WO2019124049A1 - 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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- WO2019124049A1 WO2019124049A1 PCT/JP2018/044511 JP2018044511W WO2019124049A1 WO 2019124049 A1 WO2019124049 A1 WO 2019124049A1 JP 2018044511 W JP2018044511 W JP 2018044511W WO 2019124049 A1 WO2019124049 A1 WO 2019124049A1
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- acrylate
- curable composition
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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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/34—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
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (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
- C08F220/10—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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
-
- 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
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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
- C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
Definitions
- the present invention relates to an active energy ray-curable composition capable of forming a hard coat layer and a film using the same.
- Resin film is a film for preventing scratches on the surface of flat panel display (FPD) such as liquid crystal display (LCD), organic EL display (OLED), plasma display (PDP), etc., decorative film (sheet) for interior and exterior of automobile, window It is used for various uses such as low reflection films for heat treatment and heat ray cut films.
- FPD flat panel display
- LCD liquid crystal display
- OLED organic EL display
- PDP plasma display
- sheet decorative film for interior and exterior of automobile, window
- a hard coat agent composed of an active energy ray curable composition or the like is coated on the film surface and cured to provide a hard coat layer on the film surface for the purpose of compensating for this. That is commonly done.
- triacetyl cellulose (TAC) films and cycloolefin polymer (COP) films have been the mainstream as resin films used in the production of FPD, but due to the trend of cost reduction, they are relatively inexpensive. And the usage rate of the film with a hard-coat layer which used the polymethylmethacrylate base material which has low moisture permeability and high dimensional stability as a support base is increasing.
- the polymethyl methacrylate base has relatively high solvent resistance (erosion resistance), and there is a problem that interference fringes are easily generated at the interface between the hard coat layer and the base.
- the problem to be solved by the present invention is an active energy ray curable composition capable of forming a hard coat layer which is excellent in coating film appearance and antistatic property and which hardly causes interference fringes at the interface with a substrate, and the same To provide a film that was
- 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-1) represented by the following general formula (1).
- An active energy ray curable composition comprising the organic solvent (C) in the range of 1% by mass to less than 15% by mass and a film using the same.
- R 1 represents a linear or branched alkyl group having 1 to 10 carbon atoms, an allyl group, a phenyl group or a benzyl group, and n is an integer of 1 to 3) Show)
- the active energy ray-curable composition of the present invention is excellent in coating stability, coating film appearance and antistatic property, and can form a hard coat layer which hardly generates interference fringes at the interface with the substrate.
- a film having a hard coat layer composed of a cured coating film of the active energy ray curable composition of the present invention is a flat panel display such as a liquid crystal display (LCD), an organic EL display (OLED), a plasma display (PDP) It can be suitably used as an optical film used for FPD.
- LCD liquid crystal display
- OLED organic EL display
- PDP plasma display
- the active energy ray curable composition of the present invention comprises an active energy ray curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, and a specific organic solvent (c-1). It contains the organic solvent (C) which contains the quantity.
- Examples of the active energy ray curable compound (A) include high refractive index polymerizable monomers (A-1) having a refractive index of 1.55 or more and polymerizable monomers other than the above (A-1). (A-2) or the like can be used. These monomers may be used alone or in combination of two or more. Among these, when a high refractive index is required, it is preferable to contain the above (A-1), and in other cases, it is not necessary to contain the above (A-1).
- the polymerizable monomer (A-1) may be any one having a high refractive index before curing of 1.55 or more, and, for example, an aromatic polymer having 2 to 6 aromatic rings A monomer, a fluorene type polymerizable monomer, etc. are mentioned preferably.
- polymerizable monomer (A) examples include compounds represented by the following general formula (1); phenylbenzyls such as o-phenylbenzyl (meth) acrylate and p-phenylbenzyl (meth) acrylate (Meth) acrylate compound having a group; (meth) acrylate compound having a phenylphenol group such as phenylphenol EO acrylate; propoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, oxyethylene group And bisphenol compounds having in the range of 2 to 4 (meth) acryloyl groups such as bisphenol A di (meth) acrylate having an oxyethylene group and bisphenol A tri (meth) acrylate having an oxyethylene group.
- These polymerizable monomers (A) may be used alone or in combination of two or more.
- a compound represented by the following general formula (3) a (meth) acrylate compound having a phenylbenzyl group
- a (meth) acrylate compound having a benzyl group it is preferable that the mass ratio is the range of 30/70-70/30. .
- R 1 and R 2 each represent a hydrogen atom or a methyl group, and m and n each represent an integer of 0 to 5.
- (meth) acrylate refers to one or both of acrylate and methacrylate
- (meth) acryloyl refers to one or both of acryloyl and methacryloyl.
- the content in the case of using the polymerizable monomer (A-1) is preferably in the range of 3 to 30% by mass, and more preferably 5 to 20% by mass, in the active energy ray curable compound (A). Is more preferred.
- polymerizable monomers (A-2) other than the above (A-1) for example, polyfunctional (meth) acrylates, urethane (meth) acrylates and the like can be used. These may be used alone or in combination of two or more.
- the polyfunctional (meth) acrylate is a compound having three or more (meth) acryloyl groups in one molecule, and, for example, 1,4-butanediol di (meth) acrylate, 3-methyl-1,5- Pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2 -Ethyl-1,3-propanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Dipropylene glycol di (meth) aclay , Di (meth) acrylate
- polyfunctional (meth) acrylates may be used alone or in combination of two or more. Further, among these polyfunctional (meth) acrylates, it is preferable to use a polyfunctional (meth) acrylate having three or more (meth) acryloyl groups, from the viewpoint of obtaining even more excellent scratch resistance.
- the urethane (meth) acrylate is obtained, for example, by reacting polyisocyanate (a2-1) with (meth) acrylate (a2-2) having a hydroxyl group, and one (meth) acryloyl group is used. Or it has two.
- polyisocyanate (a2-1) examples include aliphatic polyisocyanates and aromatic polyisocyanates, and since aliphatic pigments can be used to reduce the coloration of the cured coating film of the active energy ray-curable composition of the present invention, aliphatic poly It is preferred to use an isocyanate.
- the said aliphatic polyisocyanate is a compound in which the site
- this aliphatic polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate and lysine triisocyanate; norbornane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), and 1,3-bis (isocyanate) And cycloaliphatic polyisocyanates such as methyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane and the like.
- trimerized trimerized aliphatic polyisocyanate or alicyclic polyisocyanate can also be used as the aliphatic polyisocyanate.
- aliphatic polyisocyanates may be used alone or in combination of two or more.
- 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) Bivalents such as acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate hydroxypivalate Mono (meth) acrylate of alcohol; trimethylolpropane di (meth) acrylate, ethylene oxide (EO) modified trimethylolpropane (meth) acrylate, propylene oxide (PO) modified trimethylolprop
- (meth) acrylates (a2-2) may be used alone or in combination of two or more.
- pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tripentaerythritol hepta (meth) acrylate are selected from the viewpoint that even more excellent scratch resistance can be obtained.
- one or more compounds are used.
- the reaction of the polyisocyanate (a2-1) with the (meth) acrylate (a2-2) can be carried out by a conventional urethanation 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 include organotin compounds such as diacetate and tin octylate, and organozinc compounds such as zinc octylate.
- the mixing ratio is in the range of 40/60 to 90/10 in order to obtain even better abrasion resistance. Is preferable, and the range of 50/50 to 80/20 is more preferable.
- the polyfunctional monomer In addition to acrylate and / or urethane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenyl glycol (meth) acrylate, and a compound represented by the following general formula (2) It is preferable to contain one or more types of compounds selected from the group consisting of
- R 2 and R 4 each independently represent a hydrogen atom or a methyl group
- R 3 represents an alkylene group having 1 to 10 carbon atoms
- m represents an integer of 1 to 4) .
- R 3 represents an alkylene group having 2 to 6 carbon atoms from the viewpoint that interference fringes can be further hardly generated at the interface with the base material, and m is It is preferable to use one showing an integer of 1 to 4.
- the total amount used in the case of using the tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenyl glycol (meth) acrylate and the compound represented by the general formula (2) is interference at the interface with the substrate
- the range of 0.1 to 20% by mass in the active energy ray-curable compound (A) is preferable, and the range of 1 to 10% by mass is more preferable, in order to make it difficult to generate streaks.
- the above-mentioned polyfunctional (meth) acrylate, urethane (meth) acrylate, tetrahydrifurofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenyl glycol (meth) acrylate, and Epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate etc. can be used as active energy ray curable compound (A) other than the compound shown by 2).
- the resin (B) must have an alicyclic structure and a quaternary ammonium salt in order to obtain excellent antistatic properties.
- the resin (B) for example, a polymerizable monomer (b1) having an alicyclic structure and a polymerizable monomer (b2) having a quaternary ammonium salt as essential components
- a polymerizable monomer (b1) having an alicyclic structure and a polymerizable monomer (b2) having a quaternary ammonium salt as essential components
- the method of copolymerizing the monomer (b1) and the said polymerizable monomer (b2), and the copolymerizable polymerizable monomer (b3) is mentioned. These copolymerization reactions can be carried out with an organic solvent (C) described later.
- the polymerizable monomer (b1) is a polymerizable monomer having an alicyclic structure.
- the alicyclic structure include monocyclic alicyclic structures such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring and the like; bicycloundecane ring, decahydro 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, Dicyclopentenyl oxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, etc. are mentioned. These polymerizable monomers (b1) may be used alone or in combination of two or more.
- Examples of the polymerizable monomer (b2) include ones in which the counter anion such as 2-[(meth) acryloyloxy] ethyltrimethylammonium chloride, 3-[(meth) acryloyloxy] propyltrimethylammonium chloride is chloride; Counter anions such as 2-[(meth) acryloyloxy] ethyltrimethylammonium bromide, 3-[(meth) acryloyloxy] propyltrimethylammonium bromide which are bromide; 2-[(meth) acryloyloxy] ethyltrimethylammonium methylphenyl Sulfonate, 2-[(meth) acryloyloxy] ethyltrimethylammonium methyl sulfonate, 3-[(meth) acryloyloxy] propyltrimethylammonium methyl Phenylsulfonate, 3-[(Meth) acryloyloxy] propyltrimethyl
- Examples of the polymerizable monomer (b3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and 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, octoxy polyethylene glycol / polypropylene glycol mono (meth) acrylate, lauroxy polyethylene glycol
- polyalkylene glycol mono (meth) acrylates are preferable because they can further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention, and methoxy polyethylene More preferred are glycol mono (meth) acrylates.
- (meth) acrylates having a fluorinated alkyl group are also preferable because they have the effect of further improving the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention.
- the antistatic properties of the cured coating film of the active energy ray-curable composition of the present invention can be further improved, so that the raw materials of the mono (meth) acrylates of the polyalkylene glycols and
- the number average molecular weight of the polyalkylene glycol is preferably 200 to 8,000, more preferably 300 to 6,000, still more preferably 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) to the total amount of the raw material of the resin (B) can improve the antistatic property of the cured coating film of the active energy ray curable composition of the present invention, so 5 to 55
- 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) to the total amount of the raw material of the resin (B) can 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 preferable, the range of 40-80% by mass is more preferable, and the range of 45-70% by mass is more preferable.
- the ratio of mono (meth) acrylate of polyalkylene glycol to the total amount of the raw material of the resin (B) is preferably in the range of 5 to 60% by mass, more preferably in the range of 10 to 50% by mass, and 20 to 40% by mass Is more preferable.
- the antistatic property of the cured coating film of the active energy ray curable composition of this invention can be improved more.
- 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, and 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, since the antistatic property of the cured coating film of the active energy ray curable composition of the present invention can be further improved, and 2,000 The range of ⁇ 50,000 is more preferable, and the range of 3,000 to 30,000 is more preferable.
- the weight average molecular weight in the present invention is a value in terms of polystyrene measured by gel permeation chromatography (GPC).
- the compounding quantity of the said resin (B) can improve the antistatic property of the cured coating film of the active energy ray curable composition of this invention more, It is 100 mass parts of said active energy ray curable compounds (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) contains an organic solvent (c-1) represented by the following general formula (1) in order to obtain a hard coat layer which hardly causes interference fringes at the interface with the substrate. .
- R 1 represents a linear or branched alkyl group having 1 to 10 carbon atoms, an allyl group, a phenyl group or a benzyl group, and n is an integer of 1 to 3) Show)
- the above (c-1) has a relatively high boiling point, segregates the resin (B) on the surface, and as a compatibilizer between the active energy ray curable compound (A) and the resin (B) Since it acts, high antistatic property and an excellent coating film appearance can be obtained. In addition, it is considered that the generation of interference fringes can be suppressed by the high substrate erodibility (c-1).
- the organic solvent (c-1) may be used alone or in combination of two or more.
- organic solvent in which R 1 represents an alkyl group having a linear or branched structure having 1 to 10 carbon atoms are, for example, methyl glycol, methyl diglycol, methyl triglycol And isopropyl glycol, isopropyl diglycol, butyl glycol, butyl diglycol, butyl triglycol, isobutyl glycol, isobutyl diglycol, hexyl glycol, hexyl diglycol, 2-ethylhexyl glycol and the like.
- the content of (c-1) is 0.1% by mass or more and less than 15% by mass in the organic solvent (C).
- the content of (c-1) is less than 0.1% by mass, the effects of the above effects are reduced, and interference fringes are not generated, and a good coating film appearance can not be obtained.
- the content of (c-1) is preferably in the range of 1.5 to 12% by mass in the organic solvent (C) from the viewpoint that the coating film appearance and the suppression effect of the interference fringes can be further improved. It is preferably present, and more preferably in the range of 2 to 10% by mass.
- the organic solvent (C) contains the above (c-1) as an essential component, and as the other organic solvents, for example, hydrophobic solvents (c-2) and hydrophilic solvents other than the above (c-1) (C-3) can be used.
- hydrophobic solvent (c-2) examples include diethyl ether, benzene, toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, xylene, n-butanol, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate , Chloroform, propylene glycol monomethyl ether acetate and the like. These solvents may be used alone or in combination of two or more.
- hydrophilic solvent (c-3) examples include acetone, methanol, ethanol, n-propanol, isopropyl alcohol, diacetone alcohol, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dioxolane, tetrahydrofuran, tetrahydropyran, dimethyl Formamide and the like can be mentioned. These solvents may be used alone or in combination of two or more.
- the hydrophilic solvent (c-3) refers to a solvent having a solubility in water of at least 10 g / 100 ml, and this and any other solvent than the above (c-1) are hydrophobic solvents ( c-2).
- the solubility of the organic solvent in water accounts for the solubility in 100 ml of water (25 ° C.).
- the coating stability of the active energy ray-curable composition can be further improved, and it is possible to prevent the occurrence of cracks in the cured coating film.
- the amount is preferably in the range of 5 to 30% by mass, more preferably 10 to 25% by mass, in the organic solvent (C), from the viewpoint of obtaining an excellent coating film appearance.
- the compounding quantity of the said organic solvent (C) in the active energy ray curable composition of this invention sets it as the quantity used as the viscosity suitable for the coating method mentioned later.
- the active energy ray curable composition of this invention can be made into a cured coating film by irradiating an active energy ray after coating on a base material.
- the active energy ray refers 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 the curability.
- a photosensitizer (E) can be further added to improve the curability.
- Examples of the photopolymerization initiator (D) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo ⁇ 2-hydroxy-2-methyl-1- [4- (4) 1-Methylvinyl) phenyl] propanone ⁇ , benzyl dimethyl 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; acyl phosphine oxide compounds such as 2,4,6
- photosensitizer (E) for example, tertiary amine compounds such as diethanolamine, N-methyldiethanolamine, tributylamine, urea compounds such as o-tolylthiourea, sodium diethyl dithiophosphate, s-benzylisothiolo And sulfur compounds such as sodium-p-toluenesulfonate.
- tertiary amine compounds such as diethanolamine, N-methyldiethanolamine, tributylamine, urea compounds such as o-tolylthiourea, sodium diethyl dithiophosphate, s-benzylisothiolo And sulfur compounds such as sodium-p-toluenesulfonate.
- the total amount used in the case of using the above-mentioned photopolymerization initiator (D) and photosensitizer (E) is the active energy ray curable composition (A) in the active energy ray curable composition of the present invention
- the amount is preferably 0.05 to 20 parts by mass with respect to 100 parts by mass, and more preferably 0.5 to 10 parts by mass.
- a polymerization inhibitor In the active energy ray-curable composition of the present invention, a polymerization inhibitor, a surface control agent, an antistatic agent according to the use and required properties, as other ingredients other than the above components (A) to (E).
- Antifoaming agent Inorganic fillers such as silicon oxide, aluminum oxide, titanium oxide, zirconia, antimony pentoxide, etc. can be blended. These other compounds may 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 on 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 substrate used in the film of the present invention is preferably a highly transparent resin, for example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polypropylene, polyethylene, polymethylpentene-1 And 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 such as cellulose nitrate; Acrylic resins such as methyl methacrylate; vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; polyvinyl alcohol; ethylene-acetic acid Polynyl; Polycarbonate; Polysulfone; Polyether sulfone; Polyether ether ketone; Polyimide resin such as polyimide, polyether imide, etc
- Zeroor Modified Norbornene-based resins (for example, “Arton” manufactured by JSR Corporation), cyclic olefin copolymers (for example, “Aper” manufactured by Mitsui Chemicals, Inc.), and the like. Furthermore, you may use what bonded the base material which consists of these resin in 2 or more types.
- the coating stability, the coating film appearance and the antistatic property are excellent. It is possible to form a hard coat layer excellent in interference fringe suppression.
- the polymethyl methacrylate base (hereinafter abbreviated as "PMMA") is a base made of a polymer containing polymethyl methacrylate as a main component (preferably 100% by mass), for example, “Sumitomo Chemical Co., Ltd.” Technoroy S014G, Technoloy S001G, Technoroy S000, "Acriprene HBS006", “Acriprene HBXN 47", "Acriprene HBS010", Mitsubishi Chemical Corp., "Acryprene HBS010", “Panlight film PC-2151”, etc., manufactured by Teijin Chemicals Ltd. It can be obtained as an item.
- the film substrate may be film-like or sheet-like, and the thickness thereof is, for example, in the range of 20 to 500 ⁇ m.
- the thickness thereof 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.
- the active energy ray-curable composition of the present invention for example, die coating, microgravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, dip coating , Spinner coat, brush coating, silk screen beta coat, wire bar coat, flow coat and the like.
- the organic solvent (C) is volatilized and the resin (B) is applied to the coated film surface before the active energy ray is irradiated.
- the conditions of the heat drying include, for example, heat drying at a temperature of 50 to 100 ° C. for a time of 0.5 to 10 minutes.
- the active energy ray for curing the active energy ray-curable composition of the present invention is, as described above, ionizing radiation such as ultraviolet light, electron beam, ⁇ -ray, ⁇ -ray and ⁇ -ray.
- ionizing radiation such as ultraviolet light, electron beam, ⁇ -ray, ⁇ -ray and ⁇ -ray.
- an ultraviolet ray as an active energy ray, as an apparatus which irradiates the ultraviolet ray, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an electrodeless lamp (fusion lamp), a chemical lamp, Black light lamps, mercury-xenon lamps, short arc lamps, helium-cadmium lasers, argon lasers, sunlight, LED lamps and the like can be mentioned.
- the film thickness of the cured coating film at the time of forming the cured coating film of the active energy ray curable composition of the present invention on the film substrate makes the hardness of the cured coating film sufficient and cures the coating film
- 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 because curling of the film due to shrinkage can be suppressed.
- the active energy ray-curable composition of the present invention is excellent in coating stability, coating film appearance and antistatic property, and can form a hard coat layer which hardly generates interference fringes at the interface with the substrate. is there.
- a film having a hard coat layer composed of a cured coating film of the active energy ray curable composition of the present invention is a flat panel display such as a liquid crystal display (LCD), an organic EL display (OLED), a plasma display (PDP) It can be suitably used as an optical film used for FPD.
- LCD liquid crystal display
- OLED organic EL display
- PDP plasma display
- Production Example 1 Synthesis of Urethane Acrylate (A2-1) Composition 55.5 parts by mass of butyl acetate, 222 parts by mass of isophorone diisocyanate (hereinafter referred to as "IPDI”), and 0.5 parts by mass of p-methoxyphenol in a flask equipped with a stirrer, a gas introduction pipe, a cooling pipe, and a thermometer Then, 0.5 parts by mass of dibutyltin diacetate is charged, and after raising the temperature to 70 ° C., pentaerythritol triacrylate (hereinafter referred to as “PE3A”) / pentaerythritol tetraacrylate (hereinafter referred to as “PE4A”) mixture ( 993.4 parts by mass of an 80% by weight butyl acetate solution (a mixture of 75/25 in mass ratio) was dropped over 1 hour.
- PE3A pentaerythritol triacrylate
- PE4A pent
- urethane acrylate (A2-1) / PE4A mixture A mixture having a mass ratio of 80/20, a nonvolatile content of 100% by mass, hereinafter, abbreviated as “urethane acrylate (A2-1) composition” was obtained.
- the molecular weight of the urethane acrylate (A2-1) was 818.
- the weight average molecular weight of the resin (B-1) obtained above was measured by gel permeation chromatography (GPC) 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 used in series connection. "TSKgel G5000" (7.8 mm ID ⁇ 30 cm) ⁇ 1 "TSK gel G 4000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 "TSK gel G 3000" (7.8 mm ID ⁇ 30 cm) ⁇ 1 This "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 volume: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4% by mass) Standard sample: A calibration curve was prepared using the following standard polystyrene.
- Example 1 65 parts by weight of PE4A, 35 parts by weight of the urethane acrylate (UA) composition obtained in Production Example 1 (28 parts by weight as (UA), 7 parts by weight of PE4A), 10 parts by weight of 1-hydroxycyclohexyl phenyl ketone, obtained in Production Example 2 Methyl ethyl ketone (hereinafter, abbreviated as "MEK”), dimethyl carbonate (hereinafter, abbreviated as "DMC”), PGME, phenyl glycol (hereinafter, referred to as "the solid portion of the resin (B-1)"
- MEK Methyl ethyl ketone
- DMC dimethyl carbonate
- PGME phenyl glycol
- the mixture was
- Examples 2 to 19 The procedure of Example 1 was repeated except that the composition was changed to the composition shown in Tables 1 and 2, to obtain active energy ray curable compositions (2) to (19).
- Example 1 (Comparative Examples 1 to 7) The procedure of Example 1 was repeated except that the composition was changed to the composition shown in Table 3, to obtain active energy ray-curable compositions (R1) to (R7).
- the active energy ray curable composition is coated on a 60 ⁇ m thick PMMA film with a bar coater to a film thickness of 5 ⁇ m, dried at 25 ° C. for 15 seconds, then dried at 60 ° C. for 1.5 minutes, and then nitrogen Irradiation was performed three times at an irradiation light quantity of 1 kJ / m 2 using an ultraviolet irradiation apparatus (high pressure mercury lamp manufactured by Eye Graphics Co., Ltd.) under an atmosphere to obtain a PMMA film having a cured coating film as a sample for evaluation.
- an ultraviolet irradiation apparatus high pressure mercury lamp manufactured by Eye Graphics Co., Ltd.
- the cured coating films of the active energy ray curable compositions of the present invention of Examples 1 to 19 are excellent in coating stability and coating film appearance, and the surface resistance value is It was confirmed that the antistatic property is also high on the order of 10 to 8 to 9 powers. It was also found that interference fringes did not occur even when polymethyl methacrylate was used as the substrate.
- Comparative Examples 1 and 2 are examples using an active energy ray curable composition containing no resin (B) and no organic solvent (c-1), but bumps and cracks have occurred in the cured coating film. The surface resistance value also exceeded 10 13 and the antistatic property was also poor. Further, in Comparative Example 1, interference fringes were also confirmed at the interface with the polymethyl methacrylate substrate.
- Comparative Examples 3 to 4 are examples in which the active energy ray-curable composition containing no organic solvent (c-1) was used, but whitening or cracking occurred in the cured coating. Further, in Comparative Example 4, interference fringes were also confirmed at the interface with the polymethyl methacrylate substrate.
- Comparative Examples 5 to 7 are embodiments in which the content of the organic solvent (c-1) exceeds the range specified in the present invention, but whitening occurred in the cured coating.
- the surface resistance value also exceeded 10 ⁇ 13>, and the antistatic property was also poor.
- Example 21 to 38 The procedure of Example 1 was repeated except that the composition was changed to the composition shown in Tables 4 to 5, to obtain active energy ray curable compositions (21) to (38).
- the cured coating films of the active energy ray-curable compositions of the present invention of Examples 20 to 38 are excellent in coating stability and coating film appearance, and have high refractive index. It has been confirmed that the antistatic property is also high on the order of 8 to 9 to the surface resistance value of 10. It was also found that interference fringes did not occur even when polymethyl methacrylate was used as the substrate.
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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、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、真空乾燥による脱溶剤の後、ウレタンアクリレート(A2-1)/PE4A混合物(質量比80/20の混合物、不揮発分100質量%、以下、「ウレタンアクリレート(A2-1)組成物」と略記する。)を得た。なお、ウレタンアクリレート(A2-1)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54.2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(以下、「MeOH」と略記する。)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(以下、「PGME」と略記する。)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、MeOH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43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。
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」
PE4A65質量部、製造例1で得られたウレタンアクリレート(UA)組成物35質量部((UA)として28質量部、PE4A7質量部)、1-ヒドロキシシクロヘキシルフェニルケトン10質量部、製造例2で得られた樹脂(B-1)の固形分5質量部を、メチルエチルケトン(以下、「MEK」と略記する。)、ジメチルカーボネート(以下、「DMC」と略記する。)、PGME、フェニルグリコール(以下、「PhG」と略記する。)で希釈し、溶剤組成がMEK/DMC/PGME/MeOH/PhG=67.5/19.9/7.5/4.6/0.5(質量比)となるよう調整し、均一に混合して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)~(19)を得た。
表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)~(R7)を得た。
活性エネルギー線硬化性組成物を、厚さ60μmのPMMAフィルムに、バーコーターで膜厚5μmとなるように塗工し、25℃で15秒間、次いで60℃で1.5分間乾燥した後、窒素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1kJ/m2で3回照射し、硬化塗膜を有するPMMA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を目視観察し、以下のように評価した。
(1)ブツがないものを「○」、ブツがあるものを「×」
(2)白化がないものを「○」、白化が一部確認できるものを「△」、白化が著しく確認できるものを「×」
(3)塗膜に割れが生じていないものを「○」、塗膜に割れが生じているものを「×」
上記で得られた評価用サンプルのPMMAフィルム側を黒板に貼り付け、3波長蛍光灯およびナトリウムランプをあて、目視にて干渉縞の有無を判定し以下のように評価した。
「◎」:3波長蛍光灯およびナトリウムランプの下でも干渉縞が確認されない。
「○」:ナトリウムランプの下では干渉縞が確認されるが、3波長蛍光灯の下では干渉縞が確認されない。
「×」:3波長蛍光灯およびナトリウムランプの下で干渉縞が確認される。
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C2139:2008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。
「PhDG」;フェニルジグリコール
「BzG」;ベンジルグリコール
「BzDG」;ベンジルジグリコール
「BuG」;ブチルグリコール
「BuDG」;ブチルジグリコール
「MG」;メチルグリコール
「THFA」;テトラヒドロフルフリルアクリレート
「BzA」;ベンジルアクリレート
「TAC」;トリアセチルセルロースフィルム
高屈折率重合性単量体(9,9-ビス[4-(2-アクリロイルオキシエトキシ)フェニル]フルオレン、屈折率1.616)(以下、「高屈(1)」と略記する。)15質量部、PE4A 55質量部、製造例1で得られたウレタンアクリレート(UA)組成物45質量部((UA)として36質量部、PE4A9質量部)、製造例2で得られた樹脂(B-1)の固形分5質量部を、メチルエチルケトン(以下、「MEK」と略記する。)、ジメチルカーボネート(以下、「DMC」と略記する。)、PGME、フェニルグリコール(以下、「PhG」と略記する。)で希釈し、溶剤組成がMEK/DMC/PGME/MeOH/PhG=67.5/19.9/7.5/4.6/0.5(質量比)となるよう調整し、均一に混合して活性エネルギー線硬化性組成物(20)を得た。
表4~5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(21)~(38)を得た。
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。なお、屈折率が1.55以上であれば、高い屈折率を有すると判断した。
Claims (12)
- 前記有機溶剤(C)が、更に疎水性溶剤(c-2)を含有するものである請求項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、更に有機溶剤(c-1)以外の親水性溶剤(c-3)を含有するものである請求項2記載の活性エネルギー線硬化性組成物。
- 前記親水性溶剤(c-3)の含有量が、前記有機溶剤(C)中5~30質量%の範囲である請求項3記載の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5~55質量%用いた重合体である請求項1~4のいずれか1項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1~5のいずれか1項記載の活性エネルギー線硬化性組成物。
- 前記活性エネルギー線硬化性化合物(A)が、屈折率が1.55以上の高屈折率重合性単量体(A-1)、及び/又は、前記(A-1)以外の重合性単量体(A-2)を含有するものである請求項1~6のいずれか1項記載の活性エネルギー線硬化性組成物。
- 前記重合性単量体(A-2)が、(メタ)アクリロイル基を3つ以上有する多官能(メタ)アクリレート、及び/又は、ウレタン(メタ)アクリレートを含有するものである請求項1~7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1~9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1~9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。
- ポリメチルメタクリレート基材の少なくとも一方の面に前記硬化塗膜を有するものである請求項11記載のフィルム。
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JP2005200658A (ja) * | 2005-02-14 | 2005-07-28 | Toppan Printing Co Ltd | 樹脂組成物およびその成型体 |
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JP2005200658A (ja) * | 2005-02-14 | 2005-07-28 | Toppan Printing Co Ltd | 樹脂組成物およびその成型体 |
JP2011153109A (ja) * | 2010-01-28 | 2011-08-11 | Kohjin Co Ltd | 不飽和第4級アンモニウム塩化合物からなる帯電防止剤及び帯電防止組成物 |
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CN111566129A (zh) | 2020-08-21 |
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