JP2002046217A - Film-reinforced glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide film-reinforced glass excellent in impact resistance, penetration resistance and crime preventing properties and also in durability due to good adhesion, thin in thickness and besides easy to manufacture. SOLUTION: The film-reinforced glass 1 is constituted by laminating and bonding a glass sheet 2 and an organic resin film 3 with an adhesive resin layer intarlaid. The adhesive resin layer has a first adhesive resin layer 4 on the glass sheet 2 side constituted mainly of a polyvinyl butyral resin and a second adhesive resin layer 5 on the organic resin film 3 side constituted mainly of an ethylene-vinyl acetate copolymer resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thin, lightweight film-reinforced glass used in automobiles, railway vehicles, buildings, showcases, etc., which is excellent in impact resistance, penetration resistance, crime prevention and the like.

[0002]

2. Description of the Related Art Conventionally, laminated glass having a structure in which an organic resin film (intermediate film) is sandwiched between two glass plates is generally used for glass used for automobiles, particularly for windshields. As this organic resin film, a polyvinyl butyral (PVB) resin film is generally used because of its excellent impact resistance, and the penetration resistance and the like of the laminated glass are enhanced by the presence of this organic resin film. In addition, the broken glass fragments remain adhered to the organic resin film in response to an external impact, so that scattering of the broken glass fragments is prevented. Therefore, even if the laminated glass of an automobile is broken for the purpose of theft, intrusion, or the like, the window cannot be freely opened, so that it is also useful as security glass.

[0003] On the other hand, for example, door glass and glazing of automobiles are generally less likely to be destroyed in an accident.
Further, since it does not require the penetration resistance or the like of the above-mentioned windshield, a slightly strengthened low-strength glass sheet is used. However, when only one such glass plate is used, it is inferior to laminated glass in terms of impact resistance, penetration resistance and the like. If it is destroyed for the purpose of theft, intrusion, or the like, it breaks into many pieces, and the windows can be freely opened. Therefore, it is desired to use a glass having a strength comparable to that of a laminated glass for a door glass, a fitted glass, and the like.

[0004] Such laminated glass, particularly for door glass of automobiles, is disclosed in, for example, JP-A-6-3215.
No. 87 proposes a laminated glass for automobiles having a five-layer structure in which an outer plate made of silicate glass and a polycarbonate plate core material which have been strengthened in advance, and the outer plate covers the polycarbonate core material plate with a thermoplastic polyurethane layer.

[0005]

However, as described above, the door glass and the like are usually a single piece of glass, and the thickness, strength and the like of the laminated glass for the windshield are usually required. Absent. Further, since the laminated glass has a certain thickness, it may not be possible to use the laminated glass for, for example, a side glass of a small car having a relatively small size and a fitted glass. Further, the production of a laminated glass having a multilayer structure is more complicated than that of a single-pane glass.

[0006] Further, not only such glass for automobiles but also almost all industrial products are required to be thin, small, and lightweight.

Accordingly, an object of the present invention is to provide a film reinforced glass which is excellent in impact resistance, penetration resistance and crime prevention, is thin, and is easy to manufacture.

[0008]

Means for Solving the Problems The film reinforced glass of the present invention is a film reinforced glass obtained by laminating and bonding a glass plate and an organic resin film via an adhesive resin layer.
The adhesive resin layer is made of polyvinyl butyral (P
VB) Ethylene-vinyl acetate copolymer (EVA) on the first adhesive resin layer mainly composed of resin and the organic resin film side
A second adhesive resin layer containing a resin as a main component.

In the following, the first adhesive resin layer mainly composed of PVB resin is referred to as "PVB layer" and EVA
The second adhesive resin layer containing a resin as a main component is referred to as an “EVA layer”.

[0010] Since the film-reinforced glass of the present invention is formed by laminating and bonding an organic resin film to one glass plate via an adhesive resin layer, it is thin and lightweight.

As the adhesive resin layer, the PVB layer is excellent in shock absorption resistance and penetration resistance, and has good adhesion to glass, but has a drawback that adhesion to an organic resin film is weak. On the other hand, the EVA layer exhibits excellent adhesive strength to both glass and organic resin films, but has insufficient shock absorption resistance and penetration resistance for use as a film-reinforced glass.

In the present invention, the adhesive resin layer has a two-layer structure,
PVB layer with excellent shock absorption and penetration resistance and good adhesion to glass is used as the adhesive resin layer on the glass plate side. Adhesion with organic resin film is slightly inferior in shock absorption and penetration resistance. By using the EVA layer having excellent durability as the adhesive resin layer on the organic resin film side, a film-reinforced glass having excellent mechanical properties and durability can be realized.

The EVA resin has excellent water resistance, and therefore has the following advantages. That is, for example, when the film-reinforced glass of the present invention is used for a door glass of an automobile, the door glass is freely moved up and down, so that it frequently comes into contact with a window frame and peeling is likely to occur. However, since the film-reinforced glass of the present invention has improved water resistance, peeling between the glass plate and the organic resin film can be significantly prevented.

In the film-reinforced glass of the present invention, since the adhesive resin layer between the EVA layer and the PVB layer is provided, even if the glass plate is broken for criminal purposes, the presence of the adhesive resin layer prevents The fragments remain attached and are not useful for opening windows, which is useful as security glass.

Such a film-reinforced glass of the present invention can be easily manufactured by laminating and bonding an adhesive resin layer to a glass plate via two adhesive resin layers.

In the present invention, the EVA resin of the EVA layer preferably has a vinyl acetate content of 10 to 50% by weight and is cured by a crosslinking agent.

Further, as the organic resin film, a polyethylene terephthalate (PET) resin film is suitable, and its surface is preferably subjected to a hard coat treatment.

The thickness of the PVB layer of the adhesive resin layer is 10
It is preferable that the thickness of the EVA layer is 5 to 600 μm.

[0019]

Embodiments of the present invention will be described below in detail.

FIG. 1 is a sectional view showing an embodiment of the film-reinforced glass of the present invention.

As shown in FIG.
Is formed by bonding a glass plate 2 and an organic resin film 3 with a PVB layer 4 and an EVA layer 5.

As the glass plate 2, silicate glass is usually used. The thickness of the glass plate 2 varies depending on the use of the film-reinforced glass and the like. For example, when it is used for a side glass or a fitted glass of an automobile, it is not necessary to make it thick like a windshield, and it is generally 1 to 10 mm, preferably 3 to 5 mm. This glass plate 2
Preferably, it is chemically or thermally reinforced. Further, a transparent conductive layer made of metal and / or metal oxide may be provided on the surface of the glass plate 2.

On the other hand, the organic resin film 3 is
The organic resin film 3 is preferably provided as a PET resin film, and the thickness of the organic resin film 3 is determined according to the application. The range of about 2 to 2 mm is general, and the range of 0.5 to 1 mm is preferable.

It is preferable that a hard coat layer is formed on the surface of the organic resin film 3 in order to improve the scratch resistance and the like of the surface.

As the resin used for the hard coat treatment, a UV (ultraviolet) curable resin is suitable, but any other resin having a low molecular weight and polyfunctionality suitable for the hard coat treatment is not particularly limited. Absent. Examples of the UV-curable resin include oligomers such as urethane oligomers, polyester oligomers and epoxy oligomers having a plurality of ethylenic double bonds, pentaerythritol tetraacrylate (PETA), pentaerythritol tetramethacrylate, and dipentaerythritol hexaacrylate (DPEHA). ), Or an oligomer such as benzoin, benzophenone, benzoylmethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether or dibenzyl. The UV-curable resin generally uses a reactive diluent and a photopolymerization initiator, and may further contain various additives. 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 weight with respect to 100 parts by weight of the UV-curable resin.
5 to 5 parts by weight are preferred. The content of the photopolymerization initiator is U
It is preferably 5 parts by weight or less based on 100 parts by weight of the V-curable resin.

The PVB resin of the PVB layer 4 contains 70 to 95% by weight of a polyvinyl acetal unit, 1 to 15% by weight of a polyvinyl acetate unit, and has an average degree of polymerization of 200 to 30%.
00, particularly preferably 300 to 2500,
VB resin is used as a resin composition containing a plasticizer.

Examples of the plasticizer of the PVB resin composition include organic plasticizers such as monobasic acid esters and polybasic acid esters, and phosphoric acid plasticizers.

The monobasic acid esters include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptanoic acid, n-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-
Esters obtained by the reaction of an organic acid such as nonylic acid) and decylic acid with triethylene glycol, and more preferably triethylene-di-2-ethylbutyrate and triethylene glycol-di-2-ethylhexo. Ethates, triethylene glycol-di-capronate, triethylene glycol-di-n-octoate and the like. Note that an ester of the above organic acid with tetraethylene glycol or tripropylene glycol can also be used.

As the polybasic acid ester-based plasticizer, for example, an ester of an organic acid such as adipic acid, sebacic acid, azelaic acid and a linear or branched alcohol having 4 to 8 carbon atoms is preferable, and more preferably. , Dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate and the like.

Examples of the phosphoric acid plasticizer include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate and the like.

In the PVB resin composition, if the amount of the plasticizer is small, the film-forming property is reduced, and if the amount is large, the durability under heat is impaired. Therefore, the plasticizer is added in an amount of 5 to 100 parts by weight of the polyvinyl butyral resin. 50 parts by weight, preferably 10-4
0 parts by weight.

The PVB resin composition may further contain additives such as a stabilizer, an antioxidant, and a UV absorber for preventing deterioration.

The EVA resin of the EVA layer 5 preferably has a vinyl acetate content of 10 to 50% by weight, particularly 15 to 40% by weight. If the vinyl acetate content is less than 10% by weight, the transparency of the resin obtained when cross-linking and curing at a high temperature is not sufficient, and if it exceeds 50% by weight, the impact resistance of the security glass is reduced. The penetration resistance tends to be insufficient.

The EVA resin composition used for the EVA layer 5 can contain various additives such as a plasticizer, an organic peroxide as a cross-linking agent, and an adhesion improver.

The plasticizer is not particularly limited, but generally, esters of polybasic acids and esters of polyhydric alcohols are used. Examples thereof include dioctyl phthalate, dihexyl adipate and triethylene glycol-2. -Ethyl butyrate, butyl sebacate, tetraethylene glycol diheptanoate and triethylene glycol diperargonate. One type of these plasticizers may be used, or two or more types may be used in combination. The content of the plasticizer is EVA resin 1
The range is preferably not more than 5 parts by weight to 00 parts by weight.

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, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, t-butylperoxybenzoate,
Benzoyl peroxide, t-butyl peroxyacetate, methyl ethyl ketone peroxide, 2,5-
Dimethylhexyl-2,5-bisperoxybenzoate, butyl hydroperoxide, p-menthane hydroperoxide, p-chlorobenzoyl peroxide, hydroxyheptyl peroxide, chlorohexanone peroxide, octanoyl peroxide,
Decanoyl peroxide, lauroyl peroxide, cumyl peroxy octoate, succinic peroxide, acetyl peroxide, t-butyl veroxy (2-ethylhexanoate), m-toluoyl peroxide, t-butyl peroxy Mention may be made of isobutyrate and 2,4-dichlorobenzoyl peroxide. One of these organic peroxides may be used, or two or more thereof may be used in combination. The content of the organic peroxide is 0.1 to 100 parts by weight of the EVA resin.
A range of 1 to 5 parts by weight is preferred.

By including such an organic peroxide, the EVA layer 5 having improved curability by heating can be obtained.
Film strength can be improved.

As an adhesion improver, a silane coupling agent can be added. Examples of the silane coupling agent include γ-chloropropylmethoxysilane, vinylethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrisilane. Methoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- β-
(Aminoethyl) -γ-aminopropyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more. The content of the silane coupling agent is E
The amount is preferably 5 parts by weight or less based on 100 parts by weight of the VA resin.

Further, the EVA resin composition constituting the EVA layer 5 has various physical properties of the EVA layer 5 (mechanical strength, adhesive properties, optical properties such as transparency, heat resistance, light resistance, crosslinking speed, etc.). It is preferable to contain an acryloxy group-containing compound, a methacryloxy group-containing compound, and / or an epoxy group-containing compound in order to improve or adjust the content, especially the mechanical strength.

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 the ester residue include linear alkyl groups such as methyl, ethyl, dodecyl, stearyl, lauryl, cyclohexyl, tetrahydrofurfuryl, aminoethyl, 2-hydroxyethyl, 3-hydroxypropyl, A 3-chloro-2-hydroxypropyl group can be mentioned. Further, esters of polyhydric alcohols such as ethylene glycol, triethylene glycol, polypropylene glycol, polyethylene glycol, trimethylolpropane and pentaerythritol with acrylic acid or methacrylic acid can also be mentioned.

Examples of the amide include diacetone acrylamide.

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

Examples of the epoxy group-containing compound include 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.

The content of the acryloxy group-containing compound, the methacryloxy group-containing compound and / or the epoxy group-containing compound is preferably 5 parts by weight or less based on 100 parts by weight of the EVA resin.

In the film-reinforced glass 1 of the present invention,
If the thickness of the PVB layer 4 is too small, sufficient shock absorption resistance,
If the penetration resistance cannot be obtained, and if the thickness is too large, the thickness of the film-reinforced glass is impaired, and the transparency is also lowered. Therefore, the thickness is preferably 25 to 250 μm, particularly preferably 25 to 100 μm.

When the thickness of the EVA layer 5 is too small, sufficient adhesiveness cannot be obtained. When the thickness is too large, the thickness of the film-reinforced glass is impaired, and the transparency is also lowered. In particular, the thickness is preferably 5 to 200 μm.

In order to manufacture the film-reinforced glass of the present invention, first, a PVB resin film and an EVA resin film for forming the PVB layer 4 and the EVA layer 5 are formed, and the glass plate 2, the PVB resin film, and the EVA resin film are formed. The resin film and the organic resin film 3 may be laminated in this order, and after degassing the laminated body, the laminate may be pressed under heating and bonded and integrated. When the organic resin film 3 is subjected to a hard coat treatment, the surface of the organic resin film 3 may be subjected to a hard coat treatment after the bonding.

The PVB resin film and the EVA resin film can be produced by forming the above-mentioned resin composition into a sheet by ordinary extrusion molding, calender molding or the like. Alternatively, the resin composition may be dissolved in a solvent, and this solution may be coated on a suitable support with a suitable coating machine (coater) and dried to form a coating film, thereby forming a sheet.

The PVB layer and the EVA layer are formed by using a PVB / EVA composite resin film by two-layer extrusion molding of a PVB resin and an EVA resin, in addition to forming the respective resin films. It is also good to use a resin film formed by coating one of the resin films with the other resin composition and, for example, applying an EVA resin composition to a previously formed PVB resin film to form a two-layer resin film. May be formed.

The film reinforced glass of the present invention is excellent in impact resistance, penetration resistance, etc., and particularly excellent in crime prevention, thin and light, so that it can be fitted into automobiles, side glass and rear glass, railway vehicles, for example, ordinary vehicles. , Express vehicles,
Door glass, window glass and indoor door glass for passengers such as limited express vehicles and sleeping vehicles, window glass and indoor door glass, window glass and indoor door glass in buildings such as buildings, showcases and show windows for indoor exhibitions, and preferably for automobiles. It is useful as side or rear glass, window glass for railway vehicles, especially as door glass for automobiles.

[0052]

The present invention will be described more specifically with reference to the following examples and comparative examples.

In the following, a glass plate, an organic resin film, a PVB resin film, an EVA resin film,
The following were used as PVA / EVA resin films. Glass plate: 5 mm thick silicate glass plate which has been washed and dried beforehand Organic resin film: PET resin film having a thickness of 100 μm PVB resin film: PVB resin composition having the following composition formed into a film having a thickness of 380 μm PVB resin composition Formulation (parts by weight) PVB resin (acetalization degree: 66 mol%): 100 Plasticizer (triethylene glycol-di (2-ethylbutyrate)): 40 Adhesion regulator (potassium acetate): 0.1 EVA resin film : EVA resin composition having the following composition formed into a film with a thickness of 380 μm EVA resin composition composition (parts by weight) EVA resin (vinyl acetate content 26% by weight): 100 Crosslinking agent (1,1-bis (t- Butylperoxy) 3,3,5-trimethylcyclohexane): 2.0 Silane coupling agent (γ-methacryloxypropyl trime) Xysilane): 0.5 Crosslinking aid (triallyl isocyanurate): 2.0 Ultraviolet adsorbent (2-hydroxy-4-octylbenzophenone): 0.15 PVB / EVA resin film PVA resin film and EVA resin composition Is applied, and the PVB resin layer thickness is 380 μm and the EVA resin layer thickness is 2
A two-layer film of 00 μm

Example 1 The above-mentioned PVB / EVA resin film and PET resin film were laminated on a glass plate, placed in a rubber bag, degassed under vacuum, and preliminarily pressed at a temperature of 110 ° C. 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 to produce the film-reinforced glass of the present invention shown in FIG.

The adhesion, impact resistance and penetration resistance of this film-reinforced glass were examined by the following methods. The results are shown in Table 1. [Adhesiveness] According to JIS K 6854, a peeling test was performed to determine whether or not the PET film was peeled. The numerical values in the table indicate the peel strength. “X” indicates that the adhesiveness is poor. [Impact resistance] According to the method of JIS R 3211, an impact is applied from the glass surface, and the impact resistance is good (○), not good (×)
Was examined. [Penetration resistance] According to the method of JIS R 3211, a shock is applied from the glass surface, and the penetration resistance is good (○), not good (×)
Was examined.

Comparative Example 1 A film reinforced glass was produced in the same manner as in Example 1 except that a PVB resin film was used instead of the PVB / EVA resin film, and the adhesion was examined in the same manner. Indicated.

Comparative Example 2 A film reinforced glass was produced in the same manner as in Example 1 except that an EVA resin film was used instead of the PVB / EVA resin film.
The penetration resistance was examined, and the results are shown in Table 1.

[0058]

[Table 1]

Table 1 shows that the film-reinforced glass of the present invention is excellent in adhesiveness, impact resistance and penetration resistance.

[0060]

As described in detail above, the film-reinforced glass of the present invention has excellent impact resistance, penetration resistance and crime prevention properties, and also has excellent adhesiveness, so that it has excellent durability and thickness. Provided is a thin film reinforced glass which is thin and easy to manufacture.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an embodiment of a film-reinforced glass of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Film reinforced glass 2 Glass plate 3 Organic resin film 4 PVB layer 5 EVA layer

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F006 AA35 AB39 BA02 DA04 4F071 AA15X AA28X AA29A AA46 AB28B AH07 AH08 CA01 CB06 CB08 CD01 CD03 4F100 AG00A AK01B AK23G AK42B AK68G AS00JBA EJ23 EC03 J02 EC01

Claims (6)

[Claims] 1. A film-reinforced glass obtained by laminating and bonding a glass plate and an organic resin film via an adhesive resin layer, wherein the adhesive resin layer has a first adhesion mainly composed of polyvinyl butyral resin on the glass plate side. A film-reinforced glass comprising: a resin layer; and a second adhesive resin layer mainly composed of an ethylene-vinyl acetate copolymer resin on an organic resin film side. 2. The film-reinforced glass according to claim 1, wherein the ethylene-vinyl acetate copolymer resin of the second adhesive resin layer is cured by a crosslinking agent. 3. The film reinforced glass according to claim 1, wherein the organic resin film is a polyethylene terephthalate resin film. 4. The method according to claim 1, wherein the thickness of the first adhesive resin layer is 100 to 1000 μm.
Wherein the thickness of the second adhesive resin layer is 5 to 600 μm. 5. The film reinforced glass according to claim 1, wherein the surface of the organic resin film is subjected to a hard coat treatment. 6. The method according to claim 1, wherein the ethylene-vinyl acetate copolymer resin of the second adhesive resin layer has a vinyl acetate content of 10 to 50% by weight. Film toughened glass.