KR102008476B1 - Resin laminated body provided with protective film - Google Patents

Abstract

In the manufacturing and distribution process, which is preferably used in a display device, a poor appearance such as digging hardly occurs, and a resin laminate which is preferably used in a display device or the like is provided. Protective film (D) and (E) which have a film base material at least on both surfaces of the resin laminated body which has an intermediate | middle layer (A) and the thermoplastic resin layer (B) and (C) which exist in both sides of the said intermediate | middle layer (A), respectively. As a resin laminated body provided with the protective film which respectively bonded together, the said intermediate | middle layer (A) is 10-90 mass% of (meth) acrylic resin and 90 based on all resin contained in the said intermediate | middle layer (A). The resin laminated body provided with the protective film containing ~ 10 mass% vinylidene fluoride resin, and the weight average molecular weight (Mw) of the said (meth) acrylic resin is 100,000-300,000.

Description

Resin laminated body provided with protective film

This invention relates to the resin laminated body provided with the protective film used preferably in a display apparatus, for example.

In recent years, display devices, such as a smart phone, a portable game machine, an audio player, a tablet terminal, etc., have increased with the touch screen. Although the glass sheet is normally used for the surface of such a display apparatus, development of the plastic sheet used as a substitute of a glass sheet is performed from the viewpoint of the weight reduction of a display apparatus, and workability. For example, Patent Document 1 discloses a transparent sheet containing a methacryl resin and vinylidene fluoride resin as a plastic sheet that is a substitute for a glass sheet, and the transparent sheet sufficiently satisfies the transparency and the dielectric constant. It is described.

Japanese Patent Application Laid-Open No. 2013-244604

The present invention relates to a plastic sheet. When the dielectric material is added for the purpose of imparting sufficient dielectric constant for use in a display device or the like, the sheet itself may be softened. In the manufacturing and distribution process of such a sheet, for example, foreign matter such as fine dust existing in the air adheres to the sheet, whereby small dents occur on the surface of the plastic sheet. When the plastic sheet with such recesses is used for the display device, there is a fear that the visibility in the display device is disturbed. For this reason, an object of this invention is to provide the resin laminated body which can avoid appearance defects, such as a recess, used preferably in a display apparatus etc.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the present inventors studied in detail about the resin laminated body used preferably in a display apparatus, and came to complete this invention.

That is, this invention includes the following preferable aspects.

[1] A protective film (D) having at least a film base material on both surfaces of the resin laminate having at least the thermoplastic resin layers (B) and (C), which are present on both sides of the intermediate layer (A) and the intermediate layer (A), respectively. And (E) bonded together, a resin laminate comprising a protective film,

The said intermediate | middle layer (A) contains 10-90 mass% (meth) acrylic resin and 90-10 mass% vinylidene fluoride resin based on all resin contained in the said intermediate | middle layer (A), The said (meth The resin laminated body provided with the protective film whose weight average molecular weight (Mw) of an acrylic resin is 100,000-300,000.

[2] A resin laminate comprising a protective film according to the above [1], wherein the protective films (D) and (E) each have an adhesive layer and are bonded to both surfaces of the resin laminate via the adhesive layer. .

[3] A resin laminate comprising the protective film according to the above [1] or [2], in which the protective films (D) and (E) each satisfy the following relationship.

E × L ³ ≥0.13

[In formula, E represents the tensile elasticity modulus (MPa) of a protective film, L represents the average value (mm) of the film thickness of the film base material of a protective film.]

[4] The film base material of the protective films (D) and (E) is at least one member selected from the group consisting of a low density polyethylene film, a high density polyethylene film, a polypropylene film, a polyethylene terephthalate film, an acrylic resin film, and a polycarbonate film. The resin laminated body provided with the protective film in any one of said [1]-[3] which is a film of said.

[5] The resin laminate comprising the protective film according to any one of the above [1] to [4], wherein the film substrates of the protective films (D) and (E) are high density polyethylene films or polyethylene terephthalate films.

[6] The resin laminate comprising the protective film according to any one of the above [1] to [5], wherein the film substrates of the protective films (D) and (E) have an average value of a film thickness of 40 µm or more.

[7] The intermediate layer (A) includes 35 to 45 mass% of (meth) acrylic resin and 65 to 55 mass% of vinylidene fluoride resin based on the total resin contained in the intermediate layer (A). The resin laminated body provided with the protective film in any one of [1]-[6].

[8] Resin provided with the protective film in any one of said [1]-[7] whose content of the alkali metal in an intermediate | middle layer (A) is 50 ppm or less based on all resin contained in the said intermediate | middle layer (A). Laminate.

[9] (meth) acrylic resin,

(a1) homopolymers of methyl methacrylate, and / or

(a2) It originates in the structural unit derived from 50-99.9 mass% methyl methacrylate based on all the structural units which comprise a polymer, and (meth) acrylic acid ester represented by 0.1-50 mass% of formula (1). The resin laminated body provided with the protective film in any one of said [1]-[8] which is a copolymer containing the at least 1 structural unit mentioned above.

[In formula, R <_1> represents a hydrogen atom or a methyl group, when R <_1> is a hydrogen atom, R <_2> represents a C1-C8 alkyl group and when R <_1> is a methyl group, R <_2> represents a C2-C8 alkyl group. .]

[10] A resin laminate comprising the protective film according to any one of the above [1] to [9], wherein the vinylidene fluoride resin is polyvinylidene fluoride.

[11] The melt mass-flow rate of vinylidene fluoride resin is 0.1 to 40 g / 10 minutes as measured at 3.8 kg load and 230 ° C., according to any one of the above [1] to [10]. Resin laminate.

[12] The above-mentioned [1] to [11], 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 provided with the protective film in any one.

[13] A resin laminate comprising the protective film according to any one of the above [1] to [12], wherein the vicat softening temperature of the thermoplastic resin contained in the thermoplastic resin layers (B) and (C) is 100 to 160 ° C, respectively. sieve.

[14] The resin laminate comprising the protective film according to any one of the above [1] to [13], wherein the thermoplastic resin layers (B) and (C) are a (meth) acrylic resin layer or a polycarbonate resin layer.

[15] The above-mentioned [1] to [14], wherein 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 provided with the protective film in any one.

[16] A resin laminate comprising the protective film according to the above [15], wherein the weight average molecular weight of the (meth) acrylic resin contained in the thermoplastic resin layers (B) and (C) is 50,000 to 300,000.

The resin laminated body provided with the protective film of this invention hardly generate | occur | produces external appearance defects, such as a dent, in a manufacturing and distribution process, and is used suitably for a display apparatus etc.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the manufacturing apparatus of the resin laminated body in the resin laminated body provided with the protective film of this invention used for the Example.
It is a cross-sectional schematic diagram which shows preferable one form of the liquid crystal display device containing the resin laminated body in the resin laminated body provided with the protective film of this invention.

The resin laminated body provided with the protective film of this invention contains the resin laminated body which has the intermediate | middle layer (A) and the thermoplastic resin layer (B) and (C) which exist in the both sides of the said intermediate | middle layer (A), respectively. In other words, the resin laminated body in the resin laminated body provided with the protective film of this invention has the structure which the thermoplastic resin layer (B) / intermediate | middle layer (A) / thermoplastic resin layer (C) laminated at least in this order. It is a resin laminated body.

An intermediate | middle layer (A) contains 10-90 mass% (meth) acrylic resin and 90-10 mass% vinylidene fluoride resin based on all resin contained in the said intermediate | middle layer (A). When the amount of the (meth) acrylic resin is lower than the above lower limit, sufficient transparency of the resin laminate is not obtained, and when the amount of the (meth) acrylic resin is higher than the above upper limit, sufficient dielectric constant is not obtained. When the amount of vinylidene fluoride resin is lower than the above lower limit, sufficient dielectric constant is not obtained, and when the amount of vinylidene fluoride resin is higher than the upper limit, durability of the resin laminate and sufficient transparency are not obtained.

The intermediate | middle layer (A) is 30-60 mass% of (meth) acrylic resin and 70-40 based on all resin contained in the said intermediate | middle layer (A) from a viewpoint of increasing dielectric constant and improving transparency of a resin laminated body. It is preferable to contain the mass% vinylidene fluoride resin, It is more preferable to contain 35-45 mass% (meth) acrylic resin and 65-55 mass% vinylidene fluoride resin, and it is 37-45 mass% It is still more preferable to contain a (meth) acrylic resin and 63-55 mass% vinylidene fluoride resin, and it contains 38-45 mass% (meth) acrylic resin and 62-55 mass% vinylidene fluoride resin It is especially preferable that it is 38-43 mass% (meth) acrylic resin, and 62-57 mass% vinylidene fluoride resin is very preferable.

As (meth) acrylic resin contained in the intermediate | middle layer (A) of the resin laminated body provided with the protective film of this invention, For example, (meth) acrylic monomers, such as (meth) acrylic acid ester and (meth) acrylonitrile, The homopolymer, the copolymer of 2 or more types of (meth) acryl monomer, the copolymer of monomers other than a (meth) acryl monomer, and a (meth) acryl monomer, etc. are mentioned. In addition, in this specification, the term "(meth) acryl" means "acryl" or "methacryl".

It is preferable that (meth) acrylic resin is methacryl resin from a viewpoint of raising the hardness, weather resistance, and transparency of a resin laminated body. Methacrylic resin is a polymer of the monomer mainly having methacrylic acid ester (alkyl methacrylate), For example, the homopolymer (polyalkyl methacrylate) of methacrylic acid ester, 2 or more types of methacrylic acid ester And copolymers of monomers other than 50% by mass or more of methacrylic acid esters and 50% by mass or less of methacrylic acid esters. As a copolymer of methacrylic acid ester and monomers other than methacrylic acid ester, it is 70 mass% or more of methacrylic acid ester and 30 mass% or less with respect to the total amount of a monomer from a viewpoint of easy to improve an optical characteristic and weather resistance. The copolymer with a monomer is preferable, and the copolymer of 90 mass% or more methacrylic acid ester and 10 mass% or less other monomer is more preferable.

As monomers other than methacrylic acid ester, the monofunctional monomer which has one polymerizable carbon-carbon double bond in an acrylic acid ester and a molecule | numerator is mentioned.

As a monofunctional monomer, For example, Styrene monomers, such as styrene, (alpha) -methylstyrene, and vinyltoluene; Cyanide alkenyl such as acrylonitrile and methacrylonitrile; Acrylic acid; Methacrylic acid; Maleic anhydride; N-substituted maleimide; Etc. can be mentioned.

 N-substituted maleimide, such as phenyl maleimide, cyclohexyl maleimide, and methyl maleimide, may be copolymerized to (meth) acrylic resin from a heat resistant viewpoint, and also in molecular chain (also known as a main skeleton in a polymer or in a main chain) Lactone ring structure, glutaric anhydride structure, glutarimide structure, or the like may be introduced.

(Meth) acrylic resin specifically, from a viewpoint of raising the hardness, weather resistance, and transparency of a resin laminated body, specifically,

(a1) homopolymers of methyl methacrylate, and / or

(a2) Structural unit derived from 50-99.9 mass%, Preferably 70.0-99.9 mass%, More preferably, 80.0-99.9 mass% methyl methacrylate based on all the structural units which comprise a copolymer, and , 0.1 to 50% by mass, preferably 0.2 to 30% by mass, more preferably a copolymer containing at least one structural unit derived from (meth) acrylic acid ester represented by formula (1) of 0.3 to 20% by mass. It is preferable. Here, content of each structural unit can be computed by analyzing the obtained polymer by pyrolysis gas chromatography and measuring the peak area corresponding to each monomer.

[In formula, R <_1> represents a hydrogen atom or a methyl group, when R <_1> is a hydrogen atom, R <_2> represents a C1-C8 alkyl group and when R <_1> is a methyl group, R <_2> represents a C2-C8 alkyl group. .]

In formula (1), R <_1> represents a hydrogen atom or a methyl group, when R <_1> is a hydrogen atom, R <_2> represents a C1-C8 alkyl group, and when R <_1> is a methyl group, R <_2> is C2-C8 An alkyl group is shown. 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. It is preferable that it is a C2-C4 alkyl group from a heat resistant viewpoint, and, as for R <_2> , it is more preferable that it is an ethyl group.

The weight average molecular weight (Hereinafter, it may be described as Mw.) Of the (meth) acrylic resin contained in an intermediate | middle layer (A) is 100,000-300,000. When Mw is lower than the said lower limit, transparency at the time of exposure in high temperature, high humidity environment is not enough, and when Mw is higher than the said upper limit, the film-forming property at the time of manufacturing a resin laminated body is not obtained. It is preferable that it is 120,000 or more, and, as for Mw of (meth) acrylic resin, it is more preferable that it is 150,000 or more from a viewpoint which is easy to raise transparency when it exposes in high temperature, high humidity environment. It is preferable that it is 250,000 or less, and, as for Mw of (meth) acrylic resin from a film formability at the time of manufacturing a resin laminated body, it is more preferable that it is 200,000 or less. The weight average molecular weight is measured by gel permeation chromatography (GPC) measurement.

(Meth) acrylic resin is measured at 3.8 kg load and 230 degreeC, and melt mass flow rate of 0.1-20 g / 10 minutes normally, Preferably it is 0.2-5 g / 10 minutes, More preferably, 0.5-3 g / 10 minutes (Hereinafter, referred to as MFR). Since MFR is easy to raise the intensity | strength of a resin laminated body, it is preferable that it is below the said upper limit, and it is preferable from a viewpoint of the film formability of a resin laminated body that it is more than the said minimum. MFR can be measured based on the method prescribed | regulated to JISK7210: 1999 "Test method of the melt mass flow rate (MFR) and melt volume flow rate (MVR) of a plastics-thermoplastic plastic." About the material of a poly (methyl methacrylate) system, it is prescribed | regulated to this JIS to measure by temperature 230 degreeC and a load of 3.80 kg (37.3 N).

From the viewpoint of heat resistance, the (meth) acrylic resin is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, even more preferably 102 ° C. or higher, and a bicat softening temperature (hereinafter referred to as VST). ) Although the upper limit of VST is not specifically limited, Usually, it is 150 degrees C or less. VST can be measured by the B50 method described here based on JISK7206: 1999. VST can be adjusted in said range by adjusting the kind and ratio of a monomer.

(Meth) acrylic resin can be prepared by superposing | polymerizing said monomer by well-known methods, such as suspension polymerization and bulk polymerization. In that case, MFR, Mw, VST, etc. can be adjusted to a preferable range by adding a suitable chain transfer agent. A suitable commercial item can be used for a 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 requested | required, etc.

As a vinylidene fluoride resin contained in the intermediate | middle layer (A) of the resin laminated body provided with the protective film of this invention, the homopolymer of vinylidene fluoride, a copolymer of vinylidene fluoride, and another monomer is mentioned. The vinylidene fluoride resin is selected from the group consisting of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether, and ethylene from the viewpoint of increasing transparency of the resin laminate. It is preferable that it is a copolymer of at least 1 sort (s) of monomer chosen and vinylidene fluoride, and / or a homopolymer (polyvinylidene fluoride) of vinylidene fluoride, and it is more preferable that it is 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, even more preferably 200,000 to 450,000, particularly preferably 350,000 to 450,000. It is preferable that Mw is more than the said lower limit, since transparency of a resin laminated body is easy to be heightened when it exposes the resin laminated body of this invention in the environment of high temperature, high humidity (for example, 60 degreeC, 90% relative humidity). Moreover, since Mw is below the said upper limit, since it is easy to raise the film-formability of a resin laminated body, it is preferable. The weight average molecular weight is measured by gel permeation chromatography (GPC) measurement.

The vinylidene fluoride resin is measured at a load of 3.8 kg and 230 ° C, preferably 0.1 to 40 g / 10 minutes, more preferably 0.1 to 30 g / 10 minutes, still more preferably 0.1 to 25 g / 10 minutes Has a mass flow rate (MFR). MFR becomes like this. More preferably, it is 0.2 g / 10 minutes or more, More preferably, it is 0.5 g / 10 minutes or more. Moreover, MFR becomes like this. More preferably, it is 20 g / 10 minutes or less, More preferably, it is 5 g / 10 minutes or less, Especially preferably, it is 2 g / 10 minutes or less. It is preferable that MFR is below the said upper limit, since it is easy to suppress the fall of transparency at the time of using a resin laminated body for a long time. It is preferable that MFR is more than the said minimum because it is easy to raise the film-formability of a resin laminated body. MFR can be measured based on the method prescribed | regulated to JISK7210: 1999 "Test method of the melt mass flow rate (MFR) and melt volume flow rate (MVR) of a plastics-thermoplastic plastic."

Vinylidene fluoride resin is industrially manufactured by suspension polymerization method or emulsion polymerization method. The suspension polymerization method is performed by using water as a medium, dispersing the monomer as a droplet in the medium with a dispersant, and polymerizing the organic peroxide dissolved in the monomer as a polymerization initiator, thereby obtaining a granular polymer having a particle size of 100 to 300 µm. Obtained. The suspension polymer is preferable because the production process is simpler than the emulsion polymer, the handleability of the powder is excellent, and the emulsion polymer does not contain an emulsifier or salting agent containing an alkali metal like the emulsion polymer.

You may use a commercial item for vinylidene fluoride resin. As an example of a preferable commercial item, "KF polymer (trademark) T # 1300, T # 1100, T # 1000, T # 850, W # 850, W # 1000, W # 1100 and W # 1300" by Kureha Co., Ltd., are manufactured by Solvay Corporation. (I) "SOLEF (registered trademark) 6012, 6010, and 6008" are mentioned.

The intermediate layer (A) may further include other resins different from the (meth) acrylic resin and the vinylidene fluoride resin. When it contains another 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 the other resin is preferably 15% by mass or less, more preferably 10% by mass or less, based on all the resins contained in the intermediate layer (A), and 5% by mass. It is more preferable that it is below. As another resin, a polycarbonate resin, a polyamide resin, an acrylonitrile styrene copolymer, the methyl methacrylate styrene copolymer, a polyethylene terephthalate, etc. are mentioned, for example. Although the intermediate | middle layer (A) may contain another resin further, from a transparency viewpoint, it is preferable that the quantity of other resin is 1 mass% or less, and resin contained in an intermediate | middle layer (A) is a (meth) acrylic resin and vinylidene fluoride resin only. It is more preferable that is.

The content of the 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 based on all the resins contained in the intermediate layer (A). Is 1 ppm or less. It is preferable that content of the alkali metal in an intermediate | middle layer (A) is below the said upper limit, since it is easy to suppress the fall of transparency when using a resin laminated body in high temperature, high humidity environment for a long time. It is very preferable that the lower limit of content of the alkali metal in an intermediate | middle layer (A) is 0, and is not contained substantially from a viewpoint which is easy to suppress the fall of the transparency of a resin laminated body. Here, in the (meth) acrylic resin and / or vinylidene fluoride resin contained in an intermediate | middle layer (A), the trace amount of emulsifiers used at the manufacturing process, etc. remain. For this reason, alkali metals, such as sodium and potassium, are contained in an intermediate | middle layer (A), for example, 0.05 ppm or more derived from the emulsifier which remains. Especially when the (meth) acrylic resin and / or vinylidene fluoride resin contained in an intermediate | middle layer (A) is obtained by emulsion polymerization, the quantity of the emulsifier remaining in resin increases, and the alkali metal in an intermediate | middle layer (A) Also increases the content. It is preferable to use resin with little content of an alkali metal as (meth) acrylic resin and vinylidene fluoride resin contained in an intermediate | middle layer (A) from a viewpoint which is easy to suppress the fall of transparency of a resin laminated body.

In order to make content of the alkali metal in resin into the said range, what is necessary is just to reduce the usage-amount of the compound containing an alkali metal at the time of superposition | polymerization of a resin, or to increase the washing | cleaning process after superposition | polymerization, and to remove the compound containing an alkali metal. Content of an alkali metal can be calculated | required by inductively coupled plasma mass spectrometry (ICP / MS), for example. As the inductively coupled plasma mass spectrometry, for example, the sample pellets to be measured are sampled by appropriate methods such as high temperature ash melting method, high temperature ash dissolving method, Ca addition ash dissolving method, combustion absorption method, and low temperature ash dissolving method. What is necessary is just to incinerate, to melt | dissolve this in an acid, to justify this melt | dissolution liquid, and to measure content of an alkali metal by the inductively coupled plasma mass spectrometry.

The resin laminated body provided with the protective film of this invention has the thermoplastic resin layer (B) and (C) which exist in the both sides of an intermediate | middle layer (A), respectively. The same layer may be sufficient as a thermoplastic resin layer (B) and a thermoplastic resin layer (C), and a layer different from each other may be sufficient as it.

The thermoplastic resin layers (B) and (C) contain at least one thermoplastic resin. From the viewpoint of easy molding processability, the thermoplastic resin layers (B) and (C) are preferably 60% by mass or more, more preferably 70% by mass or more, based on all the resins contained in each thermoplastic resin layer. Even more preferably, 80 mass% or more of thermoplastic resins are included. The upper limit of the quantity of a thermoplastic resin is 100 mass%. Examples of the thermoplastic resins include (meth) acrylic resins, polycarbonate resins, cycloolefin resins, and the like. It is preferable that a thermoplastic resin is (meth) acrylic resin or a polycarbonate resin from a viewpoint of easy adhesiveness of a thermoplastic resin layer (B) and (C) and an intermediate | middle layer (A). The thermoplastic resin layers (B) and (C) may contain the same thermoplastic resin or may include different thermoplastic resins. It is preferable that a thermoplastic resin layer (B) and (C) contain the same thermoplastic resin from a viewpoint which is easy to suppress the curvature of a resin laminated body.

From the viewpoint of the heat resistance of the resin laminate, the thermoplastic resins contained in the thermoplastic resin layers (B) and (C) are preferably 100 to 160 ° C, more preferably 102 to 155 ° C, even more preferably 102 to Vicat softening temperature of 152 ℃. Here, the said bicat softening temperature is the bicat softening temperature of the resin, when a thermoplastic resin layer contains 1 type of thermoplastic resin, and when a thermoplastic resin layer contains 2 or more types of thermoplastic resin, Vicat softening temperature of the mixture of thermoplastic resins. The vicat softening temperature of a thermoplastic resin is measured based on the B50 method prescribed | regulated to JISK7206: 1999 "The plastics thermoplastic thermoplastic vicat softening temperature (VST) test method." Vicat softening temperature can be measured using a heat distortion tester (for example, "148-6 mold type" by Yasuda Seiki Co., Ltd.). A measurement may be performed using the test piece which press-molded each raw material to thickness 3mm.

The thermoplastic resin layers (B) and (C) may further contain other resins (for example, thermosetting resins such as fillers and resin particles) other than the thermoplastic resin for the purpose of increasing the strength, elasticity, and the like of the thermoplastic resin layer. In this case, the amount of the other resin is preferably 40% by mass or less, more preferably 30% by mass or less, 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 resin is 0 mass%.

The thermoplastic resin layers (B) and (C) have a good moldability and are preferably a (meth) acrylic resin layer or a polycarbonate resin layer from the viewpoint of easily adhering to the intermediate layer (A).

EMBODIMENT OF THE INVENTION One aspect of this invention whose thermoplastic resin layers (B) and (C) are a (meth) acrylic resin layer is demonstrated below. In this embodiment, the thermoplastic resin layers (B) and (C) contain at least one (meth) acrylic resin. From the viewpoint of surface hardness, the thermoplastic resin layers (B) and (C) are preferably 50% by mass or more, more preferably 60% by mass or more, based on all the resins contained in each thermoplastic resin layer. Preferably it contains 70 mass% or more of (meth) acrylic resin.

As (meth) acrylic resin, resin described about the (meth) acrylic resin contained in an intermediate | middle layer (A) is mentioned. Preferable (meth) acrylic resin described about the intermediate | middle layer (A) is also likewise suitable as (meth) acrylic resin contained in thermoplastic resin layers (B) and (C) unless there is particular notice. 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 has good molding processability and is preferably 50,000 to 300,000, and more preferably 70,000 to 250,000 from the viewpoint of increasing the mechanical strength. The weight average molecular weight is measured by gel permeation chromatography (GPC) measurement.

In this aspect, the thermoplastic resin layers (B) and (C) may further include thermoplastic resins other than one or more (meth) acrylic resins. As thermoplastic resins other than (meth) acrylic resin, the thermoplastic resin compatible with (meth) acrylic resin is preferable. Specifically, methyl methacrylate-styrene-maleic anhydride copolymer (for example, "denspy" by Denki Chemical Co., Ltd.) and methyl methacrylate-methacrylic acid copolymer (for example, alchema "altoglass HT121"). And polycarbonate resins. Thermoplastic resins other than the (meth) acrylic resin are measured in accordance with JIS K 7206: 1999 from the viewpoint of heat resistance, and are preferably 115 ° C or higher, more preferably 117 ° C or higher, even more preferably 120 ° C or higher. It is desirable to have a cart softening temperature. Moreover, from a viewpoint of heat resistance and surface hardness, it is preferable that thermoplastic resin layers (B) and (C) do not contain vinylidene fluoride resin substantially.

In this aspect, the pencil hardness of the thermoplastic resin layers (B) and (C) is preferably at least HB, more preferably at least F, and even more preferably at least H from the viewpoint of increasing the scratch resistance. Do.

Next, the other aspect of this invention whose thermoplastic resin layers (B) and (C) are polycarbonate resin layers is demonstrated below. In this embodiment, the thermoplastic resin layers (B) and (C) contain at least one polycarbonate resin. From the viewpoint of impact resistance, the thermoplastic resin layers (B) and (C) are preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably based on the total resin contained in each thermoplastic resin layer. Preferably at least 80% by mass of polycarbonate resin.

As the polycarbonate resin, for example, a polymer obtained by a phosgene method for reacting various dihydroxydiaryl compounds and phosgene or a transesterification method for reacting a carbonate ester such as a dihydroxydiaryl compound and diphenyl carbonate may be used. Specifically, the polycarbonate resin manufactured by 2, 2-bis (4-hydroxyphenyl) propane (common name bisphenol A) is mentioned.

As said dihydroxy diaryl compound, in addition to bisphenol A, 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-hydroxy-3-methylphenyl) propane, 1,1-bis (4 -Hydroxy-3-tertiary butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromo Bis (hydroxyaryl) alkanes such as phenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1 Bis (hydroxyaryl) cycloalkanes such as 1, bis- (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenylether, 4,4'-dihydroxy-3,3 ' Dihydroxy diaryl ethers such as -dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-di Dihydroxydiaryl sulfoxides such as hydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4, And dihydroxy diaryl sulfones such as 4'-dihydroxy-3,3'-dimethyldiphenyl sulfone.

These are used individually or in mixture of 2 or more types, In addition, you may mix and use a piperazine, a dipiperidyl hydroquinone, a resorcin, 4,4'- dihydroxy diphenyl, etc. in addition to these.

Moreover, you may mix and use the said dihydroxy aryl compound and the trihydric or more phenol compound as shown below. Examples of the trivalent or higher phenol include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-trimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2- And bis- [4,4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane.

As polycarbonate resins other than the said polycarbonate resin, the polycarbonate synthesize | combined from isosorbide and aromatic diol is mentioned. As an example of the said polycarbonate, Mitsubishi Chemical Corporation "DURABIO (trademark registration)" is mentioned.

A commercial item may be used as polycarbonate resin, for example, "Caliber (trademark) 301-4, 301-10, 301-15, 301-22, 301-30, 301-40 made by Sumika styrene polycarbonate Corporation , SD2221W, SD2201W, TR2201 ”, and the like.

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

In this embodiment, the polycarbonate resin contained in the thermoplastic resin layer (B) and (C), measured under the conditions of temperature 300 ℃ and load 1.2kg, and preferably ³ ~ 120cm 3/10 min, and more preferably is (also referred to ^{below, MVR.) 3 ~ 80cm 3} /10 minutes, and more preferably, from 4 ~ 40cm ^3/10 minutes, particularly preferably 10 ~ 40cm ^3/10 bun melt volume flow rate has. When the MVR is higher than the above lower limit, the fluidity is sufficiently high, and it is preferable because it is easy to be molded in melt coextrusion molding or the like and appearance defects are less likely to occur. When MVR is lower than said upper limit, since it is easy to raise mechanical characteristics, such as the strength of a polycarbonate resin layer, it is preferable. MVR can be measured on condition of 300 degreeC under the load of 1.2 kg based on JISK7110.

In this aspect, the thermoplastic resin layers (B) and (C) may further contain thermoplastic resins other than one or more polycarbonate resins. As thermoplastic resins other than polycarbonate resin, the thermoplastic resin compatible with polycarbonate resin is preferable, (meth) acrylic resin is more preferable, and methacryl resin which has an aromatic ring or cycloolefin in a structure is still more preferable. When the thermoplastic resin layers (B) and (C) contain a polycarbonate resin and the above-mentioned (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 compared with that.

At least one layer of an intermediate | middle layer (A), a thermoplastic resin layer (B), and (C) in the resin laminated body provided with the protective film of this invention is generally used in the range which does not impair the effect of this invention. You may further include the various additives which become. Examples of the additive include colorants such as stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, foaming agents, lubricants, mold release agents, antistatic agents, flame retardants, polymerization inhibitors, flame retardant aids, reinforcing agents, nucleating agents, and bluing agents.

As a coloring agent, the compound which has an anthraquinone skeleton, the compound which has a phthalocyanine skeleton, etc. are mentioned. Among these, the compound which has an anthraquinone frame | skeleton is preferable from a heat resistant viewpoint.

When at least one layer of an intermediate | middle layer (A), a thermoplastic resin layer (B), and (C) further contains a coloring agent, content of the coloring agent in each layer can be suitably selected according to the objective, the kind of coloring agent, etc. When using a bluing agent as a coloring agent, the content can be made into about 0.01-10 ppm based on all resin contained in each layer containing a bluing agent. This content becomes like this. Preferably it is 0.01 ppm or more, More preferably, it is 0.05 ppm or more, More preferably, it is 0.1 ppm or more, More preferably, it is 7 ppm or less, More preferably, it is 5 ppm or less, More preferably, it is 4 ppm or less Especially preferably, it is 3 ppm or less. A bluing agent can use a well-known thing suitably, For example, Macrorex (registered trademark) Blue RR (made by Bayer Corporation), Macrorex (registered trademark) Blue 3R (made by Bayer Corporation), Sumiplast (registered trademark) is a brand name, respectively. And Viloet B (manufactured by Sumica Chemtex Co., Ltd.) and polycinrene (registered trademark) blue RLS (manufactured by Clariant Corporation), Diaresin Violet D, Diaresin Blue G, and Diaresin Blue N (above, manufactured by Mitsubishi Chemical Corporation).

It does not specifically limit as a ultraviolet absorber, You may use various conventionally well-known ultraviolet absorbers. For example, the ultraviolet absorber which has an absorption maximum in 200-320 nm or 320-400 nm is mentioned. Specifically, a triazine ultraviolet absorber, a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a benzoate ultraviolet absorber, and a cyanoacrylate ultraviolet absorber are mentioned. As a ultraviolet absorber, you may use individually by 1 type of such ultraviolet absorbers or in combination of 2 or more type. The combination of at least one ultraviolet absorber having an absorption maximum at 200 to 320 nm and at least one ultraviolet absorber having an absorption maximum at 320 to 400 nm can also be effectively prevented from damage caused by ultraviolet rays. desirable. A commercial item may be used as a ultraviolet absorber, for example, "Kemisorb 102" (2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-N-octyl) by the chemical company Kemipro Kasei Co., Ltd. Oxyphenyl) -1,3,5-triazine) (absorbance 0.1), "ADEKASTAB LA-F70" made by ADEKA Corporation (2,4,6-tris (2-hydroxy-4-hexyloxy-) 3-methylphenyl) -1,3,5-triazine) (absorbance 0.6), `` adecastab LA-31, LA-31RG, LA-31G '' (2,2'-methylenebis (4- (1,1 , 3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol) (absorbance 0.2), "ADEKASTAB LA-46" made by ADEKA Corporation (2- (4,6- Diphenyl-1,3,5-triazin-2-yl) -5- (2- (2-ethylhexanoyloxy) ethoxy) phenol) (absorbance 0.05) or BASF Japan Co., Ltd. "tinuvin 1577" (2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine) (absorbance 0.1), etc. The absorbance of the illustrated ultraviolet absorber is, Absorbance at 380 nm, which is 10 mg / L It can be measured using a spectrophotometer (for example, spectrophotometer U-4100 made from HITACHI) by dissolving a ultraviolet absorber in chloroform at a density | concentration.

When at least one layer of an intermediate | middle layer (A), a thermoplastic resin layer (B), and (C) further contains an ultraviolet absorber, content of the ultraviolet absorber in each layer is suitably selected according to the objective, the kind of ultraviolet absorber, etc. You may also For example, content of a ultraviolet absorber can be made into about 0.005-2.0 mass% based on all resin contained in each layer containing a ultraviolet absorber. Content of a ultraviolet absorber becomes like this. Preferably it is 0.01 mass% or more, More preferably, it is 0.02 mass% or more, More preferably, it is 0.03 mass% or more. Moreover, content of a ultraviolet absorber becomes like this. Preferably it is 1.5 mass% or less, More preferably, it is 1.0 mass% or less. It is preferable that content of a ultraviolet absorber is more than the said minimum at the point which is easy to raise an ultraviolet absorption effect, and it is easy to prevent the change of the color tree (for example, yellowness YI) of a resin laminated body that it is below the said upper limit. It is preferable because of that. For example, it is preferable to use the said commercial item "adecastab LA-31, LA-31RG, LA-31G" in the said quantity.

In another aspect of the present invention, the thermoplastic resin layers (B) and (C) are polycarbonate resin layers and contain 0.005 to 2.0% by mass of an ultraviolet absorber based on all the resins contained in each thermoplastic resin layer. It is preferable because it is easy to obtain the resin laminated body excellent in light resistance.

In the resin laminated body provided with the protective film of this invention, the average value of the film thickness of an intermediate | middle layer (A) becomes like this from a viewpoint of dielectric constant, Preferably it is 100 micrometers or more, More preferably, it is 200 micrometers or more, More preferably, It is 300 micrometers or more. Moreover, from a transparency viewpoint, 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 | middle layer (A) cut | disconnects a resin laminated body perpendicularly | vertically with respect to a surface direction, and grinds the cross section using sand paper, and then uses a microscope (for example, a microscope made from a microsquare). It can measure by observing. The average value which performed the said measurement in arbitrary ten points is made into the average value of film thickness.

In the resin laminated body provided with the protective film of this invention, the average value of the film thickness of a thermoplastic resin layer (B) and (C) is respectively 10 micrometers or more from a viewpoint which is easy to raise surface hardness, Preferably it is more preferable. Preferably it is 30 micrometers or more, More preferably, it is 50 micrometers or more. In terms of dielectric constant, each is preferably 200 µm or less, more preferably 175 µm or less, even more preferably 150 µm or less. The average value of the film thickness of a thermoplastic resin layer can be measured similarly to the method described above about an intermediate | middle layer.

In the resin laminated body provided with the protective film 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 thermoplastic resin layers (B) and (C) is 10-200 micrometers, respectively. It is preferable from the viewpoint of being easy to suppress the curvature of the said laminated body.

The average value of the film thickness is preferably 100 µm or more, more preferably 200 µm or more, even more preferably 300 µm or more from the viewpoint of easily increasing the rigidity of the resin laminate. Moreover, from a transparency viewpoint of the laminated body after peeling, Preferably it is 2000 micrometers or less, More preferably, it is 1500 micrometers or less, More preferably, it is 1000 micrometers or less. A film thickness is measured by a digital micrometer, and makes the average value of the measured value in arbitrary 10 points into the average value of film thickness.

From the viewpoint of obtaining a function sufficient for use in a display device such as a touch panel, the resin laminate in the resin laminate including the protective film of the present invention is preferably 3.5 or more, more preferably 4.0 or more, Even more preferably has a dielectric constant of 4.1 or greater. The upper limit of the dielectric constant is not particularly limited, but is usually 20. Dielectric constant can be adjusted to the said range by adjusting the kind and quantity of vinylidene fluoride resin contained in the intermediate | middle layer (A) of the resin laminated body of this invention, or adding high dielectric constant compounds, such as ethylene carbonate and a propylene carbonate. . The dielectric constant is based on JIS K 6911: 1995, and the resin laminate after peeling off the protective films (D) and (E) is allowed to stand for 24 hours in an environment of 50% relative humidity at 23 ° C. Is a value measured at 3 V and 100 kHz by the automatic balancing bridge method. A commercially available instrument may be used for measurement, for example, "precision LCR meter HP4284A" by Agilent Technologies, Inc. may be used.

In the resin laminated body provided with the protective film of this invention, when a resin laminated body is observed visually, it is preferable that it is transparent. Specifically, the resin laminate after peeling the protective films (D) and (E) is measured in accordance with JIS K7361-1: 1997, preferably 85% or more, more preferably 88% or more, even more preferably Has a total light transmittance Tt of 90% or more. The upper limit of total light transmittance is 100%. It is preferable that the laminated body after exposure for 120 hours in 60 degreeC environment of 90% of a relative humidity also has the total light transmittance of the said range.

The resin laminated body after peeling off protective film (D) and (E) is measured based on JISK7136: 2000 using the laminated body after 120 hours exposure in 60 degreeC environment of 90% relative humidity, Preferably It has a haze of 2.0% or less, more preferably 1.8% or less, even more preferably 1.5% or less. In addition, the resin laminated body after peeling protective film (D) and (E) is measured according to JIS Z 8722: 2009, using the resin laminated body after exposure for 120 hours in 60 degreeC environment of 90% of a relative humidity, Preferably it has a yellowness (Yellow Index: YI value) of 1.5 or less, more preferably 1.4 or less, even more preferably 1.3 or less. The resin laminated body after peeling the said protective film (D) and (E) which have said haze and yellowness is hard to produce curvature even if it uses in environments, such as high temperature, high humidity, maintains transparency, and suppresses yellowing It is preferable at the point which is easy to do.

In the resin laminated body provided with the protective film of this invention, in addition to an intermediate | middle layer (A) and a thermoplastic resin layer (B) and (C), the resin laminated body may have at least 1 functional layer. It is preferable that a functional layer exists in the surface on the opposite side to an intermediate | middle layer (A) of a thermoplastic resin layer (B) and / or (C). For example, when a functional layer exists in the surface on the opposite side to the intermediate | middle layer (A) of a thermoplastic resin layer (B) and / or (C), a protective film may be stuck to the surface of the said functional layer. As a functional layer, a hard coat layer, an antireflection layer, an anti-glare layer, an antistatic layer, an anti-fingerprint layer, etc. are mentioned, for example. Such a functional layer may be laminated | stacked on the resin laminated body via the adhesion layer, and the coating layer laminated | stacked by the coating may be sufficient. As a functional layer, you may use the hardened film as described, for example in Unexamined-Japanese-Patent No. 2013-86273. The functional layer may be, for example, an antireflection layer added to one or both surfaces of at least one functional layer selected from the group consisting of a hard coating layer, an antiglare layer, an antistatic layer, and an anti-fingerprint layer by coating, sputtering, vacuum deposition, or the like. May be a layer coated with a layer or may be a layer having an antireflective sheet bonded to one or both surfaces of the at least one functional layer.

Although the thickness of a functional layer may be suitably selected according to the objective of each functional layer, From a viewpoint which a function is easy to express, Preferably it is 1 micrometer or more, More preferably, it is 3 micrometers or more, More preferably, it is 5 micrometers or more, From the viewpoint of easy cracking of the functional layer, the thickness is preferably 100 µm or less, more preferably 80 µm or less, even more preferably 70 µm or less.

The resin laminated body provided with the protective film of this invention further has protective films (D) and (E) which have at least the film base material bonded together on both surfaces of the said resin laminated body. The protective film may be bonded to both surfaces of the resin laminate by, for example, electrostatic attraction or the like, or may be pasted through the adhesive layer. It is preferable that a protective film further has an adhesion layer, and is stuck together on both surfaces of a resin laminated body through the said adhesion layer. The protective film (D) and (E) may be the same film, and a film different from each other may be sufficient as it. In a preferred embodiment of the present invention in which the protective film has a film base material and an adhesive layer, the protective films (D) and (E) may have the same film base material and the adhesive layer, and different film base materials and the adhesive layer from each other. You may have, a mutually same film base material and mutually different adhesion layer, and may have a mutually different film base material and mutually same adhesion layer.

Protective films (D) and (E) are pasted on the surfaces of the thermoplastic resin layers (B) and (C), respectively, for the purpose of protecting the surface. In the resin laminated body provided with the protective film of this invention, since the resin laminated body which has an intermediate | middle layer (A), a thermoplastic resin layer (B), and (C) at least is soft, the surface of a resin laminated body has a dust etc. in the air. It is easy to generate recesses due to foreign matters. It is preferable that each of the protective films (D) and (E) satisfies the following relationship from the viewpoint of easily avoiding such recession.

[In formula, E represents the tensile elasticity modulus (MPa) of a protective film, and L represents the average value (mm) of the film thickness of the film base material of a protective film.]

The protective film which satisfy | fills the said relationship has rigidity especially suitable for the protection of the surface of a resin laminated body. Here, elastic modulus is a numerical value determined by the kind of resin which comprises a film base material, or a protective film, when a protective film has an adhesion layer. For this reason, the protective film which satisfy | fills the said relationship can be obtained by adjusting suitably the kind of film base material, the average value of a film thickness, the kind of adhesion layer, etc. as needed. Here, the tensile elasticity modulus of a protective film can be measured, for example by the electromechanical universal testing machine of Instron company based on JIS-K7127. When a protective film has an adhesion layer, the tensile elasticity modulus is measured using the protective film containing an adhesion layer. The average value of the film thickness of a film base material is measured by a digital micrometer, and makes the average value of the measured value in arbitrary ten points into an average value of film thickness.

Although the film base material of protective films (D) and (E) is not specifically limited as long as the surface of a resin laminated body can be protected, It is preferable that it is a plastic film from a viewpoint of raising the protective property of the surface of a resin laminated body easily, and it is low density. At least one film selected from the group consisting of polyethylene (LDPE) film, high density polyethylene (HDPE) film, polypropylene (PP) film, polyethylene terephthalate (PET) film, acrylic resin film, polycarbonate (PC) film It is more preferable. From the viewpoint of easily protecting the surface of the resin laminate, the film base materials of the protective films (D) and (E) are more preferably HDPE films, PP films or PET films, and very preferably HDPE films or PET films. desirable. A single layer may be sufficient as the film base material of protective films (D) and (E), and the multilayer which laminated several plastic films may be sufficient as it. As an example of a multilayer film base material, the film base material which has the following structures is mentioned, for example: LLDPE (linear low density polyethylene) / LDPE / PP, LLDPE / HDPE / PP, EVA (ethylene-vinyl acetate copolymer) / HDPE / PP, EVA / HDPE / LDPE etc.

The tensile modulus of the protective films (D) and (E) is preferably 100 MPa or more, more preferably 150 MPa or more, even more preferably 200 MPa or more from the viewpoint of easily increasing the protective property of the surface of the resin laminate. In addition, the tensile modulus of the film base materials of the protective films (D) and (E) is preferably 5,000 MPa or less, more preferably from the viewpoint of maintaining the protective property of the surface of the resin laminate even when a large foreign material is present. It is preferably at most 4,500 MPa, even more preferably at most 4,000 MPa. The measuring method of the tensile elasticity modulus of a protective film is as showing above.

As for the average value of the film thickness of the film base material of protective films (D) and (E), it is 45 micrometers or more, More preferably, it is 50 micrometers or more from a viewpoint which is easy to raise the protective property of the surface of a resin laminated body. Preferably it is 60 micrometers or more. The average value of the film thicknesses of the film substrates of the protective films (D) and (E) is preferably 200 µm or less, more preferably 175 µm or less, even more preferably 150 µm from the viewpoint of ease of bonding. It is as follows. The measuring method of the average value of the film thickness of a film base material is as showing above.

In one aspect of the present invention wherein the film substrates of the protective films (D) and (E) are polyethylene terephthalate films, the average value of the film thickness of the film substrate is preferably from the viewpoint of increasing the protective property of the surface of the resin laminate. Preferably it is 50 micrometers or more, More preferably, it is 60 micrometers or more, More preferably, it is 70 micrometers or more. In addition, in this aspect, the average value of the film thickness of a film base material is 200 micrometers or less, More preferably, it is 175 micrometers or less, More preferably, it is 150 micrometers or less from a viewpoint of the ease of pasting. The measuring method of the average value of the film thickness of a film base material is as showing above.

In one aspect of the present invention wherein the protective films (D) and (E) are high-density polyethylene films, the average value of the film thicknesses of the protective films (D) and (E) is a viewpoint of increasing the protective property of the surface of the resin laminate. Is preferably 50 μm or more, more preferably 60 μm or more, even more preferably 70 μm or more. In addition, in this aspect, the average value of the film thicknesses of the protective films (D) and (E) is preferably 200 µm or less, more preferably 175 µm or less, even more preferably from the viewpoint of ease of bonding. It is 150 micrometers or less. The measuring method of the average value of the film thickness of a protective film is the same as the method shown above about a film base material.

Protective films (D) and (E) are bonded to the surface of a resin laminated body, respectively. Here, protective films (D) and (E) are films which are bonded together for the purpose of protecting the surface of a resin laminated body, for example in a manufacturing process or a distribution process. For this reason, in the manufacturing process of a display apparatus, etc., protective films (D) and (E) are peeled off from the surface of thermoplastic resin layers (B) and (C), and an intermediate | middle layer (A) and a thermoplastic resin layer (B) and ( The resin laminated body which has C) at least is incorporated in a display apparatus as a component.

Next, the preferable aspect of this invention in which protective films (D) and (E) further have an adhesion layer is demonstrated. The said adhesion layer is adhesiveness sufficient to maintain the state which the protective films (D) and (E) adhered to the surface of a resin laminated body in a manufacturing process, a distribution process, etc., for example, and a protective film from the surface of a resin laminated body. It is required to have peelability which is easy to remove (D) and (E). From this point of view, the protective films (D) and (E) preferably have a low adhesive strength enough to be peeled off by hand from the surface of the resin laminate, and specifically, preferably 0.4 N / 25 mm or less. More preferably, it is more preferable to have peeling strength of 0.35 N / 25 mm or less, More preferably, it is 0.3 N / 25 mm or less. Moreover, from a viewpoint of being easy to maintain the state which the protective film (D) and (E) stuck together on the surface of the resin laminated body, Preferably it is 0.01 N / 25 mm or more, More preferably, it is 0.02 N / 25 mm or more, More More preferably, it has a peeling strength of 0.03 N / 25 mm or more. In addition, peeling strength is measured by peeling rate 0.3mm / min, peeling angle 180 degrees, and measuring width 25mm based on JIS-Z0237.

Although the adhesion layers of protective films (D) and (E) are not specifically limited as long as it has said adhesiveness and peelability, For example, acrylic resin, rubber resin, ethylene vinyl acetate copolymer type resin, polyester resin, acetate It is preferable to contain a resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin and the like as an adhesive. From a practical point of view, it is more preferable that an adhesion layer contains acrylic resin or ethylene vinyl acetate copolymer type resin as an adhesive.

The adhesive layers of protective films (D) and (E) may contain the other component of an adhesive. As another component, an antistatic agent, a coloring agent, a ultraviolet absorber, etc. are mentioned, for example.

The resin laminated body in the resin laminated body provided with the protective film of this invention provides the resin composition (A) which gives an intermediate | middle layer (A), the resin composition (B) and which respectively give (C) a thermoplastic resin layer (B). ) And (C). In addition, in this specification, resin composition (B) and (C) should just contain resin which gives a thermoplastic resin layer (B) and (C) at least, and 2 or more types of components, such as resin and arbitrary additives, The composition containing may be sufficient and one type of resin may be sufficient.

A resin composition (A) is obtained by kneading a (meth) acrylic resin and vinylidene fluoride resin normally. Kneading can be performed by the method including the process of melt-kneading at the shear rate of 10-1000 / sec, for example at the temperature of 150-350 degreeC.

The temperature at the time of melt kneading is preferable because it can melt | dissolve resin sufficiently, and it is preferable that it is 350 degrees C or less, since it is easy to suppress thermal decomposition of resin. Moreover, it is preferable that the shear rate at the time of melt kneading is 10 / sec or more because it is easy to fully knead resin, and it is preferable because it is easy to suppress decomposition | disassembly of resin in 1000 / second or less.

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

As a device used for melt kneading, a conventional mixer or kneader can be used. Specific examples thereof include a single screw kneader, a twin screw kneader, a twin screw extruder, a Henschel mixer, a half-variable mixer, a kneader, a roll mill, and the like. In addition, when making shear rate large in the said range, you may use a high shearing apparatus etc.

Resin composition (B) and (C) can also be manufactured similarly to resin composition (A), for example by melt-kneading etc. under said temperature and shear rate. For example, when a thermoplastic resin layer (B) and (C) contains one type of thermoplastic resin, you may manufacture a resin laminated body by melt extrusion mentioned later, without melt-kneading beforehand.

When the intermediate layer (A), the thermoplastic resin layers (B), and (C) contain an additive, the additive may be previously contained in the resin contained in each layer, may be added during melt kneading of the resin, and the resin is melted. You may add after kneading | mixing and you may add when manufacturing a resin laminated body using a resin composition.

The resin laminate which has at least the intermediate | middle layer (A) and the thermoplastic resin layer (B) and (C) which exists in both sides of an intermediate | middle layer (A), for example, melt-extrusion molding method, solution casting film forming method, heat press method, Each layer (A)-(C) is produced separately from resin composition (A)-(C) by injection molding method, etc., You may manufacture these, for example, sticking together via an adhesive or an adhesive, and a resin composition (A (C) may be manufactured by laminating and unifying by melt coextrusion molding. When manufacturing a resin laminated body by bonding, it is preferable to use the injection molding method and the melt extrusion molding method for preparation of each layer, and it is more preferable to use the melt extrusion molding method. It is preferable to manufacture a resin laminated body by melt coextrusion molding resin compositions (A)-(C), since the resin laminated body which is easy to secondary molding is obtained compared with the resin laminated body manufactured by pasting normally. Do.

Melt coextrusion molding, for example, after separately putting the resin composition (A) and the resin composition (B) and (C) into two or three single screw or twin screw extruders separately and kneading And an intermediate layer (A) formed of the resin composition (A), the thermoplastic resin layers (B), and (C) are laminated and integrated through a feed block die, a multi-manifold die, and the like. When the resin compositions (B) and (C) are the same composition, one composition melt-kneaded in one extruder is divided into two via a feedblock die or the like, and the thermoplastic resin layers (B) and (C) are divided into two. You may form. It is preferable that the obtained film | membrane is cooled and solidified by a roll unit etc., for example.

The protective films (D) and (E) apply | coat an adhesive liquid and the coating liquid containing solvent, such as another component and water, on one surface of a film base material, for example, and let it dry, and make an adhesion layer It can manufacture by forming. Or the adhesive layer previously shape | molded in the sheet form can be stuck together and manufactured on one surface of a film base material. You may use what is marketed as a protective film. As a commercially available protective film, the polyolefin film "PAC-2 type" by Sunei Chemical Co., Ltd., "PET base marking SAT116 type", "E-2035" by Sumon Corporation, etc. are mentioned, for example.

The resin laminated body provided with the protective film of this invention can be manufactured by pasting the said protective film on the resin laminated body manufactured as mentioned above.

Although the size of the resin laminated body provided with the protective film of this invention is not specifically limited, For example, it distribute | circulates in the form of the resin laminated body provided with the protective film which has the width 500-3000 mm and the size of 500-3000 mm in length. do.

The resin laminated body provided with the protective film of this invention is a form of the resin laminated body obtained by peeling a protective film, and can be used in various display apparatuses. The 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 a display apparatus, a liquid crystal display device, an organic electroluminescent (EL) display apparatus, an inorganic electroluminescent (EL) display apparatus, a touch panel display apparatus, an electron emission display apparatus (for example, an electric field emission display apparatus (FED) , Surface field emission display (SED), electronic paper (display using electronic ink or electrophoretic element), plasma display, projection display (e.g. grating light valve (GLV) display, digital micro mirror device) (Display device having a DMD), a piezoelectric ceramic display, and the like. 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. Such a display device may be a display device which displays a two-dimensional image, or may be a three-dimensional display device which displays a three-dimensional image. The resin laminated body in the resin laminated body provided with the protective film of this invention is used suitably as a front plate or a transparent electrode in these display apparatuses, for example.

When using the resin laminated body in the resin laminated body provided with the protective film of this invention as a transparent electrode in a touchscreen etc., a transparent conductive film is formed in at least one surface of a resin laminated body, and a transparent conductive sheet is manufactured, The transparent electrode can be manufactured from the transparent conductive sheet.

As a method of forming a transparent conductive film in at least one surface of a resin laminated body, you may form a transparent conductive film directly in the surface of a resin laminated body, and may laminate | stack the plastic film in which the transparent conductive film was formed previously on the surface of a resin laminated body.

As a film base material of the plastic film in which the transparent conductive film was formed previously, if it is a base material which can form a transparent conductive film as a transparent film, it will not specifically limit, For example, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylic resin, polyamide, Such mixtures or laminates may be mentioned. Moreover, before forming a transparent conductive film, you may coat the said film for the purpose of improving surface hardness, prevention of a Newton ring, provision of antistatic property, etc.

The method of laminating | stacking the film in which the transparent conductive film was formed previously on the surface of a resin laminated body may be any method as long as there is no bubble etc. and it is a method in which a uniform and transparent sheet is obtained. You may use the method of laminating | stacking using the adhesive agent hardened by normal temperature, a heating, an ultraviolet-ray, or a visible light, and may stick together by a transparent adhesive tape.

As a film formation method of a transparent conductive film, the vacuum vapor deposition method, the sputtering method, the CVD method, the ion plating method, the spray method, etc. are known, Such a method can be used suitably according to the film thickness required.

In the case of the sputtering method, for example, a conventional 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 the reactive gas, or means such as ozone addition, plasma irradiation, or ion assist may be used in combination. Moreover, you may apply bias, such as direct current, alternating current, and high frequency, to a board | substrate as needed. Examples of the transparent conductive metal oxide used in the transparent conductive film include indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide, indium-zinc composite oxide, and the like. . Among these, indium-tin composite oxide (ITO) is preferable from the viewpoint of environmental stability and circuit workability.

Moreover, as a method of forming a transparent conductive film, the coating agent containing various conductive polymers which can form a transparent conductive film is apply | coated to the surface of a resin laminated body, and a coating is hardened | cured by irradiating ionizing radiation, such as heat or an ultraviolet-ray. The method can also be applied. As the conductive polymer, polythiophene, polyaniline, polypyrrole and the like are known, and such a conductive polymer 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 50-2000 kPa normally, Preferably it is 70-2000 kPa. It is excellent in both electroconductivity and transparency as it is this range.

The thickness of a transparent conductive sheet is not specifically limited, The optimal thickness according to the request of the product specification of a display can be selected.

The touch sensor panel can be manufactured using the resin laminated body in the resin laminated body provided with the protective film of this invention as a display panel faceplate, and using the transparent conductive sheet manufactured by the resin laminated body as transparent electrodes, such as a touchscreen. Can be. Specifically, the resin laminate of the present invention can be used as a window sheet for a touch screen, and the transparent conductive sheet can be used as an electrode substrate of a resistive touch screen or a capacitive touch screen. By arrange | positioning this touchscreen on the front surface of a liquid crystal display device, an organic electroluminescence display, etc., the external touch sensor panel which has a touchscreen function is obtained.

2, the preferable one aspect | mode of the liquid crystal display device containing the resin laminated body in the resin laminated body provided with the protective film of this invention is shown in a cross-sectional schematic diagram. The resin laminated body 10 in the resin laminated body provided with the protective film of this invention is laminated | stacked on the polarizing plate 11 through the optical adhesion layer 12, and this laminated body is a liquid crystal cell 13 Can be placed on the side of the viewer. Usually, the polarizing plate 11 is arrange | positioned at the back side of the liquid crystal cell 13. The liquid crystal display device 14 is comprised from such a member. 2 is an example of a liquid crystal display device, and the display device of this invention is not limited to this structure.

Example

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

In Example, the vicat softening temperature, content of alkali metal, MFR, MVR, total light transmittance, haze, and YI value were measured with the following method, respectively.

[Bikat softening temperature]

It measured based on the B50 method prescribed | regulated to JISK7206: 1999 "The plastics-thermoplastic-bikat softening temperature (VST) test method." Vicat softening temperature was measured by the heat distortion tester ("148-6 mold type" by Yasuda Seiki Co., Ltd.). The test piece at that time press-molded each raw material to thickness of 3 mm, and measured it.

[Content of alkali metal]

It was measured by inductively coupled plasma mass spectrometry.

(MFR)

It measured according to the method prescribed | regulated to JISK7210: 1999 "The test method of the melt mass flow rate (MFR) and melt volume flow rate (MVR) of a plastics-thermoplastic plastic." About the material of a poly (methyl methacrylate) system, it is prescribed | regulated to this JIS to measure by temperature 230 degreeC and a load of 3.80 kg (37.3 N).

(MVR)

About the material of polycarbonate-type resin, it measured on the conditions of 300 degreeC under 1.2 kg load by "Tokyo Seiki Indexer 2A" by Toyo Seiki Co., Ltd. based on JISK7110.

[Full light transmittance and haze]

JIS K 7361-1: 1997 It measured with the haze transmittance meter ("HR-100" by Murakami Color Technology Research Institute) based on "Test method-Part 1: Single beam method of the total light transmittance of a plastic-transparent material."

(YI value)

It measured with "Spectrophotometer SQ2000" made by Nippon Denshoku Kogyo Co., Ltd.

[Average value of film thickness]

The film thickness of the resin laminated body was measured by the digital micrometer. The average value which performed the said measurement in ten points was made into the average value of the film thickness of the resin laminated body.

The measurement of the film thickness of each layer of an intermediate | middle layer (A), a thermoplastic resin layer (B), and (C) cuts a resin laminated body perpendicularly | vertically with respect to a surface direction, and polished a cross section using sand paper, It measured by observing with a square microscope. The average value which performed the said measurement in ten points was made into the average value of the film thickness of each layer.

[Peel strength]

A resin laminated body provided with a protective film was set in a tensileron tester ("Tensilon RTC-1210" made by ORIENTEC Co., Ltd.), and a peeling rate of 0.3 mm / min and a peeling angle of 180 were obtained according to JIS-Z0237 using a 10N load cell. It measured by 25 mm of measurement widths.

[Tensile modulus]

In accordance with JIS-K7127, a tensile test was performed using a test speed of 5 mm / min and a load cell of 5 kN in accordance with JIS-K7127, and the tensile modulus of elasticity was measured.

[Production example 1]

97.7 mass parts of methyl methacrylate and 2.3 mass parts of methyl acrylate were mixed, 0.05 mass part of chain transfer agents (octyl mercaptan) and 0.1 mass part of mold release agents (stearyl alcohol) were added, and the monomer liquid mixture was obtained. Furthermore, 0.036 mass part of polymerization initiators [1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane] were added to 100 mass parts of methyl methacrylates, and the initiator liquid mixture was obtained. The mixture was continuously supplied to a fully mixed polymerization reactor so that the flow rate ratio of the monomer mixture solution and the initiator mixture solution was 8.8: 1, and the polymerization was carried out to an average polymerization rate of 54% at an average residence time of 20 minutes at a temperature of 175 ° C to obtain a partial polymer. The obtained partially polymerized product was heated to 200 ° C., guided by a devolatilizing extruder equipped with a vent, and devolatilized unreacted monomer from the vent at 240 ° C., and the polymer after devolatilization was extruded and melted in a molten state, It cut and obtained the pellet-shaped methacryl resin (i).

The obtained pellet-shaped methacryl resin composition was analyzed by pyrolysis gas chromatography under the conditions shown below, and the respective peak areas corresponding to methyl methacrylate and acrylic acid ester were measured. As a result, the structural unit derived from methyl methacrylate was 97.0 mass%, and the structural unit derived from methyl acrylate was 3.0 mass% of methacryl resin (i).

[Content of structural unit by pyrolysis gas chromatography]

(Pyrolysis condition)

Sample preparation: The methacryl resin composition was precisely weighed (standard 2-3 mg), placed in the center portion of the metal cell in the shape of a gutter, and the metal cell was folded, and both ends were lightly pressed with a pliers to enclose it.

Pyrolysis device: CURIE POINT PYROLYZER JHP-22 (made by Nippon Bunseki Kogyo Co., Ltd.)

Metal cell: Pyrofoil F590 (manufactured by Nippon Bunseki Kogyo Co., Ltd.)

Set temperature of thermostat: 200 ℃

Set temperature of heat insulation pipe: 250 ℃

Pyrolysis Temperature: 590 ℃

Pyrolysis time: 5 seconds

(Gas chromatography analysis conditions)

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

Detection Method: FID

Column: 7G 3.2m × 3.1 mmφ (manufactured by Shimadzu Corporation)

Filler: FAL-M (Shimazu Corporation)

Carrier gas: Air / N2 / H2 = 50/100/50 (kPa), 80 ml / min

Temperature raising conditions of a column: After holding 15 minutes at 100 degreeC, it heated up to 150 degreeC at 10 degreeC / min, and held at 150 degreeC for 14 minutes.

INJ temperature: 200 ℃

DET temperature: 200 ℃

Peak area (a1) corresponding to methyl methacrylate and peak area corresponding to acrylate ester detected when the methacryl resin composition is thermally decomposed under the above-described pyrolysis conditions and the resulting decomposition product is measured under the above-mentioned gas chromatography analysis conditions. (b1) was measured. And the peak area ratio A (= b1 / a1) was calculated | required from these peak areas. On the other hand, the standard product of the methacrylic resin whose weight ratio of the acrylic ester unit to the methyl methacrylate unit is W ₀ (base) is pyrolyzed under the above pyrolysis conditions, and the resulting decomposition product is measured under the above gas chromatography analysis conditions. The peak area (a ₀ ) corresponding to methyl methacrylate detected at the time of performing and the peak area (b ₀ ) corresponding to acrylic acid ester are measured, and the peak area ratio A ₀ (= b ₀ / a ₀ from these peak areas). Saved. Also, the peak area ratio from the A ₀ and the weight ratio W _0, was determined the factor _{f (= W 0 / A 0} ).

By multiplying the said peak area ratio A by the said factor f, the weight ratio W of the acrylic ester unit with respect to the methyl methacrylate unit in the copolymer contained in the said methacrylic resin composition is calculated | required, and it is methyl methacrylate from the said weight ratio W. The ratio (mass%) of the methyl methacrylate unit with respect to the sum total of a unit and the acrylic ester unit, and the ratio (mass%) of the acrylic ester unit with respect to the said sum were computed.

[Production example 2]

A pellet-shaped methacryl resin (ii) was obtained in the same manner as in Production Example 1 except that 98.9 parts by mass of methyl methacrylate, 1.1 parts by mass of methyl acrylate, and 0.16 parts by mass of a chain transfer agent were obtained, and the content of the structural unit Was measured. The structural unit derived from methyl methacrylate was 97.5 mass%, and the methacryl resin (ii) was 2.5 mass% of the structural unit derived from methyl acrylate.

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

[Production example 3]

In order to masterize the bluing agent (MB), 99.99 parts by mass of the methacryl resin (i) obtained in Production Example 1 and 0.01 parts by mass of the colorant were dry blended, and a 40 mm diameter single screw extruder (manufactured by Tanabe Plastic Machinery Co., Ltd.) was used. It melt-mixed at the preset temperature of 250-260 degreeC, and obtained the colored masterbatch pellet (MB (i)). As a coloring agent, a blueing agent ("Sumiplast (trademark registered) Violet B" by Sumica Chemtex Co., Ltd.) was used.

In Examples and Comparative Examples, commercially available vinylidene fluoride resin having physical properties shown in Table 2 was used.

Vinylidene fluoride resin (i): polyvinylidene fluoride prepared by suspension polymerization

Vinylidene fluoride resin (ii): polyvinylidene fluoride prepared by suspension polymerization

Vinylidene fluoride resin (iii): polyvinylidene fluoride prepared by emulsion polymerization

The weight average molecular weight (Mw) of vinylidene fluoride resin was measured by GPC. To prepare a calibration curve for GPC, a polystyrene was used as a standard reagent, a calibration curve was created from the elution time and the 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 the measuring device, two "TSKgel SuperHM-H" and one "SuperH2500", which are columns manufactured by Tosoh Corporation, were arranged in series, and an RI detector was used as the detector.

In the Example, polycarbonate (i) was used as polycarbonate resin of a thermoplastic resin layer. The physical properties of the resin are shown in Table 3.

Polycarbonate resin (i): "Caliber (registered trademark) 301-30" made by Sumika styrene polycarbonate Co., Ltd.

The weight average molecular weight of the polycarbonate resin was measured by gel permeation chromatography (GPC). To prepare a calibration curve for GPC, a molecular weight distribution was used, using a methacrylic resin of known Showa Denko Co., Ltd. as a standard reagent, a calibration curve was prepared from the elution time and the molecular weight, and the weight average molecular weight of each resin composition was determined. Measured. Specifically, 40 mg of the resin was dissolved in 20 ml of a tetrahydrofuran (THF) solvent to prepare a measurement sample. As the measuring device, two "TSKgel SuperHM-H" and one "SuperH2500", which are columns manufactured by Tosoh Corporation, were arranged in series, and an RI detector was used as the detector.

[Manufacture of the resin laminated body provided with the protective film of Examples 1-9, Comparative Example 10, and Comparative Example 1]

Resin for mixing the methacryl resin and vinylidene fluoride resin shown in Table 1 and Table 2, and the master batch pellet MB (i) obtained by the manufacture example 3 by the ratio shown in Table 4, and forming an intermediate | middle layer (A). The composition (A) was obtained. As a resin composition (B) and (C) for forming a thermoplastic resin layer (B) and (C), the methacryl resin shown in Table 1 or the polycarbonate resin shown in Table 3 was used. From such a resin composition, the resin laminated body was manufactured using the apparatus shown in FIG. Specifically, the resin composition (A) is 65 mm φ single screw extruder 2 (manufactured by Toshiba Machine Co., Ltd.), and the resin compositions (B) and (C) are 45 mm φ single screw extruder 1 and 3 [Hitachi Manufactured by Josen Corporation]. Subsequently, these are laminated | stacked so that it may become the structure shown by said B layer / A layer / C layer via the feed block 4 (made by Hitachizosen Co., Ltd.) of 230-270 degreeC of set temperature, and the multi-manifold type dice 5 It extruded from [Hitachizosen Co., Ltd. product, two types, three layer distribution], and obtained film-form molten resin (6). In the present embodiment, the B layer and the C layer are layers of the same composition. And the obtained film-form molten resin 6 is sandwiched between the 1st cooling roll 7 and the 2nd cooling roll 8 which opposely arranged, and then wound around the 2nd cooling roll 8, After sandwiching between the 2 cooling rolls 8 and the 3rd cooling roll 9, it is wound around the 3rd cooling roll 9, shape | molded and cooled, and each layer has an average value of the film thickness shown in Table 5. The resin laminated body 10 of laminated constitution was obtained. The obtained resin laminated body 10 had a total film thickness of about 800 micrometers, and when it observed with the naked eye, it was colorless and transparent. It bonded together on both surfaces of the obtained resin laminated body, pressing the protective film which has the physical property shown in Table 5, and obtained the resin laminated body provided with a protective film.

[Appearance evaluation]

The resin laminated body provided with the protective film manufactured as mentioned above was cut | disconnected to the magnitude | size of width 1500mm, length 1500mm, and 20 sheets of resin laminated bodies provided with this protective film were laminated | stacked, and left still for 48 hours. After 48 hours, the protective film of the resin laminate provided with the protective film was peeled off, and the appearance of the surface of the thermoplastic resin layer was evaluated. Evaluation selects the resin laminated body provided with arbitrary 3 sheets of protective films from 18 sheets except the one which overlapped the top and bottom among the resin laminated bodies provided with 20 protective films, and, for each, is 1 m The number of visible holes per ^two was counted visually. The average value of three sheets was computed and it evaluated in four steps according to the evaluation criteria shown in Table 6. The evaluation results are shown in Table 7. In addition, the number of foreign matter in the air in the manufacturing environment (near the die) of the resin laminated body provided with a protective film, and the said stationary environment was measured using the particle size instrument (air particle counter) made from Leon Corporation. Table 8 shows the measurement results.

The dielectric constant of the resin laminated body in the resin laminated body provided with the protective films of Examples 1-9, Comparative Example 10, and Comparative Example 1 is 5.2 in Examples 1-9, 5.3 in Comparative Example 10, and Comparative Example In 1 it was 4.4. It was confirmed that any resin laminate has sufficient dielectric constant for use in display devices such as touch panels.

The total light transmittance (Tt) and haze (Haze) were measured using the resin laminated body provided with the protective films of Examples 1-9, Comparative Example 10, and Comparative Example 1. Furthermore, the resin laminated body provided with the protective films of Examples 1-9, Comparative Example 10, and Comparative Example 1 was exposed at 60 degreeC in the environment of 90% of a relative humidity for 120 hours, and the resin laminated body provided with the protective film after an durability test Similarly, the total light transmittance and the haze of the sieve were measured. The obtained results are shown in Table 9.

The resin laminated body provided with the protective film of this invention shown in Examples 1-9 had high transparency, and it was confirmed that appearance defects, such as dent, are hard to produce. Moreover, it was confirmed that high transparency is maintained even after the durability test under high temperature, high humidity conditions.

1 single screw extruder (extrudes melt of resin composition B)
2 Single Screw Extruder (Extrudes Melt of Resin Composition A)
3 Single Screw Extruder (Extrudes Melt of Resin Composition C)
4 feed blocks
5 Multi Manifold Dies
6 film-shaped molten resin
7 1st cooling roll
8 second cooling roll
9 third cooling roll
10 resin laminate
10A middle layer (A)
10B thermoplastic resin layer (B)
10C thermoplastic resin layer (C)
11 polarizer
12 optical adhesive layer
13 liquid crystal cell
14 liquid crystal display

Claims (16)

Protective film (D) and (E) which have a film base material at least on both surfaces of the resin laminated body which has an intermediate | middle layer (A) and the thermoplastic resin layer (B) and (C) which exist in both sides of the said intermediate | middle layer (A), respectively. As a resin laminated body provided with the protective film which respectively bonded),
The said intermediate | middle layer (A) contains 10-90 mass% (meth) acrylic resin and 90-10 mass% vinylidene fluoride resin based on all resin contained in the said intermediate | middle layer (A), The said (meth The weight average molecular weight (Mw) of the acrylic resin is 100,000-300,000,
Content of the alkali metal in an intermediate | middle layer (A) is 50 ppm or less based on all resin contained in the said intermediate | middle layer (A),
The resin laminated body provided with the protective film for display devices which protective film (D) and (E) satisfy | fill the following relationship, respectively.
E × L ³ ≥0.17
[In formula, E represents the tensile elasticity modulus (MPa) of a protective film, and L represents the average value (mm) of the film thickness of the film base material of a protective film.] The method of claim 1,
The protective film (D) and (E) have an adhesion layer, The resin laminated body provided with the protective film which are respectively stuck together on both surfaces of a resin laminated body through the said adhesion layer. delete The method according to claim 1 or 2,
The film base material of protective films (D) and (E) is at least 1 sort (s) of film chosen from the group which consists of a low density polyethylene film, a high density polyethylene film, a polypropylene film, a polyethylene terephthalate film, an acrylic resin film, and a polycarbonate film. A resin laminated body provided with a protective film. The method according to claim 1 or 2,
The film base material of protective films (D) and (E) is a resin laminated body provided with the protective film which is a high density polyethylene film or a polyethylene terephthalate film. The method according to claim 1 or 2,
The film base material of protective films (D) and (E) is a resin laminated body provided with the protective film which has an average value of the film thickness of 40 micrometers or more. The method according to claim 1 or 2,
The intermediate | middle layer (A) is equipped with the protective film containing 35-45 mass% (meth) acrylic resin and 65-55 mass% vinylidene fluoride resin based on all resin contained in the said intermediate | middle layer (A). Resin laminated body to do. The method according to claim 1 or 2,
(Meth) acrylic resin,
(a1) homopolymers of methyl methacrylate, and
(a2) It originates in the structural unit derived from 50-99.9 mass% methyl methacrylate based on all the structural units which comprise a polymer, and (meth) acrylic acid ester represented by 0.1-50 mass% of formula (1). The resin laminated body provided with the protective film which is any one or more of the copolymers containing at least 1 structural unit.

[In formula, R <_1> represents a hydrogen atom or a methyl group, when R <_1> is a hydrogen atom, R <_2> represents a C1-C8 alkyl group and when R <_1> is a methyl group, R <_2> represents a C2-C8 alkyl group. .] The method according to claim 1 or 2,
Vinylidene fluoride resin is a resin laminated body provided with the protective film which is polyvinylidene fluoride. The method according to claim 1 or 2,
Melt mass flow rate of vinylidene fluoride resin is a resin laminated body provided with the protective film which is measured at 3.8 kg load and 230 degreeC, and is 0.1-40 g / 10min. The method according to claim 1 or 2,
The resin laminated body provided with the protective film whose average value of the film thickness of a resin laminated body is 100-2000 micrometers, and whose average value of the film thickness of a thermoplastic resin layer (B) and (C) is 10-200 micrometers, respectively. The method according to claim 1 or 2,
The resin laminated body provided with the protective film whose vicat softening temperature of the thermoplastic resin contained in a thermoplastic resin layer (B) and (C) is 100-160 degreeC, respectively. The method according to claim 1 or 2,
The thermoplastic resin layer (B) and (C) are resin laminated bodies provided with the protective film which is a (meth) acrylic resin layer or a polycarbonate resin layer. The method according to claim 1 or 2,
The thermoplastic resin layer (B) and (C) are resin laminated bodies provided with a protective film containing 50 mass% or more of (meth) acrylic resin based on all resin contained in each thermoplastic resin layer. The method of claim 14,
The resin laminated body provided with the protective film whose weight average molecular weights of the (meth) acrylic resin contained in a thermoplastic resin layer (B) and (C) are 50,000-300,000. delete

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