WO2016002808A1 - Adhesive composition and polarizing plate containing same - Google Patents

Adhesive composition and polarizing plate containing same Download PDF

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Publication number
WO2016002808A1
WO2016002808A1 PCT/JP2015/068892 JP2015068892W WO2016002808A1 WO 2016002808 A1 WO2016002808 A1 WO 2016002808A1 JP 2015068892 W JP2015068892 W JP 2015068892W WO 2016002808 A1 WO2016002808 A1 WO 2016002808A1
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WO
WIPO (PCT)
Prior art keywords
polyvinyl alcohol
adhesive composition
weight
polarizer
water
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Application number
PCT/JP2015/068892
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French (fr)
Japanese (ja)
Inventor
天煕 趙
▲恵▼琳 權
重萬 朴
武藤　清
Original Assignee
住友化学株式会社
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Priority claimed from KR1020150015914A external-priority patent/KR102282040B1/en
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to CN201580034603.6A priority Critical patent/CN106471403B/en
Priority to JP2016531405A priority patent/JP7121466B2/en
Publication of WO2016002808A1 publication Critical patent/WO2016002808A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J129/00—Adhesives based on 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; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09J129/04—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

Definitions

  • the present invention relates to an adhesive composition and a polarizing plate in which a polarizer and a polarizer protective film are bonded using the adhesive composition.
  • the polarizing plate is useful as one of the optical components constituting the liquid crystal display device.
  • a polarizing plate usually has a structure in which protective films are laminated on both sides of a polarizer, and is inserted into a liquid crystal display device. It is also known that a protective film is provided only on one side of a polarizer, but in many cases, a protective film is not provided on the other side, but a layer having an optical function, for example, as a separate function. Also joined together.
  • an iodine-based film in which iodine is adsorbed and oriented in polyvinyl alcohol and a dye-based film in which dichroic dye is adsorbed and oriented in polyvinyl alcohol are used as a polarizer, and an aqueous solution of a polyvinyl alcohol-based resin on at least one side of the film
  • TAC triacetyl cellulose
  • a polarizing plate having improved resistance to moisture and heat by bonding a polarizer (polarizing film) and a protective film using a polyvinyl alcohol-based adhesive and then drying by heating at a temperature of 90 to 100 ° C.
  • polarizer polarizing film
  • a protective film using a polyvinyl alcohol-based adhesive
  • JP-A-07-134212 discloses an adhesive composition containing a polyvinyl alcohol resin, glyoxal, and zinc chloride.
  • This invention provides the adhesive composition for polarizing plates which improved water resistance, without the adhesive force and polarization degree falling.
  • the present invention includes an acetoacetyl group-modified polyvinyl alcohol resin, a dialdehyde, and a water-soluble chelate compound, does not include a crosslinking regulator, and the average degree of polymerization of the acetoacetyl group-modified polyvinyl alcohol resin is 1500 or less.
  • the adhesive composition for polarizing plates is provided.
  • the acetoacetyl group-modified polyvinyl alcohol resin may be included in an amount of 3 to 9% by weight based on the solid content weight of the adhesive composition.
  • dialdehydes are contained in an amount of 20 to 50 parts by weight and a water-soluble chelate compound is contained in an amount of 2 to 10 parts by weight with respect to 100 parts by weight of an acetoacetyl group-modified polyvinyl alcohol resin. It may be.
  • dialdehyde may be glyoxal.
  • the water-soluble chelate compound may be one or more selected from the group consisting of zinc chloride, cobalt chloride, magnesium chloride, magnesium acetate, aluminum nitrate, zinc nitrate, and zinc sulfate. .
  • the present invention also provides a polyvinyl alcohol polarizer; an adhesive layer laminated on one or both sides of the polarizer and containing the adhesive composition; and a polarization laminated on one or both sides on the adhesive layer.
  • a polarizing plate comprising a child protective film.
  • the adhesive composition for polarizing plates of this invention has the effect that water resistance improves, without the adhesive force and polarization degree falling.
  • FIG. 1 is a diagram schematically showing a water resistance evaluation test method according to an experimental example.
  • the present invention includes an acetoacetyl group-modified polyvinyl alcohol resin, a dialdehyde, and a water-soluble chelate compound, does not include a crosslinking regulator, and the average degree of polymerization of the acetoacetyl group-modified polyvinyl alcohol resin is 1500 or less.
  • the polarizing plate adhesive composition for polarizing plates and the polarizing plate by which the polarizer and the polarizer protective film were joined using the said adhesive composition are provided.
  • the adhesive composition of the present invention solves the problem of liquid preparation stability by improving the process of charging the adhesive, and is adhesive and durable without the addition of a crosslinking regulator that causes a decrease in the degree of polarization due to wet heat deterioration. It has the effect of having sex. That is, the present invention increases the content of acetoacetyl group-modified polyvinyl alcohol resins, dialdehydes, and water-soluble chelate compounds, which are the composition of the adhesive excluding the cross-linking regulator, so that the water resistance is maintained without decreasing the degree of polarization. Is characterized by an improvement.
  • the acetoacetyl group-modified polyvinyl alcohol (PVA) resin contains functional groups that are more reactive than modified polyvinyl alcohol resins such as carboxyl group modified, methylol group modified, amino group modified, etc. Excellent in terms of improving the performance.
  • the acetoacetyl group-modified polyvinyl alcohol resin can be obtained by reacting a polyvinyl alcohol resin and diketene by a known method. Specifically, after the polyvinyl alcohol resin is dispersed in a solvent such as acetic acid, a method of adding diketene thereto, after the polyvinyl alcohol resin is previously dissolved in a solvent such as dimethylformamide or dioxane, It can be obtained by a method of adding diketene or a method of directly contacting a diketene gas or liquid diketene with a polyvinyl alcohol resin.
  • the acetoacetyl group-modified polyvinyl alcohol resin is not particularly limited as long as the degree of acetoacetyl group modification is 0.1 mol% or more, preferably 0.1 to 40 mol%, more preferably 1 to 20 mol. %, More preferably 2 to 7 mol%.
  • the degree of modification of acetoacetyl group is less than 0.1 mol%, the adhesive layer has insufficient water resistance and is incompatible, and when the degree of modification of acetoacetyl group exceeds 40 mol%, The improvement effect can be insignificant.
  • the saponification degree of the acetoacetyl group-modified polyvinyl alcohol resin is not particularly limited, but is preferably 80 mol% or more, and more preferably 85 mol% or more. If the degree of saponification of the polyvinyl alcohol-based resin contained in the adhesive composition is low, sufficient water solubility is hardly expressed, and thus the adhesiveness tends to be insufficient.
  • the average polymerization degree of the acetoacetyl group-modified polyvinyl alcohol resin is 1500 or less, preferably 1400 or less, more preferably 1300 or less.
  • the reaction rate is delayed and the stability of liquid preparation is improved.
  • Examples of products include Z-100, Z-200, Z-200H, Z-210, Z-220 and Z-320 (Nippon Synthetic Chemical Industry).
  • the acetoacetyl group-modified polyvinyl alcohol resin may be contained in an amount of 3 to 9% by weight based on the solid content of the adhesive composition. If it is less than 3% by weight based on the above criteria, there is a problem that the water resistance is lowered due to insufficient curing, and if it exceeds 9% by weight, the viscosity increases and bubbles are mixed in during the joining process. Can occur.
  • Dialdehydes contained in the adhesive composition include an acetoacetyl group-modified polyvinyl alcohol (PVA) resin, a polyvinyl alcohol (PVA) polarizer and a protective film such as a cellulose film, an olefin film, and the like. It plays a role of improving the adhesive strength and water resistance.
  • Examples of dialdehydes include glyoxal, propane dial, butane dial, and the like. In particular, glyoxal having a simple structure and high reactivity is preferable.
  • glyoxal is demonstrated, as a dialdehyde, conventionally well-known things can be used as mentioned above, and it is not limited to glyoxal.
  • Glyoxal is presumed that the aldehyde part of glyoxal undergoes a condensation reaction with the acetoacetyl group of the polyvinyl alcohol resin and functions as a crosslinking agent.
  • the weight ratio of glyoxal contained in the adhesive composition is preferably in the range of 20 to 50 parts by weight with respect to 100 parts by weight of the acetoacetyl group-modified polyvinyl alcohol resin.
  • the weight ratio of glyoxal is less than 20 parts by weight based on the above criteria, the water resistance of the adhesive layer when it is made into a polarizing plate is not sufficiently exhibited, and the weight ratio of glyoxal exceeds 50 parts by weight The preparation stability decreases.
  • the water-soluble chelate compound contained in the adhesive composition increases the degree of crosslinking between the adhesive layer and a protective film such as a polyvinyl alcohol (PVA) polarizer and a protective film such as a cellulose film or an olefin film. It can serve to improve water resistance, and can serve as an additive with no problem with optical durability.
  • a protective film such as a polyvinyl alcohol (PVA) polarizer and a protective film such as a cellulose film or an olefin film. It can serve to improve water resistance, and can serve as an additive with no problem with optical durability.
  • the water-soluble chelate compound is added to accelerate the curing of glyoxal.
  • type of chelate compound zinc chloride, cobalt chloride, magnesium chloride, magnesium acetate, aluminum nitrate, zinc nitrate, zinc sulfate and the like can be added.
  • zinc chloride, zinc nitrate, and aluminum nitrate, which are excellent in the role of a crosslinking catalyst, are preferable.
  • the weight ratio of the water-soluble chelate compound contained in the adhesive composition is preferably in the range of 2 to 10 parts by weight with respect to 100 parts by weight of the acetoacetyl group-modified polyvinyl alcohol resin.
  • the weight ratio of the water-soluble chelate compound is less than 2 parts by weight based on the above criteria, the water resistance of the adhesive layer when it is made into a polarizing plate is not sufficiently exhibited, and the weight ratio exceeds 10 parts by weight.
  • the optical characteristics deteriorate.
  • Crosslinking regulator The adhesive composition for polarizing plates according to this embodiment does not contain a crosslinking regulator.
  • the crosslinking regulator is a polyvinyl alcohol resin having no acetoacetyl group, and examples thereof include a polyvinyl alcohol resin and a carboxylic acid-modified polyvinyl alcohol resin.
  • the viscosity of the adhesive composition at 20 ° C. is preferably in the range of 3 to 25 mPa ⁇ sec.
  • the viscosity of the adhesive composition is less than 3 mPa ⁇ sec, the water resistance when the polarizing plate is formed cannot be sufficiently expressed, and when the viscosity exceeds 25 mPa ⁇ sec, the optical properties of the polarizing plate Decreases.
  • the adhesive composition in the present invention is a conventionally known appropriate addition such as a plasticizer, a silane coupling agent, an antistatic agent, fine particles, an alcohol for improving diffusibility, and a leveling agent, as long as the effects of the present invention are not impaired. You may form using what added the agent.
  • the form of the adhesive composition is not particularly limited, but is preferably a liquid type in order to form a uniform adhesive layer on the surface of the polarizer or protective film that is the adherend.
  • a liquid type adhesive a solution type or a dispersion type of various solvents can be used.
  • a solution type is preferable in consideration of the coating property of the substrate, and water is considered in consideration of stability.
  • a solution type or a dispersion type using a solvent is suitable.
  • a polyvinyl alcohol resin for forming a polarizer can be obtained by saponifying a polyvinyl acetate resin.
  • the polyvinyl acetate resin include a copolymer of vinyl acetate and another monomer copolymerizable therewith in addition to polyvinyl acetate which is a homopolymer of vinyl acetate.
  • examples of other monomers copolymerized with vinyl acetate include unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, vinyl ethers, and acrylamides having an ammonium group.
  • the saponification degree of the polyvinyl alcohol resin is usually 85 to 100 mol%, preferably 98 mol% or more.
  • This polyvinyl alcohol-based resin may be further modified, and for example, a polyvinyl polymer or polyvinyl acetal modified with aldehydes may be used.
  • the average degree of polymerization of the polyvinyl alcohol resin constituting the polarizer is usually 1,000 to 10,000, preferably 1,500 to 5,000.
  • a film obtained by forming such a polyvinyl alcohol-based resin into a film is used as an original film of a polarizer (polarizing film).
  • the method for forming the polyvinyl alcohol-based resin is not particularly limited, and a known film forming method can be employed.
  • the film thickness of the polyvinyl alcohol-type resin film used as a raw material is not specifically limited, For example, it is 10 to 150 micrometers.
  • a polarizer (polarizing film) is usually a process of uniaxially stretching a polyvinyl alcohol-based resin film that becomes such a raw material, and the polyvinyl alcohol-based resin film is dyed with a dichroic dye to adsorb the dichroic dye. And a step of treating the polyvinyl alcohol resin film on which the dichroic dye is adsorbed with a boric acid aqueous solution and a step of washing with water after the treatment with the boric acid aqueous solution.
  • Uniaxial stretching may be performed before dyeing, may be performed simultaneously with dyeing, or may be performed after dyeing.
  • uniaxial stretching may be performed before boric acid treatment, may be performed during boric acid treatment, or may be performed after boric acid treatment.
  • the raw film may be uniaxially stretched between different rolls or may be uniaxially stretched using a hot roll.
  • it may be dry stretching such as stretching in the air, or may be wet stretching in which stretching is performed in a state swollen with a solvent.
  • the draw ratio is usually 3 to 8 times.
  • the polyvinyl alcohol resin film can be immersed in an aqueous solution containing the dichroic dye.
  • iodine or a dichroic dye is used as the dichroic dye.
  • the polyvinyl alcohol-type resin film is immersed in water before the dyeing process.
  • iodine When iodine is used as the dichroic dye, a method of immersing and dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide is usually employed.
  • the content of iodine in this aqueous solution is usually 0.01 to 1 part by weight per 100 parts by weight of water, and the content of potassium iodide is usually 0.5 to 20 parts by weight per 100 parts by weight of water.
  • the temperature of the aqueous solution used for dyeing is usually 20 to 40 ° C., and the immersion time in this aqueous solution is usually 20 to 1800 seconds.
  • a method of immersing and dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye is usually employed.
  • the content of the dichroic dye in this aqueous solution is usually 1 ⁇ 10 ⁇ 4 to 10 parts by weight, preferably 1 ⁇ 10 ⁇ 3 to 1 part by weight per 100 parts by weight of water.
  • This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing assistant.
  • the temperature of the aqueous dye solution used for dyeing is usually 20 to 80 ° C., and the immersion time in this aqueous solution is usually 10 to 1800 seconds.
  • the boric acid treatment after dyeing with the dichroic dye is performed by immersing the dyed polyvinyl alcohol resin film in a boric acid-containing aqueous solution.
  • the amount of boric acid in the boric acid-containing aqueous solution is usually 2 to 15 parts by weight, preferably 5 to 12 parts by weight per 100 parts by weight of water.
  • the boric acid-containing aqueous solution preferably contains potassium iodide.
  • the amount of potassium iodide in the boric acid-containing aqueous solution is usually 0.1 to 15 parts by weight, preferably 5 to 12 parts by weight, per 100 parts by weight of water.
  • the immersion time in the boric acid-containing aqueous solution is usually 60 to 1,200 seconds, preferably 150 to 600 seconds, more preferably 200 to 400 seconds.
  • the temperature of the boric acid-containing aqueous solution is usually 50 ° C. or higher, preferably 50 to 85 ° C., more preferably 60 to 80 ° C.
  • the polyvinyl alcohol-based resin film after the boric acid treatment is usually washed with water.
  • the water washing treatment is performed, for example, by immersing a boric acid-treated polyvinyl alcohol resin film in water.
  • the temperature of water in the washing treatment is usually 5 to 40 ° C., and the immersion time is usually 1 to 120 seconds.
  • a drying process is performed to obtain a polarizer (polarizing film).
  • the drying process is usually performed using a hot air dryer or a far infrared heater.
  • the temperature of the drying treatment is usually 30 to 100 ° C, preferably 50 to 80 ° C.
  • the drying time is usually 60 to 600 seconds, preferably 120 to 600 seconds.
  • the polyvinyl alcohol-based resin film is uniaxially stretched, dyed with a dichroic dye, and treated with boric acid to obtain a polarizer (polarizing film).
  • the thickness of this polarizer (polarizing film) is usually in the range of 5 to 40 ⁇ m, preferably in the range of 10 to 35 ⁇ m.
  • the protective film is laminated
  • a protective film various transparent resin films, such as a cellulose resin film, a cycloolefin resin film, an acrylic resin film, and a polyester resin film, can be used, for example.
  • a cellulose resin film When a cellulose resin film is used as the protective film, a cellulose acetate resin in which at least a part of cellulose is esterified is preferable.
  • a cellulose acetate resin in which at least a part of cellulose is esterified is preferable.
  • triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate and the like can be mentioned.
  • the cycloolefin resin is a thermoplastic resin having a cycloolefin monomer unit such as norbornene or a polycyclic norbornene monomer, and the cycloolefin ring-opening polymer or two or more kinds of cycloolefins. It may be a hydrogenated product of a ring-opening copolymer using, and may be an addition copolymer of a cycloolefin with a chain olefin or an aromatic compound having a vinyl group. Moreover, the polar group may be introduce
  • Bonding of a polarizer (polarizing film) using an adhesive composition and a protective film can be performed by an appropriate method, for example, casting method, Mayer bar coating method, gravure coating method, die coating method, dip coating method. And a method of applying an adhesive composition to the adhesive surface of a polarizer (polarizing film) and / or a protective film by a spraying method and superimposing the two. With the casting method, the adhesive composition is applied to the surface of the object to be coated while the polarizer (polarizing film) or protective film is moved in a generally vertical direction, a generally horizontal direction, or an oblique direction between the two. It is a method to do.
  • a polarizer polarizing film
  • a protective film are pinched
  • the surface of the polarizer (polarizing film) and / or protective film may be appropriately subjected to surface treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, frame treatment, and saponification treatment.
  • surface treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, frame treatment, and saponification treatment.
  • saponification treatment include a method of immersing in an aqueous solution of an alkali such as sodium hydroxide or potassium hydroxide.
  • a drying process is performed.
  • the drying process is performed, for example, by spraying hot air, and the temperature at that time is appropriately selected in the range of 50 to 100 ° C.
  • the drying time is usually 30 to 1,000 seconds.
  • a 75 ⁇ m-thick polyvinyl alcohol film having an average degree of polymerization of 2,400 and a saponification degree of 99.9 mol% or more is uniaxially stretched about 5 times in a dry manner and maintained at 60 ° C. while maintaining the stretched state. After being immersed in (distilled water) for 1 minute, it was immersed in a 28 ° C. aqueous solution having a weight ratio of iodine / potassium iodide / distilled water of 0.05 / 5/100 for 60 seconds. Then, after immersing in a 72 ° C.
  • aqueous solution having a weight ratio of potassium iodide / boric acid / distilled water of 8.5 / 8.5 / 100 for 300 seconds and washing with 26 ° C. distilled water for 20 seconds, 65 ° C. And a polarizer having iodine adsorbed and oriented on a PVA film.
  • KC8UX (Konica, T), which is a triacetyl cellulose film, was used after saponification.
  • Acetate group-modified polyvinyl alcohol resin (Z200, Nippon Synthetic Chemical Industry Co., Ltd., average polymerization degree 1200) having a saponification degree of 99.2 mol% is dissolved in water (distilled water) to form a solid adhesive composition.
  • An acetoacetyl group-modified polyvinyl alcohol-based resin aqueous solution was obtained by adding 6% by weight of acetoacetyl group-modified polyvinyl alcohol on a weight basis.
  • the acetoacetyl group-modified polyvinyl alcohol-based resin aqueous solution and glyoxal (40% aqueous solution, gold tejonate) are mixed so as to be 20 parts by weight with respect to 100 parts by weight of the acetoacetyl group-modified polyvinyl alcohol-based resin.
  • the compound zinc chloride (gold gold) was mixed at 2 parts by weight with respect to 100 parts by weight of the acetoacetyl group-modified polyvinyl alcohol resin to produce an adhesive composition.
  • a cellulose-based protective film Konica, KC8UX (trade name), triacetyl cellulose) Film
  • the bonded polarizing plate was dried with a hot air dryer at 80 ° C. for 5 minutes to produce a polarizing plate.
  • the adhesive composition was manufactured by changing only the ratio in the same manner as in Example 1 (unit: parts by weight, see Table 1).
  • Example 9 An adhesive composition was produced under the same conditions as in Example 1 except that the water-soluble chelate compound aluminum sulfate (Aldrich) was mixed to 5 parts by weight with respect to 100 parts by weight of the acetoacetyl group-modified polyvinyl alcohol resin. (See Table 1).
  • Example 9 the water-soluble chelate compound aluminum sulfate (Aldrich) was mixed to 5 parts by weight with respect to 100 parts by weight of the acetoacetyl group-modified polyvinyl alcohol resin. (See Table 1).
  • Aldrich water-soluble chelate compound aluminum sulfate
  • An adhesive composition was produced under the same conditions as in Example 1 except that 3% by weight of acetoacetyl group-modified polyvinyl alcohol was included based on the weight of the solid content of the adhesive composition (see Table 1).
  • An adhesive composition was produced under the same conditions as in Example 1 except that 9% by weight of acetoacetyl group-modified polyvinyl alcohol was included based on the solid content weight of the adhesive composition (see Table 1).
  • An adhesive composition was produced under the same conditions as in Example 1 except that 2% by weight of acetoacetyl group-modified polyvinyl alcohol was included based on the solid content weight of the adhesive composition (see Table 1).
  • An adhesive composition was produced under the same conditions as in Example 1 except that 10% by weight of acetoacetyl group-modified polyvinyl alcohol was included based on the weight of the solid content of the adhesive composition (see Table 1).
  • An adhesive composition was produced under the same conditions as in Example 1 except that sodium glyoxylate (Sigma Aldrich) was mixed with acetoacetyl group-modified polyvinyl alcohol resin instead of glyoxal (see Table 1).
  • FIG. 1 is a diagram schematically showing a water resistance evaluation test method, in which (A) shows a sample (1) before immersion in warm water, and (B) shows a sample (1) after immersion in warm water. . As shown in FIG.
  • one short side of the sample was gripped by the gripper (5), and about 80% of the length direction was immersed in a 60 ° C. water bath and maintained for 4 hours. Then, the sample (1) was taken out from the water tank and the moisture was wiped off.
  • the polarizer (polarizing film) (4) of the polarizing plate contracts by immersion in warm water.
  • the polarizer (polarizing film) (4) located in the center of a polarizing plate is contracted by immersion in warm water, so that the polarizer (polarizing film) is interposed between protective films.
  • Iodine elutes from the peripheral portion of (4), and a portion (3) where the color is lost is generated at the peripheral portion of sample (1).
  • This degree of decolorization was evaluated by measuring the distance from the end of the contracted polarizer (polarizing film) (4) at the center of the short side of the sample (1) to the region where the color peculiar to the polarizing plate remained, The length was missing.
  • the total of the shrinkage length and the length from which iodine was removed was defined as the total erosion length X.
  • the total erosion length X is the distance from the end (1a) of the sample (1) to the region where the color peculiar to the polarizing plate remains at the center of the short side of the sample (1).
  • Total erosion length X is less than 2 mm
  • Total erosion length X is 2 mm or more and less than 3 mm
  • Total erosion length X is 3 mm or more and less than 5 mm
  • Total erosion length X is 5 mm or more
  • the manufactured polarizing plate was cut into a size of 4 cm ⁇ 4 cm to prepare a specimen, and after attaching the specimen to a measurement holder, an ultraviolet-visible light spectrometer (V-7100, manufactured by JASCO) was used. The results are shown in Table 2.
  • Examples 1 to 14 exhibited superior adhesion, water resistance, and optical properties as compared with Comparative Examples 1 to 8.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)

Abstract

An adhesive composition for a polarizing plate contains an acetoacetyl group-modified polyvinyl alcohol resin, a dialdehyde, and a water-soluble chelate compound, and does not contain a crosslinking modifier, the acetoacetyl group-modified polyvinyl alcohol resin having an average polymerization degree of 1500 or less.

Description

接着剤組成物及びこれを含む偏光板Adhesive composition and polarizing plate containing the same
　本発明は、接着剤組成物及び前記接着剤組成物を用いて偏光子と偏光子保護フィルムとが接合された偏光板に関する。 The present invention relates to an adhesive composition and a polarizing plate in which a polarizer and a polarizer protective film are bonded using the adhesive composition.
　偏光板は、液晶表示装置を構成する光学部品の１つとして有用である。偏光板は通常、偏光子の両面に保護フィルムが積層された構造を有し、液晶表示装置に挿入される。偏光子の一方の面にのみ保護フィルムを設けることも知られているが、多くの場合、他方の面には単純な保護フィルムではなく、別途の機能として例えば光学機能を有する層が保護フィルムを兼ねて接合される。 The polarizing plate is useful as one of the optical components constituting the liquid crystal display device. A polarizing plate usually has a structure in which protective films are laminated on both sides of a polarizer, and is inserted into a liquid crystal display device. It is also known that a protective film is provided only on one side of a polarizer, but in many cases, a protective film is not provided on the other side, but a layer having an optical function, for example, as a separate function. Also joined together.
　現在一般的に、ポリビニルアルコールにヨウ素を吸着配向させたヨウ素系フィルムやポリビニルアルコールに二色性染料を吸着配向させた染料系フィルムを偏光子として用い、少なくともフィルムの片面にポリビニルアルコール系樹脂の水溶液（ポリビニルアルコール系接着剤）を用いて形成された接着層を通じてトリアセチルセルロース（ＴＡＣ）などの保護フィルムを接合した構成の偏光板が用いられているが、このような構成の偏光板には、湿熱下で長時間用いた場合、保護フィルムと偏光子の端面が剥離しやすいという問題がある。 Currently, an iodine-based film in which iodine is adsorbed and oriented in polyvinyl alcohol and a dye-based film in which dichroic dye is adsorbed and oriented in polyvinyl alcohol are used as a polarizer, and an aqueous solution of a polyvinyl alcohol-based resin on at least one side of the film A polarizing plate having a configuration in which a protective film such as triacetyl cellulose (TAC) is bonded through an adhesive layer formed using (polyvinyl alcohol-based adhesive) is used. When it uses for a long time under wet heat, there exists a problem that the end surface of a protective film and a polarizer tends to peel.
　これにより、偏光子（偏光フィルム）と保護フィルムとをポリビニルアルコール系接着剤を用いて接合した後、９０～１００℃の温度で加熱乾燥することで耐湿熱性を改良した偏光板が提案されているが、依然として湿熱下で長時間用いた場合、保護フィルムと偏光子の端面が容易に剥離されるという問題点が解決されていない。 Accordingly, there has been proposed a polarizing plate having improved resistance to moisture and heat by bonding a polarizer (polarizing film) and a protective film using a polyvinyl alcohol-based adhesive and then drying by heating at a temperature of 90 to 100 ° C. However, the problem that the protective film and the end face of the polarizer are easily peeled off when used for a long time under wet heat has not been solved.
このような問題点を改善すべく、特開平０７－１３４２１２号ではポリビニルアルコール系樹脂、グリオキサール、及び塩化亜鉛を含む接着剤組成物を開示している。 In order to improve such problems, JP-A-07-134212 discloses an adhesive composition containing a polyvinyl alcohol resin, glyoxal, and zinc chloride.
特開平０７－１３４２１２号JP 07-134212 A
しかしながら、前記接着剤組成物の場合、湿熱劣化による偏光度の低下が発生することがわかった。
本発明は、接着力と偏光度とが低下することなく耐水性が向上した偏光板用接着剤組成物を提供する。 However, in the case of the adhesive composition, it has been found that the degree of polarization decreases due to wet heat deterioration.
This invention provides the adhesive composition for polarizing plates which improved water resistance, without the adhesive force and polarization degree falling.
本発明は、アセトアセチル基変性ポリビニルアルコール系樹脂、ジアルデヒド類、及び水溶性キレート化合物を含み、架橋調節剤を含んでおらず、前記アセトアセチル基変性ポリビニルアルコール系樹脂の平均重合度が１５００以下である、偏光板用接着剤組成物を提供する。 The present invention includes an acetoacetyl group-modified polyvinyl alcohol resin, a dialdehyde, and a water-soluble chelate compound, does not include a crosslinking regulator, and the average degree of polymerization of the acetoacetyl group-modified polyvinyl alcohol resin is 1500 or less. The adhesive composition for polarizing plates is provided.
他の一具現例は、アセトアセチル基変性ポリビニルアルコール系樹脂が接着剤組成物の固形分重量を基準として３ないし９重量％で含まれるものであってもよい。 In another embodiment, the acetoacetyl group-modified polyvinyl alcohol resin may be included in an amount of 3 to 9% by weight based on the solid content weight of the adhesive composition.
さらに他の一具現例は、アセトアセチル基変性ポリビニルアルコール系樹脂１００重量部に対して、ジアルデヒド類は２０ないし５０重量部で含まれ、水溶性キレート化合物は２ないし１０重量部で含まれるものであってもよい。 In another embodiment, dialdehydes are contained in an amount of 20 to 50 parts by weight and a water-soluble chelate compound is contained in an amount of 2 to 10 parts by weight with respect to 100 parts by weight of an acetoacetyl group-modified polyvinyl alcohol resin. It may be.
さらに他の一具現例は、ジアルデヒド類がグリオキサールであってもよい。 In another embodiment, the dialdehyde may be glyoxal.
さらに他の一具現例は、水溶性キレート化合物が、塩化亜鉛、塩化コバルト、塩化マグネシウム、酢酸マグネシウム、硝酸アルミニウム、硝酸亜鉛、及び硫酸亜鉛からなる群より選択される１種以上であってもよい。 In another embodiment, the water-soluble chelate compound may be one or more selected from the group consisting of zinc chloride, cobalt chloride, magnesium chloride, magnesium acetate, aluminum nitrate, zinc nitrate, and zinc sulfate. .
また、本発明は、ポリビニルアルコール系偏光子；前記偏光子の一面又は両面に積層され、前記接着剤組成物を含有する接着剤層；及び前記接着剤層上に一面又は両面に積層された偏光子保護フィルムを含む偏光板を提供する。 The present invention also provides a polyvinyl alcohol polarizer; an adhesive layer laminated on one or both sides of the polarizer and containing the adhesive composition; and a polarization laminated on one or both sides on the adhesive layer. Provided is a polarizing plate comprising a child protective film.
本発明の偏光板用接着剤組成物は、接着力と偏光度が低下することなく耐水性が向上するという効果を有する。 The adhesive composition for polarizing plates of this invention has the effect that water resistance improves, without the adhesive force and polarization degree falling.
図１は、実験例による耐水性の評価試験方法を模式的に示した図である。FIG. 1 is a diagram schematically showing a water resistance evaluation test method according to an experimental example.
以下、本発明を詳しく説明する。 The present invention will be described in detail below.
本発明は、アセトアセチル基変性ポリビニルアルコール系樹脂、ジアルデヒド類、及び水溶性キレート化合物を含み、架橋調節剤を含んでおらず、前記アセトアセチル基変性ポリビニルアルコール系樹脂の平均重合度が１５００以下である、偏光板用接着剤組成物及び前記接着剤組成物を用いて偏光子と偏光子保護フィルムとが接合された偏光板を提供する。 The present invention includes an acetoacetyl group-modified polyvinyl alcohol resin, a dialdehyde, and a water-soluble chelate compound, does not include a crosslinking regulator, and the average degree of polymerization of the acetoacetyl group-modified polyvinyl alcohol resin is 1500 or less. The polarizing plate adhesive composition for polarizing plates and the polarizing plate by which the polarizer and the polarizer protective film were joined using the said adhesive composition are provided.
本発明の接着剤組成物は、調液安定性の問題を接着剤の投入プロセスを改善して解決し、湿熱劣化によって偏光度の低下を発生させる架橋調節剤を添加しなくとも接着性及び耐久性を有するという効果を有する。すなわち本発明は、架橋調節剤を除いた接着剤の組成であるアセトアセチル基変性ポリビニルアルコール系樹脂、ジアルデヒド類、及び水溶性キレート化合物の含量を増加させて偏光度が低下することなく耐水性が向上したことを特徴とする。 The adhesive composition of the present invention solves the problem of liquid preparation stability by improving the process of charging the adhesive, and is adhesive and durable without the addition of a crosslinking regulator that causes a decrease in the degree of polarization due to wet heat deterioration. It has the effect of having sex. That is, the present invention increases the content of acetoacetyl group-modified polyvinyl alcohol resins, dialdehydes, and water-soluble chelate compounds, which are the composition of the adhesive excluding the cross-linking regulator, so that the water resistance is maintained without decreasing the degree of polarization. Is characterized by an improvement.
以下、接着剤組成物の構成についてさらに詳しく説明する。 Hereinafter, the configuration of the adhesive composition will be described in more detail.
アセトアセチル基変性ポリビニルアルコール系樹脂Acetoacetyl group-modified polyvinyl alcohol resin
アセトアセチル基変性ポリビニルアルコール（ＰＶＡ）系樹脂は、カルボキシル基変性、メチロール基変性、アミノ基変性などのような変性されたポリビニルアルコール樹脂に比べて反応性の高い官能基を含有しており、耐久性の向上の面で優れている。 The acetoacetyl group-modified polyvinyl alcohol (PVA) resin contains functional groups that are more reactive than modified polyvinyl alcohol resins such as carboxyl group modified, methylol group modified, amino group modified, etc. Excellent in terms of improving the performance.
アセトアセチル基変性ポリビニルアルコール系樹脂は、ポリビニルアルコール系樹脂とジケテン（ｄｉｋｅｔｅｎｅ）とを公知の方法で反応させて得ることができる。具体的には、ポリビニルアルコール系樹脂を酢酸などの溶媒中に分散させた後、これにジケテンを添加する方法、ポリビニルアルコール系樹脂をジメチルホルムアミド又はジオキサンなどの溶媒に予め溶解させた後、これにジケテンを添加する方法、又はポリビニルアルコール系樹脂にジケテンガス又は液状ジケテンを直接接触させる方法などによって得ることができる。アセトアセチル基変性ポリビニルアルコール系樹脂は、アセトアセチル基変性度が０．１モル％以上のものであれば特に剤限されず、好ましくは０．１ないし４０モル％、より好ましくは１ないし２０モル％、さらに好ましくは２ないし７モル％のものがよい。アセトアセチル基の変性度が０．１モル％未満である場合は接着剤層の耐水性が不十分で不適合であり、アセトアセチル基の変性度が４０モル％を超過する場合は、耐水性の向上効果が微々たるものとなり得る。 The acetoacetyl group-modified polyvinyl alcohol resin can be obtained by reacting a polyvinyl alcohol resin and diketene by a known method. Specifically, after the polyvinyl alcohol resin is dispersed in a solvent such as acetic acid, a method of adding diketene thereto, after the polyvinyl alcohol resin is previously dissolved in a solvent such as dimethylformamide or dioxane, It can be obtained by a method of adding diketene or a method of directly contacting a diketene gas or liquid diketene with a polyvinyl alcohol resin. The acetoacetyl group-modified polyvinyl alcohol resin is not particularly limited as long as the degree of acetoacetyl group modification is 0.1 mol% or more, preferably 0.1 to 40 mol%, more preferably 1 to 20 mol. %, More preferably 2 to 7 mol%. When the degree of modification of acetoacetyl group is less than 0.1 mol%, the adhesive layer has insufficient water resistance and is incompatible, and when the degree of modification of acetoacetyl group exceeds 40 mol%, The improvement effect can be insignificant.
アセトアセチル基変性ポリビニルアルコール系樹脂のけん化度も特に剤限されないが、８０モル％以上であることが好ましく、さらには８５モル％以上であることがより好ましい。接着剤組成物に含まれるポリビニルアルコール系樹脂のけん化度が低いと、十分な水溶性が発現しにくくなるため接着性が不十分になりやすい。 The saponification degree of the acetoacetyl group-modified polyvinyl alcohol resin is not particularly limited, but is preferably 80 mol% or more, and more preferably 85 mol% or more. If the degree of saponification of the polyvinyl alcohol-based resin contained in the adhesive composition is low, sufficient water solubility is hardly expressed, and thus the adhesiveness tends to be insufficient.
前記アセトアセチル基変性ポリビニルアルコール系樹脂の平均重合度は１５００以下であり、好ましくは１４００以下、より好ましくは１３００以下である。平均重合度が１５００以下であることによって反応速度を遅らせて調液安定性が向上するようになる。 The average polymerization degree of the acetoacetyl group-modified polyvinyl alcohol resin is 1500 or less, preferably 1400 or less, more preferably 1300 or less. When the average degree of polymerization is 1500 or less, the reaction rate is delayed and the stability of liquid preparation is improved.
一例の製品としては、Ｚ－１００、Ｚ－２００、Ｚ－２００Ｈ、Ｚ－２１０、Ｚ－２２０及びＺ－３２０（日本合成化学工業社）などがある。 Examples of products include Z-100, Z-200, Z-200H, Z-210, Z-220 and Z-320 (Nippon Synthetic Chemical Industry).
前記アセトアセチル基変性ポリビニルアルコール系樹脂は、接着剤組成物の固形分重量基準で３ないし９重量％で含まれるものであってもよい。上記基準で３重量％未満である場合、硬化が不足して耐水性が低下するという問題点があり、９重量％を超過する場合、粘度が高くなり接合工程中に気泡が混入するという問題点が発生し得る。 The acetoacetyl group-modified polyvinyl alcohol resin may be contained in an amount of 3 to 9% by weight based on the solid content of the adhesive composition. If it is less than 3% by weight based on the above criteria, there is a problem that the water resistance is lowered due to insufficient curing, and if it exceeds 9% by weight, the viscosity increases and bubbles are mixed in during the joining process. Can occur.
ジアルデヒド類Dialdehydes
接着剤組成物に含まれるジアルデヒド類は、アセトアセチル（ａｃｅｔｏａｃｅｔｙｌ）基変性ポリビニルアルコール（ＰＶＡ）系樹脂をポリビニルアルコール（ＰＶＡ）系偏光子及びセルロース系フィルム、オレフィン系フィルムなどのような保護フィルムとの接着力及び耐水性を向上させる役割をする。
ジアルデヒド類としては、例えば、グリオキサール、プロパンジアール、ブタンジアールなどが挙げられる。特に、構造が簡潔で反応性に富むグリオキサールが好ましい。
以下、グリオキサールについて説明するが、ジアルデヒド類としては、上述のように従来公知のものを用いることが可能であり、グリオキサールに限定するものでない。 Dialdehydes contained in the adhesive composition include an acetoacetyl group-modified polyvinyl alcohol (PVA) resin, a polyvinyl alcohol (PVA) polarizer and a protective film such as a cellulose film, an olefin film, and the like. It plays a role of improving the adhesive strength and water resistance.
Examples of dialdehydes include glyoxal, propane dial, butane dial, and the like. In particular, glyoxal having a simple structure and high reactivity is preferable.
Hereinafter, although glyoxal is demonstrated, as a dialdehyde, conventionally well-known things can be used as mentioned above, and it is not limited to glyoxal.
グリオキサールは、グリオキサールのアルデヒド部分がポリビニルアルコール系樹脂のアセトアセチル基と縮合反応を進行し、架橋剤として機能すると推測される。 Glyoxal is presumed that the aldehyde part of glyoxal undergoes a condensation reaction with the acetoacetyl group of the polyvinyl alcohol resin and functions as a crosslinking agent.
接着剤組成物に含まれるグリオキサールの重量比は、アセトアセチル基変性ポリビニルアルコール系樹脂１００重量部に対して２０ないし５０重量部の範囲にあることが好ましい。上記基準でグリオキサールの重量比が２０重量部未満である場合は、偏光板にしたときの接着剤層の耐水性が十分に発現しにくくなり、またグリオキサールの重量比が５０重量部を超過する場合は、調液安定性が低下する。 The weight ratio of glyoxal contained in the adhesive composition is preferably in the range of 20 to 50 parts by weight with respect to 100 parts by weight of the acetoacetyl group-modified polyvinyl alcohol resin. When the weight ratio of glyoxal is less than 20 parts by weight based on the above criteria, the water resistance of the adhesive layer when it is made into a polarizing plate is not sufficiently exhibited, and the weight ratio of glyoxal exceeds 50 parts by weight The preparation stability decreases.
水溶性キレート化合物Water-soluble chelate compound
接着剤組成物に含まれる水溶性キレート化合物は、接着剤層とポリビニルアルコール（ＰＶＡ）系偏光子及びセルロース系フィルム、オレフィン系フィルムなどのような保護フィルム間の架橋度を上昇させて接着力及び耐水性を向上させる役割をすることができ、光学耐久性も問題のない添加剤の役割をすることができる。 The water-soluble chelate compound contained in the adhesive composition increases the degree of crosslinking between the adhesive layer and a protective film such as a polyvinyl alcohol (PVA) polarizer and a protective film such as a cellulose film or an olefin film. It can serve to improve water resistance, and can serve as an additive with no problem with optical durability.
水溶性キレート化合物は、グリオキサールの硬化促進のために添加する。キレート化合物の種類は、塩化亜鉛、塩化コバルト、塩化マグネシウム、酢酸マグネシウム、硝酸アルミニウム、硝酸亜鉛、硫酸亜鉛などを添加することができる。特に架橋触媒の役割に優れた塩化亜鉛及び硝酸亜鉛、硝酸アルミニウムが好ましい。 The water-soluble chelate compound is added to accelerate the curing of glyoxal. As the type of chelate compound, zinc chloride, cobalt chloride, magnesium chloride, magnesium acetate, aluminum nitrate, zinc nitrate, zinc sulfate and the like can be added. In particular, zinc chloride, zinc nitrate, and aluminum nitrate, which are excellent in the role of a crosslinking catalyst, are preferable.
接着剤組成物に含まれる水溶性キレート化合物の重量比は、アセトアセチル基変性ポリビニルアルコール系樹脂１００重量部に対して２ないし１０重量部の範囲にあることが好ましい。上記基準で水溶性キレート化合物の重量比が２重量部未満である場合は、偏光板にしたときの接着剤層の耐水性が十分に発現しにくくなり、重量比が１０重量部を超過する場合は、光特性が低下する。
架橋調節剤
本実施形態に係る偏光板用接着剤組成物は、架橋調節剤を含まない。架橋調節剤とは、アセトアセチル基を有さないポリビニルアルコール系樹脂であり、例えば、ポリビニルアルコール樹脂、カルボン酸変性ポリビニルアルコール樹脂などが挙げられる。 The weight ratio of the water-soluble chelate compound contained in the adhesive composition is preferably in the range of 2 to 10 parts by weight with respect to 100 parts by weight of the acetoacetyl group-modified polyvinyl alcohol resin. When the weight ratio of the water-soluble chelate compound is less than 2 parts by weight based on the above criteria, the water resistance of the adhesive layer when it is made into a polarizing plate is not sufficiently exhibited, and the weight ratio exceeds 10 parts by weight. The optical characteristics deteriorate.
Crosslinking regulator The adhesive composition for polarizing plates according to this embodiment does not contain a crosslinking regulator. The crosslinking regulator is a polyvinyl alcohol resin having no acetoacetyl group, and examples thereof include a polyvinyl alcohol resin and a carboxylic acid-modified polyvinyl alcohol resin.
接着剤組成物の２０℃における粘度は３ないし２５ｍＰａ・ｓｅｃの範囲にあることが好ましい。接着剤組成物の粘度が３ｍＰａ・ｓｅｃ未満である場合は、偏光板にしたときの耐水性を十分に発現することができず、粘度が２５ｍＰａ・ｓｅｃを超越する場合は、偏光板の光学特性が低下する。 The viscosity of the adhesive composition at 20 ° C. is preferably in the range of 3 to 25 mPa · sec. When the viscosity of the adhesive composition is less than 3 mPa · sec, the water resistance when the polarizing plate is formed cannot be sufficiently expressed, and when the viscosity exceeds 25 mPa · sec, the optical properties of the polarizing plate Decreases.
本発明における接着剤組成物は、本発明の効果を阻害しない範囲で、可塑剤、シランカップリング剤、帯電防止剤、微粒子、拡散性を良好にするアルコール、レベリング剤など従来公知の適切な添加剤が添加されたものを用いて形成されてもよい。 The adhesive composition in the present invention is a conventionally known appropriate addition such as a plasticizer, a silane coupling agent, an antistatic agent, fine particles, an alcohol for improving diffusibility, and a leveling agent, as long as the effects of the present invention are not impaired. You may form using what added the agent.
接着剤組成物の形態は特に剤限されないが、被着体である偏光子又は保護フィルムの表面に均一な接着剤層を形成するために液型であることが好ましい。このような液型の接着剤は、各種溶剤の溶液型又は分散液型を用いることができ、基材の塗工性の面を考慮すると溶液型が好ましく、安定性の面を考慮すると水を溶媒とした溶液型又は分散液型が適する。 The form of the adhesive composition is not particularly limited, but is preferably a liquid type in order to form a uniform adhesive layer on the surface of the polarizer or protective film that is the adherend. As such a liquid type adhesive, a solution type or a dispersion type of various solvents can be used. A solution type is preferable in consideration of the coating property of the substrate, and water is considered in consideration of stability. A solution type or a dispersion type using a solvent is suitable.
以下、偏光板の構成について詳しく説明する。 Hereinafter, the configuration of the polarizing plate will be described in detail.
偏光子（偏光フィルム）Polarizer (polarizing film)
偏光子を形成するためのポリビニルアルコール系樹脂は、ポリ酢酸ビニル系樹脂をけん化することで得られる。ポリ酢酸ビニル系樹脂としては、酢酸ビニルの単独重合体であるポリ酢酸ビニル以外に、酢酸ビニルとそれに共重合可能な他の単量体との共重合体などが例示される。酢酸ビニルに共重合される他の単量体としては、例えば不飽和カルボン酸類、不飽和スルホン酸類、オレフィン類、ビニルエーテル類、アンモニウム基を有するアクリルアミド類などが挙げられる。ポリビニルアルコール系樹脂のけん化度は、通常８５ないし１００モル％、好ましくは９８モル％以上である。このポリビニルアルコール系樹脂はさらに変性されていてもよく、例えばアルデヒド類で変性されたポリビニル重合体やポリビニルアセタールなどを用いてもよい。偏光子を構成するポリビニルアルコール系樹脂の平均重合度は、通常１，０００ないし１０，０００、好ましくは１，５００ないし５，０００である。 A polyvinyl alcohol resin for forming a polarizer can be obtained by saponifying a polyvinyl acetate resin. Examples of the polyvinyl acetate resin include a copolymer of vinyl acetate and another monomer copolymerizable therewith in addition to polyvinyl acetate which is a homopolymer of vinyl acetate. Examples of other monomers copolymerized with vinyl acetate include unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, vinyl ethers, and acrylamides having an ammonium group. The saponification degree of the polyvinyl alcohol resin is usually 85 to 100 mol%, preferably 98 mol% or more. This polyvinyl alcohol-based resin may be further modified, and for example, a polyvinyl polymer or polyvinyl acetal modified with aldehydes may be used. The average degree of polymerization of the polyvinyl alcohol resin constituting the polarizer is usually 1,000 to 10,000, preferably 1,500 to 5,000.
このようなポリビニルアルコール系樹脂をフィルム状に製膜したもの（ポリビニルアルコール系樹脂フィルム）が偏光子（偏光フィルム）の原反フィルムに用いられる。ポリビニルアルコール系樹脂を製膜する方法は特に限定されるものではなく、公知の製膜方法を採用することができる。原反となるポリビニルアルコール系樹脂フィルムの膜厚は特に限定されないが、例えば１０ないし１５０μｍである。 A film obtained by forming such a polyvinyl alcohol-based resin into a film (polyvinyl alcohol-based resin film) is used as an original film of a polarizer (polarizing film). The method for forming the polyvinyl alcohol-based resin is not particularly limited, and a known film forming method can be employed. Although the film thickness of the polyvinyl alcohol-type resin film used as a raw material is not specifically limited, For example, it is 10 to 150 micrometers.
偏光子（偏光フィルム）は、通常、このような原反となるポリビニルアルコール系樹脂フィルムを１軸延伸する工程、ポリビニルアルコール系樹脂フィルムを２色性色素で染色してその２色性色素を吸着させる工程、２色性色素が吸着されたポリビニルアルコール系樹脂フィルムをホウ酸水溶液で処理する工程、及びこのホウ酸水溶液による処理後に水洗する工程を含む方法によって製造される。 A polarizer (polarizing film) is usually a process of uniaxially stretching a polyvinyl alcohol-based resin film that becomes such a raw material, and the polyvinyl alcohol-based resin film is dyed with a dichroic dye to adsorb the dichroic dye. And a step of treating the polyvinyl alcohol resin film on which the dichroic dye is adsorbed with a boric acid aqueous solution and a step of washing with water after the treatment with the boric acid aqueous solution.
１軸延伸は、染色前に行ってもよく、染色と同時に行ってもよく、染色後に行ってもよい。１軸延伸を染色後に行う場合は、１軸延伸はホウ酸処理前に行ってもよく、ホウ酸処理中に行ってもよく、ホウ酸処理後にも行うことができる。勿論、これらの複数のステップにより１軸延伸を行うことも可能である。１軸延伸においては、原反フィルムを異なるロール間で１軸延伸してもよく、熱ロールを用いて１軸延伸してもよい。また、大気中で延伸を行うなどの乾式延伸であってもよく、溶剤で膨潤させた状態で延伸を行う湿式延伸であってもよい。延伸倍率は通常３ないし８倍である。 Uniaxial stretching may be performed before dyeing, may be performed simultaneously with dyeing, or may be performed after dyeing. When uniaxial stretching is performed after dyeing, uniaxial stretching may be performed before boric acid treatment, may be performed during boric acid treatment, or may be performed after boric acid treatment. Of course, it is also possible to perform uniaxial stretching by these plural steps. In the uniaxial stretching, the raw film may be uniaxially stretched between different rolls or may be uniaxially stretched using a hot roll. Further, it may be dry stretching such as stretching in the air, or may be wet stretching in which stretching is performed in a state swollen with a solvent. The draw ratio is usually 3 to 8 times.
ポリビニルアルコール系樹脂フィルムを２色性色素で染色するためには、例えば２色性色素を含有する水溶液にポリビニルアルコール系樹脂フィルムを浸漬することができる。２色性色素として具体的には、ヨウ素又は２色性染料が用いられる。また、ポリビニルアルコール系樹脂フィルムは染色処理前に水に浸漬処理を施しておくことが好ましい。 In order to dye a polyvinyl alcohol resin film with a dichroic dye, for example, the polyvinyl alcohol resin film can be immersed in an aqueous solution containing the dichroic dye. Specifically, iodine or a dichroic dye is used as the dichroic dye. Moreover, it is preferable that the polyvinyl alcohol-type resin film is immersed in water before the dyeing process.
２色性色素としてヨウ素を用いる場合は通常、ヨウ素及びヨウ化カリウムを含有する水溶液にポリビニルアルコール系樹脂フィルムを浸漬して染色する方法が採用される。この水溶液におけるヨウ素の含有量は通常、水１００重量部当たり０．０１ないし１重量部であり、ヨウ化カリウムの含有量は通常、水１００重量部当たり０．５ないし２０重量部である。染色に用いる水溶液の温度は通常２０ないし４０℃であり、またこの水溶液への浸漬時間は通常２０ないし１８００秒である。 When iodine is used as the dichroic dye, a method of immersing and dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide is usually employed. The content of iodine in this aqueous solution is usually 0.01 to 1 part by weight per 100 parts by weight of water, and the content of potassium iodide is usually 0.5 to 20 parts by weight per 100 parts by weight of water. The temperature of the aqueous solution used for dyeing is usually 20 to 40 ° C., and the immersion time in this aqueous solution is usually 20 to 1800 seconds.
２色性色素として２色性染料を用いる場合は通常、水溶性２色性染料を含む水溶液にポリビニルアルコール系樹脂フィルムを浸漬して染色する方法が採用される。この水溶液における２色性染料の含有量は、水１００重量部当たり通常１×１０－４ないし１０重量部、好ましくは１×１０－３ないし１重量部である。この水溶液は硫酸ナトリウムなどの無機塩を染色助剤として含有してもよい。染色に用いる染料水溶液の温度は通常２０ないし８０℃であり、またこの水溶液に対する浸漬時間は通常１０ないし１，８００秒である。 When a dichroic dye is used as the dichroic dye, a method of immersing and dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye is usually employed. The content of the dichroic dye in this aqueous solution is usually 1 × 10 −4 to 10 parts by weight, preferably 1 × 10 −3 to 1 part by weight per 100 parts by weight of water. This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing assistant. The temperature of the aqueous dye solution used for dyeing is usually 20 to 80 ° C., and the immersion time in this aqueous solution is usually 10 to 1800 seconds.
２色性色素による染色後のホウ酸処理は、染色されたポリビニルアルコール系樹脂フィルムをホウ酸含有水溶液に浸漬することによって行われる。ホウ酸含有水溶液におけるホウ酸の量は、水１００重量部当たり通常２ないし１５重量部、好ましくは５ないし１２重量部である。２色性色素としてヨウ素を用いる場合は、このホウ酸含有水溶液はヨウ化カリウムを含有することが好ましい。ホウ酸含有水溶液におけるヨウ化カリウムの量は、水１００重量部当たり通常０．１ないし１５重量部、好ましくは５ないし１２重量部である。ホウ酸含有水溶液への浸漬時間は、通常６０ないし１，２００秒、好ましくは１５０ないし６００秒、より好ましくは２００ないし４００秒である。ホウ酸含有水溶液の温度は、通常５０℃以上であり、好ましくは５０ないし８５℃、より好ましくは６０ないし８０℃である。 The boric acid treatment after dyeing with the dichroic dye is performed by immersing the dyed polyvinyl alcohol resin film in a boric acid-containing aqueous solution. The amount of boric acid in the boric acid-containing aqueous solution is usually 2 to 15 parts by weight, preferably 5 to 12 parts by weight per 100 parts by weight of water. When iodine is used as the dichroic dye, the boric acid-containing aqueous solution preferably contains potassium iodide. The amount of potassium iodide in the boric acid-containing aqueous solution is usually 0.1 to 15 parts by weight, preferably 5 to 12 parts by weight, per 100 parts by weight of water. The immersion time in the boric acid-containing aqueous solution is usually 60 to 1,200 seconds, preferably 150 to 600 seconds, more preferably 200 to 400 seconds. The temperature of the boric acid-containing aqueous solution is usually 50 ° C. or higher, preferably 50 to 85 ° C., more preferably 60 to 80 ° C.
ホウ酸処理後のポリビニルアルコール系樹脂フィルムは、通常水洗処理される。水洗処理は、例えばホウ酸処理されたポリビニルアルコール系樹脂フィルムを水に浸漬することによって行われる。水洗処理における水の温度は通常５ないし４０℃であり、浸漬時間は通常１ないし１２０秒である。水洗後には乾燥処理が施され、偏光子（偏光フィルム）が得られる。乾燥処理は通常、熱風乾燥機や遠赤外線ヒータを用いて行われる。乾燥処理の温度は通常３０ないし１００℃、好ましくは５０ないし８０℃である。乾燥処理の時間は通常６０ないし６００秒であり、好ましくは１２０ないし６００秒である。 The polyvinyl alcohol-based resin film after the boric acid treatment is usually washed with water. The water washing treatment is performed, for example, by immersing a boric acid-treated polyvinyl alcohol resin film in water. The temperature of water in the washing treatment is usually 5 to 40 ° C., and the immersion time is usually 1 to 120 seconds. After washing with water, a drying process is performed to obtain a polarizer (polarizing film). The drying process is usually performed using a hot air dryer or a far infrared heater. The temperature of the drying treatment is usually 30 to 100 ° C, preferably 50 to 80 ° C. The drying time is usually 60 to 600 seconds, preferably 120 to 600 seconds.
このようにしてポリビニルアルコール系樹脂フィルムに１軸延伸、２色性色素による染色及びホウ酸処理が施され、偏光子（偏光フィルム）が得られる。この偏光子（偏光フィルム）の厚さは、通常５ないし４０μｍの範囲内、好ましくは１０ないし３５μｍの範囲内である。 In this way, the polyvinyl alcohol-based resin film is uniaxially stretched, dyed with a dichroic dye, and treated with boric acid to obtain a polarizer (polarizing film). The thickness of this polarizer (polarizing film) is usually in the range of 5 to 40 μm, preferably in the range of 10 to 35 μm.
保護フィルムProtective film
本発明の偏光板としては、偏光子（偏光フィルム）の少なくとも一方の面に前述した接着剤層を介して保護フィルムが積層されたものである。保護フィルムとしては、例えば、セルロース系樹脂フィルム、シクロオレフィン系樹脂フィルム、アクリル系樹脂フィルム、ポリエステル系樹脂フィルムなど各種透明樹脂フィルムを用いることができる。 As a polarizing plate of this invention, the protective film is laminated | stacked through the adhesive bond layer mentioned above on the at least one surface of a polarizer (polarizing film). As a protective film, various transparent resin films, such as a cellulose resin film, a cycloolefin resin film, an acrylic resin film, and a polyester resin film, can be used, for example.
保護フィルムとしてセルロース系樹脂フィルムを用いる場合は、セルロースの少なくとも一部がエステル化された酢酸セルロース系樹脂が好ましい。例えばトリアセチルセルロース、ジアセチルセルロース、セルロースアセテートプロピオネートなどが挙げられる。 When a cellulose resin film is used as the protective film, a cellulose acetate resin in which at least a part of cellulose is esterified is preferable. For example, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate and the like can be mentioned.
シクロオレフィン系樹脂は、例えばノルボルネンや多環ノルボルネン系単量体のようなシクロオレフィンの単量体ユニットを有する熱可塑性の樹脂であり、前記シクロオレフィンの開環重合体や２種以上のシクロオレフィンを用いた開環共重合体の水素添加物であってもよいだけでなく、シクロオレフィンと鎖状オレフィンやビニル基を有する芳香族化合物との付加共重合体であってもよい。また、シクロオレフィン系樹脂に極性基が導入されていてもよい。 The cycloolefin resin is a thermoplastic resin having a cycloolefin monomer unit such as norbornene or a polycyclic norbornene monomer, and the cycloolefin ring-opening polymer or two or more kinds of cycloolefins. It may be a hydrogenated product of a ring-opening copolymer using, and may be an addition copolymer of a cycloolefin with a chain olefin or an aromatic compound having a vinyl group. Moreover, the polar group may be introduce | transduced into cycloolefin type resin.
接着剤組成物を用いた偏光子（偏光フィルム）と保護フィルムとの接合は適切な方法で行うことができ、例えば流延法、マイヤーバーコーティング法、グラビアコーティング法、ダイコーティング法、浸漬コーティング法、噴霧法などによって偏光子（偏光フィルム）及び／又は保護フィルムの接着面に接着剤組成物を塗布し、両者を重ね合わせる方法が挙げられる。流延法とは、被塗布物である偏光子（偏光フィルム）又は保護フィルムを概ね垂直方向、概ね水平方向、又は両者間の斜めの方向に移動させながら、その表面に接着剤組成物を塗布する方法である。 Bonding of a polarizer (polarizing film) using an adhesive composition and a protective film can be performed by an appropriate method, for example, casting method, Mayer bar coating method, gravure coating method, die coating method, dip coating method. And a method of applying an adhesive composition to the adhesive surface of a polarizer (polarizing film) and / or a protective film by a spraying method and superimposing the two. With the casting method, the adhesive composition is applied to the surface of the object to be coated while the polarizer (polarizing film) or protective film is moved in a generally vertical direction, a generally horizontal direction, or an oblique direction between the two. It is a method to do.
接着剤組成物を塗布した後、偏光子（偏光フィルム）と保護フィルムとをニップロールによって挟んで接合させる。 After apply | coating an adhesive composition, a polarizer (polarizing film) and a protective film are pinched | interposed and joined by a nip roll.
また、接着性を向上させるため、偏光子（偏光フィルム）及び／又は保護フィルムの表面にプラズマ処理、コロナ処理、紫外線照射処理、フレーム処理、けん化処理などの表面処理を適切に施してもよい。けん化処理としては、水酸化ナトリウム、水酸化カリウムなどのアルカリの水溶液に浸漬する方法が挙げられる。 In order to improve adhesiveness, the surface of the polarizer (polarizing film) and / or protective film may be appropriately subjected to surface treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, frame treatment, and saponification treatment. Examples of the saponification treatment include a method of immersing in an aqueous solution of an alkali such as sodium hydroxide or potassium hydroxide.
偏光子（偏光フィルム）と保護フィルムとを積層した後には乾燥処理が施される。乾燥処理は、例えば熱風を噴霧することによって行われるが、そのときの温度は５０ないし１００℃の範囲で適切に選択される。乾燥時間は通常３０ないし１，０００秒である。 After laminating a polarizer (polarizing film) and a protective film, a drying process is performed. The drying process is performed, for example, by spraying hot air, and the temperature at that time is appropriately selected in the range of 50 to 100 ° C. The drying time is usually 30 to 1,000 seconds.
以下、本発明を実施例、比較例及び実験例を用いてさらに詳しく説明する。しかし、下記の実施例、比較例及び実験例は、本発明を例示するためのものであって、本発明は下記の実施例、比較例及び実験例によって限定されず、多様に修正及び変更され得る。 Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples, and Experimental Examples. However, the following examples, comparative examples, and experimental examples are for illustrating the present invention, and the present invention is not limited by the following examples, comparative examples, and experimental examples, and various modifications and changes may be made. obtain.
製造例１．偏光子の製造Production Example 1 Polarizer manufacturing
平均重合度が２，４００であり、けん化度が９９．９モル％以上である７５μｍの厚さのポリビニルアルコールフィルムを乾式で約５倍に一軸延伸し、延伸状態を維持したまま６０℃の水（蒸留水）に１分間浸漬した後、ヨウ素／ヨウ化カリウム／蒸留水の重量比が０．０５／５／１００である２８℃の水溶液で６０秒間浸漬した。その後、ヨウ化カリウム／ホウ酸／蒸留水の重量比が８．５／８．５／１００である７２℃の水溶液に３００秒間浸漬し、２６℃の蒸留水で２０秒間洗浄した後、６５℃で乾燥してＰＶＡ系フィルムにヨウ素が吸着配向された偏光子を製造した。 A 75 μm-thick polyvinyl alcohol film having an average degree of polymerization of 2,400 and a saponification degree of 99.9 mol% or more is uniaxially stretched about 5 times in a dry manner and maintained at 60 ° C. while maintaining the stretched state. After being immersed in (distilled water) for 1 minute, it was immersed in a 28 ° C. aqueous solution having a weight ratio of iodine / potassium iodide / distilled water of 0.05 / 5/100 for 60 seconds. Then, after immersing in a 72 ° C. aqueous solution having a weight ratio of potassium iodide / boric acid / distilled water of 8.5 / 8.5 / 100 for 300 seconds and washing with 26 ° C. distilled water for 20 seconds, 65 ° C. And a polarizer having iodine adsorbed and oriented on a PVA film.
製造例２．保護フィルムの製造Production Example 2 Production of protective film
トリアセチルセルロース系フィルムであるＫＣ８ＵＸ（コニカ社、Ｔ）をけん化して用いた。 KC8UX (Konica, T), which is a triacetyl cellulose film, was used after saponification.
実施例１Example 1
（１）接着剤組成物の製造 (1) Production of adhesive composition
水（蒸留水）にけん化度が９９．２モル％であるアセトアセチル基変性ポリビニルアルコール系樹脂（Ｚ２００、日本合成化学工業（株）、平均重合度１２００）を溶解して接着剤組成物の固形分重量基準で６重量％のアセトアセチル基変性ポリビニルアルコールを添加して、アセトアセチル基変性ポリビニルアルコール系樹脂水溶液を得た。 Acetate group-modified polyvinyl alcohol resin (Z200, Nippon Synthetic Chemical Industry Co., Ltd., average polymerization degree 1200) having a saponification degree of 99.2 mol% is dissolved in water (distilled water) to form a solid adhesive composition. An acetoacetyl group-modified polyvinyl alcohol-based resin aqueous solution was obtained by adding 6% by weight of acetoacetyl group-modified polyvinyl alcohol on a weight basis.
前記アセトアセチル基変性ポリビニルアルコール系樹脂水溶液と、グリオキサール（４０％水溶液、テジョン化金）をアセトアセチル基変性ポリビニルアルコール系樹脂１００重量部に対して２０重量部になるように混合し、水溶性キレート化合物塩化亜鉛（テジョン化金）をアセトアセチル基変性ポリビニルアルコール系樹脂１００重量部に対して２重量部になるように混合して接着剤組成物を製造した。 The acetoacetyl group-modified polyvinyl alcohol-based resin aqueous solution and glyoxal (40% aqueous solution, gold tejonate) are mixed so as to be 20 parts by weight with respect to 100 parts by weight of the acetoacetyl group-modified polyvinyl alcohol-based resin. The compound zinc chloride (gold gold) was mixed at 2 parts by weight with respect to 100 parts by weight of the acetoacetyl group-modified polyvinyl alcohol resin to produce an adhesive composition.
（２）偏光子と保護フィルムとの接合（偏光板の製造） (2) Bonding of polarizer and protective film (production of polarizing plate)
製造例１で製造された偏光子の両面に前記接着剤組成物を乾燥膜厚が０．１μｍになるように塗布した後、セルロース系保護フィルム（コニカ社、ＫＣ８ＵＸ（商品名）、トリアセチルセルロースフィルム）をニップロールを用いて接合させた。接合された偏光板を８０℃の熱風乾燥機で５分間乾燥して偏光板を製造した。 After applying the adhesive composition on both sides of the polarizer produced in Production Example 1 so that the dry film thickness is 0.1 μm, a cellulose-based protective film (Konica, KC8UX (trade name), triacetyl cellulose) Film) was bonded using a nip roll. The bonded polarizing plate was dried with a hot air dryer at 80 ° C. for 5 minutes to produce a polarizing plate.
実施例２～６及び比較例１～７Examples 2 to 6 and Comparative Examples 1 to 7
前記実施例１と同一の方法で割合のみ異ならせて接着剤組成物を製造した（単位：重量部、表１を参照）。 The adhesive composition was manufactured by changing only the ratio in the same manner as in Example 1 (unit: parts by weight, see Table 1).
実施例７Example 7
水溶性キレート化合物硫酸亜鉛（テジョン化金）をアセトアセチル基変性ポリビニルアルコール系樹脂１００重量部に対して５重量部となるように混合したこと以外は実施例１と同一の条件で接着剤組成物を製造した（表１を参照）。 Adhesive composition under the same conditions as in Example 1 except that the water-soluble chelate compound zinc sulfate (gold tejongo) was mixed at 5 parts by weight with respect to 100 parts by weight of the acetoacetyl group-modified polyvinyl alcohol resin. (See Table 1).
実施例８Example 8
水溶性キレート化合物硫酸アルミニウム（アルドリッチ）をアセトアセチル基変性ポリビニルアルコール系樹脂１００重量部に対して５重量部となるように混合したこと以外は実施例１と同一の条件で接着剤組成物を製造した（表１を参照）。
実施例９ An adhesive composition was produced under the same conditions as in Example 1 except that the water-soluble chelate compound aluminum sulfate (Aldrich) was mixed to 5 parts by weight with respect to 100 parts by weight of the acetoacetyl group-modified polyvinyl alcohol resin. (See Table 1).
Example 9
水溶性キレート化合物硫酸マグネシウム（テジョン化金）をアセトアセチル基変性ポリビニルアルコール系樹脂１００重量部に対して５重量部となるように混合したこと以外は実施例１と同一の条件で接着剤組成物を製造した（表１を参照）。
実施例１０ Adhesive composition under the same conditions as in Example 1 except that the water-soluble chelate compound magnesium sulfate (gold tejongo) was mixed so as to be 5 parts by weight with respect to 100 parts by weight of the acetoacetyl group-modified polyvinyl alcohol resin. (See Table 1).
Example 10
接着剤組成物の固形分重量基準で３重量％のアセトアセチル基変性ポリビニルアルコールを含んだこと以外は実施例１と同一の条件で接着剤組成物を製造した（表１を参照）。 An adhesive composition was produced under the same conditions as in Example 1 except that 3% by weight of acetoacetyl group-modified polyvinyl alcohol was included based on the weight of the solid content of the adhesive composition (see Table 1).
実施例１１Example 11
接着剤組成物の固形分重量基準で９重量％のアセトアセチル基変性ポリビニルアルコールを含んだこと以外は実施例１と同一の条件で接着剤組成物を製造した（表１を参照）。 An adhesive composition was produced under the same conditions as in Example 1 except that 9% by weight of acetoacetyl group-modified polyvinyl alcohol was included based on the solid content weight of the adhesive composition (see Table 1).
実施例１２Example 12
接着剤組成物の固形分重量基準で２重量％のアセトアセチル基変性ポリビニルアルコールを含んだこと以外は実施例１と同一の条件で接着剤組成物を製造した（表１を参照）。 An adhesive composition was produced under the same conditions as in Example 1 except that 2% by weight of acetoacetyl group-modified polyvinyl alcohol was included based on the solid content weight of the adhesive composition (see Table 1).
実施例１３Example 13
接着剤組成物の固形分重量基準で１０重量％のアセトアセチル基変性ポリビニルアルコールを含んだこと以外は実施例１と同一の条件で接着剤組成物を製造した（表１を参照）。 An adhesive composition was produced under the same conditions as in Example 1 except that 10% by weight of acetoacetyl group-modified polyvinyl alcohol was included based on the weight of the solid content of the adhesive composition (see Table 1).
実施例１４Example 14
接着剤組成物中のアセトアセチル基変性ポリビニルアルコール系樹脂をＺ２００からＺ１００（日本合成化学工業（株）、平均重合度６５０）に変更したこと以外は実施例１と同一の条件で接着剤組成物を製造した（表１を参照）。 Adhesive composition under the same conditions as in Example 1 except that the acetoacetyl group-modified polyvinyl alcohol resin in the adhesive composition was changed from Z200 to Z100 (Nippon Synthetic Chemical Industry Co., Ltd., average polymerization degree 650). (See Table 1).
比較例８Comparative Example 8
グリオキサールに変えてグリオキシル酸ナトリウム（Ｓｉｇｍａ　Ａｌｄｒｉｃｈ社）を、アセトアセチル基変性ポリビニルアルコール系樹脂と混合したこと以外は実施例１と同一の条件で接着剤組成物を製造した（表１を参照）。 An adhesive composition was produced under the same conditions as in Example 1 except that sodium glyoxylate (Sigma Aldrich) was mixed with acetoacetyl group-modified polyvinyl alcohol resin instead of glyoxal (see Table 1).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
＊ＰＶＡ－１１７Ｈ（クラレ（株）、重合度１７００） * PVA-117H (Kuraray Co., Ltd., polymerization degree 1700)
実験例Experimental example
（１）接着力（カッター評価） (1) Adhesive strength (cutter evaluation)
製造された偏光板を１時間常温で放置した後、偏光板の各フィルムの間（偏光子と偏光子保護フィルムとの間）にカッターの刃を入れ、刃を押し進めたときの刃が入る方式を下記の基準で評価し、その結果を下記表２に示した。 After leaving the manufactured polarizing plate at room temperature for 1 hour, insert the blade of the cutter between the films of the polarizing plate (between the polarizer and the polarizer protective film), and insert the blade when the blade is pushed forward Were evaluated according to the following criteria and the results are shown in Table 2 below.
◎：カッターの刃がいずれのフィルム間にも入らない。 A: The cutter blade does not enter between any films.
○：刃を押し進めたとき、少なくともいずれか一方のフィルム間に刃が１ないし２ｍｍ入ったときに止まる。 ○: When the blade is pushed forward, it stops when the blade enters 1 to 2 mm between at least one of the films.
△：刃を押し進めたとき、少なくともいずれか一方のフィルム間に刃が３ないし５ｍｍ入ったときに止まる。 Δ: When the blade is pushed forward, it stops when the blade enters 3 to 5 mm between at least one of the films.
×：刃を押し進めたとき、少なくともいずれか一方のフィルム間に刃が無理なく入る。 X: When the blade is pushed forward, the blade enters between at least one of the films without difficulty.
（２）耐水性 (2) Water resistance
２３℃、相対湿度５５％の環境下で２４時間放置した各偏光板に対して、以下の耐温水性試験を行い、耐水性を評価した。偏光板の吸収軸を長辺として５ｃｍ×２ｃｍのストリップ状に偏光板を切断してサンプルとし、その長辺方向の寸法を正確に測定した。ここでサンプルは偏光子（偏光フィルム）に吸着されたヨウ素に起因して全面にわたり均一に特有の色を示している。図１は、耐水性の評価試験方法を模式的に示した図であり、（Ａ）は、温水浸漬前のサンプル（１）、（Ｂ）は温水浸漬後のサンプル（１）を示している。図１の（Ａ）に示したように、サンプルの一短辺側を把持具（５）で把持し、長さ方向の８割程度を６０℃の水槽に浸漬し、４時間維持した。その後、サンプル（１）を水槽から取り出して水分を拭き取った。 The following warm water resistance test was performed on each polarizing plate left for 24 hours in an environment of 23 ° C. and relative humidity 55% to evaluate the water resistance. The polarizing plate was cut into a strip shape of 5 cm × 2 cm with the absorption axis of the polarizing plate as the long side to obtain a sample, and the dimension in the long side direction was accurately measured. Here, the sample shows a unique color uniformly over the entire surface due to iodine adsorbed on the polarizer (polarizing film). FIG. 1 is a diagram schematically showing a water resistance evaluation test method, in which (A) shows a sample (1) before immersion in warm water, and (B) shows a sample (1) after immersion in warm water. . As shown in FIG. 1A, one short side of the sample was gripped by the gripper (5), and about 80% of the length direction was immersed in a 60 ° C. water bath and maintained for 4 hours. Then, the sample (1) was taken out from the water tank and the moisture was wiped off.
温水浸漬によって偏光板の偏光子（偏光フィルム）（４）は収縮する。この偏光子（偏光フィルム）（４）の収縮程度を、サンプル（１）の短辺中央における端部（１ａ）（保護フィルム（２）の端）から収縮した偏光子（偏光フィルム）（４）の端部までの距離を測定することで評価し、収縮長さとした。また、図１の（Ｂ）に示したように、温水浸漬によって偏光板の中央に位置する偏光子（偏光フィルム）（４）が収縮されることで、保護フィルムの間に偏光子（偏光フィルム）（４）の周縁部からヨウ素が溶出し、サンプル（１）の周縁部に色が抜けた部分（３）が生じる。この脱色程度をサンプル（１）の短辺中央における収縮した偏光子（偏光フィルム）（４）の端部から偏光板特有の色が残っている領域までの距離を測定することによって評価し、ヨウ素が抜けた長さとした。前記収縮長さとヨウ素が抜けた長さとの合計を総浸食長さＸとした。総浸食長さＸとは、サンプル（１）の短辺中央における、サンプル（１）の端部（１ａ）から偏光板特有の色が残っている領域までの距離である。収縮長さ、ヨウ素の抜けた長さ及び総浸食長さＸが小さいほど、水の存在下における接着性が高いと判断することができる。そして、総浸食長さＸによって以下の４段階で評価し、その結果を表２に示した。 The polarizer (polarizing film) (4) of the polarizing plate contracts by immersion in warm water. Polarizer (polarizing film) (4) in which the degree of contraction of the polarizer (polarizing film) (4) is contracted from the end (1a) (end of the protective film (2)) at the center of the short side of sample (1) It was evaluated by measuring the distance to the end of the film, and the contraction length. Moreover, as shown to (B) of FIG. 1, the polarizer (polarizing film) (4) located in the center of a polarizing plate is contracted by immersion in warm water, so that the polarizer (polarizing film) is interposed between protective films. ) Iodine elutes from the peripheral portion of (4), and a portion (3) where the color is lost is generated at the peripheral portion of sample (1). This degree of decolorization was evaluated by measuring the distance from the end of the contracted polarizer (polarizing film) (4) at the center of the short side of the sample (1) to the region where the color peculiar to the polarizing plate remained, The length was missing. The total of the shrinkage length and the length from which iodine was removed was defined as the total erosion length X. The total erosion length X is the distance from the end (1a) of the sample (1) to the region where the color peculiar to the polarizing plate remains at the center of the short side of the sample (1). It can be determined that the smaller the shrinkage length, the length from which iodine is removed, and the total erosion length X, the higher the adhesion in the presence of water. The total erosion length X was evaluated in the following four stages, and the results are shown in Table 2.
◎：総浸食長さＸが２ｍｍ未満 A: Total erosion length X is less than 2 mm
○：総浸食長さＸが２ｍｍ以上３ｍｍ未満 ○: Total erosion length X is 2 mm or more and less than 3 mm
△：総浸食長さＸが３ｍｍ以上５ｍｍ未満 Δ: Total erosion length X is 3 mm or more and less than 5 mm
×：総浸食長さＸが５ｍｍ以上 X: Total erosion length X is 5 mm or more
（３）透過率、偏光度（％） (3) Transmittance, polarization degree (%)
製造された偏光板を４ｃｍ×４ｃｍの大きさに切断して試片を作製し、この試片を測定ホルダに付着させた後、紫外可視光線分光計（Ｖ－７１００、ＪＡＳＣＯ社製）を用いて測定し、その結果を表２に示した。 The manufactured polarizing plate was cut into a size of 4 cm × 4 cm to prepare a specimen, and after attaching the specimen to a measurement holder, an ultraviolet-visible light spectrometer (V-7100, manufactured by JASCO) was used. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
表２に示したように、実施例１ないし１４は比較例１ないし８に比べて優れた接着性、耐水性及び光特性を示した。 As shown in Table 2, Examples 1 to 14 exhibited superior adhesion, water resistance, and optical properties as compared with Comparative Examples 1 to 8.
１…偏光板のサンプル、２…偏光子保護フィルム、３…色が抜けた部分、４…偏光子、５…把持具。 DESCRIPTION OF SYMBOLS 1 ... Sample of polarizing plate, 2 ... Polarizer protective film, 3 ... Colored part, 4 ... Polarizer, 5 ... Holding tool.

Claims (6)

  1. 　アセトアセチル基変性ポリビニルアルコール系樹脂、ジアルデヒド類、及び水溶性キレート化合物を含み、
    　架橋調節剤を含んでおらず、
    　前記アセトアセチル基変性ポリビニルアルコール系樹脂の平均重合度が１５００以下である、偏光板用接着剤組成物。     Including an acetoacetyl group-modified polyvinyl alcohol resin, dialdehydes, and a water-soluble chelate compound,
    Does not contain a crosslinking regulator,
    The adhesive composition for polarizing plates whose average polymerization degree of the said acetoacetyl group modified polyvinyl alcohol-type resin is 1500 or less.
  2. 　前記アセトアセチル基変性ポリビニルアルコール系樹脂は、接着剤組成物の固形分重量を基準として３ないし９重量％で含まれる、請求項１記載の偏光板用接着剤組成物。 The adhesive composition for a polarizing plate according to claim 1, wherein the acetoacetyl group-modified polyvinyl alcohol resin is contained in an amount of 3 to 9% by weight based on the solid content weight of the adhesive composition.
  3. 　アセトアセチル基変性ポリビニルアルコール系樹脂１００重量部に対して、
    　ジアルデヒド類は２０ないし５０重量部で含まれ、
    　前記水溶性キレート化合物は２ないし１０重量部で含まれる、請求項１又は２記載の偏光板用接着剤組成物。     For 100 parts by weight of the acetoacetyl group-modified polyvinyl alcohol resin,
    Dialdehydes are included in 20 to 50 parts by weight,
    The adhesive composition for polarizing plates according to claim 1 or 2, wherein the water-soluble chelate compound is contained in an amount of 2 to 10 parts by weight.
  4. 　ジアルデヒド類は、グリオキサールである、請求項１～３のいずれか１項記載の偏光板用接着剤組成物。 The adhesive composition for polarizing plates according to any one of claims 1 to 3, wherein the dialdehyde is glyoxal.
  5. 　水溶性キレート化合物は、塩化亜鉛、塩化コバルト、塩化マグネシウム、酢酸マグネシウム、硝酸アルミニウム、硝酸亜鉛、及び硫酸亜鉛からなる群より選択される１種以上である、請求項１～４のいずれか１項記載の偏光板用接着剤組成物。 The water-soluble chelate compound is one or more selected from the group consisting of zinc chloride, cobalt chloride, magnesium chloride, magnesium acetate, aluminum nitrate, zinc nitrate, and zinc sulfate. The adhesive composition for polarizing plates as described.
  6. 　ポリビニルアルコール系偏光子；
    　前記偏光子の一面又は両面に積層され、請求項１ないし５のいずれか一項の接着剤組成物を含有する接着剤層；及び
    　前記接着剤層上に一面又は両面に積層された偏光子保護フィルムを含む偏光板。     Polyvinyl alcohol polarizer;
    An adhesive layer that is laminated on one or both sides of the polarizer and contains the adhesive composition according to any one of claims 1 to 5; and a polarizer protection laminated on one or both sides on the adhesive layer A polarizing plate including a film.
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Publication number Priority date Publication date Assignee Title
JP2018025798A (en) * 2016-08-08 2018-02-15 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． Polarizing plate and method for manufacturing the same
JP2018028077A (en) * 2016-08-08 2018-02-22 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． Adhesive composition, and polarizing plate and image display device comprising the same
WO2022075148A1 (en) * 2020-10-05 2022-04-14 住友化学株式会社 Polarizing plate and image display device

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JP2008257025A (en) * 2007-04-06 2008-10-23 Sumitomo Chemical Co Ltd Polarizing plate, optical member provided with the same and liquid crystal display device
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WO2005033754A1 (en) * 2003-09-30 2005-04-14 Nitto Denko Corporation Process for manufacturing polarizing plate, polarizing plate, optical film and image display
JP2008257025A (en) * 2007-04-06 2008-10-23 Sumitomo Chemical Co Ltd Polarizing plate, optical member provided with the same and liquid crystal display device
JP2012041533A (en) * 2010-08-13 2012-03-01 Dongwoo Fine-Chem Co Ltd Adhesive composition for polarizing plate and polarizing plate using the same
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JP2018025798A (en) * 2016-08-08 2018-02-15 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． Polarizing plate and method for manufacturing the same
JP2018028077A (en) * 2016-08-08 2018-02-22 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． Adhesive composition, and polarizing plate and image display device comprising the same
WO2022075148A1 (en) * 2020-10-05 2022-04-14 住友化学株式会社 Polarizing plate and image display device
JP7519861B2 (en) 2020-10-05 2024-07-22 住友化学株式会社 Polarizing plate and image display device

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