TW202019987A - Polarizer, polarizing film, optical film, and image display unit - Google Patents

Abstract

To provide a polarizer and a polarizing film that prevent a deterioration in optical characteristics even under a humidified environment. A polarizer comprises a durability improving layer on at least one surface, wherein the durability improving layer is formed of a curable composition containing a compound (A) in which in a titration test at 60 DEG C, even when 0.5 equivalent of a basic component is added, the increase in pH is 3.0 or less. The compound (A) is preferably [gamma]-butyrolactone (meth)acrylate. The curable composition is preferably polymerized with at least part of the compound (A); the curable composition further preferably contains a polymerization initiator; the durability improving layer is preferably formed of a cured product layer of the curable composition.

Description

Polarizer, polarizing film, optical film and image display device

The invention relates to a polarizer with a durability enhancing layer on at least one surface. Moreover, the present invention relates to a polarizing film having a transparent protective film on at least one area of the polarizer. The polarizing film can be used alone or in the form of an optical film to form an image display device such as a liquid crystal display device (LCD), an organic EL display device, a CRT, and a PDP.

Background of the invention The market for liquid crystal display devices for clocks, mobile phones, PDAs, notebook computers, computer screens, DVD players and TVs is rapidly expanding. The liquid crystal display device visualizes the polarization state through the switching of the liquid crystal, and a polarizer is used based on its display principle. Especially in applications such as TV, Yi Trend pursues high brightness, high contrast, and wide viewing angles, thereby pursuing high transmittance, high polarization, and high color reproducibility of polarizing films.

As a polarizer, iodine-based polarizers are most widely used in view of their high transmittance and high polarization degree. The structure of the iodine-based polarizer is, for example, polyvinyl alcohol (hereinafter also simply referred to as "PVA") to adsorb iodine And extended. Generally speaking, a polarizing film is obtained by bonding a transparent protective film on both sides of a polarizer with a so-called water-based adhesive, which is a product obtained by dissolving a polyvinyl alcohol-based material in water (Patent Document 1 below) ). The transparent protective film is made of triethyl cellulose with high moisture permeability. When using the aforementioned water-based adhesive (so-called wet lamination), a drying step is required after the polarizer and the transparent protective film are laminated.

On the other hand, an active energy ray hardening adhesive has been proposed to replace the aforementioned water-based adhesive. When using an active energy ray-curable adhesive to manufacture a polarizing film, since a drying step is not required, the productivity of the polarizing film can be improved. For example, a radical polymerization type active energy ray-curable adhesive using N-substituted amide-based monomer as a curable component has been proposed (Patent Document 2 below). For example, in a water resistance test for evaluating the presence or absence of discoloration and peeling after being immersed in warm water at 60° C. for 6 hours, the adhesive layer formed using the active energy ray-curable adhesive described in Patent Document 2 can pass the test completely. However, in recent years, the adhesive for polarizing film has been gradually required to further improve the water resistance to the following degree: the severity of the more severe water resistance test can be evaluated by peeling the end after immersion (saturation) in water, for example. .

The following Patent Document 3 reports a technique for forming a resin layer on the surface of the polarizer for the purpose of suppressing the deterioration of the polarizer, but it is known that there is still room for improvement if it is to sufficiently suppress the deterioration of the polarizer under severe humidification conditions .

Prior technical literature Patent Literature Patent Document 1: Japanese Patent Laid-Open No. 2001-296427 Patent Document 2: Japanese Patent Application Publication No. 2012-052000 Patent Document 3: Japanese Patent Laid-Open No. 2000-199819

Summary of the invention Problems to be solved by invention The present invention has been developed in view of the above circumstances, and an object thereof is to provide a polarizer and a polarizing film in which deterioration of optical characteristics is suppressed even in a humidified environment.

Furthermore, an object is to provide an optical film using the polarizing film and an image display device using the polarizing film or the optical film.

Means to solve the problem In order to solve the above-mentioned problems, the present inventors have repeatedly conducted active research. As a result, it has been found that since at least one surface of the polarizer uses a hardening composition containing a compound having a simulated buffering effect as a raw material to form a durability enhancement layer, even Under the humidified environment, the deterioration of the optical characteristics of the polarizer and the polarizing film provided with the polarizer can still be suppressed, and the present invention is solved.

That is, the present invention relates to a polarizer having a durability enhancing layer on at least one surface. The polarizer is characterized in that the durability enhancing layer is formed of a hardening composition containing a compound (A). In the titration test at 60° C., the compound (A) is the one where the alkaline component is added at 0.5 equivalent and the pH rise is still within 3.0.

In the polarizer, the compound (A) is preferably γ-butyrolactone (meth)acrylate.

In the polarizer, at least a part of the compound (A) contained in the curable composition is preferably polymerized.

In the polarizer, the curable composition preferably further contains a polymerization initiator.

In the polarizer, the durability-enhancing layer is preferably formed of a hardened layer of the curable composition.

The present invention also relates to a polarizing film provided with the polarizing member as described in any one of the foregoing.

It is preferable that the polarizing film is provided with a transparent protective film on at least one area of the polarizer, and the transparent protective film is laminated on the side of the durability enhancing layer provided with the polarizer.

The polarizing film is preferably provided with an adhesive layer between the durability improving layer and the transparent protective film.

Furthermore, the present invention relates to an optical film characterized by laminating at least one polarizing film as described above or an image display device characterized by using a polarizing film as described above or an optical film as described above .

Effect of invention As described above, the polarizer generally uses an iodine-based polarizer having a structure in which PVA adsorbs iodine and extends. In the present invention, the polarizer is provided with a durability enhancing layer on at least one surface thereof. The durability enhancing layer is formed of a curable composition containing a compound (A) having a simulated cushioning effect, specifically the compound ( A) In the titration test at 60°C, even if an alkaline component is added at 0.5 equivalent, the pH rise is still within 3.0. Therefore, the deterioration of the optical characteristics of the polarizer can be suppressed even in a humidified environment. The reason why the above effect can be obtained is not yet known, but one of the reasons is that if the surface of the polarizer is provided with a durability improvement layer having a simulated buffering effect, the large pH change of the polarizer can be reduced even in a humidified environment Therefore, the iodine complex existing on the surface of the polarizer can be stabilized.

In addition, in the polarizing film having a transparent protective film on at least one area of the polarizer of the present invention, for example, when there is an adhesive layer between the polarizer and the transparent protective film, the optical properties of the polarizing film can be suppressed even in a humidified environment Degraded characteristics. The reason for obtaining the above-mentioned effects is not yet known, but the use of the durability-enhancing layer can reduce the large pH variation of the polarizer even under a humidified environment, and thus can suppress functional groups such as hydroxyl groups and adhesives present on the surface of the polarizer The covalent bond or hydrogen bond formed between the functional groups of the layer is hydrolyzed. Therefore, one of the reasons we speculate is that it can stabilize the iodine complex present on the surface of the polarizer.

In addition, as long as the polarizing film of the present invention is provided with a polarizer provided with the specific durability enhancing layer on at least one surface, it is not necessary to provide a transparent protective film on the durability enhancing layer. In the polarizing film, the durability improving layer can suppress the deterioration of the optical characteristics of the polarizer under a humidified environment, and at the same time, the durability improving layer can also replace the transparent protective film to play a protective function.

Forms for carrying out the invention The invention relates to a polarizer with a durability enhancing layer on at least one surface. Each structure will be described below.

>Durability Enhancement Layer> The durability-enhancing layer is formed of a hardenable composition containing the compound (A), which has a pH increase within 3.0 even when an alkaline component is added at 0.5 equivalent in a titration test at 60°C.

Compound (A) is a compound that can exhibit a simulated buffering effect, for example, a compound that can exhibit the following behavior: after adjusting to 100 ml of a 0.1M_aqueous solution, when 0.1M_NaOH aqueous solution is added thereto and the pH is measured, the drop amount of NaOH, The pH rise will stabilize first, then show the inflection point and then the pH will rise. By demonstrating the buffering effect, the large pH variation of the polarizer can be reduced even in a humidified environment.

The compound (A) is not particularly limited as long as it is a compound whose pH rises within 3.0 even if 0.5 equivalent of an alkaline component is added in a titration test at 60°C. Examples of the compound include γ-butyrolactone (meth)acrylate.

In addition, the compound (A) may be directly contained in the curable composition, or may be contained in a state where at least a part of the compound (A) is polymerized. Furthermore, at least a part of the compound (A) may be copolymerized with other copolymerizable monomers. When at least a part of the compound (A) is contained in the curable composition in a polymerized state, for example, a layer composed of the curable composition may also be provided on at least one surface of the polarizer using a coating method to be described later. Drying is required to form a durability enhancing layer.

In the durability improving layer, if the content of the compound (A) is too small, the deterioration of the optical characteristics of the polarizer may not be sufficiently suppressed under a humidified environment. Therefore, in the durability improving layer, the content of the compound (A) is preferably 50% by weight or more, and preferably 70% by weight or more, and more preferably 80% by weight or more.

The hardenable composition that can be used as a raw material for forming the durability-improving layer may be composed of only the compound (A), and may contain a polymerization initiator, a solvent, an additive, and the general formula (1) described later in addition to the compound (A) Compound (B) shown.

When the curable composition contains a polymerization initiator in addition to the compound (A), and the durability improvement layer is formed of the cured material layer of the curable composition, the compound (A) and its polymer are fixed to Near the polarizer, the durability of the polarizer can be improved. As a result, it is preferable because the deterioration of the optical characteristics of the polarizer can be suitably suppressed. The method of forming the durability enhancement layer using the hardened material layer includes, for example, applying a hardening composition containing at least the compound (A) and a polymerization initiator to a polarizer, and irradiating active energy rays as described later, thereby curing The method of hardening the sexual composition to form a hardened layer (durability enhancement layer). The usable active energy rays are described later.

、2-氯9-氧硫𠮿

、2-甲基9-氧硫𠮿

、2,4-二甲基9-氧硫𠮿

、異丙基-9-氧硫𠮿

、2,4-二氯9-氧硫𠮿

、2,4-二乙基9-氧硫𠮿

、2,4-二異丙基9-氧硫𠮿

、十二基9-氧硫𠮿

等的9-氧硫𠮿

系化合物；樟腦醌；鹵化酮；醯基氧化膦；醯基膦酸酯等。In the present invention, a photopolymerization initiator is preferably used as a polymerization initiator. The photopolymerization initiator can be appropriately selected according to the active energy ray. When it is hardened by ultraviolet or visible light, a photopolymerization initiator that cracks by ultraviolet or visible light is used. Examples of the aforementioned photopolymerization initiator include diphenyl ethanedione (benzil), diphenyl ketone, benzoyl benzoic acid, 3,3'-dimethyl-4-methoxydiphenyl ketone, etc. Phenyl ketone compounds; 4-(2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α'-dimethylacetophenone, 2-methyl- Aromatic ketone compounds such as 2-hydroxyphenylacetone and α-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethyl Acetophenone compounds such as oxyacetophenone, 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinyl propane-1; benzoin methyl ether, benzene Benzoin ether-based compounds such as diethyl ethyl ether, benzoin isopropyl ether, benzoin butyl ether, anisein methyl ether, etc.; aromatic ketal compounds such as benzyl dimethyl ketal ; Aromatic sulfonyl chloride compounds such as 2-naphthalene sulfonyl chloride; photoactive oxime compounds such as 1-benzophenone-1,1-propanedione-2-(o-ethoxycarbonyl)oxime; 9-oxygen Sulfur 𠮿

、2-chloro9-oxygen and sulfur 𠮿

、2-Methyl 9-Oxysulfur 𠮿

、2,4-Dimethyl 9-oxysulfur 𠮿

、Isopropyl-9-oxysulfur 𠮿

、2,4-Dichloro 9-oxygen and sulfur 𠮿

、2,4-Diethyl 9-oxysulfur 𠮿

、2,4-Diisopropyl 9-oxysulfur 𠮿

, Dodecyl 9-oxygen sulfide 𠮿

9-Oxygen Sulfur 𠮿

Compounds; camphorquinone; halogenated ketones; acylphosphine oxide; acylphosphonate, etc.

(式中，R⁶ 及R⁷ 表示-H、-CH₂ CH₃ 、-iPr或Cl，且R⁶ 及R⁷ 可相同或相異)。相較於單獨使用對380nm以上的光有高感度之光聚合起始劑的情形，使用通式(3)所示化合物時之接著性較佳。通式(3)所示化合物當中，以R⁶ 及R⁷ 為-CH₂ CH₃ 之二乙基9-氧硫𠮿

尤佳。硬化性組成物中通式(3)所示化合物的組成比率相對於化合物(A)宜為0.5~4.0重量%，更宜為1.0~2.5重量%。The aforementioned photopolymerization initiator is preferably used alone or in combination with the compound represented by the following general formula (3) and a photopolymerization initiator having a high sensitivity to light of 380 nm or more as described below: [Chemical Formula 1 ]

(In the formula, R ⁶ and R ⁷ represent -H, -CH ₂ CH ₃ , -iPr or Cl, and R ⁶ and R ⁷ may be the same or different). Compared with the case where a photopolymerization initiator having high sensitivity to light of 380 nm or more is used alone, the adhesiveness when using the compound represented by the general formula (3) is better. Among the compounds represented by the general formula (3), R ⁶ and R ⁷ are -CH ₂ CH ₃ diethyl 9-oxysulfur 𠮿

Especially good. The composition ratio of the compound represented by the general formula (3) in the curable composition is preferably 0.5 to 4.0% by weight relative to the compound (A), and more preferably 1.0 to 2.5% by weight.

In addition, it is preferable to add a polymerization initiation aid as needed. Examples of the polymerization start aid include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl ester, 4-dimethylaminobenzoic acid Ethyl acetate, isoamyl 4-dimethylaminobenzoate, etc., particularly preferably ethyl 4-dimethylaminobenzoate. When using the polymerization initiation aid, the amount of addition relative to the total amount of the compound (A) is generally 0 to 5% by weight, preferably 0 to 4% by weight, and 0 to 3% by weight.

In addition, a known photopolymerization initiator can be used in combination as required. The transparent protective film with UV absorption energy will not transmit light below 380nm, so the photopolymerization initiator should be a photopolymerization initiator with high sensitivity to light above 380nm. Specifically, for example, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinylphenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholin Linyl)phenyl)-1-butanone, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzyl) -Phenylphosphine oxide, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl) titanium Wait.

(式中，R⁸ 、R⁹ 及R¹⁰ 表示-H、-CH₃ 、-CH₂ CH₃ 、-iPr或Cl，且R⁸ 、R⁹ 及R¹⁰ 可相同或相異)。通式(4)所示化合物可適當使用亦屬市售品的2-甲-1-(4-甲基硫基苯基)-2-嗎福林基丙-1-酮(商品名：IRGACURE907，製造商：BASF)。除此之外，2-苄-2-二甲胺基-1-(4-嗎福林基苯基)-丁-1-酮(商品名：IRGACURE369，製造商：BASF)、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎福林基)苯基]-1-丁酮(商品名：IRGACURE379，製造商：BASF)由於感度高，因此較為理想。硬化性組成物中通式(4)所示化合物的組成比率相對於化合物(A)宜為0.5~4.0重量%，更宜為1.0~2.5重量%。In particular, as the photopolymerization initiator, in addition to the photopolymerization initiator of the general formula (3), it is also preferable to use the compound represented by the following general formula (4): [Chemical Formula 2]

(In the formula, R ⁸ , R ⁹ and R ¹⁰ represent -H, -CH ₃ , -CH ₂ CH ₃ , -iPr or Cl, and R ⁸ , R ⁹ and R ¹⁰ may be the same or different). As the compound represented by the general formula (4), 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone (trade name: IRGACURE907), which is also a commercially available product, can be suitably used. , Manufacturer: BASF). In addition, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one (trade name: IRGACURE369, manufacturer: BASF), 2-(di Methylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: IRGACURE379, manufacturer: BASF) is ideal because of its high sensitivity. The composition ratio of the compound represented by the general formula (4) in the curable composition is preferably 0.5 to 4.0% by weight relative to the compound (A), and more preferably 1.0 to 2.5% by weight.

The solvent that can be contained in the hardenable composition is preferably a substance that can stabilize and dissolve or disperse the compound (A) and its polymer and polymerization initiator. As the solvent, an organic solvent, water, or a mixed solvent thereof can be used. The aforementioned solvent may be selected from the following, for example: ethyl acetate, butyl acetate, 2-hydroxyethyl acetate and other esters; methyl ethyl ketone, acetone, cyclohexanone, methyl isobutyl ketone, diethyl ketone, Ketones such as methyl-n-acetone and acetone; cyclic ethers such as tetrahydrofuran (THF) and dioxane; aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane; aromatics such as toluene and xylene Hydrocarbons; aliphatic or alicyclic alcohols such as methanol, ethanol, n-propanol, isopropanol, cyclohexanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether Glycol ethers such as basic ethers; glycol ether acetates such as diethylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate.

The additives that the curable composition may contain include, for example, surfactants, plasticizers, tackifiers, low molecular weight polymers, polymerizable monomers, surface lubricants, leveling agents, antioxidants, preservatives, light stabilizers Agent, ultraviolet absorber, polymerization inhibitor, silane coupling agent, titanate coupling agent, inorganic or organic filler, metal powder, granular, foil, etc.

Regarding the method of forming the durability enhancing layer on the polarizer using the curable composition, a method of directly immersing the polarizer in the treatment bath of the curable composition or a known coating method can be suitably used. The aforementioned coating method specifically includes, for example, roll coating, gravure coating, reverse coating, roll brush, spray cloth, air knife coating, and curtain coating method, but is not limited thereto.

When the curable composition contains a polymerization initiator, the durability enhancement layer can be formed by hardening the curable composition on at least one surface of the polarizer to form a hardened layer, or by at least one of the polarizer A durability enhancement layer composed of an uncured curable composition is formed on the surface, and after being laminated with a transparent protective film, the curable composition is cured to form a durability enhancement layer composed of a cured material layer.

>polarizer> The polarizer is not particularly limited, and various polarizers can be used. Examples of polarizers include hydrophilic polymer films such as polyvinyl alcohol-based films, partially formalized polyvinyl alcohol-based films, and ethylene-vinyl acetate copolymer-based partially saponified films that adsorb iodine or dichroic dyes. The dichromatic material is uniaxially stretched, and the polyene oriented film such as polyvinyl alcohol dehydration treatment or polyvinyl chloride dehydrochlorination treatment etc. Among them, a polarizer composed of a polyvinyl alcohol-based film and a dichroic substance such as iodine is preferable. The thickness of the polarizers is usually 1-30 μm.

The polarizing member in which the polyvinyl alcohol-based film is dyed with iodine and uniaxially stretched can be produced by, for example, immersing polyvinyl alcohol in an iodine aqueous solution and dyeing it, and stretching it to 3 to 7 times its original length. It can also be immersed in an aqueous solution of boric acid or potassium iodide according to requirements. Further, if necessary, the polyvinyl alcohol-based film is immersed in water and washed with water before dyeing. By washing the polyvinyl alcohol-based film with water, the dirt and anti-caking agent on the surface of the polyvinyl alcohol-based film can be washed. In addition, the polyvinyl alcohol-based film swells to prevent uneven dyeing and other unevenness. The stretching may be performed after dyeing with iodine, or it may be stretched while dyeing, or it may be dyed with iodine after stretching. It can also be extended in an aqueous solution such as boric acid or potassium iodide or in a water bath.

However, for mobile applications such as mobile phones, from the viewpoint of design and miniaturization, the demand for thin polarizers with a thickness of less than 10 μm is increasing, but if the thickness of the polarizer becomes thinner, especially in a humidified environment Next, the deterioration of the optical characteristics tends to become significant. However, the polarizer of the present invention is a thin polarizer with a thickness of 10 μm or less and has an optical enhancement layer on at least one surface, so the deterioration of optical characteristics can be suppressed even in a humidified environment. The thickness of the polarizer is preferably 1 to 7 μm from the viewpoint of thinning. Such a thin polarizer has less unevenness in thickness, excellent visibility, and small dimensional change, and the thickness of the polarizing film can also be made thinner, which is ideal from the viewpoint.

The thin polarizer is typically listed in Japanese Patent Laid-Open No. 51-069644, Japanese Patent Laid-Open No. 2000-338329, WO2010/100917 Manual, PCT/JP2010/001460, or Japanese Patent No. 2010 -269002 specification or Japanese Patent Application No. 2010-263692 specification thin polarizing film. These thin polarizing films can be produced by a manufacturing method including a step of extending and dyeing a layer of a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) and a resin substrate for extension in the state of a laminate . As long as this manufacturing method is used, even if the PVA-based resin layer is very thin, it is supported by the resin substrate for stretching, so that it can be stretched without being broken due to stretching.

As the aforementioned thin polarizing film, in the manufacturing method including the step of stretching in the state of the laminate and the step of dyeing, from the viewpoint of being able to stretch at a high magnification to improve the polarizing performance, it is desirable to use, for example, WO2010/ 100917 manual, PCT/JP2010/001460 specification, or Japanese Patent Application No. 2010-269002 or Japanese Patent Application No. 2010-263692 described in the method including the step of extending in boric acid aqueous solution It is particularly desirable to use a method that includes the steps of performing auxiliary air stretching before stretching in an aqueous boric acid solution as described in Japanese Patent Application No. 2010-269002 or Japanese Patent Application No. 2010-263692 By.

The surface modification treatment of the polarizer may also be performed before the formation of the aforementioned durability enhancing layer and the easy-adhesion layer described later. The surface modification treatment may include corona treatment, plasma treatment, and ITRO treatment (flame silane treatment). Corona treatment is particularly preferred. By performing corona treatment, reactive functional groups such as carbonyl groups or amine groups can be formed on the surface of the polarizer, thereby improving the adhesion to the durability improving layer. In addition, the ashing effect can remove surface foreign substances and reduce surface irregularities, so that a polarizing film with excellent appearance characteristics can be made.

(惟，X為含有反應性基之官能基，R¹ 及R² 分別獨立表示氫原子或可具有取代基之脂肪族烴基、芳基或雜環基)。於偏光件上形成有含有化合物(B)的易接著層時，化合物(B)具有之硼酸基及/或硼酸酯基會與偏光件具有之羥基等官能基反應，並且亦會與用於形成耐久性提升層的化合物(A)反應。因此，可提升偏光件與耐久性提升層之密著性故而為佳。The polarizer of the present invention may also form an easy adhesion layer on the polarizer before forming the durability enhancement layer, and form a durability enhancement layer on the easy adhesion layer. The easy adhesion layer preferably contains the compound (B) represented by the following general formula (1): [Chemical Formula 3]

(However, X is a functional group containing a reactive group, and R ¹ and R ² each independently represent a hydrogen atom or an aliphatic hydrocarbon group, an aryl group, or a heterocyclic group which may have a substituent). When an easy-adhesion layer containing the compound (B) is formed on the polarizer, the boric acid group and/or borate ester group possessed by the compound (B) will react with the functional groups such as the hydroxyl group possessed by the polarizer, and will also react with the The compound (A) forming the durability enhancing layer reacts. Therefore, it is preferable to improve the adhesion between the polarizer and the durability improving layer.

Examples of the aforementioned aliphatic hydrocarbon group include linear or branched alkyl groups which may have a C 1-20 substituent, cyclic alkyl groups which may have a C 3-20 substituent, and C 2-20 alkenyl groups. Aryl groups can be exemplified by phenyl groups which may have a C 6-20 substituent, naphthyl groups which may be a C 10-20 substituent, etc.; heterocyclic groups may be exemplified by containing at least one heteroatom and may have a substitution Based on the 5 member ring or 6 member ring group. These can be connected to each other to form a ring. In the general formula (1), R ¹ and R ^{2 are} preferably a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, and the hydrogen atom is the best.

In addition, the compound (B) represented by the general formula (1) may exist in the unreacted state in the easy-adhesion layer, or the state in which each functional group has reacted may be in between. In addition, "the compound (B) represented by the general formula (1) is contained in the easy-adhesion layer" means that, for example, there is at least one molecule of the compound (B) represented by the general formula (1) in the easy-adhesion layer. However, in order to improve the adhesion between the polarizer and the durability-enhancing layer, and to more appropriately suppress the deterioration of the optical durability of the polarizer, it is preferable to use an easy-adhesive composition containing the compound (B) represented by the general formula (1). At least a part of the surface of the part on which the durability enhancing layer is to be formed forms an easy adhesion layer, and it is better to form the easy adhesion layer on the entire surface of the surface of the polarizing member on which the durability improving layer is to be formed.

X in the compound (B) represented by the general formula (1) is a functional group containing a reactive group. The reactive group contained in X can be exemplified by a hydroxyl group, an amine group, an aldehyde group, a carboxyl group, a vinyl group, a (meth)acryloyl group, a styryl group, a (meth)acrylamide group, a vinyl ether group, an epoxy group Group, oxetanyl group, α,β-unsaturated carbonyl group, mercapto group, halogen group, etc. However, to make it react with the carbon-carbon double bond of the monomer (A) to improve the adhesion between the polarizer and the durability-improving layer, the reactive group contained in X is preferably selected from vinyl, Group) at least one reactive group in the group consisting of acryl, styryl, (meth)acryl, vinyl ether, epoxy, oxetanyl and mercapto groups, and More preferably, it is at least one kind of reactive group selected from the group consisting of (meth)acryloyl group, styryl group and (meth)acrylamide group.

(惟，Y為有機基，X、R¹ 及R² 與前述相同)。更佳可舉以下化合物(1a)~(1d)。 [化學式5]

Specific examples of the compound (B) represented by the general formula (1) include compounds represented by the following general formula (1′): [Chemical Formula 4]

(However, Y is an organic group, and X, R ¹ and R ^{2 are the} same as described above). More preferably, the following compounds (1a) to (1d) can be mentioned. [Chemical Formula 5]

In the present invention, the compound (B) represented by the general formula (1) may be a group in which a reactive group is directly bonded to a boron atom. As shown in the foregoing specific example, the compound (B) represented by the general formula (1) is preferably a reaction The sex group and the boron atom are bonded through the organic group, that is, the compound (B) represented by the general formula (1'). When the compound (B) represented by the general formula (1) is, for example, bonded to a reactive group via an oxygen atom bonded to a boron atom, the optical characteristics of the polarizer tend to deteriorate. On the other hand, the compound (B) represented by the general formula (1) is not a boron-oxygen bond, but a boron-carbon bond and a reactive group containing a boron-carbon bond to an organic group (through (Equation (1')) is preferable because it can suppress the deterioration of the optical characteristics of the polarizer. The aforementioned organic group specifically means an organic group having 1 to 20 carbon atoms which may have a substituent, and more specifically, for example, a linear or branched alkylene group which may have a substituent having 1 to 20 carbon atoms, may have a carbon Cyclic alkylene groups with 3 to 20 substituents, phenylene groups with 6 to 20 carbon substituents, naphthyl groups with 10 to 20 carbon substituents, etc.

The compound (B) represented by the general formula (1) may include, in addition to the compounds exemplified above, esters of hydroxyethylacrylamide and boric acid, esters of hydroxymethylacrylamide and boric acid, hydroxyethyl acrylate and boric acid Esters, and esters of (meth)acrylate and boric acid such as hydroxybutyl acrylate and boric acid.

On the surface of the polarizer on which the durability improving layer is to be formed, a method of forming an easy-adhesion layer using an easy-adhesive composition containing the compound (B) represented by the general formula (1) can be exemplified by: manufacturing a compound containing the general formula (1) The method of forming the easily adhering composition of the compound (B) shown and applying it to the surface of the polarizer on the side where the durability improving layer is to be formed. In the easy-adhesion composition, substances that can be contained other than the compound (B) represented by the general formula (1) include solvents, additives, and radically polymerizable compounds described below.

When the easy-adhesion composition contains a solvent, the easy-adhesion composition may be coated on the surface of the polarizer on which the durability improving layer is to be formed, and a drying step or hardening treatment (heat treatment, etc.) may be performed as necessary.

Solvents and additives that may be contained in the easy-to-adhere composition may use solvents and additives that may be contained in the hardenable composition. Regarding the method of forming the easy-adhesive layer on the polarizer using the easy-adhesive composition, the same method as the method of forming the durability enhancing layer on the polarizer using the hardenable composition described above can be used.

If the content of the compound (B) represented by the general formula (1) in the easy-adhesion layer is too small, the ratio of the compound (B) represented by the general formula (1) existing on the surface of the easy-adhesion layer will decrease, and the effect of the easy-adhesion may decrease. . Therefore, the content of the compound (B) represented by the general formula (1) in the easy adhesion layer is preferably 1% by weight or more, preferably 20% by weight or more, and more preferably 40% by weight or more.

In the present invention, when the thickness of the easy-adhesive layer provided in the polarizer is too thick, the cohesive force of the easy-adhesive layer is reduced, and the easy-adhesive effect may be reduced. Therefore, the thickness of the easy adhesion layer is preferably 2000 nm or less, preferably 1000 nm or less, and more preferably 500 nm or less. On the other hand, in order for the easy-adhesion layer to fully exert its effect, the lowest limit of the thickness may be at least the thickness of the monomolecular film of the compound represented by the general formula (1), preferably 1 nm or more, preferably 2 nm or more, and 3 nm or more Better.

As described above, the compound (B) represented by the general formula (1) is not only used for forming an easy-adhesion layer, but can also be added to the curable composition together with the compound (A). At this time, the compound (B) will react and/or interact with the polarizer and the compound (A), so that the compound (A) is more firmly fixed in the vicinity of the polarizer, thereby further improving the durability improvement of the polarizer. As a result, the deterioration of the optical characteristics of the polarizer can be suitably suppressed, which is preferable.

The polarizing film of the present invention includes a polarizer having a durability enhancing layer on at least one surface, the durability enhancing layer is formed of a curable composition containing a compound (A), and the compound (A) has a carbon-carbon double bond and Ring skeleton. Moreover, the polarizing film of the present invention may be a transparent protective film on at least one area of the polarizer. The polarizer and the transparent protective film may be laminated via a durability enhancement layer, and the durability enhancement layer and the transparent protective film of the polarizer may be laminated via an adhesive. The adhesive layer will be described below.

>Adhesive layer> The thickness of the adhesive layer is preferably 0.01 to 3.0 μm. If the thickness of the adhesive layer is too thin, the peeling force will be reduced due to insufficient cohesive force of the adhesive layer, which is not good. When the thickness of the adhesive layer is too thick, peeling is likely to occur when stress is applied to the cross section of the polarizing film, and poor peeling due to impact occurs, which is not good. The thickness of the adhesive layer is preferably 0.1 to 2.5 μm, and most preferably 0.5 to 1.5 μm.

The adhesive layer is formed by hardening the adhesive composition. The hardened form of the adhesive composition can be roughly divided into heat hardening and active energy ray hardening. Thermosetting resins include polyvinyl alcohol resins, epoxy resins, unsaturated polyesters, urethane resins, acrylic resins, urea resins, melamine resins, phenol resins, etc., and can be used in combination with a hardener as needed. As the thermosetting resin, polyvinyl alcohol resin or epoxy resin can be more suitably used. Active energy ray-curable resins are classified by active energy rays, and can be roughly classified into electron beam-curable, ultraviolet-curable, and visible-ray curable. In addition, the hardened form can be divided into a radically polymerizable adhesive composition and a cationically polymerizable adhesive composition. In the present invention, active energy rays with a wavelength range of 10 nm to less than 380 nm are marked as ultraviolet rays, and active energy rays with a wavelength range of 380 nm to 800 nm are marked as visible rays.

In the production of the polarizing film of the present invention, as described above, it is preferably active energy ray curable. In addition, the visible light curing with 380nm to 450nm visible light is particularly good.

Examples of the hardenable component contained in the radical polymerizable adhesive composition include radical polymerizable compounds used in the radical polymerizable adhesive composition. Examples of the radically polymerizable compound include compounds having a radically polymerizable functional group such as a (meth)acryloyl group and a vinyl group such as a carbon-carbon double bond. As these hardening components, any of a monofunctional radical polymerizable compound or a bifunctional or higher polyfunctional radical polymerizable compound can be used. In addition, these radically polymerizable compounds may be used alone or in combination of two or more. The radical polymerizable compound is preferably a compound having a (meth)acryloyl group. In the present invention, the term "(meth)acryloyl" refers to acryloyl and/or methacryloyl, which is synonymous with "(meth)" below.

(惟，R³ 為氫原子或甲基，R⁴ 及R⁵ 分別獨立為氫原子、烷基、羥烷基、烷氧基烷基或環狀醚基，且R⁴ 及R⁵ 亦可形成環狀雜環)。烷基、羥烷基及/或烷氧基烷基之烷基部分的碳數並無特別限定，可舉例如1~4個者。此外，R⁴ 及R⁵ 亦可形成之環狀雜環可舉例如N-丙烯醯基嗎福林。Examples of the monofunctional radical polymerizable compound are compounds represented by the following general formula (2): [Chemical formula 6]

(However, R ³ is a hydrogen atom or a methyl group, R ⁴ and R ⁵ are independently a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, or a cyclic ether group, and R ⁴ and R ⁵ may also be formed Cyclic heterocycle). The carbon number of the alkyl portion of the alkyl group, hydroxyalkyl group, and/or alkoxyalkyl group is not particularly limited, and examples thereof include 1 to 4 carbon atoms. In addition, the cyclic heterocyclic ring which R ⁴ and R ⁵ may form may be exemplified by N-propenyl morpholin.

Specific examples of the compound represented by the general formula (2) include, for example, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl( N-alkyl-containing (meth)acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide, N-hexyl (meth)acrylamide ( Meth) acrylamide derivatives; N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxymethyl-N-propane (meth) acrylamide N-hydroxyalkyl-containing (meth)acrylamide derivatives such as amines; N-alkoxymethyl-acrylamide, N-ethoxymethacrylamide and other N-alkoxy-containing (meth Group) acrylamide derivatives and the like. Further, the (meth)acrylamide derivative containing a cyclic ether group may include a heterocyclic-containing (meth)acrylamide derivative in which the nitrogen atom of the (meth)acrylamide group forms a heterocycle, and For example, N-propenyl morpholin, N-propenyl piperidine, N-methacryl piperidine, N-propenyl pyrrolidine and the like can be mentioned. From the viewpoint of good reactivity, the viewpoint of obtaining a hardened product with a high elastic coefficient, and the viewpoint of excellent adhesion to polarizers, N-hydroxyethylacrylamide or N-acrylamide can be suitably used among them Forint.

From the viewpoint of improving the adhesion and water resistance of the polarizer and the transparent protective film through the adhesive layer, the content of the compound described in the general formula (2) in the adhesive composition is preferably 0.01 to 80% by weight. It is more preferably 5 to 40% by weight.

In addition, the adhesive composition used in the present invention may contain other monofunctional radical polymerizable compounds as the hardening component in addition to the compound represented by the general formula (2). Examples of the monofunctional radical polymerizable compound include various (meth)acrylic acid derivatives having (meth)acryloyloxy groups. Specifically, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-methyl-2-nitro Propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, secondary butyl (meth)acrylate, tertiary butyl (meth)acrylate, (methyl ) N-pentyl acrylate, tertiary pentyl (meth) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, Cetyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 4-methyl-2-propylpentyl (meth)acrylate, (meth) (Meth) acrylic acid (C 1-20) alkyl esters such as n-octadecyl acrylate.

In addition, the (meth)acrylic acid derivatives include, for example, cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate and cyclopentyl (meth)acrylate; benzyl (meth)acrylate and other (meth) )) aralkyl acrylate; (meth)acrylic acid-2-isobornyl ester, (meth)acrylic acid-2-norbornyl methyl ester, (meth)acrylic acid-5-norbornen-2-yl-methyl Ester, 3-methyl-2-norbornyl methyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, (meth) Polycyclic (meth)acrylates such as dicyclopentyl acrylate; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, (meth)acrylic acid- 2-methoxymethoxyethyl, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxyethyl (meth)acrylate, alkylbenzene Alkoxy or phenoxy-containing (meth)acrylates and the like such as oxypolyethylene glycol (meth)acrylates. Among these, from the viewpoint of good adhesion to various protective films, dicyclopentenyloxyethyl acrylate and phenoxyethyl acrylate are preferred.

Furthermore, examples of the (meth)acrylic acid derivatives include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (Meth)acrylic acid-2-hydroxybutyl ester, (meth)acrylic acid-4-hydroxybutyl ester, (meth)acrylic acid-6-hydroxyhexyl ester, (meth)acrylic acid-8-hydroxyoctyl ester, (meth) Group) hydroxyalkyl (meth)acrylates such as -10-hydroxydecyl acrylate, -12-hydroxylauryl (meth)acrylate; or [4-(hydroxymethyl)cyclohexyl] methacrylate, cyclic Hydroxy-containing (meth)acrylates such as hexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate; glycidyl (meth)acrylate, ( (Meth)acrylic acid 4-hydroxybutyl ester glycidyl ether and other epoxy-containing (meth)acrylate; (meth)acrylic acid 2,2,2-trifluoroethyl, (meth)acrylic acid 2, 2,2-trifluoroethyl ethyl ester, tetrafluoropropyl (meth)acrylate, hexafluoropropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptafluorodecyl (meth)acrylate Ester, (meth)acrylic acid-3-chloro-2-hydroxypropyl ester and other halogen-containing (meth)acrylate; dimethylaminoethyl (meth)acrylate and other (meth)acrylic acid alkylamino group Alkyl esters; (meth)acrylic acid-3-oxetanyl methyl ester, (meth)acrylic acid-3-methyl-oxetanyl methyl ester, (meth)acrylic acid-3-ethyl- Oxyheteroyl methyl esters, (meth)acrylic acid-3-butane-oxetanyl methyl esters, (meth)acrylic acid-3-hex-oxetanyl methyl esters, etc. (Meth)acrylates of cyclobutane; tetrahydrofurfuryl (meth)acrylate, butyrolactone (meth)acrylate and other (meth)acrylates with heterocycles; and neopentyl hydroxytrimethylacetate Glycol (meth)acrylic acid adducts, p-phenylphenol (meth)acrylate, etc. Among these, 2-hydroxy-3-phenoxypropyl acrylate is preferable because of its excellent adhesion to various protective films.

The monofunctional radical polymerizable compound may be exemplified by (meth)acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and other carboxyl-containing monomers. body.

、乙烯基吡

、乙烯基吡咯、乙烯基咪唑、乙烯基㗁唑、乙烯基嗎福林等具有含氮雜環之乙烯基系單體等等。In addition, examples of the monofunctional radical polymerizable compound include lactamyl vinyl monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and methylvinylpyrrolidone; ethylene Pyridinium, vinyl piperidone, vinyl pyrimidine, vinyl piperidine

Vinylpyridine

, Vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholine and other vinyl monomers with nitrogen-containing heterocycles and the like.

In the adhesive composition used in the present invention, if it contains highly polar hydroxyl-containing (meth)acrylate, carboxyl-containing (meth)acrylate or phosphoric acid group-containing monofunctional radical polymerizable compound (Meth) acrylate, etc., will increase the adhesion to various substrates. The content of (meth)acrylate containing hydroxyl groups is preferably 1% to 30% by weight relative to the resin composition. When the content is too large, the water absorption rate of the hardened product will increase and the water resistance may deteriorate. The content of the (meth)acrylate containing carboxyl groups is preferably 1% to 20% by weight relative to the resin composition. When the content is too much, the optical durability of the polarizing film will be reduced, which is not good. Examples of the (meth)acrylate containing a phosphoric acid group include 2-(meth)acryloyloxyethyl acid phosphate; its content is preferably 0.1% by weight to 10% by weight relative to the resin composition. When the content is too much, the optical durability of the polarizing film will be reduced, which is not good.

As the monofunctional radical polymerizable compound, a radical polymerizable compound having an active methylene group can be used. A radical polymerizable compound having an active methylene group is a compound having an active double bond group such as (meth)acryl acetyl group at the terminal or molecule and having an active methylene group. The active methylene group can be exemplified by: acetylacetoyl, alkoxypropanediamide, cyanoacetate, and the like. In addition, the aforementioned active methylene group is preferably acetylacetoyl. Specific examples of the radically polymerizable compound having an active methylene group include 2-acetylacetoxyethyl (meth)acrylate, 2-acetylacetoxypropyl (meth)acrylate , 2-Ethylacetoxy-1-methylethyl (meth)acrylate, etc. Ethylacetoxyalkyl (meth)acrylate; 2-ethoxypropanedioxyethyl (Meth)acrylate, 2-cyanoacetoxyethyl (meth)acrylate, N-(2-cyanoacetoxyethyl)acrylamide, N-(2-propionyl) Acetyloxybutyl) acrylamide, N-(4-acetylacetoxymethylbenzyl)acrylamide, N-(2-acetylacetethylamidoethyl)acrylamide, etc. . In addition, the radically polymerizable compound having an active methylene group is preferably acetyl acetyl oxyalkyl (meth) acrylate.

Examples of the multifunctional radical polymerizable compound having more than two functions include N,N'-methylenebis(meth)acrylamide and tripropylene glycol di(meth)acrylamide derivatives which are polyfunctional (meth)acrylamide derivatives. Meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1, 10-decanediol diacrylate, 2-ethyl-2-butylpropanediol di(meth)acrylate, bisphenol A di(meth)acrylate, bisphenol A ethylene oxide adduct di(meth) Base) acrylate, bisphenol A propylene oxide adduct di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol di(meth)acrylate , Tricyclodecane dimethanol di(meth)acrylate, cyclic trimethylolpropane methylal (meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri( Methacrylates, neopentaerythritol tri(meth)acrylates, neopentaerythritol tetra(meth)acrylates, dipentaerythritol penta(meth)acrylates, dipentaerythritol hexa(meth)acrylates Methacrylic acid ester, EO modified diglycerol tetra(meth)acrylic acid ester and other esters of (meth)acrylic acid and polyhydric alcohol, 9,9-bis[4-(2-(meth)acryloyloxy) Ethoxy)phenyl] stilbene. Specific examples include ARONIX M-220 (manufactured by East Asia Synthetic Corporation), LIGHT-ACRYLATE 1, 9ND-A (manufactured by Kyoeisha Chemical Company), LIGHT-ACRYLATE DGE-4A (manufactured by Kyoeisha Chemical Company), LIGHT-ACRYLATE DCP -A (made by Kyoeisha Chemical Co., Ltd.), SR-531 (made by Sartomer), CD-536 (made by Sartomer), etc. are preferable. In addition, as required, various epoxy (meth)acrylates, urethane (meth)acrylates, polyester (meth)acrylates, various (meth)acrylate-based monomers, etc. may be mentioned. . In addition, the polyfunctional (meth)acrylamide derivative has a fast polymerization rate and excellent productivity, and is excellent in crosslinkability when the resin composition is made into a cured product, so it is preferably contained in the adhesive composition.

From the viewpoint of taking into consideration the adhesion with polarizers or various transparent protective films and the optical durability in harsh environments, the radically polymerizable compound uses a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound together Better. In general, it is preferable to use a ratio of 3 to 80% by weight of a monofunctional radical polymerizable compound and 20 to 97% by weight of a polyfunctional radical polymerizable compound with respect to 100% by weight of the radical polymerizable compound.

The adhesive composition used in the present invention can be used in the form of an active energy ray-curable adhesive composition when the curable component is used as an active energy ray-curable component. When the active energy ray-curable adhesive composition described above uses electron beams or the like as the active energy ray, the active energy ray-curable adhesive composition does not necessarily contain a photopolymerization initiator, but is used for ultraviolet rays or visible rays. When used as an active energy ray, it should contain a photopolymerization initiator. The photopolymerization initiator may be the same as that used to form the durability enhancing layer.

In the above active energy ray-curable adhesive composition, when a radically polymerizable compound having an active methylene group is used as a radically polymerizable compound, it is preferably used in combination with a radical polymerization initiator having a hydrogen abstraction effect. With the aforementioned configuration, even if it is just taken out from a high-humidity environment or water (non-dry state), the adhesiveness of the adhesive layer of the polarizing film will still be significantly improved. This reason is not clear, but it can be presumed as the following reasons. That is, the radical polymerizable compound having an active methylene group will be incorporated into the main chain and/or side chain of the base polymer in the adhesive layer while polymerizing together with other radical polymerizable compounds constituting the adhesive layer, An adhesive layer is formed. In the aforementioned polymerization process, once a radical polymerization initiator having a hydrogen abstraction effect is present, it will take away hydrogen from a radically polymerizable compound having an active methylene group while forming the base polymer constituting the adhesive layer, and Free radicals are generated in the methylene group. As a result, the free-radical methylene group reacts with the hydroxyl group of the polarizer such as PVA to form a covalent bond between the adhesive layer and the polarizer. As a result, it can be inferred that even in the non-dry state, the adhesion of the adhesive layer of the polarizing film is still significantly improved.

系自由基聚合起始劑、二苯基酮系自由基聚合起始劑等。前述自由基聚合起始劑以9-氧硫𠮿

系自由基聚合起始劑為佳。作為9-氧硫𠮿

系自由基聚合起始劑，可舉例如上述通式(3)所示化合物。通式(3)所示化合物之具體例可舉出9-氧硫𠮿

系、二甲基9-氧硫𠮿

系、二乙基9-氧硫𠮿

、異丙基9-氧硫𠮿

系、氯9-氧硫𠮿

系等。通式(3)所示化合物當中，以R⁶ 及R⁷ 為-CH₂ CH₃ 之二乙基9-氧硫𠮿

尤佳。In the present invention, the radical polymerization initiator having a hydrogen abstraction effect can be exemplified by 9-oxosulfur 𠮿

Radical polymerization initiators, diphenyl ketone radical polymerization initiators, etc. The aforementioned radical polymerization initiator starts with 9-oxosulfur 𠮿

It is preferably a radical polymerization initiator. As 9-oxygen sulfur 𠮿

Examples of the radical polymerization initiator include compounds represented by the above general formula (3). Specific examples of the compound represented by the general formula (3) include 9-oxysulfur 𠮿

Department, dimethyl 9-oxysulfur 𠮿

Department, diethyl 9-oxosulfur 𠮿

、Isopropyl 9-oxysulfur 𠮿

Department, Chlorine 9-Oxygen Sulphur 𠮿

Department etc. Among the compounds represented by the general formula (3), R ⁶ and R ⁷ are -CH ₂ CH ₃ diethyl 9-oxysulfur 𠮿

Especially good.

When the active energy ray-curable adhesive composition described above contains a radically polymerizable compound having an active methylene group and a radical polymerization initiator having a hydrogen abstraction function, the total amount of the curable component is defined as When it is 100% by weight, it should preferably contain 1-50% by weight of the aforementioned radically polymerizable compound having an active methylene group, and it should preferably contain 0.1-10% by weight of the radical polymerization start relative to the total amount of the adhesive composition Agent.

As described above, in the present invention, in the presence of a radical polymerization initiator having a hydrogen abstraction function, the methylene group of the radically polymerizable compound having an active methylene group generates radicals, and the aforementioned methylene group will react with The hydroxyl groups of polarizers such as PVA react to form covalent bonds. Therefore, in order to generate radicals of the methylene group of the radical polymerizable compound having an active methylene group and sufficiently form the aforementioned covalent bond, when the total amount of the curable component is set to 100% by weight, it has an active methylene group The radical polymerizable compound preferably contains 1 to 50% by weight, and further preferably contains 3 to 30% by weight. In order to sufficiently improve the water resistance and enhance the adhesion in the non-dry state, the radically polymerizable compound having an active methylene group is preferably set to 1% by weight or more. On the other hand, if it exceeds 50% by weight, the adhesive layer may be hardly cured. In addition, the radical polymerization initiator having a hydrogen abstraction effect is preferably contained in an amount of 0.1 to 10% by weight relative to the total amount of the adhesive composition, more preferably 0.3 to 9% by weight. In order to allow the hydrogen abstraction reaction to proceed sufficiently, it is preferable to use a radical polymerization initiator of 0.1 wt% or more. On the other hand, if it exceeds 10% by weight, it may not be completely dissolved in the composition.

The cationic polymerizable compound used in the cationic polymerization hardening adhesive composition can be classified into a monofunctional cationic polymerizable compound having one cationic polymerizable functional group in the molecule, and a cationic polymerizable compound having two or more in the molecule Polyfunctional cationic polymerizable compound. The liquid viscosity of the monofunctional cationic polymerizable compound is relatively low, so that if it is contained in the resin composition, the liquid viscosity of the resin composition can be reduced. In addition, most of the monofunctional cationic polymerizable compounds have functional groups that can express various functions. When contained in the resin composition, the resin composition and/or the cured product of the resin composition can exhibit various functions. The polyfunctional cationic polymerizable compound can cause the cured product of the resin composition to undergo three-dimensional crosslinking, so it is preferably contained in the resin composition. The ratio of the monofunctional cationic polymerizable compound to the polyfunctional cationic polymerizable compound is preferably in the range of 10 parts by weight to 1000 parts by weight with respect to 100 parts by weight of the monofunctional cationic polymerizable compound. Examples of the cationic polymerizable functional group include epoxy groups, oxetanyl groups, and vinyl ether groups. Examples of the compound having an epoxy group include aliphatic epoxy compounds, alicyclic epoxy compounds, and aromatic epoxy compounds. The cationic polymerization hardening adhesive composition of the present invention preferably contains an alicyclic epoxy compound. Because of its excellent hardenability and adhesion. Examples of alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxy The caprolactone modified product, trimethylcaprolactone modified product or valerolactone modified product of cyclohexane carboxylic acid ester, etc. Specifically, CELLOXIDE 2021, CELLOXIDE 2021A, CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085 (above, DAICEL Chemical Industry Co., Ltd.), Cyracure UVR-6105, Cyracure UVR-6107, Cyracure 30, R-6110 (above, DOW CHEMICAL Japan Co., Ltd.), etc. of oxetane groups The compound has the effects of improving the curability of the cationic polymerization hardening adhesive composition of the present invention and lowering the liquid viscosity of the composition, etc., so it is preferable to contain the compound. Compounds having an oxetane group can be exemplified by 3-ethyl -3-hydroxymethyloxetane, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 3-ethyl-3-(phenoxy Methyl) oxetane, di[(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3-(2-ethylhexyloxymethyl) oxetane Butane, phenol novolak oxetane, etc., and commercially available ARON OXETANE OXT-101, ARON OXETANE OXT-121, ARON OXETANE OXT-211, ARON OXETANE OXT-221, ARON OXETANE OXT-212 (above, East Asia (Synthetic Co., Ltd.) etc. The compound having a vinyl ether group has the effects of improving the curability of the cationic polymerization hardening adhesive composition of the present invention and reducing the liquid viscosity of the composition, so it is preferable to contain the compound. Examples of the compounds include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol divinyl ether , Cyclohexane dimethanol divinyl ether, cyclohexane dimethanol monovinyl ether, tricyclodecane vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl ethylene Ether, neopentyl alcohol type tetravinyl ether, etc.

The cationic polymerization hardening adhesive composition contains at least one compound selected from the above-described compounds having an epoxy group, compounds having an oxetane group, and compounds having a vinyl ether group as a hardening component And, all of them can be hardened by cationic polymerization, so photo-cationic polymerization initiator can be blended. The photo-cationic polymerization initiator is irradiated with active energy rays such as visible rays, ultraviolet rays, X-rays, electron rays, etc., which will generate cationic species or Lewis acid, and initiate the polymerization reaction of epoxy groups or oxetanyl groups. As the photocationic polymerization initiator, a photoacid generator described later is suitably used. In addition, when the adhesive composition used in the present invention is used with visible light curability, it is preferable to use a photo-cationic polymerization initiator that has high sensitivity especially for light of 380 nm or more, but the photo-cationic polymerization initiator is generally The compound that shows the maximum absorption value in the vicinity of 300nm or a shorter wavelength region, so it can be photosensitized to show the maximum absorption value for the longer wavelength region, specifically the light longer than 380nm by blending A chemical agent to induce light at a wavelength near it and promote the production of cationic species or acids derived from photocationic polymerization initiators. Examples of the photosensitizer include anthracene compounds, pyrene compounds, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes, etc. Use 2 or more types by mixing. In particular, the anthracene compound is very desirable because of its excellent photosensitization effect, and specific examples include ANTHRACURE UVS-1331 and ANTHRACURE UVS-1221 (manufactured by Kawasaki Chemicals). The content of the photosensitizer is preferably 0.1% by weight to 5% by weight, and preferably 0.5% by weight to 3% by weight.

The adhesive composition used in the present invention preferably contains the following components in addition to the above components.

The active energy ray-curable adhesive composition used in the present invention may contain an acrylic oligomer obtained by polymerizing a (meth)acrylic monomer in addition to the curable component of the radical polymerizable compound. The active energy ray-curable adhesive composition contains components, which can reduce curing shrinkage when the composition is irradiated with active energy rays to harden it, and can reduce the interface between the adhesive and the adherend such as polarizers and transparent protective films stress. As a result, the adhesion between the adhesive layer and the adherend can be suppressed from decreasing. In order to sufficiently suppress the curing shrinkage of the cured product layer (adhesive layer), the content of the acrylic oligomer is preferably 20% by weight or less relative to the total amount of the adhesive composition, and preferably 15% by weight or less. If the content of the acrylic oligomer in the adhesive composition is too large, the reaction speed will be drastically reduced after the active energy ray is irradiated to the composition, and the hardening may be poor. On the other hand, the acrylic oligomer is preferably contained in an amount of 3% by weight or more based on the total amount of the adhesive composition, and more preferably in an amount of 5% by weight or more.

In consideration of workability and uniformity during coating, the active energy ray-curable adhesive composition preferably has a low viscosity, so acrylic oligomers obtained by polymerizing (meth)acrylic monomers also have a low viscosity. good. As the acrylic oligomer having a low viscosity and preventing hardening and shrinkage of the adhesive layer, the weight average molecular weight (Mw) is preferably 15,000 or less, more preferably 10,000 or less, and particularly preferably 5000 or less. On the other hand, in order to sufficiently suppress the curing shrinkage of the cured product layer (adhesive layer), the weight average molecular weight (Mw) of the acrylic oligomer is preferably 500 or more, more preferably 1000 or more, and particularly preferably 1500 or more. The (meth)acrylic monomer constituting the acrylic oligomer, specifically, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, (meth) Isopropyl acrylate, 2-methyl-2-nitropropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, S-butyl (meth)acrylate, ( Tertiary butyl methacrylate, n-pentyl (meth) acrylate, tertiary pentyl (meth) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethyl (meth) acrylate Butyl ester, n-hexyl (meth)acrylate, cetyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 4-methyl (meth)acrylate (Meth)acrylic acid (carbon number 1-20) alkyl esters such as -2-propylpentyl ester, N-octadecyl (meth)acrylate; and, for example, cycloalkyl (meth)acrylate (for example, (Cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, etc.), aralkyl (meth)acrylate (eg, benzyl (meth)acrylate, etc.), polycyclic (meth)acrylate (E.g. (meth)acrylic acid-2-isocamphenyl ester, (meth)acrylic acid 2-norbornyl methyl ester, (meth)acrylic acid 5-norcamphenyl-2-yl-methyl ester, (meth)acrylic acid 3-methyl-2-norbornyl methyl ester, etc.), hydroxyl-containing (meth)acrylates (for example, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,3- Dihydroxypropylmethyl-butyl(meth)methacrylate, etc.), (meth)acrylates containing alkoxy or phenoxy groups (2-methoxyethyl (meth)acrylate, 2-Methoxyethyl (meth)acrylate, 2-methoxymethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (methyl ) Acrylate, phenoxyethyl (meth)acrylate, etc.), epoxy-containing (meth)acrylates (for example, glycidyl (meth)acrylate, etc.), halogen-containing (meth) Acrylic esters (e.g. 2,2,2-trifluoroethyl (meth)acrylate, 2,2,2-trifluoroethyl ethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, ( Hexafluoropropyl methacrylate, octafluoropentyl (meth)acrylate, heptafluorodecyl (meth)acrylate, etc.), alkylaminoalkyl (meth)acrylate (e.g. dimethylamine Ethyl (meth)acrylate, etc.). These (meth)acrylates can be used alone or in combination of two or more. Specific examples of acrylic oligomers include "ARUFON" manufactured by Toya Synthetic Corporation, "ACTFLOW" manufactured by Kken Chemical Co., Ltd., and "JONCRYL" manufactured by BASF JAPAN.

The active energy ray-curable adhesive composition may contain a photoacid generator. When the photo-acid generator is included in the active energy ray-curable adhesive composition, the water resistance and durability of the adhesive layer can be dramatically improved compared to the case where the photo-acid generator is not included. The photoacid generator can be represented by the following general formula (5).

(惟，L⁺ 表示任意的鎓陽離子；又，X^- 表示選自於由PF₆ ^- 、SbF₆ ^- 、AsF₆ ^- 、SbCl₆ ^- 、BiCl₅ ^- 、SnCl₆ ^- 、ClO₄ ^- 、二硫胺基甲酸酯陰離子、SCN-所構成群組中的相對陰離子)。Formula (5) [Chemical Formula 7]

(However, L ⁺ represents an arbitrary cation; and, X ^- represents a group selected consisting of _{^{PF 6 -, SbF 6 -,}} AsF 6 -, SbCl 6 -, BiCl 5 -, SnCl 6 -, ClO 4 -, disulfide Urethane anions, SCN-relative anions in the group).

Next, the relative anion X ^- in the general formula (5) will be described.

The relative anion X ^- in the general formula (5) is not particularly limited in principle, and non-nucleophilic anions are preferred. When the relative anion X ^{-is a} non-nucleophilic anion, the nucleophilic reaction of the cations coexisting in the molecule or the various materials used together is not easy to occur, and as a result, the photoacid generator itself represented by general formula (4) or Use the stability of the composition over time. The non-nucleophilic anions herein refer to anions with low ability to initiate nucleophilic reactions. Examples of the anion includes, for example _{^{PF 6 -, SbF 6 -,}} AsF 6 -, SbCl 6 -, BiCl 5 -, SnCl 6 -, ClO 4 -, two thiocarbamoyl anions, SCN ^- and the like.

Preferable specific examples of the photoacid generator of the present invention include, for example, "Cyracure-UVI-6992", "Cyracure-UVI-6974" (the above is manufactured by Dow Chemical Japan Co., Ltd.), ``ADEKA OPTOMER SP150'', ``ADEKA OPTOMER SP152'', ``ADEKA OPTOMER SP170'', ``ADEKA OPTOMER SP172'' (above are made by ADEKA Co., Ltd.), ``IRGACURE250'' (Ciba Specialty Chemicals ) Manufactured by the company), ``CI-5102'', ``CI-2855'' (above manufactured by Soda Japan), ``SANEIDO SI-60L'', ``SANEIDO SI-80L'', ``SANEIDO SI-100L'', ``SANEIDO SI- 110L'', ``SANEIDO SI-180L'' (above manufactured by Sanxin Chemical Co., Ltd.), ``CPI-100P'', ``CPI-100A'' (above manufactured by Sanya Apro Co., Ltd.), ``WPI-069 '', ``WPI-113'', ``WPI-116'', ``WPI-041'', ``WPI-044'', ``WPI-054'', ``WPI-055'', ``WPAG-281'', ``WPAG-567'', "WPAG-596" (above manufactured by Wako Pure Chemical Industries).

The content of the photoacid generator is 10% by weight or less relative to the total amount of the adhesive composition, and is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, and particularly preferably 0.1 to 3% by weight.

The active energy ray-curable adhesive composition described above may be used in combination with a compound containing a photoacid generator and an alkoxy group or an epoxy group in the active energy ray-curable adhesive composition.

When using a compound with more than one epoxy group in the molecule or a polymer (epoxy resin) with more than two epoxy groups in the molecule, it can also be used in combination with more than two functions reactive with epoxy groups in the molecule Based compounds. Here, the functional group reactive with an epoxy group includes a carboxyl group, a phenolic hydroxyl group, a mercapto group, a first- or second-stage aromatic amine group, and the like. Considering the three-dimensional hardenability, it is preferable to have two or more of these functional groups in one molecule.

Examples of the polymer having one or more epoxy groups in the molecule include epoxy resin, and there are bisphenol A epoxy resin derived from bisphenol A and epichlorohydrin, and bisphenol F and epichlorohydrin. Derivative bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin Type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fuze type epoxy resin, 3-functional type Multifunctional epoxy resins such as epoxy resins and 4-functional epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, hydantoin epoxy resins, and triisocyanate epoxy resins Resins, aliphatic chain epoxy resins, etc. These epoxy resins can also be halogenated or hydrogenated. Commercially available epoxy resin products include, for example, JERCoat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, and YX4000 manufactured by Japan Epoxy Resins Corporation; Epiclon 830 manufactured by DIC Corporation; EXA835LV, HP4032D, HP820; EP4100 series, EP4000 series, EPU series made by ADEKA Corporation; CELLOXIDE series (2021, 2021P, 2083, 2085, 3000, etc.) made by DAICEL Chemical Co., Ltd., EPOLEAD series, EHPE series; Nippon Steel YD series, YDF series, YDCN series, YDB series, phenoxy resins (polyhydroxy polyethers synthesized from bisphenols and epichlorohydrin and having epoxy groups at both ends; YP series, etc.); NAGASE CHEMTEX's DENACOL series; Kyoeisha Chemical Co.'s Epolite series, etc., but not limited to these. Two or more of these epoxy resins may be used in combination.

The compound having an alkoxy group in the molecule is not particularly limited as long as it has one or more alkoxy groups in the molecule, and a known one can be used. Examples of such compounds include melamine compounds, amine-based resins, and silane coupling agents.

The compounding amount of the compound containing any of the alkoxy group or epoxy group is usually 30% by weight or less relative to the total amount of the adhesive composition. If the content of the compound in the composition is too large, the adhesion will be reduced , The impact resistance of the drop test may deteriorate. The content of the compound in the composition is preferably 20% by weight or less. On the other hand, from the viewpoint of water resistance, the composition preferably contains 2% by weight or more of the compound, and preferably contains 5% by weight or more.

In the case where the adhesive composition used in the present invention is active energy ray curable, the silane coupling agent preferably uses an active energy ray curable compound, but even if it is not active energy ray curable, the same water resistance can be imparted Sex.

As a specific example of the silane coupling agent, the organosilicon compound exemplified above can be used.

The blending amount of the silane coupling agent is preferably in the range of 0.01 to 20% by weight relative to the total amount of the adhesive composition, preferably 0.05 to 15% by weight, and more preferably 0.1 to 10% by weight. When the blending amount is greater than 20% by weight, the storage stability of the adhesive composition will be deteriorated, while if it is less than 0.1% by weight, the effect of the adhesive water resistance cannot be fully exerted.

When the adhesive composition used in the present invention contains a compound having a vinyl ether group, the water resistance of the polarizer and the adhesive layer will be improved, which is very desirable. Although the reason for obtaining this effect is unclear, it is speculated that one of the reasons is that the vinyl ether group of the compound interacts with the polarizer, thereby increasing the adhesion between the polarizer and the adhesive layer. In order to further improve the water resistance of the polarizer and the adhesive layer, the compound is preferably a radical polymerizable compound having a vinyl ether group. In addition, the content of the compound is preferably 0.1 to 19% by weight relative to the total amount of the adhesive composition.

The adhesive composition used in the present invention may contain a compound that can generate keto-enol tautomerism. For example, in an adhesive composition containing a cross-linking agent or an adhesive composition in which a cross-linking agent is blended and used, it may be suitable to adopt the aspect including the compound that can generate the keto-enol tautomerism described above. As a result, the viscosity of the adhesive composition excessively increases or gelation after the organic metal compound is blended, and the generation of microgels is suppressed, and the effect of prolonging the service life of the composition can be achieved.

Various β-dicarbonyl compounds can be used as the above-mentioned compounds that can generate keto-enol tautomerism. Specific examples include acetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhex-3,5-dione, 6-methylheptan-2,4-dione. , Β-diketones such as 2,6-dimethylheptane-3,5-dione; methyl acetoacetate, ethyl acetate, isopropyl acetoacetate, tertiary butyl acetoacetate Acetyl acetates; Acrylic ethyl acetate, Acrylic ethyl acetate, Acrylic isopropyl acetate, Acrylic tertiary butyl acetate, etc. Acrylic acetates; Acetic acid ethyl acetate , Ethyl isobutylacetate, isopropyl isobutylacetate, tertiary butyl isobutylacetate and other isobutylacetate; methyl malonate, ethyl malonate and other malonates. Examples of suitable compounds include acetone acetone and acetyl acetate. The compound that can generate keto-enol tautomerism can be used alone or in combination of two or more.

The amount of the compound that can generate keto-enol tautomerism is, for example, 0.05 to 10 parts by weight, preferably 0.2 to 3 parts by weight relative to 1 part by weight of the organometallic compound (e.g. 0.3 parts by weight ~ 2 parts by weight). If the use amount of the above compound is less than 0.05 part by weight with respect to 1 part by weight of the organometallic compound, it may be difficult to exert a sufficient use effect. On the other hand, if the use amount of the compound exceeds 10 parts by weight with respect to 1 part by weight of the organometallic compound, there will be excessive interaction with the organometallic compound, and it may be difficult to exhibit the desired water resistance.

、2,6-二-三級丁基-4-甲苯酚等聚合抑制劑；聚合起始助劑；調平劑；濕潤性改良劑；界面活性劑；塑化劑；紫外線吸收劑；無機填充劑；顏料；染料等。In addition, the adhesive composition used in the present invention can be blended with various additives as other arbitrary components within a range that does not impair the object and effect of the present invention. Examples of such additives include epoxy resins, polyamides, polyamides, imines, polyurethanes, polybutadiene, polychloroprene, polyethers, polyesters, and styrene-butadiene. Polymers or oligomers such as block copolymers, petroleum resins, xylene resins, ketone resins, cellulose resins, fluorine-based oligomers, polysiloxane-based oligomers, polythioether-based oligomers; phenothiol

, 2,6-Di-tertiary butyl-4-cresol and other polymerization inhibitors; polymerization initiation aids; leveling agents; wettability modifiers; surfactants; plasticizers; ultraviolet absorbers; inorganic fillers Agent; pigment; dye etc.

The total amount of the above additives relative to the adhesive composition is usually 0 to 10% by weight, preferably 0 to 5% by weight, and most preferably 0 to 3% by weight.

From the viewpoint of applicability, the viscosity of the adhesive composition used in the present invention is preferably 100 cp or less at 25°C. On the other hand, if the adhesive composition of the present invention is higher than 100 cp at 25°C, the temperature of the adhesive composition can be controlled at the time of coating and adjusted to 100 cp or less. The more ideal range of viscosity is 1~80cp, the most suitable is 10~50cp. Viscosity can be measured using TVE22LT, an E-type viscometer manufactured by Toki Industry Corporation.

In addition, from the viewpoint of safety, the adhesive composition used in the present invention is preferably a material having low skin irritation as the aforementioned hardening component. Skin irritation can be judged by P.I.I index. P.I.I is a widely used indicator that indicates the degree of skin damage, and is measured by the Chui test (Draize method). The measured value is expressed in the range of 0 to 8. The smaller the value is, the lower the irritation is, but the error of the measured value is large, so it is better as a reference value. P.I.I is preferably 4 or less, preferably 3 or less, and most preferably 2 or less.

>Polarizing film> The polarizing film of the present invention includes a polarizer having a durability enhancing layer on at least one surface, the durability enhancing layer is formed of a curable composition containing a compound (A), and the compound (A) has a carbon-carbon double bond and Ring skeleton. Moreover, the polarizing film of the present invention may be a transparent protective film on at least one area of the polarizer. It is more suitable to have an adhesive layer between the durability enhancing layer and the transparent protective film. The following example illustrates a polarizing film further provided with an adhesive layer between the durability enhancing layer and the transparent protective film.

The polarizing film of the present invention can be manufactured by, for example, the following manufacturing method: A method for manufacturing a polarizing film, comprising: a first coating step, which is to apply a hardening composition containing a compound (A) to the bonding surface of the polarizer to form a durable enhancement layer; and a hardening step to improve the durability of the composition The hardening composition of the layer is hardened; the second coating step is to apply the adhesive composition to the bonding surface of the transparent protective film; the bonding step is to bond the durability enhancing layer forming surface of the polarizer and the transparent protective film Coated surface of the adhesive composition; and the next step is to irradiate active energy rays from the polarizer surface side or the transparent protective film side to harden the adhesive composition to produce an adhesive layer, and then pass the adhesive layer to polarize Parts and transparent protective film. In addition, an easy adhesion layer forming step of forming an easy adhesion layer on at least one side of the polarizer may be added before the first coating step, and then a hardening composition may be coated on the easy adhesion layer formation surface of the polarizer The first coating step. In addition, before the step of forming the easy-adhesion layer, a processing step of performing surface modification treatment on at least one side of the polarizer can be performed.

Not only polarizers, but also transparent protective film surface modification. The surface modification treatment may include corona treatment, plasma treatment, and ITRO treatment (flame silane treatment). Corona treatment is particularly preferred.

The method of applying the adhesive composition to the transparent protective film can be appropriately selected according to the viscosity of the adhesive composition or the desired thickness, and examples include a reverse coater, a gravure coater (direct, reverse or indirect), Bar type reverse coater, roll coater, die coater, bar coater, rod coater, etc. The viscosity of the adhesive composition used in the present invention is preferably 3 to 100 mPa·s, more preferably 5 to 50 mPa·s, and most preferably 10 to 30 mPa·s. When the viscosity of the adhesive composition is high, the smoothness of the surface after coating is poor, resulting in poor appearance, which is not good. The adhesive composition used in the present invention can be heated or cooled to adjust the viscosity to a preferred range and then coated.

Through the adhesive composition applied as described above, the polarizer and the transparent protective film are bonded together. The lamination of the polarizer and the transparent protective film can be performed using a roll laminator or the like.

The adhesive composition used in the present invention is preferably used as an active energy ray-curable adhesive composition. The active energy ray hardening adhesive composition can be used in the form of electron beam hardening, ultraviolet light hardening, and visible light hardening. The aspect of the aforementioned adhesive composition is preferably a visible light-curable adhesive composition from the viewpoint of productivity.

After the active energy ray-curable adhesive composition is bonded to the polarizer and the transparent protective film, the active energy ray (electron rays, ultraviolet rays, visible light, etc.) is irradiated to harden the active energy ray-curable adhesive composition to form an adhesive.剂层。 Agent layer. The irradiation direction of active energy rays (electron rays, ultraviolet rays, visible rays, etc.) can be irradiated from any and appropriate directions. It is desirable to irradiate from the side of the transparent protective film. When irradiated from the polarizer side, the polarizer may be deteriorated by active energy rays (electron rays, ultraviolet rays, visible rays, etc.).

Regarding electron beam curability, any and appropriate conditions can be adopted as long as the irradiation conditions of the electron beam are such that the active energy ray curable adhesive composition can be cured. For example, when irradiating electron beams, the acceleration voltage should be 5 kV to 300 kV, and more preferably 10 kV to 250 kV. When the acceleration voltage is lower than 5kV, the electron beam will not reach the adhesive and there is a risk of insufficient hardening; when the acceleration voltage exceeds 300kV, the penetration force through the sample will be too strong, which may cause damage to the transparent protective film or polarizer. The irradiation dose is 5 to 100 kGy, preferably 10 to 75 kGy. When the irradiation dose is less than 5kGy, the adhesive will be insufficiently hardened; when it exceeds 100kGy, it will cause damage to the transparent protective film or polarizer, resulting in a decrease in mechanical strength or yellowing, and failure to obtain predetermined optical properties.

Electron beam irradiation is usually carried out in an inert gas, but if necessary, it can also be carried out in the atmosphere or under the condition of introducing a small amount of oxygen. Although it depends on the material of the transparent protective film, proper introduction of oxygen can intentionally generate an oxygen barrier on the surface of the transparent protective film that the electron beam will initially contact to prevent the transparent protective film from being damaged, and can effectively The agent is irradiated with electron rays.

In the manufacturing method of the polarizing film of the present invention, the active energy ray is preferably a ray containing visible light with a wavelength range of 380 nm to 450 nm, especially the active energy ray with the largest exposure amount using visible light with a wavelength range of 380 nm to 450 nm Better. Among the ultraviolet curable and visible light curable, if a transparent protective film (ultraviolet-transmissive transparent protective film) with ultraviolet absorption energy is used, light with a wavelength shorter than about 380nm will be absorbed, so light with a wavelength shorter than 380nm will not It will reach the active energy ray hardening adhesive composition, but it does not help its polymerization reaction. In addition, light with a wavelength shorter than 380 nm absorbed by the transparent protective film is converted into heat, which causes the transparent protective film to generate heat, causing curling, wrinkling and other defects in the polarizing film. Therefore, when ultraviolet curability and visible light curability are used in the present invention, the active energy ray generating device is preferably a device that does not emit light having a wavelength shorter than 380 nm, more specifically, the cumulative illuminance in the wavelength range of 380 to 440 nm The ratio of the cumulative illuminance to the wavelength range of 250 to 370 nm is preferably 100:0 to 100:50, preferably 100:0 to 100:40. The active energy ray of the present invention is preferably a metal halogen lamp filled with gallium and an LED light source that can emit a wavelength range of 380 to 440 nm. Or you can use low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, incandescent bulbs, xenon lamps, halogen lamps, carbon arc lamps, metal halogen lamps, fluorescent lamps, tungsten filament lamps, gallium lamps, including excimer laser or Sunlight and other ultraviolet and visible light sources can also be used with bandpass filters to block ultraviolet rays with a shorter wavelength than 380nm. In order to improve the adhesion performance of the adhesive layer between the polarizer and the transparent protective film, and at the same time prevent the polarizing film from curling, it is appropriate to use: use a metal halogen lamp filled with gallium and pass a bandpass filter that can shield light with a wavelength shorter than 380nm The obtained active energy ray or the active energy ray with a wavelength of 405 nm obtained by using an LED light source.

Regarding the ultraviolet curability or visible light curability, it is preferable to heat the active energy ray curable adhesive composition (heating before irradiation) before irradiating ultraviolet light or visible light. In this case, it is preferable to heat to 40°C or higher It is better to heat to above 50℃. In addition, it is also suitable to heat the active energy ray-curable adhesive composition after irradiation with ultraviolet rays or visible rays (heating after irradiation). In this case, it is better to heat to 40°C or higher, preferably to 50°C or higher. .

The active energy ray-curable adhesive composition used in the present invention is particularly suitable for forming an adhesive layer for adhering a polarizer to a transparent protective film having a light transmittance of less than 5% at a wavelength of 365 nm. At this time, the active energy ray-curable adhesive composition of the present invention can harden to form an adhesive when irradiated with ultraviolet rays through a transparent protective film having UV absorption energy by containing the photopolymerization initiator of the above general formula (3) Floor. Therefore, even if the polarizing film is formed by a transparent protective film having UV absorption energy on both areas of the polarizer, the adhesive layer can be hardened. As a matter of course, the polarizing film formed by laminating a transparent protective film without UV absorption energy can also harden the adhesive layer. In addition, the so-called transparent protective film with UV absorption energy means a transparent protective film whose transmittance to light at 380 nm is less than 10%.

The method of imparting UV absorption energy to the transparent protective film includes, for example, a method of containing an ultraviolet absorber in the transparent protective film, and a method of a surface treatment layer containing an ultraviolet absorber on the surface layer of the transparent protective film.

系化合物等。Specific examples of the ultraviolet absorber include, for example, known oxygen diphenyl ketone compounds, benzotriazole compounds, salicylate compounds, diphenyl ketone compounds, cyanoacrylate compounds, and nickel complex salts. Compound, three

Department of compounds.

After the polarizer and the transparent protective film are attached, active energy rays (electron rays, ultraviolet rays, visible rays, etc.) are irradiated to harden the active energy ray-curable adhesive composition to form an adhesive layer. The irradiation direction of active energy rays (electron rays, ultraviolet rays, visible rays, etc.) can be irradiated from any and appropriate directions. It is desirable to irradiate from the side of the transparent protective film. When irradiated from the polarizer side, the polarizer may be deteriorated by active energy rays (electron rays, ultraviolet rays, visible rays, etc.).

When the polarizing film of the present invention is manufactured by a continuous production line, the production line speed is determined according to the hardening time of the adhesive composition, but preferably 1 to 500 m/min, and preferably 5 to 300 m/min, preferably 10 to 100 m/min Better. When the production line speed is too low, productivity is poor, or excessive damage is caused to the transparent protective film, making it impossible to produce a polarizing film that can withstand durability tests. When the production line speed is too high, the curing of the adhesive composition will be insufficient, and the desired adhesiveness may not be obtained.

In addition, the polarizing film of the present invention is ideally for bonding the polarizer and the transparent protective film through the adhesive layer formed by the hardened layer of the active energy ray-curable adhesive composition, except that the transparent protective film and the adhesive layer The second easy layer can be set in between. The second easy-adhesion layer may be formed of various resins having, for example, the following skeletons: polyester skeleton, polyether skeleton, polycarbonate skeleton, polyurethane skeleton, polysilicone, polyamide skeleton, polyimide Skeleton, polyvinyl alcohol skeleton, etc. These polymer resins can be used alone or in combination of two or more. In addition, other additives may be added when the second easy adhesion layer is formed. Specifically, stabilizers such as tackifiers, ultraviolet absorbers, antioxidants, heat-resistant stabilizers, and the like can be used.

The second easy-adhesive layer is usually provided on the transparent protective film first, and then the side of the second easy-adhesive layer of the transparent protective film is attached to the polarizer by the adhesive layer. The formation of the second easy-adhesion layer is performed by applying the forming material of the second easy-adhesion layer to the transparent protective film by a known technique and then drying. The forming material of the second easy-adhesive layer is usually adjusted to a solution that has been diluted to an appropriate concentration in consideration of the thickness after drying and the smoothness of coating. The thickness of the second easy-adhesion layer after drying is 0.01-5 μm, preferably 0.02-2 μm, and more preferably 0.05-1 μm. In addition, the second easy-adhesive layer may be provided in multiple layers. In this case, the total thickness of the second easy-adhesive layer should preferably fall within the above range.

>Transparent protective film> The transparent protective film should preferably be excellent in transparency, mechanical strength, thermal stability, moisture blocking property and isotropy. Examples include: polyester-based polymers such as polyethylene terephthalate or polyethylene naphthalate; cellulose-based polymers such as diethyl cellulose or triethyl cellulose; polymethacrylate Acrylic polymers such as esters; styrene polymers such as polystyrene or acrylonitrile-styrene copolymers (AS resins); and polycarbonate polymers. In addition, the following polymers can be cited as examples of the polymer forming the above-mentioned transparent protective film: polyethylene, polypropylene, polyolefin having a ring system or a norbornene structure, and polyolefin polymerization such as ethylene-propylene copolymer Substances, vinyl chloride-based polymers, nylon-based or aromatic polyamide-based amide-based polymers, amide-imide-based polymers, lanyard-based polymers, polyether lanthanide-based polymers, polyetheretherketone-based polymers, poly Phenylene sulfide-based polymer, vinyl alcohol-based polymer, chlorinated vinylidene-based polymer, vinyl butyral-based polymer, aryl ester-based polymer, polyoxymethylene-based polymer, epoxy-based polymer or the above-mentioned polymerization Blend of substances. The transparent protective film may contain one or more arbitrary and appropriate additives. Examples of additives include ultraviolet absorbers, antioxidants, slip agents, plasticizers, mold release agents, anti-colorants, flame retardants, nucleating agents, antistatic agents, pigments, and colorants. The content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, preferably 50 to 99% by weight, more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. When the content of the above-mentioned thermoplastic resin in the transparent protective film is 50% by weight or less, there is a possibility that the inherent high transparency of the thermoplastic resin may not be fully exerted.

In addition, as the transparent protective film, there may be mentioned the polymer film described in Japanese Patent Laid-Open No. 2001-343529 (WO01/37007), for example, one containing (A) a substituted and/or unsubstituted amide imide group in the side chain A resin composition of a thermoplastic resin and a thermoplastic resin having a substituted and/or unsubstituted phenyl group and a nitrile group in the side chain. Specific examples include films containing a resin composition of an alternating copolymer composed of isobutylene and N-methylmaleimide and an acrylonitrile-styrene copolymer. For the film, a film composed of a mixed extruded product of a resin composition or the like can be used. Due to the small phase difference and small photoelastic coefficient, these films can eliminate the defects such as unevenness caused by the strain of the polarizing film, and have excellent humidification durability due to low moisture permeability.

In the polarizing film, the transparent protective film preferably has a moisture permeability of 150 g/m ² /24h or less. According to the above configuration, it is difficult for moisture in the air to enter the polarizing film, and the change in the moisture content of the polarizing film itself can be suppressed. As a result, the bending and dimensional change of the polarizing film caused by the storage environment can be suppressed.

The transparent protective film provided on one or both sides of the polarizer is preferably excellent in transparency, mechanical strength, thermal stability, moisture blocking property and isotropy, especially the moisture permeability is 150g/m ² / the following are preferred 24h, 120g / m ² / 24h or less is a ^{plus, 5 ~ 70g / m 2 /} 24h or less are preferred. The moisture permeability can be obtained by the method described in the examples.

For the formation material of the transparent protective film satisfying the aforementioned low moisture permeability, polyester resins such as polyethylene terephthalate or polyethylene naphthalate; polycarbonate resins; aryl ester resins; nylon or aromatic Acrylate-based resins such as polyamidoamines; polyethylene, polypropylene, polyolefin polymers such as ethylene-propylene copolymers, cyclic olefin-based resins having a ring system or norbornene structure, (meth)acrylic acid Resin or these mixtures. Among the aforementioned resins, polycarbonate resins, cyclic polyolefin resins, and (meth)acrylic resins are preferred, and cyclic polyolefin resins and (meth)acrylic resins are particularly preferred.

The thickness of the transparent protective film can be appropriately determined. Generally speaking, from the viewpoint of workability such as strength and operability, and thinness, etc., it is preferably 5 to 100 μm. In particular, 10 to 60 μm is preferred, and 13 to 40 μm is preferred.

The method of bonding the polarizer and the protective film can be carried out using a roller press. The method of layering the protective film on the two areas of the polarizer can be selected from the following methods: a method of bonding the polarizer and one protective film and then another protective film; and, a method of bonding the polarizer and two protective films at the same time . Using the former method can significantly reduce the entrapped air bubbles generated during lamination, which is ideal, that is, the method of laminating the polarizer and one protective film and then laminating the other protective film.

>Optical film> When the polarizing film of the present invention is actually used, it can be used as an optical film laminated with other optical layers. The optical layer is not particularly limited, and examples include phase difference films (including wavelength plates of 1/2 or 1/4, etc.), visual compensation films, brightness enhancement films, reflective plates, and semi-transmissive plates. The optical layer of a liquid crystal display device or the like. These optical layers can be used as the base film of the base film with an easy-adhesion layer in the present invention, and can have reactive functional groups such as hydroxyl groups, carbonyl groups, or amine groups by performing surface modification treatment as needed. Therefore, the easy-to-process retardation film having the compound represented by the general formula (1) on at least one surface of the retardation film containing at least a reactive functional group on the surface, in particular, a compound containing the compound represented by the general formula (1) is formed The phase difference film attached to the easy adhesion layer of the easy adhesion layer can improve the adhesion between the retardation film and the adhesive layer. As a result, the adhesion can be particularly improved, which is suitable.

As the aforementioned retardation film, a retardation film having a retardation with a frontal retardation of 40 nm or more and/or a retardation in the thickness direction of 80 nm or more can be used. The frontal phase difference is usually controlled in the range of 40~200nm, and the thickness direction phase difference is usually controlled in the range of 80~300nm.

Examples of the retardation film include a birefringent film obtained by uniaxially or biaxially stretching a polymer material, an alignment film of liquid crystal polymer, and an alignment layer in which the film supports the liquid crystal polymer. The thickness of the retardation film is not particularly limited, but is generally about 20 to 150 μm.

As the retardation film, a reverse wavelength dispersion-type retardation film satisfying the following formulas (1) to (3) can also be used: 0.70＜Re[450]/Re[550]＜0.97…(1) 1.5×10-3＜Δn＜6×10-3…(2) 1.13＜NZ＜1.50…(3) (In the formula, Re[450] and Re[550] are the in-plane retardation values of the retardation film measured at 23°C with light of wavelength 450nm and 550nm; Δn is the direction of the slow axis of the retardation film respectively 1. When the refractive index in the fast axis direction is nx and ny, the in-plane birefringence of nx-ny; NZ means that nz is the refractive index in the thickness direction of the retardation film. Nx-ny ratio of refraction).

On the polarizing film or the optical film having at least one polarizing film laminated thereon, an adhesive layer for adhering to other members such as liquid crystal cells may also be provided. The adhesive forming the adhesive layer is not particularly limited, and can be appropriately selected from acrylic polymers, polysiloxane polymers, polyesters, polyurethanes, polyamides, polyethers, fluorine-based or rubber-based polymers. The material is used as the base polymer material. It is particularly preferable to use an acrylic adhesive that exhibits excellent optical transparency, moderate wettability, cohesiveness, and adhesive properties, and has excellent weather resistance and heat resistance.

The adhesive layer may also be provided on one or both sides of the polarizing film or the optical film in the form of an overlapping layer of objects of different compositions or types. In addition, in the case of being disposed on both sides, the front and back of the polarizing film or the optical film can also be made into an adhesive layer of different composition, type or thickness. The thickness of the adhesive layer can be appropriately determined according to the purpose of use or adhesion, and is generally 1 to 500 μm, preferably 1 to 200 μm, and particularly preferably 1 to 100 μm.

In order to prevent the exposed surface of the adhesive layer from being contaminated, it can be temporarily attached and covered with a separating member during the period before it is actually used. In this way, it is possible to prevent the adhesive layer from being contacted in a normal operation state. As the separator, in addition to the above-mentioned thickness conditions, suitable articles in accordance with conventional knowledge can be used, for example, plastic film, rubber sheet, paper, cloth, non-woven fabric, mesh, foamed sheet or metal foil and the lamination of these can be used Appropriate flakes, such as the body, should be coated with an appropriate release agent such as polysiloxane-based or long-chain alkyl-based, fluorine-based, or molybdenum sulfide.

>Image display device> The polarizing film or optical film of the present invention can be suitably used in the formation of various devices such as liquid crystal display devices and the like. The formation of the liquid crystal display device can act as before. That is, a liquid crystal display device is generally formed by appropriately assembling and assembling a liquid crystal cell, a polarizing film or an optical film, and a component such as a lighting system according to needs into a driving circuit, etc. In the present invention, in addition to using the polarizing light of the present invention The film or the optical film is not particularly limited except for this point, and may be based on conventional knowledge. As for the liquid crystal cell, any type such as TN type, STN type, or π type can be used.

A liquid crystal display device in which a polarizing film or an optical film is arranged on one side or both sides of a liquid crystal cell can be formed, or a suitable liquid crystal display device using a backlight or a reflective plate in a lighting system. At this time, the polarizing film or optical film of the present invention may be disposed on one side or both sides of the liquid crystal cell. When polarizing films or optical films are provided on both sides, they may be the same or different. In addition, when forming a liquid crystal display device, one or more layers such as a diffusion plate, an anti-glare layer, an anti-reflection film, a protective plate, a lens array, a lens array sheet, a light diffusion plate, a backlight Pieces and other appropriate parts. Examples

The embodiments of the present invention are described below, but the embodiments of the present invention are not limited thereto.

>polarizer> First, a laminated body with a PVA layer with a thickness of 9 μm is formed on an amorphous PET substrate, and the extended layered body is formed by air-assisted stretching at a stretching temperature of 130° C. Then, the colored layered body is formed by dyeing the stretched layered body and then used for stretching Boric acid water stretching at a temperature of 65 degrees stretches the colored laminate integrally with the amorphous PET substrate so that the total stretching magnification becomes 5.94 times, and an optical film laminate including a PVA layer with a thickness of 5 μm is produced. As a result, an optical film laminate including a PVA layer with a thickness of 5 μm for forming a thin polarizer can be obtained, and the PVA molecules formed on the PVA layer of the amorphous PET substrate through the optical film laminate are extended through the two stages. Highly oriented, and the iodine adsorbed by dyeing is highly oriented in one direction in the form of polyiodide ion complex.

系紫外線吸收劑(ADEKA公司製，商品名：T-712)0.62重量份於220℃下混合，而製出樹脂丸粒。使所獲得之樹脂丸粒在100.5kPa、100℃下乾燥12小時，並以單軸擠製機於模具溫度270℃下從T型模頭擠製出而成形為薄膜狀(厚度160μm)。並再將該薄膜在150℃的氣體環境下沿其輸送方向延伸(厚度80μm)，接著塗佈含有水性胺甲酸酯樹脂的易接著劑後，在150℃的氣體環境下沿正交於薄膜輸送方向的方向延伸，而製得厚度40μm(透濕度58g/m² /24h)的透明保護薄膜。>Transparent protective film> Using a biaxial kneader, 100 parts by weight and three parts of the imidized MS resin described in Production Example 1 of Japanese Patent Laid-Open No. 2010-284840

0.62 parts by weight of an ultraviolet absorber (manufactured by ADEKA Corporation, trade name: T-712) was mixed at 220°C to produce resin pellets. The obtained resin pellets were dried at 100.5 kPa and 100° C. for 12 hours, and extruded from a T-die at a mold temperature of 270° C. using a uniaxial extruder to form a film (thickness 160 μm). Then, the film is extended in the transport direction (thickness 80 μm) under a gas environment of 150° C., and then an easy adhesive agent containing an aqueous urethane resin is applied, and then perpendicular to the film under a gas environment of 150° C. The direction of the conveying direction was extended to obtain a transparent protective film with a thickness of 40 μm (moisture permeability 58 g/m ² /24h).

>Active energy rays> Active energy rays use visible light (metal halide lamp filled with gallium), irradiation device: Light HAMMER10 manufactured by Fusion UV Systems, Inc., bulb: V bulb, peak illuminance: 1600mW/cm ² , cumulative Irradiation 1000/mJ/cm ² (wavelength 380~440nm). In addition, the illuminance of visible light was measured using the Sola-Check system manufactured by Solatell.

(Titration test of compound (A)) Γ-butyrolactone acrylate (GBLA) was selected as the compound (A) for the titration test, thereby confirming that GBLA will exhibit a simulated buffering effect. As shown in Table 1, after dropping 0.1M_NaOH aqueous solution into the 0.1M_GBLA aqueous solution adjusted to 60°C and measuring its pH rise, even if 50.2g (=0.5 equivalent) of 0.1M_NaOH aqueous solution was dropped, the pH still only increased compared to before the addition 2.5. From the titration test results, it can be understood that GBLA will exhibit a simulated buffering effect.

[Table 1]

(Adjust hardenable composition) Based on 100 parts by weight of GBLA, an adhesive composition containing 3 parts by weight of IRGACURE 907 (polymerization initiator, manufactured by BASF) and 3% by weight of KAYACURE DETX-S (polymerization initiator, manufactured by Nippon Kayaku) was adjusted. .

(Adjust the easy-to-adhere composition) Relative to 6.9 parts by weight of an isopropanol solution adjusted to 15% by weight of 4-vinylbenzeneboronic acid, adjusted to contain 5.1 parts by weight of acryloylmorphine, 0.2 parts by weight of Olfine EXP4200 (manufactured by Nissin Chemical Co., Ltd.), pure 87.9 parts by weight of water is easily adhered to the composition.

>Polarizer with easy adhesion layer>The above-mentioned easy adhesion composition is coated on the PVA surface of the optical film laminate including a PVA layer with a thickness of 5 μm using the wire rod (manufactured by No. 2). Then, it was dried at 60°C for 2 minutes to remove the solvent, and a polarizer with an easy adhesion layer was produced.

(Adjustment of adhesive composition) Based on 100 parts by weight of 1,9-nonanediol diacrylate (produced by Kyoeisha Chemical Co., Ltd.), 3 parts by weight of IRGACURE 907 (polymerization initiator, manufactured by BASF) and KAYACURE DETX-S (from Starter, manufactured by Nippon Kayaku Co., Ltd.) 3% by weight of adhesive composition.

(Making polarizing film) Example 1 Using an MCD coater (manufactured by Fuji Machinery Co., Ltd.) (groove shape: honeycomb shape, gravure roller line number: 1000 lines/inch, rotation speed 140%/relative production line speed) Next, on the layer side, the above-mentioned curable composition was applied to a thickness of 0.7 μm to form a durability improving layer. Next, the transparent protective film was bonded from the durability-improving layer side of the polarizer using a rolling machine. After that, the visible light is irradiated from the bonded transparent protective film side with an active energy ray irradiation device to harden the curable composition constituting the durability improving layer, and then the polarizer and the transparent protective film are adhered at 70°C Hot air drying was performed for 3 minutes, and the amorphous PET substrate layered on the other side of the polarizer was peeled off and removed, thereby producing a polarizing film having a transparent protective film on one side of the polarizer. The production line speed of lamination is carried out at 25m/min.

Example 2 Using an MCD coater (manufactured by Fuji Machinery Co., Ltd.) (groove shape: honeycomb shape, gravure roller line number: 1000 lines/inch, rotation speed 140%/relative production line speed) Next, on the layer side, the above-mentioned curable composition was applied to a thickness of 0.7 μm to form a durability improving layer. Next, a polyester film (manufactured by DIAFOIL S-100 38 μm Mitsubishi Chemical Co.) was bonded from the durability enhancing layer side of the polarizer using a rolling machine. After that, the visible light rays are irradiated from the bonded polyester film side through an active energy ray irradiation device to harden the curable composition constituting the durability-enhancing layer. Then peel off the polyester film. Using an MCD coater (manufactured by Fuji Machinery Co., Ltd.) (groove shape: honeycomb shape, gravure roller line number: 1000 lines/inch, rotation speed 140%/relative production line speed), the bonding surface of the transparent protective film is bonded to the above The agent composition was applied to a thickness of 0.7 μm, and the surface of the durability-improving layer of the polarizer was applied to the application surface of the adhesive composition of the transparent protective film using a rolling machine. After that, the visible light is irradiated from the bonded transparent protective film side with an active energy ray irradiation device to harden the adhesive composition constituting the adhesive layer, and then dried at 70° C. for 3 minutes with hot air, and the layer is polarized. The amorphous PET substrate on the other side of the member is peeled off and removed, thereby producing a polarizing film having a transparent protective film on one side of the polarizing member. The production line speed of lamination is carried out at 25m/min.

Example 3 Using an MCD coater (manufactured by Fuji Machinery Co., Ltd.) (groove shape: honeycomb shape, gravure roller line number: 1000 lines/inch, rotation speed 140%/relative production line speed) Next, on the layer side, the above-mentioned curable composition was applied to a thickness of 0.7 μm to form a durability improving layer. Next, a polyester film (manufactured by DIAFOIL S-100 38 μm Mitsubishi Chemical Co.) was bonded from the durability enhancing layer side of the polarizer using a rolling machine. After that, the visible light rays are irradiated from the bonded polyester film side through an active energy ray irradiation device to harden the curable composition constituting the durability-enhancing layer. Then, the polyester film is peeled off, thereby obtaining a polarizing film composed of a polarizing member having a durability improving layer on one surface.

Comparative example 1 A polarizer without a durability enhancing layer was used as the polarizer, except that a polarizing film was produced in the same manner as in Example 2.

Comparative example 2 A polarizing film composed of a polarizer having an adhesive layer on one surface was produced in the same manner as in Example 3 except that the adhesive composition was applied instead of the curable composition.

The polarizing films obtained in the above examples and comparative examples were evaluated as follows. The evaluation results are listed in Table 1.

(Humidity durability test) The transmittance and degree of polarization of the manufactured polarizing film were measured using a spectroscopic transmittance measuring instrument with an integrating sphere (Dot-3c from Murakami Color Technology Research Institute). In addition, the degree of polarization P is the transmittance (parallel transmittance: Tp) when two identical polarizing films are overlapped in parallel with the transmission axes of both of them and the transmittance when orthogonally overlapped with the transmission axes of the two (orthogonal transmission) Rate: Tc) obtained by applying the following formula. Polarization P(%)={(Tp-Tc)/(Tp+Tc)}1/2×100 Each transmittance is expressed as a Y value obtained by correcting the light visual performance with a 2 degree field of view (C light source) of JIS Z8701 so that the complete polarization obtained by the Glan-Taylor polarizer is 100%. After applying a corona treatment to the polarizer surface of the polarizing film, apply an acrylic adhesive with a thickness of 20 μm, and attach an alkali-free glass to the other surface of the acrylic adhesive, and then measure the polarization degree P and transmittance as defined above The initial value. Next, after putting the polarizing film with glass into an environment of 60°C and 95% RH for 48 hours, the degree of polarization over time of the polarizing film with glass was measured. The value obtained by subtracting the initial polarization degree P from the polarization degree P over time is regarded as the change in polarization degree. The smaller the absolute value of the change in polarization degree, the better the humidification durability.

[Table 2]

Claims (10)

A polarizer with a durability enhancing layer on at least one surface, the polarizer is characterized by: The aforementioned durability enhancing layer is formed of a hardening composition containing the compound (A), and the compound (A) is a pH increase within 3.0 equivalents even if an alkaline component is added at 0.5 equivalent in a titration test at 60°C . The polarizer according to claim 1, wherein the aforementioned compound (A) is γ-butyrolactone (meth)acrylate. The polarizer according to claim 1 or 2, wherein at least a part of the aforementioned compound (A) contained in the aforementioned curable composition is polymerized. The polarizing member according to any one of claims 1 to 3, wherein the curable composition further contains a polymerization initiator. The polarizer according to claim 4, wherein the durability improving layer is formed of a hardened layer of the hardenable composition. A polarizing film provided with the polarizing member according to any one of claims 1 to 5. The polarizing film according to claim 6, wherein at least one area layer of the polarizer has a transparent protective film, and The transparent protective film is laminated on the durability enhancing layer side of the polarizer. The polarizing film according to claim 7, wherein an adhesive layer is further provided between the durability improving layer and the transparent protective film. An optical film, characterized in that at least one polarizing film according to any one of claims 6 to 8 is laminated. An image display device characterized by using a polarizing film as in any one of claims 6 to 8, or an optical film as in claim 8.