JP6407918B2 - Resin laminate, display device and polarizing plate - Google Patents

Description

  The present invention relates to a resin laminate suitably used in, for example, a display device, a display device including the resin laminate, and a polarizing plate with a resin laminate in which the resin laminate and a polarizing plate are laminated.

  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 from the viewpoint of weight reduction and workability of the display device, development of a plastic sheet as a substitute for the glass sheet has been performed. 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

  The plastic sheet is required to have an ultraviolet absorbing ability for the purpose of preventing deterioration of elements such as a polarizing plate used in the display device due to ultraviolet rays. In particular, discoloration of the polarizing plate may be caused by ultraviolet rays having a UV-A wavelength of 320 to 400 nm. Therefore, an object of this invention is to provide the resin laminated body which has a UV absorption ability especially suitable for protection of a polarizing plate.

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

により算出されるＸが、０.０１以上０.２５以下である、樹脂積層体。
〔２〕３２０〜４００ｎｍに吸収極大を有する紫外線吸収剤は、トリアジン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤、ベンゾエート系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤およびシアノアクリレート系紫外線吸収剤からなる群から選択される少なくとも１種である、前記〔１〕に記載の樹脂積層体。
〔３〕中間層（Ａ）は、該中間層（Ａ）に含まれる全樹脂に基づいて、３５〜４５質量％の（メタ）アクリル樹脂及び６５〜５５質量％のフッ化ビニリデン樹脂を含む、前記〔１〕又は〔２〕に記載の樹脂積層体。
〔４〕中間層（Ａ）におけるアルカリ金属の含有量が、該中間層（Ａ）に含まれる全樹脂に基づいて５０ｐｐｍ以下である、前記〔１〕〜〔３〕のいずれかに記載の樹脂積層体。
〔５〕（メタ）アクリル樹脂が、
（ａ１）メタクリル酸メチルの単独重合体、及び／又は
（ａ２）重合体を構成する全構造単位に基づいて５０〜９９.９質量％のメタクリル酸メチルに由来する構造単位、及び、０．１〜５０質量％の式（１）：

［式中、Ｒ_１は水素原子又はメチル基を表し、Ｒ_１が水素原子のときＲ_２は炭素数１〜８のアルキル基を表し、Ｒ_１がメチル基のときＲ_２は炭素数２〜８のアルキル基を表す。］
で示される（メタ）アクリル酸エステルに由来する少なくとも１つの構造単位を含む共重合体
である、前記〔１〕〜〔４〕のいずれかに記載の樹脂積層体。
〔６〕フッ化ビニリデン樹脂はポリフッ化ビニリデンである、前記〔１〕〜〔５〕のいずれかに記載の樹脂積層体。
〔７〕フッ化ビニリデン樹脂のメルトマスフローレイトは、３.８ｋｇ荷重、２３０℃で測定して、０.１〜４０ｇ／１０分である、前記〔１〕〜〔６〕のいずれかに記載の樹脂積層体。
〔８〕樹脂積層体の膜厚の平均値が１００〜２０００μｍであり、熱可塑性樹脂層（Ｂ）及び（Ｃ）の膜厚の平均値がそれぞれ１０〜２００μｍである前記〔１〕〜〔７〕のいずれかに記載の樹脂積層体。
〔９〕熱可塑性樹脂層（Ｂ）及び（Ｃ）に含まれる熱可塑性樹脂のビカット軟化温度がそれぞれ１００〜１６０℃である、前記〔１〕〜〔８〕のいずれかに記載の樹脂積層体。
〔１０〕熱可塑性樹脂層（Ｂ）及び（Ｃ）は（メタ）アクリル樹脂層又はポリカーボネート樹脂層である、前記〔１〕〜〔９〕のいずれかに記載の樹脂積層体。
〔１１〕熱可塑性樹脂層（Ｂ）及び（Ｃ）は、それぞれの熱可塑性樹脂層に含まれる全樹脂に基づいて５０質量％以上の（メタ）アクリル樹脂を含む、前記〔１〕〜〔１０〕のいずれかに記載の樹脂積層体。
〔１２〕熱可塑性樹脂層（Ｂ）及び（Ｃ）に含まれる（メタ）アクリル樹脂の重量平均分子量が５０,０００〜３００,０００である、前記〔１１〕に記載の樹脂積層体。
〔１３〕前記〔１〕〜〔１２〕のいずれかに記載の樹脂積層体を含む表示装置。
〔１４〕前記〔１〕〜〔１２〕のいずれかに記載の樹脂積層体及び偏光板が積層された樹脂積層体付き偏光板。
〔１５〕前記〔１４〕に記載の樹脂積層体付き偏光板を含む表示装置。 That is, the present invention includes the following preferred embodiments.
[1] A resin laminate having at least an intermediate layer (A) and thermoplastic resin layers (B) and (C) present on both sides of the intermediate layer (A),
The intermediate layer (A) contains 10 to 90% by mass of (meth) acrylic resin and 90 to 10% by mass of vinylidene fluoride resin based on the total resin contained in the intermediate layer (A), The weight average molecular weight (Mw) of the (meth) acrylic resin is 100,000 to 300,000,
At least one of the intermediate layer (A), the thermoplastic resin layers (B) and (C) includes at least one ultraviolet absorber having an absorption maximum at 320 to 400 nm,
Intermediate layer (A), the thermoplastic resin layer (B) and the film average thickness of (C), _{respectively,} and T A, _{T B} and _{T C} ([mu] m), intermediate layer (A), the thermoplastic resin layer ( When the contents of the ultraviolet absorbers in B) and (C) are respectively W _A , W _B and W _C (mass%), the following formula:

A resin laminate in which X calculated by the formula is 0.01 or more and 0.25 or less.
[2] The ultraviolet absorber having an absorption maximum at 320 to 400 nm is a group consisting of a triazine ultraviolet absorber, a benzotriazole ultraviolet absorber, a benzoate ultraviolet absorber, a benzophenone ultraviolet absorber, and a cyanoacrylate ultraviolet absorber. The resin laminate according to [1], which is at least one selected from the group consisting of:
[3] The intermediate layer (A) contains 35 to 45% by mass of (meth) acrylic resin and 65 to 55% by mass of vinylidene fluoride resin based on the total resin contained in the intermediate layer (A). The resin laminate according to [1] or [2].
[4] The resin according to any one of [1] to [3], wherein the content of alkali metal in the intermediate layer (A) is 50 ppm or less based on the total resin contained in the intermediate layer (A). Laminated body.
[5] (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 wt% of 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; ]
The resin laminate according to any one of [1] to [4], which is a copolymer containing at least one structural unit derived from a (meth) acrylic acid ester represented by:
[6] The resin laminate according to any one of [1] to [5], wherein the vinylidene fluoride resin is polyvinylidene fluoride.
[7] The melt mass flow rate of the vinylidene fluoride resin is 0.1 to 40 g / 10 minutes as measured at a load of 3.8 kg and 230 ° C., according to any one of the above [1] to [6]. Resin laminate.
[8] The above [1] to [7], wherein the average value of the film thickness of the resin laminate is 100 to 2000 μm, and the average value of the film thickness of the thermoplastic resin layers (B) and (C) is 10 to 200 μm, respectively. ] The resin laminated body in any one of.
[9] The resin laminate according to any one of [1] to [8], wherein the Vicat softening temperatures of the thermoplastic resins contained in the thermoplastic resin layers (B) and (C) are 100 to 160 ° C., respectively. .
[10] The resin laminate according to any one of [1] to [9], wherein the thermoplastic resin layers (B) and (C) are a (meth) acrylic resin layer or a polycarbonate resin layer.
[11] The thermoplastic resin layers (B) and (C) contain 50% by mass or more of (meth) acrylic resin based on the total resin contained in each thermoplastic resin layer. ] The resin laminated body in any one of.
[12] The resin laminate according to [11], wherein the (meth) acrylic resin contained in the thermoplastic resin layers (B) and (C) has a weight average molecular weight of 50,000 to 300,000.
[13] A display device comprising the resin laminate according to any one of [1] to [12].
[14] A polarizing plate with a resin laminate, in which the resin laminate and the polarizing plate according to any one of [1] to [12] are laminated.
[15] A display device comprising the polarizing plate with a resin laminate according to [14].

  Since the resin laminate of the present invention has an ultraviolet absorbing ability, it is particularly suitable for protecting a polarizing plate and is suitably used in a display device including a polarizing plate.

It is the schematic of the manufacturing apparatus of the resin laminated body of this invention used for the Example. It is a cross-sectional schematic diagram which shows one preferable form of the liquid crystal display device containing the resin laminated body of this invention.

  The resin laminate of the present invention has at least an intermediate layer (A) and thermoplastic resin layers (B) and (C) present on both sides of the intermediate layer (A). In other words, the resin laminate of the present invention has at least a configuration in which the thermoplastic resin layer (B) / intermediate layer (A) / thermoplastic resin layer (C) are laminated in this order.

  The intermediate layer (A) contains 10 to 90% by mass of (meth) acrylic resin and 90 to 10% by mass of vinylidene fluoride resin based on the total resin contained in the intermediate layer (A). 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, a sufficient dielectric constant cannot be obtained, and when the amount of vinylidene fluoride resin is higher than the above upper limit, durability and sufficient transparency of the resin laminate are obtained. I can't.

  The intermediate layer (A) has a dielectric constant of 30 to 60% by weight (meth) acrylic resin based on the total resin contained in the intermediate layer (A) from the viewpoint of easily increasing the dielectric constant and the transparency of the resin laminate. 70 to 40% by mass of vinylidene fluoride resin, preferably 35 to 45% by mass of (meth) acrylic resin and 65 to 55% by mass of vinylidene fluoride resin, more preferably 37 to 45% by mass. % Of (meth) acrylic resin and 63 to 55% by mass of vinylidene fluoride resin are more preferable, and 38 to 45% by mass of (meth) acrylic resin and 62 to 55% by mass of vinylidene fluoride resin are included. It is particularly preferable that it contains 38 to 43% by mass of (meth) acrylic resin and 62 to 57% by mass of vinylidene fluoride resin.

  Examples of the (meth) acrylic resin contained in the intermediate layer (A) of the resin laminate of the present invention include, for example, homopolymers of (meth) acrylic monomers such as (meth) acrylic acid esters and (meth) acrylonitrile, 2 types The copolymer of the above (meth) acryl monomer, the copolymer of monomers other than (meth) acryl monomer and (meth) acryl monomer, etc. are mentioned. 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).

［式中、Ｒ_１は水素原子又はメチル基を表し、Ｒ_１が水素原子のときＲ_２は炭素数１〜８のアルキル基を表し、Ｒ_１がメチル基のときＲ_２は炭素数２〜８のアルキル基を表す。］
で示される（メタ）アクリル酸エステルに由来する少なくとも１つの構造単位を含む共重合体
であることが好ましい。ここで、各構造単位の含有量は、得られた重合体を熱分解ガスクロマトグラフィーにより分析し、各単量体に対応するピーク面積を測定することにより算出できる。 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, 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 2 to 8 alkyl groups. 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 (A) is 100,000 to 300,000. When Mw is lower than the above lower limit, transparency when exposed to a high temperature and high humidity environment is not sufficient, and when Mw is higher than the above upper limit, film formability when producing a resin laminate cannot be obtained. . 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 producing a resin laminate. 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 it is easy to increase the strength of the obtained film, and is preferably not less than the above lower limit from the viewpoint of film formability of the resin laminate. 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 (A) of the resin laminate of the present invention include vinylidene fluoride homopolymers and copolymers 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 (A) is preferably 100,000 to 500,000, more preferably 150,000 to 450,000, and even more preferably 200,000 to 450,000, particularly preferably 350,000-450,000. It is easy for the transparency of the resin laminate to be increased when the resin laminate of the present invention is exposed to a high-temperature and high-humidity environment (for example, 60 ° C. and relative humidity 90%) that Mw is equal to or more than the above lower limit. preferable. Moreover, it is preferable that Mw is not more than the above upper limit because the film-forming property of the resin laminate is 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 resin laminate is used for a long period of time. It is preferable that the MFR is not less than the above lower limit because the film formability of the resin laminate 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 # 1300 from Kureha Corporation. "SOLEF (registered trademark) 6012, 6010 and 6008" manufactured by Solvay.

  The intermediate layer (A) 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 a resin laminated body is impaired remarkably. From the viewpoint of the hardness and weather resistance of the resin laminate, the amount of other resins is preferably 15% by mass or less, preferably 10% by mass or less, based on the total resin contained in the intermediate layer (A). Is more preferable, and it is still more preferable that it is 5 mass% or less. Examples of other resins include polycarbonate resins, polyamide resins, acrylonitrile-styrene copolymers, methyl methacrylate-styrene copolymers, and polyethylene terephthalate. The intermediate layer (A) 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 (A) is ( More preferably, it is only a (meth) acrylic resin and a vinylidene fluoride resin.

  The content of alkali metal in the intermediate layer (A) is preferably 50 ppm or less, more preferably 30 ppm or less, even more preferably 10 ppm or less, particularly preferably 1 ppm or less, based on the total resin contained in the intermediate layer (A). It is. It is preferable that the content of alkali metal in the intermediate layer (A) is not more than the above upper limit because it is easy to suppress a decrease in transparency when the resin laminate 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 (A) 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 resin laminate. Here, in the (meth) acrylic resin and / or vinylidene fluoride resin contained in the intermediate layer (A), a trace amount of emulsifier used in the production process remains. Therefore, the intermediate layer (A) contains, for example, 0.05 ppm or more of alkali metal such as sodium or potassium derived from the remaining emulsifier. In particular, when the (meth) acrylic resin and / or vinylidene fluoride resin contained in the intermediate layer (A) is obtained by emulsion polymerization, the amount of the emulsifier remaining in the resin increases, and the intermediate layer (A) The alkali metal content is also increased. From the viewpoint of easily suppressing a decrease in transparency of the resin laminate, 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 (A). .

  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. 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 of the present invention has at least thermoplastic resin layers (B) and (C) present on both sides of the intermediate layer (A). The thermoplastic resin layer (B) and the thermoplastic resin layer (C) may be the same layer or different layers.

  The thermoplastic resin layers (B) and (C) contain at least one kind of thermoplastic resin. The thermoplastic resin layers (B) and (C) are preferably 60% by mass or more, more preferably 70% by mass, based on the total resin contained in each thermoplastic resin layer, from the viewpoint of easily improving moldability. As described above, even more preferably, 80% by mass or more of the 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 layers (B) and (C) and the intermediate layer (A). The thermoplastic resin layers (B) and (C) may contain the same thermoplastic resin or may contain different thermoplastic resins. The thermoplastic resin layers (B) and (C) preferably contain the same thermoplastic resin from the viewpoint of easily suppressing warpage of the resin laminate.

  The thermoplastic resin contained in the thermoplastic resin layers (B) and (C) is preferably 100 to 160 ° C., more preferably 102 to 155 ° C., and still more preferably 102 to 150 ° C. from the viewpoint of heat resistance of the resin laminate. It has a Vicat softening temperature of 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. The Vicat softening temperature of the thermoplastic resin layer is measured according to the B50 method defined in JIS K 7206: 1999 “Plastics—Thermoplastic Plastic—Vicat Softening Temperature (VST) Test Method”. The Vicat softening temperature can be measured using a heat distortion tester (for example, “148-6 continuous type” manufactured by Yasuda Seiki Seisakusho Co., Ltd.). The measurement may be performed using a test piece obtained by press-molding each raw material to a thickness of 3 mm.

  The thermoplastic resin layers (B) and (C) are provided with other resins (for example, thermosetting resins such as fillers and resin particles) other than the thermoplastic resin for the purpose of increasing the strength and elasticity of the thermoplastic resin layer. May be included. 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 contained in each thermoplastic resin layer. . The lower limit of the amount of other resins is 0% by mass.

  The thermoplastic resin layers (B) and (C) are preferably a (meth) acrylic resin layer or a polycarbonate resin layer from the viewpoint of good molding processability and easy enhancement of adhesion to the intermediate layer (A). .

  One embodiment of the present invention in which the thermoplastic resin layers (B) and (C) are (meth) acrylic resin layers will be described below. In this embodiment, the thermoplastic resin layers (B) and (C) contain one or more (meth) acrylic resins. The thermoplastic resin layers (B) and (C) are preferably 50% by mass or more based on the total resin contained in each thermoplastic resin layer, more preferably 60% by mass or more, and even more, from the viewpoint of surface hardness. Preferably 70 mass% or more of (meth) acrylic resin is included.

  Examples of the (meth) acrylic resin include the resins described for the (meth) acrylic resin contained in the intermediate layer (A). Unless it mentions specially, the preferable (meth) acrylic resin described about the intermediate | middle layer (A) is similarly preferable also as a (meth) acrylic resin contained in a thermoplastic resin layer (B) and (C). The (meth) acrylic resin contained in the thermoplastic resin layers (B) and (C) and the (meth) acrylic resin contained in the intermediate layer (A) 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. 1,000. The weight average molecular weight is measured by gel permeation chromatography (GPC) measurement.

  In this embodiment, the thermoplastic resin layers (B) and (C) 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, as measured 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 (B) and (C) does not contain a vinylidene fluoride resin substantially from a viewpoint of heat resistance and surface hardness.

  In this aspect, the pencil hardness of the thermoplastic resin layers (B) and (C) is preferably HB or more, more preferably F or more, and more preferably H or more, from the viewpoint of enhancing scratch resistance. Is even more preferred.

  Next, another embodiment of the present invention in which the thermoplastic resin layers (B) and (C) are polycarbonate resin layers will be described below. In this embodiment, the thermoplastic resin layers (B) and (C) contain one or more polycarbonate resins. The thermoplastic resin layers (B) and (C) are preferably 60% by mass or more, more preferably 70% by mass or more based on the total resin contained in each thermoplastic resin layer, from the viewpoint of impact resistance. More preferably, 80% by mass or more of 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 layers (B) and (C) is preferably ³ to 120 cm 3/10 minutes, more preferably measured under conditions of a temperature of 300 ° C. and a load of 1.2 kg. 3~80cm ^3/10 min, 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. MVR can be measured at 300 ° C. under a load of 1.2 kg in accordance with JIS K 7210.

  In this embodiment, the thermoplastic resin layers (B) and (C) 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. When the thermoplastic resin layers (B) and (C) contain a polycarbonate resin and the above (meth) acrylic resin, the surface hardness of the thermoplastic resin layers (B) and (C) includes only the polycarbonate resin. It is preferable because it can be made higher than that.

  In the resin laminate of the present invention, at least one of the intermediate layer (A), the thermoplastic resin layer (B), and (C) is included in the display device when the resin laminate is used for a display device or the like. For the purpose of protecting other components such as a polarizing plate, it contains at least one ultraviolet absorber having an absorption maximum at 320 to 400 nm. From the viewpoint of easily increasing the ultraviolet absorbing ability of the resin laminate, the content of the ultraviolet absorber is 0.01% by mass or more, preferably 0.05 based on the total resin contained in each layer containing the ultraviolet absorber. It is at least mass%, more preferably at least 0.10 mass%. The upper limit of the content of the ultraviolet absorber having an absorption maximum at 320 to 400 nm is that all layers contained in each layer containing the ultraviolet absorber are easy to suppress bleed out from the layer and easily avoid yellowing of the layer. Preferably it is 2.0 mass% or less based on resin, More preferably, it is 1.75 mass% or less, More preferably, it is 1.5 mass% or less. From the viewpoint of easily increasing the ultraviolet absorbing ability of the resin laminate, at least one of the thermoplastic resin layers (B) and (C) contains at least one ultraviolet absorber having an absorption maximum at 320 to 400 nm. It is preferable that both the thermoplastic resin layers (B) and (C) contain at least one ultraviolet absorber having an absorption maximum at 320 to 400 nm.

  It does not specifically limit as an ultraviolet absorber which has an absorption maximum in 320-400 nm, You may use a conventionally well-known various ultraviolet absorber. Examples thereof include triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and benzotriazole-based ultraviolet absorbers having an absorption maximum at 320 to 400 nm. As an ultraviolet absorber, you may use 1 type of these ultraviolet absorbers individually or in combination of 2 or more types.

  Examples of the triazine ultraviolet absorber having an absorption maximum at 320 to 400 nm include 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine.

  Examples of the benzophenone ultraviolet absorber having an absorption maximum at 320 to 400 nm include 2,2′-dihydroxy-4-methoxy-benzophenone.

  Examples of the benzotriazole ultraviolet absorber having an absorption maximum at 320 to 400 nm include 2- (2′-hydroxy-5-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-di-t. -Butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2- (2 '-Hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy) -3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole, 2,2'-methylenebis (4- (1,1,3,3-tetra Methylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 (2 '-Hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, (2 (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) -5-chlorobenzo Triazole, 2 (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, (2 (2'-hydroxy-3', 5'-di tert- amyl phenyl) -5-chloro benzotriazole.

  A commercially available product may be used as the ultraviolet absorber having an absorption maximum at 320 to 400 nm. For example, as a triazine-based ultraviolet absorber, “Adeka Stab LA-F70 (2,4,6-Tris ( 2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine) ”(absorbance 0.6),“ Adeka Stub LA-31, LA manufactured by ADEKA Corporation as a benzotriazole-based ultraviolet absorber. -31RG, LA-31G (2,2'-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol) "(absorbance 0.2 ), “Kemisorb 279 (2,2′-methylene bis (4- (1,1,3,3-tetramethylbutyl)- -(2H-benzotriazol-2-yl) phenol) "(absorbance 0.1), etc. The absorbance of the exemplified UV absorber is such that the concentration of the UV absorber is 10 mg / L in chloroform. It melt | dissolved and the numerical value in 380 nm was measured with the spectrophotometer U-4100 made from HITACHI.

  In the resin laminate of the present invention, at least one of the intermediate layer (A), the thermoplastic resin layer (B), and (C) has an effect of protecting other components such as a polarizing plate included in the display device from ultraviolet rays. In addition to the above-described ultraviolet absorber having an absorption maximum at 320 to 400 nm, an ultraviolet absorber having an absorption maximum at 200 to 320 nm may be further included.

  The ultraviolet absorber having an absorption maximum at 200 to 320 nm is not particularly limited, and various conventionally known ultraviolet absorbers may be used. Examples thereof include triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers. As the ultraviolet absorber, one or more of these ultraviolet absorbers may be used in combination with the ultraviolet absorber having the absorption maximum at 320 to 400 nm.

  Examples of the triazine-based ultraviolet absorber having an absorption maximum at 200 to 320 nm include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine and 2,4-diphenyl-6. -(2-hydroxy-4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl -(2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,6 -Diphenyl-4- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octylo) Ciphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2- Hydroxy-4-benzyloxyphenyl) -1,3,5-triazine, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-N-octyloxyphenyl) -1,3 , 5-triazine, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (2- (2-ethylhexanoyloxy) ethoxy) phenol.

  Examples of the benzophenone ultraviolet absorber having an absorption maximum at 200 to 320 nm include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy- 4-dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2,2'-dihydroxy-4-methoxy-benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-benzophenone, 2,2 ', 4,4'-tetrahydroxy-benzophenone.

  Examples of the benzotriazole ultraviolet absorber having an absorption maximum at 200 to 320 nm include 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazole.

  Examples of the benzoate ultraviolet absorber having an absorption maximum at 200 to 320 nm include 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, 2,6-dibenzoate, -T-butylphenyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, n-octadecyl-3,5 -Di-t-butyl-4-hydroxybenzoate.

  Examples of the cyanoacrylate ultraviolet absorber having an absorption maximum at 200 to 320 nm include 2'-ethylhexyl-2-cyano-3,3-diphenyl acrylate, ethyl-2-cyano-3- (3 ', 4'-methylenedi Oxyphenyl) -acrylate.

  A commercially available product may be used as the UV absorber having an absorption maximum at 200 to 320 nm. For example, as a triazine UV absorber, “Kemisorb 102 (2,4-bis (2,4-bis Dimethylphenyl) -6- (2-hydroxy-4-N-octyloxyphenyl) -1,3,5-triazine) ”(absorbance 0.1),“ Adekastab LA-46 (2- (4,6-diphenyl) -1,3,5-triazin-2-yl) -5- (2- (2-ethylhexanoyloxy) ethoxy) phenol) "(absorbance 0.05)," TINUVIN 1577 (2 , 4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine) ”(absorbance 0.1). The absorbance of the exemplified ultraviolet absorber is the absorbance at 380 nm. This can be measured by dissolving a UV absorber in chloroform at a concentration of 10 mg / L and using a spectrophotometer (for example, a spectrophotometer U-4100 manufactured by HITACHI).

  In the resin laminate of the present invention, at least one of the intermediate layer (A), the thermoplastic resin layer (B), and (C) may contain a combination of the above-mentioned commercially available products. A combination of “Kemisorb 102” and at least one of “ADEKA STAB LA-F70”, “ADEKA STAB LA-31, LA-31RG, LA-31G” manufactured by ADEKA Corporation, “ADK STAB LA-46” manufactured by ADEKA Corporation, and A combination of at least one of “ADK STAB LA-31, LA-31RG, LA-31G” and “ADK STAB LA-F70”, or “TINUBIN 1577” manufactured by BASF Japan Ltd. and “ADK STAB manufactured by ADEKA Corporation” "LA-F70" and "Adeka Stub LA-31, LA-31RG, LA-31G" A combination of one and Kutomo the like. The ultraviolet absorbers that can be used are not limited to those exemplified.

  The ultraviolet absorber that can be contained in at least one of the intermediate layer (A), the thermoplastic resin layer (B), and (C) is a mol at the wavelength of the absorption maximum from the viewpoint of easily enhancing the ultraviolet absorbing ability of the resin laminate. The extinction coefficient is preferably 10 L / mol · cm or more, and more preferably 15 L / mol · cm or more. When the molar extinction coefficient of the ultraviolet absorber is not less than the above lower limit, the ultraviolet absorption ability of the resin laminate of the present invention is further improved, and the content of the ultraviolet absorber in at least one layer of the resin laminate is reduced. can do.

  The ultraviolet absorber preferably has a weight average molecular weight of 500 to 1000, more preferably 550 to 800. It is preferable that the weight average molecular weight of the ultraviolet absorber is not less than the above lower limit because it is easy to suppress smoke generation during the molding process. Moreover, it is preferable that the weight average molecular weight of a ultraviolet absorber is below the said upper limit, since it is easy to improve compatibility with resin contained in the layer containing a ultraviolet absorber.

により算出されるＸは、０.０１以上０.２５以下であることが好ましい。Ｘが上記の下限以上であると、紫外線からの偏光子の保護効果を高めやすい。同様の観点から、Ｘは好ましくは０．０１５以上、より好ましくは０．０２以上、さらにより好ましくは０．０２５以上である。Ｘが上記の上限以下であると、樹脂積層体自体のＹＩを低くし、良好な外観を得やすい。同様の観点から、Ｘは好ましくは０．２４５以下、より好ましくは０．２４以下、さらにより好ましくは０．２３５以下である。 In the resin laminate of the present invention, the intermediate layer (A), the thermoplastic resin layer (B) and the film average thickness of (C), _{respectively,} and T A, _{T B} and _{T C} ([mu] m), intermediate layer ( a), the thermoplastic resin layer (B) and the content of the ultraviolet absorber in (C), _{respectively,} when the W a, _{W B} and _{W C} (mass%), the following formula:

X calculated by is preferably 0.01 or more and 0.25 or less. When X is not less than the above lower limit, it is easy to enhance the effect of protecting the polarizer from ultraviolet rays. From the same viewpoint, X is preferably 0.015 or more, more preferably 0.02 or more, and even more preferably 0.025 or more. When X is not more than the above upper limit, the YI of the resin laminate itself is lowered and a good appearance is easily obtained. From the same viewpoint, X is preferably 0.245 or less, more preferably 0.24 or less, and even more preferably 0.235 or less.

  At least one of the intermediate layer (A), the thermoplastic resin layer (B), and (C) in the resin laminate of the present invention is a variety of commonly used additives as long as the effects of the present invention are not impaired. May further be included. Examples of additives include stabilizers, antioxidants, light stabilizers, foaming agents, lubricants, mold release agents, antistatic agents, flame retardants, mold release agents, polymerization inhibitors, flame retardant aids, reinforcing agents, Examples thereof include coloring agents such as 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 (A), the thermoplastic resin layer (B), and (C) further contains a colorant, the content of the colorant in each layer is appropriately determined according to the purpose, the type of the colorant, and the like. You can choose. When using a bluing agent as a coloring agent, the content can be made into about 0.01-10 ppm based on the total resin 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) Viloet B (manufactured by Sumika Chemtex Co., Ltd.) and Polycinslen (registered trademark) Blue RLS (manufactured by Clariant), Diaresin Violet D, Diaresin Blue G, Diaresin Blue N (above, Mitsubishi Chemical Corporation) It is done.

  As for the resin laminated body of this invention, the average value of the film thickness of a resin laminated body is 100-2000 micrometers, and the average value of the film thickness of a thermoplastic resin layer (B) and (C) is 10-200 micrometers, respectively. From the viewpoint of easily suppressing warpage of the resin laminate of the present invention.

  The average value of the film thickness of the resin 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, from the viewpoint of the rigidity of the resin laminate. 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 is measured with a digital micrometer. Let the average value which performed the said measurement in 10 points | pieces of a resin laminated body be an average value of a film thickness.

  In the resin laminate of the present invention, the average values of the film thicknesses of the thermoplastic resin layers (B) and (C) are each preferably 10 μm or more, more preferably 30 μm or more, and even more, from the viewpoint of easily increasing the surface hardness. Preferably it is 50 micrometers or more. 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 of the present invention, the average value of the film thickness of the intermediate layer (A) 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 (A) 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 of the present invention is preferably a dielectric 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 a rate. 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 kind and amount of the vinylidene fluoride resin contained in the intermediate layer (A) of the resin laminate of the present invention, or by adding a high dielectric constant compound such as ethylene carbonate or propylene carbonate. Can be adjusted within the range. The dielectric constant is based on JIS K 6911: 1995, and the resin laminate of the present invention is allowed to stand for 24 hours in an environment of relative humidity of 50% at 23 ° C., and in this environment, 3 V , Measured at 100 kHz. For the measurement, commercially available equipment may be used, for example, “precision LCR meter HP4284A” manufactured by Agilent Technologies, Inc. may be used.

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

  The resin laminate of the present invention is measured in accordance with JIS K7136: 2000, preferably 2.0% or less, using the resin laminate after exposure for 120 hours in an environment of 60 ° C. and 90% relative humidity. More preferably, the haze (haze value) is 1.8% or less, and even more preferably 1.5% or less. Further, the resin laminate of the present invention is measured according to JIS Z 8722: 2009 using a resin laminate after exposure 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. The resin laminate of the present invention having the above-described haze and yellowness is not easily warped even when used in an environment such as high temperature and high humidity, and maintains transparency and easily suppresses yellowing. To preferred.

  The resin laminate of the present invention may further have at least one functional layer in addition to the intermediate layer (A) and the thermoplastic resin layers (B) and (C). The functional layer is preferably present on the surface of the thermoplastic resin layer (B) and / or (C) opposite to the intermediate layer (A). Examples of the functional layer include a hard coat layer, an antireflection layer, an antiglare layer, an antistatic layer, and an anti-fingerprint layer. These functional layers may be laminated on the resin laminate of the present invention via an adhesive layer, or may be a coating layer laminated by coating. As the functional layer, for example, a cured film as described in JP 2013-86273 A may be used. The functional layer is, for example, coated on one side or both sides of at least one functional layer selected from the group consisting of a hard coat layer, an antiglare layer, an antistatic layer, and an anti-fingerprint layer by a coating method, a sputtering method, a vacuum deposition method, etc. The antireflection layer may be a further 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, the thickness is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 70 μm or less.

  The resin laminate of the present invention is produced from the resin composition (A) that gives the intermediate layer (A), and the resin compositions (B) and (C) that give the thermoplastic resin layers (B) and (C), respectively. Can do. In the present specification, the resin compositions (B) and (C) need only contain at least a resin that gives the thermoplastic resin layers (B) and (C). A composition containing more than one kind of component may be used, or a single type of resin may be used.

  The resin composition (A) 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 twin-screw kneader, another-screw extruder, 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 (B) and (C) can also be produced in the same manner as resin composition (A), for example, by melt kneading under the above temperature and shear rate. Further, for example, when the thermoplastic resin layers (B) and (C) contain one kind of thermoplastic resin, a resin laminate may be manufactured by performing melt extrusion described later without melt-kneading in advance.

  When the intermediate layer (A), the thermoplastic resin layers (B) and (C) contain additives, the additives may be included in advance in the resin contained in each layer, and are added when the resin is melt-kneaded. Alternatively, the resin may be added after melt-kneading, or may be added when a resin laminate is produced using the resin composition.

  The resin laminate of the present invention having at least the intermediate layer (A) and the thermoplastic resin layers (B) and (C) present on both sides of the intermediate layer (A) can be produced by, for example, melt extrusion molding, solution casting Each layer (A)-(C) is produced separately from the resin composition (A)-(C) by a film-forming method, a hot press method, an injection molding method, etc., and these are pasted through, for example, an adhesive or an adhesive. The resin compositions (A) to (C) may be laminated and integrated by melt coextrusion molding. In the case of producing a resin laminate by bonding, it is preferable to use an injection molding method and a melt extrusion molding method for producing each layer, and it is more preferable to use a melt extrusion molding method. The resin laminate of the present invention can be produced by melt coextrusion molding of the resin compositions (A) to (C), as compared with the resin laminate produced by bonding, usually secondary molding. This is preferable because a resin laminate that can be easily processed is obtained.

  In the melt coextrusion molding, for example, the resin composition (A) and the resin compositions (B) and (C) are separately fed into two or three uniaxial or biaxial extruders and melted respectively. After kneading, the intermediate layer (A) formed from the resin composition (A) and the thermoplastic resin layers (B) and (C) are laminated and integrated through a feed block die, a multi-manifold die, and the like. This is a molding method. When the resin compositions (B) and (C) are the same composition, one composition melt-kneaded in one extruder is divided into two via a feed block die and the thermoplastic resin layer (B) and (C) may be formed. The obtained film is preferably cooled and solidified by, for example, a roll unit.

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

  The resin laminate of the present invention can be used in various display devices. A display device is a device having a display element and includes a light-emitting element or a light-emitting device as a light-emitting source. 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 resin laminate of the present invention is suitably used in these display devices, for example, as a front plate or a transparent electrode.

  When the resin laminate of the present invention is used as a transparent electrode in a touch panel or the like, a transparent conductive film is produced by forming a transparent conductive film on at least one surface of the resin laminate of the present invention, and the transparent electrode is formed from the transparent conductive sheet. Can be manufactured.

  As a method for forming a transparent conductive film on at least one surface of the resin laminate of the present invention, the transparent conductive film may be directly formed on the surface of the resin laminate of the present invention, or a transparent conductive film is previously formed. A plastic film may be laminated on the surface of the resin laminate of the present invention.

  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.

  Any method may be used for laminating a film, on which a transparent conductive film has been previously formed, on the surface of the resin laminate of the present invention as long as it is free from bubbles and provides 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 of 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 of the present invention, 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 resin laminate of the present invention as a display panel face plate and using a transparent conductive sheet manufactured from the resin laminate of the present invention as a transparent electrode such as a touch screen. Specifically, the resin 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 for 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 resin laminate of the present invention. The display device of the present invention can be, for example, the display device described above.

  The present invention also provides a polarizing plate with a resin laminate in which the resin laminate of the present invention and a polarizing plate are laminated, and a display device including the polarizing plate with a resin laminate. In the polarizing plate with a resin laminate of the present invention, the resin laminate of the present invention is laminated on the polarizing plate via an optical adhesive such as an adhesive and a pressure-sensitive adhesive. As the adhesive or pressure-sensitive adhesive, a known one may be used as appropriate.

  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 of the present invention is laminated on the polarizing plate 11 via the optical adhesive layer 12, and this laminate can be disposed on the viewing side of the liquid crystal cell 13. A polarizing plate 11 is usually disposed on the back side of the liquid crystal cell 13. The liquid crystal display device 14 is composed of such members. 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 polycarbonate-type material, it measured on 300 degreeC conditions under the load of 1.2 kg with the "semi auto melt indexer 2A" by the Toyo Seiki Seisakusho Co., Ltd. based on JISK7210.

[Total light transmittance and haze]
Haze transmittance meter ("HR-100" manufactured by Murakami Color Research Laboratory Co., Ltd.) according to JIS K 7361-1: 1997 "Plastics-Test method for total light transmittance of transparent materials-Part 1: Single beam method" ).

[YI value]
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 arbitrary 10 points was defined as the average value of the film thickness of the resin laminate.
The thickness of each layer of the intermediate layer (A), the thermoplastic resin layer (B) and (C) is measured after cutting the resin laminate perpendicularly to the surface direction and polishing the cross section with sandpaper It was measured by observing with a microscope manufactured by Micro Square. The average value obtained by performing the above measurement at any 10 points was defined as the average value of the film thickness of each layer.

[Production Example 1]
Mix 97.7 parts by weight of methyl methacrylate and 2.3 parts by weight of methyl acrylate, add 0.05 part by weight of chain transfer agent (octyl mercaptan) and 0.1 part by weight of release agent (stearyl alcohol). 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, the temperature was 175 ° C, and the average polymerization rate was 54%. 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 97.0% by mass, and the structural unit derived from methyl acrylate was 3.0% by mass.

[Content of structural unit by pyrolysis gas chromatography]
(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.
Pyrolysis device: CURIE POINT PYROLYZER JHP-22 (manufactured by Nippon Analytical Industrial Co., Ltd.)
Metal cell: Pyrofoil F590 (Nippon Analytical Industrial Co., 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 heating conditions: Hold at 100 ° C. for 15 minutes, then increase to 150 ° C. at 10 ° C./min. 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 acrylic ester 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, the 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.

[Production Example 2]
A pellet-like methacrylic resin (ii) was prepared in the same manner as in Production Example 1 except that 98.9 parts by weight of methyl methacrylate, 1.1 parts by weight of methyl acrylate, and 0.16 parts by weight 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 97.5% by mass, and the structural unit derived from methyl acrylate was 2.5% by mass.

Table 1 shows the physical properties of the methacrylic resins (i) and (ii) obtained in Production Examples 1 and 2.

[Production Example 3]
In order to make the bluing agent into a master batch (MB), 99.99 parts by mass of the methacrylic resin (i) obtained in Production Example 1 and 0.01 parts by mass of the colorant were dry blended, and a 40 mmφ single screw extruder ( Tanabe Plastic Machinery Co., Ltd.) was melt-mixed at a preset temperature of 250 to 260 ° C. to obtain colored master batch pellets (MB (i)). As a colorant, a bluing agent (“Sumiplast (registered trademark) Violet B” manufactured by Sumika Chemtex Co., Ltd.) was used.

[Production Example 4]
In order to contain the ultraviolet absorber in the thermoplastic resin layer, methacrylic resins (iii) to (viii) containing the ultraviolet absorber in advance with the composition shown in Table 2 were produced. Specifically, the methacrylic resin (ii) and “LA-31RG” manufactured by ADEKA Co., Ltd., which is an ultraviolet absorber having an absorption maximum at 320 to 400 nm, are melted at 240 to 250 ° C. with the composition shown in Table 2. Kneaded.

[Production Example 5]

In the examples and comparative examples, the following commercially available products were used as polycarbonate resins. Table 3 shows the physical properties of the resin.
Polycarbonate resin (i): “Caliver (registered trademark) 301-30” manufactured by Sumika Stylon Polycarbonate Co., Ltd.

  The weight average molecular weight of the polycarbonate resin was measured by GPC. A methacrylic resin manufactured by Showa Denko KK with a narrow molecular weight distribution and known molecular weight was used as a standard reagent, a calibration curve was created from the elution time and molecular weight, and the weight average molecular weight was measured. Specifically, 40 mg of resin was dissolved in 20 ml of tetrahydrofuran (THF) solvent to prepare a measurement sample. As a measuring device, two columns “TSKgel SuperHM-H”, which is a column made by Tosoh Corporation, and one “SuperH2500” were installed in series, and an RI detector was used as a detector.

A polycarbonate resin (ii) and (iii) were produced by previously containing polycarbonate resin (i) with an ultraviolet absorber and a colorant in the composition shown in Table 4 (hereinafter, PC (ii) and (iii) respectively) Called). Specifically, the polycarbonate resin (i), “LA-31RG” manufactured by ADEKA Co., Ltd., which is an ultraviolet absorber having an absorption maximum at 320 to 400 nm, and “Sumiplast” manufactured by Sumika Chemtex Co., Ltd. (Trademark registration) Violet B ") was melt kneaded at 250 to 260 ° C with the composition shown in Table 4.

In the examples, commercially available vinylidene fluoride resins having the physical properties shown in Table 5 were used.
Vinylidene fluoride resin (i): Polyvinylidene fluoride resin produced by suspension polymerization (ii): Polyvinylidene fluoride produced by emulsion polymerization

  The weight average molecular weight (Mw) of the vinylidene fluoride resin was measured by gel permeation chromatography (GPC). Using polystyrene 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. As a measuring device, two columns “TSKgel SuperHM-H”, which is a column made by Tosoh Corporation, and one “SuperH2500” were installed in series, and an RI detector was used as a detector.

[Production of Resin Composition A1]
39 parts by mass of methacrylic resin (i), 60 parts by mass of vinylidene fluoride resin (i), and 1 part by mass of master batch pellet MB (i) obtained in Production Example 3 were mixed at a ratio shown in Table 4, and an intermediate layer ( A resin composition A1 for forming A) was obtained.

[Production of Resin Composition A2]
39 parts by mass of methacrylic resin (i), 60 parts by mass of vinylidene fluoride resin (ii), and 1 part by mass of master batch pellet MB (i) obtained in Production Example 3 were mixed at a ratio shown in Table 4, and an intermediate layer ( A resin composition A2 for forming A) was obtained.

[Production of resin laminates of Examples 1 to 8 and Comparative Examples 1 to 3]
As a resin composition for forming the intermediate layer (A), the resin composition A1 was used in Examples 1 to 7 and Comparative Examples 1 to 3, and the resin composition A2 was used in Example 8.
Resins shown in Table 6 were used as the resin compositions (B) and (C) for forming the thermoplastic resin layers (B) and (C). A resin laminate was manufactured from these resin compositions using the apparatus shown in FIG. Specifically, the resin composition (A) is 65 mmφ single screw extruder 2 (manufactured by Toshiba Machine Co., Ltd.), and the resin compositions (B) and (C) are 45 mmφ single screw extruders 1 and 3 (manufactured by Hitachi Zosen Corporation). ] To melt each. Subsequently, these are laminated so as to be represented by the above-mentioned B layer / A layer / C layer through a feed block 4 (manufactured by Hitachi Zosen Corporation) having a set temperature of 230 to 270 ° C. Extruded from 5 [manufactured by Hitachi Zosen Co., Ltd., 2-type, 3-layer distribution] to obtain a film-like molten resin 6 In this embodiment, the B layer and the C layer are layers having the same composition. Then, 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, the product was wound around a third cooling roll 9, molded and cooled to obtain a resin laminate 10 having a three-layer structure in which each layer has an average thickness shown in Table 4. Each of the obtained resin laminates 10 had a total film thickness of about 800 μm, and was visually transparent when visually observed.

  In the resin laminates of Examples 1 to 8 and Comparative Examples 1 to 3, the alkali metal (Na and K) content in the intermediate layer (A) is 0.3 ppm in Examples 1 to 7 and Comparative Examples 1 and 3. In Comparative Example 2, it was 0.5 ppm, and in Example 8, it was 100 ppm.

  In the resin laminates of Examples 1 to 8 and Comparative Examples 1 to 3, the dielectric constant is 5.2 in Examples 1 and 5, 5.3 in Examples 2 to 4, 6 and 7, and 4 in Example 8. .9, and Comparative Examples 1 to 3 were 5.1. It was confirmed that any of the resin laminates has a dielectric constant sufficient for use in a display device such as a touch panel.

Using the resin laminates of Examples 1 to 8 and Comparative Examples 1 to 3, total light transmittance (Tt) and haze were measured. The results obtained are shown in Table 7. Further, the resin laminates of Examples 1 to 7 and Comparative Examples 1 to 3 were exposed to an environment of 90% relative humidity at 60 ° C. for 120 hours, and the total light transmittance was similarly applied to the resin laminates after the durability test. And haze measurement.

  It is confirmed that the resin laminates of the present invention shown in Examples 1 to 8 are resin laminates having a low transmittance at 380 nm, a high UV protection effect and a suppressed yellowing, and having high transparency. It was done.

1 Single screw extruder (extrudes the melt of resin composition B)
2 Single screw extruder (extrudes the melt of resin composition A)
3 Single screw extruder (extruded melt of resin composition C)
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 10A Intermediate layer (A)
10B Thermoplastic resin layer (B)
10C Thermoplastic resin layer (C)
DESCRIPTION OF SYMBOLS 11 Polarizing plate 12 Optical adhesion layer 13 Liquid crystal cell 14 Liquid crystal display device

Claims (36)

A resin laminate having at least an intermediate layer (A) and thermoplastic resin layers (B) and (C) respectively present on both sides of the intermediate layer (A),
The intermediate layer (A) includes 35 to 45 % by mass of (meth) acrylic resin and 65 to 55 % by mass of vinylidene fluoride resin based on the total resin contained in the intermediate layer (A), The weight average molecular weight (Mw) of the (meth) acrylic resin is 100,000 to 300,000,
At least one of the intermediate layer (A), the thermoplastic resin layers (B) and (C) includes at least one ultraviolet absorber having an absorption maximum at 320 to 400 nm,
Intermediate layer (A), the thermoplastic resin layer (B) and the film average thickness of (C), _{respectively,} and T A, _{T B} and _{T C} ([mu] m), intermediate layer (A), the thermoplastic resin layer ( When the contents of the ultraviolet absorbers in B) and (C) are respectively W _A , W _B and W _C (mass%), the following formula:

A resin laminate in which X calculated by the formula is 0.01 or more and 0.25 or less.   The UV absorber having an absorption maximum at 320 to 400 nm is selected from the group consisting of triazine UV absorbers, benzotriazole UV absorbers, benzoate UV absorbers, benzophenone UV absorbers, and cyanoacrylate UV absorbers. The resin laminate according to claim 1, which is at least one kind. The resin laminate according to claim 1 or 2 , wherein the content of alkali metal in the intermediate layer (A) is 50 ppm or less based on the total resin contained in the intermediate layer (A). (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 wt% of 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; ]
The resin laminated body in any one of Claims 1-3 which is a copolymer containing the at least 1 structural unit derived from the (meth) acrylic acid ester shown by these. The resin laminate according to any one of claims 1 to 4 , wherein the vinylidene fluoride resin is polyvinylidene fluoride. Melt mass flow rate of the vinylidene fluoride resin, 3.8 kg load, as measured at 230 ° C., a 0.1 to 40 g / 10 min, the resin laminate according to any one of claims 1-5. The average value of the film thickness of the resin laminate 100 to 2000, the average value of the thickness of the thermoplastic resin layer (B) and (C) is 10~200μm respectively, to one of the claims 1-6 The resin laminate described. The resin laminate according to any one of claims 1 to 7 , wherein the Vicat softening temperatures of the thermoplastic resins contained in the thermoplastic resin layers (B) and (C) are 100 to 160 ° C, respectively. The resin laminate according to any one of claims 1 to 8 , wherein the thermoplastic resin layers (B) and (C) are a (meth) acrylic resin layer or a polycarbonate resin layer. The thermoplastic resin layer (B) and (C), based on the total resin contained in each of the thermoplastic resin layer containing at least 50 wt% of (meth) acrylic resin, according to any one of claims 1-9 Resin laminate. The resin laminate according to claim 10 , wherein the (meth) acrylic resin contained in the thermoplastic resin layers (B) and (C) has a weight average molecular weight of 50,000 to 300,000. A display device comprising a resin laminate having at least an intermediate layer (A) and thermoplastic resin layers (B) and (C) respectively present on both sides of the intermediate layer (A),
  The intermediate layer (A) contains 10 to 90% by mass of (meth) acrylic resin and 90 to 10% by mass of vinylidene fluoride resin based on the total resin contained in the intermediate layer (A), The weight average molecular weight (Mw) of the (meth) acrylic resin is 100,000 to 300,000,
  At least one of the intermediate layer (A), the thermoplastic resin layers (B) and (C) includes at least one ultraviolet absorber having an absorption maximum at 320 to 400 nm,
  The average values of the film thicknesses of the intermediate layer (A), the thermoplastic resin layers (B) and (C) are respectively T _A , T _B And T _C (Μm), and the contents of the ultraviolet absorber in the intermediate layer (A), the thermoplastic resin layer (B) and (C) are respectively W _A , W _B And W _C (% By mass), the following formula:

A display device in which X calculated by the above is 0.01 or more and 0.25 or less. The UV absorber having an absorption maximum at 320 to 400 nm is selected from the group consisting of triazine UV absorbers, benzotriazole UV absorbers, benzoate UV absorbers, benzophenone UV absorbers, and cyanoacrylate UV absorbers. The display device according to claim 12, wherein the display device is at least one kind. The intermediate layer (A) contains 35 to 45 mass% (meth) acrylic resin and 65 to 55 mass% vinylidene fluoride resin based on the total resin contained in the intermediate layer (A). Or the display apparatus of 13. The display device according to claim 12, wherein the content of alkali metal in the intermediate layer (A) is 50 ppm or less based on the total resin contained in the intermediate layer (A). (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% by weight of formula (1):

[Wherein R ₁ Represents a hydrogen atom or a methyl group, R ₁ R is hydrogen atom ₂ Represents an alkyl group having 1 to 8 carbon atoms, and R ₁ R is methyl ₂ Represents an alkyl group having 2 to 8 carbon atoms. ]
A copolymer comprising at least one structural unit derived from a (meth) acrylic acid ester represented by
The display device according to claim 12, wherein The display device according to claim 12, wherein the vinylidene fluoride resin is polyvinylidene fluoride. The display device according to any one of claims 12 to 17, wherein the melt mass flow rate of the vinylidene fluoride resin is 0.1 to 40 g / 10 minutes as measured at a load of 3.8 kg and 230 ° C. In any one of Claims 12-18 whose average value of the film thickness of a resin laminated body is 100-2000 micrometers, and the average value of the film thickness of a thermoplastic resin layer (B) and (C) is 10-200 micrometers, respectively. The display device described. The display device according to any one of claims 12 to 19, wherein the Vicat softening temperatures of the thermoplastic resins contained in the thermoplastic resin layers (B) and (C) are 100 to 160 ° C, respectively. The display device according to any one of claims 12 to 20, wherein the thermoplastic resin layers (B) and (C) are a (meth) acrylic resin layer or a polycarbonate resin layer. The thermoplastic resin layers (B) and (C) include 50% by mass or more (meth) acrylic resin based on the total resin contained in each thermoplastic resin layer. Display device. The display device according to claim 22, wherein the (meth) acrylic resin contained in the thermoplastic resin layers (B) and (C) has a weight average molecular weight of 50,000 to 300,000. With a resin laminate comprising a resin laminate having at least an intermediate layer (A) and thermoplastic resin layers (B) and (C) present on both sides of the intermediate layer (A), and a polarizing plate. A polarizing plate,
  The intermediate layer (A) contains 10 to 90% by mass of (meth) acrylic resin and 90 to 10% by mass of vinylidene fluoride resin based on the total resin contained in the intermediate layer (A), The weight average molecular weight (Mw) of the (meth) acrylic resin is 100,000 to 300,000,
  At least one of the intermediate layer (A), the thermoplastic resin layers (B) and (C) includes at least one ultraviolet absorber having an absorption maximum at 320 to 400 nm,
  The average values of the film thicknesses of the intermediate layer (A), the thermoplastic resin layers (B) and (C) are respectively T _A , T _B And T _C (Μm), and the contents of the ultraviolet absorber in the intermediate layer (A), the thermoplastic resin layer (B) and (C) are respectively W _A , W _B And W _C (% By mass), the following formula:

A polarizing plate with a resin laminate, wherein X calculated by the above is 0.01 or more and 0.25 or less. The UV absorber having an absorption maximum at 320 to 400 nm is selected from the group consisting of triazine UV absorbers, benzotriazole UV absorbers, benzoate UV absorbers, benzophenone UV absorbers, and cyanoacrylate UV absorbers. The polarizing plate with a resin laminate according to claim 24, which is at least one kind. The intermediate layer (A) contains 35 to 45 mass% (meth) acrylic resin and 65 to 55 mass% vinylidene fluoride resin based on the total resin contained in the intermediate layer (A). Or the polarizing plate with a resin laminated body of 25. 27. The polarizing plate with a resin laminate according to claim 24, wherein the content of alkali metal in the intermediate layer (A) is 50 ppm or less based on the total resin contained in the intermediate layer (A). (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% by weight of formula (1):

[Wherein R ₁ Represents a hydrogen atom or a methyl group, R ₁ R is hydrogen atom ₂ Represents an alkyl group having 1 to 8 carbon atoms, and R ₁ R is methyl ₂ Represents an alkyl group having 2 to 8 carbon atoms. ]
A copolymer comprising at least one structural unit derived from a (meth) acrylic acid ester represented by
The polarizing plate with a resin laminate according to any one of claims 24 to 27. The polarizing plate with a resin laminate according to any one of claims 24 to 28, wherein the vinylidene fluoride resin is polyvinylidene fluoride. The polarizing plate with a resin laminate according to any one of claims 24 to 29, wherein the melt mass flow rate of the vinylidene fluoride resin is 0.1 to 40 g / 10 minutes as measured at a load of 3.8 kg and 230 ° C. . The average value of the film thickness of the resin laminate is 100 to 2000 µm, and the average value of the film thicknesses of the thermoplastic resin layers (B) and (C) is 10 to 200 µm, respectively. The polarizing plate with a resin laminated body of description. The polarizing plate with a resin laminate according to any one of claims 24 to 31, wherein the Vicat softening temperatures of the thermoplastic resins contained in the thermoplastic resin layers (B) and (C) are 100 to 160 ° C, respectively. The polarizing plate with a resin laminate according to any one of claims 24 to 32, wherein the thermoplastic resin layers (B) and (C) are a (meth) acrylic resin layer or a polycarbonate resin layer. The thermoplastic resin layers (B) and (C) contain 50% by mass or more of a (meth) acrylic resin based on the total resin contained in each thermoplastic resin layer. Polarizing plate with resin laminate. The polarizing plate with a resin laminate according to claim 34, wherein the (meth) acrylic resin contained in the thermoplastic resin layers (B) and (C) has a weight average molecular weight of 50,000 to 300,000. The display apparatus containing the polarizing plate with a resin laminated body of Claim 35.

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