WO2015047004A1 - 라디칼 경화형 접착제 조성물, 이를 포함하는 편광판 및 광학 부재 - Google Patents
라디칼 경화형 접착제 조성물, 이를 포함하는 편광판 및 광학 부재 Download PDFInfo
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- WO2015047004A1 WO2015047004A1 PCT/KR2014/009136 KR2014009136W WO2015047004A1 WO 2015047004 A1 WO2015047004 A1 WO 2015047004A1 KR 2014009136 W KR2014009136 W KR 2014009136W WO 2015047004 A1 WO2015047004 A1 WO 2015047004A1
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- formula
- group
- adhesive composition
- meth
- curable adhesive
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- LPSXSORODABQKT-UHFFFAOYSA-N C(C1)CC2C1C1CC2CC1 Chemical compound C(C1)CC2C1C1CC2CC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 description 1
- OWIWFJAZRBUKLZ-UHFFFAOYSA-N C=CC(NCCOP(OCCOC(C=C)=O)(OCCOC(C=C)=O)=O)=O Chemical compound C=CC(NCCOP(OCCOC(C=C)=O)(OCCOC(C=C)=O)=O)=O OWIWFJAZRBUKLZ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- 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
-
- 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
- C09J7/22—Plastics; Metallised plastics
-
- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
Definitions
- the present invention relates to a radically curable adhesive composition, a polarizing plate and an optical member comprising the same, and more particularly, to a radical curable adhesive composition having excellent adhesion between the polarizer and the protective film, and excellent in water resistance and heat resistance, and a polarizing plate including the same. It relates to an optical member.
- the polarizing plate has been commonly used as a structure in which a protective film is laminated using one or both sides of a polarizer made of a polyvinyl alcohol (hereinafter referred to as 'PVA')-based resin dyed with dichroic dye or iodine.
- a triacetyl cellulose (TAC) film has been mainly used as a polarizer protective film, but such a TAC film has a problem in that it is easily deformed in a high temperature and high humidity environment.
- protective films of various materials that can replace TAC films have been developed. For example, polyethylene terephthalate (PET), cycloolefin polymer (COP, cycloolefin polymer), and acrylic films may be used alone. Or a mixed use has been proposed.
- an aqueous adhesive composed mainly of an aqueous solution of polyvinyl alcohol-based resin is used as the adhesive used to attach the polarizer and the protective film.
- the water-based adhesive when using an acrylic film or a COP film other than TAC as a protective film, there is a problem that its use is limited depending on the film material because the adhesive strength is weak.
- the water-based adhesive in addition to the problem of poor adhesion to the material, if the material of the protective film applied to both sides of the PVA device is different, the problem of curl generation of the polarizing plate by the drying process of the water-based adhesive and initial optical Problems such as deterioration of physical properties occur.
- the non-aqueous adhesive for polarizing plates proposed to date can be divided into radical curable adhesives and cationic curable adhesives according to the curing method.
- Cationic curable adhesives have the advantage of having excellent adhesion to films of various materials, but have a number of disadvantages in the manufacturing process due to the slow curing rate and low curing degree.
- a radical curable adhesive having an acrylic or acrylamide compound as a main component has been proposed.
- a radically curable adhesive mainly composed of an acryl- or acrylamide-based compound, although the curing speed is faster than that of the cation-curable adhesive, the water resistance is not good.
- Iodine ions in the polarizer may be affected to deteriorate the appearance, such as decolorization.
- the radically curable adhesive containing the acrylic or acrylamide compound as a main component since the glass transition temperature of the adhesive after radical curing is low, there is a problem that heat resistance reliability of the polarizing plate manufactured by using the adhesive is not good.
- the display device has been generally used as a structure in which a polarizer is attached to the upper and / or lower substrate of the display panel for generating an image using an adhesive, and recently, one side of the polarizer for thinning the display device Only a protective film is laminated using an adhesive, and a method of using the opposite side of the surface on which the protective film of the polarizer is laminated is directly attached to the display panel using a pressure-sensitive adhesive without a protective film.
- an acrylic pressure sensitive adhesive is mainly used as the pressure sensitive adhesive used to attach the polarizing plate of the above structure to a display panel.
- the acrylic pressure-sensitive adhesive is usually required to have a thickness of at least about 20 ⁇ m in order to maintain a moderate adhesive force, there is a problem that it is difficult to meet the trend of thinning and weight of the display device.
- the acrylic pressure-sensitive adhesive is generally formed by applying a pressure-sensitive adhesive composition to the release film, drying the solvent, and then transferring to the sample surface to form a pressure-sensitive adhesive layer, there is a lot of trouble in attaching the polarizing plate to the display device, productivity This has the disadvantage of falling.
- the acrylic pressure-sensitive adhesive is usually a glass transition temperature of 0 °C or less
- the thermal reliability is inferior, such as cracks in the polarizer in the thermal shock reliability test.
- the present invention is to solve the above problems, while having excellent adhesion between the polarizer and the protective film, excellent water resistance and heat resistance, it is possible to form a thin, as well as attaching the polarizer and the protective film as well as the polarizer and the display panel It is intended to provide a radical curable adhesive composition, a polarizing plate and an optical member comprising the same, which can also be used for the attachment of the same.
- the invention provides a polymerizable compound comprising (A) a radically polymerizable compound having at least one hydrophilic functional group in a molecule; (B) phosphate compounds having three (meth) acryl groups in the molecule; And (C) provides a radical curable adhesive composition comprising a radical initiator.
- the radical curable adhesive composition is based on 100 parts by weight of the radical curable adhesive composition, (A) 40 to 93 parts by weight of the radical polymerizable compound; (B) 1 to 30 parts by weight of the phosphate compound; And (C) 0.5 to 20 parts by weight of a radical initiator.
- the (A) radically polymerizable compound includes: a radically polymerizable first compound including at least one hydroxy group and at least one (meth) acryl group in a molecule (a-1); And (a-2) a radically polymerizable second compound comprising at least two hydroxy groups, at least one benzene ring or cyclohexane ring, and at least two (meth) acryl groups in the molecule.
- the (a-1) first compound may be at least one selected from the group consisting of the following [Formula 1] to [Formula 21].
- the (a-2) second compound may be at least one selected from the group consisting of the following [Formula 22] to [Formula 24].
- the (B) phosphate compound is a compound represented by the following [Formula I].
- R 1, R 2 and R 3 are each independently a substituted or unsubstituted C 1 ⁇ 10 alkyl group, a substituted or unsubstituted C 4 ⁇ 14 cycloalkyl group, a substituted or unsubstituted C 6-14 arylene group, or combinations thereof, and; R 4 , R 5 and R 6 are each independently hydrogen or a methyl group; X 1 , X 2 and X 3 are each independently O (oxygen) or N (nitrogen).
- the radical curable adhesive composition may further include a phosphate compound having one or two (meth) acryl groups in the (D) molecule.
- the (D) phosphate-based compound is more preferably contained in 5 to 40 parts by weight in 100 parts by weight of the radical curable adhesive composition.
- the (D) phosphate-based compound is more preferably a compound represented by the following [Formula II] and / or [Formula III].
- R 7 and R 8 are independently a substituted or unsubstituted C 1 ⁇ 10 alkyl group, a substituted or unsubstituted C 4 ⁇ 14 cycloalkyl group, a substituted or unsubstituted C 6 ⁇ 14 unsubstituted ring respectively An arylene group, or a combination thereof; R 9 and R 10 are each independently hydrogen or a methyl group; X 4 and X 5 are each independently O (oxygen) or N (nitrogen).
- R 11 is a substituted or unsubstituted C 1 ⁇ 10 alkyl group, a substituted or unsubstituted C 4 ⁇ 14 cycloalkyl group, a substituted or unsubstituted C 6 ⁇ 14 aryl group, or their Combination;
- Each R 12 is independently hydrogen or a methyl group;
- X 6 are each independently O (oxygen) or N (nitrogen).
- the said radical curable adhesive composition may be what contains (E) polyfunctional (meth) acrylic-type compound further.
- the (E) polyfunctional (meth) acrylic compound is contained at 5 to 40 parts by weight in 100 parts by weight of the radical curable adhesive composition.
- the (E) polyfunctional (meth) acrylic compound is more preferably at least one member selected from the group consisting of compounds represented by the following [Formula IV] to [Formula VI].
- R 13 and R 14 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group.
- R 15 , R 16 and R 17 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group
- R 18 is a (meth) acryloyloxy group, (meth ) Acryloyloxyalkyl group, a hydroxy group, or a substituted or unsubstituted C 1-10 alkyl group.
- R 19 is substituted or unsubstituted C 1-10 alkylene, and R 20 and R 21 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group.
- the thickness of the contact bonding layer formed of the said radical adhesive composition is 10 micrometers or less.
- the radical curable adhesive composition preferably has a glass transition temperature of 50 ° C. or more after curing.
- the radical curable adhesive composition preferably has a viscosity of 70 cP or less.
- the invention provides a polarizer; An adhesive layer formed on at least one surface of the polarizer; And a polarizing plate comprising a polarizer protective film formed on the adhesive layer, wherein the adhesive layer provides a polarizing plate is formed using the radical curable adhesive composition.
- the invention provides a display panel; And a polarizer attached to the outermost surface of the display panel via an adhesive layer, wherein the adhesive layer is formed using the radically curable adhesive composition.
- the radically curable adhesive composition according to the present invention has excellent adhesion to films of various materials, for example, TAC film, acrylic film, COP film, PET film, and the like, and does not cause discoloration of the polarizer even under high humidity. It is excellent, the glass transition temperature after curing is high bar heat resistance of the polarizing plate manufactured by using this, and further has a low viscosity can form a thinner adhesive layer, and also excellent workability.
- the radical curable adhesive composition according to the present invention may also be used to attach the polarizer and the display panel, in which case it is possible to thin compared to the acrylic pressure-sensitive adhesive commonly used in the past, in-line (in-line) process As an adhesive layer can be formed between the polarizer and the display panel, excellent productivity can be imparted. In addition, the thermal reliability is excellent compared to the acrylic pressure-sensitive adhesive and the like commonly used in the prior art.
- the present inventors have conducted extensive research, and when the phosphate-based compound having three (meth) acryl groups in a molecule is mixed with an adhesive composition having a hydrophilic functional group, not only the adhesive force is excellent, but also the water resistance and the heat resistance are excellent. Furthermore, the inventors have found that low viscosity can be achieved and completed the present invention.
- the radical curable adhesive composition of this invention is a radically polymerizable compound which has at least 1 hydrophilic functional group in (A) molecule
- the radical curable adhesive composition of the present invention comprises (A) 40 to 93 parts by weight of the radically curable adhesive composition, (B) 1 to 30 parts by weight of the phosphate compound, and (C) 0.5 to 20 parts by weight of the radical initiator.
- the radically polymerizable compound having at least one hydrophilic functional group in the (A) molecule included in the radical curable adhesive composition according to the present invention is a component for implementing the adhesive force of the adhesive, and has at least one hydrophilic functional group in the molecule. It is possible to implement the adhesive force through the hydrogen bond, and can also be used without particular limitation as long as the radical polymerization is possible by the presence of an unsaturated double bond between carbons in the molecule as a radical polymerizable compound.
- the hydrophilic functional group is not particularly limited as long as the hydrogen bond, such as hydroxy group, carboxyl group, urethane group, amine group, amide group, etc. is possible, but is particularly preferable for the implementation of excellent adhesive strength among the hydroxy group.
- the radical polymerizable compound (A) may include a radical polymerizable first compound including at least one hydroxy group and at least one (meth) acryl group in a molecule (a-1); And (a-2) a mixture of a radically polymerizable second compound comprising at least two hydroxy groups, at least one benzene ring or cyclohexane ring, and at least two (meth) acryl groups in a molecule to implement the effects of the present invention. It is especially preferable for that.
- the (a-1) first compound may be used without particular limitation as long as it includes at least one hydroxy group in the molecule, and includes at least one (meth) acryl group, but is described below in (a- 2) The thing corresponding to a 2nd compound is excluded from a 1st compound (a-1).
- the first compound (a-1) is not limited thereto, for example, may be one or more selected from the group consisting of the following [Formula 1] to [Formula 21].
- the (a-2) second compound may be used without particular limitation as long as it contains at least two hydroxy groups, at least one benzene ring or a cyclohexane ring, and at least two (meth) acryl groups in the molecule. This is possible.
- the second compound (a-2) is not limited thereto, and may be, for example, one or more selected from the group consisting of the following Chemical Formulas 22 to 24.
- the content of the radically polymerizable compound of the present invention may be about 40 to 93 parts by weight, preferably about 40 to 90 parts by weight, and more preferably about 45 to 90 parts by weight based on 100 parts by weight of the total adhesive composition. have. If it is included in such a content because it is possible to implement excellent adhesion.
- the phosphate compound having three (meth) acryl groups in the (B) molecule included in the radical curable adhesive composition according to the present invention further improves the adhesive strength of the adhesive, and furthermore, as a component for securing excellent water resistance and heat resistance.
- Various phosphate compounds containing three (meth) acryl groups in the molecule can be used.
- the said (B) phosphate type compound is a compound represented by following [Formula I]. This is because the above effects are particularly excellent.
- R 1, R 2 and R 3 are each independently a substituted or unsubstituted C 1 ⁇ 10 alkyl group, a substituted or unsubstituted C 4 ⁇ 14 cycloalkyl group, a substituted or unsubstituted C 6-14 arylene group, or combinations thereof, and; R 4 , R 5 and R 6 are each independently hydrogen or a methyl group; X 1 , X 2 and X 3 are each independently O (oxygen) or N (nitrogen).
- the alkylene group refers to a straight or branched chain divalent hydrocarbon moiety of 1 to 10, or 1 to 8, or 1 to 4 carbon atoms,
- the alkylene group may include at least one unsaturated bond in the molecule.
- the alkylene group includes, but is not limited to, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, nonamethylene, decamethylene and the like.
- One or more hydrogen atoms included in the alkylene group may be substituted with any substituent.
- the cycloalkylene group is 4 to 14, or 4 to 10, or 4 to 6 non-aromatic divalent monocyclic, bicyclic or It means a tricyclic hydrocarbon moiety, wherein the alkylene group may include at least one unsaturated bond in the molecule.
- a bivalent cyclopentane ring, a cyclohexane ring, etc. are mentioned as an example.
- One or more hydrogen atoms included in the cycloalkylene group may be substituted with any substituent.
- the arylene group means a divalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having 6 to 14, or 6 to 12 ring atoms
- the bivalent, benzene ring, naphthalene ring, anthracene ring, biphenyl ring, and the like can be given as examples thereof.
- One or more hydrogen atoms included in the arylene group may be substituted with any substituent.
- R 1, R 2 and R 3 are, but are not limited to, it is inter alia a substituted or unsubstituted C 1 ⁇ 10 alkylene group is preferred, and a substituted or unsubstituted C 1 ⁇ 8 alkylene group more preferably, and more preferably substituted or unsubstituted C 1 ⁇ 4 alkylene group.
- the present invention is not limited thereto, but the phosphate-based compound (B) may be at least one selected from the group consisting of the following [Formula 25] to [Formula 30].
- the content of the (B) phosphate compound of the present invention is about 1 to 30 parts by weight, preferably about 5 to 30 parts by weight, and more preferably about 6 to 29 parts by weight based on 100 parts by weight of the total adhesive composition.
- the phosphate-based compound is added with less than this, it is difficult to secure thermal shock stability and water resistance, and the viscosity is high. In addition, when used in addition to more than this results in a decrease in adhesion.
- radical initiators generally used in the art may be used without limitation, for example, 1-hydroxy-cyclohexyl-phenyl-ketone (1-Hydroxy-cyclohexyl-phenyl-ketone) , 2-hydroxy-2-methyl-1-phenyl-1-propanone (2-Hydroxy-2-methyl-1-phenyl-1-propanone), 2-hydroxy-1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-methyl-1-propanone (2-Hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propanone), methylbenzoylformate, Oxy-phenyl-acetic acid-2- [2 oxo-2phenyl-acetoxy-ethoxy] -ethyl ester (
- the content of the (C) radical initiator is preferably about 0.5 to 20 parts by weight, 0.5 to 15 parts by weight or 0.5 to 10 parts by weight based on 100 parts by weight of the radical curable adhesive composition. This is because when the content of the radical initiator satisfies the numerical range, the adhesive may be smoothly cured.
- the radical curable adhesive composition according to the present invention may further include a phosphate compound having one or two (meth) acryl groups in the molecule (D) in order to obtain better adhesion and water resistance effects.
- the radical curable adhesive composition which concerns on this invention is a (A) radically polymerizable compound which has at least 1 hydrophilic functional group in a molecule
- the (D) phosphate-based compound is not particularly limited, and various phosphate-based compounds including one or two (meth) acryl groups in a molecule may be used.
- the present invention is not limited thereto, but the (D) phosphate compound is more preferably a compound represented by the following [Formula II] and / or [Formula III]. This is because the above effects are particularly excellent.
- R 7 and R 8 are independently a substituted or unsubstituted C 1 ⁇ 10 alkyl group, a substituted or unsubstituted C 4 ⁇ 14 cycloalkyl group, a substituted or unsubstituted C 6 ⁇ 14 unsubstituted ring respectively An arylene group, or a combination thereof; R 9 and R 10 are each independently hydrogen or a methyl group; X 4 and X 5 are each independently O (oxygen) or N (nitrogen).
- the alkylene group refers to a straight or branched divalent hydrocarbon moiety of 1 to 10, or 1 to 8, or 1 to 4 carbon atoms
- the alkylene group may contain at least one unsaturated bond in the molecule.
- the alkylene group includes, but is not limited to, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, nonamethylene, decamethylene and the like.
- One or more hydrogen atoms included in the alkylene group may be substituted with any substituent.
- the cycloalkylene group is 4 to 14, or 4 to 10, or 4 to 6 non-aromatic divalent monocyclic, bicyclic or tricyclic It means a hydrocarbon site, wherein the alkylene group may include at least one unsaturated bond in the molecule.
- a bivalent cyclopentane ring, a cyclohexane ring, etc. are mentioned as an example.
- One or more hydrogen atoms included in the cycloalkylene group may be substituted with any substituent.
- the arylene group means a divalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having 6 to 14, or 6 to 12 ring atoms, and the like.
- divalent, benzene ring, naphthalene ring, anthracene ring, biphenyl ring, etc. are mentioned as an example.
- One or more hydrogen atoms included in the arylene group may be substituted with any substituent.
- the R 7 and R 8 are, thereby but are not limited, among others, and preferably a substituted or unsubstituted C 1 ⁇ 10 alkylene group, and a substituted or more preferably unsubstituted C 1 ⁇ 8 alkylene group More preferably a substituted or unsubstituted C 1-4 alkylene group.
- R 11 is a substituted or unsubstituted C 1 ⁇ 10 alkyl group, a substituted or unsubstituted C 4 ⁇ 14 cycloalkyl group, a substituted or unsubstituted C 6 ⁇ 14 aryl group, or their Combination;
- Each R 12 is independently hydrogen or a methyl group;
- X 6 are each independently O (oxygen) or N (nitrogen).
- the alkylene group refers to a straight or branched chain divalent hydrocarbon moiety of 1 to 10, or 1 to 8, or 1 to 4 carbon atoms, in the present specification
- the group may comprise at least one unsaturated bond in the molecule.
- the alkylene group includes, but is not limited to, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, nonamethylene, decamethylene and the like.
- One or more hydrogen atoms included in the alkylene group may be substituted with any substituent.
- the cycloalkylene group may be selected from 4 to 14, or 4 to 10, or 4 to 6 non-aromatic divalent monocyclic, bicyclic or tricyclic hydrocarbon moieties.
- the alkylene group may include at least one unsaturated bond in the molecule.
- a bivalent cyclopentane ring, a cyclohexane ring, etc. are mentioned as an example.
- One or more hydrogen atoms included in the cycloalkylene group may be substituted with any substituent.
- the arylene group means a divalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having 6 to 14, or 6 to 12 ring atoms, but is not limited thereto. And divalent, benzene ring, naphthalene ring, anthracene ring, biphenyl ring and the like. One or more hydrogen atoms included in the arylene group may be substituted with any substituent.
- the R 12 include, but are not limited to this, it is preferable that among a substituted or unsubstituted C 1 ⁇ 10 alkylene group, and more preferably substituted or unsubstituted C 1 ⁇ 8 alkylene group, a substituted or unsubstituted C 1 ⁇ 4 alkylene group is more preferable.
- the (D) phosphate-based compound may be at least one selected from the group consisting of the following [Formula 31] to [Formula 34].
- the (D) phosphate-based compound is preferably contained in 5 to 40 parts by weight, more preferably about 5 to 35 parts by weight, still more preferably 5 to 30 parts by weight in 100 parts by weight of the radical curable adhesive composition. May be enough. If the content of the (D) phosphate-based compound is greater than the above range, the adhesive force may not be sufficient, and if less than the above range, the water resistance may be weak.
- the radical curable adhesive composition according to the present invention may further include (E) a polyfunctional (meth) acrylic compound in order to obtain more excellent adhesion and water resistance effects.
- the radical curable adhesive composition which concerns on this invention is a (A) radically polymerizable compound which has at least 1 hydrophilic functional group in a molecule
- the (E) polyfunctional (meth) acrylic compound is not particularly limited, and various polyfunctional (meth) acrylic compounds well known in the art by having at least two (meth) acryl groups in a molecule are not particularly limited. Can be used. In the present specification, except for the polyfunctional (meth) acrylic compounds listed in the following examples, the compounds corresponding to the above-mentioned (A) to (D) compounds are excluded from the polyfunctional (meth) acrylic compounds.
- the (E) polyfunctional (meth) acrylic compound ethylene glycol di (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (Meth) acrylate, 1,6-hexanedioldi (meth) acrylate, 1,9-nonanedioldi (meth) acrylate, neopentyl glycoldi (meth) acrylate, trimethylolpropanedi (meth) acrylic Rate, pentaerythritol di (meth) acrylate, ditrimethylolpropanedi (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) Acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol
- the present invention is not limited thereto, but the polyfunctional (meth) acrylic compound (E) is more preferably one or more selected from the group consisting of compounds represented by the following [Formula IV] to [VI]. This is because the water resistance improvement effect is more excellent.
- R 13 and R 14 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group.
- the alkyl of the (meth) acryloyloxyalkyl group is a straight or branched chain hydrocarbon site of 1 to 10, or 1 to 8, or 1 to 4 carbon atoms. Meaning, the (meth) acryloyloxy group may be substituted at any position of the alkyl group. The remaining one or more hydrogen atoms included in the alkyl may be substituted with any substituent.
- R 15 , R 16 and R 17 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group
- R 18 is a (meth) acryloyloxy group, (meth ) Acryloyloxyalkyl group, a hydroxy group, or a substituted or unsubstituted C 1-10 alkyl group.
- the alkyl of the (meth) acryloyloxyalkyl group is 1 to 10, or 1 to 8, or a straight chain of 1 to 4 carbon atoms or A branched hydrocarbon moiety, wherein the (meth) acryloyloxy group can be substituted at any position of the alkyl group.
- the remaining one or more hydrogen atoms included in the alkyl may be substituted with any substituent.
- the alkyl group means a straight or branched chain hydrocarbon site of 1 to 10, or 1 to 8, or 1 to 4 carbon atoms, at least one hydrogen contained in the alkyl group The atom may be substituted with any substituent.
- R 19 is substituted or unsubstituted C 1-10 alkylene, and R 20 and R 21 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group.
- the alkylene refers to a straight or branched chain divalent hydrocarbon moiety of 1 to 10, or 1 to 8, or 1 to 6 carbon atoms, the alkylene herein The group may comprise at least one unsaturated bond in the molecule.
- the alkylene group includes, but is not limited to, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, nonamethylene, decamethylene and the like.
- One or more hydrogen atoms included in the alkylene may be substituted with any substituent.
- the alkyl of the (meth) acryloyloxyalkyl group may be a straight or branched chain hydrocarbon site of 1 to 10, or 1 to 8, or 1 to 4 carbon atoms. Meaning, the (meth) acryloyloxy group may be substituted at any position of the alkyl group. The remaining one or more hydrogen atoms included in the alkyl may be substituted with any substituent.
- the (E) polyfunctional (meth) acrylic compound is particularly preferably one or more selected from the group consisting of compounds represented by the following [Formula 35] to [Formula 38].
- the content of the (E) polyfunctional (meth) acrylic compound of the present invention is about 5 to 40 parts by weight, preferably about 5 to 35 parts by weight, more preferably 5 to 100 parts by weight of the total adhesive composition. To about 30 parts by weight.
- the adhesive force may not be sufficient, and when less than the above range, the water resistance may be weak.
- the thickness of the adhesive layer formed by the radical-curable adhesive composition of the present invention as described above is preferably more than 0 to about 10 ⁇ m or less, preferably 0.1 to 10 ⁇ m or about 0.1 to 5 ⁇ m. If the thickness of the adhesive layer is less than 0.1 ⁇ m, the uniformity and adhesion of the adhesive layer may be lowered, and if the thickness of the adhesive layer exceeds 10 ⁇ m, it is difficult to reduce the thickness, the problem of wrinkles in the appearance of the polarizing plate including the same Can be.
- the radically curable adhesive composition according to the present invention may have a glass transition temperature of 50 ° C. or higher after curing, for example, 70 to 150 ° C. or 70 to 140 ° C.
- the polarizing plate manufactured using the radical curable adhesive composition according to the present invention having the glass transition temperature in the numerical range as described above has an advantage of excellent heat resistance and water resistance.
- the radical curable adhesive composition according to the present invention may have a viscosity of 70 cP or less, for example, 10 to 70 cP or 10 to 65 cP.
- the viscosity of the adhesive composition satisfies the numerical range, the thickness of the adhesive layer may be thinly formed, and since the adhesive composition has a low viscosity, there is an excellent workability.
- the radically curable adhesive composition of the present invention as described above not only has excellent adhesion to films of various materials, but also has excellent water resistance, heat resistance, and viscosity characteristics, and thus may be very usefully applied to a polarizing plate.
- the above-described radical curable adhesive composition of the present invention can implement the above excellent adhesion between the polarizer and the display panel, can form an adhesive layer thin, excellent thermal resistance, and further in-line (in-line) Since the productivity is excellent, such as an adhesive layer can be formed between the polarizer and the display panel in the step), it can be usefully used even when directly attaching the polarizer to the display panel.
- Polarizing plate of the present invention is a polarizer; An adhesive layer formed on at least one surface of the polarizer; And a protective film formed on the adhesive layer, wherein the adhesive layer is formed using the radical curable adhesive composition of the present invention described above.
- the polarizer is not particularly limited, and a film made of polyvinyl alcohol (PVA) including a polarizer well known in the art, for example, iodine or a dichroic dye, may be used.
- PVA polyvinyl alcohol
- the polarizer may be prepared by dyeing iodine or dichroic dye on the PVA film, but a method of manufacturing the same is not particularly limited.
- the polarizer means a state not including a protective film
- the polarizing plate means a state including a polarizer and a protective film.
- the adhesive layer is formed by using the radical curable adhesive composition according to the present invention described above, and may be formed by a method well known in the art.
- the adhesive composition may be applied to one surface of a polarizer or a protective film to form an adhesive layer, and then laminated with a polarizer and a protective film, followed by curing.
- the coating may be performed by coating methods well known in the art, for example, spin coating, bar coating, roll coating, gravure coating, blade coating, and the like.
- the curing may be carried out by irradiating active energy rays, such as light curing, more specifically ultraviolet light, visible light, electron beam X-rays.
- active energy rays such as light curing, more specifically ultraviolet light, visible light, electron beam X-rays.
- it can be carried out by a method of irradiating ultraviolet light of about 10 to 2500mJ / cm 2 using a ultraviolet irradiation device (Metal halide lamp).
- the curing may be carried out by thermal curing, more specifically thermal curing at a curing temperature of 80 ° C. or higher.
- a known amine initiator may be further added to the composition in order to increase the curing rate upon thermal curing.
- the curing may be to additionally perform the thermal curing after the photo-curing, may be to perform the additional photo-cure after the thermal curing.
- the protective film is to support and protect the polarizer
- protective films of various materials generally known in the art for example, cellulose-based film, polyethylene terephthalate (PET) film, Cycloolefin polymer (COP, cycloolefin polymer) film, acrylic film and the like can be used without limitation. Among them, it is particularly preferable to use an acrylic film in view of optical properties, durability, economy and the like.
- the acrylic film usable in the present invention can be obtained by molding a molding material containing (meth) acrylate-based resin as a main component by extrusion molding.
- the (meth) acrylate-based resin is a resin containing a (meth) acrylate-based unit as a main component, as well as a homopolymer resin consisting of (meth) acrylate-based units, as well as (meth) acrylate-based units
- the concept also includes a blend resin blended with other resin.
- the (meth) acrylate-based unit may be, for example, an alkyl (meth) acrylate-based unit.
- the alkyl (meth) acrylate-based unit means both an alkyl acrylate-based unit and an alkyl methacrylate-based unit
- the alkyl group of the alkyl (meth) acrylate-based unit is preferably 1 to 10 carbon atoms, It is more preferable that it is C1-C4.
- a styrene type unit, a maleic anhydride type unit, a maleimide type unit, etc. are mentioned as a monomeric unit copolymerizable with the said (meth) acrylate type unit.
- the styrene-based unit is not limited thereto, and examples thereof include styrene, ⁇ -methylstyrene, and the like;
- the maleic anhydride monomer include, but are not limited to, maleic anhydride, methyl maleic anhydride, cyclohexyl maleic anhydride, phenyl maleic anhydride, and the like;
- the maleimide monomers include, but are not limited to, maleimide, N-methyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, and the like. These may be used alone or in combination.
- the acrylic film may be a film containing a (meth) acrylate resin having a lactone ring structure.
- (meth) acrylate type resin which has a lactone ring structure it is the lactone described, for example in Unexamined-Japanese-Patent No. 2000-230016, Unexamined-Japanese-Patent No. 2001-151814, 2002-120326, etc.
- (Meth) acrylate type resin which has a ring structure is mentioned.
- the method for producing the acrylic film is not particularly limited, and for example, (meth) acrylate-based resin and other polymers, additives, and the like are sufficiently mixed by any suitable mixing method to prepare a thermoplastic resin composition, which is then film-molded. Or (meth) acrylate-based resin and other polymers, additives and the like may be prepared in a separate solution and then mixed to form a uniform mixed solution and then film-molded.
- the acrylic film may be any of an unstretched film or a stretched film. In the case of a stretched film, it may be a uniaxial stretched film or a biaxially stretched film, and in the case of a biaxially stretched film, it may be either a simultaneous biaxially stretched film or a successive biaxially stretched film.
- the polarizing plate of the present invention may further include a primer layer between the adhesive layer and the protective film in order to further improve the adhesive force.
- the primer layer may be formed by coating and drying a coating solution containing a water dispersible polymer resin, water dispersible fine particles and water on a protective film using a bar coating method, a gravure coating method, or the like.
- the water-dispersible polymer resin may be, for example, a water-based polyurethane resin, a water-based acrylic resin, a water-based polyester resin, or a combination thereof, and the water-dispersible microparticles may be inorganic fine particles such as silica, titania, alumina, zirconia, or the like.
- organic fine particles made of silicone resin, fluorine resin, (meth) acrylic resin, crosslinked polyvinyl alcohol and melamine resin, or a combination thereof may be used, but are not limited thereto.
- An optical member of the present invention a display panel; And a polarizer attached to the outermost surface of the display panel via an adhesive layer, wherein the adhesive layer is formed using the radical curable adhesive composition of the present invention described above.
- the display panel applicable to the present invention is not particularly limited, and for example, a liquid crystal panel of various modes used in the liquid crystal display device may be applied to the present invention.
- the specific configuration of the liquid crystal panel is not particularly limited, and may be, for example, an upper transparent substrate / color filter / protective film / transparent conductive film electrode / alignment film / liquid crystal / alignment film / thin film transistor / lower transparent substrate.
- the optical member of the present invention may be a polarizer attached to the outermost surface of the display panel, that is, the upper transparent substrate or the lower transparent substrate via an adhesive layer, wherein the adhesive layer is a radical curable adhesive of the present invention described above It is formed using the composition.
- the material of the transparent substrate to which the polarizer is attached via the adhesive layer is not particularly limited, and a known glass substrate, a transparent polymer film, or the like may be used without limitation.
- the polarizer is not particularly limited as described above, and a film made of polyvinyl alcohol (PVA) including a polarizer well known in the art, for example, iodine or a dichroic dye, may be used.
- PVA polyvinyl alcohol
- the polarizer may be prepared by dyeing iodine or dichroic dye on the PVA film, but is not particularly limited thereto.
- the polarizer may attach a separate protective film through the adhesive layer to support and protect the polarizer on the opposite side of the surface attached to the display panel.
- specific contents of the protective film are as described above.
- the polarizer and the protective film is attached to the surface of the polarizer or the protective film using a roll coater, gravure coater, bar coater, knife coater or capillary coater, etc., and then heat lamination with a lamination roll, It may be carried out by a method of pressing at room temperature and laminating or a method of UV irradiation after lamination.
- the adhesive is not limited to the radically curable adhesive of the present invention described above, various polarizing plate adhesives used in the art, for example, polyvinyl alcohol-based adhesives, polyurethane-based adhesives, acrylic adhesives, cationic or Radical adhesives and the like can be used without limitation.
- the adhesive layer is formed using the radical curable adhesive composition of the present invention described above, and may be formed through an in-line process well known in the art.
- the formation of the adhesive layer is the radically curable adhesive composition of the present invention by a coating method well known in the art on the surface of the polarizer while unwinding a polarizer or a polarizing plate with a protective film on one surface of the polarizer from a roll.
- the coating it may be carried out by laminating it on the display panel and curing the applied adhesive composition layer.
- the curing may be performed by photo curing as described above.
- Adhesive layer of the present invention can be formed through the in-line (in-line) process, there is an advantage that the productivity is excellent, such as continuous production.
- the adhesive layer has a thickness of about 10 ⁇ m or less, preferably about 0.1 to 10 ⁇ m or about 0.1 to 5 ⁇ m.
- Conventional acrylic pressure sensitive adhesives used to attach polarizers (or polarizers) to display panels typically require a thickness of at least 20 ⁇ m in order to maintain a moderate adhesive force, but there is a limit in thinning a display device including the same.
- the adhesive layer can be formed in such a thin thickness bar has an advantage that can be manufactured to a thinner display device including the same.
- the raw material hopper is a resin composition obtained by uniformly mixing poly (N-cyclohexylmaleimide-co-methylmethacrylate), styrene-maleic anhydride copolymer resin and phenoxy resin in a weight ratio of 100: 2.5: 5. From the extruder to a nitrogen-substituted 24 ⁇ extruder and melted at 250 ° C. to prepare a raw material pellet.
- the poly (N-cyclohexylmaleimide-co-methylmethacrylate) resin was used in which the content of N-cyclohexylmaleimide was 6.5% by weight as a result of NMR analysis.
- the obtained raw material pellets were vacuum-dried and melted with an extruder at 260 degreeC, passed through the T-die of a coat hanger type, and the film of 150 micrometers in thickness was produced through the chrome plating casting roll, a drying roll, etc.
- the film was stretched at a rate of 170% using a speed difference of the roll in the MD direction at 125 ° C. using a pilot stretching equipment to produce an acrylic film.
- Irgacure- a radical initiator
- HEA hydroxyethyl acrylate
- BPA type epoxy di-acrylate EB600 manufactured by Cytec
- tri- (acryloyloxy ethyl) phosphate 3 weight part of 819 (Ciba company) was added, and the adhesive composition A for polarizing plates was produced.
- HEA hydroxyethyl acrylate
- BPA BPA type epoxy di-acrylate
- EB600 Cytec
- 14.3 wt% tri- (acryloyloxy ethyl) phosphate 14.3 wt% di- (methacryloyloxy ethyl) phosphate 3 parts by weight of irgacure-819 (Ciba), which is a radical initiator, was added to 100 parts by weight of the resin composition to prepare an adhesive composition B for a polarizing plate.
- irgacure-819 irgacure-819
- HEA hydroxyethyl acrylate
- BPA BPA type epoxy di-acrylate
- Siba irgacure-819
- HEA hydroxyethyl acrylate
- EB600, Cytec BPA type epoxy di-acrylate
- DCPDA dimethylol tricyclodecane diacrylate
- Resin composition prepared by adding 16.7% by weight of hydroxyethyl acrylate (HEA), 50% by weight of glyceryl methacrylate (GLM), 16.6% by weight of BPA type epoxy di-acrylate (EB600, Cytec), and 16.7% by weight of tri- (acryloyloxy ethyl) phosphate 3 parts by weight of a radical initiator irgacure-819 (Ciba) was added to 100 parts by weight to prepare an adhesive composition E for a polarizing plate.
- HSA hydroxyethyl acrylate
- GLM glyceryl methacrylate
- EB600, Cytec BPA type epoxy di-acrylate
- Ciba a radical initiator
- HEA hydroxyethyl acrylate 50% by weight
- BPA type epoxy di-acrylate EB600, Cytec
- DCPDA Dimethylol tricyclodecane diacrylate
- irgacure-819 Ciba
- Adhesive composition H was prepared.
- Irgacure- a radical initiator
- HEA hydroxyethyl acrylate
- BPA type epoxy di-acrylate EB600 manufactured by Cytec
- di- (methacryloyloxy ethyl) phosphate 3 parts by weight of 819 (Ciba) was added to prepare an adhesive composition I for a polarizing plate.
- Irgacure- a radical initiator
- HEA hydroxyethyl acrylate
- BPA type epoxy di-acrylate EB600 manufactured by Cytec
- mono- (methacryloyloxy ethyl) phosphate 3 weight part of 819 (Ciba company) was added, and the adhesive composition J for polarizing plates was manufactured.
- the adhesive composition A was applied to the primer layer of the acrylic film-based protective film prepared in Preparation Example 1 with a dropper, laminated on both sides of the polarizer (PVA device), and the conditions were adjusted so that the thickness of the final adhesive layer was 1 to 2 ⁇ m. After setting, the laminator (5 m / min) was passed. Then, a polarizing plate was prepared by irradiating 1000 mJ / cm 2 ultraviolet rays to a surface of the acrylic film laminated using a UV irradiation device (metal halide lamp). On the other hand, the polarizing plate was manufactured on the conditions of 20 degreeC of temperature, and 50% of humidity.
- PVA device polarizer
- a polarizing plate was prepared in the same manner as in Example 1.
- a polarizing plate was manufactured in the same manner as in Example 1, except that C was used as the adhesive composition.
- a polarizing plate was manufactured in the same manner as in Example 1, except that D was used as the adhesive composition.
- a polarizing plate was manufactured in the same manner as in Example 1, except that E was used as the adhesive composition.
- a polarizing plate was manufactured in the same manner as in Example 1, except that F was used as the adhesive composition.
- a polarizing plate was manufactured in the same manner as in Example 1, except that G was used as the adhesive composition.
- a polarizing plate was manufactured in the same manner as in Example 1, except that H was used as the adhesive composition.
- a polarizing plate was manufactured in the same manner as in Example 1, except that I was used as the adhesive composition.
- the peel force of the polarizing plates prepared in Examples and Comparative Examples was measured and shown in the following [Table 1]. Specifically, the polarizing plates prepared in Examples and Comparative Examples were left for 4 days at a temperature of 20 ° C. and a humidity of 70%, and then cut into a width of 20 mm and a length of 100 mm, and a texture analyzer (TA-XT Plus from Stable Micro Systems) ), The peel force of the polarizer and the protective film was measured at a speed of 300 m / min and 90 degrees.
- the water resistance of the polarizing plates prepared in Examples and Comparative Examples was measured and shown in the following [Table 1]. Specifically, after laminating the polarizing plates of the above Examples and Comparative Examples on a glass substrate (glass lamination), the polarizing plate was immersed in a 60 ° C thermostat, and after 8 hours, the water resistance was judged by the discoloration of the ends of the polarizing plate, and the case of no deformation was excellent. , When there was some discoloration was marked as good, the case where a lot of discoloration occurred was marked as bad.
- the thermal shock stability of the polarizers prepared in Examples and Comparative Examples was measured and shown in the following [Table 1]. Specifically, the lamination of the polarizing plates of the above Examples and Comparative Examples on a glass substrate (glass lamination), it was left for 30 minutes at -40 °C, it was again performed for 100 minutes to leave it at 80 °C for 30 minutes. . Then, visual evaluation of the deformation of the polarizing plate appearance. The case where the appearance of the polarizing plate was not deformed was excellent, the case where cracks of less than 1 mm were generated was good, and the case where cracks of 1 mm or more occurred was marked as bad.
- the adhesive composition A was apply
- an optical member having a polarizer attached to a glass substrate was prepared by irradiating 1000 mJ / cm 2 ultraviolet rays to a surface on which the polarizer and the protective film were laminated using a UV irradiator (Metal halide lamp).
- the optical member was manufactured on the conditions of 20 degreeC of temperature, and 50% of humidity.
- Peel force of the polarizing plate prepared in Example 8 was measured and shown in the following [Table 3]. Specifically, the optical member manufactured in Example 8 was left for 4 days at a temperature of 20 ° C. and a humidity of 70%, and then cut into a width of 20 mm and a length of 100 mm, and a texture analyzer device (TA-XT Plus from Stable Micro Systems) The peel force of the polarizer and the glass substrate was measured at a speed of 300 m / min and 90 degrees. At this time, when the peeling force was excellent in 2.0 N / 2 cm or more, 1.0 N / 2 cm or more and less than 2.0 N / 2 cm, it was shown as the case where it was good and less than 1.0 N / 2 cm. In addition, the measuring methods, such as peeling force, which are further described in Table 2 below, are the same as above.
- the adhesive composition of the present invention has excellent adhesion between the polarizer and the glass substrate.
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Abstract
Description
구분 | 접착제 조성물 | 박리력 | 내수성 | 열충격 안정성 | 점도[cP] |
실시예 1 | A | ○ | 우수 | 우수 | 42 |
실시예 2 | B | ◎ | 우수 | 우수 | 65 |
실시예 3 | C | ○ | 우수 | 우수 | 55 |
실시예 4 | D | ◎ | 우수 | 우수 | 63 |
실시예 5 | E | ◎ | 우수 | 양호 | 50 |
실시예 6 | F | ○ | 우수 | 양호 | 47 |
실시예 7 | G | ◎ | 양호 | 우수 | 68 |
비교예 1 | H | XX | 나쁨 | 나쁨 | 90 |
비교예 2 | I | ○ | 나쁨 | 양호 | 72 |
비교예 3 | J | ○ | 나쁨 | 양호 | 75 |
구분 | 접착제 조성물 | 박리력 | 내수성 | 열충격 안정성 | 점도[cP] |
실시예 8 | A | 우수 | 우수 | 우수 | 42 |
Claims (17)
- (A) 분자 내에 적어도 1개의 친수성 관능기를 갖는 라디칼 중합성 화합물;(B) 분자 내에 3개의 (메트)아크릴기를 갖는 포스페이트계 화합물; 및(C) 라디칼 개시제를 포함하는 라디칼 경화형 접착제 조성물.
- 제 1 항에 있어서,라디칼 경화형 접착제 조성물 100 중량부에 있어서, (A) 라디칼 중합성 화합물 40 내지 93 중량부; (B) 포스페이트계 화합물 1 내지 40 중량부; 및 (C) 라디칼 개시제 0.5 내지 20 중량부를 포함하는 라디칼 경화형 접착제 조성물.
- 제 1 항에 있어서,상기 (A) 라디칼 중합성 화합물은,(a-1) 분자 내에 적어도 1개의 히드록시기 및 적어도 1개의 (메트)아크릴기를 포함하는 라디칼 중합성 제 1 화합물; 및(a-2) 분자 내에 적어도 2개의 히드록시기, 적어도 1개의 벤젠 고리 또는 시클로헥산 고리, 및 적어도 2개의 (메트)아크릴기를 포함하는 라디칼 중합성 제 2 화합물의 혼합물인 라디칼 경화형 접착제 조성물.
- 제 1 항에 있어서,상기 라디칼 경화형 접착제 조성물은 (D) 분자 내에 1개 또는 2개의 (메트)아크릴기를 갖는 포스페이트계 화합물을 더 포함하는 라디칼 경화형 접착제 조성물.
- 제 7 항에 있어서,상기 (D) 포스페이트계 화합물은 라디칼 경화형 접착제 조성물 100 중량부에 있어서 5 내지 40 중량부로 포함되는 것인 라디칼 경화형 접착제 조성물.
- 제 7 항에 있어서,상기 (D) 포스페이트계 화합물은 하기 [화학식 Ⅱ] 및 [화학식 Ⅲ]로 표시되는 화합물로 이루어진 군으로부터 선택되는 1종 이상인 라디칼 경화형 접착제 조성물.[화학식 Ⅱ]상기 [화학식 Ⅱ]에서, R7 및 R8은 각각 독립적으로 치환 또는 비치환된 C1~10 알킬렌기, 치환 또는 비치환된 C4~14 시클로알킬렌기, 치환 또는 비치환된 C6~14 아릴렌기, 또는 이들의 조합이고; R9 및 R10은 각각 독립적으로 수소 또는 메틸기이며; X4 및 X5는 각각 독립적으로 O(산소) 또는 N(질소)임.[화학식 Ⅲ]상기 [화학식 Ⅲ]에서, R11은 치환 또는 비치환된 C1~10 알킬렌기, 치환 또는 비치환된 C4~14 시클로알킬렌기, 치환 또는 비치환된 C6~14 아릴렌기, 또는 이들의 조합이고; R12는 각각 독립적으로 수소 또는 메틸기이며; X6는 각각 독립적으로 O(산소) 또는 N(질소)임.
- 제 1 항에 있어서,상기 라디칼 경화형 접착제 조성물은 (E) 다관능성 (메트)아크릴계 화합물을 더 포함하는 라디칼 경화형 접착제 조성물.
- 제 10 항에 있어서,상기 (E) 다관능성 (메트)아크릴계 화합물은 라디칼 경화형 접착제 조성물 100 중량부에 있어서 5 내지 40 중량부로 포함되는 것인 라디칼 경화형 접착제 조성물.
- 제 10 항에 있어서,상기 (E) 다관능성 (메트)아크릴계 화합물은 하기 [화학식 Ⅳ] 내지 [화학식 Ⅵ]로 표시되는 화합물로 이루어진 군으로 선택된 1종 이상인 라디칼 경화형 접착제 조성물.[화학식 Ⅳ]상기 [화학식 Ⅳ]에서, R13 및 R14는 각각 독립적으로 (메트)아크릴로일옥시기 또는 (메트)아크릴로일옥시알킬기임.[화학식 Ⅴ]상기 [화학식 Ⅴ]에서, R15, R16 및 R17는 각각 독립적으로 (메트)아크릴로일옥시기 또는 (메트)아크릴로일옥시알킬기이고, R18는 (메트)아크릴로일옥시기, (메트)아크릴로일옥시알킬기, 히드록시기, 또는 치환 또는 비치환된 C1~10 알킬기임.[화학식 Ⅵ]상기 [화학식 Ⅵ]에서, R19는 치환 또는 비치환된 C1~10 알킬렌이고, R20 및 R21은 각각 독립적으로 (메트)아크릴로일옥시기 또는 (메트)아크릴로일옥시알킬기임.
- 제 1 항에 있어서,상기 라디칼 접착제 조성물에 의해 형성되는 접착층의 두께는 10㎛ 이하인 라디칼 경화형 접착제 조성물.
- 제 1 항에 있어서,상기 라디칼 경화형 접착제 조성물은 경화 후 유리전이온도가 50℃ 이상인 라디칼 경화형 접착제 조성물.
- 제 1 항에 있어서,상기 라디칼 경화형 접착제 조성물은 점도가 70cP 이하인 라디칼 경화형 접착제 조성물.
- 편광자;상기 편광자의 적어도 일면에 형성되는 접착제층; 및상기 접착제층 상에 형성되는 편광자 보호 필름;을 포함하며, 상기 접착제층은 제 1 항 내지 제 15 항 중 어느 한 항의 라디칼 경화형 접착제 조성물을 이용하여 형성되는 것인 편광판.
- 디스플레이 패널; 및상기 디스플레이 패널의 최외면에 접착제층을 매개로 부착되는 편광자;를 포함하며, 상기 접착제층은 제 1 항 내지 제 15 항 중 어느 한 항의 라디칼 경화형 접착제 조성물을 이용하여 형성되는 것인 광학 부재.
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CN201480046265.3A CN105555890B (zh) | 2013-09-30 | 2014-09-29 | 自由基可固化的粘合剂组合物及包含其的偏光板和光学构件 |
JP2016533261A JP6275842B2 (ja) | 2013-09-30 | 2014-09-29 | ラジカル硬化型接着剤組成物、これを含む偏光板および光学部材 |
US14/902,535 US9790403B2 (en) | 2013-09-30 | 2014-09-29 | Radical curable adhesive composition, and polarizing plate and optical member comprising same |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20020056447A (ko) * | 2000-12-29 | 2002-07-10 | 성재갑 | 편광판용 아크릴계 점착제 조성물 |
KR20090071716A (ko) * | 2007-12-28 | 2009-07-02 | 제일모직주식회사 | 대전방지 코팅층을 포함하는 편광필름 |
JP4459880B2 (ja) * | 2005-09-15 | 2010-04-28 | 電気化学工業株式会社 | エネルギー線硬化性樹脂組成物とそれを用いた接着剤 |
JP2011076058A (ja) * | 2009-09-04 | 2011-04-14 | Toyo Ink Mfg Co Ltd | 偏光板及び偏光板形成用光硬化性接着剤 |
KR20130040725A (ko) * | 2011-10-14 | 2013-04-24 | 주식회사 엘지화학 | 편광판용 접착제 및 이를 포함하는 편광판 |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20020056447A (ko) * | 2000-12-29 | 2002-07-10 | 성재갑 | 편광판용 아크릴계 점착제 조성물 |
JP4459880B2 (ja) * | 2005-09-15 | 2010-04-28 | 電気化学工業株式会社 | エネルギー線硬化性樹脂組成物とそれを用いた接着剤 |
KR20090071716A (ko) * | 2007-12-28 | 2009-07-02 | 제일모직주식회사 | 대전방지 코팅층을 포함하는 편광필름 |
JP2011076058A (ja) * | 2009-09-04 | 2011-04-14 | Toyo Ink Mfg Co Ltd | 偏光板及び偏光板形成用光硬化性接着剤 |
KR20130040725A (ko) * | 2011-10-14 | 2013-04-24 | 주식회사 엘지화학 | 편광판용 접착제 및 이를 포함하는 편광판 |
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