JP2002127286A - Polymeric resin laminate and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize a polymeric resin/hard coat laminate excellent in all of abrasion resistance, surface hardness, light fastness and water resistance. SOLUTION: An active ray curable layer, of which the thickness is 2-50 μm and pencil handness is F or more as an independent layer, and a hard coat layer, of which the thickness formed by a vapor deposition process is 1.5-10 μm, maximum displacement obtained when the surface of the layer is subjected to nano identation measurement under a maximum load condition of 100 μN is 120 nm or less, Young's modulus is 15 GPa or more and plastic deformation hardness is 3 GPa or more, are laminated on at least one surface of a polymeric resin substrate to produce the polymeric resin laminate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer resin laminate having an excellent surface hardness, and more particularly to a laminate of a polycarbonate molded product having an excellent surface hardness. Window material (including windshield).

[0002] The polymer resin laminate of the present invention may be used for, for example, window materials in various buildings other than the above-mentioned applications (here, window materials are those which can be seen through at least).
, Transparent sound insulation plates for highways, etc., surface protection plates for solar cell panels, liquid crystal displays (LCDs), plasma displays (PDPs), electroluminescence displays (E
L), it can be suitably used for surface protection plates of various image / information display devices such as CRTs, or transparent electrode substrates of transparent tablets used in various portable information terminals, touch panel input devices and the like. is there.

[0003]

2. Description of the Related Art Polycarbonate resins have excellent transparency,
Because of its light weight and high impact resistance, it has been widely applied and developed as window materials and structural materials for various buildings, automobiles and the like.

However, hardness, abrasion resistance, weather resistance,
There is a disadvantage that it is significantly inferior to glass from the viewpoint of chemical resistance. Therefore, a method of coating a hard coat layer having a function of covering these properties on polycarbonate (for example, JP-A-48-81928, JP-A-
138565, JP-A-53-138476) have been proposed.

[0005]

The hard coat layer is formed of a hydrolyzed condensate of silicon alkoxide or a composition obtained by mixing other types of alkoxides and various ultrafine particles in addition thereto in an appropriate ratio. Layers which are hardened dynamically and layers which are obtained by polymerizing a polyfunctional acrylate by irradiation with actinic rays such as ultraviolet rays or electron beams are often used.

However, when the polymer resin / hard coat laminate is to be used mainly for outdoor applications such as the above-mentioned window materials for automobiles and buildings, the properties such as abrasion resistance and surface hardness are required. In addition to the demand for extremely high properties, it is necessary to exhibit excellent performance in light resistance (resistance to ultraviolet ray deterioration) and water resistance.

The present invention has been made in view of such circumstances, and has been made with the object of realizing a polymer resin / hard coat laminate excellent in all of abrasion resistance, surface hardness, light resistance, and water resistance of the laminate. Things.

[0008]

That is, the present invention is as follows.

1. On at least one surface of the polymer resin substrate, an actinic ray-cured layer having a thickness of 2 to 50 μm and having a pencil hardness of F or more by itself, and a thickness of 1.5 mm formed by using a vacuum film forming process. A hard coat layer having a maximum displacement of 120 nm or less, a Young's modulus of 15 GPa or more, and a plastic deformation hardness of 3 GPa or more when performing nanoindentation measurement on the surface of the layer at a maximum load of 100 μN under a condition of 10 μm to 10 μm. , A polymer resin laminate laminated in this order.

[0010] 2. The above polymer resin laminate, wherein the vacuum film formation process is a vacuum deposition method.

3. The hard coat layer is a layer composed of two layers in which a layer formed by a vacuum deposition method and a layer having a thickness of 0.02 to 0.5 μm formed by a sputtering method are laminated in this order from the substrate side. The polymer resin laminate described above, which is characterized in that:

4. The hard coat layer is a layer containing at least 50% by weight of silicon oxide at least or a layer composed of two layers in which each layer contains at least 50% by weight of silicon oxide. Polymer resin laminate.

5. The actinic ray-curable layer contains 50% by weight or more of one or more (meth) acrylate components having two or more (meth) acryloyl groups in a molecule or a unit repeating structure in a nonvolatile component. The polymer resin laminate described above, which is a layer formed by irradiating an actinic ray to a precursor material and curing the precursor material.

6. The above-mentioned polymer resin laminate, wherein the actinic ray-curable layer is a layer having a water absorption of 2% or less.

[0015] 7. The actinic ray-curable layer has a wavelength of 295 to 450 nm and an illuminance of 100 mW.
/ Cm ² of the light transmitted through the layer before and after irradiation for 100 hours, the increase in the chromaticity index b ^* value of the L ^* a ^* b ^* color system specified in Japanese Industrial Standard Z8729, that is, the value of the color difference ｂb ^* Is an actinic ray-curable layer wherein is at least 2 or less.

8. As the actinic ray-curable layer, a layer obtained by curing a precursor material containing at least 50% by weight of dicyclopentanyl diacrylate and / or dicyclopentanyl dimethacrylate in a nonvolatile component is used. The above polymer resin laminate.

9. The product of the amount (% by weight) of the ultraviolet absorber added to the non-volatile component of the precursor of the actinic ray curable layer and the thickness (μm) of the actinic ray curable layer is 30 to 300% by weight.
The polymer resin laminate described above, which is in the range of μm.

10. 300-350 n of actinic ray cured layer
The polymer resin laminate according to the above, wherein the light absorptivity in the wavelength region of m is 99% or more.

11. As an ultraviolet absorber mixed with the actinic ray-curable layer, 2- (4,6-diphenyl-1,3,5-
Triazin-2-yl) -5-[(hexyl) oxy]
-The above polymer resin laminate, wherein phenol is used as a main component of the ultraviolet absorbent.

[12] The thickness of the polymer resin substrate is 0.2mm
The polymer resin laminate according to the above, characterized in that:

13. The above polymer resin laminate, wherein the polymer resin substrate is a molded substrate of polycarbonate.

14. The polymer resin laminate described above, wherein the haze of the polymer resin laminate is 5% or less.

[15] After raising the temperature of the polymer resin substrate coated with the precursor of the actinic ray curable layer to a temperature of 50 to 130 ° C., the actinic ray is irradiated to form an actinic ray curable layer on the polymer substrate. The method for producing a polymer resin laminate described above.

16. The polymer resin substrate on which the actinic ray-curable layer is formed is subjected to a heat treatment at a temperature near the glass transition temperature of the polymer substrate, and then a hard coat layer is laminated on the actinic ray-curable layer. A method for producing a polymer resin laminate.

17. An automotive window material comprising the above polymer resin laminate.

Here, the nanoindentation measurement of the hard coat layer formed by using the vacuum film forming process was performed as follows.

That is, using a nano-intention tester ENT-1100 manufactured by Elionix Inc., using a triangular pyramid indenter with a ridge interval of 115 degrees as an indenter, applying a pushing load in steps of 1 μN / sec.
After reaching the maximum load, the pushing load is similarly gradually reduced in a step-like manner. The measurement was performed under a constant temperature condition of 25 ° C. After sufficiently stabilizing the temperature of the measurement device and the sample, the load / displacement curve was measured under the conditions of a maximum load of 100 μN and a maximum load holding time of 30 seconds, and the measurement was performed 10 times. The measured value was the average value of the continuous measurements.

In general, according to this method, it is possible to measure the mechanical properties of a layer having a thickness of several μm or more without being affected by the mechanical properties of the underlying layer. Of the layer, Young's modulus and plastic deformability of the layer, hardness and the like can be evaluated.

The pencil hardness of the actinic ray-curable layer was measured by laminating and curing the actinic ray-curable layer on a glass plate having a thickness of 2 mm to a thickness of about 7 μm, and then measuring the surface of the layer.

In performing these measurements, it is preferable to provide a primer layer between the active light-cured layer and the quartz plate in order to improve the adhesion between the active light-cured layer and the quartz plate. Will be Preferred examples of the primer layer include polymethyl methacrylate, a layer of a copolymer of methyl methacrylate and 2-hydroxyethyl methacrylate, and a layer of a copolymer of methyl methacrylate and γ-methacryloxypropyltrimethoxysilane. You. The thickness of the primer layer is preferably in the range of 1 to 2 μm from the viewpoint of preventing the pencil hardness from affecting the measurement result.

The measurement of the water absorption of the actinic ray cured layer was performed as follows. That is, after an actinic radiation-cured layer is formed directly on a glass plate with a thickness of about 20 μm, the cured layer is scraped off from the glass plate with a knife or the like in an amount of about 1 g. Next, the film piece is thermally dried in a vacuum dryer at 100 ° C. for 2 hours (to remove volatile substances in the film by volatilization), and then the film piece is accurately weighed (A). Next, the membrane piece was placed at 30 ° C,
After being kept in a thermo-hygrostat at 95% RH for 48 hours, the membrane piece was taken out of the thermo-hygrostat and immediately weighed accurately (a), {(a) / (a)}-1. With the value of
The value of the water absorption of the actinic ray cured layer was used. In addition, here, repeated measurement was performed five times, and the average value of these measured values was adopted.

That is, the present inventors have found that by producing a polymer resin laminate satisfying the following three points at the same time, a high abrasion resistance particularly suitable as a window material for automobiles is exhibited. The present invention has been achieved.

One of the points is that the maximum displacement is 120 nm or less when the surface of the layer is formed as the outermost surface layer of the laminate by a vacuum film forming process and the surface of the layer is measured by a nanoindentation measurement under a maximum load of 100 μN. Laminating a hard coat layer having a Young's modulus of 15 GPa or more and a plastic deformation hardness of 3 GPa or more.

Second, the thickness of the hard coat layer is at least 1.5 μm.

The third point is that an active light-cured layer having a pencil hardness of F or more and a film thickness of 2 to 50 μm is laminated between the hard coat layer and the polymer resin substrate. is there.

[0036]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

As described above, the outermost layer of the polymer resin laminate is formed by a vacuum film forming process, and the surface of the layer is subjected to a maximum load of 100 μN by a nanoindentation method.
When measured under the conditions of the maximum displacement is 120nm or less,
And a Young's modulus of 15 GPa or more and a plastic deformation hardness of 3
It is preferable that a hard coat layer having a GPa or more is laminated.

Here, the maximum displacement due to the nanoindentation is more preferably 100 nm or less, the Young's modulus is more preferably 25 GPa or more, and the plastic deformation hardness is more preferably 5 GPa or more.

As the vacuum film forming process, a vacuum evaporation method,
Sputtering method, chemical vapor deposition (deposition) method (CVD)
Among them, it is preferable to mainly use a vacuum deposition method, which generally has a feature that the film forming speed is high and the cost is excellent.

In the vacuum deposition method, usually, after evacuation is performed so that the pressure in the apparatus becomes at least 10 ^-1 Pa or less, a heated and vaporized material is deposited on a substrate in the apparatus to form a layer. How to get. In general, as a method of heating and vaporizing a material, a material filled in a crucible or the like is heated by applying an electron beam or an ion beam, or a material filled in a resistance wire such as a tungsten boat is converted into a resistance wire. For example, a method of heating by applying an electric current is used.

In particular, in the case of using the former heating method using an electron beam or an ion beam, by controlling the amount of beam emission, it is possible to achieve a high deposition rate and a stable vacuum deposition for a long time. μ
This is preferable because a layer having a thickness exceeding m can be obtained relatively easily and economically.

Here, a method of ionizing vapor-deposited particles in a vacuum chamber by an appropriate method, accelerating the electric field and depositing the particles on a substrate (often referred to as ionized vapor deposition, electric field assisted vapor deposition, etc.). ), Etc., various kinds of vacuum deposition methods in which a step of increasing the kinetic energy of the deposited particles is applied can be used as necessary.

As the hard coat layer, a layer formed by the above-described vacuum deposition method (hereinafter, referred to as a vapor deposition layer) and a layer formed by the sputtering method (hereinafter, referred to as a sputter layer) are formed from the substrate side. A layer composed of two layers stacked in order may be used.

In the sputtering method (generally called a magnetron sputtering method), similarly to the vacuum evaporation method, after the inside of the apparatus is evacuated to a pressure of at least 10 ^-1 Pa or less, an inert gas or slightly An inert gas mixed with a reactive gas is introduced, a high electric field (AC and / or DC) and a magnetic field are applied between the material target and the substrate to induce a plasma state, and the gas accelerated in the plasma is applied to the material target. In this method, the material on the surface of the target is scattered in the form of atoms / molecules by the impact of the collision and adheres to the substrate to obtain a layer.

In general, the sputtering method has a feature that a denser and harder layer can be easily obtained. However, the deposition rate is much slower than that of the above-mentioned vacuum evaporation method, and 0.5 μm
It takes a very long time to form a layer having a thickness exceeding.
That is, the thickness of the sputtered layer is preferably 0.5 μm or less, more preferably 0.25 μm or less, mainly from an economic viewpoint.

The thickness of the sputtered layer must be at least 0.02 μm or more, more preferably 0.05 μm or more, and still more preferably 0.1 μm or more in order to obtain the effect of improving the characteristics by the lamination.

When the deposition layer and the sputter layer are laminated as described above, the vacuum deposition step and the sputtering step may be performed in the same vacuum chamber or in two or more vacuum chambers continuous with a movable sill plate interposed therebetween. It is also possible to perform the process continuously while moving the substrate in the (vacuum chamber), and it is preferably performed from the advantages of preventing surface contamination and shortening the vacuum evacuation time.

Examples of the material of such a hard coat layer include inorganic oxides such as silicon oxide, aluminum oxide, cerium oxide, silicon nitride, aluminum nitride, and silicon carbide, nitrides, and carbides. Among them, in order to make the hard coat layer have high transparency and excellent mechanical properties, it is preferable to use silicon oxide as a main component, and silicon oxide is at least 50% by weight or more of the whole layer, more preferably. It preferably accounts for 75% by weight.

For the purpose of obtaining higher transparency, the value of n of SiOn, which indicates the oxidation number of silicon oxide, is preferably about 2.0.

As described above, the hard coat layer preferably uses silicon oxide as a main component, but if necessary, uses a material obtained by mixing other types of inorganic oxides as an auxiliary component at an appropriate ratio. Is also possible.

Preferred examples of such subcomponents include magnesium oxide, zirconium oxide, and titanium oxide, which increase the hardness and improve the brittleness of the hard coat layer and the refractive index difference between the hard coat layer and the actinic ray cured layer. Are mixed for the purpose of adjusting the refractive index for the purpose of reducing the optical interference fringes derived from the above.

In order to obtain excellent abrasion resistance of the polymer resin laminate, the thickness of the hard coat layer is preferably 1.5 μm or more, more preferably, as shown in FIG. Is 2.5 μm or more, more preferably 3.5 μm
That is all. However, when the film thickness exceeds 10 μm, cracks are generated in the layer and the adhesion is often decreased, which is not preferable.

In some cases, it is preferable to appropriately heat the substrate in a vacuum chamber during the lamination of the hard coat layer, if necessary. As a method for heating the substrate, a halogen lamp or the like can be used. The heating temperature is preferably in the range of about 50 to 120 ° C., for the purpose of alleviating the residual stress of the deposited film, improving the adhesion of the deposited film, and particularly preventing the deterioration of the adhesion of the deposited film due to a change in the ambient temperature of the laminate. May be preferred.

Regarding the reduction of the light interference fringes of the hard coat layer, the refractive index of the hard coat layer and the refractive index of the actinic light cured layer are sandwiched between the actinic light curing layer and the hard coat layer. The value (optical film thickness) obtained by multiplying the thickness of the layer by the refractive index is 100 to 160
The effect may also be obtained by laminating the layers to a thickness of about nm, and this is performed as necessary.

As the actinic ray-curable layer in the present invention,
As described above, in order to obtain the effect of improving the abrasion resistance of the polymer resin laminate, a layer alone having a pencil hardness of F or more is preferably used. The pencil hardness of the actinic ray-curable layer is more preferably 2H or more.

The reason why the wear resistance is improved by sandwiching and laminating an actinic ray-curable layer having a pencil hardness of F or more between the polymer resin substrate and the hard coat layer is not clear. However, considering the results of the finite element method simulation performed by the present inventors, it occurs with friction (shear deformation) of the hard coat layer surface,
It is considered that the interfacial stress (delamination force or shear force) between the hard coat layer and the actinic ray cured layer may be reduced.

The thickness of the actinic ray-curable layer is preferably in the range of 2 to 50 μm. If the film thickness is less than 2 μm, the effect of improving the abrasion resistance described above tends to be reduced, and the film is liable to be affected by the curing failure due to atmospheric oxygen during the curing with active light rays, which is not preferable. When the thickness of the actinic ray-curable layer exceeds 50 μm, internal stress due to curing shrinkage increases, the adhesion between the polymer resin substrate and the actinic ray-curable layer is reduced, or cracks are easily generated in the cured layer. Absent. However, depending on the material composition of the actinic ray-curable layer, even if it is formed to a thickness exceeding 50 μm, the adhesion may not be reduced and cracks may not occur. In such a case, a layer having a thickness exceeding 50 μm may be formed as necessary.

The actinic ray-curable layer preferably has a glass transition temperature or softening temperature of about 120 ° C. or higher. These values can be evaluated by, for example, an endothermic peak in differential thermal analysis (DSC), analysis of dynamic viscoelasticity by thermal scanning, or another method (a simple evaluation method was employed in the examples of the present application). it can.

Since the glass transition temperature or the softening temperature of the actinic ray-curable layer is high, even when the temperature of the hard coat layer increases due to the deposition of energetic deposited particles and the heat radiation from the target during vacuum deposition of the hard coat layer, It becomes possible to support the hard coat layer mechanically and firmly.

On the other hand, when the glass transition temperature or softening temperature of the actinic ray-curable layer is low, problems such as poor adhesion between the actinic ray-curable layer and the hard coat layer and cracks in the hard coat layer may be caused. There are many.

As such an actinic ray-curable layer, for example, one or a mixture of two or more (meth) acrylates having two or more functional groups in a molecule or in a unit repeating structure is used. To the non-volatile component of 50
A layer obtained by curing a precursor material containing not less than% by weight by actinic rays such as ultraviolet rays and electron beams is preferably used.

Examples of such (meth) acrylates include dicyclopentanyl diacrylate, dicyclopentanyl dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane ethylene oxide modified triacrylate, and trimethylolpropane propylene oxide modified triacrylate. , Pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, polyfunctional (meth) containing isocyanuric ring
Acrylate (number of functional groups: about 3 to 15), polyfunctional (meth) acrylate having an isocyanate bond (number of functional groups: about 2 to 6; these are often often referred to as urethane acrylates), so-called polyester acrylates (for example, "Toagosei Chemical" Aronix M8030, M
8060, M8100, M8530, M8560, M9
050 ") and the like.

In the actinic ray-curable layer, if necessary, the number of functional groups contained in the molecule or in the unit repeating structure is 1 in a proportion of less than 50% by weight of the nonvolatile component as a subcomponent (meth). Acrylates, compounds having a vinyl group or an allyl group, various alkoxide components including silicon alkoxides, ultrafine particles having an average particle diameter (diameter) of 3 to 30 nm, a curing agent or curing catalyst such as a photopolymerization initiator,
Photopolymerization initiation aid (sensitizer), leveling agent, light absorber (ultraviolet absorber), light stabilizer (antioxidant), defoamer,
A thickener and the like are mixed as necessary.

The addition amount of the auxiliary component is more preferably 3
It is less than 0%, more preferably less than 20%.

The (meth) acrylate having one functional group in the molecule or in the unit repeating structure includes, for example, acryloylmorpholine, isobornyl (meth) acrylate, N-vinyl-2-pyrrolidone, γ- ( (Meth) acryloxypropyltrimethoxysilane and the like.

Examples of the ultrafine particles having an average particle diameter of 3 to 30 nm include ultrafine particles made of inorganic oxides such as silicon oxide, aluminum oxide, aluminum chloride, titanium oxide, zinc oxide, zirconium oxide, cerium oxide, and tin oxide.
Ultrafine particles of organic crosslinked fine particles obtained by crosslinking methyl methacrylate or divinylbenzene with an acid or imide are suitable. It is more preferable that the surface of these ultrafine particles is previously treated with a component containing various organic groups. Since it is particularly preferable that the organic group contains a (meth) acryloyl group as an organic group, γ- (meth) acryloxypropyltrimethoxysilane is preferably exemplified as a component used for the surface treatment.

These subcomponents reduce the curing shrinkage of the actinic ray-curable layer, improve the adhesion to the substrate or the silicon oxide layer by vacuum evaporation, improve the weather resistance, improve the water resistance, and improve the surface properties. It is mixed for the purpose of improving and improving the hardness of the actinic ray cured layer and imparting various functions such as matching of the refractive index with the silicon oxide layer by a vacuum deposition method.

The active light-cured layer has a water absorption of 2%.
Or less, more preferably 1% or less. That is, when the water absorption of the layer exceeds 2%, the water resistance of the polymer resin laminate is often insufficient. It is presumed that the reason for this is probably that the adhesion between the active light-cured layer and the vapor-deposited layer becomes poor due to an increase in the interface stress between the active light-cured layer and the vapor-deposited layer due to the volume expansion of the layer due to moisture adsorption. This is a particularly serious problem when the laminate is used for applications requiring excellent water resistance (such as outdoor use).

At the same time, when the water absorption of the actinic ray-cured layer is high, the release of water into the vacuum chamber during vacuum deposition increases, and the degree of vacuum deteriorates and the film quality of the deposited layer deteriorates. Often, it is undesirable.

When the polymer resin laminate of the present invention is used for applications requiring excellent light resistance (UV light resistance) (outdoor use, etc.), the actinic ray-curable layer having a thickness of 7 μm is particularly preferable. L ^* a ^* of the transmitted light of the layer before and after irradiating the actinic radiation cured layer with light having a wavelength of 295 to 450 nm and an illuminance of 100 mW / cm ² for 100 hours as defined in Japanese Industrial Standard Z8729.
It is more preferable that the active light-cured layer has an increase in the b ^* value of the chromaticness index b ^* of the b ^* color system, that is, an actinic ray-curable layer having a color difference Δb ^* of 2 or less. Incidentally, the Δ b ^* value is more preferably 1 or less. This is because, when the polymer resin laminate of the present invention is used particularly in an outdoor environment, when the discoloration (coloring) of the actinic ray-curable layer occurs due to long-term exposure to ultraviolet light, the appearance of the laminate is significantly deteriorated. It is.

The actinic ray-curable layer does not necessarily have to satisfy all of these various properties depending on the application, but it is necessary that at least the layer alone has a pencil hardness of F or more. Further, when the polymer resin laminate of the present invention is used for a wide range of applications, it is more preferable that the layer satisfies these various properties at the same time.

From such a viewpoint, the various (meta)
Among the acrylates, as those more preferably used, for example, dicyclopentanyl diacrylate and / or dicyclopentanyl dimethacrylate have low water absorption of an actinic ray curable layer obtained by curing these as a main component, It is excellent in water resistance and also excellent in various properties such as transparency, hardness and light resistance of the layer, and is particularly preferably used.

The above-mentioned polyester acrylates often bring about an improvement in adhesion and water resistance, and isobornyl (meth) acrylate has a characteristic of low water absorption, and is preferably used.

As described above, the actinic ray-curable layer is prepared by diluting the above-mentioned material with various solvents as necessary, coating the material on a substrate, and applying an electron beam, ultraviolet light (which may contain visible light) or the like. Irradiation with actinic light allows the material to be cured and formed.

The electron beam curing method generally has a feature that the penetration depth is determined by the electron acceleration voltage and the density of the cured layer, and is not affected by the light absorption (mainly in the ultraviolet region) of the cured layer itself. In addition, since the ultraviolet absorption wavelength region is not used, it is a particularly effective curing method when an ultraviolet absorber is mixed in the cured layer for the purpose of improving the weather resistance (for example, ultraviolet aging) of the polymer resin laminate. .

In the case of performing ultraviolet curing, it is preferable to add an appropriate amount of a photopolymerization initiator as an auxiliary component, and also to add various sensitizers as needed for the purpose of improving the efficiency of the curing reaction. .

In any of the electron beam curing method and the ultraviolet ray curing method, in order to suppress the curing failure due to oxygen,
Replacing oxygen in the surrounding atmosphere with an inert gas such as nitrogen is also performed as necessary.

Examples of the photopolymerization initiator include diethoxyacetophenone, 2-methyl-1- {4- (methylthio) phenyl} -2-morpholinopropane and 2-hydroxy-2-methyl-1-phenylpropane-1 Acetophenone compounds such as -one and 1-hydroxycyclohexylphenyl ketone; benzoin compounds such as benzoin and benzyldimethylketal; benzophenone;
Benzophenone compounds such as benzoylbenzoic acid; and thioxanthone compounds such as thioxanthone and 2,4-dichlorothioxanthone. Further, a copolymerizable photopolymerization initiator having an acryloyl group, a methacryloyl group, an allyl group, or a vinyl group added to these skeletons is also preferably used.Examples thereof include α-allylbenzoin, α-allylbenzoin aryl ether, and acrylated benzophenone. Is exemplified.

The addition amount of the photopolymerization initiator is preferably from 0.1 to 10% by weight based on the total amount of the nonvolatile components of the precursor of the actinic ray-curable layer. Here, the amount of addition is preferably 1 to 10% by weight when oxygen in the surrounding atmosphere is not replaced at the time of ultraviolet irradiation, and 0.1 to 3% by weight when replacement with an inert gas is performed.

The actinic ray-curable layer itself preferably has a sufficient ultraviolet absorbing property. That is, it is preferable to use a method of adding an ultraviolet absorber as a subcomponent in the actinic ray-curable layer. This is an optimal method as a countermeasure against the problem that the polymer resin used for the substrate is significantly discolored (colored) by long-term outdoor exposure to ultraviolet light.

When an ultraviolet absorber is added as an auxiliary component to the actinic ray-curable layer as described above, at least 300 to 35
An ultraviolet absorber having a large absorption in a wavelength range of a wavelength range of 0 nm is preferably used, and among them, a compound containing a benzotriazole skeleton or a triazine skeleton in a molecule is particularly preferable.

Examples of these are, for example, 2- (2H
-Benzotriazol-2-yl) -p-cresol,
2- (2H-benzotriazol-2-yl) -4,6
-Bis (1-methyl-1-phenylethyl) phenol, 2-benzotriazol-2-yl-4,6-di-
tert-butylphenol, 2- [5-chloro (2
H) -Benzotriazol-2-yl] -4-methyl-
6- (tert-butyl) phenol, 2,4-di-t
tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 2- (2H-benzotriazole -2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl ) Oxy]-
Phenol, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -4,6-bis (2,4
-Dimethylphenyl) -1,3,5-triazine and the like.

Among these, 2- (4,6-diphenyl-1,3,3), which is a triazine type ultraviolet absorber, is particularly preferred.
5-Triazin-2-yl) -5-[(hexyl) oxy] -phenol is very preferably used because it is less susceptible to chemical decomposition and remains stable in the actinic radiation-cured layer. When this ultraviolet absorber is used, even when the actinic ray-curable layer is cured by irradiation of ultraviolet rays (in many cases, a photopolymerization initiator coexists), curing inhibition is small and the layer is cured well. Can do things.

Further, as an ultraviolet absorber, a compound obtained by copolymerizing a compound having a benzotriazole skeleton or a triazine skeleton with a compound having a methacryloyl group, an acryloyl group or a vinyl group (for example, 2-
(2′-hydroxy-5′-methacryloxyphenyl)
-H-benzotriazole, etc.) is called a reactive ultraviolet absorber capable of causing a crosslinking reaction with an acrylate component or a methacrylate component mainly forming the actinic ray-curable layer. It is preferably used for the purpose of stably fixing an ultraviolet absorbent to improve durability.

In order to make the weather resistance (ultraviolet aging resistance) of the polymer resin laminate sufficient, the active light-cured layer 3
The light absorptance is at least 99% or more, more preferably 9 at any wavelength in the wavelength range of 00 to 350 nm.
It is preferred to be 9.9% or more. Note that 4. "The light absorption of the actinic radiation-curable layer (A) in the wavelength region of 300 to 350 nm is 99% or more"
This means that "the light absorption rate is at least 99% or more at any wavelength in the wavelength range of 300 to 350 nm".

For this purpose, the product of the addition amount (% by weight) of the ultraviolet absorber in the nonvolatile component of the precursor of the actinic ray-curable layer and the thickness (μm) of the actinic ray-curable layer is 30 to
It is preferably in the range of 300% by weight · μm, more preferably 50 to 150% by weight · um.

In the case where an ultraviolet absorber is mixed with the precursor of the actinic ray curable layer and the layer is cured by irradiating ultraviolet rays, the wavelength of the ultraviolet light that induces curing (photopolymerization) and the absorption wavelength of the ultraviolet absorber are used. Is preferably somewhat different from That is, as described above, the ultraviolet absorber is 300
Since it is preferable to use a material having a large absorption in a wavelength region of from 350 nm to 350 nm, it is preferable that the wavelength of the ultraviolet light for inducing photopolymerization is 350 nm or more or 300 nm or less.

For this purpose, the wavelength region having large light absorption is 350 to 400 nm and / or 220 to 30 nm.
There is a method using a photopolymerization initiator having a thickness of 0 nm.
Examples of these include 2-hydroxy-2-methyl-1
-Phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-
1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzyl dimethyl ketal, benzoyl benzoic acid, Methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenylsulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4 dimethylthioxanthone , Isopropylthioxanthone, 2,
4-diethylthioxanthone, 2,4-diisopropylthioxanthone, dibenzosuberone, methylphenylglyoxylate, 1-phenyl-1,2-propanedione-2 (O-ethoxycarbonyl) oxime and the like are exemplified. .

For the same purpose, it is also preferable to use a photopolymerization initiation aid (sensitizer) having a large light absorption at 220 to 300 nm and / or 350 to 400 nm in combination with the photopolymerization initiator. Will be

Examples of the photopolymerization initiation aid include, for example, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid (n
-Butoxy) ethyl, isoamyl 4-dimethylaminobenzoate, 4,4-bis (diethylamino) benzophenone, 4-dimethylaminoacetophenone and the like.

It is preferable that such a photopolymerization initiation aid is mixed at a ratio of 10 to 40% by weight based on the mixing amount of the photopolymerization initiator.

The method for coating these actinic ray-curable layers on a polymer resin substrate includes, for example, (Doctor)
Knife coating, microgravure coating, direct gravure coating, offset gravure, reverse gravure, reverse roll coating, (Meier) bar coating, die coating, spray coating, dip coating, etc. are preferably applied. it can.

Here, the polymer resin substrate coated with the precursor of the actinic ray curable layer is used to improve the leveling property of the precursor material liquid and the adhesion between the actinic ray curable layer and the polymer resin substrate. 50-1 once before irradiating with actinic rays for the purpose
It may be preferable to raise the temperature to 30 ° C.

After laminating the actinic ray-curable layer on the polymer resin substrate and before laminating the hard coat layer, the laminate is heated to a temperature near the glass transition temperature of the polymer resin substrate (preferably from the glass transition temperature). The heat treatment is preferably performed at a temperature lower by about 20 ° C.). By performing such heat treatment,
The residual stress of the polymer resin substrate on which the actinic ray cured layer is laminated is thermally relaxed, and the adhesion of the layer is improved, and at the same time, the volatile components contained in the actinic ray cured layer (mainly photopolymerization) The decomposition product of the initiator is volatilized and removed, and the effect of reducing the amount of volatile components released into the vacuum chamber during vacuum film formation is reduced.

Similarly, after laminating the actinic ray-curable layer on the polymer resin substrate and before laminating the hard coat layer,
This laminate is subjected to heat molding (such as hot bending),
It is also possible to perform vacuum molding, insert molding or the like using the laminate, and to laminate a hard coat layer on the actinic radiation cured layer after molding.

When laminating an actinic ray-curable layer on a polymer resin substrate or laminating a hard coat layer on an actinic ray-curable layer, it is necessary to form a layer on the polymer resin substrate or the actinic ray-curable layer. Various surface treatments may be performed thereon. As such a surface treatment, for example, known methods such as plasma treatment, corona treatment, and UV-ozone treatment are preferably used.
Effects such as improvement of the adhesion of the layer by the surface activation and improvement of the coating property of the precursor material can be obtained.

In order to mainly improve the adhesion between the polymer resin substrate and the actinic ray-curable layer, it is also possible to sandwich an appropriate primer layer between them and to laminate them. As such a primer layer, for example, polymethyl methacrylate or a layer obtained by copolymerizing an acrylate component with polymethyl methacrylate is preferably used.

As the polymer resin substrate, for example, polycarbonate, polyarylate, polyethylene terephthalate, polyethylene naphthalate and various polyolefin resins (for example, trade name “ARTON” of JSR, trade name “ZEONEX” of Zeon Corporation) And the like.

The thickness of the polymer resin substrate is preferably at least 0.2 mm, and more preferably 0 mm or more, from the viewpoint of reducing curling of the polymer resin laminate due to internal stress during lamination of the hard coat layer. 0.4 mm or more, more preferably 0.8 mm or more.

The above-mentioned ultraviolet absorbent, light stabilizer (antioxidant), various visible light absorbents (pigments, dyes, etc.), infrared light absorption, etc. An agent, an antistatic agent (conductive substance), a flame retardant, and the like may be mixed.

In applications such as window materials for automobiles and buildings, polycarbonate is particularly preferred from the viewpoints of impact resistance, transparency, moldability and the like. Here, the polycarbonate means a polycondensate of an aromatic dihydroxy compound and a carbonic acid bond-forming compound.

Specific examples of the aromatic dihydroxy compound include bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane,
2,2-bis (4-hydroxy-3-methylphenyl)
Propane, 2,2-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) Propane, bis (4-
Bis (4-hydroxyaryl) alkanes such as hydroxyphenyl) phenylmethane, 4,4-dihydroxyphenyl-1,1′-m-diisopropylbenzene, and 4,4′-dihydroxyphenyl-9,9-fluorene; 1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-methyl-1- (4-hydroxyphenyl) -4- (dimethyl-4-hydroxyphenyl) methyl- Cyclohexane, 4- [1- [3- (4-hydroxyphenyl) -4-methylcyclohexyl] -1-methylethyl] -phenol, 4,4 ′-[1-methyl-4
-(1-methylethyl) -1,3-cyclohexanediyl] bisphenol, 2,2,2 ', 2'-tetrahydro-3,3,3', 3'-tetramethyl-1,1'-spirobis- [ Bis (hydroxyaryl) cycloalkanes such as 1H-indene] -6,6′-diol, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether,
Dihydroxyaryl ethers such as 4'-dihydroxy-3,3'-dimethylphenyl ether;
Dihydroxydiaryl sulfides such as -dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, and 4,4'-
Dihydroxydiarylsulfoxides such as dihydroxydiphenylsulfoxide and 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfoxide;
4,4'-dihydroxydiphenyl sulfone, 4,4 '
Dihydroxydiarylsulfones such as -dihydroxy-3,3'-dimethyldiphenylsulfone;
Dihydroxydiarylisatins such as 4'-dihydroxydiphenyl-3,3'-isatin, dihydroxydiarylxanthenes such as 3,6-dihydroxy-9,9-dimethylxanthene, resorcinol, 3-methylresorcinol, and 3-ethylresorcinol , 3-butylresorcin, 3-t-butylresorcin, 3-phenylresorcin, 3-cumylresorcin, hydroquinone, 2-methylhydroquinone, 2-ethylhydroquinone, 2-butylhydroquinone, 2-t-butylhydroquinone, 2- Dihydroxybenzenes such as phenylhydroquinone and 2-cumylhydroquinone; and dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl and 3,3′-dichloro-4,4′-dihydroxydiphenyl.

Among them, 2,2-bis (4-hydroxyphenyl) propane is preferred.

Specific examples of the compound capable of forming a carbonic acid bond include phosgene such as phosgene, trichloromethylchloroformate and bis (trichloromethyl) carbonate; diarylcarbonates such as diphenylcarbonate and ditolylcarbonate; dimethylcarbonate; Examples thereof include dialkyl carbonates such as carbonate, and alkylaryl carbonates such as methylphenyl carbonate and ethylphenyl carbonate.

When phosgenes are used, polycarbonate is produced by a solution method, and when carbonates having a carbonate bond are used, they are produced by a melting method.

Among the carbonates, diphenyl carbonate is preferably used.

These compounds can be used alone or in combination.

It should be noted that those containing other components as copolymerized or blended components may also be used. In the category of polycarbonate.

The most suitable compound for the present invention uses 2,2-bis (4-hydroxyphenyl) propane as the aromatic dihydroxy compound, and phosgenes or carbonates having a carbonate bond as the carbonate bond-forming compound. This is the polycarbonate used.

If the copolymerization ratio or the blending ratio of the other components is high, the characteristics of the polycarbonate are weakened. Therefore, the copolymerization ratio or the blending ratio is desirably 20% by weight or less.
0% by weight or less is more desirable.

The shape of the polymer resin substrate is not particularly limited, but a molded product having a film-like or sheet-like shape is particularly preferably used because a uniform layer can be easily coated. Although a molded product having a complicated shape such as a curved surface or unevenness can be used, there is a case where a coating method of a layer is restricted (a dip coating method is mainly used) in some cases.

When laminating the above-mentioned actinic ray-curable layer, these polymer resin substrates may be subjected to a surface treatment of the substrate in advance or a suitable primer layer may be laminated, if necessary. As such a surface treatment, a known plasma treatment, corona treatment, UV-ozone treatment, or the like is preferably used, and has an effect of improving the adhesion of the cured layer or improving the coatability of the precursor material. Obtainable.

As the primer layer, those having a function of improving the adhesion of the cured layer and the weather resistance (for example, resistance to ultraviolet aging) of the laminate are preferably used.

As such a primer layer, for example, polymers of various methacrylic esters and acrylic esters, or copolymers of these with other components are preferable. Such a copolymer component is preferably a component having an amino group and an epoxy group in the molecule.

For the purpose of improving the weather resistance, the primer layer may contain an appropriate amount of components such as various ultraviolet absorbers and antioxidants, if necessary.

The thickness of the primer layer is 0.1 to 15 μm
Is preferably applied, and more preferably 0.3 to 10 μm.

The polymer resin laminate of the present invention needs to have high transparency of the laminate. Specifically, the haze value of the laminate is preferably 5% or less, more preferably 3% or less, and further preferably 2% or less.

However, it is generally desired that the light transmittance of the polymer resin laminate is high, and the total light transmittance is 50%.
% Or more, and more preferably 70% or more. However, depending on the application, a high light transmittance may not always be desired.For example, in a window material for a rear seat of an automobile, for the purpose of suppressing a rise in the temperature inside the vehicle due to direct sunlight, for example, the inside of a polymer resin substrate is used. In some cases, the light transmittance of the laminate is intentionally reduced by a method such as mixing a visible light absorber (a pigment, a dye, or the like).

[0119]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below. However, the present invention is not limited to this. “Parts” are “parts by weight” unless otherwise specified.

The evaluation of various characteristics in the examples was performed in the following manner.

(Nano Indentation Measurement) Nano Indentation Tester manufactured by Elionix Inc.
Using ENT-1100, various physical property values of the hard coat layer were measured. That is, the ridge spacing 11 is used as an indenter.
Using a 5-degree triangular pyramid indenter, an indentation load is applied in steps of 1 μN / sec, and after reaching the maximum load, the indentation load is similarly gradually reduced in steps. The measurement is performed under a constant temperature condition of 25 ° C. After sufficiently stabilizing the temperature of the measurement device and the sample, the maximum load is 100 μN, and the maximum load holding time is 3.
The load / displacement curve was measured under the condition of 0 second, and the average value of 10 consecutive measurements was taken as the measured value.

Since errors in the measurement data may occur due to wear of the tip of the indenter or the like, before measuring each sample, first measure a commercially available silicon wafer and measure the silicon under a maximum load of 1 mN. After confirming that the value of the maximum displacement when the wafer is pushed is within the range of 55 nm ± 3 nm, the sample is measured. still,
If the value of the maximum displacement deviates from this range, a new indenter shall be replaced.

For reference, the results of measuring a molded plate of plate glass and polycarbonate (used as a polymer resin substrate in Example 1) by the above method are described. The former shows a maximum displacement of 18 nm and a Young's modulus of 234. 2 GPa and plastic deformation hardness 61.1 GPa, the latter having a maximum displacement of 140 n
m, Young's modulus 5.8 GPa, plastic deformation hardness 0.47 GP
a.

(Measurement of water absorption of actinic ray-cured layer) After forming an actinic ray-cured layer with a thickness of about 20 μm directly on a glass plate, the cured layer was cut into a piece of film from the glass plate with a knife or the like.
Take off the amount of g. Next, this film piece is placed in a vacuum dryer for 10 minutes.
After performing thermal drying (volatilization removal of volatile substances in the film) at 0 ° C. for 2 hours, the film pieces are accurately weighed (A). Next, after keeping the film piece in a thermo-hygrostat at 30 ° C. and 95% RH for 48 hours, the film piece is taken out of the thermo-hygrostat and immediately weighed accurately (a), Δ (a) ) / (A)｝-1
Was used as the value of the water absorption of the actinic ray-curable layer.
In addition, here, repeated measurement was performed five times, and the average value of these measured values was adopted.

(Measurement of weight loss rate before and after boiling water immersion test of actinic ray cured layer) After forming an actinic ray curable layer with a thickness of about 20 μm directly on a glass plate, the cured layer was cut with a blade or the like. 0.5 g of a piece of the film scraped off from the top was weighed and immersed in boiling water for 1 hour in a beaker in which pure water was supplied so that the amount of water was always 200 cc or more. The whole amount was subjected to suction filtration through a membrane filter having a pore size of 5 μm, and the dry weight of the solid matter remaining on the membrane filter was measured to determine the weight loss before and after the test.

(Measurement of Pencil Hardness) Japanese Industrial Standard K540
The measurement was carried out in accordance with the pencil hardness measurement method described in No. 0. In this example, from the viewpoint of improving the reproducibility of the measurement, the sample was placed on a glass plate having a thickness of 2 mm with an epoxy-based adhesive (Nichiban). The pencil was scanned in the plane direction in a state where the pencil was fixed using a product name of “Araldite Rapid”).

This is because by firmly fixing the sample, it is possible to eliminate the influence of distortion or bending of the sample when scanning with a pencil, and it is particularly effective in improving the reproducibility when the thickness of the sample is 1 mm or less. There is.

The determination of the presence or absence of scratches on the sample
The measurement is performed with the naked eye of the measurer in accordance with the above standard. If the judgment of the damage is delicate, the depth of the scratch (recess) is measured with a commercially available stylus-type surface roughness meter, and measured at five different locations. When the average value of the depth measured in the step is 0.2 μm or more, it was determined that “scratch occurred”.

The pencil hardness of the actinic ray-curable layer described in the examples was determined by coating the following precursor solution P for forming a primer layer on a glass plate having a thickness of 2 mm in a thickness of 1 μm in advance, and heating at 130 ° C. for 10 minutes. After the heat treatment to laminate the primer layer, the measurement was performed on a sample in which the actinic ray-curable layer was laminated to a thickness of 7 μm.

(Preparation of Precursor Liquid P for Forming Primer Layer) In a flask equipped with a reflux condenser and a stirring apparatus and purged with nitrogen, 95.1 parts by weight of methyl methacrylate, 12.4 parts by weight of 3-methacryloxypropyltrimethoxysilane Parts, 0.16 parts by weight of azobisisobutyronitrile and 200 parts by weight of 1,2-dimethoxyethane were added and dissolved.

The reaction system obtained by stirring at 70 ° C. for 6 hours was poured into n-hexane to cause precipitation, and the copolymer 95
Parts by weight were obtained.

The weight average molecular weight of this polymer was 150,000 as measured by GPC.

10 parts by weight of this polymer was dissolved in a mixed solvent consisting of 63 parts by weight of methyl isobutyl ketone and 27 parts by weight of 2-butanol, followed by filtration through a 3 μm filter to obtain a precursor liquid P for forming a primer layer.

(Evaluation of Softening Temperature of Active Light Cured Layer) A test piece for evaluation was prepared in exactly the same manner as the above-described laminated active light curable layer on glass for measuring the pencil hardness, and the test piece was heated with a heater. While the surface of the actinic ray-curable layer was lightly pressed with a glass rod, the temperature at which the flexibility and tackiness (tackiness) of the layer began to change significantly was examined, and this temperature was taken as the softening temperature of the actinic ray-curable layer.

(Measurement of Taber Abrasion) Using a Taber abrasion tester (manufactured by Toyo Seiki Co., Ltd.), a wear wheel CS-10 was used.
F, the surface of the test piece (the surface on which the silicon oxide layer was laminated) was worn under the conditions of a load of 4.9 N and 1000 cycles, and the haze value obtained from the following equation was evaluated by the difference (ΔH) between before and after the wear.

Haze (%) = (diffuse transmittance / total light transmittance) × 100 (measurement of haze value and total light transmittance) A measuring instrument manufactured by Nippon Denshoku Industries Co., Ltd. (trade name “COH-300”)
A ").

(Measurement of UV Absorbance of Active Light Cured Layer)
The measurement was performed using a Hitachi spectrophotometer U-3500.
In the measurement, in order to eliminate the influence of ultraviolet absorption by the polymer resin substrate or the like, the active light-cured layer was formed on two quartz plates having a thickness of 2 mm with the same film thickness (however, in the examples, Using a sample separately formed in the above manner, [((UV transmittance of quartz plate when no active light-cured layer is laminated)) − (quartz when active light-cured layer is laminated) UV transmittance of plate)] /
The ultraviolet ray absorbance of the actinic ray-curable layer was determined by taking the value of (ultraviolet transmittance of the quartz plate when no actinic ray-curable layer was laminated). Here, before laminating the actinic ray-curable layer on the quartz plate, the above-mentioned precursor solution P for forming a primer layer was coated in advance, dried at 130 ° C. for 10 minutes, and then 2 μm thick.
m of primer layers are laminated.

(Adhesion test) Measurement was carried out in accordance with the cross cut tape test method described in Japanese Industrial Standard K5400.

(Water Resistance Test) A sample of the polymer resin laminate was immersed in boiling water (pure water) for 30 minutes, then dried naturally in a room, visually observed for deterioration of the appearance of the laminate, and further subjected to the method described above. Was checked for the deterioration of the adhesion between the respective layers.

(Light fastness test) I-Super UV tester SUV-F11 manufactured by Iwasaki Electric Co., Ltd. 295-450
Irradiation is performed for 150 hours at an intensity of 100 mW / cm ² in the ultraviolet / visible region of nm. The light transmission spectrum of the sample was measured before and after the light irradiation, and the Japanese Industrial Standard Z of the transmitted light was measured.
The degree of coloring of the sample was evaluated by comparing the increase in the chromaticness index b ^* value of the L ^* a ^* b ^* color system defined in No. 8729, that is, the value of the color difference Δb ^* .

The transmission spectrum was measured in a spectrophotometer U3500 manufactured by Hitachi in an integrating sphere measurement mode at an incident angle of 0 °. The b ^* value was calculated using standard light C specified in Japanese Industrial Standard Z8720. Adopted and used twice viewing conditions.

The (single) light resistance of the actinic ray-curable layer was evaluated by coating the above-mentioned precursor solution P for forming a primer layer on a quartz plate having a thickness of 2 mm, followed by drying at 130 ° C. for 10 minutes. A sample obtained by laminating a 1 μm-thick primer layer and then laminating an actinic ray-curable layer to a thickness of 7 μm is used.

Example 1 As a polymer resin substrate, a polycarbonate resin synthesized from bisphenol A and diphenyl carbonate was 1 mm thick, 350 mm long and 350 mm wide.
mm × 250 mm molded plate (“PANLITE P” manufactured by Teijin Chemicals Limited)
C-1151 "was used.

The substrate was coated with the following precursor for forming an actinic ray-curable layer using a bar coater.
After drying at a temperature of 1 ° C. for 1 minute, ultraviolet rays having an integrated light amount of 1.2 J / cm ² were irradiated from a high-pressure mercury lamp of 160 W / cm to form an active light-cured layer having a thickness of 40 μm.

The precursors for forming the actinic ray-curable layer were 90 parts by weight of dicyclopentanyl diacrylate (trade name “Light Acrylic DCP-A” manufactured by Kyoeisha Chemical) and dipentaerythritol hexaacrylate (Kyoeisha Chemical Co., Ltd.). Name "Light acrylate DPE-6E")
10 parts by weight, 7 parts by weight of a photopolymerization initiator (“Irgacure 184” manufactured by Ciba Specialty Chemicals) and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5 as an ultraviolet absorber -[(Hexyl) oxy]-
1.7 parts by weight of phenol (trade name “Tinuvin 1577FF” manufactured by Ciba Specialty Chemicals) and a leveling agent (“SH28PA” manufactured by Dow Silicone Toray)
0.05 parts by weight and 80 parts by weight of normal propyl alcohol were mixed and used. The addition amount of the ultraviolet absorber in the nonvolatile component of the precursor of the actinic ray-curable layer was about 1.5.
%, And the product of the thickness and the thickness (μm) of the actinic ray-curable layer was about 60% by weight · μm. 300-350nm
Was 99% or more.

Incidentally, the pencil hardness of this actinic ray cured layer is 3H.
The softening temperature was 200 ° C. or higher, and the water absorption was 0.7%. As for light fastness, Δb ^* value was about 0.3, and there was almost no discoloration.

Next, a polycarbonate molded plate on which the actinic ray-curable layer was laminated was cut into a size of 10 cm square.
After a heat treatment at 140 ° C. for 1 hour, the substrate was set in a vacuum chamber of a vacuum evaporation apparatus and evacuated for 3 hours. After reaching a degree of vacuum of 2 × 10 ⁻³ Pa, electron beam evaporation was performed. The molten mass of silicon oxide filled in the crucible was sublimated by a method (EB evaporation method), and a 3.2 μm-thick silicon oxide layer was laminated on the cured layer of dicyclopentanyl diacrylate.

At this time, the distance between the crucible and the sample is about 60
cm, and a movable shutter was arranged between the crucible and the sample, and the film was formed by opening the shutter only during vapor deposition on the sample.

The result of measurement of the silicon oxide layer formed by vacuum deposition by nanoindentation shows that the maximum displacement is 42 n
m, Young's modulus is 42 GPa, plastic deformation hardness is 8.2 GP
a.

The appearance of this polymer resin laminate was very good, the total light transmittance was 91.1%, the haze was 0.9%,
Pencil hardness is H, haze rise due to Taber abrasion is 1.4
% And adhesion were 100/100. No change in appearance or deterioration in adhesion due to the water resistance test was observed. Further, the light fastness was very good with a Δb ^* value of 0.8 and a small degree of discoloration.

[Example 2] A two-layer hard coat layer in which a silicon oxide layer was further laminated by a sputtering method on the silicon oxide layer formed by vacuum deposition of the polymer resin laminate of Example 1 Was laminated on the actinic ray-curable layer.

That is, the same laminate as that prepared in Example 1 was set in a vacuum chamber, evacuated for 3 hours, and after reaching a degree of vacuum of 2 × 10 ⁻³ Pa, A
A mixed gas of r / O ₂ = 95: 5 was introduced, and the atmospheric pressure was set to 0.27 Pa.

As a sputtering target, a target of silicon oxide (100%) was used, and the input power density was 1 W / cm ² by RF magnetron sputtering.
Under the conditions described above, a silicon oxide layer having a thickness of 0.18 μm was formed.

The measurement results of the two hard coat layers by nanoindentation show that the maximum displacement is 24
nm, Young's modulus is 134 GPa, plastic deformation hardness is 44 G
Pa.

The appearance of this hard coat laminate was very good, with a total light transmittance of 90.8% and a haze of 0.9.
%, The pencil hardness was H, the haze increase due to Taber abrasion was 0.8%, and the adhesion was 100/100. No change in appearance or deterioration in adhesion due to the water resistance test was observed. Further, the light fastness was very good with a Δb ^* value of 0.8 and a small degree of discoloration.

Example 3 The following precursor materials were coated on the polymer resin substrate used in Example 1 with a bar coater, dried at 70 ° C. for 1 minute, and then irradiated with an electron beam irradiator TYPE manufactured by ESI: CB250 / 15/180
L, acceleration voltage 150KV, irradiation dose 300KGY
After irradiating with an electron beam under the conditions of m / min, an actinic ray-cured layer having a thickness of 30 μm was laminated, followed by heat treatment at 140 ° C. for 1 hour, and then 0.2 J / cm ^Two
, And a polymer resin laminate was formed in exactly the same manner as in Example 1 except that the vacuum discharge was performed in the same manner as in Example 1.

As a precursor material for forming an actinic ray-curable layer, 100 parts by weight of dicyclopentanyl dimethacrylate (trade name “DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.) and 2- (4,6-diphenyl) as an ultraviolet absorber were used. 2.3 parts by weight of -1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (trade name “Tinuvin 1577FF” manufactured by Ciba Specialty Chemicals) and a leveling agent (Dow Silicone Toray) 0.05 parts by weight of "SH28PA" and 80 parts by weight of normal propyl alcohol were mixed.

The addition amount of the ultraviolet absorber in the nonvolatile component of the precursor of the actinic ray-curable layer was about 2.2% by weight.
The product of the actinic ray curable layer and the film thickness (μm) is about 66% by weight.
μm. The absorptance in the wavelength region of 300 to 350 nm was 99% or more.

Incidentally, the pencil hardness of this actinic ray cured layer is 5H.
The softening temperature was 200 ° C. or higher, and the water absorption was 0.5%. As for light resistance, Δb ^* value was about 0.2, and there was almost no discoloration.

The appearance of the polymer resin laminate thus obtained was very good, the total light transmittance was 90.8%, the haze was 1.0%, the pencil hardness was 2H, and the haze increase due to Taber abrasion was 1%. 0.9% and adhesion was 100/100. No change in appearance or deterioration in adhesion due to the water resistance test was observed. Further, the light fastness was very good with a Δb ^* value of 0.9 and a small degree of discoloration.

Example 4 A polymer having a thickness of 5 μm was laminated as the actinic ray-curable layer using the following materials, and the thickness of the deposited layer was changed to 2 μm. A resin laminate was prepared.

As the precursor for forming the actinic ray-curable layer,
100 parts by weight of dipentaerythritol hexaacrylate (trade name “DPE-6A” manufactured by Kyoeisha Chemical), 3 parts by weight of a photopolymerization initiator (“IRGACURE 184” manufactured by Ciba Specialty Chemicals), and a leveling agent (“SH28PA” manufactured by Dow Silicone Toray Silicone) 0.05 parts by weight and 80 parts by weight of normal propyl alcohol were mixed, and no ultraviolet absorber was added.

Incidentally, the pencil hardness of this actinic ray cured layer is 9H.
The softening temperature is 200 ° C. or higher, the water absorption is 1.3%,
The light fastness was Δb ^* value of about 0.6.

The appearance of the polymer resin laminate thus obtained was very good, adhesion was 100/100, total light transmittance was 91.1%, haze was 0.7%, pencil hardness was F, The haze increase due to Taber abrasion was 4.9%.

Comparative Example 1 A polymer resin laminate was prepared in the same manner as in Example 1 except that the vapor-deposited layer was directly laminated on the polycarbonate plate without laminating the actinic ray-curable layer. .

Incidentally, the measurement result of the silicon oxide layer formed by vacuum deposition by nanoindentation shows that the maximum displacement is 4%.
6 nm, Young's modulus 39 GPa, plastic deformation hardness 7.6
In GPa, there was almost no difference from the deposited film of Example 1.

[0167] Appearance of the polymer resin laminate, the light transmittance was good adhesiveness 100/100, haze increases due to Taber abrasion 20.8%, light resistance by △ b ^* value 32. 9. In the water resistance test, the deposited layer is completely peeled off.
The performance was remarkably inferior to that of Example 1.

Comparative Example 2 A polymer was obtained in the same manner as in Example 2 except that the active light-cured layer was not laminated on the polycarbonate plate, and the vapor deposition layer and the sputtered layer were laminated in this order. A resin laminate was prepared.

The appearance of the polymer resin laminate was good and the adhesion was 100/100, but the pencil hardness was HB, the haze increase due to Taber abrasion was 15.8%, and the light resistance was Δb.
^* Value was 33.2, which was significantly inferior to Example 2.

Comparative Example 3 A polymer resin laminate was prepared in the same manner as in Example 2 except that the active light-cured layer and the vapor-deposited layer were not laminated and only the sputtered layer was directly laminated. Created.

Although the appearance of this polymer resin laminate was good, the adhesiveness was 0/100, the pencil hardness was 2B, the haze increase due to Taber abrasion was 35.7%, and the light resistance was Δb ^* value of 34. .4, which was significantly inferior to Example 2.

Comparative Example 4 The same procedure as in Example 2 was repeated except that the active light-cured layer and the sputtered layer were laminated on the substrate in this order without depositing the vapor-deposited layer. Created body.

The appearance of this polymer resin laminate was good, the adhesion was 100/100, the pencil hardness was H, and the light resistance was Δb ^*.
Although the value was 1.0, the haze increase due to Taber abrasion was 25.6%, which was significantly inferior to Example 2.

[Comparative Example 5] In Example 1, the following materials were used as the precursor of the actinic ray-curable layer, and the film thickness was 30 μm.
A polymer resin laminate was produced in exactly the same manner as in Example 1 except that m layers were laminated.

That is, 100 parts by weight of triethylene glycol diacrylate (trade name “Light Acrylate 3EG-A” manufactured by Kyoeisha Chemical) and 7 parts by weight of a photopolymerization initiator (“Irgacure 184” manufactured by Ciba Specialty Chemicals) were used as precursor materials. , 2- (4,
6-diphenyl-1,3,5-triazin-2-yl)
-5-[(hexyl) oxy] -phenol (trade name “Tinuvin 1577F, manufactured by Ciba Specialty Chemicals)
F "), and 2.5 parts by weight of a leveling agent (" SH28PA "manufactured by Toray Dow Silicone) was mixed with 80 parts by weight of normal propyl alcohol.

The amount of the ultraviolet absorber added in the nonvolatile component of the precursor of the actinic ray curable layer was about 2.3% by weight, and the product of the actinic ray curable layer and the film thickness (μm) was about 69%. % By weight · μm. The absorptance in the wavelength region of 300 to 350 nm was 99% or more. The actinic ray-cured layer had a pencil hardness of 2B, a softening temperature of about 90 ° C., a water absorption of 2.8%, and a light resistance of Δb ^* of about 0.8.

The measurement result of the silicon oxide layer formed by vacuum deposition by nanoindentation shows that the maximum displacement is 4%.
8 nm, Young's modulus 37 GPa, plastic deformation hardness 7.3
In GPa, there was almost no difference from the vapor deposition layer of Example 1.

The appearance of the polymer resin laminate thus produced was good, the adhesion was 100/100, and the light resistance was Δ.
The b ^* value was about 1.5, but the pencil hardness was B, the haze increase due to Taber abrasion was 22.3%, and the adhesion between the actinic ray-cured layer and the deposited layer deteriorated in the water resistance test. In addition, the performance was remarkably inferior to that of Example 1 such that defects such as spontaneous peeling of the deposited film were observed.

[Comparative Example 6] In Example 1, the following materials were used as precursors for the actinic ray-curable layer, and the film thickness was 30 μm.
A polymer resin laminate was produced in exactly the same manner as in Example 1 except that m layers were laminated.

That is, as a precursor, 80 parts by weight of bisphenol A ethylene oxide-modified diacrylate (trade name “Light Acrylate BP-4EA” manufactured by Kyoeisha Chemical Co., Ltd.) and N-vinyl-2-pyrrolidone (“Aronix M150” manufactured by Toagosei Chemicals Co., Ltd.) ) 20 parts by weight and a photopolymerization initiator (“Irgacure 1” manufactured by Ciba Specialty Chemicals)
84 ") 7 parts by weight and 2- (4,6
-Diphenyl-1,3,5-triazin-2-yl)-
5-[(hexyl) oxy] -phenol (trade name “Tinuvin 1577F manufactured by Ciba Specialty Chemicals)
F "), and 2.5 parts by weight of a leveling agent (" SH28PA "manufactured by Toray Dow Silicone) was mixed with 80 parts by weight of normal propyl alcohol.

The amount of the ultraviolet absorber added in the nonvolatile component of the precursor of the actinic ray-curable layer was about 2.3% by weight, and the product of the actinic ray-curable layer and the film thickness (μm) was about 69%. % By weight · μm. The absorptance in the wavelength region of 300 to 350 nm was 99% or more.

Further, the pencil hardness of this actinic ray cured layer is 2
B, the softening temperature was about 80 ° C., the water absorption was 1.7%, and the light resistance was Δb ^* value of about 2.3.

The result of measurement of the silicon oxide layer formed by vacuum deposition by nanoindentation showed that the maximum displacement was 4%.
5 nm, Young's modulus 40 GPa, plastic deformation hardness 7.8
In GPa, there was almost no difference from the vapor deposition layer of Example 1.

Although the appearance of the polymer resin laminate thus produced was good and the adhesion was 100/100,
Pencil hardness is B, haze rise due to Taber abrasion is 2
1.4%, and the light resistance was Δb ^* value of about 5.3, and the discoloration of the laminate was clearly confirmed with the naked eye.

Comparative Example 7 The procedure of Example 4 was repeated, except that the thickness of the deposited layer was changed to 1 μm.
A polymer resin laminate was prepared.

The appearance of the polymer resin laminate was good, the adhesion was 100/100, and the pencil hardness was F. However, the haze increase due to Taber abrasion was 13.5%, which was inferior to that of Example 4. .

[0187]

According to the present invention, a polymer having excellent abrasion resistance, surface hardness, light resistance and water resistance can be obtained by applying the present invention to a resin molded product having low hardness and abrasion resistance such as polycarbonate. A resin laminate can be obtained, and can be used for window materials such as automobiles and building materials, structural materials requiring transparency, and other wide-ranging applications.

[Brief description of the drawings]

FIG. 1 shows the abrasion resistance of a polymer resin laminate of the present invention and a hard coat layer (a silicon oxide layer formed by a vacuum deposition method).
6 is an example of actual measurement data showing a relationship with a film thickness.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Rionao Iwai 2-1 Hinode-cho, Iwakuni-shi, Yamaguchi Prefecture Teijin Co., Ltd. Inside the Iwakuni Research Center (72) Inventor Satoshi Omori 2-1 Hinode-cho, Iwakuni-shi, Yamaguchi Prefecture Teijin Inside the Iwakuni Research Center Co., Ltd. (72) Inventor Hiromasa Minematsu 2-1 Hinodecho, Iwakuni-shi, Yamaguchi Prefecture Teijin Co., Ltd. F-term in the Iwakuni Research Center 4F100 AA20C AA20D AA20E AH07B AH07H AK01A AK25B AK25E AK45A AR00B AT00A BA03 BA04 BA03 BA04 BA06 BA07 BA10A BA10C BA13 CA07B CC00C CC00E EH462 EH66C EH66D EH66E EH662 EJ52B EJ52E EJ522 EJ542 GB07 GB32 JA20A JA20B JA20C JA20D JA20E JB07 JB14B JB14E JD14B JD15B JD15E JK01C JK07C JK07E JK09 JK12 JK12B JK12C JK12E JK14 JN01 JN30 YY00 YY00A YY00B YY00C YY00D YY00E

Claims (17)

[Claims] 1. An active light-cured layer having a thickness of 2 to 50 μm and having a pencil hardness of F or more by itself on at least one surface of a polymer resin substrate, and a vacuum film forming process. When the thickness is 1.5 to 10 μm and the surface of the layer is subjected to nanoindentation measurement under the condition of a maximum load of 100 μN, the maximum displacement is 120 nm or less, the Young's modulus is 15 GPa or more, and the plastic deformation hardness is 3 GPa or more. A polymer resin laminate obtained by laminating a hard coat layer in this order. 2. The polymer resin laminate according to claim 1, wherein the vacuum film forming process is a vacuum deposition method. 3. The hard coat layer is a two-layer structure in which a layer formed by a vacuum evaporation method and a layer having a thickness of 0.02 to 0.5 μm formed by a sputtering method are laminated in this order from the substrate side. The polymer resin laminate according to claim 1, wherein the polymer resin laminate is a layer comprising: 4. The hard coat layer is a layer containing at least 50% by weight of silicon oxide or at least 50% by weight of silicon oxide. The polymer resin laminate according to any one of claims 1 to 3, wherein: 5. The actinic ray-curable layer comprises one or more (meth) acrylate components having two or more (meth) acryloyl groups in a molecule or a unit repeating structure, and 50% by weight of a non-volatile component. %. The polymer resin laminate according to any one of claims 1 to 4, wherein the precursor material is a layer obtained by irradiating an actinic ray to a precursor material containing at least 10% of the precursor material. 6. The polymer resin laminate according to claim 1, wherein the actinic ray-curable layer is a layer having a water absorption of 2% or less. 7. The actinic ray-curable layer has a wavelength of 295 to 450 nm and an illuminance of 100 mW /
An increase in the chromaticity index b ^* value of the L ^* a ^* b ^* color system defined in Japanese Industrial Standard Z8729 of the transmitted light of the layer before and after irradiation with light of 100 cm ² for 100 hours, that is, the value of the color difference ｂb ^* The polymer resin laminate according to any one of claims 1 to 6, wherein the active light-cured layer is at least 2 or less. 8. A layer obtained by curing a precursor material containing at least 50% by weight of a nonvolatile component of dicyclopentanyl diacrylate and / or dicyclopentanyl dimethacrylate as an actinic ray-curable layer. The polymer resin laminate according to claim 1, wherein: 9. The product of the amount (% by weight) of the ultraviolet absorber added to the nonvolatile component of the precursor of the actinic ray-curable layer and the thickness (μm) of the actinic ray-curable layer is 30 to 300% by weight · μ.
The polymer resin laminate according to any one of claims 1 to 8, wherein m is in the range of m. 10. The actinic ray-curable layer has a thickness of 300 to 350 nm.
The polymer resin laminate according to any one of claims 1 to 9, wherein the light absorptance in the wavelength region of (a) is 99% or more. 11. An ultraviolet absorber to be mixed with the actinic ray-curable layer, as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy]-
The polymer resin laminate according to any one of claims 1 to 10, wherein phenol is used as a main component of the ultraviolet absorber. 12. The polymer resin laminate according to claim 1, wherein the thickness of the polymer resin substrate is 0.2 mm or more. 13. The polymer resin laminate according to claim 1, wherein the polymer resin substrate is a molded polycarbonate substrate. 14. The polymer resin laminate according to claim 1, wherein the haze of the polymer resin laminate is 5% or less. 15. A polymer resin substrate coated with a precursor of an actinic ray curable layer is heated to a temperature of 50 to 130 ° C., and then irradiated with actinic light to form an actinic ray curable layer on the polymer substrate. The method for producing a polymer resin laminate according to any one of claims 1 to 14, wherein: 16. A method of laminating a hard coat layer on an actinic ray curable layer after subjecting a polymer resin substrate having an actinic ray curable layer formed thereon to a heat treatment at a temperature near the glass transition temperature of the polymer substrate. A method for producing a polymer resin laminate according to any one of claims 1 to 15. 17. An automotive window material comprising the polymer resin laminate according to claim 1. Description: