JP2001322197A - Polymer resin laminate, manufacturing method therefor and molding made up of polymer resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer resin laminate with high hardness, formed using a resin molding with a comparatively lower hardness such as a polycarbonate. SOLUTION: This polymer resin laminate is composed of an activated light rays-cured layer (A) having a thickness of 50-300 μm and a pencil hardness of 3 H or more and a hard coat layer (B) which is 1-20 μm thick and shows a haze increase of 10% or less by a taper abrasion test at a 4.9 N load and 1,000 cycles and a pencil hardness of 4 H or more, laminated in that order, on a polymer resin substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate of a molded article of a polymer resin having an excellent surface hardness, and more particularly to a laminate of a polycarbonate molded article having an excellent surface hardness. The present invention relates to window materials and structural materials of various kinds of automobiles and buildings used.

However, the polymer resin molded article of the present invention can sufficiently be used in addition to the above-mentioned applications, and for example, various kinds of liquid crystal display (LCD), plasma display, electroluminescence display, CRT, etc. It is also suitable as a film for protecting the surface of a display device, or as a hard coat film used in applications such as a film with a transparent electrode in a transparent tablet used in various portable information terminals and touch panel input devices, and a film for preventing scattering of a glass plate. Yes, including polycarbonate film, polyarylate film, polyethylene terephthalate film and polyethylene naphthalate film, triacetyl cellulose film and various olefin-based films and various olefin-based films and the like are preferably used as a hard coat film. Door can be.

[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 hard coat is applied to the polycarbonate surface (for example, JP-A-48-81928 and JP-A-52-81928).
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.

In general, the hardness of such a hard coat layer is often very high. For example, when a pencil hardness is measured by laminating a hard coat layer with a thickness of about 5 μm on a quartz plate having a thickness of 2 mm, the hardness is 9H. (Even a 9H pencil does not scratch).

However, when these hard coat layers are laminated with a thickness of about 5 μm on a polycarbonate molded product, the surface hardness of the molded product is not sufficiently high.

That is, when the measurement is carried out in accordance with the pencil hardness test described in Japanese Industrial Standard K5400, the pencil hardness of the polycarbonate molded product itself is about 2B to B, Even when a hard coat layer having a pencil hardness of 9H is laminated, the pencil hardness does not generally show a sufficiently high value of about F to H.

Also, when the polymer resin substrate has a slightly higher pencil hardness, for example, a molded product of polyethylene terephthalate or polyethylene naphthalate (both having a pencil hardness of about H to 2H), the pencil hardness after laminating such a hard coat layer is also considered. Is often insufficient at about 3H.

[0010] Such insufficient surface hardness is a major problem in using these polymer resin / hard coat laminates in a wider field.
The present invention is intended to solve this problem.

[0011]

That is, the present invention is as follows.

1. On the polymer resin substrate, the thickness is 50 ~
An actinic ray-curable layer (A) having a pencil hardness of 3H or more having a thickness of 300 µm, a load of 4.9 N having a thickness of 1 to 20 µm, and
A polymer resin laminate obtained by laminating a hard coat layer (B) having a haze increase of 10% or less in a Taber abrasion test of 000 cycles and a pencil hardness of 4H or more in this order.

2. When the actinic ray-curable layer (A) contains dicyclopentanyl diacrylate and / or dicyclopentanyl dimethacrylate in an amount of 50% by weight of the total nonvolatile components
2. The polymer resin laminate according to the above item 1, wherein the polymer resin laminate is a layer formed by curing the above-mentioned precursor material.

3. The actinic ray-curable layer (A) cures a precursor material in which a polyfunctional (meth) acrylate having three or more acryloyl groups and / or methacryloyl groups in a molecule is mixed at a ratio of 50% by weight or less of the entire nonvolatile component. 3. The polymer resin laminate according to the above item 2, which is a layer made of

4. 300 to 3 of actinic ray-curable layer (A)
4. The polymer laminate according to any one of the above items 1 to 3, wherein the light absorption in a wavelength region of 50 nm is 99% or more.

5. The product of the addition amount (% by weight) of the ultraviolet absorber in the non-volatile component of the precursor of the actinic ray curable layer (A) and the thickness (μm) of the actinic ray curable layer (A) is 30 to 30.
(1) to (4), wherein the content is in the range of 0% by weight · μm
The polymer laminate according to any one of the above.

6. As an ultraviolet absorber mixed with the actinic ray-curable layer (A), 2- (4,6-diphenyl-1,2
3,5-triazin-2-yl) -5-[(hexyl)
6. The polymer laminate according to any one of the above items 1 to 5, mainly comprising [oxy] -phenol.

[7] The hard coat layer (B) is composed of a trifunctional silicon alkoxide having three methoxy groups and / or ethoxy groups bonded to one silicon atom.
(1) a layer containing 0% by weight or more.
7. The polymer resin laminate according to any one of items 6 to 6.

8. (1) The hard coat layer (B) is a layer containing 50% by weight or more of a polyfunctional (meth) acrylate polymer having three or more acryloyl groups and / or methacryloyl groups in a molecule. 8. The polymer resin laminate according to any one of items 7 to 7.

9. The polymer resin laminate according to any one of the above 1 to 8, wherein the hard coat layer (B) is a layer formed by a vacuum film forming process and having a thickness of 1.5 to 10 µm.

10. (1) The hard coat layer (B) is a layer formed by a vacuum evaporation method.
9. The polymer resin laminate according to any one of Items 1 to 9.

11. A two-layer structure in which a hard coat layer (B) is formed by laminating 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 in this order from the substrate side. The polymer resin laminate according to any one of the above 1 to 10, which is a hard coat layer comprising:

12. The hard coat layer described above, wherein 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. ~ 1
1. The polymer resin laminate of 1.

13. 13. The polymer resin laminate according to any one of the above 1 to 12, wherein the polymer resin substrate is a molded substrate of polycarbonate.

14. The polymer resin laminate according to any one of the above 1 to 13, wherein the haze value of the laminate is 5% or less.

15. The method according to the above, wherein after coating the precursor of the actinic ray curable layer on the polymer resin substrate, the actinic ray curable layer (A) is formed by curing the coating film of the precursor material by irradiation with an electron beam or ultraviolet rays. The method for producing a polymer resin laminate of the above.

16. 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., irradiating with actinic light to form the actinic ray curable layer (A) on the polymer substrate. 15. The method for producing a polymer resin laminate according to the above 15, wherein

17. A molded product obtained by laminating the polymer resin laminate according to any one of claims 1 to 16 on a resin with the upper surface of the hard coat layer (B) facing outward.

18. A molded article comprising the polymer resin laminate of any one of the above 1 to 17.

19. 19. The molded article according to the above item 17 or 18, wherein the molded article is an automobile window or a window for building materials.

Here, that the active cured layer (A) and the hard coat layer (B) are laminated on the polymer resin substrate in this order means that the polymer resin substrate, the active light cured layer and the hard coat layer are arranged in this order. The upper surface of the hard coat layer (B) means that the surface is not opposed to the actinic ray curable layer (A).

The above-mentioned “in order of the polymer resin substrate, the actinic ray cured layer, and the hard coat layer” means that another layer, for example, between the polymer resin substrate, the actinic ray cured layer, and the hard coat layer, for example, This includes the case where a primer layer is included.

The pencil hardness of the actinic ray-curable layer (A) and the hard coat layer (B) was determined by setting the actinic ray-curable layer or the hard coat layer on a quartz plate having a thickness of 2 mm.
~ 300μm, after lamination and curing with a film thickness of 1-20μm,
It was measured on the surface of those layers. There is no difference in the data obtained within the above film thickness range.

The load of the hard coat layer (B) is 4.
9N, Taber abrasion of 1000 cycles, the hard coat layer is 1 to 1 mm thick on a polycarbonate plate (for example, "Panlite PC-1151" manufactured by Teijin Chemicals Ltd.)
After laminating to a thickness of 20 μm, the surface of this layer was measured. There is no difference in the data obtained within the above film thickness range.

In performing these measurements, the distance between the actinic ray-curable layer and the quartz plate, the distance between the hard coat layer and the quartz plate,
It is preferable that the adhesion between the hard coat layer and the polycarbonate plate is good.
It is preferably 100/100 in the cross-cut tape test described in 5400.

For this reason, it is preferable that the primer layer is provided between the actinic ray cured layer and the quartz plate, between the hard coat layer and the quartz plate, and between the hard coat layer and the polycarbonate plate. 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 3 μm from the viewpoint of preventing the influence of the pencil hardness on the measurement result.

The "visible wavelength range" is 400 to 750.
It means the wavelength range of nm.

The inventors of the present application have shown that 50
An actinic ray-curable layer having a thickness of not less than μm and a pencil hardness of not less than 3H, particularly a dicyclopentanyl diacrylate (hereinafter referred to as DCPA) and / or dicyclopentanyl dimethacrylate (hereinafter referred to as DCP) as a main component It has been found that by laminating a hard coat layer via an actinic ray curable layer, a high value of 4H or more can be obtained for the pencil hardness of the laminate after laminating the hard coat layer.

The inventors of the present application conducted computer simulation (finite element method analysis) to simulate the case where the surface of such a laminate was pushed in with a pencil tip in order to gain knowledge of the above reasons.

As a result, when a layer having high rigidity (hereinafter, referred to as a rigid layer) is laminated on a polymer resin substrate, the surface hardness of the laminate in which the rigid layers are laminated changes greatly depending on the thickness of the rigid layer. I understand.

In the simulation, such a laminate is considered as a cylinder having a radius of 2 mm and a thickness of 2 mm in which an underlayer (corresponding to a portion of a polymer resin substrate) and a rigid layer (corresponding to an actinic ray cured layer) are laminated. In the center of the circle on the top of the cylinder,
Cylindrical indenter with a load of 9.8 N (circle area 0.1 m)
m ² . (This is almost equal to the contact area when pushing in the pencil.)
, And the conditions such as pushing in the surface of the laminate were set.

The elastic modulus of the underlayer is 2.3 GPa, the Poisson's ratio is 0.3 (this value is a general value of a molded product of polycarbonate), and the elastic modulus of the rigid layer is 6.9 and 23 G.
FIG. 1 summarizes changes in the depth of the indentation depth on the surface of the laminate when Pa and the Poisson's ratio are 0.3 and the thickness of the rigid layer is varied.

From the results, it can be seen that as the thickness of the rigid layer increases, the indentation depth on the surface of the laminate gradually decreases. This is probably due to the improvement in pencil hardness in the actual experimental results. It is thought to correspond.

That is, the pencil has a core grade (HB, F, H
Etc.), and the pencil hardness test is considered to be a test in which the surface of the sample is pressed with a pressure substantially equal to the brittle fracture strength. Generally, a sample undergoes plastic deformation when subjected to indentation deformation of a certain size or more, and when the size of the plastic deformation becomes a size that can be confirmed with the naked eye, it is recognized that a scratch has occurred.

By keeping in mind that there is a threshold value of the indentation pressure at which the flaw is generated, the decrease in the indentation depth observed in the above simulation result is due to the indentation pressure required for the flaw to be generated. It is considered that the increase, that is, the occurrence of scratches, requires the indentation with a pencil having a higher brittle fracture strength, that is, a correspondence with the improvement of the pencil hardness.

The actual experimental results agree well with this simulation, and in order to obtain a sufficient effect of improving pencil hardness, the actinic ray-curable layer needs to have a certain thickness or more, and at least 50 μm or more. It turned out to be. More preferably, it is 70 μm or more. In addition, 3
A thickness exceeding 00 μm is not preferred because the adhesion of the layer is reduced and the economy is often inferior.

It is important that the actinic ray-curable layer itself is a layer having a pencil hardness of at least 3H by itself and, when formed in the above-mentioned thickness range, does not cause cracks or decrease in adhesion. It is preferable that the cured layer is made of a material having a small curing shrinkage.

As the material having a small curing shrinkage and a high hardness after curing, the above-mentioned DCPA and DCP are particularly preferred. These layers are 50 μm thick on a polymer resin substrate.
Even when it is formed in the above thickness, cracks and poor adhesion do not occur, and a pencil hardness of 3H or more can be obtained.

Further, using a polymer resin film as a substrate,
The laminate in which the cured layers of PA and / or DCP are laminated has a feature that the flexibility of the laminate is excellent. That is, when the laminate is bent (outwardly bent) with the hardened layer on the outside, the hardened layer can be bent with a smaller radius of curvature without causing cracks in the hardened layer. While the polymer resin film substrate is running continuously, the cured layer is formed by coating,
It is very useful when winding in a roll.

When a material containing DCPA and / or DCP as a main component and other components (hereinafter also referred to as subcomponents) is used, from the viewpoint of maintaining the above characteristics, at least the entire non-volatile component of the material is used. 50% by weight or more, more preferably 70% by weight or more of DCPA and / or D
Preferably, the CP occupies.

As subcomponents, various (meth) acrylates other than DCPA and DCP, compounds having a vinyl group and an allyl group, various alkoxide components including silicon alkoxide, and an average particle diameter (diameter) of 3 to 30 nm Ultra fine particles, curing agent or curing catalyst such as photopolymerization initiator, photopolymerization initiation auxiliary agent (sensitizer), leveling agent, light absorber, light stabilizer (antioxidant), defoamer, thickener Etc. are mixed as necessary.

These subcomponents impart various functions such as a further increase in hardness of the actinic ray-curable layer, an improvement in adhesion to a substrate and a hard coat layer, an improvement in weather resistance, and an improvement in surface properties. Mixed for purpose.

When DCPA and (meth) acrylates other than DCP are mixed as sub-components, these components are used in an amount of 50% by weight or less based on the total nonvolatile components of the actinic ray-curable layer (A).
More preferably, the ratio is 30% by weight or less,
It is preferable to mix (precursor materials).

If the content exceeds 50% by weight, one of the characteristics of the cured layer formed of the main component DCPA and / or DCP, which is one of the characteristics of low curing shrinkage and high hardness, is often lost.

There is no particular limitation on the (meth) acrylate which can be mixed as the above-mentioned auxiliary component. Examples thereof include polyol poly (meth) acrylate, modified polyol (meth) acrylate, polyester acrylate, urethane acrylate, epoxy acrylate, and melamine acrylate. And poly (meth) acrylates and mono (meth) acrylates.

Specifically, for example, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolpropane PO-modified triacrylate, trimethylolpropane EO-modified triacrylate Acrylate, ethoxylated pentaerythritol triacrylate, propoxylated pentaerythritol triacrylate, dimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyfunctional acrylate containing isocyanuric ring (functional group About 4 to 15), acryloyl morpholine, isobornyl ( Data) acrylate can be preferably used.

Of these, polyfunctional (meth) acrylates having at least three acryloyl groups and / or methacryloyl groups in the molecule, when mixed in an appropriate ratio, further increase the hardness of the actinic ray-curable layer. Perform the function.

The isobornyl (meth) exemplified above
Acrylates are difficult to mix at a high rate because they have poor adhesion to the polymer resin substrate, but have the characteristic of extremely low cure shrinkage, so they are mainly used to reduce the internal stress of the cured layer. For this purpose, an appropriate amount is preferably mixed as necessary.

The above-mentioned compound having a vinyl group or an allyl group is preferably used particularly when the actinic ray-curable layer is cured by electron beam irradiation. Preferred examples thereof include, for example, diethylene glycol allyl carbonate.

When various alkoxide components (silicon, zirconium, titanium, boron, etc.) are mixed as subcomponents, alkoxides having an acryloyl group, a methacryloyl group, an allyl group or a vinyl group bonded in the molecule are particularly preferable. It is preferably used. Examples of these include vinyltrimethoxysilane, vinyltriethoxysilane, γ-
Preferred examples include methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, and the like.

For the purpose of further increasing the hardness of the layer, it is also preferable to mix ultrafine particles having an average particle diameter of 3 to 30 nm as subcomponents. Such ultrafine particles include, for example, silicon oxide, aluminum oxide, aluminum chloride,
Ultrafine particles made of inorganic oxides such as titanium oxide, zinc oxide, zirconium oxide, cerium oxide, and tin oxide, and ultrafine particles made of organic crosslinked fine particles obtained by crosslinking methyl methacrylate or divinylbenzene with an acid or imide are preferable.

The actinic ray-curable layer is prepared by diluting the above-mentioned material with various solvents as required, coating the material on a substrate, and irradiating actinic rays such as electron beams and ultraviolet rays (which may contain visible light). By doing so, the material can be cured and formed.

Here, 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. This is an effective curing method when the thickness of the actinic ray curable layer is as thick as 50 μm or more as in the present invention.

Further, since the electron beam curing method does not use the ultraviolet absorption wavelength region, 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. This is a particularly effective curing method.

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

In any of the electron beam curing method and the ultraviolet curing method, the purpose is to suppress 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 entire 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.

When an ultraviolet absorber is added as an auxiliary component, an ultraviolet absorber having a large absorption in a wavelength region of at least 300 to 350 nm is preferably used, and among them, a benzotriazole skeleton, a triazine skeleton, etc. Compounds containing are particularly preferred.

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-based 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 containing a benzotriazole skeleton or a triazine skeleton with a compound containing 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 property) 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 film 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 absorbent 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 350-400 nm and / or 220-30.
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 initiator (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 such a photopolymerization initiation aid include 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 initiator is mixed at a ratio of 10 to 40% by weight based on the photopolymerization initiator.

These active light-cured layers are formed by applying (coating) the precursor material on a polymer resin substrate and then irradiating the applied film with active light.

Examples of the coating method include (doctor) knife coating, microgravure coating,
Direct gravure coating method, offset gravure method,
Methods such as a reverse gravure method, a reverse roll coating method, a (Meier) bar coating method, a die coating method, a spray coating method, and a dip coating method can be preferably applied.

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 to 130 before irradiation with actinic rays for the purpose
Preferably, the temperature is raised to ° C.

This effect of improving the adhesion is caused by the fact that the precursor material liquid partially penetrates into the inside of the polymer resin substrate by raising the temperature, thereby producing a so-called anchor effect. The state of the penetration of the precursor material into the inside of the substrate can be known by observing the cross section of the laminate using a scanning electron microscope (SEM).

If the substrate is kept at such a temperature for an excessively long time, the precursor liquid may permeate too much, and conversely, the curability of the layer may be reduced. Therefore, the time for holding the substrate at the above temperature is most preferably about 5 to 100 seconds.

As a method for forming the actinic ray-curable layer, a suitable shaping plate (including a film-shaped one) is irradiated with actinic light in a state in which the actinic ray-curable layer is in close contact with the coating film of the precursor of the actinic ray-curable layer. It is also preferable to use a method in which the surface shape of the shaped plate is transferred onto the actinic ray-cured layer by curing the shaped plate and then peeling the shaped plate from the layer.

Examples of the shaping plate include a polymer resin plate, a polymer resin film, a glass plate, a metal plate, and the like. It is preferably a shaped plate capable of peeling off or a shaped plate subjected to a surface treatment with a release agent or the like.

The advantage of this method is that the surface shape of the actinic ray-curable layer can be freely controlled by using shaped plates having different surface shapes. For example, a shaped plate having excellent surface smoothness is used. Thereby, an active light-cured layer having a smooth surface can be formed regardless of whether the surface smoothness of the polymer resin substrate is good or bad, and the effect of further improving the appearance of the laminate can be obtained.

By using this method, the hard coat layer is transferred onto the surface of the actinic ray curable layer simultaneously with the formation of the actinic ray curable layer having excellent surface smoothness (ie, the actinic ray curable layer is formed on the shaping plate). On the layer).

That is, a layer to be transferred, that is, a hard coat layer or a laminate of a primer and a hard coat layer, is laminated on the shaping plate in advance, and the shaping plate and the transferred layer are applied by a slight force. When the exfoliation plate is set to be releasable, the layer is cured by irradiating the shaped plate with an actinic ray in a state in which it is in close contact with the coating film of the precursor material in the same manner as described above, and then a transfer layer (hard coat layer) Or a laminate of a primer and a hard coat layer) can be laminated.

Now, the hard coat layer in the present invention is
With a pencil hardness of 4H or more, an increase in the haze value in a 1000-cycle Taber abrasion test of the hard coat layer using a Taber abrasion tester (wear wheel CS-10F, vertical load 4.9N) manufactured by Toyo Seiki Co., Ltd. , At least 10
%, Which is excellent in wear resistance.

As such a hard coat layer, for example, a layer containing 50% by weight or more of a hydrolysis-condensation product of a trifunctional silicon alkoxide in which three methoxy groups and / or ethoxy groups are bonded to one silicon atom, or a molecule containing A preferred example is a layer containing 50% by weight or more of a polyfunctional (meth) acrylate polymer having three or more acryloyl groups and / or methacryloyl groups therein.

The layer may contain not more than 50% by weight of ultrafine particles of various inorganic oxides, and various additives such as curing agents (polymerization initiators, polymerization catalysts) and leveling agents. May be contained.

The ultrafine particles made of an inorganic oxide include, for example, ultrafine particles having an average particle diameter of 3 to 30 nm made of silicon oxide, aluminum oxide, aluminum chloride, titanium oxide, zinc oxide, zirconium oxide, cerium oxide, tin oxide or the like. Is preferred.

It is to be noted that a hydrolysis condensate by a trifunctional silicon alkoxide in which three methoxy groups and / or ethoxy groups are bonded to one silicon atom, or a polycondensate having three or more acryloyl groups and / or methacryloyl groups in the molecule. If the polymer of the functional (meth) acrylate is not contained in the hard coat layer in an amount of 50% by weight or more, problems such as partial peeling and chalking are likely to occur. It is more preferably at least 60% by weight.

The layer may contain a hydrolysis condensate of tetrafunctional silicon alkoxide in which four methoxy groups and / or ethoxy groups are bonded to one silicon atom at a ratio of 25% by weight or less. Similarly, a hydrolysis condensate of an alkoxide other than silicon in a proportion of 25% by weight or less,
For example, it may contain a hydrolyzed condensate of a metal alkoxide such as aluminum, titanium, zirconium, and boron.

These trifunctional silicon alkoxides include:
For example, methyltrimethoxysilane, methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, N-β
(Aminoethyl) γ-aminopropyltrimethoxysilane, acryloylpropyltrimethoxysilane, methacryloylpropyltrimethoxysilane and the like,
Examples of the tetrafunctional silicon alkoxide include tetramethoxysilane and tetraethoxysilane.

Here, the hydrolytic condensate of silicon alkoxide refers to a mixture of silicon alkoxide, water, and an acid catalyst (mainly formic acid, acetic acid, hydrochloric acid, nitric acid, phosphoric acid, etc.) and stirring. As a result, a dealcoholation reaction takes place between the alkoxy group and water to produce a hydroxyl group (Si-OH), followed by a dehydration reaction between the hydroxyl groups or a dealcoholation reaction between the hydroxyl group and the alkoxy group. Condensate based on (Si-O-Si
Concatenation).

This condensate generally exists in a state of being dissolved in an alcoholic solvent generated by the above reaction. However, if the condensation reaction proceeds too much, gelation occurs and coating becomes impossible. Since these reaction rates greatly depend on the pH value and temperature of the solution, it is preferable to add a pH buffer (such as sodium acetate) to these solutions or store them in a refrigerated state.

After coating these solutions on a substrate,
The solvent component is volatilized and dried by natural drying (air drying) and / or heating in a coater drying oven, and thereafter, by heating to a high temperature in a drying oven, the condensation reaction remarkably progresses to form a hardened layer, that is, a hard coat layer. Form.

When these solutions or the surface of the substrate coated with these solutions are irradiated with ultraviolet rays in the wavelength range of 170 to 300 nm (especially 195 nm and 254 nm, which are the main emission wavelengths of low-pressure mercury lamps), condensation of alkoxides occurs. It is known that the reaction activity increases, and the present method is also preferably used in combination in the present invention.

However, when the method of irradiating the surface of the substrate coated with the solution with ultraviolet rays is used, the polymer resin molded product of the substrate may be deteriorated (yellowing, molecular weight decrease, etc.) by the ultraviolet rays in the above-mentioned wavelength region. Therefore, it is preferable to add an appropriate amount of an ultraviolet absorber that absorbs ultraviolet light in the above-mentioned wavelength region to the actinic ray-curable layer.

The hard coat layer is preferably exemplified by a layer containing a polyfunctional (meth) acrylate polymer having three or more acryloyl groups and / or methacryloyl groups in a molecule in an amount of 50% by weight or more.

Examples of these are, for example, trimethylolpropane triacrylate, trimethylolpropane ethylene oxide modified triacrylate, trimethylolpropane propylene oxide modified triacrylate, isocyanuric acid ethylene oxide modified triacrylate, pentaerythritol tetraacrylate, dipentaerythritol Examples include pentaacrylate and dipentaerythritol hexaacrylate.

The layer may contain a polyester-modified, urethane-modified, or epoxy-modified polyfunctional acrylate oligomer in a proportion of 50% by weight or less. These resins may be used in a single composition or in a mixture of several kinds.

The curing of these layers is promoted by irradiation of ultraviolet rays (which may include visible light) or an electron beam to form a cured product layer (hard coat layer).

As the hard coat layer, a layer formed by a vacuum film forming process is preferably used.

As such a vacuum film forming process, a vacuum evaporation method, a sputtering method, a chemical vapor deposition (deposition)
A method (CVD) method and the like can be mentioned, and among them, it is preferable to mainly use a vacuum evaporation method, which generally has a feature of high film forming speed and excellent economic efficiency.

[0109] The vacuum evaporation method generally means that after evacuation is performed so that the pressure in the apparatus is at least 10 ^-1 Pa or less, a material substance heated and vaporized 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, when the former heating method using an electron beam or an ion beam is used, by controlling the amount of emission of the beam, the deposition rate is high, and stable vacuum deposition can be performed for a long time.
Is preferable because a layer having a film thickness exceeding the above can be obtained relatively easily and economically.

Here, a method of ionizing vapor deposition particles in a vacuum chamber by an appropriate method and then accelerating the electric field to deposit the particles on a substrate (often referred to as ionization 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.

The sputtering method (generally referred to as a magnetron sputtering method) is similar to the vacuum evaporation method, except that the apparatus is evacuated so that the pressure in the apparatus becomes at least 10 ^-1 Pa or less, and then the inert gas or a small amount of gas is introduced into the apparatus. 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 higher-hardness layer is easily obtained, but the deposition rate is considerably 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 is required to 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 sputtered 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 layers made of inorganic materials such as various oxides such as silicon oxide, aluminum oxide, cerium oxide, silicon nitride, aluminum nitride, and silicon carbide; nitrides and carbides; ,
A layer made of carbon called so-called diamond-like carbon (DLC) can be mentioned. Among them, in order to make the hard coat layer have high transparency and excellent mechanical properties, silicon oxide is used as a main component. It is preferable to use silicon oxide, and it is preferable that silicon oxide accounts for at least 50% by weight or more, more preferably 75% by weight of the whole layer.

For the purpose of obtaining higher transparency, it is preferable that the value of n of SiOn indicating the oxidation number of silicon oxide is approximately 2.0.

The hard coat layer preferably uses silicon oxide as a main component as described above. However, if necessary, a material in which other types of inorganic oxides are mixed as an auxiliary component at an appropriate ratio may be used. Is also possible.

As such subcomponents, magnesium oxide, zirconium oxide, titanium oxide and the like are preferably exemplified, and the hardness increase and brittleness of the hard coat layer are improved, and the refractive index difference between the hard coat layer and the actinic ray cured layer is obtained. 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 at least 1.5 μm, more preferably at least 2.5 μm, even more preferably. Is 3.5 μm or more. 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.

With respect to 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 active light curable layer are interposed between the active light curable layer and the hard coat layer. Layers near the geometric mean with the refractive index
The value obtained by multiplying the thickness of the layer and the refractive index (optical film thickness) is 100 to 1
The effect may also be obtained by laminating so as to have a thickness of about 60 nm, and the thickness of the hard coat layer performed as needed can be appropriately selected depending on the purpose.
It is preferably in the range of 20 μm. When the film thickness is 1 μm or less, the abrasion resistance may be insufficient when repeatedly worn. If it exceeds 20 μm, the brittleness of the hard coat layer is surfaced and cracks are likely to occur on the surface, or the adhesion to the polymer resin film may be reduced. More preferably, the film thickness is in the range of 2 to 10 μm.

If necessary, actinic rays may be added for the purpose of improving the adhesion between the actinic ray-curable layer and the hard coat layer, or improving the weather resistance (for example, resistance to ultraviolet aging) of the laminate. It is possible to apply an appropriate surface treatment to the surface of the cured layer or to laminate a primer layer.

As the surface treatment, for example, well-known methods such as plasma treatment, corona treatment, and UV-ozone treatment are preferably used, and the effect of improving the adhesion of the cured layer and the coating property of the precursor material is preferably used. Can be obtained.

As the primer layer, for example, a layer made of various methacrylates or a copolymer of these with other components is preferably exemplified. In particular, polymethyl methacrylate and a copolymer of polymethyl methacrylate and other components are preferably used. A layer made of a polymer is preferably used. Preferred examples of the other components to be copolymerized include silicon alkoxides containing an acryloyl group, a methacryloyl group, a vinyl group and the like in the molecule.

For the purpose of improving the weather resistance, it is also preferable that the primer layer contains 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 method of coating the hard coat layer and the primer layer on the polymer resin substrate includes spin coating, (doctor) knife coating, various types of gravure coating, micro gravure coating, and (Meier) bar coating. In many cases, various methods such as a coating method, a reverse roll coating method, a die coating method, a spray coating method, and a dip coating method can be used.

The polymer resin substrate is not particularly limited, but, from the gist of the present invention, a polymer resin substrate having a pencil hardness of at least 3H or less is an object.

Examples of such a polymer resin substrate include polycarbonate, polyarylate, polyethylene terephthalate, polyethylene naphthalate and various polyolefin resins (for example, the trade name “ARTON” of JSR, the trade name of “Zeon Japan” Zeonex ") and the like.

The thickness of the polymer resin substrate is not particularly limited, but at least the thickness of the coating layer, ie, the total of the active light-curable layer and the hard coat layer, or the total of the active light-curable layer, the hard coat layer and the primer layer Is preferably greater than about 100 μm. In particular, when the laminate is used for applications requiring flexibility, 1
00 to 500 μm, more preferably 150 to 400 μm
Range.

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.

Of these, 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 and diethylcarbonate. 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 is to be noted that those containing other components as copolymerized or blended components may also be used in the above item 8. In the category of polycarbonate.

The compound most suitable 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 method of coating a layer is restricted (a dip coating method is mainly used).

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 as 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, a layer having a function of improving the adhesion of the cured layer or improving the weather resistance (for example, resistance to ultraviolet aging) of the laminate is 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 preferably has high transparency, and specifically, has a haze value of 5
% Or less, and more preferably 3% or less.

The light transmittance of the laminate is determined by mixing a visible light absorbing agent (eg, a pigment or a dye) in the polymer resin substrate or the active light-cured layer, or by appropriately adding light absorbing properties to the hard coat layer. The total light transmittance is 30% or more, and more preferably 50% or more, unless the light transmittance of the laminate is intentionally reduced by a method such as using a layer having the same.

Incidentally, the polymer resin laminate of the present invention is formed by laminating a hard coat layer (B) on the resin with the upper surface facing out, so that a molded product having a high surface hardness can be obtained. Can be obtained.

As the method, for example, it may be used as an insert film or sheet in so-called in-mold molding or insert molding.

That is, after the polymer resin laminate is fixed to the mold of the injection molding machine with the upper surface of the hard coat layer (B) facing the mold surface, the polymer resin such as polycarbonate or acrylic is molded. Injection in a molten state into the mold and integral molding inside the mold can produce molded articles of various shapes and sizes.

In addition, any molding technique using a mold such as extrusion molding or reaction injection molding may be used as long as a molded article for laminating the polymer resin laminate according to the present invention can be produced.

In the present invention, for example, the resin is extruded into a plate shape in a molten state, brought into contact with the polymer resin laminate of the present invention running in parallel, and pressed against each other.
A plate-like molded product is manufactured by continuously manufacturing a plate-like molded product, or by integrating the polymer resin laminate according to the present invention with a separately molded resin molded product via an appropriate adhesive layer (adhesive layer). Even in the case where the concept of a mold cannot be applied, such as in the case of manufacturing, the present invention can be applied to various existing technologies as long as a resin laminate molded article can be produced.

Further, in the present invention, "the molded product is
The molded article characterized in that it is the polymer resin laminate according to any one of the above items 1 to 13, has an advantage that the operation required for molding can be simplified. That is, if a polymer resin substrate having an appropriate shape is used, the polymer resin laminate itself can be obtained as a molded product, and in this case, there is an advantage that the operation required for molding can be simplified. .

The above-mentioned methods are suitable for the purpose of producing, with high productivity, window materials for automobiles and buildings, structural materials requiring transparency, and the like, and are preferably used.

[0157]

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.

(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”.

(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 was abraded under the conditions of a load of 4.9 N and 1000 cycles, and the difference (ΔH) between before and after abrasion of the haze value obtained from the following equation was evaluated.

Haze (%) = (diffuse transmittance / total light transmittance) × 100 The Taber abrasion of the hard coat layer is slightly improved by storage (aging) at room temperature from the time when the heat curing treatment is performed. In some cases, the Taber abrasion test was performed for each sample after the sample was prepared and stored for 7 days in an environment at a temperature of 25 ° C. and a humidity of 50%.

(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 Absorption 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 in portions other than the actinic ray cured layer such as the polymer resin substrate and the hard coat layer, the actinic ray cured layer was formed on a 2 mm thick quartz plate with the same film thickness. Using a separately laminated sample, [(Ultraviolet transmittance of quartz plate without active light cured layer)-(UV transmittance of quartz plate with active light cured layer laminated)] / (Activity The ultraviolet light absorption of the active light-curable layer was determined by taking the value of (ultraviolet transmittance of the quartz plate when the light-curable layer was not laminated).

(Measurement of Adhesion) Japanese Industrial Standard K5400
The measurement was carried out in accordance with the cross-cut tape test method described in the above section.

(Evaluation of light fastness) I-Super UV tester SUV-F11 manufactured by Iwasaki Electric Co., Ltd. 295-45
Irradiation with light in the ultraviolet / visible region of 0 nm is performed at an intensity of 100 mW / cm ₂ for 150 hours. The light transmission spectrum of the sample was measured before and after this light irradiation, and the chromaticity index b ^* value of the L ^* a ^* b ^* color system defined by Japanese Industrial Standard Z8729 for the transmitted light was increased, that is, the color difference △ b ^* The degree of coloring of the sample was evaluated by comparing the values.

The transmission spectrum was measured in a spectrophotometer U3500 manufactured by Hitachi in an integrating sphere measurement mode at an incident angle of 0 °. In calculating the b ^* value, standard light C specified in Japanese Industrial Standard Z8720 was used. And the condition of twice viewing was used.

[Preparation of Precursor Material 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, 0.16 parts by weight of azobisisobutyronitrile and 200 parts by weight of 1,2-dimethoxyethane was 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 material P for forming a primer layer.

[Preparation of Hard Coat Layer Precursor Material H1] An aqueous dispersion of ultrafine silicon oxide particles having an average particle diameter of 10 to 20 nm in 30 parts by weight of methyltrimethoxysilane (manufactured by Catalyst Chemical Industry Co., Ltd.) Product name "Cataloid SI-3
0 "solid content concentration 30% by weight) and 20 parts by weight of acetic acid 3.5
The acidic dispersion mixed with the parts by weight was added with vigorous stirring under external cooling.

After stirring at room temperature for 3 hours, 35 parts by weight of isopropyl alcohol and 0.2 parts by weight of sodium acetate were added. The pH of the system was about 5.3. 3 at room temperature
After standing for a day, the mixture was filtered through a 3 μm filter to prepare a hard coat layer forming precursor material H1.

In the precursor material H1, the hydrolytic condensate of the silicon alkoxide is in a state of being dissolved in the methanol component generated by the dealcoholation reaction of the alkoxide and the added isopropyl alcohol.

In the precursor material H1, the ultrafine particles of silicon oxide and the hydrolytic condensate of methyltrimethoxysilane correspond to the non-volatile components. That is, the ultrafine particles of silicon oxide are 6 parts by weight, and the hydrolytic condensate of methyltrimethoxysilane is 14.6 parts by weight assuming a complete condensation state.

Thus, when the hydrolysis-condensation of methyltrimethoxysilane is completely performed, trifunctional silicon alkoxide in which three methoxy groups and / or ethoxy groups are bonded to one silicon atom in the nonvolatile component of precursor material H1. Is about 71% by weight. In addition, when the hydrolysis-condensation of methyltrimethoxysilane is not completely performed, this weight ratio is further increased.

Using this precursor material H1, a hard coat layer was laminated and cured on a 2 mm-thick quartz plate with a thickness of 5 μm (laminated with a 2 μm-thick primer layer using a precursor material P for forming a primer layer). After that, the pencil strength measured on the surface of this layer was 9H, and the hard coat layer was laminated and cured to a thickness of 5 µm on a 1 mm thick polycarbonate plate using the same precursor material H1 as described above (for primer layer formation). After laminating through a 2 μm thick primer layer of precursor material P), the haze increase due to Taber abrasion measured on the surface of this layer was 2.8%.

[Preparation of precursor material H2 for forming hard coat layer] Dipentaerythritol hexaacrylate (trade name "NK Ester A-9530" manufactured by Shin-Nakamura Chemical Co., Ltd.)
100 parts by weight, 5 parts by weight of a photopolymerization initiator (“Irgacure 184” manufactured by Ciba Specialty Chemicals) and a leveling agent (“SH28PA” manufactured by Dow Silicone Toray)
0.05 parts by weight and 300 parts by weight of 1-methoxy-2-propanol were mixed and filtered through a 1 μm filter to prepare a precursor H2 for forming a hard coat layer.

The components other than 1-methoxypropanol in this precursor correspond to non-volatile components. Therefore, the proportion of the polymer of the polyfunctional (meth) acrylate having three or more acryloyl groups and / or methacryloyl groups in the molecule in the nonvolatile component of the precursor material was about 95% by weight.

Using this precursor material H2, a hard coat layer was laminated and cured on a quartz plate having a thickness of 2 mm to a thickness of 5 μm (laminated with a 2 μm thick primer layer using a precursor material P for forming a primer layer). After that, the pencil strength measured on the surface of this layer was 9H, and a hard coat layer was laminated and cured to a thickness of 5 µm on a 1 mm thick polycarbonate plate using the same precursor material H1 as described above (without a primer layer). After that, the haze increase due to Taber abrasion measured on the surface of this layer was 4.8%.

Example 1 As a polymer resin substrate, a polycarbonate resin synthesized from bisphenol A and diphenyl carbonate was 2 mm thick, 350 mm in length and width.
mm × 250 mm molded plate (“PANLITE P” manufactured by Teijin Chemicals Limited)
C-1111).

The following precursor for forming an actinic ray-curable layer was coated on this substrate with a doctor knife,
After drying at 30 ° C. for 30 seconds, 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 laminate an actinic ray cured layer having a thickness of 90 μm.

As the precursor for forming the actinic ray-curable layer, 100 parts by weight of dicyclopentanyl diacrylate (trade name “light acrylate DCP-A” manufactured by Kyoeisha Chemical Co., Ltd.) and a photopolymerization initiator (“Ciba Specialty Chemicals”) 3 parts by weight of Irgacure 184), 0.05 parts by weight of a leveling agent ("SH28PA" manufactured by Toray Dow Silicone Co., Ltd.) and 30 parts by weight of normal propyl alcohol were used without mixing with an ultraviolet absorber.

All components other than normal propyl alcohol in the precursor for forming an actinic ray cured layer correspond to non-volatile components. Therefore, the ratio of dicyclopentanyl diacrylate in the non-volatile component of the precursor for forming an actinic ray-curable layer is about 97% by weight, and is a polyfunctional compound having three or more acryloyl groups and / or methacryloyl groups in the molecule. The (meth) acrylate is not mixed.

Using the same precursor material as described above, an actinic ray-cured layer was laminated and cured on a quartz plate having a thickness of 2 mm to a thickness of 90 μm (2 μm by a precursor material P for forming a primer layer).
After laminating via a thick primer layer), the measured pencil strength was 3H.

Subsequently, the surface of the polycarbonate substrate on which the actinic ray-curable layer was laminated was treated with a UV-ozone treatment apparatus (OC2506 type manufactured by Eye Graphic Co., Ltd.) for 1 minute, and then the precursor material for forming a primer layer was formed on the surface. P
Was coated using a bar coater, air-dried for 10 minutes in a dry air stream, and then dried at 120 ° C. for 2 minutes to form a 2 μm-thick primer layer.

Subsequently, a hard coat layer forming precursor material H1 was coated on the primer layer using a bar coater, and was naturally dried for 10 minutes under a stream of dry air.
Heat cured at 130 ° C. for 30 minutes and the film thickness is 5 μm
Was formed.

The appearance of the hard coat laminate thus obtained was very good, the total light transmittance was 90.2%, the haze was 0.9%, the pencil hardness was 4H, and the haze increase due to Taber abrasion was 3. 1%, and the adhesion was as good as 100/100.

However, the Δb ^* value in the light resistance test was 23.5, and yellow coloring was clearly observed with the naked eye.

Example 2 As a polymer resin substrate, a polycarbonate resin synthesized from bisphenol A and diphenyl carbonate was 0.3 mm thick, 3 mm wide and 3 mm wide.
A hard coat laminate was prepared in exactly the same manner as in Example 1 except that a 50 mm × 250 mm film (“Panelite PC-2151” manufactured by Teijin Chemicals Co., Ltd.) was used and the following materials were used as precursors for forming an actinic ray-curable layer. Created.

As the precursor for forming the actinic ray-curable layer,
Photopolymerization with 80 parts by weight of dicyclopentanyl diacrylate (trade name "light acrylate DCP-A" manufactured by Kyoeisha Chemical) and 20 parts by weight of dipentaerythritol hexaacrylate (trade name "NK Ester A-9530" manufactured by Shin-Nakamura Chemical Co., Ltd.) 3 parts by weight of an initiator (“IRGACURE 184” manufactured by Ciba Specialty Chemicals) and a leveling agent (Toray
0.05 parts by weight of "SH28PA" made by Dow Silicone and 30 parts by weight of normal propyl alcohol were mixed, and no ultraviolet absorber was mixed.

All components other than normal propyl alcohol in this precursor for forming an actinic ray cured layer correspond to non-volatile components. That is, the ratio of dicyclopentanyl diacrylate in the non-volatile component of the precursor for forming an actinic ray curable layer was about 77% by weight. In the actinic ray-curable layer, the ratio of the polyfunctional (meth) acrylate having three or more acryloyl groups and / or methacryloyl groups in the molecule to the entire nonvolatile component was about 19% by weight. Using the same precursor material as above, an actinic ray-cured layer was formed on a quartz plate having a thickness of 2 mm by 50 mm.
Lamination curing with a thickness of μm (Primer layer forming precursor material P
After laminating through a 2 μm thick primer layer)
The measured pencil strength was 5H.

The appearance of the thus obtained hard coat layer laminate was very good, and the total light transmittance was 90.1%.
The haze was 1.1%, the pencil hardness was 6H, the haze increase due to Taber abrasion was 3.3%, and the adhesion was 100/100, which was good.

However, the Δb ^* value in the light resistance test was 31.7, and yellow coloring was clearly observed with the naked eye.

Example 3 As a polymer resin substrate, a polycarbonate resin synthesized from bisphenol A and diphenyl carbonate was 0.3 mm in thickness, 2 in length and 2 in width.
A 00 mm × 150 mm film (“Panlite PC-2151” manufactured by Teijin Chemicals Limited) was used.

The following precursor for forming an actinic ray-curable layer was coated on this substrate with a doctor knife,
After drying at 0 ° C. for 30 seconds, an electron beam is irradiated by an electron beam irradiation device TYPE: CB250 / 15 / 180L manufactured by ESI under the conditions of an acceleration voltage of 150 KV and an irradiation dose of 300 KGY · m / min, and an actinic ray having a thickness of 90 μm. A hard coat laminate was formed in exactly the same manner as in Example 1 except that the cured layer was laminated.

As a precursor for forming an actinic radiation-curable layer, 100 parts by weight of dicyclopentanyl dimethacrylate (trade name “NK Ester DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.) and 0.9 parts by weight of an ultraviolet absorber (manufactured by Ciba Specialty Chemicals) Product name "Tinuvin 329") and leveling agent (Toray
0.05 parts by weight of "SH28PA" made by Dow Silicone and 30 parts by weight of normal propyl alcohol were mixed.

All components other than normal propyl alcohol in this precursor for forming an actinic ray cured layer correspond to non-volatile components. That is, the ratio of dicyclopentanyl dimethacrylate in the non-volatile component of the precursor for forming an actinic radiation-curable layer was about 99% by weight. In the actinic ray-curable layer, a polyfunctional (meth) acrylate having three or more acryloyl groups and / or methacryloyl groups in the molecule is not mixed.

The addition amount of the ultraviolet absorber in the non-volatile component of the precursor of the actinic ray curable layer was about 0.9% by weight. Therefore, the product of the actinic ray curable layer and the film thickness (μm) was 81%. % By weight · μm.

Using the same precursor material as above, an actinic ray-cured layer was laminated and cured on a quartz plate having a thickness of 2 mm to a thickness of 50 μm (2 μm by a primer layer forming precursor material P).
After laminating through the thick primer layer), the measured pencil strength was 5H, and the absorptance in the wavelength region of 300 to 350 nm was 99.9% or more.

The thus obtained hard coat layer laminate had a very good appearance, a total light transmittance of 90.0%,
The haze was 1.3%, the pencil hardness was 6H, the haze rise due to Taber abrasion was 3.6%, and the adhesion was 100/100, which was good.

Further, in the light resistance test, Δb ^* value was 1.1, the coloring of the laminated body was extremely small, and the light resistance was excellent.

Example 4 A 0.3 mm-thick and 500 mm-wide film ("Panlite PC-2151" manufactured by Teijin Chemicals Ltd.) of a polycarbonate resin synthesized from bisphenol A and diphenyl carbonate was unwound from a roll and continuously run. While applying 0.2 J /
After performing corona treatment with an integrated discharge amount of cm ² , the following precursor for forming an actinic ray-curable layer was coated by a die coating method, passed through a drying oven at 60 ° C. for 30 seconds, and then subjected to an electron beam manufactured by ESI. Irradiation device TYPE: CB200
Acceleration voltage 150KV, irradiation dose 1 according to / 45/300
Irradiation with an electron beam under the condition of 00KGY · m / min.
After forming an actinic ray-curable layer having a thickness of 0 μm, the layer was wound around a roll.

As the precursor for forming the actinic ray curable layer, 100 parts by weight of dicyclopentanyl diacrylate (trade name “Light Acrolate DCP-A” manufactured by Kyoeisha Chemical Co., Ltd.) and a leveling agent (trade name manufactured by Dow Silicone Toray) 0.05 parts by weight of “SH28PA” and 2- (2′-hydroxy-5′-methacryloxyphenyl) -2H-benzotriazole (trade name “RUVA-93” manufactured by Otsuka Chemical Co., Ltd.) as a reactive ultraviolet absorber 0 9.9 parts by weight and 15 parts by weight of normal propyl alcohol were mixed and used.

All components other than normal propyl alcohol in the precursor for forming an actinic ray cured layer correspond to non-volatile components. That is, the ratio of dicyclopentanyl diacrylate in the non-volatile component of the precursor for forming an actinic radiation-curable layer was about 99% by weight. The actinic ray-curable layer contains a polyfunctional (meth) having three or more acryloyl groups and / or methacryloyl groups in the molecule.
Acrylate is not mixed.

The addition amount of the ultraviolet absorber in the non-volatile component of the precursor of the actinic ray-curable layer was about 0.9% by weight. Therefore, the product of the actinic ray-curable layer and the film thickness (μm) was 81%. % By weight · μm.

Using the same precursor material as described above, an actinic radiation-cured layer was laminated and cured on a quartz plate having a thickness of 2 mm to a thickness of 90 μm (2 μm by the precursor material P for forming a primer layer).
After laminating through a thick primer layer), the measured pencil strength was 3H, and the absorptance in the wavelength region of 300 to 350 nm was 99.9% or more.

Next, the film was unwound again and allowed to run continuously, and after a corona treatment was applied to the film surface on which the cured layer of dicyclopentanyl diacrylate was laminated at an integrated discharge amount of 0.4 J / cm ² , The precursor material P for forming a primer layer is coated by a microgravure method,
After passing through a drying oven at 0 ° C. for 2 minutes to carry out solvent drying and heat treatment, a 2 μm-thick primer layer was laminated and wound up on a roll.

Further, the film was unwound again, the upper surface of the primer layer was coated with a hard coat layer forming precursor material H1 by a microgravure method, passed through a drying oven at 130 ° C. for 5 minutes, subjected to a thermosetting treatment, and A 5 μm hard coat layer was laminated and wound up on a roll.

[0211] The appearance of the film laminate on which the hard coat layer was laminated was very good, and the total light transmittance was 90.
1%, haze 1.2%, pencil hardness 4H, haze increase due to Taber abrasion 5.4%, adhesion 100/10
0 was good.

Further, in the light resistance test, the Δb ^* value was 0.9, the coloring of the laminate was very slight, and the light resistance was excellent.

Example 5 The thickness was 188 μm and the width was 130
Using a 0 mm polyethylene terephthalate film (OFL-188, manufactured by Teijin), the same precursor for forming an actinic radiation-curable layer as used in Example 1 was coated by a die coating method, and passed through a drying oven at 60 ° C. for 30 seconds. rear,
Integrated light quantity of 1.2 using 160 W / cm high pressure mercury lamp
The layer was irradiated with ultraviolet rays of J / cm ² to form a 90 μm-thick actinic ray cured layer, and then wound around a roll.

Next, the film was unwound again and allowed to run continuously, and a corona treatment was performed on the film surface on which the cured layer of dicyclopentanyl diacrylate was laminated at an integrated discharge amount of 0.6 J / cm ² , followed by the primer layer. The precursor material P for forming was coated by a microgravure method, passed through a drying oven at 120 ° C. for 2 minutes, subjected to solvent drying and heat treatment, and after laminating a 2 μm-thick primer layer, it was wound around a roll.

Further, the film was unwound again, the upper surface of the primer layer was coated with the hard coat layer forming precursor material H1 by a microgravure method, passed through a drying oven at 120 ° C. for 5 minutes, subjected to a thermosetting treatment, and A 5 μm hard coat layer was laminated and wound up on a roll.

The appearance of the film laminate on which the hard coat layer was laminated was very good, and the total light transmittance was 89.
7%, haze 1.6%, pencil hardness 4H, haze increase due to Taber abrasion 5.9%, adhesion 100/10
0 was good.

[Example 6] In Example 5, 0.6 J / c was applied on the upper surface of the cured layer of dicyclopentanyl diacrylate.
After performing a corona treatment with an integrated discharge amount of m ^2, the precursor material H for forming a hard coat layer directly without laminating a primer layer
2 was coated using a microgravure method and 70
After drying the solvent by passing it through a drying oven at
1.0 J integrated light quantity by 60 W / cm high pressure mercury lamp
/ Cm ² UV light to cure the layer and make it 5 μm thick
Were laminated.

The appearance of the film laminate on which the hard coat layer was laminated was very good, and the total light transmittance was 89.4.
%, Haze is 1.5%, pencil hardness is 4H, haze rise by Taber abrasion is 5.3%, and adhesion is 100/100.
And was good.

[Example 7] In Example 3, the ultraviolet absorber added to the precursor for forming the actinic ray-curable layer was changed to 2
-(4,6-diphenyl-1,3,5-triazine-2
-Yl) -5-[(hexyl) oxy] -phenol (trade name: Tinuvin 1 manufactured by Ciba Specialty Chemicals)
577FF ", 0.9 parts by weight added) and hard coat lamination in exactly the same manner as in Example 3 except that the amount of the photopolymerization initiator (" Irgacure 184 "manufactured by Ciba Specialty Chemicals) was changed to 6 parts by weight. Formed body. The addition amount of the ultraviolet absorber in the nonvolatile component of the precursor of the actinic ray-curable layer was about 0.85% by weight.
The product of the actinic ray-curable layer and the film thickness (μm) is 76% by weight · μ
m.

Further, using the same precursor material as described above, an actinic ray-cured layer was laminated and cured on a quartz plate having a thickness of 2 mm to a thickness of 90 μm (2 μm by a primer layer forming precursor material P).
After laminating through a thick primer layer), the measured pencil strength was 3H, and the absorptance in the wavelength region of 300 to 350 nm was 99% or more.

Incidentally, the appearance of the hard coat laminate thus obtained was very good, and the total light transmittance was 90.2%.
%, Haze is 1.1%, pencil hardness is 4H, haze rise due to Taber abrasion is 5.2%, and adhesion is 100/100.
And was good.

Furthermore, the light resistance was as excellent as 0.2 in Δb ^* value.

Example 8 A molded plate of polycarbonate having a cured layer of dicyclopentanyl diacrylate having a thickness of 70 μm was cut into a 10 cm square size in the same manner as in Example 1 (primer in Example 1). The layer and the hard coat layer are not laminated here).
After performing a heat treatment at 1 ° C. for 1 hour, it was set in a vacuum chamber of a vacuum evaporation apparatus and evacuated for 3 hours, and a pressure of 2 × 1
After reaching a degree of vacuum of 0 ⁻³ Pa, a molten mass of silicon oxide (SiO ₂ content: 95% or more) filled in the crucible was sublimated by electron beam evaporation (EB evaporation), A 3.2 μm-thick silicon oxide layer was laminated on the cured layer of cyclopentanyl 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.

When this hard coat layer was formed directly on a glass plate, the pencil hardness of the layer was 9H, and the increase in haze in a Taber abrasion test under a load of 4.9N and 1000 cycles was 2.8%. Met.

The appearance of the hard coat laminate was very good, the total light transmittance was 91.0%, the haze was 1.0%, the pencil hardness was 4H, and the haze increase due to Taber abrasion was 2.1%. , And the adhesion was as good as 100/100.

Further, this hard coat laminate had a feature excellent in water resistance. That is, the laminate is heated
Even after the test of immersion in boiling water for 30 minutes, no deterioration in performance such as a change in appearance or a decrease in adhesion was observed.

Example 9 A silicon oxide layer was further laminated by a sputtering method on a silicon oxide layer obtained by vacuum deposition of the hard coat laminate of Example 8.

That is, the same hard coat laminate as that prepared in Example 8 was set in a vacuum chamber and evacuated for 3 hours, and after reaching a degree of vacuum of 2 × 10 ⁻³ Pa, A mixed gas of Ar / O ₂ = 95: 5 was introduced,
The atmospheric pressure was set to 0.27 Pa.

A silicon oxide target (SiO ₂ content: 95% or more) was used as a sputtering target.
A 0.18 μm-thick silicon oxide layer was formed by RF magnetron sputtering under the conditions of a power density of 1 W / cm ² .

When the hard coat layer was formed directly on a glass plate, the pencil hardness of the layer was 9H, and the increase in haze in a Taber abrasion test under a load of 4.9N under 1,000 cycles was 1.9%. Met.

The appearance of this hard coat laminate was very good, the total light transmittance was 90.9%, the haze was 1.0%, the pencil hardness was 4H, and the haze increase due to Taber abrasion was 1.4%. , And the adhesion was as good as 100/100.

Further, this hard coat laminate had very excellent water resistance. That is, even after the test in which the laminate was immersed in boiling water at 100 ° C. for one hour, no deterioration in performance such as a change in appearance or a decrease in adhesion was observed.

[Comparative Example 1] Except that a primer layer and a hard coat layer (a hard coat layer made of the precursor material H1) were directly formed on the polycarbonate plate without laminating an actinic ray-curable layer in the same manner as in Example 1, but this was carried out at all. In the same manner as in Example 1, a hard coat laminate was prepared.

The appearance of this hard coat laminate was very good, and the haze increase due to Taber abrasion was 2.8%, almost the same as that of Example 1, but the pencil hardness was F.

Comparative Example 2 A hard coat laminate was prepared in the same manner as in Example 1, except that the thickness of the actinic ray-curable layer was changed to 30 μm.

The appearance of this hard coat laminate was very good, and the haze increase due to Taber abrasion was 3.0%, which was almost the same as in Example 1, but the pencil hardness was H.

Comparative Example 3 A hard coat laminate was prepared in exactly the same manner as in Example 4 except that the primer layer and the hard coat layer were formed directly without laminating the actinic ray curable layer. did.

The appearance of this hard coat laminate was very good, and the haze increase due to Taber abrasion was 5.2%, almost the same as that of Example 4, but the pencil hardness was 3H.

[Comparative Example 4] In Example 1, dicyclopentanyl diacrylate in the precursor for forming an actinic ray-curable layer was replaced by dipentaerythritol which is a polyfunctional acrylate having three or more acryloyl groups in the molecule. A hard coat laminate was prepared in exactly the same manner as in Example 1 except that an actinic ray-curable layer having a thickness of 40 μm was laminated, completely replacing with hexaacrylate.

In this hard coat laminate, the cracks occurred on one surface of the actinic ray-cured layer and the appearance became poor, and the coating of the primer layer and the hard coat layer on the layer became impossible. did.

[Comparative Example 5] A hard disk was formed in the same manner as in Example 8 except that a silicon oxide layer was directly formed on a polycarbonate substrate by a vacuum evaporation method without forming an actinic ray-curable layer. A coated laminate was made.

The appearance and light transmittance of this hard coat laminate were very good, and the adhesion was good at 100/100, but the pencil hardness was F and the haze increase due to Taber abrasion was 20.8%. It was remarkably inferior to Example 8.

Further, after the test of immersing this laminate in boiling water at 100 ° C. for 30 minutes, the deposited film was completely peeled off and was poor in water resistance.

[0245]

According to the present invention, a polymer resin laminate having a high hardness can be obtained by applying the present invention to a resin molded product having a relatively low hardness such as polycarbonate, and a window material such as an automobile or a building material can be obtained. It can be used for structural materials that require transparency and a wide range of other uses.

[Brief description of the drawings]

FIG. 1 is a graph showing the results of a finite element method simulation on a change in the indentation depth on the surface of a laminate according to the thickness of a rigid layer.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 27/20 B32B 27/20 Z 27/30 27/30 A 27/36 102 27/36 102 B60J 1 / 00 B60J 1/00 H C08F 2/44 C08F 2/44 B 2/48 2/48 C08J 7/04 CFD C08J 7/04 CFDZ // C08L 69:00 C08L 69:00 (72) Inventor Rina Iwai Yamaguchi No. 1, Hinode-cho, Iwakuni-shi, Iwate Prefecture Inside the Iwakuni Research Center, Teijin Co., Ltd. (72) Inventor Satoshi Omori No. 1, Hinode-machi, Iwakuni-shi, Yamaguchi Prefecture Inside, Iwakuni Research Center, Teijin Co., Ltd. (72) Hiromasa Minematsu, Iwakuni, Yamaguchi Prefecture 2-1, Hinodecho, Teijin Co., Ltd. F-term in Iwakuni Research Center, Teijin Limited 4D075 AE03 AE27 BB23Y BB26Z BB42Y BB42Z BB46Y BB46Z BB47Y BB47Z BB85Z BB92Y BB92Z BB93Y CA 02 CA13 CA32. CA07H CA18 CC02B EH46B EH66C EH66D EJ42B EJ53B EJ54B EJ65 GB07 GB32.

Claims (19)

[Claims] 1. A polymer resin substrate having a thickness of 50 to 30
An actinic ray-curable layer (A) having a pencil hardness of 3H or more having a thickness of 1 μm and a load of 4.9 N having a thickness of 1 to 20 μm;
A polymer resin laminate obtained by laminating a hard coat layer (B) having a haze increase of 10% or less and a pencil hardness of 4H or more in a 00 cycle Taber abrasion test in this order. 2. The actinic ray-curable layer (A) is a layer obtained by curing a precursor material in which dicyclopentanyl diacrylate and / or dicyclopentanyl dimethacrylate occupies 50% by weight or more of the entire nonvolatile component. The polymer resin laminate according to claim 1, wherein: 3. The actinic ray-curable layer (A) is a mixture of a polyfunctional (meth) acrylate having at least three acryloyl groups and / or methacryloyl groups in a molecule in a proportion of not more than 50% by weight of the whole nonvolatile component. The polymer resin laminate according to claim 2, wherein the polymer resin laminate is a layer obtained by curing a precursor material. 4. 300-350 of the actinic ray-curable layer (A)
The polymer laminate according to any one of claims 1 to 3, wherein a light absorptivity in a wavelength region of nm is 99% or more. 5. The product of the addition amount (% by weight) of the ultraviolet absorber in the non-volatile component of the precursor of the actinic ray curable layer (A) and the thickness (μm) of the actinic ray curable layer (A) is 30. The polymer laminate according to any one of claims 1 to 4, wherein the thickness is in the range of from about 300% by weight to about 300% by weight. 6. An ultraviolet absorber mixed with the actinic ray-curable layer (A) as 2- (4,6-diphenyl-1,3,5).
The polymer laminate according to any one of claims 1 to 5, wherein -triazin-2-yl) -5-[(hexyl) oxy] -phenol is mainly used. 7. The hard coat layer (B) is a layer containing at least 50% by weight of a hydrolytic condensate of a trifunctional silicon alkoxide in which three methoxy groups and / or ethoxy groups are bonded to one silicon atom. Claims 1 to
7. The polymer resin laminate according to any one of 6. 8. The hard coat layer (B) comprises a polymer of a polyfunctional (meth) acrylate having three or more acryloyl groups and / or methacryloyl groups in the molecule.
The polymer resin laminate according to any one of claims 1 to 7, which is a layer containing 0% by weight or more. 9. The method according to claim 1, wherein the hard coat layer (B) is a layer having a thickness of 1.5 to 10 μm formed by a vacuum film forming process. Molecular resin laminate. 10. The hard coat layer (B) is a layer formed by a vacuum deposition method.
10. The polymer resin laminate according to any one of 9. 11. A hard coat layer (B) is formed by laminating 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 in this order from the substrate side. The polymer resin laminate according to any one of claims 1 to 10, wherein the polymer resin laminate is a hard coat layer composed of two layers. 12. 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. Claims 1 to 11 characterized by the above-mentioned.
The polymer resin laminate according to any one of the above. 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 a haze value of the laminate is 5% or less. 15. An actinic light-cured layer (A) is formed by applying a precursor of an actinic ray-curable layer on a polymer resin substrate and then curing the applied film of the precursor material by irradiation with an electron beam or ultraviolet rays. The method for producing a polymer resin laminate according to any one of claims 1 to 14, wherein: 16. 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 (A) on the polymer substrate. 17. The method for producing a polymer resin laminate according to claim 15, wherein 17. A molded product obtained by laminating the polymer resin laminate according to claim 1 on a resin with the upper surface of the hard coat layer (B) facing outward. 18. A molded article, characterized in that the molded article is the polymer resin laminate according to any one of claims 1 to 17. 19. The molded product according to claim 17, wherein the molded product is an automobile window or a window for a building material.