Active energy ray-curable composition and antistatic film

Information

  • Patent Grant
  • 9914788
  • Patent Number
    9,914,788
  • Date Filed
    Friday, March 24, 2017
    7 years ago
  • Date Issued
    Tuesday, March 13, 2018
    6 years ago
  • Inventors
    • Yamashita; Masako
  • Original Assignees
  • Examiners
    • Whiteley; Jessica
    Agents
    • Sughrue Mion, PLLC
Abstract
Provided are an active energy ray-curable composition that has good antistatic properties, scratch resistance, and transparency after curing, and an antistatic film using the same. The active energy ray-curable composition of the present invention is an active energy ray-curable composition, including a photopolymerization initiator A represented by the following Formula (I) and an antistatic compound B,
Description
BACKGROUND OF THE INVENTION

1. Field of the Invention


The present invention relates to an active energy ray-curable composition and an antistatic film.


2. Description of the Related Art


Generally, resin materials exhibit excellent electrical insulating properties and are therefore very useful for applications requiring electrical insulating properties such as insulators, but surfaces thereof are easily charged with static electricity, which is thus likely to result in dust adsorption and electrostatic troubles.


To solve such problems, it is known to use various antistatic agents (in particular, cationic antistatic agents).


For example, JP2011-12240A discloses an “antistatic agent including a quaternary cationic (meth)acrylamide-based monomer represented by General Formula (1) (in the formula, R1 represents a hydrogen atom or a methyl group, R2 and R3 each independently represent an alkyl group having 1 to 3 carbon atoms and may be same as or different from each other, R4 represents an alkyl group having 1 to 3 carbon atoms or a benzyl group, A represents an alkylene group having 1 to 3 carbon atoms, and X represents an anion) which is an onium salt including ammonium as a positive ion, and at least one ion selected from alkyl sulfonic acid having 1 to 20 carbon atoms, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethane sulfonic acid as a negative ion” ([claim 1]), and also discloses that a photoinitiator to be added when the quaternary cationic (meth)acrylamide-based monomer is photo-cured “may be appropriately selected from common photoinitiators such as an acetophenone-based photoinitiator, a benzoin-based photoinitiator, a benzophenone-based photoinitiator, and a thioxanthone-based photoinitiator” ([0045]).




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SUMMARY OF THE INVENTION

The present inventors have studied the antistatic agent described in JP2011-12240A and have found that, depending on the type and combination of monomers and photoinitiators to be used, there is a case where antistatic properties may be poor and there is also a case where scratch resistance and transparency may be inferior.


Accordingly, an object of the present invention is to provide an active energy ray-curable composition that has good antistatic properties, scratch resistance, and transparency after curing, and an antistatic film using the same.


As a result of extensive studies to achieve the above-mentioned object, the present inventors have found that a composition containing a polymerizable compound being capable of forming a polymer having antistatic properties and, together with a photopolymerization initiator having a specific structure, becomes good in all of antistatic properties, scratch resistance, and transparency after curing. The present invention has been completed based on such a finding.


That is, it has been found that it is possible to achieve the foregoing object by the following configurations.


[1] An active energy ray-curable composition, comprising: a photopolymerization initiator A represented by Formula (I) to be described hereinafter; and an antistatic compound B.


[2] The active energy ray-curable composition according to [1], in which the antistatic compound B is at least one polymerizable compound selected from the group consisting of compounds represented by Formulae (1) to (5) to be described hereinafter.


[3] The active energy ray-curable composition according to [1] or [2], further comprising: a polymerizable compound C which is different from the antistatic compound B and contains an ethylenically unsaturated group.


[4] The active energy ray-curable composition according to [2] or [3], in which the antistatic compound B is a cationic polymerizable compound represented by Formula (1) to be described hereinafter.


[5] The active energy ray-curable composition according to any one of [2] to [4], in which the antistatic compound B is a cationic polymerizable compound represented by Formula (1) to be described hereinafter and is an ammonium salt represented by the Formula (6) to be described hereinafter.


[6] The active energy ray-curable composition according to any one of [3] to [5], in which the polymerizable compound C is a methacrylic or acrylic compound.


[7] The active energy ray-curable composition according to [6], in which the polymerizable compound C is a polymerizable compound C-1 represented by the following Formula (7)


[8] The active energy ray-curable composition according to [6], in which the polymerizable compound C is a polymerizable compound C-2 having a hydrophilic group.


[9] The active energy ray-curable composition according to [8], in which the hydrophilic group is a hydroxy group or a carboxyl group.


[10] The active energy ray-curable composition according to any one of [1] to [9], in which the content of the photopolymerization initiator A is 0.5 to 10 parts by mass with respect to 100 parts by mass of the total polymerizable compound contained in the composition.


[11] The active energy ray-curable composition according to [10], in which the content of the antistatic compound B is 10 to 60 parts by mass with respect to 100 parts by mass of the total polymerizable compound contained in the composition.


[12] The active energy ray-curable composition according to [11], in which the content of the polymerizable compound C-1 is 10 to 50 parts by mass with respect to 100 parts by mass of the total polymerizable compound contained in the composition.


[13] The active energy ray-curable composition according to [11], in which the content of the polymerizable compound C-2 is 5 to 20 parts by mass with respect to 100 parts by mass of the total polymerizable compound contained in the composition.


[14] The active energy ray-curable composition according to any one of [1] to [13], in which the photopolymerization initiator A has n of 1 in Formula (I).


[15] The active energy ray-curable composition according to any one of [1] to [14], which is used in an antistatic agent.


[16] An antistatic film comprising an antistatic layer formed by applying the active energy ray-curable composition according to any one of [1] to [15] onto a substrate and curing the applied composition by active energy rays.


According to the present invention, it is possible to provide an active energy ray-curable composition that has good antistatic properties, scratch resistance, and transparency after curing, and an antistatic film using the same.







DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, the present invention will be described in detail.


The description of constituent features given below is often made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.


Further, the numerical value ranges shown with “to” in the present specification means ranges including the numerical values indicated before and after “to” as the lower limit and the upper limit, respectively.


[Active Energy Ray-Curable Composition]


The active energy ray-curable composition of the present invention (hereinafter, also referred to as the “composition of the present invention”) is an active energy ray-curable composition containing a photopolymerization initiator A represented by Formula (1) to be described hereinafter, and an antistatic compound B.


By including a photopolymerization initiator A and an antistatic compound B, the composition of the present invention becomes good in all of antistatic properties, scratch resistance, and transparency after curing.


The reason why all of antistatic properties, scratch resistance, and transparency become good is not clear in detail, but it is approximately thought that the following is true.


First, it is considered that due to the presence of the ethylene oxide structure (hereinafter, also referred to as “EO chain”) represented by the predetermined number n of repeating units, in the structure of the photopolymerization initiator A represented by the following Formula (1), the EO chain remains as a residue even after an active species is generated by active energy rays.


Then, the residue has a surface activating ability, and thus the antistatic compound B or the polymer of the antistatic compound B can be localized on a surface, whereby antistatic properties and scratch resistance become good.


Further, it is considered that by including the EO chain in the photopolymerization initiator A, compatibility of the photopolymerization initiator A and the antistatic compound B is increased, and as a result, it is possible to not only localize the antistatic compound B or the polymer of the antistatic compound B on the surface but also to uniformly disperse the antistatic compound B or the polymer of the antistatic compound B in the cured product, so transparency becomes good.


It can be assumed from the fact that the effect is not exhibited in the photopolymerization initiator (Irgacure 2959, see the following structural formula) which does not have the EO chain and used in Comparative Example 1.




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Further, it was found that, by incorporation of the photopolymerization initiator A and the antistatic compound B, surprisingly, the composition of the present invention also becomes good in antistatic properties under a low humidity environment, and a change (deterioration) in the antistatic properties was not observed even after a thermocycle test.


This can be considered that antistatic properties become good even under a low humidity environment, because the residue containing the above-mentioned EO chains derived from the photopolymerization initiator A not only has a surface activating ability, but also contributes to moisture-retaining properties.


Further, it is considered that, as described above, the compatibility of the photopolymerization initiator A and the antistatic compound B is increased and, as a result, the unreacted antistatic compound B can be uniformly dispersed in the cured product, consequently aggregation of the unreacted polymerizable compound can be suppressed, whereby deterioration in the antistatic properties was not observed even after a thermocycle test.


Hereinafter, the photopolymerization initiator A and the antistatic compound B, and an arbitrary polymerizable compound C contained in the composition of the present invention will be described in detail.


[Photopolymerization Initiator A]


The photopolymerization initiator A contained in the composition of the present invention is a photopolymerization initiator represented by the following Formula (I).




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In Formula (I), V1, V2, V3, and V4 each independently represent a hydrogen atom or a substituent, and n represents an integer of 1 to 5.


In the present invention, when n in Formula (I) is an integer of 1 to 5, the function by the action of the above-mentioned EO chain is expressed, and therefore antistatic properties, scratch resistance, and transparency after curing become good.


In terms of that these effects are further improved, n in Formula (1) is preferably an integer of 1 to 3, more preferably an integer of 1 or 2, and still more preferably 1.


In V1 to V4, examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, an alkylthio group, a mercapto group, an acyl group, and an amino group.


In V1 to V4, the halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.


In V1 to V4, the number of carbon atoms in the alkyl group is preferably 1 to 6 and more preferably 1 to 3.


In V1 to V4, the alkyl group may be a linear alkyl group or a branched alkyl group. Further, the alkyl group may have an alicyclic structure.


Examples of the alkyl group in V1 to V4 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, and a cyclohexyl group. Preferred is a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.


In V1 to V4, the number of carbon atoms in the alkoxy group is preferably 1 to 6 and more preferably 1 to 3.


In V1 to V4, the alkoxy group may be a linear alkoxy group or a branched alkoxy group. Further, the alkoxy group may have an alicyclic structure.


Examples of the alkoxy group in V1 to V4 include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentyloxy group, an n-hexyloxy group, and a cyclohexyloxy group. Preferred is a methoxy group, an ethoxy group, an n-propyloxy group, or an isopropyloxy group.


In V1 to V4, the number of carbon atoms in the alkylthio group is preferably 1 to 6 and more preferably 1 to 4.


In V1 to V4, the alkylthio group may be a linear alkylthio group or a branched alkylthio group. Further, an alkylthio group may have an alicyclic structure.


Examples of the alkylthio group in V1 to V4 include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, a sec-butylthio group, a tert-butylthio group, an n-pentylthio group, an n-hexylthio group, and a cyclohexyloxy group. Preferred is a methylthio group, an ethylthio group, an n-propylthio group, or an isopropylthio group.


In V1 to V4, the number of carbon atoms in the acyl group is preferably 1 to 6 and more preferably 1 to 3.


In V1 to V4, the acyl group may be a linear acyl group or a branched acyl group.


Examples of the acyl group in V1 to V4 include a formyl group, an acetyl group, an ethylacyl group, an n-propylacyl group, and an isopropylacyl group. Preferred is a formyl group, an acetyl group, or an ethylacyl group.


V1 to V4 are preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an alkylthio group, more preferably a hydrogen atom, an alkoxy group, or an alkylthio group, and most preferably a hydrogen atom.


Further, a more preferred form of the compound represented by Formula (I) may be, for example, a form in which two or more (preferably three or more, and most preferably four) of V1 to V4 are a hydrogen atom.


Specific examples of the compound represented by Formula (I) (exemplary compounds) are shown below, but the compound represented by Formula (I) is not limited thereto.









TABLE 1







(I)








              Exem- plary com-


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pounds
n
V1
V2
V3
V4





(I)-1 
1
H
H
H
H


(I)-2 
2
H
H
H
H


(I)-3 
3
H
H
H
H


(I)-4 
5
H
H
H
H


(I)-5 
1
CH3
H
H
H


(I)-6 
1
H
CH3
H
H


(I)-7 
1
H
OCH3
H
H


(I)-8 
1
H
Cl
H
H


(I)-9 
1
H
Br
H
H


(I)-10
1
H
OH
H
H


(I)-11
1
Cl
Cl
H
H


(I)-12
1
SCH3
H
H
H


(I)-13
2
Cl
H
Cl
H


(I)-14
2
H
CH3
H
H


(I)-15
2
H
N(CH3)2
Cl
H


(I)-16
2
CH3
CH3
H
H


(I)-17
3
H
OH
H
H


(I)-18
3
H
CH3
H
H


(I)-19
5
H
COCH3
H
H


(I)-20
5
H
CH3
H
H









The compound (polymerization initiator) represented by Formula (I) can be synthesized in accordance with the method described, for example, in paragraphs [0067] to [0071] and [0112] to [0115] of JP2000-186242A.


In the present invention, the content of the photopolymerization initiator A is preferably 0.5 to 10 parts by mass and more preferably 1 to 8 parts by mass with respect to 100 parts by mass of the total polymerizable compound contained in the composition, from the viewpoint of curability, moisture-retaining properties under a low humidity environment, and dispersibility of the unreacted antistatic compound B.


As used herein, the term “100 parts by mass of the total polymerizable compound” refers to 100 parts by mass of total of the antistatic compound B to be described hereinafter and the arbitrary polymerizable compound C to be described hereinafter.


Further, in the present invention, other initiators may be used in combination in addition to the above-mentioned photopolymerization initiator A.


Examples of other initiators include photo-radical polymerization initiators. Specifically, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used.


More specifically, for example, aminoacetophenone-based initiators described in JP1998-291969A (JP-H10-291969A), and acylphosphine oxide-based initiators described in JP4225898B may also be used.


Commercially available products IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (trade names, all manufactured by BASF Corporation) may be used as the hydroxyacetophenone-based initiator. Commercially available products IRGACURE-907, IRGACURE-369 and IRGACURE-379 (trade names, all manufactured by BASF Corporation) may be used as the aminoacetophenone-based initiator. The compounds described in JP2009-191179A, whose absorption wavelength is matched to a light source having a long wavelength such as 365 nm or 405 nm, may also be used as the aminoacetophenone-based initiator. Commercially available products IRGACURE-819 and DAROCUR-TPO (trade names, both manufactured by BASF Corporation) may be used as the acylphosphine-based initiator.


[Antistatic Compound B]


The antistatic compound B contained in the composition of the present invention may be a polymerizable compound being capable of forming a conventionally known polymer having antistatic properties.


In the present invention, in terms of that antistatic properties after curing become better and reactivity with the photopolymerization initiator A becomes good, the antistatic compound B is preferably at least one polymerizable compound selected from the group consisting of compounds represented by the following Formulae (1) to (5).




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In Formulae (1) to (5), R1's each independently represent a hydrogen atom, a halogen atom, a cyano group, a monovalent hydrocarbon group, —COO—C2, or —COO—C2 bonded through a hydrocarbon, and C2 represents a hydrogen atom or a hydrocarbon group which may have a substituent.


In Formulae (1) to (5), Z's each independently represent —COO—, —CONH—, —OCO—, —CH2OCO—, —CH2COO—, —O—, —SO2—, —CO—, —CONHCOO—, —CONHCONH—, —CONHSO2—, —CON(P3)—, —SO2N(G)-, —C6H4—, or an alkylene group having 1 to 30 carbon atoms, and G represents a hydrogen atom or a hydrocarbon group.


In Formulae (1) to (5), A′s each independently represent a single bond or a divalent or higher valent linking group, and j's each independently represent an integer of 0 to 30.


In Formula (1), Y+ represents a cationic group, X represents an anionic group, u represents an integer of 1 to 3, and r represents an integer of 1 to 4.


In Formula (2), R2 represents an alkylene group having 2 to 5 carbon atoms which may have a substituent, R3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent, and m represents an integer of 2 to 200.


In Formula (3), Q+ represents an ammonium cation, a sulfonium cation, an iodonium cation, a phosphonium cation, or a pyridinium cation, L1 represents a single bond or a divalent or higher valent linking group, T represents COO, SO3 or OPO(O)(ORp), and Rp represents an alkyl group. p represents an integer of 1 to 3.


In Formula (4), L2 represents a single bond or a divalent or higher valent linking group, U+ represents an ammonium or phosphonium cation which may have a substituent, and q represents an integer of 1 to 3.


In Formula (5), J represents COO, OPO(OH)O or SO3, V+ represents a cationic group, and w represents an integer of 1 to 3.


Here, R1 in Formulae (1) to (5) is preferably a hydrogen atom or a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include alkyl groups having 1 to 10 carbon atoms. Among them, preferred is a methyl group.


Z in Formulae (1) to (5) is preferably —COO—, —CONH—, or an alkylene group having 1 to 30 carbon atoms. Examples of the alkylene group having 1 to 30 carbon atoms include a methylene group, an ethylene group, and a propylene group. Among them, preferred is a methylene group.


A in Formulae (1) to (5) is preferably a single bond or a divalent linking group. Examples of the divalent linking group include alkylene groups having 1 to 10 carbon atoms. Among them, preferred is an ethylene group or a propylene group.


Y+ (cationic group) in Formula (1) is preferably an ammonium cation. Examples of X (anionic group) include Cl, Br, I, SO3, NCS, ROSO3, ROSO2, RSO3, R—C6H4—SO3, (RO)2PO2, R4B (in which R represents an alkyl group which may have a substituent, an alicyclic alkyl group, or an aromatic group), (CF3SO2)2N, and (SO2C2F5)2N.


R2 in Formula (2) is preferably an ethylene group, R3 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and m is preferably an integer of 2 to 30.


Q+ in Formula (3) is preferably an ammonium cation. L1 is preferably a single bond or a divalent linking group. Examples of the divalent linking group include alkylene groups having 1 to 10 carbon atoms. Among them, preferred is a methylene group, an ethylene group, a propylene group or a butylene group. T is preferably COO or SO3.


L2 in Formula (4) is preferably a single bond or a divalent linking group. Examples of the divalent linking group include alkylene groups having 1 to 10 carbon atoms. Among them, preferred is a methylene group, an ethylene group, a propylene group or a butylene group. U+ is preferably an ammonium cation.


J in Formula (5) is preferably SO3. Examples of the cationic group of V+ include Na+, K+, a quaternary ammonium cation, and a pyridinium cation.


In the present invention, in terms of that antistatic properties after curing become better and compatibility with the photopolymerization initiator A becomes better, the antistatic compound B is preferably a cationic polymerizable compound represented by Formula (1) among compounds represented by Formulae (1) to (5), and is more preferably an ammonium salt represented by the following Formula (6).




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In Formula (6), R1 and A each have the same definition of R1 and A in Formula (1).


Z represents —COO—, —CONH—, or —CH2—, and j represents an integer of 0 to 10.


L3, L4, and L5 each independently represent an alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group having 1 to 20 carbon atoms which may have a substituent, and at least two of L3, L4, and L5 may be bonded to each other to form a ring.


Specific examples of polymerizable compounds represented by Formulae (1) and (6) include (B)-a1-1 to (B)-a1-11 shown below.




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Specific examples of polymerizable compounds represented by Formula (2) include (B)-a2-1 to (B)-a2-3 shown below.




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Specific examples of polymerizable compounds represented by Formula (3) include (B)-a3-1 to (B)-a3-7 shown below.




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Specific examples of polymerizable compounds represented by Formula (4) include (B)-a4-1 to (B)-a4-2 shown below.




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Specific examples of polymerizable compounds represented by Formula (5) include (B)-a5-1 shown below.




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In the present invention, the content of the antistatic compound B is preferably 10 to 60 parts by mass and more preferably 15 to 50 parts by mass with respect to 100 parts by mass of the total polymerizable compound contained in the composition, in terms of that antistatic properties after curing become better.


[Polymerizable Compound C]


It is preferable that the composition of the present invention includes a polymerizable compound C which is different from the antistatic compound B and contains an ethylenically unsaturated group, in terms of that scratch resistance after curing become better and aggregation of the unreacted antistatic compound B can be suppressed.


Specific examples of the ethylenically unsaturated group include polymerizable functional groups such as a (meth)acryloyl group, a vinyl group, a styryl group, and an allyl group.


As used herein, the term “(meth)acryloyl group” is notation of a concept that includes a methacryloyl group or an acryloyl group, and the same concept will be applied to the expressions of (meth)acrylic, (meth)acrylate, and (meth)acrylic acid to be described hereinafter.


In the present invention, it is preferable that the polymerizable compound C is a methacrylic or acrylic compound (hereinafter, also referred to simply as “(meth)acrylic compound”) which includes a (meth)acryloyl group containing a methacryloyl group or an acryloyl group as an ethylenically unsaturated group, in terms of that compatibility or reactivity with the photopolymerization initiator A is high.


Examples of the (meth)acrylic compound include polyfunctional (meth)acrylate, polyfunctional (meth)acrylamide, monofunctional (meth)acrylate, and monofunctional (meth)acrylamide. These compounds may be used alone or in combination of two or more thereof.


<Polyfunctional (meth)acrylate and polyfunctional (meth)acrylamide>


Specific examples of the polyfunctional (meth)acrylate include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra (meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate [hereinafter, dipentaerythritol hexaacrylate is also referred to simply as “DPHA”], dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate. These compounds may be used alone or in combination of two or more thereof.


Specific examples of the polyfunctional (meth)acrylamide include N,N′-methylenebis(meth)acrylamide, 1,2-bis[(meth)acrylamide]ethane, 1,3-bis[(meth)acrylamide]propane, 1,6-bis[(meth)acrylamide]hexane, and polymerizable compounds 1 to 12 described in paragraph [0031] of Journal of Technical Disclosure 2013-502654. These compounds may be used alone or in combination of two or more thereof.


Further, polyfunctional (meth)acrylates and polyfunctional (meth)acrylamides may be used in combination.


<Monofunctional (meth)acrylate and monofunctional (meth)acrylamide>


Specific examples of the monofunctional (meth)acrylate include alkyl acrylates such as methyl acrylate [hereinafter, also referred to simply as “MA”], ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, and propargyl acrylate; and alkyl methacrylates such as methyl methacrylate [hereinafter, also referred to simply as “MMA”], ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate. These compounds may be used alone or in combination of two or more thereof.


Specific examples of the monofunctional (meth)acrylamide include acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, vinyl acrylamide, vinyl methacrylamide, N,N-diallyl acrylamide, N,N-diallyl methacrylamide, allyl acrylamide, allyl methacrylamide, and N-(2-acetamidoethyl)-N-(2-hydroxyethyl)acrylamide. These compounds may be used alone or in combination of two or more thereof.


Further, monofunctional (meth)acrylates and monofunctional (meth)acrylamides may be used in combination.


The polymerizable compound C other than the (meth)acrylic compounds exemplified above is preferably a polymerizable compound C-1 represented by the following Formula (7), in terms of that antistatic properties become better due to high compatibility with the photopolymerization initiator A.

CH2═C(R4)COO(AO)nR5  (7)


In Formula (7), R4 represents a hydrogen atom or CH3, R5 represents a hydrogen atom or a hydrocarbon group having 6 to 25 carbon atoms which may have a substituent, A represents an alkylene group having 2 to 5 carbon atoms which may have a substituent, and n represents an integer of 3 to 50.


Specific examples of the polymerizable compound C-1 represented by Formula (7) include (B)-b-1 to (B)-b-5 shown below.




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The polymerizable compound C other than the (meth)acrylic compounds exemplified above is preferably a polymerizable compound C-2 having a hydrophilic group, in terms of that antistatic properties become better due to high compatibility with the photopolymerization initiator A.


Examples of the hydrophilic group include a hydroxy group and a carboxyl group. Among them, preferred is a hydroxy group.


The polymerizable compound C-2 having a hydroxy group is preferably a compound represented by the following Formula (8).

CH2═C(R6)COO(BO)H  (8)


In Formula (8), R6 represents a hydrogen atom or CH3, and B represents an alkylene group having 2 to 5 carbon atoms which may be branched.


Among compounds represented by Formula (8), the alkylene group indicated by B is preferably an ethylene group, in terms of that compatibility with the photopolymerization initiator A is high and antistatic properties become better, thus the antistatic properties being less likely to deteriorate even after a thermocycle test.


Specific examples of the compound represented by Formula (8) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate [hereinafter, also referred to simply as “HEMA”], 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropyl methacrylate [hereinafter, also referred to simply as “HPMA”], 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate. These compounds may be used alone or in combination of two or more thereof.


In the present invention, in a case where the polymerizable compound C is contained, the polymerizable compound C-1 represented by Formula (7) and the polymerizable compound C-2 having a hydrophilic group are preferably used in combination, in terms of that antistatic properties become better.


In the present invention, in a case where the polymerizable compound C is contained, the content thereof is preferably 5 to 90 parts by mass and more preferably 40 to 90 parts by mass with respect to 100 parts by mass of the total polymerizable compound contained in the composition.


In particularly, in a case where the polymerizable compound C-1 represented by Formula (7) is contained as the polymerizable compound C, the content thereof is preferably 10 to 50 parts by mass with respect to 100 parts by mass of the total polymerizable compound contained in the composition.


Further, in a case where the polymerizable compound C-2 having a hydrophilic group is contained as the polymerizable compound C, the content thereof is preferably 5 to 20 parts by mass with respect to 100 parts by mass of the total polymerizable compound contained in the composition.


The composition of the present invention may contain a solvent, if necessary.


Examples of the solvent to be used include water, an organic solvent and a mixed solvent thereof.


Specific examples of the organic solvent include alcohols such as methanol and isopropyl alcohol (hereinafter, also referred to simply as “IPA”); ketones such as acetone; amides such as formamide; sulfoxides such as dimethyl sulfoxide; esters such as ethyl acetate; and ethers.


Depending on the intended use, the composition of the present invention may contain other optional components such as a pigment, a dye, a surfactant, an anti-blocking agent, a binder, a crosslinking agent, an antioxidant, and an ultraviolet absorber which may be used in combination.


[Antistatic Film]


The antistatic film of the present invention is an antistatic film which has an antistatic layer formed by applying the composition of the present invention onto a substrate, and curing the applied composition by active energy rays.


[Substrate]


The substrate in the antistatic film of the present invention is preferably a substrate formed of a material having good transparency. Specific examples of the material for a substrate include polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, nylon 6, nylon 66, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, cellophane, polystyrene, polyarylate, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polymethyl terpene, polyether sulfone, polymethyl methacrylate, polyvinyl alcohol, polyimide, and polycycloolefin.


[Antistatic Layer]


The method of applying the composition of the present invention onto a substrate is not particularly limited, and example thereof include coating methods such as by a gravure coater, a comma coater, a bar coater, a knife coater, a die coater, and a roll coater.


After applying the composition of the present invention onto a substrate to form a coating film, a drying process may be carried out, if necessary, prior to carrying out a curing process to be described hereinafter. By carrying out the drying process, it is possible to remove volatile components (such as a solvent) contained in the coating film. The method of drying process is not particularly limited, and examples thereof include a method of carrying out a heat treatment at a temperature (for example, 60° C. to 100° C.) at which the polymerization of a polymerizable compound does not proceed, and a method of carrying out an air-drying process.


The method of applying the composition of the present invention onto a substrate to form a coating film and then curing the coating film by active energy rays is not particularly limited.


As used herein, the ten “active energy rays” refers to energy rays capable of generating an active species by decomposing a compound (photopolymerization initiator A) which generates the active species. Examples of such active energy rays include light rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays; electromagnetic waves such as X-rays and γ-rays; an electron beams, proton beams, and neutron rays. From the viewpoint of a curing rate, easy availability of an irradiation device, and costs, ultraviolet rays are preferable.


UV irradiation can be carried out using a high-pressure mercury lamp, ultra-high pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp, electrodeless discharge lamp, ultraviolet LED or the like which emits light of a 150 to 450 nm wavelength range.


Further, the illuminance of light irradiation performed on a coating film is not particularly limited, but it is preferably 0.1 to 1,000 mW/cm2 and more preferably 1 to 800 mW/cm2 from the viewpoint of the balance of properties and productivity of the resulting antistatic film.


The exposure dose at the time of light irradiation is not particularly limited, but it is preferably 2,000 mJ/cm2 or less, more preferably 1,750 mJ/cm2 or less, and still more preferably 1,500 mJ/cm2 or less from the viewpoint of the balance of properties and productivity of the resulting antistatic film. The lower limit is not particularly limited, but it is preferably 500 mJ/cm2 or more from the viewpoint of properties of an antistatic film.


The atmosphere at the time of light irradiation is not particularly limited and may be in the air or under an inert gas atmosphere.


The thickness of the antistatic layer formed using the composition of the present invention is preferably 0.01 to 100 μm and more preferably 0.05 to 50 μm.


The hardness of the antistatic layer is preferably HB or more and more preferably H or more, as determined by a pencil hardness test.


The common logarithmic value (Log SR) of the surface resistivity SR(Ω/sq) of the antistatic layer is preferably 13 or less and more preferably 12 or less.


Here, the surface resistivity represents a value measured at 25° C. and 60% relative humidity.


EXAMPLES

The present invention will be described in more detail with reference to the following Examples. Materials, used amounts, ratios, processing contents, processing procedures and the like shown in the following Examples may be appropriately changed without departing from the scope and sprit of the present invention. Accordingly, the scope of the present invention should not be limitatively interpreted by the following Examples.


[Synthesis of Polymerization Initiator]


<Synthesis of Intermediate (2)-1>


97.2 g (0.95 mol) of an acetic anhydride was added dropwise to 170.0 g (0.93 mol) of phenyl diglycol (PhDG, manufactured by Nippon Nyukazai Co., Ltd.) heated to 90° C., followed by stirring under heating at 120° C. for 6 hours. Then, the reaction mixture was concentrated under reduced pressure to give 204.4 g (yield: 98%) of Intermediate (2)-1. The structure of the resulting Intermediate (2)-1 was determined using a nuclear magnetic resonance apparatus (solvent used: CDCl3) and was therefore identified as a compound of the following Formula (2)-1. The measurement data of 1H-NMR is shown below.




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1H-NMR(CDCl3)


δ: 2.10 (3H, s), 3.78 (2H, m), 3.87 (2H, m), 4.15 (2H, 4.26 (2H, m), 6.90-6.98 (3H, m), 7.25-7.32 (2H, m).


<Synthesis of Intermediate (3)-1>


120.0 g (0.90 mol) of aluminum chloride (III) was added to 270 mL (2.39 mol) of o-dichlorobenzene and the mixture was cooled to 0° C. 44.26 mL (0.36 mol) of 2-bromoisobutyryl bromide was added dropwise thereto, followed by stirring for 15 minutes. Thereafter, 67.28 g (0.30 mol) of Intermediate (2)-1 was added dropwise over 30 minutes, while maintaining the temperature of the reaction liquid at 0° C. The reaction liquid after the dropwise addition was allowed to return to room temperature (22° C.) and stirred for 2 hours. Then, the reaction liquid was added in several divided portions to 300 mL of water cooled to 5° C. The organic phase was washed twice with 300 mL of water, 135 mL of sodium bicarbonate water, and then 135 mL of saturated saline. 300 mL of water was added to the organic phase, followed by azeotropic concentration under reduced pressure to give 110.8 g (yield: 95%) of Intermediate (3)-1. The structure of the resulting Intermediate (3)-1 was determined using a nuclear magnetic resonance apparatus (solvent used: CDCl3) and was therefore identified as a compound of the following Formula (3)-1. The measurement data of 1H-NMR is shown below.




embedded image



1H-NMR(CDCl3)


δ: 2.04 (6H, s), 2.08 (3H, s), 3.79 (2H, m), 3.85 (2H, m), 4.21 (2H, m), 4.26 (2H, 6.94 (2H, d), 8.21 (2H, d).


<Synthesis of Photopolymerization Initiator A: Compound (1)-1>


100.0 g (0.27 mol) of Compound (3)-1 was dissolved in 200 mL of isopropyl alcohol to which 214 g of a 25 mass % sodium hydroxide aqueous solution was then added dropwise, followed by stirring for 2 hours. Thereafter, stirring was stopped, and the organic phase was washed twice with saturated saline and then neutralized with hydrochloric acid. The organic phase was concentrated under reduced pressure, 72 mL of methyl ethyl ketone was added thereto, and the precipitated salt was filtered. After the filtrate was concentrated under reduced pressure, 72 mL of water was added, and azeotropic concentration under reduced pressure was carried out to give 56.8 g (yield: 87%) of Compound (I)-1.




embedded image



1H-NMR(CDCl3)


δ: 1.64 (6H, s), 3.69 (2H, m), 3.78 (2H, m), 3.91 (2H, 4.22 (2H, m), 4.26 (1H, s), 6.97 (2H, d), 8.06 (2H, d).


[Synthesis of Other Photopolymerization Initiators]


As the compound represented by Formula (I), a compound represented by the following Formula (I)-2, a compound represented by the following Formula (I)-4, and a compound represented by Formula (IB) were synthesized with reference to the above-mentioned procedure.


Further, as shown in Table 5 to be described hereinafter, a commercially available product “Irgacure 2959” (Irg2959) (trade name, manufactured by BASF Corporation) was used as the compound used in Comparative Examples. As shown in the following formula, Irg2959 corresponds to a compound of n=0 in Formula (I).




embedded image


Examples 1 to 24 and Comparative Examples 1 to 3

(Preparation of Active Energy Ray-Curable Composition)


The components shown in Tables 2 to 5 were mixed in blending amounts (parts by mass) shown in Tables 2 to 5 and stirred to obtain compositions.


In Tables 2 to 5, “DPHA” represents dipentaerythritol hexaacrylate, “HEMA” represents 2-hydroxyethyl methacrylate, “HPMA” represents 2-hydroxypropyl methacrylate, and “MAA” represents methacrylic acid.


<Preparation of Antistatic Film>


Each of the prepared compositions was applied onto a polyethylene terephthalate film (Cosmo Shine A4100 manufactured by Toyobo Co., Ltd.) using a bar coater, the solvent was removed in a hot air oven, ultraviolet rays were irradiated for 10 seconds by a high-pressure mercury lamp having an output of 80 W/cm, and the coating layer (thickness: 5 μm) was cured to prepare an antistatic film.


The thus-prepared antistatic film was cut into a size of width 100 mm×length 100 mm with a cutter and the resulting sample was evaluated according to the following evaluation method. The results are shown in Tables 2 to 5 below.


(Antistatic Properties)


The antistatic properties were evaluated by allowing the cut sample to stand for 24 hours under an atmosphere of 25° C. and 40% relative humidity, and applying an applied voltage of 100 V to the sample under conditions of 25° C. and 40% relative humidity and then measuring surface resistivity (Ω/□) after 1 minute using a surface electrical resistance meter (SME-8310, Toa Electronics Co., Ltd).


In addition, the antistatic properties under low humidity were evaluated by allowing the sample to stand for 24 hours under an atmosphere of 25° C. and 15% relative humidity and measuring surface resistivity (Ω/□) in the same manner as described above.


The antistatic properties were evaluated on a 6-point scale according to the following evaluation standards. The article with a grade of D or higher can be used without any practical problem.


A: Superior (surface electrical resistance value of less than 109 Ω/area)


B: Excellent (surface electrical resistance value of 109 Ω/area or more and less than 1010 Ω/area)


C: Good (surface electrical resistance value of 1010 Ω/area or more and less than 1011 Ω/area)


D: Moderate (surface electrical resistance value of 1011 Ω/area or more and less than 1012 Ω/area)


E: Slightly bad (surface electrical resistance value of 1012 Ω/area or more and less than 1013 Ω/area)


F: Bad (surface electrical resistance value of 1013 Ω/area or more)


(Variation in Antistatic Properties after Thermocycles)


After carrying out a thermocycle test of 20 cycles each consisting of temperature changes (20° C. for 50 hours under 45% relative humidity atmosphere→−20° C. for 50 hours under 20% relative humidity atmosphere 50° C. for 50 hours under 85% relative humidity atmosphere) as one cycle, the surface resistivity (Ω/□) was measured in the same manner as described above. From the values of surface resistivity before and after the therinocycle test, a variation was calculated according to the following equation.


Variation=(surface electrical resistance value after test)/(surface electrical resistance value before test)


(Scratch Resistance)


The presence or absence of occurrence of scratches on the surface was evaluated by reciprocating #0000 steel wool under a load of 200 g/cm2 10 times on the entire surface of the layer having an antistatic film.


A: No scratch is visible even with very careful watching.


B: Slightly weak scratch is visible with very careful watching.


C: Weak scratch is visible on part of sample.


D: Streaky scratch is found over entire surface of coating film.


E: Peeling of coating film occurs.


(Transparency)


The transparency was evaluated in terms of haze (%). The measurement of haze was carried out using a haze meter “NDH 5000” manufactured by Nippon Denshoku Industries Co., Ltd., after 3-week storage of individual antistatic films obtained in Examples and Comparative Examples under the condition of −20° C. In addition, a polyethylene terephthalate film having no antistatic film was subjected to the same measurement and taken as blank.


A: Less than 0.5%


B: 0.5% or more











TABLE 2









Examples



















1
2
3
4
5
6
7
8
9





Polymerizable
(B)-a1-1
100
40
10
60
40
40
40
40
40


compound B
(B)-a1-2



(B)-a1-11


Polymerizable
DPHA

60
90
40
35
50
10
25
20


compound C
(B)-b-1




25
10
50
25
25



HEMA







10
5



HPMA



MAA


Solvent
IPA
300
300
300
300
300
300
300
300
300


Photopolymerization
(I)-1
5
5
5
5
5
5
5
5
5


initiator A
(I)-2



(I)-4
















Antistatic properties
B
B
B
B
B
B
B
A
A


Antistatic properties under low
C
C
C
C
C
C
C
B
B


humidity environment


Variation in antistatic properties
0.65
0.73
0.7
0.68
0.81
0.79
0.75
0.91
0.87


after thermocycles


Scratch resistance
B
A
A
A
A
A
A
A
A


Transparency
A
A
A
A
A
A
A
A
A












Examples



















10
11
12
13
14
15
16
17
18





Polymerizable
(B)-a1-1
40
40
40


100
100
100
100


compound B
(B)-a1-2



100



(B)-a1-11




100


Polymerizable
DPHA
15
25
25


compound C
(B)-b-1
25
25
25



HEMA
20



HPMA

10



MAA


10


Solvent
IPA
300
300
300
300
300
300
300
300
300


Photopolymerization
(I)-1
5
5
5
5
5
1
10


initiator A
(I)-2







5



(I)-4








5
















Antistatic properties
A
A
A
B
B
C
B
C
C


Antistatic properties under low
B
B
B
C
D
D
C
D
D


humidity environment


Variation in antistatic properties
0.85
0.9
0.88
0.63
0.58
0.54
0.51
0.63
0.55


after thermocycles


Scratch resistance
A
A
A
B
B
C
C
C
C


Transparency
A
A
A
A
A
A
A
A
A


















TABLE 3









Examples











19
20
21















Polymerizable compound B
(B)-a3-1
100





(B)-a3-2

100



(B)-a3-3


100


Polymerizable compound C
DPHA



(B)-b-1



HEMA



HPMA



MAA


Solvent
IPA
300
300
300


Photopolymerization
(I)-1
5
5
5


initiator A
(I)-2



(I)-4










Antistatic properties
B
B
B


Antistatic properties under low humidity
D
D
D


environment


Variation in antistatic properties after
0.54
0.53
0.52


thermocycles


Scratch resistance
B
B
B


Transparency
A
A
A


















TABLE 4









Examples











22
23
24















Polymerizable compound B
(B)-a2-1
100





(B)-a2-2

100



(B)-a2-3


100


Polymerizable compound C
DPHA



(B)-b-1



HEMA



HPMA



MAA


Solvent
IPA
300
300
300


Photopolymerization
(I)-1
5
5
5


initiator A
(I)-2



(I)-4










Antistatic properties
C
C
C


Antistatic properties under low humidity
D
D
D


environment


Variation in antistatic properties after
0.64
0.63
0.62


thermocycles


Scratch resistance
C
C
C


Transparency
A
A
A


















TABLE 5









Comparative



Example











1
2
3















Polymerizable compound B
(B)-a1-1
100
100
100


Polymerizable compound C
DPHA



(B)-b-1



HEMA



HPMA



MAA


Solvent
IPA
300
300
300


Photopolymerization
Irgacure2959
5

1


initiator
(IB)

5










Antistatic properties
D
C
D


Antistatic properties under low humidity
F
E
F


environment


Variation in antistatic properties after
0.1>
0.65
0.1>


thermocycles


Scratch resistance
E
D
D


Transparency
B
A
A









From the results shown in Table 5, it was found that antistatic properties and scratch resistance were poor even when the blending amount were changed (Comparative Examples 1 and 3), in a case where a commercially available product (Irg2959 manufactured by BASF Corporation) is used as the photopolymerization initiator.


Further, it was found that antistatic properties were improved, but scratch resistance was poor (Comparative Example 2), in a case where an initiator in which n in Formula (I) corresponds to 9 was used as the photopolymerization initiator.


In contrast, as shown in Tables 2 to 4, it was found that all of antistatic properties, scratch resistance, and transparency after curing become good (Examples 1 to 24), when the photopolymerization initiator A and the antistatic compound B were blended.


Further, from the comparison of the results shown in Tables 2 to 4, it was found that antistatic properties and scratch resistance tended to become better when the antistatic compound B was a cationic polymerizable compound represented by Formula (1).


Further, from the comparison of Examples 1, 17, and 18, it was found that antistatic properties and scratch resistance tended to become better when a photopolymerization initiator in which n in Formula (I) is 1 was used as the photopolymerization initiator A.


Further, from the comparison of Examples 1 to 12, it was found that scratch resistance become better when the polymerizable compound C is contained.


Further, from the comparison of Example 2 with Examples 5 to 12, in Examples 5 to 12 in which the polymerizable compound C-1 represented by Formula (7) was used as the polymerizable compound C, it was found that antistatic properties, in particular, antistatic properties after a thermocycle test become better, and among these, in Examples 8 to 12 in which as the polymerizable compound C-2 having a hydrophilic group, HEMA (2-hydroxyethyl methacrylate) or HPMA (2-hydroxypropyl methacrylate) is used in combination with the polymerizable compound C-1, it was found that antistatic properties become better.

Claims
  • 1. An active energy ray-curable composition, comprising: a photopolymerization initiator A represented by the following Formula (I);an antistatic compound B; anda polymerizable compound C which is different from the antistatic compound B and contains an ethylenically unsaturated group,wherein the polymerizable compound C is a methacrylic or acrylic compound,the polymerizable compound C is a polymerizable compound C-1 represented by the following Formula (7) and/or a polymerizable compound C-2 having a hydrophilic group,
  • 2. The active energy ray-curable composition according to claim 1, wherein the antistatic compound B is at least one polymerizable compound selected from the group consisting of compounds represented by the following Formulae (1) to (5),
  • 3. The active energy ray-curable composition according to claim 2, wherein the antistatic compound B is a cationic polymerizable compound represented by Formula (1).
  • 4. The active energy ray-curable composition according to claim 2, wherein the antistatic compound B is a cationic polymerizable compound represented by Formula (1) and is an ammonium salt represented by the following Formula (6),
  • 5. The active energy ray-curable composition according to claim 1, wherein the hydrophilic group is a hydroxy group or a carboxyl group.
  • 6. The active energy ray-curable composition according to claim 1, wherein the content of the photopolymerization initiator A is 0.5 to 10 parts by mass with respect to 100 parts by mass of the total polymerizable compound contained in the composition.
  • 7. The active energy ray-curable composition according to claim 6, wherein the content of the antistatic compound B is 10 to 60 parts by mass with respect to 100 parts by mass of the total polymerizable compound contained in the composition.
  • 8. The active energy ray-curable composition according to claim 7, wherein the content of the polymerizable compound C-1 is 10 to 50 parts by mass with respect to 100 parts by mass of the total polymerizable compound contained in the composition.
  • 9. The active energy ray-curable composition according to claim 7, wherein the content of the polymerizable compound C-2 is 5 to 20 parts by mass with respect to 100 parts by mass of the total polymerizable compound contained in the composition.
  • 10. The active energy ray-curable composition according to claim 1, wherein the photopolymerization initiator A has n of 1 in Formula (I).
  • 11. The active energy ray-curable composition according to claim 1, which is used in an antistatic agent.
  • 12. An antistatic film comprising an antistatic layer formed by applying the active energy ray-curable composition according to claim 1 onto a substrate and curing the applied composition by active energy rays.
  • 13. An antistatic film comprising an antistatic layer formed by applying the active energy ray-curable composition according to claim 2 onto a substrate and curing the applied composition by active energy rays.
Priority Claims (1)
Number Date Country Kind
2014-198486 Sep 2014 JP national
CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of PCT International Application No. PCT/JP2015/075832 filed on Sep. 11, 2015, which claims priority under 35 U.S.C. § 119(a) to Japanese Patent Application No. 2014-198486 filed on Sep. 29, 2014. The above application is hereby expressly incorporated by reference, in its entirety, into the present application.

US Referenced Citations (2)
Number Name Date Kind
20140292966 Haijima Oct 2014 A1
20150353748 Yofu Dec 2015 A1
Foreign Referenced Citations (4)
Number Date Country
2011-012240 Jan 2011 JP
2011-012240 Jan 2011 JP
2014-198774 Oct 2014 JP
2014148290 Sep 2014 WO
Non-Patent Literature Citations (5)
Entry
Kudo et al, JP 2011-012240 Machine Translation, Jan. 20, 2011.
Written Opinion of the International Searching Authority of PCT/JP2015/075832 dated Dec. 8, 2015.
International Search Report of PCT/JP2015/075832 dated Dec. 8, 2015.
International Preliminary Report on Patentability issued from the International Bureau in counterpart International Application No. PCT/JP2015/075832, dated Apr. 13, 2017.
Office Action dated Nov. 14, 2017, issued by the Korean Intellectual Property Office in counterpart Korean Application No. 10-2017-7007109.
Related Publications (1)
Number Date Country
20170198063 A1 Jul 2017 US
Continuations (1)
Number Date Country
Parent PCT/JP2015/075832 Sep 2015 US
Child 15468413 US