JP7114874B2 - Active energy ray-curable composition and film using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to an active energy ray-curable composition and a film using the same.

Various resin films are used for preventing scratches 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 automobile interior and exterior, It is used in various applications such as low-reflection films for windows and heat-shielding films. However, since the resin film surface is soft and has low scratch resistance, it is possible to provide a hard coat layer on the film surface by coating and curing a hard coating agent composed of a UV-curable composition or the like on the film surface for the purpose of compensating for this. commonly practiced. To summarize the process of providing the hard coat layer, the original film wound in a roll is sent to the coating machine, the hard coating agent is applied, and the hard coat layer is formed by curing with ultraviolet irradiation, and then again. It is wound into a roll.

During the winding process, static electricity is generated on the surface of the film due to friction between the films, so when the film is unwound from the roll during reprocessing, the film sticks to itself. I had a problem. Moreover, when this film is used in a liquid crystal display or the like, there is a problem that the generated static electricity causes the display to malfunction.

In order to suppress the generation of static electricity on the film surface, a technique of adding an antistatic agent to the hard coating agent is generally employed. For example, a method has been proposed in which a compound having a polyoxyethylene chain and a quaternary ammonium salt is added as an antistatic agent to a hard coating agent (see, for example, Patent Document 1).

Also, a method has been proposed in which two types of copolymers made from polymerizable monomers having a quaternary ammonium salt are added as antistatic agents to a hard coating agent (see, for example, Patent Document 2).

However, the hard coat agents containing these antistatic agents do not have sufficient antistatic performance. Furthermore, when a large amount of antistatic agent is blended, the antistatic performance is improved, but there is a problem that the antistatic agent bleeds after use under moist heat conditions.

Japanese Patent Application Laid-Open No. 2004-143303 JP 2004-123924 A

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 both excellent antistatic properties and bleeding resistance, and a film using the same.

The present invention provides an active energy ray-curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, and a compound (C) having a quaternary ammonium salt and not having an alicyclic structure. and an organic solvent (D), and provide a film using the same.

The active energy ray-curable composition of the present invention can be applied to a film surface and cured to form a hard coat layer having excellent antistatic properties and pencil hardness. 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 sticking prevention and dust adhesion prevention due to static electricity. Therefore, the film having the cured coating film of the active energy ray-curable composition of the present invention can avoid problems such as sticking and adhesion of dust when wound into a roll and when unwound from the roll. It is possible to provide a film excellent in handling. Furthermore, the cured coating film of the active energy ray-curable composition of the present invention has excellent bleeding resistance, and even after use under moist heat conditions, the antistatic agent does not bleed, There is also little change in preventive properties.

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 used for flat panel displays such as liquid crystal displays (LCD), organic EL displays (OLED), and plasma displays (PDP). It can be suitably used as an optical film used for FPD). Furthermore, since it has excellent antistatic properties when used for these purposes, adhesion of dust and the like can be suppressed. Furthermore, when this film is used in a liquid crystal display or the like, malfunction of the display due to generated static electricity can be prevented.

The active energy ray-curable composition of the present invention has an active energy ray-curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt, and a quaternary ammonium salt, and an alicyclic It contains a compound (C) having no structure and an organic solvent (D).

As the active energy ray-curable compound (A), for example, polyfunctional (meth)acrylates, urethane (meth)acrylates, and the like can be used.

Examples of the polyfunctional (meth)acrylate include 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, acrylates, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, tricyclode Kandimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, etc. dihydric alcohol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, neopentyl glycol 4 per mol di(meth)acrylate of a diol obtained by adding ethylene oxide or propylene oxide in an amount of 1 mol or more, di(meth)acrylate of a diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, trimethylol Propane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, tris (2-(meth)acryloyloxyethyl)isocyanurate, glycerin tri(meth)acrylate, pentaerythritol 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, polypentaerythritol poly(meth)acrylate, etc. mentioned. These compounds may be used alone or in combination of two or more.

As the urethane (meth)acrylate, a reaction product of polyisocyanate and a (meth)acrylate having a hydroxyl group can be used.

Examples of the polyisocyanate include aliphatic polyisocyanate and aromatic polyisocyanate. Aliphatic polyisocyanate is preferable because it can reduce the coloring 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 portion other than the isocyanate group is composed of an aliphatic hydrocarbon. Specific examples of this aliphatic polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate and lysine triisocyanate; cycloaliphatic polyisocyanates such as methyl)cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane and 2-methyl-1,5-diisocyanatocyclohexane; A trimerized product obtained by trimerizing the aliphatic polyisocyanate or the alicyclic polyisocyanate can also be used as the aliphatic polyisocyanate. Moreover, these aliphatic polyisocyanates can be used either singly or in combination of two or more.

In order to improve the scratch resistance of the coating film among the aliphatic polyisocyanates, hexamethylene diisocyanate, which is a diisocyanate of a linear aliphatic hydrocarbon, norbornane diisocyanate, which is an alicyclic diisocyanate, and isophorone Diisocyanates are preferred.

The (meth)acrylate is a compound having a hydroxyl group and a (meth)acryloyl group. Specific examples of this (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,5 - Dihydric alcohol mono (meth) acrylate such as pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, neopentyl glycol hydroxypivalate mono (meth) acrylate ) acrylate; trimethylolpropane di(meth)acrylate, ethylene oxide (EO)-modified trimethylolpropane (meth)acrylate, propylene oxide (PO)-modified trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, bis( 2-(Meth)acryloyloxyethyl)hydroxyethyl isocyanurate, mono- or di(meth)acrylates of trihydric alcohols, or mono- and di(meth)acrylates having hydroxyl groups partially modified with ε-caprolactone. Di(meth)acrylates; compounds having a monofunctional hydroxyl group and a tri- or more functional (meth)acryloyl group such as pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate Alternatively, polyfunctional (meth)acrylates having a hydroxyl group obtained by further modifying the compound with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (Meth) acrylate having an oxyalkylene chain such as acrylate; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) acrylate having a block structure oxyalkylene chain ( meth) acrylate; poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate having a random structure oxyalkylene chain, etc. be done. These (meth)acrylates can be used alone or in combination of two or more.

The reaction between the polyisocyanate and the (meth)acrylate can be carried out by a conventional urethanization reaction. Moreover, in order to accelerate 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 urethanization catalyst include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, and dibutyltin. Diacetate, organic tin compounds such as tin octylate, organic zinc compounds such as zinc octylate, and the like.

In the present invention, "(meth)acrylate" refers to one or both of acrylate and methacrylate, and "(meth)acryloyl" refers to one or both of acryloyl and methacryloyl.

As the active energy ray-curable compound (A), it is preferable to use a compound having a hydroxyl value of 40 mgKOH/g or less among the above-mentioned compounds, since even more excellent antistatic property and high hardness can be obtained. , dipentaerythritol hexaacrylate, and/or pentaerythritol tetraacrylate are more preferably used.

The resin (B) must contain a quaternary ammonium salt in order to obtain excellent antistatic properties.

The resin (B) must have an alicyclic structure and a quaternary ammonium salt in order to obtain excellent antistatic properties.

Specific examples of the resin (B) include, for example, a polymerizable monomer (b1) having an alicyclic structure, a polymerizable monomer (b2) having a quaternary ammonium salt, and the ( Examples include copolymers of b1) and (b2) with other polymerizable monomers (b3).

The polymerizable monomer (b1) has an alicyclic structure. Examples of the alicyclic structure include monocyclic alicyclic structures such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, and cyclodecane ring; 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. 3.1.1]dodecane ring, spiro[3.4]octane ring and other polycyclic alicyclic structures. Further, specific examples of the polymerizable monomer (b1) 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. These polymerizable monomers (b1) can be used alone or in combination of two or more.

Examples of the polymerizable monomer (b2) having a quaternary ammonium salt include counters such as 2-[(meth)acryloyloxy]ethyltrimethylammonium chloride and 3-[(meth)acryloyloxy]propyltrimethylammonium chloride. Those whose anion is chloride; Those whose counter anions are bromide such as 2-[(meth)acryloyloxy]ethyltrimethylammonium bromide, 3-[(meth)acryloyloxy]propyltrimethylammonium bromide; 2-[(meth)acryloyloxy ] Ethyltrimethylammonium methylphenylsulfonate, 2-[(meth)acryloyloxy]ethyltrimethylammonium methylsulfonate, 3-[(meth)acryloyloxy]propyltrimethylammoniummethylphenylsulfonate, 3-[(meth)acryloyloxy]propyltrimethyl Non-halogen counter anions such as ammonium methylsulfonate, 2-[(meth)acryloyloxy]ethyltrimethylammonium methylsulfate, 3-[(meth)acryloyloxy]propyltrimethylammonium methylsulfate; dimethylaminoethyl ( meth)acrylamide methyl chloride quaternary salt, dimethylaminopropyl(meth)acrylamide methyl chloride quaternary salt and the like. These polymerizable monomers (b2) can be used alone or in combination of two or more.

Examples of the other 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 acrylates and dodecyl (meth)acrylate; Glycol mono(meth)acrylate, phenoxypolyethylene glycol mono(meth)acrylate, phenoxypolyethylene glycol/polypropylene glycol mono(meth)acrylate, nonylphenoxypolypropylene glycol mono(meth)acrylate, nonylphenoxypoly(ethylene glycol/propylene glycol) mono( mono(meth)acrylates of polyalkylene glycol such as meth)acrylate; and (meth)acrylates having a fluorinated alkyl group such as 2-perfluorohexylethyl (meth)acrylate. These polymerizable monomers (b3) can be used alone or in combination of two or more.

As the polymerizable monomer (b3), a (meth)acrylate having a fluorinated alkyl group and/or a polyalkylene glycol mono(meth)acrylate is used from the viewpoint of obtaining even better antistatic properties. It is preferable to use methoxypolyethylene glycol mono(meth)acrylate as the polyalkylene glycol mono(meth)acrylate.

Among the polyalkylene glycol mono (meth) acrylates, the number average molecular weight of the polyalkylene glycol used as a raw material for the polyalkylene glycol mono (meth) acrylate is from 200 to 200 from the viewpoint of obtaining even more excellent antistatic properties. A range of 8,000 is preferred, a range of 300 to 6,000 is more preferred, a range of 400 to 4,000 is even more preferred, and a range of 400 to 2,000 is particularly preferred.

The ratio of the polymerizable monomer (b1) in the total amount of raw material of the resin (B) is 5 to 55 because it can further improve the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention. A range of % by mass is preferred, a range of 10 to 50% by mass is more preferred, and a range of 12 to 45% by mass is even more preferred.

In addition, the ratio of the polymerizable monomer (b2) in the total amount of raw materials of the resin (B) is 30, 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 ∼90% by mass is preferable, the range of 40 to 80% by mass is more preferable, and the range of 45 to 70% by mass is more preferable.

When the polyalkylene glycol mono(meth)acrylate is used as the polymerizable monomer (b3), 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 polyalkylene glycol mono (meth) acrylate in the total amount of raw materials of 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 in the range of 20 to 40% by mass. is more preferred.

Further, when the (meth)acrylate having the fluorinated alkyl group is used as the polymerizable monomer (b3), the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved. Therefore, the ratio of (meth)acrylate having a fluorinated alkyl group in the total amount of 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. , 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, and preferably 2,000, because the antistatic property of the cured coating film of the active energy ray-curable composition of the present invention can be further improved. A range of up to 50,000 is more preferred, and a range of 3,000 to 30,000 is even more preferred. In addition, the weight average molecular weight in the present invention is a value in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

Since the amount of the resin (B) added can further improve the antistatic property and bleeding resistance of the cured coating film of the active energy ray-curable composition of the present invention, the active energy ray-curable composition (A) 100 It is preferably in the range of 0.1 to 10 parts by mass, more preferably in the range of 1.3 to 5 parts by mass, and even more preferably in the range of 1.5 to 2 parts by mass.

The compound (C) has a quaternary ammonium salt and does not have an alicyclic structure. By using the compound (C) and the resin (B) in combination, even when the amount of the antistatic agent (the resin (B) and the compound (C)) used is reduced, the cured coating film is excellent. Antistatic property can be exhibited, and bleeding can also be suppressed.

Examples of the compound (C) include the polymerizable monomer (b2) having the quaternary ammonium salt and the polymerizable monomer having the quaternary ammonium salt, which can be used as a raw material for the resin (B). A copolymer of (b2) and the other polymerizable monomer (b3) can be used.

The weight average molecular weight of the compound (C) is preferably in the range of 100 to 1,000, more preferably in the range of 130 to 500, from the viewpoint of obtaining even better antistatic properties and bleeding resistance. , 150-300 is more preferred.

The compound (C) more preferably has an active energy ray-curable functional group from the viewpoint of enhancing bleeding resistance.

As the compound (C), among the above, 2-[(meth)acryloyloxy]ethyltrimethylammonium chloride, 3-[(meth)acryloyl It is preferable to use one or more compounds selected from the group consisting of oxy]propyltrimethylammonium chloride, dimethylaminoethyl(meth)acrylamide methyl chloride quaternary salt, and dimethylaminopropyl(meth)acrylamide methyl chloride quaternary salt. .

The compounding amount of the compound (C) can further improve the antistatic property and bleeding resistance of the cured coating film of the active energy ray-curable composition of the present invention, so the active energy ray-curable composition (A) 100 It is preferably in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass, and even more preferably in the range of 3 to 8 parts by mass.

The total blending amount of the resin (B) and the compound (C) can further improve the balance between the antistatic property and the bleeding resistance, and the antistatic property does not change even after use under moist heat conditions. 1 to 10 parts by mass, more preferably 3 to 8 parts by mass, based on 100 parts by mass of the active energy ray-curable compound (A).

As the mass ratio [(B)/(C)] of the resin (B) and the compound (C), the balance between antistatic property and bleeding resistance can be further improved, and after use under moist heat conditions Also, from the viewpoint of little change in antistatic properties, it is preferably in the range of 5/95 to 40/60, more preferably in the range of 10/90 to 30/70, and in the range of 13/87 to 20/80. More preferred.

The organic solvent (D) 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. Examples of the organic solvent (D) include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol and t-butanol; esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate. ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; These organic solvents may be used alone or in combination of two or more.

The amount of the organic solvent (D) blended in the active energy ray-curable composition of the present invention is preferably an amount that provides a viscosity suitable for the coating method described below.

In addition, the active energy ray-curable composition of the present invention can be formed into a cured coating film by applying an active energy ray to a substrate and then irradiating it with an active energy ray. This active energy ray means ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When a cured coating film is formed by irradiating ultraviolet rays as active energy rays, it is preferable to add a photopolymerization initiator (E) to the active energy ray-curable composition of the present invention to improve curability. Moreover, if necessary, a photosensitizer can be further added to improve curability. On the other hand, when ionizing radiation such as electron beams, α-rays, β-rays, and γ-rays is used, rapid curing can be performed without using a photopolymerization initiator (E) or a photosensitizer. It is not necessary to add agent (E) or photosensitizer.

Examples of the photopolymerization initiator (E) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo{2-hydroxy-2-methyl-1-[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-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl )-butanone and other acetophenone compounds; benzoin, benzoin methyl ether, benzoin isopropyl ether and other benzoin compounds; 2,4,6-trimethylbenzoindiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine Acylphosphine oxide compounds such as oxide; benzyl (dibenzoyl), methylphenylglyoxyester, oxyphenylacetic acid 2-(2-hydroxyethoxy)ethyl ester, oxyphenylacetic acid 2-(2-oxo-2-phenylacetoxyethoxy) Benzyl compounds such as ethyl esters; benzophenone, methyl o-benzoylbenzoate-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylated benzophenone, 3 ,3′,4,4′-tetra(t-butylperoxycarbonyl)benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, benzophenone compounds such as 4-methylbenzophenone; Thioxanthone compounds such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone; Aminobenzophenone compounds such as Michler-ketone and 4,4'-diethylaminobenzophenone; -butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-( 4-methylphenylsulfonyl) and propan-1-one. These photopolymerization initiators (E) can be used alone or in combination of two or more.

Examples of the photosensitizer include tertiary amine compounds such as diethanolamine, N-methyldiethanolamine and tributylamine, urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiuronium-p. - sulfur compounds such as toluenesulfonate;

The amount of the photopolymerization initiator (E) and the photosensitizer used is 0.05 for each of 100 parts by mass of the active energy ray-curable (A) in the active energy ray-curable composition of the present invention. ~20 mass parts is preferable, and 0.5 to 10 mass% is more preferable.

In the active energy ray-curable composition of the present invention, other ingredients other than the above components (A) to (E) may include a polymerization inhibitor, a surface conditioner, and an antifoaming agent, depending on the application and required properties. , Additives such as viscosity modifiers, light stabilizers, weather stabilizers, heat stabilizers, UV absorbers, antioxidants, leveling agents, organic pigments, inorganic pigments, pigment dispersants, silica beads, organic beads; Silicon oxide , aluminum oxide, titanium oxide, zirconia, and antimony pentoxide. These other formulations 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 an active energy ray to form a cured coating film. be.

As the material of the film substrate used in the film of the present invention, highly transparent resins are preferable. Examples include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; Cellulose 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, etc.; Acrylic resins such as methyl methacrylate; vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; polyvinyl alcohol; ethylene-vinyl acetate copolymer; polystyrene; Polyimide-based resins such as polyimide and polyetherimide; , "Appel" manufactured by Mitsui Chemicals, Inc.). Furthermore, two or more types of base materials made of these resins may be bonded together to be used.

Further, the film substrate may be film-like or sheet-like, and its thickness is preferably in the range of 20 to 500 μm. When a film-like base film is used, its thickness is preferably in the range of 20 to 200 μm, more preferably in the range of 30 to 150 μm, even more preferably in the range of 40 to 130 μm. By setting the thickness of the film substrate within this range, curling can be easily suppressed even when a hard coat layer is provided on one side of the film using the active energy ray-curable composition of the present invention.

Examples of methods for applying the active energy ray-curable composition of the present invention to the film substrate include die coating, micro gravure 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 organic solvent contained in the active energy ray-curable composition of the present invention is volatilized after applying the active energy ray-curable composition to the base film and before irradiating the active energy ray, and the resin In order to segregate (B) and compound (C) 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, but usually the temperature is in the range of 50 to 100° C. and the time is in the range of 0.5 to 10 minutes. preferable.

As described above, the active energy rays for curing the active energy ray-curable composition of the present invention include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Here, when ultraviolet rays are used as active energy rays, devices for irradiating the ultraviolet rays include, for example, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-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, LED lamps and the like.

When forming a cured coating film of the active energy ray-curable composition of the present invention on the film substrate, the thickness of the cured coating film is such that the cured coating film has sufficient hardness and the coating film is cured. Since curling of the film due to shrinkage can be suppressed, the range is preferably 1 to 30 μm, more preferably 3 to 15 μm, and even more preferably 4 to 10 μm.

As described above, the active energy ray-curable composition of the present invention can form a hard coat layer having excellent antistatic properties and bleeding resistance. The surface resistance value of the cured coating film of the active energy ray-curable composition is preferably in the range of 1×10 ⁷ to 9.99×10 ⁹ Ω/□, and 1×10 ⁸ to 9.99× A range of 10 ⁸ Ω/□ is more preferred. The method for measuring the surface resistance of the cured coating film will be described in Examples.

EXAMPLES Hereinafter, the present invention will be described more specifically 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 stirrer, a reflux condenser and a nitrogen inlet tube to replace the air in the flask with nitrogen gas. Then, 54.7 parts by mass of 2-(methacryloyloxy)ethyltrimethylammonium chloride, 19.9 parts by mass of cyclohexyl methacrylate, and methoxypolyethylene glycol methacrylate (manufactured by NOF Corporation "Blenmer PME-1000"; repeating unit number n ≈ 23, molecular weight 1,000) 24.9 parts by weight, 0.5 parts by weight of methacrylic acid, 50 parts by weight of methanol and 10 parts by weight of PGME were added. 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° C. for 3 hours. Then, methanol was added for dilution to obtain a 45% by mass solution of resin (B-2) having an alicyclic structure and a quaternary ammonium salt. The weight average molecular weight of the obtained resin (B-1) was 10,000.

(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 inlet tube to replace the air in the flask with nitrogen gas. Then, 53.7 parts by mass of 2-(methacryloyloxy)ethyltrimethylammonium chloride, 29.3 parts by mass of cyclohexyl methacrylate, and methoxypolyethylene glycol methacrylate (manufactured by NOF Corporation "Blenmer PME-1000"; repeating unit number n ≈ 23, molecular weight 1,000) 14.6 parts by weight, 1.9 parts by weight of 2-perfluorohexylethyl acrylate, 0.5 parts by weight of methacrylic acid, 50 parts by weight of methanol and 10 parts by weight of propylene glycol monomethyl ether were added. 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° C. for 3 hours. Then, methanol was added for dilution to obtain a 45% by mass solution of resin (B-2) having an alicyclic structure and a quaternary ammonium salt. The weight average molecular weight of the obtained resin (B-1) was 10,000.

The weight average molecular weights of resins (B-1) and (B-2) obtained above were 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 connected in series and used.
"TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000" (7.8mm I.D. x 30cm) x 1 "TSKgel G3000" (7.8mm I.D. x 30cm) x 1 Book "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (differential refractometer)
Column temperature: 40°C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL/min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: A calibration curve was created 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 compound was measured as follows using the hydroxyl value measuring method described in JIS-K0070.
25 g of acetic anhydride was placed in a 100 ml volumetric flask, pyridine was added to bring the total amount to 100 ml, and 5 ml of the mixture was uniformly mixed. Acetic anhydride is reacted with hydroxyl groups in the active energy ray-curable compound. After allowing to cool, 1 ml of water is added and mixed with stirring, followed by further stirring at 100° C. for 10 minutes to decompose excess acetic anhydride. After allowing to cool, wash the walls of the flask with 5 ml of ethanol. A few drops of phenolphthalein solution are added as an indicator, and titrated with 0.5 mol/L potassium hydroxide ethanol solution (titration amount β ml). A blank measurement without using the active energy ray-curable compound is similarly titrated (titration amount β ₀ ml). A hydroxyl value is calculated|required from following formula (1).
Hydroxyl value (mgKOH/g) = (β ₀ - β) x f x 28.05/S + D (1)
However, f: Factor S of 0.5 mol/L potassium hydroxide ethanol solution: Active energy ray-curable compound actual collected weight (unit: g)
D: Acid value (mgKOH/g)

(Example 1)
100 parts by mass of dipentaerythritol hexaacrylate (hereinafter abbreviated as "DPHA"), 2.22 parts by mass of the resin (B-1) solution obtained in Production Example 1 (1 part by mass as resin (B-1) ), dimethylaminopropyl acrylamide methyl chloride quaternary salt (hereinafter abbreviated as (C-1).) 5 parts by mass, photopolymerization initiator (1-hydroxycyclohexylphenyl ketone) 5 parts by mass, solvent (ethanol/n- 100 parts by mass of propyl alcohol/methanol = 85.5/9.6/4.9 (mass ratio) were uniformly mixed to obtain an active energy ray-curable composition (1).

(Example 2, Comparative Examples 1 to 3)
Active energy ray-curable compositions (2) and (R1) to (R3) were obtained in the same manner as in Example 1 except that the composition was changed to that shown in Table 1.

[Preparation of sample for evaluation]
The active energy ray-curable composition was applied to a 60 μm-thick triacetyl cellulose (TAC) film (manufactured by Fujifilm Corporation) with a bar coater so that the film thickness was 5 μm, and the composition was applied at 60° C. for 1.5 minutes. After drying, it was irradiated with 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 to obtain a TAC film having a cured coating film as an evaluation sample. .
In addition, this evaluation sample was allowed to stand for 300 hours under conditions of temperature: 65°C and humidity: 95%, and this was used as an evaluation sample after the humidity and heat resistance test.

[Measurement of surface resistance value (evaluation of antistatic property)]
Regarding the evaluation sample obtained above and the surface of the cured coating film of the evaluation sample after the durability test, in accordance with JIS test method K6911-1995, a high resistivity meter (manufactured by Mitsubishi Chemical Analytech Co., Ltd. "Hiresta-UP MCP-HT450") was used to measure surface resistance at an applied voltage of 500 V and a measurement time of 10 seconds.

[Method for evaluating bleed resistance]
The evaluation sample obtained above and the surface of the cured coating film of the evaluation sample after the durability test were visually observed and evaluated as follows.
"◯": No bleeding was observed.
"X": Bleeding is confirmed.

[Method for evaluating pencil hardness]
The evaluation sample obtained above and the surface of the cured coating film of the evaluation sample after the durability test were measured for pencil hardness according to JIS test method K5600-5-4:1999.

The abbreviations shown in Table 1 refer to the following compounds.
"PETA": pentaerythritol tetraacrylate "(C-2)": 2-[methacryloyloxy] ethyltrimethylammonium chloride

It was confirmed that the cured coating film of the active energy ray-curable composition of the present invention has an excellent pencil hardness, a surface resistance value of the order of 10 to the 8th power to the 9th power, and a high antistatic property. In addition, even after the wet heat resistance test, the change in surface resistance was small, and no bleeding was observed.

On the other hand, Comparative Example 1, in which the resin (B) was not blended, had a surface resistance value of the order of 10 to the 13th power and was poor in antistatic properties.

Comparative Example 2, in which the compound (C) was not blended, had a surface resistance value of the order of 10 to the 11th power and was poor in antistatic properties.

Comparative Example 3 is also an embodiment in which the compound (C) is not blended, and although the surface resistance value is good, significant bleeding was confirmed after the moist heat resistance test.

Claims (7)

an active energy ray-curable compound (A), a resin (B) having an alicyclic structure and a quaternary ammonium salt,
a compound (C) having a quaternary ammonium salt and not having an alicyclic structure;
containing an organic solvent (D),
The resin (B) is a polymerizable monomer (b1) having an alicyclic structure, a polymerizable monomer (b2) having a quaternary ammonium salt, and copolymerizable with the (b1) and (b2). Other polymerizable monomer (b3) is copolymerized, and the resin (B) is a copolymer using 5 to 55% by mass of the polymerizable monomer (b1) as a raw material and
The polymerizable monomer (b1) includes cyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl ( meth) acrylate, and one or more monomers selected from the group consisting of dicyclopentanyl (meth) acrylate,
The polymerizable monomer (b2) is 2-[(meth)acryloyloxy]ethyltrimethylammonium chloride, 3-[(meth)acryloyloxy]propyltrimethylammonium chloride, 2-[(meth)acryloyloxy]ethyltrimethyl ammonium bromide, 3-[(meth)acryloyloxy]propyltrimethylammonium bromide, 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) ) one or more monomers selected from the group consisting of acryloyloxy]propyltrimethylammonium methylsulfate, dimethylaminoethyl(meth)acrylamide methyl chloride quaternary salt, and dimethylaminopropyl(meth)acrylamide methyl chloride quaternary salt is the body,
The compound (C) is 2-[(meth)acryloyloxy]ethyltrimethylammonium chloride, 3-[(meth)acryloyloxy]propyltrimethylammonium chloride, dimethylaminoethyl(meth)acrylamide methyl chloride quaternary salt, and dimethyl One or more compounds selected from the group consisting of aminopropyl (meth)acrylamide methyl chloride quaternary salts,
An active energy ray-curable composition, wherein the mass ratio [(B)/(C)] of the resin (B) and the compound (C) is in the range of 5/95 to 40/60. 2. The active energy ray-curable composition according to claim 1 , wherein the resin (B) has a weight average molecular weight in the range of 1,000 to 100,000. 3. The active energy ray-curable composition according to claim 1, wherein said compound (C) has a weight average molecular weight in the range of 100 to 1,000. Any one of claims 1 to 3 , wherein the total amount of the resin (B) and the compound (C) is in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the active energy ray-curable compound (A). 1. The active energy ray-curable composition according to claim 1. The active energy ray-curable composition according to any one of claims 1 to 4 , wherein the active energy ray-curable compound (A) has a hydroxyl value of 40 mgKOH/g or less. A cured product of the active energy ray-curable composition according to any one of claims 1 to 5 . A film comprising a cured coating film of the active energy ray-curable composition according to any one of claims 1 to 6 .