Classifications

• • 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
  • C08F290/12—Polymers provided for in subclasses C08C or C08F
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
• • 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
• • 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
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds

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 in a flat panel display or a surface protective film for a touch panel, 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 cured coating film has an extremely high surface hardness, transparency, and an active energy ray-curable resin composition that exhibits excellent workability, and the resin composition It is providing the coating film containing this, the coating film consisting of this coating material, and the laminated film which has this coating film layer.
• An active energy ray-curable resin composition comprising an acrylic polymer (A) having a hydroxyl group and a (meth) acryloyl group and an isocyanate compound (B) exhibits a very high surface hardness after curing.
• the present invention has been completed by finding that it is rich in workability (flexibility) when applied and cured on a plastic substrate.
• the present invention relates to an acrylic polymer having a weight average molecular weight (Mw) in the range of 3,000 to 60,000 and having a hydroxyl group and a (meth) acryloyl group in the polymer structure.
• An active energy ray-curable resin composition containing a coalescence (A) and an isocyanate compound (B), a coating material containing the same, a cured coating film, and a laminated film having the coating layer Is to provide.
• 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 is an acrylic polymer having a weight average molecular weight (Mw) in the range of 3,000 to 60,000, and a hydroxyl group and (meth) in the polymer structure. It contains an acrylic polymer (A) having an acryloyl group and an isocyanate compound (B).
• the acrylic polymer (A) has a weight average molecular weight (Mw) in the range of 3,000 to 60,000, the crosslinking density in the reaction with the isocyanate compound (B) described later is appropriate, High hardness and workability can be imparted to the cured coating film.
• 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% by weight tetrahydrofuran solution in terms of resin solids filtered through microfilter (100 ⁇ l)
• the (meth) acryloyl group equivalent of the acrylic polymer (A) is in the range of 150 g / eq to 800 g / eq in that a cured coating film having high surface hardness and excellent workability can be easily obtained. It is preferable that it is 200 g / eq to 550 g / eq, more preferably 220 g / eq to 320 g / eq.
• the acrylic polymer (A) is, for example, an acrylic polymer obtained by polymerizing a compound (a-1) having a functional group such as a hydroxyl group, a glycidyl group, or a carboxyl group and a (meth) acryloyl group as an essential component. (A) is reacted with a functional group having reactivity with these functional groups and a compound (a-2) having a (meth) acryloyl group to form a (meth) acryloyl group on the side chain of the acrylic polymer.
• the hydroxyl group is converted into a compound (a-2 )
• the acrylic polymer (A) after the reaction can be obtained as a functional group.
• a compound having a hydroxyl group as a functional group in the compound (a-1) when used, a homopolymer of a compound having a hydroxyl group and a (meth) acryloyl group, or the compound ( A copolymer with a meth) acrylic acid ester (hereinafter abbreviated as “precursor (1)”) and a compound having an isocyanate group and a (meth) acryloyl group are obtained with respect to the hydroxyl group. And a polymer (A-1) obtained by reacting with use such that the number of isocyanate groups is reduced.
• examples of the compound having a hydroxyl group and a (meth) acryloyl group as a raw material of the precursor (1) include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3- Examples thereof include dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, and 2,3-dihydroxypropyl methacrylate.
• 2-hydroxyethyl is easy in that the (meth) acryloyl group equivalent in the obtained polymer (A) can be easily adjusted to the above-mentioned preferred range, and a polymer having a high hydroxyl value can be obtained. It is preferable to use acrylate or 2-hydroxypropyl acrylate.
• the (meth) acrylic acid ester that can be polymerized together with the compound having the hydroxyl group and the (meth) acryloyl group includes methyl (meth) acrylate and (meth) acrylic acid.
• (Meth) acrylic acid esters having an alkyl group having 1 to 22 carbon atoms and (meth) acrylic acid esters having an alicyclic alkyl group are preferred, It is particularly preferable to use methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and t-butyl (meth) acrylate.
• the mass ratio of both at the time of copolymerization [compound having a hydroxyl group and a (meth) acryloyl group] : (Meth) acrylic acid ester] is preferably used as a precursor in a ratio of 10/90 to 90/10, preferably 15/85 to 80/20. More preferably, it is more preferably in the range of 20/80 to 50/50, and most preferably in the range of 25/75 to 45/55.
• the precursor (1) is, for example, a compound having the hydroxyl 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 compound and (meth) acrylic. It can be produced by addition polymerization in combination with an acid ester, and in the case of a copolymer, any of a random copolymer, a block copolymer, a graft copolymer and the like may be used.
• a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, or the like can be used. Among these, the production of the precursor (1) and the subsequent reaction of the precursor (1) with a compound having an isocyanate group and a (meth) acryloyl group can be continuously performed. In this respect, the solution polymerization method is preferable.
• the solvent used when the precursor (1) is produced by the solution polymerization method is preferably a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone from the viewpoint of excellent solubility of the resulting acrylic polymer (A-1).
• the catalyst used in the production of the precursor (1) is, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′- Azo compounds such as azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, t-butylperoxyethylhexanoate, 1,1'-bis- Examples thereof include organic peroxides such as (t-butylperoxy) cyclohexane, t-amylperoxy-2-ethylhexanoate, and t-hexylperoxy-2-ethylhexanoate, and hydrogen peroxide.
• 2,2′-azobisisobutyronitrile 2,2′-azobis- (2,4-dimethylvaleronitrile)
• 2,2′- Azo compounds such as
• 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) obtained in this way is prepared by reacting a compound having an isocyanate group and a (meth) acryloyl group with a hydroxyl group in an amount of less than an equimolar amount with respect to the target acrylic polymer.
• the union (A-1) can be obtained.
• the precursor (1) is polymerized by a solution polymerization method, a compound having an isocyanate group and a (meth) acryloyl group is added to the reaction system, and octanoic acid is added in a temperature range of 50 to 120 ° C. It can be performed by a method such as appropriately using a catalyst such as tin (II).
• Examples of the compound having an isocyanate group and a (meth) acryloyl group used here include a compound represented by the following general formula: a monomer having one isocyanate group and one (meth) acryloyl group, one Monomer having an isocyanate group and two (meth) acryloyl groups, a monomer having one isocyanate group and three (meth) acryloyl groups, a monomer having one isocyanate group and four (meth) acryloyl groups And monomers having one isocyanate group and five (meth) acryloyl groups.
• R 1 is a hydrogen atom or a methyl group
• R 3 is an alkylene group having 2 to 4 carbon atoms
• m is an integer of 1 to 5.
• these compounds having an isocyanate group and a (meth) acryloyl group include 2-acryloyloxyethyl isocyanate (trade name: “Karenz AOI” manufactured by Showa Denko KK), 2-methacryloyloxyethyl, etc. Examples thereof include isocyanate (trade name: “Karenz MOI” manufactured by Showa Denko KK) and 1,1-bis (acryloyloxymethyl) ethyl isocyanate (trade name: “Karenz BEI” manufactured by Showa Denko KK).
• Diisocyanate compounds used in the reaction are butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, m-tetramethyl.
• Aliphatic diisocyanates such as xylylene diisocyanate; Fatty acids such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate Cyclic diisocyanate; 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-di E sulfonyl dimethyl methane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyl diphenyl methane diisocyanate, tetraalkyl diphenyl methane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene di
• the acrylic polymer (A-1) to be obtained becomes a more multifunctional compound, and has two or more (meth) acryloyl groups in one molecule from the viewpoint of easily obtaining a coating film with higher hardness.
• 1,1-bis (acryloyloxymethyl) ethyl isocyanate is preferable. Any of the aforementioned hydroxyl group-containing (meth) acrylate compounds to be added to these can be used.
• the (meth) acryloyl group equivalent of the polymer (A-1) thus obtained is preferably in the range of 150 to 800 g / eq as described above, and this is because the precursor (1) and the above-mentioned It can adjust by the reaction ratio of the compound which has an isocyanate group and a (meth) acryloyl group.
• the (meta) of the polymer (A-1) obtained is reacted with 1 mol of the hydroxyl group of the precursor (1) so that the isocyanate group is in the range of 0.7 to 0.9 mol. ) It is easy to adjust the acryloyl equivalent to the above preferred range, and it is possible to leave the hydroxyl group.
• the homopolymer of the compound which has a glycidyl group and a (meth) acryloyl group, or this compound and (meth) acrylic acid An acrylic polymer obtained by reacting a copolymer with an ester (hereinafter abbreviated as “precursor (2)”) and a compound having a carboxyl group and a (meth) acryloyl group. (A-2).
• the compound having a glycidyl group and a (meth) acryloyl group as a raw material of the precursor (2) is, for example, glycidyl (meth) acrylate, glycidyl ⁇ -ethyl (meth) acrylate, ⁇ -n-propyl ( Glycidyl (meth) 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-epoxycyclohex
• glycidyl (meth) acrylate and glycidyl ⁇ -ethyl (meth) acrylate are easy in that the (meth) acryloyl group equivalent of the obtained polymer (A) can be easily adjusted to the above-described preferable range.
• ⁇ -n-propyl (meth) acrylate glycidyl are 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.
• (meth) acrylic acid ester having an alkyl group having 1 to 22 carbon atoms and (meth) acrylic acid ester having an alicyclic alkyl group are preferable, and those having 1 to 22 carbon atoms are preferable.
• a (meth) acrylic acid ester having an alkyl group is more preferable.
• methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (n-butyl) (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate It is particularly preferred to use isobornyl (meth) acrylate.
• the mass ratio of the two at the time of copolymerization [compound having a glycidyl group and a (meth) acryloyl group]: [(meth) acrylic acid ester] ranges from 15/85 to 95/5 It is preferable to use at a ratio that becomes, and it is more preferable to use at a ratio that is in the range of 30/90 to 90/10. Furthermore, it is preferably in the range of 60/40 to 90/10, more preferably in the range of 80/20 to 90/10, from the viewpoint of obtaining an active energy ray-curable resin composition having excellent temporal stability. Particularly preferred.
• the precursor (2) has an epoxy group derived from a compound having the glycidyl group and a (meth) acryloyl group, but the epoxy equivalent of the precursor (2) is the acrylic polymer (A -2) is preferably in the range of 145 to 900 g / eq, more preferably in the range of 150 to 500 g / eq in that it is easy to adjust the acryloyl equivalent of 150 to 800 g / eq. Preferably, it is in the range of 150 to 250 g / eq, more preferably in the range of 150 to 180 g / eq.
• the precursor (2) 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 (2) is produced by the solution polymerization method preferably has a boiling point of 80 ° C. or higher in view of the reaction temperature.
• Ketone solvent; ether solvents such as n-butyl ether, diisoamyl ether, dioxane; ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol Monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol Dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol
• ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, acetic acid-n-propyl are preferable because of the excellent solubility of the resulting precursor (2) and the lack of reactivity with the isocyanate compound (B).
• An ester solvent such as isopropyl acetate and acetic acid-n-butyl is preferable.
• Examples of the catalyst used in the production of the precursor (2) 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 (2) thus obtained can then be reacted with a compound having a carboxyl group and a (meth) acryloyl group to obtain the desired acrylic polymer (A-2).
• the precursor (2) 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-2) is preferably in the range of 150 to 800 g / eq.
• the precursor (2), the carboxyl group and the (meth) acryloyl group It can adjust with the reaction ratio with the compound which has these.
• 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, and the like, because it is easy to adjust the (meth) acryloyl group equivalent of the resulting acrylic polymer (A-2) to the above preferred range. 2-carboxyethyl acid and 3-carboxypropyl acrylate are preferred, and (meth) acrylic acid is particularly preferred.
• the acrylic polymer (A-2) thus obtained has a hydroxyl group generated by a reaction between an epoxy group and a carboxyl group in its molecular structure.
• the said polymer (A) is a homopolymer of the compound which has a carboxyl group and a (meth) acryloyl group, or this compound and (meth) acryl.
• a copolymer with an acid ester (hereinafter abbreviated as “precursor (3)”) is obtained, and an acrylic polymer obtained by reacting this with a compound having a glycidyl group and a (meth) acryloyl group is obtained.
• precursor (3) an acrylic polymer obtained by reacting this with a compound having a glycidyl group and a (meth) acryloyl group is obtained.
• a combination (A-3) is a combination (A-3).
• the compound having a carboxyl group and a (meth) acryloyl group as a raw material of the precursor (3) is, for example, (meth) acrylic acid, (acryloyloxy) acetic acid, 2-carboxyethyl acrylate, acrylic acid 3 -Carboxypropyl, succinic acid 1- [2- (acryloyloxy) ethyl], 1- (2-acryloyloxyethyl) phthalate, 2- (acryloyloxy) ethyl hexahydrophthalate, and lactone-modified products thereof Unsaturated monocarboxylic acid; unsaturated dicarboxylic acid such as maleic acid; obtained by reacting acid anhydride such as succinic anhydride and maleic anhydride with hydroxyl-containing polyfunctional (meth) acrylate monomer such as pentaerythritol triacrylate A carboxyl group-containing polyfunctional (meth) acrylate may be mentioned.
• (meth) acrylic acid, (acryloyloxy) acetic acid, acrylic acid is easy in that the (meth) acryloyl group equivalent of the resulting acrylic polymer (A-3) can be easily adjusted to the above preferred range.
• 2-Carboxyethyl and 3-carboxypropyl acrylate are preferred, with (meth) acrylic acid being particularly preferred.
• any of the (meth) acrylic acid esters that can be polymerized together with the compound having the carboxyl group and the (meth) acryloyl group can be used.
• a (meth) acrylic acid ester having an alkyl group having 1 to 22 carbon atoms and a (meth) acrylic acid ester having an alicyclic alkyl group are preferable in that a rich product can be easily obtained.
• the mass ratio of the two at the time of copolymerization [compound having a carboxyl group and a (meth) acryloyl group]: [(meth) acrylic acid ester] is 15/85 to 95/5. It is preferably used in a proportion that falls within the range, and more preferably used in a proportion that falls within the range of 30/90 to 90/10. Furthermore, it is preferably in the range of 60/40 to 90/10, more preferably in the range of 80/20 to 90/10, from the viewpoint of obtaining an active energy ray-curable resin composition having excellent temporal stability. Particularly preferred.
• the precursor (3) is, for example, a compound having the carboxyl group and the (meth) acryloyl group alone or in the presence of a polymerization initiator in a temperature range of 60 ° C. to 150 ° C. )
• the solvent used when the precursor (3) is produced by the solution polymerization method has a boiling point of 80 ° C. or higher in consideration of the reaction temperature.
• Coal ether solvent acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl, acetic acid-n-amyl, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol Ester solvents such as monomethyl ether acetate, ethyl-3-ethoxypropionate; isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, diacetone alcohol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 3- Alcohol solvents such as methyl-3-methoxybutanol; toluene, xylene, Solvesso 100, Solvesso 150, Swazol 1 800, Swazol 310, Isopar E, Isopar G, Exxon naphtha No
• ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, acetic acid-n-propyl are preferable because of the excellent solubility of the resulting precursor (3) and the lack of reactivity with the isocyanate compound (B).
• An ester solvent such as isopropyl acetate and acetic acid-n-butyl is preferable.
• Examples of the catalyst used in the production of the precursor (3) 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 (3) thus obtained can then be reacted with a compound having a glycidyl group and a (meth) acryloyl group to obtain the desired acrylic polymer (A-3).
• the precursor (3) is polymerized by a solution polymerization method, a compound having a glycidyl 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 acrylic polymer (A-3) thus obtained preferably has a (meth) acryloyl group equivalent in the range of 150 to 800 g / eq. This is because the precursor (3), the glycidyl group, It can adjust with the reaction ratio with the compound which has a (meth) acryloyl group.
• the obtained acrylic polymer (A-3) has a hydroxyl group generated by a reaction between a carboxyl group and a glycidyl group in its molecular structure.
• acrylic polymers (A) described in detail above when the inorganic fine particles (D) to be described later are used, the acrylic polymers are familiar with the inorganic fine particles and are excellent in storage stability of the resulting composition. (A-2) and (A-3) are preferred.
• the hydroxyl value of the polymers (A-2) and (A-3) is such that the reactivity with the isocyanate compound (B) described later is good, and the inorganic fine particles (D) in the composition
• it is preferably in the range of 75 to 380 mgKOH / g, more preferably in the range of 110 to 360 mgKOH / g, still more preferably in the range of 230 to 360 mgKOH / g, A range of 360 mgKOH / g is particularly preferred.
• the acrylic polymer (A-2) is preferable because it can be produced by a method that is easier to synthesize.
• glycidyl (meth) acrylate is used, and this is copolymerized with a (meth) acrylic ester to give a precursor.
• the active energy ray-curable resin composition of the present invention is obtained by increasing the crosslinking point by reacting the hydroxyl group in the acrylic polymer (A) with the isocyanate group in the isocyanate compound (B). It is assumed that the processability of the coating film can be improved by increasing the surface hardness of the film and including a urethane bond. Accordingly, the isocyanate compound (B) is not particularly limited as long as it is a compound having an isocyanate group, but from the viewpoint of further increasing the crosslinking density, from an isocyanate group and an acryloyl group in one molecule. A compound having two or more functional groups selected is preferable.
• isocyanate compound (B) examples include hexamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanatomethyl ester, lysine triisocyanate, m-xylidine.
• 2,5-diisocyanatothiophene 2,5-bis (isocyanatomethyl) thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis (isocyanatomethyl) tetrahydrothiophene 3,4-bis (isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanate Nato-1,4-dithiane, 2,5-bis (isocyanatomethyl) -1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis (isocyanatomethyl) -1, Examples include heterocyclic polyisocyanate compounds such as 3-dithiolane, and biuret bodies, nurate bodies, allophanate bodies, polyol adduct bodies, and blocked isocyanates, which are derivatives of these isocyanate compounds. May be.
• hexamethylene isocyanate hexamethylene isocyanate biuret
• hexamethylene isocyanate nurate are used from the viewpoint of excellent processability of the resulting coating film, transparency, and resistance to yellowing. preferable.
• the (meth) acrylate 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 polymer (A). A range of 1,000 is more preferable.
• These compounds (C) 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 (C) 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 polymer (A), the isocyanate compound (B), and other (meth) acrylate (C) used in combination as necessary is not particularly limited, although it can be set as appropriate in view of the hardness and workability of the target cured coating film, as well as transparency and scratch resistance, etc., it is easy to form a coating film with particularly high surface hardness and good workability.
• the mass ratio (A) / (B) of the acrylic polymer (A) to the isocyanate compound (B) is preferably in the range of 98/2 to 50/50, particularly 98 / The range of 2 to 70/30 is preferable, and the range of 98/2 to 80/20 is more preferable.
• the mass ratio (A) / (C) between the acrylic polymer (A) and the (meth) acrylate (C) is preferably in the range of 10/90 to 90/10, particularly the acrylic polymer (A).
• the mass ratio (A) / (B) / (C) of the isocyanate compound (B) and (meth) acrylate (C) is preferably in the range of 10/88/2 to 62/7/31. .
• inorganic fine particles (D) can be used in combination for the purpose of further increasing the surface hardness of the coating film or imparting other performances such as anti-blocking properties.
• the blending ratio of the inorganic fine particles (D) can be appropriately set according to the target performance, but a coating film having a high coating film hardness can be obtained and a coating film having a high transparency can be obtained.
• the inorganic fine particles (D) are preferably contained in the range of 30 to 55 parts by mass with respect to 100 parts by mass of the nonvolatile content in the active energy ray-curable resin composition. That is, when the content of the inorganic fine particles (D) is 30 parts by mass or more, the effect of improving the coating film hardness at the time of curing and the scratch resistance becomes remarkable.
• 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 (D) are contained in the range of 35 to 50 parts by mass.
• the average particle diameter of the inorganic fine particles (D) is in the range of 95 to 250 nm as a value measured by a dynamic light scattering method in a state of being dispersed in the composition, and the surface hardness and transparency of the coating film 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 (D) 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 (D) 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 (D) 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 aggregated 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 (D) may be those obtained by introducing a reactive functional group 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 (D) By introducing a reactive functional group on the surface of the inorganic fine particles (D), the miscibility with the organic component such as the acrylic polymer (A) and other (meth) acrylate (C) 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 polymer (A) may be removed once, and another solvent may be used.
• solvents used include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; esters such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene and xylene; Examples include alcohol solvents such as Tol, Cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; and glycol ether solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monopropyl ether.
• ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone
• cyclic ether solvents such as tetrahydro
• a ketone solvent is preferable and methyl ethyl ketone and methyl isobutyl ketone are more preferable in that the resin composition is excellent in storage stability and excellent in 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 wide range of wavelengths, preferably for high-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.
• a urethanization catalyst such as tin (II) octoate may be used in the resin composition of the present invention.
• the use ratio is preferably in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the resin composition.
• 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, and an attritor when inorganic particles (D) are used in combination ,
• the method of mixing and dispersing in the resin component which consists of the said isocyanate compound (B) and the said (meth) acrylate (C) is mentioned.
• the inorganic fine particles (D) 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 (D) 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 (D) includes, for example, a vessel filled with media 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.
• 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 (D), the polymer (A), and the (meth) acrylate (C) are supplied from the supply port of the wet ball mill as an apparatus.
• the resin component is supplied to the vessel, the rotating shaft and the stirring blade are rotated in the vessel, and the medium and the raw material are stirred and mixed, whereby the inorganic fine particles (D) are pulverized and the inorganic
• the fine particles (D) are dispersed in the resin component and then discharged from the discharge port.
• 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 film is dried by heating and semi-cured (B-tage).
• 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.
• the paint of the present invention is applied to a surface protective film 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 high hardness and high transparency. It becomes a protective film that combines the properties.
• 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 polymer (A1) 229 parts by mass of methyl isobutyl ketone was charged into a reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introduction tube, and the system temperature was increased to 110 ° C while stirring. Then, the temperature is 309 parts by mass of glycidyl methacrylate, 34 parts by mass of methyl methacrylate, and 10 parts by mass of t-butyl peroxy-2-ethylhexanoate (“Perbutyl O” manufactured by Nippon Emulsifier Co., Ltd.). The mixture was dropped from the dropping funnel over 3 hours and then held at 110 ° C. for 15 hours.
• Synthesis Example 2 Acrylic polymer (A2) In Synthesis Example 1, 283 parts by mass of methyl isobutyl ketone, 149 parts by mass of glycidyl methacrylate, 276 parts by mass of methyl methacrylate, t-butyl peroxy-2-ethylhexanoate (“Perbutyl O” manufactured by Nippon Emulsifier Co., Ltd.) 25 The same procedure as in Synthetic Example 1 except that the content is in parts by mass.
• the property values of the acrylic polymer (A2) were as follows. Weight average molecular weight (Mw): 15,000, Theoretical acryloyl group equivalent in terms of solid content: 478 g / eq, Hydroxyl value 117 mg KOH / g.
• Example 1 To 160 parts by mass of the methyl isobutyl ketone solution of the acrylic polymer (A) obtained in Synthesis Example 1, 5 parts by mass of Duranate 24A-100 as the isocyanate compound (B) and DPHA (Aronix M as the (meth) acrylate (C) -404 Toagosei Co., Ltd.) 20 parts by mass and 4 parts by mass of Irgacure 184 as a polymerization initiator were added to obtain an active energy ray-curable resin composition.
• This active energy ray-curable resin composition was applied onto a PET film (75 ⁇ A 4300, manufactured by Toyobo Co., Ltd.) so as to have a dry film thickness of 18 ⁇ m, cured at 500 mJ / cm 2 by an irradiator equipped with a high-pressure mercury lamp, and further 80 A heat treatment was performed at 30 ° C. for 30 minutes to obtain a laminated film.
• Example 2-11 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 addition, Example 11 mix
• 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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• Polymers & Plastics (AREA)
• Materials Engineering (AREA)
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• Macromonomer-Based Addition Polymer (AREA)
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• 2015
  • 2015-05-28 WO PCT/JP2015/065389 patent/WO2015198787A1/ja active Application Filing
  • 2015-05-28 JP JP2015554920A patent/JPWO2015198787A1/ja active Pending
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