WO2018003294A1 - 活性エネルギー線硬化性組成物及びそれを用いたフィルム - Google Patents
活性エネルギー線硬化性組成物及びそれを用いたフィルム Download PDFInfo
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- WO2018003294A1 WO2018003294A1 PCT/JP2017/017496 JP2017017496W WO2018003294A1 WO 2018003294 A1 WO2018003294 A1 WO 2018003294A1 JP 2017017496 W JP2017017496 W JP 2017017496W WO 2018003294 A1 WO2018003294 A1 WO 2018003294A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F220/34—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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
-
- 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
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- 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
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- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- 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
Definitions
- the present invention relates to an active energy ray-curable composition capable of forming a hard coat layer having excellent antistatic properties on a film surface by coating and curing the film surface, and a film using the same.
- Various resin films include scratch prevention films on the surface of flat panel displays (FPD) such as liquid crystal displays (LCD), organic EL displays (OLED), plasma displays (PDP), decorative films (sheets) for interior and exterior of automobiles, It is used for various applications such as low reflection film for windows and heat ray cut film.
- FPD flat panel displays
- LCD liquid crystal displays
- OLED organic EL displays
- PDP plasma displays
- decorative films sheets for interior and exterior of automobiles
- a hard coat layer comprising a UV curable composition or the like may be applied to the film surface and cured to provide a hard coat layer on the film surface in order to compensate for this.
- a hard coat layer comprising a UV curable composition or the like may be applied to the film surface and cured to provide a hard coat layer on the film surface in order to compensate for this.
- the outline of the process of providing a hard coat layer is sent out from a film roll wound in a roll shape to a coating machine, a hard coat agent is applied, cured by ultraviolet irradiation to form a hard coat layer, and again It is wound up into a roll.
- a method of adding an antistatic agent to the hard coat agent is generally performed.
- a method of blending a compound having a polyoxyethylene chain and a quaternary ammonium salt into a hard coat agent as an antistatic agent has been proposed (for example, see Patent Document 1).
- the hard coat agent containing these antistatic agents does not have sufficient antistatic performance. Therefore, there has been a demand for an active energy ray-curable composition that can form a hard coat layer having better antistatic properties.
- the problem to be solved by the present invention is to provide an active energy ray-curable composition capable of forming a hard coat layer having excellent antistatic properties and a film using the same.
- the present inventors have obtained excellent antistatic properties by blending a resin having an alicyclic structure and a quaternary ammonium salt into an active energy ray-curable composition.
- the present inventors have found that a hard coat layer having can be formed and completed the present invention.
- the present invention comprises an active energy ray-curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, and an organic solvent (C).
- a curable composition and a film using the same are provided.
- the active energy ray-curable composition of the present invention can form a hard coat layer having excellent antistatic properties by coating and curing on the film surface. 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, functions such as sticking prevention and adhesion of dust due to static electricity can be imparted to various films. Therefore, the film having a cured coating film of the active energy ray-curable composition of the present invention is environmentally friendly, and troubles such as sticking and adhesion of dust, etc. when winding up into a roll or unwinding from the roll. Therefore, a film excellent in subsequent handling can be provided.
- the film which has a hard-coat layer which consists of a cured coating film of the active energy ray curable composition of this invention is flat panel displays, such as a liquid crystal display (LCD), an organic electroluminescent display (OLED), and a plasma display (PDP) ( It can be suitably used as an optical film used for FPD). Furthermore, since it has excellent antistatic properties when used in these applications, adhesion of dust and the like can be suppressed. Furthermore, when this film is used for a liquid crystal display or the like, malfunction of the display due to generated static electricity can be prevented.
- LCD liquid crystal display
- OLED organic electroluminescent display
- PDP plasma display
- the active energy ray-curable composition of the present invention contains an active energy ray-curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, and an organic solvent (C). is there.
- Examples of the active energy ray-curable compound (A) include polyfunctional (meth) acrylate (A1) and urethane (meth) acrylate (A2). These can be used alone or in combination of two or more.
- (meth) acrylate refers to one or both of acrylate and methacrylate
- (meth) acryloyl refers to one or both of acryloyl and methacryloyl.
- the polyfunctional (meth) acrylate (A1) is a compound having two or more (meth) acryloyl groups in one molecule.
- Specific examples of the polyfunctional (meth) acrylate (a1) include 1,4-butanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, and 1,6-hexanediol.
- polyfunctional (meth) acrylates (A1) can be used alone or in combination of two or more.
- these polyfunctional (meth) acrylates (A1) since the scratch resistance of the cured coating film of the active energy ray-curable composition of the present invention is improved, dipentaerythritol hexa (meth) acrylate, di Pentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and pentaerythritol tri (meth) acrylate are preferred.
- the urethane (meth) acrylate (A2) is obtained by reacting polyisocyanate (a2-1) with (meth) acrylate (a2-2) having a hydroxyl group.
- polyisocyanate (a2-1) examples include aliphatic polyisocyanates and aromatic polyisocyanates. Since the coloring of the cured coating film of the active energy ray-curable composition of the present invention can be reduced, Isocyanates are preferred.
- the aliphatic polyisocyanate is a compound in which a portion excluding an 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; norbornane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanato).
- cycloaliphatic polyisocyanates such as methyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane and 2-methyl-1,5-diisocyanatocyclohexane.
- a trimerized product obtained by trimming the aliphatic polyisocyanate or the alicyclic polyisocyanate can also be used as the aliphatic polyisocyanate.
- these aliphatic polyisocyanates can be used alone or in combination of two or more.
- aliphatic polyisocyanates in order to improve the scratch resistance of the coating film, among the aliphatic polyisocyanates, hexamethylene diisocyanate, which is a linear aliphatic hydrocarbon diisocyanate, norbornane diisocyanate, which is an alicyclic diisocyanate, isophorone Diisocyanate is preferred.
- the (meth) acrylate (a2-2) is a compound having a hydroxyl group and a (meth) acryloyl group.
- Specific examples of the (meth) acrylate (a2-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth).
- Divalent compounds such as acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, and hydroxypivalate neopentyl glycol mono (meth) acrylate Mono (meth) acrylate of alcohol; trimethylolpropane di (meth) acrylate, ethylene oxide (EO) modified trimethylolpropane (meth) acrylate, propylene oxide (PO) modified trimethylolpropane di (meta) Mono- or di (meth) acrylate of trivalent alcohol such as acrylate, glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or a part of these alcoholic hydroxyl groups Mono- and di (meth) acrylates having hydroxyl groups modified with
- the urethane (meth) acrylate (A2) since it can improve the scratch resistance of the cured coating film of the active energy ray-curable composition of the present invention, it has four or more (meth) acryloyl groups in one molecule. Those are preferred. Since the urethane (meth) acrylate (A2) has four or more (meth) acryloyl groups in one molecule, the (meth) acrylate (a2-2) has 2 (meth) acryloyl groups. Those having at least two are preferred.
- Examples of such (meth) acrylate (a2-2) include trimethylolpropane di (meth) acrylate, ethylene oxide modified trimethylolpropane di (meth) acrylate, propylene oxide modified trimethylolpropane di (meth) acrylate, Glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Can be mentioned.
- (meth) acrylates (a2-2) can be used alone or in combination of two or more with respect to one of the aliphatic polyisocyanates.
- pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable because they can improve scratch resistance.
- the reaction of the polyisocyanate (a2-1) and the (meth) acrylate (a2-2) can be carried out by a conventional urethanization reaction. Moreover, in order to accelerate
- urethanization catalyst examples include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin Examples thereof include organic tin compounds such as diacetate and tin octylate, and organic zinc compounds such as zinc octylate.
- active energy ray-curable compound (A) other than said polyfunctional (meth) acrylate (A1) and urethane (meth) acrylate (A2) epoxy (meth) acrylate, polyester (meth) An acrylate, a polyether (meth) acrylate, etc. can be used.
- the epoxy (meth) acrylate include those obtained by reacting (meth) acrylic acid with bisphenol-type epoxy resin, novolac-type epoxy resin, polyglycidyl methacrylate and the like and esterifying it.
- polyester (meth) acrylate (meth) acrylic acid is made to react and esterify with the polyester which the both terminal obtained by polycondensation of polyhydric carboxylic acid and polyhydric alcohol is a hydroxyl group, for example. Or a product obtained by reacting (meth) acrylic acid with ester obtained by adding an alkylene oxide to a polyvalent carboxylic acid.
- polyether (meth) acrylate what was obtained by reacting (meth) acrylic acid with polyether polyol and esterifying is mentioned, for example.
- the resin (B) has an alicyclic structure and a quaternary ammonium salt.
- Examples of the method for producing the resin (B) include the polymerizable monomer (b1) having an alicyclic structure and the polymerizable monomer (b2) having a quaternary ammonium salt as essential components. Examples thereof include a method of copolymerizing the monomer (b1) and the polymerizable monomer (b2) with a copolymerizable polymerizable monomer (b3).
- the polymerizable monomer (b1) is a polymerizable monomer having an alicyclic structure.
- 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, and a cyclodecane ring; a bicycloundecane ring, a decahydro ring Naphthalene (decalin) ring, tricyclo [5.2.1.0 2,6 ] decane ring, bicyclo [4.3.0] nonane ring, tricyclo [5.3.1.1] dodecane ring, tricyclo [5.
- polymerizable monomer (b1) examples include cyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Examples include dicyclopentenyloxyethyl (meth) acrylate and dicyclopentanyl (meth) acrylate.
- polymerizable monomers (b1) can be used alone or in combination of two or more.
- Examples of the polymerizable monomer (b2) include those in which the counter anion such as 2-[(meth) acryloyloxy] ethyltrimethylammonium chloride and 3-[(meth) acryloyloxy] propyltrimethylammonium chloride is chloride; Counter anions such as 2-[(meth) acryloyloxy] ethyltrimethylammonium bromide, 3-[(meth) acryloyloxy] propyltrimethylammonium bromide and the like, wherein 2-[(meth) acryloyloxy] ethyltrimethylammonium methylphenyl Sulfonate, 2-[(meth) acryloyloxy] ethyltrimethylammonium methylsulfonate, 3-[(meth) acryloyloxy] propyltrimethylammonium methyl Phenylsulfonate, 3-[(meth) acryloyloxy] propyltrimethylam
- Examples of the polymerizable monomer (b3) include 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, Alkyl (meth) acrylates such as dodecyl (meth) acrylate; methoxypolyethylene glycol mono (meth) acrylate, octoxypolyethyleneglycol / polypropyleneglycol mono (meth) acrylate, lauroxypoly
- the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved, mono (meth) acrylate of polyalkylene glycol is preferable, and methoxypolyethylene Glycol mono (meth) acrylate is more preferred.
- the (meth) acrylate which has a fluorinated alkyl group is also preferable from the effect that the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved.
- the number average molecular weight of the polyalkylene glycol is preferably in the range of 200 to 8,000, more preferably in the range of 300 to 6,000, still more preferably in the range of 400 to 4,000, and 400 to 2 Those in the range of 1,000 are particularly preferred.
- the ratio of the polymerizable monomer (b1) in the total amount of the raw material of the resin (B) can further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention.
- the range of mass% is preferable, the range of 10 to 50 mass% is more preferable, and the range of 12 to 45 mass% is more preferable.
- the ratio of the polymerizable monomer (b2) in the total amount of the raw material of the resin (B) can further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention.
- the range of ⁇ 90% by mass is preferred, the range of 40 ⁇ 80% by mass is more preferred, and the range of 45 ⁇ 70% by mass is more preferred.
- the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved.
- the ratio of the poly (alkylene glycol) mono (meth) acrylate in the total amount of the raw material of the resin (B) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and 20 to 40% by mass. The range of is more preferable.
- the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved.
- the ratio of the (meth) acrylate having a fluorinated alkyl group in the total amount of the raw material 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. The range of 1 to 5% by mass is more preferable.
- the weight average molecular weight of the resin (B) is preferably in the range of 1,000 to 100,000 because the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved.
- the range of ⁇ 50,000 is more preferred, and the range of 3,000 ⁇ 30,000 is more preferred.
- the weight average molecular weight in this invention is the value in polystyrene conversion measured by the gel permeation chromatography (GPC) method.
- the compounding amount of the resin (B) can further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention, it is based on 100 parts by mass of the active energy ray-curable composition (A).
- the range of 0.1 to 30 parts by mass is preferable, the range of 0.5 to 20 parts by mass is more preferable, the range of 1 to 10 parts by mass is more preferable, and the range of 1.5 to 7 parts by mass is particularly preferable .
- the organic solvent (C) can be used without particular limitation as long as it can dissolve other components in the active energy ray-curable composition of the present invention. Further, since the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved, the dispersion term ( ⁇ D) in the Hansen solubility parameter is in the range of 15.5 to 16.1 MPa 0.5 . It is preferable that the polarization term ( ⁇ P) is in the range of 6.3 to 10.4 MPa 0.5 and the hydrogen bond term ( ⁇ H) is in the range of 5.1 to 11.6 MPa 0.5 .
- Hansen solubility parameters For the definition and calculation of Hansen solubility parameters, please refer to Charles M. Hansen, “Hansen Solubility Parameters: A Users Handbook (CRC Press, 2007)”. Further, by using the computer software “Hansen Solubility Parameters in Practice (HSPiP)”, the Hansen solubility parameter can be estimated from the chemical structure of an organic solvent whose parameter value is not described in the literature. In the present invention, the value is used for an organic solvent whose parameter value is described in the literature, and the parameter value estimated using HSPiP version 4.1.06 is used for the organic solvent whose parameter value is not described in the literature. Use.
- the organic solvent (C) can be used as a single organic solvent or as a mixed solvent in combination of two or more organic solvents.
- the value which carried out the weighted average of three parameters of the Hansen solubility parameter of each organic solvent can be used in the said range.
- the blending amount of the organic solvent (C) in the active energy ray-curable composition of the present invention is preferably an amount that provides a viscosity suitable for a coating method described later.
- the active energy ray-curable composition of the present invention can be formed into a cured coating film by irradiating active energy rays after coating on a substrate.
- the active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
- a photopolymerization initiator (D) to the active energy ray curable composition of the present invention to improve curability.
- a photosensitizer (E) can be further added to improve curability.
- Examples of the photopolymerization initiator (D) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo ⁇ 2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propanone ⁇ , benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy -2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Acetophenone compounds such as butanone; benzoin, benzoin methyl ether, benzo Benzoin compounds such as isopropyl ether; acylphosphine oxide compounds such as 2,4,6-
- Examples of the photosensitizer (E) include tertiary amine compounds such as diethanolamine, N-methyldiethanolamine and tributylamine, urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiuro And sulfur compounds such as nitro-p-toluenesulfonate.
- tertiary amine compounds such as diethanolamine, N-methyldiethanolamine and tributylamine
- urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiuro
- sulfur compounds such as nitro-p-toluenesulfonate.
- the usage-amount of said photoinitiator (D) and a photosensitizer (E) is with respect to 100 mass parts of said active energy ray curable compositions (A) in the active energy ray curable composition of this invention.
- a polymerization inhibitor as a compound other than the above components (A) to (E), a polymerization inhibitor, a surface conditioner, and an antistatic agent can be used depending on applications and required properties. Addition of antifoaming agent, viscosity modifier, light stabilizer, weathering stabilizer, heat stabilizer, UV absorber, antioxidant, leveling agent, organic pigment, inorganic pigment, pigment dispersant, silica beads, organic beads, etc. Agents: Inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, and antimony pentoxide can be blended. These other blends can be used alone or in combination of two or more.
- 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 active energy ray to form a cured coating film. is there.
- the material of the film base used in the film of the present invention is preferably a highly transparent resin, for example, a polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; polypropylene, polyethylene, polymethylpentene-1 Polyolefin resins such as cellulose acetate (diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate, cellulose acetate phthalate, cellulose nitrate and other cellulose resins; poly Acrylic resins such as methyl methacrylate; polyvinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; polyvinyl alcohol; ethylene-acetic acid Nyl copolymer; polystyrene; polyamide; polycarbonate; polysulfone; polyethersulfone; polyetheretherketone; polyimide resin
- the film substrate may be in the form of a film or a sheet, and the thickness is preferably in the range of 20 to 500 ⁇ m.
- the thickness is preferably in the range of 20 to 200 ⁇ m, more preferably in the range of 30 to 150 ⁇ m, and still more preferably in the range of 40 to 130 ⁇ m.
- 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, comma coating, air knife coating, kiss coating, spray coating, and dip coating. , Spinner coating, brush coating, solid coating by silk screen, wire bar coating, flow coating and the like.
- the active energy ray-curable composition of the present invention contains an organic solvent
- the organic solvent In order to volatilize and to segregate the resin (B) on the coating film surface, it is preferable to heat or dry at room temperature.
- the conditions for heat drying are not particularly limited as long as the organic solvent volatilizes. Usually, the heat drying is performed at a temperature in the range of 50 to 100 ° C. and for a time in the range of 0.5 to 10 minutes. preferable.
- the active energy rays for curing the active energy ray-curable composition of the present invention are ionizing radiations such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
- ultraviolet rays examples of devices that emit ultraviolet rays include low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, electrodeless lamps (fusion lamps), chemical lamps, Examples thereof include a black light lamp, a mercury-xenon lamp, a short arc lamp, a helium / cadmium laser, an argon laser, sunlight, and an LED lamp.
- the film thickness of the cured coating film when forming the cured coating film of the active energy ray-curable composition of the present invention on the film substrate is sufficient for the hardness of the cured coating film and curing of the coating film. Since the curling of the film due to shrinkage can be suppressed, the range of 1 to 30 ⁇ m is preferable, the range of 3 to 15 ⁇ m is more preferable, and the range of 4 to 10 ⁇ m is more preferable.
- methanol was added for dilution to obtain a 45% by mass solution of a resin (B-2) having an alicyclic structure and a quaternary ammonium salt.
- the weight average molecular weight of the obtained resin (B-2) was 10,000.
- the obtained resin (B′-1) had a weight average molecular weight of 10,000.
- the obtained resin (B′-2) had a weight average molecular weight of 10,000.
- the weight average molecular weights of the resins (B-1), (B-2), (B′-1) and (B′-2) obtained above were determined by gel permeation chromatography (GPC) method. The measurement was performed under the following conditions.
- Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series. "TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000” (7.8 mm ID x 30 cm) x 1 "TSKgel G3000” (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 detector: RI (differential refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection amount: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was prepared using the following standard polystyrene.
- Example 1 Polyfunctional acrylate mixture (mixture of dipentaerythritol hexaacrylate 64% by mass, dipentaerythritol pentaacrylate 17% by mass, dipentaerythritol tetraacrylate 19% by mass; hereinafter, abbreviated as “polyfunctional acrylate (A1)”) 100 11 parts by mass (5 parts by mass as the resin (B-2)), a photopolymerization initiator (BASF Japan Ltd.
- “Irgacure 184” ; 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone), 60 parts by mass of methyl ethyl ketone (hereinafter abbreviated as” MEK ”) and 40 parts by mass of PGME are uniformly mixed to cure active energy rays having a nonvolatile content of 50% by mass. Sex composition (1) was obtained.
- Example 2 to 4 Active energy ray-curable compositions (2) to (7) were obtained in the same manner as in Example 1 except that the compositions shown in Tables 1 and 2 were changed.
- the active energy ray-curable composition was applied to a 60 ⁇ m-thick triacetylcellulose (TAC) film (manufactured by Fuji Film Co., Ltd.) with a bar coater so as to have a film thickness of 5 ⁇ m, and then at 60 ° C. for 1.5 minutes. After drying, irradiation was performed at an irradiation light amount of 3 kJ / m 2 using an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., high-pressure mercury lamp) in an air atmosphere, and a TAC film having a cured coating film was obtained as an evaluation sample. .
- TAC triacetylcellulose
- the cured coating films of the active energy ray-curable compositions of the present invention of Examples 1 to 4 have a surface resistance value of the order of 10 9 and high antistatic properties. It could be confirmed.
- Comparative Examples 1 to 5 are examples using a resin having no alicyclic structure and having a quaternary ammonium salt. These surface resistance values exceeded 10 13, and it was confirmed that the antistatic property was inferior.
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Abstract
Description
攪拌機、ガス導入管、冷却管、及び温度計を備えたフラスコに、酢酸ブチル55.5質量部、IPDI222質量部、p-メトキシフェノール0.5質量部、ジブチル錫ジアセテート0.5質量部を仕込み、70℃に昇温した後、ビス(2-アクリロイルオキシエチル)ヒドロキシエチルイソシアヌレート(以下、「BAHIC」という。)/トリス(2-アクリロイルオキシエチル)イソシアヌレート(以下、「TAIC」という。)混合物(質量比56/44の混合物)の不揮発分80質量%の酢酸ブチル溶液823.6質量部を1時間かけて滴下し、滴下終了後70℃で3時間反応させた。その後、PE3A/PE4A混合物(質量比75/25の混合物)の不揮発分80質量%の酢酸ブチル溶液496.6質量部を1時間かけて滴下し、滴下終了後70℃で3時間反応させ、さらにイソシアネート基を示す2250cm-1の赤外線吸収スペクトルが消失するまで反応を行い、ウレタンアクリレート(A2-1)/TAIC/PE4Aの混合物(質量比69/23/8の混合物、不揮発分80質量%の酢酸ブチル溶液)を得た。なお、ウレタンアクリレート(A2-1)の分子量は889であった。
攪拌機、ガス導入管、冷却管、及び温度計を備えたフラスコに、酢酸ブチル55.5質量部、イソホロンジイソシアネート(以下、「IPDI」という。)222質量部、p-メトキシフェノール0.5質量部、ジブチル錫ジアセテート0.5質量部を仕込み、70℃に昇温した後、ペンタエリスリトールトリアクリレート(以下、「PE3A」という。)/ペンタエリスリトールテトラアクリレート(以下、「PE4A」という。)混合物(質量比75/25の混合物)の80質量%酢酸ブチル溶液993.4質量部を1時間かけて滴下した。滴下終了後、70℃で3時間反応させ、さらにイソシアネート基を示す2250cm-1の赤外線吸収スペクトルが消失するまで反応を行い、ウレタンアクリレート(A2-2)/PE4A混合物(質量比80/20の混合物、不揮発分80質量%の酢酸ブチル溶液)を得た。なお、ウレタンアクリレート(A2-2)の分子量は818であった。
攪拌装置、還流冷却管及び窒素導入管を備えたフラスコ中に、窒素ガスを導入して、フラスコ内の空気を窒素ガスで置換した。その後、フラスコに2-(メタクリロイルオキシ)エチルトリメチルアンモニウムクロライド53.7質量部、シクロヘキシルメタクリレート29.3質量部、メトキシポリエチレングリコールメタクリレート(日油株式会社製「ブレンマー PME-1000」;繰り返し単位数n≒23、分子量1,000)14.6質量部、2-パーフルオロヘキシルエチルアクリレート1.9質量部、メタクリル酸0.5質量部、メタノール50質量部及びプロピレングリコールモノメチルエーテル10質量部を加えた。次いで、重合開始剤(アゾビスイソブチロニトリル)0.1質量部をプロピレングリコールモノメチルエーテル2.4質量部で溶解した溶液を30分かけて滴下した後、65℃で3時間反応させた。次いで、メタノールを加えて希釈し、脂環構造及び4級アンモニウム塩を有する樹脂(B-1)の45質量%溶液を得た。得られた樹脂(B-1)の重量平均分子量は1万であった。
攪拌装置、還流冷却管及び窒素導入管を備えたフラスコ中に、窒素ガスを導入して、フラスコ内の空気を窒素ガスで置換した。その後、フラスコに2-(メタクリロイルオキシ)エチルトリメチルアンモニウムクロライド54.7質量部、シクロヘキシルメタクリレート19.9質量部、メトキシポリエチレングリコールメタクリレート(日油株式会社製「ブレンマー PME-1000」;繰り返し単位数n≒23、分子量1,000)24.9質量部、メタクリル酸0.5質量部、メタノール50質量部及びPGME10質量部を加えた。次いで、重合開始剤(アゾビスイソブチロニトリル)0.1質量部をPGME2.4質量部で溶解した溶液を30分かけて滴下した後、65℃で3時間反応させた。次いで、メタノールを加えて希釈し、脂環構造及び4級アンモニウム塩を有する樹脂(B-2)の45質量%溶液を得た。得られた樹脂(B-2)の重量平均分子量は1万であった。
攪拌装置、還流冷却管及び窒素導入管を備えたフラスコ中に、窒素ガスを導入して、フラスコ内の空気を窒素ガスで置換した。その後、フラスコに2-(メタクリロイルオキシ)エチルトリメチルアンモニウムクロライド54.0質量部、メトキシポリエチレングリコールメタクリレート(日油株式会社製「ブレンマー PME-1000」;繰り返し単位数n≒23、分子量1,000)44.1質量部、2-パーフルオロヘキシルエチルアクリレート1.9質量部、メタノール50質量部及びPGME10質量部を加えた。次いで、重合開始剤(アゾビスイソブチロニトリル)0.1質量部をPGME2.4質量部で溶解した溶液を30分かけて滴下した後、65℃で3時間反応させた。次いで、メタノールを加えて希釈し、脂環構造及び4級アンモニウム塩を有する樹脂(B’-1)の45質量%溶液を得た。得られた樹脂(B’-1)の重量平均分子量は1万であった。
攪拌装置、還流冷却管及び窒素導入管を備えたフラスコ中に、窒素ガスを導入して、フラスコ内の空気を窒素ガスで置換した。その後、フラスコに2-(メタクリロイルオキシ)エチルトリメチルアンモニウムクロライド54.7質量部、メトキシポリエチレングリコールメタクリレート(日油株式会社製「ブレンマー PME-1000」;繰り返し単位数n≒23、分子量1,000)44.8質量部、メタクリル酸0.5質量部、メタノール50質量部及びPGME10質量部を加えた。次いで、重合開始剤(アゾビスイソブチロニトリル)0.1質量部をPGME2.4質量部で溶解した溶液を30分かけて滴下した後、65℃で3時間反応させた。次いで、メタノールを加えて希釈し、脂環構造及び4級アンモニウム塩を有する樹脂(B’-2)の45質量%溶液を得た。得られた樹脂(B’-2)の重量平均分子量は1万であった。
カラム:東ソー株式会社製の下記のカラムを直列に接続して使用した。
「TSKgel G5000」(7.8mmI.D.×30cm)×1本
「TSKgel G4000」(7.8mmI.D.×30cm)×1本
「TSKgel G3000」(7.8mmI.D.×30cm)×1本
「TSKgel G2000」(7.8mmI.D.×30cm)×1本
検出器:RI(示差屈折計)
カラム温度:40℃
溶離液:テトラヒドロフラン(THF)
流速:1.0mL/分
注入量:100μL(試料濃度0.4質量%のテトラヒドロフラン溶液)
標準試料:下記の標準ポリスチレンを用いて検量線を作成した。
東ソー株式会社製「TSKgel 標準ポリスチレン A-500」
東ソー株式会社製「TSKgel 標準ポリスチレン A-1000」
東ソー株式会社製「TSKgel 標準ポリスチレン A-2500」
東ソー株式会社製「TSKgel 標準ポリスチレン A-5000」
東ソー株式会社製「TSKgel 標準ポリスチレン F-1」
東ソー株式会社製「TSKgel 標準ポリスチレン F-2」
東ソー株式会社製「TSKgel 標準ポリスチレン F-4」
東ソー株式会社製「TSKgel 標準ポリスチレン F-10」
東ソー株式会社製「TSKgel 標準ポリスチレン F-20」
東ソー株式会社製「TSKgel 標準ポリスチレン F-40」
東ソー株式会社製「TSKgel 標準ポリスチレン F-80」
東ソー株式会社製「TSKgel 標準ポリスチレン F-128」
東ソー株式会社製「TSKgel 標準ポリスチレン F-288」
東ソー株式会社製「TSKgel 標準ポリスチレン F-550」
多官能アクリレート混合物(ジペンタエリスリトールヘキサアクリレート64質量%、ジペンタエリスリトールペンタアクリレート17質量%、ジペンタエリスリトールテトラアクリレート19質量%の混合物;以下、「多官能アクリレート(A1)」と略記する。)100質量部、製造例4で得られた樹脂(B-2)の45質量%溶液11.11質量部(樹脂(B-2)として5質量部)、光重合開始剤(BASFジャパン株式会社「イルガキュア 184」;1-ヒドロキシシクロヘキシルフェニルケトン)5質量部、メチルエチルケトン(以下、「MEK」と略記する。)60質量部及びPGME40質量部を均一に混合して、不揮発分50質量%の活性エネルギー線硬化性組成物(1)を得た。
表1~2に示した組成に変更した以外は実施例1と同様に行い、活性エネルギー線硬化性組成物(2)~(7)を得た。
表2~3に示した組成に変更した以外は実施例1と同様に行い、活性エネルギー線硬化性組成物(R1)~(R5)を得た。
活性エネルギー線硬化性組成物を、厚さ60μmのトリアセチルセルロース(TAC)フィルム(富士フイルム株式会社製)に、バーコーターで膜厚5μmとなるように塗工し、60℃で1.5分間乾燥した後、空気雰囲気下で紫外線照射装置(アイグラフィックス株式会社製、高圧水銀ランプ)を用いて照射光量3kJ/m2で照射し、硬化塗膜を有するTACフィルムを評価用サンプルとして得た。
上記で得られた評価用サンプルの硬化塗膜の表面について、JIS試験方法K5600-5-4:1999に準拠して、鉛筆硬さを測定した。
上記で得られた評価用フィルムの硬化塗膜の表面について、クロックメーター形摩擦試験機(株式会社東洋精機製作所製「平面摩擦試験機」、測定条件:直径25mm円形摩擦子、スチールウール#0000、荷重500g、10往復)を用いて試験を行い、試験後の硬化塗膜表面の傷の有無を目視で確認し、下記の基準により耐擦傷性を評価した。
◎:傷がない。
○:傷の数が1~2本である。
△:傷の数が3~10本である。
×:傷の数が10本を超える。
上記で得られた評価用サンプルについて、JIS試験方法K7136:2000に準拠して、ヘーズメーター(日本電色工業株式会社製「NDH2000」)を用いてヘーズ値を測定した。
上記で得られた評価用サンプルについて、JIS試験方法K7142:2014のA法に準拠して、アッベ屈折率計(株式会社アタゴ製「DR-M2」)を用いて屈折率を測定した。
上記で得られた評価用サンプルの硬化塗膜の表面について、JIS試験方法K6911-1995に準拠して、高抵抗率計(株式会社三菱化学アナリテック製「ハイレスタ-UP MCP-HT450」)を用いて、印加電圧500V、測定時間10秒で表面抵抗値を測定した。
Claims (6)
- 活性エネルギー線硬化性化合物(A)と、脂環構造及び4級アンモニウム塩を有する樹脂(B)と、有機溶剤(C)とを含有することを特徴とする活性エネルギー線硬化性組成物。
- 前記樹脂(B)が、原料として脂環構造を有する重合性単量体を5~40質量%用いた重合体である請求項1記載の活性エネルギー線硬化性組成物。
- 前記有機溶剤(C)が、ハンセン溶解度パラメータでの分散項(δD)が15.5~16.1MPa0.5の範囲であり、分極項(δP)が6.3~10.4MPa0.5の範囲であり、水素結合項(δH)が5.1~11.6MPa0.5の範囲であるものである請求項1又は2記載の活性エネルギー線硬化性組成物。
- 前記樹脂(B)の配合量が、前記活性エネルギー線硬化性化合物(A)100質量部に対して、0.1~30質量部の範囲である請求項1~3のいずれか1項記載の活性エネルギー線硬化性組成物。
- 請求項1~4のいずれか1記載の活性エネルギー線硬化性組成物の硬化物。
- 請求項1~4のいずれか1記載の活性エネルギー線硬化性組成物の硬化塗膜を有することを特徴とするフィルム。
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| KR1020187036815A KR20190011755A (ko) | 2016-06-27 | 2017-05-09 | 활성 에너지선 경화성 조성물 및 그것을 사용한 필름 |
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| JP2022034529A (ja) * | 2020-08-18 | 2022-03-03 | 三菱ケミカル株式会社 | 硬化性樹脂組成物および積層フィルム |
| JPWO2022186019A1 (ja) * | 2021-03-02 | 2022-09-09 |
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2017
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- 2017-05-09 WO PCT/JP2017/017496 patent/WO2018003294A1/ja not_active Ceased
- 2017-05-09 CN CN201780039288.5A patent/CN109328198B/zh active Active
- 2017-05-09 JP JP2018503689A patent/JP6418474B2/ja active Active
- 2017-05-31 TW TW106117792A patent/TWI740952B/zh active
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| JP2022034529A (ja) * | 2020-08-18 | 2022-03-03 | 三菱ケミカル株式会社 | 硬化性樹脂組成物および積層フィルム |
| JPWO2022186019A1 (ja) * | 2021-03-02 | 2022-09-09 | ||
| WO2022186019A1 (ja) * | 2021-03-02 | 2022-09-09 | Dic株式会社 | 活性エネルギー線硬化性組成物、硬化物及びフィルム |
| JP7533763B2 (ja) | 2021-03-02 | 2024-08-14 | Dic株式会社 | 活性エネルギー線硬化性組成物、硬化物及びフィルム |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109328198A (zh) | 2019-02-12 |
| TW201819423A (zh) | 2018-06-01 |
| KR20190011755A (ko) | 2019-02-07 |
| CN109328198B (zh) | 2021-09-14 |
| JPWO2018003294A1 (ja) | 2018-07-12 |
| TWI740952B (zh) | 2021-10-01 |
| JP6418474B2 (ja) | 2018-11-07 |
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