WO2013021650A1 - Adamantane-containing polymer - Google Patents
Adamantane-containing polymer Download PDFInfo
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- WO2013021650A1 WO2013021650A1 PCT/JP2012/005071 JP2012005071W WO2013021650A1 WO 2013021650 A1 WO2013021650 A1 WO 2013021650A1 JP 2012005071 W JP2012005071 W JP 2012005071W WO 2013021650 A1 WO2013021650 A1 WO 2013021650A1
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- acrylate
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
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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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
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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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
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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
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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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
- C08F2810/00—Chemical modification of a polymer
- C08F2810/30—Chemical modification of a polymer leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
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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
- C08F2810/00—Chemical modification of a polymer
- C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
Definitions
- the present invention relates to a polymer, a resin composition containing the polymer, and a hard coat film having a cured layer obtained from the resin composition.
- Patent Document 1 discloses a method of providing two or more hard coat layers on at least one surface of a plastic film.
- this method has a problem that the coating process for providing two or more hard coat layers becomes complicated and the production cost increases.
- Patent Document 2 discloses that a reactive polymer obtained by addition-reacting an unsaturated monocarboxylic acid to an epoxy group-containing (meth) acrylic copolymer is used for the hard coat layer. It was hard to say that the balance of curl suppression was sufficient.
- An object of the present invention is to provide a polymer capable of producing a hard coat film having high hardness and curling suppressed.
- a polymer comprising a structure represented by the following formula (I).
- R ⁇ 1 >, R ⁇ 4 > and R ⁇ 6 > are a hydrogen atom or a methyl group, respectively.
- R 2 and R 5 are each a divalent aliphatic hydrocarbon group containing one or more selected from a hydroxyl group, a halogen atom and a hetero atom, a divalent aliphatic hydrocarbon group or a single bond.
- R 3 is a hydrocarbon group, a halogen-substituted hydrocarbon group, a cyclic hydrocarbon group, a halogen-substituted cyclic hydrocarbon group, a halogen atom, a hydroxyl group, a carboxyl group, or an oxo group.
- m represents an integer of 0 to 15.
- the polymer represented by the formula (I) is a polymer 1 in which R 2 is a single bond and m is 0. 3.
- a polymer obtained by reacting (meth) acrylic acid with an epoxy group of a copolymer obtained by copolymerizing (meth) acrylate having an adamantyl group and (meth) acrylate having an epoxy group bonded, or an adamantyl group having been bonded A polymer obtained by reacting (meth) acrylate having an epoxy group bonded to a carboxyl group of a copolymer obtained by copolymerizing (meth) acrylate and (meth) acrylic acid. 4.
- a resin composition comprising the polymer according to any one of 1 to 3 and a photopolymerization initiator.
- a polymer capable of producing a hard coat film with high hardness and curling suppressed can be provided.
- the polymer of the present invention includes a structure represented by the following formula (I).
- R ⁇ 1 >, R ⁇ 4 > and R ⁇ 6 > are a hydrogen atom or a methyl group, respectively.
- R 2 and R 5 are each a divalent aliphatic hydrocarbon group containing one or more selected from a hydroxyl group, a halogen atom and a hetero atom, a divalent aliphatic hydrocarbon group or a single bond.
- R 3 is a hydrocarbon group, a halogen-substituted hydrocarbon group, a cyclic hydrocarbon group, a halogen-substituted cyclic hydrocarbon group, a halogen atom, a hydroxyl group, a carboxyl group, or an oxo group ( ⁇ O).
- m represents an integer of 0 to 15.
- Each group of the polymer represented by the formula (I) is as follows.
- Examples of the divalent aliphatic hydrocarbon group containing one or more selected from a hydroxyl group, a halogen atom and a hetero atom of R 2 and R 5 include the following three structures. (In the formula, n is an integer of 0 or more.)
- Examples of the divalent aliphatic hydrocarbon group for R 2 and R 5 include a methylene group, an ethylene group, and a butylene group.
- Examples of the hydrocarbon group for R 3 include a methyl group, an ethyl group, a butyl group, and a t-butyl group.
- Examples of the cyclic hydrocarbon group for R 3 include a cyclopentyl group and a cyclohexyl group.
- the halogen-substituted hydrocarbon group for R 3 is a group obtained by substituting the hydrogen atom of the hydrocarbon group with a halogen atom.
- the halogen-substituted cyclic hydrocarbon group for R 3 is a group obtained by substituting the hydrogen atom of the cyclic hydrocarbon group with a halogen atom.
- oxo group of R 3 two of R 3 are attached to the same carbon atom of the adamantane skeleton, and the two R 3 are both hydroxyl groups and the case where these hydroxyl groups are condensed.
- the polymer represented by the formula (I) is preferably a polymer in which R 2 is a single bond (directly bonded) and m is 0.
- the polymer containing the structure represented by the formula (I) is obtained by copolymerizing (meth) acrylate having an adamantyl group bonded thereto and (meth) acrylate having an epoxy group bonded thereto. (Meth) acrylic acid is reacted; or (meth) acrylate having adamantyl group bonded thereto and (meth) acrylic acid are copolymerized, and then an epoxy group is bonded to the carboxyl group of the resulting copolymer (meth) It can be produced by reacting acrylate.
- (Meth) acrylate to which an adamantyl group is bonded is, for example, a compound having the following structure. (In the formula, R 1 , R 2 , R 3 and m are the same as in formula (I).)
- the (meth) acrylate to which the epoxy group is bonded is, for example, a compound having the following structure.
- a group in which R 5 ′ and a ring-opened epoxy group are combined corresponds to R 5 .
- R 4 is the same as in formula (I).
- R 5 ′ is a divalent aliphatic hydrocarbon group containing at least one selected from a hydroxyl group, a halogen atom and a hetero atom, a divalent aliphatic hydrocarbon group or a single bond.
- (Meth) acrylic acid is a compound having the following structure, for example. (Wherein R 6 is the same as in formula (I).)
- the above copolymerization can be carried out, for example, by a known radical polymerization method, and may be performed using a radical polymerization initiator or the like in a solvent or without a solvent.
- the radical polymerization initiator include azo initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis-methylbutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide Peroxide initiators, such as an oxide, are mentioned.
- chain transfer agents such as a dodecyl mercaptan, a lauryl mercaptan, a thioglycolic acid ester, and a mercaptoethanol, as needed.
- the amount of radical polymerization initiator used is the total of (meth) acrylates to which copolymerized adamantyl groups are bonded and (meth) acrylates to which epoxy groups are bonded, or (meth) acrylates and (meth) acrylic acids to which adamantyl groups are bonded.
- the amount is usually 0.01 to 50 parts by mass, preferably 0.01 to 30 parts by mass with respect to 100 parts by mass.
- Solvents used for copolymerization include alkyl alcohols such as methanol, ethanol, n-propanol and isopropanol; glycol ethers such as methyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; ethers such as tetrahydrofuran, dioxane and diisopropyl ether; acetone, methyl ethyl ketone and methyl isobutyl Ketones such as ketone and cyclohexanone; methyl acetate, ethyl acetate, acetic acid-n-propyl
- the solvent used for copolymerization is a copolymer component ((meth) acrylate having an adamantyl group bonded and (meth) acrylate having an epoxy group bonded, or (meth) acrylate and (meth) acrylic acid having an adamantyl group bonded)).
- the total concentration is, for example, 0.5% by mass or more, preferably 5% by mass or more.
- the copolymer component may be in a suspended state, but is preferably dissolved.
- the reaction temperature for the copolymerization reaction is usually 0 to 200 ° C., preferably 20 to 150 ° C. When the temperature is lower than 0 ° C., the reaction rate may decrease. On the other hand, when the temperature is higher than 200 ° C., the resulting polymer may be intensely colored.
- the reaction pressure for the copolymerization reaction is usually 0.01 to 10 MPa in absolute pressure, preferably normal pressure to 1 MPa. When the pressure exceeds 10 MPa, there is a problem in terms of safety, and a special device is required, which is not preferable.
- the reaction time depends on the type and amount of the polymerization initiator, the reaction temperature, etc., but is usually 1 minute to 24 hours, preferably 1 to 10 hours.
- (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) Examples thereof include acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and ⁇ -butyrolactone (meth) acrylate.
- Addition reaction after copolymerization reaction that is, a reaction of adding (meth) acrylic acid to a copolymer of (meth) acrylate bonded with an adamantyl group and (meth) acrylate bonded with an epoxy group; or an adamantyl group bonded
- the reaction of adding a (meth) acrylate having an epoxy group bonded to a copolymer of (meth) acrylate and (meth) acrylic acid may be carried out in a solvent.
- Solvents that can be used for the addition reaction include cyclohexane, methylcyclohexane, ethylcyclohexane, toluene, xylene, MEK (methyl ethyl ketone), MIBK (methyl isobutyl ketone), DMF (dimethylformamide), NMP (N-methyl-2-pyrrolidone), Examples include DMAc (N, N-dimethylacetamide), DMSO (dimethyl sulfoxide), and propylene glycol monomethyl ether acetate.
- a catalyst may be used during the addition reaction, and examples of the catalyst include tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, triphenylphosphine, and pyridine.
- the constitutional unit ratio (molar ratio) of the adamantyl unit and (meth) acryl unit of the polymer containing the structure represented by the formula (I) reflects the blending ratio at the time of copolymerization, and the adamantyl unit is 1% to 99%, preferably Is 10% to 90%.
- the adamantyl unit is less than 10%, the curl of the obtained hard coat film may increase, and even when it exceeds 90%, there is no significant difference in the physical properties of the obtained hard coat film.
- the polymerization form of the polymer represented by the formula (I) is not particularly limited, for example, it is a random copolymer.
- the polymer containing the structure represented by the formula (I) is a polymer composed only of an adamantyl unit of the formula (I) and a (meth) acryl unit (that is, a polymer represented by the formula (I)), or an adamantyl of the formula (I) It is a polymer consisting essentially of units and (meth) acrylic units. “Substantially” means that the sum of the adamantyl unit of formula (I) and the (meth) acryl unit in the polymer is, for example, 90 mol% or more, 95 mol% or more, 98 mol% or more, or 99 mol% or more. In addition, it means a case where an unreacted epoxy end, an unreacted (meth) acrylate end, and the like are further included within a range not impairing the effects of the present invention.
- the weight average molecular weight of the polymer represented by the formula (I) is not particularly limited, but is preferably 1,000 to 100,000. When the molecular weight is less than 1,000, curling of the obtained hard coat film may be increased. On the other hand, if the molecular weight exceeds 100,000, the solution viscosity of the resin may increase, and handling may be difficult.
- the composition of the present invention comprises the above-described polymer of the present invention and a photopolymerization initiator.
- photopolymerization initiator known photopolymerization initiators can be used, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2- Methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2 , 4,6-trimethylbenzoyl) -phenylphosphine oxide and the like. These can be used alone or
- Tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, etc.
- the photoinitiator aid may be added.
- a titanocene compound such as CGI-784 (manufactured by Ciba Specialty Chemicals Co., Ltd.) having absorption in the visible light region may be added in order to promote the photoreaction.
- the photopolymerization initiator is not limited to a photopolymerization initiator or a photoinitiator, as long as it is a compound that absorbs light in the ultraviolet or visible light region and radically polymerizes a photosensitive unsaturated double bond. Can be used.
- the content of the photopolymerization initiator in the composition is, for example, 0.1 to 20% by mass, preferably 1 to 10% by mass.
- the content of the photopolymerization initiator is less than 0.1% by mass, the photocurability may be lowered.
- the content exceeds 20% by mass, the precipitation of the photopolymerization initiator crystals or the lower part of the coating film may occur. There is a risk of poor photocuring.
- composition of this invention should just contain the polymer represented by a formula (I), and a photoinitiator, may consist essentially of these components, and may consist only of these components. “Substantially” means that the content of these components in the composition is, for example, 90% by mass or more, 95% by mass or more, 97% by mass or more, 98% by mass or more, or It means 99 mass% or more.
- solvent The composition of the present invention may be dissolved in a solvent as necessary.
- Solvents include alkyl alcohols such as methanol, ethanol, n-propanol, and isopropanol; glycol ethers such as methyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; benzene, toluene Aromatic hydrocarbons such as xylene and ethylbenzene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; ethers such as tetrahydrofuran, dioxane and diisopropyl ether; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone ( MIBK), ketones such as cyclohexanone; methyl acetate
- composition of the present invention may further contain other (meth) acrylic compounds, inorganic fine particles, leveling agents and the like as long as the effects of the present invention are not impaired and the balance of performance is not impaired.
- (meth) acrylic compounds include methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and isobornyl (meth) acrylate.
- the inorganic fine particles those having a particle size of several nanometers to 10 ⁇ m can be used depending on applications, and examples thereof include known inorganic fine particles such as glass powder, silica powder, titania, zinc oxide, zirconia and alumina.
- the leveling agent include silicone-based and fluorine-based leveling agents.
- the composition of the present invention can be suitably used as a hard coat resin composition (hard coat agent) for forming a hard coat layer.
- the hard coat layer is made to have high hardness by the adamantane skeleton of the polymer of the present invention, curling of the hard coat layer is suppressed, and the (meth) acrylate becomes a crosslinking unit, whereby the hard coat can be made to have higher hardness.
- the polyester film can be formed without performing a surface treatment such as corona treatment when forming the hard coat layer.
- a hard coat film can be obtained by directly coating and curing the composition on the surface.
- the polyester film usually precipitates by heating, the film becomes clouded and haze increases, but by laminating hard coat layers obtained by curing the composition of the present invention on both sides of the polyester film. , A hard coat film that does not become clouded even when heated or can reduce clouding can be obtained.
- the hard coat agent is a material mainly for improving chemical resistance and preventing scratches such as polycarbonate resin, acrylic resin, and polyethylene terephthalate resin.
- a hard coat resin composition is applied and cured by a coating method such as spin coating, spraying, flow, or dip, and a hard coat layer having a thickness of 2 to 10 ⁇ m is formed on the base material. Abrasion resistance can be imparted.
- the curing method of the composition of the present invention is not particularly limited, and usually a heat curing method or a curing method by ultraviolet irradiation can be used.
- the curing temperature is usually about 50 to 200 ° C., preferably 100 to 180 ° C. Setting it to 50 ° C. or higher does not cause poor curing, and setting it to 200 ° C. or lower eliminates coloring and the like.
- the curing time varies depending on the components contained in the composition, but is usually preferably 0.5 to 6 hours.
- the curing method by ultraviolet irradiation the ultraviolet light quantity is usually, 50 ⁇ 5000mJ / cm 2, preferably about irradiated to be 100 ⁇ 4000mJ / cm 2. Post-heating may be performed after the ultraviolet irradiation, and it is preferably performed at 70 to 200 ° C. for 0.5 to 12 hours.
- Example 1 To a 1000 mL round bottom flask equipped with a reflux condenser, stirrer, thermometer and nitrogen inlet tube, 88.1 g of 1-adamantyl methacrylate, 56.9 g of glycidyl methacrylate, and 300 g of methyl isobutyl ketone were added, and nitrogen bubbling was performed for 30 minutes. went. Thereafter, 8.2 g of azobisisobutyronitrile was further added, and the mixture was heated to 80 ° C. and reacted for 3 hours.
- reaction solution is cooled to room temperature, the nitrogen introduction tube is replaced with an air introduction tube, acrylic acid 29.4 g, triphenylphosphine 2.3 g and methoquinone 35 mg are added, and the temperature is raised to 110 ° C. while bubbling air.
- the reaction was continued for 12 hours until the acid value reached 5 mg-KOH / g or less.
- the obtained polymer solution was lowered to room temperature, and MIBK was added so that the solid content concentration was 35 wt% to obtain a reactive polymer A solution.
- Example 2 Example 1 except that 112.2 g of 1-adamantyl methacrylate, 33.5 g of glycidyl methacrylate, 7.5 g of azobisisobutyronitrile, 17.3 g of acrylic acid, and 1.4 g of triphenylphosphine were used. In the same manner, a reactive polymer B solution was obtained.
- Example 3 Example 1 except that 52.9 g of 1-adamantyl methacrylate, 79.6 g of glycidyl methacrylate, 8.8 g of azobisisobutyronitrile, 41.2 g of acrylic acid, and 3.3 g of triphenylphosphine were used. Thus, a reactive polymer C solution was obtained.
- Example 4 To a 1000 mL round bottom flask equipped with a reflux condenser, stirrer, thermometer and nitrogen inlet tube, 88.1 g of 1-adamantyl methacrylate, 34.4 g of methacrylic acid, and 300 g of methyl isobutyl ketone were added, and nitrogen bubbling was performed for 30 minutes. went. Thereafter, 8.2 g of azobisisobutyronitrile was further added, and the mixture was heated to 80 ° C. and reacted for 3 hours.
- reaction solution was cooled to room temperature, the nitrogen introduction tube was replaced with an air introduction tube, and 56.9 g of glycidyl methacrylate, 2.7 g of triphenylphosphine, and 35 mg of methoquinone were added. Air was bubbled, the temperature was raised to 110 ° C., and the reaction was continued for 12 hours until the acid value reached 5 mg-KOH / g or less. The obtained polymer solution was lowered to room temperature, and MIBK was added so that the solid content concentration was 35 wt% to obtain a reactive polymer D solution.
- Example 5 A reactive polymer E solution was obtained in the same manner as in Example 1 except that 94.5 g of 3-hydroxy-1-adamantyl methacrylate was used instead of 1-adamantyl methacrylate.
- Example 6 Instead of 1-adamantyl methacrylate, 117.6 g of perfluoro-1-adamantyl methacrylate, 79.6 g of glycidyl methacrylate, 8.8 g of azobisisobutyronitrile, 400 g of methyl isobutyl ketone, 41.2 g of acrylic acid, A reactive polymer F solution was obtained in the same manner as in Example 1 except that 3.3 g of phenylphosphine was used.
- Example 7 Instead of 1-adamantyl methacrylate, 55.1 g of methyl methacrylate was used, 78.2 g of glycidyl methacrylate, 12.3 g of azobisisobutyronitrile, 40.4 g of acrylic acid, and 3.2 g of triphenylphosphine. Otherwise, a reactive polymer G solution was obtained in the same manner as in Example 1.
- Example 8 2.1 g of 1-hydroxy-cyclohexyl-phenyl-ketone (product name: Irgacure 184) was added as a polymerization initiator to 200 g of the reactive polymer A solution prepared in Example 1 to prepare a hard coat resin solution.
- the prepared hard coat resin solution was applied to a PET film having a thickness of 100 ⁇ m (Lumilar T60 manufactured by Toray Industries, Inc.) using a bar coater and dried at 90 ° C. for 2 minutes. Then, it irradiated with 500 mJ / min using the high pressure mercury lamp, the coating layer was hardened, and the hard-coat layer of thickness 5 micrometers was formed.
- the following items were evaluated for the hard coat film which is a laminate of the obtained PET film and the hard coat layer. The results are shown in Table 2.
- [Pencil hardness] According to JIS K5600, the pencil hardness of the hard coat film was measured using a pencil scratch tester with a load of 750 g. [Abrasion resistance] A load of 200 gf was applied to Steel Wool # 0000, and the hard coat layer of the hard coat film was reciprocated 10 times. The condition of the scratches on the surface was visually observed and evaluated according to the following criteria. ⁇ : No scratch ⁇ : Less than 10 scratches ⁇ : 10 or more scratches [Curl] The hard coat film was cut into 10 cm ⁇ 10 cm, the height of the warp at the four corners of the film was measured, and the average value was defined as curl.
- Example 9-14 and Comparative Example 1-2 According to the blending amounts shown in Table 1, hard coat resin solutions were prepared in the same manner as in Example 8, and using the prepared hard coat resin solutions, hard coat films were produced in the same manner as in Example 8, and evaluated. did. The results are shown in Table 2.
- Example 15 The hard coat liquid prepared in Example 12 was applied to a PET film having a thickness of 100 ⁇ m (Lumilar T60 manufactured by Toray Industries, Inc.) using a bar coater and dried at 90 ° C. for 2 minutes. Thereafter, irradiation was performed at 500 mJ / min using a high-pressure mercury lamp, the coating layer was cured, and a hard coat layer having a thickness of 3 ⁇ m was formed. This operation was similarly performed on the opposite side of the film to obtain a PET film having a hard coat layer formed on both sides. The obtained hard coat film was heated at 150 ° C. for 1 hour, and the total light transmittance and haze before and after heating were measured. Haze was measured with a haze meter in accordance with JIS K7136. The results are shown in Table 3.
- Comparative Example 3 A hard coat film having a hard coat layer formed on both sides of the PET film was produced and evaluated in the same manner as in Example 15 except that the hard coat solution prepared in Comparative Example 2 was used. The results are shown in Table 3.
- the hard coat film having a hard coat layer obtained from the composition containing the polymer of the present invention has high hardness and can suppress curling, and is useful as a display film, particularly a touch panel film.
Abstract
A polymer which contains a structure represented by formula (I).
Description
本発明は、ポリマー、それを含む樹脂組成物及びその樹脂組成物から得られる硬化層を有するハードコートフィルムに関する。
The present invention relates to a polymer, a resin composition containing the polymer, and a hard coat film having a cured layer obtained from the resin composition.
液晶ディスプレイ、プラズマディスプレイ、有機ＥＬディスプレイ等にはさまざまな機能性フィルムが使用されている。なかでも、近年スマートフォンに代表されるようなタッチパネル形式のデバイスが普及してきており、より硬く、傷がつきにくいフィルムが要望されている。
Various functional films are used for liquid crystal displays, plasma displays, organic EL displays, etc. In particular, touch panel devices such as smartphones have become popular in recent years, and there is a demand for films that are harder and less scratched.
フィルムに硬度を付与する方法としては、紫外線硬化型樹脂をハードコートする方法が一般的である。しかし、紫外線硬化型樹脂の硬化収縮によってフィルムがカールする問題があり、ディスプレイ表面への貼り合わせ工程での生産性が低下してしまう他、貼り合わせ後の耐久性にも問題があった。
As a method of imparting hardness to the film, a method of hard coating an ultraviolet curable resin is common. However, there is a problem that the film curls due to curing shrinkage of the ultraviolet curable resin, and productivity in the bonding process to the display surface is lowered, and there is a problem in durability after bonding.
上記問題を解決するため、特許文献１は、プラスチックフィルムの少なくとも一方の面に２層以上のハードコート層を設ける方法を開示する。しかしながら、当該方法は、２層以上のハードコート層を設けるための塗工工程が煩雑になり、生産コストが高くなるという問題がある。
また、特許文献２は、エポキシ基含有（メタ）アクリル系共重合体に不飽和モノカルボン酸を付加反応させた反応性ポリマーをハードコート層に用いることを開示するが、ハードコート層の硬度及びカールの抑制のバランスは充分とは言いがたかった。 In order to solve the above problem, Patent Document 1 discloses a method of providing two or more hard coat layers on at least one surface of a plastic film. However, this method has a problem that the coating process for providing two or more hard coat layers becomes complicated and the production cost increases.
Patent Document 2 discloses that a reactive polymer obtained by addition-reacting an unsaturated monocarboxylic acid to an epoxy group-containing (meth) acrylic copolymer is used for the hard coat layer. It was hard to say that the balance of curl suppression was sufficient.
また、特許文献２は、エポキシ基含有（メタ）アクリル系共重合体に不飽和モノカルボン酸を付加反応させた反応性ポリマーをハードコート層に用いることを開示するが、ハードコート層の硬度及びカールの抑制のバランスは充分とは言いがたかった。 In order to solve the above problem, Patent Document 1 discloses a method of providing two or more hard coat layers on at least one surface of a plastic film. However, this method has a problem that the coating process for providing two or more hard coat layers becomes complicated and the production cost increases.
Patent Document 2 discloses that a reactive polymer obtained by addition-reacting an unsaturated monocarboxylic acid to an epoxy group-containing (meth) acrylic copolymer is used for the hard coat layer. It was hard to say that the balance of curl suppression was sufficient.
本発明の目的は、高硬度でカールが抑制されたハードコートフィルムが製造可能なポリマーを提供することである。
An object of the present invention is to provide a polymer capable of producing a hard coat film having high hardness and curling suppressed.
本発明によれば、以下のポリマー等が提供される。
１．下記式（Ｉ）で表わされる構造を含むポリマー。
（式中、Ｒ１、Ｒ４及びＲ６は、それぞれ水素原子又はメチル基である。
Ｒ２及びＲ５は、それぞれ水酸基、ハロゲン原子及びヘテロ原子から選択される１以上を含む２価の脂肪族炭化水素基、２価の脂肪族炭化水素基又は単結合である。
Ｒ３は、炭化水素基、ハロゲン置換炭化水素基、環式炭化水素基、ハロゲン置換環式炭化水素基、ハロゲン原子、水酸基、カルボキシル基、又はオキソ基である。
ｍは、０～１５の整数を表す。）
２．前記式（Ｉ）で表わされるポリマーのＲ２が単結合であり、ｍが０である１にポリマー。
３．アダマンチル基が結合した（メタ）アクリレートとエポキシ基が結合した（メタ）アクリレートを共重合した共重合体のエポキシ基に（メタ）アクリル酸を反応させて得られるポリマー、又はアダマンチル基が結合した（メタ）アクリレートと（メタ）アクリル酸を共重合した共重合体のカルボキシル基にエポキシ基が結合した（メタ）アクリレートを反応させて得られるポリマー。
４．１～３のいずれかに記載のポリマー及び光重合開始剤を含む樹脂組成物。
５．４に記載の樹脂組成物から得られる硬化層を有するハードコートフィルム。 According to the present invention, the following polymers and the like are provided.
1. A polymer comprising a structure represented by the following formula (I).
(In formula, R < 1 >, R < 4 > and R < 6 > are a hydrogen atom or a methyl group, respectively.
R 2 and R 5 are each a divalent aliphatic hydrocarbon group containing one or more selected from a hydroxyl group, a halogen atom and a hetero atom, a divalent aliphatic hydrocarbon group or a single bond.
R 3 is a hydrocarbon group, a halogen-substituted hydrocarbon group, a cyclic hydrocarbon group, a halogen-substituted cyclic hydrocarbon group, a halogen atom, a hydroxyl group, a carboxyl group, or an oxo group.
m represents an integer of 0 to 15. )
2. The polymer represented by the formula (I) is a polymer 1 in which R 2 is a single bond and m is 0.
3. A polymer obtained by reacting (meth) acrylic acid with an epoxy group of a copolymer obtained by copolymerizing (meth) acrylate having an adamantyl group and (meth) acrylate having an epoxy group bonded, or an adamantyl group having been bonded ( A polymer obtained by reacting (meth) acrylate having an epoxy group bonded to a carboxyl group of a copolymer obtained by copolymerizing (meth) acrylate and (meth) acrylic acid.
4. A resin composition comprising the polymer according to any one of 1 to 3 and a photopolymerization initiator.
A hard coat film having a cured layer obtained from the resin composition according to 5.4.
１．下記式（Ｉ）で表わされる構造を含むポリマー。
Ｒ２及びＲ５は、それぞれ水酸基、ハロゲン原子及びヘテロ原子から選択される１以上を含む２価の脂肪族炭化水素基、２価の脂肪族炭化水素基又は単結合である。
Ｒ３は、炭化水素基、ハロゲン置換炭化水素基、環式炭化水素基、ハロゲン置換環式炭化水素基、ハロゲン原子、水酸基、カルボキシル基、又はオキソ基である。
ｍは、０～１５の整数を表す。）
２．前記式（Ｉ）で表わされるポリマーのＲ２が単結合であり、ｍが０である１にポリマー。
３．アダマンチル基が結合した（メタ）アクリレートとエポキシ基が結合した（メタ）アクリレートを共重合した共重合体のエポキシ基に（メタ）アクリル酸を反応させて得られるポリマー、又はアダマンチル基が結合した（メタ）アクリレートと（メタ）アクリル酸を共重合した共重合体のカルボキシル基にエポキシ基が結合した（メタ）アクリレートを反応させて得られるポリマー。
４．１～３のいずれかに記載のポリマー及び光重合開始剤を含む樹脂組成物。
５．４に記載の樹脂組成物から得られる硬化層を有するハードコートフィルム。 According to the present invention, the following polymers and the like are provided.
1. A polymer comprising a structure represented by the following formula (I).
R 2 and R 5 are each a divalent aliphatic hydrocarbon group containing one or more selected from a hydroxyl group, a halogen atom and a hetero atom, a divalent aliphatic hydrocarbon group or a single bond.
R 3 is a hydrocarbon group, a halogen-substituted hydrocarbon group, a cyclic hydrocarbon group, a halogen-substituted cyclic hydrocarbon group, a halogen atom, a hydroxyl group, a carboxyl group, or an oxo group.
m represents an integer of 0 to 15. )
2. The polymer represented by the formula (I) is a polymer 1 in which R 2 is a single bond and m is 0.
3. A polymer obtained by reacting (meth) acrylic acid with an epoxy group of a copolymer obtained by copolymerizing (meth) acrylate having an adamantyl group and (meth) acrylate having an epoxy group bonded, or an adamantyl group having been bonded ( A polymer obtained by reacting (meth) acrylate having an epoxy group bonded to a carboxyl group of a copolymer obtained by copolymerizing (meth) acrylate and (meth) acrylic acid.
4. A resin composition comprising the polymer according to any one of 1 to 3 and a photopolymerization initiator.
A hard coat film having a cured layer obtained from the resin composition according to 5.4.
本発明によれば、高硬度でカールが抑制されたハードコートフィルムが製造可能なポリマーが提供できる。
According to the present invention, a polymer capable of producing a hard coat film with high hardness and curling suppressed can be provided.
本発明のポリマーは、下記式（Ｉ）で表わされる構造を含む。
（式中、Ｒ１、Ｒ４及びＲ６は、それぞれ水素原子又はメチル基である。
Ｒ２及びＲ５は、それぞれ水酸基、ハロゲン原子及びヘテロ原子から選択される１以上を含む２価の脂肪族炭化水素基、２価の脂肪族炭化水素基又は単結合である。
Ｒ３は、炭化水素基、ハロゲン置換炭化水素基、環式炭化水素基、ハロゲン置換環式炭化水素基、ハロゲン原子、水酸基、カルボキシル基、又はオキソ基（＝Ｏ）である。
ｍは、０～１５の整数を表す。） The polymer of the present invention includes a structure represented by the following formula (I).
(In formula, R < 1 >, R < 4 > and R < 6 > are a hydrogen atom or a methyl group, respectively.
R 2 and R 5 are each a divalent aliphatic hydrocarbon group containing one or more selected from a hydroxyl group, a halogen atom and a hetero atom, a divalent aliphatic hydrocarbon group or a single bond.
R 3 is a hydrocarbon group, a halogen-substituted hydrocarbon group, a cyclic hydrocarbon group, a halogen-substituted cyclic hydrocarbon group, a halogen atom, a hydroxyl group, a carboxyl group, or an oxo group (═O).
m represents an integer of 0 to 15. )
Ｒ２及びＲ５は、それぞれ水酸基、ハロゲン原子及びヘテロ原子から選択される１以上を含む２価の脂肪族炭化水素基、２価の脂肪族炭化水素基又は単結合である。
Ｒ３は、炭化水素基、ハロゲン置換炭化水素基、環式炭化水素基、ハロゲン置換環式炭化水素基、ハロゲン原子、水酸基、カルボキシル基、又はオキソ基（＝Ｏ）である。
ｍは、０～１５の整数を表す。） The polymer of the present invention includes a structure represented by the following formula (I).
R 2 and R 5 are each a divalent aliphatic hydrocarbon group containing one or more selected from a hydroxyl group, a halogen atom and a hetero atom, a divalent aliphatic hydrocarbon group or a single bond.
R 3 is a hydrocarbon group, a halogen-substituted hydrocarbon group, a cyclic hydrocarbon group, a halogen-substituted cyclic hydrocarbon group, a halogen atom, a hydroxyl group, a carboxyl group, or an oxo group (═O).
m represents an integer of 0 to 15. )
式（Ｉ）で表わされるポリマーの各基は、以下の通りである。
Ｒ２及びＲ５の水酸基、ハロゲン原子及びヘテロ原子から選択される１以上を含む２価の脂肪族炭化水素基としては、例えば下記３つの構造が挙げられる。
（式中、ｎは０以上の整数である。）
Each group of the polymer represented by the formula (I) is as follows.
Examples of the divalent aliphatic hydrocarbon group containing one or more selected from a hydroxyl group, a halogen atom and a hetero atom of R 2 and R 5 include the following three structures.
(In the formula, n is an integer of 0 or more.)
Ｒ２及びＲ５の水酸基、ハロゲン原子及びヘテロ原子から選択される１以上を含む２価の脂肪族炭化水素基としては、例えば下記３つの構造が挙げられる。
Examples of the divalent aliphatic hydrocarbon group containing one or more selected from a hydroxyl group, a halogen atom and a hetero atom of R 2 and R 5 include the following three structures.
Ｒ２及びＲ５の２価の脂肪族炭化水素基としては、メチレン基、エチレン基、ブチレン基等が挙げられる。
Ｒ３の炭化水素基としては、メチル基、エチル基、ブチル基、ｔ－ブチル基等が挙げられる。
Ｒ３の環式炭化水素基としては、シクロペンチル基、シクロヘキシル基等が挙げられる。
Ｒ３のハロゲン置換炭化水素基は、上記炭化水素基の水素原子をハロゲン原子で置換した基である。同様に、Ｒ３のハロゲン置換環式炭化水素基は、上記環式炭化水素基の水素原子をハロゲン原子で置換した基である。
尚、Ｒ３のオキソ基は、２つのＲ３がアダマンタン骨格の同一炭素原子に結合しており、且つ当該２つのＲ３が共に水酸基であり、これら水酸基が縮合した場合である。 Examples of the divalent aliphatic hydrocarbon group for R 2 and R 5 include a methylene group, an ethylene group, and a butylene group.
Examples of the hydrocarbon group for R 3 include a methyl group, an ethyl group, a butyl group, and a t-butyl group.
Examples of the cyclic hydrocarbon group for R 3 include a cyclopentyl group and a cyclohexyl group.
The halogen-substituted hydrocarbon group for R 3 is a group obtained by substituting the hydrogen atom of the hydrocarbon group with a halogen atom. Similarly, the halogen-substituted cyclic hydrocarbon group for R 3 is a group obtained by substituting the hydrogen atom of the cyclic hydrocarbon group with a halogen atom.
Incidentally, oxo group of R 3, two of R 3 are attached to the same carbon atom of the adamantane skeleton, and the two R 3 are both hydroxyl groups and the case where these hydroxyl groups are condensed.
Ｒ３の炭化水素基としては、メチル基、エチル基、ブチル基、ｔ－ブチル基等が挙げられる。
Ｒ３の環式炭化水素基としては、シクロペンチル基、シクロヘキシル基等が挙げられる。
Ｒ３のハロゲン置換炭化水素基は、上記炭化水素基の水素原子をハロゲン原子で置換した基である。同様に、Ｒ３のハロゲン置換環式炭化水素基は、上記環式炭化水素基の水素原子をハロゲン原子で置換した基である。
尚、Ｒ３のオキソ基は、２つのＲ３がアダマンタン骨格の同一炭素原子に結合しており、且つ当該２つのＲ３が共に水酸基であり、これら水酸基が縮合した場合である。 Examples of the divalent aliphatic hydrocarbon group for R 2 and R 5 include a methylene group, an ethylene group, and a butylene group.
Examples of the hydrocarbon group for R 3 include a methyl group, an ethyl group, a butyl group, and a t-butyl group.
Examples of the cyclic hydrocarbon group for R 3 include a cyclopentyl group and a cyclohexyl group.
The halogen-substituted hydrocarbon group for R 3 is a group obtained by substituting the hydrogen atom of the hydrocarbon group with a halogen atom. Similarly, the halogen-substituted cyclic hydrocarbon group for R 3 is a group obtained by substituting the hydrogen atom of the cyclic hydrocarbon group with a halogen atom.
Incidentally, oxo group of R 3, two of R 3 are attached to the same carbon atom of the adamantane skeleton, and the two R 3 are both hydroxyl groups and the case where these hydroxyl groups are condensed.
式（Ｉ）で表わされるポリマーは、好ましくはＲ２が単結合（直接結合する）であり、ｍが０であるポリマーである。
The polymer represented by the formula (I) is preferably a polymer in which R 2 is a single bond (directly bonded) and m is 0.
式（Ｉ）で表わされる構造を含むポリマーは、アダマンチル基が結合した（メタ）アクリレートとエポキシ基が結合した（メタ）アクリレートを共重合させた後、得られた共重合体のエポキシ基に（メタ）アクリル酸を反応させる；又は、アダマンチル基が結合した（メタ）アクリレートと（メタ）アクリル酸を共重合させた後、得られた共重合体のカルボキシル基にエポキシ基が結合した（メタ）アクリレートを反応させることにより製造できる。
The polymer containing the structure represented by the formula (I) is obtained by copolymerizing (meth) acrylate having an adamantyl group bonded thereto and (meth) acrylate having an epoxy group bonded thereto. (Meth) acrylic acid is reacted; or (meth) acrylate having adamantyl group bonded thereto and (meth) acrylic acid are copolymerized, and then an epoxy group is bonded to the carboxyl group of the resulting copolymer (meth) It can be produced by reacting acrylate.
アダマンチル基が結合した（メタ）アクリレートは、例えば下記構造を有する化合物である。
（式中、Ｒ１、Ｒ２、Ｒ３及びｍは、式（Ｉ）と同様である。）
(Meth) acrylate to which an adamantyl group is bonded is, for example, a compound having the following structure.
(In the formula, R 1 , R 2 , R 3 and m are the same as in formula (I).)
エポキシ基が結合した（メタ）アクリレートは、例えば下記構造を有する化合物である。下記式中において、Ｒ５’と開環したエポキシ基を併せた基がＲ５に対応する。
（式中、Ｒ４は、式（Ｉ）と同様である。
Ｒ５’は、それぞれ水酸基、ハロゲン原子及びヘテロ原子から選択される１以上を含む２価の脂肪族炭化水素基、２価の脂肪族炭化水素基又は単結合である。） The (meth) acrylate to which the epoxy group is bonded is, for example, a compound having the following structure. In the following formula, a group in which R 5 ′ and a ring-opened epoxy group are combined corresponds to R 5 .
(Wherein R 4 is the same as in formula (I).
R 5 ′ is a divalent aliphatic hydrocarbon group containing at least one selected from a hydroxyl group, a halogen atom and a hetero atom, a divalent aliphatic hydrocarbon group or a single bond. )
Ｒ５’は、それぞれ水酸基、ハロゲン原子及びヘテロ原子から選択される１以上を含む２価の脂肪族炭化水素基、２価の脂肪族炭化水素基又は単結合である。） The (meth) acrylate to which the epoxy group is bonded is, for example, a compound having the following structure. In the following formula, a group in which R 5 ′ and a ring-opened epoxy group are combined corresponds to R 5 .
R 5 ′ is a divalent aliphatic hydrocarbon group containing at least one selected from a hydroxyl group, a halogen atom and a hetero atom, a divalent aliphatic hydrocarbon group or a single bond. )
（メタ）アクリル酸は、例えば下記構造を有する化合物である。
（式中、Ｒ６は、式（Ｉ）と同様である。）
(Meth) acrylic acid is a compound having the following structure, for example.
(Wherein R 6 is the same as in formula (I).)
上記共重合は、例えば公知のラジカル重合法により実施でき、溶媒中もしくは無溶媒でラジカル重合開始剤等を用いて重合すればよい。
ラジカル重合開始剤としては、例えば２，２'－アゾビスイソブチロニトリル、２，２'－アゾビス－メチルブチロニトリル等のアゾ系開始剤；過酸化ベンゾイル、メチルエチルケトンパーオキサイド、メチルイソブチルケトンパーオキサイド等の過酸化物開始剤が挙げられる。
また、必要に応じてドデシルメルカプタン、ラウリルメルカプタン、チオグリコール酸エステル、メルカプトエタノール等の連鎖移動剤を用いてもよい。 The above copolymerization can be carried out, for example, by a known radical polymerization method, and may be performed using a radical polymerization initiator or the like in a solvent or without a solvent.
Examples of the radical polymerization initiator include azo initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis-methylbutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide Peroxide initiators, such as an oxide, are mentioned.
Moreover, you may use chain transfer agents, such as a dodecyl mercaptan, a lauryl mercaptan, a thioglycolic acid ester, and a mercaptoethanol, as needed.
ラジカル重合開始剤としては、例えば２，２'－アゾビスイソブチロニトリル、２，２'－アゾビス－メチルブチロニトリル等のアゾ系開始剤；過酸化ベンゾイル、メチルエチルケトンパーオキサイド、メチルイソブチルケトンパーオキサイド等の過酸化物開始剤が挙げられる。
また、必要に応じてドデシルメルカプタン、ラウリルメルカプタン、チオグリコール酸エステル、メルカプトエタノール等の連鎖移動剤を用いてもよい。 The above copolymerization can be carried out, for example, by a known radical polymerization method, and may be performed using a radical polymerization initiator or the like in a solvent or without a solvent.
Examples of the radical polymerization initiator include azo initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis-methylbutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide Peroxide initiators, such as an oxide, are mentioned.
Moreover, you may use chain transfer agents, such as a dodecyl mercaptan, a lauryl mercaptan, a thioglycolic acid ester, and a mercaptoethanol, as needed.
ラジカル重合開始剤の使用量は、共重合させるアダマンチル基が結合した（メタ）アクリレート及びエポキシ基が結合した（メタ）アクリレート、又はアダマンチル基が結合した（メタ）アクリレート及び（メタ）アクリル酸の合計１００質量部に対して、通常、０．０１～５０質量部であり、好ましくは０．０１～３０質量部である。ラジカル重合開始剤の使用量を当該範囲とすることにより、反応時間及び収率等を良好にでき、また、目的とする重量平均分子量が得られる。
The amount of radical polymerization initiator used is the total of (meth) acrylates to which copolymerized adamantyl groups are bonded and (meth) acrylates to which epoxy groups are bonded, or (meth) acrylates and (meth) acrylic acids to which adamantyl groups are bonded. The amount is usually 0.01 to 50 parts by mass, preferably 0.01 to 30 parts by mass with respect to 100 parts by mass. By making the usage-amount of a radical polymerization initiator into the said range, reaction time, a yield, etc. can be made favorable and the target weight average molecular weight is obtained.
共重合に使用する溶媒としては、メタノール、エタノール、ｎ－プロパノール、イソプロパノール等のアルキルアルコール類；メチルセロソルブ、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等のグリコールエーテル類；ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素類；シクロペンタン、シクロヘキサン、メチルシクロヘキサン等の脂環族炭化水素類；テトラヒドロフラン、ジオキサン、ジイソプロピルエーテル等のエーテル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類；酢酸メチル、酢酸エチル、酢酸－ｎ－プロピル、プロピオン酸エチル、プロピレングリコールモノエチルエーテルアセテート等のエステル類等が挙げられる。これら溶媒は、１種単独又は２種以上を組み合わせて使用できる。
共重合に使用する溶媒は、共重合成分（アダマンチル基が結合した（メタ）アクリレート及びエポキシ基が結合した（メタ）アクリレート、又はアダマンチル基が結合した（メタ）アクリレート及び（メタ）アクリル酸）の合計濃度が、例えば０．５質量％以上、好ましくは５質量％以上となる量を使用するとよい。このとき、共重合成分は、懸濁状態でもよいが、溶解していると好ましい。 Solvents used for copolymerization include alkyl alcohols such as methanol, ethanol, n-propanol and isopropanol; glycol ethers such as methyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; ethers such as tetrahydrofuran, dioxane and diisopropyl ether; acetone, methyl ethyl ketone and methyl isobutyl Ketones such as ketone and cyclohexanone; methyl acetate, ethyl acetate, acetic acid-n-propyl, ethyl propionate, Esters such as Russia propylene glycol monoethyl ether acetate. These solvents can be used alone or in combination of two or more.
The solvent used for copolymerization is a copolymer component ((meth) acrylate having an adamantyl group bonded and (meth) acrylate having an epoxy group bonded, or (meth) acrylate and (meth) acrylic acid having an adamantyl group bonded)). The total concentration is, for example, 0.5% by mass or more, preferably 5% by mass or more. At this time, the copolymer component may be in a suspended state, but is preferably dissolved.
共重合に使用する溶媒は、共重合成分（アダマンチル基が結合した（メタ）アクリレート及びエポキシ基が結合した（メタ）アクリレート、又はアダマンチル基が結合した（メタ）アクリレート及び（メタ）アクリル酸）の合計濃度が、例えば０．５質量％以上、好ましくは５質量％以上となる量を使用するとよい。このとき、共重合成分は、懸濁状態でもよいが、溶解していると好ましい。 Solvents used for copolymerization include alkyl alcohols such as methanol, ethanol, n-propanol and isopropanol; glycol ethers such as methyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; ethers such as tetrahydrofuran, dioxane and diisopropyl ether; acetone, methyl ethyl ketone and methyl isobutyl Ketones such as ketone and cyclohexanone; methyl acetate, ethyl acetate, acetic acid-n-propyl, ethyl propionate, Esters such as Russia propylene glycol monoethyl ether acetate. These solvents can be used alone or in combination of two or more.
The solvent used for copolymerization is a copolymer component ((meth) acrylate having an adamantyl group bonded and (meth) acrylate having an epoxy group bonded, or (meth) acrylate and (meth) acrylic acid having an adamantyl group bonded)). The total concentration is, for example, 0.5% by mass or more, preferably 5% by mass or more. At this time, the copolymer component may be in a suspended state, but is preferably dissolved.
共重合反応の反応温度としては、通常、０～２００℃であり、好ましくは２０～１５０℃である。温度が０℃未満の場合、反応速度が低下するおそれがある。一方、温度が２００℃超の場合、得られるポリマーの着色が激しくなるおそれがある。
共重合反応の反応圧力としては、通常、絶対圧力で０．０１～１０ＭＰａであり、好ましくは常圧～１ＭＰａである。圧力が１０ＭＰａ超の場合、安全上、問題があるうえ、特別な装置が必要となり好ましくない。
反応時間としては、重合開始剤の種類や量、反応温度等に左右されるが、通常、１分～２４時間であり、好ましくは１～１０時間である。 The reaction temperature for the copolymerization reaction is usually 0 to 200 ° C., preferably 20 to 150 ° C. When the temperature is lower than 0 ° C., the reaction rate may decrease. On the other hand, when the temperature is higher than 200 ° C., the resulting polymer may be intensely colored.
The reaction pressure for the copolymerization reaction is usually 0.01 to 10 MPa in absolute pressure, preferably normal pressure to 1 MPa. When the pressure exceeds 10 MPa, there is a problem in terms of safety, and a special device is required, which is not preferable.
The reaction time depends on the type and amount of the polymerization initiator, the reaction temperature, etc., but is usually 1 minute to 24 hours, preferably 1 to 10 hours.
共重合反応の反応圧力としては、通常、絶対圧力で０．０１～１０ＭＰａであり、好ましくは常圧～１ＭＰａである。圧力が１０ＭＰａ超の場合、安全上、問題があるうえ、特別な装置が必要となり好ましくない。
反応時間としては、重合開始剤の種類や量、反応温度等に左右されるが、通常、１分～２４時間であり、好ましくは１～１０時間である。 The reaction temperature for the copolymerization reaction is usually 0 to 200 ° C., preferably 20 to 150 ° C. When the temperature is lower than 0 ° C., the reaction rate may decrease. On the other hand, when the temperature is higher than 200 ° C., the resulting polymer may be intensely colored.
The reaction pressure for the copolymerization reaction is usually 0.01 to 10 MPa in absolute pressure, preferably normal pressure to 1 MPa. When the pressure exceeds 10 MPa, there is a problem in terms of safety, and a special device is required, which is not preferable.
The reaction time depends on the type and amount of the polymerization initiator, the reaction temperature, etc., but is usually 1 minute to 24 hours, preferably 1 to 10 hours.
共重合反応時に、本発明の効果を損なわない範囲で、他の（メタ）アクリル系モノマーを共重合成分として加えてもよい。
他の（メタ）アクリル系モノマーとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、γ－ブチロラクトン（メタ）アクリレート等が挙げられる。 During the copolymerization reaction, another (meth) acrylic monomer may be added as a copolymerization component as long as the effects of the present invention are not impaired.
Other (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) Examples thereof include acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and γ-butyrolactone (meth) acrylate.
他の（メタ）アクリル系モノマーとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、γ－ブチロラクトン（メタ）アクリレート等が挙げられる。 During the copolymerization reaction, another (meth) acrylic monomer may be added as a copolymerization component as long as the effects of the present invention are not impaired.
Other (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) Examples thereof include acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and γ-butyrolactone (meth) acrylate.
共重合反応後の付加反応、即ちアダマンチル基が結合した（メタ）アクリレートとエポキシ基が結合した（メタ）アクリレートの共重合体に、（メタ）アクリル酸を付加する反応；又はアダマンチル基が結合した（メタ）アクリレートと（メタ）アクリル酸の共重合体に、エポキシ基が結合した（メタ）アクリレートを付加する反応は、これらを溶媒中で反応させればよい。
Addition reaction after copolymerization reaction, that is, a reaction of adding (meth) acrylic acid to a copolymer of (meth) acrylate bonded with an adamantyl group and (meth) acrylate bonded with an epoxy group; or an adamantyl group bonded The reaction of adding a (meth) acrylate having an epoxy group bonded to a copolymer of (meth) acrylate and (meth) acrylic acid may be carried out in a solvent.
付加反応に使用できる溶媒としては、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、トルエン、キシレン、ＭＥＫ（メチルエチルケトン）、ＭＩＢＫ（メチルイソブチルケトン）、ＤＭＦ（ジメチルホルムアミド）、ＮＭＰ（Ｎ－メチル－２－ピロリドン）、ＤＭＡｃ（Ｎ，Ｎ－ジメチルアセトアミド）、ＤＭＳＯ（ジメチルスルホキシド）、及びプロピレングリコールモノメチルエーテルアセテート等が挙げられる。
Solvents that can be used for the addition reaction include cyclohexane, methylcyclohexane, ethylcyclohexane, toluene, xylene, MEK (methyl ethyl ketone), MIBK (methyl isobutyl ketone), DMF (dimethylformamide), NMP (N-methyl-2-pyrrolidone), Examples include DMAc (N, N-dimethylacetamide), DMSO (dimethyl sulfoxide), and propylene glycol monomethyl ether acetate.
付加反応時に触媒を使用してもよく、当該触媒としては、テトラメチルアンモニウムクロライド、テトラメチルアンモニウムブロマイド、テトラエチルアンモニウムクロライド、テトラエチルアンモニウムブロマイド、トリフェニルホスフィン、ピリジン等が挙げられる。
A catalyst may be used during the addition reaction, and examples of the catalyst include tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, triphenylphosphine, and pyridine.
式（Ｉ）で表わされる構造を含むポリマーのアダマンチルユニットと（メタ）アクリルユニットの構成単位比率（モル比）は、共重合時の配合比が反映され、アダマンチルユニットが１％～９９％、好ましくは１０％～９０％である。アダマンチルユニットが１０％未満であると得られるハードコートフィルムのカールが大きくなる可能性があり、９０％を超えても得られるハードコートフィルムの物性に大きな違いはない。
尚、式（Ｉ）で表わされるポリマーの重合形態は特に限定されないが、例えばランダム共重合体である。
The constitutional unit ratio (molar ratio) of the adamantyl unit and (meth) acryl unit of the polymer containing the structure represented by the formula (I) reflects the blending ratio at the time of copolymerization, and the adamantyl unit is 1% to 99%, preferably Is 10% to 90%. When the adamantyl unit is less than 10%, the curl of the obtained hard coat film may increase, and even when it exceeds 90%, there is no significant difference in the physical properties of the obtained hard coat film.
In addition, although the polymerization form of the polymer represented by the formula (I) is not particularly limited, for example, it is a random copolymer.
尚、式（Ｉ）で表わされるポリマーの重合形態は特に限定されないが、例えばランダム共重合体である。
In addition, although the polymerization form of the polymer represented by the formula (I) is not particularly limited, for example, it is a random copolymer.
式（Ｉ）で表わされる構造を含むポリマーは、式（Ｉ）のアダマンチルユニットと（メタ）アクリルユニットのみからなるポリマー（即ち、式（Ｉ）で表わされるポリマー）、又は式（Ｉ）のアダマンチルユニットと（メタ）アクリルユニットから実質的になるポリマーである。
「実質的になる」とは、ポリマー中の式（Ｉ）のアダマンチルユニットと（メタ）アクリルユニットの合計が、例えば９０モル％以上、９５モル％以上、９８モル％以上、又は９９モル％以上であって、本発明の効果を損なわない範囲で、さらに未反応エポキシ末端、未反応（メタ）アクリレート末端等を含む場合をいう。 The polymer containing the structure represented by the formula (I) is a polymer composed only of an adamantyl unit of the formula (I) and a (meth) acryl unit (that is, a polymer represented by the formula (I)), or an adamantyl of the formula (I) It is a polymer consisting essentially of units and (meth) acrylic units.
“Substantially” means that the sum of the adamantyl unit of formula (I) and the (meth) acryl unit in the polymer is, for example, 90 mol% or more, 95 mol% or more, 98 mol% or more, or 99 mol% or more. In addition, it means a case where an unreacted epoxy end, an unreacted (meth) acrylate end, and the like are further included within a range not impairing the effects of the present invention.
「実質的になる」とは、ポリマー中の式（Ｉ）のアダマンチルユニットと（メタ）アクリルユニットの合計が、例えば９０モル％以上、９５モル％以上、９８モル％以上、又は９９モル％以上であって、本発明の効果を損なわない範囲で、さらに未反応エポキシ末端、未反応（メタ）アクリレート末端等を含む場合をいう。 The polymer containing the structure represented by the formula (I) is a polymer composed only of an adamantyl unit of the formula (I) and a (meth) acryl unit (that is, a polymer represented by the formula (I)), or an adamantyl of the formula (I) It is a polymer consisting essentially of units and (meth) acrylic units.
“Substantially” means that the sum of the adamantyl unit of formula (I) and the (meth) acryl unit in the polymer is, for example, 90 mol% or more, 95 mol% or more, 98 mol% or more, or 99 mol% or more. In addition, it means a case where an unreacted epoxy end, an unreacted (meth) acrylate end, and the like are further included within a range not impairing the effects of the present invention.
式（Ｉ）で表わされるポリマーの重量平均分子量に特に制限はないが、好ましくは１，０００～１００，０００である。分子量が１，０００未満であると得られるハードコートフィルムのカールが大きくなる可能性がある。一方、分子量が１００，０００を超えると樹脂の溶液粘度が高くなり、ハンドリングが困難になる場合も考えられる。
The weight average molecular weight of the polymer represented by the formula (I) is not particularly limited, but is preferably 1,000 to 100,000. When the molecular weight is less than 1,000, curling of the obtained hard coat film may be increased. On the other hand, if the molecular weight exceeds 100,000, the solution viscosity of the resin may increase, and handling may be difficult.
本発明の組成物は、上記の本発明のポリマー及び光重合開始剤を含む。
［光重合開始剤］
光重合開始剤は、公知の光重合開始剤が使用でき、例えば２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、２－ヒロドキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド等が挙げられる。
これらは、単独で又は２種以上を混合して用いることができる。 The composition of the present invention comprises the above-described polymer of the present invention and a photopolymerization initiator.
[Photopolymerization initiator]
As the photopolymerization initiator, known photopolymerization initiators can be used, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2- Methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- { 4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2 , 4,6-trimethylbenzoyl) -phenylphosphine oxide and the like.
These can be used alone or in admixture of two or more.
［光重合開始剤］
光重合開始剤は、公知の光重合開始剤が使用でき、例えば２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、２－ヒロドキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド等が挙げられる。
これらは、単独で又は２種以上を混合して用いることができる。 The composition of the present invention comprises the above-described polymer of the present invention and a photopolymerization initiator.
[Photopolymerization initiator]
As the photopolymerization initiator, known photopolymerization initiators can be used, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2- Methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- { 4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2 , 4,6-trimethylbenzoyl) -phenylphosphine oxide and the like.
These can be used alone or in admixture of two or more.
上記光重合開始剤に、Ｎ，Ｎ－ジメチルアミノ安息香酸エチルエステル、Ｎ，Ｎ－ジメチルアミノ安息香酸イソアミルエステル、ペンチル－４－ジメチルアミノベンゾエート、トリエチルアミン、トリエタノールアミン等の第三級アミン類等の光開始助剤を加えてもよい。また、可視光領域に吸収のあるＣＧＩ－７８４等（チバ・スペシャルティ・ケミカルズ（株）製）のチタノセン化合物等も、光反応を促進するために添加してもよい。
尚、光重合開始剤は、紫外光もしくは可視光領域で光を吸収し、感光性の不飽和二重結合をラジカル重合させる化合物であれば、光重合開始剤、光開始助剤に限らず、使用できる。 Tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, etc. The photoinitiator aid may be added. Further, a titanocene compound such as CGI-784 (manufactured by Ciba Specialty Chemicals Co., Ltd.) having absorption in the visible light region may be added in order to promote the photoreaction.
The photopolymerization initiator is not limited to a photopolymerization initiator or a photoinitiator, as long as it is a compound that absorbs light in the ultraviolet or visible light region and radically polymerizes a photosensitive unsaturated double bond. Can be used.
尚、光重合開始剤は、紫外光もしくは可視光領域で光を吸収し、感光性の不飽和二重結合をラジカル重合させる化合物であれば、光重合開始剤、光開始助剤に限らず、使用できる。 Tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, etc. The photoinitiator aid may be added. Further, a titanocene compound such as CGI-784 (manufactured by Ciba Specialty Chemicals Co., Ltd.) having absorption in the visible light region may be added in order to promote the photoreaction.
The photopolymerization initiator is not limited to a photopolymerization initiator or a photoinitiator, as long as it is a compound that absorbs light in the ultraviolet or visible light region and radically polymerizes a photosensitive unsaturated double bond. Can be used.
組成物中の光重合開始剤の含有量は、例えば０．１～２０質量％であり、好ましくは１～１０質量％である。光重合開始剤の含有量が、０．１質量％未満の場合、光硬化性が低下するおそれがある、一方、２０質量％を越える場合、光重合開始剤の結晶の析出や塗膜下部の光硬化不良が起こるおそれがある。
The content of the photopolymerization initiator in the composition is, for example, 0.1 to 20% by mass, preferably 1 to 10% by mass. When the content of the photopolymerization initiator is less than 0.1% by mass, the photocurability may be lowered. On the other hand, when the content exceeds 20% by mass, the precipitation of the photopolymerization initiator crystals or the lower part of the coating film may occur. There is a risk of poor photocuring.
本発明の組成物は、式（Ｉ）で表わされるポリマー及び光重合開始剤を含めばよく、これら成分から実質的になってもよく、これら成分のみからなっていてもよい。
「実質的になる」とは、これら成分の組成物中の含有量が、例えば９０質量％以上である、９５質量％以上である、９７質量％以上である、９８質量％以上である、又は９９質量％以上であることをいう。 The composition of this invention should just contain the polymer represented by a formula (I), and a photoinitiator, may consist essentially of these components, and may consist only of these components.
“Substantially” means that the content of these components in the composition is, for example, 90% by mass or more, 95% by mass or more, 97% by mass or more, 98% by mass or more, or It means 99 mass% or more.
「実質的になる」とは、これら成分の組成物中の含有量が、例えば９０質量％以上である、９５質量％以上である、９７質量％以上である、９８質量％以上である、又は９９質量％以上であることをいう。 The composition of this invention should just contain the polymer represented by a formula (I), and a photoinitiator, may consist essentially of these components, and may consist only of these components.
“Substantially” means that the content of these components in the composition is, for example, 90% by mass or more, 95% by mass or more, 97% by mass or more, 98% by mass or more, or It means 99 mass% or more.
［溶剤］
本発明の組成物は、必要に応じて、溶剤に溶解させた状態でもよい。
溶剤としては、メタノール、エタノール、ｎ－プロパノール、イソプロパノール等のアルキルアルコール類；メチルセロソルブ、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等のグリコールエーテル類；ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素類；シクロペンタン、シクロヘキサン、メチルシクロヘキサン等の脂環族炭化水素類；テトラヒドロフラン、ジオキサン、ジイソプロピルエーテル等のエーテル類；アセトン、メチルエチルケトン（ＭＥＫ）、メチルイソブチルケトン（ＭＩＢＫ）、シクロヘキサノン等のケトン類；酢酸メチル、酢酸エチル、酢酸－ｎ－プロピル、プロピオン酸エチル、プロピレングリコールモノエチルエーテルアセテート等のエステル類等が挙げられる。これらは、単独で又は２種以上を混合して用いることができる。
溶剤の含有量は、例えば５質量％～９０質量％であり、乾燥の観点から、好ましくは１０質量％～５０質量％である。 [solvent]
The composition of the present invention may be dissolved in a solvent as necessary.
Solvents include alkyl alcohols such as methanol, ethanol, n-propanol, and isopropanol; glycol ethers such as methyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; benzene, toluene Aromatic hydrocarbons such as xylene and ethylbenzene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; ethers such as tetrahydrofuran, dioxane and diisopropyl ether; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone ( MIBK), ketones such as cyclohexanone; methyl acetate, ethyl acetate, acetic acid-n-propyl, propionic acid Le, esters such as propylene glycol monomethyl ether acetate, and the like. These can be used alone or in admixture of two or more.
The content of the solvent is, for example, 5% by mass to 90% by mass, and preferably 10% by mass to 50% by mass from the viewpoint of drying.
本発明の組成物は、必要に応じて、溶剤に溶解させた状態でもよい。
溶剤としては、メタノール、エタノール、ｎ－プロパノール、イソプロパノール等のアルキルアルコール類；メチルセロソルブ、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等のグリコールエーテル類；ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素類；シクロペンタン、シクロヘキサン、メチルシクロヘキサン等の脂環族炭化水素類；テトラヒドロフラン、ジオキサン、ジイソプロピルエーテル等のエーテル類；アセトン、メチルエチルケトン（ＭＥＫ）、メチルイソブチルケトン（ＭＩＢＫ）、シクロヘキサノン等のケトン類；酢酸メチル、酢酸エチル、酢酸－ｎ－プロピル、プロピオン酸エチル、プロピレングリコールモノエチルエーテルアセテート等のエステル類等が挙げられる。これらは、単独で又は２種以上を混合して用いることができる。
溶剤の含有量は、例えば５質量％～９０質量％であり、乾燥の観点から、好ましくは１０質量％～５０質量％である。 [solvent]
The composition of the present invention may be dissolved in a solvent as necessary.
Solvents include alkyl alcohols such as methanol, ethanol, n-propanol, and isopropanol; glycol ethers such as methyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; benzene, toluene Aromatic hydrocarbons such as xylene and ethylbenzene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; ethers such as tetrahydrofuran, dioxane and diisopropyl ether; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone ( MIBK), ketones such as cyclohexanone; methyl acetate, ethyl acetate, acetic acid-n-propyl, propionic acid Le, esters such as propylene glycol monomethyl ether acetate, and the like. These can be used alone or in admixture of two or more.
The content of the solvent is, for example, 5% by mass to 90% by mass, and preferably 10% by mass to 50% by mass from the viewpoint of drying.
［その他の成分］
本発明の組成物は、本発明の効果を損なわず、性能のバランスを損なわない範囲内で、他の（メタ）アクリル系化合物、無機微粒子、レべリング剤等をさらに含んでもよい。 [Other ingredients]
The composition of the present invention may further contain other (meth) acrylic compounds, inorganic fine particles, leveling agents and the like as long as the effects of the present invention are not impaired and the balance of performance is not impaired.
本発明の組成物は、本発明の効果を損なわず、性能のバランスを損なわない範囲内で、他の（メタ）アクリル系化合物、無機微粒子、レべリング剤等をさらに含んでもよい。 [Other ingredients]
The composition of the present invention may further contain other (meth) acrylic compounds, inorganic fine particles, leveling agents and the like as long as the effects of the present invention are not impaired and the balance of performance is not impaired.
他の（メタ）アクリル化合物としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、γ－ブチロラクトン（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、アダマンタンジオールジ（メタ）アクリレート、アダマンタンジメタノールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、アダマンタントリオールトリ（メタ）アクリレート、アダマンタントリメタノールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ビスフェノールＡエポキシ（メタ）アクリレート等が挙げられる。
Other (meth) acrylic compounds include methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and isobornyl (meth) acrylate. , Benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, γ-butyrolactone (meth) acrylate, ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, adamantanediol di (meth) acrylate, adamantane dimethanol di (meth) acrylate, pentaerythritol tri (meth) acrylate , Adamantanetriol tri (meth) acrylate, adamantanetrimethanol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy ( And (meth) acrylate.
無機微粒子としては、用途に応じて粒径が数ｎｍ～１０μｍのものが使用でき、例えば、ガラス粉末、シリカ粉末、チタニア、酸化亜鉛、ジルコニア及びアルミナ等の公知の無機微粒子が挙げられる。
レべリング剤としては、シリコーン系、フッ素系のレベリング剤が挙げられる。 As the inorganic fine particles, those having a particle size of several nanometers to 10 μm can be used depending on applications, and examples thereof include known inorganic fine particles such as glass powder, silica powder, titania, zinc oxide, zirconia and alumina.
Examples of the leveling agent include silicone-based and fluorine-based leveling agents.
レべリング剤としては、シリコーン系、フッ素系のレベリング剤が挙げられる。 As the inorganic fine particles, those having a particle size of several nanometers to 10 μm can be used depending on applications, and examples thereof include known inorganic fine particles such as glass powder, silica powder, titania, zinc oxide, zirconia and alumina.
Examples of the leveling agent include silicone-based and fluorine-based leveling agents.
本発明の組成物は、ハードコート層を形成するハードコート樹脂組成物（ハードコート剤）として好適に用いることができる。本発明のポリマーのアダマンタン骨格によってハードコート層を高硬度とし、かつハードコート層のカールが抑制され、（メタ）アクレートが架橋ユニットになることよって、ハードコートをより高硬度とすることができる。
The composition of the present invention can be suitably used as a hard coat resin composition (hard coat agent) for forming a hard coat layer. The hard coat layer is made to have high hardness by the adamantane skeleton of the polymer of the present invention, curling of the hard coat layer is suppressed, and the (meth) acrylate becomes a crosslinking unit, whereby the hard coat can be made to have higher hardness.
本発明の樹脂組成物を硬化してなるハードコート層は、ポリエステルフィルムとの密着性に優れるため、ハードコート層を形成する際には、コロナ処理等の表面処理をしなくても、ポリエステルフィルム表面に直接組成物を塗布、硬化することでハードコートフィルムとすることができる。
また、通常ポリエステルフィルムは、加熱によりオリゴマーが析出してフィルムが白濁化し、ヘーズが大きくなってしまうが、本発明の組成物を硬化してなるハードコート層をポリエステルフィルムの両面に積層することで、加熱しても白濁化しない又は白濁化を低減できるハードコートフィルムとすることができる。 Since the hard coat layer formed by curing the resin composition of the present invention is excellent in adhesion to the polyester film, the polyester film can be formed without performing a surface treatment such as corona treatment when forming the hard coat layer. A hard coat film can be obtained by directly coating and curing the composition on the surface.
In addition, the polyester film usually precipitates by heating, the film becomes clouded and haze increases, but by laminating hard coat layers obtained by curing the composition of the present invention on both sides of the polyester film. , A hard coat film that does not become clouded even when heated or can reduce clouding can be obtained.
また、通常ポリエステルフィルムは、加熱によりオリゴマーが析出してフィルムが白濁化し、ヘーズが大きくなってしまうが、本発明の組成物を硬化してなるハードコート層をポリエステルフィルムの両面に積層することで、加熱しても白濁化しない又は白濁化を低減できるハードコートフィルムとすることができる。 Since the hard coat layer formed by curing the resin composition of the present invention is excellent in adhesion to the polyester film, the polyester film can be formed without performing a surface treatment such as corona treatment when forming the hard coat layer. A hard coat film can be obtained by directly coating and curing the composition on the surface.
In addition, the polyester film usually precipitates by heating, the film becomes clouded and haze increases, but by laminating hard coat layers obtained by curing the composition of the present invention on both sides of the polyester film. , A hard coat film that does not become clouded even when heated or can reduce clouding can be obtained.
ハードコート剤は、主にポリカーボネート樹脂、アクリル樹脂、ポリエチレンテレフタレート樹脂等の耐薬品性の向上及び傷つき防止のための材料である。例えば、スピンコート、スプレー、フロー、ディップ等の塗工方法により、ハードコート樹脂組成物を塗布及び硬化し、基材上に膜厚２～１０μｍのハードコート層を形成することで、基材に耐擦傷性を付与することができる。
The hard coat agent is a material mainly for improving chemical resistance and preventing scratches such as polycarbonate resin, acrylic resin, and polyethylene terephthalate resin. For example, a hard coat resin composition is applied and cured by a coating method such as spin coating, spraying, flow, or dip, and a hard coat layer having a thickness of 2 to 10 μm is formed on the base material. Abrasion resistance can be imparted.
本発明の組成物の硬化方法は、特に制限はなく、通常、加熱硬化法又は紫外線照射による硬化法を用いることができる。
加熱硬化法としては、硬化温度が、通常、５０～２００℃程度、好ましくは１００～１８０℃である。５０℃以上とすることにより硬化不良となることがなく、２００℃以下とすることにより着色等を生じることが無くなる。
硬化時間は、組成物が含む成分によって異なるが、通常、０．５～６時間が好ましい。
紫外線照射による硬化法としては、紫外線を、光量が、通常、５０～５０００ｍＪ／ｃｍ２程度、好ましくは１００～４０００ｍＪ／ｃｍ２になるように照射する。紫外線照射後に後加熱を行ってもよく、７０～２００℃で０．５～１２時間行うことが好ましい。 The curing method of the composition of the present invention is not particularly limited, and usually a heat curing method or a curing method by ultraviolet irradiation can be used.
In the heat curing method, the curing temperature is usually about 50 to 200 ° C., preferably 100 to 180 ° C. Setting it to 50 ° C. or higher does not cause poor curing, and setting it to 200 ° C. or lower eliminates coloring and the like.
The curing time varies depending on the components contained in the composition, but is usually preferably 0.5 to 6 hours.
The curing method by ultraviolet irradiation, the ultraviolet light quantity is usually, 50 ~ 5000mJ / cm 2, preferably about irradiated to be 100 ~ 4000mJ / cm 2. Post-heating may be performed after the ultraviolet irradiation, and it is preferably performed at 70 to 200 ° C. for 0.5 to 12 hours.
加熱硬化法としては、硬化温度が、通常、５０～２００℃程度、好ましくは１００～１８０℃である。５０℃以上とすることにより硬化不良となることがなく、２００℃以下とすることにより着色等を生じることが無くなる。
硬化時間は、組成物が含む成分によって異なるが、通常、０．５～６時間が好ましい。
紫外線照射による硬化法としては、紫外線を、光量が、通常、５０～５０００ｍＪ／ｃｍ２程度、好ましくは１００～４０００ｍＪ／ｃｍ２になるように照射する。紫外線照射後に後加熱を行ってもよく、７０～２００℃で０．５～１２時間行うことが好ましい。 The curing method of the composition of the present invention is not particularly limited, and usually a heat curing method or a curing method by ultraviolet irradiation can be used.
In the heat curing method, the curing temperature is usually about 50 to 200 ° C., preferably 100 to 180 ° C. Setting it to 50 ° C. or higher does not cause poor curing, and setting it to 200 ° C. or lower eliminates coloring and the like.
The curing time varies depending on the components contained in the composition, but is usually preferably 0.5 to 6 hours.
The curing method by ultraviolet irradiation, the ultraviolet light quantity is usually, 50 ~ 5000mJ / cm 2, preferably about irradiated to be 100 ~ 4000mJ / cm 2. Post-heating may be performed after the ultraviolet irradiation, and it is preferably performed at 70 to 200 ° C. for 0.5 to 12 hours.
実施例１
還流冷却管、攪拌機、温度計及び窒素導入管を備え付けた１０００ｍＬ丸底フラスコに、１－アダマンチルメタクリレートを８８．１ｇ、グリシジルメタクリレートを５６．９ｇ、及びメチルイソブチルケトンを３００ｇ加え、３０分間窒素バブリングを行った。その後、アゾビスイソブチロニトリル８．２ｇをさらに加え、８０℃に昇温して３時間反応させた。その後、反応液を室温まで冷却し、窒素導入管を空気導入管に付け替え、アクリル酸２９．４ｇ、トリフェニルホスフィン２．３ｇ及びメトキノン３５ｍｇを加え、空気をバブリングしながら、１１０℃まで昇温し、酸価が５ｍｇ－ＫＯＨ／ｇ以下になるまで１２時間反応させた。
得られたポリマー溶液を室温にまで下げ、固形分濃度が３５ｗｔ％になるようＭＩＢＫを加え、反応性ポリマーＡ溶液を得た。 Example 1
To a 1000 mL round bottom flask equipped with a reflux condenser, stirrer, thermometer and nitrogen inlet tube, 88.1 g of 1-adamantyl methacrylate, 56.9 g of glycidyl methacrylate, and 300 g of methyl isobutyl ketone were added, and nitrogen bubbling was performed for 30 minutes. went. Thereafter, 8.2 g of azobisisobutyronitrile was further added, and the mixture was heated to 80 ° C. and reacted for 3 hours. Thereafter, the reaction solution is cooled to room temperature, the nitrogen introduction tube is replaced with an air introduction tube, acrylic acid 29.4 g, triphenylphosphine 2.3 g and methoquinone 35 mg are added, and the temperature is raised to 110 ° C. while bubbling air. The reaction was continued for 12 hours until the acid value reached 5 mg-KOH / g or less.
The obtained polymer solution was lowered to room temperature, and MIBK was added so that the solid content concentration was 35 wt% to obtain a reactive polymer A solution.
還流冷却管、攪拌機、温度計及び窒素導入管を備え付けた１０００ｍＬ丸底フラスコに、１－アダマンチルメタクリレートを８８．１ｇ、グリシジルメタクリレートを５６．９ｇ、及びメチルイソブチルケトンを３００ｇ加え、３０分間窒素バブリングを行った。その後、アゾビスイソブチロニトリル８．２ｇをさらに加え、８０℃に昇温して３時間反応させた。その後、反応液を室温まで冷却し、窒素導入管を空気導入管に付け替え、アクリル酸２９．４ｇ、トリフェニルホスフィン２．３ｇ及びメトキノン３５ｍｇを加え、空気をバブリングしながら、１１０℃まで昇温し、酸価が５ｍｇ－ＫＯＨ／ｇ以下になるまで１２時間反応させた。
得られたポリマー溶液を室温にまで下げ、固形分濃度が３５ｗｔ％になるようＭＩＢＫを加え、反応性ポリマーＡ溶液を得た。 Example 1
To a 1000 mL round bottom flask equipped with a reflux condenser, stirrer, thermometer and nitrogen inlet tube, 88.1 g of 1-adamantyl methacrylate, 56.9 g of glycidyl methacrylate, and 300 g of methyl isobutyl ketone were added, and nitrogen bubbling was performed for 30 minutes. went. Thereafter, 8.2 g of azobisisobutyronitrile was further added, and the mixture was heated to 80 ° C. and reacted for 3 hours. Thereafter, the reaction solution is cooled to room temperature, the nitrogen introduction tube is replaced with an air introduction tube, acrylic acid 29.4 g, triphenylphosphine 2.3 g and methoquinone 35 mg are added, and the temperature is raised to 110 ° C. while bubbling air. The reaction was continued for 12 hours until the acid value reached 5 mg-KOH / g or less.
The obtained polymer solution was lowered to room temperature, and MIBK was added so that the solid content concentration was 35 wt% to obtain a reactive polymer A solution.
実施例２
１－アダマンチルメタクリレートを１１２．２ｇ、グリシジルメタクリレートを３３．５ｇ、アゾビスイソブチロニトリルを７．５ｇ、アクリル酸を１７．３ｇ、及びトリフェニルホスフィンを１．４ｇとした他は実施例１と同様にして反応性ポリマーＢ溶液を得た。 Example 2
Example 1 except that 112.2 g of 1-adamantyl methacrylate, 33.5 g of glycidyl methacrylate, 7.5 g of azobisisobutyronitrile, 17.3 g of acrylic acid, and 1.4 g of triphenylphosphine were used. In the same manner, a reactive polymer B solution was obtained.
１－アダマンチルメタクリレートを１１２．２ｇ、グリシジルメタクリレートを３３．５ｇ、アゾビスイソブチロニトリルを７．５ｇ、アクリル酸を１７．３ｇ、及びトリフェニルホスフィンを１．４ｇとした他は実施例１と同様にして反応性ポリマーＢ溶液を得た。 Example 2
Example 1 except that 112.2 g of 1-adamantyl methacrylate, 33.5 g of glycidyl methacrylate, 7.5 g of azobisisobutyronitrile, 17.3 g of acrylic acid, and 1.4 g of triphenylphosphine were used. In the same manner, a reactive polymer B solution was obtained.
実施例３
１－アダマンチルメタクリレートを５２．９ｇ、グリシジルメタクリレートを７９．６ｇ、アゾビスイソブチロニトリルを８．８ｇ、アクリル酸を４１．２ｇ、トリフェニルホスフィンを３．３ｇとした他は実施例１と同様にして反応性ポリマーＣ溶液を得た。 Example 3
Example 1 except that 52.9 g of 1-adamantyl methacrylate, 79.6 g of glycidyl methacrylate, 8.8 g of azobisisobutyronitrile, 41.2 g of acrylic acid, and 3.3 g of triphenylphosphine were used. Thus, a reactive polymer C solution was obtained.
１－アダマンチルメタクリレートを５２．９ｇ、グリシジルメタクリレートを７９．６ｇ、アゾビスイソブチロニトリルを８．８ｇ、アクリル酸を４１．２ｇ、トリフェニルホスフィンを３．３ｇとした他は実施例１と同様にして反応性ポリマーＣ溶液を得た。 Example 3
Example 1 except that 52.9 g of 1-adamantyl methacrylate, 79.6 g of glycidyl methacrylate, 8.8 g of azobisisobutyronitrile, 41.2 g of acrylic acid, and 3.3 g of triphenylphosphine were used. Thus, a reactive polymer C solution was obtained.
実施例４
還流冷却管、攪拌機、温度計及び窒素導入管を備え付けた１０００ｍＬ丸底フラスコに、１－アダマンチルメタクリレートを８８．１ｇ、メタクリル酸を３４．４ｇ、及びメチルイソブチルケトンを３００ｇ加え、３０分間窒素バブリングを行った。その後、アゾビスイソブチロニトリル８．２ｇをさらに加え、８０℃に昇温して３時間反応させた。その後、反応液を室温まで冷却し、窒素導入管を空気導入管に付け替え、グリシジルメタクリレート５６．９ｇ、トリフェニルホスフィン２．７ｇ、メトキノン３５ｍｇを加えた。空気をバブリングし、１１０℃まで昇温し酸価が５ｍｇ－ＫＯＨ／ｇ以下になるまで１２時間反応させた。
得られたポリマー溶液を室温にまで下げ、固形分濃度が３５ｗｔ％になるようＭＩＢＫを加え、反応性ポリマーＤ溶液を得た。 Example 4
To a 1000 mL round bottom flask equipped with a reflux condenser, stirrer, thermometer and nitrogen inlet tube, 88.1 g of 1-adamantyl methacrylate, 34.4 g of methacrylic acid, and 300 g of methyl isobutyl ketone were added, and nitrogen bubbling was performed for 30 minutes. went. Thereafter, 8.2 g of azobisisobutyronitrile was further added, and the mixture was heated to 80 ° C. and reacted for 3 hours. Thereafter, the reaction solution was cooled to room temperature, the nitrogen introduction tube was replaced with an air introduction tube, and 56.9 g of glycidyl methacrylate, 2.7 g of triphenylphosphine, and 35 mg of methoquinone were added. Air was bubbled, the temperature was raised to 110 ° C., and the reaction was continued for 12 hours until the acid value reached 5 mg-KOH / g or less.
The obtained polymer solution was lowered to room temperature, and MIBK was added so that the solid content concentration was 35 wt% to obtain a reactive polymer D solution.
還流冷却管、攪拌機、温度計及び窒素導入管を備え付けた１０００ｍＬ丸底フラスコに、１－アダマンチルメタクリレートを８８．１ｇ、メタクリル酸を３４．４ｇ、及びメチルイソブチルケトンを３００ｇ加え、３０分間窒素バブリングを行った。その後、アゾビスイソブチロニトリル８．２ｇをさらに加え、８０℃に昇温して３時間反応させた。その後、反応液を室温まで冷却し、窒素導入管を空気導入管に付け替え、グリシジルメタクリレート５６．９ｇ、トリフェニルホスフィン２．７ｇ、メトキノン３５ｍｇを加えた。空気をバブリングし、１１０℃まで昇温し酸価が５ｍｇ－ＫＯＨ／ｇ以下になるまで１２時間反応させた。
得られたポリマー溶液を室温にまで下げ、固形分濃度が３５ｗｔ％になるようＭＩＢＫを加え、反応性ポリマーＤ溶液を得た。 Example 4
To a 1000 mL round bottom flask equipped with a reflux condenser, stirrer, thermometer and nitrogen inlet tube, 88.1 g of 1-adamantyl methacrylate, 34.4 g of methacrylic acid, and 300 g of methyl isobutyl ketone were added, and nitrogen bubbling was performed for 30 minutes. went. Thereafter, 8.2 g of azobisisobutyronitrile was further added, and the mixture was heated to 80 ° C. and reacted for 3 hours. Thereafter, the reaction solution was cooled to room temperature, the nitrogen introduction tube was replaced with an air introduction tube, and 56.9 g of glycidyl methacrylate, 2.7 g of triphenylphosphine, and 35 mg of methoquinone were added. Air was bubbled, the temperature was raised to 110 ° C., and the reaction was continued for 12 hours until the acid value reached 5 mg-KOH / g or less.
The obtained polymer solution was lowered to room temperature, and MIBK was added so that the solid content concentration was 35 wt% to obtain a reactive polymer D solution.
実施例５
１－アダマンチルメタクリレートの代わりに３－ヒドロキシ－１－アダマンチルメタクリレートを９４．５ｇ使用した他は実施例１と同様にして反応性ポリマーＥ溶液を得た。 Example 5
A reactive polymer E solution was obtained in the same manner as in Example 1 except that 94.5 g of 3-hydroxy-1-adamantyl methacrylate was used instead of 1-adamantyl methacrylate.
１－アダマンチルメタクリレートの代わりに３－ヒドロキシ－１－アダマンチルメタクリレートを９４．５ｇ使用した他は実施例１と同様にして反応性ポリマーＥ溶液を得た。 Example 5
A reactive polymer E solution was obtained in the same manner as in Example 1 except that 94.5 g of 3-hydroxy-1-adamantyl methacrylate was used instead of 1-adamantyl methacrylate.
実施例６
１－アダマンチルメタクリレートの代わりにパーフルオロ－１－アダマンチルメタクリレート１１７．６ｇ、グリシジルメタクリレートを７９．６ｇ、アゾビスイソブチロニトリルを８．８ｇ、メチルイソブチルケトンを４００ｇ、アクリル酸を４１．２ｇ、トリフェニルホスフィンを３．３ｇとした他は実施例１と同様にして反応性ポリマーＦ溶液を得た。 Example 6
Instead of 1-adamantyl methacrylate, 117.6 g of perfluoro-1-adamantyl methacrylate, 79.6 g of glycidyl methacrylate, 8.8 g of azobisisobutyronitrile, 400 g of methyl isobutyl ketone, 41.2 g of acrylic acid, A reactive polymer F solution was obtained in the same manner as in Example 1 except that 3.3 g of phenylphosphine was used.
１－アダマンチルメタクリレートの代わりにパーフルオロ－１－アダマンチルメタクリレート１１７．６ｇ、グリシジルメタクリレートを７９．６ｇ、アゾビスイソブチロニトリルを８．８ｇ、メチルイソブチルケトンを４００ｇ、アクリル酸を４１．２ｇ、トリフェニルホスフィンを３．３ｇとした他は実施例１と同様にして反応性ポリマーＦ溶液を得た。 Example 6
Instead of 1-adamantyl methacrylate, 117.6 g of perfluoro-1-adamantyl methacrylate, 79.6 g of glycidyl methacrylate, 8.8 g of azobisisobutyronitrile, 400 g of methyl isobutyl ketone, 41.2 g of acrylic acid, A reactive polymer F solution was obtained in the same manner as in Example 1 except that 3.3 g of phenylphosphine was used.
実施例７
１－アダマンチルメタクリレートの代わりにメチルメタクリレートを５５．１ｇ使用し、グリシジルメタクリレートを７８．２ｇ、アゾビスイソブチロニトリルを１２．３ｇ、アクリル酸を４０．４ｇ及びトリフェニルホスフィンを３．２ｇとした他は実施例１と同様にして反応性ポリマーＧ溶液を得た。 Example 7
Instead of 1-adamantyl methacrylate, 55.1 g of methyl methacrylate was used, 78.2 g of glycidyl methacrylate, 12.3 g of azobisisobutyronitrile, 40.4 g of acrylic acid, and 3.2 g of triphenylphosphine. Otherwise, a reactive polymer G solution was obtained in the same manner as in Example 1.
１－アダマンチルメタクリレートの代わりにメチルメタクリレートを５５．１ｇ使用し、グリシジルメタクリレートを７８．２ｇ、アゾビスイソブチロニトリルを１２．３ｇ、アクリル酸を４０．４ｇ及びトリフェニルホスフィンを３．２ｇとした他は実施例１と同様にして反応性ポリマーＧ溶液を得た。 Example 7
Instead of 1-adamantyl methacrylate, 55.1 g of methyl methacrylate was used, 78.2 g of glycidyl methacrylate, 12.3 g of azobisisobutyronitrile, 40.4 g of acrylic acid, and 3.2 g of triphenylphosphine. Otherwise, a reactive polymer G solution was obtained in the same manner as in Example 1.
［組成物の調製及びハードコート層の評価］
実施例８
実施例１で調製した反応性ポリマーＡ溶液２００ｇに、重合開始剤として１－ヒドロキシ－シクロヘキシル－フェニル－ケトン（製品名：イルガキュア１８４）を２．１ｇ加え、ハードコート樹脂溶液を調製した。
厚さ１００μｍのＰＥＴフィルム（東レ（株）製ルミラーＴ６０）に、調製したハードコート樹脂溶液をバーコーターを用いて塗布し、９０℃で２分乾燥させた。その後、高圧水銀ランプを用いて５００ｍＪ／ｍｉｎで照射し、塗布層を硬化させ、厚さ５μｍのハードコート層を形成した。
得られたＰＥＴフィルムとハードコート層の積層体であるハードコートフィルムについて、以下の項目を評価した。結果を表２に示す。 [Preparation of composition and evaluation of hard coat layer]
Example 8
2.1 g of 1-hydroxy-cyclohexyl-phenyl-ketone (product name: Irgacure 184) was added as a polymerization initiator to 200 g of the reactive polymer A solution prepared in Example 1 to prepare a hard coat resin solution.
The prepared hard coat resin solution was applied to a PET film having a thickness of 100 μm (Lumilar T60 manufactured by Toray Industries, Inc.) using a bar coater and dried at 90 ° C. for 2 minutes. Then, it irradiated with 500 mJ / min using the high pressure mercury lamp, the coating layer was hardened, and the hard-coat layer of thickness 5 micrometers was formed.
The following items were evaluated for the hard coat film which is a laminate of the obtained PET film and the hard coat layer. The results are shown in Table 2.
実施例８
実施例１で調製した反応性ポリマーＡ溶液２００ｇに、重合開始剤として１－ヒドロキシ－シクロヘキシル－フェニル－ケトン（製品名：イルガキュア１８４）を２．１ｇ加え、ハードコート樹脂溶液を調製した。
厚さ１００μｍのＰＥＴフィルム（東レ（株）製ルミラーＴ６０）に、調製したハードコート樹脂溶液をバーコーターを用いて塗布し、９０℃で２分乾燥させた。その後、高圧水銀ランプを用いて５００ｍＪ／ｍｉｎで照射し、塗布層を硬化させ、厚さ５μｍのハードコート層を形成した。
得られたＰＥＴフィルムとハードコート層の積層体であるハードコートフィルムについて、以下の項目を評価した。結果を表２に示す。 [Preparation of composition and evaluation of hard coat layer]
Example 8
2.1 g of 1-hydroxy-cyclohexyl-phenyl-ketone (product name: Irgacure 184) was added as a polymerization initiator to 200 g of the reactive polymer A solution prepared in Example 1 to prepare a hard coat resin solution.
The prepared hard coat resin solution was applied to a PET film having a thickness of 100 μm (Lumilar T60 manufactured by Toray Industries, Inc.) using a bar coater and dried at 90 ° C. for 2 minutes. Then, it irradiated with 500 mJ / min using the high pressure mercury lamp, the coating layer was hardened, and the hard-coat layer of thickness 5 micrometers was formed.
The following items were evaluated for the hard coat film which is a laminate of the obtained PET film and the hard coat layer. The results are shown in Table 2.
［鉛筆硬度］
ＪＩＳ Ｋ５６００に従い、７５０ｇ荷重の鉛筆引っかき試験機を用いて、ハードコートフィルムの鉛筆硬度を測定した。
［耐擦傷性］
スチールウール＃００００に２００ｇｆの荷重をかけて、ハードコートフィルムのハードコート層上を１０往復させ、表面の傷の状況を目視により観察し、以下の基準により評価した。
○：傷なし
△：傷１０本未満
×：傷１０本以上
［カール］
ハードコートフィルムを１０ｃｍ×１０ｃｍに切り出し、フィルム４隅の反りの高さを測定し、その平均値をカールとした。
［密着性］
ＪＩＳ Ｋ５６００に従い、ハードコート層に碁盤目の切り込み（１ｍｍ×１ｍｍ、１００枡）をいれ、セロハンテープによる剥離試験を実施し、剥離試験後のハードコート層の残存数を密着性と評価した。例えば、例えば剥離がない場合は残存数が１００となり、すべて剥離した場合は残存数が０となる。
［全光線透過率］
ＨＧＭ－２ＤＰ（スガ試験機社製）を用いて、ＪＩＳ Ｋ７１０５に準拠してハードコートフィルムの全光線透過率を測定した（単位：％）。 [Pencil hardness]
According to JIS K5600, the pencil hardness of the hard coat film was measured using a pencil scratch tester with a load of 750 g.
[Abrasion resistance]
A load of 200 gf was applied to Steel Wool # 0000, and the hard coat layer of the hard coat film was reciprocated 10 times. The condition of the scratches on the surface was visually observed and evaluated according to the following criteria.
○: No scratch Δ: Less than 10 scratches ×: 10 or more scratches [Curl]
The hard coat film was cut into 10 cm × 10 cm, the height of the warp at the four corners of the film was measured, and the average value was defined as curl.
[Adhesion]
According to JIS K5600, grid cuts (1 mm × 1 mm, 100 mm) were made in the hard coat layer, a peel test with a cellophane tape was performed, and the remaining number of hard coat layers after the peel test was evaluated as adhesion. For example, when there is no peeling, the remaining number is 100, and when all are peeled, the remaining number is zero.
[Total light transmittance]
Using HGM-2DP (manufactured by Suga Test Instruments Co., Ltd.), the total light transmittance of the hard coat film was measured according to JIS K7105 (unit:%).
ＪＩＳ Ｋ５６００に従い、７５０ｇ荷重の鉛筆引っかき試験機を用いて、ハードコートフィルムの鉛筆硬度を測定した。
［耐擦傷性］
スチールウール＃００００に２００ｇｆの荷重をかけて、ハードコートフィルムのハードコート層上を１０往復させ、表面の傷の状況を目視により観察し、以下の基準により評価した。
○：傷なし
△：傷１０本未満
×：傷１０本以上
［カール］
ハードコートフィルムを１０ｃｍ×１０ｃｍに切り出し、フィルム４隅の反りの高さを測定し、その平均値をカールとした。
［密着性］
ＪＩＳ Ｋ５６００に従い、ハードコート層に碁盤目の切り込み（１ｍｍ×１ｍｍ、１００枡）をいれ、セロハンテープによる剥離試験を実施し、剥離試験後のハードコート層の残存数を密着性と評価した。例えば、例えば剥離がない場合は残存数が１００となり、すべて剥離した場合は残存数が０となる。
［全光線透過率］
ＨＧＭ－２ＤＰ（スガ試験機社製）を用いて、ＪＩＳ Ｋ７１０５に準拠してハードコートフィルムの全光線透過率を測定した（単位：％）。 [Pencil hardness]
According to JIS K5600, the pencil hardness of the hard coat film was measured using a pencil scratch tester with a load of 750 g.
[Abrasion resistance]
A load of 200 gf was applied to Steel Wool # 0000, and the hard coat layer of the hard coat film was reciprocated 10 times. The condition of the scratches on the surface was visually observed and evaluated according to the following criteria.
○: No scratch Δ: Less than 10 scratches ×: 10 or more scratches [Curl]
The hard coat film was cut into 10 cm × 10 cm, the height of the warp at the four corners of the film was measured, and the average value was defined as curl.
[Adhesion]
According to JIS K5600, grid cuts (1 mm × 1 mm, 100 mm) were made in the hard coat layer, a peel test with a cellophane tape was performed, and the remaining number of hard coat layers after the peel test was evaluated as adhesion. For example, when there is no peeling, the remaining number is 100, and when all are peeled, the remaining number is zero.
[Total light transmittance]
Using HGM-2DP (manufactured by Suga Test Instruments Co., Ltd.), the total light transmittance of the hard coat film was measured according to JIS K7105 (unit:%).
実施例９－１４及び比較例１－２
表１に示す配合量に従って、実施例８と同様にしてハードコート樹脂溶液をそれぞれ調製し、調製したハードコート樹脂溶液を用いて、実施例８と同様にしてハードコートフィルムをそれぞれ製造し、評価した。結果を表２に示す。 Example 9-14 and Comparative Example 1-2
According to the blending amounts shown in Table 1, hard coat resin solutions were prepared in the same manner as in Example 8, and using the prepared hard coat resin solutions, hard coat films were produced in the same manner as in Example 8, and evaluated. did. The results are shown in Table 2.
表１に示す配合量に従って、実施例８と同様にしてハードコート樹脂溶液をそれぞれ調製し、調製したハードコート樹脂溶液を用いて、実施例８と同様にしてハードコートフィルムをそれぞれ製造し、評価した。結果を表２に示す。 Example 9-14 and Comparative Example 1-2
According to the blending amounts shown in Table 1, hard coat resin solutions were prepared in the same manner as in Example 8, and using the prepared hard coat resin solutions, hard coat films were produced in the same manner as in Example 8, and evaluated. did. The results are shown in Table 2.
実施例１５
厚さ１００μｍのＰＥＴフィルム（東レ（株）製ルミラーＴ６０）に、実施例１２で調製したハードコート液をバーコーターを用いて塗布し、９０℃で２分乾燥させた。その後、高圧水銀ランプを用いて５００ｍＪ／ｍｉｎで照射し、塗布層を硬化させ、厚さ３μｍのハードコート層を形成した。この操作をフィルムの反対面にも同様に行い、両面にハードコート層を形成したＰＥＴフィルムを得た。
得られたハードコートフィルムを１５０℃で１時間加熱し、加熱前後の全光線透過率とヘーズを測定した。ヘーズはＪＩＳ Ｋ７１３６に準拠してヘーズメーターにて測定した。結果を表３に示す。 Example 15
The hard coat liquid prepared in Example 12 was applied to a PET film having a thickness of 100 μm (Lumilar T60 manufactured by Toray Industries, Inc.) using a bar coater and dried at 90 ° C. for 2 minutes. Thereafter, irradiation was performed at 500 mJ / min using a high-pressure mercury lamp, the coating layer was cured, and a hard coat layer having a thickness of 3 μm was formed. This operation was similarly performed on the opposite side of the film to obtain a PET film having a hard coat layer formed on both sides.
The obtained hard coat film was heated at 150 ° C. for 1 hour, and the total light transmittance and haze before and after heating were measured. Haze was measured with a haze meter in accordance with JIS K7136. The results are shown in Table 3.
厚さ１００μｍのＰＥＴフィルム（東レ（株）製ルミラーＴ６０）に、実施例１２で調製したハードコート液をバーコーターを用いて塗布し、９０℃で２分乾燥させた。その後、高圧水銀ランプを用いて５００ｍＪ／ｍｉｎで照射し、塗布層を硬化させ、厚さ３μｍのハードコート層を形成した。この操作をフィルムの反対面にも同様に行い、両面にハードコート層を形成したＰＥＴフィルムを得た。
得られたハードコートフィルムを１５０℃で１時間加熱し、加熱前後の全光線透過率とヘーズを測定した。ヘーズはＪＩＳ Ｋ７１３６に準拠してヘーズメーターにて測定した。結果を表３に示す。 Example 15
The hard coat liquid prepared in Example 12 was applied to a PET film having a thickness of 100 μm (Lumilar T60 manufactured by Toray Industries, Inc.) using a bar coater and dried at 90 ° C. for 2 minutes. Thereafter, irradiation was performed at 500 mJ / min using a high-pressure mercury lamp, the coating layer was cured, and a hard coat layer having a thickness of 3 μm was formed. This operation was similarly performed on the opposite side of the film to obtain a PET film having a hard coat layer formed on both sides.
The obtained hard coat film was heated at 150 ° C. for 1 hour, and the total light transmittance and haze before and after heating were measured. Haze was measured with a haze meter in accordance with JIS K7136. The results are shown in Table 3.
比較例３
比較例２で調製したハードコート液を用いた他は実施例１５と同様にしてＰＥＴフィルムの両面にハードコート層を形成したハードコートフィルムを製造し、評価した。結果を表３に示す。 Comparative Example 3
A hard coat film having a hard coat layer formed on both sides of the PET film was produced and evaluated in the same manner as in Example 15 except that the hard coat solution prepared in Comparative Example 2 was used. The results are shown in Table 3.
比較例２で調製したハードコート液を用いた他は実施例１５と同様にしてＰＥＴフィルムの両面にハードコート層を形成したハードコートフィルムを製造し、評価した。結果を表３に示す。 Comparative Example 3
A hard coat film having a hard coat layer formed on both sides of the PET film was produced and evaluated in the same manner as in Example 15 except that the hard coat solution prepared in Comparative Example 2 was used. The results are shown in Table 3.
比較例４
ＰＥＴフィルム（東レ（株）製ルミラーＴ６０）について、実施例１５と同様の評価を行った。結果を表３に示す。 Comparative Example 4
Evaluation similar to Example 15 was performed about PET film (Toray Co., Ltd. product Lumirror T60). The results are shown in Table 3.
ＰＥＴフィルム（東レ（株）製ルミラーＴ６０）について、実施例１５と同様の評価を行った。結果を表３に示す。 Comparative Example 4
Evaluation similar to Example 15 was performed about PET film (Toray Co., Ltd. product Lumirror T60). The results are shown in Table 3.
本発明のポリマーを含む組成物から得られるハードコート層を有するハードコートフィルムは、硬度が高く、カールを抑制することができ、ディスプレイ用フィルム、特にタッチパネル用のフィルムとして有用である。
The hard coat film having a hard coat layer obtained from the composition containing the polymer of the present invention has high hardness and can suppress curling, and is useful as a display film, particularly a touch panel film.
上記に本発明の実施形態及び／又は実施例を幾つか詳細に説明したが、当業者は、本発明の新規な教示及び効果から実質的に離れることなく、これら例示である実施形態及び／又は実施例に多くの変更を加えることが容易である。従って、これらの多くの変更は本発明の範囲に含まれる。
この明細書に記載の文献及び本願のパリ優先の基礎となる日本出願明細書の内容を全てここに援用する。 Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
The contents of the documents described in this specification and the specification of the Japanese application that is the basis of Paris priority of the present application are all incorporated herein.
この明細書に記載の文献及び本願のパリ優先の基礎となる日本出願明細書の内容を全てここに援用する。 Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
The contents of the documents described in this specification and the specification of the Japanese application that is the basis of Paris priority of the present application are all incorporated herein.
Claims (5)
- 下記式（Ｉ）で表わされる構造を含むポリマー。
Ｒ２及びＲ５は、それぞれ水酸基、ハロゲン原子及びヘテロ原子から選択される１以上を含む２価の脂肪族炭化水素基、２価の脂肪族炭化水素基又は単結合である。
Ｒ３は、炭化水素基、ハロゲン置換炭化水素基、環式炭化水素基、ハロゲン置換環式炭化水素基、ハロゲン原子、水酸基、カルボキシル基、又はオキソ基である。
ｍは、０～１５の整数を表す。） A polymer comprising a structure represented by the following formula (I).
R 2 and R 5 are each a divalent aliphatic hydrocarbon group containing one or more selected from a hydroxyl group, a halogen atom and a hetero atom, a divalent aliphatic hydrocarbon group or a single bond.
R 3 is a hydrocarbon group, a halogen-substituted hydrocarbon group, a cyclic hydrocarbon group, a halogen-substituted cyclic hydrocarbon group, a halogen atom, a hydroxyl group, a carboxyl group, or an oxo group.
m represents an integer of 0 to 15. ) - 前記式（Ｉ）で表わされるポリマーのＲ２が単結合であり、ｍが０である請求項１にポリマー。 The polymer according to claim 1, wherein R 2 of the polymer represented by the formula (I) is a single bond, and m is 0.
- アダマンチル基が結合した（メタ）アクリレートとエポキシ基が結合した（メタ）アクリレートを共重合した共重合体のエポキシ基に（メタ）アクリル酸を反応させて得られるポリマー、又はアダマンチル基が結合した（メタ）アクリレートと（メタ）アクリル酸を共重合した共重合体のカルボキシル基にエポキシ基が結合した（メタ）アクリレートを反応させて得られるポリマー。 A polymer obtained by reacting (meth) acrylic acid with an epoxy group of a copolymer obtained by copolymerizing (meth) acrylate having an adamantyl group and (meth) acrylate having an epoxy group bonded, or an adamantyl group having been bonded ( A polymer obtained by reacting (meth) acrylate having an epoxy group bonded to a carboxyl group of a copolymer obtained by copolymerizing (meth) acrylate and (meth) acrylic acid.
- 請求項１～３のいずれかに記載のポリマー及び光重合開始剤を含む樹脂組成物。 A resin composition comprising the polymer according to any one of claims 1 to 3 and a photopolymerization initiator.
- 請求項４に記載の樹脂組成物から得られる硬化層を有するハードコートフィルム。 A hard coat film having a cured layer obtained from the resin composition according to claim 4.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020147000152A KR101959586B1 (en) | 2011-08-10 | 2012-08-09 | Adamantane-containing polymer |
| JP2013527902A JP6099565B2 (en) | 2011-08-10 | 2012-08-09 | Adamantane polymer |
| CN201280039112.7A CN103717629B (en) | 2011-08-10 | 2012-08-09 | Adamantane based polymer |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011175145 | 2011-08-10 | ||
| JP2011-175145 | 2011-08-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2013021650A1 true WO2013021650A1 (en) | 2013-02-14 |
Family
ID=47668185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2012/005071 WO2013021650A1 (en) | 2011-08-10 | 2012-08-09 | Adamantane-containing polymer |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6099565B2 (en) |
| KR (1) | KR101959586B1 (en) |
| CN (1) | CN103717629B (en) |
| TW (2) | TWI595013B (en) |
| WO (1) | WO2013021650A1 (en) |
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| JP2013155235A (en) * | 2012-01-27 | 2013-08-15 | Dic Corp | Fluorine atom containing silicone based polymerizable resin, active energy ray curable composition using the same, cured material thereof, and article |
| JP2017514722A (en) * | 2014-03-31 | 2017-06-08 | コーロン インダストリーズ インク | Polyester film and transparent electrode film using the same |
| WO2020095774A1 (en) * | 2018-11-08 | 2020-05-14 | 昭和電工株式会社 | Copolymer, and resin composition containing copolymer |
| WO2021085241A1 (en) * | 2019-10-29 | 2021-05-06 | 積水化学工業株式会社 | Photocurable resin composition for electronic devices |
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- 2012-08-09 JP JP2013527902A patent/JP6099565B2/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| CN103717629A (en) | 2014-04-09 |
| JPWO2013021650A1 (en) | 2015-03-05 |
| TW201731887A (en) | 2017-09-16 |
| TW201321422A (en) | 2013-06-01 |
| JP6099565B2 (en) | 2017-03-22 |
| KR101959586B1 (en) | 2019-03-18 |
| TWI616462B (en) | 2018-03-01 |
| TWI595013B (en) | 2017-08-11 |
| KR20140044845A (en) | 2014-04-15 |
| CN103717629B (en) | 2016-05-18 |
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