KR20180028749A - Crosslinkable Composition - Google Patents
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- KR20180028749A KR20180028749A KR1020160116486A KR20160116486A KR20180028749A KR 20180028749 A KR20180028749 A KR 20180028749A KR 1020160116486 A KR1020160116486 A KR 1020160116486A KR 20160116486 A KR20160116486 A KR 20160116486A KR 20180028749 A KR20180028749 A KR 20180028749A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/387—Block-copolymers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
Abstract
This application relates to crosslinkable compositions and uses thereof. The present application can provide a crosslinkable composition capable of forming, for example, a pressure-sensitive adhesive or an adhesive as the crosslinkable composition. The pressure-sensitive adhesive or adhesive has excellent heat resistance and endurance reliability, and can exhibit excellent stress relaxation and warpage suppression characteristics even when it is combined with an optical film or a conductive film of a thin film.
Description
This application relates to crosslinkable compositions and uses thereof.
The crosslinkable composition can be applied to various applications. Exemplary applications include a pressure-sensitive adhesive or an adhesive applied to a display device such as a liquid crystal display device or a conductive film.
Description of the Related Art [0002] A liquid crystal display device (hereinafter, referred to as " LCD device ") typically includes a liquid crystal panel and an optical film containing a liquid crystal component injected between two transparent substrates. As the optical film, a polarizing film, a retardation film, a brightness enhancement film, and the like are often used. In many cases, a pressure-sensitive adhesive for an optical film is often used to laminate the optical films or attach the optical films to an adherend such as a liquid crystal panel. As the pressure sensitive adhesive, acrylic polymers, rubbers, urethane resins, silicone resins, or ethylene vinyl acetate (EVA) resins and the like are used. As the pressure sensitive adhesive for optical films, particularly polarizing plates, transparency, resistance to oxidation or yellowing Adhesives containing this good acrylic copolymer are generally used.
The main physical properties required in the pressure-sensitive adhesive composition for an optical film include cohesive force, adhesive force, reworkability, low light leakage property and stress relaxation property. In Patent Documents 1 to 3, a pressure-sensitive adhesive composition for achieving the above properties has been proposed.
The present application provides crosslinkable compositions and uses thereof. When applied as an adhesive layer or an adhesive layer to an optical film or an electrically conductive film, the present application can provide a crosslinkable composition capable of suppressing warping of an optical film or a conductive film while securing durability.
The term crosslinkable composition means a composition comprising a component capable of forming a crosslinked structure. In the above, the crosslinking structure may mean a chemical crosslinking structure or a physical crosslinking. The crosslinkable composition of the present application comprises a block copolymer capable of forming physical crosslinking itself by so-called phase separation or self-assembling property and, when necessary, introducing a crosslinkable functional group capable of chemical crosslinking into the block copolymer , A physical crosslinking structure and a chemical crosslinking structure can be simultaneously formed.
Such a crosslinkable composition may be, for example, a pressure-sensitive adhesive composition or an adhesive composition. In the above, the pressure-sensitive adhesive composition or the adhesive composition may mean a composition containing a crosslinked structure or a composition capable of exhibiting the properties of the pressure-sensitive adhesive or adhesive before the crosslinked structure is formed.
The crosslinkable composition may comprise a block copolymer. The term " block copolymer " can refer to a copolymer comprising blocks of different polymerized monomers, which are different from each other. The crosslinkable composition may include a block copolymer as a main component. As used herein, the inclusion of a component as a major component in a subject means that the ingredient is present in the subject in an amount of at least 50 wt%, at least 55 wt%, at least 60 wt%, at least 65 wt%, at least 70 wt% 75% by weight or more, 80% by weight or more, 85% by weight or more, or 90% by weight or more. The upper limit of the content of the component contained in the main component in the subject is not particularly limited and may be, for example, about 100. [ On the other hand, the content of each component in the crosslinkable composition is based on the solid content.
The block copolymer may include a first block having a glass transition temperature of 50 캜 or higher and a second block having a glass transition temperature of -10 캜 or lower. As used herein, the "glass transition temperature of a given block" of a block copolymer may refer to a glass transition temperature measured from a polymer formed only of the monomers contained in the block.
In another example, the glass transition temperature of the first block may be at least 60 ° C, at least 65 ° C, at least 70 ° C, or at least 75 ° C. The upper limit of the glass transition temperature of the first block is not particularly limited. For example, the glass transition temperature of the first block may be 200 占 폚 or lower, 190 占 폚 or lower, 180 占 폚 or lower, 170 占 폚 or lower, 140 deg. C, 130 deg. C, 120 deg. C, 110 deg. C or 100 deg. C or lower.
In the above, the glass transition temperature of the second block may be -15 캜 or lower, -20 캜 or lower, -25 캜 or lower or about -30 캜 or lower. The lower limit of the glass transition temperature of the second block is not particularly limited. For example, the glass transition temperature of the second block may be -100 ° C or higher, -90 ° C or higher, -80 ° C or higher, -70 ° C or higher, 60 deg. C or higher or -55 deg. C or higher.
The block copolymer containing at least two kinds of blocks having such a glass transition temperature can form a phase separation structure in the crosslinkable composition to form an appropriate physical crosslinking structure, for example. Such a block copolymer exhibits an appropriate cohesive force and stress relaxation property in accordance with a change in temperature and can form a pressure-sensitive adhesive or an adhesive which maintains excellent physical properties required for an optical film or a conductive film, such as durability reliability, light- have.
The first block of the block copolymer may have a Number Average Molecular Weight (Mn) in the range of 2,500 to 150,000, for example. The number average molecular weight of the first block may mean, for example, the number average molecular weight of the polymer produced by polymerizing only the monomer forming the first block. The number average molecular weight referred to in the present specification can be measured by the method shown in the examples using GPC (Gel Permeation Chromatograph). The number average molecular weight of the first block may be 5,000 or more, 10,000 or more, 15,000 or more, or 20,000 or more in another example. In another example, the number average molecular weight may be about 100,000 or less, about 90,000 or less, about 80,000 or less, about 70,000 or less, about 60,000 or less, about 50,000 or less, about 40,000 or less about 30,000 or less.
The block copolymer may have a number average molecular weight in the range of 50,000 to 300,000. The number average molecular weight of the block copolymer can be in the range of 70,000 or more, 90,000 or more, 110,000 or more, 130,000 or more, 150,000 or more, or 170,000 or more. The number average molecular weight may be less than 280,000, less than 260,000 or less than 240,000 in other examples.
The block copolymer has a molecular weight distribution (PDI; Mw / Mn), that is, a ratio (Mw / Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) within a range of 1.0 to 4.0, Can be. The molecular weight distribution may be about 1.2 or more or about 1.4 or more in another example. In another example, the molecular weight distribution may be about 3.8 or less, about 3.6 or less, about 3.4 or less, about 3.2 or less, about 3.0 or less, about 2.8 or less, or about 2.6 or less.
By controlling the molecular weight characteristics as described above, a crosslinkable composition having excellent physical properties can be provided.
The block copolymer may be a crosslinkable copolymer having a crosslinkable functional group. Examples of the crosslinkable functional group include a hydroxyl group, a carboxyl group, an isocyanate group or a glycidyl group, and for example, a hydroxy group or a carboxyl group can be used.
In the case of containing a crosslinkable functional group, the functional group may be included in, for example, a second block having a low glass transition temperature. In one example, the first block having a high glass transition temperature may not contain a crosslinkable functional group, and the second block may contain a crosslinkable functional group. When the crosslinkable functional group is included in the second block, it exhibits appropriate cohesive force and stress relaxation property in accordance with a change in temperature, and can maintain excellent physical properties required for an optical film or a conductive film such as durability reliability, light- .
In one example, the first block may include a (meth) acrylic acid ester monomer as a monomer unit. As used herein, the inclusion of a component as a monomer unit means that the monomer is polymerized to form a skeleton of the polymer or block, for example, a main chain or a side chain . Unless otherwise stated, the polymer or block may include any monomer, which may mean that the monomer is included as a monomer unit.
In one example, considering the control of cohesion, glass transition temperature and tackiness, alkyl (meth) acrylates having an alkyl group of 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms Methacrylate may be used. Examples of such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (Meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate and lauryl (meth) acrylate. Can be selected and used.
In consideration of the ease of controlling the glass transition temperature and the like, the first block is preferably a methacrylic acid ester monomer such as alkyl methacrylate, specifically having 1 to 20 carbon atoms, 1 to 20 carbon atoms, 16, an alkyl methacrylate having an alkyl group having 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms.
The first block may contain, as a monomer unit, the alkyl methacrylate as a main component.
The second block of the block copolymer may be an alkyl (meth) acrylate having an alkyl group of 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms and 1 to 4 carbon atoms, Acrylate may be used. Considering the ease of controlling the glass transition temperature, alkyl acrylate may be applied to the second block in the above-mentioned monomers.
The second block may contain, as a monomer unit, the alkyl acrylate as a main component.
In order to maximize the anti-flexural property of the pressure-sensitive adhesive or adhesive formed by the crosslinkable composition, the second block preferably comprises an alkyl acrylate having an alkyl group having 1 to 5 carbon atoms and an alkyl acrylate having an alkyl group having 6 or more carbon atoms among the alkyl acrylates Rate.
Examples of the alkyl acrylate having an alkyl group of 1 to 5 carbon atoms include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, Acrylate, pentyl (meth) acrylate, and the like.
In the above alkyl acrylate having 6 or more carbon atoms, the alkyl group may have 6 to 20, 6 to 18, 6 to 16, 6 to 14, 7 to 14 or 8 to 14 carbon atoms. Examples of such monomers include, but are not limited to, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate or lauryl acrylate.
By controlling such monomer components, heat resistance durability of the crosslinkable composition can be ensured, and flexural strength can be maximized by imparting flexibility.
In one example, the second block may include alkyl acrylate having an alkyl group having 6 or more carbon atoms in a ratio of about 1 to about 100 parts by weight based on 100 parts by weight of alkyl acrylate having an alkyl group having 1 to 5 carbon atoms. In another example, the weight ratio of the alkyl acrylate having an alkyl group having 6 or more carbon atoms may be about 5 parts by weight or more, about 10 parts by weight or more, or about 15 parts by weight or more based on 100 parts by weight of alkyl acrylate having an alkyl group having 1 to 5 carbon atoms have. In another example, the weight ratio of the alkyl acrylate having an alkyl group having 6 or more carbon atoms is about 95 parts by weight or less, about 90 parts by weight or less, about 90 parts by weight or less, about 100 parts by weight or less, about 100 parts by weight of alkyl acrylate having an alkyl group having 1 to 5 carbon atoms, Up to 85 parts by weight, up to about 80 parts by weight, up to about 75 parts by weight, or up to about 70 parts by weight.
In the present specification, the unit weight portion may mean the ratio of the weight between each component. By controlling the ratio of the two types of alkyl acrylates contained in the second block as described above, the effect of using the two kinds of monomers can be maximized.
When a crosslinkable functional group is introduced into the second block, the second block may further include, as a monomer unit, a copolymerizable monomer having a crosslinkable functional group. Such a monomer may be contained, for example, at a ratio of about 0.1 to 70 parts by weight based on 100 parts by weight of the alkyl acrylate contained in the second block. In another example, the ratio may be at least about 0.3 parts by weight, at least about 0.5 parts by weight, at least about 0.7 parts by weight, or at least about 0.9 part by weight, in other embodiments up to about 65 parts by weight, up to about 60 parts by weight, About 50 parts by weight or less, about 45 parts by weight or less, about 40 parts by weight or less, about 35 parts by weight or less, about 30 parts by weight or less, about 25 parts by weight or less, about 20 parts by weight or less, about 15 parts by weight or less , Up to about 10 parts by weight, or up to about 5 parts by weight.
Examples of the copolymerizable monomer having a crosslinkable functional group include a copolymerizable monomer having a moiety copolymerizable with other monomers contained in the block copolymer such as the above (meth) acrylic acid ester monomer and having a crosslinkable functional group, For example, a monomer having a hydroxyl group or the like can be used. In the production of pressure-sensitive adhesives, a variety of copolymerizable monomers having the above-mentioned crosslinkable functional groups are known, and all of these monomers can be used in the polymer. Examples of the copolymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) Hydroxyalkyl (meth) acrylate or 2-hydroxypropyleneglycol (meth) acrylate such as hydroxyalkyl (meth) acrylate or 8-hydroxyoctyl (Meth) acrylic acid, 2- (meth) acryloyloxyacetic acid, 3 (meth) acryloyloxyacetic acid, and the like. Examples of the copolymerizable monomer having a carboxyl group include A carboxyl group-containing compound such as (meth) acryloyloxypropyl acid, 4- (meth) acryloyloxybutyl acid, acrylic acid dimer, itaconic acid, maleic acid or maleic anhydride, or an anhydride thereof However, without being limited thereto. Hydroxyalkyl acrylate or hydroxyalkylene glycol acrylate among the above monomers may be used in consideration of reactivity with other monomers forming the second block and easiness of controlling the glass transition temperature and the like. no.
The first block and / or the second block may further comprise any other comonomer, if necessary, for example, for controlling the glass transition temperature and the like, and the monomer may be included as polymerized units have.
Examples of the comonomer include (meth) acrylonitrile, (meth) acrylamide, N-methyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-vinylpyrrolidone, Nitrogen-containing monomers such as lactam and the like; (Meth) acrylic acid esters, alkoxy alkylene glycol (meth) acrylic acid esters, alkoxy alkylene glycol (meth) acrylic acid esters, alkoxy alkylene glycol (Meth) acrylic acid esters, phenoxy alkylene glycol (meth) acrylic acid esters, phenoxy alkylene glycol (meth) acrylic acid esters, phenoxy trialkylene glycol Alkylene oxide group-containing monomers such as polyalkylene glycol (meth) acrylic acid esters and the like; Styrene-based monomers such as styrene or methylstyrene; Glycidyl group-containing monomers such as glycidyl (meth) acrylate; And carboxylic acid vinyl esters such as vinyl acetate, but are not limited thereto. These comonomers may be included in the polymer by selecting one kind or more than two types as appropriate according to need. Such comonomers may be included in the block copolymer, for example, in a proportion of 20 parts by weight or less, or 0.1 part by weight to 15 parts by weight, based on the weight of the other monomers in each block.
The block copolymer may include, for example, 10 parts by weight to 50 parts by weight of the first block and 50 parts by weight to 90 parts by weight of the second block. The ratio of the weight between the first block and the second block is adjusted as described above to provide the pressure-sensitive adhesive composition and the pressure-sensitive adhesive having excellent physical properties. In another example, the block copolymer may comprise from 5 to 45 parts by weight of the first block and from 55 to 95 parts by weight of the second block or from 5 to 45 parts by weight of the first block and from 60 to 60 parts by weight of the second block, 95 parts by weight.
In another example, the block copolymer may comprise about 50 to 90 wt%, about 55 to 95 wt%, or about 60 to 95 wt% of the second block based on the total weight of the first and second blocks have.
In one example, the block copolymer may be a diblock copolymer comprising the first and second blocks, i.e. a block copolymer comprising only two blocks of the first and second blocks . By using the diblock copolymer, the durability of the pressure-sensitive adhesive, the stress relaxation property, and the reworkability can be maintained more excellent.
In one example, the block copolymer may be a triblock copolymer comprising the first block, the second block and the first block. The triblock copolymer may have a structure of a first block - a second block - a first block or a structure of a second block - a first block - a second block. When there are two or more types of the first block and / or the second block, each of the first block and / or the second block may be the same or different. By using a triblock copolymer, physical properties such as durability, viscosity and adhesive property can be maintained more excellent.
The method for producing the block copolymer is not particularly limited and can be produced by a conventional method. The block polymer is polymerized by, for example, an LRP (Living Radical Polymerization) method. Examples of the block polymer include an organic rare earth metal complex as a polymerization initiator or an organic alkali metal compound as a polymerization initiator to produce an alkali metal or alkaline earth metal Anion polymerization which is synthesized in the presence of an inorganic acid salt such as a salt, an anionic polymerization method in which an organic alkali metal compound is used as a polymerization initiator and synthesized in the presence of an organoaluminum compound, an atomic transfer radical polymerization (ATRP), Atomic Transfer Radical Polymerization (ATRP), ICAR (Initiators), which conducts polymerization under an organic or inorganic reducing agent that generates electrons using an atom transfer radical polymerization agent as a polymerization initiator for continuous activator regeneration) Atom Transfer Radical Polymerization (ATRP) (RAFT) using a reversible addition-cleavage chain transfer agent using a reducing agent addition-cleavage chain transfer agent, or a method using an organic tellurium compound as an initiator. Among these methods, an appropriate method can be selected and applied.
The crosslinkable composition may further comprise a crosslinking agent capable of crosslinking the block copolymer. As the crosslinking agent, a crosslinking agent having at least two functional groups capable of reacting with the crosslinkable functional group contained in the block copolymer may be used. Examples of such a crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent or a metal chelate crosslinking agent, and for example, an isocyanate crosslinking agent may be used.
Examples of the isocyanate crosslinking agent include diisocyanate compounds such as tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoboron diisocyanate, tetramethylxylene diisocyanate and naphthalene diisocyanate, A compound obtained by reacting a diisocyanate compound with a polyol can be used. As the polyol, for example, trimethylolpropane and the like can be used.
The cross-linking composition may contain one or more of the above-mentioned cross-linking agents, but the cross-linking agents that can be used are not limited thereto.
The specific ratio of the crosslinking agent is not particularly limited, but may be, for example, about 0.01 to 10 parts by weight relative to 100 parts by weight of the block copolymer. In another example, the cross-linking agent may be at least about 0.05 part by weight or at least about 0.07 part by weight, and in another example at least about 9 parts by weight, up to about 8 parts by weight, up to about 7 parts by weight, up to about 6 parts by weight, About 4 parts by weight or less, about 3 parts by weight or less, or about 2 parts by weight or less.
The crosslinkable composition may further include a silane coupling agent. As the silane coupling agent, for example, a silane coupling agent having a beta-cyano group or an acetoacetyl group can be used. Such a silane coupling agent can be used, for example, so that a pressure-sensitive adhesive formed by a copolymer having a low molecular weight can exhibit excellent adhesion and adhesion stability, and can maintain excellent durability reliability under heat and moisture and heat have.
As the silane coupling agent having a beta-cyano group or an acetoacetyl group, for example, a compound represented by the following formula (1) or (2) can be used.
[Chemical Formula 1]
(R 1 ) m Si (R 2 ) (4-n)
(2)
(R 3 ) n Si (R 2 ) (4-n)
Wherein R 1 is a beta-cyanoacetyl group or a beta-cyanoacetylalkyl group, R 3 is an acetoacetyl group or an acetoacetylalkyl group, R 2 is an alkoxy group, and n is an integer of 1 to 3 ≪ / RTI >
In the general formula (1) or (2), the alkyl group may be an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, and the alkyl group may be linear, branched or cyclic have. In the general formula (1) or (2), the alkoxy group may be an alkoxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, and the alkoxy group may be linear, Can be. In Formula 1 or 2, n may be, for example, 1 to 3, 1 to 2, or 1.
Examples of the compound represented by the general formula (1) or (2) include acetoacetylpropyltrimethoxysilane, acetoacetylpropyltriethoxysilane, beta-cyanoacetylpropyltrimethoxysilane or beta-cyanoacetylpropyltriethoxysilane , But are not limited thereto.
In the crosslinkable composition, the silane coupling agent may be contained in an amount of 0.01 to 5 parts by weight or 0.01 to 1 part by weight based on 100 parts by weight of the block copolymer, and the desired properties may be effectively imparted to the pressure-sensitive adhesive within this range .
The crosslinkable composition may further comprise a tackifier as necessary. Examples of the tackifier include a hydrocarbon resin or hydrogenated product thereof, a rosin resin or hydrogenated product thereof, a rosin ester resin or hydrogenated product thereof, a terpene resin or hydrogenated product thereof, a terpene phenol resin or hydrogenated product thereof, Polymerized rosin ester resin, and the like, or a mixture of two or more of them may be used, but the present invention is not limited thereto.
The tackifier may be contained in the crosslinkable composition in an amount of 100 parts by weight or less based on 100 parts by weight of the block copolymer.
The crosslinkable composition may further comprise, if necessary, at least one additive selected from the group consisting of an epoxy resin, a curing agent, a UV stabilizer, an antioxidant, a colorant, a reinforcing agent, a filler, a defoamer, a surfactant and a plasticizer.
The crosslinkable composition may be used as a pressure-sensitive adhesive composition for a protective film. In the use of each of the crosslinkable compositions mentioned below, the pressure-sensitive adhesive composition may contain the crosslinkable composition as a main component based on the solid content. The protective film can be used, for example, for protecting the surface of various optical films.
The crosslinkable composition may also be used as a pressure-sensitive adhesive composition for a conductive film.
The crosslinkable composition may be a pressure-sensitive adhesive composition for an optical film. The pressure-sensitive adhesive composition for an optical film can be produced by, for example, laminating an optical film such as a polarizing film, a retardation film, an anti-glare film, a wide viewing angle compensation film or a brightness enhancement film to each other, And can be used for adhering to an adherend. In one example, the crosslinkable composition is a pressure-sensitive adhesive composition for a polarizing plate, and can be used for adhering a polarizing film to a liquid crystal panel.
The present application is also directed to a pressure-sensitive adhesive optical laminate. Exemplary optical stacks include optical films; And a pressure-sensitive adhesive layer formed on one side or both sides of the optical film. The pressure-sensitive adhesive layer may be, for example, a pressure-sensitive adhesive layer for adhering the optical film to another optical film such as a liquid crystal panel of a LCD device or a touch panel. The pressure-sensitive adhesive layer may include the cross-linkable composition of the present invention described above. The crosslinkable composition may be included in the pressure-sensitive adhesive layer in a state of realizing a crosslinked structure. The crosslinkable composition may be included as a main component of the pressure-sensitive adhesive composition. Examples of the optical film include a polarizing film, a retardation film, a brightness enhancement film, a conductive film, or a laminate in which two or more of the above are laminated.
The present application also relates to an adhesive polarizing plate. The polarizing plate may have, for example, a structure in which the optical film is a polarizing film in the adhesive optical laminate.
The kind of the polarizing film included in the polarizing plate is not particularly limited, and for example, general types known in the art such as a polyvinyl alcohol polarizing film and the like can be employed without limitation.
A polarizing film is a functional film capable of extracting only light vibrating in one direction from incident light while vibrating in various directions. Such a polarizing film may be, for example, a form in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based resin film. The polyvinyl alcohol-based resin constituting the polarizing film can be obtained by, for example, gelling a polyvinyl acetate-based resin.
In this case, the polyvinyl acetate-based resin that can be used may include not only homopolymers of vinyl acetate but also copolymers of vinyl acetate and other monomers copolymerizable therewith. Examples of the monomer copolymerizable with vinyl acetate include monomers such as unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group, or a mixture of two or more thereof. no.
The degree of gelation of the polyvinyl alcohol-based resin may be generally from 85 mol% to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin may be further modified. For example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used. The degree of polymerization of the polyvinyl alcohol-based resin may be about 1,000 to 10,000 or about 1,500 to 5,000.
The polarizing film is obtained by stretching a polyvinyl alcohol-based resin film as described above, for example, a process of uniaxially or biaxially stretching, a process of dyeing a polyvinyl alcohol-based resin film with a dichroic dye and adsorbing the dichroic dye, A process of treating a polyvinyl alcohol resin film adsorbed with a coloring pigment with an aqueous solution of boric acid and a process of washing with an aqueous solution of boric acid after washing.
As the dichroic dye, iodine or dichroic organic dyes may be used.
The polarizing plate may further include a protective film attached to one side or both sides of the polarizing film. In this case, the pressure sensitive adhesive layer may be formed on one side of the protective film. The kind of the protective film is not particularly limited and includes, for example, a cellulose-based film such as TAC (triacetyl cellulose); Polycarbonate film or PET (poly (ethylene terephthalate)); Polyethersulfone-based films; Or a polyolefin film produced by using a polyethylene film, a polypropylene film, a resin having a cyclo or norbornene structure, or an ethylene-propylene copolymer, or the like, or a film having a laminate structure of two or more layers. Particularly, it is more effective in improving heat resistance durability when PET-based, polyolefin-based film and acrylic-based film having good moisture barrier properties are applied.
The polarizing plate may further include at least one functional layer selected from the group consisting of a protective layer, a reflective layer, an antiglare layer, a retardation plate, a wide viewing angle compensation film, and a brightness enhancement film.
The method for forming the pressure-sensitive adhesive layer on the polarizing plate or the optical film as described above is not particularly limited, and for example, a method of directly coating the crosslinkable composition on a polarizing plate or an optical film and curing the crosslinked structure Or a method of forming a crosslinked structure by coating and curing the crosslinkable composition on the release treated surface of a release film and then transferring the crosslinked structure onto a polarizing plate or an optical film.
The method for coating the crosslinkable composition is not particularly limited, and for example, a method of applying the crosslinkable composition by a conventional means such as a bar coater may be used.
The multifunctional crosslinking agent contained in the crosslinkable composition during the coating process is preferably controlled in such a manner that the crosslinking reaction of the functional groups is not proceeded from the viewpoint of performing a uniform coating process so that the crosslinking agent is cured and hardened The crosslinking structure is formed to improve the cohesive force of the pressure-sensitive adhesive, and the adhesive property and cuttability can be improved.
The coating process is also preferably performed after sufficiently removing the bubble-inducing component such as volatile components or reaction residues in the crosslinkable composition, so that the crosslinking density or the molecular weight of the pressure-sensitive adhesive is too low to lower the elastic modulus, It is possible to prevent the problem that the bubbles existing between the glass plate and the adhesive layer become large to form a scattering body therein.
The method of curing the crosslinkable composition by subsequent curing of the above-mentioned coating is not particularly limited. For example, the coating layer may be appropriately adjusted so that a cross-linking reaction of the block copolymer contained in the coating layer and the multi- A method in which the temperature is maintained at a predetermined temperature, or the like.
The present application is also directed to a display device, e.g., an LCD device.
An exemplary display device may include a liquid crystal panel and the polarizing plate or optical laminate attached to one or both sides of the liquid crystal panel. The polarizing plate or the optical laminate may be attached to the liquid crystal panel by the above-described pressure-sensitive adhesive.
Examples of the liquid crystal panel in the apparatus include passive matrix type panels such as TN (twisted nematic) type, STN (super twisted nematic) type, F (ferroelectic) type or PD (polymer dispersed) type; An active matrix type panel such as a two terminal or a three terminal; A known panel such as an in-plane switching (IPS) panel and a vertical alignment (VA) panel may be used.
Other types of liquid crystal display devices, such as a color filter substrate or an array substrate, are not particularly limited, and configurations known in the art can be employed without limitation.
The crosslinkable composition can also be used for forming a pressure-sensitive adhesive in a conductive film. For example, the conductive film has a film base and a transparent conductor layer laminated on one side of the film base, wherein the crosslinkable composition is formed on the other side of the film base or on the side of the transparent conductor layer Sensitive adhesive layer can be formed. Such a conductive film can be used as a transparent conductive film with a pressure-sensitive adhesive layer used in a capacitive touch panel. Conductive films having such a structure are well known in the art. The crosslinkable composition forming the pressure-sensitive adhesive layer in the above may include a block copolymer and a crosslinking agent. As the block copolymer, the above-mentioned block copolymer can be applied. For example, the polymer segment having a different glass transition temperature has the first block and the second block described above, and in the second block, A copolymerizable monomer having a crosslinkable functional group may be contained as a monomer unit. In this structure, the thickness of the pressure-sensitive adhesive layer can be adjusted within a range of, for example, about 30 μm to 300 μm.
The present application can provide a crosslinkable composition capable of forming, for example, a pressure-sensitive adhesive or an adhesive as the crosslinkable composition. The pressure-sensitive adhesive or adhesive has excellent heat resistance and endurance reliability, and can exhibit excellent stress relaxation and warpage suppression characteristics even when it is combined with an optical film or a conductive film of a thin film.
Hereinafter, the crosslinkable composition will be described in detail through examples and comparative examples, but the scope of the pressure-sensitive adhesive composition is not limited by the following examples.
The physical properties of the present examples and comparative examples were evaluated in the following manner.
1. Evaluation of molecular weight characteristics
The number average molecular weight (Mn) and the molecular weight distribution (PDI) of the copolymer were measured using GPC (Gel Permeation Chromatography), and the measurement conditions of GPC were as follows. The calibration curve was prepared using standard polystyrene (Aglient system).
≪ GPC measurement condition >
Measurer: Aglient GPC (Aglient 1200 series, U.S.)
Column: Two PL Mixed B connections
Column temperature: 40 ° C
Eluent: THF (Tetrahydrofuran)
Flow rate: 1.0 mL / min
Concentration: ~ 1 mg / mL (100 μL injection)
2. Measurement of bending distance
Prepare STN sodalime glass (4x41 cm2, 0.4 t) for bending. If there is no foreign matter, use it without washing. If there is foreign material, clean it with EAc and IPA solvent and dry it with air-gun. Prepare a polarizing plate (coated product) with adhesive on 3.5 × 40 cm2 long MD direction and attach the specimen using a laminator to the prepared glass for bending. After measuring the initial value of glass with specimen, store it at 60 ℃ for 72 hours. Prepare a device to fix the sample in the chamber as shown in the figure below, fix it on one side of the bending sample, and measure the distance from the reference point. Prepare three samples for the same prescription and calculate the average value.
3. Evaluation of durability
The polarizing plates prepared in Examples and Comparative Examples were cut to have a width of about 180 mm and a length of about 320 mm, and they were attached to a commercially available liquid crystal panel of 19 inches. Thereafter, the liquid crystal panel with the polarizer attached thereto is stored in an autoclave (50 DEG C, 5 atm) for about 20 minutes to prepare a sample. The durability against moisture and heat of the prepared sample was evaluated by observing the occurrence of bubbles and peeling at the adhesive interface after the sample was left at 60 ° C and 90% relative humidity for 500 hours. The durability was evaluated by the following criteria: Lt; [deg.] ≫ C for 500 hours, the occurrence of air bubbles and peeling was observed and evaluated according to the following criteria.
<Heat resistance evaluation standard>
A: No polarizing plate front bubble
B: One to 20 front bubbles
C: More than 20 front bubbles
<Evaluation criteria for wet heat>
A: No bubbles and peeling occurred
B: Bubbles and / or slight peeling occurred
C: large amount of bubbles and / or peeling occurred
4. Glass transition temperature
The glass transition temperature (Tg) of each block of the block copolymer or the block copolymer was calculated according to the following equation (A).
≪ Formula A >
1 / Tg =? Wn / Tn
In the formula A, Wn is the weight fraction of the monomer applied to each block of the block copolymer or the copolymer, and Tn is the glass transition temperature when each of the monomers forms a homopolymer. That is, in the formula (A), the value obtained by dividing the weight fraction of the used monomers by the glass transition temperature (Wn / Tn) obtained when the monomers are formed into the homopolymer is calculated for each monomer to be.
Manufacturing example 1. Preparation of block copolymer (A1)
0.032 g of EBiB (ethyl 2-bromoisobutyrate), 11.4 g of methyl methacrylate (MMA) and 2.9 g of butyl methacrylate (BMA) were mixed in 6.1 g of ethyl acetate (EAc). The reactor containing the mixture was sealed, nitrogen purged and stirred at about 25 캜 for about 30 minutes, and dissolved oxygen was removed through bubbling. Then 0.002 g of CuBr2, 0.006 g of TPMA (tris (2-pyridylmethyl) amine) and 0.003 g of 2,2'-azobis (2,4-dimethyl valeronitrile) were added to the deoxygenated mixture And the reaction was initiated by immersing the reaction mixture in a reaction tank at about 67 DEG C (polymerization of the first block). At the time when the conversion of methyl methacrylate was about 70%, 112.1 g of butyl acrylate (BA) previously bubbled with nitrogen, 1.61 g of hydroxybutyl acrylate (HBA), 20.07 g of ethylhexyl acrylate (EHA) And 75 g of ethyl acetate (EAc) were added in the presence of nitrogen. Then, 0.004 g of CuBr 2, 0.01 g of TPMA and 0.01 g of V-65 were added to the reactor, and chain extension reaction was carried out (polymerization of the second block). When the conversion of the monomer (BA) reaches 80% or more, the reaction mixture is exposed to oxygen, diluted with an appropriate solvent, and the reaction is terminated to prepare a block copolymer (in the above process, V- The reaction mixture was appropriately divided and added until the end of the reaction.)
Manufacturing example 2 to 8. The block copolymers (A2, A3, A4, A5, A6 And B1, B2 )
A block copolymer was prepared in the same manner as in Preparation Example 1, except that the raw materials used in the polymerization of the first block and the second block were adjusted in the same ratios as in Table 1
BA: butyl acrylate (homopolymer Tg: about -54 ° C)
HBA: 4-hydroxybutyl acrylate (homopolymer Tg: about -80 ° C)
MMA: methyl methacrylate (homopolymer Tg: about 110 ° C)
BMA: butyl methacrylate (homopolymer Tg: about 27 ° C)
EHA: Ethylhexyl acrylate (homopolymer Tg: approx. -50 ° C)
LA: Lauryl acrylate (homopolymer Tg: about -3 ° C)
Tg: glass transition temperature
Mn: number average molecular weight
PDI: molecular weight distribution
Manufacturing example 3. Preparation of random copolymer (B3)
58.8 parts by weight of n-butylacrylate (BA), 1.2 parts by weight of hydroxybutyl acrylate, 1 part by weight of lauryl acrylate : LA). Then, ethylacetate (EAc) was added as a solvent to the reaction TSC 50. After nitrogen gas was purged for 60 minutes to remove oxygen, the temperature was maintained at 60 DEG C, and 0.09 parts by weight of azobisisobutyronitrile (AIBN) as a reaction initiator was added thereto. The reaction was conducted for 8 hours, To prepare a copolymer (B3). A weight average molecular weight of 42,000, and a molecular weight distribution of 5.0.
Manufacturing example 4. Preparation of random copolymer (B4)
A 1 L reactor equipped with a cooling device equipped with a nitrogen gas refluxing and easy temperature control was charged with a mixture of monomers consisting of 98.8 parts by weight of n-butylacrylate (BA) and 1.2 parts by weight of hydroxybutyl acrylate . Then, 150 parts by weight of ethylacetate (EAc) was added as a solvent. After nitrogen gas was purged for 60 minutes to remove oxygen, the temperature was maintained at 60 DEG C, and 0.09 parts by weight of azobisisobutyronitrile (AIBN) as a reaction initiator was added thereto. The reaction was conducted for 8 hours, To prepare a copolymer (B4). The weight average molecular weight was 440,000, and the molecular weight distribution was 5.0.
Example One.
Preparation of coating liquid (pressure-sensitive adhesive composition)
0.13 part by weight of a TDI cross-linking agent (Coronate L, manufactured by NPU of Japan), 0.15 part by weight of DBTDL (Dibutyltin dilaurate) and 100 parts by weight of a silane coupling agent having a beta-cyanoacetyl group were added to 100 parts by weight of the block copolymer (A1) , And ethyl acetate as a solvent were mixed to prepare a coating liquid (pressure-sensitive adhesive composition) by adjusting the coating solid content to about 30% by weight.
Production of adhesive polarizer
The coating liquid thus prepared was coated on a release treated surface of poly (ethylene terephthalate) (MRF-38, manufactured by Mitsubishi) having a thickness of 38 탆 and subjected to release treatment so that the thickness after drying was about 23 탆, And maintained for 3 minutes. After drying, a coating layer formed on the releasing PET was laminated on one side of a polarizing plate (COP / PVA / COP laminated structure: COP = cyclopolyolefin, PVA = polyvinyl alcohol polarizing film) to produce a pressure-sensitive polarizing plate.
Example 1 to 6 and Comparative Example 1 to 4
A pressure-sensitive adhesive composition (coating solution) and a pressure-sensitive polarizing plate were prepared in the same manner as in Example 1, except that components and ratios were controlled as shown in Table 2 below.
Cross-linking agent: Coronate L, Japan NPU
DBTDL: Dibutyltin dilaurate
SCA: Silane coupling agent having a? -Cyano acetyl group (M812, manufactured by LG Chemical)
The results of the physical properties evaluation of each of the above Examples and Comparative Examples are shown in Table 3 below.
Claims (14)
Wherein the pressure-sensitive adhesive layer comprises a block copolymer and a cross-linking agent,
Wherein the block copolymer is a (meth) acrylic polymer segment having a glass transition temperature different from each other, wherein the first block has a glass transition temperature of 50 ° C or higher and a glass transition temperature of -10 ° C or lower, A second block comprising an alkyl acrylate having an alkyl group and an alkyl acrylate having an alkyl group having 6 or more carbon atoms,
Wherein the second block comprises, as a monomer unit, a copolymerizable monomer having a crosslinkable functional group,
Wherein the thickness of the pressure-sensitive adhesive layer is in the range of 30 to 300 占 퐉.
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| KR1020160116486A KR20180028749A (en) | 2016-09-09 | 2016-09-09 | Crosslinkable Composition |
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| KR1020160116486A KR20180028749A (en) | 2016-09-09 | 2016-09-09 | Crosslinkable Composition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109609020A (en) * | 2018-12-03 | 2019-04-12 | 宁波激智科技股份有限公司 | A kind of coating composition and a kind of optical brightening membrane of that resist warping and preparation method thereof |
| KR20210009865A (en) * | 2019-07-18 | 2021-01-27 | 주식회사 엘지화학 | presuure-sensitive adhesive composition, protective film, optical laminate and display device |
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2016
- 2016-09-09 KR KR1020160116486A patent/KR20180028749A/en not_active Application Discontinuation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109609020A (en) * | 2018-12-03 | 2019-04-12 | 宁波激智科技股份有限公司 | A kind of coating composition and a kind of optical brightening membrane of that resist warping and preparation method thereof |
| CN109609020B (en) * | 2018-12-03 | 2021-03-16 | 宁波激智科技股份有限公司 | Anti-warping optical brightness enhancement film and preparation method thereof |
| KR20210009865A (en) * | 2019-07-18 | 2021-01-27 | 주식회사 엘지화학 | presuure-sensitive adhesive composition, protective film, optical laminate and display device |
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