TW202026163A - Polarization film and production method therefor - Google Patents

Abstract

This polarization film comprises a first resin layer, a polarizer, an alignment film, and a second resin layer, which are stacked in this order, wherein the first resin layer is a cured product of a first curable composition containing a (meth)acrylic compound, the polarizer is a cured product of a composition that is for forming the polarizer and that contains a dichroic dye and a polymerizable liquid crystal compound having a (meth) acryloyl group, the alignment film is a cured product of a composition that is for forming the alignment film and that contains a (meth)acrylic compound, the second resin layer is a cured product of a second curable composition containing a (meth)acrylic compound, and the first curable composition and/or the second curable composition contains, as the (meth)acrylic compound, a urethane (meth)acrylate compound having 40*10-4 or less (meth) acryloyl groups per unit molecular weight.

Description

Polarizing film and manufacturing method thereof

The invention relates to a polarizing film and a manufacturing method thereof.

Polarizing films are used in flat panel display devices (FPD). As such a polarizing film, a polarizing film obtained by attaching a polarizing element in which a dichroic dye such as iodine is adsorbed on a polyvinyl alcohol-based resin film to a substrate is known, or a polymerizable liquid crystal compound The polarizing film is coated on the substrate and polymerized. For example, Patent Document 1 discloses a polarizing film having a dye diffusion prevention layer on both sides of a polarizing element containing a polymer of a polymerizable liquid crystal compound and a dichroic dye. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2017-083843

[The problem to be solved by the invention]

The object of the present invention is to provide a polarizing film with excellent adhesion between layers and a manufacturing method thereof. [Technical means to solve the problem]

The inventors of the present invention made diligent studies to solve the above-mentioned problems. As a result, they found that in a polarizing film in which a first resin layer, a polarizing element, an alignment film, and a second resin layer were sequentially laminated, the first resin layer, the polarizing element, and the alignment The film and the second resin layer are each a cured product of a composition containing a compound having a (meth)acryloyl group, and at least one of the first curable composition and the second curable composition includes ( A urethane (meth)acrylate compound having a number of meth)acryl groups of 40×10 ^-4 or less is used as a (meth)acrylic compound to solve the above-mentioned problems, thereby completing the present invention. That is, the following aspects are included in the present invention.

[1] A polarizing film in which a first resin layer, a polarizing element, an alignment film, and a second resin layer are sequentially laminated, and the first resin layer includes a first curable combination of a (meth)acrylic compound The cured product of the object, the polarizing element is a cured product of a composition for forming a polarizing element containing a polymerizable liquid crystal compound having a (meth)acrylic acid group and a dichroic dye, and the alignment film contains a (meth)acrylic compound The cured product of the composition for forming an alignment film, the second resin layer is a cured product of the second curable composition containing a (meth)acrylic compound, at least one of the first curable composition and the second curable composition It contains a urethane (meth)acrylate compound whose number of (meth)acrylic groups per unit molecular weight is 40×10 ^-4 or less as the (meth)acrylic compound. [2] The polarizing film as described in [1], wherein at least one of the first curable composition and the second curable composition further includes a multifunctional (meth)acrylate compound as the (meth)acrylic Compound. [3] The polarizing film as described in [2], wherein the number of (meth)acrylic groups in the polyfunctional (meth)acrylate compound is 6 or less. [4] The polarizing film as described in [2] or [3], wherein the polyfunctional (meth)acrylate compound has a branched structure, and the branched structure is connected to the closest (meth)acrylic acid group The number of atoms in the chain between the branch point and the (meth)acryloyl group is 2 or more. [5] A method of manufacturing a polarizing film as described in any one of [1] to [4], comprising the steps of: polarizing a layered body in which a second resin layer, an alignment film, and a polarizing element are sequentially laminated The first curable composition is applied or laminated on the surface of the element to cure the first curable composition. [6] A method of manufacturing a polarizing film as described in any one of [1] to [4], comprising the steps of: making the first curable composition formed on the release film and the layered layer in sequence The second resin layer, the alignment film, and the polarizing element of the layered body of the polarizing element overlap, and active energy rays are irradiated from the release film side to harden the first curable composition, thereby obtaining a release film and second 1 A laminate of a resin layer, a polarizing element, an alignment film, and a second resin layer, and the release film is peeled from the laminate. [Effects of Invention]

The polarizing film of the present invention has excellent adhesion between layers.

[Polarizing Film] The polarizing film of the present invention has a first resin layer, a polarizing element, an alignment film, and a second resin layer laminated in this order. The first resin layer is a cured product of the first curable composition containing a (meth)acrylic compound, and the polarizing element is formed of a polarizing element containing a polymerizable liquid crystal compound having a (meth)acrylic acid group and a dichroic dye The cured product of the composition, the alignment film is a cured product of an alignment film forming composition containing a (meth)acrylic compound, and the second resin layer is of the second curable composition containing a (meth)acrylic compound Hardened object. In this way, each layer of the polarizing film of the present invention contains a cured product of a composition containing a compound having a (meth)acryloyl group, that is, a polymer containing a compound having a (meth)acryloyl group, so the phase of each layer interface It has high capacitance and can show excellent adhesion between layers. In addition, in the polarizing film of the present invention, at least one of the first curable composition forming the first resin layer and the second curable composition forming the second resin layer contains the number of (meth)acrylic groups per unit molecular weight A urethane (meth)acrylate compound of 40×10 ^-4 or less is a (meth)acrylic compound, so it can also have excellent flexibility. Therefore, the polarizing film of the present invention can achieve excellent adhesion and flexibility at the same time.

＜Polarizing element＞ The polarizing element contained in the polarizing film of the present invention is formed on the surface of the alignment film opposite to the second resin layer. The polarizing element is a cured product of a composition for forming a polarizing element containing a polymerizable liquid crystal compound having a (meth)acryloyl group and a dichroic dye. In this type of polarizing element, the dichroic dye is contained in the polymerizable liquid crystal compound, polymerized and cured in a state where the polymerizable liquid crystal compound and the dichroic dye are aligned, but if exposed to a high temperature environment, there will be The dichroic dye thermally diffuses from the polarizing element to the first resin layer or the second resin layer, and tends to decrease the polarization performance over time. In a suitable aspect of the present invention, the first resin layer and the second resin layer each contain a cured product of a curable composition containing a specific (meth)acrylic compound, so there is a pigment capable of inhibiting dichroic formation. The diffused cross-linked structure can effectively inhibit the degradation of polarization performance. Furthermore, in this specification, the so-called heat resistance means that even if exposed to a high temperature environment for a long time, it can suppress the degradation of the polarization performance, such as the change in the degree of polarization or transmittance, and the so-called increased or improved heat resistance means that it is caused by high temperature. The degradation or change of the polarization performance becomes less.

In the polarizing film of the present invention, the polymerizable liquid crystal compound (hereinafter, sometimes referred to as "polymerizable liquid crystal compound (A)") contained in the composition for forming a polarizing element has at least one (meth)acrylic acid The base liquid crystal compound is preferably a liquid crystal compound having two or more (meth)acrylic groups from the viewpoint of improving the adhesion, flexibility, and heat resistance of the polarizing film. In addition, the polymerizable liquid crystal compound (A) may contain a polymerizable group other than the (meth)acryloyl group. The so-called polymerizable group refers to a group that can participate in the polymerization reaction using living radicals or acids generated by the polymerization initiator. Examples of polymerizable groups other than the (meth)acryloyl group include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, oxirane, and oxetanyl. Base etc. In the present invention, the polymerizable group of the polymerizable liquid crystal compound (A) preferably contains a (meth)acrylic acid group, and more preferably contains ( Meth) propylene oxy group.

In the present invention, the polymerizable liquid crystal compound (A) is preferably a compound exhibiting smectic liquid crystallinity. By using a polymerizable liquid crystal compound exhibiting smectic liquid crystallinity, a polarizing element with a high degree of alignment order can be formed. The liquid crystal state displayed by the polymerizable liquid crystal compound (A) is a smectic phase (smectic liquid crystal state). From the viewpoint of achieving a higher degree of alignment order, the higher order smectic phase (higher order smectic Liquid crystal state). Here, the so-called higher order smectic phase refers to smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase , Smectic K phase and smectic L phase, among them, smectic B phase, smectic F phase and smectic I phase are more preferred. The liquid crystallinity may be either a thermotropic liquid crystal or a liquid liquid crystal. In terms of controlling a dense film thickness, a thermotropic liquid crystal is preferred. In addition, the polymerizable liquid crystal compound (A) may be a monomer, an oligomer obtained by polymerizing a polymerizable group, or a polymer.

The polymerizable liquid crystal compound (A) is not particularly limited as long as it is a liquid crystal compound having at least one (meth)acryloyl group. Well-known polymerizable liquid crystal compounds can be used, and it is preferable to exhibit smectic liquid crystal properties. The compound. As such a polymerizable liquid crystal compound, for example, a compound represented by the following formula (A1) (hereinafter, may be referred to as "polymerizable liquid crystal compound (A1)") is mentioned. U ¹ -V ¹ -W ¹ -(X ¹ -Y ¹ -) _n -X ² -W ² -V ² -U ² (A1) [In formula (A1), X ¹ and X ² independently represent two A valence aromatic group or a divalent alicyclic hydrocarbon group, where the hydrogen atom contained in the divalent aromatic group or a divalent alicyclic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms, A fluoroalkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons, a cyano group or a nitro group. The carbon atoms constituting the divalent aromatic group or divalent alicyclic hydrocarbon group can be substituted with oxygen atoms or A sulfur atom or a nitrogen atom; wherein at least one of X ¹ and X ² is a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent; Y ¹ It is a single bond or a divalent linking group; n is 1 to 3, when n is 2 or more, a plurality of X ¹ may be the same or different from each other; X ² may be any or all of the plurality of X ¹ The same or different; and when n is 2 or more, a plurality of Y ¹ may be the same or different from each other; from the viewpoint of liquid crystallinity, n is preferably 2 or more; U ¹ represents a hydrogen atom or (form Group) propylene oxy group; U ² represents (meth) propylene oxy group; W ¹ and W ² are independently a single bond or a divalent linking group; V ¹ and V ² independently represent a group that may have a substituent An alkanediyl group with 1 to 20 carbon atoms, the -CH ₂ -constituting the alkanediyl group may be substituted with -O-, -CO-, -S- or NH-]

In the polymerizable liquid crystal compound (A1), X ¹ and X ² are each independently preferably 1,4-phenylene which may have a substituent, or cyclohexane-1,4-diyl which may have a substituent , At least one of X ¹ and X ² is 1,4-phenylene which may have substituents or cyclohexane-1,4-diyl which may have substituents, preferably trans-cyclohexyl Alkyl-1,4-diyl. As the substituent optionally possessed by the 1,4-phenylene group which may have a substituent or the cyclohexane-1,4-diyl group which may have a substituent group, carbons such as methyl, ethyl and butyl can be mentioned. Alkyl group, cyano group, and halogen atom such as chlorine atom and fluorine atom of number 1 to 4. It is preferably unsubstituted.

Furthermore, regarding the polymerizable liquid crystal compound (A1), in terms of easily expressing smectic liquid crystallinity, in the formula (A1), the formula (A1-1): -(X ¹ -Y ¹ -) _n -X ^2- (A1-1) [In the formula, X ¹ , Y ¹ , X ² and n each have the same meaning as above] The part represented [hereinafter referred to as partial structure (A1-1)] is not Symmetrical structure. Examples of the polymerizable liquid crystal compound (A1) whose partial structure (A1-1) is an asymmetric structure include a polymerizable liquid crystal compound (A1) in which n is 1, and X ¹ and X ² are different from each other. In addition, it can also be enumerated: a compound in which n is 2, two Y ¹ are mutually the same structure, two X ¹ are mutually the same structure, and one X ² is a different structure from the two X ¹ the polymerizable liquid crystal compound (A1); 2 pieces of X and W is ^a sum of X ¹ bonded to another structure different from X ¹ and X ² of ^1, and the other X ¹ and X ² are the same as each other polymeric structures Sexual liquid crystal compound (A1). Furthermore, a polymerizable liquid crystal compound in which n is 3, three Y ¹ are mutually the same structure, and any one of three X ¹ and one X ² is different from all other three structures (A1).

Y ^{1 is} preferably -CH ₂ CH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ O-, -COO-, -OCOO-, single bond, -N=N-, -CR ^a =CR ^b- , -C≡C-, -CR ^a =N- or CO-NR ^a -. R ^a and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. More preferably Y ¹ is -CH ₂ CH ₂ -, - COO- or a single bond when, in the case of presence of a plurality of Y ^1, X ² and Y ¹ bonded to it is more preferably -CH ₂ CH ₂ - or CH ₂ O -. When both X ¹ and X ² have the same structure, it is preferable that there are two or more Y ^1s that are mutually different bonding methods. When there are a plurality of Y ^1s with mutually different bonding methods, they exhibit an asymmetric structure, and therefore tend to show smectic liquid crystallinity.

U ² is (meth)acryloyloxy. U ¹ is a hydrogen atom or a (meth)acryloxy group, preferably a (meth)acryloxy group. From the viewpoint of improving the adhesion, flexibility, and heat resistance between layers of the polarizing film, it is preferable that both U ¹ and U ² are (meth)acryloxy groups. The (meth)acryloxy group may be in a polymerized state or in an unpolymerized state, and is preferably in an unpolymerized state.

Examples of the alkanediyl groups represented by V ¹ and V ² include methylene, ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4- Diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane-1,10- Diyl, tetradecane-1,14-diyl and eicosan-1,20-diyl, etc. V ¹ and V ^{2 are} preferably an alkanediyl group having 2 to 12 carbons, and more preferably an alkanediyl group having 6 to 12 carbons.

The substituent optionally possessed by the alkanediyl group includes a cyano group and a halogen atom. The alkanediyl group is preferably unsubstituted, and more preferably an unsubstituted linear alkanediyl group.

W ¹ and W ² are each independently preferably a single bond, -O-, -S-, -COO- or OCOO-, more preferably a single bond or -O-.

The polymerizable liquid crystal compound (A) is not particularly limited as long as it is a polymerizable liquid crystal compound having at least one (meth)acryloyl group, and a known polymerizable liquid crystal compound can be used, and preferably exhibits a smectic structure. Liquid crystallinity, as a structure that easily exhibits smectic liquid crystallinity, a molecular structure having asymmetry in the molecular structure is preferable, and specifically, it is more preferable to have the following partial structures (Aa) to (Ai) A polymerizable liquid crystal compound, and a polymerizable liquid crystal compound showing smectic liquid crystallinity. It is more preferable to have a partial structure of (A-a), (A-b), or (A-c) from the viewpoint of easily showing high-order smectic liquid crystallinity. In addition, in the following (A-a) to (A-i), * represents a bonding bond (single bond).

Specific examples of the polymerizable liquid crystal compound (A) include compounds represented by formula (A-1) to formula (A-25), and the like. When the polymerizable liquid crystal compound (A) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans form.

Among them, it is preferred to be selected from formula (A-2), formula (A-3), formula (A-4), formula (A-5), formula (A-6), formula (A-7) ), formula (A-8), formula (A-13), formula (A-14), formula (A-15), formula (A-16) and formula (A-17) At least one species in the group. As the polymerizable liquid crystal compound (A), one kind may be used alone, or two or more kinds may be used in combination.

The polymerizable liquid crystal compound (A) can be produced by a known method described in, for example, Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996), or Japanese Patent No. 4719156.

In the present invention, the composition for forming a polarizing element may contain polymerizable liquid crystal compounds other than the polymerizable liquid crystal compound (A). From the viewpoint of obtaining a polarizing element with a high degree of alignment, the polymerizable liquid crystal compound (A) The ratio with respect to the total mass of the fully polymerizable liquid crystal compound contained in the composition for forming a polarizing element is preferably 51% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more.

When the composition for forming a polarizing element contains two or more polymerizable liquid crystal compounds (A), at least one of them may be a polymerizable liquid crystal compound (A1), and all of them may be a polymerizable liquid crystal compound (A1) . By combining a plurality of polymerizable liquid crystal compounds, the liquid crystallinity may be temporarily maintained even at a temperature below the liquid crystal-crystal phase transition temperature.

Regarding the content of the polymerizable liquid crystal compound in the composition for forming a polarizing element, relative to the solid content of the composition for forming a polarizing element, it is preferably 40 to 99.9% by mass, more preferably 60 to 99% by mass, and more preferably It is preferably 70 to 99% by mass. If the content of the polymerizable liquid crystal compound is within the above range, the orientation of the polymerizable liquid crystal compound tends to increase. In addition, in this specification, the so-called solid content means the total amount of the components obtained by removing the solvent from the composition for forming a polarizing element.

In the present invention, the composition for forming a polarizing element contains a dichroic dye. Here, the so-called dichroic dye refers to a dye having different properties between the absorbance in the long axis direction of the molecule and the absorbance in the short axis direction of the molecule. The dichroic dye that can be used in the present invention is not particularly limited as long as it has the above-mentioned properties, and it may be a dye or a pigment. In addition, two or more types of dyes or pigments can be combined and used, respectively, or a combination of dyes and pigments can be used. In addition, the dichroic dye may have polymerizability or liquid crystallinity.

As a dichroic dye, one having a maximum absorption wavelength (λ _MAX ) in the range of 300 to 700 nm is preferable. Examples of such dichroic dyes include acridine dyes, cyanine dyes, naphthalene dyes, azo dyes, and anthraquinone dyes.

Examples of azo dyes include monoazo dyes, bisazo dyes, trisazo dyes, tetrasazo dyes, and stilbene azo dyes, etc., preferably bisazo dyes and trisazo dyes, for example, The compound represented by formula (I) (hereinafter also referred to as "compound (I)"). K ¹ (-N=NK ² ) _p -N=NK ³ (I) [In formula (I), K ¹ and K ³ independently represent a substituted phenyl group, a substituted naphthyl group or A monovalent heterocyclic group which may have a substituent; K ² represents a p-phenylene which may have a substituent, a naphthalene-1,4-diyl which may have a substituent or a divalent heterocyclic group which may have a substituent; p Represents an integer of 1 to 4. When p is an integer of 2 or more, a plurality of K ² may be the same or different from each other; the -N=N- bond can be substituted with the range of absorption in the visible light range -C=C-, -COO-, -NHCO-, -N=CH-key]

Examples of the monovalent heterocyclic group include: quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, azole, benzoxazole, etc., obtained by removing one hydrogen atom from a heterocyclic compound base. As the divalent heterocyclic group, a group obtained by removing two hydrogen atoms from the aforementioned heterocyclic compound can be mentioned.

As a substituent optionally possessed by the phenyl group, naphthyl group, and monovalent heterocyclic group in K ¹ and K ³ , and the para-phenylene group, naphthalene-1,4-diyl group, and divalent heterocyclic group in K ² Examples include: alkyl groups with 1 to 20 carbons, alkyl groups with 1 to 20 carbons and alkenyl groups with 1 to 4 carbons having a polymerizable group; carbon numbers such as methoxy, ethoxy, butoxy, etc. Alkoxy with 1-20; Alkoxy with 1-20 carbons with polymerizable group; Fluorinated alkyl with 1 to 4 carbons such as trifluoromethyl; cyano; nitro; halogen atom; amine group , Diethylamino, pyrrolidinyl and other substituted or unsubstituted amino groups (the so-called substituted amino group refers to an amino group having 1 or 2 alkyl groups with 1 to 6 carbon atoms, One or two amine groups of a C1-C6 alkyl group with a polymerizable group, or two substituted alkyl groups are bonded to each other to form an amine group of a C2-C8 alkanediyl group; unsubstituted amine The base is -NH ₂ ) and so on. In addition, here, as the above-mentioned polymerizable group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, etc. are mentioned.

[式(I-1)～(I-8)中， B¹ ～B³⁰ 相互獨立地表示氫原子、碳數1～6之烷基、碳數1～6之烯基、碳數1～4之烷氧基、氰基、硝基、經取代或未經取代之胺基(經取代之胺基及未經取代之胺基之定義如上所述)、氯原子或三氟甲基； n1～n4相互獨立地表示0～3之整數； 於n1為2以上之情形時，複數個B² 相互可相同亦可不同， 於n2為2以上之情形時，複數個B⁶ 相互可相同亦可不同， 於n3為2以上之情形時，複數個B⁹ 相互可相同亦可不同， 於n4為2以上之情形時，複數個B¹⁴ 相互可相同亦可不同]Among the compounds (I), a compound represented by any one of the following formulas (I-1) to (I-6) is preferred.

[In formulas (I-1) to (I-8), B ¹ to B ³⁰ independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, an alkenyl group with 1 to 6 carbons, and a carbon number of 1 to 4 Alkoxy, cyano, nitro, substituted or unsubstituted amine (the definitions of substituted amine and unsubstituted amine are as described above), chlorine atom or trifluoromethyl; n1～ n4 represents an integer from 0 to 3 independently of each other; when n1 is 2 or more, plural B ² may be the same or different from each other, and when n2 is 2 or more, plural B ⁶ may be the same or different from each other , When n3 is 2 or more, plural B ⁹ may be the same or different from each other, and when n4 is 2 or more, plural B ¹⁴ may be the same or different from each other]

[式(I-9)中， R¹ ～R⁸ 相互獨立地表示氫原子、-R^x 、-NH₂ 、-NHR^x 、-NR^x ₂ 、-SR^x 或鹵素原子； R^x 表示碳數1～4之烷基或碳數6～12之芳基]The anthraquinone dye is preferably a compound represented by formula (I-9).

[In formula (I-9), R ¹ to R ⁸ independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom; R ^x represents the number of carbon atoms 1～4 alkyl group or 6～12 aryl group]

[式(I-8)中， R⁹ ～R¹⁵ 相互獨立地表示氫原子、-R^x 、-NH₂ 、-NHR^x 、-NR^x ₂ 、-SR^x 或鹵素原子； R^x 表示碳數1～4之烷基或碳數6～12之芳基]The ketone dye is preferably a compound represented by formula (I-10).

[In formula (I-8), R ⁹ to R ¹⁵ independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom; R ^x represents the number of carbons 1～4 alkyl group or 6～12 aryl group]

[式(I-11)中， R¹⁶ ～R²³ 相互獨立地表示氫原子、-R^x 、-NH₂ 、-NHR^x 、-NR^x ₂ 、-SR^x 或鹵素原子； R^x 表示碳數1～4之烷基或碳數6～12之芳基] 於式(I-9)、式(I-10)及式(I-11)中，作為R^x 之碳數1～6之烷基，可列舉：甲基、乙基、丙基、丁基、戊基及己基等，作為碳數6～12之芳基，可列舉：苯基、甲苯甲醯基、二甲苯基及萘基等。The acridine dye is preferably a compound represented by formula (I-11).

[In formula (I-11), R ¹⁶ to R ²³ independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x or a halogen atom; R ^x represents the number of carbons 1 to 4 alkyl group or 6 to 12 carbon aryl group] In formula (I-9), formula (I-10) and formula (I-11), it is the C 1 to 6 alkyl group of R ^x Examples of the group include methyl, ethyl, propyl, butyl, pentyl and hexyl. Examples of the aryl group having 6 to 12 carbon include phenyl, tolyl, xylyl and naphthyl. Wait.

[式(I-12)中， D¹ 及D² 相互獨立地表示式(I-12a)～式(I-12d)中之任一者所表示之基；

n5表示1～3之整數]

[式(I-13)中， D³ 及D⁴ 相互獨立地表示式(I-13a)～式(1-13h)中之任一者所表示之基；

n6表示1～3之整數]As said cyanine pigment, the compound represented by formula (I-12) and the compound represented by formula (I-13) are preferable.

[In formula (I-12), D ¹ and D ² independently represent a group represented by any one of formula (I-12a) to formula (I-12d);

n5 represents an integer from 1 to 3]

[In formula (I-13), D ³ and D ⁴ independently represent a group represented by any one of formula (I-13a) to formula (1-13h);

n6 represents an integer from 1 to 3]

Among these dichroic dyes, since the linearity is relatively high, it is preferably an azo dye suitable for making a polarizing element with excellent polarization performance. In the present invention, the weight average molecular weight of the dichroic dye is generally 300-2000, preferably 400-1000.

The content of the dichroic dye in the composition for forming a polarizing element can be appropriately determined according to the type of the dichroic dye used, etc., and is preferably 0.1-50 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound, and more Preferably it is 0.1-20 mass parts, More preferably, it is 0.1-12 mass parts. If the content of the dichroic pigment is within the above range, the alignment of the polymerizable liquid crystal compound is not easily disturbed, and a polarizing element with a higher degree of alignment order can be obtained.

In the present invention, the composition for forming a polarizing element may contain a polymerization initiator. The polymerization initiator is a compound capable of starting the polymerization reaction of the polymerizable liquid crystal compound. In terms of starting the polymerization reaction under lower temperature conditions, a photopolymerization initiator is preferred. Specifically, photopolymerization initiators that can generate active radicals or acids by the action of light can be cited, and among them, photopolymerization initiators that can generate free radicals by the action of light are preferred. The polymerization initiator can be used alone or in combination of two or more kinds.

系化合物、鹵代苯乙酮系化合物、二烷氧基苯乙酮系化合物、鹵代雙咪唑系化合物、鹵代三𠯤系化合物、三𠯤系化合物等。As the photopolymerization initiator, a known photopolymerization initiator can be used. For example, as a photopolymerization initiator for generating living radicals, there are self-cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators. Agent. As a self-cleavable photopolymerization initiator, self-cleavable benzoin-based compounds, acetophenone-based compounds, hydroxyacetophenone-based compounds, α-aminoacetophenone-based compounds, and oxime ester-based compounds can be used , Amino phosphine oxide compounds, azo compounds, etc. In addition, as hydrogen abstraction type photopolymerization initiators, hydrogen abstraction type benzophenone compounds, benzoin ether compounds, benzal ketal compounds, dibenzocycloheptanone compounds, and anthraquinone compounds can be used. Compounds, xanthone compounds, 9-oxysulfur 𠮿

-Based compounds, halogenated acetophenone-based compounds, dialkoxy acetophenone-based compounds, halogenated bisimidazole-based compounds, halogenated tris-based compounds, tris-based compounds, etc.

As an acid-generating photopolymerization initiator, iodonium salt, sulphur salt, etc. can be used.

Among them, from the viewpoint of preventing the dissolution of the pigment, the reaction at low temperature is preferred, and from the viewpoint of the reaction efficiency at low temperature, the self-cleavable photopolymerization initiator is preferred, and acetophenone is particularly preferred. Based compounds, hydroxyacetophenone based compounds, α-aminoacetophenone based compounds, oxime ester based compounds.

Examples of the photopolymerization initiator include the following. Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2-hydroxy-2-methyl -1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-[4-(1-methyl Hydroxyacetophenone compounds such as oligomers of propan-1-one; 2-Methyl-2-morpholinyl-1-(4-methylthienyl)propan-1-one, 2-dimethylamino-2-benzyl-1-(4-morpholinylphenyl) ) Α-aminoacetophenone compounds such as butane-1-one; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-methyl Benzyl)-9H-carbazol-3-yl]-,1-(O-acetoxime) and other oxime ester compounds; 2,4,6-trimethylbenzyl diphenyl phosphine oxide and bis(2,4,6-trimethylbenzyl) phenyl phosphine oxide and other phosphonium oxide compounds; Benzophenone, methyl phthalate benzoate, 4-phenylbenzophenone, 4-benzyl-4'-methyl diphenyl sulfide, 3,3',4,4'- Benzophenone compounds such as tetrakis(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone; Dialkoxy acetophenone compounds such as diethoxyacetophenone; 2,4-Bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris, 2,4-bis(trichloromethyl)-6-(4- Methoxynaphthyl)-1,3,5-tris, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tris, 2,4-Bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-tri𠯤, 2,4-bis(trichloromethyl Yl)-6-[2-(furan-2-yl)vinyl]-1,3,5-tris, 2,4-bis(trichloromethyl)-6-[2-(4-diethyl) -Amino-2-methylphenyl)vinyl]-1,3,5-tris and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxy Phenyl) vinyl] -1,3,5-tris, and other tris series compounds. The photopolymerization initiator may be appropriately selected from the above-mentioned photopolymerization initiator based on the relationship with the polymerizable liquid crystal compound contained in the composition for forming a polarizing element.

In addition, a commercially available photopolymerization initiator can be used. Commercially available polymerization initiators include: Irgacure (registered trademark) 907, 184, 651, 819, 250, and 369, 379, 127, 754, OXE01, OXE02, OXE03 (manufactured by BASF Corporation); Omnirad BCIM, Esacure 1001M, Esacure KIP160 (manufactured by IDM Resins BV); Seikuol (registered trademark) BZ, Z, and BEE (manufactured by Seiko Chemical Co., Ltd.); Kayacure (registered trademark) BP100, and UVI-6992 (Dow Chemical Co., Ltd.) Manufacturing); Adeka Optomer SP-152, N-1717, N-1919, SP-170, Adekaarc Luz NCI-831, Adekaarc Luz NCI-930 (made by ADEKA Co., Ltd.); TAZ-A, and TAZ-PP (Nihon SiberHegner Co., Ltd.); and TAZ-104 (Sanhe Chemical Co., Ltd.), etc.

Regarding the content of the polymerization initiator in the composition for forming a polarizing element, relative to 100 parts by mass of the polymerizable liquid crystal compound, it is preferably 1-10 parts by mass, more preferably 1-8 parts by mass, and still more preferably 2 ~8 parts by mass, particularly preferably 4-8 parts by mass. If the content of the polymerization initiator is within the above range, the polymerization reaction of the polymerizable liquid crystal compound can proceed without greatly disrupting the alignment of the polymerizable liquid crystal compound.

Regarding the polymerization rate of the polymerizable liquid crystal compound in the present invention, from the viewpoint of production line contamination or handling during production, it is preferably 60% or more, more preferably 65% or more, and still more preferably 70% or more.

等氧雜蒽酮化合物(例如2,4-二乙基-9-氧硫𠮿

、2-異丙基-9-氧硫𠮿

等)；蒽、含烷氧基之蒽(例如二丁氧基蒽等)等蒽化合物；啡噻𠯤及紅螢烯等。光敏劑可單獨使用或組合兩種以上而使用。The composition for forming a polarizing element may further contain a photosensitizer. By using a photosensitizer, the polymerization reaction of the polymerizable liquid crystal compound can be further promoted. Examples of photosensitizers include: xanthone, 9-oxysulfur 𠮿

And other xanthone compounds (e.g. 2,4-diethyl-9-oxysulfur 𠮿

, 2-isopropyl-9-oxysulfur 𠮿

Etc.); anthracene compounds such as anthracene, alkoxy-containing anthracene (such as dibutoxyanthracene, etc.); phenanthrene and red fluorene. The photosensitizer can be used alone or in combination of two or more kinds.

When the composition for forming a polarizing element contains a photosensitizer, its content may be appropriately determined according to the type and amount of the polymerization initiator and polymerizable liquid crystal compound, and is preferably relative to 100 parts by mass of the polymerizable liquid crystal compound It is 0.1-30 parts by mass, more preferably 0.5-10 parts by mass, and still more preferably 0.5-8 parts by mass.

The composition for forming a polarizing element may further contain a leveling agent. The leveling agent has a function of adjusting the fluidity of the composition for forming a polarizing element and making the coating film obtained by coating the composition for forming a polarizing element more flat. Specifically, a surfactant can be mentioned. The leveling agent is preferably at least one selected from the group consisting of a leveling agent having a polyacrylate compound as a main component and a leveling agent having a fluorine atom-containing compound as a main component. The leveling agent can be used individually or in combination of 2 or more types.

As a leveling agent mainly composed of polyacrylate compounds, for example, "BYK-350", "BYK-352", "BYK-353", "BYK-354", "BYK-355", "BYK" -358N", "BYK-361N", "BYK-380", "BYK-381" and "BYK-392" (BYK Chemie).

As a leveling agent with a fluorine atom-containing compound as the main component, for example, "MEGAFAC (registered trademark) R-08", the same series "R-30", the same series "R-90", and the same series "F -410", same series "F-411", same series "F-443", same series "F-445", same series "F-470", same series "F-471", same series "F-477" ", the same series "F-479", the same series "F-482" and the same "F-483" (DIC Co., Ltd.); "Surflon (registered trademark) S-381", the same series "S-382", Same series "S-383", same series "S-393", same series "SC-101", same series "SC-105", "KH-40" and "SA-100" (AGC Seimi Chemical Co., Ltd. ); "E1830", "E5844" (Daikin Institute of Fine Chemicals Co., Ltd.); "Eftop EF301", "Eftop EF303", "Eftop EF351" and "Eftop EF352" (Mitsubishi Materials Electronic Chemicals Co., Ltd.).

When the composition for forming a polarizing element contains a leveling agent, the content is preferably 0.05 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. If the content of the leveling agent is within the above range, it is easy to align the polymerizable liquid crystal compound horizontally, and unevenness is unlikely to occur, and a smoother polarizing element tends to be obtained.

The composition for forming a polarizing element may contain additives other than a photosensitizer and a leveling agent. Examples of other additives include colorants such as antioxidants, release agents, stabilizers, and bluing agents, flame retardants, lubricants, and the like. When the composition for forming a polarizing element contains other additives, the content of the other additives relative to the solid content of the composition for forming a polarizing element is preferably more than 0% and 20% by mass or less, more preferably more than 0 % And 10% by mass or less.

The composition for forming a polarizing element can be produced by a previously known preparation method of a composition for forming a polarizing element, usually by mixing a polymerizable liquid crystal compound and a dichroic dye, and optionally a polymerization initiator and the above additives Wait and stir to prepare. In addition, compounds that generally exhibit smectic liquid crystallinity have relatively high viscosity. Therefore, from the viewpoint of improving the coating properties of the composition for forming a polarizing element and making it easier to form a polarizing element, it can be added to the composition for forming a polarizing element. Add solvent to adjust viscosity.

The solvent used in the composition for forming a polarizing element can be appropriately selected according to the solubility of the polymerizable liquid crystal compound and the dichroic dye used. Specifically, for example, alcohol solvents such as water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, Ester solvents such as ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone , Methyl isobutyl ketone and other ketone solvents; pentane, hexane, heptane and other aliphatic hydrocarbon solvents; toluene, xylene and other aromatic hydrocarbon solvents; acetonitrile and other nitrile solvents; tetrahydrofuran, dimethoxyethane and other ethers Solvents; and chlorinated hydrocarbon solvents such as chloroform and chlorobenzene. These solvents can be used alone or in combination of two or more. The content of the solvent is preferably 100 to 1900 parts by mass, more preferably 150 to 900 parts by mass, and still more preferably 180 to 600 parts by mass relative to 100 parts by mass of the solid content of the composition for forming a polarizing element.

In the polarizing film of the present invention, the polarizing element is preferably a polarizing element with a higher degree of alignment. The polarizing element with a higher degree of alignment shows the Bourget peak derived from the hexagonal phase or the higher order structure of the crystal in the X-ray diffraction measurement. The so-called Burrge peak refers to the peaks derived from the surface periodic structure of molecular alignment. Therefore, it is preferable that the polarizing element constituting the polarizing film of the present invention exhibits a Boureg peak in X-ray diffraction measurement. That is, in the polarizing element constituting the polarizing film of the present invention, the polymerizable liquid crystal compound or polymer thereof is preferably aligned in such a way that the polarizing element exhibits the Bourget peak in the X-ray diffraction measurement, more preferably The "horizontal alignment" in which the molecules of the polymerizable liquid crystal compound are aligned along the direction of absorbing light. In the present invention, it is preferable to use a polarizing element in which the molecular alignment of the plane period interval is 3.0 to 6.0 Å. For example, the higher degree of alignment order of the Boule peak can be achieved by controlling the type of polymerizable liquid crystal compound used, the type or amount of dichroic pigment, and the type or amount of polymerization initiator. .

In one embodiment of the present invention, the polarizing element can be obtained by a method including the following steps: forming a coating film of the composition for forming a polarizing element on the alignment film; removing the solvent from the coating film; After the phase transition of the liquid crystal compound is higher than the temperature of the liquid phase, the temperature is lowered to make the polymerizable liquid crystal compound phase transition into a smectic phase; and the polymerizable liquid crystal compound is polymerized while maintaining the smectic phase.

As a method of applying the composition for forming a polarizing element to an alignment film, etc., spin coating method, extrusion coating method, gravure coating method, die coating method, bar coating method, application method, etc. Known methods such as printing methods such as coating method and soft plate method.

Then, a dry coating film is formed by removing the solvent by drying or the like under the condition that the polymerizable liquid crystal compound contained in the coating film obtained by the composition for forming a polarizing element is not polymerized. As a drying method, a natural drying method, a ventilation drying method, heat drying, and a reduced-pressure drying method, etc. are mentioned.

Furthermore, in order to make the polymerizable liquid crystal compound phase transition into the liquid phase, the temperature is raised to a temperature higher than the temperature at which the polymerizable liquid crystal compound phase transitions into the liquid phase and then the temperature is lowered to make the polymerizable liquid crystal compound phase transition into a smectic phase (smectic liquid crystal state) . This phase transfer can be carried out after the removal of the solvent in the above-mentioned coating film, or can be carried out simultaneously with the removal of the solvent.

By polymerizing the polymerizable liquid crystal compound while maintaining the smectic liquid crystal state of the polymerizable liquid crystal compound, the polarizing element is formed as a hardened layer of the composition for forming the polarizing element. As the polymerization method, a photopolymerization method is preferred. In photopolymerization, the light irradiated to the dry coating film is based on the type of polymerizable liquid crystal compound contained in the dry coating film (especially the type of polymerizable group possessed by the polymerizable liquid crystal compound), polymerization The type of the starting agent and the amount are selected appropriately. As a specific example, one or more active energy rays or active electron beams selected from the group consisting of visible light, ultraviolet light, infrared light, X-ray, α-ray, β-ray, and γ-ray can be cited. Among them, in terms of easily controlling the progress of the polymerization reaction, or in terms of being used by a wide range of users in the field as a photopolymerization device, ultraviolet light is preferable, and ultraviolet light is preferably used so that light can be carried out. For the polymerization method, the type of polymerizable liquid crystal compound or polymerization initiator contained in the composition for forming a polarizing element is selected in advance. In addition, during polymerization, the dry coating film may be cooled by an appropriate cooling method, and light may be irradiated to control the polymerization temperature. During photopolymerization, patterned polarizing elements can also be obtained by masking or developing.

As the light source of the above-mentioned active energy rays, there may be mentioned: low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, halogen lamp, carbon arc lamp, tungsten lamp, gallium lamp, excimer laser, emitting wavelength range of 380～ 440 nm light LED (Light Emitting Diode) light source, chemical lamp, black light lamp, microwave excited mercury lamp, metal halide lamp, etc.

The intensity of ultraviolet radiation is usually 10 to 3,000 mW/cm ² . The intensity of ultraviolet irradiation is preferably an intensity within a wavelength range effective for activation of the polymerization initiator. The time for irradiating light is usually 0.1 second to 10 minutes, preferably 1 second to 5 minutes, more preferably 5 seconds to 3 minutes, and still more preferably 10 seconds to 1 minute. If irradiated with such ultraviolet radiation intensity once or multiple times, the cumulative light amount is 10 to 3,000 mJ/cm ² , preferably 50 to 2,000 mJ/cm ² , and more preferably 100 to 1,000 mJ/cm ² .

By performing photopolymerization, the polymerizable liquid crystal compound is polymerized while maintaining the liquid crystal state of the smectic phase, preferably the higher-order smectic phase, to form a polarizing element. The polarizing element obtained by polymerizing the polymerizable liquid crystal compound in the state of maintaining the liquid crystal state of the smectic phase also accompanies the effect of the above-mentioned dichroic dye, which is different from the previous host-guest polarizing film, that is, the liquid crystal state containing the nematic phase. Compared with the polarizing element, it has the advantage of higher polarization performance. Furthermore, there is also an advantage of superior strength compared with those coated with only dichroic dyes or liquid-tropic liquid crystals.

The thickness of the polarizing element can be appropriately selected according to the applied display device, and is preferably a film of 0.1-5 μm, more preferably 0.3-4 μm, and still more preferably 0.5-3 μm. If the film thickness of the polarizing element is more than the above lower limit, it is easy to prevent the desired light absorption from being unable to be obtained, and if it is less than the above upper limit, it is easy to suppress the occurrence of alignment defects caused by the decrease in the alignment regularity of the alignment film. In addition, the polarizing film, the polarizing element, the alignment film, the first resin layer and the second resin layer, and the following polarizing plate can be measured with a laser microscope or a film thickness meter, respectively.

＜Alignment film＞ The alignment film contained in the polarizing film of the present invention is formed on the surface of the polarizing element on the side opposite to the first resin layer. The alignment film is one that has alignment restriction that allows the polymerizable liquid crystal compound to align the liquid crystal in the desired direction. As the alignment film, it is preferable to have solvent resistance that does not dissolve due to coating of the above-mentioned polarizing film forming composition, etc., and to have heat resistance for solvent removal or heat treatment for alignment of polymerizable liquid crystal compounds Sex. In the present invention, the alignment film is a cured product of an alignment film forming composition containing a (meth)acrylic compound, and has excellent adhesion between the interface with the polarizing element and the interface with the second resin layer. From the viewpoint of improving adhesion and flexibility, the alignment film in the present invention is preferably a photo-alignment formed by curing the composition for forming an alignment film by polarized light (preferably polarized light UV (Ultra Violet, ultraviolet)). membrane.

The (meth)acrylic compound in the composition for forming an alignment film means a compound having at least one (meth)acrylic group, and the (meth)acrylic compound may be a monomer, an oligomer, or a polymer. In the case of oligomers or polymers, (meth)acrylic double bonds can be polymerized. The (meth)acrylic compound contained in the composition for forming a photo-alignment film preferably has a photoreactive group in addition to the (meth)acryloyl group.

The so-called photoreactive group refers to a group that produces liquid crystal alignment ability by light irradiation. Specifically, examples include groups that participate in photoreactions that are the origin of the alignment ability of liquid crystals, such as orientation induction or isomerization reactions, dimerization reactions, photocrosslinking reactions, or photolysis reactions of molecules generated by light irradiation. Among them, in terms of excellent alignment, a group that participates in a dimerization reaction or a photocrosslinking reaction is preferred. The photoreactive group is preferably a group having an unsaturated bond, especially a double bond, and particularly preferably a group having a carbon-carbon double bond (C=C bond) and a carbon-nitrogen double bond (C=N bond) , At least one group in the group consisting of nitrogen-nitrogen double bond (N=N bond) and carbon-oxygen double bond (C=O bond).

Examples of the photoreactive group having a C=C bond include a vinyl group, a polyalkenyl group, a stilbene group, a styrylpyridyl group, an azastilbyl group, a chalcone group, and a cinnamyl group. Examples of the photoreactive group having a C=N bond include groups having structures such as aromatic Schiff bases and aromatic hydrazones. Examples of the photoreactive group having N=N bond include: azophenyl, azonaphthyl, aromatic heterocyclic azo, bisazo, formazan, and those having an oxyazobenzene structure Base etc. As a photoreactive group which has a C=O bond, a benzophenone group, a coumarin group, an anthraquinone group, a maleimide group, etc. are mentioned. These groups may have substituents such as alkyl groups, alkoxy groups, aryl groups, allyloxy groups, cyano groups, alkoxycarbonyl groups, hydroxyl groups, sulfonic acid groups, and halogenated alkyl groups.

Among them, the photoreactive group that participates in the photodimerization reaction is preferred. In terms of easily obtaining a photoalignment film with relatively small amount of irradiated polarization required for photoalignment, and excellent thermal stability or stability over time, Preferred are cinnamon group and chalcone group. The (meth)acrylic oligomer or polymer contained in the composition for forming a photo-alignment film is particularly preferably one having a cinnamyl group exhibiting a cinnamic acid structure at the end of the side chain of the oligomer or polymer.

In one embodiment of the present invention, the photo-alignment film can be formed by coating a photo-alignment film-forming composition containing a (meth)acrylic compound and a solvent on the second resin layer and irradiating it with polarized light (preferably Obtained for polarized light (UV). Examples of the solvent contained in the composition for forming a photo-alignment film include the same solvents as those exemplified above as a solvent that can be used in the formation of a polarizing element. The solvent can be based on the solubility of the (meth)acrylic compound. And choose appropriately.

The content of the (meth)acrylic compound in the composition for forming a photo-alignment film can be appropriately adjusted according to the type of the (meth)acrylic compound or the thickness of the target photo-alignment film, compared to the composition for forming a photo-alignment film The mass is preferably at least 0.2% by mass, and more preferably in the range of 0.3-10% by mass. The composition for forming the photo-alignment film may also contain polymer materials such as polyvinyl alcohol or polyimide or a photosensitizer within the range that does not significantly impair the characteristics of the photo-alignment film.

As a method of coating the composition for forming a photo-alignment film on the second resin layer, and a method of removing the solvent from the composition for forming a photo-alignment film that has been applied, there may be mentioned as coating of the composition for forming a polarizing element The method of distributing the alignment film and the method of removing the solvent are the methods exemplified above.

The polarized light can be irradiated directly with the polarized UV light obtained by removing the solvent from the photo-alignment film forming composition coated on the second resin layer, or the polarized light can be irradiated from the side of the second resin layer to transmit the polarized light And the form of irradiation. Furthermore, it is particularly preferable if the polarized light is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably within the wavelength range in which the photoreactive group of the (meth)acrylic compound and/or the (meth)acryl group can absorb light energy. Specifically, UV (ultraviolet rays) with a wavelength of 250 to 400 nm is particularly preferred. As the light source used in the irradiation of the polarized light, a xenon lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, KrF, ArF and other ultraviolet lasers, etc., are more preferably a high-pressure mercury lamp, an ultra-high pressure mercury lamp, and a metal halide lamp. . Among them, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferable because of the higher luminous intensity of ultraviolet light with a wavelength of 313 nm. Polarized UV can be irradiated by passing light from the above-mentioned light source through an appropriate polarizing element. As the polarizing element, a polarizing filter or a polarizing element such as Glan Thompson or Glan Taylor or a wire grid type can be used.

Furthermore, when rubbing or polarized light irradiation is performed, if masking is performed, a plurality of regions (patterns) with different directions of liquid crystal alignment can also be formed.

The thickness of the alignment film is preferably 10-5000 nm, more preferably 10-1000 nm, and still more preferably 30-300 nm. If the thickness of the alignment film is in the above range, it can exhibit good adhesion with the interface with the polarizing element or the interface with the second resin layer, and exert the alignment regularity, so that the polarization element can be formed in a higher alignment order.

<The first resin layer and the second resin layer> The first resin layer contained in the polarizing film of the present invention is a cured product of the first curable composition containing a (meth)acrylic compound, and is formed on the surface of the polarizing element opposite to the alignment film side. In the present invention, the first resin layer and the polarizing element are both formed of a compound having a (meth)acryloyl group, so the compatibility between the layers is relatively high, and the (methyl) contained in the first curable composition ) The acrylic compound and the (meth)acrylic compound contained in the alignment film can form a crosslinked structure. Therefore, the polarizing film of the present invention can exhibit excellent adhesion at the interface of the first resin layer. The second resin layer contained in the polarizing film of the present invention is a cured product of a second curable composition containing a (meth)acrylic compound, and is formed on the surface of the alignment film opposite to the polarizing element side. In the present invention, the second resin layer and the alignment film are both formed of a compound having a (meth)acryloyl group, so the compatibility between the layers is high. In addition, the (methyl) layer contained in the second curable composition ) The acrylic compound and the polymerizable liquid crystal compound having a (meth)acrylic acid group contained in the polarizing element can form a crosslinked structure. Therefore, the polarizing film of the present invention can exhibit excellent adhesion at the interface of the second resin layer.

The (meth)acrylic compound contained in the first curable composition and the second curable composition is a compound having at least one (meth)acrylic group, and may be a monomer, oligomer, or polymer .

In the present invention, at least one of the first curable composition and the second curable composition, preferably both, contains an amine having a (meth)acrylic acid group per unit molecular weight of 40×10 ^-4 or less A carbamic acid ester (meth)acrylate compound is used as a (meth)acrylic compound. If such a urethane (meth)acrylate compound is included, it can exhibit excellent flexibility. Furthermore, the number of (meth)acrylic groups per unit molecular weight can be determined by the formula: the number of (meth)acrylic groups of the urethane (meth)acrylate compound/weight average molecular weight (Mw) Figure out. In this specification, the so-called flexibility refers to the characteristic that can suppress the occurrence of cracks and the like when the polarizing film is bent.

In the aforementioned urethane (meth)acrylate compound, the number of (meth)acrylic groups per unit molecular weight is preferably 30×10 ^-4 or less, more preferably 20×10 ^-4 or less. If the number of (meth)acrylic acid groups per unit molecular weight is in the above range, it is easier to improve the flexibility of the polarizing film. In addition, the lower limit of the number of (meth)acrylic acid groups per unit molecular weight is preferably 1×10 ^-5 or more, more preferably 1×10 ^-4 or more.

The aforementioned urethane (meth)acrylate compound generally refers to a reactant of an isocyanate compound, a polyol compound, and a (meth)acrylate compound, and preferably has two or more (meth)acrylic acid in the molecule. Multifunctional urethane (meth)acrylate compound of oxy group. The polyfunctional urethane (meth)acrylate compound can form a cross-linked structure that is favorable for bending, so it is easy to improve the flexibility of the polarizing film.

As the polyfunctional urethane (meth)acrylate compound, the number of functional groups is preferably 2-5 from the viewpoint of flexibility.

The weight average molecular weight (Mw) of the above-mentioned urethane (meth)acrylate compound is calculated as polystyrene, and is preferably 300 or more, more preferably 400 or more, still more preferably 1000 or more, and particularly preferably 2000 or more, and preferably 10,000 or less, more preferably 7,000 or less, and still more preferably 5,000 or less. When the Mw of the urethane (meth)acrylate compound is in the above range, it is easy to improve adhesion and flexibility. In addition, the weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC), for example.

The first curable composition and/or the second curable composition may include one or more types of urethane (meth)acrylate compounds. In addition, when two or more types of urethane (meth)acrylate compounds are included, among the urethane (meth)acrylate compounds, the (meth)acrylic acid per unit molecular weight The base number, weight average molecular weight, etc. may also be different.

Regarding the content of the urethane (meth)acrylate compound whose number of (meth)acrylic groups per unit molecular weight in the first curable composition or the second curable composition is 40×10 ^-4 or less, It is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, and preferably 100 parts by mass or less with respect to 100 parts by mass of the solid content of the curable composition. When the content of the urethane (meth)acrylate compound is in the above range, it is easy to improve the adhesion, flexibility, and heat resistance of the polarizing film.

In one embodiment of the present invention, at least one of the first curable composition and the second curable composition may further include a multifunctional (meth)acrylate compound as a (meth)acrylic compound. If such a polyfunctional (meth)acrylate compound is contained, it is easy to improve the flexibility of the polarizing film. Moreover, by combining with the above-mentioned urethane (meth)acrylate compound, heat resistance can also be improved. In the present invention, the above-mentioned polyfunctional (meth)acrylate compound is usually a (meth)acrylate compound without a urethane bond, which is different from the urethane (meth)acrylate compound. Compound.

The polyfunctional (meth)acrylate compound refers to a compound having two or more (meth)acryloxy groups in the molecule. As an example, for example, there may be mentioned: having two (meth)acryloxy groups in the molecule The bifunctional (meth)acrylate monomer, the trifunctional or more (meth)acrylate monomer having 3 or more (meth)acryloxy groups in the molecule, etc. Furthermore, in this specification, the term "(meth)acrylate" refers to "acrylate" or "methacrylate", and the term "(meth)acryloyl" also refers to "acrylic acid" in the same way. Group" or "methacrylic acid group".

The first curable composition or the second curable composition may contain two or more types of polyfunctional (meth)acrylate compounds as the polyfunctional (meth)acrylate compound. In addition, when two or more types of polyfunctional (meth)acrylate compounds are included, the number of (meth)acryloxy groups may be the same or different among the polyfunctional (meth)acrylate compounds. The molecular weight of the polyfunctional (meth)acrylate compound is preferably 100-2000, more preferably 200-1500.

Examples of bifunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, and 1,4-butanediol di(meth)acrylate. (Meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate and neopentyl glycol di(meth)acrylate, etc. Alkyl glycol di(meth)acrylate; diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate Polyoxyalkylene glycols such as meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate and polytetramethylene glycol di(meth)acrylate Di(meth)acrylate; di(meth)acrylate of halogen-substituted alkylene glycol such as tetrafluoroethylene glycol di(meth)acrylate; trimethylolpropane di(meth)acrylate, Di-trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate and other aliphatic polyol di(meth)acrylate; hydrogenated dicyclopentadienyl di(meth)acrylic acid Hydrogenated dicyclopentadiene or tricyclodecanediol di(meth)acrylate such as ester, tricyclodecane dimethanol di(meth)acrylate, etc.; 1,3-dioxane-2,5 -Diyl di(meth)acrylate [alias: dioxanediol di(meth)acrylate] and other dioxanediols or dioxanediol di(meth)acrylates; bisphenol A. Ethylene oxide adduct diacrylate, bisphenol F ethylene oxide adduct diacrylate, etc. Bisphenol A or bisphenol F alkylene oxide adduct di(meth)acrylate ；Acrylic acid adduct of bisphenol A diglycidyl ether, acrylic acid adduct of bisphenol F diglycidyl ether, etc. Epoxy di(meth)acrylate of bisphenol A or bisphenol F; polysiloxane di(meth) Meth) acrylate; neopentyl glycol hydroxypivalate di(meth)acrylate; 2,2-bis[4-(meth)acryloyloxyethoxyethoxyphenyl]propane ; 2,2-bis[4-(meth)propenyloxyethoxyethoxycyclohexyl]propane; 2-(2-hydroxy-1,1-dimethylethyl)-5-ethyl -5-hydroxymethyl-1,3-dioxane] di(meth)acrylate; tris(hydroxyethyl)isocyanuric acid di(meth)acrylate, etc.

A monomer having three (meth)acryloyloxy groups in the molecule of a trifunctional (meth)acrylate single system. Examples thereof include: glycerol tri(meth)acrylate, trimethylolpropane Tri(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, reaction product of pentaerythritol tri(meth)acrylate and acid anhydride, caprolactone modification Trimethylolpropane tri(meth)acrylate, caprolactone modified pentaerythritol tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, ethylene oxide Alkyl modified pentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified pentaerythritol tri(meth)acrylate, isocyanuric acid tri(meth)acrylate Base) acrylate, caprolactone modified pentaerythritol tri(meth)acrylate and acid anhydride reactant, ethylene oxide modified pentaerythritol tri(meth)acrylate reactant with acid anhydride, propylene oxide modified pentaerythritol The reactant of tri(meth)acrylate and acid anhydride, etc.

A tetrafunctional (meth)acrylate monomer system having 4 (meth)acryloyloxy groups in the molecule, as an example, for example, di-trimethylolpropane tetra(meth)acrylate , Pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, tripentaerythritol tetra (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified three Pentaerythritol tetra(meth)acrylate, ethylene oxide modified pentaerythritol tetra(meth)acrylate, ethylene oxide modified tripentaerythritol tetra(meth)acrylate, propylene oxide modified pentaerythritol tetra(meth)acrylate ) Acrylate, propylene oxide modified tripentaerythritol tetra(meth)acrylate, etc.

Examples of the 5-functional (meth)acrylate monomer include: dipentaerythritol penta(meth)acrylate, tripentaerythritol penta(meth)acrylate, and a reaction product of dipentaerythritol penta(meth)acrylate and acid anhydride , Caprolactone modified dipentaerythritol penta(meth)acrylate, caprolactone modified tripentaerythritol penta(meth)acrylate, ethylene oxide modified dipentaerythritol penta(meth)acrylate, ethylene oxide Alkyl modified tripentaerythritol penta(meth)acrylate, propylene oxide modified dipentaerythritol penta(meth)acrylate, propylene oxide modified tripentaerythritol penta(meth)acrylate, caprolactone modified dipentaerythritol The reactant of penta(meth)acrylate and acid anhydride, the reactant of ethylene oxide modified dipentaerythritol penta(meth)acrylate and acid anhydride, the reactant of propylene oxide modified dipentaerythritol penta(meth)acrylate and acid anhydride The reactants and so on.

Examples of the hexafunctional (meth)acrylate monomer include dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate , Caprolactone modified tripentaerythritol hexa(meth)acrylate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate, ethylene oxide modified tripentaerythritol hexa(meth)acrylate, epoxy Propane modified dipentaerythritol hexa(meth)acrylate, propylene oxide modified tripentaerythritol hexa(meth)acrylate, etc.

Examples of 7-functional (meth)acrylate monomers include: tripentaerythritol hepta (meth)acrylate, the reaction product of tripentaerythritol hepta (meth)acrylate and acid anhydride, and caprolactone-modified tripentaerythritol hepta( Meth) acrylate, caprolactone modified tripentaerythritol hepta(meth)acrylate and acid anhydride reactant, ethylene oxide modified tripentaerythritol hepta(meth)acrylate, ethylene oxide modified tripentaerythritol The reactant of hepta(meth)acrylate and acid anhydride, the reactant of propylene oxide modified tripentaerythritol hepta(meth)acrylate, the reactant of propylene oxide modified tripentaerythritol hepta(meth)acrylate and acid anhydride, etc.

An 8-functional (meth)acrylate monomer system has 8 (meth)acryloyloxy groups in the molecule. As examples, examples include: tripentaerythritol octa(meth)acrylate, caprolactone modified Tripentaerythritol octa(meth)acrylate, ethylene oxide modified tripentaerythritol octa(meth)acrylate, propylene oxide modified tripentaerythritol octa(meth)acrylate, etc. These polyfunctional (meth)acrylate compounds can be used individually or in combination of 2 or more types.

In one embodiment of the present invention, the number of (meth)acrylic groups in the multifunctional (meth)acrylate compound is preferably 6 or less. If the number of (meth)acrylic groups is 6 or less, the cross-linking density is reduced and a cross-linked structure favorable for bending can be formed. Therefore, it is easier to improve the flexibility of the polarizing film. In addition, heat resistance can be further improved.

Examples of the polyfunctional (meth)acrylate compound having a number of (meth)acryloyl groups of 6 or less include the above-mentioned bifunctional (meth)acrylate monomers having two (meth)acryloyloxy groups in the molecule. 3-6 functional (meth)acrylate monomers having 3-6 (meth)acryloxy groups in the molecule, etc.

In one embodiment of the present invention, from the viewpoint of controlling the crosslinking density and improving the adhesion and flexibility, the polyfunctional (meth)acrylate compound has a branched structure, and connects the closest branched structure The number of atoms of the branch point of the (meth)acryloyl group and the chain of the (meth)acryloyl group (sometimes referred to as the linking chain) is preferably 2 or more, more preferably 4 or more, and still more preferably 7 the above. If the number of atoms is less than or equal to the above upper limit, the crosslinking density of the first resin layer or the second resin layer is reduced, and the flexibility of the polarizing film is easily improved. Here, when there are a plurality of the connecting chains, at least one connecting chain should satisfy the above-mentioned atomic number range. From the viewpoint of improving flexibility, it is preferable that all connecting chains satisfy the above-mentioned atomic number range. .

Among the above-mentioned polyfunctional (meth)acrylate compounds, from the viewpoint of the adhesion and flexibility of the polarizing film, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, Ethylene oxide modified tripentaerythritol hexa(meth)acrylate, propylene oxide modified dipentaerythritol hexa(meth)acrylate, propylene oxide modified tripentaerythritol hexa(meth)acrylate, more preferably cyclic Oxyethane modified dipentaerythritol hexa(meth)acrylate.

When the first curable composition or the second curable composition contains a polyfunctional (meth)acrylate compound, the content of the polyfunctional (meth)acrylate compound is relative to the solid form of the curable composition 100 parts by mass, preferably 50 parts by mass or more, more preferably 60 parts by mass or more, still more preferably 70 parts by mass or more, preferably 95 parts by mass or less, still more preferably 90 parts by mass or less . If the content of the polyfunctional (meth)acrylate compound is in the above range, it is easy to improve the adhesion, flexibility, and heat resistance between the layers of the polarizing film. Furthermore, in this specification, the so-called solid component of the curable composition, when a solvent is included in the curable composition, means the total amount of the components obtained by removing the solvent from the curable composition.

In the case where the first curable composition or the second curable composition contains a multifunctional (meth)acrylate compound and a urethane (meth)acrylate compound, it is preferably 95: 5-50:50, more preferably 90:10-70:30 ratio (multifunctional (meth)acrylate compound: urethane (meth)acrylate compound, mass ratio) containing polyfunctional (meth) Yl)acrylate compound and urethane (meth)acrylate compound. By including the polyfunctional (meth)acrylate compound and the urethane (meth)acrylate compound in the above-mentioned mixing ratio, it is easy to improve the adhesion, flexibility, and heat resistance of the polarizing film.

The first curable composition or the second curable composition may contain a (meth)acrylic compound other than the urethane (meth)acrylate compound and the polyfunctional (meth)acrylate compound. Examples of such (meth)acrylic compounds include epoxy (meth)acrylate compounds; carboxyl modified epoxy (meth)acrylate compounds; (meth)acrylic polyester compounds; monofunctional ( Meth)acrylate compounds and the like. These can be used individually or in combination of 2 or more types.

The monofunctional (meth)acrylate compound may be a monomer, oligomer, or polymer, and among these, a monofunctional (meth)acrylate monomer can be suitably used. Examples of monofunctional (meth)acrylate monomers include: methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, Isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate , 2- or 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxy (meth)acrylate Ethyl propyl ester, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, ethyl carbitol (meth)acrylate, 2-phenoxyethyl (meth)acrylate , Phenoxy polyethylene glycol (meth)acrylate, 2-(N,N-dimethylamino)ethyl (meth)acrylate, 2-carboxyethyl (meth)acrylate, phthalic acid 1-[2-(meth)propenoxyethyl] formate, 1-[2-(meth)propenoxyethyl] hexahydrophthalate, 1-[2- succinate (Meth) propylene oxyethyl] ester and trimellitic acid 4-[2-(meth) propylene oxyethyl] ester, tetrahydrofurfuryl (meth)acrylate, (meth)acrylic acid Dicyclopentyl ester and (meth)acrylate dicyclopentenyl acid etc. A monofunctional (meth)acrylate monomer can be used individually or in combination of 2 or more types.

When the first curable composition or the second curable composition contains a monofunctional (meth)acrylate compound, the content of the monofunctional (meth)acrylate compound is relative to the solid content of the curable composition 100 parts by mass of the ingredients are preferably 5 parts by mass or more, more preferably 20 parts by mass or more, and preferably 50 parts by mass or less. If the content of the monofunctional (meth)acrylate compound is in the above range, the coating properties are improved from the viewpoint of viscosity adjustment of the curable composition.

等9-氧硫𠮿

系起始劑；雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦等醯基氧化膦系起始劑；此外之氧雜蒽酮、茀酮、樟腦醌、苯甲醛、蒽醌等。該等自由基聚合起始劑可單獨使用或組合兩種以上而使用。From the viewpoint of improving curability, it is preferable that at least one of the first curable composition and the second curable composition, and it is preferable that both contain a radical polymerization initiator. The radical polymerization initiator is not particularly limited as long as it is capable of starting the curing of the curable compound by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams. Specific examples thereof include benzene. Ethyl ketone, 3-methylacetophenone, benzil dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-methyl -1-[4-(Methylthio)phenyl]-2-morpholinopropane-1-one and 2-hydroxy-2-methyl-1-phenylpropane-1-one and other acetophenone series Starter; Benzophenone-based initiators such as benzophenone, 4-chlorobenzophenone and 4,4'-diaminobenzophenone; 2,2-Dimethoxy-1,2 -Diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl ketone and other alkyl phenone-based initiators; benzoin propyl ether and benzoin ethyl ether and other benzoin ether-based initiators; 4-isopropyl- 9-oxysulfur 𠮿

Wait 9-oxysulfur 𠮿

Initiator; Bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide and other phosphine oxide initiators; In addition, xanthones, quinones, camphorquinones, benzene Formaldehyde, anthraquinone, etc. These radical polymerization initiators can be used alone or in combination of two or more kinds.

When the first curable composition or the second curable composition contains a radical polymerization initiator, the content of the radical polymerization initiator is preferably relative to 100 parts by mass of the solid content of the curable compound It is 1-10 parts by mass, more preferably 2-8 parts by mass. If the content of the radical polymerization initiator is more than the above lower limit, the polymerization initiation ability is sufficiently exhibited and the curability is improved. On the other hand, if the content of the polymerization initiator is equal to or less than the above upper limit, the radical polymerization initiator is unlikely to remain and it is easy to suppress the decrease in visible light transmittance.

The first curable composition or the second curable composition may contain other additives other than the radical polymerization initiator as necessary, such as ultraviolet absorbers, antistatic agents, stabilizers, antioxidants, colorants, and surface regulators Wait. Other additives can be used alone or in combination of two or more. The content of other additives is preferably about 0.1-20% by mass relative to the mass of the solid content of the curable composition.

The first curable composition or the second curable composition can be prepared by mixing a (meth)acrylic compound and, if necessary, additives and stirring. Moreover, in order to improve coatability, viscosity adjustment may be performed by adding a solvent to the first curable composition or the second curable composition.

The solvent may be any solvent that can dissolve the components constituting the first curable composition or the second curable composition, for example, aliphatic hydrocarbons such as hexane and octane; aromatic hydrocarbons such as toluene and xylene; ethanol, Alcohol solvents such as 1-propanol, isopropanol, and 1-butanol; ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate, butyl acetate, and isobutyl acetate; B Glycol ether solvents such as glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc.; ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate Among the esterified glycol ether solvents, etc., it is appropriately selected and used. These solvents can be used alone or in combination of two or more. The type and content of the solvent are appropriately selected according to the type or content, shape, coating method, thickness of the resin layer, etc. of the components contained in the first curable composition or the second curable composition, for example, regarding the content of the solvent , Relative to 100 parts by mass of the solid content of the curable composition, preferably 3 to 1000 parts by mass, more preferably 5 to 100 parts by mass, and still more preferably 7 to 80 parts by mass.

In an embodiment of the present invention, the first resin layer can be obtained by coating the first curable composition on the polarizing element or the release film to harden the composition. The second resin layer can be obtained by applying a second curable composition on a substrate, a release film, or an alignment film, and curing the composition.

As a coating method of the 1st curable composition or the 2nd curable composition, the coating method exemplified in the section of <Polarizer> can be mentioned. In addition, the curing of the curable composition is preferably performed by irradiating active energy rays to polymerize polymerizable components such as (meth)acrylic compounds contained in the composition. The active energy rays are appropriately selected according to the types of polymerizable components such as (meth)acrylic compounds, the types of radical polymerization initiators, and the amounts thereof. As a specific example, one or more active energy rays selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays can be cited. Among them, in terms of easy control of the progress of the polymerization reaction, or in terms of being used as a photopolymerization device by a wide range of users in the field, ultraviolet light is preferred. As the light source of the active energy ray, the light sources exemplified in the section of <Polarizing Element> can be cited. As long as the ultraviolet irradiation intensity, irradiation time, and accumulated light amount are appropriately used, the ranges of ultraviolet irradiation intensity, irradiation time, and accumulated light amount exemplified in the section of <Polarizing Element> can be used appropriately.

The thickness of the first resin layer and the second resin layer is preferably 0.1-10 μm, more preferably 0.2-5 μm, and still more preferably 0.3-3 μm. If the thickness of the first resin layer or the second resin layer is in the above range, the adhesion between the first resin layer and the polarizing element and the adhesion between the second resin layer and the alignment film are easily improved, and the flexibility is easily improved.

＜Polarizing film＞ As described above, the polarizing film of the present invention has excellent adhesion between the layers, and can further exhibit excellent heat resistance. Furthermore, in a suitable aspect, in addition to adhesion and flexibility, it can also have excellent heat resistance, so even in a high-temperature environment, the diffusion of the dichroic dye contained in the polarizing element can be effectively suppressed. Therefore, the polarizing film of the present invention can be suitably used for display devices such as organic EL (Electroluminescence) display devices or touch panel display devices.

The manufacturing method of the polarizing film of the present invention is not particularly limited as long as the first resin layer, the polarizing element, the alignment film, and the second resin layer can be sequentially laminated. For example, a method including the following steps: forming a second resin layer, An alignment film is formed on the second resin layer, and a polarizing element is formed on the alignment film to obtain a layered body in which a second resin layer, an alignment film, and a polarizing element are sequentially laminated, on the polarizing element surface of the layered body, The first curable composition is applied or overlapped, and the first curable composition is cured.

In a suitable embodiment of the present invention, the polarizing film of the present invention is manufactured by a method including the following steps: a layered body in which a second resin layer, an alignment film, and a polarizing element are laminated on a release film The surface of the polarizing element is coated with the first curable composition, and active energy rays are irradiated from the side of the first curable composition to cure the first curable composition, thereby obtaining a release film, a second resin layer, and A laminate of the alignment film, the polarizing element, and the first resin layer, and the release film is peeled from the laminate.

In a suitable embodiment of the present invention, the polarizing film of the present invention is manufactured by a method including the following steps: a first curable composition formed on a release film and a second resin layered in sequence Layers, alignment films, and polarizing elements are laminated on the polarizing element surface, and active energy rays are irradiated from the release film side to harden the first curable composition, thereby obtaining a release film and a first resin layer laminated in sequence , A laminate of a polarizing element, an alignment film, and a second resin layer, and the release film is peeled from the laminate.

The polarizing film of the present invention only needs to laminate the first resin layer, the polarizing element, the alignment film, and the second resin layer in this order. As long as the effect of the present invention is not impaired, it is placed on the side of the first resin layer opposite to the polarizing element side The surface of the second resin layer, the surface of the second resin layer opposite to the side of the alignment film, or the functional layer may be included between the layers. Examples of the functional layer include an ultraviolet absorbing layer, a hard coat layer, a primer layer, a gas barrier layer, a hue adjustment layer, a refractive index adjustment layer, an anti-reflection layer, an antistatic layer, an adhesive layer, and an adhesive layer. These functional layers can be used alone or in combination of two or more.

[Polarizer] The polarizing film of the present invention can also be combined with a retardation film to form a polarizing plate. That is, the polarizing plate in the present invention includes the above-mentioned polarizing film and retardation film. The retardation film can be laminated on the surface of the first resin layer or the surface of the second resin layer of the polarizing film via an adhesive layer or an adhesive layer, for example. It is preferable to laminate the retardation axis (optical axis) of the retardation film and the absorption axis of the polarizing film (polarizing element) so as to be substantially 45°. By stacking the retardation axis (optical axis) of the retardation film and the absorption axis of the polarizing film (polarizing element) so that it becomes substantially 45°, the function as an elliptical polarizing plate can be obtained. Furthermore, the so-called substantially 45° is usually in the range of 45±5°.

In the polarizing plate, the retardation film preferably satisfies the following formula (X): 100≦Re(550)≦180 (X) [In the formula, Re(550) represents the in-plane retardation value at a wavelength of 550 nm]. If the retardation film has the in-plane retardation value indicated by (X) above, it functions as a so-called λ/4 plate. The above formula (X) is preferably 100 nm≦Re(550)≦180 nm, and more preferably 120 nm≦Re(550)≦160 nm.

Furthermore, the retardation film preferably satisfies the following formula (Y): Re(450)/Re(550)<1 (Y) [In the formula, Re(450) and Re(550) represent the in-plane retardation values at wavelengths of 450 nm and 550 nm, respectively]. The retardation film that satisfies the above formula (Y) has so-called inverse wavelength dispersion and exhibits excellent polarization performance. The value of Re(450)/Re(550) is preferably 0.93 or less, more preferably 0.88 or less, still more preferably 0.86 or less, and preferably 0.80 or more, more preferably 0.82 or more.

The above-mentioned retardation film may be a stretched film that imparts a retardation by stretching a polymer. From the viewpoint of thinning the polarizing plate, it is preferably a polymerizable liquid crystal composition composed of a polymer containing a polymerizable liquid crystal compound (Hereinafter, it is also referred to as a polymerizable liquid crystal composition (B)). In the above retardation film, the polymerizable liquid crystal compound is usually polymerized in an aligned state. The polymerizable liquid crystal compound (hereinafter, also referred to as "polymerizable liquid crystal compound (B)") forming the retardation film refers to a liquid crystal compound having a polymerizable functional group, especially a photopolymerizable functional group. The so-called photopolymerizable functional group refers to a group that can participate in a polymerization reaction by using active radicals or acids generated by a photopolymerization initiator. Examples of photopolymerizable functional groups include vinyl groups, vinyloxy groups, 1-chlorovinyl groups, isopropenyl groups, 4-vinylphenyl groups, acryloxy groups, methacryloxy groups, and oxirane groups. , Oxetanyl, etc. Among them, propyleneoxy group, methacryloxy group, ethyleneoxy group, oxirane group and oxetanyl group are preferred, and propyleneoxy group is more preferred. The liquid crystallinity may be either a thermotropic liquid crystal or a liquid crystal. As a phase order structure, it may be a nematic liquid crystal or a smectic liquid crystal. As the polymerizable liquid crystal compound, only one type may be used, or two or more types may be used in combination.

As the polymerizable liquid crystal compound (B), from the viewpoint of ease of film formation and imparting retardation represented by the above formula (Y), compounds satisfying all of the following (a) to (d) can be cited.

(a) A compound having thermotropic liquid crystal properties. (b) It has π electrons in the long axis direction (a) of the polymerizable liquid crystal compound. (c) There are π electrons in the direction crossing the long axis direction (a) [crossing direction (b)]. (d) Let the total of π electrons existing in the long axis direction (a) be N(πa), and let the total of the molecular weights existing in the long axis direction be N(Aa), which is represented by the following formula (i) The defined π electron density in the long axis direction (a) of the polymerizable liquid crystal compound: D(πa)=N(πa)/N(Aa) (i), and Let the total of π electrons existing in the cross direction (b) be N(πb), and let the total of the molecular weights existing in the cross direction (b) be N(Ab) and be defined by the following formula (ii) Π electron density in the cross direction (b) of the polymerizable liquid crystal compound: D(πb)=N(πb)/N(Ab) (ii) In 0≦[D(πa)/D(πb)]≦1 The relationship [that is, the π electron density in the cross direction (b) is greater than the π electron density in the long axis direction (a)]. Furthermore, the polymerizable liquid crystal compound (B) that satisfies all of the above (a) to (d) can be formed into nematic by coating on an alignment film formed by rubbing treatment, and heating it to a phase transition temperature or higher. phase. In the nematic phase formed by the alignment of the polymerizable liquid crystal compound (B), the alignment is usually performed such that the long axis directions of the polymerizable liquid crystal compound become parallel to each other, and the long axis direction becomes the alignment direction of the nematic phase .

。 上述式(II)所表示之化合物可單獨使用或組合兩種以上而使用。The polymerizable liquid crystal compound (B) having the above-mentioned characteristics usually shows reverse wavelength dispersion in many cases. As a compound satisfying the characteristics of the above (a) to (d), specifically, for example, a compound represented by the following formula (II) can be cited:

. The compound represented by the above formula (II) can be used alone or in combination of two or more kinds.

In formula (II), Ar represents a divalent aromatic group which may have a substituent. The aromatic group here is a group with a planar cyclic structure, and refers to the number of π electrons in the cyclic structure is [4n+2] according to Shocker's rule. Here, n represents an integer. When a ring structure is formed by including heteroatoms such as -N= or -S-, the shocker's rule is satisfied including non-covalent bond electron pairs on these heteroatoms, and it is also included in the case of aromaticity . In the divalent aromatic group, it is preferable to include at least one of a nitrogen atom, an oxygen atom, and a sulfur atom.

In formula (II), G ¹ and G ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 4 carbons, a fluoroalkyl group having 1 to 4 carbons, and 1 to 4 of alkoxy, cyano or nitro, the carbon atoms constituting the divalent aromatic group or divalent alicyclic hydrocarbon group may be substituted with oxygen atoms, sulfur atoms or nitrogen atoms.

In formula (II), L ¹ , L ² , B ¹ and B ² are each independently a single bond or a divalent linking group.

In the formula (II), k and l each independently represent an integer of 0 to 3, and satisfy the relationship of 1≦k+1. Here, in the case of 2≦k+1, B ¹ and B ² , G ¹ and G ² may be the same or different from each other.

In formula (II), E ¹ and E ² each independently represent an alkanediyl group having 1 to 17 carbon atoms. Here, the hydrogen atom contained in the alkanediyl group may be substituted by a halogen atom, and the alkanediyl group contains The -CH ₂ -can be substituted with -O-, -S-, -Si-. P ¹ and P ² independently represent a polymerizable group or a hydrogen atom, and at least one of them is a polymerizable group.

In formula (II), G ¹ and G ² are independent of each other, and preferably are 1,4-extension which can be substituted with at least one substituent selected from the group consisting of halogen atoms and alkyl groups with 1 to 4 carbon atoms. Phenyldiyl, 1,4-cyclohexanediyl which may be substituted with at least one substituent selected from the group consisting of halogen atoms and alkyl groups with 1 to 4 carbon atoms, more preferably substituted by methyl 1,4-phenylenediyl, unsubstituted 1,4-phenylenediyl, or unsubstituted 1,4-trans-cyclohexanediyl, especially unsubstituted 1,4-Phenylenediyl or unsubstituted 1,4-trans-cyclohexanediyl. In addition, at least one of G ¹ and G ² in which there are plural is preferably a divalent alicyclic hydrocarbon group, and at least one of G ¹ and G ² bonded to L ¹ or L ^{2 is} more preferably Divalent alicyclic hydrocarbon group.

In formula (II), L ¹ and L ² are each independently preferably a single bond, an alkylene having 1 to 4 carbon atoms, -O-, -S-, -R ^a1 OR ^a2 -, -R ^a3 COOR ^a4 -, -R ^a5 OCOR ^a6 -, R ^a7 OC=OOR ^a8 -, -N=N-, -CR ^c =CR ^d -, or C≡C-. Here, R ^a1 to R ^a8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, and R ^c and R ^d represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. L ¹ and L ² are each independently more preferably a single bond, -OR ^a2-1 -, -CH ₂ -, -CH ₂ CH ₂ -, ^{-COOR a4-1} -, or OCOR ^a6-1 -. ^{Here, R a2-1, R a4-1, R} a6-1 each independently represent a single bond, -CH ₂ - of any one of -, - CH ₂ CH _2. L ¹ and L ² are each independently a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, or OCO-.

In a suitable embodiment of the present invention, at least one of G ¹ and G ² in formula (II) is a divalent alicyclic hydrocarbon group, and the divalent alicyclic hydrocarbon group can be used as a substituted A polymerizable liquid crystal compound in which the bivalent aromatic group Ar is bonded to L ¹ and/or L ^{2 of} -COO-.

In formula (II), B ¹ and B ² are each independently preferably a single bond, an alkylene having 1 to 4 carbon atoms, -O-, -S-, -R ^a9 OR ^a10 -, -R ^a11 COOR ^a12 -, -R ^a13 OCOR ^a14 -, or R ^a15 OC=OOR ^a16 -. Here, ^Ra9 to ^Ra16 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms. B ¹ and B ² are each independently more preferably a single bond, -OR ^a10-1 -, -CH ₂ -, -CH ₂ CH ₂ -, ^{-COOR a12-1} -, or OCOR ^a14-1 -. Here, R ^a10-1 , R ^a12-1 and R ^a14-1 each independently represent any one of a single bond, -CH ₂ -, and -CH ₂ CH ₂ -. B ¹ and B ² are each independently a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, -OCO-, or OCOCH ₂ CH ₂ -.

In formula (II), k and l are preferably in the range of 2≦k+1≦6 from the viewpoint of inverse wavelength dispersion performance, preferably k+1=4, and more preferably k=2 and l=2. If k=2 and l=2, it becomes a symmetrical structure, so it is more preferable.

In formula (II), E ¹ and E ² are each independently preferably an alkanediyl group having 1 to 17 carbon atoms, and more preferably an alkanediyl group having 4 to 12 carbon atoms.

In the formula (II), examples of the polymerizable group represented by P ¹ or P ² include epoxy, vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, Allyloxy, methacryloxy, oxiranyl, and oxetanyl groups. Among these, propyleneoxy group, methacryloxy group, ethyleneoxy group, oxirane group and oxetanyl group are preferred, and propyleneoxy group is more preferred.

In the formula (II), Ar preferably has at least one selected from the group consisting of an optionally substituted aromatic hydrocarbon ring, an optionally substituted aromatic heterocyclic ring, and an electron withdrawing group. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring, and a benzene ring and a naphthalene ring are preferred. Examples of the aromatic heterocyclic ring include furan ring, benzofuran ring, pyrrole ring, indole ring, thiophene ring, benzothiophene ring, pyridine ring, pyridine ring, pyrimidine ring, triazole ring, and triazole ring. , Pyrroline ring, imidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, thienothiazole ring, azole ring, benzoazole ring, and phenanthroline ring. Among these, it is preferable to have a thiazole ring, a benzothiazole ring, or a benzofuran ring, and it is more preferable to have a benzothiazolyl group. In addition, when a nitrogen atom is contained in Ar, the nitrogen atom preferably has π electrons.

In the formula (II), the total number N _π of the π electrons contained in the divalent aromatic group represented by Ar is preferably 8 or more, more preferably 10 or more, still more preferably 14 or more, and particularly preferably 16 the above. Moreover, it is preferably 30 or less, more preferably 26 or less, and still more preferably 24 or less.

Examples of the aromatic group represented by Ar include groups of the following formulas (Ar-1) to (Ar-23).

In formulas (Ar-1) to (Ar-23), the * mark indicates the connecting portion, and Z ⁰ , Z ¹ and Z ² each independently indicate a hydrogen atom, a halogen atom, an alkyl group with 1 to 12 carbon atoms, and a cyano group , Nitro, C1-C12 alkylsulfinyl group, C1-C12 alkylsulfinyl group, carboxyl group, C1-C12 fluoroalkyl group, C1-C6 alkoxy group , Alkylthio with 1-12 carbons, N-alkylamino with 1-12 carbons, N,N-dialkylamino with 2-12 carbons, N-alkyl with 1-12 carbons Sulfamoyl or N,N-dialkyl sulfamoyl with 2-12 carbon atoms.

The formula (Ar-1) in the formula - (Ar-23), Q ¹ and Q ² each independently represent ^{-CR 2 'R 3' -,} - S -, - NH -, - NR 2 '-, - CO- or O-, R ^{2 'and} R ^3' each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms of.

In formulas (Ar-1) to (Ar-23), J ¹ and J ² each independently represent a carbon atom or a nitrogen atom.

In formulas (Ar-1) to (Ar-23), Y ¹ , Y ² and Y ³ each independently represent a substituted aromatic hydrocarbon group or aromatic heterocyclic group.

In formulas (Ar-1) to (Ar-23), W ¹ and W ² each independently represent a hydrogen atom, a cyano group, a methyl group, or a halogen atom, and m represents an integer of 0-6.

Examples of the aromatic hydrocarbon groups in Y ¹ , Y ² and Y ³ include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl, naphthyl, anthryl, phenanthryl, and biphenyl. Preferred is phenyl, Naphthyl is more preferably phenyl. Examples of the aromatic heterocyclic group include furyl, pyrrolyl, thienyl, pyridyl, thiazolyl, benzothiazolyl and the like, which contain at least one heteroatom such as a nitrogen atom, an oxygen atom, and a sulfur atom, with carbon numbers of 4 to The aromatic heterocyclic group of 20 is preferably furyl, thienyl, pyridyl, thiazolyl, and benzothiazolyl.

Y ¹ and Y ² may each independently be a substituted polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group. The polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic assembly ring. The polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from an aromatic assembly ring.

In formulas (Ar-1) to (Ar-23), Z ⁰ , Z ¹ and Z ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbons, a cyano group, a nitro group, An alkoxy group having 1 to 12 carbons, Z ^{0 is} more preferably a hydrogen atom, an alkyl group having 1 to 12 carbons, or a cyano group, and Z ¹ and Z ^{2 are} more preferably a hydrogen atom, a fluorine atom, or a chlorine atom , Methyl, cyano.

The formula (Ar-1) in the formula - (Ar-23), Q ¹ and Q ² is preferably -NH -, - S -, - NR 2 '-, - O-, R 2' is preferably a hydrogen atom. Among them, -S-, -O-, and -NH- are particularly preferred.

Among the formulas (Ar-1) to (Ar-23), the formula (Ar-6) and the formula (Ar-7) are preferred from the viewpoint of molecular stability.

In formulas (Ar-17) to (Ar-23), Y ¹ can form an aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z ⁰ . Examples of the aromatic heterocyclic group include those described above as the aromatic heterocyclic ring that Ar may have, such as pyrrole ring, imidazole ring, pyrroline ring, pyridine ring, pyridine ring, pyrimidine ring, and indole Dole ring, quinoline ring, isoquinoline ring, purine ring, pyrrolidine ring, etc. The aromatic heterocyclic group may have a substituent. In addition, Y ¹ may be the above-mentioned substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z ⁰ . For example, a benzofuran ring, a benzothiazole ring, a benzoxazole ring, etc. are mentioned. In addition, the compound represented by the above formula (II) can be produced, for example, according to the method described in JP 2010-31223 A.

The content of the polymerizable liquid crystal compound (B) in the polymerizable liquid crystal composition (B) constituting the retardation film is, for example, 70-99.5 mass parts relative to 100 parts by mass of the solid content of the polymerizable liquid crystal composition (B) Parts, preferably 80 to 99 parts by mass, more preferably 90 to 98 parts by mass. If the content is within the above range, the orientation of the retardation film tends to increase. Here, the solid content refers to the total amount of the components obtained by removing volatile components such as solvents from the polymerizable liquid crystal composition (B).

The polymerizable liquid crystal composition (B) may also contain a polymerization initiator for starting the polymerization reaction of the polymerizable liquid crystal compound (B). As a polymerization initiator, it can be appropriately selected and used from previous users in the field. It can be a thermal polymerization initiator or a photopolymerization initiator, which can start the polymerization reaction under lower temperature conditions. From the aspect, a photopolymerization initiator is preferable. The same ones as those exemplified above as the photopolymerization initiator that can be used in the composition for forming a polarizing element can be suitably cited. In addition, the polymerizable liquid crystal composition (B) may contain a photosensitizer, a leveling agent, and additives exemplified as additives contained in the composition for forming a polarizing element as necessary. As the photosensitizer and the leveling agent, the same as those exemplified above as a user that can be used in the composition for forming a polarizing element can be mentioned.

The polymerizable liquid crystal composition (B) is prepared, for example, by mixing and stirring the polymerizable liquid crystal compound (B), a polymerization initiator, additives, etc., if necessary. In addition, in order to improve coatability, a solvent may be added to the polymerizable liquid crystal composition (B) to adjust the viscosity. Examples of the solvent include the solvents exemplified above as the solvent contained in the composition for forming a polarizing element.

In the retardation film, the polymerizable liquid crystal composition (B) can be coated on the substrate or the alignment film, the solvent can be removed by drying, and the polymerizable liquid crystal compound in the obtained coating film can be made by heating and/or active energy rays (B) Obtained by hardening. As the alignment film, the same as those exemplified above as a user who can be used when manufacturing the polarizing element of the present invention can be cited.

The solvent used in the composition for forming a retardation film, the coating method of the composition for forming a retardation film, the curing conditions using active energy rays, etc. can be exemplified by those that can be used in the method of manufacturing the polarizing element of the present invention Same thing.

The thickness of the retardation film can be appropriately selected according to the applied display device. From the viewpoints of thinning and flexibility, it is preferably 0.1 to 10 μm, more preferably 1 to 5 μm, and still more preferably 1 to 3 μm.

The polarizing plate in the present invention may include a polarizing film, a retardation film, and an adhesive layer or other layers such as a protective film. In a preferred aspect, regarding the polarizing plate of the present invention, the polarizing film and the retardation film are bonded via an adhesive layer or an adhesive layer.

Regarding the thickness of the polarizing plate of the present invention, from the viewpoint of flexibility or visibility of the display device, it is preferably 1-100 μm, more preferably 2-70 μm, and still more preferably 3-60 μm.

The polarizing film or polarizing plate of the present invention may have a front panel. A schematic cross-sectional view of the layer composition of the polarizing film with the front panel in one embodiment of the present invention is shown in FIG. 1. The polarizing film 1 with a front panel has a front panel 3 formed on the first resin layer 4 of the polarizing film 2. The polarizing film 2 has a first resin layer 4, a polarizing element 5, an alignment film 6, and a second resin layer 7 laminated in this order from the front panel 3 side. The polarizing film 1 with a front panel can impart surface hardness and light resistance by having a front panel. Furthermore, the polarizing film 1 with the front panel may also form an adhesive layer or an adhesive layer between the front panel 3 and the first resin layer 4.

A schematic cross-sectional view of the layer structure of the polarizing plate with the front panel in one embodiment of the present invention is shown in FIG. 2. The polarizing plate 8 with a front panel has a front panel 3 formed on the polarizing plate 9. In the polarizing plate 9, a first resin layer 4, a polarizing element 5, an alignment film 6, a second resin layer 7, and a retardation film 10 are laminated in this order from the front panel 3 side. The polarizing plate 8 with a front panel can impart surface hardness and light resistance by having a front panel. Furthermore, the polarizing plate 8 with the front panel may form an adhesive layer or an adhesive layer between the front panel 3 and the first resin layer 4 and/or between the second resin layer 7 and the retardation film 10. Furthermore, in FIG. 1 and FIG. 2, in order to make the drawings easy to observe, the size or ratio of each layer may be appropriately different.

A schematic cross-sectional view of the layer composition of the polarizing film with the front panel in another embodiment of the present invention is shown in FIG. 3. The polarizing film 11 with a front panel has a front panel 3 formed on the second resin layer 7 of the polarizing film 2. The polarizing film 2 has a second resin layer 7, an alignment film 6, a polarizing element 5, and a first resin layer 4 laminated in this order from the front panel 3 side. The polarizing film 11 with a front panel can impart surface hardness and light resistance by having a front panel. Furthermore, the polarizing film 11 with the front panel may also form an adhesive layer or an adhesive layer between the front panel 3 and the second resin layer 7.

A schematic cross-sectional view of the layer structure of a polarizing plate with a front panel in another embodiment of the present invention is shown in FIG. 4. The polarizing plate 12 with a front panel has a front panel 3 formed on the polarizing plate 13. The polarizing plate 13 has a second resin layer 7, an alignment film 6, a polarizing element 5, a first resin layer 4, and a retardation film 10 laminated in this order from the front panel 3 side. The polarizing plate 13 with a front panel can impart surface hardness and light resistance by having a front panel. Furthermore, the polarizing plate 13 with the front panel may form an adhesive layer or an adhesive layer between the front panel 3 and the second resin layer 7 and/or between the first resin layer 4 and the retardation film 10. Furthermore, in FIG. 3 and FIG. 4, in order to make the drawings easy to observe, the size or ratio of each layer may be appropriately different.

＜Display device＞ The polarizing film of the present invention or the above-mentioned polarizing plate can be applied to a display device. The display device can be obtained, for example, by bonding the polarizing film of the present invention or the above-mentioned polarizing plate to the surface of the display device via an adhesive layer or an adhesive layer. The so-called display device is a device with a display mechanism and includes a light-emitting element or a light-emitting device as a light-emitting source. Examples of display devices include: liquid crystal display devices, organic electroluminescence (EL) display devices, inorganic electroluminescence (EL) display devices, touch panel display devices, electron emission display devices (field emission display devices (FED, etc.) , Surface field emission display device (SED)), electronic paper (display device using electronic ink or electrophoresis element), plasma display device, projection display device (grating light valve (GLV) display device, device with digital micromirror (DMD) display devices, etc.) and piezoelectric ceramic displays. Liquid crystal display devices also include any one of transmissive liquid crystal display devices, semi-transmissive liquid crystal display devices, reflective liquid crystal display devices, direct-view liquid crystal display devices, and projection liquid crystal display devices. The display devices may be display devices that display 2-dimensional images, or stereoscopic display devices that display 3-dimensional images. In particular, as the display device of the present invention, an organic EL display device and a touch panel display device are preferable, and an organic EL display device is particularly preferable. [Example]

Hereinafter, examples and comparative examples are shown to further specifically explain the present invention, but the present invention is not limited by these examples. Hereinafter, the parts and% representing the usage amount, content, and% are based on quality unless otherwise specified.

＜Evaluation of adhesion＞ The surface of the second resin layer of the polarizing film obtained in the Examples and Comparative Examples was attached to the glass via a pressure-sensitive adhesive, and a transparent tape (trade name Sellotape; Sellotape was attached to the surface of the first resin layer opposite to the glass surface; Nichiban company (manufactured by Nichiban Co.) was followed by a peel test to evaluate the adhesion of the polarizing film. The case where the peeling phenomenon was confirmed inside the polarizing film was evaluated as "×", and the case where the peeling phenomenon could not be confirmed was evaluated as "○".

＜Evaluation of heat resistance＞ The polarization degree Py and the monomer transmittance Ty of the polarizing films obtained in the examples and comparative examples were measured in the following manner. In the wavelength range from 380 nm to 780 nm, it is used in a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation) with a folder with a polarizing element installed, and the transmission is measured by the double beam method The transmittance in the axial direction (Ta) and the transmittance in the absorption axis (Tb). Regarding the clamp, the reference side is provided with a screen that cuts off 50% of the light. Use the following equations (Equation 1) and (Equation 2) to calculate the transmittance and polarization of the monomer at each wavelength, and then use the 2 degree field of view (C light source) of JIS Z 8701 to correct the visual sensitivity and calculate the visual sensitivity The monomer transmittance (Ty) and visual sensitivity are corrected to correct the polarization (Py). Monomer transmittance Ty(%)=(Ta＋Tb)/2 (Equation 1) Polarization Py(%)=(Ta－Tb)/(Ta＋Tb)×100 (Equation 2)

After heating the polarizing films obtained in the Examples and Comparative Examples at 85°C for 240 hours under dry conditions, the polarization degree Py and the monomer transmittance Ty of the polarizing film were measured again to calculate the change in Py before and after the heat resistance test ΔPy( = Py after the heat resistance test-Py before the heat resistance test), and the change in Ty before and after the heat resistance test ΔTy (= Ty after the heat resistance test-Ty before the heat resistance test).

＜Evaluation of Flexibility＞ The evaluation of the bendability was performed in the following manner using the general test method for coatings described in JIS-K-5600-5-1-bending resistance (cylindrical mandrel method). The polarizing films obtained in the examples and comparative examples were cut into 25 mm×200 mm squares, and a cylindrical mandrel method bending resistance tester type II (manufactured by TP Giken Co., Ltd.) was used at a temperature of 25°C and relative Under the condition of humidity 55%RH, the cut film is wound on a mandrel rod with a diameter of 2 mm (bending radius R = 1 mm) so that the hardened layer of the first resin layer forming composition becomes the outside , And conduct a bending test. The film after the test was used to visually confirm the occurrence of cracks in a darkroom environment with illuminated transmitted light. As a result, the crack was judged as "×" and the crack could not be judged as "○".

＜Film thickness of each layer＞ The thickness of the polarizing element, the alignment film, the first resin layer and the second resin layer are measured using a laser microscope (OLS3000 manufactured by Olympus Co., Ltd.).

[Manufacturing Examples 1-7] <Preparation of compositions (A) to (G) for forming resin layers> The respective components described in Table 1 were mixed and stirred at 50°C for 4 hours to obtain resin layer forming compositions (A) to (G), respectively.

[Manufacturing Example 8] <Preparation of composition (H) for forming resin layer> The composition (H) for forming a resin layer was obtained by mixing the following components and stirring at 23°C for 4 hours. ・Celloxide 2021P: 70 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (manufactured by Daicel Chemical Co., Ltd.) ・30 parts of 2-ethylhexyl glycidyl ether ・CPI-100P: Triaryl hexafluorophosphate 50% propylene carbonate solution (manufactured by San-Apro Co., Ltd.) 2.5 parts ・SH710: Polysiloxane-based leveling agent (manufactured by Toray Dow Corning Co., Ltd.) 0.25 parts

[Manufacturing Example 9] <Preparation of composition (I) for forming resin layer> The composition (I) for forming a resin layer was obtained by mixing the following components and stirring at 23°C for 4 hours. ・Celloxide 2021P: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (made by Daicel Chemical Co., Ltd.) 32.5 parts ・EHPE3150: 1,2-epoxy-4-(2-epoxyethylene) cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (manufactured by Daicel Chemical Co., Ltd.) ) 17.5 copies ・OXT-221: 50 parts of bis(3-ethyl-3-oxetanylmethyl) ether (manufactured by Toagosei Co., Ltd.) ・CPI-100P: Triaryl hexafluorophosphate 50% propylene carbonate solution (manufactured by San-Apro Co., Ltd.) 2.5 parts ・SH710: Polysiloxane-based leveling agent (manufactured by Toray Dow Corning Co., Ltd.) 0.25 parts

[Manufacturing Example 10] <Preparation of composition (J) for forming resin layer> Acetylene modified polyvinyl alcohol resin (GOHSEFIMERZ200, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., saponification degree: 98.5 mol% or more) was stirred in pure water at 90°C for 4 hours to make it Dissolve, and prepare a 5 wt% aqueous solution. Mix the above-mentioned polyvinyl alcohol-based resin aqueous solution and a 10% by weight aqueous solution of sodium glyoxylate so that the weight ratio of the solid content of the acetyl acetaldehyde modified polyvinyl alcohol resin: sodium glyoxylate becomes 1:0.1, and then It was diluted with pure water so that the weight ratio of the solid content of the polyvinyl alcohol-based resin relative to 100 parts of water was 3.0 to prepare a resin layer forming composition (J).

[Table 1] Composition for forming resin layer Acrylic compound Free radical polymerization initiator Solvent Multifunctional acrylate monomer Urethane acrylate polymer (1) (2) (1) (2) (3) (4) (5) (1) (2) (1) Manufacturing example 1 (A) - - - 100 - - - - 4 50 Manufacturing example 2 (B) - - - - 100 - - - 4 50 Manufacturing example 3 (C) - - - - - 100 - - 4 50 Manufacturing example 4 (D) - - - - - - 100 - 4 50 Manufacturing example 5 (E) - - 100 - - - - - 4 50 Manufacturing example 6 (F) 70 - - 30 - - - 3 - 10 Manufacturing example 7 (G) - 90 - 10 - - - 3 - 10

Each component in Table 1 is shown below. Multifunctional acrylate monomer (1): Ethylene oxide (6) dipentaerythritol hexaacrylate (manufactured by Shinnakamura Chemical Co., Ltd., "NK ESTER A-DPH-6E"), the most connected branch structure The number of atoms close to the branch point of the (meth)acryloyl group and the chain of the (meth)acryloyl group is 5.

Multifunctional acrylate monomer (2): Ethylene oxide (12) dipentaerythritol hexaacrylate (manufactured by Shinnakamura Chemical Co., Ltd., "NK ESTER A-DPH-12E"), the most connected branch structure The number of atoms in the chain close to the branch point of the (meth)acryloyl group and the (meth)acryloyl group is 8.

Urethane acrylate polymer (1): Urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., "Violet UV-7650B"), the number of functional groups is 4 to 5, and the weight average molecular weight Mw is 2300, the number of functional groups per unit molecular weight is 19.6×10 ^-4 .

Urethane acrylate polymer (2): Urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., "Violet UV-3310B"), the number of functional groups is 2, the weight average molecular weight Mw is 5000, The number of functional groups per unit molecular weight is 4.0×10 ^-4 .

Urethane acrylate polymer (3): Urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., "Violet UV-6640B"), the number of functional groups is 2, the weight average molecular weight Mw is 5000, The number of functional groups per unit molecular weight is 4.0×10 ^-4 .

Urethane acrylate polymer (4): Urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., "Violet UV-7510B"), the number of functional groups is 3, the weight average molecular weight Mw is 3500, The number of functional groups per unit molecular weight is 8.6×10 ^-4 .

Urethane acrylate polymer (5): Urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., "Violet UV-7550B"), the number of functional groups is 3, and the weight average molecular weight Mw is 2400, The number of functional groups per unit molecular weight is 12.5×10 ^-4 .

Radical polymerization initiator (1): Phenylbis(2,4,6-trimethylbenzyl) phosphine oxide (manufactured by BASF Corporation, "Irgacure 819") Radical polymerization initiator (2): 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Corporation, "Irgacure 184")

Solvent (1): methyl ethyl ketone

・二色性色素： 偶氮色素；

・光聚合起始劑： 2-二甲基胺基-2-苄基-1-(4-嗎啉基苯基)丁烷-1-酮(Irgacure 369；Ciba Specialty Chemicals股份有限公司製造)          6份 ・調平劑： 聚丙烯酸酯化合物(BYK-361N；BYK-Chemie公司製造)      1.2份 ・溶劑： 鄰二甲苯     400份[Manufacturing Example 8] <Preparation of the composition for forming a polarizing film> The composition for forming a polarizing film was obtained by mixing the following components and stirring at 80°C for 1 hour. As the dichroic dye, the azo dye described in the Examples of JP 2013-101328 A was used.・Polymerizable liquid crystal compound:

・Dichroic pigment: Azo pigment;

・Photopolymerization initiator: 2-dimethylamino-2-benzyl-1-(4-morpholinylphenyl)butan-1-one (Irgacure 369; manufactured by Ciba Specialty Chemicals Co., Ltd.) 6 Parts・Leveling agent: Polyacrylate compound (BYK-361N; manufactured by BYK-Chemie) 1.2 parts・Solvent: 400 parts of o-xylene

[Example 1] (1) The second resin layer was produced on the release treatment surface of a polyethylene terephthalate film (SP-PLR382050 manufactured by LINTEC Corporation) (release film) subjected to release treatment After corona treatment , the resin layer forming composition (A) as the second curable composition was applied by the bar coating method (#2 30 mm/s), and the UV irradiation device (SPOT CURE SP -7; manufactured by Ushio Electric Co., Ltd.) to irradiate the coating layer of the resin layer forming composition with an exposure dose of 500 mJ/cm ² (365 nm standard) of ultraviolet rays, thereby obtaining a second layer formed on the surface of the release film Release film with resin layer attached to resin layer. The thickness of the second resin layer is 1.5 μm.

・溶劑： 鄰二甲苯     98份(2) Preparation of photo-alignment film (i) Preparation of photo-alignment film-forming composition by mixing the following photo-alignment polymer and the following solvent in the following ratio, and stirring the obtained mixture at 80°C for 1 hour , And obtain a composition for forming a photo-alignment film. Furthermore, the following photoalignment polymer is a polymer produced by the method described in Synthesis Example 1 of JP 2013-033249 A, and has a number average molecular weight of 28,200 and Mw/Mn of 1.82.・Optical alignment polymer:

・Solvent: 98 parts of o-xylene

(ii) Formation of photo-alignment film Then, after corona treatment is performed on the surface of the second resin layer of the release film with the resin layer, the photo-alignment film forming composition is applied and dried at 120° C. to obtain a dry film. Polarized UV is irradiated on the dry coating film to form a photo-alignment film, and a laminate A having a release film, a second resin layer, and a photo-alignment film in this order is obtained. The polarized UV treatment is performed using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Electric Co., Ltd.) under the condition that the intensity measured at a wavelength of 365 nm is 100 mJ. The thickness of the optical alignment film is 100 nm.

(3) The polarizing element is made on the surface of the photo-alignment film of the laminate A obtained by the above method, and the polarizing film forming composition is coated by the bar coating method (#9 30 mm/s), using 120°C The drying oven is heated and dried for 1 minute, thereby making the polymerizable liquid crystal compound phase transition into a liquid phase, and then cooling to room temperature to make the polymerizable liquid crystal compound phase transition into a smectic liquid crystal state. Next, a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Electric Co., Ltd.) was used to irradiate the layer formed of the polarizing film forming composition with an exposure amount of 1000 mJ/cm ² (365 nm standard) of ultraviolet rays, thereby The polymerizable liquid crystal compound contained in the dry coating film is polymerized while maintaining the smectic liquid crystal state of the polymerizable liquid crystal compound, and a polarizing element (polarizing film) is formed by the dry coating film. The thickness of the polarizing element is 2.3 μm. In the above manner, a laminate B having a release film, a second resin layer, an optical alignment film, and a polarizing element in this order is obtained. For this polarizing element, the same X-ray diffraction measurement was performed using an X-ray diffraction device X'Pert PRO MPD (manufactured by Spectris Co., Ltd.). As a result, the peak half-height width (FWHM) = about 2θ=20.2° was obtained. The steep diffraction peak of 0.17° (Brugge peak). The order period (d) calculated from the peak position is about 4.4 Å, and it is confirmed that the structure reflects the higher order stratigraphic facies.

(4) The production of the first resin layer is performed by corona treatment on the surface of the polarizing element of the laminate B obtained by the above method, and then coated again by the bar coating method (#2 30 mm/s) as the second 1 The curable composition resin layer forming composition (A), and using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Electric Co., Ltd.), the exposure amount is irradiated to the coating layer of the resin layer forming composition Ultraviolet rays of 500 mJ/cm ² (365 nm reference) were used to obtain a laminate C having a release film, a second resin layer, an optical alignment film, a polarizing element, and a first resin layer in this order. Then, by peeling off the release film, a polarizing film having a second resin layer, an optical alignment film, a polarizing element, and a first resin layer in this order is obtained. Furthermore, the thickness of the first resin layer is 1.5 μm.

[Examples 2-7 and Comparative Examples 1 and 2] As shown in Table 2, the resin layer forming compositions (B) to (I) were used instead of the resin layer forming composition (A), respectively, and Examples 2 to 7 were obtained in the same manner as in Example 1 And the polarizing films of Comparative Examples 1 and 2. The polarizing films obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were evaluated for adhesion and flexibility. The results are shown in Table 2.

[Comparative Example 3] (1) Production of the second resin layer After corona treatment is applied to the release treatment surface of the polyethylene terephthalate film (SP-PLR382050 manufactured by LINTEC) (release film), the release treatment is carried out by the bar coating method ( #30 30 mm/s) Apply the resin layer forming composition (J) as the second curable composition and dry it at 100°C for 1 minute to obtain a second resin formed on the surface of the release film Release film with resin layer attached to the layer. The thickness of the second resin layer is 1.5 μm.

(2) Production of optical alignment film Then, after corona treatment is performed on the surface of the second resin layer of the release film with the resin layer, the photo-alignment film forming composition is applied and dried at 120° C. to obtain a dry film. The dried coating film is irradiated with polarized light UV to form a photo-alignment film, and a laminate K having a release film, a second resin layer, and a photo-alignment film in this order is obtained. The polarized UV treatment is performed using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Electric Co., Ltd.) under the condition that the intensity measured at a wavelength of 365 nm is 100 mJ. The thickness of the optical alignment film is 100 nm.

(3) The production of polarizing element is directed to the surface of the photo-alignment film of the laminate K obtained by the above method. The polarizing film forming composition is coated by the bar coating method (#9 30 mm/s) and used Heat and dry in a drying oven at 120° C. for 1 minute, thereby making the polymerizable liquid crystal compound phase transition into a liquid phase, and then cooling to room temperature to make the polymerizable liquid crystal compound phase transition into a smectic liquid crystal state. Next, a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Electric Co., Ltd.) was used to irradiate the layer formed of the polarizing film forming composition with an exposure amount of 1000 mJ/cm ² (365 nm standard) of ultraviolet rays, thereby The polymerizable liquid crystal compound contained in the dry coating film is polymerized while maintaining the smectic liquid crystal state of the polymerizable liquid crystal compound, and a polarizing element (polarizing film) is formed by the dry coating film. The thickness of the polarizing element is 2.3 μm. In the above manner, a laminate L having a release film, a second resin layer, a photo-alignment film, and a polarizing element in this order is obtained.

(4) Production of the first resin layer After corona treatment is applied to the surface of the polarizing element of the laminate L obtained by the above method, the resin layer as the first curable composition is coated again by the bar coating method (#30 30 mm/s) The composition (L) was dried at 100°C for 1 minute to obtain a laminate M having a release film, a second resin layer, an optical alignment film, a polarizing element, and a first resin layer in this order. Then, by peeling off the release film, a polarizing film having a second resin layer, an optical alignment film, a polarizing element, and a first resin layer in this order is obtained. Furthermore, the thickness of the first resin layer is 1.5 μm.

The polarizing film obtained in Comparative Example 3 was evaluated for adhesiveness and flexibility. The results are shown in Table 2.

[Table 2] 1st resin layer 2nd resin layer Adhesion evaluation Flexibility evaluation Example 1 (A) (A) ○ ○ Example 2 (B) (B) ○ ○ Example 3 (C) (C) ○ ○ Example 4 (D) (D) ○ ○ Example 5 (E) (E) ○ ○ Example 6 (F) (F) ○ ○ Example 7 (G) (G) ○ ○ Comparative example 1 (H) (H) × ○ Comparative example 2 (I) (I) × ○ Comparative example 3 (J) (J) × ○

The polarizing film obtained in Example 7 was evaluated for heat resistance. As a result, ΔPy was -1.5 and ΔTy was -0.2.

As shown in Table 2, it was confirmed that the results of the adhesion evaluation of the polarizing films obtained in Examples 1 to 7 and Comparative Examples 1 to 3 were ○, indicating that the adhesion between layers was excellent. In addition, it can be seen that the result of the evaluation of the flexibility was also ○, and the flexibility was excellent. On the other hand, the result of the adhesion evaluation of the polarizing films obtained in Comparative Examples 1 to 3 was ×, and the adhesion was poor. Furthermore, it can be seen that the ΔPy and ΔTy of the polarizing film obtained in Example 7 are close to 0 and also have excellent heat resistance.

1: Polarizing film with front panel 2: Polarizing film 3: Front panel 4: The first resin layer 5: Polarizing element 6: Alignment film 7: The second resin layer 8: Polarizing plate with front panel 9: Polarizing plate 10: retardation film 11: Polarizing film with front panel 12: Polarizing plate with front panel 13: Polarizing plate

Fig. 1 is a schematic cross-sectional view of a layer structure of a polarizing film with a front panel laminated as a polarizing film of one aspect of the present invention. Fig. 2 is a schematic cross-sectional view of a layer structure of a polarizing plate with a front panel laminated with a polarizing film as one aspect of the present invention. Fig. 3 is a schematic cross-sectional view of a layer structure in which a polarizing film with a front panel is laminated as one aspect of the present invention. Fig. 4 is a schematic cross-sectional view of a layer structure of a polarizing plate with a front panel laminated with a polarizing film as one aspect of the present invention.

1: Polarizing film with front panel

2: Polarizing film

3: Front panel

4: The first resin layer

5: Polarizing element

6: Alignment film

7: The second resin layer

Claims (6)

A polarizing film, which is laminated with a first resin layer, a polarizing element, an alignment film, and a second resin layer in this order, and the first resin layer is cured by a first curable composition containing a (meth)acrylic compound The polarizing element is a cured product of a composition for forming a polarizing element containing a polymerizable liquid crystal compound having a (meth)acrylic acid group and a dichroic dye, and the alignment film is formed of an alignment film containing a (meth)acrylic compound For the cured product of the composition, the second resin layer is a cured product of the second curable composition containing a (meth)acrylic compound, and at least one of the first curable composition and the second curable composition contains each A urethane (meth)acrylate compound whose number of (meth)acrylic groups per unit molecular weight is 40×10 ^-4 or less is used as a (meth)acrylic compound. The polarizing film of claim 1, wherein at least one of the first curable composition and the second curable composition further contains a multifunctional (meth)acrylate compound as the (meth)acrylic compound. The polarizing film of claim 2, wherein the number of (meth)acrylic groups of the polyfunctional (meth)acrylate compound is 6 or less. The polarizing film of claim 2 or 3, wherein the polyfunctional (meth)acrylate compound has a branched structure, and the branch point closest to the (meth)acryloyl group in the branched structure is the same as the (meth)acrylic acid group. The number of atoms of the chain linked by the acryl group is 2 or more. A method of manufacturing a polarizing film as claimed in any one of claims 1 to 4, which comprises the following steps: coating or superimposing a second resin layer, an alignment film, and a polarizing element on the surface of the polarizing element of a laminate layered in sequence. 1 curable composition to harden the first curable composition. A method of manufacturing a polarizing film according to any one of claims 1 to 4, which comprises the following steps: a first curable composition formed on a release film, a second resin layer and an alignment film are sequentially laminated , The polarizing element surface of the laminated body of the polarizing element is overlapped, and active energy rays are irradiated from the release film side to harden the first curable composition, thereby obtaining a release film, a first resin layer, a polarizing element, The laminate of the alignment film and the second resin layer, and the release film is peeled from the laminate.

Images