WO2016003239A1 - Composition adhésive pour film optique, couche adhésive, film optique de type adhésif et dispositif d'affichage - Google Patents

Composition adhésive pour film optique, couche adhésive, film optique de type adhésif et dispositif d'affichage Download PDF

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Publication number
WO2016003239A1
WO2016003239A1 PCT/KR2015/006882 KR2015006882W WO2016003239A1 WO 2016003239 A1 WO2016003239 A1 WO 2016003239A1 KR 2015006882 W KR2015006882 W KR 2015006882W WO 2016003239 A1 WO2016003239 A1 WO 2016003239A1
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Prior art keywords
weight
pressure
sensitive adhesive
adhesive layer
optical film
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PCT/KR2015/006882
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English (en)
Korean (ko)
Inventor
스와타츠히로
오가와히로시
Original Assignee
삼성에스디아이 주식회사
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Priority claimed from JP2014137711A external-priority patent/JP2016014827A/ja
Application filed by 삼성에스디아이 주식회사 filed Critical 삼성에스디아이 주식회사
Priority to JP2017520849A priority Critical patent/JP6630728B2/ja
Priority to CN201580035472.3A priority patent/CN106661402B/zh
Publication of WO2016003239A1 publication Critical patent/WO2016003239A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers

Definitions

  • the present invention relates to an adhesive composition for an optical film, an adhesive layer, an adhesive optical film, and a display device including the same.
  • the display device includes a display element such as a liquid crystal cell.
  • a display element such as a liquid crystal cell.
  • Such display elements may affix various films according to a desired function and objective.
  • the liquid crystal cell includes a polarizing film on both sides in accordance with a unique image forming method.
  • the liquid crystal cell may further include a retardation plate, a viewing angle expanding film, a brightness enhancing film, various protective films, and the like for improving the image quality.
  • the film affixed on a display element is called an optical film collectively.
  • the display element may include one or more optical films.
  • the optical film may be directly attached to the display element, or a plurality of optical films may be laminated to the display element. In such a case, the optical film may be attached to the display element or another optical film using an adhesive.
  • the optical film is often used in the form of an adhesive optical film having an adhesive layer formed on at least one surface.
  • the pressure-sensitive adhesive optical film there is an advantage such that the drying step of the pressure-sensitive adhesive can be omitted.
  • re-peelability means that the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive for optical film does not destroy the display element during peeling, and does not leave contamination such as a residual adhesive on the display element during peeling.
  • the adhesive force of the pressure-sensitive adhesive for optical film should be lowered.
  • This reworkability is more important for thinner optical films and display devices as in recent trends. For example, when the thickness of an optical film and a display element becomes thin due to thinning, their breaking strength becomes small. Therefore, the adhesive used for a thin optical film and a display element needs to further reduce adhesive force in order to prevent damage.
  • the adhesive also requires the reliability (durability) which can stably bind an optical film and an optical film or an optical film and a display element.
  • durability durability
  • the adhesion reliability may be greatly impaired.
  • Patent Document 1 JP2010-275524 A
  • Patent Document 2 JP2008-503638 A
  • Patent Document 3 JP1996-199130 A
  • Patent Document 4 JP1996-209103 A
  • Patent Literature 1 the adhesive composition for optical films containing the (meth) acrylic-type polymer and the polyether which has a reactive silyl group is proposed.
  • the pressure-sensitive adhesive disclosed in Patent Literature 1 could not lower the adhesive force to a degree sufficient to rework the thin, thin optical film and the display element.
  • Patent Document 2 discloses an acrylic pressure-sensitive adhesive composition
  • Patent document 3 and 4 disclose the adhesive composition characterized by mix
  • the amount of carboxyl groups in the acrylic resin was large, the adhesive force could not be sufficiently lowered.
  • the technique of patent documents 3 and 4 was not able to ensure rework property with respect to especially a thin soft optical film and a display element.
  • An object of the present invention is to provide a pressure-sensitive adhesive composition for an optical film that is not only capable of achieving reworkability and reliability but also excellent in workability.
  • Another object of the present invention is to provide an adhesive layer formed of the pressure-sensitive adhesive composition for an optical film, an adhesive optical film, and a display device including the same.
  • the pressure-sensitive adhesive composition for an optical film of the present invention includes an adhesive resin having an acid value of about 0 mgKOH / g to about 20.0 mgKOH / g, a silicate oligomer represented by the following Chemical Formula 1, and a crosslinking agent.
  • R 1 to R 4 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
  • X 1 and X 2 are each independently hydrogen, having 1 to 20 carbon atoms. It is an alkyl group or a C6-C20 aryl group, n is an integer of 1-100.
  • the pressure-sensitive adhesive layer of one embodiment of the present invention may be formed of the pressure-sensitive adhesive composition for the optical film.
  • a pressure-sensitive adhesive layer of another embodiment of the present invention is a pressure-sensitive adhesive layer formed of a composition comprising a (meth) acrylic polymer, a urethane polymer and a pressure-sensitive resin containing at least one of polyester, a silicate oligomer represented by the following formula (1) and a peroxide-based crosslinking agent
  • the gel fraction according to Formula 1 may be about 40 wt% to about 95 wt% after being left for about 1 hour from the pressure-sensitive adhesive layer formation.
  • R 1 to R 4 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
  • X 1 and X 2 are each independently hydrogen, having 1 to 20 carbon atoms.
  • n is an integer of 1 to 100
  • Wb is a weight of about 0.2g of the adhesive layer wrapped with a fluorine resin (TEMISHNTF-1122, Nito Denko), and Wa is the weight of the fluorine resin.
  • Wc immersed the adhesive layer wrapped with the fluorine resin in about 40 ml of ethyl acetate at about 23 ° C. for about 7 days to extract the soluble component, and the adhesive layer wrapped with the fluorine resin on the aluminum cup at about 130 ° C. for about 2 hours. After drying, it is the weight of the adhesive layer wrapped with the fluorine resin from which the soluble component is removed.
  • the pressure-sensitive adhesive optical film of the present invention may include one of a polarizer, a protective layer formed on one surface of the polarizer, and the adhesive layer formed on the other surface of the polarizer.
  • the display device of the present invention may include the adhesive optical film.
  • the present invention is not only capable of achieving both reworkability and reliability, but also has an effect of providing a pressure-sensitive adhesive composition for an optical film, a pressure-sensitive adhesive layer, a pressure-sensitive adhesive optical film, and a display device including the same.
  • FIG. 1 is a cross-sectional view showing a pressure-sensitive adhesive optical film according to an embodiment.
  • FIG. 2 is a cross-sectional view showing a pressure-sensitive adhesive optical film of another embodiment.
  • FIG 3 is a cross-sectional view illustrating a display device according to one embodiment.
  • FIG. 4 is a cross-sectional view illustrating a display device of another embodiment.
  • the pressure-sensitive adhesive composition for an optical film of the present invention includes a pressure-sensitive resin, a silicate oligomer and a crosslinking agent having an acid value of about 0 mgKOH / g to about 20.0 mgKOH / g.
  • a pressure-sensitive resin e.g., a polystyrene resin
  • silicate oligomer e.g., a silicate oligomer
  • crosslinking agent having an acid value of about 0 mgKOH / g to about 20.0 mgKOH / g.
  • the adhesive resin of one embodiment has an acid value of about 0 mgKOH / g to about 20 mgKOH / g.
  • the adhesive resin has an acid value of about 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0 mgKOH / g can be.
  • the adhesive resin may have an acid value in a range of at least one of the above values and at most one of the above values.
  • the acid value of the adhesive resin may be about 10 mgKOH / g or less, more specifically about 3 mgKOH / g or less, and more specifically about 1 mgKOH / g or less.
  • the adhesive resin may have an acid value of more than about 0 mgKOH / g and about 20 mgKOH / g or less.
  • the adhesive resin in the above range is excellent in the adhesion and reliability of the pressure-sensitive adhesive composition, it can be balanced with the reworkability.
  • Adhesive resin can contain as a structural unit the monomer containing a hydroxyl-containing monomer as a structural unit.
  • the hydroxyl group-containing monomer may include (meth) acrylate having a hydroxyl group, polyol, and the like, but is not limited thereto.
  • the adhesive resin is not particularly limited as long as it is adhesive and has an acid value of about 0 mgKOH / g to about 20 mgKOH / g.
  • Such adhesive resins may include, for example, one or more of (meth) acrylic polymers, urethane polymers, and polyesters.
  • the adhesive resin may be composed of any one of these, or may be composed of a mixture of these resins.
  • the adhesive resin may be a copolymer of these resins. When using such an adhesive resin, the adhesive composition is advantageous to satisfy the optical properties of the optical film.
  • the adhesive resin of one embodiment may include a (meth) acrylic polymer.
  • the (meth) acrylic polymer includes a polymer containing an alkyl (meth) acrylate monomer as a polymerized unit constituting the main skeleton; Or a copolymer comprising an alkyl (meth) acrylate monomer and other comonomers as a polymerized unit (hereinafter, an alkyl (meth) acrylate copolymer).
  • the alkyl (meth) acrylate may be exemplified that the monomer has 1 to 18 carbon atoms of a linear or branched alkyl group.
  • the alkyl group is 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, furnace A nil group, a decyl group, an isodecyl group, a dodecyl group, an isomyristyl, a lauryl group, a tridecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, etc. can be illustrated. These can be used individually or in combination.
  • the alkyl (meth) acrylate copolymer may be prepared by copolymerizing an alkyl (meth) acrylate monomer and one or more comonomers.
  • the comonomer means a monomer polymerizable with an alkyl (meth) acrylate monomer, and is not particularly limited as long as it is polymerizable with the alkyl (meth) acrylate monomer.
  • the at least one comonomer may have a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group. In such a case, the adhesive resin may have improved adhesiveness or heat resistance.
  • the comonomer is, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, (meth) Hydroxyl group-containing monomers such as 8-hydroxyoctyl acrylic acid, 10-hydroxydecyl (meth) acrylic acid, 12-hydroxylauryl (meth) acrylic acid, and (4-hydroxymethylcyclohexyl) -methyl acrylate; Carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid; Acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; Caprolactone adducts of acrylic acid; Styrene sulfonic acid or aryl
  • the comonomer is, for example, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methyl (N-substituted) amide monomers such as allpropane (meth) acrylamide; (Meth) acrylic-acid alkylaminoalkyl type monomers, such as amino ethyl (meth) acrylate, N, N- dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; Alkoxy alkyl (meth) acrylate monomers, such as (meth) acrylic-acid methoxyethyl and (meth) acrylate ethoxyethyl; N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhe
  • the comonomers are, for example, vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole as modified monomers.
  • Vinyl monomers such as vinylimidazole, vinyl oxazole, vinyl morpholine, N-vinyl carboxylic acid amides, styrene, ⁇ -methyl styrene, and N-vinyl caprolactam; Cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; Epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; Glycol-based acrylic ester monomers such as (meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol, and (meth) acrylic acid methoxy polypropylene glycol; Acrylic ester ester monomers, such as (meth) acrylic acid tetrahydrofurfuryl, a fluorine (meth) acrylate, silicone (meth) acrylate, and 2-methoxyethyl acrylate, can also be used. Moreover, isoprene,
  • the comonomer may include, for example, a silane monomer containing a silicon atom.
  • silane monomers include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, and 4-vinylbutyltriethoxysilane.
  • the comonomer is tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl Ether di (meth) acrylate, neopentylglycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate (Meth) acrylic acid, such as a dipentaerythritol penta (meth) acrylate, a dipentaerythritol hexa (meth) acrylate, and a caprolactone modified dipentaerythritol hexa (meth) acrylate; (Meth) acryloyl groups, such as esterified substance with an
  • the comonomer is a polyester (meth) acrylate in which two or more unsaturated double bonds such as (meth) acryloyl groups and vinyl groups are added to a skeleton such as polyester, epoxy, urethane, or the like as the monomer component. , Epoxy (meth) acrylate, urethane (meth) acrylate, and the like.
  • the content of the comonomer is about 0% to about 20% by weight, about 0.1% to about 15% by weight, based on the total weight of the total monomers (monomers used as polymerized units of the alkyl (meth) acrylate copolymer), Specifically, about 0.1% to about 10% by weight.
  • the pressure-sensitive adhesive composition is advantageous for achieving both reworkability and reliability.
  • the (meth) acrylic copolymer of one embodiment may use a hydroxyl group-containing monomer as a comonomer.
  • a hydroxyl group-containing monomer as a comonomer.
  • the adhesiveness and durability of the pressure-sensitive adhesive composition can be improved.
  • the hydroxyl group-containing monomer is rich in reactivity with the crosslinking agent, the cohesiveness and heat resistance of the pressure-sensitive adhesive composition can be further improved.
  • the hydroxyl group-containing monomer may further improve the reworkability of the pressure-sensitive adhesive composition.
  • the ratio is about 0.01% to about 15%, about 0.03% to about 10%, about 0.05% to about 7% by weight based on the total weight of the total monomers. Weight percent.
  • the (meth) acrylic copolymer of another embodiment may use a carboxyl group-containing monomer as a comonomer.
  • the comonomer can form a reaction point with the crosslinking agent when the pressure-sensitive adhesive composition contains a crosslinking agent.
  • the comonomer may further improve the reworkability of the pressure-sensitive adhesive composition.
  • the ratio is about 0.05% to about 10%, about 0.1% to about 8%, about 0.2% to about 6% by weight based on the total weight of the total monomers. Weight percent.
  • the (meth) acrylic copolymer of another embodiment may use a combination of a hydroxyl group-containing monomer and a carboxyl group-containing monomer as a comonomer.
  • the (meth) acrylic polymer may have a weight average molecular weight of about 300,000 to about 3 million. Specifically, the weight average molecular weight of the (meth) acrylic polymer may be about 500,000 to about 2.5 million, more specifically about 800,000 to about 2.3 million. In this case, the pressure-sensitive adhesive composition can be improved in durability and heat resistance. More specifically, the weight average molecular weight of the (meth) acrylic polymer may be about 700,000 to about 2.3 million. Within this range, the pressure-sensitive adhesive composition may further improve heat resistance, and the viscosity may be appropriate, which may be advantageous for coating. In addition, the process of adding a large amount of diluting solvent can be omitted, thereby reducing the cost.
  • a weight average molecular weight means the value computed by polystyrene conversion measured by GPC (gel permeation chromatography).
  • the glass transition temperature of the (meth) acrylic polymer may be about ⁇ 10 ° C. or less and about ⁇ 25 ° C. or less. Within this range, the pressure-sensitive adhesive composition can improve flexibility and initial tack, and can exhibit sufficient adhesion even at low pressure.
  • the lower limit of the glass transition temperature may be about ⁇ 100 ° C. or more, about ⁇ 80 ° C. or more, or about ⁇ 70 ° C. or more. Within such a range, the heat resistance of polyester can be prevented from falling.
  • the (meth) acrylic-type polymer As a polymerization method of a (meth) acrylic-type polymer, well-known polymerization methods, such as solution polymerization, block polymerization, emulsion polymerization, and various radical polymerization, can be selected suitably.
  • the (meth) acrylic-type polymer obtained by the said polymerization method may be any of a random copolymer, a block copolymer, and a graft copolymer.
  • the (meth) acrylic polymer can be prepared by solution polymerization.
  • ethyl acetate, toluene or the like may be used as the polymerization solvent.
  • solution polymerization may be carried out under reaction conditions of about 5 hours to about 30 hours, usually about 50 ° C. to about 85 ° C., by adding a polymerization initiator under an inert gas stream such as nitrogen.
  • the (meth) acrylic polymer may be prepared by radical polymerization.
  • a polymerization initiator, a chain transfer agent, an emulsifier, etc. used for radical polymerization are not specifically limited, It can select suitably and can use.
  • the polymerization initiator, the chain transfer agent, etc. can control the weight average molecular weight of a (meth) acrylic-type polymer by adjusting the usage-amount, reaction conditions, etc.
  • the polymerization initiator is, for example, 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'-di Azo initiators such as methylene isobutyl amidine) and 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (from Wako Pure Chemical Industries, Ltd., VA-057); Redox initiators such as a combination of a peroxide and a reducing agent such as an initiator, a combination of persulfate and sodium bisulfite, a combination of peroxide and sodium ascorbate, and the like, may be used.
  • Redox initiators such as a combination
  • the said polymerization initiator can be used individually, and can mix and use 2 or more types.
  • the content of the polymerization initiator may be, for example, about 0.005 parts by weight to about 1 part by weight and about 0.02 parts by weight to about 0.5 parts by weight based on 100 parts by weight of the total monomers.
  • the (meth) acrylic polymer (A) of the said weight average molecular weight can be manufactured using 2,2'- azobisisobutyronitrile as a polymerization initiator.
  • the specific amount of the polymerization initiator may be about 0.06 parts by weight to about 0.2 parts by weight, or about 0.08 parts by weight to about 0.175 parts by weight based on 100 parts by weight of the total amount of the monomer components.
  • chain transfer agent for example, lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, thioglucolic acid 2-ethylhexyl, 2,3-dimercapto-1 Propanol and the like.
  • a chain transfer agent can be used individually, and can mix and use 2 or more types. Content of a chain transfer agent may be about 0.1 weight part or less with respect to 100 weight part of all monomer components.
  • the emulsifier examples include anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate and sodium polyoxyethylene alkylphenyl ether sulfate, and polyoxyethylene.
  • anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate and sodium polyoxyethylene alkylphenyl ether sulfate, and polyoxyethylene.
  • nonionic emulsifiers such as alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, and polyoxyethylene-polyoxypropylene block polymers. These emulsifiers may be used independently or may
  • emulsifier into which radically polymerizable functional groups, such as a propenyl group and an allyl ether group, were introduce transduced as a reactive emulsifier
  • radically polymerizable functional groups such as a propenyl group and an allyl ether group
  • transduced as a reactive emulsifier For example, Aquaron HS-10, HS-20, KH-10, BC-05, BC-10 and BC-20 (all of which are manufactured by Dai-Ichi Kogyo Seiyaku Co., Ltd.), Adekaria Soap SE10N, SR-10N (ADEKA CHEMICAL Co., Ltd.), and the like.
  • the amount of the emulsifier used is about 0.3 parts by weight to about 5 parts by weight based on 100 parts by weight of the total amount of the monomer components, and from about polymerization stability or mechanical stability, 0.5 parts to about 2 parts by weight.
  • the urethane polymer that may be used as the adhesive resin may be, for example, a reaction of a polyol and an isocyanate.
  • the polyol include polyester polyols and polyether polyols.
  • polyester polyol a known polyester polyol may be used.
  • the polyester polyol of one embodiment may be obtained by dehydration polymerization of an acid component and a bivalent or higher polyol component.
  • the acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid and the like.
  • the divalent or higher polyol component is, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentane Diol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, 2-butyl-3-ethyl-1 Dihydric alcohols including, 5-pentanediol, 2-butyl-4-ethyl-1,5-pentanediol and the like; Trihydric alcohols including glycerine, trimethylolpropane; And one or more of tetrahydric alcohols including pentaerythritol and the like.
  • the polyester polyol of another specific example may be a polyester polyol obtained by ring-opening-polymerizing lactones such as polycaprolactone, poly ( ⁇ -methyl- ⁇ -valerolactone), and polyvalerolactone.
  • the molecular weight of the polyester polyol can be used from low molecular weight to high molecular weight. Specifically, polyester polyols having a molecular weight of about 1,000 to about 5,000, more specifically polyester polyols having a molecular weight of about 2,500 to about 3,500 can be used. Within this range, the polyester polyol can prevent gelation of the polyurethane and improve the cohesion of the polyurethane itself.
  • the amount of the polyester polyol may be about 10 mol% to about 70 mol%, more specifically about 35 mol% to about 65 mol% of the polyol constituting the polyurethane.
  • polyether polyol a known polyether polyol may be used.
  • the polyether polyol is a low molecular weight polyol such as propylene glycol, ethylene glycol, glycerine, trimethylolpropane, and the like, for example, ethylene oxide, propylene oxide, butylene oxide, It may be a polyether polyol obtained by polymerizing oxirane compounds such as tetrahydrofuran. Specifically, the polyether polyol may be exemplified by having two or more functional groups including polypropylene glycol, polyethylene glycol, polytetramethylene glycol, and the like.
  • the initiator is a glycol such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerine, trimethylolpropane, pentaerythritol ;
  • polyhydric amines such as ethylene diamine, N-aminoethylethanol amine, isophorone diamine, xylylene diamine, and the like.
  • the molecular weight of the polyether polyol can be used from low molecular weight to high molecular weight.
  • the polyether polyol may specifically have a weight average molecular weight of about 1,000 to about 5,000, more specifically about 2,500 to about 3,500. Within this range, the polyether polyol can prevent gelation of the urethane polymer and improve the cohesion of the polyurethane itself.
  • the content of the polyether polyol may be about 20 mol% to about 80 mol%, more specifically about 40 mol% to about 65 mol% of the polyol constituting the polyurethane.
  • the polyether polyols may also utilize bifunctional polyether polyols.
  • the polyether polyols may comprise polyether polyols having a molecular weight of about 1,000 to about 5,000 and at the same time having at least three or more hydroxyl groups in one molecule.
  • the polyether polyol may implement a balance of adhesion and re-peelability to the urethane polymer.
  • the polyether polyols may utilize some or all of the polyols having a molecular weight of about 2,500 to about 3,500 and at the same time at least trifunctional. In this case, the polyether polyol can prevent gelation of the urethane polymer, improve reactivity, and improve cohesion of the polyurethane itself.
  • the isocyanate used in one embodiment may be an organopolyisocyanate compound including known aromatic polyisocyanates, aliphatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and the like.
  • the aromatic polyisocyanate is, for example, 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2, 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate , 4,4'-diphenylether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, and the like.
  • Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, Dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.
  • the aromatic aliphatic polyisocyanate is ⁇ , ⁇ '-diisocyanate-1,3-dimethylbenzene, ⁇ , ⁇ '-diisocyanate-1,4-dimethylbenzene, ⁇ , ⁇ '-diisocyanate-1,4-di Ethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.
  • Alicyclic polyisocyanates include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl -2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylene bis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane, 1,4- Bis (isocyanatemethyl) cyclohexane and the like.
  • isocyanate can also use together the trimethylolpropane adduct of the said polyisocyanate, the biuret reacted with water, and the trimer which has an isocyanurate ring.
  • the polyisocyanate is, for example, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) ) Can be used.
  • a well-known catalyst can be used as a catalyst used for the synthesis
  • a tertiary amine compound, an organometallic compound, etc. are mentioned.
  • tertiary amine compound examples include triethylamine, triethylene diamine, 1,8-diazabicyclo (5,4,0) -undecene-7 (DBU), and the like.
  • organometallic compound examples include tin compounds and non-tin compounds.
  • examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, Tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, 2-ethylhexane Acid tin etc. are mentioned as an example.
  • non-tin compound examples include titanium-based compounds such as dibutyl titanium dichloride, tetrabutyl titanate and butoxy titanium trichloride, lead systems such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate;
  • lead systems such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate;
  • examples thereof include iron-based irons such as iron 2-ethylhexanoate and iron acetylacetonate, cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc-based zinc such as zinc naphthenate and zinc 2-ethylhexanoate, and zirconium naphthenate.
  • iron-based irons such as iron 2-ethylhexanoate and iron acetylacetonate
  • cobalt-based compounds such as cobalt be
  • Tertiary amine / organic metal-based, tin-based / tin-based, tin-based / tin-based, etc. may be used as the two or more catalyst combinations, specifically, tin-based / tin-based, more specifically, dibutyltin dilaurate and Combinations of tin 2-ethylhexanoate can be used.
  • the weight ratio of dibutyltin dilaurate: tin 2-ethylhexanoate is about 1: May be less than one. Specifically, about 1: 0.2 to about 1: 0.6. Within this range, the effect of lowering the gelation of the urethane polymer can be further improved.
  • the amount of the aforementioned catalyst may be about 0.01% to about 1.0% by weight based on the total amount of polyol and isocyanate.
  • the polyurethane of one embodiment may be used in admixture with a polyfunctional isocyanate compound.
  • the polyfunctional isocyanate compound may include, for example, the aforementioned organopolyisocyanate compound and trimethylolpropane adducts thereof, a biuret reacted with water, or a trimer having an isocyanurate ring.
  • the polyfunctional isocyanate when a combination of the urethane polymer and the polyfunctional isocyanate is used, may be included in an amount of about 1 part by weight to about 20 parts by weight based on 100 parts by weight of the urethane polymer. Specifically, it is about 2 parts by weight to about 10 parts by weight. Within this range, the adhesion and cohesion of the adhesive resin containing the urethane polymer can be further improved.
  • the reaction temperature may be about 100 ° C. or less. More specifically, it may be about 85 °C to about 95 °C. Within this range, it is advantageous to control the crosslinked structure of the urethane polymer, through which a polyurethane having a predetermined molecular weight and chemical structure can be obtained.
  • the polyurethane may have a weight average molecular weight of about 10,000 to about 200,000, specifically about 15,000 to about 100,000, more specifically about 20,000 to about 50,000.
  • a weight average molecular weight of about 10,000 to about 200,000, specifically about 15,000 to about 100,000, more specifically about 20,000 to about 50,000.
  • the flexibility of the adhesive resin can prevent the loss, thereby improving the initial adhesiveness and overall adhesion. In such a case, the pressure-sensitive adhesive composition can be easily adhered even at low pressure.
  • the glass transition temperature of the polyurethane of one embodiment may be about ⁇ 10 ° C. or less and about ⁇ 25 ° C. or less. Within this range, the flexibility of the adhesive resin can prevent the loss, thereby improving the initial adhesiveness and overall adhesive strength. In such a case, the pressure-sensitive adhesive composition can be easily adhered even at low pressure.
  • the glass transition temperature may specifically have a lower limit of about -100 ° C or more, about -80 ° C or more and about -70 ° C or more. Within this range, the heat resistance of the adhesive resin can be further improved.
  • a solvent used for dilution of the urethane polymer may be a known solvent.
  • a solvent for example, water, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, etc. are mentioned.
  • toluene may be used as the solvent. In such a case, the solubility of a urethane polymer, the boiling point of a solvent, etc. may be excellent.
  • the polyester of one embodiment can be obtained by using what consists of a polyol component and a carboxylic acid component as a raw material, and polycondensing them.
  • the polyol component used in the synthesis of the polyester may include at least one of a diol having an alkoxy group in the side chain and a polyol other than the diol having an alkoxy group in the side chain.
  • the diol having an alkoxy group in the side chain is methoxyethylene glycol, methoxypropylene glycol, methoxybutylene glycol, ethoxyethylene glycol, ethoxypropylene glycol, ethoxybutylene glycol Lycol, dimethoxyethylene glycol, dimethoxypropylene glycol, dimethoxybutylene glycol, diethoxyethylene glycol, diethoxypropylene glycol, diethoxybutylene glycol and the like can be used. It is not limited thereto.
  • polyols other than the diol which has an alkoxy group in a side chain ethylene glycol, a propylene glycol, 1, 3- propanediol, 1, 4- butanediol, 1, 5- pentanediol, for example Linear aliphatic diols such as 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol; Neopentylglycol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2 -Butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5- Ali
  • polyols other than diols having an alkoxy group in the side chain include straight-chain aliphatic diols having 2 to 6 carbon atoms, specifically 1,4-butanediol, 1,6-hexanediol, ethylene glycol
  • an aliphatic diol having a hydrocarbon group side chain having 1 to 4 carbon atoms, more specifically, neopentyl glycol can be used. In such a case, the initial adhesiveness, mechanical strength, and heat resistance of the pressure-sensitive adhesive composition can be well balanced.
  • the polyol component used in the synthesis of the polyester may further include at least one of polyetherdiol and a trivalent or higher polyhydric alcohol.
  • polyetherdiol polyethyleneglycol, polypropylene glycol, polytetramethylene glycol, etc. which ring-opened-polymerized ethylene oxide, a propion oxide, tetrahydrofuran, etc. are mentioned, These are mentioned 1 type or It can use 2 or more types.
  • trihydric or higher polyhydric alcohol examples include trimethylolethane, trimethylolpropane, glycerine, pentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2, 6-hexane triol etc. can be mentioned as an example, These can be used 1 type, or 2 or more types.
  • trimethylolpropane may be used in the above-described trivalent or higher polyhydric alcohol.
  • the polyester can be further improved in heat resistance.
  • the content of the trihydric or higher polyhydric alcohol is not particularly limited, but may be, for example, about 0.1 mol% to about 5.0 mol%, specifically about 0.5 mol% to about 3.0 mol%.
  • the carboxylic acid component used in the synthesis of the polyester is not particularly limited.
  • the carboxylic acid which has an alkoxy group in a side chain can be included.
  • an alkoxy group can be introduce
  • any of the above-mentioned polyol component and carboxylic acid component can use the raw material component which contains an alkoxy group in a side chain.
  • carboxylic acids having a number average molecular weight of about 500 to about 3,000 and having an alkoxy group can be used.
  • the polyester can be made to have a good balance of initial adhesiveness, mechanical strength, and heat resistance.
  • carboxylic acids other than the carboxylic acid which has an alkoxy group in a side chain For example, aromatic dicarboxylic acid, such as terephthalic acid, isophthalic acid, orthophthalic acid, 1, 5- naphthalene dicarboxylic acid, 2, 6- naphthalene dicarboxylic acid, p-oxybenzoic acid, Saturated dicarboxylic acids such as aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, and octadecanedicarboxylic acid; Unsaturated dicarboxylic acids such as fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, tetracurolphthalic acid, hexahydrophthalic acid, dimer acids, and the like, and the like, and these may be used alone or in combination of two or
  • the carboxylic acid component of one embodiment may be, for example, trivalent or more such as trimellitic acid, trimesic acid, pyromellitic acid, 1,2,4-butane tricarboxylic acid, 1,2,5-hexane tricarboxylic acid, or the like, as necessary. It may further comprise a carboxylic acid. In one embodiment, among these, aromatic dicarboxylic acid, specifically terephthalic acid, isophthalic acid, aliphatic dicarboxylic acid having 6 to 12 carbon atoms (including carbon of carboxyl group), and more specifically sebacic acid can be used. In such a case, polyester can make the initial adhesiveness of an adhesive composition, mechanical strength, and heat resistance compatible with a good balance.
  • the content of the alkoxy group in the polyester resin of one specific example is not specifically limited, About 5 to about 300 alkoxy groups and about 60 to about 150 alkoxy groups can be introduce
  • the blending ratio of the polyol component may be about 1 equivalent or more, about 1.2 equivalents or more, and about 2.0 equivalents or less of the polyol component per 1 equivalent of the carboxylic acid component.
  • the molecular weight of the polyester can be adjusted to an appropriate range, and the yield can be further improved.
  • a polymerization (esterification) reaction may be performed first, and then a condensation reaction may be performed.
  • a catalyst can be used.
  • the catalyst for the esterification reaction is a catalyst such as titanium-based such as tetraisopropyl titanate or tetrabutyl titanate, antimony-based such as antimony trioxide, germanium-based such as germanium oxide, zinc acetate, manganese acetate, dibutyltin, or the like.
  • An oxide etc. can be mentioned as an example, These 1 type, or 2 or more types can be used.
  • the blending amount of the esterification catalyst may be about 1 ppm to about 10,000 ppm, about 10 ppm to about 5,000 ppm, and about 10 ppm to about 3,000 ppm with respect to the total of the total reactants. Within this range, it is possible to implement the effect of improving the degree of polymerization of the reaction, shortening the reaction time, and further lowering side reactions.
  • the reaction temperature in the polymerization (esterification) reaction may be about 160 ° C to about 260 ° C, specifically about 180 ° C to about 250 ° C, more specifically about 200 ° C to about 250 ° C. Within this range, it is possible to implement the effect of improving the degree of polymerization of the reaction, shortening the reaction time, and further lowering side reactions.
  • the polymerization (esterification) reaction can be carried out under normal pressure.
  • the condensation reaction can be carried out.
  • an additional catalyst may be further added.
  • the catalyst used for the condensation reaction in the synthesis of polyester can be used in the same amount as the same kind of catalyst that can be used in the above-described esterification reaction.
  • the condensation reaction may be carried out at a reaction temperature of about 220 ° C. to about 260 ° C., more specifically about 230 ° C. to about 250 ° C., to gradually depressurize the reaction system and finally react at about 5 hPa or less. Within this reaction temperature range, the reactivity of the reactants can be improved, and side reactions such as decomposition of the polyester can be further lowered.
  • the polyester has a weight average molecular weight of about 10,000 to about 200,000, specifically about 15,000 to about 100,000, more specifically about 20,000 to about 50,000. Within the range of the weight average molecular weight, sufficient cohesive force can be obtained when applied to the pressure-sensitive adhesive composition, and further excellent heat resistance and mechanical strength can be ensured. In addition, within the above range, the pressure-sensitive adhesive composition can be improved in flexibility and initial tack, and can exhibit sufficient adhesion even at low pressure.
  • the glass transition temperature of the polyester of one embodiment may be about ⁇ 10 ° C. or less and about ⁇ 25 ° C. or less. Within this range, the pressure-sensitive adhesive composition can improve flexibility and initial tack, and can exhibit sufficient adhesion even at low pressure.
  • the lower limit of the glass transition temperature may be about ⁇ 100 ° C. or more, about ⁇ 80 ° C. or more, or about ⁇ 70 ° C. or more. Within such a range, the heat resistance of polyester can be prevented from falling.
  • a solvent used for dilution of the polyester may be a known solvent.
  • a solvent for example, water, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, etc. are mentioned.
  • methyl ethyl ketone and ethyl acetate may be used as the solvent.
  • the solubility of polyester, the boiling point of a solvent, etc. may be excellent.
  • the silicate oligomer of one embodiment is represented by the following formula (1).
  • R 1 to R 4 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
  • X 1 and X 2 are each independently hydrogen, having 1 to 20 carbon atoms. It is an alkyl group or a C6-C20 aryl group, n is an integer of 1-100.
  • the alkyl group and the aryl group may or may not be substituted.
  • the alkyl group may be linear or branched structure.
  • R 1 to R 4 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms
  • X 1 and X 2 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or 6 to 6 carbon atoms. It may be an aryl group of 12.
  • R 1 to R 4 may be each independently a methyl group, an ethyl group, or a phenyl group.
  • the silicate oligomer may be a single species of oligomer or a mixture of plural kinds of oligomers.
  • the weight average molecular weight of the silicate oligomer may be about 300 to about 30,000.
  • the pressure-sensitive adhesive composition can be compatible with even more excellent reworkability and adhesion.
  • the silicate oligomer is a silicate oligomer having R 1 to R 4 , X 1 and X 2 in the formula (1) is a methyl group and a weight average molecular weight of about 300 to about 20,000, R 1 to R 4 , X 1 in the formula ( 1) And a silicate oligomer having X 2 a methyl group and a weight average molecular weight greater than about 20,000 and up to about 30,000, and a silicate oligomer comprising R 1 , R 2 , R 3 , R 4 , X 1, or X 2 in the formula (1). It may contain the above.
  • Methyl silicate oligomer having the weight average molecular weight of about 300 to about 20,000 Methyl silicate oligomer having a weight average molecular weight of greater than about 20,000 or less than about 30,000 or R 1 , R 2 , R 3 , R 4 , X 1 or X 2 of Formula 1
  • the pressure-sensitive adhesive composition may be compatible with more excellent reworkability and adhesion.
  • the weight average molecular weight of the silicate oligomer may be specifically about 500 to about 25,000, more specifically about 600 to about 5,000, more specifically about 800 to about 3,500.
  • the pressure-sensitive adhesive composition may include about 0.01 part by weight to about 50 parts by weight of the silicate oligomer based on 100 parts by weight of the adhesive resin.
  • the pressure-sensitive adhesive composition has a silicate oligomer of about 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6 based on 100 parts by weight of the adhesive resin. , 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 or 50 parts by weight.
  • the silicate oligomer may be in the range of at least one of the above numerical values and at most one of the above numerical values. For example, about 0.01 parts by weight to about 50 parts by weight of silicate oligomer, specifically about 0.5 parts by weight to about 20 parts by weight, more specifically about 0.5 parts by weight to about 10 parts by weight, more preferably 100 parts by weight of the tacky resin. More specifically, about 1 part to about 5 parts by weight. Within this range, the initial reworkability of the pressure-sensitive adhesive composition and the adhesion after heating may be further improved. Within this range, the pressure-sensitive adhesive composition may be compatible with more excellent reworkability and adhesion.
  • the pressure-sensitive adhesive composition of one embodiment may contain a crosslinking agent.
  • an organic type crosslinking agent or a polyfunctional metal chelate can be used as a crosslinking agent.
  • the organic crosslinking agent include isocyanate crosslinking agents, carbodiimide crosslinking agents, oxazoline crosslinking agents, peroxide crosslinking agents, epoxy crosslinking agents, imine crosslinking agents and the like.
  • the polyfunctional metal chelate include those in which a polyvalent metal is covalently or coordinating with an organic compound.
  • the polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. Can be.
  • an oxygen atom etc. can be illustrated,
  • An alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, a ketone compound, etc. can be illustrated as an organic compound.
  • the crosslinking agent may use at least one of an isocyanate crosslinking agent, a carbodiimide crosslinking agent, and a peroxide crosslinking agent.
  • a peroxide crosslinking agent When using a peroxide crosslinking agent, the adhesive layer which does not need aging can be manufactured. In the manufacturing process of an adhesive layer, the adhesive layer which does not need aging is strongly requested
  • the adhesive layer, which does not require aging has an advantage in that reworkability and reliability are excellent, and handleability of the adhesive layer manufacturing process is improved.
  • Isocyanate-based crosslinking agents include, for example, isocyanate monomers such as tolylene diisocyanate, chlorophenylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate or the above isocyanate monomers.
  • isocyanate monomers such as tolylene diisocyanate, chlorophenylene diisocyanate, tetramethylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate or the above isocyanate monomers.
  • Isocyanate compound which added to trimethylol propane etc . and urethane prepolymer isocyanates obtained by addition reaction of isocyanurate or isocyanate biuret compound with polyether polyol or polyester polyol, acryl polyol, polybutadiene polyol, polyisoprene polyol and the like; It may include one or more of.
  • the isocyanate-based crosslinking agent may be a polyisocyanate compound, and more specifically, may be one or a polyisocyanate compound selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate. .
  • the one or more polyisocyanate compounds selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate and isophorone diisocyanate are hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, polyol-modified hexa Methylene diisocyanate, polyol modified hydrogenated xylylene diisocyanate, trimer type hydrogenated xylylene diisocyanate, polyol modified isophorone diisocyanate and the like.
  • the polyisocyanate compounds exemplified above may have excellent crosslinking reaction rates with hydroxyl groups.
  • the exemplified polyisocyanate compound can accelerate the crosslinking reaction by using the acid and the base contained in the polymer as a catalyst, and thus can contribute particularly to the accelerated crosslinking.
  • the carbodiimide compound may be, for example, a high molecular weight polycarbodiimide produced by decarbonation condensation of diisocyanate in the presence of a carbodiimide catalyzed catalyst. More specifically, the polycarbodiimide compound may be one obtained by decarboxylation of the following diisocyanate.
  • diisocyanate used for the polycarbodiimide compound 4,4'-diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-diphenylmethane diisocyanate, 3,3'-di Methyl-4,4'-diphenylmethane diisocyanate, 4,4'-diphenylether diisocyanate, 3,3'-dimethyl-4,4'-diphenylether diisocyanate, 2,4-tolylene di
  • isocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate The above can be used. Moreover, the mixture of 2 or more types in the said illustration can also be used.
  • 1-phenyl-2-phosphorene-1-oxide, 3-methyl-2-phosphorene-1-oxide, 1-ethyl-3-methyl-2- Phosphorene oxides, such as a phosphorene-1-oxide, a 1-ethyl- 2-phosphorene-1-oxide, or these 3-phosphorene isomers can be used.
  • the high molecular weight polycarbodiimide compound includes the carbodilite series manufactured by Nisshin Boseiki Co., Ltd. Especially, when carbodilite V-01, 03, 05, 07, 09 is used, compatibility with an organic solvent may be excellent.
  • the peroxide crosslinking agent can be used without limitation as long as it generates radically active species by heating or light irradiation to advance the crosslinking of the base polymer of the pressure-sensitive adhesive composition.
  • a peroxide crosslinking agent having a half-life temperature of about 50 ° C to about 160 ° C or about 60 ° C to about 140 ° C for 1 minute can be used. In such a case, workability or stability may be improved.
  • the peroxide crosslinking agent may be, for example, di (2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: about 90.6 ° C.), di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life).
  • di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half life temperature: about 92.1 degreeC
  • dilauroyl peroxide (1 minute half life temperature: about 116.4 degreeC)
  • Dibenzoyl peroxide (1 minute half-life temperature: about 130.0 ° C.), and the like are specifically used.
  • the peroxide half life is an index indicating the decomposition rate of the peroxide, and means the time until the residual amount of the peroxide is half.
  • the decomposition temperature, half-life, and the like of the peroxide may be as described, for example, in each manufacturer catalog or the like. For example, it is described in Nihon Yushi Co., Ltd. "The organic peroxide catalog ninth edition (May 2003)" etc.
  • the oxazoline-based crosslinking agents are specifically 2-isopropyl-2-oxazoline, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxa May include one or more of sleepy, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline This is not restrictive.
  • An oxazoline type crosslinking agent can use what is commercially available.
  • oxazoline group-containing acrylic polymers such as epocros WS-300, epocros WS-500, epocros WS-700, epocros K-1000 series, and epocros K-2000 series from Japan Catalyst Co., Ltd. can be used alone or in combination of two or more. It can be used, but is not limited thereto.
  • the amount of the crosslinking agent may be about 0.01 parts by weight to about 20 parts by weight, and about 0.03 parts by weight to about 10 parts by weight based on 100 parts by weight of the adhesive resin.
  • the cohesive force of the pressure-sensitive adhesive composition is excellent, it is possible to lower the foaming incidence upon heating, excellent moisture resistance, reworkability can be improved in reliability tests and the like.
  • one type of isocyanate type crosslinking agent may be used alone or two or more types may be used as a crosslinking agent.
  • the content of the isocyanate-based crosslinking agent in this embodiment is about 0.01 parts by weight to about 2 parts by weight, about 0.02 parts by weight to about 2 parts by weight, about 0.05 parts by weight to about 1.5 parts by weight based on 100 parts by weight of the adhesive resin. Can be. Within this range, the cohesion force of the pressure-sensitive adhesive composition, the reworkability in the durability test, and the like can be further improved.
  • a peroxide type crosslinking agent can be used individually by 1 type or in mixture of 2 or more types as a crosslinking agent.
  • the adhesive layer which does not need aging can be manufactured.
  • the adhesive layer which does not require an aging from a viewpoint of handling improvement is strongly demanded. Therefore, the need for aging of the pressure-sensitive adhesive layer is a great advantage in the manufacturing process.
  • the adhesive layer, which does not require aging has an advantage in that reworkability and reliability are excellent, and handleability of the adhesive layer manufacturing process is improved.
  • the content of the peroxide crosslinking agent in this embodiment is about 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, It may contain 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2.0 parts by weight.
  • the peroxide-based cross-linking agent content may be in the range of about one or more of the above values and about one or less of the above values based on 100 parts by weight of the adhesive resin.
  • the peroxide-based crosslinking agent content is about 0.01 parts by weight to about 2 parts by weight, specifically about 0.02 parts by weight to about 2 parts by weight, and more specifically about 0.04 parts by weight to about 1.5 parts by weight of the adhesive resin. By weight, even more specifically from about 0.05 part by weight to about 1 part by weight. Within this range, processability, reworkability, crosslinking stability, reworkability, and the like of the pressure-sensitive adhesive composition can be further improved.
  • the pressure-sensitive adhesive composition of one embodiment may further contain a silane coupling agent.
  • silane coupling agents are, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxy Epoxy group-containing silane coupling agents such as cyclohexyl) ethyl trimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl Amino group-containing silane coupling agents such as -N- (1,3-dimethylbutylidene) propylamine and N-phenyl- ⁇ -aminopropyltrimethoxysilane, 3-acryloxypropy
  • the content of the silane coupling agent is about 0.001 parts by weight to about 10 parts by weight, about 0.001 parts by weight to about 5 parts by weight, about 0.01 parts by weight to about 1 parts by weight, and about 0.02 parts by weight based on 100 parts by weight of the above-mentioned adhesive resin. To about 1 part by weight, about 0.05 part by weight to about 0.6 part by weight. Within the above range, durability of the pressure-sensitive adhesive composition can be improved, and adhesive strength to optical members such as liquid crystal cells can be ensured.
  • the pressure-sensitive adhesive composition of one embodiment may further include an additive other than the above-described components.
  • additives include polyether compounds of polyalkylene glycols such as polypropylene glycol, powders such as colorants, pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, It can add suitably according to the use which uses antioxidant, antioxidant, a light stabilizer, a ultraviolet absorber, a polymerization inhibitor, an inorganic or organic filler, metal powder, a particle form, a foil form, etc.
  • the redox-type additive which added the reducing agent can also be used within the range which can be controlled.
  • the pressure-sensitive adhesive layer can be formed on various optical films.
  • the optical film in which such an adhesion layer was formed is also called adhesive optical film.
  • the method of forming an adhesion layer includes the method of apply
  • coating of an adhesive composition you may add a 1 or more types of solvent other than a polymerization solvent newly.
  • a silicone liner may be specifically used.
  • a liner may be, for example, a silicone-based release agent on one side of the liner.
  • a silicone type release agent can facilitate the transfer of the adhesive composition formed in the separator to an optical film.
  • the method of forming a specific adhesive layer may include a method of applying a pressure-sensitive adhesive composition on a separator or an optical film to form a coating film. It may also include a method of heating and drying the coating film after the formation of the coating film.
  • the heat drying temperature may be about 40 ° C to about 200 ° C, specifically about 50 ° C to about 180 ° C, and more specifically about 70 ° C to about 170 ° C. By making heating temperature into the said range, the adhesive composition which has the outstanding adhesive characteristic can be obtained.
  • drying time appropriate time can be employ
  • the drying time may be specifically about 5 seconds to about 20 minutes, more specifically about 5 seconds to about 10 minutes, in particular about 10 seconds to about 5 minutes.
  • the adhesive layer is formed on the surface of the optical film after various kinds of easy adhesion treatment such as forming treatment, corona treatment, plasma treatment, etc. (adhesive auxiliary layer) )can do. Moreover, you may perform an easy adhesion
  • the coating method of the pressure-sensitive adhesive composition is not particularly limited, but for example, a roll coat, a kiss roll coat, a gravure coat, a reverse coat, a roll brush, a spray coat, a dip roll coat, a bar coat, a knife coat, an air knife coat, a curtain coat, Methods, such as the extrusion coating method by a lip coat and a die coat, are mentioned.
  • Crosslinking treatment may be performed when the adhesive layer is formed. Such a crosslinking process may be performed at the temperature at the time of the drying process of an adhesion layer, and you may provide and perform a crosslinking treatment process separately after a drying process.
  • the said crosslinking process can fully consider the influence of crosslinking process temperature and crosslinking process time, while adjusting the addition amount of the whole crosslinking agent.
  • the crosslinking treatment temperature, the crosslinking treatment time and the like can be adjusted according to the crosslinking agent to be used.
  • the crosslinking treatment temperature in the formation of the pressure-sensitive adhesive composition may be about 170 ° C or less and specifically about 130 ° C or less. Energy efficiency may be improved when the pressure-sensitive adhesive layer is formed in the above range.
  • a specific separator for example, PET
  • foreign substances such as oligomers can suppress the production.
  • the foreign material (eg, oligomer) may be produced at about 30 ppm or less, specifically about 10 ppm or less. It is suitable to use it as an adhesive for optical films in the said range.
  • the crosslinking treatment time can be set in consideration of productivity and workability.
  • the crosslinking treatment time in forming the pressure-sensitive adhesive composition may be about 0.2 minutes to about 20 minutes, about 0.5 to about 10 minutes.
  • the cross-linking treatment may be performed by performing a peroxide crosslinking treatment with a peroxide-based crosslinking agent to form an adhesive layer.
  • the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer formed by a crosslinking treatment of a pressure-sensitive adhesive composition comprising a pressure-sensitive resin comprising at least one of a (meth) acrylic polymer, a urethane polymer, and a polyester, a silicate oligomer represented by the following general formula (1), and a peroxide-based crosslinking agent,
  • a pressure-sensitive adhesive composition comprising a pressure-sensitive resin comprising at least one of a (meth) acrylic polymer, a urethane polymer, and a polyester, a silicate oligomer represented by the following general formula (1), and a peroxide-based crosslinking agent,
  • the gel fraction according to Equation 1 may be about 40 wt% to about 95 wt% after being left for about 1 hour from adhesion layer formation.
  • R 1 to R 4 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
  • X 1 and X 2 are each independently hydrogen, having 1 to 20 carbon atoms. It is an alkyl group or a C6-C20 aryl group, n is an integer of 1-100.
  • Wb is a weight of about 0.2g of the adhesive layer wrapped with a fluorine resin (TEMISHNTF-1122, Nito Denko), and Wa is the weight of the fluorine resin.
  • Wc immersed the adhesive layer wrapped with the fluorine resin in about 40 ml of ethyl acetate at about 23 ° C. for about 7 days to extract the soluble component, and the adhesive layer wrapped with the fluorine resin on the aluminum cup at about 130 ° C. for about 2 hours. After drying, it is the weight of the adhesive layer wrapped with the fluorine resin from which the soluble component is removed.
  • the gel fraction after about 1 hour is about 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94 or 95%.
  • the gel fraction after 1 hour may be in the range of one or more of the above values and one or less of the above values.
  • the gel fraction after 1 hour is about 40 wt% to about 95 wt%, specifically about 65 wt% to about 95 The range of weight% may be satisfied.
  • the pressure-sensitive adhesive layer has no fear of crushing and deterioration of durability, does not require aging, and therefore has an advantage of excellent workability.
  • the peroxide crosslinking treatment time may be a peroxide crosslinking treatment of at least a half-life time corresponding to a peroxide crosslinking treatment temperature (about 170 ° C. or less, specifically about 130 ° C. or less).
  • the adhesive resin has an acid value of about 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0 mgKOH / can be g.
  • the adhesive resin may have an acid value in a range of at least one of the above values and at most one of the above values.
  • the acid value of the tacky resin may range from about 0 mgKOH / g to about 20.0 mgKOH / g, specifically from about 0 mgKOH / g to about 10.0 mgKOH / g, more specifically from about 0 mgKOH / g to about 5.0 mgKOH / g, even more specifically about 0 mgKOH / g to about 3.0 mgKOH / g.
  • the pressure-sensitive adhesive composition is excellent in adhesive strength and reliability, and can achieve a balance between rework properties.
  • the composition may include a peroxide crosslinking agent to form an adhesive layer by peroxide crosslinking.
  • the peroxide crosslinking treatment can decompose at least about 50% by weight of the peroxide crosslinking agent.
  • the gel fraction of the pressure-sensitive adhesive layer may be about 40% by weight to about 95% by weight.
  • the adhesive layer may have a difference between an initial adhesive force and an adhesive force after heating about 1 N / 25 mm or less. It is excellent in the rework property and reliability of an adhesion layer in the said range.
  • the initial adhesive force is the adhesive force to the following initial glass plate
  • the adhesive force after heating is the adhesive force to the glass plate after the heating
  • the initial glass plate and the glass plate after heating are produced as follows.
  • An adhesive polarizing film (sample) is cut out to about 25 mm in width x about 100 mm in length, and affixed on the alkali free glass plate (Corning Corporation product, Eagle XG) of thickness about 0.5 mm using a laminator.
  • the polarizing film is completely stuck to the alkali free glass by autoclaving the glass plate with a polarizing film at about 50 degreeC and about 5 atm for about 15 minutes. Thereby, an initial glass plate is produced. And the said initial glass plate is heated for about 48 hours under about 50 degreeC dry conditions, and a glass plate is produced after heating.
  • the adhesive force of an initial glass plate and a glass plate after a heating is measured by the following method.
  • the adhesive force (N / 25mm) at the time of removing a polarizing film from each glass plate is measured using the tensile tester (Tensilon Universal Testing Machine STA-1150 by Orient Tech Co., Ltd.). Measurement conditions are about 23 degreeC, relative humidity about 50%, peeling angle about 180 degrees, and peeling rate about 300 mm / min. In addition, peeling is based on the method of the adhesive tape and adhesive sheet test of JISZ0237.
  • the adhesive layer may have an adhesive strength of about 3 N / 25 mm or less, specifically about 2.5 N / 25 mm or less after heating. It is excellent in the rework property and reliability of an adhesion layer in the said range.
  • the thickness of the adhesive layer is not particularly limited, but may be, for example, about 1 ⁇ m to about 100 ⁇ m. Specifically, it is about 2 ⁇ m to about 50 ⁇ m, more specifically about 2 ⁇ m to about 40 ⁇ m, and more specifically about 5 ⁇ m to about 35 ⁇ m. Within this range, the adhesive force and the rework property of the adhesive layer can be effectively compatible.
  • a release agent-treated separator (second separator) may be further formed to protect the adhesive layer. This second separator is used after removing the adhesive layer.
  • the adhesive optical film of the present invention may include an optical film and the adhesive layer formed on one or both surfaces of the optical film.
  • the adhesive optical film may include a polarizer, a protective layer formed on one surface of the polarizer, and an adhesive layer formed on the other surface of the polarizer, and the adhesive layer may be formed of the pressure-sensitive adhesive composition for the optical film.
  • the polarizer may include a transparent protective film on at least one side of the polarizer.
  • a polarizer is not specifically limited,
  • the dichroism of an iodine or a dichroic dye is used for hydrophilic polymer films, such as a polyvinyl alcohol film, a partially foamed polyvinyl alcohol film, and an ethylene-vinyl acetate copolymerization partially saponified film.
  • Hydrophilic polymer films such as a polyvinyl alcohol film, a partially foamed polyvinyl alcohol film, and an ethylene-vinyl acetate copolymerization partially saponified film.
  • Polyene type orientation films such as the thing which made the material adsorb
  • a polarizer made of a divinyl substance such as a polyvinyl alcohol film and iodine may be used as the polarizer.
  • the degree of opticality and handleability of the polarizing film may be further excellent.
  • the thickness of the polarizer is not particularly limited, but may be, for example, about 5 ⁇ m to about 80 ⁇ m.
  • the protective layer is not limited as long as it can protect the polarizer.
  • the protective layer may be a transparent protective film.
  • the transparent protective film may be bonded to one or both sides of the polarizer by an adhesive layer.
  • An adhesive agent is used for the adhesion
  • an adhesive agent an isocyanate adhesive, a polyvinyl alcohol adhesive, a gelatin adhesive, a vinyl latex type, an aqueous polyester, etc. can be illustrated.
  • the adhesive is usually used as an adhesive consisting of an aqueous solution, and may contain, for example, about 0.5% by weight to about 60% by weight solids.
  • the adhesive agent of a polarizer and a transparent protective film are mentioned as an adhesive agent of a polarizer and a transparent protective film.
  • the adhesive agent for electron beam hardening type polarizing films shows suitable adhesiveness with respect to the said various transparent protective films.
  • the adhesive for bonding the polarizer and the transparent protective film of one embodiment may further contain a metal compound filler.
  • thermoplastic resin which is excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, etc.
  • thermoplastic resins include cellulose resins such as triacetyl cellulose, polyester resins, polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, and (meth) acrylic resins.
  • Cyclic polyolefin resin (norbornene-based resin), polyarylate resin, polystyrene resin, polyvinyl alcohol resin, and mixtures thereof.
  • a polarizer has a transparent protective film bonded by an adhesive bond layer, on the other side, it is a thermosetting resin, such as a (meth) acrylic-type, urethane type, an acryl urethane type, an epoxy type, a silicone type, or ultraviolet curing type as a transparent protective film. Resin can be used. One or more types of arbitrary appropriate additives may be contained in the transparent protective film. As an additive, a ultraviolet absorber, antioxidant, a lubricating agent, a plasticizer, a mold release agent, a coloring inhibitor, a flame retardant, a nucleating agent, an antistatic agent, a pigment, a coloring agent, etc. are mentioned, for example.
  • the content of the thermoplastic resin in the transparent protective film is specifically about 50 to about 100% by weight, more specifically about 50 to about 99% by weight, more specifically about 60 to about 98% by weight, particularly specifically From about 70 to about 97 weight percent.
  • content of the said thermoplastic resin in a transparent protective film is about 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.
  • the thickness of a transparent protective film can be suitably determined, it is generally about 1 micrometer-about 500 micrometers in terms of workability, thinness, etc., such as strength and handleability. In particular from about 1 ⁇ m to about 300 ⁇ m, from about 5 ⁇ m to about 200 ⁇ m.
  • the pressure-sensitive adhesive layer is suitable when a pressure-sensitive adhesive layer is directly formed on a thin transparent protective film having a thickness of about 40 ⁇ m or less.
  • the protective layer can be a protective coating layer.
  • the protective coating layer may be formed of an active energy ray curable resin composition comprising an active energy ray curable compound and an initiator.
  • the active energy ray curable compound may include at least one of an acrylic compound, an epoxy compound, and an isocyanurate compound.
  • the protective coating layer may have a thickness of about 5 ⁇ m to about 200 ⁇ m, specifically about 5 ⁇ m to about 20 ⁇ m, and more specifically about 4 ⁇ m to about 10 ⁇ m. In the above range, the protective coating layer can be formed directly on the polarizer without using an adhesive, and can thin the polarizing plate.
  • the said adhesive optical film can be laminated
  • formation of a liquid crystal display device such as a reflecting plate, a semi-transmissive plate, a retardation film (including wavelength plates, such as 1/2 or 1/4), a visual compensation film, a brightness enhancement film, etc.
  • the thing used as the optical layer which may be used for is mentioned.
  • the adhesive optical film may further include a retardation film formed on the adhesive layer.
  • stacked the said optical layer on the adhesive optical film can also be formed also by the method of laminating
  • stacked previously and made it into the optical film is stability of quality and granulation.
  • Excellent work and the like has the advantage of improving the manufacturing process, such as a liquid crystal display device.
  • Suitable lamination means such as an adhesion layer, can be used for lamination.
  • the optical axis can be set to an appropriate placement angle in accordance with a desired phase difference characteristic or the like.
  • the polarizer which dyed a polyvinyl alcohol-type film with iodine and uniaxially stretched can be created by dyeing polyvinyl alcohol by immersing it in the aqueous solution of iodine, and extending
  • swelling of the polyvinyl alcohol-based film can also prevent the unevenness of dyeing and the like.
  • Stretching may be performed after dyeing with iodine, or may be performed while dyeing, or may be dyed with iodine after stretching. It can extend
  • liquid crystal displays such as a reflecting plate, a semi-transmissive plate, a retardation film (including wavelength plates, such as 1/2 and a quarter), a visual compensation film, a brightness enhancement film, a surface treatment film, etc.
  • the thing used as the optical layer which may be used for formation of an apparatus etc. is mentioned. These can be used independently as an optical film, can be laminated
  • the pressure-sensitive adhesive optical film including the optical film and the pressure-sensitive adhesive layer may further include a phase difference film formed on the pressure-sensitive adhesive layer.
  • the adhesive composition which concerns on one Embodiment is a rework property with respect to an optical film even if an optical film is thin (for example, about 100 micrometers or less). While securing, it has high reliability.
  • the adhesion auxiliary layer is a layer whose wettability with respect to the adhesion layer is larger than the optical film.
  • attachment auxiliary layer is produced by corona-processing an optical film, for example. You may prepare an adhesion
  • the adhesive auxiliary layer may be formed on at least one of the optical film surface and the adhesive layer surface.
  • the adhesive optical film 10 shown in FIG. 1 includes an optical film 11 and an adhesive layer 12 formed on one surface of the optical film 11.
  • the adhesive layer 12 is formed on the optical film 11 by apply
  • the optical film 11 may be a polarizer, for example.
  • the adhesive composition may be used as an adhesive layer previously formed on an optical film.
  • the adhesion layer 12 may be formed on both surfaces of the optical film 11. 2 shows a modification of the adhesive optical film 10.
  • the adhesive optical film 10 shown in FIG. 2 has the adhesion
  • the adhesion auxiliary layer 11a is a layer whose wettability with respect to the adhesion layer 12 is larger than the optical film 11.
  • the display device of the present invention may include the adhesive optical film.
  • Examples of the display device include a liquid crystal display device, an organic electroluminescent display device, and the like.
  • FIG. 3 and 4 show a configuration example of a display device in which an adhesive layer according to one embodiment is formed.
  • the display device 20 shown in FIG. 3 includes a display element 21, an adhesive layer 22, and an optical film 23.
  • the optical film 23 is arrange
  • the display device 20 is a modification of the display device 20. As shown in FIG. 4, you may provide the multiple optical film on the display element 21.
  • the adhesive layer 24 and the optical film 25 are further provided on the optical film 23 of the display device 20 shown in FIG. 3.
  • the adhesion layer 24 and the optical film 25 are provided on the optical film 23 by the method similar to the adhesion layer 22 and the optical film 23.
  • the display device 20 may be, for example, a liquid crystal display device, an organic EL display device, or the like.
  • the display element 21 becomes a liquid crystal cell
  • the optical film 23 becomes a polarizing film.
  • the optical film 25 becomes a viewing angle enlargement film, a brightness improving film, various protective films, etc., for example.
  • the display device 20 becomes a liquid crystal display device, you may arrange
  • the retardation plate and the display element 21 may be bonded by an adhesive layer.
  • the film thickness of the display element 21 is not specifically limited, although the adhesive composition which concerns on one Embodiment is a case where the display element 21 is thin (for example, 200 micrometers or less), it is not necessary for the display element 21 to be retained. While ensuring workability, it has high reliability. That is, even when either or both of an optical film and a display element is thin, the adhesive composition which concerns on one Embodiment has high reliability, ensuring rework property for these.
  • the pressure-sensitive adhesive layer manufacturing method of the present invention includes the step of forming an adhesive layer with a pressure-sensitive adhesive composition for an optical film on one or both sides of the substrate, the pressure-sensitive adhesive composition for the optical film has an acid value of about 0 mgKOH / g to about 20.0 mgKOH / g It may include a pressure-sensitive adhesive resin and a silicate oligomer represented by the formula (1).
  • R 1 to R 4 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
  • X 1 and X 2 are each independently hydrogen, having 1 to 20 carbon atoms. It is an alkyl group or a C6-C20 aryl group
  • n is an integer of 1-100.
  • R 1 to R 4 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms
  • X 1 and X 2 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or 6 to 6 carbon atoms. It may be an aryl group of 12.
  • R 1 to R 4 may be a methyl group, an ethyl group, or a phenyl group.
  • the substrate may be an optical film.
  • optical film what is used for formation of image display apparatuses, such as a liquid crystal display device, is used, The kind in particular is not restrict
  • the optical film is substantially the same as described in the pressure-sensitive adhesive layer.
  • a polarizing film is mentioned as an optical film.
  • the forming of the pressure-sensitive adhesive layer may include forming a layer including the pressure-sensitive adhesive composition for an optical film on one or both sides of the substrate, and performing a peroxide crosslinking treatment on the layer including the pressure-sensitive adhesive composition for the optical film.
  • Peroxide crosslinking may be performed in the preparation of the adhesive layer. This crosslinking treatment is substantially the same as described in the adhesive layer formation process, and specifically, the peroxide crosslinking treatment may be decomposed about 50 wt% or more of the peroxide crosslinking agent, and may be performed at about 130 ° C. or less, and the adhesive layer.
  • the gel fraction may be from about 40% to about 95% by weight.
  • the pressure-sensitive adhesive composition for an optical film includes about 0.01 part by weight to about 2 parts by weight, and about 0.02 part by weight to about 2 parts by weight, and about 0.04 parts by weight, based on about 100 parts by weight of the adhesive resin. About 1.5 parts by weight, about 0.05 parts by weight to about 1 part by weight may be further included.
  • the pressure-sensitive adhesive composition for an optical film may contain about 0.01 parts by weight to about 50 parts by weight, specifically about 0.5 parts by weight to about 20 parts by weight, and more specifically about 0.5 parts by weight of the silicate oligomer based on 100 parts by weight of the adhesive resin. To about 10 parts by weight, even more specifically about 1 part to about 5 parts by weight. Within this range, the initial reworkability of the pressure-sensitive adhesive composition and the adhesion after heating may be further improved.
  • the pressure-sensitive adhesive composition for an optical film may further include a crosslinking agent.
  • the crosslinking agent may be an isocyanate crosslinking agent, a carbodiimide crosslinking agent, an oxazoline crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent, an imine crosslinking agent, or the like, but is not limited thereto.
  • the concentration of the solution is expressed in weight percent relative to the total weight of the solution.
  • the acrylic resin (polymer A1) which is an example of adhesive resin was produced.
  • a stirring vane a thermometer
  • a nitrogen gas introduction tube a thermometer
  • a nitrogen gas introduction tube a thermometer
  • a nitrogen gas introduction tube a thermometer
  • a nitrogen gas introduction tube a thermometer
  • a nitrogen gas introduction tube a thermometer
  • a nitrogen gas introduction tube a thermometer
  • a nitrogen gas introduction tube a thermometer
  • a nitrogen gas introduction tube 0.15 parts by weight of nitrile was injected together with 100 parts by weight of ethyl acetate.
  • nitrogen gas was introduce
  • the liquid temperature in the flask was maintained at about 55 ° C, and the monomers were allowed to undergo a polymerization reaction for 5 hours. This produced the solution of the polymer A1.
  • the weight average molecular weight (Mw) of the polymer A1 was 2.1 million.
  • the acid value of the polymer A1 was 0 mgKOH / g.
  • Table 1 shows the composition of the polymer A1 (weight ratio of the monomers constituting the polymer A1), the weight average molecular weight and the acid value.
  • the weight average molecular weight of polymer A1 was measured by GPC (gel permeation chromatography).
  • the measuring apparatus and measuring conditions are as follows.
  • the acid value of the polymer A1 was measured by the following process.
  • a mixed solvent containing toluene, isopropyl alcohol, and distilled water in a weight ratio of 50: 49.5: 0.5 was prepared.
  • about 0.5 g (based on solids) of Polymer A1 was precisely weighed and dissolved in 50 g of the mixed solvent.
  • This sample solution was neutralized and titrated with a 0.1% KOH aqueous solution using a titration device manufactured by Hiranma (MA), form "COMTITE-550".
  • the acid value of the polymer A1 was computed by the obtained result and following [formula 2].
  • polymer A2-A6 were produced by performing the process similar to Production Example 1.
  • the weight average molecular weights and the acid value of polymers A2 to A7 were measured by the same method as in Production Example 1. The results are summarized in Table 1.
  • the urethane resin (polymer A8) was produced by the following process. 51.9 g of polyester polyol P-1010 (bifunctional polyester polyol, OH of 112 mg / g, manufactured by Kuraray Co., Ltd.) in a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen introducing tube, a thermometer, and a dropping funnel; Adeka polyether G-1500 (trifunctional polyether poly, trifunctional, OH value 109 mg / g, manufactured by ADEKA Corporation) 32.2 g, isophorone diisocyanate (IPDI) (manufactured by Sumitomo Bayer Corporation) 15.9 g, 66.7 g of toluene, 0.03 g of iron 2-ethylhexanoate and 0.04 g of lead naphthenate were added as a catalyst.
  • polyester polyol P-1010 bifunctional polyester polyol, OH of 112 mg / g,
  • the mixed solution was gradually heated up to 90 ° C, and the monomers were polymerized for 4 hours.
  • the residual isocyanate group was confirmed by an infrared spectrophotometer (IR), the reaction was terminated at the timing when the peak corresponding to the isocyanate group disappeared, and the mixed solution after the reaction, that is, the solution of the urethane resin was cooled.
  • the solution of urethane resin was colorless transparent and 60 weight% of solid content.
  • the weight average molecular weight and the acid value were measured by the same method as in Production Example 1, and the weight average molecular weight was 50,000 and the acid value was 0.5 KOHmg / g.
  • Table 2 shows the composition (weight ratio of monomers constituting polymer A8), weight average molecular weight and acid value of polymer A8.
  • the polyester resin (polymer A9) was produced with the following process. In a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 11.7 g of ethylene glycol, 18.6 g of neopentyl glycol, 11.8 g of isophthalic acid, 57.9 g of sebacic acid, and tetra-n-butyl titanate 0.15 g was added. Then, esterification reaction was performed by heating a mixed solution at 150-270 degreeC for 150 minutes, and then the pressure of the reaction system was gradually lowered to 133 Pa after 30 minutes, and reaction was performed for 180 minutes, continuing pressure reduction.
  • the solution of the polyester resin was obtained by diluting the mixed solution after reaction with ethyl acetate. Solid content of this solution was 60 weight%.
  • the weight average molecular weight and the acid value of the polyester resin were measured by the same method as in Production Example 1, and the weight average molecular weight was 38,000 and the acid value was 0.3 KOHmg / g.
  • the composition (weight ratio of the monomers which comprise Polymer A8), the weight average molecular weight, and the acid value of polymer A9 are shown in Table 3.
  • the high molecular weight type silicate oligomer B1 was produced. 152 g (1 mol, 4 equivalents) of tetramethoxysilane was dissolved in 500 g of tetrahydrofuran (hereinafter also referred to as "THF"). Next, 72 g (8 equivalents) of 0.35% by weight aqueous hydrochloric acid solution was added to the obtained solution and mixed. Next, the tetramethoxysilane was hydrolyzed by standing the mixed solution at 20 ° C for 1 hour.
  • THF tetrahydrofuran
  • the polymethoxysiloxane ("MKC silicate MS-51" by Mitsubishi Chemical Co., Ltd.) was added to the solution after hydrolysis, ie, the reaction solution, and refluxed for 2 hours. Then, THF was made to flow out by raising the temperature of the reaction solution to 150 degreeC. This gave the silicate oligomer B1 of the colorless and transparent liquid form. The weight average molecular weight of the silicate oligomer B1 was 25,000.
  • the polymethoxysiloxane (“MKC silicate MS-51”) of a raw material is an oligomer of 900 with a weight average molecular weight.
  • R 1 to R 4 , X 1 and X 2 of the silicate oligomer B1 are all represented by Formula 1, which is a methyl group.
  • the measurement of the weight average molecular weight of the silicate oligomer B1 was measured by GPC (gel permeation chromatography).
  • the measuring apparatus and measuring conditions are as follows.
  • silicate oligomer B2 in which R 1 to R 4 , X 1 and X 2 are phenyl groups or methyl groups (R 1 to R 4 , X 1, or X 2 is a phenyl group) was prepared. 400 g (1 mole, 4 equivalents) of tetraphenoxysilane was dissolved in 500 g of THF. Next, 72 g (8 equivalents) of 0.35% by weight aqueous hydrochloric acid solution was added to the obtained solution and mixed. Next, the tetraphenoxysilane was hydrolyzed by standing the mixed solution at 20 ° C for 1 hour.
  • silicate MS-51 by Mitsubishi Chemical Co., Ltd.
  • THF was made to flow out by raising the temperature of the reaction solution to 150 degreeC.
  • the weight average molecular weight of the silicate oligomer B2 was measured in the same manner as in Production Example 10, and the weight average molecular weight of the silicate oligomer B2 was 5,000.
  • polymethoxysiloxane which is a raw material is an oligomer of 900 molecular weight.
  • MKC silicate MS-51 polymethoxysiloxane
  • the hydrolyzed tetraphenoxysilane and the polymethoxysiloxane were bonded to each other to produce a silicate oligomer B2 wherein R 1 to R 4 , X 1 and X 2 are phenyl groups or methyl groups.
  • the single protection polarizing film was produced as an optical film.
  • a 20-micrometer-thick polyvinyl alcohol film was stretched up to three times while dyeing in a 0.3 wt% iodine solution at 30 ° C for 1 minute between rolls having different speed ratios. Thereafter, the stretched film was stretched to 6 times while immersing the stretched film in an aqueous solution containing 60 ° C., 4 wt% boric acid, and 10 wt% potassium iodide for 0.5 minute. Next, the stretched film was washed by immersion for 10 seconds in an aqueous solution containing 30 ° C and 1.5% by weight of potassium iodide, and then dried at 50 ° C for 4 minutes. This obtained the polarizer.
  • the acrylic film (lactone modified acrylic resin film) of 20 micrometers in thickness was bonded to one surface of the polarizer with the polyvinyl alcohol-type adhesive agent.
  • An acrylic film is an example of a protective film. This produced the single protection polarizing film whose total thickness is 27 micrometers.
  • the thickness of the adhesive layer after drying was carried out on one side of the polyethylene terephthalate (PET) film (Mitsubishi Chemical Co., Ltd. product, MRF38, the oligomer prevention layer) of 38 micrometers in thickness which siliconized the said adhesive composition solution. It applied so that it might become 20 micrometers.
  • PET polyethylene terephthalate
  • the coating layer was dried at 100 ° C. for 2 minutes to form an adhesive layer.
  • a pressure-sensitive adhesive polarizing film was produced by bonding an adhesive layer to a polarizer surface (corona treated surface) subjected to corona treatment at a corona discharge amount of 80 [W ⁇ min / m 2] to the single protective polarizing film prepared in Production Example 12. It was.
  • Adhesive resin Silicate Oligomer B Crosslinking agent 1 Crosslinking agent 2 Silane coupling agent kinds Mass parts Kinds Amount Mw Kinds Amount Kinds Amount Kinds Amount (Parts by weight) (Parts by weight) (Parts by weight) (Parts by weight) (Parts by weight) (Parts by weight)
  • Example 1 A1 100 B3 5 550 D-110N 0.1 - - KBM-403 0.1
  • Example 2 A1 100 B4 5 900 D-110N 0.1 - - - - Example 3
  • A1 100 B4 30 900 D-110N 0.1 - - - - Example 5
  • A1 100 B6 5 1300 D-110N 0.1 - - - - - Example 6 A1 100 B7 5 1400 D-110N 0.1 - - - - - Example 7
  • Example 12 A1 100 B2 3 5000 D-110N 0.1 - - - - Example 13 A1 100 B5 5 3200 D-110N 0.1 - - - - Example 14 A2 100 B4 5 900 D-110N 0.1 - - - - Example 15 A2 100 B4 5 900 V-05 0.1 - - - - Example 16 A1 100 B5 5 3200 WS-700 0.1 - - - - Example 17 A1 100 B5 5 3200 Tetrad X 0.1 - - - - - Example 18 A3 100 B4 5 900 D-110N 0.1 - - -
  • the silicate oligomer B3 is methyl silicate 51 having R 1 to R 4 , X 1 and X 2 all being methyl groups and having a weight average molecular weight of 600.
  • the silicate oligomer B4 is methyl silicate 53A (manufactured by Cole Coat Co., Ltd.), wherein R 1 to R 4 , X 1 and X 2 are all methyl groups and a weight average molecular weight is 900.
  • Silicate oligomer B5 is R 1 to R 4 , X 1 and X 2 are butyl groups (15%), the rest are methyl groups (85%), and MKC silicate MS58B15 (manufactured by Mitsubishi Kagaku Co., Ltd.) with a weight average molecular weight of 3,200. .
  • a silicate oligomer B6 is R 1 to R 4, X 1 and X 2 is a methyl group (50%) and an ethyl group (50%), and a weight average molecular weight of 1,300 of EMS-485 (Cole Coat Co., Ltd.).
  • the silicate oligomer B7 is ethyl silicate 48 (manufactured by Cole Coat Co., Ltd.), wherein R 1 to R 4 , X 1 and X 2 are all ethyl groups and have a weight average molecular weight of 1,400.
  • PEROYL TCP is a peroxide crosslinking agent manufactured by NOF CORPORATION.
  • the adhesive polarizing film adheresive optical film which concerns on each Example and the comparative example.
  • the pressure-sensitive adhesive polarizing film (sample) is cut out into a 37-inch size (56.4 cm x 75.2 cm size) and laminated to an alkali-free glass (Corning Company, Eagle XG) having a thickness of 0.5 mm. It was attached using a laminater (laminating machine).
  • an alkali free glass is used as a liquid crystal cell glass substrate.
  • what attached two sheets of alkali free glass of thickness 0.25mm is used for an actual liquid crystal cell.
  • an adhesive type polarizing film is affixed on both surfaces of such an alkali free glass. Therefore, what is excellent in these characteristics means that an adhesive type polarizing film can be used suitably as a polarizing film of a liquid crystal cell.
  • the sample was completely adhered to the alkali free glass by autoclaving the glass plate with a polarizing film at 50 degreeC and 0.5 Mpa for 15 minutes.
  • the glass plate with a polarizing film (henceforth a "initial glass plate” hereafter) with which this process was performed was hold
  • the initial stage glass plate was processed for 500 hours in 60 degreeC / 95% RH (relative humidity) atmosphere (humidification test).
  • the adhesive force evaluation test was done about the adhesive polarizing film (adhesive optical film) which concerns on each Example and the comparative example. Specifically, the adhesive polarizing film (sample) was cut out to width 25mm x length 100mm, and was affixed on the alkali free glass plate (Corning Company, Eagle XG) of thickness 0.5mm using a laminator. Next, the polarizing film was completely stuck to the alkali free glass by autoclaving a glass plate with a polarizing film at 50 degreeC and 5atm for 15 minutes. This produced the initial glass plate. Next, the initial glass plate was heated for 48 hours under 50 ° C drying conditions. This produced the glass plate after heating. And the adhesive force of the initial glass plate and the glass plate after heating was measured by the following method.
  • the adhesive force (N / 25mm) at the time of removing a polarizing film from each glass plate was measured using the tensile tester (Tensilon universal material tester STA-1150 by Orient Tech Co., Ltd.). Measurement conditions were made into 23 degreeC, 50% of a relative humidity, 180 degree of peeling angles, and 300 mm / min of peeling rates. In addition, peeling was performed based on the method of the adhesive tape and adhesive sheet test of JISZ0237.
  • the rework property evaluation test was done about the adhesive polarizing film (sample). Specifically, the initial glass plate and the glass plate after heating were produced by first performing the process similar to the adhesive force evaluation test with respect to an adhesive polarizing film (sample). However, the magnitude
  • Example 1 ⁇ ⁇ ⁇ 1.1 ⁇ 1.9 ⁇
  • Example 2 ⁇ ⁇ ⁇ 0.5 ⁇ 0.8 ⁇
  • Example 3 ⁇ ⁇ ⁇ 1.6 ⁇ 2.5 ⁇
  • Example 4 ⁇ ⁇ ⁇ 0.2 ⁇ 0.4 ⁇
  • Example 5 ⁇ ⁇ ⁇ 1.9 ⁇ 2.8 ⁇
  • Example 6 ⁇ ⁇ ⁇ 2.3 ⁇ 2.9 ⁇
  • Example 7 ⁇ ⁇ ⁇ 0.4 ⁇
  • Example 8 ⁇ ⁇ 0.5 ⁇ 0.8 ⁇
  • Example 9 ⁇ ⁇ 0.6 ⁇
  • Example 10 ⁇ ⁇ ⁇ 1.2 ⁇ 2.2 ⁇
  • Example 11 ⁇ ⁇ ⁇ 0.3 ⁇ 0.9 ⁇
  • Example 12 ⁇ ⁇ ⁇ 0.5 ⁇ 1.3 ⁇
  • Example 13 ⁇ ⁇ ⁇ 0.4 ⁇ 0.9 ⁇
  • Example 14 ⁇ ⁇ ⁇ 1.3 ⁇ 2 ⁇
  • Example 15 ⁇ ⁇ ⁇ One ⁇ 1.5 ⁇
  • Example # 16 ⁇ ⁇ ⁇ 0.8 ⁇ 1.3 ⁇
  • Example 17 ⁇ ⁇ ⁇ 0.7 ⁇ 1.2 ⁇
  • Example 18 ⁇ ⁇ ⁇ 2.6 ⁇ 3.5 ⁇
  • Example 19 ⁇ ⁇ ⁇ 2.2 ⁇ 2.7 ⁇
  • Example # 20 ⁇ ⁇ ⁇ 0.9 ⁇ 1.2 ⁇
  • Example 21 ⁇ ⁇ ⁇ 1.2 ⁇ 1.8 ⁇
  • Example 22 ⁇ ⁇ ⁇ 0.5 0.8 ⁇
  • the pressure-sensitive adhesive composition according to the present example is compatible with reworkability and reliability.
  • both the polarizing film and the alkali free glass used in the evaluation test were thin, but when the pressure-sensitive adhesive composition according to the present example was used, the polarizing film and the alkali free glass could be peeled off from the alkali free glass almost without destroying it.
  • according to Table 9 when adhesive force exceeds 3 N / 25mm, it may be a thing which tends to be inferior to rework property.
  • silicate oligomers As silicate oligomers, the silicate oligomers used in the Examples for A. Reworkability and Reliability Evaluation were prepared. Specifically, the above-mentioned silicate oligomer B1 (preparation example 10), B2 (preparation example 11), ⁇ methyl silicate 51 (silicate oligomer B3), methyl silicate 53A (silicate oligomer B4) MKC silicate MS58B15 (silicate oligomer B5), EMS-485 ( Silicate oligomer B6) and ethyl silicate 48 (silicate oligomer B7).
  • Perbutyl ND (1 minute half-life temperature 103.5 ° C) in addition to peroyl TCP (1 minute half-life temperature 92.1 ° C.) used in Examples for reworkability and reliability evaluation And perbutyl PV '(1 minute half life temperature of 110.3 ° C) was prepared.
  • the optical film (fragmentation protective polarizing film) used by the Example for reworkability and reliability evaluation was prepared.
  • a pressure-sensitive adhesive polarizing film was produced in the same manner as in Example 1 except that the composition of the pressure-sensitive adhesive composition was changed to the composition shown in Tables 10 and 11 and the drying temperature was applied at the temperatures shown in Tables 10 and 11. Specifically, the drying temperature was applied differently depending on the type of peroxide crosslinking agent. For example, Example 23 applied a drying temperature of peroyl TCP, 120 ° C. (2 minutes), with a 1 minute half life temperature of 92.1 ° C. At least 50% by weight of the peroxide crosslinking agent was decomposed by this drying treatment.
  • Adhesive resin Silicate oligomer (B) Crosslinking agent Peroxide Crosslinking Agent Silane coupling agent Drying temperature (°C) / hour (minutes) 100 parts by weight Kinds Content (parts by weight) Molecular Weight (Mw) Kinds Content (parts by weight) Kinds Content (parts by weight) Kinds Content (parts by weight)
  • Example 23 A1 B3 5 550 D-110N 0.1 Peroyl TCP 0.3 - - 120/2
  • Example 24 A1 B4 5 900 D-110N 0.1 Peroyl TCP 0.3 - - 120/2
  • Example 25 A1 B4 0.5 900 D-110N 0.1 Peroyl TCP 0.3 - - 120/2
  • Example 26 A1 B4 30 900 D-110N 0.1 Peroyl TCP 0.3 - - 120/2
  • Example 27 A1 B6 5 1300 D-110N 0.1 Peroyl TCP 0.3 - - 120/2
  • Example 28 A1 B7 5 1400 D
  • Adhesive resin Silicate oligomer (B) Crosslinking agent Peroxide Crosslinking Agent Silane coupling agent Drying temperature (°C) / hour (minutes) 100 parts by weight Kinds Content (parts by weight) Molecular Weight (Mw) Kinds Content (parts by weight) Kinds Content (parts by weight) Kinds Content (parts by weight)
  • Example 39 A1 B4 5 900 D-110N 0.1 Peroyl TCP 0.3 - - 140/2
  • Example 40 A7 B4 5 900 D-110N 0.1 Peroyl TCP 0.3 - - 120/2
  • Example 41 A2 B4 5 900 D-110N 0.1 Peroyl TCP 0.3 - - 120/2
  • Example 42 A2 B4 5 900 V-05 0.1 Peroyl TCP 0.3 - - 120/2
  • Example 43 A2 B4 5 900 WS-500 0.1 Peroyl TCP 0.3 - - 120/2
  • Example 44 A2 B4 5 900 Tetrad
  • V-05 is a carbodiimide crosslinking agent manufactured by NISSHINBO Co., Ltd.
  • WS-500 is an oxazoline crosslinking agent of Nippon Catalyst
  • Tetrad X is an epoxy crosslinking agent of Mitsubishi Gas Chemical.
  • Wb is a weight in which 0.2g of the adhesive layer is wrapped with a fluorine resin (TEMISHNTF-1122, Nito Denko), and Wa is the weight of the fluorine resin.
  • Wc was immersed in 40 ml of ethyl acetate at 23 ° C. for 7 days to extract the soluble component, and Wc was dried on an aluminum cup at 130 ° C. for 2 hours, and then soluble. It is the weight of the adhesion layer wrapped with the fluorine resin from which the powder was removed.
  • the pressing phenomenon means that when pressed together with a pressure-sensitive adhesive optical film (sample) for evaluation of reworkability and reliability, the pressing is visually confirmed on the surface of the optical film.
  • a pressure-sensitive adhesive optical film (sample) for evaluation of the reliability and reliability 420mmX320mm
  • the hand and the naked eye on the side of the polarizing film This means that adhesiveness is observed or surface contamination of the polarizing film is observed.
  • PET oligomer deposition amount The separator was removed after leaving the above-mentioned adhesive polarizing film (including separator) at 60 ° C. and 90% RH for 500 hours. Subsequently, about 0.025 g of the adhesive layer was taken from the adhesive type polarizing film, 1 ml of chloroform was added, and after shaking for 18 hours at room temperature, 5 ml of acetonitrile was further extracted and shaken for 3 hours.
  • the obtained solution was filtered with a 0.45 ml membrane filter, a standard product of PET oligomer of trimer was adjusted to a constant concentration to prepare a calibration curve, and the calibration curve was used to request the amount (ppm) of PET oligomer contained in the pressure-sensitive adhesive.
  • the calibration curve was determined by HPLC (high performance liquid chromatography) using a sample of known PET oligomer concentration (ppm). HPLC apparatus, HPLC measurement conditions, and PET oligomer amount quantification method are as follows.
  • HPLC instrument Agilent Technologies 1200 Series
  • Quantitative method A standard sample of PET oligomer trimer was dissolved in chloroform and diluted with acetonitrile to adjust the sample to a constant concentration. The calibration curve was created in the HPLC area and the adjusted concentration. The sample PET oligomer amount (the amount of oligomer deposited on the adhesive layer) was determined along the calibration curve. The results are shown in Table 12 and Table 13.
  • the pressure-sensitive adhesive composition according to the embodiment contains an adhesive resin (A), a silicate oligomer (B), and a peroxide-based crosslinking agent having an acid value of 0 mgKOH / g to 20.0 mgKOH / g as a base polymer. .
  • the adhesive optical film which has the adhesion layer obtained from such an adhesive composition since the said adhesion layer contains a silicate oligomer (B), the adhesive force immediately after sticking an adhesive optical film to a liquid crystal cell etc. can be made low.
  • the adhesive optical film can be easily peeled from the liquid crystal cell and the like, and the reworkability is excellent. That is, the adhesive optical film can be reused without damaging or contaminating the liquid crystal cell.
  • peeling of the planar adhesive optical film was difficult for the large liquid crystal cell especially, according to this invention, a planar adhesive optical film can be easily peeled also in a large liquid crystal cell.
  • the coating film of the adhesive composition solution when the coating film of the adhesive composition solution is heated and dried by including a peroxide-based crosslinking agent in a pressure-sensitive adhesive composition at a specific ratio, it does not require aging, so it is excellent in workability, excellent in reworkability and reliability, and manufactured. Provides an adhesive optical film having excellent handling properties in terms of process.
  • the deposition temperature of the oligomer in the pressure-sensitive adhesive layer can be reduced by setting the drying temperature to 130 ° C or lower.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Une composition adhésive de la présente invention comprend une composition adhésive pour un film optique, qui contient une résine adhésive ayant une valeur acide d'environ 0 mg de KOH/g à environ 20,0 mg de KOH/g, et un oligomère de silicate représenté par la formule chimique 1, ce qui permet la compatibilité de l'aptitude au re-façonnage et de la fiabilité.
PCT/KR2015/006882 2014-07-03 2015-07-03 Composition adhésive pour film optique, couche adhésive, film optique de type adhésif et dispositif d'affichage WO2016003239A1 (fr)

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JP2017520849A JP6630728B2 (ja) 2014-07-03 2015-07-03 光学フィルム用粘着剤組成物、粘着層、粘着型光学フィルム及び表示装置
CN201580035472.3A CN106661402B (zh) 2014-07-03 2015-07-03 用于光学膜的粘着剂组成物、粘着层、粘着型光学膜及显示装置

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JP2014137711A JP2016014827A (ja) 2014-07-03 2014-07-03 光学フィルム（ｆｉｌｍ）用粘着剤、光学フィルム、及び表示装置
KR1020150092561A KR101933262B1 (ko) 2014-07-03 2015-06-29 광학 필름용 점착제 조성물, 점착층, 점착형 광학 필름 및 표시장치
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JP2017193118A (ja) * 2016-04-21 2017-10-26 三菱ケミカル株式会社 積層ポリエステルフィルム
JP2017200736A (ja) * 2016-05-06 2017-11-09 三菱ケミカル株式会社 積層ポリエステルフィルム
JP2017202647A (ja) * 2016-05-13 2017-11-16 三菱ケミカル株式会社 積層ポリエステルフィルム
JP2018095844A (ja) * 2016-12-13 2018-06-21 三星エスディアイ株式会社Samsung SDI Co., Ltd. 光学フィルム用粘着剤組成物、粘着剤層、光学部材、および画像表示装置
JP2018095843A (ja) * 2016-12-13 2018-06-21 三星エスディアイ株式会社Samsung SDI Co., Ltd. 光学フィルム用粘着剤組成物、粘着剤層、光学部材、および画像表示装置
CN114085619A (zh) * 2021-12-23 2022-02-25 泰州亚德胶粘制品有限公司 一种耐高温低粘着光学胶粘剂及其制备方法

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KR20130070568A (ko) * 2010-04-23 2013-06-27 아사히 가라스 가부시키가이샤 점착 적층체 및 표면 보호 시트
EP2684690A1 (fr) * 2011-03-09 2014-01-15 Kaneka Corporation Structure à liaison adhésive comprenant une composition adhésive et un matériau bois
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JPH08199130A (ja) * 1995-01-24 1996-08-06 Nippon Synthetic Chem Ind Co Ltd:The 粘着剤組成物
KR19990028236A (ko) * 1995-06-19 1999-04-15 쓰끼하시 다미까따 광촉매 담지 구조체 및 광촉매 코팅제
US20140039133A1 (en) * 2002-11-01 2014-02-06 Kaneka Corporation Curable composition and methods for improving recovery properties and creep properties
KR20130070568A (ko) * 2010-04-23 2013-06-27 아사히 가라스 가부시키가이샤 점착 적층체 및 표면 보호 시트
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Publication number Priority date Publication date Assignee Title
JP2017193118A (ja) * 2016-04-21 2017-10-26 三菱ケミカル株式会社 積層ポリエステルフィルム
JP2017200736A (ja) * 2016-05-06 2017-11-09 三菱ケミカル株式会社 積層ポリエステルフィルム
JP2017202647A (ja) * 2016-05-13 2017-11-16 三菱ケミカル株式会社 積層ポリエステルフィルム
JP2018095844A (ja) * 2016-12-13 2018-06-21 三星エスディアイ株式会社Samsung SDI Co., Ltd. 光学フィルム用粘着剤組成物、粘着剤層、光学部材、および画像表示装置
JP2018095843A (ja) * 2016-12-13 2018-06-21 三星エスディアイ株式会社Samsung SDI Co., Ltd. 光学フィルム用粘着剤組成物、粘着剤層、光学部材、および画像表示装置
JP7044516B2 (ja) 2016-12-13 2022-03-30 三星エスディアイ株式会社 光学フィルム用粘着剤組成物、粘着剤層、光学部材、および画像表示装置
CN114085619A (zh) * 2021-12-23 2022-02-25 泰州亚德胶粘制品有限公司 一种耐高温低粘着光学胶粘剂及其制备方法
CN114085619B (zh) * 2021-12-23 2022-07-15 泰州亚德胶粘制品有限公司 一种耐高温低粘着光学胶粘剂及其制备方法

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