WO2015020046A1 - Film polymère à base d'alcool vinylique - Google Patents

Film polymère à base d'alcool vinylique Download PDF

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Publication number
WO2015020046A1
WO2015020046A1 PCT/JP2014/070605 JP2014070605W WO2015020046A1 WO 2015020046 A1 WO2015020046 A1 WO 2015020046A1 JP 2014070605 W JP2014070605 W JP 2014070605W WO 2015020046 A1 WO2015020046 A1 WO 2015020046A1
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WIPO (PCT)
Prior art keywords
film
group
vinyl alcohol
alcohol polymer
pva
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PCT/JP2014/070605
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English (en)
Japanese (ja)
Inventor
勝啓 高藤
磯▲ざき▼　孝徳
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株式会社クラレ
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Application filed by 株式会社クラレ filed Critical 株式会社クラレ
Priority to KR1020167003468A priority Critical patent/KR102216810B1/ko
Priority to JP2014557262A priority patent/JP6420153B2/ja
Priority to CN201480042973.XA priority patent/CN105431751B/zh
Publication of WO2015020046A1 publication Critical patent/WO2015020046A1/fr

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Classifications

    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
    • 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
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • 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
    • C08J2329/00—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 at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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

Definitions

  • the present invention relates to a vinyl alcohol polymer film useful as a raw film for producing an optical film, and a method for producing an optical film such as a polarizing film using the same.
  • a polarizing plate having a light transmission and shielding function is a basic component of a liquid crystal display (LCD) together with a liquid crystal that changes a polarization state of light.
  • LCD liquid crystal display
  • Many polarizing plates have a structure in which a protective film such as a cellulose triacetate (TAC) film is bonded to the surface of a polarizing film.
  • TAC cellulose triacetate
  • a polarizing film a vinyl alcohol polymer film (hereinafter referred to as “vinyl alcohol-based heavy film”) is used.
  • iodine based dye coalescing the may be referred to as" PVA ) in a matrix formed by uniaxial stretching (I 3 - and I 5 -, etc.) or a dichroic dye such as dichroic organic dyes which are adsorbed Has become the mainstream.
  • LCDs have come to be used in a wide range of small devices such as calculators and watches, mobile phones, notebook computers, liquid crystal monitors, liquid crystal color projectors, liquid crystal televisions, in-vehicle navigation systems, and measurement devices used indoors and outdoors.
  • polarizing films there has been a demand for higher display quality.
  • high performance is also demanded for polarizing films.
  • polarizing films that have high degree of polarization and transparency, excellent optical properties, and excellent hue and durability. ing.
  • an object of the present invention is to provide a PVA film capable of easily producing an optical film excellent in any of optical properties, hue and durability, and a method for producing an optical film using the PVA film.
  • the above problem is solved if the total ratio of the amount of crystal components and the amount of constrained amorphous components in the PVA film is within a specific range.
  • the present invention was completed through further studies based on the finding and the findings.
  • the present invention [1] From the spin-spin relaxation time T 2 obtained by performing pulse NMR measurement (observation nucleus: 1 H) after processing at 60 ° C. for 1 hour, the amount of crystal component (a 1 ), the amount of constrained amorphous component (a 2 ) And the amount of amorphous component (a 3 ), the amount of crystal component (a 1 ) relative to the sum of the amount of crystal component (a 1 ), the amount of constrained amorphous component (a 2 ), and the amount of amorphous component (a 3 ) (a 1 ) and a PVA film in which the total proportion of the constrained amorphous component amount (a 2 ) is 10 to 32%; [2] crystalline component amount (a 1), are constrained amorphous component amount (a 2) and amorphous component amount (a 3) restraining amorphous component amount to the sum of (a 2) the proportion of 5% or more The PVA film of [1] above; [3] The PVA contained in the
  • R 1 represents a hydrogen atom, a methyl group or an ethyl group.
  • R 2 represents a hydrogen atom, a methyl group or an ethyl group
  • X 2 represents a hydroxyalkyl group having 2 or more carbon atoms having one or more hydroxyl groups.
  • X 3 and X 4 each independently represent a hydroxyalkyl group having 1 or more carbon atoms having one or more hydroxyl groups.
  • X 3 and X 4 each independently represent a hydroxyalkyl group having 1 or more carbon atoms having one or more hydroxyl groups.
  • a PVA film capable of easily producing an optical film excellent in any of optical properties, hue and durability, and a method for producing an optical film using the PVA film are provided.
  • the PVA film of the present invention is processed at 60 ° C. for 1 hour and then subjected to pulsed NMR measurement (observation nucleus: 1 H). From the spin-spin relaxation time T 2 obtained, the crystal component amount (a 1 ), constrained amorphous component When the amount (a 2 ) and the amount of amorphous component (a 3 ) are determined, the crystal with respect to the sum of the amount of crystal component (a 1 ), the amount of restrained amorphous component (a 2 ) and the amount of amorphous component (a 3 ) The total proportion of the component amount (a 1 ) and the constrained amorphous component amount (a 2 ) is in the range of 10 to 32%.
  • pulsed NMR can measure each relaxation time of 1 H nuclei associated with molecular mobility in the system and its high quantification. This is an analysis method that can determine the existence ratio of each motion component in the system by using the property.
  • the spin-spin relaxation time T 2 of 1 H is used to determine the amount of crystal component (a 1 ), the amount of constrained amorphous component (a 2 ) and the amount of amorphous component (a 3 ) in the PVA film.
  • a 1 is a positive value so that the free induction decay (FID) signal obtained in the measurement of the spin-spin relaxation time T 2 of 1 H approximately fits the following equation (4).
  • a 1 corresponds to the amount of crystalline component (a 1 )
  • a 2 corresponds to the amount of restrained amorphous component (a 2 )
  • a 3 corresponds to the amount of amorphous component (a It falls under 3 ).
  • specific conditions for the pulsed NMR measurement conditions described later in the examples can be employed.
  • the PVA film to be measured is previously treated at 60 ° C. for 1 hour.
  • the treatment can be performed in a state in which the PVA film to be measured is immersed in water.
  • the PVA film is overlapped in an NMR tube or the like. It is preferable to carry out in the state immersed in water.
  • a method described later in the embodiment can be employed.
  • the PVA film of the present invention is processed at 60 ° C. for 1 hour and then subjected to pulsed NMR measurement (observation nucleus: 1 H). From the spin-spin relaxation time T 2 obtained, the crystal component amount (a 1 ), constrained amorphous component When the amount (a 2 ) and the amount of amorphous component (a 3 ) are determined, the crystal with respect to the sum of the amount of crystal component (a 1 ), the amount of restrained amorphous component (a 2 ) and the amount of amorphous component (a 3 ) The ratio of the total amount of the component amount (a 1 ) and the constrained amorphous component amount (a 2 ) needs to be in the range of 10 to 32%.
  • the proportion is less than 10%, the durability of the optical film obtained using the PVA film is deteriorated.
  • the ratio exceeds 32%, the hue of the optical film obtained using the PVA film is lowered.
  • the present invention is not limited in any way, the reason for this is that the influence on the state of the dichroic dye used may be different for each of the above components, and the ratio may be adjusted. It is estimated that it is extremely important in the effect of the present invention.
  • Total of crystal component amount (a 1 ), constrained amorphous component amount (a 2 ), and amorphous component amount (a 3 ) account for the sum of crystal component amount (a 1 ) and constrained amorphous component amount (a 2 )
  • the ratio is preferably 10.5% or more, more preferably 11% or more, and preferably 31.5% or less from the viewpoint of the hue and durability of the obtained optical film. More preferably, it is 31% or less.
  • the PVA film preferably has a constrained amorphous component.
  • the PVA film has a crystal component amount (a 1 ) and a constrained amorphous component amount (a 2 ) and the proportion of the constrained amorphous component amount (a 2 ) to the total of the amorphous component amount (a 3 ) is preferably 5% or more, and more preferably 6% or more.
  • PVA contained in the PVA film is composed of a structural unit (1) represented by the following formula (1), a structural unit (2) represented by the following formula (2), and a structural unit (3) represented by the following formula (3).
  • a structural unit (1) represented by the following formula (1) a structural unit represented by the following formula (1)
  • a structural unit (2) represented by the following formula (2) a structural unit (3) represented by the following formula (3).
  • the content of the structural units (1) to (3) is n 1 to n 3 mol% and the vinyl ester unit content is n 4 mol%, including at least one structural unit selected from the group 0.6 ⁇ n 1 + n 2 + 2 ⁇ n 3 + n 4 ⁇ 1.4 is preferably satisfied.
  • R 1 represents a hydrogen atom, a methyl group or an ethyl group.
  • R 2 represents a hydrogen atom, a methyl group or an ethyl group
  • X 2 represents a hydroxyalkyl group having 2 or more carbon atoms having one or more hydroxyl groups.
  • X 3 and X 4 each independently represent a hydroxyalkyl group having 1 or more carbon atoms having one or more hydroxyl groups.
  • R 1 represents a hydrogen atom, a methyl group or an ethyl group.
  • R 1 is preferably a methyl group or an ethyl group because the PVA film in which the ratio of the amount of crystalline component (a 1 ) and the amount of constrained amorphous component (a 2 ) satisfies the above range can be more easily obtained. More preferred is a methyl group.
  • R 2 represents a hydrogen atom, a methyl group or an ethyl group.
  • R 2 is preferably a hydrogen atom or a methyl group because a PVA film in which the ratio of the amount of crystal component (a 1 ) and the amount of constrained amorphous component (a 2 ) satisfies the above range can be more easily obtained.
  • X 2 represents a hydroxyalkyl group having 2 or more carbon atoms having one or more hydroxyl groups.
  • the number of carbon atoms of the hydroxyalkyl group is 8 or less because it becomes easier to obtain a PVA film in which the proportion of the amount of crystal component (a 1 ) and the amount of constrained amorphous component (a 2 ) satisfy the above range. Is preferably 6 or less, more preferably 4 or less, and the number of hydroxyl groups of the hydroxyalkyl group is preferably 1 or 2.
  • hydroxyalkyl group examples include, for example, 2-hydroxyethyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 4-hydroxybutyl group, Examples include 2-hydroxy-2-methylpropyl group, 3-hydroxy-2-methylpropyl group, 5-hydroxypentyl group, 8-hydroxyoctyl group, 1,2-dihydroxyethyl group, 2,3-dihydroxypropyl group, etc. It is done.
  • a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group, a 5-hydroxypentyl group, and a 1,2-dihydroxyethyl group are preferable, and a 1,2-dihydroxyethyl group is more preferable.
  • X 3 and X 4 each independently represent a hydroxyalkyl group having 1 or more carbon atoms having one or more hydroxyl groups.
  • the number of carbon atoms of the hydroxyalkyl group is 8 or less because it becomes easier to obtain a PVA film in which the proportion of the amount of crystal component (a 1 ) and the amount of constrained amorphous component (a 2 ) satisfy the above range. It is preferably 6 or less, more preferably 4 or less, and the number of hydroxyl groups of the hydroxyalkyl group is 1 or 2 depending on the number of carbon atoms of the hydroxyalkyl group. It is preferable that it is a piece.
  • hydroxyalkyl group examples include hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 4- Examples thereof include a hydroxybutyl group, a 2-hydroxy-2-methylpropyl group, a 3-hydroxy-2-methylpropyl group, an 8-hydroxyoctyl group, a 1,2-dihydroxyethyl group, and a 2,3-dihydroxypropyl group.
  • a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group, and a 1,2-dihydroxyethyl group are preferable, and a hydroxymethyl group is more preferable.
  • X 3 and X 4 may be the same or different from each other, and are preferably the same.
  • Examples of the PVA include those containing the structural unit (1) but not the structural units (2) and (3); those containing the structural unit (2) and not containing the structural units (1) and (3) Including structural unit (3) and not including structural units (1) and (2); including structural units (1) and (2) but not including structural unit (3); structural units (1) and ( 3) including structural unit (2); including structural units (2) and (3) but not including structural unit (1); including any of structural units (1) to (3) In consideration of the ease of production, the structural unit (1) and the structural unit (2) and (3) are excluded; the structural unit (2) and the structural unit (1) and (3) ); Or including structural unit (3) and structural unit (1) and (2) it does not include those are preferred.
  • the PVA contained in the PVA film preferably does not contain the structural unit (3).
  • the PVA exemplified above includes the structural unit (1) but does not include the structural units (2) and (3); the structural unit (2) includes the structural unit (1) and (3). ); Or those containing the structural units (1) and (2) but not the structural unit (3) are preferred.
  • the exemplified PVA may or may not contain a vinyl ester unit, but it is preferable to contain a vinyl ester unit in consideration of ease of production.
  • the vinyl ester unit typically includes a structural unit derived from a vinyl ester monomer used for the production of PVA as described later.
  • the PVA exemplified above has 0.6 ⁇ n when the content of the structural units (1) to (3) is n 1 to n 3 mol% and the content of the vinyl ester unit is n 4 mol%. 1 + n 2 + 2 ⁇ n 3 + n 4 ⁇ 1.4 is satisfied.
  • n 1 + n 2 + 2 ⁇ n 3 + n 4 is 0.6 mol% or more, the hue of the optical film obtained using the PVA film containing the PVA is improved.
  • the value of n 1 + n 2 + 2 ⁇ n 3 + n 4 is 1.4 mol% or less, the durability of the optical film obtained using the PVA film containing the PVA is improved.
  • the value of n 1 + n 2 + 2 ⁇ n 3 + n 4 is preferably 0.63 mol% or more, and more preferably 0.65 mol% or more. Moreover, it is more preferable that it is 1.38 mol% or less, and it is further more preferable that it is 1.35 mol% or less.
  • the structural unit means a repeating unit constituting the polymer, and the content of the structural units (1) to (3) is relative to the number of moles of all the structural units constituting the PVA.
  • the proportion of the number of moles of the structural units (1) to (3) is meant, and the content of vinyl ester units means the proportion of the number of moles of vinyl ester units to the number of moles of all structural units constituting the PVA.
  • the content of vinyl ester units is not particularly limited as long as the value of n 1 + n 2 + 2 ⁇ n 3 + n 4 is in the above range, but the amount of crystal component (a 1 ) and the amount of restrained amorphous component Considering that it becomes easier to obtain a PVA film in which the proportion of (a 2 ) satisfies the above range, ease of production, etc., it is preferably 1.35 mol% or less, and 1.3 mol% or less. More preferably, it is 1 mol% or less, more preferably 0.5 mol% or less, furthermore 0.3 mol% or less, and preferably 0.01 mol% or more. 0.05 mol% or more is more preferable, and 0.1 mol% or more is more preferable.
  • the method for producing the PVA exemplified above is not particularly limited.
  • a vinyl ester monomer is copolymerized with an unsaturated monomer that can be copolymerized therewith and can be converted into at least one structural unit selected from the group consisting of structural units (1) to (3).
  • the vinyl ester unit of the obtained vinyl ester copolymer is converted into a vinyl alcohol unit, and further unsaturated that can be converted into at least one structural unit selected from the group consisting of structural units (1) to (3)
  • Examples thereof include a method of converting a structural unit derived from a monomer into at least one structural unit selected from the group consisting of structural units (1) to (3).
  • Examples of the unsaturated monomer that can be converted into the structural unit (1) include an unsaturated monomer represented by the following formula (5).
  • the unsaturated monomer shown by following formula (6) is mentioned, for example.
  • the unsaturated monomer shown by following formula (7) is mentioned, for example.
  • R 1 represents a hydrogen atom, a methyl group or an ethyl group
  • Y 1 represents a hydromethyl group or a group having a structure in which a hydroxyl group of the hydroxymethyl group is protected by a protecting group.
  • R 2 represents a hydrogen atom, a methyl group or an ethyl group
  • Y 2 represents a hydroxyalkyl group having 2 or more carbon atoms having one or more hydroxyl groups or a hydroxyl group of the hydroxyalkyl group depending on a protecting group. A group having a protected structure is shown.
  • Y 3 and Y 4 are each independently a hydroxyalkyl group having 1 or more carbon atoms having one or more hydroxyl groups, or a group having a structure in which the hydroxyl groups of the hydroxyalkyl groups are protected by protecting groups. Indicates. ]
  • Y 1 represents a group having a structure in which the hydroxyl group of the hydroxymethyl group is protected by a protecting group
  • the protecting group includes an acyl group such as an acetyl group or a propionyl group; an acetal group; A carbonate group etc. are mentioned, Among these, since the said protective group can be removed when converting a vinyl ester unit into a vinyl alcohol unit, an acyl group is preferable and an acetyl group is more preferable.
  • Y 1 is preferably a group having a structure in which a hydroxyl group of a hydroxymethyl group is protected by a protecting group.
  • description of the number 2 or more hydroxyalkyl group having a carbon having one or more hydroxyl groups represented by Y 2 has the formula (2) in the X 2 number of 2 or more carbons with one or more hydroxyl groups shown This is the same as the description regarding the hydroxyalkyl group, and redundant description is omitted here.
  • the protecting group may be an acyl group such as an acetyl group or a propionyl group; an acetal such as an isopropylidene group; Examples include a carbonate group and the like.
  • acyl group is preferable and an acetyl group is more preferable because the protective group can be removed when the vinyl ester unit is converted to a vinyl alcohol unit.
  • Y 2 represents a group having a structure in which the hydroxyl group of the hydroxyalkyl group is protected by a protecting group
  • specific examples thereof include, for example, 2-acetoxyethyl group, 3-acetoxypropyl group, 1-acetoxy- 1-methylethyl group, 2-acetoxy-1-methylethyl group, 4-acetoxybutyl group, 2-acetoxy-2-methylpropyl group, 3-acetoxy-2-methylpropyl group, 8-acetoxyoctyl group, 1, Examples include 2-diacetoxyethyl group and 2,3-diacetoxypropyl group.
  • Y 2 is a group having a structure in which a hydroxyl group of a hydroxyalkyl group having 2 or more carbon atoms having one or more hydroxyl groups is protected by a protecting group because the exemplified PVA can be easily produced. Is preferred.
  • Examples of the unsaturated monomer represented by the formula (6) include 4-acetoxy-1-butene, 5-acetoxy-1-pentene, 6-acetoxy-1-hexene, 7-acetoxy-1-heptene, 3 4,4-diacetoxy-1-butene, and 3,4-diacetoxy-1-butene is preferred.
  • the description regarding the hydroxyalkyl group having 1 or more carbon atoms having one or more hydroxyl groups represented by Y 3 and / or Y 4 is the one represented by X 3 and / or X 4 in the formula (3). This is the same as the above description regarding a hydroxyalkyl group having 1 or more carbon atoms having a hydroxyl group, and redundant description is omitted here.
  • the protecting group may be an acyl group such as an acetyl group or a propionyl group; An acetal group such as a redene group; a carbonate group, and the like.
  • an acyl group is preferable and an acetyl group is more preferable because the protective group can be removed when converting a vinyl ester unit to a vinyl alcohol unit. preferable.
  • Y 3 and / or Y 4 represents a group having a structure in which the hydroxyl group of the hydroxyalkyl group is protected by a protecting group
  • specific examples thereof include, for example, an acetoxymethyl group, a 2-acetoxyethyl group, 3 -Acetoxypropyl group, 1-acetoxy-1-methylethyl group, 2-acetoxy-1-methylethyl group, 4-acetoxybutyl group, 2-acetoxy-2-methylpropyl group, 3-acetoxy-2-methylpropyl group , 8-acetoxyoctyl group, 1,2-diacetoxyethyl group, 2,3-diacetoxypropyl group and the like.
  • Y 3 and / or Y 4 has a structure in which the hydroxyl group of a hydroxyalkyl group having 1 or more carbon atoms having one or more hydroxyl groups is protected by a protective group because the production of the exemplified PVA is easy. It is preferable that both Y 3 and Y 4 are groups having a structure in which the hydroxyl group of the hydroxyalkyl group having 1 or more carbon atoms having one or more hydroxyl groups is protected by a protecting group. More preferred.
  • Examples of the unsaturated monomer represented by the formula (7) include 1,3-diacetoxy-2-methylenepropane, 1,3-dipropionyloxy-2-methylenepropane, and 1,3-dibutyryloxy-2. -Methylenepropane and the like, and 1,3-diacetoxy-2-methylenepropane is preferred.
  • the vinyl ester monomer used for the production of the above-mentioned PVA is not particularly limited.
  • vinyl acetate is preferred.
  • the polymerization method may be any of batch polymerization, semi-batch polymerization, continuous polymerization, semi-continuous polymerization, etc., and the polymerization method is known as bulk polymerization method, solution polymerization method, suspension polymerization method, emulsion polymerization method, etc. The method can be applied.
  • a bulk polymerization method or a solution polymerization method in which polymerization proceeds in a solvent-free or solvent such as alcohol is usually employed.
  • an emulsion polymerization method is also preferred.
  • the solvent of the solution polymerization method is not particularly limited, for example, alcohol.
  • the alcohol used as the solvent for the solution polymerization method is, for example, a lower alcohol such as methanol, ethanol, or propanol.
  • the amount of solvent used in the polymerization system may be selected in consideration of the chain transfer of the solvent according to the degree of polymerization of the target PVA.
  • the solvent is methanol
  • the polymerization initiator to be used may be selected from known polymerization initiators such as azo initiators, peroxide initiators, and redox initiators according to the polymerization method.
  • azo initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile).
  • peroxide initiator examples include percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and diethoxyethyl peroxydicarbonate; t-butyl peroxyneodecanate, ⁇ - Perester compounds such as cumylperoxyneodecanate; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate; acetyl peroxide. Potassium persulfate, ammonium persulfate, hydrogen peroxide, or the like may be combined with the above initiator to form a polymerization initiator.
  • percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and diethoxyethyl peroxydicarbonate
  • the redox initiator is, for example, a polymerization initiator in which the peroxide initiator is combined with a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, or longalite.
  • a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, or longalite.
  • the amount of the polymerization initiator used varies depending on the type of the polymerization initiator and cannot be determined unconditionally, but may be selected according to the polymerization rate. For example, when 2,2′-azobisisobutyronitrile or acetyl peroxide is used as the polymerization initiator, 0.01 to 0.2 mol% is preferable with respect to the vinyl ester monomer, and 0.02 to 0 More preferred is 15 mol%.
  • Chain transfer agent examples include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethanethiol; and phosphinic acid salts such as sodium phosphinate monohydrate. Of these, aldehydes and ketones are preferably used.
  • the amount of chain transfer agent used can be determined according to the chain transfer coefficient of the chain transfer agent to be used and the degree of polymerization of the target PVA. 1 to 10 parts by mass is preferred.
  • the PVA exemplified above can be obtained by saponifying the vinyl ester copolymer obtained. By saponifying the vinyl ester copolymer, the vinyl ester unit in the vinyl ester copolymer is converted to a vinyl alcohol unit.
  • the unsaturated monomer represented by the formula (3) when Y 1 is a group having a structure in which the hydroxyl group of the hydroxymethyl group is protected by an acyl group, the unsaturated monomer that can be copolymerized and is converted into at least one structural unit selected from the group consisting of structural units (1) to (3) has a hydroxyl group protected by an acyl group, the unsaturated monomer The ester bond of the acyl group portion in the structural unit derived from the monomer is also saponified to produce a hydroxyl group. Therefore, the PVA can be produced without further reaction such as hydrolysis after saponification.
  • the saponification of the vinyl ester copolymer can be performed in a state where the vinyl ester copolymer is dissolved in, for example, alcohol or hydrous alcohol.
  • the alcohol used for saponification include lower alcohols such as methanol and ethanol, preferably methanol.
  • the alcohol used for saponification may contain other solvents such as acetone, methyl acetate, ethyl acetate, and benzene at a ratio of 40% by mass or less of the mass, for example.
  • the catalyst used for saponification is, for example, an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an alkali catalyst such as sodium methylate, or an acid catalyst such as mineral acid.
  • the temperature at which saponification is performed is not limited, but is preferably within the range of 20 to 60 ° C.
  • the product is pulverized, washed and dried to obtain PVA.
  • the saponification method is not limited to the method described above, and a known method can be applied.
  • the exemplified PVA can further include other structural units other than the structural units (1) to (3), the vinyl alcohol unit, and the vinyl ester unit.
  • the other structural unit include a structural unit derived from an ethylenically unsaturated monomer copolymerizable with a vinyl ester monomer.
  • Units structural units that have not been converted into at least one structural unit selected from the group consisting of structural units (1) to (3) in the deprotection process
  • the proportion of the total of the structural units (1) to (3), the vinyl alcohol unit and the vinyl ester unit in the PVA exemplified above is 90 mol%, where the number of moles of all structural units constituting the PVA is 100 mol%.
  • it is 98 mol% or more, more preferably 99 mol% or more, 99.5 mol% or more, 99.8 mol% or more, 99.9 mol% or more, Furthermore, 100 mol% may be sufficient.
  • ethylenically unsaturated monomer examples include ⁇ -olefins such as ethylene, propylene, n-butene, isobutylene and 1-hexene; acrylic acid and salts thereof; unsaturated monomer having an acrylate group.
  • Body methacrylic acid and salts thereof; unsaturated monomer having methacrylic ester group; acrylamide; N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamidepropanesulfonic acid and salts thereof Acrylamide derivatives such as acrylamidepropyldimethylamine and salts thereof (for example, quaternary salts); methacrylamide; N-methyl methacrylamide, N-ethyl methacrylamide, methacrylamide propane sulfonic acid and salts thereof, methacrylamide propylene Methacrylamide derivatives such as dimethylamine and its salts (eg quaternary salts); methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether , Vinyl
  • the degree of polymerization of the exemplified PVA can be obtained more easily by obtaining a PVA film in which the ratio of the amount of crystal component (a 1 ) and the amount of constrained amorphous component (a 2 ) satisfies the above range. From the viewpoint of improving the hue of the optical film obtained, it is preferably 3,000 or less, more preferably 2,900 or less, and even more preferably 2,800 or less. On the other hand, the degree of polymerization is preferably more than 2,000, more preferably more than 2,100, because the durability of the optical film obtained using the PVA film containing PVA is improved. More preferably, it exceeds 200. In this specification, the degree of polymerization of PVA means an average degree of polymerization measured according to the description of JIS K6726-1994.
  • the molecular weight distribution of the above exemplified PVA is such that the PVA film in which the ratio of the crystal component amount (a 1 ) and the constrained amorphous component amount (a 2 ) satisfies the above range is more easily obtained.
  • the molecular weight distribution is preferably 2.2 or more, more preferably 2.4 or more, and even more preferably 3.8 or less. More preferably, it is as follows.
  • the molecular weight distribution of PVA in this specification is a value calculated by mass average molecular weight (Mw) / number average molecular weight (Mn).
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) were obtained by using monodisperse polymethyl methacrylate as a standard, hexafluoroisopropanol containing 20 mmol / L sodium trifluoroacetate as a mobile phase, 40 ° C., flow rate 0 It can be determined by measuring gel permeation chromatography (manufactured by Tosoh Corporation, apparatus: HLC-8220GPC, column: GMHHR-H (S)) at 2 mL / min.
  • the PVA film of the present invention can contain a plasticizer in addition to the above PVA.
  • Preferred plasticizers include polyhydric alcohols, and specific examples include ethylene glycol, glycerin, propylene glycol, diethylene glycol, diglycerin, triethylene glycol, tetraethylene glycol, trimethylolpropane, and the like.
  • the PVA film of the present invention can contain one or more of these plasticizers. Among these, glycerin is preferable in terms of the effect of improving stretchability.
  • the content of the plasticizer in the PVA film of the present invention is preferably 1 part by mass or more, more preferably 3 parts by mass or more, with respect to 100 parts by mass of PVA contained in the PVA film. Further, it is preferably 20 parts by mass or less, more preferably 17 parts by mass or less, and further preferably 15 parts by mass or less. When the content is 1 part by mass or more, the stretchability of the film is further improved. On the other hand, when the content is 20 parts by mass or less, it is possible to prevent the film from becoming too flexible and handling properties from being lowered.
  • the PVA film of the present invention further includes a filler, a processing stabilizer such as a copper compound, a weather resistance stabilizer, a colorant, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a flame retardant, Additives such as thermoplastic resins, lubricants, fragrances, defoamers, deodorants, extenders, release agents, mold release agents, reinforcing agents, crosslinking agents, fungicides, preservatives, crystallization rate retarders These can be blended as needed.
  • a processing stabilizer such as a copper compound, a weather resistance stabilizer, a colorant, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a flame retardant
  • Additives such as thermoplastic resins, lubricants, fragrances, defoamers, deodorants, extenders, release agents, mold release agents, reinforcing agents, crosslinking agents, fungicides, preservatives, crystallization rate retarders
  • the proportion of the total of PVA and plasticizer in the PVA film of the present invention is preferably 80% by mass or more, more preferably 90% by mass or more, and 95% by mass or more based on the mass of the PVA film. More preferably.
  • the degree of swelling of the PVA film of the present invention is preferably in the range of 160 to 240%, more preferably in the range of 170 to 230%, and particularly preferably in the range of 180 to 220%. .
  • the degree of swelling is 160% or more, it is more effective that the total ratio of the amount of crystal component (a 1 ) and the amount of constrained amorphous component (a 2 ) after treatment at 60 ° C. for 1 hour becomes too high.
  • the hue of the optical film obtained using the PVA film can be prevented.
  • the degree of swelling is 240% or less, it is more effective that the total ratio of the amount of crystal component (a 1 ) and the amount of constrained amorphous component (a 2 ) after treatment at 60 ° C.
  • the degree of swelling of the PVA film is obtained by dividing the mass when the PVA film is immersed in distilled water at 30 ° C. for 30 minutes by the mass after drying at 105 ° C. for 16 hours. It means the percentage of the value, and specifically can be measured by the method described later in the examples.
  • the degree of swelling can be adjusted, for example, by changing the conditions for heat treatment, and the degree of swelling can usually be lowered by increasing the heat treatment temperature and lengthening the heat treatment time.
  • the thickness of the PVA film is preferably 1 to 60 ⁇ m, more preferably 5 to 55 ⁇ m, and particularly preferably 10 to 50 ⁇ m.
  • stretch breakage tends to occur during uniaxial stretching treatment for producing an optical film such as a polarizing film.
  • the said thickness is too thick, there exists a tendency for a stretch spot to generate
  • the width of the PVA film of the present invention is not particularly limited, and can be determined according to its use. In recent years, when the screen size of liquid crystal televisions and liquid crystal monitors has been increasing, it is preferable that the width of the PVA film is 3 m or more for use as an end product. On the other hand, if the width of the PVA film is too large, problems such as difficulty in uniformly performing uniaxial stretching itself may occur when an optical film is produced with a practical device.
  • the width of the film is preferably 7 m or less.
  • the production method of the PVA film of the present invention is not particularly limited, and a production method in which the thickness and width of the film after film formation are more uniform can be preferably adopted.
  • the above-described PVA constituting the PVA film and necessary Depending on the film forming stock solution in which one or more of the plasticizers, additives and surfactants described later are dissolved in a liquid medium, PVA and, if necessary, further plasticizers, additions It can be manufactured using a film-forming stock solution containing one or more of an agent, a surfactant, a liquid medium, and the like, in which PVA is melted.
  • the film-forming stock solution contains at least one of a plasticizer, an additive, and a surfactant, it is preferable that these components are uniformly mixed.
  • liquid medium used for the preparation of the membrane forming stock solution examples include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. , Trimethylolpropane, ethylenediamine, diethylenetriamine and the like, and one or more of them can be used. Among these, water is preferable from the viewpoint of environmental load and recoverability.
  • the volatile fraction of the film-forming stock solution (content ratio in the film-forming stock solution of volatile components such as liquid media removed by volatilization or evaporation during film formation) varies depending on the film-forming method, film-forming conditions, etc. Specifically, it is preferably in the range of 50 to 95% by mass, more preferably in the range of 55 to 90% by mass, and still more preferably in the range of 60 to 85% by mass.
  • the film-forming stock solution has a volatile content of 50% by mass or more, so that the viscosity of the film-forming stock solution does not become too high, and filtration and defoaming are smoothly performed during the preparation of the film-forming stock solution, and there are few foreign substances and defects. Is easy to manufacture.
  • the volatile fraction of the film-forming stock solution is 95% by mass or less, the concentration of the film-forming stock solution does not become too low, and industrial film production is facilitated.
  • the film forming stock solution preferably contains a surfactant.
  • a surfactant By including the surfactant, the film-forming property is improved and the occurrence of uneven thickness of the film is suppressed, and the film is easily peeled off from the metal roll or belt used for film formation.
  • the film may contain a surfactant.
  • the kind of said surfactant is not specifically limited, From a viewpoint of the peelability from a metal roll or a belt, an anionic surfactant or a nonionic surfactant is preferable.
  • anionic surfactant for example, a carboxylic acid type such as potassium laurate; a sulfuric acid ester type such as polyoxyethylene lauryl ether sulfate and octyl sulfate; and a sulfonic acid type such as dodecylbenzene sulfonate are suitable.
  • a carboxylic acid type such as potassium laurate
  • a sulfuric acid ester type such as polyoxyethylene lauryl ether sulfate and octyl sulfate
  • a sulfonic acid type such as dodecylbenzene sulfonate
  • Nonionic surfactants include, for example, alkyl ether types such as polyoxyethylene oleyl ether; alkylphenyl ether types such as polyoxyethylene octylphenyl ether; alkyl ester types such as polyoxyethylene laurate; polyoxyethylene laurylamino Alkylamine type such as ether; alkylamide type such as polyoxyethylene lauric acid amide; polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether; alkanolamide type such as lauric acid diethanolamide and oleic acid diethanolamide; polyoxy An allyl phenyl ether type such as alkylene allyl phenyl ether is preferred.
  • surfactants can be used alone or in combination of two or more.
  • the content thereof is preferably in the range of 0.01 to 0.5 parts by weight with respect to 100 parts by weight of PVA contained in the film-forming stock solution, and 0.02 It is more preferably in the range of -0.3 parts by mass, and particularly preferably in the range of 0.05-0.1 parts by mass.
  • the content is 0.01 mass part or more, film forming property and peelability improve more.
  • the content is 0.5 parts by mass or less, it is possible to suppress that the surfactant bleeds out to the surface of the PVA film to cause blocking, and the handleability is deteriorated.
  • Examples of the film forming method for forming a PVA film using the above-described film forming stock solution include a cast film forming method, an extrusion film forming method, a wet film forming method, and a gel film forming method. These film forming methods may be used alone or in combination of two or more. Among these film forming methods, the cast film forming method and the extrusion film forming method are preferable because a PVA film having a uniform thickness and width and good physical properties can be obtained. The formed film can be dried or heat-treated as necessary.
  • a T-type slit die, a hopper plate, an I-die, a lip coater die or the like is used, and the above film forming stock solution is positioned on the most upstream side. It discharges or casts uniformly on the peripheral surface of the rotating heated first roll (or belt), and volatilizes from one surface of the film discharged or cast on the peripheral surface of the first roll (or belt). Evaporate and dry the sexual components, and then further dry on the circumference of one or more rotating heated rolls located downstream, or pass through a hot air dryer to further dry Then, the method of winding with a winding device can be preferably employed industrially. Drying with a heated roll and drying with a hot air dryer may be performed in an appropriate combination.
  • an optical film since an optical film excellent in all of an optical characteristic, a hue, and durability can be manufactured easily, an optical film is used. It is preferable to use it as a raw film for manufacturing. Examples of such an optical film include a polarizing film and a retardation film, and a polarizing film is preferable. Such an optical film can be produced, for example, by a method using the PVA film of the present invention as a raw film for producing an optical film and having a step of uniaxial stretching.
  • the PVA film itself, or the PVA film derived from the PVA film of the present invention produced by applying the swelling treatment described later (hereinafter referred to as “the PVA film of the present invention” and “the PVA film derived from the PVA film of the present invention”). ” May be collectively referred to as“ PVA film according to the present invention ”).
  • the method for producing a polarizing film using the PVA film of the present invention is not particularly limited, and any method conventionally employed may be employed. Examples of such a method include a method of dyeing and uniaxially stretching a PVA film based on the present invention, or uniaxially stretching a PVA film based on the present invention containing a dye.
  • the PVA film based on the present invention is subjected to swelling, dyeing, uniaxial stretching, and, if necessary, crosslinking treatment, fixing treatment, drying, heat treatment, etc.
  • the method of giving is mentioned.
  • the order of each treatment such as swelling, dyeing, crosslinking treatment, uniaxial stretching, and fixing treatment is not particularly limited, and one or two or more treatments can be performed simultaneously. Also, one or more of each process can be performed twice or more.
  • Swelling can be performed by immersing the PVA film according to the present invention in water.
  • the temperature of the water when immersed in water is preferably in the range of 20 to 40 ° C., more preferably in the range of 22 to 38 ° C., and preferably in the range of 25 to 35 ° C. Further preferred.
  • the time for immersion in water is preferably in the range of 0.1 to 5 minutes, for example, and more preferably in the range of 0.5 to 3 minutes.
  • the water at the time of immersing in water is not limited to pure water, The aqueous solution in which various components melt
  • Dyeing can be performed by bringing a dichroic dye into contact with the PVA film according to the present invention.
  • the dichroic dye an iodine dye is generally used.
  • the dyeing time may be any stage before uniaxial stretching, during uniaxial stretching, or after uniaxial stretching.
  • Dyeing is generally performed by immersing the PVA film in a solution (particularly an aqueous solution) containing iodine-potassium iodide which is a dyeing bath, and such a dyeing method is also suitably employed in the present invention.
  • the iodine concentration in the dyeing bath is preferably in the range of 0.01 to 0.5% by mass, and the potassium iodide concentration is preferably in the range of 0.01 to 10% by mass.
  • the temperature of the dyeing bath is preferably 20 to 50 ° C., particularly 25 to 40 ° C.
  • the crosslinking treatment is preferably performed after the treatment for bringing the dichroic dye into contact and before the uniaxial stretching.
  • the crosslinking treatment can be performed by immersing the PVA film according to the present invention in an aqueous solution containing a crosslinking agent.
  • a crosslinking agent one or more of boron compounds such as boric acid and borate such as borax can be used.
  • the concentration of the crosslinking agent in the aqueous solution containing the crosslinking agent is preferably in the range of 1 to 15% by mass, more preferably in the range of 2 to 7% by mass, and in the range of 3 to 6% by mass. More preferably. Sufficient stretchability can be maintained when the concentration of the crosslinking agent is in the range of 1 to 15% by mass.
  • the aqueous solution containing a crosslinking agent may contain potassium iodide and the like.
  • the temperature of the aqueous solution containing the crosslinking agent is preferably in the range of 20 to 50 ° C., particularly in the range of 25 to 40 ° C. By setting the temperature within the range of 20 to 50 ° C., crosslinking can be performed efficiently.
  • Uniaxial stretching of the PVA film according to the present invention may be performed by either a wet stretching method or a dry stretching method.
  • the wet stretching method it can be carried out in an aqueous solution containing boric acid, or can be carried out in the dyeing bath described above or in a fixing treatment bath described later.
  • the stretching may be performed at room temperature, may be performed while heating, or may be performed in the air using a PVA film after water absorption.
  • the wet stretching method is preferable because it can be uniformly stretched in the width direction, and uniaxial stretching is more preferable in an aqueous solution containing boric acid.
  • the concentration of boric acid in the boric acid aqueous solution is preferably within the range of 0.5 to 6.0% by mass, more preferably within the range of 1.0 to 5.0% by mass, It is particularly preferably within the range of ⁇ 4.0% by mass.
  • the aqueous boric acid solution may contain potassium iodide, and the concentration of potassium iodide is preferably in the range of 0.01 to 10% by mass.
  • the stretching temperature in the uniaxial stretching is preferably in the range of 30 to 90 ° C, more preferably in the range of 40 to 80 ° C, and particularly preferably in the range of 50 to 70 ° C.
  • the draw ratio in uniaxial stretching is preferably 6.6 times or more, more preferably 6.8 times or more, and 7.0 times or more from the viewpoint of the polarizing performance of the obtained polarizing film. Is particularly preferred.
  • the upper limit of the draw ratio is not particularly limited, but the draw ratio is preferably 8 times or less.
  • the direction of uniaxial stretching in the case of uniaxially stretching a long PVA film is not particularly limited, and uniaxial stretching or lateral uniaxial stretching in the long direction can be adopted, but a polarizing film having excellent polarization performance can be obtained.
  • Uniaxial stretching in the longitudinal direction can be performed by changing the peripheral speed between the rolls using a stretching apparatus including a plurality of rolls parallel to each other.
  • lateral uniaxial stretching can be performed using a tenter type stretching machine.
  • the fixing treatment bath used for the fixing treatment an aqueous solution containing one or more of boron compounds such as boric acid and borax can be used. Moreover, you may add an iodine compound and a metal compound in a fixed treatment bath as needed.
  • the concentration of the boron compound in the fixing treatment bath is generally about 2 to 15% by mass, particularly about 3 to 10% by mass. By setting the concentration within the range of 2 to 15% by mass, the adsorption of the dichroic dye can be further strengthened.
  • the temperature of the fixing treatment bath is preferably 15 to 60 ° C., particularly 25 to 40 ° C.
  • Drying conditions are not particularly limited, but it is preferable to perform the drying at a temperature within the range of 30 to 150 ° C, particularly within the range of 50 to 130 ° C.
  • a polarizing film excellent in dimensional stability can be easily obtained by drying at a temperature in the range of 30 to 150 ° C.
  • the polarizing film obtained as described above is usually used as a polarizing plate by attaching an optically transparent protective film having mechanical strength to both sides or one side.
  • an optically transparent protective film having mechanical strength to both sides or one side.
  • a cellulose triacetate (TAC) film, a cycloolefin polymer (COP) film, an acetic acid / cellulose butyrate (CAB) film, an acrylic film, a polyester film, or the like is used.
  • the adhesive for bonding include PVA adhesives, urethane adhesives, acrylate ultraviolet curable adhesives, and the like.
  • the polarizing plate obtained as described above can be used as an LCD component after being coated with an acrylic adhesive or the like and bonded to a glass substrate. At the same time, it may be bonded to a retardation film, a viewing angle improving film, a brightness improving film, or the like.
  • PVA Primary structure of PVA
  • the primary structure of PVA used in the following examples and comparative examples was analyzed using 400 MHz 1 H-NMR. Deuterated DMSO was used as a solvent for the 1 H-NMR measurement.
  • Crystal component amount (a 1 ) and constrained amorphous component amount (a 2 ) in the PVA film A sample (100 mg) obtained from the PVA film obtained in the following examples or comparative examples was cut into a size of about 5 mm ⁇ 5 mm, and then poured into an NMR tube together with 1 mL of heavy water. This NMR tube was immersed in a constant temperature bath at 60 ° C. for 1 hour. Then, it stored at 20 degreeC for 24 hours, and was set as the measurement sample. This measurement sample was measured for 1 H spin-spin relaxation time T 2 using pulsed NMR (“minispec mq20 WVT” manufactured by Bruker BioSpin Corporation). The measurement conditions are as follows.
  • Pulse sequence Solid-Echo method (90x- ⁇ -90y) RF pulse width (Pw1): 2.1 ⁇ s ⁇ Pulse interval (Pi1): 1 ⁇ s ⁇ Pulse repetition time: 1s ⁇ Measurement temperature: 30 °C
  • the free induction decay (FID) signal obtained by the above measurement is fitted to the above equation (4) by the linear least square method, and the crystal component amount (a 1 ) and the constrained amorphous component amount (a 2 ) and the amount of amorphous component (a 3 ) were determined, and the ratio of each component to the total amount of these three components was calculated.
  • Optical properties of polarizing film (dichroic ratio) (1) Measurement of transmittance Ts From the central part of the polarizing film obtained in the following examples or comparative examples, two 2 cm samples were taken in the length direction of the polarizing film, and a spectrophotometer with an integrating sphere (Japan) Using “V7100” manufactured by Spectroscopic Co., Ltd., in accordance with JIS Z 8722 (measuring method of object color), the visibility of the visible light region of the C light source and 2 ° field of view is corrected.
  • the transmittance Ts (%) and the degree of polarization V (%) were determined by the method described above, and the transmittance Ts (%) was plotted on the horizontal axis and the degree of polarization for each example and comparative example.
  • V (%) as the vertical axis, a total of 5 points including one point based on the transmittance Ts (%) and the degree of polarization V (%) of the polarizing film obtained in each example or comparative example are plotted on a graph.
  • V (%) as the vertical axis
  • a total of 5 points including one point based on the transmittance Ts (%) and the degree of polarization V (%) of the polarizing film obtained in each example or comparative example are plotted on a graph.
  • an approximate curve was obtained, and from the approximate curve, the degree of polarization V 44 (%) when the transmittance Ts (%) was 44% was obtained.
  • the dichroic ratio at a transmittance of 44% was determined by the following formula (11), and used as an index of polarization performance.
  • the higher the dichroic ratio the better the optical properties of the polarizing film.
  • Dichroic ratio when the transmittance 44% log (44 / 100-44 / 100 ⁇ V 44/100) / log (44/100 + 44/100 ⁇ V 44/100) (11)
  • the four polarizing films produced in the above-mentioned “Optical characteristics of the polarizing film (dichroic ratio)” with different amounts of adsorption of the dichroic dye, and each example or comparative example were obtained.
  • the absorbance (orthogonal absorbance) at a wavelength of 610 nm obtained when the transmittance was in the range of 44 to 45% and the transmittance T ⁇ (%) was measured out of the total of five polarizing films obtained.
  • One polarizing film of 2.95 to 3.05 was selected. The polarizing film was exposed for 4 hours in an environment of 60 ° C.
  • Example 1 to 6 and Comparative Examples 1 to 5 (1) Copolymer of vinyl acetate and 2-methyl-2-propenyl acetate, 3,4-diacetoxy-1-butene, 7-acetoxy-1-heptene or 1,3-diacetoxy-2-methylenepropane (
  • Comparative Example 1 100 parts by mass of PVA shown in Table 1 obtained by saponifying a vinyl acetate homopolymer), 10 parts by mass of glycerin as a plasticizer, and sodium polyoxyethylene lauryl ether sulfate as a surfactant 0.1
  • an aqueous solution containing 10 parts by mass and containing 10 parts by mass of PVA as a film-forming stock solution this is dried on a metal roll at 80 ° C., and the resulting film is heated at a predetermined temperature in a hot air dryer.
  • the degree of swelling was adjusted to 200% by heat treatment for 1 minute, and a PVA film having a thickness of 30 ⁇ m was produced.
  • the ratio of the crystal component amount (a 1 ) and the constrained amorphous component amount (a 2 ) was determined by the above-described method, and the stretchability was evaluated. The results are shown in Table 1.
  • the length was 1.1 times (2.6 times in total) while being immersed in an aqueous solution (crosslinking bath) (temperature 30 ° C.) containing 3% by weight of boric acid and 3% by weight of potassium iodide. Uniaxially stretched in the direction. Further, while dipping in an aqueous solution (stretching bath) containing 4% by mass of boric acid and 6% by mass of potassium iodide (the temperature at which the limiting stretching ratio determined in the above “stretchability of PVA film” is highest). The film was uniaxially stretched in the length direction to a magnification 0.2 times lower than the limit draw ratio.

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Abstract

　Le problème décrit par la présente invention est de fournir un film APV permettant de fabriquer facilement un film optique ayant d'excellentes caractéristiques optiques, de teinte et de durabilité et de fournir un procédé de fabrication d'un film optique en utilisant le film APV. La solution selon l'invention passe par un film APV dans lequel le rapport entre la somme de la quantité de composés cristallins (ａ1) et de la quantité de composés amorphes restreints (ａ2) et la somme de la quantité de composés cristallins (ａ1), de la quantité de composés amorphes restreints (ａ2) et de la quantité de composés amorphes (ａ3) est de 10-32% quand la quantité de composés cristallins (ａ1), la quantité de composés amorphes restreints (ａ2) et la quantité de composés amorphes (ａ3) sont calculées à partir du temps de relaxation spin-spin (T)2 obtenu par une mesure en RMN à impulsions (noyau observé : 1H) après une heure de traitement à 60 °C. L'invention concerne également un procédé de fabrication d'un film optique en utilisant le film APV, le procédé ayant une étape d'étirage uniaxial.
PCT/JP2014/070605 2013-08-09 2014-08-05 Film polymère à base d'alcool vinylique WO2015020046A1 (fr)

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WO2019151206A1 (fr) * 2018-01-30 2019-08-08 株式会社クラレ Film de poly(alcool vinylique) et procédé de fabrication associé
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WO2019189687A1 (fr) * 2018-03-30 2019-10-03 積水化学工業株式会社 Film de poly(alcool vinylique) et procédé de production d'un film polarisant
WO2019189697A1 (fr) * 2018-03-30 2019-10-03 積水化学工業株式会社 Film de poly(alcool vinylique) et procédé de production d'un film polarisant
WO2019189693A1 (fr) * 2018-03-30 2019-10-03 積水化学工業株式会社 Film de poly (vinyle alcool) et procédé de production de film polarisant
JP2019184992A (ja) * 2018-08-01 2019-10-24 積水化学工業株式会社 ポリビニルアルコールフィルム、及び偏光フィルムの製造方法
WO2020138445A1 (fr) 2018-12-28 2020-07-02 株式会社クラレ Film de base de transfert hydraulique et film d'impression par transfert hydraulique
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CN105431751A (zh) 2016-03-23
TW201509957A (zh) 2015-03-16
KR102216810B1 (ko) 2021-02-17
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