WO2020136762A1 - 光学フィルム用粘着剤組成物、光学フィルム用粘着剤層、及び、粘着剤層付光学フィルム - Google Patents

光学フィルム用粘着剤組成物、光学フィルム用粘着剤層、及び、粘着剤層付光学フィルム Download PDF

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WO2020136762A1
WO2020136762A1 PCT/JP2018/047873 JP2018047873W WO2020136762A1 WO 2020136762 A1 WO2020136762 A1 WO 2020136762A1 JP 2018047873 W JP2018047873 W JP 2018047873W WO 2020136762 A1 WO2020136762 A1 WO 2020136762A1
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Prior art keywords
meth
acrylate
mass
sensitive adhesive
adhesive layer
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PCT/JP2018/047873
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English (en)
French (fr)
Japanese (ja)
Inventor
寛大 小野
晶子 杉野
智之 木村
雄祐 外山
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日東電工株式会社
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Priority to PCT/JP2018/047873 priority Critical patent/WO2020136762A1/ja
Priority to KR1020247007099A priority patent/KR20240033175A/ko
Priority to CN201880100511.7A priority patent/CN113227297B/zh
Priority to KR1020217022913A priority patent/KR20210107756A/ko
Priority to JP2020562021A priority patent/JP7307749B2/ja
Publication of WO2020136762A1 publication Critical patent/WO2020136762A1/ja

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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
    • 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
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition for an optical film, a pressure-sensitive adhesive layer for an optical film, and an optical film with a pressure-sensitive adhesive layer.
  • the optical film it is possible to use a polarizing film (polarizing plate), a retardation film, an optical compensation film, a brightness enhancement film, or a laminate of these.
  • polarizing films are attached.
  • various optical elements have been used in liquid crystal panels in order to improve the display quality of displays.
  • a retardation film for preventing coloration a viewing angle widening film for improving the viewing angle of a liquid crystal display, and a brightness enhancement film for enhancing the contrast of the display are used.
  • These films are collectively called optical films.
  • the pressure-sensitive adhesive When attaching an optical member such as the optical film to a liquid crystal cell, an adhesive is usually used.
  • the adhesion between the optical film and the liquid crystal cell or the optical film usually reduces the loss of light, so that the respective materials are adhered using an adhesive.
  • the pressure-sensitive adhesive since the pressure-sensitive adhesive has advantages such as not requiring a drying step to fix the optical film, the pressure-sensitive adhesive is an optical layer with a pressure-sensitive adhesive layer previously provided as a pressure-sensitive adhesive layer on one side of the optical film. Films are commonly used.
  • a release film is usually attached to the adhesive layer of the optical film with an adhesive layer.
  • the necessary properties required for the pressure-sensitive adhesive layer include heating the pressure-sensitive adhesive layer in a state where the pressure-sensitive adhesive layer is attached to an optical film, and further when the pressure-sensitive adhesive layer-attached optical film is attached to a glass substrate of a liquid crystal panel.
  • High durability is required under humidified conditions, for example, in a durability test such as heating and humidification that is usually performed as an environmental promotion test, problems such as foaming, peeling, and floating due to the adhesive layer do not occur. Adhesion reliability is required.
  • adhesive layers and optical films with adhesive layers used for in-vehicle displays such as car navigation systems and mobile phones, which are used outdoors and are expected to be used in hot vehicles, have high adhesive reliability and durability at high temperatures. Sex is required.
  • optical films eg, polarizing films
  • pressure-sensitive adhesive layer itself is also deformed due to the shrinkage of the polarizing film.
  • Patent Document 1 Various pressure-sensitive adhesive compositions for forming the pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-carrying optical film have been proposed (for example, Patent Document 1).
  • Patent Document 1 proposes a pressure-sensitive adhesive composition in which 4 to 20 parts by mass of an isocyanate crosslinking agent is mixed with 100 parts by mass of an acrylic polymer containing a polar monomer such as an aromatic ring-containing monomer and an amide group-containing monomer. ing.
  • an acrylic polymer containing a polar monomer such as an aromatic ring-containing monomer and an amide group-containing monomer.
  • the pressure-sensitive adhesive composition of Patent Document 1 contains a large amount of the crosslinking agent, it tends to peel off in the durability test.
  • the present invention can suppress the occurrence of foaming, peeling, and the like even when the adherend (optical film) is exposed to heating and humidifying conditions, and has durability (heat resistance, moisture resistance). It is an object of the present invention to provide a pressure-sensitive adhesive composition for an optical film, which is capable of obtaining a pressure-sensitive adhesive layer for an optical film having excellent peeling resistance) and reworkability.
  • Another object of the present invention is to provide a pressure-sensitive adhesive layer for an optical film and a pressure-sensitive adhesive layer-attached optical film having the pressure-sensitive adhesive layer for an optical film.
  • the pressure-sensitive adhesive composition for an optical film of the present invention is a pressure-sensitive adhesive composition for an optical film containing a (meth)acrylic polymer and a crosslinking agent, and the (meth)acrylic polymer is a monomer unit, An amide group-containing monomer and an alkoxy group-containing alkyl (meth)acrylate are contained, and the alkoxy group-containing alkyl (meth)acrylate is added to 20% of the total amount of monomer units constituting the (meth)acrylic polymer of 100% by mass. It is characterized by containing up to 80% by mass.
  • the "pressure-sensitive adhesive composition for optical film” may be simply referred to as "pressure-sensitive adhesive composition" below.
  • the pressure-sensitive adhesive composition for an optical film according to the present invention contains 0.9 to 7% by mass of the amide group-containing monomer, and the alkoxy group based on 100% by mass of the total amount of monomer units constituting the (meth)acrylic polymer. It is preferable to contain 25 to 75% by mass of a group-containing alkyl (meth)acrylate.
  • the pressure-sensitive adhesive composition for an optical film according to the present invention comprises 0.9 to 3% by mass of the amide group-containing monomer, and 100% by mass of the total amount of monomer units constituting the (meth)acrylic polymer. It is preferable to contain 35 to 75% by mass of a group-containing alkyl (meth)acrylate.
  • the pressure-sensitive adhesive composition for an optical film according to the present invention comprises 0.9 to 3% by mass of the amide group-containing monomer, and 100% by mass of the total amount of monomer units constituting the (meth)acrylic polymer. It is preferable to contain 50 to 75% by mass of a group-containing alkyl (meth)acrylate.
  • the (meth)acrylic polymer does not contain a carboxyl group-containing monomer as a monomer unit.
  • the pressure-sensitive adhesive layer for an optical film of the present invention is preferably formed from the pressure-sensitive adhesive composition for an optical film.
  • the pressure-sensitive adhesive layer-attached optical film of the present invention preferably has the pressure-sensitive adhesive layer for an optical film on at least one surface of the optical film.
  • the pressure-sensitive adhesive layer for an optical film formed by the pressure-sensitive adhesive composition for an optical film of the present invention in a state of being attached to the optical film, even when exposed to heating and humidifying conditions, such as foaming and peeling. Generation is suppressed, and high adhesion reliability, reworkability, and durability (heat resistance, moisture resistance, peeling resistance) are obtained, which is useful. Further, even when the pressure-sensitive adhesive layer-attached optical film using the pressure-sensitive adhesive layer for an optical film is also exposed to heating and humidifying conditions, it is possible to suppress display unevenness due to foaming or peeling, which is useful. ..
  • the pressure-sensitive adhesive composition for an optical film of the present invention contains a (meth)acrylic polymer, and the (meth)acrylic polymer has, as a monomer unit, an amide group-containing monomer, and an alkoxy group-containing alkyl(meth)acrylate. And the alkoxy group-containing alkyl (meth)acrylate is contained in an amount of 20 to 80% by mass based on 100% by mass of the total amount of monomer units constituting the (meth)acrylic polymer.
  • (meth)acrylate means acrylate and/or methacrylate, and (meth) of the present invention has the same meaning.
  • the alkoxy group-containing alkyl(meth)acrylate is not particularly limited, but examples thereof include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, methoxytriethylene glycol acrylate, 3-methoxypropyl acrylate, and acrylic acid 3 -Ethoxypropyl, 4-methoxybutyl acrylate, 4-ethoxybutyl acrylate and the like can be mentioned.
  • the alkoxy group-containing alkyl (meth)acrylate can be used alone or in combination of two or more kinds.
  • the alkoxy group-containing alkyl (meth)acrylate is contained in an amount of 20 to 80% by mass, preferably 22 to 80% by mass, and more preferably 100% by mass of the total monomer units constituting the (meth)acrylic polymer. Is 25 to 78% by mass, more preferably 25 to 75% by mass, particularly preferably 35 to 75% by mass, and most preferably 50 to 75% by mass.
  • content of the alkoxy group-containing monomer is less than 20% by mass, reworkability and durability (heat resistance, moisture resistance, peeling resistance) are insufficient.
  • it exceeds 80% by mass the moisture content of the pressure-sensitive adhesive becomes high and the foaming resistance becomes insufficient.
  • the amide group-containing monomer is preferably a compound containing an amide group in its structure and a polymerizable unsaturated double bond such as a (meth)acryloyl group or a vinyl group.
  • the amide group-containing monomer is not particularly limited, and examples thereof include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropylacrylamide, N-methyl(meth) ) Acrylamide, N-butyl(meth)acrylamide, N-hexyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methylol-N-propane(meth)acrylamide, aminomethyl(meth)acrylamide, aminoethyl(meth) ) Acrylamide-based monomers such as acrylamide, mercaptomethyl(meth)acrylamide, mercaptoethyl(meth)acrylamide; N-(meth)acryl
  • N-vinyl group-containing lactam monomers such as N-vinylpyrrolidone and N-vinyl- ⁇ -caprolactam.
  • the amide group-containing monomer is preferable for satisfying the durability, and among the amide group-containing monomers, the N-vinyl group-containing lactam monomer is particularly preferable for satisfying the durability and reworkability.
  • the amide group-containing monomer is preferably contained in an amount of 0.1 to 15% by mass, more preferably 0.3 to 12% by mass, based on 100% by mass of the total amount of monomer units constituting the (meth)acrylic polymer. %, more preferably 0.5 to 10% by mass, particularly preferably 0.9 to 7% by mass, and most preferably 0.9 to 3% by mass. If the mass ratio of the amide group-containing monomer (particularly, the N-vinyl group-containing lactam monomer) is within the above range, reworkability and durability (heat resistance, moisture resistance, peeling resistance) can be particularly satisfied. .. If it exceeds 15% by mass, it is not preferable from the viewpoint of reworkability.
  • the pressure-sensitive adhesive composition for an optical film of the present invention is a pressure-sensitive adhesive composition for an optical film containing a (meth)acrylic polymer and a crosslinking agent, and the (meth)acrylic polymer is an amide group as a monomer unit. 20 to 80 of the alkoxy group-containing alkyl (meth)acrylate based on 100% by mass of the total amount of the monomer units containing the monomer and the alkoxy group-containing alkyl (meth)acrylate, which constitutes the (meth)acrylic polymer.
  • the content of the amide group-containing monomer, and the amount of the alkoxy group-containing alkyl (meth) acrylate are 100% by mass of the total amount of monomer units constituting the (meth) acrylic polymer.
  • the amide group-containing monomer is contained in an amount of 0.9 to 3% by mass
  • the alkoxy group-containing alkyl (meth)acrylate is contained in an amount of 35 to 75% by mass, based on 100% by mass of the total amount of the monomer units.
  • the adhesiveness can be improved without using the carboxyl group-containing monomer that contributes to the improved adhesiveness, and the durability is improved. It has excellent properties (heat resistance, moisture resistance, peeling resistance) and reworkability, and is a preferred embodiment.
  • the adhesiveness is further improved and the reworkability is excellent, and in addition to this, a monomer having an acidic functional group such as a carboxyl group-containing monomer is not used.
  • the metal corrosion resistance (for example, the ITO corrosion resistance when ITO is used for the adherend) is excellent, which is a preferred embodiment.
  • the (meth)acrylic polymer preferably contains an alkyl (meth)acrylate as a monomer unit in addition to the amide group-containing monomer and the alkoxy group-containing alkyl (meth)acrylate.
  • alkyl (meth)acrylate include linear or branched alkyl groups having 1 to 18 carbon atoms.
  • alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, hexyl group, cyclohexyl group, heptyl group, 2-ethylhexyl group, isooctyl group, nonyl group, decyl group.
  • Examples thereof include a group, an isodecyl group, a dodecyl group, an isomyristyl group, a lauryl group, a tridecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group. These can be used alone or in combination.
  • the average carbon number of these alkyl groups is preferably 3-9.
  • the alkyl (meth)acrylate is preferably contained in an amount of 1 to 75% by mass, more preferably 3 to 70% by mass, based on 100% by mass of the total amount of monomer units constituting the (meth)acrylic polymer. It is preferably 5 to 65 mass %. It is preferable to set the mass ratio of the alkyl (meth)acrylate within the above range in order to secure the adhesiveness.
  • the (meth)acrylic polymer contains a hydroxyl group-containing monomer as a monomer unit.
  • the hydroxyl group-containing monomer is preferably a compound containing a hydroxyl group in its structure and a polymerizable unsaturated double bond such as a (meth)acryloyl group or a vinyl group.
  • hydroxyl group-containing monomer examples include, for example, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate and 8- Examples thereof include hydroxyalkyl (meth)acrylates such as hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, and 12-hydroxylauryl (meth)acrylate, and (4-hydroxymethylcyclohexyl)-methyl acrylate.
  • 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferable, and 4-hydroxybutyl (meth)acrylate is particularly preferable, from the viewpoint of durability.
  • the amount of the hydroxyl group-containing monomer is preferably 0.01 to 7% by mass, more preferably 0.1 to 5% by mass, based on 100% by mass of the total amount of monomer units constituting the (meth)acrylic polymer. %, and more preferably 0.3 to 3% by mass.
  • the mass ratio of the hydroxyl group-containing monomer is less than 0.01% by mass, the pressure-sensitive adhesive layer may be insufficiently crosslinked, and durability and adhesive properties may not be satisfied. On the other hand, when it exceeds 7% by mass, durability May not be satisfied.
  • the hydroxyl group-containing monomer is highly reactive with the intermolecular cross-linking agent, and thus is preferably used from the viewpoints of improving the cohesiveness and heat resistance of the obtained pressure-sensitive adhesive layer and reworkability.
  • the (meth)acrylic polymer contains an aromatic ring-containing monomer as a monomer unit.
  • the aromatic ring-containing monomer is preferably a compound containing an aromatic ring structure in its structure and a (meth)acryloyl group (hereinafter sometimes referred to as aromatic ring-containing (meth)acrylate).
  • the aromatic ring include a benzene ring, a naphthalene ring and a biphenyl ring.
  • the aromatic ring-containing monomer satisfies durability and can improve display unevenness due to light leakage.
  • aromatic ring-containing monomer examples include styrene, p-tert-butoxystyrene, and p-acetoxystyrene.
  • aromatic ring-containing (meth)acrylate examples include benzyl (meth)acrylate, phenyl (meth)acrylate, o-phenylphenol (meth)acrylate phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxy.
  • aromatic ring-containing (meth)acrylate benzyl (meth)acrylate and phenoxyethyl (meth)acrylate are preferable, and phenoxyethyl (meth)acrylate is particularly preferable, from the viewpoint of adhesive properties and durability.
  • the aromatic ring-containing monomer is preferably 3 to 25% by mass, more preferably 8 to 22% by mass, and still more preferably 12% based on 100% by mass of the total amount of monomer units constituting the (meth)acrylic polymer. It is up to 20% by mass.
  • the mass ratio of the aromatic ring-containing monomer is within the above range, display unevenness due to light leakage can be sufficiently suppressed and durability is excellent, which is preferable.
  • the mass ratio of the aromatic ring-containing monomer exceeds 25 mass %, display unevenness is rather suppressed, and the durability is lowered.
  • the (meth)acrylic polymer may contain a carboxyl group-containing monomer in an amount of generally 0.3% by mass or less as a monomer unit. When containing the carboxyl group-containing monomer, it can be expected to improve the adhesiveness, but it may not be able to satisfy the metal corrosion resistance (for example, ITO corrosion resistance) required when sticking to ITO. It is preferable that the (meth)acrylic polymer does not contain a carboxyl group-containing monomer as a monomer unit.
  • the carboxyl group-containing monomer includes a carboxyl group in its structure, and a (meth)acryloyl group
  • vinyl A compound having a polymerizable unsaturated double bond such as a group is preferable.
  • Specific examples of the carboxyl group-containing monomer include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like.
  • carboxyl group-containing monomers acrylic acid is preferable from the viewpoint of copolymerizability, price, and adhesive property. If a small amount of the above-mentioned carboxyl group-containing monomer is used, it is possible to suppress an increase in adhesive strength over time and improve adhesion. When the carboxyl group-containing monomer is used, it is preferably applied to applications where metal corrosion resistance is not required.
  • the (meth)acrylic polymer in addition to the monomer unit, it is not particularly necessary to contain another monomer unit, but for the purpose of improving adhesiveness and heat resistance, a (meth)acryloyl group
  • one or more copolymerizable monomers having a polymerizable functional group having an unsaturated double bond such as a vinyl group can be introduced by copolymerization.
  • Such a copolymerization monomer include acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; caprolactone adducts of acrylic acid; allylsulfonic acid, 2-(meth)acrylamido-2-methylpropane.
  • acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride
  • caprolactone adducts of acrylic acid allylsulfonic acid, 2-(meth)acrylamido-2-methylpropane.
  • examples thereof include sulfonic acid group-containing monomers such as sulfonic acid, (meth)acrylamide propane sulfonic acid, and sulfopropyl (meth)acrylate; and phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate.
  • alkylaminoalkyl(meth)acrylates such as aminoethyl(meth)acrylate, N,N-dimethylaminoethyl(meth)acrylate, t-butylaminoethyl(meth)acrylate; methoxyethyl(meth)acrylate, ethoxyethyl( Alkoxyalkyl (meth)acrylates such as (meth)acrylate; N-(meth)acryloyloxymethylenesuccinimide, N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, N-(meth)acryloyl-8-oxyoctamethylenesuccinimide, etc.
  • Succinimide-based monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide and N-phenylmaleimide; N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N- Itaconic imide-based monomers such as octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl itaconimide, N-lauryl itaconimide and the like are also mentioned as examples of monomers for modification.
  • vinyl monomers such as vinyl acetate and vinyl propionate; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate; polyethylene glycol (meth).
  • Glycol-based (meth)acrylates such as acrylate, polypropylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate; tetrahydrofurfuryl (meth)acrylate, fluorine (meth)acrylate, silicone (meth) ) Acrylate and (meth)acrylate monomers such as 2-methoxyethyl acrylate can also be used. Further, isoprene, butadiene, isobutylene, vinyl ether and the like can be mentioned.
  • examples of copolymerizable monomers other than the above include silane-based monomers containing a silicon atom.
  • examples of the silane-based monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane.
  • the copolymerization monomer tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neo Pentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate , Polyfunctional having two or more unsaturated double bonds such as (meth)acryloyl groups and vinyl groups such as esterification products of (meth)acrylic acid such as caprolactone-modified dipentaerythritol hexa(meth)acrylate
  • the copolymerizable monomer is preferably about 0 to 10% by mass, more preferably about 0 to 7% by mass, based on 100% by mass of the total amount of monomer units constituting the (meth)acrylic polymer. More preferably, it is about 0 to 5% by mass.
  • the weight average molecular weight (Mw) of the (meth)acrylic polymer is preferably 900,000 to 3,000,000, and the weight average molecular weight is more preferably 1,000,000 to 2.8,000,000 in consideration of durability, particularly heat resistance. , 1.2 to 2.6 million are more preferable, and 1.4 to 2.4 million are particularly preferable.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) is less than 900,000, the amount of low molecular weight polymer components increases, and the crosslink density of the gel (adhesive layer) increases, which causes the adhesive layer to become hard and stress relaxation. Is deteriorated, which is not preferable. Further, if the weight average molecular weight is more than 3,000,000, the viscosity is increased and gelation occurs during polymerization of the polymer, which is not preferable.
  • the polydispersity (molecular weight distribution, weight average molecular weight (Mw)/number average molecular weight (Mn)) of the (meth)acrylic polymer is preferably 6 or less, more preferably 2.5 to 5.5. Yes, and more preferably 3-5.
  • Mw/Mn weight average molecular weight
  • a cross-linking agent to increase the gel fraction of the pressure-sensitive adhesive layer. Excessive cross-linking agent reacts with the gelled polymer to increase the cross-linking density of the gel (pressure-sensitive adhesive layer), which causes the pressure-sensitive adhesive layer to become hard and impairs stress relaxation, which is not preferable.
  • the pressure-sensitive adhesive layer may be segregated near the pressure-sensitive adhesive layer interface that is in contact with the adherend. It is presumed that a fragile layer is formed inside, but when the pressure-sensitive adhesive layer is exposed to a heated/humidified environment, the pressure-sensitive adhesive layer is destroyed in the vicinity of the fragile layer and peels off the pressure-sensitive adhesive layer. It is presumed that this may cause the above problem. Therefore, the polydispersity (Mw/Mn) is preferably adjusted to 6 or less. The weight average molecular weight (Mw) and the polydispersity (Mw/Mn) are obtained from the values calculated by polystyrene measurement by GPC (gel permeation chromatography).
  • the production of such a (meth)acrylic polymer can be appropriately selected from known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerization. Among them, solution polymerization is easy and versatile. preferable. Further, the (meth)acrylic polymer obtained may be any of a random copolymer, a block copolymer, a graft copolymer and the like.
  • solution polymerization ethyl acetate, toluene, etc. are used as a polymerization solvent.
  • the reaction is usually carried out under a flow of an inert gas such as nitrogen and a polymerization initiator at about 50 to 70° C. for about 10 minutes to 30 hours.
  • an inert gas such as nitrogen
  • a polymerization initiator at about 50 to 70° C. for about 10 minutes to 30 hours.
  • the polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited and can be appropriately selected and used.
  • the weight average molecular weight of the (meth)acrylic polymer can be controlled by the amount of the polymerization initiator and the chain transfer agent used and the reaction conditions, and the amount used is appropriately adjusted depending on the types of these.
  • polymerization initiator examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-amidinopropane)dihydrochloride, 2,2′-azobis[2-(5-methyl-2) -Imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine)disulfate, 2,2'-azobis(N,N'-dimethyleneisobutylamidine),2,2 '-Azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate (VA-057 manufactured by Wako Pure Chemical Industries, Ltd.) and other azo initiators, potassium persulfate, ammonium persulfate and other persulfates , Di(2-ethylhexyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate
  • the above polymerization initiators may be used alone or in combination of two or more, but the total content is 0.005 to 100 parts by mass based on 100 parts by mass of the total amount of the monomer components.
  • the amount is preferably about 1 part by mass, more preferably about 0.02 to 0.5 part by mass.
  • the polymerization initiator is used as the polymerization initiator to produce a (meth)acrylic polymer having the weight average molecular weight (Mw) and the polydispersity (Mw/Mn).
  • Mw weight average molecular weight
  • Mw/Mn polydispersity
  • the amount of the polymerization initiator used is preferably about 0.06 to 0.2 parts by mass, and more preferably 0.08 to 0.175 parts by mass, based on 100 parts by mass of the total amount of the monomer components. It is preferably about the same.
  • chain transfer agent examples include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol.
  • the chain transfer agent may be used alone or in combination of two or more, but the total content is 0.1 parts by mass with respect to 100 parts by mass of the total amount of the monomer components. It is below the level.
  • emulsifier used in the case of emulsion polymerization for example, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate, anionic emulsifiers such as sodium polyoxyethylene alkylphenyl ether sulfate, polyoxy Examples thereof include nonionic emulsifiers such as ethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene-polyoxypropylene block polymer. These emulsifiers may be used alone or in combination of two or more kinds.
  • a reactive emulsifier having a radically polymerizable functional group such as a propenyl group or an allyl ether group introduced therein can be used, and specifically, Aqualon HS-10, HS-20, KH-10, Examples include BC-05, BC-10, BC-20 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and ADEKA REASOAP SE10N (manufactured by Asahi Denka Co., Ltd.). Since the reactive emulsifier is incorporated into the polymer chain after the polymerization, the water resistance is improved, which is preferable.
  • the amount of the emulsifier used is preferably 0.3 to 5 parts by mass, more preferably 0.5 to 1 part by mass, based on 100 parts by mass of the total amount of the monomer components, and polymerization stability and mechanical stability.
  • the pressure-sensitive adhesive composition for an optical film of the present invention is characterized by containing a crosslinking agent, preferably an isocyanate crosslinking agent and/or a peroxide crosslinking agent, more preferably an isocyanate crosslinking agent and a peroxide crosslinking agent. That is, an oxide-based crosslinking agent is used in combination.
  • a crosslinking agent preferably an isocyanate crosslinking agent and/or a peroxide crosslinking agent, more preferably an isocyanate crosslinking agent and a peroxide crosslinking agent. That is, an oxide-based crosslinking agent is used in combination.
  • the use of a peroxide-based cross-linking agent makes it difficult to peel off, which is a preferred embodiment.
  • the isocyanate-based crosslinking agent is used alone, it takes time to crosslink the pressure-sensitive adhesive and the productivity may be reduced.
  • the isocyanate cross-linking agent a compound having at least two isocyanate groups can be used.
  • known aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates and the like which are generally used for urethanization reaction are used.
  • aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4- Examples include trimethylhexamethylene diisocyanate.
  • Examples of the alicyclic isocyanate include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate. Examples thereof include hydrogenated tetramethylxylylene diisocyanate.
  • aromatic diisocyanate examples include phenylene diisocyanate, 2,4-tolylene diisosonate, 2,6-tolylene diisosonate, 2,2′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4, 4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate and the like can be mentioned.
  • Examples of the isocyanate-based cross-linking agent include multimers of the diisocyanate (dimers, trimers, pentamers, etc.), urethane modified products reacted with polyhydric alcohols such as trimethylolpropane, urea modified products, Examples include biuret modified products, alphanate modified products, isocyanurate modified products, and carbodiimide modified products.
  • Examples of commercially available products of the isocyanate-based cross-linking agent include, for example, trade names “Millionate MT”, “Millionate MTL”, “Millionate MR-200”, “Millionate MR-400”, “Coronate L”, “Coronate HL”, “Coronate HX” [above, Tosoh Corporation]; Trade name “Takenate D-110N” "Takenate D-120N” "Takenate D-140N” "Takenate D-160N” "Takenate D-165N” "Takenate D-170HN” "Takenate D-178N” " Takenate 500, Takenate 600 [above, Mitsui Chemicals, Inc.]; and the like. These compounds may be used alone or in combination of two or more.
  • aliphatic polyisocyanate and its modified aliphatic polyisocyanate compound are preferable.
  • the aliphatic polyisocyanate-based compound has a more flexible cross-linking structure than other isocyanate-based cross-linking agents, easily relaxes the stress associated with the expansion/contraction of the optical film, and is less likely to peel off in the durability test.
  • the aliphatic polyisocyanate compound hexamethylene diisocyanate and its modified products are particularly preferable.
  • the peroxide-based cross-linking agent (may be simply referred to as a peroxide) is a base polymer ((meth)acrylic polymer) of the pressure-sensitive adhesive composition that generates radical active species by heating or light irradiation. Any compound can be used as long as it promotes crosslinking, but in consideration of workability and stability, it is preferable to use a peroxide having a 1-minute half-life temperature of 80 to 160° C. It is more preferred to use a peroxide which is 140°C.
  • peroxides examples include di(2-ethylhexyl)peroxydicarbonate (1 minute half-life temperature: 90.6° C.), di(4-t-butylcyclohexyl)peroxydicarbonate (1 Minute half-life temperature: 92.1° C.), di-sec-butyl peroxydicarbonate (1 minute half-life temperature: 92.4° C.), t-butyl peroxy neodecanoate (1 minute half-life temperature: 103 0.5° C.), t-hexyl peroxypivalate (1 minute half-life temperature: 109.1° C.), t-butyl peroxypivalate (1 minute half-life temperature: 110.3° C.), dilauroyl peroxide ( 1-minute half-life temperature: 116.4°C), di-n-octanoyl peroxide (1-minute half-life temperature: 117.4°C), 1,1,3,3-tetramethylbutylperoxy-2-ethy
  • the half-life of peroxide is an index showing the decomposition rate of peroxide, and means the time until the residual amount of peroxide is halved.
  • the decomposition temperature for obtaining a half-life at an arbitrary time and the half-life time at an arbitrary temperature are described in the manufacturer's catalog and the like. (May 2003)” and the like.
  • HPLC high performance liquid chromatography
  • each of the pressure-sensitive adhesive composition after the reaction treatment is taken out, immersed in 10 mL of ethyl acetate, shake-extracted at 120 rpm for 3 hours at 25° C. with a shaker, and then at room temperature. Let stand for 3 days. Then, 10 mL of acetonitrile was added, and the mixture was shaken at 120 rpm for 30 minutes at 25° C., and about 10 ⁇ L of the extract obtained by filtering with a membrane filter (0.45 ⁇ m) was injected into HPLC for analysis, and after the reaction treatment, It can be the amount of peroxide.
  • the amount of the cross-linking agent used is preferably 0.01 to 3 parts by mass, more preferably 0.03 to 2 parts by mass, and still more preferably 0.05 to 100 parts by mass with respect to 100 parts by mass of the (meth)acrylic polymer. 1 part by mass is preferable. If the amount of the cross-linking agent is less than 0.01 parts by mass, the pressure-sensitive adhesive layer may be insufficiently cross-linked, and durability and adhesive properties may not be satisfied, while if it is more than 3 parts by mass, the pressure-sensitive adhesive layer may be too hard. The durability tends to decrease.
  • the blending ratio of the isocyanate crosslinking agent and the peroxide crosslinking agent is preferably 0:100 to 50:50, and more preferably 0:100 to 40:60. preferable.
  • the pressure-sensitive adhesive composition for an optical film of the present invention may contain a silane coupling agent.
  • the durability can be improved by using the silane coupling agent.
  • the silane coupling agent include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3, Epoxy group-containing silane coupling agent such as 4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl- Amino group-containing silane coupling agents such as N-(1,3-dimethylbutylidene)propylamine, N-phenyl- ⁇ -aminopropyltrimethoxysilane, 3-acryloxypropyltri
  • silane coupling agent one having a plurality of alkoxysilyl groups in the molecule can be used.
  • a silane coupling agent having a plurality of alkoxysilyl groups in these molecules is difficult to volatilize, and is effective in improving durability because it has a plurality of alkoxysilyl groups, and thus is preferable.
  • the silane coupling agent having a plurality of alkoxysilyl groups in the molecule preferably has an epoxy group in the molecule, and more preferably has a plurality of epoxy groups in the molecule.
  • a silane coupling agent having a plurality of alkoxysilyl groups in the molecule and an epoxy group tends to have good durability.
  • Specific examples of the silane coupling agent having a plurality of alkoxysilyl groups in the molecule and having an epoxy group include X-41-1053, X-41-1059A and X-41-1056 manufactured by Shin-Etsu Chemical Co., Ltd. In particular, X-41-1056 manufactured by Shin-Etsu Chemical Co., which has a high epoxy group content, is preferable.
  • the silane coupling agent may be used alone, or two or more kinds may be mixed and used, but the total content is 100 parts by mass of the (meth)acrylic polymer, and
  • the silane coupling agent is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 1 part by mass, further preferably 0.02 to 1 part by mass, particularly preferably 0.05 to 0.6 part by mass.
  • the amount is preferably such that the durability is improved and the adhesive force to glass or the like is appropriately maintained.
  • the pressure-sensitive adhesive composition for an optical film may contain other known additives within a range that does not impair the properties, for example, an antistatic agent (ionic liquid or an ion such as an alkali metal salt).
  • an antistatic agent ionic liquid or an ion such as an alkali metal salt.
  • Compounds), colorants, powders such as pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, antioxidants, light stabilizers, ultraviolet rays Absorbents, polymerization inhibitors, inorganic or organic fillers, metal powders, particles, foils and the like can be appropriately added depending on the intended use.
  • a redox system to which a reducing agent is added may be adopted within a controllable range.
  • These additives are preferably used in an amount of 5 parts by mass or less, more preferably 3 parts by mass or less, and further preferably 1 part by mass or less with respect to 100 parts by mass
  • a pressure-sensitive adhesive layer for an optical film can be formed, and in forming the pressure-sensitive adhesive layer, the crosslinking agent temperature and the crosslinking treatment time can be adjusted together with the amount of the crosslinking agent used. It is preferable to fully consider the effect of.
  • ⁇ Crosslinking temperature and crosslinking time can be adjusted depending on the crosslinking agent used.
  • the crosslinking treatment temperature is preferably 170° C. or lower.
  • the cross-linking treatment may be carried out at the temperature during the drying step of the pressure-sensitive adhesive layer, or a separate cross-linking treatment step may be provided after the drying step.
  • the cross-linking treatment time can be set in consideration of productivity and workability, but is usually about 0.2 to 20 minutes, preferably about 0.5 to 10 minutes.
  • the pressure-sensitive adhesive layer-carrying optical film of the present invention is preferably one in which the pressure-sensitive adhesive layer for an optical film is formed on at least one side of an optical film.
  • the pressure-sensitive adhesive layer-attached optical film using the pressure-sensitive adhesive layer for an optical film is useful because it can suppress display unevenness due to foaming or peeling even when exposed to heating/humidifying conditions.
  • a polarizing film polarizing plate
  • a retardation film an optical compensation film
  • a brightness enhancement film or a laminate of these may be used as the optical film.
  • a method for forming a pressure-sensitive adhesive layer for example, a method of applying the pressure-sensitive adhesive composition to a release-treated separator or the like, and transferring it to an optical film after forming a pressure-sensitive adhesive layer by drying and removing a polymerization solvent, or the like, or It is prepared by a method of applying the pressure-sensitive adhesive composition to an optical film, drying and removing a polymerization solvent and the like to form a pressure-sensitive adhesive layer on the optical film.
  • one or more solvents other than the polymerization solvent may be newly added as appropriate.
  • a silicone release liner is preferably used as the release-treated separator.
  • a method for drying the pressure-sensitive adhesive an appropriate method is appropriately adopted depending on the purpose. obtain.
  • a method of heating and drying a film coated with the pressure-sensitive adhesive composition (coating film) is used.
  • the heating and drying temperature is preferably 40 to 200° C., more preferably 50 to 180° C., and particularly preferably 70 to 170° C. By setting the heating temperature in the above range, a pressure-sensitive adhesive having excellent pressure-sensitive adhesive properties can be obtained.
  • the drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.
  • an adhesive layer can be formed on the surface of the optical film after forming an anchor layer or performing various types of easy-adhesion treatment such as corona treatment and plasma treatment. Further, the surface of the pressure-sensitive adhesive layer may be subjected to easy adhesion treatment.
  • Various methods are used for forming the pressure-sensitive adhesive layer. Specifically, for example, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples of the method include an extrusion coating method.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited and is, for example, about 1 to 100 ⁇ m.
  • the thickness is preferably 2 to 50 ⁇ m, more preferably 2 to 40 ⁇ m, and further preferably 5 to 35 ⁇ m.
  • the pressure-sensitive adhesive layer When the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a release-treated sheet (separator) until practical use.
  • constituent material of the separator examples include plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and non-woven fabric, nets, foam sheets, metal foils, and laminates thereof.
  • suitable thin leaves include plastic films, but plastic films are preferably used because of their excellent surface smoothness.
  • the plastic film is not particularly limited as long as it is a film capable of protecting the pressure-sensitive adhesive layer, and examples thereof include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, and vinyl chloride. Examples thereof include polymer films, polyethylene terephthalate films, polybutylene terephthalate films, polyurethane films, ethylene-vinyl acetate copolymer films and the like.
  • the thickness of the separator is usually 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
  • a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, release and antifouling treatment with silica powder or the like, coating type, kneading type, vapor deposition type It is also possible to perform antistatic treatment such as. Particularly, by appropriately performing a peeling treatment such as a silicone treatment, a long-chain alkyl treatment, or a fluorine treatment on the surface of the separator, the peelability from the pressure-sensitive adhesive layer can be further enhanced.
  • release-treated sheet used in the production of the pressure-sensitive adhesive layer-carrying optical film can be used as it is as a separator for the pressure-sensitive adhesive layer-carrying optical film, and the process can be simplified.
  • the optical film one used for forming an image display device such as a liquid crystal display device is used, and the type thereof is not particularly limited.
  • the optical film may be a polarizing film.
  • the polarizing film may include a polarizer and have a transparent protective film on one side or both sides of the polarizer.
  • the polarizer is not particularly limited, and various types can be used.
  • the polarizer include hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene/vinyl acetate copolymer partially saponified films, and dichroic dyes such as iodine and dichroic dyes.
  • hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene/vinyl acetate copolymer partially saponified films
  • dichroic dyes such as iodine and dichroic dyes.
  • examples thereof include polyene-oriented films in which substances are adsorbed and uniaxially stretched, polyvinyl alcohol dehydration products, polyvinyl chloride dehydrochlorination products, and the like.
  • a polarizer made of a polyvinyl alcohol-based film and a dichroic material such as iodine is preferable.
  • a uniaxially stretched polarizer obtained by dyeing a polyvinyl alcohol film with iodine can be produced, for example, by dyeing a polyvinyl alcohol film by immersing it in an aqueous solution of iodine and stretching it 3 to 7 times its original length. it can. If necessary, it can be immersed in an aqueous solution of potassium iodide or the like which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed with water before dyeing.
  • Stretching may be performed after dyeing with iodine, stretching while dyeing, or stretching and then dyeing with iodine. Stretching can be carried out in an aqueous solution of boric acid or potassium iodide or in a water bath.
  • the thickness of the polarizer is preferably 5 to 40 ⁇ m. From the viewpoint of thinning, the thickness is more preferably 30 ⁇ m or less, further preferably 25 ⁇ m or less. Such a thin polarizer has little thickness unevenness, excellent visibility, and little dimensional change, and therefore has excellent durability even under heating/humidifying conditions, and is less likely to cause foaming or peeling. It is preferable that the polarizing film can be thinned.
  • the thin polarizer typically, JP-A-51-0696644, JP-A-2000-338329, WO 2010/100917 pamphlet, PCT/JP2010/001460, or Japanese Patent Application No. 2010- Examples thereof include thin polarizing films described in Japanese Patent No. 269002 and Japanese Patent Application No. 2010-263692.
  • These thin polarizing films can be obtained by a production method including a step of stretching a polyvinyl alcohol-based resin (hereinafter, also referred to as PVA-based resin) layer and a stretching resin base material in a laminate state and a dyeing step. According to this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched without trouble such as breakage due to stretching because it is supported by the stretching resin base material.
  • PVA-based resin polyvinyl alcohol-based resin
  • WO 2010/100917 pamphlet As the thin polarizing film, among manufacturing methods including a step of stretching in a laminate state and a step of dyeing, WO 2010/100917 pamphlet, PCT/PCT/ Those obtained by a process including a step of stretching in an aqueous solution of boric acid as described in JP 2010/001460, or Japanese Patent Application Nos. 2010-269002 and 2010-263692 are preferable, and particularly preferable. What is obtained by the production method described in Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692, which includes a step of auxiliary stretching in air before stretching in a boric acid aqueous solution is preferable.
  • thermoplastic resin having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropic property, etc.
  • a thermoplastic resin having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropic property, etc.
  • thermoplastic resin include cellulose resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth)acrylic resins, and cyclic resins.
  • examples thereof include polyolefin resins (norbornene-based resins), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof.
  • a transparent protective film is attached to one side of the polarizer with an adhesive layer, while a transparent protective film is attached to the other side as a (meth)acrylic type, urethane type, acrylic urethane type, epoxy type, silicone type.
  • a thermosetting resin such as a system or an ultraviolet curable resin can be used.
  • One or more kinds of any appropriate additive may be contained in the transparent protective film. Examples of the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a release agent, an anti-coloring agent, a flame retardant, a nucleating agent, an antistatic agent, a pigment and a coloring agent.
  • the content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by mass, more preferably 50 to 99% by mass, further preferably 60 to 98% by mass, and particularly preferably 70 to 97% by mass. ..
  • the content of the thermoplastic resin in the transparent protective film is less than 50% by mass, the high transparency and other properties inherent in the thermoplastic resin may not be sufficiently exhibited.
  • the adhesive used for laminating the polarizer and the transparent protective film is not particularly limited as long as it is optically transparent, and various types of water-based, solvent-based, hot-melt-based, radical-curable and cation-curable types are used. However, a water-based adhesive or a radical curable adhesive is preferable.
  • an optical film for example, a liquid crystal display device such as a reflection plate, an anti-transmission plate, a retardation film (including a wavelength plate such as 1/2 or 1/4), a visual compensation film, a brightness enhancement film, etc.
  • a liquid crystal display device such as a reflection plate, an anti-transmission plate, a retardation film (including a wavelength plate such as 1/2 or 1/4), a visual compensation film, a brightness enhancement film, etc.
  • a liquid crystal display device such as a reflection plate, an anti-transmission plate, a retardation film (including a wavelength plate such as 1/2 or 1/4), a visual compensation film, a brightness enhancement film, etc.
  • a retardation film including a wavelength plate such as 1/2 or 1/4
  • a visual compensation film such as 1/2 or 1/4
  • the optical film obtained by laminating the optical layer on the polarizing film can be formed by a method of sequentially laminating separately in the manufacturing process of a liquid crystal display device or the like. It is excellent in stability and assembling work and has an advantage that the manufacturing process of a liquid crystal display device can be improved.
  • Appropriate adhesion means such as an adhesive layer may be used for lamination. When the polarizing film and other optical layers are adhered, their optical axes can be arranged at appropriate angles depending on the intended retardation characteristics and the like.
  • the pressure-sensitive adhesive layer-attached optical film of the present invention can be preferably used for forming various image display devices such as liquid crystal display devices.
  • the liquid crystal display device can be formed in a conventional manner. That is, a liquid crystal display device is generally formed by appropriately assembling a display panel such as a liquid crystal cell and an optical film with an adhesive layer, and optionally a component such as a lighting system and incorporating a drive circuit, In the present invention, there is no particular limitation except that the pressure-sensitive adhesive layer-carrying optical film according to the present invention is used, and the conventional method can be applied.
  • the liquid crystal cell may be of any type such as TN type, STN type, ⁇ type, VA type, and IPS type.
  • liquid crystal display device in which an optical film with an adhesive layer is arranged on one side or both sides of a display panel such as a liquid crystal cell, or a suitable liquid crystal display device such as one using a backlight or a reflector for an illumination system. ..
  • the pressure-sensitive adhesive layer-carrying optical film according to the present invention can be installed on one side or both sides of a display panel such as a liquid crystal cell.
  • optical films are provided on both sides, they may be the same or different.
  • a diffusion layer for example, a diffusion layer, an anti-glare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusion sheet, a back light, and other appropriate components are provided at appropriate positions in one layer or Two or more layers can be arranged.
  • ⁇ Analyzer HLC-8120GPC manufactured by Tosoh Corporation ⁇ Column: Tosoh Corp., G7000H XL + GMH XL + GMH XL ⁇ Column size: 7.8mm ⁇ 30cm each, 90cm in total ⁇ Column temperature: 40°C ⁇ Flow rate: 0.8 mL/min ⁇ Injection volume: 100 ⁇ L ⁇ Eluent: Tetrahydrofuran ⁇ Detector: Differential refractometer (RI) ⁇ Standard sample: polystyrene
  • a polyvinyl alcohol film having a thickness of 60 ⁇ m was stretched up to 3 times while being dyed in a 0.3% concentration iodine solution at 30° C. for 1 minute between rolls having different speed ratios. Then, while being immersed in an aqueous solution containing boric acid having a concentration of 4% and potassium iodide having a concentration of 10% at 60° C. for 0.5 minutes, it was stretched to a total stretching ratio of 6 times. Then, the plate was washed by dipping it in an aqueous solution containing potassium iodide having a concentration of 1.5% at 30° C. for 10 seconds, and then dried at 50° C.
  • polarizer having a thickness of 22 ⁇ m.
  • a saponified 40 ⁇ m thick triacetyl cellulose (TAC) film was attached to both sides of the polarizer with a polyvinyl alcohol-based adhesive to form a polarizing film (polarizing plate).
  • TAC triacetyl cellulose
  • Example 1 (Preparation of (meth)acrylic polymer (A1)) In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a condenser, 2-methoxyethyl acrylate 20 parts, butyl acrylate 62.1 parts, 4-hydroxybutyl acrylate 1 part, phenoxyethyl acrylate 16 Part, a monomer mixture containing 0.9 part of N-vinyl-pyrrolidone.
  • Example 2 to 10 and Comparative Examples 1 to 4 In Examples 2 to 10 and Comparative Examples 1 to 4, as in Example 1, as shown in Table 1, the types of monomers and the usage ratios thereof were changed, and the production conditions were controlled. Solutions of the (meth)acrylic polymers (A2) to (A12) having the polymer properties shown (weight average molecular weight (Mw) and polydispersity (Mw/Mn)) were prepared. Further, for each of the obtained (meth)acrylic polymer solutions, as shown in Table 1, in the same manner as in Example 1, a solution of the acrylic pressure-sensitive adhesive composition was prepared. The same amounts as in Example 1 were used for the polymerization initiator and the silane coupling agent, which are not shown in the table for their compounding amounts. Furthermore, using the solution of the acrylic pressure-sensitive adhesive composition, as shown in Table 1, a polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1.
  • the sample subjected to such treatment is subjected to treatment for 500 hours in each atmosphere of 105° C. and 65° C. ⁇ 95% RH, and then, between the polarizing film, the ITO glass and the alkali-free glass.
  • the appearance was visually evaluated according to the following criteria. (Evaluation criteria) ⁇ : No change in appearance such as foaming or peeling. There is no problem in practical use. ⁇ : Peeling or foaming at the end, although slightly, but practically no problem. ⁇ : There is peeling or foaming at the end, but there is no practical problem unless it is used for a special purpose. X: Peeling was noticeable at the edges, which was a problem in practical use.
  • a polarizing film with an adhesive layer cut into a length of 120 mm and a width of 25 mm was used as a sample.
  • the sample was applied to an ITO glass (manufactured by Geomatec Co., Ltd.) with a thickness of 20 mm formed on a 0.7 mm-thick non-alkali glass (EG-XG manufactured by Corning Co.) with a Sn ratio of 3%.
  • the sample was pasted and then autoclaved at 50° C. and 5 atm for 15 minutes for complete contact, and the adhesive strength of the sample was measured.
  • the adhesive force is measured by a tensile tester (Autograph SHIMAZU AG-1 10KN) at a peeling angle of 90° and a peeling speed of 300 mm/min. (N/25 mm, measuring length 80 mm) was obtained by doing. The measurement was performed twice, and the average value was used as the measured value. (Evaluation criteria) ⁇ : Adhesive strength less than 10 N (no problem in practical use) ⁇ : Adhesive strength 10 to less than 13 N (no problem in practical use) ⁇ : Adhesive strength 13 to less than 16 N (no problem in practical use) ⁇ : Adhesive force 16 N or more (problem in practical use)
  • ITO corrosion resistance A polarizing film with an adhesive layer cut into 15 mm ⁇ 15 mm was used as a sample.
  • the sample was laminated on an ITO glass (manufactured by Geomatec Co., Ltd.) 20 mm ⁇ 20 mm formed to have a film thickness of 20 nm with a Sn ratio of 3%, and then autoclaved at 50° C. for 5 minutes at 5 atm. It was used as a measurement sample for corrosion resistance.
  • the resistance value of the obtained measurement sample was measured using the measuring device described later, and this was defined as the "initial resistance value”.
  • the measurement sample was put into an environment of 65° C. ⁇ 95% RH for 500 hours, and then the resistance value was measured and defined as “resistance value after wet heat”.
  • the above resistance value is Accent.
  • the measurement was performed using HL5500PC, manufactured by Optical Technologies. From the "initial resistance value” and the “resistance value after moist heat” measured as described above, the "change in resistance value” was calculated by the following formula and evaluated according to the following criteria. (Evaluation criteria) ⁇ : Resistance value change is 1.20 or less ⁇ : Resistance value change is larger than 1.20
  • Comparative Examples by using a (meth) acrylic polymer that does not contain a specific monomer, or does not contain a specific monomer in a specific ratio, those that can satisfy all the evaluation items of durability at the same time I could't get it.
  • Comparative Example 4 using acrylic acid, which is a carboxyl group-containing monomer was inferior in metal corrosion resistance (ITO corrosion resistance).

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  • Organic Chemistry (AREA)
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PCT/JP2018/047873 2018-12-26 2018-12-26 光学フィルム用粘着剤組成物、光学フィルム用粘着剤層、及び、粘着剤層付光学フィルム WO2020136762A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
PCT/JP2018/047873 WO2020136762A1 (ja) 2018-12-26 2018-12-26 光学フィルム用粘着剤組成物、光学フィルム用粘着剤層、及び、粘着剤層付光学フィルム
KR1020247007099A KR20240033175A (ko) 2018-12-26 2018-12-26 광학 필름용 점착제 조성물, 광학 필름용 점착제층, 및, 점착제층 구비 광학 필름
CN201880100511.7A CN113227297B (zh) 2018-12-26 2018-12-26 光学膜用粘合剂组合物、光学膜用粘合剂层、及带粘合剂层的光学膜
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