KR20190052712A - Resin laminate and manufacturing method thereof - Google Patents

Abstract

It is an object of the present invention to provide a resin laminate which is suitably used in a display device or the like and is capable of suppressing occurrence of defective defects. (A) comprising a (meth) acrylic resin and a vinylidene fluoride resin as a resin component and a resin (B) having resin layers (B) and (C) present on both sides of the intermediate layer As the laminate, the vinylidene fluoride resin contained in the intermediate layer (A) has a crystallinity of 15.5 to 50%.

Description

Resin laminate and manufacturing method thereof

The present invention relates to a resin laminate, a display device including the resin laminate, and a process for producing the resin laminate.

2. Description of the Related Art Recently, a display device such as a smart phone, a portable game machine, an audio player, or a tablet terminal is increasingly equipped with a touch screen. Although a glass sheet is usually used on the surface of such a display device, a plastic sheet as a substitute for a glass sheet has been developed in view of the tendency of the display device to be lightweight and workability. For example, Patent Document 1 discloses a transparent sheet comprising a methacrylic resin and a vinylidene fluoride resin as a plastic sheet to be a substitute for a glass sheet, and the transparency and the dielectric constant are sufficiently satisfied .

Japanese Unexamined Patent Application Publication No. 2013-244604

BACKGROUND ART As regards a plastic sheet, in the manufacturing and distribution processes, for example, when a foreign matter such as fine dust present in the air is adhered to a sheet, a small indentation may occur on the surface of the plastic sheet. If such a defective plastic sheet is used for a display device, the visibility of the display device may be hindered. Therefore, it is an object of the present invention to provide a resin laminate which can be suitably used in a display device or the like and which can suppress the occurrence of pitting defects.

Means for Solving the Problems In order to solve the above problems, the inventors of the present invention have conducted extensive studies on a resin laminate suitably used in a display device, and have completed the present invention.

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

(1) A resin laminate having an intermediate layer (A) containing a (meth) acrylic resin and a vinylidene fluoride resin as a resin component and resin layers (B) and (C) present on both sides of the intermediate layer , And the crystallinity of the vinylidene fluoride resin contained in the intermediate layer (A) is 15.5 to 50%.

[2] The resin laminate according to [1], wherein the vinylidene fluoride resin to be contained in the intermediate layer (A) has a ratio of beta -deposition (crystal) in the vinylidene fluoride resin is 15 to 50%.

[3] The resin laminate according to [1] or [2], wherein the heterogeneous bonding ratio in the vinylidene fluoride resin contained in the intermediate layer (A) of the resin laminate is 10% or less.

(4) The intermediate layer (A) of the resin laminate contains 35 to 45 mass% of a (meth) acrylic resin and 65 to 55 mass% of a vinylidene fluoride resin based on the total resin component contained in the intermediate layer (A) The resin laminate according to any one of [1] to [3],

[5] The resin laminate according to any one of [1] to [4], wherein the (meth) acrylic resin has a weight average molecular weight (Mw) of 100,000 to 300,000.

[6] The alkali metal content in the intermediate layer (A) of the resin laminate is not more than 50 ppm based on the total resin component contained in the intermediate layer (A). The resin laminate according to any one of [1] to [5] sieve.

[7] The positive resist composition according to [

(a1) a homopolymer of methyl methacrylate, or

(a2) a structural unit derived from methyl methacrylate in an amount of 50 to 99.9 mass% and a structural unit derived from a structural unit derived from 0.1 to 50 mass% of the structural unit (1) based on the total structural units constituting the polymer,

[Chemical Formula 1]

(Wherein R ₁ represents a hydrogen atom or a methyl group and R ₁ represents a hydrogen atom, R ₂ represents an alkyl group of 1 to 8 carbon atoms, and when R ₁ represents a methyl group, R ₂ represents an alkyl group of ₂ to 8 ≪ / RTI >

A copolymer comprising at least one structural unit derived from a (meth) acrylic acid ester represented by the following formula

(a1) and (a2)

The resin laminate according to any one of [1] to [6].

[8] The resin laminate according to any one of [1] to [7], wherein the vinylidene fluoride resin is polyvinylidene fluoride.

[9] The resin laminate according to any one of [1] to [8], wherein the melt mass flow rate of the vinylidene fluoride resin is 0.1 to 40 g / 10 min as measured at 230 ° C. under a load of 3.8 kg.

[10] The resin laminate according to any one of [1] to [9], wherein at least one of the intermediate layer (A), the resin layer (B) and the layer (C) further comprises a colorant.

[11] The resin laminate according to any one of [1] to [10], wherein at least one of the intermediate layer (A), the resin layers (B) and (C) comprises an ultraviolet absorber.

[12] The resin laminate according to any one of [1] to [11], wherein an average thickness of the resin laminate is 100 to 2000 μm.

[13] The resin laminate according to any one of [1] to [12], wherein the average thickness of the resin layers (B) and (C) is 10 to 200 μm.

[14] The resin laminate according to any one of [1] to [13], wherein the softening temperatures of the resin layers (B) and (C) are 100 to 160 ° C, respectively.

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

[16] The resin laminate according to any one of [1] to [15], wherein the resin laminate has a tensile modulus of elasticity of 1400 MPa or more and 4000 MPa or less.

[17] A method for imparting at least one function of at least one function selected from the group consisting of a hard coating layer, an antireflection layer, an antiglare layer, an antistatic layer and an antiglare layer to at least one surface of the resin laminate The resin laminate according to any one of [1] to [16], further comprising a layer.

[18] The resin laminate according to any one of [1] to [17], which has a protective film on at least one of the outermost surfaces of the resin laminate.

[19] A display device comprising the resin laminate according to any one of [1] to [18].

[20] A method for producing a resin laminate as described in [1] to [18]

1) a step of laminating films formed from resin compositions (b), (a) and (c) respectively in this order to obtain a laminated film, and

2) a step of annealing the laminated film

/ RTI >

Wherein the resin composition (a) comprises at least a (meth) acrylic resin and a vinylidene fluoride resin which form the intermediate layer (A), and the resin compositions (b) and (c) And at least one thermoplastic resin or thermosetting resin contained in the resin compositions (b) and (c) is at least one kind of thermoplastic resin or thermosetting resin forming at least one thermoplastic resin or thermosetting resin, Way.

[21] The method according to [20], wherein the step 2) is performed by heating the laminated film to a temperature of 40 ° C to 90 ° C.

[22] The method according to [20] or [21], wherein the laminated film is cut, stacked, and annealed in step 2).

[23] The method described in any one of [20] to [22], wherein an annealing treatment is performed with a protective film and / or buffer material between the stacked laminated films.

INDUSTRIAL APPLICABILITY The resin laminate of the present invention is suitably used in a display device or the like because it is difficult to cause appearance defects such as pitting defects during manufacturing and distribution processes and also has small dimensional change before and after heating.

1 is a schematic view of an apparatus for producing a resin laminate of the present invention used in Examples.
2 is a schematic cross-sectional view showing a preferred embodiment of a liquid crystal display device including the resin laminate of the present invention.

The resin laminate of the present invention has an intermediate layer (A) comprising a (meth) acrylic resin and a vinylidene fluoride resin as resin components, and resin layers (B) and (C) present on both sides of the intermediate layer. The resin laminate of the present invention is a resin laminate in which a resin layer (B), an intermediate layer (A) and a resin layer (C) are laminated at least in this order.

The vinylidene fluoride resin contained in the intermediate layer (A) has a crystallinity of 15.5 to 50%. When the crystallinity of the vinylidene fluoride resin is lower than the above lower limit, the effect of suppressing the pitting defects can not be obtained and the dimensional change before and after heating tends to increase. The intermediate layer (A) preferably has a crystallinity of 16.0 to 45.0%, more preferably 17.0 to 40.0%, still more preferably 17.0 to 35.0%, particularly preferably 18.0 to 33.0%, still more preferably 19.0 to 40.0% 30.0%, particularly not less than 19.0% and less than 30.0%. In the present invention, the degree of crystallinity of the vinylidene fluoride resin refers to the ratio of the total of? -Chign and? -Definition in the vinylidene fluoride resin.

The crystallinity was evaluated by structural analysis of the vinylidene fluoride resin by ¹⁹ F-solid NMR spectroscopy. From the result of the waveform separation of the obtained spectrum, α-keto (-82, -96 ppm), ß-kole (-96 ppm) Based on the area ratio of the peaks derived from the amorphous (-91 ppm) and the heterogeneous (-113, -115 ppm) peaks, and calculating the sum of the angles of positive definite and positive definite.

¹⁹ F-solid NMR spectroscopy is described in Polymer Journal, Vol. 60, No. 4, pp. 145-157 (2003), as follows.

The resin laminate was freeze-pulverized and filled into a sample tube of 2.5 mmφ. Nuclear magnetic resonance apparatus: Measurement was carried out using AVANCEIII 400WB manufactured by Bruker Biospin under the following conditions.

Radionuclide: 19F

Observation frequency: 376.5 ㎒

Measurement method: MAS method (32 kHz)

Measuring temperature: 5 ℃

Chemical shift standard: PTFE (? = -122 ppm)

In the intermediate layer (A), the crystallinity in the above range can be obtained by a method of annealing a film containing a (meth) acrylic resin and a vinylidene fluoride resin as a resin component. For example, a resin composition containing a (meth) acrylic resin and a vinylidene fluoride resin as a resin component is melted and molded into a film, cooled and solidified, and then annealed at a temperature of 40 to 90 캜 .

The ratio of? In the vinylidene fluoride resin to the intermediate layer (A) is preferably 15.0 to 50.0%, more preferably 16.0 to 40.0%, further preferably 17.0 to 30.0%, particularly preferably 18.0 to 28.0% Still more preferably 19.0 to 27.5%. When the β definition ratio is within the above range, the crystallinity of the vinylidene fluoride resin increases while maintaining transparency in the resin laminate, thereby suppressing the pitting defects and reducing the dimensional change before and after heating. And a resin laminate having sufficient transparency tends to be obtained.

The? Definition ratio in the vinylidene fluoride resin was determined by the ¹⁹ F-solid NMR spectrum measurement described above.

The proportion of? In the vinylidene fluoride resin as the intermediate layer (A) is preferably 0.5 to 20.0%, more preferably 0.55 to 10.0%, and still more preferably 0.6 to 5.0%.

If the ratio of? definition is within the above range, sufficient transparency tends to be obtained in the resin laminate.

The definition of? In the vinylidene fluoride resin was obtained by the ¹⁹ F-solid NMR spectrum measurement described above.

The intermediate layer (A) is usually contained in an amount of 35 to 45 mass% (metha) based on the total resin component contained in the intermediate layer (A) from the viewpoint of increasing the dielectric constant and increasing the transparency of the resin laminate of the present invention. ) Acrylic resin and 55 to 65 mass% of vinylidene fluoride resin, and it preferably contains 36 to 43 mass% of a (meth) acrylic resin and 57 to 64 mass% of a vinylidene fluoride resin, (Meth) acrylic resin and 59 to 63 mass% vinylidene fluoride resin, and more preferably 37 to 40 mass% (meth) acrylic resin and 60 to 63 mass% vinylidene fluoride resin . In other words, the (meth) acrylic resin may be usually contained in an amount of about 53.8 to 81.8 parts by mass based on 100 parts by mass of the vinylidene fluoride resin, and it is preferable that the (meth) acrylic resin is contained in an amount of 56.2 to 75.4 parts by mass, More preferably 69.4 parts by mass of (meth) acrylic resin, and still more preferably 58.7 to 66.6 parts by mass of (meth) acrylic resin.

Examples of the (meth) acrylic resin contained in the intermediate layer (A) include homopolymers of (meth) acrylic monomers such as (meth) acrylic acid esters and (meth) acrylonitrile, homopolymers of (meth) And copolymers of (meth) acrylic monomers with monomers other than (meth) acrylic monomers. In the present specification, the term " (meth) acrylic " means " acrylic " or " methacrylic "

The (meth) acrylic resin is preferably a methacrylic resin from the viewpoint of enhancing hardness, weather resistance and transparency of the resin laminate. The methacrylic resin is a polymer of a monomer mainly composed of methacrylic acid ester (also referred to as alkyl methacrylate), and includes, for example, a homopolymer of methacrylic acid ester (also referred to as polyalkyl methacrylate) A copolymer of a methacrylic ester, and a copolymer of 50 mass% or more of methacrylic acid ester and 50 mass% or less of a monomer other than methacrylic acid ester. As the copolymer of the methacrylic acid ester and the monomer other than the methacrylic acid ester, from 70% by mass or more of the methacrylic acid ester and 30% by mass or less of the total amount of the monomers A copolymer with other monomers is preferable, and a copolymer of 90 mass% or more of methacrylic acid ester and 10 mass% or less of other monomers is more preferable.

Examples of the monomer other than the methacrylic acid ester include an acrylic acid ester and a monofunctional monomer having one polymerizable carbon-carbon double bond in the molecule.

Examples of monofunctional monomers include styrene monomers such as styrene,? -Methylstyrene and vinyltoluene; Cyanated alkenyl such as acrylonitrile and methacrylonitrile; Acrylic acid; Methacrylic acid; Maleic anhydride; N-substituted maleimides; And the like.

(Meth) acrylic resin may be copolymerized with N-substituted maleimide such as N-phenylmaleimide, N-cyclohexylmaleimide and N-methylmaleimide from the viewpoint of heat resistance, A lactone ring structure, a glutaric anhydride structure, or a glutarimide structure may be introduced into the skeleton or the main chain.

From the viewpoint that the hardness, weather resistance, and transparency of the resin laminate are easily increased, the (meth) acrylic resin is more specifically,

(a1) a homopolymer of methyl methacrylate, or

(a2) a structural unit derived from methyl methacrylate in an amount of 50 to 99.9% by mass, preferably 70.0 to 99.8% by mass, more preferably 80.0 to 99.7% by mass based on the total structural units constituting the copolymer, and (1) of 0.1 to 50 mass%, preferably 0.2 to 30 mass%, more preferably 0.3 to 20 mass%, still more preferably 0.3 to 10 mass%, and particularly preferably 0.3 to 5 mass% :

(2)

[Wherein, R ₁ is a hydrogen atom or a methyl group, R ₁ is R ₂ when one hydrogen atom is an alkyl group having 1 to 8 carbon atoms, when R ₁ is a methyl group R ₂ represents an alkyl group having a carbon number of 2 to 8 A copolymer comprising at least one structural unit derived from a (meth) acrylic acid ester represented by the following formula

(a1) and (a2)

. Here, the content of each structural unit can be calculated by analyzing the obtained polymer by pyrolysis gas chromatography and measuring the peak area corresponding to each monomer.

In the formula _(1), R 1 is a hydrogen atom or a methyl group, R ₁ is R _2, when one hydrogen atom is an alkyl group of 1~8 carbon atoms, R ₁ is a methyl group R ₂ is one when the number of carbon atoms Represents an alkyl group having 2 to 8 carbon atoms. Examples of the alkyl group having 2 to 8 carbon atoms include ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, From the viewpoint of heat resistance, R ₂ is preferably an alkyl group having 2 to 4 carbon atoms, more preferably an ethyl group.

The weight average molecular weight (hereinafter sometimes referred to as Mw) of the (meth) acrylic resin contained in the intermediate layer (A) is preferably 100,000 to 300,000, and when Mw is the lower limit or higher, When exposed, the transparency is sufficiently obtained. When the Mw is not more than the above-mentioned upper limit, the film-forming property at the time of producing the resin laminate tends to be enhanced. The Mw of the (meth) acrylic resin is more preferably 120,000 or more, and more preferably 150,000 or more, from the viewpoint of enhancing transparency when exposed under a high temperature and high humidity environment. The Mw of the (meth) acrylic resin is more preferably 250,000 or less, and more preferably 200,000 or less, from the viewpoint of film formation in the production of the resin laminate. The weight average molecular weight is measured by Gel Permeation Chromatography (GPC) measurement.

(Meth) acrylic resin is a melt of usually 0.1 to 20 g / 10 min, preferably 0.2 to 5 g / 10 min, more preferably 0.5 to 3 g / 10 min, measured at 230 캜 under a load of 3.8 kg And a mass flow rate (hereinafter sometimes referred to as MFR). The MFR is preferably not more than the above-mentioned upper limit because it is easy to increase the strength of the obtained film, and it is preferable from the viewpoint of film formation of the resin laminate that the lower limit is above. The MFR can be measured in accordance with the method specified in JIS K 7210: 1999 "Testing method of melt-mass flow rate (MFR) and melt volume flow rate (MVR) of plastic-thermoplastic plastics". For the poly (methyl methacrylate) type material, measurement at a temperature of 230 ° C and a load of 3.80 kg (37.3 N) is specified in this JIS.

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

The (meth) acrylic resin can be prepared by polymerizing the above monomers by a known method such as suspension polymerization or bulk polymerization. At that time, MFR, Mw, VST, etc. can be adjusted to a preferable range by adding a suitable chain transfer agent. The chain transfer agent may be a suitable commercially available product. The addition amount of the chain transfer agent may be suitably determined in accordance with the type and proportion of the monomers, the required characteristics, and the like.

Examples of the vinylidene fluoride resin contained in the intermediate layer (A) of the resin laminate of the present invention include homopolymers of vinylidene fluoride and copolymers of vinylidene fluoride and other monomers. From the viewpoint of enhancing the transparency of the resin laminate to be obtained, the vinylidene fluoride resin is preferably at least one selected from the group consisting of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether, (Vinylidene fluoride) copolymer, and / or a homopolymer of vinylidene fluoride (also referred to as polyvinylidene fluoride), and more preferably polyvinylidene fluoride .

In the vinylidene fluoride resin, the proportion of the hetero-bonds is preferably 1 to 20%, more preferably 3 to 17%, and further preferably 5 to 15%. The proportion of the hetero-bonds in the vinylidene fluoride resin was determined by the ¹⁹ F-solid NMR spectrum measurement described above.

The weight average molecular weight (Mw) of the vinylidene fluoride resin contained in the intermediate layer (A) is preferably 100,000 to 500,000, more preferably 150,000 to 450,000, and still more preferably 170,000 to 400,000. The Mw is preferably at least the lower limit described above because it is easy to increase the transparency of the resin laminate when the resin laminate of the present invention is exposed under an environment of high temperature and high humidity (for example, at 60 DEG C and a relative humidity of 90%). Further, it is preferable that the Mw is not more than the above upper limit because the film-forming property of the resin laminate is easily increased. The weight average molecular weight is measured by Gel Permeation Chromatography (GPC) measurement.

The vinylidene fluoride resin preferably has a weight of 0.1 to 40 g / 10 min, more preferably 0.5 to 35 g / 10 min, more preferably 1.0 to 30 g / 10 min, as measured at 230 캜 under a load of 3.8 kg Gt; (MFR) < / RTI > It is preferable that the MFR is not more than the upper limit of the above range because it is easy to suppress the decrease in transparency when the resin laminate is used for a long period of time. The MFR is preferably at least the lower limit of the above range because it is easy to form the resin laminate. The MFR can be measured in accordance with the method specified in JIS K 7210: 1999 "Testing method of melt-mass flow rate (MFR) and melt volume flow rate (MVR) of plastic-thermoplastic plastics".

The vinylidene fluoride resin is industrially produced by a suspension polymerization method or an emulsion polymerization method.

The suspension polymerization is carried out by using water as a medium, dispersing the monomer as a dispersant in a medium as a droplet, and polymerizing the organic peroxide dissolved in the monomer as a polymerization initiator. The polymerization is carried out in the presence of a polymer having a particle size of 100 to 300 mu m Is obtained. The suspension polymer is preferred because it is simple in the production process as compared with the emulsion polymer, has excellent handleability of powder, and does not contain an emulsifier or salting agent containing an alkali metal such as an emulsion polymer.

A commercially available product may be used as the vinylidene fluoride resin. Examples of preferable commercially available products include "KF Polymer (registered trademark) T # 1300, T # 1100, T # 1000, T # 850, W # 850, W # 1000, W # 1100 and W # 1300" &Quot; SOLEF (registered trademark) 6012, 6010 and 6008 "

The intermediate layer (A) may further contain another resin different from the (meth) acrylic resin and the vinylidene fluoride resin. In the case of containing other resin, the kind thereof is not particularly limited as long as the transparency of the resin laminate is not significantly impaired. From the viewpoint of the hardness and weather resistance of the resin laminate, the amount of other resin is preferably 15 mass% or less, more preferably 10 mass% or less, and more preferably 5 mass% or less based on the total resin contained in the intermediate layer (A) % Or less. Examples of the other resin include a polycarbonate resin, a polyamide resin, an acrylonitrile-styrene copolymer, a methyl methacrylate-styrene copolymer, and a polyethylene terephthalate. The intermediate layer (A) may further contain other resins, but from the viewpoint of transparency, the amount of other resins is preferably 1 mass% or less, and the resin contained in the intermediate layer (A) It is more preferable that the number is only a few.

The content of the alkali metal in the intermediate layer (A) may be 50 ppm or less, preferably 30 ppm or less, more preferably 10 ppm or less, and still more preferably 10 ppm or less, based on the total resin contained in the intermediate layer Is not more than 1 ppm. The content of the alkali metal in the intermediate layer (A) is preferably not more than the upper limit of the above range because it is easy to suppress the decrease in transparency when the resin laminate is used for a long time under a high temperature and high humidity environment. The lower limit value of the alkali metal content in the intermediate layer (A) is 0, and it is very preferable that the lower limit value of the alkali metal content in the intermediate layer (A) is substantially not included from the viewpoint of suppressing the decrease in transparency of the resin laminate. Here, in the (meth) acrylic resin and / or vinylidene fluoride resin contained in the intermediate layer (A), a small amount of emulsifier used in the production process remains. Therefore, an alkali metal such as sodium or potassium originating from the remaining emulsifier is contained in the intermediate layer (A), for example, 0.05 ppm or more. In particular, when the (meth) acrylic resin and / or the vinylidene fluoride resin contained in the intermediate layer (A) are obtained by emulsion polymerization, the amount of the emulsifier remaining in the resin increases and the amount of the alkali metal . It is preferable to use a resin having a small alkali metal content as the (meth) acrylic resin and the vinylidene fluoride resin contained in the intermediate layer (A) from the viewpoint of easily suppressing the decrease in transparency of the resin laminate.

In order to keep the content of the alkali metal in the resin within the above range, the amount of the alkali metal-containing compound used in polymerization of the resin may be reduced, or the cleaning process after polymerization may be increased to remove the alkali metal-containing compound. The content of the alkali metal can be determined, for example, by inductively coupled plasma mass spectrometry (ICP / MS). As the inductively coupled plasma mass spectrometry, for example, the sample pellets to be measured are subjected to a suitable method such as a high-temperature ashing melting method, a high-temperature painting acid dissolution method, a Ca addition painting acid dissolution method, a combustion absorption method, , The sample is dissolved, dissolved in an acid, the solution is adjusted, and the content of the alkali metal is measured by inductively coupled plasma mass spectrometry.

The resin laminate of the present invention has resin layers (B) and (C) present on both sides of the intermediate layer (A). In other words, in the resin laminate of the present invention, at least a resin layer (B), an intermediate layer (A) and a resin layer (C) are laminated in this order. Each of the resin layers (B) and (C) may be either a thermoplastic resin layer containing at least one thermoplastic resin or a thermosetting resin layer containing at least one thermosetting resin, and is preferably a thermoplastic resin layer . The resin layer (B) and the resin layer (C) may be the same resin layer or different resin layers.

The thermoplastic resin layer is preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 70% by mass or more, based on the total resin contained in each thermoplastic resin layer, Contains at least 80% by mass of a thermoplastic resin. The upper limit of the amount of the thermoplastic resin is 100% by mass. Examples of the thermoplastic resin include a thermoplastic (meth) acrylic resin, a polycarbonate resin, and a cycloolefin resin. The thermoplastic resin is preferably a thermoplastic (meth) acrylic resin or a polycarbonate resin from the viewpoint of enhancing adhesion between the resin layers (B) and (C) and the intermediate layer (A). The thermoplastic resin layer may contain the same thermoplastic resin or may include different thermoplastic resins. The thermoplastic resin layer preferably contains the same thermoplastic resin from the viewpoint that the warpage of the resin laminate can be easily suppressed. Hereinafter, the term "(meth) acrylic resin" in the description of the thermoplastic resin layer means "thermoplastic (meth) acrylic resin".

From the viewpoint of the heat resistance of the resin laminate, the thermoplastic resin contained in the thermoplastic resin layer preferably has a softening temperature of 100 to 160 DEG C, more preferably 102 to 155 DEG C, and still more preferably 102 to 152 DEG C . Here, the above-mentioned Vicat softening temperature is a Vicat softening temperature of the resin when the thermoplastic resin layer contains one kind of thermoplastic resin, and when the thermoplastic resin layer contains two or more kinds of thermoplastic resins, Of the mixture of thermoplastic resins. The Vicat softening temperature of the thermoplastic resin layer is measured according to the B50 method specified in JIS K 7206: 1999 " Plastics-Thermoplastics-Vicat softening temperature (VST) test method ". The Vicat softening temperature can be measured using a heat distortion tester (for example, "148-6 type" manufactured by Yasuda Seiki Co., Ltd.). The measurement may be performed by using a test piece having each raw material press-molded to a thickness of 3 mm.

The thermoplastic resin layer may further include a resin other than the thermoplastic resin, for example, a filler made of a thermosetting resin, resin particles or the like, for the purpose of enhancing the strength, elasticity, etc. of the thermoplastic resin layer. In this case, the amount of the other resin is preferably 40 mass% or less, more preferably 30 mass% or less, further preferably 20 mass% or less, based on the total resin contained in each thermoplastic resin layer. The lower limit of the amount of other resins is 0 mass%. As the thermosetting resin, those exemplified as thermosetting resins to be used in a thermosetting resin layer described later can be used.

In the case where the resin layer (B) and / or the resin layer (C) is a thermoplastic resin layer, the resin layer (B) and / or the resin layer (C) are excellent in moldability and easily adhered to the intermediate layer (A) Preferably a (meth) acrylic resin layer or a polycarbonate resin layer.

An embodiment of the present invention in which the resin layer (B) and / or the resin layer (C) is a (meth) acrylic resin layer will be described below. In this aspect, the (meth) acrylic resin layer includes at least one (meth) acrylic resin. (Meth) acrylic resin layer is preferably at least 50% by mass, more preferably at least 60% by mass, and still more preferably at least 60% by mass, based on the total resin contained in each (meth) acrylic resin layer, from the viewpoint of surface hardness (Meth) acrylic resin of 70 mass% or more.

Examples of the (meth) acrylic resin include resins described for the (meth) acrylic resin contained in the intermediate layer (A). The preferred (meth) acrylic resin described for the intermediate layer (A) is also preferably the same as the (meth) acrylic resin contained in the (meth) acrylic resin layer unless otherwise stated. (Meth) acrylic resin contained in the (meth) acrylic resin layer and the (meth) acrylic resin contained in the intermediate layer (A) may be the same or different.

The weight average molecular weight (Mw) of the (meth) acrylic resin is preferably 50,000 to 300,000, and more preferably 70,000 to 250,000 from the viewpoint of good molding processability and easy increase in mechanical strength. The weight average molecular weight is measured by Gel Permeation Chromatography (GPC) measurement.

In the embodiment wherein the resin layer (B) and / or the resin layer (C) is a (meth) acrylic resin layer, the (meth) acrylic resin layer may further include a thermoplastic resin other than (meth) acrylic resin. As the thermoplastic resin other than the (meth) acrylic resin, a thermoplastic resin compatible with the (meth) acrylic resin is preferable. Specific examples thereof include methyl methacrylate-styrene-maleic anhydride copolymer (for example, "Regispie" manufactured by Denki Kagaku Kogyo Co., Ltd.) and methyl methacrylate-methacrylic acid copolymer (for example, Glass HT121 "), polycarbonate resin. The thermoplastic resin other than the (meth) acrylic resin is preferably measured in accordance with JIS K 7206: 1999, preferably at least 115 ° C, more preferably at least 117 ° C, more preferably at least 120 ° C, It is preferable to have a softening temperature. From the viewpoints of heat resistance and surface hardness, it is preferable that the (meth) acrylic resin layer does not substantially contain a vinylidene fluoride resin.

In the embodiment wherein the resin layer (B) and / or the resin layer (C) is a (meth) acrylic resin layer, the pencil hardness of the (meth) acrylic resin layer is preferably not less than HB, More preferably H or more.

Next, another embodiment of the present invention in which the resin layer (B) and / or the resin layer (C) is a polycarbonate resin layer will be described below. In this aspect, the polycarbonate resin layer includes at least one polycarbonate resin. The polycarbonate resin layer is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, based on the total resin contained in each polycarbonate resin layer, from the viewpoint of impact resistance And a polycarbonate resin.

As the polycarbonate resin, for example, a phosgene method in which various dihydroxy diaryl compounds are reacted with phosgene, or an ester exchange method in which a dihydroxy diaryl compound is reacted with a carbonic ester such as diphenyl carbonate And specific examples thereof include polycarbonate resins prepared from 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A).

Examples of the dihydroxy diaryl compound include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2- , 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 3-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2- (Hydroxyaryl) alkanes such as 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxy-3,5-dichlorophenyl) (Hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy- Dihydroxydiaryl sulfide such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfide such as 4,4'-dihydroxydiphenyl sulfide, Dihydroxydiaryl sulfoxides such as dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, And dihydroxydiarylsulfone such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone.

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

The dihydroxyaryl compound may be used in combination with a trivalent or higher phenol compound as shown below. Examples of phenols having three or more valences include fluoroglucine, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6- - (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -Bis- [4,4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane, and the like.

As the polycarbonate resin other than the polycarbonate resin, polycarbonate synthesized from isosorbate and aromatic diol can be mentioned. An example of such a polycarbonate is DURABIO (registered trademark) manufactured by Mitsubishi Chemical Corporation.

As a polycarbonate resin, a commercially available product may be used. For example, " Cariba (registered trademark) 301-4, 301-10, 301-15, 301-22, 301-30, 40, SD2221W, SD2201W, TR2201 "

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

In the case where the resin layer (B) and / or the polycarbonate resin layer (C) is a polycarbonate resin layer, the polycarbonate resin contained in the polycarbonate resin layer is preferably measured at a temperature of 300 캜 and a load of 1.2 kg, (Hereinafter, referred to as " melt volume flow rate ") of from 1 to 120 cm 3/10 min, more preferably from 3 to 80 cm 3/10 min, more preferably from 4 to 40 cm 3/10 min, and particularly preferably from 10 to 40 cm 3 / MVR "). When the MVR is higher than the lower limit described above, the flowability is sufficiently high and molding is easy in melt co-extrusion molding or the like, and appearance defects are unlikely to occur. When the MVR is lower than the upper limit, the mechanical properties such as the strength of the polycarbonate resin layer are easily increased, which is preferable. The MVR can be measured under the condition of 300 DEG C under a load of 1.2 kg in accordance with JIS K 7210.

In the case where the resin layer (B) and / or the resin layer (C) is a polycarbonate resin layer, the polycarbonate resin layer may further include a thermoplastic resin other than one or more polycarbonate resins. The thermoplastic resin other than the polycarbonate resin is preferably a thermoplastic resin compatible with a polycarbonate resin, more preferably a (meth) acrylic resin, and more preferably a methacrylic resin having an aromatic ring or a cycloolefin in its structure. It is preferable that the polycarbonate resin layer contains a polycarbonate resin and the above (meth) acrylic resin because the surface hardness of the polycarbonate resin layer can be made higher than in the case of containing only polycarbonate resin.

Next, the thermosetting resin layer will be described. The thermosetting resin layer is preferably not less than 60% by mass, more preferably not less than 70% by mass, and more preferably not less than 80% by mass, based on the total resin contained in each thermosetting resin layer, Mass% or more of thermosetting resin. The upper limit of the amount of the thermosetting resin is 100% by mass. Examples of the thermosetting resin include a phenol resin, an epoxy resin, a thermosetting acrylic resin, a melamine resin, a urea resin, an unsaturated polyester resin, an alkyd resin, a polyurethane, and a thermosetting polyimide.

The thermosetting resin is preferably an epoxy resin, a thermosetting acrylic resin, or a thermosetting polyimide from the viewpoint of facilitating the adhesion between the resin layers (B) and (C) and the intermediate layer (A).

The thermosetting resin layer may contain the same thermosetting resin or may include different thermosetting resins. It is preferable that the thermosetting resin layer contains the same thermosetting resin from the viewpoint of easily suppressing the warpage of the resin laminated body.

The thermosetting resin contained in the thermosetting resin layer is preferably 90 to 250 占 폚 or higher, more preferably 95 to 220 占 폚 or higher, and more preferably 90 to 250 占 폚 or higher, in view of the heat resistance of the resin laminate, Lt; 0 > C or higher. Here, the above-mentioned load deflection temperature is a load deflection temperature of the resin when the thermosetting resin layer includes one kind of thermosetting resin, and when the thermosetting resin layer contains two or more kinds of thermosetting resins, It is the load deflection temperature of the mixture of resin. The load deflection temperature of the thermosetting resin layer is measured under a load condition of 1.80 MPa in accordance with Method A in the flat wise test prescribed in JIS K 7191: 2007 "Plastics - Determination of deflection temperature under load". The load deflection temperature can be measured using a heat distortion tester (for example, "148-6 type" manufactured by Yasuda Seiki KK).

The thermosetting resin layer may further include other resins such as a filler or a resin particle made of a thermosetting resin, a thermoplastic resin used for the above-mentioned thermoplastic resin layer, etc. for the purpose of increasing the strength and elasticity of the thermosetting resin layer . In this case, the amount of the other resin is preferably 40 mass% or less, more preferably 30 mass% or less, further preferably 20 mass% or less, based on the total resin contained in each thermosetting resin layer. The lower limit of the amount of other resins is 0 mass%.

When the resin layers (B) and (C) are thermosetting resin layers, the resin layers (B) and (C) are excellent in moldability and the adhesion between the resin layers (B) and (C) From the viewpoint of easy increase, it is preferably a thermosetting acrylic resin layer.

An embodiment of the present invention in which the resin layer (B) and / or the resin layer (C) is a thermosetting acrylic resin layer will be described below. In this aspect, the thermosetting acrylic resin layer comprises at least one thermosetting acrylic resin. The thermosetting acrylic resin layer is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, based on the total resin contained in each thermosetting acrylic resin layer, Or more thermosetting acrylic resin.

In the case where the resin layer (B) and / or the resin layer (C) is a thermosetting acrylic resin layer, the thermosetting acrylic resin layer may further include a thermosetting resin other than the thermosetting acrylic resin. The thermosetting resin other than the thermosetting acrylic resin is preferably a thermosetting resin compatible with the thermosetting acrylic resin. Specific examples thereof include epoxy resins and polyurethane resins. It is preferable that the thermosetting acrylic resin layer does not substantially contain a vinylidene fluoride resin.

At least one of the intermediate layer (A), the resin layers (B) and (C) in the resin laminate of the present invention further contains various commonly used additives within the range not impairing the effect of the present invention . Examples of the additives include colorants such as stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, foaming agents, lubricants, release agents, antistatic agents, flame retardants, mold release agents, polymerization inhibitors, flame retardant additives, reinforcing agents, nucleating agents and bluing agents .

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

When at least one of the intermediate layer (A), the resin layers (B) and (C) further comprises a coloring agent, the content of the coloring agent in each layer can be appropriately selected depending on the purpose, type of coloring agent and the like. When a bluing agent is used as the colorant, its content may be about 0.01 to 10 ppm based on the total resin contained in each layer containing the bluing agent. The content is preferably 0.01 ppm or more, more preferably 0.05 ppm or more, still more preferably 0.1 ppm or more, further preferably 7 ppm or less, further preferably 5 ppm or less, further preferably 4 ppm or less , Particularly preferably 3 ppm or less.

The blueing agent can be any of those known in the art and can be suitably used, for example, under the trade names of Mark Rolex (registered trademark) Blue RR (manufactured by Bayer), Markorox (registered trademark) Blue 3R (manufactured by Bayer), Sumiplast (Manufactured by Mitsubishi Chemical Co., Ltd.), and polyesters (registered trademark) Viloet B (manufactured by Sumika Chemical) and Polysincrene (registered trademark) Blue RLS (manufactured by Clariant), Diaresin Violet D, Diaresin Blue G and Diaresin Blue N have.

The ultraviolet absorber is not particularly limited, and various conventionally known ultraviolet absorbers may be used. For example, an ultraviolet absorber having an absorption maximum at 200 to 320 nm or 320 to 400 nm. Specific examples include triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers. As the ultraviolet absorber, one of these ultraviolet absorbers may be used alone or two or more of them may be used in combination. The use 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 be more effectively prevented from being damaged by ultraviolet rays desirable. Commercially available products may be used as the ultraviolet absorber. For example, "Kemisorb 102" (2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy- (Absorbance 0.1), "Adekastab LA-F70" (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'- (Absorbance: 0.2), "Adecastab LA-46" (2- (4,6-dihydroxybenzyl) (2- (2-ethylhexanoyloxy) ethoxy) phenol) (absorbance 0.05) or "Tinuvin 1577" manufactured by BASF Japan Co., (Absorbance: 0.1), etc. The absorbance of the exemplified ultraviolet absorbent is, for example, Absorbance at 380 nm This is an absorbance at 10 mg / L Concentration was dissolved in chloroform and the ultraviolet absorber, the spectrophotometer (for instance, the spectrophotometer HITACHI U-4100) can be measured by using the.

When at least one of the intermediate layer (A), the resin layers (B) and (C) further comprises an ultraviolet absorber, the content of the ultraviolet absorber in each layer is appropriately selected depending on the purpose, type of ultraviolet absorber, . For example, the content of the ultraviolet absorber may be about 0.005 to 2.0% by mass based on the total resin contained in each layer containing the ultraviolet absorber. The content of the ultraviolet absorber is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and still more preferably 0.03% by mass or more. The content of the ultraviolet absorber is preferably 1.5% by mass or less, more preferably 1.0% by mass or less. The content of the ultraviolet absorber is preferably at least the lower limit described above from the viewpoint of easily increasing the ultraviolet absorbing effect and it is easier to prevent the change of the color tone (for example, the yellowness YI) of the resin laminate desirable. For example, it is preferable to use the commercially available products "adecastab LA-31, LA-31RG, and LA-31G" in the amounts described above.

In another aspect of the present invention, it is preferable that the resin layers (B) and (C) are polycarbonate resin layers and include 0.005 to 2.0 mass% of ultraviolet absorbent based on the total resin contained in each resin layer. A resin laminate excellent in light resistance is easily obtained.

In the resin laminate of the present invention, the average value of the film thickness of the intermediate layer (A) is preferably 100 占 퐉 or more, more preferably 200 占 퐉 or more, and still more preferably 300 占 퐉 or more from the viewpoint of the dielectric constant. From the viewpoint of transparency, it is preferably 1500 占 퐉 or less, more preferably 1200 占 퐉 or less, and further preferably 1000 占 퐉 or less. The average value of the film thicknesses of the intermediate layer (A) is obtained by cutting the resin laminate perpendicularly to the surface direction, polishing the end surface with sandpaper, observing with a microscope (for example, a microscope made of micro- . The average value obtained by performing the measurement at arbitrary ten points is taken as an average value of the film thicknesses.

In the resin laminate of the present invention, the average value of the film thicknesses of the resin layers (B) and (C) is preferably 10 탆 or more, more preferably 30 탆 or more , And more preferably not less than 50 mu m. From the viewpoint of the dielectric constant, it is preferably not more than 200 mu m, more preferably not more than 175 mu m, further preferably not more than 150 mu m. The average value of the film thicknesses of the resin layers (B) and (C) can be measured in the same manner as described above for the intermediate layer.

In the resin laminate of the present invention, it is preferable that the mean value of the film thickness of the resin laminate is 100 to 2000 占 퐉 and the average value of the film thicknesses of the resin layers (B) and (C) It is preferable from the viewpoint that the warping of the sieve can be easily suppressed.

The average value of the above film thicknesses is preferably 100 占 퐉 or more, more preferably 200 占 퐉 or more, and still more preferably 300 占 퐉 or more from the viewpoint of easily increasing the rigidity of the resin laminate. From the viewpoint of transparency of the resin laminate, the thickness is preferably 2000 占 퐉 or less, more preferably 1,500 占 퐉 or less, and even more preferably 1,000 占 퐉 or less. The film thickness is measured by a digital micrometer, and the average value of the measured values at arbitrary ten points is taken as the average value of the film thickness.

The resin laminate of the present invention preferably has a dielectric constant of at least 3.5, more preferably at least 4.0, and even more preferably at least 4.1 from the viewpoint of obtaining a sufficient function for use in a display device such as a touch panel. The upper limit value of the dielectric constant is not particularly limited, but is usually 20. The dielectric constant can be adjusted within the above range by adjusting the type and amount of the vinylidene fluoride resin contained in the intermediate layer (A) of the resin laminate of the present invention, or by adding a high dielectric constant compound such as ethylene carbonate or propylene carbonate . The permittivity was determined in accordance with JIS K 6911: 1995, and the resin laminate was allowed to stand for 24 hours under an environment of a relative humidity of 50% at 23 DEG C, and under these circumstances, the resin laminate was subjected to an auto- . A commercially available instrument may be used for the measurement. For example, " precision LCR meter HP4284A " manufactured by Agilent Technologies, Inc. may be used.

The resin laminate of the present invention is preferably transparent when observed with naked eyes. Specifically, the resin laminate has a total light transmittance of not less than 85%, more preferably not less than 88%, more preferably not less than 89%, particularly preferably not less than 90% as measured according to JIS K7361-1: 1997 (Tt). The upper limit of the total light transmittance is 100%. It is preferable that the resin laminate after the 120-hour exposure at 60 DEG C and a relative humidity of 90% has a total light transmittance in the above range.

The resin laminate of the present invention may have a tensile elastic modulus of 1400 to 4000 MPa, preferably 1500 to 3500 MPa, more preferably 1600 to 3300 MPa, and further preferably 1700 to 3100 MPa. If the tensile modulus is within the above range, defective defects tend not to occur. The tensile modulus of the resin laminate was measured in accordance with JIS K7127 using an electromechanical universal testing machine manufactured by Instron using a test speed of 5 mm / min and a load cell of 5 kN to measure a tensile modulus of elasticity.

In the resin laminate of the present invention, the maximum load by the indentation test is preferably 30 to 300 N, more preferably 35 to 200 N, and even more preferably 40 to 150 N. If the maximum load by the indentation test is within the above range, defective defects tend to be hard to occur.

In the indentation test, by applying a constant load to the resin laminate, the maximum value of the load in which the surface of the resin laminate did not show any indentation was determined. Specifically, an indenter of 5 mmφ was attached to the tip of a load cell (MODEL-3050) for tensile compression using a precision load measuring instrument ("MODEL-1605VCL" manufactured by Aiko Engineering Co., Ltd.) , The load cell was dropped on the surface of the resin laminate, and after reaching the evaluation load, the laminate was allowed to stand for 15 seconds, and a load was applied to the resin laminate.

In the evaluation, when the appearance of the resin laminate one hour after weight lifting was visually observed, the load in which the pendulum was not seen was referred to as a maximum load.

The resin laminate of the present invention has a small dimensional change before and after the weather resistance test, and preferably has a dimensional change rate of -0.15 to 0.15%, more preferably -0.14 to 0.14%, after the weathering at 65 캜 for 30 minutes, , And more preferably -0.13 to 0.13%.

The dimensional change rate was obtained by the following equation.

[Equation 1]

The resin laminate is preferably not more than 2%, more preferably not more than 1.5%, as measured according to JIS K7136: 2000, using a resin laminate after exposure for 120 hours under an environment of a relative humidity of 90% at 60 캜 , More preferably not more than 1.0%, particularly preferably not more than 0.5%. The resin laminate is measured in accordance with JIS Z 8722: 2009 using a resin laminate after exposure to 120 hours at 60 캜 and a relative humidity of 90%, preferably 1.5 or less, more preferably 1.4 or less , And more preferably 1.3 or less (Yellow Index: YI value). The resin laminate having haze and yellowness described above is preferable because it is easy to maintain transparency and suppress yellowing in addition to being less prone to warp even when used in an environment of high temperature and high humidity.

The resin laminate of the present invention may further have at least one functional layer in addition to the intermediate layer (A) and the resin layers (B) and (C). It is preferable that the functional layer is present on the side of the resin layer (B) and / or the side of the resin layer (C) opposite to the intermediate layer (A). Examples of the functional layer include a hard coating layer, an antireflection layer, an antiglare layer, an antistatic layer, and an antiglare layer. These functional layers may be laminated on the resin laminate via an adhesive layer, or may be a coating layer laminated by coating. As the functional layer, for example, a cured coating film described in JP-A-2013-86273 may be used. The functional layer may be formed on one surface 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 a coating method, a sputtering method, Or may be a layer coated with an antireflective sheet on one side or both sides of the at least one functional layer.

The thickness of the functional layer may be appropriately selected depending on the purpose of each functional layer, but it is preferably at least 1 탆, more preferably at least 3 탆, even more preferably at least 5 탆 from the viewpoint of easy functioning Is preferably 100 占 퐉 or less, more preferably 80 占 퐉 or less, and even more preferably 70 占 퐉 or less from the viewpoint of easily preventing breakage of the functional layer.

The resin laminate of the present invention may further include a protective film described later on at least one of the outermost surfaces.

The resin laminate of the present invention can be produced by annealing the laminated film.

The laminated film refers to a resin laminate before the annealing treatment, and is a resin laminate comprising a resin composition (b) containing at least one kind of thermoplastic resin or a thermosetting resin, a resin composition containing a (meth) acrylic resin and a vinylidene fluoride resin and a film formed from a resin composition (c) comprising at least one thermoplastic resin or a thermosetting resin are laminated in this order. The films formed from the resin compositions (a), (b), and (c) respectively become the intermediate layer (A), the resin layer (B), and the resin layer (C) in the resin laminate after the annealing treatment of the laminated film. The at least one thermoplastic resin or thermosetting resin contained in the resin compositions (b) and (c) may be the same or different.

Therefore, the production method of the resin laminate of the present invention is characterized in that 1) a step of laminating the films formed respectively from the resin compositions (b), (a) and (c) in this order to obtain a laminated film, and 2) Wherein the resin composition (a) comprises at least a (meth) acrylic resin and a vinylidene fluoride resin forming the intermediate layer (A), and the resin compositions (b) and (c) Wherein at least one thermoplastic resin or thermosetting resin contained in the resin compositions (b) and (c) comprises at least one kind of thermoplastic resin or thermosetting resin forming the stratum layers (B) and (C) May or may not be.

The resin composition (a) may contain at least the (meth) acrylic resin and the vinylidene fluoride resin which give the intermediate layer (A) of the resin laminate of the present invention described above, A composition containing other components such as a resin different from the vinylidene fluoride resin, or a composition containing only (meth) acrylic resin and vinylidene fluoride.

As the (meth) acrylic resin, the vinylidene fluoride resin, optional additives as optional components, and other resins different from the (meth) acrylic resin and the vinylidene fluoride resin, which are optional components, contained in the resin composition (a) (A) of the resin laminate of the present invention can be used.

The resin composition (a) is obtained by usually kneading a (meth) acrylic resin and a vinylidene fluoride resin. The kneading can be carried out, for example, by a method including melt kneading at a temperature of 150 to 350 DEG C at a shear rate of 10 to 1000 / sec.

The temperature at which the melt-kneading is carried out is preferably 150 ° C or higher, because the resin can be sufficiently melted, and 350 ° C or lower is preferable because thermal decomposition of the resin is easily suppressed. The shear rate at the time of melt kneading is preferably 10 / sec or more because the resin is easily kneaded sufficiently, and 1000 / sec or less is preferable because decomposition of the resin is easily suppressed.

In order to obtain a resin composition in which each component is more uniformly mixed, melt kneading is preferably performed at a temperature of 180 to 300 캜, more preferably 200 to 300 캜, preferably 20 to 700 / Lt; RTI ID = 0.0 > 500 / sec. ≪ / RTI >

As a device used for melt kneading, a usual mixer or kneader can be used. Specific examples thereof include a uniaxial kneader, a twin-screw kneader, a twin-screw extruder, a Henschel mixer, a Banbury mixer, a kneader, and a roll mill. When the shearing speed is increased within the above range, a high-level shearing machine or the like may be used.

The resin composition (a) preferably contains 35 to 45 mass% of a (meth) acrylic resin and 55 to 65 mass% of a vinylidene fluoride resin based on the total resin component in the resin composition (a) (Meth) acrylic resin and 57 to 64 mass% vinylidene fluoride resin, and more preferably 37 to 41 mass% (meth) acrylic resin and 59 to 63 mass% vinylidene fluoride (Meth) acrylic resin and 60 to 63 mass% of vinylidene fluoride resin is particularly preferable.

The content of the other resin in the resin composition (a) is preferably 15 mass% or less, more preferably 10 mass% or less, and most preferably 5 mass% or less, based on the total resin component. From the viewpoint of transparency, the content of the other resin is preferably 1% by mass or less.

The content of the alkali metal in the resin composition (a) is preferably 50 ppm or less, more preferably 30 ppm or less, further preferably 10 ppm or less, particularly preferably 1 ppm or less, based on the total resin component .

The resin compositions (b) and (c) may contain at least a thermoplastic resin or a thermosetting resin for imparting the resin layers (B) and (C), respectively. The thermoplastic resin or the thermosetting resin, and the thermoplastic resin or the thermosetting resin Or any other additive, and may be a single kind of thermoplastic resin or a thermosetting resin. The resin compositions (b) and (c) may contain a thermoplastic resin or a thermosetting resin as a raw material constituting them. For example, the thermoplastic resin or the thermosetting resin may contain monomers and other components as required .

As the thermoplastic resin or thermosetting resin, the thermoplastic resin or any other resin other than the thermosetting resin and optional additives contained in the resin compositions (b) and (c), the resin layer (B ) And (C) can be used.

Each of the resin layers (B) and (C) may be either a thermoplastic resin layer containing at least one thermoplastic resin or a thermosetting resin layer containing at least one thermosetting resin, and is preferably a thermoplastic resin layer .

When the resin layer (B) and / or the thermoplastic resin layer (C) is a thermoplastic resin layer, the thermoplastic resin layer is preferably 60 mass% or more, more preferably 70 mass% or more based on the entire resin component contained in the thermoplastic resin layer %, More preferably at least 80 mass% of the thermoplastic resin. The upper limit of the amount of the thermoplastic resin is 100% by mass.

In the case where the resin layer (B) and / or the resin layer (C) is a thermosetting resin layer, the thermosetting resin layer is preferably 60 mass% or more, more preferably 70 mass% or more based on the total resin component contained in the thermosetting resin layer %, More preferably at least 80 mass% of the thermosetting resin. The upper limit of the amount of the thermosetting resin is 100% by mass.

The resin layers (B) and (C) are preferably 40 mass% or less, more preferably 30 mass% or less, and even more preferably 20 mass% or less based on the total resin component contained in each resin layer Of other resins. The lower limit of the amount of other resins is 0 mass%.

The resin compositions (b) and (c) used in the production of the thermoplastic resin layer can also be produced, for example, by melt-kneading at the above-mentioned temperature and shear rate in the same manner as the resin composition (a). If, for example, the thermoplastic resin layer contains one kind of thermoplastic resin, the film may be produced by melt-extrusion as described below without preliminarily melting and kneading.

The thermosetting resin layer formed from the resin compositions (b) and (c) can be obtained by, for example, mixing a monomer of a thermosetting resin and / or a thermosetting resin with other components in a batch, Heat, ultraviolet ray or the like.

When the resin compositions (a), (b) and (c) contain an additive, the additive may be contained in the resin contained in each layer in advance, or may be added at the time of melting and kneading the resin, Or may be added when the film is prepared using the resin composition. The content of the additives in the resin compositions (a), (b) and (c) may be a content of various commonly used additives within the range not impairing the effects of the present invention, and may be appropriately adjusted and used by those skilled in the art.

The method for producing a resin laminate according to the present invention comprises a step 1) of obtaining a laminated film by laminating films respectively formed from resin compositions (b), (a) and (c) in this order, and 2) a step of annealing the laminated film . First, the above step 1) will be described. (A), (b) and (c) can be obtained by, for example, a melt extrusion molding method, a solution casting film forming method, a hot press method, an injection molding method, (A), (b) and (c) may be a step of forming a laminated film by separately forming a film and bonding them together through a pressure-sensitive adhesive or an adhesive, Or may be a step of forming a laminated film by integrating the compositions (a), (b) and (c). When a laminated film is obtained by bonding, it is preferable to use an injection molding method or a melt extrusion molding method for the production of each layer, and it is more preferable to use a melt extrusion molding method. The step of forming a laminated film is a step of forming a laminated film by laminating the melted resin compositions (a), (b) and (c) by integrating the resin compositions (a), (b) and (c) , It is preferable because a resin laminate which is easily subjected to secondary molding is obtained in comparison with a laminated film obtained by bonding.

The melt co-extrusion molding may be carried out, for example, by putting the resin composition (a) and the resin compositions (b) and (c) separately into two or three single- or twin-screw extruders, (A), (b), and (c) are laminated and integrated through a feed block die or a multi-manifold die or the like. When the resin compositions (b) and (c) are the same composition, a single melted and melted composition in one extruder may be divided into two through a feed block die or the like to form a film. The obtained laminated film is preferably cooled and solidified by using, for example, a roll unit or the like, since it is easy to increase the degree of crystallization in a later annealing step.

Next, the step 2) for annealing the laminated film will be described. The annealing treatment can be performed by heating the laminated film at a temperature of 40 to 90 占 폚, preferably 45 to 85 占 폚, more preferably 50 to 80 占 폚. When the annealing treatment is carried out at the temperature within the above range, the degree of crystallization of the vinylidene fluoride resin in the intermediate layer (A) is easily increased. As a result, defects on the surface can be suppressed while maintaining transparency.

The time for heating the laminated film is not particularly limited as long as it can sufficiently increase the degree of crystallization, but it may be generally from 1 minute to 120 minutes, preferably from 5 minutes to 100 minutes, more preferably from 10 minutes to 80 minutes, It is 15 to 70 minutes.

The annealing treatment is preferably performed within 1 minute to 5000 hours after the laminated film is formed, more preferably within 6 hours to 3000 hours, and more preferably within 12 hours to 1000 hours.

The annealing process can be performed by using an apparatus capable of heating the laminated film to a predetermined temperature. Examples thereof include a heating oven, a hot air circulating type oven, an infrared ray heating furnace, a vacuum oven and a hot plate, and preferably a heating oven, a hot air circulating oven and an infrared ray heating furnace, Oven and infrared heating furnace.

The annealing process may be performed in a batch or in-line manner, or a combination thereof. In the case of performing the annealing process in the batch method, the laminated film can be cut, piled up, and annealed. When the laminated film is cut, the laminated film can be cut to a width of 500 to 3000 mm and a length of 500 to 3000 mm, for example. In the case of performing the annealing process in an in-line manner, for example, the annealing process can be performed after cooling and solidifying by a roll unit or the like. In this case, examples of the annealing treatment include a method of bringing the laminated film into contact with a temperature-controlled roll, a method of passing the laminated film through a heating oven, a hot air circulating oven, an infrared heating furnace, or a vacuum oven.

In the case where the annealing treatment is performed in a batch manner, it is preferable to carry out the annealing treatment by providing a protective film and / or a buffer material between the laminated film and the laminated film. In the case where a protective film and / or a buffer material is present between the laminated films, it is possible to suppress the occurrence of small pitting defects on the surface of the resin laminated body even when the laminated films having foreign substances such as fine dust are stacked on the surface Therefore, it is preferable.

The protective film may be a single layer film or a laminated film composed of a plurality of layers. When the protective film is a single-layer film, the base film becomes a protective film. The protective film may be stuck to at least one surface of the laminated film, for example, by electrostatic attraction, or may be stuck through the adhesive layer. The protective film is preferably applied to both surfaces of the laminated film, and it is more preferable that the protective film having an adhesive layer is applied to both surfaces of the laminated film through the adhesive layer. When a protective film is applied to both surfaces of the laminated film, the protective film may be the same film or different films. When the protective film having the film base material and the adhesive layer is applied to both surfaces of the laminated film, the protective film may have the same film base material and adhesive layer, may have different film base materials and adhesive layers, They may have the same film substrate and different adhesive layers, or may have different film substrates and the same adhesive layer. The protective film having the above-described film base material and the pressure-sensitive adhesive layer also includes a film substrate having adhesiveness.

The protective film may be laminated before cutting the laminated film, or may be laminated after cutting the laminated film. It is preferable that the protective film is attached before cutting the laminated film.

The film base of the protective film is not particularly limited as long as it can protect the surface of the laminated film. However, it is preferably a plastic film from the viewpoint of enhancing the protection of the surface of the laminated film and is preferably a low density polyethylene (LDPE) film, It is more preferably at least one film selected from the group consisting of a high density polyethylene (HDPE) film, a polypropylene (PP) film, a polyethylene terephthalate (PET) film, an acrylic resin film and a polycarbonate (PC) film. The film substrate of the protective film is more preferably an HDPE film, a PP film, or a PET film from the viewpoint of easily increasing the protection of the surface of the laminated film, and it is highly desirable that the film is a HDPE film or a PET film.

The tensile modulus of elasticity of the protective film is preferably 100 MPa or more, more preferably 150 MPa or more, and further preferably 200 MPa or more, from the viewpoint of easily enhancing the protection of the surface of the laminated film. The tensile modulus of elasticity of the protective film is preferably 5,000 MPa or less, more preferably 4,500 MPa or less, still more preferably 4,000 MPa or less, from the viewpoint of easily protecting the surface of the laminated film even in the presence of large foreign matters. MPa or less. The tensile modulus of elasticity of the protective film can be measured by, for example, an electromechanical universal testing machine manufactured by Instron, in accordance with JIS K7127. When the protective film has an adhesive layer, the tensile modulus of elasticity is measured using a protective film containing an adhesive layer.

The average value of the film thickness of the film base material of the protective film is preferably not less than 35 占 퐉, more preferably not less than 40 占 퐉, more preferably not less than 45 占 퐉, from the viewpoint of easily enhancing the protection of the surface of the laminated film. The average value of the film thickness of the film base material of the protective film is preferably 200 占 퐉 or less, more preferably 175 占 퐉 or less, and even more preferably 150 占 퐉 or less, from the viewpoint of easiness of coalescence. The average value of the film thickness of the film base material is measured by a digital micrometer, and the average value of the measured values at arbitrary ten points is taken as the average value of the film thickness.

The protective film acts as a role for suppressing the occurrence of indentation on the surface of the laminated film due to foreign matter or the like in the case where the annealing treatment is performed in a batch manner. However, after the annealing treatment, the surface of the obtained laminated resin is subjected to, for example, Or a protective role in the manufacturing process of the display device. The protective film is peeled from the surfaces of the resin layers (B) and (C) and the resin laminate having at least the intermediate layer (A) and the resin layers (B) and (C) And assembled as component parts.

The pressure-sensitive adhesive layer can be used, for example, in a manufacturing process, a circulation process, or the like, a pressure-sensitive adhesive layer having sufficient adhesiveness to maintain a state in which a protective film is stuck to the surface of the resin laminate, . From such a viewpoint, it is preferable that the protective film has a low adhesive force so that the protective film can be peeled off from the surface of the resin laminate by hand. Specifically, it is preferably 0.4 N / 25 mm or less, more preferably 0.35 N / 25 mm or less, more preferably 0.3 N / 25 mm or less. From the viewpoint of easily holding the protective film on the surface of the resin laminate, it is preferably 0.01 N / 25 mm or more, more preferably 0.02 N / 25 mm or more, still more preferably 0.03 N / And more preferably has a peel strength of 25 mm or more. The peel strength was measured according to JIS Z0237 at a peel rate of 0.3 mm / min, a peel angle of 180, and a measurement width of 25 mm.

The adhesive layer of the protective film is not particularly limited as long as it has the above-mentioned sticking property and releasability, and examples thereof include acrylic resin, rubber resin, ethylene-vinyl acetate copolymer resin, polyester resin, acetate resin, (LLDPE) or the like as a pressure-sensitive adhesive, for example, a pressure-sensitive adhesive, a pressure-sensitive adhesive, a pressure-sensitive adhesive, a pressure-sensitive adhesive, From the standpoint of practicality, it is more preferable that the pressure-sensitive adhesive layer contains acrylic resin, ethylene-vinyl acetate copolymer resin or linear low-density polyethylene (LLDPE) as a pressure-sensitive adhesive.

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

As the buffer material, a sheet made of foamed polyethylene, a hard urethane foam, a rubber urethane foam, a foamed urethane foam, an EPDM rubber sponge, a chloroprene rubber sponge, a natural rubber sponge and the like are preferable. The thickness of the buffer material is usually 0.5 to 3 mm, preferably 0.5 to 2 mm, and more preferably 0.5 to 1 mm.

The buffering agent may be adhered to the surface of the buffering agent by pasting with a pressure-sensitive adhesive, and the buffering agent may be laminated with the lamination film before or after cutting, or the buffering material may be interposed between the lamination film and the lamination film.

The resin laminate of the present invention can be used in various display devices. 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 the display device, a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, an electron emission display device (for example, (Display device using electronic ink or electrophoretic element), a plasma display device, a projection display device (for example, a grating light valve (GLV) display device, a digital micromirror A display device having a device (DMD)), and a piezoelectric ceramic display. The liquid crystal display device includes any of a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct viewing type liquid crystal display device, and a projection type liquid crystal display device. These display devices may be a display device for displaying a two-dimensional image or a stereoscopic display device for displaying a three-dimensional image. The resin laminate of the present invention is suitably used as, for example, a front plate or a transparent electrode in these display devices.

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

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

The film substrate of the plastic film in which the transparent conductive film has been formed in advance is not particularly limited as long as it is a transparent film capable of forming a transparent conductive film, And mixtures or laminates thereof. Before the formation of the transparent conductive film, the film may be coated with the object of improving the surface hardness, preventing Newton ring, imparting antistatic properties, and the like.

The method of laminating the plastic film on which the transparent conductive film has been formed in advance on the surface of the resin laminate of the present invention may be any method as long as it is a method in which there is no bubble or the like and a uniform and transparent sheet can be obtained. A method of lamination using an adhesive which is cured at room temperature, by heating, ultraviolet ray or visible light, or by a transparent adhesive tape.

As a film formation method of the transparent conductive film, there are known a vacuum deposition method, a sputtering method, a CVD method, an ion plating method, a spraying method and the like, and these methods can suitably be used depending on the required film thickness.

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

As a method of forming the transparent conductive film, a coating agent containing various conductive polymers capable of forming a transparent conductive film is applied to the surface of the resin laminate of the present invention and irradiated with ionizing radiation such as heat or ultraviolet rays A method of curing the coating, and the like can be applied.

As the conductive polymer, polythiophene, polyaniline, polypyrrole, and the like are known, and these conductive polymers can be used.

The thickness of the transparent conductive film is not particularly limited, but when a transparent conductive metal oxide is used, it is usually 50 to 2000 angstroms, preferably 70 to 5000 angstroms. In this range, both of conductivity and transparency are excellent.

The thickness of the transparent conductive sheet is not particularly limited, and it is possible to select the optimum thickness according to the specifications of the display product specification.

The touch panel can be manufactured by using the resin laminate of the present invention as a front panel of a display panel and using the transparent conductive sheet produced from the resin laminate of the present invention as a transparent electrode such as a touch screen. Specifically, the resin laminate of the present invention can be used as a window sheet for a touch screen, and the transparent conductive sheet can be used as an electrode substrate of a resistive film type or capacitive type touch screen. By disposing the touch screen on the front surface of a liquid crystal display device, an organic EL display device, or the like, an external mount type touch sensor panel having a touch screen function is obtained.

The present invention also provides a display device comprising the resin laminate of the present invention. The display device of the present invention can be, for example, the above-described display device.

Fig. 2 is a schematic cross-sectional view of a preferred embodiment of a liquid crystal display device including the resin laminate of the present invention. The resin laminate 10 of the present invention is laminated on the polarizing plate 11 via the optical adhesive layer 12 and this laminate can be disposed on the viewer side of the liquid crystal cell 13. [ On the back side of the liquid crystal cell 13, a polarizing plate 11 is usually disposed. The liquid crystal display device 14 is composed of such members. 2 is an example of a liquid crystal display device, and the display device of the present invention is not limited to this configuration.

Example

[Vicat softening temperature]

Measured according to JIS K 7206: 1999 " Plastics-Thermoplastic Plastics-Vicat Softening Temperature (VST) Test Method ". The Vicat softening temperature was measured with a heat distortion tester (" 148-6 type ", manufactured by Yasuda Seiki KK). The test piece at that time was press molded into each of the raw materials to a thickness of 3 mm and measured.

[Content of alkali metal]

Inductively coupled plasma mass spectrometry.

[MFR]

Was measured according to the method specified in JIS K 7210: 1999 " Test Method of Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Plastics-Thermoplastic Plastics ". For the poly (methyl methacrylate) type material, measurement at a temperature of 230 ° C and a load of 3.80 kg (37.3 N) is specified in this JIS.

[Overall light transmittance and haze]

("HR-100" manufactured by Murakami Color Research Laboratory Co., Ltd.) in accordance with JIS K 7361-1: 1997 "Test method for total light transmittance of plastic-transparent material - Part 1: Single beam method".

[Average value of film thickness]

The film thickness of the resin laminate was measured by a digital micrometer. The average value obtained by performing the above measurement at 10 points was regarded as an average value of the film thickness of the resin laminate.

The film thicknesses of the intermediate layer and the resin layer were measured by cutting the resin laminate perpendicularly to the surface direction, polishing the end surface with sandpaper, and observing with a micro-square microscope. The average value obtained by performing the above measurement at 10 points was regarded as an average value of the film thicknesses of the respective layers.

[Conditions for measuring ¹⁹ F-solid NMR spectrum]

Sample preparation: The resin laminate was freeze-pulverized and filled into a sample tube of 2.5 mmφ.

Nuclear magnetic resonance apparatus: manufactured by Bruker Biospin, AVANCE III 400WB

Radionuclide: 19F

Observation frequency: 376.5 ㎒

Measurement method: MAS method (32 kHz)

Measuring temperature: 5 ℃

Chemical shift standard: PTFE (? = -122 ppm)

From the results of the waveforms of the obtained spectra, it was found that the ratio of the peaks derived from? -Quinolones (-82, -96 ppm),? -Quinolin (-96 ppm), undifferentiated (-91 ppm) Then, the structural analysis of the vinylidene fluoride resin was carried out, and the respective ratios were calculated.

References: Polymer Journal, Vol. 60, No. 4, pp. 145-157 (2003)

[Indenter indentation test]

The appearance of the surface was evaluated by applying a constant load to the resin laminate with a precision load measuring instrument ("MODEL-1605VCL" manufactured by Aiko Engineering Co., Ltd.). The load was applied to the end of the tensile compression load cell (MODEL- A load was applied to the resin laminate by placing the indenter of mmφ and dropping the load cell at 1 mm / min, reaching the evaluation load, and standing for 15 seconds. When the appearance of the laminate was visually observed, the load at which the pendulum was not seen was referred to as a maximum load.

[Measurement of tensile modulus of elasticity]

The tensile elastic modulus was measured at room temperature (23 ° C) using an electromechanical universal testing machine manufactured by Instron, using a test speed of 5 mm / min and a load cell of 5 kN in accordance with JIS K7127.

(Production Example 1)

98.5 parts by mass of methyl methacrylate and 1.5 parts by mass of methyl acrylate were mixed, and 0.16 parts by mass of a chain transfer agent (octylmercaptan) and 0.1 part by mass of a release agent (stearyl alcohol) were added to obtain a monomer mixture. Further, 0.036 part by mass of a polymerization initiator [1,1-di (tert-butylperoxy) 3,3,5-trimethylcyclohexane] was added to 100 parts by mass of methyl methacrylate to obtain an initiator mixture. The mixture was continuously fed into a complete mixing type polymerization reactor so that the flow rate ratio of the monomer mixture liquid and the initiator mixture liquid was 8.8: 1, and the polymerization was carried out at an average polymerization time of 20 minutes and a temperature of 175 ° C at an average polymerization rate of 54%. The resulting partial polymer was heated to 200 ° C and introduced into a vented devolatilizing extruder. The unreacted monomer was deflected from the vent at 240 ° C., and the polymer after devolatilization was extruded in a molten state. After water cooling, To obtain a pellet-shaped methacrylic resin (i).

The obtained pellet-shaped methacrylic resin composition was analyzed by pyrolysis gas chromatography under the following conditions, and the respective peak areas corresponding to methyl methacrylate and acrylic ester were measured. As a result, the methacrylic resin (i) had a structural unit derived from methyl methacrylate of 97.5% by mass and a structural unit derived from methyl acrylate of 2.5% by mass.

(Pyrolysis condition)

Sample Preparation: The methacrylic resin composition was precisely weighed (standard: 2 to 3 mg) and placed in the center of a metal cell in the shape of a trough, and the metal cells were folded and both ends were lightly pushed .

Pyrolysis apparatus: CURIE POINT PYROLYZER JHP-22 (manufactured by Japan Analytical Industry Co., Ltd.)

Metal cell: Pyrofoil F590 (manufactured by Japan Analytical Industry Co., Ltd.)

Setting temperature of thermostat: 200 ℃

Setting temperature of heat pipe: 250 ℃

Pyrolysis temperature: 590 ℃

Pyrolysis time: 5 seconds

(Gas chromatographic analysis conditions)

Gas chromatographic analysis apparatus: GC-14B (manufactured by Shimadzu Corporation)

Detection method: FID

Column: 7G 3.2 m x 3.1 mm (manufactured by Shimadzu Corporation)

Filler: FAL-M (manufactured by Shimadzu Corporation)

Carrier gas: Air / N2 / H2 = 50/100/50 (㎪), 80 ml / min Column temperature elevation condition: After holding for 15 minutes at 100 ° C, the temperature was raised to 150 ° C at 10 ° C / 14 minutes at

INJ Temperature: 200 ° C

DET temperature: 200 DEG C

(A1) corresponding to the methyl methacrylate and a peak area corresponding to the acrylic acid ester which is detected when the decomposition product is measured under the above gas chromatography analysis conditions by thermally decomposing the methacrylic resin composition under the pyrolysis conditions (b1) was measured. Then, the peak area ratio A (= b1 / a1) was obtained from these peak areas. On the other hand, a standard product of a methacrylic resin (PMMA Standard M-75 manufactured by Showa Denko KK) having a weight ratio of structural units derived from acrylic acid ester to structural units derived from methyl methacrylate of W ₀ (known) (A ₀ ) corresponding to methyl methacrylate and a peak area (b ₀ ) corresponding to the acrylic acid ester which are detected when the decomposition products are subjected to the measurement under the gas chromatographic analysis conditions, And a peak area ratio A ₀ (= b ₀ / a ₀ ) was determined from these peak areas. Then, a factor f (= W ₀ / A ₀ ) was obtained from the peak area ratio A ₀ and the weight ratio W ₀ .

The weight ratio W of the structural units derived from the acrylic acid ester to the structural units derived from methyl methacrylate in the copolymer contained in the methacrylic resin composition is determined by multiplying the peak area ratio A by the factor f, (% By mass) of the structural unit derived from methyl methacrylate to the total of the structural unit derived from methyl methacrylate and the structural unit derived from acrylic ester from the weight ratio W and the ratio The ratio of the structural units (% by mass) was calculated.

The obtained methacrylic resin (i) had a structural unit derived from methyl acrylate of 2.5 mass%, MFR of 2 g / 10 min, Mw of 120,000, Vicat softening temperature of 110 占 폚, Na content of less than 0.01 ppm, K content Was less than 0.01 ppm.

The weight average molecular weight (Mw) of the (meth) acrylic resin was measured by gel permeation chromatography (GPC). For preparing the calibration curve of GPC, a calibration curve was prepared from the elution time and the molecular weight, using a methacrylic resin made by Showa Denko Co., Ltd. having a narrow molecular weight distribution and a known molecular weight as a standard reagent, The average molecular weight was measured. Specifically, 40 mg of the resin was dissolved in 20 ml of a tetrahydrofuran (THF) solvent to prepare a measurement sample. Two TSKgel SuperHM-H columns and one SuperH2500 column, which are columns made by TOSOH CORPORATION, were used in parallel as a measuring apparatus, and an RI detector was employed as a detector. The measured molecular weight distribution curve was fitting by using the normal distribution function by taking the logarithm of the molecular weight of the abscissa, and fitting was performed using the normal distribution function of the following formula.

&Quot; (2) "

(Production Example 2)

A methacrylic resin (ii) in the form of pellets was obtained in the same manner as in Production Example 1, except that 97.7 parts by mass of methyl methacrylate, 2.3 parts by mass of methyl acrylate and 0.05 parts by mass of chain transfer agent were used, Respectively. The methacrylic resin (ii) had 97.0% by mass of a structural unit derived from methyl methacrylate and 3.0% by mass of a structural unit derived from methyl acrylate.

The obtained methacrylic resin (ii) had a structural unit derived from methyl acrylate of 3 mass%, MFR of 0.5 g / 10 min, Mw of 180,000, Vicat softening temperature of 106 占 폚, Na content of less than 0.01 ppm, K content Was less than 0.01 ppm.

Table 1 shows the vinylidene fluoride resin used in Examples and their physical properties.

[Table 1]

The weight average molecular weight (Mw) of vinylidene fluoride was measured by GPC. For preparing the calibration curve of GPC, polystyrene was used 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 was measured. Specifically, 40 mg of the resin was dissolved in 20 ml of N-methylpyrrolidone (NMP) solvent to prepare a measurement sample. Two TSKgel SuperHM-H columns and one SuperH2500 column, which are columns made by Tosoh Corporation, were used as the measuring apparatuses, which were arranged side by side in series and an RI detector was employed as the detector.

(Production Example 3)

The methacrylic resin (ii) and the colorant were dry-blended at a ratio of 99.99: 0.01 in order to prepare a bluing agent masterbatch (MB), and the resulting blend was melt-kneaded with a 40 mmφ single screw extruder (Tanabe Plastic Machinery Co., Ltd.) And melted and mixed at 250 to 260 캜 to obtain a colored master batch pellet. As the coloring agent, a bluing agent ("Sumiplast (registered trademark) Violet B" manufactured by Sumika Chemtex Co., Ltd.) was used.

(Examples 1 to 3 and Comparative Example 1)

First, the methacrylic resin (ii), the resin 1, and the master batch pellets prepared in Production Example 3 were mixed at a ratio of 39: 60: 1 as the forming material of the intermediate layer to obtain a resin composition for use in the intermediate layer of the present invention . Subsequently, a lamination film was produced by using a manufacturing apparatus as illustrated in Fig. 2, 100 parts by mass of the methacrylic resin (i) as a material for forming the resin layer was extruded into a 45 mmφ single screw extruder 2 (manufactured by Toshiba Machine Co., Ltd.) with a 65 mmφ single screw extruder 2, (1 and 3) (manufactured by Hitachi, Ltd.). Subsequently, they were laminated so as to have a structure represented by the above-mentioned resin layer / intermediate layer / resin layer via a feed block 4 (manufactured by Hitachi, Ltd.) having a set temperature of 250 to 270 캜, 5) (distribution of two kinds of three layers, made by Hitachi, Ltd.) to obtain a film-like molten resin 6. The molten resin 6 thus obtained was sandwiched between the first cooling roll 7 (100 ° C) and the second cooling roll 8 (95 ° C) opposed to each other, and then the second cooling Is inserted between the second cooling roll 8 and the third cooling roll 9 (90 DEG C) while being wound around the roll 8, and wound around the third cooling roll 9 to be molded and cooled , A film thickness of the intermediate layer of 600 mu m, and a film thickness of the resin layer of 100 mu m. The total film thickness of the obtained laminated film 10 was 800 占 퐉, and when observed with naked eyes, it was colorless and transparent. The amount of the alkali metal (Na + K) contained in the intermediate layer was determined to be 0.21 ppm. The obtained laminated film 10 was heat-treated at a temperature shown in Table 2 for one hour to obtain a resin laminate.

[Table 2]

The dielectric constants of the resin laminate obtained in Examples 1 to 3 and Comparative Example 1 were 4.7 in Example 1, 4.5 in Example 2, 4.3 in Example 3, and 5.1 in Comparative Example 1. It has been confirmed that any one of the resin laminate has a sufficient dielectric constant for use in a display device such as a touch panel.

Using the resin laminate obtained in Examples 1 to 3 and Comparative Example 1, haze was measured according to JIS K7136: 2000, and the total light transmittance (Tt) was measured according to JIS K7361: 19971 . The obtained results are shown in Table 3.

Structural analysis of the vinylidene fluoride resin contained in the intermediate layer (A) was carried out by the solid-state NMR method using the resin laminate obtained in Examples 1 to 3 and Comparative Example 1. The obtained results are shown in Table 3.

Using the resin laminate obtained in Examples 1 to 3 and Comparative Example 1, the indentation indentation test was carried out to measure the maximum load at which the resin laminate did not protrude. The obtained results are shown in Table 3.

The tensile modulus of elasticity was measured using the resin laminate obtained in Examples 1 to 3 and Comparative Example 1. The obtained results are shown in Table 3.

The resin laminate obtained in Examples 1 to 3 and Comparative Example 1 was cut into a size of 110 mm x 60 mm, and the dimensional change after exposure at 65 占 폚 for 30 minutes was measured. The obtained results are shown in Table 3.

[Table 3]

As shown in Table 3, the resin laminate of the present invention shown in Examples 1 to 3 has a high maximum transparency and a high maximum load showing difficulty in peeling due to a high crystallinity and a high? , It was confirmed that generation of pitting defects was suppressed and the dimensional change was small. Therefore, it is understood that the resin laminate of the present invention is suitably used in a display device or the like.

A 1: 1 screw extruder (extruding the melt of the resin composition (b)
2: Single screw extruder (extruding the melt of the resin composition (a))
3: Single screw extruder (extruding the melt of the resin composition (c))
4: Feed block
5: Multi-manifold type die
6: Film-like molten resin
7: first cooling roll
8: Second cooling roll
9: Third cooling roll
10: laminated film
10A: intermediate layer (A)
10B: Resin layer (B)
10C: resin layer (C)
11: polarizer
12: Optical adhesive layer
13: liquid crystal cell
14: Liquid crystal display

Claims (15)

A resin laminate having an intermediate layer (A) containing a (meth) acrylic resin and a vinylidene fluoride resin as resin components and resin layers (B) and (C) present on both sides of the intermediate layer (A) And the crystallinity of the vinylidene fluoride resin contained in the intermediate layer (A) is 15.5 to 50%. The method according to claim 1,
The vinylidene fluoride resin contained in the intermediate layer (A) has a? Definition ratio of 15 to 50% in the vinylidene fluoride resin. 3. The method according to claim 1 or 2,
The intermediate layer (A) of the resin laminate contains 35 to 45% by mass of a (meth) acrylic resin and 65 to 55% by mass of a vinylidene fluoride resin based on the total resin component contained in the intermediate layer (A) Resin laminate. 4. The method according to any one of claims 1 to 3,
Wherein the weight average molecular weight (Mw) of the (meth) acrylic resin is 100,000 to 300,000. 5. The method according to any one of claims 1 to 4,
(Meth) acrylic resin,
(a1) a homopolymer of methyl methacrylate, or
(a2) a structural unit derived from methyl methacrylate in an amount of 50 to 99.9 mass% and a structural unit derived from a structural unit derived from 0.1 to 50 mass% of the structural unit (1) based on the total structural units constituting the polymer,
[Chemical Formula 1]

(Wherein R ₁ represents a hydrogen atom or a methyl group and R ₁ represents a hydrogen atom, R ₂ represents an alkyl group of 1 to 8 carbon atoms, and when R ₁ represents a methyl group, R ₂ represents an alkyl group of ₂ to 8 ≪ / RTI >
A copolymer comprising at least one structural unit derived from a (meth) acrylic acid ester represented by the following formula
is a mixture of (a1) and (a2). 6. The method according to any one of claims 1 to 5,
Wherein the vinylidene fluoride resin is polyvinylidene fluoride. 7. The method according to any one of claims 1 to 6,
Wherein the melt mass flow rate of the vinylidene fluoride resin is 0.1 to 40 g / 10 minutes as measured at 230 占 폚 under a load of 3.8 kg. 8. The method according to any one of claims 1 to 7,
Wherein the resin layers (B) and (C) are a (meth) acrylic resin layer or a polycarbonate resin layer. 9. The method according to any one of claims 1 to 8,
Wherein the resin laminate has a tensile elastic modulus of 1400 MPa or more and 4000 MPa or less. 10. The method according to any one of claims 1 to 9,
And a protective film on at least one of the outermost surfaces of the resin laminate. A display device comprising the resin laminate according to any one of claims 1 to 10. The method for producing a resin laminate according to any one of claims 1 to 10,
1) a step of laminating films formed from resin compositions (b), (a) and (c) respectively in this order to obtain a laminated film, and
2) annealing the laminated film,
Wherein the resin composition (a) comprises at least a (meth) acrylic resin and a vinylidene fluoride resin which form the intermediate layer (A), and the resin compositions (b) and (c) And at least one thermoplastic resin or thermosetting resin contained in the resin compositions (b) and (c) is at least one kind of thermoplastic resin or thermosetting resin forming at least one thermoplastic resin or thermosetting resin, Way. 13. The method of claim 12,
Step 2) is carried out by heating the laminated film to a temperature of 40 캜 to 90 캜. The method according to claim 12 or 13,
In the step 2), the laminated film is cut, and the laminated film is stacked and annealed. 15. The method of claim 14,
And a protective film and / or a buffer material are present between the stacked laminated films to perform an annealing treatment.

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