JP3535410B2 - Laminated transparent plate - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated transparent plate having excellent impact resistance, which is preferably used as, for example, a bulletproof surface, a bulletproof shield, a glazing material for various vehicles, a partition plate for a counter of a financial institution, a security door, and the like.

[0002]

2. Description of the Prior Art Impact-resistant transparent plates are used for public facilities,
It is used as a glazing material for exercise facilities, a partition plate for bank counters, a glazing material for security doors, and a glazing material for various vehicles.

As such a transparent plate, in addition to a silicate glass plate, a polycarbonate resin plate, etc., a laminated transparent plate obtained by joining a silicate glass plate and a polycarbonate resin plate using a methacrylate syrup-like material (Japanese Patent Laid-Open No. 52-100515). Japanese Laid-Open Patent Publication No. 59-12), a laminated transparent plate formed by bonding a plurality of polycarbonate resin plates through an adhesive layer made of a thermoplastic polyurethane resin (Japanese Patent Publication No. 59-12).
520, JP-A-4-301448, JP-A-4-361034, etc.) are known. However, in these transparent plates, it is necessary to increase the thickness in order to improve the impact resistance, which increases the weight,
There was a problem of lack of practicality.

As a solution to this problem, there has been proposed a transparent plate in which an acrylic resin plate and a polycarbonate resin plate are joined together via an adhesive layer (Japanese Patent Laid-Open No. 7-2.
56831, JP-A-7-290657, etc.). By these means, it has become possible to secure excellent impact resistance while reducing the weight.

[0005]

However, in the above-mentioned prior art, the impact resistance when repeatedly impacted a plurality of times was not sufficiently satisfactory. That is, although the protection performance against a strong impact itself is sufficiently exerted, when a shock is applied multiple times, especially when the same position is applied multiple times, small debris is scattered from the periphery of the impact part, There is a problem in that the debris from the impact point of the transparent plate may be lost and the visibility from the impact point may be reduced. In addition, if such a missing part is assumed to be used continuously,
It is not very desirable as a product appearance. From such a background, it has been desired to develop a transparent plate having sufficiently improved impact resistance when repeatedly subjected to multiple impacts without impairing various properties such as lightness and transparency.

The present invention has been made in view of the above technical background, and is lightweight and excellent in transparency, and
An object of the present invention is to provide a laminated transparent plate that can exhibit sufficient protection performance against a strong impact and is also excellent in impact resistance when repeatedly receiving such an impact multiple times.

[0007]

In order to achieve the above object, the inventors of the present invention have earnestly studied, and as a result, the acrylic resin plate and the polycarbonate resin plate have a glass transition temperature (Tg) of 50 ° C. or less. The first surface layer made of a polycarbonate resin is joined and integrated to the surface of the acrylic resin plate in the laminated substrate formed by joining the resin layer, which is a second surface layer made of an acrylic resin. As a result, they have found that the impact resistance against a plurality of impacts can be further improved while securing the lightness and the transparency, and have completed the present invention.

That is, in the laminated transparent plate according to the present invention, a second base plate made of a polycarbonate resin is formed on one surface of a first base plate made of an acrylic resin, and a resin having a glass transition temperature of 50 ° C. or lower. A first surface layer made of a polycarbonate resin is bonded to the other surface of the first base plate via a second surface layer made of an acrylic resin while being bonded via an elastic bonding layer. It is characterized by. Since the laminated substrate is composed of an acrylic resin plate and a polycarbonate resin plate bonded via an elastic bonding layer made of a resin having a glass transition temperature of 50 ° C. or less, it is lightweight and transparent. It is excellent and exhibits sufficient protection performance against strong impact. Moreover, since the first surface layer made of polycarbonate resin is bonded to the other surface of the acrylic resin plate via the second surface layer made of acrylic resin, sufficient lightness and transparency are ensured. At the same time, it is also excellent in impact resistance when repeatedly subjected to a strong impact multiple times.

In another laminated transparent plate of the present invention, a third base plate made of a polycarbonate resin has a first bonding layer made of an acrylic resin on one surface of a first base plate made of an acrylic resin. The second base plate made of a polycarbonate resin is further bonded to the other surface of the third base plate via an elastic bonding layer made of a resin having a glass transition temperature of 50 ° C. or lower, A first surface layer made of a polycarbonate resin is bonded to the other surface of the first base plate via a second surface layer made of an acrylic resin. The laminated substrate is formed by laminating a first bonding layer, a third base plate, an elastic bonding layer having a glass transition temperature of 50 ° C. or less, and a second base plate in this order on one surface of the first base plate. Therefore, it is lightweight, has excellent transparency, and exhibits sufficient protection performance against strong impact. Moreover, since the first surface layer made of a polycarbonate resin is bonded to the other surface of the first base plate via the second surface layer made of an acrylic resin, sufficient lightness and transparency are secured. It is also said to have excellent impact resistance when repeatedly subjected to a strong impact multiple times. Furthermore, since the third transparent base plate made of a polycarbonate resin is laminated at a specific position, the laminated transparent plate according to this configuration can reduce the warpage during the production even if it has a large configuration. The work is easy and the work efficiency is excellent, the warpage of the laminated transparent plate is reduced, and the bonding strength is excellent. In this respect, the laminated transparent plate according to the present configuration is superior to the laminated transparent plate according to the former configuration.

In the above, the first base plate contains the multilayer elastic particles in an amount of 0.1 to 0.1 parts by weight with respect to 100 parts by weight of the acrylic resin.
It is preferably contained in an amount of 72 parts by weight. In this case, impact resistance is further improved, and more excellent protection performance against strong impact can be exhibited.

The glass transition temperature of the resin constituting the elastic bonding layer is preferably -30 to 40 ° C. As a result, the impact resistance is further improved, the protection performance is further improved, and the impact resistance when repeatedly receiving a strong impact a plurality of times, that is, the repeated impact resistance is further improved.

The resin forming the elastic bonding layer is preferably an epoxy resin or an acrylic resin. With such a structure, the adhesiveness of the elastic bonding layer can be further improved, and the impact resistance and transparency of the laminated transparent plate can be further improved.

The resin constituting the elastic bonding layer is preferably a bisphenol type epoxy-based curable resin, which further improves the adhesiveness of the bonding layer, and
Impact resistance and transparency as a laminated transparent plate are further improved.

In the above, it is preferable that the resin forming the second surface layer has a Vicat softening point of 50 to 90 ° C. and a haze ratio of 1 to 60% at a thickness of 50 μm. If the Vicat softening point deviates from the above specified range, it tends to be difficult to join in a good state,
It is preferable to use a Vicat softening point of 50 to 90 [deg.] C. because the joint strength is lowered. Also,
When the haze ratio is within the above-specified range, it is possible to achieve sufficient air release during lamination and ensure sufficient transparency as a laminated transparent plate. For the same reason, the resin forming the first bonding layer has a Vicat softening point of 50 to 90 ° C., and the haze ratio of the resin at a thickness of 50 μm is 1 to 1.
It is preferably 60%.

The thickness of the second surface layer is preferably 10 to 1000 μm from the viewpoint of ensuring sufficient adhesive strength and excellent repeated impact resistance while maintaining low cost. For the same reason, the thickness of the first bonding layer is 10 to 1
It is desirable to set it to 000 μm.

The thickness of the first surface layer is 0.1 to 3 mm.
It is desirable that this ensures excellent repeated impact resistance while maintaining sufficient lightness.

Further, the thickness of the first base plate is 3 to 30 mm.
It is desirable that the second base plate has a thickness of 3 to 15 mm, and thereby, further excellent protection performance can be secured while maintaining sufficient lightness.

Further, the thickness of the elastic bonding layer is 0.1 to 4 mm.
Is desirable, which ensures excellent impact resistance while maintaining sufficient lightness.

The thickness of the third base plate is 0.1 to 3 m.
It is desirable that the thickness be m, whereby a further excellent protection performance is secured while maintaining sufficient lightness. In addition, even if the structure is large, it is possible to sufficiently prevent warpage.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of a laminated transparent plate according to the present invention will be described below with reference to the drawings.

The laminated transparent plate (1) of the first invention is, as shown in FIG. 1, a first base plate (2) made of an acrylic resin.
A second base plate (3) made of a polycarbonate-based resin is bonded to one surface of the substrate through an elastic bonding layer (8) made of a resin having a glass transition temperature (Tg) of 50 ° C. or lower, and the first base plate A first surface layer (5) made of a polycarbonate resin is bonded to the other surface of the base plate (2) via a second surface layer (6) made of an acrylic resin. On the surface of the first base plate (2) in the laminated substrate (9) composed of the first base plate (2), the elastic bonding layer (8), and the second base plate (3), the first base plate (2) made of acrylic resin is used. By joining the first surface layer (5) made of a polycarbonate resin via the two surface layers (6), that is, by laminating and integrating these surface layers (5) and (6), it is possible to withstand multiple impacts. The impact resistance was further improved. In addition, since the elastic bonding layer (8) is composed of a resin having a glass transition temperature (Tg) of 50 ° C. or lower, in combination with the structure of the surface layers (5) and (6), The impact resistance against impact can be remarkably improved.

The laminated transparent plate (1) according to the second invention
As shown in FIG. 2, the third base plate (4) made of a polycarbonate resin has a first bonding layer (7) made of an acrylic resin on one surface of the first base plate (2) made of an acrylic resin. The second base plate (3) made of a polycarbonate resin is bonded to the other surface of the third base plate (4) via a resin having a glass transition temperature (Tg) of 50 ° C. or lower. While being bonded via an elastic bonding layer (8), a second surface layer (5) made of a polycarbonate resin and a second surface layer made of an acrylic resin is formed on the other surface of the first base plate (2). It is joined through the surface layer (6). The surface of the first base plate (2) in the laminated substrate (9) composed of the first base plate, the first bonding layer, the third base plate, the elastic bonding layer, and the second base plate is made of an acrylic resin. By joining the first surface layer (5) made of a polycarbonate resin via the second surface layer (6), that is, by laminating and integrating these surface layers (5) and (6), a plurality of impacts are performed. It was possible to further improve the impact resistance to. In addition, since the elastic bonding layer (8) is made of a resin having a glass transition temperature (Tg) of 50 ° C. or less, the elastic bonding layer (8) is used a plurality of times in combination with the function of the surface layer (5) (6). It was possible to remarkably improve the impact resistance against the impact. Furthermore, since the third base plate made of polycarbonate resin is laminated at a specific position, even in the case of a large-sized structure, the warp at the time of manufacturing can be reduced, the manufacturing work is easy and the work efficiency is excellent. The warp of the transparent plate is also reduced, resulting in a high quality product with excellent bonding strength. In this respect, the laminated transparent plate according to the second invention is superior to the laminated transparent plate according to the first invention.

The acrylic resin which constitutes the first base plate (2) is not particularly limited, but for example, polymethylmethacrylate, methylmethacrylate and other monomers copolymerizable therewith can be used. Examples thereof include polymers. Other monomers copolymerizable with methyl methacrylate include, for example, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, and other alkyl methacrylates having an alkyl group having 2 to 8 carbon atoms, methyl acrylate, ethyl acrylate, propyl acrylate. , Butyl acrylate, octyl acrylate, and other alkyl acrylates having an alkyl group having 1 to 8 carbon atoms, methacrylic acid, acrylic acid, methacrylamide, acrylamide, styrene, glycidyl methacrylate, glycidyl acrylate, and the like, and mixtures thereof.

Among such acrylic resins, a copolymer of 90% by weight or more of methyl methacrylate and 10% by weight or less of one or two compounds selected from glycidyl methacrylate and glycidyl acrylate has a glass transition temperature of 50. It is preferably used because it has excellent bonding strength with the elastic bonding layer (8) having a temperature of not higher than 0 ° C.

The acrylic resin can be produced by a known method in which methyl methacrylate alone, or methyl methacrylate and another monomer are cast, emulsion, suspension or bulk polymerized.

The acrylic resin may be crosslinked. When crosslinked, surface hardness and solvent resistance are improved. To obtain a crosslinked acrylic resin, the total amount of the above methyl methacrylate and other monomers is 10
A crosslinking agent may be added in an amount of 20 parts by weight or less with respect to 0 parts by weight for polymerization.

As the cross-linking agent, one having a plurality of polymerizable unsaturated bonds in the molecule is usually used. For example, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, diethylene glycol di Examples thereof include (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and allyl (meth) acrylate.

The first base plate (2) is a layer made of the above acrylic resin. The acrylic resin contains multilayer elastic particles, but the impact resistance is further improved and it is more excellent. It is preferable in that the protective performance can be obtained.

The multilayer elastic particles are the same as those usually used for an acrylic resin plate having impact resistance. For example, the inner core layer is a crosslinked acrylate copolymer and the outer core layer is an acrylic ( Two-layer structure elastic particles which are a copolymer), the inner core layer is a crosslinked methacrylate-based (co) polymer, and the intermediate layer is a crosslinked acrylate-based copolymer,
Examples thereof include three-layer structure elastic particles in which the outer core layer is an acrylic (co) polymer.

The acrylic (co) polymers constituting the outer core layer of the two-layer structure elastic particles and the outer core layer of the three-layer structure elastic particles include, for example, an alkyl group having 1 to 4 carbon atoms. Mention may be made of 60-100% by weight of methacrylate and 40-0% by weight of other monomers having double bonds (co) polymers. Here, examples of the alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and a mixture thereof. Further, as the other monomer having a double bond, for example, an alkyl acrylate such as methyl acrylate or ethyl acrylate, or a monomer copolymerizable with an alkyl methacrylate such as styrene, acrylonitrile, methacrylate, or 2-hydroxymethacrylate. And so on.

The cross-linked acrylate-based copolymer constituting the inner core layer of the two-layer structure elastic particles and the intermediate layer of the three-layer structure elastic particles is, for example, an alkyl acrylate monomer having an alkyl group having 1 to 8 carbon atoms. 45-99.5% by weight, aromatic vinyl monomer 0-40% by weight, polyfunctional monomer 0-1
A crosslinked acrylate-based copolymer obtained by copolymerizing a mixture of 0% by weight and 0.5 to 5% by weight of a grafting monomer can be mentioned. Here, examples of the alkyl acrylate monomer having an alkyl group having 1 to 8 carbon atoms include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and octyl acrylate. Examples of aromatic vinyl monomers include α
-Methylstyrene, chlorostyrene, p-tert-butylstyrene and the like. Examples of polyfunctional monomers include ethylene glycol diacrylate, 1,2
Examples include alkylene glycol diacrylates such as propylene glycol diacrylate and 1,3-propylene glycol diacrylate, and alkylene glycol dimethacrylates such as ethylene glycol dimethacrylate and triethylene glycol dimethacrylate. Examples of the grafting monomer include α, β-
Examples include unsaturated carboxylic acid, dicarboxylic acid allyl ester, methallyl ester, and crotyl ester.
Of these, allyl methacrylate and diallyl methacrylate are preferable.

The crosslinked methacrylate (co) polymer constituting the inner core layer of the three-layer structure elastic particles includes, for example, 60 to 99.8% by weight of alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms and a double bond. Other monomer having 0
A cross-linked methacrylate (co) polymer obtained by copolymerizing a mixture of ˜40% by weight, a polyfunctional monomer of 0-5% by weight and a grafting monomer of 0.2-2% by weight. Here, as the alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms, another monomer having a double bond, a polyfunctional monomer, and a grafting monomer, an inner core layer of a two-layer structure elastic particle is used. And compounds similar to those mentioned for the outer core layer.

Such multilayer elastic particles can be produced by a known method.

When the first base plate (2) contains the multilayer elastic particles, the content thereof is preferably 0.1 to 72 parts by weight with respect to 100 parts by weight of the acrylic resin,
More preferably 5 to 33 parts by weight, particularly preferably 8 to
It is in the range of 25 parts by weight. If the amount is less than 0.1 parts by weight, the effect of improving impact resistance is poor and the effect of using the multilayer elastic particles cannot be sufficiently obtained, which is not preferable. On the other hand, 7
On the other hand, if the amount exceeds 2 parts by weight, the impact resistance tends to decrease, and the portion is likely to be whitened when an impact is applied, which is not preferable.

In order to ensure the transparency of the obtained first base plate (2), the refractive index of the multilayer elastic particles used is the first.
It is preferable that the refractive index of the acrylic resin forming the base plate (2) is substantially the same.

In order to make the first base plate (2) contain the multi-layered elastic particles, the multi-layered elastic particles and the above-mentioned acrylic resin may be melt-kneaded, or may be previously kneaded when the acrylic resin is polymerized. The multilayer elastic particles may be added together with the additives described below.

A first base plate (2) made of an acrylic resin containing the multi-layered elastic particles thus obtained.
Can be produced by a known method (for example, JP-B-55-27576, JP-A-8-151498, etc.) and may be a commercially available product. Examples of such commercially available products include Sumipex GT (Sumitomo Chemical Co., Ltd.)
Manufactured by Sumitomo Chemical Co., Ltd.) and the like.

Further, the acrylic resin may contain additives. Examples of the additive include an ultraviolet absorber,
Antioxidants, plasticizers, colorants and the like can be mentioned.

Examples of the ultraviolet absorber include Tinuvin P
(Ciba-Geigy Co., Ltd.), Sumisorb 340 (Sumitomo Chemical Co., Ltd.) and other benzotriazole compounds, Seesorb 101S (Cypro Kasei Co., Ltd.), Sumisorb 110
Benzophenone compounds such as (Sumitomo Chemical Co., Ltd.), Tinuvin 770 (Ciba-Gaigi Co., Ltd.), Sanol L
Examples of the UV absorber include a hindered amine compound such as S2626 (Sankyo Co., Ltd.). When an ultraviolet absorber is added, the amount added is 10
It is usually 1 part by weight or less, preferably 0.0 with respect to 0 part by weight.
It is in the range of 1 to 0.2 parts by weight.

Examples of the antioxidant include Sumilizer BO101 (Sumitomo Chemical Co., Ltd.) and Sumilizer GM.
(Sumitomo Chemical Co., Ltd.) and other phenolic compounds, Mark PEP-8 (ADEKA CORPORATION), Mark PEP-24
(Adeka Corp.) and other phosphorus compounds.

Examples of the plasticizer include aromatic carboxylic acids such as dibutyl phthalate and dioctyl phthalate,
Examples thereof include aliphatic polybasic acid esters such as dioctyl adipate and acetyltributyl citrate.

As the colorant, for example, Sumiplast Gr
eenG (Sumitomo Chemical Co., Ltd.), Sumiplast Blu
Examples thereof include anthraquinone dyes such as eOR (Sumitomo Chemical Co., Ltd.) and perinone dyes such as Sumiplast Orange HRP (Sumitomo Chemical Co., Ltd.).

The thickness of the first base plate (2) is 3 to 3
It is preferably 0 mm. If it is less than 3 mm, excellent impact resistance cannot be secured, which is not preferable.
If it exceeds mm, not only is the weight increased, the weight cannot be sufficiently reduced, but also the cost is increased, which is not preferable. Above all, it is more preferably 5 to 15 mm, and particularly preferably 8 to 13 mm.

Next, the polycarbonate resin constituting the first surface layer (5) is not particularly limited, but examples thereof include high-molecular thermoplastic polycarbonate, and among them, those comprising dihydroxydiarylalkane. It is particularly preferably used because it has excellent impact resistance.

The thickness of the first surface layer (5) is 0.1 to
It is preferably 3 mm. If it is less than 0.1 mm, the impact resistance cannot be sufficiently ensured when repeatedly subjected to multiple impacts, which is not preferable. On the other hand, if the thickness exceeds 3 mm, not only the weight increases but sufficient lightness cannot be ensured, but also the cost increases, which is not preferable. Above all 0.3
3 mm is more preferable, and 0.5 is particularly preferable.
~ 2 mm.

Next, the second surface layer (6) will be described. The second surface layer (6) has a function of firmly bonding the first base plate (2) and the first surface layer (5), and
It also contributes to the improvement of impact resistance when repeatedly impacted multiple times. The acrylic resin forming the second surface layer (6) is not particularly limited, and examples thereof include the same compounds as the compounds listed as the acrylic resin forming the first base plate (2). Of these, it is preferable to use one having a Vicat softening point of 50 to 90 ° C. among these. If the Vicat softening point deviates from the above specified range, it tends to be difficult to join in a good state, and the joining strength decreases, so it is preferable to use a Vicat softening point of 50 to 90 ° C. .

The haze ratio of the acrylic resin constituting the second surface layer (6) at a thickness of 50 μm is 1 to 60.
% Is desirable. When the second surface layer (6) is laminated, it is preferable that the surface of the acrylic resin layer is slightly uneven so that air can easily escape.
The haze ratio at 0 μm is 1 to 60%. If the haze ratio is less than 1%, the escape of air during lamination becomes insufficient, and if it exceeds 60%, the transparency of the laminated transparent plate is deteriorated, which is not preferable. The haze ratio is more preferably 1 to 10%, particularly preferably 2 to 5%.

As a commercial product of an acrylic resin sheet having a Vicat softening point of 50 to 90 ° C. and a haze ratio of 1 to 60% at a thickness of 50 μm, for example, Sanjuren 002AN manufactured by Kanegafuchi Chemical Industry is suitable. .

The thickness of the second surface layer (6) is 10 to 1
The thickness is preferably 000 μm. If it is less than 10 μm, not only is it impossible to ensure sufficient impact resistance when repeatedly subjected to multiple impacts, but the adhesive strength between the first base plate and the first surface layer decreases, which is not preferable. While 1000
Even if it exceeds μm, it is not preferable because the effect more than that corresponding to the increase in thickness cannot be obtained and the cost is increased unnecessarily. Above all, it is more preferably 20 to 200 μm, and particularly preferably 40 to 120 μm.

On the other hand, examples of the polycarbonate-based resin constituting the second base plate (3) include, for example, high-molecular thermoplastic polycarbonates as described above, and among them, those made of dihydroxydiarylalkane have particularly high impact resistance. It is preferably used because it is excellent. The thickness of the second base plate (3) is preferably 3 to 15 mm. If it is less than 3 mm, excellent impact resistance cannot be ensured, which is not preferable. On the other hand, if it exceeds 15 mm, not only is the weight increased to prevent sufficient weight reduction, but also the cost is increased, which is not preferable. Above all, it is more preferably 3 to 8 mm.

Next, the kind of resin constituting the elastic bonding layer (8) is not particularly limited, and examples thereof include polyvinyl butyral, epoxy resin, urethane resin, silicon resin, acrylic resin, and the like. Among these, a resin having a glass transition temperature (Tg) of 50 ° C. or lower is used. This is because if the glass transition temperature exceeds 50 ° C., not only the impact resistance is lowered and the protective performance is lowered, but also the impact resistance when repeatedly receiving a strong impact, that is, the repeated impact resistance is also lowered. . Among them, the glass transition temperature (Tg) of the elastic bonding layer (8) is preferably -50 to 50 ° C. If the Tg is lower than -50 ° C, the impact resistance decreases, which is not preferable. Among them, the glass transition temperature (Tg) of the elastic bonding layer (8) is more preferably −30 to 40 ° C., and particularly preferably −20 to 30 ° C. In addition, T
g can be measured by a differential thermal analysis method (DSC method). Usually, when the temperature at which the laminated transparent plate (1) is used is low, a resin having a relatively low glass transition temperature is used.

Epoxy resin and acrylic resin are suitable as the kind of resin constituting the elastic bonding layer (8). If these resins are used, the elastic bonding layer (8)
This is because it is possible to further improve the adhesiveness of 1 and further improve the impact resistance and transparency of the laminated transparent plate. Of these, a bisphenol type epoxy-based curable resin is particularly suitable.

The bisphenol epoxy resin is a cured resin obtained by curing a bisphenol epoxy resin, and can be obtained by reacting a bisphenol epoxy resin with a curing agent, for example.

[0054] The bisphenol type epoxy resin, a bisphenol type epoxy resin having 2 or more epoxy groups, specifically include bisphenol A type epoxy resin, bisphenol F type epoxy resins such Doya, each epoxy resin And the like. Above all, it is desirable to use a mixture containing 5 to 30 parts by weight of the bisphenol A type epoxy resin with respect to 100 parts by weight of the bisphenol F type epoxy resin. With this configuration, transparency and flexibility of the elastic bonding layer (8) at room temperature can be obtained. It is possible to obtain a laminated transparent plate (1) having better flexibility. Furthermore, it is more preferable to use a mixture containing 10 to 25 parts by weight of the bisphenol A type epoxy resin with respect to 100 parts by weight of the bisphenol F type epoxy resin.

As the curing agent, for example, an aliphatic hydrocarbon compound having two or more amino groups is used, and specifically, an aliphatic diamine such as polymethylenediamine and polyetherdiamine, diethylenetriamine and triethylenetetramine. , 1,2-substituted diamines, substituted polyamines, dimethylaminopropylamine, aminoethylethanolamine, methyliminopropylamine and other aliphatic polyamines, methanediamine, 1,3-diaminocyclohexane and other aliphatic polyamines.
Among them, it is preferable to use polyether diamine because it is less colored and a laminated transparent plate (1) having excellent flexibility of the elastic bonding layer (8) can be obtained. The amount of the curing agent used is usually about 25 to 140 parts by weight, preferably 80 to 1 with respect to 100 parts by weight of the bisphenol type epoxy resin.
20 parts by weight.

Thus, the bisphenol type epoxy-based curable resin can be formed by a method of curing a mixture of the bisphenol type epoxy resin and the curing agent.

When curing, for example, a bisphenol type epoxy resin and a curing agent may be mixed and then heated. The heating temperature is usually 20 to 150 ° C., preferably 20.
~ 80 ° C. Even if the heating temperature is lower than 20 ° C., the composition is cured, but it tends not to be sufficiently cured, which is not preferable.

Upon curing, a reactive diluent or a non-reactive diluent may be mixed.

Examples of the reactive diluent include monoepoxy compounds such as styrene oxide and octylene oxide, polyepoxy compounds such as diglycidyl ether and butanediol glycidyl ether, and mixtures thereof. The amount thereof is bisphenol. It is usually 80 parts by weight or less with respect to 100 parts by weight of the type epoxy resin.

Examples of the non-reactive diluent include solvents such as xylene and glycol, and plasticizers such as phthalic acid ester. The amount thereof is usually 80 parts by weight or less per 100 parts by weight of bisphenol type epoxy resin. . It is preferable to use such a non-reactive diluent from the viewpoint that a laminated transparent body (1) having a more flexible elastic bonding layer (8) can be obtained.

The acrylic resin constituting the elastic bonding layer (8) is, for example, 77 to 98.9% by weight of an acrylic monomer or its partial polymer, 1 to 20% by weight of a plasticizer, and polyfunctional. A preferable example is a resin obtained by polymerizing a mixture of 0.1 to 3% by weight of a monomer.

The acrylic monomer has 5 carbon atoms.
To alkyl methacrylate having an alkyl group of 8 to 50
To 100% by weight, 0 to 10% by weight of alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, and 0 to 40% by weight of alkyl methacrylate having an alkyl group of 1 to 4 carbon atoms. Examples of the alkyl methacrylate having an alkyl group having 5 to 8 carbon atoms include amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, and the like, and examples of the alkyl acrylate having an alkyl group having 1 to 8 carbon atoms include: Methyl acrylate,
Examples thereof include ethyl acrylate, propyl acrylate, butyl acrylate, and octyl acrylate. Examples of the alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms include methyl methacrylate and ethyl methacrylate.

Examples of the plasticizer include known external plasticizers for acrylic resins such as phthalic acid, adipic acid, sebacic acid, dimethyl phthalate, dioctyl phthalate, dioctyl adipate, dioctyl sebacate and acetyl tributyl citrate. To be

Examples of the polyfunctional monomer include divinylbenzene, ethylene glycol dimethacrylate,
Examples thereof include butylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate and the like.

Therefore, the elastic bonding layer (8) made of an acrylic resin is prepared by adding a suitable polymerization initiator to a mixture of an acrylic polymer or its partial polymer, a plasticizer and a polyfunctional monomer. It can be formed by a method of polymerizing and curing.

The elastic bonding layer (8) may contain various additives such as an ultraviolet absorber, an antioxidant and a coloring agent.

Examples of the ultraviolet absorber include the same benzotriazole compounds, benzophenone compounds, and hindered amine compounds as mentioned above.

Examples of the antioxidant include phenolic compounds and phosphorus compounds similar to those mentioned above, as well as inorganic phosphorus such as disodium hydrogen phosphite pentahydrate and sodium hypophosphite. Examples thereof include acid salts.

Examples of colorants include anthraquinone dyes and perinone dyes similar to those mentioned above, fluorescein, thioflavin, eosin, rhodamine, coumarin, imidazole, oxazole, triazole, and the like.
Carbazole, pyridine, naphthalic acid, imidazolone,
Examples thereof include fluorescent whitening dyes such as diaminostilbene disulfonic acid and derivatives thereof.

Also, 100% modulus of the elastic bonding layer (8) (value measured by JIS K 6251)
Is preferably 5 to 150 kgf / cm ² .

Further, the thickness of the elastic bonding layer (8) is 0.1 to 10.
It is preferably 4 mm. If it is less than 0.1 mm, it is not preferable because sufficient bonding strength cannot be secured. On the other hand, if it exceeds 4 mm, sufficient impact resistance cannot be obtained.
This is not preferable because it also increases the cost. Above all, 1-3m
More preferably, it is m.

Next, the acrylic resin constituting the first bonding layer (7) is not particularly limited, and for example, the second resin can be used.
The same resins as those listed as the acrylic resin forming the surface layer (6) can be exemplified.

It is preferable that the acrylic resin constituting the first bonding layer (7) has a Vicat softening point of 50 to 90 ° C. and a haze ratio of 1 to 60% at a resin thickness of 50 μm. The reason why the material having such a range is preferable is the same as the reason for limitation described in the description of the second surface layer. Above all, the thickness of the resin constituting the first bonding layer (7) is 5
The haze ratio at 0 μm is more preferably 1 to 10%, particularly preferably 2 to 5%.

The thickness of the first bonding layer (7) is 10 to 1
The thickness is preferably 000 μm. If it is less than 10 μm, not only is it impossible to ensure sufficient impact resistance when repeatedly subjected to multiple impacts, but the adhesive strength between the first base plate and the second base plate decreases, which is not preferable. While 100
Even if the thickness exceeds 0 μm, it is not preferable because the effect more than that corresponding to the increase in thickness cannot be obtained and the cost is unnecessarily increased.
Above all, it is more preferably 20 to 200 μm, and particularly preferably 40 to 120 μm.

Next, examples of the polycarbonate-based resin constituting the third base plate (4) include high-molecular thermoplastic polycarbonate, etc., as described above, and among them, those composed of dihydroxydiarylalkanes are particularly impact resistant. It is preferably used because it has excellent properties. The thickness of the third base plate (4) is preferably 0.1 to 3 mm. If it is less than 0.1 mm, it becomes difficult to suppress the warp, which is not preferable. On the other hand, if it exceeds 3 mm, not only the weight increases to prevent sufficient weight reduction but also the cost increases, which is not preferable. Above all, 0.5-2m
More preferably, it is m.

In order to manufacture the laminated transparent body of the first invention, for example, a polycarbonate resin plate (first plate) is formed on one surface of a first base plate made of acrylic resin with an acrylic resin film (second surface layer) interposed therebetween. 1 surface layer) and then the first
A second base plate made of a polycarbonate resin may be bonded to the other surface of the base plate via a resin layer (elastic bonding layer) having a glass transition temperature of 50 ° C. or lower, or made of an acrylic resin. On one surface of the first base plate,
A second base plate made of a polycarbonate resin is bonded via a resin layer (elastic bonding layer) having a glass transition temperature of 50 ° C. or lower, and then an acrylic resin film (second resin film) is formed on the other surface of the first base plate. The polycarbonate resin plate (first surface layer) may be joined via the surface layer). Of course, all of these constituent materials may be laminated at the same time, and the order of lamination is not particularly limited.

In order to manufacture the laminated transparent body of the second invention, for example, a polycarbonate resin plate (first plate) is formed on one surface of the first base plate made of acrylic resin with an acrylic resin film (second surface layer) interposed therebetween. 1 surface layer) and the polycarbonate resin plate (3rd base plate) are simultaneously bonded to the other surface of the 1st base plate via the acrylic resin film (1st bonding layer), and then the other surface of the 3rd base plate. The second base plate made of polycarbonate resin on the surface of the
It may be bonded via a resin layer (elastic bonding layer) having a temperature of 0 ° C. or lower, or the second base plate and the third base plate may be bonded with a resin layer having a glass transition temperature of 50 ° C. or lower first. After bonding by bonding, other layers may be sequentially stacked. Of course, all of these constituent materials may be laminated at the same time, and the order of lamination is not particularly limited.

The first base plate made of acrylic resin is
It can be manufactured by a method such as an extrusion molding method or a cast molding method.

An acrylic resin film (second surface layer) is formed on one surface of the first base plate made of the acrylic resin.
In order to bond the polycarbonate resin plate (first surface layer) via the, for example, a method of stacking an acrylic resin film and a polycarbonate resin plate in this order on one surface of the first base plate, and then hot pressing, Alternatively, there may be mentioned a method of vacuum bonding in the state of being stacked.

For hot pressing, for example, a first base plate made of an acrylic resin, an acrylic resin film and a polycarbonate resin plate may be stacked in this order between a pair of heated molds and pressed. The heating temperature of the mold is usually 120 to 200 ° C., preferably 140 to 180 ° C., and the pressing pressure is usually 5 to 80 kgf / cm ² ,
The range is preferably 30 to 50 kgf / cm ² . Heating temperature is less than 120 ° C, press pressure is 5kg
If it is less than f / cm ² , it is between the first base plate and the acrylic resin film (second surface layer) or between the acrylic resin film (second surface layer) and the polycarbonate resin plate (first
It is not preferable because bubbles may form between the surface layer) and the bonding strength becomes insufficient. Also, the heating temperature exceeds 200 ° C, and the pressing pressure is 80 kgf / cm ²
If it exceeds, the polycarbonate resin plate (first surface layer)
The first base plate may flow or be deformed during pressing, which is not preferable.

For vacuum bonding, for example, a state in which an acrylic resin film is held between a first base plate made of acrylic resin and a polycarbonate resin plate in a vacuum bag for vacuum bonding laminated glass Then, the inside of the vacuum bag is decompressed, heated to 100 to 180 ° C., and bonded. Then, by heating again, the polycarbonate resin plate (first surface layer) is provided on one surface of the acrylic resin plate with the acrylic resin film (second surface layer) interposed therebetween.
Can be joined. The heating temperature in the reheating is usually 100 to 200 ° C, preferably 130 to 170 ° C.
Is the range. The reheating is preferably performed under a pressure of 1 atm or more. When pressurizing, the pressure is usually 15 atm or less, preferably about 6 to 12 atm.

In the production of the laminated transparent body of the first invention, a second base plate made of a polycarbonate resin is provided on one surface of a first base plate made of an acrylic resin, and a resin having a glass transition temperature of 50 ° C. or lower. For bonding via a layer (elastic bonding layer), for example, a resin having a glass transition temperature of 50 ° C. or lower is provided by arranging a first base plate and a second base plate with a gap so as to face each other. Then, a curing agent may be injected and cured. Reactive diluents, non-reactive diluents, and various additives can be injected together with the resin having a glass transition temperature of 50 ° C. or lower. For injection, first
To dispose the base plate and the second base plate with a space therebetween, they may be arranged via a spacer. The thickness of the spacer is determined according to the intended thickness of the elastic bonding layer (8).

To cure after injection, it may be left at room temperature as it is, but since the polymerization takes a long time and the polymerization is likely to be incomplete, it may be heated, and usually the temperature is gradually raised. Temperature rise up to 150 ℃, preferably 80 ℃
Is done until. The heating time is usually about 10 to 50 hours. If the heating temperature exceeds 150 ° C., the first base plate and the second base plate may flow or deform.

In the production of the laminated transparent body of the second invention, a polycarbonate resin plate (third part) is formed on one surface of the first base plate made of an acrylic resin via an acrylic resin film (first bonding layer). To join the base plate),
For example, an acrylic resin film and a polycarbonate resin plate are stacked in this order on one surface of the first base plate,
Then, a method of hot pressing in the same manner as described above, or a method of vacuum laminating in the same state as described above in a state of being overlapped with each other can be used.

Furthermore, in the production of the laminated transparent body of the second invention, a second base plate made of a polycarbonate resin is provided on one surface of the third base plate made of a polycarbonate resin at a glass transition temperature of 50 ° C. or lower. For joining via a resin layer (elastic joining layer), for example, the third base plate and the second base plate are arranged with a gap so as to face each other,
A resin having a glass transition temperature of 50 ° C. or lower and a curing agent may be injected into the gap and cured. Reactive diluents, non-reactive diluents, and various additives can be injected together with the resin having a glass transition temperature of 50 ° C. or lower.

At the time of injection, in order to arrange the second base plate and the third base plate with a space therebetween, it is sufficient to arrange them through a spacer. The thickness of the spacer is determined according to the intended thickness of the elastic bonding layer (8).

To cure after injection, it may be left at room temperature as it is, but since the polymerization takes time and the polymerization is likely to be incomplete, it may be heated, and the temperature is usually gradually raised. Temperature rise up to 150 ℃, preferably 80 ℃
Is done until. The heating time is usually about 10 to 50 hours. If the heating temperature exceeds 150 ° C., the second base plate and the third base plate may flow or deform.

In the laminated transparent plate according to the first invention, when a large-sized laminated transparent plate is to be manufactured, a polycarbonate resin plate (first surface layer) (5), an acrylic resin film (second surface layer) (6), the laminated plate composed of three layers of the first base plate (2) made of an acrylic resin is liable to warp, and therefore the first base plate (2) and the second base plate (3) are warped. The injected liquid easily leaks from the gap, and the joint tends to be insufficient. For example, 2000 mm x 1
When a laminated transparent plate of 000 mm (construction of the first invention) is manufactured, the resulting laminated transparent plate has a warp of about 10 mm (when the laminated transparent body is placed on a flat plate, the flat plate reference surface of the central convex portion). (The height from the height), the injected liquid is likely to leak, which makes the injection work difficult, and the leakage also reduces the bonding strength.

The problem of warpage in the case of constructing such a large-sized laminated transparent plate is that the specific third base plate (4) is laminated on the structure of the first invention, that is, 2 It can be solved by adopting the configuration according to the invention.
That is, the second invention is particularly excellent in the case of forming a large-sized laminated transparent plate as compared with the first invention. That is, the second
The invention can remarkably reduce the warp even in the case of a large-sized structure, and thus can form a laminated transparent plate having excellent bonding strength. Therefore, it is not necessary to take special measures to correct the warp. In this way, the laminated transparent plate of the second invention is simply a specific third base plate (4).
Even when a large-sized structure is formed by stacking layers, it is possible to reduce the warp during manufacturing, do not hinder the liquid injection work during manufacturing, and obtain the warped laminated transparent plate (1). Can also be reduced, which in turn can be of high quality with excellent bonding strength.

The laminated transparent plate (1) of the present invention may be a flat plate or may have a curved surface. In order to obtain the laminated transparent plate (1) having such a curved surface, for example, in the first invention, the first base plate to be used, the second base plate, and the polycarbonate resin plate constituting the first surface layer are preliminarily aimed. Those having curved surfaces may be used respectively. In this case, it is preferable to use a vacuum bonding method to bond the polycarbonate resin plate forming the first surface layer to one surface of the first base plate via the acrylic resin film.

The laminated transparent plate (1) of the present invention thus obtained may be subjected to antifogging treatment, light resistance treatment, surface hardening treatment or the like on one side or both sides thereof.

[0092]

EXAMPLES Hereinafter, specific examples of the present invention will be described, but the present invention is not limited to these examples.

<Material used> (Acrylic resin plate A) Methyl methacrylate monomer 10
To 0 parts by weight, 20 parts by weight of a powder of a methyl methacrylate resin (methyl methacrylate unit 98% by weight, methyl acrylate unit 2% by weight) obtained by a suspension polymerization method was added with stirring, and at 60 ° C. The stirring was continued for 2 hours to dissolve the methyl methacrylate resin. Then, 15 parts by weight of a multilayer elastic particle having a three-layer structure (multilayer elastic particle having an elastomer content of 25.2% by weight obtained by the method described in JP-B-55-27576, Example 3) was added with stirring. 1
After stirring for a period of time, it was cooled to room temperature to obtain a syrup in which the multilayer elastic particles were uniformly dispersed.

To 100 parts by weight of this syrup, 2,2'-
After adding and dissolving 0.15 parts by weight of azobisisobutyronitrile and degassing, a cell constituted by two glass plates and a vinyl chloride resin gasket so that the gap between the glass plates becomes 10 mm ( Area 300 mm x 300 mm)
And was polymerized in a water bath at 65 ° C. for 4 hours. Furthermore, after heat-treating in a hot air drying oven at 120 ° C. for 2 hours and cooling to near room temperature, the glass plate is removed and an acrylic resin plate containing multilayer elastic particles (thickness 10 mm, 300
mm × 300 mm), and the acrylic resin plate A
(First base plate).

(Acrylic resin film B) "Sanjuren 002AN" (thickness 100 μm, manufactured by Kanebuchi Chemical Industry Co., Ltd.) (acrylic resin plate C) "SUMIPEX" (polymethyl methacrylate plate, thickness 10 mm, 300 mm × 300)
mm, manufactured by Sumitomo Chemical Co., Ltd., containing no multilayer elastic body) (Polycarbonate-based resin plate A) "Polycarbonate ECK"
100 "(thickness 6 mm, 300 x 300 mm, manufactured by Tsutsunaka Plastic Industry Co., Ltd.) (Polycarbonate-based resin plate B)" Polycarbonate EC1 "
00 "(thickness 0.5 mm, 300 mm x 300 mm, manufactured by Tsutsunaka Plastic Industry Co., Ltd.).

Example 1 A polycarbonate resin plate B is placed on one surface of the acrylic resin plate A (first base plate) facing each other with a space therebetween, and an acrylic resin film is placed therebetween. Insert B (“Sanjuren 002AN”) into the press molding machine with a heating plate temperature of 150 ° C. and a preheating time of 2
Minute, press pressure of 50 kgf / cm ² for 1 minute, and then press in a cooling press at a press pressure of 50 kgf / cm ² for 4 minutes to form a polycarbonate resin plate on one side of the acrylic resin plate A (first base plate). B (first surface layer) was bonded via acrylic resin B (second surface layer).

Next, the polycarbonate resin plate A was placed on the other surface of the acrylic resin plate A (first base plate) facing each other with a space of 2 mm. The space between the acrylic resin plate A and the polycarbonate resin plate A is 2
It was opened by sandwiching a soft vinyl chloride hose having a thickness of mm. In this interval, a mixture of 42.5 parts by weight of bisphenol F type epoxy resin and 7.5 parts by weight of bisphenol A type epoxy resin ("XNR3351", manufactured by Nagase & Co., Ltd.) and a curing agent (polyetheramine curing). Agent, polyoxypropylenediamine, "XNH3351", manufactured by Nagase & Co., Ltd.) 50 parts by weight and injected at 20 ° C to 10 ° C.
The temperature is raised to 80 ° C. over a period of time to polymerize, and a polycarbonate resin plate A (second base plate) is attached to the other surface of the acrylic resin plate A (first base plate) to form a bisphenol epoxy cured resin layer ( A laminated transparent plate joined via an elastic joining layer) was obtained. The 100% modulus of the obtained bisphenol type epoxy-based cured resin layer was 39.4 kgf.
/ Cm ² and Tg were 10 ° C (DSC method).

Example 2 A polycarbonate resin plate B is placed on one surface of an acrylic resin plate A so as to face each other with a space therebetween, and an acrylic resin film B (Sanjuren 002AN) is inserted therebetween. Then, put it in a vacuum bag,
The air in the vacuum bag was evacuated by a vacuum pump at an ambient temperature of 135 ° C. to perform temporary bonding. After that, put it in an autoclave, raise the temperature from room temperature / atmospheric pressure to 150 ° C / 9 atm over 60 minutes, pressurize and hold at 150 ° C / 9 atm for 30 minutes, and then cool down to room temperature / atmosphere over 50 minutes.・ Step down
On one side of the acrylic resin plate A (first base plate), attach the polycarbonate resin plate B (first surface layer) to the acrylic resin B.
It joined through (2nd surface layer).

Then, in the same manner as in Example 1, the polycarbonate resin plate A (second base plate) was attached to the other surface of the acrylic resin plate A (first base plate) by a bisphenol epoxy cured resin layer (bonding). Layers) to obtain a laminated transparent plate. The 100% modulus of the obtained bisphenol type epoxy-based cured resin layer was 39.4 kgf.
/ Cm ² and Tg were 10 ° C (DSC method).

<Example 3> A laminated transparent plate is obtained in the same manner as in Example 1 except that the acrylic resin plate C is used instead of the acrylic resin plate A. This plate also has good transparency, and even if the same place is subjected to a plurality of impacts, whitening hardly occurs at the impacted place.

<Embodiment 4> A polycarbonate resin plate B (third base plate) is placed on one surface of the acrylic resin plate A (first base plate) so as to face each other with a space between the acrylic resin plate B (third base plate). While inserting the resin film B (first bonding layer), the polycarbonate resin plate B (first surface layer) is placed on the other surface side of the acrylic resin plate A so as to face each other at the same interval, and the acrylic resin plate B (first surface layer) is placed between them. Insert resin film B (second surface layer) and heat these in a press molding machine at a heating plate temperature of 1
50 ° C, preheating time 2 minutes, press pressure 50 kgf / cm ²
After pressing for 1 minute in a cold press, press pressure 5
A laminated substrate was obtained by pressing at 0 kgf / cm ² for 4 minutes.

Then, on the other surface (unbonded surface) of the third base plate of the above-mentioned laminated substrate, the polycarbonate resin plate A is formed.
The (second base plates) were placed facing each other with a space of 2 mm. The space was made by sandwiching a soft vinyl chloride hose having a thickness of 2 mm between the polycarbonate resin plate A (second base plate) and the polycarbonate resin plate B (third base plate). Bisphenol F type epoxy resin 42.
5 parts by weight and bisphenol A type epoxy resin 7.5
A mixture of 50 parts by weight of a mixture (XNR3351, manufactured by Nagase & Co., Ltd.) and 50 parts by weight of a curing agent (polyetheramine-based curing agent, polyoxypropylenediamine, XNH3351, manufactured by Nagase & Co., Ltd.) is injected, and from 20 ° C. 1
The temperature is raised to 80 ° C. over a period of 0 hours to polymerize, and a polycarbonate resin plate A (second base plate) is attached to the unbonded surface of the third base plate of the laminated base with a bisphenol epoxy cured resin layer (elastic bonding). To obtain a laminated transparent plate which is joined via the (layer). The 100% modulus of the obtained second bonding layer was 39.4 kgf / cm ² , and the Tg was 10 ° C (DSC).
Law).

Example 5 A laminated transparent plate is obtained in the same manner as in Example 4 except that the acrylic resin plate C is used instead of the acrylic resin plate A. This plate also has good transparency, and even if the same place is subjected to a plurality of impacts, whitening hardly occurs at the impacted place.

Comparative Example 1 A laminated transparent plate was prepared in the same manner as in Example 2 except that an ethylene-vinyl acetate copolymer film (thickness: 250 μm) was used in place of the acrylic resin film B (Sandren 002AN). Obtained.

<Comparative Example 2> Polycarbonate resin plate B
An adhesive film (PET25PA-T1, manufactured by Lintec Co., Ltd.) made of polyethylene terephthalate resin was attached to one surface of the acrylic resin plate A using a hand roll, and the release film was peeled off. Temporary bonding, then autoclave (40 ℃
・ Acrylic resin plate A after 0.5 hour at 7 atmospheres
Polycarbonate resin plate B on one side of (first base plate)
The (first surface layer) was bonded via a polyethylene terephthalate resin layer.

Then, in the same manner as in Example 1, the polycarbonate resin plate A (second base plate) was attached to the other surface of the acrylic resin plate A (first base plate) by a bisphenol type epoxy resin cured resin layer (elasticity). Bonding via a bonding layer)
A laminated transparent plate was obtained.

<Comparative Example 3> Polycarbonate resin plate B
Instead of (thickness 0.5 mm), polyethylene terephthalate resin plate (300 mm x 300 mm, thickness 0.25 m)
m, corresponding to the first surface layer) was used to carry out the same operation as in Example 2 to obtain a laminated transparent plate.

<Comparative Example 4> An acrylic resin plate (SUMIPEX XT100, Sumitomo Chemical Co., Ltd.) as the first base plate.
Manufactured, thickness 10 mm) and the laminated transparent plate was obtained in the same manner as in Example 1 except that the first surface layer and the second surface layer were not provided.

<Example 6> The first surface layer (thickness) was the same as in Example 1 except that a polycarbonate resin plate having a thickness of 1.5 mm was used as the resin plate constituting the first surface layer. 1.5 mm), second surface layer (thickness 100 μm), first
Base plate (thickness 10 mm) consisting of three layers of laminated plate (20
00 mm × 1000 mm) was obtained.

Three more sheets of this laminate were produced in the same manner,
The amount of warpage was measured. That is, the height of the central convex portion when the laminate was placed on a flat plate was measured to be 15 to 27 mm from the flat plate reference surface.

Using these laminates, the second base plate was joined to the other surface (non-joint surface) of the first base plate through the elastic joining layer in the same manner as in Example 1 to form a laminate. A transparent plate was obtained. The resulting laminated transparent plate also has good transparency,
In addition, even if the same place is subjected to a plurality of impacts, almost no whitening occurs at the impacted place.

However, since the plate is large and the warp on the side of the first base plate is large, the epoxy resin composition is liable to leak during the above joining, the workability and the production efficiency of the joining are not so good, and the laminated The yield of the transparent plate was also not good.

Example 7 The first surface layer (thickness) was formed in the same manner as in Example 4 except that a polycarbonate resin plate having a thickness of 1.5 mm was used as the resin plate forming the first surface layer. 1.5 mm), second surface layer (thickness 100 μm), first
Base plate (thickness 10 mm), first bonding layer (thickness 100 μ
m) and a third base plate (thickness: 1.5 mm) consisting of five layers to obtain a laminated plate (2000 mm × 1000 mm).

When the warpage of this laminate was measured in the same manner as in Example 6, it was 1 to 4.5 mm.

Using these laminates, the second base plate was joined to the other surface (non-joint surface) of the first base plate via the elastic joining layer in the same manner as in Example 4, and the laminate was formed. A transparent plate was obtained. At the time of the joining, there is almost no leakage of the epoxy resin composition, the workability of the joining and the production efficiency are excellent, the yield of the laminated transparent plate is extremely good, and the joining strength is excellent.

The transparency (before impact) of each laminated transparent plate produced as described above was visually evaluated based on the following criteria.

(Transparency Criteria) "○": The opposite side can be easily observed through the laminated transparent plate “△”… It is difficult to observe the other side through the laminated transparent plate "×" ... Cannot observe the other side through the laminated transparent plate

Next, the impact resistance (1 shot) was measured by the following test method.
And repeated impact resistance (2 shots) was evaluated. The results are shown in Table 1.

<Impact Test Method> Test piece support of impact tester (FIG. 3) (cylindrical, iron, diameter 100 mm) (10)
A laminated transparent plate cut into 100 mm x 100 mm was placed on top of it as a test piece (11) with its first surface layer (5) facing up, and a conical tip (2 mm) was placed on it.
The tip diameter (13a) of (13) was pressed.
A disk-shaped weight receiving support board (13b) is provided at the center of the hitch (13) in the longitudinal direction. A stainless steel weight (30 kg) facing this support board (13b)
(12) was dropped by free fall from a position of height 2.5 m (height with respect to the support plate). At this time, the test piece (1
1) is placed so that its four sides are aligned with the periphery of the test piece support base (10), and the tip (13a) of the hitch is the test piece (11).
The test piece (11) is pressed against the center of the
It was set to be in the center of (Fig. 4).

The weight (12) was dropped twice at the same place, and the presence or absence and degree of scattering of the test piece (11) (scattering of fragments) at each impact was visually observed, and based on the following criteria. evaluated.

(Impact Test Judgment Criteria) "○" ... No scattering of fragments “△”… Slightly scattered debris "×" ... A lot of debris scattered

Further, the visibility on the opposite side as viewed from the impact point through the laminated transparent plate was visually determined based on the following criteria.

(Criteria for Judgment of Visibility) "○" ... Whitening did not occur, and visibility was good "△" ... Whitening occurred slightly, but visibility was hardly decreased "X" ... Whitening Occurred and the visibility decreased.

[0124]

[Table 1]

As is clear from Table 1, the laminated transparent plates of Examples 1, 2, and 4 of the present invention have excellent transparency and
It has sufficient impact resistance against strong impact and is also excellent in impact resistance when repeatedly subjected to multiple impacts. Also, there is no whitening at the impact point (after two impacts),
Excellent transparency is ensured even after impact.

On the other hand, the laminated transparent plates of Comparative Examples 1 to 4 are inferior in impact resistance and visibility when repeatedly impacted a plurality of times.

[0127]

As described above, in the laminated transparent plate according to the first aspect of the present invention, as the laminated substrate, the acrylic resin plate and the polycarbonate resin plate are elastically joined by the resin having the glass transition temperature of 50 ° C. or less. Because it is composed of layers joined together, it is lightweight and has excellent transparency,
Sufficient protection performance against strong impact is obtained. And, on the other surface of the acrylic resin plate, the first surface layer made of a polycarbonate resin has a second surface made of an acrylic resin.
Since it is bonded through the surface layer, it is possible to secure sufficient lightness and transparency, and also to have excellent impact resistance when repeatedly subjected to a strong impact multiple times, that is, to apply impact multiple times to the same location. It is possible to obtain an excellent effect that even if it is received, fragments are not scattered from the peripheral part of the impacted part and the visibility from the impacted part is not deteriorated.

Further, the laminated transparent plate according to the second invention is a laminated substrate having a first bonding layer and a third bonding layer on one surface of the first base plate.
Since the base plate, the elastic bonding layer, and the second base plate are laminated in this order, the base plate, the elastic bonding layer, and the second base plate are light in weight, excellent in transparency, and sufficient protection performance against strong impact can be obtained. Further, since the first surface layer made of polycarbonate resin is bonded to the other surface of the first base plate via the second surface layer made of acrylic resin, sufficient lightness and transparency are ensured. At the same time, the effect of being excellent in impact resistance when repeatedly subjected to a strong impact, that is, even if the same location is subjected to multiple impacts, fragments are not scattered from the periphery of the impact location, and the impact location It is possible to obtain an excellent effect that visibility from the inside does not decrease. Further, since the third base plate made of polycarbonate resin is laminated at a specific position, even when a large-sized configuration is adopted, it is possible to reduce the warpage during manufacturing and to perform the liquid injection work during manufacturing. It is easy to manufacture with no hindrance, is excellent in manufacturing efficiency, and can reduce warpage as a laminated transparent plate, and even with a large structure, it has excellent bonding strength and high quality. Can be one.

When the first base plate contains 0.1 to 72 parts by weight of the multi-layered elastic particles with respect to 100 parts by weight of the acrylic resin, a further excellent protection performance against a strong impact is secured. To be done.

When the glass transition temperature of the resin constituting the elastic bonding layer is −30 to 40 ° C., more excellent protection performance can be ensured, and the impact resistance when repeatedly subjected to strong impact, that is, Repeated impact resistance can be further improved.

When the resin constituting the elastic bonding layer is an epoxy resin or an acrylic resin, it is possible to further improve the adhesive strength of the elastic bonding layer and further improve the impact resistance and transparency of the laminated transparent plate. Can be made.

When the resin constituting the elastic bonding layer is a bisphenol type epoxy-based cured resin, the adhesive strength of the elastic bonding layer can be further improved and the impact resistance and transparency of the laminated transparent plate can be further improved. Can be improved.

When the resin constituting the second surface layer has a Vicat softening point of 50 to 90 ° C. and a haze ratio of 1 to 60% at a thickness of 50 μm, sufficient bonding strength is secured. At the same time, the transparency can be further improved.

When the thickness of the second surface layer is 10 to 1000 μm, excellent repeated impact resistance can be ensured while maintaining low cost.

The thickness of the first surface layer is 0.1 to 3 mm.
In such a case, excellent repeated impact resistance can be ensured while maintaining sufficient lightness.

Moreover, the thickness of the first base plate is 3 to 30 mm.
In addition, when the thickness of the second base plate is 3 to 15 mm, it is possible to secure a further excellent protection performance while sufficiently reducing the weight.

When the thickness of the elastic bonding layer is 0.1 to 3 mm, it is possible to secure further excellent protection performance while sufficiently reducing the weight.

In the above-mentioned second invention, when the resin constituting the first bonding layer has a Vicat softening point of 50 to 90 ° C. and a haze ratio at a resin thickness of 50 μm of 1 to 60%, It is possible to further improve the transparency while ensuring a better bonding strength.

Similarly, in the second aspect of the present invention, when the thickness of the first bonding layer is 10 to 1000 μm, further excellent impact resistance can be secured while further reducing the cost.

Similarly, in the second aspect of the present invention, when the thickness of the third base plate is 0.1 to 3 mm, it is possible to more effectively reduce the occurrence of warpage during manufacturing while sufficiently reducing the weight, and to reduce the warpage. The cost can be reduced and the laminated transparent plate can be made of high quality with further excellent bonding strength.

[Brief description of drawings]

FIG. 1 is a schematic sectional view showing a laminated transparent plate according to an embodiment of the first invention.

FIG. 2 is a schematic sectional view showing a laminated transparent plate according to an embodiment of the second invention.

FIG. 3 is a schematic diagram of an impact tester.

FIG. 4 is an explanatory diagram showing a positional relationship between a test piece, a support, and a hitch.

[Explanation of symbols]

1. Laminated transparent plate 2 ... First base plate 3 ... Second base plate 4 ... Third base plate 5 ... First surface layer 6 ... Second surface layer 7 ... First bonding layer 8 ... Elastic bonding layer 9 ... Laminated substrate

─────────────────────────────────────────────────── --- Continuation of front page (56) Reference JP-A-6-71826 (JP, A) JP-A-7-112515 (JP, A) JP-A-7-290657 (JP, A) JP-A-7- 256831 (JP, A) Special table 55-500842 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35/00

Claims (14)

(57) [Claims] 1. A first base plate (2) made of an acrylic resin is provided on one side with a second base made of a polycarbonate resin.
The glass transition temperature of the base plate (3) is 50 ° C. or lower.
The first surface layer (5) made of polycarbonate resin is Vicat softened on the other surface of the first base plate (2) while being joined via the elastic joining layer (8) made of epoxy resin. The point is 50 to 90 ° C., and
A laminated transparent plate, which is bonded via a second surface layer (6) made of an acrylic resin having a haze ratio of 1 to 60% at a thickness of 50 μm . 2. A first base plate (2) made of an acrylic resin, and a third base made of a polycarbonate resin on one surface of the first base plate (2).
The base plate (4) is bonded via the first bonding layer (7) made of an acrylic resin, and the second surface made of a polycarbonate resin is attached to the other surface of the third base plate (4).
The base plate (3) is bonded via an elastic bonding layer (8) made of a resin having a glass transition temperature of 50 ° C. or lower, while a polycarbonate-based material is attached to the other surface of the first base plate (2). A laminated transparent plate, characterized in that a first surface layer (5) made of a resin is bonded via a second surface layer (6) made of an acrylic resin. 3. The first base plate (2) comprises 0.1 to 7 multi-layered elastic particles in 100 parts by weight of an acrylic resin.
The laminated transparent plate according to claim 1, which contains 2 parts by weight. 4. The laminated transparent plate according to claim 1, wherein a glass transition temperature of a resin forming the elastic bonding layer (8) is −30 to 40 ° C. 5. The resin forming the elastic bonding layer (8) is an epoxy resin or an acrylic resin.
The laminated transparent plate according to any one of 2 to 4. 6. The resin constituting the elastic bonding layer (8) is a bisphenol type epoxy curing resin.
The laminated transparent plate according to any one of 1 to 4 . 7. The Vicat softening point of the resin constituting the second surface layer (6) is 50 to 90 ° C., and the haze ratio of the resin at a thickness of 50 μm is 1 to 60%.
The laminated transparent plate according to any one of 2 to 6. 8. The thickness of the second surface layer (6) is 10 to 1
It is 000 micrometers, The laminated transparent plate of any one of Claims 1-7. 9. The thickness of the first surface layer (5) is 0.1 to 10.
It is 3 mm, The laminated transparent plate of any one of Claims 1-8. 10. The thickness of the first base plate (2) is 3 to.
The laminated transparent plate according to any one of claims 1 to 9, wherein the second base plate (3) has a thickness of 30 mm and a thickness of 3 to 15 mm. 11. The elastic bonding layer (8) has a thickness of 0.1.
The laminated transparent plate according to any one of claims 1 to 10, having a thickness of 4 mm. 12. The Vicat softening point of the resin constituting the first bonding layer (7) is 50 to 90 ° C., and the haze ratio of the resin at a thickness of 50 μm is 1 to 60%. 11. The laminated transparent plate according to any one of 11 above. 13. The thickness of the first bonding layer (7) is 10 to 10.
It is 1000 micrometers, The laminated transparent plate of any one of Claims 2-12. 14. The third base plate (4) has a thickness of 0.
It is 1-3 mm, The laminated transparent plate of any one of Claims 2-13.