WO2015047001A1 - Polarizing plate and image display device comprising same - Google Patents

Polarizing plate and image display device comprising same Download PDF

Info

Publication number
WO2015047001A1
WO2015047001A1 PCT/KR2014/009133 KR2014009133W WO2015047001A1 WO 2015047001 A1 WO2015047001 A1 WO 2015047001A1 KR 2014009133 W KR2014009133 W KR 2014009133W WO 2015047001 A1 WO2015047001 A1 WO 2015047001A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
group
meth
polarizing plate
compound
Prior art date
Application number
PCT/KR2014/009133
Other languages
French (fr)
Korean (ko)
Inventor
허은수
박광승
이미린
박준욱
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020140129390A external-priority patent/KR101697403B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2016545702A priority Critical patent/JP6374006B2/en
Priority to US15/025,452 priority patent/US9651716B2/en
Priority to CN201480054117.6A priority patent/CN105705970B/en
Publication of WO2015047001A1 publication Critical patent/WO2015047001A1/en

Links

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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
    • 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
    • C08F30/00—Homopolymers and 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
    • C08F30/02—Homopolymers and 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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers

Definitions

  • the present invention relates to a polarizing plate and an image display apparatus including the same, and more particularly, to a polarizer and a protective layer having excellent adhesiveness, excellent water resistance and heat resistance, and a thin polarizing plate and an image display apparatus including the same. It is about.
  • the polarizing plate has been commonly used in a structure in which a protective film is laminated on both sides of a polarizer made of a polyvinyl alcohol (hereinafter referred to as 'PVA')-based resin dyed with a dichroic dye or iodine.
  • 'PVA' polyvinyl alcohol
  • the triacetyl cellulose (TAC, triacetyl cellulose) -based film has been used a lot of films in terms of excellent optical transparency and moisture permeability.
  • the active energy ray-curable composition proposed to date can be divided into a radical curable composition and a cationic curable composition according to the curing method.
  • the transparent thin film layer is formed using the cation-curable composition, there is an advantage of having excellent adhesion with the polarizer, but has a number of disadvantages in the manufacturing process due to the slow curing rate and low curing degree.
  • the new polarizing plate which is excellent in the adhesiveness of a polarizer and a protective layer, and excellent in water resistance and heat resistance is calculated
  • the present invention is to solve the above problems, to provide a polarizing plate excellent in the adhesion between the polarizer and the protective layer, excellent in water resistance and heat resistance, and can be manufactured in a thin shape and an image display device including the same.
  • the present invention is a polarizer; And a protective layer formed on at least one surface of the polarizer, wherein the protective layer comprises: (A) a radical 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) a polarizing plate which is a cured product of a radical curable composition containing a radical initiator.
  • the radical curable composition is based on 100 parts by weight of the radical curable 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 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 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 composition may further contain the (E) polyfunctional (meth) acrylic-type compound.
  • the (E) polyfunctional (meth) acrylic compound is more preferably contained in 5 to 40 parts by weight in 100 parts by weight of the radical curable 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 radical curable composition is preferably a glass transition temperature of 50 °C or more after curing.
  • the radical curable composition preferably has a viscosity of 70 cP or less.
  • the protective layer preferably has a thickness of 0.5 to 20 ⁇ m.
  • the polarizing plate of the present invention may be further attached to the protective film via the adhesive layer on the opposite side of the surface on which the protective layer of the polarizer is formed.
  • the polarizing plate of the present invention may further include an adhesive layer on the protective layer.
  • the present invention provides an image display device including the polarizing plate.
  • the polarizing plate of the present invention is excellent in the adhesion between the polarizer and the protective layer, and excellent in water resistance, such as being able to prevent the discoloration of iodine ions in the polarizer even in a high humidity environment, and has a high glass transition temperature of the protective layer after curing. .
  • the polarizing plate of the present invention is excellent in water resistance, such as no discoloration of the polarizer even in a high humidity environment of the protective layer forming composition can be manufactured in a thin bar, and also excellent workability.
  • the present inventors have conducted extensive studies and, in the case of using a phosphate compound having three (meth) acryl groups in a molecule in a radically curable composition having a hydrophilic functional group for forming a protective layer, not only the adhesiveness is excellent, The present invention was completed by finding out that the water resistance and the heat resistance are excellent, and furthermore, low viscosity can be realized.
  • the radical curable composition of this invention is a polarizer; And a protective layer formed on at least one surface of the polarizer, wherein the protective layer comprises: (A) a radical 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) a radical curable composition comprising a radical initiator.
  • the polarizer of the present invention may use a film made of polyvinyl alcohol (PVA) containing a polarizer well known in the art, for example, iodine or dichroic dye.
  • PVA polyvinyl alcohol
  • the polarizer may be prepared by dyeing iodine or dichroic dye on a polyvinyl alcohol film, but a method of manufacturing the same is not particularly limited.
  • the polarizer means a state not including a protective layer (or protective film), and the polarizing plate means a state including a polarizer and a protective layer (or protective film).
  • the polyvinyl alcohol-based film can be used without particular limitation as long as it contains a polyvinyl alcohol resin or a derivative thereof.
  • examples of the derivative of the polyvinyl alcohol resin include, but are not limited to, polyvinyl formal resin, polyvinyl acetal resin, and the like.
  • the polyvinyl alcohol-based film may be a commercially available polyvinyl alcohol-based film commonly used in the manufacture of polarizers in the art, for example, P30, PE30, PE60 manufactured by Gurere, M3000 M6000 manufactured by Japan Synthetic, and the like. .
  • the polyvinyl alcohol-based film is not limited to this, but the degree of polymerization is preferably about 1,000 to 10,000, preferably 1,500 to 5,000. This is because when the degree of polymerization satisfies the above range, the molecular motion is free and can be mixed flexibly with iodine or dichroic dye.
  • the protective layer of the present invention is formed using the radical curable composition to support and protect the polarizer, it may be formed by a method well known in the art.
  • the radical curable composition is applied to one surface of the polarizer by a coating method well known in the art such as spin coating, bar coating, roll coating, gravure coating, blade coating, and the like to form a protective layer. It may be carried out by a method of curing through active energy ray irradiation.
  • the active energy ray irradiation method is not particularly limited, and for example, may be performed by irradiating an ultraviolet ray of about 10 to 2500 mJ / cm 2 using an ultraviolet ray irradiation apparatus (fusion lamp, D bulb).
  • the radical curable composition of the present invention as described above (A) a radically polymerizable compound having at least one hydrophilic functional group in the molecule; (B) phosphate compounds having three (meth) acryl groups in the molecule; And (C) a radical initiator.
  • the radical curable composition of the present invention comprises (A) 40 to 93 parts by weight of the radically curable composition, (B) 1 to 30 parts by weight of the phosphate compound, and ( C) 0.5 to 20 parts by weight of radical initiator.
  • the radically polymerizable compound having at least one hydrophilic functional group in the (A) molecule included in the radical curable composition according to the present invention is a component for achieving adhesion of the protective layer, and has at least one hydrophilic functional group in the molecule.
  • adhesion can be realized through hydrogen bonding, and radical polymerization is possible without radical limitation as long as there is an unsaturated carbon bond between carbon atoms in the molecule as a radical polymerizable compound.
  • the hydrophilic functional group is not particularly limited as long as it is possible to hydrogen bond such as hydroxy group, carboxyl group, urethane group, amine group, amide group, etc. Among them, the hydroxy group is particularly preferable for the implementation of excellent adhesion.
  • 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 composition. . 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 composition according to the present invention is a component for further improving the adhesiveness of the adhesive, and further securing excellent water resistance and heat resistance,
  • Various phosphate-based compounds including 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 a compound represented by the following [Formula 25] to [Formula 30].
  • the content of the (B) phosphate compound of the present invention may be 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 composition. have.
  • 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 more than this shows the result that the adhesion decreases.
  • 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 (oxy
  • 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 composition. This is because when the content of the radical initiator satisfies the numerical range, the protective layer may be smoothly cured.
  • the radical curable 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 composition which concerns on this invention is (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 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 compound is preferably contained in 5 to 40 parts by weight, more preferably about 5 to 35 parts by weight, more preferably about 5 to 30 parts by weight in 100 parts by weight of the radical curable composition. Can be. If the content of the (D) phosphate compound is greater than the above range, the adhesion may not be sufficient, and if less than the above range, the water resistance may be weak.
  • the radical curable composition according to the present invention may further comprise (E) a polyfunctional (meth) acrylic compound in order to obtain more excellent adhesion and water resistance effects.
  • the radical curable composition which concerns on this invention is (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 5 parts by weight based on 100 parts by weight of the total composition. It may be about 30 parts by weight.
  • the content of the (E) polyfunctional (meth) acrylic compound is included in more than the above range, the adhesion may not be sufficient, and when less than the above range, the water resistance may be weak.
  • the radical curable composition of the present invention as described above may have a glass transition temperature of 50 ° C. or more after curing, for example, 70 to 140 ° C. or 70 to 130 ° C.
  • the glass transition temperature in the numerical range as described above may have a good heat resistance and water resistance.
  • the radical curable composition may have a viscosity of 70 cP or less, for example, 10 to 70 cP or 10 to 65 cP.
  • the thickness of the protective layer may be thinly formed, and since the composition has a low viscosity, there is an excellent workability.
  • the thickness of the protective layer formed using the radical curable composition is preferably 0.5 to 20 ⁇ m, for example, may be 0.5 to 15 ⁇ m or 0.5 to 10 ⁇ m. This is because when the thickness of the protective layer satisfies the above range, the thickness of the polarizing plate produced can be reduced. If it is less than 0.5 ⁇ m, the thermal shock stability and curl characteristics of the polarizer are weak, and if it is 20 ⁇ m or more, the thickness of the polarizing plate is difficult.
  • the polarizing plate of the present invention may further include a protective film on one surface of the polarizer as needed. More specifically, in the polarizing plate of the present invention, when the protective layer is formed on one surface of the polarizer, a separate protective film may be attached through the adhesive layer to support and protect the polarizer on the opposite side of the surface on which the protective layer is formed. have.
  • the protective film is for supporting and protecting the polarizer
  • protective films of various materials generally known in the art for example, cellulose-based film, polyethylene terephthalate (PET) film, cyclo An olefin polymer (COP, cycloolefin polymer) film, acrylic film, or the like can be used without limitation.
  • PET polyethylene terephthalate
  • COP cycloolefin polymer
  • acrylic film or 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.
  • 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 various polarizing plate adhesives used in the art, for example, polyvinyl alcohol-based adhesives, polyurethane-based adhesives, acrylic adhesives, cationic or radical-based adhesives and the like can be used without limitation.
  • the polarizing plate of the present invention may include an adhesive layer on an upper portion of the protective layer, if necessary, for attachment to an optical film such as a display panel or a retardation film.
  • the pressure-sensitive adhesive layer may be formed using various pressure-sensitive adhesives well known in the art, and the kind thereof is not particularly limited.
  • the pressure-sensitive adhesive layer may be a rubber pressure sensitive adhesive, an acrylic pressure sensitive adhesive, a silicone pressure sensitive adhesive, a urethane pressure sensitive adhesive, a polyvinyl alcohol pressure sensitive adhesive, a polyvinylpyrrolidone pressure sensitive adhesive, a polyacrylamide pressure sensitive adhesive, a cellulose pressure sensitive adhesive, a vinyl alkyl ether pressure sensitive adhesive, or the like. It can be formed using. Among these, in consideration of transparency, heat resistance and the like, it is particularly preferable to use an acrylic pressure-sensitive adhesive.
  • the pressure-sensitive adhesive layer may be formed by applying a pressure-sensitive adhesive on the protective layer, or may be formed by a method of attaching the pressure-sensitive adhesive sheet prepared by applying the pressure-sensitive adhesive on the release sheet and dried on the protective layer.
  • the polarizing plate of the present invention as described above can be usefully applied to an image display device such as a liquid crystal display device.
  • the image display apparatus may be, for example, a liquid crystal display including a liquid crystal panel and polarizing plates provided on both surfaces of the liquid crystal panel, wherein at least one of the polarizing plates may be a polarizing plate according to the present invention.
  • the type of liquid crystal panel included in the liquid crystal display device is not particularly limited.
  • a panel of a passive matrix type such as, but not limited to, a twisted nematic (TN) type, a super twisted nematic (STN) type, a ferrolectic (F) type, or a 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.
  • IPS In Plane Switching
  • VA Vertical Alignment
  • other configurations constituting the liquid crystal display device for example, types of upper and lower substrates (eg, color filter substrates or array substrates) are not particularly limited, and configurations known in the art may be employed without limitation. Can be.
  • 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-819 a radical initiator
  • HEA hydroxyethyl acrylate
  • BPA BPA type epoxy di-acrylate
  • EB600 manufactured by Cytec
  • tri (acryloyloxy ethyl) phosphate (Ciba) 3 parts by weight was added to prepare a radical curable composition A for polarizing plates.
  • HEA hydroxyethyl acrylate
  • BPA BPA type epoxy di-acrylate
  • EB600 Cytec
  • irgacure-819 Ciba
  • Resin prepared by adding 50% by weight of HEA (hydroxyethyl acrylate), 21.4% by weight of BPA type epoxy di-acrylate (EB600, Cytec), 21.4% by weight of tri (acryloyloxy ethyl) phosphate, and 7.2% by weight of di- (methacryloyloxy ethyl) phosphate Radical curable composition C for polarizing plates was prepared by adding 3 parts by weight of irgacure-819 (Ciba), which is a radical initiator, to 100 parts by weight of the composition.
  • irgacure-819 Ciba
  • a resin composition prepared by adding 50% by weight of HEA (hydroxyethyl acrylate), 21.4% by weight of BPA type epoxy di-acrylate (EB600, Cytec), 14.3% by weight of tri (acryloyloxy ethyl) phosphate, and 14.3% by weight of dimethylol tricyclodecane diacrylate (DCPDA).
  • Radical curable composition D for polarizing plates was prepared by adding 3 parts by weight of irgacure-819 (Ciba), a radical initiator, to 100 parts by weight.
  • Resin composition 100 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 manufactured by Cytec), and 16.7% by weight of tri (acryloyloxy ethyl) phosphate Radical curable composition E for polarizing plates was prepared by adding 3 parts by weight of irgacure-819 (Ciba), which is a radical initiator, to parts by weight.
  • HEA hydroxyethyl acrylate
  • 1,4-cyclohexanedimethanol mono-acrylate 16.6% by weight of BPA type epoxy di-acrylate (EB600, Cytec)
  • EB600, Cytec BPA type epoxy di-acrylate
  • tri (acryloyloxy ethyl) phosphate Radical curable composition F for polarizing plates was prepared by adding 3 parts by weight of irgacure-819 (Ciba), which is a radical initiator, to 100 parts by weight of the resin composition.
  • irgacure-819 irgacure-819
  • HEA hydroxyethyl acrylate 50% by weight
  • BPA type epoxy di-acrylate EB600, Cytec
  • DCPDA Dimethylol tricyclodecane diacrylate
  • irgacure-819 Ciba
  • HEA hydroxyethyl acrylate
  • BPA type epoxy di-acrylate EB600, manufactured by Cytec
  • EB600 irgacure-819
  • Radical curable 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 a radical curable composition I for polarizing plates.
  • Irgacure- a radical initiator
  • HEA hydroxyethyl acrylate
  • BPA type epoxy di-acrylate EB600 manufactured by Cytec
  • mono- (methacryloyloxy ethyl) phosphate 3 parts by weight of 819 (Ciba) was added to prepare a radical curable composition J for a polarizing plate.
  • Radical curable 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 one surface of a polarizer (PVA device), and then the conditions were such that the thickness of the final adhesive layer was 1 to 2 ⁇ m. After setting, passed the laminator (5m / min). Then, the surface of the acrylic film is laminated using a UV irradiation device (metal halide lamp), by irradiating ultraviolet light of 1000mJ / cm 2 , to prepare a polarizing plate having a protective film on one surface of the polarizer.
  • a UV irradiation device metal halide lamp
  • the radical curable composition A is applied to the other surface of the surface on which the protective film of the polarizer of the prepared polarizer is laminated, the PET film having a releasing force is laminated, and the final protective layer thickness is 4 to 5 ⁇ m.
  • the laminator 5m / min.
  • the surface on which the release PET is laminated is irradiated with ultraviolet light of 1000 mJ / cm 2 using a ultraviolet halide lamp, and the PET film is removed, and a protective film is provided on one side of the polarizer, and on the other side.
  • the polarizing plate provided with a protective layer was manufactured.
  • a polarizing plate was manufactured in the same manner as in Example 1, except that B was used as the radical curable composition.
  • a polarizing plate was manufactured in the same manner as in Example 1 except that C was used as the radical curable composition.
  • a polarizing plate was manufactured in the same manner as in Example 1 except that D was used as the radical curable composition.
  • a polarizing plate was manufactured in the same manner as in Example 1 except that E was used as the radical curable composition.
  • a polarizing plate was manufactured in the same manner as in Example 1, except that F was used as the radical curable composition.
  • a polarizing plate was manufactured in the same manner as in Example 1, except that G was used as the radical curable composition.
  • a polarizing plate was manufactured in the same manner as in Example 1 except that H was used as the radical curable composition.
  • a polarizing plate was manufactured in the same manner as in Example 1 except that I was used as the radical curable composition.
  • a polarizing plate was manufactured in the same manner as in Example 1, except that J was used as the radical curable composition.
  • the adhesiveness of the protective layer of the polarizing plates manufactured by the said Example and the comparative example was measured, and is shown in following [Table 1]. Specifically, the radical curable composition used in the above Examples and Comparative Examples on the polarizer (PVA device) is applied to 4 ⁇ 5 ⁇ m, laminated on the polarizer (PVA device) and passed through the laminator, and then UV irradiation device (Metal halide) UV) was irradiated at 1000 mJ / cm 2 using a lamp) to prepare a peel force sample consisting of a polarizer / protective layer / polarizer. The sample was left for 4 days at a temperature of 20 ° C.
  • peeling force was measured. At this time, when peeling force was 1.0N / 2cm-2.0N / 2cm, it was excellent, 0.5N / 2cm or more and less than 1.0N / 2cm, and it displayed as bad if it was less than 0.5N / 2cm.
  • 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 properties of the polarizing plates prepared in Examples and Comparative Examples were measured and shown in the following [Table 1]. Specifically, the lamination of the polarizing plates prepared in Examples and Comparative Examples on a glass substrate (glass lamination), it was left for 30 minutes at -40 °C, and then it was left again for 30 minutes at 80 °C repeated 100 times It was performed by. Then, visual evaluation of the deformation of the polarizing plate appearance. The case where the occurrence of cracks of 2 mm or less in the exterior of the polarizing plate alone was excellent, and the case where only linear cracks of 5 mm or more shorter than the end were identified was good, and the case where many cracks occurred on the entire surface of the polarizing plate was indicated as bad.
  • the adhesive layer and the protective layer were manufactured using the same radical curable composition for convenience, but the present invention is not necessarily limited thereto.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polarising Elements (AREA)

Abstract

The present invention relates to a polarizing plate and an image display device comprising same, the polarizing plate comprising: a polarizer; and a protection layer formed on at least one side of the polarizer, wherein the protection layer is a cured product of a radical curable composition comprising: (A) a radical polymerizable compound having at least one hydrophilic functional group in a molecule; (B) a phosphate-based compound having three (meth)acryl groups in a molecule; and (C) a radical initiator.

Description

편광판 및 이를 포함하는 화상표시장치Polarizing plate and image display device including the same
본 발명은 편광판 및 이를 포함하는 화상표시장치에 관한 것으로, 보다 구체적으로는, 편광자 및 보호층의 밀착성이 우수하고, 내수성 및 내열성이 우수하며, 박형으로 제조가 가능한 편광판 및 이를 포함하는 화상표시장치에 관한 것이다.The present invention relates to a polarizing plate and an image display apparatus including the same, and more particularly, to a polarizer and a protective layer having excellent adhesiveness, excellent water resistance and heat resistance, and a thin polarizing plate and an image display apparatus including the same. It is about.
편광판은 통상 이색성 염료 또는 요오드로 염색된 폴리비닐알코올(Polyvinyl alcohol, 이하 'PVA'라 함)계 수지로 이루어진 편광자의 양면에 보호 필름을 적층한 구조로 사용되어 왔다. 이때, 상기 보호 필름으로는 광학적 투명성이나 투습성이 우수하다는 점에서 트리아세틸셀룰로오스(TAC, triacetyl cellulose)계 필름이 필름이 많이 사용되고 있다.The polarizing plate has been commonly used in a structure in which a protective film is laminated on both sides of a polarizer made of a polyvinyl alcohol (hereinafter referred to as 'PVA')-based resin dyed with a dichroic dye or iodine. At this time, the triacetyl cellulose (TAC, triacetyl cellulose) -based film has been used a lot of films in terms of excellent optical transparency and moisture permeability.
한편, 최근 액정표시장치의 노트북형 개인용 컴퓨터, 휴대 전화, 카 내비게이션 등의 모바일 기기로의 전개에 따라, 액정표시장치를 구성하는 편광판에는 박형 경량화가 요구되게 되고 있다. 그러나, 상기와 같이 보호 필름으로 TAC 필름 등을 적층한 편광판에서는, 작업시의 취급성이나 내구 성능의 관점에서 보호 필름의 두께를 20 ㎛ 이하로 하는 것이 곤란하여, 박형 경량화에 한계가 있었다.On the other hand, with the development of a liquid crystal display device into a mobile device such as a notebook personal computer, a mobile phone, a car navigation system, and the like, a thin and light weight is required for the polarizing plate constituting the liquid crystal display device. However, in the polarizing plate which laminated | stacked TAC film etc. with the protective film as mentioned above, it was difficult to make the thickness of a protective film 20 micrometers or less from a viewpoint of the handling property and durability at the time of work, and there existed a limit in thin weight reduction.
상기와 같은 문제점을 해결하기 위하여, 편광자의 한쪽 면에만 보호 필름을 구비하고, 반대 면에는 활성 에너지선 경화성 조성물을 도공하여, 투명 박막층을 형성하는 기술이 제안되고 있다. 한편, 현재까지 제안된 상기 활성 에너지선 경화성 조성물로는 경화방식에 따라 라디칼 경화형 조성물과 양이온 경화형 조성물로 나눌 수 있다. 이때, 양이온 경화형 조성물을 이용하여 투명 박막층을 형성하는 경우 편광자와의 우수한 밀착성을 가지는 장점이 있으나, 느린 경화속도 및 낮은 경화도로 인해 제조 공정상 많은 단점을 갖는다.In order to solve the above problems, a technique for forming a transparent thin film layer by providing a protective film on only one side of the polarizer and coating an active energy ray-curable composition on the opposite side is proposed. On the other hand, the active energy ray-curable composition proposed to date can be divided into a radical curable composition and a cationic curable composition according to the curing method. In this case, when the transparent thin film layer is formed using the cation-curable composition, there is an advantage of having excellent adhesion with the polarizer, but has a number of disadvantages in the manufacturing process due to the slow curing rate and low curing degree.
이러한 양이온 경화형 조성물의 문제점을 해결하기 위해 아크릴계 또는 아크릴 아마이드계 화합물을 주성분으로 하는 라디칼 경화형 조성물을 이용하여 투명 박막층을 형성하는 기술이 제안되었다. 그러나, 아크릴계 또는 아크릴 아마이드계 화합물을 주 성분으로 하는 라디칼 경화형 조성물의 경우, 양이온 경화형 조성물에 비해 경화 속도가 빠르기는 하나, 고습 분위기에서는 경화 속도가 느려지고, 이를 이용하여 형성된 투명 보호층이 편광자와 충분한 밀착성을 가지지 못하며, 또한 편광자 내의 요오드 이온에 영향을 주는 등 내수성이 좋지 못하다는 문제점이 있다. 또한, 상기 아크릴계 또는 아크릴 아마이드계 화합물을 주성분으로 하는 라디칼 경화형 조성물의 경우, 경화 후 보호층의 유리전이온도가 낮기 때문에, 이를 포함하는 편광판의 내열 신뢰성이 좋지 못하다는 문제점이 있다.In order to solve the problem of such a cation-curable composition, a technique of forming a transparent thin film layer using a radical curable composition containing an acrylic or acrylamide-based compound as a main component has been proposed. However, in the case of a radically curable composition containing an acrylic or acrylamide compound as a main component, although the curing speed is faster than that of the cationic curable composition, the curing speed is slow in a high humidity atmosphere, and the transparent protective layer formed by using the polarizer is sufficient There is a problem in that the adhesiveness is not good and the water resistance is poor, such as affecting iodine ions in the polarizer. In addition, in the case of the radically curable composition containing the acrylic or acrylamide compound as a main component, since the glass transition temperature of the protective layer is low after curing, there is a problem that the heat resistance reliability of the polarizing plate including the same is not good.
따라서, 라디칼 경화로 형성이 가능한 박형의 보호층을 가지면서도, 편광자 및 보호층의 밀착성이 우수하고, 내수성 및 내열성이 우수한 새로운 편광판이 요구되고 있다.Therefore, while having the thin protective layer which can be formed by radical hardening, the new polarizing plate which is excellent in the adhesiveness of a polarizer and a protective layer, and excellent in water resistance and heat resistance is calculated | required.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로, 편광자 및 보호층의 밀착성이 우수하고, 내수성 및 내열성이 우수하며, 박형으로 제조가 가능한 편광판 및 이를 포함하는 화상표시장치를 제공하고자 한다.The present invention is to solve the above problems, to provide a polarizing plate excellent in the adhesion between the polarizer and the protective layer, excellent in water resistance and heat resistance, and can be manufactured in a thin shape and an image display device including the same.
일 측면에서, 본 발명은 편광자; 및 상기 편광자의 적어도 일면에 형성되는 보호층을 포함하는 편광판이며, 상기 보호층은 (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 조성물의 경화물인 편광판을 제공한다.In one aspect, the present invention is a polarizer; And a protective layer formed on at least one surface of the polarizer, wherein the protective layer comprises: (A) a radical 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) a polarizing plate which is a cured product of a radical curable composition containing a radical initiator.
한편, 상기 라디칼 경화형 조성물은 라디칼 경화형 조성물 100 중량부에 대하여, (A) 라디칼 중합성 화합물 40 내지 93 중량부; (B) 포스페이트계 화합물 1 내지 30 중량부; 및 (C) 라디칼 개시제 0.5 내지 20 중량부를 포함하는 것이 바람직하다.On the other hand, the radical curable composition is based on 100 parts by weight of the radical curable 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.
한편, 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 것이 특히 바람직하다.On the other hand, 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.
이때, 상기 (a-1) 제 1 화합물은 하기 [화학식 1] 내지 [화학식 21]로 이루어진 군으로부터 선택되는 1종 이상일 수 있다.In this case, the (a-1) first compound may be at least one selected from the group consisting of the following [Formula 1] to [Formula 21].
[화학식 1][Formula 1]
Figure PCTKR2014009133-appb-I000001
Figure PCTKR2014009133-appb-I000001
[화학식 2][Formula 2]
Figure PCTKR2014009133-appb-I000002
Figure PCTKR2014009133-appb-I000002
[화학식 3][Formula 3]
Figure PCTKR2014009133-appb-I000003
Figure PCTKR2014009133-appb-I000003
[화학식 4][Formula 4]
Figure PCTKR2014009133-appb-I000004
Figure PCTKR2014009133-appb-I000004
[화학식 5][Formula 5]
Figure PCTKR2014009133-appb-I000005
Figure PCTKR2014009133-appb-I000005
[화학식 6][Formula 6]
Figure PCTKR2014009133-appb-I000006
Figure PCTKR2014009133-appb-I000006
[화학식 7][Formula 7]
Figure PCTKR2014009133-appb-I000007
Figure PCTKR2014009133-appb-I000007
[화학식 8][Formula 8]
Figure PCTKR2014009133-appb-I000008
Figure PCTKR2014009133-appb-I000008
[화학식 9][Formula 9]
Figure PCTKR2014009133-appb-I000009
Figure PCTKR2014009133-appb-I000009
[화학식 10][Formula 10]
Figure PCTKR2014009133-appb-I000010
Figure PCTKR2014009133-appb-I000010
[화학식 11][Formula 11]
Figure PCTKR2014009133-appb-I000011
Figure PCTKR2014009133-appb-I000011
[화학식 12][Formula 12]
Figure PCTKR2014009133-appb-I000012
Figure PCTKR2014009133-appb-I000012
[화학식 13][Formula 13]
Figure PCTKR2014009133-appb-I000013
Figure PCTKR2014009133-appb-I000013
[화학식 14][Formula 14]
Figure PCTKR2014009133-appb-I000014
Figure PCTKR2014009133-appb-I000014
[화학식 15][Formula 15]
Figure PCTKR2014009133-appb-I000015
Figure PCTKR2014009133-appb-I000015
[화학식 16][Formula 16]
Figure PCTKR2014009133-appb-I000016
Figure PCTKR2014009133-appb-I000016
[화학식 17][Formula 17]
Figure PCTKR2014009133-appb-I000017
Figure PCTKR2014009133-appb-I000017
[화학식 18][Formula 18]
Figure PCTKR2014009133-appb-I000018
Figure PCTKR2014009133-appb-I000018
[화학식 19][Formula 19]
Figure PCTKR2014009133-appb-I000019
Figure PCTKR2014009133-appb-I000019
[화학식 20][Formula 20]
Figure PCTKR2014009133-appb-I000020
Figure PCTKR2014009133-appb-I000020
[화학식 21][Formula 21]
Figure PCTKR2014009133-appb-I000021
Figure PCTKR2014009133-appb-I000021
또한, 상기 (a-2) 제 2 화합물은 하기 [화학식 22] 내지 [화학식 24]로 이루어진 군으로부터 선택되는 1종 이상일 수 있다.In addition, the (a-2) second compound may be at least one selected from the group consisting of the following [Formula 22] to [Formula 24].
[화학식 22][Formula 22]
Figure PCTKR2014009133-appb-I000022
Figure PCTKR2014009133-appb-I000022
[화학식 23][Formula 23]
Figure PCTKR2014009133-appb-I000023
Figure PCTKR2014009133-appb-I000023
[화학식 24][Formula 24]
Figure PCTKR2014009133-appb-I000024
Figure PCTKR2014009133-appb-I000024
한편, 상기 (B) 포스페이트계 화합물은 하기 [화학식 I]로 표시되는 화합물인 것이 바람직하다.On the other hand, it is preferable that the (B) phosphate compound is a compound represented by the following [Formula I].
[화학식 I][Formula I]
Figure PCTKR2014009133-appb-I000025
Figure PCTKR2014009133-appb-I000025
상기 [화학식 I]에서, R1, R2 및 R3는 각각 독립적으로 치환 또는 비치환된 C1~10 알킬렌기, 치환 또는 비치환된 C4~14 시클로알킬렌기, 치환 또는 비치환된 C6~14 아릴렌기, 또는 이들의 조합이고; R4, R5 및 R6은 각각 독립적으로 수소 또는 메틸기이며; X1, X2 및 X3는 각각 독립적으로 O(산소) 또는 N(질소)임.The Formula I] from, 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).
한편, 상기 라디칼 경화형 조성물은 (D) 분자 내에 1개 또는 2개의 (메트)아크릴기를 갖는 포스페이트계 화합물을 더 포함하는 것일 수 있다.Meanwhile, the radical curable composition may further include a phosphate compound having one or two (meth) acryl groups in the (D) molecule.
이때, 상기 (D) 포스페이트계 화합물은 라디칼 경화형 조성물 100 중량부에 있어서 5 내지 40 중량부로 포함되는 것이 보다 바람직하다.At this time, 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 composition.
또한, 상기 (D) 포스페이트계 화합물은 하기 [화학식 Ⅱ] 및/또는 [화학식 Ⅲ]로 표시되는 화합물인 것이 보다 바람직하다.In addition, the (D) phosphate-based compound is more preferably a compound represented by the following [Formula II] and / or [Formula III].
[화학식 Ⅱ][Formula II]
Figure PCTKR2014009133-appb-I000026
Figure PCTKR2014009133-appb-I000026
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.Wherein in Formula Ⅱ], 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).
[화학식 Ⅲ][Formula III]
Figure PCTKR2014009133-appb-I000027
Figure PCTKR2014009133-appb-I000027
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.The Formula Ⅲ] in, 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).
한편, 상기 라디칼 경화형 조성물은 (E) 다관능성 (메트)아크릴계 화합물을 더 포함하는 것일 수도 있다.In addition, the said radical curable composition may further contain the (E) polyfunctional (meth) acrylic-type compound.
이때, 상기 (E) 다관능성 (메트)아크릴계 화합물은 라디칼 경화형 조성물 100 중량부에 있어서 5 내지 40 중량부로 포함되는 것이 보다 바람직하다.At this time, the (E) polyfunctional (meth) acrylic compound is more preferably contained in 5 to 40 parts by weight in 100 parts by weight of the radical curable composition.
또한, 상기 (E) 다관능성 (메트)아크릴계 화합물은 하기 [화학식 Ⅳ] 내지 [화학식 Ⅵ]로 표시되는 화합물로 이루어진 군으로 선택된 1종 이상인 것이 보다 바람직하다.In addition, 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].
[화학식 Ⅳ][Formula IV]
Figure PCTKR2014009133-appb-I000028
Figure PCTKR2014009133-appb-I000028
상기 [화학식 Ⅳ]에서, R13 및 R14는 각각 독립적으로 (메트)아크릴로일옥시기 또는 (메트)아크릴로일옥시알킬기임.In [Formula IV], R 13 and R 14 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group.
[화학식 Ⅴ][Formula Ⅴ]
Figure PCTKR2014009133-appb-I000029
Figure PCTKR2014009133-appb-I000029
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.In Formula [V], R 15 , R 16 and R 17 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group, and R 18 is a (meth) acryloyloxy group, (meth ) Acryloyloxyalkyl group, a hydroxy group, or a substituted or unsubstituted C 1-10 alkyl group.
[화학식 Ⅵ][Formula VI]
Figure PCTKR2014009133-appb-I000030
Figure PCTKR2014009133-appb-I000030
상기 [화학식 Ⅵ]에서, R19는 치환 또는 비치환된 C1~10 알킬렌이고, R20 및 R21은 각각 독립적으로 (메트)아크릴로일옥시기 또는 (메트)아크릴로일옥시알킬기임.In Formula [VI], 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.
한편, 상기 라디칼 경화형 조성물은 경화 후 유리전이온도가 50℃ 이상인 것이 바람직하다.On the other hand, the radical curable composition is preferably a glass transition temperature of 50 ℃ or more after curing.
또한, 상기 라디칼 경화형 조성물은 점도가 70cP 이하인 것이 바람직하다.In addition, the radical curable composition preferably has a viscosity of 70 cP or less.
한편, 상기 보호층은 두께가 0.5 내지 20㎛인 것이 바람직하다.On the other hand, the protective layer preferably has a thickness of 0.5 to 20㎛.
한편, 본 발명의 상기 편광판은 상기 편광자의 보호층이 형성된 면의 반대면에 접착제층을 매개로 보호 필름을 더 부착될 수 있다.On the other hand, the polarizing plate of the present invention may be further attached to the protective film via the adhesive layer on the opposite side of the surface on which the protective layer of the polarizer is formed.
또한, 본 발명의 상기 편광판은 상기 보호층 상부에 점착층을 더 포함할 수 있다.In addition, the polarizing plate of the present invention may further include an adhesive layer on the protective layer.
다른 측면에서, 본 발명은 상기 편광판을 포함하는 화상표시장치를 제공한다.In another aspect, the present invention provides an image display device including the polarizing plate.
본 발명의 편광판은 편광자 및 보호층의 밀착성이 우수하고, 고습 환경에서도 편광자 내의 요오드 이온의 탈색을 방지할 수 있는 등 내수성이 우수하며, 경화 후 보호층의 유리전이온도가 높은바 내열성이 우수하다.The polarizing plate of the present invention is excellent in the adhesion between the polarizer and the protective layer, and excellent in water resistance, such as being able to prevent the discoloration of iodine ions in the polarizer even in a high humidity environment, and has a high glass transition temperature of the protective layer after curing. .
또한, 본 발명의 편광판은 보호층 형성 조성물이 높은 습도 상황에서도 편광자의 탈색이 발생하지 않는 등 내수성이 우수하고 나아가 낮은 점도를 가지는바 박형으로 제조가 가능하며, 작업성 역시 우수하다.In addition, the polarizing plate of the present invention is excellent in water resistance, such as no discoloration of the polarizer even in a high humidity environment of the protective layer forming composition can be manufactured in a thin bar, and also excellent workability.
이하, 본 발명의 바람직한 실시 형태들을 설명한다. 그러나, 본 발명의 실시형태는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 이하 설명하는 실시 형태로 한정되는 것은 아니다. 또한, 본 발명의 실시형태는 당해 기술분야에서 평균적인 지식을 가진 자에게 본 발명을 더욱 완전하게 설명하기 위해서 제공되는 것이다. Hereinafter, preferred embodiments of the present invention will be described. However, embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below. In addition, the embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.
1. 편광판1. Polarizer
본 발명자들은 연구를 거듭한 결과, 보호층을 형성하기 위한 친수성 관능기를 갖는 라디칼 경화형 조성물에 분자 내에 3개의 (메트)아크릴기를 갖는 포스페이트계 화합물을 혼합하여 사용하는 경우, 밀착성이 우수할 뿐만 아니라, 내수성 및 내열성이 우수하며, 나아가 저 점도의 구현이 가능하다는 것을 알아내고 본 발명을 완성하였다.The present inventors have conducted extensive studies and, in the case of using a phosphate compound having three (meth) acryl groups in a molecule in a radically curable composition having a hydrophilic functional group for forming a protective layer, not only the adhesiveness is excellent, The present invention was completed by finding out that the water resistance and the heat resistance are excellent, and furthermore, low viscosity can be realized.
보다 구체적으로는, 본 발명의 라디칼 경화형 조성물은, 편광자; 및 상기 편광자의 적어도 일면에 형성되는 보호층을 포함하는 편광판이며, 상기 보호층은 (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 조성물의 경화물이다.More specifically, the radical curable composition of this invention is a polarizer; And a protective layer formed on at least one surface of the polarizer, wherein the protective layer comprises: (A) a radical 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) a radical curable composition comprising a radical initiator.
1-1. 편광자1-1. Polarizer
먼저, 본 발명의 상기 편광자는 당해 기술분야에 잘 알려진 편광자, 예를 들면 요오드 또는 이색성 염료를 포함하는 폴리비닐알콜(PVA)로 이루어진 필름을 사용할 수 있다. 상기 편광자는 폴리비닐알코올 필름에 요오드 또는 이색성 염료를 염착시켜서 제조될 수 있으나, 이의 제조방법은 특별히 한정되지 않는다. 본 명세서에 있어서, 편광자는 보호층(또는 보호 필름)을 포함하지 않는 상태를 의미하며, 편광판은 편광자와 보호층(또는 보호 필름)을 포함하는 상태를 의미한다.First, the polarizer of the present invention may use a film made of polyvinyl alcohol (PVA) containing a polarizer well known in the art, for example, iodine or dichroic dye. The polarizer may be prepared by dyeing iodine or dichroic dye on a polyvinyl alcohol film, but a method of manufacturing the same is not particularly limited. In the present specification, the polarizer means a state not including a protective layer (or protective film), and the polarizing plate means a state including a polarizer and a protective layer (or protective film).
한편, 상기 편광자가 폴리비닐알코올계 필름인 경우, 폴리비닐알코올계 필름은 폴리비닐알코올 수지 또는 그 유도체를 포함하는 것이면 특별한 제한 없이 사용이 가능하다. 이때, 상기 폴리비닐알코올 수지의 유도체로는, 이에 한정되는 것은 아니나, 폴리비닐포르말 수지, 폴리비닐아세탈 수지 등을 들 수 있다. 또는, 상기 폴리비닐알코올계 필름은 당해 기술분야에 있어서 편광자 제조에 일반적으로 사용되는 시판되는 폴리비닐알코올계 필름, 예컨대, 구라레 사의 P30, PE30, PE60, 일본합성사의 M3000 M6000 등을 사용할 수도 있다.On the other hand, when the polarizer is a polyvinyl alcohol-based film, the polyvinyl alcohol-based film can be used without particular limitation as long as it contains a polyvinyl alcohol resin or a derivative thereof. In this case, examples of the derivative of the polyvinyl alcohol resin include, but are not limited to, polyvinyl formal resin, polyvinyl acetal resin, and the like. Alternatively, the polyvinyl alcohol-based film may be a commercially available polyvinyl alcohol-based film commonly used in the manufacture of polarizers in the art, for example, P30, PE30, PE60 manufactured by Gurere, M3000 M6000 manufactured by Japan Synthetic, and the like. .
한편, 상기 폴리비닐알코올계 필름은, 이로써 한정되는 것은 아니나, 중합도가 1,000 내지 10,000 정도, 바람직하게는 1,500 내지 5,000 정도인 것이 좋다. 중합도가 상기 범위를 만족할 때, 분자 움직임이 자유롭고, 요오드 또는 이색성 염료 등과 유연하게 혼합될 수 있기 때문이다.On the other hand, the polyvinyl alcohol-based film is not limited to this, but the degree of polymerization is preferably about 1,000 to 10,000, preferably 1,500 to 5,000. This is because when the degree of polymerization satisfies the above range, the molecular motion is free and can be mixed flexibly with iodine or dichroic dye.
1-2. 보호층1-2. Protective layer
다음으로, 본 발명의 상기 보호층은 편광자를 지지 및 보호하기 위하여 상기 라디칼 경화형 조성물을 이용하여 형성된 것으로, 당해 기술 분야에 잘 알려진 방법에 의해 형성될 수 있다. 예를 들면, 편광자의 일면에 상기 라디칼 경화형 조성물을 당해 기술 분야에 잘 알려진 코팅 법, 예컨대 스핀 코팅, 바 코팅, 롤 코팅, 그라비아 코팅, 블레이드 코팅 등의 방법으로 도포하여 보호층을 형성한 다음, 활성 에너지선 조사를 통해 경화시키는 방법으로 수행될 수 있다. 활성 에너지선 조사 방법은 특별히 한정되지 않으며, 예를 들면, 자외선 조사장치(fusion lamp, D bulb)를 이용하여 10 내지 2500mJ/cm2 정도의 자외선을 조사하는 방법으로 수행할 수 있다.Next, the protective layer of the present invention is formed using the radical curable composition to support and protect the polarizer, it may be formed by a method well known in the art. For example, the radical curable composition is applied to one surface of the polarizer by a coating method well known in the art such as spin coating, bar coating, roll coating, gravure coating, blade coating, and the like to form a protective layer. It may be carried out by a method of curing through active energy ray irradiation. The active energy ray irradiation method is not particularly limited, and for example, may be performed by irradiating an ultraviolet ray of about 10 to 2500 mJ / cm 2 using an ultraviolet ray irradiation apparatus (fusion lamp, D bulb).
이때, 본 발명의 상기 라디칼 경화형 조성물은 상기한 바와 같이 (A) 분자 내에 적어도 1개의 친수성 관능기를 갖는 라디칼 중합성 화합물; (B) 분자 내에 3개의 (메트)아크릴기를 갖는 포스페이트계 화합물; 및 (C) 라디칼 개시제를 포함한다.In this case, the radical curable composition of the present invention, as described above (A) a radically polymerizable compound having at least one hydrophilic functional group in the molecule; (B) phosphate compounds having three (meth) acryl groups in the molecule; And (C) a radical initiator.
보다 바람직하게는, 본 발명의 상기 라디칼 경화형 조성물은, 라디칼 경화형 조성물 100 중량부에 있어서, (A) 라디칼 중합성 화합물 40 내지 93 중량부, (B) 포스페이트계 화합물 1 내지 30 중량부, 및 (C) 라디칼 개시제 0.5 내지 20 중량부를 포함한다.More preferably, the radical curable composition of the present invention comprises (A) 40 to 93 parts by weight of the radically curable composition, (B) 1 to 30 parts by weight of the phosphate compound, and ( C) 0.5 to 20 parts by weight of radical initiator.
가. 친수성기 포함 라디칼 중합성 화합물 (A)end. Radical polymerizable compound containing a hydrophilic group (A)
먼저, 본 발명에 따른 라디칼 경화형 조성물에 포함되는 상기 (A) 분자 내에 적어도 1개의 친수성 관능기를 갖는 라디칼 중합성 화합물은 보호층의 밀착성을 구현하기 위한 성분으로, 분자 내에 적어도 하나의 친수성 관능기를 가짐으로써 수소 결합을 통한 밀착성 구현이 가능하고, 또한 라디칼 중합성 화합물로 분자 내에 탄소간 불포화 이중 결합이 존재함으로써 라디칼 중합이 가능한 것이면 특별한 제한 없이 사용이 가능하다. 이때, 상기 친수성 관능기는 히드록시기, 카르복시기, 우레탄기, 아민기, 아마이드기 등 수소 결합이 가능한 것이면 특별히 제한 되는 것은 아니나, 그 중에서도 특히 히드록시기인 것이 우수한 밀착성의 구현을 위하여 보다 바람직하다.First, the radically polymerizable compound having at least one hydrophilic functional group in the (A) molecule included in the radical curable composition according to the present invention is a component for achieving adhesion of the protective layer, and has at least one hydrophilic functional group in the molecule. As a result, adhesion can be realized through hydrogen bonding, and radical polymerization is possible without radical limitation as long as there is an unsaturated carbon bond between carbon atoms in the molecule as a radical polymerizable compound. In this case, the hydrophilic functional group is not particularly limited as long as it is possible to hydrogen bond such as hydroxy group, carboxyl group, urethane group, amine group, amide group, etc. Among them, the hydroxy group is particularly preferable for the implementation of excellent adhesion.
한편, 이에 한정되는 것은 아니나, 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 것이 본 발명의 효과를 구현하기 위하여 특히 바람직하다.On the other hand, the present invention is not limited thereto, but 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.
이때, 상기 (a-1) 제 1 화합물은 분자 내에 적어도 1개의 히드록시기를 포함하며, 적어도 1개의 (메트)아크릴기를 포함하는 것이면 특별한 제한 없이 사용이 가능하나, 다만 본 명세서에서는 후술하는 (a-2) 제 2 화합물에 해당하는 것은 (a-1) 제 1 화합물에서 제외한다.In this case, 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).
보다 구체적으로, 상기 (a-1) 제 1 화합물은, 이에 한정되는 것은 아니나, 예를 들면, 하기 [화학식 1] 내지 [화학식 21]로 이루어진 군으로부터 선택되는 1종 이상일 수 있다.More specifically, 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].
[화학식 1][Formula 1]
Figure PCTKR2014009133-appb-I000031
Figure PCTKR2014009133-appb-I000031
[화학식 2][Formula 2]
Figure PCTKR2014009133-appb-I000032
Figure PCTKR2014009133-appb-I000032
[화학식 3][Formula 3]
Figure PCTKR2014009133-appb-I000033
Figure PCTKR2014009133-appb-I000033
[화학식 4][Formula 4]
Figure PCTKR2014009133-appb-I000034
Figure PCTKR2014009133-appb-I000034
[화학식 5][Formula 5]
Figure PCTKR2014009133-appb-I000035
Figure PCTKR2014009133-appb-I000035
[화학식 6][Formula 6]
Figure PCTKR2014009133-appb-I000036
Figure PCTKR2014009133-appb-I000036
[화학식 7][Formula 7]
Figure PCTKR2014009133-appb-I000037
Figure PCTKR2014009133-appb-I000037
[화학식 8][Formula 8]
Figure PCTKR2014009133-appb-I000038
Figure PCTKR2014009133-appb-I000038
[화학식 9][Formula 9]
Figure PCTKR2014009133-appb-I000039
Figure PCTKR2014009133-appb-I000039
[화학식 10][Formula 10]
Figure PCTKR2014009133-appb-I000040
Figure PCTKR2014009133-appb-I000040
[화학식 11][Formula 11]
Figure PCTKR2014009133-appb-I000041
Figure PCTKR2014009133-appb-I000041
[화학식 12][Formula 12]
Figure PCTKR2014009133-appb-I000042
Figure PCTKR2014009133-appb-I000042
[화학식 13][Formula 13]
Figure PCTKR2014009133-appb-I000043
Figure PCTKR2014009133-appb-I000043
[화학식 14][Formula 14]
Figure PCTKR2014009133-appb-I000044
Figure PCTKR2014009133-appb-I000044
[화학식 15][Formula 15]
Figure PCTKR2014009133-appb-I000045
Figure PCTKR2014009133-appb-I000045
[화학식 16][Formula 16]
Figure PCTKR2014009133-appb-I000046
Figure PCTKR2014009133-appb-I000046
[화학식 17][Formula 17]
Figure PCTKR2014009133-appb-I000047
Figure PCTKR2014009133-appb-I000047
[화학식 18][Formula 18]
Figure PCTKR2014009133-appb-I000048
Figure PCTKR2014009133-appb-I000048
[화학식 19][Formula 19]
Figure PCTKR2014009133-appb-I000049
Figure PCTKR2014009133-appb-I000049
[화학식 20][Formula 20]
Figure PCTKR2014009133-appb-I000050
Figure PCTKR2014009133-appb-I000050
[화학식 21][Formula 21]
Figure PCTKR2014009133-appb-I000051
Figure PCTKR2014009133-appb-I000051
또한, 상기 (a-2) 제 2 화합물은 분자 내에 적어도 2개의 히드록시기를 포함하고, 적어도 1개의 벤젠 고리 또는 시클로헥산 고리를 포함하며, 적어도 2개의 (메트)아크릴기를 포함하는 것이면 특별한 제한 없이 사용이 가능하다.In addition, 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.
보다 구체적으로, 상기 (a-2) 제 2 화합물은, 이에 한정되는 것은 아니나, 예를 들면, 하기 [화학식 22] 내지 [화학식 24]로 이루어진 군으로부터 선택되는 1종 이상일 수 있다.More specifically, 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.
[화학식 22][Formula 22]
Figure PCTKR2014009133-appb-I000052
Figure PCTKR2014009133-appb-I000052
[화학식 23][Formula 23]
Figure PCTKR2014009133-appb-I000053
Figure PCTKR2014009133-appb-I000053
[화학식 24][Formula 24]
Figure PCTKR2014009133-appb-I000054
Figure PCTKR2014009133-appb-I000054
한편, 본 발명의 상기 라디칼 중합성 화합물의 함량은 전체 조성물 100 중량부에 있어서, 40 내지 93 중량부정도, 바람직하게는 40 내지 90 중량부정도, 더욱 바람직하게는 45 내지 90 중량부정도일 수 있다. 이와 같은 함량으로 포함되는 경우 우수한 밀착성 구현이 가능하기 때문이다.Meanwhile, 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 composition. . If it is included in such a content because it is possible to implement excellent adhesion.
나. 3관능성 포스페이트계 화합물 (B)I. Trifunctional Phosphate Compounds (B)
다음으로, 본 발명에 따른 라디칼 경화형 조성물에 포함되는 상기 (B) 분자 내에 3개의 (메트)아크릴기를 갖는 포스페이트계 화합물은 접착제의 밀착성을 더욱 향상시키고, 나아가 우수한 내수성 및 내열성 확보하기 위한 성분으로, 분자 내에 3개의 (메트)아크릴기를 포함하는 다양한 포스페이트계 화합물을 사용할 수 있다.Next, the phosphate compound having three (meth) acryl groups in the (B) molecule included in the radical curable composition according to the present invention is a component for further improving the adhesiveness of the adhesive, and further securing excellent water resistance and heat resistance, Various phosphate-based compounds including three (meth) acryl groups in the molecule can be used.
본 발명의 발명자들의 연구 결과에 따르면, 포스페이트계 화합물 중에서도 특히 분자 내에 세 개의 (메트)아크릴기를 포함하는 것을 사용하는 경우, 분자 내에 하나 또는 두 개의 (메트)아크릴기를 포함하는 것을 사용하는 경우 대비, 우수한 열충격 안정성내열성 역시 확보할 수 있으며, 나아가 저 점도의 구현이 더욱 용이하였다.According to the results of the inventors of the present invention, in the case of using the one containing two (meth) acryl groups in the molecule, especially the one containing two or more (meth) acryl groups in the molecule, Excellent thermal shock stability heat resistance can also be secured, and it is easier to implement low viscosity.
한편, 이에 한정되는 것은 아니나, 상기 (B) 포스페이트계 화합물은 하기 [화학식 I]로 표시되는 화합물인 것이 보다 바람직하다. 이 경우 상기한 효과가 특히 우수하기 때문이다.In addition, although it is not limited to this, It is more preferable that the said (B) phosphate type compound is a compound represented by following [Formula I]. This is because the above effects are particularly excellent.
[화학식 I][Formula I]
Figure PCTKR2014009133-appb-I000055
Figure PCTKR2014009133-appb-I000055
상기 [화학식 I]에서, R1, R2 및 R3는 각각 독립적으로 치환 또는 비치환된 C1~10 알킬렌기, 치환 또는 비치환된 C4~14 시클로알킬렌기, 치환 또는 비치환된 C6~14 아릴렌기, 또는 이들의 조합이고; R4, R5 및 R6은 각각 독립적으로 수소 또는 메틸기이며; X1, X2 및 X3는 각각 독립적으로 O(산소) 또는 N(질소)이다.The Formula I] from, 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).
이때, 상기 R1, R2 및 R3에 있어서, 상기 알킬렌기는 1 내지 10개, 또는 1 내지 8개, 또는 1 내지 4개의 탄소 원자의 직쇄 또는 분지쇄의 2가 탄화수소 부위를 의미하며, 본 명세서에서 상기 알킬렌기는 분자 내에 적어도 하나의 불포화 결합을 포함할 수도 있다. 한편, 상기 알킬렌기로는, 이에 한정되는 것은 아니나, 메틸렌, 에틸렌, 트리메틸렌, 테트라메틸렌, 펜타메틸렌, 헥사메틸렌, 헵타메틸렌, 노나메틸렌, 데카메틸렌 등을 그 예로 들 수 있다. 상기 알킬렌기에 포함되어 있는 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In this case, in the R 1 , R 2 and R 3 , 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 alkylene group may include at least one unsaturated bond in the molecule. On the other hand, 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.
또한, 상기 R1, R2 및 R3에 있어서, 상기 시클로알킬렌기는 4 내지 14개, 또는 4 내지 10개, 또는 4 내지 6개의 고리 탄소의 비방향족 2가 모노사이클릭, 바이사이클릭 또는 트리사이클릭 탄화수소 부위를 의미하며, 본 명세서에서 상기 알킬렌기는 분자 내에 적어도 하나의 불포화 결합을 포함할 수도 있다. 한편, 상기 시클로알킬렌기로는, 이에 한정되는 것은 아니나, 2가의, 시클로펜탄 고리, 시클로헥산 고리 등을 그 예로 들 수 있다. 상기 시클로알킬렌기에 포함되어 있는 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In addition, in R 1 , R 2 and R 3 , 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. In addition, as said cycloalkylene group, although it is not limited to this, 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.
또한, 상기 R1, R2 및 R3에 있어서, 상기 아릴렌기는 6 내지 14개, 또는 6 내지 12개의 고리 원자를 가지는 2가 모노시클릭, 바이시클릭 또는 트리시클릭 방향족 탄화수소 부위를 의미하며, 이에 한정되는 것은 아니나, 2가의, 벤젠 고리, 나프탈렌 고리, 안트라센 고리, 비페닐 고리 등을 그 예로 들 수 있다. 상기 아릴렌기에 포함되어 있는 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In addition, in the R 1 , R 2 and R 3 , 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.
한편, 상기 R1, R2 및 R3는, 이에 한정되는 것은 아니나, 그 중에서도 치환 또는 비치환된 C1~10 알킬렌기인 것이 바람직하고, 치환 또는 비치환된 C1~8 알킬렌기인 것이 보다 바람직하며, 치환 또는 비치환된 C1~4 알킬렌기인 것이 더욱 바람직하다.On the other hand, the 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.
보다 구체적으로, 이에 한정되는 것은 아니나, 상기 (B) 포스페이트계 화합물은 하기 [화학식 25] 내지 [화학식 30]로 표시되는 화합물일 수 있다.More specifically, the present invention is not limited thereto, but the phosphate-based compound (B) may be a compound represented by the following [Formula 25] to [Formula 30].
[화학식 25][Formula 25]
Figure PCTKR2014009133-appb-I000056
Figure PCTKR2014009133-appb-I000056
[화학식 26][Formula 26]
.
Figure PCTKR2014009133-appb-I000057
.
Figure PCTKR2014009133-appb-I000057
[화학식 27][Formula 27]
Figure PCTKR2014009133-appb-I000058
Figure PCTKR2014009133-appb-I000058
[화학식 28][Formula 28]
Figure PCTKR2014009133-appb-I000059
Figure PCTKR2014009133-appb-I000059
[화학식 29][Formula 29]
Figure PCTKR2014009133-appb-I000060
Figure PCTKR2014009133-appb-I000060
[화학식 30][Formula 30]
Figure PCTKR2014009133-appb-I000061
Figure PCTKR2014009133-appb-I000061
한편, 본 발명의 (B) 포스페이트계 화합물의 함량은 전체 조성물 100 중량부에 있어서, 1 내지 30 중량부정도, 바람직하게는 5 내지 30 중량부정도, 더욱 바람직하게는 6 내지 29 중량부정도일 수 있다. 포스페이트계 화합물을 이보다 적게 첨가하여 사용하는 경우 열충격 안정성 및 내수성 확보가 어려우며, 점도가 높다. 또한 이보다 많이 첨가하여 사용하는 경우 밀착성이 하락하는 결과를 보인다.Meanwhile, the content of the (B) phosphate compound of the present invention may be 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 composition. have. When 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 more than this shows the result that the adhesion decreases.
다. 라디칼 개시제 (C)All. Radical initiator (C)
다음으로, 본 발명에 따른 라디칼 경화형 조성물에 포함되는 상기 (C)라디칼 개시제는, 라디칼 중합성을 촉진하여 경화 속도를 향상시키기 위한 것이다. 이때, 상기 라디칼 개시제로는 당해 기술 분야에서 일반적으로 사용되는 라디칼 개시제들이 제한 없이 사용될 수 있으며, 예를 들면, 1-하이드록시-사이클로헥실-펜닐-케톤(1-Hydroxy-cyclohexyl-phenyl-ketone), 2-하이드록시-2-메틸-1-페닐-1-프로판온(2-Hydroxy-2-methyl-1-phenyl-1-propanone), 2-히드록시-1-[4-(2-하이드록시에톡시)페닐]-2-메틸-1-프로판온(2-Hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1-propanone), 메틸벤조일포르메이트(Methylbenzoylformate), 옥시-페닐-아세트산-2-[2-옥소-2-페닐-아세톡시-에톡시]-에틸 에스테르(oxy-phenyl-acetic acid -2-[2 oxo-2phenyl-acetoxy-ethoxy]-ethyl ester), 옥시-페닐-아세트산-2-[2-하이드록시-에톡시]-에틸 에스테르(oxy-phenyl-acetic acid-2-[2-hydroxy-ethoxy]-ethyl ester), 알파-디메톡시-알파-페닐아세토페논(alpha-dimethoxy-alpha-phenylacetophenone), 2-벤질-2-(디메틸아미노)1-[4-(4-모르폴리닐) 페닐]-1-부타논(2-Benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl) phenyl]-1-butanone), 2-메틸-1-[4-(메틸티오)페닐]-2-(4-모르폴리닐)-1-프로판온(2-Methyl-1-[4-(methylthio)phenyl] -2-(4-morpholinyl)-1-propanone), 디페닐 (2,4,6-트리메틸벤조일)-포스핀 옥사이드(Diphenyl (2,4,6-trimethylbenzoyl)-phosphine oxide), 페닐비스(2,4,6-트리메틸벤조일)-포스핀옥사이드(phenylbis(2,4,6-trimethylbenzoyl)-phosphineoxide)로 이루어진 그룹으로부터 선택된 1종 이상일 수 있다. 특히, 본 발명에 있어서, 페닐비스(2,4,6-트리메틸벤조일)-포스핀옥사이드(phenylbis(2,4,6-trimethylbenzoyl)-phosphineoxide)인 것이 바람직하다.Next, the said (C) radical initiator contained in the radical curable composition which concerns on this invention is for promoting radical polymerization property and improving hardening speed. In this case, as the radical initiator, 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 (oxy-phenyl-acetic acid-2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester) , Oxy-phenyl-acetic acid-2- [2-hydroxy-ethoxy] -ethyl ester, oxy-phenyl-acetic acid-2- [2-hydroxy-ethoxy] -ethyl ester, alpha-dimethoxy-alpha- Phenylacetophenone (alpha-dimethoxy-alpha-phenylacetophenone), 2-benzyl-2- (dimethylamino) 1- [4- (4-morpholi ) Phenyl] -1-butanone (2-Benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone), 2-methyl-1- [4- (methylthio) Phenyl] -2- (4-morpholinyl) -1-propanone (2-Methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone), diphenyl (2 (4,6-trimethylbenzoyl) -phosphine oxide (Diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide), phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide (phenylbis (2,4) , 6-trimethylbenzoyl) -phosphineoxide) may be one or more selected from the group consisting of. In particular, in the present invention, phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide (phenylbis (2,4,6-trimethylbenzoyl) -phosphineoxide) is preferable.
한편, 상기 (C) 라디칼 개시제의 함량은 예를 들면, 라디칼 경화형 조성물 100 중량부에 대해, 0.5 내지 20 중량부, 0.5 내지 15 중량부 또는 0.5 내지 10 중량부 정도인 것이 바람직하다. 라디칼 개시제의 함량이 상기 수치범위를 만족하는 경우, 보호층의 경화가 원활하게 이루어질 수 있기 때문이다.On the other hand, 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 composition. This is because when the content of the radical initiator satisfies the numerical range, the protective layer may be smoothly cured.
라. 추가 포스페이트계 화합물 (D)la. Additional Phosphate Compounds (D)
본 발명에 따른 라디칼 경화형 조성물은 보다 우수한 밀착성 및 내수성 효과를 얻기 위하여, (D) 분자 내에 1개 또는 2개의 (메트)아크릴기를 갖는 포스페이트계 화합물을 더 포함할 수 있다.The radical curable 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.
즉, 본 발명에 따른 라디칼 경화형 조성물은 (A) 분자 내에 적어도 1개의 친수성 관능기를 갖는 라디칼 중합성 화합물; (B) 분자 내에 3개의 (메트)아크릴기를 갖는 포스페이트계 화합물; (C) 라디칼 개시제; 및 (D) 분자 내에 1개 또는 2개의 (메트)아크릴기를 갖는 포스페이트계 화합물을 포함하는 것일 수 있다.That is, the radical curable composition which concerns on this invention is (A) radically polymerizable compound which has at least 1 hydrophilic functional group in a molecule | numerator; (B) phosphate compounds having three (meth) acryl groups in the molecule; (C) a radical initiator; And (D) a phosphate compound having one or two (meth) acryl groups in the molecule.
이때, 상기 (D) 포스페이트계 화합물은 특별히 한정되지 않으며, 분자 내에 1개 또는 2개의 (메트)아크릴기를 포함하는 다양한 포스페이트계 화합물을 사용할 수 있다.In this case, 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.
한편, 이에 한정되는 것은 아니나, 상기 (D) 포스페이트계 화합물은 하기 [화학식 Ⅱ] 및/또는 [화학식 Ⅲ]로 표시되는 화합물인 것이 보다 바람직하다. 이 경우 상기한 효과가 특히 우수하기 때문이다.On the other hand, 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.
[화학식 Ⅱ][Formula II]
Figure PCTKR2014009133-appb-I000062
Figure PCTKR2014009133-appb-I000062
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.Wherein in Formula Ⅱ], 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).
이때, 상기 R7 및 R8에 있어서, 상기 알킬렌기는 1 내지 10개, 또는 1 내지 8개, 또는 1 내지 4개의 탄소 원자의 직쇄 또는 분지쇄의 2가 탄화수소 부위를 의미하며, 본 명세서에서 상기 알킬렌기는 분자 내에 적어도 하나의 불포화 결합을 포함할 수도 있다. 한편, 상기 알킬렌기로는, 이에 한정되는 것은 아니나, 메틸렌, 에틸렌, 트리메틸렌, 테트라메틸렌, 펜타메틸렌, 헥사메틸렌, 헵타메틸렌, 노나메틸렌, 데카메틸렌 등을 그 예로 들 수 있다. 상기 알킬렌기에 포함되어 있는 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In this case, in the R 7 and R 8 , 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. On the other hand, 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.
또한, 상기 R7 및 R8에 있어서, 상기 시클로알킬렌기는 4 내지 14개, 또는 4 내지 10개, 또는 4 내지 6개의 고리 탄소의 비방향족 2가 모노사이클릭, 바이사이클릭 또는 트리사이클릭 탄화수소 부위를 의미하며, 본 명세서에서 상기 알킬렌기는 분자 내에 적어도 하나의 불포화 결합을 포함할 수도 있다. 한편, 상기 시클로알킬렌기로는, 이에 한정되는 것은 아니나, 2가의, 시클로펜탄 고리, 시클로헥산 고리 등을 그 예로 들 수 있다. 상기 시클로알킬렌기에 포함되어 있는 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In addition, in R 7 and R 8 , 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. In addition, as said cycloalkylene group, although it is not limited to this, 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.
또한, 상기 R7 및 R8에 있어서, 상기 아릴렌기는 6 내지 14개, 또는 6 내지 12개의 고리 원자를 가지는 2가 모노시클릭, 바이시클릭 또는 트리시클릭 방향족 탄화수소 부위를 의미하며, 이에 한정되는 것은 아니나, 2가의, 벤젠 고리, 나프탈렌 고리, 안트라센 고리, 비페닐 고리 등을 그 예로 들 수 있다. 상기 아릴렌기에 포함되어 있는 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In addition, in R 7 and R 8 , 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. Although not necessarily mentioned, 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.
한편, 상기 R7 및 R8는, 이에 한정되는 것은 아니나, 그 중에서도 치환 또는 비치환된 C1~10 알킬렌기인 것이 바람직하고, 치환 또는 비치환된 C1~8 알킬렌기인 것이 보다 바람직하며, 치환 또는 비치환된 C1~4 알킬렌기인 것이 더욱 바람직하다.On the other hand, 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.
[화학식 Ⅲ][Formula III]
Figure PCTKR2014009133-appb-I000063
Figure PCTKR2014009133-appb-I000063
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.The Formula Ⅲ] in, 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).
이때, 상기 R11에 있어서, 상기 알킬렌기는 1 내지 10개, 또는 1 내지 8개, 또는 1 내지 4개의 탄소 원자의 직쇄 또는 분지쇄의 2가 탄화수소 부위를 의미하며, 본 명세서에서 상기 알킬렌기는 분자 내에 적어도 하나의 불포화 결합을 포함할 수도 있다. 한편, 상기 알킬렌기로는, 이에 한정되는 것은 아니나, 메틸렌, 에틸렌, 트리메틸렌, 테트라메틸렌, 펜타메틸렌, 헥사메틸렌, 헵타메틸렌, 노나메틸렌, 데카메틸렌 등을 그 예로 들 수 있다. 상기 알킬렌기에 포함되어 있는 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In this case, in the R 11 , 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. On the other hand, 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.
또한, 상기 R11에 있어서, 상기 시클로알킬렌기는 4 내지 14개, 또는 4 내지 10개, 또는 4 내지 6개의 고리 탄소의 비방향족 2가 모노사이클릭, 바이사이클릭 또는 트리사이클릭 탄화수소 부위를 의미하며, 본 명세서에서 상기 알킬렌기는 분자 내에 적어도 하나의 불포화 결합을 포함할 수도 있다. 한편, 상기 시클로알킬렌기로는, 이에 한정되는 것은 아니나, 2가의, 시클로펜탄 고리, 시클로헥산 고리 등을 그 예로 들 수 있다. 상기 시클로알킬렌기에 포함되어 있는 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In addition, in R 11 , 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. In the present specification, the alkylene group may include at least one unsaturated bond in the molecule. In addition, as said cycloalkylene group, although it is not limited to this, 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.
또한, 상기 R11에 있어서, 상기 아릴렌기는 6 내지 14개, 또는 6 내지 12개의 고리 원자를 가지는 2가 모노시클릭, 바이시클릭 또는 트리시클릭 방향족 탄화수소 부위를 의미하며, 이에 한정되는 것은 아니나, 2가의, 벤젠 고리, 나프탈렌 고리, 안트라센 고리, 비페닐 고리 등을 그 예로 들 수 있다. 상기 아릴렌기에 포함되어 있는 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In addition, in R 11 , 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.
한편, 상기 R12는, 이에 한정되는 것은 아니나, 그 중에서도 치환 또는 비치환된 C1~10 알킬렌기인 것이 바람직하고, 치환 또는 비치환된 C1~8 알킬렌기인 것이 보다 바람직하며, 치환 또는 비치환된 C1~4 알킬렌기인 것이 더욱 바람직하다.On the other hand, 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.
보다 구체적으로, 이에 한정되는 것은 아니나, 상기 (D) 포스페이트계 화합물은 하기 [화학식 31] 내지 [화학식 34]로 이루어진 군으로부터 선택되는 1종 이상일 수 있다.More specifically, the (D) phosphate-based compound may be at least one selected from the group consisting of the following [Formula 31] to [Formula 34].
[화학식 31][Formula 31]
Figure PCTKR2014009133-appb-I000064
Figure PCTKR2014009133-appb-I000064
[화학식 32][Formula 32]
Figure PCTKR2014009133-appb-I000065
Figure PCTKR2014009133-appb-I000065
[화학식 33][Formula 33]
Figure PCTKR2014009133-appb-I000066
Figure PCTKR2014009133-appb-I000066
[화학식 34][Formula 34]
Figure PCTKR2014009133-appb-I000067
Figure PCTKR2014009133-appb-I000067
한편, 상기 (D) 포스페이트계 화합물은 라디칼 경화형 조성물 100 중량부에 있어서 5 내지 40 중량부로 포함되는 것이 바람직하며, 보다 바람직하게는 5 내지 35 중량부정도, 더욱 바람직하게는 5 내지 30 중량부정도일 수 있다. (D) 포스페이트계 화합물의 함량이 상기 범위보다 많이 포함되는 경우 밀착성이 충분하지 않을 수 있으며, 상기 범위보다 적게 포함되는 경우 내수성이 취약해질 수 있다.On the other hand, the (D) phosphate compound is preferably contained in 5 to 40 parts by weight, more preferably about 5 to 35 parts by weight, more preferably about 5 to 30 parts by weight in 100 parts by weight of the radical curable composition. Can be. If the content of the (D) phosphate compound is greater than the above range, the adhesion may not be sufficient, and if less than the above range, the water resistance may be weak.
마. 다관능성 (메트)아크릴계 화합물 (E)hemp. Multifunctional (meth) acrylic compound (E)
본 발명에 따른 라디칼 경화형 조성물은 보다 우수한 밀착성 및 내수성 효과를 얻기 위하여, (E) 다관능성 (메트)아크릴계 화합물을 더 포함하는 것일 수도 있다.The radical curable composition according to the present invention may further comprise (E) a polyfunctional (meth) acrylic compound in order to obtain more excellent adhesion and water resistance effects.
즉, 본 발명에 따른 라디칼 경화형 조성물은 (A) 분자 내에 적어도 1개의 친수성 관능기를 갖는 라디칼 중합성 화합물; (B) 분자 내에 3개의 (메트)아크릴기를 갖는 포스페이트계 화합물; (C) 라디칼 개시제; 및 (D) 분자 내에 1개 또는 2개의 (메트)아크릴기를 갖는 포스페이트계 화합물 및/또는 (E) 다관능성 (메트)아크릴계 화합물을 포함하는 것일 수 있다.That is, the radical curable composition which concerns on this invention is (A) radically polymerizable compound which has at least 1 hydrophilic functional group in a molecule | numerator; (B) phosphate compounds having three (meth) acryl groups in the molecule; (C) a radical initiator; And (D) a phosphate compound having one or two (meth) acryl groups in the molecule and / or (E) a polyfunctional (meth) acrylic compound.
이때, 상기 (E) 다관능성 (메트)아크릴계 화합물은 특별히 한정되지 않으며, 분자 내에 적어도 2개의 (메트)아크릴기를 갖는 것으로써 당해 기술분야에 널리 알려진 다양한 다관능성(메트)아크릴계 화합물을 특별한 제한 없이 사용할 수 있다. 다만, 본 명세서에서는 하기 예시로 나열한 다관능성 (메트)아크릴계 화합물을 제회하고는 상술한 (A) ~ (D) 화합물에 해당하는 화합물은 다관능성 (메트)아크릴계 화합물에서 제외한다.In this case, 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.
예를 들어, 본 발명에 있어서, 상기 (E) 다관능성 (메트)아크릴계 화합물로는, 에틸렌글리콜디(메트)아크릴레이트, 1,3-부탄디올디(메트)아크릴레이트, 1,4-부탄디올디(메트)아크릴레이트, 1,6-헥산디올디(메트)아크릴레이트, 1,9-노난디올디(메트)아크릴레이트, 네오펜틸글리콜디(메트)아크릴레이트, 트리메틸올프로판디(메트)아크릴레이트, 펜타에리트리톨디(메트)아크릴레이트, 디트리메틸올프로판디(메트)아크릴레이트, 디에틸렌글리콜디(메트)아크릴레이트, 트리에틸렌글리콜디(메트)아크릴레이트, 디프로필렌글리콜디(메트)아크릴레이트, 트리프로필렌글리콜디(메트)아크릴레이트, 폴리에틸렌글리콜디(메트)아크릴레이트, 폴리프로필렌글리콜디(메트)아크릴레이트, 폴리테트라메틸렌글리콜디(메트)아크릴레이트, 실리콘디(메트)아크릴레이트, 히드록시피발산에스테르네오펜틸글리콜디(메트)아크릴레이트, 2,2-비스[4-(메트)아크릴로일옥시에톡시에톡시페닐]프로판, 2,2-비스[4-(메트)아크릴로일옥시에톡시에톡시시클로헥실]프로판, 수소 첨가 디시클로펜타디에닐디(메트)아크릴레이트, 트리시클로데칸디메탄올디(메트)아크릴레이트, 1,3-디옥산-2,5-디일디(메트)아크릴레이트, 2-(2-히드록시-1,1-디메틸에틸)-5-에틸-5-히드록시메틸-1,3-디옥산의 디(메트)아크릴레이트, 트리스(히드록시에틸)이소시아누레이트디(메트)아크릴레이트, 글리세린트리(메트)아크릴레이트, 트리메틸올프로판트리(메트)아크릴레이트, 디트리메틸올프로판트리(메트)아크릴레이트, 디트리메틸올프로판테트라(메트)아크릴레이트, 펜타에리트리톨트리(메트)아크릴레이트, 펜타에리트리톨테트라(메트)아크릴레이트, 디펜타에리트리톨테트라(메트)아크릴레이트, 디펜타에리트리톨펜타(메트)아크릴레이트, 디펜타에리트리톨헥사(메트)아크릴레이트 등을 들 수 있다. 이들은 단독으로 또는 혼합하여 사용할 수 있다.For example, in the present invention, as 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 di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, silicone di (meth) acrylate , Hide Sifivalic acid ester neopentyl glycol di (meth) acrylate, 2,2-bis [4- (meth) acryloyloxyethoxyethoxyphenyl] propane, 2,2-bis [4- (meth) acryloyl Oxyethoxyethoxycyclohexyl] propane, hydrogenated dicyclopentadienyldi (meth) acrylate, tricyclodecanedimethanoldi (meth) acrylate, 1,3-dioxane-2,5-diyldi (meth ) Acrylate, di (meth) acrylate of 2- (2-hydroxy-1,1-dimethylethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane, tris (hydroxyethyl) Isocyanurate di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythr Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate. These can be used individually or in mixture.
한편, 이에 한정되는 것은 아니나, 상기 (E) 다관능성 (메트)아크릴계 화합물은 하기 [화학식 Ⅳ] 내지 [화학식 Ⅵ]로 표시되는 화합물들로 이루어진 군으로 선택된 1종 이상인 것이 보다 바람직하다. 이 경우 내수성 개선 효과가 더욱 우수하기 때문이다.On the other hand, 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.
[화학식 Ⅳ][Formula IV]
Figure PCTKR2014009133-appb-I000068
Figure PCTKR2014009133-appb-I000068
상기 [화학식 Ⅳ]에서, R13 및 R14는 각각 독립적으로 (메트)아크릴로일옥시기 또는 (메트)아크릴로일옥시알킬기이다.In [Formula IV], R 13 and R 14 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group.
이때, 상기 R13 및 R14에 있어서, 상기 (메트)아크릴로일옥시알킬기의 알킬은 1 내지 10개, 또는 1 내지 8개, 또는 1 내지 4개의 탄소 원자의 직쇄 또는 분지쇄의 탄화수소 부위를 의미하며, (메트)아크릴로일옥시기는 알킬기의 임의의 위치에 치환될 수 있다. 상기 알킬에 포함되어 있는 나머지 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In this case, in R 13 and R 14 , 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.
[화학식 Ⅴ][Formula Ⅴ]
Figure PCTKR2014009133-appb-I000069
Figure PCTKR2014009133-appb-I000069
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 알킬기이다.In Formula [V], R 15 , R 16 and R 17 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group, and R 18 is a (meth) acryloyloxy group, (meth ) Acryloyloxyalkyl group, a hydroxy group, or a substituted or unsubstituted C 1-10 alkyl group.
이때, 상기 R15, R16, R17 및 R18에 있어서, 상기 (메트)아크릴로일옥시알킬기의 알킬은 1 내지 10개, 또는 1 내지 8개, 또는 1 내지 4개의 탄소 원자의 직쇄 또는 분지쇄의 탄화수소 부위를 의미하며, (메트)아크릴로일옥시기는 알킬기의 임의의 위치에 치환될 수 있다. 상기 알킬에 포함되어 있는 나머지 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In this case, in the R 15 , R 16, R 17 and R 18 , 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.
또한, 상기 R18에 있어서, 상기 알킬기는 1 내지 10개, 또는 1 내지 8개, 또는 1 내지 4개의 탄소 원자의 직쇄 또는 분지쇄의 탄화수소 부위를 의미하며, 상기 알킬기에 포함되어 있는 1 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In addition, in the R 18 , 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.
[화학식 Ⅵ][Formula VI]
Figure PCTKR2014009133-appb-I000070
Figure PCTKR2014009133-appb-I000070
상기 [화학식 Ⅵ]에서, R19는 치환 또는 비치환된 C1~10 알킬렌이고, R20 및 R21은 각각 독립적으로 (메트)아크릴로일옥시기 또는 (메트)아크릴로일옥시알킬기이다.In [Formula VI], 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.
이때, 상기 R19에 있어서, 상기 알킬렌은 1 내지 10개, 또는 1 내지 8개, 또는 1 내지 6개의 탄소 원자의 직쇄 또는 분지쇄의 2가 탄화수소 부위를 의미하며, 본 명세서에서 상기 알킬렌기는 분자 내에 적어도 하나의 불포화 결합을 포함할 수도 있다. 한편, 상기 알킬렌기로는, 이에 한정되는 것은 아니나, 메틸렌, 에틸렌, 트리메틸렌, 테트라메틸렌, 펜타메틸렌, 헥사메틸렌, 헵타메틸렌, 노나메틸렌, 데카메틸렌 등을 그 예로 들 수 있다. 상기 알킬렌에 포함되어 있는 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In this case, in R 19 , 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. On the other hand, 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.
또한, 상기 R20 및 R21에 있어서, 상기 (메트)아크릴로일옥시알킬기의 알킬은 1 내지 10개, 또는 1 내지 8개, 또는 1 내지 4개의 탄소 원자의 직쇄 또는 분지쇄의 탄화수소 부위를 의미하며, (메트)아크릴로일옥시기는 알킬기의 임의의 위치에 치환될 수 있다. 상기 알킬에 포함되어 있는 나머지 하나 이상의 수소 원자는 임의의 치환기로 치환될 수 있다.In the above R 20 and R 21 , 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.
보다 구체적으로, 이에 한정되는 것은 아니나, 상기 (E) 다관능성 (메트)아크릴계 화합물은 하기 [화학식 35] 내지 [화학식 38]로 표시되는 화합물들로 이루어진 군으로 선택된 1종 이상인 것이 특히 바람직하다.More specifically, although not limited thereto, 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].
[화학식 35][Formula 35]
Figure PCTKR2014009133-appb-I000071
Figure PCTKR2014009133-appb-I000071
[화학식 36][Formula 36]
Figure PCTKR2014009133-appb-I000072
Figure PCTKR2014009133-appb-I000072
[화학식 37][Formula 37]
Figure PCTKR2014009133-appb-I000073
Figure PCTKR2014009133-appb-I000073
[화학식 38][Formula 38]
Figure PCTKR2014009133-appb-I000074
Figure PCTKR2014009133-appb-I000074
한편, 본 발명의 상기 (E) 다관능 (메트)아크릴계 화합물의 함량은 전체 조성물 100 중량부에 대하여, 5 내지 40 중량부정도, 바람직하게는 5 내지 35 중량부정도, 더욱 바람직하게는 5 내지 30 중량부정도일 수 있다. (E) 다관능 (메트)아크릴계 화합물의 함량이 상기 범위보다 많이 포함되는 경우 밀착성이 충분하지 않을 수 있으며, 상기 범위보다 적게 포함되는 경우 내수성이 취약해질 수 있다.On the other hand, 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 5 parts by weight based on 100 parts by weight of the total composition. It may be about 30 parts by weight. When the content of the (E) polyfunctional (meth) acrylic compound is included in more than the above range, the adhesion may not be sufficient, and when less than the above range, the water resistance may be weak.
바. 조성물의 물성bar. Physical properties of the composition
한편, 상기와 같은 본 발명의 라디칼 경화형 조성물은 경화 후 유리전이온도가 50℃ 이상, 예를 들면, 70 내지 140℃ 또는 70 내지 130℃ 정도일 수 있다. 상기와 같은 수치 범위의 유리전이온도를 갖는 경우 보호층이 우수한 내열성 및 내수성을 가질 수 있다.Meanwhile, the radical curable composition of the present invention as described above may have a glass transition temperature of 50 ° C. or more after curing, for example, 70 to 140 ° C. or 70 to 130 ° C. When the glass transition temperature in the numerical range as described above may have a good heat resistance and water resistance.
또한, 상기 라디칼 경화형 조성물은 점도가 70cP 이하, 예를 들면, 10 내지 70cP 또는 10 내지 65cP 정도일 수 있다. 조성물의 점도가 상기 수치범위를 만족하는 경우 보호층의 두께를 얇게 형성할 수 있고, 저점도를 갖기 때문에 작업성이 우수한 장점이 있다.In addition, the radical curable composition may have a viscosity of 70 cP or less, for example, 10 to 70 cP or 10 to 65 cP. When the viscosity of the composition satisfies the numerical range, the thickness of the protective layer may be thinly formed, and since the composition has a low viscosity, there is an excellent workability.
한편, 상기 라디칼 경화형 조성물을 이용하여 형성된 보호층의 두께는 0.5 내지 20 ㎛인 것이 바람직하며, 예를 들면, 0.5 내지 15 ㎛ 또는 0.5 내지 10 ㎛ 일 수 있다. 보호층의 두께가 상기 범위를 만족하는 경우 제조되는 편광판의 박형 경량화가 가능하기 때문이다. 0.5 ㎛ 미만인 경우 편광자의 열충격 안정성 및 컬 특성이 취약하고, 20㎛ 이상인 경우에는 편광판의 박형화가 어렵다.On the other hand, the thickness of the protective layer formed using the radical curable composition is preferably 0.5 to 20 ㎛, for example, may be 0.5 to 15 ㎛ or 0.5 to 10 ㎛. This is because when the thickness of the protective layer satisfies the above range, the thickness of the polarizing plate produced can be reduced. If it is less than 0.5 μm, the thermal shock stability and curl characteristics of the polarizer are weak, and if it is 20 μm or more, the thickness of the polarizing plate is difficult.
1-3. 보호 필름1-3. Protective film
한편, 본 발명의 상기 편광판은 필요에 따라서 편광자의 일면에 보호 필름을 더 구비할 수 있다. 보다 구체적으로, 본 발명의 상기 편광판은 상기 보호층이 편광자의 일면에 형성된 경우, 보호층이 형성된 면의 반대면에 편광자를 지지 및 보호하기 위하여 접착제층을 매개로 별도의 보호 필름을 부착할 수 있다.On the other hand, the polarizing plate of the present invention may further include a protective film on one surface of the polarizer as needed. More specifically, in the polarizing plate of the present invention, when the protective layer is formed on one surface of the polarizer, a separate protective film may be attached through the adhesive layer to support and protect the polarizer on the opposite side of the surface on which the protective layer is formed. have.
이때, 상기 보호 필름은 편광자를 지지 및 보호하기 위한 것으로, 당해 기술 분야에 일반적으로 알려져 있는 다양한 재질의 보호 필름들, 예를 들면, 셀룰로오스계 필름, 폴리에틸렌테레프탈레이트(PET, polyethylene terephthalate) 필름, 싸이클로올레핀 폴리머(COP, cycloolefin polymer) 필름, 아크릴계 필름 등이 제한없이 사용될 수 있다. 이 중에서도 광학 특성, 내구성, 경제성 등을 고려할 때, 아크릴계 필름을 사용하는 것이 특히 바람직하다. In this case, the protective film is for supporting and protecting the polarizer, protective films of various materials generally known in the art, for example, cellulose-based film, polyethylene terephthalate (PET) film, cyclo An olefin polymer (COP, cycloolefin polymer) film, acrylic film, or 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.
한편, 본 발명에서 사용 가능한 아크릴계 필름은 (메트)아크릴레이트계 수지를 주성분으로 포함하는 성형 재료를 압출 성형에 의해 성형하여 획득할 수 있다. 이때, 상기 (메트)아크릴레이트계 수지는 (메트)아크릴레이트계 단위를 포함하는 수지를 주 성분으로 하는 것으로, (메트)아크릴레이트계 단위로 이루어진 호모 폴리머 수지뿐 아니라 (메트)아크릴레이트계 단위 이외에 다른 단량체 단위가 공중합된 공중합체 수지 및 상기와 같은 (메트)아크릴레이트계 수지에 다른 수지가 블랜드된 블랜드 수지도 포함하는 개념이다.On the other hand, 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. In this case, 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 In addition to the copolymer resin copolymerized with other monomer units and the (meth) acrylate-based resin as described above, the concept also includes a blend resin blended with other resin.
한편, 상기 (메트)아크릴레이트계 단위는, 예를 들면, 알킬(메트)아크릴레이트계 단위일 수 있다. 여기서, 상기 알킬(메트)아크릴레이트계 단위는 알킬아크릴레이트계 단위 및 알킬메타크릴레이트계 단위를 모두 의미하는 것으로, 상기 알킬(메트)아크릴레이트계 단위의 알킬기는 탄소수 1 ~ 10인 것이 바람직하며, 탄소수 1 ~ 4인 것이 더욱 바람직하다. Meanwhile, the (meth) acrylate-based unit may be, for example, an alkyl (meth) acrylate-based unit. Here, 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.
또한, 상기 (메트)아크릴레이트계 단위와 공중합이 가능한 단량체 단위로는, 스티렌계 단위, 말레산 무수물계 단위, 말레이미드계 단위 등을 들 수 있다. 이때, 상기 스티렌계 단위로는, 이에 한정되는 것은 아니나, 스티렌, α-메틸스티렌 등을 그 예로 들 수 있고; 상기 말레산 무수물계 단량체로는, 이에 한정되는 것은 아니나, 말레산 무수물, 메틸 말레산 무수물, 시클로헥실 말레산 무수물, 페닐 말레산 무수물 등을 그 예로 들 수 있으며; 상기 말레이미드계 단량체로는, 이에 한정되는 것은 아니나, 말레이미드, N-메틸 말레이미드, N-시클로헥실 말레이미드, N-페닐 말레이미드 등을 그 예로 들 수 있다. 이들은 단독으로 또는 혼합하여 사용될 수 있다.Moreover, 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. In this case, the styrene-based unit is not limited thereto, and examples thereof include styrene, α-methylstyrene, and the like; Examples of the maleic anhydride monomer include, but are not limited to, maleic anhydride, methyl maleic anhydride, cyclohexyl maleic anhydride, phenyl maleic anhydride, and the like; Examples of 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.
한편, 상기 아크릴계 필름은 락톤 고리 구조를 갖는 (메트)아크릴레이트계 수지를 포함하는 필름일 수 있다. 락톤 고리 구조를 갖는 (메트)아크릴레이트계 수지의 구체적인 예로서는 예를 들어 일본 공개특허공보 제2000-230016호, 일본공개특허공보 제 2001-151814호, 일본 공개특허공보 제 2002-120326호 등에 기재된 락톤 고리 구조를 갖는 (메트)아크릴레이트계 수지를 들 수 있다. On the other hand, the acrylic film may be a film containing a (meth) acrylate resin having a lactone ring structure. As a specific example of (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.
상기 아크릴계 필름의 제조 방법은 특별히 한정되지 않으며, 예를 들어 (메트)아크릴레이트계 수지와 그 밖의 중합체, 첨가제 등을 임의의 적절한 혼합 방법에 의해 충분히 혼합하여 열가소성 수지 조성물을 제조한 후 이를 필름 성형하여 제조하거나, 또는 (메트) 아크릴레이트계 수지와, 그 밖의 중합체, 첨가제 등을 별도의 용액으로 제조한 후 혼합하여 균일한 혼합액을 형성한 후 이를 필름 성형할 수도 있다. 또한, 상기 아크릴계 필름은 미연신 필름 또는 연신 필름 중 어느 것일 수 있다. 연신 필름인 경우에는 1축 연신 필름 또는 2축 연신 필름 일 수 있고, 2축 연신 필름인 경우에는 동시 2축 연신 필름 또는 축차 2축 연신 필름 중 어느 것일 수 있다.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. In addition, 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.
한편, 본 발명의 상기 편광판은, 접착력을 더욱 향상시키기 위하여, 상기 접착제층과 상기 보호 필름 사이에 프라이머층을 더 포함할 수도 있다. 이때, 상기 프라이머층은 수분산성 고분자 수지, 수분산성 미립자 및 물을 포함하는 코팅액을 바 코팅법, 그라비어 코팅법 등을 이용하여 보호 필름 상에 도포하고 건조하는 방법에 의해 형성될 수 있다. 상기 수분산성 고분자 수지는 예를 들면, 수분산 폴리우레탄계 수지, 수분산 아크릴계 수지, 수분산 폴리에스테르계 수지 또는 이들의 조합 등일 수 있으며, 수분산성 미립자는 실리카, 티타니아, 알루미나, 지르코니아 등의 무기계 미립자나, 실리콘계 수지, 불소계 수지, (메트)아크릴계 수지, 가교 폴리비닐알코올 및 멜라민계 수지로 이루어진 유기계 미립자 또는 이들의 조합을 이용할 수 있으나, 이에 한정되는 것은 아니다.On the other hand, 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. In this case, 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. B, 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.
한편, 상기 편광자와 보호 필름의 부착은 롤 코터, 그라비어 코터, 바 코터, 나이프 코터 또는 캐필러리 코터 등을 사용하여 편광자 또는 보호 필름의 표면에 접착제를 도포한 후, 이들을 합지 롤로 가열 합지하거나, 상온 압착하여 합지하는 방법 또는 합지 후 UV 조사하는 방법 등에 의해 수행될 수 있다. 한편, 상기 접착제로는 당해 기술 분야에서 사용되는 다양한 편광판용 접착제들, 예를 들면, 폴리비닐알코올계 접착제, 폴리우레탄계 접착제, 아크릴계 접착제, 양이온계 또는 라디칼계 접착제 등이 제한 없이 사용될 수 있다.On the other hand, 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. On the other hand, as the adhesive, various polarizing plate adhesives used in the art, for example, polyvinyl alcohol-based adhesives, polyurethane-based adhesives, acrylic adhesives, cationic or radical-based adhesives and the like can be used without limitation.
1-4. 점착층1-4. Adhesive layer
한편, 본 발명의 편광판은, 표시장치 패널 또는 위상차 필름과 같은 광학 필름과의 부착을 위해, 필요에 따라, 상기 보호층의 상부에 점착층을 포함할 수 있다. Meanwhile, the polarizing plate of the present invention may include an adhesive layer on an upper portion of the protective layer, if necessary, for attachment to an optical film such as a display panel or a retardation film.
이때, 상기 점착층은 당해 기술 분야에 잘 알려져 있는 다양한 점착제들을 사용하여 형성될 수 있으며, 그 종류가 특별히 제한되는 것은 아니다. 예를 들면, 상기 점착층은 고무계 점착제, 아크릴계 점착제, 실리콘계 점착제, 우레탄계 점착제, 폴리비닐알코올계 점착제, 폴리비닐피롤리돈계 점착제, 폴리아크릴아미드계 점착제, 셀룰로오스계 점착제, 비닐알킬에테르계 점착제 등을 이용하여 형성될 수 있다. 이 중에서도 투명성 및 내열성 등을 고려할 때, 아크릴계 점착제를 사용하는 것이 특히 바람직하다. In this case, the pressure-sensitive adhesive layer may be formed using various pressure-sensitive adhesives well known in the art, and the kind thereof is not particularly limited. For example, the pressure-sensitive adhesive layer may be a rubber pressure sensitive adhesive, an acrylic pressure sensitive adhesive, a silicone pressure sensitive adhesive, a urethane pressure sensitive adhesive, a polyvinyl alcohol pressure sensitive adhesive, a polyvinylpyrrolidone pressure sensitive adhesive, a polyacrylamide pressure sensitive adhesive, a cellulose pressure sensitive adhesive, a vinyl alkyl ether pressure sensitive adhesive, or the like. It can be formed using. Among these, in consideration of transparency, heat resistance and the like, it is particularly preferable to use an acrylic pressure-sensitive adhesive.
한편, 상기 점착층은 보호층 상부에 점착제를 도포하는 방법으로 형성될 수도 있고, 이형 시트 상에 점착제를 도포한 후 건조시켜 제조되는 점착 시트를 보호층 상부에 부착하는 방법으로 형성될 수도 있다. On the other hand, the pressure-sensitive adhesive layer may be formed by applying a pressure-sensitive adhesive on the protective layer, or may be formed by a method of attaching the pressure-sensitive adhesive sheet prepared by applying the pressure-sensitive adhesive on the release sheet and dried on the protective layer.
2. 화상표시장치2. Image display device
상기와 같은 본 발명의 편광판은 액정표시장치 등과 같은 화상표시장치에 유용하게 적용될 수 있다. 상기 화상표시장치는 예를 들면, 액정 패널 및 이 액정 패널의 양면에 각각 구비된 편광판들을 포함하는 액정 표시장치일 수 있으며, 이때, 상기 편광판 중 적어도 하나가 본 발명에 따른 편광판일 수 있다. 이때, 상기 액정표시장치에 포함되는 액정 패널의 종류는 특별히 한정되지 않는다. 예를 들면, 그 종류에 제한되지 않고, TN(twisted nematic)형, STN(super twisted nematic)형, F(ferroelectic)형 또는 PD(polymer dispersed)형과 같은 수동 행렬 방식의 패널; 2단자형(two terminal) 또는 3단자형(three terminal)과 같은 능동행렬 방식의 패널; 횡전계형(IPS; In Plane Switching) 패널 및 수직배향형(VA; Vertical Alignment) 패널 등의 공지의 패널이 모두 적용될 수 있다. 또한, 액정표시장치를 구성하는 기타 구성, 예를 들면, 상부 및 하부 기판(ex. 컬러 필터 기판 또는 어레이 기판) 등의 종류 역시 특별히 제한되지 않고, 이 분야에 공지되어 있는 구성이 제한 없이 채용될 수 있다.The polarizing plate of the present invention as described above can be usefully applied to an image display device such as a liquid crystal display device. The image display apparatus may be, for example, a liquid crystal display including a liquid crystal panel and polarizing plates provided on both surfaces of the liquid crystal panel, wherein at least one of the polarizing plates may be a polarizing plate according to the present invention. In this case, the type of liquid crystal panel included in the liquid crystal display device is not particularly limited. For example, a panel of a passive matrix type such as, but not limited to, a twisted nematic (TN) type, a super twisted nematic (STN) type, a ferrolectic (F) type, or a 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. In addition, other configurations constituting the liquid crystal display device, for example, types of upper and lower substrates (eg, color filter substrates or array substrates) are not particularly limited, and configurations known in the art may be employed without limitation. Can be.
이하에서는 구체적인 실시예를 통해 본 발명을 보다 자세히 설명하기로 한다.Hereinafter, the present invention will be described in more detail with reference to specific examples.
제조예 1 - 아크릴계 보호 필름의 제조Preparation Example 1-Preparation of Acrylic Protective Film
폴리(N-시클로헥실말레이미드-co-메틸메타크릴레이트), 스티렌-무수말레산 공중합체 수지 및 페녹시계 수지를 100:2.5:5의 중량비로 균일하게 혼합한 수지 조성물을 원료 호퍼(hopper)로부터 압출기까지를 질소 치환한 24φ의 압출기에 공급하여 250℃에서 용융하여 원료 펠렛(pellet)을 제조하였다.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 24φ extruder and melted at 250 ° C. to prepare a raw material pellet.
페녹시계 수지는 InChemRez사의 PKFE(Mw=60,000, Mn=16,000, Tg=95℃)을 사용하였고, 스티렌-무수말레산 공중합체 수지는 스티렌 85 중량%, 무수말레익안하이드라이드 15 중량%인 Dylaeck 332를 사용하였으며, 폴리(N-시클로헥실말레이미드-co-메틸메타크릴레이트) 수지는 NMR 분석 결과 N-시클로헥실말레이미드의 함량이 6.5 중량%인 것을 사용하였다.The phenoxy resin was PKFE (Mw = 60,000, Mn = 16,000, Tg = 95 ° C.) manufactured by InChemRez, and the styrene-maleic anhydride copolymer resin was Dylaeck 332 having 85% by weight of styrene and 15% by weight of maleic anhydride. 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.
얻어진 원료 펠렛을 진공 건조하고 260℃에서 압출기로 용융, 코트 행거 타입의 티-다이(T-die)에 통과시키고, 크롬 도금 캐스팅 롤 및 건조 롤 등을 거쳐 두께 150 ㎛의 필름을 제조하였다. 이 필름을 파일로트 연신 장비를 사용하여 125℃에서 MD 방향으로 롤의 속도 차를 이용하여 170% 비율로 연신하여 아크릴 필름을 제조하였다. 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.
상기와 같은 과정을 통해 제조된 아크릴 필름을 코로나 처리한 후, 상기 아크릴 필름의 일면에 CK-PUD-F(조광 우레탄 분산액)을 순수로 희석하여 제조된 고형분 함량 10중량%의 프라이머 조성물에 옥사졸린 가교제 (일본촉매사, WS700) 20중량부를 첨가한 프라이머 조성물을 #7 바(bar)로 코팅한 후 TD 방향으로 130℃에서 텐더를 이용하여 190% 연신하여 최종적으로 프라이머층 두께가 400nm인 아크릴계 보호 필름을 제조하였다. After the corona treatment of the acrylic film prepared through the process described above, oxazoline in a primer composition of 10% by weight of solid content prepared by diluting CK-PUD-F (dilute urethane dispersion) with pure water on one surface of the acrylic film. After coating 20 parts by weight of a crosslinking agent (Japan Catalyst Co., Ltd., WS700) with a primer composition # 7 bar, stretched 190% using a tender at 130 ° C. in the TD direction, and finally, an acrylic protective material having a primer thickness of 400 nm. A film was prepared.
제조예 2 - 라디칼 경화형 조성물의 제조Preparation Example 2-Preparation of Radical Curable Composition
(1) 라디칼 경화형 조성물 A(1) Radical Curable Composition A
HEA(hydroxyethyl acrylate) 66.7 중량%, BPA type epoxy di-acrylate(EB600, Cytec 제품) 16.6 중량%, tri(acryloyloxy ethyl) phosphate 16.7중량%를 넣어 제조한 수지 조성물 100 중량부에 라디칼 개시제인 irgacure-819(Ciba 사) 3 중량부를 첨가하여 편광판용 라디칼 경화형 조성물 A를 제조하였다.Irgacure-819, a radical initiator, was added to 100 parts by weight of a resin composition prepared by adding 66.7% by weight of HEA (hydroxyethyl acrylate), 16.6% by weight of BPA type epoxy di-acrylate (EB600 manufactured by Cytec), and 16.7% by weight of tri (acryloyloxy ethyl) phosphate. (Ciba) 3 parts by weight was added to prepare a radical curable composition A for polarizing plates.
(2) 라디칼 경화형 조성물 B(2) Radical Curable Composition B
HEA(hydroxyethyl acrylate) 50 중량%, BPA type epoxy di-acrylate(EB600, Cytec 제품) 21.4 중량%, tri(acryloyloxy ethyl) phosphate 14.3중량%, di-(methacryloyloxy ethyl)phosphate 14.3중량%를 넣어 제조한 수지 조성물 100 중량부에 라디칼 개시제인 irgacure-819(Ciba 사) 3 중량부를 첨가하여 편광판용 라디칼 경화형 조성물 B를 제조하였다.50 wt% HEA (hydroxyethyl acrylate), 21.4 wt% BPA type epoxy di-acrylate (EB600, Cytec), 14.3 wt% tri (acryloyloxy ethyl) phosphate, 14.3 wt% di- (methacryloyloxy ethyl) phosphate Radical curable composition B for polarizing plates was prepared by adding 3 parts by weight of irgacure-819 (Ciba) which is a radical initiator to 100 parts by weight of the composition.
(3) 라디칼 경화형 조성물 C(3) Radical Curable Composition C
HEA(hydroxyethyl acrylate) 50 중량%, BPA type epoxy di-acrylate(EB600, Cytec 제품) 21.4 중량%, tri(acryloyloxy ethyl) phosphate 21.4 중량%, di-(methacryloyloxy ethyl)phosphate 7.2 중량%를 넣어 제조한 수지 조성물 100 중량부에 라디칼 개시제인 irgacure-819(Ciba 사) 3 중량부를 첨가하여 편광판용 라디칼 경화형 조성물 C를 제조하였다.Resin prepared by adding 50% by weight of HEA (hydroxyethyl acrylate), 21.4% by weight of BPA type epoxy di-acrylate (EB600, Cytec), 21.4% by weight of tri (acryloyloxy ethyl) phosphate, and 7.2% by weight of di- (methacryloyloxy ethyl) phosphate Radical curable composition C for polarizing plates was prepared by adding 3 parts by weight of irgacure-819 (Ciba), which is a radical initiator, to 100 parts by weight of the composition.
(4) 라디칼 경화형 조성물 D(4) Radical Curable Composition D
HEA(hydroxyethyl acrylate) 50 중량%, BPA type epoxy di-acrylate(EB600, Cytec 제품) 21.4 중량%, tri(acryloyloxy ethyl) phosphate 14.3 중량%, DCPDA(Dimethylol tricyclodecane diacrylate) 14.3중량%를 넣어 제조한 수지 조성물 100 중량부에 라디칼 개시제인 irgacure-819(Ciba 사) 3 중량부를 첨가하여 편광판용 라디칼 경화형 조성물 D를 제조하였다.A resin composition prepared by adding 50% by weight of HEA (hydroxyethyl acrylate), 21.4% by weight of BPA type epoxy di-acrylate (EB600, Cytec), 14.3% by weight of tri (acryloyloxy ethyl) phosphate, and 14.3% by weight of dimethylol tricyclodecane diacrylate (DCPDA). Radical curable composition D for polarizing plates was prepared by adding 3 parts by weight of irgacure-819 (Ciba), a radical initiator, to 100 parts by weight.
(5) 라디칼 경화형 조성물 E(5) Radical Curable Composition E
HEA(hydroxyethyl acrylate) 16.7 중량%, GLM(glyceryl methacrylate) 50 중량%, BPA type epoxy di-acrylate(EB600, Cytec 제품) 16.6 중량%, tri(acryloyloxy ethyl) phosphate 16.7 중량%를 넣어 제조한 수지 조성물 100 중량부에 라디칼 개시제인 irgacure-819(Ciba 사) 3 중량부를 첨가하여 편광판용 라디칼 경화형 조성물 E를 제조하였다.Resin composition 100 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 manufactured by Cytec), and 16.7% by weight of tri (acryloyloxy ethyl) phosphate Radical curable composition E for polarizing plates was prepared by adding 3 parts by weight of irgacure-819 (Ciba), which is a radical initiator, to parts by weight.
(6) 라디칼 경화형 조성물 F(6) Radical Curable Composition F
HEA(hydroxyethyl acrylate) 50 중량%, 1,4-cyclohexanedimethanol mono-acrylate 16.7 중량%, BPA type epoxy di-acrylate(EB600, Cytec 제품) 16.6 중량%, tri(acryloyloxy ethyl) phosphate 16.7 중량%를 넣어 제조한 수지 조성물 100 중량부에 라디칼 개시제인 irgacure-819(Ciba 사) 3 중량부를 첨가하여 편광판용 라디칼 경화형 조성물 F를 제조하였다.Prepared by adding 50% by weight of HEA (hydroxyethyl acrylate), 16.7% by weight of 1,4-cyclohexanedimethanol mono-acrylate, 16.6% by weight of BPA type epoxy di-acrylate (EB600, Cytec), and 16.7% by weight of tri (acryloyloxy ethyl) phosphate Radical curable composition F for polarizing plates was prepared by adding 3 parts by weight of irgacure-819 (Ciba), which is a radical initiator, to 100 parts by weight of the resin composition.
(7) 라디칼 경화형 조성물 G(7) Radical Curable Composition G
HEA(hydroxyethyl acrylate) 50 중량%, BPA type epoxy di-acrylate(EB600, Cytec 제품) 21.4 중량%, 2-(acrylamido)ethyl bis(2-(acryloyloxy)ethyl) phosphate 14.3 중량%, DCPDA(Dimethylol tricyclodecane diacrylate) 14.3중량%를 넣어 제조한 수지 조성물 100 중량부에 라디칼 개시제인 irgacure-819(Ciba 사) 3 중량부를 첨가하여 편광판용 라디칼 경화형 조성물 G를 제조하였다.HEA (hydroxyethyl acrylate) 50% by weight, BPA type epoxy di-acrylate (EB600, Cytec) 21.4% by weight, 2- (acrylamido) ethyl bis (2- (acryloyloxy) ethyl) phosphate 14.3% by weight, DCPDA (Dimethylol tricyclodecane diacrylate ) 3 parts by weight of irgacure-819 (Ciba), which is a radical initiator, was added to 100 parts by weight of the resin composition prepared by adding 14.3% by weight to prepare a radical curable composition G for a polarizing plate.
(8) 라디칼 경화형 조성물 H(8) Radical Curable Composition H
HEA(hydroxyethyl acrylate) 30 중량%, BPA type epoxy di-acrylate(EB600, Cytec 제품) 70 중량%를 넣어 제조한 수지 조성물 100 중량부에 라디칼 개시제인 irgacure-819(Ciba 사) 3 중량부를 첨가하여 편광판용 라디칼 경화형 조성물 H를 제조하였다.30 parts by weight of HEA (hydroxyethyl acrylate), 70 parts by weight of BPA type epoxy di-acrylate (EB600, manufactured by Cytec) was added to 100 parts by weight of a polar initiator by adding 3 parts by weight of irgacure-819 (Ciba), a radical initiator. Radical curable composition H was prepared.
(9) 라디칼 경화형 조성물 I(9) Radical Curable Composition I
HEA(hydroxyethyl acrylate) 66.7 중량%, BPA type epoxy di-acrylate(EB600, Cytec 제품) 16.6 중량%, di-(methacryloyloxy ethyl)phosphate 16.7 중량%를 넣어 제조한 수지 조성물 100 중량부에 라디칼 개시제인 irgacure-819(Ciba 사) 3 중량부를 첨가하여 편광판용 라디칼 경화형 조성물 I를 제조하였다.Irgacure-, a radical initiator, was added to 100 parts by weight of 6.7% by weight of HEA (hydroxyethyl acrylate), 16.6% by weight of BPA type epoxy di-acrylate (EB600 manufactured by Cytec), and 16.7% by weight of di- (methacryloyloxy ethyl) phosphate. 3 parts by weight of 819 (Ciba) was added to prepare a radical curable composition I for polarizing plates.
(10) 라디칼 경화형 조성물 J(10) Radical Curable Composition J
HEA(hydroxyethyl acrylate) 66.7 중량%, BPA type epoxy di-acrylate(EB600, Cytec 제품) 16.6 중량%, Mono-(methacryloyloxy ethyl)phosphate 16.7 중량%를 넣어 제조한 수지 조성물 100 중량부에 라디칼 개시제인 irgacure-819(Ciba 사) 3 중량부를 첨가하여 편광판용 라디칼 경화형 조성물 J를 제조하였다.Irgacure-, a radical initiator, was added to 100 weight parts of the resin composition prepared by adding 66.7 weight% of HEA (hydroxyethyl acrylate), 16.6 weight% of BPA type epoxy di-acrylate (EB600 manufactured by Cytec), and 16.7 weight% of mono- (methacryloyloxy ethyl) phosphate. 3 parts by weight of 819 (Ciba) was added to prepare a radical curable composition J for a polarizing plate.
실시예 1Example 1
제조예 1에 의해 제조된 아크릴 필름계 보호 필름의 프라이머 층에 스포이드로 라디칼 경화형 조성물 A를 도포하고, 편광자(PVA 소자)의 일면에 적층 한 다음, 최종 접착층의 두께가 1~2㎛이 되도록 조건을 설정한 후, 라미네이터(5m/min)를 통과시켰다. 그런 다음, 상기 아크릴 필름이 적층된 면에 UV 조사장치(Metal halide lamp)를 이용하여, 1000mJ/cm2의 자외선을 조사하여, 편광자의 일면에 보호 필름을 구비하는 편광판을 제조 하였다.Radical curable 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 one surface of a polarizer (PVA device), and then the conditions were such that the thickness of the final adhesive layer was 1 to 2 μm. After setting, passed the laminator (5m / min). Then, the surface of the acrylic film is laminated using a UV irradiation device (metal halide lamp), by irradiating ultraviolet light of 1000mJ / cm 2 , to prepare a polarizing plate having a protective film on one surface of the polarizer.
다음으로, 상기 제조한 편광판의 편광자의 보호 필름이 적층된 면의 타면에 라디칼 경화형 조성물 A를 도포하고, 이형력이 있는 PET 필름을 적층한 다음, 최종 보호층 두께가 4~5㎛이 되도록 조건을 설정한 후, 라미네이터(5m/min)를 통과시켰다. 그런 다음, 이형 PET가 적층된 면에 자외선 조사장치(Metal halide lamp)를 이용하여, 1000mJ/cm2의 자외선을 조사하고, PET 필름을 제거하여, 편광자의 일면에는 보호 필름을 구비하고, 타면에는 보호층을 구비하는 편광판을 제조하였다.Next, the radical curable composition A is applied to the other surface of the surface on which the protective film of the polarizer of the prepared polarizer is laminated, the PET film having a releasing force is laminated, and the final protective layer thickness is 4 to 5 μm. After setting, passed the laminator (5m / min). Then, the surface on which the release PET is laminated is irradiated with ultraviolet light of 1000 mJ / cm 2 using a ultraviolet halide lamp, and the PET film is removed, and a protective film is provided on one side of the polarizer, and on the other side. The polarizing plate provided with a protective layer was manufactured.
실시예 2Example 2
라디칼 경화형 조성물로 B를 사용한 점을 제외하고는, 실시예 1과 동일한 방법으로 편광판을 제조하였다.A polarizing plate was manufactured in the same manner as in Example 1, except that B was used as the radical curable composition.
실시예 3Example 3
라디칼 경화형 조성물로 C를 사용한 점을 제외하고는, 실시예 1과 동일한 방법으로 편광판을 제조하였다.A polarizing plate was manufactured in the same manner as in Example 1 except that C was used as the radical curable composition.
실시예 4Example 4
라디칼 경화형 조성물로 D를 사용한 점을 제외하고는, 실시예 1과 동일한 방법으로 편광판을 제조하였다.A polarizing plate was manufactured in the same manner as in Example 1 except that D was used as the radical curable composition.
실시예 5Example 5
라디칼 경화형 조성물로 E를 사용한 점을 제외하고는, 실시예 1과 동일한 방법으로 편광판을 제조하였다.A polarizing plate was manufactured in the same manner as in Example 1 except that E was used as the radical curable composition.
실시예 6Example 6
라디칼 경화형 조성물로 F를 사용한 점을 제외하고는, 실시예 1과 동일한 방법으로 편광판을 제조하였다.A polarizing plate was manufactured in the same manner as in Example 1, except that F was used as the radical curable composition.
실시예 7Example 7
라디칼 경화형 조성물로 G를 사용한 점을 제외하고는, 실시예 1과 동일한 방법으로 편광판을 제조하였다.A polarizing plate was manufactured in the same manner as in Example 1, except that G was used as the radical curable composition.
비교예 1Comparative Example 1
라디칼 경화형 조성물로 H를 사용한 점을 제외하고는, 실시예 1과 동일한 방법으로 편광판을 제조하였다.A polarizing plate was manufactured in the same manner as in Example 1 except that H was used as the radical curable composition.
비교예 2Comparative Example 2
라디칼 경화형 조성물로 I를 사용한 점을 제외하고는, 실시예 1과 동일한 방법으로 편광판을 제조하였다.A polarizing plate was manufactured in the same manner as in Example 1 except that I was used as the radical curable composition.
비교예 3Comparative Example 3
라디칼 경화형 조성물로 J를 사용한 점을 제외하고는, 실시예 1과 동일한 방법으로 편광판을 제조하였다.A polarizing plate was manufactured in the same manner as in Example 1, except that J was used as the radical curable composition.
실험예 1 - 밀착성 평가Experimental Example 1 Evaluation of Adhesion
상기 실시예 및 비교예에서 제조한 편광판의 보호층의 밀착성을 측정하여 하기 [표 1]에 나타내었다. 구체적으로, 편광자(PVA 소자) 위에 상기 실시예 및 비교예에서 사용한 라디칼 경화형 조성물을 4~5㎛으로 도포하고 그 위에 편광자(PVA 소자)를 적층하여 라미네이터를 통과시킨 다음, 자외선 조사장치(Metal halide lamp)를 이용하여 1000mJ/cm2로 UV를 조사하여, 편광자/보호층/편광자로 이루어진 박리력 샘플을 제조하였다. 제조된 샘풀을 온도 20℃, 습도 70% 조건에서 4 일간 방치한 후, 폭 20mm, 길이 100mm로 재단하고, Texture Analyzer장비(Stable Micro Systems사 TA-XT Plus)로, 속도 300m/min, 90도로 박리력을 측정하였다. 이때, 박리력이 1.0N/2cm 내지 2.0N/2cm 이면 우수, 0.5N/2cm 이상 1.0N/2cm 미만이면 양호, 0.5N/2cm 미만이면 나쁨으로 표시하였다.The adhesiveness of the protective layer of the polarizing plates manufactured by the said Example and the comparative example was measured, and is shown in following [Table 1]. Specifically, the radical curable composition used in the above Examples and Comparative Examples on the polarizer (PVA device) is applied to 4 ~ 5㎛, laminated on the polarizer (PVA device) and passed through the laminator, and then UV irradiation device (Metal halide) UV) was irradiated at 1000 mJ / cm 2 using a lamp) to prepare a peel force sample consisting of a polarizer / protective layer / polarizer. The sample 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 then subjected to a texture analyzer (TA-XT Plus from Stable Micro Systems) at a speed of 300 m / min and 90 degrees. Peel force was measured. At this time, when peeling force was 1.0N / 2cm-2.0N / 2cm, it was excellent, 0.5N / 2cm or more and less than 1.0N / 2cm, and it displayed as bad if it was less than 0.5N / 2cm.
실험예 2 - 내수성 평가Experimental Example 2-Evaluation of Water Resistance
상기 실시예 및 비교예에서 제조된 편광판의 내수성을 측정하여 하기 [표 1]에 나타내었다. 구체적으로, 상기 실시예 및 비교예의 편광판을 유리 기판에 라미네이션(glass lamination)한 후에 60℃ 항온조에 침지시키고, 8 시간 경과 후 편광판 단부의 탈색여부로 내수성을 판단하였으며, 변형이 없는 경우를 우수로, 일부 탈색이 있는 경우 양호로, 탈색이 많이 일어난 경우를 나쁨으로 표시하였다.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.
실험예 3 - 열 충격물성 평가Experimental Example 3-Evaluation of thermal shock properties
상기 실시예 및 비교예에서 제조한 편광판의 열 충격물성을 측정하여 하기 [표 1]에 나타내었다. 구체적으로, 상기 실시예 및 비교예에서 제조한 편광판을 유리 기판에 라미네이션(glass lamination)하고, 이를 -40℃에서 30분 동안 방치한 후, 이를 다시 80℃에서 30분 동안 방치하는 것을 100회 반복하여 수행하였다. 그런 다음, 편광판 외관에 변형 여부를 육안으로 평가하였다. 편광판 외관에 단부에만 2mm이하의 크랙 발생이 있는 경우를 우수로, 단부 이외의 5mm이상 짧은 선상의 크랙 만 확인되는 경우를 양호로, 편광판 전면에 다수의 크랙이 발생한 경우를 나쁨으로 표시하였다.The thermal shock properties of the polarizing plates prepared in Examples and Comparative Examples were measured and shown in the following [Table 1]. Specifically, the lamination of the polarizing plates prepared in Examples and Comparative Examples on a glass substrate (glass lamination), it was left for 30 minutes at -40 ℃, and then it was left again for 30 minutes at 80 ℃ repeated 100 times It was performed by. Then, visual evaluation of the deformation of the polarizing plate appearance. The case where the occurrence of cracks of 2 mm or less in the exterior of the polarizing plate alone was excellent, and the case where only linear cracks of 5 mm or more shorter than the end were identified was good, and the case where many cracks occurred on the entire surface of the polarizing plate was indicated as bad.
실험예 4 - 조성물의 점도 측정Experimental Example 4-Viscosity Measurement of Compositions
상기 실시예 및 비교예에서 사용된 조성물의 점도를 25℃에서 Viscometer TV-22(TOKI SANGYO)를 사용하여 측정하여, 하기 [표 1]에 나타내었다.The viscosity of the composition used in the above Examples and Comparative Examples was measured using Viscometer TV-22 (TOKI SANGYO) at 25 ℃, it is shown in Table 1 below.
표 1
구분 조성물 밀착성 내수성 열충격 안정성 점도[cP]
실시예 1 A 양호 우수 우수 42
실시예 2 B 우수 우수 우수 65
실시예 3 C 양호 우수 우수 55
실시예 4 D 우수 우수 우수 63
실시예 5 E 우수 우수 양호 50
실시예 6 F 양호 우수 양호 47
실시예 7 G 우수 양호 우수 68
비교예 1 H 나쁨 나쁨 나쁨 90
비교예 2 I 양호 나쁨 양호 72
비교예 3 J 양호 나쁨 양호 75
Table 1
division Composition Adhesiveness Water resistance Thermal shock stability Viscosity [cP]
Example 1 A Good Great Great 42
Example 2 B Great Great Great 65
Example 3 C Good Great Great 55
Example 4 D Great Great Great 63
Example 5 E Great Great Good 50
Example 6 F Good Great Good 47
Example 7 G Great Good Great 68
Comparative Example 1 H Bad Bad Bad 90
Comparative Example 2 I Good Bad Good 72
Comparative Example 3 J Good Bad Good 75
상기 표 1에서 볼 수 있듯이, 본 발명의 실시예 1 ~ 7의 경우 밀착성이 우수할 뿐 아니라, 내수성 및 열충격 안정성 역시 우수하며, 점도가 낮은 것을 알 수 있다.As can be seen in Table 1, in the case of Examples 1 to 7 of the present invention, as well as excellent adhesion, water resistance and thermal shock stability is also excellent, it can be seen that the viscosity is low.
반면, 비교예 1에서와 같이 3 관능성 포스페이트계 화합물을 포함하지 않는 경우 밀착성, 내수성, 열충격 안정성, 점도 특성이 모두 불량한 것을 알 수 있다.On the other hand, when it does not contain a trifunctional phosphate-based compound as in Comparative Example 1, it can be seen that the adhesion, water resistance, thermal shock stability, viscosity properties are all poor.
또한, 비교예 2에서와 같이 3 관능성 포스페이트계 화합물 대신 2 관능성 포스페이트계 화합물을 사용하는 경우 밀착성 및 열충격 안정성은 양호하나, 여전히 내수성 및 점도 특성이 불량한 것을 알 수 있다.In addition, in the case of using the bifunctional phosphate-based compound instead of the trifunctional phosphate-based compound as in Comparative Example 2, the adhesion and thermal shock stability is good, but it can be seen that the water resistance and viscosity properties are still poor.
또한, 비교예 3에서와 같이 3 관능성 포스페이트계 화합물 대신 단관능성 포시페이트계 화합물을 사용하는 경우 마찬가지로 밀착성 및 열충격 물성은 양호하나, 여전히 내수성 및 점도 특성이 불량한 것을 알 수 있다.In addition, when using the mono-functional phosphate-based compound instead of the tri-functional phosphate-based compound as in Comparative Example 3 similarly good adhesion and thermal shock properties, it can be seen that the water resistance and viscosity properties are still poor.
한편, 상기 실시예의 경우 편광판 제조 시 접착제층과 보호층을 편의상 동일한 라디칼 경화형 조성물을 사용하여 제조하였으나, 반드시 이에 구속되는 것은 아니다.Meanwhile, in the case of the above embodiment, the adhesive layer and the protective layer were manufactured using the same radical curable composition for convenience, but the present invention is not necessarily limited thereto.
이상에서 본 발명의 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고, 청구범위에 기재된 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 수정 및 변형이 가능하다는 것은 당 기술분야의 통상의 지식을 가진 자에게는 자명할 것이다.Although the embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and changes can be made without departing from the technical spirit of the present invention described in the claims. It will be obvious to those of ordinary skill in the field.

Claims (18)

  1. 편광자; 및Polarizer; And
    상기 편광자의 적어도 일면에 형성되는 보호층을 포함하는 편광판이며,It is a polarizing plate including a protective layer formed on at least one surface of the polarizer,
    상기 보호층이 (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 조성물의 경화물인 편광판.A radically polymerizable compound in which the protective layer has at least one hydrophilic functional group in the molecule (A); (B) phosphate compounds having three (meth) acryl groups in the molecule; And (C) a polarizing plate which is a cured product of a radical curable composition containing a radical initiator.
  2. 제 1 항에 있어서,The method of claim 1,
    상기 라디칼 경화형 조성물은 라디칼 경화형 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 것인 편광판.The radically curable composition comprises: (A) 40 to 93 parts by weight of a radical curable compound; (B) 1 to 40 parts by weight of the phosphate compound; And (C) 0.5 to 20 parts by weight of a radical initiator.
  3. 제 1 항에 있어서,The method of claim 1,
    상기 (A) 라디칼 중합성 화합물은,The (A) radically polymerizable compound,
    (a-1) 분자 내에 적어도 1개의 히드록시기 및 적어도 1개의 (메트)아크릴기를 포함하는 라디칼 중합성 제 1 화합물; 및(a-1) a radically polymerizable first compound comprising at least one hydroxy group and at least one (meth) acryl group in a molecule; And
    (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 편광판.(a-2) A polarizing plate which is 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.
  4. 제 3 항에 있어서,The method of claim 3, wherein
    상기 (a-1) 제 1 화합물은 하기 [화학식 1] 내지 [화학식 21]로 이루어진 군으로부터 선택되는 1종 이상인 편광판.The (a-1) first compound is at least one polarizing plate selected from the group consisting of the following [Formula 1] to [Formula 21].
    [화학식 1][Formula 1]
    Figure PCTKR2014009133-appb-I000075
    Figure PCTKR2014009133-appb-I000075
    [화학식 2][Formula 2]
    Figure PCTKR2014009133-appb-I000076
    Figure PCTKR2014009133-appb-I000076
    [화학식 3][Formula 3]
    Figure PCTKR2014009133-appb-I000077
    Figure PCTKR2014009133-appb-I000077
    [화학식 4][Formula 4]
    Figure PCTKR2014009133-appb-I000078
    Figure PCTKR2014009133-appb-I000078
    [화학식 5][Formula 5]
    Figure PCTKR2014009133-appb-I000079
    Figure PCTKR2014009133-appb-I000079
    [화학식 6][Formula 6]
    Figure PCTKR2014009133-appb-I000080
    Figure PCTKR2014009133-appb-I000080
    [화학식 7][Formula 7]
    Figure PCTKR2014009133-appb-I000081
    Figure PCTKR2014009133-appb-I000081
    [화학식 8][Formula 8]
    Figure PCTKR2014009133-appb-I000082
    Figure PCTKR2014009133-appb-I000082
    [화학식 9][Formula 9]
    Figure PCTKR2014009133-appb-I000083
    Figure PCTKR2014009133-appb-I000083
    [화학식 10][Formula 10]
    Figure PCTKR2014009133-appb-I000084
    Figure PCTKR2014009133-appb-I000084
    [화학식 11][Formula 11]
    Figure PCTKR2014009133-appb-I000085
    Figure PCTKR2014009133-appb-I000085
    [화학식 12][Formula 12]
    Figure PCTKR2014009133-appb-I000086
    Figure PCTKR2014009133-appb-I000086
    [화학식 13][Formula 13]
    Figure PCTKR2014009133-appb-I000087
    Figure PCTKR2014009133-appb-I000087
    [화학식 14][Formula 14]
    Figure PCTKR2014009133-appb-I000088
    Figure PCTKR2014009133-appb-I000088
    [화학식 15][Formula 15]
    Figure PCTKR2014009133-appb-I000089
    Figure PCTKR2014009133-appb-I000089
    [화학식 16][Formula 16]
    Figure PCTKR2014009133-appb-I000090
    Figure PCTKR2014009133-appb-I000090
    [화학식 17][Formula 17]
    Figure PCTKR2014009133-appb-I000091
    Figure PCTKR2014009133-appb-I000091
    [화학식 18][Formula 18]
    Figure PCTKR2014009133-appb-I000092
    Figure PCTKR2014009133-appb-I000092
    [화학식 19][Formula 19]
    Figure PCTKR2014009133-appb-I000093
    Figure PCTKR2014009133-appb-I000093
    [화학식 20][Formula 20]
    Figure PCTKR2014009133-appb-I000094
    Figure PCTKR2014009133-appb-I000094
    [화학식 21][Formula 21]
    Figure PCTKR2014009133-appb-I000095
    Figure PCTKR2014009133-appb-I000095
  5. 제 3 항에 있어서,The method of claim 3, wherein
    상기 (a-2) 제 2 화합물은 하기 [화학식 22] 내지 [화학식 24]로 이루어진 군으로부터 선택되는 1종 이상인 편광판.The second compound (a-2) is at least one polarizing plate selected from the group consisting of the following [Formula 22] to [Formula 24].
    [화학식 22][Formula 22]
    Figure PCTKR2014009133-appb-I000096
    Figure PCTKR2014009133-appb-I000096
    [화학식 23][Formula 23]
    Figure PCTKR2014009133-appb-I000097
    Figure PCTKR2014009133-appb-I000097
    [화학식 24][Formula 24]
    Figure PCTKR2014009133-appb-I000098
    Figure PCTKR2014009133-appb-I000098
  6. 제 1 항에 있어서,The method of claim 1,
    상기 (B) 포스페이트계 화합물은 하기 [화학식 I]로 표시되는 화합물인 편광판.Said (B) phosphate type compound is a polarizing plate which is a compound represented by following [Formula I].
    [화학식 I][Formula I]
    Figure PCTKR2014009133-appb-I000099
    Figure PCTKR2014009133-appb-I000099
    상기 [화학식 I]에서, R1, R2 및 R3는 각각 독립적으로 치환 또는 비치환된 C1~10 알킬렌기, 치환 또는 비치환된 C4~14 시클로알킬렌기, 치환 또는 비치환된 C6~14 아릴렌기, 또는 이들의 조합이고; R4, R5 및 R6은 각각 독립적으로 수소 또는 메틸기이며; X1, X2 및 X3는 각각 독립적으로 O(산소) 또는 N(질소)임.The Formula I] from, 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).
  7. 제 1 항에 있어서,The method of claim 1,
    상기 라디칼 경화형 조성물은 (D) 분자 내에 1개 또는 2개의 (메트)아크릴기를 갖는 포스페이트계 화합물을 더 포함하는 편광판.The radical curable composition further comprises a phosphate compound having one or two (meth) acryl groups in the (D) molecule.
  8. 제 7 항에 있어서,The method of claim 7, wherein
    상기 (D) 포스페이트계 화합물은 편광판 100 중량부에 있어서 5 내지 40 중량부로 포함되는 것인 편광판.The (D) phosphate-based compound is 5 to 40 parts by weight in 100 parts by weight of the polarizing plate is a polarizing plate.
  9. 제 7 항에 있어서,The method of claim 7, wherein
    상기 (D) 포스페이트계 화합물은 하기 [화학식 Ⅱ] 및 [화학식 Ⅲ]로 표시되는 화합물로 이루어진 군으로부터 선택되는 1종 이상인 편광판.The (D) phosphate-based compound is at least one polarizing plate selected from the group consisting of compounds represented by the following [Formula II] and [Formula III].
    [화학식 Ⅱ][Formula II]
    Figure PCTKR2014009133-appb-I000100
    Figure PCTKR2014009133-appb-I000100
    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.Wherein in Formula Ⅱ], 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).
    [화학식 Ⅲ][Formula III]
    Figure PCTKR2014009133-appb-I000101
    Figure PCTKR2014009133-appb-I000101
    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.The Formula Ⅲ] in, 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).
  10. 제 1 항에 있어서,The method of claim 1,
    상기 라디칼 경화형 조성물은 (E) 다관능성 (메트)아크릴계 화합물을 더 포함하는 편광판.The radical curable composition further comprises (E) a polyfunctional (meth) acrylic compound.
  11. 제 10 항에 있어서,The method of claim 10,
    상기 (E) 다관능성 (메트)아크릴계 화합물은 편광판 100 중량부에 있어서 5 내지 40 중량부로 포함되는 것인 편광판.Said (E) polyfunctional (meth) acrylic-type compound is contained in 5-40 weight part in 100 weight part of polarizing plates.
  12. 제 10 항에 있어서,The method of claim 10,
    상기 (E) 다관능성 (메트)아크릴계 화합물은 하기 [화학식 Ⅳ] 내지 [화학식 Ⅵ]로 표시되는 화합물로 이루어진 군으로 선택된 1종 이상인 편광판.The (E) polyfunctional (meth) acrylic compound is at least one polarizing plate selected from the group consisting of compounds represented by the following [Formula IV] to [VI].
    [화학식 Ⅳ][Formula IV]
    Figure PCTKR2014009133-appb-I000102
    Figure PCTKR2014009133-appb-I000102
    상기 [화학식 Ⅳ]에서, R13 및 R14는 각각 독립적으로 (메트)아크릴로일옥시기 또는 (메트)아크릴로일옥시알킬기임.In [Formula IV], R 13 and R 14 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group.
    [화학식 Ⅴ][Formula Ⅴ]
    Figure PCTKR2014009133-appb-I000103
    Figure PCTKR2014009133-appb-I000103
    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.In Formula [V], R 15 , R 16 and R 17 are each independently a (meth) acryloyloxy group or a (meth) acryloyloxyalkyl group, and R 18 is a (meth) acryloyloxy group, (meth ) Acryloyloxyalkyl group, a hydroxy group, or a substituted or unsubstituted C 1-10 alkyl group.
    [화학식 Ⅵ][Formula VI]
    Figure PCTKR2014009133-appb-I000104
    Figure PCTKR2014009133-appb-I000104
    상기 [화학식 Ⅵ]에서, R19는 치환 또는 비치환된 C1~10 알킬렌이고, R20 및 R21은 각각 독립적으로 (메트)아크릴로일옥시기 또는 (메트)아크릴로일옥시알킬기임.In Formula [VI], 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.
  13. 제 1 항에 있어서,The method of claim 1,
    상기 라디칼 경화형 조성물은 경화 후 유리전이온도가 50℃ 이상인 편광판.The radical curable composition has a glass transition temperature of 50 ° C. or more after curing.
  14. 제 1 항에 있어서,The method of claim 1,
    상기 라디칼 경화형 조성물은 점도가 70cP 이하인 편광판.The said radical curable composition is a polarizing plate whose viscosity is 70 cP or less.
  15. 제 1 항에 있어서,The method of claim 1,
    상기 보호층의 두께는 0.5 내지 20㎛인 편광판.The protective layer has a thickness of 0.5 to 20㎛.
  16. 제 1 항에 있어서,The method of claim 1,
    상기 편광자의 보호층이 형성된 면의 반대면에 접착제층을 매개로 보호 필름이 부착된 편광판.Polarizing plate attached to the protective film via the adhesive layer on the opposite side of the surface on which the protective layer of the polarizer is formed.
  17. 제 1 항에 있어서,The method of claim 1,
    상기 보호층 상부에 점착층을 더 포함하는 편광판.Polarizing plate further comprises an adhesive layer on the protective layer.
  18. 제 1 항 내지 제 17 항 중 어느 한 항의 편광판을 포함하는 화상표시장치.An image display apparatus comprising the polarizing plate of any one of claims 1 to 17.
PCT/KR2014/009133 2013-09-30 2014-09-29 Polarizing plate and image display device comprising same WO2015047001A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2016545702A JP6374006B2 (en) 2013-09-30 2014-09-29 Polarizing plate and image display device including the same
US15/025,452 US9651716B2 (en) 2013-09-30 2014-09-29 Polarizing plate and image display device comprising same
CN201480054117.6A CN105705970B (en) 2013-09-30 2014-09-29 Polarizer and image display device including the polarizer

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20130117043 2013-09-30
KR10-2013-0117043 2013-09-30
KR1020140129390A KR101697403B1 (en) 2013-09-30 2014-09-26 Polarizing plate and image display apparatus comprising the same
KR10-2014-0129390 2014-09-26

Publications (1)

Publication Number Publication Date
WO2015047001A1 true WO2015047001A1 (en) 2015-04-02

Family

ID=52744003

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2014/009133 WO2015047001A1 (en) 2013-09-30 2014-09-29 Polarizing plate and image display device comprising same

Country Status (1)

Country Link
WO (1) WO2015047001A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070212627A1 (en) * 2006-03-13 2007-09-13 Yoshiki Yanagawa Electrophotographic photoreceptor and method of preparing the photoreceptor, and image forming method, image forming apparatus and process cartridge therefor using the photoreceptor
JP2008105191A (en) * 2006-10-23 2008-05-08 Fujifilm Corp Optical film, antireflection film, polarizing plate, display device and manufacturing method of optical film
JP2010066484A (en) * 2008-09-10 2010-03-25 Sumitomo Chemical Co Ltd Polarizing plate, method for manufacturing the same, optical member and liquid crystal display device
KR20120015780A (en) * 2010-08-13 2012-02-22 주식회사 엘지화학 Polarizing plate and liquid crystal display comprising the same
KR20130023181A (en) * 2011-08-25 2013-03-07 주식회사 엘지화학 Polarizing plate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070212627A1 (en) * 2006-03-13 2007-09-13 Yoshiki Yanagawa Electrophotographic photoreceptor and method of preparing the photoreceptor, and image forming method, image forming apparatus and process cartridge therefor using the photoreceptor
JP2008105191A (en) * 2006-10-23 2008-05-08 Fujifilm Corp Optical film, antireflection film, polarizing plate, display device and manufacturing method of optical film
JP2010066484A (en) * 2008-09-10 2010-03-25 Sumitomo Chemical Co Ltd Polarizing plate, method for manufacturing the same, optical member and liquid crystal display device
KR20120015780A (en) * 2010-08-13 2012-02-22 주식회사 엘지화학 Polarizing plate and liquid crystal display comprising the same
KR20130023181A (en) * 2011-08-25 2013-03-07 주식회사 엘지화학 Polarizing plate

Similar Documents

Publication Publication Date Title
WO2016052951A1 (en) Polarizing plate and image display apparatus comprising same
WO2010095905A2 (en) Modified polyvinyl alcohol resins and adhesive, polarizer, and display device containing the same
WO2009091225A2 (en) Composition for liquid crystal alignment layer, preparation method of liquid crystal alignment layer using the same, and optical film comprising the liquid crystal alignment layer
WO2015016456A1 (en) Retardation film and image display device having same
WO2021118250A1 (en) Adhesive layer
WO2019117676A2 (en) Polarizing plate, polarizing plate-carrier film laminate, method for preparing polarizing plate-carrier film laminate, method for preparing polarizing plate and active energy ray curable composition
WO2017119761A1 (en) Film touch sensor and method for manufacturing same
WO2017086567A1 (en) Flexible touchscreen panel module and flexible display device comprising same
WO2013051831A2 (en) Composition for forming an alignment layer, and alignment layer and phase difference film manufactured using same
WO2015046713A1 (en) Polarizing plate
WO2019013516A1 (en) Circular polarizer
WO2014193072A1 (en) Optical film with excellent ultraviolet cut-off function and polarizing plate including same
WO2019059692A1 (en) Polarizing plate and image display device comprising same
WO2016085087A9 (en) (meth)acrylic compounds having high refractive index, preparation method therefor, optical sheet comprising same, and optical display device comprising same
WO2020153655A1 (en) Film touch sensor and manufacturing method therefor
WO2014157976A1 (en) Method for manufacturing double-sided polarizing plate and double-sided polarizing plate manufactured by same
WO2015046816A1 (en) Polarizing plate and image display device comprising same
WO2015047001A1 (en) Polarizing plate and image display device comprising same
WO2015046999A1 (en) Polarizing plate and image display apparatus comprising same
WO2021221374A1 (en) Polyamide-based composite film and display device comprising same
WO2014204142A1 (en) Radical-curable adhesive composition and polarizing plate comprising same
WO2015047004A1 (en) Radical curable adhesive composition, and polarizing plate and optical member comprising same
WO2015046997A1 (en) Polarizing plate and image display apparatus comprising same
WO2017171272A1 (en) Color filter and image display device comprising same
WO2021246851A1 (en) Polyester release film and method for manufacturing same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14847501

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 15025452

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2016545702

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14847501

Country of ref document: EP

Kind code of ref document: A1