment 1.
Using the materials No. to No. 3, a film-reinforced glass was produced as follows.

On the glass plate, a sheet for a transparent adhesive layer of EVAT (instead of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3-di-t-butyl peroxide) was used. (1 part by weight of benzoin ethyl ether) and the PET film were superimposed, the coating liquid of the ultraviolet curable resin was applied to the PET surface by a roll coater, and then a PET release sheet was overlaid on the coating layer.

The obtained laminate was put in a rubber bag, degassed under vacuum, and pre-pressed at a temperature of 80 ° C. Next, ultraviolet irradiation (1 kW / cm UV lamp, irradiation distance 20 c
m, irradiation time 30 seconds) to form a hard coat and to crosslink the organic resin film.

On the hard coat layer, a thickness of 25
An ITO film having a thickness of 0 ° and a SiO ₂ film having a thickness of 1200 ° were formed in this order by a reactive sputtering method, and an antireflection layer having a two-layer structure was provided.

Thus, a film-reinforced glass was obtained.

<Evaluation of Film-Tempered Glass> The same results as those shown in Table 1 were obtained. Example 4
In Nos. To 6, it can be said that the production is easy and the productivity is improved.

[0155]

The automobile side glass (film reinforced glass) according to the present invention described above has security properties such as impact resistance and penetration resistance close to that of laminated glass despite its thinness, and transparency, Durability such as adhesion, abrasion resistance,
It can be said that it has scratch resistance and is easy to manufacture.

[0156]

[Brief description of the drawings]

FIG. 1 is a perspective view illustrating an embodiment of a film-reinforced glass according to the present invention.

FIG. 2 is a sectional view taken along the line AA ′ in FIG.

[Explanation of symbols]

 Reference Signs List 1 1 glass plate (outside) 2 Transparent adhesive layer made of organic resin 3 Film made of organic polymer 4 Hard coat layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 123/08 C09J 123/08 131/04 131/04 139/00 139/00 F-term (Reference) 4G061 AA02 AA03 AA04 AA27 BA02 CA05 CB03 CB16 CD02 CD19 CD20 DA23 DA30 DA46 4J026 AC04 BA40 DB36 FA05 GA02 4J040 DA051 DE031 FA071 FA072 FA202 GA17 HB03 HB05 HB19 HB41 HC17 HC22 HD31 HD32 HD35 HD36 HD37 JB08 KA12 MB06 LA06

Claims (10)

[Claims] 1. An automobile side glass in which one glass plate and a film made of an organic polymer are laminated via a transparent adhesive layer made of an organic resin, wherein the transparent adhesive layer is made of ethylene vinyl acetate. A hard coat layer made of a cured film of a curable resin containing fine silica particles is provided on the surface of the organic polymer film, which is made of a crosslinked product of triallyl isocyanurate of the copolymer, and which is not in contact with the transparent adhesive layer of the organic polymer film. An automotive side glass characterized by: 2. The automobile side glass according to claim 1, wherein the transparent adhesive layer comprises a triallyl isocyanurate crosslinked product of an ethylene-vinyl acetate copolymer containing γ- (methacryloxypropyl) trimethoxysilane. 3. The automobile side glass according to claim 1, wherein the curable resin is an ultraviolet curable resin. 4. The silica fine particles have a primary particle size of 1 to 200 n.
The automobile side glass according to any one of claims 1 to 3, which is in a range of m. 5. The automobile side glass according to claim 1, wherein the silica fine particles have a polymerizable unsaturated group. 6. The vehicle side glass according to claim 1, wherein the silica fine particles are formed by reacting silica fine particles with an alkoxysilane compound having a polymerizable unsaturated group. 7. The automobile side glass according to claim 1, wherein an antireflection layer is formed on a surface of the hard coat layer. 8. The automobile side glass according to claim 1, wherein the organic polymer is polyethylene terephthalate. 9. An organic resin film of a laminate in which an organic resin film containing a photopolymerization initiator and an ethylene-vinyl acetate copolymer containing triallyl isocyanurate is placed on the surface of one glass plate. On the surface, a film made of an organic polymer is placed, and then the ultraviolet-curable resin for forming a hard coat layer according to claim 3 is applied, and the applied layer is dried,
Subsequently, the entire laminated body provided with the coating layer is vacuum-degassed and pre-compressed, and then the coating layer and the organic resin film are cured by irradiating the coating layer with ultraviolet rays. Manufacturing method. 10. An organic resin film of a laminate in which an organic resin film containing a photopolymerization initiator and an ethylene-vinyl acetate copolymer containing triallyl isocyanurate is placed on the surface of one glass plate. A film made of an organic polymer is placed on the surface, and then the ultraviolet curable resin for forming a hard coat layer according to claim 3 is applied, and a release sheet is placed on the applied layer, and then the release sheet is placed. A method for producing an automobile side glass, wherein the whole of the laminated body provided with is subjected to vacuum degassing and pre-compression bonding, and then the applied layer and the organic resin film are cured by irradiating the release layer with ultraviolet rays.