KR20080072570A - Polarizing plate and process for producing the same - Google Patents

Abstract

A polarizing plate is provided to be simply manufactured within a short time, and to be superior in chip cutting resistance and resistances to moisture and heat. A polarizing plate is obtained by laminating an adhesive layer and protective film on at least one surface of a polyvinylalcohol-based polarizing plate. The adhesive layer comprises (A) an alicyclic epoxy compound, (B) a compound containing at least one hydroxyl group and having a number average molecular weight of 500 or more, and (C) a photoacid generator. The component(A) is (A1) a compound having at least two alicyclic epoxy groups in a molecule and/or (A2) a compound having an alicyclic epoxy group represented by the following formula 1.

Description

POLARIZING PLATE AND PROCESS FOR PRODUCING THE SAME}

The present invention relates to a polarizing plate and a manufacturing method thereof.

Background Art In recent years, liquid crystal display devices have been widely used as display devices for displaying characters, images, and the like. Such a liquid crystal display device usually includes two polarizing plates and a liquid crystal cell including a glass substrate, a transparent electrode, a color filter, a light distribution film, a liquid crystal, and the like disposed therebetween.

Generally, the polarizing plate used for a liquid crystal display device is triacetyl to one side or both sides of the polarizing film (polarizer) which adsorb | sucked iodine or a dichroic dye to the polyvinyl alcohol (henceforth PVA) type | system | group sheet | seat oriented. A protective film such as a cellulose (hereinafter also referred to as TAC) film is bonded through an adhesive layer.

As such a polarizing plate, in a polarizing plate in which a protective film is bonded to at least one surface of a polyvinyl alcohol polarizing film via a polyvinyl alcohol adhesive layer, the adhesive layer contains a polyvinyl alcohol adhesive containing a water-soluble epoxy compound. A polarizing plate is proposed, wherein the ratio of the water-soluble epoxy compound in the adhesive and the polyvinyl alcohol-based resin is (5 to 50) / 100 (solid content weight ratio) (see Japanese Unexamined Patent Application Publication No. 09-258023). ). In addition, this document also describes that the said protective film is triacetyl cellulose which saponified the surface.

According to the technique described in the above document using an aqueous adhesive and a TAC protective film, the adhesive can be cured by increasing the moisture of the adhesive through a TAC protective film having high moisture permeability. Therefore, a polarizing plate can be obtained by a comparatively easy manufacturing process. Moreover, since adhesiveness is high between an aqueous adhesive agent and a TAC system protective film, the polarizing plate which has the outstanding adhesive strength can be obtained.

However, there is a problem that heat and moisture resistance is low due to the high moisture permeability of the TAC-based protective film. That is, deformation and the like can be caused in a high temperature and high humidity environment such as when the vehicle is mounted, and there is a problem that it is difficult to maintain high polarization performance.

Therefore, the method of using the cyclic olefin resin film (cycloolefin resin film; hereafter also called a COP system resin film) which has low moisture permeability instead of a TAC system protective film is proposed.

For example, on one side of a polarizing film containing a polyvinyl alcohol-based resin, a cyclone is formed through a first adhesive layer formed from an aqueous composition containing a polyester ionomer-type urethane resin and a compound having a glycidyloxy group. An olefin resin film is laminated, and on the other side, a polarizing plate is proposed, in which a cellulose acetate film is laminated via a second adhesive layer having an aqueous composition different from the first adhesive layer (Japanese Patent Laid-Open). See 2005-208456.

Moreover, in the manufacturing method of the polarizing plate which adhesively laminates the protective film of a polarizer and a polarizer, it contains at least an aqueous emulsion, a polyvinyl alcohol, and a polyisocyanate compound, and the viscosity (20 degreeC) by a Brookfield viscometer is 0.03-1 The manufacturing method of the polarizing plate which wet-laminates the said polarizer and a protective film using the aqueous urethane type adhesive adjusted to Pa * s is proposed (refer Unexamined-Japanese-Patent No. 2004-37841). On the other hand, this document also describes that the protective film contains a thermoplastic saturated norbornene-based resin.

According to the technology disclosed in JP 2005-208456 A, the water content of the water-based adhesive can be evaporated through the cellulose acetate-based film having high moisture permeability, so that the technique described in JP-A 09-258023 Similarly, a polarizing plate can be obtained by a relatively simple process.

However, since a cellulose acetate film with high moisture permeability is provided on one side, there are problems of insufficient heat and moisture resistance and insufficient adhesiveness between the first adhesive layer, which is an aqueous adhesive, and the cycloolefin resin film.

According to the technique of Unexamined-Japanese-Patent No. 2004-37841, since the protective film of both surfaces of a polarizer contains thermoplastic saturated norbornene-type resin, a polarizing plate with favorable moisture heat resistance can be obtained.

However, since a protective film with low moisture permeability is used, it takes a long time to evaporate and cure the water of the aqueous urethane-based adhesive which is an aqueous adhesive, or there is a problem that the manufacturing process is more complicated than when using a TAC-based film. Moreover, since the protective film containing thermoplastic saturated norbornene-type resin is hydrophobic, there exists a problem that adhesiveness with an aqueous adhesive is insufficient.

On the other hand, excellent chip cutting resistance is calculated | required in manufacture of a polarizing plate. That is, the polarizing plate is usually obtained by cutting the laminated sheet for polarizing plates to a desired size, but there is a problem that peeling (defect of the adhesive layer) may occur at the cutting portion (edge after cutting) during the cutting. This peeling not only lowers the polarization performance of the peeling part, but also promotes moisture absorption of the polarizing plate, and may cause deformation under high temperature and high humidity.

In addition, the polarizing plate is attached to the liquid crystal display panel via an adhesive. At this time, bubbles may enter between the polarizing plate and the liquid crystal display panel or deformation may occur in the polarizing plate. In this case, in order to reuse a liquid crystal display panel, the process of peeling a polarizing plate from a liquid crystal display panel and bonding a new polarizing plate is employ | adopted (reprocessing process). However, when the adhesive force of the protective film and polarizer which form a polarizing plate is weak, a protective film and a polarizer may peel at the time of peeling this polarizing plate. In that case, since a protective film remains in a liquid crystal display panel and the process of peeling a protective film is added, manufacturing efficiency falls.

Therefore, as a characteristic of the adhesive agent for bonding a protective film and a polarizer used at the time of manufacture of a polarizing plate, it is calculated | required to exhibit the strong adhesive strength (peel strength) between a polarizer and a protective film also at the time of reprocessing.

In addition, the polarizing plate is required to have less warpage. That is, in order to prevent a liquid crystal cell from being damaged by an ultraviolet-ray, a polarizing plate needs to add an ultraviolet absorber to one side of the protective film used for a polarizing plate, or to provide an ultraviolet absorbing layer. Therefore, when hardening an adhesive agent in manufacture of a polarizing plate, only light irradiation can be performed only from the protective film side which does not add a ultraviolet absorber substantially, and a difference arises in the irradiation strength of an adhesive layer which is two layers. As a result, warpage may arise in the laminated polarizing plate, and subsequent workability may be affected.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described background, and provides a polarizing plate excellent in chip cutting resistance (which does not cause peeling at the time of cutting) and moisture and heat resistance, and which can be manufactured in a short time due to the simple manufacturing process. For the purpose of In addition, another object of the present invention is to provide a polarizing plate having a high adhesiveness (peel strength) between the protective film and the adhesive layer, and less warpage deformation, and a method for producing the same.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, as a result of adhering a polarizing film and a protective film using the radiation curable composition containing a specific component, the polarizing plate which was excellent in chip cutting resistance, moisture-and-moisture resistance, etc. was short-lived in a simple manufacturing process. The present invention has been completed by discovering that it can be prepared.

That is, this invention provides the following [1]-[10].

[1] A polarizing plate comprising a protective film laminated on at least one surface of a polyvinyl alcohol polarizing film via an adhesive layer, wherein the adhesive layer has (A) an alicyclic epoxy compound and (B) at least one hydroxyl group and is number average. A cured product of a radiation curable composition containing a compound having a molecular weight of 500 or more and (C) a photoacid generator.

[2] The above [1], wherein the component (A) is a compound having two or more alicyclic epoxy groups in one molecule of (A1) and / or (A2) a compound having one alicyclic epoxy group represented by the following formula (1): Polarizer.

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom or a methyl group)

[3] The polarizing plate according to the above [1] or [2], wherein the number average molecular weight of the component (B) is 1,000 or more.

[4] The polarizing plate according to any one of [1] to [3], in which the component (B) is a compound represented by the following Formula (2).

HO- (R ⁴ -O-CO-O) _m- (R ⁵ -O-CO-O) _n -R ⁶ -OH

(Wherein, R ⁴ and R ⁵ each independently represent a divalent hydrocarbon group having 2 to 12 carbon atoms, R ⁶ represents the same structure as any one of R ⁴ and R ⁵ , m is 2 to 150, and n is 0 To 150 and m + n is 2 to 200).

[5] The polarizing plate according to any one of [1] to [4], wherein the component (C) is an onium salt represented by the following general formula (4).

[R ⁷ R ⁸ _a R ⁹ _b ¹⁰ _c R _d Z] ⁺ PF ₆ ^-

Wherein the cation is an onium ion, Z represents S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl or N≡N, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represents the same or different organic group from each other, a, b, c and d are each an integer of 0 to 3, and (a + b + c + d-1) is the same as the valence of Z)

[6] The polarizing plate according to any one of [1] to [5], in which the radiation curable composition further includes (D) a compound represented by the following general formula (5).

(Wherein, R ^11, R ¹² and R ¹³ are each independently a monovalent organic group, R ¹¹ to R ¹³ is two or more of -R ¹⁴ OCOCR ¹⁵ = CH ₂ and, R ¹⁴ is a group of a carbon number of 2 to 8 Divalent organic group, R ¹⁵ is a hydrogen atom or a methyl group)

[7] A polarizing plate comprising a protective film laminated on at least one surface of a polyvinyl alcohol polarizing film via an adhesive layer, wherein the adhesive layer is a (A) alicyclic epoxy compound and (C) a photo acid represented by the following general formula (4). A cured product of a radiation curable composition containing a generator, comprising a polarizing plate.

<Formula 4>

[R ⁷ R ⁸ _a R ⁹ _b ¹⁰ _c R _d Z] ⁺ PF ₆ ^-

Wherein the cation is an onium ion, Z represents S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl or N≡N, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represents the same or different organic group from each other, a, b, c and d are each an integer of 0 to 3, and (a + b + c + d-1) is the same as the valence of Z)

[8] The polarizing plate according to any one of [1] to [7], wherein the radiation curable composition is a cured product having a thickness of 200 μm, wherein the light transmittance at a wavelength of 550 nm is 70% or more.

[9] The polarizing plate according to any one of [1] to [8], in which the protective film contains a cyclic olefin resin.

[10] A method for producing a polarizing plate according to any one of [1] to [9], wherein the step of laminating a protective film on at least one surface of the polarizing film via the radiation curable composition, and the radiation curable composition The manufacturing method of the polarizing plate containing the hardening process of irradiating and hardening by light, and obtaining a polarizing plate.

Since the adhesive layer contains the hardened | cured material of the radiation curable composition which has a specific component composition, the polarizing plate of this invention has the outstanding chip | tip cutting resistance (does not cause peeling of an adhesive bond layer at the time of cutting).

Since the polarizing plate of this invention contains the hardened | cured material of the non-aqueous radiation curable composition in which an adhesive bond layer has a specific component composition, even if it uses a non-permeable cyclic olefin resin film as a protective film, it does not require evaporation of moisture, and is favorable for a short time. Adhesiveness can be obtained. Moreover, a cyclic olefin resin film can also be applied to both surfaces of a polarizing film as a protective film. In this case, particularly excellent moisture and heat resistance can be obtained, and high polarization performance can be maintained even in a high temperature and high humidity environment.

According to the manufacturing method of the polarizing plate of this invention, the protective film is laminated | stacked on one or both surfaces of a polarizing film via the radiation curable composition for adhesive bond layer formation, and by the simple operation which irradiates and hardens the said radiation curable composition. A polarizing plate can be manufactured. Therefore, it is not necessary to remove water as in the case of using an aqueous adhesive. In addition, even when a non-moisture-permeable cyclic olefin resin film is used as the protective film, the manufacturing process is not complicated and prolonged as in the case of using an aqueous adhesive, and a polarizing plate that is a laminated film having excellent adhesion between the layers can be obtained. have.

The polarizing plate of this invention is a polarizing plate in which a protective film is laminated | stacked on one side or both surfaces of a polyvinyl alcohol-type polarizing film via an adhesive bond layer.

First, each component of the radiation curable composition which forms an adhesive bond layer is demonstrated in detail.

[Component (A)]

The component (A) which comprises the composition for radiation curable adhesives is an alicyclic epoxy compound containing 1 or more of alicyclic epoxy groups in 1 molecule. As a component (A), the compound which has two or more alicyclic epoxy groups in 1 molecule of (A1), and the compound which has one alicyclic epoxy group in 1 molecule of (A2) are mentioned. In the present invention, as the component (A), any one of the component (A1) and the component (A2) can be used alone or in combination thereof.

When component (A) contains 50 mass% or more of component (A1) (alicyclic epoxy compound which has two or more alicyclic epoxy groups in 1 molecule), a more favorable hardening rate and mechanical strength can be obtained. Moreover, by using a component (A2) as a component (A), the curability (cure rate) of the composition for radiation curable adhesives can be improved, and the said composition can be made low viscosity.

Specific examples of the alicyclic epoxy compound used as component (A1) include 3,4-epoxy cyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5, 5-spiro-3,4-epoxy) cyclohexane-meth-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'- Epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3,4-epoxycyclohexyl Methyl-3 ', 4'-epoxycyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4- on And the like boring chloride-hexane-carboxylate), epoxy hexahydrophthalic acid dioctyl cyclohexane, epoxy cyclohexane hexahydrophthalic acid di-2-ethylhexyl.

Of these alicyclic epoxy compounds, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, ε-caprolactone modified 3, 4-Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, β-methyl- δ-valerolactone modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate is more preferred, and 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexane More preferred are carboxylates and bis (3,4-epoxycyclohexylmethyl) adipates.

As these commercial items, Celoxide 2021, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Eporide GT-300, Eporide GT-301, Eporide GT-302, Eporide GT-400, Epoch Lead 401, eporide 403 (above, manufactured by Daicel Chemical Industries, Ltd.), KRM2199 (manufactured by Adeka Corporation), and the like.

As a preferable example of a component (A2), the compound (alicyclic diepoxy compound) represented by following General formula (1) is mentioned.

<Formula 1>

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom or a methyl group)

Specific examples of the compound represented by the formula (1) include 1,2: 8,9-diepoxylimonene and the like. As this commercial item, Celoxide 3000 (made by Daicel Chemical Industries, Ltd.) etc. is mentioned.

The composition for radiation curable adhesives of this invention contains component (A1) and / or component (A2) as component (A).

When the composition for radiation curable adhesives contains component (A1), the content rate of component (A1) in the composition for radiation curable adhesives is the total amount of the composition for radiation curable adhesives (except the organic solvent when the composition contains an organic solvent). Total amount) to 100 mass%, 20 to 80 mass%, preferably 25 to 78 mass%, more preferably 30 to 75 mass%. When the said content rate is less than 20 mass%, there exists a tendency for the mechanical strength and heat-and-moisture resistance of an adhesive bond layer to become inadequate. When the said content rate exceeds 80 mass%, there exists a tendency for deformation | transformation, such as the curvature of the adhesive bond layer which hardens the composition for radiation curable adhesives, to become large. In addition, when using compounds (for example, polyester diol etc.) other than the polycarbonate diol represented by General formula (2) as a component (B) mentioned later, the content rate of component (A1) is 30-70 mass%. It is preferable, and it is especially preferable that it is 30-60 mass%.

When the composition for radiation curable adhesives contains a component (A2), the content rate of the component (A2) in the composition for radiation curable adhesives is the whole quantity of the composition for radiation curable adhesives (except the organic solvent when the said composition contains an organic solvent. Whole quantity) to 100 mass%, Preferably it is 3-90 mass%, More preferably, it is 5-80 mass%, Especially preferably, it is 7-70 mass%. If the content rate of component (A2) is less than 3 mass%, sclerosis | hardenability immediately after light irradiation may be inadequate, and when it exceeds 90 mass%, adhesive strength with a PVA-type molded object may fall.

[Component (B)]

The component (B) which comprises the composition for radiation curable adhesives contains one or more hydroxyl groups, and is a compound whose number average molecular weight is 500 or more.

The number of hydroxyl groups (component in one molecule) of component (B) is one or more, Preferably it is 1-4.

The number average molecular weight of component (B) is 500 or more, Preferably it is 1,000 or more. Although the upper limit of this number average molecular weight is not specifically limited, From a viewpoint of preventing excessive increase of the viscosity of the composition for adhesive agents, Preferably it is 20,000, More preferably, it is 10,000. When the said number average molecular weight is less than 500, since chip cut resistance (cutting resistance) cannot fully be improved, it is not preferable.

In addition, the number average molecular weight of component (B) measured the value (specifically, HPC-8220GPC (made by Tosho), the column TFKgel G4000HXL, G3000HXL, G2000HXL, respectively, measured according to ASTM D2503, and develops tetrahydrofuran. It is a number average molecular weight of polystyrene conversion measured at the flow volume of 1 cc / min and 40 degreeC as a solvent.

By using the component (B), a laminated film excellent in chip breaking resistance can be obtained.

Examples of the compound preferably used as component (B) include polycarbonate diols, polycaprolactone diols, polyether diols, polyester diols, other polyols, and the like.

Examples of the polycarbonate diols include polycarbonates of polytetrahydrofuran, polycarbonates of 1,6-hexanediol, and the like. Among them, polycarbonate diols represented by the following general formula (2) Is preferably used. When such polycarbonate diol is used, flexibility and film strength are provided to the cured adhesive, and both the cutting property (chip cutting property) and the peel strength can be achieved.

<Formula 2>

HO- (R ⁴ -O-CO-O) _m- (R ⁵ -O-CO-O) _n -R ⁶ -OH

(Wherein, R ⁴ and R ⁵ each independently represent a divalent hydrocarbon group having 2 to 12 carbon atoms, R ⁶ represents the same structure as any one of R ⁴ and R ⁵ , m is 2 to 150, and n is 0 To 150 and m + n is 2 to 200).

The method for producing the polycarbonate diol represented by the formula (2) is not particularly limited, and known methods such as transesterification of the diol compound and the carbonate compound, polycondensation reaction of the diol compound and the phosgene, and the like can be given. . As a diol compound used for manufacture of this polycarbonate diol, 1, 4- butanediol, 1, 6- hexanediol, 3-methyl- 1, 5- pentanediol, 1, 9- nonanediol, 2-methyl- 1,8-octanediol etc. are mentioned. In addition, in order to obtain appropriate chip cutting resistance (cutting resistance) and peel strength, polycarbonate diols containing aliphatic hydrocarbon groups having 6 carbon atoms, such as 1,6-hexanediol and 3-methyl-1,5-pentanediol, More preferred.

As a commercial item of the compound preferably used as polycarbonate diol, DN-980, 981, 982, 983 (above, Nippon Polyurethane Co., Ltd.), PC-8000 (PPG Co., Ltd.), PC-THF-CD (BASF) Co., Ltd.), Kurare polyol C-590, C-1090, C-2050, C-2090, C-3090, C-2065N, C-2015N (above, manufactured by Kuraresa), Plaxel CD CD210PL, Plaxel CD CD220PL (above, the Daicel Chemical Industries, Ltd.) etc. are mentioned.

As polycaprolactone diol, the polycaprolactone diol etc. which are obtained by making an epsilon caprolactone react with a diol, etc. are mentioned, for example. As the diol used here, for example, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl Glycol, 1,4-cyclohexanedimethanol, 1,4-butanediol, and the like. Examples of commercially available products of these polycaprolactone diols include Paxel 205, 205H, 205AL, 212, 212AL, 220, and 220AL (above, manufactured by Daicel Chemical Industries, Ltd.).

As the polyether diol, an aliphatic polyether diol is preferable, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyhepta methylene glycol, polydecamethylene glycol, and the like. Commercially available products of these polyether diols include PEG # 600, # 1000, # 1500, # 1540, # 4000 (above, manufactured by Lion Corporation), ecsenol 720, 1020, 2020, 3020, 510, preminol PPG4000 (above, Asahi Glass company) etc. are mentioned.

As polyester diol, the copolymer of an aliphatic diol compound and an aliphatic dicarboxylic acid compound is preferable. As the aliphatic diol compound, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1,5 -Pentanediol etc. are mentioned, As an aliphatic dicarboxylic acid compound, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, etc. are mentioned. An aliphatic diol compound can use 1 type (s) or 2 or more types, and an aliphatic dicarboxylic acid compound can also use 1 type (s) or 2 or more types. As a commercial item of these polyester diols, it is Kurere polyol N-2010, O-2010, P-510, P-1010, P-1050, P-2010, P-2050, P-3010, P-3050 (above, Kura) Lesa Corporation) etc. are mentioned.

As another polyol, trivalent or more polyhydric alcohols, such as trimethylol propane, glycerin, pentaerythritol, sorbitol, sucrose, and quodolol, are ethylene oxide (EO), propylene oxide (PO), butylene jade, for example. The polyether polyol obtained by denaturation with cyclic ether compounds, such as a seed and tetrahydrofuran, is mentioned. Specific examples of such compounds include EO-modified trimethylolpropane, PO-modified trimethylolpropane, tetrahydrofuran-modified trimethylolpropane, EO-modified glycerin, PO-modified glycerin, tetrahydrofuran-modified glycerin, EO-modified pentaerythritol, PO-modified pentaerythrate Itol, tetrahydrofuran-modified pentaerythritol, EO-modified sorbitol, PO-modified sorbitol, EO-modified sucrose, PO-modified sucrose, EO-modified sucrose, EO-modified cudor, and the like, among which EO-modified trimethylolpropane, PO Modified trimethylolpropane, PO modified glycerin, and PO modified sorbitol are preferred.

As these commercial items, the Sannix TP-700, the Sannix GP-1000, the Sannix SP-750, the Sannix GP-600 (above, Sanyo Kasei Co., Ltd.), etc. are mentioned.

Moreover, the polymer of a hydroxyl-containing unsaturated compound is mentioned as a polyol used preferably as a component (B). As said hydroxyl-containing unsaturated compound, hydroxyl-containing (meth) acrylate is mentioned, Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth ) Acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclo Hexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentylglycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate And pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like. Moreover, the compound obtained by addition reaction of glycidyl-group containing compounds, such as alkylglycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate, and (meth) acrylic acid is mentioned.

In the composition for radiation-curable adhesives, the content rate of component (B) is 3-50 mass%, making 100 mass% whole quantity (when the said composition contains an organic solvent, whole quantity except an organic solvent) of the composition for radiation curable adhesives. , Preferably it is 5-45 mass%, More preferably, it is 7-40 mass%, Especially preferably, it is 7-30 mass%. When the said content rate is less than 3 mass%, since the chip cutting resistance of an adhesive bond layer is inferior, it is not preferable. On the other hand, when the said content rate exceeds 50 mass%, since the viscosity of a composition for radiation curable adhesives becomes high too much and coating property worsens, or adhesive strength of an adhesive bond layer and a to-be-adhered body falls, it is unpreferable. On the other hand, when using compounds (for example, polyester diol etc.) other than the compound represented by the said Formula (2) as a component (B), it is preferable that the content rate of a component (B) is 7-20 mass%, It is especially preferable that it is 7-15 mass%.

[Component (C)]

The component (C) which comprises the composition for radiation curable adhesives is a photo-acid generator.

Photoacid generators are photocationic polymerization initiators that emit Lewis acid by receiving light.

As an example of the said photo-acid generator, the onium salt which has a structure represented by following formula (3) is mentioned, for example. This onium salt has a substantial light absorption wavelength below 400 nm.

[R ⁷ _a R ⁸ _b R ⁹ _c R ¹⁰ _d Z] ^{p +} [MX _{q + p} ] ^p-

Wherein the cation is an onium ion, Z represents S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl or N≡N, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represents the same or different organic group from each other, a, b, c and d are each an integer of 0 to 3, (a + b + c + d-p) is equal to the valence of Z, and M is the center of the halide complex [MX _{q + p} ] Metal or metalloid constituting the atom, for example, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like; Is a halogen atom such as, for example, F, Cl, Br, p is the substantial charge of the halide complex ion, q is the valence of M)

In the formula (3), specific examples of the onium ion include diphenyl iodonium, 4-methoxydiphenyl iodonium, bis (4-methylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, Diaryl iodonium such as bis (dodecylphenyl) iodonium, triarylsulfonium such as triphenylsulfonium, diphenyl-4-thiophenoxyphenylsulfonium, and bis [4- (diphenyl Sulfonio) -phenyl] sulfide, bis [4- (di (4- (2-hydroxyethyl) phenyl) sulfonio) -phenyl] sulfide, eta ⁵ -2,4- (cyclopentadienyl ) [1,2,3,4,5,6-η]-(methylethyl) -benzene] -iron (1+), etc. are mentioned.

In the above formula (3), the anion Specific examples of [MX _{q + p],} tetrafluoroborate rate (BF ₄ ^-), hexafluorophosphate (PF ₆ ^-), hexafluoroantimonate (SbF ₆ ^-), hexafluoro a Loa reuse carbonate (AsF ₆ ^-), hexachloro antimonate (SbCl ₆ ^{- -)} and the like, but, most preferably phosphate (PF ₆₎ hexafluoropropane.

That is, the onium salt represented by following formula (4) is mentioned as especially preferable (C) component (photo-acid generator) in this invention.

<Formula 4>

[R ⁷ R ⁸ _a R ⁹ _b ¹⁰ _c R _d Z] ⁺ PF ₆ ^-

Wherein the cation is an onium ion, Z represents S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl or N≡N, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represents the same or different organic group from each other, a, b, c and d are each an integer of 0 to 3, and (a + b + c + d-1) is the same as the valence of Z)

When the onium salt represented by the general formula (4) is used as the component (C), a polarizing plate having a smaller warpage can be obtained as compared with the case of using other anionic species such as SbF ₆ ⁻ . When the onium salt represented by the general formula (4) is used as the component (C), a polarizing plate having a small warpage can be obtained even when the radiation curable composition is produced without using the component (B).

In manufacture of a polarizing plate, since one protective film has the property to absorb an ultraviolet-ray, hardening of an adhesive agent is performed by light irradiation from one side of a polarizing plate. Adhesives using photoacid generators of other anionic species such as SbF ₆ ^- have a sufficient adhesive strength, but have a high curing rate. Therefore, when using as an adhesive agent of a polarizing plate, a difference tends to arise in the hardening speed of the adhesive layer of two layers for the reason that a polarizer absorbs light. On the other hand, PF ₆ ^- when using a photo acid generator in the negative ions because it has an appropriate curing rate, decreases the difference between the cure rate of the adhesive layer 2, it is considered that as a result that the deflection small.

In addition, an onium salt having an anion represented by the formula [MX _q (OH) ⁻ ] can be used. Further, perchlorate ion (ClO ₄ ^-), trifluoromethanesulfonic acid ion (CF ₃ SO ₃ ^-), a fluoroalkyl sulfonate ion (FSO ₃ ^-), toluenesulfonic acid ion, trinitrotoluene sulfonic acid anion, and trinitrotoluene other, such as acid anions Onium salts having anions can also be used.

As an example of the onium salt used as a component (C), the aromatic halonium salt as described in Unexamined-Japanese-Patent No. 50-151996, Unexamined-Japanese-Patent No. 50-158680, etc. -151997, Japanese Patent Application Laid-Open No. 52-30899, Japanese Patent Application Laid-open No. 56-55420, Japanese Patent Application Laid-Open No. 55-125105, etc. Group VA aromatic onium salt disclosed in Japanese Patent Laid-Open No. 50-158698, Japanese Patent Laid-Open No. 56-8428, Japanese Patent Laid-Open No. 56-149402, Japanese Laid-Open Patent No. 57-192429 And oxosulfonium salts described in Japanese Patent Application Laid-Open No. and the aromatic diazonium salts described in Japanese Patent Application Laid-Open No. 49-17040 and the like, and thioberyllium salts described in US Patent No. 4,139,655. Moreover, an iron / arene complex, an aluminum complex / photodecomposition silicon compound type initiator etc. are mentioned. The photoacid generator preferably used as the component (C) is an aromatic onium salt such as a diaryliodonium salt, a triarylsulfonium salt, or the like, and more preferably a triarylsulfonium salt.

(C) As an example of the commercial item of a photo-acid generator, UVI-6950, UVI-6970, UVI-6974, UVI-6990, UVI-6992 (above, Union Carbide company make), Adeka Optomer SP-150, SP-151 , SP-152, SP-170, SP-172 (above, Asahi Denka Kogyo Co., Ltd.), Irgacure 260, Irgacure 261 (above, Shiba Specialty Chemicals Co., Ltd.), CI-2481, CI-2624, CI -2639, CI-2064, CI-5102 (above, Nippon Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (above, Sartomer Co., Ltd.), DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103, MPI-103, BBI-103 (above, manufactured by Midori Chemical Co., Ltd.), PCI-061T, PCI-062T, PCI-020T, PCI-022T (above, Nippon Kayaku Inc. Manufacture), CPI-110A, CPI-101A, CPI-100P (above, produced by San Aprosa), etc. are mentioned. Among them, UVI-6970, UVI-6974, Adeka Optomer SP-170, SP-172, CD-1012, MPI-103, CPI-110A, and CPI-101A have high light curing sensitivity to the adhesive composition containing them. It is preferable at the point which can express. In addition, among these, UVI-6950, UVI-6990, UVI-6992 (above, manufactured by Union Carbide), Adeka Optomer SP-150, SP-151, SP-152 (above, manufactured by Asahi Denka Kogyo Co., Ltd.), Use of cure 260 (manufactured by Ciba Specialty Chemicals Co., Ltd.), CI-5102 (manufactured by Nippon Soda Co., Ltd.), CPI-100P (manufactured by San Afro Co., Ltd.) and the like is preferable because a polarizing plate having a small warpage deformation can be obtained.

The said photo-acid generator can be used individually by 1 type or in combination of 2 or more types.

In addition, a sensitizer can also be used together in order to accelerate generation | occurrence | production of the acid by a photo-acid generator. Examples of the sensitizer include dihydroxybenzene, trihydroxybenzene, hydroxyacetophenone, dihydroxydiphenylmethane and the like.

In the composition for radiation curable adhesives, the content rate of component (C) is 100 mass% of the total amount of the composition for radiation curable adhesives (when the composition contains an organic solvent), preferably 0.1 to 10 mass%, More preferably, it is 0.2-5 mass%, Especially preferably, it is 0.3-3 mass%. When the said content rate is less than 0.1 mass%, the radiation curability of the composition for radiation curable adhesives falls, and since the adhesive bond layer which has sufficient mechanical strength cannot be formed, it is unpreferable. On the other hand, when the said content rate exceeds 10 mass%, since a photo-acid generator may adversely affect the long-term characteristic of an adhesive bond layer, it is not preferable.

[Component (D)]

The composition for radiation curable adhesives of this invention may further contain the isocyanuric acid derivative (component (D)) which has a polymerizable unsaturated group represented by following formula (5). By using a component (D), the curability (curing rate) of the composition for radiation curable adhesives can be improved.

<Formula 5>

(Wherein, R ^11, R ¹² and R ¹³ are each independently a monovalent organic group, R ¹¹ to R ¹³ is two or more of -R ¹⁴ OCOCR ¹⁵ = CH ₂ and, R ¹⁴ is a group of a carbon number of 2 to 8 Divalent organic group, R ¹⁵ is a hydrogen atom or a methyl group)

It is preferable that component (D) has two or more polymerizable unsaturated groups in a molecule | numerator. Although a polymerizable unsaturated group is not specifically limited, It is preferable that it is a (meth) acrylate group. By having two or more polymerizable unsaturated groups, crosslinking density becomes high and the fall of hardness by adding this can be reduced.

Specific examples of the component (D) that can be used in the present invention include tris [2- (meth) acryloyloxyethyl] isocyanurate and bis [2- (meth) acryloyloxyethyl) (2-hydroxy Ethyl) isocyanurate, bis [2- (meth) acryloyloxyethyl] isocyanurate, and ethylene oxide (EO), propylene oxide or caprolactam adducts to their starting alcohols ) Acrylates and the like. Among them, tris [2- (meth) acryloyloxyethyl] isocyanurate and bis [2- (meth) acryloyloxyethyl) (2-hydroxyethyl) isocyanurate are particularly preferred.

As a commercial item which can be used suitably as a component (D), Aronix M-215, M-313, M-315, M-325, M-326, M-327 (above, Toagosei Kagaku Kogyo Co., Ltd. make), SR-368 (made by Sarmer Corporation) etc. are mentioned. The said compound can be used individually by 1 type or in combination of 2 or more types.

When the composition for radiation curable adhesives contains component (D), the content rate of component (D) is 100 mass% of the whole quantity (when the said composition contains an organic solvent except whole organic solvent) of the composition for radiation curable adhesives. Preferably it is 3-40 mass%, More preferably, it is 5-35 mass%, Especially preferably, it is 7-30 mass%. When the said content rate is less than 3 mass%, sclerosis | hardenability immediately after light irradiation may be inadequate, and when it exceeds 40 mass%, adhesive strength with a PVA-type molded object may fall.

[Component (E)]

The composition for radiation curable adhesives may further contain an aliphatic epoxy compound (component (E)). The aliphatic epoxy compound of component (E) is an optional component added in order to adjust the mechanical strength etc. of an adhesive bond layer.

As a specific example of the said aliphatic epoxy compound, 1, 4- butanediol diglycidyl ether, 1, 6- hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether Polyethylene glycol diglycidyl ether, glycerin triglycidyl ether, and polypropylene glycol diglycidyl ether; Polyglycidyl ethers of polyether polyols obtained by adding one or two or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; Diglycidyl esters of aliphatic long-chain dibasic acids; Monoglycidyl ethers of aliphatic higher alcohols; Glycidyl esters of higher fatty acids; Epoxidized soybean oil; Butyl epoxystearate; Octyl epoxystearate; Epoxidized linseed oil; Epoxidized polybutadiene etc. are mentioned.

When the composition for radiation curable adhesives contains component (E), the content rate of component (E) is 100 mass% of whole quantity (when the said composition contains an organic solvent except whole organic solvent) of the composition for radiation curable adhesives. Preferably it is 0-50 mass%, More preferably, it is 0-45 mass%, Especially preferably, it is 0-40 mass%. When the said content rate exceeds 50 mass%, since content rates, such as (A) alicyclic epoxy compound which are essential components, become small and the effect of this invention will not be acquired, it is unpreferable. On the other hand, when using compounds other than the polycarbonate diol represented by the said Formula (2) as a component (B), it is preferable that the content rate of a component (E) is 15-45 mass%, and it is 30-40 mass%. Particularly preferred.

Moreover, various additives can be mix | blended with the composition for radiation curable adhesives used by this invention as another arbitrary component in the range which does not impair the objective and effect of this invention. Such additives include epoxy resins, polyamides, polyamideimides, polyurethanes, polybutadienes, polychloroprenes, polyethers, polyesters, styrene-butadiene block copolymers, petroleum resins, xylene resins, ketone resins, cellulose resins, and fluorine-based oligomers Polymers or oligomers such as silicone oligomers and polysulfide oligomers; Polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; Polymerization initiation aids; Leveling agents; Wetting improvers; Surfactants; Plasticizers; Ultraviolet absorbers; Silane coupling agents; Inorganic fillers; Pigments; Dyes; and the like.

An example of the component composition in the composition for radiation curable adhesives of this invention is shown below. On the other hand, the content rate of each component below is the content rate at the time of making 100 mass% whole quantity (when the said composition contains an organic solvent, whole quantity except an organic solvent) of the composition for radiation curable adhesives.

[Component Composition 1: When Component (A1) Is Included and Component (A2) Is Not Included]

The content rate of component (A1) becomes like this. Preferably it is 20-80 mass%, More preferably, it is 25-70 mass%, Especially preferably, it is 30-60 mass%.

The content rate of component (B) becomes like this. Preferably it is 3-30 mass%, More preferably, it is 5-20 mass%, Especially preferably, it is 7-15 mass%.

The content rate of component (C) becomes like this. Preferably it is 0.1-10 mass%, More preferably, it is 0.2-5 mass%, Especially preferably, it is 0.3-3 mass%.

The content rate of component (E) becomes like this. Preferably it is 0-50 mass%, More preferably, it is 15-45 mass%, Especially preferably, it is 30-40 mass%.

When the content rate of component (A1) is less than 20 mass%, there exists a tendency for the mechanical strength and heat-and-moisture resistance of an adhesive bond layer to become inadequate. When the said content rate exceeds 80 mass%, there exists a tendency for deformation | transformation, such as the curvature of the adhesive bond layer which hardens the composition for radiation curable adhesives, to become large.

When the content rate of component (B) is less than 3 mass%, since the chip cutting property of an adhesive bond layer is inferior, it is not preferable. On the other hand, when the said content rate exceeds 30 mass%, since the viscosity of a composition for radiation curable adhesives becomes too high and coating property worsens, or adhesive strength of an adhesive bond layer and a to-be-adhered body falls, it is unpreferable.

When the content rate of component (C) is less than 0.1 mass%, the radiation curability of the composition for radiation curable adhesives falls, and since the adhesive bond layer which has sufficient mechanical strength cannot be formed, it is unpreferable. On the other hand, when the said content rate exceeds 10 mass%, since a photo-acid generator may adversely affect the long-term characteristic of an adhesive bond layer, it is not preferable.

When the content rate of component (E) exceeds 50 mass%, since the content rate of (A) alicyclic epoxy compound etc. which are essential components becomes small and the effect of this invention will not be acquired, it is unpreferable.

[Component Composition 2: When Component (A1) Is Included or Not Included and Component (A2) Is Included]

The content rate of component (A1) becomes like this. Preferably it is 20-80 mass%, More preferably, it is 25-75 mass%, Especially preferably, it is 30-70 mass%.

The content rate of component (A2) becomes like this. Preferably it is 3-90 mass%, More preferably, it is 5-80 mass%, Especially preferably, it is 7-70 mass%.

The content rate of component (B) becomes like this. Preferably it is 3-50 mass%, More preferably, it is 5-45 mass%, Especially preferably, it is 7-40 mass%.

The content rate of component (C) becomes like this. Preferably it is 0.1-10 mass%, More preferably, it is 0.2-5 mass%, Especially preferably, it is 0.3-3 mass%.

The content rate of component (E) becomes like this. Preferably it is 0-50 mass%, More preferably, it is 15-45 mass%, Especially preferably, it is 30-40 mass%.

The upper limit and the lower limit of the content rates of the component (A1), the component (B), the component (C) and the component (E) are determined from the same viewpoint as the component composition 1 described above.

If the content rate of component (A2) is less than 3 mass%, sclerosis | hardenability immediately after light irradiation may be inadequate, and when it exceeds 90 mass%, adhesive strength with a PVA-type molded object may fall.

[Component Composition 3: When Component (A1) Is Contained and Component (B) Is Polycarbonate Diol Represented by Formula (2)]

The content rate of component (A1) becomes like this. Preferably it is 20-80 mass%, More preferably, it is 25-70 mass%, Especially preferably, it is 30-60 mass%.

The content rate of component (B) becomes like this. Preferably it is 3-30 mass%, More preferably, it is 5-20 mass%, Especially preferably, it is 7-15 mass%.

The content rate of component (C) becomes like this. Preferably it is 0.1-10 mass%, More preferably, it is 0.2-5 mass%, Especially preferably, it is 0.3-3 mass%.

The content rate of component (E) becomes like this. Preferably it is 0-50 mass%, More preferably, it is 0-45 mass%, Especially preferably, it is 0-40 mass%.

The upper limit and lower limit of the content rate of component (A1), component (B), component (C), and component (E) are determined from the same viewpoint as component composition 1.

[Component Composition 4: Including Component (A1) and Containing Component (D)]

The content rate of component (A1) becomes like this. Preferably it is 20-80 mass%, More preferably, it is 25-75 mass%, Especially preferably, it is 30-70 mass%.

The content rate of component (B) becomes like this. Preferably it is 3-50 mass%, More preferably, it is 5-45 mass%, Especially preferably, it is 7-40 mass%.

The content rate of component (C) becomes like this. Preferably it is 0.1-10 mass%, More preferably, it is 0.2-5 mass%, Especially preferably, it is 0.3-3 mass%.

The content rate of component (D) becomes like this. Preferably it is 3-40 mass%, More preferably, it is 5-35 mass%, Especially preferably, it is 7-30 mass%.

The content rate of component (E) becomes like this. Preferably it is 0-50 mass%, More preferably, it is 0-45 mass%, Especially preferably, it is 0-40 mass%.

The upper limit and lower limit of the content rate of component (A1), component (B), component (C), and component (E) are determined from the same viewpoint as component composition 1.

If the content rate of component (D) is less than 3 mass%, sclerosis | hardenability immediately after light irradiation may be inadequate, and if it exceeds 40 mass%, adhesive strength with a PVA-type molded object may fall.

[Component Composition 5: When Component (A1) Is Contained and Photoacid Generator (Component (C)) Represented by Formula (4)]

The content rate of component (A1) becomes like this. Preferably it is 20-80 mass%, More preferably, it is 25-75 mass%, Especially preferably, it is 30-70 mass%.

The content rate of component (B) becomes like this. Preferably it is 3-50 mass%, More preferably, it is 5-45 mass%, Especially preferably, it is 7-40 mass%.

The content rate of component (C) becomes like this. Preferably it is 0.1-10 mass%, More preferably, it is 0.2-7 mass%, Especially preferably, it is 0.3-5 mass%.

The content rate of component (D) becomes like this. Preferably it is 0-40 mass%, More preferably, it is 5-35 mass%, Especially preferably, it is 7-30 mass%.

The content rate of component (E) becomes like this. Preferably it is 0-50 mass%, More preferably, it is 0-45 mass%, Especially preferably, it is 0-40 mass%.

The upper limit and lower limit of the content rate of component (A1), component (B), component (C), and component (E) are determined from the same viewpoint as component composition 1.

The upper limit and lower limit of the content rate of component (D) are determined from the same viewpoint as component composition 4.

The radiation curable composition can be produced by uniformly mixing the above components. The viscosity (25 degreeC) of the radiation curable composition obtained in this way is 2,000 mPa * s or less normally, Preferably it is 500 mPa * s or less, More preferably, it is 300 mPa * s or less.

On the other hand, solvents, such as an organic solvent, can be added to a radiation curable composition as needed. However, in this invention, a radiation curable composition can also be manufactured even without a solvent. In this invention, it is preferable not to contain a solvent in terms of maintenance of a working environment, environmental load, etc.

Moreover, the light transmittance of wavelength 550nm in the case of the hardened | cured material of thickness 200micrometer becomes like this. Preferably it is 70% or more, More preferably, it is 80% or more. When the said transmittance | permeability becomes less than 70%, since the transmittance | permeability of the polarizing plate itself also falls, it is not preferable.

Moreover, it is also preferable to use the thing which was filtered with the filter etc. as a radiation curable composition.

Next, the polarizing plate of this invention and its manufacturing method are demonstrated, referring drawings suitably.

1: is sectional drawing which shows an example of the polarizing plate of this invention typically. 2 is a flowchart illustrating an example of a method of manufacturing a polarizing plate of the present invention.

In FIG. 1, the polarizing plate 1 includes a polyvinyl alcohol polarizing film 2, adhesive layers 3 and 4 formed on both surfaces (bottom and top surfaces) of the polarizing film 2, and these adhesive layers 3 and 4. Protection film 5, 6 formed by laminating | stacking on each one surface (specifically, the lower surface of the adhesive bond layer 3 and the upper surface of the adhesive bond layer 4).

[Polarizing Film]

As the polarizing film, a polyvinyl alcohol polarizing film (hereinafter also referred to as a PVA polarizing film) is used. PVA polarizing films are generally used as polarizing films, and are oriented by adsorbing iodine or a two-color dye onto a polyvinyl alcohol-based film.

Although the thickness of a polarizing film is not specifically limited, For example, it is set so that it may become 10-40 micrometers.

Adhesive Layer

An adhesive bond layer is a hardened | cured material layer formed by carrying out radiation hardening of the radiation curable composition mentioned above.

By forming the adhesive layer using the above-mentioned radiation curable composition, excellent chip cutting resistance can be obtained, and the protective film can be excellent in adhesive strength between the protective film and the adhesive layer in either the COP system or the TAC system. have.

Although the thickness of an adhesive bond layer is not specifically limited, For example, it is set so that it may become 0.01-5.0 micrometers.

[Protective film]

As the protective film, for example, an acetate resin such as triacetyl cellulose, a polyester resin such as polyethylene terephthalate resin, a polyether sulfone resin, a polycarbonate resin, a polyamide resin, a polyimide resin, The film containing optically transparent resin, such as polyolefin resin, cyclic olefin resin, and acrylic resin, is used. Especially, a cyclic olefin resin film (COP system film) and a triacetyl cellulose resin film (TAC system film) are preferable.

The following (1)-(3) is mentioned as a structure of a polarizing plate.

(1) TAC type film / adhesive layer / PVA type polarizing film / adhesive layer / TAC type film

(2) TAC type film / adhesive layer / PVA type polarizing film / adhesive layer / COP type film

(3) COP type film / adhesive layer / PVA type polarizing film / adhesive layer / COP type film

In the present invention, it is preferable that at least one protective film is a COP-based film. That is, said (2) and (3) are preferable as a structure of a polarizing plate, and said (3) is more preferable. According to the structure of said (2), (3), since the COP type film with low moisture permeability is used as a protective film, the polarizing plate excellent in moisture-heat resistance can be obtained.

In this invention, it is necessary that one protective film is an ultraviolet absorber protective film, and the other protective film is an ultraviolet-ray protective film among upper and lower protective films.

When the polarizing plate is disposed on both sides of the liquid crystal cell, the ultraviolet protective film serves to protect the liquid crystal cell from external ultraviolet rays. A ultraviolet absorber is mix | blended suitably with an ultraviolet protective film. The light transmittance at the wavelength of 380 nm of an ultraviolet protective film is 10% or less, for example.

The said ultraviolet permeable protective film is for hardening a radiation curable composition by irradiating radiation (light irradiation) from the said protective film side. The UV-transmissive protective film does not contain or includes an ultraviolet absorber, but includes an ultraviolet ray-curable composition to the extent that it can be cured by irradiating light through the protective film. The light transmittance at the wavelength of 380 nm of an ultraviolet-ray protective film is 60% or more, for example.

Retardation can also be designed for a protective film.

Although the thickness of a protective film is not specifically limited, For example, it is set so that it may become 10-200 micrometers.

Moreover, various surface treatment can also be given to a protective film before application | coating of a radiation curable composition.

(Cyclic olefin resin film)

On the other hand, as the above-mentioned cyclic olefin resin film, the film containing resin obtained by superposing | polymerizing the monomer composition containing 1 or more types of cyclic olefin compounds, and further hydrogenating as needed is preferable.

As said cyclic olefin type compound, the cyclic olefin type compound represented by following formula (6) is mentioned, for example.

Wherein R ¹⁶ to R ¹⁹ each independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms which may have a linking group including oxygen, nitrogen, sulfur or silicon or Or an external monovalent organic group, or R ¹⁶ and R ¹⁷ or R ¹⁸ and R ¹⁹ may be bonded to each other to form an alkylidene group, and R ¹⁶ and R ¹⁷ , R ¹⁸ and R ^19, or R ¹⁷ and R ¹⁸ may be bonded to each other. To form a carbocyclic ring or a heterocycle (these carbocyclic rings or heterocycles may be monocyclic, or other rings may condense to form a polycyclic structure), and the carbocyclic or heterocyclic rings formed may be aromatic rings or Can be a non-aromatic ring, x is 0 or an integer from 1 to 3, y is 0 or 1, and y is 0 when x is 0)

As a specific example of the cyclic olefin type compound represented by General formula (6), although the compound shown below can be illustrated, it is not limited to these examples.

Bicyclo [2.2.1] hept-2-ene (norbornene)

5-Methyl-bicyclo [2.2.1] hept-2-ene

5-ethyl-bicyclo [2.2.1] hept-2-ene

5-cyclohexyl-bicyclo [2.2.1] hept-2-ene

5-phenyl-bicyclo [2.2.1] hept-2-ene

5- (4-biphenyl) -bicyclo [2.2.1] hept-2-ene

5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene

5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene

5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2-ene

5-phenylcarbonyloxy-bicyclo [2.2.1] hept-2-ene

5-Methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene

5-Methyl-5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene

5-Methyl-5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2-ene

5-vinyl-bicyclo [2.2.1] hept-2-ene

5-ethylidene-bicyclo [2.2.1] hept-2-ene

5,5-dimethyl-bicyclo [2.2.1] hept-2-ene

5,6-dimethyl-bicyclo [2.2.1] hept-2-ene

5-fluoro-bicyclo [2.2.1] hept-2-ene

5-Chloro-bicyclo [2.2.1] hept-2-ene

5-bromo-bicyclo [2.2.1] hept-2-ene

5,6-difluoro-bicyclo [2.2.1] hept-2-ene

5,6-dichloro-bicyclo [2.2.1] hept-2-ene

5,6-dibromo-bicyclo [2.2.1] hept-2-ene

5-hydroxy-bicyclo [2.2.1] hept-2-ene

5-hydroxyethyl-bicyclo [2.2.1] hept-2-ene

5-cyano-bicyclo [2.2.1] hept-2-ene

5-amino-bicyclo [2.2.1] hept-2-ene

Tricyclo [4.3.0.1 ^2,5 ] deck-3-en

Tricyclo [4.4.0.1 ^2,5 ] undec-3-yen

7-methyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7-ethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7-cyclohexyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7-phenyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7- (4-biphenyl) -tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7,8-dimethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7,8,9-trimethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

8-methyl-tricyclo [4.4.0.1 ^2,5 ] undec-3-ene

8-phenyl-tricyclo [4.4.0.1 ^2,5 ] undec-3-ene

7-fluoro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7-chloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7-bromo-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7,8-dichloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7,8,9-trichloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7-chloromethyl-tricyclo [4.3.0.1 ^2,5] deck-3-ene

7-dichloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7-trichloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7-hydroxy-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7-cyano-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7-amino-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-en

Pentacyclo [7.4.0.1 ^2,5 .1 ^8,11 .0 ^7,12 ] pentadec-3-ene

Hexacyclo [8.4.0.1 ^2,5 .1 ^7,14 .1 ^9,12 .0 ^8,13 ] heptadec-3-ene

8-methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-ethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-cyclohexyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-phenyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8- (4-biphenyl) -tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-phenoxyethylcarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-phenylcarbonyloxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-methyl-8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-methyl-8-phenoxyethylcarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-vinyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-ethylidene-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8,8-dimethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8,9-dimethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-fluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-chloro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-bromo-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8,8-dichloro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8,9-dichloro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8,8,9,9-tetrachloro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-hydroxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-methyl-8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-cyano-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-amino-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

In addition, these cyclic olefin type compounds may be used individually by 1 type, and may use 2 or more types together.

The kind and quantity of the said cyclic olefin type compound are suitably selected according to the characteristic calculated | required by resin obtained.

As a cyclic olefin compound, when a compound having a structure (hereinafter referred to as "polar structure") containing at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom in the molecule thereof, Since it is excellent in adhesiveness and adhesiveness with another raw material, it is preferable. In particular, in Formula 6, R ¹⁶ and R ¹⁸ is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, any one of R ¹⁷ or R ¹⁹ is a group having a polar structure, and The compound whose thing is a hydrogen atom or a C1-C3 hydrocarbon group is preferable because of low water absorption (wetness) of resin. Moreover, the cyclic olefin type compound in which the group which has a polar structure is group represented by following formula (7) is easy to balance the heat resistance and water absorption (wetness) of resin obtained, and can be used preferably.

-(CH ₂ ) _z COOR ²⁰

(In the formula 7, R ²⁰ denotes a hydrocarbon group of a substituted or unsubstituted 1 to 15 carbon atoms, z is an integer of 0 or 1 to 10)

In the general formula (7), the smaller the value of z, the higher the glass transition temperature of the obtained hydrogenated product and the better the heat resistance. Therefore, z is preferably an integer of 0 to 3. Moreover, the monomer whose z is 0 is preferable at the point which the synthesis | combination is easy. In terms of the more R ²⁰ is a carbon number in the formula (7), but tend to absorb (s) of the hydrogenation product of the resulting polymer to be lowered, so also tend to be the glass transition temperature is lowered, maintaining the heat resistance having 1 A hydrocarbon group of 10 to 10 is preferable, and a hydrocarbon group of 1 to 6 carbon atoms is particularly preferable.

On the other hand, in the above formula (6), when the alkyl group having 1 to 3 carbon atoms, especially the methyl group is bonded to the carbon atom to which the group represented by the formula (7) is bonded, it is preferable in terms of balance of heat resistance and water absorption (wet). In addition, in the above formula (6), x is 0 or 1, y is 0, the compound is high in reactivity, the polymer is obtained in high yield, and the polymer hydrogen additive having high heat resistance is obtained, furthermore industrially easy to obtain It is preferably used at one point.

In the cyclic olefin resin, other monomers copolymerizable with the cyclic olefin compound may be included in the monomer composition and polymerized.

As another copolymerizable monomer, for example, cyclic olefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclododecene and non-pores such as 1,4-cyclooctadiene, dicyclopentadiene and cyclododecatene Liquid cyclic polyene is mentioned.

These other copolymerizable monomers may be used alone or in combination of two or more.

As a polymerization method of the monomer composition containing the said cyclic olefin type compound, the well-known method by metathesis ring-opening polymerization and addition polymerization of Unexamined-Japanese-Patent No. 2006-201736, Unexamined-Japanese-Patent No. 2005-164632, etc. is known, for example. Can be used.

Moreover, the well-known method described in the said document can also be used about the method of hydrogenation of the obtained (co) polymer.

As a value of degree of hydrogenation it was measured by 500 MHz, ¹ H-NMR of the hydrogenated polymer, preferably at least 50%, more preferably at least 70%, more preferably at least 90%, most preferably 99% or more to be. The higher the hydrogenation rate, the better the stability against heat and light, and the stable characteristics can be obtained over a long period of time.

The intrinsic viscosity [η] _inh of the cyclic olefin resin is preferably 0.2 to 2.0 dl / g, more preferably 0.35 to 1.0 dl / g, particularly preferably 0.4 to 0.85 dl / g.

The number average molecular weight (Mn) of polystyrene conversion measured by gel permeation chromatography (GPC) of cyclic olefin resin becomes like this. Preferably it is 5,000-1 million, More preferably, it is 10,000-500,000, Especially preferably, it is 1.50,000 To 250,000.

The weight average molecular weight (Mw) of cyclic olefin resin becomes like this. Preferably it is 10,000-2 million, More preferably, it is 20,000-1 million, Especially preferably, it is 30,000-500,000.

Glass transition temperature (Tg) of cyclic olefin resin becomes like this. Preferably it is 120 degreeC or more, More preferably, it is 130 degreeC or more, Especially preferably, it is 150 degreeC or more.

The saturated water absorption of the cyclic olefin resin is preferably 1% by mass or less, more preferably 0.1 to 0.8% by mass. When a saturation water absorption exceeds 1 mass%, a problem may arise in durability, such as the protective film obtained from this resin being absorbed (wet) and deform | transformed with time depending on the environment used. On the other hand, when it is less than 0.1 mass%, a problem may arise in adhesiveness. In addition, the said saturated water absorption is a value obtained by immersing in 23 degreeC water for 1 week and measuring an increase mass according to ASTMD570.

In this invention, additives, such as antioxidant and a ultraviolet absorber, can be added further in the range which does not impair the effect of this invention.

As antioxidant, 2, 6- di-t- butyl- 4-methyl phenol, 2, 2'- dioxy- 3, 3'- di- t- butyl- 5, 5'- dimethyl diphenylmethane And tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and the like.

As a ultraviolet absorber, 2, 4- dihydroxy benzophenone, 2-hydroxy-4- methoxy benzophenone, etc. are mentioned, for example.

(Method for producing cyclic olefin resin film)

As a manufacturing method of a cyclic olefin resin film, the well-known method of Unexamined-Japanese-Patent No. 2006-201736, Unexamined-Japanese-Patent No. 2005-164632, etc. can be used. That is, a cyclic olefin resin film can be shape | molded suitably by the direct melt-molding of the said cyclic olefin resin, or by the method of melt | dissolving in a solvent and casting (cast molding).

Next, the manufacturing method of a polarizing plate is demonstrated.

In the manufacturing method of the polarizing plate of this invention, after laminating | stacking a protective film on at least one surface (specifically one surface or both surfaces) of a polarizing film via a liquid radiation curable composition, this liquid radiation curable composition is irradiated (for example, For example, ultraviolet rays) are cured by irradiation.

In FIG. 2, the manufacturing method of the polarizing plate 1 uses the radiation curable composition for adhesive bond layer formation to one side of the process (a) of preparing the polyvinyl alcohol-type polarizing film 2, and protective films 5 and 6, respectively. The top surface of the process (b) and the polyvinyl alcohol polarizing film 2 which apply | coat and obtain the laminated body 5 ', 6' of the protective film 5, 6 and radiation curable composition layers 3 ', 4'. And the step (c) of laminating the laminates 5 'and 6' on each of the lower surfaces so that the composition layers 3 'and 4' face the surface of the polarizing film 2, and the composition layer by light irradiation. Step (d) of hardening (3 ', 4') and forming adhesive bond layers 3 and 4 is included.

Hereinafter, it demonstrates for every process.

[Step (a)]

Step (a) is a step of preparing the polyvinyl alcohol polarizing film 2 (see (a) in FIG. 2).

[Step (b)]

Process (b) applies the radiation curable composition for adhesive bond layer formation to one side of protective film 5 (6), and has protective film 5 '(6') which has composition layer 3 '(4'). It is a process of obtaining (refer (b) in FIG. 2).

Specifically, the radiation curable composition for adhesive layer formation is apply | coated to each surface of each of the protective films 5 and 6, and it drys etc. as needed, and the layer (3 ', 4') containing a radiation curable composition To form.

Although it does not specifically limit as a coating method of a radiation curable composition, For example, die coating method, roll coating method, gravure coating method, spin coating method, etc. are mentioned.

[Step (c)]

The step (c) is a laminate (5 ', 6') of the protective films (5, 6) and the radiation curable composition layers (3 ', 4') on each of the upper and lower surfaces of the polyvinyl alcohol polarizing film (2). ) Is laminated (see (c) in FIG. 2). The laminate 5 'is laminated so that the composition layer 3' faces the lower surface of the polarizing film 2. The laminate 6 'is laminated so that the composition layer 4' faces the upper surface of the polarizing film 2.

[Step (d)]

Step (d) is a step of curing the composition layers (3 ', 4') to form the adhesive layer (3, 4) by irradiating the radiation (7) (see (d), (e) in FIG. 2).

Specifically, the radiation 7 is irradiated from the upper surface of the protective film 6. Thereby, the radiation curable composition layers 3 'and 4' are cured to be adhesive layers 3 and 4, and the polarizing film 2 and the protective films 5 and 6 are interposed through the adhesive layers 3 and 4, respectively. And the polarizing plate 1 formed to be bonded is completed (see (e) in FIGS. 1 and 2).

Although the irradiation amount of radiation is not specifically limited, It is preferable to irradiate and expose the light of wavelength 200-450 nm and illumination intensity 1-500 mW / cm <^2> so that irradiation amount may be 10-10,000 mJ / cm <^2> .

As the kind of radiation to be irradiated, visible light, ultraviolet rays, infrared rays, X-rays, α-rays, β-rays, γ-rays and the like can be used, but ultraviolet rays are particularly preferable. As a light irradiation apparatus, it is preferable to use a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer lamp, etc., for example.

On the other hand, in this invention, radiation is irradiated from the ultraviolet permeable protective film side. In FIG. 2, the case where the protective film 6 is an ultraviolet-ray protective film is shown.

The obtained polarizing plate is usually used after being subjected to processing such as cutting.

EXAMPLE

Hereinafter, an Example demonstrates this invention concretely.

Example 1

(Production of a composition for radiation curable adhesive)

The components (A)-(C) and arbitrary components were thrown into the container with a stirring apparatus in the compounding ratio shown in Table 1, and it stirred for 4 hours, and mixed uniformly. Stirring was stopped, it left still for 24 hours and the radiation curable composition 1 was obtained.

(Manufacture of Polarizing Plate)

The obtained radiation curable composition 1 was coated on the following TAC film 2 (protective film 1) using the wire bar coater # 3, and the following PVA film was bonded on it so that defects, such as air bubbles, may not enter. Next, the radiation curable composition 1 is coated on the following TAC film 1 (protective film 2) using the wire bar coater # 3, and it joins so that defects, such as air bubbles, may not enter on the PVA of the said bonded film. It was. On the glass plate, the four sides of the protective film 2 were fixed with a tape so that the protective film 2 could be turned upward, and light was irradiated from the protective film 2 side with a metal halide lamp (roughness 220 mW / cm ² , irradiation light quantity 1,000 mJ / cm ² ). A polarizing plate was prepared.

Moreover, the same operation was performed using the film shown below, and the various polarizing plates shown in Table 1 were manufactured.

PVA film: 20 mass parts of boric acid, 0.2 mass part of iodine, and 0.5 mass part of potassium iodide are melt | dissolved in 480 mass parts of water, and a dyeing liquid is manufactured, and PVA film (vinyllon film # 40, the ice cell company make) is made into this dyeing solution for 30 second. After immersion, the film was stretched twice in one direction and dried to prepare a PVA film having a film thickness of 30 μm.

TAC film 1: 100 mass parts of cellulose acetates (60.8% oxidation degree), 12 mass parts of triphenyl phosphates, 300 mass parts of methylene chlorides, and 50 mass parts of methanol were put into a sealed container, and it was made to keep 80 degreeC under pressure, stirring, and stirring. Completely dissolved. Next, this solution was filtered, cooled, and kept at 30 ° C, and applied with a 15-mil applicator on a PET film adhered to a glass substrate. After standing still in this state for 5 minutes, it further dried in the oven at 100 degreeC for 1 hour, and obtained the TAC film 1 (no ultraviolet absorber) of 80 micrometers in thickness.

TAC film 2: "Fuji-Taek 80D" by the Fuji Shashin film company (brand name)

Aton film 1: "Aton R5300" by JSR Corporation (brand name)

Aton film 2: "Aton R5300U" (ultraviolet absorber containing film) made from JSR company (brand name)

Zeono Film: "Zeonor ZF14-100" made by Nihon Xeon Co., Ltd. (brand name)

Apel Film: "Apel APL6013T" (trade name) manufactured by Mitsui Chemical Industries, Ltd. was dissolved in cyclopentane to obtain a resin solution having a resin concentration of 30% by mass. This resin solution was apply | coated with the bar coater on the polyethylene terephthalate film, it was left to stand for 1 hour, and it dried at 80 degreeC for 12 hours, and obtained the apel film with a film thickness of 72 micrometers.

Topas film: A 75 µm topas film was obtained in the same manner as in the preparation of the Apel film except that “TOPAS 5013” (trade name) manufactured by Polyplastics was dissolved in methylene chloride.

On the other hand, films other than the PVA film were subjected to corona discharge treatment on the film surface with a discharge amount of 320 W · min / m ² using a corona surface treatment apparatus (Gas "AGF-012" manufactured by Denki Co., Ltd.) Adhesion was performed within 1 hour after the treatment.

(evaluation)

The light transmittance of the hardened | cured material of the obtained radiation curable composition 1, the chip | tip cutting resistance of each polarizing plate, and moisture heat resistance were evaluated by the following method.

[Light transmittance of wavelength 550nm]

The PET film (film thickness 188 micrometer, surface untreated article) was fixed on the glass plate with an adhesive, and the radiation curable composition was apply | coated on the PET film using the 15-mil gap applicator. The coating film was irradiated with light using a metal halide lamp (roughness 220 mW / cm ² , irradiated light amount 1,000 mJ / cm ² ) to cure the composition, and allowed to stand at 23 ° C. and 50% RH for 24 hours. After peeling hardened | cured material from PET film and confirming that film thickness is 200 +/- 5micrometer, wavelength 550 was referred to the hardened | cured material with reference to air using the U-3410 type magnetic spectrophotometer (made by Hitachi Seisakusho). The light transmittance of nm was measured.

[Chip cut resistance]

A super dumbbell cutter (SSK-12862-06, manufactured by Dumbbell) and an SD-type lever-type sample cutter (SDL-200, manufactured by Dumbbell) were used for attaching the polarizing plate that was left standing at 23 ° C. and 50% RH for 24 hours after bonding by light irradiation. Was punched into a size of 50 mm x 80 mm. The periphery of the punched polarizing plate was visually observed and (circle) was observed and the strip | belt shape was seen in the edge part, but the case where it was not peeled off was made into (circle) and the thing where peeling was observed at the edge part was made into x.

[Moisture heat resistance]

After bonding by light irradiation, the polarizing plate which left still at 23 degreeC and 50% RH for 24 hours was exposed to the environment of 60 degreeC and 90% RH (relative humidity) for 250 hours, and evaluation of chip-cutting resistance was performed on the same determination criteria as the above. It was done.

The results are shown in Table 1.

[Examples 2 to 9 and Comparative Examples 1 to 3]

Various physical properties were measured similarly to Example 1 except having mix | blended each component by the ratio of Table 1. The results are shown in Table 1.

In addition, the compound name of each component of Table 1 is as follows.

[(A1) component]

Celoxide 2021P: 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate (made by Daicel Corporation)

KRM2199: bis (3,4-epoxycyclohexylmethyl) adipate (made by Adeca)

[(A2) component]

Celoxide 3000: 1,2: 8,9-diepoxylimonene (manufactured by Daicel Chemical Industries, Ltd.)

[(B) component]

Kuraray polyol P-510: Poly [(3-methyl-1,5-pentanediol) -alt- (adipic acid)] (made by Kuraray; number average molecular weight 500)

Kuraray polyol P-1010: Poly [(3-methyl-1,5-pentanediol) -alt- (adipic acid)] (made by Kuraray; number average molecular weight 1,000)

Preminol PPG4000: polypropylene glycol (made by Asahi Glass Co., Ltd .; number average molecular weight 4,100)

Curarepolyol C-2090: poly ((3-methyl-1,5-pentanediol; 1,6-hexanediol) carbonate) (manufactured by Curaresa; number average molecular weight 2,000)

[(C) component]

CPI-110A: diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate (manufactured by Acid Aprosa)

[Other Ingredients]

Sr-npg: neopentyl glycol diglycidyl ether (manufactured by sakamoto yakuhin high school)

Sunix GP-400: Polyoxypropylene glyceryl ether (Sanyo Kasei Kogyo Co., Ltd. make; number average molecular weight 420)

[Examples 10 to 17, Comparative Examples 4 and 5 and Reference Examples 1 to 3]

Except having mix | blended each component in the ratio of Table 2, it carried out similarly to Example 1, and obtained the radiation curable composition for adhesive layers and a polarizing plate.

The light transmittance of the cured product of the obtained radiation curable composition and the chip breaking resistance of the polarizing plate were evaluated in the same manner as in Example 1, and the peeling strength of the polarizing plate was further evaluated by the following method.

[Peel strength]

The peeling strength of the produced polarizing plate was measured according to JIS K 6854-4 adhesive- peeling adhesive strength test method part 4: the floating roller method. Specifically, the produced polarizing plate was fixed with a double-sided adhesive tape (ST-416P, Sumitomo 3M Corporation) on a metal plate (made of stainless steel, dimensions: length 200 mm, width 25 mm, thickness 1.5 mm). The edge of the longitudinal direction of the polarizing plate was peeled off using the cutter knife. According to JIS method, the sample was attached to the floating roller, the end of the peeled film sample was fixed to the grip of the tensile tester, the floating roller was raised at a speed of 300 mm / min with a tensile tester, and the average when the film was peeled off. Peel force (unit N) was measured.

"◎" for the case where the average peeling force is 1.5N or more, or a polarizing plate cannot break | break or the edge of a polarizing plate is "(circle)", and the case where average peeling force is 0.8N or more and less than 1.5N is "(circle)" and average peeling force is less than 0.8N The case was made into "x".

The results are shown in Table 2.

In addition, as Comparative Examples 4 and 5, the results obtained by measuring the peel strength in addition to the light transmittance and the chip cutting resistance of the composition having the same composition as those of the Comparative Examples 1 and 2 described above were described as Reference Examples 1 to 3, and Example 1 described above. Table 2 shows the results of measuring the peel strength in addition to the light transmittance and the chip cutting resistance of the composition having the same composition as in [3] and [3].

In addition, the compound name of each component of Table 2 is as follows.

Kurarepolyol C-590: Poly ((3-methyl-1,5-pentanediol; 1,6-hexanediol) carbonate) (made by Kuraresa; number average molecular weight 500)

Curarepolyol C-1090: poly ((3-methyl-1,5-pentanediol; 1,6-hexanediol) carbonate) (made by Curaresa; number average molecular weight 1,000)

Curarepolyol C-2050: poly ((3-methyl-1,5-pentanediol; 1,6-hexanediol) carbonate) (made by Curaresa; number average molecular weight 2,000)

Curarepolyol C-3090: poly ((3-methyl-1,5-pentanediol; 1,6-hexanediol) carbonate) (made by Curaresa; number average molecular weight 3,000)

Curarepolyol C-2065N: poly ((1,9-nonanediol; 2-methyl-1,8-octanediol) carbonate) (manufactured by Curaresa; number average molecular weight 2,000)

Curarepolyol C-2015N: poly ((1,9-nonanediol; 2-methyl-1,8-octanediol) carbonate) (manufactured by Curaresa; number average molecular weight 2,000)

Curare polyol P-510, P-1010, C-2090, preminol PPG4000, (C) component used as (A1) component, and (B) component are the same as that of Table 1.

[Examples 18 to 22, Comparative Examples 6 and 7, Reference Example 4]

Except having mix | blended each component in the ratio of Table 3, it carried out similarly to Example 1, and obtained the radiation curable composition for adhesives and a polarizing plate.

The light transmittance of the hardened | cured material of the obtained radiation curable composition, the chip | tip cutting resistance of a polarizing plate, and the heat-and-moisture resistance were evaluated like Example 1, and the initial stage chip | tip cutting resistance of a polarizing plate was further evaluated by the following method.

[Initial chip cutting resistance]

A super dumbbell cutter (SSK-12862-06, manufactured by Dumbbell) and an SD-type lever-type sample cutting machine (SDL-200, manufactured by Dumbbell) were bonded to a polarizing plate that was left standing at 23 ° C. and 50% RH for 1 hour after bonding by light irradiation. Was punched into a size of 50 mm x 80 mm. The periphery of the punched polarizing plate was visually observed and (circle) was observed and the strip | belt shape was seen in the edge part, but the case where it was not peeled off was made into (circle) and the thing where peeling was observed at the edge part was made into x.

The results are shown in Table 3.

In Comparative Examples 6 and 7, the results of measuring the initial chip cutting resistance in addition to the light transmittance, chip cutting resistance, and moisture heat resistance of the composition having the same composition as those of Comparative Examples 1 and 2 described above are described above as Reference Example 4. Table 3 shows the results of measuring the initial chip cutting properties in addition to the light transmittance, the chip cutting resistance, and the heat and humidity resistance of the composition having the same composition as in Example 2.

In addition, the compound name of each component of Table 3 is as follows.

[(D) component]

Aronix M-315: Tris [2- (meth) acryloyloxyethyl] isocyanurate (made by Toagosei Co., Ltd.)

Aronix M-215: bis [2- (meth) acryloyloxyethyl) (2-hydroxyethyl) isocyanurate (made by Toagosei Co., Ltd.)

[Other Ingredients]

Irgacure 184: 1-hydroxycyclohexylphenyl ketone (manufactured by Ciba Specialty Chemicals)

Hitachi 4861: urethane acrylate (manufactured by Hitachi Kasei Kogyo Co., Ltd.)

Kayarrad DPHA: dipentaerythritol hexaacrylate (made by Nippon Kayaku Co., Ltd.)

Curarepolyol P-510, P-1010, C-2090, C-590, (C) component used as (A1) component, (B) component, and SR-NPG and Sannix GP-400 used as another component It is the same as in Table 1 or Table 2.

[Examples 23 to 26, Comparative Example 8, Reference Examples 5 and 6]

Except having mix | blended each component by the ratio of Table 4, it carried out similarly to Example 1, and obtained the polarizing plate.

The peeling strength of the obtained polarizing plate was evaluated like Example 10, and the curvature of the polarizing plate was further evaluated by the following method.

[warp]

The produced polarizing plate is cut out to a size of 10 cm in length and 10 cm in width, and left on the flat glass plate in a state where four corners of the polarizing plate float. The distance from the glass plate of the four corners of a polarizing plate is measured, and let the average value of four points be an average amount of curvature.

(Circle) and the case exceeding 5 mm were made into the case where average curvature amount is 5 mm or less.

The results are shown in Table 4.

In addition, as a comparative example 8, the result which measured the warpage in addition to peeling strength about the composition of the composition similar to the comparative example 2 (comparative example 5) mentioned above is the same as the above-mentioned Examples 4 and 20 as reference examples 5 and 6. Table 4 together shows the results of measuring the warpage in addition to the peel strength of the composition.

In addition, the compound name of each component of Table 4 is as follows.

[(C) component]

Diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate: (manufactured by Acid Aprosa)

Irgacure 250: (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium hexafluorophosphate (manufactured by Ciba Specialty Chemicals)

Diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate: (manufactured by Acid Aprosa)

(A1) component, (B) component, and another component are the same as in Table 1 or Table 3.

From Table 1, it can be seen that the polarizing plates (Examples 1 to 9) of the present invention are excellent in chip cutting resistance (time lapses after 24 hours of light irradiation) and heat and moisture resistance. From Table 2, it can be seen that when the compound represented by the formula (2) is used as the component (B), a polarizing plate excellent in peel strength (adhesion between the protective film and the polarizer) in addition to chip cutting resistance can be obtained (execution). Examples 10-17).

From Table 3, when (D) component is further mix | blended, the polarizing plate which is excellent also in chip breaking resistance (time after 24 hours after light irradiation) and moisture heat resistance and also initial chip cutting resistance (time after 1 hour after light irradiation) can be obtained. It can be seen that (Examples 18 to 22).

From Table 4, it is possible to obtain a polarizing plate having a smaller warpage deformation than using the onium salt of formula (4) as the (C) component (onium salt having an anionic species of PF ₆ ⁻ ). It can be seen (Examples 23 to 26).

From Tables 1 to 4, in Comparative Examples 1 and 2 (corresponding to Comparative Examples 4 and 5 in Table 2 and Comparative Examples 6 and 7, in Table 3, and Comparative Example 8 in Table 4), chip breaking resistance (24 hours after light irradiation) Time), initial chip cutting resistance (time after 1 hour of light irradiation), moist heat resistance, peel strength and warpage are all inferior. From Table 1, it can be seen that the polarizing plate of Comparative Example 3 is inferior in chip cutting resistance and moisture heat resistance.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows an example of the polarizing plate of this invention typically, and FIG. 2 is a flowchart which shows an example of the manufacturing method of the polarizing plate of this invention.

Claims (10)

It is a polarizing plate in which a protective film is laminated | stacked on at least one surface of a polyvinyl alcohol-type polarizing film via an adhesive bond layer, The said adhesive bond layer has (A) alicyclic epoxy compound and (B) one or more hydroxyl groups, and the number average molecular weight is 500 The cured product of the radiation curable composition containing the above compound and (C) photo-acid generator is included, The polarizing plate characterized by the above-mentioned. The polarizing plate according to claim 1, wherein the component (A) is a compound having two or more alicyclic epoxy groups in one molecule of (A1) and / or a compound having one alicyclic epoxy group represented by the following formula (A2): . <Formula 1>

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom or a methyl group) The polarizing plate of Claim 1 or 2 whose number average molecular weights of the said component (B) are 1,000 or more. The polarizing plate of any one of Claims 1-3 whose said component (B) is a compound represented by following formula (2). <Formula 2> HO- (R ⁴ -O-CO-O) _m- (R ⁵ -O-CO-O) _n -R ⁶ -OH (Wherein, R ⁴ and R ⁵ each independently represent a divalent hydrocarbon group having 2 to 12 carbon atoms, R ⁶ represents the same structure as any one of R ⁴ and R ⁵ , m is 2 to 150, and n is 0 To 150 and m + n is 2 to 200). The polarizing plate according to any one of claims 1 to 4, wherein the component (C) is an onium salt represented by the following general formula (4). <Formula 4> [R ⁷ R ⁸ _a R ⁹ _b ¹⁰ _c R _d Z] ⁺ PF ₆ ^- Wherein the cation is an onium ion, Z represents S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl or N≡N, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represents the same or different organic group from each other, a, b, c and d are each an integer of 0 to 3, and (a + b + c + d-1) is the same as the valence of Z) The polarizing plate of any one of Claims 1-5 in which the said radiation curable composition further contains the compound represented by following formula (D) (5). <Formula 5>

(Wherein, R ^11, R ¹² and R ¹³ are each independently a monovalent organic group, R ¹¹ to R ¹³ is two or more of -R ¹⁴ OCOCR ¹⁵ = CH ₂ and, R ¹⁴ is a group of a carbon number of 2 to 8 Divalent organic group, R ¹⁵ is a hydrogen atom or a methyl group) It is a polarizing plate which a protective film is laminated | stacked on at least one surface of a polyvinyl alcohol-type polarizing film via an adhesive bond layer, The said adhesive bond layer is a (A) alicyclic epoxy compound and (C) the photo-acid generator represented by following General formula (4). A cured product of a radiation curable composition comprising a polarizing plate. <Formula 4> [R ⁷ R ⁸ _a R ⁹ _b ¹⁰ _c R _d Z] ⁺ PF ₆ ^- Wherein the cation is an onium ion, Z represents S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl or N≡N, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represents the same or different organic group from each other, a, b, c and d are each an integer of 0 to 3, and (a + b + c + d-1) is the same as the valence of Z) The polarizing plate of any one of Claims 1-7 whose light transmittance of wavelength 550nm is 70% or more, when the said radiation curable composition is made into hardened | cured material of thickness 200micrometer. The polarizing plate of any one of Claims 1-8 in which the said protective film contains cyclic olefin resin. It is a manufacturing method of the polarizing plate of any one of Claims 1-9, The process of laminating | stacking a protective film on the at least one surface of a polarizing film via the said radiation curable composition, and the said radiation curable composition, and hardened | cured The manufacturing method of the polarizing plate containing the hardening process of making it obtain a polarizing plate.

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