WO2013038829A1 - Polarizer and liquid-crystal display device - Google Patents

Polarizer and liquid-crystal display device Download PDF

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Publication number
WO2013038829A1
WO2013038829A1 PCT/JP2012/069675 JP2012069675W WO2013038829A1 WO 2013038829 A1 WO2013038829 A1 WO 2013038829A1 JP 2012069675 W JP2012069675 W JP 2012069675W WO 2013038829 A1 WO2013038829 A1 WO 2013038829A1
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WIPO (PCT)
Prior art keywords
cellulose acylate
acylate film
acid
film
polarizer
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PCT/JP2012/069675
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French (fr)
Japanese (ja)
Inventor
佐藤　英幸
Original Assignee
コニカミノルタアドバンストレイヤー株式会社
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Application filed by コニカミノルタアドバンストレイヤー株式会社 filed Critical コニカミノルタアドバンストレイヤー株式会社
Priority to KR1020147004980A priority Critical patent/KR101605978B1/en
Priority to CN201280044187.4A priority patent/CN103975260B/en
Priority to JP2013533567A priority patent/JP5888333B2/en
Publication of WO2013038829A1 publication Critical patent/WO2013038829A1/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/12—Cellulose acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • the present invention relates to a polarizing plate and a liquid crystal display device using cellulose acylate.
  • cellulose esters cellulose acylate is known to be applicable to optical films having a wide range of retardation by changing the acyl group substitution degree.
  • triacetyl cellulose (TAC) having a high degree of acetyl group substitution is suitably used for a protective film for polarizing plates because of its low retardation.
  • TAC triacetyl cellulose
  • a retardation increasing agent for example, patents
  • diacetyl cellulose (DAC) having a low degree of acetyl group substitution has high retardation expression, and therefore can function as an optical compensation film without adding a retardation increasing agent. Expected.
  • a film made of cellulose acylate having a low acyl group substitution degree is used as an optical compensation film, it is generally bonded to a polarizer to produce a polarizing plate. And when durability as a polarizing plate is considered, the adhesiveness between a cellulose acylate film and a polarizer is so preferable that it is high.
  • photo-curing adhesives have attracted attention as adhesives when laminating polarizers and polarizing plate protective films (see, for example, Patent Documents 2 to 4). Since the photocurable adhesive can be bonded to the polarizer without passing through the alkali saponification step, it can be expected to be applied to cellulose acylate having a low degree of acyl group substitution.
  • This invention is made
  • An object of the present invention is to provide a polarizing plate that improves and further reduces the decrease in the degree of polarization. Moreover, it is providing the liquid crystal display device provided with the said polarizing plate.
  • the present inventor adopts a cellulose acylate film containing a cellulose acylate having a low acyl group substitution degree and a glass transition temperature lowering agent in the course of examining the cause of the above-mentioned problem. It has been found that a high retardation value and high phase difference expression are exhibited while being a thin film.
  • the present inventors use a photocurable adhesive to bond a polarizer and a cellulose acylate film, the distribution of the glass transition temperature lowering agent on the bonding surface is made larger than that on the other surface, thereby bonding. It has been found that the adhesion of the mating surface is improved and a decrease in the degree of polarization is suppressed, and the present invention has been achieved.
  • a cellulose acylate film containing a cellulose acylate having an acyl group substitution degree in the range of 2.0 to 2.5 and a glass transition temperature lowering agent is bonded to one of the polarizers using a photocurable adhesive.
  • a polarizing plate bonded to a surface, The detected value of the glass transition temperature reducing agent on the bonding surface of the cellulose acylate film, detected using time-of-flight secondary ion mass spectrometry (TOF-SIMS), is d A , and the detected value of the other surface
  • the polarizing plate is characterized in that the r value represented by the following formula (1) is 1.1 or more, where d is B.
  • Formula (1) r d A / d B 2.
  • the glass transition temperature lowering ability of the glass transition temperature lowering agent is 3.5 ° C./part by mass or more. 4).
  • the cellulose acylate film further comprises a hydrolysis inhibitor, The polarizing plate according to any one of Items 1 to 3, wherein the hydrolysis inhibitor has an average log P value of 7.5 or more. 5.
  • a liquid crystal display device comprising the polarizing plate according to any one of items 1 to 6.
  • the adhesion between the cellulose acylate film and the polarizer can be improved, and the decrease in the degree of polarization of the polarizing plate can be alleviated.
  • the expression mechanism or action mechanism of the effect of the present invention has not been clarified, but is presumed as follows. That is, when a cellulose acylate film is bonded to a polarizer using a photocurable adhesive, the bonding surface is smaller than the other surface due to the presence of a glass transition temperature reducing agent in the bonding surface. Has a rough surface structure. This surface structure is considered to contribute to the improvement of the adhesion with the polarizer.
  • the abundance of cellulose acylate decreases with an increase in the abundance of the glass transition temperature lowering agent on the bonding surface. Therefore, it is considered that the retardation value of the cellulose acylate film in the vicinity of the bonding surface is smaller than the value of the whole cellulose acylate film.
  • the retardation value of the cellulose acylate film is higher, the decrease in the degree of polarization due to misalignment at the time of bonding is more conspicuous, and by bonding the bonding surface and the polarizer with a relatively small retardation, It is thought that the decrease in the degree of polarization is alleviated.
  • the polarizing plate of the present invention comprises a cellulose acylate film containing a cellulose acylate having an acyl group substitution degree in the range of 2.0 to 2.5 and a glass transition temperature reducing agent, and a photocurable adhesive.
  • the polarizing plate is bonded to one surface of a polarizer using the time-of-flight secondary ion mass spectrometry (TOF-SIMS), and the bonding surface of the cellulose acylate film is detected using the polarizing plate.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • the cellulose acylate is preferably diacetylcellulose having an acyl group substitution degree in the range of 2.0 to 2.5.
  • the glass transition temperature decreasing ability of the said glass transition temperature decreasing agent is 3.5 degreeC / mass part or more.
  • the said cellulose acylate film further contains a hydrolysis inhibiting agent and the average logP value of the said hydrolysis inhibiting agent is 7.5 or more.
  • the arithmetic mean roughness of the said bonding surface is larger than the other surface.
  • the polarization degree of the polarizing plate is preferably 99.99% or more.
  • the polarizing plate of the present invention can be suitably included in a liquid crystal display device.
  • ⁇ is used in the sense of including the numerical values described before and after it as the lower limit value and the upper limit value.
  • the polarizing plate according to the present invention is a photocurable adhesive comprising a cellulose acylate film having an acyl group substitution degree in the range of 2.0 to 2.5 and a glass transition temperature reducing agent. It is bonded to one surface of the polarizer using an agent.
  • the cellulose acylate film used in the present invention contains cellulose acylate having an acyl group substitution degree in the range of 2.0 to 2.5.
  • cellulose acylate having a low acyl group substitution degree in this way, high retardation development is exhibited, and even when a retardation film having a high retardation is obtained, a thin film can be obtained.
  • the stretch ratio can be kept low, and advantages such as failure such as breakage can be avoided.
  • the cellulose molecule is composed of many glucose units connected, and the glucose unit has three hydroxy groups (hydroxyl groups).
  • the number of acyl groups derived from these three hydroxy groups is called the degree of acyl group substitution.
  • diacetyl cellulose (DAC) has an acetyl group bonded to an average of 2.0 to 2.5 hydroxy groups among the three hydroxy groups of the glucose unit.
  • Examples of the cellulose acylate used in the present invention include carboxylic acid esters having about 2 to 22 carbon atoms, which may be aromatic carboxylic acid esters, but are particularly preferably lower fatty acid esters of cellulose.
  • the lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms.
  • the acyl group bonded to the hydroxy group may be linear or branched, and may form a ring. Furthermore, another substituent may be substituted.
  • the carbon number is preferably selected from acyl groups having 2 to 6 carbon atoms.
  • the acyl group preferably has 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms.
  • the acyl group substitution degree of cellulose acylate can be measured in accordance with ASTM D-817-91, and the preferred acyl group substitution degree is 2.18 to 2.45.
  • the acyl group substitution degree of cellulose acylate is 2.0 or more, it is possible to prevent the occurrence of deterioration in film surface quality due to increase in dope viscosity and haze-up due to increase in stretching tension. Further, when the acyl group substitution degree is 2.5 or less, a necessary phase difference is easily obtained.
  • the number average molecular weight (Mn) of the cellulose acylate is preferably in the range of 30000 to 300000, since the mechanical strength of the obtained cellulose acylate film is strong. Further, cellulose acylate having a number average molecular weight of 50,000 to 200,000 is preferably used.
  • the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) of the cellulose acylate is preferably in the range of 1.4 to 3.0.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) of cellulose acylate are measured using gel permeation chromatography (GPC).
  • the measurement conditions are as follows. Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three products manufactured by Showa Denko KK) Column temperature: 25 ° C Sample concentration: 0.1% by mass Detector: RI Model 504 (manufactured by GL Sciences) Pump: L6000 (manufactured by Hitachi, Ltd.) Flow rate: 1.0ml / min
  • the cellulose acylate used in the present invention can be synthesized by a known method. Specifically, it can be synthesized with reference to the method described in JP-A-10-45804.
  • Cellulose as a raw material for cellulose acylate is not particularly limited, and examples thereof include cotton linter, wood pulp (derived from coniferous tree, derived from broadleaf tree), kenaf and the like. Moreover, you may use the cellulose acylate obtained from them by mixing in arbitrary ratios, respectively.
  • a commercially available cellulose acylate may be used. Examples of commercially available cellulose acylates include L20, L30, L40, and L50 manufactured by Daicel, and Ca398-3, Ca398-6, Ca398-10, Ca398-30, and Ca394-60S manufactured by Eastman Chemical.
  • the cellulose acylate film used in the present invention contains a glass transition temperature lowering agent (hereinafter referred to as Tg lowering agent).
  • Tg lowering agent glass transition temperature lowering agent
  • the glass transition temperature Tg of the cellulose acylate which has a hard and brittle property can fall, and the workability and mechanical physical property can be improved.
  • the cellulose acylate film has a high retardation value despite being a thin film, suppresses an increase in internal haze even when stretched at a high magnification, reduces retardation unevenness, and suppresses an increase in haze even in a humid heat environment. Can be provided.
  • the Tg lowering agent used in the present invention is a glass transition temperature Tg of a cellulose acylate having an acyl group substitution degree of 2.0 to 2.5 that does not contain it. Any substance may be used as a Tg lowering agent as long as it means an additive that lowers and satisfies such a definition.
  • the value of the glass transition temperature Tg of a cellulose acylate film is a value measured by the differential scanning calorimetry (DSC).
  • cellulose acylate having an acyl group substitution degree of 2.0 to 2.5 when a substance falls within the case of not meeting the definition of a Tg reducing agent, the substance is: If it is used in combination with a cellulose acylate having an acyl group substitution degree of 2.0 to 2.5 when the definition falls within the definition of a Tg reducing agent, it can be used as a Tg reducing agent in the present invention.
  • the glass transition temperature lowering ability (hereinafter referred to as Tg lowering ability) of the Tg lowering agent is not particularly limited, but is preferably 3.5 ° C / part by mass or more, more preferably 3.8 ° C / part by mass. It is above, More preferably, it is 4.0 degrees C / mass part or more.
  • the Tg lowering ability means the ability to lower the glass transition temperature Tg per unit mass of a certain substance, and is defined by the following mathematical formula (3).
  • X represents a glass transition temperature Tg of a cellulose acylate film obtained by independently forming a cellulose acylate
  • Y represents 5 parts by mass of a Tg reducing agent with respect to 100 parts by mass of the cellulose acylate.
  • the glass transition temperature Tg of the cellulose acylate film obtained by adding a film in the same manner after the addition is shown.
  • the Tg reducing ability of the Tg reducing agent is a value within the above range, an excellent Tg reducing effect can be exhibited even with a small addition amount. For this reason, the bleed-out etc. which generate
  • the upper limit of the Tg lowering ability is not particularly limited, but is actually about 5.0 ° C./part by mass or less.
  • the substance used as the Tg lowering agent is included in the preferred range of the above Tg lowering ability. Cases and cases that are not included. In such a case, the substance is preferable as described above only when the substance is used in combination with cellulose acylate having an acyl group substitution degree of 2.0 to 2.5 when included in the preferable range of the above-described Tg reducing ability. It shall be interpreted as a Tg lowering agent that satisfies the range of Tg lowering ability.
  • Tg reducing agent used in the present invention is not particularly limited as long as the definition of the Tg reducing agent described above is satisfied, and preferably the preferable range of the Tg reducing ability described above is satisfied.
  • An example of the Tg lowering agent is a polyester compound represented by the following general formula (I).
  • General formula (I) X—O—B— ⁇ O—C ( ⁇ O) —A—C ( ⁇ O) —O—B ⁇ n —O—X wherein B is a straight chain having 2 to 6 carbon atoms A chain or branched alkylene group, or a linear or branched cycloalkylene group is represented.
  • A represents an aromatic ring having 6 to 14 carbon atoms, a linear or branched alkylene group having 2 to 6 carbon atoms, or a linear or branched cycloalkylene group having 2 to 6 carbon atoms.
  • X represents a hydrogen atom or a monocarboxylic acid residue containing an aromatic ring having 6 to 14 carbon atoms.
  • n represents a natural number of 1 or more.
  • the polyester compound represented by formula (I) has an aromatic ring (6 to 14 carbon atoms), a linear or branched alkylene group, or a linear or branched cycloalkylene group (both having 2 to 6 carbon atoms).
  • the aromatic dicarboxylic acid and the dicarboxylic acid having a linear or branched alkylene group or cycloalkylene group may be used alone or as a mixture, but from the viewpoint of compatibility with cellulose acylate. It is preferable that at least 10% or more of the aromatic dicarboxylic acid is contained. Alternatively, both ends may be sealed with a monocarboxylic acid having an aromatic ring (having 6 to 14 carbon atoms).
  • dicarboxylic acids having an aromatic ring (6 to 14 carbon atoms) that is, aromatic dicarboxylic acids having 6 to 16 carbon atoms
  • aromatic dicarboxylic acids having 6 to 16 carbon atoms include phthalic acid, isophthalic acid, terephthalic acid, 1,5-naphthalenedicarboxylic acid, 1,4- Naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,8-naphthalenedicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 4,4'- And biphenyl dicarboxylic acid.
  • terephthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-biphenyldicarboxylic acid are preferable.
  • dicarboxylic acid having a linear or branched alkylene group or cycloalkylene group examples include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and 1,2-cyclohexanedicarboxylic acid. Examples thereof include acid and 1,4-cyclohexanedicarboxylic acid. Of these, succinic acid, adipic acid, and 1,4-cyclohexanedicarboxylic acid are preferable.
  • linear or branched alkylene diol or cycloalkylene diol having 2 to 6 carbon atoms examples include ethanediol (ethylene glycol), 1,2-propanediol, 1,3-propanediol, and 1,2-butane.
  • ethanediol ethylene glycol
  • 1,2-propanediol, 1,3-propanediol, and 1,3-butanediol are preferable.
  • A is preferably a benzene ring, naphthalene ring or biphenyl ring which may have a substituent, from the viewpoint of excellent Tg lowering ability.
  • the substituent that the benzene ring, naphthalene ring or biphenyl ring may have is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
  • Examples of monocarboxylic acids having aromatic rings (6 to 14 carbon atoms) that seal both ends of the polyester compound include benzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, p-tert-butylbenzoic acid, and dimethylbenzoic acid. And paramethoxybenzoic acid. Of these, benzoic acid, p-toluic acid and p-tert-butylbenzoic acid are preferred.
  • Aromatic polyester compounds are prepared by the conventional methods of polyesterification reaction of dicarboxylic acid and alkylene diol or cycloalkylene diol, hot melt condensation method by transesterification, or interfacial condensation method of acid chlorides of these acids and glycols. It can be easily synthesized by any method. Furthermore, by adding the aromatic monocarboxylic acid described above, a polyester compound in which both ends are sealed can be synthesized.
  • aromatic polyester compounds (PES-1) to (PES-14) and (ar-1) to (ar-20) that can be used in the present invention are shown below.
  • the aromatic polyester compound represented by the general formula (I) has been described in detail as a specific example of the Tg reducing agent, but other Tg reducing agents may be used as a matter of course.
  • Tg reducing agent In the cellulose acylate film according to one embodiment of the present invention, only one Tg reducing agent may be used alone, or two or more Tg reducing agents may be used in combination.
  • the amount of the Tg reducing agent added to the cellulose acylate film according to one embodiment of the present invention is not particularly limited, but is preferably 1 to 5% by mass, more preferably 100% by mass with respect to cellulose acylate. Is 1.5 to 3.5% by mass.
  • the added amount of the Tg reducing agent is 1% by mass or more, the Tg reducing performance that is the original purpose of the Tg reducing agent can be sufficiently exhibited.
  • the addition amount of the Tg reducing agent is 5% by mass or less, the retardation development performance of the cellulose acylate film accompanying the increase in the addition amount of the T reducing agent can be prevented.
  • a cellulose acylate film according to an embodiment of the present invention is obtained by Time-Of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) on a bonding surface with a polarizer and other surfaces.
  • the detection value of the Tg lowering agent is characterized by a certain degree of bias.
  • the detected value of the Tg reducing agent on the bonding surface with the polarizer of the cellulose acylate film, detected using time-of-flight secondary ion mass spectrometry is expressed as d A , and the other surface.
  • r value shown by the following formula (1) is 1.1 or more.
  • Formula (1) r d A / d B
  • time-of-flight secondary ion mass spectrometry can measure the chemical information of atoms and molecules on a solid sample with a sensitivity of one molecular layer or less, and the distribution of specific atoms and molecules with a spatial resolution of 100 nm or less. This is an observable mass spectrometry method.
  • Time-of-flight secondary ion mass spectrometry is a type of secondary ion mass spectrometry (SIMS), in which a solid sample is irradiated with a primary ion beam, and ions emitted from the outermost surface of the sample (two Analysis is performed by detecting (secondary ions).
  • SIMS secondary ion mass spectrometry
  • TOF-MS time-of-flight mass spectrometer
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • the r value may be 1.1 or more, preferably 1.2 or more, more preferably 1.3 or more, and further preferably 1.4 or more.
  • the definition and preferred form of the r value which is an essential constituent requirement in the present invention, have been described, but as a preferred embodiment based on another viewpoint of the cellulose acylate film according to the present invention, along the thickness direction of the film.
  • a form in which there is a concentration gradient of the Tg reducing agent can be mentioned.
  • the cellulose acylate film according to the present invention when cut so as to be divided into two equal parts by a plane perpendicular to the thickness direction (a plane parallel to the plane direction of the film),
  • An embodiment in which the amount of the Tg reducing agent present in the fragment including the bonding surface with the polarizer is larger than the amount of the Tg reducing agent present in the other fragment (the fragment including the other surface) is preferably exemplified.
  • each piece An embodiment in which the amount of the Tg reducing agent present in is gradually decreased from the fragment containing the bonding surface with the polarizer toward the fragment containing the other surface is also preferably exemplified.
  • the adhesiveness with the polarizer constituting the polarizing plate is further improved by being configured so that the r value is 1.1 or more.
  • the r value is 1.1 or more.
  • cellulose acylate such as DAC having a low acyl group substitution degree is used not only as a retardation film but also as an optical compensation film for expanding a viewing angle, it is bonded to a polarizer to constitute a polarizing plate. It is common. And when durability as a polarizing plate is considered, the adhesiveness between a cellulose acylate film and a polarizer is so preferable that it is high.
  • the mechanism for improving the adhesion is not completely clear, but according to the study of the present inventor, the following mechanism is presumed.
  • the cellulose acylate film is usually produced through a step of drying a film obtained by casting a dope containing cellulose acylate and an additive on a support, peeling it, and then stretching it.
  • the r value of the obtained cellulose acylate film is 1.1 or more
  • one surface of the obtained cellulose acylate film has minute unevenness as compared with the other surface. Many were found to exhibit a rough surface structure.
  • the bonding surface of the cellulose acylate film is usually subjected to alkali saponification treatment for the purpose of improving the adhesion at the time of bonding between the polarizer and the cellulose acylate film.
  • the adhesion between the polarizer and the polarizer is improved by the mechanism as described above, so that it is expected that such alkali saponification treatment is unnecessary.
  • a cost reduction effect can be achieved by reducing the number of man-hours.
  • part of cellulose acylate present on the saponification treatment surface (bonding surface) of the cellulose acylate film may be hydrolyzed, but the adhesion is improved. If the alkali saponification treatment becomes unnecessary, the possibility of hydrolysis of the cellulose acylate during the alkali saponification treatment is eliminated, and a very superior technique is provided.
  • a preferred embodiment of the cellulose acylate film according to one aspect of the present invention is a quantitative representation of the presence of a surface structure composed of minute irregularities that contributes to improvement in adhesion to a polarizer by the above-described mechanism. is there. That is, in the cellulose acylate film according to one embodiment of the present invention, the arithmetic average roughness Ra measured by JIS B0601: 2001 on the bonding surface with the polarizer, out of the two surfaces of the film, It is preferably larger than the value on the other surface.
  • the value of the arithmetic average roughness Ra on the bonding surface is preferably 1.05 times or more, more preferably 1.1 times or more, more preferably the value of the arithmetic average roughness Ra on the other surface. Is 1.2 times or more, particularly preferably 1.3 times or more, and most preferably 1.4 times or more.
  • the cellulose acylate film according to one embodiment of the present invention provides a certain solution to such a demand. That is, according to the cellulose acylate film according to one embodiment of the present invention, even if a slight axis shift occurs during bonding with a polarizer, a decrease in the degree of polarization of the polarizing plate due to the misalignment can be alleviated. Although the mechanism is not completely clear, the following mechanism has been estimated according to the study of the present inventor.
  • the Tg lowering agent contained in the cellulose acylate film reduces the relative abundance of cellulose acylate contributing to the development of retardation as the abundance in the film increases. become.
  • the retardation values Ro and Rth of the cellulose acylate film are smaller than the macroscopic values of the entire cellulose acylate film.
  • the retardation values Ro and Rth are larger than the macroscopic values of the entire cellulose acylate film.
  • the retardation development performance as a whole film that is, the retardation values Ro and Rth are Is unchanged.
  • the higher the retardation development performance of the cellulose acylate film as the retardation film that is, the retardation values Ro and Rth
  • the axis shift of the cellulose acylate film is likely to occur due to external factors such as shrinkage of the adhesive and heat generation during curing.
  • the surface where a Tg reducing agent exists uniformly in the whole film can be used as a polarizer. Even if the same degree of axial deviation occurs as compared with the case of pasting, the degree of decrease in the degree of polarization of the polarizing plate can be small. As a result, the decrease in the degree of polarization of the polarizing plate due to the axis deviation is alleviated.
  • the cellulose acylate film according to one embodiment of the present invention can contain other additives in addition to the above-described Tg reducing agent.
  • additives that can be used in the present invention will be described.
  • the cellulose acylate film according to one embodiment of the present invention can contain a hydrolysis inhibitor.
  • a cellulose acylate film contains a hydrolysis inhibiting agent, since hydrolysis of a cellulose acylate is prevented, the water resistance of a cellulose acylate film can improve.
  • the hydrolysis inhibitor that can be used in the present invention means that the hydrolysis resistance of a cellulose acylate having no acyl group substitution degree of 2.0 to 2.5 is reduced by adding it. Any substance may be used as a hydrolysis inhibitor so long as it satisfies such a definition.
  • a mass change rate before and after saponification can be used. Specifically, the film is immersed in a 2.0 M KOH aqueous solution at 50 ° C. for 90 seconds, and the mass change rate of the film before and after that is calculated. According to the mass change rate, it is possible to grasp the ratio of cellulose acylate that has been hydrolyzed in the alkaline solution and dissolved in the saponified solution.
  • cellulose acylate having an acyl group substitution degree of 2.0 to 2.5 when a substance falls into the case where it falls under the definition of a hydrolysis inhibitor and when it does not fall, the substance is If it is used in combination with a cellulose acylate having an acyl group substitution degree of 2.0 to 2.5 when it falls under the definition of a hydrolysis inhibitor, it can be used as a hydrolysis inhibitor in the present invention.
  • the log P value is also referred to as an octanol-water partition coefficient or log Pow, and is defined as a common logarithm of the value of the ratio of the distribution concentration of a substance to each phase of a two-phase solvent system composed of n-octanol and water. .
  • the average log P value is determined by first considering the specific log P value of each compound constituting the mixture in consideration of the case where the hydrolysis inhibitor is used as a mixture of a plurality of compounds, and then the mixing ratio of each compound in the mixture. It is calculated by weighting by (mass ratio).
  • the logP value is a value measured by a flask shaking method described in JIS Z-7260-107: 2000. Further, the logP value may be a value estimated by a computational chemical method or an empirical method instead of the actual measurement.
  • the calculation method includes Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, p21 (1987)), Viswanadhan's fragmentation method ( J. Chem. Inf. Comput. Sci., 29, p163 (1989)), Broto's fragmentation method (Eur. J. Med. Chem.-Chim. Theor., 19, p71 (1984)) ClogP method (reference documents Leo, A., Jow, PYC, Silipo, C., Hansch, C., J. Med. Chem., 18, 865, 1975) and the like are preferably used.
  • Crippen's f agmentation method J.Chem.Inf.Comput.Sci., 27 vol., p21 (1987 years) are preferred. However, when the measured value by the flask shaking method mentioned above and the value estimated by the computational chemical method or the empirical method are significantly different, the measured value by the flask shaking method has priority.
  • the average log P value of the hydrolysis inhibitor used in the present invention is preferably 7.5 or more, more preferably 8.0 or more, still more preferably 9.0 or more, and particularly preferably 9.5. That's it.
  • the average log P value of the hydrolysis inhibitor is within such a range, an excellent hydrolysis prevention effect can be exhibited even with a small addition amount. For this reason, generation
  • the specific form of the hydrolysis inhibitor that can be used in the present invention is not particularly limited as long as the definition of the hydrolysis inhibitor described above is satisfied, and preferably the preferable range of the log P value described above is also satisfied.
  • An example of the hydrolysis inhibitor is a sugar ester compound represented by the following general formula (II).
  • G represents the residue of a monosaccharide or a disaccharide.
  • R 2 represents an aliphatic group or an aromatic group.
  • m represents the total number of hydroxy groups directly bonded to the monosaccharide or disaccharide residues.
  • l represents the total number of — (O—C ( ⁇ O) —R 2 ) groups directly bonded to the monosaccharide or disaccharide residue, 3 ⁇ m + l ⁇ 8, and l ⁇ 0. . ]
  • the compound having the structure represented by the general formula (II) is a single type of compound in which the total number m of hydroxy groups and the total number l of — (O—C ( ⁇ O) —R 2 ) groups are fixed. It is difficult to separate, and it is known that a compound in which several components different in m and l in the formula are mixed is obtained. Therefore, the performance as a mixture in which the number m of hydroxy groups and the number 1 of — (O—C ( ⁇ O) —R 2 ) groups are changed is important.
  • monosaccharide of the residue represented by G in the general formula (II) include, for example, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, ribose, arabinose, xylose, lyxose, and the like.
  • disaccharide of the residue represented by G examples include trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, and isotrehalose.
  • trehalose sucrose
  • maltose cellobiose
  • gentiobiose lactose
  • isotrehalose Although the structural example of the compound which has a disaccharide residue represented by general formula (II) below is shown, this invention is not limited to these specific examples.
  • the aliphatic group or aromatic group represented by R 2 may each independently have a substituent.
  • m and l are required to satisfy 3 ⁇ m + l ⁇ 8, and preferably 4 ⁇ m + l ⁇ 8. Also, l ⁇ 0.
  • the — (O—C ( ⁇ O) —R 2 ) groups may be the same or different.
  • the aliphatic group in the definition of R 2 in the general formula (II) may be linear, branched or cyclic.
  • the aliphatic group preferably has 1 to 25 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 2 to 15 carbon atoms.
  • Specific examples of the aliphatic group include, for example, methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, n-butyl, iso-butyl, tert-butyl, amyl, iso-amyl, tert-amyl, n-hexyl.
  • the aromatic group in the definition of R 2 in the general formula (II) may be an aromatic hydrocarbon group or an aromatic heterocyclic group, and more preferably an aromatic hydrocarbon group.
  • the aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms.
  • Specific examples of the aromatic hydrocarbon group include benzene, naphthalene, anthracene, biphenyl, terphenyl and the like.
  • the aromatic hydrocarbon group benzene, naphthalene, and biphenyl are particularly preferable.
  • As an aromatic heterocyclic group what contains at least 1 among an oxygen atom, a nitrogen atom, or a sulfur atom is preferable.
  • heterocyclic ring examples include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline.
  • aromatic heterocyclic group pyridine, triazine, and quinoline are particularly preferable.
  • the inside of the Kolben was depressurized to 4 ⁇ 10 2 Pa or less, and after excess pyridine was distilled off at 60 ° C., the inside of the Kolben was depressurized to 1.3 ⁇ 10 Pa or less and the temperature was raised to 120 ° C. Most of the acid and benzoic acid formed were distilled off. Then, 1 L of toluene and 300 g of a 0.5% by mass aqueous sodium carbonate solution were added, and the mixture was stirred at 50 ° C. for 30 minutes and then allowed to stand to separate a toluene layer.
  • the hydrolysis inhibitor that can be added to the cellulose acylate film according to one embodiment of the present invention exhibits the effect of imparting water resistance to the film as described above. Therefore, it is preferable that the hydrolysis inhibitor is uniformly distributed throughout the film as much as possible, unlike the Tg reducing agent described above.
  • the s value indicated by (2) is preferably less than 1.1.
  • max ⁇ d C , d D ⁇ represents the larger of d C or d D
  • min ⁇ d C , d D ⁇ represents the smaller of d C or d D.
  • this preferred embodiment of the deviation of the detected value of the hydrolysis inhibitor is, This means that the detected value of the hydrolysis inhibitor by secondary ion mass spectrometry is almost non-biased, specifically, only to the extent that the ratio is less than 1.1.
  • the s value is theoretically a real number of 1 or more.
  • the s value may be less than 1.1, but the s value is preferably 1.05 or less, more preferably 1.03 or less, still more preferably 1.02 or less, and particularly preferably 1. 01 or less, and most preferably 1.005 or less.
  • the cellulose acylate film of the present invention may contain a conventionally known plasticizer as necessary.
  • a plasticizer such as a polycarboxylic acid ester plasticizer, a glycolate plasticizer, a phthalate ester plasticizer, a fatty acid ester plasticizer, or a polyhydric alcohol ester. Selected from plasticizers, ester plasticizers, acrylic plasticizers, and the like. Of these, when two or more plasticizers are used, at least one of them is preferably a polyhydric alcohol ester plasticizer.
  • the polyhydric alcohol ester plasticizer is a plasticizer composed of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid ester, and preferably has an aromatic ring or a cycloalkyl ring in the molecule.
  • a divalent to 20-valent aliphatic polyhydric alcohol ester is preferred.
  • the polyhydric alcohol preferably used in the present invention is represented by the following general formula (III).
  • Formula (III) R 11 - (OH ) n [Wherein R 11 represents an n-valent organic group. n represents an integer of 2 or more. The OH group represents an alcoholic and / or phenolic hydroxy group. ]
  • Preferred polyhydric alcohols include, for example, adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2 -Butanediol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol Mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, xylitol and the like.
  • monocarboxylic acid used for polyhydric alcohol ester there is no restriction
  • Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto.
  • aliphatic monocarboxylic acid a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. The number of carbon atoms is more preferably 1-20, and particularly preferably 1-10.
  • acetic acid is contained, the compatibility with cellulose acylate is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid.
  • Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanoic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.
  • Examples of preferred alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, or derivatives thereof.
  • Examples of preferred aromatic monocarboxylic acids include those in which 1 to 3 alkoxy groups such as alkyl group, methoxy group or ethoxy group are introduced into the benzene ring of benzoic acid such as benzoic acid or toluic acid, biphenylcarboxylic acid, Examples thereof include aromatic monocarboxylic acids having two or more benzene rings such as naphthalenecarboxylic acid and tetralincarboxylic acid, or derivatives thereof. Benzoic acid is particularly preferable.
  • the molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably 300 to 1500, and more preferably 350 to 750. A higher molecular weight is preferable because it is less likely to volatilize, and a lower molecular weight is preferable in terms of moisture permeability and compatibility with cellulose acylate.
  • the carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.
  • polyhydric alcohol esters (ae-1) to (ae-35) are shown below.
  • the glycolate plasticizer is not particularly limited, but alkylphthalylalkyl glycolates can be preferably used.
  • alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl Glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycol Butyl phthalyl propyl glycolate, methyl phthalyl octyl
  • phthalate ester plasticizer examples include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.
  • citrate plasticizer examples include acetyl trimethyl citrate, acetyl triethyl citrate, and acetyl tributyl citrate.
  • fatty acid ester plasticizers include butyl oleate, methylacetyl ricinoleate, and dibutyl sebacate.
  • the phosphate ester plasticizer examples include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate and the like.
  • the polyvalent carboxylic acid ester compound comprises an ester of a divalent or higher, preferably 2 to 20 valent polyvalent carboxylic acid and an alcohol.
  • the aliphatic polyvalent carboxylic acid is preferably divalent to 20-valent, and in the case of an aromatic polyvalent carboxylic acid or an alicyclic polyvalent carboxylic acid, it is preferably 3 to 20 valent.
  • the polyvalent carboxylic acid is represented by the following general formula (IV).
  • Formula (IV) R 12 (COOH) m1 (OH) n1 [Wherein R 12 represents an (m1 + n1) -valent organic group, m1 represents an integer of 2 or more, n1 represents an integer of 0 or more, a COOH group represents a carboxy group, an OH group represents an alcoholic group and / or Or represents a phenolic hydroxy group. ]
  • Examples of the preferred polyvalent carboxylic acid include the following, but the present invention is not limited thereto.
  • Trivalent or higher aromatic polyvalent carboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid or derivatives thereof, succinic acid, adipic acid, azelaic acid, sebacic acid, oxalic acid, fumaric acid, maleic acid, tetrahydrophthal
  • An aliphatic polyvalent carboxylic acid such as an acid, an oxypolyvalent carboxylic acid such as tartaric acid, tartronic acid, malic acid and citric acid can be preferably used.
  • alcohol used for a polyhydric carboxylic acid ester compound there is no restriction
  • an aliphatic saturated alcohol or aliphatic unsaturated alcohol having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. More preferably, it has 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
  • alicyclic alcohols such as cyclopentanol and cyclohexanol or derivatives thereof
  • aromatic alcohols such as benzyl alcohol and cinnamyl alcohol, or derivatives thereof
  • an oxypolycarboxylic acid is used as the polycarboxylic acid
  • the alcoholic or phenolic hydroxy group of the oxypolycarboxylic acid may be esterified with a monocarboxylic acid.
  • the molecular weight of the polyvalent carboxylic acid ester compound is not particularly limited, but the molecular weight is preferably in the range of 300 to 1000, and more preferably in the range of 350 to 750. The larger one is preferable in terms of improvement in retention, and the smaller one is preferable in terms of moisture permeability and compatibility with cellulose acylate.
  • the alcohols used in the polyvalent carboxylic acid ester that can be used in the present invention may be one kind or a mixture of two or more kinds.
  • the acid value of the polyvalent carboxylic acid ester compound that can be used in the present invention is preferably 1 mgKOH / g or less, and more preferably 0.2 mgKOH / g or less. Setting the acid value in the above range is preferable because the environmental fluctuation of the retardation is also suppressed.
  • the acid value refers to the number of milligrams of potassium hydroxide necessary for neutralizing the acid (carboxy group present in the sample) contained in 1 g of the sample.
  • As the acid value a value measured according to JIS K0070 is adopted.
  • Examples of particularly preferred polyvalent carboxylic acid ester compounds are shown below, but the present invention is not limited thereto.
  • Examples include tributyl trimellitic acid and tetrabutyl pyromellitic acid.
  • the cellulose acylate film of the present invention can also contain an ultraviolet absorber.
  • the ultraviolet absorber is added for the purpose of improving the durability of the cellulose acylate film by absorbing ultraviolet rays of 400 nm or less.
  • the transmittance at a wavelength of 370 nm in the cellulose acylate film is preferably 10% or less, more preferably 5% or less, and further preferably 2% or less.
  • the ultraviolet absorber used in the present invention is not particularly limited, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, inorganic powders Examples include the body.
  • These are commercially available products made by BASF Japan and can be preferably used.
  • the ultraviolet absorber preferably used in the present invention is a benzotriazole ultraviolet absorber, a benzophenone ultraviolet absorber, or a triazine ultraviolet absorber, and particularly preferably a benzotriazole ultraviolet absorber or a benzophenone ultraviolet absorber.
  • a discotic compound such as a compound having a 1,3,5 triazine ring is also preferably used as the ultraviolet absorber.
  • a polymer UV absorber can also be preferably used, and in particular, a polymer type UV absorber described in JP-A-6-148430 is preferably used.
  • the method for adding the UV absorber is to add the UV absorber to the dope after dissolving the UV absorber in an alcohol such as methanol, ethanol, butanol, an organic solvent such as methylene chloride, methyl acetate, acetone, dioxolane, or a mixed solvent thereof. Or you may add directly in dope composition.
  • a dissolver or a sand mill is used in the organic solvent and cellulose acylate to disperse and then added to the dope.
  • the amount of UV absorber used is not uniform depending on the type of UV absorber, operating conditions, etc., but when the dry film thickness of the cellulose acylate film is 30 to 200 ⁇ m, it is 0.5 It is preferably ⁇ 10.0 mass%, more preferably 0.6-4.0 mass%.
  • Antioxidant are also referred to as deterioration inhibitors.
  • the antioxidant has a role of delaying or preventing the cellulose acylate film from being decomposed by, for example, the residual solvent amount of halogen in the cellulose acylate film or phosphoric acid of the phosphoric acid plasticizer. It is preferable to make it contain in an acylate film.
  • a hindered phenol compound is preferably used.
  • 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate] triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], oct Decyl-3- (3,5-di-t-butyl-4-hydroxyphenyl
  • 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferred.
  • hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di- A phosphorus processing stabilizer such as t-butylphenyl) phosphite may be used in combination.
  • the amount of these compounds added is preferably 1 to 5000 ppm, more preferably 10 to 1000 ppm in terms of mass ratio with respect to the cellulose acylate film.
  • acid scavenger Since cellulose acylate is accelerated by acid at high temperatures, it is preferable to contain an acid scavenger when used for the cellulose acylate film of the present invention.
  • Any useful acid scavenger can be used without limitation as long as it is a compound that reacts with an acid to inactivate the acid.
  • the epoxy described in US Pat. No. 4,137,201 is particularly useful. Compounds having a group are preferred.
  • Epoxy compounds as such acid scavengers are known in the art and are derived by condensation of diglycidyl ethers of various polyglycols, particularly about 8 to 40 moles of ethylene oxide per mole of polyglycol. Examples include polyglycol and diglycidyl ether of glycerol. Also, in or together with the vinyl chloride polymer composition, metal epoxy compounds, epoxidized ether condensation products, diglycidyl ethers of bisphenol A (ie, 4,4′- Dihydroxydiphenyldimethylmethane), epoxidized unsaturated fatty acid ester and the like can also be mentioned.
  • the epoxidized unsaturated fatty acid ester is particularly preferably an ester of a fatty acid having 2 to 22 carbon atoms and an alcohol having 2 to 4 carbon atoms, and examples thereof include butyl epoxy stearate.
  • Others include epoxidized vegetable oils and other unsaturated natural oils that may be represented and exemplified by compositions such as various epoxidized long chain fatty acid triglycerides such as epoxidized soybean oil. These fats are also referred to as epoxidized natural glycerides or unsaturated fatty acids, and the fatty acids of these fats generally contain 12 to 22 carbon atoms.
  • EPON 815C can also be preferably used as a commercially available epoxy group-containing epoxide resin compound.
  • acid scavengers that can be used in addition to the above are oxetane compounds, oxazoline compounds, organic acid salts of alkaline earth metals, acetylacetonate complexes, and paragraphs 0068 to 0105 of JP-A-5-194788. Are included.
  • an acid scavenger may be called an acid scavenger, an acid capture agent, an acid catcher, etc., in this invention, it can use without a difference by these names.
  • the cellulose acylate film of the present invention has, for example, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, hydrated calcium silicate, silicic acid in order to improve handleability. It is preferable to contain a matting agent such as inorganic fine particles such as aluminum, magnesium silicate and calcium phosphate, and a crosslinked polymer. Of these, silicon dioxide is preferable because haze of the cellulose acylate film can be reduced.
  • the primary average particle diameter of the fine particles is preferably 20 nm or less, more preferably 5 to 16 nm, and particularly preferably 5 to 12 nm.
  • These fine particles are preferably contained in the cellulose acylate film by forming secondary particles having an average particle size of 0.1 to 5.0 ⁇ m, and a more preferable average particle size is 0.1 to 2.0 ⁇ m. More preferably, the thickness is 0.2 to 0.6 ⁇ m.
  • the primary average particle diameter of the fine particles used in the present invention is measured by observing the particles with a transmission electron microscope (magnification of 500,000 to 2,000,000 times), observing 100 particles, measuring the particle diameter, and measuring the average. Let the value be the primary average particle size.
  • the method for producing a cellulose acylate film used in the present invention includes a step of stretching a film obtained by casting a dope on a metal support, drying the film, and peeling the film. Since the dope essentially includes a cellulose acylate having a degree of acyl group substitution of 2.0 to 2.5 and a Tg reducing agent, the amount of the Tg reducing agent present on both surfaces of the obtained cellulose acylate film is to some extent. The above steps are performed so that they are biased.
  • the method for producing a cellulose acylate film may be a method by a solution casting method or a method by a melt casting method, but is preferably a method by a solution casting method.
  • a solution casting method a method by a melt casting method
  • the manufacturing method of the cellulose acylate film by a solution casting method is mentioned as an example and demonstrated, it is not limited to the following form.
  • cellulose acylate having an acyl group substitution degree of 2.0 to 2.5, a Tg reducing agent, and other additives as required are dissolved in a solvent.
  • the concentration of cellulose acylate in the dope is preferable because it can reduce the drying load after casting on the metal support, but if the concentration of cellulose acylate is too high, the load during filtration increases and the filtration accuracy becomes worse.
  • the concentration that achieves both of these is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass.
  • the Tg lowering agent and other additives it is preferable to batch add a specified amount to the dope preparation kettle.
  • the solvent used for the preparation of the dope may be used alone or in combination of two or more, but it is preferable in terms of production efficiency to use a mixture of a good solvent and a poor solvent of cellulose acylate, A larger amount of good solvent is preferred from the viewpoint of the solubility of cellulose acylate.
  • the preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent.
  • the solvent which dissolves the cellulose acylate to be used alone is defined as a good solvent
  • a solvent which swells alone or does not dissolve is defined as a poor solvent. Therefore, the good solvent and the poor solvent change depending on the acyl group substitution degree of cellulose acylate.
  • the good solvent used in the present invention is not particularly limited, and examples thereof include organic halogen compounds such as methylene chloride, dioxolanes, acetone, methyl acetate, and methyl acetoacetate. Particularly preferred is methylene chloride or methyl acetate.
  • the poor solvent used in the present invention is not particularly limited, but for example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone and the like are preferably used.
  • the dope preferably contains 0.01 to 2.00% by mass of water.
  • the solvent used for dissolving cellulose acylate can be reused by collecting the solvent removed from the film by drying in the film-forming process.
  • the recovered solvent may contain trace amounts of additives added to cellulose acylate, such as plasticizers, UV absorbers, polymers, monomer components, etc. Can be purified and reused if necessary.
  • a general method can be used. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure. It is preferable to stir and dissolve while heating at a temperature not lower than the boiling point at normal pressure of the solvent and under pressure so that the solvent does not boil, because it is possible to prevent the formation of a bulk undissolved material called gel or mako.
  • Heating is preferably performed from the outside.
  • a jacket type is preferable because temperature control is easy.
  • the heating temperature with the addition of the solvent is preferably higher from the viewpoint of the solubility of cellulose acylate, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates.
  • the range of the preferred heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and further preferably 70 to 105 ° C.
  • the pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of increasing the vapor pressure of the solvent by heating. The pressure is adjusted so that the solvent does not boil at the set temperature.
  • a method for dissolving cellulose acylate a method in which cellulose acylate is mixed with a poor solvent and wetted or swollen, and then a good solvent is further added and dissolved is preferably used.
  • a cooling dissolution method is also preferably used, whereby cellulose acylate can be dissolved in a solvent such as methyl acetate.
  • the cellulose acylate solution is filtered using a suitable filter medium such as filter paper.
  • a suitable filter medium such as filter paper.
  • the filter medium it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like, but from the viewpoint of suppressing the occurrence of clogging of the filter medium, a filter medium having an absolute filtration accuracy of 0.008 mm or less is preferable.
  • a filter medium of 001 to 0.008 mm is more preferable, and a filter medium of 0.003 to 0.006 mm is more preferable.
  • the material of the filter medium there are no particular restrictions on the material of the filter medium, and ordinary filter media can be used. However, plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel can cause fibers to fall off. Less preferred. It is preferable to remove and reduce impurities, particularly bright spot foreign matter, contained in the raw material cellulose acylate by filtration.
  • Bright spot foreign matter means that when two polarizing plates are placed in a crossed Nicol state, an optical film or the like is placed between them, light is applied from one polarizing plate side, and observation is performed from the other polarizing plate side. The point (foreign matter) that the light from the opposite side appears to leak.
  • the number of bright spot foreign matters having a diameter of 0.01 mm or more is preferably 200 pieces / cm 2 or less, more preferably 100 pieces / cm 2 or less, further preferably 50 pieces / m 2 or less, Particularly preferably, it is 0 to 10 pieces / cm 2 or less. Further, it is preferable that the number of bright spot foreign matters having a diameter of 0.01 mm or less is small.
  • the dope can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and under a pressure in a range where the solvent does not boil is the filtration pressure before and after filtration.
  • the increase in the difference is small and preferable.
  • a preferred temperature range is 45 to 120 ° C, more preferably 45 to 70 ° C, and even more preferably 45 to 55 ° C.
  • a smaller filtration pressure is preferred.
  • the filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.
  • a series of steps is performed so that the existing amount of the Tg reducing agent on both surfaces of the obtained cellulose acylate film is biased to some extent.
  • r values determined from d B becomes 1.1 or more
  • the above-described series of steps is performed.
  • the above process can be performed by selecting various materials when preparing the dope.
  • the essential components of the dope there are three components, cellulose acylate, Tg lowering agent, and solvent.
  • the material is selected so that the solubility parameter value of each of these three components satisfies a predetermined relationship. select.
  • the distribution of the Tg reducing agent can be biased in the thickness direction in the obtained cellulose acylate film.
  • the Hansi solubility parameters of cellulose acylate, Tg lowering agent and solvent are HSP C , HSP G and HSP S in this order, the following formula (4) is satisfied.
  • Each material may be selected.
  • the Hansen Solubility Parameter is a parameter developed by Charles Hansen to indicate the solubility of a substance.
  • the Hansen solubility parameters HSP C , HSP G , and HSP S are described in Hansen, Charles (2007).
  • Hansen Solubility Parameters Values measured by the method described in A user's handbook, Second Edition are adopted.
  • the cellulose acylate, the Tg lowering agent and the solvent are each a mixture of two or more, but the values of HSP C , HSP G and HSP S in such a form are measured as a mixture. Adopted values.
  • HSP G -HSP C is the absolute of the difference between the value HSP C solubility parameter values HSP G cellulose acylate solubility parameter of Tg-lowering agent Mean value.
  • HSP G ⁇ HSP S means the absolute value of the difference between the solubility parameter value HSP G of the Tg lowering agent and the solubility parameter value HSP S of the solvent. Then, the fact that equation (4) is satisfied, the former is larger than the latter, that is, the value HSP G solubility parameter of Tg-lowering agent, close to the value HSP S of solvent than the value HSP C of the cellulose acylate Means.
  • the mechanism by which the distribution of the Tg reducing agent is biased in the thickness direction of the film is not completely clear, but the solubility parameters are close. Since it means that the solubility (affinity) is higher, the following mechanism has been estimated. That is, when dried on the metal support, the solvent gradually evaporates from the surface not in contact with the metal support (interface with air), so the concentration of the solvent in the thickness direction of the cellulose acylate film A gradient occurs. At that time, if the affinity of the Tg lowering agent for the solvent is higher than the affinity for the cellulose acylate, it is considered that the Tg lowering agent is biased toward the metal support having a higher solvent concentration.
  • is preferably 1.1 times or more of
  • the metal support used in the casting process is preferably a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support.
  • the cast width can be 1 to 4 m.
  • the surface temperature of the metal support in the casting step is ⁇ 50 ° C. to less than the boiling point of the solvent, and a higher temperature is preferable because the web can be dried faster. However, if the temperature is too high, the web may foam or the flatness may deteriorate.
  • the preferred support temperature range is 0 to 55 ° C, more preferably 25 to 50 ° C. It is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent.
  • the method for controlling the temperature of the metal support is not particularly limited, but there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use hot water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is shortened. When warm air is used, wind at a temperature higher than the target temperature may be used.
  • the film obtained by casting is dried and peeled off.
  • the distribution of the Tg reducing agent is biased in the thickness direction in the cellulose acylate film
  • the process conditions may be controlled so that the residual solvent amount in the film at the time of peeling from the metal support is 90% or less.
  • the amount of residual solvent in the film at the time of peeling from the metal support is preferably 85% or less, more preferably 80% or less.
  • the control according to the second mode and the control according to the first mode (selection of material at the time of dope preparation) described above may be performed together.
  • the amount of residual solvent is defined by the following formula 5.
  • Residual solvent amount (% by mass) ⁇ (MN) / N ⁇ ⁇ 100 [In the formula, M represents the mass of a sample collected at any time during or after production of the web or cellulose acylate film, and N represents the mass after heating the sample at 115 ° C. for 1 hour. ]
  • Process conditions that are controlled so that the value of the residual solvent amount is not more than a predetermined value include drying conditions before peeling the film from the metal support.
  • drying conditions There is no particular limitation on the specific form of drying conditions before film peeling from the metal support, and controlling the drying conditions so that the value of the residual solvent amount of the film at the time of peeling is not more than a predetermined value, Those skilled in the art can carry out the present invention without any particular difficulty.
  • the range of the drying temperature is preferably about 25 to 50 ° C., more preferably 35 to 45 ° C.
  • the drying time is preferably about 15 to 150 seconds, more preferably 25 to 120 seconds.
  • conditions outside these ranges may be adopted.
  • drying means employ
  • a well-known knowledge can be referred suitably.
  • Specific examples of the drying means include hot air, infrared rays, heating rollers, and microwaves, but it is preferable to carry out with hot air from the viewpoint of simplicity.
  • the film (web) peeled from the metal support is stretched. Under the present circumstances, it is especially preferable to extend
  • the peel tension from the metal support is preferably 300 N / m or less.
  • the film thickness and retardation value of the obtained cellulose acylate film can be controlled.
  • the retardation can be changed by lowering or increasing the tension in the longitudinal direction.
  • retardation can be fluctuate
  • the draw ratios in the biaxial directions orthogonal to each other are preferably finally in the range of 0.8 to 1.5 times in the longitudinal direction and 1.1 to 2.0 times in the width direction. More preferably, it is performed in the range of 0.8 to 1.1 times and in the range of 1.3 to 1.7 times in the width direction, and particularly preferably in the range of 1.3 to 1.5 times in the width direction.
  • the cellulose acylate film of the present invention is easily stretched and retardation is likely to develop, and has high resistance to process failures such as breakage.
  • the temperature range during stretching is preferably 120 ° C. to 200 ° C., more preferably 130 ° C. to 170 ° C., and further preferably more than 140 ° C. and 160 ° C. or less.
  • the range of the residual solvent amount in the film during the stretching treatment is preferably 20 to 0%, more preferably 15 to 0%. More specifically, for example, it is preferable that the residual solvent amount is stretched by 11% at a temperature of 155 ° C., or the residual solvent amount is stretched by 2% at a temperature of 155 ° C. Alternatively, it is preferable to stretch at a temperature of 160 ° C. with a residual solvent amount of 11%, or at 160 ° C. with a residual solvent amount of less than 1%.
  • the method of stretching the web There is no particular limitation on the method of stretching the web.
  • Examples thereof include a method of stretching in the direction, a method of stretching in the horizontal direction and stretching in the horizontal direction, a method of stretching in the vertical and horizontal directions and stretching in both the vertical and horizontal directions, and the like. Of course, these methods may be used in combination.
  • tenter method driving the clip portion by the linear drive method is preferable because smooth stretching can be performed and the possibility of breakage or the like can be reduced. It is preferable to carry out the width maintenance or lateral stretching in the film forming step by a tenter, and it may be a pin tenter or a clip tenter.
  • a further drying step is performed to make the residual solvent amount 1% by mass or less, more preferably 0.10% by mass or less, and further preferably 0.00 to 0.01% by mass. It is as follows.
  • the drying temperature after stretching is preferably 125 ° C. or higher, and more preferably 140 ° C. or higher. If it exceeds 150 ° C., it approaches the glass transition temperature Tg of the cellulose acylate film, which may lead to a decrease in retardation value or misalignment of the orientation angle.
  • the manufacturing method by the solution casting method was mentioned as an example, it may be manufactured by the melt casting method from the viewpoint of manufacturing cost.
  • a desired cellulose acylate film can be obtained by the control according to the second embodiment described above.
  • the molding method by melt casting that is heated and melted is a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, It can be classified into a stretch molding method.
  • the melt extrusion molding method is excellent.
  • the specific method for obtaining the cellulose acylate web by the melt casting method and known knowledge can be referred to as appropriate.
  • a cellulose acylate film in which the distribution of the Tg reducing agent is biased in the thickness direction can be produced by a co-casting method.
  • a method for producing a cellulose acylate film by a co-casting method will be described.
  • the manufacturing method according to the third embodiment includes a step of co-casting a plurality of dopes having different Tg lowering agent concentrations on a metal support, drying a film obtained by casting, and peeling the film. And a step of stretching after.
  • a plurality of dopes including a cellulose acylate, a Tg reducing agent, and other additives are prepared.
  • a dope A having a low concentration of Tg reducing agent and a dope B having a high concentration of Tg reducing agent are prepared.
  • Dope A is on the surface layer side
  • dope B is on the metal support layer side. What is necessary is just to co-cast on a metal support body so that it may become.
  • the respective dopes are laminated from the surface layer side to the metal support layer side in the order of increasing Tg reducing agent concentration.
  • the form of performing is preferable.
  • the film thickness of the cellulose acylate film used in the present invention is preferably a thin film, preferably in the range of 10 to 200 ⁇ m, preferably 10 to 100 ⁇ m, more preferably 10 to 60 ⁇ m, and still more preferably. Is 20 to 60 ⁇ m.
  • the width of the cellulose acylate film used in the present invention is 1.0 to 4.0 m. In particular, a width of 1.4 to 4.0 m is preferable, and 1.6 to 3.0 m is more preferable. When the width is 4.0 m or less, the conveyance is easy.
  • the retardation values Ro and Rth of the cellulose acylate film used in the present invention are determined by the following mathematical formulas (6) and (7).
  • Equation (6) (n x -n y) ⁇ d [nm]
  • n x represents a refractive index in a slow axis direction of the cellulose acylate film plane.
  • n y represents a fast axis direction of the refractive index of the cellulose acylate film plane.
  • nz represents the refractive index in the thickness direction of the cellulose acylate film.
  • the refractive index is a value measured at a wavelength of 590 nm in an environment of 23 ° C. and 55% RH.
  • d represents the thickness (nm) of the cellulose acylate film.
  • the retardation values Ro and Rth were obtained by cutting a sample 35 mm ⁇ 35 mm from the obtained cellulose acylate film, adjusting the humidity at 25 ° C. ⁇ 55% RH for 2 hours, and using an automatic birefringence meter (KOBRA21DH, manufactured by Oji Scientific Co., Ltd.). ) And the extrapolated value of the retardation value measured in the same manner while tilting the cellulose acylate film surface.
  • KOBRA21DH automatic birefringence meter
  • the retardation values Ro and Rth satisfy the following ranges from the viewpoint of taking advantage of high retardation development. Is preferred. 10 ⁇ Ro ⁇ 100 70 ⁇ Rth ⁇ 300
  • the retardation value Ro is preferably 30 to 70, more preferably 40 to 60, and further preferably 45 to 55.
  • the retardation value Rth is preferably 90 to 230, more preferably 100 to 170, and still more preferably 110 to 160.
  • the slow axis or the fast axis of the cellulose acylate film is present in the cellulose acylate film plane, and ⁇ 1 is preferably ⁇ 1 ° or more and + 1 ° or less, assuming that the angle formed with the film forming direction is ⁇ 1. More preferably, the angle is ⁇ 0.5 ° or more and + 0.5 ° or less.
  • This ⁇ 1 can be defined as an orientation angle, and ⁇ 1 can be measured using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments).
  • KOBRA-21ADH automatic birefringence meter
  • the moisture permeability of the cellulose acylate film is preferably 300 to 1800 g / m 2 ⁇ 24 h at 40 ° C. and 90% RH, more preferably 400 to 1500 g / m 2 ⁇ 24 h, and particularly preferably 400 to 1300 g / m 2 ⁇ 24 h. .
  • the moisture permeability can be measured according to the method described in JIS Z0208.
  • the range of the elongation at break of the cellulose acylate film is preferably 10 to 80%, and more preferably 20 to 50%.
  • the range of visible light transmittance of the cellulose acylate film is preferably 90% or more, and more preferably 93% or more.
  • the haze of the cellulose acylate film is preferably less than 1.0%, and more preferably 0.0 to 0.1%.
  • Photocurable adhesive for laminating the polarizer and the cellulose acylate film
  • a photocurable adhesive composition containing the following components ( ⁇ ) to ( ⁇ ).
  • the cationically polymerizable compound ( ⁇ ) which is a main component of the photocurable adhesive composition and serves as a component that gives adhesive force by polymerization and curing, may be any compound that can be cured by cationic polymerization. It is preferable to include an epoxy compound having one epoxy group.
  • the epoxy compound includes an aromatic epoxy compound having an aromatic ring in the molecule, an alicyclic epoxy compound having at least two epoxy groups in the molecule, and at least one of which is bonded to the alicyclic ring.
  • a fatty acid that does not have an aromatic ring in the molecule and one carbon atom of the ring containing the two carbon atoms to which it is bonded is bonded to another aliphatic carbon atom Group epoxy compounds.
  • the photocurable adhesive composition used in the present invention is preferably an epoxy resin containing no aromatic ring, particularly an alicyclic epoxy compound as a main component, as the cationic polymerizable compound ( ⁇ ). If a cationically polymerizable compound containing an alicyclic epoxy compound as a main component is used, a cured product having a high storage elastic modulus is given, and the cellulose acylate film and the polarizer are bonded via the cured product (adhesive layer). In the polarizing plate, the polarizer is difficult to break.
  • the alicyclic epoxy compound has at least two epoxy groups in the molecule, and at least one of them is bonded to the alicyclic ring.
  • the epoxy group bonded to the alicyclic ring is, as shown in the following formula (ep), two bonds in which two bonds of the epoxy group (—O—) constitute the alicyclic ring.
  • Each of the carbon atoms (usually adjacent carbon atoms).
  • ep m represents an integer of 2 to 5.
  • a compound in which one or more hydrogen atoms in (CH 2 ) m in the general formula (ep) are removed and bonded to another chemical structure can be an alicyclic epoxy compound.
  • Hydrogen constituting the alicyclic ring may be appropriately substituted with a linear alkyl group such as a methyl group or an ethyl group.
  • the compounds represented by any one of the following formulas (ep-1) to (ep-11) are further obtained because they are easily available and have a large effect of increasing the storage elastic modulus of the cured product. preferable.
  • R 3 to R 24 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and when R 3 to R 24 are alkyl groups, the position bonded to the alicyclic ring is 1 It is an arbitrary number from the first to sixth positions.
  • the alkyl group having 1 to 6 carbon atoms may be a straight chain, may be branched, or may have an alicyclic ring.
  • Y 8 represents an oxygen atom or an alkanediyl group having 1 to 20 carbon atoms.
  • Y 1 to Y 7 each independently represents a straight chain, may be branched, and may represent an alkanediyl group having 1 to 20 carbon atoms which may have an alicyclic ring.
  • n, p, q and r each independently represents a number from 0 to 20.
  • the alicyclic diepoxy compound represented by the formula (ep-2) is preferable because it is easily available.
  • the alicyclic diepoxy compound of the formula (ep-2) includes 3,4-epoxycyclohexylmethanol (an alkyl group having 1 to 6 carbon atoms may be bonded to the cyclohexane ring) and 3,4-epoxycyclohexane.
  • An ester compound with a carboxylic acid an alkyl group having 1 to 6 carbon atoms may be bonded to the cyclohexane ring).
  • an alicyclic epoxy compound in combination with an epoxy resin having substantially no alicyclic epoxy group. If a cation-polymerizable compound containing an alicyclic epoxy compound as the main component and an epoxy resin substantially free of an alicyclic epoxy group is used as a cationically polymerizable compound, the cured product has a high storage elastic modulus. However, the adhesion between the polarizer and the cellulose acylate film can be further enhanced.
  • an epoxy resin having substantially no alicyclic epoxy group means that one carbon atom of a ring (usually an oxirane ring) containing an epoxy group and two carbon atoms to which the epoxy group is bonded in the molecule.
  • a compound bonded to another aliphatic carbon atom examples thereof include polyglycidyl ether of polyhydric alcohol (phenol).
  • phenol polyhydric alcohol
  • a diglycidyl ether compound represented by the following general formula (ge) is preferable because it is easily available and has a large effect of improving the adhesion between the polarizer and the cellulose acylate film.
  • X represents a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group, O, S, SO 2 , SS, SO, CO, OCO or the following formula (ge-1 )
  • To (ge-3) represents a substituent selected from the group consisting of three types of substituents, and the alkylidene group may be substituted with a halogen atom.
  • R 25 and R 26 may be each independently substituted with a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group.
  • Good may be
  • a and D are each independently an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or 6 carbon atoms which may be substituted with a halogen atom.
  • the methylene group in the alkyl group, aryl group or arylalkyl group may be interrupted by an unsaturated bond, —O— or —S—.
  • a represents a number from 0 to 4
  • d represents a number from 0 to 4.
  • Examples of the diglycidyl ether compound of the general formula (ge) include bisphenol-type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S; glycidyl ether of tetrahydroxyphenylmethane , Glycidyl ether of tetrahydroxybenzophenone, polyfunctional epoxy resin such as epoxidized polyvinylphenol; polyglycidyl ether of aliphatic polyhydric alcohol; polyglycidyl ether of alkylene oxide adduct of aliphatic polyhydric alcohol; Examples thereof include diglycidyl ether, and among them, polyglycidyl ether of aliphatic polyhydric alcohol is preferable because it is easily available.
  • Examples of the aliphatic polyhydric alcohol include those having 2 to 20 carbon atoms. More specifically, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl -2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, -Aliphatic
  • the blending ratio of both is 50 to 50 based on the total amount of the cationic polymerizable compound. It is preferable that 95% by mass and an epoxy resin substantially not having an alicyclic epoxy group be 5% by mass or more.
  • the adhesiveness of a polarizer and a cellulose acylate film improves by mix
  • the amount of the epoxy resin having substantially no alicyclic epoxy group is 50 based on the total amount of the cation polymerizable compound when the cation polymerizable compound is a two-component system with the alicyclic epoxy compound.
  • cationically polymerizable compound ( ⁇ ) constituting the photocurable adhesive composition when using an alicyclic epoxy compound and an epoxy resin substantially free of an alicyclic epoxy group as described above, in the range where becomes the above-mentioned amount, in addition to these, other cationically polymerizable compounds may be included.
  • examples of other cationically polymerizable compounds include epoxy compounds other than formulas (ep-1) to (ep-11) and general formula (ge), oxetane compounds, and the like.
  • Epoxy compounds other than those represented by formulas (ep-1) to (ep-11) and formula (ge) include at least one alicyclic ring in the molecule other than those represented by formulas (ep-1) to (ep-11).
  • Examples of alicyclic epoxy compounds having an epoxy group bonded to at least one alicyclic ring in a molecule other than those represented by formulas (ep-1) to (ep-11) include 4-vinylcyclohexene diepoxide, 1, 2: diepoxides of vinylcyclohexenes such as 2: 8,9-diepoxy limonene.
  • Examples of the aliphatic epoxy compound having an oxirane ring bonded to an aliphatic carbon atom other than the general formula (ge) include triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, and diglycidyl ether of polyethylene glycol.
  • the aromatic epoxy compound having an aromatic ring and an epoxy group in the molecule can be a glycidyl ether of an aromatic polyhydroxy compound having at least two phenolic hydroxy groups in the molecule.
  • a hydrogenated epoxy compound having an aromatic ring hydrogenated in an aromatic epoxy compound catalyzes an aromatic polyhydroxy compound having at least two phenolic hydroxy groups in a molecule as a raw material of the aromatic epoxy compound.
  • the hydrogenated polyhydroxy compound obtained by selectively performing a hydrogenation reaction under pressure in the presence of glycidyl ether can be obtained.
  • Specific examples include diglycidyl ether of hydrogenated bisphenol A, diglycidyl ether of hydrogenated bisphenol F, diglycidyl ether of hydrogenated bisphenol S, and the like.
  • epoxy compounds other than formulas (ep-1) to (ep-11) and general formula (ge) they have an epoxy group bonded to an alicyclic ring, and are classified as the alicyclic epoxy compounds defined above.
  • the sum of the alicyclic epoxy compounds represented by the formulas (ep-1) to (ep-11) does not exceed 95% by mass based on the total amount of the cationic polymerizable compound Used in a range.
  • An oxetane compound that can be any cationically polymerizable compound is a compound having a 4-membered cyclic ether (oxetanyl group) in the molecule. Specific examples thereof include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di [ (3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (cyclohexyloxymethyl) oxetane, phenol novolak oxetane, 1,3-bis [(3-Ethyloxetane-3-yl) methoxy] benzene, oxetanylsilsesquio
  • Photocationic polymerization initiator ( ⁇ ) In the present invention, the cationically polymerizable compound as described above is cationically polymerized by irradiation with active energy rays and cured to form an adhesive layer. Therefore, the photocurable adhesive composition has photocationic polymerization initiation. It is preferable to blend the agent ( ⁇ ).
  • the cationic photopolymerization 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, and performs a polymerization reaction of the cationic polymerizable compound ( ⁇ ). It is what is started. Since the cationic photopolymerization initiator ( ⁇ ) acts catalytically by light, it is excellent in storage stability and workability even when mixed with the cationically polymerizable compound ( ⁇ ).
  • Examples of compounds that generate cation species and Lewis acids upon irradiation with active energy rays include aromatic diazonium salts; onium salts such as aromatic iodonium salts and aromatic sulfonium salts; and iron-allene complexes.
  • aromatic diazonium salt examples include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate.
  • aromatic iodonium salt examples include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and the like.
  • aromatic sulfonium salt examples include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis [diphenylsulfonio] diphenyl sulfide bishexafluoro.
  • iron-allene complexes examples include xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene-cyclopentadienyl iron (II) tris (tri Fluoromethylsulfonyl) methanide and the like.
  • photocationic polymerization initiators ( ⁇ ) may be used alone or in admixture of two or more.
  • aromatic sulfonium salts are particularly preferably used because they have ultraviolet absorption characteristics even in the wavelength region near 300 nm, and thus can provide a cured product having excellent curability and good mechanical strength and adhesive strength. .
  • the compounding amount of the photo cationic polymerization initiator ( ⁇ ) is 1 to 10 parts by mass with respect to 100 parts by mass of the whole cationic polymerizable compound ( ⁇ ).
  • the cationic photopolymerization initiator ( ⁇ ) can be sufficiently cured, and the resulting polarizing plate can be obtained.
  • the amount is increased, the ionic substance in the cured product increases, so that the hygroscopic property of the cured product increases and the durability performance of the polarizing plate may be lowered.
  • the amount of the cationic photopolymerization initiator ( ⁇ ) is preferably 2 parts by mass or more and preferably 6 parts by mass or less per 100 parts by mass of the cationic polymerizable compound ( ⁇ ).
  • the photocurable adhesive composition that can be used in the present invention is suitable for light having a wavelength longer than 380 nm in addition to the cationic polymerizable compound ( ⁇ ) and the cationic photopolymerization initiator ( ⁇ ) including the epoxy compound as described above. Contains a photosensitizer ( ⁇ ) exhibiting maximum absorption.
  • the cationic photopolymerization initiator ( ⁇ ) exhibits maximum absorption at a wavelength near or shorter than 300 nm, generates a cationic species or a Lewis acid in response to light having a wavelength near the wavelength, and generates a cationic polymerizable compound ( ⁇ ) Is initiated, but a photosensitizer ( ⁇ ) that exhibits maximum absorption in light having a wavelength longer than 380 nm is blended so as to be sensitive to light having a longer wavelength than that.
  • a photosensitizer ( ⁇ ) an anthracene compound represented by the following general formula (at) is advantageously used.
  • R 5 and R 6 each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 12 carbon atoms.
  • R 7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • anthracene compound represented by the general formula (at) include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9 , 10-dibutoxyanthracene, 9,10-dipentyloxyanthracene, 9,10-dihexyloxyanthracene, 9,10-bis (2-methoxyethoxy) anthracene, 9,10-bis (2-ethoxyethoxy) anthracene, 9 , 10-bis (2-butoxyethoxy) anthracene, 9,10-bis (3-butoxypropoxy) anthracene, 2-methyl or 2-ethyl-9,10-dimethoxyanthracene, 2-methyl or 2-ethyl-9, 10-diethoxyanthracene, 2-methyl or -Ethyl-9,10-dipropoxyanthracene,
  • the curability of the photocurable adhesive composition is improved as compared with the case where it is not blended. Curability is improved by setting the blending amount of the photosensitizer ( ⁇ ) to 100 parts by mass of the cationic polymerizable compound ( ⁇ ) constituting the photocurable adhesive composition to be 0.1 parts by mass or more. The effect is manifested. On the other hand, in order to prevent precipitation during low-temperature storage, the blending amount is 2 parts by mass or less with respect to 100 parts by mass of the cationic polymerizable compound ( ⁇ ).
  • the amount of the photosensitizer ( ⁇ ) is in the range of 0.1 to 0.5 parts by mass, further 0.1 to 0.3 parts by mass. Is preferred.
  • the photocurable adhesive composition that can be used in the present invention includes the following cationic polymerizable compound ( ⁇ ) containing an epoxy compound, a cationic photopolymerization initiator ( ⁇ ), and a photosensitizer ( ⁇ ). It contains a naphthalene-based photosensitization aid ( ⁇ ) represented by the general formula (nf). [Wherein, R 1 and R 2 are each an alkyl group having 1 to 6 carbon atoms. ]
  • naphthalene photosensitizer ( ⁇ ) examples include 1,4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, 1, 4-dibutoxynaphthalene and the like can be mentioned.
  • the curability of the photocurable adhesive composition is improved as compared with the case where it is not blended.
  • the blending amount of the naphthalene photosensitizer ( ⁇ ) is 10 parts by mass or less with respect to 100 parts by mass of the cationic polymerizable compound ( ⁇ ) in order to prevent precipitation during low-temperature storage.
  • the blending amount is 5 parts by mass or less with respect to 100 parts by mass of the cationic polymerizable compound ( ⁇ ).
  • the photocurable adhesive composition that can be used in the present invention can contain an additive component as an optional component as long as the effects of the present invention are not impaired.
  • additive components in addition to the above-mentioned photocationic polymerization initiator and photosensitizer ( ⁇ ), photosensitizers other than the photosensitizer ( ⁇ ), thermal cationic polymerization initiators, polyols, ion trapping agents , Antioxidants, light stabilizers, chain transfer agents, tackifiers, thermoplastic resins, fillers, flow regulators, plasticizers, antifoaming agents, leveling agents, dyes, organic solvents, and the like.
  • the amount of the additive component used is preferably 1000 parts by mass or less with respect to 100 parts by mass of the cationic polymerizable compound ( ⁇ ).
  • the amount used is 1000 parts by mass or less, a cationically polymerizable compound ( ⁇ ), a photocationic polymerization initiator ( ⁇ ), and a photosensitizer, which are essential components of the photocurable adhesive composition that can be used in the present invention.
  • the adhesive for laminating the polarizer and the cellulose acylate film include a photocurable adhesive that essentially contains the following three components ( ⁇ 1), ( ⁇ 2), and ( ⁇ 1).
  • a composition is included.
  • ( ⁇ 1) Epoxy compound having at least two epoxy groups in the molecule
  • ( ⁇ 2) Oxetane compound having at least one oxetanyl group in the molecule
  • the epoxy compound ( ⁇ 1), the oxetane compound ( ⁇ 2), and the photocationic polymerization initiator ( ⁇ 1) are simply referred to as the epoxy compound ( ⁇ 1), the oxetane compound ( ⁇ 2), and the photocationic polymerization initiator, respectively. It is called ( ⁇ 1).
  • the mass ratio of the epoxy compound ( ⁇ 1) to the oxetane compound ( ⁇ 2) is preferably about 90:10 to 10:90.
  • the cationic photopolymerization initiator ( ⁇ 1) is preferably blended in the composition at a ratio of about 0.5 to 20.0% by mass.
  • This photo-curable adhesive can optionally contain an unsaturated compound having at least one ethylenically unsaturated bond in the molecule as the ( ⁇ ) component.
  • an unsaturated compound ( ⁇ ) When such an unsaturated compound ( ⁇ ) is contained, it is preferable to contain a radical photopolymerization initiator as the ( ⁇ ) component.
  • this photocurable adhesive agent can also contain the other component which does not have polymerizability as ((eta)) component.
  • the unsaturated compound ( ⁇ ), the photoradical polymerization initiator as the ( ⁇ ) component, and the other non-polymerizable component as the ( ⁇ ) component are simply referred to as the unsaturated compound ( ⁇ ) and the photoradical, respectively. It is referred to as a polymerization initiator ( ⁇ ) and other component ( ⁇ ) having no polymerizability.
  • the epoxy compound ( ⁇ 1) is not particularly limited as long as it has at least two epoxy groups in the molecule, and various kinds of generally known curings.
  • a functional epoxy compound can be used.
  • An example is an alicyclic epoxy compound formed between two adjacent carbon atoms constituting an alicyclic ring.
  • the aromatic epoxy compound is not particularly limited as long as the effects of the present invention are not hindered, but bisphenol type such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and brominated bisphenol A diglycidyl ether.
  • Epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins; biphenyl type epoxy resins, hydroquinone diglycidyl ether, resorcin diglycidyl ether, terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester Epoxidized product of styrene-butadiene copolymer, epoxidized product of styrene-isoprene copolymer, terminal carboxylic acid polybutadiene and bisphenol A type epoxy resin Pressurized reactant, etc. as an example.
  • novolak epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins
  • biphenyl type epoxy resins hydroquinone diglycidyl ether, resorcin diglycidyl ether, terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester Epoxidized product
  • the epoxy resin here means a compound or polymer having an average of two or more epoxy groups in the molecule and cured by reaction.
  • a monomer may be referred to as an epoxy resin as long as it has two or more curable epoxy groups in the molecule.
  • the alicyclic epoxy compound is not particularly limited as long as the effects of the present invention are not hindered, but dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3,4.
  • Examples include compounds having at least one epoxidized cyclohexyl group such as epoxycyclohexanecarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate.
  • aliphatic epoxy compounds such as 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, polytetramethylene glycol diglycidyl ether; dihydrogenated bisphenol A Epoxy compounds with aromatic rings hydrogenated, such as glycidyl ether; compounds with both ends of hydroxy-terminated polybutadiene, glycidyl ether-terminated polybutadiene, polybutadiene internal epoxide, and styrene-butadiene copolymer double bond Partially epoxidized compound (for example, Epofriend manufactured by Daicel Chemical Industries, Ltd.), compound in which isoprene unit of block copolymer of ethylene-butylene copolymer and polyisoprene is partially epoxidized (for example, , Polymeric epoxy compounds, such as 1,6-he
  • the aromatic epoxy compound is preferable because it is excellent in durability and the like when used in a polarizing plate, and particularly excellent in adhesion to a polarizer and a cellulose acylate film.
  • preferred examples of the aromatic epoxy compound include glycidyl ethers of aromatic compounds or glycidyl esters of aromatic compounds.
  • glycidyl ethers of aromatic compounds include bisphenol type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of brominated bisphenol A; phenol novolac type epoxy resin, cresol novolak type Preferred examples include novolak-type epoxy resins such as epoxy resins; biphenyl-type epoxy resins; hydroquinone diglycidyl ether; resorcin diglycidyl ether and the like.
  • Specific examples of glycidyl esters of aromatic compounds include terephthalic acid diglycidyl ester and phthalic acid diglycidyl ester.
  • glycidyl ether of an aromatic compound is particularly preferable because it is more excellent in adhesion between a polarizer and a cellulose acylate film and durability when used for a polarizing plate.
  • particularly preferable compounds include diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and phenol novolac type epoxy resin.
  • the epoxy compound ( ⁇ 1) can be used alone or as a mixture of two or more.
  • two or more aromatic epoxy compounds can be mixed and used, or an aromatic epoxy compound as a main component and an alicyclic epoxy compound can also be mixed.
  • the oxetane compound ( ⁇ 2) is not particularly limited as long as it has at least one oxetanyl group in the molecule, and various compounds having an oxetanyl group are also used. be able to.
  • Preferred examples of the oxetane compound ( ⁇ 2) include a compound having one oxetanyl group in the molecule (hereinafter referred to as monofunctional oxetane) and a compound having two or more oxetanyl groups in the molecule (hereinafter referred to as polyfunctional oxetane). As mentioned.
  • monofunctional oxetane monofunctional oxetane containing alkoxyalkyl group such as 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, and monofunctional containing aromatic group such as 3-ethyl-3-phenoxymethyloxetane.
  • alkoxyalkyl group such as 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane
  • monofunctional containing aromatic group such as 3-ethyl-3-phenoxymethyloxetane.
  • Preferred examples include hydroxy group-containing monofunctional oxetanes such as oxetane and 3-ethyl-3-hydroxymethyloxetane.
  • polyfunctional oxetane examples include 3-ethyl-3-[(3-ethyloxetane-3-yl) methoxymethyl] oxetane, 1,4-bis [(3-ethyloxetane-3-yl) methoxymethyl] benzene, 1,4-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,2-bis [(3-ethyl Oxetane-3-yl) methoxy] benzene, 4,4'-bis [(3-ethyloxetane-3-yl) methoxy] biphenyl, 2,2'-bis [(3-ethyloxetane-3-yl) methoxy] Biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-bis [(3-
  • the oxetane compound ( ⁇ 2) is preferably liquid at room temperature with a molecular weight of 500 or less from the viewpoint of coating properties and adhesion to a cellulose acylate film when used for a polarizing plate. Furthermore, in terms of excellent durability of the polarizing plate, a monofunctional oxetane is more preferably an aromatic ring in the molecule or a polyfunctional oxetane.
  • oxetane compounds examples include 3-ethyl-3-phenoxymethyloxetane, 3-ethyl-3-[(3-ethyloxetane-3-yl) methoxymethyl] oxetane, 1,4-bis [(3 -Ethyloxetane-3-yl) methoxymethyl] benzene and the like.
  • the oxetane compound ( ⁇ 2) can also be used alone or in combination of two or more.
  • the mass ratio of the epoxy compound ( ⁇ 1) to the oxetane compound ( ⁇ 2) is 90:10 to 10:90. If this mass ratio is excessive or insufficient, the effect of curing in a short time, which is one of important characteristics in the photocurable adhesive composition that can be used in the present invention, is not sufficiently exhibited.
  • a preferred mass ratio is about 70:30 to 20:80, more preferably 60:40, because it has a low viscosity before curing, excellent coating properties, and can exhibit sufficient adhesion and flexibility after curing. It is about 25:75.
  • the photocurable adhesive composition that can be used in the present invention contains the above-described epoxy compound ( ⁇ 1) and oxetane compound ( ⁇ 2) as curing components, and these are all cured by cationic polymerization.
  • a photocationic polymerization initiator ( ⁇ 1) is blended.
  • the cationic photopolymerization initiator ( ⁇ 1) generates cationic species or a Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and initiates a polymerization reaction of an epoxy group or an oxetanyl group.
  • the cationic photopolymerization initiator ( ⁇ 1) By blending the cationic photopolymerization initiator ( ⁇ 1), curing at room temperature is possible, and there is little need to consider the heat resistance of the polarizer and distortion due to expansion or contraction, and the cellulose acylate film is adhered well. be able to.
  • the cationic photopolymerization initiator ( ⁇ 1) acts catalytically upon irradiation with active energy rays, it is excellent in storage stability and workability even when mixed with the epoxy compound ( ⁇ 1) and the oxetane compound ( ⁇ 2). .
  • Photocationic polymerization initiators ( ⁇ 1) that generate cationic species and Lewis acids upon irradiation with such active energy rays include, for example, onium salts such as aromatic diazonium salts, aromatic iodonium salts and aromatic sulfonium salts, iron- An allene complex etc. can be mentioned.
  • aromatic diazonium salt examples include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate.
  • aromatic iodonium salt examples include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and the like.
  • aromatic sulfonium salt examples include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate, diphenyl [ 4- (phenylthio) phenyl] sulfonium hexafluoroantimonate, 4,4'-bis (diphenylsulfonio) diphenyl sulfide bishexafluorophosphate, 4,4'-bis [di ( ⁇ -hydroxyethoxy) phenylsulfonio] diphenyl Sulfide bishexafluoroantimonate, 4,4'-bis [di ( ⁇ -hydroxyethoxy) phenylsulfon
  • iron-allene complexes examples include xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene-cyclopentadienyl iron (II) -tris ( (Trifluoromethylsulfonyl) methanide and the like.
  • photocationic polymerization initiators ( ⁇ 1) may be used alone or in combination of two or more.
  • aromatic sulfonium salts are particularly preferably used because they have ultraviolet absorption characteristics even in a wavelength region of 300 nm or more, and therefore can provide a cured product having excellent curability and good mechanical strength and adhesive strength. It is done.
  • cationic photopolymerization initiator ( ⁇ 1) commercially available products can be easily obtained.
  • Kayrad PCI-220 and Kayalad PCI-620 (above, manufactured by Nippon Kayaku Co., Ltd.) under the trade names, respectively.
  • UVI-6992 (manufactured by Dow Chemical Co.), Adeka optomer SP-150, Adeka optomer SP-170 (above, manufactured by ADEKA), CI-5102, CIT-1370, CIT-1682S, 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), Irgacure 250, Irgacure PAG103, Irgacure PAG108, Irgacure PAG
  • UVI-6992, CPI-100P, CPI-101A, CPI-200K, and CPI-210S containing diphenyl [4- (phenylthio) phenyl] sulfonium as a cation component are preferable.
  • the blending ratio of the photocationic polymerization initiator ( ⁇ 1) is in the range of 0.5 to 20.0% by mass based on the entire photocurable adhesive.
  • the blending ratio is 0.5% by mass or more, the photocurable adhesive is sufficiently cured, and the mechanical strength and the adhesive strength can be maintained.
  • the blending ratio is 20% by mass or less, an increase in hygroscopicity of the cured product due to an increase in ionic substances in the cured product can be suppressed, and a decrease in durability can be prevented.
  • the photocurable adhesive may contain an unsaturated compound ( ⁇ ) having at least one ethylenically unsaturated bond in the molecule, if necessary.
  • an unsaturated compound ( ⁇ ) is a (meth) acrylic compound having at least one (meth) acryloyl group in the molecule.
  • the (meth) acrylic compound is not particularly limited, and examples thereof include (meth) acrylates, (meth) acrylamides, (meth) acrylic acid, (meth) acryloylmorpholine, and (meth) acrylaldehyde.
  • the (meth) acrylates having one (meth) acryloyl group in the molecule are not particularly limited, but for example, methyl (meth) acrylate, ethyl (meth) acrylate, Propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, Alkyl (meth) acrylates such as stearyl (meth) acrylate; hydrides such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Roxyalkyl (meth)
  • (meth) acrylates having two or more (meth) acryloyl groups in the molecule are not particularly limited, and examples thereof include the following compounds.
  • Alicyclic rings such as tricyclodecane dimethylol di (meth) acrylate, 1,4-cyclohexane dimethylol di (meth) acrylate, norbornane dimethylol di (meth) acrylate, di (meth) acrylate of hydrogenated bisphenol A Di (meth) acrylates having bisphenol A ethylene oxide adduct di (meth) acrylate, bisphenol A propylene oxide adduct di (meth) acrylate containing di (meth) acrylate, bisphenol A Di (meth) acrylates having an aromatic ring such as di (meth) acrylate of A diglycidyl ether; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, penta Di (meth) acrylates of alkylene glycols such as diol di (meth) acrylate and hexanediol di (meth) acrylate; diethylene glycol di
  • (Meth) acrylamides include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropylacrylamide, N-butyl (meth) acrylamide, N -Hexyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylol-N-propane (meth) acrylamide, aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide, Examples include mercaaptmethyl (meth) acrylamide and mercaaptethyl (meth) acrylamide.
  • oligomers such as urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate can be used as the (meth) acrylic compound.
  • a compound having an ethylenically unsaturated bond other than the (meth) acryloyl group can also be used as the (meth) acrylic compound.
  • Specific examples thereof include allyl (meth) acrylate and N, N-diallyl (meth) acrylamide.
  • the unsaturated compound ( ⁇ ) is not particularly limited, and in addition to the above (meth) acrylic compounds, vinyl compounds such as N-vinyl-2-pyrrolidone, divinyl adipate and divinyl sebacate; triallyl isocyan Allyl compounds such as nurate, triallylamine, tetraallyl pyromellitate, N, N, N ′, N′-tetraallyl-1,4-diaminobutane, tetraallylammonium salt, allylamine; such as maleic acid and itaconic acid Unsaturated carboxylic acids and the like can also be used.
  • vinyl compounds such as N-vinyl-2-pyrrolidone, divinyl adipate and divinyl sebacate
  • triallyl isocyan Allyl compounds such as nurate, triallylamine, tetraallyl pyromellitate, N, N, N ′, N′-tetraallyl-1,4-diamino
  • (meth) acrylic compounds are preferable. Furthermore, when a polarizer and a cellulose acylate film are bonded via an adhesive containing the same to produce a polarizing plate, at least one alicyclic group is included in the molecule from the viewpoint of enhancing durability such as heat resistance.
  • a (meth) acrylic compound having a skeleton or an aromatic ring skeleton is more preferable. Specific examples of the (meth) acrylic compound having at least one alicyclic skeleton or aromatic ring skeleton in the molecule include the above-described alicyclic monofunctional (meth) acrylates and monofunctional having an aromatic ring.
  • Preferable examples include (meth) acrylates, di (meth) acrylates having an alicyclic ring, or di (meth) acrylates having an aromatic ring.
  • di (meth) acrylate having a tricyclodecane skeleton is preferable, and specific examples of such (meth) acrylic compounds are tricyclodecane dimethylol di (meth) acrylate and the like. be able to.
  • the unsaturated compound ( ⁇ ) can be used to adjust the curing speed, the adhesion between the polarizer and the cellulose acylate film, the elastic modulus of the adhesive layer, the durability of the adhesive, and the like.
  • An unsaturated compound ((epsilon)) can be used individually by 1 type or in mixture of 2 or more types.
  • the blending ratio is preferably 35% by mass or less based on the entire composition. Thereby, the adhesiveness between a polarizer and a cellulose acylate film becomes excellent. When the amount of the unsaturated compound ( ⁇ ) is 35% by mass or less, sufficient adhesive strength with the polarizer is easily obtained. Therefore, the blending ratio of the unsaturated compound ( ⁇ ) is more preferably 30% by mass or less, and further preferably about 5 to 25% by mass, especially about 10 to 20% by mass.
  • Photoradical polymerization initiator ( ⁇ ) When the photocurable adhesive contains an unsaturated compound ( ⁇ ), it is preferable to add a photoradical polymerization initiator ( ⁇ ) in order to promote the radical polymerizability and make the curing rate sufficient.
  • radical photopolymerization initiator ( ⁇ ) are not particularly limited, but for example, 4′-phenoxy-2,2-dichloroacetophenone, 4′-tert-butyl-2,2-dichloroacetophenone, 2,2- Dimethoxy-2-phenylacetophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1-hydroxycyclohexyl phenyl ketone, ⁇ , ⁇ -diethoxyacetophenone, 2-hydroxy-2 -Methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methyl Propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2- Acetophenone photopolymerization initiators such as tilpropan-1-one and 2-benzyl-2-di
  • the photo radical polymerization initiator ( ⁇ ) can be used alone or in combination of two or more according to the desired performance.
  • the blending ratio is preferably 10% by weight or less, based on the entire composition, from the viewpoint of obtaining sufficient curing and strength, and 0.1 to 3.0% by weight. % Is more preferable.
  • the photocurable adhesive composition that can be used in the present invention, other components different from the components ( ⁇ 1) to ( ⁇ ) are optionally blended within a range not impairing the effects of the present invention.
  • other components there may be mentioned compounds having cationic polymerizability other than the epoxy compound ( ⁇ 1) and the oxetane compound ( ⁇ 2). Specific examples include, but are not limited to, an epoxy compound having one epoxy group in the molecule, and the like.
  • other component ( ⁇ ) having no polymerizability can be exemplified.
  • the blending ratio is preferably about 10% by mass or less based on the entire composition.
  • a photosensitizer is mentioned. By blending a photosensitizer, the reactivity is improved and the mechanical strength and adhesive strength of the cured product can be improved.
  • the photosensitizer include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreductive dyes.
  • benzoin derivatives such as benzoin methyl ether, benzoin isopropyl ether, ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, o Benzophenone derivatives such as methyl benzoylbenzoate, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone, 2-isopropylthioxanthone; 2 Anthraquinone derivatives such as chloroanthraquinone and 2-methylanthraquinone; acridone derivatives such as N-methylacridone and N-butylacridone; other ⁇ , ⁇ -diethoxyacetophenone, benzyl, Luenone, xanth
  • the photo sensitizer here is particularly one that functions as a sensitizer for the photo cationic polymerization initiator ( ⁇ 1). It is not limited. These may be used alone or in combination of two or more.
  • the photosensitizer is a cationically polymerizable monomer (including the above epoxy compound ( ⁇ 1) and oxetane compound ( ⁇ 2) in the photocurable adhesive composition that can be used in the present invention, and has the other cationic polymerization properties described above.
  • the total amount of the compound (including the compound when it is blended) is preferably 100 parts by mass and is preferably contained in the range of 0.1 to 20 parts by mass.
  • thermal cationic polymerization initiator can also be used as another component ( ⁇ ) having no polymerizability.
  • the thermal cationic polymerization initiator include benzylsulfonium salt, thiophenium salt, thiolanium salt, benzylammonium salt, pyridinium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester, and amine imide. These initiators can be easily obtained as commercial products.
  • both of these initiators are indicated by trade names, and ADEKA OPTON CP77 and ADEKA OPTON CP66 (manufactured by ADEKA Corporation), CI-2639, CI- 2624 (manufactured by Nippon Soda Co., Ltd.), Sun Aid SI-60L, Sun Aid SI-80L, Sun Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like.
  • polyols have the property of promoting cationic polymerization, they can also be used as other components ( ⁇ ) that do not have polymerizability.
  • the polyols those having no acidic groups other than phenolic hydroxy groups are preferable.
  • polyol compounds having no functional groups other than hydroxy groups polyester polyol compounds, polycaprolactone polyol compounds, polyol compounds having phenolic hydroxy groups.
  • polycarbonate polyol compounds are preferable.
  • other components ( ⁇ ) having no polymerizability include silane coupling agents, ion trapping agents, antioxidants, light stabilizers, chain transfer agents, sensitizers, and tackifiers.
  • An agent, a thermoplastic resin, a filler, a flow regulator, a plasticizer, an antifoaming agent, a leveling agent, a dye, an organic solvent, and the like can also be blended.
  • a thermoplastic resin those having a glass transition temperature of 70 ° C. or higher are preferable from the viewpoint of enhancing the durability of the polarizer, and particularly preferred examples include a methyl methacrylate polymer.
  • the polarizer which is the main component of the polarizing plate, is an element that passes only light having a plane of polarization in a certain direction
  • a typical known polarizer is a polyvinyl alcohol polarizing film.
  • the polyvinyl alcohol polarizing film includes those obtained by dyeing iodine on a polyvinyl alcohol film and those obtained by dyeing a dichroic dye.
  • polarizer a polarizer obtained by forming a polyvinyl alcohol aqueous solution into a film and dyeing it by uniaxial stretching or dyeing and then uniaxially stretching and then preferably performing a durability treatment with a boron compound may be used.
  • the film thickness of the polarizer is preferably 5 to 30 ⁇ m, particularly preferably 10 to 20 ⁇ m.
  • the ethylene unit content described in JP-A-2003-248123, JP-A-2003-342322, etc. is 1 to 4 mol%
  • the degree of polymerization is 2000 to 4000
  • the degree of saponification is 99.0 to 99.99 mol%.
  • the ethylene-modified polyvinyl alcohol is also preferably used.
  • an ethylene-modified polyvinyl alcohol film having a hot water cutting temperature of 66 to 73 ° C. is preferably used.
  • a polarizer using this ethylene-modified polyvinyl alcohol film is excellent in polarization performance and durability, and has few color spots, and is particularly preferably used for a large-sized liquid crystal display device.
  • the polarizing plate is a cellulose acylate containing a cellulose acylate having an acyl group substitution degree of 2.0 to 2.5 and a Tg reducing agent on one surface of a polarizer using a photocurable adhesive. It can be manufactured by laminating rate films. During lamination, among both surfaces of the cellulose acylate film, r value satisfies the above 1.1, a surface d A is detected, bonded to the polarizer. That is, of the two surfaces of the cellulose acylate film, the surface with the larger detection value of the Tg reducing agent by time-of-flight secondary ion mass spectrometry is used as the bonding surface with the polarizer.
  • the cellulose acylate film according to the present invention may be used on the other surface of the polarizer constituting the polarizing plate, or another optical film is preferably bonded.
  • other optical films include commercially available cellulose ester films (for example, Konica Minoltak KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, KC8UE, KC8UY-HA, HC8UX-HA, HC8UX -RHA-C, KC8UXW-RHA-NC, KC4UXW-RHA-NC, manufactured by Konica Minolta Opto Co., Ltd.) are preferably used.
  • the polarizing plate has the following photo-curing adhesive on at least one of the pretreatment step for easily adhering the surface of the cellulose acylate film to which the polarizer is adhered and the adhesive surface of the polarizer and the cellulose acylate film.
  • Adhesive application process to be applied a polarizer and a cellulose acylate film are bonded and bonded via an adhesive layer, and a polarizer and a cellulose acylate film are bonded via an adhesive layer It can manufacture by the manufacturing method including the hardening process which hardens an adhesive bond layer in a state.
  • Pretreatment process the surface of the cellulose acylate film that adheres to the polarizer is subjected to an easy adhesion treatment.
  • an easy adhesion treatment is performed on each cellulose acylate film.
  • the surface subjected to the easy adhesion treatment is treated as a bonding surface with the polarizer, and therefore, among both surfaces of the cellulose acylate film, the r value satisfies 1.1 or more, d A is The detected surface is subjected to an easy adhesion treatment.
  • the photocurable adhesive is applied to at least one of the adhesive surfaces of the polarizer and the cellulose acylate film.
  • the photocurable adhesive is applied directly to the surface of the polarizer or the cellulose acylate film, there is no particular limitation on the application method.
  • various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used.
  • the method of pressurizing with a roller etc. and spreading it uniformly can also be utilized.
  • Bonding process For example, when a photocurable adhesive is applied to the surface of the polarizer in the previous application step, a cellulose acylate film is superimposed thereon.
  • a photocurable adhesive is applied to the surface of the cellulose acylate film in the previous application step, a polarizer is superimposed thereon.
  • a photocurable adhesive agent is cast between a polarizer and a cellulose acylate film, a polarizer and a cellulose acylate film are piled up in that state.
  • both sides when a cellulose acylate film is bonded to both sides of a polarizer and a photocurable adhesive is used on both sides, the cellulose acylate film is superimposed on each side of the polarizer via a photocurable adhesive. Is done.
  • both sides when the cellulose acylate film is superimposed on one side of the polarizer, the polarizer side and the cellulose acylate film side are referred to, and when the cellulose acylate film is superimposed on both sides of the polarizer, Means the cellulose acylate film side of both surfaces), and is pressed with a roller or the like.
  • the material of the roller metal, rubber or the like can be used.
  • the rollers arranged on both sides may be made of the same material or different materials.
  • an active energy ray is irradiated onto an uncured photocurable adhesive to cure an adhesive layer containing an epoxy compound or an oxetane compound, and the polarizer and cellulose layered via the photocurable adhesive Adhere to acylate film.
  • the active energy ray may be irradiated from either the polarizer side or the cellulose acylate film side.
  • bonding a cellulose acylate film on both surfaces of a polarizer either cellulose acylate film is in a state where the cellulose acylate film is superposed on both surfaces of the polarizer via a photocurable adhesive, respectively.
  • the active energy ray visible light, ultraviolet ray, X-ray, electron beam and the like can be used, but ultraviolet ray is generally preferably used because it is easy to handle and has a sufficient curing rate.
  • the light source of the active energy ray is not particularly limited, but has a light emission distribution at a wavelength of 400 nm or less. An LED lamp or the like can be used.
  • the light irradiation intensity to the photocurable adhesive is determined for each target composition and is not particularly limited, but the irradiation intensity in the wavelength region effective for activating the polymerization initiator is UV. Adjustment is preferably made so that it is in the range of 1 to 3,000 mW / cm 2 as -B (ultraviolet light in the middle wavelength range of 280 to 320 nm). If the irradiation intensity is in the range of 1 to 3,000 mW / cm 2 , an appropriate reaction time is sufficient, and the yellow of the photocurable adhesive is generated by heat radiated from the lamp and heat generated during polymerization of the photocurable adhesive. Deformation and deterioration of the polarizer can be prevented.
  • the light irradiation time to the photocurable adhesive is controlled for each composition to be cured and is not particularly limited.
  • the integrated light amount represented by the product of the irradiation intensity and the irradiation time is 10 to 5000 mJ / cm. It is preferably set to be in the range of 2 .
  • the integrated light quantity is in the range of 10 to 5000 mJ / cm 2 , active species derived from the polymerization initiator are sufficiently generated, and the adhesive layer is sufficiently cured.
  • an appropriate irradiation time is sufficient, which is suitable for improving productivity.
  • the photocurable adhesive When curing the photocurable adhesive by irradiating active energy rays, it is cured under conditions that do not deteriorate the various functions of the polarizing plate, such as the degree of polarization of the polarizer, the transmittance, the hue, and the transparency of the cellulose acylate film. It is preferable.
  • the thickness of the adhesive layer is not particularly limited, but is usually 50 ⁇ m or less, preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and further preferably 5 ⁇ m or less.
  • the polarizing plate according to the present invention can be suitably used for a liquid crystal display device.
  • the liquid crystal display device using the polarizing plate according to the present invention is excellent in visibility because a cellulose acylate film having an excellent optical compensation function is used.
  • such a liquid crystal display device has excellent durability because of high adhesion between the polarizer and the cellulose acylate film.
  • the bonding between the surface of the polarizing plate on the cellulose acylate film side and at least one surface of the liquid crystal cell can be performed by a known method. Depending on the case, it may be bonded through an adhesive layer.
  • the mode (driving method) of the liquid crystal display device is not particularly limited, and liquid crystal display devices in various drive modes such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, and OCB can be used.
  • a VA (MVA, PVA) type liquid crystal display device is preferable.
  • Example 1 ⁇ Preparation of Cellulose Acylate Film 101> (Preparation of fine particle dispersion 1) Fine particles (Aerosil R972V manufactured by Nippon Aerosil Co., Ltd.) 11 parts by weight Ethanol 89 parts by weight The above was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin to prepare a fine particle dispersion 1.
  • Fine particle additive solution 1 The fine particle dispersion 1 was slowly added to the dissolution tank containing methylene chloride with sufficient stirring.
  • the masses of methylene chloride and fine particle dispersion 1 are as follows. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution 1. 99 parts by mass of methylene chloride 5 parts by mass of fine particle dispersion 1
  • a main dope solution having the following composition was prepared.
  • methylene chloride and ethanol having the above composition were added to a pressure dissolution tank.
  • cellulose acylate having an acetyl substitution degree of 2.45 and a weight average molecular weight Mw of 135,000, and a cellulose acylate having an acetyl substitution degree of 2.45 and a weight average molecular weight of Mw of 180000 The cellulose acylate having the above composition mixed in a mass ratio was added while stirring. After heating and stirring, this was completely dissolved, and then Azumi filter paper No. 1 manufactured by Azumi Filter Paper Co., Ltd. was used.
  • the main dope solution was prepared by filtration using 244. The main dope solution was put into a sealed container and dissolved while stirring to prepare a dope solution.
  • drying was terminated while the drying zone was conveyed by a number of rolls.
  • the drying temperature was 130 ° C. and the conveyance tension was 100 N / m.
  • a cellulose acylate film 101 having a dry film thickness of 45 ⁇ m and a length of 2000 m was obtained.
  • ⁇ Preparation of cellulose acylate films 102-118> Cellulose acylate films 102 to 118 were produced in the same manner as the cellulose acylate film 101 except that the dope solution composition and production conditions were changed as shown in Table 1 below. In the production of the cellulose acylate film 101, the Tg reducing agent was not added. However, when the Tg reducing agent is added, the composition of the main dope solution includes the Tg reducing agent.
  • Table 1 shows the compounds of the Tg reducing agent contained in the main dope composition of each of the cellulose acylate films 101 to 118, the amount added, the value of the Tg reducing ability, the compound mixed as a hydrolysis inhibitor, and the mixture of the compounds The ratio, the added amount, the average log P value, and the value of the residual solvent amount in the cellulose acylate film at the time of peeling are described.
  • the following measurement method was used to determine the r value, which is the ratio of the Tg reducing agent distribution on both surfaces, the s value, which is the ratio of the hydrolysis inhibitor distribution, and the arithmetic mean.
  • the roughness Ra was measured.
  • Table 1 the Q1 surface represents the surface opposite to the surface that was in contact with the metal support during casting of the dope.
  • the Q2 plane represents the plane that was in contact with the metal support during casting of the dope.
  • Measuring device 2100TRIFT2 (Phisical Electronics) Measurement mode: Cooling measurement (temperature range -95 to -105 ° C) Primary ion: Ga (15 kV) Measurement area: 60 ⁇ m square Integration time: 2 minutes Reference ion m / Z in the case of Tg reducing agent (aromatic polyester (ar-14)): 119 Reference ion m / Z in the case of hydrolysis inhibitor (mixture of sugar ester compounds (a1), (a2), (a3), (a4)): 105 Among the detected values of Tg-lowering agent of the surface, as better the d A, the smaller the d B large, according to the above equation (1) to calculate the r value.
  • the detected values of the Tg reducing agent in the Q2 surface are higher than those in the Q1 surface in any of the cellulose acylate films 102 to 107 and 109 to 118. Was big.
  • the detection value of the hydrolysis inhibitor on each surface of the cellulose acylate films 101 to 118 was obtained using time-of-flight secondary ion mass spectrometry.
  • the larger one was d C
  • the smaller one was d D
  • the s value was calculated according to the above formula (2).
  • the aromatic polyester compound of the Tg reducing agent indicates the aromatic polyester compound (ar-5), (ar-14), (ar-16) or (PES-7) exemplified above.
  • Hydrolysis inhibitor compound no. A1 to a4 in the formulas represent the sugar ester compounds (a1), (a2), (a3), and (a4).
  • PETB represents pentaerythritol tetrabenzoate.
  • the ratio of the compound of the hydrolysis inhibitor is the compound no. The mixing ratio of the compound shown by is shown.
  • Example 2 ⁇ Preparation of polarizing plates 201-221> (Production of polarizer) A 70 ⁇ m thick polyvinyl alcohol film was swollen with water at 35 ° C. The obtained film was immersed in an aqueous solution consisting of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and further immersed in an aqueous solution at 45 ° C. consisting of 3 g of potassium iodide, 7.5 g of boric acid and 100 g of water. . The obtained film was uniaxially stretched under conditions of a stretching temperature of 55 ° C. and a stretching ratio of 5 times. The uniaxially stretched film was washed with water and dried to obtain a polarizer having a thickness of 20 ⁇ m.
  • Triarylsulfonium hexafluorophosphate was blended as a 50% propylene carbonate solution, and the solid content of triarylsulfonium hexafluorophosphate was shown below.
  • Polarizing plates using the cellulose acylate films 101 to 118 were produced as follows. First, a KC6UY (Konica Minolta Opto Co., Ltd.) film was prepared, and the surface was subjected to corona discharge treatment. The corona discharge treatment was performed at a corona output intensity of 2.0 kW and a line speed of 18 m / min. Next, the adhesive solution prepared above was applied to the corona discharge treated surface of the film with a bar coater so that the film thickness after curing was about 3 ⁇ m to form an adhesive layer. A polyvinyl alcohol-iodine polarizer prepared as described above was bonded to the obtained adhesive layer.
  • KC6UY Konica Minolta Opto Co., Ltd.
  • the surfaces of the cellulose acylate films 101 to 118 were subjected to corona discharge treatment.
  • the conditions for the corona discharge treatment were a corona output intensity of 2.0 kW and a line speed of 18 m / min.
  • the adhesive solution prepared above was applied to the corona discharge treated surfaces of the cellulose acylate films 101 to 118 with a bar coater so that the film thickness after curing was about 3 ⁇ m to form an adhesive layer. In that case, it bonded so that the slow axis of a cellulose acylate film and the absorption axis of a polarizer might become mutually orthogonal.
  • a polarizer polarizer having a KC6UY (Konica Minolta Opto Co., Ltd.) film bonded on one side is bonded to this adhesive layer, and cellulose acylate films 101 to 118 / polarizer / KC6UY (Konica Minolta) are bonded.
  • An optical film laminate was obtained. From the cellulose acylate film 101 to 118 side of this laminate, using a UV irradiation device with a belt conveyor (the lamp uses a D bulb manufactured by Fusion UV Systems) so that the integrated light quantity becomes 750 mJ / cm 2. The adhesive layer was cured by irradiating with ultraviolet rays.
  • polarizing plates 201 to 221 in which a polarizer was sandwiched between two films were prepared using each of the cellulose acylate films 101 to 118.
  • Table 2 below shows which of the cellulose acylate films 101 to 118 used for the production of each of the polarizing plates 201 to 221 and whether the bonding surface with the polarizer is the Q1 surface or the Q2 surface. As shown.
  • the polarizing plates 201 to 218 have the Q2 surface of the cellulose acylate films 101 to 118 as the bonding surface with the polarizer, and the polarizing plates 219 to 221 have the cellulose acylate film 102,
  • the Q1 surface of 104 and 109 was used as a bonding surface with a polarizer.
  • the polarizing plates 201 to 221 were allowed to stand for 500 hours under wet heat conditions of a temperature of 60 ° C. and 90% RH. Thereafter, the adhesion was evaluated depending on whether the polarizer constituting the polarizing plates 201 to 221 and the cellulose acylate film can be peeled by hand.
  • the evaluation criteria are as follows. ⁇ : Can not be peeled by hand. X: It was able to peel by hand.
  • the parallel transmittance (H0) is a transmittance value of a parallel laminated polarizing plate produced by superposing two identical polarizing plates so that their absorption axes are parallel to each other.
  • the orthogonal transmittance (H90) is a transmittance value of an orthogonal laminated polarizing plate produced by superposing two identical polarizing plates so that their absorption axes are orthogonal to each other.
  • These transmittances are Y values obtained by correcting the visibility using a two-degree field of view (C light source) of JIS Z 8701 (1982 edition).
  • the evaluation criteria for the degree of polarization are as follows. ⁇ : Polarization degree is 99.990 or more ⁇ : Polarization degree is 99.980 or more and less than 99.990 ⁇ : Polarization degree is less than 99.980
  • It can be used in the field of liquid crystal display technology and can be applied to polarizing plates and liquid crystal display devices using cellulose acylate.

Abstract

Provided is a polarizer which is configured of a cellulose acylate film and a polarizing element and in which improved adhesion between the film and the polarizing element has been attained with a photocurable adhesive to inhibit the degree of polarization from decreasing. Also provided is a liquid-crystal display device equipped with the polarizer. The polarizer is a polarizer obtained by laminating a cellulose acylate film that comprises a cellulose acylate having a degree of substitution with an acyl group in the range of 2.0-2.5 and a glass transition temperature lowering agent to one surface of a polarizing element using a photocurable adhesive, and is characterized in that when the amount of the glass transition temperature lowering agent present in the laminating-side surface of the cellulose acylate film and the amount of the agent present in the other surface of the film, the amounts being determined using time-of-flight secondary-ion mass spectroscopy (TOF-SIMS), are expressed by dA and dB, respectively, then the value of r represented by equation (1) is 1.1 or larger. Equation (1) r = dA/dB

Description

偏光板及び液晶表示装置Polarizing plate and liquid crystal display device
　本発明は、セルロースアシレートを用いた偏光板及び液晶表示装置に関する。 The present invention relates to a polarizing plate and a liquid crystal display device using cellulose acylate.
　セルロースエステルのなかでも、セルロースアシレートは、アシル基置換度を変化させることにより、幅広いリターデーションを持つ光学フィルムに適用できることが知られている。一般的に、アセチル基置換度の高いトリアセチルセルロース（ＴＡＣ）は、リターデーションが低いため、偏光板の保護フィルムに好適に用いられている。一方、トリアセチルセルロースを、ＶＡ型やＴＮ型等各種の液晶モードの光学補償フィルムとして用いるにはリターデーションの発現が不足することから、リターデーション上昇剤を添加する必要があった（例えば、特許文献１参照）。 Among cellulose esters, cellulose acylate is known to be applicable to optical films having a wide range of retardation by changing the acyl group substitution degree. Generally, triacetyl cellulose (TAC) having a high degree of acetyl group substitution is suitably used for a protective film for polarizing plates because of its low retardation. On the other hand, in order to use triacetyl cellulose as an optical compensation film in various liquid crystal modes such as VA type and TN type, since the expression of retardation is insufficient, it is necessary to add a retardation increasing agent (for example, patents) Reference 1).
　これに対し、アセチル基置換度の小さいジアセチルセルロース（ＤＡＣ）は、リターデーションの発現性が高いため、リターデーション上昇剤を添加しなくても、光学補償フィルムとしての機能を発揮することができると期待されている。 On the other hand, diacetyl cellulose (DAC) having a low degree of acetyl group substitution has high retardation expression, and therefore can function as an optical compensation film without adding a retardation increasing agent. Expected.
　アシル基置換度の小さいセルロースアシレートからなるフィルムが光学補償フィルムとして用いられる場合、偏光子と貼合され、偏光板が作製されるのが一般的である。そして、偏光板としての耐久性を考えた場合には、セルロースアシレートフィルムと偏光子との間の密着性は高いほど好ましい。 When a film made of cellulose acylate having a low acyl group substitution degree is used as an optical compensation film, it is generally bonded to a polarizer to produce a polarizing plate. And when durability as a polarizing plate is considered, the adhesiveness between a cellulose acylate film and a polarizer is so preferable that it is high.
　また、セルロースアシレートフィルムと偏光子とを貼合する際、セルロースアシレートフィルムの遅相軸と偏光子の吸収軸とを厳密に平行又は直角に重ね合わせる工程が必要とされる。これら２つの軸がわずかでもずれ、軸ずれと呼ばれる現象が起こると、偏光板の偏光度が低下するからである。セルロースアシレートフィルムの位相差発現性能が高ければ高いほど、偏光度の低下は顕著に現れるため、軸ずれに起因する偏光度の低下を緩和し得る手段の開発が望まれている。 In addition, when the cellulose acylate film and the polarizer are bonded, a step of superimposing the slow axis of the cellulose acylate film and the absorption axis of the polarizer exactly in parallel or at right angles is required. This is because the polarization degree of the polarizing plate decreases when these two axes are slightly shifted and a phenomenon called axial shift occurs. The higher the retardation development performance of the cellulose acylate film, the more pronounced the decrease in the degree of polarization. Therefore, it is desired to develop a means that can alleviate the decrease in the degree of polarization caused by the axis deviation.
　これまで、偏光子とセルロースアシレートからなる偏光板保護フィルムとの接着には、ポリビニルアルコール系接着剤が広く用いられてきた。その際、セルロースアシレートフィルムをあらかじめアルカリケン化液等で表面を親水化する必要があった。しかし、アシル基置換度の低いセルロースアシレートフィルムは、アルカリケン化工程において、フィルムの一部がアルカリケン化液に溶出し、工程を汚染するといった問題点があった。従って、アルカリケン化工程を必要としない接着剤が望まれていた。 Until now, polyvinyl alcohol adhesives have been widely used for bonding between a polarizer and a polarizing plate protective film made of cellulose acylate. At that time, it was necessary to hydrophilize the surface of the cellulose acylate film in advance with an alkali saponification solution or the like. However, the cellulose acylate film having a low degree of acyl group substitution has a problem that in the alkali saponification step, a part of the film is eluted into the alkali saponification solution and contaminates the step. Therefore, an adhesive that does not require an alkali saponification step has been desired.
　近年、偏光子と偏光板保護フィルムを貼合する際の接着剤として、光硬化性接着剤が注目を集めている（例えば、特許文献２～４参照）。光硬化性接着剤は、アルカリケン化工程を経なくても偏光子と接着できるので、アシル基置換度の小さなセルロースアシレートに適用されることが期待できる。 In recent years, photo-curing adhesives have attracted attention as adhesives when laminating polarizers and polarizing plate protective films (see, for example, Patent Documents 2 to 4). Since the photocurable adhesive can be bonded to the polarizer without passing through the alkali saponification step, it can be expected to be applied to cellulose acylate having a low degree of acyl group substitution.
　しかし、本発明者らはアシル基置換度の小さなセルロースアシレートからなる光学補償フィルムと偏光子とを、光硬化性接着剤を用いて接着した場合、偏光子との密着性が十分でなく、また偏光板の偏光度が大きく低下するという問題点を見出した。これは、光硬化性接着剤の硬化時の発熱や硬化収縮により、光学補償フィルムの微小な配向角のずれが生じ、軸ずれが発生することが原因と推定される。 However, when the present inventors bonded the optical compensation film made of cellulose acylate having a small acyl group substitution degree and the polarizer using a photocurable adhesive, the adhesion with the polarizer is not sufficient, Moreover, the problem that the polarization degree of a polarizing plate falls significantly was discovered. This is presumed to be caused by a slight misalignment of the orientation angle of the optical compensation film due to heat generation or curing shrinkage during curing of the photocurable adhesive, resulting in an axial misalignment.
欧州特許第９１１６５６号明細書European Patent No. 91656 特開２０１０－３９２９８号公報JP 2010-39298 A 特開２００９－２４４８６０号公報JP 2009-244860 A 特開２００９－２１１０５７号公報JP 2009-211057 A
　本発明は、上記問題・状況に鑑みてなされたものであり、その解決課題は、光硬化性接着剤を使用した場合に、偏光板を構成するセルロースアシレートフィルムと偏光子との密着性を向上させ、さらに偏光度の低下を緩和した偏光板を提供することである。また、当該偏光板が具備された液晶表示装置を提供することである。 This invention is made | formed in view of the said problem and the situation, and the solution subject is the adhesiveness of the cellulose acylate film which comprises a polarizing plate, and a polarizer, when using a photocurable adhesive agent. An object of the present invention is to provide a polarizing plate that improves and further reduces the decrease in the degree of polarization. Moreover, it is providing the liquid crystal display device provided with the said polarizing plate.
　本発明者は、上記課題を解決すべく、上記問題の原因等について検討する過程において、アシル基置換度が小さいセルロースアシレートとガラス転移温度低下剤を含むセルロースアシレートフィルムを採用することで、薄膜でありながら高いリターデーション値、高い位相差発現性が発揮されることを見出した。また、本発明者は光硬化性接着剤を用いて偏光子とセルロースアシレートフィルムを貼合する際、その貼合面のガラス転移温度低下剤の分布を他方の面より大きくすることにより、貼合面の密着性が向上し、偏光度の低下が抑制されることを見出し、本発明に至った。 In order to solve the above-mentioned problems, the present inventor adopts a cellulose acylate film containing a cellulose acylate having a low acyl group substitution degree and a glass transition temperature lowering agent in the course of examining the cause of the above-mentioned problem. It has been found that a high retardation value and high phase difference expression are exhibited while being a thin film. In addition, when the present inventors use a photocurable adhesive to bond a polarizer and a cellulose acylate film, the distribution of the glass transition temperature lowering agent on the bonding surface is made larger than that on the other surface, thereby bonding. It has been found that the adhesion of the mating surface is improved and a decrease in the degree of polarization is suppressed, and the present invention has been achieved.
　すなわち、本発明に係る上記課題は、以下の手段により解決される。
１．アシル基置換度が２．０～２．５の範囲内にあるセルロースアシレートと、ガラス転移温度低下剤と、を含むセルロースアシレートフィルムを、光硬化性接着剤を用いて偏光子の一方の面に貼り合わせた偏光板であって、
　飛行時間型二次イオン質量分析法（ＴＯＦ－ＳＩＭＳ）を用いて検出される、前記セルロースアシレートフィルムの貼合面の前記ガラス転移温度低下剤の検出値をｄＡ、他方の面の検出値をｄＢとしたとき、下記式（１）により示されるｒ値が１．１以上であることを特徴とする偏光板。
　式（１）　ｒ＝ｄＡ／ｄＢ
２．前記セルロースアシレートは、アシル基置換度が２．０～２．５の範囲内にあるジアセチルセルロースであることを特徴とする前記第１項に記載の偏光板。
３．前記ガラス転移温度低下剤のガラス転移温度低下能が、３．５℃／質量部以上であることを特徴とする前記第１項又は第２項に記載の偏光板。
４．前記セルロースアシレートフィルムは、加水分解防止剤をさらに含み、
　前記加水分解防止剤の平均ｌｏｇＰ値が、７．５以上であることを特徴とする前記第１項～第３項のいずれか一項に記載の偏光板。
５．前記貼合面の算術平均粗さが、他方の面より大きいことを特徴とする前記第１項～第４項のいずれか一項に記載の偏光板。
６．前記偏光板の偏光度が９９．９９％以上であることを特徴とする前記第１項～第５項のいずれか一項に記載の偏光板。
７．前記第１項～第６項のいずれか一項に記載の偏光板が、具備されていることを特徴とする液晶表示装置。 That is, the said subject which concerns on this invention is solved by the following means.
1. A cellulose acylate film containing a cellulose acylate having an acyl group substitution degree in the range of 2.0 to 2.5 and a glass transition temperature lowering agent is bonded to one of the polarizers using a photocurable adhesive. A polarizing plate bonded to a surface,
The detected value of the glass transition temperature reducing agent on the bonding surface of the cellulose acylate film, detected using time-of-flight secondary ion mass spectrometry (TOF-SIMS), is d A , and the detected value of the other surface The polarizing plate is characterized in that the r value represented by the following formula (1) is 1.1 or more, where d is B.
Formula (1) r = d A / d B
2. 2. The polarizing plate according to item 1, wherein the cellulose acylate is diacetyl cellulose having an acyl group substitution degree in the range of 2.0 to 2.5.
3. The glass transition temperature lowering ability of the glass transition temperature lowering agent is 3.5 ° C./part by mass or more.
4). The cellulose acylate film further comprises a hydrolysis inhibitor,
The polarizing plate according to any one of Items 1 to 3, wherein the hydrolysis inhibitor has an average log P value of 7.5 or more.
5. The polarizing plate according to any one of the first to fourth aspects, wherein an arithmetic average roughness of the bonding surface is larger than that of the other surface.
6). 6. The polarizing plate as described in any one of 1 to 5 above, wherein the polarizing degree of the polarizing plate is 99.99% or more.
7). A liquid crystal display device comprising the polarizing plate according to any one of items 1 to 6.
　本発明の上記手段により、セルロースアシレートフィルムと偏光子との密着性を向上させ、偏光板の偏光度の低下を緩和することができる。
　本発明の効果の発現機構ないし作用機構は明らかになっていないが、以下のように推察される。
　すなわち、光硬化性接着剤を用いてセルロースアシレートフィルムを偏光子に貼り合せる際、ガラス転移温度低下剤が貼合面に豊富に存在することによって、貼合面が他方の面より微小な凹凸が多く荒れた表面構造を有する。この表面構造が偏光子との密着性の向上に寄与しているものと考えられる。
　また、貼合面におけるガラス転移温度低下剤の存在量の増加に伴い、セルロースアシレートの存在量は減少する。そのため、貼合面近傍におけるセルロースアシレートフィルムのリターデーションの値は、セルロースアシレートフィルム全体の値と比較して小さくなっていると考えられる。セルロースアシレートフィルムのリターデーションの値が高いほど、貼合時の軸ずれによる偏光度の低下は顕著であることから、リターデーションが比較的小さい貼合面と偏光子を貼合することにより、偏光度の低下は緩和されると考えられる。 By the above means of the present invention, the adhesion between the cellulose acylate film and the polarizer can be improved, and the decrease in the degree of polarization of the polarizing plate can be alleviated.
The expression mechanism or action mechanism of the effect of the present invention has not been clarified, but is presumed as follows.
That is, when a cellulose acylate film is bonded to a polarizer using a photocurable adhesive, the bonding surface is smaller than the other surface due to the presence of a glass transition temperature reducing agent in the bonding surface. Has a rough surface structure. This surface structure is considered to contribute to the improvement of the adhesion with the polarizer.
Moreover, the abundance of cellulose acylate decreases with an increase in the abundance of the glass transition temperature lowering agent on the bonding surface. Therefore, it is considered that the retardation value of the cellulose acylate film in the vicinity of the bonding surface is smaller than the value of the whole cellulose acylate film. As the retardation value of the cellulose acylate film is higher, the decrease in the degree of polarization due to misalignment at the time of bonding is more conspicuous, and by bonding the bonding surface and the polarizer with a relatively small retardation, It is thought that the decrease in the degree of polarization is alleviated.
　本発明の偏光板は、アシル基置換度が２．０～２．５の範囲内にあるセルロースアシレートと、ガラス転移温度低下剤と、を含むセルロースアシレートフィルムを、光硬化性接着剤を用いて偏光子の一方の面に貼り合わせた偏光板であって、飛行時間型二次イオン質量分析法（ＴＯＦ－ＳＩＭＳ）を用いて検出される、前記セルロースアシレートフィルムの貼合面の前記ガラス転移温度低下剤の検出値をｄＡ、他方の面の検出値をｄＢとしたとき、前記式（１）により示されるｒ値が１．１以上であることを特徴とする。この特徴は、請求項１から請求項７までの請求項に係る発明に共通する技術的特徴である。 The polarizing plate of the present invention comprises a cellulose acylate film containing a cellulose acylate having an acyl group substitution degree in the range of 2.0 to 2.5 and a glass transition temperature reducing agent, and a photocurable adhesive. The polarizing plate is bonded to one surface of a polarizer using the time-of-flight secondary ion mass spectrometry (TOF-SIMS), and the bonding surface of the cellulose acylate film is detected using the polarizing plate. when the detected value of the glass transition temperature lowering agent and d a, the detection value of the other surface and d B, and wherein the r value represented by the formula (1) is 1.1 or more. This feature is a technical feature common to the inventions according to claims 1 to 7.
　本発明の実施態様としては、本発明の効果発現の観点から、前記セルロースアシレートは、アシル基置換度が２．０～２．５の範囲内にあるジアセチルセルロースであることが好ましい。また、前記ガラス転移温度低下剤のガラス転移温度低下能が、３．５℃／質量部以上であることが好ましい。また、前記セルロースアシレートフィルムは、加水分解防止剤をさらに含み、前記加水分解防止剤の平均ｌｏｇＰ値が、７．５以上であることが好ましい。また、前記貼合面の算術平均粗さが、他方の面より大きいことが好ましい。また、前記偏光板の偏光度が９９．９９％以上であることが好ましい。
　本発明の偏光板は、液晶表示装置に好適に具備され得る。 As an embodiment of the present invention, from the viewpoint of manifesting the effects of the present invention, the cellulose acylate is preferably diacetylcellulose having an acyl group substitution degree in the range of 2.0 to 2.5. Moreover, it is preferable that the glass transition temperature decreasing ability of the said glass transition temperature decreasing agent is 3.5 degreeC / mass part or more. Moreover, it is preferable that the said cellulose acylate film further contains a hydrolysis inhibiting agent and the average logP value of the said hydrolysis inhibiting agent is 7.5 or more. Moreover, it is preferable that the arithmetic mean roughness of the said bonding surface is larger than the other surface. The polarization degree of the polarizing plate is preferably 99.99% or more.
The polarizing plate of the present invention can be suitably included in a liquid crystal display device.
　以下、本発明とその構成要素及び本発明を実施するための形態・態様について詳細な説明をする。なお、本願において、「～」はその前後に記載される数値を下限値及び上限値として含む意味で使用する。 Hereinafter, the present invention, its constituent elements, and modes and modes for carrying out the present invention will be described in detail. In the present application, “˜” is used in the sense of including the numerical values described before and after it as the lower limit value and the upper limit value.
＜偏光板＞
　本発明に係る偏光板は、アシル基置換度が２．０～２．５の範囲内にあるセルロースアシレートフィルムと、ガラス転移温度低下剤と、を含むセルロースアシレートフィルムを、光硬化性接着剤を用いて偏光子の一方の面に貼り合わせてなる。 <Polarizing plate>
The polarizing plate according to the present invention is a photocurable adhesive comprising a cellulose acylate film having an acyl group substitution degree in the range of 2.0 to 2.5 and a glass transition temperature reducing agent. It is bonded to one surface of the polarizer using an agent.
＜セルロースアシレートフィルム＞
　本発明に用いられるセルロースアシレートフィルムは、アシル基置換度が２．０～２．５の範囲内にあるセルロースアシレートを含む。このようにアシル基置換度が小さいセルロースアシレートを採用することで、高い位相差発現性が発揮され、位相差の高い位相差フィルムとする場合であっても薄膜化が可能となる。また、高い位相差を発現させる場合にも延伸倍率を低く抑えることができ、破断等の故障を回避できる等の利点が得られる。 <Cellulose acylate film>
The cellulose acylate film used in the present invention contains cellulose acylate having an acyl group substitution degree in the range of 2.0 to 2.5. By adopting cellulose acylate having a low acyl group substitution degree in this way, high retardation development is exhibited, and even when a retardation film having a high retardation is obtained, a thin film can be obtained. In addition, even when a high phase difference is developed, the stretch ratio can be kept low, and advantages such as failure such as breakage can be avoided.
　ここで、セルロース分子はグルコースユニットが多数連結したものからなっており、グルコースユニットに３個のヒドロキシ基（水酸基）がある。この３個のヒドロキシ基にアシル基が誘導された数を、アシル基置換度という。例えば、ジアセチルセルロース（ＤＡＣ）は、グルコースユニットの３個のヒドロキシ基のうち、平均して２．０～２．５個のヒドロキシ基に、アセチル基が結合している。 Here, the cellulose molecule is composed of many glucose units connected, and the glucose unit has three hydroxy groups (hydroxyl groups). The number of acyl groups derived from these three hydroxy groups is called the degree of acyl group substitution. For example, diacetyl cellulose (DAC) has an acetyl group bonded to an average of 2.0 to 2.5 hydroxy groups among the three hydroxy groups of the glucose unit.
　本発明に用いられるセルロースアシレートとしては、炭素数２～２２程度のカルボン酸エステルが挙げられ、芳香族カルボン酸のエステルでもよいが、特にセルロースの低級脂肪酸エステルであることが好ましい。セルロースの低級脂肪酸エステルにおける低級脂肪酸とは炭素原子数が６以下の脂肪酸を意味する。ヒドロキシ基に結合するアシル基は、直鎖であっても分岐してもよく、また環を形成してもよい。さらに別の置換基が置換してもよい。炭素数としては炭素数２～６のアシル基の中で選択することが好ましい。当該アシル基の炭素数は２～４であることが好ましく、炭素数が２～３であることがより好ましい。 Examples of the cellulose acylate used in the present invention include carboxylic acid esters having about 2 to 22 carbon atoms, which may be aromatic carboxylic acid esters, but are particularly preferably lower fatty acid esters of cellulose. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. The acyl group bonded to the hydroxy group may be linear or branched, and may form a ring. Furthermore, another substituent may be substituted. The carbon number is preferably selected from acyl groups having 2 to 6 carbon atoms. The acyl group preferably has 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms.
　例えば、セルロースアセテート、セルロースプロピオネート、セルロースブチレート等や、特開平１０－４５８０４号、同８－２３１７６１号、米国特許第２，３１９，０５２号等に記載されているようなセルロースアセテートプロピオネート、セルロースアセテートブチレート、セルロースアセテートフタレート等の混合脂肪酸エステルを用いることが好ましい。 For example, cellulose acetate, cellulose propionate, cellulose butyrate and the like, and cellulose acetate propio as described in JP-A Nos. 10-45804, 8-231761, US Pat. No. 2,319,052, etc. It is preferable to use mixed fatty acid esters such as nate, cellulose acetate butyrate, and cellulose acetate phthalate.
　セルロースアシレートのアシル基置換度の測定は、ＡＳＴＭのＤ－８１７－９１に準じて実施することができ、好ましいアシル基置換度は、２．１８～２．４５である。
　セルロースアシレートのアシル基置換度が２．０以上である場合、ドープ粘度の上昇によるフィルム面品質の劣化、延伸張力の上昇によるヘイズアップ等の発生を防止できる。また、アシル基置換度が２．５以下である場合、必要な位相差が得られやすい。 The acyl group substitution degree of cellulose acylate can be measured in accordance with ASTM D-817-91, and the preferred acyl group substitution degree is 2.18 to 2.45.
When the acyl group substitution degree of cellulose acylate is 2.0 or more, it is possible to prevent the occurrence of deterioration in film surface quality due to increase in dope viscosity and haze-up due to increase in stretching tension. Further, when the acyl group substitution degree is 2.5 or less, a necessary phase difference is easily obtained.
　セルロースアシレートの数平均分子量（Ｍｎ）は３００００～３０００００の範囲が、得られたセルロースアシレートフィルムの機械的強度が強く好ましい。さらに５００００～２０００００の数平均分子量のセルロースアシレートが好ましく用いられる。
　セルロースアシレートの重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）の値は、１．４～３．０の範囲内であることが好ましい。 The number average molecular weight (Mn) of the cellulose acylate is preferably in the range of 30000 to 300000, since the mechanical strength of the obtained cellulose acylate film is strong. Further, cellulose acylate having a number average molecular weight of 50,000 to 200,000 is preferably used.
The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) of the cellulose acylate is preferably in the range of 1.4 to 3.0.
　セルロースアシレートの数平均分子量（Ｍｎ）及び重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて測定される。
　測定条件は、以下の通りである。
　溶媒：　　　メチレンクロライド
　カラム：　　Ｓｈｏｄｅｘ　Ｋ８０６、Ｋ８０５、Ｋ８０３Ｇ（昭和電工（株）製を３本接続して使用する）
　カラム温度：２５℃
　試料濃度：　０．１質量％
　検出器：　　ＲＩ　Ｍｏｄｅｌ　５０４（ＧＬサイエンス社製）
　ポンプ：　　Ｌ６０００（日立製作所（株）製）
　流量：　　　１．０ｍｌ／ｍｉｎ
　校正曲線：　標準ポリスチレンＳＴＫ　ｓｔａｎｄａｒｄ　ポリスチレン（東ソー（株）製）Ｍｗ＝１００００００～５００の１３サンプルによる校正曲線を使用する。１３サンプルは、ほぼ等間隔に用いる。 The number average molecular weight (Mn) and the weight average molecular weight (Mw) of cellulose acylate are measured using gel permeation chromatography (GPC).
The measurement conditions are as follows.
Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three products manufactured by Showa Denko KK)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Co., Ltd.) Mw = 1000000-500 13 calibration curves are used. Thirteen samples are used at approximately equal intervals.
　本発明に用いられるセルロースアシレートは、公知の方法により合成され得る。具体的には、特開平１０－４５８０４号に記載の方法を参考にして合成することができる。
　セルロースアシレートの原料のセルロースとしては、特に限定はないが、綿花リンター、木材パルプ（針葉樹由来、広葉樹由来）、ケナフ等が挙げられる。また、それらから得られたセルロースアシレートを、それぞれ任意の割合で混合して使用してもよい。
　一方、セルロースアシレートの市販品を用いてもよい。セルロースアシレートの市販品としては、ダイセル社のＬ２０、Ｌ３０、Ｌ４０、Ｌ５０、イーストマンケミカル社のＣａ３９８－３、Ｃａ３９８－６、Ｃａ３９８－１０、Ｃａ３９８－３０、Ｃａ３９４－６０Ｓが挙げられる。 The cellulose acylate used in the present invention can be synthesized by a known method. Specifically, it can be synthesized with reference to the method described in JP-A-10-45804.
Cellulose as a raw material for cellulose acylate is not particularly limited, and examples thereof include cotton linter, wood pulp (derived from coniferous tree, derived from broadleaf tree), kenaf and the like. Moreover, you may use the cellulose acylate obtained from them by mixing in arbitrary ratios, respectively.
On the other hand, a commercially available cellulose acylate may be used. Examples of commercially available cellulose acylates include L20, L30, L40, and L50 manufactured by Daicel, and Ca398-3, Ca398-6, Ca398-10, Ca398-30, and Ca394-60S manufactured by Eastman Chemical.
　＜ガラス転移温度低下剤＞
　本発明に用いられるセルロースアシレートフィルムは、ガラス転移温度低下剤（以下、Ｔｇ低下剤という。）を含む。このように、セルロースアシレートフィルムがＴｇ低下剤を含むことにより、硬く脆い性質を有するセルロースアシレートのガラス転移温度Ｔｇが低下し、その加工性や機械的物性が改善され得る。そしてその結果、薄膜でありながら高リターデーション値を有し、高倍率な延伸でも内部ヘイズの上昇が抑えられ、位相差ムラも小さく、しかも湿熱環境下でもヘイズの上昇が抑えられるセルロースアシレートフィルムが提供され得る。 <Glass transition temperature lowering agent>
The cellulose acylate film used in the present invention contains a glass transition temperature lowering agent (hereinafter referred to as Tg lowering agent). Thus, when a cellulose acylate film contains a Tg reducing agent, the glass transition temperature Tg of the cellulose acylate which has a hard and brittle property can fall, and the workability and mechanical physical property can be improved. As a result, the cellulose acylate film has a high retardation value despite being a thin film, suppresses an increase in internal haze even when stretched at a high magnification, reduces retardation unevenness, and suppresses an increase in haze even in a humid heat environment. Can be provided.
　本発明において用いられるＴｇ低下剤とは、それを含まない、アシル基置換度が２．０～２．５であるセルロースアシレート単独でのガラス転移温度Ｔｇの値が、それを添加することによって低下する添加剤を意味し、このような定義を満足する限り、いかなる物質がＴｇ低下剤として用いられてもよい。
　なお、セルロースアシレートフィルムのガラス転移温度Ｔｇの値は、示差走査熱量測定法（ＤＳＣ）により測定された値である。 The Tg lowering agent used in the present invention is a glass transition temperature Tg of a cellulose acylate having an acyl group substitution degree of 2.0 to 2.5 that does not contain it. Any substance may be used as a Tg lowering agent as long as it means an additive that lowers and satisfies such a definition.
In addition, the value of the glass transition temperature Tg of a cellulose acylate film is a value measured by the differential scanning calorimetry (DSC).
　なお、アシル基置換度が２．０～２．５であるセルロースアシレートの種類に応じて、ある物質がＴｇ低下剤の定義に該当する場合と該当しない場合とが生じる場合、当該物質は、Ｔｇ低下剤の定義に該当する場合におけるアシル基置換度が２．０～２．５であるセルロースアシレートとの併用であれば、本発明においてＴｇ低下剤として用いられ得る。 Note that, depending on the type of cellulose acylate having an acyl group substitution degree of 2.0 to 2.5, when a substance falls within the case of not meeting the definition of a Tg reducing agent, the substance is: If it is used in combination with a cellulose acylate having an acyl group substitution degree of 2.0 to 2.5 when the definition falls within the definition of a Tg reducing agent, it can be used as a Tg reducing agent in the present invention.
　Ｔｇ低下剤のガラス転移温度低下能（以下、Ｔｇ低下能という。）についても、特に制限はないが、好ましくは３．５℃／質量部以上であり、より好ましくは３．８℃／質量部以上であり、さらに好ましくは４．０℃／質量部以上である。
　ここで、Ｔｇ低下能とは、ある物質の単位質量あたりのガラス転移温度Ｔｇを低下させる能力をいい、下記数式（３）により定義される。
Figure JPOXMLDOC01-appb-M000001
 〔式中、Ｘはセルロースアシレートを単独で製膜して得られたセルロースアシレートフィルムのガラス転移温度Ｔｇを表し、Ｙは当該セルロースアシレート１００質量部に対し、Ｔｇ低下剤を５質量部添加した後に同様に製膜して得られたセルロースアシレートフィルムのガラス転移温度Ｔｇを表す。〕 The glass transition temperature lowering ability (hereinafter referred to as Tg lowering ability) of the Tg lowering agent is not particularly limited, but is preferably 3.5 ° C / part by mass or more, more preferably 3.8 ° C / part by mass. It is above, More preferably, it is 4.0 degrees C / mass part or more.
Here, the Tg lowering ability means the ability to lower the glass transition temperature Tg per unit mass of a certain substance, and is defined by the following mathematical formula (3).
Figure JPOXMLDOC01-appb-M000001
 [Wherein, X represents a glass transition temperature Tg of a cellulose acylate film obtained by independently forming a cellulose acylate, and Y represents 5 parts by mass of a Tg reducing agent with respect to 100 parts by mass of the cellulose acylate. The glass transition temperature Tg of the cellulose acylate film obtained by adding a film in the same manner after the addition is shown. ]
　Ｔｇ低下剤のＴｇ低下能が、上記範囲内の値であると、少ない添加量でも優れたＴｇ低下効果が発揮され得る。このため、添加剤を多量に添加せざるを得ない場合等に発生するブリードアウト等が防止され得る。一方、Ｔｇ低下能の上限値については特に制限はないが、実際には５．０℃／質量部以下程度である。 When the Tg reducing ability of the Tg reducing agent is a value within the above range, an excellent Tg reducing effect can be exhibited even with a small addition amount. For this reason, the bleed-out etc. which generate | occur | produce when the additive must be added in large quantities can be prevented. On the other hand, the upper limit of the Tg lowering ability is not particularly limited, but is actually about 5.0 ° C./part by mass or less.
　なお、Ｔｇ低下能についても、アシル基置換度が２．０～２．５であるセルロースアシレートの種類によっては、Ｔｇ低下剤として用いた物質が、上述したＴｇ低下能の好ましい範囲に含まれる場合と、含まれない場合とが生じうる。このような場合、当該物質は、上述したＴｇ低下能の好ましい範囲に含まれる場合におけるアシル基置換度が２．０～２．５であるセルロースアシレートと併用される場合に限り、上述の好ましいＴｇ低下能の範囲を満たすＴｇ低下剤として解釈されるものとする。 Regarding the Tg lowering ability, depending on the type of cellulose acylate having an acyl group substitution degree of 2.0 to 2.5, the substance used as the Tg lowering agent is included in the preferred range of the above Tg lowering ability. Cases and cases that are not included. In such a case, the substance is preferable as described above only when the substance is used in combination with cellulose acylate having an acyl group substitution degree of 2.0 to 2.5 when included in the preferable range of the above-described Tg reducing ability. It shall be interpreted as a Tg lowering agent that satisfies the range of Tg lowering ability.
　本発明において用いられるＴｇ低下剤の具体的な形態については、上述したＴｇ低下剤の定義を満たす限り、好ましくはさらに上述したＴｇ低下能の好ましい範囲を満たす限り、特に制限はない。Ｔｇ低下剤の一例としては、下記一般式（Ｉ）で表されるポリエステル化合物が挙げられる。
　一般式（Ｉ）　Ｘ－Ｏ－Ｂ－｛Ｏ－Ｃ（＝Ｏ）－Ａ－Ｃ（＝Ｏ）－Ｏ－Ｂ｝ｎ－Ｏ－Ｘ〔式中、Ｂは炭素数２～６の直鎖若しくは分岐のアルキレン基、又は直鎖若しくは分岐のシクロアルキレン基を表す。Ａは炭素数６～１４の芳香環、炭素数２～６の直鎖若しくは分岐のアルキレン基、又は炭素数２～６の直鎖若しくは分岐のシクロアルキレン基を表す。Ｘは水素原子又は炭素数６～１４の芳香環を含むモノカルボン酸残基を表す。ｎは１以上の自然数を表す。〕 The specific form of the Tg reducing agent used in the present invention is not particularly limited as long as the definition of the Tg reducing agent described above is satisfied, and preferably the preferable range of the Tg reducing ability described above is satisfied. An example of the Tg lowering agent is a polyester compound represented by the following general formula (I).
General formula (I) X—O—B— {O—C (═O) —A—C (═O) —O—B} n —O—X wherein B is a straight chain having 2 to 6 carbon atoms A chain or branched alkylene group, or a linear or branched cycloalkylene group is represented. A represents an aromatic ring having 6 to 14 carbon atoms, a linear or branched alkylene group having 2 to 6 carbon atoms, or a linear or branched cycloalkylene group having 2 to 6 carbon atoms. X represents a hydrogen atom or a monocarboxylic acid residue containing an aromatic ring having 6 to 14 carbon atoms. n represents a natural number of 1 or more. ]
　一般式（Ｉ）で表されるポリエステル化合物は、芳香環（炭素数６～１４）、直鎖若しくは分岐のアルキレン基、又は直鎖若しくは分岐のシクロアルキレン基（ともに炭素数２～６）を有するジカルボン酸と、炭素数２～６の直鎖若しくは分岐のアルキレンジオール又はシクロアルキレンジオールとの交互共重合により得られる交互共重合体である。
　芳香族ジカルボン酸と、直鎖若しくは分岐のアルキレン基又はシクロアルキレン基を有するジカルボン酸とは、それぞれ単独で用いても、混合物として用いても構わないが、セルロースアシレートとの相溶性の点から、少なくとも芳香族ジカルボン酸が１０％以上含まれることが好ましい。また、芳香環（炭素数６～１４）を有するモノカルボン酸で両末端を封止してもよい。 The polyester compound represented by formula (I) has an aromatic ring (6 to 14 carbon atoms), a linear or branched alkylene group, or a linear or branched cycloalkylene group (both having 2 to 6 carbon atoms). An alternating copolymer obtained by alternating copolymerization of a dicarboxylic acid and a linear or branched alkylene diol or cycloalkylene diol having 2 to 6 carbon atoms.
The aromatic dicarboxylic acid and the dicarboxylic acid having a linear or branched alkylene group or cycloalkylene group may be used alone or as a mixture, but from the viewpoint of compatibility with cellulose acylate. It is preferable that at least 10% or more of the aromatic dicarboxylic acid is contained. Alternatively, both ends may be sealed with a monocarboxylic acid having an aromatic ring (having 6 to 14 carbon atoms).
　芳香環（炭素数６～１４）を有するジカルボン酸、つまり炭素数６～１６の芳香族ジカルボン酸としては、例えばフタル酸、イソフタル酸、テレフタル酸、１，５－ナフタレンジカルボン酸、１，４－ナフタレンジカルボン酸、１，８－ナフタレンジカルボン酸、２，３－ナフタレンジカルボン酸、２，６－ナフタレンジカルボン酸、２，８－ナフタレンジカルボン酸、２，２′－ビフェニルジカルボン酸、４，４′－ビフェニルジカルボン酸、等が挙げられる。そのなかでも好ましくは、テレフタル酸、２，６－ナフタレンジカルボン酸、４，４′－ビフェニルジカルボン酸である。 Examples of dicarboxylic acids having an aromatic ring (6 to 14 carbon atoms), that is, aromatic dicarboxylic acids having 6 to 16 carbon atoms include phthalic acid, isophthalic acid, terephthalic acid, 1,5-naphthalenedicarboxylic acid, 1,4- Naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,8-naphthalenedicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 4,4'- And biphenyl dicarboxylic acid. Among these, terephthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-biphenyldicarboxylic acid are preferable.
　直鎖若しくは分岐のアルキレン基又はシクロアルキレン基（炭素数２～６）を有するジカルボン酸としては、例えばマロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、１，２－シクロヘキサンジカルボン酸、１，４－シクロヘキサンジカルボン酸等が挙げられる。そのなかでも好ましくは、コハク酸、アジピン酸、１，４－シクロヘキサンジカルボン酸である。 Examples of the dicarboxylic acid having a linear or branched alkylene group or cycloalkylene group (having 2 to 6 carbon atoms) include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and 1,2-cyclohexanedicarboxylic acid. Examples thereof include acid and 1,4-cyclohexanedicarboxylic acid. Of these, succinic acid, adipic acid, and 1,4-cyclohexanedicarboxylic acid are preferable.
　また、炭素数が２～６の直鎖若しくは分岐のアルキレンジオール又はシクロアルキレンジオールとしては、例えばエタンジオール（エチレングリコール）、１，２－プロパンジオール、１，３－プロパンジオール、１，２－ブタンジオール、１，３－ブタンジオール、２－メチル－１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、３－メチル－１，５－ペンタンジオール、１，６－ヘキサンジオール、１，４－シクロヘキサンジオール、１，４－シクロヘキサンジメタノール等が挙げられる。そのなかでも、好ましくはエタンジオール（エチレングリコール）、１，２－プロパンジオール、１，３－プロパンジオール、１，３－ブタンジオールである。 Examples of the linear or branched alkylene diol or cycloalkylene diol having 2 to 6 carbon atoms include ethanediol (ethylene glycol), 1,2-propanediol, 1,3-propanediol, and 1,2-butane. Diol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexane Examples thereof include diol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. Among these, ethanediol (ethylene glycol), 1,2-propanediol, 1,3-propanediol, and 1,3-butanediol are preferable.
　なかでも、Ａが置換基を有していてもよいベンゼン環、ナフタレン環又はビフェニル環であることが、Ｔｇ低下能に優れるという観点から好ましい。ここで、ベンゼン環、ナフタレン環又はビフェニル環が有し得る置換基とは、炭素数１～６のアルキル基、炭素数２～６のアルケニル基又は炭素数１～６のアルコキシ基である。 Among these, A is preferably a benzene ring, naphthalene ring or biphenyl ring which may have a substituent, from the viewpoint of excellent Tg lowering ability. Here, the substituent that the benzene ring, naphthalene ring or biphenyl ring may have is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
　ポリエステル化合物の両末端を封止する、芳香環（炭素数６～１４）を有するモノカルボン酸としては、例えば安息香酸、オルトトルイル酸、メタトルイル酸、パラトルイル酸、パラターシャリブチル安息香酸、ジメチル安息香酸、パラメトキシ安息香酸等が挙げられる。そのなかでも好ましくは安息香酸、パラトルイル酸、パラターシャリブチル安息香酸である。 Examples of monocarboxylic acids having aromatic rings (6 to 14 carbon atoms) that seal both ends of the polyester compound include benzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, p-tert-butylbenzoic acid, and dimethylbenzoic acid. And paramethoxybenzoic acid. Of these, benzoic acid, p-toluic acid and p-tert-butylbenzoic acid are preferred.
　芳香族ポリエステル化合物は、常法により上述したジカルボン酸とアルキレンジオール又はシクロアルキレンジオールとのポリエステル化反応、エステル交換反応による熱溶融縮合法、又はこれら酸の酸クロライドとグリコール類との界面縮合法のいずれかの方法によって容易に合成することができる。さらに、上述した芳香族モノカルボン酸を加えることにより、両末端が封止されたポリエステル化合物を合成することができる。 Aromatic polyester compounds are prepared by the conventional methods of polyesterification reaction of dicarboxylic acid and alkylene diol or cycloalkylene diol, hot melt condensation method by transesterification, or interfacial condensation method of acid chlorides of these acids and glycols. It can be easily synthesized by any method. Furthermore, by adding the aromatic monocarboxylic acid described above, a polyester compound in which both ends are sealed can be synthesized.
　以下に、本発明において用いられ得る芳香族ポリエステル化合物（ＰＥＳ－１）～（ＰＥＳ－１４）、（ａｒ－１）～（ａｒ－２０）を例示する。
Figure JPOXMLDOC01-appb-C000002
 Examples of aromatic polyester compounds (PES-1) to (PES-14) and (ar-1) to (ar-20) that can be used in the present invention are shown below.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　以上、Ｔｇ低下剤の具体例として、一般式（Ｉ）で表される芳香族ポリエステル化合物について詳細に説明したが、その他のＴｇ低下剤が用いられてももちろんよい。
　本発明の一形態に係るセルロースアシレートフィルムにおいて、Ｔｇ低下剤は、１種のみが単独で用いられてもよいし、２種以上が併用されてもよい。また、本発明の一形態に係るセルロースアシレートフィルムにおけるＴｇ低下剤の添加量についても特に制限はないが、セルロースアシレート１００質量％に対して、好ましくは１～５質量％であり、より好ましくは１．５～３．５質量％である。Ｔｇ低下剤の添加量が１質量％以上であれば、Ｔｇ低下剤の本来の目的であるＴｇ低下性能が十分に発揮され得る。一方、Ｔｇ低下剤の添加量が５質量％以下であれば、Ｔ低下剤の添加量の増加に伴うセルロースアシレートフィルムの位相差発現性能の低下が防止され得る。 As described above, the aromatic polyester compound represented by the general formula (I) has been described in detail as a specific example of the Tg reducing agent, but other Tg reducing agents may be used as a matter of course.
In the cellulose acylate film according to one embodiment of the present invention, only one Tg reducing agent may be used alone, or two or more Tg reducing agents may be used in combination. The amount of the Tg reducing agent added to the cellulose acylate film according to one embodiment of the present invention is not particularly limited, but is preferably 1 to 5% by mass, more preferably 100% by mass with respect to cellulose acylate. Is 1.5 to 3.5% by mass. If the added amount of the Tg reducing agent is 1% by mass or more, the Tg reducing performance that is the original purpose of the Tg reducing agent can be sufficiently exhibited. On the other hand, if the addition amount of the Tg reducing agent is 5% by mass or less, the retardation development performance of the cellulose acylate film accompanying the increase in the addition amount of the T reducing agent can be prevented.
　本発明の一形態に係るセルロースアシレートフィルムは、偏光子との貼合面とその他の表面における飛行時間型二次イオン質量分析法（Time-Of-Flight Secondary Ion Mass Spectrometry：ＴＯＦ－ＳＩＭＳ）によるＴｇ低下剤の検出値に、ある程度の偏りがあるという特徴を有している。
　これを定量的に表現すると、飛行時間型二次イオン質量分析法を用いて検出される、セルロースアシレートフィルムの偏光子との貼合面のＴｇ低下剤の検出値をｄＡ、他方の面の検出値をｄＢとしたとき、下記式（１）により示されるｒ値が１．１以上である。
　式（１）　ｒ＝ｄＡ／ｄＢ A cellulose acylate film according to an embodiment of the present invention is obtained by Time-Of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) on a bonding surface with a polarizer and other surfaces. The detection value of the Tg lowering agent is characterized by a certain degree of bias.
When this is expressed quantitatively, the detected value of the Tg reducing agent on the bonding surface with the polarizer of the cellulose acylate film, detected using time-of-flight secondary ion mass spectrometry, is expressed as d A , and the other surface. when the detected value was d B, is r value shown by the following formula (1) is 1.1 or more.
Formula (1) r = d A / d B
　ここで、飛行時間型二次イオン質量分析法とは、固体試料上の原子や分子の化学情報を一分子層以下の感度で測定でき、特定の原子や分子の分布を１００ｎｍ以下の空間分解能で観察可能な質量分析法である。飛行時間型二次イオン質量分析法は、二次イオン質量分析法（ＳＩＭＳ）の１種であり、一次イオンビームを固体試料に照射し、その際に試料の最表面から放出されるイオン（二次イオン）を検出することによって、分析が行われる。質量分析計として飛行時間型質量分析計（ＴＯＦ－ＭＳ）が用いられることから、ＴＯＦ－ＳＩＭＳと称される。
　飛行時間型二次イオン質量分析法によれば、イオンビームをパルス的に試料に照射することによって、実質的に非破壊的な試料測定が可能であることから、現在では有機材料、高分子材料の分析にも広く応用されるに至っている。 Here, time-of-flight secondary ion mass spectrometry can measure the chemical information of atoms and molecules on a solid sample with a sensitivity of one molecular layer or less, and the distribution of specific atoms and molecules with a spatial resolution of 100 nm or less. This is an observable mass spectrometry method. Time-of-flight secondary ion mass spectrometry is a type of secondary ion mass spectrometry (SIMS), in which a solid sample is irradiated with a primary ion beam, and ions emitted from the outermost surface of the sample (two Analysis is performed by detecting (secondary ions). Since a time-of-flight mass spectrometer (TOF-MS) is used as the mass spectrometer, it is referred to as TOF-SIMS.
According to time-of-flight secondary ion mass spectrometry, it is possible to measure a sample substantially non-destructively by irradiating the sample with an ion beam in a pulsed manner. It has been widely applied to the analysis of
　上記ｒ値は１．１以上であればよいが、好ましくは１．２以上であり、より好ましくは１．３以上であり、さらに好ましくは１．４以上である。一方、偏光板製造時において、カールの発生を抑えやすくなることから、通常は１．５以下であることが好ましい。 The r value may be 1.1 or more, preferably 1.2 or more, more preferably 1.3 or more, and further preferably 1.4 or more. On the other hand, since it becomes easy to suppress generation | occurrence | production of a curl at the time of polarizing plate manufacture, it is usually preferable that it is 1.5 or less.
　以上、本発明における必須の構成要件であるｒ値の定義及び好ましい形態について説明したが、本発明に係るセルロースアシレートフィルムの別の観点に基づく好ましい実施形態として、フィルムの厚さ方向に沿ってＴｇ低下剤の濃度勾配が存在するという形態が挙げられる。例えば、最も簡単な例として、本発明に係るセルロースアシレートフィルムを、その厚さ方向に垂直な面で（フィルムの面方向に平行な面で）２等分されるように切断したときに、偏光子との貼合面を含む断片に存在するＴｇ低下剤の量が、他方の断片（他方の表面を含む断片）に存在するＴｇ低下剤の量よりも多い、という実施形態が好ましく例示される。これを一般化すると、本発明に係るセルロースアシレートフィルムを、その厚さ方向に垂直な面で（フィルムの面方向に平行な面で）ｋ等分されるように切断したときに、各断片に存在するＴｇ低下剤の量が、偏光子との貼合面を含む断片から他方の表面を含む断片に向かうに従って、徐々に減少するという実施形態もまた、好ましく例示される。当該実施形態において、ｋ＝２の場合については上記で別途説明したが、ｋは好ましくは３以上であり、より好ましくは５以上であり、さらに好ましくは１０以上であり、特に好ましくは２０以上である。 As described above, the definition and preferred form of the r value, which is an essential constituent requirement in the present invention, have been described, but as a preferred embodiment based on another viewpoint of the cellulose acylate film according to the present invention, along the thickness direction of the film. A form in which there is a concentration gradient of the Tg reducing agent can be mentioned. For example, as the simplest example, when the cellulose acylate film according to the present invention is cut so as to be divided into two equal parts by a plane perpendicular to the thickness direction (a plane parallel to the plane direction of the film), An embodiment in which the amount of the Tg reducing agent present in the fragment including the bonding surface with the polarizer is larger than the amount of the Tg reducing agent present in the other fragment (the fragment including the other surface) is preferably exemplified. The When this is generalized, when the cellulose acylate film according to the present invention is cut so as to be divided into k equal parts by a plane perpendicular to the thickness direction (a plane parallel to the plane direction of the film), each piece An embodiment in which the amount of the Tg reducing agent present in is gradually decreased from the fragment containing the bonding surface with the polarizer toward the fragment containing the other surface is also preferably exemplified. In this embodiment, the case where k = 2 is described separately above, but k is preferably 3 or more, more preferably 5 or more, further preferably 10 or more, and particularly preferably 20 or more. is there.
　本発明の一形態に係るセルロースアシレートフィルムによれば、ｒ値が１．１以上となるように構成されていることで、偏光板を構成する偏光子との密着性をより一層向上させることが可能となる。アシル基置換度の小さい、例えばＤＡＣ等のセルロースアシレートが、位相差フィルムだけでなく、視野角を拡大する光学補償フィルムとして用いられる場合には、偏光子と貼合されて偏光板を構成するのが一般的である。そして、偏光板としての耐久性を考えた場合、セルロースアシレートフィルムと偏光子との間の密着性は高いほど好ましい。 According to the cellulose acylate film according to one embodiment of the present invention, the adhesiveness with the polarizer constituting the polarizing plate is further improved by being configured so that the r value is 1.1 or more. Is possible. When cellulose acylate such as DAC having a low acyl group substitution degree is used not only as a retardation film but also as an optical compensation film for expanding a viewing angle, it is bonded to a polarizer to constitute a polarizing plate. It is common. And when durability as a polarizing plate is considered, the adhesiveness between a cellulose acylate film and a polarizer is so preferable that it is high.
　密着性を向上させるメカニズムについては完全には明らかではないが、本発明者の検討によれば、以下のメカニズムが推察されている。
　後述するが、セルロースアシレートフィルムは、通常セルロースアシレート及び添加剤を含むドープを支持体上に流延して得られたフィルムを乾燥し、剥離した後に延伸する工程を経て製造される。得られたセルロースアシレートフィルムのｒ値が１．１以上となるような製造手法を採用した場合、得られたセルロースアシレートフィルムの一方の表面が、他方の表面と比較して微小な凹凸が多く、荒れた表面構造を呈することが判明した。
　これは、セルロースアシレートのガラス転移温度Ｔｇを低下させるＴｇ低下能を持つＴｇ低下剤が、一方の表面にリッチに存在していることで、延伸の際にセルロースアシレートが柔軟に移動することができるようになった結果であろうと考えられている。そして、このような微小な凹凸を多数有する荒れた表面構造が、偏光子との密着性の向上に寄与しているものと考えられている。 The mechanism for improving the adhesion is not completely clear, but according to the study of the present inventor, the following mechanism is presumed.
As will be described later, the cellulose acylate film is usually produced through a step of drying a film obtained by casting a dope containing cellulose acylate and an additive on a support, peeling it, and then stretching it. When adopting a production method in which the r value of the obtained cellulose acylate film is 1.1 or more, one surface of the obtained cellulose acylate film has minute unevenness as compared with the other surface. Many were found to exhibit a rough surface structure.
This is because the cellulose acylate moves flexibly during stretching because the Tg lowering agent having the ability to lower the glass transition temperature Tg of the cellulose acylate is present on one surface in a rich manner. This is thought to be the result of the fact that And it is thought that the rough surface structure which has many such micro unevenness | corrugation contributes to the improvement of adhesiveness with a polarizer.
　なお、通常は偏光子とセルロースアシレートフィルムとの貼合時に、密着性の向上を目的として、セルロースアシレートフィルムの貼合面がアルカリケン化処理される。しかし、本発明により提供されるセルロースアシレートフィルムによれば、上述したようなメカニズムによって偏光子との間の密着性が向上することから、このようなアルカリケン化処理が不要となることも期待され、工数の削減によるコスト低減効果を図ることができる。
　また、アルカリケン化処理を施すと、セルロースアシレートフィルムのケン化処理表面（貼合面）に存在するセルロースアシレートの一部が、加水分解されてしまう可能性があるが、密着性の向上によってアルカリケン化処理が不要となれば、アルカリケン化処理時のセルロースアシレートの加水分解の可能性もなくなり、非常に優位性の高い技術が提供されることになる。 In addition, the bonding surface of the cellulose acylate film is usually subjected to alkali saponification treatment for the purpose of improving the adhesion at the time of bonding between the polarizer and the cellulose acylate film. However, according to the cellulose acylate film provided by the present invention, the adhesion between the polarizer and the polarizer is improved by the mechanism as described above, so that it is expected that such alkali saponification treatment is unnecessary. In addition, a cost reduction effect can be achieved by reducing the number of man-hours.
Moreover, when alkali saponification treatment is performed, part of cellulose acylate present on the saponification treatment surface (bonding surface) of the cellulose acylate film may be hydrolyzed, but the adhesion is improved. If the alkali saponification treatment becomes unnecessary, the possibility of hydrolysis of the cellulose acylate during the alkali saponification treatment is eliminated, and a very superior technique is provided.
　本発明の一形態に係るセルロースアシレートフィルムの好ましい実施形態は、上述のメカニズムにより、偏光子との密着性の向上に寄与する微小な凹凸からなる表面構造の存在を定量的に表現したものである。すなわち、本発明の一形態に係るセルロースアシレートフィルムにおいては、フィルムの２つの表面のうち、偏光子との貼合面の、ＪＩＳ　Ｂ０６０１：２００１によって測定される算術平均粗さＲａの値が、他方の表面における値よりも大きいことが好ましい。この際、貼合面における算術平均粗さＲａの値は、他方の表面における算術平均粗さＲａの値の、好ましくは１．０５倍以上であり、より好ましくは１．１倍以上、さらに好ましくは１．２倍以上であり、特に好ましくは１．３倍以上、最も好ましくは１．４倍以上である。 A preferred embodiment of the cellulose acylate film according to one aspect of the present invention is a quantitative representation of the presence of a surface structure composed of minute irregularities that contributes to improvement in adhesion to a polarizer by the above-described mechanism. is there. That is, in the cellulose acylate film according to one embodiment of the present invention, the arithmetic average roughness Ra measured by JIS B0601: 2001 on the bonding surface with the polarizer, out of the two surfaces of the film, It is preferably larger than the value on the other surface. At this time, the value of the arithmetic average roughness Ra on the bonding surface is preferably 1.05 times or more, more preferably 1.1 times or more, more preferably the value of the arithmetic average roughness Ra on the other surface. Is 1.2 times or more, particularly preferably 1.3 times or more, and most preferably 1.4 times or more.
　また、従来、セルロースアシレートフィルムと偏光子とを貼合して偏光板を作製する際、位相差フィルムとしてのセルロースアシレートフィルムの遅相軸と、偏光子の吸収軸とを厳密に重ね合わせる工程が必要とされていた。貼合の際に、これら２つの軸がわずかでもずれ、いわゆる軸ずれが生じると、偏光板の偏光度が低下してしまうという問題があった。偏光板を構成するセルロースアシレートフィルムの位相差発現性能が高ければ高いほど、この偏光度の低下は顕著に現れることになるため、上述したような軸ずれに起因する偏光度の低下を緩和しうる手段の開発もまた、強く望まれていた。 Conventionally, when a polarizing plate is produced by laminating a cellulose acylate film and a polarizer, the slow axis of the cellulose acylate film as a retardation film and the absorption axis of the polarizer are precisely overlapped. A process was needed. When pasting, even if these two axes are shifted slightly, so-called axial shift occurs, there is a problem that the polarization degree of the polarizing plate is lowered. The higher the retardation development performance of the cellulose acylate film that constitutes the polarizing plate, the more the reduction in the polarization degree appears. Therefore, the reduction in the polarization degree due to the axis deviation as described above is alleviated. The development of possible means was also highly desired.
　本発明の一形態に係るセルロースアシレートフィルムは、このような要望に対しても一定の解決をもたらす。すなわち、本発明の一形態に係るセルロースアシレートフィルムによれば、偏光子との貼合時にわずかな軸ずれが生じても、それに起因する偏光板の偏光度の低下が緩和され得る。そのメカニズムについては完全には明らかではないが、本発明者の検討によれば、以下のメカニズムが推定されている。 The cellulose acylate film according to one embodiment of the present invention provides a certain solution to such a demand. That is, according to the cellulose acylate film according to one embodiment of the present invention, even if a slight axis shift occurs during bonding with a polarizer, a decrease in the degree of polarization of the polarizing plate due to the misalignment can be alleviated. Although the mechanism is not completely clear, the following mechanism has been estimated according to the study of the present inventor.
　本発明の一形態に係るセルロースアシレートフィルムに含まれるＴｇ低下剤は、フィルム内部での存在量の増加に伴って、位相差発現に寄与するセルロースアシレートの相対的な存在量を減少させることになる。本発明のセルロースアシレートフィルムにおいては、偏光子との貼合面に、他方の表面よりも多くのＴｇ低下剤が存在していることから、貼合面近傍について微視的に観察すれば、セルロースアシレートフィルムのリターデーション値Ｒｏ、Ｒｔｈは、セルロースアシレートフィルム全体についての巨視的な値よりも小さくなっていると考えられる。逆に、他方の表面近傍について微視的に観察すれば、リターデーション値Ｒｏ、Ｒｔｈは、セルロースアシレートフィルム全体についての巨視的な値よりも大きくなっていると考えられる。 The Tg lowering agent contained in the cellulose acylate film according to one aspect of the present invention reduces the relative abundance of cellulose acylate contributing to the development of retardation as the abundance in the film increases. become. In the cellulose acylate film of the present invention, since there are more Tg reducing agents on the bonding surface with the polarizer than on the other surface, if it is observed microscopically in the vicinity of the bonding surface, It is considered that the retardation values Ro and Rth of the cellulose acylate film are smaller than the macroscopic values of the entire cellulose acylate film. On the contrary, if the other surface vicinity is observed microscopically, it can be considered that the retardation values Ro and Rth are larger than the macroscopic values of the entire cellulose acylate film.
　このような場合であっても、フィルム全体に含まれるＴｇ低下剤の量及びセルロースアシレートフィルムの厚さが一定であれば、フィルム全体としての位相差発現性能、つまりリターデーション値Ｒｏ、Ｒｔｈは不変である。上述のように、セルロースアシレートフィルムの位相差フィルムとしての位相差発現性能、つまりリターデーション値Ｒｏ、Ｒｔｈが高いほど、偏光子との軸ずれによる偏光度の低下が大きい。また、偏光子との貼合面において、接着剤の収縮及び硬化時の発熱といった外的要因により、セルロースアシレートフィルムの軸ずれが発生しやすい。よって、リターデーション値Ｒｏ、Ｒｔｈが微視的に小さくなるように構成されている貼合面を偏光子と貼合する場合は、フィルム全体に均一にＴｇ低下剤が存在する面を偏光子に貼合する場合と比較して、同程度の軸ずれが生じても、偏光板の偏光度の低下の度合いが小さくてすむ。結果として、軸ずれに起因する偏光板の偏光度の低下が緩和される。 Even in such a case, if the amount of the Tg reducing agent contained in the whole film and the thickness of the cellulose acylate film are constant, the retardation development performance as a whole film, that is, the retardation values Ro and Rth are Is unchanged. As described above, the higher the retardation development performance of the cellulose acylate film as the retardation film, that is, the retardation values Ro and Rth, the greater the decrease in the degree of polarization due to the axial misalignment with the polarizer. In addition, on the bonding surface with the polarizer, the axis shift of the cellulose acylate film is likely to occur due to external factors such as shrinkage of the adhesive and heat generation during curing. Therefore, when bonding the bonding surface comprised so that retardation values Ro and Rth become microscopically small with a polarizer, the surface where a Tg reducing agent exists uniformly in the whole film can be used as a polarizer. Even if the same degree of axial deviation occurs as compared with the case of pasting, the degree of decrease in the degree of polarization of the polarizing plate can be small. As a result, the decrease in the degree of polarization of the polarizing plate due to the axis deviation is alleviated.
　従来、セルロースアシレートフィルムを構成するのに用いられる添加剤は、通常、フィルムの内部において可能な限り均一に分布するように種々の工夫がなされていた。つまり、セルロースアシレートフィルムへの各種の添加剤の添加を検討する当業者であれば、より均一な配合を念頭に置くことはあっても、添加剤の配合に分布を持たせようとすることはしないはずである。従って、このような技術常識の下で、あえてＴｇ低下剤の配合に分布を持たせたことにより、上述したような優れた作用効果を発揮することができる本発明は、先行技術に対して極めて優位性の高い技術を提供するものであるといえる。 Conventionally, various additives have been devised so that the additives used for constituting the cellulose acylate film are normally distributed as uniformly as possible inside the film. In other words, those skilled in the art who consider the addition of various additives to the cellulose acylate film should try to have a distribution in the additive formulation even though they may have a more uniform formulation in mind. Should not. Therefore, the present invention capable of exerting the above-described excellent effects by providing the distribution of the Tg lowering agent intentionally under such technical common sense is extremely different from the prior art. It can be said that it provides a technology with high advantage.
＜その他の添加剤＞
　本発明の一形態に係るセルロースアシレートフィルムは、上述したＴｇ低下剤に加えて、その他の添加剤を含有することができる。以下、本発明に用いられ得る添加剤について、説明する。 <Other additives>
The cellulose acylate film according to one embodiment of the present invention can contain other additives in addition to the above-described Tg reducing agent. Hereinafter, additives that can be used in the present invention will be described.
（加水分解防止剤）
　本発明の一形態に係るセルロースアシレートフィルムは、加水分解防止剤を含むことができる。このように、セルロースアシレートフィルムが加水分解防止剤を含むことで、セルロースアシレートの加水分解が防止されることから、セルロースアシレートフィルムの耐水性が向上し得る。 (Hydrolysis inhibitor)
The cellulose acylate film according to one embodiment of the present invention can contain a hydrolysis inhibitor. Thus, since a cellulose acylate film contains a hydrolysis inhibiting agent, since hydrolysis of a cellulose acylate is prevented, the water resistance of a cellulose acylate film can improve.
　本発明において用いられ得る加水分解防止剤とは、それを含まないアシル基置換度が２．０～２．５であるセルロースアシレート単独での耐加水分解性が、それを添加することによって低下する添加剤を意味し、このような定義を満足する限り、いかなる物質が加水分解防止剤として用いられてもよい。 The hydrolysis inhibitor that can be used in the present invention means that the hydrolysis resistance of a cellulose acylate having no acyl group substitution degree of 2.0 to 2.5 is reduced by adding it. Any substance may be used as a hydrolysis inhibitor so long as it satisfies such a definition.
　ある物質が加水分解防止剤の概念に含まれるか否かを判定するための、セルロースアシレートフィルムの耐加水分解性の指標としては、ケン化前後での質量変化率が用いられ得る。具体的には、フィルムを５０℃の２．０ＭのＫＯＨ水溶液に９０秒間浸漬して、その前後のフィルムの質量変化率を計算する。質量変化率によれば、アルカリ溶液中で、加水分解され、ケン化液中に溶け出したセルロースアシレートの割合を把握できる。セルロースアシレートのみで製膜したフィルムの質量変化率をｄ１％、セルロースアシレート１００質量部に対して、添加剤５質量部添加したフィルムの質量変化率をｄ２％として、｜ｄ１｜＞｜ｄ２｜を満たす場合に、当該添加剤はセルロースアシレートに対する加水分解防止剤であると判断することができる。 As a measure of hydrolysis resistance of a cellulose acylate film for determining whether or not a certain substance is included in the concept of a hydrolysis inhibitor, a mass change rate before and after saponification can be used. Specifically, the film is immersed in a 2.0 M KOH aqueous solution at 50 ° C. for 90 seconds, and the mass change rate of the film before and after that is calculated. According to the mass change rate, it is possible to grasp the ratio of cellulose acylate that has been hydrolyzed in the alkaline solution and dissolved in the saponified solution. | D1 |> | d2 where d1% is the mass change rate of a film formed only with cellulose acylate, and d2% is the mass change rate of 5 mass parts of the additive with respect to 100 mass parts of cellulose acylate. When | is satisfied, it can be determined that the additive is a hydrolysis inhibitor for cellulose acylate.
　また、アシル基置換度が２．０～２．５であるセルロースアシレートの種類に応じて、ある物質が加水分解防止剤の定義に該当する場合と該当しない場合とが生じるときには、当該物質は加水分解防止剤の定義に該当する場合におけるアシル基置換度が２．０～２．５であるセルロースアシレートとの併用であれば、本発明において加水分解防止剤として用いられ得る。 In addition, depending on the type of cellulose acylate having an acyl group substitution degree of 2.0 to 2.5, when a substance falls into the case where it falls under the definition of a hydrolysis inhibitor and when it does not fall, the substance is If it is used in combination with a cellulose acylate having an acyl group substitution degree of 2.0 to 2.5 when it falls under the definition of a hydrolysis inhibitor, it can be used as a hydrolysis inhibitor in the present invention.
　加水分解防止剤の加水分解防止能について特に制限はないが、加水分解防止剤の疎水性の指標である平均ｌｏｇＰ値によって表すことができる。平均ｌｏｇＰ値が高いほど、加水分解防止剤として好ましい性能を有しているといえる。 Although there is no restriction | limiting in particular about the hydrolysis inhibiting ability of a hydrolysis inhibiting agent, It can represent with the average logP value which is a hydrophobic parameter | index of a hydrolysis inhibiting agent. It can be said that the higher the average log P value, the better the performance as a hydrolysis inhibitor.
　ここで、ｌｏｇＰ値は、オクタノール－水分配係数やｌｏｇＰｏｗとも称され、ｎ－オクタノール及び水からなる二相溶媒系の各相へのある物質の分配濃度の比の値の常用対数として定義される。そして、平均ｌｏｇＰ値は、加水分解防止剤が複数種の化合物の混合物として用いられる場合を考慮し、混合物を構成する各化合物の固有のｌｏｇＰ値をまず求めた後、混合物における各化合物の混合比率（質量比）によって重み付けすることにより算出される。
　ｌｏｇＰ値は、ＪＩＳ　Ｚ－７２６０－１０７：２０００に記載のフラスコ振盪法により測定された値である。また、ｌｏｇＰ値は、実測に代わって、計算化学的手法又は経験的方法により見積もられた値であってもよい。 Here, the log P value is also referred to as an octanol-water partition coefficient or log Pow, and is defined as a common logarithm of the value of the ratio of the distribution concentration of a substance to each phase of a two-phase solvent system composed of n-octanol and water. . The average log P value is determined by first considering the specific log P value of each compound constituting the mixture in consideration of the case where the hydrolysis inhibitor is used as a mixture of a plurality of compounds, and then the mixing ratio of each compound in the mixture. It is calculated by weighting by (mass ratio).
The logP value is a value measured by a flask shaking method described in JIS Z-7260-107: 2000. Further, the logP value may be a value estimated by a computational chemical method or an empirical method instead of the actual measurement.
　計算化学的手法によってｌｏｇＰ値を求める場合、その計算方法としては、Ｃｒｉｐｐｅｎ’ｓ　ｆｒａｇｍｅｎｔａｔｉｏｎ法（Ｊ．Ｃｈｅｍ．Ｉｎｆ．Ｃｏｍｐｕｔ．Ｓｃｉ．，２７巻、ｐ２１（１９８７年））、Ｖｉｓｗａｎａｄｈａｎ’ｓ　ｆｒａｇｍｅｎｔａｔｉｏｎ法（Ｊ．Ｃｈｅｍ．Ｉｎｆ．Ｃｏｍｐｕｔ．Ｓｃｉ．，２９巻、ｐ１６３（１９８９年））、Ｂｒｏｔｏ’ｓ　ｆｒａｇｍｅｎｔａｔｉｏｎ法（Ｅｕｒ．Ｊ．Ｍｅｄ．Ｃｈｅｍ．－Ｃｈｉｍ．Ｔｈｅｏｒ．，１９巻、ｐ７１（１９８４年））、ＣＬｏｇＰ法（参考文献Ｌｅｏ，Ａ．，Ｊｏｗ，Ｐ．Ｙ．Ｃ．，Ｓｉｌｉｐｏ，Ｃ．，Ｈａｎｓｃｈ，Ｃ．，Ｊ．Ｍｅｄ．Ｃｈｅｍ．，１８，８６５　１９７５年）等が好ましく用いられるが、Ｃｒｉｐｐｅｎ’ｓ　ｆｒａｇｍｅｎｔａｔｉｏｎ法（Ｊ．Ｃｈｅｍ．Ｉｎｆ．Ｃｏｍｐｕｔ．Ｓｃｉ．，２７巻、ｐ２１（１９８７年））が好ましい。ただし、上述したフラスコ振盪法による実測値と、計算化学的手法又は経験的方法によって見積もられた値とが有意に異なる場合、フラスコ振盪法による実測値が優先する。 When the logP value is obtained by a computational chemistry method, the calculation method includes Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, p21 (1987)), Viswanadhan's fragmentation method ( J. Chem. Inf. Comput. Sci., 29, p163 (1989)), Broto's fragmentation method (Eur. J. Med. Chem.-Chim. Theor., 19, p71 (1984)) ClogP method (reference documents Leo, A., Jow, PYC, Silipo, C., Hansch, C., J. Med. Chem., 18, 865, 1975) and the like are preferably used. Crippen's f agmentation method (J.Chem.Inf.Comput.Sci., 27 vol., p21 (1987 years)) are preferred. However, when the measured value by the flask shaking method mentioned above and the value estimated by the computational chemical method or the empirical method are significantly different, the measured value by the flask shaking method has priority.
　本発明において用いられる加水分解防止剤の平均ｌｏｇＰ値は、好ましくは７．５以上であり、より好ましくは８．０以上であり、さらに好ましくは９．０以上であり、特に好ましくは９．５以上である。加水分解防止剤の平均ｌｏｇＰ値が、このような範囲内の値であると、少ない添加量でも優れた加水分解防止効果が発揮され得る。このため、添加剤を多量に添加せざるを得ない場合等に発生するブリードアウト等の発生が防止され得る。一方、加水分解防止剤の平均ｌｏｇＰ値の上限値について特に制限はないが、セルロースアシレートとの相溶性という観点から、通常は１３．０以下程度であることが好ましい。 The average log P value of the hydrolysis inhibitor used in the present invention is preferably 7.5 or more, more preferably 8.0 or more, still more preferably 9.0 or more, and particularly preferably 9.5. That's it. When the average log P value of the hydrolysis inhibitor is within such a range, an excellent hydrolysis prevention effect can be exhibited even with a small addition amount. For this reason, generation | occurrence | production of the bleedout etc. which generate | occur | produce when the additive must be added in large quantities can be prevented. On the other hand, although there is no restriction | limiting in particular about the upper limit of the average logP value of a hydrolysis inhibitor, Usually, it is preferable that it is about 13.0 or less from a viewpoint of compatibility with a cellulose acylate.
　本発明において用いられ得る加水分解防止剤の具体的な形態については、上述した加水分解防止剤の定義を満たす限り、好ましくは上述したｌｏｇＰ値の好ましい範囲も満たす限り、特に制限はない。加水分解防止剤の一例としては、下記一般式（II）で表される糖エステル化合物が挙げられる。
　一般式（II）　（ＨＯ）ｍ－Ｇ－（Ｏ－Ｃ（＝Ｏ）－Ｒ２）ｌ
〔式中、Ｇは単糖類又は二糖類の残基を表す。Ｒ２は脂肪族基又は芳香族基を表す。ｍは単糖類又は二糖類の残基に、直接結合しているヒドロキシ基の数の合計を表す。ｌは単糖類又は二糖類の残基に直接結合している－（Ｏ－Ｃ（＝Ｏ）－Ｒ２）基の数の合計を表し、３≦ｍ＋ｌ≦８であり、ｌ≠０である。〕 The specific form of the hydrolysis inhibitor that can be used in the present invention is not particularly limited as long as the definition of the hydrolysis inhibitor described above is satisfied, and preferably the preferable range of the log P value described above is also satisfied. An example of the hydrolysis inhibitor is a sugar ester compound represented by the following general formula (II).
Formula (II) (HO) m -G- (OC (= O) -R 2 ) l
[In formula, G represents the residue of a monosaccharide or a disaccharide. R 2 represents an aliphatic group or an aromatic group. m represents the total number of hydroxy groups directly bonded to the monosaccharide or disaccharide residues. l represents the total number of — (O—C (═O) —R 2 ) groups directly bonded to the monosaccharide or disaccharide residue, 3 ≦ m + l ≦ 8, and l ≠ 0. . ]
　一般式（II）で表される構造を有する化合物は、ヒドロキシ基の合計数ｍ、－（Ｏ－Ｃ（＝Ｏ）－Ｒ２）基の合計数ｌが固定された単一種の化合物として単離することは困難であり、式中のｍ、ｌの異なる成分が数種類混合された化合物となることが知られている。従って、ヒドロキシ基の数ｍ、－（Ｏ－Ｃ（＝Ｏ）－Ｒ２）基の数ｌが各々変化した混合物としての性能が重要である。
　本発明のセルロースアシレートフィルムの場合、ヘイズ特性に対し、一般式（II）で表される構造を有し、かつｍ＝０の成分と、ｍ＞０の成分との混合比率が４５：５５～０：１００の範囲内である化合物が好ましい。さらに性能的、コスト的により好ましくは、ｍ＝０の成分と、ｍ＞０の成分との混合比率が１０：９０～０．１：９９．９の範囲である。なお、上記ｍ＝０の成分とｍ＞０の成分は、常法により高速液体クロマトグラフィによって測定することが可能である。 The compound having the structure represented by the general formula (II) is a single type of compound in which the total number m of hydroxy groups and the total number l of — (O—C (═O) —R 2 ) groups are fixed. It is difficult to separate, and it is known that a compound in which several components different in m and l in the formula are mixed is obtained. Therefore, the performance as a mixture in which the number m of hydroxy groups and the number 1 of — (O—C (═O) —R 2 ) groups are changed is important.
In the case of the cellulose acylate film of the present invention, the mixing ratio of the component represented by the general formula (II) and the component m = 0 and the component m> 0 is 45:55 with respect to the haze characteristics. Compounds that are in the range of ~ 0: 100 are preferred. More preferably, in terms of performance and cost, the mixing ratio of the component m = 0 and the component m> 0 is in the range of 10:90 to 0.1: 99.9. In addition, the component of m = 0 and the component of m> 0 can be measured by high performance liquid chromatography by a conventional method.
　上記一般式（II）においてＧが表す残基の単糖類の具体例としては、例えばアロース、アルトロース、グルコース、マンノース、グロース、イドース、ガラクトース、タロース、リボース、アラビノース、キシロース、リキソース等が挙げられる。 Specific examples of the monosaccharide of the residue represented by G in the general formula (II) include, for example, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, ribose, arabinose, xylose, lyxose, and the like. .
　以下に、一般式（II）で表される、単糖類残基を有する化合物の構造例を示すが、本発明はこれらの具体例に限定されるものではない。
Figure JPOXMLDOC01-appb-C000008
 Examples of the structure of the compound having a monosaccharide residue represented by the general formula (II) are shown below, but the present invention is not limited to these specific examples.
Figure JPOXMLDOC01-appb-C000008
　また、Ｇが表す残基の二糖類の具体例としては、例えばトレハロース、スクロース、マルトース、セロビオース、ゲンチオビオース、ラクトース、イソトレハロース等が挙げられる。
　以下に、一般式（II）で表される、二糖類残基を有する化合物の構造例を示すが、本発明はこれらの具体例に限定されるものではない。
Figure JPOXMLDOC01-appb-C000009
 Specific examples of the disaccharide of the residue represented by G include trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, and isotrehalose.
Although the structural example of the compound which has a disaccharide residue represented by general formula (II) below is shown, this invention is not limited to these specific examples.
Figure JPOXMLDOC01-appb-C000009
　一般式（II）において、Ｒ２が表す脂肪族基又は芳香族基は、それぞれ独立に置換基を有していてもよい。 In general formula (II), the aliphatic group or aromatic group represented by R 2 may each independently have a substituent.
　一般式（II）において、ｍ、ｌは、３≦ｍ＋ｌ≦８であることが必要であり、４≦ｍ＋ｌ≦８であることが好ましい。また、ｌ≠０である。なお、ｌが２以上である場合、－（Ｏ－Ｃ（＝Ｏ）－Ｒ２）基は互いに同じでもよいし異なっていてもよい。 In the general formula (II), m and l are required to satisfy 3 ≦ m + l ≦ 8, and preferably 4 ≦ m + l ≦ 8. Also, l ≠ 0. When l is 2 or more, the — (O—C (═O) —R 2 ) groups may be the same or different.
　一般式（II）のＲ２の定義における脂肪族基は、直鎖であっても、分岐であっても、環状であってもよい。脂肪族基の炭素数は、炭素数１～２５が好ましく、炭素数１～２０がより好ましく、炭素数２～１５がさらに好ましい。脂肪族基の具体例としては、例えばメチル、エチル、ｎ－プロピル、ｉｓｏ－プロピル、シクロプロピル、ｎ－ブチル、ｉｓｏ－ブチル、ｔｅｒｔ－ブチル、アミル、ｉｓｏ－アミル、ｔｅｒｔ－アミル、ｎ－ヘキシル、シクロヘキシル、ｎ－ヘプチル、ｎ－オクチル、ビシクロオクチル、アダマンチル、ｎ－デシル、ｔｅｒｔ－オクチル、ドデシル、ヘキサデシル、オクタデシル、ジデシル等が挙げられる。 The aliphatic group in the definition of R 2 in the general formula (II) may be linear, branched or cyclic. The aliphatic group preferably has 1 to 25 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 2 to 15 carbon atoms. Specific examples of the aliphatic group include, for example, methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, n-butyl, iso-butyl, tert-butyl, amyl, iso-amyl, tert-amyl, n-hexyl. Cyclohexyl, n-heptyl, n-octyl, bicyclooctyl, adamantyl, n-decyl, tert-octyl, dodecyl, hexadecyl, octadecyl, didecyl and the like.
　また、一般式（II）のＲ２の定義における芳香族基は、芳香族炭化水素基でもよいし、芳香族複素環基でもよく、より好ましくは芳香族炭化水素基である。芳香族炭化水素基としては、炭素数が６～２４のものが好ましく、６～１２のものがさらに好ましい。芳香族炭化水素基の具体例としては、例えばベンゼン、ナフタレン、アントラセン、ビフェニル、ターフェニル等が挙げられる。芳香族炭化水素基としては、ベンゼン、ナフタレン、ビフェニルが特に好ましい。芳香族複素環基としては、酸素原子、窒素原子又は硫黄原子のうち少なくとも１つを含むものが好ましい。複素環の具体例としては、例えばフラン、ピロール、チオフェン、イミダゾール、ピラゾール、ピリジン、ピラジン、ピリダジン、トリアゾール、トリアジン、インドール、インダゾール、プリン、チアゾリン、チアジアゾール、オキサゾリン、オキサゾール、オキサジアゾール、キノリン、イソキノリン、フタラジン、ナフチリジン、キノキサリン、キナゾリン、シンノリン、プテリジン、アクリジン、フェナントロリン、フェナジン、テトラゾール、ベンズイミダゾール、ベンズオキサゾール、ベンズチアゾール、ベンゾトリアゾール、テトラザインデン等が挙げられる。芳香族複素環基としては、ピリジン、トリアジン、キノリンが特に好ましい。 In addition, the aromatic group in the definition of R 2 in the general formula (II) may be an aromatic hydrocarbon group or an aromatic heterocyclic group, and more preferably an aromatic hydrocarbon group. The aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms. Specific examples of the aromatic hydrocarbon group include benzene, naphthalene, anthracene, biphenyl, terphenyl and the like. As the aromatic hydrocarbon group, benzene, naphthalene, and biphenyl are particularly preferable. As an aromatic heterocyclic group, what contains at least 1 among an oxygen atom, a nitrogen atom, or a sulfur atom is preferable. Specific examples of the heterocyclic ring include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiazoline, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline. Phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazaindene and the like. As the aromatic heterocyclic group, pyridine, triazine, and quinoline are particularly preferable.
　次に、一般式（II）で表される化合物の好ましい例を下記に示すが、本発明はこれらの具体例に限定されるものではない。
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
 Next, although the preferable example of a compound represented by general formula (II) is shown below, this invention is not limited to these specific examples.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
　以下、一般式（II）で表される化合物の合成例を示す。
　撹拌装置、還流冷却器、温度計及び窒素ガス導入管を備えた四頭コルベンに、ショ糖３４．２ｇ（０．１モル）、無水安息香酸１８０．８ｇ（０．８モル）、ピリジン３７９．７ｇ（４．８モル）を仕込み、撹拌下に窒素ガス導入管から窒素ガスをバブリングさせながら昇温し、７０℃で５時間エステル化反応を行った。次に、コルベン内を４×１０２Ｐａ以下に減圧し、６０℃で過剰のピリジンを留去した後に、コルベン内を１．３×１０Ｐａ以下に減圧し、１２０℃まで昇温させ、無水安息香酸、生成した安息香酸の大部分を留去した。そして、次にトルエン１Ｌ、０．５質量％の炭酸ナトリウム水溶液３００ｇを添加し、５０℃で３０分間撹拌後、静置して、トルエン層を分取した。最後に、分取したトルエン層に水１００ｇを添加し、常温で３０分間水洗後、トルエン層を分取し、減圧下（４×１０２Ｐａ以下）、６０℃でトルエンを留去させ、下記例示化合物（Ｃ－１）、（Ｃ－２）、（Ｃ－３）、（Ｃ－４）及び（Ｃ－５）の混合物を得た。得られた混合物をＨＰＬＣ及びＬＣ－ＭＡＳＳで解析したところ、（Ｃ－１）が７質量％、（Ｃ－２）が５８質量％、（Ｃ－３）が２３質量％、（Ｃ－４）が９質量％、（Ｃ－５）が３質量％であった。なお、得られた混合物の一部をシリカゲルカラムクロマトグラフィーにより精製することで、それぞれ純度１００％の（Ｃ－１）、（Ｃ－２）、（Ｃ－３）、（Ｃ－４）及び（Ｃ－５）を得た。 Hereinafter, synthesis examples of the compound represented by the general formula (II) are shown.
A four-headed colben equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen gas inlet tube was mixed with 34.2 g (0.1 mol) of sucrose, 180.8 g (0.8 mol) of benzoic anhydride, 379. 7 g (4.8 mol) was charged, the temperature was raised while bubbling nitrogen gas from a nitrogen gas introduction tube with stirring, and an esterification reaction was carried out at 70 ° C. for 5 hours. Next, the inside of the Kolben was depressurized to 4 × 10 2 Pa or less, and after excess pyridine was distilled off at 60 ° C., the inside of the Kolben was depressurized to 1.3 × 10 Pa or less and the temperature was raised to 120 ° C. Most of the acid and benzoic acid formed were distilled off. Then, 1 L of toluene and 300 g of a 0.5% by mass aqueous sodium carbonate solution were added, and the mixture was stirred at 50 ° C. for 30 minutes and then allowed to stand to separate a toluene layer. Finally, 100 g of water was added to the collected toluene layer, and after washing with water at room temperature for 30 minutes, the toluene layer was collected, and toluene was distilled off at 60 ° C. under reduced pressure (4 × 10 2 Pa or less). A mixture of exemplary compounds (C-1), (C-2), (C-3), (C-4) and (C-5) was obtained. When the obtained mixture was analyzed by HPLC and LC-MASS, (C-1) was 7% by mass, (C-2) was 58% by mass, (C-3) was 23% by mass, (C-4) Was 9% by mass, and (C-5) was 3% by mass. A part of the obtained mixture was purified by silica gel column chromatography to obtain (C-1), (C-2), (C-3), (C-4) and (C-4) having a purity of 100%. C-5) was obtained.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　本発明の一形態に係るセルロースアシレートフィルムに添加され得る加水分解防止剤は、上述したようにフィルムに耐水性を付与するという作用効果を発揮する。従って、この加水分解防止剤は、上述したＴｇ低下剤とは異なり、可能な限り、フィルム全体に均一に分布していることが好ましい。 The hydrolysis inhibitor that can be added to the cellulose acylate film according to one embodiment of the present invention exhibits the effect of imparting water resistance to the film as described above. Therefore, it is preferable that the hydrolysis inhibitor is uniformly distributed throughout the film as much as possible, unlike the Tg reducing agent described above.
　このことを定量的に表現すれば、飛行時間型二次イオン質量分析法を用いて検出される、フィルムの両面における加水分解防止剤の検出値をそれぞれｄＣ、ｄＤとしたとき、下記数式（２）により示されるｓ値が、１．１未満であることが好ましい。
Figure JPOXMLDOC01-appb-M000013
 〔式中、ｍａｘ｛ｄＣ，ｄＤ｝はｄＣ又はｄＤのうち大きい方を表し、ｍｉｎ｛ｄC，ｄD｝はｄC又はｄDのうち大きくない方を表す。〕 Expressing this quantitatively, when the detected values of the hydrolysis inhibitor on both sides of the film, detected using time-of-flight secondary ion mass spectrometry, are d C and d D , respectively, The s value indicated by (2) is preferably less than 1.1.
Figure JPOXMLDOC01-appb-M000013
 [Wherein, max {d C , d D } represents the larger of d C or d D , and min {d C , d D } represents the smaller of d C or d D. ]
　Ｔｇ低下剤の検出値の偏りについて上述した説明から理解されるように、加水分解防止剤の検出値の偏りについてのこの好ましい実施形態は、要するに、セルロースアシレートフィルムの両面における、飛行時間型二次イオン質量分析法による加水分解防止剤の検出値にほとんど偏りがない、具体的にはその比が１．１未満となる程度しか偏りがない、ということを意味する。 As can be understood from the above description of the deviation of the detected value of the Tg reducing agent, this preferred embodiment of the deviation of the detected value of the hydrolysis inhibitor is, This means that the detected value of the hydrolysis inhibitor by secondary ion mass spectrometry is almost non-biased, specifically, only to the extent that the ratio is less than 1.1.
　なお、好ましい実施形態では、ｓ値は理論上、１以上の実数である。ｓ値は１．１未満であればよいが、ｓ値は好ましくは１．０５以下であり、より好ましくは１．０３以下であり、さらに好ましくは１．０２以下であり、特に好ましくは１．０１以下であり、最も好ましくは１．００５以下である。 In the preferred embodiment, the s value is theoretically a real number of 1 or more. The s value may be less than 1.1, but the s value is preferably 1.05 or less, more preferably 1.03 or less, still more preferably 1.02 or less, and particularly preferably 1. 01 or less, and most preferably 1.005 or less.
（可塑剤）
　本発明のセルロースアシレートフィルムは、本発明の効果を得る上で、必要に応じて、従来公知の可塑剤を含有してもよい。上述した一般式（Ｉ）や一般式（II）で表される化合物は、可塑剤としても用いられるが、これら以外の可塑剤を含有することもできる。
　他の可塑剤の具体的な形態は特に限定されないが、好ましくは、多価カルボン酸エステル系可塑剤、グリコレート系可塑剤、フタル酸エステル系可塑剤、脂肪酸エステル系可塑剤、多価アルコールエステル系可塑剤、エステル系可塑剤、アクリル系可塑剤等から選択される。これらのうち、可塑剤を２種以上用いる場合は、少なくとも１種は多価アルコールエステル系可塑剤であることが好ましい。 (Plasticizer)
In order to obtain the effects of the present invention, the cellulose acylate film of the present invention may contain a conventionally known plasticizer as necessary. Although the compound represented by the general formula (I) or the general formula (II) described above is also used as a plasticizer, it can also contain other plasticizers.
The specific form of the other plasticizer is not particularly limited, but is preferably a polycarboxylic acid ester plasticizer, a glycolate plasticizer, a phthalate ester plasticizer, a fatty acid ester plasticizer, or a polyhydric alcohol ester. Selected from plasticizers, ester plasticizers, acrylic plasticizers, and the like. Of these, when two or more plasticizers are used, at least one of them is preferably a polyhydric alcohol ester plasticizer.
　多価アルコールエステル系可塑剤は、２価以上の脂肪族多価アルコールとモノカルボン酸のエステルとからなる可塑剤であり、分子内に芳香環又はシクロアルキル環を有することが好ましい。好ましくは２～２０価の脂肪族多価アルコールエステルである。 The polyhydric alcohol ester plasticizer is a plasticizer composed of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid ester, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. A divalent to 20-valent aliphatic polyhydric alcohol ester is preferred.
　本発明に好ましく用いられる多価アルコールは、次の一般式（III）で表される。
　一般式（III）　Ｒ１１－（ＯＨ）ｎ
　〔式中、Ｒ１１はｎ価の有機基を表す。ｎは２以上の整数を表す。ＯＨ基はアルコール性及び／又はフェノール性ヒドロキシ基を表す。〕 The polyhydric alcohol preferably used in the present invention is represented by the following general formula (III).
Formula (III) R 11 - (OH ) n
[Wherein R 11 represents an n-valent organic group. n represents an integer of 2 or more. The OH group represents an alcoholic and / or phenolic hydroxy group. ]
　好ましい多価アルコールとしては、例えばアドニトール、アラビトール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、ジプロピレングリコール、トリプロピレングリコール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、ジブチレングリコール、１，２，４－ブタントリオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、ヘキサントリオール、ガラクチトール、マンニトール、３－メチルペンタン－１，３，５－トリオール、ピナコール、ソルビトール、トリメチロールプロパン、トリメチロールエタン、キシリトール等が挙げられる。特に、トリエチレングリコール、テトラエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、ソルビトール、トリメチロールプロパン、キシリトールが好ましい。 Preferred polyhydric alcohols include, for example, adonitol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2 -Butanediol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol Mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, trimethylolethane, xylitol and the like. In particular, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, and xylitol are preferable.
　多価アルコールエステルに用いられるモノカルボン酸としては、特に制限はなく、公知の脂肪族モノカルボン酸、脂環族モノカルボン酸、芳香族モノカルボン酸等を用いることができる。脂環族モノカルボン酸、芳香族モノカルボン酸を用いると透湿性、保留性を向上させる点で好ましい。 There is no restriction | limiting in particular as monocarboxylic acid used for polyhydric alcohol ester, Well-known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid, etc. can be used. Use of an alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention.
　好ましいモノカルボン酸の例としては以下のようなものを挙げることができるが、本発明はこれに限定されるものではない。
　脂肪族モノカルボン酸としては、炭素数１～３２の直鎖又は側鎖を有する脂肪酸を好ましく用いることができる。炭素数は１～２０であることがさらに好ましく、１～１０であることが特に好ましい。酢酸を含有させるとセルロースアシレートとの相溶性が増すため好ましく、酢酸と他のモノカルボン酸を混合して用いることも好ましい。
　好ましい脂肪族モノカルボン酸としては、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、２－エチル－ヘキサン酸、ウンデシル酸、ラウリン酸、トリデシル酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、ヘプタデシル酸、ステアリン酸、ノナデカン酸、アラキン酸、ベヘン酸、リグノセリン酸、セロチン酸、ヘプタコサン酸、モンタン酸、メリシン酸、ラクセル酸等の飽和脂肪酸、ウンデシレン酸、オレイン酸、ソルビン酸、リノール酸、リノレン酸、アラキドン酸等の不飽和脂肪酸等を挙げることができる。 Examples of preferred monocarboxylic acids include the following, but the present invention is not limited thereto.
As the aliphatic monocarboxylic acid, a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. The number of carbon atoms is more preferably 1-20, and particularly preferably 1-10. When acetic acid is contained, the compatibility with cellulose acylate is increased, and it is also preferable to use a mixture of acetic acid and another monocarboxylic acid.
Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanoic acid, undecylic acid, lauric acid, tridecylic acid, Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, laccelic acid, undecylenic acid, olein Examples thereof include unsaturated fatty acids such as acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.
　好ましい脂環族モノカルボン酸の例としては、シクロペンタンカルボン酸、シクロヘキサンカルボン酸、シクロオクタンカルボン酸、又はそれらの誘導体を挙げることができる。
　好ましい芳香族モノカルボン酸の例としては、安息香酸、トルイル酸等の安息香酸のベンゼン環にアルキル基、メトキシ基又はエトキシ基等のアルコキシ基を１～３個を導入したもの、ビフェニルカルボン酸、ナフタリンカルボン酸、テトラリンカルボン酸等のベンゼン環を２個以上有する芳香族モノカルボン酸、又はそれらの誘導体を挙げることができる。特に安息香酸が好ましい。 Examples of preferred alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, or derivatives thereof.
Examples of preferred aromatic monocarboxylic acids include those in which 1 to 3 alkoxy groups such as alkyl group, methoxy group or ethoxy group are introduced into the benzene ring of benzoic acid such as benzoic acid or toluic acid, biphenylcarboxylic acid, Examples thereof include aromatic monocarboxylic acids having two or more benzene rings such as naphthalenecarboxylic acid and tetralincarboxylic acid, or derivatives thereof. Benzoic acid is particularly preferable.
　多価アルコールエステルの分子量は特に制限はないが、３００～１５００であることが好ましく、３５０～７５０であることがさらに好ましい。分子量が大きい方が揮発し難くなるため好ましく、透湿性、セルロースアシレートとの相溶性の点では小さい方が好ましい。
　多価アルコールエステルに用いられるカルボン酸は１種類でもよいし、２種以上の混合であってもよい。また、多価アルコール中のＯＨ基は、全てエステル化してもよいし、一部をＯＨ基のままで残してもよい。 The molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably 300 to 1500, and more preferably 350 to 750. A higher molecular weight is preferable because it is less likely to volatilize, and a lower molecular weight is preferable in terms of moisture permeability and compatibility with cellulose acylate.
The carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.
　以下に、多価アルコールエステルの具体的化合物（ａｅ－１）～（ａｅ－３５）を例示する。
Figure JPOXMLDOC01-appb-C000014
 Specific examples of polyhydric alcohol esters (ae-1) to (ae-35) are shown below.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　グリコレート系可塑剤は特に限定されないが、アルキルフタリルアルキルグリコレート類が好ましく用いることができる。
　アルキルフタリルアルキルグリコレート類としては、例えばメチルフタリルメチルグリコレート、エチルフタリルエチルグリコレート、プロピルフタリルプロピルグリコレート、ブチルフタリルブチルグリコレート、オクチルフタリルオクチルグリコレート、メチルフタリルエチルグリコレート、エチルフタリルメチルグリコレート、エチルフタリルプロピルグリコレート、メチルフタリルブチルグリコレート、エチルフタリルブチルグリコレート、ブチルフタリルメチルグリコレート、ブチルフタリルエチルグリコレート、プロピルフタリルブチルグリコレート、ブチルフタリルプロピルグリコレート、メチルフタリルオクチルグリコレート、エチルフタリルオクチルグリコレート、オクチルフタリルメチルグリコレート、オクチルフタリルエチルグリコレート等が挙げられる。 The glycolate plasticizer is not particularly limited, but alkylphthalylalkyl glycolates can be preferably used.
Examples of alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl Glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycol Butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl glycolate, octyl phthalyl methyl glycolate, octyl phthalate Ethyl glycolate, and the like.
　フタル酸エステル系可塑剤としては、ジエチルフタレート、ジメトキシエチルフタレート、ジメチルフタレート、ジオクチルフタレート、ジブチルフタレート、ジ－２－エチルヘキシルフタレート、ジオクチルフタレート、ジシクロヘキシルフタレート、ジシクロヘキシルテレフタレート等が挙げられる。 Examples of the phthalate ester plasticizer include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.
　クエン酸エステル系可塑剤としては、クエン酸アセチルトリメチル、クエン酸アセチルトリエチル、クエン酸アセチルトリブチル等が挙げられる。
　脂肪酸エステル系可塑剤として、オレイン酸ブチル、リシノール酸メチルアセチル、セバシン酸ジブチル等が挙げられる。 Examples of the citrate plasticizer include acetyl trimethyl citrate, acetyl triethyl citrate, and acetyl tributyl citrate.
Examples of fatty acid ester plasticizers include butyl oleate, methylacetyl ricinoleate, and dibutyl sebacate.
　リン酸エステル系可塑剤としては、トリフェニルホスフェート、トリクレジルホスフェート、クレジルジフェニルホスフェート、オクチルジフェニルホスフェート、ジフェニルビフェニルホスフェート、トリオクチルホスフェート、トリブチルホスフェート等が挙げられる。
　多価カルボン酸エステル化合物としては、２価以上、好ましくは２～２０価の多価カルボン酸とアルコールのエステルよりなる。また、脂肪族多価カルボン酸は２～２０価であることが好ましく、芳香族多価カルボン酸、脂環式多価カルボン酸の場合は３～２０価であることが好ましい。 Examples of the phosphate ester plasticizer include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate and the like.
The polyvalent carboxylic acid ester compound comprises an ester of a divalent or higher, preferably 2 to 20 valent polyvalent carboxylic acid and an alcohol. The aliphatic polyvalent carboxylic acid is preferably divalent to 20-valent, and in the case of an aromatic polyvalent carboxylic acid or an alicyclic polyvalent carboxylic acid, it is preferably 3 to 20 valent.
　多価カルボン酸は次の一般式（IV）で表される。
　一般式（IV）　Ｒ１２（ＣＯＯＨ）ｍ１（ＯＨ）ｎ１
〔式中、Ｒ１２は（ｍ１＋ｎ１）価の有機基を表し、ｍ１は２以上の整数を表し、ｎ１は０以上の整数を表し、ＣＯＯＨ基はカルボキシ基を表し、ＯＨ基はアルコール性及び／又はフェノール性ヒドロキシ基を表す。〕 The polyvalent carboxylic acid is represented by the following general formula (IV).
Formula (IV) R 12 (COOH) m1 (OH) n1
[Wherein R 12 represents an (m1 + n1) -valent organic group, m1 represents an integer of 2 or more, n1 represents an integer of 0 or more, a COOH group represents a carboxy group, an OH group represents an alcoholic group and / or Or represents a phenolic hydroxy group. ]
　好ましい多価カルボン酸の例としては、以下を挙げることができるが、本発明はこれらに限定されるものではない。
　トリメリット酸、トリメシン酸、ピロメリット酸のような３価以上の芳香族多価カルボン酸又はその誘導体、コハク酸、アジピン酸、アゼライン酸、セバシン酸、シュウ酸、フマル酸、マレイン酸、テトラヒドロフタル酸のような脂肪族多価カルボン酸、酒石酸、タルトロン酸、リンゴ酸、クエン酸のようなオキシ多価カルボン酸等を好ましく用いることができる。特にオキシ多価カルボン酸を用いることが、保留性向上等の点で好ましい。 Examples of the preferred polyvalent carboxylic acid include the following, but the present invention is not limited thereto.
Trivalent or higher aromatic polyvalent carboxylic acids such as trimellitic acid, trimesic acid, pyromellitic acid or derivatives thereof, succinic acid, adipic acid, azelaic acid, sebacic acid, oxalic acid, fumaric acid, maleic acid, tetrahydrophthal An aliphatic polyvalent carboxylic acid such as an acid, an oxypolyvalent carboxylic acid such as tartaric acid, tartronic acid, malic acid and citric acid can be preferably used. In particular, it is preferable to use an oxypolycarboxylic acid from the viewpoint of improving the retention.
　多価カルボン酸エステル化合物に用いられるアルコールとしては特に制限はなく、公知のアルコール、フェノール類を用いることができる。
　例えば炭素数１～３２の直鎖又は側鎖を持った脂肪族飽和アルコール又は脂肪族不飽和アルコールを好ましく用いることができる。炭素数１～２０であることがさらに好ましく、炭素数１～１０であることが特に好ましい。 There is no restriction | limiting in particular as alcohol used for a polyhydric carboxylic acid ester compound, Well-known alcohol and phenols can be used.
For example, an aliphatic saturated alcohol or aliphatic unsaturated alcohol having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used. More preferably, it has 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
　また、シクロペンタノール、シクロヘキサノール等の脂環式アルコール又はその誘導体、ベンジルアルコール、シンナミルアルコール等の芳香族アルコール又はその誘導体等も好ましく用いることができる。
　多価カルボン酸としてオキシ多価カルボン酸を用いる場合は、オキシ多価カルボン酸のアルコール性又はフェノール性のヒドロキシ基を、モノカルボン酸を用いてエステル化してもよい。 In addition, alicyclic alcohols such as cyclopentanol and cyclohexanol or derivatives thereof, aromatic alcohols such as benzyl alcohol and cinnamyl alcohol, or derivatives thereof can also be preferably used.
When an oxypolycarboxylic acid is used as the polycarboxylic acid, the alcoholic or phenolic hydroxy group of the oxypolycarboxylic acid may be esterified with a monocarboxylic acid.
　多価カルボン酸エステル化合物の分子量は特に制限はないが、分子量３００～１０００の範囲であることが好ましく、３５０～７５０の範囲であることがさらに好ましい。保留性向上の点では大きい方が好ましく、透湿性、セルロースアシレートとの相溶性の点では小さい方が好ましい。
　本発明に用いることのできる多価カルボン酸エステルに用いられるアルコール類は１種類でもよいし、２種以上の混合物であってもよい。
　本発明に用いることのできる多価カルボン酸エステル化合物の酸価は１ｍｇＫＯＨ／ｇ以下であることが好ましく、０．２ｍｇＫＯＨ／ｇ以下であることがさらに好ましい。酸価を上記範囲にすることによって、リターデーションの環境変動も抑制されるため好ましい。 The molecular weight of the polyvalent carboxylic acid ester compound is not particularly limited, but the molecular weight is preferably in the range of 300 to 1000, and more preferably in the range of 350 to 750. The larger one is preferable in terms of improvement in retention, and the smaller one is preferable in terms of moisture permeability and compatibility with cellulose acylate.
The alcohols used in the polyvalent carboxylic acid ester that can be used in the present invention may be one kind or a mixture of two or more kinds.
The acid value of the polyvalent carboxylic acid ester compound that can be used in the present invention is preferably 1 mgKOH / g or less, and more preferably 0.2 mgKOH / g or less. Setting the acid value in the above range is preferable because the environmental fluctuation of the retardation is also suppressed.
　なお、酸価とは、試料１ｇ中に含まれる酸（試料中に存在するカルボキシ基）を中和するために必要な水酸化カリウムのミリグラム数をいう。酸価の値としては、ＪＩＳ　Ｋ００７０に準拠して測定した値を採用するものとする。 The acid value refers to the number of milligrams of potassium hydroxide necessary for neutralizing the acid (carboxy group present in the sample) contained in 1 g of the sample. As the acid value, a value measured according to JIS K0070 is adopted.
　特に好ましい多価カルボン酸エステル化合物の例を以下に示すが、本発明はこれに限定されるものではない。
　例えば、トリエチルシトレート、トリブチルシトレート、アセチルトリエチルシトレート（ＡＴＥＣ）、アセチルトリブチルシトレート（ＡＴＢＣ）、ベンゾイルトリブチルシトレート、アセチルトリフェニルシトレート、アセチルトリベンジルシトレート、酒石酸ジブチル、酒石酸ジアセチルジブチル、トリメリット酸トリブチル、ピロメリット酸テトラブチル等が挙げられる。 Examples of particularly preferred polyvalent carboxylic acid ester compounds are shown below, but the present invention is not limited thereto.
For example, triethyl citrate, tributyl citrate, acetyl triethyl citrate (ATEC), acetyl tributyl citrate (ATBC), benzoyl tributyl citrate, acetyl triphenyl citrate, acetyl tribenzyl citrate, dibutyl tartrate, diacetyl dibutyl tartrate, Examples include tributyl trimellitic acid and tetrabutyl pyromellitic acid.
（紫外線吸収剤）
　本発明のセルロースアシレートフィルムは、紫外線吸収剤を含有することもできる。紫外線吸収剤は４００ｎｍ以下の紫外線を吸収することにより、セルロースアシレートフィルムの耐久性の向上を目的として添加される。セルロースアシレートフィルムにおける波長３７０ｎｍでの透過率が１０％以下であることが好ましく、より好ましくは５％以下、さらに好ましくは２％以下である。 (UV absorber)
The cellulose acylate film of the present invention can also contain an ultraviolet absorber. The ultraviolet absorber is added for the purpose of improving the durability of the cellulose acylate film by absorbing ultraviolet rays of 400 nm or less. The transmittance at a wavelength of 370 nm in the cellulose acylate film is preferably 10% or less, more preferably 5% or less, and further preferably 2% or less.
　本発明に用いられる紫外線吸収剤は特に限定されないが、例えばオキシベンゾフェノン系化合物、ベンゾトリアゾール系化合物、サリチル酸エステル系化合物、ベンゾフェノン系化合物、シアノアクリレート系化合物、トリアジン系化合物、ニッケル錯塩系化合物、無機粉体等が挙げられる。
　例えば、５－クロロ－２－（３，５－ジ－ｓｅｃ－ブチル－２－ヒドロキシルフェニル）－２Ｈ－ベンゾトリアゾール、（２－２Ｈ－ベンゾトリアゾール－２－イル）－６－（直鎖及び側鎖ドデシル）－４－メチルフェノール、２－ヒドロキシ－４－ベンジルオキシベンゾフェノン、２，４－ベンジルオキシベンゾフェノン等があり、また、チヌビン１０９、チヌビン１７１、チヌビン２３４、チヌビン３２６、チヌビン３２７、チヌビン３２８等のチヌビン類があり、これらはいずれもＢＡＳＦジャパン社製の市販品であり好ましく使用できる。 Although the ultraviolet absorber used in the present invention is not particularly limited, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, inorganic powders Examples include the body.
For example, 5-chloro-2- (3,5-di-sec-butyl-2-hydroxylphenyl) -2H-benzotriazole, (2-2H-benzotriazol-2-yl) -6- (linear and side Chain dodecyl) -4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxybenzophenone, and the like, and tinuvin 109, tinuvin 171, tinuvin 234, tinuvin 326, tinuvin 327, tinuvin 328, etc. These are commercially available products made by BASF Japan and can be preferably used.
　本発明で好ましく用いられる紫外線吸収剤は、ベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、トリアジン系紫外線吸収剤であり、特に好ましくはベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤である。
　この他、１，３，５トリアジン環を有する化合物等の円盤状化合物も紫外線吸収剤として好ましく用いられる。 The ultraviolet absorber preferably used in the present invention is a benzotriazole ultraviolet absorber, a benzophenone ultraviolet absorber, or a triazine ultraviolet absorber, and particularly preferably a benzotriazole ultraviolet absorber or a benzophenone ultraviolet absorber.
In addition, a discotic compound such as a compound having a 1,3,5 triazine ring is also preferably used as the ultraviolet absorber.
　また、紫外線吸収剤としては高分子紫外線吸収剤も好ましく用いることができ、特に特開平６－１４８４３０号記載のポリマータイプの紫外線吸収剤が好ましく用いられる。
　紫外線吸収剤の添加方法は、メタノール、エタノール、ブタノール等のアルコールやメチレンクロライド、酢酸メチル、アセトン、ジオキソラン等の有機溶媒若しくはこれらの混合溶媒に紫外線吸収剤を溶解してからドープに添加するか、又は直接ドープ組成中に添加してもよい。 As the UV absorber, a polymer UV absorber can also be preferably used, and in particular, a polymer type UV absorber described in JP-A-6-148430 is preferably used.
The method for adding the UV absorber is to add the UV absorber to the dope after dissolving the UV absorber in an alcohol such as methanol, ethanol, butanol, an organic solvent such as methylene chloride, methyl acetate, acetone, dioxolane, or a mixed solvent thereof. Or you may add directly in dope composition.
　無機粉体のように有機溶媒に溶解しないものは、有機溶媒とセルロースアシレート中にディゾルバーやサンドミルを使用し、分散してからドープに添加する。
　紫外線吸収剤の使用量は、紫外線吸収剤の種類、使用条件等により一様ではないが、セルロースアシレートフィルムの乾燥膜厚が３０～２００μｍの場合は、フィルムの全質量に対して０．５～１０．０質量％が好ましく、０．６～４．０質量％がさらに好ましい。 For an inorganic powder that does not dissolve in an organic solvent, a dissolver or a sand mill is used in the organic solvent and cellulose acylate to disperse and then added to the dope.
The amount of UV absorber used is not uniform depending on the type of UV absorber, operating conditions, etc., but when the dry film thickness of the cellulose acylate film is 30 to 200 μm, it is 0.5 It is preferably ˜10.0 mass%, more preferably 0.6-4.0 mass%.
（酸化防止剤）
　酸化防止剤は劣化防止剤とも称される。高湿高温の状態に液晶画像表示装置等が置かれた場合には、セルロースアシレートフィルムの劣化が起こる場合がある。
　酸化防止剤は、例えば、セルロースアシレートフィルム中の残留溶媒量のハロゲンやリン酸系可塑剤のリン酸等によりセルロースアシレートフィルムが分解するのを遅らせたり、防いだりする役割を有するので、セルロースアシレートフィルム中に含有させることが好ましい。 (Antioxidant)
Antioxidants are also referred to as deterioration inhibitors. When a liquid crystal image display device or the like is placed in a high humidity and high temperature state, the cellulose acylate film may be deteriorated.
The antioxidant has a role of delaying or preventing the cellulose acylate film from being decomposed by, for example, the residual solvent amount of halogen in the cellulose acylate film or phosphoric acid of the phosphoric acid plasticizer. It is preferable to make it contain in an acylate film.
　このような酸化防止剤としては、ヒンダードフェノール系の化合物が好ましく用いられ、例えば、２，６－ジ－ｔ－ブチル－ｐ－クレゾール、ペンタエリスリチル－テトラキス〔３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート〕、トリエチレングリコール－ビス〔３－（３－ｔ－ブチル－５－メチル－４－ヒドロキシフェニル）プロピオネート〕、１，６－ヘキサンジオール－ビス〔３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート〕、２，４－ビス－（ｎ－オクチルチオ）－６－（４－ヒドロキシ－３，５－ジ－ｔ－ブチルアニリノ）－１，３，５－トリアジン、２，２－チオ－ジエチレンビス〔３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート〕、オクタデシル－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、Ｎ，Ｎ′－ヘキサメチレンビス（３，５－ジ－ｔ－ブチル－４－ヒドロキシ－ヒドロシンナマミド）、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）ベンゼン、トリス－（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）－イソシアヌレート等を挙げることができる。 As such an antioxidant, a hindered phenol compound is preferably used. For example, 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], oct Decyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxy Benzyl) -isocyanurate and the like.
　特に、２，６－ジ－ｔ－ブチル－ｐ－クレゾール、ペンタエリスリチル－テトラキス〔３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート〕、トリエチレングリコール－ビス〔３－（３－ｔ－ブチル－５－メチル－４－ヒドロキシフェニル）プロピオネート〕が好ましい。また、例えば、Ｎ，Ｎ′－ビス〔３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオニル〕ヒドラジン等のヒドラジン系の金属不活性剤やトリス（２，４－ジ－ｔ－ブチルフェニル）フォスファイト等のリン系加工安定剤を併用してもよい。
　これらの化合物の添加量は、セルロースアシレートフィルムに対して質量割合で１～５０００ｐｐｍが好ましく、１０～１０００ｐｐｍがさらに好ましい。 In particular, 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferred. Further, for example, hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di- A phosphorus processing stabilizer such as t-butylphenyl) phosphite may be used in combination.
The amount of these compounds added is preferably 1 to 5000 ppm, more preferably 10 to 1000 ppm in terms of mass ratio with respect to the cellulose acylate film.
（酸捕捉剤）
　セルロースアシレートは高温下では酸によっても分解が促進されるため、本発明のセルロースアシレートフィルムに用いる場合においては酸捕捉剤を含有することが好ましい。
　有用な酸捕捉剤としては、酸と反応して酸を不活性化する化合物であれば制限なく用いることができるが、なかでも米国特許第４，１３７，２０１号明細書に記載されているエポキシ基を有する化合物が好ましい。 (Acid scavenger)
Since cellulose acylate is accelerated by acid at high temperatures, it is preferable to contain an acid scavenger when used for the cellulose acylate film of the present invention.
Any useful acid scavenger can be used without limitation as long as it is a compound that reacts with an acid to inactivate the acid. Among them, the epoxy described in US Pat. No. 4,137,201 is particularly useful. Compounds having a group are preferred.
　このような酸捕捉剤としてのエポキシ化合物は、当該技術分野において既知であり、種々のポリグリコールのジグリシジルエーテル、特にポリグリコール１モル当たりに約８～４０モルのエチレンオキシド等の縮合によって誘導されるポリグリコール、グリセロールのジグリシジルエーテル等がある。また、塩化ビニルポリマー組成物において、又は塩化ビニルポリマー組成物とともに、従来から利用されているような金属エポキシ化合物、エポキシ化エーテル縮合生成物、ビスフェノールＡのジグリシジルエーテル（すなわち、４，４′－ジヒドロキシジフェニルジメチルメタン）、エポキシ化不飽和脂肪酸エステル等も挙げられる。エポキシ化不飽和脂肪酸エステルは、特に、炭素数２～２２の脂肪酸と、炭素数２～４のアルコールとのエステルが好ましく、例えばブチルエポキシステアレート等が挙げられる。他にも、エポキシ化大豆油等のような種々のエポキシ化長鎖脂肪酸トリグリセリド等の組成物によって代表され、例示され得るエポキシ化植物油、他の不飽和天然油が含まれる。これら油脂は、エポキシ化天然グリセリド又は不飽和脂肪酸とも呼ばれ、これら油脂の脂肪酸は一般に１２～２２個の炭素原子を含有している。また、市販のエポキシ基含有エポキシド樹脂化合物として、ＥＰＯＮ　８１５Ｃも好ましく用いることができる。 Epoxy compounds as such acid scavengers are known in the art and are derived by condensation of diglycidyl ethers of various polyglycols, particularly about 8 to 40 moles of ethylene oxide per mole of polyglycol. Examples include polyglycol and diglycidyl ether of glycerol. Also, in or together with the vinyl chloride polymer composition, metal epoxy compounds, epoxidized ether condensation products, diglycidyl ethers of bisphenol A (ie, 4,4′- Dihydroxydiphenyldimethylmethane), epoxidized unsaturated fatty acid ester and the like can also be mentioned. The epoxidized unsaturated fatty acid ester is particularly preferably an ester of a fatty acid having 2 to 22 carbon atoms and an alcohol having 2 to 4 carbon atoms, and examples thereof include butyl epoxy stearate. Others include epoxidized vegetable oils and other unsaturated natural oils that may be represented and exemplified by compositions such as various epoxidized long chain fatty acid triglycerides such as epoxidized soybean oil. These fats are also referred to as epoxidized natural glycerides or unsaturated fatty acids, and the fatty acids of these fats generally contain 12 to 22 carbon atoms. Moreover, EPON 815C can also be preferably used as a commercially available epoxy group-containing epoxide resin compound.
　さらに上記以外に用いることが可能な酸捕捉剤としては、オキセタン化合物やオキサゾリン化合物、アルカリ土類金属の有機酸塩、アセチルアセトナート錯体、特開平５－１９４７８８号公報の段落００６８～０１０５に記載されている化合物が含まれる。
　なお、酸捕捉剤は酸掃去剤、酸捕獲剤、酸キャッチャー等と称されることもあるが、本発明においてはこれらの呼称による差異なく用いることができる。 Further, acid scavengers that can be used in addition to the above are oxetane compounds, oxazoline compounds, organic acid salts of alkaline earth metals, acetylacetonate complexes, and paragraphs 0068 to 0105 of JP-A-5-194788. Are included.
In addition, although an acid scavenger may be called an acid scavenger, an acid capture agent, an acid catcher, etc., in this invention, it can use without a difference by these names.
（微粒子）
　本発明のセルロースアシレートフィルムには、取扱性を向上させるため、例えば二酸化ケイ素、二酸化チタン、酸化アルミニウム、酸化ジルコニウム、炭酸カルシウム、カオリン、タルク、焼成ケイ酸カルシウム、水和ケイ酸カルシウム、ケイ酸アルミニウム、ケイ酸マグネシウム、リン酸カルシウム等の無機微粒子や架橋高分子等のマット剤を含有させることが好ましい。なかでも二酸化ケイ素が、セルロースアシレートフィルムのヘイズを小さくできるため、好ましい。 (Fine particles)
The cellulose acylate film of the present invention has, for example, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, hydrated calcium silicate, silicic acid in order to improve handleability. It is preferable to contain a matting agent such as inorganic fine particles such as aluminum, magnesium silicate and calcium phosphate, and a crosslinked polymer. Of these, silicon dioxide is preferable because haze of the cellulose acylate film can be reduced.
　微粒子の１次平均粒径としては、２０ｎｍ以下が好ましく、より好ましくは５～１６ｎｍであり、特に好ましくは５～１２ｎｍである。
　これらの微粒子は、平均粒径が０．１～５．０μｍの２次粒子を形成してセルロースアシレートフィルムに含まれることが好ましく、より好ましい平均粒径は０．１～２．０μｍであり、さらに好ましくは０．２～０．６μｍである。これにより、セルロースアシレートフィルムの表面に、高さ０．１～１．０μｍ程度の凹凸を形成することができ、凹凸によって表面に適切な滑り性を与えることができる。 The primary average particle diameter of the fine particles is preferably 20 nm or less, more preferably 5 to 16 nm, and particularly preferably 5 to 12 nm.
These fine particles are preferably contained in the cellulose acylate film by forming secondary particles having an average particle size of 0.1 to 5.0 μm, and a more preferable average particle size is 0.1 to 2.0 μm. More preferably, the thickness is 0.2 to 0.6 μm. As a result, irregularities having a height of about 0.1 to 1.0 μm can be formed on the surface of the cellulose acylate film, and appropriate slipperiness can be imparted to the surface by the irregularities.
　本発明に用いられる微粒子の１次平均粒子径の測定は、透過型電子顕微鏡（倍率５０万～２００万倍）で粒子の観察を行い、粒子１００個を観察し、粒子径を測定しその平均値をもって、１次平均粒子径とする。 The primary average particle diameter of the fine particles used in the present invention is measured by observing the particles with a transmission electron microscope (magnification of 500,000 to 2,000,000 times), observing 100 particles, measuring the particle diameter, and measuring the average. Let the value be the primary average particle size.
＜セルロースアシレートフィルムの製造方法＞
　本発明に用いられるセルロースアシレートフィルムの製造方法は、ドープを金属支持体上に流延して得られたフィルムを乾燥し、剥離した後に延伸する工程を含む。当該ドープは、アシル基置換度が２．０～２．５であるセルロースアシレート及びＴｇ低下剤を必須に含むので、得られたセルロースアシレートフィルムの両表面におけるＴｇ低下剤の存在量がある程度偏るように、上記工程を行う。 <Method for producing cellulose acylate film>
The method for producing a cellulose acylate film used in the present invention includes a step of stretching a film obtained by casting a dope on a metal support, drying the film, and peeling the film. Since the dope essentially includes a cellulose acylate having a degree of acyl group substitution of 2.0 to 2.5 and a Tg reducing agent, the amount of the Tg reducing agent present on both surfaces of the obtained cellulose acylate film is to some extent. The above steps are performed so that they are biased.
　セルロースアシレートフィルムの製造方法は、溶液流延法による方法であってもよいし、溶融流延法による方法であってもよいが、好ましくは溶液流延法による方法である。
　以下、溶液流延法によるセルロースアシレートフィルムの製造方法を例に挙げて説明するが、下記の形態には限定されない。 The method for producing a cellulose acylate film may be a method by a solution casting method or a method by a melt casting method, but is preferably a method by a solution casting method.
Hereinafter, although the manufacturing method of the cellulose acylate film by a solution casting method is mentioned as an example and demonstrated, it is not limited to the following form.
　溶液流延法によるセルロースアシレートフィルムの製造は、例えばアシル基置換度が２．０～２．５であるセルロースアシレート及びＴｇ低下剤並びに必要に応じてその他の添加剤を溶媒に溶解させてドープを調製する工程、無限に移行する無端の金属支持体上にドープを流延する工程、流延したドープをウェブとして乾燥する工程、金属支持体から剥離する工程、延伸又は幅保持する工程、さらに乾燥する工程、仕上がったフィルムを巻取る工程を経る。 For producing a cellulose acylate film by a solution casting method, for example, cellulose acylate having an acyl group substitution degree of 2.0 to 2.5, a Tg reducing agent, and other additives as required are dissolved in a solvent. A step of preparing a dope, a step of casting the dope on an endless metal support that moves infinitely, a step of drying the cast dope as a web, a step of peeling from the metal support, a step of stretching or maintaining the width, Furthermore, the process of drying and the process of winding up the finished film are passed.
　まず、ドープを調製する工程について説明する。
　ドープ中のセルロースアシレートの濃度は、濃い方が金属支持体に流延した後の乾燥負荷が低減できることから好ましいが、セルロースアシレートの濃度が濃過ぎると濾過時の負荷が増えて、濾過精度が悪くなる。これらを両立する濃度としては、１０～３５質量％が好ましく、さらに好ましくは、１５～２５質量％である。また、Ｔｇ低下剤やその他の添加剤については、ドープ調製釜に規定量をバッチ添加することが好ましい。 First, the process for preparing the dope will be described.
The concentration of cellulose acylate in the dope is preferable because it can reduce the drying load after casting on the metal support, but if the concentration of cellulose acylate is too high, the load during filtration increases and the filtration accuracy Becomes worse. The concentration that achieves both of these is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass. As for the Tg lowering agent and other additives, it is preferable to batch add a specified amount to the dope preparation kettle.
　ドープの調製に用いられる溶媒は、単独で用いても２種以上を併用してもよいが、セルロースアシレートの良溶媒と貧溶媒とを混合して使用することが生産効率の点で好ましく、良溶媒が多い方がセルロースアシレートの溶解性の点で好ましい。 The solvent used for the preparation of the dope may be used alone or in combination of two or more, but it is preferable in terms of production efficiency to use a mixture of a good solvent and a poor solvent of cellulose acylate, A larger amount of good solvent is preferred from the viewpoint of the solubility of cellulose acylate.
　良溶媒と貧溶媒との混合比率の好ましい範囲は、良溶媒が７０～９８質量％であり、貧溶媒が２～３０質量％である。良溶媒、貧溶媒とは、使用するセルロースアシレートを単独で溶解する溶媒が良溶媒と定義され、単独で膨潤するか又は溶解しない溶媒が貧溶媒と定義される。そのため、セルロースアシレートのアシル基置換度によって、良溶媒、貧溶媒が変わる。 The preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent. With a good solvent and a poor solvent, the solvent which dissolves the cellulose acylate to be used alone is defined as a good solvent, and a solvent which swells alone or does not dissolve is defined as a poor solvent. Therefore, the good solvent and the poor solvent change depending on the acyl group substitution degree of cellulose acylate.
　本発明に用いられる良溶媒は特に限定されないが、メチレンクロライド等の有機ハロゲン化合物、ジオキソラン類、アセトン、酢酸メチル、アセト酢酸メチル等が挙げられる。特に好ましくはメチレンクロライド又は酢酸メチルが挙げられる。 The good solvent used in the present invention is not particularly limited, and examples thereof include organic halogen compounds such as methylene chloride, dioxolanes, acetone, methyl acetate, and methyl acetoacetate. Particularly preferred is methylene chloride or methyl acetate.
　また、本発明に用いられる貧溶媒は特に限定されないが、例えば、メタノール、エタノール、ｎ－ブタノール、シクロヘキサン、シクロヘキサノン等が好ましく用いられる。また、ドープ中に０．０１～２．００質量％の水が含まれていることが好ましい。 Further, the poor solvent used in the present invention is not particularly limited, but for example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone and the like are preferably used. The dope preferably contains 0.01 to 2.00% by mass of water.
　セルロースアシレートの溶解に用いられた溶媒は、フィルム製膜工程で乾燥によりフィルムから除去された溶媒を回収することにより、再利用され得る。
　回収溶媒中に、セルロースアシレートに添加されている添加剤、例えば可塑剤、紫外線吸収剤、ポリマー、モノマー成分等が微量含有されていることもあるが、これらが含まれていても好ましく再利用することができるし、必要であれば精製して再利用することもできる。 The solvent used for dissolving cellulose acylate can be reused by collecting the solvent removed from the film by drying in the film-forming process.
The recovered solvent may contain trace amounts of additives added to cellulose acylate, such as plasticizers, UV absorbers, polymers, monomer components, etc. Can be purified and reused if necessary.
　上記ドープを調製する時の、セルロースアシレートの溶解方法としては、一般的な方法を用いることができる。加熱と加圧を組み合わせると常圧における沸点以上に加熱できる。
　溶媒の常圧での沸点以上、かつ加圧下で、溶媒が沸騰しない範囲の温度で加熱しながら攪拌溶解すると、ゲルやママコと呼ばれる塊状未溶解物の発生を防止することができ、好ましい。 As a method for dissolving cellulose acylate when preparing the dope, a general method can be used. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure.
It is preferable to stir and dissolve while heating at a temperature not lower than the boiling point at normal pressure of the solvent and under pressure so that the solvent does not boil, because it is possible to prevent the formation of a bulk undissolved material called gel or mamako.
　加熱は外部から行うことが好ましく、例えばジャケットタイプのものは温度コントロールが容易で好ましい。
　溶媒を添加しての加熱温度は、高い方がセルロースアシレートの溶解性の観点から好ましいが、加熱温度が高過ぎると必要とされる圧力が大きくなり生産性が悪くなる。
　好ましい加熱温度の範囲は４５～１２０℃であり、６０～１１０℃がより好ましく、７０～１０５℃がさらに好ましい。
　加圧は、窒素ガス等の不活性気体を圧入する方法や、加熱によって溶媒の蒸気圧を上昇させる方法によって行ってもよい。圧力は設定温度で溶媒が沸騰しないように調整される。 Heating is preferably performed from the outside. For example, a jacket type is preferable because temperature control is easy.
The heating temperature with the addition of the solvent is preferably higher from the viewpoint of the solubility of cellulose acylate, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates.
The range of the preferred heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and further preferably 70 to 105 ° C.
The pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of increasing the vapor pressure of the solvent by heating. The pressure is adjusted so that the solvent does not boil at the set temperature.
　また、セルロースアシレートの溶解方法として、セルロースアシレートを貧溶媒と混合して湿潤又は膨潤させた後、さらに良溶媒を添加して溶解させる方法も好ましく用いられる。
　その他、冷却溶解法も好ましく用いられ、これによって酢酸メチル等の溶媒にセルロースアシレートを溶解させることができる。 As a method for dissolving cellulose acylate, a method in which cellulose acylate is mixed with a poor solvent and wetted or swollen, and then a good solvent is further added and dissolved is preferably used.
In addition, a cooling dissolution method is also preferably used, whereby cellulose acylate can be dissolved in a solvent such as methyl acetate.
　次に、このセルロースアシレート溶液を濾紙等の適当な濾過材を用いて濾過する。濾過材としては、不溶物等を除去するために絶対濾過精度が小さい方が好ましいが、濾過材の目詰まりの発生を抑える観点から、絶対濾過精度が０．００８ｍｍ以下の濾材が好ましく、０．００１～０．００８ｍｍの濾材がより好ましく、０．００３～０．００６ｍｍの濾材がさらに好ましい。 Next, the cellulose acylate solution is filtered using a suitable filter medium such as filter paper. As the filter medium, it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like, but from the viewpoint of suppressing the occurrence of clogging of the filter medium, a filter medium having an absolute filtration accuracy of 0.008 mm or less is preferable. A filter medium of 001 to 0.008 mm is more preferable, and a filter medium of 0.003 to 0.006 mm is more preferable.
　濾材の材質は特に制限はなく、通常の濾材を使用することができるが、ポリプロピレン、テフロン（登録商標）等のプラスチック製の濾材や、ステンレススティール等の金属製の濾材が、繊維の脱落等がなく好ましい。
　濾過により、原料のセルロースアシレートに含まれていた不純物、特に輝点異物を除去、低減することが好ましい。 There are no particular restrictions on the material of the filter medium, and ordinary filter media can be used. However, plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel can cause fibers to fall off. Less preferred.
It is preferable to remove and reduce impurities, particularly bright spot foreign matter, contained in the raw material cellulose acylate by filtration.
　輝点異物とは、２枚の偏光板をクロスニコル状態にして配置し、その間に光学フィルム等を置き、一方の偏光板の側から光を当てて、他方の偏光板の側から観察した時に反対側からの光が漏れて見える点（異物）のことをいう。
　径が０．０１ｍｍ以上である輝点異物の数が２００個／ｃｍ２以下であることが好ましく、より好ましくは１００個／ｃｍ２以下であり、さらに好ましくは５０個／ｍ２以下であり、特に好ましくは０～１０個／ｃｍ２以下である。また、径が０．０１ｍｍ以下の輝点異物も少ない方が好ましい。 Bright spot foreign matter means that when two polarizing plates are placed in a crossed Nicol state, an optical film or the like is placed between them, light is applied from one polarizing plate side, and observation is performed from the other polarizing plate side. The point (foreign matter) that the light from the opposite side appears to leak.
The number of bright spot foreign matters having a diameter of 0.01 mm or more is preferably 200 pieces / cm 2 or less, more preferably 100 pieces / cm 2 or less, further preferably 50 pieces / m 2 or less, Particularly preferably, it is 0 to 10 pieces / cm 2 or less. Further, it is preferable that the number of bright spot foreign matters having a diameter of 0.01 mm or less is small.
　ドープの濾過は通常の方法で行うことができるが、溶媒の常圧での沸点以上、かつ加圧下で、溶媒が沸騰しない範囲の温度で加熱しながら濾過する方法が、濾過前後の濾圧の差の上昇が小さく、好ましい。
　好ましい温度範囲は４５～１２０℃であり、４５～７０℃がより好ましく、４５～５５℃がさらに好ましい。
　濾圧は小さい方が好ましい。濾圧は１．６ＭＰａ以下であることが好ましく、１．２ＭＰａ以下であることがより好ましく、１．０ＭＰａ以下であることがさらに好ましい。 The dope can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and under a pressure in a range where the solvent does not boil is the filtration pressure before and after filtration. The increase in the difference is small and preferable.
A preferred temperature range is 45 to 120 ° C, more preferably 45 to 70 ° C, and even more preferably 45 to 55 ° C.
A smaller filtration pressure is preferred. The filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.
　ここで、上述したように、得られるセルロースアシレートフィルムの両表面におけるＴｇ低下剤の存在量がある程度偏るように、一連の工程を行う。具体的には、製造されたセルロースアシレートフィルムの偏光子との貼合面と他方の面とにおけるＴｇ低下剤の検出値ｄＡ、ｄＢから定まるｒ値が、１．１以上となるように、上記の一連の工程を行う。 Here, as described above, a series of steps is performed so that the existing amount of the Tg reducing agent on both surfaces of the obtained cellulose acylate film is biased to some extent. Specifically, as the produced cellulose acylate film detection value d A of the Tg-lowering agent in the bonding surface and the other surface of the polarizer, r values determined from d B becomes 1.1 or more In addition, the above-described series of steps is performed.
　ｒ値が１．１以上となるように上記工程を行う具体的な手法については特に制限がなく、種々の手法が採用され得る。以下、代表的な３つの実施形態（第１の形態～第３の形態）について説明するが、このような形態に限定されない。 There is no particular limitation on the specific method for performing the above steps so that the r value is 1.1 or more, and various methods can be adopted. Hereinafter, three typical embodiments (first to third embodiments) will be described, but the present invention is not limited to such embodiments.
（第１の形態）
　第１の形態は、ドープを調製する際の各種材料の選択により、上記工程の実施を可能とする。具体的には、ドープの必須成分として、セルロースアシレート、Ｔｇ低下剤及び溶媒の３成分があるが、これら３成分のそれぞれのハンセンの溶解度パラメーターの値が、所定の関係を満たすように材料を選択する。これにより、得られたセルロースアシレートフィルムにおいてＴｇ低下剤の分布を厚さ方向に偏らせることができることが判明した。より詳細には、セルロースアシレート、Ｔｇ低下剤及び溶媒のそれぞれのハンセンの溶解度パラメーターの値を、この順に、ＨＳＰＣ、ＨＳＰＧ、ＨＳＰＳとしたとき、下記数式（４）を満足するようにそれぞれの材料を選択すればよい。
　数式（４）　　｜ＨＳＰＧ－ＨＳＰＣ｜＞｜ＨＳＰＧ－ＨＳＰＳ｜ (First form)
In the first embodiment, the above process can be performed by selecting various materials when preparing the dope. Specifically, as the essential components of the dope, there are three components, cellulose acylate, Tg lowering agent, and solvent. The material is selected so that the solubility parameter value of each of these three components satisfies a predetermined relationship. select. Thereby, it was found that the distribution of the Tg reducing agent can be biased in the thickness direction in the obtained cellulose acylate film. More specifically, when the Hansi solubility parameters of cellulose acylate, Tg lowering agent and solvent are HSP C , HSP G and HSP S in this order, the following formula (4) is satisfied. Each material may be selected.
Formula (4) | HSP G -HSP C |> | HSP G -HSP S |
　ハンセンの溶解度パラメーター（ＨＳＰ）は、チャールズ・ハンセンによって開発された、物質の溶解性を示すためのパラメーターである。上記ハンセンの溶解度パラメーターＨＳＰＣ、ＨＳＰＧ、ＨＳＰＳの値として、Ｈａｎｓｅｎ，　Ｃｈａｒｌｅｓ　（２００７）．　Ｈａｎｓｅｎ　Ｓｏｌｕｂｉｌｉｔｙ　Ｐａｒａｍｅｔｅｒｓ：　Ａ　ｕｓｅｒ’ｓ　ｈａｎｄｂｏｏｋ，　Ｓｅｃｏｎｄ　Ｅｄｉｔｉｏｎに記載された方法により測定された値を採用する。なお、セルロースアシレート、Ｔｇ低下剤及び溶媒が、それぞれ２種以上の混合物となっている形態もあり得るが、そのような形態におけるＨＳＰＣ、ＨＳＰＧ、ＨＳＰＳの値としては、混合物として測定された値を採用する。 The Hansen Solubility Parameter (HSP) is a parameter developed by Charles Hansen to indicate the solubility of a substance. The Hansen solubility parameters HSP C , HSP G , and HSP S are described in Hansen, Charles (2007). Hansen Solubility Parameters: Values measured by the method described in A user's handbook, Second Edition are adopted. In addition, there may be a form in which the cellulose acylate, the Tg lowering agent and the solvent are each a mixture of two or more, but the values of HSP C , HSP G and HSP S in such a form are measured as a mixture. Adopted values.
　上記数式（４）の技術的意義について簡単に説明すると、｜ＨＳＰＧ－ＨＳＰＣ｜は、Ｔｇ低下剤の溶解度パラメーターの値ＨＳＰＧとセルロースアシレートの溶解度パラメーターの値ＨＳＰＣとの差の絶対値を意味する。一方、｜ＨＳＰＧ－ＨＳＰＳ｜は、Ｔｇ低下剤の溶解度パラメーターの値ＨＳＰＧと溶媒の溶解度パラメーターの値ＨＳＰＳとの差の絶対値を意味する。そして、数式（４）が成立するということは、前者が後者よりも大きい、すなわちＴｇ低下剤の溶解度パラメーターの値ＨＳＰＧが、セルロースアシレートの値ＨＳＰＣよりも溶媒の値ＨＳＰＳに近いことを意味する。 Briefly the technical significance of the above equation (4), | HSP G -HSP C | is the absolute of the difference between the value HSP C solubility parameter values HSP G cellulose acylate solubility parameter of Tg-lowering agent Mean value. On the other hand, | HSP G −HSP S | means the absolute value of the difference between the solubility parameter value HSP G of the Tg lowering agent and the solubility parameter value HSP S of the solvent. Then, the fact that equation (4) is satisfied, the former is larger than the latter, that is, the value HSP G solubility parameter of Tg-lowering agent, close to the value HSP S of solvent than the value HSP C of the cellulose acylate Means.
　数式（４）を満たすように材料を選択したとき、得られたセルロースアシレートフィルムにおいて、Ｔｇ低下剤の分布がフィルムの厚さ方向に偏るメカニズムは完全には明らかではないが、溶解度パラメーターが近いほど溶解性（親和性）がより高いことを意味することから、以下のようなメカニズムが推定されている。すなわち、金属支持体上で乾燥させたときに、金属支持体に接していない面（空気との界面）から徐々に溶剤が揮発していくため、セルロースアシレートフィルムの厚さ方向で溶剤の濃度勾配が発生する。その際、Ｔｇ低下剤の溶剤に対する親和性が、セルロースアシレートに対する親和性よりも高ければ、より溶剤濃度の大きな金属支持体側に偏って存在することになると考えられる。 When the material is selected so as to satisfy Equation (4), in the obtained cellulose acylate film, the mechanism by which the distribution of the Tg reducing agent is biased in the thickness direction of the film is not completely clear, but the solubility parameters are close. Since it means that the solubility (affinity) is higher, the following mechanism has been estimated. That is, when dried on the metal support, the solvent gradually evaporates from the surface not in contact with the metal support (interface with air), so the concentration of the solvent in the thickness direction of the cellulose acylate film A gradient occurs. At that time, if the affinity of the Tg lowering agent for the solvent is higher than the affinity for the cellulose acylate, it is considered that the Tg lowering agent is biased toward the metal support having a higher solvent concentration.
　溶解度パラメーターの値ＨＳＰＣ、ＨＳＰＧ、ＨＳＰＳが、上記数式（４）を満たす場合、｜ＨＳＰＧ－ＨＳＰＣ｜は、｜ＨＳＰＧ－ＨＳＰＳ｜の１．１倍以上であることが好ましく、１．２倍以上であることがより好ましく、１．５倍以上であることがさらに好ましい。このような範囲とすることにより、製造されたセルロースアシレートフィルムにおけるＴｇ低下剤の厚さ方向の分布の偏りを確実に発現させることが可能となる。 When the solubility parameter values HSP C , HSP G , and HSP S satisfy the above formula (4), | HSP G −HSP C | is preferably 1.1 times or more of | HSP G −HSP S |. 1.2 times or more is more preferable, and 1.5 times or more is more preferable. By setting it as such a range, it becomes possible to express the bias | inclination of the distribution of the thickness direction of the Tg reducing agent in the manufactured cellulose acylate film reliably.
　続いて、ドープの流延（キャスト）について説明する。
　流延（キャスト）工程に用いられる金属支持体は、表面を鏡面仕上げしたものが好ましく、金属支持体としては、ステンレススティールベルト又は鋳物で表面をメッキ仕上げしたドラムが好ましく用いられる。 Next, dope casting will be described.
The metal support used in the casting process is preferably a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support.
　キャストの幅は１～４ｍとすることができる。流延工程の金属支持体の表面温度は－５０℃～溶媒の沸点未満の温度で、温度が高い方がウェブの乾燥速度が速くできるので好ましい。しかし、あまり温度が高過ぎるとウェブが発泡したり、平面性が劣化したりする場合がある。
　好ましい支持体温度の範囲は０～５５℃であり、２５～５０℃がさらに好ましい。
　また、冷却することによってウェブをゲル化させて残留溶媒を多く含んだ状態でドラムから剥離することも好ましい方法である。 The cast width can be 1 to 4 m. The surface temperature of the metal support in the casting step is −50 ° C. to less than the boiling point of the solvent, and a higher temperature is preferable because the web can be dried faster. However, if the temperature is too high, the web may foam or the flatness may deteriorate.
The preferred support temperature range is 0 to 55 ° C, more preferably 25 to 50 ° C.
It is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent.
　金属支持体の温度を制御する方法は特に制限されないが、温風又は冷風を吹きかける方法や、温水を金属支持体の裏側に接触させる方法がある。温水を用いる方が熱の伝達が効率的に行われるため、金属支持体の温度が一定になるまでの時間が短くなり好ましい。温風を用いる場合、目的の温度よりも高い温度の風を使う場合がある。 The method for controlling the temperature of the metal support is not particularly limited, but there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use hot water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is shortened. When warm air is used, wind at a temperature higher than the target temperature may be used.
　次に、流延によって得られたフィルムを乾燥し、剥離する。
　ここで、セルロースアシレートフィルムにおいてＴｇ低下剤の分布を厚さ方向に偏らせる第２の実施形態として、ドープを金属支持体上に流延した後のプロセス条件を制御する方法が挙げられる。
　具体的には、フィルムを金属支持体から剥離する時点におけるフィルム中の残留溶媒量を少なめにする。すなわち、より過酷な条件下で乾燥することにより、得られたセルロースアシレートフィルムにおいてＴｇ低下剤の分布が厚さ方向に偏ったものとすることが可能となることが判明した。 Next, the film obtained by casting is dried and peeled off.
Here, as a second embodiment in which the distribution of the Tg reducing agent is biased in the thickness direction in the cellulose acylate film, there is a method of controlling the process conditions after casting the dope on the metal support.
Specifically, the amount of residual solvent in the film at the time of peeling the film from the metal support is reduced. That is, it has been found that by drying under more severe conditions, it is possible to make the distribution of the Tg reducing agent biased in the thickness direction in the obtained cellulose acylate film.
　より詳細には、金属支持体から剥離する時点におけるフィルム中の残留溶媒量が、９０％以下となるようにプロセス条件を制御すればよい。なお、金属支持体から剥離する時点におけるフィルム中の残留溶媒量は、好ましくは８５％以下であり、より好ましくは８０％以下である。また、この第２の形態による制御と、上述した第１の形態（ドープ調製時の材料の選択）による制御とが併せて実施されてもよい。もちろん、いずれか一方のみの制御によっても、Ｔｇ低下剤の分布の偏りを有するセルロースアシレートフィルムを製造することが可能である。 More specifically, the process conditions may be controlled so that the residual solvent amount in the film at the time of peeling from the metal support is 90% or less. The amount of residual solvent in the film at the time of peeling from the metal support is preferably 85% or less, more preferably 80% or less. In addition, the control according to the second mode and the control according to the first mode (selection of material at the time of dope preparation) described above may be performed together. Of course, it is possible to produce a cellulose acylate film having an uneven distribution of the Tg reducing agent by controlling only one of them.
　残留溶媒量は、下記数式５で定義される。
　数式（５）　　残留溶媒量（質量％）＝｛（Ｍ－Ｎ）／Ｎ｝×１００
〔式中、Ｍはウェブ又はセルロースアシレートフィルムを製造中又は製造後の任意の時点で採取した試料の質量を表し、Ｎは当該試料を１１５℃にて１時間加熱した後の質量を表す。〕 The amount of residual solvent is defined by the following formula 5.
Formula (5) Residual solvent amount (% by mass) = {(MN) / N} × 100
[In the formula, M represents the mass of a sample collected at any time during or after production of the web or cellulose acylate film, and N represents the mass after heating the sample at 115 ° C. for 1 hour. ]
　残留溶媒量の値を所定の値以下とするために制御されるプロセス条件としては、金属支持体からフィルムを剥離する前の乾燥条件が挙げられる。金属支持体からのフィルム剥離前の乾燥条件の具体的な形態について特に制限はなく、剥離時点でのフィルムの残留溶媒量の値が所定の値以下となるように乾燥条件を制御することは、当業者であれば特段の困難性を伴うことなく実施することが可能である。乾燥条件の一例を挙げると、乾燥温度の範囲は、好ましくは２５～５０℃程度であり、より好ましくは３５～４５℃である。また、乾燥時間は、好ましくは１５～１５０秒間程度であり、より好ましくは２５～１２０秒間である。剥離時点でのフィルムの残留溶媒量の値が所定の値以下となるのであれば、これらの範囲を外れる条件が採用されてもよいことはもちろんである。 Process conditions that are controlled so that the value of the residual solvent amount is not more than a predetermined value include drying conditions before peeling the film from the metal support. There is no particular limitation on the specific form of drying conditions before film peeling from the metal support, and controlling the drying conditions so that the value of the residual solvent amount of the film at the time of peeling is not more than a predetermined value, Those skilled in the art can carry out the present invention without any particular difficulty. As an example of the drying conditions, the range of the drying temperature is preferably about 25 to 50 ° C., more preferably 35 to 45 ° C. The drying time is preferably about 15 to 150 seconds, more preferably 25 to 120 seconds. Of course, if the value of the residual solvent amount of the film at the time of peeling is not more than a predetermined value, conditions outside these ranges may be adopted.
　乾燥工程において採用される乾燥手段について特に制限はなく、公知の知見が適宜参照され得る。乾燥手段の具体例としては、熱風、赤外線、加熱ローラー、マイクロ波等が挙げられるが、簡便さの観点から、熱風で行うことが好ましい。 There is no restriction | limiting in particular about the drying means employ | adopted in a drying process, A well-known knowledge can be referred suitably. Specific examples of the drying means include hot air, infrared rays, heating rollers, and microwaves, but it is preferable to carry out with hot air from the viewpoint of simplicity.
　次に、金属支持体から剥離されたフィルム（ウェブ）を延伸する。この際、剥離されたフィルム（ウェブ）の両端を、クリップ等で把持するテンター方式で幅方向（フィルムの面内で製膜方向に直交する方向）に延伸を行うことが特に好ましい。また、金属支持体からの剥離張力は、３００Ｎ／ｍ以下とすることが好ましい。 Next, the film (web) peeled from the metal support is stretched. Under the present circumstances, it is especially preferable to extend | stretch in the width direction (direction orthogonal to the film forming direction within the surface of a film) by the tenter system which hold | grips both ends of the peeled film (web) with a clip etc. The peel tension from the metal support is preferably 300 N / m or less.
　延伸処理時の条件を調節することによって、得られたセルロースアシレートフィルムの膜厚や、リターデーション値を制御することができる。
　例えば、長手方向の張力を低く又は高くすることでリターデーションを変動させることが可能となる。また、フィルムの長手方向（製膜方向又は流延方向ともいう）と幅方向に対して、逐次又は同時に、２軸延伸又は１軸延伸することでリターデーションを変動させることができる。 By adjusting the conditions during the stretching treatment, the film thickness and retardation value of the obtained cellulose acylate film can be controlled.
For example, the retardation can be changed by lowering or increasing the tension in the longitudinal direction. Moreover, retardation can be fluctuate | varied by carrying out biaxial stretching or uniaxial stretching sequentially or simultaneously with respect to the longitudinal direction (it is also called the film forming direction or casting direction) and the width direction of a film.
　互いに直交する２軸方向の延伸倍率は、それぞれ最終的には長手方向に０．８～１．５倍、幅方向に１．１～２．０倍の範囲とすることが好ましく、長手方向に０．８～１．１倍、幅方向に１．３～１．７倍の範囲で行うことがより好ましく、幅方向に１．３～１．５倍の範囲で行うことが特に好ましい。
　本発明のセルロースアシレートフィルムは延伸しやすく、またリターデーションが発現しやすいこともあり、破断等の工程故障に関して耐性が高い。 The draw ratios in the biaxial directions orthogonal to each other are preferably finally in the range of 0.8 to 1.5 times in the longitudinal direction and 1.1 to 2.0 times in the width direction. More preferably, it is performed in the range of 0.8 to 1.1 times and in the range of 1.3 to 1.7 times in the width direction, and particularly preferably in the range of 1.3 to 1.5 times in the width direction.
The cellulose acylate film of the present invention is easily stretched and retardation is likely to develop, and has high resistance to process failures such as breakage.
　延伸時の温度範囲は１２０℃～２００℃が好ましく、より好ましくは１３０℃～１７０℃であり、さらに好ましくは１４０℃を超えて１６０℃以下である。延伸処理の際のフィルム中の残留溶媒量の範囲は２０～０％が好ましく、より好ましくは１５～０％である。より詳細には、例えば温度１５５℃で残留溶媒量が１１％で延伸するか、温度１５５℃で残留溶媒量が２％で延伸することが好ましい。或いは、温度１６０℃で残留溶媒量が１１％で延伸するか、１６０℃で残留溶媒量が１％未満で延伸することが好ましい。 The temperature range during stretching is preferably 120 ° C. to 200 ° C., more preferably 130 ° C. to 170 ° C., and further preferably more than 140 ° C. and 160 ° C. or less. The range of the residual solvent amount in the film during the stretching treatment is preferably 20 to 0%, more preferably 15 to 0%. More specifically, for example, it is preferable that the residual solvent amount is stretched by 11% at a temperature of 155 ° C., or the residual solvent amount is stretched by 2% at a temperature of 155 ° C. Alternatively, it is preferable to stretch at a temperature of 160 ° C. with a residual solvent amount of 11%, or at 160 ° C. with a residual solvent amount of less than 1%.
　ウェブを延伸する方法には特に限定はない。例えば、複数のローラーに周速差をつけ、その周速差を利用して縦方向に延伸する方法、ウェブの両端をクリップやピンで固定し、クリップやピンの間隔を進行方向に広げて縦方向に延伸する方法、同様に横方向に広げて横方向に延伸する方法、又は縦横同時に広げて縦横両方向に延伸する方法等が挙げられる。もちろんこれらの方法は、組み合わせて用いてもよい。 There is no particular limitation on the method of stretching the web. For example, a method in which a circumferential speed difference is applied to a plurality of rollers and the longitudinal speed difference is used to stretch in the longitudinal direction, both ends of the web are fixed with clips and pins, and the distance between the clips and pins is widened in the traveling direction. Examples thereof include a method of stretching in the direction, a method of stretching in the horizontal direction and stretching in the horizontal direction, a method of stretching in the vertical and horizontal directions and stretching in both the vertical and horizontal directions, and the like. Of course, these methods may be used in combination.
　いわゆるテンター法の場合、リニアドライブ方式でクリップ部分を駆動すると滑らかな延伸を行うことができ、破断等の可能性を減少できるので好ましい。
　製膜工程のこれらの幅保持又は横方向の延伸はテンターによって行うことが好ましく、ピンテンターでもクリップテンターでもよい。 In the case of the so-called tenter method, driving the clip portion by the linear drive method is preferable because smooth stretching can be performed and the possibility of breakage or the like can be reduced.
It is preferable to carry out the width maintenance or lateral stretching in the film forming step by a tenter, and it may be a pin tenter or a clip tenter.
　上述した延伸後に、さらに乾燥する工程を行い、残留溶媒量を１質量％以下にすることが好ましく、より好ましくは０．１０質量％以下であり、さらに好ましくは０．００～０．０１質量％以下である。
　延伸後の乾燥温度としては、１２５℃以上であることが好ましく、１４０℃以上であることがさらに好ましい。１５０℃を超えると、セルロースアシレートフィルムのガラス転移温度Ｔｇに近づくことから、リターデーション値の低下や配向角のズレ等が生じる場合があり、好ましくない。 After the stretching described above, a further drying step is performed to make the residual solvent amount 1% by mass or less, more preferably 0.10% by mass or less, and further preferably 0.00 to 0.01% by mass. It is as follows.
The drying temperature after stretching is preferably 125 ° C. or higher, and more preferably 140 ° C. or higher. If it exceeds 150 ° C., it approaches the glass transition temperature Tg of the cellulose acylate film, which may lead to a decrease in retardation value or misalignment of the orientation angle.
　以上、溶液流延法による製造方法を例に挙げて説明したが、製造コストの観点から、溶融流延法によって製造してもよい。この場合には、上述した第２の形態による制御によって、所望のセルロースアシレートフィルムを得ることができる。 As mentioned above, although the manufacturing method by the solution casting method was mentioned as an example, it may be manufactured by the melt casting method from the viewpoint of manufacturing cost. In this case, a desired cellulose acylate film can be obtained by the control according to the second embodiment described above.
　溶液流延法において用いられる溶媒（例えば塩化メチレン等）を用いずに、加熱溶融する溶融流延による成形法は、溶融押出成形法、プレス成形法、インフレーション法、射出成形法、ブロー成形法、延伸成形法等に分類できる。これらのなかで、機械的強度及び表面精度等に優れるセルロースアシレートフィルムを得るためには、溶融押出成形法が優れている。溶融流延法によってセルロースアシレートのウェブを得るための具体的な手法について特に制限はなく、公知の知見が適宜参照され得る。 Without using the solvent used in the solution casting method (for example, methylene chloride, etc.), the molding method by melt casting that is heated and melted is a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, It can be classified into a stretch molding method. Among these, in order to obtain a cellulose acylate film excellent in mechanical strength, surface accuracy and the like, the melt extrusion molding method is excellent. There is no particular limitation on the specific method for obtaining the cellulose acylate web by the melt casting method, and known knowledge can be referred to as appropriate.
　溶液流延法、溶融流延法の他にも、共流延法によって厚さ方向にＴｇ低下剤の分布が偏ったセルロースアシレートフィルムを製造することができる。
　以下、セルロースアシレートフィルムにおけるＴｇ低下剤の分布を厚さ方向に偏らせる第３の形態として、共流延法によるセルロースアシレートフィルムの製造方法を説明する。具体的には、第３の形態に係る製造方法は、Ｔｇ低下剤の濃度が異なる複数のドープを金属支持体上に共流延する工程、流延して得られたフィルムを乾燥し、剥離した後に延伸する工程を含む。 In addition to the solution casting method and the melt casting method, a cellulose acylate film in which the distribution of the Tg reducing agent is biased in the thickness direction can be produced by a co-casting method.
Hereinafter, as a third embodiment in which the distribution of the Tg reducing agent in the cellulose acylate film is biased in the thickness direction, a method for producing a cellulose acylate film by a co-casting method will be described. Specifically, the manufacturing method according to the third embodiment includes a step of co-casting a plurality of dopes having different Tg lowering agent concentrations on a metal support, drying a film obtained by casting, and peeling the film. And a step of stretching after.
（第３の形態）
　まず、セルロースアシレート、Ｔｇ低下剤、その他の添加剤を含む複数のドープを調製する。共流延するドープが２つの場合、Ｔｇ低下剤の濃度が低いドープＡと、Ｔｇ低下剤の濃度が高いドープＢとを調製し、ドープＡが表面層側、ドープＢが金属支持体層側となるように金属支持体上に共流延すればよい。Ｔｇ低下剤の濃度が異なる３つ以上のドープを共流延する場合、Ｔｇ低下剤の濃度が高くなる順に、表面層側から金属支持体層側に向かって各ドープを積層して共流延を行うという形態が好ましく挙げられる。なお、この第３の形態におけるドープ中のＴｇ低下剤の濃度の具体的な値について特に制限はなく、得られるセルロースアシレートフィルム全体のリターデーション値を考慮して、適宜調節すればよい。 (Third form)
First, a plurality of dopes including a cellulose acylate, a Tg reducing agent, and other additives are prepared. When two co-cast dopes are prepared, a dope A having a low concentration of Tg reducing agent and a dope B having a high concentration of Tg reducing agent are prepared. Dope A is on the surface layer side, and dope B is on the metal support layer side. What is necessary is just to co-cast on a metal support body so that it may become. When co-casting three or more dopes having different Tg lowering agent concentrations, the respective dopes are laminated from the surface layer side to the metal support layer side in the order of increasing Tg reducing agent concentration. The form of performing is preferable. In addition, there is no restriction | limiting in particular about the specific value of the density | concentration of the Tg reducing agent in dope in this 3rd form, What is necessary is just to adjust suitably in consideration of the retardation value of the whole cellulose acylate film obtained.
＜セルロースアシレートフィルムの物性＞
　本発明に用いられるセルロースアシレートフィルムの膜厚は、薄膜であることが好ましく、１０～２００μｍの範囲が用いられ、１０～１００μｍであることが好ましく、より好ましくは１０～６０μｍであり、さらに好ましくは２０～６０μｍである。
　本発明に用いられるセルロースアシレートフィルムの幅は、１．０～４．０ｍである。特に１．４～４．０ｍの幅が好ましく、より好ましくは１．６～３．０ｍである。幅が４．０ｍ以下であると、搬送が容易である。 <Physical properties of cellulose acylate film>
The film thickness of the cellulose acylate film used in the present invention is preferably a thin film, preferably in the range of 10 to 200 μm, preferably 10 to 100 μm, more preferably 10 to 60 μm, and still more preferably. Is 20 to 60 μm.
The width of the cellulose acylate film used in the present invention is 1.0 to 4.0 m. In particular, a width of 1.4 to 4.0 m is preferable, and 1.6 to 3.0 m is more preferable. When the width is 4.0 m or less, the conveyance is easy.
　本発明に用いられるセルロースアシレートフィルムのリターデーション値Ｒｏ、Ｒｔｈは、下記数式（６）、（７）により求められる。
　数式（６）　Ｒｏ＝（ｎｘ－ｎｙ）×ｄ　［ｎｍ］
　数式（７）　Ｒｔｈ＝｛（ｎｘ＋ｎｙ）／２－ｎｚ｝×ｄ　［ｎｍ］
〔式中、ｎｘはセルロースアシレートフィルム面内の遅相軸方向の屈折率を表す。ｎｙはセルロースアシレートフィルム面内の進相軸方向の屈折率を表す。ｎｚはセルロースアシレートフィルムの厚さ方向の屈折率を表す。屈折率は２３℃、５５％ＲＨの環境下、波長５９０ｎｍで測定した値である。ｄはセルロースアシレートフィルムの厚さ（ｎｍ）を表す。〕 The retardation values Ro and Rth of the cellulose acylate film used in the present invention are determined by the following mathematical formulas (6) and (7).
Equation (6) Ro = (n x -n y) × d [nm]
Formula (7) Rth = {(n x + n y ) / 2−n z } × d [nm]
Wherein, n x represents a refractive index in a slow axis direction of the cellulose acylate film plane. n y represents a fast axis direction of the refractive index of the cellulose acylate film plane. nz represents the refractive index in the thickness direction of the cellulose acylate film. The refractive index is a value measured at a wavelength of 590 nm in an environment of 23 ° C. and 55% RH. d represents the thickness (nm) of the cellulose acylate film. ]
　上記リターデーション値Ｒｏ、Ｒｔｈは、得られたセルロースアシレートフィルムから試料３５ｍｍ×３５ｍｍを切り出し、２５℃×５５％ＲＨで２時間調湿し、自動複屈折計（ＫＯＢＲＡ２１ＤＨ、王子計測（株）製）で、５９０ｎｍにおける垂直方向から測定した値と、セルロースアシレートフィルム面を傾けながら同様に測定したリターデーション値の外挿値から算出することができる。 The retardation values Ro and Rth were obtained by cutting a sample 35 mm × 35 mm from the obtained cellulose acylate film, adjusting the humidity at 25 ° C. × 55% RH for 2 hours, and using an automatic birefringence meter (KOBRA21DH, manufactured by Oji Scientific Co., Ltd.). ) And the extrapolated value of the retardation value measured in the same manner while tilting the cellulose acylate film surface.
　本発明に用いられるセルロースアシレートフィルムは、求められる光学補償効果によって必要とされる位相差は異なるものの、高い位相差発現性を活かす観点から、リターデーション値Ｒｏ、Ｒｔｈが、下記範囲を満たすことが好ましい。
　　１０ ≦Ｒｏ ≦ １００
　　７０ ≦ Ｒｔｈ≦ ３００
　ここで、リターデーション値Ｒｏは、好ましくは３０～７０であり、より好ましくは４０～６０であり、さらに好ましくは４５～５５である。
　また、リターデーション値Ｒｔｈは、好ましくは９０～２３０であり、より好ましくは１００～１７０であり、さらに好ましくは１１０～１６０である。 Although the retardation required for the cellulose acylate film used in the present invention differs depending on the required optical compensation effect, the retardation values Ro and Rth satisfy the following ranges from the viewpoint of taking advantage of high retardation development. Is preferred.
10 ≦ Ro ≦ 100
70 ≦ Rth ≦ 300
Here, the retardation value Ro is preferably 30 to 70, more preferably 40 to 60, and further preferably 45 to 55.
The retardation value Rth is preferably 90 to 230, more preferably 100 to 170, and still more preferably 110 to 160.
　セルロースアシレートフィルムの遅相軸又は進相軸が、セルロースアシレートフィルム面内に存在し、製膜方向とのなす角をθ１とすると、θ１は－１°以上＋１°以下であることが好ましく、－０．５°以上＋０．５°以下であることがより好ましい。 The slow axis or the fast axis of the cellulose acylate film is present in the cellulose acylate film plane, and θ1 is preferably −1 ° or more and + 1 ° or less, assuming that the angle formed with the film forming direction is θ1. More preferably, the angle is −0.5 ° or more and + 0.5 ° or less.
　このθ１は配向角として定義でき、θ１の測定は、自動複屈折計ＫＯＢＲＡ－２１ＡＤＨ（王子計測機器）を用いて行うことができる。θ１が各々上記範囲を満たすことは、表示画像において高い輝度を得ること、光漏れを抑制又は防止することに寄与でき、カラー液晶表示装置においては忠実な色再現を得ることに寄与できる。 This θ1 can be defined as an orientation angle, and θ1 can be measured using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments). When each θ1 satisfies the above range, it is possible to contribute to obtaining high luminance in the display image, suppressing or preventing light leakage, and obtaining faithful color reproduction in the color liquid crystal display device.
　セルロースアシレートフィルムの透湿度は、４０℃、９０％ＲＨで３００～１８００ｇ／ｍ２・２４ｈが好ましく、さらに４００～１５００ｇ／ｍ２・２４ｈが好ましく、４００～１３００ｇ／ｍ２・２４ｈが特に好ましい。透湿度はＪＩＳ　Ｚ０２０８に記載の方法に従い測定することができる。 The moisture permeability of the cellulose acylate film is preferably 300 to 1800 g / m 2 · 24 h at 40 ° C. and 90% RH, more preferably 400 to 1500 g / m 2 · 24 h, and particularly preferably 400 to 1300 g / m 2 · 24 h. . The moisture permeability can be measured according to the method described in JIS Z0208.
　セルロースアシレートフィルムの破断伸度の範囲は、１０～８０％であることが好ましく、２０～５０％であることがより好ましい。
　セルロースアシレートフィルムの可視光透過率の範囲は、９０％以上であることが好ましく、９３％以上であることがより好ましい。
　セルロースアシレートフィルムのヘイズは、１．０％未満であることが好ましく、０．０～０．１％であることがより好ましい。 The range of the elongation at break of the cellulose acylate film is preferably 10 to 80%, and more preferably 20 to 50%.
The range of visible light transmittance of the cellulose acylate film is preferably 90% or more, and more preferably 93% or more.
The haze of the cellulose acylate film is preferably less than 1.0%, and more preferably 0.0 to 0.1%.
＜光硬化性接着剤＞
　偏光子とセルロースアシレートフィルムとを貼合するための光硬化性接着剤の好ましい例には、以下の（α）～（δ）の各成分を含有する光硬化性接着剤組成物が含まれる。 <Photocurable adhesive>
Preferred examples of the photocurable adhesive for laminating the polarizer and the cellulose acylate film include a photocurable adhesive composition containing the following components (α) to (δ). .
　（α）カチオン重合性化合物
　（β）光カチオン重合開始剤
　（γ）３８０ｎｍより長い波長の光に極大吸収を示す光増感剤
　（δ）ナフタレン系光増感助剤 (Α) Cationic polymerizable compound (β) Photocationic polymerization initiator (γ) Photosensitizer exhibiting maximum absorption in light having a wavelength longer than 380 nm (δ) Naphthalene photosensitizer
（カチオン重合性化合物（α））
　光硬化性接着剤組成物の主成分であり、重合硬化により接着力を与える成分となるカチオン重合性化合物（α）は、カチオン重合により硬化する化合物であればよいが、特に分子内に少なくとも２個のエポキシ基を有するエポキシ化合物を含むことが好ましい。エポキシ化合物には、分子内に芳香環を有する芳香族エポキシ化合物、分子内に少なくとも２個のエポキシ基を有し、そのうちの少なくとも１個が脂環式環に結合している脂環式エポキシ化合物、分子内に芳香環を有さず、エポキシ基とそれが結合する２個の炭素原子を含む環（通常はオキシラン環）の一方の炭素原子が別の脂肪族炭素原子に結合している脂肪族エポキシ化合物等がある。本発明に用いる光硬化性接着剤組成物は、カチオン重合性化合物（α）として、芳香環を含まないエポキシ樹脂、特に脂環式エポキシ化合物を主成分とするものが好ましい。脂環式エポキシ化合物を主成分とするカチオン重合性化合物を用いれば、貯蔵弾性率の高い硬化物を与え、その硬化物（接着剤層）を介してセルロースアシレートフィルムと偏光子が接着された偏光板において、偏光子が割れにくくなる。 (Cationically polymerizable compound (α))
The cationically polymerizable compound (α), which is a main component of the photocurable adhesive composition and serves as a component that gives adhesive force by polymerization and curing, may be any compound that can be cured by cationic polymerization. It is preferable to include an epoxy compound having one epoxy group. The epoxy compound includes an aromatic epoxy compound having an aromatic ring in the molecule, an alicyclic epoxy compound having at least two epoxy groups in the molecule, and at least one of which is bonded to the alicyclic ring. A fatty acid that does not have an aromatic ring in the molecule and one carbon atom of the ring containing the two carbon atoms to which it is bonded (usually an oxirane ring) is bonded to another aliphatic carbon atom Group epoxy compounds. The photocurable adhesive composition used in the present invention is preferably an epoxy resin containing no aromatic ring, particularly an alicyclic epoxy compound as a main component, as the cationic polymerizable compound (α). If a cationically polymerizable compound containing an alicyclic epoxy compound as a main component is used, a cured product having a high storage elastic modulus is given, and the cellulose acylate film and the polarizer are bonded via the cured product (adhesive layer). In the polarizing plate, the polarizer is difficult to break.
　脂環式エポキシ化合物は上述のように、分子内に少なくとも２個のエポキシ基を有し、そのうちの少なくとも１個が脂環式環に結合しているものである。ここで、脂環式環に結合しているエポキシ基とは、次式（ｅｐ）に示すように、エポキシ基（－Ｏ－）の２本の結合手が脂環式環を構成する２個の炭素原子（通常は隣り合う炭素原子）にそれぞれ直接結合していることを意味する。下記一般式（ｅｐ）において、ｍは２～５の整数を表す。
Figure JPOXMLDOC01-appb-C000018
 As described above, the alicyclic epoxy compound has at least two epoxy groups in the molecule, and at least one of them is bonded to the alicyclic ring. Here, the epoxy group bonded to the alicyclic ring is, as shown in the following formula (ep), two bonds in which two bonds of the epoxy group (—O—) constitute the alicyclic ring. Each of the carbon atoms (usually adjacent carbon atoms). In the following general formula (ep), m represents an integer of 2 to 5.
Figure JPOXMLDOC01-appb-C000018
　一般式（ｅｐ）における（ＣＨ２）ｍ中の水素原子を１個又は複数個取り除いた形の基が、他の化学構造に結合した化合物が、脂環式エポキシ化合物となり得る。脂環式環を構成する水素は、メチル基やエチル基のように、直鎖状アルキル基で適宜置換されていてもよい。なかでも、エポキシシクロペンタン環（上記一般式（ｅｐ）においてｍ＝３のもの）や、エポキシシクロヘキサン環（上記一般式（ｅｐ）においてｍ＝４のもの）を有する化合物が好ましい。 A compound in which one or more hydrogen atoms in (CH 2 ) m in the general formula (ep) are removed and bonded to another chemical structure can be an alicyclic epoxy compound. Hydrogen constituting the alicyclic ring may be appropriately substituted with a linear alkyl group such as a methyl group or an ethyl group. Among these, a compound having an epoxycyclopentane ring (m = 3 in the general formula (ep)) or an epoxycyclohexane ring (m = 4 in the general formula (ep)) is preferable.
　脂環式エポキシ化合物のなかでも、入手が容易で硬化物の貯蔵弾性率を高める効果が大きいことから、下記式（ｅｐ－１）～（ｅｐ－１１）のいずれかで表される化合物がさらに好ましい。
Figure JPOXMLDOC01-appb-C000019
 Among the alicyclic epoxy compounds, the compounds represented by any one of the following formulas (ep-1) to (ep-11) are further obtained because they are easily available and have a large effect of increasing the storage elastic modulus of the cured product. preferable.
Figure JPOXMLDOC01-appb-C000019
　上記式中、Ｒ３～Ｒ２４は、各々独立に水素原子又は炭素原子数１～６のアルキル基を表し、Ｒ３～Ｒ２４がアルキル基の場合、脂環式環に結合する位置は１位～６位の任意の数である。炭素原子数１～６のアルキル基は、直鎖でもよく、分岐を有していてもよく、脂環式環を有していてもよい。Ｙ８は、酸素原子又は炭素原子数１～２０のアルカンジイル基を表す。Ｙ１～Ｙ７は、各々独立に直鎖でもよく、分岐を有していてもよく、脂環式環を有していてもよい炭素原子数１～２０のアルカンジイル基を表す。ｎ、ｐ、ｑ及びｒは、各々独立に０～２０の数を表す。 In the above formula, R 3 to R 24 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and when R 3 to R 24 are alkyl groups, the position bonded to the alicyclic ring is 1 It is an arbitrary number from the first to sixth positions. The alkyl group having 1 to 6 carbon atoms may be a straight chain, may be branched, or may have an alicyclic ring. Y 8 represents an oxygen atom or an alkanediyl group having 1 to 20 carbon atoms. Y 1 to Y 7 each independently represents a straight chain, may be branched, and may represent an alkanediyl group having 1 to 20 carbon atoms which may have an alicyclic ring. n, p, q and r each independently represents a number from 0 to 20.
　上記式（ｅｐ－１）～（ｅｐ－１１）で表される化合物のうち、式（ｅｐ－２）で示される脂環式ジエポキシ化合物が、入手が容易なので好ましい。式（ｅｐ－２）の脂環式ジエポキシ化合物は、３，４－エポキシシクロヘキシルメタノール（そのシクロヘキサン環に炭素数１～６のアルキル基が結合していてもよい）と、３，４－エポキシシクロヘキサンカルボン酸（そのシクロヘキサン環に炭素数１～６のアルキル基が結合していてもよい）とのエステル化合物である。そのようなエステル化合物の具体例として、３，４－エポキシシクロヘキシルメチル３，４－エポキシシクロヘキサンカルボキシレート（式（ｅｐ－２）において、Ｒ５＝Ｒ６＝Ｈ、ｎ＝０である化合物）、３，４－エポキシ－６－メチルシクロヘキシルメチル３，４－エポキシ－６－メチルシクロヘキサンカルボキシレート（式（ｅｐ－２）において、Ｒ５＝６－メチル、Ｒ６＝６－メチル、ｎ＝０である化合物）等が挙げられる。 Of the compounds represented by the above formulas (ep-1) to (ep-11), the alicyclic diepoxy compound represented by the formula (ep-2) is preferable because it is easily available. The alicyclic diepoxy compound of the formula (ep-2) includes 3,4-epoxycyclohexylmethanol (an alkyl group having 1 to 6 carbon atoms may be bonded to the cyclohexane ring) and 3,4-epoxycyclohexane. An ester compound with a carboxylic acid (an alkyl group having 1 to 6 carbon atoms may be bonded to the cyclohexane ring). Specific examples of such an ester compound include 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (a compound in which R 5 = R 6 = H and n = 0 in the formula (ep-2)), 3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexanecarboxylate (in formula (ep-2), R 5 = 6-methyl, R 6 = 6-methyl, n = 0 A certain compound).
　また、脂環式エポキシ化合物に、脂環式エポキシ基を実質的に有さないエポキシ樹脂を併用することが有効である。脂環式エポキシ化合物を主成分とし、これに脂環式エポキシ基を実質的に有さないエポキシ樹脂を併用したものを、カチオン重合性化合物とすれば、硬化物の高い貯蔵弾性率を保持しながら、偏光子とセルロースアシレートフィルムとの密着性を一層高めることができる。ここでいう脂環式エポキシ基を実質的に有さないエポキシ樹脂とは、分子内にエポキシ基とそれが結合する２個の炭素原子を含む環（通常はオキシラン環）の一方の炭素原子が別の脂肪族炭素原子に結合している化合物である。その例として、多価アルコール（フェノール）のポリグリシジルエーテルを挙げることができる。なかでも、入手が容易で偏光子とセルロースアシレートフィルムとの密着性を高める効果が大きいことから、下記一般式（ｇｅ）で示されるジグリシジルエーテル化合物が好ましい。
Figure JPOXMLDOC01-appb-C000020
 〔式中、Ｘは直接結合、メチレン基、炭素原子数１～４のアルキリデン基、脂環式炭化水素基、Ｏ、Ｓ、ＳＯ２、ＳＳ、ＳＯ、ＣＯ、ＯＣＯ又は下記式（ｇｅ－１）～（ｇｅ－３）で表される３種の置換基からなる群から選ばれる置換基を表し、アルキリデン基はハロゲン原子で置換されていてもよい。〕
Figure JPOXMLDOC01-appb-C000021
 In addition, it is effective to use an alicyclic epoxy compound in combination with an epoxy resin having substantially no alicyclic epoxy group. If a cation-polymerizable compound containing an alicyclic epoxy compound as the main component and an epoxy resin substantially free of an alicyclic epoxy group is used as a cationically polymerizable compound, the cured product has a high storage elastic modulus. However, the adhesion between the polarizer and the cellulose acylate film can be further enhanced. As used herein, an epoxy resin having substantially no alicyclic epoxy group means that one carbon atom of a ring (usually an oxirane ring) containing an epoxy group and two carbon atoms to which the epoxy group is bonded in the molecule. A compound bonded to another aliphatic carbon atom. Examples thereof include polyglycidyl ether of polyhydric alcohol (phenol). Among these, a diglycidyl ether compound represented by the following general formula (ge) is preferable because it is easily available and has a large effect of improving the adhesion between the polarizer and the cellulose acylate film.
Figure JPOXMLDOC01-appb-C000020
 [Wherein, X represents a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group, O, S, SO 2 , SS, SO, CO, OCO or the following formula (ge-1 ) To (ge-3) represents a substituent selected from the group consisting of three types of substituents, and the alkylidene group may be substituted with a halogen atom. ]
Figure JPOXMLDOC01-appb-C000021
　式（ｇｅ－１）において、Ｒ２５及びＲ２６は、それぞれ独立して水素原子、炭素原子数１～３のアルキル基、炭素原子数１～１０のアルキル基又はアルコキシ基により置換されてもよいフェニル基あるいは炭素原子数１～１０のアルキル基又はアルコキシ基により置換されてもよい炭素原子数３～１０のシクロアルキル基を表し、Ｒ２５及びＲ２６は互いに連結して環を形成してもよい。
　式（ｇｅ－２）において、Ａ及びＤは、それぞれ独立して、ハロゲン原子で置換されていてもよい炭素原子数１～１０のアルキル基、ハロゲン原子で置換されていてもよい炭素原子数６～２０のアリール基、ハロゲン原子で置換されていてもよい炭素原子数７～２０のアリールアルキル基、ハロゲン原子で置換されていてもよい炭素原子数２～２０の複素環基又はハロゲン原子を表し、当該アルキル基、アリール基、アリールアルキル基中のメチレン基は、不飽和結合、－Ｏ－又は－Ｓ－で中断されていてもよい。ａは０～４の数を表し、ｄは０～４の数を表す。 In the formula (ge-1), R 25 and R 26 may be each independently substituted with a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group. Represents a cycloalkyl group having 3 to 10 carbon atoms which may be substituted by a phenyl group, an alkyl group having 1 to 10 carbon atoms or an alkoxy group, and R 25 and R 26 may be linked to each other to form a ring. Good.
In the formula (ge-2), A and D are each independently an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or 6 carbon atoms which may be substituted with a halogen atom. Represents an aryl group of ˜20, an arylalkyl group of 7 to 20 carbon atoms that may be substituted with a halogen atom, a heterocyclic group of 2 to 20 carbon atoms that may be substituted with a halogen atom, or a halogen atom; The methylene group in the alkyl group, aryl group or arylalkyl group may be interrupted by an unsaturated bond, —O— or —S—. a represents a number from 0 to 4, and d represents a number from 0 to 4.
　一般式（ｇｅ）のジグリシジルエーテル化合物としては、例えばビスフェノールＡのジグリシジルエーテル、ビスフェールＦのジグリシジルエーテル、ビスフェノールＳのジグリシジルエーテルのようなビスフェノール型エポキシ樹脂；テトラヒドロキシフェニルメタンのグリシジルエーテル、テトラヒドロキシベンゾフェノンのグリシジルエーテル、エポキシ化ポリビニルフェノールのような多官能型のエポキシ樹脂；脂肪族多価アルコールのポリグリシジルエーテル；脂肪族多価アルコールのアルキレンオキサイド付加物のポリグリシジルエーテル；アルキレングリコールのジグリシジルエーテル等が挙げられ、なかでも、脂肪族多価アルコールのポリグリシジルエーテルが、入手が容易なので好ましい。 Examples of the diglycidyl ether compound of the general formula (ge) include bisphenol-type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S; glycidyl ether of tetrahydroxyphenylmethane , Glycidyl ether of tetrahydroxybenzophenone, polyfunctional epoxy resin such as epoxidized polyvinylphenol; polyglycidyl ether of aliphatic polyhydric alcohol; polyglycidyl ether of alkylene oxide adduct of aliphatic polyhydric alcohol; Examples thereof include diglycidyl ether, and among them, polyglycidyl ether of aliphatic polyhydric alcohol is preferable because it is easily available.
　上記の脂肪族多価アルコールとしては、例えば炭素数２～２０の範囲内のものを例示できる。より具体的には、例えばエチレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、２－メチル－１，３－プロパンジオール、２－ブチル－２－エチル－１，３－プロパンジオール、１，４－ブタンジオール、ネオペンチルグリコール、３－メチル－２，４－ペンタンジオール、２，４－ペンタンジオール、１，５－ペンタンジオール、３－メチル－１，５－ペンタンジオール、２－メチル－２，４－ペンタンジオール、２，４－ジエチル－１，５－ペンタンジオール、１，６－ヘキサンジオール、１，７－ヘプタンジオール、３，５－ヘプタンジオール、１，８－オクタンジオール、２－メチル－１，８－オクタンジオール、１，９－ノナンジオール、１，１０－デカンジオール等の脂肪族ジオール；シクロヘキサンジメタノール、シクロヘキサンジオール、水添ビスフェノールＡ、水添ビスフェノールＦ等の脂環式ジオール；トリメチロールエタン、トリメチロールプロパン、ヘキシトール類、ペンチトール類、グリセリン、ポリグリセリン、ペンタエリスリトール、ジペンタエリスリトール、テトラメチロールプロパン等の三価以上のポリオールが挙げられる。 Examples of the aliphatic polyhydric alcohol include those having 2 to 20 carbon atoms. More specifically, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl -2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, -Aliphatic diols such as methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol; cyclohexanedi Cycloaliphatic diols such as ethanol, cyclohexanediol, hydrogenated bisphenol A, hydrogenated bisphenol F; trimethylolethane, trimethylolpropane, hexitols, pentitols, glycerin, polyglycerin, pentaerythritol, dipentaerythritol, tetramethylol Examples include trivalent or higher polyols such as propane.
　脂環式エポキシ化合物と脂環式エポキシ基を実質的に有さないエポキシ樹脂を併用する場合、両者の配合割合は、カチオン重合性化合物全体の量を基準に、脂環式エポキシ化合物を５０～９５質量％、そして脂環式エポキシ基を実質的に有さないエポキシ樹脂を５質量％以上とするのが好ましい。脂環式エポキシ化合物をカチオン重合性化合物全体中で５０質量％以上配合することにより、硬化物の８０℃における貯蔵弾性率が１，０００ＭＰａ以上になり、このような硬化物（接着剤層）を介して偏光子とセルロースアシレートフィルムとが接着された偏光板において、偏光子が割れにくくなる。また、脂環式エポキシ基を実質的に有さないエポキシ樹脂を、カチオン重合性化合物全体に対して５質量％以上配合することにより、偏光子とセルロースアシレートフィルムとの密着性が向上する。脂環式エポキシ基を実質的に有さないエポキシ樹脂の量は、カチオン重合性化合物が脂環式エポキシ化合物との二成分系である場合には、カチオン重合性化合物全体の量を基準に５０質量％まで許容されるが、硬化物の貯蔵弾性率の低下を抑え、偏光子の割れを防止する観点から、カチオン重合性化合物全体の量を基準に４５質量％以下とするのが好ましい。 When an alicyclic epoxy compound and an epoxy resin having substantially no alicyclic epoxy group are used in combination, the blending ratio of both is 50 to 50 based on the total amount of the cationic polymerizable compound. It is preferable that 95% by mass and an epoxy resin substantially not having an alicyclic epoxy group be 5% by mass or more. By blending 50% by mass or more of the alicyclic epoxy compound in the whole cationic polymerizable compound, the storage elastic modulus at 80 ° C. of the cured product becomes 1,000 MPa or more, and such a cured product (adhesive layer) is obtained. In the polarizing plate in which the polarizer and the cellulose acylate film are bonded to each other, the polarizer is hardly broken. Moreover, the adhesiveness of a polarizer and a cellulose acylate film improves by mix | blending 5 mass% or more of epoxy resins which do not have an alicyclic epoxy group substantially with respect to the whole cationically polymerizable compound. The amount of the epoxy resin having substantially no alicyclic epoxy group is 50 based on the total amount of the cation polymerizable compound when the cation polymerizable compound is a two-component system with the alicyclic epoxy compound. Although it is permissible up to mass%, it is preferable to make it 45 mass% or less on the basis of the total amount of the cationic polymerizable compound from the viewpoint of suppressing a decrease in storage elastic modulus of the cured product and preventing cracking of the polarizer.
　光硬化性接着剤組成物を構成するカチオン重合性化合物（α）として、以上説明したような脂環式エポキシ化合物及び脂環式エポキシ基を実質的に有さないエポキシ樹脂を併用する場合、それぞれが上述した量となる範囲において、これらに加えて、他のカチオン重合性化合物を含んでいてもよい。他のカチオン重合性化合物としては、式（ｅｐ－１）～（ｅｐ－１１）及び一般式（ｇｅ）以外のエポキシ化合物、オキセタン化合物等が挙げられる。 As the cationically polymerizable compound (α) constituting the photocurable adhesive composition, when using an alicyclic epoxy compound and an epoxy resin substantially free of an alicyclic epoxy group as described above, In the range where becomes the above-mentioned amount, in addition to these, other cationically polymerizable compounds may be included. Examples of other cationically polymerizable compounds include epoxy compounds other than formulas (ep-1) to (ep-11) and general formula (ge), oxetane compounds, and the like.
　式（ｅｐ－１）～（ｅｐ－１１）及び式（ｇｅ）以外のエポキシ化合物には、式（ｅｐ－１）～（ｅｐ－１１）以外の分子内に少なくとも１個の脂環式環に結合するエポキシ基を有する脂環式エポキシ化合物、式（ｇｅ）以外の脂肪族炭素原子に結合するオキシラン環を有する脂肪族エポキシ化合物、分子内に芳香環とエポキシ基を有する芳香族エポキシ化合物、芳香族エポキシ化合物における芳香環が水素化されている水素化エポキシ化合物等がある。 Epoxy compounds other than those represented by formulas (ep-1) to (ep-11) and formula (ge) include at least one alicyclic ring in the molecule other than those represented by formulas (ep-1) to (ep-11). An alicyclic epoxy compound having an epoxy group to be bonded, an aliphatic epoxy compound having an oxirane ring bonded to an aliphatic carbon atom other than the formula (ge), an aromatic epoxy compound having an aromatic ring and an epoxy group in the molecule, aromatic There are hydrogenated epoxy compounds in which aromatic rings in group epoxy compounds are hydrogenated.
　式（ｅｐ－１）～（ｅｐ－１１）以外の分子内に少なくとも１個の脂環式環に結合するエポキシ基を有する脂環式エポキシ化合物の例として、４－ビニルシクロヘキセンジエポキシドや１，２：８，９－ジエポキシリモネンのようなビニルシクロヘキセン類のジエポキシド等がある。 Examples of alicyclic epoxy compounds having an epoxy group bonded to at least one alicyclic ring in a molecule other than those represented by formulas (ep-1) to (ep-11) include 4-vinylcyclohexene diepoxide, 1, 2: diepoxides of vinylcyclohexenes such as 2: 8,9-diepoxy limonene.
　一般式（ｇｅ）以外の脂肪族炭素原子に結合するオキシラン環を有する脂肪族エポキシ化合物の例として、グリセリンのトリグリシジルエーテル、トリメチロールプロパンのトリグリシジルエーテル、ポリエチレングリコールのジグリシジルエーテル等がある。 Examples of the aliphatic epoxy compound having an oxirane ring bonded to an aliphatic carbon atom other than the general formula (ge) include triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, and diglycidyl ether of polyethylene glycol.
　分子内に芳香環とエポキシ基を有する芳香族エポキシ化合物は、分子内に少なくとも２個のフェノール性ヒドロキシ基を有する芳香族ポリヒドロキシ化合物のグリシジルエーテルであることができ、その具体例として、ビスフェノールＡのジグリシジルエーテル、ビスフェノールＦのジグリシジルエーテル、ビスフェノールＳのジグリシジルエーテル、フェノールノボラック樹脂のグリシジルエーテル等がある。 The aromatic epoxy compound having an aromatic ring and an epoxy group in the molecule can be a glycidyl ether of an aromatic polyhydroxy compound having at least two phenolic hydroxy groups in the molecule. Diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S, glycidyl ether of phenol novolac resin, and the like.
　芳香族エポキシ化合物における芳香環が水素化されている水素化エポキシ化合物は、上記の芳香族エポキシ化合物の原料である分子内に少なくとも２個のフェノール性ヒドロキシ基を有する芳香族ポリヒドロキシ化合物を、触媒の存在下、加圧下で選択的に水素化反応を行って、得られた水素化ポリヒドロキシ化合物をグリシジルエーテル化して得ることができる。具体例として、水素化ビスフェノールＡのジグリシジルエーテル、水素化ビスフェノールＦのジグリシジルエーテル、水素化ビスフェノールＳのジグリシジルエーテル等が挙げられる。 A hydrogenated epoxy compound having an aromatic ring hydrogenated in an aromatic epoxy compound catalyzes an aromatic polyhydroxy compound having at least two phenolic hydroxy groups in a molecule as a raw material of the aromatic epoxy compound. The hydrogenated polyhydroxy compound obtained by selectively performing a hydrogenation reaction under pressure in the presence of glycidyl ether can be obtained. Specific examples include diglycidyl ether of hydrogenated bisphenol A, diglycidyl ether of hydrogenated bisphenol F, diglycidyl ether of hydrogenated bisphenol S, and the like.
　これら式（ｅｐ－１）～（ｅｐ－１１）及び一般式（ｇｅ）以外のエポキシ化合物のうち、脂環式環に結合するエポキシ基を有し、先に定義した脂環式エポキシ化合物に分類される化合物を配合する場合は、式（ｅｐ－１）～（ｅｐ－１１）で示される脂環式エポキシ化合物との和が、カチオン重合性化合物の合計量を基準に９５質量％を超えない範囲で用いられる。 Of these epoxy compounds other than formulas (ep-1) to (ep-11) and general formula (ge), they have an epoxy group bonded to an alicyclic ring, and are classified as the alicyclic epoxy compounds defined above. When the compound is added, the sum of the alicyclic epoxy compounds represented by the formulas (ep-1) to (ep-11) does not exceed 95% by mass based on the total amount of the cationic polymerizable compound Used in a range.
　また、任意のカチオン重合性化合物となりうるオキセタン化合物は、分子内に４員環エーテル（オキセタニル基）を有する化合物である。その具体例としては、３－エチル－３－ヒドロキシメチルオキセタン、１，４－ビス〔（３－エチル－３－オキセタニル）メトキシメチル〕ベンゼン、３－エチル－３－（フェノキシメチル）オキセタン、ジ〔（３－エチル－３－オキセタニル）メチル〕エーテル、３－エチル－３－（２－エチルヘキシルオキシメチル）オキセタン、３－エチル－３－（シクロヘキシルオキシメチル）オキセタン、フェノールノボラックオキセタン、１，３－ビス〔（３－エチルオキセタン－３－イル）メトキシ〕ベンゼン、オキセタニルシルセスキオキサン、オキセタニルシリケート等が挙げられる。 An oxetane compound that can be any cationically polymerizable compound is a compound having a 4-membered cyclic ether (oxetanyl group) in the molecule. Specific examples thereof include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di [ (3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (cyclohexyloxymethyl) oxetane, phenol novolak oxetane, 1,3-bis [(3-Ethyloxetane-3-yl) methoxy] benzene, oxetanylsilsesquioxane, oxetanyl silicate and the like.
　カチオン重合性化合物全体の量を基準に、オキセタン化合物を３０質量％以下の割合で配合することにより、エポキシ化合物だけをカチオン重合性化合物として用いた場合に比べ、硬化性が向上するといった効果が期待できることがある。 By blending the oxetane compound at a ratio of 30% by mass or less based on the total amount of the cationic polymerizable compound, an effect of improving curability is expected compared to the case where only the epoxy compound is used as the cationic polymerizable compound. There are things you can do.
（光カチオン重合開始剤（β））
　本発明では、以上のようなカチオン重合性化合物を、活性エネルギー線の照射によってカチオン重合させて硬化させ、接着剤層を形成することから、光硬化性接着剤組成物には、光カチオン重合開始剤（β）を配合することが好ましい。 (Photocationic polymerization initiator (β))
In the present invention, the cationically polymerizable compound as described above is cationically polymerized by irradiation with active energy rays and cured to form an adhesive layer. Therefore, the photocurable adhesive composition has photocationic polymerization initiation. It is preferable to blend the agent (β).
　光カチオン重合開始剤（β）は、可視光線、紫外線、Ｘ線、電子線のような活性エネルギー線の照射によって、カチオン種又はルイス酸を発生させ、カチオン重合性化合物（α）の重合反応を開始するものである。光カチオン重合開始剤（β）は、光で触媒的に作用するため、カチオン重合性化合物（α）に混合しても保存安定性や作業性に優れる。活性エネルギー線の照射によりカチオン種やルイス酸を生じる化合物として、例えば、芳香族ジアゾニウム塩；芳香族ヨードニウム塩や芳香族スルホニウム塩のようなオニウム塩；鉄－アレン錯体等を挙げることができる。 The cationic photopolymerization initiator (β) 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, and performs a polymerization reaction of the cationic polymerizable compound (α). It is what is started. Since the cationic photopolymerization initiator (β) acts catalytically by light, it is excellent in storage stability and workability even when mixed with the cationically polymerizable compound (α). Examples of compounds that generate cation species and Lewis acids upon irradiation with active energy rays include aromatic diazonium salts; onium salts such as aromatic iodonium salts and aromatic sulfonium salts; and iron-allene complexes.
　芳香族ジアゾニウム塩としては、例えばベンゼンジアゾニウムヘキサフルオロアンチモネート、ベンゼンジアゾニウムヘキサフルオロホスフェート、ベンゼンジアゾニウムヘキサフルオロボレート等が挙げられる。 Examples of the aromatic diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate.
　芳香族ヨードニウム塩としては、例えばジフェニルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、ジフェニルヨードニウムヘキサフルオロホスフェート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ジ（４－ノニルフェニル）ヨードニウムヘキサフルオロホスフェート等が挙げられる。 Examples of the aromatic iodonium salt include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and the like.
　芳香族スルホニウム塩としては、例えばトリフェニルスルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、４，４′－ビス〔ジフェニルスルホニオ〕ジフェニルスルフィドビスヘキサフルオロホスフェート、４，４′－ビス〔ジ（β－ヒドロキシエトキシ）フェニルスルホニオ〕ジフェニルスルフィドビスヘキサフルオロアンチモネート、４，４′－ビス〔ジ（β－ヒドロキシエトキシ）フェニルスルホニオ〕ジフェニルスルフィドビスヘキサフルオロホスフェート、７－〔ジ（ｐ－トルイル）スルホニオ〕－２－イソプロピルチオキサントンヘキサフルオロアンチモネート、７－〔ジ（ｐ－トルイル）スルホニオ〕－２－イソプロピルチオキサントンテトラキス（ペンタフルオロフェニル）ボレート、４－フェニルカルボニル－４′－ジフェニルスルホニオ－ジフェニルスルフィドヘキサフルオロホスフェート、４－（ｐ－ｔｅｒｔ－ブチルフェニルカルボニル）－４′－ジフェニルスルホニオ－ジフェニルスルフィドヘキサフルオロアンチモネート、４－（ｐ－ｔｅｒｔ－ブチルフェニルカルボニル）－４′－ジ（ｐ－トルイル）スルホニオ－ジフェニルスルフィドテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 Examples of the aromatic sulfonium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis [diphenylsulfonio] diphenyl sulfide bishexafluoro. 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluoroantimonate, 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexa Fluorophosphate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate, 7- [di (p-toluyl) sulfoni O] -2-Isopropylthioxanthone tetrakis (pentafluorophenyl) borate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide hexafluorophosphate, 4- (p-tert-butylphenylcarbonyl) -4'-diphenylsulfo Nio-diphenyl sulfide hexafluoroantimonate, 4- (p-tert-butylphenylcarbonyl) -4'-di (p-toluyl) sulfonio-diphenyl sulfide tetrakis (pentafluorophenyl) borate and the like.
　鉄－アレン錯体としては、例えばキシレン－シクロペンタジエニル鉄（II）ヘキサフルオロアンチモネート、クメン－シクロペンタジエニル鉄（II）ヘキサフルオロホスフェート、キシレン－シクロペンタジエニル鉄（II）トリス（トリフルオロメチルスルホニル）メタナイド等が挙げられる。 Examples of iron-allene complexes include xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene-cyclopentadienyl iron (II) tris (tri Fluoromethylsulfonyl) methanide and the like.
　これらの光カチオン重合開始剤（β）は、それぞれ単独で使用してもよいし、２種以上を混合して使用してもよい。これらのなかでも特に芳香族スルホニウム塩は、３００ｎｍ付近の波長領域でも紫外線吸収特性を有することから、硬化性に優れ、良好な機械強度や接着強度を有する硬化物を与えることができ、好ましく用いられる。 These photocationic polymerization initiators (β) may be used alone or in admixture of two or more. Among these, aromatic sulfonium salts are particularly preferably used because they have ultraviolet absorption characteristics even in the wavelength region near 300 nm, and thus can provide a cured product having excellent curability and good mechanical strength and adhesive strength. .
　光カチオン重合開始剤（β）の配合量は、カチオン重合性化合物（α）全体１００質量部に対して１～１０質量部とする。カチオン重合性化合物（α）１００質量部あたり光カチオン重合開始剤（β）を１質量部以上配合することにより、カチオン重合性化合物（α）を十分に硬化させることができ、得られる偏光板に高い機械強度と接着強度を与える。一方、その量が多くなると、硬化物中のイオン性物質が増加することで硬化物の吸湿性が高くなり、偏光板の耐久性能を低下させる可能性があるため、光カチオン重合開始剤（β）の量は、カチオン重合性化合物（α）１００質量部あたり１０質量部以下とする。
　光カチオン重合開始剤（β）の配合量は、カチオン重合性化合物（α）１００質量部あたり２質量部以上とするのが好ましく、また６質量部以下とするのが好ましい。 The compounding amount of the photo cationic polymerization initiator (β) is 1 to 10 parts by mass with respect to 100 parts by mass of the whole cationic polymerizable compound (α). By blending 1 part by mass or more of the cationic photopolymerization initiator (β) per 100 parts by mass of the cationic polymerizable compound (α), the cationic polymerizable compound (α) can be sufficiently cured, and the resulting polarizing plate can be obtained. Gives high mechanical strength and adhesive strength. On the other hand, when the amount is increased, the ionic substance in the cured product increases, so that the hygroscopic property of the cured product increases and the durability performance of the polarizing plate may be lowered. ) Is 10 parts by mass or less per 100 parts by mass of the cationically polymerizable compound (α).
The amount of the cationic photopolymerization initiator (β) is preferably 2 parts by mass or more and preferably 6 parts by mass or less per 100 parts by mass of the cationic polymerizable compound (α).
（光増感剤（γ））
　本発明に用いられ得る光硬化性接着剤組成物は、以上のようなエポキシ化合物を含むカチオン重合性化合物（α）及び光カチオン重合開始剤（β）に加えて、３８０ｎｍより長い波長の光に極大吸収を示す光増感剤（γ）を含有する。上記光カチオン重合開始剤（β）は、３００ｎｍ付近又はそれより短い波長に極大吸収を示し、その付近の波長の光に感応して、カチオン種又はルイス酸を発生させ、カチオン重合性化合物（α）のカチオン重合を開始させるが、それよりも長い波長の光にも感応するように、３８０ｎｍより長い波長の光に極大吸収を示す光増感剤（γ）が配合される。
　このような光増感剤（γ）としては、下記一般式（ａｔ）で示されるアントラセン系化合物が有利に用いられる。
Figure JPOXMLDOC01-appb-C000022
 〔式中、Ｒ５及びＲ６は、それぞれ独立に炭素数１～６のアルキル基又は炭素数２～１２のアルコキシアルキル基を表す。Ｒ７は、水素原子又は炭素数１～６のアルキル基を表す。〕 (Photosensitizer (γ))
The photocurable adhesive composition that can be used in the present invention is suitable for light having a wavelength longer than 380 nm in addition to the cationic polymerizable compound (α) and the cationic photopolymerization initiator (β) including the epoxy compound as described above. Contains a photosensitizer (γ) exhibiting maximum absorption. The cationic photopolymerization initiator (β) exhibits maximum absorption at a wavelength near or shorter than 300 nm, generates a cationic species or a Lewis acid in response to light having a wavelength near the wavelength, and generates a cationic polymerizable compound (α ) Is initiated, but a photosensitizer (γ) that exhibits maximum absorption in light having a wavelength longer than 380 nm is blended so as to be sensitive to light having a longer wavelength than that.
As such a photosensitizer (γ), an anthracene compound represented by the following general formula (at) is advantageously used.
Figure JPOXMLDOC01-appb-C000022
 [Wherein, R 5 and R 6 each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 2 to 12 carbon atoms. R 7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]
　一般式（ａｔ）で示されるアントラセン系化合物の具体例としては、９，１０－ジメトキシアントラセン、９，１０－ジエトキシアントラセン、９，１０－ジプロポキシアントラセン、９，１０－ジイソプロポキシアントラセン、９，１０－ジブトキシアントラセン、９，１０－ジペンチルオキシアントラセン、９，１０－ジヘキシルオキシアントラセン、９，１０－ビス（２－メトキシエトキシ）アントラセン、９，１０－ビス（２－エトキシエトキシ）アントラセン、９，１０－ビス（２－ブトキシエトキシ）アントラセン、９，１０－ビス（３－ブトキシプロポキシ）アントラセン、２－メチル又は２－エチル－９，１０－ジメトキシアントラセン、２－メチル又は２－エチル－９，１０－ジエトキシアントラセン、２－メチル又は２－エチル－９，１０－ジプロポキシアントラセン、２－メチル又は２－エチル－９，１０－ジイソプロポキシアントラセン、２－メチル又は２－エチル－９，１０－ジブトキシアントラセン、２－メチル又は２－エチル－９，１０－ジペンチルオキシアントラセン、２－メチル又は２－エチル－９，１０－ジヘキシルオキシアントラセン等が挙げられる。 Specific examples of the anthracene compound represented by the general formula (at) include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9 , 10-dibutoxyanthracene, 9,10-dipentyloxyanthracene, 9,10-dihexyloxyanthracene, 9,10-bis (2-methoxyethoxy) anthracene, 9,10-bis (2-ethoxyethoxy) anthracene, 9 , 10-bis (2-butoxyethoxy) anthracene, 9,10-bis (3-butoxypropoxy) anthracene, 2-methyl or 2-ethyl-9,10-dimethoxyanthracene, 2-methyl or 2-ethyl-9, 10-diethoxyanthracene, 2-methyl or -Ethyl-9,10-dipropoxyanthracene, 2-methyl or 2-ethyl-9,10-diisopropoxyanthracene, 2-methyl or 2-ethyl-9,10-dibutoxyanthracene, 2-methyl or 2- Examples include ethyl-9,10-dipentyloxyanthracene, 2-methyl or 2-ethyl-9,10-dihexyloxyanthracene.
　光硬化性接着剤組成物に上記のような光増感剤（γ）を配合することにより、それを配合しない場合に比べて、光硬化性接着剤組成物の硬化性が向上する。光硬化性接着剤組成物を構成するカチオン重合性化合物（α）の１００質量部に対する光増感剤（γ）の配合量を、０．１質量部以上とすることにより、硬化性が向上する効果が発現する。一方、低温保管時の析出を防ぐため、カチオン重合性化合物（α）１００質量部に対して２質量部以下の配合量とする。偏光板のニュートラルグレーを維持する観点から、偏光子とセルロースアシレートフィルムとの接着性が適度に保たれる範囲で、光増感剤（γ）の配合量を少なくするほうが有利である。例えば、カチオン重合性化合物（α）１００質量部に対し、光増感剤（γ）の量を０．１～０．５質量部、さらには０．１～０．３質量部の範囲とするのが好ましい。 By blending the photosensitizer (γ) as described above into the photocurable adhesive composition, the curability of the photocurable adhesive composition is improved as compared with the case where it is not blended. Curability is improved by setting the blending amount of the photosensitizer (γ) to 100 parts by mass of the cationic polymerizable compound (α) constituting the photocurable adhesive composition to be 0.1 parts by mass or more. The effect is manifested. On the other hand, in order to prevent precipitation during low-temperature storage, the blending amount is 2 parts by mass or less with respect to 100 parts by mass of the cationic polymerizable compound (α). From the viewpoint of maintaining the neutral gray of the polarizing plate, it is advantageous to reduce the blending amount of the photosensitizer (γ) as long as the adhesiveness between the polarizer and the cellulose acylate film is maintained appropriately. For example, with respect to 100 parts by mass of the cationically polymerizable compound (α), the amount of the photosensitizer (γ) is in the range of 0.1 to 0.5 parts by mass, further 0.1 to 0.3 parts by mass. Is preferred.
（光増感助剤（δ））
　本発明に用いられ得る光硬化性接着剤組成物は、上述したエポキシ化合物を含むカチオン重合性化合物（α）、光カチオン重合開始剤（β）及び光増感剤（γ）に加えて、下記一般式（ｎｆ）で示されるナフタレン系光増感助剤（δ）を含有する。
Figure JPOXMLDOC01-appb-C000023
 〔式中、Ｒ１及びＲ２はそれぞれ、炭素数１～６のアルキル基である。〕 (Photosensitizer (δ))
The photocurable adhesive composition that can be used in the present invention includes the following cationic polymerizable compound (α) containing an epoxy compound, a cationic photopolymerization initiator (β), and a photosensitizer (γ). It contains a naphthalene-based photosensitization aid (δ) represented by the general formula (nf).
Figure JPOXMLDOC01-appb-C000023
 [Wherein, R 1 and R 2 are each an alkyl group having 1 to 6 carbon atoms. ]
　ナフタレン系光増感助剤（δ）の具体例としては、１，４－ジメトキシナフタレン、１－エトキシ－４－メトキシナフタレン、１，４－ジエトキシナフタレン、１，４－ジプロポキシナフタレン、１，４－ジブトキシナフタレン等が挙げられる。 Specific examples of the naphthalene photosensitizer (δ) include 1,4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, 1, 4-dibutoxynaphthalene and the like can be mentioned.
　光硬化性接着剤組成物にナフタレン系光増感助剤（δ）を配合することにより、それを配合しない場合に比べて、光硬化性接着剤組成物の硬化性が向上する。光硬化性接着剤組成物を構成するカチオン重合性化合物（α）の１００質量部に対するナフタレン系光増感助剤（δ）の配合量を０．１質量部以上とすることにより、硬化性が向上する効果が発現する。一方、ナフタレン系光増感助剤（δ）の配合量は、低温保管時の析出を防ぐため、カチオン重合性化合物（α）１００質量部に対して１０質量部以下の配合量とする。好ましくは、カチオン重合性化合物（α）１００質量部に対して５質量部以下の配合量である。 By blending the naphthalene-based photosensitization aid (δ) with the photocurable adhesive composition, the curability of the photocurable adhesive composition is improved as compared with the case where it is not blended. By setting the blending amount of the naphthalene photosensitizer (δ) to 100 parts by mass of the cationic polymerizable compound (α) constituting the photocurable adhesive composition to be 0.1 parts by mass or more, curability is improved. The improvement effect is manifested. On the other hand, the amount of the naphthalene-based photosensitization aid (δ) is 10 parts by mass or less with respect to 100 parts by mass of the cationic polymerizable compound (α) in order to prevent precipitation during low-temperature storage. Preferably, the blending amount is 5 parts by mass or less with respect to 100 parts by mass of the cationic polymerizable compound (α).
　さらに、本発明に用いられ得る光硬化性接着剤組成物には、本発明の効果を損なわない限り、任意成分である他の成分として、添加剤成分を含有させることができる。添加剤成分としては、前述の光カチオン重合開始剤及び光増感剤（γ）の他、光増感剤（γ）以外の光増感剤、熱カチオン重合開始剤、ポリオール類、イオントラップ剤、酸化防止剤、光安定剤、連鎖移動剤、粘着付与剤、熱可塑性樹脂、充填剤、流動調整剤、可塑剤、消泡剤、レベリング剤、色素、有機溶剤等を配合することができる。 Furthermore, the photocurable adhesive composition that can be used in the present invention can contain an additive component as an optional component as long as the effects of the present invention are not impaired. As additive components, in addition to the above-mentioned photocationic polymerization initiator and photosensitizer (γ), photosensitizers other than the photosensitizer (γ), thermal cationic polymerization initiators, polyols, ion trapping agents , Antioxidants, light stabilizers, chain transfer agents, tackifiers, thermoplastic resins, fillers, flow regulators, plasticizers, antifoaming agents, leveling agents, dyes, organic solvents, and the like.
　添加剤成分を含有させる場合、添加剤成分の使用量は、前述のカチオン重合性化合物（α）の１００質量部に対して１０００質量部以下であることが好ましい。使用量が１０００質量部以下である場合、本発明に用いられ得る光硬化性接着剤組成物の必須成分であるカチオン重合性化合物（α）、光カチオン重合開始剤（β）、光増感剤（γ）及び光増感助剤（δ）の組合せによる、保存安定性の向上、変色防止、硬化速度の向上、良好な接着性の確保という効果を良好に発揮させることができる。 When the additive component is contained, the amount of the additive component used is preferably 1000 parts by mass or less with respect to 100 parts by mass of the cationic polymerizable compound (α). When the amount used is 1000 parts by mass or less, a cationically polymerizable compound (α), a photocationic polymerization initiator (β), and a photosensitizer, which are essential components of the photocurable adhesive composition that can be used in the present invention. By combining (γ) and the photosensitizing aid (δ), the effects of improving storage stability, preventing discoloration, improving curing speed, and ensuring good adhesion can be exhibited well.
　偏光子とセルロースアシレートフィルムとを貼合するための接着剤の好ましい他の例には、以下の（α１）、（α２）及び（β１）の３成分を必須に含有する光硬化性接着剤組成物が含まれる。
　（α１）分子内に少なくとも２個のエポキシ基を有するエポキシ化合物
　（α２）分子内に少なくとも１個のオキセタニル基を有するオキセタン化合物
　（β１）光カチオン重合開始剤 Other preferable examples of the adhesive for laminating the polarizer and the cellulose acylate film include a photocurable adhesive that essentially contains the following three components (α1), (α2), and (β1). A composition is included.
(Α1) Epoxy compound having at least two epoxy groups in the molecule (α2) Oxetane compound having at least one oxetanyl group in the molecule (β1) Photocationic polymerization initiator
　以下、上記（α１）のエポキシ化合物、上記（α２）のオキセタン化合物、上記（β１）の光カチオン重合開始剤を、それぞれ単に、エポキシ化合物（α１）、オキセタン化合物（α２）、光カチオン重合開始剤（β１）という。 Hereinafter, the epoxy compound (α1), the oxetane compound (α2), and the photocationic polymerization initiator (β1) are simply referred to as the epoxy compound (α1), the oxetane compound (α2), and the photocationic polymerization initiator, respectively. It is called (β1).
　エポキシ化合物（α１）とオキセタン化合物（α２）の質量比（エポキシ化合物（α１）：オキセタン化合物（α２））は、９０：１０～１０：９０程度となるようにすることが好ましい。また、光カチオン重合開始剤（β１）は、組成物中に約０．５～２０．０質量％の割合で配合することが好ましい。 The mass ratio of the epoxy compound (α1) to the oxetane compound (α2) (epoxy compound (α1): oxetane compound (α2)) is preferably about 90:10 to 10:90. The cationic photopolymerization initiator (β1) is preferably blended in the composition at a ratio of about 0.5 to 20.0% by mass.
　この光硬化性接着剤は任意に、（ε）成分として分子内に少なくとも１個のエチレン性不飽和結合を有する不飽和化合物を含有することができる。このような不飽和化合物（ε）を含有する場合は、（ζ）成分として光ラジカル重合開始剤を含有することが好ましい。さらにこの光硬化性接着剤は、（η）成分として重合性を有しない他の成分を含有することもできる。 This photo-curable adhesive can optionally contain an unsaturated compound having at least one ethylenically unsaturated bond in the molecule as the (ε) component. When such an unsaturated compound (ε) is contained, it is preferable to contain a radical photopolymerization initiator as the (ζ) component. Furthermore, this photocurable adhesive agent can also contain the other component which does not have polymerizability as ((eta)) component.
　上記（ε）成分の不飽和化合物、（ζ）成分としての光ラジカル重合開始剤、（η）成分としての重合性を有しない他の成分を、それぞれ単に、不飽和化合物（ε）、光ラジカル重合開始剤（ζ）、重合性を有しない他の成分（η）という。 The unsaturated compound (ε), the photoradical polymerization initiator as the (ζ) component, and the other non-polymerizable component as the (η) component are simply referred to as the unsaturated compound (ε) and the photoradical, respectively. It is referred to as a polymerization initiator (ζ) and other component (η) having no polymerizability.
（エポキシ化合物（α１））
　本発明に用いられ得る光硬化性接着剤組成物において、エポキシ化合物（α１）は、分子内に少なくとも２個のエポキシ基を有するものであれば特に限定されず、一般に知られている各種の硬化性エポキシ化合物を用いることができる。好ましいエポキシ化合物（α１）として、分子内に少なくとも２個のエポキシ基と少なくとも１個の芳香環を有する芳香族系エポキシ化合物や、分子内に少なくとも２個のエポキシ基を有し、そのうちの少なくとも１個は脂環式環を構成する隣り合う２個の炭素原子との間で形成されている脂環式エポキシ化合物等が例として挙げられる。 (Epoxy compound (α1))
In the photo-curable adhesive composition that can be used in the present invention, the epoxy compound (α1) is not particularly limited as long as it has at least two epoxy groups in the molecule, and various kinds of generally known curings. A functional epoxy compound can be used. As a preferable epoxy compound (α1), an aromatic epoxy compound having at least two epoxy groups and at least one aromatic ring in the molecule, or at least two epoxy groups in the molecule, at least one of them. An example is an alicyclic epoxy compound formed between two adjacent carbon atoms constituting an alicyclic ring.
　上記芳香族系エポキシ化合物としては、本発明の効果を妨げない限り、特に限定されないが、ビスフェノールＡのジグリシジルエーテル、ビスフェノールＦのジグリシジルエーテル、臭素化ビスフェノールＡのジグリシジルエーテルのようなビスフェノール型エポキシ樹脂；フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂のようなノボラック型エポキシ樹脂；その他、ビフェニル型エポキシ樹脂、ヒドロキノンジグリシジルエーテル、レゾルシンジグリシジルエーテル、テレフタル酸ジグリシジルエステル、フタル酸ジグリシジルエステル、スチレン－ブタジエン共重合体のエポキシ化物、スチレン－イソプレン共重合体のエポキシ化物、末端カルボン酸ポリブタジエンとビスフェノールＡ型エポキシ樹脂の付加反応物等が例として挙げられる。 The aromatic epoxy compound is not particularly limited as long as the effects of the present invention are not hindered, but bisphenol type such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and brominated bisphenol A diglycidyl ether. Epoxy resins; novolak epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins; biphenyl type epoxy resins, hydroquinone diglycidyl ether, resorcin diglycidyl ether, terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester Epoxidized product of styrene-butadiene copolymer, epoxidized product of styrene-isoprene copolymer, terminal carboxylic acid polybutadiene and bisphenol A type epoxy resin Pressurized reactant, etc. as an example.
　ここでのエポキシ樹脂とは、分子中に平均２個以上のエポキシ基を有し、反応により硬化する化合物又はポリマーをいう。この分野での慣例に従い、硬化性のエポキシ基を分子内に２個以上有するものであれば、モノマーであってもエポキシ樹脂ということがある。 The epoxy resin here means a compound or polymer having an average of two or more epoxy groups in the molecule and cured by reaction. In accordance with the practice in this field, a monomer may be referred to as an epoxy resin as long as it has two or more curable epoxy groups in the molecule.
　上記脂環式エポキシ化合物としては、本発明の効果を妨げない限り特に限定されないが、ジシクロペンタジエンジオキサイド、リモネンジオキサイド、４－ビニルシクロヘキセンジオキサイド、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、ビス（３，４－エポキシシクロヘキシルメチル）アジペートのようなエポキシ化シクロヘキシル基を少なくとも１つ有する化合物等が例として挙げられる。 The alicyclic epoxy compound is not particularly limited as long as the effects of the present invention are not hindered, but dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3,4. Examples include compounds having at least one epoxidized cyclohexyl group such as epoxycyclohexanecarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate.
　上記以外にも、１，６－ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ペンタエリスリトールテトラグリシジルエーテル、ポリテトラメチレングリコールジグリシジルエーテルのような脂肪族系エポキシ化合物；水添ビスフェノールＡのジグリシジルエーテルのような芳香環が水素化されているエポキシ化合物；両末端ヒドロキシ基のポリブタジエンの両末端がグリシジルエーテル化された化合物、ポリブタジエンの内部エポキシ化物、スチレン－ブタジエン共重合体の二重結合が一部エポキシ化された化合物（例えば、ダイセル化学工業（株）製のエポフレンド）、エチレン－ブチレン共重合体とポリイソプレンのブロックコポリマーのイソプレン単位が一部エポキシ化された化合物（例えば、ＫＲＡＴＯＮ社製のＬ－２０７）のようなポリマー系のエポキシ化合物等も、エポキシ化合物（α１）となり得る。 In addition to the above, aliphatic epoxy compounds such as 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, polytetramethylene glycol diglycidyl ether; dihydrogenated bisphenol A Epoxy compounds with aromatic rings hydrogenated, such as glycidyl ether; compounds with both ends of hydroxy-terminated polybutadiene, glycidyl ether-terminated polybutadiene, polybutadiene internal epoxide, and styrene-butadiene copolymer double bond Partially epoxidized compound (for example, Epofriend manufactured by Daicel Chemical Industries, Ltd.), compound in which isoprene unit of block copolymer of ethylene-butylene copolymer and polyisoprene is partially epoxidized (for example, , Polymeric epoxy compounds, such as KRATON manufactured by L-207) or the like may also be epoxy compound ([alpha] 1).
　これらのなかでも、芳香族系エポキシ化合物が、偏光板に用いられたときの耐久性等に優れ、特に偏光子及びセルロースアシレートフィルムに対する接着性に優れることから好ましい。さらに、この芳香族系エポキシ化合物としては、芳香族化合物のグリシジルエーテル又は芳香族化合物のグリシジルエステル等が好ましい例として挙げられる。芳香族化合物のグリシジルエーテルの具体例として、ビスフェノールＡのジグリシジルエーテル、ビスフェノールＦのジグリシジルエーテル、臭素化ビスフェノールＡのジグリシジルエーテルのようなビスフェノール型エポキシ樹脂；フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂のようなノボラック型エポキシ樹脂；ビフェニル型エポキシ樹脂；ヒドロキノンジグリシジルエーテル；レゾルシンジグリシジルエーテル等が好ましく挙げられる。また芳香族化合物のグリシジルエステルの具体例としては、テレフタル酸ジグリシジルエステル、フタル酸ジグリシジルエステル等が好ましく挙げられる。 Among these, the aromatic epoxy compound is preferable because it is excellent in durability and the like when used in a polarizing plate, and particularly excellent in adhesion to a polarizer and a cellulose acylate film. Furthermore, preferred examples of the aromatic epoxy compound include glycidyl ethers of aromatic compounds or glycidyl esters of aromatic compounds. Specific examples of glycidyl ethers of aromatic compounds include bisphenol type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of brominated bisphenol A; phenol novolac type epoxy resin, cresol novolak type Preferred examples include novolak-type epoxy resins such as epoxy resins; biphenyl-type epoxy resins; hydroquinone diglycidyl ether; resorcin diglycidyl ether and the like. Specific examples of glycidyl esters of aromatic compounds include terephthalic acid diglycidyl ester and phthalic acid diglycidyl ester.
　なかでも、芳香族化合物のグリシジルエーテルが、偏光子とセルロースアシレートフィルム間の密着性や、偏光板に用いたときの耐久性においてより優れるため、特に好ましい。芳香族化合物のグリシジルエーテルのなかでも、とりわけ好ましい化合物として、ビスフェノールＡのジグリシジルエーテル、ビスフェノールＦのジグリシジルエーテル、フェノールノボラック型エポキシ樹脂が挙げられる。 Among them, glycidyl ether of an aromatic compound is particularly preferable because it is more excellent in adhesion between a polarizer and a cellulose acylate film and durability when used for a polarizing plate. Among the glycidyl ethers of aromatic compounds, particularly preferable compounds include diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and phenol novolac type epoxy resin.
　エポキシ化合物（α１）は、１種類を単独で用いることもできるし、２種類以上を混合して用いることもできる。例えば、芳香族系エポキシ化合物を２種類以上混合して用いることもできるし、芳香族系エポキシ化合物を主体とし、脂環式エポキシ化合物を混合することもできる。 The epoxy compound (α1) can be used alone or as a mixture of two or more. For example, two or more aromatic epoxy compounds can be mixed and used, or an aromatic epoxy compound as a main component and an alicyclic epoxy compound can also be mixed.
（オキセタン化合物（α２））
　本発明に用いられ得る光硬化性接着剤において、オキセタン化合物（α２）は、分子内に少なくとも１個のオキセタニル基を有するものであれば特に限定されず、やはりオキセタニル基を有する種々の化合物を用いることができる。オキセタン化合物（α２）として、分子内に１個のオキセタニル基を有する化合物（以下、単官能オキセタンという）、分子内に２個以上のオキセタニル基を有する化合物（以下、多官能オキセタンという）が好ましい例として挙げられる。 (Oxetane compound (α2))
In the photocurable adhesive that can be used in the present invention, the oxetane compound (α2) is not particularly limited as long as it has at least one oxetanyl group in the molecule, and various compounds having an oxetanyl group are also used. be able to. Preferred examples of the oxetane compound (α2) include a compound having one oxetanyl group in the molecule (hereinafter referred to as monofunctional oxetane) and a compound having two or more oxetanyl groups in the molecule (hereinafter referred to as polyfunctional oxetane). As mentioned.
　単官能オキセタンとしては、３－エチル－３－（２－エチルヘキシロキシメチル）オキセタンのようなアルコキシアルキル基含有単官能オキセタン、３－エチル－３－フェノキシメチルオキセタンのような芳香族基含有単官能オキセタン、３－エチル－３－ヒドロキシメチルオキセタンのようなヒドロキシ基含有単官能オキセタン等が好ましい例として挙げられる。 As monofunctional oxetane, monofunctional oxetane containing alkoxyalkyl group such as 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, and monofunctional containing aromatic group such as 3-ethyl-3-phenoxymethyloxetane. Preferred examples include hydroxy group-containing monofunctional oxetanes such as oxetane and 3-ethyl-3-hydroxymethyloxetane.
　多官能オキセタンとしては、例えば３－エチル－３－〔（３－エチルオキセタン－３－イル）メトキシメチル〕オキセタン、１，４－ビス〔（３－エチルオキセタン－３－イル）メトキシメチル〕ベンゼン、１，４－ビス〔（３－エチルオキセタン－３－イル）メトキシ〕ベンゼン、１，３－ビス〔（３－エチルオキセタン－３－イル）メトキシ〕ベンゼン、１，２－ビス〔（３－エチルオキセタン－３－イル）メトキシ〕ベンゼン、４，４′－ビス〔（３－エチルオキセタン－３－イル）メトキシ〕ビフェニル、２，２′－ビス〔（３－エチルオキセタン－３－イル）メトキシ〕ビフェニル、３，３′，５，５′－テトラメチル－４，４′－ビス〔（３－エチルオキセタン－３－イル）メトキシ〕ビフェニル、２，７－ビス〔（３－エチルオキセタン－３－イル）メトキシ〕ナフタレン、ビス〔４－｛（３－エチルオキセタン－３－イル）メトキシ｝フェニル〕メタン、ビス〔２－｛（３－エチルオキセタン－３－イル）メトキシ｝フェニル〕メタン、２，２－ビス〔４－｛（３－エチルオキセタン－３－イル）メトキシ｝フェニル〕プロパン、ノボラック型フェノール－ホルムアルデヒド樹脂の３－クロロメチル－３－エチルオキセタンによるエーテル化変性物、３（４），８（９）－ビス〔（３－エチルオキセタン－３－イル）メトキシメチル〕－トリシクロ［５．２．１．０２．６］デカン、２，３－ビス〔（３－エチルオキセタン－３－イル）メトキシメチル〕ノルボルナン、１，１，１－トリス〔（３－エチルオキセタン－３－イル）メトキシメチル〕プロパン、１－ブトキシ－２，２－ビス〔（３－エチルオキセタン－３－イル）メトキシメチル〕ブタン、１，２－ビス〔｛２－（３－エチルオキセタン－３－イル）メトキシ｝エチルチオ〕エタン、ビス〔｛４－（３－エチルオキセタン－３－イル）メチルチオ｝フェニル〕スルフィド、１，６－ビス〔（３－エチルオキセタン－３－イル）メトキシ〕－２，２，３，３，４，４，５，５－オクタフルオロヘキサン、３－〔（３－エチルオキセタン－３－イル）メトキシ〕プロピルトリエトキシシランの加水分解縮合物、テトラキス〔（３－エチルオキセタン－３－イル）メチル〕シリケートの縮合物等が挙げられる。 Examples of the polyfunctional oxetane include 3-ethyl-3-[(3-ethyloxetane-3-yl) methoxymethyl] oxetane, 1,4-bis [(3-ethyloxetane-3-yl) methoxymethyl] benzene, 1,4-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,2-bis [(3-ethyl Oxetane-3-yl) methoxy] benzene, 4,4'-bis [(3-ethyloxetane-3-yl) methoxy] biphenyl, 2,2'-bis [(3-ethyloxetane-3-yl) methoxy] Biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4′-bis [(3-ethyloxetane-3-yl) methoxy] biphenyl, 2,7-bis [(3-ethy Oxetane-3-yl) methoxy] naphthalene, bis [4-{(3-ethyloxetane-3-yl) methoxy} phenyl] methane, bis [2-{(3-ethyloxetane-3-yl) methoxy} phenyl] Etherified modification of methane, 2,2-bis [4-{(3-ethyloxetane-3-yl) methoxy} phenyl] propane, novolak type phenol-formaldehyde resin with 3-chloromethyl-3-ethyloxetane, 3 (4), 8 (9) -Bis [(3-ethyloxetane-3-yl) methoxymethyl] -tricyclo [5.2.1.02.6] decane, 2,3-bis [(3-ethyloxetane -3-yl) methoxymethyl] norbornane, 1,1,1-tris [(3-ethyloxetane-3-yl) methoxymethyl] propane, Butoxy-2,2-bis [(3-ethyloxetane-3-yl) methoxymethyl] butane, 1,2-bis [{2- (3-ethyloxetane-3-yl) methoxy} ethylthio] ethane, bis [ {4- (3-Ethyloxetane-3-yl) methylthio} phenyl] sulfide, 1,6-bis [(3-ethyloxetane-3-yl) methoxy] -2,2,3,3,4,4,4 Hydrolysis condensate of 5,5-octafluorohexane, 3-[(3-ethyloxetane-3-yl) methoxy] propyltriethoxysilane, condensation of tetrakis [(3-ethyloxetane-3-yl) methyl] silicate Thing etc. are mentioned.
　オキセタン化合物（α２）は、塗工性や、偏光板に用いたときのセルロースアシレートフィルムとの密着性の観点から、分子量５００以下の室温で液状のものが好ましい。さらに、偏光板が優れた耐久性を持つ点で、単官能オキセタンであれば分子内に芳香環を有するもの又は多官能オキセタンが、より好ましい。このような好ましいオキセタン化合物の例として、３－エチル－３－フェノキシメチルオキセタン、３－エチル－３－〔（３－エチルオキセタン－３－イル）メトキシメチル〕オキセタン、１，４－ビス〔（３－エチルオキセタン－３－イル）メトキシメチル〕ベンゼン等が挙げられる。
　オキセタン化合物（α２）も、１種類を単独で用いることができる他、２種類以上を混合して用いることもできる。 The oxetane compound (α2) is preferably liquid at room temperature with a molecular weight of 500 or less from the viewpoint of coating properties and adhesion to a cellulose acylate film when used for a polarizing plate. Furthermore, in terms of excellent durability of the polarizing plate, a monofunctional oxetane is more preferably an aromatic ring in the molecule or a polyfunctional oxetane. Examples of such preferred oxetane compounds include 3-ethyl-3-phenoxymethyloxetane, 3-ethyl-3-[(3-ethyloxetane-3-yl) methoxymethyl] oxetane, 1,4-bis [(3 -Ethyloxetane-3-yl) methoxymethyl] benzene and the like.
The oxetane compound (α2) can also be used alone or in combination of two or more.
　エポキシ化合物（α１）とオキセタン化合物（α２）の質量比（エポキシ化合物（α１）：オキセタン化合物（α２））は、９０：１０～１０：９０とする。この質量比に過不足があると、本発明に用いられ得る光硬化性接着剤組成物における重要な特性の１つである、短時間で硬化させるという効果が充分に発揮されない。好ましい質量比は、硬化前には低粘度で塗工性に優れ、硬化後に充分な密着性と可撓性を発現できることから、７０：３０～２０：８０程度であり、より好ましくは６０：４０～２５：７５程度である。 The mass ratio of the epoxy compound (α1) to the oxetane compound (α2) (epoxy compound (α1): oxetane compound (α2)) is 90:10 to 10:90. If this mass ratio is excessive or insufficient, the effect of curing in a short time, which is one of important characteristics in the photocurable adhesive composition that can be used in the present invention, is not sufficiently exhibited. A preferred mass ratio is about 70:30 to 20:80, more preferably 60:40, because it has a low viscosity before curing, excellent coating properties, and can exhibit sufficient adhesion and flexibility after curing. It is about 25:75.
（光カチオン重合開始剤（β１））
　本発明に用いられ得る光硬化性接着剤組成物は、硬化成分として上述のエポキシ化合物（α１）及びオキセタン化合物（α２）を含有し、これらはいずれもカチオン重合により硬化するものであることから、そのカチオン重合を開始させるため、光カチオン重合開始剤（β１）が配合される。光カチオン重合開始剤（β１）は、可視光線、紫外線、Ｘ線、電子線等の活性エネルギー線の照射によって、カチオン種又はルイス酸を発生させ、エポキシ基やオキセタニル基の重合反応を開始させる。 (Photocationic polymerization initiator (β1))
The photocurable adhesive composition that can be used in the present invention contains the above-described epoxy compound (α1) and oxetane compound (α2) as curing components, and these are all cured by cationic polymerization. In order to start the cationic polymerization, a photocationic polymerization initiator (β1) is blended. The cationic photopolymerization initiator (β1) generates cationic species or a Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and initiates a polymerization reaction of an epoxy group or an oxetanyl group.
　光カチオン重合開始剤（β１）を配合することにより、常温での硬化が可能となり、偏光子の耐熱性や膨張又は収縮による歪みを考慮する必要性が小さく、セルロースアシレートフィルムを良好に接着することができる。また、光カチオン重合開始剤（β１）は、活性エネルギー線の照射で触媒的に作用するため、エポキシ化合物（α１）及びオキセタン化合物（α２）に混合しても、保存安定性や作業性に優れる。
　このような活性エネルギー線の照射によりカチオン種やルイス酸を生じさせる光カチオン重合開始剤（β１）として、例えば芳香族ジアゾニウム塩、芳香族ヨードニウム塩や芳香族スルホニウム塩のようなオニウム塩、鉄－アレン錯体等を挙げることができる。 By blending the cationic photopolymerization initiator (β1), curing at room temperature is possible, and there is little need to consider the heat resistance of the polarizer and distortion due to expansion or contraction, and the cellulose acylate film is adhered well. be able to. In addition, since the cationic photopolymerization initiator (β1) acts catalytically upon irradiation with active energy rays, it is excellent in storage stability and workability even when mixed with the epoxy compound (α1) and the oxetane compound (α2). .
Photocationic polymerization initiators (β1) that generate cationic species and Lewis acids upon irradiation with such active energy rays include, for example, onium salts such as aromatic diazonium salts, aromatic iodonium salts and aromatic sulfonium salts, iron- An allene complex etc. can be mentioned.
　芳香族ジアゾニウム塩としては、例えばベンゼンジアゾニウムヘキサフルオロアンチモネート、ベンゼンジアゾニウムヘキサフルオロホスフェート、ベンゼンジアゾニウムヘキサフルオロボレート等が挙げられる。 Examples of the aromatic diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate.
　芳香族ヨードニウム塩としては、例えばジフェニルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、ジフェニルヨードニウムヘキサフルオロホスフェート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ジ（４－ノニルフェニル）ヨードニウムヘキサフルオロホスフェート等が挙げられる。 Examples of the aromatic iodonium salt include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and the like.
　芳香族スルホニウム塩としては、例えばトリフェニルスルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、ジフェニル〔４－（フェニルチオ）フェニル〕スルホニウムヘキサフルオロホスフェート、ジフェニル〔４－（フェニルチオ）フェニル〕スルホニウムヘキサフルオロアンチモネート、４，４′－ビス（ジフェニルスルホニオ）ジフェニルスルフィドビスヘキサフルオロホスフェート、４，４′－ビス〔ジ（β－ヒドロキシエトキシ）フェニルスルホニオ〕ジフェニルスルフィドビスヘキサフルオロアンチモネート、４，４′－ビス〔ジ（β－ヒドロキシエトキシ）フェニルスルホニオ〕ジフェニルスルフィドビスヘキサフルオロホスフェート、７－〔ジ（ｐ－トルイル）スルホニオ〕－２－イソプロピルチオキサントンヘキサフルオロアンチモネート、７－〔ジ（ｐ－トルイル）スルホニオ〕－２－イソプロピルチオキサントンテトラキス（ペンタフルオロフェニル）ボレート、４－フェニルカルボニル－４′－ジフェニルスルホニオ－ジフェニルスルフィドヘキサフルオロホスフェート、４－（ｐ－ｔｅｒｔ－ブチルフェニルカルボニル）－４′－ジフェニルスルホニオ－ジフェニルスルフィドヘキサフルオロアンチモネート、４－（ｐ－ｔｅｒｔ－ブチルフェニルカルボニル）－４′－ジ（ｐ－トルイル）スルホニオ－ジフェニルスルフィドテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 Examples of the aromatic sulfonium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate, diphenyl [ 4- (phenylthio) phenyl] sulfonium hexafluoroantimonate, 4,4'-bis (diphenylsulfonio) diphenyl sulfide bishexafluorophosphate, 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl Sulfide bishexafluoroantimonate, 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenylsulfur 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) Borate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide hexafluorophosphate, 4- (p-tert-butylphenylcarbonyl) -4'-diphenylsulfonio-diphenylsulfide hexafluoroantimonate, 4- (p -Tert-butylphenylcarbonyl) -4'-di (p-toluyl) sulfonio-diphenyl sulfide tetrakis (pentafluorophenyl) borate and the like.
　鉄－アレン錯体としては、例えばキシレン－シクロペンタジエニル鉄（II）ヘキサフルオロアンチモネート、クメン－シクロペンタジエニル鉄（II）ヘキサフルオロホスフェート、キシレン－シクロペンタジエニル鉄（II）－トリス（トリフルオロメチルスルホニル）メタナイド等が挙げられる。 Examples of iron-allene complexes include xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene-cyclopentadienyl iron (II) -tris ( (Trifluoromethylsulfonyl) methanide and the like.
　これらの光カチオン重合開始剤（β１）は、それぞれ１種類を単独で用いてもよいし、２種類以上を混合して用いてもよい。これらのなかでも特に芳香族スルホニウム塩は、３００ｎｍ以上の波長領域でも紫外線吸収特性を有することから、硬化性に優れ、良好な機械強度や接着強度を有する硬化物を与えることができるため、好ましく用いられる。 These photocationic polymerization initiators (β1) may be used alone or in combination of two or more. 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 therefore can provide a cured product having excellent curability and good mechanical strength and adhesive strength. It is done.
　光カチオン重合開始剤（β１）は、市販品を容易に入手することが可能であり、例えば、それぞれ商品名で、カヤラッドＰＣＩ－２２０、カヤラッドＰＣＩ－６２０（以上、日本化薬（株）製）、ＵＶＩ－６９９２（ダウ・ケミカル社製）、アデカオプトマーＳＰ－１５０、アデカオプトマーＳＰ－１７０（以上、（株）ＡＤＥＫＡ製）、ＣＩ－５１０２、ＣＩＴ－１３７０、ＣＩＴ－１６８２、ＣＩＰ－１８６６Ｓ、ＣＩＰ－２０４８Ｓ、ＣＩＰ－２０６４Ｓ（以上、日本曹達（株）製）、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（以上、みどり化学（株）製）、ＰＩ－２０７４（ローディア社製）、イルガキュア２５０、イルガキュアＰＡＧ１０３、イルガキュアＰＡＧ１０８、イルガキュアＰＡＧ１２１、イルガキュアＰＡＧ２０３（以上、チバ社製）、ＣＰＩ－１００Ｐ、ＣＰＩ－１０１Ａ、ＣＰＩ－２００Ｋ、ＣＰＩ－２１０Ｓ（以上、サンアプロ（株）製）等が挙げられる。なかでも、ジフェニル〔４－（フェニルチオ）フェニル〕スルホニウムをカチオン成分として含む、ＵＶＩ－６９９２、ＣＰＩ－１００Ｐ、ＣＰＩ－１０１Ａ、ＣＰＩ－２００Ｋ、ＣＰＩ－２１０Ｓが好ましい。 As the cationic photopolymerization initiator (β1), commercially available products can be easily obtained. For example, Kayrad PCI-220 and Kayalad PCI-620 (above, manufactured by Nippon Kayaku Co., Ltd.) under the trade names, respectively. UVI-6992 (manufactured by Dow Chemical Co.), Adeka optomer SP-150, Adeka optomer SP-170 (above, manufactured by ADEKA), CI-5102, CIT-1370, CIT-1682S, 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), Irgacure 250, Irgacure PAG103, Irgacure PAG108, Irgacure PAG121, Irgacure PAG203 ( As mentioned above, CPI-100P, CPI-101A, CPI-200K, CPI-210S (above, San Apro Co., Ltd.) and the like can be mentioned. Among these, UVI-6992, CPI-100P, CPI-101A, CPI-200K, and CPI-210S containing diphenyl [4- (phenylthio) phenyl] sulfonium as a cation component are preferable.
　光カチオン重合開始剤（β１）の配合割合は、光硬化性接着剤全体を基準として、０．５～２０．０質量％の範囲とする。配合割合が０．５質量％以上であると、光硬化性接着剤が十分に硬化し、機械強度や接着強度を維持できる。一方、配合割合が２０質量％以下であると、硬化物中のイオン性物質の増加による硬化物の吸湿性の上昇を抑えて、耐久性の低下を防ぐことができる。 The blending ratio of the photocationic polymerization initiator (β1) is in the range of 0.5 to 20.0% by mass based on the entire photocurable adhesive. When the blending ratio is 0.5% by mass or more, the photocurable adhesive is sufficiently cured, and the mechanical strength and the adhesive strength can be maintained. On the other hand, when the blending ratio is 20% by mass or less, an increase in hygroscopicity of the cured product due to an increase in ionic substances in the cured product can be suppressed, and a decrease in durability can be prevented.
（不飽和化合物（ε））
　光硬化性接着剤は、必要に応じて、分子内に少なくとも１個のエチレン性不飽和結合を有する不飽和化合物（ε）を含有することができる。
　このような不飽和化合物（ε）の典型的な例として、分子内に少なくとも１個の（メタ）アクリロイル基を有する（メタ）アクリル系化合物を挙げることができる。 (Unsaturated compound (ε))
The photocurable adhesive may contain an unsaturated compound (ε) having at least one ethylenically unsaturated bond in the molecule, if necessary.
A typical example of such an unsaturated compound (ε) is a (meth) acrylic compound having at least one (meth) acryloyl group in the molecule.
　（メタ）アクリル系化合物としては、特に限定されないが、例えば（メタ）アクリレート類、（メタ）アクリルアミド類、（メタ）アクリル酸、（メタ）アクリロイルモルホリン、（メタ）アクリルアルデヒド等が挙げられる。 The (meth) acrylic compound is not particularly limited, and examples thereof include (meth) acrylates, (meth) acrylamides, (meth) acrylic acid, (meth) acryloylmorpholine, and (meth) acrylaldehyde.
　分子内に１個の（メタ）アクリロイル基を有する（メタ）アクリレート類（以下、単官能（メタ）アクリレートという）としては、特に限定されないが、例えばメチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレートのようなアルキル（メタ）アクリレート類；２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレートのようなヒドロキシアルキル（メタ）アクリレート類；シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、１，４－シクロヘキサンジメチロールモノ（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレートのような脂環式単官能（メタ）アクリレート類；ベンジル（メタ）アクリレート、ｐ－クミルフェノールアルキレンオキサイド付加物の（メタ）アクリレート、ｏ－フェニルフェノールアルキレンオキサイド付加物の（メタ）アクリレート、フェノールアルキレンオキサイド付加物の（メタ）アクリレート、ノニルフェノールアルキレンオキサイド付加物の（メタ）アクリレートのような芳香族環を有する単官能（メタ）アクリレート類（ここで、アルキレンオキサイドとしては、エチレンオキサイドやプロピレンオキサイド等が挙げられる）；２－メトキシエチル（メタ）アクリレート、エトキシメチル（メタ）アクリレート、２－エチルヘキシルアルコールのアルキレンオキサイド付加物の（メタ）アクリレートのようなアルコキシアルキル（メタ）アクリレート類；エチレングリコールモノ（メタ）アクリレート、プロピレングリコールモノ（メタ）アクリレート、ペンタンジオールモノ（メタ）アクリレート、ヘキサンジオールモノ（メタ）アクリレートのような二価アルコールのモノ（メタ）アクリレート類；ジエチレングリコールのモノ（メタ）アクリレート、トリエチレングリコールのモノ（メタ）アクリレート、テトラエチレングリコールのモノ（メタ）アクリレート、ポリエチレングリコールのモノ（メタ）アクリレート、ジプロピレングリコールのモノ（メタ）アクリレート、トリプロピレングリコールのモノ（メタ）アクリレート、ポリプロピレングリコールのモノ（メタ）アクリレートのようなポリアルキレングリコールのモノ（メタ）アクリレート類；グリシジル（メタ）アクリレート；テトラヒドロフルフリル（メタ）アクリレート；カプロラクトン変性テトラヒドロフルフリル（メタ）アクリレートのようなテトラヒドロフルフリル（メタ）アクリレート類；３，４－エポキシシクロヘキシルメチル（メタ）アクリレート；Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート；２－（メタ）アクリロイルオキシエチルイソシアネート等が挙げられる。 The (meth) acrylates having one (meth) acryloyl group in the molecule (hereinafter referred to as monofunctional (meth) acrylate) are not particularly limited, but for example, methyl (meth) acrylate, ethyl (meth) acrylate, Propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, Alkyl (meth) acrylates such as stearyl (meth) acrylate; hydrides such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Roxyalkyl (meth) acrylates; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 1,4-cyclohexanedimethylol mono (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Alicyclic monofunctional (meth) acrylates such as dicyclopentenyloxyethyl (meth) acrylate; benzyl (meth) acrylate, (meth) acrylate of p-cumylphenol alkylene oxide adduct, o-phenylphenol alkylene oxide (Meth) acrylates of adducts, (meth) acrylates of phenol alkylene oxide adducts, (meth) acrylates of nonylphenol alkylene oxide adducts, (Meth) acrylates (wherein alkylene oxides include ethylene oxide and propylene oxide); addition of alkylene oxide of 2-methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, 2-ethylhexyl alcohol Alkoxyalkyl (meth) acrylates such as (meth) acrylates; such as ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate Mono (meth) acrylates of dihydric alcohols; mono (meth) acrylate of diethylene glycol, mono (meth) acrylate of triethylene glycol, tetraethylene glycol Polyalkylenes such as Cole mono (meth) acrylate, Polyethylene glycol mono (meth) acrylate, Dipropylene glycol mono (meth) acrylate, Tripropylene glycol mono (meth) acrylate, Polypropylene glycol mono (meth) acrylate Mono (meth) acrylates of glycols; glycidyl (meth) acrylates; tetrahydrofurfuryl (meth) acrylates; tetrahydrofurfuryl (meth) acrylates such as caprolactone-modified tetrahydrofurfuryl (meth) acrylates; 3,4-epoxycyclohexyl Examples include methyl (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylate; 2- (meth) acryloyloxyethyl isocyanate.
　また、分子内に２個以上の（メタ）アクリロイル基を有する（メタ）アクリレート類としては、特に限定されないが、例えば、次のような化合物が挙げられる。 Further, (meth) acrylates having two or more (meth) acryloyl groups in the molecule are not particularly limited, and examples thereof include the following compounds.
　トリシクロデカンジメチロールジ（メタ）アクリレート、１，４－シクロヘキサンジメチロールジ（メタ）アクリレート、ノルボルナンジメチロールジ（メタ）アクリレート、水素添加ビスフェノールＡのジ（メタ）アクリレートのような脂環式環を有するジ（メタ）アクリレート類；ビスフェノールＡエチレンオキサイド付加物のジ（メタ）アクリレート、ビスフェノールＡプロピレンオキサイド付加物のジ（メタ）アクリレートを含むビスフェノールＡアルキレンオキサイド付加物のジ（メタ）アクリレート、ビスフェノールＡジグリシジルエーテルのジ（メタ）アクリレートのような芳香族環を有するジ（メタ）アクリレート類；エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ペンタンジオールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレートのようなアルキレングリコールのジ（メタ）アクリレート類；ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレートのようなポリアルキレングリコールのジ（メタ）アクリレート類；グリセリンのジ又はトリ（メタ）アクリレート、ジグリセリンのジ又はトリ（メタ）アクリレートのようなグリセリン類のジ又はトリ（メタ）アクリレート類；グリセリン類のアルキレンオキサイド付加物のジ又はトリ（メタ）アクリレート類；ビスフェノールＡアルキレンオキサイド付加物のジ（メタ）アクリレート、ビスフェノールＦアルキレンオキサイド付加物のジ（メタ）アクリレートのようなビスフェノールアルキレンオキサイド付加物のジ（メタ）アクリレート類；トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートのようなポリオールポリ（メタ）アクリレート類；これらポリオールのアルキレンオキサイド付加物のポリ（メタ）アクリレート類；イソシアヌル酸アルキレンオキサイド付加物のジ又はトリ（メタ）アクリレート類；１，３，５－トリ（メタ）アクリロイルヘキサヒドロ－ｓ－トリアジン等が挙げられる。 Alicyclic rings such as tricyclodecane dimethylol di (meth) acrylate, 1,4-cyclohexane dimethylol di (meth) acrylate, norbornane dimethylol di (meth) acrylate, di (meth) acrylate of hydrogenated bisphenol A Di (meth) acrylates having bisphenol A ethylene oxide adduct di (meth) acrylate, bisphenol A propylene oxide adduct di (meth) acrylate containing di (meth) acrylate, bisphenol A Di (meth) acrylates having an aromatic ring such as di (meth) acrylate of A diglycidyl ether; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, penta Di (meth) acrylates of alkylene glycols such as diol di (meth) acrylate and hexanediol di (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate; Di- or tri (meth) acrylates, di- or tri (meth) acrylates of glycerols such as di- or tri (meth) acrylates of diglycerol; glycerol Di- or tri (meth) acrylates of bisphenol alkylene oxide adducts; di (meth) acrylates of bisphenol A alkylene oxide adducts, di (meth) acrylates of bisphenol F alkylene oxide adducts (Meth) acrylates; trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Polyol poly (meth) acrylates such as pentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; And poly (meth) acrylates of polyol alkylene oxide adducts; di- or tri (meth) acrylates of isocyanuric acid alkylene oxide adducts; 1,3,5-tri (meth) acryloylhexahydro-s-triazine and the like Can be mentioned.
　（メタ）アクリルアミド類としては、Ｎ－メチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ－イソプロピルアクリルアミド、Ｎ－ブチル（メタ）アクリルアミド、Ｎ－ヘキシル（メタ）アクリルアミド、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－ヒドロキシエチル（メタ）アクリルアミド、Ｎ－メチロール－Ｎ－プロパン（メタ）アクリルアミド、アミノメチル（メタ）アクリルアミド、アミノエチル（メタ）アクリルアミド、メルカアプトメチル（メタ）アクリルアミド、メルカアプトエチル（メタ）アクリルアミド等が挙げられる。 (Meth) acrylamides include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropylacrylamide, N-butyl (meth) acrylamide, N -Hexyl (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylol-N-propane (meth) acrylamide, aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide, Examples include mercaaptmethyl (meth) acrylamide and mercaaptethyl (meth) acrylamide.
　また、ウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレート、エポキシ（メタ）アクリレートのようなオリゴマーも、（メタ）アクリル系化合物として使用できる。 Also, oligomers such as urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate can be used as the (meth) acrylic compound.
　さらに、（メタ）アクリロイル基とともに、それ以外のエチレン性不飽和結合を有する化合物も、（メタ）アクリル系化合物として使用できる。その具体例として、アリル（メタ）アクリレート、Ｎ，Ｎ－ジアリル（メタ）アクリルアミド等が挙げられる。 Furthermore, a compound having an ethylenically unsaturated bond other than the (meth) acryloyl group can also be used as the (meth) acrylic compound. Specific examples thereof include allyl (meth) acrylate and N, N-diallyl (meth) acrylamide.
　不飽和化合物（ε）としては、特に限定されず、以上の（メタ）アクリル系化合物以外にも、Ｎ－ビニル－２－ピロリドン、アジピン酸ジビニル、セバシン酸ジビニルのようなビニル化合物；トリアリルイソシアヌレート、トリアリルアミン、テトラアリルピロメリテート、Ｎ，Ｎ，Ｎ′，Ｎ′－テトラアリル－１，４－ジアミノブタン、テトラアリルアンモニウム塩、アリルアミンのようなアリル化合物；マレイン酸及びイタコン酸のような不飽和カルボン酸等も使用することもできる。 The unsaturated compound (ε) is not particularly limited, and in addition to the above (meth) acrylic compounds, vinyl compounds such as N-vinyl-2-pyrrolidone, divinyl adipate and divinyl sebacate; triallyl isocyan Allyl compounds such as nurate, triallylamine, tetraallyl pyromellitate, N, N, N ′, N′-tetraallyl-1,4-diaminobutane, tetraallylammonium salt, allylamine; such as maleic acid and itaconic acid Unsaturated carboxylic acids and the like can also be used.
　これら不飽和化合物（ε）のなかでも、（メタ）アクリル系化合物が好ましい。さらに、それを含む接着剤を介して偏光子とセルロースアシレートフィルムとを接着し、偏光板を作製したとき、耐熱性等の耐久性を高める観点から、分子内に少なくとも１個の脂環式骨格又は芳香環骨格を有する（メタ）アクリル系化合物が、より好ましい。かかる分子内に少なくとも１個の脂環式骨格又は芳香環骨格を有する（メタ）アクリル系化合物の具体例としては、上述した脂環式単官能（メタ）アクリレート類、芳香族環を有する単官能（メタ）アクリレート類、脂環式環を有するジ（メタ）アクリレート類又は芳香族環を有するジ（メタ）アクリレート類が、好ましく挙げられる。これらのなかでもとりわけ、トリシクロデカン骨格を有するジ（メタ）アクリレートが好ましく、このような特に好ましい（メタ）アクリル系化合物の具体例としては、トリシクロデカンジメチロールジ（メタ）アクリレート等を挙げることができる。 Among these unsaturated compounds (ε), (meth) acrylic compounds are preferable. Furthermore, when a polarizer and a cellulose acylate film are bonded via an adhesive containing the same to produce a polarizing plate, at least one alicyclic group is included in the molecule from the viewpoint of enhancing durability such as heat resistance. A (meth) acrylic compound having a skeleton or an aromatic ring skeleton is more preferable. Specific examples of the (meth) acrylic compound having at least one alicyclic skeleton or aromatic ring skeleton in the molecule include the above-described alicyclic monofunctional (meth) acrylates and monofunctional having an aromatic ring. Preferable examples include (meth) acrylates, di (meth) acrylates having an alicyclic ring, or di (meth) acrylates having an aromatic ring. Among these, di (meth) acrylate having a tricyclodecane skeleton is preferable, and specific examples of such (meth) acrylic compounds are tricyclodecane dimethylol di (meth) acrylate and the like. be able to.
　不飽和化合物（ε）は、硬化速度や、偏光子とセルロースアシレートフィルム間の密着性、接着層の弾性率、接着物の耐久性等を調節するために、使用することができる。不飽和化合物（ε）は、１種類を単独で又は２種類以上を混合して用いることができる。 The unsaturated compound (ε) can be used to adjust the curing speed, the adhesion between the polarizer and the cellulose acylate film, the elastic modulus of the adhesive layer, the durability of the adhesive, and the like. An unsaturated compound ((epsilon)) can be used individually by 1 type or in mixture of 2 or more types.
　不飽和化合物（ε）を配合する場合、その配合割合は、組成物全体を基準として３５質量％以下とするのが好ましい。これにより、偏光子とセルロースアシレートフィルム間の密着性が優れたものとなる。不飽和化合物（ε）の量が３５質量％以下であると、偏光子との十分な接着強度が得られやすい。そこで、不飽和化合物（ε）の配合割合は、３０質量％以下とすることがより好ましく、５～２５質量％程度、とりわけ１０～２０質量％程度とするのがさらに好ましい。 When the unsaturated compound (ε) is blended, the blending ratio is preferably 35% by mass or less based on the entire composition. Thereby, the adhesiveness between a polarizer and a cellulose acylate film becomes excellent. When the amount of the unsaturated compound (ε) is 35% by mass or less, sufficient adhesive strength with the polarizer is easily obtained. Therefore, the blending ratio of the unsaturated compound (ε) is more preferably 30% by mass or less, and further preferably about 5 to 25% by mass, especially about 10 to 20% by mass.
（光ラジカル重合開始剤（ζ））
　光硬化性接着剤が不飽和化合物（ε）を含む場合、そのラジカル重合性を促進し、硬化速度を十分なものとするために、光ラジカル重合開始剤（ζ）を配合することが好ましい。 (Photoradical polymerization initiator (ζ))
When the photocurable adhesive contains an unsaturated compound (ε), it is preferable to add a photoradical polymerization initiator (ζ) in order to promote the radical polymerizability and make the curing rate sufficient.
　光ラジカル重合開始剤（ζ）の具体例としては、特に限定されないが、例えば４′－フェノキシ－２，２－ジクロロアセトフェノン、４′－ｔｅｒｔ－ブチル－２，２－ジクロロアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、α，α－ジエトキシアセトフェノン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－（４－イソプロピルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、１－（４－ドデシルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、１－〔４－（２－ヒドロキシエトキシ）フェニル〕－２－ヒドロキシ－２－メチルプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタン－１－オンのようなアセトフェノン系光重合開始剤；ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテルのようなベンゾインエーテル系光重合開始剤；ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、４－フェニルベンゾフェノン、４－ベンゾイル－４′－メチルジフェニルサルファイド、２，４，６－トリメチルベンゾフェノンのようなベンゾフェノン系光重合開始剤；２－イソプロピルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジクロロチオキサントン、１－クロロ－４－プロポキシチオキサントンのようなチオキサントン系光重合開始剤；２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）フェニルホスフィンオキサイドのようなアシルホスフィンオキサイド系光重合開始剤；１，２－オクタンジオン，１－〔４－（フェニルチオフェニル）〕－，２－（Ｏ－ベンゾイルオキシム）のようなオキシム・エステル系光重合開始剤；カンファーキノン等が挙げられる。 Specific examples of the radical photopolymerization initiator (ζ) are not particularly limited, but for example, 4′-phenoxy-2,2-dichloroacetophenone, 4′-tert-butyl-2,2-dichloroacetophenone, 2,2- Dimethoxy-2-phenylacetophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1-hydroxycyclohexyl phenyl ketone, α, α-diethoxyacetophenone, 2-hydroxy-2 -Methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methyl Propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2- Acetophenone photopolymerization initiators such as tilpropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Benzoin ether photopolymerization initiators such as isopropyl ether and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4,6-trimethylbenzophenone Benzophenone-based photopolymerization initiators such as: 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, thioxanes such as 1-chloro-4-propoxythioxanthone 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) ) Acylphosphine oxide photopolymerization initiators such as phenylphosphine oxide; Oxime esters such as 1,2-octanedione, 1- [4- (phenylthiophenyl)]-, 2- (O-benzoyloxime) System photopolymerization initiators; camphorquinone and the like.
　光ラジカル重合開始剤（ζ）は、１種類を単独で又は２種類以上を所望の性能に応じて配合し、用いることができる。光ラジカル重合開始剤（ζ）を配合する場合、十分な硬化と強度を得る観点から、その配合割合は、組成物全体を基準として、１０質量％以下が好ましく、０．１～３．０質量％程度がより好ましい。 The photo radical polymerization initiator (ζ) can be used alone or in combination of two or more according to the desired performance. When the radical photopolymerization initiator (ζ) is blended, the blending ratio is preferably 10% by weight or less, based on the entire composition, from the viewpoint of obtaining sufficient curing and strength, and 0.1 to 3.0% by weight. % Is more preferable.
（他の成分（η））
　さらに、本発明に用いられ得る光硬化性接着剤組成物には、本発明の効果を損なわない範囲で、前記（α１）～（ζ）成分とは異なる他の成分を、任意に配合することができる。
　このような他の成分に属する一つのタイプとして、エポキシ化合物（α１）やオキセタン化合物（α２）以外のカチオン重合性を有する化合物を挙げることができる。具体例としては、特に限定されないが、分子内に１個のエポキシ基を有するエポキシ化合物等が挙げられる。また、他の成分に属する別のタイプとして、重合性を有しない他の成分（η）を挙げることができる。重合性を有しない他の成分（η）を配合する場合、その配合割合は、組成物全体を基準に１０質量％以下程度とするのが好ましい。 (Other components (η))
Furthermore, in the photocurable adhesive composition that can be used in the present invention, other components different from the components (α1) to (ζ) are optionally blended within a range not impairing the effects of the present invention. Can do.
As one type belonging to such other components, there may be mentioned compounds having cationic polymerizability other than the epoxy compound (α1) and the oxetane compound (α2). Specific examples include, but are not limited to, an epoxy compound having one epoxy group in the molecule, and the like. Further, as another type belonging to the other component, other component (η) having no polymerizability can be exemplified. When the other component (η) having no polymerizability is blended, the blending ratio is preferably about 10% by mass or less based on the entire composition.
　重合性を有しない他の成分（η）の例として、特に限定されないが、光増感剤を挙げられる。光増感剤を配合することにより、反応性が向上し、硬化物の機械強度や接着強度を向上させることができる。光増感剤としては、例えばカルボニル化合物、有機硫黄化合物、過硫化物、レドックス系化合物、アゾ及びジアゾ化合物、ハロゲン化合物、光還元性色素等が挙げられる。 Although it does not specifically limit as an example of the other component ((eta)) which does not have polymerizability, A photosensitizer is mentioned. By blending 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.
　具体的な光増感剤としては、特に限定されず、例えばベンゾインメチルエーテル、ベンゾインイソプロピルエーテル、α，α－ジメトキシ－α－フェニルアセトフェノンのようなベンゾイン誘導体；ベンゾフェノン、２，４－ジクロロベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、４，４′－ビス（ジメチルアミノ）ベンゾフェノン、４，４′－ビス（ジエチルアミノ）ベンゾフェノンのようなベンゾフェノン誘導体；２－クロロチオキサントン、２－イソプロピルチオキサントンのようなチオキサントン誘導体；２－クロロアントラキノン、２－メチルアントラキノンのようなアントラキノン誘導体；Ｎ－メチルアクリドン、Ｎ－ブチルアクリドンのようなアクリドン誘導体；その他、α，α－ジエトキシアセトフェノン、ベンジル、フルオレノン、キサントン、ウラニル化合物、ハロゲン化合物等が挙げられる。 Specific photosensitizers are not particularly limited. For example, benzoin derivatives such as benzoin methyl ether, benzoin isopropyl ether, α, α-dimethoxy-α-phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, o Benzophenone derivatives such as methyl benzoylbenzoate, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone; thioxanthone derivatives such as 2-chlorothioxanthone, 2-isopropylthioxanthone; 2 Anthraquinone derivatives such as chloroanthraquinone and 2-methylanthraquinone; acridone derivatives such as N-methylacridone and N-butylacridone; other α, α-diethoxyacetophenone, benzyl, Luenone, xanthone, uranyl compound, halogen compound and the like can be mentioned.
　これらのなかには、上記光ラジカル重合開始剤（ζ）に該当する化合物もあるが、ここでいう光増感剤は、光カチオン重合開始剤（β１）に対する増感剤として機能するものであれば特に限定されない。これらはそれぞれ単独で用いてもよいし、２種類以上を混合して用いてもよい。 Among these, there is a compound corresponding to the above-mentioned photo radical polymerization initiator (ζ), but the photo sensitizer here is particularly one that functions as a sensitizer for the photo cationic polymerization initiator (β 1). It is not limited. These may be used alone or in combination of two or more.
　光増感剤は、本発明に用いられ得る光硬化性接着剤組成物中のカチオン重合性モノマー（上記エポキシ化合物（α１）とオキセタン化合物（α２）を含み、上述した他のカチオン重合性を有する化合物が配合されている場合はそれも含む）の総量を１００質量部として、０．１～２０質量部の範囲で含有するのが好ましい。 The photosensitizer is a cationically polymerizable monomer (including the above epoxy compound (α1) and oxetane compound (α2) in the photocurable adhesive composition that can be used in the present invention, and has the other cationic polymerization properties described above. The total amount of the compound (including the compound when it is blended) is preferably 100 parts by mass and is preferably contained in the range of 0.1 to 20 parts by mass.
　また、重合性を有しない他の成分（η）として、熱カチオン重合開始剤を使用することもできる。熱カチオン重合開始剤として、ベンジルスルホニウム塩、チオフェニウム塩、チオラニウム塩、ベンジルアンモニウム塩、ピリジニウム塩、ヒドラジニウム塩、カルボン酸エステル、スルホン酸エステル、アミンイミド等を挙げることができる。これらの開始剤は、市販品を容易に入手することが可能であり、例えば、いずれも商品名で示して、アデカオプトンＣＰ７７及びアデカオプトンＣＰ６６（以上、（株）ＡＤＥＫＡ製）、ＣＩ－２６３９、ＣＩ－２６２４（以上、日本曹達（株）製）、サンエイドＳＩ－６０Ｌ、サンエイドＳＩ－８０Ｌ、サンエイドＳＩ－１００Ｌ（以上、三新化学工業（株）製）等が挙げられる。 Further, a thermal cationic polymerization initiator can also be used as another component (η) having no polymerizability. Examples of the thermal cationic polymerization initiator include benzylsulfonium salt, thiophenium salt, thiolanium salt, benzylammonium salt, pyridinium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester, and amine imide. These initiators can be easily obtained as commercial products. For example, both of these initiators are indicated by trade names, and ADEKA OPTON CP77 and ADEKA OPTON CP66 (manufactured by ADEKA Corporation), CI-2639, CI- 2624 (manufactured by Nippon Soda Co., Ltd.), Sun Aid SI-60L, Sun Aid SI-80L, Sun Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like.
　ポリオール類はカチオン重合を促進する性質を有するので、やはり重合性を有しない他の成分（η）として使用することができる。ポリオール類としては、フェノール性ヒドロキシ基以外の酸性基が存在しないものが好ましく、例えばヒドロキシ基以外の官能基を有しないポリオール化合物、ポリエステルポリオール化合物、ポリカプロラクトンポリオール化合物、フェノール性ヒドロキシ基を有するポリオール化合物、ポリカーボネートポリオール化合物等を挙げることができる。 Since polyols have the property of promoting cationic polymerization, they can also be used as other components (η) that do not have polymerizability. As the polyols, those having no acidic groups other than phenolic hydroxy groups are preferable. For example, polyol compounds having no functional groups other than hydroxy groups, polyester polyol compounds, polycaprolactone polyol compounds, polyol compounds having phenolic hydroxy groups. And polycarbonate polyol compounds.
　さらに本発明の効果を損なわない限り、重合性を有しない他の成分（η）として、シランカップリング剤、イオントラップ剤、酸化防止剤、光安定剤、連鎖移動剤、増感剤、粘着付与剤、熱可塑性樹脂、充填剤、流動調整剤、可塑剤、消泡剤、レベリング剤、色素、有機溶剤等を配合することもできる。
　重合性を有しない他の成分（η）として、セルロースアシレートフィルムとの密着性をさらに向上させる目的で、熱可塑性樹脂を配合することも有効である。熱可塑性樹脂としては、偏光子の耐久性を高める観点から、ガラス転移温度が７０℃以上であるものが好ましく、特に好ましい例としてはメチルメタクリレート系ポリマー等が挙げられる。 Furthermore, as long as the effects of the present invention are not impaired, other components (η) having no polymerizability include silane coupling agents, ion trapping agents, antioxidants, light stabilizers, chain transfer agents, sensitizers, and tackifiers. An agent, a thermoplastic resin, a filler, a flow regulator, a plasticizer, an antifoaming agent, a leveling agent, a dye, an organic solvent, and the like can also be blended.
In order to further improve the adhesion to the cellulose acylate film as another component (η) having no polymerizability, it is also effective to blend a thermoplastic resin. As the thermoplastic resin, those having a glass transition temperature of 70 ° C. or higher are preferable from the viewpoint of enhancing the durability of the polarizer, and particularly preferred examples include a methyl methacrylate polymer.
＜偏光子＞
　偏光板の主たる構成要素である偏光子は、一定方向の偏波面の光だけを通す素子であり、現在知られている代表的な偏光子は、ポリビニルアルコール系偏光フィルムである。ポリビニルアルコール系偏光フィルムには、ポリビニルアルコール系フィルムにヨウ素を染色させたものと、二色性染料を染色させたものとがある。 <Polarizer>
The polarizer, which is the main component of the polarizing plate, is an element that passes only light having a plane of polarization in a certain direction, and a typical known polarizer is a polyvinyl alcohol polarizing film. The polyvinyl alcohol polarizing film includes those obtained by dyeing iodine on a polyvinyl alcohol film and those obtained by dyeing a dichroic dye.
　偏光子としては、ポリビニルアルコール水溶液を製膜し、これを一軸延伸させて染色するか、染色した後一軸延伸してから、好ましくはホウ素化合物で耐久性処理を行った偏光子が用いられ得る。偏光子の膜厚は５～３０μｍが好ましく、特に１０～２０μｍであることが好ましい。 As the polarizer, a polarizer obtained by forming a polyvinyl alcohol aqueous solution into a film and dyeing it by uniaxial stretching or dyeing and then uniaxially stretching and then preferably performing a durability treatment with a boron compound may be used. The film thickness of the polarizer is preferably 5 to 30 μm, particularly preferably 10 to 20 μm.
　また、特開２００３－２４８１２３号公報、特開２００３－３４２３２２号公報等に記載のエチレン単位の含有量１～４モル％、重合度２０００～４０００、ケン化度９９．０～９９．９９モル％のエチレン変性ポリビニルアルコールも好ましく用いられる。なかでも、熱水切断温度が６６～７３℃であるエチレン変性ポリビニルアルコールフィルムが好ましく用いられる。このエチレン変性ポリビニルアルコールフィルムを用いた偏光子は、偏光性能及び耐久性能に優れているうえに、色斑が少なく、大型液晶表示装置に特に好ましく用いられる。 Further, the ethylene unit content described in JP-A-2003-248123, JP-A-2003-342322, etc. is 1 to 4 mol%, the degree of polymerization is 2000 to 4000, and the degree of saponification is 99.0 to 99.99 mol%. The ethylene-modified polyvinyl alcohol is also preferably used. Of these, an ethylene-modified polyvinyl alcohol film having a hot water cutting temperature of 66 to 73 ° C. is preferably used. A polarizer using this ethylene-modified polyvinyl alcohol film is excellent in polarization performance and durability, and has few color spots, and is particularly preferably used for a large-sized liquid crystal display device.
＜偏光板の製造方法＞
　偏光板は、光硬化性接着剤を用いて、偏光子の一方の面に、上述したアシル基置換度が２．０～２．５であるセルロースアシレートと、Ｔｇ低下剤とを含むセルロースアシレートフィルムを貼り合せることにより製造することができる。貼合時、セルロースアシレートフィルムの両表面のうち、ｒ値が１．１以上を満たす、ｄＡが検出された表面を、偏光子に貼り合せる。すなわち、セルロースアシレートフィルムの両表面のうち、飛行時間型二次イオン質量分析法によるＴｇ低下剤の検出値が大きい方の表面が、偏光子との貼合面とされる。 <Production method of polarizing plate>
The polarizing plate is a cellulose acylate containing a cellulose acylate having an acyl group substitution degree of 2.0 to 2.5 and a Tg reducing agent on one surface of a polarizer using a photocurable adhesive. It can be manufactured by laminating rate films. During lamination, among both surfaces of the cellulose acylate film, r value satisfies the above 1.1, a surface d A is detected, bonded to the polarizer. That is, of the two surfaces of the cellulose acylate film, the surface with the larger detection value of the Tg reducing agent by time-of-flight secondary ion mass spectrometry is used as the bonding surface with the polarizer.
　なお、偏光板を構成する偏光子の他方の面には、本発明に係るセルロースアシレートフィルムを用いてもよいし、他の光学フィルムを貼合することも好ましい。このような他の光学フィルムとしては、例えば、市販のセルロースエステルフィルム（例えば、コニカミノルタタック　ＫＣ８ＵＸ、ＫＣ５ＵＸ、ＫＣ８ＵＣＲ３、ＫＣ８ＵＣＲ４、ＫＣ８ＵＣＲ５、ＫＣ８ＵＹ、ＫＣ４ＵＹ、ＫＣ４ＵＥ、ＫＣ８ＵＥ、ＫＣ８ＵＹ－ＨＡ、ＫＣ８ＵＸ－ＲＨＡ、ＫＣ８ＵＸＷ－ＲＨＡ－Ｃ、ＫＣ８ＵＸＷ－ＲＨＡ－ＮＣ、ＫＣ４ＵＸＷ－ＲＨＡ－ＮＣ、以上コニカミノルタオプト（株）製）が好ましく用いられる。 It should be noted that the cellulose acylate film according to the present invention may be used on the other surface of the polarizer constituting the polarizing plate, or another optical film is preferably bonded. Examples of such other optical films include commercially available cellulose ester films (for example, Konica Minoltak KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, KC8UE, KC8UY-HA, HC8UX-HA, HC8UX -RHA-C, KC8UXW-RHA-NC, KC4UXW-RHA-NC, manufactured by Konica Minolta Opto Co., Ltd.) are preferably used.
　以下、光硬化性接着剤を用いた偏光板の製造方法の一例を説明する。
　偏光板は、セルロースアシレートフィルムの偏光子を接着する面を易接着処理する前処理工程と、偏光子とセルロースアシレートフィルムとの接着面のうち少なくとも一方に、下記の光硬化性接着剤を塗布する接着剤塗布工程と、接着剤層を介して偏光子とセルロースアシレートフィルムとを接着し、貼り合せる貼合工程と、接着剤層を介して偏光子とセルロースアシレートフィルムとが接着された状態で接着剤層を硬化させる硬化工程とを含む製造方法によって製造することができる。 Hereinafter, an example of the manufacturing method of the polarizing plate using a photocurable adhesive agent is demonstrated.
The polarizing plate has the following photo-curing adhesive on at least one of the pretreatment step for easily adhering the surface of the cellulose acylate film to which the polarizer is adhered and the adhesive surface of the polarizer and the cellulose acylate film. Adhesive application process to be applied, a polarizer and a cellulose acylate film are bonded and bonded via an adhesive layer, and a polarizer and a cellulose acylate film are bonded via an adhesive layer It can manufacture by the manufacturing method including the hardening process which hardens an adhesive bond layer in a state.
（前処理工程）
　前処理工程では、偏光子と接着するセルロースアシレートフィルムの表面が易接着処理される。偏光子の両面にそれぞれセルロースアシレートフィルムが接着される場合は、それぞれのセルロースアシレートフィルムに対し易接着処理が行われる。次の接着剤塗布工程では、易接着処理された表面が偏光子との貼合面として扱われるので、セルロースアシレートフィルムの両表面のうち、ｒ値が１．１以上を満たす、ｄＡが検出された表面を、易接着処理する。 (Pretreatment process)
In the pretreatment step, the surface of the cellulose acylate film that adheres to the polarizer is subjected to an easy adhesion treatment. When a cellulose acylate film is adhered to both surfaces of the polarizer, an easy adhesion treatment is performed on each cellulose acylate film. In the next adhesive application step, the surface subjected to the easy adhesion treatment is treated as a bonding surface with the polarizer, and therefore, among both surfaces of the cellulose acylate film, the r value satisfies 1.1 or more, d A is The detected surface is subjected to an easy adhesion treatment.
（接着剤塗布工程）
　接着剤塗布工程では、偏光子とセルロースアシレートフィルムとの接着面のうち少なくとも一方に、上記光硬化性接着剤が塗布される。偏光子又はセルロースアシレートフィルムの表面に直接、光硬化性接着剤を塗布する場合、その塗布方法に特別な限定はない。例えば、ドクターブレード、ワイヤーバー、ダイコーター、カンマコーター、グラビアコーター等、種々の塗工方式が利用できる。また、偏光子とセルロースアシレートフィルムの間に、光硬化性接着剤を流延させたのち、ローラー等で加圧して均一に押し広げる方法も利用できる。 (Adhesive application process)
In the adhesive application step, the photocurable adhesive is applied to at least one of the adhesive surfaces of the polarizer and the cellulose acylate film. When the photocurable adhesive is applied directly to the surface of the polarizer or the cellulose acylate film, there is no particular limitation on the application method. For example, various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used. Moreover, after casting a photocurable adhesive between a polarizer and a cellulose acylate film, the method of pressurizing with a roller etc. and spreading it uniformly can also be utilized.
（貼合工程）
　こうして光硬化性接着剤を塗布した後は、貼合工程に供される。この貼合工程では、例えば、先の塗布工程で偏光子の表面に光硬化性接着剤を塗布した場合、そこにセルロースアシレートフィルムが重ね合わされる。先の塗布工程でセルロースアシレートフィルムの表面に光硬化性接着剤を塗布した場合は、そこに偏光子が重ね合わされる。また、偏光子とセルロースアシレートフィルムの間に光硬化性接着剤を流延させた場合は、その状態で偏光子とセルロースアシレートフィルムとが重ね合わされる。偏光子の両面にセルロースアシレートフィルムを接着する場合であって、両面とも光硬化性接着剤を用いる場合は、偏光子の両面にそれぞれ、光硬化性接着剤を介してセルロースアシレートフィルムが重ね合わされる。そして通常は、この状態で両面（偏光子の片面にセルロースアシレートフィルムを重ね合わせた場合は偏光子側とセルロースアシレートフィルム側をいい、偏光子の両面にセルロースアシレートフィルムを重ね合わせた場合はその両面のセルロースアシレートフィルム側をいう）からローラー等で挟んで加圧することになる。ローラーの材質は、金属やゴム等を用いることが可能である。両面に配置されるローラーは、同じ材質であってもよいし、異なる材質であってもよい。 (Bonding process)
Thus, after apply | coating a photocurable adhesive agent, it uses for a bonding process. In this bonding step, for example, when a photocurable adhesive is applied to the surface of the polarizer in the previous application step, a cellulose acylate film is superimposed thereon. When a photocurable adhesive is applied to the surface of the cellulose acylate film in the previous application step, a polarizer is superimposed thereon. Moreover, when a photocurable adhesive agent is cast between a polarizer and a cellulose acylate film, a polarizer and a cellulose acylate film are piled up in that state. When a cellulose acylate film is bonded to both sides of a polarizer and a photocurable adhesive is used on both sides, the cellulose acylate film is superimposed on each side of the polarizer via a photocurable adhesive. Is done. Usually, in this state, both sides (when the cellulose acylate film is superimposed on one side of the polarizer, the polarizer side and the cellulose acylate film side are referred to, and when the cellulose acylate film is superimposed on both sides of the polarizer, Means the cellulose acylate film side of both surfaces), and is pressed with a roller or the like. As the material of the roller, metal, rubber or the like can be used. The rollers arranged on both sides may be made of the same material or different materials.
（硬化工程）
　硬化工程では、未硬化の光硬化性接着剤に活性エネルギー線を照射して、エポキシ化合物やオキセタン化合物を含む接着剤層を硬化させ、光硬化性接着剤を介して重ね合わせた偏光子とセルロースアシレートフィルムとを接着させる。偏光子の片面にセルロースアシレートフィルムを貼合する場合、活性エネルギー線は、偏光子側又はセルロースアシレートフィルム側のいずれから照射してもよい。また、偏光子の両面にセルロースアシレートフィルムを貼合する場合、偏光子の両面にそれぞれ光硬化性接着剤を介してセルロースアシレートフィルムを重ね合わせた状態で、いずれか一方のセルロースアシレートフィルム側から活性エネルギー線を照射し、両面の光硬化性接着剤を同時に硬化させるのが有利である。ただし、いずれか一方のセルロースアシレートフィルムに紫外線吸収剤が配合されている場合であって、活性エネルギー線が紫外線である場合、通常、紫外線吸収剤が配合されていない他方のセルロースアシレートフィルム側から紫外線が照射される。 (Curing process)
In the curing step, an active energy ray is irradiated onto an uncured photocurable adhesive to cure an adhesive layer containing an epoxy compound or an oxetane compound, and the polarizer and cellulose layered via the photocurable adhesive Adhere to acylate film. When a cellulose acylate film is bonded to one side of the polarizer, the active energy ray may be irradiated from either the polarizer side or the cellulose acylate film side. Moreover, when bonding a cellulose acylate film on both surfaces of a polarizer, either cellulose acylate film is in a state where the cellulose acylate film is superposed on both surfaces of the polarizer via a photocurable adhesive, respectively. It is advantageous to irradiate active energy rays from the side and simultaneously cure the photocurable adhesive on both sides. However, when an ultraviolet absorber is blended in one of the cellulose acylate films and the active energy ray is ultraviolet, the other cellulose acylate film side not blended with the ultraviolet absorber is usually used. Is irradiated with ultraviolet rays.
　活性エネルギー線としては、可視光線、紫外線、Ｘ線、電子線等を用いることができるが、取扱いが容易で硬化速度も十分であることから、一般には紫外線が好ましく用いられる。活性エネルギー線の光源は特に限定されないが、波長４００ｎｍ以下に発光分布を有する、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ブラックライトランプ、マイクロウェーブ励起水銀灯、メタルハライドランプ、ＬＥＤランプ等を用いることができる。 As the active energy ray, visible light, ultraviolet ray, X-ray, electron beam and the like can be used, but ultraviolet ray is generally preferably used because it is easy to handle and has a sufficient curing rate. The light source of the active energy ray is not particularly limited, but has a light emission distribution at a wavelength of 400 nm or less. An LED lamp or the like can be used.
　光硬化性接着剤への光照射強度は、目的とする組成物毎に決定されるものであって、やはり特に限定されないが、重合開始剤の活性化に有効な波長領域の照射強度が、ＵＶ－Ｂ（２８０～３２０ｎｍの中波長域紫外線）として１～３，０００ｍＷ／ｃｍ２の範囲となるように調整することが好ましい。照射強度が１～３，０００ｍＷ／ｃｍ２の範囲内であれば、適当な反応時間で足り、ランプから輻射される熱及び光硬化性接着剤の重合時の発熱による光硬化性接着剤の黄変や偏光子の劣化を防止できる。 The light irradiation intensity to the photocurable adhesive is determined for each target composition and is not particularly limited, but the irradiation intensity in the wavelength region effective for activating the polymerization initiator is UV. Adjustment is preferably made so that it is in the range of 1 to 3,000 mW / cm 2 as -B (ultraviolet light in the middle wavelength range of 280 to 320 nm). If the irradiation intensity is in the range of 1 to 3,000 mW / cm 2 , an appropriate reaction time is sufficient, and the yellow of the photocurable adhesive is generated by heat radiated from the lamp and heat generated during polymerization of the photocurable adhesive. Deformation and deterioration of the polarizer can be prevented.
　光硬化性接着剤への光照射時間は、硬化する組成物毎に制御されるものであって、特に限定されないが、照射強度と照射時間の積で表される積算光量が１０～５０００ｍＪ／ｃｍ２の範囲となるように設定されることが好ましい。積算光量が１０～５０００ｍＪ／ｃｍ２の範囲内であれば、重合開始剤に由来する活性種が十分に発生し、接着剤層の硬化が十分となる。また、適当な照射時間で足り、生産性向上に適する。 The light irradiation time to the photocurable adhesive is controlled for each composition to be cured and is not particularly limited. However, the integrated light amount represented by the product of the irradiation intensity and the irradiation time is 10 to 5000 mJ / cm. It is preferably set to be in the range of 2 . When the integrated light quantity is in the range of 10 to 5000 mJ / cm 2 , active species derived from the polymerization initiator are sufficiently generated, and the adhesive layer is sufficiently cured. In addition, an appropriate irradiation time is sufficient, which is suitable for improving productivity.
　活性エネルギー線を照射して光硬化性接着剤を硬化させるにあたっては、偏光子の偏光度、透過率、色相、セルロースアシレートフィルムの透明性といった、偏光板の諸機能が低下しない条件で硬化させることが好ましい。 When curing the photocurable adhesive by irradiating active energy rays, it is cured under conditions that do not deteriorate the various functions of the polarizing plate, such as the degree of polarization of the polarizer, the transmittance, the hue, and the transparency of the cellulose acylate film. It is preferable.
　以上のようにして得られた偏光板において、接着剤層の厚さは、特に限定されないが、通常５０μｍ以下であり、好ましくは２０μｍ以下、より好ましくは１０μｍ以下、さらに好ましくは５μｍ以下である。 In the polarizing plate obtained as described above, the thickness of the adhesive layer is not particularly limited, but is usually 50 μm or less, preferably 20 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less.
＜液晶表示装置＞
　本発明に係る偏光板は、液晶表示装置に好適に用いることができる。本発明に係る偏光板が用いられた液晶表示装置は、優れた光学補償機能を有するセルロースアシレートフィルムが用いられていることから、視認性に優れている。また、このような液晶表示装置は、偏光子とセルロースアシレートフィルム間の密着性が高いことから、耐久性にも優れている。 <Liquid crystal display device>
The polarizing plate according to the present invention can be suitably used for a liquid crystal display device. The liquid crystal display device using the polarizing plate according to the present invention is excellent in visibility because a cellulose acylate film having an excellent optical compensation function is used. In addition, such a liquid crystal display device has excellent durability because of high adhesion between the polarizer and the cellulose acylate film.
　偏光板のセルロースアシレートフィルム側の表面と、液晶セルの少なくとも一方の表面との貼合は、公知の手法により行われ得る。場合によっては、接着層を介して貼合されてもよい。
　液晶表示装置のモード（駆動方式）についても特に制限はなく、ＳＴＮ、ＴＮ、ＯＣＢ、ＨＡＮ、ＶＡ（ＭＶＡ、ＰＶＡ）、ＩＰＳ、ＯＣＢ等の各種駆動モードの液晶表示装置が用いられ得る。好ましくは、ＶＡ（ＭＶＡ，ＰＶＡ）型の液晶表示装置である。これらの液晶表示装置に、本発明に係る偏光板を用いることで、３０型以上の大画面の液晶表示装置であっても、環境変動が少なく、色味ムラ、正面コントラスト等の視認性に優れた液晶表示装置を得ることができる。 The bonding between the surface of the polarizing plate on the cellulose acylate film side and at least one surface of the liquid crystal cell can be performed by a known method. Depending on the case, it may be bonded through an adhesive layer.
The mode (driving method) of the liquid crystal display device is not particularly limited, and liquid crystal display devices in various drive modes such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, and OCB can be used. A VA (MVA, PVA) type liquid crystal display device is preferable. By using the polarizing plate according to the present invention for these liquid crystal display devices, even with a 30-inch or larger screen liquid crystal display device, there are few environmental fluctuations and excellent visibility such as uneven coloring and front contrast. A liquid crystal display device can be obtained.
　以下に実施例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお、実施例において用いられる「部」又は「％」は、特に断りがない限り、「質量部」又は「質量％」を表す。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, “part” or “%” used in Examples represents “part by mass” or “% by mass” unless otherwise specified.
〔実施例１〕
＜セルロースアシレートフィルム１０１の作製＞
（微粒子分散液１の調製）
　微粒子（アエロジル　Ｒ９７２Ｖ　日本アエロジル（株）製）　　　　　１１質量部
　エタノール　　　　　　　　　　　　　　　　　　　　　　　　　　　　８９質量部
　以上をディゾルバーで５０分間攪拌混合した後、マントンゴーリンで分散を行って、微粒子分散液１を調製した。 [Example 1]
<Preparation of Cellulose Acylate Film 101>
(Preparation of fine particle dispersion 1)
Fine particles (Aerosil R972V manufactured by Nippon Aerosil Co., Ltd.) 11 parts by weight Ethanol 89 parts by weight The above was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin to prepare a fine particle dispersion 1.
（微粒子添加液１の調製）
　メチレンクロライドを入れた溶解タンクに十分攪拌しながら、微粒子分散液１をゆっくりと添加した。メチレンクロライドと微粒子分散液１の質量は、下記の通りである。さらに、二次粒子の粒径が所定の大きさとなるようにアトライターにて分散を行った。これを日本精線（株）製のファインメットＮＦで濾過し、微粒子添加液１を調製した。
　メチレンクロライド　　　　　　　　　　　　　　　　　　　　　　　９９質量部
　微粒子分散液１　　　　　　　　　　　　　　　　　　　　　　　　　　５質量部 (Preparation of fine particle additive solution 1)
The fine particle dispersion 1 was slowly added to the dissolution tank containing methylene chloride with sufficient stirring. The masses of methylene chloride and fine particle dispersion 1 are as follows. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution 1.
99 parts by mass of methylene chloride 5 parts by mass of fine particle dispersion 1
（主ドープ液の調製）
　下記組成の主ドープ液を調製した。
　メチレンクロライド　　　　　　　　　　　　　　　　　　　　　　３４０質量部
　エタノール　　　　　　　　　　　　　　　　　　　　　　　　　　　６４質量部
　セルロースアシレート（アセチル置換度２．４５、重量平均分子量Ｍｗ１３５０００のセルロースアシレートと、アセチル置換度２．４５、重量平均分子量Ｍｗ１８００００のセルロースアシレートとを、６：４の質量比で混合した混合物）　　１００質量部
　加水分解防止剤（糖エステル化合物（ａ１）、（ａ２）、（ａ３）、（ａ４）を、１：１４：３５：４０の質量比（ａ１：ａ２：ａ３：ａ４）で混合した混合物、平均ｌｏｇＰ値＝８．７、Ｔｇ低下能＝２．１℃／質量部）　　　　　　　　　　　　　　　　　８質量部
　微粒子添加液１　　　　　　　　　　　　　　　　　　　　　　　　　　１質量部 (Preparation of main dope solution)
A main dope solution having the following composition was prepared.
Methylene chloride 340 parts by mass Ethanol 64 parts by weight Cellulose acylate (cellulose acylate having an acetyl substitution degree of 2.45 and a weight average molecular weight Mw of 135,000, and a cellulose acylate having an acetyl substitution degree of 2.45 and a weight average molecular weight of Mw of 180000 are 6: 100 parts by mass Hydrolysis inhibitors (sugar ester compounds (a1), (a2), (a3), (a4) were mixed at a mass ratio of 1: 14: 35: 40 (a1: a2: a3: a4) mixture, average log P value = 8.7, Tg lowering ability = 2.1 ° C./part by mass) 8 parts by mass Particulate additive liquid 1 1 part by mass
　まず、加圧溶解タンクに上記組成のメチレンクロライドとエタノールを添加した。この溶剤の入った加圧溶解タンクに、アセチル置換度２．４５、重量平均分子量Ｍｗ１３５０００のセルロースアシレートと、アセチル置換度２．４５、重量平均分子量Ｍｗ１８００００のセルロースアシレートとを、６：４の質量比で混合した上記組成のセルロースアシレートを、攪拌しながら投入した。これを加熱し、攪拌しながら、完全に溶解させた後、安積濾紙（株）製の安積濾紙Ｎｏ．２４４を使用して濾過し、主ドープ液を調製した。主ドープ液を密閉容器に投入し、攪拌しながら溶解してドープ液を調整した。 First, methylene chloride and ethanol having the above composition were added to a pressure dissolution tank. In a pressure dissolution tank containing this solvent, cellulose acylate having an acetyl substitution degree of 2.45 and a weight average molecular weight Mw of 135,000, and a cellulose acylate having an acetyl substitution degree of 2.45 and a weight average molecular weight of Mw of 180000 The cellulose acylate having the above composition mixed in a mass ratio was added while stirring. After heating and stirring, this was completely dissolved, and then Azumi filter paper No. 1 manufactured by Azumi Filter Paper Co., Ltd. was used. The main dope solution was prepared by filtration using 244. The main dope solution was put into a sealed container and dissolved while stirring to prepare a dope solution.
（セルロースアシレートフィルムの作製）
　次いで、無端ベルト流延装置を用い、ドープ液を温度３３℃、１５００ｍｍ幅でステンレスベルト支持体上に均一に流延した。ステンレスベルトの温度は３０℃に制御した。
　ステンレスベルト支持体上で、流延（キャスト）したセルロースアシレートフィルム中の残留溶媒量が８８％になるまで溶媒を蒸発させ、次いで剥離張力１３０Ｎ／ｍで、ステンレスベルト支持体上から剥離した。
　剥離したセルロースアシレートフィルムを、１６０℃の熱を加えながらテンターを用いて幅方向に１．１５倍延伸した。延伸開始時の残留溶媒量は１０％であった。
　次いで、乾燥ゾーンを多数のロールで搬送させながら乾燥を終了させた。乾燥温度は１３０℃、搬送張力は１００Ｎ／ｍとした。
　以上のようにして、乾燥膜厚４５μｍ、長さ２０００ｍのセルロースアシレートフィルム１０１を得た。 (Preparation of cellulose acylate film)
Next, using an endless belt casting apparatus, the dope solution was uniformly cast on a stainless steel belt support at a temperature of 33 ° C. and a width of 1500 mm. The temperature of the stainless steel belt was controlled at 30 ° C.
On the stainless steel belt support, the solvent was evaporated until the residual solvent amount in the cast (cast) cellulose acylate film was 88%, and then peeled off from the stainless steel belt support with a peeling tension of 130 N / m.
The peeled cellulose acylate film was stretched 1.15 times in the width direction using a tenter while applying heat at 160 ° C. The residual solvent amount at the start of stretching was 10%.
Next, drying was terminated while the drying zone was conveyed by a number of rolls. The drying temperature was 130 ° C. and the conveyance tension was 100 N / m.
As described above, a cellulose acylate film 101 having a dry film thickness of 45 μm and a length of 2000 m was obtained.
＜セルロースアシレートフィルム１０２～１１８の作製＞
　ドープ液組成物及び製造条件を、下記表１に示すように変更した以外は、セルロースアシレートフィルム１０１と同様にして、セルロースアシレートフィルム１０２～１１８を作製した。セルロースアシレートフィルム１０１の作製においてＴｇ低下剤を添加しなかったが、Ｔｇ低下剤を添加する場合、主ドープ液の組成にＴｇ低下剤を含む。 <Preparation of cellulose acylate films 102-118>
Cellulose acylate films 102 to 118 were produced in the same manner as the cellulose acylate film 101 except that the dope solution composition and production conditions were changed as shown in Table 1 below. In the production of the cellulose acylate film 101, the Tg reducing agent was not added. However, when the Tg reducing agent is added, the composition of the main dope solution includes the Tg reducing agent.
　表１には、各セルロースアシレートフィルム１０１～１１８の主ドープ液組成物に含まれるＴｇ低下剤の化合物、添加量、Ｔｇ低下能の値、加水分解防止剤として混合された化合物、化合物の混合比率、添加量、平均ｌｏｇＰ値、剥離時におけるセルロースアシレートフィルム中の残留溶媒量の値が記載されている。 Table 1 shows the compounds of the Tg reducing agent contained in the main dope composition of each of the cellulose acylate films 101 to 118, the amount added, the value of the Tg reducing ability, the compound mixed as a hydrolysis inhibitor, and the mixture of the compounds The ratio, the added amount, the average log P value, and the value of the residual solvent amount in the cellulose acylate film at the time of peeling are described.
＜評価＞
　上記で得られたセルロースアシレートフィルム１０１～１１８について、以下の測定方法により、両表面におけるＴｇ低下剤の分布の比であるｒ値、加水分解防止剤の分布の比であるｓ値、算術平均粗さＲａを測定した。測定結果は、下記表１に示される。表１においてＱ１面はドープの流延時に金属支持体と接していた面とは反対側の面を表す。Ｑ２面は、ドープの流延時に金属支持体と接していた面を表す。 <Evaluation>
With respect to the cellulose acylate films 101 to 118 obtained as described above, the following measurement method was used to determine the r value, which is the ratio of the Tg reducing agent distribution on both surfaces, the s value, which is the ratio of the hydrolysis inhibitor distribution, and the arithmetic mean. The roughness Ra was measured. The measurement results are shown in Table 1 below. In Table 1, the Q1 surface represents the surface opposite to the surface that was in contact with the metal support during casting of the dope. The Q2 plane represents the plane that was in contact with the metal support during casting of the dope.
（ｒ値及びｓ値の測定方法）
　下記測定条件によって、飛行時間型二次イオン質量分析法を用いて、セルロースアシレートフィルム１０１～１１８の各表面におけるＴｇ低下剤の検出値を得た。
　測定装置　：２１００ＴＲＩＦＴ２（Phisical Electronics社製）
　測定モード：冷却測定（温度範囲－９５～－１０５℃）
　一次イオン：Ｇａ（１５ｋＶ）
　測定領域　：６０μｍ角
　積算時間　：２分
　Ｔｇ低下剤（芳香族ポリエステル（ａｒ－１４））の場合の参照イオンｍ／Ｚ：１１９
　加水分解防止剤（糖エステル化合物（ａ１）、（ａ２）、（ａ３）、（ａ４）の混合物）の場合の参照イオンｍ／Ｚ：１０５
　各表面のＴｇ低下剤の検出値のうち、大きい方をｄＡ、小さい方をｄＢとして、上述の数式（１）に従って、ｒ値を算出した。
　なお、Ｔｇ低下剤が添加されていないセルロースアシレートフィルム１０１、１０８を除き、セルロースアシレートフィルム１０２～１０７、１０９～１１８のいずれも、Ｑ２面の方がＱ１面よりもＴｇ低下剤の検出値が大きかった。 (Measurement method of r value and s value)
Under the following measurement conditions, a detection value of a Tg reducing agent on each surface of the cellulose acylate films 101 to 118 was obtained using time-of-flight secondary ion mass spectrometry.
Measuring device: 2100TRIFT2 (Phisical Electronics)
Measurement mode: Cooling measurement (temperature range -95 to -105 ° C)
Primary ion: Ga (15 kV)
Measurement area: 60 μm square Integration time: 2 minutes Reference ion m / Z in the case of Tg reducing agent (aromatic polyester (ar-14)): 119
Reference ion m / Z in the case of hydrolysis inhibitor (mixture of sugar ester compounds (a1), (a2), (a3), (a4)): 105
Among the detected values of Tg-lowering agent of the surface, as better the d A, the smaller the d B large, according to the above equation (1) to calculate the r value.
In addition, except for the cellulose acylate films 101 and 108 to which no Tg reducing agent is added, the detected values of the Tg reducing agent in the Q2 surface are higher than those in the Q1 surface in any of the cellulose acylate films 102 to 107 and 109 to 118. Was big.
　同様の測定条件により、飛行時間型二次イオン質量分析法を用いて、セルロースアシレートフィルム１０１～１１８の各表面の加水分解防止剤の検出値を得た。各表面の加水分解防止剤の検出値のうち、大きい方をｄＣ、小さい方をｄＤとして、上述の数式（２）に従ってｓ値を算出した。 Under the same measurement conditions, the detection value of the hydrolysis inhibitor on each surface of the cellulose acylate films 101 to 118 was obtained using time-of-flight secondary ion mass spectrometry. Of the detected values of the hydrolysis inhibitor on each surface, the larger one was d C , and the smaller one was d D , and the s value was calculated according to the above formula (2).
（算術平均粗さＲａの測定方法）
　ＪＩＳ　Ｂ０６０１：２００１に従って、光学干渉式表面粗さ計（ＲＳＴ／ＰＬＵＳ、ＷＹＫＯ社製）で算術平均粗さＲａを測定した。 (Measurement method of arithmetic average roughness Ra)
In accordance with JIS B0601: 2001, the arithmetic average roughness Ra was measured with an optical interference surface roughness meter (RST / PLUS, manufactured by WYKO).
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
　表１において、Ｔｇ低下剤の芳香族ポリエステル化合物は、先に例示された芳香族ポリエステル化合物（ａｒ－５）、（ａｒ－１４）、（ａｒ－１６）又は（ＰＥＳ－７）を示している。
　加水分解防止剤の化合物Ｎｏ．におけるａ１～ａ４は、糖エステル化合物（ａ１）、（ａ２）、（ａ３）、（ａ４）を示している。また、ＰＥＴＢはペンタエリスリトールテトラベンゾエートを表す。加水分解防止剤の化合物の比率は、化合物Ｎｏ．で示される化合物の混合比率を示している。 In Table 1, the aromatic polyester compound of the Tg reducing agent indicates the aromatic polyester compound (ar-5), (ar-14), (ar-16) or (PES-7) exemplified above. .
Hydrolysis inhibitor compound no. A1 to a4 in the formulas represent the sugar ester compounds (a1), (a2), (a3), and (a4). PETB represents pentaerythritol tetrabenzoate. The ratio of the compound of the hydrolysis inhibitor is the compound no. The mixing ratio of the compound shown by is shown.
〔実施例２〕
＜偏光板２０１～２２１の作製＞
（偏光子の作製）
　厚さ７０μｍのポリビニルアルコールフィルムを、３５℃の水で膨潤させた。得られたフィルムを、ヨウ素０．０７５ｇ、ヨウ化カリウム５ｇ及び水１００ｇからなる水溶液に６０秒間浸漬し、さらにヨウ化カリウム３ｇ、ホウ酸７．５ｇ及び水１００ｇからなる４５℃の水溶液に浸漬した。得られたフィルムを、延伸温度５５℃、延伸倍率５倍の条件で一軸延伸した。この一軸延伸フィルムを、水洗した後、乾燥させて、厚さ２０μｍの偏光子を得た。 [Example 2]
<Preparation of polarizing plates 201-221>
(Production of polarizer)
A 70 μm thick polyvinyl alcohol film was swollen with water at 35 ° C. The obtained film was immersed in an aqueous solution consisting of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and further immersed in an aqueous solution at 45 ° C. consisting of 3 g of potassium iodide, 7.5 g of boric acid and 100 g of water. . The obtained film was uniaxially stretched under conditions of a stretching temperature of 55 ° C. and a stretching ratio of 5 times. The uniaxially stretched film was washed with water and dried to obtain a polarizer having a thickness of 20 μm.
（接着剤の調製）
　下記の各成分を混合した後、脱泡して、光硬化性接着剤液を調製した。なお、トリアリールスルホニウムヘキサフルオロホスフェートは、５０％プロピレンカーボネート溶液として配合し、下記にはトリアリールスルホニウムヘキサフルオロホスフェートの固形分量を表示した。 (Preparation of adhesive)
Each of the following components was mixed and then defoamed to prepare a photocurable adhesive liquid. Triarylsulfonium hexafluorophosphate was blended as a 50% propylene carbonate solution, and the solid content of triarylsulfonium hexafluorophosphate was shown below.
（接着剤液組成）
　３，４－エポキシシクロヘキシルメチル３，４－エポキシシクロヘキサンカルボキシレート　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　４５質量部
　エポリードＧＴ－３０１（ダイセル化学社製の脂環式エポキシ樹脂）４０質量部
　１，４－ブタンジオールジグリシジルエーテル　　　　　　　　　　１５質量部
　トリアリールスルホニウムヘキサフルオロホスフェート　　　　　　　２．３質量部
　９，１０－ジブトキシアントラセン　　　　　　　　　　　　　　　　０．１質量部
　１，４－ジエトキシナフタレン　　　　　　　　　　　　　　　　　　２．０質量部 (Adhesive solution composition)
3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate 45 parts by mass Epolide GT-301 (alicyclic epoxy resin manufactured by Daicel Chemical Industries) 40 parts by mass 1,4-butanediol diglycidyl ether 15 parts by mass Tria Reel sulfonium hexafluorophosphate 2.3 parts by mass 9,10-dibutoxyanthracene 0.1 parts by mass 1,4-diethoxynaphthalene 2.0 parts by mass
（偏光板の作製）
　セルロースアシレートフィルム１０１～１１８をそれぞれ用いた偏光板を、下記のように作製した。
　まず、ＫＣ６ＵＹ（コニカミノルタオプト（株）製）フィルムを準備し、その表面にコロナ放電処理を施した。なお、コロナ放電処理の条件は、コロナ出力強度２．０ｋＷ、ライン速度１８ｍ／分とした。次いで、当該フィルムのコロナ放電処理面に、上記調製した接着剤液を、硬化後の膜厚が約３μｍとなるようにバーコーターで塗工して接着剤層を形成した。得られた接着剤層に、前述のようにして作製したポリビニルアルコール－ヨウ素系偏光子を貼合した。 (Preparation of polarizing plate)
Polarizing plates using the cellulose acylate films 101 to 118 were produced as follows.
First, a KC6UY (Konica Minolta Opto Co., Ltd.) film was prepared, and the surface was subjected to corona discharge treatment. The corona discharge treatment was performed at a corona output intensity of 2.0 kW and a line speed of 18 m / min. Next, the adhesive solution prepared above was applied to the corona discharge treated surface of the film with a bar coater so that the film thickness after curing was about 3 μm to form an adhesive layer. A polyvinyl alcohol-iodine polarizer prepared as described above was bonded to the obtained adhesive layer.
　同様にして、セルロースアシレートフィルム１０１～１１８の表面に、コロナ放電処理を施した。コロナ放電処理の条件は、コロナ出力強度２．０ｋＷ、ライン速度１８ｍ／分とした。次いで、セルロースアシレートフィルム１０１～１１８のコロナ放電処理面に、上記調製した接着剤液を、硬化後の膜厚が約３μｍとなるようにバーコーターで塗工して接着剤層を形成した。その際に、セルロースアシレートフィルムの遅相軸と偏光子の吸収軸が互いに直交になるように貼合した。
　この接着剤層に、ＫＣ６ＵＹ（コニカミノルタオプト（株）製）フィルムが片面に貼合された偏光子の偏光子を貼合して、セルロースアシレートフィルム１０１～１１８／偏光子／ＫＣ６ＵＹ（コニカミノルタオプト（株）製）フィルムの積層物を得た。この積層物のセルロースアシレートフィルム１０１～１１８側から、ベルトコンベア付き紫外線照射装置（ランプは、フュージョンＵＶシステムズ社製のＤバルブを使用）を用いて、積算光量が７５０ｍＪ／ｃｍ２となるように紫外線を照射し、接着剤層を硬化させた。 Similarly, the surfaces of the cellulose acylate films 101 to 118 were subjected to corona discharge treatment. The conditions for the corona discharge treatment were a corona output intensity of 2.0 kW and a line speed of 18 m / min. Next, the adhesive solution prepared above was applied to the corona discharge treated surfaces of the cellulose acylate films 101 to 118 with a bar coater so that the film thickness after curing was about 3 μm to form an adhesive layer. In that case, it bonded so that the slow axis of a cellulose acylate film and the absorption axis of a polarizer might become mutually orthogonal.
A polarizer polarizer having a KC6UY (Konica Minolta Opto Co., Ltd.) film bonded on one side is bonded to this adhesive layer, and cellulose acylate films 101 to 118 / polarizer / KC6UY (Konica Minolta) are bonded. An optical film laminate was obtained. From the cellulose acylate film 101 to 118 side of this laminate, using a UV irradiation device with a belt conveyor (the lamp uses a D bulb manufactured by Fusion UV Systems) so that the integrated light quantity becomes 750 mJ / cm 2. The adhesive layer was cured by irradiating with ultraviolet rays.
　このようにして、セルロースアシレートフィルム１０１～１１８のそれぞれを用いて、偏光子が２枚のフィルムで挟持された偏光板２０１～２２１を作製した。
　各偏光板２０１～２２１の作製に用いたセルロースアシレートフィルム１０１～１１８がいずれであるか、またその偏光子との貼合面がＱ１面又はＱ２面のいずれであるかは、下記表２に示す通りである。
　すなわち、表２に示すように、偏光板２０１～２１８は、セルロースアシレートフィルム１０１～１１８のＱ２面を偏光子との貼合面とし、偏光板２１９～２２１は、それぞれセルロースアシレートフィルム１０２、１０４、１０９のＱ１面を偏光子との貼合面とした。 In this manner, polarizing plates 201 to 221 in which a polarizer was sandwiched between two films were prepared using each of the cellulose acylate films 101 to 118.
Table 2 below shows which of the cellulose acylate films 101 to 118 used for the production of each of the polarizing plates 201 to 221 and whether the bonding surface with the polarizer is the Q1 surface or the Q2 surface. As shown.
That is, as shown in Table 2, the polarizing plates 201 to 218 have the Q2 surface of the cellulose acylate films 101 to 118 as the bonding surface with the polarizer, and the polarizing plates 219 to 221 have the cellulose acylate film 102, The Q1 surface of 104 and 109 was used as a bonding surface with a polarizer.
＜偏光板の評価＞
　得られた偏光板２０１～２２１について、以下の測定方法により、偏光子とセルロースアシレートフィルムとの密着性と、偏光板の偏光度を測定し、評価した。評価結果は、下記表２に示される。 <Evaluation of polarizing plate>
The obtained polarizing plates 201 to 221 were evaluated by measuring the adhesion between the polarizer and the cellulose acylate film and the degree of polarization of the polarizing plate by the following measuring methods. The evaluation results are shown in Table 2 below.
（偏光子とセルロースアシレートフィルムとの密着性の評価方法）
　偏光板２０１～２２１を、温度６０℃、９０％ＲＨの湿熱条件下に５００時間静置した。その後、偏光板２０１～２２１を構成する偏光子とセルロースアシレートフィルムとを手で剥離することができるか否かにより、密着性を評価した。
　評価基準は、以下の通りである。
　○：手で剥離することができなかった。
　×：手で剥離することができた。 (Evaluation method for adhesion between polarizer and cellulose acylate film)
The polarizing plates 201 to 221 were allowed to stand for 500 hours under wet heat conditions of a temperature of 60 ° C. and 90% RH. Thereafter, the adhesion was evaluated depending on whether the polarizer constituting the polarizing plates 201 to 221 and the cellulose acylate film can be peeled by hand.
The evaluation criteria are as follows.
○: Could not be peeled by hand.
X: It was able to peel by hand.
（偏光板の偏光度の評価方法）
　偏光板２０１～２２１の偏光度を、日本分光（株）製「Ｖ－７１００」を用いて測定した。
　具体的には、偏光板の平行透過率（Ｈ０）及び直交透過率（Ｈ９０）を測定し、式：偏光度（％）＝｛（Ｈ０－Ｈ９０）／（Ｈ０＋Ｈ９０）｝１／２×１００より偏光度を算出した。ここで、平行透過率（Ｈ０）は、同じ偏光板２枚を互いの吸収軸が平行となるように重ね合わせて作製した平行型積層偏光板の透過率の値である。一方、直交透過率（Ｈ９０）は、同じ偏光板２枚を互いの吸収軸が直交するように重ね合わせて作製した直交型積層偏光板の透過率の値である。これらの透過率は、ＪＩＳ　Ｚ　８７０１（１９８２年版）の２度視野（Ｃ光源）により、視感度補正を行ったＹ値である。
　偏光度に対する評価基準は、以下の通りである。
　○：偏光度が９９．９９０以上
　△：偏光度が９９．９８０以上９９．９９０未満
　×：偏光度が９９．９８０未満 (Evaluation method of polarization degree of polarizing plate)
The degree of polarization of the polarizing plates 201 to 221 was measured using “V-7100” manufactured by JASCO Corporation.
Specifically, the parallel transmittance (H0) and orthogonal transmittance (H90) of the polarizing plate are measured, and the formula: degree of polarization (%) = {(H0−H90) / (H0 + H90)} 1/2 × 100 The degree of polarization was calculated. Here, the parallel transmittance (H0) is a transmittance value of a parallel laminated polarizing plate produced by superposing two identical polarizing plates so that their absorption axes are parallel to each other. On the other hand, the orthogonal transmittance (H90) is a transmittance value of an orthogonal laminated polarizing plate produced by superposing two identical polarizing plates so that their absorption axes are orthogonal to each other. These transmittances are Y values obtained by correcting the visibility using a two-degree field of view (C light source) of JIS Z 8701 (1982 edition).
The evaluation criteria for the degree of polarization are as follows.
○: Polarization degree is 99.990 or more Δ: Polarization degree is 99.980 or more and less than 99.990 ×: Polarization degree is less than 99.980
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
　評価の結果、本発明に係る偏光板は、いずれも偏光子との密着性に優れたものであり、しかも、偏光子との貼合時の軸ずれに起因する偏光板の偏光度の低下も抑制され得るものであることが示された。
　一方、比較例のセルロースアシレートフィルムを用いた偏光板は、いずれも偏光子との密着性が劣り、偏光板の偏光度の低下を満足のいくレベルで抑制できていない。 As a result of the evaluation, all of the polarizing plates according to the present invention are excellent in adhesiveness with the polarizer, and also the degree of polarization of the polarizing plate is lowered due to the axial deviation at the time of bonding with the polarizer. It was shown that it can be suppressed.
On the other hand, all the polarizing plates using the cellulose acylate film of the comparative example are inferior in adhesion to the polarizer, and the decrease in the degree of polarization of the polarizing plate cannot be suppressed at a satisfactory level.
　液晶表示技術の分野において利用することが可能であり、セルロースアシレートを用いた偏光板及び液晶表示装置に適用することができる。 It can be used in the field of liquid crystal display technology and can be applied to polarizing plates and liquid crystal display devices using cellulose acylate.

Claims (7)

  1. 　アシル基置換度が２．０～２．５の範囲内にあるセルロースアシレートと、ガラス転移温度低下剤と、を含むセルロースアシレートフィルムを、光硬化性接着剤を用いて偏光子の一方の面に貼り合わせた偏光板であって、
    　飛行時間型二次イオン質量分析法（ＴＯＦ－ＳＩＭＳ）を用いて検出される、前記セルロースアシレートフィルムの貼合面の前記ガラス転移温度低下剤の検出値をｄＡ、他方の面の検出値をｄＢとしたとき、下記式（１）により示されるｒ値が１．１以上であることを特徴とする偏光板。
    　式（１）　ｒ＝ｄＡ／ｄＢ     A cellulose acylate film containing a cellulose acylate having an acyl group substitution degree in the range of 2.0 to 2.5 and a glass transition temperature lowering agent is bonded to one of the polarizers using a photocurable adhesive. A polarizing plate bonded to a surface,
    The detected value of the glass transition temperature reducing agent on the bonding surface of the cellulose acylate film, detected using time-of-flight secondary ion mass spectrometry (TOF-SIMS), is d A , and the detected value of the other surface The polarizing plate is characterized in that the r value represented by the following formula (1) is 1.1 or more, where d is B.
    Formula (1) r = d A / d B
  2. 　前記セルロースアシレートは、アシル基置換度が２．０～２．５の範囲内にあるジアセチルセルロースであることを特徴とする請求項１に記載の偏光板。 The polarizing plate according to claim 1, wherein the cellulose acylate is diacetyl cellulose having an acyl group substitution degree in the range of 2.0 to 2.5.
  3. 　前記ガラス転移温度低下剤のガラス転移温度低下能が、３．５℃／質量部以上であることを特徴とする請求項１又は２に記載の偏光板。 3. The polarizing plate according to claim 1, wherein the glass transition temperature lowering agent has a glass transition temperature lowering ability of 3.5 ° C./mass part or more.
  4. 　前記セルロースアシレートフィルムは、加水分解防止剤をさらに含み、
    　前記加水分解防止剤の平均ｌｏｇＰ値が、７．５以上であることを特徴とする請求項１～３のいずれか一項に記載の偏光板。     The cellulose acylate film further comprises a hydrolysis inhibitor,
    The polarizing plate according to any one of claims 1 to 3, wherein an average log P value of the hydrolysis inhibitor is 7.5 or more.
  5. 　前記貼合面の算術平均粗さが、他方の面より大きいことを特徴とする請求項１～４のいずれか一項に記載の偏光板。 The polarizing plate according to any one of claims 1 to 4, wherein an arithmetic average roughness of the bonding surface is larger than that of the other surface.
  6. 　前記偏光板の偏光度が、９９．９９％以上であることを特徴とする請求項１～５のいずれか一項に記載の偏光板。 The polarizing plate according to any one of claims 1 to 5, wherein a degree of polarization of the polarizing plate is 99.99% or more.
  7. 　請求項１～６のいずれか一項に記載の偏光板が、具備されていることを特徴とする液晶表示装置。 A liquid crystal display device comprising the polarizing plate according to any one of claims 1 to 6.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110054997A (en) * 2013-06-28 2019-07-26 琳得科株式会社 Active energy ray-curable adhesive sheet and laminated body

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017013948A1 (en) * 2015-07-22 2017-01-26 コニカミノルタ株式会社 Polarizing plate and liquid-crystal display device in which same is used
WO2019160025A1 (en) 2018-02-14 2019-08-22 富士フイルム株式会社 Polymerizable liquid crystal composition, production method for polymerizable liquid crystal composition, optically anisotropic film, optical film, polarizing plate, and image display device

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08216320A (en) * 1995-02-14 1996-08-27 Bridgestone Corp Polarizing plate for liquid crystal display device
JP2008257199A (en) * 2007-03-15 2008-10-23 Sumitomo Chemical Co Ltd Photocurable adhesive agent, polarizing plate using the photocurable adhesive agent, method for production of the polarizing plate, optical member, and liquid crystal display device
JP2009265598A (en) * 2008-03-31 2009-11-12 Fujifilm Corp Protective film for sheet polarizer
JP2010008928A (en) * 2008-06-30 2010-01-14 Fujicopian Co Ltd Photocurable adhesive composition and polarizing plate using the same
JP2010271620A (en) * 2009-05-25 2010-12-02 Konica Minolta Opto Inc Polarizing plate protectingfilm
JP2010286603A (en) * 2009-06-10 2010-12-24 Fujifilm Corp Optical compensation film
JP2011105924A (en) * 2009-06-05 2011-06-02 Fujifilm Corp Cellulose ester film, optical compensation film, polarizing plate, and liquid crystal display

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001064301A (en) * 1999-08-24 2001-03-13 Konica Corp Cellulose ester film
JP2001131301A (en) * 1999-11-10 2001-05-15 Konica Corp Cellulose ester film
JP3849377B2 (en) * 1999-11-29 2006-11-22 コニカミノルタホールディングス株式会社 Optical film and manufacturing method thereof
US7252865B2 (en) * 2004-09-20 2007-08-07 Eastman Kodak Company Protective films containing compatible plasticizer compounds useful in polarizing plates for displays and their method of manufacture
WO2008023502A1 (en) * 2006-08-25 2008-02-28 Konica Minolta Opto, Inc. Optical film, method for manufacturing the same, and polarizing plate using the optical film
JP5286914B2 (en) * 2008-04-24 2013-09-11 東レ株式会社 Uncured sheet for optical waveguide, optical waveguide member and optical waveguide using the same
JP2009299014A (en) * 2008-05-12 2009-12-24 Fujifilm Corp Polymer film, phase difference film, polarizing plate, and liquid crystal display device
JP2011118339A (en) * 2009-04-28 2011-06-16 Fujifilm Corp Cellulose acylate laminate film, method for producing the same, polarizer, and liquid crystal display device
WO2011001700A1 (en) * 2009-06-30 2011-01-06 コニカミノルタオプト株式会社 Cellulose ester film, polarizing plate using same, and liquid crystal display device
CN102472857B (en) * 2009-07-15 2013-10-30 柯尼卡美能达精密光学株式会社 Polarizing plate, method of manufacturing same and liquid crystal display employing same
US20120295040A1 (en) * 2010-01-08 2012-11-22 Konica Minolta Advanced Layers ,Inc. Hard coat film, polarizing plate and liquid crystal display device
JP2014167494A (en) * 2011-06-22 2014-09-11 Konica Minolta Inc Cellulose acylate film and production method of the same, and polarizing plate and liquid crystal display device using the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08216320A (en) * 1995-02-14 1996-08-27 Bridgestone Corp Polarizing plate for liquid crystal display device
JP2008257199A (en) * 2007-03-15 2008-10-23 Sumitomo Chemical Co Ltd Photocurable adhesive agent, polarizing plate using the photocurable adhesive agent, method for production of the polarizing plate, optical member, and liquid crystal display device
JP2009265598A (en) * 2008-03-31 2009-11-12 Fujifilm Corp Protective film for sheet polarizer
JP2010008928A (en) * 2008-06-30 2010-01-14 Fujicopian Co Ltd Photocurable adhesive composition and polarizing plate using the same
JP2010271620A (en) * 2009-05-25 2010-12-02 Konica Minolta Opto Inc Polarizing plate protectingfilm
JP2011105924A (en) * 2009-06-05 2011-06-02 Fujifilm Corp Cellulose ester film, optical compensation film, polarizing plate, and liquid crystal display
JP2010286603A (en) * 2009-06-10 2010-12-24 Fujifilm Corp Optical compensation film

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110054997A (en) * 2013-06-28 2019-07-26 琳得科株式会社 Active energy ray-curable adhesive sheet and laminated body

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