CN109666325B - Active energy ray-curable composition, and cured product and film using same - Google Patents

Active energy ray-curable composition, and cured product and film using same Download PDF

Info

Publication number
CN109666325B
CN109666325B CN201811182465.8A CN201811182465A CN109666325B CN 109666325 B CN109666325 B CN 109666325B CN 201811182465 A CN201811182465 A CN 201811182465A CN 109666325 B CN109666325 B CN 109666325B
Authority
CN
China
Prior art keywords
meth
acrylate
active energy
energy ray
curable composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811182465.8A
Other languages
Chinese (zh)
Other versions
CN109666325A (en
Inventor
西泽茂年
男庭一辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=66142156&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN109666325(B) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by DIC Corp filed Critical DIC Corp
Publication of CN109666325A publication Critical patent/CN109666325A/en
Application granted granted Critical
Publication of CN109666325B publication Critical patent/CN109666325B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • 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
    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • 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
    • C08F290/02—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 end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
    • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
    • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
    • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/025—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Paints Or Removers (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention provides an active energy ray-curable composition, and a cured product and a film using the same, wherein the active energy ray-curable composition comprises: an active energy ray-curable compound (A) having a hydroxyl value of 60mgKOH/g or less, a resin (B) having a quaternary ammonium salt, and an organic solvent (C). The active energy ray-curable compound (a) preferably contains a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, and/or a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. The present invention addresses the problem of providing an active energy ray-curable composition that can form a hard coat layer having excellent antistatic properties and pencil hardness, and a film using the same.

Description

Active energy ray-curable composition, and cured product and film using same
Technical Field
The present invention relates to an active energy ray-curable composition, and a cured product and a film using the same.
Background
Various resin films are used in various applications such as a film for preventing scratches on the surface of a Flat Panel Display (FPD) such as a Liquid Crystal Display (LCD), an Organic Electroluminescent Display (OLED), a Plasma Display (PDP), and the like, a decorative film (sheet) for interior and exterior decoration of an automobile, a low reflection film for windows, a heat ray cut-off film, and the like. However, since the surface of the resin film is soft and has low scratch resistance, in order to compensate for the above-mentioned drawbacks, a hard coating layer is usually provided on the surface of the film by applying a hard coating agent containing an Ultraviolet (UV) curable composition or the like to the surface of the film and curing the hard coating agent. To summarize the procedure of providing the hard coat layer, the film blank wound into a roll is conveyed to a coating machine, a hard coat agent is applied, and the hard coat layer is formed by curing by ultraviolet irradiation, and then the film blank is wound into a roll again.
In the winding step, static electricity is generated on the film surface by friction between the films, and therefore, there is a problem that the films adhere to each other when the films are drawn out from the roll during reprocessing, or dust or the like is easily attached to the film surface due to static electricity. In addition, when the film is used for a liquid crystal display or the like, there is a problem that the display malfunctions due to static electricity generated.
In order to suppress the generation of static electricity on the film surface, a method of blending an antistatic agent into a hard coating agent is generally performed. For example, a method of blending a compound having a polyoxyethylene chain and a quaternary ammonium salt as an antistatic agent in a hard coat agent has been proposed (for example, see patent document 1).
Further, a method of blending two kinds of copolymers, which are obtained by using polymerizable monomers having quaternary ammonium salts as raw materials, as antistatic agents in a hard coat agent has been proposed (for example, see patent document 2).
However, the antistatic properties of hard coat agents formulated with these antistatic agents are not sufficient. Furthermore, when an antistatic agent is blended, there is a problem that the hardness of the coating film surface is lowered, and a hard coating agent having both excellent antistatic property and hardness is demanded.
[ Prior art documents ]
[ patent document ]
[ patent document 1] Japanese patent laid-open No. 2004-143303
[ patent document 2] Japanese patent laid-open No. 2004-123924
Disclosure of Invention
[ problems to be solved by the invention ]
The present invention addresses the problem of providing an active energy ray-curable composition capable of forming a hard coat layer having excellent antistatic properties and pencil hardness, and a film using the same.
[ means for solving the problems ]
The invention provides an active energy ray-curable composition and a film using the same, the active energy ray-curable composition comprising: an active energy ray-curable compound (A) having a hydroxyl value of 60mgKOH/g or less, a resin (B) having a quaternary ammonium salt, and an organic solvent (C).
[ Effect of the invention ]
The active energy ray-curable composition of the present invention can form a hard coat layer having excellent antistatic properties and pencil hardness by applying the composition to the surface of a film and curing the composition. Therefore, the cured coating film of the active energy ray-curable composition of the present invention can suppress the generation of static electricity on the film surface. Therefore, various films can be provided with functions such as adhesion prevention, prevention of adhesion of dust due to static electricity, and the like. Therefore, the film having a cured coating film of the active energy ray-curable composition of the present invention can avoid problems such as adhesion and adhesion of dust when wound into a roll shape and when pulled out from the roll, and therefore can provide a film having excellent handling properties after winding. Further, the cured coating film of the active energy ray-curable composition of the present invention has excellent pencil hardness, and thus can be used in a wide range of applications such as electronic blackboards.
In addition, a film having a hard coat layer comprising a cured coating film of the active energy ray-curable composition of the present invention can be preferably used as an optical film used in a Flat Panel Display (FPD) such as a Liquid Crystal Display (LCD), an organic EL display (OLED), a Plasma Display (PDP), and the like. Further, since the antistatic property is excellent even when the resin composition is used for these applications, adhesion of dust and the like can be suppressed. Further, when the film is used for a liquid crystal display or the like, malfunction of the display due to static electricity generated can be prevented.
Detailed Description
The active energy ray-curable composition of the present invention comprises: an active energy ray-curable compound (A) having a hydroxyl value of 60mgKOH/g or less, a resin (B) having a quaternary ammonium salt, and an organic solvent (C).
The active energy ray-curable compound (A) is required to have a hydroxyl value of 60mgKOH/g or less in view of excellent antistatic properties and pencil hardness. The hydroxyl value of the active energy ray-curable compound (A) is more preferably in the range of 3 to 55mgKOH/g, still more preferably in the range of 3 to 40mgKOH/g, from the viewpoint of obtaining more excellent antistatic properties and pencil hardness. The method for measuring the hydroxyl value of the active energy ray-curable compound (a) is described in examples described later. When a mixture of two or more kinds is used as the active energy ray-curable compound (a), the hydroxyl value of the mixture is represented.
Examples of the active energy ray-curable compound (a) include: <xnotran> 3232 zxft 3232- () ,3- -3238 zxft 3238- () , 3262 zxft 3262- () , () , 2- -3234 zxft 3234- () , 2- -2- -3236 zxft 3236- () , () , () , () , () , () , () () , () , () , (2- ) () , 1 4 () , 1 A 2 () , () , () , () , </xnotran> Polyfunctional (meth) acrylates such as di-trimethylolpropane tri (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, and polypentaerythritol poly (meth) acrylate. These compounds may be used alone or in combination of two or more. Since the active energy ray-curable compound (a) can achieve higher density, it is preferable to use a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate and/or a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in order to obtain more excellent antistatic properties and pencil hardness.
In the present invention, the "(meth) acrylate" means one or both of an acrylate and a methacrylate, and the "(meth) acryloyl group" means one or both of an acryloyl group and a methacryloyl group.
The mass ratio ([ pentaerythritol triacrylate/pentaerythritol tetraacrylate ]) when a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate is used as the active energy ray-curable compound (a) is preferably within a range of 32/68 to 2/98, more preferably within a range of 21/79 to 2/98, in view of obtaining more excellent antistatic properties and pencil hardness.
Further, the mass ratio ([ dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate ]) when a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate is used as the active energy ray-curable compound (a) is preferably in the range of 56/44 to 3/97, more preferably in the range of 50/50 to 3/97, and still more preferably in the range of 37/63 to 3/97, in terms of obtaining more excellent antistatic properties and pencil hardness.
The active energy ray-curable compound (a) may be used in combination with a urethane (meth) acrylate, if necessary, in addition to the polyfunctional (meth) acrylate.
The urethane (meth) acrylate may use a reactant of polyisocyanate and (meth) acrylate having a hydroxyl group.
The polyisocyanate includes aliphatic polyisocyanates and aromatic polyisocyanates, but aliphatic polyisocyanates are preferable in terms of reducing the coloration of the cured coating film of the active energy ray-curable composition of the present invention.
The aliphatic polyisocyanate is a compound in which the site other than the isocyanate group is composed of an aliphatic hydrocarbon. Specific examples of the aliphatic polyisocyanate include: aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; alicyclic polyisocyanates such as norbornane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, and 2-methyl-1,5-diisocyanatocyclohexane. In addition, a trimer obtained by trimerizing the aliphatic polyisocyanate or the alicyclic polyisocyanate may be used as the aliphatic polyisocyanate. One kind of these aliphatic polyisocyanates may be used, or two or more kinds thereof may be used in combination.
Among the aliphatic polyisocyanates, hexamethylene diisocyanate, which is a diisocyanate of a linear aliphatic hydrocarbon, norbornane diisocyanate, which is an alicyclic diisocyanate, and isophorone diisocyanate are preferable in order to improve the scratch resistance of a coating film.
The (meth) acrylate is a compound having a hydroxyl group and a (meth) acryloyl group. Specific examples of the (meth) acrylic acid ester include: mono (meth) acrylates of glycols such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, hydroxypivalic acid neopentyl glycol mono (meth) acrylate, and the like; trimethylolpropane di (meth) acrylate, ethylene Oxide (EO) modified trimethylolpropane (meth) acrylate, propylene Oxide (PO) modified trimethylolpropane di (meth) acrylate, glycerol di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, and the like trihydric alcohol mono-or di (meth) acrylate, or hydroxyl group-containing mono-and di (meth) acrylate obtained by modifying a part of these alcoholic hydroxyl groups with e-caprolactone; a compound having a monofunctional hydroxyl group and a trifunctional or higher (meth) acryloyl group such as pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, or a polyfunctional (meth) acrylate having a hydroxyl group obtained by modifying the compound with e-caprolactone; (meth) acrylates having an oxyalkylene chain such as dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polyethylene glycol mono (meth) acrylate; (meth) acrylates having an oxyalkylene chain with a block structure such as polyethylene glycol-polypropylene glycol mono (meth) acrylate and polyoxybutylene-polyoxypropylene mono (meth) acrylate; and (meth) acrylates having an oxyalkylene chain of a random structure such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate. One kind of these (meth) acrylates may be used, or two or more kinds thereof may be used in combination.
The reaction of the polyisocyanate with the (meth) acrylate can be carried out using a urethanization reaction of a conventional method. In order to promote the progress of the urethanization reaction, it is preferable to carry out the urethanization reaction in the presence of a urethanization catalyst. Examples of the urethane-forming catalyst include: amine compounds such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; and organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate, and tin octylate, and organic zinc compounds such as zinc octylate.
The resin (B) must be a resin having a quaternary ammonium salt in terms of attaining excellent antistatic properties.
The resin (B) may be, for example, a copolymer containing a polymerizable monomer (B1) having a quaternary ammonium salt as an essential component, and the polymerizable monomer (B2) copolymerizable with the (B1).
Examples of the polymerizable monomer (b 1) having a quaternary ammonium salt include: counter anions such as 2- [ (meth) acryloyloxy ] ethyltrimethylammonium chloride and 3- [ (meth) acryloyloxy ] propyltrimethylammonium chloride are chloride ions; bromide as counter anion such as 2- [ (meth) acryloyloxy ] ethyltrimethylammonium bromide and 3- [ (meth) acryloyloxy ] propyltrimethylammonium bromide; a non-halogen counter anion such as 2- [ (meth) acryloyloxy ] ethyltrimethylammonium methylphenylsulfonate, 2- [ (meth) acryloyloxy ] ethyltrimethylammonium methylsulfonate, 3- [ (meth) acryloyloxy ] propyltrimethylammonium methylphenylsulfonate, 3- [ (meth) acryloyloxy ] propyltrimethylammonium methylsulfonate, 2- [ (meth) acryloyloxy ] ethyltrimethylammonium methylsulfate, 3- [ (meth) acryloyloxy ] propyltrimethylammonium methylsulfate, etc.; dimethylaminoethyl (meth) acrylamide chloromethyl quaternary salt, dimethylaminopropyl (meth) acrylamide chloromethyl quaternary salt, and the like. One kind of the polymerizable monomers (b 1) may be used, or two or more kinds may be used in combination.
Examples of the polymerizable monomer (b 2) include: alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, and dodecyl (meth) acrylate; mono (meth) acrylates of polyalkylene glycols such as methoxypolyethylene glycol mono (meth) acrylate, octyloxypolyethylene glycol-polypropylene glycol mono (meth) acrylate, dodecyloxypolyethylene glycol mono (meth) acrylate, octadecyloxypolyethylene glycol mono (meth) acrylate, phenoxypolyethylene glycol-polypropylene glycol mono (meth) acrylate, nonylphenoxypolypropylene glycol mono (meth) acrylate, and nonylphenoxypoly (ethylene glycol-propylene glycol) mono (meth) acrylate; aromatic mono (meth) acrylates such as benzyl (meth) acrylate; and (meth) acrylates having a fluorinated alkyl group such as 2-perfluorohexylethyl (meth) acrylate. One kind of the polymerizable monomers (b 2) may be used, or two or more kinds may be used in combination.
In view of obtaining more excellent antistatic properties, the polymerizable monomer (b 2) is preferably a (meth) acrylate having a fluorinated alkyl group and/or a mono (meth) acrylate of a polyalkylene glycol, and the mono (meth) acrylate of a polyalkylene glycol is more preferably a methoxypolyethylene glycol mono (meth) acrylate.
Among the mono (meth) acrylates of polyalkylene glycols, those having a number average molecular weight of polyalkylene glycol as a raw material of the mono (meth) acrylate of polyalkylene glycol in the range of 200 to 8,000, more preferably 300 to 6,000, still more preferably 400 to 4,000, and particularly preferably 400 to 2,000 are preferable in terms of more excellent antistatic properties.
As the resin (B), a resin having an alicyclic structure is more preferably used in terms of more excellent antistatic property.
Examples of the resin (B) having an alicyclic structure include a resin obtained by copolymerizing a polymerizable monomer (B3) having an alicyclic structure with the polymerizable monomer (B1) and the polymerizable monomer (B2).
The polymerizable monomer (b 3) is a polymerizable monomer having an alicyclic structure. Examples of the alicyclic structure include: a monocyclic alicyclic structure such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, or a cyclodecane ring; bicyclic undecane ring, decahydronaphthalene (decalin) ring, tricyclic [5.2.1.0 ] 2,6 ]Decane ring, bicyclo [4.3.0]Nonane ring, tricyclo [5.3.1.1]Dodecyl ring, spiro [3.4 ]]And polycyclic alicyclic structures such as octane rings. Specific examples of the polymerizable monomer (b 1) include: cyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like. One kind of the polymerizable monomers (b 3) may be used, or two or more kinds may be used in combination.
In addition, in order to further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention, the ratio of the polymerizable monomer (B1) in the total amount of the raw materials of the resin (B) is preferably within a range of 30 to 90 mass%, more preferably within a range of 40 to 80 mass%, and still more preferably within a range of 45 to 70 mass%.
In the case where the polyalkylene glycol mono (meth) acrylate is used as the polymerizable monomer (B2), the ratio of the polyalkylene glycol mono (meth) acrylate in the total amount of the raw materials of the resin (B) is preferably in the range of 5 to 60 mass%, more preferably in the range of 10 to 50 mass%, and still more preferably in the range of 20 to 40 mass%, in terms of further improving the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention.
In addition, in the case where the (meth) acrylate having a fluorinated alkyl group is used as the polymerizable monomer (B2), the ratio of the (meth) acrylate having a fluorinated alkyl group in the total amount of the raw materials of the resin (B) is preferably in the range of 0.1 to 20% by mass, more preferably in the range of 0.5 to 10% by mass, and still more preferably in the range of 1 to 5% by mass, in terms of further improving the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention.
In the case where the resin (B) having an alicyclic structure is used, the proportion of the polymerizable monomer (B3) in the total amount of the raw materials of the resin (B) is preferably in the range of 5 to 55% by mass, more preferably in the range of 10 to 50% by mass, and still more preferably in the range of 12 to 45% by mass, in terms of further improving the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention.
In order to further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention, the weight average molecular weight of the resin (B) is preferably in the range of 1,000 to 100,000, more preferably in the range of 2,000 to 50,000, and still more preferably in the range of 3,000 to 30,000. The weight average molecular weight in the present invention is a value in terms of polystyrene measured by a Gel Permeation Chromatography (GPC) method.
In order to further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention, the amount of the resin (B) to be blended is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 1.5 to 20 parts by mass, and still more preferably in the range of 5 to 18 parts by mass, based on 100 parts by mass of the active energy ray-curable composition (a).
The organic solvent (C) is not particularly limited as long as it can dissolve other components in the active energy ray-curable composition of the present invention. Examples of the organic solvent (C) include: aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and tert-butanol; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and the like; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; glycols such as propylene glycol monomethyl ether. These organic solvents may be used alone or in combination of two or more.
The amount of the organic solvent (C) to be blended in the active energy ray-curable composition of the present invention is preferably an amount that has a viscosity suitable for a coating method described later.
The active energy ray-curable composition of the present invention can be applied to a substrate and then irradiated with an active energy ray to form a cured coating film. The active energy ray is an ionizing ray such as an ultraviolet ray, an electron beam, an alpha ray, a beta ray, or a gamma ray. When a cured coating film is formed by irradiating ultraviolet rays as an active energy ray, it is preferable to add a photopolymerization initiator (D) to the active energy ray-curable composition of the present invention to improve the curability. If necessary, a photo sensitizer may be further added to improve the curing properties. On the other hand, when ionizing radiation such as electron beam, α -ray, β -ray, γ -ray or the like is used, the curing proceeds rapidly without using the photopolymerization initiator (D) or the photosensitizer, and therefore, it is not necessary to add the photopolymerization initiator (D) or the photosensitizer in particular.
Examples of the photopolymerization initiator (D) include: acetophenone compounds such as diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo { 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl ] propanone }, benzildimethylketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholinyl (4-thiomethylphenyl) propan-1-one, and 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin isopropyl ether, etc.; acylphosphine oxide-based compounds such as 2,4,6-trimethylbenzoin diphenylphosphine oxide and bis (2,4,6-trimethylbenzoin) -phenylphosphine oxide; benzil-based compounds such as benzil (dibenzoyl), methylphenylglyoxylic acid ester, oxyphenylacetic acid 2- (2-hydroxyethoxy) ethyl ester, oxyphenylacetic acid 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester and the like; benzophenone-based compounds such as benzophenone, methyl o-benzoylbenzoate-4-phenylbenzophenone, 4,4' -dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4 ' -methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4' -tetrakis (t-butylperoxycarbonyl) benzophenone, 3,3' -dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, and 4-methylbenzophenone; thioxanthone compounds such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone; aminobenzophenone-based compounds such as milone and 4,4' -diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1- [4- (4-benzoylphenylthio) phenyl ] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, and the like. One kind of the photopolymerization initiator (D) may be used, or two or more kinds thereof may be used in combination.
Examples of the photosensitizer include: tertiary amine compounds such as diethanolamine, N-methyldiethanolamine and tributylamine, urea compounds such as o-tolylthiourea, and sulfur compounds such as sodium diethyldithiophosphate and s-benzylisothiouronium-p-toluenesulfonate.
The amounts of the photopolymerization initiator (D) and the photosensitizer used are preferably 0.05 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, respectively, per 100 parts by mass of the active energy ray-curable compound (a) in the active energy ray-curable composition of the present invention.
The active energy ray-curable composition of the present invention may contain additives such as a polymerization inhibitor, a surface modifier, an antifoaming agent, a viscosity modifier, a light-resistant stabilizer, a weather-resistant stabilizer, a heat-resistant stabilizer, an ultraviolet absorber, an antioxidant, a leveling agent, an organic pigment, an inorganic pigment, a pigment dispersant, silica beads, and organic beads, depending on the application and the required characteristics; inorganic fillers such as silica, alumina, titania, zirconia, and antimony pentoxide, and the like, as other formulations than the components (a) to (D). These other formulations may be used in one kind, or two or more kinds may be used in combination.
The film of the present invention is obtained by applying the active energy ray-curable composition of the present invention to at least one surface of a film substrate and then irradiating the film with active energy rays to form a cured coating film.
The material of the film base used in the film of the present invention is preferably a highly transparent resin, and examples thereof include: polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin resins such as polypropylene, polyethylene and polymethylpentene-1; cellulose resins such as cellulose acetate (e.g., diacetylcellulose and triacetylcellulose), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, and cellulose nitrate; acrylic resins such as polymethyl methacrylate; vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; polyvinyl alcohol; ethylene-vinyl acetate copolymers; polystyrene; a polyamide; a polycarbonate; polysulfones; polyether sulfone; polyether ether ketone; polyimide resins such as polyimide and polyetherimide; norbornene-based resins (for example, "canola (Zeonor)", manufactured by nippon (ZEON) corporation), modified norbornene-based resins (for example, "atone (Arton)", manufactured by JSR corporation), cyclic olefin copolymers (for example, "appel (Apel)", manufactured by mitsui chemical corporation), and the like. Further, a laminate of two or more substrates containing these resins may be used.
The film base may be in the form of a film or a sheet, and the thickness thereof is preferably in the range of 20 to 500 μm. When a film-like base film is used, the thickness thereof is preferably in the range of 20 to 200. Mu.m, more preferably in the range of 30 to 150. Mu.m, and still more preferably in the range of 40 to 130. Mu.m. When the thickness of the film base material is within the above range, even when a hard coat layer is provided on one surface of the film by the active energy ray-curable composition of the present invention, curling is easily suppressed.
Examples of the method for applying the active energy ray-curable composition of the present invention to the film substrate include: die coating, microgravure coating, gravure coating, roll coating, unfilled-corner wheel coating, air knife coating, kiss coating, spray coating, dip coating, spin coating, brush coating, full-thickness coating by screen printing, wire bar coating, flow coating, and the like.
In the case where the active energy ray-curable composition of the present invention contains an organic solvent, it is preferable to heat or dry the composition at room temperature so that the organic solvent is volatilized after the active energy ray-curable composition is applied to the substrate film and before the active energy ray is irradiated, and the resin (B) is segregated on the surface of the coating film. The conditions for the heat drying are not particularly limited as long as the organic solvent is volatilized, but it is generally preferable to perform the heat drying at a temperature in the range of 50 to 100 ℃ for a time in the range of 0.5 to 10 minutes.
The active energy ray for curing the active energy ray-curable composition of the present invention is an ionizing ray such as ultraviolet ray, electron beam, α ray, β ray, or γ ray as described above. In the case where ultraviolet rays are used as the active energy rays, examples of the means for irradiating the ultraviolet rays include: low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, electrodeless lamps (fusion lamps), chemical lamps, black-Light lamps, mercury-xenon lamps, short-arc lamps, helium-cadmium lasers, argon lasers, sunlight, light Emitting Diode (LED) lamps, and the like.
The thickness of the cured coating film when the cured coating film of the active energy ray-curable composition of the present invention is formed on the film base material is preferably in the range of 1 to 30 μm, more preferably in the range of 3 to 15 μm, and even more preferably in the range of 4 to 10 μm, in terms of sufficient hardness of the cured coating film and suppression of curling of the film due to curing shrinkage of the coating film.
As described above, the active energy ray-curable composition of the present invention can form a hard coat layer having excellent antistatic properties and pencil hardness. The surface resistance of the cured coating film of the composition curable with active energy rays is preferably 1X 10 7 Ω/□～9.99×10 9 Omega/□, more preferably 1 × 10 7 Ω/□～9.99×10 8 Omega/□. The method for measuring the surface resistance value of the cured coating film is described in examples.
[ examples ]
The present invention will be described in more detail with reference to examples.
( Production example 1: production of resin (B-1) having alicyclic Structure and Quaternary ammonium salt )
Nitrogen gas was introduced into a flask equipped with a stirring device, a reflux condenser and a nitrogen gas introduction tube, and the air in the flask was replaced with nitrogen gas. Then, 54.7 parts by mass of 2- (methacryloyloxy) ethyltrimethyl ammonium chloride, 19.9 parts by mass of cyclohexyl methacrylate, 24.9 parts by mass of methoxypolyethylene Glycol methacrylate ("Brelmar (Blemmer) PME-1000" manufactured by Nichigan oil Co., ltd.; repeating unit number n ≈ 23, molecular weight 1,000), 0.5 part by mass of methacrylic acid, 50 parts by mass of methanol, and 10 parts by mass of Propylene Glycol Monomethyl Ether (PGME) were charged into the flask. Then, a solution prepared by dissolving 0.1 part by mass of a polymerization initiator (azobisisobutyronitrile) in 2.4 parts by mass of PGME was added dropwise over 30 minutes, followed by reaction at 65 ℃ for 3 hours. Subsequently, methanol was added and diluted to obtain a 45 mass% solution of the resin (B-1) having an alicyclic structure and a quaternary ammonium salt. The weight-average molecular weight of the resulting resin (B-1) was 1 ten thousand.
( Production example 2: production of resin (B-2) having alicyclic Structure and Quaternary ammonium salt )
Nitrogen gas was introduced into a flask equipped with a stirrer, a reflux condenser and a nitrogen gas inlet tube, and the air in the flask was replaced with nitrogen gas. Then, 53.7 parts by mass of 2- (methacryloyloxy) ethyltrimethyl ammonium chloride, 29.3 parts by mass of cyclohexyl methacrylate, 14.6 parts by mass of methoxypolyethylene glycol methacrylate ("Brelmar (Blemmer) PME-1000" manufactured by Nichigan oil Co., ltd.; repeating unit number n ≈ 23, molecular weight 1,000), 1.9 parts by mass of 2-perfluorohexylethyl acrylate, 0.5 parts by mass of methacrylic acid, 50 parts by mass of methanol, and 10 parts by mass of propylene glycol monomethyl ether were charged into the flask. Then, a solution prepared by dissolving 0.1 part by mass of a polymerization initiator (azobisisobutyronitrile) in 2.4 parts by mass of propylene glycol monomethyl ether was added dropwise over 30 minutes, followed by reaction at 65 ℃ for 3 hours. Subsequently, methanol was added and diluted to obtain a 45 mass% solution of the resin (B-2) having an alicyclic structure and a quaternary ammonium salt. The weight-average molecular weight of the resulting resin (B-2) was 1 ten thousand.
The weight average molecular weights of the resin (B-1) and the resin (B-2) thus obtained were measured by a Gel Permeation Chromatography (GPC) method under the following conditions.
A measuring device: high speed GPC apparatus ("HLC-8220 GPC" manufactured by Tosoh corporation.)
Pipe column: the following columns manufactured by Tosoh corporation were connected in series and used.
"TSKgel G5000" (7.8mmI.D.. Times.30 cm). Times.1 tubes
"TSKgel G4000" (7.8mmI.D.. Times.30 cm). Times.1 tubes
"TSKgel G3000" (7.8mmI.D.. Times.30 cm). Times.1 tubes
"TSKgel G2000" (7.8mmI.D.. Times.30 cm). Times.1 pieces
A detector: RI (differential refractometer)
Temperature of the pipe column: 40 deg.C
And (3) dissolving and separating liquid: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Injection amount: 100 μ L (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: the standard curve was prepared using the following standard polystyrene.
(Standard polystyrene)
"TSKgel Standard polystyrene A-500" manufactured by Tosoh corporation "
"TSKgel Standard polystyrene A-1000" manufactured by Tosoh corporation "
TSKgel Standard polystyrene A-2500 manufactured by Tosoh corporation "
"TSKgel Standard polystyrene A-5000" manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-1 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-2 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-4 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-10 manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-20 manufactured by Tosoh corporation "
"TSKgel Standard polystyrene F-40" manufactured by Tosoh corporation "
"TSKgel Standard polystyrene F-80" manufactured by Tosoh corporation "
"TSKgel Standard polystyrene F-128" manufactured by Tosoh corporation "
TSKgel Standard polystyrene F-288 manufactured by Tosoh corporation "
"TSKgel Standard polystyrene F-550" manufactured by Tosoh corporation "
[ method for measuring hydroxyl value ]
The hydroxyl value of the active energy ray-curable composition was measured by the following method using the hydroxyl value measurement method described in Japanese Industrial Standards (JIS) -K0070.
25g of acetic anhydride was weighed out into 100ml of a total flask, pyridine was added to make the total amount to be 100ml, the mixture was weighed to 5ml, and after dissolving the active energy ray-curable compound therein, acetic anhydride was reacted with a hydroxyl group in the active energy ray-curable compound at 100 ℃ for 1 hour. In the placingAfter cooling, 1ml of water was added thereto, followed by mixing with stirring, further stirring at 100 ℃ for 10 minutes to decompose excess acetic anhydride, and after leaving to cool, the wall of the flask or the like was washed with 5ml of ethanol. Several drops of phenolphthalein solution were added as an indicator, and titration was performed using 0.5mol/L potassium hydroxide ethanol solution (titration amount. Beta.ml). Blank measurement without using an active energy ray-curable compound was performed in the same manner, and titration (titration amount. Beta.) was performed 0 ml). The hydroxyl value is determined by the following formula (1).
Hydroxyl value (mgKOH/g) = (beta) 0 -β)×f×28.05/S+D (1)
Wherein, f: factor of 0.5mol/L potassium hydroxide ethanol solution
S: actual weight (unit: g) of the active energy ray-curable compound
D: acid value (mgKOH/g)
(example 1)
An active energy ray-curable composition (1) was obtained by uniformly mixing 100 parts by mass of a polyfunctional acrylate mixture (a mixture of 4% by mass of pentaerythritol triacrylate and 96% by mass of pentaerythritol tetraacrylate; hydroxyl value: 8 mgKOH/g), 33.3 parts by mass of the resin (B-1) solution obtained in production example 1 (15 parts by mass of the resin (B-1)), 5 parts by mass of a photopolymerization initiator (1-hydroxycyclohexylphenylketone), and 100 parts by mass of methyl ethyl ketone (hereinafter, abbreviated as "MEK").
(examples 2 to 5, comparative examples 1 to 2)
The active energy ray-curable compositions (2) to (5), and the active energy ray-curable compositions (R1) to (R2) were obtained in the same manner as in example 1, except that the compositions shown in table 1 were changed.
[ preparation of sample for evaluation ]
The active energy ray-curable composition was applied to a Triacetyl Cellulose (TAC) film (manufactured by Fuji film Ltd.) having a thickness of 60 μm by a bar coater so as to have a film thickness of 5 μm, dried at 60 ℃ for 1.5 minutes, and then irradiated with ultraviolet rays (Eye Graphics) under an air atmosphere using an ultraviolet irradiation apparatus (Eye Graphics) part Gu LafeiHigh-pressure mercury lamp manufactured by limited) to irradiate an amount of light of 3kJ/m 2 Irradiated to obtain a TAC film having a cured coating film as a sample for evaluation.
[ measurement of Pencil hardness ]
The surface of the cured coating film of the obtained evaluation sample was measured for pencil hardness based on JIS test method K5600-5-4.
[ measurement of surface resistance value (evaluation of antistatic Property) ]
The surface of the hardened coating film of the obtained evaluation sample was measured for surface resistance value at an applied voltage of 500V for a measurement time of 10 seconds using a high resistivity meter ("Hiresta (Hiresta) UP MCP-HT 450") manufactured by Mitsubishi Chemical analysis technology (Mitsubishi Chemical analytical instruments) based on JIS test method K6911-1995.
[ Table 1]
Figure BDA0001825336930000141
The abbreviations shown in table 1 represent the following compounds.
"PETA": pentaerythritol triacrylate
"PETTA": pentaerythritol tetraacrylate
"DPPA": dipentaerythritol pentaacrylate
"DPHA": dipentaerythritol hexaacrylate
It was confirmed that the cured coating film of the active energy ray-curable composition of the present invention has excellent pencil hardness, a surface resistance value of less than 10 on the order of 9, and good antistatic properties.
On the other hand, in comparative examples 1 to 2, the hydroxyl value of the active energy ray-curable compound (a) exceeded the range specified in the present invention, but the surface resistance thereof exceeded 13 th power of 10, and it was confirmed that the antistatic property was poor.

Claims (5)

1. An active energy ray-curable composition characterized by comprising: an active energy ray-curable compound (A) having a hydroxyl value of 60mgKOH/g or less, a resin (B) having a quaternary ammonium salt, and an organic solvent (C),
the resin (B) having a quaternary ammonium salt is obtained by copolymerizing only a polymerizable monomer (B1) having at least a quaternary ammonium salt, a polymerizable monomer (B2), and a polymerizable monomer (B3) having an alicyclic structure,
the polymerizable monomer (b 1) is one or more monomers selected from the group consisting of 2- [ (meth) acryloyloxy ] ethyltrimethylammonium chloride, 3- [ (meth) acryloyloxy ] propyltrimethylammonium chloride, 2- [ (meth) acryloyloxy ] ethyltrimethylammonium bromide, 3- [ (meth) acryloyloxy ] propyltrimethylammonium bromide, 2- [ (meth) acryloyloxy ] ethyltrimethylammonium methylphenylsulfonate, 2- [ (meth) acryloyloxy ] ethyltrimethylammonium methylsulfonate, 3- [ (meth) acryloyloxy ] propyltrimethylammonium methylphenylsulfonate and 3- [ (meth) acryloyloxy ] propyltrimethylammonium methylsulfonate,
the polymerizable monomer (b 2) is one or more monomers selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, octyloxypolyethylene glycol polypropylene glycol mono (meth) acrylate, dodecyloxypolyethylene glycol mono (meth) acrylate, octadecyloxypolyethylene glycol mono (meth) acrylate, phenoxypolyethylene glycol polypropylene glycol mono (meth) acrylate, nonylphenoxypolypropylene glycol mono (meth) acrylate, nonylphenoxypolyethylene glycol propylene glycol mono (meth) acrylate, benzyl (meth) acrylate, and 2-perfluorohexylethyl (meth) acrylate,
the polymerizable monomer (b 3) is one or more selected from the group consisting of cyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopentanyl (meth) acrylate,
the active energy ray-curable compound (A) contains a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate and/or a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate,
the mass ratio of the pentaerythritol triacrylate to the pentaerythritol tetraacrylate is 32/68 to 2/98,
the mass ratio of the dipentaerythritol pentaacrylate to the dipentaerythritol hexaacrylate is 56/44-3/97.
2. The active energy ray-curable composition according to claim 1, wherein the resin (B) is a polymer obtained by using 5 to 55 mass% of the polymerizable monomer (B3) as a raw material.
3. The active energy ray-curable composition according to claim 1 or 2, wherein the amount of the resin (B) is in the range of 0.1 to 30 parts by mass per 100 parts by mass of the active energy ray-curable compound (a).
4. A cured product of the active energy ray-curable composition according to any one of claims 1 to 3.
5. A film characterized by having a cured coating film of the active energy ray-curable composition according to any one of claims 1 to 3.
CN201811182465.8A 2017-10-16 2018-10-11 Active energy ray-curable composition, and cured product and film using same Active CN109666325B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-200262 2017-10-16
JP2017200262A JP7024309B2 (en) 2017-10-16 2017-10-16 Active energy ray-curable composition and film using it

Publications (2)

Publication Number Publication Date
CN109666325A CN109666325A (en) 2019-04-23
CN109666325B true CN109666325B (en) 2022-12-30

Family

ID=66142156

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811182465.8A Active CN109666325B (en) 2017-10-16 2018-10-11 Active energy ray-curable composition, and cured product and film using same

Country Status (4)

Country Link
JP (1) JP7024309B2 (en)
KR (1) KR102597331B1 (en)
CN (1) CN109666325B (en)
TW (1) TWI791642B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113406861A (en) * 2020-03-16 2021-09-17 荒川化学工业株式会社 Active energy ray-curable resin composition, cured film, and film
JP7533763B2 (en) * 2021-03-02 2024-08-14 Dic株式会社 Active energy ray curable composition, cured product and film
KR102685640B1 (en) * 2022-01-24 2024-07-19 (주)더존테크 A composition of hard coating having high hardness and weather resistance
WO2024058031A1 (en) * 2022-09-12 2024-03-21 荒川化学工業株式会社 Actinic-ray-curable resin composition, cured object, and multilayered object

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102906126A (en) * 2009-10-30 2013-01-30 3M创新有限公司 Optical device with antistatic property
CN103197363A (en) * 2012-08-30 2013-07-10 湖北航天化学技术研究所 Scratch-proof optics diffusion film and preparation method thereof
CN103819616A (en) * 2013-02-01 2014-05-28 江阴摩尔化工新材料有限公司 Photosensitive acrylic AED resin and negative photoresist composition comprising same, and preparation method thereof
CN106459240A (en) * 2014-06-27 2017-02-22 Dic株式会社 Active energy ray-curable composition and film using same
CN106626854A (en) * 2009-09-30 2017-05-10 爱克工业株式会社 Active energy ray-curable resin composition, transfer sheet, decorative board, and method for producing decorative board

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3963447B2 (en) 2002-10-03 2007-08-22 竹本油脂株式会社 Antistatic agent for polyester film and antistatic method for polyester film
JP4229228B2 (en) 2002-10-25 2009-02-25 日本合成化学工業株式会社 Urethane (meth) acrylate compound and active energy ray-curable resin composition using the same
JP2012031297A (en) 2010-07-30 2012-02-16 Arakawa Chem Ind Co Ltd Antistatic agent for active energy ray-curable type resin composition, active energy ray-curable type composition, cured coating film, and antistatic-treated optical film
JP6244153B2 (en) * 2013-09-27 2017-12-06 伊東　謙吾 Conductive BN electrolyte / clay composite material
JP6725864B2 (en) 2015-08-21 2020-07-22 Dic株式会社 Active energy ray curable composition and film using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106626854A (en) * 2009-09-30 2017-05-10 爱克工业株式会社 Active energy ray-curable resin composition, transfer sheet, decorative board, and method for producing decorative board
CN102906126A (en) * 2009-10-30 2013-01-30 3M创新有限公司 Optical device with antistatic property
CN103197363A (en) * 2012-08-30 2013-07-10 湖北航天化学技术研究所 Scratch-proof optics diffusion film and preparation method thereof
CN103819616A (en) * 2013-02-01 2014-05-28 江阴摩尔化工新材料有限公司 Photosensitive acrylic AED resin and negative photoresist composition comprising same, and preparation method thereof
CN106459240A (en) * 2014-06-27 2017-02-22 Dic株式会社 Active energy ray-curable composition and film using same

Also Published As

Publication number Publication date
JP7024309B2 (en) 2022-02-24
KR102597331B1 (en) 2023-11-06
TWI791642B (en) 2023-02-11
TW201917138A (en) 2019-05-01
KR20190042450A (en) 2019-04-24
JP2019073616A (en) 2019-05-16
CN109666325A (en) 2019-04-23

Similar Documents

Publication Publication Date Title
CN109666325B (en) Active energy ray-curable composition, and cured product and film using same
KR101784239B1 (en) Active energy ray-curable composition and film using same
CN110402258B (en) Active energy ray-curable composition, cured product, and film
JP6725864B2 (en) Active energy ray curable composition and film using the same
CN109328198B (en) Active energy ray-curable composition and film using same
CN109312012B (en) Active energy ray-curable composition and film using same
CN111566129B (en) Active energy ray-curable composition and film using same
KR102625535B1 (en) Active energy ray-curable composition and film using the same
CN109666173B (en) Laminate body
CN116888162A (en) Active energy ray-curable composition, cured product, and film

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant