WO2018034230A1 - アクリル系粘着剤組成物、及びそれを用いてなる粘着剤、偏光板用粘着剤、ならびに画像表示装置 - Google Patents
アクリル系粘着剤組成物、及びそれを用いてなる粘着剤、偏光板用粘着剤、ならびに画像表示装置 Download PDFInfo
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- WO2018034230A1 WO2018034230A1 PCT/JP2017/029081 JP2017029081W WO2018034230A1 WO 2018034230 A1 WO2018034230 A1 WO 2018034230A1 JP 2017029081 W JP2017029081 W JP 2017029081W WO 2018034230 A1 WO2018034230 A1 WO 2018034230A1
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- sensitive adhesive
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- adhesive composition
- acrylic
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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
- C09J133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09J133/16—Homopolymers or copolymers of esters containing halogen atoms
-
- 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
- C09J133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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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
- C09J133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- 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 acrylic pressure-sensitive adhesive composition, a pressure-sensitive adhesive using the same, and a pressure-sensitive adhesive for a polarizing plate. More specifically, the heat-resistant whitening resistance under wet heat conditions and the storage stability of the pressure-sensitive adhesive layer are excellent.
- the present invention relates to an acrylic pressure-sensitive adhesive composition that forms a pressure-sensitive adhesive.
- a polarizing plate made of a polyvinyl alcohol film or the like having a polarizing property is coated on a surface of a liquid crystal cell in which a liquid crystal component oriented between two glass plates is sandwiched between two glass plates.
- image display devices are manufactured.
- the lamination of the polarizing plate on the surface of the liquid crystal cell is usually performed by bringing the pressure-sensitive adhesive layer provided on the surface of the polarizing plate into contact with the liquid crystal cell surface and pressing it.
- An adhesive containing a polyvinyl alcohol resin is preferably used as an adhesive for laminating the protective film and the polarizer.
- an aqueous solution obtained by blending a polyvinyl alcohol resin and a crosslinking agent is used as the polarizer.
- a polarizing plate is produced by heating and drying. In the manufacturing process of the polarizing plate, it is preferable that moisture contained in the adhesive permeate the protective film, and a highly permeable triacetyl cellulose film (TAC film) has been suitably used as the protective film. .
- an olefin film particularly a cycloolefin film (COP film) is used as a protective film for a polarizing plate instead of a TAC film from the viewpoint of dimensional stability and durability.
- COP film cycloolefin film
- the wet heat resistance of the polarizing plate is improved, but when the liquid crystal display device in which the polarizing plate is bonded to the liquid crystal cell through the adhesive is exposed to a wet heat environment, the adhesive is used. There was a problem that the whitening phenomenon of the layer was likely to occur.
- the pressure-sensitive adhesive for laminating the polarizing plate and the liquid crystal cell is required to have durability such as heat resistance and heat-and-moisture resistance.
- a silane coupling agent is generally used. It is known to contain. The silane coupling agent is hydrolyzed with water to form silanol, and the adhesiveness is improved by reacting with and binding to the hydroxyl group on the glass surface.
- Patent Document 1 describes that an acrylic pressure-sensitive adhesive using an acrylic resin copolymerized with a larger amount of hydroxyl monomers than usual has excellent moisture and heat whitening resistance. ing.
- the pressure-sensitive adhesive described in Patent Document 1 has a high content of hydroxyl monomers (polar group-containing monomers) in acrylic resins, it is excellent in moisture and heat whitening resistance, but on the other hand, it has high hydrophilicity and is in a normal environment. Even underneath, moisture easily enters the pressure-sensitive adhesive layer.
- a pressure-sensitive adhesive layer is provided on a release-treated film, and the pressure-sensitive adhesive layer side opposite to the release film is attached to the polarizing plate to form a polarizing plate with a pressure-sensitive adhesive layer. It is manufactured, and then, when bonded to the liquid crystal cell, the release film is peeled off, and the pressure-sensitive adhesive layer and the glass substrate of the liquid crystal cell are bonded.
- an acrylic adhesive composition containing an acrylic resin and a silane coupling agent a relatively large number of structural units derived from polar group-containing monomers.
- a silane coupling agent having a specific alkoxy group By using a acryl-based resin and a silane coupling agent having a specific alkoxy group, whitening of the pressure-sensitive adhesive layer can be suppressed even under wet heat conditions, and a pressure-sensitive adhesive having excellent storage stability can be obtained. I found.
- the present invention is an acrylic pressure-sensitive adhesive composition containing an acrylic resin (A) and a silane coupling agent (B) containing at least one reactive functional group and an alkoxy group in the structure.
- the acrylic resin (A) contains 5 to 50% by weight of a structural unit derived from at least one polar group-containing monomer (a1) selected from a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and a nitrogen-containing monomer.
- a first gist is an acrylic pressure-sensitive adhesive composition which is a resin and at least one of the alkoxy groups contained in the silane coupling agent (B) is an alkoxy group having 2 to 8 carbon atoms.
- the present invention relates to a polarization obtained by using the pressure-sensitive adhesive obtained by crosslinking the acrylic pressure-sensitive adhesive composition according to the first aspect with a crosslinking agent (C), and using the pressure-sensitive adhesive according to the second aspect.
- An image display apparatus comprising a plate adhesive and a liquid crystal cell bonded together with a plate adhesive as a third summary and a second summary adhesive is a fourth summary.
- the present invention is an acrylic pressure-sensitive adhesive composition containing an acrylic resin (A) and a silane coupling agent (B) containing at least one reactive functional group and an alkoxy group in the structure
- the acrylic resin (A) is an acrylic resin containing 5 to 50% by weight of a structural unit derived from at least one polar group-containing monomer (a1) selected from a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and a nitrogen-containing monomer.
- an acrylic pressure-sensitive adhesive composition in which at least one of the alkoxy groups contained in the silane coupling agent (B) is an alkoxy group having 2 to 8 carbon atoms.
- the pressure-sensitive adhesive obtained using the acrylic pressure-sensitive adhesive composition of the present invention is excellent in durability and moisture and heat whitening resistance even when used as a pressure-sensitive adhesive that bonds a polarizing plate and a glass substrate.
- the storage stability of the pressure-sensitive adhesive layer is also excellent. Therefore, by using this acrylic pressure-sensitive adhesive composition, it is possible to obtain an image display device exhibiting excellent optical characteristics without deterioration in performance even when used in a severer environment than usual, such as under wet heat conditions. it can.
- the pressure-sensitive adhesive layer has excellent resistance to moist heat and whitening and the storage stability of the pressure-sensitive adhesive layer. It is very useful as an adhesive.
- the polar group-containing monomer (a1) is a hydroxyl group-containing monomer, it is more excellent in moisture and heat whitening resistance and excellent in adhesive properties.
- the alkoxy group having 2 to 8 carbon atoms contained in the silane coupling agent (B) is an ethoxy group, the durability and the storage stability of the pressure-sensitive adhesive layer are more excellent.
- the alkoxy group contained in the silane coupling agent (B) is an ethoxy group or a methoxy group, the durability and the storage stability of the pressure-sensitive adhesive layer are further improved.
- the silane coupling agent (B) contains an alkoxy group in an amount of 5% by weight or more, the durability and the storage stability of the pressure-sensitive adhesive layer are further improved, and the reworkability is also excellent.
- the reactive functional group equivalent of the silane coupling agent (B) is 50 to 1000 g / mol, the durability and reworkability are further improved.
- (meth) acryl means acryl or methacryl
- (meth) acryloyl means acryloyl or methacryloyl
- (meth) acrylate means acrylate or methacrylate.
- the acrylic resin is a resin obtained by polymerizing a polymerization component containing at least one (meth) acrylate monomer.
- the acrylic pressure-sensitive adhesive composition of the present invention contains an acrylic resin (A) and a silane coupling agent (B) as essential components.
- the acrylic resin (A) used in the present invention is an acrylic resin containing 5 to 50% by weight of a structural unit derived from the polar group-containing monomer (a1). It is obtained by copolymerizing a copolymer component containing 50% by weight.
- the copolymer component of the acrylic resin (A) may contain a (meth) acrylic acid alkyl ester monomer (a2) and other copolymerizable ethylenically unsaturated monomers (a3) as necessary.
- the polar group-containing monomer (a1) is at least one selected from a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and a nitrogen-containing monomer.
- hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl ( Hydroxyalkyl esters of acrylic acid such as (meth) acrylate, caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth) acrylate, oxyalkylene-modified monomers such as diethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, etc.
- Primary hydroxyl group-containing monomers such as acryloyloxyethyl-2-hydroxyethylphthalic acid, N-methylol (meth) acrylamide, and hydroxyethylacrylamide
- Secondary hydroxyl group-containing monomers such as 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-chloro-2-hydroxypropyl (meth) acrylate; 2,2-dimethyl 2-hydroxyethyl (meth) acrylate
- tertiary hydroxyl group-containing monomers such as
- hydroxyl group-containing monomers a primary hydroxyl group-containing monomer is preferable in that it has excellent reactivity with a crosslinking agent and moisture and heat whitening resistance is improved, and 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are more preferable. It is preferable in that it has few impurities such as di (meth) acrylate and is easy to produce.
- the content rate of di (meth) acrylate which is an impurity is 0.5 weight% or less, More preferably, 0.2 weight% or less, Particularly preferred is 0.1% by weight or less.
- 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and 2-hydroxypropyl acrylate are preferable.
- carboxyl group-containing monomer examples include dimer acid of acrylic acid such as (meth) acrylic acid and ⁇ -carboxyethyl acrylate. Among them, in terms of resistance to moist heat whitening and stability during polymerization ( (Meth) acrylic acid is preferred.
- nitrogen-containing monomer examples include amino group-containing monomers and amide group-containing monomers.
- amino group-containing monomer examples include primary amino group-containing monomers such as aminomethyl (meth) acrylate and aminoethyl (meth) acrylate, secondary amino group-containing monomers such as tert-butylaminoethyl (meth) acrylate, And tertiary amino group-containing monomers such as ethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate.
- primary amino group-containing monomers such as aminomethyl (meth) acrylate and aminoethyl (meth) acrylate
- secondary amino group-containing monomers such as tert-butylaminoethyl (meth) acrylate
- tertiary amino group-containing monomers such as ethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate,
- amide group-containing monomer examples include methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, isopropoxymethyl (meth) acrylamide, n-butoxymethyl (meth) acrylamide, and isobutoxy.
- Alkoxyalkyl (meth) acrylamide monomers such as methyl (meth) acrylamide; dialkyl (meth) acrylamide monomers such as dimethyl (meth) acrylamide and diethyl (meth) acrylamide; (meth) acrylamide; N- (hydroxymethyl) acrylamide; (Meth) acryloylmorpholine and the like can be mentioned.
- alkoxyalkyl (meth) acrylamide monomers and dialkyl (meth) acrylamide monomers are preferable from the viewpoint of the stability of the resin solution and the suppression of migration of the antistatic agent.
- polar group-containing monomers (a1) a hydroxyl group-containing monomer and a carboxyl group-containing monomer are preferable in terms of moisture and heat whitening resistance and adhesive physical properties, and further a hydroxyl group in terms of excellent moisture and heat whitening resistance and long-term reworkability. Containing monomers are preferred.
- said polar group containing monomer (a1) can be used individually or in combination of 2 or more types.
- the content of the polar group-containing monomer (a1) (when two or more types are used in combination, the total content thereof) is 5 to 50% by weight, particularly 6 to 30% by weight, based on the entire copolymerization component. %, More preferably 7 to 25% by weight, especially 8 to 20% by weight.
- the content is too small, the heat-and-moisture whitening resistance decreases, and when the content is too large, the storage stability of the pressure-sensitive adhesive decreases.
- the alkyl group usually has 1 to 20 carbon atoms (preferably 1 to 18, particularly preferably 1 to 12, more preferably 1 to 8). Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-propyl ( (Meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) An acrylate etc. are mentioned. These may be used alone or in combination of two or more.
- methyl acrylate, ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate are preferable in terms of versatility and adhesive properties.
- the content of the (meth) acrylic acid alkyl ester monomer (a2) is preferably 20 to 95% by weight, particularly preferably 40 to 94% by weight, more preferably 45 to 45% by weight based on the entire copolymerization component. 93% by weight, in particular 50 to 92% by weight. If the content is too small, it tends to be difficult to balance the physical properties of the adhesive. If the content is too large, the wet heat whitening property tends to decrease.
- Examples of the other copolymerizable ethylenically unsaturated monomer (a3) include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) )
- Aromatic ring-containing monomers such as acrylate and orthophenylphenoxyethyl (meth) acrylate; cyclohexyl (meth) acrylate, cyclohexyloxyalkyl (meth) acrylate, tert-butylcyclohexyloxyethyl (meth) acrylate, isobornyl (meth) acrylate , Alicyclic monomers such as dicyclopentanyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxy Chill (meth
- an aromatic ring-containing monomer is preferable (particularly preferably benzyl (meth) acrylate, phenoxy (meth) ethyl acrylate, phenoxydiethylene glycol (meth) acrylate) in terms of easy adjustment of refractive index and birefringence.
- An alicyclic-containing monomer is preferable in that it is easy to adjust the refractive index and birefringence, and is excellent in adhesion to a low-polar adherend (for example, cycloolefin).
- the content of the aromatic ring-containing monomer or alicyclic monomer is adjusted in terms of light leakage resistance, and the birefringence of the entire member after the durability test It is preferable to adjust the birefringence of the pressure-sensitive adhesive so as to be small.
- the content of the other copolymerizable ethylenically unsaturated monomer (a3) is preferably 35% by weight or less, and more preferably 25% by weight or less.
- the acrylic resin (A) used in the present invention comprises a polar group-containing monomer (a1), preferably a (meth) acrylic acid alkyl ester monomer (a2) and other copolymerizable ethylenically unsaturated monomers ( It can be produced by appropriately selecting and polymerizing a copolymer component containing a3).
- the polymerization can be performed by a conventionally known method such as solution radical polymerization, suspension polymerization, bulk polymerization, emulsion polymerization or the like.
- a polymerization component containing a polar group-containing monomer (a1) and a polymerization initiator are mixed or dropped in an organic solvent and polymerized under predetermined polymerization conditions.
- solution radical polymerization and bulk polymerization are preferable, and solution radical polymerization is more preferable.
- organic solvent used in the polymerization reaction examples include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, esters such as ethyl acetate and butyl acetate, n-propyl alcohol, and isopropyl alcohol.
- aromatic hydrocarbons such as toluene and xylene
- aliphatic hydrocarbons such as hexane
- esters such as ethyl acetate and butyl acetate
- n-propyl alcohol and isopropyl alcohol.
- Aliphatic alcohols such as acetone, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
- organic solvents ethyl acetate, acetone, methyl ethyl ketone, butyl acetate, toluene, and methyl isobutyl ketone are used for ease of polymerization reaction, chain transfer effect, ease of drying during adhesive coating, and safety. More preferred are ethyl acetate, acetone and methyl ethyl ketone. These organic solvents may be used alone or in combination of two or more.
- Examples of the polymerization initiator used in such radical polymerization include 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, which are usual radical polymerization initiators, Azo initiators such as 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (methylpropionic acid), benzoyl peroxide, lauryl peroxide, di-tert-butyl peroxide, cumene Examples thereof include organic peroxides such as hydroperoxide, which can be appropriately selected according to the monomer used. These polymerization initiators may be used alone or in combination of two or more.
- the acrylic resin (A) used in the present invention contains 5 to 50% by weight of structural units derived from the polar group-containing monomer (a1), preferably 6 to 30% by weight, particularly 7 to 25% by weight. %, Particularly 8 to 20% by weight. If the number of structural units derived from the polar group-containing monomer (a1) is too small, the heat-and-moisture whitening resistance decreases, and if it is too large, the reworkability and durability decrease.
- the weight average molecular weight of the acrylic resin (A) is preferably 600,000 to 2,500,000, particularly preferably 800,000 to 2,000,000, more preferably 1,000,000 to 1,800,000, particularly preferably 1.1 million to 1,600,000. If the weight average molecular weight is too small, the durability tends to decrease, and if the weight average molecular weight is too large, a large amount of diluent solvent is required during production, the drying property decreases, and the residual solvent increases in the pressure-sensitive adhesive layer. , Heat resistance tends to decrease.
- the degree of dispersion (weight average molecular weight / number average molecular weight) of the acrylic resin (A) is preferably 10 or less, particularly preferably 7 or less, and further preferably 5 or less. If the degree of dispersion is too high, the reworkability tends to decrease or the durability tends to decrease. Note that the lower limit of the degree of dispersion is usually 1.
- said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, a column is made into a high performance liquid chromatograph (The Japan Waters company “Waters 2695 (main body)” and “Waters 2414 (detector)”). : Shodex GPC KF-806L (exclusion limit molecular weight: 2 ⁇ 10 7 , separation range: 100 to 2 ⁇ 10 7 , theoretical plate number: 10,000 plates / piece, filler material: styrene-divinylbenzene copolymer, filler The number average molecular weight can also be measured by the same method. The degree of dispersion is determined from the weight average molecular weight and the number average molecular weight.
- the glass transition temperature (Tg) of the acrylic resin (A) is preferably ⁇ 80 to 0 ° C., particularly preferably ⁇ 60 to ⁇ 10 ° C., and further preferably ⁇ 50 to ⁇ 20 ° C. If the glass transition temperature is too high, the tack tends to decrease, and if it is too low, the heat resistance tends to decrease.
- the glass transition temperature is calculated from the following Fox equation.
- Tg Glass transition temperature (K) of acrylic resin (A)
- Tga Glass transition temperature (K) of monomer A homopolymer
- Wa Weight fraction of monomer A
- Tgb Glass transition temperature of homopolymer of monomer B
- Wb Weight fraction of monomer B
- Tgn Homogeneity of monomer N
- the glass transition temperature (Tg) of the acrylic resin (A) is the glass transition temperature and the weight fraction when the respective monomers constituting the acrylic resin (A) are homopolymers. It is a value calculated by fitting.
- the glass transition temperature when the monomer constituting the acrylic resin (A) is a homopolymer is usually measured by a differential scanning calorimeter (DSC). JIS K7121-1987 and JIS K6240 It can measure by the method based on.
- the refractive index of the acrylic resin (A) is usually 1.440 to 1.600, preferably 1.460 to 1.550, particularly preferably 1.470 to 1.500. For such a refractive index, it is preferable to reduce the difference in refractive index of the laminated members because light loss is reduced at the member interface.
- the refractive index is a value obtained by measuring a thin acrylic resin (A) at a NaD line at 23 ° C. using a refractive index measuring device (“Abbe Refractometer 1T” manufactured by Atago Co., Ltd.).
- the haze of the acrylic resin (A) single layer is preferably 1.0 or less, more preferably 0.8 or less, and particularly preferably 0.5 or less.
- the haze is preferably 1.0 or less, more preferably 0.8 or less, and particularly preferably 0.5 or less.
- the acrylic resin (A) used in the present invention is obtained.
- the silane coupling agent is an organosilicon compound containing one or more reactive functional groups and alkoxy groups in the structure.
- the present invention uses, as an essential component, a silane coupling agent (B) that contains one or more reactive functional groups and alkoxy groups in the structure, and at least one of the alkoxy groups is an alkoxy group having 2 to 8 carbon atoms. Is.
- regulated by this invention points out the alkoxy group derived from alkoxysilane, and the alkoxy group contained in the molecule
- the polyether chain end of the polyether-modified silane and the polyether structure are not included as an alkoxy group.
- Examples of the reactive functional group include an epoxy group, a (meth) acryloyl group, a mercapto group, a hydroxyl group, a carboxyl group, an amino group, an amide group, and an isocyanate group.
- durability and reworkability are exemplified. From the viewpoint, an epoxy group and a mercapto group are preferable, and an epoxy group is particularly preferable from the viewpoint of durability and storage stability.
- At least one of the contained alkoxy groups may be an alkoxy group having 2 to 8 carbon atoms, but from the viewpoint of durability and storage stability, an alkoxy group having 2 to 8 carbon atoms is preferable. An ethoxy group is preferred.
- the silane coupling agent (B) preferably contains both an ethoxy group and a methoxy group as an alkoxy group in the structure from the viewpoint of durability and storage stability.
- the silane coupling agent (B) may have an organic substituent other than the reactive functional group and the alkoxy group, such as an alkyl group and a phenyl group.
- the structure preferably contains 5% by weight or more of an alkoxy group, particularly preferably 5 to 80% by weight, It is preferably 15 to 70% by weight, particularly preferably 30 to 60% by weight.
- an alkoxy group particularly preferably 5 to 80% by weight
- the storage stability and durability under heat and humidity resistance tend to decrease
- the content is too large, the reworkability tends to decrease.
- the silane coupling agent (B) preferably has a reactive functional group equivalent of 50 to 1000 g / mol, more preferably 100 to 900 g / mol, and particularly preferably 300 to 850 g / mol. If the reactive functional group equivalent is too small, the reworkability tends to decrease, and if it is too large, the durability under wet heat resistance tends to decrease.
- the weight average molecular weight of the silane coupling agent (B) is preferably 500 to 20,000, more preferably 1,000 to 15,000, since it does not volatilize during drying and the reworkability tends to improve. More preferably, it is 2,000 to 14,000.
- said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, and can be measured by the following method.
- the number average molecular weight can also be measured by the same method, and the degree of dispersion (weight average molecular weight / number average molecular weight) can be determined from the weight average molecular weight and the number average molecular weight.
- Gel permeation chromatograph detector differential refractive index detector RI (RI-8020, manufactured by Tosoh Corporation, sensitivity 32)
- Flow rate 1.0 mL / min
- silane coupling agent (B) even if it is a monomer-type organosilicon compound, an oligomer-type organosilicon compound such as a dimer or trimer obtained by hydrolysis and polycondensation of a part of the organosilicon compound although it may be an (organosiloxane compound), from the viewpoint of reworkability and long-term storage stability, it is preferable to use a dimer or higher oligomer type organosilicon compound.
- silane coupling agent (B) for example, organosilicon compounds such as ⁇ -glycidoxypropyltriethoxysilane and ⁇ -glycidoxypropylmethyldiethoxysilane, and some of the organosilicon compounds are hydrolyzed.
- Epoxy group-containing silane coupling agents such as polycondensed oligomeric organosilicon compounds (such as epoxy group-containing silicone alkoxy oligomers) or organosilicon compounds obtained by ether-modifying a part of these organosilicon compounds; ⁇ -mercaptopropyltriethoxysilane And a mercapto group-containing silane coupling agent of an oligomer type organosilicon compound (such as a mercapto group-containing silicone alkoxy oligomer) in which a part of the organosilicon compound is hydrolyzed and polycondensed.
- polycondensed oligomeric organosilicon compounds such as epoxy group-containing silicone alkoxy oligomers
- organosilicon compounds obtained by ether-modifying a part of these organosilicon compounds
- ⁇ -mercaptopropyltriethoxysilane And a mercapto group-containing silane coupling agent of an oligomer type organosilicon compound (such as a
- silane coupling agent (B) used in the present invention specifically, “X-41-1059A” (containing reactive functional group; epoxy group, containing alkoxy), which is a commercial product manufactured by Shin-Etsu Chemical Co., Ltd. Group: methoxy group and ethoxy group), “X-41-1805” (containing reactive functional group: mercapto group, containing alkoxy group: methoxy group and ethoxy group), “X-41-1818” (containing reactive functional group) : Mercapto group, contained alkoxy group: ethoxy group) or the like may be used.
- “X-41-1059A” is particularly preferable in terms of excellent reworkability and storage stability.
- the content of the silane coupling agent (B) is preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.5 part by weight with respect to 100 parts by weight of the acrylic resin (A). Part, particularly preferably 0.025 to 0.15 part by weight. If the content of the silane coupling agent (B) is too large, bleeding tends to decrease the durability under heat-resistant conditions, and if it is too small, the heat-and-moisture resistance decreases or the storage stability decreases. Tend to.
- the silane coupling agent (B) may be used alone or in combination of two or more.
- a silane coupling agent other than the silane coupling agent (B) can be used as long as the effect of the present invention is not impaired.
- the content of the silane coupling agent is specifically preferably 0.5 parts by weight or less with respect to 100 parts by weight of the acrylic resin (A). More preferably, it is 0.3 parts by weight or less, particularly preferably 0.2 parts by weight or less.
- the acrylic pressure-sensitive adhesive composition of the present invention preferably contains a crosslinking agent (C) and an antistatic agent (D) in addition to the acrylic resin (A) and the silane coupling agent (B).
- crosslinking agent (C) examples include isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, melamine crosslinking agents, aldehyde crosslinking agents, amine crosslinking agents, and metal chelate crosslinking agents. Among these, it is preferable to use an isocyanate-based cross-linking agent in terms of improving the adhesion to the substrate and excellent reactivity with the acrylic resin (A).
- isocyanate crosslinking agent examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, hexamethylene.
- epoxy-based crosslinking agent examples include bisphenol A / epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, and 1,6-hexanediol diglycidyl ether. , Trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl erythritol, diglycerol polyglycidyl ether and the like.
- aziridine-based crosslinking agent examples include tetramethylolmethane-tri- ⁇ -aziridinylpropionate, trimethylolpropane-tri- ⁇ -aziridinylpropionate, N, N′-diphenylmethane-4,4.
- melamine crosslinking agent examples include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine, hexapentyloxymethyl melamine, hexahexyloxymethyl melamine, and melamine resin.
- aldehyde-based crosslinking agent examples include glyoxal, malondialdehyde, succindialdehyde, maleindialdehyde, glutardialdehyde, formaldehyde, acetaldehyde, benzaldehyde and the like.
- amine-based crosslinking agent examples include hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetraamine, diethylenetriamine, triethyltetraamine, isophoronediamine, amino resin, and polyamide.
- metal chelate-based crosslinking agent examples include acetylacetone and acetoacetyl ester coordination compounds of polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, panadium, chromium, and zirconium. Can be mentioned.
- the said crosslinking agent (C) may be used independently and may use 2 or more types together.
- an isocyanate cross-linking agent is preferably used from the viewpoint of improving the adhesion to the substrate and the reactivity with the acrylic resin (A).
- isocyanate-based crosslinking agents tolylene diisocyanate is preferable in terms of pot life and durability, xylylene diisocyanate or isocyanate containing a nurate skeleton is preferable in terms of shortening the aging time, and non-aromatic isocyanate is preferable in terms of yellowing resistance. preferable.
- tolylene diisocyanate, xylylene diisocyanate, adducts and isocyanurates of hexamethylene diisocyanate and trimethylolpropane are preferable because of excellent balance of durability, pot life, and crosslinking rate.
- the content of the crosslinking agent (C) is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 1 part by weight, particularly preferably 100 parts by weight of the acrylic resin (A). Is 0.1 to 0.5 parts by weight. If the content of the cross-linking agent (C) is too small, the durability tends to decrease. If the content is too large, the stress relaxation property decreases and the substrate tends to warp, or long-term aging is required. Tend to.
- the acrylic pressure-sensitive adhesive composition of the present invention preferably further contains an antistatic agent (D), and the ionic compound (D1) is particularly suitable as the antistatic agent (D).
- the ionic compound (D1) preferably contains an ionic compound composed of at least one of a metal salt and an organic salt in terms of countermeasures against static electricity.
- metal salt examples include alkali metal salts such as lithium salts, sodium salts, calcium salts, and potassium salts, and phosphonium salts.
- organic salt examples include onium salts such as ammonium salt, imidazolium salt, pyridinium salt, piperidinium salt, pyrrolidinium salt, and sulfonium salt.
- an organic salt is preferable from the viewpoint of compatibility with the resin and corrosion resistance, and more preferably ammonium salt, imidazolium salt, pyridinium salt, piperidinium salt, pyrrolidinium.
- An onium salt composed of a nitrogen-containing cation such as a salt, particularly preferably an alkylammonium salt, more preferably an ammonium salt composed of an acyclic tetraalkylammonium cation and an N, N-bis (trifluoromethanesulfonyl) imide anion.
- the melting point of the ionic compound (D1) is preferably 10 to 100 ° C., particularly preferably 20 to 80 ° C., and further preferably 25 to 50 ° C. If the melting point is too high, it tends to precipitate at a low temperature, and if it is too low, color loss of the polarizing plate tends to occur in a moist heat environment.
- the content of the antistatic agent (D) is preferably 0.5 to 10 parts by weight, more preferably 2 to 8 parts by weight, still more preferably 2 to 5 parts by weight with respect to 100 parts by weight of the acrylic resin (A). Particularly preferred is 2.5 to 4.5 parts by weight. If the content of the antistatic agent (D) is too small, the antistatic performance cannot be obtained and display unevenness due to static electricity tends to occur. If the content is too large, the degree of polarization of the polarizing plate decreases, or heat and heat whitening resistance There is a tendency that the durability is lowered or the durability is lowered by bleeding out.
- the acrylic pressure-sensitive adhesive composition of the present invention includes other components such as a resin component, an acrylic monomer, a polymerization inhibitor, an antioxidant, a corrosion inhibitor, and a crosslinking accelerator, as long as the effects of the present invention are not impaired.
- Various additives such as an agent, radical generator, peroxide, radical scavenger, metal, resin particles, and the like can be blended.
- a small amount of impurities contained in the raw materials for producing the constituent components of the acrylic pressure-sensitive adhesive composition may be contained.
- the content of the other components is preferably 5 parts by weight or less, particularly 1 part by weight or less, and more preferably 0.5 parts by weight or less with respect to 100 parts by weight of the acrylic resin (A). preferable. When there is too much this content, compatibility with acrylic resin (A) will fall, and there exists a tendency for moisture-and-heat whitening resistance to fall.
- the acrylic pressure-sensitive adhesive composition of the present invention is prepared by mixing the acrylic resin (A) and the silane coupling agent (B), if necessary, the crosslinking agent (C), the antistatic agent (D) and other components. Can be obtained.
- the mixing method is not particularly limited, and various methods such as a method of mixing each component at once or a method of mixing any components and then mixing the remaining components at once or sequentially are adopted. can do.
- the acrylic pressure-sensitive adhesive composition of the present invention can be made into a pressure-sensitive adhesive by curing (crosslinking), and further, a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive is laminated on an optical member (optical laminate). Thereby, an optical member with an adhesive layer can be obtained.
- the optical member with the pressure-sensitive adhesive layer it is preferable to further provide a release sheet on the surface opposite to the optical member surface of the pressure-sensitive adhesive layer.
- [1] A method in which an acrylic pressure-sensitive adhesive composition is applied onto an optical member, dried, and then a release sheet is bonded thereto, and a treatment is performed by aging at room temperature (23 ° C.) or at least one of a heated state, [2] A method of applying an acrylic pressure-sensitive adhesive composition on a release sheet, drying, then bonding an optical member, and performing treatment by aging in at least one of room temperature or a heated state, Etc.
- the method of aging at room temperature by the method [2] is preferable in that the optical member is not damaged and the adhesiveness with the optical member is excellent.
- the optical member is particularly effective when it is a polarizing plate.
- Such an aging treatment is carried out in order to balance the physical properties of the adhesive as the reaction time of the chemical crosslinking of the adhesive.
- the aging conditions are as follows: the temperature is usually from room temperature to 70 ° C., and the time is usually from 1 to 30 days. Specifically, for example, the treatment may be performed under conditions such as 23 ° C. for 1 to 20 days, 23 ° C. for 3 to 10 days, 40 ° C. for 1 to 7 days, and the like.
- the acrylic pressure-sensitive adhesive composition When applying the acrylic pressure-sensitive adhesive composition, it is preferable to dilute the acrylic pressure-sensitive adhesive composition in a solvent, and the dilution concentration is preferably 5 to 60% by weight, particularly as a solid content concentration. Preferably, it is 10 to 30% by weight.
- the solvent is not particularly limited as long as it dissolves the acrylic pressure-sensitive adhesive composition.
- ester solvents such as methyl acetate, ethyl acetate, methyl acetoacetate, ethyl acetoacetate, acetone,
- a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone
- an aromatic solvent such as toluene and xylene
- an alcohol solvent such as methanol, ethanol and propyl alcohol
- ethyl acetate and methyl ethyl ketone are preferably used from the viewpoints of solubility, drying property, price, and the like.
- the acrylic pressure-sensitive adhesive composition can be applied by a conventional method such as roll coating, die coating, gravure coating, comma coating, or screen printing.
- the gel fraction of the pressure-sensitive adhesive layer produced by the above method is preferably 30 to 95% by weight, particularly preferably 40 to 85% by weight, more preferably 40% by weight from the viewpoint of durability performance and suppression of polarization degree reduction. Is 60 to 80% by weight. If the gel fraction is too low, the reworkability tends to be lowered, and if it is too high, the float or peel tends to occur.
- the gel fraction is a measure of the degree of crosslinking (curing degree), and is calculated, for example, by the following method. That is, the pressure-sensitive adhesive was picked up from a pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer was formed on a substrate such as an optical member, particularly a polarizing plate, and the pressure-sensitive adhesive was wrapped in a 200-mesh SUS wire mesh and adjusted to 23 ° C. The weight percentage of the insoluble adhesive component remaining in the wire mesh for 24 hours is defined as the gel fraction.
- the pressure-sensitive adhesive layer produced by the above method preferably has a good tack feeling when touched with a finger, because it has good wettability when actually applied to an adherend, and therefore tends to improve workability. .
- a low surface resistance value is preferable as a countermeasure against static electricity, particularly preferably 5 ⁇ 10 12 ⁇ / cm 2 or less, and more preferably. Is 1 ⁇ 10 11 ⁇ / cm 2 or less, particularly preferably 5 ⁇ 10 10 ⁇ / cm 2 or less. If the surface resistance value is too high, the polarizing plate and the pressure-sensitive adhesive layer tend to be charged and display unevenness tends to occur.
- the thickness of the pressure-sensitive adhesive layer after drying in the obtained optical member with the pressure-sensitive adhesive layer is preferably 5 to 200 ⁇ m, particularly preferably 10 to 100 ⁇ m, and further preferably 10 to 30 ⁇ m. If the thickness of the pressure-sensitive adhesive layer is too thin, the adhesive physical properties tend to be difficult to stabilize, and if it is too thick, the amount of moisture intrusion from the end portion tends to increase and storage stability tends to decrease.
- the optical member with the pressure-sensitive adhesive layer particularly the polarizing plate with the pressure-sensitive adhesive layer is directly or after having peeled off the release sheet, the pressure-sensitive adhesive layer surface is bonded to a glass substrate, for example, It is used for an image display device.
- the initial adhesive strength of the adhesive layer is appropriately determined according to the material of the adherend. For example, when bonding to a glass substrate, it preferably has an adhesive strength of 15 N / 25 mm or less, particularly preferably 0.1 to 12 N / 25 mm, and more preferably 0.5 to 8 N / 25 mm. .
- the initial adhesive strength is calculated as follows. About the polarizing plate with an adhesive layer, it cuts to width 25mm width, peels off a release film, presses the adhesive layer side to a non-alkali glass board (Corning company make, "Eagle XG"), A glass plate is bonded. Then, after autoclaving (50 ° C. ⁇ 0.5 MPa ⁇ 20 minutes), the sample is left at 23 ° C. ⁇ 50% RH for 24 hours, and then subjected to a peeling test at a peeling angle of 180 ° and a peeling speed of 300 mm / min.
- a non-alkali glass board Corning company make, "Eagle XG”
- the acrylic pressure-sensitive adhesive composition of the present invention is capable of obtaining a pressure-sensitive adhesive having excellent durability and moisture-and-heat whitening resistance, as well as excellent storage stability and reworkability, and is a pressure-sensitive adhesive for optical members.
- it is useful as an adhesive for polarizing plates that bonds a polarizing plate and a glass substrate.
- the protective film constituting the polarizing plate examples include triacetyl cellulose-based film, acrylic film, polyethylene-based film, polypropylene-based film, cycloolefin-based film, etc., and the present invention is a polarizing plate using any protective film.
- a polarizing plate laminated with a cycloolefin film is particularly preferable in that the effects of the present invention can be easily obtained.
- an image display device can be produced by laminating a polarizing plate and a liquid crystal cell, and the obtained image display device can be produced with high accuracy and has excellent durability.
- acrylic resins were prepared as follows. In addition, about the weight average molecular weight, dispersion degree, and glass transition temperature of acrylic resin (A), it measured in accordance with the above-mentioned method. In addition, regarding the measurement of a viscosity, it measured according to the 4.5.3 rotational viscometer method of JISK5400 (1990).
- an acrylic resin (A-1) solution solid content of 20 0.9%, a viscosity of 4,770 mPa ⁇ s / 25 ° C., an acrylic resin (A-1): a glass transition temperature of ⁇ 43 ° C., a weight average molecular weight of 1,290,000, and a dispersity of 4.3).
- the monomer used above was from the following manufacturer. ⁇ 2-Hydroxyethyl acrylate (Tg-15 °C, Osaka Organic Chemical Co., Ltd.) ⁇ Acrylic acid (Mitsubishi Chemical Tg106 °C) ⁇ Butyl acrylate (Tg-56 °C, manufactured by Mitsubishi Chemical Corporation) ⁇ Benzyl acrylate (Biscoat # 160 Tg6 ° C, Osaka Organic Chemical Co., Ltd.) The above Tg is the Tg of the homopolymer of each monomer.
- silane coupling agent (B) The following were prepared as the silane coupling agent (B). The weight average molecular weight and dispersity of the silane coupling agent (B) were measured according to the method described above. Moreover, about the containing reactive functional group, the reactive functional group equivalent, the containing alkoxy group, and the alkoxy group content, catalog values were adopted unless otherwise noted.
- B′-1 Methoxy group-containing silane coupling agent (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd., contained reactive functional group: epoxy group, reactive functional group equivalent: 236.3 g / mol (calculated value) , Contained alkoxy group: methoxy group, alkoxy group content: 39% (calculated value), molecular weight: 236.3)
- the reactive functional group equivalent of B′-1 was calculated as the molecular weight with respect to 1 mol of epoxy group.
- the alkoxy group content a value obtained by dividing the weight of the methoxy group by the molecular weight was adopted (number of methoxy groups: 3, weight of one methoxy group: 31, molecular weight: 236.6).
- B′-2 methoxy group-containing silane coupling agent (“KBM-803” manufactured by Shin-Etsu Chemical Co., Ltd., contained reactive functional group: mercapto group, reactive functional group equivalent: 196.4 g / mol (calculated value) , Contained alkoxy group: methoxy group, alkoxy group content: 47% (calculated value), molecular weight: 196.4)
- the reactive functional group equivalent of B′-2 was calculated as the molecular weight with respect to 1 mol of mercapto group.
- a value obtained by dividing the weight of the methoxy group by the molecular weight was employed (number of methoxy groups: 3, weight of one methoxy group: 31, molecular weight: 196.4).
- C Crosslinking agent
- (C-1) Adduct body of tolylene diisocyanate and trimethylolpropane (“Coronate L55E” manufactured by Tosoh Corporation: 55% active ingredient)
- TAC film 1 / PVA film (polarizer) / TAC film 2 / pressure-sensitive adhesive layer / release sheet Note that the TAC film is a triacetyl cellulose film (TAC film 1: thickness 60 ⁇ m). TAC film 2: thickness 40 ⁇ m).
- the above TAC film is a triacetyl cellulose film (thickness 50 ⁇ m)
- the COP film is a cycloolefin film (thickness 60 ⁇ m).
- the following evaluation was performed using polarizing plate [I] with an adhesive layer and polarizing plate [II] with an adhesive layer.
- the pressure-sensitive adhesive layer-attached polarizing plate [I] obtained above was cut to a width of 25 mm, the release sheet was peeled off, and the pressure-sensitive adhesive layer surface was made into alkali-free glass (Corning “Eagle XG”: thickness 1.1 mm). After pressing, bonding with a 2 kg roller, and autoclaving (0.5 MPa ⁇ 50 ° C. ⁇ 20 minutes), the sample was left standing in an environment of 23 ° C. ⁇ 50% RH for 24 hours, and then the peel angle was 180 °.
- the adhesive strength when peeled at a peeling speed of 300 mm / min was measured and evaluated according to the following criteria.
- the obtained polarizing plate with pressure-sensitive adhesive layer [I] was previously exposed to an environment of 45 ° C. ⁇ 90% RH for 3 days, and then deteriorated by adjusting the temperature and humidity for 1 week in an environment of 23 ° C. ⁇ 50% RH.
- a polarizing plate with an adhesive layer after promotion was obtained.
- the obtained polarizing plate was cut into 20 cm ⁇ 15 cm, the release sheet was peeled off, and the pressure-sensitive adhesive layer surface was pressed against alkali-free glass (Corning “Eagle XG”: thickness 1.1 mm) and reciprocated twice with a 2 kg roller.
- the obtained polarizing plate with pressure-sensitive adhesive layer [I] was previously exposed to an environment of 45 ° C. ⁇ 90% RH for 3 days, and then deteriorated by adjusting the temperature and humidity for 1 week in an environment of 23 ° C. ⁇ 50% RH.
- a polarizing plate with an adhesive layer after promotion was obtained.
- the obtained polarizing plate was cut into 20 cm ⁇ 15 cm, the release sheet was peeled off, and the pressure-sensitive adhesive layer surface was pressed against alkali-free glass (Corning “Eagle XG”: thickness 1.1 mm) and reciprocated twice with a 2 kg roller. Then, autoclaving (0.5 MPa ⁇ 50 ° C.
- Examples 1 to 5 using an adhesive containing an acrylic resin having a polar group of 5 to 50% by weight and a silane coupling agent containing an alkoxy group having 2 or more carbon atoms are moist heat and whitening resistance and storage stability. It turns out that it is excellent in.
- Comparative Examples 1 and 2 in which the acrylic resin has a small number of polar groups are inferior in moisture and heat whitening resistance, and the acrylic resin has a relatively large number of polar groups, but includes Comparative Examples 3 to 3 containing a silane coupling agent consisting only of methoxy groups.
- No. 5 is excellent in moisture and heat whitening resistance but inferior in storage stability due to ingress of moisture, and inferior in durability after a deterioration acceleration test.
- an image display device was produced by laminating a polarizing plate and a liquid crystal cell using a pressure-sensitive adhesive obtained by crosslinking the acrylic pressure-sensitive adhesive compositions of Examples 1 to 5, the obtained image display device was obtained as follows. It was able to be produced with high accuracy and had excellent durability.
- the acrylic pressure-sensitive adhesive composition of the present invention is excellent in durability and moist heat whitening resistance when used as a pressure-sensitive adhesive for laminating a polarizing plate and a glass substrate, and has storage stability (durability after aging). ), A pressure-sensitive adhesive with excellent reworkability can be obtained, and a pressure-sensitive adhesive for optical members for bonding a display and optical components constituting the display, particularly a polarizing plate and a liquid crystal cell glass substrate, etc. It is useful as a pressure-sensitive adhesive for polarizing plates for bonding together.
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Abstract
Description
これは、長時間湿熱条件下におかれると粘着剤層に徐々に水分が浸入し、常温に戻した際には該水分が粘着剤層中で結露するが、COPフィルムは透湿性が低く、粘着剤層中の水分の放出が抑制されるためである。
更に本発明は、上記第1の要旨のアクリル系粘着剤組成物が、架橋剤(C)により架橋されてなる粘着剤を第2の要旨とし、第2の要旨の粘着剤を用いてなる偏光板用粘着剤を第3の要旨とし、更に第2の要旨の粘着剤で、偏光板と液晶セルを貼り合わせてなる画像表示装置を第4の要旨とするものである。
なお、本発明において、(メタ)アクリルとはアクリルあるいはメタクリルを、(メタ)アクリロイルとはアクリロイルあるいはメタクリロイルを、(メタ)アクリレートとはアクリレートあるいはメタクリレートをそれぞれ意味するものである。また、アクリル系樹脂とは、少なくとも1種の(メタ)アクリレート系モノマーを含む重合成分を重合して得られる樹脂である。
本発明で用いられるアクリル系樹脂(A)は、極性基含有モノマー(a1)由来の構造単位を5~50重量%含有するアクリル系樹脂であり、例えば、極性基含有モノマー(a1)を5~50重量%含む共重合成分を共重合して得られるものである。アクリル系樹脂(A)の共重合成分には、必要に応じて(メタ)アクリル酸アルキルエステル系モノマー(a2)やその他の共重合可能なエチレン性不飽和モノマー(a3)を含んでもよい。
上記アミノ基含有モノマーの中でも、樹脂溶液の保存安定性及び、架橋促進効果の点で3級アミノ基含有モノマーが好ましく、ジメチルアミノエチル(メタ)アクリレートが特に好ましい。
かかる含有量が少なすぎると、粘着物性のバランスを取りにくくなる傾向があり、多すぎると湿熱白化性が低下する傾向にある。
上記その他の共重合可能なエチレン性不飽和モノマー(a3)の含有量としては35重量%以下が好ましく、更に好ましくは25重量%以下である。その他の共重合可能なエチレン性不飽和モノマー(a3)が多すぎると耐光漏れ性が低下する傾向にある。
例えば、有機溶媒中に、極性基含有モノマー(a1)を含有する重合成分、重合開始剤を混合あるいは滴下し所定の重合条件にて重合する。これら重合方法のうち、溶液ラジカル重合、塊状重合が好ましく、更に好ましくは溶液ラジカル重合である。
これらの有機溶媒の中でも、重合反応のしやすさや連鎖移動の効果や粘着剤塗工時の乾燥のしやすさ、安全上から、酢酸エチル、アセトン、メチルエチルケトン、酢酸ブチル、トルエン、メチルイソブチルケトンが好ましく、更に好ましくは、酢酸エチル、アセトン、メチルエチルケトンである。
これら有機溶媒は、単独で用いてもよいし2種以上を併用してもよい。
かかる重量平均分子量が小さすぎると耐久性が低下する傾向があり、重量平均分子量が大きすぎると製造時に希釈溶剤が大量に必要となり、乾燥性が低下し、粘着剤層中に残溶剤が多くなり、耐熱性が低下する傾向がある。
かかる分散度が高すぎるとリワーク性が低下したり耐久性が低下したりする傾向がある。なお、かかる分散度の下限は通常1である。
かかるガラス転移温度が高すぎるとタックが低下しやすくなる傾向があり、低すぎると耐熱性が低下する傾向がある。
Tg:アクリル系樹脂(A)のガラス転移温度(K)
Tga:モノマーAのホモポリマーのガラス転移温度(K) Wa:モノマーAの重量分率
Tgb:モノマーBのホモポリマーのガラス転移温度(K) Wb:モノマーBの重量分率
Tgn:モノマーNのホモポリマーのガラス転移温度(K) Wn:モノマーNの重量分率
(Wa+Wb+・・・+Wn=1)
なお、アクリル系樹脂(A)を構成するモノマーをホモポリマーとした際のガラス転移温度は、通常、示差走査熱量計(DSC)により測定されるものであり、JIS K7121-1987や、JIS K 6240に準拠した方法で測定することができる。
上記屈折率は、薄膜にしたアクリル系樹脂(A)を屈折率測定装置(アタゴ社製「アッベ屈折計1T」)を用いてNaD線、23℃で測定した値である。
ヘイズは、拡散透過率及び全光線透過率を、HAZE MATER NDH2000(日本電色工業社製)を用いて測定し、得られた拡散透過率と全光線透過率の値を下記式に代入して、算出したものである。なお、本機はJIS K7361-1に準拠している。
ヘイズ(%)=(拡散透過率/全光線透過率)×100
通常、シランカップリング剤とは、構造中に反応性官能基とアルコキシ基をそれぞれ1つ以上含有する有機ケイ素化合物である。
本発明は、構造中に反応性官能基とアルコキシ基をそれぞれ1つ以上含有し、アルコキシ基の少なくとも1つが炭素数2~8のアルコキシ基であるシランカップリング剤(B)を必須成分として用いるものである。
例えば、ポリエーテル変性シランのポリエーテル鎖末端やポリエーテル構造はアルコキシ基として含まれない。
装置:ゲル浸透クロマトグラフ
検出器:示差屈折率検出器RI(東ソー社製 RI-8020型、感度32)
カラム:TSKgel guardcolumn HHR-H(1本)(東ソー社製 φ6mm×4cm)、TSKgel GMHHR-N(2本)(東ソー社製 φ7.8mm×30cm)
溶媒:テトラヒドロフラン(THF)
カラム温度:23℃
流速:1.0mL/分
本発明に用いられる架橋剤(C)は、例えば、イソシアネート系架橋剤、エポキシ系架橋剤、アジリジン系架橋剤、メラミン系架橋剤、アルデヒド系架橋剤、アミン系架橋剤、金属キレート系架橋剤が挙げられるが、これらの中でも基材との接着性を向上させる点やアクリル系樹脂(A)との反応性に優れる点で、イソシアネート系架橋剤を用いることが好ましい。
上記架橋剤(C)の中でも基材との密着性を向上させる点やアクリル系樹脂(A)との反応性の点で、イソシアネート系架橋剤が好適に用いられる。
イソシアネート系架橋剤のなかでも、トリレンジイソシアネートがポットライフと耐久性の点で好ましく、キシリレンジイソシアネートまたはヌレート骨格含有イソシアネートがエージング時間短縮の点で好ましく、非芳香族イソシアネートが耐黄変性の点で好ましい。これらの中でも具体的には、トリレンジイソシアネート、キシリレンジイソシアネート、ヘキサメチレンジイソシアネートとトリメチロールプロパンのアダクト体、イソシアヌレート体が耐久性やポットライフ、架橋速度のバランスに優れている点で好ましい。
かかる架橋剤(C)の含有量が少なすぎると、耐久性が低下しやすい傾向があり、多すぎると応力緩和性が低下して基板が反りやすくなったり、長時間のエージングが必要となったりする傾向がある。
本発明のアクリル系粘着剤組成物には、更に帯電防止剤(D)を含有することが好ましく、帯電防止剤(D)としては特にイオン性化合物(D1)が好適である。
かかるイオン性化合物(D1)としては、金属塩及び有機塩の少なくとも一方からなるイオン性化合物を含有することが静電対策の点で好ましい。
上記粘着剤層付き光学部材には、粘着剤層の光学部材面とは逆の面に、更に離型シートを設けることが好ましい。
〔1〕光学部材上に、アクリル系粘着剤組成物を塗布、乾燥した後、離型シートを貼合し、室温(23℃)または加温状態の少なくとも一方でのエージングによる処理を行なう方法、
〔2〕離型シート上に、アクリル系粘着剤組成物を塗布、乾燥した後、光学部材を貼合し、室温または加温状態の少なくとも一方でのエージングによる処理を行なう方法、
等が挙げられる。これらの中でも、〔2〕の方法で、室温状態でエージングする方法が、光学部材を痛めない点、光学部材との密着性に優れる点で好ましい。
なお、上記において、光学部材としては、偏光板である場合に特に有効である。
また、上記溶剤としては、アクリル系粘着剤組成物を溶解させるものであれば特に限定されることなく、例えば、酢酸メチル、酢酸エチル、アセト酢酸メチル、アセト酢酸エチル等のエステル系溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤、トルエン、キシレン等の芳香族系溶剤、メタノール、エタノール、プロピルアルコール等のアルコール系溶剤を用いることができる。これらの中でも、溶解性、乾燥性、価格等の点から酢酸エチル、メチルエチルケトンが好適に用いられる。
粘着剤層付き偏光板について、幅25mm幅に裁断し、離型フィルムを剥離して、粘着剤層側を無アルカリガラス板(コーニング社製、「イーグルXG」)に押圧して、偏光板とガラス板とを貼合する。その後、オートクレーブ処理(50℃×0.5MPa×20分間)を行った後、23℃×50%RHで24時間放置後に、引き剥がし角度180°、剥離速度300mm/分で剥離試験を行なう。
なお、粘度の測定に関しては、JIS K5400(1990)の4.5.3回転粘度計法に準じて測定した。
〔アクリル系樹脂(A-1)の製造〕
還流冷却器、撹拌器、窒素ガスの吹き込み口及び温度計を備えた4ツ口丸底フラスコに、2-ヒドロキシエチルアクリレート(a1)6部、アクリル酸(a1)0.7部、n-ブチルアクリレート(a2)73.3部、ベンジルアクリレート(a3)20部、酢酸エチル54.9部、アセトン42部、重合開始剤としてアゾビスイソブチロニトリル(AIBN)0.013部を仕込み、反応を開始し、AIBNを0.04%含有する酢酸エチル溶液を30部滴下しながら還流温度で3.25時間反応後、酢酸エチルにて希釈してアクリル系樹脂(A-1)溶液(固形分20.9%、粘度4,770mPa・s/25℃、アクリル系樹脂(A-1):ガラス転移温度-43℃、重量平均分子量129万、分散度4.3)を得た。
・2-ヒドロキシエチルアクリレート(大阪有機化学社製 Tg―15℃)
・アクリル酸(三菱化学社製 Tg106℃)
・ブチルアクリレート(三菱化学社製 Tg-56℃)
・ベンジルアクリレート(大阪有機化学社製 ビスコート#160 Tg6℃)
また、上記Tgは各モノマーのホモポリマーのTgである。
下記表1に記載の共重合成分を用いて、上記アクリル系樹脂(A-1)の製造方法に準じて行い、アクリル系樹脂(A-2)~(A-4)及び(A’-1)、(A’-2)溶液を得た。また、得られたアクリル系樹脂(A-2)~(A-4)及び(A’-1)、(A’-2)溶液は下記表1に記載の通りのものである。
シランカップリング剤(B)として、以下のものを用意した。なお、シランカップリング剤(B)の重量平均分子量、分散度に関しては、前述の方法にしたがって測定した。また、含有反応性官能基、反応性官能基当量、含有アルコキシ基、アルコキシ基含有量については、断りのない限りカタログ値を採用した。
(信越化学工業社製「X41-1059A」、含有反応性官能基:エポキシ基、反応性官能基当量:350g/mol、含有アルコキシ基:メトキシ基及びエトキシ基、アルコキシ基含有量:42%、重量平均分子量:2,270、分散度:1.86)
(信越化学工業社製「X41-1805」、含有反応性官能基:メルカプト基、反応性官能基当量:800g/mol、含有アルコキシ基:メトキシ基及びエトキシ基、アルコキシ基含有量:50%、重量平均分子量:3,450、分散度:1.85)
(信越化学工業社製「KBM-403」、含有反応性官能基:エポキシ基、反応性官能基当量:236.3g/mol(計算値)、含有アルコキシ基:メトキシ基、アルコキシ基含有量:39%(計算値)、分子量:236.3)
なお、上記B’-1の反応性官能基当量はエポキシ基1molに対する分子量として計算した。また、アルコキシ基含有量に関しては、メトキシ基の重量を分子量で除した値を採用した(メトキシ基数:3、メトキシ基一つの重量:31、分子量:236.6)。
(信越化学工業社製「KBM-803」、含有反応性官能基:メルカプト基、反応性官能基当量:196.4g/mol(計算値)、含有アルコキシ基:メトキシ基、アルコキシ基含有量:47%(計算値)、分子量:196.4)
なお、上記B’-2の反応性官能基当量は、メルカプト基1molに対する分子量として計算した。また、アルコキシ基含有量に関しては、メトキシ基の重量を分子量で除した値を採用した(メトキシ基数:3、メトキシ基一つの重量:31、分子量:196.4)。
(信越化学工業社製「X-24-9590」、含有反応性官能基:エポキシ基、官能基当量:592g/mol、含有アルコキシ基:メトキシ基、アルコキシ基含有量:9.5%、重量平均分子量:13,700、分散度:3.44)
架橋剤(C)として以下のものを用意した。
(C-1):トリレンジイソシアネートとトリメチロールプロパンのアダクト体(東ソー社製「コロネートL55E」:有効成分55%)
帯電防止剤(D)として以下のものを用意した。
(D1-1):トリ-n―ブチルメチルアンモニウムN,N-ビス(トリフルオロメタンスルホニル)イミド(スリーエム社製、「FC-4400」)
上記の成分(A)~(D)を下記表2の通りに配合し、酢酸エチルにて固形分濃度を12.5%に調整し、アクリル系粘着剤組成物を得た。
上記で得られたアクリル系粘着剤組成物を乾燥後の厚みが25μmになるように厚み38μmの離型シート(三井化学東セロ社製「ルミラーSP-0138BU」)に塗布し、100℃で3分間乾燥した後、離型シートと反対側の粘着剤層面に以下の2種類の構成からなる偏光板を貼り合わせ、その後23℃×50%RHの環境下で7日間エージングし、粘着剤層付き偏光板を得た。
なお、上記TACフィルムはトリアセチルセルロースフィルム(TACフィルム1:厚み60μm、TACフィルム2:厚み40μm)である。
・粘着剤層付き偏光板[II]:TACフィルム/PVAフィルム(偏光子)/COPフィルム(コロナ処理)/粘着剤層/離型シート
なお、上記のTACフィルムはトリアセチルセルロースフィルム(厚み50μm)、COPフィルムはシクロオレフィンフィルム(厚み60μm)である。
粘着剤層付き偏光板[I]及び粘着剤層付き偏光板[II]を用いて以下の評価を行った。
上記で得られた粘着剤層付き偏光板[I]を25mm幅にカットし、離型シートを剥離して粘着剤層面を無アルカリガラス(コーニング社製「イーグルXG」:厚み1.1mm)に押しつけ、2kgローラーにて貼り合わせ、オートクレーブ処理(0.5MPa×50℃×20分間)を行った後、23℃×50%RHの環境下で24時間静置し、その後、引き剥がし角度180°、300mm/分の剥離速度で引き剥がした時の粘着力を測定し、下記基準にて評価した。
(評価基準)
◎・・・10N/25mm未満
○・・・10N/25mm以上、16N/25mm未満
△・・・16N/25mm以上、20N/25mm未満
×・・・20N/25mm以上、もしくは糊残りが発生
上記粘着剤層付き偏光板[II]を、3.5cm×3.5cmにカットし、離型シートを剥離して粘着剤層側を無アルカリガラス(コーニング社製「イーグルXG」:厚み1.1mm)に押しつけ、2kgローラーにて2往復して貼り合わせた後、オートクレーブ処理(0.5MPa×50℃×20分間)を行い、耐湿熱白化試験用のサンプルを作製した。
得られた試験用サンプルを用いて、下記の通り粘着剤層の耐湿熱白化性を評価した。
上記耐湿熱白化性試験用サンプルを60℃×90%RHの環境下に250時間暴露した後、取出し室温(23℃)に放置した。取り出し直後、及び取り出してから3時間後のヘイズを測定し、耐湿熱白化性を下記の基準で評価した。なお、ヘイズ値は1.1mm無アルカリガラスの値をブランクとして差し引いた値である。
(評価基準)
・取り出し直後のヘイズ
◎・・・1%未満
○・・・1%以上、2%未満
△・・・2%以上、4%未満
×・・・4%以上
・取り出し3時間後のヘイズ
◎・・・1%未満
○・・・1%以上、2%未満
△・・・2%以上、4%未満
×・・・4%以上
<耐湿熱評価>
得られた粘着剤層付き偏光板[I]を20cm×15cmにカットし、離型シートを剥離して粘着剤層面を無アルカリガラス(コーニング社製「イーグルXG」:厚み1.1mm)に押しつけ2kgローラーにて2往復して貼り合わせた後、オートクレーブ処理(0.5MPa×50℃×20分間)を行い、初期耐久性試験用のサンプルを作製した。
得られたサンプルを60℃×90%RHの環境下に250時間暴露して耐久性試験を行い、取り出した後、下記の通り耐久性を評価した。
(評価基準)
○・・・偏光板の全面に発泡もしくは端部の浮きがみられなかった
×・・・偏光板の前面に発泡もしくは端部の浮きがみられた
得られた粘着剤層付き偏光板[I]及び[II]を20cm×15cmにカットし、離型シートを剥離して粘着剤層面を無アルカリガラス(コーニング社製「イーグルXG」:厚み1.1mm)に押しつけ2kgローラーにて2往復して貼り合わせたのち、オートクレーブ処理(0.5MPa×50℃×20分間)を行い、初期耐久性試験用のサンプルを作製した。
得られたサンプルを80℃の環境下に250時間暴露して耐久試験を行い、取り出した後、下記の通り耐久性を評価した。
(評価基準)
○・・・偏光板の全面に発泡もしくは端部の浮きがみられなかった
×・・・偏光板の前面に発泡もしくは端部の浮きがみられた
<耐湿熱性>
得られた粘着剤層付き偏光板[I]をあらかじめ45℃×90%RHの環境下に3日間暴露した後、23℃×50%RHの環境下で1週間調温・調湿して劣化促進後の粘着剤層付偏光板を得た。
得られた偏光板を20cm×15cmにカットし、離型シートを剥離して粘着剤層面を無アルカリガラス(コーニング社製「イーグルXG」:厚み1.1mm)に押しつけ2kgローラーにて2往復して貼り合わせた後、オートクレーブ処理(0.5MPa×50℃×20分間)を行い、劣化促進試験後耐久性用のサンプルを作製した。
得られたサンプルを60℃×90%RHの環境下に250時間暴露して耐久性試験を行い、取り出した後、下記の通り耐久性を評価した。
(評価基準)
○・・・偏光板の全面に発泡もしくは端部の浮きがみられなかった
×・・・偏光板の前面に発泡もしくは端部の浮きがみられた
得られた粘着剤層付き偏光板[I]をあらかじめ45℃×90%RHの環境下に3日間暴露した後、23℃×50%RHの環境下で1週間調温・調湿して劣化促進後の粘着剤層付き偏光板を得た。
得られた偏光板を20cm×15cmにカットし、離型シートを剥離して粘着剤層面を無アルカリガラス(コーニング社製「イーグルXG」:厚み1.1mm)に押しつけ2kgローラーにて2往復して貼り合わせた後、オートクレーブ処理(0.5MPa×50℃×20分間)を行い、劣化促進試験後耐久性用のサンプルを作製した。
得られたサンプルを80℃の環境下に250時間暴露して耐久性試験を行い、取り出した後、下記の通り耐久性を評価した。
(評価基準)
○・・・偏光板の全面に発泡もしくは端部の浮きがみられなかった
×・・・偏光板の前面に発泡もしくは端部の浮きがみられた
得られた粘着剤層付き偏光板[I]の離型シートを剥離し、粘着剤層面から粘着剤をピッキングしSUS製の200メッシュ金網で包んだ後、23℃に調整した酢酸エチルに24時間浸漬し、金網中に残存した不溶解の粘着剤成分の重量百分率をゲル分率(%)とした。
<表面抵抗値>
上記粘着剤層付き偏光板[I]を23℃×50%RHの雰囲気下で24時間静置した後、粘着剤層の離型シートを外し表面抵抗率測定装置(三菱化学アナリテック社製、装置名「Hiresta-UP MCP-HT450」)を用い粘着剤層の表面抵抗値を測定した。
Claims (11)
- アクリル系樹脂(A)、及び、構造中に反応性官能基とアルコキシ基をそれぞれ1つ以上含有するシランカップリング剤(B)を含有するアクリル系粘着剤組成物であって、
上記アクリル系樹脂(A)が、水酸基含有モノマー、カルボキシル基含有モノマー、窒素含有モノマーから選ばれる少なくとも1つの極性基含有モノマー(a1)由来の構造単位を5~50重量%含有するアクリル系樹脂であり、上記シランカップリング剤(B)の含有するアルコキシ基の少なくとも1つが炭素数2~8のアルコキシ基であることを特徴とするアクリル系粘着剤組成物。 - 上記極性基含有モノマー(a1)が水酸基含有モノマーであることを特徴とする請求項1記載のアクリル系粘着剤組成物。
- 上記シランカップリング剤(B)の含有する炭素数2~8のアルコキシ基がエトキシ基であることを特徴とする請求項1または2記載のアクリル系粘着剤組成物。
- 上記シランカップリング剤(B)の含有するアルコキシ基が、エトキシ基とメトキシ基であることを特徴とする請求項1~3のいずれか一項に記載のアクリル系粘着剤組成物。
- 上記シランカップリング剤(B)が、その構造中にアルコキシ基を5重量%以上含有すること特徴とする請求項1~4のいずれか一項に記載のアクリル系粘着剤組成物。
- 上記シランカップリング剤(B)の反応性官能基当量が50~1000g/molであることを特徴とする請求項1~5のいずれか一項に記載のアクリル系粘着剤組成物。
- 更に架橋剤(C)を含有することを特徴とする請求項1~6のいずれか一項に記載のアクリル系粘着剤組成物。
- 更に帯電防止剤(D)を含有することを特徴とする請求項1~7のいずれか一項に記載のアクリル系粘着剤組成物。
- 請求項1~8のいずれか一項に記載のアクリル系粘着剤組成物が、架橋剤(C)により架橋されてなることを特徴とする粘着剤。
- 請求項9記載の粘着剤を用いてなることを特徴とする偏光板用粘着剤。
- 請求項9記載の粘着剤で、偏光板と液晶セルを貼り合わせてなることを特徴とする画像表示装置。
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Cited By (5)
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JP2018100399A (ja) * | 2016-12-16 | 2018-06-28 | 日本合成化学工業株式会社 | 粘着剤組成物、およびそれを用いてなる偏光板用粘着剤、粘着剤層付偏光板、ならびに画像表示装置 |
US20190194511A1 (en) * | 2017-12-27 | 2019-06-27 | Samsung Display Co. Ltd. | Double-sided tape and display device including the same |
KR20200067669A (ko) * | 2018-12-04 | 2020-06-12 | 삼성에스디아이 주식회사 | 편광판용 점착 필름, 이를 포함하는 편광판 및 이를 포함하는 광학표시장치 |
JP2021033164A (ja) * | 2019-08-28 | 2021-03-01 | 日東電工株式会社 | 粘着剤層付偏光フィルム積層体、及び、該粘着剤層付偏光フィルム積層体が使用される光学表示パネル |
JP2021127463A (ja) * | 2017-04-28 | 2021-09-02 | 藤森工業株式会社 | 粘着剤組成物、及び粘着フィルム |
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JP2021033164A (ja) * | 2019-08-28 | 2021-03-01 | 日東電工株式会社 | 粘着剤層付偏光フィルム積層体、及び、該粘着剤層付偏光フィルム積層体が使用される光学表示パネル |
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JP7309522B2 (ja) | 2019-08-28 | 2023-07-18 | 日東電工株式会社 | 粘着剤層付偏光フィルム積層体、及び、該粘着剤層付偏光フィルム積層体が使用される光学表示パネル |
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TW201817838A (zh) | 2018-05-16 |
CN109476970B (zh) | 2021-09-14 |
JP6950530B2 (ja) | 2021-10-13 |
JPWO2018034230A1 (ja) | 2019-06-20 |
KR20190040183A (ko) | 2019-04-17 |
CN109476970A (zh) | 2019-03-15 |
KR102358557B1 (ko) | 2022-02-04 |
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