WO2018034232A1 - 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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- WO2018034232A1 WO2018034232A1 PCT/JP2017/029083 JP2017029083W WO2018034232A1 WO 2018034232 A1 WO2018034232 A1 WO 2018034232A1 JP 2017029083 W JP2017029083 W JP 2017029083W WO 2018034232 A1 WO2018034232 A1 WO 2018034232A1
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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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- 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
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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
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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 acrylic pressure-sensitive adhesive composition exhibits excellent reworkability over a long period of time and is resistant to the influence of moisture.
- the present invention relates to an acrylic pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive that does not cause deterioration in properties.
- 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.
- 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.
- TAC film highly permeable triacetyl cellulose film
- an olefin film, particularly a cycloolefin film (COP film) has been used as a protective film for a polarizer instead of a TAC film.
- the pressure-sensitive adhesive used for bonding such a polarizing plate and a liquid crystal cell (glass substrate) is required to have durability such as heat resistance and moisture heat resistance.
- moisture enters the pressure-sensitive adhesive layer, resulting in a decrease in adhesion to the glass substrate, and the polarizing plate may partially float or peel off from the glass substrate. It was.
- improvement in moisture and heat resistance has been achieved by blending a silane coupling agent with the pressure-sensitive adhesive.
- a silane coupling agent is blended, the silane coupling agent is Due to the gradual reaction, there was a problem that the adhesive strength increased and the long-term reworkability decreased.
- the pressure-sensitive adhesive layer is whitened due to the condensation phenomenon when it is exposed to a humid heat environment (wet heat whitening phenomenon).
- the pressure-sensitive adhesives used in conventional polarizing plates are used differently depending on the type of polarizing plate.
- pressure-sensitive adhesives that can be used even when the type of polarizing plate is different are required in terms of cost and workability. It was.
- Patent Document 1 discloses that 100 parts by weight of the adhesive resin (A), an epoxy equivalent of 100 to 2000 g / mol, and an alkoxyl group are contained.
- An adhesive composition that is one or more selected from the group consisting of an adhesive resin (A1), a urethane-based adhesive resin (A2), and a polyester-based adhesive resin (A3) is described.
- Patent Document 2 describes a pressure-sensitive adhesive using an acrylic resin into which a large amount of polar group-containing monomers are introduced in consideration of heat and heat whitening resistance.
- the functional group equivalent and the alkoxy group content are both widely defined for the silane coupling agent (silicone alkoxy oligomer) to be used, and various types of silane coupling agents.
- silane coupling agent silicon alkoxy oligomer
- various types of silane coupling agents there is room for improvement in the moisture and heat whitening resistance when a protective film having a low moisture permeability such as a cycloolefin film is used.
- Patent Document 2 in consideration of moisture and heat whitening resistance has a description that it can be used for various optical members, a large amount of polar group-containing monomer is introduced into the acrylic resin, so that it is hydrophilic.
- a TAC or acrylic film having a high moisture permeability is used as the protective film, hydrolysis of the silane coupling agent is promoted and long-term reworkability is lowered.
- the present invention provides an acrylic pressure-sensitive adhesive composition that can provide a pressure-sensitive adhesive that exhibits reworkability and does not cause whitening even when exposed to a high-temperature and high-humidity environment.
- an adhesive composition containing an acrylic resin and a silane coupling agent an acrylic containing a relatively large number of structural units derived from polar group-containing monomers.
- Adhesive that exhibits excellent reworkability over a long period of time and does not cause whitening under high-temperature and high-humidity conditions by using a combination of an epoxy resin and an oligomer-type silane coupling agent with a low alkoxy group content It was found that an agent can be obtained.
- the present invention is an acrylic pressure-sensitive adhesive composition containing an acrylic resin (A) and a silane coupling agent (B) containing one or more reactive functional groups and alkoxy groups 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
- the first gist of the present invention is an acrylic pressure-sensitive adhesive composition containing an oligomer type silane coupling agent (B1) having an alkoxy group content of 15% by weight or less.
- the present invention provides a pressure-sensitive adhesive obtained by crosslinking the acrylic pressure-sensitive adhesive composition according to the first aspect with a crosslinking agent (C), and a polarizing plate using the pressure-sensitive adhesive according to the second aspect.
- An image display device comprising a polarizing plate and a liquid crystal cell bonded together with the adhesive for the third aspect and the adhesive of the second aspect is a fourth aspect.
- 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
- the silane coupling agent (B) is an acrylic pressure-sensitive adhesive composition containing an oligomer type silane coupling agent (B1) having an alkoxy group content of 15% by weight or less.
- the pressure-sensitive adhesive obtained using the acrylic pressure-sensitive adhesive composition of the present invention is used as a pressure-sensitive adhesive used for laminating a polarizing plate (protective film) and a liquid crystal cell (glass) when manufacturing an image display device.
- the pressure-sensitive adhesive exhibits excellent reworkability over a long period of time, and is excellent in moisture and heat whitening resistance and durability, and is very useful as a pressure-sensitive adhesive for polarizing plates.
- the reactive functional group equivalent of the oligomer type silane coupling agent (B1) is 1,600 g / mol or less, the durability is further improved.
- the weight average molecular weight of the oligomer type silane coupling agent (B1) is 3,000 or more, reworkability and durability are more excellent.
- the moisture and heat whitening resistance is 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 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.
- An acrylic resin obtained by copolymerization is preferred.
- 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.
- 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 will be described.
- 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 And the like.
- a primary hydroxyl group-containing monomer is preferable in terms of excellent reactivity with a crosslinking agent and improvement in resistance to moist heat whitening, and 2-hydroxyethyl (meth) acrylate in terms of stability during polymerization. It is preferable to use 4-hydroxybutyl (meth) acrylate because it has high reactivity with the crosslinking agent and shortens aging. Furthermore, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable because they have few impurities such as di (meth) acrylate and are easy to produce.
- hydroxyl group-containing monomer it is also preferable to use a monomer having a content of di (meth) acrylate as an impurity of 0.5% by weight or less, particularly preferably 0.2% by weight or less, and more preferably 0%. .1% by weight or less.
- a monomer having a content of di (meth) acrylate as an impurity of 0.5% by weight or less, particularly preferably 0.2% by weight or less, and more preferably 0%. .1% by weight or less.
- 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and 2-hydroxypropyl acrylate are particularly 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 atom-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,
- a heterocyclic amine monomer such as (meth) acryloylmorpholine is preferable in terms of excellent durability and excellent adhesion to metals and metal oxides.
- dimethylaminoethyl (meth) acrylate and (meth) acryloylmorpholine are particularly preferable.
- amide group-containing monomer examples include (meth) acrylamide; methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, isopropoxymethyl (meth) acrylamide, and n-butoxymethyl (meth).
- Alkoxyalkyl (meth) acrylamide monomers such as acrylamide and isobutoxymethyl (meth) acrylamide; Dialkyl (meth) acrylamide monomers such as dimethyl (meth) acrylamide and diethyl (meth) acrylamide; N- (hydroxymethyl) acrylamide and the like Hydroxyl group-containing amide monomers; (meth) acryloylmorpholine; and the like.
- alkoxyalkyl (meth) acrylamide monomers and dialkyl (meth) acrylamide monomers are preferable from the viewpoint of stability of the resin solution and suppression of migration of the antistatic agent.
- polar group-containing monomers (a1) it is preferable to use a hydroxyl group-containing monomer in terms of excellent heat and heat whitening resistance. Moreover, this polar group containing monomer (a1) may be used independently, and may use 2 or more types together. It is also preferable to use a hydroxyl group-containing monomer and a carboxyl group-containing monomer, or a hydroxyl group-containing monomer and a tertiary amine monomer in combination because the aging tends to be shortened.
- the content of the polar group-containing monomer (a1) (when two or more types are used in combination, the total content) needs to be 5 to 50% by weight with respect to the entire copolymerization component. It is preferably 6 to 30% by weight, particularly preferably 7 to 25% by weight, and further preferably 8 to 20% by weight. If the content is too small, the moist heat whitening resistance tends to decrease, and if it is too large, the storage stability as an acrylic resin solution tends to decrease.
- the content in the case of containing a hydroxyl group-containing monomer as the polar group-containing monomer (a1) is preferably 5 to 50% by weight, particularly preferably 6 to 35% by weight, based on the entire copolymerization component. It is preferably 7 to 25% by weight, particularly preferably 8 to 20% by weight.
- the content of the hydroxyl group-containing monomer is too small, the heat and heat whitening resistance tends to be lowered, and when too much, the storage stability as an acrylic resin solution tends to be lowered.
- the content when the polar group-containing monomer (a1) contains a carboxyl group-containing monomer is preferably 1% by weight or less based on the entire copolymerization component.
- 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) Acrylate, and the like. 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 excellent 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.
- 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-containing monomers such as dicyclopentanyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxy Butyl
- an aromatic ring-containing monomer is preferable in terms of easy adjustment of the refractive index and birefringence and excellent light leakage resistance (particularly preferably benzyl (meth) acrylate, phenoxy (meth) ethyl acrylate, phenoxydiethylene glycol (meth) ) Acrylate), refractive index and birefringence are easy to adjust, and an alicyclic-containing monomer is preferable from the viewpoint of excellent adhesion to a low-polar adherend (such as 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 (a3).
- these polymerization components can be used, for example, by mixing or dropping the polymerization component and polymerization initiator in an organic solvent and polymerizing them.
- the polymerization reaction can be carried out by a conventionally known polymerization method such as solution radical polymerization, suspension polymerization, bulk polymerization, emulsion polymerization, etc. Among them, solution radical polymerization and bulk polymerization are preferable, and solution radical polymerization is particularly preferable. Polymerization.
- 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, methyl, due to the ease of polymerization reaction, chain transfer effect, ease of drying during adhesive coating, and high safety.
- Isobutyl ketone is preferably used, and more preferably 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 for such solution radical polymerization include 2,2′-azobisisobutyronitrile and 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, Examples thereof include organic peroxides such as cumene 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 needs to contain 5 to 50% by weight of a structural unit derived from the polar group-containing monomer (a1), preferably 6 to 35% by weight, particularly The amount is preferably 7 to 25% by weight, more preferably 8 to 20% by weight.
- a structural unit derived from the polar group-containing monomer preferably 6 to 35% by weight, particularly The amount is preferably 7 to 25% by weight, more preferably 8 to 20% by weight.
- the acrylic resin (A) preferably has a weight average molecular weight of 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 160,000. It is ten thousand. If the weight average molecular weight is too small, the durability tends to decrease. If the weight average molecular weight is too large, a large amount of a diluent solvent is required at the time of manufacture, the drying property decreases, the residual solvent increases in the pressure-sensitive adhesive layer, and the heat resistance is increased. There is a tendency 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 ⁇ 60 to 0 ° C., particularly preferably ⁇ 50 to ⁇ 20 ° C., and further preferably ⁇ 45 to ⁇ 25 ° 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 when the homopolymer of the monomer constituting the acrylic resin (A) is usually measured by a differential scanning calorimeter (DSC), and is JIS K7121-1987 or JIS K6240. It can measure by the method based on.
- DSC differential scanning calorimeter
- the refractive index of the acrylic resin (A) is usually from 1.440 to 1.600, preferably from 1.460 to 1.550, particularly preferably from 1.470 to 1.500. For such a refractive index, it is preferable to reduce the difference in refractive index between the laminated members because the optical loss at the member interface is reduced.
- 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, particularly preferably 0.8 or less, and further preferably 0.5 or less.
- the haze is too high, the image quality of a display using the haze tends to be deteriorated.
- 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.
- an oligomer type silane coupling agent (B1) having an alkoxy group content of 15% by weight or less. It contains.
- regulated by this invention points out the alkoxy group derived from alkoxysilane, and the alkoxy group contained in a molecule other than that is not included.
- the end of the polyether part 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.
- an epoxy group and a mercapto group are preferable in terms of excellent durability and reworkability.
- alkoxy group examples include a methoxy group, an ethoxy group, and a propoxy group.
- an alkyl group having 1 to 8 carbon atoms is preferable, an alkyl group having 1 to 2 carbon atoms is particularly preferable, and specifically, a methoxy group or an ethoxy group.
- 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 alkoxy group content of the oligomer type silane coupling agent (B1) needs to be 15% by weight or less, preferably 1 to 15% by weight, particularly preferably 3 to 14.5% by weight, and still more preferably. 5 to 14.5% by weight. If the alkoxy group content is too large, the long-term reworkability tends to decrease. If the amount is too small, the durability tends to decrease.
- the weight average molecular weight of the oligomer type silane coupling agent (B1) is preferably 3,000 or more, particularly preferably 4,000 to 30,000, and further preferably 4,500 to 20,000. When the weight average molecular weight is in the above range, the balance between long-term reworkability and durability tends to be excellent.
- said weight average molecular weight is a weight average molecular weight by standard polystyrene molecular weight conversion, and can be measured with the following method.
- Apparatus Gel permeation chromatograph detector: differential refractive index detector RI (RI-8020, manufactured by Tosoh Corporation, sensitivity 32) Column: TSKgel guardcolumn H HR -H (1) (Tosoh ⁇ 6mm ⁇ 4cm), TSKgel GMH HR- N (2) (Tosoh ⁇ 7.8mm ⁇ 30cm)
- Solvent tetrahydrofuran (THF) Column temperature: 23 ° C Flow rate: 1.0 mL / min
- the reactive functional group equivalent of the oligomer type silane coupling agent (B1) is preferably 1,600 g / mol or less, particularly preferably 100 to 900 g / mol, and further preferably 300 to 700 g / mol. When the reactive functional group equivalent is within the above range, durability tends to be superior.
- the oligomer type silane coupling agent (B1) is an oligomer type silane coupling agent.
- an oligomer type silane coupling agent such as a dimer or trimer obtained by hydrolysis and polycondensation of a part of an organosilicon compound. It is an organosilicon compound (organosiloxane compound).
- oligomer type silane coupling agent (B1) for example, an oligomer in which a part of an organosilicon compound such as ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane is hydrolyzed and polycondensed is used.
- Type organosilicon compounds (epoxy group-containing silicone alkoxy oligomers, etc.), or oligomer type organosilicon compounds obtained by ether-modifying a part of these oligomer type organosilicon compounds; oligomer type epoxy group-containing silane coupling agents; ⁇ -mercaptopropyl
- An oligomer type mercapto group-containing silane coupling agent such as an oligomer type organosilicon compound (such as a mercapto group-containing silicone alkoxy oligomer) obtained by hydrolysis and polycondensation of a part of an organosilicon compound such as triethoxysilane.
- the oligomer type silane coupling agent (B1) may be appropriately selected and used so as to satisfy the respective conditions. Moreover, the said oligomer type silane coupling agent (B1) may use only 1 type, and may use 2 or more types together.
- oligomer type silane coupling agent (B1) specifically, “X-24-9590” (weight average molecular weight: 13,700, containing alkoxy group: methoxy group, which is a commercial product manufactured by Shin-Etsu Chemical Co., Ltd., Alkoxy group content: 9.5% by weight, reactive functional group: epoxy group, epoxy equivalent: 592 g / mol), “X-24-9589” (weight average molecular weight: 4,700, contained alkoxy group: ethoxy group, Alkoxy group content: 13.2%, reactive functional group: epoxy group, epoxy equivalent: 1509 g / mol) and the like.
- “X-24-9590” is particularly preferable.
- the content of the oligomer type silane coupling agent (B1) is preferably 0.001 to 1 part by weight, particularly preferably 0.015 to 0.5 part per 100 parts by weight of the acrylic resin (A). Parts by weight, more preferably 0.020 to 0.3 parts by weight, still more preferably 0.025 to 0.15.
- the content is too large, the durability tends to decrease, and when the content is too small, the long-term reworkability tends to decrease.
- a silane coupling agent other than the oligomer type silane coupling agent (B1) can be used as long as the effects of the invention are not impaired.
- the content of the silane coupling agent other than the oligomer type silane coupling agent (B1) is specifically 0.5 parts by weight or less with respect to 100 parts by weight of the acrylic resin (A). Is more preferably 0.3 parts by weight or less, particularly preferably 0.1 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 adhesiveness to the substrate and excellent in reactivity with the acrylic resin (A).
- isocyanate crosslinking agent examples include, for example, tolylene diisocyanate crosslinking agents such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, xylylene diisocyanate crosslinking agents such as 1,3-xylylene diisocyanate, Diphenylmethane-based crosslinkers such as diphenylmethane-4,4-diisocyanate, aromatic isocyanate-based crosslinkers such as naphthalene diisocyanate-based crosslinkers such as 1,5-naphthalene diisocyanate; isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 4,4 '-Dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, 1,3-diisocyanato
- tolylene diisocyanate-based crosslinking agents are preferable in terms of pot life and durability, and xylylene diisocyanate-based crosslinking agents or isocyanurate skeleton-containing isocyanate-based crosslinking agents are preferable in terms of shortening the aging time.
- An aromatic non-containing isocyanate-based crosslinking agent is preferable in terms of yellowing resistance.
- tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and trimethylolpropane adduct, and isocyanurate are excellent in balance of durability, pot life, and crosslinking speed. preferable.
- 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.
- Examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexaptoxymethyl 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 cross-linking agent (C) may be used alone or in combination of two or more.
- the content of the crosslinking agent (C) is preferably 0.01 to 5 parts by weight, particularly preferably 0.05 to 1.5 parts by weight, with respect to 100 parts by weight of the acrylic resin (A). More preferably, it is 0.1 to 0.5 parts by weight. When the content is too small, the durability tends to be lowered, and when the content is too large, the stress relaxation property is lowered and the substrate is likely to be warped, or long-term aging is required.
- 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, alkaline earth metal 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.
- organic salts are preferable in terms of excellent corrosion prevention, long-term reworkability, and excellent storage stability, and more preferably ammonium cations, imidazolium cations, pyridinium cations, piperidinium cations, pyrrolidis.
- An onium salt comprising a nitrogen-containing cation such as a cation, particularly preferably an alkyl ammonium salt, more preferably an acyclic tetraalkylammonium cation and an N, N-bis (trifluoromethanesulfonyl) imide anion, an ammonium cation and an N, N -Ammonium salt composed of bis (fluorosulfonyl) imide anion.
- the melting point of the ionic compound (D1) is preferably 10 ° C. to 100 ° C., particularly preferably 20 ° C. to 80 ° C., more 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, and still more preferably 2 parts per 100 parts by weight of the acrylic resin (A). To 5 parts by weight, particularly preferably 2.5 to 4.5 parts by weight. If the content 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 polarization degree of the polarizing plate decreases, the heat-and-whitening resistance decreases, There is a tendency for durability to fall 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 and the like contained in the raw materials for producing the constituent components of the pressure-sensitive adhesive composition may be contained.
- the content of the other components is preferably 5 parts by weight or less, particularly preferably 1 part by weight or less, and further preferably 0.5 parts by weight or less with respect to 100 parts by weight of the acrylic resin (A). .
- 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.
- the method of aging at room temperature by the method [2] is preferable in that the optical member is not damaged and the adhesiveness to 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 is preferably diluted with a solvent, and the dilution concentration is preferably 5 to 60% by weight, particularly preferably as a solid content concentration. 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, and an alcohol solvent such as methanol, ethanol and propyl alcohol can be used.
- ester solvents such as methyl acetate, ethyl acetate, methyl acetoacetate, ethyl acetoacetate, acetone
- a ketone solvent such as methyl ethyl ketone and methyl isobuty
- the acrylic pressure-sensitive adhesive composition is 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 90% by weight, more preferably 40% from the viewpoint of durability performance and suppression of decrease in polarization degree. Is 60 to 85% 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. It is immersed in ethyl for 24 hours, and the weight percentage of the insoluble adhesive component remaining in the wire mesh 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. .
- the surface resistance value is preferably 1 ⁇ 10 12 ⁇ or less, particularly preferably 1 ⁇ 10 11 ⁇ or less, more preferably. Is 5 ⁇ 10 10 ⁇ or less. If the surface resistance is too high, the polarizing plate and the pressure-sensitive adhesive layer are likely 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 is too thin, the physical properties of the adhesive tend to be difficult to stabilize. If the thickness is too thick, the amount of moisture intrusion from the end portion tends to increase, and the long-term reworkability 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 adhesive strength (reworkability) of the adhesive of the present invention is appropriately determined according to the material of the adherend.
- the adhesive strength after 1 day of bonding is preferably 0.1 to 10 N / 25 mm, and more preferably 0.1 to 5 N / 25 mm.
- the adhesive strength after 20 days is preferably from 0.1 to 20 N / 25 mm, more preferably from 0.1 to 15 N / 25 mm, particularly preferably from 0.1 to 10 N / 25 mm.
- the adhesive strength after 50 days is preferably from 0.1 to 20 N / 25 mm, more preferably from 0.1 to 15 N / 25 mm, particularly preferably from 0.1 to 10 N / 25 mm.
- the adhesive strength is calculated as follows. About a polarizing plate with an adhesive layer, it cut
- 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.
- Examples of the protective film constituting the polarizing plate include a triacetyl cellulose film, an acrylic film, a polyethylene film, a polypropylene film, a cycloolefin film, and the like.
- the present invention is applied to any polarizing film 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) and a silane coupling agent (B), it measured according to 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).
- ⁇ Acrylic resin (A)> Manufacture of acrylic resin (A-1)
- a 4-neck round bottom flask equipped with a reflux condenser, a stirrer, a nitrogen gas inlet and a thermometer 6 parts of 2-hydroxyethyl acrylate (a1), 0.7 parts of acrylic acid (a1), n-butyl Charge 73.3 parts of acrylate (a2), 20 parts of benzyl acrylate (a3), 53 parts of ethyl acetate, 42 parts of acetone, 0.013 part of azobisisobutyronitrile (AIBN) as a polymerization initiator, and bring the internal temperature to the boiling point. To start the reaction.
- AIBN azobisisobutyronitrile
- 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 of the silane coupling agent (B) was measured according to the method described above. Moreover, about the alkoxy group content, the reactive functional group, the epoxy equivalent or the mercapto equivalent, and the contained alkoxy group, catalog values were adopted unless otherwise specified.
- the alkoxy group content of “X-24-9589” was measured by the following method, and the alkoxy group content was calculated. 1. Measurement Approximately 50 mg of a sample was weighed into a vial, and 1 mL of d-chloroform was added and dissolved to prepare a 5% (w / v) chloroform solution. This was put into a sample tube for NMR measurement, and 1 HNMR measurement was performed under the following conditions. The obtained 1 HNMR spectrum is shown in FIG. ⁇ Measurement conditions ⁇ Measuring device: Ascend TM 400 manufactured by Bruker Probe: cryo probe Pulse program: Single pulse Measurement temperature: 23 ° C (296K) Integration count: 16 times Pulse delay time: 10 sec 2.
- the number of organic substituents is X
- the number of alkoxy groups ethoxy group, propenyloxy group
- R the number of alkoxy groups
- R the main chain (—SiO—) is (X + R) / 2. did.
- C Crosslinking agent (C)> The following were prepared as a crosslinking agent (C).
- C-1) Adduct body of tolylene diisocyanate and trimethylolpropane (manufactured by Tosoh Corporation, “Coronate L55E”)
- (D-2) an ionic compound comprising an aromatic ring-containing ammonium cation and bis (fluorosulfonylimide) (Daiichi Kogyo Seiyaku Co., Ltd., “MP-446”, melting point: 37 ° C.)
- the obtained acrylic pressure-sensitive adhesive composition was applied to a release sheet having a thickness of 38 ⁇ m (“Lumirror SP-0138BU” manufactured by Mitsui Chemicals, Inc.) so that the thickness after drying was 25 ⁇ m and dried at 100 ° C. for 3 minutes. After that, the surface of the pressure-sensitive adhesive layer opposite to the release sheet is bonded to one TAC film surface of a polarizing plate on which triacetyl cellulose (TAC) films are laminated on both sides, and the environment is 23 ° C. ⁇ 50% RH for 7 days.
- TAC triacetyl cellulose
- a polarizing plate [I] with an adhesive layer layer structure: release sheet / adhesive layer / TAC film 1 / polarizer / TAC film 2, TAC film 1: thickness 40 ⁇ m, TAC film 2: 60 ⁇ m.
- a pressure-sensitive adhesive layer-attached polarizing plate [II] was obtained in the same manner except that the COP surface and the pressure-sensitive adhesive layer surface of the cycloolefin-based film / polarizer / TAC-based film subjected to corona treatment were bonded together.
- the TAC film is a triacetylcellulose film (thickness 60 ⁇ m), and the COP film is a cycloolefin film (thickness 50 ⁇ 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), left in an environment of 23 ° C. ⁇ 50% RH for 1, 20, and 50 days, then The adhesive strength when peeled at a peeling angle of 180 ° and a peeling speed of 300 mm / min was measured and evaluated according to the following criteria. (Evaluation criteria) 1 day later A ...
- the obtained polarizing plate [II] with the pressure-sensitive adhesive layer was cut into 3.5 cm ⁇ 3.5 cm, the release sheet was peeled off, and the pressure-sensitive adhesive layer surface was alkali-free glass (Corning “Eagle XG”: thickness 1. 1 mm) and then reciprocally bonded by a 2 kg roller, followed by autoclave treatment (0.5 MPa ⁇ 50 ° C. ⁇ 20 minutes) to prepare a sample for a moisture and heat whitening resistance test.
- the obtained sample was exposed to an environment of 60 ° C. ⁇ 90% RH for 250 hours, then taken out and left at room temperature.
- haze is the value which deducted the value of 1.1 mm non-alkali glass as a blank. (Evaluation criteria) ⁇ Haze immediately after removal ⁇ ⁇ ⁇ ⁇ less than 1% ⁇ ⁇ ⁇ ⁇ 1% or more, less than 3% ⁇ ⁇ ⁇ ⁇ 3% or more, less than 4% ⁇ ⁇ ⁇ ⁇ 4% or more ⁇ Haze 3 hours after removal ⁇ ⁇ ⁇ Less than 1% ⁇ ⁇ ⁇ ⁇ 1% or more, less than 2% ⁇ ⁇ ⁇ ⁇ 2% or more, less than 3% ⁇ ... 3% or more
- the silane coupling agent is hydrolyzed by moisture in the pressure-sensitive adhesive system, and improves adhesion by bonding to the glass surface via a silanol group.
- An acrylic resin that contains a large amount of polar monomer to such an extent that it has good resistance to moist heat whitening tends to take up moisture in the environment and is susceptible to hydrolysis. Therefore, long-term reworkability tends to be lower than usual.
- Comparative Examples 1 and 2 using an acrylic resin that does not contain a large amount of polar group monomer long-term reworkability is not a problem even when a silane coupling agent having an alkoxy group content of greater than 15% by weight is used. Recognize.
- an oligomeric silane coupling agent (B1) having an alkoxy group content of 15% by weight or less even when an acrylic resin containing a large amount of polar monomer to such an extent that the resistance to moist heat whitening is good is used.
- 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 12, 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 used as a pressure-sensitive adhesive used for laminating a polarizing plate (protective film) and a liquid crystal cell (glass) at the time of manufacturing a liquid crystal display device, the rework is excellent over a long period of time. Even when using a polarizing plate with a low polarity film such as a cycloolefin film as a protective film, it is possible to obtain a pressure-sensitive adhesive with excellent resistance to moisture and heat whitening. It is useful as a pressure-sensitive adhesive for optical members for bonding optical components to be constituted, particularly as a pressure-sensitive adhesive for polarizing plates for bonding a polarizing plate and a glass substrate of a liquid crystal cell.
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Abstract
Description
また、従来偏光板に使用される粘着剤は、偏光板の種類によって使いわけられているが、コストや作業性の点で、偏光板の種類が異なった場合でも使用可能な粘着剤が求められていた。
また、特許文献2には、耐湿熱白化性を考慮して、極性基含有モノマーを多く導入したアクリル系樹脂を使用した粘着剤が記載されている。
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)としては、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ることが必要であり、例えば、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)を5~50重量%含む共重合成分を共重合して得られるアクリル系樹脂であることが好ましい。
上記アミノ基含有モノマーの中でも、架橋促進効果が高い点、樹脂の保存安定性が高い点で3級アミノ基含有モノマーが好ましい。
また耐久性に優れている点、金属や金属酸化物との密着性に優れている点で(メタ)アクリロイルモルホリン等の複素環式アミンモノマーが好ましい。これらの中でも特に好ましくはジメチルアミノエチル(メタ)アクリレート及び(メタ)アクリロイルモルホリンである。
上記アミド基含有モノマーの中でも、樹脂溶液の安定性の点や、帯電防止剤の移行を抑制する点でアルコキシアルキル(メタ)アクリルアミド系モノマー、ジアルキル(メタ)アクリルアミド系モノマーが好ましい。
また、かかる極性基含有モノマー(a1)は、単独で用いてもよいし2種以上を併用してもよい。エージングが短くなる傾向にある点で、水酸基含有モノマーとカルボキシル基含有モノマー、水酸基含有モノマーと3級アミン系モノマーを併用する事も好ましい。
かかる含有量が少なすぎると耐湿熱白化性が低下する傾向にあり、多すぎるとアクリル系樹脂溶液としての保存安定性が低下する傾向にある。
水酸基含有モノマーの含有量が少なすぎると、耐湿熱白化性が低下する傾向があり、多すぎるとアクリル系樹脂溶液としての保存安定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。
上記重合反応は、溶液ラジカル重合、懸濁重合、塊状重合、乳化重合等の従来公知の重合方法により行なうことができるが、これらの中でも、溶液ラジカル重合、塊状重合が好ましく、特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、安全性の高さから、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用いられ、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、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)
即ち、アクリル系樹脂(A)のガラス転移温度(Tg)とは、アクリル系樹脂(A)を構成するそれぞれのモノマーをホモポリマーとした際のガラス転移温度及び重量分率をFoxの式に当てはめて算出した値である。
なお、アクリル系樹脂(A)を構成するモノマーの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。
本発明では、構造中に反応性官能基とアルコキシ基をそれぞれ1つ以上含有するシランカップリング剤(B)として、アルコキシ基含有量が15重量%以下であるオリゴマー型シランカップリング剤(B1)を含有するものである。
例えば、ポリエーテル変性シランのポリエーテル部の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。
かかるアルコキシ基含有量が多すぎると長期リワーク性が低下する傾向にある。なお、少なすぎると耐久性が低下する傾向にある。
かかる重量平均分子量が上記範囲にあると長期リワーク性と耐久性のバランスに優れる傾向にある。
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
かかる反応性官能基当量が上記範囲であれば、耐久性により優れる傾向にある。
これらの中から、オリゴマー型シランカップリング剤(B1)の、それぞれの条件を満足するように適宜選択して用いればよい。また、上記オリゴマー型シランカップリング剤(B1)は、1種のみを用いてもよいし、2種以上を併用してもよい。
これらの中でも、特に好ましくは、「X-24-9590」である。
架橋剤(C)としては、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。
かかる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、光学部材との接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。
例えば、液晶セル等のガラス基板に貼合する場合には、貼合1日後の粘着力として、0.1~10N/25mmが好ましく、更には0.1~5N/25mmが好ましい。また、20日後の粘着力として、0.1~20N/25mmが好ましく、更には0.1~15N/25mm、特には0.1~10N/25mmが好ましい。更に、50日後の粘着力として、0.1~20N/25mmが好ましく、更には0.1~15N/25mm、特には0.1~10N/25mmが好ましい。
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。また長期リワーク性に関しては、オートクレーブ処理後23℃×50%RHで所定の期間放置した後に引き剥がし角度180°、剥離速度300mm/分で剥離試験を行う。
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53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、内温を沸点まで上昇させて反応を開始させた。次いでAIBNを0.04%含む酢酸エチル溶液を30部滴下し、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。
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)の重量平均分子量に関しては、前述の方法にしたがって測定した。また、アルコキシ基含有量、反応性官能基、エポキシ当量またはメルカプト当量、含有アルコキシ基については、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、「X-24-9590」、重量平均分子量:13,700、アルコキシ基含有量:9.5%、反応性官能基:エポキシ基、エポキシ当量:592g/mol、含有アルコキシ基:メトキシ基)
(信越化学工業社製、「X-24-9589」、重量平均分子量:4,700、アルコキシ基含有量:14.5%(測定値)、反応性官能基:エポキシ基、エポキシ当量:1,509g/mol、含有アルコキシ基:エトキシ基:エトキシ基及びプロペイルオキシ基)
1.測定
試料約50mgをバイアル瓶に秤量し、d-クロロホルム1mLを加えて溶解させ5%(w/v)クロロホルム溶液を調製した。これをNMR測定用サンプルチューブへ入れ、以下の条件にて1HNMR測定を行った。得られた1HNMRスペクトルを図1に示す。
≪測定条件≫
測定装置 :Bruker社製AscendTM400
プローブ :cryoプローブ
パルスプログラム:シングルパルス
測定温度 :23℃(296K)
積算回数 :16回
パルス遅延時間 :10sec
2.アルコキシ基含有量の計算
1HNMRスペクトルのシグナルA~Fについて、A(6.2,6.0ppm):プロペニルオキシ基、B(3.6ppm):エチレンオキシド鎖、C(3.4ppm):エチレンオキシド鎖末端メトキシ基、D(3.1,2.8,2.6ppm):エポキシ基、E(1.2ppm):エトキシ基、F(0.1ppm):メチル基と帰属し、これらのシグナルの積分値よりアルコキシ基含有量を求めた。
なお、有機置換基(エポキシ基、メチル基)数をX、アルコキシ基(エトキシ基、プロペニルオキシ基)数をRとして、主鎖(-SiO-)は(X+R)/2含まれているものとした。
(信越化学工業社製、「X-41-1059A」、重量平均分子量:2,270アルコキシ基含有量:42%、反応性官能基:エポキシ基、エポキシ当量:350g/mol、含有アルコキシ基:メトキシ基、エトキシ基)
(信越化学工業社製、「X-41-1805」、重量平均分子量:3,450、アルコキシ基含有量:50%、反応性官能基:メルカプト基、メルカプト当量:800g/mol、含有アルコキシ基:メトキシ基、エトキシ基)
(信越化学工業社製、「X-41-1810」、重量平均分子量:640、アルコキシ基含有量:30%、反応性官能基:メルカプト基、メルカプト当量:450g/mol、含有アルコキシ基:メトキシ基)
3-グリシドキシプロピルトリメトキシシラン(信越化学工業社製、「KBM-403」、分子量:236.6、アルコキシ基含有量:39%(計算値)、反応性官能基:エポキシ基、エポキシ当量:236.6g/mol(計算値)含有アルコキシ基:メトキシ基)
なお、B’-4の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)。エポキシ当量はエポキシ基1molに対する分子量として計算した。
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」)
帯電防止剤(D)として以下のものを用意した。
(D-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」、融点27.5℃)
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。
得られたアクリル系粘着剤組成物を厚み38μmの離型シート(三井化学東セロ社製「ルミラーSP-0138BU」)に乾燥後の厚みが25μmとなるように塗布し、100℃で3分間乾燥したのち、トリアセチルセルロース(TAC)フィルムを両面に積層した偏光板の一方のTACフィルム表面に、離型シートと反対側の粘着剤層面を貼り合わせ、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[I]を得た(層構成;離型シート/粘着剤層/TACフィルム1/偏光子/TACフィルム2、TACフィルム1:厚み40μm、TACフィルム2:60μm)。
コロナ処理を施したシクロオレフィン系フィルム/偏光子/TAC系フィルムのCOP面と粘着剤層面を貼り合わせた以外は同様にして粘着剤層付き偏光板[II]を得た。
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60μm)、COPフィルムはシクロオレフィンフィルム(厚み50μm)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1日、20日、50日静置し、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)
・1日後
A・・・5N/25mm以下
B・・・5N/25mm超え、10N/25mm以下
C・・・10N/25mm超え、または糊残りが発生またはもしくは基材が破断
・20日後
A・・・5N/25mm以下
B・・・5N/25mm超え、10N/25mm以下
C・・・10N/25mm超え、15N/25mm以下
D・・・15N/25mm超え、20N/25mm以下
E・・・20N/25mm超え、または糊残りが発生またはもしくは基材が破断
・50日後
A・・・5N/25mm以下
B・・・5N/25mm超え、10N/25mm以下
C・・・10N/25mm超え、15N/25mm以下
D・・・15N/25mm超え、20N/25mm以下
E・・・20N/25mm超え、または糊残りが発生またはもしくは基材が破断
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。
得られたサンプルについて、(1)耐熱性(80℃×500時間)、の条件に暴露した後の偏光板について以下の評価を行った。
(評価基準)
○・・・偏光板の全面に発砲もしくは端部に浮きが見られない
×・・・偏光板の全面に発泡もしくは端部に浮きが見られる
〔耐湿熱白化性〕
得られた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、耐湿熱白化性試験用のサンプルを作製した。
得られたサンプルについて、60℃×90%RHの環境下に250時間暴露した後、取出し室温に放置した。そして、取り出してから3時間後のヘイズを測定し、耐湿熱白化性を評価した。なお、ヘイズは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、3%未満
△・・・3%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、3%未満
×・・・3%以上
得られた粘着剤層付偏光板〔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率を測定した。
また、極性基含有モノマーを通常より多く含むアクリル系樹脂(A)とアルコキシ基量が15重量%より大きいシランカップリング剤を使用したアクリル系粘着剤組成物から得られる粘着剤を使用した比較例3~9では、耐湿熱白化性には優れるものの長期リワーク性に劣ることがわかる。
Claims (9)
- 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%含むアクリル系樹脂であり、
上記シランカップリング剤(B)が、アルコキシ基含有量が15重量%以下であるオリゴマー型シランカップリング剤(B1)を含有することを特徴とするアクリル系粘着剤組成物。 - 上記オリゴマー型シランカップリング剤(B1)の反応性官能基当量が、1,600g/mol以下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。
- 上記オリゴマー型シランカップリング剤(B1)の重量平均分子量が、3,000以上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。
- 上記極性基含有モノマー(a1)が、少なくとも水酸基モノマーを含有す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。
- 更に架橋剤(C)を含有することを特徴とする請求項1~4のいずれか一項に記載のアクリル系粘着剤組成物。
- 更に帯電防止剤(D)を含有することを特徴とする請求項1~5のいずれか一項に記載のアクリル系樹脂組成物。
- 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7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7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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JP2018076489A (ja) * | 2016-11-01 | 2018-05-17 | 日本合成化学工業株式会社 | 偏光板用粘着剤組成物、偏光板用粘着剤、並びに粘着剤層付偏光板 |
CN111662646A (zh) * | 2019-03-08 | 2020-09-15 | 日东电工株式会社 | 切割带和带有粘接薄膜的切割带 |
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KR102424024B1 (ko) * | 2019-10-02 | 2022-07-25 | 주식회사 케이씨씨 | 유리 접착제용 프라이머 조성물 |
CN115657178B (zh) * | 2022-12-28 | 2023-04-18 | 深圳市全正科技有限公司 | 一种冷固化贴合反射膜及其制备方法、光学显示器件 |
CN116041612A (zh) * | 2022-12-30 | 2023-05-02 | 江苏斯迪克新材料科技股份有限公司 | 丙烯酸酯共聚物原胶、压敏胶及其制备方法 |
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JP6977562B2 (ja) | 2021-12-08 |
JP2021107564A (ja) | 2021-07-29 |
TWI731142B (zh) | 2021-06-21 |
JP7137159B2 (ja) | 2022-09-14 |
CN109476971A (zh) | 2019-03-15 |
TW201817840A (zh) | 2018-05-16 |
JPWO2018034232A1 (ja) | 2019-06-20 |
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