WO2011108647A1 - Adhesive for polarizing plate, polarizing plate, method for producing same, optical film, and image display device - Google Patents
Adhesive for polarizing plate, polarizing plate, method for producing same, optical film, and image display device Download PDFInfo
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- WO2011108647A1 WO2011108647A1 PCT/JP2011/054925 JP2011054925W WO2011108647A1 WO 2011108647 A1 WO2011108647 A1 WO 2011108647A1 JP 2011054925 W JP2011054925 W JP 2011054925W WO 2011108647 A1 WO2011108647 A1 WO 2011108647A1
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- adhesive
- polarizing plate
- protective film
- polarizer
- silicate
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
Definitions
- the present invention relates to an adhesive for polarizing plates. Moreover, this invention relates to the polarizing plate using the said adhesive agent for polarizing plates, and its manufacturing method.
- the polarizing plate can form an image display device such as a liquid crystal display device, an organic EL display device, or a PDP alone or as an optical film obtained by laminating the polarizing plate.
- a polarizer is obtained by dyeing a polyvinyl alcohol film with a dichroic material such as iodine, cross-linking with a cross-linking agent, and forming a film by uniaxial stretching. Since the polarizer is made by stretching, it easily contracts. In addition, since the polyvinyl alcohol film uses a hydrophilic polymer, it is very easily deformed particularly under humidified conditions. Moreover, since the mechanical strength of the film itself is weak, there is a problem that the film is torn.
- a polarizing plate in which a transparent protective film such as triacetyl cellulose is bonded to both sides or one side of the polarizer to supplement the strength.
- the polarizing plate is manufactured by bonding a polarizer and a transparent protective film with an adhesive.
- liquid crystal display devices Recently, the use of liquid crystal display devices has been expanded, and a wide range of development has been progressing from portable terminals to large-sized TVs for home use, and various standards have been established according to each application. Particularly in portable terminal applications, since it is assumed that the user carries around, the demand for durability is very strict. For example, a polarizing plate is required to have water resistance that does not change its characteristics and shape even under humidified conditions that cause condensation.
- the polarizer is used as a polarizing plate whose strength is reinforced by a transparent protective film.
- a water-system adhesive agent is preferable, for example, the polyvinyl alcohol-type adhesive agent which mixed the crosslinking agent in the polyvinyl alcohol aqueous solution is used.
- the polyvinyl alcohol-based adhesive may peel off at the interface between the polarizer and the transparent protective film under humidified conditions. This may be because the polyvinyl alcohol resin, which is the main component of the adhesive, is a water-soluble polymer, and the adhesive may be dissolved under the dew condensation condition.
- Patent Document 1 a polarizing plate adhesive containing a polyvinyl alcohol-based resin containing an acetoacetyl group and a crosslinking agent has been proposed. Further, there has been proposed a water-based adhesive for polarizing elements containing a polyvinyl alcohol resin, a resin containing a maleic anhydride skeleton in the structure, and a crosslinking agent (Patent Document 2).
- a nick is a local irregularity defect that occurs at the interface between a polarizer and a transparent protective film.
- a method of laminating a transparent protective film on a surface of a polyvinyl alcohol film adjusted in water content with a calender roll under predetermined conditions as a polarizer (Patent Document 3).
- the nick is particularly likely to occur when a polyvinyl alcohol resin containing an acetoacetyl group is used as the polyvinyl alcohol adhesive.
- an adhesive for polarizing plates comprising a resin solution containing a polyvinyl alcohol resin, a crosslinking agent, and a metal compound colloid having an average particle size of 1 to 100 nm (Patent Document 4).
- the metal compound colloid has a higher refractive index than that of the polyvinyl alcohol resin
- the adhesive layer using the polarizing plate adhesive tends to have a higher refractive index. Therefore, interface reflection of light is likely to occur between the polarizer and the adhesive layer and between the transparent protective film and the adhesive layer, and the light transmittance of the polarizing plate may be reduced.
- improvement in optical characteristics of polarizing plates has been demanded more.
- Patent Document 5 proposes a laminated flexible polarizer in which a polarizing core layer and an outer layer are bonded using a silicate layer, and the laminated flexible polarizer has thermal stability and flexibility. Is described.
- Patent Document 6 proposes a laminated polarizer in which a polarizing core layer and a covering layer are bonded with a silicate layer, and describes that the laminated polarizer has thermal stability and flexibility. .
- crosslinking agents for polyvinyl alcohol resins.
- amino-formaldehyde resins having excellent reactivity with acetoacetyl groups are preferably used from the viewpoint of water resistance.
- amino-formaldehyde resins contain formaldehyde, there are concerns about the impact on the working environment due to strong pungent odors and safety due to remaining in the product.
- amino-formaldehyde resin is highly reactive with acetoacetyl groups, crosslinking reaction is likely to proceed at room temperature, resulting in increased workability due to thickening during storage, or eventually becoming gelled and unusable. And had problems such as shortened pot life.
- JP-A-7-198945 International Publication No. 2005/085383 Pamphlet Japanese Patent Laid-Open No. 10-166519 Japanese Patent No. 4039682 JP-A-8-68908 JP-A-9-178944
- this invention is excellent in adhesive force, can prevent the fall of the light transmittance of a polarizing plate, and can suppress generation
- the second aspect of the present invention is an adhesive for polarizing plates that is excellent in adhesive strength, can prevent a decrease in light transmittance of the polarizing plate, and is excellent in liquid stability.
- the polarizing plate can be used in a humidified environment. It aims at providing the adhesive agent for polarizing plates which a light transmittance does not fall easily.
- Another object of the present invention is to provide a polarizing plate using the polarizing plate adhesive and a method for producing the same. Furthermore, an object of the present invention is to provide an optical film in which the polarizing plate is laminated, and to provide an image display device such as a liquid crystal display device using the polarizing plate and the optical film.
- the present inventors have found that the above object can be achieved by the following polarizing plate adhesive, and have completed the present invention.
- the first present invention is an adhesive for polarizing plates used for providing a transparent protective film on at least one side of a polarizer
- the said adhesive agent for polarizing plates is related with the adhesive agent for polarizing plates characterized by being the resin solution containing polyvinyl alcohol-type resin and water-soluble silicate.
- the blending amount of the water-soluble silicate is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin.
- the blending amount of the water-soluble silicate is less than 1 part by weight, it becomes difficult to suppress the occurrence of nicks, or the refractive index of the adhesive layer becomes too high. Interfacial reflection of light tends to occur between the respective layers between the adhesive layers, and the light transmittance of the polarizing plate tends to decrease.
- the amount exceeds 100 parts by weight the adhesive strength of the adhesive layer is reduced, or the refractive index of the adhesive layer is too low, so that between the polarizer and the adhesive layer and between the transparent protective film and the adhesive layer. Interfacial reflection of light is likely to occur between the respective layers, and the light transmittance of the polarizing plate tends to decrease.
- the water-soluble silicate is preferably at least one selected from the group consisting of lithium silicate, sodium silicate, and potassium silicate.
- Lithium silicate preferably has a SiO 2 / Li 2 O molar ratio of 2 to 8. If the molar ratio is less than 2, the alkalinity of the adhesive layer becomes high, and the light transmittance of the polarizing plate tends to decrease in a humidified environment. On the other hand, when the molar ratio exceeds 8, it does not become a water-soluble silicate.
- Sodium silicate preferably has a SiO 2 / Na 2 O molar ratio of 2 to 5.
- the potassium silicate preferably has a SiO 2 / K 2 O molar ratio of 2 to 5.
- the molar ratio is less than 2, the alkalinity of the adhesive layer becomes high, and the light transmittance of the polarizing plate tends to decrease in a humidified environment. On the other hand, when the molar ratio exceeds 5, it does not become a water-soluble silicate.
- the present invention is particularly suitable when a polyvinyl alcohol resin containing an acetoacetyl group is used as the polyvinyl alcohol resin.
- An adhesive using a polyvinyl alcohol-based resin containing an acetoacetyl group can form an adhesive layer having excellent water resistance.
- a water-soluble silicate should be blended.
- the occurrence of nicks in the polarizing plate adhesive using a polyvinyl alcohol-based resin containing an acetoacetyl group can be suppressed.
- the adhesive agent for polarizing plates which has water resistance and can suppress generation
- the second present invention is an adhesive for polarizing plate used for providing a transparent protective film on at least one surface of a polarizer
- the polarizing plate adhesive is a resin solution containing a polyvinyl alcohol resin, a silicate, and an amino acid having at least one amino group and at least one acidic group and / or a sulfur-containing amino acid. It relates to the adhesive agent for polarizing plates.
- an adhesive for polarizing plate having excellent adhesive strength can be obtained.
- the polarizing plate adhesive of the present invention is used, an adhesive layer that hardly peels off at the interface between the polarizer and the transparent protective film even when immersed in warm water can be formed.
- the increase in the refractive index of the adhesive layer can be suppressed, light interface reflection between the polarizer and the adhesive layer and between the transparent protective film and the adhesive layer is less likely to occur. A decrease in transmittance can be suppressed.
- the amount of the amino acid and / or sulfur-containing amino acid is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin. When the amount is less than 5 parts by weight, the water resistance of the adhesive layer is lowered, and when it exceeds 50 parts by weight, the adhesive force of the adhesive layer tends to be lowered.
- the acidic group is preferably a carboxyl group or a sulfo group.
- the polyvinyl alcohol resin is preferably a polyvinyl alcohol resin containing an acetoacetyl group. Thereby, an adhesive layer having excellent water resistance can be formed.
- the silicate is preferably at least one selected from the group consisting of water-soluble lithium silicate, water-soluble sodium silicate, and water-soluble potassium silicate.
- the water-soluble lithium silicate preferably has a SiO 2 / Li 2 O molar ratio of 2 to 8. If the molar ratio is less than 2, the alkalinity of the adhesive layer becomes high, and the light transmittance of the polarizing plate tends to decrease in a humidified environment. On the other hand, when the molar ratio exceeds 8, it does not become a water-soluble silicate.
- the water-soluble sodium silicate preferably has a SiO 2 / Na 2 O molar ratio of 2 to 5.
- the water-soluble potassium silicate preferably has a SiO 2 / K 2 O molar ratio of 2 to 5. If the molar ratio is less than 2, the alkalinity of the adhesive layer becomes high, and the light transmittance of the polarizing plate tends to decrease in a humidified environment. On the other hand, when the molar ratio exceeds 5, it does not become a water-soluble silicate.
- the adhesive layer is formed of the polarizing plate adhesive.
- the present invention relates to a polarizing plate.
- a water-soluble silicate is contained in the adhesive layer, and knick defects generated when the polarizer and the transparent protective film are bonded are suppressed.
- the light transmittance of the polarizing plate of the present invention is unlikely to decrease in a humidified environment.
- the thickness of the adhesive layer is preferably 10 to 300 nm.
- the thickness of the adhesive layer is less than 10 nm, the adhesive force is not sufficient, and when it exceeds 300 nm, the optical reliability and the moisture-resistant adhesive force tend to decrease.
- the refractive index of the adhesive layer is preferably 1.47 to 1.54.
- the refractive index of the adhesive layer is too low or too high, and therefore between the polarizer and the adhesive layer and between the transparent protective film and the adhesive. Interfacial reflection of light tends to occur between the layers between the layers, and the light transmittance of the polarizing plate tends to decrease.
- the present invention provides a method for producing a polarizing plate in which a transparent protective film is provided on at least one surface of a polarizer via an adhesive layer.
- the present invention relates to a method for producing a polarizing plate, comprising a step of bonding a polarizer and a transparent protective film.
- the present invention also relates to an optical film in which at least one polarizing plate is laminated.
- this invention relates to the image display apparatus containing the said polarizing plate or the said optical film.
- the adhesive for polarizing plates of the first aspect of the present invention uses a polyvinyl alcohol resin and a water-soluble silicate in combination, so that it has excellent adhesive strength, and the occurrence of nicks can be suppressed by the action of the water-soluble silicate. . Thereby, the yield at the time of producing a polarizing plate improves, and the productivity of a polarizing plate improves.
- the adhesive layer made of the adhesive for polarizing plate containing a water-soluble silicate has a small difference in refractive index with the polarizer and a difference in refractive index with the transparent protective film, and therefore between the polarizer and the adhesive layer and Interfacial reflection of light hardly occurs between each layer between the transparent protective film and the adhesive layer, and a decrease in light transmittance of the polarizing plate can be prevented.
- the adhesive layer formed by the polarizing plate adhesive of the second aspect of the present invention is an adhesive layer that is excellent in adhesive strength and water resistance and hardly peels off at the interface between the polarizer and the transparent protective film.
- the refractive index of the adhesive layer has a small difference between the refractive index of the polarizer and the transparent protective film, light is transmitted between the polarizer and the adhesive layer and between the transparent protective film and the adhesive layer. It is difficult for the interface reflection to occur, and the light transmittance of the polarizing plate is difficult to decrease.
- the adhesive for polarizing plates of the present invention is not only excellent in liquid stability because of low reactivity at room temperature, but also has the advantage that the working environment is improved and the safety of the product is increased because it does not contain formaldehyde. There is.
- the adhesive for polarizing plates of the first present invention is a resin solution containing a polyvinyl alcohol-based resin and a water-soluble silicate.
- the adhesive for polarizing plates of the second invention is a resin solution containing a polyvinyl alcohol resin, a silicate, and an amino acid and / or a sulfur-containing amino acid having one or more amino groups and one or more acidic groups. It is.
- polyvinyl alcohol resins examples include polyvinyl alcohol resins and polyvinyl alcohol resins having an acetoacetyl group.
- the polyvinyl alcohol resin having an acetoacetyl group is a polyvinyl alcohol-based adhesive having a highly reactive functional group, and is preferable because the durability of the polarizing plate is improved.
- Polyvinyl alcohol resin is polyvinyl alcohol obtained by saponifying polyvinyl acetate; a derivative thereof; a saponified product of a copolymer of vinyl acetate and a monomer having copolymerizability; Examples thereof include modified polyvinyl alcohols that have been converted into ethers, ethers, grafts, or phosphoric esters.
- Examples of the monomer include unsaturated carboxylic acids such as (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid, (meth) acrylic acid, and esters thereof; ⁇ -olefins such as ethylene and propylene; (meth) Examples include allyl sulfonic acid (soda), sulfonic acid soda (monoalkylmalate), disulfonic acid soda alkylmalate, N-methylolacrylamide, acrylamide alkylsulfonic acid alkali salt, N-vinylpyrrolidone, and N-vinylpyrrolidone derivatives. . These polyvinyl alcohol resins can be used singly or in combination of two or more.
- the polyvinyl alcohol resin is not particularly limited, but from the viewpoint of adhesiveness, the average degree of polymerization is about 100 to 5000, preferably 1000 to 4000, and the average saponification degree is about 85 to 100 mol%, preferably 90 to 100 mol%. It is.
- a polyvinyl alcohol-based resin containing an acetoacetyl group is obtained by reacting a polyvinyl alcohol-based resin with diketene by a known method.
- a method in which diketene gas or liquid diketene is brought into direct contact with polyvinyl alcohol.
- the degree of acetoacetyl group modification of the polyvinyl alcohol resin containing an acetoacetyl group is not particularly limited as long as it is 0.1 mol% or more. If it is less than 0.1 mol%, the water resistance of the adhesive layer is insufficient and unsuitable.
- the degree of acetoacetyl group modification is preferably about 0.1 to 40 mol%, more preferably 1 to 20 mol%, and particularly preferably 2 to 7 mol%. When the acetoacetyl group modification degree exceeds 40 mol%, the effect of improving water resistance is small.
- the degree of acetoacetyl modification is a value measured by NMR.
- a crosslinking agent may be added to the resin solution.
- a crosslinking agent what is used for the polyvinyl alcohol-type adhesive agent can be especially used without a restriction
- a compound having at least two functional groups having reactivity with the polyvinyl alcohol resin can be used.
- Dialdehydes amino-formaldehyde resins such as methylol urea, methylol melamine, alkylated methylol urea, alkylated methylolated melamine, acetoguanamine, condensate of benzoguanamine and formaldehyde; zirconium acetate, zirconium nitrate, zirconium carbonate, zirconium hydroxide Zirconium compounds such as zirconium oxychloride; metal glyoxylate (metals include, for example, lithium, sodium, potassium Alkali metals such as magnesium, alkaline earth metals such as magnesium and calcium, transition metals such as titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper, zinc, aluminum, etc.), glyoxylic acid amine salts (Examples of the amine include glyoxylates such as ammonia, monomethylamine, dimethylamine, and trimethylamine);
- an amino acid or a sulfur-containing amino acid having one or more basic groups and one or more acidic groups can be used alone or in combination of two or more.
- the basic group is preferably an amino group
- the acidic group is preferably a carboxyl group or a sulfo group.
- the amino acids include glycine, alanine, phenylalanine, valine, leucine, isoleucine, lysine, proline, serine, threonine, tryptophan, histidine, tyrosine, arginine, asparagine, aspartic acid, aspartame, glutamine, glutamic acid, and these amino acids.
- Examples include copolymers with (meth) acrylic acid.
- Examples of the sulfur-containing amino acid include methionine, cysteine, cystine, and taurine. Among these, it is particularly preferable to use a sulfur-containing amino acid having a sulfo group such as taurine.
- coupling agents such as a silane coupling agent and a titanium coupling agent, can be used.
- the amount of the crosslinking agent can be appropriately designed according to the type of polyvinyl alcohol resin, etc., but is usually about 0.1 to 50 parts by weight, preferably 0.2 parts per 100 parts by weight of the polyvinyl alcohol resin. About 30 to 30 parts by weight, more preferably 0.5 to 20 parts by weight. In such a range, good adhesiveness can be obtained.
- a polyvinyl alcohol resin containing an acetoacetyl group is used. Also in this case, the amount of the crosslinking agent is the same as described above. When the amount of the crosslinking agent is too large, the liquid stability is lowered, the pot life as an adhesive is shortened, and industrial use becomes difficult.
- the water-soluble silicate used in the first present invention is a compound represented by the general formula M 2 O ⁇ nSiO 2 , and M is an alkali metal, an organic base, or the like.
- the alkali metal include lithium, sodium, and potassium
- examples of the organic base include tertiary ammonium, quaternary ammonium, and guanidinium.
- n is preferably 2 to 8.
- Lithium silicate preferably has a SiO 2 / Li 2 O molar ratio of 2 to 8.
- Sodium silicate preferably has a SiO 2 / Na 2 O molar ratio of 2 to 5, more preferably 2.5 to 5.
- Potassium silicate preferably has a SiO 2 / K 2 O molar ratio of 2 to 5, more preferably 2.5 to 5.
- the blending amount of the water-soluble silicate is preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, and further preferably 1 to 30 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin. It is.
- the polarizing plate adhesive of the first invention is a resin solution containing a polyvinyl alcohol-based resin and a water-soluble silicate, and is usually used as an aqueous solution.
- concentration of the resin solution is not particularly limited, but is preferably from 0.1 to 15% by weight, more preferably from 0.5 to 10% by weight in consideration of coating property and storage stability.
- the viscosity of the resin solution is not particularly limited, but a resin solution in the range of 1 to 50 mPa ⁇ s is usually used.
- the nick generated in the production of the polarizing plate tends to increase as the viscosity of the resin solution decreases.
- the polarizing plate adhesive of the first aspect of the present invention it is 1-20 mPa ⁇ s. Even in such a low viscosity range, the occurrence of nicks can be suppressed, and the occurrence of nicks can be suppressed regardless of the viscosity of the resin solution.
- the polyvinyl alcohol resin containing an acetoacetyl group cannot be made higher in polymerization degree than a general polyvinyl alcohol resin, and has been used at a low viscosity as described above. Even when a polyvinyl alcohol-based resin containing a group is used, generation of nicks caused by low viscosity of the resin solution can be suppressed.
- an amino acid or sulfur-containing amino acid having one or more amino groups and one or more acidic groups is used as a crosslinking agent.
- the acidic group is preferably a carboxyl group or a sulfo group.
- amino acids examples include glycine, alanine, phenylalanine, valine, leucine, isoleucine, lysine, proline, serine, threonine, tryptophan, histidine, tyrosine, arginine, asparagine, aspartic acid, aspartame, glutamine, glutamic acid, and these amino acids.
- sulfur-containing amino acid examples include methionine, cysteine, cystine, and taurine. These can be used alone or in combination of two or more. Among these, it is particularly preferable to use a sulfur-containing amino acid having a sulfo group such as taurine.
- the blending amount of the amino acid and / or sulfur-containing amino acid is preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin. However, when amino acids and sulfur-containing amino acids are used in combination, the total amount is meant.
- crosslinking agents may be added to the resin solution. However, when adding another crosslinking agent, the addition amount is 50 weight% or less with respect to the whole crosslinking agent. Examples of other cross-linking agents include those described above.
- a polyvinyl alcohol resin containing an acetoacetyl group is used. Also in this case, the amount of the crosslinking agent is the same as described above. When the amount of the crosslinking agent is too large, the liquid stability is lowered, the pot life as an adhesive is shortened, and industrial use becomes difficult.
- Silicate is a compound represented by the general formula M 2 O ⁇ nSiO 2 , where M is an alkali metal, an organic base, or the like.
- M is an alkali metal, an organic base, or the like.
- the alkali metal include lithium, sodium, and potassium
- examples of the organic base include tertiary ammonium, quaternary ammonium, and guanidinium.
- n is preferably 2 to 8.
- At least 1 sort (s) selected from the group which consists of water-soluble lithium silicate, water-soluble sodium silicate, and water-soluble potassium silicate as a silicate.
- the water-soluble lithium silicate preferably has a SiO 2 / Li 2 O molar ratio of 2 to 8.
- the water-soluble sodium silicate preferably has a SiO 2 / Na 2 O molar ratio of 2 to 5, more preferably 2.5 to 5.
- the water-soluble potassium silicate preferably has a SiO 2 / K 2 O molar ratio of 2 to 5, more preferably 2.5 to 5.
- the amount of the silicate is preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, and further preferably 1 to 30 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin. .
- the amount of silicate is less than 1 part by weight, the refractive index of the adhesive layer becomes too high, so that light is not transmitted between the polarizer and the adhesive layer and between the transparent protective film and the adhesive layer. Interface reflection tends to occur, and the light transmittance of the polarizing plate tends to decrease.
- the amount exceeds 100 parts by weight the adhesive strength of the adhesive layer is reduced, or the refractive index of the adhesive layer is too low, so that between the polarizer and the adhesive layer and between the transparent protective film and the adhesive layer. Interfacial reflection of light is likely to occur between the respective layers, and the light transmittance of the polarizing plate tends to decrease.
- the adhesive for polarizing plates of the second invention is a resin solution containing a polyvinyl alcohol resin, a silicate, and an amino acid and / or a sulfur-containing amino acid having one or more amino groups and one or more acidic groups. Usually, it is used as an aqueous solution.
- the concentration of the resin solution is not particularly limited, but is preferably from 0.1 to 15% by weight, more preferably from 0.5 to 10% by weight in consideration of coating property and storage stability.
- the viscosity of the resin solution is not particularly limited, but a resin solution in the range of 1 to 50 mPa ⁇ s is usually used.
- the method for preparing the resin solution, which is the polarizing plate adhesive of the present invention is not particularly limited.
- a polyvinyl alcohol-based resin and a crosslinking agent are mixed, and a resin solution is prepared by blending silicate (water-soluble silicate) with an appropriately adjusted concentration.
- silicate water-soluble silicate
- the polyvinyl alcohol-based resin and the silicate After mixing the water-soluble silicate, the crosslinking agent may be mixed in consideration of the use time of the resin solution obtained.
- concentration of the resin solution which is an adhesive agent for polarizing plates can also be adjusted suitably after preparing a resin solution.
- stabilizers such as various tackifiers, ultraviolet absorbers, antioxidants, heat stabilizers, hydrolysis stabilizers, etc. can also be blended in the polarizing plate adhesive.
- the polarizing plate of the present invention is produced by laminating a transparent protective film and a polarizer using the adhesive.
- the transparent protective film is provided in the one side or both sides of the polarizer through the adhesive bond layer formed with the said polarizing plate adhesive.
- the application of the adhesive may be performed on either the transparent protective film or the polarizer, or may be performed on both.
- the application of the adhesive is preferably performed so that the thickness of the adhesive layer after drying is about 10 to 300 nm.
- the thickness of the adhesive layer is more preferably from 10 to 200 nm, particularly preferably from 20 to 150 nm, from the viewpoint of obtaining a uniform in-plane thickness and obtaining sufficient adhesive strength.
- the method of adjusting the thickness of the adhesive layer is not particularly limited, and examples thereof include a method of adjusting the solid content concentration of the adhesive solution and an adhesive application device.
- the method for measuring the thickness of the adhesive layer is not particularly limited, but cross-sectional observation measurement by SEM (Scanning Electron Microscopy) or TEM (Transmission Electron Microscopy) is preferably used.
- the application operation of the adhesive is not particularly limited, and various means such as a roll method, a spray method, and an immersion method can be employed.
- the polarizer and transparent protective film are bonded together using a roll laminator or the like.
- a drying process is performed to form an adhesive layer composed of a coating dry layer.
- the drying temperature is about 5 to 150 ° C., preferably 30 to 120 ° C., and the drying time is 120 seconds or more, preferably 300 seconds or more.
- the polarizer is not particularly limited, and various types can be used.
- the polarizer include hydrophilic polymers such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene / vinyl acetate copolymer partially saponified film, and two colors such as iodine and dichroic dye.
- polyene-based oriented films such as those obtained by adsorbing a functional material and uniaxially stretched, polyvinyl alcohol dehydrated products, and polyvinyl chloride dehydrochlorinated products.
- a polarizer composed of a polyvinyl alcohol film and a dichroic material such as iodine is preferable.
- the thickness of these polarizers is not particularly limited, but is generally about 5 to 80 ⁇ m.
- a polarizer in which a polyvinyl alcohol film is dyed with iodine and uniaxially stretched can be prepared, for example, by dyeing polyvinyl alcohol in an aqueous solution of iodine and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution of boric acid or potassium iodide. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with dirt and anti-blocking agents by washing the polyvinyl alcohol film with water, it also has the effect of preventing unevenness such as uneven coloring by swelling the polyvinyl alcohol film. is there.
- Stretching may be performed after dyeing with iodine, or may be performed while dyeing, or may be performed with iodine after stretching.
- the film can be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.
- the material forming the transparent protective film provided on one or both sides of the polarizer is preferably a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like.
- polyester polymers such as polyethylene terephthalate and polyethylene naphthalate
- cellulose polymers such as diacetyl cellulose and triacetyl cellulose
- acrylic polymers such as polymethyl methacrylate
- styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin) -Based polymer
- AS resin acrylonitrile / styrene copolymer
- a transparent protective film is usually bonded to the polarizer by an adhesive layer.
- thermosetting such as (meth) acrylic, urethane-based, acrylurethane-based, epoxy-based, silicone-based, etc.
- Resin or ultraviolet curable resin can be used.
- One or more kinds of arbitrary appropriate additives may be contained in the transparent protective film. Examples of the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a release agent, a coloring inhibitor, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent.
- the content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. .
- content of the said thermoplastic resin in a transparent protective film is 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.
- the transparent protective film examples include a polymer film described in JP-A-2001-343529 (WO01 / 37007), for example, (A) a thermoplastic resin having a substituted and / or unsubstituted imide group in the side chain, B) Resin compositions containing thermoplastic resins having substituted and / or unsubstituted phenyl and nitrile groups in the side chains.
- a specific example is a film of a resin composition containing an alternating copolymer of isobutylene and N-methylmaleimide and an acrylonitrile / styrene copolymer.
- As the film a film made of a mixed extruded product of the resin composition or the like can be used. Since these films have a small phase difference and a small photoelastic coefficient, problems such as unevenness due to the distortion of the polarizing plate can be eliminated, and since the moisture permeability is small, the humidification durability is excellent.
- the thickness of the transparent protective film can be appropriately determined, but is generally about 1 to 500 ⁇ m from the viewpoints of workability such as strength and handleability, and thin layer properties. 1 to 300 ⁇ m is particularly preferable, and 5 to 200 ⁇ m is more preferable. Knicks are more likely to occur as the transparent protective film becomes thinner. Therefore, the transparent protective film is particularly suitable when it is 5 to 100 ⁇ m.
- the protective film which consists of the same polymer material may be used for the front and back, and the protective film which consists of a different polymer material etc. may be used.
- the transparent protective film of the present invention it is preferable to use at least one selected from cellulose resin, polycarbonate resin, cyclic polyolefin resin and (meth) acrylic resin.
- Cellulose resin is an ester of cellulose and fatty acid.
- Specific examples of the cellulose ester resin include cellulose triacetate, cellulose diacetate, cellulose tripropionate, and cellulose dipropionate. Among these, cellulose triacetate is particularly preferable.
- Many products of cellulose triacetate are commercially available, which is advantageous in terms of availability and cost. Examples of commercially available cellulose triacetate products are trade names “UV-50”, “UV-80”, “SH-80”, “TD-80U”, “TD-TAC”, “UZ-” manufactured by FUJIFILM Corporation. TAC ”,“ KC series ”manufactured by Konica, and the like. In general, these cellulose triacetates have an in-plane retardation (Re) of almost zero, but a thickness direction retardation (Rth) of about 60 nm.
- Re in-plane retardation
- Rth thickness direction retardation
- a cellulose resin film having a small thickness direction retardation can be obtained, for example, by treating the cellulose resin.
- a base film such as polyethylene terephthalate, polypropylene or stainless steel coated with a solvent such as cyclopentanone or methyl ethyl ketone is bonded to a general cellulose film and dried by heating (for example, at 80 to 150 ° C. for about 3 to 10 minutes) ) And then peeling the base film; a solution obtained by dissolving norbornene resin, (meth) acrylic resin, etc. in a solvent such as cyclopentanone, methyl ethyl ketone, etc. is applied to a general cellulose resin film and dried by heating ( For example, a method of peeling the coated film after 80 to 150 ° C. for about 3 to 10 minutes) is mentioned.
- a fatty acid cellulose resin film with a controlled degree of fat substitution can be used as the cellulose resin film having a small thickness direction retardation.
- triacetyl cellulose has an acetic acid substitution degree of about 2.8.
- the Rth can be reduced by controlling the acetic acid substitution degree to 1.8 to 2.7.
- a plasticizer such as dibutyl phthalate, p-toluenesulfonanilide, acetyltriethyl citrate, etc.
- Rth can be controlled to be small.
- the addition amount of the plasticizer is preferably 40 parts by weight or less, more preferably 1 to 20 parts by weight, and further preferably 1 to 15 parts by weight with respect to 100 parts by weight of the fatty acid cellulose resin.
- cyclic polyolefin resin is preferably a norbornene resin.
- the cyclic olefin-based resin is a general term for resins that are polymerized using a cyclic olefin as a polymerization unit, and is described in, for example, JP-A-1-240517, JP-A-3-14882, JP-A-3-122137, and the like. Resin.
- cyclic olefin ring-opening (co) polymers examples include cyclic olefin addition polymers, cyclic olefins and ⁇ -olefins such as ethylene and propylene (typically random copolymers), And graft polymers obtained by modifying them with an unsaturated carboxylic acid or a derivative thereof, and hydrides thereof.
- cyclic olefin include norbornene monomers.
- Various products are commercially available as cyclic polyolefin resins.
- trade names “ZEONEX” and “ZEONOR” manufactured by ZEON CORPORATION trade names “ARTON” manufactured by JSR Corporation, “TOPASS” manufactured by TICONA, and trade names manufactured by Mitsui Chemicals, Inc. “APEL”.
- Tg glass transition temperature
- the polarizing plate can be excellent in durability.
- the upper limit of Tg of the (meth) acrylic resin is not particularly limited, it is preferably 170 ° C. or less from the viewpoint of moldability. From the (meth) acrylic resin, a film having in-plane retardation (Re) and thickness direction retardation (Rth) of almost zero can be obtained.
- any appropriate (meth) acrylic resin can be adopted as long as the effects of the present invention are not impaired.
- poly (meth) acrylic acid ester such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester copolymer, methyl methacrylate-acrylic acid ester- (Meth) acrylic acid copolymer, (meth) methyl acrylate-styrene copolymer (MS resin, etc.), a polymer having an alicyclic hydrocarbon group (for example, methyl methacrylate-cyclohexyl methacrylate copolymer, Methyl methacrylate- (meth) acrylate norbornyl copolymer, etc.).
- Preferable examples include C1-6 alkyl poly (meth) acrylates such as polymethyl (meth) acrylate. More preferred is a methyl methacrylate resin containing methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight).
- (meth) acrylic resin for example, (meth) acrylic resin having a ring structure in the molecule described in Acrypet VH and Acrypet VRL20A manufactured by Mitsubishi Rayon Co., Ltd. And a high Tg (meth) acrylic resin system obtained by intramolecular crosslinking or intramolecular cyclization reaction.
- (Meth) acrylic resin having a lactone ring structure can also be used as the (meth) acrylic resin. It is because it has high mechanical strength by high heat resistance, high transparency, and biaxial stretching.
- Examples of the (meth) acrylic resin having a lactone ring structure include JP 2000-230016, JP 2001-151814, JP 2002-120326, JP 2002-254544, and JP 2005. Examples thereof include (meth) acrylic resins having a lactone ring structure described in Japanese Patent No. 146084.
- the (meth) acrylic resin having a lactone ring structure preferably has a ring pseudo structure represented by the following general formula (Formula 1).
- R 1 , R 2 and R 3 each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.
- the organic residue may contain an oxygen atom.
- the content of the lactone ring structure represented by the general formula (Formula 2) in the structure of the (meth) acrylic resin having a lactone ring structure is preferably 5 to 90% by weight, more preferably 10 to 70% by weight, More preferably, it is 10 to 60% by weight, and particularly preferably 10 to 50% by weight.
- the content of the lactone ring structure represented by the general formula (Chemical Formula 2) in the structure of the (meth) acrylic resin having a lactone ring structure is less than 5% by weight, heat resistance, solvent resistance, and surface hardness are reduced. May be insufficient. If the content of the lactone ring structure represented by the general formula (Chemical Formula 2) in the structure of the (meth) acrylic resin having a lactone ring structure is more than 90% by weight, molding processability may be poor.
- the (meth) acrylic resin having a lactone ring structure has a mass average molecular weight (sometimes referred to as a weight average molecular weight) of preferably 1,000 to 2,000,000, more preferably 5,000 to 1,000,000, still more preferably 10,000 to 500,000, and particularly preferably. Is from 50,000 to 500,000. If the mass average molecular weight is out of the above range, it is not preferable from the viewpoint of molding processability.
- the (meth) acrylic resin having a lactone ring structure preferably has a Tg of 115 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 125 ° C. or higher, and particularly preferably 130 ° C. or higher. Since Tg is 115 ° C. or higher, for example, when incorporated into a polarizing plate as a transparent protective film, it has excellent durability.
- the upper limit of Tg of the (meth) acrylic resin having the lactone ring structure is not particularly limited, it is preferably 170 ° C. or less from the viewpoint of moldability and the like.
- the (meth) acrylic resin having a lactone ring structure is more preferable as the total light transmittance of a molded product obtained by injection molding measured by a method according to ASTM-D-1003 is higher, preferably 85 % Or more, more preferably 88% or more, and still more preferably 90% or more.
- the total light transmittance is a measure of transparency. If the total light transmittance is less than 85%, the transparency may be lowered.
- the transparent protective film those having a front retardation of less than 40 nm and a thickness direction retardation of less than 80 nm are usually used.
- the slow axis direction is the direction that maximizes the refractive index in the film plane. ].
- a transparent protective film has as little color as possible.
- a protective film having a retardation value in the thickness direction of ⁇ 90 nm to +75 nm is preferably used.
- the thickness direction retardation value (Rth) is more preferably ⁇ 80 nm to +60 nm, and particularly preferably ⁇ 70 nm to +45 nm.
- a retardation plate having a retardation with a front retardation of 40 nm or more and / or a thickness direction retardation of 80 nm or more can be used as the transparent protective film.
- the front phase difference is usually controlled in the range of 40 to 200 nm
- the thickness direction phase difference is usually controlled in the range of 80 to 300 nm.
- the retardation plate functions also as a transparent protective film, so that the thickness can be reduced.
- the transparent protective film can be appropriately selected according to the applied liquid crystal display device.
- VA including Vertical Alignment, MVA, PVA
- nx> ny nz
- nx> ny> nz nx> nz> ny
- both the upper and lower sides of the liquid crystal cell may have a phase difference, or any one of the upper and lower transparent protective films may have a phase difference.
- both cases where the transparent protective film on one side of the polarizing plate has a phase difference or not can be used.
- the liquid crystal cell has no phase difference both above and below (cell side).
- the liquid crystal cell has a phase difference, it is desirable that the liquid crystal cell has a phase difference on both the upper and lower sides.
- nx> ny nz
- the film having the retardation can be separately attached to a transparent protective film having no retardation to give the above function.
- the surface of the transparent protective film that adheres to the polarizer can be subjected to easy adhesion treatment.
- the easy adhesion treatment include dry treatment such as plasma treatment and corona treatment, chemical treatment such as alkali treatment (saponification treatment), and coating treatment for forming an easy adhesive layer.
- a coating treatment or an alkali treatment for forming an easy-adhesive layer is preferable.
- various easy-adhesive materials such as polyol resin, polycarboxylic acid resin, and polyester resin can be used.
- the thickness of the easy-adhesive layer is usually about 0.001 to 10 ⁇ m, more preferably about 0.001 to 5 ⁇ m, and particularly preferably about 0.001 to 1 ⁇ m.
- the surface of the transparent protective film to which the polarizer is not adhered may be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, antisticking, diffusion or antiglare.
- the antireflection layer, the antisticking layer, the diffusion layer, the antiglare layer and the like can be provided on the transparent protective film itself, or can be provided separately from the transparent protective film as an optical layer.
- the polarizing plate of the present invention can be used as an optical film laminated with another optical layer in practical use.
- the optical layer is not particularly limited.
- a liquid crystal display device such as a reflection plate, a semi-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), and a viewing angle compensation film.
- One or more optical layers that may be used can be used.
- a reflective polarizing plate or a semi-transmissive polarizing plate in which a polarizing plate or a semi-transmissive reflecting plate is further laminated on the polarizing plate of the present invention an elliptical polarizing plate or a circularly polarizing plate in which a retardation plate is further laminated on the polarizing plate.
- a wide viewing angle polarizing plate obtained by further laminating a viewing angle compensation film on a plate or a polarizing plate, or a polarizing plate obtained by further laminating a brightness enhancement film on the polarizing plate is preferable.
- the polarizing plate or optical film of the present invention can be preferably used for forming various devices such as a liquid crystal display device.
- the liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally formed by appropriately assembling components such as a liquid crystal cell, a polarizing plate or an optical film, and an illumination system as necessary, and incorporating a drive circuit. There is no limitation in particular except the point which uses the polarizing plate or optical film by invention, and it can apply according to the former.
- the liquid crystal cell any type such as a TN type, an STN type, or a ⁇ type can be used.
- liquid crystal display devices such as a liquid crystal display device in which a polarizing plate or an optical film is disposed on one side or both sides of a liquid crystal cell, or a backlight or a reflector used in an illumination system can be formed.
- the polarizing plate or optical film by this invention can be installed in the one side or both sides of a liquid crystal cell.
- a polarizing plate or an optical film on both sides they may be the same or different.
- a single layer or a suitable part such as a diffusion plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusion plate, a backlight, Two or more layers can be arranged.
- TAC triacetyl cellulose
- Example 2 to 11 Comparative Examples 1 to 4, and Reference Example 1
- An adhesive aqueous solution was prepared in the same manner as in Example 1 with the formulation shown in Table 1.
- a polarizing plate was prepared in the same manner as in Example 1 using the prepared aqueous adhesive solution.
- the single-piece transmittance Ts was measured using a spectrophotometer (manufactured by JASCO Corporation, V7100).
- Adhesion At the end of the polarizing plate, a cutter edge was inserted between the polarizer and the transparent protective film. In the insertion part, the polarizer and the transparent protective film were grasped and pulled in opposite directions. At this time, when the polarizer and / or the transparent protective film was broken and could not be peeled off, the adhesion was good: when judged as “ ⁇ ” and partly peeled off between the polarizer and the transparent protective film Slightly poor adhesion: judged as “ ⁇ ”, and when all peeled between the polarizer and the transparent protective film, poor adhesion was judged as “x”.
- a sample was prepared by cutting out the polarizing plate to be 1000 mm ⁇ 1000 mm.
- a sample polarizing plate was placed under a fluorescent lamp.
- Another polarizing plate was installed on the light source side of the sample polarizing plate so that the respective absorption axes were perpendicular to each other, and the number of spots (point defects, knick defects) where light was lost in this state was counted.
- TAC triacetyl cellulose
- Examples 2 to 7 and Comparative Examples 1 to 5 An adhesive aqueous solution was prepared in the same manner as in Example 1 with the formulation shown in Table 1. A polarizing plate was prepared in the same manner as in Example 1 using the prepared aqueous adhesive solution.
- Adhesion At the end of the polarizing plate, a cutter edge was inserted between the polarizer and the transparent protective film. In the insertion portion, the polarizer and the transparent protective film were gripped and pulled in opposite directions. At this time, when the polarizer and / or the transparent protective film was broken and could not be peeled off, the adhesion was good: when judged as “ ⁇ ” and partly peeled off between the polarizer and the transparent protective film Slightly poor adhesion: judged as “ ⁇ ”, and when all peeled between the polarizer and the transparent protective film, poor adhesion was judged as “x”.
- the adhesive for polarizing plates of this invention is used in order to adhere
- the obtained polarizing plate or an optical film in which the polarizing plate is laminated is used for an image display device such as a liquid crystal display device, an organic EL display device, and a PDP.
Abstract
Description
前記偏光板用接着剤は、ポリビニルアルコール系樹脂、及び水溶性珪酸塩を含有する樹脂溶液であることを特徴とする偏光板用接着剤、に関する。 That is, the first present invention is an adhesive for polarizing plates used for providing a transparent protective film on at least one side of a polarizer,
The said adhesive agent for polarizing plates is related with the adhesive agent for polarizing plates characterized by being the resin solution containing polyvinyl alcohol-type resin and water-soluble silicate.
前記偏光板用接着剤は、ポリビニルアルコール系樹脂、珪酸塩、及び1つ以上のアミノ基と1つ以上の酸性基とを有するアミノ酸及び/又は含硫アミノ酸を含有する樹脂溶液であることを特徴とする偏光板用接着剤、に関する。 On the other hand, the second present invention is an adhesive for polarizing plate used for providing a transparent protective film on at least one surface of a polarizer,
The polarizing plate adhesive is a resin solution containing a polyvinyl alcohol resin, a silicate, and an amino acid having at least one amino group and at least one acidic group and / or a sulfur-containing amino acid. It relates to the adhesive agent for polarizing plates.
前記偏光板用接着剤を調製する工程、偏光子の前記接着剤層を形成する面及び/又は透明保護フィルムの前記接着剤層を形成する面に前記偏光板用接着剤を塗布する工程、及び偏光子と透明保護フィルムとを貼り合わせる工程を含むことを特徴とする偏光板の製造方法、に関する。 Further, the present invention provides a method for producing a polarizing plate in which a transparent protective film is provided on at least one surface of a polarizer via an adhesive layer.
The step of preparing the polarizing plate adhesive, the step of applying the polarizing plate adhesive to the surface of the polarizer forming the adhesive layer and / or the surface of the transparent protective film forming the adhesive layer, and The present invention relates to a method for producing a polarizing plate, comprising a step of bonding a polarizer and a transparent protective film.
実施例1
(偏光子)
平均重合度2400、ケン化度99.9モル%の厚み75μmのポリビニルアルコールフィルムを、30℃の温水中に60秒間浸漬し膨潤させた。次いで、ヨウ素/ヨウ化カリウム(重量比=0.5/8)の濃度0.3%の水溶液に浸漬し、3.5倍まで延伸させながらフィルムを染色した。その後、65℃のホウ酸エステル水溶液中で、トータルの延伸倍率が6倍となるように延伸を行った。延伸後に、40℃のオーブンにて3分間乾燥を行い、偏光子を得た。分光光度計(日本分光製、V7100)を用いて、単体透過率Tsを測定したところ、光透過率は42.50%であった。 [First Invention]
Example 1
(Polarizer)
A polyvinyl alcohol film having an average polymerization degree of 2400 and a saponification degree of 99.9 mol% and a thickness of 75 μm was immersed in warm water at 30 ° C. for 60 seconds to swell. Next, the film was dyed while being immersed in an aqueous solution of 0.3% concentration of iodine / potassium iodide (weight ratio = 0.5 / 8) and stretched to 3.5 times. Then, it extended | stretched so that the total draw ratio might be 6 times in 65 degreeC borate ester aqueous solution. After extending | stretching, it dried for 3 minutes in 40 degreeC oven, and obtained the polarizer. When the single transmittance Ts was measured using a spectrophotometer (manufactured by JASCO Corporation, V7100), the light transmittance was 42.50%.
厚さ80μmのトリアセチルセルロース(TAC)フィルムを用いた。 (Transparent protective film)
A 80 μm thick triacetyl cellulose (TAC) film was used.
アセトアセチル(AA)基を含有するポリビニルアルコール(PVA)系樹脂(平均重合度:1200,ケン化度:98.5モル%,アセトアセチル化度:5モル%)100部に対し、珪酸ナトリウム(SiO2/Na2Oのモル比:4)10部を30℃の温度条件下で純水に溶解し、固形分濃度4%に調整して接着剤水溶液を得た。 (Preparation of adhesive aqueous solution)
Polyvinyl alcohol (PVA) -based resin containing acetoacetyl (AA) group (average polymerization degree: 1200, saponification degree: 98.5 mol%, acetoacetylation degree: 5 mol%) to 100 parts of sodium silicate ( SiO 2 / Na 2 O molar ratio: 4) 10 parts were dissolved in pure water under a temperature condition of 30 ° C. and adjusted to a solid content concentration of 4% to obtain an aqueous adhesive solution.
上記透明保護フィルムの片面に、上記接着剤水溶液を乾燥後の接着剤層の厚みが80nmとなるように塗布した。次いで、23℃の温度条件下で偏光子の両面に接着剤付きの透明保護フィルムをロール機で貼り合せ、その後55℃で6分間乾燥して偏光板を作成した。 (Creation of polarizing plate)
The adhesive aqueous solution was applied to one side of the transparent protective film so that the thickness of the adhesive layer after drying was 80 nm. Next, a transparent protective film with an adhesive was bonded to both sides of the polarizer under a temperature condition of 23 ° C. with a roll machine, and then dried at 55 ° C. for 6 minutes to prepare a polarizing plate.
表1記載の配合で実施例1と同様の方法で接着剤水溶液を調製した。調製した接着剤水溶液を用いて、実施例1と同様にして偏光板を作成した。 Examples 2 to 11, Comparative Examples 1 to 4, and Reference Example 1
An adhesive aqueous solution was prepared in the same manner as in Example 1 with the formulation shown in Table 1. A polarizing plate was prepared in the same manner as in Example 1 using the prepared aqueous adhesive solution.
(接着剤層の屈折率)
調製した接着剤水溶液を透明フィルムの上にアプリケーターで塗布し、70度で10分間乾燥して接着剤層を形成した。その後、接着剤層(5μm)を透明フィルムから剥離し、当該接着剤層の屈折率をプリズムカプラー(Sairon Technology,Inc.、SPA-4000)を用いて測定した。 [Measurement and evaluation]
(Refractive index of adhesive layer)
The prepared aqueous adhesive solution was applied onto a transparent film with an applicator and dried at 70 degrees for 10 minutes to form an adhesive layer. Thereafter, the adhesive layer (5 μm) was peeled from the transparent film, and the refractive index of the adhesive layer was measured using a prism coupler (Sairon Technology, Inc., SPA-4000).
分光光度計(日本分光製、V7100)を用いて、単体透過率Tsを測定した。 (Light transmittance of polarizing plate)
The single-piece transmittance Ts was measured using a spectrophotometer (manufactured by JASCO Corporation, V7100).
偏光板の端部において、偏光子と透明保護フィルムとの間にカッターの刃先を挿入した。当該挿入部において、偏光子と透明保護フィルムとを掴み、それぞれ反対方向に引っ張った。このとき、偏光子および/または透明保護フィルムが破断して剥離できなかった場合は、密着性が良好:「○」と判断し、偏光子と透明保護フィルムとの間で一部剥離した場合は、密着性にやや乏しい:「△」と判断し、偏光子と透明保護フィルムとの間で全部剥離した場合は、密着性に乏しい:「×」と判断した。 (Adhesion)
At the end of the polarizing plate, a cutter edge was inserted between the polarizer and the transparent protective film. In the insertion part, the polarizer and the transparent protective film were grasped and pulled in opposite directions. At this time, when the polarizer and / or the transparent protective film was broken and could not be peeled off, the adhesion was good: when judged as “◯” and partly peeled off between the polarizer and the transparent protective film Slightly poor adhesion: judged as “Δ”, and when all peeled between the polarizer and the transparent protective film, poor adhesion was judged as “x”.
偏光板を、偏光子の吸収軸方向に50mm、吸収軸に直交する方向に25mmになるように切り出してサンプルを調製した。当該サンプルを60℃、95%RHの加温加湿雰囲気下に200時間放置した。このとき、偏光子/保護フィルム間に剥がれが生じなかった場合は○、端部が浮いた場合は△、すべて剥がれてしまった場合は×と判断した。 (Peeling)
A sample was prepared by cutting the polarizing plate so as to be 50 mm in the absorption axis direction of the polarizer and 25 mm in the direction perpendicular to the absorption axis. The sample was left in a heated and humidified atmosphere of 60 ° C. and 95% RH for 200 hours. At this time, when peeling did not occur between the polarizer / protective film, it was judged as ◯, when the end part was lifted, Δ, and when all peeled off, it was judged as x.
偏光板を1000mm×1000mmになるように切り出してサンプルを調製した。サンプルの偏光板を、蛍光灯下に置いた。サンプルの偏光板の光源側に別の偏光板を、それぞれの吸収軸が直行するように設置し、この状態で光抜けする箇所(点欠点、クニック欠陥)の個数をカウントした。 (Appearance evaluation: Knick defect)
A sample was prepared by cutting out the polarizing plate to be 1000 mm × 1000 mm. A sample polarizing plate was placed under a fluorescent lamp. Another polarizing plate was installed on the light source side of the sample polarizing plate so that the respective absorption axes were perpendicular to each other, and the number of spots (point defects, knick defects) where light was lost in this state was counted.
偏光子の吸収軸方向に50mm、吸収軸に直交する方向に25mmになるように切り出した偏光板を粘着剤を介してガラス板に接着してサンプルを調製し、当該サンプルの光透過率を分光光度計(日本分光製、V7100)を用いて測定した。その後、当該サンプルを60℃、95%RHの加温加湿雰囲気下に200時間放置し、同様に光透過率を測定した。加温加湿試験前後の光透過率の変化量(差)を表1に示す。また、当該サンプルを85℃、85%RHの加温加湿雰囲気下に200時間放置し、同様に光透過率を測定した。加温加湿試験前後の光透過率の変化量(差)を表1に示す。 (Heating and humidification test)
A polarizing plate cut out to be 50 mm in the absorption axis direction of the polarizer and 25 mm in the direction orthogonal to the absorption axis is adhered to a glass plate via an adhesive, and a sample is prepared. It measured using the photometer (the JASCO make, V7100). Thereafter, the sample was left in a heated and humidified atmosphere of 60 ° C. and 95% RH for 200 hours, and the light transmittance was measured in the same manner. Table 1 shows the amount of change (difference) in light transmittance before and after the warming and humidification test. Further, the sample was left in a heated and humidified atmosphere of 85 ° C. and 85% RH for 200 hours, and the light transmittance was measured in the same manner. Table 1 shows the amount of change (difference) in light transmittance before and after the warming and humidification test.
実施例1
(偏光子)
平均重合度2400、ケン化度99.9モル%の厚み75μmのポリビニルアルコールフィルムを、30℃の温水中に60秒間浸漬し膨潤させた。次いで、ヨウ素/ヨウ化カリウム(重量比=0.5/8)の濃度0.3%の水溶液に浸漬し、3.5倍まで延伸させながらフィルムを染色した。その後、65℃のホウ酸エステル水溶液中で、トータルの延伸倍率が6倍となるように延伸を行った。延伸後に、40℃のオーブンにて3分間乾燥を行い、偏光子を得た。分光光度計(日本分光製、V7100)を用いて、単体透過率Tsを測定したところ、光透過率は42.50%であった。 [Second Invention]
Example 1
(Polarizer)
A polyvinyl alcohol film having an average polymerization degree of 2400 and a saponification degree of 99.9 mol% and a thickness of 75 μm was immersed in warm water at 30 ° C. for 60 seconds to swell. Next, the film was dyed while being immersed in an aqueous solution of 0.3% concentration of iodine / potassium iodide (weight ratio = 0.5 / 8) and stretched to 3.5 times. Then, it extended | stretched so that the total draw ratio might be 6 times in 65 degreeC borate ester aqueous solution. After extending | stretching, it dried for 3 minutes in 40 degreeC oven, and obtained the polarizer. When the single transmittance Ts was measured using a spectrophotometer (manufactured by JASCO Corporation, V7100), the light transmittance was 42.50%.
厚さ80μmのトリアセチルセルロース(TAC)フィルムを用いた。 (Transparent protective film)
A 80 μm thick triacetyl cellulose (TAC) film was used.
アセトアセチル(AA)基を含有するポリビニルアルコール(PVA)系樹脂(平均重合度:1200,ケン化度:98.5モル%,アセトアセチル化度:5モル%)100部、珪酸ナトリウム(SiO2/Na2Oのモル比:4)10部、タウリン50部を30℃の温度条件下で純水に溶解して接着剤水溶液(粘度9mPa・s)を得た。 (Preparation of adhesive aqueous solution)
Polyvinyl alcohol (PVA) -based resin containing acetoacetyl (AA) group (average polymerization degree: 1200, saponification degree: 98.5 mol%, acetoacetylation degree: 5 mol%), 100 parts, sodium silicate (SiO 2 / Na 2 O molar ratio: 4) 10 parts of taurine and 50 parts of taurine were dissolved in pure water under a temperature condition of 30 ° C. to obtain an aqueous adhesive solution (viscosity 9 mPa · s).
上記透明保護フィルムの片面に、上記接着剤水溶液を乾燥後の接着剤層の厚みが80nmとなるように塗布した。次いで、23℃の温度条件下で偏光子の両面に接着剤付きの透明保護フィルムをロール機で貼り合せ、その後55℃で6分間乾燥して偏光板を作成した。 (Creation of polarizing plate)
The adhesive aqueous solution was applied to one side of the transparent protective film so that the thickness of the adhesive layer after drying was 80 nm. Next, a transparent protective film with an adhesive was bonded to both sides of the polarizer under a temperature condition of 23 ° C. with a roll machine, and then dried at 55 ° C. for 6 minutes to prepare a polarizing plate.
表1記載の配合で実施例1と同様の方法で接着剤水溶液を調製した。調製した接着剤水溶液を用いて、実施例1と同様にして偏光板を作成した。 Examples 2 to 7 and Comparative Examples 1 to 5
An adhesive aqueous solution was prepared in the same manner as in Example 1 with the formulation shown in Table 1. A polarizing plate was prepared in the same manner as in Example 1 using the prepared aqueous adhesive solution.
(接着剤層の屈折率)
調製した接着剤水溶液を透明フィルムの上にアプリケーターで塗布し、70度で10分間乾燥して接着剤層を形成した。その後、接着剤層(5μm)を透明フィルムから剥離し、当該接着剤層の屈折率をプリズムカプラー(Sairon Technology,Inc.、SPA-4000)を用いて測定した。 [Measurement and evaluation]
(Refractive index of adhesive layer)
The prepared aqueous adhesive solution was applied onto a transparent film with an applicator and dried at 70 degrees for 10 minutes to form an adhesive layer. Thereafter, the adhesive layer (5 μm) was peeled from the transparent film, and the refractive index of the adhesive layer was measured using a prism coupler (Sairon Technology, Inc., SPA-4000).
偏光板の端部において、偏光子と透明保護フィルムとの間にカッターの刃先を挿入した。当該挿入部において、偏光子と透明保護フィルムとを掴み、それぞれ反対方向に引っ張った。このとき、偏光子および/または透明保護フィルムが破断して剥離できなかった場合は、密着性が良好:「○」と判断し、偏光子と透明保護フィルムとの間で一部剥離した場合は、密着性にやや乏しい:「△」と判断し、偏光子と透明保護フィルムとの間で全部剥離した場合は、密着性に乏しい:「×」と判断した。 (Adhesion)
At the end of the polarizing plate, a cutter edge was inserted between the polarizer and the transparent protective film. In the insertion portion, the polarizer and the transparent protective film were gripped and pulled in opposite directions. At this time, when the polarizer and / or the transparent protective film was broken and could not be peeled off, the adhesion was good: when judged as “◯” and partly peeled off between the polarizer and the transparent protective film Slightly poor adhesion: judged as “Δ”, and when all peeled between the polarizer and the transparent protective film, poor adhesion was judged as “x”.
偏光板を、偏光子の吸収軸方向に50mm、吸収軸に直交する方向に25mmになるように切り出してサンプルを調製した。当該サンプルを60℃の温水に浸漬し、5時間経過後のサンプルの端部の剥がれ量(mm)をノギスで測定した。 (Peeling)
A sample was prepared by cutting the polarizing plate so as to be 50 mm in the absorption axis direction of the polarizer and 25 mm in the direction perpendicular to the absorption axis. The sample was immersed in warm water at 60 ° C., and the amount of peeling (mm) at the end of the sample after 5 hours was measured with a caliper.
偏光子の吸収軸方向に50mm、吸収軸に直交する方向に25mmになるように切り出した偏光板を粘着剤を介してガラス板に接着してサンプルを調製し、当該サンプルの光透過率を分光光度計(日本分光製、V7100)を用いて測定した。その後、当該サンプルを60℃、95%RHの加温加湿雰囲気下に200時間放置し、同様に光透過率を測定した。加温加湿試験前後の光透過率の変化量(差)を表2に示す。 (Heating and humidification test)
A polarizing plate cut out to be 50 mm in the absorption axis direction of the polarizer and 25 mm in the direction orthogonal to the absorption axis is adhered to a glass plate via an adhesive, and a sample is prepared. It measured using the photometer (the JASCO make, V7100). Thereafter, the sample was left in a heated and humidified atmosphere of 60 ° C. and 95% RH for 200 hours, and the light transmittance was measured in the same manner. Table 2 shows the amount of change (difference) in light transmittance before and after the warming and humidification test.
調製した接着剤水溶液の粘度を、レオメーターRS1(Haake社製)、共軸円筒として型式222-1267及び222-1549を用いて、23℃の液温及び気温にて測定し、接着剤水溶液の粘度が50cpsを超えるまでの時間を測定した。 (Pot life)
The viscosity of the prepared aqueous adhesive solution was measured at 23 ° C. liquid temperature and temperature using rheometer RS1 (manufactured by Haake) and models 222-1267 and 222-1549 as coaxial cylinders. The time until the viscosity exceeded 50 cps was measured.
The adhesive for polarizing plates of this invention is used in order to adhere | attach a transparent protective film on the at least single side | surface of a polarizer. The obtained polarizing plate or an optical film in which the polarizing plate is laminated is used for an image display device such as a liquid crystal display device, an organic EL display device, and a PDP.
Claims (20)
- 偏光子の少なくとも片面に透明保護フィルムを設けるために用いる偏光板用接着剤において、
前記偏光板用接着剤は、ポリビニルアルコール系樹脂、及び水溶性珪酸塩を含有する樹脂溶液であることを特徴とする偏光板用接着剤。 In the adhesive for polarizing plates used to provide a transparent protective film on at least one side of the polarizer,
The polarizing plate adhesive is a resin solution containing a polyvinyl alcohol-based resin and a water-soluble silicate. - 水溶性珪酸塩の配合量は、ポリビニルアルコール系樹脂100重量部に対して、1~100重量部である請求項1記載の偏光板用接着剤。 The adhesive for polarizing plates according to claim 1, wherein the amount of the water-soluble silicate is 1 to 100 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin.
- 水溶性珪酸塩が、珪酸リチウム、珪酸ナトリウム、及び珪酸カリウムからなる群より選択される少なくとも1種である請求項1記載の偏光板用接着剤。 The polarizing plate adhesive according to claim 1, wherein the water-soluble silicate is at least one selected from the group consisting of lithium silicate, sodium silicate, and potassium silicate.
- 珪酸リチウムは、SiO2/Li2Oのモル比が2~8である請求項3記載の偏光板用接着剤。 The adhesive for polarizing plates according to claim 3, wherein the lithium silicate has a SiO 2 / Li 2 O molar ratio of 2 to 8.
- 珪酸ナトリウムは、SiO2/Na2Oのモル比が2~5である請求項3記載の偏光板用接着剤。 The polarizing plate adhesive according to claim 3, wherein the sodium silicate has a SiO 2 / Na 2 O molar ratio of 2 to 5.
- 珪酸カリウムは、SiO2/K2Oのモル比が2~5である請求項3記載の偏光板用接着剤。 The adhesive for polarizing plates according to claim 3, wherein the potassium silicate has a SiO 2 / K 2 O molar ratio of 2 to 5.
- 偏光子の少なくとも片面に透明保護フィルムを設けるために用いる偏光板用接着剤において、
前記偏光板用接着剤は、ポリビニルアルコール系樹脂、珪酸塩、及び1つ以上のアミノ基と1つ以上の酸性基とを有するアミノ酸及び/又は含硫アミノ酸を含有する樹脂溶液であることを特徴とする偏光板用接着剤。 In the adhesive for polarizing plates used to provide a transparent protective film on at least one side of the polarizer,
The polarizing plate adhesive is a resin solution containing a polyvinyl alcohol resin, a silicate, and an amino acid having at least one amino group and at least one acidic group and / or a sulfur-containing amino acid. An adhesive for polarizing plate. - アミノ酸及び/又は含硫アミノ酸の配合量は、ポリビニルアルコール系樹脂100重量部に対して、5~50重量部である請求項7記載の偏光板用接着剤。 The polarizing plate adhesive according to claim 7, wherein the compounding amount of the amino acid and / or sulfur-containing amino acid is 5 to 50 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin.
- 酸性基は、カルボキシル基又はスルホ基である請求項7記載の偏光板用接着剤。 The adhesive for polarizing plates according to claim 7, wherein the acidic group is a carboxyl group or a sulfo group.
- 珪酸塩が、水溶性珪酸リチウム、水溶性珪酸ナトリウム、及び水溶性珪酸カリウムからなる群より選択される少なくとも1種である請求項7記載の偏光板用接着剤。 The adhesive for polarizing plates according to claim 7, wherein the silicate is at least one selected from the group consisting of water-soluble lithium silicate, water-soluble sodium silicate, and water-soluble potassium silicate.
- ポリビニルアルコール系樹脂が、アセトアセチル基を含有するポリビニルアルコール系樹脂である請求項1又は7記載の偏光板用接着剤。 The polarizing plate adhesive according to claim 1 or 7, wherein the polyvinyl alcohol resin is a polyvinyl alcohol resin containing an acetoacetyl group.
- 偏光子の少なくとも一方の面に、接着剤層を介して透明保護フィルムが設けられている偏光板において、前記接着剤層が請求項1記載の偏光板用接着剤により形成されていることを特徴とする偏光板。 In the polarizing plate in which a transparent protective film is provided on at least one surface of the polarizer via an adhesive layer, the adhesive layer is formed of the polarizing plate adhesive according to claim 1. A polarizing plate.
- 偏光子の少なくとも一方の面に、接着剤層を介して透明保護フィルムが設けられている偏光板において、前記接着剤層が請求項7記載の偏光板用接着剤により形成されていることを特徴とする偏光板。 A polarizing plate in which a transparent protective film is provided on at least one surface of a polarizer via an adhesive layer, wherein the adhesive layer is formed of the polarizing plate adhesive according to claim 7. A polarizing plate.
- 接着剤層の厚みが、10~300nmである請求項12又は13記載の偏光板。 The polarizing plate according to claim 12 or 13, wherein the adhesive layer has a thickness of 10 to 300 nm.
- 接着剤層の屈折率が、1.47~1.54である請求項12記載の偏光板。 The polarizing plate according to claim 12, wherein the adhesive layer has a refractive index of 1.47 to 1.54.
- 接着剤層の屈折率が、1.47~1.55である請求項13記載の偏光板。 The polarizing plate according to claim 13, wherein the adhesive layer has a refractive index of 1.47 to 1.55.
- 偏光子の少なくとも一方の面に、接着剤層を介して透明保護フィルムが設けられている偏光板を製造する方法において、
請求項1又は7記載の偏光板用接着剤を調製する工程、偏光子の前記接着剤層を形成する面及び/又は透明保護フィルムの前記接着剤層を形成する面に前記偏光板用接着剤を塗布する工程、及び偏光子と透明保護フィルムとを貼り合わせる工程を含むことを特徴とする偏光板の製造方法。 In the method for producing a polarizing plate in which at least one surface of the polarizer is provided with a transparent protective film via an adhesive layer,
The process for preparing the adhesive agent for polarizing plates of Claim 1 or 7, the surface which forms the said adhesive bond layer of a polarizer, and / or the surface which forms the said adhesive bond layer of a transparent protective film, The said adhesive agent for polarizing plates The manufacturing method of the polarizing plate characterized by including the process to apply | coat, and the process of bonding a polarizer and a transparent protective film together. - 請求項12又は13記載の偏光板が、少なくとも1枚積層されている光学フィルム。 An optical film in which at least one polarizing plate according to claim 12 or 13 is laminated.
- 請求項12又は13記載の偏光板を含む画像表示装置。 An image display device comprising the polarizing plate according to claim 12 or 13.
- 請求項18記載の光学フィルムを含む画像表示装置。
An image display device comprising the optical film according to claim 18.
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CN201180007014.0A CN102741717B (en) | 2010-03-05 | 2011-03-03 | Adhesive for polarizing plate, polarizing plate, method for producing same, optical film, and image display device |
US13/581,916 US9366900B2 (en) | 2010-03-05 | 2011-03-03 | Adhesive for polarizing plate, polarizing plate, method for producing same, optical film, and image display device |
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JP2010222791A JP5143204B2 (en) | 2010-09-30 | 2010-09-30 | Polarizing plate adhesive, polarizing plate, optical film, and image display device |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013076773A (en) * | 2011-09-29 | 2013-04-25 | Nippon Shokubai Co Ltd | Polarizer protective film and use of the same |
JP2018010327A (en) * | 2017-10-13 | 2018-01-18 | 住友化学株式会社 | Apparatus for manufacturing and method for manufacturing polarizing film, and polarizing film |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5533478B2 (en) * | 1972-06-22 | 1980-08-30 | ||
JPH02311582A (en) * | 1989-05-26 | 1990-12-27 | Kazuhiko Takagi | Water glass-isocyanate adhesive |
JPH07198645A (en) * | 1993-12-29 | 1995-08-01 | Ricoh Co Ltd | Thin film gas sensor and method of driving thereof |
WO2005085383A1 (en) * | 2004-03-03 | 2005-09-15 | Nippon Kayaku Kabushiki Kaisha | Water-based adhesive for polarizing element and polarizer obtained with the same |
JP2008015483A (en) * | 2006-06-09 | 2008-01-24 | Nitto Denko Corp | Adhesive for polarizing plate, polarizing plate, method for manufacturing the same, optical film and image display device |
-
2011
- 2011-03-03 WO PCT/JP2011/054925 patent/WO2011108647A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5533478B2 (en) * | 1972-06-22 | 1980-08-30 | ||
JPH02311582A (en) * | 1989-05-26 | 1990-12-27 | Kazuhiko Takagi | Water glass-isocyanate adhesive |
JPH07198645A (en) * | 1993-12-29 | 1995-08-01 | Ricoh Co Ltd | Thin film gas sensor and method of driving thereof |
WO2005085383A1 (en) * | 2004-03-03 | 2005-09-15 | Nippon Kayaku Kabushiki Kaisha | Water-based adhesive for polarizing element and polarizer obtained with the same |
JP2008015483A (en) * | 2006-06-09 | 2008-01-24 | Nitto Denko Corp | Adhesive for polarizing plate, polarizing plate, method for manufacturing the same, optical film and image display device |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013076773A (en) * | 2011-09-29 | 2013-04-25 | Nippon Shokubai Co Ltd | Polarizer protective film and use of the same |
JP2018010327A (en) * | 2017-10-13 | 2018-01-18 | 住友化学株式会社 | Apparatus for manufacturing and method for manufacturing polarizing film, and polarizing film |
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