JP6609075B2 - Polarizing film and method for manufacturing the same, optical film and image display device - Google Patents

Description

  The present invention relates to a polarizing film and a method for producing the same. The polarizing film can form an image display device such as a liquid crystal display device (LCD), an organic EL display device, a CRT, or a PDP alone or as an optical film obtained by laminating the polarizing film.

  Liquid crystal display devices are rapidly expanding in watches, mobile phones, PDAs, notebook computers, personal computer monitors, DVD players, TVs, and the like. The liquid crystal display device visualizes the polarization state by switching of the liquid crystal, and a polarizer is used from the display principle. In particular, in applications such as TV, higher brightness, higher contrast, and wider viewing angle are required, and polarizing films are also required to have higher transmittance, higher degree of polarization, and higher color reproducibility.

As the polarizer, since it has a high transmittance and a high degree of polarization, for example, an iodine-based polarizer having a stretched structure by adsorbing iodine to polyvinyl alcohol (hereinafter also simply referred to as “PVA”) is most widely used. in use. In general, a polarizing film in which a transparent protective film is bonded to both surfaces of a polarizer by a so-called aqueous adhesive in which a polyvinyl alcohol-based material is dissolved in water is used (Patent Document 1 and Patent Document 2 below). ). As the transparent protective film, triacetyl cellulose having a high moisture permeability is used.

  When manufacturing a polarizing film, when a water-based adhesive such as a polyvinyl alcohol-based adhesive is used (so-called wet lamination), a drying step is required after the polarizer and the transparent protective film are bonded together. . In order to improve the productivity of the polarizing film, it is desirable to shorten the drying process or employ another bonding method that does not require the drying process.

  In addition, when using a water-based adhesive, in order to enhance the adhesion with the polarizer, the water content of the polarizer must be relatively high (usually the water content of the polarizer is about 30%). A polarizing film with good adhesion cannot be obtained. However, the polarizing film obtained in this way has problems such as large dimensional changes and poor optical properties at high temperatures and high temperatures and high humidity. On the other hand, in order to suppress a dimensional change, the moisture content of a polarizer can be reduced or a transparent protective film with low moisture permeability can be used. However, when such a polarizer and a transparent protective film are bonded together using a water-based adhesive, drying efficiency decreases, polarization characteristics decrease, or appearance defects occur, and a substantially useful polarizing film is obtained. I can't.

  Further, as represented by TV in particular, as the screen size of image display devices has been increasing in recent years, the enlargement of the polarizing film has become very important from the viewpoint of productivity and cost (yield and increase in number of products). Yes. However, in the polarizing film using the above-mentioned aqueous adhesive, the so-called light omission (unevenness) that the polarizing film causes a dimensional change due to the heat of the backlight, which becomes uneven and a black display appears white in a part of the entire screen. ) Becomes prominent.

  In order to solve the above-described problems in wet lamination, an active energy ray-curable adhesive that does not contain water or an organic solvent has been proposed. For example, in the following Patent Document 3, (A) a radical polymerizable compound containing a polar group and having a molecular weight of 1,000 or less, and (B) a radical polymerizable compound containing no polar group and having a molecular weight of 1,000 or less, An active energy ray curable adhesive containing (D) a photopolymerization initiator is disclosed. However, the combination of radically polymerizable compounds (monomers) constituting such an adhesive is designed particularly for the purpose of improving the adhesion to norbornene-based resin films, and therefore tends to have poor adhesion to the polarizing film. It was.

  Patent Document 4 below discloses an active energy ray-curable adhesive having a photopolymerization initiator having a molar extinction coefficient of 400 or more at a wavelength of 360 to 450 nm and an ultraviolet curable compound as essential components. However, since the combination of monomers constituting such an adhesive is designed mainly for the purpose of preventing warpage and deformation when adhering an optical disk or the like, when used for a polarizing film, There was a tendency to be inferior in adhesiveness.

  In the following Patent Document 5, a (meth) acrylic compound having two or more (meth) acryloyl groups in the molecule (A) in a total amount of 100 parts by weight of the (meth) acrylic compound, and a hydroxyl group in the molecule (B). And a (meth) acrylic compound having only one polymerizable double bond and (C) a phenol ethylene oxide-modified acrylate or nonylphenol ethylene oxide-modified acrylate. ing. However, there is a concern that the combination of monomers constituting such an adhesive has relatively low compatibility between the monomers, phase separation proceeds accordingly, and transparency of the adhesive layer decreases. Further, such an adhesive is intended to improve adhesion by softening a cured product (adhesive layer) (lowering Tg), and there is a concern that durability such as crack resistance is deteriorated. The crack resistance can be evaluated by a thermal shock test (heat shock test).

  The present inventors have developed a radical polymerization type active energy ray-curable adhesive using an N-substituted amide monomer as a curable component (Patent Document 6 and Patent Document 7 below). Such an adhesive exhibits excellent durability under harsh environments under high humidity and high temperature. However, in the market, there is a demand for an adhesive that can further improve adhesiveness and / or water resistance. There was a real situation.

  In the following Patent Document 8, a protective film (A) having ultraviolet impermeability is bonded to one side of a polarizer, and a protective film (B) having ultraviolet transmissivity is bonded to the other side via an ultraviolet curable adhesive. Then, a method for producing a polarizing plate is described in which ultraviolet rays are irradiated from the outside of the protective film (B) to simultaneously cure the ultraviolet curable adhesive disposed on the front and back of the polarizer. Such a manufacturing method is characterized in that the ultraviolet curable adhesive disposed on the front and back of the polarizer is simultaneously cured by ultraviolet irradiation from one side (ultraviolet irradiation of one step), thereby increasing cost merit.

JP 2006-220732 A JP 2001-296427 A JP 2008-009329 A JP 09-31416 A JP 2008-174667 A JP 2008-287207 A JP 2010-78700 A Japanese Patent No. 5090695

  However, the manufacturing method described in Patent Document 8 has the following problems. That is, the reaction rate of the ultraviolet curable adhesive interposed between the protective film (A) having ultraviolet impermeability and the polarizer is not sufficient only by ultraviolet irradiation from one side, and in some cases, the protective film (A ) And the polarizer may peel off. Here, in order to increase the reaction rate of the UV curable adhesive interposed between the protective film (A) and the polarizer, increasing the UV irradiation intensity increases the amount of UV that reaches the polarizer, and the polarization characteristics. In some cases, the polarizing film curls due to shrinkage of the polarizer or contraction of the polarizer. Furthermore, in order to increase the reaction rate of the ultraviolet curable adhesive interposed between the protective film (A) and the polarizer, increasing the ultraviolet irradiation intensity increases the amount of ultraviolet light reaching the protective film (A), In some cases, the protective film (A) generates heat as it absorbs ultraviolet rays, and the polarizing film curls.

  As described above, in the conventional method for producing a polarizing film, it is difficult to prevent curling of the polarizing film while increasing the reaction rate of the adhesive composition interposed between the polarizer and the transparent protective film. It was a fact. In addition, in the conventional active energy ray-curable adhesive composition, the adhesiveness of a polarizer having a low moisture content may be insufficient, and the actual situation is that further improvement in adhesiveness is required. It was.

  The present invention has been made in view of the above circumstances, and its purpose is to produce a polarizing film capable of preventing the curling of the polarizing film while enhancing the adhesive performance of the adhesive layer between the polarizer and the transparent protective film. It is to provide a method. Furthermore, the present invention is to provide a polarizing film, an optical film, and an image display device provided with an adhesive layer that improves the adhesion between the polarizer and the transparent protective film and has improved durability and water resistance.

  As a result of intensive studies to solve the above problems, the present inventors have transparently protected both surfaces of the polarizer via an adhesive layer obtained by irradiating an active energy ray-curable adhesive composition with active energy rays. In the manufacturing method of a polarizing film provided with a film, it discovered that the said subject could be solved by devising the irradiation method of an active energy ray.

Furthermore, the present inventors paid attention to the SP value (solubility parameter) of the curable component in the active energy ray-curable adhesive composition in order to solve the above problems. In general, it can be said that substances having close SP values have high affinity. Therefore, for example, when the SP values of the radical polymerizable compounds are close to each other, the compatibility thereof increases, and when the SP values of the radical polymerizable compound and the polarizer in the active energy ray-curable adhesive composition are close, Adhesiveness between the adhesive layer and the polarizer is enhanced. Similarly, when the SP value of the radically polymerizable compound in the active energy ray-curable adhesive composition and the protective film (for example, triacetyl cellulose film (TAC), acrylic film, cycloolefin film) is close, the adhesive layer Adhesion with the protective film is enhanced. Based on these tendencies, the present inventors conducted extensive studies,
(I) In the active energy ray-curable adhesive composition, each SP value of at least three kinds of radically polymerizable compounds is designed within a specific range, and an optimum composition ratio is set. It has been found that the above-mentioned problems can be solved by containing an acrylic oligomer (D) obtained by polymerizing an acrylic monomer.

  The present invention has been made as a result of the above-described studies, and achieves the above-described object with the following configuration.

  That is, the present invention is a method for producing a polarizing film in which a first transparent protective film is provided on one side of a polarizer and a second transparent protective film is provided on the other side through an adhesive layer, the polarizer, A coating step of applying an active energy ray-curable adhesive composition to at least one surface of the first transparent protective film or the second transparent protective film; the polarizer and the first transparent protective film; and A pasting step of bonding the polarizer and the second transparent protective film, and first irradiating active energy rays from the first transparent protective film side and then irradiating active energy rays from the second transparent protective film side. And through the adhesive layer obtained by curing the active energy ray-curable adhesive composition, the polarizer and the first transparent protective film, Method for producing a polarizing film characterized in that the Rabbi comprising said polarizer and bonding process for bonding the second transparent protective film, a.

In the method for producing a polarizing film according to the present invention, first, active energy rays are irradiated from the first transparent protective film side, and then active energy rays are irradiated from the second transparent protective film side (two-stage irradiation). As a result, the reaction rate of the adhesive layer can be increased and the adhesion between the polarizer and the transparent protective film can be enhanced while preventing the curling of the transparent protective film as compared with the conventional one-step irradiation.

  In the present invention, as the first transparent protective film and the second transparent protective film, an ultraviolet transmission transparent protective film having a light transmittance of 80% or more at a wavelength of 365 nm and / or a light transmittance of 365 nm or less is less than 5%. Various combinations of the UV-opaque transparent protective film can be selected.

That is, in the manufacturing method of the polarizing film,
(1) The first transparent protective film has a light transmittance at a wavelength of 365 nm of 80% or more, and the second transparent protective film has a light transmittance at a wavelength of 365 nm of less than 5%.
(2) The first transparent protective film has a light transmittance at a wavelength of 365 nm of less than 5%, and the second transparent protective film has a light transmittance at a wavelength of 365 nm of 80% or more.
(3) The first transparent protective film and the second transparent protective film have a light transmittance of less than 5% at a wavelength of 365 nm, and (4) the first transparent protective film and the second transparent protective film are The light transmittance at a wavelength of 365 nm is preferably 80% or more. In any combination of the above (1) to (4), polarized light having improved adhesive rate between the polarizer and the transparent protective film while preventing the transparent protective film from curling and increasing the reaction rate of the adhesive layer A film can be produced.

  Moreover, in the manufacturing method of the said polarizing film, it is preferable that the said active energy ray contains visible light with a wavelength range of 380-450 nm.

  Moreover, in the manufacturing method of the said polarizing film, it is preferable that the ratio of the integrated illumination intensity of the wavelength range 380-440 nm and the integrated illumination intensity of the wavelength range 250-370 nm is 100: 0-100: 50.

  Furthermore, in the method for producing a polarizing film, it is preferable that the active energy ray is obtained by blocking ultraviolet rays of 380 nm or less using a gallium lamp as a light source and a bandpass filter.

（式中、Ｒ^１およびＲ^２は−Ｈ、−ＣＨ_２ＣＨ_３、−ＩＰｒまたはＣｌを示し、Ｒ^１およびＲ^２は同一または異なっても良い）を含有することが好ましい。 The active energy ray-curable adhesive composition is a compound represented by the following general formula (1) as a photopolymerization initiator;

(Wherein R ¹ and R ² represent —H, —CH ₂ CH ₃ , —IPr or Cl, and R ¹ and R ² may be the same or different).

（式中、Ｒ^３、Ｒ^４およびＲ^５は−Ｈ、−ＣＨ_３、−ＣＨ_２ＣＨ_３、−ＩＰｒまたはＣｌを示し、Ｒ^３、Ｒ^４およびＲ^５は同一または異なっても良い）を含有することが好ましい。 Moreover, in the manufacturing method of the said polarizing film, as a photoinitiator, the compound further represented with following General formula (2);

Wherein R ³ , R ⁴ and R ⁵ represent —H, —CH ₃ , —CH ₂ CH ₃ , —IPr or Cl, and R ³ , R ⁴ and R ⁵ may be the same or different. It is preferable to contain.

  An ultraviolet curable adhesive having a wavelength of 360 to 370 nm with the largest irradiation amount, for example, an ultraviolet ray using a metal halide lamp or a high-pressure mercury lamp as a light source, and irradiating the ultraviolet ray through a transparent protective film having ultraviolet transparency. When the composition is cured, since the transparent protective film absorbs ultraviolet rays and generates heat, curling may occur in the transparent protective film.

  On the other hand, in the method for producing a polarizing film according to the present invention, when visible light having a wavelength range of 380 to 450 nm is used, the ratio between the integrated illuminance of the wavelength range 380 to 440 nm and the integrated illuminance of the wavelength range 250 to 370 nm is 100 When using an active energy ray of 0 to 100: 50, it is possible to remarkably suppress the absorption of the active energy ray in the transparent protective film, unlike the case of using normal ultraviolet rays. As a result, it is possible to prevent the polarization film from curling due to heat generation in the transparent protective film accompanying active energy ray absorption.

  Since the photopolymerization initiator of the general formula (1) can initiate polymerization by light having a long wavelength that passes through a transparent protective film having UV absorption ability, the adhesive composition can be used even through an ultraviolet opaque transparent protective film. Can be cured. The active energy ray-curable adhesive composition containing the photopolymerization initiator of the general formula (1) is particularly a transparent protective film (ultraviolet opaque opaque transparent protection) having a light transmittance of less than 5% with a polarizer and a wavelength of 365 nm. It can be suitably used for forming an adhesive layer for adhering to a film. When the active energy ray-curable adhesive composition contains the photopolymerization initiator of the general formula (1) described above, the active energy ray (visible light) is irradiated through the UV-opaque transparent protective film, The adhesive layer can be hardened. Therefore, an adhesive bond layer can be hardened also in a polarizing film which laminated a UV light impermeable type transparent protective film on both sides of a polarizer. However, as a matter of course, the adhesive layer can be cured also in a polarizing film in which an ultraviolet transmission transparent protective film is laminated.

  Moreover, by using together the photoinitiator of the said General formula (1) and General formula (2), reaction becomes highly efficient by these photosensitization reaction, and the adhesiveness of an adhesive bond layer improves especially.

  Moreover, in the manufacturing method of the said polarizing film, it is preferable that the thickness of the said polarizer is 10 micrometers or less. Furthermore, the total thickness of the polarizing film is preferably 150 μm or less. In the polarizing film, the degree of curling after the adhesive layer is formed is affected by the thickness of the polarizer and further the total thickness of the polarizing film. The thinner the thickness, the more likely the curling occurs in the polarizing film. . In other words, in a polarizing film using a thin polarizer, and further in a thin polarizing film, there is a specific problem caused by being thin. However, according to the polarizing film manufacturing method of the present invention, a polarizing film using a thin polarizer, and even an adhesive between the polarizer and the transparent protective film, even when manufacturing a thin polarizing film. A polarizing film in which the occurrence of curling is prevented while improving the adhesion performance of the layer can be produced.

Moreover, in the manufacturing method of the said polarizing film, the said active energy ray hardening-type adhesive composition contains the radically polymerizable compound (A), (B) and (C) as a sclerosing | hardenable component, and a (meth) acryl monomer. Containing a polymerized acrylic oligomer (D),
The radical polymerizable compound (A) has an SP value of 29.0 (MJ / m ³ ) ^1/2 or more and 32.0 or less (MJ / m ³ ) ^1/2 .
The radical polymerizable compound (B) has an SP value of 18.0 (MJ / m ³ ) ^1/2 or more and less than 21.0 (MJ / m ³ ) ^1/2 ,
The radical polymerizable compound (C) has an SP value of 21.0 (MJ / m ³ ) ^1/2 or more and 23.0 (MJ / m ³ ) ^1/2 or less,
When the total amount of the composition is 100% by weight, the radical polymerizable compound (B) is preferably contained in an amount of 25 to 80% by weight.

The SP value of the radical polymerizable compound (B) is 18.0 (MJ / m ³ ) ^1/2 or more and less than 21.0 (MJ / m ³ ) ^1/2 , and the composition ratio is 25 to 80% by weight. Preferably there is. Such radically polymerizable compound (B) has a low SP value, and is far away from water (SP value 47.9), which greatly contributes to improving the water resistance of the adhesive layer. The SP value of the radical polymerizable compound (B) is, for example, the SP value (for example, SP value 18.6) of a cyclic polyolefin resin (for example, trade name “ZEONOR” manufactured by Nippon Zeon Co., Ltd.) as a transparent protective film. Since it is near, it contributes also to the adhesive improvement with this transparent protective film. In order to further improve the water resistance of the adhesive layer, the SP value of the radical polymerizable compound (B) is preferably less than 20.0 (MJ / m ³ ) ^1/2 . Considering the water resistance of the adhesive layer in particular, when the total amount of the composition is 100% by weight, the radical polymerizable compound (B) is preferably 30% by weight or more, more preferably 40% by weight or more. . On the other hand, if the radically polymerizable compound (B) is too much, the contents of the radically polymerizable compounds (A) and (C) are inevitably reduced, and the adhesion to the adherend tends to be reduced. . In addition, since the SP value of the radical polymerizable compound (B) is greatly separated from the radical polymerizable compound (A), if the composition ratio is too large, the balance of compatibility between the radical polymerizable compounds is lost, With the progress of phase separation, there is a concern about deterioration of the transparency of the adhesive layer. Therefore, in consideration of the adhesion to the adherend and the transparency of the adhesive layer, when the total amount of the composition is 100% by weight, the composition ratio of the radical polymerizable compound (B) is 75% by weight or less. It is preferable to make it 70% by weight or less.

In the active energy ray-curable adhesive composition used in the present invention, the SP value of the radical polymerizable compound (A) is 29.0 (MJ / m ³ ) ^1/2 or more and 32.0 or less (MJ / m ³ ). It is preferable that it is ^1/2 . Such a radical polymerizable compound (A) has a high SP value, for example, a PVA polarizer (for example, SP value 32.8) and a saponified triacetyl cellulose (TAC; for example, SP value 32.7) as a transparent protective film, It greatly contributes to the improvement of adhesiveness with the adhesive layer. In particular, considering the adhesiveness between the polarizer and / or TAC and the adhesive layer, when the total amount of the composition is 100% by weight, the radical polymerizable compound (A) is preferably 3% by weight or more, preferably 5% by weight. % Or more is more preferable. On the other hand, the radical polymerizable compound (A) is incompatible with the acrylic oligomer (D) obtained by polymerizing the (meth) acryl monomer, and the adhesive layer after curing is uneven due to the progress of phase separation. It may become. Therefore, in order to ensure the uniformity and transparency of the adhesive layer, when the total amount of the composition is 100% by weight, the radical polymerizable compound (A) is preferably 40% by weight or less, preferably 30% by weight. More preferably, it is as follows.

The SP value of the radical polymerizable compound (C) is preferably 21.0 (MJ / m ³ ) ^1/2 or more and less than 23.0 (MJ / m ³ ) ^1/2 . As described above, the radically polymerizable compound (A) and the radically polymerizable compound (B) have a large SP value and are not compatible with each other. However, since the SP value of the radical polymerizable compound (C) is located between the SP value of the radical polymerizable compound (A) and the SP value of the radical polymerizable compound (B), the radical polymerizable compound (A) In addition to the radically polymerizable compound (B) and the radically polymerizable compound (C), the compatibility of the composition as a whole is improved in a well-balanced manner. Furthermore, the SP value of the radical polymerizable compound (C) is close to the SP value (for example, 23.3) of unsaponified triacetyl cellulose as a transparent protective film and the SP value (for example, 22.2) of an acrylic film, for example. It also contributes to the improvement of adhesion with these transparent protective films. Therefore, in order to improve water resistance and adhesiveness in a well-balanced manner, the composition ratio of the radical polymerizable compound (C) is preferably 5 to 55% by weight. In consideration of the compatibility of the composition as a whole and the adhesion to the transparent protective film, the composition ratio of the radical polymerizable compound (C) is more preferably 10% by weight or more. In consideration of water resistance, the composition ratio of the radical polymerizable compound (C) is more preferably 30% by weight or less.

  The active energy ray-curable adhesive composition used in the present invention is obtained by polymerizing a (meth) acrylic monomer in addition to the radically polymerizable compounds (A), (B) and (C) as curable components. It is preferable to contain an acrylic oligomer (D). By containing the component (D) in the active energy ray-curable adhesive composition, the shrinkage of curing when the active energy ray is irradiated and cured on the composition is reduced, and the adhesive, the polarizer, and the transparent protection Interfacial stress with an adherend such as a film can be reduced. As a result, it is possible to suppress a decrease in adhesiveness between the adhesive layer and the adherend. In order to sufficiently suppress the curing shrinkage of the cured product layer (adhesive layer), the adhesive composition preferably contains 3% by weight or more of the acrylic oligomer (D), and contains 5% by weight or more. Is more preferable. On the other hand, when there is too much content of the acrylic oligomer (D) in adhesive composition, the fall of the reaction rate at the time of irradiating an active energy ray to this composition is intense, and it may become a curing defect. Therefore, the content of the acrylic oligomer (D) in the adhesive composition is preferably 20% by weight or less, and more preferably 15% by weight or less.

  In the manufacturing method of the said polarizing film, it is preferable to contain the radically polymerizable compound which has an active methylene group, and the radical polymerization initiator (E) which has a hydrogen abstraction effect | action. According to such a configuration, the adhesiveness of the adhesive layer of the polarizing film is remarkably improved even in a high humidity environment or immediately after being taken out from water (non-dried state). The reason for this is not clear, but the following causes are considered. That is, the radical polymerizable compound having an active methylene group is taken 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 agent layer is formed. In such a polymerization process, when a radical polymerization initiator (E) having a hydrogen abstracting action is present, hydrogen is extracted from the radical polymerizable compound having an active methylene group while the base polymer constituting the adhesive layer is formed, A radical is generated in the methylene group. And the methylene group which the radical generate | occur | produced, and the hydroxyl group of polarizers, such as PVA, react, and a covalent bond is formed between an adhesive bond layer and a polarizer. As a result, it is speculated that the adhesiveness of the adhesive layer of the polarizing film is remarkably improved even in a non-dry state. Examples of the radical polymerization initiator (E) having a hydrogen abstracting action include compounds represented by the general formula (1).

  In the manufacturing method of the said polarizing film, it is preferable that the said active methylene group is an acetoacetyl group.

  In the manufacturing method of the said polarizing film, it is preferable that the radically polymerizable compound which has the said active methylene group is an acetoacetoxyalkyl (meth) acrylate.

  In the manufacturing method of the said polarizing film, it is preferable that the said radical polymerization initiator (E) is a thioxanthone type radical polymerization initiator.

  In the manufacturing method of the said polarizing film, when the composition whole quantity shall be 100 weight%, the radically polymerizable compound which has the said active methylene group is 1-50 weight%, and radical polymerization initiator (E) is 0.1-10. It is preferable to contain by weight.

  In the production method of the polarizing film, when the glass transition temperature (Tg) of each of the homopolymers of the radical polymerizable compounds (A), (B) and (C) is 60 ° C. or higher, the durability of the adhesive layer Is particularly excellent, and it is preferable because the occurrence of heat shock cracks can be prevented. Here, “heat shock crack” means, for example, a phenomenon in which when a polarizer contracts, it tears in the stretching direction, and in order to prevent this, it is polarized in a heat shock temperature range (−40 ° C. to 60 ° C.). It is important to suppress the expansion / contraction of the child. When the glass transition temperature (Tg) of each of the radically polymerizable compounds (A), (B) and (C) is 60 ° C. or higher as described above, when the adhesive layer is formed, the Tg is Get higher. As a result, a rapid change in elastic modulus of the adhesive layer in the heat shock temperature range can be suppressed, and the expansion / contraction force acting on the polarizer can be reduced, so that the occurrence of heat shock cracks can be prevented. .

  Here, the calculation method of the SP value (solubility parameter) in the present invention will be described below.

(Calculation method of solubility parameter (SP value))
In the present invention, the solubility parameter (SP value) of a radically polymerizable compound, a polarizer, various transparent protective films and the like is calculated by the FEDORS calculation method [“Polymer Engineering and Science (POLYMER ENG. & SCI.)”, No. 14, Vol. 2 (1974), pages 148-154]

（ただしΔｅｉは原子または基に帰属する２５℃における蒸発エネルギー、Δｖｉは２５℃におけるモル体積である）にて計算して求めることができる。

(Where Δei is the evaporation energy at 25 ° C. belonging to the atom or group, and Δvi is the molar volume at 25 ° C.).

  In the above formula, Δei and Δvi represent constant numerical values given to I atoms and groups in the main molecule. Also, representative examples of numerical values of Δe and Δv given to atoms or groups are shown in Table 1 below.

In the method for producing a polarizing film, when the total amount of the radical polymerizable compound in the active energy ray-curable adhesive composition is 100 parts by weight, the radical polymerizable compound (A),
It is preferable to contain 70 to 100 parts by weight of (B) and (C) and an acrylic oligomer (D) obtained by polymerizing a (meth) acrylic monomer. According to this configuration, since the ratio of the radical polymerizable compounds (A), (B) and (C) and the acrylic oligomer (D) in the adhesive composition can be sufficiently secured, the adhesiveness of the adhesive layer And durability and water resistance can be further improved. In order to further improve the adhesion, durability and water resistance in a balanced manner, the radically polymerizable compounds (A), (B) and (C) and the acrylic oligomer (D) are contained in a total of 80 to 100 parts by weight. It is preferable to contain 90 to 100 parts by weight.

  In the manufacturing method of the said polarizing film, it is preferable that the said radically polymerizable compound (A) is hydroxyethyl acrylamide and / or N-methylol acrylamide. Moreover, in the manufacturing method of the said polarizing film, it is preferable that the said radically polymerizable compound (B) is tripropylene glycol diacrylate. Furthermore, in the manufacturing method of the said polarizing film, it is preferable that the said radically polymerizable compound (C) is acryloyl morpholine and / or N-methoxymethyl acrylamide. According to these structures, the adhesiveness, durability, and water resistance of the adhesive layer can be improved in a balanced manner.

  Moreover, the polarizing film according to the present invention is a polarizing film in which a transparent protective film is provided on both surfaces of a polarizer via an adhesive layer, and is manufactured by any one of the polarizing film manufacturing methods described above. It is characterized by that. Such a polarizing film is prevented from curling and has high adhesiveness of the adhesive layer.

In the polarizing film, it is preferable moisture permeability of the transparent protective film is not more than 150g ^/ m 2 ^/ 24h. According to such a configuration, it is difficult for moisture in the air to enter the polarizing film, and a change in the moisture content of the polarizing film itself can be suppressed. As a result, the curling and dimensional change of the polarizing film caused by the storage environment can be suppressed.

  In the manufacturing method of the said polarizing film, it is preferable that the moisture content of the said polarizer at the time of the said bonding process is less than 15%. According to this manufacturing method, the adhesive load between the polarizer and the transparent protective film is excellent, and the durability and water resistance of the adhesive layer are reduced while reducing the drying load of the polarizing film obtained after the bonding step (laminating). A polarizing film provided with an excellent adhesive layer can be produced.

  The optical film according to the present invention is characterized in that at least one polarizing plate described above is laminated.

  Furthermore, the image display device according to the present invention is characterized by using the polarizing film and / or the optical film described above. In such an optical film and image display device, the polarizer of the polarizing film and the transparent protective film are firmly bonded via the adhesive layer, and the adhesive layer is excellent in durability and water resistance.

The conceptual diagram which shows an example of the manufacturing method of the polarizing film which concerns on this invention The conceptual diagram which shows an example of the polarizing film which concerns on this invention The conceptual diagram which shows an example of the manufacturing method of the polarizing film which concerns on this invention provided with the thin polarizer as a polarizer.

  In FIG. 1, the conceptual diagram which shows an example of the manufacturing method of the polarizing film which concerns on this invention is shown. However, the manufacturing method of the polarizing film which concerns on this invention is not limited to the example shown in FIG. In the method for producing a polarizing film according to this embodiment, an active energy ray-curable adhesive composition is applied to at least one surface of the polarizer 1, the first transparent protective film 2, or the second transparent protective film 3. First, the first transparent protective film 2, the bonding step of bonding the polarizer 1 and the first transparent protective film 2, the bonding step of bonding the polarizer 1 and the second transparent protective film 3, Through the adhesive layer obtained by irradiating active energy rays from the side, then irradiating active energy rays from the second transparent protective film 3 side, and curing the active energy ray-curable adhesive composition, An adhesion step of adhering the polarizer 1 and the first transparent protective film 2 and the polarizer 1 and the second transparent protective film 3 is included. In the bonding step, the polarizer 1 and the first transparent protective film 2 and the polarizer 1 and the second transparent protective film 3 may be bonded simultaneously, or may be bonded sequentially, continuously, or intermittently. .

(Coating process)
In the coating process, the active energy ray-curable adhesive composition is applied to at least one surface of the polarizer 1, the first transparent protective film 2, or the second transparent protective film 3. Specifically, the active energy ray-curable adhesive composition may be applied to one side or both sides of the polarizer 1, and the polarizer 1 of the first transparent protective film 2 and / or the second transparent protective film 3. You may apply an active energy ray hardening-type adhesive composition to the surface of the side stuck on. In the example shown in FIG. 1, an active energy ray curable adhesive is used on the surface of the first transparent protective film 2 and the second transparent protective film 3 on the side to be bonded to the polarizer 1 by using an adhesive coating machine 4 ′. The agent composition is applied.

  The polarizer 1 and the transparent protective films 2 and 3 may be subjected to a surface modification treatment before applying the active energy ray-curable adhesive composition. Specific examples of the treatment include corona treatment, plasma treatment, and saponification treatment.

  The coating method of the active energy ray-curable adhesive composition is appropriately selected depending on the viscosity of the composition and the target thickness. Examples of coating methods include reverse coaters, gravure coaters (direct, reverse and offset), bar reverse coaters, roll coaters, die coaters, bar coaters, rod coaters and the like. In addition, for coating, a method such as a dapping method can be appropriately used.

(Bonding process)
The polarizer 1 and the transparent protective films 2 and 3 are bonded together via the adhesive applied as described above. Bonding of the polarizer 1 and the transparent protective films 2 and 3 can be performed by a roll laminator or the like.

  When the moisture content of the said polarizer at the time of the said bonding process is less than 15%, since the drying load of the polarizing film obtained after a bonding process (lamination) can be reduced, it is preferable. Examples of such a low moisture content polarizer include a thin polarizer that can easily reduce the moisture content during drying by heating. The thin polarizer will be described later.

  As will be described later, a thin polarizer (thin high-performance polarizing film) can be suitably manufactured by forming a thin high-performance polarizing film on one surface of a resin substrate. When implementing the manufacturing method which concerns on this invention using this thin polarizer, you may implement a coating process and a bonding process 2 times each. Specifically, for example, when a thin polarizer is used in the production method according to the present invention, the active energy ray curable type is provided on the surface of the laminate film in which the thin polarizer is laminated on one surface of the resin substrate. A first coating step of coating the adhesive composition, a first bonding step of bonding a first transparent protective film from the coating surface side of the thin polarizer, and peeling the resin substrate from the thin polarizer A peeling step, a second coating step of applying an active energy ray-curable adhesive composition to the surface of the thin polarizer from which the resin substrate is peeled, and a coating surface of the thin polarizer You may have the 2nd bonding process of bonding a 2nd transparent protective film from the side. In the first coating step, instead of applying the active energy ray-curable adhesive composition to the thin polarizer, the active energy is applied to the bonding surface of the first transparent protective film with the thin polarizer. A wire curable adhesive composition may be applied. Also, in the second coating step, instead of coating the active energy ray-curable adhesive composition on the thin polarizer, the active energy is applied to the bonding surface of the second transparent protective film with the thin polarizer. A wire curable adhesive composition may be applied.

  In FIG. 2, the conceptual diagram which shows an example of the polarizing film which concerns on this invention is shown. As shown in FIG. 2, in the polarizing film 10 which concerns on this embodiment, the 1st transparent protective film 2 on the single side | surface of the polarizer 1 through the layer of an active energy ray hardening-type adhesive composition by the bonding process, A second transparent protective film 3 is provided on the other surface, and the adhesive layer 4 is formed by curing the layer.

(Adhesion process)
The bonding process will be described with reference to FIG. First, it is obtained by irradiating active energy rays from the first transparent protective film 2 side and then irradiating active energy rays from the second transparent protective film 3 side to cure the active energy ray-curable adhesive composition. The polarizer 1 and the first transparent protective film 2 as well as the polarizer 1 and the second transparent protective film 3 are bonded through the adhesive layer thus formed. In the example shown in FIG. 1, the active energy ray irradiator 5A that is a light source is used to irradiate the active energy ray from the first transparent protective film 2 side, and then the active energy ray irradiator 5B that is a light source is used. The active energy ray-curable adhesive composition is cured by irradiating active energy rays from the second transparent protective film 3 side.

  In the present invention, as the first transparent protective film and the second transparent protective film, an ultraviolet transmission transparent protective film having a light transmittance of 80% or more at a wavelength of 365 nm and / or a light transmittance of 365 nm or less is less than 5%. Various patterns of the UV-opaque transparent protective film can be selected.

(Pattern 1: Transmission → Non-transmission pattern)
First, an active energy ray is irradiated from the first transparent protective film (ultraviolet transparent transparent film) side having a light transmittance of 80% or more at a wavelength of 365 nm (first irradiation), and then the light transmittance at a wavelength of 365 nm is An active energy ray is irradiated from the side of the second protective film (ultraviolet opaque transparent protective film) that is less than 5% (second irradiation) to bond the polarizer and the transparent protective film. In the present invention, the curing reaction proceeds even in the active energy ray-curable adhesive composition interposed between the second transparent protective film and the polarizer by the first irradiation, but the reaction rate is not sufficiently high. . That is, when only the first irradiation is performed, the adhesiveness between the second transparent protective film and the polarizer is insufficient, and there is a possibility that peeling occurs between them. However, by further performing the second irradiation, the curing reaction proceeds sufficiently even in the active energy ray-curable adhesive composition interposed between the second transparent protective film and the polarizer, and the adhesiveness of the adhesive layer is improved. While increasing, curl generation in the polarizing film can be prevented.

  Similarly, in the present invention, the following pattern can be adopted as the bonding step. In any pattern, the curing reaction sufficiently proceeds even in the active energy ray-curable adhesive composition interposed between the second transparent protective film and the polarizer, and the adhesiveness of the adhesive layer is increased. Curling in the polarizing film can be prevented.

(Pattern 2: Impervious → Transparent pattern)
First, an active energy ray is irradiated from the first transparent protective film (ultraviolet non-transmissive protective film) side having a light transmittance of less than 5% at a wavelength of 365 nm (first irradiation), and then the light transmittance at a wavelength of 365 nm is The active energy ray is irradiated from the second protective film (ultraviolet transparent transparent protective film) side which is 80% or more (second irradiation), and the polarizer and the transparent protective film are bonded.

(Pattern 3: Impervious → Impervious pattern)
First, an active energy ray is irradiated from the first transparent protective film (ultraviolet non-transmissive protective film) side having a light transmittance of less than 5% at a wavelength of 365 nm (first irradiation), and then the light transmittance at a wavelength of 365 nm is An active energy ray is irradiated from the side of the second protective film (ultraviolet opaque transparent protective film) that is less than 5% (second irradiation) to bond the polarizer and the transparent protective film.

(Pattern 4: Transmission → Transmission pattern)
First, active energy rays are irradiated from the first transparent protective film (ultraviolet transmission protective film) side having a light transmittance of 80% or more at a wavelength of 365 nm (first irradiation), and then a light transmittance at a wavelength of 365 nm is 80. % Of the second protective film (ultraviolet transparent transparent protective film) side is irradiated with active energy rays (second irradiation) to adhere the polarizer and the transparent protective film.

  As the active energy ray, an electron beam, one containing visible light having a wavelength range of 380 nm to 450 nm can be used. The long wavelength limit of visible light is about 780 nm, but visible light exceeding 450 nm does not contribute to the absorption of the polymerization initiator, but may cause heat generation of the transparent protective film and the polarizer. For this reason, in the present invention, it is preferable to block visible light on the long wavelength side exceeding 450 nm using a band-pass filter.

  As long as the irradiation conditions of an electron beam are conditions which can harden the said active energy ray hardening-type adhesive composition, arbitrary appropriate conditions are employable. For example, in the electron beam irradiation, the acceleration voltage is preferably 5 kV to 300 kV, and more preferably 10 kV to 250 kV. If the acceleration voltage is less than 5 kV, the electron beam may not reach the adhesive and may be insufficiently cured. If the acceleration voltage exceeds 300 kV, the penetration force through the sample is too strong and damages the transparent protective film and the polarizer. There is a risk of giving. The irradiation dose is 5 to 100 kGy, more preferably 10 to 75 kGy. When the irradiation dose is less than 5 kGy, the adhesive becomes insufficiently cured, and when it exceeds 100 kGy, the transparent protective film and the polarizer are damaged, resulting in a decrease in mechanical strength and yellowing, thereby obtaining predetermined optical characteristics. I can't.

  Electron beam irradiation is usually performed in an inert gas, but if necessary, it may be performed in the atmosphere or under a condition in which a small amount of oxygen is introduced. Depending on the material of the transparent protective film, by appropriately introducing oxygen, the transparent protective film surface where the electron beam first hits can be obstructed to prevent oxygen damage and prevent damage to the transparent protective film. An electron beam can be irradiated efficiently.

  However, in the method for producing a polarizing film according to the present invention, in order to prevent the polarizing film from curling while enhancing the adhesive performance of the adhesive layer between the polarizer and the transparent protective film, the wavelength range is used as an active energy ray. It is preferable to use an active energy ray that contains visible light having a wavelength of 380 nm to 450 nm, particularly that having the largest irradiation amount of visible light having a wavelength range of 380 nm to 450 nm. When using a transparent protective film (ultraviolet non-transparent transparent protective film) imparted with ultraviolet absorbing ability, light having a wavelength shorter than 380 nm is absorbed, so that light having a wavelength shorter than 380 nm is an active energy ray-curable adhesive composition. Since it does not reach the product, it does not contribute to the polymerization reaction. Furthermore, light having a wavelength shorter than 380 nm absorbed by the transparent protective film is converted into heat, and the transparent protective film itself generates heat, which causes defects such as curling and wrinkling of the polarizing film. Therefore, in the present invention, it is preferable to use a device that does not emit light having a wavelength shorter than 380 nm as the active energy ray generator, and more specifically, the integrated illuminance in the wavelength range of 380 to 440 nm and the wavelength range of 250 to 370 nm. Is preferably 100: 0 to 100: 50, and more preferably 100: 0 to 100: 40. As the active energy ray satisfying such a relationship of integrated illuminance, a gallium-filled metal halide lamp and an LED light source that emits light in the wavelength range of 380 to 440 nm are preferable. Alternatively, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, super high pressure mercury lamp, incandescent lamp, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, excimer laser or sunlight as the light source, It is also possible to use a light having a wavelength shorter than 380 nm by using a band pass filter. In order to prevent the curling of the polarizing film while improving the adhesive performance of the adhesive layer between the polarizer and the transparent protective film, it is obtained by using a bandpass filter capable of blocking light having a wavelength shorter than 400 nm. It is preferable to use an active energy ray having a wavelength of 405 nm obtained by using an active energy ray or an LED light source.

  In the visible light curable type, it is preferable to warm the active energy ray-curable adhesive composition before irradiation with visible light (pre-irradiation warming), in which case it is preferable to heat to 40 ° C. or higher. It is more preferable to heat to more than ° C. It is also preferable to warm the active energy ray-curable adhesive composition after irradiation with visible light (heating after irradiation), in which case it is preferable to warm to 40 ° C. or higher, and warm to 50 ° C. or higher. It is more preferable.

  The active energy ray-curable adhesive composition containing the photopolymerization initiator of the general formula (1) is particularly an adhesive layer that bonds a polarizer and a transparent protective film having a light transmittance of less than 5% at a wavelength of 365 nm. It can be suitably used when forming. The active energy ray-curable adhesive composition contains the photopolymerization initiator represented by the general formula (1) described above, so that the adhesive layer is cured by irradiating ultraviolet rays through a transparent protective film having UV absorption ability. Can be formed. Therefore, an adhesive bond layer can be hardened also in a polarizing film which laminated a transparent protective film which has UV absorption ability on both sides of a polarizer. However, as a matter of course, the adhesive layer can also be cured in a polarizing film in which a transparent protective film having no UV absorbing ability is laminated.

  Examples of the method for imparting UV absorbing ability to the transparent protective film include a method of containing an ultraviolet absorber in the transparent protective film and a method of laminating a surface treatment layer containing an ultraviolet absorber on the surface of the transparent protective film.

  Specific examples of the ultraviolet absorber include conventionally known oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, triazine compounds, and the like. .

  When the polarizing film according to the present invention is produced in a continuous line, the line speed depends on the curing time of the adhesive, but is preferably 1 to 500 m / min, more preferably 5 to 300 m / min, and still more preferably 10 to 100 m / min. min. When the line speed is too low, the productivity is poor, or the damage to the transparent protective film is too great, and a polarizing film that can withstand the durability test cannot be produced. When the line speed is too high, the adhesive is not sufficiently cured, and the target adhesiveness may not be obtained.

  In the polarizing film of the present invention, a polarizer and a transparent protective film are bonded together via an adhesive layer formed by a cured product layer of the active energy ray-curable adhesive composition. An easily adhesive layer can be provided between the adhesive layer and the adhesive layer. The easy adhesion layer can be formed of, for example, various resins having a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a silicone-based, a polyamide skeleton, a polyimide skeleton, a polyvinyl alcohol skeleton, and the like. These polymer resins can be used alone or in combination of two or more. Moreover, you may add another additive for formation of an easily bonding layer. Specifically, a stabilizer such as a tackifier, an ultraviolet absorber, an antioxidant, and a heat resistance stabilizer may be used.

  The easy adhesion layer is usually provided in advance on a transparent protective film, and the easy adhesion layer side of the transparent protective film and the polarizer are bonded together with an adhesive layer. The easy-adhesion layer is formed by coating and drying the material for forming the easy-adhesion layer on the transparent protective film by a known technique. The material for forming the easy-adhesion layer is usually adjusted as a solution diluted to an appropriate concentration in consideration of the thickness after drying and the smoothness of coating. The thickness of the easy adhesion layer after drying is preferably 0.01 to 5 μm, more preferably 0.02 to 2 μm, and still more preferably 0.05 to 1 μm. Note that a plurality of easy-adhesion layers can be provided, but also in this case, the total thickness of the easy-adhesion layers is preferably in the above range.

（式中、Ｒ^１およびＲ^２は−Ｈ、−ＣＨ_２ＣＨ_３、−ＩＰｒまたはＣｌを示し、Ｒ^１およびＲ^２は同一または異なっても良い）を単独で使用するか、あるいは一般式（１）で表される化合物と後述する３８０ｎｍ以上の光に対して高感度な光重合開始剤とを併用することが好ましい。一般式（１）で表される化合物を使用した場合、３８０ｎｍ以上の光に対して高感度な光重合開始剤を単独で使用した場合に比べて接着性に優れる。一般式（１）で表される化合物の中でも、Ｒ^１およびＲ^２が−ＣＨ_２ＣＨ_３であるジエチルチオキサントンが特に好ましい。組成物中の一般式（１）で表される化合物の組成比率は、組成物全量を１００重量％としたとき、０．１〜５．０重量％であることが好ましく、０．５〜４．０重量％であることがより好ましく、０．９〜３．０重量％であることがさらに好ましい。 In the active energy ray-curable adhesive composition used in the present invention, as a photopolymerization initiator, a compound represented by the following general formula (1);

(Wherein R ¹ and R ² represent —H, —CH ₂ CH ₃ , —IPr or Cl, and R ¹ and R ² may be the same or different), respectively, or a general formula ( It is preferable to use together the compound represented by 1) and a photopolymerization initiator that is highly sensitive to light of 380 nm or more, which will be described later. When the compound represented by the general formula (1) is used, the adhesiveness is excellent as compared with a case where a photopolymerization initiator having high sensitivity to light of 380 nm or more is used alone. Among the compounds represented by the general formula (1), diethylthioxanthone in which R ¹ and R ² are —CH ₂ CH ₃ is particularly preferable. The composition ratio of the compound represented by the general formula (1) in the composition is preferably 0.1 to 5.0% by weight when the total amount of the composition is 100% by weight, and preferably 0.5 to 4%. It is more preferably 0.0% by weight, and even more preferably 0.9 to 3.0% by weight.

  Moreover, it is preferable to add a polymerization initiation assistant as required. Examples of polymerization initiators include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and the like. Among them, ethyl 4-dimethylaminobenzoate is particularly preferable. When a polymerization initiation assistant is used, the addition amount is usually 0 to 5% by weight, preferably 0 to 4% by weight, most preferably 0 to 3% by weight when the total amount of the composition is 100% by weight. .

  Moreover, a well-known photoinitiator can be used together as needed. Since the transparent protective film having UV absorbing ability does not transmit light of 380 nm or less, it is preferable to use a photopolymerization initiator that is highly sensitive to light of 380 nm or more as the photopolymerization initiator. Specifically, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2- (Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine Oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (Η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) 1-yl) -phenyl) titanium and the like.

（式中、Ｒ^３、Ｒ^４およびＲ^５は−Ｈ、−ＣＨ_３、−ＣＨ_２ＣＨ_３、−ＩＰｒまたはＣｌを示し、Ｒ^３、Ｒ^４およびＲ^５は同一または異なっても良い）を使用することが好ましい。一般式（２）で表される化合物としては、市販品でもある２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オン（商品名：ＩＲＧＡＣＵＲＥ９０７ メーカー：ＢＡＳＦ）が好適に使用可能である。その他、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１（商品名：ＩＲＧＡＣＵＲＥ３６９ メーカー：ＢＡＳＦ）、２−（ジメチルアミノ）−２−［（４−メチルフェニル）メチル］−１−［４−（４−モルホリニル）フェニル］−１−ブタノン（商品名：ＩＲＧＡＣＵＲＥ３７９ メーカー：ＢＡＳＦ）が感度が高いため好ましい。 In particular, as a photopolymerization initiator, in addition to the photopolymerization initiator of the general formula (1), a compound represented by the following general formula (2);

Wherein R ³ , R ⁴ and R ⁵ represent —H, —CH ₃ , —CH ₂ CH ₃ , —IPr or Cl, and R ³ , R ⁴ and R ⁵ may be the same or different. It is preferable to use it. As the compound represented by the general formula (2), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE907 manufacturer: BASF) which is also a commercially available product is suitable. Can be used. In addition, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE369 manufacturer: BASF), 2- (dimethylamino) -2-[(4-methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379 manufacturer: BASF) is preferable because of its high sensitivity.

The active energy ray-curable adhesive composition used in the present invention has an SP value of 29.0 (MJ / m ³ ) ^1/2 or more and 32.0 or less (MJ / m ³ ) ^1/2 as a curable component. A radical polymerizable compound (A), an SP value of 18.0 (MJ / m ³ ) ^1/2 or more and less than 21.0 (MJ / m ³ ) ^1/2 , and It is obtained by polymerizing a radical polymerizable compound (C) having an SP value of 21.0 (MJ / m ³ ) ^1/2 or more and 23.0 (MJ / m ³ ) ^1/2 or less and a (meth) acrylic monomer. An acrylic oligomer (D) is contained, and when the total amount of the composition is 100% by weight, the radical polymerizable compound (B) is contained in an amount of 25 to 80% by weight. In the present invention, the “composition total amount” means the total amount including various initiators and additives in addition to the radical polymerizable compound.

The radically polymerizable compound (A) has a radically polymerizable group such as a (meth) acrylate group and has an SP value of 29.0 (MJ / m ³ ) ^1/2 or more and 32.0 or less (MJ / m ³ ) ^Any compound that is ^½ can be used without limitation. Specific examples of the radical polymerizable compound (A) include hydroxyethyl acrylamide (SP value 29.6), N-methylol acrylamide (SP value 31.5) and the like. In the present invention, the (meth) acrylate group means an acrylate group and / or a methacrylate group.

The radical polymerizable compound (B) has a radical polymerizable group such as a (meth) acrylate group, and has an SP value of 18.0 (MJ / m ³ ) ^1/2 or more and 21.0 (MJ / m ³ ). ^Any compound that is less than ^½ can be used without limitation. Specific examples of the radically polymerizable compound (B) include, for example, tripropylene glycol diacrylate (SP value 19.0), 1,9-nonanediol diacrylate (SP value 19.2), and tricyclodecane dimethanol dimer. Acrylate (SP value 20.3), cyclic trimethylolpropane formal acrylate (SP value 19.1), dioxane glycol diacrylate (SP value 19.4), EO-modified diglycerin tetraacrylate (SP value 20.9), etc. Is mentioned. In addition, as a radically polymerizable compound (B), a commercial item can also be used conveniently, for example, Aronix M-220 (made by Toagosei Co., Ltd., SP value 19.0), light acrylate 1,9ND-A (Kyoeisha Chemical Co., Ltd.). Manufactured, SP value 19.2), light acrylate DGE-4A (manufactured by Kyoeisha Chemical Co., SP value 20.9), light acrylate DCP-A (manufactured by Kyoeisha Chemical Co., SP value 20.3), SR-531 (SARTOMER) SP value 19.1), CD-536 (manufactured by SARTOMER, SP value 19.4), and the like.

The radically polymerizable compound (C) has a radically polymerizable group such as a (meth) acrylate group and has an SP value of 21.0 (MJ / m ³ ) ^1/2 or more and 23.0 (MJ / m ³ ). ^Any compound that is ^½ or less can be used without limitation. Specific examples of the radical polymerizable compound (C) include, for example, acryloylmorpholine (SP value 22.9), N-methoxymethylacrylamide (SP value 22.9), N-ethoxymethylacrylamide (SP value 22.3). Etc. In addition, as a radically polymerizable compound (C), a commercial item can also be used suitably, for example, ACMO (the Kojin company make, SP value 22.9), Wasmer 2MA (the Kasano Kosan company make, SP value 22.9). , Wasmer EMA (manufactured by Kasano Kosan Co., Ltd., SP value 22.3), Wasmer 3MA (manufactured by Kasano Kosan Co., Ltd., SP value 22.4), and the like.

  When the glass transition temperature (Tg) of each of the radical polymerizable compounds (A), (B), and (C) is 60 ° C. or higher, the Tg of the adhesive layer is increased and the durability is particularly excellent. It will be. As a result, for example, when an adhesive layer of a polarizer and a transparent protective film is used, occurrence of heat shock cracks in the polarizer can be prevented. Here, the Tg of the homopolymer of the radical polymerizable compound means Tg when the radical polymerizable compound is cured (polymerized) alone. A method for measuring Tg will be described later.

  The active energy ray-curable adhesive composition preferably has a low viscosity when considering workability and uniformity during coating, and therefore an acrylic oligomer (D) formed by polymerizing a (meth) acrylic monomer. It is also preferable that the viscosity is low. The acrylic oligomer having a low viscosity and capable of preventing curing shrinkage of the adhesive layer preferably has a weight average molecular weight (MW) of 15000 or less, more preferably 10,000 or less, and particularly preferably 5000 or less. preferable. On the other hand, in order to sufficiently suppress the curing shrinkage of the cured product layer (adhesive layer), the acrylic oligomer (D) preferably has a weight average molecular weight (MW) of 500 or more, preferably 1000 or more. More preferably, it is particularly preferably 1500 or more. Specific examples of the (meth) acrylic monomer constituting the acrylic oligomer (D) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, N-propyl (meth) acrylate, isopropyl (meth) acrylate, 2 -Methyl-2-nitropropyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, S-butyl (meth) acrylate, T-butyl (meth) acrylate, N-pentyl (meth) acrylate, T-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) acryl (Meth) acrylic acid (carbon number 1-20) alkyl esters such as 4-methyl-2-propylpentyl (meth) acrylate and N-octadecyl (meth) acrylate, and further, for example, cycloalkyl (meth) Acrylate (eg, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, etc.), aralkyl (meth) acrylate (eg, benzyl (meth) acrylate, etc.), polycyclic (meth) acrylate (eg, 2-isobornyl (meth) Acrylate, 2-norbornylmethyl (meth) acrylate, 5-norbornen-2-yl-methyl (meth) acrylate, 3-methyl-2-norbornylmethyl (meth) acrylate, etc.), hydroxyl group-containing (meth) Acrylic esters (e.g., Droxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropylmethyl-butyl (meth) methacrylate, etc.), alkoxy group or phenoxy group-containing (meth) acrylic acid esters (2-methoxyethyl ( (Meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxymethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, etc.), epoxy Group-containing (meth) acrylic acid esters (for example, glycidyl (meth) acrylate), halogen-containing (meth) acrylic acid esters (for example, 2,2,2-trifluoroethyl (meth) acrylate, 2,2 , 2-trifluoroethylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, etc.), alkylaminoalkyl (Meth) acrylate (for example, dimethylaminoethyl (meth) acrylate etc.) etc. are mentioned. These (meth) acrylates can be used alone or in combination of two or more. Specific examples of the acrylic oligomer (D) include “ARUFON” manufactured by Toagosei Co., Ltd., “Act Flow” manufactured by Soken Chemical Co., Ltd., “JONCRYL” manufactured by BASF Japan.

The active energy ray-curable adhesive composition preferably further contains a radical polymerizable compound having an active methylene group and a radical polymerization initiator (E) having a hydrogen abstracting action.

  The radical polymerizable compound having an active methylene group is a compound having an active methylene group having an active double bond group such as a (meth) acryl group at the terminal or in the molecule. Examples of the active methylene group include an acetoacetyl group, an alkoxymalonyl group, and a cyanoacetyl group. Specific examples of the radical polymerizable compound having an active methylene group include 2-acetoacetoxyethyl (meth) acrylate, 2-acetoacetoxypropyl (meth) acrylate, 2-acetoacetoxy-1-methylethyl (meth) acrylate, and the like. Acetoacetoxyalkyl (meth) acrylate; 2-ethoxymalonyloxyethyl (meth) acrylate, 2-cyanoacetoxyethyl (meth) acrylate, N- (2-cyanoacetoxyethyl) acrylamide, N- (2-propionylacetoxybutyl) Examples include acrylamide, N- (4-acetoacetoxymethylbenzyl) acrylamide, and N- (2-acetoacetylaminoethyl) acrylamide. The SP value of the radically polymerizable compound having an active methylene group is not particularly limited, and a compound having an arbitrary value can be used.

In the present invention, examples of the radical polymerization initiator (E) having a hydrogen abstracting action include thioxanthone radical polymerization initiators and benzophenone radical polymerization initiators. Examples of the thioxanthone radical polymerization initiator include compounds represented by the above general formula (1). Specific examples of the compound represented by the general formula (1) include thioxanthone, dimethylthioxanthone, diethylthioxanthone, isopropylthioxanthone, and chlorothioxanthone. Among the compounds represented by the general formula (1), diethylthioxanthone in which R ¹ and R ² are —CH ₂ CH ₃ is particularly preferable.

  As described above, in the present invention, radicals are generated in the methylene group of the radical polymerizable compound having an active methylene group in the presence of the radical polymerization initiator (E) having a hydrogen abstraction action. The hydroxyl group of the polarizer reacts to form a covalent bond. Accordingly, in order to generate radicals in the methylene group of the radically polymerizable compound having an active methylene group and to sufficiently form such a covalent bond, the radical polymerizable property having an active methylene group when the total amount of the composition is 100% by weight. It is preferable to contain 1 to 50% by weight of the compound and 0.1 to 5.0% by weight of the radical polymerization initiator (E), 3 to 30% by weight of the radical polymerizable compound having an active methylene group, and a radical The polymerization initiator (E) is more preferably contained in an amount of 0.5 to 4.0% by weight. Furthermore, it is particularly preferable to contain 0.9 to 3.0% by weight of the radical polymerization initiator (E). If the radically polymerizable compound having an active methylene group is less than 1% by weight, the effect of improving the adhesiveness in a non-dry state is low, and the water resistance may not be sufficiently improved. Insufficient curing of the agent layer may occur. Further, if the radical polymerization initiator (E) having a hydrogen abstraction action is less than 0.1% by weight, the hydrogen abstraction reaction may not sufficiently proceed. If it exceeds 5.0% by weight, It may not dissolve completely.

  The active energy ray-curable adhesive composition used in the present invention contains 25 to 80% by weight of the radical polymerizable compound (B) when the total amount of the composition is 100% by weight. Further, in the active energy ray-curable adhesive composition, when the total amount of the composition is 100% by weight, 3 to 40% by weight of the radical polymerizable compound (A) and 5 to 5% of the radical polymerizable compound (C). It is preferable to contain 55% by weight and 3 to 20% by weight of the acrylic oligomer (D).

  Moreover, various additives can be mix | blended with the active energy ray hardening-type adhesive composition used in this invention as another arbitrary component in the range which does not impair the objective and effect of this invention. Such additives include epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, Polymers or oligomers such as silicone oligomers and polysulfide oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-T-butyl-4-methylphenol; polymerization initiators; leveling agents; wettability improvers; Plasticizer; UV absorber; Silane coupling agent; Inorganic filler; Pigment;

  Among the above additives, the silane coupling agent acts on the polarizer surface and can impart further water resistance. When a silane coupling agent is used, the amount added is usually 0 to 10% by weight, preferably 0 to 5% by weight, most preferably 0 to 3% by weight when the total amount of the composition is 100% by weight. .

  As the silane coupling agent, an active energy ray-curable compound is preferably used, but the same water resistance can be imparted even if it is not active energy ray-curable.

  Specific examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycid as active energy ray-curable compounds. Xylpropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, P-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy Examples thereof include silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

  Specific examples of silane coupling agents that are not active energy ray curable include N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2. (Aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N -Phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3 -Mercaptopropylmethyldimethoxysilane, - mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanate propyltriethoxysilane, etc. imidazole silane.

  Preferable are 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane.

  The adhesive layer formed by the active energy ray-curable adhesive composition has higher durability than the aqueous adhesive layer. In the present invention, it is preferable to use an adhesive layer having a Tg of 60 ° C. or higher. Moreover, it is preferable to control so that the thickness of an adhesive bond layer may be set to 0.01-7 micrometers. Thus, in the polarizing film of the present invention, when using the active energy ray-curable adhesive composition in which the adhesive layer has a high Tg of 60 ° C. or higher, and the thickness of the adhesive layer is controlled within the above range, Durability in harsh environments under high humidity and high temperature can be satisfied. In consideration of the durability of the polarizing film, in the present invention, in particular, when Tg (° C.) of the adhesive layer is defined as A and the thickness (μm) of the adhesive layer is defined as B, Formula (1): A− It is preferable that 12 × B> 58 is satisfied.

  As described above, the active energy ray-curable adhesive composition is preferably selected so that the Tg of the adhesive layer formed thereby is 60 ° C. or higher, and more preferably 70 ° C. or higher. Further, it is preferably 75 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 120 ° C. or higher. On the other hand, if the Tg of the adhesive layer becomes too high, the flexibility of the polarizing film is lowered. Therefore, the Tg of the adhesive layer is preferably 300 ° C. or lower, more preferably 240 ° C. or lower, and further preferably 180 ° C. or lower.

  Moreover, as above-mentioned, the thickness of an adhesive bond layer becomes like this. Preferably it is 0.01-7 micrometers, More preferably, it is 0.01-5 micrometers, More preferably, it is 0.01-2 micrometers, Most preferably, it is 0.01-1 micrometer. When the thickness of the adhesive layer is smaller than 0.01 μm, the cohesive force of the adhesive force itself cannot be obtained, and the adhesive strength may not be obtained. On the other hand, if the thickness of the adhesive layer exceeds 7 μm, the polarizing film cannot satisfy the durability.

  As for the polarizing film of this invention, the transparent protective film is bonded together on both surfaces of the polarizer through the adhesive bond layer formed of the hardened | cured material layer of the said active energy ray hardening-type adhesive composition.

  The polarizer is not particularly limited, and various types can be used. Examples of the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene / vinyl acetate copolymer partially saponified film, and two colors such as iodine and dichroic dye. And polyene-based oriented films such as those obtained by adsorbing a functional material and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products. Among these, a polarizer composed of a polyvinyl alcohol film and a dichroic material such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 80 μm or less.

  A polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous solution of iodine and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution of boric acid or potassium iodide. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with dirt and anti-blocking agents by washing the polyvinyl alcohol film with water, it also has the effect of preventing unevenness such as uneven coloring by swelling the polyvinyl alcohol film. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.

  As the polarizer, a thin polarizer having a thickness of 10 μm or less can be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing film can be reduced. Further, since the thin polarizer can easily reduce the moisture content during heat drying, it can be suitably used as a polarizer having a moisture content of less than 15%.

  As the thin polarizer, representatively, JP-A-51-069644, JP-A-2000-338329, WO2010 / 100917 pamphlet, PCT / JP2010 / 001460 specification, or Japanese Patent Application 2010- The thin polarizing film described in 269002 specification and Japanese Patent Application No. 2010-263692 specification can be mentioned. These thin polarizing films can be obtained by a production method including a step of stretching a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin base material in a laminated state and a step of dyeing. With this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.

  As the thin polarizing film, among the production methods including the step of stretching in the state of a laminate and the step of dyeing, WO2010 / 100917 pamphlet, PCT / PCT / PCT / JP 2010/001460 specification, or Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692 as described in the manufacturing method including a step of stretching in a boric acid aqueous solution is preferable. What is obtained by the manufacturing method including the process of extending | stretching in the air auxiliary | assistant before extending | stretching in the boric acid aqueous solution as described in Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692 is preferable.

  The thin high-performance polarizing film described in the specification of PCT / JP2010 / 001460 is a thin film having a thickness of 7 μm or less made of a PVA-based resin oriented with a dichroic material, which is integrally formed on a resin base material. It is a high-functional polarizing film, and has optical properties such as a single transmittance of 42.0% or more and a degree of polarization of 99.95% or more.

  The thin high-performance polarizing film generates a PVA-based resin layer by applying and drying a PVA-based resin on a resin substrate having a thickness of at least 20 μm, and the generated PVA-based resin layer is used as a dichroic dyeing solution. So that the dichroic substance is adsorbed on the PVA resin layer, and the PVA resin layer on which the dichroic substance is adsorbed is integrated with the resin base material in the boric acid aqueous solution so that the total draw ratio is the original length. It can manufacture by extending | stretching so that it may become 5 times or more.

  Moreover, it is a method for producing a laminate film including a thin high-performance polarizing film in which a dichroic substance is oriented, and includes a resin base material having a thickness of at least 20 μm and a PVA resin on one side of the resin base material. The said laminated body containing the process of producing | generating the laminated body film containing the PVA-type resin layer formed by apply | coating and drying aqueous solution, and the PVA-type resin layer formed in the single side | surface of the resin base material A step of adsorbing the dichroic substance to the PVA resin layer contained in the laminate film by immersing the film in a dye solution containing the dichroic substance, and a PVA resin adsorbing the dichroic substance A step of stretching the laminate film including a layer in a boric acid aqueous solution so that the total stretching ratio is 5 times or more of the original length, and a PVA resin layer on which a dichroic substance is adsorbed Stretched together with As a result, a thickness of 7 μm or less, a single transmittance of 42.0% or more, and a degree of polarization of 99.95% or more are formed of a PVA resin layer in which a dichroic material is oriented on one side of a resin base The thin high-performance polarizing film can be manufactured by including a step of manufacturing a laminate film on which a thin high-performance polarizing film having the above optical characteristics is formed.

  The above-mentioned Japanese Patent Application Nos. 2010-269002 and 2010-263692 are thin polarizing films, which are polarizing films of a continuous web made of a PVA-based resin in which a dichroic material is oriented, and are amorphous esters. A laminate including a PVA-based resin layer formed on a thermoplastic resin base material is stretched in a two-stage stretching process consisting of air-assisted stretching and boric acid-water stretching to a thickness of 10 μm or less. It is. Such a thin polarizing film has P> − (100.929T-42.4-1) × 100 (where T <42.3) and P ≧ 99, where T is the single transmittance and P is the polarization degree. .9 (where T ≧ 42.3) is preferable.

  Specifically, the thin polarizing film is a stretch intermediate formed of an oriented PVA resin layer by high-temperature stretching in the air with respect to the PVA resin layer formed on the amorphous ester thermoplastic resin substrate of the continuous web. A colored intermediate product comprising a PVA-based resin layer in which a dichroic material (preferably iodine or a mixture of iodine and an organic dye) is oriented by adsorption of the dichroic material to the stretched intermediate product and a step of generating the product. A thin polarizing film comprising a step of forming a product, and a step of generating a polarizing film having a thickness of 10 μm or less comprising a PVA-based resin layer in which a dichroic material is oriented by stretching in a boric acid solution with respect to a colored intermediate product It can be manufactured by a manufacturing method.

In this production method, the total draw ratio of the PVA resin layer formed on the amorphous ester thermoplastic resin base material by high-temperature drawing in air and drawing in boric acid solution should be 5 times or more. desirable. The liquid temperature of the boric acid aqueous solution for boric-acid water extending | stretching can be 60 degreeC or more. Before stretching the colored intermediate product in the aqueous boric acid solution, it is desirable to insolubilize the colored intermediate product. In this case, the colored intermediate product is added to the aqueous boric acid solution whose liquid temperature does not exceed 40 ° C. It is desirable to do so by dipping. The amorphous ester-based thermoplastic resin base material is amorphous polyethylene containing copolymerized polyethylene terephthalate copolymerized with isophthalic acid, copolymerized polyethylene terephthalate copolymerized with cyclohexanedimethanol, or other copolymerized polyethylene terephthalate. It can be terephthalate and is preferably made of a transparent resin, and the thickness thereof can be 7 times or more the thickness of the PVA resin layer to be formed. Moreover, the draw ratio of the high temperature stretching in the air is preferably 3.5 times or less, and the stretching temperature of the high temperature stretching in the air is preferably not less than the glass transition temperature of the PVA resin, specifically in the range of 95 ° C to 150 ° C. When performing high temperature stretching in the air by free end uniaxial stretching, the total stretching ratio of the PVA resin layer formed on the amorphous ester thermoplastic resin base material is preferably 5 to 7.5 times . In addition, when performing high-temperature stretching in the air by uniaxial stretching at the fixed end, the total stretching ratio of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin base material is 5 times or more and 8.5 times or less. Is preferred.
More specifically, a thin polarizing film can be produced by the following method.

  A base material of a continuous web of isophthalic acid copolymerized polyethylene terephthalate (amorphous PET) in which 6 mol% of isophthalic acid is copolymerized is prepared. The glass transition temperature of amorphous PET is 75 ° C. A laminate comprising a continuous web of amorphous PET substrate and a polyvinyl alcohol (PVA) layer is prepared as follows. Incidentally, the glass transition temperature of PVA is 80 ° C.

  A 200 μm-thick amorphous PET base material and a 4-5% concentration PVA aqueous solution in which PVA powder having a polymerization degree of 1000 or more and a saponification degree of 99% or more are dissolved in water are prepared. Next, a PVA aqueous solution is applied to a 200 μm thick amorphous PET substrate and dried at a temperature of 50 to 60 ° C. to obtain a laminate in which a 7 μm thick PVA layer is formed on the amorphous PET substrate. .

  A laminated body including a PVA layer having a thickness of 7 μm is subjected to the following steps including a two-step stretching process of air-assisted stretching and boric acid water stretching to produce a thin high-functional polarizing film having a thickness of 3 μm. In the first-stage aerial auxiliary stretching step, the laminate including the 7 μm-thick PVA layer is integrally stretched with the amorphous PET substrate to produce a stretched laminate including the 5 μm-thick PVA layer. Specifically, in this stretched laminate, a laminate including a 7 μm-thick PVA layer is subjected to a stretching apparatus disposed in an oven set to a stretching temperature environment of 130 ° C. so that the stretching ratio is 1.8 times. Are stretched uniaxially at the free end. By this stretching treatment, the PVA layer contained in the stretched laminate is changed to a 5 μm thick PVA layer in which PVA molecules are oriented.

  Next, a colored laminate in which iodine is adsorbed on a PVA layer having a thickness of 5 μm in which PVA molecules are oriented is generated by a dyeing process. Specifically, this colored laminate has a single layer transmittance of the PVA layer constituting the high-performance polarizing film that is finally produced by using the stretched laminate in a staining solution containing iodine and potassium iodide at a liquid temperature of 30 ° C. Iodine is adsorbed to the PVA layer contained in the stretched laminate by dipping for an arbitrary period of time so as to be 40 to 44%. In this step, the staining solution uses water as a solvent and an iodine concentration in the range of 0.12 to 0.30% by weight and a potassium iodide concentration in the range of 0.7 to 2.1% by weight. The concentration ratio of iodine and potassium iodide is 1 to 7. Incidentally, potassium iodide is required to dissolve iodine in water. More specifically, by immersing the stretched laminate in a dyeing solution having an iodine concentration of 0.30% by weight and a potassium iodide concentration of 2.1% by weight for 60 seconds, iodine is applied to a 5 μm-thick PVA layer in which PVA molecules are oriented. A colored laminate is adsorbed on the substrate.

  Further, the colored laminated body is further stretched integrally with the amorphous PET base material by the second stage boric acid underwater stretching step to produce an optical film laminate including a PVA layer constituting a highly functional polarizing film having a thickness of 3 μm. To do. Specifically, this optical film laminate is stretched by applying a colored laminate to a stretching apparatus provided in a treatment apparatus set to a boric acid aqueous solution having a liquid temperature range of 60 to 85 ° C. containing boric acid and potassium iodide. It is stretched uniaxially at the free end so that the magnification is 3.3 times. More specifically, the liquid temperature of the boric acid aqueous solution is 65 ° C. It also has a boric acid content of 4 parts by weight with respect to 100 parts by weight of water and a potassium iodide content of 5 parts by weight with respect to 100 parts by weight of water. In this step, the colored laminate with adjusted iodine adsorption amount is first immersed in a boric acid aqueous solution for 5 to 10 seconds. After that, the colored laminate is passed as it is between a plurality of sets of rolls having different peripheral speeds, which is a stretching apparatus provided in the processing apparatus, and the stretching ratio is freely increased to 3.3 times over 30 to 90 seconds. Stretch uniaxially. By this stretching treatment, the PVA layer contained in the colored laminate is changed into a PVA layer having a thickness of 3 μm in which the adsorbed iodine is oriented higher in one direction as a polyiodine ion complex. This PVA layer constitutes a highly functional polarizing film of the optical film laminate.

  Although not an indispensable step for the production of an optical film laminate, the optical film laminate was removed from the boric acid aqueous solution and adhered to the surface of the 3 μm-thick PVA layer formed on the amorphous PET substrate by the washing step. It is preferable to wash boric acid with an aqueous potassium iodide solution. Thereafter, the washed optical film laminate is dried by a drying process using hot air at 60 ° C. The cleaning process is a process for eliminating appearance defects such as boric acid precipitation.

  Similarly, it is not an indispensable process for producing an optical film laminate, but an adhesive is applied to the surface of a 3 μm-thick PVA layer formed on an amorphous PET substrate by a bonding and / or transfer process. However, after bonding the 80 μm thick triacetyl cellulose film, the amorphous PET substrate can be peeled off, and the 3 μm thick PVA layer can be transferred to the 80 μm thick triacetyl cellulose film.

[Other processes]
The manufacturing method of said thin-shaped polarizing film may include another process other than the said process. Examples of other steps include an insolubilization step, a crosslinking step, and a drying (adjustment of moisture content) step. The other steps can be performed at any appropriate timing.
The insolubilization step is typically performed by immersing the PVA resin layer in a boric acid aqueous solution. By performing the insolubilization treatment, water resistance can be imparted to the PVA resin layer. The concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water. The liquid temperature of the insolubilizing bath (boric acid aqueous solution) is preferably 20 ° C to 50 ° C. Preferably, the insolubilization step is performed after the laminate is manufactured and before the dyeing step and the underwater stretching step.
The crosslinking step is typically performed by immersing the PVA resin layer in an aqueous boric acid solution. By performing the crosslinking treatment, water resistance can be imparted to the PVA resin layer. The concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water. Moreover, when performing a bridge | crosslinking process after the said dyeing | staining process, it is preferable to mix | blend iodide further. By blending iodide, elution of iodine adsorbed on the PVA resin layer can be suppressed. The blending amount of iodide is preferably 1 part by weight to 5 parts by weight with respect to 100 parts by weight of water. Specific examples of the iodide are as described above. The liquid temperature of the crosslinking bath (boric acid aqueous solution) is preferably 20 ° C to 50 ° C. Preferably, the crosslinking step is performed before the second boric acid aqueous drawing step. In a preferred embodiment, the dyeing step, the crosslinking step, and the second boric acid aqueous drawing step are performed in this order.

  In the manufacturing method of the polarizing film which concerns on this invention, the thin polarizer formed into a film on the single side | surface of the resin base material can be used conveniently as a polarizer. FIG. 3 shows an example of a method for producing a polarizing film according to the present invention, which includes a thin polarizer as a polarizer. In the example shown in FIG. 3, the 1st coating process of applying an active energy ray hardening-type adhesive composition to the bonding surface with the thin polarizer 1 of the 1st transparent protective film 2, and the single side | surface of a resin base material The thin polarizer 1 and the laminated film 1 in which the thin polarizer 1 is laminated (in FIG. 3, the description of the resin substrate is omitted, but the resin substrate is laminated on the lower layer side of the thin polarizer 1). The 1st bonding process of bonding 1 transparent protective film 2 is implemented. Next, using the active energy ray irradiator 5A, the thin polarizer 1 and the first transparent protective film 2 are adhered by irradiating the active energy rays from the first transparent protective film 2 side (first adhesion). Process). Next, the resin base material is peeled from the thin polarizer 1 (peeling step). Next, the second coating step of applying the active energy ray-curable adhesive composition to the bonding surface of the second transparent protective film 3 to the thin polarizer 1, and the resin substrate of the thin polarizer 1 The 2nd bonding process which bonds the thin polarizer 1 and the 2nd transparent protective film 3 from the surface side of the peeled side is implemented. Next, the active energy ray irradiator 5B is used to bond the thin polarizer 1 and the second transparent protective film 3 by irradiating active energy rays from the second transparent protective film 3 side (second adhesion). Process). Thereby, a polarizing film provided with the thin polarizer 1 can be manufactured.

As a material for forming a transparent protective film provided on one or both sides of the polarizer, a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like is preferable. / ^m, more preferably not more 2 / 24h or less, particularly preferably those following 140 g ^/ m 2 / 24h, further preferably the following 120 g ^/ m 2 / 24h. The moisture permeability is determined by the method described in the examples.

  The thickness of the transparent protective film can be appropriately determined, but is generally about 1 to 500 μm, preferably 1 to 300 μm, more preferably 5 to 200 μm from the viewpoints of workability such as strength and handleability and thin layer properties. preferable. Furthermore, 10-200 micrometers is preferable and 20-80 micrometers is preferable.

  Examples of the material for forming the transparent protective film satisfying the low moisture permeability include polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate resins; arylate resins; amide resins such as nylon and aromatic polyamide; polyethylene and polypropylene Polyolefin polymers such as ethylene / propylene copolymers, cyclic olefin resins having a cyclo or norbornene structure, (meth) acrylic resins, or a mixture thereof can be used. Among the resins, polycarbonate resins, cyclic polyolefin resins, and (meth) acrylic resins are preferable, and cyclic polyolefin resins and (meth) acrylic resins are particularly preferable.

  A specific example of the cyclic polyolefin resin is preferably a norbornene resin. The cyclic olefin-based resin is a general term for resins that are polymerized using a cyclic olefin as a polymerization unit, and is described in, for example, JP-A-1-240517, JP-A-3-14882, JP-A-3-122137, and the like. Resin. Specific examples include ring-opening (co) polymers of cyclic olefins, addition polymers of cyclic olefins, cyclic olefins and soot-olefins such as ethylene and propylene (typically random copolymers), And graft polymers obtained by modifying them with an unsaturated carboxylic acid or a derivative thereof, and hydrides thereof. Specific examples of the cyclic olefin include norbornene monomers.

  Various products are commercially available as the cyclic polyolefin resin. As specific examples, trade names “ZEONEX” and “ZEONOR” manufactured by ZEON CORPORATION, product names “ARTON” manufactured by JSR Corporation, “TOPAS” manufactured by TICONA, and product names manufactured by Mitsui Chemicals, Inc. “APEL”.

  The (meth) acrylic resin preferably has a Tg (glass transition temperature) of 115 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 125 ° C. or higher, and particularly preferably 130 ° C. or higher. When Tg is 115 ° C. or higher, the polarizing plate can be excellent in durability. Although the upper limit of Tg of the (meth) acrylic resin is not particularly limited, it is preferably 170 ° C. or lower from the viewpoint of moldability and the like. From (meth) acrylic resin, a film having in-plane retardation (RE) and thickness direction retardation (RTH) of almost zero can be obtained.

As the (meth) acrylic resin, any appropriate (meth) acrylic resin can be adopted as long as the effects of the present invention are not impaired. For example, poly (meth) acrylic acid ester such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester copolymer, methyl methacrylate-acrylic acid ester- (Meth) acrylic acid copolymer, (meth) methyl acrylate-styrene copolymer (MS resin, etc.), polymer having an alicyclic hydrocarbon group (for example, methyl methacrylate-cyclohexyl methacrylate copolymer, Methyl methacrylate- (meth) acrylate norbornyl copolymer, etc.). Preferably, poly (meth) acrylate C1-6 alkyl such as poly (meth) acrylate methyl is used. More preferred is a methyl methacrylate resin containing methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight).

  Specific examples of (meth) acrylic resins include (meth) acrylic resins having a ring structure in the molecule described in, for example, Acrypet VH and Acrypet VRL20A manufactured by Mitsubishi Rayon Co., Ltd., and JP-A-2004-70296. And high Tg (meth) acrylic resins obtained by intramolecular crosslinking or intramolecular cyclization reaction.

  As the (meth) acrylic resin, a (meth) acrylic resin having a lactone ring structure can also be used. It is because it has high mechanical strength by high heat resistance, high transparency, and biaxial stretching.

  Examples of the (meth) acrylic resin having a lactone ring structure include JP 2000-230016, JP 2001-151814, JP 2002-120326, JP 2002-254544, and JP 2005. Examples thereof include (meth) acrylic resins having a lactone ring structure described in Japanese Patent No. 146084.

  In addition, the transparent protective film of the low moisture permeability provided on both surfaces of the polarizer may use a transparent protective film made of the same polymer material on the front and back, or may use a transparent protective film made of a different polymer material or the like. Good.

  As the transparent protective film, a phase difference plate having a phase difference of 40 nm or more and / or a thickness direction retardation of 80 nm or more can be used. The front phase difference is usually controlled in the range of 40 to 200 nm, and the thickness direction phase difference is usually controlled in the range of 80 to 300 nm. When a retardation plate is used as the transparent protective film, the retardation plate functions also as a transparent protective film, so that the thickness can be reduced.

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

  In addition, the film which has the said phase difference can be separately bonded to the transparent protective film which does not have a phase difference, and the said function can be provided.

  A functional layer such as a hard coat layer, an antireflection layer, an antisticking layer, a diffusion layer or an antiglare layer can be provided on the surface of the transparent protective film to which the polarizer is not adhered. The functional layers such as the hard coat layer, antireflection layer, antisticking layer, diffusion layer and antiglare layer can be provided on the transparent protective film itself, and separately provided separately from the transparent protective film. You can also.

  The polarizing film of the present invention can be used as an optical film laminated with another optical layer in practical use. The optical layer is not particularly limited. For example, for forming a liquid crystal display device such as a reflection plate, a semi-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), and a viewing angle compensation film. One or more optical layers that may be used can be used. In particular, a reflective polarizing film or semi-transmissive polarizing film in which a polarizing plate or a semi-transmissive reflecting plate is further laminated on the polarizing film of the present invention, an elliptical polarizing film or circularly polarizing film in which a retardation film is further laminated on a polarizing film. A wide viewing angle polarizing film obtained by further laminating a viewing angle compensation film on a film or a polarizing film, or a polarizing film obtained by further laminating a brightness enhancement film on the polarizing film is preferred.

  An optical film obtained by laminating the above optical layer on a polarizing film can be formed by a method of sequentially laminating separately in the manufacturing process of a liquid crystal display device or the like. It is excellent in stability and assembly work, and has the advantage of improving the manufacturing process of a liquid crystal display device and the like. Appropriate bonding means such as an adhesive layer can be used for lamination. When adhering the above polarizing film and other optical films, their optical axes can be set at an appropriate arrangement angle in accordance with the target retardation characteristics.

  An adhesive layer for adhering to other members such as a liquid crystal cell can be provided on the polarizing film described above or an optical film in which at least one polarizing film is laminated. The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited. For example, an acrylic polymer, silicone-based polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based polymer is appropriately selected. Can be used. In particular, those having excellent optical transparency such as an acrylic pressure-sensitive adhesive, exhibiting appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and being excellent in weather resistance, heat resistance and the like can be preferably used.

  The pressure-sensitive adhesive layer can be provided on one side or both sides of a polarizing film or an optical film as an overlapping layer of different compositions or types. Moreover, when providing in both surfaces, it can also be set as adhesive layers, such as a different composition, a kind, and thickness, in the front and back of a polarizing film or an optical film. The thickness of the pressure-sensitive adhesive layer can be appropriately determined according to the purpose of use and adhesive force, and is generally 1 to 500 μm, preferably 1 to 200 μm, and particularly preferably 1 to 100 μm.

  The exposed surface of the adhesive layer is temporarily covered with a separator for the purpose of preventing contamination until it is put into practical use. Thereby, it can prevent contacting an adhesion layer in the usual handling state. As the separator, except for the above thickness conditions, for example, an appropriate thin leaf body such as a plastic film, rubber sheet, paper, cloth, non-woven fabric, net, foamed sheet, metal foil, or a laminate thereof, and a silicone-based or long sheet as necessary. Appropriate ones according to the prior art, such as those coated with an appropriate release agent such as a chain alkyl type, fluorine type or molybdenum sulfide, can be used.

  The polarizing film or the optical film of the present invention can be preferably used for forming various devices such as a liquid crystal display device. The liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally formed by appropriately assembling components such as a liquid crystal cell, a polarizing film or an optical film, and an illumination system as necessary, and incorporating a drive circuit. There is no limitation in particular except the point which uses the polarizing film or optical film by invention, and it can apply to the former. As the liquid crystal cell, for example, any type such as a TN type, an STN type, and a bowl type can be used.

  An appropriate liquid crystal display device such as a liquid crystal display device in which a polarizing film or an optical film is disposed on one side or both sides of a liquid crystal cell, or a backlight or a reflecting plate that is used in an illumination system can be formed. In that case, the polarizing film or optical film by this invention can be installed in the one side or both sides of a liquid crystal cell. When providing a polarizing film or an optical film on both sides, they may be the same or different. Further, when forming the liquid crystal display device, for example, a single layer or a suitable layer such as a diffusing plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusing plate, a backlight, etc. Two or more layers can be arranged.

  Examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

<Tg: Glass transition temperature>
Tg was measured under the following measurement conditions using a TA Instruments dynamic viscoelasticity measuring device RSAIII.
Sample size: width 10mm, length 30mm,
Clamp distance 20mm,
Measurement mode: Tensile, Frequency: 1HZ, Temperature increase rate: 5 ° C./min Dynamic viscoelasticity was measured and adopted as the temperature Tg of tan δ peak top.

<Water vapor permeability of transparent protective film>
The moisture permeability was measured according to a moisture permeability test (cup method) of JIS Z0208. A sample cut to a diameter of 60 mm was set in a moisture permeable cup containing about 15 G of calcium chloride and the temperature was 40 ° C. and the humidity was 90% R.D. H. The placed in a constant temperature machine, to determine the moisture permeability by measuring the weight increase of calcium chloride before and after allowing to stand for 24 hours ^{(g / m 2 / 24h)} .

<Transparent protective film>
A biaxially stretched film of 55 μm-thick norbornene resin (manufactured by Nippon Zeon Co., Ltd., trade name: ZEONOR) was used as the UV-transmissive transparent protective film having a light transmittance of 365% at a wavelength of 365 nm. 91.1% The light transmittance of the wavelength 365nm of the norbornene resin film, the moisture permeability is ^{11 (g / m 2 / 24h} ), a front retardation is 55 nm, the thickness direction retardation was 135 nm.
In addition, as a UV-opaque transparent protective film having a light transmittance at a wavelength of 365 nm of less than 5%, a 60 μm-thick triacetylcellulose film (TAC) (SP value 23.3) is subjected to saponification and corona treatment, etc. (Hereinafter, TAC that has not been subjected to saponification / corona treatment or the like is also referred to as “untreated TAC”). The untreated TAC 0.1% is the light transmittance of wavelength 365nm of the film, the moisture permeability was ^{507 (g / m 2 / 24h} ).

<Active energy rays>
Visible light (gallium filled metal halide lamp) as an active energy ray Irradiation device: FUSION UV SYSTEMS, INC. LIGHT HAMMER10 bulb: V bulb Peak illuminance: 1600 mW / cm ² , integrated irradiation dose 1000 / mJ / cm ²
(Wavelength 380-440 nm) was used. The illuminance of visible light was measured using a SOLA-CHECK system manufactured by SOLATEL.

(Adjustment of active energy ray-curable adhesive composition)
Each component used is as follows.

(1) Radical polymerizable compound (A)
HEAA (hydroxyethyl acrylamide), SP value 29.6, homopolymer Tg 123 ° C., manufactured by Kojin Co., Ltd. (2) Radical polymerizable compound (B)
ARONIX M-220 (M-220) (tripropylene glycol diacrylate), SP value 19.0, homopolymer Tg 69 ° C., manufactured by Toagosei Co., Ltd. (3) Radical polymerizable compound (C)
ACMO (acryloylmorpholine), SP value 22.9, homopolymer Tg 150 ° C., (4) acrylic oligomer (D) made by polymerizing (meth) acrylic monomer
ARUFON UP-1190 (UP-1190), manufactured by Toagosei Co., Ltd. (5) AAEM (2-acetoacetoxyethyl methacrylate), SP value 20.23 (MJ / M ³ ) ^1/2 , Tg of homopolymer, 9 ° C., Japan synthesis Chemical (6) Compound represented by general formula (1) KAYACURE DETX-S (DETX-S) (diethylthioxanthone), Nippon Kayaku Co., Ltd. (7) Photopolymerization initiator (represented by general formula (2) Compound)
IRGACURE907 (IRG907) (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one), manufactured by BASF

Example 1
As an active energy ray-curable adhesive composition, HEAA / M-220 / ACMO / UP-1190 / AAEM / IRGACURE907 / KAYACURE DETX-S = 16.4 / 32.8 / 32.8 / 8.2 / 5. 7 / 2.5 / 1.6 (values are weight% when the total amount of the composition is 100% by weight), and stirred at 50 ° C. for 1 hour to prepare an active energy ray-curable adhesive composition did.

(Production of thin polarizing film X and production of polarizing film using it)
In order to produce the thin polarizing film X, first, a laminate in which a PVA layer having a thickness of 24 μm is formed on an amorphous PET base material is produced by air-assisted stretching at a stretching temperature of 130 ° C., and then, A colored laminate is produced by dyeing the stretched laminate, and the colored laminate is stretched integrally with the amorphous PET substrate so that the total stretch ratio is 5.94 times by stretching in boric acid water at a stretching temperature of 65 degrees. An optical film laminate comprising a 10 μm thick PVA layer was produced. The PVA molecules in the PVA layer formed on the amorphous PET substrate by such two-stage stretching are oriented in the higher order, and the iodine adsorbed by the dyeing is oriented in the one direction as the polyiodine ion complex. In addition, an optical film laminate including a PVA layer having a thickness of 10 μm constituting the high-functional polarizing film X could be produced. Furthermore, the active energy ray-curable adhesive composition is applied to a norbornene-based resin film (first transparent protective film, UV transparent transparent protective film) with an MCD coater (manufactured by Fuji Machine) (cell shape: honeycomb, number of gravure roll wires). : 1000 pieces / INCH, rotational speed 140% / vs. Line speed) is applied to a thickness of 0.5 μm (first coating process), and the optical film laminate is thinly polarized from the adhesive coating surface. It bonded together on the surface of the film | membrane X (moisture content 5.0%) (1st bonding process). Next, the active energy ray-curable adhesive composition was cured by irradiating active energy rays from the norbornene-based resin film (first transparent protective film) side (first adhesion step). Subsequently, the amorphous PET base material was peeled from the thin polarizing film X (peeling step). Furthermore, the active energy ray-curable adhesive composition is applied to the surface of the thin polarizing film X on the side where the amorphous PET substrate is peeled (second coating step), and untreated from the coated surface side. A TAC film (second transparent protective film, ultraviolet opaque transparent protective film) was bonded (second bonding step). Next, after irradiating active energy rays from the untreated TAC film (second transparent protective film) side to cure the active energy ray-curable adhesive composition (second adhesion step), it is dried with hot air at 70 ° C. for 3 minutes. Thus, a polarizing film was produced. The line speed of bonding was 25 m / min. The adhesive strength and curl evaluation of the obtained polarizing film were evaluated based on the following conditions.

Example 2
A polarizing film was produced in the same manner as in Example 1 except that an untreated TAC film was used as the first transparent protective film and a norbornene resin film was used as the second transparent protective film.

Example 3
A polarizing film was produced in the same manner as in Example 1 except that an untreated TAC film was used as the first transparent protective film and the second transparent protective film.

Example 4
A polarizing film was produced by the same method as in Example 1 except that the first bonding step was performed after the second bonding step.

Comparative Example 1
Irradiate active energy rays only from the norbornene-based resin film (first transparent protective film) side and do not irradiate active energy rays from the untreated TAC film (second transparent protective film) side. A polarizing film was produced in the same manner as in Example 1 except that the irradiation was performed.

<Adhesive strength>
The polarizing film was cut out to a size of 200 mm parallel to the stretching direction of the polarizer and 20 mm in the orthogonal direction, and the polarizing film was bonded to a glass plate. A cut is made between the transparent protective film and the polarizer (SP value 32.8) with a cutter knife, and the protective film and the polarizer are peeled off in a 90-degree direction with Tensilon at a peeling speed of 500 mm / min. Was measured. Moreover, the infrared absorption spectrum of the peeling surface after peeling was measured by ATR method, and the peeling interface was evaluated based on the following reference | standard.
A: Cohesive fracture of protective film B: Interfacial delamination between protective film / adhesive layer C: Interfacial delamination between adhesive layer / polarizer D: Cohesive fracture of polarizer This means that the adhesive strength is very excellent. On the other hand, B and C mean that the adhesive force at the interface of the protective film / adhesive layer (adhesive layer / polarizer) is insufficient (adhesive strength is poor). Taking these into consideration, the adhesive strength in the case of A or D is ○, A · B (“cohesive failure of protective film” and “interfacial peeling between protective film / adhesive layer” occur simultaneously) or A · C (Adhesive strength in the case of “cohesive failure of protective film” and “interfacial peeling between adhesive layer / polarizer” occur simultaneously) is Δ, and adhesive strength in the case of B or C is x.

<Evaluation of curling properties of polarizing film>
A sample was cut out at 100 mm × 150 mm so that the long side of the polarizing plate was in the stretching direction. The convex surface was placed on a horizontal plane, and the distance from the horizontal plane at the four end portions of the sample was measured. At this time, curling was suppressed when the average value of the four locations was less than 30 mm, and the usable level (◯) was defined as a polarizing plate. On the other hand, a case where the average value exceeds 30 mm was regarded as an unusable level (x) as a polarizing plate with marked curl.

Claims (20)

A method for producing a polarizing film in which a first transparent protective film is provided on one side of a polarizer and a second transparent protective film is provided on the other side through an adhesive layer,
At least one surface of the surface of the polarizer or the surface of the first transparent protective film on the side to be bonded to the one surface of the polarizer, and the other surface of the polarizer or the polarizer of the second transparent protective film. A coating step of applying an active energy ray-curable adhesive composition to at least one surface of the surface to be bonded to the other surface;
A bonding step of bonding the polarizer and the first transparent protective film; a bonding step of bonding the polarizer and the second transparent protective film;
First, by irradiating active energy rays from the first transparent protective film side and then irradiating active energy rays from the second transparent protective film side to cure the active energy ray-curable adhesive composition. Including the bonding step of bonding the polarizer and the first transparent protective film, and the polarizer and the second transparent protective film through the obtained adhesive layer;
The active energy ray-curable adhesive composition is an acrylic oligomer (D) obtained by polymerizing radical polymerizable compounds (A), (B) and (C) as curable components and a (meth) acrylic monomer. And containing
The radical polymerizable compound (A) has an SP value of 29.0 (MJ / m ³ ) ^1/2 or more and 32.0 (MJ / m ³ ) ^1/2 or less,
The radical polymerizable compound (B) has an SP value of 18.0 (MJ / m ³ ) ^1/2 or more and less than 21.0 (MJ / m ³ ) ^1/2 ,
The radical polymerizable compound (C) has an SP value of 21.0 (MJ / m ³ ) ^1/2 or more and 23.0 (MJ / m ³ ) ^1/2 or less,
A method for producing a polarizing film, comprising 25 to 80% by weight of the radical polymerizable compound (B) when the total amount of the composition is 100% by weight.   2. The polarizing film according to claim 1, wherein the first transparent protective film has a light transmittance of 80% or more at a wavelength of 365 nm, and the second transparent protective film has a light transmittance of a wavelength of 365 nm of less than 5%. Production method.   2. The method for producing a polarizing film according to claim 1, wherein the first transparent protective film and the second transparent protective film have a light transmittance of a wavelength of 365 nm of less than 5%.   2. The method for producing a polarizing film according to claim 1, wherein the first transparent protective film and the second transparent protective film have a light transmittance of 80% or more at a wavelength of 365 nm.   The said active energy ray is a manufacturing method of the polarizing film in any one of Claims 1-4 containing visible light with a wavelength range of 380-450 nm.   6. The polarizing film according to claim 1, wherein the active energy ray has a ratio of an integrated illuminance in a wavelength range of 380 to 440 nm and an integrated illuminance in a wavelength range of 250 to 370 nm of 100: 0 to 100: 50. Production method.   The method for producing a polarizing film according to any one of claims 1 to 6, wherein the active energy ray is a gallium lamp as a light source and a UV ray having a wavelength of 380 nm or less is blocked using a bandpass filter. The active energy ray-curable adhesive composition is a compound represented by the following general formula (1) as a photopolymerization initiator;

(Wherein R ¹ and R ² represent —H, —CH ₂ CH ₃ , —IPr or Cl, and R ¹ and R ² may be the same or different). The manufacturing method of the polarizing film of description. As a photopolymerization initiator, a compound represented by the following general formula (2);

Wherein R ³ , R ⁴ and R ⁵ represent —H, —CH ₃ , —CH ₂ CH ₃ , —IPr or Cl, and R ³ , R ⁴ and R ⁵ may be the same or different. The manufacturing method of the polarizing film of Claim 8 contained.   The total thickness of the said polarizing film is 150 micrometers or less, The manufacturing method of the polarizing film in any one of Claims 1-9. The manufacturing method of the polarizing film in any one of Claims 1-10 containing the radically polymerizable compound which has an active methylene group, and the radical polymerization initiator (E) which has a hydrogen abstraction action. The method for producing a polarizing film according to claim 11, wherein the active methylene group is an acetoacetyl group. The method for producing a polarizing film according to claim 11 or 12, wherein the radical polymerizable compound having an active methylene group is acetoacetoxyalkyl (meth) acrylate. The method for producing a polarizing film according to claim 11, wherein the radical polymerization initiator (E) is a thioxanthone radical polymerization initiator. The composition comprising 1 to 50% by weight of the radically polymerizable compound having an active methylene group and 0.1 to 10% by weight of the radical polymerization initiator (E) when the total amount of the composition is 100% by weight. The method for producing a polarizing film according to any one of 14.   When the total amount of the composition is 100% by weight, the radical polymerizable compound (A) is 3 to 40% by weight, the radical polymerizable compound (C) is 5 to 55% by weight, and the acrylic oligomer (D) is 3%. The manufacturing method of the polarizing film in any one of Claims 1-15 containing -20weight%.   The glass transition temperature (Tg) of each of the radical polymerizable compounds (A), (B), and (C) is 60 ° C. or higher. The production of the polarizing film according to claim 1. Method.   The method for producing a polarizing film according to claim 1, wherein the radical polymerizable compound (A) is hydroxyethyl acrylamide and / or N-methylol acrylamide.   The method for producing a polarizing film according to claim 1, wherein the radical polymerizable compound (B) is tripropylene glycol diacrylate.   The method for producing a polarizing film according to claim 1, wherein the radical polymerizable compound (C) is acryloylmorpholine and / or N-methoxymethylacrylamide.

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