WO2013191150A1 - Film de protection de plaque de polarisation et plaque de polarisation pourvue de ce dernier - Google Patents

Film de protection de plaque de polarisation et plaque de polarisation pourvue de ce dernier Download PDF

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Publication number
WO2013191150A1
WO2013191150A1 PCT/JP2013/066641 JP2013066641W WO2013191150A1 WO 2013191150 A1 WO2013191150 A1 WO 2013191150A1 JP 2013066641 W JP2013066641 W JP 2013066641W WO 2013191150 A1 WO2013191150 A1 WO 2013191150A1
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resin
polarizing plate
protective film
plate protective
solvent
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PCT/JP2013/066641
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English (en)
Japanese (ja)
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瀧本　正高
美典 玉川
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コニカミノルタ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • G02B1/105—
    • 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
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/08—Cellulose derivatives
    • C08J2401/10—Esters of organic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/08—Cellulose derivatives
    • C08J2401/14—Mixed esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/08—Cellulose derivatives
    • C08J2401/26—Cellulose ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates

Definitions

  • the present invention relates to a polarizing plate protective film and a polarizing plate provided with the same.
  • a liquid crystal display device generally includes a liquid crystal cell in which a transparent electrode, a liquid crystal layer, a color filter, and the like are sandwiched between glass plates, and two polarizing plates provided on both sides of the liquid crystal cell.
  • Each polarizing plate is usually configured by sandwiching a polarizer between two polarizing plate protective films, and a cellulose ester film such as triacetyl cellulose is used as the polarizing plate protective film.
  • TAC film triacetyl cellulose film
  • the moisture permeability deteriorates or the dimensional stability is lowered, especially in a thin film of less than 40 ⁇ m. Due to the significant decrease in physical properties, it was difficult to realize a thin polarizing plate.
  • the liquid crystal panel is manufactured by attaching a polarizing plate to the surface of the liquid crystal cell.
  • a polarizing plate depending on the situation such as poor attachment or defective polarizing plate, it is necessary to remove and reattach the polarizing plate (also called rework).
  • the stress at the breaking point of the film is high, and it is necessary to have a characteristic that does not break even by bending, but it is becoming difficult to ensure reworkability as the polarizing plate becomes larger and thinner. .
  • Patent Document 2 uses an acrylic resin and a cellulose ester resin, which are excellent in transparency and dimensional stability and have a low hygroscopic property, and are improved in brittleness, which is a drawback of acrylic resins, and are suitable for polarizing plate protective films.
  • This optical film does not have sufficient stress at break and bending strength, causing problems in reworkability.
  • the present invention has been made in view of the above-mentioned problems and situations, and the problem to be solved is the provision of a polarizing plate protective film having a high stress at break and bending strength, and the reworkability provided with the polarizing plate protective film. It is to provide an excellent polarizing plate.
  • the cause of the above problem of the resin composed of the acrylic resin and the cellulose ester resin is that the molecules of the acrylic resin and the cellulose ester resin do not form a film in a uniform compatible state.
  • the polarizing plate protective film containing the resin A and the resin B is an average of the resin A and the resin B as reworkability.
  • the heel also behaved as if it became another resin, and it was found that the stress at break and the bending strength may be greatly improved.
  • a polarizing plate protective film having at least a resin A and a resin B having different solubility in an organic solvent and having a film thickness within a range of 15 to 100 ⁇ m, and dissolving at a certain amount of resin, a certain amount of solvent, and a certain temperature
  • the resin A is a good solvent
  • the resin B is a poor solvent at least the minimum amount required to completely dissolve the resin A alone.
  • the polarizing plate protective film containing the constant amount of the resin A is dissolved at the constant temperature, the insoluble part remains and the mass of the resin A contained in the insoluble matter is
  • the polarizing plate protective film is characterized by being 10% or more based on the mass of the resin A contained in the polarizing plate protective film before dissolution.
  • a polarizing plate comprising the polarizing plate protective film according to any one of items 1 to 4.
  • the resin A in the polarizing plate protective film composed of the resin A and the resin B may not be dissolved and an insoluble part may remain. This is probably because the molecules of the resins A and B are entangled and the behavior of one molecule is developed. That is, the interaction between the constituent molecules of the resin A and the constituent molecules of the resin B is stronger than the interaction between the constituent molecules of the resin A and the solvent molecules, and there is a structural entanglement between the two. It is thought that it was inhibited. For this reason, it is considered that the stress at break increased. Further, even when stress such as bending is applied due to molecular entanglement, it is considered that the entanglement is loosened to some extent, the bending strength is increased, and cracks are less likely to occur.
  • the polarizing plate protective film of the present invention is a polarizing plate protective film having at least a resin A and a resin B having different solubility in an organic solvent and having a film thickness in a range of 15 to 100 ⁇ m, and having a certain amount of resin, In a certain amount of solvent and solubility evaluation test at a constant temperature, the resin A is a good solvent, but the resin B is a poor solvent.
  • the polarizing plate protective film containing the certain amount of the resin A is dissolved at the certain temperature using at least the minimum amount required to dissolve in the undissolved part, and the insoluble matter remains in the insoluble matter.
  • the mass of the resin A contained in the resin is 10% or more with respect to the mass of the resin A contained in the polarizing plate protective film before the dissolution.
  • the resin A is a cellulose ester resin or a cellulose ether resin because an effect of entanglement of the resin can be easily obtained by ingenuity of the blending method and insolubilization can be easily achieved.
  • the resin A is a cellulose ester resin or a cellulose ether resin
  • the resin B is an acrylic resin because an entanglement effect is easily obtained and insolubilization is facilitated.
  • the polarizing plate protective film of the present invention can be suitably provided for a polarizing plate.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • Resin A and Resin B When a film is produced by blending Resin A and Resin B, the properties of Resin A and Resin B are expressed as an average value only by normal blending. That is, the reworkability is generally the average value of the resin A and the resin B. However, although it was the same composition, it showed the behavior as if it became another resin, and found that the stress at break and the bending strength could be greatly improved.
  • the reworkability means that after a polarizing plate protective film and a polarizer are bonded together to produce a polarizing plate, the polarizing plate is once bonded to a glass substrate of a liquid crystal cell, and then the polarizing plate is peeled off again. It means the ability to re-paste.
  • a solvent a which is a good solvent for the resin A but a poor solvent for the resin B in a certain amount of resin, a certain amount of solvent, and a solubility evaluation test at a certain temperature.
  • the polarizing plate protective film containing the predetermined amount of the resin A is used at the constant temperature, using at least the minimum amount required for completely dissolving the resin A contained in the polarizing plate protective film alone. When dissolved, the insoluble part remains and the mass of the resin A contained in the insoluble material is 10 with respect to the mass of the resin A contained in the polarizing plate protective film before the dissolution. % Or more.
  • the polarizing plate protective film containing at least the resin A and the resin B having different solubility in the organic solvent is used at least at the minimum amount required for completely dissolving the resin A alone at the constant temperature.
  • the insoluble part remains and the mass of the resin A contained in the insoluble material is 10% with respect to the mass of the resin A contained in the polarizing plate protective film before the dissolution. If this is the case, the interaction between the constituent molecules of the resin A and the solvent molecules is stronger than the interaction between the constituent molecules of the resin A and the constituent molecules of the resin B, and there is a structural entanglement between them. It is thought that dissolution of A was inhibited.
  • the result of the solubility evaluation test reflects the interaction between the constituent molecules of the resin A and the constituent molecules of the resin B and the ease of structural entanglement between the two. Furthermore, this evaluation result shows the interaction between the constituent molecules of the resin A and the constituent molecules of the resin B when the resin A and the resin B are mixed (blended) regardless of the presence of the solvent, and the structural entanglement between the two. It can be considered as an index for inferring ease based on various experimental results described later.
  • “good solvent” refers to a solvent in which a base resin having a molecular weight of 10,000 or more dissolves in a range of 10 g or more with respect to 100 ml of the good solvent at 23 ° C. and no turbidity is observed.
  • the “poor solvent” refers to a solvent that dissolves a base resin having a molecular weight of 10,000 or more in a range of 5 g or less with respect to 100 ml of the poor solvent at 23 ° C.
  • the good solvent and the poor solvent differ from each other when the target resin is different.
  • a solvent a that is a good solvent for the resin A but a poor solvent for the resin B is used.
  • the resin A and the resin B to be evaluated are evaluated under the same conditions. Therefore, in the evaluation test of each evaluation sample, a certain amount of resin and a certain amount of solvent are used. It is necessary to evaluate with.
  • a cellulose ester resin when used as the resin A, it is preferable to adopt the following conditions as a certain amount of resin, a certain amount of solvent, and a certain temperature.
  • the fixed amount of resin used in the solubility evaluation test refers to 50 g of a base resin constituting a mass ratio of 10% by mass or more with respect to the polarizing plate protective film.
  • a certain amount of solvent refers to 100 ml of solvent used to dissolve 50 g of the base resin.
  • Constant temperature means 23 ° C.
  • the evaluation test is conducted by regarding each of the base resins having a mass ratio of 10% or more constituting the polarizing plate protective film as the resin A. Even when there are three or more kinds of base resins having a mass ratio of 10% or more, each resin is regarded as a resin A and an evaluation test is performed.
  • the amount by which resin A is completely dissolved alone is determined by the following method.
  • Resin A is stirred for 30 minutes in 100 ml of solvent at a temperature of 23 ° C.
  • the solubility By measuring the mass of the insoluble portion, the amount of the resin dissolved in 100 ml of the solvent, that is, the solubility can be determined. From this solubility, the minimum amount of solvent required to dissolve a certain amount of resin is calculated.
  • the target resin is a good or poor solvent.
  • the minimum amount required to completely dissolve 50 g of resin is determined to be 100 ml.
  • the evaluation test of the solubility of the polarizing plate protective film was carried out at 23 ° C. using 10 g of the polarizing plate protective film and the above-obtained at least the minimum amount of solvent a required for completely dissolving the resin A. Perform an evaluation test.
  • the amount of resin A contained in the polarizing plate protective film is calculated from the original blend ratio, and the minimum amount required for complete dissolution determined above is determined for this resin amount. For example, when the blend ratio of the resin A is 80% and there is no other additive, 8 g of the resin A is contained in the polarizing plate protective film 10 g. When the solubility determined above is 16 g / 100 ml, the minimum amount required to completely dissolve the resin A8 g contained in 10 g of the polarizing plate protective film is 50 ml.
  • Resin is made into a film having a thickness of 100 ⁇ m or less so that it can be easily dissolved, cut into an appropriate size, and stirred at a temperature of 23 ° C. for 30 minutes. If the dissolution time is too short, the insoluble part may remain due to the dissolution rate, and if the stirring time is increased, the soot in the insoluble part will behave like a single molecule. This is because the mass of the insoluble part may become inaccurate. After stirring for 30 minutes, the insoluble part is taken out and the amount of resin A in the insoluble part is measured.
  • the evaluation test is conducted by regarding each of the base resins having a mass ratio of 10% or more constituting the polarizing plate protective film as the resin A. Even when there are three or more kinds of base resins having a mass ratio of 10% or more, each resin is regarded as a resin A and an evaluation test is performed.
  • the mass of the resin A contained in the insoluble portion is 10% by mass or more based on the mass of the resin A contained in the polarizing plate protective film before dissolution. If so, the effect of the present invention can be exhibited. Preferably, it is 30% by mass or more with respect to the mass of the resin A before dissolution, and more preferably 50% by mass or more with respect to the mass of the resin A before dissolution.
  • the upper limit is not particularly limited, but in order to increase this ratio, it takes about 80% because the blending takes a long time or molecules may be cut by shearing during blending.
  • Quantitative analysis of the insoluble part can use NMR to estimate the degree of insolubilization of the blended resin from the total integral value of the protons at the peaks unique to each resin and the proportion of protons in the insoluble matter.
  • NMR can be measured using, for example, FT-NMR Lambda400 manufactured by JEOL.
  • Such solvents vary depending on the target resin, but can be selected from the following solvents through a solubility evaluation test.
  • chlorinated organic solvents include methylene chloride, chloroform, and non-chlorinated organic solvents include methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, gamma Butyrolactone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3 3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane Dimethyl sulfoxide (DMSO), acetonitrile and the like, methylene chloride, methyl acetate, vinegar E
  • the resin used as the resin A and the resin B is preferably a thermoplastic resin. These resins are used as a base resin. For example, it can be obtained by conducting the above-described solubility evaluation test from the following resins.
  • thermoplastic resin examples include cellulose ester resin, cellulose ether resin, polycarbonate resin, polyether sulfone resin, acrylic resin, polysulfone resin, polyarylate resin, polyethylene resin, polystyrene resin, polyvinyl chloride resin, polyamide resin, polyimide resin. , Polyester resin, polyether ketone resin, polyamideimide resin, polyesterimide resin, and alicyclic olefin polymer.
  • a cellulose ester resin, a cellulose ether resin, an acrylic resin, a polycarbonate resin, and a polyester resin are preferable from the viewpoint of manifesting the effects of the present invention. More preferred are cellulose ester resins, cellulose ether resins and acrylic resins.
  • Acrylic resins that can be used in the present invention also include methacrylic resins. Although it does not restrict
  • alkyl methacrylates having 2 to 18 carbon atoms in the alkyl group alkyl acrylates having 1 to 18 carbon atoms in the alkyl group, acrylic acid, and methacrylic acid.
  • Examples thereof include unsaturated nitrile, maleic anhydride, maleimide, N-substituted maleimide, and glutaric anhydride, and these can be used alone or in combination of two or more.
  • methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable from the viewpoint of thermal decomposition resistance and fluidity of the copolymer.
  • n-Butyl acrylate is particularly preferably used.
  • the acrylic resin used for the polarizing plate protective film of the present invention has a weight average molecular weight (Mw) of 80,000 or more, particularly in terms of brittleness as a polarizing plate protective film and transparency when mixed with, for example, a cellulose ester resin.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) of the acrylic resin is more preferably in the range of 80,000 to 1,000,000, particularly preferably in the range of 100,000 to 600,000, and most preferably in the range of 150,000 to 400,000.
  • the upper limit of the weight average molecular weight (Mw) of an acrylic resin is not specifically limited, It is a preferable form that it shall be 1 million or less from a viewpoint on manufacture.
  • the weight average molecular weight of the acrylic resin according to the present invention can be measured by gel permeation chromatography.
  • the measurement conditions are as follows.
  • the production method of the acrylic resin in the present invention is not particularly limited, and any known method such as suspension polymerization, emulsion polymerization, bulk polymerization, or solution polymerization may be used.
  • a polymerization initiator a normal peroxide type and an azo type can be used, and a redox type can also be used.
  • suspension or emulsion polymerization may be carried out within a range of 30 to 100 ° C.
  • bulk or solution polymerization may be carried out within a range of 80 to 160 ° C.
  • polymerization can be carried out using alkyl mercaptan or the like as a chain transfer agent.
  • acrylic resins can be used as the acrylic resin of the present invention.
  • Delpet 60N, 80N (Asahi Kasei Chemicals Co., Ltd.), Dialal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd.), KT75 (Electrochemical Industry Co., Ltd.) and the like can be mentioned. .
  • the cellulose ester resin that can be used in the present invention is preferably a cellulose ester resin substituted with an acyl group.
  • Cellulose ester resins have an acyl group total substitution degree of 2.0 to 3.0 and an acyl group of 3 to 7 carbon atoms, particularly from the viewpoint of improving brittleness and transparency when mixed with an acrylic resin, for example.
  • the group substitution degree is preferably in the range of 1.2 to 3.0.
  • the total degree of substitution is preferably 1.3 or less.
  • the total substitution degree of the acyl group of the cellulose ester resin is more preferably in the range of 2.5 to 3.0.
  • the acyl group may be an aliphatic acyl group or an aromatic acyl group. In the case of an aliphatic acyl group, it may be linear or branched and may further have a substituent.
  • the number of carbon atoms of the acyl group in the present invention includes an acyl group substituent.
  • the number of substituents X substituted on the aromatic ring is preferably 0 to 5. Also in this case, it is necessary to pay attention so that the substitution degree of the acyl group having 3 to 7 carbon atoms including the substituent is in the range of 1.2 to 3.0. For example, since the benzyl group has 7 carbon atoms, when it has a substituent containing carbon, the benzyl group has 8 or more carbon atoms and is not included in the acyl group having 3 to 7 carbon atoms. Become.
  • substituents substituted on the aromatic ring when the number of substituents substituted on the aromatic ring is 2 or more, they may be the same or different from each other, but they may be linked together to form a condensed polycyclic compound (for example, naphthalene, indene, indane, phenanthrene, quinoline). , Isoquinoline, chromene, chroman, phthalazine, acridine, indole, indoline, etc.).
  • a condensed polycyclic compound for example, naphthalene, indene, indane, phenanthrene, quinoline.
  • Isoquinoline chromene, chroman, phthalazine, acridine, indole, indoline, etc.
  • a structure having at least one kind of a substituted or unsubstituted aliphatic acyl group having 3 to 7 carbon atoms is used as a structure used in the cellulose resin of the present invention.
  • the cellulose ester resin of the present invention is preferably at least one selected from cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate benzoate, cellulose propionate, and cellulose butyrate, that is, having 3 carbon atoms. Or what has an acyl group of 4 as a substituent is preferable.
  • particularly preferable cellulose ester resins are cellulose acetate propionate and cellulose propionate.
  • the portion not substituted with an acyl group is usually present as a hydroxy group. These can be synthesized by known methods.
  • substitution degree of the acetyl group and the substitution degree of other acyl groups were determined by the method prescribed in ASTM-D817-96.
  • the weight average molecular weight (Mw) of the cellulose ester resin of the present invention is 75000 or more, particularly from the viewpoint of improvement in compatibility with acrylic resin, brittleness and heat resistance, and is preferably in the range of 75,000 to 300,000. More preferably within the range of ⁇ 24,000, particularly preferably within the range of 160000 to 240000.
  • Cellulose ether resin Cellulose ether can also be used suitably. Examples include, but are not limited to, methylcellulose, ethylcellulose, carboxymethylcellulose, carboxymethylethylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, and the like.
  • cellulose ether resins having an alkyl group substitution degree of 2.0 to 2.80 such as cellulose methyl ether, cellulose ethyl ether, and cellulose propyl ether are more preferable.
  • the cellulose ether resin may be used alone or in combination with the cellulose ester resin.
  • the content of the cellulose ether resin and the cellulose ester resin is not particularly limited, assuming that the total of the cellulose ether resin and the cellulose ether resin is 100% by mass, but the cellulose ester resin is 80 to 99% by mass, the cellulose ether 1 to It is preferably in the range of 20% by mass, more preferably in the range of 85 to 97% by mass of cellulose acylate and 3 to 15% by mass of cellulose ether.
  • the molecular weight of the cellulose ether resin to be used is not particularly limited.
  • the number average molecular weight is 30,000 to 150. 1,000 (polystyrene equivalent) is preferably used.
  • the molecular weight is 30,000 or more, the film does not become brittle.
  • the combination of the resin A according to the polarizing plate protective film of the present invention can be obtained by conducting the solubility evaluation test described above.
  • the combination of resins is not particularly limited as long as the combination satisfies the requirements for the solubility evaluation test.
  • the following combinations of resins can be subjected to the solubility evaluation test.
  • the resin A is preferably a cellulose ester resin or a cellulose ether resin.
  • the good solvent for the cellulose ester resin or the cellulose ether resin include acetonitrile, tetrahydrofuran (THF), dichloromethane and the like.
  • a solvent that is a poor solvent is selected for the other resin B to be combined, and a solubility evaluation test is performed using the solvent to select the resin A according to the polarizing plate protective film of the present invention.
  • the resin A is a cellulose ester or a cellulose ether resin because an effect of entanglement of the resin can be easily obtained by ingenuity of the blending method, and the resin A can be easily insolubilized.
  • the resin A according to the protective film for polarizing plate of the present invention is a cellulose ester resin or a cellulose ether resin
  • the resin B is an acrylic resin because an entanglement effect is easily obtained and insolubilization is facilitated.
  • the acrylic resin and the cellulose ester resin are preferably contained in a mass ratio of 95: 5 to 30:70. More preferred is a mass ratio of 95: 5 to 50:50, and still more preferred is a mass ratio in the range of 90:10 to 60:40.
  • the weight average molecular weight (Mw) of the acrylic resin, the weight average molecular weight (Mw) of the cellulose ester resin and the degree of substitution in the polarizing plate protective film of the present invention are classified using the difference in solubility in the solvent of both resins. Then, it is obtained by measuring each.
  • the total mass of the acrylic resin (A) and the cellulose ester resin (B) in the polarizing plate protective film of the present invention is preferably 55% by mass or more of the polarizing plate protective film, more preferably 60% by mass or more, Most preferably, it is 70 mass% or more.
  • These resins can be synthesized by a known method.
  • the polarizing plate protective film of the present invention is not dependent on the resin blending method, and the expression of the effect is determined by the solubility evaluation test of the polarizing plate protective film described above.
  • a polarizing plate protective film using a resin blended by the method is preferable.
  • the solvent addition kneading method involves kneading in a swollen state using a small amount of solvent of about 2 to 20% by mass with respect to the resin. This is a kneading method for increasing the interaction.
  • the pulverization combined method is a method of increasing the mixing efficiency by pulverizing the resin in advance with a ball mill or the like, reducing the particle size with a disperser, and then kneading and pelletizing.
  • the high shear method is a kneading method in which the shear rate is increased and the interaction between molecules is increased as compared with a normal blend method.
  • the shear rate is preferably about 4000 sec ⁇ 1 or more.
  • the polarizing plate protective film of this invention can contain additives, such as a plasticizer, a ultraviolet absorber, antioxidant, other than resin as base resin mentioned above.
  • a plasticizer in the polarizing plate protective film of the present invention, a plasticizer can be used in combination in order to improve the fluidity and flexibility of the composition.
  • the plasticizer include phthalate ester, fatty acid ester, trimellitic ester, phosphate ester, polyester, and epoxy.
  • polyester-based and phthalate-based plasticizers are preferably used.
  • Polyester plasticizers are superior in non-migration and extraction resistance compared to phthalate ester plasticizers such as dioctyl phthalate, but are slightly inferior in plasticizing effect and compatibility.
  • the polyester plasticizer is a reaction product of a monovalent or tetravalent carboxylic acid and a monovalent or hexavalent alcohol, and is mainly obtained by reacting a divalent carboxylic acid with a glycol.
  • Representative divalent carboxylic acids include glutaric acid, itaconic acid, adipic acid, phthalic acid, azelaic acid, sebacic acid and the like.
  • glycol examples include glycols such as ethylene, propylene, 1,3-butylene, 1,4-butylene, 1,6-hexamethylene, neopentylene, diethylene, triethylene, and dipropylene. These divalent carboxylic acids and glycols may be used alone or in combination.
  • the ester plasticizer may be any of ester, oligoester, and polyester types, and the molecular weight is preferably in the range of 100 to 10,000, but preferably in the range of 600 to 3000, the plasticizing effect is large.
  • the viscosity of the plasticizer has a correlation with the molecular structure and molecular weight, but in the case of an adipic acid plasticizer, a range of 200 to 5000 mPa ⁇ s (25 ° C.) is preferable in view of compatibility and plasticization efficiency. Furthermore, some polyester plasticizers may be used in combination.
  • the plasticizer is preferably added in an amount of 0.5 to 30 parts by mass with respect to 100 parts by mass of the polarizing plate protective film of the present invention.
  • the addition amount of the plasticizer is within 30 parts by mass, the surface is not sticky.
  • the polarizing plate protection of the present invention preferably contains an ultraviolet absorber, and examples of the ultraviolet absorber used include benzotriazole, 2-hydroxybenzophenone and salicylic acid phenyl ester.
  • the ultraviolet absorber used include benzotriazole, 2-hydroxybenzophenone and salicylic acid phenyl ester.
  • ultraviolet absorbers having a molecular weight of 400 or more are less likely to volatilize at a high boiling point and are difficult to disperse even during high-temperature molding, so that the weather resistance is effectively improved with a relatively small amount of addition. be able to.
  • Examples of the ultraviolet absorber having a molecular weight of 400 or more include 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2-benzotriazole, 2,2-methylenebis [4- (1, 1,3,3-tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol], bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ( Hindered amines such as 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid Bis (1,2,2,6,6-pentamethyl-4-piperidyl), 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] Such as til] -4- [3- (3,5-di-tert-butyl
  • 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2-benzotriazole and 2,2-methylenebis [4- (1,1,3,3- Tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol] is particularly preferred.
  • antioxidant what is generally known can be used for a polarizing plate protective film as antioxidant.
  • lactone, sulfur, phenol, double bond, hindered amine, and phosphorus compounds can be preferably used.
  • those including those commercially available from BASF Japan under the trade names of “IrgafosXP40” and “IrgafosXP60” are preferable.
  • the phenolic compound preferably has a 2,6-dialkylphenol structure.
  • BASF Japan Ltd. “Irganox 1076”, “Irganox 1010”, and ADEKA “ADEKA STAB AO-50” are trade names. What is marketed is preferable.
  • the phosphorous compounds are, for example, from Sumitomo Chemical Co., Ltd., “Sumizer GP”, from ADEKA Co., Ltd., “ADK STAB PEP-24G”, “ADK STAB PEP-36” and “ADK STAB 3010”, from BASF Japan Co., Ltd. IRGAFOS P-EPQ ", commercially available from Sakai Chemical Industry Co., Ltd. under the trade name" GSY-P101 "is preferred.
  • the hindered amine compound is preferably commercially available from BASF Japan KK under the trade names of “Tinuvin 144” and “Tinvin 770”, and from ADEKA Corporation as “ADK STAB LA-52”.
  • the above-mentioned sulfur compounds are preferably commercially available from Sumitomo Chemical Co., Ltd. under the trade names “Sumilizer TPL-R” and “Sumilizer TP-D”.
  • the above-mentioned double bond compound is preferably commercially available from Sumitomo Chemical Co., Ltd. under the trade names of “Sumilizer GM” and “Sumilizer GS”.
  • the amount of these antioxidants and the like to be added is appropriately determined in accordance with the process for recycling and use, but generally 0.05 to 20% by mass, preferably with respect to the resin as the main raw material of the film Is added in the range of 0.1 to 1% by mass.
  • antioxidants can obtain a synergistic effect by using several different types of compounds in combination rather than using only one kind.
  • the combined use of lactone, phosphorus, phenol and double bond compounds is preferred.
  • an antistatic agent can be added to the polarizing plate protective film of the present invention to impart antistatic performance to the optical film.
  • a flame retardant acrylic resin composition containing a phosphorus flame retardant may be used.
  • Phosphorus flame retardants used here include red phosphorus, triaryl phosphate ester, diaryl phosphate ester, monoaryl phosphate ester, aryl phosphonate compound, aryl phosphine oxide compound, condensed aryl phosphate ester, halogenated alkyl phosphorus. Examples thereof include one or a mixture of two or more selected from acid esters, halogen-containing condensed phosphates, halogen-containing condensed phosphonates, halogen-containing phosphites, and the like.
  • triphenyl phosphate 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenylphosphonic acid, tris ( ⁇ -chloroethyl) phosphate, tris (dichloropropyl) Examples thereof include phosphate and tris (tribromoneopentyl) phosphate.
  • the polarizing plate protective film may be a film manufactured by the solution casting method or a film manufactured by the melt casting method, but is preferably a film manufactured by the melt casting method.
  • the solution casting method forms a film by casting a solution dissolved in a solvent and evaporating and drying the solvent. Therefore, the equipment investment and the production cost for the production line such as the removal of the solvent and the recovery of the evaporated solvent are enormous.
  • the above-described drying load and equipment load do not occur.
  • fine foaming is likely to occur at the time of molding, so that optical properties such as haze, transmittance, and retardation are deteriorated, and coating failure is likely to occur in the post-processing process.
  • the resin used for the polarizing plate protective film of the present invention is melt cast, not only the mechanical strength is increased, but also the occurrence of haze and the like is reduced, the optical characteristics are improved, and the coating failure can be reduced.
  • Pelletization may be performed by a known method. For example, a polymer, a plasticizer, and other additives that form a film are fed to an extruder with a feeder and kneaded using a single-screw or twin-screw extruder. Extruded into a shape, water-cooled or air-cooled and cut.
  • Pre-drying of raw materials before extrusion is important for preventing decomposition of the raw materials.
  • the polymer forming the polarizing plate protective film is easy to absorb moisture, it is dried for 3 hours or more in a temperature range of 70 to 140 ° C. with a dehumidifying hot air dryer or vacuum dryer, and the moisture content is set to 300 ppm or less, and further to 100 ppm or less. It is preferable.
  • Additives may be mixed before being supplied to the extruder, or may be supplied by individual feeders. A small amount of an additive such as an antioxidant is preferably mixed in advance in order to mix uniformly.
  • Mixing of the antioxidants may be performed by mixing solids, and if necessary, the antioxidant may be dissolved in a solvent and impregnated with a polymer that forms a polarizing plate protective film, or mixed. You may spray and mix.
  • a vacuum nauter mixer or the like is preferable because drying and mixing can be performed simultaneously. Further, if the contact with air, such as the exit from the feeder unit or die, it is preferable that the atmosphere such as dehumidified air and dehumidified N 2 gas.
  • the extruder is preferably processed at as low a temperature as possible so that the resin can be pelletized so that the resin does not deteriorate (molecular weight reduction, coloring, gel formation, etc.).
  • a twin screw extruder it is preferable to rotate in the same direction using a deep groove type screw. From the uniformity of kneading, the meshing type is preferable.
  • the produced pellets are extruded using a single-screw or twin-screw type extruder, the melting temperature Tm at the time of extrusion is about 200 to 350 ° C., filtered by a filtration device to remove foreign matters, and then cast from a T die into a film. Then, it solidifies on the cooling roll and casts while pressing with the elastic touch roll.
  • Tm is the temperature of the die exit portion of the extruder.
  • defects are also referred to as die lines, but in order to reduce surface defects such as die lines, it is preferable to have a structure in which the resin retention portion is minimized in the piping from the extruder to the die. . It is preferable to use a die that has as few scratches as possible inside the lip.
  • the inner surface that comes into contact with the molten resin is preferably subjected to surface treatment that makes it difficult for the molten resin to adhere to the surface by reducing the surface roughness or using a material with low surface energy.
  • a hard chrome plated or ceramic sprayed material is polished so that the surface roughness is 0.2 S or less.
  • the cooling roll is a roll having a structure in which a heat medium or a coolant that can be controlled in temperature flows with a highly rigid metal roll, and the size is not limited, but the film is melt extruded.
  • the diameter of the cooling roll is usually about 100 mm to 1 m.
  • the surface material of the cooling roll includes carbon steel, stainless steel, aluminum, titanium and the like. Further, in order to increase the hardness of the surface or improve the releasability from the resin, it is preferable to perform a surface treatment such as hard chrome plating, nickel plating, amorphous chrome plating, or ceramic spraying.
  • the surface roughness of the chill roll surface is preferably 0.1 ⁇ m or less in terms of Ra, and more preferably 0.05 ⁇ m or less.
  • the smoother the roll surface the smoother the surface of the resulting film.
  • the surface processed is further polished to have the above-described surface roughness.
  • Examples of the elastic touch roll include JP-A-03-124425, JP-A-08-224772, JP-A-07-1000096, JP-A-10-272676, WO97 / 028950, JP-A-11-235747, JP-A-2002-36332.
  • No. 2005-172940 and JP-A 2005-280217 can use a silicon rubber roll coated with a thin film metal sleeve.
  • the film obtained as described above is preferably stretched by a stretching operation after passing through a step in contact with a cooling roll.
  • the stretching method a known roll stretching machine or tenter can be preferably used.
  • the stretching temperature is usually preferably in the temperature range of Tg to Tg + 60 ° C. of the resin constituting the film.
  • the thickness of the polarizing plate protective film of the present invention is in the range of 15 to 100 ⁇ m. When it becomes thinner than 15 ⁇ m, the strength of the polarizing plate protective film is lowered and the reworkability is inferior. On the other hand, if the thickness of the polarizing plate protective film exceeds 100 ⁇ m, not only the cost is increased but also the bending strength is lowered and the reworkability is lowered, which is not preferable.
  • the end Before winding, the end may be slit and cut to the product width, and knurled (embossed) may be applied to both ends to prevent sticking and scratching during winding.
  • the knurling method can process a metal ring having an uneven pattern on its side surface by heating or pressing.
  • grip part of the clip of both ends of a film is cut out and reused.
  • a polarizing plate When using the protective film for polarizing plates of this invention, a polarizing plate can be produced by a general method. It is preferable that an adhesive layer is provided on the back surface side of the protective film for polarizing plate of the present invention, and is bonded to at least one surface of a polarizer produced by dipping and stretching in an iodine solution.
  • the polarizing plate protective film of the present invention may be used on the other surface, or another polarizing plate protective film may be used, but it is preferable to use the polarizing plate protective film of the present invention on both sides.
  • protective films include cellulose ester films (for example, Konica Minoltac KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KV8UY-HA, KV8UX-RH Advanced Layer Co., Ltd.) is preferably used.
  • cellulose ester films for example, Konica Minoltac KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KV8UY-HA, KV8UX-RH Advanced Layer Co., Ltd.
  • a polarizer which is a main component of a polarizing plate, is an element that transmits only light having a plane of polarization in a certain direction.
  • a typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol. There are one in which iodine is dyed on a system film and one in which dichroic dye is dyed.
  • the polarizer is formed by forming a polyvinyl alcohol aqueous solution into a film and dyeing the film by uniaxial stretching or dyeing or uniaxially stretching, and then performing a durability treatment with a boron compound.
  • a pressure-sensitive adhesive having a storage elastic modulus at 25 ° C. in the range of 1.0 ⁇ 10 4 Pa to 1.0 ⁇ 10 9 Pa in at least a part of the pressure-sensitive adhesive layer is used.
  • a curable pressure-sensitive adhesive that forms a high molecular weight body or a crosslinked structure by various chemical reactions after the pressure-sensitive adhesive is applied and bonded is suitably used.
  • urethane adhesives examples include, for example, urethane adhesives, epoxy adhesives, aqueous polymer-isocyanate adhesives, curable adhesives such as thermosetting acrylic adhesives, moisture-curing urethane adhesives, polyether methacrylate types
  • curable adhesives such as thermosetting acrylic adhesives, moisture-curing urethane adhesives, polyether methacrylate types
  • anaerobic pressure-sensitive adhesives such as ester-based methacrylate type and oxidized polyether methacrylate, cyanoacrylate-based instantaneous pressure-sensitive adhesives, and acrylate-peroxide-based two-component instantaneous pressure-sensitive adhesives.
  • the above-mentioned pressure-sensitive adhesive may be a one-component type or a type in which two or more components are mixed before use.
  • the pressure-sensitive adhesive may be a solvent system using an organic solvent as a medium, or an aqueous system such as an emulsion type, a colloidal dispersion type, or an aqueous solution type that is a medium containing water as a main component. It may be a solvent type.
  • concentration of the pressure-sensitive adhesive solution may be appropriately determined depending on the film thickness after adhesion, the coating method, the coating conditions, and the like, and is usually in the range of 0.1 to 50% by mass.
  • A-1 Cellulose acetate propionate: acyl group total substitution degree 2.75, acetyl group substitution degree 0.19, propionyl group substitution degree 2.56, Mw 200000
  • Resin A 20.00 parts by mass Resin B (B-1) 80.00 parts by mass Additive GSY-P101 (manufactured by Sakai Chemical Industry Co., Ltd.) 0.25 parts by mass Irganox 1010 (BASF Japan Ltd.) Manufactured) 0.50 parts by mass Sumilizer GS (manufactured by Sumitomo Chemical Co., Ltd.) 0.24 parts by mass
  • Additive GSY-P101 manufactured by Sakai Chemical Industry Co., Ltd.
  • Irganox 1010 BASF Japan Ltd.
  • Sumilizer GS manufactured by Sumitomo Chemical Co., Ltd.
  • Blend method 1 is a solvent addition kneading method.
  • methanol is supplied to the liquid addition nozzle installed at the position immediately before the kneading disk by using a plunger pump so as to be 5% with respect to the resin composition, and methanol is supplied from the liquid addition nozzle into the cylinder. Injected.
  • the resin is heated to 230 ° C., melted, extruded from a strand die mounted on a twin screw extruder, and cut to form a cylindrical resin A-1, a resin B-1 having a length of 4 mm and a diameter of 3 mm.
  • the pellet of the resin composition 1 which blended the additive was produced.
  • the pellets were dried with a hopper at 100 ° C. for 4 hours.
  • the water content at this time was 520 ppm.
  • This pellet was made into a film using the following single screw extruder.
  • the extruder and T-die were set at a temperature of 250 ° C.
  • the T-die is a coat hanger type, has a width of 150 mm, has an inner wall plated with hard chrome, and has a mirror finish with a surface roughness of 0.1S.
  • the lip gap of the T die was set to 1 mm.
  • the extruded film was taken up with a cast roll having a surface temperature of 120 ° C., cooled to room temperature, and formed into a film having an average film thickness of 110 ⁇ m before stretching.
  • the film was heated to 165 ° C., stretched 2.1 times in the MD (Machine Direction) direction and 2.1 times in the TD (Transverse Direction) direction, and wound to prepare a polarizing plate protective film 1 having an average film thickness of 25 ⁇ m. .
  • Resin compositions 2-16 and Polarizing Plate Protective Films 2-16 were prepared in the same manner as in the preparation of resin composition 1, except that resin A-1 and resin B-1, and only the blending method and film forming method were changed as shown in Table 1. 2 to 16 were produced.
  • the blending method and film forming method are shown below.
  • Blending method 2 is a pulverization combined method.
  • Resin A, Resin B, and additives were mixed at 2300 r / min for 60 seconds using a Henschel mixer. Then, it grind
  • the mixed and pulverized thermoplastic resin composition was dried at 100 ° C. for 4 hours. The water content at this time was 510 ppm.
  • the resin was heated to 250 ° C., melted, and extruded from a T die attached to a twin screw extruder to produce a film.
  • the T-die is a coat hanger type, has a width of 150 mm, has an inner wall plated with hard chrome, and has a mirror finish with a surface roughness of 0.1S.
  • the lip gap of the T die was set to 1 mm.
  • the extruded film was taken up with a cast roll having a surface temperature of 120 ° C., cooled to room temperature, and formed into a film having an average film thickness of 110 ⁇ m before stretching. Subsequently, the film was heated to 165 ° C., stretched 2.1 times in the MD (Machine Direction) direction and 2.1 times in the TD (Transverse Direction) direction, and wound to prepare a polarizing plate protective film having an average film thickness of 25 ⁇ m.
  • Blend method 3 is a high shear method.
  • Resin A, resin B, and additives were mixed in a V-type mixer for 30 minutes, then charged from the hopper of a DSM twin-screw kneader and kneaded at 250 ° C. for 15 minutes. At this time, the shear rate was set to 4000 sec ⁇ 1 by adjusting the distance between the screw and the cylinder and the screw rotation speed.
  • extrusion was performed from a T die (coat hanger type, width 55 mm, lip interval 1 mm) attached to the injection port.
  • the extruded film was taken up by a cast roll having a surface temperature of 120 ° C. and cooled to room temperature to obtain a film having a width of 50 mm.
  • the average film thickness of the polarizing plate protective film was adjusted to 25 ⁇ m by adjusting the extrusion amount of the resin and the take-up speed.
  • Blending method 4 is a normal pelletizing method.
  • Resin is a resin composition in which cylindrical resins A and B having a length of 4 mm and a diameter of 3 mm are blended by extruding and cutting a resin from a strand die mounted on a twin-screw extruder by heating and melting at 230 ° C. A pellet was prepared. The pellets were dried with a hopper at 100 ° C. for 4 hours. The water content at this time was 520 ppm.
  • This pellet was made into a film using the following single screw extruder.
  • Nitrogen gas was sealed from the vicinity of the material supply port, and the inside of the extruder 1 was kept in a nitrogen atmosphere.
  • the temperature of the extruder 1 and the T die was set to 250 ° C.
  • the T-die is a coat hanger type, has a width of 150 mm, has an inner wall plated with hard chrome, and has a mirror finish with a surface roughness of 0.1S.
  • the lip gap of the T die was set to 1 mm.
  • the extruded film was taken up with a cast roll having a surface temperature of 120 ° C., cooled to room temperature, and formed into a film having an average film thickness of 110 ⁇ m before stretching. Subsequently, the film was heated to 165 ° C., stretched 2.1 times in the MD (Machine Direction) direction and 2.1 times in the TD (Transverse Direction) direction, and wound to prepare a polarizing plate protective film having an average film thickness of 25 ⁇ m.
  • the polarizing plate protective film 1 will be described as an example.
  • resin A-1 is a good solvent, A-1 is usually not included in the insoluble matter. However, by blending by blending method 1, resin A-1 that should be dissolved does not dissolve and is not dissolved. It can be seen that the resin A-1 and the resin B-1 are entangled in the melt.
  • this evaluation result shows the interaction between the constituent molecules of the resin A and the constituent molecules of the resin B when the resin A and the resin B are mixed (blended) regardless of the presence of the solvent, and the structural entanglement between the two. It may be an index for inferring ease.
  • the polarizing plate protective film was cut out by 70 mm (TD: width direction) ⁇ 10 mm (MD: longitudinal direction), and the tensile stress at break was measured at an environment of 23 ° C. and 55% at a chuck length of 50 mm and a speed of 50 mm / min.
  • the polarizing plate protective film was cut out at 100 mm (TD) ⁇ 10 mm (MD), folded at the central part in the vertical direction once into a mountain fold and a valley fold, and this evaluation was measured three times. It was evaluated as follows. In addition, breaking of evaluation here represents having broken into two or more pieces.
  • the polarizing plate protective films 1 to 11 of the present invention have a good solvent for the base resin compared to the comparative polarizing plate protective films 12 to 16, even though the resin composition is a good solvent. It can be seen that the proportion of insolubilized resin is high, and the stress at break and the bending strength are good. Further, it can be seen that the polarizing plate protective film of the present invention produced by the melt casting method has few roll stains, bubbles and perforation failures when forming a film-like material, and has good haze.
  • Example 2 Production of Polarizing Plates 1 to 16 >> A 120 ⁇ m-thick polyvinyl alcohol film was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide, and 100 g of water for 60 seconds, and then immersed in an aqueous solution at 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid, and 100 g of water. . This was washed with water and dried to obtain a polarizing film.
  • the polarizing film and the prepared polarizing plate protective films 1 to 16 were bonded to prepare polarizing plates 1 to 16, respectively.
  • Step 1 Polarizing plate protective films 1 to 16 were each immersed in a 2 mol / L sodium hydroxide solution at 50 ° C. for 90 seconds, then washed with water and dried.
  • a commercially available cellulose ester film was immersed in a 2 mol / L sodium hydroxide solution at 50 ° C. for 90 seconds, then washed with water and dried.
  • Step 2 The polarizing film described above was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.
  • Step 3 Excess adhesive adhered to the polarizing film in Step 2 was lightly removed, and it was sandwiched by using two identical polarizing plate protective films treated with alkali in Step 1 and laminated.
  • Step 4 The two rotating rollers were bonded together at a pressure of 20 to 30 N / cm 2 and a speed of about 2 m / min. At this time, care was taken to prevent bubbles from entering.
  • Step 5 The sample prepared in Step 4 in a dryer at 80 ° C. was dried for 2 minutes to prepare polarizing plates 1 to 16, respectively.
  • Each of the polarizing plates 1 to 16 was cut into a size of 100 mm ⁇ 100 mm, and attached to a glass plate using a substrate-less double-sided tape LUCIACS CS9621T (manufactured by Nitto Denko Corporation). After aging at 23 ° C. and 55% for 24 hours, the polarizing plate was peeled off from the glass plate by hand, and the state of the film at that time was evaluated as follows. ⁇ : The film can be peeled cleanly without tearing. ⁇ : The film sometimes shreds but can be removed somehow. ⁇ : The film is immediately shredded and cannot be peeled. Table 2 shows the above results.
  • Example 3 In the production of the polarizing plate protective film 1 of Example 1, the thickness of the film before stretching was changed by adjusting the extrusion amount of the resin by changing the screw rotation speed of the single screw extruder, and the average film thickness after stretching. However, it adjusted so that it might become 12 micrometers, 15 micrometers, 100 micrometers, and 120 micrometers, respectively, and produced the polarizing plate protective film, respectively. Next, in the same manner as in the production of the polarizing plate 1 described in Example 2, a corresponding polarizing plate was produced.
  • the polarizing plate protective film of the present invention has a high stress at break and bending strength, and can be suitably used for a polarizing plate having excellent reworkability.

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Abstract

La présente invention a pour objet de proposer un film de protection de plaque de polarisation qui présente une contrainte en pointe de fissure élevée et une résistance à la flexion élevée, ainsi qu'une plaque de polarisation qui est pourvue d'un tel film de protection de plaque de polarisation et qui présente une excellente aptitude au remaniement. Ce film de protection de plaque de polarisation comprend au moins une résine (A) et une résine (B) qui présentent des solubilités différentes dans des solvants organiques et possède une épaisseur de film comprise entre 15 et 100 µm, et est caractérisé en ce que, lors des tests d'évaluation de la solubilité d'une quantité prescrite de résine dans une quantité prescrite de solvant à une température prescrite, lorsque la dissolution est effectuée sous certaines conditions à l'aide d'au moins la quantité minimale d'un solvant (a), qui est un bon solvant de la résine (A) mais un mauvais solvant de la résine (B), nécessaire pour dissoudre complètement la seule résine (A), une partie non dissoute subsiste et la masse de la résine (A) dans la matière non dissoute fait au moins 10 % en poids par rapport à la résine (A) contenue dans le film de protection de plaque de polarisation avant la dissolution.
PCT/JP2013/066641 2012-06-21 2013-06-18 Film de protection de plaque de polarisation et plaque de polarisation pourvue de ce dernier WO2013191150A1 (fr)

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JP2012139304A JP2015163907A (ja) 2012-06-21 2012-06-21 偏光板保護フィルム及びそれが具備された偏光板
JP2012-139304 2012-06-21

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6365728B1 (ja) * 2017-05-25 2018-08-01 富士ゼロックス株式会社 樹脂組成物および樹脂成形体
WO2019171611A1 (fr) * 2018-03-06 2019-09-12 富士ゼロックス株式会社 Composition de résine, et corps moulé de résine

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JP6365728B1 (ja) * 2017-05-25 2018-08-01 富士ゼロックス株式会社 樹脂組成物および樹脂成形体
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