WO2015030550A1 - 블록 공중합체 - Google Patents
블록 공중합체 Download PDFInfo
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- WO2015030550A1 WO2015030550A1 PCT/KR2014/008138 KR2014008138W WO2015030550A1 WO 2015030550 A1 WO2015030550 A1 WO 2015030550A1 KR 2014008138 W KR2014008138 W KR 2014008138W WO 2015030550 A1 WO2015030550 A1 WO 2015030550A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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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
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
Definitions
- the present application relates to a block copolymer, a method for producing a block copolymer, a curable resin composition, and a film.
- Block copolymers with two or more immiscible blocks are phase-separated when the film is formed, and are spherical, gyroid, cylindrical, and multilayer depending on the content ratio of each block. (lamellar) and the like phase.
- the spherical structure phase is a phase in which spherical domains are interspersed in the matrix, and since the spherical domains can serve as physical crosslinking points, application areas requiring thermoplastic properties, for example, high heat resistance and It can be used in the technical field where durability is required.
- the present application provides a block copolymer, a method for producing the block copolymer, a curable resin composition and a film.
- the block copolymer may include a hard segment having a glass transition temperature of 25 ° C. or higher; And a soft segment having a glass transition temperature of 10 ° C. or less and having a polymerized unit derived from a crosslinkable monomer, wherein the concentration of the polymerized unit derived from the crosslinkable monomer is added to the hard segment in a region adjacent to the hard segment. Higher than non-adjacent areas Accordingly, in the soft segment of the block copolymer, the crosslinkable functional groups are present at high density in the region adjacent to the hard segment.
- the phase-separation film is formed and crosslinked using the block copolymer, a shell layer having a high crosslinking density surrounding the hard segment is formed, and thus the temperature is higher than the glass transition temperature of the hard segment. Even under the conditions, the shell layer can prevent the phenomenon that the hard segments are completely loosened and the image disappears, whereby the film can further secure durability under high temperature and harsh conditions.
- the block copolymer of the present application includes a hard segment having a glass transition temperature of 25 ° C. or more and a soft segment having a glass transition temperature of 10 ° C. or less.
- the "hard segment” refers to a part having a relatively rigid physical property in the block copolymer
- the “soft segment” refers to a part having a relatively soft physical property in the block copolymer
- the glass transition temperature of the hard segment may be 25 °C or more, for example, 30 °C to 200 °C, 50 °C to 100 °C or 55 °C to 90 °C. Within the range of the glass transition temperature as described above, the hard segment may exist in a glass phase at room temperature, and may have hard physical properties.
- the glass transition temperature of the soft segment may be 10 °C or less, for example, -80 °C to 10 °C, -80 °C to 5 °C or -80 °C to 0 °C.
- the soft segment may have molecular flowability at room temperature, and thus may have soft physical properties.
- room temperature is a natural temperature that is not reduced or warmed, for example, about 10 ° C to 30 ° C, about 15 ° C to 30 ° C, about 20 ° C to 30 ° C, 25 ° C or 23 ° C. It can mean a degree of temperature.
- the monomer forming the hard segment is not particularly limited as long as it is a monomer capable of providing a hard segment having a glass transition temperature of 25 ° C. or higher.
- the hard segment may be derived from a methacrylic monomer. And polymerized units.
- the kind of the methacrylic monomer is not particularly limited, and may be, for example, an alkyl methacrylate having a C1-C18 alkyl group, polyethylene glycol methacrylate, polyethylene glycol methacrylate alkyl ester, benzyl methacrylate, or the like. have.
- the alkyl group included in the alkyl methacrylate when the alkyl group included in the alkyl methacrylate is too long, it is difficult to control the glass transition temperature (Tg), so that the carbon number is 1 to 14, preferably Preference is given to using alkyl methacrylates having alkyl groups of 1 to 12.
- Such monomers include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, sec-butyl methacrylate, pentyl methacrylate, 2-ethylhexyl methacrylate, 2 -Ethylbutyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, isononyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, adamantyl methacrylate And tetradecyl methacrylate can be used one or two or more kinds selected from the group consisting of.
- an aromatic monomer such as styrene may be used to form a hard segment having a high glass transition temperature
- the efficiency of the chain extension reaction is lower than that of methacrylate. Problems of low efficiency of copolymer synthesis may occur, and in the block copolymer of the present application, the above problems may be solved by forming hard segments using a methacrylic monomer.
- the hard segment may be included in an amount of 5 to 25 wt%, for example, 5 to 15 wt%, 10 to 25 wt%, or 7 to 17 wt% of the total block copolymer.
- the soft segment has a polymerized unit derived from a crosslinkable monomer comprising a crosslinkable functional group.
- the crosslinkable monomer increases the chemical crosslink density around the hard segment without increasing the glass transition temperature of the hard segment, and is included in a polymerized form in the soft segment as a structure for suppressing complete separation of the hard segment at a high temperature. .
- FIG. 1 is a diagram schematically showing an exemplary block copolymer of the present application.
- the concentration of polymerized units derived from a crosslinkable monomer comprising a crosslinkable functional group is added to the hard segment in a region adjacent to the hard segment.
- more crosslinkable functional groups may be distributed in the region adjacent to the hard segment than in the region not adjacent to the hard segment. That is, in the soft segment of the block copolymer, the crosslinkable functional groups are present at a higher density in the region adjacent to the hard segment than in the region not adjacent to the hard segment.
- FIG. 2 is a diagram schematically illustrating a phase separation structure including spherical domains generated when a phase separation film is formed using the block copolymer according to the present application.
- the crosslinking density surrounding the hard segment is high due to the concentration distribution of the crosslinkable functional groups in the soft segment.
- a layer is formed, and the shell layer may serve to prevent the hard segment from completely loosening even in the harsh conditions above the glass transition temperature of the hard segment, thereby eliminating the spherical domain, thereby further improving the durability of the film in the harsh conditions. It can be secured.
- concentration of a polymerized unit derived from a crosslinkable monomer refers to the number of crosslinkable functional groups per 100 repeating units of an acrylic monomer in a polymer forming a soft segment, and the higher the concentration, the more crosslinkable functional groups. Means more quantity is distributed.
- the crosslinkable functional group may be 0.1 to 5, preferably 0.5 to 3, per 100 repeating units of the acrylic monomer in the polymer.
- the "area adjacent to the hard segment” and the “area not adjacent to the hard segment” are “area relatively close to the hard segment within the soft segment” and “area relatively far from the hard segment within the soft segment”, respectively. Means.
- the monomer forming the soft segment is not particularly limited as long as it is a monomer capable of providing a soft segment having a glass transition temperature of 10 ° C. or lower.
- the soft segment may be formed from an acrylic monomer and a crosslinkable monomer. Polymerized units to be derived.
- the type of the acrylic monomer is not particularly limited, and may be, for example, alkyl acrylate, polyethylene glycol acrylate, polyethylene glycol acrylate alkyl ester, or the like having an alkyl group having 1 to 18 carbon atoms.
- alkyl acrylates having alkyl groups having 1 to 14 carbon atoms, preferably 1 to 12 carbon atoms in view of ease of glass transition temperature control.
- acrylic monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, sec-butyl acrylate, pentyl acrylate, 2-ethylhexyl acrylate, 2-ethylbutyl acrylate,
- One or two or more kinds selected from the group consisting of n-octyl acrylate, isooctyl acrylate, isononyl acrylate, lauryl acrylate and tetradecyl acrylate can be used.
- the crosslinkable monomer may be a monomer including at least one crosslinkable functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, a glycidyl group, an isocyanate group, an amide group, an amino group and an alkoxysilyl group.
- crosslinkable monomer containing the said hydroxy group for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxy Monomers containing hydroxy groups such as hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxyethylene glycol (meth) acrylate, glycerol (meth) acrylate or hydroxypropylene glycol (meth) acrylate It may be used, but may also be used a monomer mixed with one or more of these, but is not limited thereto.
- carboxyl group-containing monomer for example, (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like may be used, but are not limited thereto. no.
- crosslinkable monomer including the glycidyl group for example, an epoxy alkyl (meth) acrylate such as glycidyl (meth) acrylate or epoxycyclohexylmethyl (meth) acrylate may be used.
- the present invention is not limited thereto.
- crosslinkable monomer containing the isocyanate group examples include 2-isocyanatoethyl (meth) acrylate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, and (meth) acryloyloxy ethyl isocyanate.
- amide group-containing monomer examples include (meth) acrylamide, N-vinylpyrrolidone, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N- Dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, diacetone (meth) acrylamide, and the like can be used, but are not limited thereto.
- amino group-containing monomer for example, 2-aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and the like can be used. However, the present invention is not limited thereto.
- alkoxysilyl group-containing monomer 3- (trimethoxysilyl) propyl (meth) acrylate or 2-allyloxyethyl (meth) acrylate may be used, but is not limited thereto.
- (meth) acrylate means an acrylate or methacrylate, and the same is also true for other terms in which “(meth)” is used.
- the number average molecular weight of the block copolymer according to the present application is not particularly limited and may be 5000 to 500,000, for example, 30,000 to 300,000 or 50,000 to 200,000.
- the number average molecular weight is less than 5000, the molecular weight is too small to cause phase separation, and the problem of low crosslinking efficiency may occur in the crosslinking step.
- the number average molecular weight exceeds 500,000, it is difficult to prepare substantially by the living free radical polymerization method to be described later, when the molecular weight is too large may cause a problem of high viscosity when prepared as a solution, high workability.
- the molecular weight distribution of the block copolymer may have a value in the range of more than 1 3 or less, for example, 1.01 to 3, 1.05 to 2.8, preferably 1.1 to 2.0.
- phase separation may not occur or a problem may occur in which it is difficult to implement a desired phase separation structure.
- block copolymer is not particularly limited, but, for example, a diblock copolymer of AB type, a triblock copolymer of ABA type or BAB type, or a gradient having an unclear boundary between blocks. Block copolymers.
- Another embodiment of the present application provides a method of preparing the aforementioned block copolymer.
- the preparation method includes a first polymerization step and a second polymerization step.
- the first polymerization step is a step of polymerizing a monomer that provides a hard segment having a glass transition temperature of 25 ° C. or more, and the monomer that provides a hard segment of 25 ° C. or more of the glass transition temperature may be the aforementioned metaacryl monomer.
- the monomer and crosslinkability of the monomer having a glass transition temperature of 25 ° C. or more and the conversion of the monomers providing a hard segment having a glass transition temperature of 10 ° C. or less are terminated at 60% or more.
- the monomer is put into a reactor and polymerized.
- the monomer providing the soft segment having a glass transition temperature of 10 ° C. or less may be the aforementioned acrylic monomer, and the crosslinkable monomer is the same as described above, and thus description thereof will be omitted.
- the second polymerization step is 2 to 50% by weight of the acrylic monomer and the total cross-linkable monomer contained in the block copolymer 60 to 100% by weight based on the total acrylic monomer contained in the block copolymer Step (a) of the cross-linkable monomer of the polymerization and the conversion of the introduced acrylic monomer is 5 to 90%, 50 to 98% by weight of the acrylic monomer and the block air with respect to the total acrylic monomer included in the block copolymer
- the addition of 0 to 40% by weight of the crosslinkable monomer relative to the total crosslinkable monomer included in the copolymer may include step (b) of polymerization.
- the concentration of the crosslinkable monomer is relatively high at the beginning of the reaction in which the chain extension reaction is started, and after the addition of the monomer mixture, the concentration of the crosslinkable monomer is relatively low, so that the crosslinkable monomer in the longitudinal direction of the polymer chain naturally occurs. Deviation in concentration occurs.
- the second polymerization step, the step (c) and the step of polymerizing 2 to 100% by weight of the acrylic monomer and methacrylic cross-linking monomer relative to the total acrylic monomer contained in the block copolymer When the conversion rate of the monomer added in (c) is 5 to 90%, the addition of 0 to 98% by weight of the acrylic monomer with respect to the total acrylic monomer included in the block copolymer may include the step (d) have.
- 2 to 100% by weight of the acrylic crosslinkable monomer may be optionally added, in which case, the hard because the rate of addition of the methacryl crosslinkable monomer is higher than that of the acrylic crosslinkable monomer.
- a block copolymer having a high distribution of the methacrylic crosslinkable monomer around the segment can be prepared. Furthermore, if the acrylic monomer is further added through step (d), since the concentration of the methacryl-based crosslinkable monomer is relatively low, the concentration variation of the crosslinkable functional group in the longitudinal direction of the polymer chain is further increased.
- the polymerization may be carried out by various known polymerization methods capable of producing a block copolymer, and in terms of convenience of reaction conditions, variety of selectable functional groups, and the like, preferably living free radicals It may be carried out by a polymerization method.
- the "living free radical polymerization method” refers to a living polymerization method in which polymerization is performed in a state in which the terminal of the active polymer chain is present as a free radical, and unlike the free radical polymerization method, an initiation reaction with almost no transfer reaction and stop reaction and It means a polymerization method consisting of only the growth reaction.
- the radical active species is rapidly and reversibly converted into a more stable covalently linked species in order to effectively control the transfer reaction and the stop reaction caused by the side reactions generated by the highly reactive radical active species. You can build a system that can be converted.
- radical active species may be generated by various methods, for example, radical active species may be generated by physical external stimulation, or the radical activity may be caused by chemical stimulation. Can produce species.
- the method for generating radically active species by the chemical stimulation by applying heat to the polymerization initiator TEMPO, NMP radical polymerization method (Ntroxide Mediated Radical Polymerization) by radicals activated by a reversible reaction, the carbon-halogen bond at the end of the initiator Atom Transfer Radial Polymerization (ATRP) by radicals formed by reversibly being activated by this transition metal, and RAFT in which growth radicals are generated in such a way that the terminal is attacked by radicals and the functional groups at the terminal are reversibly moved. (Reversible Addition Fragmentation Chain Transfer) radical polymerization method and the like can be exemplified.
- Another embodiment of the present application provides a curable resin composition comprising the block copolymer described above, and in one example, the resin composition may be an adhesive composition.
- the resin composition may further include a crosslinking agent in addition to the block copolymer.
- the crosslinking agent may be additionally included to cause a crosslinking reaction between the acrylic polymers, and may serve to improve adhesion reliability by maintaining cohesion of the pressure-sensitive adhesive layer at elevated temperatures through the formation of a crosslinked structure.
- the crosslinking agent is not particularly limited, and various kinds of known crosslinking agents such as monofunctional crosslinking agents or polyfunctional crosslinking agents may be used in consideration of the crosslinking functional groups included in the resin composition.
- the crosslinking agent may be an isocyanate compound if the crosslinkable functional group in the block copolymer is a hydroxy group
- a polyacid compound may be used if the crosslinkable functional group in the block copolymer is an epoxy group, in addition to the epoxy compound, aziri
- One or more selected from the group consisting of a dine-based compound and a metal chelate-based compound may be used, but is not limited thereto.
- the isocyanate compound is not particularly limited, but for example, toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoborone diisocyanate, tetramethylxylene diisocyanate, naphthalene diisocyanate
- polyols such as triphenylmethane triisocyanate, methylenebis (4-phenylmethane) triisocyanate and trimethylolpropane thereof can be used.
- the epoxy compound is, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, triglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diol Glycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, N, N, N ', N'-tetraglycidyl ethylenediamine and N, N, N', N'-tetraglycidyl
- One or more selected from the group consisting of -1,3-dimethylbenzene may be used, but is not limited thereto.
- Exemplary aziridine-based compounds include N, N'-toluene-2,4-bis (1-aziridinecarboxamide), N, N'-diphenylmethane-4,4'-bis (1-aziri Dinecarboxamide), triethylene melamine, bisisoprotaloyl-1- (2-methylaziridine), and tri-1-aziridinylphosphine oxide may be used. It is not limited.
- the crosslinking agent may be included in an amount of 0.01 parts by weight to 10 parts by weight based on 100 parts by weight of the resin composition, for example, 0.1 parts by weight to 3 parts by weight, based on 100 parts by weight of the resin composition, 1 part by weight to 7 parts by weight, 2 parts by weight to 5 parts by weight, 0.01 parts by weight to 5 parts by weight may be included in the resin composition, but is not limited thereto. It is possible to maintain excellent cohesion and durability of the pressure-sensitive adhesive layer in the above range.
- the resin composition in addition to the above-described block copolymer, within the range that does not affect the effect of the present application, in addition to the above-mentioned block copolymer, tackifier resin, silane coupling agent, antistatic agent, near infrared absorber, ultraviolet stabilizer, antioxidant, colorant, reinforcing agent
- tackifier resin silane coupling agent, antistatic agent, near infrared absorber, ultraviolet stabilizer, antioxidant, colorant, reinforcing agent
- One or more additives selected from the group consisting of fillers, antifoams, surfactants, crosslinking catalysts, leveling agents and plasticizers may be further included.
- the resin composition of the present application may further include a tackifying resin, thereby making it possible to obtain tackiness.
- a tackifying resin is not specifically limited, For example, an epoxy resin, a hydrocarbon resin or its hydrogenated substance, rosin resin or its hydrogenated substance, rosin ester resin or its hydrogenated substance, terpene resin or its hydrogenated substance, terpene phenol
- One or more mixtures, such as resin or its hydrogenated substance, polymeric rosin resin, or polymeric rosin ester resin can be used.
- the tackifying resin may be included in an amount of 1 part by weight to 100 parts by weight based on 100 parts by weight of the resin composition. At 1 part by weight or more, the addition effect can be expected, and at 100 parts by weight or less, it can be expected to improve the compatibility and cohesion.
- the said resin composition can also contain a silane coupling agent further.
- silane coupling agent examples include ethyltrimethoxysilane, ⁇ - (3,4 epoxycyclohexyl), ⁇ -glycidoxypropyl triethoxysilane, and ⁇ -glycidoxypropyl trimethoxysilane.
- the silane coupling agent may be included in the resin composition in an amount of 0.01 parts by weight to 5 parts by weight based on 100 parts by weight of the resin composition.
- the content may be included in the resin composition in an amount of 0.1 part by weight to 3 parts by weight, 1 part by weight to 4 parts by weight, 2 parts by weight to 3 parts by weight, and 0.01 parts by weight to 1 part by weight based on 100 parts by weight of the resin composition.
- the present invention is not limited thereto.
- the content of the silane coupling agent can be expected to increase the adhesion at 0.01 parts by weight or more, and at 5 parts by weight or less, there is no fear that durability durability is lowered.
- the resin composition may further include an antistatic agent, and the antistatic agent is excellent in compatibility with other components included in the composition such as an acrylate copolymer, transparency, workability and durability of the pressure-sensitive adhesive Any compound can be used as long as it can impart antistatic performance to the pressure-sensitive adhesive without adversely affecting it.
- an antistatic agent is excellent in compatibility with other components included in the composition such as an acrylate copolymer, transparency, workability and durability of the pressure-sensitive adhesive Any compound can be used as long as it can impart antistatic performance to the pressure-sensitive adhesive without adversely affecting it.
- the antistatic agent may be included in an amount of 0.01 parts by weight to 5 parts by weight based on 100 parts by weight of the resin composition.
- it may be included in the resin composition in an amount of 0.1 parts by weight to 3 parts by weight, 1 parts by weight to 4 parts by weight, 2 parts by weight to 3 parts by weight, and 0.01 parts by weight to 2 parts by weight based on 100 parts by weight of the resin composition.
- the present invention is not limited thereto.
- the content is 0.01 parts by weight or more, the desired antistatic effect can be obtained, and in 5 parts by weight or less, excellent compatibility with other components, there is no fear of deteriorating the durability or transparency of the pressure-sensitive adhesive.
- the resin composition may further include a crosslinking catalyst
- the crosslinking catalyst is not particularly limited as long as it is a catalyst capable of adjusting the curing rate, dibutyltin dilaurate, triethylamine, diethylenetriamine, One or more selected from the group consisting of bismuth carboxylate and zirconium chelate may be used.
- the crosslinking catalyst may be included in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of solids of the resin composition.
- the resin composition may further include a near-infrared absorber and an ultraviolet stabilizer for light curing, and additives such as antioxidants, colorants, reinforcing agents, fillers, antifoaming agents, surfactants, or plasticizers to supplement physical properties as necessary. It may further include.
- the resin composition may be variously used in the technical field requiring excellent durability.
- the resin composition may be used for a polarizer, an adhesive for protective films of various displays, or a gap filler for various displays, but is not limited thereto. .
- Another embodiment of the present application is formed by the curable resin composition, and provides a film, for example, an adhesive film comprising a cured product of the resin composition.
- the resin composition includes a block copolymer, and thus, when the resin composition is formed into a film, it includes a phase separation structure.
- the phase separation structures comprise spherical domains.
- the spherical domain may serve as a physical crosslinking point in the film, and the phase-separated copolymer film having the physical crosslinking point may exhibit excellent physical durability as compared with a general copolymer film. Therefore, the film having a phase-separated structure having a spherical domain prepared from the above-described block copolymer may exhibit high durability compared to the physical durability of the film that can be realized by random copolymers having the same molecular weight, and may also be a relatively low molecular weight copolymer. Desired physical durability can be satisfied.
- the film having a phase-separated structure according to the present application is a block copolymer film having both chemical crosslinking and physical crosslinking, it is condensed in the film or the substrate due to softening of the hard segment at high temperature compared to the block copolymer film consisting of only chemical crosslinking.
- an adhesive film or a gap filler for a display to which a thin glass substrate is applied It can be usefully applied.
- the hard segment of the block copolymer film when softened at a temperature higher than the glass transition temperature, it exhibits a stress relaxation effect, but may be repeatedly exposed to high temperature, thereby deteriorating durability. This is because, in the absence of solvent, the two phases mixed at or above the glass transition temperature cannot easily undergo phase separation and reformation of physical crosslinking points as compared with film production. In addition, it is not possible to increase the glass transition temperature of the hard segment indefinitely in order to improve durability at high temperature, which is an advantage that occurs when maintaining a high concentration of solids by increasing the viscosity of the polymer when the glass transition temperature of the hard segment is high. It is lost.
- the block copolymer film according to the present application can increase the chemical crosslinking density around the hard segment without increasing the glass transition temperature of the hard segment, thereby suppressing the complete separation of the hard segment even under severe conditions, thus improving stress relaxation characteristics. And high temperature durability at the same time.
- the adhesive film may be applied to, for example, a polarizing plate.
- the substrate layer For example, the present application, the substrate layer; And an optical member formed on one surface or both surfaces of the substrate layer and including an adhesive film containing the resin composition.
- the base layer may be a polarizer, a polarizing plate, a retardation plate, a viewing angle compensation film, or a brightness enhancing film.
- the base layer may be a polarizing plate.
- the kind of polarizing film included in the polarizing plate is not particularly limited, and for example, a general kind known in the art such as polyvinyl alcohol-based polarizing film can be used without limitation.
- the polarizing film is a functional film capable of extracting only light vibrating in one direction from incident light while vibrating in various directions.
- a polarizing film may be a form in which a dichroic dye is adsorbed and oriented in a polyvinyl alcohol-based resin film, for example.
- Polyvinyl alcohol-type resin which comprises a polarizing film can be obtained by gelatinizing polyvinylacetate-type resin, for example.
- the polyvinylacetate resin which can be used may include not only a homopolymer of vinyl acetate but also a copolymer of vinyl acetate and other monomers copolymerizable with the above.
- Examples of the monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and a mixture of one or two or more kinds of acrylamides having an ammonium group, but are not limited thereto. no.
- the polarizing film is a step of stretching the polyvinyl alcohol resin film as described above (ex. Uniaxial stretching), dyeing the polyvinyl alcohol resin film with a dichroic dye, adsorbing the dichroic dye, and a dichroic dye.
- the adsorbed polyvinyl alcohol-based resin film can be produced through a process of treating with boric acid aqueous solution, and a process of washing with water after treating with boric acid aqueous solution.
- the dichroic dye iodine or a dichroic organic dye may be used.
- the polarizing plate may further include a protective film attached to one side or both sides of the polarizing film, in which case, the adhesive film may be formed on one side of the protective film.
- the type of protective film is not particularly limited, and includes, for example, a cellulose film such as triacetyl cellulose (TAC); Polyester film such as polycarbonate film or PET (poly (ethylene terephthalet)); Polyether sulfone-based film; Alternatively, a film having a laminated structure of one layer or two or more layers, such as a polyethylene film, a polypropylene film or a polyolefin-based film produced using a resin having a cyclo or norbornene structure, an ethylene-propylene copolymer, or the like can be used.
- the polarizing plate may further include one or more functional layers selected from the group consisting of a protective layer, a reflective layer, an antiglare layer, a retardation plate, a wide viewing angle compensation film, and a brightness enhancing film.
- a method of forming an adhesive film on the polarizing plate as described above is not particularly limited.
- the resin composition or a coating liquid containing the same may be applied to a substrate or the like by a common means such as a comma coater or a bar coater, and then cured.
- coating and hardening a resin composition on the surface of a peelable base material once can be used.
- the method of curing the resin composition in the above process is also not particularly limited, and for example, the acrylic polymer and the crosslinking agent included in the composition may be subjected to an appropriate aging process or to induce a polymerization reaction of the photopolymerizable compound. It can carry out through irradiation of light which can be performed, for example, ultraviolet irradiation. In one example, the ultraviolet irradiation may be performed using, for example, a high pressure mercury lamp, an electrodeless lamp, or a xenon lamp. In addition, during UV curing.
- the irradiation amount of light is not particularly limited as long as it is controlled to such a degree that sufficient curing is achieved without impairing the overall physical properties, for example, illuminance is 50 mW / cm 2 to 1,000 mW / cm 2 , and light amount 50 mJ / cm 2 to 1,000 It is preferable that it is mJ / cm ⁇ 2> .
- the present application may relate to a liquid crystal display device attached to a liquid crystal panel by an adhesive film of the optical member.
- the optical member may be a polarizing plate.
- the liquid crystal panel in the apparatus may be, for example, a passive matrix panel such as twisted nematic (TN) type, super twisted nematic (STN) type, ferroelectic (F) type or polymer dispersed (PD) type; Active matrix panels such as two-terminal or three-terminal; All known panels, such as an In Plane Switching (IPS) panel and a Vertical Alignment (VA) panel, can be applied.
- TN twisted nematic
- STN super twisted nematic
- F ferroelectic
- PD polymer dispersed
- Active matrix panels such as two-terminal or three-terminal
- All known panels such as an In Plane Switching (IPS) panel and a Vertical Alignment (VA) panel, can be applied.
- IPS In Plane Switching
- VA Vertical Alignment
- liquid crystal display device for example, upper and lower substrates such as a color filter substrate or an array substrate, are not particularly limited, and configurations known in the art may be employed without limitation.
- the chemical crosslink density around the hard segment can be increased without increasing the glass transition temperature of the hard segment, so that the complete separation of the hard segment can be suppressed even under the harsh conditions of high temperature, thereby improving the high temperature durability. I can keep it.
- FIG. 1 is a diagram schematically showing an exemplary block copolymer of the present application.
- FIG. 2 is a diagram schematically illustrating a phase separation structure including spherical domains generated when a phase separation film is formed using the block copolymer according to the present application.
- MMA methyl methacrylate
- BMA butyl methacrylate
- EA ethyl acetate
- ethyl 2-bromo as monomers for preparing hard segments
- 0.65 g of Sobutyrate (ethyl 2-bromoisobutyrate) ATRP initiator was placed in a 500 mL round bottom flask and the flask was sealed.
- the reaction flask was deoxygenated by nitrogen bubbling for 30 minutes and immersed in an oil bath heated to 60 ° C.
- the reaction temperature was controlled to be 60 ° C. while maintaining a nitrogen atmosphere.
- a catalyst solution containing 0.016 g of CuBr 2 , 0.052 g of Tris (2-pyridylmethyl) amine (TPMA), and 1.4 mL of DMF was prepared, added to a reactor, and tin dioctoate as a catalyst reducing agent. 0.75 g of tin dioctoate was added to initiate the reaction.
- the conversion rate of the reaction was measured by 1 H-NMR, when the conversion rate of BA reached 30%, a mixture of 250 g of BA and EA 250 g, which had been previously deoxygenated, was added to the reactor and the temperature of the reactor was maintained at 60 ° C.
- P (MMA-co-CHMA) macro by adding 50 g of MMA, 84 g of cyclohexyl methacrylate (CHMA), 134 g of EA, 0.65 g of EBiB, 0.24 g of CuBr, and 0.44 g of PMDETA in the same manner as in Preparation Example 1
- MI2 Initiator
- MI2 Initiator
- Oxygen was removed by nitrogen bubbling for 30 minutes.
- the reaction temperature was controlled to be 60 ° C. while maintaining a nitrogen atmosphere.
- a catalyst solution containing 0.016 g of CuBr 2 , 0.052 g of TPMA, and 1.4 mL of DMF was prepared, added to a reactor, and 0.75 g of tin dioctoate was added as a catalyst reducing agent to initiate a reaction.
- the conversion rate of the reaction was measured by 1 H-NMR and the conversion rate of the EHA reached 50%, a mixture of 250 g of EHA and 250 g of EA previously removed from oxygen was added to the reactor and the temperature of the reactor was maintained at 60 ° C.
- MI3 PMMA macroinitiator
- 30 g of purified MI3, 92 g of BA, 15 g of glycidyl methacrylate (GMA), and 107 g of EA were added to a 1 L reactor, and oxygen was removed by nitrogen bubbling for 30 minutes.
- the reaction temperature was controlled to be 60 ° C. while maintaining a nitrogen atmosphere.
- a catalyst solution containing 0.016 g of CuBr 2 , 0.052 g of TPMA, and 1.4 mL of DMF was prepared, added to a reactor, and 0.75 g of tin dioctoate was added as a catalyst reducing agent to initiate a reaction.
- the conversion rate of the reaction was measured by 1 H-NMR, when the conversion rate of BA reached 30%, a mixture of BA 185 g and EA 185 g, which had been previously deoxygenated, was added to the reactor and the temperature of the reactor was maintained at 60 ° C. At this point, the GMA had a 67% conversion rate.
- MI3 30g of Preparation Example 4 n-butyl acrylate (BA) 92g, N, N-dimethylaminoethyl methacrylate (N, N-dimethylaminoethyl methacrylate, DMAEA) 15g, EA 107g, CuBr 2 0.016 g, TPMA 0.052g, tin dioctoate 0.75g was added to the reaction in the same manner as in Preparation Example 4.
- BA n-butyl acrylate
- N, N-dimethylaminoethyl methacrylate N, N-dimethylaminoethyl methacrylate, DMAEA 15g
- EA 107g CuBr 2 0.016 g
- TPMA 0.052g tin dioctoate 0.75g
- AIBN 2,2′-azobisisobutyronitrile
- styrene (S) 100 g of styrene (S), 100 g of EA, and 0.65 g of EBiB were placed in a round bottom flask to seal the flask.
- the reaction flask was deoxygenated by nitrogen bubbling for 30 minutes and immersed in an oil bath heated to 60 ° C.
- 0.24 g of CuBr was added to the prepared 10 mL vial bottle to remove oxygen, and 0.44 g of PMDETA and 7 mL of deoxygenated DMF were added to prepare an ATRP catalyst solution.
- the catalyst solution prepared under a nitrogen atmosphere was put in a flask to initiate a reaction.
- the flask prepared above was bubbled with nitrogen for 30 minutes to remove oxygen from the solution and then heated in a 60 ° C. oil bath.
- a composition solution having a solid content of 30% was prepared in the same manner as in Example 1 except that the block copolymer of Comparative Preparation Example 1 was used.
- a phase separation film was prepared in the same manner as in Example 1 using the solution.
- a composition solution having a solid content of 30% was prepared in the same manner as in Example 4 except that the block copolymer of Comparative Preparation Example 2 was used.
- a phase separation film was prepared in the same manner as in Example 1 using the solution.
- a composition solution having a solid content of 30% was prepared in the same manner as in Example 4 except that the random copolymer of Comparative Preparation Example 3 was used. Using the solution to prepare a film in the same manner as in Example 1. In this case, since a random copolymer resin was used, no microphase appeared.
- a composition solution having a solid content of 30% was prepared in the same manner as in Example 4 except that the block copolymer of Comparative Preparation Example 4 was used. Using the solution to prepare a film in the same manner as in Example 1. In this case, spherical phase formation could not be observed because the copolymer had a relatively high molecular weight distribution value (Mw / Mn).
- the adhesive layer between the glass substrate and the polarizing plate was formed using the resin composition containing the block copolymer and the random copolymer prepared in Examples 1 and 2 and Comparative Examples 1 and 3.
- Polar resin plate specimens were prepared by attaching the resin films prepared in Example 1, Comparative Example 1, and Comparative Example 3 to a polarizing plate.
- the polarizing plate specimens were cut to a size of 180 cm ⁇ 320 cm (length ⁇ width) and attached to a 0.7 mm thick LCD commercial panel. Thereafter, the panel was stored at 50 ° C. and 5 atmospheres for 20 minutes to prepare a sample polarizing plate.
- the prepared sample polarizing plate was left for about 300 hours under conditions of 90 ° C., and then visually observed whether bubbles or peeling phenomenon occurred at the adhesive interface.
- compositions including the block copolymers prepared in Examples 3, 4, and 5 and Comparative Examples 2 and 4 were applied to the adhesive for attaching the film to protect the hard coating layer of ITO glass.
- the films prepared using the resin compositions prepared in Examples 3, 4, and 5 and Comparative Examples 2 and 4 were attached to a hard coating layer opposite to the ITO layer of ITO glass and subjected to ITO annealing at 150 ° C. for 1 hour.
- Durability rating is the same as the case of the pressure-sensitive adhesive for the polarizing plate, the evaluation results are shown in Table 2 below.
- the block copolymer according to the present application does not completely decompose the hard segment, thereby maintaining excellent durability, and due to the presence of physical crosslinking points, even in comparison with random copolymers. High durability.
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Abstract
Description
고분자 종류 | 하드 세그먼트의 Tg | 내구성 | |
실시예 1 | 블록 고분자 | 55℃ | ○ |
실시예 2 | 블록 고분자 | 55℃ | ○ |
비교예 1 | 블록 고분자 | 55℃ | × |
비교예 3 | 랜덤 고분자 | - | × |
고분자 종류 | 하드 세그먼트의 Tg | 내구성 | |
실시예 3 | 블록 고분자 | 91℃ | ○ |
실시예 4 | 블록 고분자 | 105℃ | ○ |
실시예 5 | 블록 고분자 | 105℃ | ○ |
비교예 2 | 블록 고분자 | 105℃ | × |
비교예 4 | 블록 고분자 | 100℃ | × |
Claims (22)
- 유리전이온도가 25℃ 이상인 하드 세그먼트; 및 유리전이온도가 10℃ 이하인 소프트 세그먼트를 포함하고,상기 소프트 세그먼트는 가교성 단량체로부터 유도되는 중합 단위를 가지며, 상기 가교성 단량체로부터 유도된 중합 단위의 농도가 상기 하드 세그먼트에 인접하는 영역에서 상기 하드 세그먼트에 인접하지 않은 영역 보다 높은 블록 공중합체.
- 제 1 항에 있어서, 하드 세그먼트는 메타 아크릴계 단량체로부터 유도되는 중합 단위를 포함하는 블록 공중합체.
- 제 1 항에 있어서, 소프트 세그먼트는 아크릴계 단량체 및 가교성 단량체로부터 유도되는 중합 단위를 포함하는 블록 공중합체.
- 제 1 항에 있어서, 하드 세그먼트의 유리전이온도는 30℃ 내지 200℃인 블록 공중합체.
- 제 1 항에 있어서, 소프트 세그먼트의 유리전이온도는 -80℃ 내지 0℃인 블록 공중합체.
- 제 1 항에 있어서, 가교성 단량체는 히드록시기, 카르복실기, 에폭시기, 글리시딜기, 이소시아네이트기, 아마이드기, 아미노기 및 알콕시실릴기로 이루어진 군으로부터 선택된 하나 이상의 관능기를 포함하는 블록 공중합체.
- 제 1 항에 있어서, 전체 블록 공중합체에 대한 하드 세그먼트의 함량이 5 내지 25 중량%인 블록 공중합체.
- 제 1 항에 있어서, 수평균분자량이 5000 내지 50만인 블록 공중합체.
- 제 1 항에 있어서, 분자량 분포가 1 초과 3 이하인 블록 공중합체.
- 제 1 항에 있어서, 블록 공중합체는 A-B형의 디블록 공중합체; A-B-A형 또는 B-A-B 형의 트리블록 공중합체; 및 그래디언트(gradient) 블록 공중합체로 이루어진 군으로부터 선택된 어느 하나인 블록 공중합체.
- 유리전이온도가 25℃ 이상의 하드 세그먼트를 제공하는 단량체를 중합시키는 제 1 중합 단계; 및 상기 유리전이온도가 25℃ 이상의 하드 세그먼트를 제공하는 단량체의 전환율이 60% 이상에서 중합을 종료하고, 유리전이온도가 10℃ 이하의 소프트 세그먼트를 제공하는 단량체 및 가교성 단량체를 반응기에 넣고 반응시키는 제 2 중합 단계를 포함하는 블록 공중합체의 제조 방법.
- 제 11 항에 있어서, 유리전이온도가 25℃ 이상의 하드 세그먼트를 제공하는 단량체는 메타 아크릴계 단량체인 블록 공중합체의 제조 방법.
- 제 11 항에 있어서, 유리전이온도가 10℃ 이하의 소프트 세그먼트를 제공하는 단량체는 아크릴계 단량체인 블록 공중합체의 제조 방법.
- 제 13 항에 있어서, 제 2 중합 단계는, 블록 공중합체에 포함되는 전체 아크릴계 단량체에 대하여 2 내지 50 중량%의 아크릴계 단량체 및 블록 공중합체에 포함되는 전체 가교성 단량체에 대하여 60 내지 100 중량%의 가교성 단량체를 투입하고 중합시키는 단계 (a); 및 상기 단계 (a)에서 투입된 단량체의 전환율이 5 내지 90%에서, 상기 블록 공중합체에 포함되는 전체 아크릴계 단량체에 대하여 50 내지 98 중량%의 아크릴계 단량체 및 블록 공중합체에 포함되는 전체 가교성 단량체에 대하여 0 내지 40 중량%의 가교성 단량체를 추가로 투입하여 중합시키는 단계 (b)를 포함하는 블록 공중합체의 제조 방법.
- 제 13 항에 있어서, 제 2 중합 단계는, 블록 공중합체에 포함되는 전체 아크릴계 단량체에 대하여 2 내지 100 중량%의 아크릴계 단량체 및 메타아크릴계 가교성 단량체를 투입하고 중합시키는 단계 (c); 및 상기 단계 (c)에서 투입된 단량체의 전환율이 5 내지 90%에서, 상기 블록 공중합체에 포함되는 전체 아크릴계 단량체에 대하여 0 내지 98 중량%의 아크릴계 단량체를 추가로 투입하여 중합시키는 단계 (d)를 포함하는 블록 공중합체의 제조 방법.
- 제 15 항에 있어서, 단계 (c)에서, 아크릴계 가교성 단량체 2 내지 100 중량%를 추가로 투입하는 블록 공중합체의 제조 방법.
- 제 11 항에 있어서, 리빙 자유 라디칼 중합법에 의하여 수행되는 블록 공중합체의 제조 방법.
- 제 1 항의 블록 공중합체 및 가교제를 포함하는 경화성 수지 조성물.
- 제 18 항에 있어서, 점착성 부여 수지, 실란계 커플링제, 대전 방지제, 근적외선 흡수제, 자외선 안정제, 산화 방지제, 조색제, 보강제, 충진제, 소포제, 계면 활성제, 가교 촉진제, 레벨링제 및 가소제로 이루어진 군으로부터 선택된 하나 이상의 첨가제를 추가로 포함하는 수지 조성물.
- 제 18 항의 경화성 수지 조성물의 경화물을 포함하는 필름.
- 제 20 항에 있어서, 구형의 도메인을 포함하는 상분리 구조를 포함하는 필름.
- 제 20 항에 있어서, 상기 필름은 점착 필름인 필름.
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JP2016538864A JP6315298B2 (ja) | 2013-08-30 | 2014-09-01 | ブロック共重合体 |
US14/915,107 US10308751B2 (en) | 2013-08-30 | 2014-09-01 | Block copolymer |
EP14841182.0A EP3040354B1 (en) | 2013-08-30 | 2014-09-01 | Block copolymer |
CN201480054102.XA CN105593256B (zh) | 2013-08-30 | 2014-09-01 | 嵌段共聚物 |
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