Classifications

• • 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
• • 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
• • 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
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • 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
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
• • 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
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
• • 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
  • 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
  • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
  • C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links

Definitions

• the present invention relates to a urethane (meth) acrylate resin excellent in various properties such as scratch resistance, curl resistance, flexibility and impact resistance in a cured coating film, a curable composition containing the resin, a cured product thereof, and a laminate Related to film.
• Plastic films manufactured using polyethylene terephthalate resin (PET), acrylic resin, polycarbonate resin, acetylated cellulose resin, etc. are used in industrial applications such as polarizing plate protective films incorporated into flat panel displays and touch panel surface protective films. It is often used in. Since these plastic films are insufficient in performance, such as the surface is easily damaged by itself, the processability is low, and cracks and cracks are likely to occur, usually a coating layer made of active energy ray curable resin etc. is provided on the surface, It is used supplementing these performances.
• a coating agent for reinforcing plastic film for example, a resin composition containing urethane acrylate obtained by reacting dipentaerythritol polyacrylate having a hydroxyl value in the range of 80 to 120 mgKOH / g and hexamethylene diisocyanate is known. (See Patent Document 1). Although the resin composition described in Patent Document 1 has a high surface hardness in a cured product and excellent scratch resistance, curling is likely to occur, and the toughness and flexibility of the coating film are not sufficient. It was easy to produce a crack by.
• the problem to be solved by the present invention is a urethane (meth) acrylate resin excellent in various properties such as scratch resistance, curl resistance, flexibility, impact resistance, etc. in a cured coating film, and a curable composition containing the same. And a cured product thereof, and a laminated film.
• the present inventor obtained by reacting a polyisocyanate compound having an aromatic ring or alicyclic structure in the molecule with dipentaerythritol (meth) acrylate as essential components. It was found that the urethane (meth) acrylate resin to be solved solves the above problems, and the present invention has been completed.
• the present invention relates to a urethane (meth) acrylate resin having a polyisocyanate compound (A) having an aromatic ring or alicyclic structure in a molecule and dipentaerythritol (meth) acrylate (B) as essential reaction materials.
• the present invention further relates to a curable composition containing the urethane (meth) acrylate resin and a photopolymerization initiator.
• the present invention further relates to a cured product obtained by curing the curable composition.
• the present invention further relates to a laminated film having a layer made of the cured product and another plastic film layer.
• urethane (meth) acrylate resin excellent in various performances such as scratch resistance and curl resistance, flexibility, impact resistance in a cured coating film, a curable composition containing the same, and a cured product thereof, And a laminated film
• the curable composition containing the urethane (meth) acrylate resin of the present invention can be suitably used as a reinforcing coating agent for various plastic films, and the laminated film obtained using the curable composition of the present invention is resistant to In addition to excellent scratch resistance and curl resistance, it has high flexibility and is resistant to cracking when bent or wound, and also has impact resistance that is resistant to cracking when there is a fallen object on the film.
• the urethane (meth) acrylate resin of the present invention uses a polyisocyanate compound (A) having an aromatic ring or alicyclic structure in the molecule and dipentaerythritol (meth) acrylate (B) as essential reaction raw materials.
• the polyisocyanate compound (A) is not particularly limited as long as it has an aromatic ring or alicyclic structure in the molecule, and a wide variety of compounds can be used. Among them, as the polyisocyanate compound (A) that can be preferably used in the present invention, the following three types of polyisocyanate compounds (A) can be exemplified. 1. The following structural formulas (A1-1) to (A1-3)
• R 1 is each independently an alkyl group having 1 to 4 carbon atoms, and j is 0 or an integer of 1 to 4.
• R 2 is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Any of alkyl groups.
• a diisocyanate compound (A1) represented by any of the above or a modified product thereof. Structural formula (A2-1) or (A2-2)
• R 3 is each independently an alkyl group having 1 to 4 carbon atoms, or a structural moiety represented in parentheses in the formula. And is a bonding point linked via a methylene group marked with *, k is 0, 1 or 2, and n is 0 or an integer of 1 to 8.) 2.
• the polyisocyanate compound (A) is any one of the diisocyanate compound (A1) or a modified product thereof
• the polyisocyanate compound (A2) or a modified product thereof isophorone diisocyanate or a modified product thereof (A3).
• the preferred form of the urethane (meth) acrylate resin is described in detail below.
• the urethane (meth) acrylate resin of the present invention in this case is referred to as urethane (meth) acrylate resin (1).
• the urethane (meth) acrylate resin (1) has a feature of excellent adhesion to various plastic substrates in addition to scratch resistance, curl resistance, flexibility, impact resistance, and the like in a cured coating film.
• R 1 in the structural formulas (A1-1) to (A1-3) is each independently an alkyl group having 1 to 4 carbon atoms, and n is 0 or 1 to 4 It is an integer. Especially, since it becomes urethane (meth) acrylate resin (1) excellent in the balance of the surface hardness in a cured coating film, a softness
• R 2 in the structural formulas (A1-1) to (A1-3) is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Especially, since it becomes urethane (meth) acrylate resin (1) which is excellent in the balance of the surface hardness in a cured coating film, a softness
• the modified form of the diisocyanate compound (A1) is a modified polyisocyanate compound using the diisocyanate compound (A1) as a raw material. For example, isocyanurate modification obtained by converting the diisocyanate compound (A1) to isocyanurate. And adduct modified products obtained by reacting the diisocyanate compound (A1) with a polyol compound, biuret modified products of the diisocyanate compound (A1), and allophanate modified products of the diisocyanate compound (A1).
• the diisocyanate compound (A1) or a modified product thereof may be used alone or in combination of two or more.
• the dipentaerythritol (meth) acrylate (B) is obtained by (meth) acrylate-converting a part of the hydroxyl groups of dipentaerythritol and has a hydroxyl group that can react with the diisocyanate compound (A).
• a single compound may be sufficient and the mixture of several compounds may be sufficient.
• dipentaerythritol (meth) acrylate (B) dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol Tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate are each used alone.
• dipentaerythritol mono (meth) acrylate dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate 1 type or multiple types of this, and may contain dipentaerythritol hexa (meth) acrylate as needed.
• the dipentaerythritol (meth) acrylate (B) is dipentaerythritol tetra ( It is preferable to contain (meth) acrylate (b1) as an essential component, more preferably dipentaerythritol tetra (meth) acrylate (b1) and dipentaerythritol penta (meth) acrylate (b2), It is particularly preferable to contain erythritol tetra (meth) acrylate (b1), dipentaerythritol penta (meth) acrylate (b2) and dipentaerythritol hexa (meth) acrylate (b3).
• dipentaerythritol (meth) acrylate (B) contains dipentaerythritol tetra (meth) acrylate (b1) as an essential component, its content is preferably in the range of 1 to 30%. A range of 25% is more preferable, and a range of 3 to 20% is particularly preferable.
• the content of each component in the dipentaerythritol (meth) acrylate (B) and the ratio of the content of each component are calculated from the area ratio of the liquid chromatography chart measured under the following conditions. Value.
• Eluent Water / acetonitrile, 0.4 mL / min Detector: PDA, MS Sample preparation: 1.
• the ratio of the contents of both [(b1) / (B2)] is preferably in the range of 1/99 to 50/50, more preferably in the range of 5/95 to 30/70.
• dipentaerythritol (meth) acrylate (B) contains dipentaerythritol hexa (meth) acrylate (b3)
• the content is preferably in the range of 1 to 60%, and in the range of 5 to 50%. It is more preferable that
• the hydroxyl value of the dipentaerythritol (meth) acrylate (B) is a urethane (meth) acrylate resin (1) having an excellent balance of surface hardness, flexibility and impact resistance in the cured coating film, 50 It is preferably in the range of -140 mgKOH / g, more preferably in the range of 65-130 mgKOH / g, and particularly preferably in the range of 75-115 mgKOH / g.
• the hydroxyl value of dipentaerythritol (meth) acrylate (B) is calculated from an actual value measured according to JIS K 0070, or a composition ratio of each component calculated from an area ratio of a liquid chromatography chart. It is a calculated value.
• the production method of the dipentaerythritol (meth) acrylate (B) is not particularly limited, and examples thereof include a method of producing dipentaerythritol and acrylic acid by an esterification reaction.
• a high molecular weight component (b ′) such as an addition reaction product of dipentaerythritol (meth) acrylate (B), etc. May generate.
• the high molecular weight component (b ′) may be purified and removed, or the dipentaerythritol (meth) acrylate (B) containing the high molecular weight component (b ′) may be used as a raw material for the urethane (meth) acrylate resin (1). good.
• the content of the high molecular weight component (b ′) in the dipentaerythritol (meth) acrylate (B) crude product is preferably in the range of 1 to 20% by mass.
• the hydroxyl value of the dipentaerythritol (meth) acrylate (B) crude product is a urethane (meth) acrylate resin (1) which has an excellent balance of surface hardness, flexibility and impact resistance in the cured coating film. Therefore, the range of 60 to 150 mgKOH / g is preferable, and the range of 85 to 135 mgKOH / g is particularly preferable.
• the hydroxyl value of dipentaerythritol (meth) acrylate (B) is an actual value measured according to JIS K 0070.
• the urethane (meth) acrylate resin (1) uses the diisocyanate compound (A1) or a modified product thereof and dipentaerythritol (meth) acrylate (B) as essential reaction raw materials, but further uses compounds other than these as reaction raw materials. May be. Specifically, in addition to the diisocyanate compound (A1) or a modified product thereof, and dipentaerythritol (meth) acrylate (B), other polyisocyanate compounds (C) and other monohydroxy (meth) acrylate compounds (D), what is obtained by making other polyol compound (E) etc. react is mentioned.
• Examples of the other polyisocyanate compound (C) include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; isophorone diisocyanate Alicyclic diisocyanate compounds such as hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as diphenylmethane diisocyanate and 1,5-naphthalene diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (1); These isocyanurate modified body, biuret modified body, allophanate modified body, etc. are mentioned. These may be used alone or in combination of two or more.
• R 3 is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
• R 4 is each independently an alkyl group having 1 to 4 carbon atoms, or a bonding point linked to a structural moiety represented by the structural formula (1) via a methylene group marked with *.
• m is 0 or an integer of 1 to 3
• l is an integer of 1 or more.
• the diisocyanate compound (A1) or a modified product thereof and the other polyisocyanate compound (C) are used.
• the ratio of the diisocyanate compound (A1) or a modified product thereof to the total mass is preferably 30% by mass or more, more preferably in the range of 40 to 90% by mass, and in the range of 50 to 70% by mass. Is particularly preferred.
• Examples of the other monohydroxy (meth) acrylate compound (D) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerin di (meth) acrylate.
• Aliphatic (meth) acrylate compounds such as trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate; 4-hydroxyphenyl acrylate, ⁇ -hydroxyphenethyl acrylate, 4-hydroxyphenethyl acrylate, acrylic acid
• Aromatic ring-containing (meth) acrylate compounds such as 1-phenyl-2-hydroxyethyl, 3-hydroxy-4-acetylphenyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate;
• Polyether modified (meta) obtained by ring-opening polymerization of acrylate compounds with various cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether
• cured material an aliphatic (meth) acrylate compound or its polyether modified body and a lactone modified body are preferable.
• these other monohydroxy (meth) acrylate compounds (D) are used, the effects of the present invention are sufficiently exhibited, so that the dipentaerythritol (meth) acrylate (B) and the monohydroxy (meth) acrylate are used.
• the ratio of the dipentaerythritol (meth) acrylate (B) to the total mass with the compound (D) is preferably 70% by mass or more, and more preferably 90% by mass or more.
• Examples of the other polyol compound (E) include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, and 3-methyl-1,3-butane.
• Polyol monomers such as (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate; the polyol monomer, succinic acid, adipic acid, azelaic acid, sebashi Co-condensation with dicarboxylic acids such as acid, terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutac
• These other polyol compounds (E) may be used alone or in combination of two or more.
• the total mass of the dipentaerythritol (meth) acrylate (B) and the other polyol compounds (E) is obtained because the effects of the present invention are sufficiently exhibited.
• the ratio of the dipentaerythritol (meth) acrylate (B) to is preferably 70% by mass or more, and more preferably 90% by mass or more.
• the method for producing the urethane (meth) acrylate resin (1) of the present invention includes, for example, the diisocyanate compound (A1) or a modified product thereof and dipentaerythritol (meth) acrylate (B), the diisocyanate compound (A1) or
• the molar ratio [(NCO) / (OH)] between the isocyanate group of the modified product and the hydroxyl group of the dipentaerythritol (meth) acrylate (B) is 1 / 0.95 to 1 / 1.05.
• Examples thereof include a method of using a known and usual urethanization catalyst, if necessary, within a temperature range of 20 to 120 ° C.
• the other polyisocyanate compound (C) and the other monohydroxy (meth) acrylate compound ( D) In the case of reacting the other polyol compound (E), a method of reacting these three components at a time may be used, or an intermediate is obtained by first reacting a polyisocyanate component and a polyol component, A method of reacting a monoalcohol component or a method of reacting the polyisocyanate component and the monoalcohol component first to obtain an intermediate and then reacting the polyol component may be used.
• the reaction ratio of each component is such that the total molar ratio [(NCO) / (OH)] of the isocyanate group of the polyisocyanate component and the hydroxyl group of the alcohol component is in the range of 1 / 0.95 to 1 / 1.05. It is preferable that the ratio is
• the urethane (meth) acrylate resin (1) has a (meth) acryloyl group equivalent of 100 to 500 g / eq because the urethane (meth) acrylate resin (1) has excellent curability and high surface hardness in the cured coating film. Is preferable, and the range of 100 to 200 g / eq is more preferable.
• the (meth) acryloyl group equivalent of the urethane (meth) acrylate resin (1) is a value calculated as a theoretical value from the reaction raw materials.
• the urethane (meth) acrylate resin (1) has a weight average molecular weight (Mw) of 2,000 to 60, because the urethane (meth) acrylate resin (1) has an excellent balance of performance in the cured product. It is preferably in the range of 000, more preferably in the range of 2,000 to 15,000.
• the molecular weight of the resin is a value measured by gel permeation chromatography (GPC) under the following conditions.
• Measuring device HLC-8220GPC manufactured by Tosoh Corporation Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation + Tosoh Corporation TSK-GEL SuperHZM-M ⁇ 4 Detector: RI (differential refractometer)
• Data processing Multi-station GPC-8020model II manufactured by Tosoh Corporation Measurement conditions: Column temperature 40 ° C Solvent Tetrahydrofuran Flow rate 0.35 ml / min Standard; Monodisperse polystyrene Sample; Filtered 0.2% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 ⁇ l)
• the urethane (meth) acrylate resin of the present invention in this case is referred to as urethane (meth) acrylate resin (2).
• L in the structural formula (A2-1) or (A2-2) is 0 or an integer of 1 or more. Especially, since it becomes urethane (meth) acrylate resin (2) excellent in the balance of the surface hardness in a cured coating film, a softness
• each R 4 is independently an alkyl group having 1 to 4 carbon atoms, k is 0, 1 or 2, and n is 0 or an integer of 1 to 8. It is more preferable that it is the diliocyanate compound represented by either.
• the modified product of the polyisocyanate compound (A2) is a modified polyisocyanate compound using the polyisocyanate compound (A2) as a raw material, and is obtained by, for example, converting the polyisocyanate compound (A2) to isocyanurate. Isocyanurate-modified product, adduct-modified product obtained by reacting the polyisocyanate compound (A2) with a polyol compound, biuret-modified product of the polyisocyanate compound (A2), and allophanate-modified product of the polyisocyanate compound (A2) Etc.
• the polyisocyanate compound (A2) or a modified product thereof one type may be used alone, or two or more types may be used in combination.
• the dipentaerythritol (meth) acrylate (B) is obtained by converting a part of the hydroxyl group of dipentaerythritol into (meth) acrylate and having a hydroxyl group capable of reacting with the polyisocyanate compound (A).
• a single compound or a mixture of a plurality of compounds may be used.
• dipentaerythritol (meth) acrylate (B) dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol Tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate are each used alone.
• dipentaerythritol mono (meth) acrylate dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate 1 type or multiple types of this, and may contain dipentaerythritol hexa (meth) acrylate as needed.
• the dipentaerythritol (meth) acrylate (B) is dipentaerythritol tetra ( It is preferable to contain (meth) acrylate (b1) as an essential component, more preferably dipentaerythritol tetra (meth) acrylate (b1) and dipentaerythritol penta (meth) acrylate (b2), It is particularly preferable to contain erythritol tetra (meth) acrylate (b1), dipentaerythritol penta (meth) acrylate (b2) and dipentaerythritol hexa (meth) acrylate (b3).
• dipentaerythritol (meth) acrylate (B) contains dipentaerythritol tetra (meth) acrylate (b1) as an essential component, its content is preferably in the range of 1 to 30%. A range of 25% is more preferable, and a range of 3 to 20% is particularly preferable.
• the content of each component in the dipentaerythritol (meth) acrylate (B) and the ratio of the content of each component are calculated from the area ratio of the liquid chromatography chart measured under the following conditions. Value.
• Eluent Water / acetonitrile, 0.4 mL / min Detector: PDA, MS Sample preparation: 1.
• the ratio of the contents of both [(b1) / (B2)] is preferably in the range of 1/99 to 50/50, more preferably in the range of 5/95 to 30/70.
• dipentaerythritol (meth) acrylate (B) contains dipentaerythritol hexa (meth) acrylate (b3)
• the content is preferably in the range of 1 to 60%, and in the range of 5 to 50%. It is more preferable that
• the hydroxyl value of the dipentaerythritol (meth) acrylate (B) is a urethane (meth) acrylate resin (2) having an excellent balance of surface hardness, flexibility and impact resistance in the cured coating film, 50 It is preferably in the range of -140 mgKOH / g, more preferably in the range of 65-130 mgKOH / g, and particularly preferably in the range of 75-115 mgKOH / g.
• the hydroxyl value of dipentaerythritol (meth) acrylate (B) is calculated from an actual value measured according to JIS K 0070, or a composition ratio of each component calculated from an area ratio of a liquid chromatography chart. It is a calculated value.
• the production method of the dipentaerythritol (meth) acrylate (B) is not particularly limited, and examples thereof include a method of producing dipentaerythritol and acrylic acid by an esterification reaction.
• a high molecular weight component (b ′) such as an addition reaction product of dipentaerythritol (meth) acrylate (B), etc. May generate.
• the high molecular weight component (b ′) may be purified and removed, or the dipentaerythritol (meth) acrylate (B) containing this may be used as a raw material for the urethane (meth) acrylate resin (2). good.
• the content of the high molecular weight component (b ′) in the dipentaerythritol (meth) acrylate (B) crude product is preferably in the range of 1 to 20% by mass.
• the hydroxyl value of the dipentaerythritol (meth) acrylate (B) crude product should be a urethane (meth) acrylate resin (2) excellent in the balance of surface hardness, flexibility and impact resistance in the cured coating film. Therefore, the range of 60 to 150 mgKOH / g is preferable, and the range of 85 to 135 mgKOH / g is particularly preferable.
• the hydroxyl value of dipentaerythritol (meth) acrylate (B) is an actual value measured according to JIS K 0070.
• the urethane (meth) acrylate resin (2) uses the polyisocyanate compound (A2) or a modified product thereof and dipentaerythritol (meth) acrylate (B) as essential reaction raw materials, and further uses compounds other than these as reaction raw materials. It may be used. Specifically, in addition to the polyisocyanate compound (A2) or a modified product thereof, and dipentaerythritol (meth) acrylate (B), other polyisocyanate compounds (C) and other monohydroxy (meth) acrylates What is obtained by making a compound (D), another polyol compound (E), etc. react is mentioned.
• Examples of the other polyisocyanate compound (C) include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; isophorone diisocyanate And alicyclic diisocyanate compounds such as these isocyanurate-modified products, biuret-modified products, and allophanate-modified products. These may be used alone or in combination of two or more.
• the other polyisocyanate compound (C) When the other polyisocyanate compound (C) is used, the effects of the present invention are sufficiently exerted, so the polyisocyanate compound (A2) or a modified product thereof and the other polyisocyanate compound (C)
• the ratio of the polyisocyanate compound (A2) or the modified product thereof to the total mass of is preferably 30% by mass or more, more preferably 50% by mass or more, and particularly preferably 90% by mass or more.
• Examples of the other monohydroxy (meth) acrylate compound (D) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerin di (meth) acrylate.
• Aliphatic (meth) acrylate compounds such as trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate; 4-hydroxyphenyl acrylate, ⁇ -hydroxyphenethyl acrylate, 4-hydroxyphenethyl acrylate, acrylic acid
• Aromatic ring-containing (meth) acrylate compounds such as 1-phenyl-2-hydroxyethyl, 3-hydroxy-4-acetylphenyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate;
• Polyether modified (meta) obtained by ring-opening polymerization of acrylate compounds with various cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether
• cured material an aliphatic (meth) acrylate compound or its polyether modified body and a lactone modified body are preferable.
• these other monohydroxy (meth) acrylate compounds (D) are used, the effects of the present invention are sufficiently exhibited, so that the dipentaerythritol (meth) acrylate (B) and the monohydroxy (meth) acrylate are used.
• the ratio of the dipentaerythritol (meth) acrylate (B) to the total mass with the compound (D) is preferably 70% by mass or more, and more preferably 90% by mass or more.
• Examples of the other polyol compound (E) include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, and 3-methyl-1,3-butane.
• Polyol monomers such as (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate; the polyol monomer, succinic acid, adipic acid, azelaic acid, sebashi Co-condensation with dicarboxylic acids such as acid, terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutac
• These other polyol compounds (E) may be used alone or in combination of two or more.
• the total mass of the dipentaerythritol (meth) acrylate (B) and the other polyol compounds (E) is obtained because the effects of the present invention are sufficiently exhibited.
• the ratio of the dipentaerythritol (meth) acrylate (B) to is preferably 70% by mass or more, and more preferably 90% by mass or more.
• the method for producing the urethane (meth) acrylate resin (2) according to the present invention includes, for example, the polyisocyanate compound (A2) or a modified product thereof and dipentaerythritol (meth) acrylate (B). Or a molar ratio [(NCO) / (OH)] between the isocyanate group of the modified product and the hydroxyl group of the dipentaerythritol (meth) acrylate (B) is 1 / 0.95 to 1/1. Examples thereof include a method of using a known and usual urethanization catalyst, if necessary, within a temperature range of 20 to 120 ° C., at a ratio in the range of 05.
• the other polyisocyanate compound (C) and the other monohydroxy (meth) acrylate compound In addition to the polyisocyanate compound (A2) or a modified product thereof, and the dipentaerythritol (meth) acrylate (B), the other polyisocyanate compound (C) and the other monohydroxy (meth) acrylate compound.
• D) When the other polyol compound (E) is reacted, a method of reacting these three components at a time may be used, or an intermediate is obtained by reacting a polyisocyanate component and a polyol component first, Next, a method of reacting the monoalcohol component or a method of reacting the polyisocyanate component and the monoalcohol component first to obtain an intermediate and then reacting the polyol component may be used.
• the reaction ratio of each component is such that the total molar ratio [(NCO) / (OH)] of the isocyanate group of the polyisocyanate component and the hydroxyl group of the alcohol component is in the range of 1 / 0.95 to 1 / 1.05. It is preferable that the ratio is
• the urethane (meth) acrylate resin (2) has a (meth) acryloyl group equivalent of 100 to 500 g / eq because the urethane (meth) acrylate resin (2) has excellent curability and high surface hardness in the cured coating film. It is preferable that it is the range of these.
• the (meth) acryloyl group equivalent of the urethane (meth) acrylate resin (2) is a value calculated as a theoretical value from the reaction raw materials.
• the urethane (meth) acrylate resin (2) has a weight average molecular weight (Mw) of 2,000 to 60, because the urethane (meth) acrylate resin (2) has an excellent balance of performance in the cured product. It is preferably in the range of 000, more preferably in the range of 2,000 to 15,000.
• the urethane (meth) acrylate resin of the present invention in this case is referred to as a urethane (meth) acrylate resin (3).
• a modified product of isophorone diisocyanate is a modified polyisocyanate compound using isophorone diisocyanate as a raw material, for example, isocyanurate modification obtained by converting isophorone diisocyanate to isocyanurate. And adduct modified products obtained by reacting isophorone diisocyanate with a polyol compound, biuret modified products of isophorone diisocyanate, and allophanate modified products of isophorone diisocyanate.
• one type of isophorone diisocyanate or a modified product thereof (A3) may be used alone, or two or more types may be used in combination.
• the dipentaerythritol (meth) acrylate (B) is obtained by converting a part of the hydroxyl group of dipentaerythritol into (meth) acrylate and having a hydroxyl group capable of reacting with the polyisocyanate compound (A).
• a single compound or a mixture of a plurality of compounds may be used.
• dipentaerythritol (meth) acrylate (B) dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol Tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate are each used alone.
• dipentaerythritol mono (meth) acrylate dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate 1 type or multiple types of this, and may contain dipentaerythritol hexa (meth) acrylate as needed.
• the dipentaerythritol (meth) acrylate (B) is dipentaerythritol tetra ( (Meth) acrylate (b1) and dipentaerythritol penta (meth) acrylate (b2) are contained, and the ratio of the content of both ((b1) / (b2)) is in the range of 5/95 to 30/70. It is preferable.
• the content of each component in the dipentaerythritol (meth) acrylate (B) and the ratio of the content of each component are calculated from the area ratio of the liquid chromatography chart measured under the following conditions. Value.
• Eluent Water / acetonitrile, 0.4 mL / min Detector: PDA, MS Sample preparation: 1.
• dipentaerythritol tetra (meth) acrylate (b1) and dipentaerythritol penta It is more preferable to contain dipentaerythritol hexa (meth) acrylate (b3) in addition to (meth) acrylate (b2).
• the content of dipentaerythritol tetra (meth) acrylate (b1) in the dipentaerythritol (meth) acrylate (B) is preferably in the range of 1 to 30%, more preferably in the range of 1 to 25%. A more preferred range is 3 to 20%.
• the content of dipentaerythritol hexa (meth) acrylate (b3) in the dipentaerythritol (meth) acrylate (B) is preferably in the range of 1 to 60%, more preferably in the range of 5 to 50%. More preferred.
• the hydroxyl value of the dipentaerythritol (meth) acrylate (B) is a urethane (meth) acrylate resin (3) having an excellent balance of surface hardness, flexibility and impact resistance in the cured coating film, 50 It is preferably in the range of -140 mgKOH / g, more preferably in the range of 65-130 mgKOH / g, and particularly preferably in the range of 75-115 mgKOH / g.
• the hydroxyl value of dipentaerythritol (meth) acrylate (B) is calculated from an actual value measured according to JIS K 0070, or a composition ratio of each component calculated from an area ratio of a liquid chromatography chart. It is a calculated value.
• the production method of the dipentaerythritol (meth) acrylate (B) is not particularly limited, and examples thereof include a method of producing dipentaerythritol and acrylic acid by an esterification reaction.
• a high molecular weight component (b ′) such as an addition reaction product of dipentaerythritol (meth) acrylate (B), etc. May generate.
• the high molecular weight component (b ′) may be purified and removed, or the dipentaerythritol (meth) acrylate (B) crude product containing this may be used as a raw material for the urethane (meth) acrylate resin (3). good.
• the content of the high molecular weight component (b ′) in the dipentaerythritol (meth) acrylate (B) crude product is preferably in the range of 1 to 20% by mass.
• the hydroxyl value of the dipentaerythritol (meth) acrylate (B) crude product should be a urethane (meth) acrylate resin (3) excellent in the balance of surface hardness, flexibility and impact resistance in the cured coating film. Therefore, the range of 60 to 150 mgKOH / g is preferable, and the range of 85 to 135 mgKOH / g is particularly preferable.
• the hydroxyl value of dipentaerythritol (meth) acrylate (B) is an actual value measured according to JIS K 0070.
• the urethane (meth) acrylate resin (3) uses the isophorone diisocyanate or its modified product (A3) and dipentaerythritol (meth) acrylate (B) as essential reaction raw materials, but further uses compounds other than these as reaction raw materials. May be.
• other polyisocyanate compounds (C) and other monohydroxy (meth) acrylate compounds examples thereof include those obtained by reacting D) and other polyol compounds (E) and the like.
• Examples of the other polyisocyanate compound (C) include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate Alicyclic diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate; Polymethylene polyphenyl polyisocyanate having a repeating structure represented by the structural formula (1) ; These isocyanurate modified product, a biuret modified product, and allophanate modified compounds and the like. These may be
• R 3 is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
• R 4 is each independently an alkyl group having 1 to 4 carbon atoms, or a bonding point linked to a structural moiety represented by the structural formula (1) via a methylene group marked with *.
• m is 0 or an integer of 1 to 3
• l is an integer of 1 or more.
• the ratio of the isophorone diisocyanate or its modified product (A3) to the total mass is preferably 30% by mass or more, more preferably 50% by mass or more, and particularly preferably 90% by mass or more.
• Examples of the other monohydroxy (meth) acrylate compound (D) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerin di (meth) acrylate.
• Aliphatic (meth) acrylate compounds such as trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate; 4-hydroxyphenyl acrylate, ⁇ -hydroxyphenethyl acrylate, 4-hydroxyphenethyl acrylate, acrylic acid
• Aromatic ring-containing (meth) acrylate compounds such as 1-phenyl-2-hydroxyethyl, 3-hydroxy-4-acetylphenyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate;
• Polyether modified (meta) obtained by ring-opening polymerization of acrylate compounds with various cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether
• cured material an aliphatic (meth) acrylate compound or its polyether modified body and a lactone modified body are preferable.
• these other monohydroxy (meth) acrylate compounds (D) are used, the effects of the present invention are sufficiently exhibited, so that the dipentaerythritol (meth) acrylate (B) and the monohydroxy (meth) acrylate are used.
• the ratio of the dipentaerythritol (meth) acrylate (B) to the total mass with the compound (D) is preferably 70% by mass or more, and more preferably 90% by mass or more.
• Examples of the other polyol compound (E) include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, and 3-methyl-1,3-butane.
• Polyol monomers such as (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate; the polyol monomer, succinic acid, adipic acid, azelaic acid, sebashi Co-condensation with dicarboxylic acids such as acid, terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutac
• These other polyol compounds (E) may be used alone or in combination of two or more.
• the total mass of the dipentaerythritol (meth) acrylate (B) and the other polyol compounds (E) is obtained because the effects of the present invention are sufficiently exhibited.
• the ratio of the dipentaerythritol (meth) acrylate (B) to is preferably 70% by mass or more, and more preferably 90% by mass or more.
• the method for producing the urethane (meth) acrylate resin (3) of the present invention includes, for example, the isophorone diisocyanate or its modified product (A3) and dipentaerythritol (meth) acrylate (B), and the isophorone diisocyanate or its modified product.
• the molar ratio [(NCO) / (OH)] of the isocyanate group of (A3) to the hydroxyl group of the dipentaerythritol (meth) acrylate (B) is 1 / 0.95 to 1 / 1.05. Examples thereof include a method of using a known and usual urethanization catalyst, if necessary, within a temperature range of 20 to 120 ° C.
• the other polyisocyanate compound (C) and the other monohydroxy (meth) acrylate compound (D ) In the case of reacting the other polyol compound (E), a method of reacting these three components at once may be used, or a polyisocyanate component and a polyol component are first reacted to obtain an intermediate, A method of reacting the alcohol component or a method of reacting the polyisocyanate component and the monoalcohol component first to obtain an intermediate and then reacting the polyol component may be used.
• the reaction ratio of each component is such that the total molar ratio [(NCO) / (OH)] of the isocyanate group of the polyisocyanate component and the hydroxyl group of the alcohol component is in the range of 1 / 0.95 to 1 / 1.05. It is preferable that the ratio is
• the (meth) acryloyl group equivalent of the urethane (meth) acrylate resin (3) of the present invention is 100 to 500 g because it becomes a urethane (meth) acrylate resin (3) having excellent curability and high surface hardness in the cured coating film. It is preferably in the range of / eq, and more preferably in the range of 100 to 135 g / eq.
• the (meth) acryloyl group equivalent of the urethane (meth) acrylate resin (3) is a value calculated as a theoretical value from the reaction raw materials.
• the urethane (meth) acrylate resin (3) has a weight average molecular weight (Mw) of 2,000 to 60, because the urethane (meth) acrylate resin (3) has an excellent balance of performance in the cured product. It is preferably in the range of 000, more preferably in the range of 2,000 to 15,000.
• the curable composition of the present invention contains the urethane (meth) acrylate resin and a photopolymerization initiator.
• the photopolymerization initiator include benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 4,4′-bisdimethylaminobenzophenone, 4,4′-bisdiethylaminobenzophenone, and 4,4′-dichloro.
• Various benzophenones such as benzophenone, Michler's ketone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone;
• Xanthones such as xanthone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, and 2,4-diethylthioxanthone; thioxanthones; various acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether;
• ⁇ -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 the high curability curable composition used.
• the addition amount of the photopolymerization initiator is an amount that can sufficiently exhibit the function as a photopolymerization initiator, and is preferably in a range in which precipitation of crystals and deterioration of physical properties of the coating film do not occur. 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 curable composition.
• the curable composition of the present invention may contain 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.
• the curable composition of the present invention is further a photocurable compound (R) other than the urethane (meth) acrylate resin of the present invention, an organic solvent, an ultraviolet absorber, an antioxidant, a silicon-based additive, Fluorine-based additives, silane coupling agents, phosphate ester compounds, organic beads, inorganic fine particles, inorganic fillers, rheology control agents, defoaming agents, antifogging agents, colorants and the like may be contained.
• Examples of the other photo-curable compound (R) include various (meth) acrylate monomers (R1) and other urethane (meth) acrylate resins (R2) other than the urethane (meth) acrylate resin of the present invention. ), Epoxy (meth) acrylate resin (R3), dendrimer type (meth) acrylate resin (R4), (meth) acryloyl group-containing acrylic resin (R5), and the like.
• Examples of the (meth) acrylate monomer (R1) 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, benz
• the other urethane (meth) acrylate resin (R2) is, for example, a urethane (meth) acrylate resin using a compound other than the polyisocyanate compound (A) having an aromatic ring or an alicyclic structure in the molecule as a polyisocyanate compound. And urethane (meth) acrylate resin using a compound other than dipentaerythritol (meth) acrylate (B) as a hydroxy (meth) acrylate compound.
• Examples of the epoxy (meth) acrylate resin (R3) include compounds obtained by reacting various epoxy resins such as bisphenol type epoxy resin and novolac type epoxy resin with (meth) acrylic acid or a derivative thereof to (meth) acrylate. .
• the dendrimer type (meth) acrylate resin (R4) refers to a resin having a regular multi-branched structure and having a (meth) acryloyl group at the end of each branched chain. It is called a branch type or a star polymer. Examples of such compounds include, but are not limited to, those represented by the following structural formulas (2-1) to (2-8), and a regular multi-branched structure is not limited thereto. Any resin can be used as long as it has a (meth) acryloyl group at the end of each branched chain.
• R 3 is a hydrogen atom or a methyl group
• R 4 is a hydrocarbon group having 1 to 4 carbon atoms.
• the dendrimer type (meth) acrylate resin (R4) preferably has a mass average molecular weight (Mw) in the range of 1,000 to 30,000. Further, those having an average (meth) acryloyl group number per molecule of 5 to 30 are preferable.
• the (meth) acryloyl group-containing acrylic resin (R5) is obtained by polymerizing, for example, a (meth) acrylate monomer ( ⁇ ) having a reactive functional group such as a hydroxyl group, a carboxy group, an isocyanate group, or a glycidyl group as an essential component. What can be obtained by introducing a (meth) acryloyl group by further reacting the resulting acrylic resin intermediate with a (meth) acrylate monomer ( ⁇ ) having a reactive functional group capable of reacting with these functional groups. It is done.
• the (meth) acrylate monomer ( ⁇ ) having a reactive functional group is, for example, a hydroxyl group-containing (meth) acrylate monomer such as hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate; a carboxy such as (meth) acrylic acid Group-containing (meth) acrylate monomer; isocyanate group-containing (meth) acrylate monomer such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate; glycidyl (meth) acrylate And glycidyl group-containing (meth) acrylate monomers such as 4-hydroxybutyl acrylate glycidyl ether. These may be used alone or in combination of two or more.
• the acrylic resin intermediate may be a copolymer obtained by copolymerizing other polymerizable unsaturated group-containing compound as required in addition to the (meth) acrylate monomer ( ⁇ ).
• the other polymerizable unsaturated group-containing compound include (meth) methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.
• Acrylic acid alkyl ester Cyclo ring-containing (meth) acrylate such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl acrylate Aromatic ring-containing (meth) acrylates; silyl group-containing (meth) acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, ⁇ -methylstyrene, chlorostyrene, etc. . These may be used alone or in combination of two or more. Among these, it is preferable to use the alkyl (meth) acrylate.
• the reaction ratio of both is excellent in curability. Since it becomes the (meth) acryloyl group-containing acrylic resin (R5), the ratio of the (meth) acrylate monomer ( ⁇ ) to the total of both is preferably in the range of 20 to 70 parts by mass, and 30 to 60% by mass. More preferably, it is in the range of part%.
• the acrylic resin intermediate can be produced by the same method as a general acrylic resin.
• it can be produced, for example, by polymerizing various monomers in the temperature range of 60 ° C. to 150 ° C. in the presence of a polymerization initiator.
• the polymerization method include a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method.
• the polymerization mode include random copolymers, block copolymers, and graft copolymers.
• a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone
• a glycol ether solvent such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether is preferably used.
• a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone
• a glycol ether solvent such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether is preferably used.
• the (meth) acrylate monomer ( ⁇ ) is not particularly limited as long as it can react with the reactive functional group of the (meth) acrylate monomer ( ⁇ ), but is the following combination from the viewpoint of reactivity. Is preferred. That is, when the hydroxyl group-containing (meth) acrylate is used as the (meth) acrylate monomer ( ⁇ ), it is preferable to use an isocyanate group-containing (meth) acrylate as the (meth) acrylate monomer ( ⁇ ).
• the carboxy group-containing (meth) acrylate is used as the (meth) acrylate monomer ( ⁇ )
• the isocyanate group-containing (meth) acrylate is used as the (meth) acrylate monomer ( ⁇ )
• the hydroxyl group-containing (meth) acrylate is preferably used as the (meth) acrylate monomer ( ⁇ ).
• the carboxy group-containing (meth) acrylate is preferably used as the (meth) acrylate monomer ( ⁇ ).
• the reaction between the acrylic resin intermediate and the (meth) acrylate monomer ( ⁇ ) is, for example, an esterification catalyst such as triphenylphosphine in a temperature range of 60 to 150 ° C. when the reaction is an esterification reaction. Can be used as appropriate. Further, when the reaction is a urethanization reaction, a method of reacting the acrylic resin intermediate while dropping the compound ( ⁇ ) in a temperature range of 50 to 120 ° C. can be used.
• the (meth) acryloyl group-containing acrylic resin (R5) preferably has a mass average molecular weight (Mw) in the range of 5,000 to 80,000.
• the (meth) acryloyl group equivalent is preferably in the range of 200 to 500 g / equivalent.
• These other photocurable compounds (R) may be used alone or in combination of two or more. Especially, since it becomes a composition excellent in sclerosis
• the urethane (meth) of the present invention in a total of 100 parts by mass of the urethane (meth) acrylate resin of the present invention and the other photocurable compound (R).
• the acrylate resin is preferably used at a ratio of 5 parts by mass or more, more preferably 20 parts by mass or more, and particularly preferably 80 parts by mass or more.
• organic solvent examples include acetone, methyl ethyl ketone, methyl isobutyl ketone (ketone solvents such as tetrahydrofuran; 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; 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 These may be used alone or in combination of two or more.
• ketone solvents such as tetrahydrofuran
• cyclic ether solvents such as tetrahydrofuran
• organic solvents are mainly used for the purpose of adjusting the viscosity of the curable composition, but it is usually preferable to adjust so that the nonvolatile content is in the range of 10 to 80% by mass.
• 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 2,5-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. These may be used alone or in combination of two or more.
• 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.
• fluorine-based additive examples include DIC Corporation “Megaface” series. These may be used alone or in combination of two or more.
• 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-methacryloxypropylmethyl Diethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (amino Til) -3-aminopropyl
• 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 may be used alone or in combination of two or more.
• Examples of commercially available phosphoric acid ester compounds include, for example, “Kayamar PM-2” and “Kayamar PM-21” manufactured by Nippon Kayaku Co., Ltd., which are phosphoric acid ester compounds having a (meth) acryloyl group in the molecular structure.
• 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. These may be used alone or in combination of two or more. These organic beads preferably have an average particle size in the range of 1 to 10 ⁇ m.
• the inorganic fine particles include 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.
• the average particle size of these inorganic fine particles is preferably in the range of 95 to 250 nm, and more preferably in the range of 100 to 180 nm.
• a dispersion aid may be further used.
• the dispersion aid include phosphate esters such as isopropyl acid phosphate, triisodecyl phosphite, and ethylene oxide-modified phosphate dimethacrylate. Compounds and the like. These may be used alone or in combination of two or more.
• Examples of commercially available dispersion aids include “Kayamar PM-21” and “Kayamar PM-2” manufactured by Nippon Kayaku Co., Ltd. and “Light Ester P-2M” manufactured by Kyoeisha Chemical Co., Ltd.
• the curable composition of the present invention can be used for coating applications, and the coating is applied as a coating layer that protects the surface of the substrate by coating on various substrates and irradiating and curing with active energy rays. be able to.
• the curable composition of the present invention may be directly applied to the surface-protecting member, or one applied on a plastic film may be used as the protective film.
• what applied the curable composition of this invention on the plastic film, and formed the coating film may be used as optical films, such as an antireflection film, a diffusion film, and a prism sheet.
• the cured coating film of the curable composition of the present invention is characterized by high surface hardness and excellent flexibility and impact resistance. Therefore, it is applied to various types of plastic films with a film thickness according to the application, and a protective film. It can be used as a use or a film-like molded product.
• the plastic film is, for example, a plastic film made of polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, cycloolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, 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 comprising the curable composition of the present invention has a high surface hardness even when a triacetyl cellulose film is used as a base material, and has an effect of excellent curling resistance, flexibility, transparency and impact resistance. Can be suitably used.
• the coating amount when applying the curable composition 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 10 ⁇ m. It is preferable to apply to.
• 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 includes, for example, polyethylene terephthalate, and its thickness is generally about 20 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 curable composition of the present invention is such that the film thickness after drying ranges from 1 to 100 ⁇ m, preferably from 1 to 20 ⁇ m, in accordance with the application. It is preferable to apply in such a range.
• a cured coating film having a thickness exceeding 20 ⁇ m tends to curl greatly as compared with a case where the film thickness is thin. Curling hardly occurs even when the film is applied with a relatively high film thickness exceeding 50, and 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 films are generally relatively thick and durable, with a thickness of about 50 to 2,000 ⁇ m, and are suitable for applications that require particularly high surface hardness, such as liquid crystal display front plate applications. It is the film used for.
• the coating amount when applying the curable composition of the present invention is in the range of 1 to 100 ⁇ m after drying, preferably 1 to It is preferable to apply in a range of 20 ⁇ m.
• 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.
• cycloolefin polymer films are generally weak against lateral forces such as tearing, and are known to have poor folding resistance.
• the area of use is expanding.
• the cured coating film obtained from the curable composition of the present invention can effectively increase its flexibility and impact resistance even in such a fragile film.
• the thickness of the cured coating film is preferably adjusted in the range of 1 to 10 ⁇ m. Examples of 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 curable composition 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, an LED or the like as a light source is used, and the amount of light, the arrangement of the light source, 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 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 curable composition of the present invention is applied is suitably used not only as a plastic film but also as a surface coating agent for various plastic molded articles, for example, cellular phones, electric appliances, automobile bumpers and the like. be able to.
• 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.
• the laminated film of the present invention has a cured coating film or the like of the curable composition of the present invention and a plastic film layer, and additionally has functional film layers such as an antireflection film, a diffusion film, and a polarizing film. You may do it.
• These various layer configurations may be formed by a method in which a resin raw material is directly applied and dried or cured, or may be formed by a method of bonding through an adhesive layer.
• 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: Tosoh Corporation guard column H XL -H + 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 mass tetrahydrofuran solution in terms of resin solids filtered through microfilter (100 ⁇ l)
• Production Example 1 Production of Dipentaerythritol Polyacrylate (B1) Crude Product In a flask equipped with a thermometer, a stirrer, and a condenser, 300 g of acrylic acid, 180 g of dipentaerythritol, 15 g of sulfuric acid, 1.5 g of cupric chloride, 300 g of toluene was charged. The temperature was raised to 105 ° C. with stirring, and the reaction was carried out at the same temperature for 12 hours while refluxing the system. The produced water was 68.5 g. To the reaction mixture, 425 g of toluene was added and washed with 200 g of distilled water.
• the hydroxy value of the dipentaerythritol polyacrylate (B1) crude product is 88 mgKOH / g
• the content of dipentaerythritol tetraacrylate (b1) calculated from the area ratio of the liquid chromatography chart is 7.2%
• dipentaerythritol The content of pentaacrylate (b2) was 48.3%
• the content of dipentaerythritol hexaacrylate (b3) was 30.7%
• the content of the high molecular weight component (b ′) was 13.8%.
• the hydroxyl value of dipentaerythritol polyacrylate (B1) calculated from the content ratio of each component is 79.9 mgKOH / g.
• Production Examples 2 to 4 Production of Dipentaerythritol Polyacrylates (B2) to (B4) Crude Products Dipentapentite was prepared in the same manner as in Production Example 1 except that the amount of acrylic acid charged and the reaction time were changed as shown in Table 1. Crude products of erythritol polyacrylates (B2) to (B4) were obtained. Dipentaerythritol polyacrylate (B2) to (B4) The hydroxyl value of the crude product, the content of each component calculated from the area ratio of the liquid chromatography chart, the dipentaerythritol poly calculated from the content ratio of each component Table 1 shows the hydroxyl values of acrylates (B2) to (B4).
• Example 1 Production of Urethane (Meth) acrylate Resin (1-1) Composition
• 638 g of the dipentaerythritol polyacrylate (B1) crude product obtained in Production Example 1 was obtained.
• 0.2 g of dibutyltin dilaurate and 0.2 g of hydroquinone were added, and stirring was started.
• the urethane (meth) acrylate resin (1-1) calculated from the raw material charge ratio had an acryloyl group equivalent of 117 g / equivalent, and a weight average molecular weight (Mw) of 4,100.
• Example 2 Production of Urethane (Meth) acrylate Resin (1-2) Composition
• 0.2 g of dibutyltin dilaurate and 0.2 g of hydroquinone were added, and stirring was started.
• the flask was heated to an internal temperature of 50 ° C., and 97 g of 1,3-bis (isocyanatomethyl) cyclohexane (“Takenate 600” manufactured by Mitsui Chemicals, Inc.) was added in portions over about one hour. After reacting at 80 ° C.
• the urethane (meth) acrylate resin (1-2) calculated from the raw material charge ratio had an acryloyl group equivalent of 118 g / equivalent, and a weight average molecular weight (Mw) of 4,500.
• Example 3 Production of urethane (meth) acrylate resin (1-3) composition
• 432 g of the dipentaerythritol polyacrylate (B3) crude product obtained in Production Example 3 was obtained.
• 0.2 g of dibutyltin dilaurate and 0.2 g of hydroquinone were added, and stirring was started.
• the flask was heated to an internal temperature of 50 ° C., and 97 g of 1,3-bis (isocyanatomethyl) cyclohexane (“Takenate 600” manufactured by Mitsui Chemicals, Inc.) was added in portions over about one hour.
• 1,3-bis (isocyanatomethyl) cyclohexane (“Takenate 600” manufactured by Mitsui Chemicals, Inc.) was added in portions over about one hour.
• the urethane (meth) acrylate resin (1-3) calculated from the raw material charge ratio had an acryloyl group equivalent of 122 g / equivalent and a weight average molecular weight (Mw) of 8,000.
• Example 4 Production of Urethane (Meth) acrylate Resin (2-1) Composition
• 638 g of the dipentaerythritol polyacrylate (B1) crude product obtained in Production Example 1 was obtained.
• 0.2 g of dibutyltin dilaurate and 0.2 g of hydroquinone were added, and stirring was started.
• the flask was heated until the internal temperature of the flask reached 50 ° C., and 131.2 g of 4,4-methylenedicyclohexyl-diisocyanate (“VESTANAT H12MDI” manufactured by Evonik Degussa Japan) was added in portions over about one hour. After reacting at 80 ° C. for 3 hours and confirming the disappearance of the isocyanate group by infrared absorption spectrum, the nonvolatile content was adjusted to 80% by mass using butyl acetate, and the urethane (meth) acrylate resin (2-1) composition I got a thing.
• the urethane (meth) acrylate resin (2-1) calculated from the raw material charge ratio had an acryloyl group equivalent of 120 g / equivalent and a weight average molecular weight (Mw) of 4,100.
• Example 5 Production of Urethane (Meth) acrylate Resin (2-2) Composition
• 524 g of the dipentaerythritol polyacrylate (B2) crude product obtained in Production Example 2 was obtained.
• 0.2 g of dibutyltin dilaurate and 0.2 g of hydroquinone were added, and stirring was started.
• the flask was heated until the internal temperature of the flask reached 50 ° C., and 90 g of tolylene diisocyanate was added in portions over about one hour. After reacting at 80 ° C.
• the urethane (meth) acrylate resin (2-2) calculated from the raw material charge ratio had an acryloyl group equivalent of 116 g / equivalent, and a weight average molecular weight (Mw) of 4,700.
• Example 6 Production of urethane (meth) acrylate resin (2-3) composition
• a flask equipped with a thermometer, a stirrer, and a condenser 432 g of the dipentaerythritol polyacrylate (B3) crude product obtained in Production Example 2 was obtained.
• 0.2 g of dibutyltin dilaurate and 0.2 g of hydroquinone were added, and stirring was started.
• the flask was heated until the internal temperature of the flask reached 50 ° C., and 131.2 g of 4,4-methylenedicyclohexyl-diisocyanate (“VESTANAT H12MDI” manufactured by Evonik Degussa Japan) was added in portions over about one hour. After reacting at 80 ° C. for 3 hours and confirming the disappearance of the isocyanate group by infrared absorption spectrum, the nonvolatile content was adjusted to 80% by mass using butyl acetate, and the urethane (meth) acrylate resin (2-3) composition I got a thing.
• the urethane (meth) acrylate resin (2-3) calculated from the raw material charge ratio had an acryloyl group equivalent of 130 g / equivalent and a weight average molecular weight (Mw) of 7,800.
• Example 7 Production of Urethane (Meth) acrylate Resin (3-1) Composition
• 638 g of the dipentaerythritol polyacrylate (B1) crude product obtained in Production Example 1 was obtained.
• 0.2 g of dibutyltin dilaurate and 0.2 g of hydroquinone were added, and stirring was started.
• the flask was heated until the internal temperature reached 50 ° C., and 111 g of isophorone diisocyanate was added in portions over about one hour. After reacting at 80 ° C.
• the nonvolatile content was adjusted to 80 mass% using butyl acetate, and the urethane (meth) acrylate resin (3-1) composition I got a thing.
• the acryloyl group equivalent of the urethane (meth) acrylate resin (3-1) calculated from the raw material charge ratio was 117 g / equivalent, and the weight average molecular weight (Mw) was 3,800.
• Example 8 Production of Urethane (Meth) acrylate Resin (3-2) Composition
• 0.2 g of dibutyltin dilaurate and 0.2 g of hydroquinone were added, and stirring was started.
• the flask was heated until the internal temperature reached 50 ° C., and 111 g of isophorone diisocyanate was added in portions over about one hour. After reacting at 80 ° C.
• the urethane (meth) acrylate resin (3-2) calculated from the raw material charge ratio had an acryloyl group equivalent of 116 g / equivalent and a weight average molecular weight (Mw) of 4,400.
• Example 9 Production of Urethane (Meth) acrylate Resin (3-3) Composition
• 432 g of the dipentaerythritol polyacrylate (B3) crude product obtained in Production Example 2 was obtained.
• 0.2 g of dibutyltin dilaurate and 0.2 g of hydroquinone were added, and stirring was started.
• the flask was heated until the internal temperature reached 50 ° C., and 111 g of isophorone diisocyanate was added in portions over about one hour. After reacting at 80 ° C.
• the acryloyl group equivalent of the urethane (meth) acrylate resin (3-3) calculated from the raw material charge ratio was 126 g / equivalent, and the weight average molecular weight (Mw) was 7,800.
• the nonvolatile content was adjusted to 80% by mass using butyl acetate, and the urethane (meth) acrylate resin (1 ′) composition Got.
• the urethane (meth) acrylate resin (1 ′) calculated from the raw material charge ratio had an acryloyl group equivalent of 112 g / equivalent and a weight average molecular weight (Mw) of 3,700.
• Examples 10 to 18 and Comparative Example 1 125 parts by mass of the urethane (meth) acrylate resin composition obtained in Examples 1 to 9 and Comparative Production Example, 4 parts by mass of photoinitiator (“Irgacure # 184” manufactured by Ciba Specialty Chemicals) and 75 parts by mass of methyl ethyl ketone were mixed. A curable composition was obtained. The curable composition was subjected to various evaluation tests by the following methods. The results are shown in Tables 2-4.
• Laminated Film 1 The curable composition was applied onto a PET film having a thickness of 100 ⁇ m with a bar coater and dried at 80 ° C. for 2 minutes. Next, ultraviolet light was irradiated at 300 mJ / cm 2 with an 80 W high-pressure mercury lamp in a nitrogen atmosphere to obtain a laminated film 1 having a cured coating film having a thickness of 5 ⁇ m on the PET film.
• Pencil Hardness Test With respect to the laminated film 1, the pencil hardness of the cured coating film surface of the curable composition was measured under a load condition of 500 g according to JIS K5600-5-4. The hardness was measured 5 times for each hardness, and the hardness of the cured coating film was determined as the hardness at which the measurement without scratches was 4 times or more.
• Scratch resistance test 0.5 W of steel wool (“Bonster # 0000” manufactured by Nippon Steel Wool Co., Ltd.) is wrapped with a disc-shaped indenter having a diameter of 2.4 cm, and a load of 500 g is applied to the indenter to form a laminated film.
• a wear test was performed in which the surface of the cured film 1 was reciprocated 200 times.
• the haze value of the coating film before and after the abrasion test was measured using an automatic haze computer (“HZ-2” manufactured by Suga Test Instruments Co., Ltd.), and the scratch resistance was evaluated by the difference value (dH). The smaller the difference value, the higher the resistance to scratches.
• Curl resistance test A 5 cm square coating film was cut out from the laminated film 1 to obtain a test piece. The test piece was measured for floating from four sides horizontally, and the average value (mm) was evaluated. The smaller the value, the smaller the curl and the better the curl resistance.
• the weight was hung at a position where the distance from the surface of the laminated film 1 to the lower end of the weight was 50 mm, and it was dropped on the laminated film 1 after confirming that the shaking and rotation stopped. 3.
• the laminated film 1 after the drop test was left in the room for 1 hour, and then the coating surface was examined for damage. 4).
• the test was continued by separating the distance from the surface of the laminated film 1 to the lower end of the weight by 10 mm, and the evaluation was performed at the maximum distance at which the cured coating film was not cracked or peeled off.
• Adhesion test The curable composition was applied onto an acrylic film having a thickness of 60 ⁇ m with a bar coater and dried at 80 ° C. for 2 minutes. Next, ultraviolet light was irradiated at 50 mJ / cm 2 with an 80 W high-pressure mercury lamp in a nitrogen atmosphere to obtain a laminated film 2 having a cured coating film having a thickness of 5 ⁇ m on the acrylic film. Make a cut with a cutter knife on the cured coating surface of the laminated film 2 to make 100 1mm x 1mm grids, and paste the cellophane adhesive tape on top of it, and then peel it off rapidly. The remaining grids were counted and evaluated according to the following evaluation criteria. A: The number of remaining grids is 80 or more B: The number of remaining grids is 50 or more C: The number of remaining grids is 30 or more D: The number of remaining grids is 29 or less

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Paints Or Removers (AREA)
• Laminated Bodies (AREA)

Priority Applications (2)

Applications Claiming Priority (6)

Publications (1)

Family

ID=60784125

Family Applications (1)

Country Status (4)

Families Citing this family (1)

Citations (8)

Family Cites Families (5)

• 2017
  • 2017-06-08 WO PCT/JP2017/021282 patent/WO2017221726A1/ja active Application Filing
  • 2017-06-08 CN CN201780038152.2A patent/CN109312047A/zh active Pending
  • 2017-06-08 KR KR1020187036682A patent/KR102351943B1/ko active IP Right Grant
  • 2017-06-19 TW TW106120300A patent/TWI775756B/zh active

Patent Citations (8)

Also Published As

Similar Documents

Legal Events