WO2018048216A1 - 고분자 조성물 - Google Patents
고분자 조성물 Download PDFInfo
- Publication number
- WO2018048216A1 WO2018048216A1 PCT/KR2017/009813 KR2017009813W WO2018048216A1 WO 2018048216 A1 WO2018048216 A1 WO 2018048216A1 KR 2017009813 W KR2017009813 W KR 2017009813W WO 2018048216 A1 WO2018048216 A1 WO 2018048216A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- block
- polymer composition
- polymer
- glass transition
- transition temperature
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
- C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
-
- 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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
-
- 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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/005—Modified block copolymers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/387—Block-copolymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
-
- 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
- C09J2453/00—Presence of block copolymer
Definitions
- the present invention relates to a polymer composition, an optical laminate and a display device.
- the polymer composition is used in various fields and is typically used as an adhesive.
- One of the fields in which the pressure-sensitive adhesive is used is a liquid crystal display device (hereinafter referred to as "LCD device").
- the LCD device usually includes a liquid crystal panel and an optical film containing a liquid crystal component injected between two transparent substrates.
- a polarizing film, retardation film, a brightness improving film, etc. are mentioned.
- the adhesive for optical films is often used in order to laminate
- the pressure-sensitive adhesives include acrylic polymers, rubbers, urethane resins, silicone resins or ethylene vinyl acetate (EVA) resins.
- EVA ethylene vinyl acetate
- the main physical properties required in the pressure-sensitive adhesive composition for an optical film include cohesive force, adhesive force, reworkability, low light leakage property, stress relaxation property, and the like.
- the adhesive composition for achieving the above physical properties is proposed.
- Patent Document 1 Republic of Korea Patent No. 1023839
- Patent Document 2 Republic of Korea Patent No. 1171976
- Patent Document 3 Republic of Korea Patent No. 1171977
- the present invention provides a polymer composition, an optical laminate, a polarizing plate, and a display device.
- the polymer composition of the present invention comprises a block copolymer comprising a first block and a second block.
- the polymer composition may refer to a composition including a chemical crosslinking generally known and a component capable of simultaneously implementing a physical crosslinking structure by a physical method.
- the polymer composition may be, for example, a polymer composition capable of forming an adhesive composition.
- the block copolymer may be, for example, a block copolymer including a first block and a second block in the form of a triblock copolymer, wherein the second block is respectively bonded to both ends of the first block.
- the second block is bonded to both ends of the first block means that the second block is covalently linked through both ends of the chain of the first block.
- the block copolymer may include, for example, a first block having a glass transition temperature of 20 ° C. or more, and a second block having a glass transition temperature of 10 ° C. or less.
- the "glass transition temperature of a predetermined block” may mean a glass transition temperature measured from a polymer formed only of monomers included in the block.
- the glass transition temperature of the first block may be 20 ° C or more, 40 ° C or more or 60 ° C or more.
- the upper limit of the glass transition temperature of the first block is not particularly limited, but may be, for example, 200 ° C or less, 180 ° C or less, or 160 ° C or less.
- the glass transition temperature of the second block may be 10 ° C or less, 0 ° C or less, or -10 ° C or less.
- the lower limit of the glass transition temperature of the second block is not particularly limited, but may be, for example, -80 ° C or more, -70 ° C or more, or -60 ° C or more.
- the first block may be in the form of a tri block copolymer.
- the triblock copolymer may include, for example, an A block and a B block, and the A blocks may be respectively bonded to both ends of the B block.
- the A block is bonded to both ends of the B block means that the B block is covalently linked through both ends of the chain of the A block. Since the first block has the above-described ABA-type tree block structure, it is possible to effectively alleviate the warpage of the display due to heat generated under the condition that the display with the optical film of the present invention is driven, and thus the light leakage phenomenon It can be significantly improved.
- the A block and the B block of the first block exhibit a fine phase separation structure.
- a polymer composition capable of forming a pressure-sensitive adhesive layer having excellent stress relaxation characteristics including a stress relaxation structure consisting of a B block that can effectively disperse external stress in a physical crosslinked structure consisting of a first block Can provide.
- the first block may form a sphere, a cylinder, a gyroid, or a lamellae through fine phase separation.
- the phase type of microphase separation can be identified by imaging the surface of the polymer using an atomic force microscope (AFM) or by observing with a high magnification electron microscope.
- AFM atomic force microscope
- the first block of the present invention does not particularly limit the type of the phase, but in the case of a spear phase, it is possible to provide a polymer composition having excellent adhesive properties and physical crosslinking properties.
- the composition is not particularly limited as long as the first block can satisfy the glass transition temperature of the first block described above.
- the first block may include A blocks and B blocks having different glass transition temperatures from each other.
- the glass transition temperature of the above-mentioned A block may be 30 ° C or more, 40 ° C or more, or 50 ° C or more.
- the upper limit of the glass transition temperature of the A block is not particularly limited, but may be, for example, 200 ° C or less, 180 ° C or less, or 160 ° C or less.
- the glass transition temperature of the above-described B block may be 0 ° C or less, -10 ° C or less, or -20 ° C or less.
- the lower limit of the glass transition temperature of the B block is not particularly limited, but may be, for example, -80 ° C or more, -70 ° C or more, or -60 ° C or more.
- the A block is not particularly limited in composition if it can satisfy the above-mentioned glass transition temperature, but for example, alkyl methacrylate, acrylamide, N-alkyl acrylamide, styrene, styrene derivative, maleimide and acrylonitrile It may include as a main component a polymerized unit derived from one or more selected from the group consisting of.
- alkyl methacrylate and N-alkyl acrylamide having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 12 carbon atoms, in consideration of cohesion, glass transition temperature and the control of adhesion
- One having 8 or an alkyl group having 1 to 4 carbon atoms can be used.
- one or more of ⁇ -methylstyrene, t-butylstyrene, p-chlorostyrene, chloromethylstyrene and vinyltoluene may be used as the styrene derivative.
- the A block may preferably contain, as a main component, polymerized units derived from one or more selected from the group consisting of methyl methacrylate and styrene.
- the A block may include, as a main component, polymerized units derived from methyl methacrylate and styrene.
- the inclusion as a main component means that the inclusion of more than 50%, 55%, 65%, 75% or 95% by weight.
- the B block is not particularly limited as long as it can satisfy the above-mentioned glass transition temperature, but for example, a polymer unit derived from at least one selected from the group consisting of alkyl acrylates, olefin compounds, diene compounds, and alkylene oxides. It may include as a main component.
- the alkyl acrylate is a 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms in consideration of the control of cohesion, glass transition temperature and adhesion Alkyl acrylates having an alkyl group can be used.
- the olefin compound and the diene compound 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to carbon atoms in consideration of control of cohesion, glass transition temperature and adhesion
- the olefin compound and diene compound which are 4 can be used.
- the alkylene oxide, having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms in consideration of control of cohesion, glass transition temperature and adhesion Alkylene oxides having an alkylene group can be used.
- the B block may preferably contain, as a main component, a polymerized unit derived from butyl acrylate, ethylene glycol or 2-ethylhexyl acrylate.
- a B block contains the polymer unit mentioned above as a main component, the polymer composition which can form the adhesive layer suitable for an optical laminated body and a display apparatus can be provided.
- the first block may have a number average molecular weight (Mn) of 15,000 or more, 20,000 or more, or 25,000 or more.
- the upper limit of the number average molecular weight Mn of the first block may be 150,000 or less, 100,000 or less, or 50,000 or less.
- the first block may have a polydispersity (PDI; Mw / Mn), that is, a ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of 3 or less, 2.2 or less, or 1.4 or less.
- the lower limit of the polydispersity (Mw / Mn) may be 1.01 or more, 1.15 or more, or 1.3 or more.
- the number average molecular weight and the weight average molecular weight can be measured by, for example, the method shown in the Examples using GPC (Gel Permeation Chromatograph).
- GPC Gel Permeation Chromatograph
- the second block is not particularly limited in composition as long as it can satisfy the above-mentioned glass transition temperature.
- the second block may include a polymer unit derived from alkyl acrylate as a main component.
- the alkyl acrylate is a 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms in consideration of the control of cohesion, glass transition temperature and adhesion Alkyl acrylates having an alkyl group can be used.
- the alkyl acrylate may be butyl acrylate.
- the second block may further include, for example, polymerized units derived from at least 0.1 part by weight, at least 0.3 part by weight, or at least 0.5 part by weight of the crosslinkable monomer relative to 100 parts by weight of the alkyl acrylate.
- the second block may further include polymerized units derived from, for example, 5 parts by weight or less, 3.3 parts by weight or less, or 1.5 parts by weight or less of the crosslinkable monomer with respect to 100 parts by weight of the alkyl acrylate.
- the block copolymer In order for the block copolymer to form a physical crosslinked structure, it is preferable that the first block and the second block do not mix with each other (immiscible) to exhibit a fine phase separation structure.
- the block copolymer of the present invention for example, by including the first block and the second block having the above-described glass transition temperature, the first block and the second block can form a fine phase separation structure.
- the block copolymer of the present invention may form, for example, a microphase separation structure including the first block and the second block including the polymerized unit.
- a polymer composition capable of forming a pressure-sensitive adhesive layer having excellent stress relaxation characteristics including a stress relaxation structure consisting of a second block capable of effectively dispersing external stress in a physical crosslinked structure consisting of a first block Can be provided.
- the block copolymer may form a sphere, a cylinder, a gyroid, a lamellar phase through a fine phase separation phenomenon.
- the phase type of microphase separation can be identified by imaging the surface of the polymer using an atomic force microscope (AFM) or by observing with a high magnification electron microscope.
- AFM atomic force microscope
- the block copolymer of the present invention is not particularly limited in kind, but in the case of a spear phase, it is possible to provide a polymer composition having excellent adhesive properties and physical crosslinking properties.
- the block copolymer may have the first block or the second block include a chemical crosslinkable functional group.
- a chemical crosslinkable functional group a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, an amine group, an alkoxy silyl group, a vinyl group, etc. can be illustrated.
- the crosslinkable functional group of the present invention may be a hydroxy group.
- the adhesive layer can form the adhesive layer which has the outstanding adhesive reliability, reworkability, and cutting property.
- the crosslinkable functional group may be included in, for example, a second block having a low glass transition temperature.
- a crosslinkable functional group in the second block having a relatively low glass transition temperature, it is possible to provide a polymer composition which is excellent in warpage suppression characteristics and can form an adhesive layer in which adhesive strength is maintained according to temperature change.
- the block copolymer may have a weight ratio of the second block of 65% by weight, 75% by weight, 80% by weight, or 85% by weight or more based on the total weight of the first and second blocks.
- the upper limit of the weight ratio of the second block may be 95 wt% or less, 93 wt% or less, 91 wt% or less, or 87 wt% or less.
- the block copolymer may have a number average molecular weight (Mn) of 100,000 or more, 150,000 or more, or 200,000 or more.
- the upper limit of the number average molecular weight (Mn) of the block copolymer may be 800,000 or less, 600,000 or less, or 400,000 or less.
- the block copolymer may have a polydispersity (PDI; Mw / Mn), that is, a ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of 5 or less, 4.1 or less, or 3.2 or less.
- the lower limit of the polydispersity (Mw / Mn) may be 1.1 or more, 1.45 or more, or 1.8 or more.
- the method for producing the block copolymer is not particularly limited and can be prepared in a conventional manner.
- the block polymer may be polymerized by, for example, a Living Radical Polymerization (LRP) method, for example, an organic rare earth metal complex may be used as a polymerization initiator, or an organic alkali metal compound may be used as a polymerization initiator.
- LRP Living Radical Polymerization
- ATRP Atomic radical polymerization
- a bifunctional polymer initiator consisting of B blocks is prepared using a bifunctional initiator, and a chain extension reaction is performed on the A block to prepare an A-B-A type bifunctional triblock polymer initiator as a first block. Thereafter, a chain extension reaction is performed on the second block to prepare a block copolymer of the present invention.
- the polymer composition of the present invention may include a multifunctional crosslinking agent.
- the multifunctional crosslinking agent is not particularly limited as long as it has at least two functional groups capable of reacting with each other by crosslinking functional groups contained in the block copolymer of the present invention.
- an isocyanate crosslinking agent An epoxy crosslinking agent, an aziridine crosslinking agent, a metal chelate crosslinking agent, etc. can be used,
- an isocyanate type crosslinking agent can be used.
- isocyanate crosslinking agent For example, diisocyanate compounds, such as tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoborone diisocyanate, tetramethyl xylene diisocyanate, or naphthalene diisocyanate, Alternatively, a compound obtained by reacting the diisocyanate compound with a polyol may be used. As the polyol, for example, trimethylol propane may be used.
- crosslinking agents may be used in the pressure-sensitive adhesive composition, but a crosslinking agent that may be used is not limited thereto.
- the multifunctional crosslinking agent may be included in the polymer composition at least 0.05 part by weight or at least 0.1 part by weight relative to 100 parts by weight of the block copolymer.
- the upper limit of the content of the multifunctional crosslinking agent may be 0.35 parts by weight or less or 0.3 parts by weight or less. Within this range, the gel fraction, cohesion force, adhesive force and durability of the pressure-sensitive adhesive layer formed of the polymer composition can be maintained excellent.
- the invention also relates to an optical laminate.
- Exemplary optical laminates include optical films; And it may include an adhesive layer formed on one surface of the optical film.
- the pressure-sensitive adhesive layer may be, for example, a pressure-sensitive adhesive layer for attaching the optical film to a liquid crystal panel or the like of another display device or another optical film.
- the pressure-sensitive adhesive layer may include a crosslinked product of the polymer composition of the present invention as a main component.
- a polarizing film, a retardation film, a brightness enhancing film, or the like, or a laminate in which two or more kinds thereof are laminated may be exemplified.
- an optical laminated body may be an optical laminated body whose optical film is a polarizing film.
- the kind of polarizing film included in the optical laminate is not particularly limited, and for example, a general kind known in the art such as a polyvinyl alcohol polarizing film can be used without limitation.
- the polarizing film is a functional film capable of extracting only light vibrating in one direction from incident light while vibrating in various directions.
- a polarizing film may be a form in which a dichroic dye is adsorbed and oriented in a polyvinyl alcohol-based resin film, for example.
- Polyvinyl alcohol-type resin which comprises a polarizing film can be obtained by gelatinizing polyvinylacetate-type resin, for example.
- the polyvinylacetate resin which can be used may include not only a homopolymer of vinyl acetate but also a copolymer of vinyl acetate and other monomers copolymerizable with the above.
- Examples of the monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and a mixture of one or two or more kinds of acrylamides having an ammonium group, but are not limited thereto. no.
- the degree of gelation of the polyvinyl alcohol-based resin is usually 85 mol% to 100 mol%, preferably 98 mol% or more.
- the polyvinyl alcohol-based resin may be further modified, for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used.
- the degree of polymerization of the polyvinyl alcohol-based resin may be about 1,000 to 10,000 or about 1,500 to 5,000.
- the polarizing film is a step of stretching the polyvinyl alcohol resin film as described above (ex. Uniaxial stretching), dyeing the polyvinyl alcohol resin film with a dichroic dye, adsorbing the dichroic dye, and a dichroic dye.
- the adsorbed polyvinyl alcohol-based resin film can be produced through a process of treating with boric acid aqueous solution, and a process of washing with water after treating with boric acid aqueous solution.
- the dichroic dye iodine or a dichroic organic dye may be used.
- the polarizing plate may further include a protective film attached to one side or both sides of the polarizing film, and in this case, the pressure-sensitive adhesive layer may be formed on one side of the protective film.
- the type of protective film is not particularly limited, and includes, for example, a cellulose film such as triacetyl cellulose (TAC); Polyester film such as polycarbonate film or PET (poly (ethylene terephthalet)); Polyether sulfone-based film; Alternatively, a film having a laminated structure of one layer or two or more layers, such as a polyethylene film, a polypropylene film or a polyolefin-based film produced using a resin having a cyclo or norbornene structure, an ethylene-propylene copolymer, or the like can be used.
- the polarizing plate may further include one or more functional layers selected from the group consisting of a protective layer, a reflective layer, an antiglare layer, a retardation plate, a wide viewing angle compensation film, and a brightness enhancing film.
- the present invention also relates to an adhesive optical film.
- Exemplary pressure-sensitive adhesive optical film of the present invention may be provided with a pressure-sensitive adhesive layer through the undercoat layer on the optical film.
- the pressure-sensitive adhesive layer is a (meth) acrylic polymer (A ') segment having a glass transition temperature of 0 ° C or less, -10 ° C or less or -20 ° C or less as a base polymer, and a glass transition temperature of 30 ° C or more, 40 ° C or more or 50 °. It may be formed by a pressure-sensitive adhesive containing a block copolymer having a (meth) acrylic polymer (B ') segment that is C or more.
- the lower limit of the glass transition temperature of the A ′ segment is not particularly limited, but may be, for example, -80 ° C or more, -70 ° C or more, or -60 ° C or more.
- the upper limit of the glass transition temperature of the B ′ segment is not particularly limited, but may be, for example, 200 ° C. or less, 180 ° C. or less, or 160 ° C. or less.
- the A 'segment is not particularly limited in composition as long as it can satisfy the above-mentioned glass transition temperature, but for example, polymerization derived from at least one selected from the group consisting of alkyl acrylates, olefin compounds, diene compounds and alkylene oxides.
- the unit may be included as a main component.
- the alkyl acrylate is a 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms in consideration of the control of cohesion, glass transition temperature and adhesion Alkyl acrylates having an alkyl group can be used.
- the olefin compound and the diene compound 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to carbon atoms in consideration of control of cohesion, glass transition temperature and adhesion
- the olefin compound and diene compound which are 4 can be used.
- the alkylene oxide, having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms in consideration of control of cohesion, glass transition temperature and adhesion Alkylene oxides having an alkylene group can be used.
- the segment A ′ may preferably comprise, as a main component, polymerized units derived from butyl acrylate, ethylene glycol or 2-ethylhexyl acrylate.
- the base polymer which can form the adhesive layer suitable for an adhesive optical film can be provided when A 'segment contains the polymer unit mentioned above as a main component.
- the B 'segment is not particularly limited in composition as long as it can satisfy the above-mentioned glass transition temperature, but for example, alkyl methacrylate, acrylamide, N-alkyl acrylamide, styrene, styrene derivative, maleimide and acryl Polymeric units derived from one or more selected from the group consisting of nitriles may be included as a main component.
- alkyl methacrylate and N-alkyl acrylamide having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 12 carbon atoms, in consideration of cohesion, glass transition temperature and the control of adhesion
- One having 8 or an alkyl group having 1 to 4 carbon atoms can be used.
- one or more of ⁇ -methylstyrene, t-butylstyrene, p-chlorostyrene, chloromethylstyrene and vinyltoluene may be used as the styrene derivative.
- the segment B ′ may preferably comprise, as its main component, polymerized units derived from one or more selected from the group consisting of methyl methacrylate and styrene.
- the segment B ′ may alternatively comprise, as its main component, polymerized units derived from methyl methacrylate and styrene.
- the base polymer which can form the adhesive layer suitable for an adhesive optical film can be provided by the B 'segment containing the polymer unit mentioned above as a main component.
- the base polymer may be a triblock copolymer in which A 'and B' segments are connected in a B'-A'-B 'form.
- the base polymer has a triblock structure connected in the above-described B'-A'-B 'form to effectively alleviate warping of the display due to heat generated under conditions in which the display with the adhesive optical film of the present invention is driven.
- the light leakage phenomenon can be significantly improved.
- the A ⁇ segment and the B ⁇ segment of the base polymer exhibit a fine phase separation structure.
- the base polymer may form a pressure-sensitive adhesive layer having excellent stress relaxation characteristics, including a stress relaxation structure composed of A ′ segments capable of effectively dispersing external stresses in the physical crosslinked structure of the base polymer.
- the base polymer may further include, for example, a polymer (C) segment connected to the B ′ segment and having a glass transition temperature of 10 ° C. or less, 0 ° C. or less, or ⁇ 10 ° C. or less.
- the lower limit of the glass transition temperature of the C segment is not particularly limited, but may be, for example, -80 ° C or higher, -70 ° C or higher, or -60 ° C or higher.
- the base polymer and the C segment have a fine phase separation structure to be described later to form a physical crosslink which can form a structure including a stress relaxation point.
- a crosslinkable composition capable of forming an adhesive layer having excellent adhesion reliability, reworkability and cutting properties.
- the C segment is not particularly limited in composition as long as it can satisfy the above-described glass transition temperature.
- the C segment may include a polymer unit derived from alkyl acrylate as a main component.
- the alkyl acrylate is a 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms in consideration of the control of cohesion, glass transition temperature and adhesion Alkyl acrylates having an alkyl group can be used.
- the alkyl acrylate may be butyl acrylate.
- the C segment may comprise a chemical crosslinkable functional group.
- a chemical crosslinkable functional group a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, an amine group, an alkoxy silyl group, a vinyl group, etc.
- the crosslinkable functional group of the present invention may be a hydroxy group.
- the base polymer may, for example, have a weight ratio of C segment at least 65 wt%, at least 75 wt% and at least 80 wt% or at least 85 wt%.
- the upper limit of the weight ratio of the C segment may be 95 wt% or less, 93 wt% or less, 91 wt% or less, or 87 wt% or less.
- the molecular weight, polydispersity, and preparation method of the base polymer are the same as described in the above-described molecular weight, polydispersity, and preparation method of the block copolymer of the polymer composition of the present invention.
- the undercoat is formed by a undercoat containing polymers and antioxidants. It is preferable that the material of the said polymers can form the film which shows favorable adhesiveness to any of an adhesive layer and an optical film, for example, a liquid crystal optical compensation layer, and is excellent in cohesion force.
- polymers examples include polyurethane-based resins, polyester-based resins, and polymers containing amino groups in molecules.
- the use form of a polymer may be any of a solvent soluble type, a water dispersion type, and a water-soluble dissolution type.
- water-soluble polyurethane, water-soluble polyester, water-soluble polyamide, etc., and water-dispersible resin ethylene-vinyl acetate emulsion, (meth) acrylic emulsion, etc. are mentioned.
- the water dispersion type emulsifies various resins, such as a polyurethane, polyester, and polyamide, using an emulsifier, and introduce
- polymers have a functional group which has reactivity with an isocyanate type compound, when an adhesive layer contains an isocyanate type compound, for example.
- numerator is preferable.
- a terminal having a primary amino group at the terminal is preferably used, and the reaction with an isocyanate compound is more firmly adhered, and the durability is improved.
- the polymer which has a primary amino group at the terminal the poly (meth) acrylic acid ester which has a primary amino group at the terminal is preferable.
- polymers containing an amino group in the molecule include polymers of amino group-containing monomers such as polyethyleneimine, polyallylamine, polyvinylamine, polyvinylpyridine, polyvinylpyrrolidine and ethyl dimethylaminoacrylate.
- polyethyleneimine type is preferable.
- a polyethyleneimine type material what has a polyethyleneimine structure is preferable,
- the polyethyleneimine and the ethyleneimine adduct to polyacrylic acid ester, and / or a polyethyleneimine adduct are mentioned.
- ethyleneimine adducts and / or polyethyleneimine adducts to polyacrylic acid esters which are poly (meth) acrylic acid esters having a primary amino group at the terminal.
- Polyethylenimine is not specifically limited, Various things can be used.
- the weight average molecular weight of polyethyleneimine is not particularly limited but is generally about 1 to 1 million.
- Examples of commercially available products of polyethyleneimine include Epomin SP series (SP-003, SP006, SP012, SP018, SP103, SP110, SP200, and the like), Epomin P-1000, and the like. Among them, epomin P-1000 is suitable.
- the polyacrylic acid ester of the ethyleneimine adduct and / or the polyethyleneimine adduct to the polyacrylic acid ester is obtained by emulsion polymerization of the alkyl (meth) acrylate and its copolymerization monomer constituting the base polymer (acrylic polymer) of the acrylic pressure sensitive adhesive described later. .
- a copolymerization monomer in order to make ethylene imine etc. react, the monomer which has functional groups, such as a carboxyl group, is used.
- the use ratio of monomer which has functional groups, such as a carboxyl group is suitably adjusted with the ratio of ethylene imine etc. made to react.
- styrene monomer as a copolymerization monomer.
- the adduct which grafted the polyethyleneimine can also be used by making polyethyleneimine synthesize
- Nihon Shokubai Co., Ltd. portfolio NK-380 is mentioned as an example of a commercial item.
- ethyleneimine adducts and / or polyethyleneimine adducts of acrylic polymer emulsions may be used.
- Nippon Shokubai Co., Ltd. portfolio SK-1000, etc. are mentioned as an example of a commercial item.
- the poly (meth) acrylic acid ester which has a primary amino group at the terminal is obtained by copolymerizing the said (meth) acrylic acid ester and the monomer which has a primary amino group at the terminal.
- a monomer which has a primary amino group at the terminal aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, etc. are mentioned, for example.
- additives such as antioxidants
- various types of additives such as antioxidants, may be suitably used for the undercoating layer as necessary without departing from the object of the present invention.
- antioxidant contained in the undercoat layer examples include phenol-based, phosphorus-based, sulfur-based, and amine-based antioxidants, and at least one selected from these can be used. Among these, a phenolic antioxidant is preferable.
- phenolic antioxidant examples include 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethyl phenol and 2,6-dicyclohexyl-4 as monocyclic phenol compounds.
- phosphorus antioxidants include trioctyl phosphite, trilauryl phosphite, tris tridecyl phosphite, tris isodecyl phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, and phenyl di (tridecyl) phosphate.
- the polyhydric alcohol ester of dialkylthio dipropionate and alkylthio propionic acid As sulfur type antioxidant, it is preferable to use the polyhydric alcohol ester of dialkylthio dipropionate and alkylthio propionic acid.
- dialkylthiodipropionate used herein a dialkylthiodipropionate having an alkyl group having 6 to 20 carbon atoms is preferable, and as the polyhydric alcohol ester of alkylthio propionic acid, an alkylthio propionic acid having an alkyl group having 4 to 20 carbon atoms is used.
- Polyhydric alcohol esters of are preferred.
- examples of the polyhydric alcohol constituting the polyhydric alcohol ester include glycerin, trimethylol ethane, trimetholpropane, pentaerythritol, tris hydroxyethyl isocyanurate, and the like.
- examples of such dialkylthiodipropionate include dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and the like.
- polyhydric alcohol ester of alkylthio propionic acid for example, glycerin tributyl thio propionate, glycerin trioctyl thio propionate, glycerin trilauryl thiopropionate, glycerin tristearyl thio propion Esters, trimethylol ethane tributyl thio propionate, trimethylol ethane trioctyl thio propionate, trimethylol ethane trilauryl thiopropionate, trimethylol ethane tristearyl thio propion ester propionate), pentaerythritol tetrabutyl thio propionate, pentaerythritol tetraoctyl thio propionate and pentaerythritol tetralauryl thiopropionate, pentaerythritol tetralauryl thio
- amine antioxidant examples include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2 Polycondensates of 6,6-tetramethylpiperidine ethanol, N, N ', N' ', N' ⁇ '-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2 , 6,6-tetramethylpiperidin-4-yl) amino) -triazin2-yl) -4,7-diazadecan-1,10-diamine, dibutyl amine 1,3,5-triazine N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl 1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl ) Polycondensates of butyl amine, poly [ ⁇ 6- (1,1,3,3-tetramethylbutyl)
- the undercoat When the undercoat includes polymers and antioxidants, it may generally include 0.01 to 500 parts by weight of antioxidant based on 100 parts by weight of polymers. When the ratio of use of the antioxidant falls within the above range, it is possible to provide an undercoat layer having good anchoring properties and appearance and excellent antioxidant performance.
- the use ratio of antioxidant is preferably 0.1 to 300 parts by weight, or 1 to 100 parts by weight based on 100 parts by weight of the polymers.
- the undercoat may contain a crosslinking agent together with the polymers.
- strength of an undercoat layer can be improved by mixing and crosslinking the crosslinking agent which reacts with the polymer containing an amino group.
- Epoxy compounds etc. are mentioned as a crosslinking agent which reacts with the polymer containing an amino group, for example.
- the production of the pressure-sensitive adhesive optical film of the present invention is carried out by forming an undercoat on an optical film, for example, a liquid crystal optical compensation layer, and forming an adhesive layer.
- the undercoat layer may be formed by, for example, applying and drying the undercoat solution containing the polymer and the antioxidant using a coating method such as a coating method, a dipping method, and a spray method.
- the thickness of the undercoat is preferably 10 to 5000 nm or 50 to 500 nm. If the thickness of the undercoat layer becomes thin, the undercoat layer may not exhibit sufficient strength, and sufficient adhesion may not be obtained. In addition, too thick may result in deterioration of the optical properties.
- the application amount (solid content) of an undercoat layer is 0.1-5 cubic centimeters, 0.1-1 cubic centimeters, or 0.1-0.5 cubic centimeters per square meter.
- Formation of an adhesive layer is performed by laminating
- the coating method may be a roll coating method such as reverse coating or gravure coating, a spin coating method, a screen coating method, a fountain coating method, a dipping method, a spray method, or the like.
- the constituent material of the release sheet examples include synthetic resin films such as paper, polyethylene, polypropylene, and polyethylene terephthalate, rubber sheets, paper, cloth, nonwoven fabrics, nets, foamed sheets and metal foils, and suitable thin films such as laminates thereof. have.
- the surface of a release sheet may be given peeling processes, such as a silicone treatment, a long chain alkyl treatment, and a fluorine treatment, as needed.
- the invention also relates to a display device, for example a liquid crystal display device.
- the exemplary display device may include a liquid crystal panel and the polarizing plate or the optical laminate attached to one or both surfaces of the liquid crystal panel.
- the polarizing plate or the optical laminate may be attached to the liquid crystal panel by the pressure-sensitive adhesive described above.
- the liquid crystal panel in the apparatus may be, for example, a passive matrix panel such as twisted nematic (TN) type, super twisted nematic (STN) type, ferroelectic (F) type or polymer dispersed (PD) type; Active matrix panels such as two-terminal or three-terminal; All known panels, such as an In Plane Switching (IPS) panel and a Vertical Alignment (VA) panel, can be applied.
- TN twisted nematic
- STN super twisted nematic
- F ferroelectic
- PD polymer dispersed
- Active matrix panels such as two-terminal or three-terminal
- All known panels such as an In Plane Switching (IPS) panel and a Vertical Alignment (VA) panel, can be applied.
- IPS In Plane Switching
- VA Vertical Alignment
- liquid crystal display device for example, upper and lower substrates such as a color filter substrate or an array substrate, are not particularly limited, and a configuration known in the art may be employed without limitation.
- the present invention is excellent in workability, excellent durability and dimensional stability through a polymer capable of forming a physical crosslinked structure in addition to a chemical crosslinked structure and can form an adhesive layer that can effectively alleviate the warpage phenomenon of the display
- a polymer composition may be provided, and an optical laminate including a crosslinked product of the polymer composition and a display device including the same may be provided.
- FIG. 1 is a view showing the structure of an exemplary adhesive optical film of the present invention.
- Mw weight average molecular weight
- Mn number average molecular weight
- Mn number average molecular weight
- PDI molecular weight distribution
- the pressure-sensitive adhesive polarizing plate prepared in Example or Comparative Example was cut to have a length of 320cm and a length of 180cm to prepare a specimen.
- the prepared specimen was attached to a commercially available LCD panel having a thickness of about 0.7 mm through the pressure-sensitive adhesive layer, and the panel to which the specimen was attached was stored at 50 ° C and 5 atmospheres for about 20 minutes to prepare a sample. After maintaining the prepared sample at 80 ° C. for 300 hours to observe the occurrence of bubbles or peeling phenomenon at the adhesive interface of the pressure-sensitive adhesive layer to evaluate the durability according to the following criteria.
- the pressure-sensitive adhesive polarizing plate prepared in Example or Comparative Example was cut to have a length of 3 cm and a length of 40.5 cm to prepare a specimen.
- the prepared specimen is attached to the LCD panel having a thickness of about 0.7 mm and a width of 4 cm and a length of 42 cm via the pressure-sensitive adhesive layer.
- One end of the specimen is attached to the oven wall with the iron support using a magnet and the other end is measured from the wall (d1).
- the warpage is measured by measuring the distance (d2) from the wall of the oven. Relative fraction of warpage is calculated based on the warpage of the specimen using the random copolymer of Comparative Example 3.
- ethylene bis (2-bromoisobutyrate), 15.5 g butyl acrylate (BA) and 16 g ethyl acetate (Ethyl acetate) are placed in a 500 mL round bottom flask and sealed for about 40 minutes Ring to remove oxygen. After deoxygenation, the flask was placed in an oil bath heated to 65 ° C. and 0.002 g CuBr 2 and 0.006 g TPMA (tris (2-pyridylmethyl) amine) were deoxygenated in 0.1 mL DMF (N, N-dimethylformamide). The dissolved solution was added to the flask.
- DMF N, N-dimethylformamide
- ethylene bis (2-bromoisobutyrate), 28.2 g of butyl acrylate (BA) and 30 g of ethyl acetate are placed in a 500 mL round bottom flask and sealed for about 40 minutes Ring to remove oxygen. After deoxygenation, the flask was placed in an oil bath heated to 65 ° C. and 0.005 g of CuBr 2 and 0.013 g of TPMA (tris (2-pyridylmethyl) amine) were deoxygenated in 0.2 mL DMF (N, N-dimethylformamide). The dissolved solution was added to the flask.
- TPMA tris (2-pyridylmethyl) amine
- the chain extension reaction was initiated by introducing 3.3 g of a solution containing 5% by weight of azobisisobutyronitrile (AIBN) and a solvent of ethyl acetate. The reaction was terminated when the reaction conversion rate reached about 80% to prepare a block copolymer solution having a molecular weight (Mn) of 250,000 and a molecular weight distribution (Mw / Mn) of 2.88.
- the weight ratio of the first block and the second block is about 15:85.
- the chain extension reaction was initiated by introducing 3.3 g of a solution containing 5% by weight of azobisisobutyronitrile (AIBN) and a solvent of ethyl acetate. The reaction was terminated when the reaction conversion rate reached about 85% to prepare a block copolymer solution having a molecular weight (Mn) of 240,000 and a molecular weight distribution (Mw / Mn) of 3.15.
- Mn molecular weight
- Mw / Mn molecular weight distribution
- the weight ratio of the first block and the second block is about 13:87.
- ethylene glycol di-alphabromoisobutyrate 0.33 g of ethylene glycol di-alphabromoisobutyrate, 22.9 g of 2-ethylhexyl acrylate (2-EHA) and 25 g of ethyl acetate were placed in a 500 mL round bottom flask and sealed. Oxygen was removed by nitrogen bubbling for about 40 minutes. After deoxygenation, the flask was placed in an oil bath heated to 65 ° C. and 0.003 g of CuBr 2 and 0.007 g of TPMA (tris (2-pyridylmethyl) amine) were deoxygenated in 0.2 mL DMF (N, N-dimethylformamide). The dissolved solution was added to the flask.
- 2-EHA 2-ethylhexyl acrylate
- azobisisobutyronitrile (AIBN) 5% EA solution was added as a catalyst reducing agent to initiate the reaction.
- AIBN azobisisobutyronitrile
- MMA methyl methacrylate
- ethyl acetate which had been previously deoxygenated
- Chain extension was carried out by adding 4.6 g of a solution containing 5% by weight of isobutisoronitrile (AIBN) and a solvent of ethyl acetate. When the conversion reached 80%, the reaction mixture was transferred entirely to the 3 L polymerization reactor via a pump. Into a 3 L reactor, 1185 g of butyl acrylate (BA), 12.0 g of 4-hydroxybutyl acrylate (4-HBA) and 1000 g of ethyl acetate were added and about 60 minutes While bubbling with nitrogen to remove oxygen.
- BA butyl acrylate
- 4-HBA 4-hydroxybutyl acrylate
- ethyl acetate 1000 g
- the catalyst solution was mixed with 0.036 g of CuBr 2 , 0.093 g of TPMA (tris (2-pyridylmethyl) amine) and 5 mL of DMF (N, N-dimethylformamide) while maintaining the reaction temperature at about 65 ° C.
- the chain extension reaction was initiated by adding 3.0 g of a solution containing Azobisisobutyronitrile (AIBN) at 5% by weight and a solvent of ethyl acetate. The reaction was terminated when the reaction conversion rate reached about 70% to prepare a block copolymer solution having a molecular weight (Mn) of 220,000 and a molecular weight distribution (Mw / Mn) of 2.85.
- the weight ratio of the first block and the second block is about 15:85.
- composition and physical properties of the block copolymers prepared in Preparation Examples 1 to 4 above are summarized as follows.
- Preparation Example 1 Preparation Example 2
- Preparation Example 3 Preparation Example 4
- A1 A2 A3 A4 Block copolymer First block (A-B-A) The composition of A block MMA MMA + St MMA MMA Composition of B block BA BA PEG EHA Tg of A block 105 ° C 103 ° C 105 ° C 105 ° C Tg of B block -54 ° C -54 ° C -85 ° C -50 ° C 1st block Tg 77 ° C 62 ° C 59 ° C 58 ° C A: B weight ratio 11:89 18:82 14:86 17:83 Mn 85000 70000 76000 65000 Dispersion (Mw / Mn) 1.32 1.75 1.58 1.62 Second block Furtherance BA + HBA BA + HBA BA + HBA BA + HBA BA + HBA Tg -54 ° C -54 ° C -54 ° C -54 ° C 1st block: 2nd
- Chain extension was carried out by adding 6 g of a solution containing 5% by weight of isobutisoronitrile (AIBN) and a solvent of ethyl acetate. When the conversion reached 80%, the reaction mixture was transferred entirely to the 3 L polymerization reactor via a pump. Into a 3 L reactor, 1300 g of butyl acrylate (BA), 13.1 g of 4-hydroxybutyl acrylate (4-HBA) and 1000 g of ethyl acetate were added and about 60 minutes While bubbling with nitrogen to remove oxygen.
- BA butyl acrylate
- 4-HBA 4-hydroxybutyl acrylate
- ethyl acetate 1000 g
- a catalyst solution containing 0.035 g of CuBr 2 , 0.090 g of TPMA (tris (2-pyridylmethyl) amine) and 5 mL of DMF (N, N-dimethylformamide) was added while maintaining the reaction temperature at about 65 ° C.
- the chain extension reaction was initiated by introducing 3.3 g of a solution containing 5% by weight of azobisisobutyronitrile (AIBN) and a solvent of ethyl acetate. The reaction was terminated when the reaction conversion rate reached about 80% to prepare a block copolymer solution having a molecular weight (Mn) of 240,000 and a molecular weight distribution (Mw / Mn) of 2.84.
- Mn molecular weight
- Mw / Mn molecular weight distribution
- the weight ratio of the first block and the second block is about 15:85.
- Comparative Preparation Example 2 Preparation of Diblock Copolymer (B2) 0.28 g of ethyl alpha bromoisobutyrate, 190 g of methyl methacrylate (MMA) and 190 g of ethyl acetate were added thereto, followed by nitrogen for 40 minutes. Bubbled to remove oxygen. When the temperature of the reactant reaches 65 degrees, 0.036 g of CuBr 2 and 0.092 g of TPMA (tris (2-pyridylmethyl) amine) are dissolved in 1.5 mL DMF (N, N-dimethylformamide), which is deoxygenated.
- DMF N, N-dimethylformamide
- Chain extension was carried out by adding 6 g of a solution containing 5 wt% of butyronitrile (Azobisisobutyronitrile, AIBN) and ethyl acetate (Ethyl acetate). When the conversion reached 80%, the reaction mixture was transferred entirely to the 3 L polymerization reactor via a pump. Into a 3 L reactor, 1300 g of butyl acrylate (BA), 13.1 g of 4-hydroxybutyl acrylate (4-HBA) and 1000 g of ethyl acetate were added and about 60 minutes While bubbling with nitrogen to remove oxygen.
- BA butyl acrylate
- 4-HBA 4-hydroxybutyl acrylate
- ethyl acetate 1000 g
- a catalyst solution containing 0.035 g of CuBr 2 , 0.090 g of TPMA (tris (2-pyridylmethyl) amine) and 5 mL of DMF (N, N-dimethylformamide) was added while maintaining the reaction temperature at about 65 ° C.
- the chain extension reaction was initiated by introducing 3.3 g of a solution containing 5% by weight of azobisisobutyronitrile (AIBN) and a solvent of ethyl acetate. The reaction was terminated when the reaction conversion rate reached about 80% to prepare a block copolymer solution having a molecular weight (Mn) of 260,000 and a molecular weight distribution (Mw / Mn) of 2.87.
- the weight ratio of the first block and the second block is about 15:85.
- Random copolymer B2 introduced with only chemical crosslinking was prepared as follows. 200 g of butyl acrylate (BA), 2.0 g of 4-hydroxybutyl acrylate (4-HBA) and 600 g of ethyl acetate were added to the flask, followed by bubbling nitrogen for 60 minutes to dissolve oxygen. Remove it. When the reaction temperature reaches 65 ° C. 2 wt% ethyl acetate solution containing 0.10 g of Azobisisobutyronitrille (AIBN) is added to start the reaction. When reaction conversion became about 70%, reaction was complete
- a pressure-sensitive adhesive polarizing plate was manufactured in the same manner as in Example 1, except that the pentablock copolymers (A2, A3, A4) prepared in Preparation Examples 2 to 4 were used.
- a pressure-sensitive adhesive polarizing plate was manufactured in the same manner as in Example 1, except that the block copolymers (B1, B2) and random copolymers prepared in Comparative Preparation Examples 1 to 3 were used.
- Example Comparative example A1 A2 A3 A4 B1 B2 B3 (reference specimen) Torture structure Pentablock Pentablock Pentablock Pentablock Tree block Deblock random High temperature durability A A A A A A A B % Relative deflection 71 69 66 66 92 87 100
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Graft Or Block Polymers (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polarising Elements (AREA)
Abstract
Description
제조예 1 | 제조예 2 | 제조예 3 | 제조예 4 | |||
A1 | A2 | A3 | A4 | |||
블록공중합체 | 제1블록(A-B-A) | A블록의 조성 | MMA | MMA+St | MMA | MMA |
B블록의 조성 | BA | BA | PEG | EHA | ||
A블록의 Tg | 105°C | 103°C | 105°C | 105°C | ||
B블록의 Tg | -54°C | -54°C | -85°C | -50°C | ||
제 1 블록 Tg | 77°C | 62°C | 59°C | 58°C | ||
A:B 중량비 | 11:89 | 18:82 | 14:86 | 17:83 | ||
Mn | 85000 | 70000 | 76000 | 65000 | ||
분산도(Mw/Mn) | 1.32 | 1.75 | 1.58 | 1.62 | ||
제 2 블록 | 조성 | BA+HBA | BA+HBA | BA+HBA | BA+HBA | |
Tg | -54°C | -54°C | -54°C | -54°C | ||
제 1 블록: 제 2 블록 중량비 | 14:86 | 15:85 | 13:87 | 15:85 | ||
Mn | 350000 | 250000 | 240000 | 220000 | ||
분산도(Mw/Mn) | 1.84 | 2.88 | 3.15 | 2.85 | ||
MMA: 메틸메타크릴레이트St: 스티렌BA: 부틸 아크릴레이트PEG: 폴리에틸렌글리콜EHA: 2-에틸헥실아크릴레이트HBA: 4-히드록시부틸아크릴레이트 |
실시예 | 비교예 | ||||||
A1 | A2 | A3 | A4 | B1 | B2 | B3(기준시편) | |
고문자 구조 | 펜타블록 | 펜타블록 | 펜타블록 | 펜타블록 | 트리블록 | 디블록 | 랜덤 |
고온 내구 특성 | A | A | A | A | A | A | B |
휨 상대분율(%) | 71 | 69 | 66 | 66 | 92 | 87 | 100 |
Claims (18)
- 유리전이온도가 20°C 이상이며, 트리 블록 공중합체 형태인 제 1 블록 및 유리전이온도가10°C 이하인 제 2 블록을 포함하고,상기 제 1 또는 제 2 블록은 가교성 관능기를 포함하며,상기 제 2 블록은 상기 제 1 블록의 양 말단에 각각 결합되어 있는 블록 공중합체를 포함하는 고분자 조성물.
- 제 1 항에 있어서, 제 1 블록은 유리전이온도가 30°C 이상인 A 블록과 유리전이온도가0°C 이하인 B 블록을 포함하고, 상기 A 블록이 상기 B 블록의 양 말단에 각각 결합되어 있으며, 제 2 블록이 상기 A 블록의 말단에 결합되어 있는 고분자 조성물.
- 제 2 항에 있어서, A블록은 알킬 메타크릴레이트, 아크릴아미드, N-알킬 아크릴아미드, 스티렌, 스티렌 유도체, 말레이미드 및 아크릴로니트릴로 이루어진 군으로부터 선택된 하나 이상으로 유래된 중합 단위를 주성분으로 포함하는 고분자 조성물.
- 제 2 항에 있어서, B블록은 알킬 아크릴레이트, 올레핀 화합물, 디엔 화합물 및 알킬렌옥시드로 이루어진 군으로부터 선택된 하나 이상으로 유래된 중합 단위를 주성분으로 포함하는 고분자 조성물.
- 제2 항에 있어서, A 및 B 블록 합계 중량을 기준으로 A 블록의 중량 비율이 50 내지 95 중량%의 범위 내인 고분자 조성물.
- 제 1 항에 있어서, 제 1 블록의 수평균분자량은 15,000 내지 150,000 의 범위 내에 있는 고분자 조성물.
- 제 1 항에 있어서, 제 1 블록의 다분산도(Mw/Mn)는 1.01 내지 3 의 범위 내에 있는 고분자 조성물.
- 제 1 항에 있어서, 제 2 블록은 알킬 아크릴레이트로부터 유래한 중합 단위를 주성분으로 포함하는 고분자 조성물.
- 제 1항에 있어서, 제 2 블록은 알킬 아크릴레이트 100 중량부 대비 0.1 내지 5 중량부의 가교성 단량체로부터 유래한 중합 단위를 추가로 포함하는 고분자 조성물.
- 제 1 항에 있어서, 제 1 및 제 2 블록의 합계 중량을 기준으로 하는 제 2 블록의 중량 비율은, 65 내지 95중량%의 범위 내인 고분자 조성물.
- 제 1 항에 있어서, 블록 공중합체는 수평균분자량(Mn)이 10만 내지 80만의 범위 내인 고분자 조성물.
- 제 1 항에 있어서, 블록 공중합체는 다분산도(Mw/Mn)가 5 이하인 고분자 조성물.
- 제 1 항에 있어서, 블록 공중합체는, 상분리 구조를 형성하는 고분자 조성물.
- 제 13 항에 있어서, 상분리 구조는 스피어 구조인 고분자 조성물.
- 제 1 항에 있어서, 가교성 관능기와 반응하는 관능기를 가지는 다관능성 가교제를 추가로 포함하는 고분자 조성물.
- 광학 필름; 및 상기 광학 필름의 일면에 형성되어 있는 점착제층을 포함하고, 상기 점착제층은 제 1 항의 고분자 조성물의 가교물을 포함하는 광학 적층체.
- 광학 필름에 하도층을 통해 점착제층이 설치되어 있는 점착형 광학 필름에 있어서, 점착제층이 유리 전이 온도가 0℃이하의 (메타) 아크릴계 중합체(A’) 세그먼트 및 유리 전이 온도가 40℃이상의 (메타) 아크릴계 중합체(B’) 세그먼트를 가지는 블록 공중합체인 베이스 폴리머를 함유하는 점착제에 의해 형성되어 있고, 또한 상기 하도층은 폴리머류를 함유하며, 상기 베이스 폴리머에서 A’ 및 B’ 세그먼트는 B’-A’-B’ 형태로 연결되어 있고, 상기 베이스 폴리머는, 상기 B’ 세그먼트에 연결되어 있고, 유리전이온도가 10℃ 이하인 중합체(C) 세그먼트를 추가로 포함하는 것을 특징으로 하는 점착형 광학 필름.
- 제 16 항의 광학 적층체를 포함하는 디스플레이 장치.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16/305,296 US11180597B2 (en) | 2016-09-08 | 2017-09-07 | Polymer composition |
JP2018544232A JP6785870B2 (ja) | 2016-09-08 | 2017-09-07 | 高分子組成物 |
EP17849100.7A EP3434745A4 (en) | 2016-09-08 | 2017-09-07 | POLYMER COMPOSITION |
CN201780016605.1A CN108779319B (zh) | 2016-09-08 | 2017-09-07 | 聚合物组合物 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2016-0115609 | 2016-09-08 | ||
KR1020160115609A KR102097817B1 (ko) | 2016-09-08 | 2016-09-08 | 고분자 조성물 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018048216A1 true WO2018048216A1 (ko) | 2018-03-15 |
Family
ID=61562464
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2017/009813 WO2018048216A1 (ko) | 2016-09-08 | 2017-09-07 | 고분자 조성물 |
Country Status (7)
Country | Link |
---|---|
US (1) | US11180597B2 (ko) |
EP (1) | EP3434745A4 (ko) |
JP (1) | JP6785870B2 (ko) |
KR (1) | KR102097817B1 (ko) |
CN (1) | CN108779319B (ko) |
TW (1) | TWI642745B (ko) |
WO (1) | WO2018048216A1 (ko) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3702376B1 (en) | 2018-09-24 | 2020-12-23 | Infineum International Limited | Method of making polymers |
JPWO2021045072A1 (ko) * | 2019-09-03 | 2021-03-11 | ||
JP7451938B2 (ja) * | 2019-10-25 | 2024-03-19 | 東亞合成株式会社 | 粘着剤組成物及び粘着性製品 |
JP7400572B2 (ja) | 2020-03-19 | 2023-12-19 | 三菱ケミカル株式会社 | 活性エネルギー線硬化性剥離型粘着剤組成物および剥離型粘着シート |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6288173B1 (en) * | 1999-06-03 | 2001-09-11 | Ppg Industries Ohio, Inc. | Block copolymers |
JP2010106230A (ja) * | 2008-09-30 | 2010-05-13 | Sekisui Chem Co Ltd | 粘着剤組成物 |
KR20110008028A (ko) * | 2008-03-07 | 2011-01-25 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 대전 방지 블록 코폴리머 감압성 접착제 및 물품 |
KR101023839B1 (ko) | 2008-07-24 | 2011-03-22 | 주식회사 엘지화학 | 점착제 조성물, 상기를 포함하는 편광판 및 액정표시장치 |
US20120029139A1 (en) * | 2009-01-30 | 2012-02-02 | Centre National De La Recherche Scientifique (Cnrs | Block copolymers having associative groups, and adhesive containing same |
KR101171976B1 (ko) | 2007-12-29 | 2012-08-08 | 주식회사 엘지화학 | 아크릴계 점착제 조성물, 이를 포함하는 편광판 및액정표시장치 |
KR101171977B1 (ko) | 2008-06-05 | 2012-08-08 | 주식회사 엘지화학 | 아크릴계 점착제 조성물, 이를 포함하는 편광판 및액정표시장치 |
KR20140119167A (ko) * | 2012-01-31 | 2014-10-08 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | 공중합체를 포함하는 필름, 물품 및 방법 |
KR20160115609A (ko) | 2015-03-27 | 2016-10-06 | 아이디에이씨 홀딩스, 인크. | 실수 m진 신호 부호화 방법, 및 이를 이용한 부호화 장치 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19855062A1 (de) | 1998-11-28 | 2000-05-31 | Bayer Ag | Blockcopolymere auf Vinylcyclohexanbasis |
JP4572006B2 (ja) | 1998-12-08 | 2010-10-27 | 日東電工株式会社 | 粘着剤組成物およびその製造方法と粘着シ―ト類 |
DE10129608A1 (de) * | 2001-06-20 | 2003-05-28 | Tesa Ag | Stripfähige Systeme auf Basis von Acrylatblockcopolymeren |
DE10248380A1 (de) * | 2002-10-17 | 2004-08-05 | Tesa Ag | Haftklebrige Formteile |
DE10256782A1 (de) * | 2002-12-05 | 2004-08-05 | Tesa Ag | Haftklebeartikel |
WO2006077855A1 (ja) * | 2005-01-21 | 2006-07-27 | Nippon Soda Co., Ltd. | 高分子、架橋高分子、高分子固体電解質用組成物、高分子固体電解質及び接着性組成物 |
WO2006104097A1 (ja) * | 2005-03-28 | 2006-10-05 | Kaneka Corporation | アクリル系ブロック共重合体、反応性ホットメルト接着剤組成物 |
DE102006035786A1 (de) * | 2006-07-28 | 2008-03-13 | Tesa Ag | Haftklebefolie mit hoher optischer Transparenz zur Verklebung als Splitterschutz auf Glasscheiben in Konsumgüterelektronikbauteilen |
DE102007039535A1 (de) | 2007-08-21 | 2009-02-26 | Evonik Röhm Gmbh | Verfahren zur Herstellung von Pentablockcopolymeren mit OH-funktionalisierten Blöcken auf (Meth)acrylatbasis |
CA2800729C (en) * | 2010-06-04 | 2017-11-21 | Kuraray Co., Ltd. | Pressure-sensitive adhesive composition for optical films and pressure-sensitive adhesion type optical film |
US9334423B2 (en) * | 2012-08-31 | 2016-05-10 | Basf Se | Compositions comprising an acrylic block copolymer and a UV-curable copolymer and methods of making and using the same |
EP2993194B1 (en) * | 2013-05-02 | 2019-07-03 | LG Chem, Ltd. | Multi-block copolymer |
JP6315298B2 (ja) * | 2013-08-30 | 2018-04-25 | エルジー・ケム・リミテッド | ブロック共重合体 |
WO2015030550A1 (ko) * | 2013-08-30 | 2015-03-05 | 주식회사 엘지화학 | 블록 공중합체 |
JP6378559B2 (ja) * | 2014-07-08 | 2018-08-22 | 日東電工株式会社 | アンカー層形成用組成物、アンカー層、粘着剤層付光学フィルム、及び、画像表示装置 |
CN107849201B (zh) * | 2015-08-21 | 2021-05-14 | 株式会社日本触媒 | 嵌段共聚物 |
-
2016
- 2016-09-08 KR KR1020160115609A patent/KR102097817B1/ko active IP Right Grant
-
2017
- 2017-09-07 EP EP17849100.7A patent/EP3434745A4/en not_active Ceased
- 2017-09-07 US US16/305,296 patent/US11180597B2/en active Active
- 2017-09-07 WO PCT/KR2017/009813 patent/WO2018048216A1/ko active Application Filing
- 2017-09-07 JP JP2018544232A patent/JP6785870B2/ja active Active
- 2017-09-07 CN CN201780016605.1A patent/CN108779319B/zh active Active
- 2017-09-08 TW TW106130731A patent/TWI642745B/zh active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6288173B1 (en) * | 1999-06-03 | 2001-09-11 | Ppg Industries Ohio, Inc. | Block copolymers |
KR101171976B1 (ko) | 2007-12-29 | 2012-08-08 | 주식회사 엘지화학 | 아크릴계 점착제 조성물, 이를 포함하는 편광판 및액정표시장치 |
KR20110008028A (ko) * | 2008-03-07 | 2011-01-25 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 대전 방지 블록 코폴리머 감압성 접착제 및 물품 |
KR101171977B1 (ko) | 2008-06-05 | 2012-08-08 | 주식회사 엘지화학 | 아크릴계 점착제 조성물, 이를 포함하는 편광판 및액정표시장치 |
KR101023839B1 (ko) | 2008-07-24 | 2011-03-22 | 주식회사 엘지화학 | 점착제 조성물, 상기를 포함하는 편광판 및 액정표시장치 |
JP2010106230A (ja) * | 2008-09-30 | 2010-05-13 | Sekisui Chem Co Ltd | 粘着剤組成物 |
US20120029139A1 (en) * | 2009-01-30 | 2012-02-02 | Centre National De La Recherche Scientifique (Cnrs | Block copolymers having associative groups, and adhesive containing same |
KR20140119167A (ko) * | 2012-01-31 | 2014-10-08 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | 공중합체를 포함하는 필름, 물품 및 방법 |
KR20160115609A (ko) | 2015-03-27 | 2016-10-06 | 아이디에이씨 홀딩스, 인크. | 실수 m진 신호 부호화 방법, 및 이를 이용한 부호화 장치 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3434745A4 |
Also Published As
Publication number | Publication date |
---|---|
TWI642745B (zh) | 2018-12-01 |
EP3434745A1 (en) | 2019-01-30 |
TW201816054A (zh) | 2018-05-01 |
CN108779319B (zh) | 2021-01-15 |
JP6785870B2 (ja) | 2020-11-18 |
CN108779319A (zh) | 2018-11-09 |
KR102097817B1 (ko) | 2020-04-07 |
KR20180028215A (ko) | 2018-03-16 |
EP3434745A4 (en) | 2019-06-12 |
US11180597B2 (en) | 2021-11-23 |
JP2019512560A (ja) | 2019-05-16 |
US20200010600A1 (en) | 2020-01-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2018048216A1 (ko) | 고분자 조성물 | |
CN105189681B (zh) | 压敏粘合剂组合物 | |
TWI510587B (zh) | 壓敏性黏著組成物 | |
KR20140112388A (ko) | 점착제층이 형성된 편광 필름 및 화상 표시 장치 | |
WO2013180524A1 (ko) | 점착제 조성물 | |
CN105593328B (zh) | 压敏粘合剂组合物 | |
CN104812864B (zh) | 压敏粘合剂组合物 | |
WO2017099537A1 (ko) | 점착제 조성물 | |
TWI582195B (zh) | 壓敏性黏著劑組成物 | |
KR20180033698A (ko) | 점착 편광판 | |
TWI544053B (zh) | 光學膜 | |
JP6089287B2 (ja) | 粘着剤組成物 | |
KR20180033697A (ko) | 점착 조성물 | |
KR102159486B1 (ko) | 가교성 조성물 | |
KR20180028749A (ko) | 가교성 조성물 | |
KR102211418B1 (ko) | 점착형 광학 부재 | |
KR101910147B1 (ko) | 가교성 조성물 | |
KR102497341B1 (ko) | 점착형 편광판 | |
KR102122383B1 (ko) | 고분자 조성물 | |
KR20190025342A (ko) | 점착 조성물 | |
KR20190017470A (ko) | 점착형 광학 부재 | |
KR20190017448A (ko) | 가교성 조성물 | |
KR20170047616A (ko) | 점착제 조성물 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2018544232 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2017849100 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2017849100 Country of ref document: EP Effective date: 20181022 |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17849100 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |