TW201819168A - Resin laminate with transparent pressure-sensitive adhesive and display device having the same - Google Patents

Abstract

An object of the present invention is to provide a resin laminate with a transparent pressure-sensitive adhesive having durability with respect to high temperature and high humidity. The resin laminate with transparent pressure-sensitive adhesive of the present invention comprises: a resin laminate (A) which at least has an intermediate layer and a thermoplastic resin layer presented on both sides of the intermediate layer, and a transparent adhesive (B) presented on at least one surface of the resin laminate (A), wherein the intermediate layer of the resin laminate (A) has 35 to 45% by mass of (meth) acrylic resin and 65 to 55% by mass of vinylidene fluoride resin based on the total resin components contained in the intermediate layer; the weight average molecular weight (Mw) of the (meth) acrylic resin is 100,000 to 300,000; and the content of the alkali metal in the intermediate layer is 50 ppm or less based on the total resin components contained in the intermediate layer.

Description

   Resin laminate with transparent adhesive and display device containing the same   

The present invention relates to a resin laminate with a transparent adhesive and a display device containing the resin laminate.

In recent years, the number of display devices such as smart phones, portable game consoles, audio players, and tablet devices with touch screens has been increasing. The surface of such a display device usually uses glass flakes. However, from the viewpoint of the trend of weight reduction or processability of display devices, the development of plastic sheets as a substitute for glass flakes is currently underway. For example, in Patent Document 1, a plastic sheet as a substitute for a glass sheet discloses a transparent sheet containing a methacrylic resin and a vinylidene fluoride resin, and describes that the transparent sheet sufficiently satisfies transparency and specific permittivity.

    [Prior technical literature]         [Patent Literature]    

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

In recent years, since a display device is used in various environments due to its high versatility, it is required to have durability in a severe environment such as high temperature and high humidity. Moreover, in a display device containing a plastic sheet, the plastic sheet is used by being attached to a polarizing plate or a touch sensing panel. Therefore, a plastic sheet with a transparent adhesive for attaching to a polarizing plate or a touch sensing panel is sought.

In the conventional transparent sheet system described in Patent Document 1, for example, white turbidity may occur in an environment of high temperature and high humidity of 60 ° C. and a relative humidity of 90%, and there is room for improvement in durability.

In order to solve the above-mentioned problems, the present inventors have repeatedly studied the resin laminate suitable for use in a display device in detail to complete the present invention.

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

[1] A resin laminate with a transparent adhesive, comprising a resin laminate (A) and a transparent adhesive (B) existing on at least one surface of the resin laminate (A), and the resin laminate (A ) Includes at least an intermediate layer and thermoplastic resin layers that are respectively present on both sides of the intermediate layer; wherein the intermediate layer of the resin laminate (A) is based on the entire resin component contained in the intermediate layer and contains (methyl ) Acrylic resin 35 to 45% by mass and vinylidene fluoride resin 65 to 55% by mass. The weight average molecular weight (Mw) of the (meth) acrylic resin is 100,000 to 300,000, and the content of the alkali metal in the aforementioned intermediate layer is based on The total resin content contained in the intermediate layer is 50 ppm or less based on the reference.

[2] The resin laminate with a transparent adhesive as described in [1], wherein the (meth) acrylic resin is: (a1) a homopolymer of methyl methacrylate, and / or (a2) a copolymer The substance includes a structural unit derived from methyl methacrylate based on 50 to 99.9% by mass of the total structural units constituting the polymer, and a (meth) derived from formula (1) derived from 0.1 to 50% by mass. ) At least one structural unit of acrylate; (In the formula, R ₁ represents a hydrogen atom or a methyl group. When R ₁ represents a hydrogen atom, R ₂ represents an alkyl group having 1 to 8 carbon atoms. When R ₁ represents a methyl group, R ₂ represents a carbon atom. Number 2 to 8 alkyl).

[3] The resin laminate with a transparent adhesive according to [1] or [2], wherein the vinylidene fluoride resin is polyvinylidene fluoride.

[4] The resin laminate with a transparent adhesive according to any one of [1] or [3], in which the melt mass flow rate of the vinylidene fluoride resin is 0.1 to 0.1 to 230 ℃ when measured at a load of 3.8 kg. 30g / 10 minutes.

[5] The resin laminate with a transparent adhesive according to any one of [1] or [4], wherein at least one of the intermediate layer and the thermoplastic resin layer further contains a colorant.

[6] The resin laminate with a transparent adhesive according to any one of [1] or [5], wherein the average value of the film thickness of the resin laminate is 100 to 2000 μm.

[7] The resin laminate with a transparent adhesive according to any one of [1] or [6], wherein the thermoplastic resin layer is a (meth) acrylic resin layer or a polycarbonate resin layer.

[8] The resin laminate with a transparent adhesive according to any one of [1] or [7], wherein the average value of the film thickness of the thermoplastic resin layer is 10 to 200 μm, respectively.

[9] The resin laminate with a transparent adhesive according to any one of [1] or [8], wherein the Vicat softening temperature of the thermoplastic resin layer is 100 to 160 ° C, respectively.

[10] The resin laminate with a transparent adhesive according to any one of [1] or [9], wherein at least one outermost surface of the resin laminate (A) further has a hard coating layer.

[11] The resin laminate with a transparent adhesive according to any one of [1] or [10], wherein the water contact angle on the outermost surface of the hard coating layer on the resin laminate (A) side is 100 ° or more .

[12] The resin laminated body with a transparent adhesive as described in any one of [1] or [11], wherein a resin film on the resin laminated body (A) side of the resin laminated body with a transparent adhesive is provided with a protective film .

[13] The resin laminated body with a transparent adhesive as described in any one of [1] or [12], wherein the transparent adhesive (B) side of the resin laminated body with a transparent adhesive has a separation film on the outermost surface .

[14] A display device comprising the resin laminated body with a transparent adhesive as described in any one of [1] or [13].

The resin laminated system with a transparent adhesive according to the present invention has high dielectric constant and can maintain transparency during long-term use in a high-temperature and high-humidity environment, so it can be suitably used in display devices and the like.

1‧‧‧Single-screw extruder (extrusion of molten thermoplastic resin)

2‧‧‧Single-screw extruder (extruded melt of vinylidene fluoride resin)

3‧‧‧Single-screw extruder (extrusion of molten thermoplastic resin)

4‧‧‧feeding mold

5‧‧‧Multi-manifold Die

6‧‧‧ film-like molten resin

7‧‧‧The first cooling roller

8‧‧‧ 2nd cooling roller

9‧‧‧3rd cooling roller

10‧‧‧Resin laminate (A)

10A‧‧‧Intermediate

10B‧‧‧Thermoplastic resin layer

10C‧‧‧Thermoplastic resin layer

11‧‧‧ polarizing plate

12‧‧‧ Transparent Adhesive (B)

13‧‧‧LCD cell

14‧‧‧ Liquid crystal display device

FIG. 1 is a schematic diagram of a film manufacturing apparatus of the present invention used in the examples.

FIG. 2 is a schematic cross-sectional view showing an example of a layer configuration of a liquid crystal display device including a resin laminate with a transparent adhesive according to the present invention in a preferred form.

The resin laminated body with a transparent adhesive of the present invention (hereinafter also referred to as the laminated body of the present invention) has: a resin laminated body (A), which includes at least an intermediate layer and a thermoplastic resin layer respectively present on both sides of the intermediate layer And, the transparent adhesive (B) is present on at least one surface of the resin laminate (A).

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

From the viewpoint of easily improving the dielectric constant and improving the transparency of the laminated body of the present invention, the intermediate layer is preferably based on the total resin component contained in the intermediate layer, and contains 36 to 44% by mass of (meth) acrylic resin. And 64 to 56% by mass of vinylidene fluoride resin, more preferably 37 to 43% by mass of (meth) acrylic resin and 63 to 57% by mass of vinylidene fluoride resin, and even more preferably 38 to 42 (Meth) acrylic resin and 62 to 58% by mass of vinylidene fluoride resin, particularly preferred are 39 to 41% by mass of (meth) acrylic resin and 61 to 59% by mass of vinylidene fluoride resin It is excellent that it contains 40% by mass of (meth) acrylic resin and 60% by mass of vinylidene fluoride resin.

Examples of the (meth) acrylic resin contained in the intermediate layer of the resin laminate (A) include homopolymers of (meth) acrylic monomers such as (meth) acrylate and (meth) acrylonitrile, A copolymer of two or more types of (meth) acrylic monomers, a copolymer of (meth) acrylic monomers and monomers other than (meth) acrylic monomers, and the like. In the present specification, the term "(meth) acrylic acid" means "acrylic acid" or "methacrylic 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 monomers mainly composed of methacrylate (alkyl methacrylate), and examples thereof include a homopolymer of methacrylate (polyalkyl methacrylate), and two types A copolymer of the above methacrylate, a copolymer of a monomer other than 50% by mass of the methacrylate and a monomer other than 50% by mass of the methacrylate, and the like. The copolymer of methacrylate and monomers other than methacrylate is preferably a methacrylate having a mass of 70% by mass or more based on the total amount of monomers from the viewpoint of easily improving optical characteristics and weather resistance. The copolymer with 30% by mass or less of other monomers is more preferably a copolymer of 90% by mass or more of methacrylate and 10% by mass or less of other monomers.

Examples of the single system other than methacrylate include acrylate and a monofunctional monomer having one polymerizable carbon-carbon double bond in the molecule.

Examples of monofunctional single systems include: styrene monomers such as styrene, α-methylstyrene, and vinyltoluene; cyanoolefins such as acrylonitrile and methacrylonitrile; acrylic acid; methacrylic acid; Anhydrides; N-substituted maleimide; etc.

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

From the viewpoint of easily improving the hardness, weather resistance, and transparency of the resin laminate, specifically, the meth) acrylic resin is preferably: (a1) a homopolymer of methyl methacrylate, and / or (a2 ) Copolymers, which contain structural units derived from methyl methacrylate based on the total structural units constituting the copolymer of 50 to 99.9% by mass, preferably 70.0 to 99.8% by mass, and more preferably 80.0 to 99.7% by mass, And at least one structural unit derived from (meth) acrylate represented by the following formula (1) from 0.1 to 50% by mass, preferably 0.2 to 30% by mass, and more preferably 0.3 to 20% by mass: [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. ]. Here, the content of each structural unit is such that the polymer obtained can be analyzed by a thermal decomposition gas chromatograph, and the peak area corresponding to each monomer is calculated.

In formula (1), R ₁ represents a hydrogen atom or a methyl group, when R ₁ represents a hydrogen atom, R ₂ represents an alkyl group having 1 to 8 carbon atoms, and when R ₁ represents a methyl group, R _{2 represents} Represents an alkyl group having 2 to 8 carbon atoms. Examples of the alkyl group having 2 to 8 carbon atoms include ethyl, propyl, isopropyl, butyl, second butyl, third butyl, pentyl, hexyl, heptyl, octyl and the like. From the viewpoint of heat resistance, R ₂ is preferably an alkyl group having 2 to 4 carbon atoms, and 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 lower than the lower limit described above, the transparency is insufficient when exposed to a high temperature and high humidity environment. When Mw is higher than the upper limit described above, the film-forming property at the time of manufacturing the resin laminate (A) cannot be obtained. The Mw of the (meth) acrylic resin is more preferably 120,000 or more, and more preferably 150,000 or more, from the viewpoint of easily improving the transparency when exposed 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 the film-forming property at the time of producing the resin laminate (A). The weight average molecular weight is measured by gel permeation chromatography (GPC) measurement.

The (meth) acrylic resin is measured under a load of 3.8 kg and 230 ° C, and usually has a melting mass of 0.1 to 20 g / 10 minutes, preferably 0.2 to 5 g / 10 minutes, and more preferably 0.5 to 3 g / 10 minutes. Flow rate (hereinafter sometimes referred to as MFR). MFR is below the above upper limit, and it is preferable to increase the strength of the obtained film. It is preferably above the above lower limit, and is preferably from the viewpoint of the film-forming property of the resin laminate (A). MFR can be measured according to the method specified in JIS K 7210: 1999 "Test Methods for Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Plastics-Thermoplastics". Regarding poly (methyl methacrylate) -based materials, measurement at a temperature of 230 ° C and a load of 3.80 kg (37.3 N) is specified in this JIS.

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

The (meth) acrylic resin can be prepared by polymerizing the aforementioned monomers by polymerization in 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 moving agent, a suitable commercially available product can be used. The amount of the chain-shifting agent to be added may be appropriately determined in accordance with the type of the monomer or its ratio, the characteristics to be obtained, and the like.

Examples of the vinylidene fluoride resin contained in the intermediate layer of the resin laminate (A) include homopolymers of vinylidene fluoride and copolymers of vinylidene fluoride and other monomers. The vinylidene fluoride resin is preferably selected from the group consisting of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, and perfluoroalkylvinyl, from the viewpoint of easily improving the transparency of the obtained resin laminate. Copolymer of at least one monomer in a group consisting of ether and ethylene and vinylidene fluoride, and / or homopolymer of polyvinylidene fluoride (polyvinylidene fluoride), and polyvinylidene fluoride For the better.

The weight average molecular weight (Mw) of the vinylidene fluoride resin contained in the intermediate layer is preferably 100,000 to 500,000, more preferably 150,000 to 450,000, still more preferably 200,000 to 450,000, and particularly preferably 350,000 to 450,000. Mw is above the lower limit. When the laminated body of the present invention is exposed to a high-temperature and high-humidity environment (for example, 60 ° C. and a relative humidity of 90%), it is preferable to improve the transparency of the laminated body of the present invention. Moreover, Mw is below the said upper limit, and since it is easy to improve the film-forming property of a resin laminated body (A), it is preferable. The weight average molecular weight is measured by gel permeation chromatography (GPC) measurement.

The vinylidene fluoride resin is measured under the conditions of a load of 3.8 kg and 230 ° C. It has a preferable range of 0.1 to 40 g / 10 minutes, more preferably 0.1 to 30 g / 10 minutes, and even more preferably 0.1 to 25 g / 10 minutes. Melt Mass Flow Rate (MFR). MFR is more preferably 0.2 g / 10 minutes or more, and even more preferably 0.5 g / 10 minutes or more. The MFR is more preferably 20 g / 10 minutes or less, even more preferably 5 g / 10 minutes or less, and particularly preferably 2 g / 10 minutes or less. The MFR is below the upper limit described above, and it is preferable because it is easy to suppress a decrease in transparency when the laminated body of the present invention is used for a long period of time. MFR is more than the said lower limit, and since it is easy to improve the film-forming property of a resin laminated body (A), it is preferable. MFR can be measured according to the method specified in JIS K 7210: 1999 "Test Methods for Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Plastics-Thermoplastics".

The vinylidene fluoride resin is industrially manufactured according to a suspension polymerization method or an emulsion polymerization method. Suspension polymerization is carried out by using water as the medium, dispersing the monomer in the medium as droplets, and dissolving the organic peroxide dissolved in the monomer as the polymerization initiator to carry out the polymerization. It can obtain 100 to 300 μm particles. Like polymer. Compared to emulsified polymers, suspended polymers are preferred because of the simpler manufacturing steps and superior powder handling, and the emulsified polymers generally do not contain alkali metal-containing emulsifiers or salting-out agents.

A commercially available vinylidene fluoride resin can be used. Examples of preferred commercially available products are, 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.

The intermediate layer system may further contain other resins different from (meth) acrylic resin and vinylidene fluoride resin. When other resins are contained, the type is not particularly limited as long as the transparency of the laminated body of the present invention is not significantly impaired. From the viewpoint of the hardness and weather resistance of the laminated body of the present invention, the amount of other resins is based on the total resin content contained in the intermediate layer, preferably 15% by mass or less, and more preferably 10% by mass or less. 5 mass% or less is even more preferred. Other resins include polycarbonate resin, polyamide resin, acrylic nitrile-styrene copolymer, methyl methacrylate-styrene copolymer, polyethylene terephthalate, and the like. The intermediate layer may further contain other resins, but from the viewpoint of transparency, the amount of other resins is preferably 1% by mass or less. The resin contained in the intermediate layer is only (meth) acrylic resin and Vinylidene fluoride resin is more preferred.

The content of the alkali metal in the intermediate layer is 50 ppm or less based on the entire resin component contained in the intermediate layer. When the content of the alkali metal in the intermediate layer exceeds the above-mentioned upper limit, when the laminated body of the present invention is used in a high-temperature and high-humidity environment for a long period of time, a decrease in transparency may occur. The content of the alkali metal in the intermediate layer is preferably 30 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less. When the content of the alkali metal in the intermediate layer is below the above-mentioned upper limit, it is easy to suppress a decrease in transparency when the laminated body 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, and from the viewpoint of easily suppressing the decrease in the transparency of the laminated body of the present invention, it is excellent that it does not substantially contain it. Here, trace amounts of emulsifiers and the like used in the manufacturing process remain in the (meth) acrylic resin and / or vinylidene fluoride resin contained in the intermediate layer. Therefore, the residual emulsifier contains an alkali metal such as sodium or potassium in an amount of 0.05 ppm or more. Especially when the (meth) acrylic resin and / or 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 amount of alkali metals in the intermediate layer increases. The content also becomes higher. From the viewpoint that the transparency of the laminated body of the present invention is easily suppressed, the (meth) acrylic resin and vinylidene fluoride resin contained in the intermediate layer are preferably resins containing less alkali metal. .

In order to keep the content of the alkali metal in the resin within the above range, the resin may be polymerized by reducing the amount of the alkali metal-containing compound or increasing the washing step after the polymerization to remove the alkali metal-containing compound. The content of the alkali metal can be obtained by, for example, inductively coupled plasma mass spectrometry (ICP / MS). Inductively coupled plasma mass analysis method is, for example, using high temperature ashing melting method, high temperature ashing acid dissolving method, Ca adding ashing acid dissolving method, combustion absorption method, low temperature ashing acid dissolving method, etc. A suitable method is to ash the sample, and then dissolve it in the acid, as long as the volume of the solution is determined and the content of alkali metal is determined by inductively coupled plasma mass analysis.

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

The thermoplastic resin layer contains at least one type of thermoplastic resin. The thermoplastic resin layer preferably contains 60% by mass or more, more preferably 70% by mass or more, based on all resin components contained in the respective thermoplastic resin layers, from the viewpoint of easily improving the moldability. 80% by mass or more of thermoplastic resin. The upper limit of the amount of the thermoplastic resin is 100% by mass. Examples of the thermoplastic resin system include (meth) acrylic resin, polycarbonate resin, and 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 types of thermoplastic resin.

From the viewpoint of the heat resistance of the resin laminate (A), the thermoplastic resin contained in the thermoplastic resin layer is measured in accordance with JIS K 7206: 1999, preferably having a temperature of 100 to 160 ° C, more preferably 102 to 155 ° C, and More preferably, it is a Ficca softening temperature of 102 to 152 ° C. Here, when the above-mentioned Fika softening temperature includes one type of thermoplastic resin in the thermoplastic resin layer, the Fika softening temperature of the resin is a mixture of a plurality of thermoplastic resins when the thermoplastic resin layer contains two or more types of thermoplastic resin. Fica softening temperature. In the present invention, the Ficca softening temperature is measured according to the B50 method specified in JIS K 7206: 1999 "Plastic-Thermoplastic-Vicat Softening Temperature (VST) Test Method". Fica softening temperature is measured by Heat Distortion Tester ["148-6 continuous type" manufactured by Yasuda Seiki Co., Ltd.]. The test piece at this time was measured by extruding each raw material to a thickness of 3 mm.

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

The thermoplastic resin layer is good in terms of molding processability, and is preferably a (meth) acrylic resin layer or a polycarbonate resin layer from the viewpoint of easily improving the adhesion with the intermediate layer.

One aspect of the present invention in which the thermoplastic resin layer is a (meth) acrylic resin layer will be described below. In this aspect, the thermoplastic resin layer contains one or more (meth) acrylic resins. From the viewpoint of surface hardness, the thermoplastic resin layer is based on all resin components contained in the respective thermoplastic resin layers, and preferably contains 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more of (meth) acrylic resin.

Examples of the (meth) acrylic resin include those described in relation to the (meth) acrylic resin contained in the intermediate layer. As long as the (meth) acrylic resin described in the intermediate layer is not specifically mentioned, it is also preferable as the (meth) acrylic resin contained in the thermoplastic resin layer. 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 terms of molding processability. From the viewpoint of easily improving the mechanical strength, it is preferably 50,000 to 300,000, and more preferably 70,000 to 250,000. The weight average molecular weight is measured by gel permeation chromatography (GPC) measurement.

In this aspect, the thermoplastic resin layer may further contain a thermoplastic resin other than one or more (meth) acrylic resins. The thermoplastic resin other than the (meth) acrylic resin is preferably a thermoplastic resin that is compatible with the (meth) acrylic resin. Specific examples thereof include a methyl methacrylate-styrene-maleic anhydride copolymer (for example, "Rejisufai" manufactured by Denki Chemical Industries), and a methyl methacrylate-methacrylic copolymer (for example, "Altuglass HT121" manufactured by Arkema). ), Polycarbonate resin. From the viewpoint of heat resistance, thermoplastic resins other than (meth) acrylic resins are measured in accordance with JIS K 7206: 1999, preferably having a temperature of 115 ° C or higher, more preferably 117 ° C or higher, and even more preferably 120 ° C or higher. Fica softening temperature. From the viewpoint of heat resistance and surface hardness, it is preferable that the thermoplastic resin layer does not substantially contain vinylidene fluoride resin.

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

Next, another aspect of the present 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 polycarbonate resins. From the standpoint of impact resistance, the thermoplastic resin layer is based on the total resin content of each thermoplastic resin layer, and preferably contains 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more of polycarbonate resin.

Examples of the polycarbonate resin are polymers obtained by a phosgene method in which various dihydroxy diaryl compounds are reacted with phosgene, or by using a dihydroxy diaryl compound and diphenyl. The polymer obtained by the transesterification reaction of carbonates such as carbonates is specifically a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A).

Examples of the dihydroxydiaryl compound include bisphenol A, and examples thereof include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis ( 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-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2- Bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, bis (hydroxyaryl) alkanes, such as 1, 1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (hydroxyaryl) cycloalkanes, such as 4,4'-dihydroxydibenzene Ethers, dihydroxydiaryl ethers of 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, such as dihydroxydiaryl of 4,4'-dihydroxydiphenyl sulfide Sulfides, such as 4,4'-dihydroxydiphenylsulfinium, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfinium, and dihydroxydiarylsulfinium, Such as 4,4'-dihydroxydiphenylfluorene, 4,4'-dihydroxy-3,3'-dimethyldiphenylfluorene's dihydroxydiarylfluorenes.

These systems can be used alone or as a mixture of two or more of them. , Dipiperidinyl hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl and the like.

Further, the above-mentioned dihydroxyaryl compound may be used in combination with a ternary or higher phenol compound shown below. Examples of phenols having three or more members include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, and 2,4,6-dione. Methyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4 -Hydroxyphenyl) -ethane and 2,2-bis- [4,4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

Examples of the polycarbonate resin other than the polycarbonate resin include polycarbonates synthesized from isosorbide and an aromatic diol. Examples of the polycarbonate include "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-" manufactured by Sumika Styron Polycarbonate Co., Ltd. can be used. 40, SD2221W, SD2201W, TR2201 "and so on.

In this aspect, the weight average molecular weight (Mw) of the polycarbonate resin is preferably 20,000 to 70,000, and more preferably 25,000 to 60,000, from the viewpoint of easily improving impact resistance and molding processability. The weight average molecular weight is measured by a 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 more preferably 4 minutes to train to 40cm ^3/10 min, particularly preferably based melt volume flow rate of 10 to 40cm ^3/10 minutes (hereinafter, also referred to as MVR). When the MVR is above the lower limit described above, the fluidity is high enough, and it is easy to perform molding processing during melt coextrusion molding and the like, and it is not easy to cause appearance defects, so it is preferable. When the MVR is lower than the above upper limit, it is preferable because mechanical properties such as the strength of the polycarbonate resin layer can be easily improved. The MVR system can measure the material of the polycarbonate resin in accordance with JIS K 7210 under conditions of a load of 1.2 kg and 300 ° C.

In this aspect, the thermoplastic resin layer may further contain a thermoplastic resin other than a polycarbonate resin. The thermoplastic resin other than the polycarbonate resin is preferably a thermoplastic resin compatible with the polycarbonate resin, more preferably a (meth) acrylic resin, and a methacrylic acid having an aromatic ring or a cycloolefin in the structure. Resin is even better. The thermoplastic resin layer contains a polycarbonate resin and the above-mentioned (meth) acrylic resin, which 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.

As long as the effect of the present invention is not hindered, at least one of the intermediate layer and the thermoplastic resin layer in the resin laminate (A) may further contain various additives generally used. Examples of the additives include stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, foaming agents, slip agents, release agents, antistatic agents, flame retardants, release agents, polymerization inhibitors, and flame retardant additives. , Reinforcing agents, nucleating agents, blueing agents and other coloring agents.

Examples of the colorant system include a compound having anthraquinone skeleton and a compound having phthalocyanine skeleton. Among these, compounds having anthraquinone skeleton are preferred from the viewpoint of heat resistance.

When at least one of the intermediate layer and the thermoplastic resin layer further contains a colorant, the content of the colorant in each layer can be appropriately selected according to the purpose, the type of the colorant, and the like. When the bluing agent is used as the coloring agent, the content is based on the total resin content contained in each layer containing the bluing agent, and can be set to about 0.01 to 10 ppm. The content is preferably 0.01 ppm or more, more preferably 0.05 ppm or more, still more preferably 0.1 ppm or more, still more preferably 7 ppm or less, even more preferably 5 ppm or less, even more preferably 4 ppm or less, and particularly preferably 3 ppm or less. The bluing agent can be appropriately used by a publicly known agent, and is represented by a trade name, for example, Macrolex (registered trademark) Blue RR (manufactured by Bayer), Macrolex (registered trademark) Blue 3R (manufactured by Bayer), Sumiplast (registered trademark) Viloet B (manufactured by Sumika Chemtex) and Polysynthren (registered trademark) Blue RLS (manufactured by Clariant), Diaresin Violet D, Diaresin Blue G, and Diaresin Blue N (above, manufactured by Mitsubishi Chemical Corporation).

The ultraviolet absorber is not particularly limited, and various conventionally known ultraviolet absorbers can be used. For example, an ultraviolet absorber having a large absorption at 200 to 320 nm or 320 to 400 nm can be mentioned. Specifically, for example, three UV absorber, benzophenone UV absorber, benzotriazole UV absorber, benzoate UV absorber, cyanoacrylate UV absorber. As the ultraviolet absorber, one kind of these ultraviolet absorbers can be used alone or in combination of two or more kinds. From the viewpoint of more effectively preventing damage caused by ultraviolet rays, a combination of at least one type of ultraviolet absorbent having a maximum absorption at 200 to 320 nm and at least one type of ultraviolet absorber having a maximum absorption at 320 to 400 nm is also used. Is better. As the ultraviolet absorber, a commercially available product such as "Kemisorb 102" (2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4) manufactured by Chemipro Chemical Co., Ltd. can be used. -N-octyloxyphenyl) -1,3,5-tri ) (Absorbance 0.1), "Adecastab LA-F70" (2,4,6-ginseng (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5 manufactured by ADEKA Corporation -three ) (Absorbance 0.6), "Adecastab LA-31, LA-31RG, LA-31G"(2,2'-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6 -(2H-benzotriazol-2-yl) phenol) (absorbance 0.2), "Adk Stab LA-46" (2- (4,6-diphenyl-1,3,5) manufactured by ADEKA Corporation -three -2-yl) -5- (2- (2-ethylhexyloxy) ethoxy) phenol) (absorbance 0.05) or "Tinuvin 1577" (2,4-diphenyl) manufactured by BASF Japan Co., Ltd. Phenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-tri ) (Absorbance 0.1) and so on.

When at least one of the intermediate layer and the thermoplastic resin layer further contains an ultraviolet absorber, the content of the ultraviolet absorber in each layer can be appropriately selected depending on the purpose, the type of the ultraviolet absorber, and the like. For example, the content of the ultraviolet absorber may be about 0.005 to 2.0% by mass based on the total resin content contained in each layer containing the ultraviolet absorber. The content of the ultraviolet absorber is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and still more preferably 0.03% by mass or more. The content of the ultraviolet absorber is preferably 1.5% by mass or less, and more preferably 1.0% by mass or less. The content of the ultraviolet absorbent is at least the above lower limit. From the viewpoint of easily improving the ultraviolet absorption effect, the content is preferably lower than the above upper limit, because it is easy to prevent the color tone (such as yellowness YI) of the resin laminate from changing. It is better. For example, it is preferable to use the above-mentioned commercially available "Adk Stab LA-31, LA-31RG, LA-31G" in the above-mentioned amount.

In another aspect of the present invention, at least one thermoplastic resin layer is a polycarbonate resin layer. Based on the total resin content of each thermoplastic resin layer, it contains 0.005 to 2.0% by mass of an ultraviolet absorber. Since it is easy to obtain the resin laminated body which is excellent in light resistance, it is preferable.

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

The average value of the film thickness of the resin laminate (A) is from the viewpoint of the rigidity of the laminate of the present invention, preferably 100 μm or more, more preferably 200 μm or more, and even more preferably 300 μm or more. From the viewpoint of transparency, the thickness is preferably 2000 μm or less, more preferably 1500 μm or less, and even more preferably 1000 μm or less. The film thickness of the resin laminate (A) was measured with a digital micrometer. The average value of the above-mentioned measurement at 10 points of the resin laminate (A) was taken as the average value of the film thickness.

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

In the resin laminate (A), the average value of the film thickness of the intermediate layer is from the viewpoint of the dielectric constant, preferably 100 μm or more, more preferably 200 μm or more, and even more preferably 300 μm or more. From the viewpoint of transparency, the thickness is preferably 1500 μm or less, more preferably 1200 μm or less, and even 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 average value of the film thickness of the thermoplastic resin layer.

The resin laminate (A) may have 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 composed of a hardening compound that imparts abrasion resistance as an essential component, and may contain, for example, a hardening catalyst, conductive particles, a solvent, a leveling agent, a stabilizer, an antioxidant, a colorant, etc. .

Examples of the hardening compound include an acrylate compound, a urethane acrylate compound, an epoxy acrylate compound, a carboxyl modified epoxy acrylate compound, a polyester acrylate compound, a copolymer acrylate compound, and an alicyclic ring. Formula epoxy resin, glycidyl ether epoxy resin, vinyl ether compound, oxetane compound and the like. The hardening compound is preferably a polyfunctional acrylate compound, a polyfunctional urethane acrylate compound, a polyfunctional epoxy acrylate compound, or the like from the viewpoint of easily improving the scratch resistance of the obtained hard coat layer. Hardening compounds based on polymer polymerization, or hardening compounds based on thermal polymerization such as alkoxysilane and alkylalkoxysilane. These hardenable compounds are preferably those which are hardened by irradiating energy rays such as electron beams, radiation, and ultraviolet rays, or those which are hardened by heating. These curable compounds may be used individually, or two or more compounds may be used in combination.

The hardening compound is preferably a compound having at least three (meth) acrylic fluorenyloxy groups in the molecule from the viewpoint of easily improving the transparency and surface hardness of the hard coat layer. Examples of the hardening compound having at least three (meth) acryloxy groups in the molecule include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, Glycerol tri (meth) acrylate, pentaglycerol tri (meth) acrylate, neopentaerythritol tri- or tetra- (meth) acrylate, dinepentaerythritol tri-, tetra-, penta- or hexa -(Meth) acrylic acid esters, poly (meth) acrylic acid esters of tri- or higher polyhydric alcohols of tri-pentaerythritol tetra-, penta-, hexa-, or hepta- (meth) acrylate; A compound having at least two isocyanate groups and a (meth) acrylic acid ester having a hydroxyl group are obtained by reacting a hydroxyl group with an equal molar ratio of isocyanate group or more, and the (meth) acrylic acid in the molecule is Urethane (meth) acrylates with 3 or more oxy groups [for example, by reacting diisocyanate with neopentaerythritol tri (meth) acrylate, 6-functional amino formic acid can be obtained Ester (meth) acrylate]; reference to (2-hydroxyethyl) tris (meth) acrylate of isocyanuric acid and the like. Although monomers are exemplified here, these monomers may be used directly, for example, those in the form of oligomers such as dimers and trimers may be used. A monomer and an oligomer may be used in combination. These (meth) acrylate compounds can be used alone or in combination of two or more.

As the curable compound having at least three (meth) acrylic fluorenyloxy groups in the molecule, a commercially available one can also be used. Specific examples include "NK Hard M101" (urethane acrylate), "NK Ester A-TMM-3L" (neopentaerythritol) manufactured by Shin Nakamura Chemical Industry Co., Ltd. Triacrylate), NK Ester A-TMMT (nepentaerythritol tetraacrylate), NK Ester A-9530 (dipentaerythritol pentaacrylate), and NK Ester A-DPH (secondary Pentaerythritol hexaacrylate), KAYARAD DPCA (di-nepentaerythritol hexaacrylate) made by Nippon Kayaku Co., Ltd., and Nopcocure 200 series made by San nopco (stock), Dainippon Ink Chemical Industry ( "Unidic" series, etc.

When a compound having at least three (meth) acryloxy groups in the molecule is used as the hardening compound, other hardening compounds may be used in combination, such as ethylene glycol di (meth) acrylate, diethylene glycol, as required. Alcohol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate have 2 (meth) acrylic acid groups in the molecule The amount of the compound used is usually up to 20 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 agent composition is hardened with ultraviolet rays, it is preferable to use a photopolymerization initiator as a curing catalyst from the viewpoint of easily improving the surface hardness and adhesion of the hard coating layer. Examples of the photopolymerization initiator system include benzyl, benzophenone and its derivatives, thiaxanthone, benzyldimethylacetal, α-hydroxyalkyl phenone, and hydroxyketone. , Amino alkyl phenols, fluorenyl phosphine oxides, etc. The photopolymerization initiator may be used alone or in combination of two or more kinds. The amount of the photopolymerization initiator 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, compared with a case where a photopolymerization initiator is not used, there is a tendency that the curing rate does not easily increase.

A commercially available photopolymerization initiator can be used. Specific examples include "IRGACURE 651", "IRGACURE 184", "IRGACURE 500", "IRGACURE 1000", "IRGACURE 2959", "DAROCUR 1173" made of Ciba‧Specialty‧Chemicals (shares). , "IRGACURE 907", "IRGACURE 369", "IRGACURE 1700", "IRGACURE 1800", "IRGACURE 819", "IRGACURE 784" and other IRGACURE series and DAROCUR series. "KAYACURE ITX", "KAYACURE DETX-S", "KAYACURE BP-100", "KAYACUREBMS", "KAYACURE 2-EAQ" and other KAYACURE series.

By including conductive particles in the hard coat composition, antistatic properties can be imparted to the hard coat layer. The conductive particles are preferably made of antimony-tin composite oxide, antimony oxide containing phosphorus, antimony 5 oxide, etc., antimony-zinc composite oxide, titanium oxide, indium-tin composite oxide (ITO). Inorganic particles. The conductive particles may be used in the form of a sol having a solid content 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 even more preferably 0.05 μm or less, from the viewpoint of easily improving the transparency of the hard coat layer. From the viewpoint of easily improving the antistatic property of the hard coat layer, the average particle diameter is preferably 0.001 μm or more.

The conductive particle system can be produced by, for example, a vapor phase decomposition method, a plasma evaporation method, an alkoxide decomposition method, a co-precipitation method, a hydrothermal method, and the like. The surface of the conductive particles may be surface-treated with, for example, a nonionic surfactant, a cationic surfactant, an anionic surfactant, a polysiloxane coupling agent, or an aluminum coupling agent.

When the hard coating composition contains conductive particles, the content is preferably 2 to 50 parts by mass, and more preferably 3 to 20 parts by mass based on 100 parts by mass of the curable compound. The more the content of the conductive particles, the more the antistatic property of the hard coating layer tends to be improved. However, if the amount of the conductive particles is too much, the transparency of the hard coating layer is reduced, which is not good.

The hard coating composition may contain a solvent for the purpose of viscosity adjustment and the like. In particular, when conductive particles are contained in the hard coating composition, it is preferable to contain a solvent in order to disperse the conductive particles well. When the hard coating composition contains a solvent and conductive particles, for example, the hard coating composition can be prepared by mixing conductive particles and a solvent, dispersing the conductive particles in a solvent, and mixing the dispersion with a hardening compound to produce the hard coating composition. The hardening compound and the solvent can be mixed, and then the conductive particles are dispersed in this mixed solution to produce the same.

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

The hard coating composition may contain a leveling agent from the viewpoint of easily improving the uniformity of coating of the hard coating agent. The leveling agent is preferably a silicone oil, and examples thereof include dimethyl silicone oil, phenylmethyl silicone oil, alkyl / aralkyl modified silicone oil, Fluoropolysiloxane, polyether modified polysiloxane, fatty acid ester modified polysiloxane, methyl hydrogen polysiloxane, polysiloxane containing silanol groups, polysiloxane containing alkoxy groups Oxygen oil, polysiloxane oil containing phenolic group, modified silicone oil based on methacrylic acid, modified silicone oil based on amine, modified silicone oil based on carboxylic acid, modified silicone oil based on carbitol , Epoxy modified polysiloxane, hydrogen sulfur modified polysiloxane, fluorine modified polysiloxane, polyether modified polysiloxane, etc. These leveling agents can be used alone or in combination of two or more. The amount of the leveling agent used is usually 0.01 to 5 parts by mass based on 100 parts by mass of the hardening compound.

As the leveling agent, a commercially available one can be used. Specifically, for example, "SH200-100cs", "SH28PA", "SH29PA", "SH30PA", "ST83PA", "ST80PA", "ST97PA" and "ST200PA" made by Toray Dow Corning Silicone "ST86PA", "BYK-302", "BYK-307", "BYK-320", and "BYK-330" made by BYK Chemie Japan.

The hard coating composition obtained in this manner is applied to at least one side of the laminated body having the intermediate layer and the thermoplastic resin layer to form a curable coating film, and is then cured to form a cured coating, thereby obtaining abrasion resistance. Hard coating. The coating system of the hard coating composition may be, for example, a bar coating method, a micro gravure coating method, a roll coating method, a vertical flow coating method, a dip coating method, a spin coating method, or a die seam coating method. The coating method such as spray coating method may be used. The curing of the curable coating film may be performed by irradiation with energy rays or heating in accordance with the type of the hard coating composition.

Examples of the energy ray system to be hardened by irradiation with the energy ray include, for example, ultraviolet rays, electron beams, radiation, and the like, and conditions such as intensity and irradiation time can be appropriately selected according to the type of the hard coating composition. In addition, when curing by heating, conditions such as temperature and time can be appropriately selected according to the type of the hard coating composition, but in order to avoid deformation of the resin substrate, the heating temperature is generally preferably 100 ° C or lower. . When the hard coating agent composition contains a solvent, after coating, the hardening coating film may be hardened after the solvent is volatilized, or the volatilization of the solvent and the hardening coating film may be hardened simultaneously.

The average film thickness of the hard coat layer is preferably 0.5 to 50 μm, and more preferably 1 to 20 μm. The smaller the thickness of the hard coating, the less prone to cracking. If it is too small, the abrasion resistance is insufficient and it is not good. 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-mentioned measurement at any 10 points of the hard coat layer is the average value of the film thickness.

On the surface of the hard coating layer, if necessary, an anti-reflection treatment may be performed by a coating method, a sputtering method, a vacuum evaporation method, or the like. In addition, a separately prepared anti-reflective sheet may be bonded to one or both sides of the hard coat layer to impart an anti-reflective effect.

The water contact angle of the hard coating layer is preferably 100 ° or more, more preferably 105 ° or more, and even more preferably 110 ° or more. The water contact angle is measured in accordance with JIS R3257: 199 using a contact angle meter (image processing type contact angle meter "FACE CA-X type" manufactured by Kyowa Interface Science Co., Ltd.).

The resin laminate (A) may have at least one functional layer in addition to the intermediate layer and the thermoplastic resin layer. The functional layer is preferably present on the surface of the thermoplastic resin layer opposite to the intermediate layer. Examples of the functional layer include an anti-reflection layer, an anti-glare layer, an anti-static layer, and an anti-fingerprint layer. These functional layers may be laminated on the laminated body of the present invention through an adhesive layer, or may be a coating layer laminated by coating. As the functional layer, for example, a hardened film described in Japanese Patent Application Laid-Open No. 2013-86273 can be used. The functional layer can 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, and can be applied by a coating method, a sputtering method, or a vacuum evaporation method The layer further coated with the anti-reflection layer may be a layer in which an anti-reflection sheet is laminated on one or both sides 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, but from the viewpoint of easily showing 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, the thickness is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 70 μm or less.

The transparent adhesive (B) may be appropriately selected according to the member to be bonded, and may be, for example, acrylic, rubber, urethane, polysiloxane, polyvinyl ether, or the like. From the viewpoint of particularly excellent transparency, weather resistance, and heat resistance, an acrylic adhesive containing an acrylic resin is suitable. In addition, as the transparent adhesive (B), an aqueous adhesive and an active energy ray-curable adhesive can also be used.

The acrylic adhesive is generally an adhesive containing an acrylic resin and a crosslinking agent. Examples of monomer components constituting the acrylic resin include: (meth) acrylic acid alkyl esters; one (meth) acrylfluorenyl group belonging to an olefinic double bond in the molecule; and a hydroxyl group and a carboxyl group in the same molecule Compounds having a polar functional group such as an amino group, an amino group, an epoxy group (hereinafter, referred to as a (meth) acrylic monomer having a polar functional group), and the like.

Examples of the alkyl (meth) acrylate system include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and iso (meth) acrylate C _1-10 alkyl (meth) acrylates such as octyl ester, 2-ethylhexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, and ethoxymethyl (meth) acrylate -Esters and the like.

Examples of the (meth) acrylic acid monosystem having a polar functional group include (meth) acrylic hydroxyl C ₁ such as (meth) acrylic acid, 2-hydroxypropyl (meth) acrylate, and hydroxyethyl (meth) acrylate. _-6 alkyl ester, (meth) acrylamidonium, N, N-dimethylamino ethyl ester, (meth) acrylate, glycidyl (meth) acrylate, and the like. Among these, hydroxy C _1-6 alkyl (meth) acrylates such as 2-hydroxypropyl (meth) acrylate and hydroxyethyl (meth) acrylate are preferred.

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

It is preferable to use a resin containing a (meth) acrylic acid alkyl ester as a main component and containing a small amount of a (meth) acrylic monomer having a polar functional group.

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

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

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

The (meth) acrylic resin constituting the acrylic adhesive has a weight average molecular weight Mw in terms of standard polystyrene obtained by a gel permeation chromatography (GPC), preferably in the range of 1 to 2 million. When the weight average molecular weight Mw is 1 million or more, the adhesion under high temperature and high humidity is improved, and it is easy to suppress the floating or peeling between the transparent adhesive (B) and the polarizing plate bonded to the adhesive. Occur, and there is a tendency to increase the reworkability, so it is better. In addition, when the above-mentioned weight average molecular weight Mw of the acrylic resin is 2 million or less, even if the size of a polarizing plate or the like bonded to the adhesive changes, the adhesive changes in accordance with the dimensional change. Therefore, it is used in, for example, a liquid crystal cell. At this time, there is a tendency that the dew or color unevenness of the display is suppressed, so it is preferable. Furthermore, 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. In addition, the acrylic resin contained in the acrylic adhesive may be composed of only the relatively high molecular weights described above, or may be composed of an acrylic resin different from the acrylic resin, such as a structural unit derived from a (meth) acrylate, as a main component. A mixture having a weight average molecular weight in the range of 50,000 to 300,000 and the like.

The above-mentioned acrylic resin constituting the acrylic adhesive can be produced by a known method such as a solution polymerization method, an emulsion polymerization method, a block polymerization method, a suspension polymerization method, or the like. In the production of this acrylic resin, a polymerization initiator is usually used. Examples of the polymerization initiator include azo compounds, organic peroxides, inorganic peroxides, and redox initiators in which peroxide and reducing agent are used in combination. Among these, 2,2'-azobisisobutyronitrile, benzamidine peroxide, ammonium persulfate and the like are preferably used. The polymerization initiator is usually used at a ratio of about 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of the monomers as a raw material of the acrylic resin.

The cross-linking agent is a compound having at least two functional groups in a molecule that can be cross-linked with a structural unit derived from a (meth) acrylic monomer having a polar functional group in an acrylic resin, and examples thereof include isocyanates. Compounds, epoxy compounds, metal chelate compounds, aziridine compounds, and the like.

Among these crosslinking agents, an isocyanate-based compound is preferably used. Isocyanate compounds are addition compounds, dimers, trimers, etc. obtained by reacting them with a polyhydric alcohol in addition to compounds having at least two isocyanate groups (-NCO) in the molecule. Use of forms. Specific examples include toluene diisocyanate, an adduct obtained by reacting toluene diisocyanate with a polyol, a dimer of toluene diisocyanate, a terpolymer of toluene diisocyanate, a hexamethylene diisocyanate, and a hexamethylene diisocyanate. Adducts obtained by reacting methylene diisocyanate with a polyol, dimers of hexamethylene diisocyanate, terpolymers of hexamethylene diisocyanate, and the like.

The crosslinking agent is usually formulated at a ratio of about 0.01 to 5 parts by mass relative to 100 parts by mass of the acrylic resin, preferably 0.1 to 5 parts by mass, and more preferably 0.2 to 3 parts by mass. If the blending amount of the crosslinking agent with respect to 100 parts by mass of the acrylic resin is set to 0.01 parts by mass or more, preferably 0.1 part by mass or more, the durability of the resin laminate with a transparent adhesive tends to be improved.

Other components can be blended in the adhesive system as needed. Other components that can be blended include, for example, metal fine particles, metal oxide fine particles, or metal-coated fine particles, conductive fine particles, ion conductive compositions, ionic compounds having organic cations or anions, and silane coupling agents. Agents, cross-linking catalysts, weather-resistant stabilizers, tackifiers, plasticizers, softeners, dyes, pigments, inorganic fillers, resins other than the aforementioned acrylic resins, and light-diffusing fine particles such as organic particles. In addition, an ultraviolet curable compound is blended in the adhesive to form an adhesive layer, and then it is irradiated with ultraviolet rays to harden it, which is also useful as a harder adhesive layer.

The method for applying the adhesive to the resin laminate (A) (or coating or bonding) includes, for example, a laminator, a bar coating method, a micro gravure coating method, a roll coating method, a dip coating method, A spin coating method, a die coating method, a casting transfer method, a vertical flow coating method, a spray coating method, and the like.

Specifically, the resin laminate system of the present invention can be directly coated on one or both sides of the resin laminate (A) by an adhesive composition in which the adhesive is dissolved in an appropriate solvent (such as ethyl acetate), and dried. In addition, it is also possible to use a separation membrane (release film) as a substrate, and apply an adhesive with a separation membrane formed by applying the above-mentioned adhesive composition to the separation membrane to one side of the resin laminate (A). Or both sides.

The water-based adhesive is generally a composition using, for example, a polyvinyl alcohol resin or a urethane resin as a main component, and a cross-linking agent such as an isocyanate compound, an epoxy compound, or a hardening compound, in order to improve adhesion. .

When a polyvinyl alcohol-based resin is used as the main component of the water-based adhesive, in addition to partially saponified polyvinyl alcohol and fully saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol and acetic acid-modified vinyl alcohol may also be used. , Methylol modified polyvinyl alcohol, and amino modified polyvinyl alcohol modified polyvinyl alcohol resin. Although an aqueous solution of such a polyvinyl alcohol-based resin can be used as an aqueous adhesive, the concentration of the polyvinyl alcohol-based resin in the aqueous adhesive is usually 1 to 10 parts by mass with respect to 100 parts by mass of water, and preferably 1 to 10 parts by mass. 5 parts by mass.

In an aqueous adhesive composed of an aqueous solution of a polyvinyl alcohol-based resin, in order to improve the adhesiveness, the hardening properties of polyhydric aldehydes, water-soluble epoxy resins, melamine-based compounds, zirconia-based compounds, and zinc compounds can be adjusted. Compound. For example, a water-soluble epoxy resin is a polyamine polyamine obtained by reacting a polyalkylene polyamine such as diethylenetriamine, triethylenetetramine, and a dicarboxylic acid such as adipic acid, and Epichlorohydrin is a water-soluble polyamine epoxy resin. As for such commercially available products of polyamide epoxy resin, there are "Sumirez Resin 650" and "Sumirez Resin 675" sold by Sumika Chemtex Co., Ltd., and "WS- 525 "and so on. When the water-soluble epoxy resin is prepared, the added amount is usually about 1 to 100 parts by mass, and preferably 1 to 50 parts by mass based on 100 parts by mass of the polyvinyl alcohol resin.

When a urethane resin is used as the main component of the aqueous adhesive, it is effective to make the polyester-based ionic polymer-type urethane resin the main component of the aqueous adhesive. The polyester-based ionic polymer-based urethane resin used herein refers to a urethane resin having a polyester skeleton, and a small amount of an ionic component (hydrophilic component) is introduced therein. Such an ionic polymer urethane resin can be used as an aqueous adhesive because it is emulsified directly in water without using an emulsifier to become an emulsion. When using a polyester-based ionic polymer urethane resin, it is effective to mix a water-soluble epoxy compound as a crosslinking agent. Adhesive systems using a polyester-based ionic polymer-based urethane resin as a polarizing plate are described in, for example, Japanese Patent Application Laid-Open No. 2005-70140 and Japanese Patent Application Laid-Open No. 2005-208456.

The aqueous adhesive is usually used in the form of an aqueous adhesive composition dissolved in water. The resin laminated system of the present invention can be obtained by applying a water-based adhesive composition to one or both sides of the resin laminated body (A) and drying it. The components which are not dissolved in the water contained in the aqueous adhesive may be dispersed in the system.

In addition, for example, in the case where the resin laminated body of the present invention is bonded to a polarizing plate or the like, an aqueous adhesive is injected between the polarizing plate and the resin laminated body (A), and then heating is performed to evaporate water, and a thermal crosslinking reaction is performed at the same time. , Which can give them sufficient adhesion.

The active energy ray hardening type adhesive is hardened by irradiation with active energy ray, and can be used to achieve practical strength for polarizing plates and the like of a resin laminate to which a transparent adhesive is attached. For example, a cationic polymerizable active energy ray hardening type adhesive containing an epoxy compound and a cationic polymerization initiator, and a radical polymerizable active energy ray hardening type adhesive containing an acrylic hardening component and a radical polymerization initiator may be mentioned. Agent, both containing a cationically polymerizable hardening component such as an epoxy compound and a radically polymerizable hardening component such as an acrylic compound, and the activity of a cationic polymerization initiator and a radical polymerization initiator Energy-ray-curable adhesives, and electron-beam-curable adhesives that irradiate an active energy-ray-curable adhesive that does not contain a starter with an electron beam to harden it. A radically polymerizable active energy ray hardening type adhesive containing an acrylic hardening component and a radical polymerization initiator is preferred. Moreover, a cationic polymerizable active energy ray hardening type adhesive containing an epoxy compound and a cationic polymerization initiator which can be used substantially without a solvent is preferable.

The cationically polymerizable epoxy compound is selected, and it is a liquid at room temperature. Even if there is no solvent, it has moderate fluidity. It is given the appropriate hardening and bonding strength, and it is obtained by blending with a suitable cationic polymerization initiator. The active energy ray hardening type adhesive is used in the manufacturing equipment of polarizing plates, and the drying equipment usually necessary in the step of bonding the laminated body and the polarizer of the present invention can be omitted. In addition, by irradiating an appropriate amount of active energy rays, it can also accelerate the hardening speed and increase the production speed.

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 glycidylamino group of a compound having an amine group, or a chain having a CC double bond. Epoxide, glycidyloxy or epoxyethyl bonded directly or through an alkylene group to a saturated carbocyclic ring, or an alicyclic epoxy compound having an epoxy group directly bonded to a saturated carbocyclic ring Wait. These epoxy compounds can be used individually or in combination of a plurality of different types. Among them, alicyclic epoxy compounds are preferred because of their excellent cationic polymerizability.

The glycidyl etherate of an aromatic compound or a chain compound having a hydroxyl group can be produced by, for example, a method of subjecting the hydroxyl group of an aromatic compound or a chain compound and epichlorohydrin to addition condensation under alkaline conditions. . Such a glycidyl etherate of an aromatic compound or a chain compound having a hydroxyl group includes: a diglycidyl ether of a bisphenol, a polyaromatic cyclic epoxy resin, an alkylene glycol, or a polyalkylene diene. Glycidyl ethers of alcohols and the like.

Examples of diglycidyl ethers of bisphenols include glycidyl etherate of bisphenol A and its oligomers, glycidyl etherification of bisphenol F and its oligomers, 3,3 ', 5, Glycidyl etherate of 5'-tetramethyl-4,4'-biphenol and its oligomers.

Examples of polyaromatic epoxy resins include glycidyl etherification of phenol novolac resin, glycidyl etherification of cresol novolac resin, glycidyl etherification of phenol aralkyl resin, and naphthol arane. Glycidyl etherification of resins, glycidyl etherification of phenol dicyclopentadiene resins, and the like. Furthermore, glycidyl etherates of ginseng phenols and oligomers thereof also belong to polyaromatic cyclic epoxy resins.

Examples of the diglycidyl ether of alkylene glycol or polyalkylene glycol include, for example, glycidyl etherification of ethylene glycol, glycidyl etherification of diethylene glycol, and 1,4-butanediol. Glycidyl etherate, glycidyl etherate of 1,6-hexanediol, and the like.

The glycidyl amine compound of the compound having an amine group is produced, for example, by a method in which the amine group of the compound and epichlorohydrin are subjected to addition condensation under basic conditions. The compound having an amine group may have a hydroxyl group at the same time. The glycidyl amine of such an amine-containing compound is a glycidyl amine of 1,3-phenylenediamine and its oligomer, and a glycidyl amine of 1,4-phenylenediamine And its oligomers, glycidyl amination and glycidyl etherification of 3-aminophenol and its oligomers, glycidyl amination and glycidyl etherification of 4-aminophenol and its Oligomers, etc.

The epoxide of a chain compound having a C-C double bond can be produced by using a peroxide under basic conditions to epoxidize the C-C double bond of the chain compound. The chain compound system having a C-C double bond includes butadiene, polybutadiene, isoprene, pentadiene, hexadiene, and the like. In addition, terpenes having a double bond can also be used as an epoxidation raw material. Examples of the acyclic monoterpenes include linalool and the like. Examples of the peroxide system used for the epoxidation include hydrogen peroxide, peracetic acid, and tert-butyl hydroperoxide.

The alicyclic epoxy compound bonded to a glycidyloxy group or an epoxyethyl group directly or through an alkylene group on a saturated carbocyclic ring may be a hydroxy group-containing aromatic compound represented by a bisphenol as an example. A glycidyl etherate of a hydrogenated polyhydroxy compound obtained by hydrogenating an aromatic ring of a group compound, a glycidyl etherate of a cycloalkane compound having a hydroxyl group, an epoxide of a cycloalkane compound having a vinyl group, and the like.

The epoxy compounds described above can be easily obtained from commercially available products and are represented by their respective trade names. Examples include the "j ER" series sold by Mitsubishi Chemical Corporation and the "Epiclon" sold by DIC Corporation. "," Epotohto (registered trademark) "sold by Toto Kasei 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," Tepic (registered trademark) "sold by Nissan Chemical Industry 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 a non-aromatic cyclic ring having a CC double bond in the ring by using a peroxide under basic conditions, for example. It is produced by epoxidizing CC double bond of compound. Examples of the non-aromatic cyclic compound having a CC double bond in the ring include a compound having a cyclopentene ring, a compound having a cyclohexene ring, and at least two further bonds to the cyclopentene ring or the cyclohexene ring. Polycyclic compounds such as carbon atoms to form additional rings. A non-aromatic cyclic compound having a C-C double bond in the ring may have another C-C double bond outside the ring. Examples of non-aromatic cyclic compounds having a C-C double bond in the ring include cyclohexene, 4-vinylcyclohexene, limonene and α-pinene, which are monocyclic monoterpenes.

An alicyclic epoxy compound having an epoxy group directly bonded to a saturated carbocyclic ring can be an alicyclic type having at least two epoxy groups directly bonded to the above-mentioned ring through an appropriate linking group. Structured compounds. The term “linking group” used herein includes, for example, an ester bond, an ether bond, and an alkylene bond.

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-epoxycyclohexylmethyl (Meth) acrylate, 2,2-bis (hydroxymethyl) -1-butanol and 4-epoxyethyl-1,2-epoxycyclohexane as adducts (3,4-epoxycyclohexanecarboxylic acid ester), oxodiethylene bis (3,4-epoxycyclohexanecarboxylic acid ester), 1,4-cyclohexanedimethylbis ( 3,4-epoxycyclohexanecarboxylate), 3- (3,4-epoxycyclohexylmethoxycarbonyl) propyl 3,4-epoxycyclohexanecarboxylate, and the like.

The alicyclic epoxy compound in which the epoxy group described above is directly bonded to a saturated carbocyclic ring can also be easily obtained as a commercial product, which are respectively represented by trade names. "Cyclomer", "Cyracure UVR" series sold by Dow Chemical, etc.

The epoxy compound-containing curable adhesive system may further contain an active energy ray-curable compound other than the epoxy compound. Examples of active energy ray-curable compounds other than epoxy compounds include oxetane compounds and acrylic compounds. Among them, an oxetane compound is preferably used in combination because it has the possibility of promoting the hardening 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) oxetan Alkane, bis (3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- ( Cyclohexyloxymethyl) oxetane, phenol novolac oxetane, 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, and the like.

The oxetane compounds can also be easily obtained from commercial products, and are respectively expressed by trade names. For example, the "Aron Oxetane (registered trademark)" series sold by Toa Kosei Co., Ltd. ETERNACOLL (registered trademark) "series.

The hardening compound containing an epoxy compound or an oxetane compound is preferably a solvent that is not diluted with an organic solvent or the like in order to make the adhesives formulated in such a solvent-free. In addition, compared with those dissolved in an organic solvent, they are other components constituting an adhesive, and include a small amount of a cation polymerization initiator or a sensitizer described later, or a powder obtained by removing / drying the compound of the organic solvent. A body or liquid is preferred.

The cationic polymerization initiator is a compound that generates cationic species upon irradiation with active energy rays such as ultraviolet rays. As long as the adhesive strength and the hardening speed required for the adhesive prepared can be provided, examples thereof include aromatic diazonium salts; aromatic sulfonium salts or onium salts of aromatic sulfonium salts; iron-arene complexes Wait. These cationic polymerization initiators may be used individually or in combination of a plurality of different types.

Examples of the aromatic diazonium salt system are as follows.

Benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium hexafluoroborate, etc.

Examples of the aromatic sulfonium salts are as follows.

Diphenylsulfonium (pentafluorophenyl) borate, diphenylsulfonium hexafluorophosphate, diphenylsulfonium hexafluoroantimonate, bis (4-nonylphenyl) sulfonium hexafluorophosphate, and the like.

Examples of the aromatic sulfonium salts are as follows.

Triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium (pentafluorophenyl) borate, diphenyl (4-phenylthiophenyl) hexafluoroantimony Acid salt, 4,4'-bis (diphenyldihydrothio) diphenylsulfide dihexafluorophosphate, 4,4'-bis [bis (β-hydroxyethoxyphenyl) dihydrosulfide Phenyl] diphenyl sulfide bishexafluoroantimonate, 4,4'-bis [bis (β-hydroxyethoxyphenyl) dihydrothio] diphenyl sulfide bishexafluorophosphate, 7- [Di (p-tolylmethyl) dihydrothio] -2-isopropylthiaxanthone hexafluoroantimonate, 7- [bis (p-tolylmethyl) dihydrothio] -2 -Isopropylthioanthrone (pentafluorophenyl) borate, 4-phenylcarbonyl-4'-diphenyldihydrothiodiphenylsulfide hexafluorophosphate, 4- (p- Tributylphenylcarbonyl) -4'-diphenyldihydrothiodiphenylsulfide hexafluoroantimonate, 4- (p-third-butylphenylcarbonyl) -4'-bis (p- Tolylmethyl) dihydrothio-diphenyl sulfide (pentafluorophenyl) borate and the like.

Examples of the iron-arene complex system are as follows.

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

Among the cationic polymerization initiators, the aromatic sulfonium salt also has an ultraviolet absorption property in a wavelength range of 300 nm or more, and can provide an adhesive (or an adhesive layer) having excellent hardenability, good mechanical strength, and adhesive strength. More suitable for use.

Cationic polymerization initiators can also be easily obtained from commercially available products, and are represented by trade names, for example, "Kayarad (registered trademark)" series sold from Nippon Kayaku Co., Ltd., and "Cyracure UVI" sold by Dow Chemical Co., Ltd. Series, photoacid generator "CPI" series sold by San-Apro Co., Ltd., photoacid generators "TAZ", "BBI" and "DTS" sold by Green Chemical Co., Ltd., "Adeka Optomer" series, "RHODORSIL (registered trademark)" sold by Rhodia.

In the active energy ray hardening type adhesive, the total amount of the cationic polymerization initiator relative to the active energy ray hardening type adhesive is 100 parts by mass, and it is usually formulated at a ratio of 0.5 to 20 parts by mass. . When the amount is too small, hardening is insufficient, and sometimes the mechanical strength or adhesion strength of the adhesive (adhesive layer) after hardening is reduced. Moreover, when it is too much, the ionic substance in an adhesive will increase, and the hygroscopicity of an adhesive will become high, and the durability of the laminated body of this invention may fall.

When an active energy ray hardening type adhesive is used in an electron beam hardening type, it is not particularly necessary to include a photopolymerization initiator in the composition, but in the case of using an ultraviolet hardening type, a photo radical generator is preferably used. Examples of the photo-radical generator include a hydrogen abstraction-type photo radical generator and a cleavage-type photo-radical generator.

Examples of the dehydrogenation type free radical generator include 1-methylnaphthalene, 2-methylnaphthalene, 1-fluoronaphthalene, 1-chloronaphthalene, 2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, 1 -Naphthalene derivatives such as iodonaphthalene, 2-iodonaphthalene, 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dicyanonaphthalene, anthracene, 1, 2-benzoanthracene, 9,10-dichloroanthracene, 9,10-dibromoanthracene, 9,10-diphenylanthracene, 9-cyanoanthracene, 9,10-dicylanthracene, 2,6, Anthracene derivatives such as 9,10-tetracyanoanthracene, fluorene derivatives, carbazole, 9-methylcarbazole, 9-phenylcarbazole, 9-propen-2-yl-9H-carbazole, 9-propyl 9-9-carbazole, 9-vinylcarbazole, 9H-carbazole-9-ethanol, 9-methyl-3-nitro-9H-carbazole, 9-methyl-3,6-dinitro -9H-carbazole, 9-octylcarbazole, 9-carbazole methanol, 9-carbazole propionic acid, 9-carbazole propionitrile, 9-ethyl-3,6-dinitro-9H-carbazole, 9-ethyl-3-nitrocarbazole, 9-ethylcarbazole, 9-isopropylcarbazole, 9- (ethoxycarbonylmethyl) carbazole, 9- (morpholinylmethyl) carbine Azole, 9-ethenylcarbazole, 9-allylcarbazole, 9-benzyl-9H-carbazole, 9-carbazoleacetic acid, 9- (2-nitrophenyl) carbazole, 9- (4-methoxyphenyl) carbazole, 9- (1-ethoxy-2-methyl-propane ) -9H-carbazole, 3-nitrocarbazole, 4-hydroxycarbazole, 3,6-dinitro-9H-carbazole, 3,6-diphenyl-9H-carbazole, 2-hydroxycarbazole Carbazole derivatives such as azole, 3,6-diethylfluorenyl-9-ethylcarbazole, benzophenone, 4-phenylbenzophenone, 4,4'-bis (dimethoxy) di Benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2-benzylbenzoic acid methyl ester 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] -phenylmethanone, xanthone , Thiaxanthone, 2-chlorothiaxanthone, 4-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylsulfan Hexanthone derivatives such as heteroanthrone, 2,4-diethylthiaxanthone, 1-chloro-4-propoxythioanthrone, or coumarin derivatives, and the like.

The cleavage type photo radical generator is a type of photo radical generator that generates a radical by cleavage of the compound by irradiating an active energy ray. Specific examples thereof include benzoin ether derivatives and acetophenone derivatives. Compounds such as aryl alkyl ketones, oxime ketones, fluorenylphosphine oxides, thiobenzoic acid S-phenyl esters, titanocene, and their derivatives with high molecular weight, but not Limited to this. Commercially available cleavable photo radical generators include, for example, 1- (4-dodecylbenzyl) -1-hydroxy-1-methylethane, 1- (4-isopropylbenzene (Methylamino) -1-hydroxy-1-methylethane, 1-benzylidene-1-hydroxy-1-methylethane, 1- [4- (2-hydroxyethoxy) -benzyl Fluorenyl] -1-hydroxy-1-methylethane, 1- [4- (propenyloxyethoxy) -benzylidene] -1-hydroxy-1-methylethane, diphenyl Ketone, phenyl-1-hydroxy-cyclohexyl ketone, benzyldimethylacetal, bis (cyclopentadienyl) -bis (2,6-difluoro-3-fluorenyl-phenyl) titanium, (η 6-cumylbenzene)-(η 5-cyclopentadienyl) -iron (II) hexafluorophosphate, trimethylbenzyldiphenylphosphine oxide, bis (2,6-di (Methoxy-benzyl)-(2,4,4-trimethyl-pentyl) -phosphine oxide, bis (2,4,6-trimethylbenzyl) -2,4-di Pentyloxyphenylphosphine oxide or bis (2,4,6-trimethylbenzyl) phenyl-phosphine oxide, (4-morpholinylbenzyl) -1-benzyl-1- Dimethylaminopropane, 4- (methylthiobenzyl) -1-methyl-1-morpholinylethane, and the like are not limited thereto.

Among the active energy hardening type adhesives used in the present invention, any of the photoradical generator contained in the electron beam hardening type, that is, a dehydrogenation type or a cracking type photoradical generator can be used separately. In addition, a plurality of them may be used in combination, but in terms of the stability of the photoradical generator monomer and in terms of hardenability, it is more preferably a combination of one or more kinds of photolytic radical generators. Among the cleavable photo radical generators, fluorenylphosphine oxides are preferred, and more specifically, trimethylbenzyldiphenylphosphine oxide (trade name "DAROCURE TPO", Ciba ‧ Japan (stock )), Bis (2,6-dimethoxy-benzylidene)-(2,4,4-trimethyl-pentyl) -phosphine oxide (trade name "CGI 403", Ciba‧Japan (stock )), Or bis (2,4,6-trimethylbenzyl) -2,4-dipentyloxyphenylphosphine oxide (trade name "Irgacure819", Ciba‧Japan (stock)) is preferred .

The active energy ray hardening type adhesive agent may contain a sensitizer as needed. By using a sensitizer, the reactivity is improved, and the mechanical strength or adhesion strength of the hardened adhesive (adhesive layer) can be further improved. As the sensitizer, the foregoing can be suitably used.

When the sensitizer is prepared, the amount of the sensitizer is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the total amount of the active energy ray-curable adhesive.

Various types of additives can be blended in the active energy ray hardening type adhesive agent within a range that does not impair the effect. Examples of additives that can be formulated include ion trapping agents, antioxidants, chain shifting agents, tackifiers, thermoplastic resins, fillers, flow regulators, plasticizers, and defoamers.

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 laminated system of the present invention can be obtained by coating the adhesive composition on one or both sides of the resin laminated body (A) and drying it. In addition, the components which will not dissolve in water contained in the adhesive need only be dispersed in the system.

The active energy ray hardening type adhesive agent can be applied to the resin laminate (A) by the aforementioned coating method. At this time, the viscosity of the active energy ray-curable adhesive agent is only required to have a viscosity that can be applied by various methods, but its 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‧sec is more preferable. When the viscosity is too small, it tends to be 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 uniform coating film without unevenness. Here, the so-called viscosity is a value measured at 60 rpm after a B-type viscometer is used to adjust the temperature of the adhesive to 25 ° C.

The active energy ray-curable adhesive can be used in the form of an electron beam-curable type or an ultraviolet-curable type. The so-called active energy ray is defined as an energy ray that can decompose compounds that produce active species to generate active species. Examples of such active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, alpha rays, beta rays, gamma rays, and electron beams.

In the electron beam curing type, any appropriate conditions can be adopted as long as the irradiation conditions of the electron beam are those that can harden the above-mentioned active energy ray curing type adhesive. For example, when the electron beam is irradiated, the acceleration voltage is preferably 5 kV to 300 kV, and more preferably 10 kV to 250 kV. When the acceleration voltage does not reach 5 kV, the electron beam may not reach the adhesive and may cause insufficient hardening. When the acceleration voltage exceeds 300 kV, the penetration force of the sample is too strong and the electron beam rebounds. There is a problem with the resin laminate (A), etc. Risk of injury. The radiation dose is 5 to 100 kGy, and more preferably 10 to 75 kGy. When the radiation dose is less than 5 kGy, the adhesive will be insufficiently hardened. When it exceeds 100 kGy, the resin laminate (A) will be damaged, resulting in a reduction in mechanical strength or yellowing, and the desired optical characteristics will not be obtained.

Electron beam irradiation is usually performed in an inert gas, but if necessary, it can be performed in the atmosphere or with a slight introduction of oxygen. It also differs according to the material of the laminated body of the present invention, but by properly introducing oxygen, when the surface of the resin laminated body irradiated with the initial electron beam still generates oxygen, it can prevent damage to the laminated body of the present invention, and only The adhesive agent efficiently irradiates the electron beam.

In the ultraviolet curing type, the light irradiation intensity of the active energy ray curing type adhesive is determined depending on each composition of the adhesive, and is not particularly limited, and preferably 10 to 5000 mW / cm ² . When the light irradiation intensity is less than 10 mW / cm ² , the reaction time is too long. When it exceeds 5000 mW / cm ² , due to the heat radiated from the light source and the heat generated during the polymerization of the adhesive, yellowing of the laminated body of the present invention or Degradation. In addition, the irradiation intensity is preferably the intensity in a wavelength range effective for activation of the photocationic polymerization initiator, more preferably the intensity in a wavelength range below 400 nm, and even more preferably in a wavelength range between 280 and 320 nm. The intensity. It is preferable to set such a light irradiation intensity once or a plurality of times so that the accumulated light amount becomes 10 mJ / cm ² or more, preferably 10 to 5,000 mJ / cm ² . When the cumulative light amount is less than 10 mJ / cm ² , the generation of active species derived from the polymerization initiator is insufficient, and the curing of the adhesive becomes insufficient. On the other hand, when the accumulated light amount exceeds 5,000 mJ / cm ² , the irradiation time is very long, which is disadvantageous for improving productivity. At this time, depending on whether the resin laminate (A) or the combination of the adhesive species is different, it is necessary to have a cumulative light amount in any wavelength region (UVA (320 to 390 nm) or UVB (280 to 320 nm), etc.).

The light source used for polymerization and hardening of the adhesive by irradiation with active energy rays in the present invention is not particularly limited, but examples thereof include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, halogen lamps, Carbon arc lamps, tungsten filament lamps, gallium lamps, excimer lasers, LED light sources that produce light in the wavelength range of 380 to 440 nm, chemical lamps, black light lamps, microwave excited mercury lamps, metal halide lamps. From the viewpoint of energy stability or simplicity of the device, an ultraviolet light source having a light emission distribution at a wavelength of 400 nm or less is preferable.

The film thickness of the transparent adhesive (B) is preferably 5 to 500 μm, and more preferably 10 to 350 μm. By setting the thickness of the adhesive layer to 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 a polarizing plate or the like to which the adhesive layer is attached. And there is a tendency to increase the reworkability. In addition, by making the thickness of 5 μm or more, even if the size of the polarizing plates bonded here changes, the adhesive layer changes in accordance with the dimensional change, so the durability against dimensional changes is improved.

The transparent adhesive (B) preferably 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 lower than the above lower limit, when it is laminated with the resin laminate (A), sufficient transparency cannot be obtained.

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

From the viewpoint of obtaining a sufficient function when the laminated system of the present invention is used in a display device such as a touch panel, it is preferably a dielectric constant of 3.5 or more, more preferably 4.0 or more, and even more preferably 4.1 or more. The upper limit of the dielectric constant is not particularly limited, but is usually 20. The permittivity can be adjusted to the type or amount of the vinylidene fluoride resin contained in the intermediate layer of the laminated body of the present invention, or by adding a high-permittivity compound such as vinyl carbonate and propylene carbonate. The above range. The dielectric constant is a value measured in accordance with JIS K 6911: 1995 at a temperature of 23 ° C. and a relative humidity of 50% for 24 hours under an environment of 3V and 100 kHz by an automatic balance bridge method. As the measurement system, a commercially available machine can be used, and for example, "precision LCR meter HP4284A" manufactured by Agilent Technologies, Inc. can be used.

The laminated system of the present invention is preferably transparent when visually observed. Specifically, the laminated system of the present invention is measured in accordance with JIS K7361-1: 1997, and preferably has a total light transmittance (Tt) of 85% or more, more preferably 88% or more, and even more preferably 90% or more. The upper limit of total light transmittance is 100%. The laminated body of the present invention after having been exposed to an environment of 60 ° C. and a relative humidity of 90% for 120 hours has a full light transmittance of the above range.

The laminated system of the present invention uses the laminated body of the present invention after being exposed to the environment of 60 ° C and a relative humidity of 90% for 120 hours. It is measured in accordance with JIS K7136: 2000, preferably having 2.0% or less, and more preferably 1.8% or less. , And more preferably the haze (price) below 1.5%. In addition, the laminated system of the present invention uses the laminated body of the present invention after being exposed to an environment of 60 ° C. and a relative humidity of 90% for 120 hours, and is measured in accordance with JIS Z 8722: 2009. It is preferably 1.5 or less, more preferably 1.4. Hereinafter, the yellowness (YeIIow Index: YI value) below 1.3 is even more preferable.

The film thickness of the laminated body of the present invention is from the viewpoint of the rigidity of the resin laminated body, preferably 100 μm or more, more preferably 200 μm or more, and even more preferably 300 μm or more. From the viewpoint of transparency, the thickness is preferably 2000 μm or less, more preferably 1500 μm or less, and even more preferably 1000 μm or less. The film thickness of the laminated body of the present invention is measured based on a digital micrometer. The average value of the above-mentioned measurement at 10 points of the resin laminate (A) was taken as the average value of the film thickness.

The laminate system of the present invention first manufactures a resin laminate (A), and as described above, a transparent adhesive (B) is applied to at least one surface of the resin laminate (A).

The resin laminated body (A) can be manufactured from the resin composition α provided to the intermediate layer, and the resin compositions β and γ provided to the thermoplastic resin layer on both surfaces of the intermediate layer, respectively.

The resin composition α is generally obtained by kneading a (meth) acrylic resin and a vinylidene fluoride resin. The kneading system can be implemented by a method including a step of performing melt kneading at a temperature of 150 to 350 ° C. and a shear rate of 10 to 1000 / second.

The temperature at the time of melt-kneading can sufficiently melt the resin, so it is preferably 150 ° C or higher, and it is easy to suppress the thermal decomposition of the resin, so it is preferably 350 ° C or lower. Furthermore, since it is easy to sufficiently knead the resin, it is preferable that the shear rate during melt-kneading is 10 / second or more, and since decomposition of the resin is easily suppressed, 1000 / second or less is preferable.

In order to obtain a more uniformly mixed resin composition, melt-kneading is preferably performed at a temperature of 180 to 300 ° C, more preferably at a temperature of 200 to 300 ° C, preferably 20 to 700 / second, and more preferably 30 Implemented at a shear rate of 500 / sec.

The machine used in the melt kneading can be a general mixer or a kneader. Specific examples include single-shaft kneading machines, multi-shaft kneading machines (e.g., two-shaft kneading machines, etc.), Henschel mixer, Banbury mixer, kneader, and roller mill Wait. When the shear rate is increased within the above range, a high-shear processing device or the like can be used.

Resin compositions β and γ can be produced by, for example, melt-kneading at the above-mentioned temperature and shear rate in the same manner as resin composition α. For example, when the thermoplastic resin layer contains one type of thermoplastic resin, a resin laminate can be produced by performing melt extrusion described later without performing melt kneading in advance.

When the intermediate layer and the thermoplastic resin layer contain additives, the additives may be included in the resin contained in each layer in advance, or may be added during the melt-kneading of the resin, and may be added after the resin is melt-kneaded, or the resin composition may be used. It is added when a resin laminate is produced.

The resin laminate (A) having at least an intermediate layer and thermoplastic resin layers on both sides of the intermediate layer can be formed by, for example, a melt extrusion molding method, a solution casting film forming method, a hot pressing method, or injection molding. Each layer is made from resin compositions α, β, and γ, and is produced by laminating them with, for example, an adhesive or an adhesive. The resin compositions α, β, and γ can also be formed by melt coextrusion. Multi-layer integration to manufacture. When the resin laminate (A) is produced by bonding, 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 coextrusion of resin compositions α, β, and γ, and is generally easier to manufacture than the resin laminate (A) produced by lamination. The secondary resin laminate (A) is preferred.

Melt co-extrusion molding system, for example, puts the resin composition α, β, and γ into two or three uniaxial or biaxial extruders, respectively, and melt-knead them separately, and then passes through a feed die or a manifold manifold die. Etc., a molding method in which an intermediate layer formed of the resin composition α and a thermoplastic resin layer formed of the resin compositions β and γ are laminated and integrated. When the resin composition β and γ are the same composition, one composition after melt-kneading in one extruder can be divided into two through a feeding die, and thermoplastic resins are formed on both surfaces of the intermediate layer. Floor. The obtained resin laminated system is preferably cooled and solidified by a roll unit or the like, for example.

The laminated body of the present invention can be prepared by applying the transparent adhesive (B) on at least one surface of the resin laminated body (A) obtained in this manner as described above.

The resin laminated system with a transparent adhesive of the present invention is obtained by cutting out the laminated body of the present invention manufactured as described above, and is in the form of a resin laminated body having a width of 500 to 3000 mm and a length of 500 to 3000 mm, for example. Delivery.

The present invention also provides a resin laminate with a transparent adhesive having a protective film on the outermost surface of the resin laminate (A) (hereinafter, this type of laminate is sometimes referred to as a laminate with a protective film).

Such a laminated body with a protective film preferably has a protective film having at least a film substrate and an adhesive layer bonded to each other with an adhesive layer interposed on the outermost surface of the resin laminated body (A).

The protective film is for the purpose of protecting the surface, and is adhered to the surface of the thermoplastic resin layer through an adhesive layer.

The film base material of the protective film is not particularly limited as long as it can protect the surface of the resin laminated body. From the viewpoint of easily improving the protective property of the surface of the resin laminated body, a plastic film is preferable. For example, it may be Polyethylene (PE) film, polypropylene (PP) film, polyethylene terephthalate (PET) film, acrylic resin film, polycarbonate (PC) film, etc.

The tensile elastic modulus of the film substrate of the protective film is from the viewpoint of easily improving the protective property of the surface of the resin laminate, preferably 100 MPa or more, more preferably 150 MPa or more, and even more preferably 200 MPa or more. The tensile elastic modulus of the film substrate of the protective film is preferably 5,000 MPa or less, more preferably 4,500 MPa or less, and even more preferably 4,000 MPa or less, from the viewpoint of ease of bonding.

The average value of the film thickness of the film substrate of the protective film is from the viewpoint of easily improving the protective property of the surface of the resin laminate, preferably 45 μm or more, more preferably 50 μm or more, and even more preferably 60 μm or more. In addition, the average value of the film thickness of the film base material of the protective film is 200 μm or less, more preferably 175 μm or less, and even more preferably 150 μm or less from the viewpoint of ease of bonding. The average value of the film thickness of the film substrate is measured by a digital micrometer, and the average value of the measured values at any 10 points is used as the average value of the film thickness.

The protective film is adhered to the surface of the resin laminated body (A) via an adhesive layer. Here, the protective film is a film attached for the purpose of protecting the surface of the resin laminate (A) during, for example, a manufacturing process or a distribution process. Therefore, in the manufacturing steps of the display device, the protective film is peeled from the surface of the resin laminate (A), and the resin laminate system with a transparent adhesive is bonded to the display device with the transparent adhesive (B) interposed, and assembled as Components of a display device.

The adhesive layer of the protective film is required to have both sufficient adhesion to maintain the state where the protective film is bonded to the surface of the resin laminated body (A) during the manufacturing process and the distribution process, and it is easy to remove the resin laminated body (A). Remove the protective film from the surface. From such a viewpoint, it is preferable that the protective film has a low adhesive force to the extent that it can be peeled off from the surface of the resin laminated body by hand, specifically, it is preferably 0.4N / 25mm or less, and more preferably 0.35N / 25mm. The following peel strength. From the viewpoint of easily maintaining a state in which the protective film is bonded to the surface of the resin laminate, it is preferable to have a peel strength of 0.01 N / 25 mm or more, and more preferably 0.02 N / 25 mm or more. The peel strength was measured at a peel speed of 0.3 mm / min, a peel angle of 180 °, and a measurement width of 25 mm in accordance with JIS-Z 0237.

The adhesive layer of the protective film is not particularly limited as long as it has the above-mentioned adhesiveness and peelability. For example, it may contain an acrylic resin, a rubber resin, an ethylene vinyl acetate copolymer resin, a polyester resin, and an acetate resin. A resin, a polyether fluorene resin, a polycarbonate resin, a polyamine resin, a polyimide resin, a polyolefin resin, or the like is preferably used as the adhesive.

The adhesive layer of the protective film may contain components other than an adhesive. Other components include, for example, antistatic agents, colorants, and ultraviolet absorbers.

The resin laminated system with a protective film of the present invention can be produced by bonding the surface of the resin laminated body (A) of the resin laminated body with a transparent adhesive to the above-mentioned protective film.

The present invention also provides a resin laminated body with a transparent adhesive having a separation film (release film) on the outermost surface of the transparent adhesive (B) side (hereinafter, this type of laminated body is sometimes referred to as a laminated body with a separation film). ). In this way, by having a separation film, the transparent adhesive (B) can be protected, and the laminated body of the present invention can be made more rational.

The separation film (peeling film) is, for example, a film base material such as the film listed above, or a polybutylene terephthalate film, a polyarylate film, or the like as a protective film.

The average value of the film thickness of the separation membrane is from the viewpoint of easily improving the protective property of the surface of the resin laminate, preferably 45 μm or more, more preferably 50 μm or more, and even more preferably 60 μm or more. In this aspect, the average value of the film thickness of the separation membrane is 200 μm or less, more preferably 175 μm or less, and particularly preferably 150 μm or less in terms of ease of bonding. The method of measuring the average value of the film thickness of the separation membrane is the same as that described above for the film substrate of the protective film.

The separation membrane is required to have both sufficient adhesion in a state where the separation membrane is adhered to the surface of the transparent adhesive (B), and easy removal from the surface of the transparent adhesive (B). Peelability of the separation membrane. From such a viewpoint, it is preferable that the separation membrane has a low adhesive force to the extent that it can be peeled off from the surface of the transparent adhesive (B) by hand, specifically, it is preferably 0.4N / 25mm or less, and more preferably 0.35. Peel strength below N / 25mm. In addition, from the viewpoint of easily maintaining a state in which the separation film is bonded to the surface of the transparent adhesive (B), the peeling strength is preferably 0.01 N / 25 mm or more, and more preferably 0.02 N / 25 mm or more. The peel strength can be measured in accordance with JIS-Z 0237.

The laminated system with a separation membrane can be manufactured by laminating the transparent adhesive (B) on the surface of the transparent adhesive (B) of the resin laminate with a transparent adhesive layer, and the transparent adhesive (B) can be dissolved in an appropriate solvent. The obtained adhesive composition is coated on a separation membrane, and the obtained transparent adhesive with a separation membrane is bonded to one side or both sides of the resin laminate (A) to produce it. In addition, the separation film on one side of the double-sided separation film type adhesive coated with the transparent adhesive (B) on both sides of the separation film can be peeled off and then bonded to the surface of the resin laminate (A), thereby obtaining the present invention. The invention is a laminated body with a separation membrane. In addition, the double-sided separation film type adhesive is a commercially available product, and the commercially available product may be, for example, a non-carrier adhesive film or a substrate-free adhesive sheet sold by LINTEC Corporation or Nitto Denko Corporation. Wait.

The separation film is, for example, a film that is bonded to the surface of the transparent adhesive (B) for the purpose of protection during the manufacturing process and the distribution process. Therefore, in the manufacturing steps of the display device, the separation film is peeled from the surface of the transparent adhesive (B), and the resin laminated system with the transparent adhesive of the present invention is bonded to the display device via the transparent adhesive (B). , Is assembled as a constituent member of the display device.

The laminated system of the present invention can be bonded to a polarizing plate, a touch panel, and the like, and 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 (such as an electric field emission display device (FED), Surface electric field emission display device (SED)), electronic paper (display device using electronic printing ink or electrophoretic element), plasma display device, projection display device (e.g. grid light valve (GLV) display device, digital micro-reflection Chip (DMD) display devices) and piezoelectric ceramic displays. The liquid crystal display device includes any one of a transmissive liquid crystal display device, a semi-transmissive liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, and a projection liquid crystal display device. These display devices may be display devices that display two-dimensional images, and may be three-dimensional display devices that display three-dimensional images. The laminated system of the present invention is suitably used as a front panel or a transparent electrode in such display devices.

When the laminated body of the present invention is bonded to a polarizing plate or a touch panel, when the transparent adhesive (B) is an activated energy ray-curable adhesive, it can be bonded to a polarizing plate or a touch panel sheet. Thereafter, it is performed by irradiating the active energy rays.

When the laminated body of the present invention is used as a transparent electrode in a touch panel or the like, a transparent conductive film is formed on the surface of the resin laminated body (A) to manufacture a transparent conductive sheet. A transparent adhesive (B) can be applied to the transparent conductive sheet After that, a transparent electrode is manufactured.

The method for forming a transparent conductive film is to form a transparent conductive film directly on the surface of the resin laminate (A), or to laminate a plastic film formed with a transparent conductive film in advance.

The film base material of the plastic film in which the transparent conductive film is formed in advance is not particularly limited as long as it is a base material that can form a transparent conductive film, and examples thereof include polyethylene terephthalate and polyethylene naphthalate. Ethylene glycol, polycarbonate, acrylic resin, polyamide, mixtures or laminates thereof, and the like. Before forming a transparent conductive film, the film may be coated for the purposes of improving surface hardness, preventing Newton's rings, and imparting antistatic properties.

A method of laminating a film having a transparent conductive film formed on the surface of the resin laminate (A) in advance is any method as long as it is a method of obtaining a uniform and transparent sheet without bubbles and the like. It can be laminated by using an adhesive that hardens due to normal temperature, heating, ultraviolet rays or visible light, or it can be laminated by a transparent adhesive tape.

As a method for forming a transparent conductive film, a vacuum evaporation method, a sputtering method, a CVD method, an ion plating method, and a spray coating method are known. These methods can be suitably used according to the necessary film thickness.

In the case of a sputtering method, for example, a general sputtering method using an oxide target, a reactive sputtering method using a metal target, or the like can be used. In this case, for the reactive gas, oxygen, nitrogen, or the like may be introduced, or a combination of ozone addition, plasma irradiation, and ion assist may be used. In addition, as required, a bias voltage such as DC, AC, or high frequency can be applied to the substrate. Examples of transparent conductive metal oxides used in transparent conductive films include indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide, and indium-zinc. Compound oxides and so on. Among these, an indium-tin composite oxide (ITO) is suitable from the viewpoint of environmental stability or circuit workability.

In addition, the method for forming a transparent conductive film can also be applied by applying a coating agent containing various conductive polymers capable of forming a transparent conductive film to the surface of the resin laminate (A), and irradiating heat or ultraviolet rays. A method of hardening the coating by ionizing radiation, and the like. As the conductive polymer, polythiophene, polyaniline, and polypyrrole are known, and these conductive polymers can be used.

The thickness of the transparent conductive film is not particularly limited, but when a transparent conductive metal oxide is used, it is usually 50 to 2000Å, preferably 70 to 000Å. Within this range, both conductivity and transparency are excellent.

The thickness of the transparent conductive sheet is not particularly limited, and the most appropriate thickness can be selected according to the requirements of the product specifications of the display.

By using the laminated body of the present invention as a display panel, and using the transparent conductive sheet manufactured from the laminated body of the present invention as a transparent electrode such as a touch screen, a touch sensor panel can be manufactured. Specifically, the laminated body of the present invention can be used as a window sheet for a touch screen, and a transparent conductive sheet can be used as an electrode substrate for a touch screen of a resistance film method or a capacitance method. By disposing the touch screen on the front surface of a liquid crystal display device or an organic EL display device, a touch sensor panel with a touch screen function can be obtained.

The present invention also provides a display device including the laminated body 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 including the resin laminate of the present invention. The resin laminated body 10 is laminated on the polarizing plate 11 via a transparent adhesive layer 12. This laminated system can be arranged on the viewing side of the liquid crystal cell 13. A polarizing plate 11 is usually arranged on the back side of the liquid crystal cell 13. The liquid crystal display device 14 is composed of such a member. The second figure 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 with examples and comparative examples, but the present invention is not limited to these examples.

    [Example]    

[Fica softening temperature]

Measured in accordance with the B50 method specified in JIS K 7206: 1999 "Plastic-Thermoplastic-Fica Softening Temperature (VST) Test Method". Fica softening temperature was measured with a Heat Distortion Tester ("148-6 continuous type" manufactured by Yasuda Seiki Seisakusho Co., Ltd.). The test piece at this time was measured by extrusion molding each raw material to a thickness of 3 mm.

[Content of alkali metal]

Determined by inductively coupled plasma mass spectrometry.

〔MFR〕

Measured in accordance with the method specified in JIS K 7210: 1999 "Test Methods for Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Plastics-Thermoplastics". Poly (methyl methacrylate) -based materials are measured at a temperature of 230 ° C and a load of 3.80 kg (37.3 N). The matter is specified in this JIS.

〔MVR〕

The material of the polycarbonate resin was measured using a "Semi-auto melt Indexer" manufactured by Toyo Seiki Co., Ltd. in accordance with JIS K 7210 under a load of 1.2 kg and 300 ° C.

[Total light transmittance and haze]

Based on JIS K 7361-1: 1997 "Test method for total light transmittance of plastics-transparent materials-Part 1: Single-beam method" (Murakami Color Research Institute Co., Ltd. " HR-100 ").

〔YI value〕

Measured with "Spectrophotometer SQ2000" manufactured by Nippon Denshoku Industries Co., Ltd.

[Average of film thickness]

The film thickness of the resin laminate was measured with a digital micrometer. The average value of the above measurement at 10 points was taken as the average value of the film thickness of the resin laminate.

The film thickness of each layer of the intermediate layer, the thermoplastic resin layers (B), and (C) is measured by cutting the resin laminate at right angles to the surface direction, grinding the cross section with sandpaper, and observing with a MicroSquare microscope. The average value of the above measurements at 10 points was taken as the average value of the film thickness of each layer.

〔Water contact angle〕

The resin laminated body was horizontally installed on a contact angle meter so that the hard coating layer on the resin laminated body (A) side faced up (image processing type contact angle meter "FACE CA-X type" manufactured by Kyowa Interface Science Co., Ltd.) 1 microliter of pure water was dropped on the surface of the measurement object, and the contact angle with water was measured by the θ / 2 method.

(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 parts by mass of a release agent (stearyl alcohol) were added to obtain a monomer mixed solution. In addition, 100 parts by mass of methyl methacrylate was added with 0.036 parts by mass of a polymerization initiator [1,1-bis (third butyl peroxide) 3,3,5-trimethylcyclohexane]. Starter mixture. Continuously supplied to the fully-mixed polymerization reactor such that the flow ratio of the monomer mixed liquid to the initiator mixed liquid became 8.8: 1, and polymerized to an average polymerization rate of 54% with an average residence time of 20 minutes and a temperature of 175 ° C. Part of the polymer was obtained. The obtained part of the polymer was heated to 200 ° C and introduced into a devolatilizing extruder with a vent hole. At 240 ° C, the unreacted monomer was devolatilized from the vent hole, and the devolatilized polymer was melted at the same time. It was extruded in a state, water-cooled, and then cut to obtain granular methacrylic resin (i).

The obtained granular methacrylic resin composition was analyzed by a thermal decomposition gas chromatograph under the conditions shown below, and the area of each peak corresponding to methyl methacrylate and acrylate was 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) methacrylic resin composition is placed in the center of a cylindrical metal unit, a metal battery is stacked, and both ends are gently pressed with pliers to seal.

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

Metal unit: PyrofoiI F590 (made by Japan Analytical Industry Co., Ltd.)

Setting temperature of constant temperature bath: 200 ℃

Set temperature of insulation pipe: 250 ℃

Thermal decomposition temperature: 590 ° C

Thermal decomposition time: 5 seconds

(Gas chromatography analysis conditions)

Gas chromatograph analysis device: GC-14B (manufactured by Shimadzu Corporation)

Detection method: FID

String: 7G 3.2m × 3.1mm (Shimadzu Corporation)

Filler: FAL-M (made by Shimadzu Corporation)

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

Heating conditions of the column: After being held at 100 ° C for 15 minutes, the temperature was raised to 150 ° C at 10 ° C / minute, and held at 150 ° C for 14 minutes.

INJ temperature: 200 ℃

DET temperature: 200 ℃

The methacrylic resin composition was thermally decomposed under the above thermal decomposition conditions, and a peak area corresponding to methyl methacrylate detected when the generated decomposition product was measured under the above-mentioned gas chromatography analysis conditions ( a1) and acrylate corresponding peak area (b1). Then, the spectral peak area ratio A (= b1 / a1) was obtained from these spectral peak areas. On the other hand, a standard product of a methacrylic resin having a weight ratio of W ₀ (known) to the methacrylate unit of the methyl methacrylate unit was thermally decomposed under the above-mentioned thermal decomposition conditions, and it was measured that the Chromatographic analysis conditions The peak area (a ₀ ) corresponding to methyl methacrylate and the peak area (b ₀ ) corresponding to acrylate are detected when the generated decomposition product is measured. The output peak area ratio A ₀ (= b ₀ / a ₀ ). Then, a factor f (= W ₀ / A ₀ ) is obtained from the spectral peak area ratio A ₀ and the weight ratio W ₀ .

By multiplying the aforementioned spectral peak area ratio A by the aforementioned factor f, a weight ratio W of an acrylate unit to a methyl methacrylate unit in a copolymer contained in the methacrylic resin composition is determined. The ratio W is used to calculate the ratio (mass%) of the methyl methacrylate unit to the total of the methyl methacrylate unit and the acrylate unit, and the ratio (mass%) of the acrylate unit to the total.

The obtained methacrylic resin (i) was 2.5% by weight of MA, Mg was 2g / 10 minutes, Mw was 120,000, Fica softening temperature was 110 ° C, Na content was less than 0.01ppm, and K content was less than 0.01ppm. .

The weight average molecular weight (Mw) of the (meth) acrylic resin is measured by gel permeation chromatography (GPC). GPC's calibration curve is prepared by using a methacrylic resin made by Showa Denko Corporation with a narrow molecular weight distribution and a known molecular weight as a standard reagent. A calibration curve is prepared from the dissolution time and molecular weight to determine the weight of each resin composition. Average molecular weight. Specifically, 40 mg of the resin was dissolved in 20 ml of a tetrahydrofuran (THF) solvent to prepare a measurement sample. In the measurement device, two "TSKgeI SuperHM-H" and one "SuperH2500" pipe column made of Tosoh (stock) were used in parallel and arranged in series, and an RI detector was used in the detector. The measured molecular weight distribution curve is the logarithm of the molecular weight on the horizontal axis, fitted using a normal distribution function, and fitted using a normal distribution function of the following formula.

(Manufacturing example 2)

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

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

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

The weight average molecular weight (Mw) of vinylidene fluoride is measured by GPC. The production of the calibration curve of GPC uses polystyrene as a standard reagent, and a calibration curve is prepared from the dissolution time and molecular weight, and the weight average molecular weight of each resin is measured. Specifically, 40 mg of the resin was dissolved in 20 ml of an N-methylpyrrolidone (NMP) solvent to prepare a measurement sample. In the measurement device, two "TSKgel SuperHM-H" and one "SuperH2500" tube columns made of Tosoh (stock) were used in parallel and arranged in series, and an RI detector was used for the detector.

(Manufacture example 3)

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

(Examples 1 to 2 and Comparative Examples 1 to 3)

The resin laminated body in this invention is manufactured as follows.

First, as for the material for forming the intermediate layer, a (meth) acrylic resin, a vinylidene fluoride resin, and masterbatch particles (MB particles) produced in Production Example 3 were mixed in a combination and proportion shown in Table 2 to obtain The resin composition of the present invention. Then, the resin composition was adjusted to 65 mm. The uniaxial extruder 2 [manufactured by Toshiba Machine Co., Ltd.] was melted, and 100 parts by mass of methacrylic resin (i) as a material for forming the thermoplastic resin layer was 45 mm. The uniaxial extruders 1 and 3 [made by Hitachi Shipbuilding Co., Ltd.] were melted. Next, these are supplied to three types of three-layer distribution-type feed dies 4 with a set temperature of 230 to 270 ° C. After being divided into three layers, the multi-manifold die 5 (made by Hitachi Shipbuilding Co., Ltd., two types) Three-layer distribution] Extruded and laminated with a structure represented by B layer / A layer / C layer to obtain a film-like molten resin 6. The obtained film-like molten resin 6 is sandwiched between the first cooling roller 7 and the second cooling roller 8 which are arranged opposite to each other, and then is wound between the second roller 8 and the second roller 8 while being wound around the second roller 8. After being wound between the third rolls 9, the film was wound around a third cooling roll 9 and formed / cooled to obtain a film 10 having a three-layer thickness with the thickness shown in Table 2 of each layer. The total film thickness of any of the obtained films 10 was 800 μm, and was colorless and transparent when visually observed. An acrylic adhesive organic solvent solution obtained by adding an isocyanate-based crosslinking agent to a copolymer of butyl acrylate, methyl acrylate, and hydroxyethyl acrylate as a transparent adhesive (B) to the obtained resin laminate. , Obtained by applying a die coater to a thickness of 50 μm after drying on a mold-treated surface of a polyethylene terephthalate film (release film) having a thickness of 75 μm subjected to a mold release treatment A sheet-shaped adhesive with a release film, and the obtained sheet-shaped adhesive with a release film was laminated with a laminator without bubbles, thereby preparing a resin laminate with a transparent adhesive.

The amount of alkali metal (Na + K) contained in the intermediate layer was determined. As a result, Example 1 was 0.21 ppm, Example 2 was 0.21 ppm, Comparative Example 1 was 0.25 ppm, Comparative Example 2 was 0.18 ppm, and Comparative Example 3 It is 108ppm.

(Example 3)

A resin laminate with a transparent adhesive was prepared in the same manner as in Example 1 except that the surface of the thermoplastic resin layer was hard-coated. The hard coating agent is a photopolymerization initiator [IRGACURE 184 of Ciba Specialty Chemicals (stock)] by using 50 parts of dipentaerythritol hexaacrylate and 50 parts of neopentaerythritol tetraacrylate as hardening compounds. 6 Parts, and 125 parts of isobutanol and 125 parts of 1-methoxy-2-propanol as a solvent were mixed and prepared. This hard coating agent was applied to both surfaces of the resin laminate by a dip coating method, and then 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, a high-pressure mercury lamp of 120 W was used to irradiate ultraviolet rays of 0.5 J / cm2 to harden the coating film, and a hard-coated resin laminate with a thickness of 3.0 μm was obtained.

(Comparative Example 4)

In Example 1, except that the laminated body (A) was replaced with Technolloy (C101, polycarbonate resin film, 800 μm thick) manufactured by Escarbo Sheet, the rest was prepared in the same manner as in Example 1 to obtain a transparent adhesive. Resin laminate.

For the resin laminates with transparent adhesives of Examples 1 to 3 and Comparative Examples 1 to 4, the dielectric constant was measured with a precison LCR meter HP4284A (manufactured by Agilent Technology) in accordance with JIS K 6911: 1995, and the results are shown in table 3. The dielectric constant is the value at 3V and 100kHz measured by the auto-balanced bridge method in a test sample (film) under the environment of 23 ° C and 50% relative humidity for 24 hours.

The obtained film was placed in a constant temperature and humidity oven at 60 ° C. and an absolute humidity of 90% for 120 hours, and subjected to a durability test. For the films before and after the endurance test, the value of haze (haze) measured according to JIS K7136: 2000 and the total light transmittance (Tt) measured according to JIS K7361-: 19971 are shown in Table 3.

In the endurance test, the resin laminated system with a transparent adhesive of the present invention shown in Examples 1 to 3 can have a high dielectric constant while maintaining transparency. Therefore, the resin laminated system with a transparent adhesive of the present invention has high dielectric constant, and at the same time, it can maintain transparency even under long-term use in a high-temperature and high-humidity environment, so it can be known that it can be used in smart phones and portable Display devices such as game consoles, audio players, and tablet devices.

Claims (14)

    A resin laminate with a transparent adhesive is a resin laminate (A) and a transparent adhesive (B) existing on at least one surface of the resin laminate (A). The resin laminate (A) is at least It includes an intermediate layer and thermoplastic resin layers respectively present on both sides of the intermediate layer; wherein the intermediate layer of the resin laminate (A) is based on the entire resin component contained in the intermediate layer and contains (meth) acrylic resin 35 to 45 mass% and vinylidene fluoride resin 65 to 55 mass%. The weight average molecular weight (Mw) of the (meth) acrylic resin is 100,000 to 300,000. The content of the alkali metal in the foregoing intermediate layer is determined in the intermediate layer. The total resin content contained is 50 ppm or less based on the standard.     The resin laminate with a transparent adhesive according to item 1 of the scope of the patent application, wherein the (meth) acrylic resin is: (a1) a homopolymer of methyl methacrylate, and / or (a2) a copolymer It includes: from 50 to 99.9% by mass of structural units derived from methyl methacrylate based on the total structural units constituting the polymer, and from 0.1 to 50% by mass of (meth) derived from the formula (1) At least one structural unit of acrylate; Formula, R ₁ is a hydrogen atom or a methyl-based, R ₁ is ₂ represents an alkyl group of 1 to 8 carbon atoms and R a hydrogen atom, R ₁ is a methyl group R ₂ represents an alkyl group having a carbon number of 2 to 8 .     The resin laminate with a transparent adhesive as described in item 1 or 2 of the scope of patent application, wherein the vinylidene fluoride resin is polyvinylidene fluoride.         The resin laminate with a transparent adhesive as described in any one of claims 1 to 3, wherein the melt mass flow rate of the vinylidene fluoride resin is 0.1 to 30 g measured at a load of 3.8 kg and 230 ° C. /10 minutes.         The resin laminate with a transparent adhesive as described in any one of claims 1 to 4, wherein at least one of the intermediate layer and the thermoplastic resin layer further contains a colorant.         The resin laminate with a transparent adhesive as described in any one of claims 1 to 5, wherein the average value of the film thickness of the resin laminate is 100 to 2000 μm.         The resin laminate with a transparent adhesive according to any one of claims 1 to 6, wherein the thermoplastic resin layer is a (meth) acrylic resin layer or a polycarbonate resin layer.         According to the resin laminate with a transparent adhesive as described in any one of claims 1 to 7, the average value of the film thickness of the thermoplastic resin layer is 10 to 200 μm, respectively.         According to the resin laminate with a transparent adhesive as described in any one of claims 1 to 8 of the scope of application for a patent, the Fica softening temperatures of the thermoplastic resin layer are 100 to 160 ° C, respectively.         As described in any one of claims 1 to 9, the resin laminate with a transparent adhesive, wherein at least one outermost surface of the resin laminate (A) further has a hard coating layer.         According to the resin laminate with a transparent adhesive as described in any one of claims 1 to 10 of the scope of patent application, the water contact angle of the outermost surface of the hard coating layer on the resin laminate (A) side is 100 ° or more.         The resin laminated body with a transparent adhesive as described in any one of claims 1 to 11, wherein the resin laminated body with a transparent adhesive has a protective film on the outermost side of the resin laminated body (A).         The resin laminate with a transparent adhesive as described in any one of claims 1 to 12, wherein the transparent adhesive (B) side of the resin laminate with a transparent adhesive has a separation film on the outermost surface.         A display device includes a resin laminate with a transparent adhesive as described in any one of claims 1 to 13 of the scope of patent application.