Hydrophilic film, laminate, and method for producing laminate

Abstract

To provide a hydrophilic film capable of improving hydrophilicity and visibility, a laminate having the hydrophilic film, and a method for producing the laminate.SOLUTION: There is provided a hydrophilic film containing a compound (I) having a sulfonic acid group and at least one functional group having a polymerizable carbon-carbon double bond, a compound (II) having two or more functional groups having a polymerizable carbon-carbon double bond (provided that the compound has no sulfonic acid group), a surfactant (III) (provided that the surfactant (III) has no polymerizable carbon-carbon double bond) and a polymer of a polymerizable composition (α) containing a pigment compound (B) having a solubility in water of 1 g / 100 g or less, wherein the water contact angle of the hydrophilic film is 30° or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a hydrophilic film, a laminate having a hydrophilic film, and a method for producing the laminate. [Background technology]

[0002] The present inventors have already proposed hydrophilic films that have hydrophilic properties and excellent antifogging, antifouling, antistatic, anticondensation, etc., and have a high concentration of hydrophilic groups on the surface (for example, Patent Document 1, Patent Document 2, etc.). For example, if this hydrophilic film is applied to a bathroom window, it can make it difficult for limescale to accumulate, suppress the whitening of the window glass caused by limescale, and reduce the number of times it needs to be cleaned.It is an excellent material.

[0003] For transparent members such as the above-mentioned window glass that require improved visibility, it may be desirable to further cut light in a wavelength range known as yellow light. One method for cutting this specific wavelength range is to include in the hydrophilic film a dye compound capable of absorbing light in a specific wavelength range. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2012 / 014829 [Patent Document 2] International Publication No. 2015 / 087810 Summary of the Invention [Problem to be solved by the invention]

[0005] However, according to the studies of the present inventors, even if a dye compound that is expected to be able to absorb light in a specific wavelength range is added, the hydrophilicity is impaired, and in some cases the improvement in visibility is not sufficient.

[0006] An object of the present disclosure is to provide a hydrophilic film that can improve hydrophilicity and visibility, a laminate having the hydrophilic film, and a method for producing the laminate. [Means for solving the problem]

[0007] As a result of intensive research into solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a hydrophilic film or the like made from a polymerizable composition containing a specific polymerizable compound, a specific dye, or the like.

[0008] That is, the present disclosure includes the following aspects. [1] A hydrophilic film comprising a polymer of a polymerizable composition (α) containing the following compound (I), the following compound (II), a surfactant (III) (provided that the surfactant (III) does not have a polymerizable carbon-carbon double bond), and the following dye compound (B): The hydrophilic film has a water contact angle of 30° or less. Compound (I): a compound having a sulfonic acid group and at least one functional group having a polymerizable carbon-carbon double bond; Compound (II): a compound having two or more functional groups each having a polymerizable carbon-carbon double bond (but not having a sulfonic acid group); Pigment compound (B): A pigment compound with a solubility in water of 1 g / 100 g or less. [2] The hydrophilic film according to [1], wherein the dye compound (B) is a tetraazaporphyrin compound.

[0009] [3] A compound (I) having a sulfonic acid group and at least one functional group having a polymerizable carbon-carbon double bond; A compound (II) having two or more functional groups each having a polymerizable carbon-carbon double bond (provided that the compound does not have a sulfonic acid group), surfactant (III) (provided that surfactant (III) does not have a polymerizable carbon-carbon double bond); a dye compound (B) having a solubility in water of 1 g / 100 g or less, and The solubility parameter (SP) is 9.3 to 10.5 (cal / cm 3) 1 / 2 A polymerizable composition (α1) containing a solvent (C) which is a solvent. [4] The polymerizable composition (α1) according to [3], wherein the solvent (C) contains at least one selected from the group consisting of an ester solvent, an alcohol solvent, and a ketone solvent.

[0010] [5] A step of applying the polymerizable composition (α1) according to [3] or [4] to a substrate to form a composition layer, A step of removing at least a part of the solvent (C) from the composition layer, and A step of polymerizing a monomer containing the compound (I) and the compound (II) of the composition layer after the removal of the solvent (C), including A method for producing a laminate having a hydrophilic film and a substrate.

[0011] [6] A laminate having at least one hydrophilic film according to [1] or [2] and a substrate. [7] The laminate according to [6], wherein the substrate is a polyethylene terephthalate substrate. [8] The laminate according to [6] or [7], wherein a hydrophilic film is formed on one surface side of the substrate, and an adhesive layer is formed on the surface side of the substrate where the hydrophilic film is not formed. [Effect of the Invention]

[0012] According to the present disclosure, a hydrophilic film capable of improving hydrophilicity and visibility, and a laminate having the hydrophilic film can be obtained. [Embodiments for Carrying Out the Invention]

[0013] In this specification, the numerical range n1 to n2 means n1 or more and n2 or less when n1 < n2, and means n2 or more and n1 or less when n1 > n2. In this specification, when a plurality of lower limit values and upper limit values are described for the description of an element, a numerical range formed by combining a value arbitrarily selected from the described lower limit values and a value arbitrarily selected from the described upper limit values is also regarded as being described.

[0014] In this specification, when the units of the values ​​written before and after "~" indicating a numerical range are the same, the unit of the values ​​written before "~" may be omitted. For example, "10 parts by weight to 100 parts by weight" may be written as "10 to 100 parts by weight."

[0015] In this specification, the amount of each component in a composition means the total amount of the multiple substances present in the composition, unless otherwise specified, when multiple substances corresponding to that component are present in the composition. In this specification, unless otherwise specified, the composition may contain one type of each component, or two or more types. As used herein, a combination of two or more preferred embodiments is a more preferred embodiment.

[0016] The polymerizable composition (α) of the present disclosure contains the following compound (I), compound (II), and surfactant (III). The polymerizable composition (α) is suitable for producing the hydrophilic film of the present disclosure.

[0017] [Compound (I)] Compound (I) is a compound having a sulfonic acid group and at least one functional group having a polymerizable carbon-carbon double bond. By polymerizing the polymerizable composition (α) containing such a compound having a sulfonic acid group and a functional group having a carbon-carbon double bond, hydrophilicity can be imparted to the resulting polymer (cured product).

[0018] The sulfonic acid group may be contained in the compound (I) in the form of a salt. Therefore, typically, the sulfonic acid group may be contained in the compound (I) in the form of the following formula (α). -SO3M (α) In the above formula (α), M is at least one monovalent cation selected from a hydrogen ion, an ammonium ion, an alkali metal ion, and a half atom of an alkaline earth metal ion.

[0019] The ammonium ion referred to in this specification is a cation formed by binding a hydrogen ion to ammonia, a primary amine, a secondary amine, or a tertiary amine. From the viewpoint of hydrophilicity, the ammonium ion is preferably a cation formed by binding a hydrogen ion to ammonia or an amine having a small number of carbon atoms, and more preferably an ammonium ion formed by binding a hydrogen ion to ammonia or methylammonium.

[0020] Examples of the alkali metal include lithium, sodium, potassium, and rubidium.

[0021] Examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, and barium.

[0022] Among the above M, alkali metal ions are preferred, and sodium ions, potassium ions, and rubidium ions are more preferred.

[0023] The functional group having a polymerizable carbon-carbon double bond is not particularly limited as long as the functional group is capable of radical polymerization or ionic polymerization, and examples thereof include an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylthio group, a methacryloylthio group, an acrylamide group, a methacrylamide group, an allyl group, a vinyl group, an isopropenyl group, a maleyl group (-CO-CH=CH-CO-), an itaconyl group (-CO-CH=CH-CO-), and a styryl group. Note that in this specification, acryloyl and methacryloyl are sometimes collectively referred to as (meth)acryloyl, acryloyloxy and methacryloyloxy are sometimes collectively referred to as (meth)acryloyloxy, acryloylthio and methacryloylthio are sometimes collectively referred to as (meth)acryloylthio, and acrylamide and methacrylamide are sometimes collectively referred to as (meth)acrylamide.

[0024] The compound (I) is preferably a compound represented by the following general formula (100).

[0025] [ka] In the above formula (100), A represents an organic group having 2 to 100 carbon atoms and having 1 to 5 functional groups each having a polymerizable carbon-carbon double bond, CD represents a group represented by the following general formula (101), n ​​represents the number of As bonded to CD and represents 1 or 2, and n0 represents the number of CDs bonded to A and represents an integer of 1 to 5.

[0026] [ka] In the above formula (101), M represents a hydrogen atom, an alkali metal, a half atom of an alkaline earth metal, or an ammonium ion, and #1 represents a bond bonded to the carbon atom included in A in formula (100).

[0027] In the above formula (100), A is preferably an organic group having 2 to 100 carbon atoms and having one or two functional groups with a polymerizable carbon-carbon double bond, as represented by the following general formulae (120) to (130).

[0028] [ka] In the above formula (120), X represents -O-, -S-, -NH-, or -NCH3-, r represents a hydrogen atom or a methyl group, r1 to r4 each independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group, m1 represents an integer of 0 to 10, n1 represents an integer of 0 to 100, and #2 represents a bond bonded to #1 contained in the group represented by the above general formula (101).

[0029] [ka] In the above formula (121), X represents -O-, -S-, -NH-, or -NCH3-; r represents a hydrogen atom or a methyl group; r1 to r6 independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group; r7 and r8 independently represent a hydrogen atom, a methylidene group, a methyl group, an ethyl group, or a hydroxyl group; the bond between the carbon atom to which r5 and r6 are bonded and the carbon atom to which r7 and r8 are bonded may be a single bond or a double bond; m1 and m3 independently represent an integer of 0 to 10; n1 represents an integer of 0 to 100; and #2 represents a bond bonded to #1 contained in the group represented by the above general formula (101).

[0030] [ka] In the above formula (122), X represents -O-, -S-, -NH-, or -NCH3-, r represents a hydrogen atom or a methyl group, r1 to r4 independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group, m2 represents an integer of 0 to 5, m1 represents an integer of 0 to 10, n0 represents an integer of 1 to 5, n1 represents an integer of 0 to 100, and #2 represents a bond bonded to #1 contained in the group represented by the above general formula (101).

[0031] [ka] In the above formula (123), r represents a hydrogen atom or a methyl group, r1 and r2 independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group, m1 represents an integer of 0 to 10, and #2 represents a bond bonded to #1 contained in the group represented by the above general formula (101).

[0032] [ka] In the above formula (124), r represents a hydrogen atom or a methyl group, r1 and r2 independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group, m1 represents an integer of 0 to 10, m2 independently represents an integer of 0 to 5, n0 represents an integer of 1 to 5, and #2 represents a bond bonded to #1 contained in the group represented by the above general formula (101).

[0033] [ka] In the above formula (125), r1 and r2 independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group, and #2 represents a bond bonded to #1 contained in the group represented by the above general formula (101).

[0034] [ka] In the above formula (126), r1 represents a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group, and #2 represents a bond bonded to #1 contained in the group represented by the above general formula (101).

[0035] [ka] In the above formula (127), X represents -O-, -S-, -NH-, or -NCH3-; r and r0 independently represent a hydrogen atom or a methyl group; r5 and r6 independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group; R 10 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a benzyl group, a hydroxyl group, a hydroxymethyl group, or a hydroxyethyl group; m0 represents an integer of 1 to 10; and #2 represents a bond bonded to #1 contained in the group represented by the above general formula (101).

[0036] [ka] In the above formula (128), r independently represents a hydrogen atom or a methyl group, r5 and r6 independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group, r7 and r8 independently represent a hydrogen atom, a methylidene group, a methyl group, an ethyl group, or a hydroxyl group, the bond between the carbon atom to which r5 and r6 are bonded and the carbon atom to which r7 and r8 are bonded may be a single bond or a double bond, m1 represents an integer of 0 to 10, and #2 represents a bond to #1 contained in the group represented by the above general formula (101).

[0037] [ka] In the above formula (129), r independently represents a hydrogen atom or a methyl group, r5 and r6 independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group, r7 and r8 independently represent a hydrogen atom, a methylidene group, a methyl group, an ethyl group, or a hydroxyl group, the bond between the carbon atom to which r5 and r6 are bonded and the carbon atom to which r7 and r8 are bonded may be a single bond or a double bond, m1 represents an integer of 0 to 10, and #2 represents a bond to #1 contained in the group represented by the above general formula (101).

[0038] [ka] In the above formula (130), r independently represents a hydrogen atom or a methyl group, r5 and r6 independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group, r7 and r8 independently represent a hydrogen atom, a methylidene group, a methyl group, an ethyl group, or a hydroxyl group, the bond between the carbon atom to which r5 and r6 are bonded and the carbon atom to which r7 and r8 are bonded may be a single bond or a double bond, m1 represents an integer of 0 to 10, and #2 represents a bond to #1 contained in the group represented by the above general formula (101).

[0039] Among the above compounds (I), compounds represented by the following general formulae (Ia), (Ib), (Ic) and (Id) are preferred.

[0040] [ka] In the above formula (Ia), q represents 0 or 1; R represents a divalent aliphatic hydrocarbon group having 1 to 600 carbon atoms which may contain at least one group selected from an aromatic ring, an aliphatic cyclic group, an ether group, and an ester group; D1 represents a (meth)acryloyloxy group, a (meth)acryloylthio group, a (meth)acrylamide group, a vinyl group, an allyl group, an isopropenyl group, or a styryl group when q is 1; and D1 represents a vinyl group, an allyl group, an isopropenyl group, or a styryl group when q is 0; and M represents a hydrogen ion, an ammonium ion, an alkali metal ion, or a half-atom alkaline earth metal ion.

[0041] [ka] In the above formula (Ib), X represents -O-, -S-, -NH-, or -NCH3-; r and r0 independently represent a hydrogen atom or a methyl group; r5 and r6 independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group; R 10 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a benzyl group, a hydroxyl group, a hydroxymethyl group, or a hydroxyethyl group; m0 represents an integer of 1 to 10; and M represents a hydrogen ion, an ammonium ion, an alkali metal ion, or a half-atom alkaline earth metal ion. Specific examples of the compound represented by the general formula (Ib) include the compounds described in paragraph

[0068] of WO 2015 / 087810.

[0042] [ka] In the above formula (Ic), D3, R3, and SO3M are groups bonded to carbon atoms on the ring contained in the above formula, and D3 each independently represents a vinyl group, allyl group, isopropenyl group, or styryl group, R3 each independently represents a hydrogen atom, methyl group, ethyl group, methoxy group, ethoxy group, fluorine atom, chlorine atom, bromine atom, or iodine atom, M represents a hydrogen ion, ammonium ion, alkali metal ion, or 1 / 2 atom alkaline earth metal ion, k represents an integer of 0 to 10, l and m independently represent integers of 1 to 11, and n represents an integer of 0 to 3, satisfying k+l+m=2 to 6+2n, provided that when l is 2 or greater, D3s may be the same or different from one another, and when k is 2 or greater, R3s may be the same or different from one another, and when m is 2 or greater, Ms may be the same or different from one another. For convenience, it is desirable that compounds that are represented by the above general formula (Ic) and can also be represented by the above general formula (Ia) are excluded from the compounds represented by the above general formula (Ic).

[0043] In addition, in the above formula (Ic), k, l, m, and n can be rephrased as follows: n is an integer of 0 to 3, and when n=0, k is an integer of 0 to 4, l and m are independently integers of 1 to 5, provided that k+l+m is an integer of 2 to 6; when n=1, k is an integer of 0 to 6, l and m are independently integers of 1 to 7, provided that k+l+m is an integer of 2 to 8; when n=2, k is an integer of 0 to 8, l and m are independently integers of 1 to 9, provided that k+l+m is an integer of 2 to 10; and when n=3, k is an integer of 0 to 10, l and m are independently integers of 1 to 11, provided that k+l+m is an integer of 2 to 12.

[0044] [ka] In the above formula (Id), D3, R3, and SO3M are groups bonded to carbon atoms on the ring contained in the above formula, D3 each independently represents a vinyl group, allyl group, isopropenyl group, or styryl group, R3 each independently represents a hydrogen atom, methyl group, ethyl group, methoxy group, ethoxy group, fluorine atom, chlorine atom, bromine atom, or iodine atom, M represents a hydrogen ion, ammonium ion, alkali metal ion, or 1 / 2 atom alkaline earth metal ion, r represents an integer of 0 to 6, q and p independently represent integers of 1 to 7, and satisfy the relationship p + q + r = 2 to 8, provided that when p is 2 or greater, D3's may be the same or different from one another, when r is 2 or greater, R3's may be the same or different from one another, and when q is 2 or greater, M's may be the same or different from one another.

[0045] Among the compounds (I), the compounds represented by the general formula (Ia) are one preferred embodiment. Among the compounds represented by the general formula (Ia), the compounds represented by the following general formula (Ia-1) are preferred, and the compounds represented by the following general formulas (Ia-2), (Ia-3) and (Ia-4) are also preferred.

[0046] [ka] In the above formula (Ia-1), x represents an integer of 0 to 10, y and v independently represent an integer of 0 to 10, w represents 0 or 1, provided that when either v or y is 0, w is 0, D1 represents a vinyl group, an allyl group, an isopropenyl group, or a styryl group when x is 0 and y is 0, and represents a (meth)acryloyloxy group, a (meth)acryloylthio group, a (meth)acrylamide group, a vinyl group, an allyl group, an isopropenyl group, or a styryl group when either x or y is 1 or more, R1 to R4 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; M represents a hydrogen ion, an ammonium ion, an alkali metal ion, or a half-atom alkaline earth metal ion; when v is 2 or greater, R1s and R2s may be the same or different from each other; when y is 2 or greater, R3s and R4s may be the same or different from each other; and when x is 2 or greater, R1s and R2s may be the same or different from each other.

[0047] Among the compounds represented by the above general formula (Ia-1), compounds in which v=w=x=0 and y=an integer of 1 to 10 are preferred, and compounds in which v=w=x=0 and y=an integer of 1 to 3 are more preferred. Specific examples of the compound represented by the general formula (Ia-1) include the compounds exemplified as compounds represented by formula (Ia-1) in paragraph

[0077] of WO 2015 / 087810.

[0048] [ka] In the above formula (Ia-2), X represents -O-, -S-, -NH-, or -NCH3-; r represents a hydrogen atom or a methyl group; r1 to r4 each independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group; m1 represents an integer of 0 to 10; n1 represents an integer of 0 to 100; and M represents a hydrogen ion, an ammonium ion, an alkali metal ion, or a half-atom alkaline earth metal ion. Specific examples of the compound represented by the general formula (Ia-2) include the compounds exemplified as compounds represented by formula (Ia-a) in paragraph

[0079] of WO 2015 / 087810.

[0049] [ka] In the above formula (Ia-3), r represents a hydrogen atom or a methyl group, r1 and r2 independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group, m1 represents an integer of 0 to 10, M represents a hydrogen ion, an ammonium ion, an alkali metal ion, or a half-atom alkaline earth metal ion, and n1 represents an integer of 1 to 10. Specific examples of the compound represented by the general formula (Ia-3) include the compounds exemplified as compounds represented by formula (Ia-c) in paragraph

[0081] of WO 2015 / 087810.

[0050] [ka] In the above formula (Ia-4), r represents a hydrogen atom or a methyl group, r1 and r2 independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group, m1 represents an integer of 0 to 10, m2 represents an integer of 0 to 5, n0 represents an integer of 1 to 5, M represents a hydrogen ion, an ammonium ion, an alkali metal ion, or a half-atom alkaline earth metal ion, and n1 represents an integer of 1 to 10. Specific examples of the compound represented by the general formula (Ia-4) include the compounds exemplified as compounds represented by formula (Ia-d) in paragraph

[0083] of WO 2015 / 087810.

[0051] Among the compounds represented by the above general formula (Ib), the compound represented by the following general formula (Ib-1) is preferred.

[0052] [ka] In the above formula (Ib-1), R5 and R6 represent a hydrogen atom or a methyl group, R7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, M represents a hydrogen ion, an ammonium ion, an alkali metal ion, or a half-atom alkaline earth metal ion, and n1 represents an integer of 1 to 10. Specific examples of the compound represented by the general formula (Ib-1) include the compounds exemplified as compounds represented by formula (Ib-b) in paragraph

[0086] of WO 2015 / 087810.

[0053] The molecular weight of the compound (I) is usually 72 to 18,000, preferably 72 to 3,000, and more preferably 72 to 1,000.

[0054] The compound (I) may be used alone or in combination of two or more.

[0055] The polymerizable composition (α) contains the compound (I), and at least a part of the compound (I) may be reacted to form an oligomer, which is contained in the composition. The oligomer here usually contains 2 to 20 repeating units formed from the compound (I).

[0056] The compound (I) can be produced by a known method or a method similar to a known method, and is also commercially available.

[0057] [Compound (II)] The compound (II) contained in the polymerizable composition (α) is a compound having two or more functional groups each having a polymerizable carbon-carbon double bond. However, unlike the compound (I), the compound (II) does not have a sulfonic acid group. By polymerizing the polymerizable composition (α) containing such a compound (II), a sufficiently crosslinked polymer (cured product) can be obtained.

[0058] Compound (II) preferably does not have an anionic hydrophilic group or a cationic hydrophilic group such as a sulfonic acid group, a carboxyl group, or a phosphate group.

[0059] The functional group having a polymerizable carbon-carbon double bond is not particularly limited as long as the functional group is capable of radical polymerization or ionic polymerization, and examples thereof include the same functional groups as those exemplified for compound (I). Among these functional groups having a polymerizable carbon-carbon double bond, a (meth)acryloyl group is preferred.

[0060] Examples of the (meth)acryloyl group include a (meth)acryloyloxy group, a (meth)acryloylthio group, and a (meth)acrylamide group. Among these (meth)acryloyl groups, a (meth)acryloyloxy group and a (meth)acryloylthio group are preferred.

[0061] Among the above compounds (II), preferred are compounds having one or more hydroxyl groups and two or more (meth)acryloyl groups, compounds having one or more bonds selected from an ether bond and a thioether bond and two or more (meth)acryloyl groups, compounds having one or more ester bonds (excluding ester bonds at the portion directly bonded to a (meth)acryloyl group) and two or more (meth)acryloyl groups, compounds having one or more groups selected from an alicyclic group and an aromatic group and two or more (meth)acryloyl groups, and compounds having one or more heterocycles and two or more (meth)acryloyl groups.

[0062] Examples of the compound (II) include ethylene glycol di(meth)acrylate, 1,2-propanediol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl 1,3-propanediol di(meth)acrylate, 1,2-bis{3-(meth)acryloyloxy-2-hydroxy-propyloxy}ethane, 1,2-bis{3-(meth)acryloyloxy-2-hydroxy-propyloxy}propane, 1,3-bis{3-(meth)acryloyloxy-2-hydroxy-propyloxy}propane, 1,4-bis{3-(meth)acryloyloxy-2-hydroxy-propyloxy}butane, 1,6-bis{3-(meth)acryloyloxy-2-hydroxy-propyloxy}hexane; Neopentyl glycol hydroxypivalic acid di(meth)acrylate; Polyethylene glycol di(meth)acrylate, 1,2-polypropylene glycol di(meth)acrylate, 1,3-polypropylene glycol di(meth)acrylate, 1,4-polybutylene glycol di(meth)acrylate, polyethylene glycol-bis{3-(meth)acryloyloxy-2-hydroxy-propyl} ether, 1,2-polypropylene glycol-bis{3-(meth)acryloyloxy-2-hydroxy-propyl} ether; 1,2-Polypropylene glycol-bis{(meth)acryloyl-poly(oxyethylene)}ether; Examples include 1,3-polypropylene glycol di(meth)acrylate, 1,4-polybutylene glycol di(meth)acrylate, and 1,4-polybutylene glycol-bis{3-(meth)acryloyloxy-2-hydroxypropyl} ether.

[0063] Examples of the compound (II) include bis{2-(meth)acryloylthio-ethyl}sulfide, bis{5-(meth)acryloylthio-3-thiapentyl}sulfide; Cyclohexanediol di(meth)acrylate, bis{(meth)acryloyloxy-methyl}cyclohexane, bis{7-(meth)acryloyloxy-2,5-dioxaheptyl}cyclohexane, bis{(meth)acryloyloxy-poly(ethyleneoxy)-methyl}cyclohexane; Tricyclodecane dimethanol di(meth)acrylate; 2-propenoic acid {2-(1,1-dimethyl-2-{(1-oxo-2-propenyl)oxy}ethyl)-5-ethyl-1,3-dioxan-5-yl}methyl ester (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD R-604"); N,N',N"-Tris{2-(meth)acryloyloxy-ethyl}isocyanurate; Xylylenediol di(meth)acrylate, bis{7-(meth)acryloyloxy-2,5-dioxaheptyl}benzene, bis{(meth)acryloyloxy-poly(ethyleneoxy)-methyl}benzene; Bisphenol A di(meth)acrylate, bis{(meth)acryloyl-oxyethyl}bisphenol A, bis{(meth)acryloyl-oxypropyl}bisphenol A, bis{(meth)acryloyl-poly(oxyethylene)}bisphenol A, bis{(meth)acryloyl-poly(oxy-1,2-propylene)}bisphenol A, bis{3-(meth)acryloyloxy-2-hydroxy-propyl}bisphenol A, bis{3-(meth)acryloyloxy-2-hydroxy-propyl-oxyethyl}bisphenol A, bis{3-(meth)acryloyloxy-2-hydroxy-propyl-oxypropyl}bisphenol A, bis{3-(meth)acryloyloxy-2-hydroxy-propyl-poly(oxyethylene)}bisphenol A, bis{3-(meth)acryloyloxy-2-hydroxy-propyl-poly(oxy-1,2-propylene)}bisphenol A; Bis{(meth)acryloyl-oxyethyl-oxypropyl}bisphenol A, bis{(meth)acryloylpoly(oxyethylene)-poly(oxy-1,2-propylene)}bisphenol A; Naphthalenediol di(meth)acrylate, bis{3-(meth)acryloyloxy-2-hydroxy-propyl-oxy}naphthalene; 9,9-fluorenediol di(meth)acrylate, 9,9-bis{4-(2-(meth)acryloyloxy-ethyl-oxy)}fluorene, 9,9-bis{3-phenyl-4-(meth)acryloyloxy-poly(ethyleneoxy)}fluorene; and the like.

[0064] Further examples of the compound (II) include phenol novolac epoxy (meth)acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade names "NK Oligo EA-6320, EA-7120, EA-7420"); Glycerin-1,3-di(meth)acrylate, 1-acryloyloxy-2-hydroxy-3-methacryloyloxy-propane, 2,6,10-trihydroxy-4,8-dioxaundecane-1,11-di(meth)acrylate, 1,3-bis{3-(meth)acryloyloxy-2-hydroxy-propyl-oxy}-2-hydroxypropane, 1,2,3-tris{3-(meth)acryloyloxy-2-hydroxy-propyl-oxy}propane, 1,2, 3-tris{2-(meth)acryloyloxy-ethyl-oxy}propane, 1,2,3-tris{2-(meth)acryloyloxy-propyl-oxy}propane, 1,2,3-tris{(meth)acryloyloxy-poly(1,2-ethyleneoxy)}propane, 1,2,3-tris{(meth)acryloyloxy-poly(1,2-propyleneoxy)}propane, 1,2,3-tris{(meth)acryloyloxy-poly(1,3-propyleneoxy)}propane; Trimethylolpropane tri(meth)acrylate, trimethylolpropane-tris{(meth)acryloyloxy-ethyl-oxy} ether, trimethylolpropane-tris{2-(meth)acryloyloxy-propyl-oxy} ether, trimethylolpropane-tris{(meth)acryloyloxy-poly(ethyleneoxy)} ether, trimethylolpropane-tris{(meth)acryloyloxy-poly(1,2-propyleneoxy)} ether, pentaerythritol tri( meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol-tetrakis{(meth)acryloyloxy-ethyl-oxy} ether, pentaerythritol-tetrakis{2-(meth)acryloyloxy-propyl-oxy} ether, pentaerythritol-tetrakis{(meth)acryloyloxy-poly(ethyleneoxy)} ether, pentaerythritol-tetrakis{(meth)acryloyloxy-poly(1,2-propyleneoxy)} ether; Ditrimethylolpropane tetra(meth)acrylate, ditrimethylolpropane tetrakis{(meth)acryloyloxy-ethyl-oxy} ether, ditrimethylolpropane tetrakis{2-(meth)acryloyloxy-propyl-oxy} ether, ditrimethylolpropane tetrakis{(meth)acryloyloxy-poly(ethyleneoxy)} ether, ditrimethylolpropane tetrakis{(meth)acryloyloxy-poly(1,2-propyleneoxy)} ether, dipentaerythritol dipentaerythritol-hexa{(meth)acryloyloxy-ethyl-oxy}ether, dipentaerythritol-hexa{2-(meth)acryloyloxy-propyl-oxy}ether, dipentaerythritol-hexa{(meth)acryloyloxy-poly(ethyleneoxy)}ether, dipentaerythritol-hexa{(meth)acryloyloxy-poly(1,2-propyleneoxy)}ether; and the like.

[0065] Additionally, examples of the compound (II) include urethane reaction products of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, or 4-hydroxybutyl (meth)acrylate with hexamethylene diisocyanate; urethane reaction products of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, or 4-hydroxybutyl (meth)acrylate with isophorone diisocyanate; urethane reaction products of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, or 4-hydroxybutyl (meth)acrylate with bis(isocyanatomethyl)norbornane; urethane reaction products of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, or 4-hydroxybutyl (meth)acrylate with norbis(4-isocyanatocyclohexyl)methane; urethane reaction products of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, or 4-hydroxybutyl (meth)acrylate with 1,3-bis(isocyanatomethyl)cyclohexane; Examples thereof include urethane reaction products of 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, or 4-hydroxybutyl (meth)acrylate with m-xylylene diisocyanate; and the like.

[0066] The compound (II) may be used alone or in combination of two or more. The compound (II) may be produced by a known method or a method similar to a known method, or may be commercially available.

[0067] The blending ratio of compound (I) and compound (II) is preferably 0.1 to 50 wt% of compound (I) and 99.9 to 50 wt% of compound (II) relative to the weight of compound (I) and compound (II), more preferably 0.3 to 30 wt% of compound (I) and 99.7 to 70 wt% of compound (II), and even more preferably 0.5 to 20 wt% of compound (I) and 99.5 to 80 wt% of compound (II).

[0068] [Surfactant (III)] The polymerizable composition (α) contains the above-mentioned compound (I) and compound (II) as well as a surfactant (III). However, the surfactant (III) does not have a polymerizable carbon-carbon double bond. The surfactant is usually a substance having a hydrophilic moiety such as an anionic hydrophilic group, a cationic hydrophilic group, or a hydroxyl group, and a hydrophobic moiety such as an organic residue.

[0069] By polymerizing the polymerizable composition (α) containing the surfactant (III), the sulfonic acid groups derived from the compound (I) are more likely to be concentrated on the surface of the polymer (cured product), and for example, the sulfonic acid groups are more likely to be inclined on the surface of a hydrophilic film containing the polymer.

[0070] Among the surfactants (III), surfactants (III') having a sulfonic acid group and a molecular weight of 200 to 1,000,000 are preferred. By polymerizing the polymerizable composition (α) containing the surfactant (III'), a polymer (cured product) can be obtained that not only has high hydrophilicity but also has high hydrophilic durability and high surface smoothness.

[0071] By including the surfactant (III') in the polymerizable composition (α), the surface energy of the surface of the composition that is in contact with the outside air is reduced, and the surface smoothness (leveling ability) of the polymer obtained from the polymerizable composition (α) can be improved without reducing the hydrophilicity.

[0072] As the surfactant (III'), when it is desired to improve hydrophilicity, a compound having a larger number of sulfonic acid groups tends to be preferred. When it is desired to improve leveling properties, a compound having a relatively small number of sulfonic acid groups and a large molecular weight of the organic residue portion tends to be preferred. The molecular weight of the surfactant (III') is usually in the range of 200 to 1,000,000, preferably in the range of 250 to 100,000, and more preferably in the range of 300 to 10,000. When the molecular weight is in the above range, a polymer having high hydrophilicity and excellent leveling properties, for example, a hydrophilic film containing the polymer, can be obtained.

[0073] Among the above surfactants, the compound represented by the following general formula (300) is preferred.

[0074] [ka] In the above formula (300), R represents an organic residue having 4 to 100 carbon atoms, FG represents a hydrophilic group containing at least one group selected from an anionic hydrophilic group, a cationic hydrophilic group, and a hydroxyl group, n represents the number of R bonded to FG and represents 1 or 2, n0 represents the number of FG bonded to R and represents an integer of 1 to 5, and when FG is a group containing one hydroxyl group, n0 represents an integer of 2 to 5.

[0075] Examples of the group containing an anionic hydrophilic group that serves as FG include hydrophilic groups represented by the following general formula (301).

[0076] [ka] In the above formula (301), M represents a hydrogen atom, an alkali metal, a half atom of an alkaline earth metal, or an ammonium ion, and #3 represents a bond bonded to the carbon atom included in R in formula (300).

[0077] Examples of surfactants in which FG is represented by the above general formula (301) include alkylsulfonic acid surfactants, alkenylsulfonic acid surfactants (however, the alkenyl group contained in the surfactant is not polymerizable), alkylacetic acid sulfonic acid surfactants, N-acylated sulfonic acid surfactants, hydroxyalkanesulfonic acid surfactants, arylsulfonic acid surfactants, sulfosuccinate surfactants, etc. Among these, alkylsulfonic acid surfactants and sulfosuccinate surfactants are preferred.

[0078] Examples of alkylsulfonic acid surfactants include sodium butylsulfonate, sodium pentylsulfonate, sodium hexylsulfonate, sodium heptylsulfonate, octyl sulfonic acid, sodium octyl sulfonate, potassium octyl sulfonate, ammonium octyl sulfonate, magnesium octyl sulfonate, calcium octyl sulfonate, nonyl sulfonic acid, sodium nonyl sulfonate, potassium nonyl sulfonate, ammonium nonyl sulfonate, magnesium nonyl sulfonate, calcium nonyl sulfonate, decyl sulfonic acid, sodium decyl sulfonate, potassium decyl sulfonate, ammonium decyl sulfonate, magnesium decyl sulfonate, calcium decyl sulfonate, sodium undecyl sulfonate, dodecyl sulfonic acid, sodium dodecyl sulfonate, potassium dodecyl sulfonate, ammonium dodecyl sulfonate, and magnesium dodecyl sulfonate. , calcium dodecyl sulfonate, sodium tridecyl sulfonate, tetradecyl sulfonic acid, sodium tetradecyl sulfonate, potassium tetradecyl sulfonate, ammonium tetradecyl sulfonate, magnesium tetradecyl sulfonate, calcium tetradecyl sulfonate, sodium pentadecyl sulfonate, hexadecyl sulfonic acid, sodium hexadecyl sulfonate, potassium hexadecyl sulfonate, ammonium hexadecyl sulfonate, magnesium hexadecyl sulfonate, calcium hexadecyl sulfonate, sodium hexadecyl sulfonate, sodium heptadecyl sulfonate, octadecyl sulfonic acid, sodium octadecyl sulfonate, potassium octadecyl sulfonate, ammonium octadecyl sulfonate, magnesium octadecyl sulfonate, calcium octadecyl sulfonate, sodium nonadecyl sulfonate, and sodium icosanyl sulfonate.

[0079] Among the surfactants in which FG is represented by general formula (301), compounds having an organic residue having 6 to 100 carbon atoms are preferred, compounds having an organic residue having 8 to 60 carbon atoms are more preferred, and compounds having an organic residue having 10 to 40 carbon atoms are even more preferred. Furthermore, among the above surfactants, sulfosuccinate surfactants are relatively preferred.

[0080] Among the surfactants (III'), a compound represented by the following general formula (301-A), which is a sulfosuccinate surfactant, is a preferred embodiment. In this compound, the sulfonic acid group is located relatively near the center of the organic residue, and the molecular weight of the entire organic residue is relatively large. Therefore, when a composition containing this compound is applied to a substrate or the like, the compound tends to be uniformly dispersed on the surface exposed to the air, which tends to reduce the surface tension and improve leveling properties.

[0081] [ka] In the formula (301-A), Z represents a hydrogen ion, an ammonium ion, an alkali metal ion, or a half-atom alkaline earth metal ion. Among these Z, an alkali metal ion is preferred, and a sodium ion or a potassium ion is more preferred.

[0082] In the above formula (301-A), R1 and R2 each independently represent an ester residue having 1 to 100 carbon atoms. Among these R1 and R2, an ester residue having 4 to 50 carbon atoms is preferred, and an ester residue having 6 to 30 carbon atoms is more preferred. As the ester residue, alkyl esters, alkylaryl esters, alkyl ether alkylene esters, and alkylaryl ether alkyl esters tend to be preferred, and alkyl esters tend to be more preferred.

[0083] Examples of the compound represented by the general formula (301-A) in which the ester residue is an alkyl ester include methyl sulfosuccinate, methyl sulfosuccinate sodium, methyl sulfosuccinate potassium, ethyl sulfosuccinate, ethyl sulfosuccinate sodium, ethyl sulfosuccinate potassium, propyl sulfosuccinate, propyl sulfosuccinate sodium, propyl sulfosuccinate potassium, butyl sulfosuccinate, butyl sulfosuccinate sodium, butyl sulfosuccinate potassium, pentyl sulfosuccinate, pentyl sulfosuccinate sodium, pentyl sulfosuccinate potassium, hexyl sulfosuccinate, hexyl sulfosuccinate sodium, hexyl sulfosuccinate potassium, octyl sulfosuccinate, octyl sulfosuccinate sodium, octyl sulfosuccinate potassium, nonyl sulfosuccinate, nonyl sulfosuccinate sodium, sulfosuccinate Nonyl potassium succinate, decyl sulfosuccinate, sodium decyl sulfosuccinate, potassium decyl sulfosuccinate, undecyl sulfosuccinate, sodium undecyl sulfosuccinate, potassium undecyl sulfosuccinate, lauryl sulfosuccinate, sodium lauryl sulfosuccinate, potassium lauryl sulfosuccinate, myristyl sulfosuccinate, sodium myristyl sulfosuccinate, potassium myristyl sulfosuccinate, cetyl sulfosuccinate, sodium cetyl sulfosuccinate, cetyl potassium sulfosuccinate, stearyl sulfosuccinate, sodium stearyl sulfosuccinate, potassium stearyl sulfosuccinate, oleyl sulfosuccinate, sodium oleyl sulfosuccinate, potassium oleyl sulfosuccinate, linolyl sulfosuccinate, sodium linolyl sulfosuccinate, and potassium linolyl sulfosuccinate.

[0084] The surfactant (III) may be used alone or in combination of two or more.

[0085] In the polymerizable composition (α), the surfactant (III) is typically contained in an amount ranging from 0.0001 to 50 wt %, preferably from 0.001 to 20 wt %, and more preferably from 0.01 to 10 wt %, based on the total amount of compound (I) and compound (II). Polymerizing a composition containing surfactant (III) in this range facilitates the concentration of hydrophilic groups derived from compound (I) on the surface of the polymerized product. For example, in the case of a hydrophilic film containing the polymerized product, the hydrophilic groups are more likely to be inclined toward the surface, enhancing hydrophilicity. Furthermore, the surface smoothness (leveling ability) of the product obtained from the polymerizable composition (α) can be improved. Furthermore, the leveling ability tends to improve with increasing surfactant (III) addition, but excessive addition may result in reduced transparency of the resulting cured product. Therefore, adding surfactant (III) in the above-mentioned range improves leveling ability while maintaining high transparency.

[0086] [Pigment compound (B)] The polymerizable composition (α) further contains a dye compound (B). The dye compound (B) has a water solubility of 1 g / 100 g or less. In this specification, the water solubility refers to the solubility in water at 25°C under atmospheric pressure. The water solubility can be determined by adding x g of the dye compound (B) to 100 g of water at 25°C under atmospheric pressure in a beaker, stirring with a stirrer for 1 hour, and then visually checking for any undissolved matter. By including a dye compound having such water solubility in the polymerizable composition (α), not only can the visibility of the polymer obtained from the polymerizable composition (α) be improved, but also the hydrophilicity of the polymer is not impaired.

[0087] Although the detailed mechanism is unclear, it is presumed that the following phenomenon occurs when the polymerizable composition (α) is applied to a substrate or the like. Specifically, the hydrophobic portion (organic residue) other than the hydrophilic portion (e.g., sulfonic acid group) contained in the surfactant (III) has a lower cohesive energy and is more hydrophobic than the hydrophilic portion. Therefore, when the polymerizable composition (α) is applied to a substrate or the like, the portion centered on the organic residue contained in the surfactant (III) is presumed to attempt to migrate to the surface exposed to the air and form some kind of ordered structure on that surface. This action of the surfactant (III) near the surface exposed to the air can improve surface smoothness (leveling). It is also presumed that the portion centered on the hydrophilic portion contained in the surfactant (III) faces away from the surface of the composition (toward the interior). As a result, the portion centered on this hydrophilic part interacts with the portion centered on the sulfonic acid group contained in compound (I), and the sulfonic acid group derived from compound (I) tends to concentrate near the surface of polymerizable composition (α) that is in contact with the outside air, making it easier to form a structure in which the sulfonic acid group is inclined toward the surface. In this case, if the solubility of the dye compound in water is high, exceeding 1 g / 100 g, and surfactant (III) prevents the dye compound from moving to the surface exposed to the air, the interaction between the sulfonic acid group-centered portion of compound (I) and the hydrophilic portion of surfactant (III) may be weakened, making it difficult to form the above-mentioned structure in which the sulfonic acid group is tilted toward the surface. On the other hand, when the solubility of the dye compound in water is as low as 1 g / 100 g or less, the dye compound does not adversely affect the surfactant (III) and the compound (I), and a structure in which the sulfonic acid groups are inclined on the surface is formed. Then, by polymerizing the polymerizable composition (α) having such a structure, this structure is fixed, and a polymer in which the sulfonic acid groups are segregated on the surface in contact with the outside air is obtained, and the water contact angle of the surface can be made low, for example, 30° or less.

[0088] From the viewpoint of the hydrophilicity of the resulting polymer, the solubility of the dye compound (B) in water is preferably 1 g / 100 g or less, more preferably 0.5 g / 100 g or less, and is usually 0.001 g / 100 g or more.

[0089] The coloring compound (B) is not particularly limited as long as its solubility in water is within the above-mentioned range, and may be, for example, either an inorganic compound or an organic compound classified as a dye or pigment. The range of the maximum absorption wavelength of the dye compound (B) is preferably 570 nm or more, more preferably 575 nm or more, even more preferably 580 nm or more, and is preferably 605 nm or less, more preferably 600 nm or less, even more preferably 595 nm or less, and still more preferably 590 nm or less. When the dye compound (B) has a maximum absorption wavelength in the above range, the appearance of the resulting hydrophilic film containing the polymer is improved, and the performance balance between transparency and visibility can be further improved.

[0090] The dye compound (B) preferably contains at least one selected from the group consisting of tetraazaporphyrin compounds and azo compounds, and more preferably contains a tetraazaporphyrin compound. The azo compound is a compound having an azo skeleton. The tetraazaporphyrin compound may have various substituents on the tetraazaporphyrin skeleton, and is preferably, for example, a compound represented by the following general formula (B1).

[0091] [ka]

[0092] In formula (B1), R1 to R8 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a linear, branched, or cyclic alkyl group, a linear, branched, or cyclic alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkyloxy group, a linear, branched, or cyclic halogenoalkyl group, a linear, branched, or cyclic halogenoalkoxy group, a substituted or unsubstituted amino group, a linear, branched, or cyclic alkoxy ... halogenoalkoxy group, a substituted or unsubstituted amino group, a linear, branched, or cyclic halogenoalkoxy group, a substituted or unsubstituted amino group, a linear, branched, or cyclic halogenoalkoxy group, a substituted or unsubstituted amino group, a linear, branched, or cyclic halogenoalkoxy group, a substituted or unsubstituted amino group, a linear, branched, or cyclic halogenoalkoxy group, a substituted or unsubstituted amino group, a linear, branched, or cyclic halogenoalkoxy group, a represents a cyclic alkoxyalkoxyalkyl group, a substituted or unsubstituted aryloxyalkyl group, a substituted or unsubstituted aralkyloxyalkyl group, or a linear, branched, or cyclic halogenoalkoxyalkyl group; further, adjacent groups selected from R1 to R8 may be bonded to each other to form a substituted or unsubstituted carbocyclic aliphatic ring together with the substituting carbon atoms; and M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or an oxidized metal atom. In this specification, the term "aryl group" refers to a carbocyclic aromatic group such as a phenyl group or a naphthyl group, or a heterocyclic aromatic group such as a furyl group, a thienyl group or a pyridyl group, and preferably refers to a carbocyclic aromatic group.

[0093] In the compound represented by general formula (B1), preferably, R1 to R8 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 24 carbon atoms, a substituted or unsubstituted aryl group having 4 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 4 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 5 to 30 carbon atoms, a substituted or unsubstituted aralkyloxy group having 5 to 30 carbon atoms, a linear, branched or cyclic halogenoalkyl group having 1 to 24 carbon atoms, a substituted or unsubstituted aryloxy group having 5 ...aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 24 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or R1 to R8 each represent one or more selected from the group consisting of a C1 to C2 alkyl group, a C1 to C2 alkyl group, a C2 to C3 alkyl group, a C3 to C4 alkyl group, a C4 to C6 alkyl group, a C5 to C6 alkyl group, a C6 to C8 alkyl group, a C7 to C8 alkyl group, a C8 to C9 alkyl group, a C9 to C10 alkyl group, a C1 to C12 alkyl group, a C1 to C12 alkyl group, a C1 to C12 alkyl group, a C1 to C12 alkyl group, a C1 to C12 alkyl group, a C1 to C12 alkyl group, a C2 to C12 alkyl group, a C2 to C12 alkyl group, a C3 to C12 alkyl group, a C4 to C12 alkyl group, a C5 to C12 alkyl group, a C6 to C12 alkyl group, a C7 to C12 alkyl group, a C8 to C12 alkyl group, a C8 to C12 alkyl group, a C9 to C12 alkyl group, a C1 ...

[0094] In general formula (B1), M is more preferably Cu, Zn, Fe, Co, Ni, Pd, Mn, Mg, VO, or TiO, even more preferably Cu, Ni, Pd, or VO, and particularly preferably Cu or VO. Suitable examples of the tetraazaporphyrin compound used as the dye compound (B) include compounds represented by the following formulae (B1-1) to (B1-72).

[0095] [ka]

[0096] [ka]

[0097] [ka]

[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108] The dye compound (B) may be used alone or in combination of two or more.

[0109] In the polymerizable composition (α), the dye compound (B) is typically contained in an amount of 0.01 to 1% by weight, preferably 0.05 to 0.5% by weight, and more preferably 0.1 to 0.5% by weight, based on the total amount of the compounds (I) and (II). By polymerizing a composition containing the dye compound (B) in such a range, a polymer having improved visibility and excellent transparency can be obtained without impairing the hydrophilicity of the resulting polymer.

[0110] [Other ingredients] The polymerizable composition (α) may further contain other components, if necessary.

[0111] Examples of other components include silica particles (V). When the polymerizable composition (α) contains silica particles (V), it is possible to improve leveling properties and impart a matte effect (gloss control).

[0112] In the polymerizable composition (α), the silica particles (V) are contained in an amount of usually 0.00001 to 50% by weight, preferably 0.0001 to 30% by weight, more preferably 0.001 to 20% by weight, and even more preferably 0.001 to 15% by weight, based on the total weight of the compound (I) and the compound (II).

[0113] In addition to the silica particles (V), the polymerizable composition (α) may contain other components, such as additives, for example, a polymerization initiator, a polymerization accelerator, an ultraviolet absorber, a hindered amine light stabilizer (HALS), a solvent, a catalyst, an infrared absorber, a radical scavenger, an internal mold release agent, an antioxidant, a polymerization inhibitor, a dye other than the dye compound (B), a binder, a dispersant, and a leveling agent.

[0114] When a polymer, for example, a hydrophilic film containing a polymer, is produced from the polymerizable composition (α), the composition is polymerized. When the polymerization is carried out by radiation, for example, ultraviolet light, a photopolymerization initiator is usually contained in the polymerizable composition (α). When the polymerization is carried out by heat, a thermal polymerization initiator is usually contained in the polymerizable composition (α).

[0115] Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator. Among these photopolymerization initiators, a photoradical polymerization initiator is preferred.

[0116] Examples of the photoradical polymerization initiator include Irgacure 127 (manufactured by Ciba Specialty Chemicals), Irgacure 651 (manufactured by Ciba Specialty Chemicals), Irgacure 184 (manufactured by Ciba Specialty Chemicals), Darocur 1173 (manufactured by Ciba Specialty Chemicals), benzophenone, 4-phenylbenzophenone, Irgacure 500 (manufactured by Ciba Specialty Chemicals), and the like. Mikals), Irgacure 2959 (Ciba Specialty Chemicals), Irgacure 907 (Ciba Specialty Chemicals), Irgacure 369 (Ciba Specialty Chemicals), Irgacure 1300 (Ciba Specialty Chemicals), Irgacure 819 (Ciba Specialty Chemicals), Irgacure 1800 (Ciba Specialty Chemicals) Chemicals), Darocure TPO (Ciba Specialty Chemicals), Darocure 4265 (Ciba Specialty Chemicals), Irgacure OXE01 (Ciba Specialty Chemicals), Irgacure OXE02 (Ciba Specialty Chemicals), Esacure KT55 (Lamberty), Esacure ONE (Lamberty), Esacure KIP150 ( Examples of suitable antibacterial agents include Esacure KIP100F (manufactured by Lamberty), Esacure KT37 (manufactured by Lamberty), Esacure KTO46 (manufactured by Lamberty), Esacure 1001M (manufactured by Lamberty), Esacure KIP / EM (manufactured by Lamberty), Esacure DP250 (manufactured by Lamberty), Esacure KB1 (manufactured by Lamberty), and 2,4-diethylthioxanthone.

[0117] Among these photopolymerization initiators, Irgacure 127 (manufactured by Ciba Specialty Chemicals), Irgacure 184 (manufactured by Ciba Specialty Chemicals), Darocur 1173 (manufactured by Ciba Specialty Chemicals), Irgacure 500 (manufactured by Ciba Specialty Chemicals), Irgacure 819 (manufactured by Ciba Specialty Chemicals), Darocur TPO (manufactured by Ciba Specialty Chemicals), Esacure ONE (manufactured by Lamberty), Esacure KIP100F (manufactured by Lamberty), Esacure KT37 (manufactured by Lamberty), and Esacure KTO46 (manufactured by Lamberty) are preferred.

[0118] Examples of the photocationic polymerization initiator include Irgacure 250 (manufactured by Ciba Specialty Chemicals), Irgacure 784 (manufactured by Ciba Specialty Chemicals), Esacure 1064 (manufactured by Lamberty Chemicals), CYRAURE UVI6990 (manufactured by Union Carbide Japan), ADEKA OPTOMER SP-172 (manufactured by Asahi Denka), ADEKA OPTOMER SP-170 (manufactured by Asahi Denka), ADEKA OPTOMER SP-152 (manufactured by Asahi Denka), and ADEKA OPTOMER SP-150 (manufactured by Asahi Denka).

[0119] Examples of the thermal polymerization initiator include ketone peroxides such as methyl isobutyl ketone peroxide and cyclohexanone peroxide; Diacyl peroxides such as isobutyryl peroxide, o-chlorobenzoyl peroxide, and benzoyl peroxide; Dialkyl peroxides such as tris(t-butylperoxy)triazine and t-butylcumyl peroxide; Peroxyketals such as 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane and 2,2-di(t-butylperoxy)butane; Alkyl peresters such as α-cumyl peroxyneodecanoate, t-butyl peroxypivalate, 2,4,4-trimethylpenyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, and t-butyl peroxy-3,5,5-trimethylhexanoate; Examples thereof include percarbonates such as di-3-methoxybutyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyisopropyl carbonate, and diethylene glycol bis(t-butylperoxycarbonate).

[0120] The amount of the photopolymerization initiator and thermal polymerization initiator used is preferably in the range of 0.1 to 20% by weight, more preferably in the range of 0.5 to 10% by weight, and even more preferably in the range of 1 to 5% by weight, based on the total amount of compounds (I) and (II).

[0121] When the photopolymerization initiator is used, a photopolymerization accelerator may be used in combination, such as 2,2-bis(2-chlorophenyl)-4,5'-tetraphenyl-2'H-<1,2'>biimidazolyl, tris(4-dimethylaminophenyl)methane, 4,4'-bis(dimethylamino)benzophenone, 2-ethylanthraquinone, or camphorquinone.

[0122] In order to use a hydrophilic film containing a polymer of the polymerizable composition (α) as, for example, an antifouling material or an antifogging material and to prevent deterioration even when exposed to the outside for a long period of time, it is desirable to prepare a weather-resistant composition by further adding an ultraviolet absorber and a hindered amine-based light stabilizer to the polymerizable composition (α).

[0123] The ultraviolet absorber is not particularly limited, and various ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, propanediol-based ultraviolet absorbers, and oxanilide-based ultraviolet absorbers can be used.

[0124] Examples of the ultraviolet absorber include 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2H-benzotriazol-2-yl)-4-tert-butylphenol, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-butylphenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-6-(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-4-(3-one-4-oxa-dodecyl)-6-tert-butyl-phenol, 2-{5-chloro(2H)-benzotriazol-2-yl} ... benzotriazole-based ultraviolet absorbers such as 2-{5-chloro(2H)-benzotriazol-2-yl}-4-methyl-6-tert-butyl-phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol, 2-{5-chloro(2H)-benzotriazol-2-yl}-4,6-di-tert-butylphenol, 2-(2H-benzotriazol-2-yl)-4-tert-octylphenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-n-dodecylphenol, and reaction products of methyl-3-{3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl}propionate / polyethylene glycol 300; 2-(4-phenoxy-2-hydroxy-phenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-oxa-hexadecyloxy)-4,6-di(2,4-dimethyl-phenyl)-1,3,5-triazine, 2-(2-hydroxy-4-oxa-heptadecyloxy)-4,6-di(2,4-dimethyl-phenyl)-1,3,5-triazine, 2-(2-hydroxy-4-iso-octyloxy- triazine-based ultraviolet absorbers such as (2,4-dimethylphenyl)-4,6-di(2,4-dimethylphenyl)-1,3,5-triazine, trade name TINUVIN 400 (manufactured by Ciba Specialty Chemicals Co., Ltd.), trade name TINUVIN 405 (manufactured by Ciba Specialty Chemicals Co., Ltd.), trade name TINUVIN 460 (manufactured by Ciba Specialty Chemicals Co., Ltd.), and trade name TINUVIN 479 (manufactured by Ciba Specialty Chemicals Co., Ltd.); Benzophenone-based ultraviolet absorbers such as 2-hydroxy-4-n-octoxybenzophenone; benzoate-based ultraviolet absorbers such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; propanediocic acid ester-based ultraviolet absorbers such as propanediocic acid-{(4-methoxyphenyl)-methylene}-dimethyl ester, trade name Hostavin PR-25 (manufactured by Clariant Japan Co., Ltd.), trade name Hostavin B-CAP (manufactured by Clariant Japan Co., Ltd.); Examples include oxanilide-based ultraviolet absorbers such as 2-ethyl-2'-ethoxy-oxanilide, trade name Sanduvor VSU (manufactured by Clariant Japan Co., Ltd.) Among these ultraviolet absorbers, triazine-based ultraviolet absorbers tend to be preferred.

[0125] The hindered amine light stabilizer (HALS) is generally a general term for compounds having a 2,2,6,6-tetramethylpiperidine skeleton, and is broadly classified into low molecular weight HALS, medium molecular weight HALS, high molecular weight HALS, and reactive HALS depending on the molecular weight. Examples of hindered amine light stabilizers include Tinuvin 111FDL (manufactured by Ciba Specialty Chemicals), bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate (Tinuvin 123 (manufactured by Ciba Specialty Chemicals)), Tinuvin 144 (manufactured by Ciba Specialty Chemicals), and Tinuvin 292 (manufactured by Ciba Specialty Chemicals). (manufactured by Chiba Specialty Chemicals Co., Ltd.), trade name TINUVIN 765 (manufactured by Chiba Specialty Chemicals Co., Ltd.), trade name TINUVIN 770 (manufactured by Chiba Specialty Chemicals Co., Ltd.), N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine condensate (trade name CHIMASSORB119FL (manufactured by Chiba Specialty Chemicals Co., Ltd.)), trade name CHIMASSORB2020FDL (manufactured by Chiba Specialty Chemicals Co., Ltd.), dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate (trade name CHIMASSORB622LD (manufactured by Chiba Specialty Chemicals Co., Ltd.) Poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyllauryl-4-piperidyl)imino}] (trade name CHIMASSORB944FD, manufactured by Ciba Specialty Chemicals Co., Ltd.), Sanduvor 3050 Liquid (manufactured by Clariant Japan Co., Ltd.), Sanduvor 3052 Liquid (manufactured by Clariant Japan Co., Ltd.), and Sanduvor 3058 Liquid (manufactured by Clariant Japan Co., Ltd.).(manufactured by Clariant Japan Co., Ltd.), trade name Sanduvor 3051 Powder (manufactured by Clariant Japan Co., Ltd.), trade name Sanduvor 3070 Powder (manufactured by Clariant Japan Co., Ltd.), trade name VP Sanduvor PR-31 (manufactured by Clariant Japan Co., Ltd.), trade name Hostavin N20 (manufactured by Clariant Japan Co., Ltd.), trade name Hostavin N24 (manufactured by Clariant Japan Co., Ltd.), trade name Hostavin N30 (manufactured by Clariant Japan Co., Ltd.), trade name Hostavin N321 (manufactured by Clariant Japan Co., Ltd.), trade name Hostavin PR-31 (manufactured by Clariant Japan Co., Ltd.), trade name Hostavin 845 (manufactured by Clariant Japan Co., Ltd.), trade name Nylostab S-EED (manufactured by Clariant Japan Co., Ltd.), and the like.

[0126] The amounts of the UV absorber and hindered amine light stabilizer added are not particularly limited. Based on the total amount of compounds (I) and (II), the UV absorber is typically 0.1 to 20% by weight, preferably 0.5 to 10% by weight, and the hindered amine light stabilizer is typically 0.1 to 10% by weight, preferably 0.5 to 5% by weight, and more preferably 1 to 3% by weight. When the amounts of the UV absorber and hindered amine light stabilizer added are within the above ranges, the weather resistance of the polymerized product obtained from the polymerizable composition (α), for example, a hydrophilic film containing the polymerized product, is significantly improved. When the amounts of the UV absorber and hindered amine light stabilizer added are less than the above ranges, the weather resistance of the resulting polymerized product, for example, a hydrophilic film containing the polymerized product, tends to be less improved. On the other hand, when the amounts of the UV absorber and hindered amine light stabilizer added are greater than the above ranges, the polymerization of the polymerizable composition (α) may be insufficient.

[0127] In addition, additives other than those described above may be added to the polymerizable composition (α) as needed. For example, titanium oxide, other metals, metal oxides, etc. may be added to the polymerizable composition (α) for the purpose of improving the mechanical and thermal strength of the resulting hydrophilic film containing the polymer, or for the purpose of imparting photoresponsiveness and bactericidal properties, etc. For example, a compound having a sulfur atom may be added to the polymerizable composition (α) for the purpose of increasing the refractive index of the resulting hydrophilic film containing the polymer. For example, metal salts such as silver and lithium, iodine, and iodonium salts may be added to the polymerizable composition (α) for the purpose of imparting bactericidal and antibacterial properties, etc. The amount of these additives added can be appropriately determined depending on the purpose, but is usually in the range of 0.01 to 200 wt %, preferably 0.1 to 100 wt %, of the total weight of Compound (I) and Compound (II).

[0128] The polymerizable composition (α) can be used, for example, in the production of a laminate having a hydrophilic film and a substrate, which comprises a step of applying the polymerizable composition (α) to a substrate to form a composition layer, and a step of polymerizing the monomers containing compound (I) and compound (II) of the composition layer.

[0129] [solvent] In consideration of the workability when producing a hydrophilic film, for example, a laminate having a hydrophilic film and a substrate, from the polymerizable composition (α), it is a preferred embodiment that the polymerizable composition (α) contains a solvent. The solvent is not particularly limited as long as the water contact angle of the hydrophilic film containing the polymer obtained from the polymerizable composition (α) is 30° or less, but solvents that have too strong an interaction, such as reacting with the components contained in the polymerizable composition (α) or forming a salt with the components, and solvents with too high a boiling point, for example, solvents with a boiling point above 200°C, are not preferred. For example, ethanolamine-based compounds having a hydroxyethylamino structure, such as ethanolamine, diethanolamine, triethanolamine, N-ethylethanolamine, N-(2-ethylhexyl)ethanolamine, N-butyldiethanolamine, N-hexyldiethanolamine, N-lauryldiethanolamine, and N-cetyldiethanolamine [NRaRb(CH2CH2OH): Ra and Rb are independently hydrogen, an alkyl group having 1 to 15 carbon atoms, or a CH2CH2OH group] are preferred. ] interacts with the hydrophilic groups contained in compound (I), for example, with anionic hydrophilic groups such as sulfonic acid groups, and easily forms a salt or a salt-like form. Furthermore, it is difficult to evaporate, so even if you try to remove the solvent from the applied mixture, it tends to remain inside rather than moving to the surface exposed to the outside air. Therefore, the hydrophilic groups contained in compound (I) tend not to be inclined (concentrated) toward the surface exposed to the outside air of the applied material. Therefore, the above ethanolamine compounds are not desirable as solvents.

[0130] As the solvent, any appropriate solvent can be used, except for the solvents mentioned above, taking into consideration the solubility of compound (I), compound (II), surfactant (III), and dye compound (B), etc.

[0131] Examples of the solvent include alcohol-based solvents such as monohydric alcohols such as methanol, ethanol, isopropanol (IPA), 1-propanol, 1-butanol, isobutanol, 2-butanol, 1-pentanol (1-amyl alcohol), isopentanol, methoxyethanol, isopropoxyethanol, n-butoxyethanol, 1-methoxy-2-propanol, and 2-methoxy-1-propanol, and polyhydric alcohols such as ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, and glycerin; Ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, methyl isobutyl ketone, and cyclohexanone; Carboxylic acid solvents such as formic acid, acetic acid, and propionic acid; Carboxylic acid esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, and isobutyl acetate; carbonate esters such as ethylene carbonate and 1,2-propylene carbonate; and other ester solvents; ether solvents such as diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, and tetrahydrofuran; aprotic sulfonic solvents such as sulfolane; Aprotic sulfoxide solvents such as DMSO (dilauryl sulfoxide); Amide solvents such as N,N'-dimethylformamide (DMF), N,N'-dimethylimidazolidinone (DMI), and N,N'-dimethylacetamide (DMAC); Nitrile solvents such as acetonitrile and butyronitrile; and water; and mixtures of the above solvents, such as mixtures of water and alcohol-based solvents. In one preferred embodiment, the solvent that can be contained in the polymerizable composition (α) includes at least one solvent selected from the group consisting of ester solvents, alcohol solvents, and ketone solvents.

[0132] The solvent is a relatively highly polar solvent. When a solvent is added to the polymerizable composition (α), a highly polar solvent tends to be preferred. When a highly polar solvent is included in the polymerizable composition (α), it is usually desirable to remove at least a certain amount of the solvent from the polymerizable composition (α) before polymerizing the polymerizable composition (α). During this solvent removal process, the sulfonic acid group-containing compound (I) is removed from the surface of the polymerizable composition (α) (a coated product of the polymerizable composition (α), such as the composition layer of the polymerizable composition (α) described below) that is exposed to the outside air. As a result, the compound (I) is inclined (concentrated) toward the surface of the polymerizable composition (α) that is exposed to the outside air, forming a gradient structure of hydrophilic groups toward the surface. Therefore, to facilitate this inclination (concentration), it is preferable that the solvent have a moderate interaction with the sulfonic acid groups contained in the polymerizable composition (α). It is also desirable that the inclusion of the dye compound (B) does not inhibit the above-mentioned function.

[0133] The solubility parameter (SP) is widely known as an index that represents such polarity. The solubility parameter (SP) value (hereinafter also referred to as "SP value") can be easily calculated using the following simple calculation method.

[0134] Solubility parameter (SP) calculation formula 1) Latent heat of vaporization per 1 mol Hb = 21 x (273 + Tb) (unit: cal / mol), Tb: boiling point (°C) 2) Latent heat of vaporization per mol at 25°C H25 = Hb × {1 + 0.175 × (Tb - 25) / 100} (unit: cal / mol), Tb: boiling point (°C) 3) Intermolecular bond energy E=H25-596 (unit: cal / mol) 4) 1 ml of solvent (cm 3 ) intermolecular bond energy per E1 = E × D / Mw (unit: cal / cm 3 ),D: Density (g / cm 3 ), MW: molecular weight 5) SP value σ = (E1) 1 / 2 (unit: cal / cm3 ) 1 / 2

[0135] The solvent contained in the polymerizable composition (α) has an SP value of 9.3 to 10.5 (cal / cm) calculated by the above-mentioned simple calculation method. 3 ) 1 / 2 The solvent (C) is preferably a solvent having an SP value of 9.3 to 10.5 (cal / cm 3 ) 1 / 2 The polymerizable composition (α) containing the solvent is also referred to as polymerizable composition (α1). When the solvent (C) is a mixture of a plurality of compounds, the SP value of the solvent is the sum of the products of the SP values ​​of each solvent and the weight fractions of the solvents. For example, in a mixed solvent where solvent 1 has an SP value of σ1 and a weight fraction of W1, and solvent 2 has an SP value of σ2 and a weight fraction of W2, the SP value of the mixed solvent can be calculated as follows. SP value of a mixed solvent of solvent 1 and solvent 2 = (W1 × σ1) + (W2 × σ2) Similarly, in the case of a mixed solvent of three or more solvents, Solvent 1 to Solvent n (n is the number of solvents contained, which is three or more), the SP value of each solvent is calculated as σ1 to σ n , the weight fraction of each solvent is W1 to W n Then, it can be calculated as follows: SP value of mixed solvents of solvent 1 to solvent n = (W1 × σ1) + (W2 × σ2) + … + (W n ×σn) A polymer obtained from the polymerizable composition (α1) containing the solvent (C) having an SP value in the above range, for example, a hydrophilic film containing the polymer, has superior hydrophilicity and visibility.

[0136] From the viewpoint of the hydrophilicity and visibility of the obtained polymer, the SP value of the solvent (C) contained in the polymerizable composition (α1) is preferably 9.3 to 10.5 (cal / cm 3 ) 1 / 2 , more preferably 9.5 to 10.3 (cal / cm 3 ) 1 / 2 is.

[0137] In one preferred embodiment, the solvent (C) contained in the polymerizable composition (α1) has an SP value within the above-mentioned range and contains at least one solvent selected from the group consisting of ester solvents, alcohol solvents, and ketone solvents. Among these solvents (C), alcohol-based solvents such as methanol, ethanol, propanol, and 1-methoxy-2-propanol, ester-based solvents such as ethyl acetate, and ketone-based solvents such as methyl ethyl ketone, 2-pentanone, and methyl isobutyl ketone, mixtures of these solvents, and mixtures of these solvents with water are preferred. When the solvent (C) is a mixture of multiple compounds, it is sufficient that the SP value of the mixture calculated according to the above-mentioned calculation method is within the above-mentioned preferred range, and it is not necessary for the SP values ​​of all of the compounds constituting the mixture to be within the preferred range.

[0138] The amount of the solvent contained in the polymerizable composition (α) can be appropriately determined taking into consideration the polymer obtained from the polymerizable composition (α), the physical properties of the hydrophilic film containing the polymer, economic efficiency, and the like.

[0139] The amount of the solvent used is typically 1% by weight or more, preferably 10 to 90% by weight, more preferably 20 to 80% by weight, and even more preferably 30 to 70% by weight, in terms of the concentration (solids / (solids+solvent)×100) of the solids contained in the polymerizable composition (α) (the total amount of components contained in the polymerizable composition (α) other than the solvent, i.e., compound (I), compound (II), surfactant (III), dye compound (B), silica (IV) which is contained as needed, and the above-mentioned additives).

[0140] The hydrophilic film containing the polymerized product of the polymerizable composition (α) can be obtained by polymerizing the polymerizable composition (α) or the polymerizable composition (α1). For example, the hydrophilic film can be formed by applying the polymerizable composition (α) or the polymerizable composition (α1) to the surface of a substrate, removing the solvent contained in the composition as necessary, and then polymerizing the composition. The suitable polymerization conditions for the polymerizable composition (α) or the polymerizable composition (α1) are the same as the suitable conditions for polymerizing the monomers containing the compound (I) and the compound (II) in the composition layer of the laminate described below. When the polymerizable composition (α1) is used, it is preferable to carry out the polymerization after removing the solvent (C), and the suitable conditions for removing the solvent (C) are the same as the suitable conditions for removing the solvent (C) from the laminate described below.

[0141] The water contact angle of the hydrophilic film of the present disclosure thus obtained is usually 30° or less, preferably 20° or less, and more preferably 10° or less. A hydrophilic film having such a water contact angle has excellent hydrophilicity.

[0142] The hydrophilic film of the present disclosure is usually provided on at least one surface of a substrate. The reason why such a highly hydrophilic film can be obtained is thought to be that when the polymerizable composition (α) or the polymerizable composition (α1) is applied to a substrate or the like and polymerized by heat, radiation (e.g., ultraviolet light), etc., the sulfonic acid groups self-assemble on the surface exposed to the air, and then a hydrophilic film containing the polymerized product is formed. Furthermore, when a dye compound with a solubility in water of 1 g / 100 g or less is added, the function of such sulfonic acid groups is not hindered, contributing to improved visibility.

[0143] As described above, the hydrophilic film of the present disclosure is believed to have a high concentration of the above-mentioned hydrophilic groups on its surface, and therefore has excellent antifogging properties, antifouling or self-cleaning properties, antistatic properties or dust-resistant properties, and the like, and also has excellent visibility due to the inclusion of the dye compound (B).

[0144] In this highly hydrophilic membrane, sulfonic acid groups are preferably distributed from the depth of the membrane on the substrate side to the surface, and have a concentration difference (gradient (hydrophilic group concentration ratio) (Sa / Da)) such that they are distributed in large numbers particularly on the outermost surface of the hydrophilic membrane that comes into contact with the outside air.

[0145] In the hydrophilic membrane of the present disclosure, the gradient (hydrophilic group concentration ratio) (Sa / Da) of the surface concentration (Sa) of sulfonic acid groups to the deep concentration (Da) of sulfonic acid groups at a point halfway through the membrane thickness of the hydrophilic membrane is preferably 1.1 or more, more preferably 1.2 or more, even more preferably 1.3 or more, and even more preferably 1.5 or more. The gradient (hydrophilic group concentration ratio) (Sa / Da) is preferably 20.0 or less.

[0146] The gradient (hydrophilic group concentration ratio) is determined by cutting a hydrophilic membrane sample obliquely, measuring the sulfonic acid group concentrations at the surface of the hydrophilic membrane exposed to the outside air and at a point halfway through the membrane thickness as fragment ion intensities using a time-of-flight secondary ion mass spectrometer (TOF-SIMS), and then calculating the values ​​(relative intensities) of the sulfonic acid groups.

[0147] Hydrophilic films with a water contact angle below the above-mentioned value are highly hydrophilic and easily absorb (wet) water, making them excellent hydrophilic materials. Therefore, they are useful, for example, for anti-fogging materials, anti-fogging films (hereinafter also referred to as anti-fogging coats), anti-fouling materials, anti-fouling films, or self-cleaning coats, as well as anti-static materials, anti-static films, or dust-resistant coats. For example, when used as an anti-fogging coat, water droplets spread across the film surface, forming a water film, providing excellent anti-fogging effects. When used as a self-cleaning coat, water penetrates between the dirt and the coating surface, lifting and removing the dirt, providing excellent anti-fouling effects. Furthermore, in hydrophilic films, the evaporation area expands as water spreads, improving the evaporation rate and resulting in faster drying.

[0148] Furthermore, since the hydrophilic film of the present disclosure is believed to have a high concentration of sulfonic acid groups segregated (concentrated) on the surface, it has superior antistatic properties compared to conventional hydrophilic coatings in which hydrophilic groups are not segregated. Furthermore, since the hydrophilic film of the present disclosure has sulfonic acid groups as hydrophilic groups, it has superior antistatic properties compared to conventional coatings containing nonionic hydrophilic groups. Therefore, the hydrophilic film of the present disclosure is also useful as an antistatic material, antistatic coating, dust-proof coating, etc.

[0149] When the water contact angle is 30° or less, preferably 20° or less, and more preferably 10° or less, the hydrophilic film of the present disclosure is particularly preferably used as an anti-fogging material, an anti-fouling material, a quick-drying material, or an anti-static material. The water contact angle is usually 0° or more.

[0150] Polymerization of the polymerizable composition (α) or (α1) containing surfactant (III) allows hydrophilic groups derived from compound (I) to segregate (gradient) to the surface of the resulting hydrophilic film, and also allows hydrophilic films containing hydrophilic polymers to be obtained under a wider range of conditions. Furthermore, the inclusion of surfactant (III) relatively enhances the transparency of the resulting hydrophilic film, likely due to a compatibility effect that inhibits separation of compound (I) and compound (II). Furthermore, the inclusion of surfactant (III) allows hydrophilic films in which hydrophilic groups are segregated (gradient) to the surface to be obtained from compositions containing general hydrophilic polymerizable compounds (e.g., hydrophilic polymerizable compounds other than those claimed in WO 2007 / 064003), which could not be graded by conventional methods (e.g., WO 2007 / 064003) in which the hydrophilic groups are graded to the surface by accompanying the evaporation of a polar solvent. Furthermore, compositions containing the hydrophilic compounds described in the above publications tend to give hydrophilic films with higher hydrophilicity, in which hydrophilic groups are segregated (graded) on the surface.

[0151] Furthermore, by polymerizing the polymerizable composition (α) or the polymerizable composition (α1) containing the surfactant (III) (typically the compound (III')), a hydrophilic film having excellent leveling properties and high hydrophilicity, or a laminate having the hydrophilic film and a substrate, can be obtained. Furthermore, such a hydrophilic film having high surface smoothness (leveling properties) is resistant to external attack (for example, erosion by hot water, etc.), and its durability also tends to be improved.

[0152] The thickness of the hydrophilic film of the present disclosure can be determined appropriately depending on the application, but is usually in the range of 0.0001 to 500 μm, preferably 0.05 to 500 μm, more preferably 0.1 to 300 μm, even more preferably 0.5 to 100 μm, still more preferably 1 to 50 μm, and particularly preferably 2 to 30 μm.

[0153] The laminate of the present disclosure has a hydrophilic film containing the polymerizable composition (α) or a polymer of the polymerizable composition (α1) and a substrate. A preferred embodiment of the laminate of the present disclosure is a laminate in which the hydrophilic film is formed on the surface of a substrate. For example, when the hydrophilic film is an anti-fogging film, an anti-fouling film, a quick-drying film, or an anti-static film, a laminate in which the substrate is coated with the anti-fogging film, the anti-fouling film, the quick-drying film, or the anti-static film is obtained.

[0154] Examples of the substrate include substrates made of non-base materials such as glass, silica, metals, and metal oxides; Substrates made of organic materials such as polyacrylamide, polyisopropylacrylamide, polyacrylonitrile, polymethyl methacrylate (PMMA), polycarbonate, polyethylene terephthalate, polyethylene, polypropylene, polystyrene, polyurethane resin, epoxy resin, vinyl chloride resin, silicone resin, paper, and pulp; Organic-inorganic substrates such as SMC and BMC, which are composites of unsaturated polyester resin, fillers such as calcium carbonate, and glass fibers; and Examples of the substrate include a substrate having a coating layer made of a cured coating material, which is formed by coating the surface of a substrate made of these inorganic materials, organic materials, or organic-inorganic composite materials. When the laminate of the present disclosure is used by being attached to a transparent material (for example, glass), among the above substrates, a polyethylene terephthalate substrate is one preferred embodiment.

[0155] Furthermore, if necessary, the surface of these substrates may be subjected to physical or chemical treatments such as corona treatment, ozone treatment, low-temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, flame treatment, etc., for the purpose of activating the surface of the substrate. Furthermore, instead of or in addition to these treatments, primer treatment, undercoat treatment, or anchor coat treatment may be performed.

[0156] Examples of coating agents that can be used in the primer treatment, undercoat treatment, and anchor coat treatment include those containing, as the main component of the vehicle, a polyester resin, a polyamide resin, a polyurethane resin, an epoxy resin, a phenolic resin, a (meth)acrylic resin, a polyvinyl acetate resin, a polyolefin resin such as polyethylene or polypropylene, or a copolymer or modified resin thereof, a cellulose resin, etc. The coating agent may be either a solvent-based coating agent or a water-based coating agent.

[0157] Among these coating agents, modified polyolefin-based coating agents, ethyl vinyl alcohol-based coating agents, polyethyleneimine-based coating agents, polybutadiene-based coating agents, polyurethane-based coating agents; Polyester-based polyurethane emulsion coating agent, polyvinyl chloride emulsion coating agent, urethane acrylic emulsion coating agent, silicone acrylic emulsion coating agent, vinyl acetate acrylic emulsion coating agent, acrylic emulsion coating agent; Preferred are styrene-butadiene copolymer latex coating agents, acrylonitrile-butadiene copolymer latex coating agents, methyl methacrylate-butadiene copolymer latex coating agents, chloroprene latex coating agents, rubber-based latex coating agents such as polybutadiene latex, polyacrylic acid ester latex coating agents, polyvinylidene chloride latex coating agents, polybutadiene latex coating agents, and coating agents consisting of carboxylic acid-modified latexes or dispersions of the resins contained in these latex coating agents.

[0158] These coating agents can be applied by, for example, gravure coating, reverse roll coating, knife coating, kiss coating, etc., and the amount applied to the substrate is usually 0.05 g / m after removing the solvent contained in the composition. 2 ~10g / m 2 , preferably 0.05 g / m 2 ~5g / m 2 is.

[0159] Among these coating agents, polyurethane-based coating agents are more preferred. Polyurethane-based coating agents have urethane bonds in the main chain or side chain of the resin contained in the coating agent. Polyurethane-based coating agents are coating agents containing polyurethane obtained by reacting a polyol such as polyester polyol, polyether polyol, or acrylic polyol with an isocyanate compound.

[0160] Among these polyurethane coating agents, polyurethane coating agents obtained by mixing a polyester polyol such as a condensation polyester polyol or a lactone polyester polyol with an isocyanate compound such as tolylene diisocyanate, hexamethylene diisocyanate, or xylene diisocyanate are preferred because of their excellent adhesion.

[0161] The method for mixing the polyol compound and the isocyanate compound is not particularly limited. The compounding ratio is also not particularly limited, but since too little isocyanate compound may cause poor curing, it is preferable that the ratio of OH groups of the polyol compound to NCO groups of the isocyanate compound is in the range of 2 / 1 to 1 / 40 in terms of equivalents.

[0162] The substrate used in the laminate may have a substrate surface that has been subjected to the surface activation treatment.

[0163] The laminate of the present disclosure can be produced, for example, through a step of applying the polymerizable composition (α) or the polymerizable composition (α1) to a substrate to form a composition layer, and a step of polymerizing the monomers containing the compound (I) and the compound (II) of the composition layer. In particular, when a laminate is produced from the polymerizable composition (α1), A step of applying the polymerizable composition (α1) to a substrate to form a composition layer; removing at least a portion of the solvent (C) from the composition layer; and In one preferred embodiment, the laminate is produced by a production method including a step of polymerizing a monomer containing compound (I) and compound (II) in the composition layer after removal of the solvent (C).

[0164] In the method for producing the laminate, first, the polymerizable composition (α1) is applied to a substrate to form a composition layer. The method for applying the polymerizable composition (α1) to the substrate is not particularly limited, and for example, it can be applied by gravure coating, reverse roll coating, knife coating, kiss coating, etc. The amount of the polymerizable composition (α1) to be applied to the substrate can be determined appropriately depending on the application, but is usually 0.05 g / m in a state in which the solvent contained in the polymerizable composition (α1) has been removed. 2 ~10g / m 2 , preferably 0.05 g / m 2 ~5g / m 2 is.

[0165] In the method for producing the laminate, after forming a composition layer on a substrate, at least a portion of the solvent (C) is removed from the composition layer. This solvent removal from the composition layer is preferably performed thoroughly before polymerizing the monomers containing compound (I) and compound (II) of the composition layer described below. If the solvent (C) is not sufficiently removed from the polymerizable composition (α1), the sulfonic acid groups derived from compound (I) will migrate less to the surface of the composition layer exposed to the outside air, which tends to reduce the hydrophilicity of the resulting hydrophilic film. Even if the sulfonic acid groups migrate to the surface of the composition layer exposed to the outside air, if the solvent (C) remains in the composition layer, they tend to migrate more easily into the interior of the composition layer due to repulsive interactions with the air (hydrophobicity) present on the surface exposed to the outside air. This can result in insufficient concentration (gradient) of the sulfonic acid groups on the surface exposed to the outside air in the resulting hydrophilic film, reducing the hydrophilicity and further reducing adhesion to the substrate. Therefore, it is generally preferable to have as little solvent remaining in the composition layer as possible immediately before polymerization. The amount of the solvent (C) remaining in the composition layer immediately before polymerization is usually 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less, and even more preferably 1% by weight or less.

[0166] The temperature during removal of the solvent (C) is determined appropriately, but is usually in the range of room temperature to 200°C, preferably 30 to 150°C, more preferably 40 to 120°C, and particularly preferably 40 to 100°C.

[0167] The time required for removing the solvent (C) from the composition layer may be determined as appropriate, but a shorter time tends to be preferable when productivity is taken into consideration. For example, the solvent (C) can be removed in typically 30 minutes or less, preferably 10 minutes or less, more preferably 5 minutes or less, even more preferably 3 minutes or less, and particularly preferably 2 minutes or less. The atmosphere during solvent (C) removal may be air or an inert gas such as nitrogen, but a lower humidity atmosphere tends to be preferable, as it prevents deterioration of the appearance of the resulting hydrophilic film (e.g., orange peel, reduced transparency, etc.). Specifically, the humidity of the atmosphere is preferably 80% or less, more preferably 70% or less, even more preferably 65% ​​or less, even more preferably 60% or less, and particularly preferably 55% or less.

[0168] When the solvent (C) is removed by wind, the wind speed is preferably 30 m / sec or less, more preferably in the range of 0.1 to 30 m / sec, even more preferably in the range of 0.2 to 20 m / sec, and particularly preferably in the range of 0.3 to 10 m / sec.

[0169] The pressure during removal of the solvent (C) is not particularly limited, and normal pressure or reduced pressure is relatively preferred, but slight pressure may also be used. As described above, when the hydrophilic membrane of the present disclosure itself is produced from the polymerizable composition (α1) or from the polymerizable composition (α) containing a solvent, it is desirable to remove the solvent according to the solvent removal conditions described above.

[0170] When producing the above laminate, a laminate having a hydrophilic film and a substrate can be obtained by polymerizing a monomer containing compound (I) and compound (II) of the composition layer after removal of the above-mentioned solvent (C). The polymerization method is not particularly limited, and for example, polymerization can be carried out using heat, radiation (for example, ultraviolet light), or a combination of both.

[0171] The polymerization can be carried out in the air, but is preferably carried out in an inert gas atmosphere such as nitrogen, since this shortens the polymerization time.

[0172] When polymerization is carried out using heat, the composition is usually made to contain a thermal polymerization initiator (thermal radical generator) such as an organic peroxide, and heated within a range from room temperature to 300°C or lower.

[0173] When polymerization is carried out using radiation (for example, ultraviolet light), the composition is usually made to contain a photopolymerization initiator and then irradiated with radiation. When polymerization is carried out using radiation (e.g., ultraviolet light), energy rays having a wavelength in the range of 0.0001 to 800 nm can be used. The radiation can be classified into α-rays, β-rays, γ-rays, X-rays, electron beams, ultraviolet light, visible light, etc., and can be appropriately selected and used depending on the composition of the mixture. Among these radiations, ultraviolet light is preferred, and the output peak of ultraviolet light is preferably in the range of 200 to 450 nm, more preferably in the range of 230 to 445 nm, even more preferably in the range of 240 to 430 nm, and particularly preferably in the range of 250 to 400 nm. When ultraviolet light having an output peak in the above range is used, problems such as yellowing and thermal deformation during polymerization are minimized, and polymerization can be completed in a relatively short time even when an ultraviolet absorber is added.

[0174] Furthermore, when an ultraviolet absorber or a hindered amine stabilizer is added to the polymerizable composition (α) or the polymerizable composition (α1), it is preferable to use ultraviolet light having an output peak in the range of 250 to 280 nm or 370 to 430 nm.

[0175] When polymerizing the polymerizable composition (α) or the polymerizable composition (α1) using radiation (e.g., ultraviolet light), in order to avoid polymerization inhibition by oxygen, the composition may be applied to a substrate or the like, and after removing the solvent contained in the composition as necessary, the coating layer may be covered with a coating material (e.g., a film) and irradiated with radiation to polymerize. When covering the coating layer with a coating material, it is desirable to ensure close contact between the coating layer and the coating material so that air (oxygen) is not trapped between them. By blocking oxygen, for example, the amount of (photo)polymerization initiator and the amount of radiation (e.g., ultraviolet light) exposure may be reduced.

[0176] The covering material may be any material and in any form as long as it blocks oxygen, but from the viewpoint of operability, a film is preferred, and among these films, a transparent film that is easy to polymerize by radiation (e.g., ultraviolet light) is preferred. The film thickness is usually in the range of 3 to 200 μm, with 5 to 100 μm being preferred, and 10 to 50 μm being even more preferred.

[0177] Examples of film materials that are preferably used as the above-mentioned covering material include polyvinyl alcohol (PVA), vinyl alcohol polymers such as ethylene-vinyl alcohol copolymer, polyacrylamide, polyisopropylacrylamide, polyacrylonitrile, polycarbonate (PC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polystyrene (PS), and biaxially oriented polypropylene (OPP).

[0178] Although the equipment is expensive, using an electron beam in the range of 0.01 to 0.002 nm as radiation is a preferred embodiment because it allows polymerization to be completed in a short time. As described above, the hydrophilic film of the present disclosure itself may be produced by subjecting the polymerizable composition (α) or the polymerizable composition (α1) to the polymerization conditions described above.

[0179] A preferred embodiment of the laminate of the present disclosure is a laminate in which a hydrophilic film is formed on one side of a substrate and an adhesive layer is formed on the side of the substrate on which the hydrophilic film is not formed. For example, when the substrate is a film, a preferred embodiment is one in which the hydrophilic film of the present disclosure is formed on one side of the substrate film, and an adhesive layer is formed on the side on which the hydrophilic film is not formed, and a release film is also preferably provided on the surface of the adhesive layer. If an adhesive layer is laminated on the other side of the substrate film, the laminate film (laminate) having the hydrophilic film of the present disclosure can be easily attached as an anti-fog film and an anti-fouling film to glass, mirrors in bathrooms, the surfaces of display materials such as displays and televisions, signboards, advertisements, guide boards, signs on railways and roads, the exterior walls of buildings, window glass, etc.

[0180] The adhesive used in the adhesive layer is not particularly limited, and known adhesives can be used. Examples of adhesives include acrylic adhesives, rubber adhesives, vinyl ether polymer adhesives, and silicone adhesives. The thickness of the adhesive layer is usually in the range of 2 to 50 μm, and preferably in the range of 5 to 30 μm.

[0181] In the hydrophilic film of the present disclosure and the laminate including the hydrophilic film and the substrate, the surface of the hydrophilic film that is in contact with the outside air may be covered with a covering material, which can prevent the hydrophilic film from being damaged or soiled during transportation, storage, display, etc.

[0182] As the coating material, the aforementioned coating material that has been adhered to the coating film when the hydrophilic film of the present disclosure is formed on the substrate or the like by polymerization using radiation can also be used as the coating material as is.

[0183] Examples of film materials that are preferably used as the above-mentioned covering material include polyvinyl alcohol (PVA), polyacetyl cellulose (TAC), vinyl alcohol polymers such as ethylene-vinyl alcohol copolymer, polyacrylamide, polyisopropylacrylamide, polyacrylonitrile, polycarbonate (PC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polyacrylonitrile-butadiene-styrene copolymer (ABS), polystyrene (PS), and biaxially oriented polypropylene (OPP).

[0184] Furthermore, by polymerizing the polymerizable composition (α) or the polymerizable composition (α1) in molds of various shapes, it is also possible to obtain polymers (cured products) having various shapes, such as hydrophilic films and molded articles.

[0185] The hydrophilic film of the present disclosure and a laminate having the hydrophilic film and a substrate can be suitably used as an anti-fogging material, an anti-fouling material, a quick-drying material, an anti-static material, and the like.

[0186] The hydrophilic film and the laminate having the hydrophilic film and a substrate can be used in, for example, vehicles and vehicle materials, ships and ship materials, aircraft and aircraft base materials, buildings and building materials, windows, mirrors, exterior walls, exteriors, bodies, wheels, interior walls, interiors, floors, furniture and furniture materials for vehicles, ships, aircraft and buildings, etc., utilities such as piping and wiring and materials thereof, textile products such as clothing and cloth, home appliances such as sinks, bathrooms, dressing rooms, ventilation fans, and kitchens and materials thereof, electrical appliances such as washing machines, dish dryers, refrigerators, microwave ovens, ovens, and shavers and materials thereof, displays and materials thereof, optical films, optical discs, optical lenses, etc. The composition can be used to impart hydrophilicity, antifogging, quick-drying, and antifouling properties to optical articles such as eyeglass lenses, contact lenses, and goggles, dental materials such as dentures and dentures, lighting articles such as lamps and lights and their materials, heat exchanger parts such as cooling fins and their materials, recording and printing materials such as photoresists and inkjet recording plates, cosmetic containers and their materials, reflective materials such as reflective films and reflectors, sound-insulating plates installed on highways, display materials, printing or printing primers, other primers, flat panels, touch panels, sheets, films, tapes, transparent resins, and transparent materials such as glass. It can also be used to impart anti-condensation properties and anti-static properties. [Example]

[0187] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0188] [Preparation Example 1] (Preparation of Precursor Composition A) A homogeneous polymerizable precursor composition A having a solid content of 80% by weight was prepared according to the blending ratios shown in Table 1. The abbreviations for each compound in the table are as follows:

[0189] [Table 1] SPA-K: Potassium 3-acryloyloxypropylsulfonate (potassium 3-sulfopropylacrylate) S-EED: N,N'-bis-2,2,6,6-tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide PGM: 1-methoxy-2-propanol

[0190] [ka]

[0191] [Preparation Example 2] (Preparation of 10 wt% surfactant-containing liquid) 10 g of sodium distearyl sulfosuccinate (hereinafter abbreviated as DS-Na), 30 g of water, and 60 g of 1-methoxy-2-propanol (PGM) were mixed at 15,000 rpm for 3 minutes using a homomixer (Primix Corporation, Robomix (registered trademark) S-model) to prepare a solution containing 10 wt% DS-Na.

[0192] [ka]

[0193] [Preparation Example 3] (Preparation of Coating Composition A) 10.0 g of the polymerizable precursor composition A obtained in Preparation Example 1 was mixed with 0.11 g of the 10 wt % DS-Na-containing solution obtained in Preparation Example 2 as a surfactant-containing solution, 0.24 g of Darocur 1173 (manufactured by BASF) as a UV polymerization initiator, and 5.4 g of PGM as a dilution solvent to prepare a coating composition A with a solid content of 60 wt %.

[0194] In the examples and comparative examples, the following compounds were used as dye compounds. Dye compound (B-1): Tetraazaporphyrin dye mixture consisting of tetraazaporphyrin compound isomers (Yamamoto Chemical Industry Co., Ltd., KUKKIRI Dye (registered trademark), solubility in water: <0.1 g / 100 g, maximum absorption wavelength: 585 nm) Dye compound (B'-1) Brilliant Blue FCF (Fujifilm Wako Pure Chemical Industries, Ltd., solubility in water: >1 g / 100 g, maximum absorption wavelength: 627-631 nm, CAS: 3844-45-9) Dye compound (B'-2) Methyl Red Sodium (Fujifilm Wako Pure Chemical Industries, Ltd., solubility in water: >1 g / 100 g, maximum absorption wavelengths: 437, 410, 493 nm, CAS: 845-10-3)

[0195] The physical properties of the hydrophilic surface layer and the like were evaluated as follows.

[0196] <Evaluation of Paint Appearance> The mixture of the polymerizable composition, the dye compound (B), the solvent (C), and the photoinitiator shown in Table 2 below was evaluated based on the following criteria. 〇: No undissolved matter, transparent △: No undissolved matter, but somewhat opaque ×: Undissolved matter was observed and the state was opaque

[0197] <Evaluation of Coating Film Appearance> The resulting hydrophilic surface layer was visually evaluated based on the following criteria. 〇: No foreign matter and transparent △: Some foreign matter is found, but the product is transparent ×: Many foreign objects are found and the product is opaque

[0198] <Measurement of Water Contact Angle> Using a water contact angle measuring device CA-V manufactured by Kyowa Interface Science Co., Ltd., measurements were taken at three locations per sample, and the average of these values ​​was taken as the water contact angle value.

[0199] <Measurement of Maximum Absorption Wavelength> The transmission spectrum of the obtained test film was measured using a spectrophotometer (Shimadzu Corporation, trade name: UV3150) to determine the maximum absorption wavelength.

[0200] [Example 1] (Preparation of PET film with hydrophilic surface layer) To 41.4 g of the coating composition liquid A obtained in Preparation Example 3 above, 0.12 g of (B-1) as the dye compound (B), 58.5 g of PGM as the solvent (C), and 0.75 g of Irgcure1173 as a photoinitiator were added to obtain a polymerizable composition (α1-1) (paint) with a solid content of 25 wt %. The polymerizable composition (α1-1) was applied to one side of the PET film Lumirror U403 using a bar coater #12, and the film was placed in a hot air dryer for 2 minutes at 60°C to remove the solvent contained in the composition, thereby obtaining a PET film having an uncured composition layer. The PET film having the composition layer was passed through a UV conveyor once and then irradiated with UV light (electrodeless H bulb, illuminance 240 W / cm 2 , cumulative light intensity 200mJ / cm 2 ) to form a hydrophilic film (hydrophilic film formed from a cross-linked polymer) with a thickness of about 3 μm on the PET film substrate, thereby obtaining a laminate. The appearance of the polymerizable composition (α1-1) as a coating material and the resulting laminate including the hydrophilic film were evaluated according to the above. The results are shown in Table 2.

[0201] [Examples 2 to 4, Comparative Examples 1 to 6] Polymerizable compositions with solid contents of 25% by weight were obtained in the same manner as in Experimental Example 1, except that the types and amounts of the dye compound (B) and solvent (C) added were changed as shown in Table 2 below, and PET films having uncured composition layers were also obtained. Under the same conditions as in Experimental Example 1, the PET film having the composition layer was irradiated with UV light to form a hydrophilic film (a hydrophilic film formed from a cross-linked polymer) having a thickness of approximately 3 μm on the PET film substrate. The appearance of the polymerizable composition as a coating material and the resulting laminate including the hydrophilic film were evaluated according to the above. The results are shown in Table 2.

[0202] [Table 2] [Industrial Applicability]

[0203] The hydrophilic film of the present disclosure and the laminate having the hydrophilic film and a substrate have excellent hydrophilicity and visibility, and are therefore useful in the various applications described above.

Claims

1. A hydrophilic film comprising a polymer of a polymerizable composition (α) containing the following compound (I), the following compound (II), a surfactant (III) (provided that the surfactant (III) does not have a polymerizable carbon-carbon double bond), and the following dye compound (B), The hydrophilic film has a water contact angle of 30° or less. Compound (I): a compound having a sulfonic acid group and at least one functional group having a polymerizable carbon-carbon double bond; Compound (II): a compound having two or more functional groups each having a polymerizable carbon-carbon double bond (but not having a sulfonic acid group); Dye compound (B): A dye compound having a solubility in water of 1 g / 100 g or less.

2. 2. The hydrophilic film according to claim 1, wherein the dye compound (B) is a tetraazaporphyrin compound.

3. A compound (I) having a sulfonic acid group and at least one functional group having a polymerizable carbon-carbon double bond; Compound (II) having two or more functional groups having a polymerizable carbon-carbon double bond (provided that the compound does not have a sulfonic acid group), Surfactant (III) (provided that surfactant (III) does not have a polymerizable carbon-carbon double bond), A dye compound (B) having a solubility in water of 1 g / 100 g or less, and The solubility parameter (SP) is 9.3 to 10.5 (cal / cm 3 ) 1 / 2 A polymerizable composition (α1) comprising a solvent (C)

4. The polymerizable composition (α1) according to claim 3, wherein the solvent (C) comprises at least one selected from the group consisting of an ester solvent, an alcohol solvent, and a ketone solvent.

5. A step of applying the polymerizable composition (α1) according to claim 3 to a substrate to form a composition layer; removing at least a portion of the solvent (C) from the composition layer; and a step of polymerizing the monomers containing the compound (I) and the compound (II) in the composition layer after the removal of the solvent (C). A method for producing a laminate having a hydrophilic film and a substrate.

6. A laminate comprising at least one layer of the hydrophilic film according to claim 1 and a substrate.

7. The laminate of claim 6, wherein the substrate is a polyethylene terephthalate substrate.

8. The laminate according to claim 6 , wherein a hydrophilic film is formed on one surface of the substrate, and an adhesive layer is formed on the surface of the substrate on which the hydrophilic film is not formed.

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