TWI639030B - Laminated body, manufacturing method thereof, retardation film, polarizing film, and manufacturing method of IPS liquid crystal panel - Google Patents

Abstract

A laminate comprising a multi-layer film (A), a multi-layer film (B) and a first-layer adhesive layer, wherein the multi-layer film (A) comprises a substrate (A1) and is inherently connected to the substrate (A1) a layer (A2) of a non-liquid crystal material having a positive birefringence; the double layer film (B) having a layer (B1) of a non-liquid crystal material having a negative intrinsic birefringence and a negative connection to the intrinsic birefringence a resin layer (B2) of a layer (B1) of a liquid crystal material; and the layer of the first layer is separately interposed between the layer (A2) of the non-liquid crystal material having a positive intrinsic birefringence and the substrate (A1) The surface on the opposite side and the surface (B1) of the non-liquid crystal material having a negative intrinsic birefringence are opposite to the surface on the opposite side to the resin layer (B2).

Description

Laminated body, manufacturing method thereof, retardation film, polarizing plate, and manufacturing method of IPS liquid crystal panel

The present invention relates to a laminate including an optical element, a method for producing the same, a retardation film, a polarizing plate, and an IPS liquid crystal panel.

The liquid crystal display device has advantages of high image quality, thinness, light weight, low power consumption, and the like, and is widely used in, for example, televisions, personal computers, car navigation systems, and the like. In a liquid crystal display device, liquid crystal cells are disposed between two polarizers (that is, an incident side polarizer and an output side polarizer) that are disposed so that transmission axes are orthogonal to each other, and are applied to liquid crystal cells. The voltage changes the alignment of the liquid crystal molecules to cause the image to be displayed on the screen.

In the liquid crystal display device, when the screen is generally viewed from a direction parallel to the transmission axis of the polarizer, sufficient contrast can be obtained. However, when the screen is viewed obliquely from a direction that is not parallel to the transmission axis, since the transmission axis of the incident side polarizer and the transmission axis of the emission side polarizer are not orthogonal in appearance, the linear polarization is not completely blocked. A situation in which light leakage occurs. When light leakage occurs, sufficient black cannot be obtained and the contrast is low. Therefore, in the liquid crystal display device, in order to prevent the contrast of the screen from being lowered, there is a case where an optical compensation film is attempted.

As the optical compensation film, a retardation film is usually used. For the retardation film, for example, as disclosed in Patent Documents 1 to 10, various types have been developed previously. A variety of technologies.

Prior technical literature

Patent literature

[Patent Document 1] Japanese Patent No. 3977743

[Patent Document 2] Japanese Patent No. 3962034

[Patent Document 3] Japanese Patent No. 3795512

[Patent Document 4] Japanese Patent No. 4070510

[Patent Document 5] Japanese Patent No. 4107741

[Patent Document 6] Japanese Patent No. 4636622

[Patent Document 7] Japanese Patent No. 4586326

[Patent Document 8] Japanese Patent No. 4433854

[Patent Document 9] Japanese Patent No. 4369222

[Patent Document 10] Japanese Patent No. 2660601

In recent years, for example, in a portable terminal device such as a mobile phone or a tablet type personal computer, a touch panel has been widely used. Since the display unevenness does not occur during use, it is suitable to use an IPS (In-Plane Switching) type liquid crystal cell as the liquid crystal display device used in the touch panel. Further, as the optical compensation film used in the liquid crystal display device including the IPS type liquid crystal cell, a retardation film in which a plurality of retardation films having different optical characteristics are combined is usually used.

With the recent thinning of portable terminal equipment, optical compensation Films are also required to be thinner. However, since the optical compensation film used in the liquid crystal display device of the IPS type liquid crystal cell is a phase difference film in which a plurality of retardation films are combined, it is difficult to reduce the thickness.

In the case of a specific example, when the thickness of the retardation film is generally thinned, the retardation film is easily broken, so that it is difficult to stably produce a thin optical compensation film. In particular, when a plurality of thin film retardation films having a small thickness are bonded together, it is difficult to stably perform the bonding while preventing the retardation film from being damaged. Therefore, it is difficult to employ a preferred manufacturing method in industrial production such as a roll to roll method.

Further, when the thickness of the retardation film is made thinner, the influence of the thickness variation of the retardation film on the optical performance tends to be large. Therefore, it is difficult to maintain the thickness of the optical compensation film while maintaining the same optical compensation performance as the prior art.

The present invention has been made in view of the above problems, and an object of the invention is to provide a laminated body capable of realizing a film having a desired optical performance and having a thin thickness and capable of being stably produced, and a method for producing the same, and a method for producing the same; A retardation film which is optically stable and thin, and which can be stably produced; and a polarizing plate and an IPS liquid crystal panel including the retardation film.

As a result of intensive studies to solve the above problems, the present inventors have found a laminate in which a retardation film having a desired optical performance and having a small thickness and stably produced can be realized, and the present invention has been completed. The laminated system comprises a multi-layer film (A), a multi-layer film (B) and a layer of an adhesive layer, wherein the multi-layer film (A) has a substrate (A1) and the intrinsic birefringence is positive a layer (A2) of a non-liquid crystal material; the multi-layer film (B) is provided with a layer (B1) and a resin layer (B2) of a non-liquid crystal material having a negative intrinsic birefringence; and the layer of the layer is an individual layer The surface of the layer (A2) of the non-liquid crystal material having the positive intrinsic birefringence is between the surface of the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence.

That is, the present invention is as follows.

[1] A laminate comprising a multi-layer film (A), a multi-layer film (B) and a lamination layer, wherein the multi-layer film (A) is provided with a substrate (A1) and is bonded to the substrate (A1) a layer (A2) having a positive birefringence which is a positive non-liquid crystal material; the multi-layer film (B) having a layer (B1) of a non-liquid crystal material having a negative intrinsic birefringence and a connection to the intrinsic birefringence a resin layer (B2) of a layer (B1) of a negative non-liquid crystal material; and the layer of the first layer is separately interposed between the layer (A2) of the non-liquid crystal material having a positive intrinsic birefringence and the substrate (A1) is a surface on the opposite side and a surface of the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence which is opposite to the resin layer (B2).

[2] The laminate according to [1], wherein a peeling force between the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence and the resin layer (B2) is 0.5 N/20 mm or less.

[3] The laminate according to [1] or [2], wherein a peeling force between the substrate (A1) and the layer (A2) of the non-liquid crystal material having a positive intrinsic birefringence is 0.05 N/ 20mm or less.

[4] The laminate according to any one of [1] to [3] wherein the glass transition temperature of the material of the substrate (A1) is positive and the non-liquid crystal having a positive intrinsic birefringence The difference in glass transition temperature of the material is in the range of +15 ° C to -15 ° C.

[5] The laminate according to any one of [1] to [4] wherein the glass transition temperature Tg (B1) of the non-liquid crystalline material having the intrinsic birefringence is negative and the resin layer (B2) The relationship of the glass transition temperature Tg (B2) of the resin is such that Tg(B1)>Tg(B2)+20°C is satisfied.

[6] The layered body according to any one of [1] to [5] wherein the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence has a tensile elongation at break of 20% or less.

[7] The laminate according to any one of [1] to [6] wherein the substrate (A1) is selected from the group consisting of a polymer resin having an alicyclic structure, a (meth)acrylic resin, It is formed by a resin of a group consisting of a polycarbonate resin, a (meth) acrylate-vinyl aromatic compound copolymer resin, and a polyether oxime resin.

[8] The laminate according to any one of [1] to [7] wherein the intrinsic birefringence is a positive non-liquid crystalline material selected from the group consisting of polyimine resin and maleic acid. A group consisting of an amine resin, a polyamidoximine resin, a polycarbonate resin, a polyester resin, and a polyurethane urea resin.

[9] The laminate according to any one of [1] to [8] wherein the intrinsic birefringence is a negative non-liquid crystalline material, which is selected from the group consisting of styrenes, styrenes, and cis a polymer obtained by polymerizing a monomer of one or more types consisting of a group consisting of enedioic acid, maleimide, and (meth) acrylate, and a polymer selected from the group consisting of a polycarbonate polymer and a polyester polymer And a mixture of one or more types of polymers of a group consisting of polyarylene ether polymers.

[10] The laminate according to any one of [1] to [9] wherein the resin layer (B2) is selected from a polymer resin having an alicyclic structure, (meth) propyl It is formed of a resin composed of an olefin resin, a polycarbonate resin, a (meth) acrylate-vinyl aromatic compound copolymer resin, and a polyether oxime resin.

[11] A method of producing a laminate according to any one of [1] to [10], comprising: a solution in which a non-liquid crystal material having a positive intrinsic birefringence is dissolved in a solvent a step of developing the substrate (A1); a step of drying the developed solution; and a step of stretching the substrate (A1) to obtain the multilayer film (A).

[12] A method of producing a laminate according to any one of [1] to [10], comprising: forming a non-liquid crystal material having a negative intrinsic birefringence and forming the resin layer The resin of (B2) is co-extruded to obtain a layer (B1) having the resin layer (B2), a non-liquid crystal material having a negative intrinsic birefringence, and a multi-layer film of the resin layer (B2). a step of b), a step of extending the laminated film (b); and peeling the resin layer (B2) on one side from the stretched film (b) to obtain the multilayer film (B) step.

[13] A method of producing a laminate according to any one of [1] to [10], comprising: a layer (A2) of a non-liquid crystal material having positive intrinsic birefringence; One side opposite to the base material (A1) and one side of the surface opposite to the resin layer (B2) of the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence a step of forming the aforementioned adhesive layer; The step of bonding the above-mentioned adhesive layer and the surface on which the other side of the adhesive layer is not formed is bonded.

[14] A retardation film obtained by peeling the substrate (A1) and the resin layer (B2) from the laminate according to any one of [1] to [10].

[15] A polarizing plate comprising a polarizer and a retardation film according to [14].

[16] An IPS liquid crystal panel comprising an IPS type liquid crystal cell and a polarizing plate according to [15].

According to the present invention, it is possible to provide a laminated body capable of realizing a film having a desired optical performance and having a thin thickness and capable of being stably manufactured, and a method of manufacturing the same; and providing a film having a desired optical property and having a small thickness and capable of A retardation film produced stably; and a polarizing plate and an IPS liquid crystal panel including the retardation film.

10‧‧‧Multilayer film (A)

11‧‧‧Substrate (A1)

Surface of 11U‧‧‧ substrate (A1)

12‧‧‧Layer of non-liquid crystalline material with intrinsic birefringence (A2)

12U‧‧‧Face of the non-liquid crystalline material layer (A2) having the opposite intrinsic birefringence and the opposite side of the substrate (A1)

20‧‧‧Multilayer film (B)

21‧‧‧Layer of non-liquid crystalline material with inherent birefringence (B1)

21D‧‧‧Face of the non-liquid crystalline material layer (B1) having a negative intrinsic birefringence and the opposite side of the resin layer (B2)

22‧‧‧Resin layer (B2)

30‧‧‧Next layer

100‧‧‧Layer

200‧‧‧Manufacturing device for laminated film (A)

210‧‧‧Expanding Department

220‧‧‧Drying Department

230‧‧‧Extension

240‧‧‧solution

250‧‧‧Extended film

300‧‧‧Manufacturing device for laminated film (b)

310‧‧‧ Extension of laminated film (b)

320‧‧‧Film Forming Department

321‧‧‧Mold

322‧‧‧Cooling roller

330‧‧‧Extension

340‧‧‧Multilayer film before extension (b)

400‧‧‧Manufacturing device for laminated bodies

410‧‧‧ peeling department

420‧‧‧ Coating Department

430‧‧‧Fitting Department

431‧‧‧Fitting roller

432‧‧‧pair rolls

440‧‧‧ Hardening Department

450‧‧‧Resin layer (B2)

460‧‧‧Binder

500‧‧‧Polar plate

510‧‧‧ polarizer

520‧‧‧ phase difference film

530‧‧‧Next layer or adhesive layer

600‧‧‧ LCD panel

610‧‧‧LCD

Fig. 1 is a view schematically showing a cross section of a laminated body according to an embodiment of the present invention, which is cut in a plane perpendicular to the principal surface thereof.

Fig. 2 is a schematic view showing an example of a manufacturing apparatus for producing a multi-layer film (A).

Fig. 3 is a schematic view showing an example of a manufacturing apparatus for manufacturing a multi-layer film (b).

Fig. 4 is a schematic view showing an example of an apparatus for bonding a multi-layer film (A) and a multi-layer film (B) to produce a laminate.

Fig. 5 is a view schematically showing a cross section of a polarizing plate according to an embodiment of the present invention, which is perpendicular to a plane of a principal surface.

Fig. 6 is a view schematically showing a cross section of a liquid crystal panel according to an embodiment of the present invention, which is perpendicular to a plane of a principal surface.

Form for implementing the invention

Hereinafter, the present invention will be described in detail by explaining the embodiments, the examples, and the like. However, the present invention is not limited by the embodiments and the examples disclosed below, and may be arbitrarily changed without departing from the scope of the invention and the scope of the invention.

In the following description, the term "long strip" means a length of at least 5 times or more with respect to the width, preferably 10 times or more, and specifically means that it can be wound into a roll. The length of the degree of being stored or transported.

Moreover, the "base material" and the "polarizing plate" are not only rigid members but also flexible members such as a resin film.

Further, the hysteresis value in the in-plane direction of the film is a value represented by (nx-ny) × d unless otherwise notified in advance. Further, the hysteresis value in the thickness direction of the film is a value expressed by {|nx+ny|/2-nz}×d unless otherwise notified in advance. Here, nx means a direction perpendicular to the thickness direction of the film (in-plane direction) and a refractive index in a direction providing the maximum refractive index. The ny system indicates the in-plane direction and is a refractive index in a direction orthogonal to the direction of nx. The nz line indicates the refractive index in the thickness direction. d is the thickness of the film. These hysteresis values can be obtained by using a commercially available phase difference measuring device (for example, manufactured by Oji Scientific Instruments Co., Ltd.). "KOBRA-21ADH", manufactured by Photonic Lattice, "WPA-micro" or Senarmont.

In addition, "(meth)acrylate" means "acrylate" or "methacrylate"; "(meth)acryloyl group" means "acryloyl" or "methyl" "Acrylhydrazine"; "(meth)acrylonitrile" means "acrylonitrile" or "methacrylonitrile".

In addition, "ultraviolet light" means light having a wavelength of 1 nm or more and 400 nm or less. ]

Further, the directions of the elements are "parallel", "vertical", and "orthogonal", and may be included in an error of, for example, ±5° within a range that does not impair the effects of the present invention, unless otherwise notified. Moreover, the so-called "along" in a certain direction means "parallel" to a certain direction.

Further, the MD direction is the flow direction of the film of the manufacturing line, and is usually parallel to the longitudinal direction and the longitudinal direction of the long film. Further, the traverse direction is a direction parallel to the film surface and perpendicular to the MD direction, and is generally parallel to the width direction and the lateral direction of the long film.

Further, the fact that the intrinsic birefringence is positive means that the refractive index in the extending direction is larger than the refractive index in the direction orthogonal to the extending direction, and the intrinsic birefringence is negative, which means that the stretching is longer than The refractive index in the direction orthogonal to the direction has a small refractive index in the extending direction. The value of intrinsic birefringence can also be calculated from the dielectric constant distribution.

Further, as long as the polymer described below is not specifically notified, the ratio of the structural unit contained in the polymer is usually The ratio of the total monomer of the polymer to the monomer of the aforementioned structural unit (addition ratio) is identical.

[1. Laminated body]

Fig. 1 is a view schematically showing a cross section of a laminated body according to an embodiment of the present invention, which is cut in a plane perpendicular to the principal surface thereof. As shown in Fig. 1, the laminated body 100 is provided with a multi-layer film (A) 10, a multi-layer film (B) 20, and a multi-layer film (A) 10 and a multi-layer film (B) 20 followed by a layer 30. .

[1.1. Multilayer film (A)]

As shown in Fig. 1, the multi-layer film (A) 10 is provided with a substrate (A1) 11 and a layer (A2) 12 of a non-liquid crystal material. Since the layer (A2) 12 of the non-liquid crystal material is connected to the substrate (A1) 11, no other layer is provided between the substrate (A1) 11 and the layer (A2) 12 of the non-liquid crystal material.

[1.1.1. Substrate (A1)]

As the substrate (A1), a resin film is usually used. The type of the resin to be formed (A1) is not particularly limited, and a transparent resin is preferred. Here, the term "transparent" means a light transmittance which is suitable for use in an optical member, and is, for example, a test piece having a thickness of 1 mm. The total light transmittance measured is usually 70% or more, preferably 80% or more, and particularly preferably 90% or more. Further, the upper limit of the total light transmittance is usually 100%. The rate can be measured by using a spectrophotometer (manufactured by JASCO Corporation, UV-Vis NIR spectrophotometer "V-570") in accordance with JIS K0115.

Examples of the resin forming the material of the base material (A1) include a polyolefin resin such as a polyethylene resin or a polypropylene resin; a polymer resin having an alicyclic structure such as a decene-based resin; Amine resin, polyamidamine tree Lipid, polyamide resin, polyether oxime resin, polyether ether ketone resin, polyether ketone resin, polyketone sulfide resin, polyether oxime resin, polyfluorene resin, polyphenylene sulfide resin, poly Phenyl ether resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polyacetal resin, polycarbonate resin, polyarylate resin, Methyl)acrylic resin, polyvinyl alcohol resin, polypropylene resin, cellulose resin, epoxy resin, phenol resin, (meth) acrylate-vinyl aromatic compound copolymer resin, isobutylene / N-methyl cis Butylenediamine copolymer resin, styrene/acrylonitrile copolymer resin, and the like. These types may be used alone or in combination of two or more types in any ratio. For example, an isobutylene/N-methylbutyleneimine copolymer resin and a styrene/acrylonitrile copolymer resin are preferably used in combination as a mixture.

Among these, it is selected from a polymer resin having an alicyclic structure, a (meth)acrylic resin, a polycarbonate resin, a (meth) acrylate-vinyl aromatic compound copolymer resin, and a polyether oxime. The resin of the group consisting of resins is preferred. These resins are excellent in mechanical strength and can reduce the hysteresis value which appears due to stretching.

A polymer resin having an alicyclic structure is a resin containing a polymer having an alicyclic structure. Further, the polymer having an alicyclic structure is a polymer having a structural unit containing an alicyclic structure as a structural unit of a polymer, a polymer having an alicyclic structure in a main chain, and an alicyclic ring in a side chain. Any of the polymers of the formula can be used. Further, the polymer having an alicyclic structure may be used alone or in combination of two or more kinds in any ratio. From the viewpoints of mechanical strength, heat resistance, etc., especially in the main chain containing fat A polymer of a ring structure is preferred.

Examples of the alicyclic structure include a saturated alicyclic hydrocarbon (cycloalkane) structure, an unsaturated alicyclic hydrocarbon (cycloalkenene, cycloalkyne) structure, and the like. From the viewpoints of mechanical strength, heat resistance and the like, in particular, a naphthene structure and a cycloolefin structure are preferable, and particularly a naphthene structure is particularly preferable.

The number of carbon atoms constituting the alicyclic structure is preferably 4 or more, preferably 5 or more, preferably 30 or less, preferably 20 or less, and particularly preferably 15 or less per alicyclic structure. The following range. Thereby, mechanical strength, heat resistance, and film formability can be highly balanced, which is suitable.

The ratio of the structural unit containing an alicyclic structure among the polymers having an alicyclic structure can be appropriately selected depending on the purpose of use. Specifically, the ratio is preferably 55 wt% or more, more preferably 70 wt% or more, particularly preferably 90 wt% or more, and usually 100 wt% or less. When the ratio of the structural unit containing an alicyclic structure in the polymer having an alicyclic structure is in this range, it is preferable from the viewpoint of heat resistance.

Examples of the polymer having an alicyclic structure include a norbornene-based polymer, a monocyclic cyclic olefin-based polymer, a cyclic conjugated double bond-based polymer, and a vinyl alicyclic hydrocarbon-based polymerization. And the hydrides of the materials. Among these, since the formability is good, a decene-based polymer is suitable.

Examples of the norbornene-based polymer include a ring-opening polymer having a monomer having a norbornene structure, a ring-opening copolymer having a monomer having a norbornene structure and any monomer, or the like. a hydride; an addition polymer of a monomer having a norbornene structure; or an addition copolymer of a monomer having a norbornene structure and any monomer, or a hydride of the same. Among these, from formability, heat resistance, From the viewpoints of low hygroscopicity, dimensional stability, lightness, and the like, a ring-opened (co)polymer hydride having a monomer having a norbornene structure is particularly suitable. The term "(co)polymer" as used herein means a polymer and a copolymer.

Examples of the monomer having a norbornene structure include bicyclo [2.2.1] hept-2-ene (common name: norpene) and tricyclo [4.3.0.12, 5] 癸-3, 7 -diene (common name: dicyclopentadiene), 7,8-benzotricyclo[4.3.0.12,5]non-3-ene (common name: methylenetetrahydroanthracene), tetracyclic [4.4 .0.12, 5.17, 10] dodecyl-3-ene (common name: tetracyclododecene), and derivatives of such compounds (for example, those having a substituent in the ring) and the like. Here, examples of the substituent include an alkyl group, an alkylene group, and a polar group. Further, the substituents may be the same or different and may be bonded in a plurality of bonds to form a ring. Further, the monomer having a decene-lowering structure may be used alone or in combination of two or more kinds in any ratio.

Examples of the monomer which can be ring-open-copolymerized with a monomer having a norbornene structure include, for example, monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene, and derivatives thereof; a cyclic conjugated double bond such as a diene or a cycloheptadiene or a derivative thereof. Any monomer which can be subjected to ring-opening copolymerization with a monomer having a norbornene structure may be used singly or in combination of two or more kinds in any ratio.

a ring-opening polymer of a monomer having a norbornene structure, and a ring-opening copolymer of any monomer copolymerizable with a monomer having a norbornene structure, for example, by a conventional ring opening polymerization The monomer is polymerized or copolymerized in the presence of a medium to produce.

Examples of the monomer which can be copolymerized with a monomer having a norbornene structure include, for example, ethylene, propylene, and 1-butene having 2 to 20 carbon atoms. Alpha-olefins and derivatives thereof; cyclic olefins such as cyclobutene, cycloheptene, cyclohexene and the like; and derivatives thereof; 1,4-hexadiene, 4-methyl-1,4- A non-conjugated double bond such as hexadiene or 5-methyl-1,4-hexadiene. Among these, α-olefin is preferred, and ethylene is preferred. In addition, any monomer which can be copolymerized with a monomer having a norbornene structure may be used alone or in combination of two or more kinds in any ratio.

An addition polymer of a monomer having a norbornene structure, and an addition copolymer of any monomer capable of copolymerizing a monomer having a norbornene structure, for example, can be contacted by a conventional addition polymerization In the presence of a medium, a monomer is polymerized or copolymerized to produce.

The cyclic olefin polymer which is a monocyclic ring may, for example, be an addition polymer of a cyclic olefin monomer having a single ring such as cyclohexene, cycloheptene or cyclooctene.

The cyclic conjugated double bond polymer may, for example, be an cyclization reaction of an addition polymer of a conjugated double bond monomer such as 1,3-butadiene, isoprene or chloroprene. The obtained polymer; a 1,2- or 1,4-addition polymer of a cyclic conjugated double bond monomer such as cyclopentadiene or cyclohexadiene; and such a hydride or the like.

Examples of the vinyl alicyclic hydrocarbon-based polymer include a polymer of a vinyl alicyclic hydrocarbon monomer such as vinylcyclohexene or vinylcyclohexane, and a hydrogenated product thereof; a hydrogenated product obtained by partially hydrogenating an aromatic ring contained in a polymer obtained by polymerizing a vinyl aromatic hydrocarbon monomer such as ethylene or α-methylstyrene; a vinyl alicyclic hydrocarbon monomer or ethylene; Aromatic ring hydride of a copolymer of a random aromatic copolymer or a block copolymer of any monomer capable of copolymerizing the vinyl aromatic hydrocarbon monomer Wait. Examples of the block copolymer include a diblock copolymer, a multi-block copolymer of a triblock copolymer or the like, and a tilted block copolymer.

The (meth)acrylic resin is a resin containing a (meth)acryl-based polymer. Further, the (meth)acryl-based polymer means a polymer of (meth)acrylic acid or a (meth)acrylic acid derivative. Examples of the (meth)acryl-based polymer include homopolymers and copolymers of acrylic acid, acrylate, acrylamide, acrylonitrile, methacrylic acid, and methacrylic acid ester. Further, the (meth) propylene-based polymer may be used singly or in combination of two or more kinds in any ratio. Since the (meth)acrylic resin is high in strength and hard, the strength of the laminate can be improved.

The (meth) propylene-based polymer is preferably a polymer containing a structural unit formed by polymerizing a (meth) acrylate. The (meth) acrylate is, for example, an alkyl ester of (meth)acrylic acid. In particular, it is preferred to have a structure derived from (meth)acrylic acid and an alkanol or a cycloalkanol having 1 to 15 carbon atoms, and a structure derived from an alkanol having 1 to 8 carbon atoms is Preferably.

Specific examples of the acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, second butyl acrylate, and tert-butyl acrylate. N-hexyl acrylate, cyclohexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, and the like. These types may be used alone or in combination of two or more types in any ratio.

Further, specific examples of the methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, and methacrylic acid. Isopropyl ester, n-butyl methacrylate, isobutyl methacrylate, second butyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, methacrylic acid 2-ethylhexyl ester, n-decyl methacrylate, n-dodecyl methacrylate, and the like. These types may be used alone or in combination of two or more types in any ratio.

In addition, the (meth) acrylate may have a substituent such as a hydroxyl group or a halogen atom as long as it does not significantly impair the effects of the present invention. Examples of the (meth) acrylate having such a substituent include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, and A. 2-hydroxypropyl acrylate, 4-hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, glycidyl methacrylate, and the like. Further, these substituents may be used alone or in combination of two or more kinds in any ratio.

Further, the (meth)acryl-based polymer may be a polymer of only (meth)acrylic acid or a (meth)acrylic acid derivative, or may be a (meth)acrylic acid or a (meth)acrylic acid derivative and capable of a copolymer of any monomer copolymerized therewith. Examples of the optional monomer include α,β-ethylenically unsaturated carboxylic acid ester monomers other than (meth) acrylate, and α,β-ethylenically unsaturated carboxylic acid monomers and alkenyl aromatic groups. Monomer, conjugated double bond monomer, non-conjugated double bond monomer, carboxylic acid unsaturated alcohol ester, and olefin monomer. Further, any of the monomers may be used alone or in combination of two or more kinds in any ratio.

However, the ratio of the structural unit having a structure in which (meth)acrylic acid or a (meth)acrylic acid derivative is polymerized in the (meth)acryl-based polymer is preferably 55 wt% or more, more preferably 70% by weight or more, especially good for 90% by weight or more, and usually, it is usually 100% by weight or less.

Among these acrylic polymers, polymethacrylate is preferred, and polymethyl methacrylate is preferred.

A polycarbonate resin is a resin containing a polycarbonate polymer. Further, the polycarbonate polymer is a polymer having a structural unit bonded by a carbonate bond (-O-C(=O)-O-). The polycarbonate polymer may be used singly or in combination of two or more kinds in any ratio.

In particular, as the polycarbonate polymer, those having a structural unit represented by the following formula (I) are preferred. The structural unit represented by the following formula (I) can be formed, for example, by polymerizing bisphenol Z. The resin containing such a polycarbonate polymer is, for example, Lexan manufactured by SABIC.

In the formula (I), R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or an aryl group. Further, the alkyl group, the cycloalkyl group and the aryl group may be substituted or unsubstituted. Further, the alkyl group, the cycloalkyl group, or the aryl group usually has 1 to 10 carbon atoms.

In the formula (I), R ⁹ is a hydrogen atom or an alkyl group or an aryl group. Here, the number of carbon atoms of the alkyl group and the aryl group is usually from 1 to 9.

In formula (I), the Z system together with the carbon atom to which it is bonded forms a residue of a saturated or unsaturated carbocyclic ring having 4 to 11 carbon atoms. Especially as Z, the number of carbon atoms A saturated carbon ring of 6 is preferred.

Among the above, R ¹ or R ³ is preferably an alkyl group having 1 to 10 carbon atoms, and a methyl group is preferred. Further, R ⁶ or R ⁸ is preferably an alkyl group having 1 to 10 carbon atoms, and preferably a methyl group.

In particular, the structural unit represented by the formula (I) is particularly preferably a structural unit represented by the formula (II) (bisphenol Z unit).

The polycarbonate polymer is preferably a structural unit represented by the following formula (III), in addition to the structural unit represented by the formula (I). The structural unit represented by the following formula (III) can be formed, for example, by polymerizing bisphenol A. In particular, the structural unit represented by the formula (III) is preferably a structural unit represented by the formula (IV) or (V).

In the chemical formula (III), R ¹⁰ to R ¹⁷ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, or an aryl group. Here, the alkyl group, the cycloalkyl group, and the aryl group may be substituted or unsubstituted. Further, the alkyl group, the cycloalkyl group and the aryl group have usually 1 to 10 carbon atoms.

The combination of the structural unit represented by the formula (I) and the structural unit represented by the formula (III) with respect to the structural unit 1 represented by the formula (I), the structural unit represented by the formula (III) The amount is preferably 0.6 m or more, and more preferably 1.5 m or less. Thereby, a film excellent in heat resistance and flexibility can be formed as the substrate (A1).

Further, the polycarbonate polymer may contain any structural unit other than the structural unit represented by the formula (I) or the formula (III). However, in the polycarbonate polymer, the ratio of the structural unit represented by the formula (I) or the formula (III) is preferably 55 wt% or more, more preferably 70 wt% or more, particularly preferably 90 wt% or more. Further, it is usually 100% by weight or less.

A (meth) acrylate-vinyl aromatic compound copolymer resin which is a resin of a copolymer of a (meth) acrylate and a vinyl aromatic compound. The (meth) acrylate and the vinyl aromatic compound may be used in combination of one type or two types or more in any ratio. In addition, the above-mentioned copolymer may be used singly or in combination of two or more kinds in any ratio.

As the (meth) acrylate, for example, (meth) propylene is exemplified. The examples of the acid resin are the same as those exemplified. Further, the (meth) acrylate may be used alone or in combination of two or more kinds in any ratio.

The vinyl aromatic compound may, for example, be an aromatic monomer having an ethylenically unsaturated bond. Specific examples thereof include styrene, o-methyl styrene, p-methyl styrene, p-tert-butyl styrene, 2,4-dimethyl styrene, and 2,5-dimethyl styrene. , α-methyl styrene, vinyl naphthalene, vinyl fluorene. Further, the vinyl aromatic compound may be used alone or in combination of two or more kinds in any ratio.

From the viewpoint of heat resistance, transparency, and strength of the copolymer, the polymerization ratio of the (meth) acrylate to the vinyl aromatic compound can be from 1% by weight to 80% by weight based on the (meth) acrylate. The aromatic compound is 20% by weight to 99% by weight. When the amount of the (meth) acrylate is 1% by weight or more, the strength, heat resistance and transparency of the copolymer can be sufficiently increased, and by setting it to 80% by weight or less, (meth) acrylate-ethylene can be obtained. The molding processability of the base aromatic compound copolymer resin is good.

The copolymer of the (meth) acrylate and the vinyl aromatic compound may be a copolymer obtained by further polymerizing any monomer other than the (meth) acrylate and the vinyl aromatic compound. As an arbitrary monomer, a conjugated double bond compound is mentioned, for example. Specific examples of the conjugated double bond compound include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), and 2,3-dimethyl-1. 3-butadiene, 1,3-pentadiene, 1,3-hexadiene, etc., particularly preferably 1,3-butadiene or isoprene. These may be used alone or in combination of two or more kinds in any ratio. However, in the copolymer, the ratio of the structural unit having a structure in which a (meth) acrylate or a vinyl aromatic compound is polymerized is preferably It is 55 wt% or more, more preferably 70 wt% or more, particularly preferably 90 wt% or more, and usually 100 wt% or less.

The polyether oxime resin is a resin containing a polyether oxime polymer. Further, the polyether fluorene polymer is a polymer obtained by linking a main chain of a condensed structure of an aromatic bisphenol and a dihaloaryl fluorene. The polyether fluorene polymer can be obtained, for example, by polycondensation of an aromatic bisphenol and a dihaloaryl fluorene by a polymerization method such as a solution polymerization method or a melt polymerization method in the presence of a basic catalyst. The polyether oxime polymer may be used singly or in combination of two or more kinds in any ratio.

Examples of the aromatic bisphenol include hydroquinone, 4,4'-dihydroxybiphenyl, 1,1-bis(4-hydroxyphenyl)cyclohexane, and 1,1-bis(4-hydroxybenzene). -3,3,5-trimethylcyclohexane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyl Phenyl)butane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxy-3) -methylphenyl)propane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-tert-butylphenyl)propane, 9, 9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene , 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 2,2-bis(4-hydroxyphenyl)-1,1,1-3,3,3-hexafluoropropane, etc. . These types may be used alone or in combination of two or more types in any ratio.

Further, examples of the dihaloarylsulfonium include bis(4-chlorophenyl)fluorene, bis(4-fluorophenyl)fluorene, bis(4-bromophenyl)fluorene, and 4-chloro-4'. -(p-chlorophenyl)diphenyl hydrazine, 4-fluoro-4'-(p-fluorophenyl)diphenyl hydrazine, 4-bromo-4'-(p-bromophenyl)diphenyl hydrazine, bis(4'- Chlorinated biphenyl)indole, bis(4'-fluorobiphenyl)anthracene, bis(4'-bromobiphenyl)anthracene, bis(6-chlorobinaphthyl)anthracene, bis(6-fluorobinaphthyl) ) bismuth, bis(6-bromobi-naphthyl) anthracene, bis(4-chloro-3-methylphenyl)anthracene, bis(4-fluoro-3-methylphenyl)anthracene, bis(4-bromo-) 3- Methylphenyl)anthracene, bis(3-phenyl-4-chlorophenyl)anthracene, bis(3-phenyl-4-fluorophenyl)anthracene, bis(3-phenyl-4-bromophenyl) Anthraquinone, bis(4-chloro-3-tert-butylphenyl)anthracene, bis(4-fluoro-3-tert-butylphenyl)anthracene, bis(4-bromo-3-tert-butylphenyl) )碸. These types may be used alone or in combination of two or more types in any ratio.

The polyether fluorene polymer may contain any structural unit having a structure in which a monomer other than the aromatic bisphenol and the dihaloaryl fluorene is polymerized. However, the copolymer has a ratio of a structural unit having a structure in which an aromatic bisphenol and a dihaloaryl fluorene are polymerized, and is preferably 55 wt% or more, more preferably 70 wt% or more, particularly preferably 90% by weight or more, and usually, it is usually 100% by weight or less.

The resin which forms the material of the base material (A1) can contain arbitrary components other than the above-mentioned polymer. However, the ratio of the above-mentioned polymer of the resin forming the material of the substrate (A1) is preferably 50% by weight or more, preferably 80% by weight or more, particularly preferably 90% by weight or more, and usually 100% by weight. %the following.

For example, when the base material (A1) is a (meth)acrylic resin, the (meth)acrylic resin can contain rubber particles. By containing rubber particles, the flexibility of the (meth)acrylic resin can be improved and the impact resistance of the laminate can be improved. Further, if the surface roughness of the surface of the (meth)acrylic resin layer is roughened by the rubber particles as necessary, the contact area on the surface can be reduced to improve the smoothness of the surface. In the substrate (A1), the surface on the layer (A2) side of the non-liquid crystal material is preferably small in surface roughness, and therefore, the surface on the opposite side to the layer (A2) of the non-liquid crystal material is used. Roughening of the surface roughness is preferred.

As the rubber forming the rubber particles, for example, acrylic acid is exemplified. An ester polymer rubber, a polymer rubber containing butadiene as a main component, an ethylene-vinyl acetate copolymer rubber, or the like. The acrylate polymer rubber may, for example, be a main component of a monomer unit such as butyl acrylate or 2-ethylhexyl acrylate. Among these, an acrylate polymer rubber containing butyl acrylate as a main component and a polymer rubber containing butadiene as a main component are preferred.

Further, the rubber particles may contain one type of rubber alone or two or more types of rubber. Further, the rubbers may be uniformly mixed or may be layered. Examples of the rubber particles in which the rubber is layered include particles having a core composed of a rubber elastic component and a hard resin layer (shell) having a core-shell structure. Here, the rubber elastic component is, for example, a rubber elastic component obtained by grafting an alkyl acrylate such as butyl acrylate with styrene. Further, examples of the hard resin layer include a hard resin layer composed of a copolymer of one or both of polymethyl methacrylate and methyl methacrylate and an alkyl acrylate.

The rubber particles have a number average particle diameter of preferably 0.05 μm or more, more preferably 0.1 μm or more, more preferably 0.3 μm or less, and most preferably 0.25 μm or less. By setting the number average particle diameter within the above range, appropriate irregularities can be formed on the surface of the (meth)acrylic resin layer to improve the slipperiness of the laminate.

The amount of the rubber particles is preferably 5 parts by weight or more, and preferably 50 parts by weight or less based on 100 parts by weight of the (meth)acryl-based polymer. By setting the amount of the rubber particles within the above range, the impact resistance of the laminated body can be improved and the workability can be improved.

Moreover, the resin which forms the material of the base material (A1) can contain arbitrary components, for example, a compounding agent is mentioned. When an example of a formulating agent is given, a layered crystalline compound; a fine particle; an antioxidant, a heat stabilizer, a light stabilizer, a weathering stabilizer, a UV absorber, a near-infrared absorber, etc.; a plasticizer; a coloring agent such as a dye and a pigment; an antistatic agent Wait. Further, the formulation may be used in one type or in combination of two or more types in any ratio. The dosage can be appropriately determined insofar as the effect of the present invention is not significantly impaired. For example, it is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, based on 100 parts by weight of the above polymer. It is more preferably 3 parts by weight or less, and usually it can be set to 0 parts by weight or more.

The glass transition temperature of the resin forming the material of the substrate (A1) is preferably set in accordance with the glass transition temperature of the non-liquid crystalline material forming the layer (A2). Specifically, the difference between the glass transition temperature of the material of the substrate (A1) and the glass transition temperature of the non-liquid crystalline material forming the layer (A2) is preferably -15 ° C or higher, preferably -10 ° C or higher. It is preferably -5 ° C or more, preferably +15 ° C or less, preferably +10 ° C or less, and particularly preferably + 5 ° C or less. By making the difference in the glass transition temperature of the material forming the respective layers of the multi-layer film (A) within the above range, the layer of the non-liquid crystal material can be prevented from being damaged during the stretching treatment (A2 follows the substrate (A1)). Further, the stretching process is performed, and in this way, both the MD direction and the TD direction can be uniformly stretched in the layer (A2) of the non-liquid crystal material.

The substrate (A1) has a hysteresis value Re _A1 (550) in the in-plane direction of a wavelength of 550 nm, preferably 300 nm or less, preferably 200 nm or less, particularly preferably 100 nm or less, and usually 0 nm or more. By reducing the hysteresis value Re _A1 (550) in the in-plane direction of the substrate (A1), when the multi-layer film (A) is produced, only the layer (A2) of the non-liquid crystal material can be measured while performing the stretching treatment. Hysteresis value. In particular, as the substrate (A1), it is preferred to have optical isotropy.

As the substrate (A1), a surface treatment agent which performs a treatment such as hydrophilization treatment, hydrophobizing treatment, and reduction in solubility of the substrate (A1) as necessary may be used.

The substrate (A1) may have a single layer structure formed using only one layer, or may have a multi-layer structure including two or more layers.

The thickness of the substrate (A1) is preferably 10 μm or more, more preferably 20 μm or more, particularly preferably 30 μm or more, more preferably 200 μm or less, still more preferably 150 μm or less, and particularly preferably 100 μm or less. By setting the thickness of the base material (A1) to be equal to or higher than the lower limit of the above range, it is possible to prevent occurrence of unevenness in elongation. Moreover, when it is set to the upper limit or less, the tension of the base material (A1) can not be excessively increased, and industrial productivity can be improved.

[1.1.2. Layer of non-liquid crystalline material (A2)]

The layer (A2) of the non-liquid crystal material is a layer of a non-liquid crystal material having a positive intrinsic birefringence. The non-liquid crystal material differs from the liquid crystal material in that it is applied to the surface of the substrate (A1), and has no relationship with the alignment of the substrate (A1), and can be formed transparent by the properties of the non-liquid crystal material itself. Alignment layer. Subsequently, by stretching the multi-layer film (A), it is possible to form a layer (A2) which is a non-liquid crystal material which is aligned in an arbitrary extending direction and in the same direction. Therefore, the substrate (A1) described above does not need to have a step of applying an alignment film or a step of laminating an alignment film, for example, even if it is unaligned.

As a non-liquid crystal material having a positive intrinsic birefringence, a resin having a positive intrinsic birefringence is usually used. Further, as the resin, a transparent resin is usually used. Among such resins, a suitable example is heat-resistant, chemical-resistant, and transparent, and is also rich in rigidity, and examples thereof include a polyamide resin and a polyimide. Resin, maleimide resin, polyester resin, polyether ketone resin, polyamidoximine resin, polycarbonate resin, polyester phthalimide resin, polyurethane urea resin, and the like. These types may be used alone or in combination of two or more types in any ratio. Further, when two or more types of resins are combined, for example, a mixture of a polyether ketone resin and a polyamide resin can be used in combination with resins having different functional groups. Among such resins, polyimide resin, maleimide resin, polyamidoximine resin, polycarbonate resin, polyester resin, and polyurethane urea resin are preferred. Specific examples include those described in Japanese Patent No. 3962034, No. 3897743, Japanese Patent No. 3838522, and Japanese Patent No. 3811175.

As the preferred polyimine resin, for example, a resin containing a polyimine which is high in in-plane orientation and soluble in an organic solvent is preferred. Specifically, for example, a condensation polymerization product containing 9,9-bis(amine aryl)fluorene and an aromatic tetracarboxylic dianhydride disclosed in JP-A-2000-511296, and containing a polybendimimine The resin is preferably one or more structural units represented by the following formula (VI) per molecule.

In the formula (VI), R ^1a each independently represents a phenyl group selected from a hydrogen atom; a halogen atom; a phenyl group; a halogen atom substituted by 1 to 4 halogen atoms or an alkyl group having 1 to 10 carbon atoms; The group consisting of a group of 1 to 10 alkyl groups. In particular, R ^1a is a phenyl group selected from a halogen atom; a phenyl group; a halogen atom substituted by 1 to 4 halogen atoms or an alkyl group having 1 to 10 carbon atoms; and an alkyl group having 1 to 10 carbon atoms. It is better.

In the formula (VI), A ^a represents a tetra-substituted aromatic group having 6 to 20 carbon atoms. In particular, as A ^a , it is preferred to use any of the following (1) to (3).

(1) A tetravalent group having a structure in which a hydrogen atom is removed from four carboxyl groups of pyromellitic acid.

(2) a tetravalent group of a structure obtained by removing a hydrogen atom from a polycyclic aromatic compound such as a naphthyl group, a fluorenylene group, a benzoindene group, or a fluorenyl group, and a substitution thereof derivative. Here, the substituent is a halogen atom having 1 to 10 carbon atoms and a fluorinated derivative thereof, and fluorine or chlorine.

(3) A group represented by the formula (VII).

In the formula (VII), B ^a is a covalent bond and represents a C(R ^2a ) ₂ group, a CO group, an O atom, an S atom, a SO ₂ group, a Si(C ₂ H ₅ ) ₂ group, and a N(R ^3a ) group. 2 base and combinations of these. R ^2a each independently represents a hydrogen atom or a C(R ^4a ) ₃ group. R ^3a each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ^4a each independently represents a hydrogen atom, a fluorine atom or a chlorine atom. Further, in the formula (VII), m represents an integer of 1 to 10.

As a preferred maleimide resin, for example, it may be mentioned There is a resin of a polymer represented by the formula (VIII).

The formula (VIII), R ^b and Q ^b each independently represent a substituted or unsubstituted aliphatic group, an aromatic group, a heterocyclic group, a phosphonyl group or an unsaturated hydrocarbon group.

In formula (VIII), X ^b represents an active energy ray-hardened or thermally hardenable maleimide group.

In the formula (VIII), n represents an integer of 1 or more and 10 or less.

Among the polymers represented by the formula (VIII), a polymer having a structure represented by the following formula (IX) or formula (X) is preferred. In the formula (IX) and the formula (X), n each independently represents an integer of 1 or more and 10 or less.

[化10]

Further, examples of the maleimide resin include the compounds described in U.S. Patent Application Publication No. 2008/0075961.

These maleimide resins are available, for example, from ARBROWN.

For example, the polyamidamine resin and the polyester resin described in JP-A-10-508048 can be mentioned. The structural unit contained in the polyamidoximine or polyester containing the polyamidoximine resin or the polyester resin is represented, for example, by the following chemical formula (XI).

In formula (XI), Y ^c represents -O- or -NH-.

In the formula (XI), E ^c each independently represents a covalent bond and is selected from an alkyl group having 2 carbon atoms, a alkyl group having ₂ carbon atoms halogenated, a CH ₂ group, and C (CX ^c ₃ ). A group of at least one of the group consisting of a ₂ group, a CO group, an O atom, an S atom, a SO ₂ group, a Si(R ^c ) ₂ group, and an N(R ^c ) group. Further, the E ^c systems may be the same or different. In the above E ^c , R ^c is at least one of an alkyl group having 1 to 3 carbon atoms and a halogenated alkyl group having 1 to 3 carbon atoms, and is at a meta or para position to the carbonyl group or the Y ^c group. Further, X ^c is a halogen atom or a hydrogen atom.

In the formula (XI), A ^c represents a substituent. Examples of the above A ^c include a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, and OR ^c (wherein R ^c is as defined above). The alkoxy group, the aryl group, the substituted aryl group obtained by halogenation or the like, the alkoxycarbonyl group having 1 to 9 carbon atoms, the alkylcarbonyloxy group having 1 to 9 carbon atoms, and the number of carbon atoms 1 to An aryloxycarbonyl group of 12, an arylcarbonyloxy group having 1 to 12 carbon atoms and a substituted derivative thereof, an arylaminomethylcarbonyl group having 1 to 12 carbon atoms, and an aryl group having 1 to 12 carbon atoms a carbonylamine group and a substituted derivative thereof. Further, when A ^c is a plural number, the A ^c systems may be the same or different.

In the formula (XI), A ^{c '} represents a substituent. Examples of the above A ^c' include a halogen atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a phenyl group and a substituted phenyl group. Further, when A ^{c '} is plural, A ^{c '} can be the same or different. The substituent on the phenyl ring of the substituted phenyl group may, for example, be a halogen atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, or a combination thereof.

In the formula (XI), t and z each represent the substitution number of A ^c and A ^{c '} . The above t is an integer of 0 to 4. The above z is an integer of 0 to 3.

In the formula (XI), p is an integer of 0 to 3, q is an integer of 1 to 3, and r is an integer of 0 to 3.

Further, the polyester may contain a structural unit represented by the following formula (XII) or formula (XIII).

In the above formula (XII) and formula (XIII), X ^d and Y ^d represent a substituent. X ^d each independently represents a group selected from the group consisting of a hydrogen atom, a chlorine atom and a bromine atom. Further, Y ^d represents a group represented by the following formula (XIV) or formula (XV). Further, n represents an integer of 1 or more.

Specific examples of the polyester are "VYLON" manufactured by Toyobo Co., Ltd. and "POLYESTER" manufactured by Nippon Synthetic Chemical Co., Ltd.

The polyurethane urea resin may, for example, be a polyol containing an aliphatic cyclic structure, a polyisocyanate having an aliphatic cyclic structure, a polyamine having an aliphatic cyclic structure, and a group having an active hydrogen atom. A resin of a polymer obtained by reacting an acrylic compound. As a specific example, the material and the method of the method described in JP-A-2011-132548 may be mentioned. Synthetic polymer resin. As a specific example of the polyurethane urea resin, "TYFORCE" manufactured by DIC Corporation can be suitably used.

The polycarbonate resin may, for example, be the same as those exemplified in the description of the material forming the substrate (A1). As a specific example, the Yupizeta PCZ series manufactured by Mitsubishi Gas Chemical Co., Ltd., "FPC2136" manufactured by Mitsubishi Gas Chemical Co., Ltd., and "Tough Z" manufactured by Idemitsu Kosan Co., Ltd. can be cited.

A resin which is a non-liquid crystal material having a positive intrinsic birefringence can be used, and any component other than the above polymer can be contained. However, the ratio of the above-mentioned polymer which can use a resin which is a non-liquid crystal material having a positive intrinsic birefringence is preferably 55% by weight or more, preferably 80% by weight or more, and particularly preferably 90% by weight or more. Further, it is usually 100% by weight or less.

The glass transition temperature of the non-liquid crystal material in which the intrinsic birefringence of the layer (A2) forming the non-liquid crystal material is positive is preferably 70 ° C or higher, preferably 90 ° C or higher, particularly preferably 110 ° C or higher, and 180. Preferably, it is below °C, preferably 160 ° C or less, and particularly preferably 140 ° C or less. By forming the layer (A2) using a non-liquid crystalline material having a glass transition temperature in such a range, the layer (A2) of the non-liquid crystal material can stably exhibit the required hysteresis value by the stretching treatment, and becomes A layer excellent in stability under high temperature, high temperature and high humidity.

The layer (A2) of the non-liquid crystal material is preferably a negative biaxial layer in which the relationship between the refractive indices nx, ny, and nz is nx>ny and nx>nz. Thereby, a phase difference film in which the layer (A2) of the non-liquid crystal material and the layer (B1) of the non-liquid crystal material are combined is used as the optical compensation film, and the contrast of the IPS type liquid crystal panel can be effectively improved.

The layer (A2) of the non-liquid crystal material is a hysteresis value Re _A2 (550) in the in-plane direction of a wavelength of 550 nm, preferably 50 nm or more, preferably 70 nm or more, preferably 150 nm or less, preferably 120 nm or less. . When the hysteresis value Re _A2 (550) in the in-plane direction of the layer (A2) of the non-liquid crystal material is within this range, it can be easily produced by stretching the multi-layer film (A).

Further, the layer (A2) of the non-liquid crystal material is a hysteresis value Rth _A2 (550) in the thickness direction of a wavelength of 550 nm, preferably 40 nm or more, preferably 60 nm or more, preferably 150 nm or less, and more preferably 120 nm. the following. When the hysteresis value Rth _A2 (550) in the thickness direction of the layer (A2) of the non-liquid crystal material is within this range, it can be easily produced by stretching the multi-layer film (A).

Here, the quotient obtained by dividing the hysteresis value Re _A1 (550) of the substrate (A1) at a wavelength of 550 nm by the "thickness of the substrate (A1)" is "I". In addition, the quotient obtained by dividing the hysteresis value Re _A2 (550) at a wavelength of 550 nm of the layer (A2) of the non-liquid crystal material by the thickness of the layer (A2) of the non-liquid crystal material is "J". In this case, I<J is preferable, 3I<J is preferable, 5I<J is more preferable, and 10I<J is particularly preferable. By manufacturing the multi-layer film (A) by the material satisfying the relationship between the value I and the value J described above, it is possible to accurately measure only the hysteresis value of the layer (A2) of the non-liquid crystal material while performing the stretching treatment.

The thickness of the layer (A2) of the non-liquid crystal material is preferably 0.1 μm or more, preferably 1 μm or more, and is preferably 40 μm or less from the viewpoint of improving the impact resistance, workability, and film properties, and is preferably 40 μm or less. 30 μm or less. When the thickness of the layer (A2) of the non-liquid crystal material is within this range, the laminated body can be made thinner, and the laminated body can be excellent in high-temperature durability.

The thickness deviation in the plane of the layer (A2) of the non-liquid crystal material is preferably 5% or less of the average thickness of the layer (A2), preferably 3% or less, more preferably 1%. Hereinafter, it is preferably 0%. The term "thickness deviation" as used herein refers to the difference between the maximum value and the minimum value of the thickness. By achieving excellent thickness accuracy in this manner, it is possible to obtain a laminate and a retardation film which exhibit uniform optical characteristics in the MD direction and the TD direction. Further, such thickness accuracy can be achieved, for example, by producing a multi-layer film (A) by a combination of a coating and stretching method described later.

The peeling force between the substrate (A1) and the layer (A2) of the non-liquid crystal material is preferably 0.05 N/20 mm or less, preferably 0.03 N/20 mm or less, and particularly preferably 0.01 N/20 mm or less. The peeling force can be measured in accordance with JIS K6853-2. By reducing the peeling force in this manner, the base material (A1) can be peeled off from the laminated body, and the retardation film can be easily produced. Further, the lower limit of the peeling force is preferably 0.001 N/20 mm or more, preferably 0.003 N/20 mm or more, and particularly preferably 0.005 N/20 mm or more. Such a small peeling force can be realized, for example, by a material combination of a locally selected substrate (A1) and a layer (A2) of a non-liquid crystal material, using mutually incompatible materials.

[1.1.3. Any layer]

The multi-layer film (A) may have any layer on the side opposite to the layer (A2) of the non-liquid crystal material of the substrate (A1).

[1.2. Multilayer film (B)]

As shown in Fig. 1, the multi-layer film (B) 20 is provided with a layer (B1) 21 and a resin layer (B2) 22 which are non-liquid crystal materials. Since the resin layer (B2) 22 is connected to the layer (B1) 21 of the non-liquid crystal material, no other layer is provided between the layer (B1) 21 and the resin layer (B2) 22 of the non-liquid crystal material.

[1.2.1. Layer of non-liquid crystalline material (B1)]

The layer (B1) of the non-liquid crystal material is a non-liquid crystal material having a negative intrinsic birefringence The layer of material. As a non-liquid crystal material having a negative intrinsic birefringence, a resin having a negative intrinsic birefringence is usually used. Further, as the resin, a transparent resin is usually used. The resin contains one or more types selected from the group consisting of styrene, styrene-maleic acid, maleimide, and (meth) acrylate. The polymer of the polymer obtained by polymerization is preferred. In this case, the aforementioned polymer may be a homopolymer or a copolymer. Since such a polymer generally has a negative intrinsic birefringence, the intrinsic birefringence of the resin containing the same can also be made negative.

Here, the term "styrene" means styrene and a styrene derivative. Further, examples of the styrene derivative include those in which a benzene ring or an α position of styrene is substituted with a substituent. Specific examples of the styrene derivative include alkylstyrene such as methylstyrene and 2,4-dimethylstyrene; halogenated styrene such as chlorostyrene; and chloromethylstyrene; Halogen-substituted alkylstyrene; alkoxystyrene such as methoxystyrene; and the like. Here, the styrene type may be used alone or in combination of two or more types in any ratio.

Further, the polymerization of styrene-maleic acid as a monomer means copolymerization of styrene and maleic acid. Further, maleic acid may be polymerized in the form of maleic anhydride.

In addition, examples of the maleimide group include compounds represented by the following formula (XVI).

[Chemistry 14]

In the formula (XVI), R ^1e and R ^2e each independently represent a hydrogen atom or an alkyl group.

In the formula (XVI), X ^e represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a phenyl group, a cyano group or a hydroxyl group.

Examples of the maleimide group include maleimide, N-methylbutyleneimine, N-ethylbutyleneimine, and N. -isopropyl succinimide, N-butyl maleimide, N-isobutyl maleimide, N-tert-butyl maleimide, N-cyclohexyl cis Butylene diimide, N-phenyl maleimide, N-chlorophenyl maleimide, N-methylphenyl maleimide, N-naphthyl Maleimide, N-lauryl, maleimide, N-hydroxyethyl maleimide, N-hydroxyphenyl maleimide, N-methoxy Phenylstyrene, N-carboxyphenyl maleimide, N-nitrophenyl maleimide, N-tribromophenyl-tert-butylene Amines, etc. Here, the maleimide may be used singly or in combination of two or more kinds in any ratio. Among these, N-cyclohexylmethyleneimine, N-isopropyl maleimide, and N-phenyl maleimide are preferred.

Further, examples of the (meth) acrylate include the same examples as those of the material for forming the substrate (A1). Here, the (meth) acrylate type may be used alone or in combination of two or more types in any ratio. use.

Further, the polymer obtained by polymerizing the above-mentioned monomers is not particularly damaging the effects of the present invention except for styrene, styrene-maleic acid, maleimide and (a) In addition to the acrylate, it may be a copolymer of any monomer. However, the polymer is formed by polymerizing a monomer selected from the group consisting of styrene, styrene-maleic acid, maleimide, and (meth) acrylate. The ratio of the structural unit of the structure is preferably 55 wt% or more, more preferably 70 wt% or more, particularly preferably 90 wt% or more, and usually 100 wt% or less.

Among the above polymers, a polymer using styrene as a monomer and a copolymer of maleimide and styrene are preferred. In other words, a resin containing a polymer obtained by polymerizing styrene or styrene-maleic acid and a resin containing a copolymer of maleimide and styrene are inherently A resin having a negative birefringence is preferred. By using a styrene-based polymer-based polystyrene-based polymer, by using a resin containing a polystyrene-based polymer, the hysteresis value required for the layer (B1) of the non-liquid crystal material can be stably stabilized. appear.

In addition, as a copolymer of maleimide and styrene, a polymer described in JP-A-2001-31710 and JP-A-2000-204126 can be suitably used, and specifically, it can be suitably used. "POLYIMILEX" manufactured by Nippon Shokubai Co., Ltd. and "DENKAIP" manufactured by DENKA Corporation.

Further, in particular, the polystyrene polymer is preferably a polystyrene polymer having a syndiotactic structure. The polystyrene polymer having a syndiotactic structure has high heat resistance, can suppress heat shrinkage, and can be extended by stretching The required hysteresis value appears steadily.

Here, the polystyrene polymer has a syndiotactic structure, and means that the stereochemical structure of the polystyrene polymer is a syndiotactic structure. Further, the syndiotactic structure refers to a main chain in which a side chain phenyl group is formed by a carbon-carbon bond, and a three-dimensional structure in which FISCHER projection patterns are alternately and regularly arranged in opposite directions. Compared with the conventional non-standard polystyrene polymer, the polystyrene polymer having a syndiotactic structure is excellent in characteristics such as low specific gravity and hydrolysis resistance, heat resistance, and chemical resistance.

The stereotacticity of the polystyrene polymerization can be quantified by a nuclear magnetic resonance apparatus method ( ¹³ C-NMR method) using an isotope carbon. The stereoregularity measured by the ¹³ C-NMR method can be expressed by the ratio of the existence of a plurality of consecutive structural units. Usually, for example, when the number of continuous structural units is two, it is a dyad, three is a triad, and five is a pentad. In this case, the above-mentioned polystyrene polymer having a syndiotactic structure means that the following (x) or (y) is satisfied.

(x) In the racemic dyad, it is usually 75% or more, preferably 85% or more, and 100% or less.

(y) In the racemic quinone, it is usually 30% or more, preferably 50% or more, and 100% or less.

The polystyrene-based polymer having a syndiotactic structure can be, for example, a styrene-based compound obtained by using a titanium compound and a condensation product of water and trialkylaluminum as a catalyst in an inert hydrocarbon solvent or in the absence of a solvent. It is produced by polymerization (refer to JP-A-62-187708). Further, the poly(halogenated alkylstyrene) can be produced, for example, by the method described in JP-A-4-40612.

a polymer obtained by polymerizing a monomer selected from the group consisting of styrene, styrene-maleic acid, maleimide, and (meth) acrylate, The weight average molecular weight is preferably 130,000 or more, preferably 140,000 or more, particularly preferably 150,000 or more, more preferably 300,000 or less, more preferably 270,000 or less, and particularly preferably 250,000 or less. When the weight average molecular weight is used, the glass transition temperature of the polymer can be increased to stably improve the heat resistance of the laminate.

a polymer obtained by polymerizing a monomer selected from the group consisting of styrene, styrene-maleic acid, maleimide, and (meth) acrylate, The glass transition temperature is preferably 85 ° C or higher, preferably 90 ° C or higher, and particularly preferably 95 ° C or higher. By increasing the glass transition temperature in this manner, the glass transition temperature of the non-liquid crystal material having a negative intrinsic birefringence of the formation layer (B1) can be effectively increased, and the heat resistance of the retardation film can be stably improved. Moreover, from the viewpoint of stably and easily producing a laminate, the glass transition temperature is preferably 160 ° C or lower, preferably 155 ° C or lower, and particularly preferably 150 ° C or lower.

Further, the non-liquid crystal material having a negative intrinsic birefringence of the layer (B1) forming the non-liquid crystalline material is selected from the group consisting of styrene, styrene-maleic acid, and maleimide. A polymer obtained by polymerizing a monomer having one or more types of a group consisting of (meth) acrylate, and a polymer selected from the group consisting of a polycarbonate polymer, a polyester polymer, and a polycondensation aryl ether polymer A mixture of one or more types of polymers constituting the group is preferred. By combining a polycarbonate polymer, a polyester polymer or a poly(arylene ether) polymer, the strength of the layer (B1) of the non-liquid crystal material can be increased, the glass transition temperature can be controlled, and the optical characteristics can be controlled.

The polycarbonate polymer may, for example, be the same as those exemplified in the description of the material forming the substrate (A1). Here, the polycarbonate polymer may be used singly or in combination of two or more kinds in any ratio.

Further, the polyester polymer is a polymer having a structural unit bonded by an ester bond. The polyester polymer may be used singly or in combination of two or more kinds in any ratio. The polyester polymer is obtained by dehydrating or polymerizing a polyhydric alcohol having a plurality of hydroxyl groups such as glycol or diol, a polyvalent carboxylic acid having a plurality of carboxyl groups such as a dicarboxylic acid, or an anhydride thereof.

Examples of the polyhydric alcohol include 1,2-propanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,4-pentanediol, and 3-methyl group. -1,5-pentanediol, 2,5-hexanediol, 2-methyl-1,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl -2-ethyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2,4-tri Methyl-1,6-hexanediol and the like. These types may be used alone or in combination of two or more types in any ratio.

Examples of the polyvalent carboxylic acid include adipic acid, decanoic acid, isophthalic acid, p-citric acid, maleic acid, fumaric acid, succinic acid, oxalic acid, malonic acid, glutaric acid, and gly. a dicarboxylic acid such as diacid, suberic acid, azelaic acid or sebacic acid; a polycarboxylic acid having a carboxyl group having a valence of 3 or more, such as 1,2,4-benzenetricarboxylic acid or pyroic acid; and an anhydride thereof . These types may be used alone or in combination of two or more types in any ratio.

Further, the polyester polymer may be a polymer obtained by copolymerizing any monomer other than a polyol, a polyvalent carboxylic acid or an anhydride thereof. However, in the polyester polymer, the ratio of the structural unit having a structure formed by polymerizing a polyhydric alcohol, a polyvalent carboxylic acid or an anhydride thereof is preferably 55 wt% or more, more preferably 70 wt%. The above is particularly preferably 90% by weight or more.

As a specific example of the polyester polymer, "VYLON" manufactured by Toyobo Co., Ltd. and "POLYESTER" manufactured by Nippon Synthetic Chemical Co., Ltd. can be suitably used.

The poly(arylene ether) polymer is a polymer having a structural unit containing a aryl ether skeleton in the main chain. The poly(aryl ether) polymer may be used singly or in combination of two or more kinds in any ratio. In particular, as the poly(arylene ether) polymer, a polymer containing a structural unit represented by the following formula (XVII) is preferred.

In the formula (XVII), Q ¹ each independently represents a halogen atom, a lower alkyl group (for example, an alkyl group having 7 or less carbon atoms), a phenyl group, a haloalkyl group, an amine alkyl group, a hydrocarbyloxy group, or a halogen group. Alkoxy group (however, at least 2 carbon atoms separate the halogen atom from the oxygen atom). In particular, as Q ¹ , an alkyl group and a phenyl group are preferred, and an alkyl group having 1 or more and 4 or less carbon atoms is particularly preferred. ]

In the formula (XVII), Q ² each independently represents a hydrogen atom, a halogen atom, a lower alkyl group (for example, an alkyl group having 7 or less carbon atoms), a phenyl group, a haloalkyl group, a hydrocarbyloxy group, or a halogen group. Alkoxy groups (however, at least 2 carbon atoms separate the base of their halogen atoms from oxygen atoms). In particular, a hydrogen atom is preferred as the Q ² system.

a poly-arylene ether polymer, which may have a structure of one type The homopolymer of the unit may be a copolymer having two or more types of structural units.

When the polycondensation aryl ether polymer containing the structural unit represented by the formula (XVII) is a homopolymer, a preferred example of the homopolymer is exemplified by having 2,6-dimethyl group- A homopolymer of a 1,4-phenylene ether unit (i.e., a structure represented by "-(C ₆ H ₂ (CH ₃ ) ₂ -O)-").

Further, when the polycondensation aryl ether polymer containing the structural unit represented by the formula (XVII) is a copolymer, a preferred example of the copolymer is 2,6-dimethyl-1,4. - a phenyl ether unit and a 2,3,6-trimethyl-1,4-phenylene ether unit (ie, "-(C ₆ H(CH ₃ ) ₃ -O-)-") Structure)) A random copolymer which is combined.

The poly(arylene ether) polymer may also contain structural units other than the extended aryl ether unit. At this time, the poly(aryl ether) polymer is a copolymer having an extended aryl ether unit and other structural units. However, the ratio of the aryl ether unit in the poly(arylene ether) polymer is preferably 50% by weight or more, preferably 70% by weight or more, and particularly preferably 80% by weight or more.

As described above, a monomer selected from the group consisting of styrene, styrene-maleic acid, maleimide, and (meth) acrylate is polymerized. a combination of a polymer and a polymer selected from the group consisting of a polycarbonate polymer, a polyester polymer, and a poly(arylene ether) polymer, in particular, a polystyrene polymer and A poly(arylene ether) polymer combination is preferred.

Moreover, since the hysteresis value is high and the compatibility with the poly-arylene ether polymer is good, the polystyrene-based polymer and the poly-arylene ether polymer are used. In the case of combination, a polystyrene-based polymer is preferably a styrene-based homopolymer, and a polystyrene-based polymer having a syndiotactic structure is preferred. Further, from the viewpoint of compatibility with the poly(arylene ether) polymer, even if the polystyrene polymer is a copolymer obtained by copolymerizing monomers other than styrene, monomers other than styrene The ratio is preferably less than 5% by weight.

a polymer obtained by polymerizing a monomer selected from the group consisting of styrene, styrene-maleic acid, maleimide, and (meth) acrylate, Preferably, the weight ratio of the polymer selected from the group consisting of a polycarbonate polymer, a polyester polymer, and a poly(arylene ether) polymer is from 90:10 to 55:45, preferably. It is 85:15~60:40, and the best is 80:20~65:35. By having the weight ratio within this range, the hysteresis value required for the layer (B1) of the non-liquid crystal material and the required optical characteristics can be easily exhibited by stretching.

The non-liquid crystal material having a negative birefringence in which the layer (B1) of the non-liquid crystal material is formed may be selected from styrenes, styrene-maleic acid, maleimide And a polymer obtained by polymerizing one or more types of monomers composed of a group of (meth) acrylates, and a group selected from the group consisting of polycarbonate polymers, polyester polymers, and polyaryl ether polymers Any component other than the polymer of one type or more. Examples of the optional component include an antioxidant, an ultraviolet absorber, a photostabilizer, and a crosslinking agent. However, the non-liquid crystalline material having a negative intrinsic birefringence in the formation layer (B1) will be selected from the group consisting of styrenes, styrene-maleic acid, maleimide and (meth) a polymer obtained by polymerizing one or more types of monomers composed of acrylates, and one selected from the group consisting of polycarbonate polymers, polyester polymers, and polyaryl ether polymers The ratio of the polymer or more is preferably 50% by weight or more, preferably 80% by weight or more, particularly preferably 90% by weight or more, and usually 100% by weight or less.

The glass transition temperature of the non-liquid crystal material in which the intrinsic birefringence of the layer (B1) forming the non-liquid crystal material is negative is preferably 115 ° C or higher, preferably 120 ° C or higher, and particularly preferably 125 ° C or higher. The higher the glass transition temperature of the non-liquid crystalline material having a negative intrinsic birefringence, the more excellent the heat resistance of the retardation film. However, when the glass transition temperature is excessively increased, there is a possibility that the production of the laminate is not easy. Therefore, the glass transition temperature of the non-liquid crystalline material having a negative intrinsic birefringence is usually 200 ° C or lower.

The tensile elongation at break of the layer (B1) of the non-liquid crystal material is preferably 20% or less, preferably 15% or less, and particularly preferably 10% or less. The tensile elongation at break can be measured in accordance with JIS K7162. Generally, a non-liquid crystalline material having a negative intrinsic birefringence is weak in mechanical strength. On the other hand, since the multi-layer film (B) is provided with the resin layer (B2), even if the layer (B1) of the non-liquid crystal material having a weak mechanical strength is used, it is less likely to be damaged. Further, the laminate of the present invention has a laminate of a substrate (A1), a layer (A2) of a non-liquid crystal material, an adhesive layer, a layer (B1) of a non-liquid crystal material, and a resin layer (B2) in this order. With this laminated structure, it is possible to effectively prevent breakage of the layer (B1) of the non-liquid crystal material. Therefore, from the viewpoint of further preventing the damage of the layer (B1) and improving the workability and impact resistance, as described above, the tensile elongation at break of the layer (B1) is technically significant.

The layer (B1) of the non-liquid crystal material preferably has a positive biaxial layer satisfying nz>nx>ny in terms of its refractive index nx, ny, and nz. borrow Thus, a phase difference film in which a layer (A2) of a non-liquid crystal material and a layer (B1) of a non-liquid crystal material are combined is used as an optical compensation film, and the contrast of the IPS type liquid crystal panel can be effectively improved.

The layer (B1) of the non-liquid crystal material is a hysteresis value Re _B1 (550) in the in-plane direction of a wavelength of 550 nm, preferably 40 nm or more, preferably 50 nm or more, preferably 150 nm or less, preferably 100 nm or less. . When the hysteresis value Re _B1 (550) in the in-plane direction of the layer (B1) of the non-liquid crystal material is within this range, it can be easily produced by the extension of the multi-layer film (B).

Further, the layer (B1) of the non-liquid crystal material is a hysteresis value Re _B1 (450) in the in-plane direction at a wavelength of 450 nm and a hysteresis value Re _B1 (550) in the in-plane direction at a wavelength of 550 nm to satisfy Re _B1 ( 450) / Re _B1 (550) > 1.00 is preferred. By satisfying Re _B1 (450) and Re _B1 (550) as the relationship, it is possible to obtain a retardation film which can achieve the compensation effect of the IPS liquid crystal cell in a wide wavelength range.

Further, the layer (B1) of the non-liquid crystal material is a hysteresis value Rth _B1 (550) in the thickness direction of a wavelength of 550 nm, preferably -150 nm or more, preferably -130 nm or more, and preferably -50 nm or less. Good for -60nm or less. When the hysteresis value Rth _B1 (550) in the thickness direction of the layer (B1) of the non-liquid crystal material is within this range, it can be easily produced by the extension of the multi-layer film (B).

The in-plane retardation axis of the layer (B1) of the non-liquid crystal material is generally parallel to the in-plane slow axis of the layer (A2) of the non-liquid crystal material having a positive intrinsic birefringence of the multi-layer film (A). . Thereby, in the IPS type liquid crystal panel, optical compensation can be effectively performed, and the contrast of the liquid crystal display device can be improved.

The thickness of the layer (B1) of the non-liquid crystal material is preferably 5 μm or more, preferably 7 μm or more, more preferably 30 μm or less, and still more preferably 15 μm or less. When the thickness of the layer (B1) of the non-liquid crystal material is within this range, the laminate can be made thinner, and the laminate can be excellent in high-temperature durability.

The thickness of the layer (B1) of the non-liquid crystal material varies, and the average thickness of the layer (B1) is preferably 20% or less, preferably 15% or less, more preferably 10% or less, and desirably 0%. By achieving such thickness accuracy, it is possible to obtain a laminate and a retardation film which exhibit uniform optical characteristics in the MD direction and the TD direction. Moreover, such thickness accuracy can be achieved by producing a multi-layer film (B) by, for example, a manufacturing method in which a combination of melt extrusion and stretching described later is combined.

[1.2.2. Resin layer (B2)]

The resin layer (B2) is a layer formed using a resin. As the resin, a thermoplastic resin is usually used. Further, as the resin, a transparent resin is usually used. The resin is selected from the group consisting of a polymer resin having an alicyclic structure, a (meth)acrylic resin, a polycarbonate resin, a (meth) acrylate-vinyl aromatic compound copolymer resin, and a polyether. The resin of the group consisting of enamel resin is preferred. These resins are excellent in mechanical strength, and can provide the peel strength of the layer (B1) with the non-liquid crystal material to a desired peel strength, and can also reduce the hysteresis value which appears due to stretching.

As a polymer resin having an alicyclic structure capable of forming a resin layer (B2), a (meth)acrylic resin, a polycarbonate resin, a (meth) acrylate-vinyl aromatic compound copolymer resin, and a polyether As the enamel resin, for example, the same as each resin described as the material for forming the substrate (A1) can be used. Therefore, a polymer resin having a alicyclic structure capable of forming a resin layer (B2), a (meth)acrylic resin, a polycarbonate resin, a (meth) acrylate-vinyl aromatic compound copolymer resin, and Each of the polyether oxime resins, the resin thereof can contain The type and amount of the polymer and the optional component can be the same as those described for the material forming the substrate (A1).

Among the resins, the resin forming the resin layer (B2) is preferably a polymer resin having an alicyclic structure and a (meth)acrylic resin, and particularly preferably a (meth)acrylic resin.

The glass transition temperature of the resin forming the resin layer (B2) is preferably set to a glass transition temperature of the non-liquid crystalline material which is negative in accordance with the intrinsic birefringence of the formation layer (B1). Specifically, the glass transition temperature Tg (B1) of the non-liquid crystalline material having a negative intrinsic birefringence of the layer (B1) and the glass transition temperature Tg (B2) of the resin forming the resin layer (B2) are satisfied. Tg(B1)>Tg(B2)+20°C is preferred, and it is preferred to satisfy Tg(B1)>Tg(B2)+25°C. Therefore, when the stretching treatment is performed at an extension temperature higher than the glass transition temperature Tg (B1) of the non-liquid crystal material having a negative intrinsic birefringence, the polymer layer is almost unaligned and becomes unaligned in the resin layer (B2). status. Therefore, even if a large hysteresis value is not exhibited in the resin layer (B2) by the stretching process, it is possible to accurately measure only the hysteresis value of the layer (B1) of the non-liquid crystal material while performing the stretching process.

Further, in particular, the glass transition temperature of the polymer resin having an alicyclic structure capable of forming the resin layer (B2) is preferably 80 ° C or more, preferably 90 ° C or more, preferably 150 ° C or less, more preferably It is 120 ° C or less, more preferably 110 ° C or less. By setting the glass transition temperature to be equal to or higher than the lower limit of the above range, the durability at a high temperature can be improved, and the elongation processing can be easily performed by setting it to the upper limit or lower.

Further, in particular, the glass transition temperature of the (meth)acrylic resin capable of forming the resin layer (B2) is preferably 80 ° C or more, and more preferably 90 ° C or more. It is preferably 120 ° C or lower, preferably 110 ° C or lower. By setting the glass transition temperature to be equal to or higher than the lower limit of the above range, it is possible to prevent adhesion of the resin particles when the resin particles are dried at a high temperature, so that it is possible to prevent moisture from entering. In addition, since the orientation of the (meth)acryl-based polymer at the time of stretching can be reduced, the optical layer function of the layer (B1) of the non-liquid crystal material can be suppressed from being inhibited by the resin layer (B2). .

Further, in particular, the glass transition temperature of the polycarbonate resin capable of forming the resin layer (B2) is preferably 80 ° C or higher, more preferably 90 ° C or higher, more preferably 100 ° C or higher, and particularly preferably 120 ° C or higher. It is preferably 160 ° C or lower, preferably 150 ° C or lower. By setting the glass transition temperature to be equal to or higher than the lower limit of the above range, the durability at a high temperature can be improved, and the elongation processing can be easily performed by setting it to the upper limit or lower.

The resin layer (B2) has a hysteresis value Re _B2 (550) in the in-plane direction at a wavelength of 550 nm, preferably 30 nm or less, preferably 20 nm or less, particularly preferably 10 nm or less, and usually 0 nm or more. By reducing the hysteresis value Re _B2 (550) in the in-plane direction of the resin layer (B2), when the multi-layer film (B) is produced, only the layer (B1) of the non-liquid crystal material can be measured while performing the stretching treatment. Hysteresis value.

The thickness of the resin layer (B2) is preferably 1 μm or more, more preferably 3 μm or more, particularly preferably 5 μm or more, more preferably 50 μm or less, still more preferably 30 μm or less, and particularly preferably 15 μm or less. By setting the thickness of the resin layer (B2) to be equal to or higher than the lower limit of the above range, the mechanical strength of the resin layer (B2) can be sufficiently improved. In addition, the flexibility and workability of the resin layer (B2) can be improved by setting it as the upper limit or less.

The peeling force between the layer (B1) and the resin layer (B2) of the non-liquid crystal material having a negative intrinsic birefringence is preferably 0.5 N/20 mm or less, more preferably 0.3N/20mm or less, particularly preferably 0.15N/20mm or less. The peeling force can be measured in accordance with JIS K6853-2. By reducing the peeling force in this manner, the resin layer (B2) can be peeled off from the laminated body, and the retardation film can be easily produced. Further, the lower limit of the peeling force is preferably 0.01 N/20 mm or more, preferably 0.03 N/20 mm or more, and particularly preferably 0.05 N/20 mm or more. Such a small peeling force can be realized, for example, by appropriately selecting a combination of materials of the layer (B1) and the resin layer (B2) of the non-liquid crystal material, using mutually incompatible materials.

[1.2.3. Any layer]

The multi-layer film (B) may have any layer on the side opposite to the layer (B1) of the non-liquid crystal material of the resin layer (B2).

[1.3. Next layer]

As shown in Fig. 1, the surface 12U on the opposite side to the substrate (A1) 11 of the layer (A2) 12 of the non-liquid crystal material having a positive intrinsic birefringence, and the non-liquid crystal having a negative intrinsic birefringence Between the layer (B1) 21 of the material and the surface 21D on the opposite side of the resin layer (B2) 22, a single layer of the layer 30 is provided separately. Here, the adhesion layer 30 is separately interposed between the surface 12U and the surface 21D, which means that only the adhesion layer 30 is present between the surface 12U and the surface 21D, and there is no layer other than the adhesion layer 30.

The layer is then a layer formed by the cured product of the adhesive. Here, the adhesive agent includes an adhesive having a narrow storage elastic modulus of 1 MPa to 500 MPa at 23 ° C after curing, and an adhesive having a shear storage elastic modulus of less than 1 MPa at 23 ° C. However, when the multi-layer film (A) and the multi-layer film (B) are bonded together, when the adhesive is applied, the adhesive is suppressed in order to suppress biting bubbles and biting foreign matter during bonding, and to secure strong adhesion. The thickness of the layer tends to become thicker. In this regard, by using a narrow adhesive bonding, it is possible to The thickness is thinned. Therefore, as the adhesive, an adhesive having a narrowly defined elastic modulus of shear storage of 1 MPa to 500 MPa at 23 ° C after curing is preferred.

As the adhesive, an active energy ray-curable adhesive is usually used. The active energy ray-curable adhesive refers to an adhesive that can be cured when an active energy ray such as ultraviolet rays, X-rays, or electron beams is applied. Since an inexpensive device can be used, it is preferable to use an adhesive which can be hardened by using ultraviolet rays. Here, the active energy ray to be irradiated may include any energy ray such as visible light, ultraviolet light, infrared light, or electron ray.

As an example of a suitable adhesive, those which contain (meth)acrylate in an uncured state can be used. In particular, as (meth) acrylate, the (I) oligomer type polyfunctional (meth) acrylate, and the viscosity at (II) temperature 20 ± 1.0 ° C is 10 mPa. Above s and less than 500mPa. It is preferred that the s has a (meth) acrylate combination having at least one hydroxyl group.

(I) The oligomer-type polyfunctional (meth) acrylate is preferably 3 or less, and preferably 2 or 3, per 1 molecule of the functional group. The term "functional group" as used herein means the number of functional groups capable of exhibiting radical polymerizability. When the number of functional groups is 3 or less, since the hardening shrinkage of the cured product can be reduced and the glass transition temperature of the cured product can be lowered when the adhesive is cured, the multi-layer film (A) and the multi-layer film (B) can be obtained. Good to follow.

Examples of the (I) oligomer-type polyfunctional (meth) acrylate include polyester (meth) acrylate, epoxy (meth) acrylate, and urethane (meth) acrylate. An acrylic oligomer having a functional group having a radical polymerizable property of 3 or less, such as an ester, a polyether (meth) acrylate or an anthrone (meth) acrylate. Moreover, these types may be used alone or in combination of two at any ratio. Use above class.

The polyester (meth) acrylate can be obtained, for example, by a reaction product obtained by reacting a terminal hydroxyl group of a polyester with acrylic acid or methacrylic acid, wherein the polyester is obtained from a polybasic acid and a polyhydric alcohol.

Examples of the polybasic acid include capric acid, adipic acid, maleic acid, itaconic acid, succinic acid, and p-citric acid. These types may be used alone or in combination of two or more types in any ratio.

Examples of the polyhydric alcohol include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol. These types may be used alone or in combination of two or more types in any ratio.

In the case of the polyester (meth) acrylate, EBECRYL 851, 852, 853, 884, 885 (manufactured by DAICEL-CYTEC Co., Ltd.); OLESTAR (manufactured by Mitsui Chemicals, Inc.); ARONIX M-6100, 6200, 6250, 6500 (manufactured by Toagos Corporation).

The epoxy (meth) acrylate can be obtained, for example, by a reaction product obtained by subjecting an epoxy resin to a ring-opening addition reaction of acrylic acid or methacrylic acid.

Examples of the epoxy polymer include a bisphenol A type composed of bisphenol A and epichlorohydrin, a novolac type composed of a phenol novolak and epichlorohydrin, an aliphatic type, and an alicyclic type. Examples of the aliphatic epoxy polymer include diol diepoxypropyl ether, tripropylene glycol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, and 1,4-butanediol. Di-epoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, trimethylolpropane diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, and the like. Further, for example, a butadiene-based epoxy polymer or an isoprene-based epoxy polymerization can also be used. An unsaturated fatty acid epoxy polymer such as an object. The alicyclic epoxy polymer can be, for example, vinyl-epoxycyclohexane, 1,2-epoxy-4-vinylcyclohexane, 1,2:8,9-diepene terpene, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexene carboxylate, and the like. These types may be used alone or in combination of two or more types in any ratio.

When an epoxy (meth) acrylate is mentioned as an example, EBECRYL 600, 860, 3105, 3420, 3700, 3701, 3702, 3703, 3708, 6040 (made by DAICEL-CYTEC company), NEOPOL 8101, 8250 are mentioned. , 8260, 8270, 8355, 8351, 8335, 8414, 8190, 8195, 8316, 8317, 8318, 8319, 8371 (manufactured by U-PICA, Japan); DENACOL ACRYLATE DA212, 250, 314, 721, 722, DM201 (NAGASE) (manufactured by CHEMTEX Co., Ltd.); BANBEAM (manufactured by HARIMA Chemical Co., Ltd.); Miramer PE210, PE230, EA2280 (manufactured by Toyo Chemical Co., Ltd.).

A urethane (meth) acrylate can be, for example, a reaction having a urethane skeleton at the center by reacting a (meth) propylene monomer having a hydroxyl group, a polyfunctional isocyanate, and a polyhydric alcohol. The way things are obtained.

Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylolpropane toluene diisocyanate, and diphenylmethane triisocyanate, and are particularly suitable. A hexamethylene diisocyanate having good weather resistance is used. These types may be used alone or in combination of two or more types in any ratio.

As the polyol, for example, a polyester (meth) acrylate can be used as a user.

When the urethane (meth) acrylate is exemplified as a product, EBECRYL 204, 210, 220, 230, 270, 4858, 8200, 8201, 8402, 8804, 8807, 9260, 9270, KRM8098, 7735 can be cited. , 8296 (manufactured by DAICEL-CYTEC Co., Ltd.); UX2201, 2301, 3204, 3301, 4101, 6101, 7101, 8101, 0937 (manufactured by Nippon Kagaku Co., Ltd.); UV6640B, 6100B, 3700B, 3500BA, 3520TL, 3200B, 3000B, 3310B , 3210EA, 7000B, 6630B, 7461TE (manufactured by Nippon Synthetic Chemical Co., Ltd.); U-PICA8921, 8932, 8940, 8936, 8937, 8980, 8975, 8976 (manufactured by U-PICA, Japan); Miramer PU240, PU340 (Toyo CHEMICALS) System) and so on.

The polyether (meth) acrylate can be obtained, for example, as a reaction product of a polyether polyol and acrylic acid or methacrylic acid.

Examples of the polyether (meth) acrylate include ethoxylated trimethylolpropane triacrylate and propoxylated trimethylolpropane triacrylate. In the case of the product, EBECRYL 81 (manufactured by DAICEL-CYTEC Co., Ltd.) can be cited.

The fluorenone (meth) acrylate is, for example, a reaction product obtained by reacting an organic polyoxy siloxane with an alkenyl group-containing epoxy polymer and further reacting with acrylic acid or methacrylic acid. get.

As the organic polyoxane, for example, not only a methyl hydrogenated dioxane which is blocked by a trimethylhydroxy group at both ends of the molecular chain but also a dimethyloxy group blocked by a trimethylhydroxy group at both ends of the molecular chain may be mentioned. Methyl hydrogenated dioxane copolymer, dimethyl oxane blocked by trimethylhydroxyl at the end of the molecular chain. Methyl hydrogenated dioxane. Methylphenyl decane copolymer, dimethyl methacrylate with dimethyl hydroxydiene hydroxy group blocked at both ends of the molecular chain, and dimethyl hydrogenated dihydroxy hydroxy group at both ends of the molecular chain Locked dimethyl polyoxane. Methyl hydrogenated dioxane copolymer, dimethyl hydroxydiene hydroxy-blocked dimethyl oxane at both ends of the molecular chain. Methylphenyl decane copolymer, methyl phenyl polyoxyalkylene blocked by dimethyl hydrogenated dihydroxyl hydroxyl group at both ends of the molecular chain, and one end of the molecular chain is blocked by dimethyl hydrogenated dihydroxyl group and another molecular chain A substantially linear structure such as a dimethylpolyoxyalkylene blocked by a trimethylhydroxy group at one end may be a structure containing a branched siloxane structure in a part. These may be used alone or in combination of two or more kinds in any ratio.

As the alkenyl group-containing epoxy polymer, for example, an epoxy group having a glycidoxy group or the like and having an alkenyl group can be used. Here, the number of epoxy groups of the alkenyl group-containing epoxy polymer is usually 2 or more per molecule, preferably 2 to 7, preferably 2 to 3. Further, the number of alkenyl groups of the alkenyl group-containing epoxy polymer is usually one or more per molecule, preferably from 1 to 5, more preferably from 1 to 2, particularly preferably one. Further, the number of carbon atoms of the alkenyl group is preferably 2 to 6, more preferably 2 to 4. Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, and a hexenyl group. Among them, an allyl group is particularly preferred.

The (meth)acrylic acid can be obtained by reacting (meth)acrylic acid with an epoxy group in the addition reaction product of the above organopolysiloxane and an alkenyl group-containing epoxy polymer.

In the case of the example of the fluorenone (meth) acrylate, the compound exemplified in JP-A-2004-189942, "TEGO" manufactured by EVONIK DEGUSSA JAPAN Co., Ltd., and the SQ series manufactured by TOKISHIKI Co., Ltd., and the like.

Among these oligomeric polyfunctional (meth) acrylates, Esters (meth) acrylates, epoxy (meth) acrylates, and urethane (meth) acrylates are preferred.

Further, the oligo-type polyfunctional (meth) acrylate may be used singly or in combination of two or more kinds in any ratio.

The molecular weight of the oligomer-type polyfunctional (meth) acrylate is usually 500 or more and 10,000 or less in terms of the weight average molecular weight (Mw) of the polyisoprene measured by a gel permeation chromatography.

(I) The amount of the oligomer-type polyfunctional (meth) acrylate is 15 parts by weight to 65 parts by weight based on 100 parts by weight of the (meth) acrylate contained in the uncured adhesive. good. By being within this range, a stronger adhesion can be obtained.

As the viscosity at (II) temperature 20±1.0 °C is 10mPa. Above s and less than 500mPa. Examples of s having at least one hydroxyl group (meth) acrylate include the following. Further, in the following examples, the viscosity in the brackets indicates the viscosity of the sample at 20 ± 1.0 °C.

As a viscosity at a temperature of 20 ± 1.0 ° C is 10mPa. Above s and less than 500mPa. Examples of s having at least one hydroxyl group (meth) acrylate include 2-hydroxypropyl acrylate (10.9 mPa.s), 4-hydroxybutyl acrylate (17 mPa.s), and 2-hydroxy acrylate- 3-phenoxypropyl ester (373 mPa.s), glycerol monomethacrylate (for example, "BLEMMER GLM" 150 mPa.s by Nippon Oil Co., Ltd.), polyethylene glycol monomethacrylate (for example, manufactured by Nippon Oil Co., Ltd.) BLEMMER PE-90" 15mPa.s; "BLEMMER PE-200" 30mPa.s made by Nippon Oil Co., Ltd.; "BLEMMER PE-350" 45mPa.s made by Nippon Oil Co., Ltd.), polypropylene glycol monomethacrylate (such as Nippon Oil Company) "BLEMMER PP-1000" 50mPa.s; System system "BLEMMER "PP-500" 75mPa. s), poly(ethylene propylene glycol) monomethacrylate (for example, "BLEMMER 50PEP-300" 55mPa.s by Nippon Oil Co., Ltd.), polyethylene glycol. Polypropylene glycol monomethacrylate (for example, "BLEMMER 70PEP-350B" 79mPa.s by Nippon Oil Co., Ltd.), propylene glycol. Polybutylene glycol monomethacrylate (for example, "BLEMMER 10PPB-500B" 48mPa.s by Nippon Oil Co., Ltd.), polyethylene glycol monoacrylate (for example, "BLEMMER AE-200" 15mPa.s by Nippon Oil Co., Ltd.), Polypropylene glycol monoacrylate (for example, "BLEMMER AP-400" 48mPa.s by Nippon Oil Co., Ltd.), aliphatic epoxy acrylate (for example, "EBECRYL112" manufactured by DAICEL-CYTEC Co., Ltd. 55mPa.s; "PA500" manufactured by Toho Chemical Co., Ltd. 71.8 mPa.s) and so on.

By using a viscosity at (2) temperature of 20 ± 1.0 ° C is 10 mPa. Above s and less than 500mPa. It is preferred that one of the at least one hydroxyl group (meth) acrylate has good suitability for the adhesive coating, and then the layer exhibits a stronger adhesion. The above range of viscosity at a temperature of 20 ± 1.0 ° C is preferably 50 mPa. Above s, especially good for 70mPa. Above s, preferably 400 mPa. Below s, especially good for 350mPa. s below.

The viscosity at (II) temperature 20±1.0°C is 10mPa. Above s and less than 500mPa. The amount of one (meth) acrylate having at least one hydroxyl group is preferably 35 parts by weight to 85 parts by weight based on 100 parts by weight of the (meth) acrylate contained in the uncured state. By being within this range, a stronger adhesion can be obtained.

Further, in the hardened state or the uncured state, the adhesive agent may contain any component other than the (meth) acrylate, insofar as the effect of the present invention is not significantly impaired. Examples of the optional component include a polymerization initiator, Crosslinking agent, inorganic filler, polymerization inhibitor, coloring pigment, dye, antifoaming agent, leveling agent, dispersing agent, light diffusing agent, plasticizer, antistatic agent, surfactant, non-reactive polymer (inert polymerization) ()), viscosity modifier, near-infrared absorbing material, etc. These types may be used alone or in combination of two or more types in any ratio.

The type of the polymerization initiator can be selected in accordance with the aspect of curing of the adhesive. For example, when the adhesive agent can be cured by irradiation with an active energy ray, a photopolymerization initiator can be used. At this time, a photosensitizer may be used in combination with a photopolymerization initiator.

Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 1-(4-isopropylbenzene). 2-hydroxy-2-methylpropan-1-one, thioxanthone, 2-chlorothioxantone, 2-methylthioxanthone, 2 ,2-diethylthioxanthone, methyl benzhydrazide, 2,2-diethoxyacetophenone, beta-ionone, beta-bromo Styrene, diazoaminobenzene, α-amylcinnamaldehyde, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-chlorodiphenyl ketone, p,p'- Dichlorodiphenyl ketone, p,p'-bisdiethylaminodiphenyl ketone, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-propyl ether Benzoin n-propyl ether), benzoin n-butyl ether, diphenyl sulfide, bis(2,6-methoxybenzhydryl)-2,4,4- Trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzimidyldiphenyl-phosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenyl Phosphine, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholino-1-one, 2-benzyl-2-dimethylamino 1-(4-morpholinylphenyl)-butan-1-one, decyl diphenyl ketone, α-chloropurine, diphenyl disulfide, hexachlorobutadiene, pentachlorobutadiene, Octachlorobutene, 1-chloromethylnaphthalene, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(o-benzylidene)]indole, 1-[9-B -6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone 1-(o-ethylidene), (4-methylphenyl)[4-(2-A Propyl)phenyl]iodonium hexafluorophosphate, 3-methyl-2-butynyltetramethylphosphonium hexafluoroantimonate, diphenyl-(p-phenylthiophenyl)phosphonium hexafluoroantimonate Acid esters, etc. These types may be used alone or in combination of two or more types in any ratio.

The polymerization starting dose is preferably 0.5 parts by weight or more, preferably 1 part by weight or more, and 10 parts by weight or less, based on 100 parts by weight of the (meth) acrylate contained in the uncured adhesive. Preferably, it is preferably 5 parts by weight or less.

Further, examples of the photosensitizer include n-butylamine, triethylamine, and poly-n-butylphosphine.

Examples of the antifoaming agent include BYK051, 052, 055, 057, 1790, 065, 070, 088, 354, and 392 manufactured by BYK-Chemie Japan Co., Ltd.; LR-20R, OP-80R, and OP- manufactured by Nippon Oil & Fats Co., Ltd. 83RAT, OP-85R, PP-40R, SO-80R, SP-60R, BP-70R, CP-08R, DS-60HN, etc. These types may be used alone or in combination of two or more types in any ratio.

The antifoaming agent can be used in an amount in which the adhesion of the adhesive layer is not lowered. Specifically, it is preferably 0.1 part by weight or more, and 1.0 part by weight, based on 100 parts by weight of the solid content of the adhesive in an uncured state. The following is preferred, and it is preferably 0.5 parts by weight or less.

As the crosslinking agent, for example, it is possible to use a molecular weight of less than 500 A (meth) acrylate monomer having a functional group or more. Specific examples of the crosslinking agent include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol diethylene glycol. Acrylate, glycerin dimethacrylate, 2-hydroxy-3-propenyl propyl methacrylate, tetraethylidene diacrylate, polyethylene glycol diacrylate, tricyclodecane dimethanol II Methyl) acrylate, dipentaerythritol hexaacrylate, 1,6-hexanediol di(meth) acrylate, hydroxytrimethylacetic acid neopentyl glycol diacrylate, 1,9-nonanediol Di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane tri(meth)acrylate, double Trimethylolpropane tetraacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate, ethoxylate Bisphenol A dimethacrylate. These types may be used alone or in combination of two or more types in any ratio.

The amount of the crosslinking agent is preferably 0.5 parts by weight or more, preferably 1 part by weight or more, more preferably 10 parts by weight or less, based on 100 parts by weight of the (meth) acrylate contained in the uncured adhesive. It is preferably 5 parts by weight or less. By setting the amount of the crosslinking agent to be equal to or higher than the lower limit of the above range, the mechanical strength of the adhesive layer can be effectively improved. Moreover, by setting it as an upper limit or less, the adhesive force of the multilayer film (A) and the multilayer film (B) can be improved.

As the viscosity adjuster, for example, a slurry obtained by dispersing particles of a metal oxide having a particle diameter of several nm to several hundreds nm in a solvent can be used. Examples of the metal oxide include cerium oxide, aluminum hydroxide, aluminum oxide, titanium oxide, zinc oxide, barium sulfate, magnesium citrate, and the like. Specific examples of the viscosity modifier include organic cerium oxide dissolved by Nissan Chemical Co., Ltd. Glue, methanol cerium oxide sol, IPA-ST, IPA-ST-UP, IPA-ST-ZL, EG-ST, NPC-ST-30, DMAC-ST, MEK-ST, MIBK-ST, XBA-ST, PMA-ST, PGM-ST; PL-1-IPA, PL-1-TOL, PL-2L-PGME, PL-2L-MEK, etc. manufactured by Fuso Chemical Co., Ltd. These types may be used alone or in combination of two or more types in any ratio.

The viscosity-adjusting dose is preferably 1 part by weight or more, preferably 5 parts by weight or more, based on 100 parts by weight of the (meth) acrylate contained in the uncured state. The remainder is preferably below, preferably 10 parts by weight or less. By setting the viscosity adjustment amount to be equal to or higher than the lower limit of the above range, the viscosity of the adhesive in the uncured state can be appropriately adjusted. Moreover, by setting it as an upper limit or less, the adhesive force of the multilayer film (A) and the multilayer film (B) can be improved.

Specific examples of the adhesive agent include the examples described in JP-A-7-82544.

The thickness of the layer is preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 3 μm or more, and most preferably 30 μm or less, more preferably 20 μm or less, still more preferably 10 μm or less. By setting the thickness of the adhesive layer to the lower limit of the above range, the adhesion between the multi-layer film (A) and the multi-layer film (B) can be improved. In addition, by setting it as the upper limit or less, it is possible to accelerate the curing rate of the adhesive, and it is easy to harden the adhesive, and it is possible to reduce the thickness.

[1.4. Other matters of laminated body]

In the above laminated body, the layer (A2) of the non-liquid crystal material having a positive birefringence and the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence have desired optical characteristics (especially hysteresis). value). Therefore, by taking the unwanted layers from When the laminated body is peeled off, a phase difference film in which a layer (A2) of a non-liquid crystal material having a positive intrinsic birefringence is combined and a layer (B1) of a non-liquid crystal material having a negative intrinsic birefringence can be easily obtained.

Further, in the above laminated body, the layer (A2) of the non-liquid crystal material having a positive birefringence and the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence can be obtained. In particular, since the mechanical strength of the non-liquid crystal material having a negative intrinsic birefringence is generally low, the layer (B1) of the non-liquid crystal material is easily broken. However, in the above laminated body, the layer of the non-liquid crystal material can be stably prevented. (B1) Damaged. Further, in general, even if the layer (A2) of the non-liquid crystal material having a positive intrinsic birefringence and the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence are thinned, the thickness variation can be reduced. Therefore, by peeling off an unnecessary layer from the laminated body, a retardation film having a small thickness can be easily obtained.

[1.5. Manufacturing method of laminated body]

The layered body 100 shown in Fig. 1 can be produced, for example, by a method comprising the steps of: producing a multi-layer film (A) 10; and producing a multi-layer film (B) 20; The layer 30 is a step of laminating the multi-layer film (A) 10 and the multi-layer film (B) 20. Hereinafter, this manufacturing method will be described.

[1.5.1. Example of Manufacturing Step of Multilayer Film (A)]

Fig. 2 is a schematic view showing an example of a manufacturing apparatus 200 for manufacturing a multi-layer film (A) 10. As shown in FIG. 2, when manufacturing the multi-layer film (A) 10, the manufacturing apparatus 200 provided with the expansion part 210, the drying part 220, and the extension part 230 can be used.

The development unit 210 is capable of dissolving (casting) the solution 240 in which the non-liquid crystal material having a positive intrinsic birefringence is dissolved in a solvent (A1) 11 The device on it.

As a solvent in which the non-liquid crystal material having a positive intrinsic birefringence is dissolved, a non-liquid crystal material capable of neutralizing the intrinsic birefringence can be used without causing extreme erosion of the substrate (A1). The solvent can be selected in accordance with the non-liquid crystal material and the substrate (A1) having a positive intrinsic birefringence to be used. Specific examples of the solvent include halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, dichloromethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, and o-dichlorobenzene; Phenols such as phenol and p-chlorophenol; aromatic hydrocarbons such as benzene, toluene, xylene, methoxybenzene, and 1,2-dimethoxybenzene; acetone, ethyl acetate, tert-butanol, and glycerin , ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol, ethyl 赛路苏(ethyl cellosolve), butyl cellosolve, 2-pyrrolidone, N-methyl-2-pyrrolidone, pyridine, triethylamine, dimethylformamide, dimethylacetamidine Amine, acetonitrile, butyronitrile, methyl isobutyl ketone, methyl ether ketone, cyclopentanone, carbon disulfide, and the like. Further, sulfuric acid may be used as the solvent in accordance with the type of the non-liquid crystal material having a positive intrinsic birefringence. The solvent may be used singly or in combination of two or more kinds in any ratio.

In the solution 240, in consideration of the coating property to the substrate (A1) 11 (for example, the foreign matter is mixed, the unevenness at the time of coating, and the degree of generation of a line), the concentration of the non-liquid crystal material having a positive intrinsic birefringence is 0.5 weight. More preferably, it is 1 or more, more preferably 1% by weight or more, particularly preferably 2% by weight or more, more preferably 50% by weight or less, more preferably 40% by weight or less, and particularly preferably 30% by weight or less. By setting the concentration to be equal to or higher than the lower limit of the above range, the viscosity of the solution 240 can be increased and the solution 240 can be spread at a desired thickness. Moreover, it can be lowered by setting it as an upper limit or less. The viscosity of the solution 240 prevents the surface of the layer of the solution 240 from deteriorating.

Further, the solution 240 may contain a formulation such as a surfactant, in addition to a non-liquid crystal material having a positive intrinsic birefringence and a solvent.

In the method of unfolding the expansion unit 210, a coating method is generally used. Specific examples of the coating method include a spin coating method, a roll coating method, a die coating method, and a blade coating method.

The drying unit 220 is a device capable of drying the solution 240 developed on the substrate (A1) 11. By drying the solution 240, the pre-extension film 250 having the substrate (A1) 11 and the layer (A2) of the non-liquid crystal material having a positive intrinsic birefringence in this order can be obtained. The drying section is preferably a device capable of adjusting the temperature in the range of 30 ° C to 200 ° C, and is preferably provided with a mechanism for positively controlling the temperature controlled by the controlled temperature to the film surface.

The extension portion 230 is a device capable of extending the substrate (A1) 11 after drying the solution 240. When the substrate (A1) 11 is extended, the layer (A2) of the positive non-liquid crystalline material formed thereon is also extended. Since the hysteresis value is exhibited by the extension, a layer (A2) of a non-liquid crystal material having a desired hysteresis value can be obtained. As such an extension 230, for example, a spreader can be used. The spreader machine generally has a pair of rolling passes; and a gripper that can move along the pass. The rolling pass system has a rolling groove expansion portion in which the rolling groove expanding portion is formed on the downstream side in the MD direction of the strip-shaped film, and the rolling pass width is expanded into a tapered shape in the TD direction. In such a spreader, the strip film can be extended in the TD direction by gripping both end portions of the film in the TD direction with the grip member and moving the grip member along the rolling pass.

When the multilayer film (A) is produced by using such a manufacturing apparatus 200, It is possible to use a long film-form substrate (A1) 11 and to manufacture it by a winding method. For example, the substrate (A1) 11 is pulled out from the roll of the substrate (A1) 11, and the drawn substrate (A1) 11 is continuously sent to the developing portion 210. ]

The thickness of the substrate (A1) 11 before stretching is preferably 40 μm or more, preferably 60 μm or more, from the viewpoint of improving workability and mechanical strength, and is preferably 500 μm or less from the viewpoint of improving workability. It is preferably 150 μm or less.

In the unfolding portion 210, a step of expanding (casting) the solution 240 is performed on the substrate (A1) 11. At this time, the amount of the developing solution 240 can be such that the thickness of the layer (A2) 12 of the non-liquid crystalline material having the desired thickness of the multi-layer film (A) 10 can be obtained by expanding the thickness of the solution 240 formed. Mode setting.

On the surface 11U of the substrate (A1) 11, the region where the solution 240 is unfolded is not the entire substrate (A1) 11, but is preferably a region where the grip at the time of stretching is removed. For example, the base material (A1) 11 has a strip shape, and when the strip-shaped base material (A1) 11 is extended in the TD direction, the grip portion at the time of extension, that is, the both ends in the width direction of the base material (A1) 11 Except for the portion, it is preferred to spread the solution 240 in the central portion of the substrate (A1) 11.

The substrate (A1) 11 after the solution 240 is developed on the surface 11U is sent to the drying section 220. In the drying section 220, a step of drying the solution 240 which is developed on the surface of the substrate (A1) 11 is performed.

The drying temperature may be set according to the solvent type of the solution 240, preferably 40 ° C or higher, preferably 50 ° C or higher, preferably 250 ° C or lower, and more preferably 200 ° C or lower. The drying system can be carried out at a certain temperature, or can be carried out by increasing the temperature stepwise or continuously.

The drying time is preferably 10 seconds or longer, preferably 30 seconds or longer, preferably 60 minutes or shorter, more preferably 30 minutes or shorter. By setting the drying time to be equal to or higher than the lower limit of the above range, the solvent can be sufficiently removed from the layer of the solution 240 to improve the reliability of the product. Moreover, productivity can be improved by setting it as an upper limit or less.

A layer (A2) of a non-liquid crystal material having a positive intrinsic birefringence is formed on the surface of the substrate (A1) 11 by drying. The thickness of the layer (A2) of the non-liquid crystal material having a positive intrinsic birefringence before stretching obtained in this manner is preferably thinner than the thickness of the substrate (A1) 11 before stretching, in comparison with the aforementioned substrate ( It is more preferable that half of the thickness of A1)11 is smaller. By the thickness of the layer (A2) of the non-liquid crystal material having a positive intrinsic birefringence before stretching, the thickness of the substrate (A1) 11 is relatively reduced, and uniform stretching can be performed at the time of the stretching treatment.

Further, the specific thickness of the layer (A2) of the non-liquid crystal material having a positive intrinsic birefringence before stretching can be set in accordance with the thickness of the layer (A2) of the non-liquid crystal material obtained after stretching, to 0.5. The thickness is preferably μm or more, preferably 1 μm or more, more preferably 50 μm or less, and still more preferably 30 μm or less. By setting the thickness to the lower limit or more of the above range, a sufficient hysteresis value and mechanical strength can be obtained in the layer (A2) 12 of the non-liquid crystal material of the multi-layer film (A) 10. In addition, it is possible to increase the damage resistance and workability of the layer (A2) 12 of the non-liquid crystal material of the multi-layer film (A) 10, and to reduce the thickness and further suppress the thickness. deviation.

The substrate (A1) 11 having a layer (A2) of a non-liquid crystal material having a positive intrinsic birefringence formed by drying is sent to the extending portion 230. In the extension portion 230, a step of extending the substrate (A1) 11 is performed.

In this case, it is preferable to stretch the portions of the non-liquid crystal material having the undeveloped intrinsic birefringence of the base material (A1) 11 at both ends in the TD direction. That is, it is preferable to set the holding portion for extension to be only the substrate (A1) 11. When the substrate (A1) 11 is stretched in a state in which the layer (A2) of the non-liquid crystal material having a positive in birefringence is formed on the substrate (A1) 11, the substrate (A1) 11 can be subjected to the substrate (A1) 11 The substrate (A1) 11 is uniformly extended by the tension. At this time, the uniform extension of the substrate (A1) 11 acts on the layer (A2) of the non-liquid crystalline material having the positive intrinsic birefringence because the layer having the intrinsic birefringence is a positive non-liquid crystalline material (A2) It is indirectly extended, and a more uniform extension can be performed than when the layer (A2) of the non-liquid crystalline material having the intrinsic birefringence is directly extended. That is, the substrate (A1) 11 serves as a function of the relaxation layer, and the propagation method of the extension stress from the holding portion of the substrate (A1) 11 to the layer (A2) of the non-liquid crystal material having a positive intrinsic birefringence The system becomes slow, and as a result, it can extend more evenly in the width direction. In particular, when the thickness of the layer (A2) of the non-liquid crystal material having a positive intrinsic birefringence is relatively small and the thickness of the substrate (A1) 11 is relatively decreased, since the tension system mainly causes the aforementioned substrate (A1) 11 It is particularly preferable to carry out the stretching of the layer (A2) of the non-liquid crystal material having a positive intrinsic birefringence more uniformly.

The stretching temperature is preferably in the range of a glass transition temperature of ±20 ° C of the material forming the substrate (A1) 11, and preferably less than the glass transition temperature of the non-liquid crystal material having a positive intrinsic birefringence. The specific extension temperature is preferably 40 ° C or higher, preferably 80 ° C or higher, particularly preferably 100 ° C or higher, preferably 250 ° C or lower, preferably 220 ° C or lower, and particularly preferably 200 ° C or lower. By extending at a glass transition temperature of the substrate (A1) 11 at a temperature of -20 ° C or higher, stretching can be performed with a small tension. Also, because stress concentration can be suppressed to be on the substrate (A1) 11 Since the boundary between the region of the layer (A2) having the intrinsic birefringence and the non-liquid crystal material is formed, the substrate (A1) can be prevented from being damaged. Further, by extending at a glass transition temperature of the substrate (A1) 11 at a temperature of +20 ° C or lower, the stretching of the layer (A2) of the non-liquid crystal material having a positive intrinsic birefringence can be surely performed. Further, by extending the glass transition temperature of the non-liquid crystal material having positive intrinsic birefringence or less, it is possible to stably control the stretching, and it is possible to obtain a desired hysteresis value without applying a load in the manufacturing step.

The stretching ratio is preferably 1.01 or more, more preferably 1.03 times or more, particularly preferably 1.05 times or more, more preferably 2 times or less, more preferably 1.7 times or less, and particularly preferably 1.5 times or less. By setting the stretching ratio to be equal to or higher than the lower limit of the above range, the layer (A2) 12 of the non-liquid crystal material can stably exhibit the required hysteresis value. Moreover, by setting it as the upper limit or less, it is possible to prevent unevenness of the extension and to make the hysteresis value of the layer (A2) 12 of the non-liquid crystal material uniform. Here, the number of extensions may be one or two or more.

By the above extension, the layer (A2) of the non-liquid crystal material having a positive intrinsic birefringence exhibits a hysteresis value, and a multilayer film (A) 10 having desired optical characteristics can be obtained. In the multi-layer film (A) 10, the slow phase axis in the plane of the layer (A2) 12 of the non-liquid crystal material having a positive intrinsic birefringence is generally parallel to the direction in which the extending portion 230 is extended.

Further, in the production method, steps other than the above may be performed.

For example, after the extension, the mitigation step can also be performed as necessary. In the relaxation step, the substrate (A1) 11 to be stretched is held for a predetermined time and at a predetermined temperature to shrink the substrate (A1) 11. The relaxation rate at this time is preferably within 20%, and the temperature is maintained at a glass transition temperature of ±30 ° C of the material forming the substrate (A1) 11 described above. The circumference is better, and the retention time is preferably from 1 second to 60 seconds.

Further, for example, after the stretching, the obtained multi-layer film (A) 10 can be cooled to room temperature as necessary. The cooling rate and the cooling means are not particularly limited. However, when the tension at the time of stretching is suddenly released before cooling, since wrinkles are likely to occur in the obtained multi-layer film (A) 10, it is preferable to carry out part or all of the cooling step before releasing the tension. ]

The obtained multi-layer film (A) 10 is usually taken up in a roll shape and stored. In the multi-layer film (A) 10 obtained by such a production method, the thickness deviation of the layer (A2) 12 which is a non-liquid crystal material is small, and the hysteresis value of the layer (A2) 12 of the non-liquid crystal material is uniform.

[1.5.2. Example of Manufacturing Step of Multilayer Film (b)]

The multi-layer film (B) is generally capable of comprising a multi-layer film comprising a layer (B1) of a non-liquid crystal material having a resin layer (B2) and a negative intrinsic birefringence in order, and the layer The manufacturing method of the step of stretching the film is carried out. In particular, a multi-layer film (b) having a layer (B1) and a resin layer (B2) of a non-liquid crystal material having a resin layer (B2) and a negative intrinsic birefringence in order is produced, and the multi-layer film (b) is used. After the stretching, it is preferred to peel the resin layer (B2) on one side from the stretched multi-layer film (b) to obtain a multi-layer film (B). The layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence is generally weak in mechanical strength, but by covering both surfaces of the layer (B1) of the non-liquid crystal material by using the resin layer (B2), the extension can be surely prevented. The layer (B1) of the non-liquid crystal material is broken. Moreover, since the layer (B1) of the non-liquid crystal material is sandwiched by the resin layer (B2) having high strength from both sides, it can be protected, and therefore it is possible to effectively prevent bleed out from the layer (B1) of the non-liquid crystal material. Here, the bleed out from the layer (B1) of the non-liquid crystal material means that it is contained in the layer (B1) of the non-liquid crystal material. A phenomenon in which a part of the component (for example, a formulation agent) bleeds out to the surface of the layer (B1) of the non-liquid crystalline material.

Fig. 3 is a schematic view showing an example of a manufacturing apparatus 300 for manufacturing a multi-layer film (b) 310. As shown in FIG. 3, when manufacturing the multi-layer film (b) 310, the manufacturing apparatus 300 provided with the film-molding part 320 and the extension part 330 can be used.

The film forming unit 320 is a device that includes a resin layer (B2), a layer (B1) of a non-liquid crystal material having a negative intrinsic birefringence, and a multi-layer film (b) of a resin layer (B2). Examples of the production method include a co-extrusion T-die method, a co-extrusion blow molding method, a co-extrusion lamination method, and the like; a coextrusion molding method such as dry lamination; a co-casting method; And a method of applying a coating method such as a resin solution to the surface of the resin film. In particular, from the viewpoint of production efficiency and the fact that volatile components such as a solvent are not left in the film, a co-extrusion molding method is preferred.

When the co-extrusion molding method is employed, the multi-layer film (b) can be obtained, for example, by co-extruding a non-liquid crystal material having a negative intrinsic birefringence and a resin forming the resin layer (B2). Examples of the co-extrusion molding method include a co-extruded T-die method, a co-extrusion blow molding method, a co-extrusion lamination method, and the like, and in particular, a co-extruded T-die method is preferred. Further, the co-extruded T-die method has a feed block method and a multi-manifold method, and it is particularly preferable to reduce the thickness variation by the multi-manifold method.

In Fig. 3, a multi-layer film (b) 340 before stretching is produced by co-extruding a material from a mold 321 onto a cooling roll 322.

The extension portion 330 is a device capable of extending the multi-layer film (b) 340 before stretching. By extending the pre-extended multi-layer film (b) 340, The layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence exhibits a hysteresis value and can obtain a desired multi-layer film (b). As the extension performed in the extension portion 330, for example, a method of uniaxially extending in the MD direction by the circumferential speed difference between the rolls (longitudinal uniaxial stretching) can be employed; in the TD direction using a spreader stretching machine Uniaxial extension method (transverse uniaxial extension); method of longitudinal uniaxial extension and lateral uniaxial extension in sequence (sequential biaxial extension); simultaneous longitudinal uniaxial extension and lateral uniaxial extension (simultaneous biaxial Extension); a method of extending in a direction inclined in the MD direction (inclined extension) or the like. The term "inclined direction" as used herein means a direction that is not parallel and is not orthogonal.

When the multi-layer film (b) is produced by using the manufacturing apparatus 300, the film forming unit 320 is a step of coextruding a non-liquid crystal material having a negative intrinsic birefringence and a resin forming the resin layer (B2).

In the coextrusion process, in the extruder having a mold, the melting temperature of the non-liquid crystal material having a negative intrinsic birefringence and the resin forming the resin layer (B2) is set to be higher than the non-liquid crystal materials and resins. The glass transition temperature is preferably higher than 80 ° C, preferably higher than 100 ° C, and preferably higher than 180 ° C to set higher 150 ° C. The temperature below is preferred. By setting the melting temperature of the extruder to be equal to or higher than the lower limit of the above range, the fluidity of the resin can be sufficiently improved, and by setting it as the upper limit or less, deterioration of the resin can be prevented.

By the co-extrusion, the layer (B1) in which the resin layer (B2), the non-liquid crystal material having a negative intrinsic birefringence, and the multi-layer film (b) 340 before the extension of the resin layer (B2) are obtained can be obtained. In the obtained multi-layer film (b) 340 before stretching, the thickness of the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence can be The ratio of the thickness of the layer (B1) and the resin layer (B2) of the non-liquid crystalline material of the laminated body finally obtained is set. From the viewpoint of obtaining sufficient hysteresis value and mechanical strength, the specific thickness of the layer (B1) of the non-liquid crystal material is preferably 10 μm or more, preferably 50 μm or more, and further, from the viewpoint of improving flexibility and workability. Preferably, it is 800 μm or less, preferably 600 μm or less.

Further, in the multi-layer film (b) 340 before stretching, the thickness of each layer of the resin layer (B2) is preferably 5 μm or more, and more preferably 10 μm or more, from the viewpoint of sufficiently obtaining mechanical strength. From the viewpoint of improving flexibility and workability, it is preferably 100 μm or less, and more preferably 50 μm or less.

Further, the overall thickness of the multi-layer film (b) 340 before stretching is preferably 20 μm or more, preferably 70 μm or more, more preferably 1000 μm or less, or more preferably 700 μm or less. When the value is equal to or greater than the lower limit of the above range, a sufficient hysteresis value and mechanical strength can be obtained, and if it is equal to or less than the upper limit value, flexibility and workability can be improved.

The obtained multi-layer film (b) 340 before stretching is sent to the extended portion 330. In the extending portion 330, a step of extending the multi-layer film (b) 340 before stretching is performed.

When the elongation temperature is expressed by the glass transition temperature Tg (B1) of the non-liquid crystalline material having a negative intrinsic birefringence of the formation layer (B1), it is preferably Tg (B1) -20 ° C or more, and Tg (B1). More preferably, it is -15 ° C or more, and more preferably Tg (B1) - 13 ° C or more. Further, Tg(B1)+20°C or less is preferable, Tg(B1)+2°C or less is preferable, Tg(B1)-2°C or less is more preferable, and Tg(B1)-11°C or less is preferable. Very good.

The stretching ratio is preferably 1.2 times or more, more preferably 2.5 times or more, and most preferably 6 times or less, more preferably 5.0 times or less. Extension ratio is the range At the time, the thickness is thin and a layer (B1) of a non-liquid crystalline material having a desired hysteresis value can be obtained. Here, the number of extensions may be one time or two or more times.

By the above extension, the hysteresis value is exhibited in the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence, and the multi-layer film (b) 310 having the desired optical characteristics can be obtained. In the multi-layer film (b) 310, the slow phase axis in the plane of the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence is generally perpendicular to the direction in which the extending portion 330 is extended.

Further, in the production method, steps other than the above may be performed. For example, the pre-extension coating film (b) 340 may be subjected to a pre-heat treatment.

The obtained multi-layer film (b) 310 is usually taken up in a roll shape and stored. The multilayer film (b) 310 obtained by using such a production method has mechanical strength of the layer (B1) of the non-liquid crystal material, but is not easily damaged by the resin layer (B2).

[1.5.3. Example of fitting step]

Fig. 4 is a schematic view showing an example of a device 400 for bonding a multi-layer film (A) 10 and a multi-layer film (B) 20 to produce a laminate 100. As shown in FIG. 4, when manufacturing the laminated body 100, the manufacturing apparatus 400 provided with the peeling part 410, the coating part 420, the bonding part 430, and the hardening process part 440 can be used.

The peeling portion 410 is a device in which the one-layer resin layer (B2) 450 is peeled off from the multi-layer film (b) 310 which is extended as shown in FIG. By peeling one resin layer (B2) 450, the surface on one side of the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence is exposed, and a layer having a non-liquid crystal material (B1) can be obtained. And a multi-layer film (B) 20 of the resin layer (B2).

The coating portion 420 is capable of inherent birefringence in the multilayer film (B) 20 A device for applying an adhesive layer to the exposed surface of the layer (B1) of the negative non-liquid crystal material. In other words, the application portion 420 can apply the adhesive 460 to the surface 21D of the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence of the multi-layer film (B) opposite to the resin layer (B2). . For the coating method of the adhesive layer, for example, a die coating method such as a roll coating method, a curtain coating method, a slit coating method, or the like, a spray coating method, or the like can be used, and is not particularly limited.

The bonding portion 430 is capable of bonding the layer (A2) of the adhesive layer formed in the multi-layer film (B) and the non-liquid crystal material having a positive birefringence to the multi-layer film (A) to the substrate (A1). A device that fits the face 12U on the opposite side. The method of bonding by the bonding part 430 can be performed by any lamination means. However, it is preferable to carry out the method of removing the bubbles mixed in the bonding. For example, in the continuous lamination process such as the roll-to-roll method shown in Fig. 4, for example, (i) the holding pressure between the bonding roller 431 and the counter roller 432 is increased ( Ii) reducing the lamination processing speed, (iii) when the bonding roller 431 is made of rubber and the counter roller 432 is made of metal, the total thickness of the multi-layer film (B) 20 is a composite film (A) When the total thickness of 10 is thicker, the method of the base material (A1) of the laminated film (A) 10 or the like is selected, and the incorporation of bubbles can be suppressed. Further, in the batch lamination treatment, for example, by (iv) increasing the surface pressure and (v) vacuum pressing or the like, it is possible to suppress the incorporation of bubbles.

The hardening treatment unit 440 is a device capable of performing a treatment for curing the adhesive contained in the adhesive layer. The specific hardening treatment can be appropriately treated in accordance with the adhesive to be used. For example, when an active energy ray-curable adhesive such as ultraviolet rays is used, a device capable of uniformly irradiating the active energy ray in the TD direction is exemplified. As a specific device, for example, a light source of ultraviolet light In other words, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a black light, a microwave-excited mercury lamp, a halogenated metal lamp, and the like can be cited.

When the laminated body 100 is manufactured by using such a manufacturing apparatus 400, the long laminated film (A) 10 and the multilayer film (b) 310 can be manufactured by the winding method. For example, the multi-layer film (b) 310 is pulled out from the roll of the multi-layer film (b) 310, and the pulled-up multi-layer film (b) 310 is sent to the peeling portion 410.

In the peeling portion 410, a step of peeling the one side resin layer (B2) 450 from the multi-layer film (b) 310 to obtain a multi-layer film (B) 20 is performed. The obtained multilayer film (B) 20 is sent to the coating portion 420. Further, the resin layer (B2) 450 which is peeled off from the multi-layer film (b) 310 is usually taken up in a roll shape and recovered.

The coating portion 420 is applied to the surface 21D of the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence of the multi-layer film (B) 20 opposite to the resin layer (B2), and an adhesive layer is applied. That is, the adhesive 460 is applied to the face 21D of the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence which is exposed by peeling off the resin layer (B2) 450, and the adhesive 460 in an uncured state. The layer of the layer forms the next layer.

The multi-layer film (B) 20 coated with the adhesive layer is sent to the bonding portion 430. Further, in the bonding portion 430, the multi-layer film (A) 10 drawn from the roll of the multi-layer film (A) 10 is also sent. In the bonding portion 430, the multi-layer film (A) 10 and the multi-layer film (B) 20 are sandwiched by the bonding roller 431 and the counter roller 432, and the inherent film of the multi-layer film (B) 20 is doubled. The adhesion layer formed by the surface 21D of the layer (B1) of the non-liquid crystal material having a negative refractive index, and the layer (A2) of the non-liquid crystal material having the positive birefringence of the multi-layer film (A) 10 (A1) is the opposite side of the face 12U Hehe. The layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence of the multi-layer film (B) 20 is weak in mechanical strength, but is not reinforced by the resin layer (B2).

At this time, in the multi-layer film (A) 10, the arithmetic mean roughness of the surface 12U on the opposite side to the substrate (A1) of the layer (A2) which is a non-liquid crystal material having a positive intrinsic birefringence as a bonding surface is used. The degree Ra is preferably 0.001 μm or more, more preferably 0.005 μm or more, and most preferably 0.1 μm or less, and more preferably 0.05 μm or less. By setting the arithmetic mean roughness Ra of the surface 12U of the layer (A2) of the non-liquid crystal material to be equal to or lower than the lower limit of the above range, the smoothness of the multi-layer film (A) and the roll at the time of conveyance can be improved. Moreover, by setting it as an upper limit or less, it can reduce haze.

Further, in the multi-layer film (B), the layer (B1) of the non-liquid crystal material having a negative birefringence in which the intrinsic birefringence of the multi-layer film (B) 20 serving as the bonding surface is opposite to the resin layer (B2) The arithmetic mean roughness Ra of the surface 21D is preferably 0.0005 μm or more, more preferably 0.001 μm or more, and most preferably 0.1 μm or less, and more preferably 0.05 μm or less. By setting the arithmetic mean roughness Ra of the surface 21D of the layer (B1) of the non-liquid crystal material to be equal to or lower than the lower limit of the above range, the smoothness of the multi-layer film (B) and the roll at the time of conveyance can be improved. Moreover, the haze can be reduced by setting it as an upper limit or less.

Subsequently, the multi-layer film (A) 10 and the multi-layer film (B) 20 which are bonded together by the subsequent layer are sent to the hardening treatment portion 440. In the example shown in FIG. 4, the hardening treatment unit 440 irradiates the adhesive layer with ultraviolet rays to perform the curing treatment of the adhesive layer. In this case, the irradiation intensity of ultraviolet light, based on the polymerization initiator at the activation wavelength region effective to 50mW / cm ² or more preferably, preferably 100mW / cm ² or more, particularly preferably 300mW / cm ² or more, in order to 5,000 mW/cm ² or less is preferable, preferably 3,000 mW/cm ² or less, and particularly preferably 2,000 mW/cm ² or less. By setting the irradiation intensity to be equal to or higher than the lower limit of the above range, the treatment time can be shortened, and the curing reaction can be sufficiently performed. In addition, by setting it as the upper limit or less, it is possible to prevent, for example, heat of the radiant heat from the light source, heat of the polymerization reaction, and the like, causing yellowing of the adhesive layer and deterioration of the adhesive force due to hardening and shrinkage. Further, the irradiation time can be set in accordance with the curing condition. Further, the integrated light amount expressed by the product of the irradiation intensity and the irradiation time is preferably 10 mJ/cm ² or more, more preferably 100 mJ/cm ² or more, particularly preferably 500 mJ/cm ² or more, and 5000 mJ/cm ² or less. Preferably, it is preferably 3,000 mJ/cm ² or less, and particularly preferably 2,000 mJ/cm ² or less.

The layer is hardened by a hardening treatment. Therefore, it is possible to obtain a layer (A2) having a substrate (A1), a non-liquid crystal material having a positive intrinsic birefringence, a layer (B1) of a non-liquid crystal material having a negative intrinsic birefringence, and a resin layer. The layered body 100 of (B2).

The obtained laminated body 100 is usually wound up and stored in a roll shape. As described above, in the above-described manufacturing method, the winding method can be used to continuously perform the production process in the MD direction by using the manufacturing line of the long film. Therefore, when manufacturing a laminated body, part or all of each step can be performed easily and efficiently by in line. Therefore, the laminated body can be manufactured stably and easily.

The above production method may further contain any step. For example, it may include a surface 12U opposite to the substrate (A1) and a non-liquid crystal having a negative intrinsic birefringence for the layer (A2) of the non-liquid crystal material having a positive birefringence as the bonding surface. The surface 21D of the layer of the material (B1) on the opposite side to the resin layer (B2) is subjected to a surface treatment such as corona treatment. Thereby, the laminated film can be improved (A) Adhesion to the multilayer film (B).

Moreover, the above-described manufacturing method can be further modified and implemented. For example, the surface 12U on the side opposite to the substrate (A1) of the layer (A2) of the non-liquid crystal material having a positive intrinsic birefringence may be applied, and the adhesive layer may be applied in advance, and the adhesive layer and the double layer may be applied. The layer (B1) of the negative non-liquid crystal material in which the intrinsic birefringence of the film (B) 20 is negative is bonded to the surface 21D on the opposite side to the resin layer (B2). That is, a surface 12U and a multi-layer film on the opposite side to the substrate (A1) of the layer (A2) of the non-liquid crystal material having the intrinsic birefringence of the multi-layered film (A) coated with the adhesive layer (A) are applied. (B) a step of the side of the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence and a side of the surface 21D opposite to the resin layer (B2); and the adhesive layer and the uncoated layer When the surface of the other side of the layer is bonded to the surface, the adhesive layer may be applied to either of the surface 12U and the surface 21D.

Further, for example, the above-mentioned laminated system can also directly produce a multi-layer film (B) having a layer (B1) of a non-liquid crystal material and a layer of a resin layer (B2) by extrusion, and the composite film is passed through the adhesive layer. The layer film (B) is produced by laminating the film (B).

[2. Phase difference film]

The retardation film of the present invention is obtained by peeling the base material (A1) and the resin layer (B2) from the above laminated body. Therefore, the retardation film is provided with a layer (A2) of a non-liquid crystal material having a positive intrinsic birefringence, a layer (B1) of a non-liquid crystal material having a negative intrinsic birefringence, and a layer. In the above laminated body, the layer (A2) of the non-liquid crystal material having a positive intrinsic birefringence and the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence are thin, and are uniformly in-plane. Has the required hysteresis value. Therefore, the retardation film obtained from the laminate has a structure The required optical properties are thin and thin, and can be manufactured stably.

From the viewpoint of use as an optical film, the total light transmittance of the retardation film is preferably 85% or more, more preferably 92% or more, and usually 100% or less. Here, the total light transmittance of the retardation film was measured at five points in accordance with JIS K7361-1997 and using a "turbidity meter NDH-300A" manufactured by Nippon Denshoku Industries Co., Ltd., and the average value was obtained.

The haze of the retardation film is preferably 1% or less, more preferably 0.8% or less, particularly preferably 0.5% or less, and usually 0% or more. By setting the haze to a low value, the sharpness of the display image of the display device incorporating the retardation film can be improved. Here, the haze was measured at five places in accordance with JIS K7361-1997 and using a "turbidity meter NDH-300A" manufactured by Nippon Denshoku Industries Co., Ltd., and the average value was obtained.

The retardation film system ΔYI is preferably 5 or less, more preferably 3 or less, and usually 0 or more. When the ΔYI is in the above range, it is possible to prevent coloration and to improve visibility. Here, ΔYI was measured in the same manner five times in accordance with ASTM E313 and using "Spectrophotometer SE2000" manufactured by Nippon Denshi Kogyo Co., Ltd., and obtained by arithmetic mean value.

The thickness of the retardation film is usually 5 μm or more, preferably 8 μm or more, preferably 10 μm or more, usually 500 μm or less, preferably 80 μm or less, preferably 50 μm or less, and particularly preferably 20 μm or less.

[3. Polarizer]

Fig. 5 is a view schematically showing a cross section of a polarizing plate according to an embodiment of the present invention, which is perpendicular to a plane of a principal surface. As shown in FIG. 5, the polarizing plate 500 includes a polarizing plate 510 and the above-described retardation film 520. The polarizing plate 500 The basic structure is formed by adhering the retardation film 520 of the present invention as a protective layer to one side or both sides of the polarizer 510 through the adhesive layer or the adhesive layer 530 as necessary. At this time, the direction of the retardation film 520 is arbitrary, and as shown in FIG. 5, the retardation film 520 and the polarizer 510 can be bonded to the layer (A2) 12 side of the non-liquid crystal material having a positive intrinsic birefringence. Further, in the opposite direction, the polarizer 510 may be bonded to the layer (B1) 21 of the non-liquid crystal material having a negative intrinsic birefringence.

Examples of the polarizer include a film of a suitable vinyl alcohol polymer such as polyvinyl alcohol or partially methylalized polyvinyl alcohol, and two colors such as iodine and a dichroic dye are used in an appropriate order and manner. Appropriate treatment such as dyeing treatment, elongation treatment, and crosslinking treatment of a substance. Such a polarizer is preferably one in which natural light is incident and linearly polarized light is transmitted, and in particular, it is preferable that the light transmittance and the degree of polarization are excellent. The thickness of the polarizer is usually from 5 μm to 80 μm, but is not limited thereto.

At least one side of the polarizer is attached to the retardation film of the present invention, and the other side may be provided with any protective layer. As the protective layer, any transparent film can be used. In particular, a resin film excellent in transparency, mechanical strength, thermal stability, moisture shielding property, and the like is preferable. Examples of such a resin include an acetate resin such as cellulose triacetate, a polyester resin, a polyether oxime resin, a polycarbonate resin, a polyamide resin, and a polyimide resin. A polyolefin resin, a polymer resin having an alicyclic structure, an acrylic resin, or the like. In particular, in terms of small birefringence, an acetate resin, a polymer resin having an alicyclic structure, or an acrylic resin is preferable, and transparency, low hygroscopicity, dimensional stability, and lightness are preferable. The viewpoint is particularly preferred as a polymer resin having an alicyclic structure. From The thickness of the protective layer is preferably 500 μm or less, more preferably 300 μm or less, particularly preferably 150 μm or less, and usually 5 μm or more, from the viewpoint of the thickness reduction of the polarizing plate.

As the adhesive layer or the adhesive layer, any layer of an adhesive or an adhesive can be used. Examples of the adhesive or the adhesive include an acrylic, an anthrone, a polyester, a polyurethane, a polyether, and a rubber. Among these, acrylic acid is preferred from the viewpoints of heat resistance, transparency, and the like.

Further, in the polarizing plate, the slow axis of the retardation film and the transmission axis of the polarizer are generally parallel or orthogonal.

The thickness of the polarizing plate (in order, a protective layer, a polarizer, an adhesive layer, a non-liquid crystal material layer (A2) having positive intrinsic birefringence, an adhesive layer, and a non-liquid crystal material layer having a negative intrinsic birefringence (B1) The thickness of the polarizing plate is preferably 70 μm or more, more preferably 80 μm or more, particularly preferably 90 μm or more, more preferably 150 μm or less, still more preferably 140 μm or less, and particularly preferably 120 μm or less. Such a thin polarizing plate can be realized by using the retardation film of the present invention.

Such a polarizing plate is a layer of a non-liquid crystalline material (A2) in which the base material (A1) or the resin layer (B2) is peeled off from the laminated body of the present invention, and the intrinsic birefringence is positive. The surface or the surface of the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence is bonded to the surface of the polarizer, and if necessary, the unnecessary layer is further peeled off, and the surface can be easily produced. The bonding system may be used to bond the film which has been cut to a desired size in a batch, or to use a long film and to be bonded by a winding method.

[4. LCD panel]

Fig. 6 is a view schematically showing a cross section of a liquid crystal panel according to an embodiment of the present invention, which is perpendicular to a plane of a principal surface. As shown in FIG. 6, the liquid crystal panel 600 includes a liquid crystal cell 610 and the above-described polarizing plate 500. At this time, the direction of the polarizing plate 500 is arbitrary, and as shown in FIG. 6, the retardation film 520 can be provided between the polarizer 510 and the liquid crystal cell 610.

Examples of the liquid crystal cell include an In-Plane Switching (IPS) type, a Vertically Aligned (VA) type, a MVA (Multi-domain Vertical Alignment) type, and a continuous flame-like arrangement ( CPA;Continuous Pinwheel Alignment), Twisted Nematic, Super Twisted Nematic, HAN (Hybrid Aligned Nematic), Optically Compensated Bending (OCB) ; Opticically Compenstory Bend) and so on. Among these, it can be suitably applied to an IPS type liquid crystal cell.

Generally, an ISP type liquid crystal cell system has a liquid crystal layer containing liquid crystal molecules aligned in parallel in the horizontal direction. Further, an IPS type liquid crystal panel including such an IPS type liquid crystal cell usually has two polarizers, and the transmission axes of the two polarizers are in a vertical positional relationship in which the front side of the screen is directed in the vertical direction and the horizontal direction. Therefore, when the screen of the IPS type liquid crystal panel is viewed obliquely from the up, down, left, and right directions, since the two transmission axes of the polarizer are orthogonal and viewable, the liquid crystal layer in the parallel alignment is, for example, a twisted liquid crystal. The birefringence produced by the cells is reduced, so that sufficient contrast can be obtained. On the other hand, when the screen is viewed obliquely from the direction in which the transmission axis of the polarizer is an azimuth angle of 45°, the configuration angle of the transmission axes of the two polarizers is shifted from 90°. Therefore, the previous linear polarization is not completely blocked, resulting in light leakage, resulting in I can't get enough black and the contrast is low.

On the other hand, by providing the retardation film of the present invention as an optical compensation film in the IPS type liquid crystal panel, it is possible to compensate for the hysteresis value due to the liquid crystal in the liquid crystal cell and to compensate the orthogonality of the transmission axes of the two polarizers. Configuration. Therefore, it is possible to effectively compensate for the birefringence generated by the transmitted light to prevent light leakage, and it is possible to obtain high contrast at an omnidirectional angle. This effect is considered to be similarly obtained in other types of liquid crystal panels, but this effect is particularly remarkable in the IPS type.

The retardation film of the present invention can be applied to a transmissive type, a reflective type, or a transmission in which a polarizer is disposed on one side or both sides of a liquid crystal cell. A liquid crystal panel having an arbitrary structure such as a reflective dual-purpose type. Further, the liquid crystal panel can be combined with components such as a ruthenium array sheet, a lens array sheet, a light diffusion plate, a backlight plate, and a brightness enhancement film to constitute a liquid crystal display device.

[Examples]

In the following, the present invention is specifically described by the examples, but the present invention is not limited by the examples described below, and may be arbitrarily changed without departing from the scope of the invention and the scope of the invention.

In the following description, the "%" and "parts" of the quantity are based on the weight basis unless otherwise notified in advance.

Further, the operation described below is carried out under normal temperature and normal pressure conditions unless otherwise notified in advance. Further, the so-called two-layer co-extrusion molding refers to co-extruding two kinds of resins to produce a multi-layered film having three layers. Further, the surface roughness Ra is an arithmetic mean roughness defined in JIS B0601-1994.

[test methods]

[Method for measuring hysteresis value]

The hysteresis value in the in-plane direction of each layer of the film and the hysteresis value in the thickness direction were measured using an automatic birefringence meter (Korean measuring instrument "KOBRA-21ADH") at a wavelength of 550 nm. The measurement was performed at 5 points in the vicinity of the center in the width direction of the film, and the average value thereof was taken as a measured value.

The layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence was measured by the following method. The resin layer (B2) is peeled off from the multi-layer film (B) to obtain a layer (B1) of a non-liquid crystal material having a negative intrinsic birefringence. The value measured by using the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence obtained as described above was used as a measured value.

Further, the layer (A2) of the non-liquid crystal material having positive birefringence was measured by the following method. The layer (A2) side of the non-liquid crystal material having the intrinsic birefringence of the multi-layer film (A) is adhered to the glass substrate through the adhesive layer, and the substrate (A1) is peeled off. Thereby, a composite of the glass substrate/adhesive layer/layer (A2) of the non-liquid crystal material having a positive in birefringence was prepared as a sample. The value measured using this sample was taken as a measured value.

[Method for measuring peeling force]

The peeling force was measured in accordance with JIS K6853-2 at a peeling speed of 100 mm/min and a sample width of 20 mm.

[tensile fracture elongation]

The tensile elongation at break is based on JIS K7162, and the test piece is produced in accordance with JIS K7127-1B. The tensile speed was measured at 5 mm/min.

[Example 1]

[1.1. Manufacture of multi-layer film with layer (B1) and layer (B2)]

(Preparation of resin)

70 parts of amorphous polystyrene ("HH102" manufactured by PS Japan Co., Ltd.) and 30 parts of poly(2,6-dimethyl-1,4-phenylene ether) (manufactured by ALDRICH Co., Ltd.) were biaxially extruded. The machine is kneaded to produce a pellet of a transparent thermoplastic resin (X). The resin (X) is a non-liquid crystalline material having a negative intrinsic birefringence. The glass transition temperature of the resin (X) was 134 °C.

As the thermoplastic resin (Y), a pellet of a methacrylic resin (glass transition temperature: 105 ° C) containing polymethyl methacrylate and rubber particles is placed in a uniaxial extruder on one side of a film forming apparatus. Let it melt.

Further, the pellet of the above resin (X) was placed in a uniaxial extruder on the other side of the film forming apparatus and melted.

(co-extruding step)

A two-layer three-layer film forming apparatus for co-extrusion molding was prepared.

The molten thermoplastic resin (Y) was supplied to a multi-manifold mold of a film forming apparatus through a leaf disc-shaped polymer filter having a pore opening degree of 10 μm (surface roughness Ra of the extrusion lip = Manifold on one side of 0.1 μm).

Further, the molten resin (X) was supplied to a manifold on the other side of the film forming apparatus through a leaf disc-shaped polymer filter having an opening degree of 10 μm.

The thermoplastic resin (Y) and the resin (X) were extruded to form a resin layer of a desired thickness, and extruded at a temperature of 260 ° C from the multi-manifold mold to form a thermoplastic resin ( A film-like three-layer structure of the layer (B2) of the layer Y), the layer (B1) of the resin (X), and the layer (B2) of the thermoplastic resin (Y). The molten resin thus coextruded into a film form was cast on a cooling roll adjusted to a surface temperature of 115 ° C, and secondly, passed through a surface temperature of 120 ° C. Between the cooling rollers. Thereby, a layer (B2) in which the thermoplastic resin (Y) is provided in this order, a layer (B1) of the resin (X) which is a non-liquid crystal material having a negative intrinsic birefringence, and a layer of the thermoplastic resin (Y) are obtained. (B2) 3-layer structured multi-layer film (b).

(extension step)

Next, the tension of the traction laminated film (b) and the tension of the expander chain are adjusted by extending the in-plane slow axis in parallel in the TD direction, and the simultaneous biaxial stretching is performed using a spreader. It is 1.8 times in the longitudinal direction and 1.1 times in the lateral direction. The temperature at the time of stretching was set to be 131 ° C lower than the glass transition temperature of the resin (X) which is a non-liquid crystalline material having a negative intrinsic birefringence by 3 ° C.

The thickness of each layer of the multi-layer film (b) extended in this way, the hysteresis value Re of the in-plane direction, and the hysteresis value Rth of the thickness direction were measured. The results are shown in Table 1.

[1.2. Manufacture of multi-layer film (A)]

100 parts of polycarbonate resin ("Yupizeta PCZ200" manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a non-liquid crystal material having a positive intrinsic birefringence; A degree of 137 ° C) and 400 parts of toluene were mixed to obtain a resin solution.

The base film (A1) ("ZEONOR FILM" manufactured by Zeon Corporation, Japan, ZEONOR FILM, thickness: 80 μm, glass transition temperature: 138 ° C) which is a decylene-based resin having a polymer resin having an alicyclic structure, The resin solution was applied so as to have a dry film thickness of 6 μm to form a film of a resin solution. The film of the resin solution was dried at 80 ° C for 2 minutes to obtain a multi-layer film (a) comprising a base film (A1) and a polycarbonate resin layer (A2).

The above-mentioned multi-layer film (a) was stretched at a stretching temperature of 145 ° C at a stretching ratio of 2.7 times in the TD direction at a stretching ratio of 2.7 times. Thereby, a double-layered film (A) having a two-layer structure of the base film (A1) / polycarbonate resin layer (A2) was obtained. At this time, the film thickness of the polycarbonate resin layer (A2) layer was 5 μm.

[1.3. Fit]

The layer (B2) on one side is peeled off from the multi-layer film of the three-layer structure of the layer (B2)/layer (B1)/layer (B2) to obtain a layer having the layer (B1) and the layer (B2). Film (B). The surface of the layer (B1) exposed by peeling one layer (B2) was subjected to corona treatment (wetting index 56 dyne/cm). On the surface of the layer (B1) subjected to the corona treatment, an active energy ray-curable adhesive ("ARONIX M-6100" manufactured by Toagosei Co., Ltd.) was applied to a thickness of 5 μm to form an adhesive layer.

On the other hand, on the surface of the polycarbonate resin layer (A2) of the multi-layer film (A), corona treatment (wetting index 56 dyne/cm) was performed. The above-mentioned adhesive layer was bonded to the surface of the polycarbonate resin layer (A2) subjected to the corona treatment. At the time of this bonding, the in-plane retardation axis of the polycarbonate resin layer (A2) is parallel to the in-plane slow axis of the layer (B1) of the resin (X). In terms of being parallel, it is inevitable to use a Roll to Roll fit.

After the bonding, the surface of the layer (B2) side was irradiated with ultraviolet rays, the transmission layer (B2) and the layer (B1) by using an ultraviolet irradiation device (CONVEYER UV, manufactured by Fusion UV Systems Japan Co., Ltd., integrated light amount: 350 mJ/cm ² ). The subsequent layer is irradiated with ultraviolet rays. Thereby, the layer is hardened to obtain a layer (B1) and a layer (B) of the base film (A1), the polycarbonate resin layer (A2), the adhesive layer, the resin (X), and the thermoplastic resin (Y). ) The layered body.

[1.4. Manufacture of polarizing plates]

The base film (A1) was peeled off from the produced laminate. The surface of the polycarbonate resin layer (A2) exposed by peeling off the base film (A1) was subjected to corona treatment (wetting index: 56 dyne/cm). A water-based adhesive was applied to the end portion of the surface of the polycarbonate resin layer (A2) subjected to the corona treatment so that the dry film thickness was 0.1 μm. This water-based adhesive is an aqueous solution obtained by dissolving 100 parts of "Gohsefimer Z-200" manufactured by Nippon Synthetic Co., Ltd. and 1 part of Glyoxal GX in 4949 parts of pure water. A film of a cellulose triacetate layer (thickness: 50 μm) and a polarizer (thickness: 25 μm) with a hard coat layer were prepared, and the surface of the polarizer of the film was placed opposite to the surface of the polycarbonate resin layer (A2). And use a laminating machine to fit. In the case of bonding, the in-plane retardation of the layered body of the layer (B2) of the polycarbonate resin layer (A2), the adhesive layer, the resin (X), and the layer (B2) of the thermoplastic resin (Y) is sequentially provided. The axis is parallel to the transmission axis of the polarizer. Subsequently, the layer (B2) of the thermoplastic resin (Y) is peeled off to obtain a layer including the cellulose triacetate layer, the polarizer, the adhesive layer, the polycarbonate resin layer (A2), the adhesive layer, and the resin (X) in this order. (B1) polarizing plate. The thickness of the obtained polarizing plate was 96 μm.

[1.5. Manufacture of IPS LCD Panel]

The IPS solution of the emission side polarizing plate from a commercially available IPS mode liquid crystal display device The crystal panel is peeled off. The polarizing plate from which the layer (B2) was peeled off was bonded to the surface on which the emission-side polarizing plate of the IPS liquid crystal panel was peeled off. At the time of bonding, the surface of the layer (B1) of the resin (X) of the polarizing plate is opposed to the liquid crystal cell. Further, the transmission axis of the polarizing plate to be bonded is perpendicular to the transmission axis of the incident side polarizing plate of the IPS liquid crystal panel. Further, the bonding was carried out using an adhesive layer ("MO-T006C" manufactured by LINTEC Co., Ltd., thickness: 25 μm). In this way, a layer (B1), an adhesive layer, a polycarbonate resin layer (A2), an adhesive layer, and a polarizer having an incident side polarizing plate, an IPS type liquid crystal cell, an adhesive layer, and a resin (X) are provided in this order. And a liquid crystal display device of an IPS liquid crystal panel of a cellulose triacetate layer.

When the display characteristics of the obtained liquid crystal display device were visually confirmed, the display was good and uniform when viewed from the front side or when viewed from the range of the polar angles of 0 to 80 degrees.

In addition, in order to evaluate the light leakage of the liquid crystal display device, the transmission axis of the output side polarizing plate of the liquid crystal panel is measured at azimuth angle of 45° and the black display is measured from a polar angle of −60° to 60°, and the brightness is measured. The maximum value Ymax is 0.55 (candle/m ² ; candela/m ² ).

[Embodiment 2]

A styrene-maleic anhydride copolymer ("DYLARK D332" manufactured by NOVA chemicals Japan Co., Ltd., glass transition temperature: 130 ° C) was used instead of the resin (X) as a non-liquid crystal material having a negative intrinsic birefringence. Further, the stretching temperature of the multi-layer film (b) was changed to 127 °C.

A liquid crystal display device was produced and evaluated in the same manner as in Example 1 except for the above.

[Example 3]

100 parts of bis-cis-butylene imide resin (ultraviolet cured product of "BMI1500" manufactured by ARBROWN Co., Ltd.; glass transition temperature: 90 ° C), one part of photopolymerization initiator ("Irg 907" manufactured by BASF Japan Co., Ltd.), and 202 parts Toluene and 202 parts of ethyl acetate were mixed to obtain a resin solution. In the production of the multi-layer film (A), the resin solution is used in place of a resin solution containing a polycarbonate resin as a resin solution containing a non-liquid crystal material having a positive intrinsic birefringence. The film thickness of the extended bis-butenylene imine resin layer was 4 μm.

In the production of the multi-layer film (A), a decene-based resin film (A1) ("ZEONOR film" manufactured by Zeon Corporation, Japan, thickness: 80 μm, glass transition temperature: 105 ° C) was used as the base film.

A liquid crystal display device was produced and evaluated in the same manner as in Example 1 except for the above. The thickness of the polarizing plate was 95 μm.

[Example 4]

Instead of the thermoplastic resin (Y), a norbornene-based resin ("ZEONOR" manufactured by Zeon Corporation, Japan; glass transition temperature: 105 ° C) was used.

A liquid crystal display device was produced and evaluated in the same manner as in Example 1 except for the above.

[Comparative Example 1]

The layer (B2) of the thermoplastic resin (Y)/amorphous polystyrene ("HH102" manufactured by PS Japan Co., Ltd.) and poly(2,6) were obtained in the same manner as in the step [1.1] of the first embodiment. a double-layered film of a layer (B1) of a resin (X)/layer (B2) of a thermoplastic resin (Y) of dimethyl-1,4-phenylene ether.

On the surface of the layer (B2) on one side of the multi-layer film of the three-layer structure of the layer (B2) / layer (B1) / layer (B2), corona treatment (wetting index 56 dyne / cm) was performed. An active energy ray-curable adhesive ("ARONIX M-6100" manufactured by Toagosei Co., Ltd.) was applied to the surface of the layer (B2) subjected to the corona treatment to form an adhesive layer. On the other hand, the surface of the polycarbonate resin layer (A2) of the multi-layer film (A) similar to that of Example 1 was subjected to corona treatment (wetting index 56 dyne/cm). The surface of the corona-treated polycarbonate resin layer (A2) was bonded to the above-mentioned adhesive layer. After the bonding, the subsequent layer was irradiated with ultraviolet rays by the ultraviolet irradiation device under the same conditions as in Example 1. Thereby, the layer is hardened to obtain a layer (B1) and a layer of resin (X) including the base film (A1), the polycarbonate resin layer (A2), the adhesive layer, and the thermoplastic resin (Y) in this order (B1). And a laminate of the layer (B2) of the thermoplastic resin (Y).

A polarizing plate was produced in the same manner as in the step [1.4] of Example 1, except that the laminate obtained in this manner was used. The thickness of the polarizing plate was 102 μm.

In addition, the liquid crystal display device was produced and evaluated in the same manner as in the step [1.5] of the first embodiment except that the polarizing plate obtained in this manner was used.

When the display characteristics of the obtained liquid crystal display device were visually confirmed, the display was good and uniform when viewed from the front side or when viewed from the range of the polar angles of 0 to 80 degrees.

In addition, in order to evaluate the light leakage of the liquid crystal display device, the transmission axis of the output side polarizing plate of the liquid crystal panel is measured at azimuth angle of 45° and the black display is measured from a polar angle of −60° to 60°, and the brightness is measured. The maximum value Ymax is 0.60 (candle/m ² ).

[result]

The results of the examples and comparative examples are shown in Table 2. Here, in the simple table 2 The meaning of the weighing is as follows.

The difference in Tg of the film (B) is the difference in glass transition temperature calculated by the "glass transition temperature of the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence - the glass transition temperature of the resin layer (B2)".

The difference in Tg of the film (A): the difference in glass transition temperature calculated from the glass transition temperature of the layer (A2) of the non-liquid crystal material having a positive birefringence (the glass transition temperature of the substrate (A1).

Re (550 nm): hysteresis value in the in-plane direction measured at a wavelength of 550 nm.

Rth (550 nm): hysteresis value in the thickness direction measured at a wavelength of 550 nm.

MAA resin: methacrylic resin

NBR resin: decene-based resin

PC resin: polycarbonate resin

BMI resin: bis-n-butylene imine resin

[review]

As is apparent from Table 2, in Examples 1 to 4, the comparison of the IPS type liquid crystal panel can be improved.

Therefore, it can be confirmed that the retardation films of Examples 1 to 4 have IPS The optical compensation of the liquid crystal panel is a possible optical property. Further, the retardation films of Examples 1 to 4 can each be provided with a substrate (A1), a layer (A2) of a non-liquid crystal material, an adhesive layer, a layer (B1) of a non-liquid crystal material, and a resin layer (B2). It is easy to manufacture the laminated body, and it can be confirmed that the thickness can be made thinner.

Claims (15)

A laminated body comprising: a multilayer film A comprising a substrate (A1) and a layer (A2) of a non-liquid crystal material having a positive birefringence connected to the substrate (A1); and a multi-layer film B having an inherent a layer (B1) of a non-liquid crystal material having a negative birefringence and a resin layer (B2) connected to the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence; and a layer of the subsequent layer, separately interposed therebetween a layer of the non-liquid crystal material having a positive birefringence (A2) opposite to the substrate (A1) and a layer (B1) of a non-liquid crystal material having a negative intrinsic birefringence and the resin The layer (B2) is between the faces on the opposite side; wherein the difference between the glass transition temperature of the material of the substrate (A1) and the glass transition temperature of the non-liquid crystalline material having the positive intrinsic birefringence is +15 ° C -15 a range of °C; a layer (A2) of the non-liquid crystal material having a positive intrinsic birefringence is a negative biaxial layer; and a layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence is a positive double A positive biaxial layer. The laminate according to claim 1, wherein the peeling force between the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence and the resin layer (B2) is 0.5 N/20 mm or less. The laminate according to claim 1, wherein a peeling force between the substrate (A1) and the layer (A2) of the non-liquid crystal material having a positive intrinsic birefringence is 0.05 N/20 mm or less. The laminate according to claim 1, wherein the glass transition temperature Tg (B1) of the non-liquid crystalline material having a negative intrinsic birefringence and the glass transition temperature Tg (B2) of the resin of the resin layer (B2) are the same. The relationship is to satisfy Tg(B1)>Tg(B2)+20°C. The laminate according to claim 1, wherein the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence has a tensile elongation at break of 20% or less. The laminate according to claim 1, wherein the substrate (A1) is selected from the group consisting of a polymer resin having an alicyclic structure, a (meth)acrylic resin, a polycarbonate resin, and a (meth) group. It is formed by a resin composed of an acrylate-vinyl aromatic compound copolymer resin and a polyether oxime resin. The laminate according to claim 1, wherein the intrinsic birefringence is a positive non-liquid crystalline material selected from the group consisting of a polyimide resin, a maleimide resin, and a polyamidimide. A group consisting of a resin, a polycarbonate resin, a polyester resin, and a polyurethane urea resin. The laminate according to claim 1, wherein the non-liquid crystalline material having a negative intrinsic birefringence is selected from the group consisting of styrene, styrene-maleic acid, and maleic acid. a polymer obtained by polymerizing a monomer of one or more types consisting of imines and (meth) acrylates, and a polymer selected from the group consisting of polycarbonate polymers, polyester polymers, and polyarylene ethers a mixture of polymers of one or more types consisting of a group of polymers. The laminate according to claim 1, wherein the resin layer (B2) is selected from the group consisting of a polymer resin having an alicyclic structure, a (meth)acrylic resin, a polycarbonate resin, and a (meth) group. Acrylate-vinyl aromatic compound It is formed by a resin composed of a copolymer resin and a polyether oxime resin. A method for producing a laminate according to the first aspect of the invention, comprising: dissolving a solution in which a non-liquid crystalline material having a positive intrinsic birefringence in a solvent is developed on the substrate ( a step of A1); a step of drying the developed solution; and a step of extending the substrate (A1) to obtain the multilayer film A after drying the solution. A method for producing a laminate according to the first aspect of the invention, comprising: the non-liquid crystal material having a negative intrinsic birefringence and a resin forming the resin layer (B2); a step of obtaining a layer (B1) of the non-liquid crystal material (B1) having the negative intrinsic birefringence and a multi-layer film (b) of the resin layer (B2) in the order of the co-extruding; a step of extending the multi-layer film (b); and a step of peeling the one side resin layer (B2) from the extended multi-layer film (b) to obtain the multi-layer film B. A method for producing a laminate according to the first aspect of the invention, comprising: the layer (A2) of the non-liquid crystal material having positive intrinsic birefringence and the substrate ( A1) is the surface on the opposite side and the surface on the side opposite to the surface on the side opposite to the resin layer (B2) of the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence, and the formation is continued a step of laminating the surface of the adhesive layer and the other side on which the adhesive layer is not formed The steps. A method for producing a retardation film, comprising peeling the substrate (A1) and the resin layer (B2) from the laminate according to claim 1 of the patent application. A method for producing a polarizing plate, comprising: manufacturing a retardation film by a method for producing a retardation film according to claim 13; and a non-liquid crystal material having positive intrinsic birefringence of the retardation film The surface of the layer (A2) or the surface of the layer (B1) of the non-liquid crystal material having a negative intrinsic birefringence is bonded to a polarizer. A method of manufacturing an IPS liquid crystal panel, comprising: manufacturing a polarizing plate by the method for producing a polarizing plate according to claim 14; and bonding the polarizing plate to an IPS type liquid crystal cell.