JP2017213771A - Resin laminate with transparent adhesive and display device including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin laminate with a transparent adhesive, which has durability against high temperature and high humidity.SOLUTION: The resin laminate with a transparent adhesive has: a resin laminate (A) 10 having at least an intermediate layer 10A and thermoplastic resin layers 10B and 10C present on either side of the intermediate layer 10A; and a transparent adhesive (B) 12 present on at least one surface of the resin laminate (A) 10. The intermediate layer 10A of the resin laminate (A) 10 contains 35 to 45 mass% of a (meth)acrylic resin and 65 to 55 mass% of a vinylidene fluoride resin based on the whole resin component included in the intermediate layer 10A; the (meth)acrylic resin has a weight average molecular weight (Mw) of 100,000 to 300,000; and a content of alkali metals in the intermediate layer 10A is 50 ppm or less based on the whole resin component included in the intermediate layer 10A.SELECTED DRAWING: Figure 2

Description

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

  In recent years, display devices such as a smartphone, a portable game machine, an audio player, and a tablet terminal are provided with a touch screen. A glass sheet is usually used on the surface of such a display device, but a plastic sheet as a substitute for the glass sheet has been developed from the viewpoint of weight reduction and workability of the display device. . For example, Patent Document 1 discloses a transparent sheet containing a methacrylic resin and a vinylidene fluoride resin as a plastic sheet as a substitute for a glass sheet, and this transparent sheet sufficiently satisfies transparency and relative dielectric constant. It is described.

JP2013-244604A

  In recent years, display devices are used in various environments because of their high versatility, and therefore, display devices are required to have durability in harsh environments such as high temperature and high humidity. In a display device including a plastic sheet, the plastic sheet is used by being attached to a polarizing plate, a touch sensor panel, or the like. For this reason, the plastic sheet | seat with the transparent adhesive for bonding a polarizing plate, a touch sensor panel, etc. is calculated | required.

  The conventional transparent sheet as described in Patent Document 1 may become cloudy in a high temperature and high humidity environment such as a relative humidity of 90% at 60 ° C., and there is room for improvement in durability. .

  In order to solve the above-mentioned problems, the present inventors have studied in detail the resin laminate suitably used in the display device, and have completed the present invention.

That is, the present invention includes the following preferred embodiments.
[1] A resin laminate (A) including at least an intermediate layer and thermoplastic resin layers respectively present on both surfaces of the intermediate layer, and a transparent adhesive present on at least one surface of the resin laminate (A) (B) and a resin laminate with a transparent adhesive,
The intermediate layer of the resin laminate (A) contains 35 to 45% by mass of (meth) acrylic resin and 65 to 55% by mass of vinylidene fluoride resin based on all resin components contained in the intermediate layer, ) The weight average molecular weight (Mw) of the acrylic resin is 100,000 to 300,000,
The resin laminate with a transparent adhesive, wherein the content of alkali metal in the intermediate layer is 50 ppm or less based on the total resin components contained in the intermediate layer.
[2] (Meth) acrylic resin
(A1) methyl methacrylate homopolymer and / or (a2) 50-99.9% by weight of structural units derived from methyl methacrylate based on all structural units constituting the polymer and 0.1-50 Formula of mass% (1)
(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, when R ₁ is a methyl group R ₂ represents the number of carbon atoms Represents an alkyl group of 2 to 8)
The resin laminate with a transparent adhesive according to [1], which is a copolymer containing at least one structural unit derived from a (meth) acrylic acid ester represented by:
[3] The resin laminate with a transparent adhesive according to [1] or [2], wherein the vinylidene fluoride resin is polyvinylidene fluoride.
[4] The transparent material according to any one of [1] to [3], wherein the melt mass flow rate of the vinylidene fluoride resin is 0.1 to 30 g / 10 minutes when measured at 230 ° C. under a load of 3.8 kg. Resin laminate with adhesive.
[5] The resin laminate with a transparent adhesive according to any one of [1] to [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] to [5], wherein the average 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] to [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] to [7], wherein the average 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] to [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] to [9], further comprising a hard coat layer on at least one outermost surface of the resin laminate (A).
[11] The resin laminate with a transparent adhesive according to any one of [1] to [10], wherein the water contact angle on the outermost surface of the hard coat layer on the resin laminate (A) side is 100 ° or more.
[12] The resin laminate with a transparent adhesive according to any one of [1] to [11], which has a protective film on the outermost surface on the resin laminate (A) side of the resin laminate with a transparent adhesive.
[13] The resin laminate with a transparent adhesive according to any one of [1] to [12], having a separator on the outermost surface on the transparent adhesive (B) side of the resin laminate with a transparent adhesive.
[14] A display device including the resin laminate with a transparent adhesive according to any one of [1] to [13].

  Since the resin laminate with a transparent adhesive of the present invention has a high dielectric constant and can maintain transparency even when used for a long time in a high-temperature and high-humidity environment, it can be suitably used for a display device or the like. .

It is the schematic of the manufacturing apparatus of the film | membrane of this invention used for the Example. It is a cross-sectional schematic diagram which shows the layer structural example of one preferable form of the liquid crystal display device containing the resin laminated body with a transparent adhesive of this invention.

  The resin laminate with a transparent adhesive of the present invention (hereinafter also referred to as the laminate of the present invention) is a resin laminate (A) comprising at least an intermediate layer and a thermoplastic resin layer present on each side of the intermediate layer. And a transparent adhesive (B) present on at least one surface of the resin laminate (A).

  An intermediate | middle layer contains 35-45 mass% (meth) acrylic resin and 65-55 mass% vinylidene fluoride resin based on all the resin components contained in this intermediate | middle layer. When the amount of (meth) acrylic resin is lower than the above lower limit, sufficient transparency cannot be obtained, and when the amount of (meth) acrylic resin is higher than the above upper limit, sufficient dielectric constant cannot be obtained. When the amount of vinylidene fluoride resin is lower than the above lower limit, sufficient dielectric constant cannot be obtained, and when the amount of vinylidene fluoride resin is higher than the above upper limit, durability cannot be obtained or sufficient transparency is obtained. I can't get it.

  From the viewpoint of easily increasing the dielectric constant and enhancing the transparency of the laminate of the present invention, the intermediate layer is based on the total resin components contained in the intermediate layer and includes 36 to 44% by mass of (meth) acrylic resin and 64- It is preferable to contain 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 38 to 42% by mass of ( It is even more preferable to include a (meth) acrylic resin and 62 to 58% by weight of vinylidene fluoride resin, and it is particularly preferable to include 39 to 41% by weight of (meth) acrylic resin and 61 to 59% by weight of vinylidene fluoride resin. Preferably, it contains 40% by weight of (meth) acrylic resin and 60% by weight 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) acrylic acid esters and (meth) acrylonitrile, and two or more ( Examples include a copolymer of a (meth) acrylic monomer, and a copolymer of a (meth) acrylic monomer and a monomer other than the (meth) acrylic monomer. In the present specification, the term “(meth) acryl” means “acryl” or “methacryl”.

  The (meth) acrylic resin is preferably a methacrylic resin from the viewpoint of easily increasing the hardness, weather resistance, and transparency of the resin laminate. A methacrylic resin is a polymer of a monomer mainly composed of a methacrylic acid ester (alkyl methacrylate). For example, a homopolymer of a methacrylic acid ester (polyalkyl methacrylate), a copolymer of two or more methacrylic acid esters And a copolymer of a monomer other than 50% by mass of a methacrylic acid ester and a monomer other than 50% by mass of a methacrylic acid ester. As a copolymer of a methacrylic acid ester and a monomer other than the methacrylic acid ester, from the viewpoint of easily improving optical properties and weather resistance, 70% by mass or more of the methacrylic acid ester and 30% relative to the total amount of the monomers. Copolymers with other monomers of less than or equal to mass% are preferred, and copolymers of more than 90 mass% of methacrylic acid esters with other monomers of less than or equal to 10 mass% are more preferred.

  Examples of monomers other than methacrylic acid esters include acrylic acid esters and monofunctional monomers having one polymerizable carbon-carbon double bond in the molecule.

  Monofunctional monomers include, for example, styrene monomers such as styrene, α-methylstyrene and vinyltoluene; alkenyl cyanides such as acrylonitrile and methacrylonitrile; acrylic acid; methacrylic acid; maleic anhydride; N-substituted Maleimide; and the like.

  From the viewpoint of heat resistance, the (meth) acrylic resin may be copolymerized with N-substituted maleimides such as phenylmaleimide, cyclohexylmaleimide and methylmaleimide, or in the molecular chain (in the main skeleton in the polymer or A lactone ring structure, a glutaric anhydride structure, a glutarimide structure, or the like may be introduced into the main chain).

From the viewpoint of easily increasing the hardness, weather resistance, and transparency of the resin laminate, (meth) acrylic resin, specifically,
(A1) Methyl methacrylate homopolymer and / or (a2) 50 to 99.9% by mass, preferably 70.0 to 99.8% by mass, based on all structural units constituting the copolymer Preferably structural units derived from 80.0-99.7% by weight methyl methacrylate, and 0.1-50% by weight, preferably 0.2-30% by weight, more preferably 0.3-20% by weight. % Formula (1):
[Wherein, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkyl group having 1 to 8 carbon atoms when R ₁ is a hydrogen atom, and R ₂ represents _{2 to 2} carbon atoms when R ₁ is a methyl group. Represents an alkyl group of 8; ]
It is preferable that it is a copolymer containing the at least 1 structural unit derived from the (meth) acrylic acid ester shown by these. Here, the content of each structural unit can be calculated by analyzing the obtained polymer by pyrolysis gas chromatography and measuring the peak area corresponding to each monomer.

In formula (1), _{R 1} represents a hydrogen atom or a methyl group, _{R 2} when _{R 1} is a hydrogen atom represents an alkyl group having 1 to 8 carbon atoms, _{R 2} when _{R 1} is a methyl group carbon An alkyl group having 2 to 8 atoms is represented. Examples of the alkyl group having 2 to 8 carbon atoms include ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group and octyl group. R ₂ is preferably an alkyl group having 2 to 4 carbon atoms and more preferably an ethyl group from the viewpoint of heat resistance.

  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 above lower limit, the transparency when exposed to a high temperature and high humidity environment is not sufficient, and when Mw is higher than the above upper limit, the film formability when producing the resin laminate (A) is increased. I can't get it. The Mw of the (meth) acrylic resin is preferably 120,000 or more, and more preferably 150,000 or more, from the viewpoint of easily increasing 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 film formability when the resin laminate (A) is produced. The weight average molecular weight is measured by gel permeation chromatography (GPC) measurement.

  The (meth) acrylic resin is usually 0.1 to 20 g / 10 minutes, preferably 0.2 to 5 g / 10 minutes, more preferably 0.5 to 3 g / 10, as measured at a load of 3.8 kg and 230 ° C. Minute melt mass flow rate (hereinafter sometimes referred to as MFR). The MFR is preferably not more than the above upper limit because the strength of the resulting film can be easily increased, and is preferably not less than the above lower limit from the viewpoint of the film formability of the resin laminate (A). The MFR can be measured in accordance with a method defined in JIS K 7210: 1999 “Plastic-thermoplastic melt mass flow rate (MFR) and melt volume flow rate (MVR) test method”. This JIS stipulates that poly (methyl methacrylate) -based materials are measured at a temperature of 230 ° C. and a load of 3.80 kg (37.3 N).

  From the viewpoint of heat resistance, the (meth) acrylic resin preferably has a Vicat softening temperature (hereinafter sometimes referred to as VST) of preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and even more preferably 102 ° C. or higher. . Although the upper limit of VST is not specifically limited, Usually, it is 150 degrees C or less. VST is based on JIS K 7206: 1999 and can be measured by the B50 method described therein. VST can be adjusted to the above range by adjusting the type of monomer and its ratio.

  The (meth) acrylic resin can be prepared by polymerizing the above monomers by a known method such as suspension polymerization or bulk polymerization. In that case, MFR, Mw, VST, etc. can be adjusted to a preferable range by adding a suitable chain transfer agent. As the chain transfer agent, an appropriate commercial product can be used. What is necessary is just to determine the addition amount of a chain transfer agent suitably according to the kind of monomer, its ratio, the characteristic to obtain | require, etc.

  Examples of the vinylidene fluoride resin contained in the intermediate layer of the resin laminate (A) include a homopolymer of vinylidene fluoride and a copolymer of vinylidene fluoride and other monomers. The vinylidene fluoride resin is selected from the group consisting of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether and ethylene from the viewpoint of easily increasing the transparency of the obtained resin laminate. It is preferably a copolymer of at least one monomer and vinylidene fluoride and / or a homopolymer of polyvinylidene fluoride (polyvinylidene fluoride), more preferably polyvinylidene fluoride.

  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, and even more preferably 200,000 to 450,000. Especially preferably, it is 350,000-450,000. When the laminate of the present invention is exposed to a high-temperature and high-humidity environment (for example, 60 ° C. and relative humidity of 90%), the transparency of the laminate of the present invention is likely to be increased. Therefore, it is preferable. Moreover, it is preferable that Mw is not more than the above upper limit because the film-forming property of the resin laminate (A) can be easily improved. The weight average molecular weight is measured by gel permeation chromatography (GPC) measurement.

  The vinylidene fluoride resin is preferably 0.1 to 40 g / 10 min, more preferably 0.1 to 30 g / 10 min, and even more preferably 0.1 to 25 g, measured at 3.8 kg load and 230 ° C. It has a melt mass flow rate (MFR) of / 10 minutes. The MFR is more preferably 0.2 g / 10 min or more, and even more preferably 0.5 g / 10 min or more. Further, the MFR is more preferably 20 g / 10 min or less, even more preferably 5 g / 10 min or less, and particularly preferably 2 g / 10 min or less. It is preferable that MFR is not more than the above upper limit because it is easy to suppress a decrease in transparency when the laminate of the present invention is used for a long period of time. It is preferable that MFR is not less than the above lower limit because the film-forming property of the resin laminate (A) can be easily improved. The MFR can be measured in accordance with a method defined in JIS K 7210: 1999 “Plastic-thermoplastic melt mass flow rate (MFR) and melt volume flow rate (MVR) test method”.

  The vinylidene fluoride resin is industrially produced by a suspension polymerization method or an emulsion polymerization method. The suspension polymerization method is carried out by using water as a medium, dispersing the monomer as droplets in the medium with a dispersant, and polymerizing an organic peroxide dissolved in the monomer as a polymerization initiator, A granular polymer of 100 to 300 μm is obtained. Suspension polymers are preferred because they have a simpler manufacturing process than powdered emulsions, have excellent powder handling properties, and do not contain an emulsifier or salting-out agent containing an alkali metal unlike emulsion polymers.

  A commercially available product may be used as the vinylidene fluoride resin. Examples of preferable commercially available products include “KF Polymer (registered trademark) T # 1300, T # 1100, T # 1000, T # 850, W # 850, W # 1000, W # 1100, and W # from Kureha Corporation. 1300 "," SOLEF (registered trademark) 6012, 6010 and 6008 "manufactured by Solvay.

  The intermediate layer may further include another resin different from the (meth) acrylic resin and the vinylidene fluoride resin. When it contains other resin, the kind is not specifically limited unless the transparency of the laminated body of this invention is impaired remarkably. From the viewpoint of the hardness and weather resistance of the laminate of the present invention, the amount of the other resin is preferably 15% by mass or less, and preferably 10% by mass or less, based on the total resin components contained in the intermediate layer. Is more preferable, and it is still more preferable that it is 5 mass% or less. Examples of other resins include polycarbonate resin, polyamide resin, acrylonitrile-styrene copolymer, methyl methacrylate-styrene copolymer, and polyethylene terephthalate. The intermediate layer may further contain another resin, but from the viewpoint of transparency, the amount of the other resin is preferably 1% by mass or less, and the resin contained in the intermediate layer contains (meth) acrylic resin and fluorine. More preferably, it is only vinylidene chloride resin.

  The content of alkali metal in the intermediate layer is 50 ppm or less based on the total resin components contained in the intermediate layer. When the content of the alkali metal in the intermediate layer exceeds the above upper limit, the transparency is lowered when the laminate of the present invention is used for a long time in a high temperature and high humidity environment. The content of 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. It is preferable that the content of the alkali metal in the intermediate layer is not more than the above upper limit because it is easy to suppress a decrease in transparency when the laminate of the present invention is used for a long time in a high temperature and high humidity environment. The lower limit of the content of alkali metal in the intermediate layer is 0, and it is extremely preferable that the content is not substantially contained from the viewpoint of easily suppressing the decrease in transparency of the laminate of the present invention. Here, in the (meth) acrylic resin and / or vinylidene fluoride resin contained in the intermediate layer, a trace amount of emulsifier used in the production process remains. Therefore, the intermediate layer contains alkali metal such as sodium or potassium derived from the remaining emulsifier, for example, 0.05 ppm or more. In particular, when the (meth) acrylic resin and / or vinylidene fluoride resin contained in the intermediate layer is obtained by emulsion polymerization, the amount of the emulsifier remaining in the resin increases, and the content of alkali metal in the intermediate layer also increases. Get higher. From the viewpoint of easily suppressing a decrease in the transparency of the laminate of the present invention, it is preferable to use a resin having a low alkali metal content as the (meth) acrylic resin and vinylidene fluoride resin contained in the intermediate layer.

  In order to make the content of the alkali metal in the resin within the above range, the amount of the compound containing the alkali metal is reduced during the polymerization of the resin, or the compound containing the alkali metal is increased by increasing the washing step after the polymerization. Just remove it. The alkali metal content can be determined by, for example, inductively coupled plasma mass spectrometry (ICP / MS). Examples of inductively coupled plasma mass spectrometry include sample pellets to be measured such as a high temperature ashing melting method, a high temperature ashing acid dissolution method, a Ca-added ashing acid dissolution method, a combustion absorption method, and a low temperature ashing acid dissolution method. The sample may be ashed by an appropriate method, dissolved in an acid, and the volume of the dissolved solution may be determined, and the content of alkali metal may be measured by inductively coupled plasma mass spectrometry.

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

  The thermoplastic resin layer includes at least one thermoplastic resin. The thermoplastic resin layer is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably, based on the total resin components contained in each thermoplastic resin layer, from the viewpoint of easily improving moldability. 80% by mass or more of thermoplastic resin is included. The upper limit of the amount of the thermoplastic resin is 100% by mass. Examples of the thermoplastic resin 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 include one type of thermoplastic resin or may include two or more types of thermoplastic resins.

  From the viewpoint of heat resistance of the resin laminate (A), the thermoplastic resin contained in the thermoplastic resin layer is preferably measured in accordance with JIS K 7206: 1999, preferably 100 to 160 ° C., more preferably 102 to It has a Vicat softening temperature of 155 ° C, even more preferably 102-152 ° C. Here, the Vicat softening temperature is the Vicat softening temperature of the resin when the thermoplastic resin layer contains one kind of thermoplastic resin, and the thermoplastic resin layer contains two or more kinds of thermoplastic resins. Is the Vicat softening temperature of a mixture of a plurality of thermoplastic resins. In the present invention, the Vicat softening temperature was measured according to the B50 method defined in JIS K 7206: 1999 “Plastics—Thermoplastic—Vicat Softening Temperature (VST) Test Method”. The Vicat softening temperature was measured with a heat distortion tester ["148-6 continuous type" manufactured by Yasuda Seiki Seisakusho Co., Ltd.]. The test piece at that time was measured by press-molding each raw material to a thickness of 3 mm.

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

  The thermoplastic resin layer is preferably a (meth) acrylic resin layer or a polycarbonate resin layer from the viewpoint of good moldability and easy enhancement of adhesion to the intermediate layer.

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

  Examples of the (meth) acrylic resin include the resins described for the (meth) acrylic resin contained in the intermediate layer. The preferred (meth) acrylic resin described for the intermediate layer is similarly preferred as the (meth) acrylic resin contained in the thermoplastic resin layer unless otherwise specified. The (meth) acrylic resin contained in the thermoplastic resin layer and the (meth) acrylic resin contained in the intermediate layer may be the same or different.

  The weight average molecular weight (Mw) of the (meth) acrylic resin is preferably 50,000 to 300,000, more preferably 70,000 to 250, from the viewpoint of good moldability and easy enhancement of mechanical strength. , 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. As the thermoplastic resin other than the (meth) acrylic resin, a thermoplastic resin compatible with the (meth) acrylic resin is preferable. Specifically, methyl methacrylate-styrene-maleic anhydride copolymer (for example, “Regisphi” manufactured by Denki Kagaku Kogyo), methyl methacrylate-methacrylic acid copolymer (for example, “Altglass HT121” manufactured by Arkema), polycarbonate resin Is mentioned. The thermoplastic resin other than the (meth) acrylic resin is preferably measured at 115 ° C. or higher, more preferably 117 ° C. or higher, even more preferably 120 ° C. or higher, in accordance with JIS K 7206: 1999, from the viewpoint of heat resistance. It is preferable to have a Vicat softening temperature of In addition, it is preferable that a thermoplastic resin layer does not contain a vinylidene fluoride resin substantially from a viewpoint of heat resistance and surface hardness.

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

  Next, another embodiment of the present invention in which the thermoplastic resin layer is a polycarbonate resin layer will be described below. In this embodiment, the thermoplastic resin layer includes one or more polycarbonate resins. From the viewpoint of impact resistance, the thermoplastic resin layer is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass based on the total resin components contained in each thermoplastic resin layer. The above polycarbonate resin is included.

  Examples of the polycarbonate resin include polymers obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonic ester such as diphenyl carbonate are reacted. Specifically, a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A) can be mentioned.

  Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 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 ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone Sulfone, and the like.

  These may be used alone or in combination of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, and the like may be used in combination.

  Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination. Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4′-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

  Examples of polycarbonate resins other than the above polycarbonate resins include polycarbonates synthesized from isosorbite and aromatic diols. An example of the polycarbonate is “DURABIO (registered trademark)” manufactured by Mitsubishi Chemical Corporation.

  Commercially available products may be used as the polycarbonate resin. For example, “Caliver (registered trademark) 301-4, 301-10, 301-15, 301-22, 301-30, 301-40” manufactured by Sumika Stylon Polycarbonate Co., Ltd. , SD2221W, SD2201W, TR2201 ”and the like.

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

In this embodiment, the polycarbonate resin contained in the thermoplastic resin layer is preferably ³ to 120 cm 3/10 minutes, more preferably ³ to 80 cm 3/10 minutes, as measured under conditions of a temperature of 300 ° C. and a load of 1.2 kg. , even more preferably 4~40cm ^3/10 min, particularly preferably 10 to 40 cm ^3/10 min melt volume rate (hereinafter, also referred to as MVR.) having a. When the MVR is higher than the lower limit, it is preferable because the fluidity is sufficiently high, the molding process is easy in melt coextrusion molding and the like, and the appearance is difficult to occur. When MVR is lower than the above upper limit, it is preferable because mechanical properties such as strength of the polycarbonate resin layer are easily improved. The MVR can be measured under the condition of 300 ° C. under a load of 1.2 kg in accordance with JIS K 7210 for the polycarbonate resin material.

  In this aspect, the thermoplastic resin layer may further contain a thermoplastic resin other than one or more polycarbonate resins. As the thermoplastic resin other than the polycarbonate resin, a thermoplastic resin compatible with the polycarbonate resin is preferable, a (meth) acrylic resin is more preferable, and a methacrylic resin having an aromatic ring or a cycloolefin in the structure is still more preferable. It is preferable that the thermoplastic resin layer contains a polycarbonate resin and the above (meth) acrylic resin because the surface hardness of the thermoplastic resin layer can be made higher than when only the polycarbonate resin is included.

  At least one of the intermediate layer and the thermoplastic resin layer in the resin laminate (A) may further contain various commonly used additives as long as the effects of the present invention are not impaired. Examples of additives include stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, foaming agents, lubricants, mold release agents, antistatic agents, flame retardants, mold release agents, polymerization inhibitors, and flame retardant aids. And coloring agents such as reinforcing agents, nucleating agents, and bluing agents.

  Examples of the colorant include a compound having an anthraquinone skeleton and a compound having a phthalocyanine skeleton. Among these, a compound having an anthraquinone skeleton is preferable 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 using a bluing agent as a coloring agent, the content can be about 0.01-10 ppm on the basis of all the resin components contained in each layer containing a bluing agent. This content is preferably 0.01 ppm or more, more preferably 0.05 ppm or more, even more preferably 0.1 ppm or more, and preferably 7 ppm or less, more preferably 5 ppm or less, even more preferably 4 ppm or less, Especially preferably, it is 3 ppm or less. Known bluing agents can be used as appropriate. For example, Macrolex (registered trademark) Blue RR (manufactured by Bayer), Macrolex (registered trademark) Blue 3R (manufactured by Bayer), respectively, under the trade name, Sumiplast (registered trademark) Violet B (manufactured by Sumika Chemtex Co., Ltd.) and Polysynthrene (registered trademark) Blue RLS (manufactured by Clariant), Diaresin Violet D, Diaresin Blue G, and Diaresin Blue N (manufactured by Mitsubishi Chemical Corporation) It is done.

  It does not specifically limit as a ultraviolet absorber, You may use a conventionally well-known various ultraviolet absorber. For example, the ultraviolet absorber which has an absorption maximum in 200-320 nm or 320-400 nm is mentioned. Specific examples include triazine ultraviolet absorbers, benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, benzoate ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers. As an ultraviolet absorber, you may use 1 type of these ultraviolet absorbers individually or in combination of 2 or more types. The viewpoint that the combination of at least one ultraviolet absorber having an absorption maximum at 200 to 320 nm and at least one ultraviolet absorber having an absorption maximum at 320 to 400 nm can also more effectively prevent damage from ultraviolet rays. To preferred. Commercially available products may be used as the UV absorber, such as “Kemisorb 102” (2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-N-octyl) manufactured by Chemipro Kasei Co., Ltd. Oxyphenyl) -1,3,5-triazine) (absorbance 0.1), “ADEKA STAB LA-F70” (2,4,6-tris (2-hydroxy-4-hexyloxy-3-methyl) manufactured by ADEKA Corporation Phenyl) -1,3,5-triazine) (absorbance 0.6), “Adekastab LA-31, LA-31RG, LA-31G” (2,2′-methylenebis (4- (1,1,3,3) -Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol) (absorbance 0.2), "ADEKA STAB LA-46" (2- (4,6) manufactured by ADEKA Corporation. Diphenyl-1,3,5-triazin-2-yl) -5- (2- (2-ethylhexanoyloxy) ethoxy) phenol) (absorbance 0.05) or “TINUVIN 1577” manufactured by BASF Japan Ltd. ( 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine) (absorbance 0.1) and the like.

  When at least one of the intermediate layer (A), the thermoplastic resin layer (B) and (C) further contains a UV absorber, the content of the UV absorber in each layer depends on the purpose, the type of the UV absorber, etc. You may select suitably according to it. For example, the content of the ultraviolet absorber can be about 0.005 to 2.0% by mass based on the total resin components 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 even more preferably 0.03% by mass or more. Further, the content of the ultraviolet absorber is preferably 1.5% by mass or less, more preferably 1.0% by mass or less. It is preferable that the content of the ultraviolet absorber is not less than the above lower limit from the viewpoint of easily enhancing the ultraviolet absorption effect, and being not more than the above upper limit prevents a change in the color (for example, yellowness YI) of the resin laminate. It is preferable because it is easy to do. For example, it is preferable to use the above-mentioned commercially available “ADK STAB LA-31, LA-31RG, LA-31G” in the above amounts.

  In another aspect of the present invention, the thermoplastic resin layers (B) and (C) are polycarbonate resin layers, and 0.005 to 2.0 mass based on the total resin components contained in each thermoplastic resin layer. % Ultraviolet absorber is preferable because it is easy to obtain a resin laminate having excellent light resistance.

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

  From the viewpoint of the rigidity of the laminate of the present invention, the average value of the film thickness of the resin laminate (A) is preferably 100 μm or more, more preferably 200 μm or more, and even more preferably 300 μm or more. Moreover, from a viewpoint of transparency, Preferably it is 2000 micrometers or less, More preferably, it is 1500 micrometers or less, More preferably, it is 1000 micrometers or less. The film thickness of the resin laminate (A) is measured with a digital micrometer. Let the average value which performed the said measurement in 10 points | pieces of a resin laminated body (A) be an average value of a 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 still more preferably 50 μm or more, from the viewpoint of easily increasing the surface hardness. From the viewpoint of dielectric constant, each is preferably 200 μm or less, more preferably 175 μm or less, and even more preferably 150 μm or less. The measuring method of the average value of the 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 preferably 100 μm or more, more preferably 200 μm or more, and even more preferably 300 μm or more, from the viewpoint of dielectric constant. Moreover, from a viewpoint of transparency, Preferably it is 1500 micrometers or less, More preferably, it is 1200 micrometers or less, More preferably, it is 1000 micrometers or less. The average value of the film thickness of the intermediate layer can be measured by the same method as the measurement of the average value of the film thickness of the thermoplastic resin layer.

  The resin laminate (A) can 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 from a hard coat agent composition. The hard coat agent composition contains a curable compound that provides scratch resistance as an essential component, and includes, for example, a curing catalyst, conductive particles, a solvent, a leveling agent, a stabilizer, an antioxidant, a colorant, and the like. It contains.

  Examples of the curable compound include acrylate compounds, urethane acrylate compounds, epoxy acrylate compounds, carboxyl group-modified epoxy acrylate compounds, polyester acrylate compounds, copolymer acrylate compounds, alicyclic epoxy resins, glycidyl ether epoxy resins, vinyl ether compounds, oxetanes. Compounds and the like. From the viewpoint of easily improving the scratch resistance of the obtained hard coat layer, the curable compound is a radical polymerization curable compound such as a polyfunctional acrylate compound, a polyfunctional urethane acrylate compound, or a polyfunctional epoxy acrylate compound, an alkoxysilane, A thermosetting curable compound such as alkylalkoxysilane is preferable. These curable compounds are preferably those that are cured by irradiating energy rays such as electron beams, radiation, and ultraviolet rays, or those that are cured by heating. These curable compounds may be used alone or in combination of two or more compounds.

  The curable compound is preferably a compound having at least three (meth) acryloyloxy groups in the molecule from the viewpoint of easily increasing the transparency and surface hardness of the hard coat layer. Examples of the curable compound having at least three (meth) acryloyloxy groups in the molecule include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaglycerol tri (Meth) acrylate, pentaerythritol tri- or tetra- (meth) acrylate, dipentaerythritol tri-, tetra-, penta- or hexa- (meth) acrylate, tripentaerythritol tetra-, penta-, hexa- or hepta- A poly (meth) acrylate of a trihydric or higher polyhydric alcohol such as (meth) acrylate; a compound having at least two isocyanato groups in the molecule, and a (meth) acrylate having a hydroxyl group to the isocyanato group Urethane (meth) acrylate obtained by reacting at a ratio such that the hydroxyl groups are equimolar or more and having 3 or more (meth) acryloyloxy groups in the molecule [for example, diisocyanate and pentaerythritol tri (meth) A hexafunctional urethane (meth) acrylate is obtained by the reaction of the acrylate]; and tri (meth) acrylate of tris (2-hydroxyethyl) isocyanuric acid. In addition, although the monomer was illustrated here, you may use these monomers as it is, for example, you may use what was in the form of oligomers, such as a dimer and a trimer. Moreover, you may use a monomer and an oligomer together. You may use these (meth) acrylate compounds individually or in mixture of 2 or more types.

  A commercially available compound may be used as the curable compound having at least three (meth) acryloyloxy groups in the molecule. Specifically, “NK Hard M101” (urethane acrylate type), “NK Ester A-TMM-3L” (pentaerythritol triacrylate), “NK Ester A-A” manufactured by Shin-Nakamura Chemical Co., Ltd. “TMMT” (pentaerythritol tetraacrylate), “NK ester A-9530” (dipentaerythritol pentaacrylate) and “NK ester A-DPH” (dipentaerythritol hexaacrylate), “KAYARAD DPCA” manufactured by Nippon Kayaku Co., Ltd. (Dipentaerythritol hexaacrylate), “Nopcocure 200” series manufactured by San Nopco Co., Ltd., “Unidic” series manufactured by Dainippon Ink & Chemicals, Inc., and the like.

  When a compound having at least three (meth) acryloyloxy groups in the molecule is used as the curable compound, other curable compounds such as ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate are used as necessary. , 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and other compounds having two (meth) acryloyloxy groups in the molecule may be used in combination. The amount is usually up to 20 parts by mass with respect to 100 parts by mass of the compound having at least three (meth) acryloyloxy groups in the molecule.

  When the hard coat agent composition is cured with ultraviolet rays, it is preferable to use a photopolymerization initiator as a curing catalyst from the viewpoint of easily increasing the surface hardness and adhesion of the hard coat layer. Examples of the photopolymerization initiator include benzyl, benzophenone and derivatives thereof, thioxanthones, benzyldimethyl ketals, α-hydroxyalkylphenones, hydroxyketones, aminoalkylphenones, acylphosphine oxides, and the like. As the photopolymerization initiator, the above compounds may be used alone or in combination of two or more. The usage-amount of a photoinitiator is 0.1-5 mass parts normally with respect to 100 mass parts of sclerosing | hardenable compounds. When the amount is less than 0.1 part by weight, the curing rate tends to be difficult to increase as compared with the case where no photopolymerization initiator is used.

  A commercially available photopolymerization initiator may be used. Specifically, for example, “IRGACURE 651”, “IRGACURE 184”, “IRGACURE 500”, “IRGACURE 1000”, “IRGACURE 2959”, “DAROCUR 1173”, “IRGACURE” manufactured by Ciba Specialty Chemicals Co., Ltd. 907, IRGACURE 369, IRGACURE 1700, IRGACURE 1800, IRGACURE 819, IRGACURE 784, IRGACURE series and DAROCUR (Darocur) series, both Nippon Kayaku Co., Ltd. "KAYACURE ITX", "KAYACURE DETX-S", "KAYACURE BP-100", "KAYACUREBMS", "KA" KAYACURE series such as “YACURE 2-EAQ”.

  By containing conductive particles in the hard coat agent composition, antistatic properties can be imparted to the hard coat layer. Examples of the conductive particles include antimony-tin composite oxide, tin oxide containing phosphorus, antimony oxide such as antimony pentoxide, antimony-zinc composite oxide, titanium oxide, and indium-tin composite oxide (ITO). Such inorganic particles are preferably used. 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 increasing the transparency of the hard coat layer. From the viewpoint of easily improving the antistatic property of the hard coat layer, the average particle size is preferably 0.001 μm or more.

  The conductive particles can be produced by, for example, a gas phase decomposition method, a plasma evaporation method, an alkoxide decomposition method, a coprecipitation method, a hydrothermal method, or 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 silicon coupling agent, an aluminum coupling agent, or the like.

  When making a hard-coat agent composition contain electroconductive particle, Preferably the content is 2-50 mass parts with respect to 100 mass parts of sclerosing | hardenable compounds, More preferably, it is 3-20 mass parts. As the content of the conductive particles increases, the antistatic property of the hard coat layer tends to be improved. However, if the amount of the conductive particles used is too large, the transparency of the hard coat layer is lowered, which is not preferable.

  The hard coat agent composition may contain a solvent for the purpose of adjusting the viscosity thereof. In particular, when conductive particles are contained in the hard coat agent composition, it is preferable to contain a solvent in order to disperse the conductive particles satisfactorily. When the hard coat agent composition contains a solvent and conductive particles, for example, the hard coat agent composition is mixed with the conductive particles and the solvent, and after the conductive particles are dispersed in the solvent, the dispersion is cured. It may be produced by mixing with a conductive compound, or after mixing a curable compound and a solvent, conductive particles may be dispersed in this mixed solution.

  The solvent is not particularly limited as long as it can dissolve the curable compound and can easily volatilize after coating. Examples of the solvent include alcohols such as diacetone alcohol, methanol, ethanol, isopropyl alcohol, isobutyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, and 1-methoxy-2-propanol, acetone, and methyl ethyl ketone. , Ketones such as methyl isobutyl ketone and diacetone alcohol, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, and water. What is necessary is just to adjust the usage-amount of a solvent suitably according to the property etc. of a curable compound.

  A leveling agent may be contained in the hard coat agent composition from the viewpoint of easily improving the coating uniformity of the hard coat agent. As the leveling agent, silicone oil is preferably used. Examples thereof include dimethyl silicone oil, phenylmethyl silicone oil, alkyl / aralkyl modified silicone oil, fluorosilicone oil, polyether modified silicone oil, fatty acid ester modified silicone oil, methyl Hydrogen silicone oil, silanol group-containing silicone oil, alkoxy group-containing silicone oil, phenol group-containing silicone oil, methacryl-modified silicone oil, amino-modified silicone oil, carboxylic acid-modified silicone oil, carbinol-modified silicone oil, epoxy-modified silicone oil, mercapto Examples thereof include modified silicone oil, fluorine-modified silicone oil, and polyether-modified silicone oil. These leveling agents may be used alone or in combination of two or more. The usage-amount of a leveling agent is 0.01-5 mass parts normally with respect to 100 mass parts of sclerosing | hardenable compounds.

  A commercially available leveling agent may be used. Specifically, for example, “SH200-100cs”, “SH28PA”, “SH29PA”, “SH30PA”, “ST83PA”, “ST80PA”, “ST97PA” and “ST97PA” manufactured by Toray Dow Corning Silicone Co., Ltd. “ST86PA”, all of which are “BYK-302”, “BYK-307”, “BYK-320”, “BYK-330” and the like manufactured by Big Chemie Japan, Inc.

  By applying the hard coat agent composition thus obtained to at least one surface of the laminate having the intermediate layer and the thermoplastic resin layer to form a curable coating film, and then curing to form a cured coating film. A hard coat layer having scratch resistance can be obtained. The hard coating agent composition may be applied by a coating method such as a bar coating method, a micro gravure coating method, a roll coating method, a flow coating method, a dip coating method, a spin coating method, a die coating method, or a spray coating method. The curable coating film may be cured by irradiation with energy rays, heating, or the like depending on the type of the hard coating agent composition.

  Examples of energy rays in the case of curing by irradiation with energy rays include ultraviolet rays, electron beams, radiation, and the like. Conditions such as intensity and irradiation time are appropriately selected according to the type of the hard coat agent composition. . In addition, in the case of curing by heating, conditions such as temperature and time are appropriately selected according to the type of the hard coat agent composition, but the heating temperature is generally set so that the resin substrate does not deform. Is preferably 100 ° C. or lower. When the hard coat agent composition contains a solvent, the curable coating film may be cured after the solvent is volatilized after coating, or the solvent volatilization and the curing of the curable coating film are performed simultaneously. Also good.

  The average value of the film thickness of the hard coat layer is preferably 0.5 to 50 μm, more preferably 1 to 20 μm. As the thickness of the hard coat layer is smaller, cracks tend not to occur easily. However, if the thickness is too small, the scratch resistance becomes insufficient, which is not preferable. The film thickness of the hard coat layer is measured using a microscope (for example, a microscope manufactured by Micro Square Inc.). An average value of values obtained by performing the above measurement at any 10 points of the hard coat layer is defined as an average value of the film thickness.

  If necessary, the surface of the hard coat layer may be subjected to antireflection treatment by a coating method, a sputtering method, a vacuum deposition method, or the like. Alternatively, an antireflection sheet prepared separately may be bonded to one side or both sides of the hard coat layer to give an antireflection effect.

  The hard coat layer preferably has a water contact angle of 100 ° or more, more preferably 105 ° or more, and more preferably 110 ° or more. The water contact angle was measured according to JIS R3257: 199 using a contact angle meter (image processing contact angle meter “FACE CA-X type” manufactured by Kyowa Interface Science Co., Ltd.).

  The resin laminate (A) may further 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 antireflection layer, an antiglare layer, an antistatic layer, and an anti-fingerprint layer. These functional layers may be laminated | stacked on the laminated body of this invention through the adhesive layer, and the coating layer laminated | stacked by coating may be sufficient as them. As the functional layer, for example, a cured film as described in JP 2013-86273 A may be used. The functional layer is, for example, an antireflection layer formed on one or both surfaces of at least one functional layer selected from the group consisting of an antiglare layer, an antistatic layer, and an anti-fingerprint layer by a coating method, a sputtering method, a vacuum deposition method, or the like. Further, it may be a coated layer, or may be a layer in which an antireflection sheet is bonded to one side or both sides of the at least one functional layer.

  The thickness of the functional layer may be appropriately selected according to the purpose of each functional layer, but is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 5 μm or more from the viewpoint of easily expressing the function. From the viewpoint of easily preventing cracking, it is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 70 μm or less.

  The transparent pressure-sensitive adhesive (B) can be appropriately selected depending on the member to be bonded, and may be, for example, an acrylic, rubber-based, urethane-based, silicone-based, or polyvinyl ether-based pressure-sensitive adhesive, and in particular, transparency and weather resistance. From the viewpoint of excellent properties, heat resistance and the like, an acrylic pressure-sensitive adhesive containing an acrylic resin is suitable. Moreover, a water-system adhesive agent and an active energy ray hardening-type adhesive agent can also be used as a transparent adhesive (B).

  The acrylic pressure-sensitive adhesive is generally a pressure-sensitive adhesive containing an acrylic resin and a crosslinking agent. The monomer component constituting the acrylic resin includes, for example, (meth) acrylic acid alkyl ester; one (meth) acryloyl group which is an olefinic double bond in the molecule, hydroxyl group, carboxyl group, amide group, amino And a compound having a polar functional group such as a group or an epoxy group in the same molecule (hereinafter sometimes referred to as a (meth) acrylic monomer having a polar functional group).

Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isooctyl (meth) acrylate, and (meth) acrylic. Examples include (meth) acrylic acid C _1-10 alkyl-esters such as 2-ethylhexyl acid, 2-methoxyethyl (meth) acrylate, and ethoxymethyl (meth) acrylate.

Examples of the (meth) acrylic monomer having a polar functional group include (meth) acrylic acid hydroxy C _1-6 alkyl such as (meth) acrylic acid, (meth) acrylic acid 2-hydroxypropyl, and (meth) acrylic acid hydroxyethyl. , (Meth) acrylamide, N, N-dimethylaminoethyl, (meth) acrylate, glycidyl (meth) acrylate, and the like. Among these, (meth) acrylic acid hydroxy C _1-6 alkyls such as (meth) acrylic acid 2-hydroxypropyl and (meth) acrylic acid hydroxyethyl are preferable.

  The monomer component which comprises these acrylic resins can be used individually or in combination of 2 or more types.

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

  The monomer component used as the raw material for the acrylic resin further contains a monomer other than the (meth) acrylic acid alkyl ester and the (meth) acrylic monomer having a polar functional group (hereinafter sometimes referred to as a third monomer). Also good. Examples include a monomer having one olefinic double bond and at least one aromatic ring in the molecule, a styrene monomer, a (meth) acrylic acid ester having an alicyclic structure in the molecule, and a vinyl monomer. And monomers having a plurality of (meth) acryloyl groups in the molecule.

In particular, a monomer having one olefinic double bond and at least one aromatic ring in the molecule can be preferably used. Among these, 2-phenoxyethyl (meth) acrylate, 2- (2-phenoxyethoxy) ethyl (meth) acrylate, (meth) acrylate of ethylene oxide-modified nonylphenol, and 2- (o-phenylphenoxy) ethyl (meth) acrylate are preferable. 2-phenoxyethyl acrylate is most preferred.
Monomers (third monomers) other than the (meth) acrylic acid alkyl ester and the (meth) acrylic monomer having a polar functional group may be used alone or in combination with a plurality of different types. The structural unit derived from these third monomers can usually be present in the range of 0 to 20% by weight, preferably 0 to 10% by weight, based on the entire acrylic resin.

  The (meth) acrylic resin constituting the acrylic pressure-sensitive adhesive preferably has a standard polystyrene equivalent weight average molecular weight Mw by gel permeation chromatography (GPC) in the range of 1,000,000 to 2,000,000. When this weight average molecular weight Mw is 1 million or more, the adhesiveness under high temperature and high humidity is improved, and floating or peeling between the transparent pressure-sensitive adhesive (B) and the polarizing plate to which the pressure-sensitive adhesive is bonded is improved. It is preferable because it is easy to suppress the occurrence and the reworkability tends to be improved. In addition, when the weight average molecular weight Mw of the acrylic resin is 2 million or less, even if the dimensions of the polarizing plate or the like to which the pressure-sensitive adhesive is bonded change, the pressure-sensitive adhesive changes following the dimensional change. For example, when used in a liquid crystal cell or the like, it is preferable because light leakage and color unevenness of the display tend to be suppressed. Furthermore, the molecular weight distribution represented by the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn is preferably in the range of 3-7. The acrylic resin contained in the acrylic pressure-sensitive adhesive can be composed only of a relatively high molecular weight as described above, but other acrylic resins such as (meth) acrylic acid esters can be used. It can also be composed of a mixture with a derived structural unit as a main component and a weight average molecular weight in the range of 50,000 to 300,000.

  Said acrylic resin which comprises an acrylic adhesive can be manufactured by a well-known method, for example, a solution polymerization method, an emulsion polymerization method, a block polymerization method, a suspension polymerization method etc. 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, redox initiators using a combination of peroxide and a reducing agent. Among these, 2,2'-azobisisobutyronitrile, benzoyl 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 with respect to 100 parts by mass of the total amount of monomers as raw materials for the acrylic resin.

  The cross-linking agent is a compound having in the molecule at least two functional groups capable of undergoing a cross-linking reaction with a structural unit derived from a (meth) acrylic monomer having a polar functional group in an acrylic resin. For example, an isocyanate compound, an epoxy Compound, metal chelate compound, aziridine compound and the like.

  Of these crosslinking agents, isocyanate compounds are preferably used. The isocyanate compound can be used in the form of an adduct obtained by reacting a polyol with a compound having at least two isocyanato groups (—NCO) in the molecule, a dimer, a trimer, or the like. Specifically, tolylene diisocyanate, adduct obtained by reacting tolylene diisocyanate with polyol, tolylene diisocyanate dimer, tolylene diisocyanate trimer, hexamethylene diisocyanate, hexamethylene diisocyanate react with polyol And adducts obtained by mixing, hexamethylene diisocyanate dimer, hexamethylene diisocyanate trimer, and the like.

  A crosslinking agent is normally mix | blended in the ratio of about 0.01-5 mass parts with respect to 100 mass parts of acrylic resins, Preferably it is 0.1-5 mass parts, More preferably, it is 0.2-3 mass parts. It is preferable to mix | blend in the ratio. If the blending amount of the crosslinking agent with respect to 100 parts by mass of the acrylic resin is 0.01 parts by mass or more, preferably 0.1 parts 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 pressure-sensitive adhesive as necessary. As other components that can be blended, conductive fine particles such as metal fine particles, metal oxide fine particles, or fine particles coated with metal, ion conductive compositions, ionic compounds having organic cations or anions, silane Examples include coupling agents, crosslinking catalysts, weathering stabilizers, tackifiers, plasticizers, softeners, dyes, pigments, inorganic fillers, resins other than the above acrylic resins, and light diffusing fine particles such as organic beads. It is also useful to blend a UV curable compound with the pressure-sensitive adhesive and form a pressure-sensitive adhesive layer, and then cure it by irradiating with ultraviolet rays to form a harder pressure-sensitive adhesive layer.

  Examples of methods for applying (or coating and bonding) the adhesive to the resin laminate (A) include, for example, a laminator, a bar coating method, a micro gravure coating method, a roll coating method, a dipping coating method, a spin coating method, and a die coating method. , Cast transfer method, flow coating method, spray coating method and the like.

  Specifically, in the resin laminate of the present invention, a pressure-sensitive adhesive composition in which a pressure-sensitive adhesive is dissolved in an appropriate solvent (for example, ethyl acetate) is directly applied to one side or both sides of the resin laminate (A), dried, etc. It may be obtained by using a separator (release film) as a base material, and a pressure-sensitive adhesive with a separator obtained by applying the pressure-sensitive adhesive composition to the separator is bonded to one side or both sides of the resin laminate (A). You may obtain by doing.

  As an aqueous adhesive, for example, a polyvinyl alcohol resin or a urethane resin is used as a main component, and in order to improve adhesiveness, a composition containing a crosslinking agent or a curable compound such as an isocyanate compound or an epoxy compound, and It is common to do.

  When polyvinyl alcohol 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 group-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, methylol group-modified polyvinyl alcohol, and amino A modified polyvinyl alcohol-based resin such as group-modified polyvinyl alcohol may be used. Such an aqueous solution of polyvinyl alcohol resin is used as an aqueous adhesive, and the concentration of the polyvinyl alcohol resin in the aqueous adhesive is usually 1 to 10 parts by mass, preferably 100 parts by mass of water. 1 to 5 parts by mass.

  In order to improve adhesiveness, curable compounds such as polyhydric aldehydes, water-soluble epoxy resins, melamine compounds, zirconia compounds, and zinc compounds are added to aqueous adhesives made of polyvinyl alcohol resin aqueous solutions. can do. Examples of water-soluble epoxy resins include water-soluble products obtained by reacting epichlorohydrin with polyamide polyamines obtained by reacting polyalkylene polyamines such as diethylenetriamine and triethylenetetramine with dicarboxylic acids such as adipic acid. There is a characteristic polyamide epoxy resin. Examples of such commercially available polyamide epoxy resins include “Smiles Resin 650” and “Smiles Resin 675” sold by Sumika Chemtex Co., Ltd., and “WS-525” sold by Japan PMC Co., Ltd. There is. When mix | blending a water-soluble epoxy resin, the addition amount is about 1-100 mass parts normally with respect to 100 mass parts of polyvinyl alcohol-type resin, Preferably it is 1-50 mass parts.

  When a urethane resin is used as the main component of the aqueous adhesive, it is effective to use a polyester ionomer type urethane resin as the main component of the aqueous adhesive. The polyester-based ionomer type urethane resin here is a urethane resin having a polyester skeleton, into which a small amount of an ionic component (hydrophilic component) is introduced. Such an ionomer type urethane resin is directly emulsified in water without using an emulsifier to form an emulsion, so that it can be used as an aqueous adhesive. When using a polyester ionomer type urethane resin, it is effective to blend a water-soluble epoxy compound as a crosslinking agent. The use of a polyester ionomer urethane resin as an adhesive for a polarizing plate is described in, for example, JP-A-2005-70140 and JP-A-2005-208456.

  The aqueous adhesive is usually used in the form of an aqueous adhesive composition dissolved in water. The resin laminate of the present invention may be obtained by applying the aqueous adhesive composition to one or both sides of the resin laminate (A) and drying it. In addition, the component which is not melt | dissolved in the water contained in a water-system adhesive should just be the state disperse | distributed in the system.

  Also, for example, when a polarizing plate or the like is bonded to the resin laminate of the present invention, a water-based adhesive is injected between the polarizing plate and the resin laminate (A), and then heated to evaporate the water while being thermally crosslinked. Sufficient adhesion can be given to both by advancing reaction.

  The active energy ray-curable adhesive is cured by being irradiated with active energy rays, and can be bonded to a polarizing plate or the like on which a resin laminate with a transparent adhesive is bonded with sufficient strength. For example, a cationic polymerizable active energy ray curable adhesive containing an epoxy compound and a cationic polymerization initiator, a radical polymerizable active energy ray curable adhesive containing an acrylic curing component and a radical polymerization initiator, an epoxy compound An active energy ray-curable adhesive containing both a cationic polymerizable curing component such as a radical polymerization curing component such as an acrylic compound, and a cationic polymerization initiator and a radical polymerization initiator incorporated therein, And an electron beam curable adhesive that is cured by irradiating the active energy ray curable adhesive containing no initiator with an electron beam. Preferably, it is a radical polymerizable active energy ray-curable adhesive containing an acrylic curing component and a radical polymerization initiator. Further, a cationic polymerizable active energy ray-curable adhesive containing an epoxy compound and a cationic polymerization initiator that can be used substantially in a solvent-free manner is preferable.

  A cationically polymerizable epoxy compound that is liquid at room temperature, has proper fluidity even in the absence of a solvent, and gives an appropriate cured adhesive strength, and a suitable cation The active energy ray-curable adhesive blended with the polymerization initiator can omit the drying equipment that is usually required in the step of bonding the laminate of the present invention to the polarizer in the production equipment for polarizing plates. In addition, by irradiating with an appropriate active energy dose, the curing rate can be accelerated and the production rate can be improved.

  Epoxy compounds used for such adhesives include, for example, aromatic compounds having a hydroxyl group or glycidyl etherified compounds of chain compounds, glycidyl aminated compounds of compounds having amino groups, and chain compounds having a C—C double bond. An alicyclic epoxy compound in which a glycidyloxy group or an epoxyethyl group is bonded to a saturated carbocycle directly or via alkylene, or an epoxy group is bonded directly to a saturated carbocycle it can. These epoxy compounds may be used alone or in combination with a plurality of different types. Among these, alicyclic epoxy compounds are preferably used because they are excellent in cationic polymerizability.

  The glycidyl etherified product of an aromatic compound or a chain compound having a hydroxyl group can be produced, for example, by a method in which epichlorohydrin is addition-condensed to the hydroxyl group of these aromatic compound or chain compound under basic conditions. Such glycidyl etherified products of aromatic compounds or chain compounds having a hydroxyl group include diglycidyl ethers of bisphenols, polyaromatic epoxy resins, alkylene glycols or diglycidyl ethers of polyalkylene glycols, and the like. .

  Examples of diglycidyl ethers of bisphenols include, for example, glycidyl ethers of bisphenol A and oligomers thereof, glycidyl ethers of bisphenol F and oligomers thereof, 3,3 ′, 5,5′-tetramethyl-4,4′- Examples include glycidyl etherified products of biphenol and oligomers thereof.

  Examples of polyaromatic epoxy resins include glycidyl etherified products of phenol novolac resins, glycidyl etherified products of cresol novolac resins, glycidyl etherified products of phenol aralkyl resins, glycidyl etherified products of naphthol aralkyl resins, and glycidyl ethers of phenol dicyclopentadiene resins. And the like. Further, glycidyl etherified products of trisphenols and oligomers thereof belong to the polyaromatic epoxy resin.

  Examples of diglycidyl ether of alkylene glycol or polyalkylene glycol include glycidyl etherified product of ethylene glycol, glycidyl etherified product of diethylene glycol, glycidyl etherified product of 1,4-butanediol, glycidyl etherified product of 1,6-hexanediol, etc. Can be mentioned.

  A glycidyl aminated product of a compound having an amino group can be produced, for example, by a method in which epichlorohydrin is addition-condensed to the amino group of the compound under basic conditions. The compound having an amino group may have a hydroxyl group at the same time. Examples of the glycidyl amination product of the compound having an amino group include a glycidyl amination product of 1,3-phenylenediamine and an oligomer thereof, a glycidyl amination product of 1,4-phenylenediamine and an oligomer thereof, and 3-aminophenol. Glycidyl amination and glycidyl etherification product and oligomers thereof, glycidyl amination and glycidyl etherification product of 4-aminophenol, oligomers thereof and the like are included.

  The epoxidized product of a chain compound having a C—C double bond can be produced by a method in which the C—C double bond of the chain compound is epoxidized with a peroxide under basic conditions. Examples of the chain compound having a C—C double bond include butadiene, polybutadiene, isoprene, pentadiene, hexadiene and the like. Further, terpenes having a double bond can also be used as an epoxidation raw material, and examples of acyclic monoterpenes include linalool. The peroxide used for epoxidation can be, for example, hydrogen peroxide, peracetic acid, tert-butyl hydroperoxide, and the like.

  An alicyclic epoxy compound in which a glycidyloxy group or an epoxyethyl group is bonded to a saturated carbocycle directly or via an alkylene is an aromatic ring of an aromatic compound having a hydroxyl group, typically a bisphenol. Examples thereof include a glycidyl etherified product of a hydrogenated polyhydroxy compound obtained by hydrogenation, a glycidyl etherified product of a cycloalkane compound having a hydroxyl group, and an epoxidized product of a cycloalkane compound having a vinyl group.

  The epoxy compounds described above can be easily obtained as commercial products. For example, “jER” series sold by Mitsubishi Chemical Corporation and “Epicron” sold by DIC Corporation, respectively, under the trade names. "Epototo (registered trademark)" sold by Toto Kasei Co., Ltd., "Adeka Resin (registered trademark)" sold by ADEKA Corporation, and "Denacol (registered trademark)" sold by Nagase ChemteX Corporation. ) ”,“ Dow Epoxy ”sold by Dow Chemical Company,“ Tepic (registered trademark) ”sold by Nissan Chemical Industries, Ltd., and the like.

  On the other hand, an alicyclic epoxy compound in which an epoxy group is directly bonded to a saturated carbocyclic ring is, for example, a non-aromatic cyclic compound having a C—C double bond in the ring. It can be produced by a method of epoxidation with a peroxide under conditions. As the non-aromatic cyclic compound having a C—C double bond in the ring, for example, a compound having a cyclopentene ring, a compound having a cyclohexene ring, a cyclopentene ring or a cyclohexene ring is bonded to at least two carbon atoms. Examples include polycyclic compounds forming an additional ring. The 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 in which an epoxy group is directly bonded to a saturated carbocyclic ring has an alicyclic structure having an epoxy group directly bonded to the ring as described above in the molecule through an appropriate linking group. It may be a compound in which at least two are formed. Examples of the linking group herein include an ester bond, an ether bond, and an alkylene bond.

Specific examples of alicyclic epoxy compounds in which an epoxy group is directly bonded to a saturated carbocyclic ring include the following.
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-
Adducts with epoxycyclohexane,
Ethylene bis (3,4-epoxycyclohexanecarboxylate),
Oxydiethylene bis (3,4-epoxycyclohexanecarboxylate),
1,4-cyclohexanedimethyl bis (3,4-epoxycyclohexanecarboxylate),
3- (3,4-epoxycyclohexylmethoxycarbonyl) propyl 3,4-epoxycyclohexanecarboxylate and the like.

  The alicyclic epoxy compound in which the epoxy group is directly bonded to the saturated carbocyclic ring described above can also be easily obtained as a commercial product. For example, each product is sold by Daicel Corporation under the trade name. Examples include the “Celoxide” series and “Cyclomer”, and the “Syracure UVR” series sold by Dow Chemical.

  The curable adhesive containing the epoxy compound may further contain an active energy ray-curable compound other than the epoxy compound. Examples of the active energy ray-curable compound other than the epoxy compound include an oxetane compound and an acrylic compound. Especially, since there exists a possibility that a cure rate can be accelerated | stimulated in cationic polymerization, it is preferable to use an oxetane compound together.

The oxetane compound is a compound having a 4-membered ring ether in the molecule, and examples thereof include the following.
1,4-bis [(3-ethyloxetane-3-yl) methoxymethyl] benzene,
3-ethyl-3- (2-ethylhexyloxymethyl) oxetane,
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.

  Oxetane compounds can also be easily obtained as commercial products. For example, “Aron Oxetane (registered trademark)” series sold by Toagosei Co., Ltd. and Ube Industries, Ltd. "ETERNACOLL (registered trademark)" series and the like.

  As the curable compound including the epoxy compound and the oxetane compound, it is preferable to use a compound that is not diluted with an organic solvent or the like in order to make the adhesive containing these compounds solvent-free. In addition, other components constituting the adhesive, including a small amount of components including a cationic polymerization initiator and a sensitizer described later, the organic solvent removed and dried than those dissolved in the organic solvent. It is preferable to use a powder or liquid of the compound alone.

  The cationic polymerization initiator is a compound that generates a cationic species upon irradiation with active energy rays such as ultraviolet rays. Any adhesive may be used as long as it provides the adhesive strength and curing rate required for the blended adhesive. Examples include aromatic diazonium salts; onium salts such as aromatic iodonium salts and aromatic sulfonium salts; iron-arene complexes. Etc. These cationic polymerization initiators may be used alone or in combination with a plurality of different types.

Examples of the aromatic diazonium salt include the following.
Benzenediazonium hexafluoroantimonate,
Benzenediazonium hexafluorophosphate,
Benzenediazonium hexafluoroborate, etc.

Examples of aromatic iodonium salts include the following.
Diphenyliodonium tetrakis (pentafluorophenyl) borate,
Diphenyliodonium hexafluorophosphate,
Diphenyliodonium hexafluoroantimonate,
Bis (4-nonylphenyl) iodonium hexafluorophosphate and the like.

Examples of the aromatic sulfonium salt include the following.
Triphenylsulfonium hexafluorophosphate,
Triphenylsulfonium hexafluoroantimonate,
Triphenylsulfonium tetrakis (pentafluorophenyl) borate,
Diphenyl (4-phenylthiophenyl) sulfonium hexafluoroantimonate,
4,4′-bis (diphenylsulfonio) diphenyl sulfide bishexafluorophosphate,
4,4′-bis [di (β-hydroxyethoxyphenyl) sulfonio] diphenyl sulfide bishexafluoroantimonate,
4,4′-bis [di (β-hydroxyethoxyphenyl) sulfonio] diphenyl sulfide bishexafluorophosphate,
7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate,
7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate,
4-phenylcarbonyl-4′-diphenylsulfoniodiphenyl sulfide hexafluorophosphate,
4- (p-tert-butylphenylcarbonyl) -4′-diphenylsulfoniodiphenyl sulfide hexafluoroantimonate,
4- (p-tert-butylphenylcarbonyl) -4′-di (p-toluyl) sulfonio-diphenyl sulfide tetrakis (pentafluorophenyl) borate and the like.

Examples of the iron-arene complex include the following.
Xylene-cyclopentadienyl iron (II) hexafluoroantimonate,
Cumene-cyclopentadienyl iron (II) hexafluorophosphate,
Xylene-cyclopentadienyl iron (II) Tris (trifluoromethylsulfonyl)
Methanide etc.

  Among the cationic polymerization initiators, aromatic sulfonium salts have UV absorption characteristics even in the wavelength region of 300 nm or more, and therefore are adhesives (or adhesive layers) having excellent curability and good mechanical strength and adhesive strength. Since it can be given, it is preferably used.

  Cationic polymerization initiators can also be easily obtained from commercial products. For example, the “Kayarad (registered trademark)” series sold by Nippon Kayaku Co., Ltd., sold by Dow Chemical Co., Ltd. "Syracure UVI" series, photo acid generators "CPI" series sold by Sun Apro Co., Ltd., photo acid generators "TAZ", "BBI" and "DTS" sold by Midori Chemical Co., Ltd. “Adekaoptomer” series sold by ADEKA Corporation, “RHODORSIL” (registered trademark) ”sold by Rhodia, and the like.

  In the active energy ray curable adhesive, the cationic polymerization initiator is usually blended at a ratio of 0.5 to 20 parts by mass with respect to 100 parts by mass of the total amount of the active energy ray curable adhesive. 15 parts by mass. If the amount is too small, curing may be insufficient, and the mechanical strength and adhesive strength of the cured adhesive (adhesive layer) may be reduced. Moreover, when there is too much the quantity, the ionic substance in an adhesive will increase, the hygroscopic property of an adhesive will become high, and the durable performance of the laminated body of this invention may be reduced.

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

  Examples of the hydrogen abstraction type photo radical generator include 1-methylnaphthalene, 2-methylnaphthalene, 1-fluoronaphthalene, 1-chloronaphthalene, 2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, 1-iodonaphthalene. , 2-iodonaphthalene, 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, naphthalene derivatives such as 1,4-dicyanonaphthalene, anthracene, 1,2-benzanthracene, 9,10-dichloroanthracene , 9,10-dibromoanthracene, 9,10-diphenylanthracene, 9-cyanoanthracene, 9,10-dicyanoanthracene, 2,6,9,10-tetracyanoanthracene, anthracene derivatives, pyrene derivatives, carbazole 9-methylcarbazole, 9-phenylcarbazole, 9-prop-2-ynyl-9H-carbazole, 9-propyl-9H-carbazole, 9-vinylcarbazole, 9H-carbazole-9-ethanol, 9-methyl-3-nitro -9H-carbazole, 9-methyl-3,6-dinitro-9H-carbazole, 9-octanoylcarbazole, 9-carbazolemethanol, 9-carbazolepropionic acid, 9-carbazolepropionitrile, 9-ethyl-3,6 -Dinitro-9H-carbazole, 9-ethyl-3-nitrocarbazole, 9-ethylcarbazole, 9-isopropylcarbazole, 9- (ethoxycarbonylmethyl) carbazole, 9- (morpholinomethyl) carbazole, 9-acetylcarbazole, 9- Allyl Rubazole, 9-benzyl-9H-carbazole, 9-carbazoleacetic acid, 9- (2-nitrophenyl) carbazole, 9- (4-methoxyphenyl) carbazole, 9- (1-ethoxy-2-methyl-propyl) -9H -Carbazole, 3-nitrocarbazole, 4-hydroxycarbazole, 3,6-dinitro-9H-carbazole, 3,6-diphenyl-9H-carbazole, 2-hydroxycarbazole, 3,6-diacetyl-9-ethylcarbazole, etc. Carbazole derivatives, benzophenone, 4-phenylbenzophenone, 4,4'-bis (dimethoxy) benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, methyl 2-benzoylbenzoate Ester, 2- Benzophenone derivatives such as methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, aromatic carbonyl compounds, [4- (4-methyl Phenylthio) phenyl] -phenylmethanone, xanthone, thioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 1- Examples include thioxanthone derivatives such as chloro-4-propoxythioxanthone and coumarin derivatives.

  The cleavage type photo radical generator is a type of photo radical generator that generates radicals by cleavage of the compound upon irradiation with active energy rays. Specific examples thereof include arylalkyls such as benzoin ether derivatives and acetophenone derivatives. Examples include, but are not limited to, ketones, oxime ketones, acylphosphine oxides, S-phenyl thiobenzoates, titanocenes, and derivatives obtained by increasing the molecular weight thereof. Commercially available cleavage type photo radical generators include 1- (4-dodecylbenzoyl) -1-hydroxy-1-methylethane, 1- (4-isopropylbenzoyl) -1-hydroxy-1-methylethane, 1-benzoyl. -1-hydroxy-1-methylethane, 1- [4- (2-hydroxyethoxy) -benzoyl] -1-hydroxy-1-methylethane, 1- [4- (acryloyloxyethoxy) -benzoyl] -1-hydroxy- 1-methylethane, diphenyl ketone, phenyl-1-hydroxy-cyclohexyl ketone, benzyldimethyl ketal, bis (cyclopentadienyl) -bis (2,6-difluoro-3-pyryl-phenyl) titanium, (η6-isopropylbenzene) -(Η5-cyclopentadienyl) -iron (II) hexaf Fluorophosphate, trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl) -phosphine oxide, bis (2,4,6-trimethylbenzoyl) -2, 4-dipentoxyphenylphosphine oxide or bis (2,4,6-trimethylbenzoyl) phenyl-phosphine oxide, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 4- (methylthiobenzoyl) -1 -Methyl-1-morpholinoethane may be mentioned, but is not limited thereto.

  Among the active energy curable adhesives used in the present invention, any of the photo radical generators included in the electron beam curable type, that is, hydrogen abstraction type or cleavage type photo radical generators can be used alone. In addition, a plurality of them may be used in combination, but more preferable is a combination of one or more cleavage type photoradical generators in terms of stability and curability of the photoradical generator alone. Among the cleavage type photoradical generators, acylphosphine oxides are preferable. More specifically, trimethylbenzoyldiphenylphosphine oxide (trade name “DAROCURE TPO”, Ciba Japan Co., Ltd.), bis (2,6-dimethoxy- Benzoyl)-(2,4,4-trimethyl-pentyl) -phosphine oxide (trade name “CGI 403”, Ciba Japan Ltd.) or bis (2,4,6-trimethylbenzoyl) -2,4- Dipentoxyphenylphosphine oxide (trade name “Irgacure 819”, Ciba Japan Co., Ltd.) is preferred.

  The active energy ray-curable adhesive can contain a sensitizer as necessary. By using a sensitizer, the reactivity is improved, and the mechanical strength and adhesive strength of the cured adhesive (adhesive layer) can be further improved. As the sensitizer, those described above can be appropriately applied.

  When mix | blending a sensitizer, it is preferable that the compounding quantity shall be the range of 0.1-20 mass parts with respect to 100 mass parts of total amounts of an active energy ray hardening-type adhesive agent.

  Various additives can be blended with the active energy ray-curable adhesive within a range that does not impair the effect. Examples of additives that can be blended include ion trapping agents, antioxidants, chain transfer agents, tackifiers, thermoplastic resins, fillers, flow regulators, plasticizers, and antifoaming agents.

  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 laminate of the present invention may be obtained by applying the adhesive composition to one or both sides of the resin laminate (A) and drying it. In addition, the component which does not melt | dissolve in the water contained in an adhesive should just be the state disperse | distributed in the system.

  The active energy ray-curable adhesive can be applied to the resin laminate (A) by the application method described above. In this case, the viscosity of the active energy ray-curable adhesive may be any as long as it has a viscosity that can be applied by various methods, but the viscosity at a temperature of 25 ° C. is in the range of 10 to 30,000 mPa · sec. It is preferable that it is in the range of 50 to 6,000 mPa · sec. If the viscosity is too small, it tends to be difficult to obtain a uniform coating without unevenness. On the other hand, when the viscosity is too large, it tends to be difficult to flow, and it is difficult to obtain a uniform coating film with no unevenness. The viscosity here is a value measured at 60 rpm after adjusting the temperature of the adhesive to 25 ° C. using a B-type viscometer.

  The active energy ray curable adhesive can be used in an electron beam curable type or an ultraviolet curable type. Active energy rays are defined as energy rays that can generate active species by decomposing a compound that generates active species. Examples of such active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ rays, and electron beams.

  In the electron beam curable type, any appropriate condition can be adopted as the electron beam irradiation condition as long as the active energy ray curable adhesive can be cured. For example, in the electron beam irradiation, the acceleration voltage is preferably 5 kV to 300 kV, and more preferably 10 kV to 250 kV. If the acceleration voltage is less than 5 kV, the electron beam may not reach the adhesive and may be insufficiently cured. If the acceleration voltage exceeds 300 kV, the penetration force through the sample is too strong and the electron beam rebounds, and the resin laminate ( A) may be damaged. The irradiation dose is 5 to 100 kGy, more preferably 10 to 75 kGy. When the irradiation dose is less than 5 kGy, the adhesive becomes insufficiently cured, and when it exceeds 100 kGy, the resin laminate (A) and the like are damaged, resulting in a decrease in mechanical strength and yellowing to obtain desired optical characteristics. I can't.

  Electron beam irradiation is usually performed in an inert gas, but if necessary, it may be performed in the atmosphere or under a condition in which a small amount of oxygen is introduced. Although it depends on the material of the laminate of the present invention, by appropriately introducing oxygen, if oxygen inhibition is caused on the surface of the resin laminate first hit with an electron beam, damage to the laminate of the present invention is prevented. Thus, only the adhesive can be efficiently irradiated with an electron beam.

In the ultraviolet curable type, the light irradiation intensity of the active energy ray curable adhesive is determined for each composition of the adhesive and is not particularly limited, but is preferably 10 to 5000 mW / cm ² . When the light irradiation intensity is less than 10 mW / cm ² , the reaction time becomes too long, and when it exceeds 5000 mW / cm ² , the heat of the light source and heat generated during polymerization of the adhesive cause the laminate of the present invention. May cause yellowing or deterioration. The irradiation intensity is preferably an intensity in a wavelength region effective for activation of the photocationic polymerization initiator, more preferably an intensity in a wavelength region of a wavelength of 400 nm or less, and further preferably a wavelength region of a wavelength of 280 to 320 nm. Strength. Such once with light intensity or by irradiation a plurality of times, the integrated light quantity 10 mJ / cm ² or more, preferably be set to be 10~5,000mJ / cm ^2. When the integrated light amount is less than 10 mJ / cm ² , the generation of the active species derived from the polymerization initiator is not sufficient, and the curing of the adhesive becomes insufficient. On the other hand, when the integrated light quantity exceeds 5,000 mJ / cm ² , the irradiation time becomes very long, which is disadvantageous for improving productivity. At this time, in which wavelength region (UVA (320 to 390 nm), UVB (280 to 320 nm, etc.)) the integrated light amount is required depends on the combination of the resin laminate (A) and the adhesive type.

  The light source used for polymerizing and curing the adhesive by irradiation with active energy rays in the present invention is not particularly limited. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a halogen lamp, carbon Examples include an arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, an LED light source that emits light in the wavelength range of 380 to 440 nm, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, and a metal halide lamp. From the viewpoint of energy stability and simplicity of the apparatus, 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, more preferably 10 to 350 μm. By setting the thickness of the pressure-sensitive adhesive layer to 500 μm or less, the adhesiveness under high temperature and high humidity is improved, and the occurrence of floating or peeling between the pressure-sensitive adhesive layer and the polarizing plate or the like on which the pressure-sensitive adhesive layer is bonded. It tends to be suppressed and reworkability tends to be improved. In addition, by setting the thickness to 5 μm or more, even if the size of the polarizing plate bonded thereto changes, the pressure-sensitive adhesive layer fluctuates following the dimensional change. improves.

  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, sufficient transparency cannot be obtained when it is laminated with the resin laminate (A).

  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.

  The laminate of the present invention is preferably a dielectric constant of 3.5 or more, more preferably 4.0 or more, and even more preferably 4.1 or more, from the viewpoint of obtaining a function sufficient for use in a display device such as a touch panel. Have The upper limit value of the dielectric constant is not particularly limited, but is usually 20. The dielectric constant can be adjusted by adjusting the type and amount of the vinylidene fluoride resin contained in the intermediate layer (A) of the laminate of the present invention, or by adding a high dielectric constant compound such as ethylene carbonate or propylene carbonate. Can be adjusted to the range. The dielectric constant is based on JIS K 6911: 1995, and the resin laminate is allowed to stand for 24 hours in an environment with a relative humidity of 50% at 23 ° C., and measured in this environment at 3 V and 100 kHz by the automatic equilibrium bridge method. It is the value. For the measurement, commercially available equipment may be used, for example, “precise LCR meter HP4284A” manufactured by Agilent Technologies, Inc. may be used.

  The laminate of the present invention is preferably transparent when visually observed. Specifically, the laminate of the present invention preferably has a total light transmittance of 85% or more, more preferably 88% or more, and even more preferably 90% or more as measured according to JIS K7361-1: 1997. (Tt). The upper limit of the total light transmittance is 100%. It is preferred that the laminate of the present invention after exposure for 120 hours in an environment of 60 ° C. and 90% relative humidity still has a total light transmittance in the above range.

  The laminate of the present invention is measured according to JIS K7136: 2000, preferably 2.0%, using the laminate of the present invention after exposure for 120 hours in an environment of 60 ° C. and 90% relative humidity. The haze (haze value) is preferably 1.8% or less, more preferably 1.5% or less. Further, the laminate of the present invention is measured according to JIS Z 8722: 2009 using the laminate of the present invention after being exposed for 120 hours in an environment of 90% relative humidity at 60 ° C., preferably 1.5 or less. More preferably, it has a yellowness index (Yellow Index: YI value) of 1.4 or less, and even more preferably 1.3 or less.

  From the viewpoint of the rigidity of the resin laminate, the thickness of the laminate of the present invention is preferably 100 μm or more, more preferably 200 μm or more, and even more preferably 300 μm or more. Moreover, from a viewpoint of transparency, Preferably it is 2000 micrometers or less, More preferably, it is 1500 micrometers or less, More preferably, it is 1000 micrometers or less. The film thickness of the laminate of the present invention is measured with a digital micrometer. Let the average value which performed the said measurement in 10 points | pieces of a resin laminated body (A) be an average value of a film thickness.

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

  The resin laminate (A) can be produced from a resin composition α that provides an intermediate layer, and resin compositions β and γ that respectively provide a thermoplastic resin layer on both surfaces of the intermediate layer.

  The resin composition α is usually obtained by kneading a (meth) acrylic resin and a vinylidene fluoride resin. The kneading can be performed, for example, by a method including a step of melt-kneading at a shear rate of 10 to 1000 / second at a temperature of 150 to 350 ° C.

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

  In order to obtain a resin composition in which each component is more uniformly mixed, the melt-kneading is preferably performed at a temperature of 180 to 300 ° C, more preferably 200 to 300 ° C, preferably 20 to 700 / second, and more. Preferably, it is carried out at a shear rate of 30 to 500 / sec.

  As an apparatus used for melt kneading, a normal mixer or kneader can be used. Specific examples include a single-screw kneader, a multi-screw kneader (for example, a twin-screw kneader), a Henschel mixer, a Banbury mixer, a kneader, and a roll mill. Further, when the shear rate is increased within the above range, a high shearing device or the like may be used.

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

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

  The resin laminate (A) having at least an intermediate layer and a thermoplastic resin layer present on both sides of the intermediate layer is obtained by, for example, a melt extrusion molding method, a solution casting film forming method, a heat pressing method, an injection molding method, or the like. Each layer may be prepared separately from the resin compositions α, β, and γ, and may be manufactured by, for example, bonding them through an adhesive or an adhesive, or the resin compositions α, β, and γ may be melted together. You may manufacture by carrying out lamination | stacking integration by extrusion molding. When manufacturing a resin laminated body (A) by bonding, it is preferable to use an injection molding method and a melt extrusion molding method for production of each layer, and it is more preferable to use a melt extrusion molding method. The resin laminate (A) can be produced by melt coextrusion molding of the resin compositions α, β and γ, as compared with the resin laminate (A) produced by bonding. It is preferable because a resin laminate (A) that can be easily molded is obtained.

  In melt coextrusion molding, for example, resin compositions α, β, and γ are separately fed into two or three uniaxial or biaxial extruders, melted and kneaded, respectively, and then fed block die or multi-manifold This is a molding method in which an intermediate layer formed from a resin composition α and a thermoplastic resin layer formed from resin compositions β and γ are laminated and integrated through a die or the like and extruded. When the resin compositions β and γ are the same composition, one composition melt-kneaded in one extruder is divided into two via a feed block die, etc., and both surfaces of the intermediate layer are thermoplastic. A resin layer may be formed. The obtained resin laminate is preferably cooled and solidified by, for example, a roll unit.

  By applying the transparent pressure-sensitive adhesive (B) to at least one surface of the thus obtained resin laminate (A), the laminate of the present invention can be obtained.

  The resin laminate with a transparent adhesive of the present invention is obtained by cutting out from the laminate of the present invention produced as described above, for example, a resin laminate having a size of 500 to 3000 mm in width and 500 to 3000 mm in length. It is distributed in the form.

  This invention also provides the resin laminated body with a transparent adhesive which has a protective film in the outermost surface at the side of a resin laminated body (A) (Hereinafter, the laminated body of this form may be called a laminated body with a protective film.).

  Such a laminate with a protective film preferably has a protective film having at least a film substrate and an adhesive layer bonded to the outermost surface on the resin laminate (A) side via an adhesive layer.

  The protective film is bonded to the surface of the thermoplastic resin layer via an adhesive layer for the purpose of protecting the surface.

  The film substrate of the protective film is not particularly limited as long as the surface of the resin laminate can be protected, but is preferably a plastic film from the viewpoint of easily improving the protection of the surface of the resin laminate, for example, polyethylene (PE) It may be a film, a polypropylene (PP) film, a polyethylene terephthalate (PET) film, an acrylic resin film, a polycarbonate (PC) film, or the like.

  The tensile elastic modulus of the film base material of the protective film is preferably 100 MPa or more, more preferably 150 MPa or more, and even more preferably 200 MPa or more, from the viewpoint of easily improving the protection of the surface of the resin laminate. Moreover, the tensile elastic modulus of the film base material of the protective film is preferably 5,000 MPa or less, more preferably 4,500 MPa or less, and still more preferably 4,000 MPa or less, from the viewpoint of easy bonding.

  The average value of the film thickness of the film base material of the protective film is preferably 45 μm or more, more preferably 50 μm or more, and even more preferably 60 μm or more, from the viewpoint of easily improving the protection of the surface of the resin laminate. Moreover, the average value of the film thickness of the film base material of a protective film becomes like this. From a viewpoint of the ease of bonding, Preferably it is 200 micrometers or less, More preferably, it is 175 micrometers or less, More preferably, it is 150 micrometers or less. The average value of the film thickness of the film substrate is measured with a digital micrometer, and the average value of the measured values at any 10 points is taken as the average value of the film thickness.

  The protective film is bonded to the surface of the resin laminate (A) via an adhesive layer. Here, the protective film is a film bonded for the purpose of protecting the surface of the resin laminate (A), for example, in the manufacturing process or the distribution process. Therefore, in the manufacturing process of the display device and the like, the protective film is peeled off from the surface of the resin laminate (A), the resin laminate with a transparent adhesive is bonded to the display device via the transparent adhesive (B), It is incorporated as a component of the display device.

  The adhesive layer of the protective film has, for example, sufficient adhesiveness to maintain the state in which the protective film is bonded to the surface of the resin laminate (A) in the manufacturing process or distribution process, and the surface of the resin laminate (A). It is required to have a releasability that allows easy removal of the protective film. From such a viewpoint, it is preferable that the protective film has a low adhesive strength that can be peeled off from the surface of the resin laminate, and specifically, preferably 0.4 N / 25 mm or less, more preferably 0.8. More preferably, it has a peel strength of 35 N / 25 mm or less. Moreover, from the viewpoint of easily maintaining the state in which the protective film is bonded to the surface of the resin laminate, the peel strength is preferably 0.01 N / 25 mm or more, more preferably 0.02 N / 25 mm or more. The peel strength is measured according to JIS-Z0237 at a peel rate of 0.3 mm / min, a peel angle of 180 °, and a measurement width of 25 mm.

  The adhesive layer of the protective film is not particularly limited as long as it has the above-mentioned adhesiveness and peelability. For example, acrylic resin, rubber resin, ethylene vinyl acetate copolymer resin, polyester resin, acetate resin, polyether sal It is preferable to contain a phon resin, a polycarbonate resin, a polyamide resin, a polyimide resin, a polyolefin resin, or the like as an adhesive.

  The pressure-sensitive adhesive layer of the protective film may contain other components of the pressure-sensitive adhesive. Examples of other components include an antistatic agent, a colorant, and an ultraviolet absorber.

  The resin laminated body with a protective film of this invention can be manufactured by bonding the said protective film on the surface of the resin laminated body (A) of the resin laminated body with a transparent adhesive.

  This invention also provides the resin laminated body with a transparent adhesive which has a separator (peeling film) in the outermost surface at the side of a transparent adhesive (B) (Hereinafter, the laminated body of this form may be called a laminated body with a separator.). ). Thus, by having a separator, while protecting a transparent adhesive (B), the handleability of the laminated body of this invention can be made favorable.

  As a separator (release film), the film illustrated above as a film base material of a protective film, a polybutylene terephthalate film, a polyarylate film, etc. are mentioned, for example.

  The average value of the film thickness of the separator is preferably 45 μm or more, more preferably 50 μm or more, and even more preferably 60 μm or more, from the viewpoint of easily improving the protection of the surface of the resin laminate. In this embodiment, the average value of the film thickness of the separator is preferably 200 μm or less, more preferably 175 μm or less, and particularly preferably 150 μm or less, from the viewpoint of easy bonding. The measuring method of the average value of the film thickness of a separator is the same as the method shown above about the film base material of a protective film.

  The separator removes the separator from the surface of the transparent adhesive (B) with sufficient adhesiveness to maintain the state where the separator is bonded to the surface of the transparent adhesive (B), for example, in the manufacturing process or the distribution process. It is required to have easy releasability. From such a viewpoint, the separator preferably has a low adhesive strength that can be manually peeled off from the surface of the transparent pressure-sensitive adhesive (B), specifically, preferably 0.4 N / 25 mm or less, more preferably More preferably, it has a peel strength of 0.35 N / 25 mm or less. In addition, from the viewpoint of easily maintaining the state where the separator is bonded to the surface of the transparent adhesive (B), it preferably has a peel strength of 0.01 N / 25 mm or more, more preferably 0.02 N / 25 mm or more. preferable. The peel strength can be measured according to JIS-Z0237.

  The separator-attached laminate may be produced by bonding the separator to the surface of the transparent adhesive (B) of the resin laminate with the transparent adhesive layer, and the transparent adhesive (B) is used in an appropriate solvent. You may manufacture by apply | coating the dissolved adhesive composition to a separator, and bonding the obtained transparent adhesive with a separator on the single side | surface or both surfaces of a resin laminated body (A). Moreover, the laminated body with a separator of this invention is peeled off by peeling the separator of the one side of the double-sided separator type adhesive with which the transparent adhesive (B) was apply | coated to both surfaces of the separator, and bonding to the surface of a resin laminated body (A). You may get In addition, the double-sided separator type pressure-sensitive adhesive is commercially available, and examples of the commercially available products include non-carrier pressure-sensitive adhesive films and non-carrier pressure-sensitive adhesive sheets sold by Lintec Corporation and Nitto Denko Corporation.

  The separator is a film bonded for the purpose of protecting the surface of the transparent adhesive layer (B), for example, in the production process or the distribution process. Therefore, in the manufacturing process of the display device, the separator is peeled off from the surface of the transparent adhesive layer (B), and the resin laminate with the transparent adhesive of the present invention is bonded to the display device via the transparent adhesive (B). Incorporated as a component of the display device.

  The laminate of the present invention can be attached to a polarizing plate, a touch panel or 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. As the display device, a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, an electron emission display device (for example, a field emission display device (FED), a surface field emission display device) (SED)), electronic paper (display device using electronic ink or electrophoretic element), plasma display device, projection display device (for example, a grating light valve (GLV) display device, a display having a digital micromirror device (DMD)) Apparatus) and a piezoelectric ceramic display. The liquid crystal display device includes any of a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct view liquid crystal display device, a projection liquid crystal display device, and the like. These display devices may be a display device that displays a two-dimensional image, or may be a stereoscopic display device that displays a three-dimensional image. The laminate of the present invention is suitably used in these display devices, for example, as a front plate or a transparent electrode.

  When the transparent adhesive (B) is an activated energy ray-curable adhesive, the lamination of the present invention and the polarizing plate, touch panel, etc. are activated after being bonded to the polarizing plate, touch panel sheet, etc. You may carry out by irradiating an energy ray.

  When the laminate of the present invention is used as a transparent electrode in a touch panel or the like, a transparent conductive film is produced on the surface of the resin laminate (A) to produce a transparent conductive sheet, and a transparent adhesive (B) is applied to the transparent conductive sheet. A transparent electrode can be manufactured after applying.

  As a method for forming the transparent conductive film, the transparent conductive film may be directly formed on the surface of the resin laminate (A), or a plastic film on which a transparent conductive film has been previously formed may be laminated.

  The film base material of the plastic film on which the transparent conductive film is formed in advance is not particularly limited as long as it is a transparent film and can form a transparent conductive film. For example, polyethylene terephthalate, polyethylene naphthalate , Polycarbonate, acrylic resin, polyamide, a mixture or laminate thereof. Further, before the transparent conductive film is formed, the film may be coated for the purpose of improving surface hardness, preventing Newton's ring, imparting antistatic properties, and the like.

  The method of laminating the film, on which the transparent conductive film has been previously formed, on the surface of the resin laminate (A) may be any method as long as it is free from bubbles and can provide a uniform and transparent sheet. A method of laminating using an adhesive that is cured by normal temperature, heating, ultraviolet light, or visible light may be used, or a transparent adhesive tape may be used for bonding.

  As a method for forming a transparent conductive film, a vacuum deposition method, a sputtering method, a CVD method, an ion plating method, a spray method, and the like are known, and these methods are appropriately used depending on a required film thickness. Can do.

  In the case of the sputtering method, for example, a normal sputtering method using an oxide target, a reactive sputtering method using a metal target, or the like is used. At this time, oxygen, nitrogen, or the like may be introduced as a reactive gas, or means such as ozone addition, plasma irradiation, or ion assist may be used in combination. If necessary, a bias such as direct current, alternating current, and high frequency may be applied to the substrate. The transparent conductive metal oxide used for the transparent conductive film includes indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide, and indium-zinc composite. An oxide etc. are mentioned. Of these, indium-tin composite oxide (ITO) is preferable from the viewpoints of environmental stability and circuit processability.

  Further, as a method for forming a transparent conductive film, a coating agent containing various conductive polymers capable of forming a transparent conductive film is applied to the surface of the resin laminate (A), and ionization such as heat or ultraviolet rays is performed. A method of curing the coating by irradiating with radiation can also be applied. As the conductive polymer, polythiophene, polyaniline, polypyrrole, and the like 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 2000 mm, preferably 70 to 000 mm. If it is this range, it will be excellent in both electroconductivity and transparency.

  The thickness of the transparent conductive sheet is not particularly limited, and an optimum thickness can be selected according to the demand for the product specifications of the display.

  A touch sensor panel can be manufactured by using the laminate of the present invention as a display panel face plate, and using a transparent conductive sheet manufactured from the laminate of the present invention as a transparent electrode such as a touch screen. Specifically, the laminate of the present invention can be used as a touch screen window sheet, and the transparent conductive sheet can be used as an electrode substrate of a resistive film type or capacitive type touch screen. An external touch sensor panel having a touch screen function can be obtained by arranging the touch screen on the front surface of a liquid crystal display device, an organic EL display device or the like.

  The present invention also provides a display device including the laminate of the present invention. The display device of the present invention can 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 laminate 10 is laminated on the polarizing plate 11 via the optical adhesive layer 12, and this laminate can be arranged on the viewing side of the liquid crystal cell 13. A polarizing plate 11 is usually disposed on the back side of the liquid crystal cell 13. The liquid crystal display device 14 is composed of such members. FIG. 2 is an example of a liquid crystal display device, and the display device of the present invention is not limited to this configuration.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these Examples.

[Vicat softening temperature]
Measured according to the B50 method defined in JIS K 7206: 1999 “Plastics—Thermoplastics—Vicat Softening Temperature (VST) Test Method”. The Vicat softening temperature was measured with a heat distortion tester ["148-6 continuous type" manufactured by Yasuda Seiki Seisakusho Co., Ltd.]. The test piece at that time was measured by press-molding each raw material to a thickness of 3 mm.

[Alkali metal content]
It was measured by inductively coupled plasma mass spectrometry.

[MFR]
Measured in accordance with JIS K 7210: 1999 “Plastics—Testing Methods for Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Thermoplastic Plastics”. This JIS stipulates that poly (methyl methacrylate) -based materials are measured at a temperature of 230 ° C. and a load of 3.80 kg (37.3 N).

[MVR]
About the material of polycarbonate-type resin, it measured on 300 degreeC conditions under 1.2 kg load by the "semi auto melt indexer 2A" by the Toyo Seiki Seisakusho Co., Ltd. which conforms to JISK7210.

[Total light transmittance and haze]
Haze Transmittance Meter (“HR-100” manufactured by Murakami Color Research Laboratory Co., Ltd.) in accordance with JIS K 7361-1: 1997 “Plastics—Test method for total light transmittance of transparent materials—Part 1: Single beam method” ).

[YI value]
The measurement was performed with “Spectrophotometer SQ2000” manufactured by Nippon Denshoku Industries Co., Ltd.

[Average film thickness]
The film thickness of the resin laminate was measured with a digital micrometer. The average value obtained by performing the above measurement at 10 points was defined as the average value of the film thickness of the resin laminate.
The film thickness of each layer of the intermediate layer and the thermoplastic resin layers (B) and (C) was measured by cutting the resin laminate perpendicularly to the surface direction and polishing the cross section with sandpaper. It was measured by observing with a square microscope. The average value obtained by performing the above measurement at 10 points was defined as the average value of the film thickness of each layer.

[Water contact angle]
Place the resin laminate horizontally on a contact angle meter (Kyowa Interface Science Co., Ltd. image processing contact angle meter “FACE CA-X”) so that the hard coat layer on the resin laminate (A) side is the top surface. Then, 1 microliter of pure water was dropped on the surface to be measured, and the contact angle with water was measured by the θ / 2 method.

(Production 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 transfer agent (octyl mercaptan) and 0.1 parts by mass of a release agent (stearyl alcohol) were added. A mass mixture was obtained. Further, 0.036 parts by mass of a polymerization initiator [1,1-di (tert-butylperoxy) 3,3,5-trimethylcyclohexane] was added to 100 parts by mass of methyl methacrylate to obtain an initiator mixed solution. Continuously fed to the fully mixed polymerization reactor so that the flow ratio of the monomer mixture to the initiator mixture was 8.8: 1, the average residence time was 20 minutes, and the average polymerization rate was 54% at a temperature of 175 ° C. Until partial polymerization was obtained. The resulting partially polymerized product is heated to 200 ° C. and led to a vented devolatilizing extruder, and unreacted monomers are devolatilized from the vent at 240 ° C., and the polymer after devolatilization is extruded in a molten state. After cooling with water, it was cut to obtain a pellet-shaped methacrylic resin (i).

  The obtained pellet-like methacrylic resin composition was analyzed by pyrolysis gas chromatography under the following conditions, and each peak area corresponding to methyl methacrylate and acrylate ester was measured. As a result, in the methacrylic resin (i), the structural unit derived from methyl methacrylate was 97.5% by mass, and the structural unit derived from methyl acrylate was 2.5% by mass.

(Pyrolysis conditions)
Sample preparation: A methacrylic resin composition was precisely weighed (standard 2-3 mg), placed in the center of a bowl-shaped metal cell, the metal cell was folded, and both ends were lightly pressed with pliers and sealed.
Thermal decomposition apparatus: CURIE POINT PYROLYZER JHP-22 (manufactured by Nippon Analytical Industries, Ltd.)
Metal cell: Pyrofoil F590 (manufactured by Nippon Analytical Industries, Ltd.)
Thermostatic bath set temperature: 200 ° C
Set temperature of heat insulation pipe: 250 ℃
Thermal decomposition temperature: 590 ° C
Thermal decomposition time: 5 seconds

(Gas chromatography analysis conditions)
Gas chromatography analyzer: GC-14B (manufactured by Shimadzu Corporation)
Detection method: FID
Column: 7G 3.2 m × 3.1 mmφ (manufactured by Shimadzu Corporation)
Filler: FAL-M (manufactured by Shimadzu Corporation)
Carrier gas: Air / N2 / H2 = 50/100/50 (kPa), 80 ml / min Column temperature rising condition: held at 100 ° C. for 15 minutes, then heated up to 150 ° C. at 10 ° C./minute, at 150 ° C. Hold for 14 minutes INJ temperature: 200 ° C
DET temperature: 200 ° C

The methacrylic resin composition is pyrolyzed under the above pyrolysis conditions, and the peak area (a1) corresponding to methyl methacrylate detected when the generated decomposition product is measured under the above gas chromatography analysis conditions and the acrylate ester The peak area (b1) corresponding to was measured. And peak area ratio A (= b1 / a1) was calculated | required from these peak areas. On the other hand, a standard product of a methacrylic resin having a weight ratio of acrylate units to methyl methacrylate units of W ₀ (known) is pyrolyzed under the above pyrolysis conditions, and the generated decomposition product is subjected to the above gas chromatography analysis conditions. The peak area (a ₀ ) corresponding to methyl methacrylate and the peak area (b ₀ ) corresponding to acrylate detected when the measurement is performed are measured, and the peak area ratio A ₀ (= b ₀ ) is measured from these peak areas. / A ₀ ). Then, a factor f (= W ₀ / A ₀ ) was determined from the peak area ratio A ₀ and the weight ratio W ₀ .

  By multiplying the peak area ratio A by the factor f, a weight ratio W of acrylate units to methyl methacrylate units in the copolymer contained in the methacrylic resin composition is obtained, and from the weight ratio W, methacrylic acid is obtained. The ratio (mass%) of the methyl methacrylate unit to the total of the methyl unit and the acrylate unit and the ratio (mass%) of the acrylate unit to the total were calculated.

  The resulting methacrylic resin (i) has an MA of 2.5 wt%, an MFR of 2 g / 10 min, an Mw of 120,000, a Vicat softening temperature of 110 ° C., an Na content of less than 0.01 ppm, and a K content of 0. It was less than 0.01 ppm.

The weight average molecular weight (Mw) of the (meth) acrylic resin was measured by gel permeation chromatography (GPC). To create a GPC calibration curve, use a methacrylic resin made by Showa Denko KK with a narrow molecular weight distribution and known molecular weight as a standard reagent, create a calibration curve from the elution time and molecular weight, and calculate the weight of each resin composition. Average molecular weight was measured. Specifically, 40 mg of resin was dissolved in 20 ml of tetrahydrofuran (THF) solvent to prepare a measurement sample. For the measuring device, two columns “TSKgel SuperHM-H”, which is a column made by Tosoh Corporation, and one “SuperH2500” were installed in series, and a detector employing an RI detector was used. . The measured molecular weight distribution curve was fitted using the normal distribution function by taking the logarithm of the molecular weight on the horizontal axis and fitting using the normal distribution function of the following equation.

(Production Example 2)
A pellet-like methacrylic resin (ii) was prepared in the same manner as in Production Example 1 except that 97.7 parts by mass of methyl methacrylate, 2.3 parts by mass of methyl acrylate, and 0.05 parts by mass of the chain transfer agent were changed. And the content of the structural unit was measured. In the methacrylic resin (ii), the structural unit derived from methyl methacrylate was 97.0% by mass, and the structural unit derived from methyl acrylate was 3.0% by mass.

  The resulting methacrylic resin (ii) has an MA of 3 wt%, an MFR of 0.5 g / 10 min, an Mw of 180,000, a Vicat softening temperature of 106 ° C., an Na content of less than 0.01 ppm, and a K content of 0.8. It was less than 01 ppm.

  Table 1 shows the vinylidene fluoride resins used in the examples and their physical properties.

  The weight average molecular weight (Mw) of vinylidene fluoride was measured by GPC. To prepare a GPC calibration curve, polystyrene was used as a standard reagent, a calibration curve was created from the elution time and molecular weight, and the weight average molecular weight of each resin was measured. Specifically, 40 mg of resin was dissolved in 20 ml of N-methylpyrrolidone (NMP) solvent to prepare a measurement sample. For the measuring device, two columns “TSKgel SuperHM-H”, which is a column made by Tosoh Corporation, and one “SuperH2500” were installed in series, and a detector employing an RI detector was used. .

(Production Example 3)
In order to make the blueing agent into a master batch (MB), methacrylic resin (ii) and a colorant were dry blended at a ratio of 99.99: 0.01, and a 40 mmφ single screw extruder (manufactured by Tanabe Plastic Machinery Co., Ltd.). ) And melt-mixed at a set temperature of 250 to 260 ° C. to obtain colored master batch pellets. As the colorant, a bluing agent (“Sumiplast (registered trademark) Violet B” manufactured by Sumika Chemtex Co., Ltd.) was used.

(Examples 1-2 and Comparative Examples 1-3)
The resin laminate in the present invention was produced as follows.
First, as a material for forming the intermediate layer, (meth) acrylic resin, vinylidene fluoride resin, and master batch pellets (MB pellets) produced in Production Example 3 were mixed in the combinations and proportions shown in Table 2, A resin composition was obtained. Subsequently, the resin composition was 65 mmφ single screw extruder 2 (manufactured by Toshiba Machine Co., Ltd.), and 100 parts by weight of methacrylic resin (i) as a thermoplastic resin layer forming material was added to 45 mmφ single screw extruders 1 and 3 [Hitachi Zosen ( Made by Co., Ltd.]. Next, these are supplied to a three-type three-layer distribution type feed block 4 having a set temperature of 230 to 270 ° C. and distributed so as to have a three-layer configuration, and then a multi-manifold die 5 [manufactured by Hitachi Zosen Co., Ltd., two types 3 Extruded from layer distribution] and laminated so as to have a structure represented by B layer / A layer / C layer, and a film-like molten resin 6 was obtained. The obtained film-like molten resin 6 is sandwiched between the first cooling roll 7 and the second cooling roll 8 that are arranged to face each other, and then wound around the second roll 8 while the second roll 8 and the third roll 9 are Then, the film was wound around a third cooling roll 9 and molded and cooled to obtain a film 10 having a three-layer structure in which the thickness of each layer is as shown in Table 2. All of the obtained films 10 had a total film thickness of 800 μm, and were visually transparent when observed visually. An acrylic adhesive organic solvent solution obtained by adding an isocyanate crosslinking agent to a copolymer of butyl acrylate, methyl acrylate, and hydroxyethyl acrylate as a transparent adhesive (B) to the obtained resin laminate. A sheet with a release film formed by coating a release treatment surface of a 75 μm-thick polyethylene terephthalate film (release film) that has been subjected to a release treatment with a die coater so that the thickness after drying is 50 μm. A pressure-sensitive adhesive was laminated with a laminator without bubbles to obtain a resin laminate with a transparent pressure-sensitive adhesive.

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

(Example 3)
A resin laminate with a transparent adhesive was obtained in the same manner as in Example 1 except that the surface of the thermoplastic resin layer was coated with a hard coat. The hard coating agent comprises 50 parts of dipentaerythritol hexaacrylate and 50 parts of pentaerythritol tetraacrylate as a curable compound, 6 parts of a photopolymerization initiator [IRGACURE 184 from Ciba Specialty Chemicals Co., Ltd.], and 125 parts of isobutyl alcohol as a solvent. And 125 parts of 1-methoxy-2-propanol. The hard coat agent was applied to both surfaces of the resin laminate by a dipping coat method, 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. Next, the coating film was cured by irradiating ultraviolet rays of 0.5 J / cm 2 using a 120 W high-pressure mercury lamp to obtain a resin laminate with a hard coat having a cured coating thickness of 3.0 μm.

(Comparative Example 4)
In Example 1, instead of the laminate (A), a resin laminate with a transparent adhesive was used in the same manner as in Example 1, except that Technoloy (C101, polycarbonate resin film, thickness 800 μm) was used. Got the body.

  About the resin laminated body with a transparent adhesive of Examples 1-3 and Comparative Examples 1-4, based on JISK6911: 1995, the result of having measured the dielectric constant with precision LCR meter HP4284A (Agilent Technology Co., Ltd. product). Is shown in Table 3. The dielectric constant is a numerical value at 3 kHz and 100 kHz measured by the automatic equilibrium bridge method in which the test sample (film) is allowed to stand in an environment of 50% relative humidity at 23 ° C. for 24 hours.

  Further, the durability test was performed by leaving the obtained film in a constant temperature and humidity oven at 60 ° C. and 90% absolute humidity for 120 hours. About the film | membrane before and behind an endurance test, the haze value (haze) measured based on JISK7136: 2000 and the total light transmittance (Tt) measured based on JISK7361-19971 are shown in Table 3, respectively. .

  The resin laminate with a transparent adhesive of the present invention shown in Examples 1 to 3 was able to maintain transparency while having a high dielectric constant in the durability test. Therefore, since the resin laminate with a transparent adhesive of the present invention has a high dielectric constant and can maintain transparency even when used for a long time in a high-temperature and high-humidity environment, a smartphone, a portable game machine, an audio player And it is understood that it is useful for display apparatuses, such as a tablet terminal.

1 Single screw extruder (extrudes a melt of thermoplastic resin)
2 Single screw extruder (extrudes a melt of vinylidene fluoride resin)
3 Single screw extruder (extrudes melt of thermoplastic resin)
4 Feed block 5 Multi-manifold die 6 Film-like molten resin 7 First cooling roll 8 Second cooling roll 9 Third cooling roll 10 Resin laminate (A)
10A Intermediate layer 10B Thermoplastic resin layer 10C Thermoplastic resin layer 11 Polarizing plate 12 Transparent adhesive (B)
13 Liquid crystal cell 14 Liquid crystal display device

Claims (14)

A resin laminate (A) comprising at least an intermediate layer and a thermoplastic resin layer present on both surfaces of the intermediate layer, and a transparent adhesive (B) present on at least one surface of the resin laminate (A) A resin laminate with a transparent adhesive having
The intermediate layer of the resin laminate (A) contains 35 to 45% by mass of (meth) acrylic resin and 65 to 55% by mass of vinylidene fluoride resin based on all resin components contained in the intermediate layer, ) The weight average molecular weight (Mw) of the acrylic resin is 100,000 to 300,000,
The resin laminate with a transparent adhesive, wherein the content of alkali metal in the intermediate layer is 50 ppm or less based on the total resin components contained in the intermediate layer. (Meth) acrylic resin
(A1) methyl methacrylate homopolymer and / or (a2) 50-99.9% by weight of structural units derived from methyl methacrylate based on all structural units constituting the polymer and 0.1-50 Formula of mass% (1)
(In formula, R ₁ is hydrogen or methyl, when R ₁ is hydrogen atom R ₂ represents a alkyl group having 1 to 8 carbon atoms, when R ₁ is methyl R ₂ is the number of carbon atoms Represents an alkyl group of 2 to 8)
The resin laminated body with a transparent adhesive of Claim 1 which is a copolymer containing the at least 1 structural unit derived from the (meth) acrylic acid ester shown by these.   The resin laminate with a transparent adhesive according to claim 1 or 2, wherein the vinylidene fluoride resin is polyvinylidene fluoride.   The resin laminate with a transparent adhesive according to any one of claims 1 to 3, wherein the melt mass flow rate of the vinylidene fluoride resin is 0.1 to 30 g / 10 minutes as measured at 3.8 kg load and 230 ° C. body.   The resin laminated body with a transparent adhesive in any one of Claims 1-4 in which at least 1 layer of an intermediate | middle layer and a thermoplastic resin layer further contains a coloring agent.   The resin laminated body with a transparent adhesive in any one of Claims 1-5 whose average value of the film thickness of a resin laminated body is 100-2000 micrometers.   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.   The resin laminated body with a transparent adhesive in any one of Claims 1-7 whose average value of the film thickness of a thermoplastic resin layer is 10-200 micrometers, respectively.   The resin laminated body with a transparent adhesive in any one of Claims 1-8 whose Vicat softening temperature of a thermoplastic resin layer is 100-160 degreeC, respectively.   The resin laminate with a transparent adhesive according to any one of claims 1 to 9, further comprising a hard coat layer on at least one outermost surface of the resin laminate (A).   The resin laminated body with a transparent adhesive in any one of Claims 1-10 whose water contact angle of the outermost surface of the hard-coat layer by the side of a resin laminated body (A) is 100 degrees or more. The resin laminated body with a transparent adhesive as described in any one of Claims 1-11 which has a protective film in the outermost surface at the side of the resin laminated body (A) of a resin laminated body with a transparent adhesive. The resin laminated body with a transparent adhesive as described in any one of Claims 1-12 which has a separator in the outermost surface at the side of the transparent adhesive (B) of a resin laminated body with a transparent adhesive.   The display apparatus containing the resin laminated body with a transparent adhesive in any one of Claims 1-13.