JP2009075192A - Method for manufacturing polarizing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a polarizing plate having high adhesion strength between a polarizing film and a protective layer and having excellent scratch resistance. <P>SOLUTION: The method for manufacturing a polarizing plate is characterized in that: the method includes processes of (a) supplying a composition for a radiation-curing adhesive to between a polarizing film and a first protective layer formed on a first face of the polarizing film and between the polarizing film and a second protective layer formed on the second face of the polarizing film, (b) laminating the polarizing film, the first protective layer and the second protective layer with the above composition for a radiation-curing adhesive, and (c) curing the composition for a radiation-curing adhesive composition by irradiating the layers with radiation to form radiation cured adhesive layers; and at least the first protective layer is not subjected to a saponification process. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a polarizing plate.

  A liquid crystal display (hereinafter referred to as “LCD”) is used as a display device such as a personal computer monitor, a television monitor, a mobile phone, etc. because of its thinness, light weight, and low power consumption. In recent years, LCDs are being expanded to automotive applications that require durability and heat resistance, such as car navigation and automotive inner panels.

  In general, an LCD is a liquid crystal cell that has the function of switching the passage and blocking of polarized light by controlling the alignment direction of liquid crystal molecules by applying an electric field, and two polarized light beams that are arranged with their transmission axes perpendicular to each other. Consists of plates.

  The polarizing plate is usually formed from a substrate (optical film) excellent in transparency and a polarizer. Moreover, the polarizing plate may be formed from the film | membrane (phase difference film) which extended | stretched the optical film and provided the function which gives a phase difference to transmitted light, and a polarizer.

  As the polarizer, a uniaxially oriented film in which iodine or a dichroic dye is adsorbed and dispersed in polyvinyl alcohol (hereinafter referred to as “PVA”) is generally used. Although this PVA polarizer has an excellent polarization function, it is known that the heat resistance is low, and a dimensional change occurs due to a temperature change or a change in moisture content, resulting in a decrease in the polarization function. In order to prevent this, the substrate is bonded to both surfaces of the PVA polarizer as a protective layer. Conventionally, a triacetyl cellulose resin film or a cyclic olefin-based resin film has been mainly used as the protective layer, and a water-based adhesive containing PVA is used as an adhesive. When adhering a triacetyl cellulose resin film with a water-based adhesive, in order to obtain sufficient adhesive strength, the triacetyl cellulose resin film is immersed in a high-temperature alkaline aqueous solution before bonding to saponify the acetyl groups on the surface. It is necessary to remove (see, for example, Patent Document 1 and Patent Document 2).

  On the other hand, with the recent increase in size of liquid crystal displays, there is a problem of reflection on the display, and as a countermeasure against this, it is a common practice to form an antireflection layer on the surface of the display. One of the methods is to provide a low refractive index layer having a lower refractive index than the protective layer on the display surface. It is proposed to use a cured film containing colloidal silica or hollow silica particles as the low refractive index layer. ing.

However, when a saponification treatment is performed on a film containing silica particles, particularly hollow silica particles, the hollow silica particles are eroded, causing a decrease in the scratch resistance of the antireflection layer. In order to protect the antireflection layer during the saponification treatment, there is a method of pasting a protective film, but the cost increases accordingly.
Japanese Patent Laid-Open No. 9-258023 JP-A-10-268133

  The objective of this invention is providing the manufacturing method of the polarizing plate with the high adhesive strength of a polarizing film and a protective layer, and excellent in abrasion resistance.

  The polarizing plate manufacturing method according to the present invention includes (a) a polarizing film and a first protective layer formed on the first surface of the polarizing film, and the polarizing film and the polarizing film. A step of supplying a radiation-curable adhesive composition between the second protective layer formed on the second surface, (b) the polarizing film, the first protective layer, and A step of laminating a second protective layer via the radiation curable adhesive composition; and (c) irradiating the radiation to cure the radiation curable adhesive composition to produce radiation. Forming a curable adhesive layer, wherein at least the first protective layer is not saponified.

  The manufacturing method of the polarizing plate which concerns on this invention performs a corona discharge process further on the surface which bonds the said polarizing film of a said 1st protective layer or a said 2nd protective layer before the said process (a). Steps may be included.

  In the method for manufacturing a polarizing plate according to the present invention, at least one of the first protective layer and the second protective layer may contain an ultraviolet absorber.

  In the manufacturing method of the polarizing plate which concerns on this invention, a radiation can be irradiated from the protective layer side with high ultraviolet-ray transmittance among the said 1st protective layer or the said 2nd protective layer.

  In the method for producing a polarizing plate according to the present invention, the second protective layer can also function as a retardation film.

  The method for producing a polarizing plate according to the present invention may further include a step of forming a hard coat layer on the first protective layer.

  In the method for manufacturing a polarizing plate according to the present invention, the hard coat layer may have an antistatic function.

  The method for producing a polarizing plate according to the present invention can further include a step of forming a low refractive index layer on the hard coat layer.

  In the method for producing a polarizing plate according to the present invention, the low refractive index layer may include silica-based hollow particles.

In the method for producing a polarizing plate according to the present invention, the radiation curable adhesive layer is a cured product of a radiation curable liquid resin composition containing at least the following components (d), (e), and (f). Can be.
(D) an alicyclic epoxy compound,
(E) a compound containing at least one hydroxyl group and having a number average molecular weight of 500 or more,
(F) Photoacid generator.

（Ｒ^１、Ｒ^２およびＲ^３は、それぞれ独立に一価の有機基であり、Ｒ^１〜Ｒ^３のうち少なくとも２つが−Ｒ^４ＯＣＯＣＲ^５＝ＣＨ_２であり、Ｒ^４は炭素数２〜８の２価の有機基であり、Ｒ^５は水素原子またはメチル基である。） In the method for producing a polarizing plate according to the present invention, the radiation curable liquid resin composition may further include a component represented by the following formula (1).

(R ¹ , R ² and R ³ are each independently a monovalent organic group, at least two of R ^{1 to} R ³ are —R ⁴ OCOCR ⁵ ═CH ₂ , and R ⁴ has 2 to 2 carbon atoms. 8 is a divalent organic group, and R ⁵ is a hydrogen atom or a methyl group.)

  In the method for producing a polarizing plate according to the present invention, the radiation curable liquid resin composition may further include an aliphatic epoxy compound.

  According to the method for producing a polarizing plate, the polarizing film and the protective layer are bonded via a radiation curable adhesive, so that the saponification treatment step required when using a conventional aqueous adhesive is omitted. be able to. Thereby, deterioration of a silica type hollow particle content layer can be prevented, and the fall of the abrasion resistance in a polarizing plate manufacturing process can be improved.

  Preferred embodiments of the present invention will be described below with reference to the drawings.

1. Configuration of Polarizing Plate First, the configuration of the polarizing plate manufactured by the manufacturing method of the polarizing plate according to the present embodiment will be described. FIG. 1 is a schematic diagram showing a cross section of a polarizing plate 100 according to the present embodiment. The polarizing plate 100 includes a polarizing film 10, a first protective layer 14 formed on a first surface of the polarizing film 10 via a first radiation curable adhesive layer 12, and the polarizing film 10. The second protective layer 18 is formed on the second surface of the second protective layer 18 via the second radiation curable adhesive layer 16. In the polarizing plate 100, a hard coat layer 20 is provided on the surface of the first protective layer 14. Further, the polarizing plate 100 is provided with a low refractive index layer 22 on the surface of the hard coat layer 20. In the polarizing plate 100, as shown in FIG. 1, a liquid crystal panel 90 can be installed on the surface of the second protective layer 18 via an adhesive layer 80.

  The polarizing film 10 is not particularly limited, and can be any film that has a function of dividing incident light into two polarization components perpendicular to each other, allowing only one of them to pass, and absorbing or dispersing the other components.

  At least one of the first protective layer 14 and the second protective layer 18 may contain an ultraviolet absorber. This ultraviolet absorber can protect the liquid crystal device from ultraviolet rays. However, in order to cure the radiation curable adhesive layers 12 and 16, it is necessary to irradiate ultraviolet rays from at least the first protective layer side or the second protective layer side. If the first protective layer 14 or the second protective layer 18 contains an ultraviolet absorber, the radiation curable adhesive layers 12 and 16 may not be sufficiently cured even when irradiated with ultraviolet rays. . Therefore, it is preferable to irradiate the radiation from the side of the protective layer having a high ultraviolet transmittance in the first protective layer 14 or the second protective layer 18. Of course, radiation may be applied from both sides.

  If the protective layer containing the ultraviolet absorber is on at least one surface of the polarizing film 10, the influence on the original liquid crystal device can be suppressed, but considering the influence on the polarizing film 10, It is preferable to add to 1 protective layer.

  In addition to the function of protecting the polarizing film 10, the second protective layer 18 can also function as a retardation film such as compensation by coloring the liquid crystal layer and compensation for change in retardation by viewing angle. For example, when a birefringent film obtained by stretching a polymer film is used as the second protective layer 18, the birefringence of the liquid crystal layer can be compensated and the coloring can be removed.

  The hard coat layer 20 can prevent leakage to the liquid crystal cell 90 and increase the mechanical strength of the polarizing plate 100. For example, an antistatic function can be provided by adding an antistatic agent to the hard coat layer 20.

  By providing the low refractive index layer 22, the refractive index can be lowered. Thereby, the polarizing plate 100 can be provided with an antireflection function.

  The polarizing plate 100 has a good polarizing function, and even under an atmosphere of high temperature and high humidity, the polarizing film 10 and the first protective layer 14 and the polarized light are interposed through the radiation curable adhesive layers 12 and 16. The strong adhesion between the film 10 and the second protective layer 18 is maintained for a long time. In addition, the polarizing plate 100 is excellent in characteristics such as heat resistance and chemical resistance, is less likely to be peeled off, deformed, and changed in phase even in long-term use, has high reliability, and has excellent durability. It can be suitably used for an LCD or the like.

  The functions and materials of the polarizing film, the first and second protective layers, the radiation curable adhesive layer, the hard coat layer, and the silica-based hollow particle-containing layer will be described in detail later.

2. Manufacturing method of polarizing plate The manufacturing method of the polarizing plate which concerns on this embodiment includes the following process (a)-(c), and the 1st protective layer has not performed the saponification process, It is characterized by the above-mentioned. Is.
(A) A second layer formed between the polarizing film and the first protective layer formed on the first surface of the polarizing film, and on the second surface of the polarizing film and the polarizing film. Supplying a radiation curable adhesive composition between the protective layer and
(B) a step of bonding the polarizing film, the first protective layer, and the second protective layer via the radiation curable adhesive composition;
(C) A step of curing the radiation-curable adhesive composition by irradiating with radiation to form a radiation-curable adhesive layer.

  Hereinafter, a method for manufacturing polarizing plate 100 according to the present embodiment will be specifically described with reference to the drawings. FIG. 2 is a schematic diagram for explaining a manufacturing process of the polarizing plate 100.

  In the step (a), a radiation curable adhesive composition is supplied from the first adhesive supply unit 60 between the polarizing film 10 and the first protective layer 14. Further, the radiation curable adhesive composition is supplied from the second adhesive supply unit 62 between the polarizing film 10 and the second protective layer 18.

  At a process (b), the polarizing film 10, the 1st protective layer 14, and the 2nd protective layer 18 are bonded by the bonding rolls 30 and 32 which consist of a pair of roll, and it crimps | bonds.

  In the step (c), the radiation curable adhesive composition is cured by irradiating radiation from at least one of the first radiation irradiating unit 70 and the second radiation irradiating unit 72.

  First, the step (a) will be described in detail.

  The 1st adhesive supply part 60 is supplying by injecting the composition for radiation curable adhesives between the polarizing film 10 and the 1st protective layer 14. The second adhesive supply unit 62 supplies the radiation curable adhesive composition by spraying between the polarizing film 10 and the second protective layer 18.

  Although the film thickness of a radiation-curable adhesive layer can be adjusted with the supply amount of the composition for radiation-curable adhesives, Preferably it is 0.5-5 micrometers, More preferably, it is 1-3 micrometers. Moreover, the adhesive supply parts 60 and 62 are not limited to the apparatus which injects the composition for radiation curable adhesives, It can replace with the apparatus which apply | coats the composition for radiation curable adhesives.

  A hard coat layer or a low refractive index layer may be bonded in advance to the surface of the first protective layer 14 opposite to the surface to be bonded to the polarizing film 10. For example, the hard coat layer composition is coated on the first protective layer 14 with a wire bar coater or the like to form a uniform film thickness, dried, and then irradiated with light to form a hard coat layer. can do. Furthermore, the low refractive index layer composition is coated on the hard coat layer with a wire bar coater or the like so as to have a uniform film thickness, dried, and then irradiated with light to form a low refractive index layer. be able to.

  In addition, it is good to perform a corona discharge process about the surface bonded with the polarizing film 10 of the 1st protective layer 14 and the 2nd protective layer 18 before supplying the composition for radiation-curable adhesives. Thereby, the adhesiveness of the polarizing film 10 and each protective layer can be improved. For example, when a cyclic olefin-based resin is used as the protective layer, the cyclic olefin-based resin may not have excellent adhesion because there is no polar group on the surface. In such a case, when the corona discharge treatment is performed, the resin is generated by generating corona discharge in the atmosphere using high frequency high voltage and irradiating the resin surface with the functional groups generated thereby. Surface modification can be performed.

  Next, step (b) will be described.

  The polarizing film 10, the first protective layer 14, and the second protective layer 18 are pressed and bonded together by bonding rolls 30 and 32 made of a pair of rolls. The roll bonding shown in FIG. 2 is excellent in productivity because all the layers to be laminated can be crimped at a time and the number of bonding steps can be reduced.

  Next, step (c) will be described.

  The radiation curable adhesive layer is cured by irradiating radiation from at least one of the first radiation irradiating unit 70 and the second radiation irradiating unit 72. As a light source used for the radiation irradiation unit, for example, a metal halide lamp, a hyper metal halide lamp, an LED light source, or the like can be used. The photopolymerization initiator in the radiation curable resin composition is excellent in productivity because it reacts with radiation such as ultraviolet rays and the radiation curable adhesive layer is instantaneously cured.

  Here, as a specific example according to the present embodiment, a case where the first protective layer 14 includes an ultraviolet absorber and the second protective layer 18 does not include an ultraviolet absorber will be described. In this example, since the second protective layer 18 does not contain an ultraviolet absorber, a compound having an absorption wavelength in the ultraviolet region can be selected as a photopolymerization initiator in the radiation curable resin composition. As a light source, for example, using a metal halide lamp, the radiation curable adhesive layer can be cured by irradiating ultraviolet rays containing sodium D-line (wavelength 365 nm). As a result, the polarizing film 10 and the second protective layer 14 can be bonded.

  On the other hand, since the first protective layer 14 contains an ultraviolet absorber, the first radiation curable adhesive layer 12 can be sufficiently cured even when irradiated with ultraviolet rays from the first radiation irradiation unit 70. Can not. Therefore, as a photopolymerization initiator in the radiation curable resin composition, a compound having an absorption wavelength of 400 nm or more is selected, and radiation including a wavelength of 400 nm or more is irradiated from the first radiation irradiating unit 70, thereby One radiation curable adhesive layer 12 can be cured. As the light source, for example, a hypermetal halide lamp having a strong irradiation intensity with a wavelength of 405 nm can be used. As a result, the polarizing film 10 and the first protective layer 14 can be bonded.

  The polarizing plate 100 that has been pressure-bonded through the above steps (a) to (c) is taken up by the polarizing plate take-up unit 50 via a pair of rolls 40 and 42.

  The manufacturing method of the polarizing plate according to the present embodiment uses a radiation curing without using a water-based adhesive such as a PVA-based adhesive in order to bond the polarizing film 10 to the first protective layer 14 and the second protective layer 18. Use mold adhesive. Thereby, for example, it is not necessary to perform a saponification treatment for removing acetyl groups present on the surface of a triacetyl cellulose (TAC) film conventionally used as a protective layer. According to the method for producing a polarizing plate according to this embodiment, the hollow silica particles added to the low refractive index layer are not eroded by the saponification treatment, and the antireflection function and the scratch resistance are not impaired.

3. Polarizing film In the polarizing plate according to the present embodiment, the polarizing film functions as a polarizing film, that is, splits incident light into two polarizing components perpendicular to each other, passes only one of them, and absorbs the other components. Any of those having a function of dispersing can be used, and is not particularly limited. Examples of the polarizing film used in this embodiment include a PVA / iodine polarizing film, a PVA / dye polarizing film in which a dichroic dye is adsorbed and oriented on the PVA film, and a dehydration reaction is induced from the PVA film. Polarized film having a dichroic dye on the surface and / or inside of a polyene-based polarizing film in which a polyene is formed by dehydrochlorination reaction of a polyvinyl chloride film, or a PVA-based film comprising a modified PVA containing a cationic group in the molecule A film etc. are mentioned. Of these, the most preferable one is a PVA / iodine polarizing film.

  The manufacturing method of the polarizing film used in this embodiment is not particularly limited. For example, a method of adsorbing iodine ions after stretching on a PVA film, a method of stretching a PVA film after dyeing with a dichroic dye, a method of dyeing a PVA film with a dichroic dye after stretching, a dichroic dye Well-known methods such as a method of stretching after printing on a PVA-based film and a method of printing a dichroic dye after stretching a PVA-based film may be mentioned. More specifically, iodine is dissolved in a potassium iodide solution to form higher-order iodine ions, the ions are adsorbed on a PVA film and stretched, and then a 1 to 4% boric acid aqueous solution is heated to a bath temperature of 30. A method for producing a polarizing film by immersing at ~ 40 ° C, or treating a PVA film with boric acid in the same manner and stretching it about 3 to 7 times in a uniaxial direction, and bathing in a 0.05 to 5% dichroic dye aqueous solution Examples include a method of producing a polarizing film by immersing at a temperature of 30 to 40 ° C. to adsorb a dye, drying at 80 to 100 ° C. and heat setting.

  Although the thickness of the polarizing film used by this embodiment is not specifically limited, Preferably it is 10-50 micrometers, More preferably, it is about 15-45 micrometers.

  These polarizing films may be used as they are for the production of the polarizing plate according to the present embodiment, but can be subjected to a surface treatment for the purpose of increasing the adhesive strength with the adjacent adhesive layer. Examples of the surface treatment include plasma treatment, corona treatment, alkali treatment, and coating treatment.

4). Protective layer In the polarizing plate according to this embodiment, examples of the protective layer include acetate resins such as triacetyl cellulose, polyester resins such as polyethylene terephthalate resin, polyethersulfone resins, polycarbonate resins, and polyamide resins. And films made of optically transparent resins such as polyimide resins, polyolefin resins, cyclic olefin resins, and acrylic resins.

  In the present invention, it is preferable that one of the first or second protective layers is a protective layer having ultraviolet ray preventing properties, and the other protective layer is a protective layer having ultraviolet ray transmissive properties.

  The protective layer having the ultraviolet ray preventing property plays a role of protecting the liquid crystal cell from external ultraviolet rays when the polarizing plate is disposed on both surfaces of the liquid crystal cell. As described above, a UV absorber can be appropriately blended in the protective layer having UV protection. In the polarizing plate according to this embodiment, a protective layer having an ultraviolet ray preventing property blended with an ultraviolet absorber and having a light transmittance at a wavelength of 380 nm of, for example, 10% or less can be preferably used.

  The protective layer having ultraviolet transparency is for curing the radiation curable composition by performing radiation irradiation (light irradiation) from the protective layer side. The protective layer having ultraviolet transparency does not contain an ultraviolet absorber, or contains an ultraviolet absorber to such an extent that the radiation-curable composition can be cured by irradiating light through the protective layer. it can. In the polarizing plate according to the present embodiment, a protective layer having ultraviolet light transmittance having a light transmittance at a wavelength of 380 nm of, for example, 60% or more can be preferably used.

  The protective layer can also serve as a retardation film as described above.

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

  The protective layer can also be subjected to a surface treatment before application of the radiation curable composition. Examples of the surface treatment include plasma treatment, corona discharge treatment, alkali treatment, and coating treatment. Among these, it is particularly preferable to perform corona discharge treatment.

  For example, when a cyclic olefin-based resin is used as the protective layer, the cyclic olefin-based resin may not have excellent adhesion because there is no polar group on the surface. In such a case, when the corona discharge treatment is performed, the resin is generated by generating corona discharge in the atmosphere using high frequency high voltage and irradiating the resin surface with the functional groups generated thereby. Surface modification can be performed.

5). Radiation-curable adhesive layer The radiation-curable composition used as an adhesive in the present embodiment is for adhering the first and second protective layers and the polarizing film. The radiation curable composition can contain the following (d) to (f) and other optional components.
(D): Alicyclic epoxy compound (e): Compound containing at least one hydroxyl group and having a number average molecular weight of 500 or more (f): Photoacid generator

  Hereinafter, each component will be described in detail.

5.1 Component (d)
Component (d) constituting the radiation curable composition is an alicyclic epoxy compound, preferably an alicyclic epoxy compound having two or more alicyclic epoxy groups in one molecule. When an alicyclic epoxy compound having two or more alicyclic epoxy groups in one molecule is contained in an amount of 50% by mass or more in the total amount of the component (d), a good curing rate and mechanical strength can be maintained.

  Specific examples of the alicyclic epoxy compound used as the component (d) include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5 -Spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6 -Methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4- Epoxy cyclohexylme 3 ′, 4′-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane) , Ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), epoxycyclohexahydrophthalate dioctyl, epoxycyclohexahydrophthalate di-2-ethylhexyl, etc. Is mentioned.

  Among these alicyclic epoxy compounds, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, ε-caprolactone modified 3,4-epoxy Cyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3,4-epoxy More preferred is cyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexane Cyclohexylmethyl) adipate is more preferable.

  These commercially available products include Celoxide 2021, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Epolide GT-300, Epolide GT-301, Epolide GT-302, Epolide GT-400, Epolide 401, Epolide 403 (or more, Daicel Chemical Industries, Ltd.).

  The content of the (d) alicyclic epoxy compound in the radiation curable composition is preferably 10 to 80% by mass, more preferably 12 to 75% by mass, and particularly preferably 15 to 70% by mass. When the content is less than 10% by mass, the mechanical strength and heat resistance of the adhesive layer tend to be insufficient. When this content rate exceeds 80 mass%, there exists a tendency for deformation | transformation, such as curvature of the adhesive bond layer formed by hardening | curing a radiation-curable composition, to become large.

5.2 Component (e)
Component (e) constituting the radiation curable adhesive composition is a compound containing one or more hydroxyl groups and having a number average molecular weight of 500 or more.

  Component (e) has one or more, preferably 1 to 4, hydroxyl groups in one molecule. The number average molecular weight of the component (e) is 500 or more, preferably 1,000 or more, more preferably 1,500 or more. The upper limit of the average molecular weight is not particularly limited, but is preferably 20,000, more preferably 10,000 from the viewpoint of preventing an excessive increase in the viscosity of the adhesive composition. When the average molecular weight is less than 500, the cutting resistance at the time of cutting the polarizing plate is inferior, which is not preferable. The number average molecular weight of component (e) is a value measured according to ASTM D2503. By using the component (e), a laminated film having excellent adhesive strength can be obtained.

  Examples of the compound suitably used as the component (e) include polycaprolactone diol, polyether diol, polyester diol, and other polyols.

  Examples of the polycaprolactone diol include polycaprolactone diol obtained by reacting ε-caprolactone with a diol. Examples of the diol used here include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, 1,6-hexanediol, neopentyl glycol, Examples include 1,4-cyclohexanedimethanol and 1,4-butanediol. Examples of commercially available products of these polycaprolactone diols include Plaxel 205, 205H, 205AL, 212, 212AL, 220, and 220AL (manufactured by Daicel Chemical Industries, Ltd.).

  The polyether diol is preferably an aliphatic polyether diol, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, and polydecamethylene glycol. Commercially available products of these polyether diols include PEG # 600, # 1000, # 1500, # 1540, # 4000 (above, manufactured by Lion), Exenol 720, 1020, 2020, 3020, 510, Preminol PPG4000 (above, Asahi Glass Co., Ltd.).

  The polyester diol is preferably a copolymer of an aliphatic diol compound and an aliphatic dicarboxylic acid compound. Examples of the aliphatic diol compound include 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl- 1,5-pentanediol and the like, and examples of the aliphatic dicarboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid and the like. One or more aliphatic diols can be used, and one or more aliphatic dicarboxylic acids can be used. Commercially available products of these polyester diols include Kuraray polyol N-2010, O-2010, P-510, P-1010, P-1050, P-2010, P-2050, P-3010, P-3050 (or more, Kuraray Co., Ltd.).

  Examples of other polyols include trihydric or higher polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol, sorbitol, sucrose, and quadrol, ethylene oxide (EO), propylene oxide (PO), butylene oxide, tetrahydrofuran, and the like. A polyether polyol obtained by modifying with a cyclic ether compound of Specific examples of such compounds include EO-modified trimethylolpropane, PO-modified trimethylolpropane, tetrahydrofuran-modified trimethylolpropane, EO-modified glycerol, PO-modified glycerol, tetrahydrofuran-modified glycerol, EO-modified pentaerythritol, PO-modified pentaerythritol, Tetrahydrofuran-modified pentaerythritol, EO-modified sorbitol, PO-modified sorbitol, EO-modified sucrose, PO-modified sucrose, EO-modified sucrose, EO-modified quadrole, etc. can be exemplified, and among these, EO-modified trimethylolpropane, PO-modified trimethylol Propane, PO-modified glycerin and PO-modified sorbitol are preferred.

  Commercially available products of the above other polyols include Sannix TP-700, Sannix GP-1000, Sannix SP-750, Sannix GP-400, Sannix GP-600 (above, manufactured by Sanyo Chemical Co., Ltd.), etc. Can be mentioned.

  Moreover, as a polyol used suitably as a component (e), the polymer of a hydroxyl-containing unsaturated compound can be mentioned. Examples of the hydroxyl group-containing unsaturated compound include a hydroxyl group-containing (meth) acrylate. Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6- Hexanediol mono (meth) acrylate, neopentylglycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate , Dipentaerythritol penta (meth) acrylate. Furthermore, the compound obtained by addition reaction of glycidyl group containing compounds, such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate, and (meth) acrylic acid is mentioned.

（式中、Ｒ^６およびＲ^７はそれぞれ独立に炭素数２〜１２の２価の炭化水素基を表し、Ｒ^８は、Ｒ^６とＲ^７のいずれかと同じ構造を表す。ｍは２〜１５０、ｎは０〜１５０であり、かつ、ｍ＋ｎは２〜２００である。） The component (e) is also preferably a polycarbonate diol represented by the following formula (2).

(In the formula, R ⁶ and R ⁷ each independently represent a divalent hydrocarbon group having 2 to 12 carbon atoms, R ⁸ represents the same structure as either R ⁶ or R ⁷ , and m represents 2 to 150. , N is 0 to 150, and m + n is 2 to 200.)

  The method for producing the polycarbonate diol represented by the above formula (2) is not particularly limited, and examples thereof include known methods such as a transesterification reaction between a diol compound and a carbonate compound, and a polycondensation reaction between a diol compound and phosgene. . Examples of the diol compound used for the production of the component (B) include 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, and 2-methyl. -1,8-octanediol and the like. Moreover, in order to obtain moderate adhesive strength, a polycarbonate diol containing an aliphatic hydrocarbon group having 6 carbon atoms such as 1,6-hexanediol and 3-methyl-1,5-pentanediol is more preferable.

  Commercially available compounds suitable for use as the polycarbonate diol include DN-980, 981, 982, 983 (manufactured by Nippon Polyurethane Co., Ltd.), PC-8000 (manufactured by PPG), PC-THF-CD (manufactured by BASF). ), Kuraray polyol C-590, C-1090, C-2050, C-2090, C-3090, C-2065N, C-2015N (above, manufactured by Kuraray Co., Ltd.), Plaxel CD CD210PL, Plaxel CD CD220PL (above And Daicel Chemical Industries, Ltd.).

  In the composition for radiation curable adhesive, the content of component (e) is preferably 2 to 50% by mass, more preferably 3 to 45% by mass, and particularly preferably 3 to 40% by mass. When the content is less than 2% by mass, the adhesive strength of the adhesive layer is inferior. On the other hand, if the content exceeds 50% by mass, the viscosity of the radiation curable adhesive composition becomes too high, resulting in poor coating properties and poor adhesive strength between the adhesive layer and the adherend. Is not preferable.

5.3 Component (f)
Component (f) constituting the radiation curable composition is a photoacid generator.

  The photoacid generator is a photocationic polymerization initiator that releases Lewis acid upon receiving light.

（式中、カチオンはオニウムイオンであり、ＺはＳ、Ｓｅ、Ｔｅ、Ｐ、Ａｓ、Ｓｂ、Ｂｉ、Ｏ、Ｉ、Ｂｒ、ＣｌまたはＮ_２を示し、Ｒ^９、Ｒ^１０、Ｒ^１１およびＲ^１２は、互いに同一または異なる有機基を示す。ａ、ｂ、ｃおよびｄは、それぞれ０〜３の整数であって、（ａ＋ｂ＋ｃ＋ｄ−ｐ）はＺの価数に等しい。Ｍは、ハロゲン化物錯体［ＭＸ_ｑ＋ｐ］の中心原子を構成する金属またはメタロイドを示し、例えば、Ｂ、Ｐ、Ａｓ、Ｓｂ、Ｆｅ、Ｓｎ、Ｂｉ、Ａｌ、Ｃａ、Ｉｎ、Ｔｉ、Ｚｎ、Ｓｃ、Ｖ、Ｃｒ、Ｍｎ、Ｃｏ等である。Ｘは、例えば、Ｆ、Ｃｌ、Ｂｒ等のハロゲン原子であり、ｐはハロゲン化物錯体イオンの正味の電荷であり、ｑはＭの原子価である。） Examples of the photoacid generator include an onium salt having a structure represented by the following general formula (3). This onium salt has a substantial light absorption wavelength below 400 nm.

(In the formula, the cation is an onium ion, Z represents S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, or N ₂ , and R ⁹ , R ¹⁰ , R ^11, and R 2) ¹² represents an organic group which is the same or different from each other, a, b, c and d are each an integer of 0 to 3, and (a + b + c + d−p) is equal to the valence of Z. M is a halide complex. [MX _{q + p} ] represents a metal or metalloid constituting the central atom of, for example, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, X is a halogen atom such as F, Cl, Br, etc., p is the net charge of the halide complex ion, and q is the valence of M.)

In the general formula (3), specific examples of onium ions include diphenyliodonium, 4-methoxydiphenyliodonium, bis (4-methylphenyl) iodonium, bis (4-tert-butylphenyl) iodonium, bis (dodecylphenyl). Diaryliodonium such as iodonium, triarylsulfonium such as triphenylsulfonium and diphenyl-4-thiophenoxyphenylsulfonium, bis [4- (diphenylsulfonio) -phenyl] sulfide, bis [4- (di (4- ( 2-hydroxyethyl) phenyl) sulfonio) -phenyl] sulfide, η ⁵ -2,4- (cyclopentadienyl) [1,2,3,4,5,6-η]-(methylethyl) -benzene] -Iron (1+) etc. are mentioned.

In the general formula (3), specific examples of the anion [MX _{q + p} ] include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarce. Nate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl ₆ ⁻ ) and the like.

Moreover, the onium salt which has an anion represented with general formula [ _MXq (OH) < ^- >] can be used. Furthermore, perchlorate ion (ClO ₄ ⁻ ), trifluoromethane sulfonate ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluene sulfonate ion, trinitrobenzene sulfonate anion, trinitrotoluene sulfonate Onium salts having other anions such as anions can also be used.

  Examples of onium salts used as the component (f) include aromatic halonium salts described in, for example, JP-A-50-151996, JP-A-50-158680, JP-A-50-151997, VIA group aromatic onium salts described in JP-A-52-30899, JP-A-56-55420, JP-A-55-125105, etc., VA described in JP-A-50-158698, etc. Aromatic aromatic onium salts, oxosulfoxonium salts described in JP-A-56-8428, JP-A-56-149402, JP-A-57-192429, etc., JP-A-49-17040 Aromatic diazonium salts described in U.S. Pat. No. 4,139,655, and thiobililium salts described in US Pat. No. 4,139,655. Moreover, an iron / allene complex, an aluminum complex / photolytic silicon compound-based initiator, and the like can also be mentioned. Photoacid generators preferably used as component (f) are aromatic onium salts such as diaryl iodonium salts and triaryl sulfonium salts, and more preferably triaryl sulfonium salts.

  (F) Examples of commercially available photoacid generators include UVI-6950, UVI-6970, UVI-6974, UVI-6990 (manufactured by Union Carbide), Adekaoptomer SP-150, SP-151, SP-170, SP-172 (above, manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 184, Irgacure 261 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), CI-2481, CI-2624, CI-2638, CI- 2064 (above, Nippon Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (above, made by Sartomer), DTS-102, DTS-103, NAT-103, NDS-103, TPS-103 , MDS-103, MPI-103, BBI-103 (above, manufactured by Midori Chemical Co., Ltd.), PCI- 61T, PCI-062T, PCI-020T, PCI-022T (manufactured by Nippon Kayaku Co., Ltd.), CPI-110A, CPI-101A (above, SAN-APRO Ltd.), and the like. Among these, UVI-6970, UVI-6974, Adeka optomer SP-170, SP-172, CD-1012, MPI-103, CPI-110A, CPI-101A are high in the composition containing them. It is particularly preferable because photocuring sensitivity can be expressed. Said photo-acid generator can be used individually by 1 type or in combination of 2 or more types.

  A sensitizer may be used in combination in order to promote the generation of acid by the photoacid generator. Examples of the sensitizer include dihydroxybenzene, trihydroxybenzene, hydroxyacetophenone, dihydroxydiphenylmethane, and the like.

  In the radiation curable composition, the content of the (f) photoacid generator is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and particularly preferably 0.3 to 3% by mass. It is. When the content is less than 0.1% by mass, the radiation curability of the radiation curable composition is lowered, and an adhesive layer having sufficient mechanical strength cannot be formed. If the content exceeds 10% by mass, the photoacid generator may adversely affect the long-term characteristics of the adhesive layer, which is not preferable.

5.4 Other components The following components (g) and (h) can be further added to the radiation curable composition used as an adhesive in the present embodiment.

（式（１）中、Ｒ^１、Ｒ^２およびＲ^３は、それぞれ独立に、一価の有機基であって、Ｒ^１〜Ｒ^３のうち少なくとも２つが、−Ｒ^４ＯＣＯＣＲ^５＝ＣＨ_２であり、Ｒ^４は、炭素数２〜８の２価の有機基であり、Ｒ^５は、水素原子またはメチル基である。） 5.4.1 Ingredient (g)
The said radiation-curable composition can add the isocyanuric acid derivative which has a polymerizable unsaturated group represented by following formula (1) as a component (g) further.

(In the formula (1), R ¹ , R ² and R ³ are each independently a monovalent organic group, and at least two of R ^{1 to} R ³ are —R ⁴ OCOCR ⁵ ═CH ₂ . Yes, R ⁴ is a divalent organic group having 2 to 8 carbon atoms, and R ⁵ is a hydrogen atom or a methyl group.)

  The component (g) has a function of improving the curability (curing speed) of the radiation-curable adhesive composition. The component (g) preferably has two or more polymerizable unsaturated groups in the molecule. The polymerizable unsaturated group is not particularly limited, but is preferably a (meth) acrylate group. By having two or more polymerizable unsaturated groups, the crosslinking density is increased, and the decrease in hardness due to the addition thereof can be reduced.

  Specific examples of the component (g) that can be used in the present embodiment include tris [2- (meth) acryloyloxyethyl] isocyanurate, bis [2- (meth) acryloyloxyethyl] (2-hydroxyethyl) isocyanate. Examples include nurate, bis [2- (meth) acryloyloxyethyl] isocyanurate, and (meth) acrylates of ethylene oxide (EO), propylene oxide, or caprolactam adducts to these starting alcohols. Of these, tris [2- (meth) acryloyloxyethyl] isocyanurate and bis [2- (meth) acryloyloxyethyl) (2-hydroxyethyl) isocyanurate are particularly preferred.

  As a commercial item which can be used suitably as a component (g), Aronix M-215, M-313, M-315, M-325, M-326, M-327 (above, Toa Gosei Chemical Co., Ltd. product) SR-368 (manufactured by Sartomer) and the like. Said compound can be used individually by 1 type or in combination of 2 or more types.

  In the radiation curable composition, the content of the component (g) is preferably 3 to 40% by mass, more preferably 5 to 35% by mass, particularly preferably 100% by mass of the total composition excluding the organic solvent. Is 7-30 mass%. If it is less than 3% by mass, the curability immediately after light irradiation may be insufficient, and if it exceeds 40% by mass, the adhesive strength with the PVA-based molded product may be inferior.

5.4.2 Ingredient (h)
The radiation curable composition may further contain an aliphatic epoxy compound as component (h). The aliphatic epoxy compound of component (h) is an optional component that is added to control the mechanical strength and the like of the adhesive layer.

  Specific examples of the aliphatic epoxy compound include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and polyethylene glycol diglycidyl. Ether, glycerin triglycidyl ether, polypropylene glycol diglycidyl ethers; polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin Diglycidyl esters of aliphatic long-chain dibasic acids; Monoglycidyl ethers of higher aliphatic alcohols; Glycidyl esters of higher fatty acids Ethers; epoxidized soybean oil; butyl epoxy stearate, epoxy stearic octyl, epoxidized linseed oil, epoxy polybutadiene, and the like.

  In the radiation curable composition, the content of the (h) aliphatic epoxy compound is preferably 0 to 50% by mass, more preferably 0 to 45% by mass, and particularly preferably 0 to 40% by mass. When the content exceeds 50% by mass, the content of the essential component (h) alicyclic epoxy compound and the like is decreased, and the effects of the present invention are hardly obtained, which is not preferable.

  Moreover, various additives can be mix | blended with the radiation-curable composition used by this embodiment 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; Plasticizers; UV absorbers; silane coupling agents; inorganic fillers; pigments; dyes and the like.

  The radiation curable composition can be prepared by uniformly mixing the components (d) to (f) and, if necessary, the optional components. The viscosity (25 ° C.) of the radiation curable composition thus obtained is usually 2,000 mPa · s or less, preferably 500 mPa · s or less, more preferably 300 mPa · s or less.

  In addition, solvents, such as an organic solvent, can be added to a radiation curable composition as needed. However, in the present invention, the radiation curable composition can be prepared even without solvent. In this invention, it is preferable not to contain a solvent from surfaces, such as maintenance of work environment and an environmental load. Moreover, it is also preferable to use what was filtered with the filter etc. for the radiation-curable composition.

  The radiation curable composition can be cured by irradiation with radiation. Here, the radiation is not particularly limited, but ultraviolet rays and electron beams are often used.

Radiation is preferably performed at an irradiation dose of 0.1 to 3 J / cm ² in an atmosphere containing oxygen such as air or in an atmosphere not containing oxygen due to an inert gas such as nitrogen. More preferably, the dose is / cm ² .

  The upper limit of the thickness of the radiation curable adhesive layer is not particularly limited, but is preferably 50 μm or less. The lower limit of the thickness of the radiation curable adhesive layer is not particularly limited, but is preferably 1 μm or more. The light transmittance of the radiation curable adhesive layer is preferably 80% or more, particularly preferably 90% or more.

6). Hard coat layer In the manufacturing method of the polarizing plate concerning this embodiment, a hard coat layer can be formed on the surface of the 1st protective layer as needed. The hard coat layer is a layer having a high surface hardness. Therefore, when a hard coat layer is formed on the polarizing plate, the scratch resistance and mechanical strength of the polarizing plate can be increased.

  Examples of the material for forming the hard coat layer include inorganic active energy curable resins such as silicon dioxide, or organic active energy curable resins such as epoxy resins, acrylic resins, and melamine resins. In addition, an antistatic agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a colorant such as a dye or a pigment, a plasticizer, a lubricant, a surfactant, etc. may be added to the hard coat layer as necessary. it can.

  Specifically, an antistatic agent may be added to the hard coat layer to impart an antistatic function. For example, when the first protective layer is made of a cyclic olefin-based resin, it has a property of being easily charged with static electricity because its moisture content is extremely low. When the LCD is assembled, if the first protective layer is charged with static electricity, the liquid crystal cell may be charged and cause a failure.

  Further, the hard coat layer can be antiglare treated. The antiglare treatment generally means forming a hard transparent resin layer having fine irregularities on the surface of the hard coat layer. Thereby, since external light can be diffusely reflected and the reflected image can be blurred, reflection of the surrounding environment due to light from a window or a lighting device can be prevented and visibility can be improved.

  The thickness of the hard coat layer is preferably 0.5 to 50 μm, more preferably 1 to 30 μm. The refractive index of the hard coat layer is preferably 1.45 to 1.70, more preferably 1.45 to 1.60.

7). Low Refractive Index Layer In the method for producing a polarizing plate according to this embodiment, a low refractive index layer can be formed on the surface of the hard coat layer or the first protective layer. By forming the low refractive index layer, a light reflection preventing function can be imparted to the polarizing plate.

  Examples of the material for forming the low refractive index layer include cured products such as fluorinated polymer-containing curable compositions, acrylic monomers, fluorine-containing acrylic monomers, epoxy group-containing compounds, and fluorine-containing epoxy group-containing compounds. . Further, in order to lower the refractive index of the low refractive index layer, hollow particles such as silica can be added thereto. The particle diameter of the silica-based hollow particles is preferably 5 to 100 nm, more preferably 20 to 80 nm. Within this range, an excellent low refractive index can be realized.

  For example, the polarizing plate has an excellent antireflection function by forming a low refractive index layer having a refractive index of 1.30 to 1.45 on a hard coat layer having a refractive index of 1.45 to 1.70. be able to.

  The thickness of the low refractive index layer is preferably 0.05 to 0.20 μm, more preferably 0.08 to 0.12 μm.

8). Examples Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples.

8.1 Production of Silica-Based Hollow Particle-Containing Coating Material (a) Synthesis of Hydroxyl-Containing Fluoropolymer A stainless steel autoclave with an internal volume of 2.0 liters equipped with a magnetic stirrer is sufficiently substituted with nitrogen gas, and then 400 g of ethyl acetate, Perfluoro (propyl vinyl ether) 53.2 g, ethyl vinyl ether 36.1 g, hydroxyethyl vinyl ether 44.0 g, lauroyl peroxide 1.0 g, azo group-containing polydimethylsiloxane (VPS1001 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) ) 6.0 g and 20.0 g of a nonionic reactive emulsifier (NE-30 (trade name), manufactured by Asahi Denka Kogyo Co., Ltd.), cooled to −50 ° C. with dry ice-methanol, and then again with nitrogen gas The oxygen inside was removed.

Next, 120.0 g of hexafluoropropylene was charged and the temperature increase was started. The pressure when the temperature in the autoclave reached 60 ° C. was 5.3 × 10 ⁵ Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours. When the pressure dropped to 1.7 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution having a solid content concentration of 26.4%. The obtained polymer solution was put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 220 g of a hydroxyl group-containing fluoropolymer. This is referred to as a hydroxyl group-containing fluoropolymer. Table 1 shows the amounts of monomers and solvents used.

The obtained hydroxyl group-containing fluoropolymer was measured for the number average molecular weight in terms of polystyrene by gel permeation chromatography and the fluorine content by the alizarin complexone method. ^{Further, 1 H-NMR, 13 C} -NMR both results of NMR analysis, elemental analysis and the fluorine content to determine the percentage of each monomer component constituting the hydroxyl group-containing fluoropolymer. The results are shown in Table 2.

  VPS 1001 is an azo group-containing polydimethylsiloxane having a number average molecular weight of 70 to 90,000 and a polysiloxane portion having a molecular weight of about 10,000. NE-30 is a nonionic reactive emulsifier.

(B) Synthesis of ethylenically unsaturated group-containing fluoropolymer (methacryl-modified fluoropolymer) In a 1-liter separable flask equipped with an electromagnetic stirrer, a glass condenser, and a thermometer, the above (a) 50.0 g of the hydroxyl group-containing fluoropolymer obtained in 1 above, 0.01 g of 2,6-di-t-butylmethylphenol and 370 g of methyl isobutyl ketone (hereinafter also referred to as “MIBK”) as a polymerization inhibitor were charged. At 20 ° C., the hydroxyl group-containing fluoropolymer was dissolved in MIBK and stirred until the solution became transparent and uniform. Next, 15.1 g of 2-methacryloyloxyethyl isocyanate was added to this system and stirred until the solution became homogeneous, then 0.1 g of dibutyltin dilaurate was added to start the reaction, and the temperature of the system was changed to 55 to 65. The MIBK solution of the ethylenically unsaturated group-containing fluoropolymer was obtained by maintaining the temperature at 5 ° C. and continuing stirring for 5 hours. 2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 150 ° C. for 5 minutes, and weighed to determine the solid content, which was 15.0% by weight. The compounds used, solvent and solid content are shown in Table 3.

(C) Production of specific organic compound In a dry air solution, a solution consisting of 23.0 parts of mercaptopropyltrimethoxysilane and 0.5 parts of dibutyltin dilaurate is stirred at 50 ° C. for 1 hour while stirring 60.0 parts of isophorone diisocyanate. After dropping, the mixture was stirred at 70 ° C. for 3 hours. This is made by Shin Nakamura Chemical Co., Ltd. “NK Ester A-TMM-3LM-N (60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate. Of these, the hydroxyl group is responsible for the reaction. It was only pentaerythritol triacrylate.) 202.0 parts were added dropwise at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 3 hours to obtain a specific organic compound.

In the infrared absorption spectrum of the product, the absorption peak at 2550 cm ⁻¹ characteristic for the mercapto group in the raw material and the absorption peak at 2260 cm ⁻¹ characteristic for the isocyanate group disappeared, and [−O—C (= O) -NH-] group and [-S-C (= O) -NH-] peaks characteristic 1720 cm ^-1 to the carbonyl in the group to the peak and acryloyl groups characteristic 1660 cm ^-1 was observed, A specific organic compound having both an acryloyl group as a polymerizable unsaturated group, a [—S—C (═O) —NH—] group, and a [—O—C (═O) —NH—] group has been generated. Showed that.

(D) Production of acrylic-modified hollow silica particles 3 parts of the specific organic compound synthesized in the above (c), 137 parts of hollow silica particles C-1 (manufactured by Catalytic Chemical Industry Co., Ltd., trade name “JX1009SIV”) (solid content 30 parts) ), 0.1 parts of ion-exchanged water, 0.01 parts of 0.05 mol / L dilute sulfuric acid, and 1.4 parts of methyl orthoformate were used to obtain acrylic modified hollow silica particles C-2. The solid content of the acrylic-modified hollow silica particles was determined and found to be 25% by mass.

(E) Preparation of Hollow Particle-Containing Coating Agent Composition 1 As shown in Table 4, 67 g (10 g as solid content) of MIBK solution of the ethylenically unsaturated group-containing fluoropolymer obtained in (b) above, pentaerythritol 29 g of hydroxytriacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “PET-30”), 228 g of the acrylic modified hollow silica particle C-2 dispersion obtained in (d) above (57 g as a solid content), 2- Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (manufactured by Ciba Specialty Chemicals, trade name “Irgacure 127” )), 3 g of acrylic modified polydimethylsiloxane (manufactured by Chisso Corporation, trade name “Silaplane FM-0725”) and 1 g of M 900 g of IBK and 1629 g of propylene glycol monomethyl ether acetate were charged into a glass separable flask equipped with a stirrer and stirred at room temperature for 1 hour to obtain a uniform curable resin composition. Moreover, when the solid content concentration was determined by the method described in (b) above, it was 3.5% by weight.

(F) Preparation of hollow particle-containing coating agent composition 2 As shown in Table 4, 39 g of pentaerythritol hydroxytriacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “PET-30”), hollow silica particles C-1 ( 259 g (57 g as the solid content), 2-hydroxy-1- {4- [2- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl, manufactured by Catalyst Chemical Industry Co., Ltd., trade name “JX1009SIV”) } -2-Methyl-propan-1-one (trade name “Irgacure 127” manufactured by Ciba Specialty Chemicals), acrylic modified polydimethylsiloxane (trade name “Silaplane FM-0725” manufactured by Chisso Corporation) 1 g and MIBK 926 g, propylene glycol monomethyl ether acetate 1629 g The mixture was charged into a glass separable flask equipped with a stirrer and stirred at room temperature for 1 hour to obtain a uniform curable resin composition. Moreover, when the solid content concentration was determined by the method described in (b) above, it was 3.5% by weight.

8.2 Preparation of composition for hard coat In a container where ultraviolet rays are blocked, 95 parts by mass of pentaerythritol hydroxytriacrylate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1- By stirring 5 parts by weight of ON and 100 parts by weight of MIBK at 50 ° C. for 2 hours, a composition for a hard coat layer having a uniform solution was obtained. 2 g of this composition was weighed in an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to determine the solid content, which was 50% by weight.

8.3 Production of Protective Film 1 In this example, the protective film 1 refers to a film in which three layers of a first protective layer, a hard coat layer, and a hollow particle-containing coat layer are laminated. The protective film 1 was produced by the following steps (a) to (c). Table 5 summarizes the materials and surface treatment methods used for the production of the protective films 1-1 to 1-6.

(A) Formation of hard coat layer The first protective layer was coated with the composition for hard coat layer prepared in “8.2 Preparation of composition for hard coat” to a film thickness of 6 μm using a wire bar coater. The film was dried in an oven at 80 ° C. for 1 minute to form a coating film. Subsequently, ultraviolet rays were irradiated under the light irradiation conditions of 300 mJ / cm ² using a high-pressure mercury lamp in the air to prepare a curable resin composition coating substrate.

(B) Formation of hollow particle-containing coat layer A wire bar coater is used to form a film thickness of 0.1 μm on the hard coat layer of the curable resin composition coating substrate obtained in the step (a). Thus, the hollow particle-containing coating agent composition 1 or 2 was applied and dried at 80 ° C. for 1 minute to form a coating film. Next, ultraviolet rays were irradiated under a light irradiation condition of 300 mJ / cm ² using a high-pressure mercury lamp under a nitrogen stream to produce an antireflection film.

(C) Film surface treatment (c1) Corona discharge treatment Using a corona surface treatment apparatus (“AGF-012” manufactured by Kasuga Denki Co., Ltd.), a hard coat layer and a hollow particle-containing coat layer with a discharge amount of 320 W · min / m ² Corona discharge treatment was performed on the film surface opposite to the side on which the film was formed, and bonding was performed within 1 hour after the treatment.

(C2) Saponification treatment (alkali treatment)
The TAC film on which the hard coat layer and the hollow particle-containing coat layer were formed was immersed in a 1.5 mol / L sodium hydroxide aqueous solution at 55 ° C. for 2 minutes. It wash | cleaned in the room temperature water-washing bath, and neutralized using 0.05 mol / L sulfuric acid at 30 degreeC. Again, it was washed in a water bath at room temperature and further dried with hot air at 100 ° C. In this way, both surfaces of the film were saponified.

8.4 Production of Protective Film 2 The protective film 2 refers to the second protective layer, and a liquid crystal panel is installed on the surface opposite to the surface to be bonded to the normal polarizing film. The protective film 2 was produced by the following manufacturing method.

  “Apel APL6013T” (trade name) manufactured by Mitsui Chemicals, Inc. was dissolved in cyclopentane to obtain a resin solution having a resin concentration of 30% by mass. This resin solution was applied onto a polyethylene terephthalate film with a bar coater, allowed to stand for 1 hour, and then dried at 80 ° C. for 12 hours to obtain an appel film having a thickness of 72 μm.

  “TOPAS5013” (trade name) manufactured by Polyplastics was dissolved in methylene chloride to obtain a resin solution having a resin concentration of 30% by mass. This resin solution was applied onto a polyethylene terephthalate film with a bar coater, allowed to stand for 1 hour, and then dried at 80 ° C. for 12 hours to obtain a 75 μm thick Topas film.

  100 parts by weight of cellulose acetate (acetylation degree 60.8%), 12 parts by weight of triphenyl phosphate, 300 parts by weight of methylene chloride and 50 parts by weight of methanol are put into a sealed container, kept at 80 ° C. under pressure and stirring. Dissolved completely. The solution was then filtered, cooled and kept at 30 ° C., and applied with a 15 mil applicator on a PET film affixed to a glass substrate. After standing in this state for 5 minutes, drying was further terminated in an oven at 100 ° C. for 1 hour to obtain a TAC film having a film thickness of 80 μm (no ultraviolet absorber).

  Furthermore, as the protective film 2, “Arton R5300” (trade name) manufactured by JSR Corporation, “Arton R5300U” (trade name) (trade name) manufactured by JSR Corporation, “Zeonor ZF14-100” manufactured by Nippon Zeon Co., Ltd. "(Trade name) was used. These protective films were used as they were without any particular processing.

8.5 Production of Polarizing Film A dyeing solution was prepared by dissolving 20 parts by mass of boric acid, 0.2 parts by mass of iodine, and 0.5 parts by mass of potassium iodide in 480 parts by mass of water. After a PVA film (“Vinylon film # 40” manufactured by Aicello Co., Ltd.) was immersed in this dyeing solution for 30 seconds, the film was stretched twice in one direction and dried to prepare a PVA film having a thickness of 30 μm.

8.6 Preparation of Adhesive (a) Preparation of UV Adhesive (a1) Preparation of UV Adhesive 1 12 parts of “Aronix M-315” manufactured by Toa Gosei Co., Ltd., “Celoxide 2021P” manufactured by Daicel Chemical Industries, Ltd. 32. 5 parts, Kuraray Co., Ltd. “Kuraray Polyol C-2090” 10 parts, San Apro Co., Ltd. “CPI-110A” 2.5 parts, Sakamoto Pharmaceutical Co., Ltd. “SR-NPG” 33 parts, Sanyo Chemical Industries, Ltd. 8 parts of “Sanniks GP-400” manufactured by C., and 2 parts of “Irgacure 184” manufactured by Ciba Specialty Chemicals were mixed to prepare UV adhesive 1.

(A2) Preparation of UV Adhesive 2 58.8 parts of 4-hydroxybutyl acrylate, 19.6 parts of vinyl ester resin (bisphenol vinyl ester), bis ((meth) acryloyloxymethyl) tricyclo [5.2.1. ^02,6 ] decane 19.6 parts, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 1.1 parts, Nippon Kayaku Co., Ltd. "KAYAMER PM-2" 0.1 parts, 2-mercaptobenzothiazole 0.5 part and 0.3 part of Sumitomo Chemical Co., Ltd. "Sumilizer GA80" were mixed, and UV adhesive agent 2 was prepared.

(B) Preparation of water-based adhesive Water content was added to “163-03045” (molecular weight: 22,000, saponification degree: 88 mol%) manufactured by Wako Pure Chemical Industries, Ltd., which is a polyvinyl alcohol resin, to obtain a solid content concentration. A 7% by weight aqueous solution was prepared. On the other hand, 100 parts of “WLS-201 (solid content concentration 35% by weight)” manufactured by Dainippon Ink and Chemicals, which is a polyurethane resin, is added to “CR-” manufactured by Dainippon Ink and Chemicals, which is a polyepoxy curing agent. 5 parts of 5L (100% active ingredient product) "was mixed and diluted with water to prepare an aqueous solution with a solid content of 20% by weight. The obtained polyurethane resin aqueous solution and polyvinyl alcohol resin aqueous solution were mixed at a weight ratio of 1: 1 (solid content weight ratio of 80:20), and a mixed adhesive having a solid content concentration of 15% by weight was obtained. Prepared.

8.7 Bonding Method (a) UV Adhesive UV Adhesive 1 or 2 is applied onto the protective film 2 using a wire bar coater # 3, and then “8.4 Production of Polarizing Film” on it. The produced PVA film was bonded so that defects such as bubbles would not enter. Next, the UV adhesive 1 or 2 was applied onto the protective film 1 using a wire bar coater # 3, and pasted on the PVA of the pasted film so that no defects such as bubbles would enter. Fix the four sides of the protective film 1 with tape so that the protective film 2 is on the glass plate, and light from the protective film 2 side with a metal halide lamp (illuminance 220 mW / cm ² , irradiation light quantity 1,000 mJ / cm ² ). Irradiated and allowed to stand at 23 ° C. and 50% RH for 24 hours.

(B) Aqueous adhesive A water-based adhesive is applied onto the protective film 2 using a wire bar coater # 3, and the PVA film produced in “8.4 Production of Polarizing Film” is coated with defects such as bubbles. Bonding was done so as not to enter. Next, a water-based adhesive was applied onto the protective film 1 using a wire bar coater # 3, and was bonded onto the PVA of the bonded film so as not to have defects such as bubbles. The film was fixed so as not to peel off, heated at 80 ° C. for 1 hour, and then allowed to stand at 23 ° C. and 50% RH for 24 hours.

8.8 Evaluation method (a) Scratch resistance (steel wool resistance test)
Steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) is attached to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film is 10 under a load of 500 g. By rubbing repeatedly, the presence or absence of scratches on the surface of the cured film was visually confirmed according to the following criteria. The evaluation criteria are as follows. The results are shown in Table 6 and Table 7.
A: The cured film is not damaged.
◯: Almost no peeling or scratching of the cured film is observed, or slight thin scratches are observed on the cured film.
X: Streaky scratches or peeling of the cured film is observed on the entire surface of the cured film.

  When a UV adhesive is used as the adhesive, the saponification process can be omitted. Therefore, the protective film 1 showed excellent scratch resistance regardless of the type (see Examples 1 to 11). However, when an aqueous adhesive is used as the adhesive, it is necessary to perform a saponification treatment in order to increase the adhesive strength. When it did so, the damage | wound on a stripe | line | muscle on the whole surface of the protective film 1 or peeling of the cured film was recognized by the said test (Comparative Examples 1-3).

(B) Peel strength The peel strength of the produced laminated film was measured according to "JIS K 6854-4 Adhesive-Peel Adhesive Strength Test Method Part 4: Floating roller method". The produced bonding film was fixed on a metal plate (made of stainless steel, dimensions: length 200 mm, width 25 mm, thickness 1.5 mm) with a double-sided adhesive tape (ST-416P, manufactured by Sumitomo 3M). The end in the longitudinal direction of the laminated film was peeled off using a cutter knife. According to JIS method, when the sample is attached to the floating roller, the edge of the peeled film sample is fixed to the grip of the tensile tester, and the floating roller is raised at a speed of 300 mm / min with the tensile tester, and the film peels off. The average peel force (unit: N) was measured. The results are shown in Table 6 and Table 7.

  Evaluation of peel strength is when the average peel force is 1.5 N or more, or when the laminated film is broken or the edge of the laminated film cannot be peeled off, when the peel strength is 0.6 N or more and less than 1.5 N The peel strength was Δ and the average peel force was less than 0.6 N.

  Excellent peel strength was obtained regardless of the type of adhesive, the type of protective film, and the method for treating the bonding surface of the protective film.

It is a schematic diagram which shows the cross section of the polarizing plate which concerns on this embodiment. It is a schematic diagram explaining the manufacturing method of the polarizing plate which concerns on this embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Polarizing film, 12 ... 1st radiation curable adhesive layer, 14 ... 1st protective layer, 16 ... 2nd radiation curable adhesive layer, 18 ... 2nd protective layer, 20 ... Hard-coat layer 20 ... low refractive index layer, 30, 32 ... laminating roll, 40, 42 ... roll, 50 ... polarizing plate winding part, 60, 62 ... adhesive supply part, 70, 72 ... radiation irradiation part, 80 ... adhesive Agent layer, 90 ... liquid crystal panel, polarizing plate ... 100

Claims (12)

(A) A second layer formed between the polarizing film and the first protective layer formed on the first surface of the polarizing film, and on the second surface of the polarizing film and the polarizing film. Supplying a radiation curable adhesive composition between the protective layer and
(B) bonding the polarizing film, the first protective layer, and the second protective layer via the radiation curable adhesive composition;
(C) curing the radiation curable adhesive composition by irradiating with radiation to form a radiation curable adhesive layer;
And at least the first protective layer is not subjected to saponification treatment. In claim 1,
Before the said process (a), the manufacturing method of a polarizing plate which further includes the process of performing a corona discharge process to the surface which bonds the said polarizing film of a said 1st protective layer or a said 2nd protective layer. In claim 1 or 2,
The method for producing a polarizing plate, wherein at least one of the first protective layer and the second protective layer contains an ultraviolet absorber. In any of claims 1 to 3,
The manufacturing method of a polarizing plate which irradiates a radiation from the protective layer side with high ultraviolet transmittance among said 1st protective layer or said 2nd protective layer. In any of claims 1 to 4,
The said 2nd protective layer is a manufacturing method of a polarizing plate which served as the function of retardation film. In any of claims 1 to 5,
Furthermore, the manufacturing method of a polarizing plate including the process of forming a hard-coat layer on the said 1st protective layer. In claim 6,
The said hard-coat layer is a manufacturing method of a polarizing plate which has an antistatic function. In claim 6 or 7,
Furthermore, the manufacturing method of a polarizing plate including the process of forming a low-refractive-index layer on the said hard-coat layer. In claim 8,
The said low refractive index layer is a manufacturing method of a polarizing plate containing a silica type hollow particle. In any one of Claim 1 thru | or 9,
The method for producing a polarizing plate, wherein the radiation curable adhesive layer is a cured product of a radiation curable liquid resin composition containing at least the following components (d), (e), and (f).
(D) an alicyclic epoxy compound,
(E) a compound containing at least one hydroxyl group and having a number average molecular weight of 500 or more,
(F) Photoacid generator. In claim 10,
Furthermore, the said radiation-curable liquid resin composition is a manufacturing method of a polarizing plate containing the component represented by following formula (1).

(R ¹ , R ² and R ³ are each independently a monovalent organic group, at least two of R ^{1 to} R ³ are —R ⁴ OCOCR ⁵ ═CH ₂ , and R ⁴ has 2 to 2 carbon atoms. 8 is a divalent organic group, and R ⁵ is a hydrogen atom or a methyl group.) In claim 10 or 11,
Furthermore, the said radiation-curable liquid resin composition is a manufacturing method of a polarizing plate containing an aliphatic epoxy compound.

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