JP2009075473A - Polarizing plate, manufacturing method thereof, layered optical member and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polarizing plate which hardly causes a problem such as peeling and cohesive failure between a polarizer and a protective film, to provide a layered optical member and to provide a liquid crystal display device. <P>SOLUTION: The polarizing plate 10 comprises the polarizer 13 and the protective film 11 having a face 12 made of an optical soft resin, wherein the polarizer 13 is in contact with the face 12. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polarizing plate including a polarizer, a method for producing the polarizing plate, a laminated optical member including the polarizing plate, and a liquid crystal display device including the polarizing plate or the optical member.

  A liquid crystal display device is widely used as various display devices because it has low power consumption, can operate at a low voltage, and is lightweight and thin.

  The basic configuration of the liquid crystal display device is composed of a light guide means, two polarizing plates, and a liquid crystal cell sandwiched between both polarizing plates. Since the light from the light guiding means is polarized by the two polarizing plates, it is possible to control whether the light reaches the human eye by controlling the optical rotation in the liquid crystal cell.

  A polarizing plate generally has a structure in which a transparent protective film (polarizer protective film) is laminated on both sides or one side of a polarizer made of a polyvinyl alcohol-based resin having a dichroic dye adsorbed and oriented. The reason why the protective film is laminated on the polarizer is that a polarizer made of a polyvinyl alcohol-based resin has low strength, and the polarizer alone may be broken or split.

  The polarizer is produced by a method in which a polyvinyl alcohol resin film is subjected to longitudinal uniaxial stretching and dyeing with a dichroic dye, followed by boric acid treatment to cause a crosslinking reaction, followed by washing with water and drying. As the dichroic dye, iodine or a dichroic organic dye is used. A protective film is laminated on both or one side of the polarizer thus obtained to form a polarizing plate, which is incorporated into a liquid crystal display device. As the protective film, a cellulose acetate resin film typified by triacetyl cellulose is often used, and the thickness thereof is usually about 30 to 120 μm. In addition, an adhesive composed of an aqueous solution of a polyvinyl alcohol-based resin is often used for laminating the protective film.

There is also an attempt to configure at least one protective film with a resin other than cellulose acetate. For example, Patent Document 1 describes that, in a polarizing plate in which protective films are laminated on both sides of a polarizer, at least one of the protective films is composed of a thermoplastic norbornene resin having a retardation film function. Yes. In Patent Document 2, a protective film made of an amorphous polyolefin-based resin is laminated on one surface of a polarizer made of a polyvinyl alcohol-based resin film adsorbed and oriented with iodine or a dichroic organic dye, and the other surface Describes a polarizing plate in which a protective film made of a resin different from an amorphous polyolefin resin such as a cellulose acetate resin is laminated. Furthermore, Patent Document 3 describes that a protective film made of a cycloolefin resin is laminated on a polyvinyl alcohol polarizer via an adhesive containing a urethane adhesive and a polyvinyl alcohol resin. Yes. Furthermore, Patent Document 4 describes a polarizing plate in which a protective film made of an amorphous polyolefin resin (cycloolefin resin) such as a norbornene resin is laminated. These resins are selected to have a high glass transition temperature for the purpose of protecting the protective film.
JP-A-8-43812 (published February 16, 1996) JP 2002-174729 A (released on June 21, 2002) JP 2004-334168 A (published November 25, 2004) JP 2007-65452 A (published March 15, 2007)

  However, in the conventional polarizing plate, problems such as peeling and cohesive failure may occur between the polarizer and the protective film.

  For example, a polarizing plate in which a protective film made of triacetyl cellulose is laminated on both sides or one side of a polarizer on which a dichroic dye is adsorbed and oriented via an adhesive made of an aqueous solution of a polyvinyl alcohol-based resin under wet heat conditions When used for a long time, there was a problem that the protective film and the polarizer were easily peeled off.

  Further, in Patent Document 4, when a protective film made of an amorphous polyolefin resin (cycloolefin resin) such as norbornene resin is laminated on a polarizer, the resin side of the interface between the polarizer and the protective film is disclosed. It is described that it easily causes cohesive failure.

  The present invention has been made in view of the above-described problems, and mainly provides a polarizing plate, a laminated optical member, and a liquid crystal display device that have less problems such as peeling and cohesive failure between a polarizer and a protective film. Objective.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a protective film having a high glass transition temperature has conventionally been used for the purpose of protecting a polarizer. The present inventors have found that the above-mentioned problems can be suppressed by using a soft resin.

  That is, the polarizing plate according to the present invention includes a polarizer and a protective film having a surface made of an optical soft resin, and the polarizer is in contact with the surface made of the optical soft resin. It is a feature. The polarizing plate is a polarizing plate in which a protective film is laminated on at least one surface of a polarizer, and the adhesive surface of the protective film to the polarizer is a polarizing plate made of an optical soft resin.

  In the polarizing plate according to the present invention, the polarizer may be a polarizer made of a polyvinyl alcohol-based resin film in which a dichroic dye is adsorbed and oriented.

  In the polarizing plate according to the present invention, the protective film may be a retardation film.

  In the polarizing plate according to the present invention, the protective film has one or more functions selected from the group consisting of an antireflection function, an antiglare function, an anti-scratch function, an antifouling function, an ultraviolet protection function, and an antistatic function. You may do it.

  In the polarizing plate according to the present invention, the protective film may be a multilayer film, and the protective film may include an adhesive layer.

  In the polarizing plate according to the present invention, the glass transition temperature of the optical soft resin is preferably 90 ° C. or lower.

In the polarizing plate according to the present invention, the soft optical resin may be made of one or more resins selected from the group consisting of an amorphous polyester resin, a polyamide resin, and an amorphous olefin resin. .

  In the polarizing plate according to the present invention, when the optical soft resin contains an additive, the amount of the additive is preferably 0.5 parts by weight or less with respect to 100 parts by weight of the optical soft resin. .

  In the polarizing plate according to the present invention, when a catalyst residue is contained in the optical soft resin, the amount of the catalyst residue may be 0.02 part by weight or less with respect to 100 parts by weight of the optical soft resin. preferable.

  In the polarizing plate according to the present invention, the polarizer and the protective film may be laminated via an aqueous adhesive, and the aqueous adhesive may contain a crosslinkable epoxy resin. .

  In the polarizing plate according to the present invention, the polarizer and the protective film may be laminated via a solventless epoxy adhesive, and the solventless epoxy adhesive is thermosetting or It may be photocurable.

  The method for producing a polarizing plate according to the present invention is a method for producing a polarizing plate comprising a polarizer and a protective film having a surface made of an optical soft resin, the surface comprising the polarizer and the optical soft resin. A surface treatment step of performing surface treatment on at least one of the above, and a bonding step of bonding the polarizer and the surface made of the optical soft resin through an adhesive after the surface treatment step It is characterized by that.

  In the method for producing a polarizing plate according to the present invention, the surface treatment may be one or more surface treatments selected from the group consisting of corona discharge treatment, ozone treatment, electron beam treatment, UV treatment, and anchor coat treatment. .

  The laminated optical member according to the present invention includes the polarizing plate according to the present invention.

  The laminated optical member according to the present invention may further include a retardation film.

  The liquid crystal display device according to the present invention is characterized in that the polarizing plate according to the present invention or the laminated optical member according to the present invention is bonded to a liquid crystal cell via an adhesive.

  In the polarizing plate according to the present invention, since the polarizer is in contact with the surface of the protective film made of the optical soft resin, stress strain between the polarizer and the protective film is reduced, peeling, cohesive failure, etc. Is suppressed.

  The method for producing a polarizing plate according to the present invention comprises the step of producing a polarizing plate comprising a polarizer and a protective film having a surface made of an optical soft resin, and the surface made of the polarizer and the optical soft resin. In order to carry out a surface treatment step of applying a surface treatment to either one of the polarizer and the surface made of the optical soft resin before the bonding step of bonding together with an adhesive, the polarizer and the The protective film can be firmly bonded. Therefore, according to the manufacturing method of the polarizing plate which concerns on this invention, the polarizing plate which concerns on this invention can be manufactured suitably.

  Hereinafter, the present invention will be described in detail.

  In this specification, “weight” is treated as a synonym for “mass”, and “weight%” is treated as a synonym for “mass%”. Further, “A to B” indicating the range indicates that the range is A or more and B or less.

  Moreover, in this specification, the "main component" means containing 50 mass% or more.

  The present invention provides a polarizing plate. “Polarizing plate” refers to a member having a function of polarizing light.

  FIG. 1 is a front view showing a schematic configuration of a polarizing plate according to an embodiment of the present invention. As shown in FIG. 1, the polarizing plate 10 according to this embodiment includes a protective film 11, a polarizer 13, and a retardation film 14. In addition, the adhesive surface 12 with the polarizer 13 of the protective film 11 consists of soft resin for optics.

  The polarizing plate according to the present invention is not limited to the above configuration, and a protective film is laminated on at least one surface of the polarizer, and the adhesive surface of at least one protective film to the polarizer is optical. What is necessary is just to be comprised with soft resin. In other words, the polarizing plate according to the present invention includes a polarizer and a protective film having a surface made of an optical soft resin, and the polarizer is in contact with the surface made of the optical soft resin. Therefore, in the configuration shown in FIG. 1, for example, a protective film may be provided instead of the retardation film 14, or the retardation film, the reflective layer, and the semi-transmissive film may be provided above the protective film 11 or below the retardation film 14. You may provide new layers, such as a type | mold reflection layer, a light-diffusion layer, a phase difference film, a condensing sheet, a brightness enhancement film, and an adhesion layer.

(Protective film)
The protective film 11 is not particularly limited as long as the polarizer 13 can be reinforced and the adhesive surface 12 with the polarizer 13 is made of an optical soft resin, and a crystalline resin and an amorphous resin are preferable. Can be used. Further, the protective film 11 may be a single layer film made of an optical soft resin or a multilayer film having the optical soft resin on one outermost layer. The protective film 11 preferably covers the entire surface of the polarizer 13.

  In one embodiment, the protective film 11 is made of an optical soft resin. By constituting the protective film 11 using an optical soft resin, the adhesive surface 12 of the protective film 11 with the polarizer 13 can be easily made into an optical soft resin.

  The thickness of the protective film 11 is not particularly limited and may be appropriately selected depending on the application. However, it is preferably about 5 to 1000 μm, more preferably 10 μm to 500 μm, and further preferably 15 μm to 150 μm.

In the protective film 11, the number of foreign matters having a diameter of 0.1 mm or more in the film is preferably 0.1 piece / m ² or less, and more preferably 0.01 piece / m ² or less. In order to reduce the amount of the foreign matter as described above, a polymer filter or the like may be used as described later.

  The protective film 11 may be a retardation film by a known technique, and has functions such as an antireflection function, an antiglare function, an anti-scratch function, an antifouling function, and an ultraviolet protection function. And may have an adhesive layer.

The antireflection function refers to a function of suppressing reflection by external light in a polarizing plate, a laminated optical member, and a liquid crystal display device. Specifically, it means a function of setting the reflectance in the wavelength region of visible light to preferably 2% or less, more preferably 1% or less, and still more preferably 0.2% or less. Such reflection of external light reduces the contrast of the screen display and makes it difficult to see the screen. Such an antireflection function can be imparted, for example, by forming an antireflection layer on the film surface.

  The antiglare function refers to a function of suppressing an image from being reflected by reflection of external light in a polarizing plate, a laminated optical member, and a liquid crystal display device. Specifically, as an index of the antiglare function, for example, a value of glossiness (gloss) is used, which means a function of setting the gloss at an incident angle of 60 ° to 100 or less, preferably 60 or less. Such image reflection due to reflection of external light makes it difficult to see the image display. Since the reflection is based on an image formed by regular reflection, the reflection can be suppressed by scattering the reflected light. For example, such an antiglare function can be imparted by forming an antiglare layer on the film surface.

  The scratch preventing function refers to a function of suppressing scratches on the screen in polarizing plates, laminated optical members, and liquid crystal display devices. Specifically, the pencil hardness symbol in the pencil scratch test (JIS K5400) means a function of 2H or more, preferably 4H or more, more preferably 5H or more. This function can be imparted by forming a hard coat layer on the outermost surface or reducing the friction coefficient.

  The antifouling function refers to a function of suppressing smudges such as fingerprints on the screen in polarizing plates, laminated optical members, and liquid crystal display devices. Specifically, it means a function of making the contact angle with water 80 ° or more, more preferably 100 ° or more. This function can be imparted by forming a water repellent layer using a silicon compound or a fluorine compound on the outermost surface.

  The ultraviolet ray preventing function refers to a function of making it difficult for ultraviolet rays to enter the polarizer and the liquid crystal and suppressing the optical deterioration of the polarizer and the liquid crystal in the polarizing plate, the laminated optical member, and the liquid crystal display device. Specifically, as an index of the ultraviolet ray prevention function, it means a function of setting the light transmittance at a wavelength of 380 nm or less to 10% or less and the light transmittance at a wavelength of 400 nm to 80% or less (preferably 70% or less). This function can be imparted by using an ultraviolet absorber or an ultraviolet reflector.

The antistatic function refers to a function of preventing dust or the like from being attached to the polarizing plate, the laminated optical member, or the liquid crystal display device, or preventing the circuit from being damaged by discharging. Specifically, it means a function of making the surface resistance value 10 ¹² Ω / □ or less, preferably 10 ¹¹ Ω / □ or less, more preferably 10 ¹⁰ Ω / □ or less. This function can be imparted by forming an antistatic layer on the surface or inside.

  Furthermore, the protective film used by this invention can also be used independently for an optical use. FIG. 3 is a front view showing a configuration example of the film. As shown in FIG. 3, the film may be a single layer film (FIG. 3A) composed of a layer 15 containing an optical soft resin, and includes the other layer 16, and the optical soft resin. It may be a multilayer film having at least one layer 15 containing (FIG. 3 (b) and FIG. 3 (c)). Of course, the above film can be used as a protective film adhered to a polarizer.

(Soft resin for optics)
“Optical soft resin” refers to a resin having a glass transition temperature of 90 ° C. or lower. Such resins include, for example, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polycaproamide (nylon-6), polyaminoundecanoic acid (nylon-11), polylauryllactam (nylon-12), polyhexamethylene. Polyamide resins such as diaminoazibic acid (nylon-66), polyhexamethylenediamino sebacic acid (nylon-610), polyhexamethylenediaminododecanedioic acid (nylon-612), ethylene-vinyl alcohol copolymer, ethylene- It can be prepared from styrene copolymers, olefin resins such as ethylene-vinylcyclohexane, halogen-containing resins such as polyvinyl chloride, ethylene-tetrafluoroethylene copolymer, etc. No.

  The glass transition temperature of the optical soft resin used in the present invention is 90 ° C. or lower, preferably 80 ° C. or lower, more preferably 60 ° C. or lower. The optical soft resin used in the present invention may be crystalline or non-crystalline, but preferably has a crystallinity of 1% or more, more preferably a crystallinity of 5% or more. It is. When the degree of crystallinity is less than 5%, the glass transition temperature is preferably 40 ° C. or higher, and more preferably 60 ° C. or higher. In the present specification, the glass transition temperature and the crystallinity refer to values measured by the DSC method (measured at a heating rate of 10 ° C. per minute). “Glass transition temperature” in the present invention means a value measured by a differential scanning calorimeter by the method described in JIS K7121.

  In one embodiment, the soft optical resin is made of an amorphous polyester resin, a polyamide resin, an amorphous olefin resin, or a combination of two or more thereof. In addition, an additive may be added to the optical soft resin.

  When the glass transition temperature of these resins is higher than 90 ° C., a known plasticizer or the like may be blended so that the glass transition temperature is 90 ° C. or less. As the plasticizer to be used, a plasticizer well known and commonly used by those skilled in the art may be appropriately used according to the type of the optical soft resin to be blended. For example, when polyvinyl chloride is used as the optical soft resin, the plasticizer As such, esters such as dioctyl phthalate and diethylhexyl phthalate can be used.

(Amorphous polyester resin)
An amorphous polyester-based resin having a glass transition temperature of 90 ° C. or lower can be suitably used as the optical soft resin according to the present invention. The amorphous polyester resin is a substantially amorphous polyester. The above “substantially amorphous” means that the crystallinity value measured by DSC method (measured at a heating rate of 10 ° C./min) is 10% or less, preferably 5% or less, More preferably, the melting point by the DSC method is hardly seen (that is, the degree of crystallinity is 0%). The “crystallinity” can be calculated from the value of heat of fusion obtained by DSC measurement, with a sample having a clear crystallinity fixed by the X-ray method or the like as a standard. The heat of crystal fusion was measured using a DSC (Differential Scanning Calorimetry) device, after performing nitrogen sealing at a sample amount of 10 mg and a temperature increase rate of 10 ° C./min, once increasing the temperature to the melting point or more and decreasing the temperature to room temperature. From the area of the melting peak when the temperature is raised again. The crystallinity is preferably measured from a single resin, but when measured in a mixed state, the melting peak may be obtained by subtracting the melting peak of the resin to be mixed.

  The amorphous polyester resin is not particularly limited as long as it is substantially amorphous, and includes various polyesters composed of a dicarboxylic acid component and a diol component.

Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, 5-t-butylisophthalic acid, 4,4′-biphenyldicarboxylic acid, trans-3,3′-stilbene dicarboxylic acid, and trans-4,4. '-Stilbene dicarboxylic acid, 4,4'-dibenzyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 2,2,6,6-tetramethylbiphenyl-4,4′-dicarboxylic acid, 1,1,3-trimethyl-3-phenylindene-4,5-dicarboxylic acid, 1,2- Aromatic dicarboxylic acids such as diphenoxyethane-4,4′-dicarboxylic acid, diphenyl ether dicarboxylic acid, and substituted products thereof Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, heptadecanedioic acid , Octadecanedioic acid, nonadecanedioic acid, icosanedioic acid, docosanedioic acid, 1,12-dodecanedioic acid, and substituted derivatives thereof; 1,4-decahydronaphthalenedicarboxylic acid, 1,5 -Decahydronaphthalenedicarboxylic acid, 2,6-decahydronaphthalenedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid, trans-1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and substituted products thereof And alicyclic dicarboxylic acids such as These dicarboxylic acid components can be used alone or in combination of two or more.

  Examples of the diol component include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2 -Dimethyl-1,3-propanediol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,8-octane Aliphatic acids such as diol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2,4-dimethyl-1,3-hexanediol, 1,10-decanediol, polyethylene glycol, polypropylene glycol Diol; 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4 Cycloaliphatic diols such as cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol; 2,2-bis (4′-β-hydroxyethoxydiphenyl) propane, bis (4′- Examples thereof include ethylene oxide adducts of bisphenol compounds such as β-hydroxyethoxyphenyl) sulfone and aromatic diols such as xylylene glycol. These diol components can be used alone or in combination of two or more.

  In addition to the above, the amorphous polyester-based resin includes oxycarboxylic acids such as p-oxybenzoic acid and p-oxyethoxybenzoic acid; monocarboxylic acids such as benzoic acid and benzoylbenzoic acid; A structural unit such as a monovalent alcohol such as a polyvalent carboxylic acid; a monohydric alcohol such as polyalkylene glycol monomethyl ether; a polyhydric alcohol such as glycerin, pentaerythritol, or trimethylolpropane may be included.

  The amorphous polyester resin is not particularly limited as long as it is amorphous. However, terephthalic acid is used as the dicarboxylic acid component, ethylene glycol is the main component as the diol component, and 1,4-cyclohexanedimethanol (CHDM) is used. A copolymerized polyester (hereinafter referred to as CHDM copolymerized PET) used as a copolymerization component is preferable from the viewpoints of cost, productivity, and the like. In this case, the copolymerization ratio of CHDM is preferably 10 to 40 (mol%), more preferably 20 to 30 (mol%) with respect to ethylene glycol.

(Polyamide resin)
A polyamide-based resin having a glass transition temperature of 90 ° C. or lower can be suitably used as the optical soft resin according to the present invention. The polyamide resin is a polymer having an acid amide bond. For example, polycaproamide (nylon-6), polyaminoundecanoic acid (nylon-11), polylauryllactam (nylon-12), polyhexamethylenediaminoadipine Polymers such as acid (nylon-66), polyhexamethylene diamino sebacic acid (nylon-610), polyhexamethylene diamino dodecanedioic acid (nylon-612), caprolactam / lauryl lactam copolymer (nylon-6 / 12) Caprolactam / aminoundecanoic acid copolymer (nylon-6 / 11), caprolactam / hexamethylenediaminoadipic acid copolymer (nylon-6 / 66), caprolactam / hexamethylenediaminoadipic acid / hexamethylenediaminosebacic acid (ny Down -6/6
6/610), and copolymers such as caprolactam / hexamethylenediaminoadipic acid / hexamethylenediaminododecanedioic acid (nylon-6 / 66/612). These polyamide resins can be used alone or in combination of two or more.

  Of these, caproamide is the main component, such as nylon-6, nylon-6 / 12, nylon-6 / 11, nylon-6 / 66, nylon-6 / 66/610, nylon-6 / 66/612, etc. Are preferably used. Among them, those having a caproamide component of 60% by weight or more are more preferably used because they exhibit excellent effects in improving impact resistance and the like.

(Amorphous olefin resin)
As the optical soft resin of the present invention, a polymer composed of an olefin monomer, and an amorphous olefin resin having a glass transition temperature of 90 ° C. or less can be suitably used. Those having a temperature higher than ° C. can be more suitably used.

  Examples of the olefin that is a component of the polymer include α-olefins having 3 to 20 carbon atoms. Specific examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 1-hexene. Butene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nanodecene, Linear α-olefins such as 1-eicosene; 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, 2,2,4 -Trimethyl-1-pentene etc. are mentioned.

  Furthermore, polyene compounds, cyclic olefins, vinyl aromatic compounds and the like are also preferable monomers.

  Examples of the polyene compound include conjugated polyene compounds and non-conjugated polyene compounds. Examples of the conjugated polyene compound include an aliphatic conjugated polyene compound and an alicyclic conjugated polyene compound. Examples of the non-conjugated polyene compound include an aliphatic non-conjugated polyene compound, an alicyclic non-conjugated polyene compound, and an aromatic non-conjugated polyene. Compounds and the like. These may have an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, and the like.

Examples of the cyclic olefin include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene. 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1 , 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimeta -1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a -Octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8 Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5 , 8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4
4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2- Isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene, 5,5- Dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene, 5,6-dicarboxylnorbornene anhydrate, 5-dimethylamino Norbornene, 5-cyanonorbornene, cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3, -Dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene, etc. .

  Examples of the vinyl aromatic compound include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, Examples include ethyl styrene and vinyl naphthalene.

  The said monomer may be used by 1 type and may be used in combination of 2 or more type.

  Although these polymerization methods are not limited, they can be produced by a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method or the like using a metallocene catalyst. Examples of the catalyst include JP-A-58-19309, JP-A-60-35005, JP-A-60-35006, JP-A-60-35007, and JP-A-60-35008. JP-A 61-130314, JP-A 3-163088, JP-A 4-268307, JP-A 9-12790, JP-A 9-87313, JP 10-508055, Examples thereof include metallocene catalysts described in JP-A-11-80233 and JP-T-10-508055. Further, as a particularly preferred example of the production method using a metallocene catalyst, the method of EP-A-1211287 can be exemplified.

(Additive)
The additive contained in the optical soft resin of the present invention is used as necessary, and is not particularly limited. However, the amount of the additive in the optical soft resin is preferably 1 part by weight or less with respect to 100 parts by weight of the optical soft resin, 0.5 part by weight or less, 0.3 part by weight or less, and further 0.1 part by weight. Part or less is more preferable, and 0.05 part by weight or less is particularly preferable from the viewpoint of suppressing a decrease in adhesive strength. Moreover, it is preferable that the additive amount in crystalline polyolefin resin is 0.005 mass part or more with respect to 100 mass parts of crystalline polyolefin resin.

  When the amount of the additive exceeds 1 part by weight with respect to 100 parts by weight of the optical soft resin, the adhesive force tends to be lowered due to a bleed-out phenomenon with time. The smaller the amount of the additive, the better, but it is necessary to add it to the extent that it does not deteriorate during the production of the protective film. These additives may be used alone or in combination of two or more.

Examples of the additives include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, ultraviolet absorbers, light stabilizers, peroxide scavengers, hydroxylamines, lubricants, plasticizers, flame retardants, Nucleating agent, metal deactivator, antistatic agent, surfactant (including antifogging agent), pigment, filler, anti-blocking agent, processing aid, foaming agent, foaming aid, emulsifier, brightener, medium Coloring agents such as a summing agent, 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, benzofuranones (US Pat. No. 4,325,853, 433)
No. 8244, No. 5175312, No. 5216053, No. 5252643, No. 4316611, German Patent Publication No. 4316622, No. 4316876, European Patent Application No. 589839, No. 5911102. Etc.), auxiliary stabilizers such as indolines, and crosslinking agents.

Examples of the phenol-based antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2,6-di-t-butylphenol, 2- t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t- Butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-diocudadecyl-4-methylphenol, 2,4, 6-tricyclohexylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6 (1′-methylundecyl-1′-yl) phenol, 2,4-dimethyl-6- (1′-methylheptadecyl-1′-yl) phenol, 2,4-dimethyl-6- (1′- Alkylated monophenols such as methyltridecyl-1′-yl) phenol and mixtures thereof; 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2, Alkylthiomethylphenols such as 4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol and mixtures thereof; 2,6-di-t-butyl-4-methoxyphenol, 2, 5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphene Diol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5 Hydroquinones and alkylated hydroquinones such as -di-t-butyl-4-hydroxyphenyl) adipate and mixtures thereof; tocopherols such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof; 2'-thiobis (6-t-butylphenol), 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (3 -Methyl-6-t-butylphenol), 4,4'-thiobis (2-methyl-6-t-butylphenol), Hydroxylated thiodiphenyl ethers such as 4,4′-thiobis (3,6-di-t-amylphenol), 4,4 ′-(2,6-dimethyl-4-hydroxyphenyl) disulfide; 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol )], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (4-methyl-6-nonylphenol), 2,2′-methylenebis (4,6-di-t) -Butylphenol), 2,2'-ethylidenebis (4,6-di-t-butylphenol), 2,2'-ethylidenebis (4-isobutyl-6-t-butyl) Phenol), 2,2′-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2′-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4 '-Methylenebis (6-t-butyl-2-methylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol) ), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-) 5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis ( 5-t-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis-3′-t-butyl-4′-hydroxyphenyl) butyrate], Bis (3-t-butyl-4-hydroxy-5
-Methylphenyl) dicyclopentadiene, bis [2- (3'-t-butyl-2'-hydroxy-5'-methylbenzyl) -6-t-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4) -Hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5-t-butyl-4-hydroxy-2-methylphenyl) pentane, 2-t-butyl- 6- (3′-t-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,4-di-t-pentyl-6- [1- (2-hydroxy-3, 5-di-t-pe Alkylidene bisphenol and derivatives thereof such as [tilphenyl) ethyl] phenyl acrylate and mixtures thereof; 3,5,3 ′, 5′-tetra-t-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy- 3,5-dimethylbenzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, O-, N- and S such as bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-t-butyl-4-hydroxybenzyl mercaptoacetate and mixtures thereof A benzyl derivative; dioctadecyl-2,2-bis (3,5-di-t Butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecylmercaptoethyl-2,2-bis (3,5-di-t -Butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) ) Hydroxybenzylated malonate derivatives such as malonate and mixtures thereof; 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,4 -Bis (3,5-di-t-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-t-butyl) Aromatic hydroxybenzyl derivatives such as (L-4-hydroxybenzyl) phenol and mixtures thereof; 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1 , 3,5-triazine, 2-n-octylthio-4,6-bis (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2-n-octylthio-4, 6-bis (4-hydroxy-3,5-di-t-butylphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-t-butyl-4-phenoxy) -1,3,5-triazine, tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanur 2,4,6-tris (3,5-di-t-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 2,4,6-tris (3,5-di- t-butyl-4-hydroxyphenylpropyl) -1,3,5-triazine, tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate, tris [2- (3 ′, 5′-di-t- Butyl-4'-hydroxycinnamoyloxy) ethyl] isocyanurate and mixtures thereof such as triazine derivatives; dimethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-t -Butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-t- Benzylphosphonate derivatives such as til-4-hydroxy-3-methylbenzylphosphonate, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoester and mixtures thereof; 4-hydroxylauric acid anilide; Acylaminophenol derivatives such as 4-hydroxystearic anilide, octyl-N- (3,5-di-t-butyl-4-hydroxyphenyl) carbanate and mixtures thereof; β- (3,5-di-t- (Butyl-4-hydroxyphenyl) propionic acid and methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol , Neopentyl glycol, diethylene Recall, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, Esters with mono- or polyhydric alcohols such as trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane and mixtures thereof; β- (5-t-butyl-4-hydroxy-3-methylphenyl) propionic acid and methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1, 6-hexanediol, 1 9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundeca One such as diol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane and mixtures thereof Esters with mono- or polyhydric alcohols; β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid and methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N , N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxa Esters with mono- or polyhydric alcohols such as bicyclo [2,2,2] octane and mixtures thereof; 3,5-di-tert-butyl-4-hydroxyphenylacetic acid and methanol, ethanol, octanol, octadecanol , Ethylene Recall, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, Tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha Esters with mono- or polyhydric alcohols such as 2,6,7-trioxabicyclo [2,2,2] octane and mixtures thereof; N, N′-bis [3- (3 ′, 5′- Di-t-butyl-4'-hydroxyphenyl) propioni Hydrazine, N, N′-bis [3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionyl] hexamethylenediamine, N, N′-bis [3- (3 ′, 5'-di-t-butyl-4'-hydroxyphenyl) propionyl] trimethylenediamine and mixtures thereof such as β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid amide Can be mentioned.

  Further, for example, a composite type phenolic antioxidant having a unit having both a phenolic antioxidant mechanism and a phosphorus antioxidant mechanism in one molecule may be used.

Particularly preferable examples of the phenolic antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, and 2,4-dioctylthiomethyl-6- Methylphenol, 2,2'-thiobis (6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-) Butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol)], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (4,6-di-t-butylphenol), 2,2′-ethylidenebis (4,6-di) -T-butylphenol), 4,4'-methylenebis (6-t-butyl-2-methylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-butylidenebis ( 3-methyl-6-tert-butylphenol), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1 , 3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, ethylene glycol = bis [3,3-bis-3′-tert-butyl-4′-hydroxyphenyl] butyrate], 2 -T-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,4-di-t-pentyl-6- [1- (2 Hydroxy-3,5-di-tert-pentylphenyl) ethyl] phenyl acrylate, 2,4,6-tris (3,5-di-tert-butyl-4-phenoxy) -1,3,5-triazine, tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, bis (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, tris [2- (3 ′, 5 '-Di-t-butyl-4'-hydroxycinnamoyloxy) ethyl] isocyanurate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, di-n-octadecyl-3,5-di Tert-butyl-4-hydroxybenzylphosphonate, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoester, n-octade Sil-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, neopentanetetrayltetrakis (3,5-di-t-butyl-4-hydroxycinnamate), thiodiethylenebis (3,5-di-tert-butyl-4-hydroxycinnamate), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene 3,6-dioxaoctamethylene bis (3,5-di-t-butyl-4-hydroxycinnamate), hexamethylene bis (3,5-di-t-butyl-4-hydroxycinnamate), tri Ethylene glycol = bis (5-t-tyl-4-hydroxy-3-methylcinnamate), 3,9-bis [2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) Propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5 · 5] undecane, N, N′-bis [3- (3 ′, 5′-di-t-) Butyl-4′-hydroxyphenyl) propionyl] hydrazine, N, N′-bis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionyl] hexamethylenediamine and the like, These may be used alone or in combination of two or more.

  Examples of the sulfur antioxidant include dilauryl-3,3′-thiodipropionate, tridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, and distearyl-3. , 3′-thiodipropionate, lauryl stearyl-3,3′-thiodipropionate, neopentanetetrayltetrakis (3-laurylthiopropionate), and the like.

Examples of the phosphorus antioxidant include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, Distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-6-methylphenyl) ) Pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite , Tristearyl sorbitol trifo Phyto, tetrakis (2,4-di-t-butylphenyl) -4,4'-diphenylenediphosphonite, 2,2'-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite , 2,2'-ethylidenebis (4
, 6-Di-t-butylphenyl) fluorophosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, bis (2,4-di-t-butyl-6-methyl) Phenyl) methyl phosphite, 2- (2,4,6-tri-t-butylphenyl) -5-ethyl-5-butyl-1,3,2-oxaphosphorinane, 2,2 ′, 2 ″- Nitrilo [triethyl-tris (3,3 ′, 5,5′-tetra-t-butyl-1,1′-biphenyl-2,2′-diyl) phosphite and a mixture thereof may be mentioned. Moreover, the phosphorus antioxidant described in JP-A-2002-69260 is also preferable.

  Particularly preferable examples of the phosphorus antioxidant include tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, bis (2 , 4-Di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl) -4-methylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-diphenylenediphosphonite, 2,2'-methylenebis (4,6-di-) t-butylphenyl) 2-ethylhexyl phosphite, 2,2′-ethylidenebis (4,6-di-t-butylphenol) ) Fluorophosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, 2- (2,4,6-tri-t-butylphenyl) -5-ethyl-5 Butyl-1,3,2-oxaphosphorinane, 2,2 ′, 2 ″ -nitrilo [triethyl-tris (3,3 ′, 5,5′-tetra-t-butyl-1,1′-biphenyl- 2,2′-diyl) phosphite and the like, and these may be used alone or in combination of two or more.

Examples of the ultraviolet absorber include phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, 4 -T-octylphenyl salicylate, bis (4-t-butylbenzoyl) resorcinol, benzoylresorcinol, hesisadecyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate, octadecyl-3', 5'-di Salicylates such as -t-butyl-4'-hydroxybenzoate, 2-methyl-4,6-di-t-butylphenyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate and mixtures thereof Derivatives; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4- Cutoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2 ', 4,4'-tetrahydroxybenzophenone and mixtures thereof 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3 ′, 5′-di-t-butyl-2′-hydroxyphenyl) benzotriazole, 2- ( 5'-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (3-t-butyl-2-hydroxy-5- Methylphenyl) -5-chlorobenzotriazole, 2- (3′-s-butyl-2′-hydroxy-5′-t-butyl) Ruphenyl) benzotriazole, 2- (2′-hydroxy-4′-octyloxyphenyl) benzotriazole, 2- (3 ′, 5′-di-t-amyl-2′-hydroxyphenyl) benzotriazole, 2- [ 2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2-[(3′-t-butyl-2′-hydroxyphenyl) -5 ′-( 2-octyloxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2- [3′-t-butyl-5 ′-[2- (2-ethylhexyloxy) carbonylethyl] -2′-hydroxyphenyl] -5 -Chlorobenzotriazole, 2- [3'-t-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl] -5-chlorobenzotria 2- [3'-t-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl] benzotriazole, 2- [3'-t-butyl-2'-hydroxy-5- (2-octyloxycarbonylethyl) phenyl] benzotriazole, 2- [3′-t-butyl-2′-hydroxy-5 ′-[2- (2-ethylhexyloxy) carbonylethyl] phenyl] benzotriazole, 2- [2-Hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5 Chlorobenzotriazole, 2- (3′-dodecyl-2′-hydroxy-5′-methylphenyl) benzotriazole and 2- [3′-tert-butyl-2′-hy Roxy-5 ′-(2-isooctyloxycarbonylethyl) phenyl] benzotriazole mixture, 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3, 3-tetramethylbutyl) phenol, 2,2′-methylenebis [4-tert-butyl-6- (2H-benzotriazol-2-yl) phenol], poly (3-11) (ethylene glycol) and 2- [ A condensate with 3′-t-butyl-2′-hydroxy-5 ′-(2-methoxycarbonylethyl) phenyl] benzotriazole, poly (3-11) (ethylene glycol) and methyl-3- [3- ( 2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionate condensate, 2-ethylhexyl-3- [3-tert-butyl 5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, octyl-3- [3-t-butyl-5- (5-chloro-2H-benzotriazole-2) -Yl) -4-hydroxyphenyl] propionate, methyl-3- [3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, 3- [3 2- (2′-hydroxyphenyl) benzotriazole such as -t-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionic acid and mixtures thereof .

  Particularly preferable examples of the ultraviolet absorber include phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-. Hydroxybenzoate, 4-t-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3 ′ , 5'-Di-t-butyl-2'-hydroxyphenyl) benzoto Azole, 2- (5'-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (3-t-butyl-2 -Hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (3'-s-butyl-2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-4) '-Octyloxyphenyl) benzotriazole, 2- (3', 5'-di-t-amyl-2'-hydroxyphenyl) benzotriazole, 2- [2'-hydroxy-3 ', 5'-bis (α , Α-dimethylbenzyl) phenyl] -2H-benzotriazole and the like, and these may be used alone or in admixture of two or more.

Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ((2,2,6,6-tetramethyl-4-piperidyl) succinate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6) -Pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl-2,2,6,6-tetramethyl) Ru-4-piperidyl) -2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1,2,2,6,6-pentamethyl-4) -Piperidyl decandioate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -1- [ 2- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2, 6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) ) -1, , 3,4-Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4 Mixed esterified product of butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol; 1,2,3,4-butanetetrabonic acid and 2,2,6,6 -Mixed esterified product of tetramethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3, 9- Mixed esterified product with bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5 · 5] undecane, 1,2,3,4- Butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [ 5.5 mixed esterified product with undecane, polycondensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, poly [(6- Morpholino-1,3,5-triazine-2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl) imino) hexamethylene ((2,2,6,6-tetramethyl- 4-piperidyl) imino)], poly [(6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl ((2,2,6,6) -Tetramethyl-4-pi Lysyl) imino) hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)], N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexa A polycondensate of methylenediamine and 1,2-dibromoethane, N, N ′, 4,7-tetrakis [4,6-bis (N-butyl-N- (2,2,6,6-tetramethyl- 4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, N, N ′, 4-tris [4,6-bis (N-butyl) -N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, N, N ', 4,7-tetrakis [4,6-bis (N-butyl-N- (1,2,2 6,6-pentamethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, N, N ′, 4-tris [4,6 -Bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1, Hindered amine light stabilizers such as 10-diamine and mixtures thereof, ethyl-α-cyano-β, β-diphenyl acrylate, isooctyl-α-cyano-β, β-diphenyl acrylate, methyl-α-carbomethoxycinnamate, Methyl α-cyano-β-methyl-p-methoxycinnamate, butyl-α-cyano-β-methyl-p-methoxycinnamate, methyl-α-carbomethoxy-p-methoxycinnamate Acrylate light stabilizers such as namate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline and mixtures thereof, 2,2′-thiobis- [4- (1,1,3,3- Nickel-based light stabilizers such as nickel complex of tetramethylbutyl) phenol], nickel dibutyldithiocarbamate, nickel salt of monoalkyl ester, nickel complex of ketoxime and mixtures thereof, 4,4′-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-t-butylanilide, 2,2'-didodecyloxy-5,5'-di-t-butylanilide 2-ethoxy-2′-ethyloxanilide, N, N′-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl Oxamide-based light stabilizers such as 2′-ethoxyanilide, 2-ethoxy-5,4′-di-t-butyl-2′-ethyloxanilide and mixtures thereof, 2,4,6-tris (2 -Hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3 5-triazine, 2- [2,4-dihydroxyphenyl-4,6-bis (2,4-dimethylphenyl] -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxy) Phenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1, 3,5-tri Gin, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2- Hydroxy-3-butyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyl) 2- (2-hydroxyphenyl) -1,3,5-triazines such as oxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and mixtures thereof Examples thereof include light stabilizers.

Further, particularly preferable examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-piperidyl). Sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di -T-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) -2,2-bis (3,5-di − -Butyl-4-hydroxybenzyl) -2-butylmalonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -1- [2- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl Oxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6, 6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1 2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl Mixed esterified product of -4-piperidinol and 1-tridecanol, mixed esterified product of 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2, Mixed esterified product of 4,8,10-tetraoxaspiro [5.5] undecane, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4 -Mixed esterified product of piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5 · 5] undecane, dimethyl succinate and 1- Polycondensate with (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, poly [(6-morpholino-1,3,5-triazine-2,4-diyl) ( (2,2,6,6-tetramethyl-4-piperidyl) imino) hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)], poly [(6- (1,1 , 3,3-tetramethylbutyl) -1,3,5-triazine-2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl) imino) hexamethylene ((2,2 , 6,6-Tetrame -4-piperidyl) imino)], and the like, which may be used alone or in combination, respectively.

  Examples of the metal deactivator include N, N′-diphenyloxamide, N-salicyl-N′-salicyloylhydrazine, N, N′-bis (salicyloyl) hydrazine, N, N′-bis ( 3,5-di-t-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bis Examples thereof include phenyl hydrazide, N, N′-bis (salicyloyl) oxalyl dihydrazide, N, N′-bis (salicyloyl) thiopropionyl dihydrazide, and mixtures thereof.

  Examples of the hydroxylamine include N, N-dibenzylhydroxyamine, N, N-diethylhydroxyamine, N, N-dioctylhydroxyamine, N, N-dilaurylhydroxyamine, and N, N-ditetradecylhydroxy. Examples thereof include amines, N, N-dihexadecylhydroxyamine, N, N-dioctadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-heptadecyl-N-octadecylhydroxyamine, and mixtures thereof.

  Examples of the neutralizing agent include calcium stearate, zinc stearate, magnesium stearate, hydrotalcite (basic magnesium, aluminum, hydroxy, carbonate, hydrate), melamine, amine, polyamide, polyurethane, and mixtures thereof. Can be mentioned.

  Examples of the lubricant include aliphatic hydrocarbons such as paraffin and wax, higher aliphatic acids having 8 to 22 carbon atoms such as stearic acid, and higher aliphatic acid metals having 8 to 22 carbon atoms (Al, Ca, Mg, Zn) salt, aliphatic alcohol having 8 to 22 carbon atoms, polyglycol, ester of higher fatty acid having 4 to 22 carbon atoms and aliphatic monohydric alcohol having 4 to 18 carbon atoms, higher aliphatic having 8 to 22 carbon atoms Examples include amides, silicone oils, rosin derivatives, and the like. For example, erucic acid amide, oleic acid amide, ethylene bisstearylamide, erucylamide, dimethylpolysiloxane and the like can be mentioned.

  The antistatic agent may be any of a polymer type, an oligomer type, and a monomer type. Examples thereof include polyhydric alcohol fatty acid esters such as glycerin fatty acid esters, polyoxyethylene alkylamine mixed compositions, nonionic surfactants, and the like. Also, for example, alkyl diethanolamides, alkyl diethanol monoesters, lauryl diethanolamide, myristyl diethanolamide, palmityl diethanolamide, stearyl diethanolamide, alkyl diethanolamide monolaurate, alkyl diethanolamide monomyristic ester, Examples thereof include monopalmitic acid esters of alkyldiethanolamide, monostearic acid esters of alkyldiethanolamide, and the like.

Examples of the surfactant include cationic surfactants, anionic surfactants, amphoteric surfactants, and nonionic surfactants, and are not particularly limited, but are compatible with resins and heat stable. From the viewpoint of safety, a nonionic surfactant is preferably used. Specifically, sorbitan-based interfaces such as sorbitan fatty acid esters such as sorbitan monopalmitate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monomontanate, sorbitan monooleate, sorbitan dioleate, and alkylene oxide adducts thereof. Activator: glycerin monopalmitate, glycerin monostearate, diglycerin distearate, triglycerin monostearate, tetraglycerin dimontanate, glycerin monooleate, diglycerin monooleate, diglycerin sesquioleate, tetraglycerin Monooleate, hexaglycerin monooleate, hexaglycerin trioleate, tetraglycerin trioleate, tetraglycerin monolaurate, hexaglyceride Glycerin surfactants such as glycerin fatty acid esters such as phosphorus monolaurate and alkylene oxide adducts thereof; polyethylene glycol surfactants such as polyethylene glycol monopalmitate and polyethylene glycol monostearate; alkylene oxide adducts of alkylphenols; Esters of sorbitan / glycerin condensate and organic acid, polyoxyethylene (2 mol) stearylamine, polyoxyethylene (4 mol) stearylamine, polyoxyethylene (2 mol) stearylamine monostearate, polyoxyethylene (4 Mol) Polyoxyethylene alkylamines such as laurylamine monostearate and fatty acid esters thereof.

  Examples of the surfactant include fluorine compounds having a perfluoroalkyl group, ω-hydrofluoroalkyl group, etc. (especially fluorine surfactants), silicone compounds having an alkylsiloxane group (particularly silicone surfactants), and the like. Is mentioned. Specific examples of the fluorosurfactant include “Unidyne DS-403”, “DS-406”, “DS-401” (trade name) manufactured by Daikin Industries, Ltd., and “Surflon” manufactured by Seimi Chemical Co., Ltd. KC-40 "(trade name) and the like, and examples of the silicone surfactant include" SH-3746 "(trade name) manufactured by Toray Dow Corning Silicon Co., Ltd.

  As the anti-blocking agent, fine particles having a spherical shape or a shape close thereto can be used regardless of inorganic type or organic type. Specific examples include calcium carbonate, silicon dioxide, polymethylsilsesquioxane, aluminum silicate salt, and a crosslinked polymethyl methacrylate.

  Examples of the nucleating agent include sorbitol nucleating agents, organophosphate nucleating agents, and polymer nucleating agents such as polyvinylcycloalkane. Specifically, sodium = 2, 2 '-Methylenebis (4,6-di-t-butylphenyl) phosphate, [phosphoric acid-2,2'-methylenebis (4,6-di-t-butylphenyl)] = dihydroxyaluminum, bis [phosphoric acid- 2,2′-methylenebis (4,6-di-t-butylphenyl)] hydroxyaluminum, tris [phosphate-2,2′-methylenebis (4,6-di-t-butylphenyl)] aluminum, sodium = Bis (4-tert-butylphenyl) phosphate, benzoic acid metal salts such as sodium benzoate, aluminum pt-butylbenzoate, 1,3: 2,4-bis (o-benzyli) ) Sorbitol, 1,3: 2,4-bis (o-methylbenzylidene) sorbitol, 1,3: 2,4-bis (o-ethylbenzylidene) sorbitol, 1,3-o-3,4-dimethylbenzylidene -2,4-o-benzylidene sorbitol, 1,3-o-benzylidene-2,4-o-3,4-dimethylbenzylidene sorbitol, 1,3: 2,4-bis (o-3,4-dimethylbenzylidene Sorbitol, 1,3-op-chlorobenzylidene-2,4-o-3,4-dimethylbenzylidene sorbitol, 1,3-o-3,4-dimethylbenzylidene-2,4-op-chloro Benzylidene sorbitol, 1,3: 2,4-bis (op-chlorobenzylidene) sorbitol and mixtures thereof, rosin-based alkali metal salts, Earth metal salts, particularly lithium salts of rosin, sodium salts, potassium salts, calcium salts, magnesium salts, compounds such as aluminum salts. Moreover, polymer nucleating agents such as polyvinylcycloalkane are also used. These may be used alone or in combination of two or more.

  Examples of the filler include calcium carbonate, silicate, glass fiber, asbestos, talc, kaolin, mica, barium sulfate, carbon black, carbon fiber, zeolite, and mixtures thereof, and these are used alone. Alternatively, two or more kinds may be used in combination.

  Examples of the foaming agent and foaming aid include azocarboxylic acid derivatives such as azodicarboxylic acid amide, N.I. Examples thereof include nitroso compounds such as N'-dinitrosopentamethylenetetramine, and sulfonyl hydrazide compounds such as p, p'-oxybisbenzenesulfonyl hydrazide.

  Examples of the crosslinking agent include dicumyl peroxide, t-butylcumyl peroxide, 3,5-dimethyl-2,5- (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di -(T-butyl-peroxy) hexane-3,4,4'-bis (t-butylperoxy) diisopropylbenzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, etc. Is mentioned. Among these additives, phenol antioxidants, phosphorus antioxidants, ultraviolet absorbers, hindered amine light stabilizers, peroxide scavengers and neutralizers are preferably used.

  The addition method of the said additive will not be specifically limited if it can disperse | distribute uniformly, It can add by a normal method. For example, an additive may be added to the polymerization reaction mixture during the polymerization reaction or immediately after the completion of the polymerization reaction in the polymerization step for producing the optical soft resin. The additive may be added as a solution dissolved in a solvent, may be added as a dispersant pulverized into a powder form so that it can be easily dispersed, or may be added in a molten state by heating. .

  Further, after the additive is added while melt-kneading the optical soft resin, it may be further melt-kneaded. These melt-kneading is performed using, for example, a kneader such as a ribbon blender, a mixing roll, a Banbury mixer, a roll, various kneaders, a single screw extruder, a twin screw extruder or the like. After the melt-kneading, the obtained composition may be subjected to a molding process in a molten state without being cooled, or may be cooled to pellets and then heated again to be subjected to a molding process. Moreover, after cooling, you may use for shaping | molding processes by methods, such as press molding, with a cooling state. When using a plurality of additives, there is no limitation on the addition method, and each additive may be added simultaneously, or may be added before and after each timing of addition.

In addition, as described in JP-A-2005-161696, when a resin composition is produced by melt-kneading a resin and a plurality of additives, the following first to fourth steps,
1st process: The process which mixes at least 2 or more types of additives which are powder at normal temperature with resin of a powder as needed, and manufactures an additive masterbatch beforehand;
Second step: storing the additive master batch in an additive storage hopper;
Third step: a step of transferring the additive master batch of the additive storage hopper to the additive supply hopper;
4th process: The process which measures the said additive masterbatch, supplies it to a melt-kneader, melt-kneads with resin, and manufactures a fat composition (pellet);
A manufacturing method or the like characterized by containing can also be used.

  These processes are more preferably performed in an inert gas atmosphere such as nitrogen gas. It is also more preferable to carry out a series of steps from polymerization powder to pelletization in a clean room environment. Furthermore, it is more preferable to incorporate a foreign matter removal system such as a polymer filter upstream of the die of the melt kneader (granulator) in this step.

As a matter of course, as for the film forming process, a series of processes as described above are performed in a clean room environment, performed in an inert gas atmosphere such as nitrogen gas, and the die of the melt extruder in the process Incorporating a foreign substance removal system such as a polymer filter upstream is a preferable method. In addition, it is preferable to completely remove cellulose fibers, chemically synthesized fibers, and the like that are likely to be mixed as foreign substances from the working environment of a series of processes by means such as not handling them in all processes.

(Catalyst residue)
In the optical soft resin according to the present embodiment, a catalyst residue during polymerization usually remains. It is preferable that the catalyst residue is small because appearance defects such as fish eyes when formed into a film are reduced.

  The amount of the catalyst residue is preferably 0.02 parts by mass or less, more preferably 0.01 parts by mass or less, and particularly preferably 0.005 parts by mass or less with respect to 100 parts by mass of the optical soft resin. Further, the amount of silicon in the catalyst residue is preferably 0.01 parts by mass or less, more preferably 0.005 parts by mass or less, with respect to 100 parts by mass of the optical soft resin. The amount of the catalyst residue and the amount of silicon in the catalyst residue can be quantified by the method described below.

<Measurement of catalyst residue>
100 g of the optical soft resin sample is precisely weighed and incinerated in an electric furnace at 800 ° C. The ashed sample is precisely weighed and the amount of catalyst residue can be determined by the following equation.
Catalyst residue (ppm by mass) = (Soft optical resin after ashing (g) / Soft optical resin before ashing (g)) × 10 ⁶
<Measurement of silicon content>
An optical soft resin sample (1 g) is placed in a platinum dish, 1 ml of sulfuric acid is added, carbonized with a hot plate, and then incinerated at 550 ° C. in an electric furnace. To the residue after ashing, 0.5 g of sodium carbonate was added, melted with a burner, adjusted to 50 ml with ultrapure water, and then IICP-AES (inductively coupled plasma emission spectrometer model: Optima 3000) manufactured by PerkinElmer. The amount of silicon can be quantified.

  Also, as a protective film, the residue when incinerated by the method according to the above <Measurement of catalyst residue> is 0.05 parts by mass or less, further 0.02 parts by mass or less, based on 100 parts by mass of the protective film, In particular, the amount is preferably 0.001 part by mass or less.

(Method for producing protective film)
The production method of the protective film according to the present invention is not particularly limited, and is an extrusion molding method from a molten resin, a solvent casting method in which a resin dissolved in an organic solvent is cast on a flat plate, and the solvent is removed to form a film. Any known method may be used. In terms of cost, an extrusion molding method from a molten resin is excellent, and a T-die molding method, an inflation molding method and the like are preferably used. In the case of a multilayer, a multilayer T-die molding method, a multilayer inflation molding method, an extrusion laminate molding method, a sand laminate molding method, a dry laminate molding method, a wet laminate molding method, a hot melt laminate molding method and the like are preferably used. In the T-die molding method and the multilayer T-die molding method, a film having a small in-plane retardation can be obtained by minimizing the stress applied to the film at the time of molding by a method such as an air chamber, an air knife, or electrostatic pinning. . Further, in the case of a cooling method using a soft nip method such as a flex roll or a steel belt method, there is an advantage that transparency can be improved.

  Taking an extrusion molding method from a molten resin as an example, it is preferable to filter small foreign matter with a polymer filter disposed between the extruder and the die, and to extrude the molten film from the die, and between the extruder and the polymer filter. In addition, the breaker plate or screen changer and gear pump should be arranged in this order, and large foreign matters should be filtered with the screen arranged on the breaker plate or screen changer, and small foreign matters should be filtered with the polymer filter via the gear pump. preferable.

In order to reduce the number of foreign matters having a diameter of 0.1 mm or more in the film to 0.1 pieces / m ² or less, more preferably 0.01 pieces / m ² or less, the polymer filter has a filtration accuracy of 3 to 3. A 80 μm one may be used.

  One embodiment of the polymer filter is shown in FIG. The polymer filter is formed by adjusting the filtration area by attaching a plurality of leaf disk filters 2 to the center post 3 disposed in the housing 1 so that foreign matter is filtered most efficiently. The leaf disk filter 2 is made by laminating and sintering nonwoven fabrics of metal fine fibers so that the filtration accuracy becomes higher sequentially from the upstream side to the downstream side. The polymer filter has the highest filtration accuracy of 3 to 80 μm. If the filtration accuracy is lower than this, the effect of reducing foreign matters is low, and if the filtration accuracy is high, the back pressure becomes too high, and a very large filtration area is required. Therefore, the residence time in the polymer filter becomes long, such as the number of leaf discs becoming extremely large or the diameter of the leaf discs becoming large, and thermal degradation is likely to occur, and clogging with foreign substances is also severe, which is preferable. Absent.

(Polarizer)
The polarizer is obtained by adsorbing and orienting a dichroic dye on a polyvinyl alcohol-based resin film so as to obtain predetermined polarization characteristics. As the dichroic dye, iodine or a dichroic organic dye is used. Therefore, specific examples of the polarizer include an iodine polarizing film in which iodine is adsorbed and oriented on a polyvinyl alcohol resin film, and a dye polarizing film in which a dichroic organic dye is adsorbed and oriented on a polyvinyl alcohol resin film. be able to.

  The polyvinyl alcohol resin can be obtained by saponifying a polyvinyl acetate resin. Examples of the polyvinyl acetate resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith. Examples of other monomers copolymerized with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, and unsaturated sulfonic acids. The polyvinyl alcohol-based resin may be modified. For example, polyvinyl formal modified with aldehydes, polyvinyl acetal, polyvinyl butyral, and the like can also be used.

(Production method of polarizing plate)
The polarizing plate is usually a humidity adjusting step for adjusting the moisture of the polyvinyl alcohol-based resin film, a step for uniaxially stretching the polyvinyl alcohol-based resin film, and the dichroic pigment by dyeing the polyvinyl alcohol-based resin film with a dichroic pigment. The process of adsorbing, the process of treating the polyvinyl alcohol resin film on which the dichroic dye is adsorbed and oriented with a boric acid aqueous solution, the washing process of washing off the boric acid aqueous solution, and the dichroic dye are adsorbed and oriented by performing these steps. It is manufactured through a step of attaching a protective film to the uniaxially stretched polyvinyl alcohol resin film. Uniaxial stretching may be performed before dyeing, may be performed during dyeing, or may be performed during boric acid treatment after dyeing. Moreover, it may be uniaxially stretched in these multiple stages. For uniaxial stretching, rolls having different peripheral speeds may be uniaxially stretched or uniaxially stretched using a hot roll. Moreover, the dry-type extending | stretching which extends | stretches in air | atmosphere may be sufficient, and the wet extending | stretching which extends | stretches in the state swollen with the solvent may be sufficient. The draw ratio is usually about 4 to 8 times. The thickness of the polyvinyl alcohol polarizer is, for example, about 5 to 50 μm.

It is also effective to laminate a resin film on a surface different from the surface on which the protective film is laminated in the polarizing plate of the present invention. Examples of the resin for the resin film include cellulose acetate resins such as triacetyl cellulose and diacetyl cellulose, amorphous polyolefin resins (cycloolefin resins), optical soft resins, acrylic resins, and polycarbonate resins. . Considering the ease of adhesion with the polarizer and the ease of forming the surface treatment layer, a cellulose acetate resin film, particularly a triacetyl cellulose film is preferably used. When a cellulose acetate resin film is used as the protective film, it is desirable to saponify the surface with an alkaline aqueous solution prior to bonding with the polarizer. The thickness of a resin film is about 30-200 micrometers normally, Preferably it is 30-120 micrometers, More preferably, it is 30-85 micrometers. Various polarizing layers such as an antireflection layer and an antiglare layer may be provided on the polarizing plate surface on the side different from the surface to be bonded to the liquid crystal cell.

  For adhesion between the polarizer and the protective film, for example, an adhesive containing an epoxy resin, a urethane resin, a cyanoacrylate resin, an acrylamide resin, or the like as a component can be used. A preferable adhesive from the viewpoint of thinning the adhesive layer includes an aqueous adhesive, that is, an adhesive component dissolved in water or dispersed in water. Another preferred adhesive is a solventless adhesive, specifically, an adhesive that forms a layer of adhesive by reacting and curing a monomer or oligomer by heating or irradiation with active energy rays.

(Water-based adhesive)
Hereinafter, the water-based adhesive will be described. Examples of the adhesive component that can be a water-based adhesive include water-soluble crosslinkable epoxy resins and urethane resins.

  Examples of water-soluble crosslinkable epoxy resins include polyamides obtained by reacting epichlorohydrin with polyamide polyamines obtained by reacting polyalkylene polyamines such as diethylenetriamine and triethylenetetramine with dicarboxylic acids such as adipic acid. An epoxy resin is mentioned. Examples of such commercially available polyamide epoxy resins include “Smiles Resin 650” and “Smiles Resin 675” (both trade names) sold by Sumika Chemtex Co., Ltd.

  When a water-soluble epoxy resin is used as the adhesive component, it is preferable to mix other water-soluble resins such as a polyvinyl alcohol-based resin in order to further improve coatability and adhesiveness. Polyvinyl alcohol resins include partially saponified polyvinyl alcohol and fully saponified polyvinyl alcohol, as well as modified polyvinyl alcohol such as carboxyl group-modified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, methylol group-modified polyvinyl alcohol, and amino group-modified polyvinyl alcohol. Alcohol-based resin may be used. Among these, a saponified product of a copolymer of vinyl acetate and an unsaturated carboxylic acid or a salt thereof, that is, carboxyl group-modified polyvinyl alcohol is preferably used. Here, the “carboxyl group” includes not only a carboxyl group (—COOH) but also a salt thereof.

  Suitable examples of the commercially available carboxyl group-modified polyvinyl alcohol include “Kuraray Poval KL-506”, “Kuraray Poval KL-318” and “Kuraray Poval KL-118” (available from Kuraray Co., Ltd.) All are trade names), “GOHSENAL T-330” and “GOHSENAL T-350” (trade name) sold by Nippon Synthetic Chemical Industry Co., Ltd., “DR” sold by Denki Kagaku Kogyo Co., Ltd. -0415 "(trade name)," AF-17 "," AT-17 ", and" AP-17 "(all trade names) sold by Nippon Vinegar Poval Co., Ltd.

  When an adhesive containing a water-soluble epoxy resin is used as the adhesive, the epoxy resin and other water-soluble resin such as a polyvinyl alcohol-based resin added as necessary are dissolved in water to obtain an adhesive solution. create. In this case, the water-soluble epoxy resin preferably has a concentration in the range of about 0.2 to 2 parts by mass per 100 parts by mass of water. Moreover, when mix | blending polyvinyl alcohol-type resin, it is preferable to make the quantity into the range of about 1-10 mass parts per 100 mass parts of water, and it is still more preferable to set it as the range of about 1-5 mass parts. .

On the other hand, when a water-based adhesive containing a urethane resin is used, examples of suitable urethane resins include ionomer-type urethane resins, particularly polyester-based ionomer-type urethane resins.

  Here, the ionomer type is obtained by introducing a small amount of an ionic component (hydrophilic component) into the urethane resin constituting the skeleton. The polyester ionomer type urethane resin is a urethane resin having a polyester skeleton, into which a small amount of an ionic component (hydrophilic component) is introduced. Such an ionomer-type urethane resin is suitable as a water-based adhesive because it is emulsified directly in water without using an emulsifier to form an emulsion. Examples of commercially available polyester ionomer-type urethane resins include “Hydran AP-20” and “Hydran APX-101H” (both trade names) sold by Dainippon Ink and Chemicals, Inc. Both are available in the form of emulsions.

  When an ionomer type urethane resin is used as an adhesive component, it is usually preferable to further add a crosslinking agent such as an isocyanate-based crosslinking agent. The isocyanate-based crosslinking agent is a compound having at least two isocyanate groups (—NCO) in the molecule. Examples thereof include 2,4-tolylene diisocyanate, phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1, In addition to polyisocyanate monomers such as 6-hexamethylene diisocyanate and isophorone diisocyanate, adducts in which a plurality of these molecules are added to a polyhydric alcohol such as trimethylolpropane, and 3 molecules of diisocyanate are each at one terminal isocyanate group. There are a trifunctional isocyanurate body in which an isocyanurate ring is formed, a polyisocyanate modified body such as a burette body formed by hydration and decarboxylation of three diisocyanate molecules at each one-end isocyanate group. Examples of commercially available isocyanate-based crosslinking agents that can be suitably used include “Hydran Assist C-1” (trade name) sold by Dainippon Ink and Chemicals, Inc.

  In the case of using an aqueous adhesive containing an ionomer type urethane resin, from the viewpoint of viscosity and adhesiveness, the concentration of the urethane resin is within a range of about 10 to 70% by mass, and further 20% by mass or more, and 50% by mass. What was dispersed in water so that it may become% or less is preferable. When the isocyanate crosslinking agent is blended, the blending amount may be appropriately selected so that the isocyanate crosslinking agent is within the range of about 5 to 100 parts by mass with respect to 100 parts by mass of the urethane resin.

  A water-based adhesive as described above can be applied to the protective film and / or the adhesive surface of the polarizer and bonded together to form a polarizing plate.

  The method of laminating the polarizer and the protective film is not particularly limited. For example, an adhesive is uniformly applied to the surface of the polyvinyl alcohol polarizer or the protective film, and the other film is applied to the coated surface. For example, a method of stacking them together with a roll or the like and drying them. Drying is performed at a temperature in the range of about 60 to 100 ° C., for example. After drying, it is preferable to carry out curing for about 1 to 10 days at a temperature slightly higher than room temperature, for example, a temperature in the range of about 30 to 50 ° C., from the viewpoint of further increasing the adhesive strength.

(Solvent-free adhesive)
Next, the solventless adhesive will be described. The solventless type adhesive does not contain a significant amount of solvent, and is generally an adhesive composed of a curable compound that is polymerized by heating or irradiation with active energy rays, and a polymerization initiator. . From the viewpoint of reactivity, those that are cured by cationic polymerization are preferred, and epoxy adhesives are particularly preferred.

In the polarizing plate according to the present embodiment, in one preferred embodiment, the polarizer and the protective film are laminated via a solventless epoxy adhesive. The adhesive is more preferably cured by cationic polymerization by heating or irradiation with active energy rays. In particular, from the viewpoint of weather resistance, refractive index, and the like, an epoxy compound that does not contain an aromatic ring in the molecule is suitably used as the curable compound.

  An adhesive using an epoxy compound that does not contain an aromatic ring in the molecule is described in, for example, Japanese Patent Application Laid-Open No. 2004-245925. Examples of such an epoxy compound that does not contain an aromatic ring include a hydride of an aromatic epoxy compound, an alicyclic epoxy compound, an aliphatic epoxy compound, and the like. The curable epoxy compound used for the adhesive usually has two or more epoxy groups in the molecule.

  The hydride of the aromatic epoxy compound can be obtained by selectively hydrogenating the aromatic epoxy compound to the aromatic ring under pressure in the presence of a catalyst.

  Examples of the aromatic epoxy compound include bisphenol-type epoxy compounds such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of bisphenol S; phenol novolac epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde Examples thereof include novolak-type epoxy resins such as phenol novolak epoxy resins; polyfunctional epoxy compounds such as glycidyl ether of tetrahydroxydiphenylmethane, glycidyl ether of tetrahydroxybenzophenone, and epoxidized polyvinylphenol. Among these hydrides of aromatic epoxy compounds, hydrogenated bisphenol A diglycidyl ether is preferred.

  Next, an alicyclic epoxy compound is demonstrated. The alicyclic epoxy compound is a compound having at least one epoxy group bonded to the alicyclic ring in the molecule, as shown in the following formula.

(In the formula, m represents an integer of 2 to 5)
A compound in which a group in the form of removing one or more hydrogen atoms in (CH ₂ ) _m in the above formula is bonded to another chemical structure is an alicyclic epoxy compound. Further, the hydrogen forming the alicyclic ring may be appropriately substituted with a linear alkyl group such as a methyl group or an ethyl group. Among these, it is more preferable to use a compound having an epoxycyclopentane ring (m = 3 in the above formula) or an epoxycyclohexane ring (m = 4 in the above formula). Specific examples of the alicyclic epoxy compound include the following compounds.

That is, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, ethylene bis (3,4 -Epoxycyclohexanecarboxylate), bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, diethylene glycol bis (3,4-epoxycyclohexylmethyl ether), ethylene glycol Bis (3,4-epoxycyclohexyl methyl ether), 2,3,4,15-diepoxy-7,11,18,21-tetraoxatrispiro- [5.2.2.5.2.2] henicosane ( Or 3, -Epoxycyclohexane spiro-2 ', 6'-dioxane spiro-3'',5''-dioxanespiro-3''', 4 '''-compound that can also be named epoxycyclohexane), 4- (3,4 Epoxycyclohexyl) -2,6-dioxa-8,9-epoxyspiro [5.5] undecane, 4-vinylcyclohexene dioxide, bis-2,3-epoxycyclopentyl ether, dicyclopentadiene dioxide and the like.

  Examples of the aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. Specifically, for example, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, Polyethers of polyether polyols obtained by adding one or more alkylene oxides (ethylene oxide or propylene oxide) to aliphatic polyhydric alcohols such as diglycidyl ether of propylene glycol, ethylene glycol, propylene glycol and glycerin A glycidyl ether etc. are mentioned.

  The epoxy compounds illustrated here may be used alone or in combination with a plurality of epoxy compounds.

  The epoxy equivalent of the epoxy compound used for the solventless adhesive is usually in the range of 30 to 3,000 g / equivalent, and preferably in the range of 50 to 1,500 g / equivalent. When the epoxy equivalent is less than 30 g / equivalent, there is a possibility that the flexibility of the protective film after curing is lowered or the adhesive strength is lowered. On the other hand, if it exceeds 3,000 g / equivalent, the compatibility with other components may be reduced.

  In order to cure the epoxy compound by cationic polymerization, a cationic polymerization initiator is blended. The cationic polymerization initiator generates a cationic species or a Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, or by heating, and initiates an epoxy group polymerization reaction. Regardless of the type of cationic polymerization initiator, it is preferable from the viewpoint of workability that potential is imparted.

  Hereinafter, the cationic photopolymerization initiator will be described. When a photocationic polymerization initiator is used, curing at room temperature becomes possible, the need to consider the heat resistance of the polarizer or distortion due to expansion is reduced, and the protective film can be satisfactorily adhered. Moreover, since the photocationic polymerization initiator acts catalytically by light, it is excellent in storage stability and workability even when mixed with an epoxy compound.

  Examples of the compound that generates a cation species or a Lewis acid by irradiation with active energy rays include aromatic diazonium salts, onium salts such as aromatic iodonium salts and aromatic sulfonium salts, and iron-allene complexes. Among these, aromatic sulfonium salts are particularly preferably used because they have ultraviolet absorption characteristics even in a wavelength region of 300 nm or more, and can provide a cured product having excellent curability and good mechanical strength and adhesive strength. It is done.

These photocationic polymerization initiators can be easily obtained as commercial products, for example, “Kayarad PCI-220” and “Kayarad PCI-620” (manufactured by Nippon Kayaku Co., Ltd.) under the trade names, respectively. "UVI-6990" (manufactured by Union Carbide), "Adekaoptomer SP-150", "Adekaoptomer SP-170" (manufactured by ADEKA Corporation), "CI-5102", "CIT-1370"",CIT-1682","CIP-1866S","CIP-2048S","CIP-2064S" (manufactured by Nippon Soda Co., Ltd.), "DPI-101", "DPI-102", "DPI" -103 "," DPI-105 "," MPI-103 "," MPI-105 "," BBI-101 "," BBI-102 "," BBI-103 " , “BBI-105”, “TPS-101”, “TPS
-102 "," TPS-103 "," TPS-105 "," MDS-103 "," MDS-105 "," DTS-102 "," DTS-103 "(manufactured by Midori Chemical Co., Ltd.), “PI-2074” (manufactured by Rhodia) and the like. In particular, “CI-5102” manufactured by Nippon Soda Co., Ltd. is one of preferred initiators.

  The compounding quantity of a photocationic polymerization initiator is in the range of 0.5-20 mass parts normally with respect to 100 mass parts of epoxy compounds, Preferably it is 1 mass part or more, Preferably it is 15 mass parts or less.

  Furthermore, a photosensitizer can be used in combination as necessary. By using a photosensitizer, the reactivity is improved, and the mechanical strength and adhesive strength of the cured product can be improved. Examples of the photosensitizer include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreductive dyes. When mix | blending a photosensitizer, the quantity exists in the range of about 0.1-20 mass parts, for example by making photocationic polymerizable epoxy resin composition into 100 mass parts.

  Next, the thermal cationic polymerization initiator will be described. Examples of the compound that generates a cationic species or a Lewis acid by heating include benzylsulfonium salt, thiophenium salt, thiolanium salt, benzylammonium, pyridinium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester, and amine imide. These thermal cationic polymerization initiators can also be easily obtained as commercial products. For example, “ADEKA OPTON CP77” and “ADEKA OPTON CP66” (manufactured by ADEKA Corporation), “CI-” 2639 "and" CI-2624 "(manufactured by Nippon Soda Co., Ltd.)," Sun-Aid SI-60L "," Sun-Aid SI-80L "and" Sun-Aid SI-100L "(manufactured by Sanshin Chemical Industry Co., Ltd.) ) And the like.

  In addition, it is also a useful technique to use the above-described photocationic polymerization and thermal cationic polymerization in combination.

  The epoxy adhesive may further contain a compound that promotes cationic polymerization, such as oxetanes and polyols.

  Even when a solventless adhesive is used, the adhesive can be applied to the protective film and / or the adhesive surface of the polarizer, and both can be bonded to form a polarizing plate. There is no particular limitation on the method of applying the solventless adhesive to the polarizer or the protective film. For example, various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater are used. be able to. Moreover, since each coating method has an optimum viscosity range, the viscosity may be adjusted using a small amount of solvent. The solvent used for this purpose only needs to dissolve the epoxy adhesive well without degrading the optical performance of the polarizer. For example, hydrocarbons typified by toluene, esters typified by ethyl acetate, and the like. Organic solvents, such as a kind, can be used. When using an epoxy adhesive, the thickness of the adhesive layer is usually 50 μm or less, preferably 20 μm or less, more preferably 10 μm or less, and usually 1 μm or more.

As described above, after the protective film is bonded to the polarizer through the uncured adhesive layer, the epoxy adhesive layer is cured by irradiating active energy rays or heating, and the protective film. Is fixed on the polarizer. In the case of curing by irradiation with active energy rays, ultraviolet rays are preferably used. Specific examples of the ultraviolet light source include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a black light lamp, and a metal halide lamp. What is necessary is just to select suitably the irradiation intensity | strength and irradiation amount of an active energy ray or an ultraviolet-ray so that a polymerization initiator may be activated sufficiently and an adhesive layer, a polarizer, and a protective film after hardening may not be adversely affected.

  In addition, when curing by heating, it can be heated by a generally known method, and the temperature and time at that time sufficiently activate the polymerization initiator, and the cured adhesive layer or polarizer The protective film may be appropriately selected so as not to adversely affect the protective film.

  When the protective film is laminated on one side of the polarizer and the resin film is laminated on the other side, the same adhesive as described above may be used, or a different adhesive may be used. However, it is more preferable to use the same adhesive on both sides of the polarizer because the number of steps and materials can be reduced.

  In the production of the polarizing plate according to the present embodiment, various surface treatments such as corona discharge treatment, ozone treatment, electron beam treatment, UV treatment, anchor coat treatment and the like are performed on the adhesive surface of the polarizer and / or protective film. It is preferable that Thereby, the adhesive force of the surface which consists of an optical soft resin of a protective film after bonding a polarizer through the above adhesives, and a polarizer can be heightened. Among the various surface treatments, corona discharge treatment is more preferable.

  The corona discharge treatment is a treatment in which a high voltage is applied between the electrodes to discharge and activate the film disposed between the electrodes. The effect of the corona discharge treatment varies depending on the type of electrode, electrode interval, voltage, humidity, type of film used, etc. The conditions of the corona discharge treatment are, for example, the electrode interval within the range of 1 to 5 mm, and the moving speed. It is preferable to set within a range of about 3 to 20 m / min. After the corona discharge treatment, a polarizer is bonded to the treated surface via an adhesive as described above. In the case where the protective film is laminated on one side of the polarizer and the resin film is laminated on the other side, the same surface treatment as described above may be used.

  Thus, a protective film is laminated on at least one surface of a polarizer made of a polyvinyl alcohol-based resin on which a dichroic dye is adsorbed and oriented, and a polarizing plate whose adhesive surface to the polarizer is made of an optical soft resin Is provided.

  The polarizing plate thus obtained can be made into a polarizing plate with an adhesive by forming an adhesive layer on the outside of one protective film. In this case, the surface of the pressure-sensitive adhesive layer is usually covered with a release film.

(Laminated optical member)
When the polarizing plate is used, a laminated optical member in which an optical layer showing an optical function other than the polarizing function is provided on at least one surface can be used. Examples of the optical layer that can be laminated on the polarizing plate for the purpose of forming a laminated optical member include a reflective layer, a transflective reflective layer, a light diffusing layer, a retardation film, a light condensing sheet, a brightness enhancement film, and the like. Examples include various optical layers used for forming a display device. Among these, the reflective layer, the transflective reflective layer, and the light diffusing layer are used when forming a laminated optical member composed of a reflective or transflective or diffusive polarizing plate. .

  A laminated optical member as a reflective polarizing plate is used in a liquid crystal display device of a type that reflects and displays incident light from the viewing side. Since a light source such as a backlight can be omitted, the liquid crystal display device can be easily thinned. The laminated optical member as a transflective polarizing plate is used in a liquid crystal display device of a type that displays as a reflective type in a bright place and displays through a light source such as a backlight in a dark place.

A laminated optical member as a reflective polarizing plate can be produced, for example, by attaching a foil or vapor deposition film made of a metal such as aluminum to a protective film on a polarizer and forming a reflective layer. A laminated optical member as a transflective polarizing plate is formed, for example, by using the above reflective layer as a half mirror, or by adhering a reflective plate exhibiting light transmittance to the polarizing plate by containing a pearl pigment or the like. can do. On the other hand, a laminated optical member as a diffusion type polarizing plate can be applied to various methods such as a method of performing a mat treatment on a protective film on a polarizing plate, a method of applying a resin containing fine particles, and a method of adhering a film containing fine particles. Can be produced by forming a fine relief structure on the surface.

  Further, the laminated optical member can be formed as a reflection / diffusion polarizing plate by, for example, a method of providing a reflective layer reflecting the fine concavo-convex structure on the surface of the diffusion-type polarizing plate. . The reflective layer having a fine concavo-convex structure has the advantage that incident light can be diffused by irregular reflection, directivity and glare can be prevented, and uneven brightness can be suppressed. In addition, the resin layer or film containing fine particles has an advantage that incident light and its reflected light are diffused when passing through the fine particle-containing layer, and uneven brightness can be further suppressed.

  The reflective layer reflecting the surface fine concavo-convex structure can be formed, for example, by directly attaching a metal to the surface of the fine concavo-convex structure by a method such as vacuum deposition, ion plating, sputtering, or other vapor deposition or plating. . Examples of the fine particles to be blended to form the surface fine uneven structure include, for example, silica, aluminum oxide, titanium oxide, zirconia, tin oxide, indium oxide, cadmium oxide having an average particle diameter in the range of 0.1 to 30 μm, and Inorganic fine particles made of antimony oxide or the like, organic fine particles made of a crosslinked or uncrosslinked polymer, or the like can be used.

  On the other hand, the above-mentioned retardation film as an optical layer is used for the purpose of compensation of retardation by a liquid crystal cell. Examples thereof include a birefringent film composed of stretched films of various plastics, a film in which a discotic liquid crystal or a nematic liquid crystal is oriented and fixed, and a film in which the above liquid crystal layer is formed on a film substrate. In this case, a cellulose-based resin film such as triacetyl cellulose is preferably used as the film substrate that supports the oriented liquid crystal layer.

  Examples of the plastic forming the birefringent film include amorphous polyolefin resins (cycloolefin resins), cellulose acetate resins, polycarbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polypropylene and other polyolefins, polyacrylates, Examples thereof include polyamide.

  The stretched film may be processed by an appropriate stretching method such as uniaxial stretching or biaxial stretching. Moreover, the birefringent film which controlled the refractive index of the thickness direction of a film by applying a shrinkage force and / or extending | stretching force under adhesion | attachment with a heat-shrinkable film may be sufficient. Note that two or more retardation films may be used in combination for the purpose of controlling optical characteristics such as broadening the bandwidth.

  The light condensing sheet is used for the purpose of optical path control and can be formed as a prism array sheet, a lens array sheet, a dot-attached sheet, or the like.

  The brightness enhancement film is used for the purpose of improving the brightness in a liquid crystal display device or the like. For example, a plurality of thin film films having different refractive index anisotropies are laminated to make the reflectance anisotropy. Examples thereof include a reflection-type polarization separation sheet designed so as to occur, a circularly polarized light separation sheet in which an alignment film of a cholesteric liquid crystal polymer and an alignment liquid crystal layer thereof are supported on a film substrate.

The laminated optical member is a single layer or two selected from the polarizing plate, the reflective layer, the transflective reflective layer, the light diffusion layer, the retardation film, the condensing sheet, and the brightness enhancement film described above according to the purpose of use. Two or more optical layers can be combined to form a laminate of two layers or three or more layers. In that case, two or more optical layers such as a light diffusion layer, a retardation film, a condensing sheet, and a brightness enhancement film may be disposed. There is no particular limitation on the arrangement of each optical layer.

  The various optical layers forming the laminated optical member are integrated using an adhesive, but the adhesive used for this purpose is not particularly limited as long as the adhesive layer is well formed. For example, “( The adhesive mentioned above in the section “C) Polarizing plate” can be mentioned. Moreover, it is also preferable to use the adhesive mentioned later from the viewpoints of easy bonding work and prevention of optical distortion.

  Such a laminated optical member is also bonded to the liquid crystal cell on the desired surface via an adhesive, like the polarizing plate. As the pressure-sensitive adhesive, those using a base polymer such as an acrylic ester, methacrylic ester, butyl rubber, or silicone can be used. More specifically, polymers based on (meth) acrylate esters such as butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Polymers based on copolymers using two or more of these (meth) acrylic acid esters are preferably used.

  The pressure-sensitive adhesive usually has a polar monomer copolymerized in these base polymers. Examples of the polar monomer include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, and (meth) acrylic acid 2. And monomers having a carboxyl group, a hydroxyl group, an amino group, an epoxy group, and the like, such as -hydroxypropyl, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, and glycidyl (meth) acrylate.

  Examples of the crosslinking agent include divalent or polyvalent metal salts that form a carboxylic acid metal salt with a carboxyl group, polyisocyanate compounds that form an amide bond with a carboxyl group, and the like. One or two or more crosslinking agents are used as a mixture with the base polymer. The thickness of a general pressure-sensitive adhesive layer is in the range of about 5 to 50 μm. When the pressure-sensitive adhesive layer is applied to the polarizing plate, surface treatment such as corona treatment may be applied to the protective film surface of the polarizing plate depending on the situation.

(Liquid crystal display device)
The polarizing plate or the laminated optical member according to the present embodiment may be attached to a liquid crystal cell via an adhesive in a state of being laminated with another optical layer as described above as necessary to form a liquid crystal display device. it can. In the liquid crystal display device, as described above, an adhesive layer is formed on the outside of one protective film to form a polarizing plate with an adhesive, and the adhesive layer side is bonded so that the liquid crystal cell faces. In the case of a laminated optical member, it may be bonded to the liquid crystal cell on the surface other than the protective film of the polarizing plate. The liquid crystal cell constituting the liquid crystal display device is a liquid crystal of various modes known in this field such as TN (Twisted Nematic), STN (Super Twisted Nematic), VA (Vertical Alignment), IPS (In-Plane Switching), etc. A cell can be employed.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

  Moreover, all the academic literatures and patent literatures described in this specification are incorporated herein by reference.

  The present invention can be used for various liquid crystal display devices.

It is a front view which shows schematic structure of the polarizing plate which concerns on one Embodiment of this invention. It is sectional drawing which shows schematic structure of the polymer filter used for the manufacturing method of the polarizing plate which concerns on one Embodiment of this invention. It is a front view which shows schematic structure of the film which concerns on one Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Housing 2 Leaf disk 3 Center post 4 Inlet 5 Outlet 10 Polarizing plate 11 Protective film 12 Surface 13 Polarizer 14 Retardation film 15 Layer containing soft optical resin 16 layers

Claims (17)

A polarizer,
A protective film having a surface made of a soft optical resin,
The polarizing plate is characterized in that the polarizer is in contact with a surface made of the optical soft resin.   The polarizing plate according to claim 1, wherein the protective film is a retardation film.   The protective film has one or more functions selected from the group consisting of an antireflection function, an antiglare function, a scratch prevention function, an antifouling function, an ultraviolet protection function, and an antistatic function. The polarizing plate according to claim 1 or 2.   The polarizing plate according to claim 1, wherein the protective film is a multilayer film.   The polarizing plate according to claim 4, wherein the protective film includes an adhesive layer.   The polarizing plate according to claim 1, wherein the optical soft resin has a glass transition temperature of 90 ° C. or lower.   The optical soft resin is made of one or more resins selected from the group consisting of amorphous polyester resins, polyamide resins, and amorphous olefin resins. The polarizing plate as described in a term. The optical soft resin contains an additive,
8. The polarizing plate according to claim 1, wherein the amount of the additive is 0.5 parts by weight or less with respect to 100 parts by weight of the optical soft resin. The optical soft resin contains a catalyst residue,
The polarizing plate according to claim 1, wherein the amount of the catalyst residue is 0.02 parts by weight or less with respect to 100 parts by weight of the optical soft resin.   The polarizing plate according to any one of claims 1 to 9, wherein the polarizer and the protective film are laminated via an aqueous adhesive.   The polarizing plate according to claim 10, wherein the water-based adhesive contains a crosslinkable epoxy resin.   The polarizing plate according to any one of claims 1 to 9, wherein the polarizer and the protective film are laminated via a solventless epoxy adhesive.   The polarizing plate according to claim 12, wherein the solventless epoxy adhesive is thermosetting or photocurable. A method for producing a polarizing plate comprising a polarizer and a protective film having a surface made of a soft optical resin,
A surface treatment step of performing a surface treatment on at least one of the surface of the polarizer and the optical soft resin;
A method for producing a polarizing plate, comprising, after the surface treatment step, a bonding step of bonding the polarizer and the surface made of the optical soft resin through an adhesive.   A laminated optical member comprising the polarizing plate according to claim 1.   The laminated optical member according to claim 15, further comprising a retardation film.   A polarizing plate according to any one of claims 1 to 13 or a laminated optical member according to claim 15 or 16 is bonded to a liquid crystal cell via an adhesive. .

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