WO2018025715A1 - Laminate film - Google Patents

Abstract

[Problem] To provide a laminate film which can maintain a high degree of polarization even in a hot and humid environment. [Solution] This laminate film comprises: a polarizer layer in which a dichroic dye is oriented in a polyvinyl alcohol resin; a resin film in which the forming material is a resin film that has a slow axis in the direction oblique to the absorption axis of the polarizer layer; and an adhesive layer which bonds together the polarizer layer and the resin film. The resin layer contains a plasticizer. The adhesive layer contains, as the forming material, the cured product of an adhesive composition, and the adhesive composition contains a compound having at least one (meth)acryloyl group in the molecule.

Description

Laminated film

The present invention relates to a laminated film.

Conventionally, a polarizing plate has been widely used as a polarized light supplying element and a polarized light detecting element in a display device such as a liquid crystal display device. A polarizing plate having a configuration in which a protective film is bonded to one side or both sides of a polarizing film (polarizer layer) using an adhesive or the like is known.

As a polarizing film, a film made of a polyvinyl alcohol-based resin in which a dichroic dye such as iodine is oriented is known. Iodine in the polarizing film exists as an iodine complex, and the iodine complex itself is oriented depending on the orientation of the polyvinyl alcohol resin. It is known that this iodine complex absorbs light in the visible region, so that the polarizing film exhibits polarization characteristics (polarization degree).

By the way, when applying a polarizing plate to a display device, various optical layers (resin layers) such as a phase difference plate and an optical compensation film having optical properties are provided on a polarizing film provided with a protective film, if necessary. Is bonded (for example, Patent Document 1). The optical layer may contain an additive such as a plasticizer for the purpose of improving the performance of the film.

JP 2011-186482 A

However, when the polarizing plate described in Patent Document 1 is left in a humid heat environment (for example, at room temperature of 60 ° C. and humidity of 95%), the degree of polarization may decrease.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a laminated film that can maintain a high degree of polarization even in a humid heat environment.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have transferred the plasticizer contained in the optical layer to the polarizing film in a humid heat environment and reacted with the iodine complex contributing to the polarization. It was estimated that the degree of polarization of the resulting polarizing plate was reduced by the disappearance of the iodine complex. On the other hand, the adhesive layer interposed between the polarizing film and the optical layer contains a cured product of the adhesive composition as a forming material, and the adhesive composition has at least one (meth) acryloyl group in the molecule. It was anticipated that the transition of the plasticizer to the polarizing film could be suppressed by including a compound having the above, and the present invention was completed.

One embodiment of the present invention is a material for forming a polarizer film in which a dichroic dye is oriented in a polyvinyl alcohol resin, and a resin film having a slow axis in a direction oblique to the absorption axis of the polarizer layer A resin layer, an adhesive layer that bonds the polarizer layer and the resin layer, the resin layer includes a plasticizer, and the adhesive layer is formed by using a cured product of the adhesive composition as a forming material. And the adhesive composition provides a laminated film comprising a compound having at least one (meth) acryloyl group in the molecule.

In one embodiment of the present invention, both the polarizer layer and the resin layer may be long.

According to one embodiment of the present invention, a laminated film capable of maintaining a high degree of polarization even in a humid heat environment is provided.

It is a cross-sectional schematic diagram which shows an example of the laminated constitution of the laminated film of this embodiment. It is a cross-sectional schematic diagram which shows the modification of the layer structure of the laminated | multilayer film of this embodiment.

<Laminated film>
FIG. 1 is a schematic cross-sectional view showing an example of the layer configuration of the laminated film of the present embodiment. As shown in FIG. 1, the laminated film 1 of this embodiment includes a polarizer layer 11, a resin layer 21, and an adhesive layer 31 that bonds the polarizer layer 11 and the resin layer 21. In another embodiment, a protective film may be further laminated on the side of the polarizer layer 11 opposite to the resin layer 21.

The laminated film of the present embodiment may be long or may be a sheet obtained by cutting the long laminated film into a predetermined length. The long laminated film includes a long polarizer layer and a long resin layer. The long polarizer layer and the long resin layer will be described later.

[Polarizer layer]
A polarizer layer refers to an optical film having the property of absorbing linearly polarized light having a vibration plane parallel to the optical axis and transmitting linearly polarized light having a vibration plane perpendicular to the optical axis. Specifically, the polarizer layer 11 of this embodiment is a film in which a dichroic dye is oriented in a polyvinyl alcohol-based resin (hereinafter sometimes referred to as “PVA-based resin”).

The thickness of the polarizer layer 11 is preferably 30 μm or less, more preferably 25 μm or less, further preferably 15 μm or less, particularly preferably 10 μm or less, and particularly preferably 7 μm or less. preferable.

When the polarizer layer 11 is a film in which a dichroic dye is oriented in a PVA-based resin, the polarizer layer 11 may be obtained by stretching a film original containing the PVA-based resin. When the thickness of the polarizer layer 11 is 7 μm or less, the polarizer layer 11 may be obtained by stretching a coating film containing a PVA-based resin formed on the substrate together with the substrate, and then peeling the substrate.

Examples of the substrate that may be used in the present embodiment include a polypropylene film, a polyethylene terephthalate film, a polycarbonate film, a triacetyl cellulose film, a norbornene film, a polyester film, and a polystyrene film.

Examples of the PVA resin used in the present embodiment include a saponified polyvinyl acetate resin. Examples of the polyvinyl acetate resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having ammonium groups.

The saponification degree of the PVA resin is preferably 80 mol% or more, more preferably 90 mol% or more and 99.5 mol% or less, and further preferably 94 mol% or more and 99 mol% or less. . When the degree of saponification is 80 mol% or more, the moisture and heat resistance of the resulting laminated film 1 is improved. Moreover, the laminated | multilayer film 1 which has sufficient polarization | polarized-light performance as saponification degree is 99.5 mol% or less is obtained.

The PVA resin may be a modified polyvinyl alcohol partially modified. For example, olefin modification with ethylene, propylene, etc .; unsaturated carboxylic acid modification with acrylic acid, methacrylic acid, crotonic acid, etc .; one modified with an alkyl ester of unsaturated carboxylic acid, acrylamide or the like may be used.

The rate of modification of the PVA resin is preferably less than 30 mol%, more preferably less than 10%. When a PVA resin having a modification ratio of less than 30 mol% is used, the dichroic dye can be sufficiently adsorbed, and a polarizer having sufficient polarization performance can be obtained.

The average degree of polymerization of the PVA-based resin is preferably 100 or more and 10,000 or less, more preferably 1500 or more and 8000 or less, and further preferably 2000 or more and 5000 or less. When the average degree of polymerization is 100 or more, a polarizer having sufficient polarization performance can be obtained. Moreover, when the average degree of polymerization is 10,000 or less, the solubility in a solvent becomes good, and the formation of a film containing a PVA resin is easy.

Commercially available PVA-based resins can be easily obtained, and preferable examples of commercially available products are trade names, “PVA124” and “PVA117” (both saponification degrees) manufactured by Kuraray Co., Ltd. : 98 to 99 mol%), "PVA624" (degree of saponification: 95 to 96 mol%), "PVA617" (degree of saponification: 94.5 to 95.5 mol%); manufactured by Nippon Synthetic Chemical Industry Co., Ltd. "N-300" and "NH-18" (both saponification degree: 98 to 99 mol%), "AH-22" (saponification degree: 97.5 to 98.5 mol%), "AH-26 "(Saponification degree: 97 to 98.8 mol%);" JC-33 "(saponification degree: 99 mol% or more)," JF-17 "," JF-17L "by Nippon Vinegar Poval Co., Ltd. And "JF-20" (both saponification degrees: 98-99 %), “JM-26” (degree of saponification: 95.5 to 97.5 mol%), “JM-33” (degree of saponification: 93.5 to 95.5 mol%), “JP-45” (Saponification degree: 86.5 to 89.5 mol%).

Examples of the dichroic dye used in the present embodiment include iodine or a dichroic organic dye. Dichroic organic dyes include Red BR, Red LR, Red R, Pink LB, Rubin BL, Bordeaux GS, Sky Blue LG, Lemon Yellow, Blue BR, Blue 2R, Navy RY, Green LG, Violet LB, Violet B , Black H, Black B, Black GSP, Yellow 3G, Yellow R, Orange LR, Orange 3R, Scarlet GL, Scarlet KGL, Congo Red, Brilliant Violet BK, Spura Blue G, Spura Blue GL, Spura Orange GL, Direct Sky Blue , Direct First Orange S, and First Black.

Only one type of dichroic dye may be used alone, or two or more types may be used in combination.

[Resin layer]
The resin layer 21 of the present embodiment uses a resin film having a slow axis in a direction oblique to the absorption axis of the polarizer layer 11 as a forming material. Such a resin film can be manufactured through a stretching process, and the resin film is left with a tensile stress in a direction oblique to the absorption axis of the polarizer layer 11. The residual stress remaining in the resin film can contribute to a decrease in the degree of polarization of the polarizing plate.

The resin layer 21 has a slow axis in a direction oblique to the absorption axis of the polarizer layer 11. For example, the angle of the slow axis is 45 ± 10 ° or 135 with respect to the absorption axis of the polarizer layer 11. It is preferably ± 10 °. When the angle of the slow axis is in the above range, the difference between the light phase in the fast axis direction and the light phase in the slow axis direction is π / 2. When the phase difference between the fast axis and the slow axis is π / 2, when the laminated film 1 of the present embodiment is applied to a display device, the light that has passed through the laminated film 1 can be made into circularly polarized light. . Therefore, even when viewed through a polarizing glass, a configuration with excellent visibility can be obtained.

The resin layer 21 of the present embodiment is preferably a retardation layer having retardation characteristics and wavelength dispersion characteristics that satisfy the following formulas (1) to (4). When the resin layer 21 satisfies the formulas (1) to (4), when the laminated film 1 of the present embodiment is incorporated into a display device, the screen is viewed from various directions (azimuth and polar angles) through the polarizing glass. It is possible to effectively suppress the color change when viewing the screen. Thereby, the visibility of the image display device can be improved.

(1) 100 nm ≦ R _e (590) ≦ 180 nm,
(2) 0.5 <R _th (590) / R _e (590) ≦ 0.8,
(3) 0.85 ≦ R _e (450) / R _e (550) <1.00, and (4) 1.00 <R _e (630) / R _e (550) ≦ 1.1

In the formula, R _e (590), R _e (450), R _e (550), and R _e (630) represent in-plane retardation values at measurement wavelengths of 590 nm, 450 nm, 550 nm, and 630 nm, respectively, and R _th ( 590) represents a thickness direction retardation value at a measurement wavelength of 590 nm. These in-plane retardation value and thickness direction retardation value are values measured in an environment of a temperature of 23 ° C. and a relative humidity of 55%.

Plane retardation value R _e, and the thickness direction retardation value R _th, refraction of the refractive index in the in-plane slow axis direction n _x, plane fast axis direction (perpendicular to the plane slow axis direction) When the rate is n _y , the refractive index in the thickness direction is n _z , and the thickness of the optical film is d, it is defined by the following formulas (S1) and (S2).

(S1) R _e = (n _x −n _y ) × d
(S2) R _th = [{(n _x + _ny ) / 2} −n _z ] × d

From the viewpoint of more effectively suppressing the color change in the laminated film 1, R _e (590) in the formula (1) is preferably 105 to 170 nm. R _th (590) / R _e (590) in the formula (2) is preferably 0.6 to 0.75. In the formula (3), R _e (450) / R _e (550) is preferably 0.86 to 0.98. In the formula (4), R _e (630) / R _e (550) is preferably 1.01 to 1.06.

For example, the resin layer 21 can be produced by stretching a film containing a resin described later. Examples of the stretching treatment include uniaxial stretching and biaxial stretching.

Examples of the stretching direction include a machine flow direction (MD) of an unstretched film, a direction perpendicular to the machine flow direction (TD), and a direction oblique to the machine flow direction (MD). Here, the unstretched film refers to a film that is not stretched. In uniaxial stretching, an unstretched film is stretched in any one of these directions. On the other hand, the biaxial stretching may be simultaneous biaxial stretching that simultaneously stretches in two stretching directions, or may be sequential biaxial stretching that stretches in another direction after stretching in a predetermined direction.

For the stretching process, for example, two or more pairs of nip rolls with increased peripheral speed on the outlet side are used to stretch in the longitudinal direction (machine flow direction: MD), or the both ends of the unstretched film are gripped with a chuck and machine flow is performed. It can be performed by spreading in a direction (TD) orthogonal to the direction. At this time, the retardation value and the wavelength dispersion can be controlled within the ranges of the above formulas (1) to (4) by adjusting the thickness of the film or adjusting the draw ratio.

Further, the chromatic dispersion value can be controlled within the range of the above formulas (3) to (4) by adding a chromatic dispersion adjusting agent to the resin.

Generally, a long polarizing film (polarizer layer) has an absorption axis in the long side direction. The long resin layer and the long polarizer layer can be bonded by roll-to-roll, and the angle between the absorption axis and the slow axis of the resin layer is within the above range. It is preferable that the resin layer 21 is manufactured by being obliquely stretched by biaxial stretching.

Examples of the resin forming the resin film include cellulose acetate resin, cycloolefin resin, polyolefin resin, acrylic resin, polyimide resin, polycarbonate resin, and polyester resin.

The cellulose acetate resin is composed of a cellulose portion or a complete acetate ester. Examples of the cellulose acetate resin include triacetyl cellulose and diacetyl cellulose.

A resin film made of a cellulose acetate resin can be easily obtained as a commercial product. As a preferable example of the commercial product, all of them are trade names of “Fujitac (registered)” sold by FUJIFILM Corporation. Trademarks) TD80 "," Fujitac (registered trademark) TD80UF "and" Fujitac (registered trademark) TD80UZ "," KC8UX2M "and" KC8UY "sold by Konica Minolta Opto Corporation.

The cycloolefin resin forming the resin film is, for example, a thermoplastic amorphous resin having a monomer unit composed of a cyclic olefin (cycloolefin) such as norbornene or a polycyclic norbornene monomer (non-crystalline polyolefin). Also called resin.) The cycloolefin-based resin may be a hydrogenated product of the above-mentioned cycloolefin ring-opening polymer or a hydrogenated product of a ring-opening copolymer using two or more kinds of cycloolefins. It may be an addition copolymer with an olefin and / or an aromatic compound having a vinyl group. In addition, a polar group may be introduced.

In the case where a resin film is formed using a copolymer of a cycloolefin and a chain olefin and / or an aromatic compound having a vinyl group, examples of the chain olefin include ethylene and propylene. Examples of the aromatic compound having a vinyl group include styrene, α-methylstyrene, and nuclear alkyl-substituted styrene. In such a copolymer, the unit of the monomer composed of cycloolefin may be 50 mol% or less, preferably 15 to 50 mol%.

In particular, when a terpolymer of a cycloolefin, a chain olefin, and an aromatic compound having a vinyl group is used, the monomer unit composed of the cycloolefin can be used in a relatively small amount as described above. In such a terpolymer, the unit of monomer composed of a chain olefin is preferably 5 to 80 mol%. The unit of the monomer composed of an aromatic compound having a vinyl group is preferably 5 to 80 mol%.

Cycloolefin-based resins can be easily obtained from commercial products, and preferable examples of commercially available products are all trade names, manufactured by TOPAS ADVANCED POLYMERS GmbH, sold in Japan by Polyplastics Co., Ltd. "TOPAS (registered trademark)", "Arton (registered trademark)" sold by JSR Corporation, "ZEONOR (registered trademark)" and "ZEONEX" sold by ZEON Corporation ) (Registered trademark) ”,“ Apel (registered trademark) ”sold by Mitsui Chemicals, Inc., and the like.

When the resin layer 21 of the present embodiment is a retardation layer, the thickness of the retardation layer is preferably 10 μm or more and 50 μm or less.

The resin layer 21 of the present embodiment contains a plasticizer for the purpose of imparting flexibility to the resin film and facilitating stretching in addition to the resin forming the resin film. Examples of the plasticizer include polyhydric alcohols such as ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and trimethylolpropane.

The plasticizer may be used alone or in combination of two or more. In particular, ethylene glycol and glycerin are preferably used.

[Adhesive layer]
The adhesive layer 31 of the present embodiment includes a cured product of the adhesive composition as a forming material (hereinafter, the “adhesive composition” may be referred to as “the present composition”). The adhesive composition contains a compound having at least one (meth) acryloyl group in the molecule. The compound having at least one (meth) acryloyl group in the molecule may be referred to as a compound having at least one (meth) acryloyloxy group in the molecule (hereinafter referred to as “(meth) acrylic compound”). ), A compound having at least one (meth) acrylamide group in the molecule (hereinafter sometimes referred to as “(meth) acrylamide-based compound”), and the like. These compounds are radically polymerizable compounds and can be cured by irradiation with active energy rays (for example, ultraviolet rays, visible light, electron beams, X-rays, etc.).

In this specification, “(meth) acryloyl group” means a methacryloyl group or an acryloyl group. The “(meth) acryloyloxy group” and “(meth) acrylamide group” have the same meaning as described above.

The thickness of the adhesive layer is preferably 0.01 μm or more and 5 μm or less, more preferably 0.01 μm or more and 2 μm or less, and further preferably 0.01 μm or more and 1 μm or less. Sufficient adhesiveness can be acquired as the thickness of the adhesive bond layer 31 is 0.01 micrometer or more. Moreover, when the thickness of the adhesive layer 31 is 5 μm or less, the laminated film 1 is unlikely to have a poor appearance.

The adhesive layer is such that the moisture permeability of an evaluation sample obtained by applying and curing the adhesive composition on a triacetyl cellulose film to a thickness of 2 to 3 μm is 300 g / m ² · 24 hr or less. It is preferable to select one. Although the lower limit of moisture permeability is not particularly limited, it is, for example, 50 g / m ² · 24 hr. By using an adhesive layer having such a moisture permeability, a decrease in polarization degree can be further reduced.

The evaluation sample can be produced as follows. First, the adhesive composition is applied on a triacetyl cellulose film so as to have a thickness of 2 to 3 μm to form an adhesive composition layer. The triacetyl cellulose film for measuring the moisture permeability of the evaluation sample has a thickness of 57.5 μm and moisture permeability (value calculated by the cup method (JIS Z 0208, temperature 40 ° C., humidity 90% RH)). Is 553 g / m ² · 24 hr. Next, ultraviolet rays are applied from the adhesive composition layer side so that the integrated light amount is 400 mJ / cm ^2, and the adhesive composition layer is cured to obtain an evaluation sample. The moisture permeability of the obtained evaluation sample was measured by a cup method (JIS Z 0208, temperature 40 ° C., humidity 90% RH).

(Radically polymerizable compound)
The (meth) acrylic compound used in the present embodiment includes a (meth) acrylate monomer having at least one (meth) acryloyloxy group in the molecule, and at least two (meth) acryloyloxy groups in the molecule. And (meth) acrylate oligomers having These may be used alone or in combination of two or more. When two or more types are used in combination, two or more (meth) acrylate monomers may be used, two or more (meth) acrylate oligomers may be used, and, of course, one or more (meth) acrylate monomers. One or more (meth) acrylate oligomers may be used in combination.

The above (meth) acrylate monomer includes a monofunctional (meth) acrylate monomer having one (meth) acryloyloxy group in the molecule, and a bifunctional (meth) methacrylate having two (meth) acryloyloxy groups in the molecule. ) Acrylate monomers and polyfunctional (meth) acrylate monomers having 3 or more (meth) acryloyloxy groups in the molecule.

Monofunctional (meth) acrylate monomers include tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, cyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol monoa Relate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dimethylamino Examples thereof include ethyl (meth) acrylate, ethyl carbitol (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and the like.

As the monofunctional (meth) acrylate monomer, a carboxyl group-containing (meth) acrylate monomer may be used. Monofunctional (meth) acrylate monomers containing carboxyl groups include 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, carboxyethyl (meth) acrylate, 2- (meth) Examples include acryloyloxyethyl succinic acid, N- (meth) acryloyloxy-N ′, N′-dicarboxymethyl-p-phenylenediamine, and 4- (meth) acryloyloxyethyl trimellitic acid.

Examples of the (meth) acrylamide compound used in the present embodiment include N-substituted (meth) acrylamide compounds. An N-substituted (meth) acrylamide compound is a (meth) acrylamide compound having a substituent at the N-position. A typical example of the substituent is an alkyl group. The N-position substituents may be bonded to each other to form a ring, and —CH ₂ — constituting the ring may be substituted with an oxygen atom. Further, a substituent such as an alkyl group or an oxo group (═O) may be bonded to the carbon atom constituting the ring. N-substituted (meth) acrylamides can generally be prepared by reaction of (meth) acrylic acid or its chloride with a primary or secondary amine.

The N-substituted (meth) acrylamide compound is preferably a compound represented by the following formula (III). In the following formula (III), Q ¹ represents a hydrogen atom or a methyl group, Q ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Q ³ represents a carbon number that may have a hydroxyl group or an amino group. 1 to 6 alkyl groups are represented, or Q ² and Q ³ are bonded to each other to form a 5-membered ring or 6-membered ring in which —CH ₂ — may be substituted with an oxygen atom. The hydrogen atom of the amino group may be substituted with an alkyl group.

An example where Q ³ is an alkyl group having a hydroxyl group is a hydroxyalkyl group. Examples where Q ³ is an alkyl group having an amino group include an aminoalkyl group, an N-alkylaminoalkyl group and an N, N-dialkylaminoalkyl group. When Q ² and Q ³ are bonded to each other to form a 5-membered or 6-membered ring in which —CH ₂ — may be substituted with an oxygen atom, examples of the 5-membered or 6-membered ring are represented by N In the form of a group leading to carbonyl (C═O) at the —position, 1-pyrrolidinyl (C ₄ H ₈ N—), 2-oxazolidinon-3-yl [C ₂ H ₄ OC (═O) N—] , Piperidino (C ₅ H ₁₀ N—), morpholino (C ₂ H ₄ OC ₂ H ₄ N—) and the like.

N-substituted (meth) acrylamide compounds in which Q ² is a hydrogen atom and Q ³ is an alkyl group include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, There are N-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-hexyl (meth) acrylamide and the like. Similarly, examples of N-substituted (meth) acrylamide in which both Q ² and Q ³ are alkyl groups include N, N-dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide.

N-substituted (meth) acrylamide compounds in which Q ² is a hydrogen atom and Q ³ is an alkyl group having a hydroxyl group include N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide. N- (2-hydroxypropyl) (meth) acrylamide. Examples of N-substituted (meth) acrylamide compounds in which Q ² is a hydrogen atom and Q ³ is an alkyl group having an amino group include N- [2- (N, N-dimethylamino) ethyl] (meth) acrylamide, N- [2- (N, N-diethylamino) ethyl] (meth) acrylamide, N- [3- (N, N-dimethylamino) propyl] (meth) acrylamide, N- [1-methyl-1- (N , N-dimethylamino) ethyl] (meth) acrylamide and the like.

As an N-substituted (meth) acrylamide compound in which Q ² and Q ³ are bonded to each other to form a 5-membered ring or 6-membered ring in which —CH ₂ — may be substituted with an oxygen atom, N-acryloyl Examples include pyrrolidine, 3-acryloyl-2-oxazolidinone, 4-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine and the like.

Among the N-substituted (meth) acrylamide compounds, N-hydroxyalkyl (meth) acrylamides such as N-hydroxymethylacrylamide and N- (2-hydroxyethyl) acrylamide, and N, N-dimethylacrylamide and N, N, N-dialkyl (meth) acrylamides such as N-diethylacrylamide are preferred, and N- (2-hydroxyethyl) acrylamide or N, N-dimethylacrylamide is particularly preferred.

In addition, N-alkyl (meth) acrylamide having a long chain alkyl such as N-dodecyl (meth) acrylamide, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide and N- (alkoxyalkyl) (meth) acrylamides such as N- (butoxymethyl) acrylamide can also be used as the N-substituted (meth) acrylamide compound constituting the active energy ray-curable compound.

Bifunctional (meth) acrylate monomers include alkylene glycol di (meth) acrylate, polyoxyalkylene glycol di (meth) acrylate, halogen-substituted alkylene glycol di (meth) acrylate, aliphatic polyol di (meth) acrylate, hydrogenated Di (meth) acrylate of dicyclopentadiene or tricyclodecane dialkanol, di (meth) acrylate of dioxane glycol or dioxane dialkanol, di (meth) acrylate, bisphenol A or bisphenol of alkylene oxide adduct of bisphenol A or bisphenol F A typical example is F epoxy di (meth) acrylate.

Examples of the bifunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di ( (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, ditrimethylolpropane di (meth) acrylate , Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, silicone di (meth) acrylate, di (meth) acrylate of hydroxypivalic acid neopentyl glycol ester, 2,2-bis [4 -(Meth) acryloyloxyethoxyethoxyphenyl] propane, 2,2-bis [4- (meth) acryloyloxyethoxyethoxycyclohexyl] propane, hydrogenated dicyclopentadienyl di (meth) acrylate, tricyclodecane dimethanol di (Meth) acrylate, 1,3-dioxane-2,5-diyldi (meth) acrylate (also called dioxane glycol di (meth) acrylate), hydroxypivalaldehyde and trimethylolpropane Di (meth) acrylate, tris (hydroxyethyl) isocyanurate of tar compound [chemical name: 2- (2-hydroxy-1,1-dimethylethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane] Examples include di (meth) acrylate.

The trifunctional or higher polyfunctional (meth) acrylate monomers include glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol. Tri- or higher functional aliphatic polyols such as tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate Of poly (meth) acrylate. In addition, poly (meth) acrylates of tri- or higher functional halogen-substituted polyols, tri (meth) acrylates of alkylene oxide adducts of glycerol, tri (meth) acrylates of alkylene oxide adducts of trimethylolpropane, 1,1,1- Examples include tris [(meth) acryloyloxyethoxyethoxy] propane, tris (hydroxyethyl) isocyanurate tri (meth) acrylates, and the like.

Examples of (meth) acrylate oligomers include urethane (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and epoxy (meth) acrylate oligomers.

The urethane (meth) acrylate oligomer is a compound having a urethane bond (—NHCOO—) and at least two (meth) acryloyloxy groups in the molecule. Specifically, the product of the urethanization reaction between a hydroxyl group-containing (meth) acrylate monomer having at least one (meth) acryloyloxy group and at least one hydroxyl group in the molecule and a polyisocyanate, or a polyol and a polyisocyanate. Product of urethane reaction containing terminal isocyanate group-containing urethane compound obtained by reacting and a (meth) acrylate monomer each having at least one (meth) acryloyloxy group and at least one hydroxyl group in the molecule Etc.

Examples of the hydroxyl group-containing (meth) acrylate monomer used in the urethanization reaction include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxy. Examples include propyl (meth) acrylate, glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

Examples of the polyisocyanate used for the urethanization reaction with the hydroxyl group-containing (meth) acrylate monomer include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and aromatics among these diisocyanates. Diisocyanates obtained by hydrogenating the above isocyanates (for example, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, etc.), diphenyl or tri-isocyanate such as triphenylmethane triisocyanate, dibenzylbenzene triisocyanate and the above-mentioned Examples thereof include polyisocyanates obtained by increasing the amount of diisocyanate.

In addition, examples of polyols used to obtain terminal isocyanate group-containing urethane compounds by reaction with polyisocyanates include aromatic polyols, aliphatic and alicyclic polyols, polyester polyols, polyether polyols, and the like. . Examples of aromatic polyols include 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4′-naphthalenediethanol, and 3,4′-naphthalenediethanol. Can be mentioned. Aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane, ditriol. Examples include methylolpropane, pentaerythritol, dipentaerythritol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutanoic acid, glycerin, and hydrogenated bisphenol A.

The polyester polyol is obtained by a dehydration condensation reaction between the above polyols and a polybasic carboxylic acid or an anhydride thereof. Examples of the polybasic carboxylic acid or its anhydride include succinic acid, succinic anhydride, adipic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, trimellitic acid, trimellitic anhydride, pyromellitic acid, anhydrous Examples include pyromellitic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, hexahydrophthalic acid, and hexahydrophthalic anhydride.

Examples of the polyether polyol include polyalkylene glycol, polyoxyalkylene-modified polyol obtained by reaction of the above polyols or dihydroxybenzenes with alkylene oxide, and the like.

The polyester (meth) acrylate oligomer is a compound having at least two ester bonds and at least two (meth) acryloyloxy groups in the molecule. Specifically, it can be obtained by dehydration condensation reaction of (meth) acrylic acid, polybasic carboxylic acid or anhydride thereof, and polyol. Polybasic carboxylic acids or their anhydrides used in the dehydration condensation reaction include succinic acid, succinic anhydride, adipic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, trimellitic acid, trimellitic anhydride Examples include acids, pyromellitic acid, pyromellitic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and the like. The polyol used in the dehydration condensation reaction is 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, trimethylol ethane, trimethylol propane. , Ditrimethylolpropane, pentaerythritol, dipentaerythritol, dimethylolheptane, dimethylolpropionic acid, dimethylolbutanoic acid, glycerin, hydrogenated bisphenol A and the like.

The epoxy (meth) acrylate oligomer has at least two (meth) acryloyloxy groups in the molecule, and can be obtained by an addition reaction between polyglycidyl ether and (meth) acrylic acid. Examples of the polyglycidyl ether used in the addition reaction include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and bisphenol A diglycidyl ether.

A compound having at least one (meth) acryloyl group in the molecule has a low affinity with the plasticizer and forms a crosslinked structure upon polymerization. Therefore, the cured product of the composition containing the compound is It is considered that the plasticizer hardly penetrates. Thereby, in the case where the plasticizer is transferred from the resin layer 21 toward the polarizer layer 11 (in the direction of the arrow in FIG. 1) in a humid heat environment (for example, an environment having a room temperature of 60 ° C. and a humidity of 95%). It is speculated that the penetration of the plasticizer can be suppressed.

The content of the radical polymerizable compound is preferably 1 part by mass or more and 70 parts by mass or less, and more preferably 10 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the present composition.

In the present composition, the radically polymerizable compound may be used alone or in combination of two or more.

(Other ingredients)
(Cationically polymerizable compound)
The present composition may contain a cationic polymerizable initiator as necessary in addition to the above-mentioned radical polymerizable compound. Examples of the cationic polymerizable compound include oxetane compounds and epoxy compounds.

Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane.

These oxetane compounds can be easily obtained as commercial products, and as the commercial products, all are trade names sold by Toagosei Co., Ltd., “Aron Oxetane (registered trademark) OXT-101”. Etc.

In the present composition, the oxetane compound may be used alone or in combination of two or more.

In addition to the above radical polymerizable compound, the present composition may contain an epoxy compound as necessary. The epoxy compound is one of cationically polymerizable compounds like the oxetane compound, and can be cured by irradiation with active energy rays. When this composition contains an epoxy compound, the adhesiveness of the resin layer 21 and the polarizer layer 11 can be improved.

Examples of the epoxy compound include an aromatic epoxy compound, a glycidyl ether of a polyol having an alicyclic ring, an aliphatic epoxy compound, and an alicyclic epoxy compound.

Aromatic epoxy compounds include bisphenol type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F and diglycidyl ether of bisphenol S; phenol novolac epoxy resins, cresol novolac epoxy resins and hydroxybenzaldehyde phenol novolacs Examples thereof include novolak-type epoxy resins such as epoxy resins; glycidyl ethers of tetrahydroxyphenylmethane, glycidyl ethers of tetrahydroxybenzophenone, and polyfunctional epoxy resins such as epoxidized polyvinylphenol.

As the glycidyl ether of a polyol having an alicyclic ring, a nuclear hydrogenated polyhydroxy compound obtained by selectively hydrogenating an aromatic polyol under pressure in the presence of a catalyst under pressure is used as a glycidyl ether. Can be listed. Examples of aromatic polyols include bisphenol type compounds such as bisphenol A, bisphenol F, and bisphenol S; novolac type resins such as phenol novolac resin, cresol novolac resin, hydroxybenzaldehyde phenol novolac resin; tetrahydroxydiphenylmethane, tetrahydroxybenzophenone, A polyfunctional compound such as polyvinylphenol is exemplified.

Glycidyl ether can be obtained by reacting an alicyclic polyol obtained by hydrogenating the aromatic ring of these aromatic polyols with epichlorohydrin.
Among these glycidyl ethers of polyols having an alicyclic ring, hydrogenated bisphenol A diglycidyl ether is preferable.

Examples of the aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. Specifically, 1,4-butanediol diglycidyl ether; 1,6-hexanediol diglycidyl ether; glycerin triglycidyl ether; trimethylolpropane triglycidyl ether; polyethylene glycol diglycidyl ether; propylene glycol Diglycidyl ether of neopentyl glycol; by adding one or more alkylene oxides (ethylene oxide or propylene oxide) to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol or glycerin The polyglycidyl ether of the polyether polyol obtained is mentioned.

Moreover, the monofunctional epoxy compound represented by following formula (I) is also mentioned as an aliphatic epoxy compound. R ¹ is an optionally branched alkyl group having 1 to 15 carbon atoms. The number of carbon atoms of the alkyl group is preferably 6 or more, more preferably 6 to 10. Of these, a branched alkyl group is preferred. Examples of the monofunctional epoxy compound represented by the formula (I) include 2-ethylhexyl glycidyl ether.

An alicyclic epoxy compound refers to a compound having at least one structure in the molecule that forms an oxirane ring with carbon atoms of the alicyclic ring. Here, “a structure in which an oxirane ring is formed together with a carbon atom of an alicyclic ring” means a structure represented by the following formula (II). N in the formula is an integer of 2 to 5.

A compound in which a group in a form in which one or a plurality of hydrogen atoms in (CH ₂ ) _n in formula (II) are removed is bonded to another chemical structure is an alicyclic epoxy compound. One or more hydrogen atoms in (CH ₂ ) _n forming the alicyclic ring may be substituted with a linear alkyl group such as a methyl group or an ethyl group.

As the epoxy compound, an alicyclic epoxy compound is preferable, and an epoxy cyclohexane (n = 4 in the above formula (II)) or epoxy cycloheptane is preferable in that an excellent protective layer can be easily obtained due to adhesion with a polarizer. Epoxy compounds having (with n = 5 in the above formula (II)) are more preferred.

In the present composition, the epoxy compound may be used alone or in combination of two or more.

(Radical polymerization initiator)
When this composition contains said radically polymerizable compound, it is preferable that the radical polymerization initiator is further included. Any radical polymerization initiator may be used as long as it can initiate polymerization of a radical polymerizable compound such as a (meth) acrylic compound by irradiation with active energy rays, and a known one can be used.

Examples of radical polymerization initiators include acetophenone, 3-methylacetophenone, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- ( Acetophenone initiators such as methylthio) phenyl-2-morpholinopropan-1-one and 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzophenone, 4-chlorobenzophenone and 4,4′-diamino Benzophenone initiators such as benzophenone; benzoin ether initiators such as benzoin propyl ether and benzoin ethyl ether; thioxanthone initiators such as 4-isopropylthioxanthone; xanthone, fluorenone, camphorquinone Benzaldehyde, such as anthraquinone, and the like.

Commercially available radical polymerization initiators can be easily obtained. For example, “Irgacure (registered trademark) 184”, “Irgacure (registered trademark) 907” and “Darocur (registered trademark)” manufactured by BASF are available. Trademark) 1173 "," Lucirin (registered trademark) TPO ", and the like.

In the present composition, the radical polymerization initiator may be used alone or in combination of two or more.

(Cationic polymerization initiator)
When this composition contains cationically polymerizable compounds, such as the said oxetane compound and the said epoxy compound, it is preferable that the cationic polymerization initiator is further included. The cationic polymerization initiator generates a cationic species or a Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and initiates a polymerization reaction of the cationic polymerizable compound. Examples of the cationic polymerization initiator include aromatic diazonium salts, onium salts such as aromatic iodonium salts and aromatic sulfonium salts, and iron-arene complexes.

Examples of the aromatic diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate.

Examples of the aromatic iodonium salt include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and the like.

Examples of the aromatic sulfonium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis [diphenylsulfonio] diphenyl sulfide bishexa Fluorophosphate, 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluoroantimonate, 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bis Hexafluorophosphate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate, 7- [di (p-toluyl) sulfo Nio] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide hexafluorophosphate, 4- (p-tert-butylphenylcarbonyl) -4'-diphenylsulfo Nio-diphenyl sulfide hexafluoroantimonate, 4- (p-tert-butylphenylcarbonyl) -4'-di (p-toluyl) sulfonio-diphenyl sulfide tetrakis (pentafluorophenyl) borate and the like.

Examples of iron-arene complexes include xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene-cyclopentadienyl iron (II) tris ( (Trifluoromethylsulfonyl) methanide and the like.

These cationic polymerization initiators can be easily obtained as commercial products. For example, “Kayarad (registered trademark) PCI-220” and “Kayarad” sold by Nippon Kayaku Co., Ltd. under the trade names, respectively. (Registered trademark) PCI-620 "," UVI-6990 "sold by Dow Chemical Company," UVACURE (registered trademark) 1590 "sold by Daicel-Cytec Corporation, sold by ADEKA Corporation "Adekaoptomer (registered trademark) SP-150" and "Adekaoptomer (registered trademark) SP-170", "CI-5102", "CIT-1370", "CIT" sold by Nippon Soda Co., Ltd. −1682 ”,“ CIP-1866S ”,“ CIP-2048S ”and“ CIP-20 ” 4S "," DPI-101 "," DPI-102 "," DPI-103 "," DPI-105 "," MPI-103 "," MPI-105 "," BBI "sold by Midori Chemical Co., Ltd. -101 "," BBI-102 "," BBI-103 "," BBI-105 "," TPS-101 "," TPS-102 "," TPS-103 "," TPS-105 "," MDS-103 " "MDS-105", "DTS-102" and "DTS-103", "PI-2074" sold by Rhodia.

Among these cationic polymerization initiators, the aromatic sulfonium salt is capable of absorbing light having a wavelength of 300 nm or more, having excellent curability, and obtaining a cured product having good mechanical strength and adhesion. preferable.

As the cationic polymerization initiator, one kind may be used alone, or two or more kinds may be mixed and used.

(Other additives)
In addition to the above compounds, the present composition may contain a photosensitizer, a solvent, a leveling agent, an antioxidant, a light stabilizer, an ultraviolet absorber, and the like as long as the effects of the present invention are not impaired.

Examples of photosensitizers that may be used in the present embodiment include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo compounds, diazo compounds, halogen compounds, and photoreductive dyes.

Examples of the solvent that may be used in the present embodiment include aliphatic hydrocarbons such as n-hexane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; methanol, ethanol, propanol, isopropanol, and n- Alcohols such as butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as methyl acetate, ethyl acetate and butyl acetate; cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve; Halogenated hydrocarbons such as methylene and chloroform.

As the leveling agent that may be used in the present embodiment, various compounds such as silicone, fluorine, polyether, acrylic acid copolymer, and titanate can be used.

Examples of the antioxidant that may be used in the present embodiment include primary antioxidants such as phenols and amines, and sulfur-based secondary antioxidants.

Examples of the light stabilizer that may be used in the present embodiment include hindered amine light stabilizers (HALS).
Examples of ultraviolet absorbers that may be used in this embodiment include benzophenone-based, benzotriazole-based, and benzoate-based compounds.

[Protective film]
FIG. 2 is a schematic cross-sectional view showing a modification of the layer configuration of the laminated film of the present embodiment. As shown in FIG. 2, in the laminated film 2, a protective film 23 can be further laminated on the side of the polarizer layer 11 opposite to the side where the resin layer 21 is laminated. As a material for forming the protective film 23, the same resin as the material for forming the resin layer 21 can be used. The material forming the resin layer 21 and the material forming the protective film 23 may be the same or different.

The protective film 23 can be laminated on the polarizer layer 11 via the adhesive layer 33.
Examples of the adhesive layer 33 include a water-based adhesive and an active energy ray-curable adhesive. Examples of the active energy ray-curable adhesive include a cationic polymerization-type active energy ray-curable adhesive and a radical polymerization-type active energy. A line curable adhesive is mentioned. An adhesive layer may be provided instead of the adhesive layer 33. Examples of the pressure-sensitive adhesive layer include a pressure-sensitive adhesive containing an acrylic resin.

An adhesive layer (not shown) may be provided on the side opposite to the surface of the polarizer layer 11 on which the resin layer 21 is laminated, or on the side of the protective film opposite to the surface on which the polarizer layer 11 is laminated. . By providing the pressure-sensitive adhesive layer, the laminated film 2 can be bonded to the liquid crystal cell of the display device. Examples of the pressure-sensitive adhesive layer include a pressure-sensitive adhesive containing an acrylic resin. The laminated film of the present invention is preferably arranged on the viewing side of the liquid crystal cell.

[Production method of laminated film]
The laminated film 1 of this embodiment is
(I) A layer of an adhesive composition containing a compound having at least one (meth) acryloyl group in the molecule on one surface of the resin layer 21 having a slow axis (hereinafter referred to as “adhesive composition layer”) Forming a process), and
(Ii) The polarizer layer 11 and the adhesive composition layer formed on the resin layer 21 in (i) above have a slow axis of 45 ± 10 ° with respect to the absorption axis of the polarizer layer 11. Or a step of obtaining a laminate in which the polarizer layer 11, the adhesive composition layer, and the resin layer 21 are laminated in this order by laminating so as to be 135 ± 10 °;
(Iii) The laminate obtained in (ii) above is irradiated with active energy rays (for example, ultraviolet rays, visible light, electron beams, X-rays, etc.), and the adhesive composition layer is cured to form an adhesive layer 31. And obtaining a process. Hereinafter, each process will be described with specific examples.

In the step shown in (i) above, first, a resin layer 21 having a slow axis is prepared. When the polarizer layer 11 is continuously manufactured, the elongated polarizer layer may have an absorption axis in the flow direction. A laminate (laminated film) can be produced by roll-to-roll, and both can be arranged so that the angle formed by the absorption axis and the slow axis of the resin layer 21 falls within the above range. The resin layer 21 is preferably manufactured by being obliquely stretched.

Examples of the stretching machine used for the oblique stretching include a tenter type stretching machine. The tenter type stretching machine can apply a feeding force, a pulling force or a pulling force at different speeds in the left and right directions in the horizontal direction or the vertical direction or in both directions. Examples of such a tenter-type stretching machine include a horizontal uniaxial stretching machine and a simultaneous biaxial stretching machine. Any suitable stretching machine can be used as long as the resin film can be continuously stretched obliquely. it can.

As a method for forming the adhesive composition layer on one surface of the resin layer 21, there is a method in which the present composition is directly applied and dried as necessary. Further, as another method, there is a method in which the present composition is applied to a transparent substrate film, dried as necessary, and then transferred to the polarizer layer 11. In the latter case, the base film is removed before the step (ii). As the transparent base film, the same resin as described above is used. Moreover, in the transparent substrate film, the application surface of the present composition may be subjected to a peeling treatment in advance.

As a coating method of the present composition, a known coating method can be employed, and examples thereof include a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater.

In the step shown in (ii) above, the polarizer layer 11 and the adhesive composition layer formed on the resin layer 21 in (i) above are bonded together, and the polarizer layer 11, the adhesive composition layer, and the resin layer 21 are bonded together. Are stacked in this order.

In the step shown in (iii) above, the adhesive composition layer is formed by irradiating the laminate obtained in (ii) with active energy rays such as visible light, ultraviolet rays, X-rays, or electron beams. It hardens | cures and it is set as the adhesive bond layer 31, and the laminated | multilayer film 1 is obtained.

The light source used for irradiation with active energy rays is not particularly limited, but a light source having a light emission distribution at a wavelength of 400 nm or less is used. Examples of such a light source include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, and a metal halide lamp.

The irradiation intensity of the active energy ray varies depending on the adhesive composition to be cured, but it is preferable that the irradiation intensity in the wavelength region effective for activating the cationic polymerization initiator is set in the range of 10 to 2500 mW / cm ² .

The irradiation time of the active energy ray varies depending on the adhesive composition to be cured, but it is preferable to set the integrated light amount represented by the product of the irradiation intensity and the irradiation time in the range of 10 to 2500 mJ / cm ² .

In the above production example, the adhesive composition layer is formed on one surface of the resin layer 21, but may be formed on one surface of the polarizer layer 11 or on both surfaces. As shown in FIG. 2, a protective film 23 may be laminated on the side of the polarizer layer 11 opposite to the side where the resin layer 21 is bonded, and further a pressure-sensitive adhesive for bonding to a liquid crystal cell. A layer (not shown) may be provided.

According to the laminated film having the above configuration, a high degree of polarization can be maintained even in a humid heat environment.

<Laminated film stock>
In the present embodiment, the polarizer layer and the resin layer may both be long. The laminated film original fabric (elongated laminated film) of the present embodiment includes a strip-shaped polarizing film original fabric (long-shaped polarizer layer), a belt-shaped resin film original fabric (long-shaped resin layer), and And an adhesive layer that bonds the polarizing film original and the resin film original.

The original polarizing film is a strip-shaped film made of a PVA-based resin, and a dichroic dye is oriented in the longitudinal direction of the film. The PVA resin and the dichroic dye are the same as described above.

The resin film raw fabric is formed by stretching a strip-shaped film made of a thermoplastic resin and a plasticizer in a direction oblique to the longitudinal direction of the film. Thereby, a roll, a toe | roll, and a roll are attained at the time of lamination | stacking with a polarizing film original fabric, and a manufacturing process can be simplified. The thermoplastic resin and the plasticizer are the same as described above.

The resin film original is preferably a retardation film original. In the resin film original fabric, a slow axis is given at an arbitrary angle with respect to the absorption axis of the polarizing film original fabric. The arbitrary angle is preferably 45 ± 10 ° or 135 ± 10 ° with respect to the absorption axis of the polarizing film original. When the angle of the slow axis is in the above range, when the laminated film original fabric of the present embodiment is applied to a display device, a configuration with excellent visibility can be obtained even when viewed through a polarizing glass.

The adhesive layer contains a cured product of the adhesive composition as a forming material, and the adhesive composition contains a compound having at least one (meth) acryloyl group in the molecule. The compound having at least one (meth) acryloyl group in the molecule is the same as described above. A compound having at least one (meth) acryloyl group in the molecule has a low affinity with the plasticizer and forms a crosslinked structure upon polymerization. Therefore, the cured product of the composition containing the compound is It is considered that the plasticizer hardly penetrates. This suppresses the intrusion of the plasticizer even in the case where the plasticizer moves from the resin film original to the polarizing film original in a humid heat environment (for example, at room temperature of 60 ° C. and humidity of 95%). Presumed to be possible.

According to the laminated film original fabric having the above-described configuration, a high degree of polarization can be maintained even in a humid heat environment.

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples. The unstretched film used in this example refers to a film that has not been stretched.

[Evaluation of heat and humidity resistance of laminated film]
The laminated films of Examples and Comparative Examples were allowed to stand for 250 hours in an environment having a temperature of 65 ° C. and a relative humidity of 90%, and the visibility correction polarization degrees before and after being left were compared. At that time, the absolute value (ΔPy) of the value obtained by subtracting the visibility-corrected polarization degree before leaving from the visibility-corrected polarization degree after being left is set to ○, and ΔPy is set to 0. What was larger than 3 was set as x. The visibility correction polarization degree was measured by the following method. The results are shown in Tables 1 to 3.

(Measurement of visibility correction polarization degree)
For the laminated films of Examples and Comparative Examples, MD transmittance and TD transmittance in a wavelength range of 380 nm to 780 nm were measured with a spectrophotometer with an integrating sphere (manufactured by JASCO Corporation, “V7100”). Next, the degree of polarization at each wavelength was calculated based on the formula (T1) using the MD transmittance and the TD transmittance.
Here, “MD transmittance” indicates the transmittance when the direction of polarized light emitted from the Glan-Thompson prism is parallel to the transmission axis of the laminated film sample. The “TD transmittance” refers to the transmittance when the direction of polarized light emitted from the Glan-Thompson prism is orthogonal to the transmission axis of the laminated film sample.

(Measurement of moisture permeability of evaluation sample)
The evaluation sample was produced as follows. First, the adhesive composition was applied onto a triacetyl cellulose film using a bar coater so as to have a thickness of 2 to 3 μm to form an adhesive composition layer. The triacetyl cellulose film for measuring the moisture permeability of the evaluation sample has a thickness of 57.5 μm and moisture permeability (value calculated by the cup method (JIS Z 0208, temperature 40 ° C., humidity 90% RH)). KC6UA manufactured by Konica Minolta Co., Ltd. having a 553 g / m ² · 24 hr was used. Next, from the adhesive composition layer side, an ultraviolet ray is irradiated using a D bulb manufactured by Fusion UV Systems Co., Ltd. so that the integrated light amount becomes 400 mJ / cm ² , the adhesive composition layer is cured, and the evaluation sample and did. The moisture permeability of the obtained evaluation sample was measured by a cup method (JIS Z 0208, temperature 40 ° C., humidity 90% RH).

[Production Example (Preparation of Adhesive Composition)]
According to the blending amounts shown in Tables 1 to 3, adhesive compositions of Examples and Comparative Examples were prepared. However, the names of the compounds used for the preparation may be indicated by abbreviations.
The cationic polymerization initiator “Adekaoptomer (registered trademark) SP-150” uses a propylene carbonate solution, but in Table 2, it is indicated by the amount of the active ingredient. The epoxy-based cross-linking agent “SUMIREZ RESIN (registered trademark) 650” is an aqueous solution, but in Table 3, it is indicated by the amount of the active ingredient.

In addition, the following compounds were used for each component of the adhesive composition.

[Active energy ray-curable adhesive composition]
(Cationically polymerizable compound)
“Celoxide (registered trademark) 2021P”: 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, obtained from Daicel Chemical Industries, Ltd.
“YX8000”: Diglycidyl ether of bisphenol, obtained from Mitsubishi Chemical Corporation.
“Aron Oxetane (registered trademark) OXT-101”: 3-ethyl-3-hydroxymethyloxetane, obtained from Toagosei Co., Ltd.

Among the above cationically polymerizable compounds, the structure of the oxetane compound is represented by the following formula (IV).

(Radically polymerizable compound)
“DMAA”: dimethylacrylamide, obtained from KJ Chemicals.
“4HBA”: 4-hydroxybutyl acrylate, obtained from Nippon Kasei Co., Ltd.
“UV-3700B”: urethane acrylate, obtained from Nippon Synthetic Chemical Industry Co., Ltd.
“CHDMMA”: 1,4-cyclohexanedimethanol monoacrylate, obtained from Nippon Kasei Co., Ltd.
“A-DCP”: tricyclodecane dimethanol diacrylate, obtained from Shin-Nakamura Chemical Co., Ltd.

(Cationic polymerization initiator)
"Adekaoptomer (registered trademark) SP-150": 4,4'-bis [diphenylsulfonio] diphenyl sulfide Bishexafluorophosphate-based photocationic polymerization initiator, obtained from ADEKA Corporation in the form of a propylene carbonate solution.

(Radical polymerization initiator)
“Darocur® 1173”: 2-hydroxy-2-methyl-1-phenyl-propan-1-one, obtained from BASF Japan Ltd.
“Irgacure (registered trademark) 907”: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, obtained from BASF Japan Ltd.

[Water-based adhesive composition]
(Polyvinyl alcohol)
“Kuraray Poval (registered trademark) KL-318”: a carboxyl group-modified polyvinyl alcohol, obtained from Kuraray Co., Ltd.

(Epoxy-based crosslinking agent)
“Smilease Resin (registered trademark) 650”: Water-soluble polyamide epoxy resin (aqueous solution with a solid content of 30%), obtained from Sumika Chemtex Co., Ltd.

[Other ingredients]
“SH710”: Silicone leveling agent, obtained from Toray Dow Corning Co., Ltd.

[Examples 1 to 5, Comparative Examples 1 to 6]
(A) Preparation of polarizer layer A polyvinyl alcohol film having an average polymerization degree of about 2400 and a saponification degree of 99.9 mol% or more and a thickness of 30 μm is uniaxially stretched about 5 times in a dry process, and further kept in a tension state After being immersed in pure water at 60 ° C. for 1 minute, it was immersed in an aqueous solution having a weight ratio of iodine / potassium iodide / water of 0.05 / 5/100 at 28 ° C. for 60 seconds. Then, it was immersed in an aqueous solution having a weight ratio of potassium iodide / boric acid / water of 8.5 / 8.5 / 100 at 72 ° C. for 300 seconds. Subsequently, the film was washed with pure water at 26 ° C. for 20 seconds, and then dried at 65 ° C. to prepare a polarizer layer in which iodine was oriented on a uniaxially stretched polyvinyl alcohol film. The thickness of the polarizer was 12 μm.

(B) Preparation of resin layer A triacetyl cellulose film produced by oblique stretching as a resin layer and containing a plasticizer was prepared.
A hard coat layer was formed on one side of the triacetyl cellulose film. Moreover, the angle of the slow axis with respect to the longitudinal direction of the film of the resin layer was about 45 ° on average.
The following materials were used as the triacetyl cellulose film produced by oblique stretching.
Triacetyl cellulose film produced by the oblique stretching: Konica Minolta Co., Ltd., KC4UGR-HC, thickness _{= 44μm, R e (590)} = 106nm, R th (590) = 75nm, R th (590) / R e ( 590) = 0.71, R _e (450) / R _e (550) = 0.96, R _e (630) / R _e (550) = 1.02)
Note that R _e (590), R _e (450), R _e (550), and R _e (630) represent in-plane retardation values at measurement wavelengths of 590 nm, 450 nm, 550 nm, and 630 nm, respectively, and R _th (590 ) Represents a thickness direction retardation value at a measurement wavelength of 590 nm.

(C) Production of laminated film Next, the adhesive composition obtained in the production example was applied to the surface of the resin layer (b) where the hard coat layer was not formed to form an adhesive composition layer. . Specifically, the adhesive composition was applied using a bar coater (manufactured by Daiichi Rika Co., Ltd.) so that the film thickness after curing was about 2 μm. Separately, a corona discharge treatment was performed on one side of an unstretched film (trade name “ZEONOR (registered trademark)” manufactured by Nippon Zeon Co., Ltd.) using a norbornene-based resin having a thickness of 23 μm as a forming material. The adhesive composition was applied to the corona discharge treated surface in the same manner as the resin layer to form an adhesive composition layer. The unstretched film is a raw material for the protective film in the laminated film.

Adhesive composition formed on the other surface of the polarizer layer and an unstretched film while bonding one surface of the polarizer layer prepared in (a) above and the adhesive composition layer formed on the resin layer. The layers were bonded together to produce a laminate. For pasting, a pasting apparatus (manufactured by Fuji Pla Co., Ltd., “LPA3301”) was used. When pasting, the angle formed by the absorption axis of the polarizer layer and the slow axis of the resin layer was set to 45 °.

Next, using an ultraviolet irradiation device with a belt conveyor (the lamp uses a “D bulb” manufactured by Fusion UV Systems), the accumulated light amount is 250 mJ / cm ² from the unstretched film side of the obtained laminate. The adhesive composition layer was cured by irradiating with UV rays. Thus, the laminated film which consists of a protective film / polarizer layer / adhesive layer / resin layer / hard coat layer was produced.

The moisture permeability of the evaluation sample obtained from the adhesive composition used in each example and comparative example was as follows.
Example ^{3: 297g / m 2 · 24hr} , Example ^{5: 251g / m 2 · 24hr} , Comparative Example ^{1: 447g / m 2 · 24hr} , Comparative Example ^{3: 307g / m 2 · 24hr} , Comparative Example 4: 428 g / m ² · 24 hr, Comparative Example 5: 529 g / m ² · 24 hr

[Comparative Example 7]
(C) A laminated film of Comparative Example 7 was produced in the same manner as in Example 1 except that the following operation was performed in the production of the laminated film.

The resin layer prepared in (b) above was bonded to one surface of the polarizer layer prepared in (a) above through the aqueous adhesive composition obtained in the production example. Then, after drying at 80 degreeC for 5 minute (s), it cured at 40 degreeC and 23% RH for 72 hours, and produced the laminated | multilayer film.

[Reference example]
(A-1) Preparation of Polarizer Layer A polarizer layer having a thickness of 30 μm in which iodine was oriented on a uniaxially stretched polyvinyl alcohol film was prepared.

(B-1) Preparation of Resin Layer A saponification treatment was prepared on a 43 μm thick triacetyl cellulose film (KC4FR-1, manufactured by Konica Minolta Opto). This film is a stretched film and contains a plasticizer.

(B-2) Preparation of protective film A triacetyl cellulose film with a hard coat layer was subjected to saponification treatment. The thickness of this film was 83 μm.

(C-1) Production of Laminated Film By means of a nip roll, one side of the polarizer layer produced in (a-1) above was passed through the aqueous adhesive composition obtained in the above production example via (b- The resin layer prepared in 1) was bonded, and the protective film prepared in (b-2) was bonded to the other surface via the same adhesive composition to prepare a laminate. At this time, the slow axis of the resin layer and the absorption axis of the polarizer layer were made substantially parallel. When the protective film prepared in (b-2) was bonded, the side without the hard coat layer was the bonding surface with the polarizer layer. Next, while maintaining the tension of the laminate, the laminate was passed through a drying furnace to dry the adhesive to obtain a laminate film.

A pressure-sensitive adhesive layer (thickness 15 μm) having a storage elastic modulus of about 0.7 MPa was provided on the opposite side of the resin layer from the adhesive surface with the polarizer layer. The laminated film was bonded to glass via this pressure-sensitive adhesive layer to obtain an evaluation sample. The sample was allowed to stand for 250 hours in an environment of a temperature of 65 ° C. and a relative humidity of 90% as in the evaluation of the heat and humidity resistance, and the visibility corrected polarization degree before and after being left was compared. As a result, the amount of change ΔPy in the visibility correction polarization degree was 0.3% or less.

From the results in Tables 1 to 3, when an adhesive composition containing a compound having at least one (meth) acryloyl group in the molecule is used, ΔPy is 0.3 or less, and high polarization even in a humid heat environment. It was shown to keep the degree.

From the above, it was confirmed that the present invention is useful.

The present invention can be used as a polarization supply element or a polarization detection element in a display device such as a liquid crystal display device.

1, 2 ... laminated film, 11 ... polarizer layer, 21 ... resin layer, 23 ... protective film, 31, 33 ... adhesive layer

Claims (2)

1. A polarizer layer in which a dichroic dye is oriented in a polyvinyl alcohol resin;
   A resin layer having a resin film having a slow axis in a direction oblique to the absorption axis of the polarizer layer; and
   An adhesive layer that bonds the polarizer layer and the resin layer;
   The resin layer includes a plasticizer,
   The adhesive layer contains a cured product of an adhesive composition as a forming material,
   The adhesive composition is a laminated film containing a compound having at least one (meth) acryloyl group in the molecule.
2. The laminated film according to claim 1, wherein both the polarizer layer and the resin layer are long.

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