CN106569296B - Polarizing plate - Google Patents

Polarizing plate Download PDF

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CN106569296B
CN106569296B CN201610872457.0A CN201610872457A CN106569296B CN 106569296 B CN106569296 B CN 106569296B CN 201610872457 A CN201610872457 A CN 201610872457A CN 106569296 B CN106569296 B CN 106569296B
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epoxy compound
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CN106569296A (en
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永安智
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Sumitomo Chemical Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polarising Elements (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Epoxy Resins (AREA)

Abstract

The purpose of the present invention is to provide a polarizing plate that can maintain optical performance without iodine migration from a polarizing film to another layer such as a protective film or an adhesive layer. A polarizing plate comprising a first cured product layer (1) formed from a cured product of a curable composition containing a polymerizable compound, and an adhesive layer, in this order, on one surface of a polarizing film containing iodine in polyvinyl alcohol, wherein the composition of the polymerizable compound contained in the curable composition is: the amount of the oxetane compound (A1) having 2 or more oxetanyl groups is 35 to 70% by mass, the amount of the aliphatic epoxy compound (A2) having 2 or more epoxy groups is 0 to 40% by mass, the amount of the alicyclic epoxy compound (A3) having 2 or more epoxy groups is 15 to 50% by mass, and the amount of the aromatic epoxy compound (A4) having 1 or more aromatic rings is 0 to 20% by mass, based on 100% by mass of the total amount of the polymerizable compounds.

Description

Polarizing plate
Technical Field
The present invention relates to a polarizing plate, and more particularly, to a polarizing plate including a cured product layer formed of a cured product of a curable composition on one surface of an iodine-containing polarizing film. The present invention also relates to a curable composition that can be suitably used as a material constituting a polarizing plate, for example, and a cured product of the curable composition.
Background
Conventionally, polarizing plates have been used in various image display panels such as liquid crystal display panels and organic electroluminescence (organic EL) display panels by bonding to image display elements such as liquid crystal cells and organic EL elements. As such a polarizing plate, a polarizing plate having a structure in which an adhesive layer for bonding to a transparent protective film and an image display element is laminated via an adhesive layer on at least one surface of a polarizing film in which iodine is adsorbed and oriented in a polyvinyl alcohol resin film is known. As an adhesive used for forming such a polarizing plate, for example, patent document 1 describes a photocationic-curable adhesive (curable composition) containing an aliphatic epoxy, an alicyclic epoxy and/or oxetane, and a photopolymerization initiator, and a cured product obtained by curing the composition functions as an adhesive.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2008-063397
Disclosure of Invention
Problems to be solved by the invention
However, when a protective film is laminated on a polarizing film containing iodine using an adhesive as described in the above patent document, the iodine contained in the polarizing film is relatively likely to permeate through the adhesive layer. When iodine permeates the adhesive layer, the optical performance of the polarizing plate may be deteriorated. Since the migration of iodine from such a polarizing film becomes remarkable particularly in a high-temperature and high-humidity environment, a polarizing plate that can maintain optical performance without migration of iodine contained in the polarizing film to an adhesive layer even in a high-temperature and high-humidity environment is required.
The purpose of the present invention is to provide a polarizing plate that is capable of maintaining optical performance without iodine migrating from the polarizing film to the adhesive layer. Further, it is an object to provide a curable composition which is particularly suitable as a material constituting such a polarizing plate.
Means for solving the problems
The present invention provides the following preferred embodiments [1] to [7 ].
[1] A polarizing plate comprising a first cured product layer (1) formed from a cured product of a curable composition containing a polymerizable compound, and an adhesive layer, in this order, on one surface of a polarizing film containing iodine in polyvinyl alcohol, wherein the composition of the polymerizable compound contained in the curable composition is: relative to 100 mass% of the total amount of the polymerizable compound,
(A1)35 to 70 mass% of an oxetane compound having 2 or more oxetanyl groups,
(A2)0 to 40 mass% of an aliphatic epoxy compound having 2 or more epoxy groups,
(A3)15 to 50% by mass of an alicyclic epoxy compound having 2 or more epoxy groups, and 0 to 20% by mass of an aromatic epoxy compound (A4) having 1 or more aromatic rings.
In the polarizing plate, the composition of the polymerizable compound contained in the curable composition may be:
(A1)35 to 70 mass% of an oxetane compound having 2 or more oxetanyl groups,
(A2)3 to 40 mass% of an aliphatic epoxy compound having 2 or more epoxy groups,
(A3)15 to 50% by mass of an alicyclic epoxy compound having 2 or more epoxy groups, and 0.1 to 20% by mass of an aromatic epoxy compound (A4) having 1 or more aromatic rings.
In the polarizing plate, the composition of the polymerizable compound contained in the curable composition may be:
(A1)35 to 70 mass% of an oxetane compound having 2 or more oxetanyl groups,
(A2) 0% by mass of an aliphatic epoxy compound having 2 or more epoxy groups,
(A3)15 to 50 mass% of an alicyclic epoxy compound having 2 or more epoxy groups and 0 mass% of (A4) an aromatic epoxy compound having 1 or more aromatic rings,
at this time, the process of the present invention,
(A3) the mass ratio (Wa3/Wa1) of the content (Wa3) of the alicyclic epoxy compound having 2 or more epoxy groups to the content (Wa1) of the oxetane compound having 2 or more oxetanyl groups (A1) is preferably 0.45 to 1.5.
In the polarizing plate, the composition of the polymerizable compound contained in the curable composition may be:
(A1)35 to 70 mass% of an oxetane compound having 2 or more oxetanyl groups,
(A2) 0% by mass of an aliphatic epoxy compound having 2 or more epoxy groups,
(A3)15 to 50 mass% of an alicyclic epoxy compound having 2 or more epoxy groups and 0.1 to 20 mass% of (A4) an aromatic epoxy compound having 1 or more aromatic rings,
at this time, the process of the present invention,
preferably, the mass ratio (Wa3/Wa1) of the content (Wa3) of the alicyclic epoxy compound having 2 or more epoxy groups to the content (Wa1) of the oxetane compound having 2 or more oxetanyl groups (a1) is 0.45 to 1.5, and the mass ratio (Wa4/Wa1) of the content (Wa4) of the aromatic epoxy compound having 1 or more aromatic rings to the content (Wa1) of the oxetane compound having 2 or more oxetanyl groups (a1) is 0.05 to 0.5.
[2] The polarizing plate according to [1], wherein the (A2) aliphatic epoxy compound having 2 or more epoxy groups is a compound represented by formula (I):
Figure BDA0001124416970000031
wherein Z represents an alkylene group having 1 to 9 carbon atoms, an alkylidene group having 3 or 4 carbon atoms, a 2-valent alicyclic hydrocarbon group, or a group represented by the formula-CmH2m-Z1-CnH2nA 2-valent group represented by (wherein, -Z1-represents-O-, -CO-O-, -O-CO-, -SO2-, -SO-or-CO-, m and n each independently represent an integer of 1 or more, and the sum of m and n is 9 or less);
the (a3) alicyclic epoxy compound having 2 or more epoxy groups is a compound represented by the formula (II):
Figure BDA0001124416970000041
[ in the formula, R1And R2Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group may or may not have an alicyclic structure when the number of carbon atoms is 3 or more,
x represents an oxygen atom, an alkanediyl group having 1 to 6 carbon atoms, or a 2-valent group represented by any one of the following formulae (IIa) to (IId):
Figure BDA0001124416970000042
(in the formula, Y1～Y4Independently represents an alkanediyl group having 1 to 20 carbon atoms, wherein the alkanediyl group may or may not have an alicyclic structure when the number of carbon atoms is 3 or more, and a and b independently represent an integer of 0 to 20).
[3] The polarizing plate according to the above [1] or [2], wherein a1 st transparent protective film is provided between the 1 st cured material layer and the adhesive layer.
[4] The polarizing plate according to any one of the above [1] to [3], wherein a2 nd cured product layer composed of a cured product of a curable composition is provided on a surface of the polarizing film opposite to the 1 st cured product layer with a2 nd transparent protective film interposed therebetween.
[5] A curable composition comprising a polymerizable compound, wherein the composition of the polymerizable compound is: relative to 100 mass% of the total amount of the polymerizable compound,
(A1)35 to 70 mass% of an oxetane compound having 2 or more oxetanyl groups,
(A2)0 to 40 mass% of an aliphatic epoxy compound having 2 or more epoxy groups,
(A3)15 to 50 mass% of an alicyclic epoxy compound having 2 or more epoxy groups and 0 to 20 mass% of (A4) an aromatic epoxy compound having 1 or more aromatic rings,
and comprises (B) a cationic polymerization photoinitiator.
In the curable composition, the composition of the polymerizable compound may be:
(A1)35 to 70 mass% of an oxetane compound having 2 or more oxetanyl groups,
(A2)3 to 40 mass% of an aliphatic epoxy compound having 2 or more epoxy groups,
(A3)15 to 50% by mass of an alicyclic epoxy compound having 2 or more epoxy groups, and 0.1 to 20% by mass of an aromatic epoxy compound (A4) having 1 or more aromatic rings.
In the curable composition, the composition of the polymerizable compound may be:
(A1)35 to 70 mass% of an oxetane compound having 2 or more oxetanyl groups,
(A2) 0% by mass of an aliphatic epoxy compound having 2 or more epoxy groups,
(A3)15 to 50 mass% of an alicyclic epoxy compound having 2 or more epoxy groups and 0 mass% of (A4) an aromatic epoxy compound having 1 or more aromatic rings,
at this time, the process of the present invention,
(A3) the mass ratio (Wa3/Wa1) of the content (Wa3) of the alicyclic epoxy compound having 2 or more epoxy groups to the content (Wa1) of the oxetane compound having 2 or more oxetanyl groups (A1) is preferably 0.45 to 1.5.
Further, in the curable composition, the composition of the polymerizable compound may be:
(A1)35 to 70 mass% of an oxetane compound having 2 or more oxetanyl groups,
(A2) 0% by mass of an aliphatic epoxy compound having 2 or more epoxy groups,
(A3)15 to 50 mass% of an alicyclic epoxy compound having 2 or more epoxy groups and 0.1 to 20 mass% of (A4) an aromatic epoxy compound having 1 or more aromatic rings,
at this time, the process of the present invention,
preferably, the mass ratio (Wa3/Wal) of the content (Wa3) of the alicyclic epoxy compound having 2 or more epoxy groups to the content (Wal) of the oxetane compound having 2 or more oxetanyl groups (a1) is 0.45 to 1.5, and the mass ratio (Wa4/Wal) of the content (Wa4) of the aromatic epoxy compound having 1 or more aromatic rings to the content (Wal) of the oxetane compound having 2 or more oxetanyl groups (a1) is 0.05 to 0.5.
[6] The curable composition according to [5], wherein the (A2) aliphatic epoxy compound having 2 or more epoxy groups is a compound represented by the formula (I):
Figure BDA0001124416970000061
wherein Z represents an alkylene group having 1 to 9 carbon atoms, an alkylidene group having 3 or 4 carbon atoms, a 2-valent alicyclic hydrocarbon group, or a group represented by the formula-CmH2m-Z1-CnH2nA 2-valent group represented by (wherein, -Z1-represents-O-, -CO-O-, -O-CO-, -SO2-, -SO-or-CO-, m and n each independently represent an integer of 1 or more, and the sum of m and n is 9 or less);
the (a3) alicyclic epoxy compound having 2 or more epoxy groups is a compound represented by the formula (II):
Figure BDA0001124416970000062
[ in the formula, R1And R2Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group may or may not have an alicyclic structure when the number of carbon atoms is 3 or more,
x represents an oxygen atom, an alkanediyl group having 1 to 6 carbon atoms, or a 2-valent group represented by any one of the following formulae (IIa) to (IId):
Figure BDA0001124416970000063
(in the formula, Y1～Y4Independently represents an alkanediyl group having 1 to 20 carbon atoms, wherein the alkanediyl group may or may not have an alicyclic structure when the number of carbon atoms is 3 or more, and a and b independently represent an integer of 0 to 20).
[7] A cured product of the curable composition according to [5] or [6 ].
Effects of the invention
According to the present invention, a polarizing plate can be provided in which iodine does not migrate from a polarizing film to an adhesive layer and excellent optical properties can be maintained. Further, a curable composition particularly suitable as a material constituting such a polarizing plate can be provided.
Drawings
Fig. 1 is a cross-sectional view showing a structure of one embodiment of a polarizing plate of the present invention.
Fig. 2 is a cross-sectional view showing a structure of one embodiment of the polarizing plate of the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the present invention.
In the following description of the structure of one embodiment of the polarizing plate of the present invention with reference to fig. 1, the polarizing plate (10) of the present invention has a structure in which a1 st cured material layer (2) and an adhesive layer (3) are sequentially laminated on one surface of a polarizing film (1). If necessary, a transparent protective film (5) may be provided on the surface of the polarizing film (1) opposite to the 1 st cured product layer, with the 2 nd cured product layer (4) interposed therebetween.
The polarizing plate of the present invention may further include a1 st transparent protective film (6) between the 1 st cured material layer (2) and the adhesive layer (3). This embodiment is shown in fig. 2. The polarizing plate (10) may be provided with a2 nd transparent protective film (5) on the surface of the polarizing film (1) opposite to the 1 st cured product layer with a2 nd cured product layer (4) therebetween, as necessary.
A liquid crystal display panel is configured by disposing the polarizing plate (10) of the present invention on one surface of a liquid crystal cell (X) through an adhesive layer, and further disposing a polarizing plate which is the same as or different from the polarizing plate of the present invention on the other surface of the liquid crystal cell.
Hereinafter, each constituent component of the polarizing plate of the present invention will be described in detail.
[ layer of No. 1 curing agent ]
The polarizing plate of the present invention has a1 st cured product layer composed of a cured product of a curable composition on one surface of a polarizing film containing iodine in polyvinyl alcohol. The curable composition contains (a1) an oxetane compound having 2 or more oxetanyl groups (oxetane rings) (hereinafter, sometimes referred to as "oxetane compound (a 1)") as a polymerizable compound.
The oxetane compound (a1) is a compound having 2 or more oxetanyl groups in the molecule, and may be an aliphatic compound, an alicyclic compound or an aromatic compound. Specific examples of the oxetane compound (A1) include bis 1, 4-bis { (3-ethyloxetan-3-yl) methoxy } methyl ] benzene (also referred to as xylylene dioxetane) and bis (3-ethyl-3-oxetanylmethyl) ether. These oxetane compounds (a1) may be used alone or in combination of two or more. Since the curable composition contains the oxetane compound (a1) having 2 or more oxetanyl groups, a cured product having a high crosslinking density and high density can be obtained by curing the curable composition. Therefore, by providing a cured product layer composed of such a cured product on one surface of the polarizing film, the movement of iodine from the polarizing film can be effectively suppressed. When the adhesive layer contains an ionic compound, the ionic compound may act on iodine in the polarizing film to degrade the optical performance when the ionic compound moves to the polarizing film, but the inclusion of the oxetane compound (a1) can suppress the movement of the ionic compound from the adhesive layer to the polarizing film.
The curable composition may contain, as the polymerizable compound, (a2) an aliphatic epoxy compound having 2 or more epoxy groups (hereinafter, sometimes referred to as "aliphatic epoxy compound (a 2)"), or may contain no aliphatic epoxy compound (a2), and the content thereof is 0 (zero) mass%. The aliphatic epoxy compound (a2) has at least 2 or more epoxy rings bonded to aliphatic carbon atoms in the molecule. Examples of the aliphatic epoxy compound (a2) include 2-functional epoxy compounds such as 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, and neopentyl glycol diglycidyl ether; and epoxy compounds having 3 or more functions such as trimethylolpropane triglycidyl ether and pentaerythritol tetraglycidyl ether.
When the aliphatic epoxy compound (a2) is contained, from the viewpoint of adhesiveness between the polarizing film and the transparent protective film, a 2-functional epoxy compound (also referred to as an aliphatic diepoxy compound) having 2 oxirane rings bonded to aliphatic carbon atoms in the molecule is preferable, and an aliphatic diepoxy compound represented by the following formula (I) is more preferable. In particular, when the curable composition contains an aliphatic diepoxy compound represented by the following formula (I) as the aliphatic epoxy compound (a2), a curable composition having a low viscosity and being easily applied can be obtained.
Figure BDA0001124416970000091
In the formula (I), Z is an alkylene group having 1 to 9 carbon atoms, an alkylidene group having 3 or 4 carbon atoms, a 2-valent alicyclic hydrocarbon group, or a group represented by the formula-CmH2m-Z1-CnH2n-a group having a valence of 2 as indicated. Further, the above formula-CmH2m-Z1-CnH2n-in, -Z1-is-O-, -CO-O-, -O-CO-, -SO2-, -SO-or-CO-, m and n each independently represent an integer of 1 or more, and the total of m and n is 9 or less.
The alicyclic hydrocarbon group having a valence of 2 may be, for example, an alicyclic hydrocarbon group having a valence of 2 and having 4 to 8 carbon atoms, and examples thereof include a residue having a valence of 2 represented by the following formula (I-1).
Figure BDA0001124416970000092
Specific examples of the compound represented by the formula (I) include diglycidyl ethers of alkane diols, diglycidyl ethers of oligoalkylene glycols having a repetition number of about 4 or less, and diglycidyl ethers of alicyclic diols.
Examples of the diol (glycol) which can form the compound represented by the formula (I) include ethylene glycol, propylene glycol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 2-butyl-2-ethyl-1, 3-propanediol, 1, 4-butanediol, neopentyl glycol, 3-methyl-2, 4-pentanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2-methyl-2, 4-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 3, 5-heptanediol, 1, 8-octanediol, 2-methyl-1, paraffin diols such as 8-octanediol and 1, 9-nonanediol;
oligoalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, and dipropylene glycol;
alicyclic diols such as cyclohexanediol and cyclohexanedimethanol.
In the present invention, the aliphatic epoxy compound (a2) is preferably 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, or neopentyl glycol diglycidyl ether, from the viewpoint that a curable composition having a low viscosity and easy coating can be formed. From the viewpoint of maintaining optical properties, 1, 6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, and pentaerythritol polyglycidyl ether are preferable. As the aliphatic epoxy compound (a2), 1 kind of aliphatic epoxy compound may be used alone, or a plurality of different kinds may be used in combination.
The curable composition contains (A3) an alicyclic epoxy compound having 2 or more epoxy groups (hereinafter, may be referred to as "alicyclic epoxy compound (A3)") as a polymerizable compound. By containing the alicyclic epoxy compound (a3), the cured product layer of the curable composition after curing becomes a cured product layer having a high elastic modulus, and cracking of the polarizing film due to thermal shrinkage can be suppressed.
The alicyclic epoxy compound (a3) is a compound having 2 or more epoxy groups bonded to an alicyclic ring in a molecule. The "epoxy group bonded to an alicyclic ring" refers to a crosslinked oxygen atom-O-in the structure represented by the following formula (a):
Figure BDA0001124416970000101
in the formula (a), m is an integer of 2 to 5.
Removal (CH2) in the above formula (a)mThe compound in which 2 or more hydrogen atoms in the form of 1 or more hydrogen atoms are bonded to another chemical structure may be an alicyclic epoxy compound (a 3). (CH)2)mIn (3), 1 or more hydrogen atoms may be appropriately substituted by a linear alkyl group such as a methyl group or an ethyl group.
Among them, from the viewpoint of high glass transition temperature of the cured product and excellent adhesiveness between the polarizing film and the transparent protective film, an alicyclic epoxy compound having an epoxycyclopentane structure [ a structure in which m is 3 in the formula (a) ] and an epoxycyclohexane structure [ a structure in which m is 4 in the formula (a) ] is preferable, and an alicyclic diepoxy compound represented by the following formula (II) is more preferable. In particular, when the curable composition contains an alicyclic diepoxy compound represented by the following formula (II) as the compound (a3), the elasticity of the cured product layer of the curable composition after curing becomes high, and cracking of the polarizing film due to thermal shrinkage can be suppressed.
Figure BDA0001124416970000102
In the formula (II), R1And R2Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and may have an alicyclic structure when the number of carbon atoms in the alkyl group is 3 or more. The alkyl group having 1 to 6 carbon atoms may be a straight-chain or branched alkyl group, and examples of the alkyl group having an alicyclic structure include a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group.
In the formula (II), X is an oxygen atom, an alkanediyl group having 1 to 6 carbon atoms, or a 2-valent group represented by any one of the following formulae (IIa) to (IId):
Figure BDA0001124416970000111
examples of the alkanediyl group having 1 to 6 carbon atoms include a methylene group, an ethylene group, and a propane-1, 2-diyl group.
When X in the formula (II) is a 2-valent group represented by any one of the formulae (IIa) to (IId), Y in each formula1～Y4Each independently an alkanediyl group having 1 to 20 carbon atoms, and the alkanediyl group may have an alicyclic structure when the number of carbon atoms is 3 or more.
a and b independently represent an integer of 0 to 20.
Examples of the compound represented by the formula (II) include the following compounds a to G. The chemical formulae a to G shown later correspond to the compounds a to G, respectively.
A: 3, 4-Epoxycyclohexanecarboxylic acid 3, 4-epoxycyclohexylmethyl ester
B: 3, 4-epoxy-6-methylcyclohexanecarboxylic acid 3, 4-epoxy-6-methylcyclohexylmethyl ester
C: ethylidenebis (3, 4-epoxycyclohexane carboxylate)
D: adipic acid di (3, 4-epoxycyclohexylmethyl) ester
E: adipic acid di (3, 4-epoxy-6-methylcyclohexylmethyl) ester
F: diethylene glycol bis (3, 4-epoxy cyclohexyl methyl ether)
G: ethylene glycol bis (3, 4-epoxy cyclohexyl methyl ether)
Figure BDA0001124416970000121
In the present invention, 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexanecarboxylate is more preferable as the alicyclic epoxy compound (a3) from the viewpoint of easy availability. As the alicyclic epoxy compound (a3), 1 kind of alicyclic epoxy compound may be used alone, or a plurality of different alicyclic epoxy compounds may be used in combination.
The curable composition may contain, as the polymerizable compound, (a4) an aromatic epoxy compound having 1 or more aromatic rings (hereinafter, sometimes referred to as "aromatic epoxy compound (a 4)"), or may contain no aromatic epoxy compound (a4), and the content thereof is 0 (zero) mass%. When the curable composition contains the aromatic epoxy compound (a4), the curable composition becomes a hydrophobic resin, and the resulting cured product layer also becomes hydrophobic. Therefore, the intrusion of moisture from the outside under high temperature and high humidity can be prevented, and the movement of iodine contained in the polarizing film can be effectively suppressed.
The aromatic epoxy compound (a4) is a compound having 1 or more aromatic rings in the molecule, and specific examples thereof include the following compounds.
A mono/poly glycidyl etherate of a 1-valent phenol having at least 1 aromatic ring such as phenol, cresol, butylphenol, or an alkylene oxide adduct thereof, for example, a glycidyl etherate or an epoxy novolac resin of bisphenol a or bisphenol F, or a compound obtained by further adding an alkylene oxide to these compounds;
glycidyl ethers of aromatic compounds having 2 or more phenolic hydroxyl groups such as resorcinol, hydroquinone, and catechol;
mono/polyglycidyl etherates of aromatic compounds having 2 or more alcoholic hydroxyl groups, such as benzenedimethanol, benzenediethanol, and benzenedibutanol;
glycidyl esters of polybasic acid aromatic compounds having 2 or more carboxylic acids, such as phthalic acid, terephthalic acid, and trimellitic acid;
glycidyl esters of benzoic acids such as benzoic acid, toluic acid, and naphthoic acid;
epoxides of styrene oxide or divinylbenzene, and the like.
When the aromatic epoxy compound (a4) is contained, it is preferable to contain at least 1 selected from the group consisting of glycidyl ethers of phenols, glycidyl etherate of aromatic compounds having 2 or more alcoholic hydroxyl groups, glycidyl etherate of polyphenols, glycidyl esters of benzoic acids, glycidyl esters of polybasic acids, and epoxides of styrene oxide or divinylbenzene, from the viewpoint of reducing the viscosity of the curable composition.
In addition, from the viewpoint of improving the curability of the curable composition, the aromatic epoxy compound (a4) is preferably an aromatic epoxy compound having an epoxy equivalent of 80 to 500.
As the aromatic epoxy compound (a4), 1 kind of aromatic epoxy compound may be used alone, or a plurality of different kinds may be used in combination.
As the aromatic epoxy compound (A4), commercially available products can be used, and examples thereof include Denacol EX-121, Denacol EX-141, Denacol EX-142, Denacol EX-145, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, ONCOAT EX-1020, ONCOAT EX-1030, ONCOAT EX-1040, ONCOAT EX-1050, ONCOAT EX-1051, ONCOAT EX-1010, ONCOAT EX-1011, and ONCOAT 1012 (manufactured by Nagase Chemtex corporation); OGSOL PG-100, OGSOL EG-200, OGSOL EG-210, OGSOL EG-250 (Osaka Gas Chemicals Co., Ltd.; supra); HP4032, HP4032D, HP4700 (product of DIC corporation); ESN-475V (New Nippon iron King chemical Co., Ltd.); EpikoteYX8800 (manufactured by Mitsubishi chemical); MARPROOF G-0105SA and MARPROOF G-0130SP (manufactured by Nichikoku Co., Ltd.); EPICLON N-665, EPICLON HP-7200 (available from DIC Co., Ltd.); EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (manufactured by Nippon chemical Co., Ltd.); adeka Glycinol ED-501, Adeka Glycinol ED-502, Adeka Glycinol ED-509, Adeka Glycinol ED-529, ADEKA RESIN EP-4000, ADEKA RESIN EP-4005, ADEKA RESIN EP-4100, ADEKA RESIN EP-4901 (manufactured by ADEKA); TECHMORVG-3101L, EPOX-MKR710, EPOX-MKR151 (manufactured by PRINTEC, INC.) and the like.
The content of the polymerizable compounds (a1) to (a4) in the curable composition is set to 100% by mass based on the total amount of all polymerizable compounds contained in the curable composition
(A1)35 to 70 mass%,
(A2)0 to 40 mass%,
(A3)15 to 50 mass%,
(A4)0 to 20 mass%.
In one embodiment of the present invention, the content of the polymerizable compounds (a1) to (a4) may be 100% by mass of the total amount of all polymerizable compounds contained in the curable composition
(A1)35 to 70 mass%,
(A2)3 to 40 mass%,
(A3)15 to 50 mass%,
(A4)0.1 to 20% by mass,
preferably, it is
(A1)45 to 55 mass%,
(A2)10 to 25 mass%,
(A3)25 to 35 mass%,
(A4)0.1 to 20 mass%.
When the content of the oxetane compound (a1) is in the above range, a dense cured product layer can be easily formed. When the content of the aliphatic epoxy compound (a2) is within the above range, the curable composition can have a low viscosity and can be easily applied. When the content of the alicyclic epoxy compound (a3) is within the above range, curing by irradiation with active energy rays such as ultraviolet rays proceeds rapidly, and a cured product layer having sufficient hardness can be easily formed. When the content of the aromatic epoxy compound (a4) is within the above range, the cured product layer becomes hydrophobic and becomes a cured product layer through which iodine is difficult to permeate.
In another embodiment of the present invention, the content of the polymerizable compounds (a1) to (a4) in the curable composition may be set to 100% by mass based on the total amount of all polymerizable compounds contained in the curable composition
(A1)35 to 70 mass%,
(A2)0 mass percent,
(A3)15 to 50 mass%,
(A4) 0% by mass.
In this case, the mass ratio (Wa3/Wa1) of the content (Wa3) of the alicyclic epoxy compound having 2 or more epoxy groups (A3) to the content (Wa1) of the oxetane compound having 2 or more oxetanyl groups (a1) is preferably 0.45 to 1.5, and more preferably 0.6 to 1.25. When the mass ratio of the content of the oxetane compound (a1) to the content of the alicyclic epoxy compound (A3) is within the above range, a more dense cured product having a high crosslinking density can be obtained by curing the curable composition.
In another embodiment of the present invention, the content of the polymerizable compounds (a1) to (a4) in the curable composition may be set to 100% by mass based on the total amount of all polymerizable compounds contained in the curable composition
(A1)35 to 70 mass%,
(A2)0 mass percent,
(A3)15 to 50 mass%,
(A4)0.1 to 20 mass%.
In this case, the mass ratio (Wa3/Wa1) of the content (Wa3) of the alicyclic epoxy compound having 2 or more epoxy groups (A3) to the content (Wa1) of the oxetane compound having 2 or more oxetanyl groups (a1) is preferably 0.45 to 1.5, and more preferably 0.6 to 1.25. The mass ratio (Wa4/Wa1) of the content (Wa4) of the aromatic epoxy compound having 1 or more aromatic rings (a4) to the content (Wa1) of the oxetane compound having 2 or more oxetanyl groups (a1) is preferably 0.05 to 0.5, and more preferably 0.1 to 0.45. When the mass ratio of the contents of the alicyclic epoxy compound (A3) and the oxetane compound (a1) is within the above range, a cured product having a high crosslinking density and a higher density can be obtained by curing the curable composition, and when the mass ratio of the contents of the aromatic epoxy compound (a4) and the oxetane compound (a1) is within the above range, a hydrophobic resin can be obtained by curing the curable composition.
The curable composition may contain, as the polymerizable compound, a polymerizable compound other than the polymerizable compounds (a1) to (a 4). In the present invention, as the polymerizable compound that can be contained in the curable composition, any polymerizable compound known in the art can be used as long as the effects of the present invention can be obtained.
Examples of such polymerizable compounds include aliphatic monoepoxide compounds and alicyclic monoepoxide compounds.
When the curable composition contains, as the polymerizable compound, a polymerizable compound other than the compounds (a1) to (a4), the content thereof is preferably 10% by mass or less, more preferably 5% by mass or less, relative to 100% by mass of the total amount of all polymerizable compounds contained in the curable composition.
In one embodiment of the present invention, the curable composition does not contain a polymerizable compound other than the compounds (a1) to (a4), and the content thereof is 0% by mass.
The curable composition usually contains a polymerization initiator for initiating polymerization. Examples of the polymerization initiator include cationic polymerization photoinitiators (B). The cationic polymerization photoinitiator is a substance that generates a cationic species or a lewis acid by irradiation with active energy rays such as visible light rays, ultraviolet rays, X-rays, or electron rays, and initiates a polymerization reaction of a cationically polymerizable compound. Since the cationic polymerization photoinitiator catalytically functions by light, it is excellent in storage stability and handling properties even when it is mixed into a polymerizable compound. Examples of the compound that generates a cationic species or a lewis acid by irradiation with an active energy ray include onium salts such as aromatic iodonium salts and aromatic sulfonium salts, aromatic diazonium salts, and iron-arene complexes.
The aromatic iodonium salt is a compound having a diaryliodonium cation, and typical examples of the cation include diphenyliodonium cation.
The aromatic sulfonium salt is a compound having a triarylsulfonium cation, and typical examples of the cation include a triphenylsulfonium cation, a4, 4' -bis (diphenylsulfonium) diphenylsulfide cation, and the like. The aromatic diazonium salt is a compound having a diazonium cation, and the cation is typically a benzenediazonium cation. Furthermore, the iron-arene complex is typically a cyclopentadienyl iron (II) arene cation complex salt.
The cations shown above are paired with anions (anions) to constitute the cationic polymerization photoinitiator. Examples of the anion constituting the cationic polymerization photoinitiator include a special phosphorus anion [ (Rf)nPF6-n]-Hexafluorophosphate radical anion PF6 -Hexafluoroantimonate anion SbF6 -Pentafluoro-hydroxyl antimonate anion SbF5(OH)-Hexafluoroarsenate anion AsF6 -Tetrafluoroborate anion BF4 -Tetrakis (pentafluorophenyl) borate anion B (C)6F5)4 -And the like. Among them, the cationic polymerization photoinitiator is preferably a specific phosphorus anion [ (Rf) from the viewpoints of curability of the polymerizable compound and safety of the obtained cured product layernPF6-n]-Hexafluorophosphate radical anion PF6 -。
The cationic polymerization photoinitiator may be used in 1 kind alone, or may be used in combination of different kinds. Among these, the aromatic sulfonium salt is preferable because it has ultraviolet absorption characteristics even in a wavelength region of about 300nm and can provide a cured product having excellent curability and good mechanical strength and adhesive strength.
The content of the cationic polymerization photoinitiator in the curable composition is usually 0.5 to 10 parts by mass, and preferably 6 parts by mass or less, per 100 parts by mass of the polymerizable compound. When the content of the cationic polymerization photoinitiator is within the above range, the polymerizable compound can be sufficiently cured, and a cured product layer composed of the obtained cured product can be imparted with high mechanical strength and adhesive strength. On the other hand, if the amount is excessively large, a product derived from the cationic polymerization photoinitiator may react with a hydroxyl group of polyvinyl alcohol constituting the polarizing film, thereby degrading the optical performance of the polarizing film.
In the present invention, the curable composition may contain additives generally used in curable compositions, as required. Examples of such additives include ion collectors, antioxidants, chain transfer agents, polymerization accelerators (e.g., polyols), sensitizers, sensitization aids, light stabilizers, adhesion imparting agents, thermoplastic resins, fillers, flow control agents, plasticizers, defoaming agents, leveling agents, silane coupling agents, pigments, antistatic agents, and ultraviolet absorbers.
As the sensitizer, for example, a light sensitizer can be cited. The photosensitizer is a compound which exhibits the maximum absorption at a wavelength longer than the maximum absorption wavelength exhibited by the cationic polymerization photoinitiator (B) and promotes the polymerization initiation reaction using the cationic polymerization photoinitiator (B). In addition, the photosensitizing assistant is a compound that further promotes the action of the photosensitizing agent. Such a photosensitizing agent and a photosensitizing auxiliary agent are preferably blended depending on the type of the transparent protective film.
The photosensitizing agent is preferably a compound which exhibits absorption maximum, for example, under light having a wavelength longer than 380 nm. The cationic polymerization photoinitiator (B) exhibits a maximum absorption at a wavelength of about 300nm or shorter, and when it is exposed to light at a wavelength of about 300nm, cationic species or lewis acid are generated to initiate cationic polymerization of the polymerizable compounds (a1) to (a4), but when such a photosensitizer is added, it is also exposed to light at a wavelength longer than that, particularly, 380 nm. As the photosensitizer, an anthracene compound can be advantageously used. Specific examples of the anthracene-based photosensitizers include the following compounds.
9, 10-dimethoxy anthracene,
9, 10-diethoxyanthracene,
9, 10-dipropoxyanthracene,
9, 10-diisopropoxylanthracene,
9, 10-dibutoxyanthracene,
9, 10-dipentyloxy anthracene,
9, 10-dihexyloxyanthracene,
9, 10-di (2-methoxyethoxy) anthracene,
9, 10-bis (2-ethoxyethoxy) anthracene,
9, 10-bis (2-butoxyethoxy) anthracene,
9, 10-bis (3-butoxypropoxy) anthracene,
2-methyl-or 2-ethyl-9, 10-dimethoxyanthracene,
2-methyl-or 2-ethyl-9, 10-diethoxyanthracene,
2-methyl-or 2-ethyl-9, 10-dipropoxyanthracene,
2-methyl-or 2-ethyl-9, 10-diisopropoxylanthracene,
2-methyl-or 2-ethyl-9, 10-dibutoxyanthracene,
2-methyl-or 2-ethyl-9, 10-dipentyloxy anthracene,
2-methyl-or 2-ethyl-9, 10-dihexyloxyanthracene, and the like.
In the polarizing plate of the present invention, the 1 st cured layer can be formed by, for example, applying a curable composition obtained by mixing polymerizable compounds (a1) to (a4) and a cationic polymerization photoinitiator, and, if necessary, polymerizable compounds other than (a1) to (a4) and additives to a polarizing film, or applying a1 st transparent protective film to the 1 st transparent protective film when the film is used, and irradiating the applied curable composition with active energy rays such as ultraviolet rays and electron beams to cure the film.
When the layer made of the curable composition is irradiated with active energy rays, cationic species or lewis acid is generated from the cationic polymerization photoinitiator. The cationic species or the lewis acid causes polymerization of the polymerizable compound even after the irradiation with the active energy ray is completed, and the curable composition is cured to form a cured product layer.
In the polarizing plate of the present invention, the thickness of the 1 st cured product layer is not particularly limited, but is preferably in the range of 0.5 to 20 μm, and more preferably in the range of 1 to 10 μm. The thickness of the 1 st cured layer is usually 0.5 μm or more in view of effectively suppressing the movement of iodine. In addition, the thickness is usually 20 μm or less from the viewpoint of sufficiently curing the curable composition.
The polarizing plate of the present invention includes the 1 st cured product layer composed of a cured product of the curable composition containing the polymerizable compounds (a1) to (a4) between the polarizing film and the adhesive layer or between the polarizing film and the transparent protective film, thereby being capable of suppressing migration of iodine contained in the polarizing film to the adhesive layer or the transparent protective film. In particular, in a high-temperature and high-humidity environment, although the migration of iodine is accelerated by the intrusion of moisture from the outside, this can be effectively suppressed (i.e., excellent durability) in the polarizing plate of the present invention. Therefore, the polarizing plate of the present invention can maintain optical properties.
In addition, when the adhesive layer constituting the polarizing plate contains, for example, an ionic compound as an antistatic agent or the like, the ionic compound present in the adhesive layer may migrate through the transparent protective film or the adhesive layer constituting the polarizing plate to the polarizing film, and cause interaction with iodine in the polarizing film to degrade the optical performance of the polarizing plate. In the polarizing plate of the present invention, since the 1 st cured product layer composed of the cured product of the curable composition described above is present between the polarizing film and the adhesive layer, the ionic compound can be inhibited from migrating from the adhesive layer, and thus the reduction in optical performance of the polarizing plate can be inhibited.
The 1 st cured product layer also functions as an adhesive layer for bonding the polarizing film and the transparent protective film.
[ adhesive layer ]
The adhesive constituting the adhesive layer may be any conventionally known adhesive without particular limitation, and for example, an adhesive containing a base polymer such as an acrylic, rubber, urethane, silicone, or polyvinyl ether may be used. Further, an energy ray curable adhesive, a thermosetting adhesive, or the like may be used. Among them, an acrylic resin excellent in transparency, adhesion, reworkability, weather resistance, heat resistance and the like is suitable as a binder of the base polymer.
When the adhesive layer in the present invention contains an acrylic resin, the acrylic resin is not particularly limited, and conventionally known acrylic resins can be used, but from the viewpoint of adhesiveness and reworkability, the adhesive layer contained in the polarizing plate in the present invention preferably contains the following acrylic resin (P).
The acrylic resin (P) is an acrylic resin containing, as a main component, a structural unit derived from an alkyl (meth) acrylate (P1) represented by the following formula (III), and further containing a structural unit derived from an unsaturated monomer (P2) having a polar functional group (hereinafter, sometimes referred to as "polar functional group-containing monomer"):
Figure BDA0001124416970000201
[ in the formula, R1Represents a hydrogen atom or a methyl group, R2Represents an alkyl group having 1 to 14 carbon atoms which may be substituted with an alkoxy group having 1 to 10 carbon atoms. Angle (c)
In the present specification, the term "(meth)" as used in the case of (meth) acrylate esters refers to the same meaning as (meth) acrylic acid.
In the above formula (III), R is R in the alkyl (meth) acrylate (P1) which is a main structural unit of the acrylic resin (P)1Is a hydrogen atom or a methyl group, R2Is an alkyl group having 1 to 14 carbon atoms。R2The hydrogen atom in each group of the alkyl group may be substituted with an alkoxy group having 1 to 10 carbon atoms.
In the alkyl (meth) acrylate (P1) represented by the formula (III), R is2Alkyl (meth) acrylates that are unsubstituted alkyl groups include, specifically, straight-chain alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, n-octyl acrylate, and lauryl acrylate; branched alkyl acrylates such as isobutyl acrylate, 2-ethylhexyl acrylate and isooctyl acrylate; linear alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, and lauryl methacrylate; branched alkyl methacrylates such as isobutyl methacrylate, 2-ethylhexyl methacrylate and isooctyl methacrylate. Among them, n-butyl acrylate is preferable, and specifically, n-butyl acrylate is preferably 50% by mass or more with respect to the total amount of all monomers constituting the acrylic resin (P).
As R2Examples of the alkyl (meth) acrylate represented by the formula (III) in the case of an alkoxyalkyl group, which is an alkyl group substituted with an alkoxy group, include, specifically, 2-methoxyethyl acrylate, ethoxymethyl acrylate, 2-methoxyethyl methacrylate, and ethoxymethyl methacrylate.
These alkyl (meth) acrylates (P1) may be used alone or in combination of two or more.
In the polar functional group-containing monomer (P2), the polar functional group may be a free carboxyl group, a hydroxyl group, an amino group, a heterocyclic group such as an epoxy ring, or the like. The polar functional group-containing monomer is preferably a (meth) acrylic compound having a polar functional group. Examples thereof include unsaturated monomers having a free carboxyl group such as acrylic acid, methacrylic acid, and β -carboxyethyl acrylate; unsaturated monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-or 3-chloro-2-hydroxypropyl (meth) acrylate, and diethylene glycol mono (meth) acrylate; unsaturated monomers having a heterocyclic group such as acryloylmorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, and 2, 5-dihydrofuran; unsaturated monomers having an amino group other than a heterocyclic ring, such as N, N-dimethylaminoethyl (meth) acrylate, and the like. The polar functional group is preferably a free carboxyl, hydroxyl, amino or epoxy ring. These polar functional group-containing monomers may be used alone or in different plural.
Among them, an unsaturated monomer having a hydroxyl group is preferably contained as one of the polar functional group-containing monomers (P2) constituting the acrylic resin (P). In addition, it is also effective to use an unsaturated monomer having another polar functional group, for example, an unsaturated monomer having a free carboxyl group, in combination with the unsaturated monomer having a hydroxyl group.
In the acrylic resin (P), the structural unit derived from the alkyl (meth) acrylate (P1) represented by the above formula (III) is preferably 80 to 96% by mass, more preferably 82% by mass or more, and further more preferably 94% by mass or less, based on the total amount of all monomers constituting the acrylic resin (P). The structural unit derived from the polar functional group-containing monomer (P2) is preferably 0.1 to 5% by mass, more preferably 0.5% by mass or more, and still more preferably 3% by mass or less, based on the total amount of all monomers constituting the acrylic resin (P).
In the polarizing plate of the present invention, the acrylic resin (P) that may constitute the adhesive layer may contain a structural unit derived from a monomer other than the alkyl (meth) acrylate (P1) represented by the formula (III) and the polar functional group-containing monomer (P2). Examples of such monomers include a structural unit derived from an unsaturated monomer (P3) (hereinafter, sometimes referred to as "aromatic ring-containing monomer") having 1 olefinic double bond and at least 1 aromatic ring in the molecule, a structural unit derived from a (meth) acrylate having an alicyclic structure in the molecule, a structural unit derived from a styrene-based monomer, a structural unit derived from a vinyl-based monomer, and a structural unit derived from a monomer having a plurality of (meth) acryloyl groups in the molecule.
The unsaturated monomer (aromatic ring-containing monomer) (P3) having 1 olefinic double bond and at least 1 aromatic ring in the molecule is preferably an unsaturated monomer having a (meth) acryloyl group as a group containing an olefinic double bond. Examples thereof include benzyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, and among them, aromatic ring-containing (meth) acrylic compounds represented by the formula (IV):
Figure BDA0001124416970000221
[ in the formula, R3Represents a hydrogen atom or a methyl group, n is an integer of 1 to 8, R4Represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group ].
In the above formula (IV), R represents an aromatic ring-containing (meth) acrylic compound4The number of carbon atoms in the alkyl group may be 1 to 9, the number of carbon atoms in the aralkyl group may be 7 to 11, and the number of carbon atoms in the aryl group may be 6 to 10. Examples of the alkyl group having 1 to 9 carbon atoms include a methyl group, a butyl group, a nonyl group and the like, examples of the aralkyl group having 7 to 11 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group and the like, and examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a naphthyl group and the like.
Specific examples of the aromatic ring-containing (meth) acrylic compound of the formula (IV) include 2-phenoxyethyl (meth) acrylate, 2- (2-phenoxyethoxy) ethyl (meth) acrylate, ethylene oxide-modified nonylphenol (meth) acrylate, and 2- (o-phenylphenoxy) ethyl (meth) acrylate. These aromatic ring-containing monomers may be used alone or in combination of two or more. Among them, 2-phenoxyethyl (meth) acrylate [ in the above formula (IV), R4Compound of formula (IV) ═ H, n ═ 1], 2- (o-phenylphenoxy) ethyl (meth) acrylate [ in the above formula (IV), R4O-phenyl group, n-1 compound, or 2- (2-phenoxyethoxy) ethyl (meth) acrylate [ in the above formula (IV), R4H, n-2 compounds asOne of the aromatic ring-containing monomers (P3) constituting the acrylic resin (P) is suitable.
The alicyclic structure is a cycloalkane structure having 5 or more carbon atoms, preferably 5 to 7 carbon atoms. Specific examples of the acrylate having an alicyclic structure include isobornyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, cyclododecyl acrylate, methylcyclohexyl acrylate, trimethylcyclohexyl acrylate, t-butylcyclohexyl acrylate, α -ethoxycyclohexyl acrylate, cyclohexylphenyl acrylate, and specific examples of the methacrylate having an alicyclic structure include isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, cyclododecyl methacrylate, methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, t-butylcyclohexyl methacrylate, cyclohexylphenyl methacrylate, and the like.
Specific examples of the styrene-based monomer include, in addition to styrene, alkylstyrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, and iodostyrene; further, nitrostyrene, acetylstyrene, methoxystyrene, divinylbenzene, etc.
Specific examples of the vinyl monomer include vinyl esters of fatty acids such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, and vinyl laurate; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene halides such as vinylidene chloride; nitrogen-containing aromatic vinyl groups such as vinylpyridine, vinylpyrrolidone and vinylcarbazole; conjugated diene monomers such as butadiene, isoprene, and chloroprene; and acrylonitrile, methacrylonitrile, and the like.
Specific examples of the monomer having a plurality of (meth) acryloyl groups in the molecule include monomers having 2 (meth) acryloyl groups in the molecule, such as 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate; and monomers having 3 (meth) acryloyl groups in a molecule, such as trimethylolpropane tri (meth) acrylate.
The monomers other than the alkyl (meth) acrylate (P1) represented by the formula (III) and the polar functional group-containing monomer (P2) may be used alone or in combination of 2 or more. When included in the binder, the structural units derived from monomers other than the alkyl (meth) acrylate (P1) and the polar functional group-containing monomer (P2) in the acrylic resin (P) are usually contained in an amount of 0 to 20 parts by mass, preferably 0 to 10 parts by mass, based on 100 parts by mass of the nonvolatile components of the resin.
The resin component constituting the adhesive composition may contain 2 or more kinds of acrylic resins containing structural units derived from the alkyl (meth) acrylate (P1) represented by the above formula (III) and the polar functional group-containing monomer (P2). In addition, an acrylic resin other than the above, for example, an acrylic resin having a structural unit derived from an alkyl (meth) acrylate of the formula (III) and containing no polar functional group, or the like may be mixed with the acrylic resin (P) and used. The acrylic resin (P) containing structural units derived from the alkyl (meth) acrylate (P1) represented by the formula (III) and the polar functional group-containing monomer (P2) is preferably 80% by mass or more, and more preferably 90% by mass or more, relative to the total amount of the acrylic resin (P).
The weight average molecular weight Mw of the acrylic resin (P), which is a copolymer of a monomer mixture comprising an alkyl (meth) acrylate (P1) represented by formula (III) and a polar functional group-containing monomer (P2), is preferably in the range of 100 to 200 ten thousand in terms of standard polystyrene by Gel Permeation Chromatography (GPC). When the weight average molecular weight in terms of standard polystyrene is within the above range, the adhesiveness under high temperature and high humidity is improved, the possibility of peeling and floating between the liquid crystal cell and the adhesive layer tends to be low, and the reworkability tends to be improved. Even if the size of the polarizing plate attached to the adhesive layer changes, the adhesive layer easily changes following the size change, and there is no difference between the luminance at the peripheral edge portion and the luminance at the central portion of the liquid crystal cell, and white leakage and color unevenness tend to be suppressed.
The molecular weight distribution represented by the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn is preferably in the range of 3 to 7. When the molecular weight distribution Mw/Mn is in the range of 3 to 7, even when the liquid crystal display panel or the liquid crystal display device is exposed to high temperature, the occurrence of defects such as white leakage can be suppressed.
In addition, the acrylic resin (P) preferably has a glass transition temperature in the range of-10 to-60 ℃ from the viewpoint of the expression of adhesiveness. The glass transition temperature of the resin can be generally measured by a differential scanning calorimeter.
The acrylic resin (P) constituting the pressure-sensitive adhesive composition can be produced by various known methods such as solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization. In the production of the acrylic resin, a polymerization initiator is generally used. The content of the polymerization initiator is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of all monomers used for producing the acrylic resin.
As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, or the like is used. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone and the like. Examples of the thermal polymerization initiator include azo compounds such as 2, 2 ' -azobisisobutyronitrile, 2 ' -azobis (2-methylbutyronitrile), 1 ' -azobis (cyclohexane-1-carbonitrile), 2 ' -azobis (2, 4-dimethylvaleronitrile), 2 ' -azobis (2, 4-dimethyl-4-methoxyvaleronitrile), dimethyl-2, 2 ' -azobis (2-methylpropionate), and 2, 2 ' -azobis (2-hydroxymethylpropionitrile); organic peroxides such as lauryl peroxide, t-butyl hydroperoxide, benzoyl peroxide, t-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, and (3, 5, 5-trimethylhexanoyl) peroxide; and inorganic peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide. Further, a redox initiator using a peroxide and a reducing agent in combination, and the like can be used as a polymerization initiator.
As the method for producing the acrylic resin (P), a solution polymerization method is particularly preferable. Specific examples of the solution polymerization method include a method of mixing a desired monomer and an organic solvent, adding a thermal polymerization initiator under a nitrogen atmosphere, and stirring at 40 to 90 ℃, preferably 50 to 80 ℃ for 3 to 10 hours. In addition, in order to control the reaction, the monomer or the thermal polymerization initiator may be continuously or intermittently added during the polymerization, or may be added in a state of being dissolved in an organic solvent. Among them, as the organic solvent, for example, aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propanol and isopropanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.
The adhesive layer included in the polarizing plate of the present invention is preferably formed by using an acrylic resin (P) and a crosslinking agent in combination. Examples of the crosslinking agent that can be used include compounds that react with a structural unit derived from a polar functional group-containing monomer (P2) in particular in the acrylic resin (P) to crosslink the acrylic resin. Specifically, an isocyanate compound, an epoxy compound, an aziridine compound, a metal chelate compound, and the like can be exemplified. Among them, the isocyanate compound, the epoxy compound and the aziridine compound have at least 2 functional groups reactive with the polar functional group in the acrylic resin (P) in the molecule.
The isocyanate-based compound is a compound having at least 2 isocyanato groups (-NCO) in the molecule, and examples thereof include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and the like. In addition, adducts obtained by reacting these isocyanate compounds with polyhydric alcohols such as glycerin and trimethylolpropane, or adducts obtained by converting the isocyanate compounds into dimers, trimers, and the like may be used as the crosslinking agent used in the adhesive. 2 or more isocyanate compounds may be used in combination.
The epoxy compound is a compound having at least 2 epoxy groups in the molecule, and examples thereof include bisphenol a type epoxy resins, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol triglycidyl ether, 1, 6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, N-diglycidylaniline, N '-tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N' -diglycidylaminomethyl) cyclohexane, and the like. 2 or more epoxy compounds may be used in combination.
The aziridine-based compound is a compound having a skeleton of a 3-membered ring having at least 2 nitrogen atoms and 2 carbon atoms, also referred to as ethyleneimine, in the molecule, and examples thereof include diphenylmethane-4, 4' -bis (1-aziridinecarboxamide), tolylene-2, 4-bis (1-aziridinecarboxamide), triethylenemelamine, isophthaloylbis-1- (2-methylazepine), tri-1-aziridinylphosphine oxide, hexamethylene-1, 6-bis (1-aziridinecarboxamide), trimethylolpropane tri- β -aziridinylpropionate, tetramethylolmethane tri- β -aziridinylpropionate, and the like.
Examples of the metal chelate compound include compounds in which acetylacetone and ethyl acetoacetate are coordinated to a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium.
Among these crosslinking agents, isocyanate compounds, particularly xylylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, adducts obtained by reacting these isocyanate compounds with polyhydric alcohols such as glycerin and trimethylolpropane, products obtained by converting these isocyanate compounds into dimers, trimers, and the like, products obtained by mixing these isocyanate compounds, and the like are preferably used. When the polar functional group-containing monomer (P2) has a polar functional group selected from the group consisting of a free carboxyl group, a hydroxyl group, an amino group and an epoxy ring, it is particularly preferable to use at least 1 isocyanate-based compound as the crosslinking agent. Among them, suitable isocyanate compounds include tolylene diisocyanate, an adduct obtained by reacting tolylene diisocyanate with a polyol, a dimer of tolylene diisocyanate, and a trimer of tolylene diisocyanate, hexamethylene diisocyanate, an adduct obtained by reacting hexamethylene diisocyanate with a polyol, a dimer of hexamethylene diisocyanate, and a trimer of hexamethylene diisocyanate.
In the adhesive layer constituting the polarizing plate of the present invention, the crosslinking agent is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the acrylic resin (P). The content of the crosslinking agent is more preferably 0.1 to 5 parts by mass, and still more preferably 0.2 to 3 parts by mass, per 100 parts by mass of the acrylic resin (P). When the amount of the crosslinking agent is within the above range, the durability of the adhesive layer tends to be improved, and moreover, white leakage of the liquid crystal display panel tends to be inconspicuous, which is preferable.
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer of the present invention preferably contains a silane compound, and particularly preferably contains a silane compound in an acrylic resin before the crosslinking agent is blended. Since the silane compound improves the adhesion to glass, the silane compound improves the adhesion between the liquid crystal cell sandwiched between the glass substrates and the adhesive layer, and thus high adhesion to the display panel can be ensured.
Examples of the silane-based compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropylethoxydimethylsilane and the like. These silane-based compounds may be used alone, or 2 or more kinds thereof may be used in combination.
The silane-based compound may be an organosilicon oligomer-type compound. When the silicone oligomer is shown as a (monomer) - (monomer) copolymer, the following silicone oligomers can be mentioned, for example.
Mercaptopropyl-containing copolymers such as 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer, and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer;
mercaptomethyl group-containing copolymers such as mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer, and mercaptomethyltriethoxysilane-tetraethoxysilane copolymer;
3-methacryloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropyltriethoxysilane-tetraethoxysilane copolymer, methacryloxypropyl-containing copolymers such as 3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer;
3-acryloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropyltriethoxysilane-tetraethoxysilane copolymer, acryloxypropyl-containing copolymers such as 3-acryloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3-acryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer;
vinyl group-containing copolymers such as vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxysilane-tetramethoxysilane copolymer, and vinylmethyldiethoxysilane-tetraethoxysilane copolymer;
and amino group-containing copolymers such as 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer.
These silane-based compounds are liquid in many cases. The amount of the silane compound to be blended in the adhesive is usually 0.01 to 10 parts by mass, preferably 0.03 to 1 part by mass, per 100 parts by mass (the total amount of 2 or more types) of the nonvolatile components of the acrylic resin (P). When the amount of the silane compound is within the above range with respect to 100 parts by mass of the nonvolatile component of the acrylic resin (P), the adhesion between the adhesive layer and the liquid crystal cell is preferably improved, and the silane compound tends to be inhibited from bleeding out of the adhesive layer.
In the present invention, the adhesive layer may contain an ionic compound. The ionic compound can function as an antistatic agent. In particular, when the acrylic resin (P) contains the aromatic ring-containing (meth) acrylic compound represented by the above formula (IV) and n in the formula (IV) is 2 or more, it is effective for suppressing white leakage, and by blending an ionic compound into a pressure-sensitive adhesive containing an acrylic resin obtained by copolymerizing the monomers, it is possible to provide a white leakage suppressing effect and also provide excellent antistatic properties. The ionic compound referred to herein is a compound in which a cation and an anion are present in combination, and the cation and the anion may be inorganic ions or organic ions, respectively, but from the viewpoint of compatibility with the acrylic resin (P), an ionic compound in which at least one of the cation and the anion contains an organic group is preferable.
Examples of the inorganic cation constituting the ionic compound include lithium cation [ Li ]+Sodium cation [ Na ]+Potassium cation [ K ]+C, cesium cation [ Cs ]+Alkali metal ions such as aluminum ions; beryllium cation [ Be ]2+Magnesium cation [ Mg ]2+Calcium cation [ Ca ]2+Alkaline earth metal ions, etc. Among them, from the viewpoint of metal corrosion resistance, lithium cation [ Li ] is preferably used+Potassium cation [ K ]+Or sodium cation [ Na ]+From the viewpoint of durability, it is further preferable to use potassium cation [ K ]+〕。
Examples of the organic cation constituting the ionic compound include the following formula (V): pyridinium cations represented by the following formula (VI), quaternary ammonium cations represented by the following formula (VI), and the like.
Figure BDA0001124416970000301
In the formula (V), R5～R9Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R10Represents an alkyl group having 1 to 16 carbon atoms. In the formula (VI), R11Represents an alkyl group having 1 to 12 carbon atoms, R12、R13And R14Each independently represents an alkyl group having 6 to 12 carbon atoms.
The total carbon number of the pyridinium cation represented by the formula (V) is 6 or more, but among them, 8 or more, particularly 10 or more in total carbon number is preferable from the viewpoint of compatibility with the acrylic resin (P). The total carbon number is 36 or less, and more preferably 30 or less. In the pyridinium cation represented by the formula (V), R is bonded to the carbon atom at the 4-position of the pyridine ring7R being alkyl and bound to another carbon atom of the pyridine ring5、R6、R8And R9The cations, each being a hydrogen atom, are one of the preferred cations.
Specific examples of the pyridinium cation represented by the formula (V) include the following cations.
N-methyl-4-hexylpyridinium cation, N-butyl-4-methylpyridinium cation, N-butyl-2, 4-diethylpyridinium cation, N-butyl-2-hexylpyridinium cation, N-hexyl-2-butylpyridinium cation, N-hexyl-4-methylpyridinium cation, N-hexyl-4-ethylpyridinium cation, N-hexyl-4-butylpyridinium cation, N-octyl-4-methylpyridinium cation, N-octyl-4-ethylpyridinium cation, N-octyl pyridinium cation, etc.
The ammonium cation represented by the above formula (VI) is a tetraalkylammonium cation, and the total carbon number of the tetraalkylammonium cation is preferably 20 or more, and further preferably 22 or more, from the viewpoint of compatibility with the acrylic resin (P). The total carbon number is 36 or less, and more preferably 30 or less.
Specific examples of the tetraalkylammonium cation represented by the formula (VI) include the following cations.
Tetrahexylammonium cation, tetraoctylammonium cation, tributylmethylammonium cation, trihexylmethylammonium cation, trioctylmethylammonium cation, tridecylmethylammonium cation, trihexylethylammonium cation, trioctylethylammonium cation, and the like.
On the other hand, examples of the anion constituting the ionic compound include the following anions.
Chloride anion [ Cl ]-Bromide anion [ Br ]-Iodine radical anion [ I ]-Tetrachloroaluminate anion [ AlCl ]4 -Heptachlorodialuminate anion [ Al ]2Cl7 -Tetrafluoroborate anion [ BF ]4 -Hexafluorophosphate anion [ PF ]6 -Perchlorate anion [ ClO ]4 -Nitrate anion [ NO ]3 -Acetic acid anion [ CH ]3COO-Trifluoroacetic anion [ CF ]3COO-Methanesulfonate anion [ CH ]3SO3 -Triflate anion [ CF ]3SO3 -Bis (trifluoromethanesulfonyl) imide anion [ (CF)3SO2)2N-Tri (trifluoromethanesulfonyl) methyl anion [ (CF)3SO2)3C-Hexafluoroarsenate anion [ AsF ]6 -Hexafluoroantimonate anion [ SbF ]6 -Hexafluoroniobate anion [ NbF ]6 -Hexafluorotantalate anion [ TaF ]6 -Fluoro (poly) fluorofluoride anion [ F (HF) ]n -N is about 1 to 3) and a thiocyanate anion [ SCN [-Dicyandiamide anion [ (CN)2N-Perfluoro butane sulfonate anion [ C ]4F9SO3 -Bis (pentafluoroethanesulfonyl) imide anion [ (C)2F5SO2)2N-Perfluorobutyrate anion [ C ]3F7COO-(trifluoromethanesulfonyl) imide anion [ (CF)3SO2)(CF3CO)N-And the like.
Specific examples of the ionic compound may be appropriately selected from the above-mentioned combinations of cations and anions. Specific examples of the ionic compound which is a combination of a cation and an anion include the following ionic compounds.
Lithium bis (trifluoromethanesulfonyl) imide, lithium hexafluorophosphate, lithium iodide (lithium iodide), lithium bis (pentafluoroethanesulfonyl) imide, lithium tris (trifluoromethanesulfonyl) methide, sodium bis (trifluoromethanesulfonyl) imide, sodium bis (pentafluoroethanesulfonyl) imide, sodium tris (trifluoromethanesulfonyl) methide, potassium bis (trifluoromethanesulfonyl) imide, potassium bis (pentafluoroethanesulfonyl) imide, potassium tris (trifluoromethanesulfonyl) methide, N-methyl-4-hexylpyridinium bis (trifluoromethanesulfonyl) imide, N-butyl-2-methylpyridinium bis (trifluoromethanesulfonyl) imide, N-hexyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide, N-octyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide, lithium hexafluorophosphate, lithium iodide (lithium iodide), lithium bis (pentafluoroethanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, sodium bis (trifluoromethanesulfonyl) imide, potassium bis (trifluoromethanesulfonyl), N-methyl-4-hexylpyridinium hexafluorophosphate, N-butyl-2-methylpyridinium hexafluorophosphate, N-hexyl-4-methylpyridinium hexafluorophosphate, N-octyl-4-methylpyridinium hexafluorophosphate, N-methyl-4-hexylpyridinium perchlorate, N-butyl-2-methylpyridinium perchlorate, N-hexyl-4-methylpyridinium perchlorate, N-octyl-4-methylpyridinium perchlorate, tetrahexylammonium bis (trifluoromethanesulfonyl) imide, tributylmethylammonium bis (trifluoromethanesulfonyl) imide, trihexylmethylammonium bis (trifluoromethanesulfonyl) imide, trioctymethylammonium bis (trifluoromethanesulfonyl) imide, N-butyl-4-methylpyridinium hexafluorophosphate, N-octyl-4-methylpyridinium hexafluorophosphate, N-methyl-4-hexylpyridinium perchlorate, N-methyl-4-trifluoromethylpyridinium perchlorate, tetrahexylammonium bis (trifluoromethanesulfonyl) imide, tributylmethylammonium bis, Tetrahexylammonium hexafluorophosphate, tributylmethylammonium hexafluorophosphate, trihexylmethylammonium hexafluorophosphate, trioctylmethylammonium hexafluorophosphate, tetrahexylammonium perchlorate, tributylmethylammonium perchlorate, trihexylmethylammonium perchlorate, trioctylmethylammonium perchlorate, and the like.
These ionic compounds may be used alone or in combination of 2 or more. When the ionic compound is contained, the amount thereof is usually 0.5 to 8 parts by mass, preferably 0.8 to 4 parts by mass, per 100 parts by mass of the acrylic resin (P).
In the present invention, the adhesive layer may further contain a crosslinking catalyst, a weather-resistant stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, a resin other than an acrylic resin, and the like.
It is also useful to prepare a harder adhesive layer by blending an ultraviolet-curable compound such as a polyfunctional acrylate and a photoinitiator in the adhesive to form an adhesive layer and then irradiating ultraviolet rays to cure the adhesive layer. It exhibits a2 nd crosslinked structure in the binder and plays a role of improving durability in heat resistance and the like. Further, when a crosslinking catalyst is used in combination with a crosslinking agent in the adhesive, the adhesive layer can be prepared by aging in a short time, and in the polarizing plate including the obtained adhesive, the occurrence of floating or peeling between the polarizing plate and the adhesive layer or the occurrence of foaming in the adhesive layer can be suppressed, and the reworkability may be improved.
Examples of the crosslinking catalyst include amine compounds such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamino resins, and melamine resins. When an amine compound is added as a crosslinking catalyst to the binder, an isocyanate compound is suitable as a crosslinking agent.
Further, the adhesive layer may contain fine particles to exhibit light scattering properties. An antioxidant, an ultraviolet absorber, or the like may be blended in the adhesive layer. Examples of the ultraviolet absorber include salicylate-based compounds, benzophenone-based compounds, benzotriazole-based compounds, cyanoacrylate-based compounds, and nickel complex salt-based compounds.
The adhesive layer may be provided by: for example, a method of preparing an organic solvent solution of the above-mentioned binder, applying the solution to a film or a layer to be laminated (for example, a polarizing film) by a die coater, a gravure coater or the like, and drying the film or layer. Alternatively, the pressure-sensitive adhesive sheet may be provided by a method of transferring a sheet-like pressure-sensitive adhesive formed on a plastic film (referred to as a separator) subjected to a release treatment onto a film or a layer to be laminated. The thickness of the adhesive layer is not particularly limited, but is preferably within a range of 2 to 40 μm, more preferably within a range of 5 to 35 μm, and still more preferably within a range of 10 to 30 μm.
The adhesive layer preferably has a storage elastic modulus of 0.10 to 5.0MPa, more preferably 0.15 to 1.0MPa, at 23 to 80 ℃. When the storage elastic modulus at 23 to 80 ℃ is 0.10MPa or more, it is preferable to suppress white leakage due to shrinkage of the polarizing plate when the liquid crystal display panel in a state where the polarizing plate is bonded to the liquid crystal cell is exposed to high temperature or the like.
Further, it is preferably 5MPa or less because the reduction of the adhesive force hardly causes the reduction of the durability. The phrase "exhibiting a storage modulus of 0.10 to 5.0MPa at 23 to 80 ℃ means that the storage modulus is a value within the above range at any temperature within the above range. Since the storage elastic modulus generally decreases gradually with an increase in temperature, if the storage elastic modulus at 23 ℃ and that at 80 ℃ both fall within the above range, it can be considered that the adhesive layer exhibits the storage elastic modulus within the above range at a temperature within the above range. The storage elastic modulus of the adhesive layer can be measured by a commercially available viscoelasticity measuring apparatus, for example, a viscoelasticity measuring apparatus "DYNAMIC ANALYZER RDAII" manufactured by REMOMETRIC.
In one preferred embodiment, the adhesive layer of the polarizing plate of the present invention is composed of an acrylic resin which is a copolymer of butyl acrylate, methyl acrylate, 2-hydroxyethyl acrylate, 2-phenoxyethyl acrylate and acrylic acid, a silane compound, an isocyanate compound as a crosslinking agent, and an antistatic component.
[ polarizing film ]
The polarizing plate of the present invention is a polarizing plate having a function of extracting linearly polarized light from incident natural light, and the present invention is a polarizing plate in which iodine is contained in a polyvinyl alcohol resin film and is adsorbed and oriented. As the polyvinyl alcohol resin constituting the polyvinyl alcohol resin film, a resin obtained by saponifying a polyvinyl acetate resin can be used. Examples of the polyvinyl acetate resin include, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and another monomer copolymerizable therewith (for example, an ethylene-vinyl acetate copolymer). Examples of the other monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.
The saponification degree of the polyvinyl alcohol resin is usually 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin may be modified, and for example, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, or the like modified with aldehydes can be used. The polymerization degree of the polyvinyl alcohol resin is usually 1000 to 10000, preferably 1500 to 5000.
The film made of such a polyvinyl alcohol resin can be used as a raw film for a polarizing film. The method for forming the film of the polyvinyl alcohol resin is not particularly limited, and the film can be formed by a conventionally known method. The thickness of the raw film made of the polyvinyl alcohol resin is not particularly limited, but is, for example, 10 to 150 μm, preferably 15 to 100 μm, and more preferably 20 to 80 μm in consideration of ease of stretching.
The polarizing film is generally manufactured through the following processes: the method for producing a polyvinyl alcohol film comprises a step of uniaxially stretching such a polyvinyl alcohol resin film, a step of adsorbing iodine by dyeing the polyvinyl alcohol resin film with iodine, a step of treating the iodine-adsorbed polyvinyl alcohol resin film with an aqueous boric acid solution, and a step of washing the polyvinyl alcohol resin film with water after the treatment with the aqueous boric acid solution.
The uniaxial stretching of the polyvinyl alcohol resin film may be performed before the iodine dyeing, simultaneously with the dyeing, or after the dyeing. In the case where the uniaxial stretching is performed after dyeing, the uniaxial stretching may be performed before or during the boric acid treatment. Uniaxial stretching may also be performed in these multiple stages. In the case of uniaxial stretching, the stretching may be performed uniaxially between rolls having different peripheral speeds, or may be performed uniaxially using a heat roll. The uniaxial stretching may be dry stretching in which stretching is performed in the air, or wet stretching in which stretching is performed in a state where the polyvinyl alcohol resin film is swollen with a solvent. The stretch ratio is preferably 8 times or less, more preferably 7.5 times or less, and still more preferably 7 times or less, from the viewpoint of suppressing deformation of the polarizing film. The stretch ratio is preferably 4.5 times or more from the viewpoint of exhibiting a function as a polarizing film.
In the present invention, a method of immersing a polyvinyl alcohol resin film in an aqueous solution containing iodine and potassium iodide to dye the film is generally employed. The content of iodine in the aqueous solution is usually 0.01 to 1 part by mass per 100 parts by mass of water, and the content of potassium iodide is usually 0.5 to 20 parts by mass per 100 parts by mass of water. The temperature of the aqueous solution for dyeing is usually 20 to 40 ℃, and the immersion time (dyeing time) in the aqueous solution is usually 20 to 1800 seconds.
The boric acid treatment after dyeing with iodine is performed by immersing the dyed polyvinyl alcohol resin film in an aqueous solution containing boric acid. The amount of boric acid in the aqueous solution containing boric acid is usually 2 to 15 parts by mass, preferably 5 to 12 parts by mass, per 100 parts by mass of water. In the present invention, the aqueous solution containing boric acid preferably contains potassium iodide. The amount of potassium iodide in the aqueous solution containing boric acid is usually 0.1 to 15 parts by mass, preferably 5 to 12 parts by mass, per 100 parts by mass of water. The immersion time in the aqueous solution containing boric acid is usually 60 to 1200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature of the aqueous solution containing boric acid is usually 50 ℃ or higher, preferably 50 to 85 ℃, and more preferably 60 to 80 ℃.
The polyvinyl alcohol resin film after the boric acid treatment is usually subjected to a water washing treatment. The water washing treatment can be performed by, for example, immersing the boric acid-treated polyvinyl alcohol resin film in water. The temperature of water in the water washing treatment is usually 5-40 ℃, and the dipping time is usually 1-120 seconds. After washing with water, the film was dried to obtain a polarizing film. The drying treatment may be performed using a hot air dryer or a far infrared heater. The temperature of the drying treatment is usually 30 to 100 ℃, preferably 40 to 95 ℃, and more preferably 50 to 90 ℃. The drying time is usually 60 to 600 seconds, preferably 120 to 600 seconds.
The polyvinyl alcohol resin film was uniaxially stretched, dyed with iodine, and boric acid-treated in this manner to obtain a polarizing film. The thickness of the polarizing film may be set to 5 to 40 μm, for example.
[2 nd cured product layer ]
The polarizing plate of the present invention may have a2 nd cured product layer made of a cured product of a curable composition on the surface of the polarizing film opposite to the 1 st cured product layer. The curable composition constituting the 2 nd cured product layer may be the same as or different from the curable composition constituting the 1 st cured product layer described above. The 2 nd cured product layer may be appropriately selected depending on the adhesiveness to the polarizing film and the 2 nd transparent protective film.
In one embodiment of the present invention, since the 2 nd cured product layer also functions as an adhesive for adhering a polarizing film to a transparent protective film (5 in fig. 1 and 2) laminated on the opposite side of the liquid crystal cell, when the curable composition constituting the 2 nd cured product layer is different from the curable composition constituting the 1 st cured product layer, for example, a photocurable adhesive known in the art can be used as the curable composition constituting the 2 nd cured product layer. Examples of the photocurable adhesive include a mixture of a photocurable epoxy resin and a cationic polymerization photoinitiator, and a mixture of a photocurable acrylic resin and a radical photopolymerization initiator. The curable composition for forming a cured product constituting the 2 nd cured product layer is appropriately selected depending on the adhesiveness to the polarizing film and the 2 nd transparent protective film, and for example, a photocurable adhesive containing a photocurable component and a cationic polymerization photoinitiator described in international publication No. 2014/129368 pamphlet can be used.
In the present invention, the 2 nd cured product layer can be formed by applying a curable composition (photocurable adhesive) to the surface of the polarizing plate opposite to the surface on which the 1 st cured product layer is laminated, by a known method. For example, a casting method, a meyer bar coating method, a gravure coating method, a comma coating method, a knife coating method, a die coating method, a dip coating method, a spray method, or the like can be used. The casting method is a method of running down an adhesive to a surface of a film as an object to be coated while moving the film in a substantially vertical direction, a substantially horizontal direction, or an oblique direction therebetween, and spreading the adhesive. After the curable composition is applied, the polarizing film and the transparent protective film attached thereto are stacked and sandwiched by a nip roll or the like to attach the films. For example, a method of uniformly spreading a film by applying a curable composition and then applying pressure with a roller or the like, a method of spreading a film by applying a curable composition and then passing between rollers and applying pressure, and the like can be used for bonding of a film using a nip roller. In this case, the material of the roller to be used may be metal, rubber, or the like. When the film is stretched by passing the film between the plurality of rollers, the plurality of rollers may be made of the same material or different materials.
When a photocurable adhesive is used, the photocurable adhesive is cured by irradiation with active energy rays. The light source of the active energy ray is not particularly limited, but an active energy ray having an emission distribution at a wavelength of 400nm or less is preferable, and specifically, 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 lamp, a microwave-excited mercury lamp, a metal halide lamp, and the like are preferable.
The irradiation intensity of the photocurable adhesive is appropriately determined depending on the composition of the photocurable adhesive, and is not particularly limited, but the irradiation intensity in a wavelength region effective for activation of the polymerization initiator is preferably 0.1 to 6000mW/cm2More preferably 10 to 1000mW/cm2More preferably 20 to 500mW/cm2. When the irradiation intensity is within the above range, the reaction time can be ensured, and yellowing of the epoxy resin and deterioration of the polarizing film due to heat radiated from the light source and heat generation during curing of the photocurable adhesive can be suppressed. The light irradiation time of the photocurable adhesive is not particularly limited as long as it is appropriately selected according to the photocurable adhesive to be cured, but the cumulative light amount expressed as the product of the irradiation intensity and the irradiation time is preferably 10 to 10000mJ/m2More preferably 50 to 1000mJ/m2More preferably 80 to 500mJ/m2Is set. When the cumulative light amount of the photocurable adhesive is within the above range, a sufficient amount of active species derived from the polymerization initiator is generated, and the curing reaction can be more reliably performed.
When the photocurable adhesive is cured by irradiation with an active energy ray, it is preferable to cure the photocurable adhesive under conditions that do not deteriorate various functions of the polarizing plate, such as the polarization degree, transmittance, and hue of the polarizing film, and the transparency of various films constituting the transparent protective film and the optical layer. The thickness of the 2 nd cured product layer is not particularly limited, but is usually 0.1 to 10 μm.
[ transparent protective film ]
In one embodiment, the polarizing plate of the present invention includes a1 st transparent protective film (6 in fig. 2) laminated on one surface of the polarizing film with a1 st cured product layer interposed therebetween. In one embodiment, the polarizing plate of the present invention includes a2 nd transparent protective film (5 in fig. 1 and 2) laminated on the other surface of the polarizing film with a2 nd cured product layer interposed therebetween. In one embodiment, the polarizing plate of the present invention has the above-described 1 st transparent protective film, from the viewpoint of contributing to prevention of shrinkage and expansion of the polarizing film and prevention of deterioration of the polarizing film due to temperature, humidity, ultraviolet rays, or the like. On the other hand, in one embodiment, the polarizing plate of the present invention does not include the 1 st transparent protective film from the viewpoint of thinning of the polarizing plate. Since the 1 st cured product layer of the present invention contributes to the prevention of the deterioration of the polarizing film instead of the transparent protective film, the polarizing plate of the present invention preferably does not include the 1 st transparent protective film from the viewpoint of achieving the prevention of the deterioration of the polarizing film and the reduction in thickness of the polarizing plate in a well-balanced manner.
As a material for forming the transparent protective film, a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like is preferable. Examples thereof include polyester polymers such AS polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such AS diacetylcellulose and triacetylcellulose, acrylic polymers such AS polymethyl methacrylate, styrene polymers such AS polystyrene and acrylonitrile-styrene copolymer (AS resin), and polycarbonate polymers. Examples of the polymer forming the transparent protective film include polyolefin polymers such as polyethylene, polypropylene, polyolefins having a ring system or a norbornene structure, and ethylene-propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers, polyether ether ketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, aryl ester polymers, polyoxymethylene polymers, epoxy polymers, and blends of the above polymers. The transparent protective film may be formed as a cured layer using a heat-curable or ultraviolet-curable resin such as an acrylic, urethane, acrylic urethane, epoxy, or silicone resin. Among them, a material containing a hydroxyl group reactive with an isocyanate crosslinking agent is preferable, and a cellulose-based polymer is particularly preferable.
In the polarizing plate of the present invention, the 1 st transparent protective film and the 2 nd transparent protective film may be made of the same material or different materials.
The thickness of the transparent protective film is not particularly limited, but the 1 st transparent protective film and the 2 nd transparent protective film are each generally 500 μm or less, preferably 1 to 300 μm, more preferably 5 to 200 μm, and still more preferably 10 to 100 μm. The transparent protective film may be formed of a transparent protective film having an optical compensation function.
In the polarizing plate of the present invention, since the 1 st cured product layer can effectively suppress the migration of iodine from the polarizing film to the adhesive layer and the migration of the ionic compound from the adhesive layer to the polarizing film, the selection range of the material constituting the 1 st transparent protective film of the polarizing plate is wide. That is, the polarizing plate can be formed using a generally inexpensive transparent protective film that easily transmits an ionic compound, without using a transparent protective film that hardly transmits an ionic compound. This can reduce production cost, and the polarizing plate of the present invention is advantageous from an industrial viewpoint.
Specifically, for example, the following transparent protective film can be used as the 1 st transparent protective film: the absorbance with respect to light of 360nm was defined as the initial absorbance, and the absorbance with respect to light of 360nm measured after immersion in a 50 mass% potassium iodide aqueous solution for 4.5 hours in an atmosphere of 23 ℃ and 60% RH in the atmosphere, taking out, washing with water at 23 ℃ for 15 seconds in the atmosphere, and drying in a dark place at 23 ℃ for 15 hours in the atmosphere showed a value greater than 5% with respect to the initial absorbance.
The polarizing plate of the present invention may further include optical layers such as a retardation film, a viewing angle compensation film, and a brightness enhancement film, if necessary. The optical layer in the polarizing plate of the present invention may be formed using materials known in the art.
The polarizing plate of the present invention can be produced by a known method. For example, a curable composition is applied to a transparent protective film to form a2 nd cured composition layer, and a polarizing film is laminated on the 2 nd cured composition layer to produce a laminate. In the case of a polarizing plate not including the 1 st protective film, the curable composition is applied to the releasable film to form the 1 st cured composition layer, and the polarizing film side of the laminate is bonded to the applied surface. Next, the 2 nd cured composition layer and the 1 st cured composition layer are cured by irradiation with active energy rays such as ultraviolet rays and electron beams, thereby forming a2 nd cured composition layer and a1 st cured composition layer. After that, the releasable film may be peeled off to form an adhesive layer on the 1 st cured product layer.
On the other hand, in the case of the polarizing plate including the 1 st transparent protective film, the curable composition may be applied to the transparent protective film to form the 1 st cured composition layer, the polarizing film side of the laminate may be bonded to the application surface thereof, then the 1 st cured composition layer may be cured by irradiation with an active energy ray such as ultraviolet ray or electron beam to form the 1 st cured composition layer, and then the adhesive layer may be formed on the 1 st transparent protective film. The polarizing plate not including the 1 st transparent protective film is preferable in that a thinner polarizing plate can be formed.
[ curable composition and cured product thereof ]
The present invention also relates to a curable composition. The curable composition of the present invention contains, as polymerizable compounds, 35 to 70% by mass of (A1) an oxetane compound having 2 or more oxetanyl groups, (A2)0 to 40% by mass of an aliphatic epoxy compound having 2 or more epoxy groups, (A3)15 to 50% by mass of an alicyclic epoxy compound having 2 or more epoxy groups, and (A4)0 to 20% by mass of an aromatic epoxy compound having 1 or more aromatic rings, relative to 100% by mass of the total amount of polymerizable compounds, and further contains (B) a cationic polymerization photoinitiator. The suitable content of the polymerizable compounds (a1) to (a4) in the curable composition of the present invention is the same as the content of the polymerizable compounds (a1) to (a4) in the curable composition constituting the 1 st cured product layer of the polarizing plate of the present invention. The polymerizable compounds (a1) to (a4) and the cationic polymerization photoinitiator (B) are the same as the polymerizable compounds (a1) to (a4) and the cationic polymerization photoinitiator (B) in the curable composition constituting the 1 st cured product layer of the polarizing plate of the present invention.
The cured product produced by curing the curable composition of the present invention is less likely to permeate iodine under high temperature and high humidity conditions, and therefore, can be suitably used as a material constituting a cured product layer or an adhesive layer of a polarizing plate used in, for example, an image display device. In particular, the cured product of the curable composition of the present invention has excellent denseness, and therefore can effectively prevent iodine contained in the polarizing film, an antistatic component (ionic compound) contained in the adhesive layer, and the like from migrating to other layers constituting the polarizing plate. Therefore, for example, by providing a cured product layer formed from a cured product of the curable composition of the present invention as 1 layer constituting a polarizing plate, it is possible to suppress the movement of various components and obtain a polarizing plate having excellent optical properties. Further, by using a cured product of the curable composition of the present invention as a substitute for a transparent protective film provided in a conventional polarizing plate, a thinner polarizing plate can be produced.
[ examples ]
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples at all. In the examples and comparative examples, "%" and "part(s)" are "% by mass" and "part(s) by mass", respectively, unless otherwise specified.
Example 1
1. Preparation of curable composition (A) constituting the 1 st cured product layer
The polymerizable compounds (a1), (a2), (A3), and (a4) were mixed with the cationic polymerization photoinitiator (B) according to the composition shown in table 1 below to prepare the curable composition (a) of example 1.
2. Preparation of curable composition (a) constituting the 2 nd cured product layer
The following polymerizable compounds (a1), (a2), (A3), and (a4) were mixed with a cationic polymerization photoinitiator (b1) to prepare a curable composition (a).
(a1)3, 4-epoxycyclohexanecarboxylic acid 3, 4-epoxycyclohexylmethyl ester: 25 parts by mass
(a2) Neopentyl diglycidyl ether: 55 parts by mass
(a3) A polymer (GMA-PMMA (polymethyl methacrylate) copolymer) having a weight average molecular weight of 15000 obtained by radical polymerization of a monomer comprising 25 parts of glycidyl methacrylate and 75 parts of methyl methacrylate: 15 parts by mass
(a4) Hydroxybutyl vinyl ether: 5 parts by mass
(b1) Triarylsulfonium hexafluorophosphate: 2.25 parts by mass
3. Preparation of adhesive composition constituting adhesive layer
The acrylic adhesive was prepared by the following procedure.
Azobisisobutyronitrile (azobisisobutyronitrile) was added as a polymerization initiator in an amount of 0.14 part by mass to 70.4 parts by mass of butyl acrylate, 20.0 parts by mass of methyl acrylate, 0.6 parts by mass of acrylic acid, 8.0 parts by mass of 2-phenoxyethyl acrylate, and 1.0 part by mass of 2-hydroxyethyl acrylate, and a polymerization reaction was carried out to prepare an acrylic resin. An organic solvent solution of an acrylic resin adhesive was prepared by adding an isocyanate-based crosslinking agent (CORONATE L: an ethyl acetate solution of trimethylolpropane adduct of tolylene diisocyanate (solid content concentration: 75%), 0.45 parts by mass of Nippon Polyurethane (manufactured by Nippon Polyurethane Co., Ltd.), a silane coupling agent (KBM-403: 3-glycidoxypropyltrimethoxysilane (liquid), 0.45 parts by mass of shin-Etsu chemical Co., Ltd.), and 3.0 parts by mass of an antistatic agent (1-hexylpyridinium hexafluorophosphate (compound represented by the following formula (VII)) to 20.0 parts by mass of the solid content of the acrylic resin.
Figure BDA0001124416970000401
4. Fabrication of polarizing plates
(1) Polarizing plate of example 1
(i) Production of laminate (1)
A surface of an acrylic resin (PMMA) film (corresponding to the 2 nd transparent protective film) containing an ultraviolet absorber and having a thickness of 60 μm (trade name "technoloy S001", manufactured by sumitomo chemical co., ltd.) was subjected to a corona discharge treatment, and the curable composition (a) prepared in the 2 above was applied to the corona discharge treated surface by a bar coater so that the film thickness after curing became about 3 μm to form a curable composition (a) layer (corresponding to the 2 nd cured product layer). Next, a polyvinyl alcohol (PVA) -iodine polarizing film having a thickness of 25 μm was laminated on the curable composition (a) layer to prepare a laminate. From the polarizing film side of the laminate, an ultraviolet irradiation device with a conveyor belt (lamp "DBulb" manufactured by Fusion UV Systems) was used so that the cumulative light amount at 280nm to 320nm became 200mJ/cm2The curable composition was cured by irradiation with ultraviolet light, thereby producing a laminate (1) composed of an acrylic resin film (2 nd transparent protective film)/2 nd cured product layer/polarizing film.
(ii) Production of laminate (2)
The curable composition (A) of example 1, prepared in 1, was coated on one surface of a cycloolefin film (trade name "ZEONOR", manufactured by Zeon Corporation) having a thickness of 50 μm using a bar coater so that the film thickness after curing became about 3 μm. On the coated surface, the polarizing film side of the laminate (1) was bonded to prepare a laminate. From the cycloolefin film side of the laminate, an ultraviolet irradiation apparatus (lamp) with a conveyor belt was usedThe cumulative light amount at 280 to 320nm was 200mJ/cm using "DBulb" manufactured by Fusion UV Systems Ltd2The method (2) is a method of irradiating ultraviolet rays to cure the curable composition (A), and then peeling off the cycloolefin-based film. In this way, a laminate (2) composed of an acrylic resin film (2 nd transparent protective film)/2 nd cured product layer/polarizing film/1 st cured product layer was produced.
(iii) Production of polarizing plate (No. 1 transparent protective film)
The organic solvent solution of the acrylic resin adhesive prepared in the above 3 was applied to a release-treated surface of a 38 μm-thick polyethylene terephthalate film (trade name: SP-PLR382050, manufactured by Lintec Corporation (hereinafter referred to as "release film")) subjected to release treatment by a die coater so that the thickness after drying became 20 μm, and was dried to prepare a release film-attached sheet adhesive. Next, on the 1 st cured product side of the laminate (2) produced in the above (ii), the surface (adhesive surface) of the sheet-like adhesive on the side opposite to the release film was laminated by a laminator, and then cured for 7 days under the conditions of a temperature of 23 ℃ and a relative humidity of 65%, to obtain a polarizing plate provided with an adhesive layer (without the 1 st transparent protective film). The polarizing plate has a structure in which a release film is bonded to an adhesive layer.
(iv) Production of polarizing plate (with No. 1 transparent protective film)
The surface of a cellulose-based transparent protective film having a thickness of 40 μm (corresponding to the 1 st transparent protective film) (trade name "ZRE 34", manufactured by fujifilm corporation) was subjected to corona discharge treatment, and the curable composition (a) of example 1 having the composition shown in table 1 was applied to the corona discharge-treated surface by a bar coater so that the cured film thickness became about 3 μm. The polarizing film side of the laminate (1) produced in the same manner as in (i) above was bonded to the coated surface to produce a laminate. From the cellulose-based transparent protective film side of the laminate, the cumulative light amount at 280nm to 320nm was 200mJ/cm using an ultraviolet irradiation device with a conveyor belt (lamp "DBulb" manufactured by Fusion UV Systems Co., Ltd.)2The curable composition (A) was cured by ultraviolet irradiation to prepare an acrylic resin film (second aspect)2 transparent protective film)/2 nd cured product layer/polarizing film/1 st cured product layer/cellulose transparent protective film (1 st transparent protective film) constituting the laminate (2'). Next, a sheet-like adhesive was attached to the cellulose-based transparent protective film side of the laminate (2') in the same manner as in (iii) above to obtain a polarizing plate provided with an adhesive layer (having a1 st transparent protective film).
(2) Polarizing plate of examples 2 to 12
Polarizing plates (without the 1 st transparent protective film) and polarizing plates (with the 1 st transparent protective film) were obtained in the same manner as the polarizing plate of example 1, using the curable compositions having the compositions shown in table 1 as the curable compositions constituting the 1 st cured product layer, respectively.
(3) Polarizing plate of comparative examples 1 to 7
As the curable composition constituting the 1 st cured product layer, a polarizing plate (without the 1 st transparent protective film) and a polarizing plate (with the 1 st transparent protective film) were obtained in the same manner as the polarizing plate of example 1 using the curable compositions having the compositions shown in table 2.
The absorbance of the cellulose-based transparent protective film [ trade name "ZRE 34", manufactured by Fuji photo film (Ltd.) against light of 360nm was measured as initial absorbance. The film was immersed in a 50 mass% potassium iodide aqueous solution at this temperature for 4.5 hours in an atmosphere of 23 ℃ and 60% RH, taken out, washed with water at 23 ℃ for 15 seconds in the atmosphere, dried in a dark place at 23 ℃ for 15 hours in the atmosphere, and then measured for absorbance at 360nm, which was an increase of 22% in initial absorbance.
5. Evaluation of durability of polarizing plate
The polarizing plates of examples 1 to 12 and comparative examples 1 to 7 were each cut to a size of 30mm × 30mm, and the release film was peeled off, and alkali-free glass (product name "EAGLE XG", manufactured by corning incorporated ") was attached to the pressure-sensitive adhesive layer side. The durability of this sample based on the optical performance was evaluated as follows.
Each sample was heated at 50 ℃ under a pressure of 5kg/cm2(490.3kPa) was autoclaved for 1 hour, and then the ring was heated at 23 ℃ and a relative humidity of 55%The mixture was left to stand for 24 hours. The sample was fixed to a "film holder with a polarizing film" selected as an accessory in an ultraviolet-visible spectrophotometer (UV2450, manufactured by Shimadzu corporation), and the transmission spectra in the transmission axis direction and the absorption axis direction of the polarizing plate in the wavelength range of 380 to 700nm were measured to determine the degree of polarization Py (unit:%). Thereafter, the plate was left standing at 85 ℃ and 85% relative humidity for 12 hours, and the transmission spectrum was measured in the same manner. The polarization degree change Δ Py was calculated from the following equation, using the polarization degree Py before standing for 12 hours in an environment of 85 ℃ and a relative humidity of 85% as an initial value. The results are shown in table 1.
Py-initial Py after test
[ Table 1]
Figure BDA0001124416970000441
[ Table 2]
Figure BDA0001124416970000451
The compounds in table 1 are as follows.
Oxetane compound (2-functional): bis (3-ethyl-3-oxetanylmethyl) ether (OXT221, manufactured by Toyo Seiya Kabushiki Kaisha)
Aliphatic epoxy compound (1) (2-functional): 1, 4-butanediol diglycidyl ether (EX-214, manufactured by Nagase ChemteX Corporation)
Aliphatic epoxy compound (2) (2-functional): 1.6-hexanediol diglycidyl ether (EX-212, manufactured by Nagase ChemteX Corporation)
Aliphatic epoxy compound (3) (2-functional): neopentyl glycol diglycidyl ether (EX-211, manufactured by Nagase ChemteXCcorporation)
Aliphatic epoxy compound (4) (2-functional): cyclohexanedimethanol diglycidyl ether (EX-216, manufactured by Nagase ChemteX Corporation)
Aliphatic epoxy compound (5) (4-functional): pentaerythritol polyglycidyl ether (EX-411, manufactured by Nagase ChemteXCcorporation)
Alicyclic epoxy compound (2-functional): 3, 4-epoxycyclohexanecarboxylic acid 3, 4-epoxycyclohexylmethyl ester (CEL2021P, manufactured by Daicel Chemical Co., Ltd.)
Aromatic epoxy compound (1) (3-functional): 2- [4- (2, 3-epoxypropoxy) phenyl ] -2- [4- [1, 1-bis [4- ([2, 3-epoxypropoxy ] phenyl ] ethyl ] phenyl ] propane (TECHMORE VG3101L, (manufactured by PRINTEC, INC.)
Aromatic epoxy compound (2) (2-functional): resorcinol diglycidyl ether (EX-201, manufactured by Nagase ChemteXCcorporation)
Aromatic epoxy compound (3) (2-functional): bisphenol F type epoxy resin (JeR806, manufactured by Mitsubishi chemical Co., Ltd.)
Aromatic epoxy compound (4) (1 function): p-tert-butylphenyl glycidyl ether (EX-146, manufactured by NagaseChemteX Corporation)
Aliphatic epoxy compound (1 functional): 2-ethylhexyl glycidyl ether (EX121, manufactured by Nagase ChemteXCcorporation)
Oxetane compound (1 functional): 3-Ethyl-3-hydroxymethyloxetane (OXT101, manufactured by Toyo Synthesis Co., Ltd.)
Cationic polymerization photoinitiator: triarylsulfonium hexafluorophosphate
Example 13
The amount of the oxetane compound (2-functional) (OXT221) (A1) used was set to 60 parts by mass,
no (A2) aliphatic epoxy compound (1) (2-functional) (EX-214) (used in an amount of 0 part by mass),
No aliphatic epoxy compound (2) (2-functional) (EX-212) (used in an amount of 0 part by mass) was used (A2),
The amount of the alicyclic epoxy compound (2-functional) (CEL2021P) (A3) used was 40 parts by mass,
a curable composition (a) was prepared in the same manner as in example 1, except that the amount of the aromatic epoxy compound (1) (3-functional) (TECHMOREVG3101L) (a4) used was changed to 0 part by mass. A polarizing plate provided with an adhesive layer (without the 1 st transparent protective film) was obtained in the same manner as in example 1 except that the curable composition (a) obtained above was used instead of the curable composition (a) obtained in example 1 as the curable composition constituting the 1 st cured product layer, and the durability evaluation was performed in the same manner as in example 1, and Δ Py was-0.04.
Example 14
A curable composition (a) was prepared in the same manner as in example 13 except that the amount of the oxetane compound (2-functional) (OXT221) (a1) was changed to 50 parts by mass and the amount of the alicyclic epoxy compound (2-functional) (CEL2021P) (A3) was changed to 50 parts by mass, to obtain a polarizing plate provided with an adhesive layer (no first transparent protective film 1), and the durability was evaluated to find that Δ Py was-0.04.
The oxetane compound (2) (2-functional) (A1) used in examples 15 to 18 described below was as follows.
(A1) Oxetane compound (2) (2 functional): xylylene dioxetane (OXT121, manufactured by Toyo Seiya Kabushiki Kaisha)
Example 15
The amount of the oxetane compound (2-functional) (OXT221) (A1) used was set to 45 parts by mass,
the amount of the oxetane compound (2) (2-functional) (OXT121) (A1) was set to 5 parts by mass, the amount of the alicyclic epoxy compound (2-functional) (CEL2021P) (A3) was set to 40 parts by mass,
a curable composition (a) was prepared in the same manner as in example 13 except that the amount of the aromatic epoxy compound (3-functional) (TECHMOREVG3101L) (a4) used was changed to 10 parts by mass, to obtain a polarizing plate (without the 1 st transparent protective film) provided with an adhesive layer, and the durability of the polarizing plate was evaluated, and Δ Py was-0.07.
Example 16
The amount of the oxetane compound (2-functional) (OXT221) (A1) used was 40 parts by mass,
the amount of the oxetane compound (2) (2-functional) (OXT121) (A1) used was set to 10 parts by mass,
the amount of the alicyclic epoxy compound (2-functional) (CEL2021P) (A3) used was 40 parts by mass,
a curable composition (a) was prepared in the same manner as in example 13, except that the amount of the aromatic epoxy compound (3-functional) (TECHMORE VG3101L) (a4) used was changed to 10 parts by mass, to obtain a polarizing plate (without the 1 st transparent protective film) provided with an adhesive layer, and the durability of the polarizing plate was evaluated, and Δ Py was-0.08.
Example 17
The amount of the oxetane compound (2-functional) (OXT221) (A1) used was set to 50 parts by mass,
(A1) oxetane compound (2) (2-functional) (OXT121) (0 part by mass) was not used, and the amount of (A3) alicyclic epoxy compound (2-functional) (CEL2021P) was set to 45 parts by mass,
a curable composition (a) was prepared in the same manner as in example 16, except that the amount of the aromatic epoxy compound (3-functional) (TECHMORE VG3101L) (a4) used was changed to 5 parts by mass, to obtain a polarizing plate (without the 1 st transparent protective film) provided with an adhesive layer, and the durability of the polarizing plate was evaluated, and Δ Py was-0.06.
Example 18
The amount of the oxetane compound (2-functional) (OXT221) (A1) used was set to 50 parts by mass,
the amount of the alicyclic epoxy compound (2-functional) (CEL2021P) (A3) used was set to 35 parts by mass,
a curable composition (a) was prepared in the same manner as in example 17 except that the amount of the aromatic epoxy compound (3-functional) (TECHMORE VG3101L) (a4) used was changed to 15 parts by mass, to obtain a polarizing plate (without the 1 st transparent protective film) provided with an adhesive layer, and the durability of the polarizing plate was evaluated to find that Δ Py was-0.05.
It was confirmed that the polarizing plates of examples 1 to 18 having the 1 st cured product layer composed of the cured product of the curable composition containing the polymerizable compounds (a1) to (a4) in the content within the range of the present invention exhibited a small change in polarization degree Δ Py, did not change optical properties much even in a severe environment of high temperature and high humidity, and exhibited high durability. On the other hand, it was found that the polarizing plates obtained in comparative examples 1 to 7 each having the 1 st cured product layer composed of a cured product of a curable composition containing polymerizable compounds (a1) to (a4) in amounts not within the range of the present invention exhibited a large change in polarization degree Δ Py, and a decrease in optical performance was observed. Further, it was found that when the curable composition constituting the 1 st cured product layer included the polymerizable compounds (a1) to (a4) in the amounts within the range of the present invention, the optical properties did not decrease even if no transparent protective film was present between the polarizing film and the adhesive layer, and high durability was exhibited (examples 1 to 18). On the other hand, it was found that when the curable composition constituting the 1 st cured product layer did not contain the polymerizable compounds (a1) to (a4) in the range of the present invention, the optical performance was greatly reduced even when the transparent protective film was present between the polarizing film and the adhesive layer (comparative examples 1 to 7).
Description of the symbols
1: polarizing film
2: 1 st cured product layer
3: adhesive layer
4: layer of No. 2 cured product
5: (2 nd) transparent protective film
6: no. 1 transparent protective film
10: polarizing plate
X: liquid crystal box

Claims (15)

1. A polarizing plate comprising a first cured product layer (1) formed from a cured product of a curable composition containing a polymerizable compound, and an adhesive layer, in this order, on one surface of a polarizing film containing iodine in polyvinyl alcohol, wherein the composition of the polymerizable compound contained in the curable composition is: relative to 100 mass% of the total amount of the polymerizable compound,
(A1)35 to 70 mass% of an oxetane compound having 2 or more oxetanyl groups,
(A2)0 to 40 mass% of an aliphatic epoxy compound having 2 or more epoxy groups,
(A3)15 to 50% by mass of an alicyclic epoxy compound having 2 or more epoxy groups, and 0 to 20% by mass of an aromatic epoxy compound (A4) having 1 or more aromatic rings.
2. The polarizing plate of claim 1, wherein the composition of the polymerizable compound is:
(A1)35 to 70 mass% of an oxetane compound having 2 or more oxetanyl groups,
(A2)3 to 40 mass% of an aliphatic epoxy compound having 2 or more epoxy groups,
(A3)15 to 50% by mass of an alicyclic epoxy compound having 2 or more epoxy groups, and 0.1 to 20% by mass of an aromatic epoxy compound (A4) having 1 or more aromatic rings.
3. The polarizing plate of claim 1, wherein the composition of the polymerizable compound is:
(A1)35 to 70 mass% of an oxetane compound having 2 or more oxetanyl groups,
(A2) 0% by mass of an aliphatic epoxy compound having 2 or more epoxy groups,
(A3)15 to 50% by mass of an alicyclic epoxy compound having 2 or more epoxy groups, and 0% by mass of an aromatic epoxy compound (A4) having 1 or more aromatic rings.
4. The polarizing plate according to claim 3, wherein a mass ratio Wa3/Wa1 of a content Wa3 of the (A3) alicyclic epoxy compound having 2 or more epoxy groups to a content Wa1 of the (A1) oxetane compound having 2 or more oxetanyl groups is 0.45 to 1.5.
5. The polarizing plate of claim 1, wherein the composition of the polymerizable compound is:
(A1)35 to 70 mass% of an oxetane compound having 2 or more oxetanyl groups,
(A2) 0% by mass of an aliphatic epoxy compound having 2 or more epoxy groups,
(A3)15 to 50% by mass of an alicyclic epoxy compound having 2 or more epoxy groups, and 0.1 to 20% by mass of an aromatic epoxy compound (A4) having 1 or more aromatic rings.
6. The polarizing plate according to claim 5, wherein a mass ratio Wa3/Wa1 of a content Wa3 of the (A3) alicyclic epoxy compound having 2 or more epoxy groups to a content Wa1 of the (A1) oxetane compound having 2 or more oxetanyl groups is 0.45 to 1.5,
(A4) the mass ratio Wa4/Wa1 of the content Wa4 of the aromatic epoxy compound having 1 or more aromatic rings to the content Wa1 of the oxetane compound having 2 or more oxetanyl groups (A1) is 0.05 to 0.5.
7. The polarizing plate according to any one of claims 1 to 6, wherein the (A2) aliphatic epoxy compound having 2 or more epoxy groups is a compound represented by formula (I):
Figure FDA0002497900740000021
wherein Z represents an alkylene group having 1 to 9 carbon atoms, an alkylidene group having 3 or 4 carbon atoms, a 2-valent alicyclic hydrocarbon group, or a group represented by the formula-CmH2m-Z1-CnH2n-a group having a valence of 2, wherein-Z1-represents-O-, -CO-O-, -O-CO-, -SO2-, -SO-or-CO-, m and n each independently represent an integer of 1 or more, and the total of m and n is 9 or less;
the (A3) alicyclic epoxy compound having 2 or more epoxy groups is a compound represented by the formula (II):
Figure FDA0002497900740000022
in the formula, R1And R2Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group may or may not have an alicyclic structure when the number of carbon atoms is 3 or more,
x represents an oxygen atom, an alkanediyl group having 1 to 6 carbon atoms, or a 2-valent group represented by any one of the following formulae (IIa) to (IId):
Figure FDA0002497900740000031
in the formula, Y1～Y4Independently represents an alkanediyl group having 1 to 20 carbon atoms, wherein the alkanediyl group may or may not have an alicyclic structure when the number of carbon atoms is 3 or more, and a and b independently represent an integer of 0 to 20.
8. The polarizing plate of any one of claims 1 to 6, wherein a1 st transparent protective film is provided between the 1 st cured layer and the adhesive layer.
9. The polarizing plate according to any one of claims 1 to 6, wherein a2 nd cured product layer formed of a cured product of a curable composition is provided on a surface of the polarizing film opposite to the 1 st cured product layer with a2 nd transparent protective film interposed therebetween.
10. A curable composition comprising a polymerizable compound having a composition comprising: relative to 100 mass% of the total amount of the polymerizable compound,
(A1)35 to 70 mass% of an oxetane compound having 2 or more oxetanyl groups,
(A2)3 to 40 mass% of an aliphatic epoxy compound having 2 or more epoxy groups,
(A3)15 to 50 mass% of an alicyclic epoxy compound having 2 or more epoxy groups and 0.1 to 20 mass% of (A4) an aromatic epoxy compound having 1 or more aromatic rings,
and comprises (B) a cationic polymerization photoinitiator.
11. A curable composition comprising a polymerizable compound having a composition comprising: relative to 100 mass% of the total amount of the polymerizable compound,
(A1)35 to 70 mass% of an oxetane compound having 2 or more oxetanyl groups,
(A2)0 to 40 mass% of an aliphatic epoxy compound having 2 or more epoxy groups,
(A3)15 to 50 mass% of an alicyclic epoxy compound having 2 or more epoxy groups and 0 to 20 mass% of (A4) an aromatic epoxy compound having 1 or more aromatic rings,
and comprises (B) a cationic polymerization photoinitiator,
(A3) the mass ratio Wa3/Wa1 of the content Wa3 of the alicyclic epoxy compound having 2 or more epoxy groups to the content Wa1 of the oxetane compound having 2 or more oxetanyl groups (A1) is 0.45 to 1.5.
12. A curable composition comprising a polymerizable compound having a composition comprising: relative to 100 mass% of the total amount of the polymerizable compound,
(A1)35 to 70 mass% of an oxetane compound having 2 or more oxetanyl groups,
(A2) 0% by mass of an aliphatic epoxy compound having 2 or more epoxy groups,
(A3)15 to 50 mass% of an alicyclic epoxy compound having 2 or more epoxy groups and 0.1 to 20 mass% of (A4) an aromatic epoxy compound having 1 or more aromatic rings,
and comprises (B) a cationic polymerization photoinitiator.
13. The curable composition according to claim 12, wherein a mass ratio Wa3/Wa1 of a content Wa3 of the alicyclic epoxy compound having 2 or more epoxy groups (A3) to a content Wa1 of the oxetane compound having 2 or more oxetanyl groups (A1) is 0.45 to 1.5,
(A4) the mass ratio Wa4/Wa1 of the content Wa4 of the aromatic epoxy compound having 1 or more aromatic rings to the content Wa1 of the oxetane compound having 2 or more oxetanyl groups (A1) is 0.05 to 0.5.
14. The curable composition according to any one of claims 10 to 13, wherein the (A2) aliphatic epoxy compound having 2 or more epoxy groups is a compound represented by formula (I):
Figure FDA0002497900740000041
wherein Z represents an alkylene group having 1 to 9 carbon atoms, an alkylidene group having 3 or 4 carbon atoms, a 2-valent alicyclic hydrocarbon group, or a group represented by the formula-CmH2m-Z1-CnH2n-a group having a valence of 2, wherein-Z1-represents-O-, -CO-O-, -O-CO-, -SO2-, -SO-or-CO-, m and n each independently represent an integer of 1 or more, and the total of m and n is 9 or less;
the (A3) alicyclic epoxy compound having 2 or more epoxy groups is a compound represented by the formula (II):
Figure FDA0002497900740000051
in the formula, R1And R2Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group may or may not have an alicyclic structure when the number of carbon atoms is 3 or more,
x represents an oxygen atom, an alkanediyl group having 1 to 6 carbon atoms, or a 2-valent group represented by any one of the following formulae (IIa) to (IId):
Figure FDA0002497900740000052
in the formula, Y1～Y4Independently represents an alkanediyl group having 1 to 20 carbon atoms, wherein the alkanediyl group may or may not have an alicyclic structure when the number of carbon atoms is 3 or more, and a and b independently represent an integer of 0 to 20.
15. A cured product of the curable composition according to any one of claims 10 to 14.
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