JPWO2016199828A1 - Compact - Google Patents

Abstract

The molded object which consists of a resin composition containing a vinylidene fluoride resin and a (meth) acrylic resin, and satisfy | fills all [I]-[III]. [I] The resin composition contains 15 to 60 parts by weight of (meth) acrylic resin and 40 to 85 parts by weight of vinylidene fluoride resin per 100 parts by weight of the total amount of (meth) acrylic resin and the vinylidene fluoride resin. [II] Molded product after exposing the molded product to an environment of 90% relative humidity at 60 ° C. for 120 hours with a small-angle X-ray scattering intensity at wave number Q = 0.012 nm−1 being I0. When the small-angle X-ray scattering intensity at wave number Q = 0.112 nm−1 is IA, I0 and IA satisfy IA / I0 <2.5. [III] The haze of the molded body measured according to JIS K7136 is 5% or less.

Description

  The present invention relates to a molded article formed from a resin composition containing a vinylidene fluoride resin and a (meth) acrylic resin.

  Films and sheets obtained by melt extrusion molding or melt injection molding of a composition comprising a vinylidene fluoride resin and a (meth) acrylic resin are touch sensors for display members because of their high transparency, molding processability, and relative dielectric constant. It is used for a window sheet of a panel (Patent Document 1).

JP2013-244604A

  However, when a film or sheet equivalent to that described in Patent Document 1 is exposed to an environment of 90% relative humidity at 60 ° C. for 120 hours, the transparency may be significantly impaired. As a result, these films or sheets may be damaged. When the display member using is used in a severe use environment of high temperature and high humidity, it may become cloudy.

  An object of the present invention is to provide a molded product that does not become cloudy even if exposed to an environment of 90% relative humidity at 60 ° C. for 120 hours while satisfying molding processability and relative dielectric constant, and a touch sensor panel including the molded product. That is.

（式中、Ｒ_１は水素原子またはメチル基を表し、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。）；
〔３〕フッ化ビニリデン樹脂が、ポリフッ化ビニリデンである〔１〕又は〔２〕記載の成形体；
〔４〕フッ化ビニリデン樹脂が、フッ化ビニリデンに由来する構造単位を５０重量％以上含むフッ化ビニリデン共重合体である〔１〕又は〔２〕記載の成形体；
〔５〕シート状又はフィルム状である〔１〕〜〔４〕のいずれかに記載の成形体；
〔６〕厚さが１００μｍ〜２０００μｍである〔５〕記載の成形体；
〔７〕〔５〕又は〔６〕記載の成形体と、コーティング層とを備える第１の積層体であって、前記コーティング層が、膜の少なくとも一方の面に配置され、少なくとも一種の機能を付与する層である第１の積層体；
〔８〕〔５〕又は〔６〕記載の成形体と熱可塑性樹脂層とを備える第２の積層体；
〔９〕〔８〕に記載の第２の積層体と、コーティング層とを備える第３の積層体であって、前記コーティング層が、膜の少なくとも一方の面に配置され、少なくとも一種の機能を付与する層である第３の積層体；
〔１０〕〔５〕又は〔６〕記載の成形体を含むタッチセンサーパネル；
〔１１〕〔７〕に記載の第１の積層体、〔８〕に記載の第２の積層体、または〔９〕に記載の第３の積層体を含むタッチセンサーパネル。
〔１２〕〔５〕又は〔６〕記載の成形体を含む表示装置。
〔１３〕〔７〕に記載の第１の積層体、〔８〕に記載の第２の積層体、または〔９〕に記載の第３の積層体を含む表示装置。That is, the present invention includes the inventions described in the following [1] to [9].
[1] A molded body formed from a resin composition containing a vinylidene fluoride resin and a (meth) acrylic resin, wherein the resin composition satisfies the following [I], and the molded body is the following [II And a molded body satisfying [III];
[I] The resin composition comprises 15 to 60 parts by weight of (meth) acrylic resin and 40 to 85 parts by weight of vinylidene fluoride resin per 100 parts by weight of the total amount of the (meth) acrylic resin and the vinylidene fluoride resin. Including.
[II] The small-angle X-ray scattering intensity at a wave number Q = 0.112 nm ⁻¹ of the molded body is I ₀ .
When the molded product 90% RH 120 hours of exposure to the environment at 60 ° C. The (expose) the molded body after the small-angle X-ray scattering intensity at a wave number Q = 0.012 nm ^-1 was _{I A,}
I ₀ and I _A satisfy the following expression (A).
I _A / I ₀ <2.5 (A)
[III] The haze of the molded body measured according to JIS K7136 is 5% or less.
[2] The molded product according to [1], wherein the (meth) acrylic resin is the following resin (a1) or (a2);
(A1) methyl methacrylate homopolymer,
(A2) 50 to 99.9% by weight of structural units derived from methyl methacrylate and 0.1 to 50% by weight of at least one structural unit derived from the (meth) acrylic acid ester represented by formula (1) Copolymer containing

(In the formula, 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);
[3] The molded article according to [1] or [2], wherein the vinylidene fluoride resin is polyvinylidene fluoride;
[4] The molded article according to [1] or [2], wherein the vinylidene fluoride resin is a vinylidene fluoride copolymer containing 50% by weight or more of a structural unit derived from vinylidene fluoride;
[5] The molded body according to any one of [1] to [4], which is in the form of a sheet or film;
[6] The molded product according to [5], having a thickness of 100 μm to 2000 μm;
[7] A first laminate comprising the molded body according to [5] or [6] and a coating layer, wherein the coating layer is disposed on at least one surface of the film and has at least one function. A first laminate which is a layer to be applied;
[8] A second laminate comprising the molded article according to [5] or [6] and a thermoplastic resin layer;
[9] A third laminate comprising the second laminate according to [8] and a coating layer, wherein the coating layer is disposed on at least one surface of the film and has at least one function. A third laminate which is a layer to be applied;
[10] A touch sensor panel including the molded article according to [5] or [6];
[11] A touch sensor panel including the first laminate according to [7], the second laminate according to [8], or the third laminate according to [9].
[12] A display device comprising the molded article according to [5] or [6].
[13] A display device including the first laminate according to [7], the second laminate according to [8], or the third laminate according to [9].

  The film or sheet formed from the molded article of the present invention is useful as a window sheet for a touch sensor panel because it satisfies high molding processability and relative dielectric constant and does not become cloudy even when used in a severe environment.

It is the schematic of the manufacturing apparatus of the sheet-like molded object of this invention used for the Example. It is a schematic diagram of the cross section of an example of the electrostatic capacitance type touch sensor panel to which the molded object or laminated body of this invention is applied. It is a schematic diagram of the cross section of an example of the liquid crystal display device to which the molded object or laminated body of this invention is applied.

  Hereinafter, the present invention will be described in detail.

<(Meth) acrylic resin>
Examples of the (meth) acrylic resin used in the present invention include a homopolymer of (meth) acrylic monomers such as (meth) acrylic acid ester and (meth) acrylonitrile, or two or more kinds of copolymers; Examples include copolymers of acrylic monomers and other monomers. In the present specification, the term “(meth) acryl” means “acryl” or “methacryl”.

  From the viewpoint of having excellent hardness, weather resistance, transparency and the like, it is preferable to use a methacrylic resin as the (meth) acrylic resin. A methacrylic resin is a polymer obtained by polymerizing a monomer mainly composed of a methacrylic acid ester (alkyl methacrylate). For example, a methacrylic acid ester homopolymer (polyalkyl methacrylate) and a methacrylic acid ester Examples thereof include a polymer, a copolymer of 50% by weight or more of a methacrylic acid ester, and a monomer other than 50% by weight or less of a methacrylic acid ester. In the case of a copolymer of a methacrylic acid ester and a monomer other than the methacrylic acid ester, the methacrylic acid ester is preferably 70% by weight or more with respect to the total monomer amount of 100% by weight, and the monomer other than the methacrylic acid ester Is 30% by weight or less, more preferably 90% by weight or more of methacrylic acid ester and 10% by weight or less of monomers other than methacrylic acid ester.

  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.

  Examples of monofunctional monomers include styrene monomers such as styrene, α-methylstyrene, and vinyl toluene; alkenyl cyanides such as acrylonitrile and methacrylonitrile; acrylic acid; methacrylic acid; maleic anhydride; , N-substituted maleimides such as cyclohexylmaleimide and methylmaleimide; From the viewpoint of heat resistance, a lactone ring structure, a glutaric anhydride structure, or a glutarimide structure is present in the molecular chain of the (meth) acrylic resin (also referred to as the main skeleton or main chain in the (meth) acrylic resin). It may be introduced.

（式中、Ｒ_１は水素原子またはメチル基を表し、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。）。More specifically, the (meth) acrylic resin is preferably the following resin (a1) or (a2). In the following (a2), the total amount of the structural unit derived from methyl methacrylate and at least one structural unit derived from the (meth) acrylic acid ester represented by the formula (1) is 100% by weight. It is preferable.
(A1) Homopolymer of methyl methacrylate (a2) 50 to 99.9% by weight of structural units derived from methyl methacrylate and at least one structure derived from (meth) acrylic acid ester represented by formula (1) Copolymer containing 0.1 to 50% by weight of unit

(In the formula, 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).

Here, when R ₁ is a hydrogen atom, the alkyl group having 1 to 8 carbon atoms represented by R ₂ is methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert- Examples thereof include a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like. Examples of the alkyl group having 2 to 8 carbon atoms represented by R ₂ when R ₁ is a methyl group include an ethyl group, a propyl group, Examples include isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like.

  The (meth) acrylic acid ester represented by the formula (1) is preferably methyl acrylate or ethyl acrylate, and more preferably methyl acrylate.

The (meth) acrylic resin preferably has a melt mass flow rate at 230 ° C. (hereinafter sometimes referred to as MFR) measured at a load of 3.8 kg in accordance with JIS K7210, usually 0.1 to 20 g / 10 min. Is 0.2 to 5 g / 10 min, more preferably 0.5 to 3 g / 10 min.
If the MFR of the (meth) acrylic resin is too large, the strength of the resulting molded product tends to decrease, and if the MFR of the (meth) acrylic resin is too small, the film formability of the molded product tends to decrease.

  The (meth) acrylic resin preferably has a weight average molecular weight (hereinafter sometimes referred to as Mw) obtained by GPC measurement of 70,000 to 300,000. The upper limit of the weight average molecular weight is more preferably 250,000, and even more preferably 200,000. The lower limit of the weight average molecular weight is more preferably 80,000, still more preferably 90,000, even more preferably 120,000, and even more preferably 150,000. The weight average molecular weight is more preferably 150,000 to 200,000, for example. The greater the Mw of the (meth) acrylic resin, the higher the transparency of the resulting molded body after exposure to an environment of 90% relative humidity at 60 ° C. The film property tends to be lowered.

  From the viewpoint of heat resistance, the (meth) acrylic resin preferably has a Vicat softening temperature (hereinafter sometimes referred to as VST) measured according to JIS K7206 of 90 ° C. or higher, more preferably 100 ° C. or higher. Preferably, it is 102 ° C. or higher. The VST of the (meth) acrylic resin can be appropriately set by adjusting the type and ratio of the monomer or the molecular weight of the (meth) acrylic resin.

  The (meth) acrylic resin can be prepared by polymerizing the monomer component by a method such as suspension polymerization or bulk polymerization. In that case, MFR, Mw, VST, etc. of (meth) acrylic resin can be adjusted to a preferable range by adding a suitable chain transfer agent. 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 calculated | required, etc.

<Vinylidene fluoride resin>
As the vinylidene fluoride resin used in the present invention, a comonomer group consisting of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether and ethylene is used from the viewpoint of the transparency of the resulting molded product. A vinylidene fluoride copolymer obtained by copolymerizing at least one monomer (comonomer) selected from the above and vinylidene fluoride, and a polymer obtained by polymerizing vinylidene fluoride alone (polyvinylidene fluoride). Polyvinylidene fluoride or a copolymer of vinylidene fluoride and hexafluoropropylene is preferable, and polyvinylidene fluoride is more preferable.
The structural unit derived from vinylidene fluoride contained in the vinylidene fluoride copolymer is preferably 50% by weight or more. The content of the structural unit derived from the comonomer is preferably 30% by weight or less, more preferably 25% by weight or less, from the viewpoint of the transparency of the obtained molded body.

  The vinylidene fluoride resin usually has a melt mass flow rate (MFR) at 230 ° C. measured at a load of 3.8 kg according to JIS K7210 of 0.1 to 40 g / 10 min. The upper limit of the MFR is preferably 35 g / 10 minutes, more preferably 30 g / 10 minutes, still more preferably 25 g / 10 minutes, and even more preferably 20 g / 10 minutes. The upper limit of the MFR is preferably 0.2 g / 10 minutes, and more preferably 0.5 g / 10 minutes. If the MFR of the vinylidene fluoride resin is too large, the resulting molded product tends to decrease in transparency when used for a long period of time. If the MFR of the vinylidene fluoride resin is too small, the film formability of the molded product decreases. Tend to.

The vinylidene fluoride resin preferably has a weight average molecular weight (Mw) determined by GPC of 100,000 to 500,000, more preferably 150,000 to 450,000, and 200,000 to 450, More preferably, it is 000.
As the Mw of the vinylidene fluoride resin increases, the resulting molded product tends to have higher transparency after being exposed to an environment of 90% relative humidity at 60 ° C. However, if the Mw is too large, the molded product is formed into a film. Tend to decrease.

  Polyvinylidene fluoride is industrially produced by a suspension polymerization method or an emulsion polymerization method. In the suspension polymerization method, water is used as a medium, the monomer is dispersed as a droplet in the medium with a dispersant, and an organic peroxide dissolved in the monomer is polymerized as a polymerization initiator to give 100 to 100- A 300 μm granular polymer is obtained. Suspension polymers are preferred because they have a simpler manufacturing process, better powder handling, and do not contain an emulsifier or salting-out agent containing an alkali metal unlike emulsion polymers.

<Resin composition>
The resin composition constituting the molded article of the present invention is 15 to 60 parts by weight of (meth) acrylic resin and 40 to 85% by weight of vinylidene fluoride resin per 100 parts by weight of the total amount of (meth) acrylic resin and vinylidene fluoride resin. Part. The resin composition preferably contains 17 to 60 parts by weight of (meth) acrylic resin and 40 to 83 parts by weight of vinylidene fluoride resin per 100 parts by weight of the total amount of (meth) acrylic resin and vinylidene fluoride resin, More preferably, it contains 20 to 55 parts by weight of (meth) acrylic resin and 45 to 80 parts by weight of vinylidene fluoride resin. The total content of the (meth) acrylic resin and the vinylidene fluoride resin in 100% by weight of the resin composition is preferably 90% by weight or more, and more preferably 95% by weight or more.

  The resin composition constituting the molded article of the present invention preferably has a total alkali metal content of 50 ppm or less.

  Furthermore, various commonly used additives may be added to the resin composition as long as the effects of the present invention are not impaired. Examples of additives include stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, colorants, foaming agents, lubricants, mold release agents, antistatic agents, flame retardants, polymerization inhibitors, flame retardant aids, Examples include coloring agents such as reinforcing agents, nucleating agents, and bluing agents.

  Examples of the colorant include a compound having an anthraquinone skeleton and a compound having a phthalocyanine skeleton. Among these, a compound having an anthraquinone skeleton is preferable from the viewpoint of heat resistance.

  When using a bluing agent as a coloring agent, the content is 0.01-5 ppm, Preferably it is 0.05-4 ppm, More preferably, it is 0.1-3 ppm. A known bluing agent can be appropriately used. For example, under each trade name, Macrolex (registered trademark) Blue RR (manufactured by Bayer), Macrolex (registered trademark) Blue 3R (manufactured by Bayer), Sumiplast (registered trademark) Violet B (manufactured by Sumika Chemtex) And Polysynthrene (registered trademark) Blue RLS (manufactured by Clariant).

  These additives only need to be present in the resin composition, and may be contained in any component of the (meth) acrylic resin or the vinylidene fluoride resin. The (meth) acrylic resin and the vinylidene fluoride resin described later are used. Or may be added after melt kneading of (meth) acrylic resin and vinylidene fluoride resin, or added when producing a molded body using a resin composition. Also good.

  The resin composition constituting the molded article of the present invention is usually obtained by kneading a (meth) acrylic resin and a vinylidene fluoride resin. Such 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.

  If the temperature during melt kneading is less than 150 ° C., the resin may not melt. On the other hand, when the temperature at the time of melt kneading exceeds 350 ° C., the resin may be thermally decomposed. Furthermore, when the shear rate at the time of melt kneading is less than 10 / second, the kneading may not be sufficiently performed. On the other hand, if the shear rate during melt-kneading exceeds 1000 / second, the resin may be decomposed.

  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, a multi-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.

<Molded body>
The molded product of the present invention is formed from the above resin composition.
The small-angle X-ray scattering intensity of the molded body at a wave number Q = 0.012 nm ⁻¹ is I ₀ ,
When molded product at 60 ° C. The relative humidity of 90% after exposure for 120 hours under the environment of the molded body, the small-angle X-ray scattering intensity at a wave number Q = 0.012 nm ^-1 was I _A,
I ₀ and I _A satisfy the following expression (A).
I _A / I ₀ <2.5 (A)
Preferably, I _A / I ₀ is 0.1 to 2.3, more preferably 0.1 to 2.1. The I _{A /} I ₀ of the compact to the above-mentioned range, by adjusting the cooling rate of the vinylidene fluoride content or in molding the resin composition can be adjusted.
The haze of the molded body measured according to JIS K7136 is 5% or less. The haze value is a value obtained by measurement performed before the molded body is exposed to a high temperature and high humidity environment.
Such a molded body is preferably in the form of a sheet or film, and preferably has a thickness of 100 to 2000 μm, more preferably 200 to 1500 μm.

<Laminate>
One embodiment of the laminate of the present invention comprises the above-mentioned sheet-like or film-like molded article and a thermoplastic resin layer (second laminate). Such a laminate is excellent in heat resistance and surface hardness. The thermoplastic resin layer only needs to be laminated on at least one surface of the sheet-like or film-like molded article of the present invention, and does not necessarily need to be in contact with the molded article, and is laminated via another layer. May be. It is preferable that the thermoplastic resin layer is laminated in contact with the molded body. From the viewpoint of maintaining the shape of the molded body, the laminate preferably includes a thermoplastic resin layer on both sides of the molded body. The laminate may further include a coating layer described later (third laminate).

  The thickness of the thermoplastic resin layer is preferably 10 to 200 μm, and more preferably 50 to 150 μm. When the laminate includes a thermoplastic resin layer on both surfaces of a sheet-like or film-like molded body, the thickness and composition of each thermoplastic resin layer may be the same or different from each other, but the shape of the molded body From the viewpoint of maintenance, it is preferable that they are substantially the same.

  The pencil hardness measured according to JIS K5600-5-4 of the thermoplastic resin layer is preferably HB or more, more preferably F or more, and even more preferably H or more. The Vicat softening temperature of the thermoplastic resin layer measured according to JIS K7206 is preferably 100 to 150 ° C.

  The thermoplastic resin layer can be selected from one or more types of (meth) acrylic resins or one or more types of thermoplastic resins other than (meth) acrylic resins. From these resins, one or more types of thermoplastic resins can be used alone or in combination. Further, the thermoplastic resin layer can have a single layer configuration or a configuration in which a plurality of layers are laminated.

  As the (meth) acrylic resin of the thermoplastic resin layer, a resin having the same primary structure as that of the (meth) acrylic resin contained in the molded article of the present invention can be used. For example, a homopolymer of methyl methacrylate, a copolymer comprising 50 to 99.9% by weight of structural units derived from methyl methacrylate and 0.1 to 50% by weight of structural units derived from methyl acrylate, a lactone ring structure Methacrylic acid resin, a copolymer consisting of a structural unit derived from methyl methacrylate and a structural unit derived from methacrylic acid, or a structural unit derived from styrene, a structural unit derived from maleic anhydride, and methacrylic acid A terpolymer composed of a structural unit derived from methyl can be used. The weight average molecular weight (Mw) of the (meth) acrylic resin is preferably 50,000 to 300,000, and more preferably 70,000 to 250,000. In a molded article including a thermoplastic resin layer, the (meth) acrylic resin contained in the thermoplastic resin layer may be the same as or different from the (meth) acrylic resin contained in the resin composition forming the molded article. Good.

  As thermoplastic resins other than (meth) acrylic resins, carbonate resins, cycloolefin resins, ethylene terephthalate resins, styrene resins, methyl methacrylate-styrene resins, acrylonitrile-styrene resins, ABS resins, etc. should be used. Can do. The thermoplastic resin other than the (meth) acrylic resin preferably has a Vicat softening temperature measured according to JIS K7206 of 115 ° C or higher, more preferably 117 ° C or higher, and 120 ° C or higher, from the viewpoint of heat resistance. More preferably it is.

An example of the carbonate resin is a polycarbonate resin. When the thermoplastic resin layer is a polycarbonate resin layer, the polycarbonate resin layer is formed from one or more types of polycarbonate resins or a composite resin of one or more types of polycarbonate resins and one or more types of thermoplastic resins. Can do. These polycarbonate resins preferably have a melt volume rate (hereinafter also referred to as MVR) measured at a temperature of 300 ° C. and a load of 1.2 kg for ³ to 120 cm 3/10 minutes. MVR is more preferably in the 3~80cm ^3/10 min, more preferably 4~40cm ^3/10 min, deliberately preferably 10 to 40 cm ^3/10 min. If MVR is less than 3 cm ^3/10 min, because the flowability is decreased, and tends to be difficult by molding such as melt co-extrusion, there is the appearance failure occurs. Further, the MVR exceeds 120 cm ^3/10 min, mechanical properties such as strength of the polycarbonate resin layer tends to decrease. MVR can be measured under the condition of 300 ° C. under a load of 1.2 kg in accordance with JIS K 7210.

  The polycarbonate resin is a polymer obtained by, for example, 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. As such, polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A) can be used.

  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.

  When the polycarbonate resin layer is formed from a composite resin of one or more types of polycarbonate resin and one or more types of thermoplastic resin, the thermoplastic resin other than the polycarbonate resin is blended within a range that does not impair the transparency. can do. As this thermoplastic resin, for example, a (meth) acrylic resin compatible with a polycarbonate resin is preferable, and a methacrylic resin having an aromatic ring or a cycloolefin in its structure is more preferable. When the polycarbonate resin contains such a tacryl resin, the surface hardness of the obtained polycarbonate resin layer can be made higher than when the polycarbonate resin is formed from the polycarbonate resin alone.

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

  The polycarbonate resin includes a release agent, an ultraviolet absorber, a dye, a pigment, a polymerization inhibitor, an antioxidant, a flame retardant, a reinforcing agent and other additives, a polymer other than the polycarbonate resin, and the like. You may make it contain in the range which does not impair an effect.

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

When two or more types of (meth) acrylic resins are used in the thermoplastic resin layer, or when the (meth) acrylic resin is used in combination with another thermoplastic resin, 100 parts by weight of the thermoplastic resin layer It is preferable to contain 50 parts by weight or more of the hit (meth) acrylic resin. As the thermoplastic resin other than the (meth) acrylic resin, a thermoplastic resin compatible with the (meth) acrylic resin is preferable. Heat compatible with a homopolymer of methyl methacrylate or a copolymer comprising 50 to 99.9% by weight of structural units derived from methyl methacrylate and 0.1 to 50% by weight of structural units derived from methyl acrylate Examples of the plastic resin include Resisti (registered trademark) R-100 and R-200 manufactured by Electrochemical Industry, Altuglas (registered trademark) HT-121 manufactured by Arkema Corporation, and the like.
It is preferable that the thermoplastic resin layer does not substantially contain a vinylidene fluoride resin.

  The molded body of the present invention is transparent when visually observed, and the total light transmittance (Tt) measured according to JIS K7361-1 is preferably 88% or more, more preferably 90% or more, and 60 This range is maintained even after 120 hours exposure at 90 ° C. and 90% relative humidity.

  The molded article of the present invention has a haze measured in accordance with JIS K7136 after exposure for 120 hours in an environment of 90% relative humidity at 60 ° C., usually 6% or less, preferably 4% or less, more preferably 3.5%. It is as follows.

  Furthermore, the molded product of the present invention has a relative dielectric constant of 3 or more, preferably 4.0 or more, at 3 V and 100 kHz, measured by an automatic equilibrium bridge method.

  The molded body of the present invention can be produced by melt molding the resin composition by, for example, a melt extrusion molding method, a hot press method, an injection molding method, or the like.

  A laminate may be produced by bonding a molded body obtained by molding the resin composition by the above molding and a thermoplastic resin layer separately molded via, for example, an adhesive or an adhesive. It is preferable to produce a laminate by laminating and integrating a resin composition and a (meth) acrylic resin by melt coextrusion molding. Thus, the laminated body manufactured by melt coextrusion molding tends to be easily subjected to secondary molding as compared with the laminated body manufactured by bonding.

  In melt coextrusion molding, for example, the above resin composition and (meth) acrylic resin are separately fed into two or three uniaxial or biaxial extruders and melt-kneaded, respectively, and then fed block die Or a multi-manifold die or the like, and the molded body of the present invention and a thermoplastic resin layer are laminated and integrated and extruded. The obtained laminate is preferably cooled and solidified by, for example, a roll unit.

  Another embodiment of the laminate of the present invention is a group consisting of the above-mentioned sheet-like or film-like molded article and scratch prevention, antireflection, antiglare and fingerprint prevention arranged on at least one surface of the molded article. And a coating layer imparting at least one function selected from (a first laminate). The coating layer should just be laminated | stacked on the at least one surface of a sheet-like or film-like molded object, and does not necessarily need to contact the molded object, and may be laminated | stacked through another layer. As the coating layer, for example, a cured film described in JP 2013-86273 A can be used.

  1-100 micrometers is preferable, as for the thickness of a coating layer, 3-80 micrometers is more preferable, and 5-70 micrometers is further more preferable. If it is thinner than 1 μm, it is difficult to express the function, and if it is thicker than 100 μm, the coating layer may be cracked.

  If necessary, the surface of the coating layer may be subjected to antireflection treatment by a coating method, a sputtering method, a vacuum deposition method, or the like. Further, for the purpose of imparting an antireflection effect, a separately prepared antireflection sheet may be bonded to one side or both sides of the coating layer. The antireflective sheet only needs to be laminated on at least one surface of the coating layer, and is not necessarily in contact with the coating layer, and may be laminated via another layer.

When the molded body is abbreviated as A layer, the thermoplastic resin layer is abbreviated as B layer, and the coating layer is abbreviated as C layer, examples of the layer structure of the molded body and laminate of the present invention include the following (1) to (12). .
(1) A layer (2) A layer / B layer (3) B layer / A layer / B layer (4) B layer / A layer / B layer / A layer / B layer (5) A layer / C layer ( 6) C layer / A layer / C layer (7) A layer / B layer / C layer (8) C layer / A layer / B layer / C layer (9) B layer / A layer / B layer / C layer ( 10) C layer / B layer / A layer / B layer / C layer (11) B layer / A layer / B layer / A layer / B layer / C layer (12) C layer / B layer / A layer / B layer / A layer / B layer / C layer

<Transparent conductive sheet>
A transparent conductive sheet can be obtained by forming a transparent conductive film on at least one surface of the molded article or laminate of the present invention.

  As a method of forming a transparent conductive film on the surface of the molded body or laminate of the present invention, a method of directly forming a transparent conductive film on the surface of the molded body or laminate of the present invention may be used. A method of forming a transparent conductive film by laminating the formed plastic film on the surface of the molded product or laminate of the present invention may be used.

  The film base of the plastic film on which the transparent conductive film is formed in advance may be a transparent film that can form a transparent conductive film. For example, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, Acrylic resin, polyamide, a mixture or laminate thereof can be exemplified. Also, before forming the transparent conductive film, it is effective to coat the film for the purpose of improving the surface hardness, preventing Newton's ring, and imparting antistatic properties.

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

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

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

  Also, as a method of forming a transparent conductive film, it is formed by applying a coating agent containing various conductive polymers that can form a transparent conductive film and curing it by irradiating with ionizing radiation such as heat or ultraviolet rays. The method of doing etc. is applicable. As the conductive polymer, polythiophene, polyaniline, polypyrrole, and the like are known, and these conductive polymers can be used.

  Although it does not specifically limit as thickness of a transparent conductive film, When using a transparent conductive metal oxide, it is 50-2000cm normally, Preferably it is 70-1000cm. 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.

<Touch sensor panel>
The molded product or laminate of the present invention and the transparent conductive sheet containing the molded product or laminate can be suitably used as transparent electrodes for display panel face plates, touch screens and the like. Specifically, the molded body or laminate of the present invention can be used as a touch screen window sheet. Moreover, the transparent conductive sheet containing the molded body or laminate of the present invention can be used as an electrode substrate of a resistive film type or capacitive type touch screen. A touch sensor panel having a touch screen function can be obtained by arranging a window sheet for a touch screen or a touch screen on the front surface of a liquid crystal display, an organic EL display, or the like.

  When the molded body or laminate of the present invention is used as a touch screen window sheet, the touch screen window sheet can be used as a substitute for a glass sheet disposed on the outermost surface of a liquid crystal display or an organic EL display. . The touch screen window sheet can also be used for a plasma display, a field emission display (FED), a SED flat display, electronic paper, and the like.

  FIG. 2 shows a schematic view of a cross section of a general capacitive touch sensor panel including the molded product or laminate of the present invention and the molded product or laminate. In the figure, 11 is a window sheet made of the molded body or laminate of the present invention, 14 is a transparent conductive sheet containing the molded body or laminate of the present invention, 12 is an optical adhesive layer, and 13 is a liquid crystal display device. . When the user makes a finger contact with an arbitrary position on the window sheet during driving, the distance from the terminal position to the contact position is detected via the transparent conductive sheet, and the contact position is detected. As a result, the coordinates of the contact portion on the panel are recognized, and an appropriate interface function is achieved.

  In FIG. 3, an example of the liquid crystal display device to which the molded object or laminated body of this invention is applied is shown with a cross-sectional schematic diagram. The molded body or laminate 20 of the present invention can be laminated on the polarizing plate 21 via an optical adhesive, and this laminate can be disposed on the viewing side of the liquid crystal cell 23. A polarizing plate is usually disposed on the back side of the liquid crystal cell. The liquid crystal display device 25 is composed of such members. FIG. 3 is an example of a liquid crystal display device and 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.

In the examples, MFR, Vicat softening temperature, and weight average molecular weight of the meth) acrylic resin were measured by the following methods.
The melt mass flow rate (MFR) was measured in accordance with the method specified in JIS K 7210: 1999 “Testing methods for melt mass flow rate (MFR) and melt volume flow rate (MVR) of plastic-thermoplastic plastic”. 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).
The Vicat softening point (VST) conforms to the B50 method defined in JIS K 7206: 1999 “Plastics-Thermoplastic Plastics-Vicat Softening Temperature (VST) Test Method”. "148-6 continuous type"]. The test piece at that time was measured by press-molding each raw material to a thickness of 3 mm.
The weight average molecular weight (Mw) of the (meth) acrylic resin was measured by gel permeation chromatography (GPC). To create a GPC calibration curve, use a methacrylic resin made by Showa Denko KK with a narrow molecular weight distribution and known molecular weight as a standard reagent, create a calibration curve from the elution time and molecular weight, and calculate the weight of each resin composition. Average molecular weight was measured. Specifically, 40 mg of resin was dissolved in 20 ml of tetrahydrofuran (THF) solvent to prepare a measurement sample. As the measuring device, two columns “TSKgel SuperHM-H” made by Tosoh Corporation and one “SuperH2500” were installed in series, and a detector employing an RI detector was used. . The measured molecular weight distribution curve was fitted using the normal distribution function by taking the logarithm of the molecular weight on the horizontal axis and fitting using the normal distribution function of the following equation.

(Production Example 1)
From the monomer composition of 97.5% by weight of methyl methacrylate and 2.5% by weight of methyl acrylate, pellet-shaped methacrylic resin (i) was obtained by bulk polymerization. The methacrylic resin (i) had a melt mass flow rate (MFR) of 0.8 g / cm ³ , a weight average molecular weight (Mw) of 180,000, and a Vicat softening temperature (VST) of 108 ° C.

  The vinylidene fluoride resins used in the examples are shown in Table 1.

Examples 1-8, Comparative Examples 1-5
After the methacrylic resin (i) and the vinylidene fluoride resin are uniformly mixed in the proportions shown in Table 2, the resin is kneaded at 260 ° C. using a single screw extruder (Laboplast Mill, manufactured by Toyo Seiki Co., Ltd.). A composition was obtained. This resin composition was press-molded at 260 ° C. and then cooled by being immersed in ice water to obtain a sheet-like molded body having a thickness of 500 μm.

Examples 9-11, Comparative Examples 6-7
The methacrylic resin (i) and the vinylidene fluoride resin are uniformly mixed in the proportions shown in Table 3, and then kneaded at 260 ° C. using a single screw extruder (Laboplast Mill, manufactured by Toyo Seiki Co., Ltd.) and blended. Pellets were obtained. This pellet was press-molded at 260 ° C. and then held in a cold press at 10 ° C. for 30 seconds to obtain a sheet-like molded body having a thickness of 500 μm.

<High temperature and high humidity exposure test>
The molded bodies obtained in Examples 1 to 11 and Comparative Examples 1 to 7 were left in a constant temperature and humidity oven at 60 ° C. and a relative humidity of 90% for 120 hours to perform a high temperature and high humidity exposure test.

<Haze>
Haze was measured according to JIS K7136: 2000 for the molded bodies obtained in Examples 1 to 11 and Comparative Examples 1 to 7 and the molded bodies after the high temperature and high humidity exposure tests. The results are shown in Table 4.

<Small angle X-ray scattering measurement>
Small angle X-ray scattering (USAXS) in the ultra small angle region was measured using BL19B2 (industrial beamline I) installed in the large synchrotron radiation facility Spring-8 (Hyogo Prefecture). The X-ray energy was 18 keV, the distance from the sample to the detector was 42 m, and the detector used was a two-dimensional detector PILATUS2M. The sample size was 50 mm × 50 mm, and the measurement temperature was room temperature (25 ° C.).
Small-angle X-ray scattering intensity I _{0 at} the wave number Q = 0.012 nm ⁻¹ of the molded bodies obtained in Examples 1 to 11 and Comparative Examples 1 to 7, respectively, and the wave number after the high temperature and high humidity exposure test of the molded bodies. The ratio of small angle X-ray scattering intensity I _A at Q = 0.012 nm ⁻¹ , I _A / I ₀ was calculated. The results are shown in Table 4.

<Relative permittivity measurement>
For the molded bodies obtained in Examples 1 to 11 and Comparative Examples 1 to 7, the relative dielectric constants at 3 V and 100 kHz were measured by the automatic equilibrium bridge method according to JIS K6911. The results are shown in Table 4.

Examples 12, 14, 16-19
When the molded body of the present invention is an A layer and the thermoplastic resin layer is a B layer, a laminate having a configuration in which the stacking order is B layer / A layer / B layer can be produced as follows. A description will be given with reference to FIG.
First, a methacrylic resin (i) and a vinylidene fluoride resin are mixed as a forming material of the A layer in a combination and a ratio shown in Table 5 to obtain a resin composition. Next, the resin composition is melted by a 65 mmφ single screw extruder 2 (manufactured by Hitachi Zosen), and 100 parts by weight of methacrylic resin (i) as a material for forming the B layer is melted by 45 mmφ single screw extruders 1 and 3, respectively. Subsequently, these are laminated so as to have a structure represented by the above-mentioned B layer / A layer / B layer through a feed block 4 (manufactured by Hitachi Zosen) at a set temperature of 250 to 270 ° C. The film-like molten resin 6 can be obtained by extruding from a die 5 (manufactured by Hitachi Zosen Co., Ltd., 2-type, 3-layer distribution). The obtained film-like molten resin 6 is sandwiched between a first cooling roll 7 and a second cooling roll 8 that are arranged opposite to each other, and then in close contact with the second cooling roll 8, the second cooling roll 8 and the third cooling roll. Then, the laminated body 10 having a three-layer structure can be obtained by being closely contacted with the third cooling roll 9 and then molded and cooled.

Examples 13 and 15
When the molded body of the present invention was an A layer and the thermoplastic resin layer was a B layer, a laminate having a configuration in which the stacking order was B layer / A layer / B layer was produced as follows. A description will be given with reference to FIG.
As a material for forming the A layer, a methacrylic resin (i) and a vinylidene fluoride resin were mixed in the combinations and proportions shown in Table 5 to obtain a resin composition. Next, the resin composition was melted by a 65 mmφ single screw extruder 2 (manufactured by Hitachi Zosen), and 100 parts by weight of methacrylic resin (i) as a material for forming the B layer was melted by 45 mmφ single screw extruders 1 and 3, respectively. . Subsequently, these are laminated so as to have a structure represented by the above-mentioned B layer / A layer / B layer through a feed block 4 (manufactured by Hitachi Zosen) at a set temperature of 250 to 270 ° C. Extrusion was performed from a die 5 (manufactured by Hitachi Zosen Co., Ltd., 2-type, 3-layer distribution) to obtain a film-like molten resin 6. The obtained film-like molten resin 6 is sandwiched between a first cooling roll 7 and a second cooling roll 8 that are arranged opposite to each other, and then in close contact with the second cooling roll 8, the second cooling roll 8 and the third cooling roll. After being sandwiched between the two, the product was brought into close contact with the third cooling roll 9 and molded and cooled to obtain a laminate having a three-layer structure.

In Examples 13 and 15, the molded body layer (A layer) of the present invention is 300 μm, the thermoplastic resin layer (B layer) is 100 μm, and these layers are B layer / A layer / B layer. The laminated body laminated | stacked in order was obtained. The obtained laminate was allowed to stand in a constant temperature and high humidity oven having a relative humidity of 90% at 60 ° C. for 120 hours, and the haze of the laminate after the high temperature and high humidity exposure test was measured in the same manner as in Example 1. The results are shown in Table 6.

Examples 20 and 21
A laminate was produced in the same manner as in Example 13 except that the thermoplastic resin layer was formed from a polycarbonate resin (Caliver (registered trademark) 301-30). The haze before and after the high-temperature and high-humidity exposure test was measured for the obtained laminate in the same manner as in Example 1. The results are shown in Table 6.

Example 22
Using the molded bodies obtained in Examples 1 to 11 or the laminates obtained in Examples 13, 15, 20 and 21 as display window sheets, the molded bodies obtained in Examples 1 to 11 were used as transparent conductive sheets. A touch sensor panel can be produced by using each as a base material.

Example 21
A display apparatus can be produced by using the molded bodies obtained in Examples 1 to 11 or the laminates obtained in Examples 13, 15, 20, and 21 as display window sheets.

  The molded body and laminate of the present invention can maintain transparency without being clouded even when exposed to an environment of 90% relative humidity at 60 ° C. for 120 hours while satisfying molding processability and relative dielectric constant. It is useful as a touch sensor panel used for a smart phone, a portable game machine, an audio player, a tablet terminal or the like, or a window sheet of a display device.

1 Single screw extruder (extrudes a melt of (meth) acrylic resin)
2 Single screw extruder (extrudes the melt of the resin composition of the present invention)
3 Single screw extruder (extrudes a melt of (meth) acrylic resin)
4 Feed block 5 Multi-manifold die 6 Film-like molten resin 7 First cooling roll 8 Second cooling roll 9 Third cooling roll 10 Melt molded body 11 Transparent conductive sheet 12 Optical adhesive layer 13 Liquid crystal display device 20 Molded body or laminate Body 21 Polarizing plate 22 Optical adhesive layer 23 Liquid crystal cell 25 Liquid crystal display device

The vinylidene fluoride resin usually has a melt mass flow rate (MFR) at 230 ° C. of 0.1 to 40 g / 10 min measured at a load of 3.8 kg in accordance with JISK7210. The upper limit of the MFR is preferably 35 g / 10 minutes, more preferably 30 g / 10 minutes, still more preferably 25 g / 10 minutes, and even more preferably 20 g / 10 minutes. Lower limit of the MFR is preferably 0.2 g / 10 min, more preferably 0.5 g / 10 min. If the MFR of the vinylidene fluoride resin is too large, transparency tends to decrease when the resulting molded product is used for a long period of time. If the MFR of the vinylidene fluoride resin is too small, the film formability of the molded product decreases. Tend to.

Polyvinylidene fluoride is industrially produced by suspension polymerization or emulsion polymerization. In the suspension polymerization method, water is used as a medium, the monomer is dispersed as a droplet in the medium with a dispersant, and an organic peroxide dissolved in the monomer is polymerized as a polymerization initiator to give 100 to 100- A 300 μm granular polymer is obtained. Suspension polymers are preferred because they have a simpler manufacturing process, better powder handling, and do not contain an emulsifier or salting-out agent containing an alkali metal unlike emulsion polymers.

Furthermore, it may be mixed using a trivalent or higher phenol compounds as shown below with the above dihydroxy di aryl compound. 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.

When the polycarbonate resin layer is formed from a composite resin of one or more types of polycarbonate resin and one or more types of thermoplastic resin, the thermoplastic resin other than the polycarbonate resin is blended within a range that does not impair the transparency. can do. As this thermoplastic resin, for example, a (meth) acrylic resin compatible with a polycarbonate resin is preferable, and a methacrylic resin having an aromatic ring or a cycloolefin in its structure is more preferable. When polycarbonate resin comprises such main methacrylic resin, the surface hardness of the obtained polycarbonate resin layer, can be higher than when it is formed from a polycarbonate resin alone.

In Examples, MFR, Vicat softening temperature, and ( meth) acrylic resin weight average molecular weight were measured by the following methods.
The melt mass flow rate (MFR) was measured in accordance with the method specified in JIS K 7210: 1999 “Testing methods for melt mass flow rate (MFR) and melt volume flow rate (MVR) of plastic-thermoplastic plastic”. 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).
The Vicat softening point (VST) conforms to the B50 method defined in JIS K 7206: 1999 “Plastics-Thermoplastic Plastics-Vicat Softening Temperature (VST) Test Method”. "148-6 continuous type"]. The test piece at that time was measured by press-molding each raw material to a thickness of 3 mm.
The weight average molecular weight (Mw) of the (meth) acrylic resin was measured by gel permeation chromatography (GPC). To create a GPC calibration curve, use a methacrylic resin made by Showa Denko KK with a narrow molecular weight distribution and known molecular weight as a standard reagent, create a calibration curve from the elution time and molecular weight, and calculate the weight of each resin composition. Average molecular weight was measured. Specifically, 40 mg of resin was dissolved in 20 ml of tetrahydrofuran (THF) solvent to prepare a measurement sample. As the measuring device, two columns “TSKgel SuperHM-H” made by Tosoh Corporation and one “SuperH2500” were installed in series, and a detector employing an RI detector was used. . The measured molecular weight distribution curve was fitted using the normal distribution function by taking the logarithm of the molecular weight on the horizontal axis and fitting using the normal distribution function of the following equation.

Examples 20 and 21
A laminate was produced in the same manner as in Example 13 except that the thermoplastic resin layer was formed from a polycarbonate resin (Caliver (registered trademark) 301-30). The haze before and after the high-temperature and high-humidity exposure test was measured for the obtained laminate in the same manner as in Example 1. The results are shown in Table 7 .

Example 23
A display apparatus can be produced by using the molded bodies obtained in Examples 1 to 11 or the laminates obtained in Examples 13, 15, 20, and 21 as display window sheets.

Claims (13)

A molded body formed from a resin composition comprising a vinylidene fluoride resin and a (meth) acrylic resin, wherein the resin composition satisfies the following [I], and the molded body is the following [II] and [ III].
[I] The resin composition comprises 15 to 60 parts by weight of (meth) acrylic resin and 40 to 85 parts by weight of vinylidene fluoride resin per 100 parts by weight of the total amount of the (meth) acrylic resin and the vinylidene fluoride resin. Including.
[II] The small-angle X-ray scattering intensity at a wave number Q = 0.112 nm ⁻¹ of the molded body is I ₀ .
When the small-angle X-ray scattering intensity at wave number Q = 0.112 nm ⁻¹ of the molded body after exposure for 120 hours at 60 ° C. in an environment of 90% relative humidity is I _A , I ₀ and I _A satisfies the following formula (A).
I _A / I ₀ <2.5 (A)
[III] The haze of the molded body measured according to JIS K7136 is 5% or less. The molded product according to claim 1, wherein the (meth) acrylic resin is the following resin (a1) or (a2).
(A1) Homopolymer of methyl methacrylate (a2) 50 to 99.9% by weight of structural units derived from methyl methacrylate and at least one structure derived from (meth) acrylic acid ester represented by formula (1) Copolymer containing 0.1 to 50% by weight of unit

(In the formula, 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. 8 represents an alkyl group.)   The molded article according to claim 1 or 2, wherein the vinylidene fluoride resin is polyvinylidene fluoride.   The molded article according to claim 1 or 2, wherein the vinylidene fluoride resin is a vinylidene fluoride copolymer containing 50% by weight or more of a structural unit derived from vinylidene fluoride.   It is a sheet form or a film form, The molded object as described in any one of Claims 1-4.   The molded body according to claim 5, wherein the thickness is 100 μm to 2000 μm. A first laminate comprising the molded body according to claim 5 or 6, and a coating layer,
The first laminate is a layer in which the coating layer is disposed on at least one surface of the film and imparts at least one function.   A 2nd laminated body provided with the molded object of Claim 5 or 6, and a thermoplastic resin layer. A third laminate comprising the second laminate according to claim 8 and a coating layer,
A third laminate in which the coating layer is a layer that is disposed on at least one surface of the film and imparts at least one function.   A touch sensor panel comprising the molded body according to claim 5.   A touch sensor panel including the first laminate according to claim 7, the second laminate according to claim 8, or the third laminate according to claim 9.   The display apparatus containing the molded object of Claim 5 or 6.   A display device comprising the first laminate according to claim 7, the second laminate according to claim 8, or the third laminate according to claim 9.

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