JP2016163990A - Laminate for organic glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate for organic glass achieving excoriation resistance, impact resistance and scratch resistance.SOLUTION: There is provided a laminate for organic glass 10 obtained by laminating a protective layer 13 on a transparent resin substrate 11, where the protective layer 13 is a cured article of an ionization radiation curable resin composition and the ionization radiation curable resin composition contains polycarbonate (meth)acrylate and polyfunctional (meth)acrylate with mass ratio of 98:2 to 70:30. There is provided the laminate for organic glass 10, where preferably the transparent resin substrate 11 consists of a polycarbonate resin and further it is preferable that the polycarbonate (meth)acrylate is bifunctional and the polyfunctional (meth)acrylate is tri- or higher functional.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate for organic glass.

Conventionally, inorganic glass has been used for automobile windows, sunroofs, etc., but it has the drawback of being easily broken. In order to improve this, for example, Patent Document 1 discloses a film reinforced glass obtained by laminating a transparent adhesive layer made of an organic resin and a film made of an organic polymer on the surface of a glass plate and bonding them together. .
However, since the tempered glass described in Patent Document 1 uses inorganic glass as a base material, it is heavy and has high thermal conductivity and poor air conditioning efficiency. Is not preferable. In particular, when used in sunroof applications, there is a possibility that a heavy object is provided at a high position on the vehicle body, which may adversely affect the exercise performance.

In order to overcome the problems of the inorganic glass described above, a technique of providing a hard coat layer on the surface of an organic glass using a synthetic resin that is light in weight, low in thermal conductivity, and difficult to break has been studied. For example, Patent Document 2 describes a transparent resin laminated sheet in which a composite base material layer containing a resin and a fibrous filler is formed on both surfaces of a transparent resin layer. However, scattering occurs at the interface between the fibrous filler and the transparent resin, which may reduce transparency, and the surface scratch resistance is not sufficient.

JP 2002-79610 A JP 2007-203475 A

Accordingly, the present inventors have studied a method for forming a protective layer using an ionizing radiation curable resin on the surface of the organic glass from the viewpoint of improving the scratch resistance of the surface. Then, when a cured product of ionizing radiation curable resin composition is provided as a protective layer on the organic glass surface, depending on the type of resin composition, the cured product itself may crack in the impact resistance test, or the protective layer It has been found that deep dents may occur when the surface of the film is scratched.

It is an object of the present invention to provide a laminate for organic glass that can enhance scratch resistance, impact resistance, and scratch resistance under such circumstances.

As a result of intensive studies to achieve the above problems, the present inventors have solved the above problems by selecting a cured product of an ionizing radiation curable resin composition having a specific tensile elastic modulus as a protective layer. I found out that I could do it. The present invention has been completed based on such findings.

That is, the present invention
[1] A laminate for organic glass formed by laminating a protective layer on a transparent resin substrate, wherein the protective layer is a cured product of an ionizing radiation curable resin composition, and the tensile elastic modulus of the protective layer is 2100 MPa. A laminate for organic glass, characterized by:
[2] The laminate for organic glass according to [1], wherein the ionizing radiation curable resin composition contains a polyfunctional (meth) acrylate,
[3] The transparent resin substrate is made of a polycarbonate resin, and the laminate for organic glass according to [1] or [2], and [4] for window material or resin cover [1] to [3]. A laminate for organic glass according to any one of
Is to provide.

ADVANTAGE OF THE INVENTION According to this invention, the laminated body for organic glass which improves scratch resistance, impact resistance, and scratch resistance can be provided.

It is a schematic diagram which shows the cross section of an example of the laminated body for organic glasses of this invention.

[Laminated body for organic glass]
The laminate for organic glass of the present invention is a laminate for organic glass formed by laminating a protective layer on a transparent resin substrate, and the protective layer is a cured product of an ionizing radiation curable resin composition, The layer has a tensile modulus of 2100 MPa or less. Hereinafter, the present invention will be described with reference to the drawings. Drawing 1 is a mimetic diagram showing the section of an example of the desirable mode of the layered product for organic glasses of the present invention.
The organic glass laminate 10 of the present invention shown in FIG. 1 has a primer layer 12 on a substrate 11.
And a protective layer 13.
Here, the organic glass refers to a member made of transparent plastic, and is generally used as a substitute member for inorganic glass such as silicate glass or quartz glass containing silicon dioxide as a main component. It is.

<< Board >>
The substrate 11 is not particularly limited as long as it is transparent, but is preferably highly transparent. Thermoplastic resins such as cycloolefin resins, silicone resins, and polycarbonate resins, epoxy resins, and acrylic resins are preferred. Examples include curable resins such as resins (polymethyl methacrylate, etc.), phenol resins, polyimide resins, benzoxazine resins, oxetane resins, etc. Of these, polycarbonate resins and acrylic resins from the viewpoint of transparency From the viewpoint of impact resistance, a polycarbonate resin is particularly preferable.

As thickness of the board | substrate 11, 1-20 mm is preferable normally and 2-10 mm is more preferable. When the thickness of the substrate 11 is 1 mm or more, practical strength such as surface rigidity is sufficient, and when it is 20 mm or less, workability is improved.
The substrate 11 only needs to have a tensile elastic modulus of 4,000 MPa or less.
The thing of 3500 MPa is preferable and the thing of 500-3000 MPa is more preferable.
The substrate 11 can be a single-layer sheet of these resins or a multilayer sheet of the same or different resins.

For the purpose of improving the adhesion with the primer layer 12 to be described later, the substrate 11 is, if desired,
One or both surfaces can be subjected to a physical or chemical surface treatment by an oxidation method, an unevenness method, or the like.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment,
Examples include an ozone / ultraviolet treatment method, and examples of the concavo-convex method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected depending on the type of the substrate 11, but in general, the corona discharge treatment method is preferably used from the viewpoints of effects and operability.

The substrate 11 may be subjected to a treatment such as forming an easy-adhesion layer for the purpose of enhancing the interlayer adhesion between the substrate 11 and the layer provided thereon, and the surface treatment as described above is performed in advance. Commercially available products and those provided with an easy-adhesive layer can also be used.

≪Primer layer≫
The laminate for organic glass of the present invention preferably further has a primer layer 12 between the substrate 11 and the protective layer 13. By providing the primer layer 12, the adhesion between the substrate 11 and the protective layer 13 can be further improved. The primer layer 12 is preferably a transparent or translucent layer, such as a polyurethane resin, a polyester resin, an acrylic resin,
One kind or a mixture of two or more kinds of resins such as vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, cellulose resin, chlorinated polyethylene, chlorinated polypropylene, etc. are used. Those using curable resins are preferred.

Examples of polyurethane two-component curable resins include vinyl chloride-vinyl acetate copolymer systems,
A polymer polyol such as polyester series, urethane series, acrylic series, polyether series, polycarbonate series, or the like, or a mixture thereof with a curing agent added just before use is used.
As the polymer polyol, an acrylic polymer polyol or a polyester polymer polyol is preferable, and an acrylic polymer polyol is more preferable.
Examples of the acrylic polymer polyol include (meth) acrylic acid alkyl esters such as ethyl (meth) acrylate, 2-hydroxyethyl acrylate, 2-hydroxy-3-
Preferred are those in which a plurality of hydroxyl groups are introduced by copolymerizing a hydroxy acrylate such as phenoxypropyl acrylate. Examples of the polyester polymer polyol include poly (ethylene adipate), poly (butylene adipate), poly (neopentyl adipate), poly (hexamethylene adipate), poly (butylene azelate), and poly (butylene sebacate). Polycaprolactone is used.
Moreover, in this invention, the mixture of said acrylic polymer polyol and urethane resin is more preferable.

As the curing agent, polyisocyanate is preferable, for example, aromatic isocyanate such as 2,4-tolylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate; 1,6-hexamethylene diisocyanate, 2 , 2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, or the like, or adducts of the above-mentioned various isocyanates. Alternatively, multimers such as adducts of tolylene diisocyanate, tolylene diisocyanate trimers, and the like can also be used.

In the present invention, the polyurethane two-component curable resin preferably has a glass transition temperature Tg of 65 ° C. or higher when the polymer polyol is uncured, and the upper limit of the glass transition temperature Tg is not particularly limited. Usually, it is about 110 degreeC, and preferable Tg is the range of 70-100 degreeC. When the glass transition temperature Tg is within the above range, excellent adhesion can be obtained.

The primer layer can also be formed using a primer layer-forming resin composition containing the polyurethane-based two-component curable resin and a binder resin.
As this binder resin, a known binder resin having a glass transition temperature Tg of 80 ° C. or lower is preferably used, and either a compound having a hydroxyl group or a compound having no hydroxyl group may be used. Specifically, a polyurethane resin, a vinyl chloride-vinyl acetate copolymer resin, a polyester resin, or the like can be used as the binder resin. The weight average molecular weight converted to standard polystyrene of a resin that can be used as a binder resin is preferably
It is 10,000 to 300,000, more preferably 5 to 200,000.
The content of the binder resin is 1 with respect to the total of the polymer polyol and the binder resin.
It is preferable that it is 0-60 mass%.

The primer layer 12 can be obtained by applying and drying a coating solution obtained by dissolving the resin in a solvent by a known method. About the thickness of the primer layer 12, it is about 0.5-20 micrometers normally, Preferably, it is the range of 1-5 micrometers.

≪Protective layer≫
The protective layer 13 is a cured product of the ionizing radiation curable resin composition and has a tensile modulus of 2 after curing.
It may be 100 MPa or less, preferably 3 to 1800 MPa,
The thing of 00 MPa is more preferable.
The ionizing radiation curable resin used in this ionizing radiation curable resin composition has an energy quantum capable of crosslinking and polymerizing molecules in electromagnetic waves or charged particle beams, that is, irradiating with ultraviolet rays or electron beams. Refers to a resin that crosslinks and cures. Specifically, it can be appropriately selected from polymerizable oligomers and polymerizable monomers conventionally used as ionizing radiation curable resins.

As the polymerizable oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, for example, acrylic (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, poly Preferred examples include ether (meth) acrylate-based, polycarbonate (meth) acrylate-based, and acrylic silicone (meth) acrylate-based oligomers. Among these oligomers, polyfunctional polymerizable oligomers are preferable, and the number of functional groups is preferably 2 to 16, more preferably 2 to 8, and still more preferably 2 to 6.

In addition, other polymerizable oligomers include (meth) on the side chain of the polybutadiene oligomer.
Highly hydrophobic polybutadiene (meth) acrylate oligomers with acrylate groups,
Silicone (meth) acrylate oligomers with polysiloxane bonds in the main chain, aminoplast resin (meth) acrylate oligomers modified with aminoplast resins with many reactive groups in small molecules, or novolak epoxy resins, bisphenol There are oligomers having cationically polymerizable functional groups in the molecule such as epoxy resin, aliphatic vinyl ether and aromatic vinyl ether. These polymerizable oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.

As the polymerizable monomer, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is suitable, and in particular, a polyfunctionality having two or more ethylenically unsaturated bonds in the molecule ( (Meth) acrylate is preferred, and one kind may be used alone, or two or more kinds may be used in combination. The number of functional groups is preferably 2-8, more preferably 2-6, and even more preferably 2-4.

In the present invention, together with the polyfunctional (meth) acrylate, for the purpose of adjusting the viscosity, methyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, etc. A monofunctional (meth) acrylate can be appropriately used in combination as long as the object of the present invention is not impaired. A monofunctional (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more type.

As the ionizing radiation curable resin composition in the present invention, among the various ionizing radiation curable resins, at least polycarbonate (meth) acrylate or acrylic silicone (
Using organic resin containing meth) acrylate and polyfunctional (meth) acrylate satisfies both excellent scratch resistance and good three-dimensional formability at the same time. It is preferable at the point which can obtain a laminated body.

When using an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate and polyfunctional (meth) acrylate, the mass ratio of polycarbonate (meth) acrylate and polyfunctional (meth) acrylate is preferably 98: It is 2-70: 30, More preferably, it is 95: 5-80: 20. When the mass ratio of the polycarbonate (meth) acrylate and the polyfunctional (meth) acrylate is larger than 98: 2 (that is, when the amount of the polycarbonate (meth) acrylate exceeds 98 mass%), the scratch resistance is lowered. On the other hand, when the mass ratio of polycarbonate (meth) acrylate and polyfunctional (meth) acrylate is smaller than 70:30 (that is, the amount of polycarbonate (meth) acrylate is 7).
If it is less than 0% by mass), the moldability is lowered.
The polycarbonate (meth) acrylate used in the present invention is not particularly limited as long as it has a carbonate bond in the polymer main chain and has (meth) acrylate in the terminal or side chain. The polycarbonate (meth) acrylate preferably has two or more functions, more preferably 2 to 5 functions, from the viewpoint of crosslinking and curing. 2
If it is functional or higher, the crosslinking density becomes sufficient, so that the protective layer 13 after curing is less likely to be damaged, and if it is pentafunctional or lower, the crosslinking density is not too high, and the moldability becomes good. .
The polycarbonate (meth) acrylate preferably has a weight average molecular weight of 500 or more measured by GPC analysis and converted to standard polystyrene.
It is more preferably 0 or more, further preferably 2,000 or more, and 5,000
It is especially preferable that it is 00 or more. The upper limit of the weight average molecular weight of the polycarbonate (meth) acrylate is not particularly limited, but it is 1 from the viewpoint of controlling the viscosity not to be too high.
00,000 or less is preferable, 50,000 or less is more preferable, and 20,000 or less is more preferable. From the viewpoint of achieving both scratch resistance and three-dimensional formability, 1,000 to 20,
000 is preferable, and 2,000 to 20,000 is more preferable.

When using an ionizing radiation curable resin composition containing acrylic silicone (meth) acrylate and polyfunctional (meth) acrylate, the mass ratio of acrylic silicone (meth) acrylate and polyfunctional (meth) acrylate is preferably 50: 50-95: 5
More preferably, it is 80: 20-95: 5.
The acrylic silicone (meth) acrylate used in the present invention is not particularly limited.
In the molecule, a part of the structure of the acrylic resin is substituted with a siloxane bond (Si—O), and a (meth) acryloyloxy group (acryloyloxy) is present as a functional group on the side chain and / or main chain terminal of the acrylic resin. Group or methacryloyloxy group) may be used.
The acrylic silicone (meth) acrylate has a weight average molecular weight measured by GPC analysis and converted to standard polystyrene of preferably 1,000 or more, and more preferably 2,000 or more. The upper limit of the weight average molecular weight of the acrylic silicone (meth) acrylate is not particularly limited, but is preferably 150,000 or less and more preferably 100,000 or less from the viewpoint of controlling the viscosity not to be too high. From the viewpoint of achieving both formability and scratch resistance, it is particularly preferably 2,000 to 100,000.

The polyfunctional (meth) acrylate used for this invention should just be bifunctional or more (meth) acrylate, and there is no restriction | limiting in particular. However, trifunctional or higher functional (meth) acrylates are preferred from the viewpoint of curability. Here, bifunctional means having two ethylenically unsaturated bonds {(meth) acryloyl group} in the molecule.
The polyfunctional (meth) acrylate may be either an oligomer or a monomer,
From the viewpoint of improving moldability, a polyfunctional (meth) acrylate oligomer is preferred.
The polyfunctional (meth) acrylate has a weight average molecular weight measured by GPC analysis and converted to standard polystyrene of preferably 500 or more, more preferably 1,000 or more, and 2,000 or more. More preferably, it is more preferably 5,000 or more. The upper limit of the weight average molecular weight of the polyfunctional (meth) acrylate is not particularly limited, but is preferably 100,000 or less from the viewpoint of controlling the viscosity not to be too high.
More preferably, it is not more than 10,000, and particularly preferably not more than 20,000. From the standpoint of achieving both scratch resistance and formability, it is more preferably 2,000 to 50,000, and particularly preferably 5,000 to 20,000.

Examples of the polyfunctional (meth) acrylate oligomer include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and polyether (meth) acrylate oligomers. Here, the urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. The epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. Examples of polyester (meth) acrylate oligomers include esterification of hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. Polyether (meth) acrylate oligomers
It can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

Furthermore, other polyfunctional (meth) acrylate oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity having (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicones (meta-methacrylate) having polysiloxane bonds in the main chain. ) Acrylate oligomers, aminoplast resin (meth) acrylate oligomers obtained by modifying aminoplast resins having many reactive groups in small molecules.

Moreover, when using ultraviolet curable resin as ionizing radiation curable resin, it is desirable to add about 0.1-5 mass parts of photopolymerization initiators with respect to 100 mass parts of ultraviolet curable resin. The initiator for photopolymerization can be appropriately selected from those conventionally used,
For example, benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; acetophenones such as acetophenone, 2,2′-diethoxyacetophenone, p-dimethylacetophenone, p-tert-butylacetophenone; benzophenone, 2-chloro Benzophenones, such as benzophenone and p, p'-bisdimethylaminobenzophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-montforinopropanone-1,2-benzyl-2-dimethylamino-
Α-aminoalkylphenones such as 1- (4-morpholiophenyl) -butanone-1; sulfur compounds such as benzyldimethyl ketal, thioxanthone, 2-chlorothioxanthone, and 2,4-diethylthioxanthone are preferable. Can be mentioned.
As the photosensitizer, for example, p-dimethylbenzoate, tertiary amines, thiol sensitizers, and the like can be used.

In the present invention, it is preferable to use an electron beam curable resin as the ionizing radiation curable resin. This is because the electron beam curable resin can be made solvent-free, is more preferable from the viewpoint of environment and health, and does not require a photopolymerization initiator, and can provide stable curing characteristics.

In the said ionizing radiation-curable resin composition, other resin can be contained in the range with the effect of this invention, for example, a thermoplastic resin can be added. However, when resistance to a solvent is required, it is preferable not to contain a thermoplastic resin.
Thermoplastic resins include (meth) acrylic resins such as (meth) acrylic acid esters, polyvinyl acetals (butyral resin) such as polyvinyl butyral, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, vinyl chloride resins, urethane resins, Polyolefins such as polyethylene and polypropylene, styrene resins such as polystyrene and α-methylstyrene, acetal resins such as polyamide, polycarbonate and polyoxymethylene, fluororesins such as ethylene-tetrafluoroethylene copolymer, polyimide, polylactic acid, Polyvinyl acetal resin, liquid crystalline polyester resin, etc. are mentioned, and these are 1
One species may be used alone, or two or more species may be used in combination. When combining 2 or more types, the copolymer of the monomer which comprises these resin may be sufficient, and each resin may be mixed and used.

Among the above thermoplastic resins, those having a (meth) acrylic resin as a main component are preferred in the present invention, and in particular, those obtained by polymerizing a monomer containing at least a (meth) acrylic acid ester as a monomer component. preferable.
More specifically, a homopolymer of (meth) acrylic acid ester, a copolymer of two or more different (meth) acrylic acid ester monomers, or a copolymer of (meth) acrylic acid ester and other monomers Is preferred.

As said thermoplastic resin, the range whose weight average molecular weight is 90,000-150,000 is used, for example. When the weight average molecular weight is within this range, it is possible to obtain at a high level all of moldability, surface wear resistance, and scratch resistance after crosslinking and curing to form a protective layer.
Here, the weight average molecular weight is gel permeation chromatography (GPC).
It is the thing of polystyrene conversion measured by. The solvent used here can be appropriately selected from those commonly used. For example, tetrahydrofuran (THF) or N-
And methyl-2-pyrrolidinone (NMP).

Further, the polydispersity (weight average molecular weight Mw / number average molecular weight Mn) of the thermoplastic resin is 1.
A range of 1 to 3.0 is preferable. If the polydispersity is within this range, it is possible to obtain a high level of moldability, surface abrasion resistance, and scratch resistance after crosslinking and curing to form a protective layer. From the above points, the polydispersity of the (meth) acrylic resin is preferably in the range of 1.5 to 2.5.

The protective layer 13 thus formed has various functions by adding various additives, for example, a so-called hard coat function, antifogging function, antifouling function, antifouling, having high hardness and scratch resistance. A glare function, an antireflection function, an ultraviolet shielding function, an infrared shielding function, and the like can also be imparted.

Examples of additives include a weather resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent,
Examples thereof include fillers, solvents, colorants, and wear resistance improvers.

In the present invention, the thickness of the protective layer 13 after curing is preferably 20 μm or less,
More preferably, it is 1-20 micrometers. When the thickness of the protective layer 13 after curing is 1 μm or more, excellent design properties such as transparency and gloss can be obtained, and furthermore, sufficient physical properties as a protective layer such as contamination resistance, scratch resistance, and weather resistance. Is obtained. On the other hand, when the thickness is 20 μm or less, the thickness of the coating film can be easily controlled, the protective layer is not cracked or whitened during molding, and the solvent remains in the layer, resulting in poor curing. Absent. From this viewpoint, the thickness of the protective layer 13 after curing is 2 to 20 μm.
The range of m is preferable, and the range of 5 to 15 μm is more preferable.

≪Method for producing laminate for organic glass≫
The laminate for organic glass of the present invention can be produced, for example, by the following steps [1] to [4].
[1] A step of subjecting the surface of the substrate 11 to corona discharge treatment or plasma treatment as desired [2] A step of laminating the primer layer 12 on the substrate 11 as desired;
[3] a step of laminating an ionizing radiation curable resin composition layer, and [4] irradiating the ionizing radiation curable resin composition layer with ionizing radiation to cure or semi-harden the ionizing radiation curable resin composition layer. Forming the protective layer 13
As a method for laminating the primer layer 12 and the protective layer 13 laminated on the substrate 11, known printing or coating means such as gravure printing or roll coating is used.

In the step of forming the protective layer 13 in the present invention, the ionizing radiation curable resin composition layer laminated on the substrate 11 or the primer layer 12 may be semi-cured or cured, When it is, surface performance will become favorable, and since the moldability will become favorable even if it is a hardened material by making this resin composition into the above-mentioned predetermined thing, it is preferred to make it harden. When the ionizing radiation curable resin composition layer is cured, the resin composition layer can be cured by irradiating it with ionizing radiation such as an electron beam or ultraviolet rays. Here, when an electron beam is used as the ionizing radiation, the accelerating voltage can be appropriately selected according to the resin used and the thickness of the layer, but the ionizing radiation curable resin composition layer is usually used at an accelerating voltage of about 70 to 300 kV. It is preferable to cure.
In the electron beam irradiation, the transmission capability increases as the acceleration voltage increases.
In the case of using a base material that is deteriorated by an electron beam as 1, an extra electron is applied to the substrate 11 by selecting an accelerating voltage so that the transmission depth of the electron beam is substantially equal to the thickness of the resin layer. Irradiation of rays can be suppressed, and deterioration of the substrate due to excess electron beams can be minimized.
The irradiation dose is preferably such that the crosslinking density of the resin composition layer is saturated, usually 5 to 300.
kGy (0.5 to 30 Mrad), preferably 10 to 60 kGy (1 to 6 Mrad) is selected.
Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type Can be used.

When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

<Evaluation method>
(1) Tensile elastic modulus The electron beam curable resin composition used for forming the protective layer was applied onto a biaxially stretched polyester film with a bar coater, and an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mra).
The electron beam of d) was irradiated and crosslinked and cured to form a protective layer (thickness: 20 μm). Using a sample obtained by peeling the protective layer from the polyester film, a sheet punched into a strip-shaped test piece (25 mm in width) in accordance with JIS K7127 is prepared, and a tensile compression test is performed in a temperature environment of 25 ° C. From the first linear part of the tensile stress-strain curve obtained by measuring using a machine (Tensilon RTC-1250A manufactured by Orientec Co., Ltd.) under the conditions of a tensile speed of 50 mm / min and a distance between chucks of 80 mm, Calculated by
E = Δρ / Δε
E: Tensile modulus Δρ: Stress difference due to the original average cross-sectional area between two points on a straight line Δε: Strain difference between the same two points (2) Scratch resistance Lamination for organic glass obtained in each example and comparative example The body was rubbed 5 times with a load of 1.5 kg using steel wool (manufactured by Nippon Steel Wool Co., Ltd., Bonstar # 0000), and the appearance was visually evaluated. The evaluation criteria are as follows.
A: No change was observed on the surface.
◯: Although fine scratches were observed on the surface, the coating film was not scraped or whitened.
Δ: Slight shaving or whitening of the coating film was observed.
X: There were significant scratches on the surface.
(3) Impact resistance It was carried out by a DuPont impact test. Place a laminate for organic glass between a wick with a tip diameter of 2/8 inch and a cradle with a dent that matches the diameter of the tip, drop a 500g heavyweight from a height of 50cm, and observe the surface of the specimen. did. Evaluation was performed according to the following criteria.
A: No change was observed on the surface.
◯: Slight whitening was confirmed to the extent that there was no practical problem on the surface.
(Triangle | delta): The fine crack of the grade which is satisfactory practically on the surface was confirmed.
X: Cracks to the extent that a practical problem occurs on the surface were confirmed.
(4) Scratch resistance The surface was scratched from the protective layer side with a thumb nail, and the appearance of the test piece was evaluated.
A: No change was observed on the surface.
A: Slight scratches on the surface were confirmed to have no practical problem.
(Triangle | delta): The dent crack | wound of the grade which is satisfactory practically on the surface was confirmed.
X: A deep dent scratch to the extent that a practical problem occurs was confirmed on the surface.

Example 1 (Production of laminate for organic glass)
On a substrate (polycarbonate plate, thickness: 2 mm, tensile modulus: 2380 MPa), a polyurethane two-component curable resin (acrylic polymer polyol and xylylene diisocyanate as a curing agent, NCO equivalent and OH equivalent in the same amount A composition containing a composition, a glass transition temperature Tg (when the polyol is uncured): 100 ° C., and 80 parts by mass of a urethane resin (glass transition point: −30 to −40 ° C.) 20 parts by mass Was applied by gravure printing to form a primer layer (thickness 1.5 μm).
Furthermore, bifunctional polycarbonate urethane acrylate (weight average molecular weight: 8,000)
0) Resin component comprising 94 parts by mass and 6 parts by mass of hexafunctional urethane acrylate (weight average molecular weight: 6,000), 1.1 parts by mass of UV absorber, 0.6 parts by mass of light stabilizer, and leveling agent 0 The ionizing radiation curable resin composition containing 2 parts by mass is coated on the primer layer with a bar coater, and is irradiated with an electron beam with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to be cured by crosslinking. A layer (thickness: 10 μm) was formed, and a laminate for organic glass having the configuration shown in FIG. 1 was produced.
The laminate for organic glass was evaluated by the above method. The evaluation results are shown in Table 1.

Example 2 and Comparative Examples 1-2
In Example 1, organic glass laminates were prepared in the same manner as in Example 1 except that the base material and ionizing radiation curable resin were those shown in Table 1, and each was evaluated by the above method. The evaluation results are shown in Table 1.

Ionizing radiation curable resin composition A (resin component): difunctional polycarbonate urethane acrylate (weight average molecular weight: 8,000) 94 parts by mass, and hexafunctional urethane acrylate (
Weight average molecular weight: 6,000) 6 parts by mass Ionizing radiation curable resin composition B (resin component): acrylic polymer (weight average molecular weight: 12
(0.0000) 60 parts by mass and trifunctional acrylate monomer (molecular weight: 298) 40 parts by mass ionizing radiation curable resin composition C (resin component): 3.9 functional urethane acrylate oligomer 30 parts by mass and bifunctional acrylate monomer 70 parts by weight

The laminate for organic glass of the present invention includes, for example, window materials and sunroof materials for automobiles, trains, ships and airplanes, openings for buildings and the like, fields of inorganic glass substitute materials such as window materials, and automobiles, trains, It can be suitably used as a transparent organic glass such as a headlamp for ships and aircraft. In addition, the laminate for organic glass of the present invention is particularly required to prevent scattering of fragments generated by impact and the like, and is used for vehicles such as automobiles, trains, ships, aircrafts, and window materials for vehicles and resin covers. It is also suitably used for these applications.

10 Laminate for Organic Glass 11 Substrate 12 Primer Layer 13 Protective Layer

Reference Example 1 and Comparative Examples 1-2
In Example 1, organic glass laminates were prepared in the same manner as in Example 1 except that the base material and ionizing radiation curable resin were those shown in Table 1, and each was evaluated by the above method. The evaluation results are shown in Table 1.

Claims (4)

  A laminate for organic glass comprising a protective layer laminated on a transparent resin substrate, wherein the protective layer is a cured product of an ionizing radiation curable resin composition, and the ionizing radiation curable resin composition is a polycarbonate (Metal). ) A laminate for organic glass comprising acrylate and polyfunctional (meth) acrylate in a mass ratio of 98: 2 to 70:30.   The laminate for organic glass according to claim 1, wherein the polycarbonate (meth) acrylate is bifunctional and the polyfunctional (meth) acrylate is trifunctional or more.   The laminate for organic glass according to claim 1, wherein the transparent resin substrate is made of a polycarbonate resin.   The laminate for organic glass according to any one of claims 1 to 3, wherein the laminate is for window material or resin cover.