TW201815581A - Resin laminate with polarizing plate and display device having the same - Google Patents

Abstract

The present invention provides a resin laminate with a polarizing plate having durability with respect to high temperature and high humidity. The resin laminate with a polarizing plate comprises: a resin laminate (A) which has an intermediate layer having a (meth) acrylic resin and a vinylidene fluoride resin as a resin component, a thermoplastic resin layer on both sides of the intermediate layer, and a hard coat layer on at least one surface of the thermoplastic resin layer; a transparent pressure-sensitive adhesive (B) presented on the surface of the hard coat layer; and a polarizing plate (C).

Description

 Resin laminate with polarizing plate and display device containing the same  

The present invention relates to a resin laminate including a polarizing plate and a display device including the laminate.

In recent years, display devices such as smart phones, portable game consoles, audio players, and tablet devices have increased in number of touch screens. Although a glass flake is usually used for the surface of such a display device, development of a plastic sheet which is a substitute for a glass flake is currently being carried out from the viewpoint of weight reduction of the display device or workability. For example, in Patent Document 1, a transparent sheet containing a methacrylic resin and a vinylidene fluoride resin is disclosed as a plastic sheet substitute for a glass sheet, and it is described that the transparent sheet sufficiently satisfies transparency and specific dielectric constant.

 [Previous Technical Literature]    [Patent Literature]  

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-244604

On the other hand, in recent years, display devices have been used in various environments due to their high versatility, and therefore, it is required to have durability in a severe environment such as high temperature and high humidity.

The conventional transparent sheet described in Patent Document 1 may be turbid in an environment of high temperature and high humidity of 60 ° C and a relative humidity of 90%, for example, and there is room for improvement in durability. Further, in the display device including the plastic sheet, when the plastic sheet is bonded to the polarizing plate and used, in a severe environment such as high temperature and high humidity, peeling or bubbles may occur between the polarizing plate and the plastic sheet.

In order to solve the above problems, the inventors of the present invention have completed the present invention by repeating a detailed study on a resin laminate which is suitably used in a display device.

That is, the present invention encompasses the following preferred aspects.

[1] A resin laminate having a polarizing plate, comprising: a resin laminate (A) having an intermediate layer containing a (meth)acrylic resin and a vinylidene fluoride resin as a resin component, and an intermediate layer in the intermediate layer a thermoplastic resin layer on both sides, and a hard coat layer on at least one outermost surface of the thermoplastic resin layer; and a transparent adhesive (B) present on a surface of at least one hard coat layer side of the resin laminate (A); And a polarizing plate (C) which is present via the transparent adhesive (B).

[2] The resin laminate with a polarizing plate according to [1], wherein the resin laminate (A) and the end face of the polarizing plate (C) are the same.

[3] The resin laminated body with a polarizing plate according to [1], wherein the end face of the polarizing plate (C) is located inside the end face of the resin laminated body (A).

[4] The resin laminated body with a polarizing plate according to any one of [1] to [3] wherein the intermediate layer of the resin laminated body (A) is an all-resin component contained in the intermediate layer. The standard contains 35 to 45 mass% of the (meth)acrylic resin and 65 to 55 mass% of the vinylidene fluoride resin.

[5] The resin laminate of the polarizing plate according to any one of [1] to [4] wherein the (meth)acrylic resin has a weight average molecular weight (Mw) of from 100,000 to 300,000.

[6] The resin laminated body with a polarizing plate according to any one of [1] to [5] wherein the content of the alkali metal in the intermediate layer of the resin laminated body (A) is contained in the intermediate layer. The total resin component is 50 ppm or less based on the standard.

[7] The resin laminated body with a polarizing plate according to any one of [1] to [6] wherein the (meth)acrylic resin is: (a1) a homopolymer of methyl methacrylate; And/or the (a2) copolymer comprises, in relation to the entire structural unit constituting the polymer, 50 to 99.9% by mass of a structural unit derived from methyl methacrylate, and 0.1 to 50% by mass of the derived structure. (1) At least one structural unit of the (meth) acrylate shown.

(wherein R ₁ represents a hydrogen atom or a methyl group, when R ₁ is a hydrogen atom, R ₂ represents an alkyl group having 1 to 8 carbon atoms, and when R ₁ is a methyl group, R ₂ represents an alkane having 2 to 8 carbon atoms. base.)

[8] The resin laminated body with a polarizing plate according to any one of [1] to [7] wherein the vinylidene fluoride resin is polyvinylidene fluoride.

[9] The resin laminated body with a polarizing plate according to any one of [1] to [8] wherein the molten mass flow rate of the vinylidene fluoride resin is 0.1 kg, and 0.1 at 230 ° C. Up to 30g/10 minutes.

[10] The resin laminated body with a polarizing plate according to any one of [1] to [9], wherein at least one of the intermediate layer and the thermoplastic resin layer further contains a coloring agent.

[11] The resin laminate of the polarizing plate according to any one of [1] to [10] wherein at least one of the resin laminate (A) or the transparent adhesive (B) contains UVA.

[12] The resin laminated body with a polarizing plate according to any one of [1] to [11] wherein the average thickness of the resin laminated body is 100 to 2000 μm.

[13] The resin laminated body with a polarizing plate according to any one of [1] to [12] wherein the thermoplastic resin layer is a (meth)acrylic resin layer or a polycarbonate resin layer.

[14] The resin laminated body with a polarizing plate according to any one of [1] to [13] wherein the average thickness of the thermoplastic resin layer is 10 to 200 μm, respectively.

[15] The resin laminated body with a polarizing plate according to any one of [1] to [14] wherein the thermoplastic resin layer has a Vicat softening temperature of 100 to 160 ° C, respectively.

[16] The resin laminated body with a polarizing plate according to any one of [1] to [15] wherein the transparent adhesive (B) has a total light transmittance of 90% or more and a haze of 2 %the following.

[17] The resin laminate with a polarizing plate according to any one of [1] to [16], wherein the resin laminate (A) has a hard coat layer on both surfaces thereof.

[18] The resin laminated body with a polarizing plate according to any one of [1] to [17], wherein the surface of the hard coat layer of the resin laminated body (A) has printing.

[19] The resin laminated body with a polarizing plate according to any one of [1] to [18], wherein the outermost surface of the side of the resin laminated body (A) is further provided with an anti-scratch selected from a functional layer of at least one of the group consisting of anti-reflection, anti-glare, and anti-fingerprint.

[20] A display device comprising the resin laminate of the polarizing plate according to any one of [1] to [19].

The resin laminated system with a polarizing plate of the present invention can be used as a front panel of a display device because of its high dielectric constant and long-term use in a high-temperature and high-humidity environment to maintain transparency.

1‧‧‧Single-axis extruder (melting of extruded thermoplastic resin)

2‧‧‧Single-axis extruder (melting of vinylidene fluoride resin)

3‧‧‧Single-axis extruder (melting of extruded thermoplastic resin)

4‧‧‧Feeding mode

5‧‧‧Multi-manifold die

6‧‧‧ Film-like molten resin

7‧‧‧1st chill roll

8‧‧‧2nd cooling roller

9‧‧‧3rd cooling roller

10‧‧‧Resin laminate (A)

10A‧‧‧Intermediate

10B‧‧‧ thermoplastic resin layer

10C‧‧‧ thermoplastic resin layer

10D‧‧‧hard coating

11‧‧‧Polarized plate (C)

12‧‧‧Transparent Adhesive (B)

13‧‧‧Liquid Crystal Unit

14‧‧‧Liquid crystal display device

Fig. 1 is a schematic view showing a manufacturing apparatus for a laminate including an intermediate layer and a thermoplastic resin layer used in the examples.

Fig. 2 is a schematic cross-sectional view showing a layer configuration example of a preferred embodiment of a liquid crystal display device including a resin laminate having a polarizing plate of the present invention.

Fig. 3 is a schematic cross-sectional view showing a layer configuration example of a preferred embodiment of a liquid crystal display device including a resin laminate having a polarizing plate of the present invention.

The resin laminated body with a polarizing plate of the present invention (hereinafter also referred to as a laminated body of the present invention) has a resin laminated body (A) containing (meth)acrylic resin and vinylidene fluoride resin as An intermediate layer of a resin component, a thermoplastic resin layer on both sides of the intermediate layer, and a hard coat layer on at least one surface of the thermoplastic resin layer; a transparent adhesive (B) present on the surface of the resin laminate (A); And polarizing plate (C).

The intermediate layer contains 35 to 45% by mass of a (meth)acrylic resin and 65 to 55% by mass of a vinylidene fluoride resin based on the total resin component contained in the intermediate layer. When the amount of the (meth)acrylic resin is less than the above lower limit, sufficient transparency cannot be obtained, and when the amount of the (meth)acrylic resin is higher than the above upper limit, a sufficient dielectric constant cannot be obtained. When the amount of the vinylidene fluoride resin is less than the above lower limit, a sufficient dielectric constant cannot be obtained, and when the amount of the vinylidene fluoride resin is higher than the above upper limit, durability cannot be obtained, or sufficient transparency cannot be obtained.

The intermediate layer is contained in an amount of 35 to 45% by mass based on the total resin component contained in the intermediate layer from the viewpoint of improving the dielectric constant and easily obtaining sufficient transparency and dielectric constant of the laminate of the present invention. The acrylic resin and the vinylidene fluoride resin are preferably 65 to 55% by mass, and more preferably contain 36 to 44% by mass of a (meth)acrylic resin and 64 to 56% by mass of a vinylidene fluoride resin. More preferably, it contains 37 to 43% by mass of (meth)acrylic resin and 63 to 57% by mass of a vinylidene fluoride resin, and contains 38 to 42% by mass of (meth)acrylic resin and 62 to 58 mass. The % vinylidene fluoride resin is particularly preferable, and it is excellent to contain 39 to 41% by mass of a (meth)acrylic resin and 61 to 59% by mass of a vinylidene fluoride resin.

The (meth)acrylic resin contained in the intermediate layer of the resin laminate (A) may, for example, be a homopolymer of a (meth)acrylic acid monomer such as (meth)acrylate or (meth)acrylonitrile, or 2 A copolymer of the above (meth)acrylic monomer, a copolymer of a (meth)acrylic monomer and a monomer other than the (meth)acrylic monomer, and the like. In the present specification, the term "(meth)acrylic" means "acrylic acid" or "methacrylic acid group".

The (meth)acrylic resin is preferably a methacrylic resin from the viewpoint of easily improving the hardness, weather resistance, and transparency of the resin laminate. The methacrylic resin is a polymer of a monomer mainly composed of methacrylate (alkyl methacrylate), and examples thereof include a homopolymer of methacrylate (polyalkyl methacrylate) and two kinds of polymers. A copolymer of the above methacrylate copolymer, a copolymer of 50% by mass or more of methacrylate and 50% by mass or less of a monomer other than methacrylate. A copolymer of a monomer other than a methacrylate and a methacrylate is 70 mass % or more of methacrylate and 30 with respect to the total amount of monomers from the viewpoint of easy improvement of optical characteristics and weather resistance. A copolymer of another monomer having a mass % or less is preferable, and a copolymer of 90% by mass or more of methacrylate and 10% by mass or less of other monomers is more preferable.

The single system other than methacrylate may, for example, be an acrylate or a monofunctional monomer having one polymerizable carbon-carbon double bond in the molecule.

The monofunctional single system may, for example, be a styrene monomer such as styrene, α-methylstyrene or vinyltoluene; a cyanide such as acrylonitrile or methacrylonitrile; acrylic acid; methacrylic acid; maleic anhydride; - replacement of maleic imine; and so on.

The (meth)acrylic resin is copolymerizable with N-substituted Malayanya such as phenylmaleimide, cyclohexylmaleimide, and methylmaleimide from the viewpoint of heat resistance. The amine may also be introduced into a lactone ring structure, a glutaric anhydride structure, or a glutarimide structure in a molecular chain (also referred to as a main skeleton in a polymer or in a main chain).

The (meth)acrylic resin is preferably a homopolymer of (a1) methyl methacrylate from the viewpoint of easily improving the hardness, weather resistance, and transparency of the resin laminate. And/or the (a2) copolymer, which comprises from 50 to 99.9% by mass, preferably from 70.0 to 99.8% by mass, more preferably from 80.0 to 99.7% by mass, based on the total structural unit constituting the copolymer. The structural unit of methyl acrylate, and the (meth) acrylate derived from the following formula (1), which is 0.1 to 50% by mass, preferably 0.2 to 30% by mass, more preferably 0.3 to 20% by mass At least 1 structural unit: Wherein R ₁ represents a hydrogen atom or a methyl group, when R ₁ is a hydrogen atom, R ₂ represents an alkyl group having 1 to 8 carbon atoms, and when R ₁ is a methyl group, R ₂ represents a carbon number 2 To 8 alkyl groups. ]. Here, the content of each structural unit is such that the obtained polymer can be analyzed by thermal decomposition gas chromatography, and the peak area corresponding to each monomer is measured and calculated.

In the formula (1), R ₁ represents a hydrogen atom or a methyl group, when R ₁ is a hydrogen atom, R ₂ represents an alkyl group having 1 to 8 carbon atoms, and when R ₁ is a methyl group, R ₂ represents a carbon number of 2 to 8 alkyl. The alkyl group having 2 to 8 carbon atoms may, for example, be an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group. From the viewpoint of heat resistance, R ₂ is preferably an alkyl group having 2 to 4 carbon atoms, more preferably an ethyl group.

The weight average molecular weight (hereinafter sometimes referred to as Mw) of the (meth)acrylic resin contained in the intermediate layer is 100,000 to 300,000. When Mw is less than the above lower limit, the transparency at the time of exposure to a high-temperature and high-humidity environment is insufficient, and when Mw is higher than the above upper limit, the film formability at the time of producing the resin laminate (A) cannot be obtained. The Mw of the (meth)acrylic resin is preferably 120,000 or more, more preferably 150,000 or more, from the viewpoint of easily improving the transparency at the time of exposure to a high-temperature and high-humidity environment. The Mw of the (meth)acrylic resin is preferably 250,000 or less and more preferably 200,000 or less from the viewpoint of film formability at the time of producing the resin laminate (A). The weight average molecular weight is determined by gel permeation chromatography (GPC).

The (meth)acrylic resin is measured at a load of 3.8 kg at 230 ° C, and usually has a melt mass flow rate of 0.1 to 20 g/10 min, preferably 0.2 to 5 g/10 min, more preferably 0.5 to 3 g/10 min. (The following may be described as MFR.). The MFR is preferably not more than the above-mentioned upper limit, and is preferably at least the above lower limit, and is preferably from the viewpoint of film formability of the resin laminate (A). The MFR system can be measured in accordance with the method specified in JIS K 7210:1999 "Test Method for Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Plastic-Thermoplastic Plastics". The poly(methyl methacrylate)-based material was measured at a temperature of 230 ° C and a load of 3.80 kg (37.3 N).

The (meth)acrylic resin is preferably 90° C. or higher, more preferably 100° C. or higher, and more preferably a phenanthrene softening temperature of 102° C. or higher from the viewpoint of heat resistance (hereinafter, it is sometimes described as VST). .). The upper limit of the VST is not particularly limited, but is usually 150 ° C or lower. The VST system can be measured in accordance with JIS K 7206:1999 and by the B50 method described therein. The VST system can be adjusted to the above range by adjusting the kind of the monomer or its ratio.

The (meth)acrylic resin can be prepared by polymerizing the above monomers by a known method such as suspension polymerization or bulk polymerization. At this time, MFR, Mw, VST, etc. can be adjusted to a preferable range by adding an appropriate chain shifting agent. As the chain shifting agent, a suitable commercial product can be used. The amount of the chain shifting agent to be added may be appropriately determined depending on the type of the monomer or the ratio thereof, the properties to be determined, and the like.

The vinylidene fluoride resin contained in the intermediate layer of the resin laminate (A) may, for example, be a homopolymer of vinylidene fluoride or a copolymer of vinylidene fluoride and another monomer. The vinylidene fluoride resin is preferably selected from the group consisting of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, and perfluoroalkyl vinyl from the viewpoint of easily improving the transparency of the obtained resin laminate. a copolymer of at least one of a group consisting of ether and ethylene and a copolymer of vinylidene fluoride, and/or a homopolymer of vinylidene fluoride (polyvinylidene fluoride), and polyvinylidene fluoride For better.

The weight average molecular weight (Mw) of the vinylidene fluoride resin contained in the intermediate layer is preferably from 100,000 to 500,000, more preferably from 150,000 to 450,000, still more preferably from 200,000 to 450,000, and particularly preferably from 350,000 to 450,000. When Mw is at least the above lower limit, and the laminate of the present invention is exposed to a high-temperature and high-humidity environment (for example, 60 ° C and a relative humidity of 90%), the transparency of the laminate of the present invention is easily improved, which is preferable. Further, Mw is preferably not more than the above upper limit, and is preferable because the film formability of the resin laminate (A) is easily increased. The weight average molecular weight is determined by gel permeation chromatography (GPC).

The vinylidene fluoride resin is measured at a load of 3.8 kg at 230 ° C, preferably having a melt quality of 0.1 to 40 g/10 min, more preferably 0.1 to 30 g/10 min, still more preferably 0.1 to 25 g/10 min. Flow rate (MFR). More preferably, the MFR is 0.2 g/10 minutes or more, and more preferably 0.5 g/10 minutes or more. Further, the MFR is preferably 20 g/10 min or less, more preferably 5 g/10 min or less, and particularly preferably 2 g/10 min or less. The MFR is not more than the above upper limit, and is preferable because it is easy to suppress a decrease in transparency when the laminate of the present invention is used for a long period of time. MFR is at least the above lower limit, and it is preferable because the film formability of the resin laminate (A) is easily increased. The MFR system can be measured in accordance with the method specified in JIS K 7210:1999 "Test Method for Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Plastic-Thermoplastic Plastics".

The vinylidene fluoride resin is industrially produced by a suspension polymerization method or an emulsion polymerization method. The suspension polymerization method is carried out by using water as a medium, dispersing a monomer in a medium as a droplet as a dispersing agent, and polymerizing an organic peroxide dissolved in a monomer as a polymerization initiator to obtain a pellet of 100 to 300 μm. Polymer. The suspension polymer is preferable to the emulsion polymer because the production process is simple and the powder has excellent handleability, and the emulsion polymer generally does not contain an alkali metal-containing emulsifier or salting-out agent.

Commercially available products can be used as the vinylidene fluoride resin. Examples of preferred commercial products include, for example, KF Polymer (registered trademark) T # 1300, T # 1100, T # 1000, T # 850, W # 850, W # 1000, W # 1100 of Kureha Co., Ltd. And W # 1300", "SOLEF (registered trademark) 6012, 6010, and 6008 manufactured by Soevay Corporation."

The intermediate layer may further contain other resins different from the (meth)acrylic resin and the vinylidene fluoride resin. When other resins are contained, the type of the laminate of the present invention is not particularly limited as long as it does not significantly impair the transparency of the laminate of the present invention. From the viewpoint of the hardness and weather resistance of the laminate of the present invention, the amount of the other resin is preferably 15% by mass or less, more preferably 10% by mass or less, based on the total resin component contained in the intermediate layer. It is more preferably 5 mass% or less. Other resins may, for example, be polycarbonate resin, polyamide resin, acrylonitrile-styrene copolymer, methyl methacrylate-styrene copolymer, polyethylene terephthalate or the like. The intermediate layer may further contain other resins, but from the viewpoint of transparency, the amount of the other resin is preferably 1% by mass or less, and the resin contained in the intermediate layer is only (meth)acrylic resin and A vinylidene fluoride resin is more preferred.

The content of the alkali metal in the intermediate layer is preferably 50 ppm or less, more preferably 30 ppm or less, still more preferably 10 ppm or less, and particularly preferably 1 ppm or less, based on the total resin component contained in the intermediate layer. When the content of the alkali metal in the intermediate layer is not more than the above upper limit, it is easy to suppress the decrease in transparency when the laminate of the present invention is used for a long period of time in a high-temperature and high-humidity environment. The lower limit of the content of the alkali metal in the intermediate layer is 0. From the viewpoint of easily suppressing the decrease in the transparency of the laminate of the present invention, it is excellent that it is substantially not contained. Here, a small amount of an emulsifier or the like used in the production step remains in the (meth)acrylic resin and/or the vinylidene fluoride resin contained in the intermediate layer. Therefore, the residual emulsifier contains, for example, 0.05 ppm or more of an alkali metal such as sodium or potassium in the intermediate layer. In particular, when the (meth)acrylic resin and/or the vinylidene fluoride resin contained in the intermediate layer are obtained by emulsion polymerization, the amount of the emulsifier remaining in the resin increases, and the alkali metal in the intermediate layer The content also becomes high. From the viewpoint of easily suppressing the low transparency of the laminate of the present invention, the (meth)acrylic resin and the vinylidene fluoride resin contained in the intermediate layer are preferably those having a small content of an alkali metal. .

In order to set the content of the alkali metal in the resin within the above range, the amount of the alkali metal-containing compound to be used in the polymerization of the resin or the step of washing after the polymerization may be increased to remove the alkali metal-containing compound. The content of the alkali metal can be determined, for example, by inductively coupled plasma mass spectrometry (ICP/MS). Inductive combined plasma mass spectrometry, for example, the sample particles to be measured by high temperature ash melting method, high temperature ash acid dissolution method, addition of Ca ash acid dissolution method, combustion absorption method, low temperature ash acid dissolution method, etc. A suitable method is to ash the sample and dissolve it in an acid, and the alkali metal content can be determined by inductively coupled plasma mass spectrometry as long as the solution is made up to volume.

The resin laminate (A) has at least a thermoplastic resin layer present on both sides of the intermediate layer. The thermoplastic resin layer may be the same on both sides of the intermediate layer, or may be a different layer.

The thermoplastic resin layer contains at least one thermoplastic resin. The thermoplastic resin layer is preferably contained in an amount of 60% by mass or more, more preferably 70% by mass or more, more preferably, based on the total resin component contained in each of the thermoplastic resin layers, from the viewpoint of easily improving the moldability. 80% by mass or more of the thermoplastic resin. The upper limit of the amount of the thermoplastic resin is 100% by mass. The thermoplastic resin may, for example, be a (meth)acrylic resin, a polycarbonate resin or a cycloolefin resin. The thermoplastic resin is preferably a (meth)acrylic resin or a polycarbonate resin from the viewpoint of easily improving the adhesion between the thermoplastic resin layer and the intermediate layer. The thermoplastic resin layer may contain one type of thermoplastic resin, or may contain two or more kinds of thermoplastic resins.

The thermoplastic resin contained in the thermoplastic resin layer is measured in accordance with JIS K 7206:1999 from the viewpoint of heat resistance of the resin laminate (A), preferably 100 to 160 ° C, more preferably 102 to 155 ° C, and further More preferably, the thicard softening temperature is from 102 to 152 °C. Here, when the above-mentioned thicard softening temperature thermoplastic resin layer contains one type of thermoplastic resin, the thicard softening temperature of the resin is a mixture of a plurality of thermoplastic resins when the thermoplastic resin layer contains two or more kinds of thermoplastic resins. The Philippine card softens the temperature.

The thermoplastic resin layer may further contain a resin other than the thermoplastic resin (for example, a thermosetting resin such as a filler or a resin particle) for the purpose of improving the strength and elasticity of the thermoplastic resin layer. In this case, the amount of the other resin is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less, based on the total resin component contained in each of the thermoplastic resin layers. The lower limit of the amount of the other resin is 0% by mass.

The thermoplastic resin layer is excellent in moldability, and is preferably a (meth)acrylic resin layer or a polycarbonate resin layer from the viewpoint of easily improving the adhesion to the intermediate layer.

Hereinafter, an aspect of the invention in which the thermoplastic resin layer is a (meth)acrylic resin layer will be described. In this aspect, the thermoplastic resin layer contains one or more kinds of (meth)acrylic resins. The thermoplastic resin layer is preferably contained in an amount of 50% by mass or more, more preferably 60% by mass or more, and more preferably 70% by mass based on the total resin component contained in each of the thermoplastic resin layers. More than % (meth)acrylic resin.

The (meth)acrylic resin may, for example, be a resin described in the (meth)acrylic resin contained in the intermediate layer. The preferred (meth)acrylic resin described in the intermediate layer is also preferably a (meth)acrylic resin contained in the thermoplastic resin layer unless otherwise specified. The (meth)acrylic resin contained in the thermoplastic resin layer and the (meth)acrylic resin contained in the intermediate layer may be the same or different.

The weight average molecular weight (Mw) of the (meth)acrylic resin is good in moldability, and is preferably from 50,000 to 300,000, more preferably from 70,000 to 250,000, from the viewpoint of easily improving the mechanical strength. The weight average molecular weight is determined by gel permeation chromatography (GPC).

In this aspect, the thermoplastic resin layer may further contain a thermoplastic resin other than one or more kinds of (meth)acrylic resins. The thermoplastic resin other than the (meth)acrylic resin is preferably a thermoplastic resin which is compatible with the (meth)acrylic resin. Specifically, for example, a methyl methacrylate-styrene-maleic anhydride copolymer (for example, "Rejisufai" manufactured by Denki Chemical Industries, Ltd.) or a methyl methacrylate-methacrylic acid copolymer (for example, "Altuglass HT121" manufactured by Arkema" may be mentioned. ), polycarbonate resin. From the viewpoint of heat resistance, the thermoplastic resin other than the (meth)acrylic resin is preferably measured in accordance with JIS K 7206:1999, and preferably has a temperature of 115 ° C or higher, more preferably 117 ° C or higher, and still more preferably 120 ° C or higher. Ficam softens the temperature. Further, from the viewpoint of heat resistance and surface hardness, the thermoplastic resin layer is preferably substantially free of vinylidene fluoride resin.

In this aspect, the pencil hardness of the thermoplastic resin layer is preferably HB or more from the viewpoint of improving scratch resistance, more preferably F or more, and still more preferably H or more.

Next, another aspect of the invention in which the thermoplastic resin layer is a polycarbonate resin layer will be described below. In this aspect, the thermoplastic resin layer contains one or more kinds of polycarbonate resins. The thermoplastic resin layer is preferably contained in an amount of 60% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass based on the total resin component contained in each of the thermoplastic resin layers. More than 100% polycarbonate resin.

The polycarbonate resin may, for example, be a polymer obtained by a phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene or by a dihydroxydiaryl compound and a diphenyl group. The polymer obtained by the transesterification method of a carbonate reaction such as a carbonate is specifically a polycarbonate resin produced by, for example, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A).

The above dihydroxydiaryl compound is, in addition to bisphenol A, exemplified by bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-dual ( 4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxyphenyl-3- Methylphenyl)propane, 1,1-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2- Bis(4-hydroxy-3,5-dibromophenyl)propane, bis(hydroxyaryl)alkane of 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, such as 1, a bis(hydroxyaryl)cycloalkane of 1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, such as 4,4'-dihydroxydiphenyl a dihydroxy diaryl ether of 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, such as dihydroxydiaryl of 4,4'-dihydroxydiphenyl sulfide Thiols such as 4,4'-dihydroxydiphenylarylene, 4,4'-dihydroxy-3,3'-dimethyldiphenylarylene dihydroxy diaryl fluorene, For example, 4,4'-dihydroxydiphenylanthracene, 4,4'-dihydroxy-3,3'-dimethyldiphenylanthracene dihydroxydiaryl fluorene.

These may be used alone or in combination of two or more, but in addition to this, it is also possible to use a mixture of , dipiperidinylhydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, and the like.

Further, the above dihydroxyaryl compound may be used in combination with a ternary or higher phenol compound shown below. The phenolic system of more than 3 yuan may, for example, be chloropropenol, 4,6-dimethyl-2,4,6-tris-(4-hydroxyphenyl)-heptene, 2,4,6-dimethyl- 2,4,6-tris-(4-hydroxyphenyl)-heptane, 1,3,5-tris-(4-hydroxyphenyl)-benzene, 1,1,1-tris-(4-hydroxybenzene Ethyl)-ethane and 2,2-bis-[4,4-(4,4'-dihydroxydiphenyl)-cyclohexyl]-propane.

The polycarbonate resin other than the above polycarbonate resin can be exemplified by a polycarbonate synthesized from isosorbide and an aromatic diol. An example of the polycarbonate is "DURABIO (trademark registration)" manufactured by Mitsubishi Chemical Corporation.

A commercially available product can be used as the polycarbonate resin, for example, "Calibre (registered trademark) 301-4, 301-10, 301-15, 301-22, 301-30, 301- by Styron Polycarbonate Co., Ltd.). 40, SD2221W, SD2201W, TR2201" and so on.

In this aspect, the weight average molecular weight (Mw) of the polycarbonate resin is preferably from 20,000 to 70,000, more preferably from 25,000 to 60,000, from the viewpoint of easily improving the impact resistance and the form processability. The weight average molecular weight is determined by gel permeation chromatography (GPC).

In this aspect, the polycarbonate resin contained in the thermoplastic resin layer at a temperature of 300 deg.] C and a load of 1.2kg of measurement, the preferred system having 3 to 120cm ^3/10 min more preferably 3 to line 80cm ^3/10 min, and still more preferably 4 to line 40cm ^3/10 min, 10 to 40cm ^3/10 ppm and particularly preferably a melt volume flow rate system (hereinafter also referred to as a MVR.). When the MVR is higher than the lower limit described above, the fluidity is sufficiently high, and it is easy to carry out the molding process in the case of melt coextrusion molding or the like, and it is less likely to cause an appearance defect, which is preferable. When the MVR is less than the above upper limit, it is preferable because the mechanical properties such as the strength of the polycarbonate resin layer are easily increased. The MVR system can be measured in accordance with JIS K 7210 under conditions of a load of 1.2 kg at 300 °C.

In this aspect, the thermoplastic resin layer may further contain one or more thermoplastic resins other than the polycarbonate resin. The thermoplastic resin other than the polycarbonate resin is preferably a thermoplastic resin which is compatible with the polycarbonate resin, more preferably a (meth)acrylic resin, and a methacrylic acid having an aromatic ring or a cyclic olefin in the structure. The resin is even better. The thermoplastic resin layer contains a polycarbonate resin and the above-mentioned (meth)acrylic resin, and is preferable because the surface hardness of the thermoplastic resin layer can be increased as compared with the case where only the polycarbonate resin is contained.

In the range which does not inhibit the effect of the present invention, at least one of the intermediate layer and the thermoplastic resin layer in the resin laminate (A) may further contain various additives which are generally used. The additive may, for example, be a stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a foaming agent, a slip agent, a mold release agent, an antistatic agent, a flame retardant, a mold release agent, a polymerization inhibitor, and a flame retardant auxiliary agent. , coloring agents such as reinforcing agents, nucleating agents, and bluing agents.

The coloring agent may, for example, be a compound having an anthracene skeleton, a compound having a phthalocyanine skeleton, or the like. Among these, the compound having an anthracene skeleton is preferred from the viewpoint of heat resistance.

When at least one of the intermediate layer and the thermoplastic resin layer further contains a coloring agent, the content of the coloring agent in each layer can be appropriately selected depending on the purpose, the kind of the coloring agent, and the like. When the bluing agent is used as the coloring agent, the content thereof may be about 0.01 to 10 ppm depending on the total resin component contained in each layer containing the bluing agent. The content is preferably 0.01 ppm or more, more preferably 0.05 ppm or more, still more preferably 0.1 ppm or more, further preferably 7 ppm or less, more preferably 5 ppm or less, still more preferably 4 ppm or less, and particularly preferably 3 ppm or less. The bluing agent can be suitably used by a known one, and each of them is represented by a brand name, and may be, for example, Macrolex (registered trademark) Blue RR (manufactured by Bayer Co., Ltd.), Macrolex (registered trademark) Blue 3R (manufactured by Bayer Co., Ltd.), and Sumip Iast (registered trademark). Viloet B (manufactured by Sumitomo Chemtex Co., Ltd.) and Polysynthren (registered trademark) blue RLS (manufactured by Clariant Co., Ltd.), Diaresin Violet D, Diaresin BIue G, and Diaresin Blue N (above, manufactured by Mitsubishi Chemical Corporation).

In the ultraviolet absorber, since the element such as the polarizing plate (C) can be prevented from being deteriorated by ultraviolet rays, it is preferable to use at least one type of ultraviolet absorber having an absorption maximum at 320 to 400 nm. When the intermediate layer and the thermoplastic resin layer contain at least one ultraviolet absorbing agent having an absorption maximum at 320 to 400 nm, the content of the ultraviolet absorbing agent in the intermediate layer and the thermoplastic resin layer is contained in accordance with the respective layers containing the ultraviolet absorbing agent. The resin component is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.10% by mass or more. The upper limit of the content of the ultraviolet absorber having a maximum absorption at 320 to 400 nm is preferably from the viewpoint of easily suppressing bleeding from the layer and easily avoiding yellowing of the layer, and is preferably based on the total resin component contained in each layer containing the ultraviolet absorber. It is 2.0% by mass or less, more preferably 1.75% by mass or less, still more preferably 1.5% by mass or less.

The ultraviolet absorber having a maximum absorption at 320 to 400 nm is not particularly limited, and various conventionally known ultraviolet absorbers can be used. For example, it has a maximum absorption of 320 to 400 nm. It is a UV absorber, a benzophenone-based UV absorber, and a benzotriazole-based UV absorber. One type of the ultraviolet absorbers may be used alone or in combination of two or more.

Has a great absorption of 320 to 400 nm The ultraviolet absorber may, for example, be 2,4,6-gin(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-tri .

The benzophenone-based ultraviolet absorber having an absorption maximum at 320 to 400 nm may, for example, be 2,2'-dihydroxy-4-methoxy-benzophenone.

The benzotriazole-based ultraviolet absorber having an absorption maximum at 320 to 400 nm may, for example, be 2-(2'-hydroxy-5-methylphenyl)benzotriazole or 2-(2'-hydroxy-3'. 5'-di-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole, 2-(2 '-Hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2-(2' -hydroxy-3'-t-butyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5- Chlorobenzotriazole, 2-(2'-hydroxy-3'-(3",4",5",6"-tetrahydroinliminemethyl)-5'-methylphenyl)benzo Triazole, 2,2'-methylenebis(4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol), 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2(2'-hydroxy-3',5'-di-t-butyl Phenyl)-5-chlorobenzotriazole, (2(2'-hydroxy-3',5'-di-t-pentylphenyl)-5-chlorobenzotriazole, 2(2'-hydroxyl) -3',5'-di-t-butylphenyl)-5-chlorobenzotriazole, (2(2'-hydroxy-3',5'-di-p-pentylphenyl)-5 - Chlorobenzotriazole.

A commercially available product can be used as the ultraviolet absorber having a maximum absorption at 320 to 400 nm, for example, as three Adk Stab LA-F70 (2,4,6-gin(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-, manufactured by ADEKA Co., Ltd., a UV absorber three "Adk Stab LA-31, LA-31RG, LA-31G (2,2'-methylene double (4-(1,1), manufactured by ADEKA Co., Ltd. as a benzotriazole-based ultraviolet absorber) , 3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol)", Chemipro Chemical Co., Ltd. "Kemisorb 279 (2,2'-subunit double ( 4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol) and the like.

Further, in the resin laminate of the present invention, at least one of the intermediate layer and the thermoplastic resin layer may contain an ultraviolet absorber having an absorption maximum at 200 to 320 nm.

The ultraviolet absorber having a maximum absorption at 200 to 320 nm is not particularly limited, and various conventionally known ultraviolet absorbers can be used. For example, three It is a UV absorber, a benzophenone type ultraviolet absorber, a benzotriazole type ultraviolet absorber, a benzoate type ultraviolet absorber, and a cyanoacrylate type ultraviolet absorber. The ultraviolet absorber can be used by combining one or two or more kinds of the ultraviolet absorbers and the above-mentioned ultraviolet absorber having a maximum absorption at 320 to 400 nm.

Has a great absorption at 200 to 320 nm The ultraviolet absorber may, for example, be 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-tri 2,4-Diphenyl-6-(2-hydroxy-4-ethoxyphenyl)-1,3,5-three 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-three 2,4-Diphenyl-(2-hydroxy-4-butoxyphenyl)-1,3,5-three 2,4-Diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-three 2,6-diphenyl-4-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-three 2,4-Diphenyl-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-three 2,4-Diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-three 2,4-Diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3,5-three 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-N-octyloxyphenyl)-1,3,5-three , 2-(4,6-diphenyl-1,3,5-three 2-yl)-5-(2-(2-ethylhexyloxy)ethoxy)phenol.

The benzophenone-based ultraviolet absorber having an absorption maximum at 200 to 320 nm may, for example, be 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, or 2-hydroxy- 4-n-octyloxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2 '-Dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2',4,4'-four Hydroxy-benzophenone.

The benzotriazole-based ultraviolet absorber having an absorption maximum at 200 to 320 nm may, for example, be 2-(2-hydroxy-3,5-di-third-pentylphenyl)benzotriazole.

The benzoate-based ultraviolet absorber having an absorption maximum at 200 to 320 nm may, for example, be 2,4-di-t-butylphenyl-3',5'-di-t-butyl-4'-hydroxybenzene. Formate, 2,6-di-t-butylphenyl-3',5'-di-t-butyl-4'-hydroxybenzoate, n-hexadecyl-3,5-di -T-butyl-4-hydroxybenzoate, n-octadecyl-3,5-di-t-butyl-4-hydroxybenzoate.

The cyanoacrylate-based ultraviolet absorber having an absorption maximum at 200 to 320 nm may, for example, be 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate or ethyl-2-cyano-3 -(3',4'-Methylenedioxyphenyl)-acrylate.

A commercially available product can be used as the ultraviolet absorber having a maximum absorption at 200 to 320 nm, for example, as three "Kemisorb 102 (2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-N-octyloxyphenyl), manufactured by Chemipro Chemical Co., Ltd., a UV absorber )-1,3,5-three )","Adk StabLA-46(2-(4,6-diphenyl-1,3,5-three -2-yl)-5-(2-(2-ethylhexyloxy)ethoxy)phenol)", manufactured by BASF Japan Co., Ltd. "Tinuvin 1577 (2,4-diphenyl-6-) (2-hydroxy-4-hexyloxyphenyl)-1,3,5-three )"Wait.

In the resin laminate of the present invention, at least one of the intermediate layer and the thermoplastic resin layer may be contained in combination with the above-mentioned commercial product, and may be, for example, "Kemisorb 102" manufactured by Chemipro and "Adk StabLA" manufactured by ADEKA Co., Ltd. -F70", a combination of at least one of "Adk StabLA-31, LA-31RG, LA-31G", "Adk Stab LA-46" by ADEKA Co., Ltd., "Adk Stab LA-31, LA-31RG, A combination of at least one of LA-31G and "Adk Stab LA-F70", "Tinuvin 1577" by BASF Japan Co., Ltd., "Adk Stab LA-F70" by ADEKA Co., Ltd., and "Adk Stab" A combination of at least one of LA-31, LA-31RG, and LA-31G. The ultraviolet absorbers that can be used are not limited to the exemplified ones.

The average thickness of the resin laminate of the resin laminate (A) is 100 to 2000 μm, and the average thickness of the thermoplastic resin layer is preferably 10 to 200 μm.

The average thickness of the resin laminate (A) is preferably 100 μm or more, more preferably 200 μm or more, and still more preferably 300 μm or more from the viewpoint of the rigidity of the resin laminate of the polarizing plate of the present invention. Further, from the viewpoint of transparency, it is preferably 2000 μm or less, more preferably 1500 μm or less, and still more preferably 1000 μm or less. The film thickness of the resin laminate (A) is measured by a micrometer. The average value of the above measurement at 10 points of the resin laminate (A) was defined as the average value of the film thickness.

In the resin laminated body (A), the average thickness of the thermoplastic resin layer is preferably 10 μm or more, more preferably 30 μm or more, and still more preferably 50 μm or more from the viewpoint of easily increasing the surface hardness. Further, from the viewpoint of the dielectric constant, it is preferably 200 μm or less, more preferably 175 μm or less, and still more preferably 150 μm or less. The method of measuring the average value of the film thickness of the thermoplastic resin layer is as described above.

In the resin laminate (A), the average thickness of the intermediate layer is preferably 100 μm or more, more preferably 200 μm or more, and still more preferably 300 μm or more from the viewpoint of dielectric constant. Further, from the viewpoint of transparency, it is preferably 1500 μm or less, more preferably 1200 μm or less, and still more preferably 1000 μm or less. The average value of the film thickness of the intermediate layer can be measured in the same manner as the measurement of the average value of the film thickness of the thermoplastic resin layer.

The resin laminate (A) has a hard coat layer on at least one surface of the thermoplastic resin layer. The hard coat layer is preferably present on both surfaces of the thermoplastic resin layer.

The hard coat layer is formed of a hard coat composition. The hard coating composition is an essential component to impart a scratch-resistant curable compound, and may contain, for example, a curing catalyst, conductive particles, a solvent, a leveling agent, a stabilizer, an antioxidant, a colorant, etc., as needed. .

Examples of the curable compound include an acrylate compound, a urethane acrylate compound, an epoxy acrylate compound, a carboxy-modified epoxy acrylate compound, a polyester acrylate compound, a copolymer acrylate compound, and an alicyclic ring. Epoxy resin, glycidyl ether epoxy resin, vinyl ether compound, oxetane compound, and the like. The curable compound is preferably a polyfunctional acrylate compound, a polyfunctional urethane acrylate compound, a polyfunctional epoxy acrylate compound, etc. from the viewpoint of easily improving the scratch resistance of the obtained hard coat layer. A curable compound of a base polymerization type, or a thermopolymerizable compound such as an alkoxysilane or an alkyl alkoxysilane. These hardening compounds are preferably cured by irradiation with an energy ray such as an electron beam, radiation, or ultraviolet rays, or hardened by heating. These curable compounds may be used singly or in combination of two or more kinds of compounds.

The curable compound is preferably a compound having at least three (meth) acryloxy groups in the molecule from the viewpoint of easily improving the transparency and surface hardness of the hard coat layer. Examples of the curable compound having at least three (meth) acryloxy groups in the molecule include trimethylolpropane tri(meth)acrylate and trimethylolethane tri(meth)acrylate. Tris(meth)acrylate, pentaglycerol tri(meth)acrylate, pentaerythritol tri- or tetra-(meth)acrylate, dipentaerythritol tri-, tetra-, five- or six Poly(meth)acrylate of a (meth) acrylate, tripentaerythritol tetra-, penta-, hexa- or hepta-(meth) acrylate of 3 or more polyols; a compound having at least two isocyanato groups and a (meth) acrylate having a hydroxyl group, which is obtained by reacting a hydroxyl group with respect to an isocyanate group in a molar ratio or more, and a (meth) acrylonitrile in the molecule The number of oxy groups is three or more urethane (meth) acrylates [for example, by reacting a diisocyanate with neopentyl alcohol tri(meth) acrylate, a hexafunctional urethane can be obtained. Ester (meth) acrylate]; tris(meth) acrylate such as (2-hydroxyethyl)isocyano cyanide. Further, although a monomer is exemplified here, these monomers may be used as they are, and for example, an oligomer in the form of a dimer or a trimer may be used. Further, monomers and oligomers may also be used in combination. These (meth) acrylate compounds can be used singly or in combination of two or more.

A commercially available one can also be used as a curable compound having at least three (meth) acryloxy groups in the molecule. Specifically, for example, "NK Hard M101" (urethane acrylate) and "NK Ester A-TMM-3L" (neopentitol) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. Triacrylate), "NK Ester A-TMMT" (neopentitol tetraacrylate), "NK Ester A-9530" (dipentaerythritol pentaacrylate) and "NK Ester A-DPH" (two new "Pentaerythritol hexaacrylate", "KAYARAD DPCA" (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd., "Nopcocure 200" series manufactured by Sannopco Co., Ltd., and Ink Chemical Industry Co., Ltd. ) The "Unidic" series, etc.

When a compound having at least three (meth) propylene oxime groups in the molecule is used as the curable compound, other curable compounds such as ethylene glycol di(meth) acrylate or diethylene may be used in combination as needed. Alcohol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate having two (meth)acryloxy groups in the molecule The compound is used in an amount of usually 100 parts by mass, based on 100 parts by mass of the compound having at least 3 (meth) acryloxy groups in the molecule.

When the hard coating composition is cured by ultraviolet rays, it is preferred to use a photopolymerization initiator as the curing catalyst from the viewpoint of easily improving the surface hardness and adhesion of the hard coat layer. The photopolymerization initiator may, for example, be benzyl, benzophenone or a derivative thereof, thioxanthone, benzyldimethyl acetal, α-hydroxyalkylphenone, or hydroxyketone. Aminoalkylphenols, mercaptophosphine oxides, and the like. The photopolymerization initiator may be used singly or in combination of two or more. The amount of the photopolymerization initiator to be used is usually 0.1 to 5 parts by mass based on 100 parts by mass of the curable compound. When it is less than 0.1 part by weight, the curing rate tends not to be large as compared with the case where the photopolymerization initiator is not used.

A photopolymerization initiator can be used by a commercially available person. Specifically, for example, "IRGACURE 651", "IRGACURE 184", "IRGACURE 500", "IRGACURE 1000", "IRGACURE 2959", "DAROCUR 1173" manufactured by Ciba‧Specialty ‧ Chemicals Co., Ltd. IRGACURE series and DAROCUR series such as "IRGACURE 907", "IRGACURE 369", "IRGACURE 1700", "IRGACURE 1800", "IRGACURE 819", "IRGACURE 784", etc., all of which are manufactured by Nippon Kayaku Co., Ltd. KAYACURE series such as "KAYACURE ITX", "KAYACURE DETX-S", "KAYACURE BP-100", "KAYACUREBMS", "KAYACURE 2-EAQ", etc.

The hard coat layer can be provided with antistatic properties by containing conductive particles in the hard coat composition. As the conductive particles, for example, a cerium-tin composite oxide, a phosphorus-containing tin oxide, a cerium oxide such as cerium oxide, a cerium-zinc composite oxide, a titanium oxide, or an indium-tin composite oxide (ITO) is preferably used. Inorganic particles. The conductive particles described above may also be used in the form of a sol having a solid concentration of about 10 to 30% by weight.

The average particle diameter of the conductive particles is preferably 0.5 μm or less, more preferably 0.1 μm or less, and still more preferably 0.05 μm or less from the viewpoint of easily improving the transparency of the hard coat layer. The average particle diameter is preferably 0.001 μm or more from the viewpoint of easily improving the charge prevention property of the hard coat layer.

The conductive particles can be produced, for example, by a gas phase decomposition method, a plasma evaporation method, an alkoxide decomposition method, a coprecipitation method, a hydrothermal method, or the like. Further, the surface of the conductive particles may be surface-treated with, for example, a nonionic surfactant, a cationic surfactant, an anionic surfactant, a polyoxygen coupling agent, or an aluminum coupling agent.

When the hard coating composition contains conductive particles, the content thereof is preferably 2 to 50 parts by mass, more preferably 3 to 20 parts by mass, per 100 parts by mass of the curable compound. The more the content of the conductive particles is, the more the antistatic property of the hard coat layer tends to increase. However, when the amount of the conductive particles used is too large, the transparency of the hard coat layer is lowered, which is not preferable.

The hard coating composition may contain a solvent for the purpose of viscosity adjustment or the like. In particular, when the conductive particles are contained in the hard coating composition, it is preferred to contain the solvent in order to disperse the conductive particles well. When the hard coating composition contains a solvent and conductive particles, the hard coating composition may be, for example, a conductive particle and a solvent, and the conductive particles may be dispersed in a solvent, and then the dispersion and the curable compound may be mixed and produced. After the curable compound and the solvent are mixed, the conductive particles are dispersed in the mixed solution to produce.

The solvent is not particularly limited as long as it can dissolve the curable compound and can be easily volatilized after coating. The solvent may, for example, be diacetone alcohol, methanol, ethanol, isopropyl alcohol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 1-methoxy- Alcohols of 2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones of diacetone alcohol, aromatic hydrocarbons of toluene and xylene, esters of ethyl acetate and butyl acetate, water, and the like. The amount of the solvent to be used may be appropriately adjusted as long as it conforms to the properties of the curable compound.

The leveling agent composition may contain a leveling agent from the viewpoint of easily improving the coating uniformity of the hard coating agent. The leveling agent is preferably a polyoxyxane oil, and examples thereof include dimethylpolyphthalic acid oil, phenylmethylpolyphthalic acid oil, and alkyl/aralkyl modified polyoxygenated oil. Fluoropolyoxygenated oil, polyether modified polyoxygenated oil, fatty acid ester modified polyoxygenated oil, methylhydrogenated polyoxygenated oil, polyoxynoxy oil containing stanol group, polysiloxane containing alkoxy group Oxygen oil, phenol-based polyoxygenated oil, methacrylic acid modified polyoxygenated oil, amine modified polyoxygenated oil, carboxylic acid modified polyoxyxene oil, carbitol modified polyoxyxide , epoxy modified polyoxynized oil, hydrogen sulfide modified polyoxynized oil, fluorine modified polyoxygenated oil, polyether modified polyoxyxide oil and the like. These leveling agents may be used singly or in combination of two or more. The amount of the leveling agent to be used is usually 0.01 to 5 parts by mass based on 100 parts by mass of the curable compound.

As the leveling agent, a commercially available person can be used. Specifically, for example, "SH200-100cs", "SH28PA", "SH29PA", "SH30PA", "ST83PA", "ST80PA", "ST97PA" manufactured by Toray Dow Corning Silicone Co., Ltd., and "ST86PA" or any of BYK Chemie Japan's "BYK-302", "BYK-307", "BYK-320" and "BYK-330".

The hard coating composition obtained in the above manner is applied to at least one surface of the laminate having the intermediate layer and the thermoplastic resin layer, and the coating composition of the hard coating composition is, for example, a bar coating method or a micro gravure coating method. The coating method such as a roll coating method, a vertical flow coating method, a dip coating method, a spin coating method, a die coating method, a casting transfer method, or a spray coating method may be carried out. The curing of the curable coating film may be carried out by irradiation of an energy ray or heating according to the type of the hard coating composition.

When the curable compound is an energy ray-curable compound, the curable compound is cured by irradiation with an energy ray to obtain a hard coat layer. The energy line system may be, for example, an electron beam, an ultraviolet ray, a visible ray, or a radiation. The conditions such as the strength and the irradiation time may be appropriately selected depending on the type of the curable compound or the thickness of the curable coating film. The activated energy ray may be irradiated in the same manner as in the case of forming a general hard coat layer. The activated energy line can be illuminated in an inert gas environment. In order to irradiate the activated energy ray in a nitrogen atmosphere, for example, the activated energy ray may be irradiated in a container sealed with an inert gas, and nitrogen, argon or the like may be used as the inert gas. When the curable compound is a thermosetting compound, the curable compound is cured by heating to obtain a hard coat layer. The conditions such as the heating temperature and the time can be appropriately selected depending on the type of the curable compound or the thickness of the curable coating film. In order not to deform the resin substrate, the heating temperature is preferably 100 ° C or lower. When the hard coating composition contains a solvent, after the application, the curable coating film may be cured after the solvent is volatilized, or the solvent may be volatilized and the curable coating film may be cured.

The average film thickness of the hard coat layer is preferably from 0.5 to 50 μm, more preferably from 1 to 20 μm. The smaller the thickness of the hard coat layer, the less likely it is to crack, and if it is too small, the scratch resistance is insufficient, which is not preferable. The film thickness of the hard coat layer is measured using a microscope (for example, a microscope manufactured by Micro Square Co., Ltd.). The average value of the values obtained by performing the above measurement at any 10 points of the hard coat layer is defined as the average value of the film thickness.

On the surface of the hard coat layer, an antireflection treatment can be carried out by a coating method, a sputtering method, a vacuum evaporation method, or the like as needed. Further, an anti-reflective sheet which can be separately produced can be attached to one side or both sides of the hard coat layer to impart an anti-reflection effect.

The hard coat layer preferably has a water contact angle of 80° or more, more preferably 90° or more, still more preferably 100° or more, particularly preferably 105° or more, and further preferably 110° or more. The surface of the hard coat layer on the side in contact with the air, for example, the water contact angle of the surface on the side of the identification side when the resin laminate (A) is applied to the display device is preferably in the above range. When the adhesive is disposed on the surface of the hard coat layer, it is preferably a water contact angle of 30° or more, more preferably 40° or more, still more preferably 50° or more, and particularly preferably 60° or more. In this case, the water contact angle is preferably 100 or less, more preferably 95 or less, still more preferably 90 or less, and particularly preferably 85 or less. The water contact angle was measured in accordance with JIS R3257:1999 using a contact angle meter (for example, image processing type contact angle meter "FACE CA-X type" manufactured by Kyowa Interface Science Co., Ltd.).

Also, printing can be performed on the hard coat layer. Printing is preferably carried out on a hard coat layer provided with an adhesive. For example, when the laminated body of the present invention is used in a display device, for example, a frame-like pattern having a frame area of a thickness of 5 to 200 μm which is a frame outside the display area is formed. At this time, it is also possible to apply a decoration such as a pattern, whereby the outer frame of the display area can be made into a beautiful appearance excellent in design.

As the binder, a vinyl resin, a polyamide resin, a polyester resin, an acrylic resin, a polyurethane resin, a polyvinyl ketal resin, an alkyd resin, or the like is used as the binder. Further, a colored resin composition containing a pigment or a dye of a suitable color as a coloring agent is subjected to a usual printing method such as screen printing, lithography, gravure printing or flexographic printing, or a mask coating method. Alternatively, the sheet containing the colorant may be cut into a predetermined pattern by die cutting or laser or the like to be laminated on the hard coat layer.

The resin laminate (A) may have at least one functional layer in addition to the intermediate layer, the thermoplastic resin layer, and the hard coat layer. The functional layer is preferably present on the surface opposite to the intermediate layer of the thermoplastic resin layer. The functional layer may, for example, be an antireflection layer, an antiglare layer, an antistatic layer, an anti-fingerprint layer or the like. These functional layers may be laminated on the resin laminate of the present invention via an adhesive layer, or may be a coating layer laminated by coating. As the functional layer, for example, a cured film described in JP-A-2013-86273 can be used. The functional layer may be, for example, one or both sides of at least one functional layer selected from the group consisting of an anti-glare layer, an antistatic layer, and an anti-fingerprint layer, by a coating method, a sputtering method, a vacuum evaporation method. The layer to which the antireflection layer is further applied may be a layer in which an antireflective sheet is bonded to one surface or both surfaces of the at least one functional layer.

The thickness of the functional layer can be appropriately selected in accordance with the purpose of each functional layer. However, from the viewpoint of facilitating the function, it is preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 5 μm or more, and it is easy to prevent the functional layer. From the viewpoint of cracking, it is preferably 100 μm or less, more preferably 80 μm or less, and still more preferably 70 μm or less.

The resin laminated body (A) is preferably a dielectric layer having a function of 3.5 or more, more preferably 4.0 or more, and still more preferably 4.1 or more, from the viewpoint of obtaining sufficient functions when used in a display device such as a touch panel. . The upper limit of the dielectric constant is not particularly limited, but is usually 20%. The dielectric constant can be adjusted by adjusting the type or amount of the vinylidene fluoride resin contained in the intermediate layer of the resin laminate (A) or by adding a high dielectric constant compound such as ethylene carbonate or propylene carbonate. The above range. Dielectric ratio According to JIS K 6911:1995, the resin laminate (A) was allowed to stand in an environment of 23 ° C and a relative humidity of 50% for 24 hours, and was measured by an automatic balance bridging method at 3 V and 100 kHZ in this environment. value. For the measurement, a commercially available machine can be used, and for example, "precision LCR meter HP4284A" manufactured by Agilent Technologies, Inc. can be used.

The resin laminate (A) is preferably transparent when visually observed. Specifically, when the resin laminated body (A) is measured in accordance with JIS K7361-1:1997, it is preferred to have a total light transmittance of 85% or more, more preferably 88% or more, and still more preferably 90% or more. (Tt). The upper limit of total light transmittance is 100%. The resin laminate (A) after exposure to an environment of 60 ° C and a relative humidity of 90% for 120 hours has a total light transmittance of the above range.

When the resin laminate (A) is exposed to an environment of 60 ° C and a relative humidity of 90% for 120 hours, and is measured according to JIS K7136:2000, it is preferably 2.0% or less, more preferably 1.8%. The haze (the price) of 1.5% or less is more preferably the following. Further, the laminate of the present invention has a laminate of the present invention after being exposed to an environment of 60 ° C and a relative humidity of 90% for 120 hours, and preferably has a thickness of 1.5 or less, preferably more preferably 1.5 or less, in accordance with JIS Z 8722:2009. It is a yellowness (Yellow Index: YI value) of 1.4 or less, and more preferably 1.3 or less.

The transparent adhesive (B) can be suitably selected according to the member to be bonded, and for example, it can be an adhesive such as an acrylic, rubber, urethane, polyoxyl, or polyvinyl ether. From the viewpoint of excellent transparency, weather resistance, heat resistance, and the like, an acrylic pressure-sensitive adhesive containing an acrylic resin is suitable. Further, as the transparent adhesive (B), an aqueous adhesive or an active energy ray-curable adhesive can also be used.

The acrylic adhesive is generally an adhesive containing a (meth)acrylic resin and a crosslinking agent. The monomer component constituting the acrylic resin is, for example, an alkyl (meth)acrylate; one (meth)acryloyl group having an olefinic double bond in the molecule, and having a hydroxyl group in the same molecule; A compound having a polar functional group such as a carboxyl group, a decylamino group, an amine group or an epoxy group (hereinafter, sometimes referred to as a (meth)acrylic monomer having a polar functional group).

Examples of the (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylic acid. Octyl ester, 2-ethylhexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, etc. C _1-10 alkyl (meth)acrylate Wait. The alkyl (meth)acrylate is preferably n-butyl acrylate, 2-methoxyethyl acrylate or ethoxymethyl (meth)acrylate.

The (meth)acrylic acid single system having a polar functional group may, for example, (meth)acrylic acid, 2-hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate or the like (meth)acrylic acid hydroxyl group C _{1 -6} alkyl ester, (meth) acrylamide, N, N-dimethylaminoethyl ester, (meth) acrylate, glycidyl (meth) acrylate, and the like. Among these, a (meth)acrylic acid hydroxy C _1-6 alkyl ester such as 2-hydroxypropyl (meth)acrylate or hydroxyethyl (meth)acrylate is preferred.

The monomer components constituting the acrylic resin may be used alone or in combination of two or more.

A resin containing a (meth)acrylic acid alkyl ester as a main component and a small amount of a (meth)acrylic monomer having a polar functional group is preferably used.

The monomer component which is a raw material of the acrylic resin may further contain the above-mentioned (meth)acrylic acid alkyl ester and a monomer other than the (meth)acrylic acid monomer having a polar functional group (hereinafter, sometimes referred to as the third monomer). Examples thereof include a monomer having one olefinic double bond and at least one aromatic ring in the molecule, a styrene monomer, a (meth) acrylate having an alicyclic structure in the molecule, and a vinyl group. A monomer or a monomer having a plurality of (meth) acrylonitrile groups in the molecule.

In particular, a monomer having one olefinic double bond and at least one aromatic ring in the molecule can be suitably used. Among them, 2-phenoxyethyl (meth) acrylate, 2-(2-phenoxyethoxy)ethyl (meth) acrylate, ethylene oxide modified phenol (A Acrylate, 2-(o-phenylphenoxy)ethyl (meth) acrylate is preferred, and 2-phenoxyethyl acrylate is preferred.

The (meth)acrylic acid alkyl ester and the monomer (third monomer) other than the (meth)acrylic acid monomer having a functional group may be used singly or in combination of plural kinds. The structural unit derived from the third monomer is usually in the range of 0 to 20% by weight, preferably 0 to 10% by weight based on the entire acrylic resin.

The standard polystyrene-equivalent weight average molecular weight Mw obtained by gel permeation chromatography (GPC) of the acrylic resin constituting the acrylic adhesive is in the range of 1,000,000 to 2,000,000. When the weight average molecular weight Mw is 1,000,000 or more, the adhesion under high temperature and high humidity is improved, and it is easy to suppress floating or peeling between the transparent adhesive (B) and a polarizing plate or the like bonded to the adhesive layer. It occurs, and it has a tendency to improve the reworkability, so it is preferable. In addition, when the weight average molecular weight Mw of the acrylic resin is 2,000,000 or less, the size of the polarizing plate or the like bonded to the adhesive layer changes, and the adhesive layer changes in accordance with the dimensional change, and is used, for example, in a liquid crystal cell. At the time of the like, there is a tendency that the display is exposed to light or color unevenness, which is preferable. Further, the molecular weight distribution represented by the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn is preferably in the range of 3 to 7. Further, the acrylic resin contained in the acrylic pressure-sensitive adhesive may be composed only of the above-mentioned relatively high molecular weight, or may be composed of an acrylic resin different therefrom, for example, a structural unit derived from (meth) acrylate as a main component. A mixture of a weight average molecular weight of 50,000 to 300,000 or the like is used.

The above acrylic resin constituting the acrylic pressure-sensitive adhesive can be produced by a known method such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, or the like. A polymerization initiator is usually used in the production of the acrylic resin. The polymerization initiator may, for example, be an azo compound, an organic peroxide, an inorganic peroxide, a redox initiator which is used in combination with a peroxide and a reducing agent, or the like. Among these, 2,2'-azobisisobutyronitrile, benzammonium peroxide, ammonium persulfate or the like is preferably used. The polymerization initiator is usually used in a ratio of about 0.001 to 5 parts by mass based on 100 parts by mass of the total of the monomers which are raw materials of the acrylic resin.

The crosslinking agent is a compound having at least two functional groups which can be crosslinked with a structural unit derived from a (meth)acrylic monomer having a polar functional group in the acrylic resin in the molecule, and examples thereof include an isocyanate system. A compound, an epoxy compound, a metal chelate compound, an aziridine compound or the like.

Among these crosslinking agents, an isocyanate compound is preferred. The isocyanate-based compound is an addition product, a dimer, a trimer or the like which can be obtained by reacting a compound having at least two isocyanato groups (-NCO) in a molecule with a polyol. Form use. Specifically, for example, toluene diisocyanate, an adduct obtained by reacting tolyl diisocyanate with a polyhydric alcohol, a dimer of tolylene diisocyanate, a terpolymer of tolylene diisocyanate, hexamethylene diisocyanate, or the like can be used. An adduct obtained by reacting hexamethylene diisocyanate with a polyhydric alcohol, a dimer of hexamethylene diisocyanate, a terpolymer of hexamethylene diisocyanate, or the like.

The crosslinking agent is usually formulated in an amount of about 0.01 to 5 parts by mass, preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, based on 100 parts by mass of the acrylic resin. The blending amount of the crosslinking agent with respect to 100 parts by mass of the acrylic resin is not less than the above lower limit, and is preferable because the durability of the transparent adhesive (B) is easily improved.

In the transparent adhesive (B), other ingredients may be blended as needed. Other components which can be adjusted include, for example, metal fine particles, metal oxide fine particles, or conductive fine particles coated with fine particles such as metal, an ion conductive composition, an ionic compound having an organic cation or an anion, and a decane coupling agent. A light-diffusing fine particle such as a solvent, a crosslinking catalyst, a weathering stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, a resin other than the above acrylic resin, or an organic particle. Further, it is also useful as a harder adhesive layer by dispersing an ultraviolet curable compound in an adhesive to form an adhesive layer and then irradiating it with ultraviolet rays.

The method of applying the transparent adhesive (B) to the resin laminate (A) (or coating or bonding) may, for example, be a laminator, a bar coating method, a micro gravure coating method, a drum coating method, or a dipping method. Coating method, spin coating method, die coating method, casting transfer method, vertical flow coating method, spray coating method, and the like.

Specifically, the resin layered system of the present invention can be directly applied to one side or both sides of the resin laminate (A) by an adhesive composition in which an adhesive is dissolved in a suitable solvent (for example, ethyl acetate or the like), and dried, etc. Alternatively, by using a release film as a substrate, an adhesive having a release film obtained by applying the above-mentioned adhesive composition to a release film may be bonded to one side or both sides of the resin laminate (A). . In addition, the release film of one side of the release sheet-type adhesive having the release film adhered to both surfaces of the transparent adhesive is peeled off and bonded to the surface of the resin laminate (A) to obtain the resin laminate of the present invention. body. Commercially available products of the double-sided separator type adhesive can be, for example, a non-carrier adhesive film or a substrate-free adhesive sheet which is sold by Lintec Co., Ltd. or Nitto Denko Co., Ltd. Further, among the components contained in the adhesive, the component which is not dissolved in water may be in a state of being dispersed in the system of the adhesive composition.

When the transparent adhesive (B) is bonded to one side or both sides of the resin laminated body (A) by using an adhesive with a release film, the release film may be, for example, polyethylene terephthalate or polyparaphenylene. a film composed of various resins of butylene dicarboxylate, polycarbonate, polyarylate, polypropylene or polyethylene as a substrate, and a release treatment by a polyoxygen treatment at a joint surface with an adhesive layer of the substrate Processed by. Such a release film is also referred to as a separation membrane or a separator.

The aqueous adhesive is generally composed of, for example, a polyvinyl alcohol-based resin or a urethane resin as a main component, and a composition such as an isocyanate-based compound, an epoxy compound crosslinking agent, or a curable compound is added in order to improve adhesion. .

When a polyvinyl alcohol-based resin is used as a main component of the aqueous binder, a partially saponified polyvinyl alcohol and a fully saponified polyvinyl alcohol may be used, for example, a carboxy-modified polyvinyl alcohol or an ethyl acetylated modified polyvinyl alcohol. A modified polyvinyl alcohol-based resin of hydroxymethyl-modified polyvinyl alcohol and an amine-modified polyvinyl alcohol. Although an aqueous solution of such a polyvinyl alcohol-based resin can be used as the aqueous adhesive, the concentration of the polyvinyl alcohol-based resin in the aqueous adhesive is usually from 1 to 10 parts by mass, preferably from 1 to 10 parts by mass per 100 parts by mass of water. 5 parts by mass.

In the aqueous adhesive comprising an aqueous solution of a polyvinyl alcohol-based resin, in order to improve the adhesion, the curability such as a polyvalent aldehyde, a water-soluble epoxy resin, a melamine-based compound, a zirconia-based compound, and a zinc compound can be adjusted. Compound. For example, a water-soluble epoxy resin is a polyamine polyamine obtained by reacting a polyalkyleneamine such as diethylenetriamine or triethylenetetramine with a dicarboxylic acid such as adipic acid, and A water-soluble polyamine epoxy resin obtained by epichlorohydrin reaction. For such a commercial product of polyamine epoxy resin, "Sumirez Resin 650" and "Sumirez Resin 675" sold by Sumitomo Chemtex Co., Ltd., "WS-" sold by Japan PMC Co., Ltd. 525" and so on. When the water-soluble epoxy resin is blended, the amount thereof is usually from about 1 to 100 parts by mass, preferably from 1 to 50 parts by mass, per 100 parts by mass of the polyvinyl alcohol-based resin.

Moreover, when a urethane resin is used as a main component of an aqueous adhesive agent, it is effective to make a polyester type ionic polymer type urethane resin as a main component of an aqueous adhesive agent. Here, the polyester-based ionic polymer type urethane resin refers to a urethane resin having a polyester skeleton, and a small amount of an ionic component (hydrophilic component) is introduced therein. Since such an ionic polymer type urethane resin is directly emulsified in water to form an emulsion without using an emulsifier, it can be used as an aqueous binder. When a polyester-based ionic polymer type urethane resin is used, it is effective to prepare a water-soluble epoxy compound as a crosslinking agent. The polyester-based ionic polymer-type urethane resin is used as an adhesive agent for a polarizing plate, for example, in JP-A-2005-70140 and JP-A-2005-208456.

The aqueous adhesive is usually used in the form of an aqueous adhesive composition dissolved in water. The aqueous adhesive composition can be applied to one side or both sides of the resin laminate (A) and dried to form a transparent adhesive (B). Further, the components which are not dissolved in the water contained in the aqueous binder may be in a state of being dispersed in the system.

Further, for example, when the resin laminate of the present invention is bonded to a polarizing plate, an aqueous adhesive is injected between the polarizing plate and the resin laminate (A), and then heated to evaporate water while performing thermal crosslinking reaction. Thereby, the transparent adhesive (B) can be formed so that the two are sufficiently adhered.

The active energy ray-curable adhesive is cured by irradiation with an active energy ray, and the resin laminate (A) and the polarizing plate are brought to a practical strength. For example, a cationically polymerizable active energy ray-curable adhesive containing an epoxy compound and a cationic polymerization initiator, and an active energy ray-curing type containing a radical polymerizable property of an acrylic hardening component and a radical polymerization initiator And an agent containing a cationically polymerizable hardening component such as an epoxy compound and a radical polymerizable hardening component such as an acrylic compound, and a cationic polymerization initiator and a radical polymerization initiator are formulated therein. An energy ray-curable adhesive and an electron beam-curable adhesive which irradiates an electron beam to an active energy ray-curable adhesive which does not contain an initiator. A radical energy polymerizable active energy ray-curable adhesive containing an acrylic curing component and a radical polymerization initiator is preferred. Further, a cationically polymerizable active energy ray-curable adhesive which can be used substantially without a solvent and which contains an epoxy compound and a cationic polymerization initiator is preferred.

An epoxy compound which is cationically polymerizable and which is itself liquid at room temperature, has moderate fluidity even in the absence of a solvent, imparts appropriate hardening strength, and is formulated with a suitable cationic polymerization initiator. The obtained active energy ray-curable adhesive is preferably used in a manufacturing apparatus of a polarizing plate because it is a drying apparatus which is usually necessary in the step of connecting the laminated body and the polarizing plate. Moreover, by irradiating an appropriate amount of active energy rays, the curing speed can be promoted, and the production speed can be increased.

The epoxy compound used in such an adhesive may be, for example, a glycidyl etherate of an aromatic compound or a chain compound having a hydroxyl group, a glycidylamine compound of a compound having an amine group, or a chain having a CC double bond. An epoxide of a compound, an alicyclic epoxy compound in which a saturated carbocyclic ring is bonded to a glycidyloxy group or an epoxy group directly or via an alkyl group, or an epoxy group is directly bonded to a saturated carbocyclic ring. Wait. These epoxy compounds may be used singly or in combination of plural kinds. Among them, the alicyclic epoxy compound is preferably used because it has excellent cationic polymerizability.

The glycidyl etherate of the aromatic compound or the chain compound having a hydroxyl group can be produced, for example, by subjecting the hydroxyl group of the aromatic compound or the chain compound to epichlorohydrin addition and condensation under basic conditions. . The glycidyl etherate of the aromatic compound or the chain compound having such a hydroxyl group includes: a bisphenol glycidyl ether, a polyaromatic ring type epoxy resin, an alkylene glycol or a polyalkylene group Alcohol diglycidyl ether and the like.

Examples of the bisphenol-based glycidyl ethers include glycidyl ethers of bisphenol A and oligomers thereof, glycidyl ethers of bisphenol F, and oligomers thereof, 3, 3', 5, A glycidyl etherate of 5'-tetramethyl-4,4'-biphenol and an oligomer thereof.

The polyaromatic epoxy resin may, for example, be a glycidyl etherate of a phenol novolak resin, a glycidyl etherate of a cresol novolak resin, a glycidyl etherate of a phenol aralkyl resin, or a naphthol aralkyl. A glycidyl etherate of a base resin, a glycidyl etherate of a phenol dicyclopentadiene resin, or the like. Further, the glycidyl etherate of phenols and oligomers thereof are also polyaromatic ring-type epoxy resins.

The diglycidyl ether of the alkylene glycol or the polyalkylene glycol may, for example, be a glycidyl etherate of ethylene glycol, a glycidyl etherate of diethylene glycol, or a 1,4-butanediol. A glycidyl etherate, a glycidyl etherate of 1,6-hexanediol, or the like.

The glycidylamine compound of the compound having an amine group can be produced, for example, by subjecting an amine group of the compound to epichlorohydrin addition and condensation under basic conditions. The compound having an amine group may have a hydroxyl group at the same time. The glycidylamine compound of such an amine group-containing compound contains glycidylamine of 1,3-phenylenediamine and oligomer thereof, glycidylamine of 1,4-phenylenediamine And oligomers thereof, glycidyl amination of 3-aminophenol and glycidyl etherate and oligomers thereof, glycidylamines and glycidyl etherates of 4-aminophenol and Oligomers, etc.

An epoxide of a chain compound having a C-C double bond can be produced by a method of epoxidizing a C-C double bond of the chain compound using a peroxide under basic conditions. The chain compound having a C-C double bond includes butadiene, polybutadiene, isoprene, pentadiene, hexadiene, and the like. Further, a terpene having a double bond may be used as an epoxidation raw material, and an acyclic monoterpene may be a linalool or the like. The peroxide used in the epoxidation may be, for example, hydrogen peroxide, peracetic acid, tert-butyl hydroperoxide or the like.

An alicyclic epoxy compound having a glycidyloxy group or an epoxy group bonded to a saturated carbocyclic ring directly or via an alkyl group may be a hydroxy group exemplified by a bisphenol. A glycidyl etherate of a hydrogenated polyhydroxy compound obtained by hydrogenating an aromatic ring of a compound, a glycidyl etherate of a cycloalkane compound having a hydroxyl group, an epoxide of a cycloalkyl compound having a vinyl group, or the like.

The epoxy compound described above can be easily taken from a commercial product, and is represented by a product name, for example, "jER" series sold by Mitsubishi Chemical Corporation, and "Epiclon" sold by DIC Corporation. "Epotote (registered trademark)" sold by Dongdu Chemical Co., Ltd., "Adeka Resin (registered trademark)" sold by ADEKA Co., Ltd., and "Denacol (registered trademark)" sold by Nagase Chemtex Co., Ltd. "Dow Epoxy" sold by Dow Chemical Co., Ltd., "Tepic (registered trademark)" sold by Nissan Chemical Industries Co., Ltd., etc.

On the other hand, an alicyclic epoxy compound in which an epoxy group is directly bonded to a saturated carbocyclic ring can be, for example, a non-aromatic ring having a CC double bond in the ring by using a peroxide under basic conditions. Manufactured by a method of CC double bond epoxidation of a compound. The non-aromatic cyclic compound having a CC double bond in the ring may, for example, be a compound having a cyclopentene ring, a compound having a cyclohexene ring, or at least two further bonded to a cyclopentene ring or a cyclohexene ring. A polycyclic compound or the like which forms an additional ring by a carbon atom. The non-aromatic cyclic compound having a C-C double bond in the ring may have other C-C double bonds outside the ring. Examples of the non-aromatic cyclic compound having a C-C double bond in the ring include cyclohexene, 4-vinylcyclohexene, limonene belonging to monocyclic monoterpene, and α-pinene.

The alicyclic epoxy compound in which an epoxy group is directly bonded to a saturated carbocyclic ring may be formed by forming at least two alicyclic groups having an epoxy group directly bonded to the above ring in the molecule via a suitable linking group. Structured compound. The linking group here includes, for example, an ester bond, an ether bond, an alkylene bond or the like.

Specific examples of the alicyclic epoxy compound in which an epoxy group is directly bonded to a saturated carbocyclic ring are as follows.

3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-vinylcyclohexane, 1,2-epoxy-4 - Epoxyethylcyclohexane, 1,2-epoxy-1-methyl-4-(1-methylepoxyethyl)cyclohexane, 3,4-epoxycyclohexyl Addition of base (meth) acrylate, 2,2-bis(hydroxymethyl)-1-butanol and 4-epoxyethyl-1,2-epoxycyclohexane, exoethyl double (3,4-epoxycyclohexanecarboxylate), oxydiethylidene bis(3,4-epoxycyclohexanecarboxylate), 1,4-cyclohexanedimethyl bis ( 3,4-epoxycyclohexanecarboxylate), 3-(3,4-epoxycyclohexylmethoxycarbonyl)propyl 3,4-epoxycyclohexanecarboxylate, and the like.

The above-described alicyclic epoxy compound in which the epoxy group is directly bonded to the saturated carbocyclic ring can be easily obtained as a commercial product, and is represented by a trade name, for example, the "Celloxide" series sold by Daicel Co., Ltd. and " Cyclomer, the "Cyracure UVR" series sold by Dowchemical.

The curable adhesive containing an epoxy compound may further contain an active energy ray-curable compound other than the epoxy compound. Examples of the active energy ray-curable compound other than the epoxy compound include an oxetane compound and an acrylic compound. Among them, an oxetane compound is preferably used in combination because it has a possibility of promoting the curing rate during cationic polymerization.

The oxetane compound is a compound having a 4-membered cyclic ether in the molecule, and examples thereof include the following.

1,4-Bis[(3-ethyloxetan-3-yl)methoxymethyl]benzene, 3-ethyl-3-(2-ethylhexyloxymethyl)oxyheterocycle Butane, bis(3-ethyl-3-oxetanylmethyl)ether, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3- (cyclohexyloxymethyl)oxetane, phenol novolac oxetane, 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, etc. .

The oxetane compound can also be easily obtained from a commercial product, and is represented by a trade name, for example, "Aron Oxetane (registered trademark)" series sold by Toagosei Co., Ltd., and sold by Ube Industries Co., Ltd. ETERNACOLL (registered trademark) series, etc.

The curable compound containing an epoxy compound or, for example, a compound is preferably a non-solvent which is not diluted with an organic solvent or the like in order to make the adhesive prepared as such a solvent-free. Further, it is a small component which comprises a cationic polymerization initiator or a sensitizer which will be described later, and is a component which is a component of a binder polymerization initiator or a sensitizer, which is a compound which has been dissolved in an organic solvent. A body or a liquid is preferred.

The cationic polymerization initiator is a compound which generates a cationic species by irradiation with an active energy ray such as ultraviolet rays. The inorganic diazonium salt; the aromatic sulfonium salt or the sulfonium salt of the aromatic sulfonium salt; the iron-aromatic hydrocarbon complex may be used as long as it can impart the bonding strength and the curing speed required for the formulation of the adhesive. Wait. These cationic polymerization initiators may be used singly or in combination of plural kinds.

The aromatic diazonium salt can be exemplified as follows.

Benzene diazo hexafluoroantimonate, benzene diazo hexafluorophosphate, benzene diazo hexafluoroborate, and the like.

The aromatic onium salt system can be exemplified as follows.

Diphenylphosphonium (pentafluorophenyl) borate, diphenylphosphonium hexafluorophosphate, diphenylphosphonium hexafluoroantimonate, bis(4-mercaptophenyl)phosphonium hexafluorophosphate, and the like.

The aromatic onium salt system can be exemplified as follows.

Triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium (pentafluorophenyl)borate, diphenyl(4-phenylthiophenyl)phosphonium hexafluoroantimonate Acid salt, 4,4'-bis(diphenyldihydrothio)diphenyl sulfide dihexafluorophosphate, 4,4'-bis[bis(β-hydroxyethoxyphenyl)dihydrogen Diphenyl sulfide dihexafluoroantimonate, 4,4'-bis[bis(β-hydroxyethoxyphenyl)dihydrothio]diphenyl sulfide dihexafluorophosphate, 7- [Bis(p-tolylmethyl)dihydrothio]-2-isopropylthioxanthone hexafluoroantimonate, 7-[bis(p-tolylmethyl)dihydrothio]-2 -isopropyl thioxanthone oxime (pentafluorophenyl) borate, 4-phenylcarbonyl-4'-diphenyldihydrothiodiphenyl sulfide hexafluorophosphate, 4-(p-- Tri-butylphenylcarbonyl)-4'-diphenyldihydrothiodiphenyl Thioether hexafluoroantimonate, 4-(p-tris-butylphenylcarbonyl)-4'-bis(p-tolylmethyl)dihydrothio-diphenyl sulfide quinone (pentafluorobenzene) Base) borate and the like.

The iron-aromatic hydrocarbon complex system can be exemplified as follows.

Xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene-cyclopentadienyl iron (II) ginseng ( Xylene-cyclopentadienyliron(II) tris(trifluoromethylsulfonyl)methanide).

Among the cationic polymerization initiators, the aromatic sulfonium salt has an ultraviolet absorbing property in the wavelength range of 300 nm or more, and can provide an adhesive (or an adhesive layer) which is excellent in curability and has good mechanical strength and adhesion strength. More suitable to use.

The cationic polymerization initiator can also be easily obtained from a commercial product, and is represented by a brand name, for example, "Kayarad (registered trademark)" series sold by Nippon Kayaku Co., Ltd., and "Cyracure UVI" sold by Dow Chemical Co., Ltd. Series, photo-acid generator "CPI" series sold by San-Apro Co., Ltd., photochemical generators "TAZ", "BBI" and "DTS" sold by Green Chemical Co., Ltd., and "ADEK Co., Ltd." "Adeka Optomer" series, "RHODORSIL" (registered trademark) sold by Rhodia.

In the active energy ray-curable adhesive, the cationic polymerization initiator is usually formulated in an amount of 0.5 to 20 parts by mass, preferably 1 to 15 by mass, based on 100 parts by mass of the total amount of the active energy ray-curable adhesive. Share. When the amount is too small, the hardening is insufficient, and the mechanical strength or the strength of the adhesive after hardening may be lowered. Moreover, when the amount is too large, the ionic substance in the transparent adhesive increases, and the hygroscopicity of the transparent adhesive becomes high, and the durability of the resin laminate may be lowered.

When an active energy ray-curing type adhesive is used for the electron beam curing type, it is not particularly necessary to contain a photopolymerization initiator in the composition. However, when it is used in an ultraviolet curing type, it is preferred to use a photoradical generator. The photoradical generating agent may, for example, be a hydrogen abstraction type photoradical generator and a cleavage photoradical generator.

Examples of the dehydrogenation type photoradical generator include 1-methylnaphthalene, 2-methylnaphthalene, 1-fluoronaphthalene, 1-chloronaphthalene, 2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, and 1 -naphthalene derivatives such as iodophthalene, 2-iodonaphthalene, 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dicyanonaphthalene, hydrazine, 1, 2-benzopyrene, 9,10-dichloropurine, 9,10-dibromoindole, 9,10-diphenylanthracene, 9-cyanoindole, 9,10-dicyanoguanidine, 2,6, 9,10-tetracyanoindole and the like anthracene derivatives, anthracene derivatives, carbazole, 9-methylcarbazole, 9-phenylcarbazole, 9-propen-2-yl-9H-carbazole, 9-propyl -9H-carbazole, 9-vinylcarbazole, 9H-carbazole-9-ethanol, 9-methyl-3-nitro-9H-carbazole, 9-methyl-3,6-dinitro -9H-carbazole, 9-octylcarbazole, 9-oxazole methanol, 9-oxazolidine acid, 9-carbazole propionitrile, 9-ethyl-3,6-dinitro-9H-carbazole, 9-ethyl-3-nitrocarbazole, 9-ethylcarbazole, 9-isopropylcarbazole, 9-(ethoxycarbonylmethyl)carbazole, 9-(morpholinylmethyl)fluorene Azole, 9-acetamidocarbazole, 9-allylcarbazole, 9-benzyl-9H-carbazole, 9-carbazoleacetic acid, 9-(2-nitrophenyl)carbazole, 9- (4-methoxyphenyl)carbazole, 9-(1-ethoxy-2-methyl-propyl )-9H-carbazole, 3-nitrocarbazole, 4-hydroxycarbazole, 3,6-dinitro-9H-carbazole, 3,6-diphenyl-9H-carbazole, 2-hydroxyindole Carbazole, carbazole derivatives such as 3,6-diethylindenyl-9-ethylcarbazole, benzophenone, 4-phenylbenzophenone, 4,4'-bis(dimethoxy) Benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-benzylidene benzoic acid methyl Ester, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2, Benzophenone derivatives such as 4,6-trimethylbenzophenone, aromatic carbonyl compounds, [4-(4-methylphenylthio)phenyl]-phenyl ketone, xanthone , thioxanthone, 2-chlorothiazepinone, 4-chlorothiazepinone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylsulfide a thioxanthone derivative such as a fluorenone, a 2,4-diethyl thia fluorenone or a 1-chloro-4-propoxy thioxanthone or a coumarin derivative.

The cleavage type photoradical generator is a photoradical generator of a type which generates a radical by cleavage of an active energy ray, and specific examples thereof include a benzoin ether derivative and an acetophenone derivative. Or arylalkyl ketones, anthrones, fluorenylphosphine oxides, thiobenzoic acid S-phenyl esters, ferrocenes, and derivatives thereof, but are not limited herein. Commercially available cleavage type photoradical generators are, for example, 1-(4-dodecylbenzylidene)-1-hydroxy-1-methylethane, 1-(4-isopropylbenzene). Mercapto)-1-hydroxy-1-methylethane, 1-benzylidene-1-hydroxy-1-methylethane, 1-[4-(2-hydroxyethoxy)-benzene Mercapto]-1-hydroxy-1-methylethane, 1-[4-(propylene methoxyethoxy)-benzylidene]-1-hydroxy-1-methylethane, diphenyl Ketone, phenyl-1-hydroxy-cyclohexyl ketone, benzyl dimethyl acetal, bis(cyclopentadienyl)-bis(2,6-difluoro-3-indolyl-phenyl)titanium, (η 6-isopropylbenzene)-(η 5-cyclopentadienyl)-iron (II) hexafluorophosphate, trimethyl benzhydryldiphenylphosphine oxide, bis(2,6-di Methoxy-benzylidene)-(2,4,4-trimethyl-pentyl)-phosphine oxide, bis(2,4,6-trimethylbenzylidene)-2,4-di Pentyloxyphenylphosphine oxide or bis(2,4,6-trimethylbenzylidene)phenyl-phosphine oxide, (4-morpholinylbenzylidene)-1-benzyl-1- Dimethylaminopropane, 4-(methylthiobenzimidyl)-1-methyl-1-morpholinylethane, and the like, but is not limited thereto.

In the active energy curing type adhesive used in the present invention, any of the photoradical generating agents contained in the electron beam curing type, that is, any of the dehydrogenating or cleavable photoradical generating agents may be used alone. In addition, it is also possible to use a combination of a plurality of cleavage type photoradical generators from the viewpoint of the stability of the photoradical generator monomer and the curability. Among the cleavable photoradical generators, fluorenylphosphine oxides are preferred, more specifically trimethyl benzhydryldiphenylphosphine oxide (trade name "DAROCURE TPO", Ciba‧Japan (shares) )), bis(2,6-dimethoxy-benzylidene)-(2,4,4-trimethyl-pentyl)-phosphine oxide (trade name "CGI 403", Ciba‧Japan )) or bis(2,4,6-trimethylbenzylidene)-2,4-dipentyloxyphenylphosphine oxide (trade name "Irgacure 819", Ciba‧ Japan (share)) is preferred .

The active energy ray-curable adhesive may contain a sensitizer as needed. By using a sensitizer, the reactivity is improved, and the mechanical strength or the subsequent strength of the adhesive (adhesive layer) after hardening is further enhanced. The sensitizer can be suitably applied to the foregoing.

When the sensitizer is formulated, the amount thereof is preferably in the range of 0.1 to 20 parts by mass based on 100 parts by mass of the total amount of the active energy ray-curable adhesive.

The active energy ray-curable adhesive can be formulated with various additives within a range that does not impair the effect. The additive to be added may, for example, be an ion scavenger, an antioxidant, a chain shifting agent, a tackifier, a thermoplastic resin, a filler, a flow regulator, a plasticizer, an antifoaming agent, or the like.

The active energy ray-curable adhesive is usually used in the form of an active energy ray-curable adhesive composition dissolved in a solvent. The layered system of the present invention can be obtained by applying the adhesive composition to one side or both sides of the resin laminate (A) and drying it. Further, the component which is not dissolved in the water contained in the adhesive may be in a state of being dispersed in the system.

The active energy ray-curable adhesive can be applied to the resin laminate (A) by the above-described coating method. In this case, the viscosity of the active energy ray-curable adhesive may be any one having a viscosity which can be applied by various methods, but the viscosity at a temperature of 25 ° C is preferably in the range of 10 to 30,000 mPa ‧ sec. A range of 50 to 6,000 mPa ‧ is preferred. When the viscosity is too small, it is difficult to obtain a uniform coating film without unevenness. On the other hand, if the viscosity is too large, it becomes difficult to flow, and similarly, it is difficult to obtain a homogeneous coating film having no unevenness. Here, the viscosity is a value measured at 60 rpm after a B-type viscometer is used and the adhesive is adjusted to 25 ° C.

The active energy ray-curable adhesive can be used in the form of an electron beam curing type or an ultraviolet curing type. The active energy ray line of the present invention is defined as an energy line that allows decomposition of a compound that produces an active species to produce an active species. Examples of such active energy lines include visible light, ultraviolet light, infrared light, X-rays, alpha rays, beta rays, gamma rays, and electron beams.

In the electron beam curing type, the irradiation conditions of the electron beam may be any suitable conditions as long as the active energy ray-curable adhesive can be cured. For example, the acceleration voltage of the electron beam irradiation is preferably 5 kV to 300 kV, more preferably 10 kV to 250 kV. When the accelerating voltage is less than 5 kV, the electron beam does not reach the adhesive and becomes insufficiently hardened. When the accelerating voltage exceeds 300 kV, the electron beam bounces due to excessive penetration of the sample, and there is a resin laminate (A) or the like. Causes damage. The amount of irradiation line is 5 to 100 kGy, more preferably 10 to 75 kGy. When the amount of the irradiation line is less than 5 kGy, the adhesive is insufficiently hardened, and when it exceeds 100 kGy, the resin laminate (A) or the like is damaged, and mechanical strength is lowered or yellowed, and desired optical characteristics are not obtained.

The electron beam irradiation is usually carried out in an inert gas, but if necessary, it can be carried out in the atmosphere or under a slight introduction of oxygen. Further, depending on the material of the resin laminate of the present invention, when the oxygen is impeded by the surface of the resin laminate which is initially irradiated by the electron beam by appropriate introduction of oxygen, damage to the resin laminate of the present invention can be prevented. The electron beam is efficiently irradiated only to the adhesive.

In the ultraviolet curing type, the light irradiation intensity of the active energy ray-curable adhesive is determined depending on the respective compositions of the adhesive, and is not particularly limited, and is preferably 10 to 5000 mW/cm ² . A / cm ² less than the light irradiation intensity of 10mW, the reaction time is too long, more than 5000 mW / cm ² when, due to heat generation during the polymerization of the radiation source and from the heat of the adhesive, it is possible to cause yellowing of the resin laminate according to the present invention Or deteriorated. Further, the irradiation intensity is preferably a strength in a wavelength region effective for activation of a photocationic polymerization initiator, more preferably a wavelength in a wavelength region of 400 nm or less, and more preferably in a wavelength region of 280 to 320 nm. Strength. In such a light irradiation intensity of exposure to 1 or a plurality of times, so that the integrated light amount became 10mJ / cm ² or more, preferably 10 to line 5,000mJ / cm ² of the embodiment is set as preferred. When the cumulative amount of light is less than 10 mJ/cm ² , the generation of the active species derived from the polymerization initiator is insufficient, and the curing of the adhesive is insufficient. On the other hand, the cumulative amount of light exceeds 5,000mJ / cm ^2, the irradiation time is very long, detrimental to productivity is improved. In this case, whether the amount of accumulated light in any of the wavelength regions (UVA (320 to 390 nm) or UVB (280 to 320 nm) or the like is required to differ is different depending on the combination of the resin laminate (A) or the adhesive species.

The light source used in the polymerization hardening of the adhesive agent by irradiation with the active energy ray in the present invention is not particularly limited, and examples thereof include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, and a halogen lamp. Carbon arc lamp, tungsten wire lamp, gallium lamp, excimer laser, LED light source that generates light with a wavelength range of 380 to 440 nm, chemical lamp, black light lamp, microwave excited mercury lamp, metal halide lamp. From the viewpoint of energy stability or the simplicity of the device, an ultraviolet light source having a light-emitting distribution at a wavelength of 400 nm or less is preferable.

The film thickness of the transparent adhesive (B) is preferably from 5 to 500 μm, more preferably from 10 to 350 μm. When the thickness of the adhesive layer is 500 μm or less, the adhesion under high temperature and high humidity is improved, and it is easy to suppress the occurrence of floating or peeling between the adhesive layer and the polarizing plate or the like to which the adhesive layer is bonded. Moreover, there is a tendency to increase the reworkability. In addition, when the thickness of the polarizing plate to be bonded is changed by 5 μm or more, the adhesive layer changes in accordance with the dimensional change, and the durability against dimensional change is improved.

The transparent adhesive (B) has a total light transmittance of 90% or more, more preferably 92% or more, and still more preferably 94% or more. When the total light transmittance of the transparent adhesive (B) is less than the above lower limit, sufficient transparency cannot be obtained when the resin laminate (A) is laminated.

The transparent adhesive (B) preferably has a haze of 2% or less, more preferably 1.5% or less, and still more preferably 1% or less.

The polarizing plate (C) is not particularly limited, and is a polarizer having a polarizer and a polarizer protective film fixed to at least one surface of the polarizer, and may be laminated with other functional films or functional sheets as needed. Examples of the polarizer include the following (a) and (b). (a) Adsorption and alignment of a film of a polyvinyl alcohol (PVA) resin, a polyvinyl acetate resin, an ethylene/vinyl acetate (EVA) resin, a polyamide resin, or a polyester resin to a dichroic dye By. (b) a molecularly-locked polyvinyl alcohol/polyvinyl copolymer having a dichroic dehydrated product of polyvinyl alcohol (polyvinyl group) in a molecularly oriented polyvinyl alcohol film.

The polyvinyl alcohol-based resin can be usually obtained by saponification using a polyvinyl acetate-based resin. The degree of saponification is usually 85 mol% or more, preferably 90 mol or more, more preferably 99 to 100 mol%. The polyvinyl acetate-based resin is, in addition to the polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of, for example, another monomer copolymerizable with vinyl acetate, such as ethylene-vinyl acetate. Copolymers, etc. Examples of the other monomer include unsaturated carboxylic acids, olefins, vinyl ethers, and unsaturated sulfonic acids. The molecular weight of the polyvinyl alcohol-based resin is not particularly limited, but is preferably from about 1,000 to 10,000, more preferably from about 1,500 to 5,000. Polyvinyl alcohol can be modified. The modified polyvinyl alcohol may, for example, be a polyethylene formaldehyde modified with an aldehyde, a polyvinyl acetal or a polyvinyl butyral.

The starting material for the production of the polarizer is preferably an unstretched film of the above polyvinyl alcohol-based resin having a thickness of 20 to 100 μm, more preferably 30 to 80 μm. The width of the film is preferably about 1,500 to 4,000 mm in the industry. The unstretched film is treated in the order of, for example, a swelling step, a dyeing step, a crosslinking step, and a water washing step, and is uniaxially stretched in the step up to the crosslinking step, and finally dried to obtain a polarizer. The polarizer usually has a thickness of 5 to 50 μm, preferably 5 to 30 μm.

The dichroic dye used in the dyeing step may, for example, be iodine or an organic dye. Examples of the organic dyes include Red BR, Red LR, Red R, Pink LB, Rubin BL, Bordeaux GS, Sky Blue LG, Lemon Yellow, Blue BR, Blue 2R, Navy RY, Green LG, Violet LB, Violet B, Black H, Black B, Black GSP, Yellow 3G, Yellow R, Orange LR, Orange 3R, Scarlet GL, Scarlet KGL, Congo Red, Brilliant Violet BK, Supra Blue G, Supra Blue GL, Supra Orange GL, Direct Sky Blue, Direct Fast Orange S, Fast Black, etc. These dichroic dyes may be used singly or in combination of two or more.

A conventionally known substance can be used as the crosslinking agent used in the crosslinking step. For example, a boron compound such as boric acid or borax, glyoxal or glutaraldehyde can be mentioned. These crosslinking agents may be used singly or in combination of two or more.

Next, the polarizer protective film will be described. The polarizer has low strength and is easily broken. The polarizer protective film is used to protect the film of such a polarizer and is fixed to at least one side of the polarizer. The polarizer protective film may, for example, be a film which has been conventionally used in the field, and examples thereof include a cycloolefin resin film, a cellulose acetate resin film, and a polyester resin film (for example, polyethylene terephthalate, poly Ethylene naphthalate or polybutylene terephthalate, a polycarbonate resin film, an acrylic resin film, a polypropylene resin film, or the like.

The polarizer protective film is preferably one having transparency and excellent chemical resistance, and more preferably a cellulose acetate resin film. The cellulose acetate-based resin is a partial or complete acetate ester, and examples thereof include triethylenesulfonyl cellulose (TAC), diethyl cellulose, cellulose acetate propionate, and the like.

The cellulose acetate-based resin film is sold, for example, Fujitac (registered trademark) TD80 (made by Fujifilm Co., Ltd.), Fujitac (registered trademark) TD80UF (made by Fujifilm Co., Ltd.), and Fujitac (registered trademark) TD80UZ. (Fuji Film Co., Ltd.), KC8UX2M (Konica Minolta Opto Co., Ltd.), KC4UY (Konica Minolta Opto Co., Ltd.), and the like.

The polarizer protective film is only required to be fixed to at least one surface of the polarizer. When the polarizer protective film is fixed on both sides of the polarizer, the polarizer protective film may be the same on both sides, or may be a different polarizer protective film. For example, triethyl fluorenyl cellulose may be fixed on both sides of the polarizer, and triethyl fluorene cellulose may be fixed on one side and other polarizer protective films may be fixed on the other side. The other polarizer protective film is not particularly limited, but a cycloolefin resin film is preferably used.

The olefin-based resin is commercially available, for example, TopAs (registered trademark) (manufactured by Ticon A Co., Ltd.), Arton (registered trademark) (manufactured by JSR Co., Ltd.), and Zeonor (ZEONOR) (registered trademark) (Japan Zeon) , Zeonex (ZEONEX) (registered trademark) (made by Japan Zeon Co., Ltd.), Alpen (registered trademark) (Mitsui Chemical Co., Ltd.), etc.

When a cycloolefin resin is produced into a film, a known method such as a solvent casting method or a melt extrusion method can be suitably used. Further, for example, Esushina (registered trademark) (manufactured by Sekisui Chemical Co., Ltd.), SCA40 (manufactured by Sekisui Chemical Co., Ltd.), and Zeonor (registered trademark) film (manufactured by Optes) can be used. A commercially available product of a cycloolefin resin film.

The polarizer protective film usually has a thickness of about 10 to 150 μm, preferably about 20 to 100 μm.

When a polarizing plate is produced, a polarizing plate, a polarizer protective film, and a functional film or a functional sheet laminated as needed are often used as a phase difference plate. The phase difference plate can be used depending on the characteristics required for the liquid crystal panel and the liquid crystal display device.

When a polarizing plate is used as the elliptically polarizing plate, the phase difference plate is provided with, for example, a quarter-wave plate. Further, when a polarizing plate is used as the linear polarizing plate, the phase difference plate is, for example, a biaxial retardation film having an optical compensation function, an anisotropic film having a surface protective function, or the like. The 1⁄4 wavelength plate is a plate (film) showing a phase difference of about 1/4 wavelength (90 degrees) for all light in the visible light wavelength region (380 to 780 nm), and has linear polarization and circular polarization. A function of mutual conversion and having a function of compensating for the viewing angle of the liquid crystal cell.

The material constituting the phase difference plate is not particularly limited, and examples thereof include a (meth)acrylic resin (such as a methyl methacrylate resin), an olefin resin, a polyvinyl chloride resin, a cellulose resin, and a styrene resin. , acrylonitrile-butadiene-styrene copolymer resin (ABS resin), acrylonitrile-styrene copolymer resin (AS resin), polyvinyl acetate resin, polyvinylidene chloride resin, polyfluorene Amine resin, polyacetal resin, polycarbonate resin, modified polyphenylene ether resin, polyester resin (polyethylene terephthalate, polybutylene terephthalate, etc.), polyfluorene A resin, a polyether oxime resin, a polyarylate resin, a polyamidoximine resin, a polyimine resin, an epoxy resin, an oxetane resin, or the like. Further, these resins may contain additives insofar as they do not impede transparency or fixability.

When a phase difference plate is used, the phase difference plate may be one layer or two or more layers. When two or more layers of phase difference plates are laminated, the same phase difference plate can be used, or a phase difference plate can be used. However, a different phase difference plate is usually used. Further, when the same phase difference plate is used, it is usually used by changing the respective axis angles, but it can be used at the same axis angle. The phase difference plate usually has a thickness of about 10 to 100 μm, preferably about 20 to 80 μm.

In a polarizing plate protective film of one surface area layer and a polarizing layer protective film of another surface area layer, the polarizing plate protective film, the adhesive protective film, the polarizing plate, the polarizer protective film, and the like are required. A laminate obtained by laminating other functional films or functional sheets is obtained by cutting to obtain a precursor film before the polarizing plate. In the polarizing laminate, the polarizer, the polarizer protective film, and other functional films or functional sheets are generally fixed by an adhesive or an adhesive. The adhesive and the adhesive are not limited as long as they do not inhibit the function as a polarizing plate, and examples thereof include a polyvinyl alcohol resin, an epoxy resin, a urethane resin, and a cyanoacrylate resin. An acrylamide-based resin or the like as a binder and a binder for the components.

One of the preferred adhesives is, for example, a solventless type of adhesive. A solventless type of adhesive refers to a hardening compound (monomer, which does not contain an effective amount of a solvent, but which is reactively hardened by irradiation with an active energy ray (for example, ultraviolet rays, visible rays, electron beams, X-rays, etc.). An oligomer or the like which exhibits a fixing function by curing of a curable compound. Such an adhesive usually contains a hardening compound and a polymerization initiator.

The laminated system of the above-mentioned embryonic membrane is configured according to the use of a desired polarizing plate, and has, for example, the following laminated structure: "Polarizing plate protective film / polarizing plate (polarizing film protective film / polarizing plate) / adhesive layer / adhesive Protective film", "polarizing plate protective film / polarizing plate (polarizer protective film / polarizer / phase difference plate) / adhesive layer / adhesive protective film", "polarizing plate protective film / polarizing plate (polarizer protective film) / polarizer / first phase difference plate / second phase difference plate) / adhesive layer / adhesive protective film", "polarizing plate protective film / polarizing plate (polarizer protective film / polarizer / polarizer protective film) / Adhesive layer/adhesive protective film", "Polarizing plate protective film/polarizing plate (polarizer protective film/polarizer/polarizer protective film/phase difference plate)/adhesive layer/adhesive protective film", "Polarizing plate" Protective film/polarizing plate (polarizer protective film/polarizer/polarizer protective film/first phase difference plate/second phase difference plate)/adhesive layer/adhesive protective film”. Further, the description of the adhesive or the adhesive for fixing the polarizer, the polarizer protective film, and the retardation film is omitted.

The thickness of the laminate (raw film) obtained in this manner can be appropriately set depending on the use of the polarizing plate of the product, and is usually about 100 to 600 μm, preferably about 150 to 400 μm. The laminate (primary film) is usually produced by winding a long sheet of a roll into a roll and performing various treatments continuously or intermittently. Further, in the present invention, usually, at any stage in the production of the laminate (primary film), the laminate is cut into a short strip before the cutting step. The resulting laminated body (sheath film) is larger than the target polarizing plate, and is, for example, a size of a plurality of polarizing plates of 4 to 80 sheets.

By cutting the above laminated body (primary film), a polarizing plate of a predetermined size of the protective film of the two-surface layer can be obtained. In this cutting step, the laminated body (the embryonic film) is cut in such a manner that the blade abuts against the surface of the adhesive protective film side. The surface of the adhesive protective film side is pressed against the blade to cut the laminated body (embryrous film), whereby a polarizing plate which is less likely to be cracked can be obtained even if moisture adheres. As shown in the comparative example described later, the blade is placed on the surface of the protective film side of the polarizing plate to cut the laminated body (the primary film), and cracks are likely to occur due to adhesion of moisture. As described above, when the laminated body (the embryonic film) is cut, the surface is abutted against the blade, and the ease of occurrence of cracks due to adhesion of moisture is different. Here, the term "surface on the side of the adhesive protective film" means the outermost surface of one side of the layer of the adhesive protective film as viewed from the layer of the polarizer, and when the laminate is directly cut (the embryonic film) The surface of the adhesive protects the surface of the film, and when the other layer (for example, a cover sheet described later) is placed on the laminate (the film) placed on the upper side of the adhesive protective film, the upper surface of the object is cut. .

When the polarizing plate protective film is defective, the resulting laminate (liquid crystal panel) is disposed of in the defect inspection of the liquid crystal panel manufacturing factory, so that in the manufacture of the polarizing plate, in order to avoid the polarizing plate protective film Causes scratches, etc., you must be careful. On the other hand, when the liquid crystal cell is attached with a polarizing plate, the adhesive protective film is peeled off, and a slight scratch is allowed. Therefore, in the production of the polarizing plate of the present invention, as in the prior art, the processing operation is generally performed such that the polarizing plate protective film is on the upper surface side, and in the cutting step, the laminated body (the primary film) is placed upside down and cut. It is better. In this cutting step, care should be taken to avoid scratching the polarizing plate protective film that becomes the lower surface.

Further, when the laminated body (the embryonic film) is cut, it is preferable that the upper surface of the adhesive protective film is covered with the covering sheet in order to prevent the occurrence of dirt (stickiness, etc.) on the surface. The cover sheet is not limited as long as it is a sheet of a material that can be cut together with the laminate (the germ film), and examples thereof include a resin film (a polyethylene film, a polypropylene film, etc.), a cloth (woven fabric, Non-woven, etc.), paper, etc. When the upper surface of the adhesive protective film is covered with a cover sheet, it is preferable to place a cover sheet on the upper surface of the adhesive protective film to remove air bubbles between the adhesive protective film and the coated sheet.

The cutting of the laminate (primary film) is carried out by a conventionally used cutting machine, and is not particularly limited. For example, when it is carried out in batch mode, as long as a laminate (primary film) conforming to the size of the cutter (usually about 500 mm × 500 mm to 1000 mm × 1000 mm) is produced, the surface of the adhesive protective film is faced upward, and the laminate (the membrane) It is fixed to the cutter, covered with a coating film as needed, and cut into a desired size. Further, in the manufacturing method of the present invention, since the laminated body (the primary film) is cut against the blade on the side of the adhesive protective film, the blade for cutting is preferably a blade which is cut by the up and down movement. (ie, cutting knife).

The polarizing plate (C) has the same position as the end surface of the resin laminate (A) and the end surface of the polarizing plate (C), and may have the same size as that of the resin laminate (A). Fig. 2 is a view showing the case where the resin laminate (A) of the present invention has the same size as the polarizing plate (C).

Further, as shown in Fig. 3, the size of the polarizing plate (C) such as the end face of the polarizing plate (C) is located more inward than the end face of the laminated body of the present invention, and may be smaller than the size of the laminated body of the present invention.

In the laminated system of the present invention, a resin laminate (A) is first produced, and then a transparent adhesive (B) is applied to one surface of the resin laminate (A) to bond the transparent adhesive (B) to the polarizing plate (C).

The resin laminate (A) can be produced by the resin composition α which is provided to the intermediate layer and the resin compositions β and γ which respectively apply the thermoplastic resin layer to both surfaces of the intermediate layer.

The resin composition α is obtained by kneading a (meth)acrylic resin and a vinylidene fluoride resin in general. The kneading system can be carried out by a method comprising, for example, a step of melt-kneading at a temperature of 150 to 350 ° C at a shear rate of 10 to 1000 / sec.

The temperature at the time of melt-kneading is preferably 150 ° C or more because the resin can be sufficiently melted, and since it is easy to suppress thermal decomposition of the resin, it is preferably 350 ° C or lower. Further, since the resin is easily kneaded sufficiently, the shear rate at the time of melt-kneading is preferably 10/sec or more, and since decomposition of the resin is easily suppressed, it is preferably 1000/sec or less.

In order to obtain a more uniformly mixed resin composition of the components, the melt kneading is preferably carried out at a temperature of from 180 to 300 ° C, more preferably from 200 to 300 ° C, more preferably from 20 to 700 / sec, more preferably from 30 Performed at a shear rate of up to 500/sec.

The machine used in the melt kneading can use a general mixer or a kneader. Specifically, for example, a uniaxial kneader, a two-axis kneader, a twin-shaft extruder, a Henschel mixer, a Banbury mixer, a kneader, a barrel mill, or the like can be given. Further, when the shear rate is increased within the above range, a high shear processing apparatus or the like can be used.

Similarly to the resin composition α, the resin compositions β and γ can be produced by, for example, melt kneading at the above temperature and shear rate. In addition, when the thermoplastic resin layer contains one type of thermoplastic resin, it is possible to produce a resin laminate by performing melt extrusion as described later without performing melt-kneading in advance.

When the intermediate layer and the thermoplastic resin layer contain an additive, the additive may be contained in the resin contained in each layer in advance, or may be added during the melt-kneading of the resin, may be added after the resin is melt-kneaded, or may be composed of a resin. The material is added at the time of producing the resin laminate.

The resin laminate (A) having at least an intermediate layer and a thermoplastic resin layer respectively present on both sides of the intermediate layer can be formed by, for example, melt extrusion molding, solution casting film forming, hot pressing, and injection molding. Each of the resin compositions α, β, and γ is formed into a layer, and these layers are produced by, for example, bonding together with an adhesive or an adhesive, and the resin compositions α, β, and γ may be formed by melt coextrusion. It is manufactured by lamination integration. When the resin laminate (A) is produced by lamination, it is preferable to use an injection molding method and a melt extrusion molding method for the production of each layer, and it is more preferable to use a melt extrusion molding method. The resin laminate (A) is produced by melt-co-molding the resin compositions α, β, and γ, and is generally easier to manufacture than the resin laminate (A) produced by lamination. The resin layered product (A) which is formed twice is preferable.

In the melt coextrusion molding system, for example, the resin compositions α, β, and γ are respectively introduced into a two- or three-seat uniaxial or two-axis extruder, and are respectively melted and kneaded, and then fed through a supply die or a multi-manifold die. The intermediate layer formed of the resin composition α and the thermoplastic resin layer formed of the resin composition β and γ are laminated and integrated, and extruded. When the resin compositions β and γ are the same composition, one composition which is melt-kneaded in one extruder can be divided into two by a supply mold or the like, and thermoplasticity is formed on both surfaces of the intermediate layer. Resin layer. The obtained resin laminated system is preferably cooled and solidified by, for example, a roll unit.

Then, a hard coat layer is formed on at least one surface of the thermoplastic resin layer. Thereafter, printing is performed on the surface of the hard coat layer as needed to form a transparent adhesive (B).

The transparent adhesive (B) is bonded to the polarizing plate (C), and when the transparent adhesive (B) is an activated energy ray-curable adhesive, it is irradiated with active energy after being bonded to the polarizing plate. Line to carry it out.

The resin laminated system with a polarizing plate of the present invention is distributed, for example, in the form of a laminate having a width of 500 to 3000 mm and a length of 500 to 3000 mm.

The resin laminated system with a polarizing plate of the present invention can be used in various display devices. A display device is a device having a display element and includes a light-emitting element or a light-emitting device as a light-emitting source. The display device may be, for example, a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, an electron emission display device (for example, an electric field emission display device (FED), Surface electric field emission display device (SED), electronic paper (display device using electronic ink or electrophoretic element), plasma display device, projection display device (such as grating light valve (GLV) display device, with digital micro-reflection A display device for a wafer (DMD), a piezoelectric ceramic display, or the like. The liquid crystal display device also includes any of a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, and a projection type liquid crystal display device. Such display devices may be display devices that display two-dimensional images, and may be stereoscopic display devices that display three-dimensional images.

A touch sensor panel can be manufactured by using the resin laminate of the present invention with a polarizing plate in a display panel. Specifically, the resin laminated body with a polarizing plate of the present invention can be used as a window sheet for a touch screen. The touch screen is disposed on the front surface of the liquid crystal display device or the organic EL display device, and a touch sensor panel having a touch screen function can be obtained.

The present invention also provides a display device comprising the laminate of the present invention. The display device of the present invention may be, for example, the display device described above.

Fig. 2 is a schematic cross-sectional view showing a preferred embodiment of a liquid crystal display device comprising the resin laminate of the present invention. The resin laminated body 10 of the present invention is laminated on the polarizing plate 11 via the optical adhesive layer 12, and the laminated system can be disposed on the viewing side of the liquid crystal cell 13. A polarizing plate 11 is usually disposed on the back side of the liquid crystal cell 13. The liquid crystal display device 14 is composed of such members. Further, Fig. 2 is an example of a liquid crystal display device, and the display device of the present invention is not limited to this configuration.

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the examples.

 [Examples]    [Fica card softening temperature]  

It is measured according to the B50 method specified in JIS K 7206:1999 "Plastic-thermoplastic plastic-Fika softening temperature (VST) test method". The Fika softening temperature was measured by a Heat Distortion Tester [148-6 continuous type manufactured by Yasuda Seiki Co., Ltd.]. At this time, the test piece was measured by extruding each raw material into a thickness of 3 mm.

 [Alkali metal content]  

Determined by inductively coupled plasma mass spectrometry.

 [MFR]  

It is measured according to the method specified in JIS K 7210:1999 "Test Method for Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Plastic-Thermoplastic Plastics". The poly(methyl methacrylate)-based material was measured at a temperature of 230 ° C and a load of 3.80 kg (37.3 N).

 [MVR]  

The "Semi-auto melt Indexer" manufactured by Toyo Seiki Co., Ltd., manufactured according to JIS K 7210, was measured under the conditions of 1.2 kg load and 300 °C.

 [Full light transmittance and haze]  

Haze transmittance meter based on JIS K 7361-1:1997 "Test method for total light transmittance of plastic-transparent materials - Part 1: Single beam method" (Murako Color Technology Co., Ltd." HR-100") measurement.

 [YI value]  

It was measured by "Spectrophotometer SQ2000" manufactured by Nippon Denshoku Industries Co., Ltd.

 [average of film thickness]  

The film thickness of the resin laminate is measured by a micrometer. The average value of the above measurement was measured at 10 o'clock as the average value of the film thickness of the resin laminate.

In the measurement of the film thickness of each of the intermediate layer and the thermoplastic resin layers (B) and (C), the resin laminate was cut perpendicularly to the surface direction, and the cross section was polished with a sandpaper and then observed by a MicroSquare microscope. The average value of the above measurements was measured at 10 o'clock as the average value of the film thicknesses of the respective layers.

 (Manufacturing Example 1)  

98.5 parts by mass of methyl methacrylate and 1.5 parts by mass of methyl acrylate were mixed, and 0.16 parts by mass of a chain shifting agent (octyl mercaptan) and 0.1 part by mass of a releasing agent (stearyl alcohol) were added to obtain a monomer mixture liquid. Further, 0.036 parts by mass of a polymerization initiator [1,1-di(t-butylperoxy) 3,3,5-trimethylcyclohexane] was added to 100 parts by mass of methyl methacrylate. Starter mixture. The mixture was continuously supplied to the fully mixed polymerization reactor at a flow ratio of the monomer mixture to the starter mixture of 8.8:1, and the polymerization was carried out to an average polymerization rate of 54% at an average residence time of 20 minutes at a temperature of 175 ° C. A part of the polymer was obtained. The obtained polymer was heated to 200 ° C, introduced into a devolatilizing extruder with a vent hole, and the unreacted monomer was devolatilized from the vent hole at 240 ° C while the devolatilized polymer was melted. The state was extruded, and after water cooling, it was cut to obtain a granulated methacrylic resin (i).

The obtained particulate methacrylic resin composition was analyzed by thermal decomposition gas chromatography under the conditions shown below, and the respective peak areas corresponding to methyl methacrylate and acrylate were measured. As a result, the structural unit derived from methyl methacrylate of the methacrylic resin (i) was 97.5% by mass, and the structural unit derived from methyl acrylate was 2.5% by mass.

 (thermal decomposition conditions)  

Sample preparation: A fine scale (about 2 to 3 mg) of a methacrylic resin composition was placed in the center of a cylindrical metal battery, and the laminated metal battery was gently sealed with both ends by a pliers.

Thermal decomposition device: CURIE POINT PYROLYZER JHP-22 (Japan Analytical Industry Co., Ltd.)

Metal battery: Pyrofoi I F590 (manufactured by Nippon Analytical Industries Co., Ltd.)

Constant temperature bath setting temperature: 200 ° C

Set temperature of insulation pipe: 250 °C

Thermal decomposition temperature: 590 ° C

Thermal decomposition time: 5 seconds

 (Gas chromatographic analysis conditions)  

Gas chromatography analyzer: GC-14B (Shimadzu Corporation)

Detection method: FID

Column: 7G 3.2m × 3.1mm (Shimadzu Manufacturing Co., Ltd.)

Filler: FAL-M (Shimadzu Corporation)

Carrier gas: Air/N ₂ /H ₂ =50/100/50 (kPa), 80 mI/min

Temperature rise condition of the column: after holding at 100 ° C for 15 minutes, the temperature is raised to 150 ° C at 10 ° C / minute, and kept at 150 ° C for 14 minutes.

INJ temperature: 200 ° C

DET temperature: 200 ° C

The methacrylic resin composition was thermally decomposed by the above thermal decomposition conditions, and the peak area corresponding to methyl methacrylate detected when the decomposition product produced by the gas chromatography analysis conditions was measured was measured ( A1) The peak area (b1) corresponding to the acrylate. Then, the peak area ratio A (= b1/a1) was obtained from the peak area. On the other hand, a standard of a methacrylic resin having a weight ratio of acrylate unit of the methyl methacrylate unit of W ₀ (known) is thermally decomposed under the above thermal decomposition conditions, and the gas phase is determined to be in the above gas phase. Chromatographic analysis conditions The peak area (a ₀ ) corresponding to methyl methacrylate detected by the decomposition product produced and the peak area (b ₀ ) corresponding to the acrylate are determined from the peak area of the spectrum. The peak area ratio A ₀ (=b ₀ /a ₀ ). Then, a factor f (= W ₀ /A ₀ ) is obtained from the aforementioned peak area ratio A ₀ and the aforementioned weight ratio W ₀ .

The weight ratio W of the acrylate unit to the methyl methacrylate unit in the copolymer contained in the methacrylic resin composition is determined by multiplying the peak area ratio A by the aforementioned factor f, from which the weight The ratio (% by mass) of the methyl methacrylate unit to the total of the methyl methacrylate unit and the acrylate unit, and the ratio (% by mass) of the acrylate unit to the total amount were calculated as the ratio W.

The obtained methacrylic resin (i) has a MA of 2.5 wt%, an MFR of 2 g/10 min, a Mw of 120,000, a Fika softening temperature of 110 ° C, a Na content of less than 0.01 ppm, and a K content of less than 0.01 ppm. .

The weight average molecular weight (Mw) of the (meth)acrylic resin is measured by gel permeation chromatography (GPC). The GPC calibration line is prepared by using a methacrylic resin made of Showa Denko Electric Co., Ltd. with a narrow molecular weight distribution and a known molecular weight as a standard reagent, and measuring the weight of each resin composition from the elution time and molecular weight. Average molecular weight. Specifically, 40 mg of a resin was dissolved in a tetrahydrofuran (THF) solvent at 20 mI to prepare a measurement sample. In the measurement device, two "TSKgeI SuperHM-H" and one "SuperH2500", which are manufactured by Tosoh, are arranged in series, and an RI detector is used in the detector. The measured molecular weight distribution curve is the logarithm of the molecular weight of the horizontal axis, fitted using a normal distribution function, and fitted using a normal distribution function of the following formula.

 (Manufacturing Example 2)  

Granular methacrylic acid was obtained in the same manner as in Production Example 1 except that the methyl methacrylate was changed to 97.7 parts by mass, the methyl acrylate was changed to 2.3 parts by mass, and the chain shifting agent was changed to 0.05 parts by mass. Resin (ii), the content of the structural unit was measured. The methacrylic resin (ii) was derived from a structural unit derived from methyl methacrylate of 97.0% by mass, and the structural unit derived from methyl acrylate was 3.0% by mass.

The obtained methacrylic resin (ii) had a MA of 3 wt%, an MFR of 0.5 g/10 min, a Mw of 180,000, a Fika softening temperature of 106 ° C, a Na content of less than 0.01 ppm, and a K content of less than 0.01 ppm.

The vinylidene fluoride resin used in the examples and its physical properties are shown in Table 1.

The weight average molecular weight (Mw) of vinylidene fluoride is measured by GPC. The GPC calibration curve was produced by using polystyrene as a standard reagent, and the weight average molecular weight of each resin was measured from the elution time and molecular weight. Specifically, 40 mg of a resin was dissolved in an N-methylpyrrolidone (NMP) solvent at 20 mI to prepare a measurement sample. In the measurement device, two "TSKgeI SuperHM-H" and one "SuperH2500", which are manufactured by Tosoh, are arranged in series, and an RI detector is used in the detector.

 (Manufacturing Example 3)  

In order to make the bluing agent masterbatch (MB), the methacrylic resin (ii) and the coloring agent are dry blended at a ratio of 99.99:0.01 to 40 mm. A single-axis extruder (manufactured by Tanabe Plastic Machinery Co., Ltd.) was melt-mixed at a set temperature of 250 to 260 ° C to obtain colored masterbatch particles. As the coloring agent, a bluing agent (Sumip Iast (trademark registration) VioIet B" manufactured by Chemex Co., Ltd.) was used.

 (Manufacture of laminated body 1)  

First, in terms of the material for forming the intermediate layer, the methacrylic resin (ii) and the resin 1 and the masterbatch pellets produced in Production Example 3 were mixed at a ratio of 39:60:1 to obtain the intermediate layer of the present invention. The resin composition. Then, the aforementioned resin composition is 65 mm Single-axis extruder 2 [manufactured by Toshiba Machine Co., Ltd.] melted, and 100 parts by mass of methacrylic resin (i) as a material for forming a thermoplastic resin layer was 45 mm. The single-shaft extruders 1 and 3 [made by Hitachi Shipbuilding Co., Ltd.] were melted. Then, these are passed through a supply mold 4 (manufactured by Hitachi Shipbuilding Co., Ltd.) having a set temperature of 250 to 270 ° C, and laminated to form a laminate as shown in the above thermoplastic resin layer/intermediate layer/thermoplastic resin layer, from the multi-manifold The die 5 (manufactured by Hitachi Shipbuilding Co., Ltd., two types of three-layer distribution) was extruded to obtain a film-shaped molten resin 6. Then, the obtained film-shaped molten resin 6 is sandwiched between the first cooling roll 7 and the second cooling roll 8 which are disposed opposite to each other, and then wound around the second roll 8 while being sandwiched by the second roll. After being separated from the third roll 9, the third cooling roll 9 is wound and formed and cooled to obtain a film 10 having a three-layer structure in which the intermediate layer has a film thickness of 600 μm and the thermoplastic resin layer has a film thickness of 100 μm. The total film thickness of any of the obtained films 10 was 800 μm, which was colorless and transparent when visually observed. The amount of the alkali metal (NA + K) contained in the intermediate layer was found to be 0.21 ppm. The dielectric laminate of the obtained resin laminate had a dielectric constant of 4.7.

 (Manufacture of polarizing plate 1)  

A polyvinyl alcohol film having a thickness of 30 μm (average degree of polymerization of about 2400, degree of saponification of 99.9 mol% or more) was longitudinally uniaxially stretched to about 5 times by dry stretching, and kept in a state of being immersed in pure water at 60 ° C in a tension state. After 1 minute, it was immersed in an aqueous solution of iodine/potassium iodide/water at a weight ratio of 0.05/5/100 in an aqueous solution of 28 ° C for 60 seconds. Thereafter, it was immersed in a 72 ° C aqueous solution having a weight ratio of potassium iodide/boric acid/water of 8.5/8.5/100 for 300 seconds. Then, after washing with pure water of 26 ° C for 20 seconds, it was dried at 65 ° C to obtain a polarizer having a thickness of 12 μm in which iodine was adsorbed and adsorbed on a polyvinyl alcohol film. Next, an aqueous adhesive is applied to both sides of the polarizer, and the aqueous adhesive dissolves 3 parts by weight of carboxy-modified polyvinyl alcohol ("KL-318" manufactured by KURARAY Co., Ltd.) in 100 parts by weight of water. An aqueous solution of polyvinyl alcohol was obtained, and 1.5 parts by weight of water-soluble polyamide resin (100% by weight of water) was added to the aqueous solution of polyvinyl alcohol (Sumirez Resin 650 (30), manufactured by Tadaoka Chemical Industry Co., Ltd.) "The solid content concentration is 30% by weight]. The protective film of the transparent polymer film is a film of an acrylic hard coat layer having a thickness of 7 μm, which is laminated with a triethyl fluorinated cellulose film (TAC) having a thickness of 25 μm ("KC2UA" manufactured by Konica Minolta Opto Co., Ltd.), and The decene-based resin ("ZEONOR" manufactured by Zeon Co., Ltd.) having a thickness of 23 μm which was not stretched was bonded, and dried at 80 ° C for 5 minutes and at 40 ° C for 168 hours. Thereafter, a 20 μm thick adhesive [trade name "#KZ" manufactured by Lintec Co., Ltd.] was bonded to the ZEONOR side surface of the protective film of the transparent polymer film to obtain an identification side polarizing plate.

 (transparent adhesive 1)  

An acrylic adhesive organic solvent solution obtained by adding an isocyanate crosslinking agent to a copolymer of butyl acrylate and methyl acrylate and hydroxyethyl acrylate, and using a die coater to have a thickness of 50 μm after drying. The film was applied to a release-treated surface of a polyethylene terephthalate film (release film) having a thickness of 75 μm subjected to release treatment to obtain a sheet-like transparent adhesive having a release film.

 (Example 1)  

A hard coat layer is formed on both surfaces of the laminated body 1 to produce a resin laminated body (A1). The formation of the hard coat layer is carried out by using 50 parts by mass of dipentaerythritol hexaacrylate as a curable compound and 50 parts by mass of pentaerythritol tetraacrylate, and a photopolymerization initiator [Ciba Specialty Chemicals] The "IRGACURE 184"] 6 parts by mass, and 125 parts by mass of isobutanol as a solvent and 125 parts by mass of 1-methoxy-2-propanol were mixed to prepare a hard coating agent. The hard coating agent was applied onto both surfaces of the laminated body 1 by a dip coating method, dried at room temperature for 5 minutes, and further dried at 50 ° C for 10 minutes to form a coating film on the surface of the thermoplastic resin layer. Then, ultraviolet rays of 0.5 J/cm ^{2 were} irradiated with a 120 W high-pressure mercury lamp to harden the coating film to obtain a resin laminate (A1) having a hard coat layer having a thickness of 3.0 μm. The outermost surface (hard coat surface) of the resin laminate (A1) and the polarizing plate 1 were bonded together using the transparent adhesive 1. This was cut into a size of 4 cm × 6 cm to obtain a resin laminate with a polarizing plate (the water contact angle of the hard coat layer was 80 degrees).

 (Comparative Example 1)  

The outermost surface (the surface of the thermoplastic resin layer) of the laminated body 1 and the polarizing plate 1 are bonded together using the transparent adhesive 1. This was cut into a size of 4 cm × 6 cm to obtain a resin laminated body with a polarizing plate.

 (Example 2)  

The resin laminate (A1) having a size of 4 cm × 6 cm and the polarizing plate 1 cut into a size of 3.5 cm × 5.5 cm were bonded together using a transparent adhesive 1 cut into a size of 3.5 cm × 5.5 cm. A resin laminated body with a polarizing plate was obtained.

 (Example 3)  

After printing the black edge on the outermost surface (hard coat surface) of one of the resin laminates (A1), the surface to be printed and the polarizing plate 1 are bonded together using the transparent adhesive 1. This was cut into a size of 4 cm × 6 cm to obtain a resin laminated body with a polarizing plate.

 (Comparative Example 2)  

One of the outermost surfaces of the Technolloy (registered trademark) film (manufactured by Escarbo Sheet Co., Ltd., C101, thickness: 800 μm) containing no vinylidene fluoride resin and the polarizing plate 1 were bonded together using the transparent adhesive 1. This was cut into a size of 4 cm x 6 cm.

 (Example 4)  

As a raw material for forming a hard coat layer on one side of the laminated body 1, 50 parts by mass of dipentaerythritol hexaacrylate as a curable compound and 50 parts by mass of pentaerythritol tetraacrylate are used as photopolymerization. 10 parts by weight of a starter (manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE 184), 0.1 part by weight of a leveling agent (SH-28 manufactured by Toray Dow Corning Co., Ltd.), and 492.9 parts by weight of propylene monomethyl ether as a diluent solvent were diluted. The hard coat layer forming material was prepared and coated with a bar coater to form a coating film (water contact angle of 110 degree of the hard coat layer) under the same conditions as in Example 1. Further, on the other hand, 50 parts by mass of dipentaerythritol hexaacrylate and 50 parts by mass of pentaerythritol tetraacrylate, photopolymerization initiator [IRGACURE 184" of Ciba Specialty Chemicals Co., Ltd.] 6 parts by mass, and a hard coating agent prepared by mixing 125 parts by mass of isobutanol as a solvent and 125 parts by mass of 1-methoxy-2-propanol, and coating with a rod coater, and Example 1 Under the same conditions, a coating film (water contact angle of the hard coat layer of 80 degrees) was formed, and a resin laminate (A2) having a hard coat layer having a thickness of 3.0 μm on both sides was obtained. The hard coat surface of the resin laminate (A2) containing no leveling agent and the polarizing plate 1 were bonded together using the transparent adhesive 1. This was cut into a size of 4 cm × 6 cm to obtain a resin laminated body with a polarizing plate.

 (Example 5)  

A resin laminate having a polarizing plate was obtained in the same manner as in Example 2 except that the resin laminate (A2) was used instead of the resin laminate (A1) in the second embodiment.

 (Example 6)  

A resin laminate having a polarizing plate was obtained in the same manner as in Example 3 except that the resin laminate (A2) was used instead of the resin laminate (A1) in the third embodiment.

The resin laminates of the polarizing plates obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were placed in a constant temperature and humidity oven at 60 ° C and an absolute humidity of 90% for 120 hours to carry out an endurance test. For the film before and after the endurance test, the haze was measured in accordance with JIS K7136:2000, and the total light transmittance (Tt) was measured in accordance with JIS K7361:19971. The results obtained are shown in Table 2.

Further, the obtained resin laminated body with a polarizing plate was placed in a constant temperature and humidity oven at 60 ° C and an absolute humidity of 90% for 500 hours to carry out an endurance test. The resin laminated body with a polarizing plate before and after the endurance test was judged to have an appearance "○" when bubbles were not formed and peeled off, and the appearance was not changed, and bubbles were formed and peeled off, and the appearance was observed to be changed. It is "X". The results are shown in Table 2.

As shown in Examples 1 to 3, according to the present invention, transparency can be maintained after the durability test. Further, the laminate of the present invention does not generate bubbles or peeling after the endurance test.

As described above, the laminate of the present invention can maintain transparency even in a high-temperature and high-humidity environment for a long period of time, and thus can be used for display devices such as smart phones, portable game machines, audio players, and tablet devices.

Claims (18)

 A resin laminated body with a polarizing plate comprising: a resin laminated body (A) having an intermediate layer containing a (meth)acrylic resin and a vinylidene fluoride resin as a resin component, and thermoplasticity on both sides of the intermediate layer a resin layer, and a hard coat layer on at least one outermost surface of the thermoplastic resin layer; a transparent adhesive (B) present on a surface of at least one hard coat layer side of the resin laminate (A); and a polarizing plate (C), which is present via the transparent adhesive (B).    The resin laminated body with a polarizing plate according to the first aspect of the invention, wherein the intermediate layer of the resin laminated body (A) contains a (meth)acrylic resin based on the total resin component contained in the intermediate layer. 35 to 45 mass% and vinylidene fluoride resin 65 to 55 mass%.    The resin laminate with a polarizing plate according to claim 1 or 2, wherein the (meth)acrylic resin has a weight average molecular weight (Mw) of from 100,000 to 300,000.    The resin laminated body with a polarizing plate according to any one of claims 1 to 3, wherein the content of the alkali metal in the intermediate layer of the resin laminated body (A) is the total resin contained in the intermediate layer. The component is 50 ppm or less based on the standard.   The resin laminate with a polarizing plate according to any one of claims 1 to 4, wherein the (meth)acrylic resin is: (a1) a homopolymer of methyl methacrylate; and/or (a2) a copolymer comprising, in relation to the entire structural unit constituting the polymer, 50 to 99.9% by mass of a structural unit derived from methyl methacrylate, and 0.1 to 50% by mass derived from the formula (1) At least one structural unit of (meth) acrylate; In the formula, R ₁ represents a hydrogen atom or a methyl group, when R ₁ is a hydrogen atom, R ₂ represents an alkyl group having 1 to 8 carbon atoms, and when R ₁ is a methyl group, R ₂ represents an alkyl group having 2 to 8 carbon atoms. .  The resin laminated body with a polarizing plate as described in any one of Claims 1 to 5, wherein the vinylidene fluoride resin is polyvinylidene fluoride.    The resin laminated body with a polarizing plate according to any one of claims 1 to 6, wherein the molten mass flow rate of the vinylidene fluoride resin is 0.1 to 30 g when measured at a load of 3.8 kg and at 230 ° C. 10 minutes.    The resin laminated body with a polarizing plate according to any one of claims 1 to 7, wherein at least one of the intermediate layer and the thermoplastic resin layer further contains a coloring agent.    The resin laminated body with a polarizing plate according to any one of the first aspect of the invention, wherein at least one of the resin laminate (A) or the transparent adhesive (B) contains an ultraviolet absorber.    The resin laminated body with a polarizing plate according to any one of claims 1 to 9, wherein the average thickness of the resin laminated body is 100 to 2000 μm.    The resin laminated body with a polarizing plate according to any one of claims 1 to 10, wherein the thermoplastic resin layer is a (meth)acrylic resin layer or a polycarbonate resin layer.    The resin laminated body with a polarizing plate according to any one of claims 1 to 11, wherein the average thickness of the thermoplastic resin layer is 10 to 200 μm, respectively.    The resin laminate of the polarizing plate according to any one of claims 1 to 12, wherein the thicard softening temperature of the thermoplastic resin layer is 100 to 160 ° C, respectively.    The resin laminated body with a polarizing plate according to any one of the above-mentioned claims, wherein the transparent adhesive (B) has a total light transmittance of 90% or more and a haze of 2% or less.    The resin laminate of the polarizing plate according to any one of the first aspect of the invention, wherein the resin laminate (A) has a hard coat layer on both surfaces thereof.    The resin laminated body with a polarizing plate as described in any one of Claims 1-15 which has the printing of the surface of the hard-coat layer of the resin laminated body (A).    The resin laminated body with a polarizing plate according to any one of claims 1 to 16, wherein the outermost surface of the side of the resin laminated body (A) is further provided with an anti-scratch, anti-reflection a functional layer of at least one of the group consisting of anti-glare and anti-fingerprint.    A display device comprising a resin laminate having a polarizing plate according to any one of claims 1 to 17.