WO2015198788A1 - Composition de résine durcissable par des rayons actiniques, composition de revêtement, film de revêtement et film stratifié - Google Patents

Composition de résine durcissable par des rayons actiniques, composition de revêtement, film de revêtement et film stratifié Download PDF

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Publication number
WO2015198788A1
WO2015198788A1 PCT/JP2015/065390 JP2015065390W WO2015198788A1 WO 2015198788 A1 WO2015198788 A1 WO 2015198788A1 JP 2015065390 W JP2015065390 W JP 2015065390W WO 2015198788 A1 WO2015198788 A1 WO 2015198788A1
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meth
acrylate
resin composition
curable resin
active energy
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PCT/JP2015/065390
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English (en)
Japanese (ja)
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伊藤　正広
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Dic株式会社
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Priority to JP2015542073A priority Critical patent/JP5935952B2/ja
Publication of WO2015198788A1 publication Critical patent/WO2015198788A1/fr

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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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention provides an active energy ray-curable resin composition, a paint containing the resin composition, and a paint film comprising the paint, which can obtain a paint film having an extremely high surface hardness and excellent workability. And a laminated film having the coating layer.
  • Plastic films produced using polyethylene terephthalate resin (PET), acrylic resin, polycarbonate resin, acetylated cellulose resin, etc. are widely used in industrial applications. These films are used as, for example, a polarizing plate protective film incorporated into a flat panel display, and these films are required to have high scratch resistance.
  • a polyfunctional acrylate having a high crosslinking density is mainly used on the film from the viewpoint of environmental advantages such as reduction of energy required for curing.
  • a method of forming a hard coat layer by applying the active energy ray-curable resin composition and curing with active energy rays such as ultraviolet rays (UV) and electron beams (EB) has been implemented.
  • Hard coating agents that can be used for such applications include acrylic polymers having a double bond in the side chain, obtained by reacting acrylic acid with an acrylic polymer containing an epoxy group, and polyfunctional acrylates.
  • An active energy ray-curable resin composition obtained by the above is known (for example, see Patent Document 1).
  • the inorganic fine particle dispersed active energy ray curable resin composition obtained by dispersing inorganic fine particles in the resin component has a higher hardness of the cured coating film compared to a resin composition consisting of only an organic material, It is provided as a new material that can be improved in performance and impart new functions such as adjusting the refractive index and imparting conductivity (see, for example, Patent Document 2).
  • a coating film obtained from a resin composition in which such inorganic fine particles are dispersed has a feature of high hardness and can be used as a hard coat layer exhibiting scratch resistance, but is inferior in processability. Therefore, it may be difficult to apply to flexible display applications.
  • the problem to be solved by the present invention is that the cured coating film has an extremely high surface hardness and exhibits an excellent workability, and an active energy ray-curable resin composition, and a paint containing the resin composition
  • Another object of the present invention is to provide a coating film comprising the coating material and a laminated film having the coating film layer.
  • an acrylic polymer (a) having a glycidyl group, a hydroxyl group, and a (meth) acryloyl group with anhydrous (meth) acrylic acid An active energy ray-curable resin composition comprising an acrylic acrylate resin (A) having a weight average molecular weight (Mw) in the range of 3,000 to 80,000 as an essential component has a very high surface after curing.
  • the present invention was completed by finding out that it has high hardness and has excellent workability (flexibility) when applied and cured on a plastic substrate.
  • the present invention has a weight average molecular weight (Mw) of 3,000 to 80, which is obtained by reacting an acrylic polymer (a) having a glycidyl group, a hydroxyl group, and a (meth) acryloyl group with anhydrous (meth) acrylic acid.
  • An active energy ray-curable resin composition containing an acrylic acrylate resin (A) in the range of 000 as an essential component, a paint containing the same, a cured coating, and a laminate having the coating layer A film is provided.
  • a cured coating film having a very high surface hardness and transparency, and a workability capable of being used as a flexible display, and an active energy ray-curable resin composition capable of providing the cured coating film A paint containing the same can be provided.
  • the active energy ray-curable resin composition of the present invention comprises a weight average molecular weight (Mw) obtained by reacting an acrylic polymer (a) having a glycidyl group, a hydroxyl group, and a (meth) acryloyl group with anhydrous (meth) acrylic acid. ) Contains an acrylic acrylate resin (A) in the range of 3,000 to 80,000.
  • the acrylic acrylate resin (A) has a weight average molecular weight (Mw) in the range of 3,000 to 80,000, the crosslinking density after curing is appropriate, and the cured coating film has a high altitude and processing. Can be imparted. From the viewpoint that these effects are more excellent and the viscosity of the active energy ray-curable resin composition is easily adjusted to one suitable for coating, the weight average molecular weight (Mw) is in the range of 8,000 to 50,000. It is preferable that it is in the range of 20,000 to 40,000.
  • the weight average molecular weight (Mw) is a value measured under the following conditions using a gel permeation chromatograph (GPC).
  • Measuring device HLC-8220 manufactured by Tosoh Corporation Column: Guard column HXL-H manufactured by Tosoh Corporation + Tosoh Corporation TSKgel G5000HXL + Tosoh Corporation TSKgel G4000HXL + Tosoh Corporation TSKgel G3000HXL + Tosoh Corporation TSKgel G2000HXL Detector: RI (differential refractometer) Data processing: Tosoh Corporation SC-8010 Measurement conditions: Column temperature 40 ° C Solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard; Polystyrene sample; 0.4 wt% tetrahydrofuran solution in terms of resin solids filtered through a microfilter (100 ⁇ l)
  • the (meth) acryloyl group equivalent of the acrylic acrylate resin (A) is in the range of 150 g / eq to 600 g / eq in that a cured coating film having high surface hardness and excellent workability can be easily obtained.
  • the range is 160 g / eq to 450 g / eq, and more preferably the range is 160 g / eq to 280 g / eq.
  • the acrylic acrylate resin (A) is, for example, a homopolymer of a compound having a glycidyl group and a (meth) acryloyl group, or a copolymer of the compound and a (meth) acrylic ester (hereinafter referred to as “precursor”). (Abbreviated as “body (1)”), and an acrylic polymer (a) obtained by reacting this with a compound having a carboxyl group and a (meth) acryloyl group is reacted with anhydrous (meth) acrylic acid.
  • the resin which consists of is mentioned.
  • An acrylic acrylate resin (A) that can be used in the present invention can be obtained by reacting anhydrous (meth) acrylic acid with a hydroxyl group produced by the reaction of a glycidyl group and a carboxyl group.
  • the compound having a glycidyl group and a (meth) acryloyl group as a raw material of the precursor (1) is, for example, glycidyl (meth) acrylate, glycidyl ⁇ -ethyl (meth) acrylate, ⁇ -n-propyl ( Glycidyl acrylate, glycidyl ⁇ -n-butyl (meth) acrylate, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid- 6,7-epoxypentyl, ⁇ -ethyl (meth) acrylic acid-6,7-epoxypentyl, ⁇ -methylglycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxycyclohexyl, lactone modified (meth) Examples include acrylic acid-3,4-epoxycyclohexyl and
  • glycidyl (meth) acrylate glycidyl ⁇ -ethyl (meth) acrylate, and the like, in that the (meth) acryloyl group equivalent of the resulting acrylic polymer (a) can be easily adjusted to a preferred range
  • glycidyl ⁇ -n-propyl (meth) acrylate is preferably used, and glycidyl (meth) acrylate is more preferably used.
  • any of the (meth) acrylic acid esters that can be polymerized with the compound having the glycidyl group and the (meth) acryloyl group can be used.
  • the mass ratio of the two at the time of copolymerization [compound having glycidyl group and (meth) acryloyl group]: [(meth) acrylic ester] is in the range of 20/80 to 95/5. It is preferably used in a proportion, and more preferably in a proportion in the range of 30/70 to 90/10. Furthermore, from the viewpoint of obtaining an active energy ray-curable resin composition having excellent coating film hardness, it is preferably in the range of 60/40 to 90/10, and in the range of 80/20 to 90/10. Is particularly preferred.
  • the precursor (1) has an epoxy group derived from a compound having the glycidyl group and (meth) acryloyl group, and the epoxy equivalent of the precursor (1) is the acryloyl of the resulting acrylic polymer (a).
  • the equivalent weight In terms of easy adjustment of the equivalent weight to the range of 145 to 750 g / eq, it is preferably in the range of 150 to 500 g / eq, more preferably in the range of 150 to 250 g / eq, and 150 to 180 g. More preferably, it is in the range of / eq.
  • the precursor (1) is, for example, a compound having the glycidyl group and the (meth) acryloyl group alone in the temperature range of 60 ° C. to 150 ° C. in the presence of a polymerization initiator, or the (meth) acrylic acid.
  • a polymerization initiator or the (meth) acrylic acid.
  • it can manufacture by superposing
  • the solvent used when the precursor (1) is produced by the solution polymerization method preferably has a boiling point of 80 ° C. or higher in consideration of the reaction temperature.
  • Ketone solvents such as n-butyl ether, diisoamyl ether, dioxane, etc .; acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl, acetic acid-n-amyl, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Ester solvents such as tate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate; toluene, xylene, Solvesso 100, Solvesso 150, Swazol 1800, Swazol 310, Isopar E And hydrocarbon solvents such as Isopar G, Exxon naphtha No. 5, Exxon naphtha No. 6 and the like. These may be used alone or in combination of two or more.
  • ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone
  • ester solvents such as isopropyl acetate and acetic acid-n-butyl are preferable from the viewpoint of excellent solubility of the obtained precursor (1).
  • Examples of the catalyst used in the production of the precursor (1) include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), and 2,2′-azobis.
  • Azo compounds such as-(4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, t-butylperoxyethylhexanoate, 1,1'-bis- ( t-butylperoxy) cyclohexane, t-amylperoxy-2-ethylhexanoate, organic peroxides such as t-hexylperoxy-2-ethylhexanoate, and hydrogen peroxide.
  • the peroxide When a peroxide is used as the catalyst, the peroxide may be used together with a reducing agent to form a redox type initiator.
  • the precursor (1) thus obtained can then be reacted with a compound having a carboxyl group and a (meth) acryloyl group to obtain an acrylic polymer (a).
  • the precursor (1) is polymerized by a solution polymerization method, a compound having a carboxyl group and a (meth) acryloyl group is added to the reaction system, and the reaction is performed in a temperature range of 60 to 150 ° C. Examples thereof include a method of appropriately using a catalyst such as phenylphosphine.
  • the (meth) acryloyl group equivalent of the acrylic polymer (a) is preferably in the range of 200 to 6,200 g / eq.
  • the precursor (1), the carboxyl group and the (meth) acryloyl group It can adjust with the reaction ratio with the compound which has these.
  • the acrylic polymer (a) is obtained by reacting with respect to 1 mol of the epoxy group of the precursor (1) so that the carboxyl group is in the range of 0.1 to 0.9 mol. It becomes easy to adjust the (meth) acryloyl equivalent to the preferred range.
  • Examples of the compound having a carboxyl group and a (meth) acryloyl group used here include (meth) acrylic acid, (acryloyloxy) acetic acid, 2-carboxyethyl acrylate, 3-carboxypropyl acrylate, and 1- [succinic acid].
  • Unsaturated monocarboxylic acids such as 2- (acryloyloxy) ethyl], 1- (2-acryloyloxyethyl) phthalate, hydrogen 2- (acryloyloxy) ethyl hexahydrophthalate, and lactone-modified products thereof; maleic acid, etc.
  • Unsaturated dicarboxylic acid carboxyl group-containing polyfunctional (meth) obtained by reacting acid anhydrides such as succinic anhydride and maleic anhydride with hydroxyl-containing polyfunctional (meth) acrylate monomers such as pentaerythritol triacrylate An acrylate etc. are mentioned. These may be used alone or in combination of two or more. Among these, (meth) acrylic acid, (acryloyloxy) acetic acid, acrylic acid 2 is easy in that the (meth) acryloyl group equivalent of the resulting acrylic polymer (a) can be easily adjusted to the above-mentioned preferable range. -Carboxyethyl and 3-carboxypropyl acrylate are preferred, and (meth) acrylic acid is particularly preferred.
  • the acrylic polymer (a) thus obtained has a hydroxyl group produced by a reaction between a glycidyl group and a carboxyl group in its molecular structure.
  • the acrylic acrylate resin (A) used in the present invention can be obtained by further reacting this hydroxyl group with anhydrous (meth) acrylic acid.
  • glycidyl (meth) acrylate is used, and this is copolymerized with (meth) acrylate to obtain precursor (1).
  • the reaction between the anhydrous (meth) acrylic acid and the hydroxyl group in the acrylic polymer (a) is not particularly limited.
  • (meth) acrylic anhydride is added to the reaction system, and a catalyst such as triphenylphosphine is appropriately used in the temperature range of 80 to 120 ° C. And so on.
  • the (meth) acryloyl group equivalent of the acrylic acrylate resin (A) thus obtained is preferably in the range of 150 to 600 g / eq.
  • the acrylic polymer (a) and anhydrous (meth) It can be adjusted by the reaction ratio with acrylic acid.
  • the carboxyl group of the compound having a carboxyl group and an acryloyl group, and the (meth) acrylic anhydride is a hydroxyl group in the acrylic polymer (a).
  • the hydroxyl value of the acrylic acrylate resin (A) is preferably in the range of 5 to 230 mgKOH / g.
  • the (meth) acrylate (B) that can be used in the present application is not particularly limited, and examples thereof include various (meth) acrylate monomers and urethane (meth) acrylate.
  • Examples of the (meth) acrylate monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) ) Acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) Acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, benzyl
  • urethane (meth) acrylate examples include urethane (meth) acrylate obtained by reacting a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound.
  • Examples of the polyisocyanate compound used as a raw material for the urethane (meth) acrylate include various diisocyanate monomers and a nurate polyisocyanate compound having an isocyanurate ring structure in the molecule.
  • diisocyanate monomer examples include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene.
  • Aliphatic diisocyanates such as range isocyanate;
  • Cycloaliphatic diisocyanates such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate;
  • 1,5-naphthylene diisocyanate 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate
  • aromatic diisocyanates such as 1,4-phenylene diisocyanate and tolylene diisocyanate.
  • Examples of the nurate polyisocyanate compound having an isocyanurate ring structure in the molecule include those obtained by reacting a diisocyanate monomer with a monoalcohol and / or a diol.
  • Examples of the diisocyanate monomer used in the reaction include the various diisocyanate monomers described above, and each may be used alone or in combination of two or more.
  • Monoalcohols used in the reaction are hexanol, octanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-heptadecanol, n- Octadecanol, n-nonadecanol and the like can be mentioned, and the diol includes ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1, Examples include 3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and the like. These monoalcohols and diols may be used alone or in combination of two or more.
  • the diisocyanate monomer is preferable, and the aliphatic diisocyanate and the alicyclic diisocyanate are more preferable in that a cured coating film having better processability can be obtained.
  • Examples of the hydroxyl group-containing (meth) acrylate compound used as a raw material for the urethane (meth) acrylate include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, glycerin diacrylate, trimethylolpropane diacrylate, Aliphatic (meth) acrylate compounds such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate;
  • hydroxyl (meth) acrylate compounds glycerin diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipentaerythritol pentane are obtained because a cured coating film having excellent processability and high surface hardness can be obtained.
  • An aliphatic (meth) acrylate compound having two or more (meth) acryloyl groups in the molecular structure such as acrylate is preferred.
  • an aliphatic (meth) acrylate compound having three or more (meth) acryloyl groups in the molecular structure such as pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc. in that a cured coating film having higher surface hardness can be obtained. Is more preferable.
  • the method for producing the urethane (meth) acrylate includes, for example, the polyisocyanate compound, the hydroxyl group-containing (meth) acrylate compound, the isocyanate group of the polyisocyanate compound, and the hydroxyl group-containing (meth) acrylate compound.
  • the molar ratio [(NCO) / (OH)] to the hydroxyl group possessed is used in a ratio in the range of 1 / 0.95 to 1 / 1.05, and within the temperature range of 20 to 120 ° C., if necessary
  • Examples of the method include using various urethanization catalysts.
  • the reaction is pentaerythritol tetra (meth) acrylate or dipentaerythritol hexa
  • the urethane (meth) acrylate obtained by such a method is obtained by reacting a raw material containing the polyisocyanate compound, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate.
  • Examples thereof include urethane (meth) acrylate obtained, urethane acrylate obtained by reacting a raw material containing polyisocyanate compound, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. .
  • the weight average molecular weight (Mw) of the urethane (meth) acrylate thus obtained is preferably in the range of 800 to 20,000 in terms of excellent compatibility with the acrylic acrylate resin (A). More preferably in the range of ⁇ 1,000.
  • These compounds (B) may be used alone or in combination of two or more.
  • a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule is preferable because a coating film with higher hardness can be obtained.
  • the polyfunctional (meth) acrylate having three or more (meth) acryloyl groups include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa. (Meth) acrylate is preferred.
  • urethane (meth) acrylate as polyfunctional (meth) acrylate having three or more (meth) acryloyl groups, diisocyanate compound, glycerin diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, dipenta Urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate compound having two or more (meth) acryloyl groups in the molecular structure such as erythritol pentaacrylate is preferred, and the diisocyanate compound and (meth) acryloyl group are A urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate compound having three or more is more preferable.
  • the (meth) acrylate (B) that can be used in the present invention may be a multi-branched (meth) acrylate.
  • a multi-branched (meth) acrylate any of those provided with names such as dendrimer, core-shell, hyperbranch and the like can be used.
  • WO08 / 047620, JP Any of those provided together with the production method thereof in Japanese Patent Application Laid-Open No. 2012-111963, Japanese Patent Application Laid-Open No. 10-508052 and the like can be suitably used.
  • SIRIUS501 etc. by Osaka Organic Chemical Co., Ltd. are mentioned.
  • the use ratio of the acrylic acrylate resin (A) and the other (meth) acrylate (B) is not particularly limited, and the hardness and workability of the desired cured coating film, Can be appropriately set in view of transparency, scratch resistance, etc., but from the viewpoint of easily obtaining a coating film having particularly high surface hardness and good workability, the acrylic acrylate resin (A) and others
  • the mass ratio (A) / (B) to (meth) acrylate (B) is preferably in the range of 10/90 to 100/0, particularly in the range of 30/70 to 90/10. Is preferable, and 30/70 to 80/20 is more preferable.
  • inorganic fine particles (C) can be used in combination for the purpose of further increasing the surface hardness of the coating film and imparting other performances such as anti-blocking properties.
  • the blending ratio of the inorganic fine particles (C) can be appropriately set according to the target performance, but from the point that a highly transparent cured coating film is obtained, the active energy ray-curable resin composition contains
  • the inorganic fine particles (C) are preferably contained in the range of 30 to 55 parts by mass with respect to 100 parts by mass of the nonvolatile content. That is, when the content of the inorganic fine particles (C) is 30 parts by mass or more, the effect of improving the hardness and scratch resistance of the coating film at the time of curing becomes remarkable. Moreover, when content of the said inorganic fine particle (C) is 55 mass parts or less, the storage stability and transparency of an active energy ray hardening-type resin composition will become favorable.
  • the resin composition is excellent in storage stability, and a cured coating film having both high surface hardness, transparency, and curl resistance can be obtained, with respect to 100 parts by mass of the nonvolatile content in the composition.
  • the inorganic fine particles (C) are contained in the range of 35 to 50 parts by mass.
  • the average particle diameter of the inorganic fine particles (C) is in the range of 95 to 250 nm as a value measured by a dynamic light scattering method in a state where the inorganic fine particles (C) are dispersed in the composition. From the point which is excellent in balance with property. That is, when the average particle diameter is 95 nm or more, the surface hardness of the obtained coating film is further increased. On the other hand, when it is 250 nm or less, the resulting coating film has good transparency.
  • the average particle diameter is more preferably in the range of 100 to 130 nm in that the obtained coating film can have both higher hardness and transparency.
  • the average particle diameter of the inorganic fine particles (C) by the dynamic light scattering method is measured according to “ISO 13321”, calculated by the cumulant method, specifically,
  • the active energy ray-curable resin composition is diluted with MIBK to prepare a MIBK solution having a concentration of 1.0%, and then the MIBK solution is used to measure the particle size (“ELSZ-2” manufactured by Otsuka Electronics Co., Ltd.). Is a measured value.
  • the inorganic fine particles (C) used here include inorganic fine particles such as silica, alumina, zirconia, titania, barium titanate, and antimony trioxide. These may be used alone or in combination of two or more.
  • silica fine particles are preferable because they are easily available and easy to handle.
  • the silica fine particles include wet silica and dry silica.
  • the wet silica include so-called precipitated silica or gel silica obtained by reacting sodium silicate with a mineral acid.
  • the average particle size of the inorganic fine particles dispersed in the resin composition finally obtained is that the average particle size in the dry state is in the range of 95 to 250 nm. It is preferable in that it is easy to adjust to a preferable value.
  • dry silica fine particles are obtained, for example, by burning silicon tetrachloride in an oxygen or hydrogen flame, and have an average primary particle diameter of 3 to 100 nm, particularly 5 to 50 nm, in a state before dispersion. It is easy to adjust the average particle diameter of the inorganic fine particles (C) in the finally obtained resin composition to the above-mentioned range of 95 to 250 nm because the dry silica fine particles in the range are secondary particles. It is preferable from the point which becomes.
  • silica fine particles dry silica fine particles are preferable in that a cured coating film having higher surface hardness can be obtained.
  • the inorganic fine particles (C) may be those obtained by introducing reactive functional groups on the surface of the inorganic fine particles using a silane coupling agent to the various inorganic fine particles described above.
  • a reactive functional group on the surface of the inorganic fine particles (C) By introducing a reactive functional group on the surface of the inorganic fine particles (C), the miscibility with the organic component such as the acrylic acrylate resin (A) and other (meth) acrylate (B) is increased, and dispersion stability is improved. Storage stability is improved.
  • silane coupling agent examples include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxy Propylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- Aminoethyl) -3-amino
  • Styrene-type silane coupling agents such as p-styryltrimethoxysilane
  • Ureido-based silane coupling agents such as 3-ureidopropyltriethoxysilane
  • Chloropropyl silane coupling agents such as 3-chloropropyltrimethoxysilane
  • Sulfide-based silane coupling agents such as bis (triethoxysilylpropyl) tetrasulfide
  • Examples include isocyanate-based silane coupling agents such as 3-isocyanatopropyltriethoxysilane. These silane coupling agents may be used alone or in combination of two or more. Among these, a (meth) acryloxy-based silane coupling agent is preferable in that a cured coating film having excellent miscibility with organic components, high surface hardness, and excellent transparency can be obtained. Methoxysilane and 3-methacryloxypropyltrimethoxysilane are more preferable.
  • the resin composition of the present invention may contain a dispersion aid as necessary.
  • the dispersion aid include phosphate ester compounds such as isopropyl acid phosphate, triisodecyl phosphite, ethylene oxide-modified phosphate dimethacrylate, and the like. These may be used alone or in combination of two or more. Among these, ethylene oxide-modified phosphoric dimethacrylate is preferable because it is excellent in dispersion assist performance.
  • Examples of commercially available dispersion aids include “Kayamar PM-21” and “Kayamar PM-2” manufactured by Nippon Kayaku Co., Ltd., “Light Ester P-2M” manufactured by Kyoeisha Chemical Co., Ltd., and the like.
  • the dispersion aid When used, it is contained in the range of 0.5 to 5.0 parts by mass in 100 parts by mass of the resin composition of the present invention in that the resin composition has higher storage stability. Is preferred.
  • the resin composition of the present invention may contain an organic solvent.
  • the organic solvent may contain the solvent used at that time as it is, or further add another solvent. May be. Or the organic solvent used at the time of manufacture of the said acrylic acrylate resin (A) may be removed once, and another solvent may be used.
  • ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone
  • cyclic ether solvents such as tetrahydrofuran and dioxolane
  • ester solvents such as methyl acetate, ethyl acetate, and butyl acetate
  • aromatic solvents such as toluene and xylene
  • Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether
  • glycol ether solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether .
  • a ketone solvent and an ester solvent are preferable, and methyl isobutyl ketone is more preferable in that the resin composition has excellent storage stability and excellent paintability when used as a paint.
  • the resin composition of the present invention further comprises an ultraviolet absorber, an antioxidant, a silicon-based additive, organic beads, a fluorine-based additive, a rheology control agent, a defoaming agent, a release agent, an antistatic agent, and an antifogging agent.
  • additives such as a colorant, an organic solvent, and an inorganic filler may be contained.
  • Examples of the ultraviolet absorber include 2- [4- ⁇ (2-hydroxy-3-dodecyloxypropyl) oxy ⁇ -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- [4- ⁇ (2-hydroxy-3-tridecyloxypropyl) oxy ⁇ -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3 Triazine derivatives such as 1,5-triazine, 2- (2'-xanthenecarboxy-5'-methylphenyl) benzotriazole, 2- (2'-o-nitrobenzyloxy-5'-methylphenyl) benzotriazole, 2- And xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, and the like.
  • antioxidants examples include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, and phosphate ester-based antioxidants. These may be used alone or in combination of two or more.
  • silicon-based additive examples include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, and fluorine-modified dimethyl.
  • examples include polyorganosiloxanes having alkyl groups and phenyl groups, such as polysiloxane copolymers and amino-modified dimethylpolysiloxane copolymers, polydimethylsiloxanes having polyether-modified acrylic groups, and polydimethylsiloxanes having polyester-modified acrylic groups. It is done. These may be used alone or in combination of two or more.
  • organic beads examples include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacryl styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, Examples thereof include polyester resin beads, polyamide resin beads, polyimide resin beads, polyfluorinated ethylene resin beads, and polyethylene resin beads.
  • a preferable value of the average particle diameter of these organic beads is in the range of 1 to 10 ⁇ m. These may be used alone or in combination of two or more.
  • fluorine-based additive examples include DIC Corporation “Mega Fuck” series. These may be used alone or in combination of two or more.
  • release agent examples include “Tegorad 2200N”, “Tegorad 2300”, “Tegorad 2100” manufactured by Evonik Degussa, “UV3500” manufactured by BYK Chemie, “Paintad 8526” manufactured by Toray Dow Corning, and “SH-29PA”. Or the like. These may be used alone or in combination of two or more.
  • antistatic agent examples include pyridinium, imidazolium, phosphonium, ammonium, or lithium salts of bis (trifluoromethanesulfonyl) imide or bis (fluorosulfonyl) imide. These may be used alone or in combination of two or more.
  • the amount of the various additives used is preferably in a range where the effect is sufficiently exhibited and ultraviolet curing is not inhibited. Specifically, in an amount of 0.01 to 40 masses per 100 mass parts of the resin composition of the present invention. It is preferable to use within the range of parts.
  • the resin composition of the present invention preferably further contains a photopolymerization initiator.
  • the photopolymerization initiator include benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4,4′-bisdimethylaminobenzophenone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, Various benzophenones such as Michler's ketone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone;
  • ⁇ -diketones such as benzyl and diacetyl; sulfides such as tetramethylthiuram disulfide and p-tolyl disulfide; various benzoic acids such as 4-dimethylaminobenzoic acid and ethyl 4-dimethylaminobenzoate;
  • photopolymerization initiators 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy- 2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2 , 4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholino
  • One or more mixed systems selected from the group of phenyl) -butan-1-one It allows more active against a broad range of wavelengths of light is preferred because highly curable coating is obtained using.
  • the amount of the photopolymerization initiator used is an amount that can sufficiently exhibit the function as a photopolymerization initiator, and is preferably within a range that does not cause precipitation of crystals and physical properties of the coating film. It is preferably used in the range of 0.05 to 20 parts by mass, particularly preferably in the range of 0.1 to 10 parts by mass, with respect to 100 parts by mass of the resin composition.
  • the resin composition of the present invention may further use various photosensitizers in combination with the photopolymerization initiator.
  • the photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds.
  • thermal polymerization initiator can also be used.
  • thermal polymerization initiator examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-).
  • Azo compounds such as 2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, t-butylperoxyethylhexanoate, 1,1′-bis- (t-butylperoxy) cyclohexane
  • Organic peroxides such as t-amylperoxy-2-ethylhexanoate and t-hexylperoxy-2-ethylhexanoate, hydrogen peroxide, and the like. It is preferably used in the range of 05 to 20 parts by mass.
  • the method for producing the active energy ray-curable resin composition of the present invention includes, for example, a disperser, a disperser having a stirring blade such as a turbine blade, a paint shaker, a roll mill, a ball mill, an attritor when the inorganic fine particles (C) are used in combination.
  • the method of mixing and dispersing in the resin component which consists of said (meth) acrylate (B) is mentioned.
  • the inorganic fine particles (C) are wet silica fine particles, a uniform and stable dispersion can be obtained when any of the above-described dispersers is used.
  • the inorganic fine particles (C) are dry silica fine particles, it is preferable to use a ball mill or a bead mill in order to obtain a uniform and stable dispersion.
  • the ball mill that can be preferably used in producing the active energy ray-curable resin composition of the present invention has, for example, a vessel filled with a medium inside, a rotating shaft, and a rotating shaft coaxial with the rotating shaft.
  • a stirring blade that is rotated by the rotational drive of the rotating shaft, a raw material supply port installed in the vessel, a dispersion outlet installed in the vessel, and a portion where the rotating shaft passes through the vessel.
  • the shaft seal device has a structure in which the shaft seal device has two mechanical seal units, and the seal portions of the two mechanical seal units are sealed with an external seal liquid.
  • a wet ball mill is mentioned.
  • a method for producing an active energy ray-curable resin composition containing inorganic fine particles (C) includes, for example, a vessel filled with media inside, a rotating shaft, and a rotating shaft coaxially with the rotating shaft.
  • a stirring blade that is rotated by the rotational drive of the rotating shaft, a raw material supply port installed in the vessel, a dispersion outlet installed in the vessel, and a portion where the rotating shaft passes through the vessel.
  • a wet ball mill having a shaft seal device, wherein the shaft seal device has two mechanical seal units, and the seal portions of the two mechanical seal units are sealed with an external seal liquid.
  • the inorganic fine particles (C), the resin (A), and the (meth) acrylate (B) are formed from the supply port of the wet ball mill as an apparatus.
  • the inorganic fine particles (C) are pulverized by supplying the resin component to the vessel and rotating the rotating shaft and the stirring blade in the vessel to stir and mix the medium and the raw material. There is a method in which (C) is dispersed in the resin component and then discharged from the outlet.
  • the active energy ray-curable resin composition of the present invention can be used for paint applications.
  • the coating material can be used as a coating layer that protects the surface of the substrate by applying the coating onto various substrates and irradiating and curing the active energy rays.
  • the coating material of the present invention may be directly applied to the surface protection member, or a material applied on a plastic film may be used as the protective film. Or you may use what applied the coating material of this invention on the plastic film, and formed the coating film as optical films, such as an antireflection film, a diffusion film, and a prism sheet.
  • the coating film obtained using the paint of the present invention is characterized by high surface hardness and excellent transparency, so it can be applied to various types of plastic film with a film thickness according to the application, and used as a protective film or film It can be used as a molded product.
  • a heat treatment step can be included before or after irradiation with active energy rays.
  • the heating temperature at this time can be appropriately selected depending on the heat resistance of the substrate (plastic film) to be used, but from the viewpoint of further increasing the surface hardness, it is in the range of 80 to 200 ° C. and 1 to 180. It is preferable to perform processing for about a minute.
  • the plastic film is, for example, a plastic film made of polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, cyclic olefin, polyimide resin, or the like. And plastic sheets.
  • the triacetyl cellulose film is a film that is particularly suitably used for polarizing plates of liquid crystal displays.
  • the thickness is generally as thin as 40 to 100 ⁇ m, the surface even when a hard coat layer is provided. It is difficult to make the hardness sufficiently high, and there is a feature that it is easily curled.
  • the coating film made of the resin composition of the present invention has a high surface hardness, excellent curl resistance, workability, and transparency even when a triacetyl cellulose film is used as a base material. Can be used.
  • the coating amount when applying the coating material of the present invention is such that the film thickness after drying is in the range of 1 to 20 ⁇ m, preferably in the range of 2 to 15 ⁇ m. It is preferable.
  • the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.
  • the polyester film is, for example, polyethylene terephthalate, and the thickness thereof is generally about 100 to 300 ⁇ m. Although it is a cheap and easy to process film, it is a film used for various applications such as a touch panel display. However, it is very soft and has a feature that it is difficult to sufficiently increase the surface hardness even when a hard coat layer is provided.
  • the coating amount when applying the coating material of the present invention is in the range of 5 to 100 ⁇ m, preferably 7 to 80 ⁇ m after drying, depending on the application. It is preferable to apply as described above.
  • the paint of the present invention is excellent in curling resistance. Since it has characteristics, curling hardly occurs even when it is applied with a relatively high film thickness exceeding 20 ⁇ m, and it can be suitably used.
  • the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.
  • polymethyl methacrylate film is generally relatively thick and durable, with a thickness of about 100 to 2,000 ⁇ m. Therefore, it is suitable for applications that require particularly high surface hardness, such as the front plate of liquid crystal displays. It is the film used for.
  • the coating amount when applying the coating material of the present invention is in the range of 3 to 100 ⁇ m, preferably 7 to 80 ⁇ m after drying according to the application. It is preferable to apply so that it becomes.
  • a coating when a coating is applied on a relatively thick film such as a polymethyl methacrylate film to a film thickness exceeding 30 ⁇ m, it becomes a laminated film having a high surface hardness, but the transparency tends to decrease.
  • the coating material of the present invention has very high transparency as compared with the conventional coating material, a laminated film having both high surface hardness and transparency can be obtained.
  • the coating method at that time include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.
  • Examples of the active energy rays irradiated when the paint of the present invention is cured to form a coating film include ultraviolet rays and electron beams.
  • an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, and an LED lamp as a light source is used, and the amount of light, the arrangement of the light sources, and the like are adjusted as necessary.
  • a high-pressure mercury lamp it is preferable to cure at a conveyance speed of 5 to 50 m / min with respect to one lamp having a light quantity that is usually in the range of 80 to 160 W / cm.
  • an electron beam accelerator it is preferably cured with an electron beam accelerator having an accelerating voltage that is usually in the range of 10 to 300 kV at a conveyance speed of 5 to 50 m / min.
  • the base material to which the paint of the present invention is applied can be suitably used not only as a plastic film but also as a surface coating agent for various plastic molded products, for example, cellular phones, electric appliances, automobile bumpers and the like.
  • examples of the method for forming the coating film include a coating method, a transfer method, and a sheet bonding method.
  • the coating method is a method in which the paint is spray-coated or coated as a top coat on a molded product using a printing device such as a curtain coater, roll coater, gravure coater, etc., and then cured by irradiation with active energy rays. is there.
  • a transfer material obtained by applying the above-described coating material of the present invention on a substrate sheet having releasability is adhered to the surface of the molded product, and then the substrate sheet is peeled off to top coat the surface of the molded product.
  • curing by irradiation with active energy rays, or by bonding the transfer material to the surface of the molded article, curing by irradiation with active energy rays, and then peeling the substrate sheet A method of transferring the top coat to the surface is mentioned.
  • a protective sheet having a coating film made of the paint of the present invention on a base sheet, or a protective sheet having a coating film made of the paint and a decorative layer on a base sheet is plastic molded.
  • a protective layer is formed on the surface of the molded product by bonding to the product.
  • the coating material of the present invention can be preferably used for the transfer method and the sheet adhesion method.
  • a transfer material is first prepared.
  • the transfer material can be produced, for example, by applying the paint alone or mixed with a polyisocyanate compound onto a base sheet and heating to semi-cure (B-stage) the coating film. .
  • the above-described paint of the present invention is applied onto a base sheet.
  • the method for applying the paint include a gravure coating method, a roll coating method, a spray coating method, a lip coating method, a coating method such as a comma coating method, and a printing method such as a gravure printing method and a screen printing method.
  • the coating thickness is preferably such that the thickness of the coating after curing is 1 to 50 ⁇ m because the wear resistance and chemical resistance are good, so that it is 3 to 40 ⁇ m. It is more preferable to paint on.
  • the coating is semi-cured (B-tage) by heating and drying.
  • the heating is usually 55 to 160 ° C, preferably 100 to 140 ° C.
  • the heating time is usually 30 seconds to 30 minutes, preferably 1 to 10 minutes, more preferably 1 to 5 minutes.
  • the surface protective layer of the molded product using the transfer material may be formed by, for example, bonding the B-staged resin layer of the transfer material and the molded product, and then irradiating active energy rays to cure the resin layer.
  • the B-staged resin layer of the transfer material is adhered to the surface of the molded product, and then the base sheet of the transfer material is peeled to remove the B-staged resin layer of the transfer material.
  • energy rays are cured by irradiation with active energy rays to cure the resin layer by cross-linking (transfer method), or the transfer material is sandwiched in a mold and the resin is placed in the cavity.
  • a transfer material is adhered to the surface, the substrate sheet is peeled off and transferred onto the molded product, and then the energy beam is cured by irradiation with active energy rays to crosslink and cure the resin layer. And the like (molding simultaneous transfer method).
  • the sheet bonding method is specifically a resin layer formed by bonding a base sheet of a protective layer forming sheet prepared in advance and a molded product, and then thermally curing by heating to form a B-stage.
  • a method of performing cross-linking curing (post-adhesion method), and the protective layer forming sheet is sandwiched in a molding die, and a resin is injected and filled in the cavity to obtain a resin molded product, and at the same time, the surface and the protective layer are formed.
  • a method in which a resin sheet is bonded and then thermally cured by heating to crosslink and cure the resin layer (molding simultaneous bonding method).
  • the coating film of the present invention is a coating film formed by applying and curing the coating material of the present invention on the above-described plastic film, or coating and curing the coating material of the present invention as a surface protective agent for plastic molded products.
  • the laminated film of the present invention is a film in which a coating film is formed on a plastic film.
  • a film obtained by applying the paint of the present invention on a plastic film and irradiating an active energy ray is used as a protective film for a polarizing plate used for a liquid crystal display, a touch panel display or the like. It is preferable to use as the coating film hardness.
  • the coating film hardness when the paint of the present invention is applied to a protective film of a polarizing plate used for a liquid crystal display, a touch panel display, etc., and the film is formed by irradiating and curing active energy rays, the cured coating film has a high hardness. It becomes a protective film that combines high transparency.
  • an adhesive layer may be formed on the opposite surface of the coating layer to which the paint of the present invention is applied.
  • the weight average molecular weight (Mw) is a value measured under the following conditions using a gel permeation chromatograph (GPC).
  • Measuring device HLC-8220 manufactured by Tosoh Corporation Column: Guard column HXL-H manufactured by Tosoh Corporation + Tosoh Corporation TSKgel G5000HXL + Tosoh Corporation TSKgel G4000HXL + Tosoh Corporation TSKgel G3000HXL + Tosoh Corporation TSKgel G2000HXL Detector: RI (differential refractometer) Data processing: Tosoh Corporation SC-8010 Measurement conditions: Column temperature 40 ° C Solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard; Polystyrene sample; 0.4% by weight tetrahydrofuran solution in terms of resin solids filtered through microfilter (100 ⁇ l)
  • Synthesis Example 1 Production of acrylic acrylate resin (A-1) A reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube was charged with 96 parts by mass of methyl isobutyl ketone, and the system temperature was 110 while stirring. The temperature was raised to 0 ° C., and then from 130 parts by weight of glycidyl methacrylate, 14 parts by weight of methyl methacrylate and 6 parts by weight of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by Nippon Emulsifier Co., Ltd.) The resulting mixture was dropped from the dropping funnel over 3 hours, and then maintained at 110 ° C. for 15 hours.
  • a reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube was charged with 96 parts by mass of methyl isobutyl ketone, and the system temperature was 110 while stirring. The temperature was raised to 0 ° C., and
  • Synthesis Examples 2-6 In Synthesis Example 1, acrylic acrylate resins (A-2), (A -3) and (A-4) were obtained. Furthermore, as Synthesis Examples 5 and 6 in which methacrylic anhydride was not used, synthesis was performed at the usage ratio shown in Table 1, and comparative resins (A′-1) and (A′-2) were synthesized. The property values of the resins obtained in each synthesis example are also shown in Table 1.
  • Example 1 Active energy ray-curable resin is obtained by adding 40 parts by mass of PETA (Aronix M-305, manufactured by Toagosei Co., Ltd.) and 4 parts by mass of Irgacure 184 to 120 parts by mass of the acrylic acrylate resin (A-1) obtained in Synthesis Example 1. A composition was obtained.
  • This active energy ray-curable resin composition was applied onto a PET film (Toyobo 75 ⁇ A 4300) so as to have a dry film thickness of 15 ⁇ m, and cured at 500 mJ / cm 2 with an irradiator equipped with a high-pressure mercury lamp. A laminated film was obtained.
  • Example 2-8 and Comparative Examples 1-2 In the same manner as in Example 1, an active energy ray-curable resin composition was prepared by blending each material with the blending amount (mass basis) shown in Table 1. In Example 7, the cured coating film was further subjected to a heat treatment at 150 ° C. for 30 minutes. In Example 8, the inorganic fine particles (C) were blended, and the preparation method was dispersion by a wet ball mill. The results are shown in Table 2.
  • Each condition of dispersion by the wet ball mill is as follows.
  • Media Zirconia beads having a median diameter of 100 ⁇ m
  • Filling ratio of resin composition with respect to the inner volume of the mill 70% by volume
  • Peripheral speed at the tip of the stirring blade 11 m / sec
  • Flow rate of resin composition 200 ml / min
  • Dispersion time 60 minutes

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Abstract

L'invention concerne : une composition de résine durcissable par des rayons actiniques qui donne un film de revêtement durci qui a une dureté de surface extrêmement élevée et qui, malgré cela, peut présenter une excellente aptitude au traitement ; une composition de revêtement comprenant la composition de résine ; un film de revêtement obtenu à partir de la composition de revêtement ; et un film ayant la couche de film de revêtement. La composition de résine durcissable par des rayons actiniques selon l'invention est caractérisée en ce qu'elle contient, en tant que constituant essentiel, une résine acrylique/d'acrylate (A) qui est obtenue par réaction d'un polymère acrylique (a) ayant des groupes glycidyle, hydroxy et (méth)acryloyle avec un anhydride (méth)acrylique et qui a une masse moléculaire moyenne en poids (Mw) de 3 000 à 80 000. Le film selon l'invention a une couche de film de revêtement obtenue par durcissement de la composition de revêtement, qui comprend la composition de résine.
PCT/JP2015/065390 2014-06-26 2015-05-28 Composition de résine durcissable par des rayons actiniques, composition de revêtement, film de revêtement et film stratifié WO2015198788A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2015198787A1 (ja) * 2014-06-26 2017-04-20 Dic株式会社 活性エネルギー線硬化型樹脂組成物、塗料、塗膜、及び積層フィルム
WO2018038101A1 (fr) * 2016-08-24 2018-03-01 パナック株式会社 Composition de résine, couche de résine non durcie, film de résine et son procédé de production, et procédé de production de stratifié
KR20200019609A (ko) * 2017-06-15 2020-02-24 디아이씨 가부시끼가이샤 경화성 조성물 및 적층 필름
JP2020100686A (ja) * 2018-12-20 2020-07-02 Dic株式会社 活性エネルギー線硬化性樹脂組成物、積層フィルム、その製造方法、及び加飾フィルムの製造方法
WO2024122173A1 (fr) * 2022-12-06 2024-06-13 株式会社レゾナック Résine (méth)acrylique
WO2024122170A1 (fr) * 2022-12-06 2024-06-13 株式会社レゾナック Composition adhésive et feuille adhésive

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