DESCRIPTION
COMPOSITION AND FILM COMPRISING SAME
5 TECHNICAL FIELD [0001]
The present invention relates to a hydrophilic film having antifogging, antifouling and antistatic properties as well as excellent abrasion resistance and weather resistance; a 10 polymerizable composition for obtaining the hydrophilic film; and use thereof.
BACKGROUND ART [0002] 15 In recent years, there has been an increasing demand for improvement against fogging and fouling that occur on substrate surfaces such as plastic surface and glass surface. [0003]
As a method for solving this problem of fogging, an 20 antifogging coating material prepared by adding a reactive
surfactant to an acrylic oligomer has been proposed and a cured film obtained from this antifogging coating material is described to have improved hydrophilicity and water absorption properties (Non-Patent Document 1} . In addition, for example, as a method

SF-2582 2
for solving the problem of fouling, antifouling materials having self-cleaning properties (antifouling properties) that improve the surface hydrophilicity and allow dirt (hydrophobic substance in ambient air, etc.) adhered to an external wall or the like to 5 come off and be efficiently removed with rainfall, sprinkled water or the like have been attracting attention (Non-patent Documents 2 and 3). [0004]
As a means of completely overcoming these problems of
10 "fogging" and "fouling", the present inventors proposed a
monolayer film in which anionic hydrophilic groups are biased (concentrated) to the surface (Patent Document 1). The hydrophilic film obtained by the invention is transparent and extremely highly hydrophilic and has excellent antifogging,
15 antifouling, antistatic and quick-drying (high drying rate of adhered water) properties as well as excellent chemical resistance, Besides, this hydrophilic film is hard and also has excellent scratch resistance. However, investigations by the present inventors revealed that the hydrophilic film is not satisfactory
20 in terms of abrasion resistance and weather resistance. [0005]
Generally, as a method for attaining excellent weather resistance and improving the abrasion resistance of a surface, a method of coating an inorganic compound is known.

SF-2582 3
Representative examples of the use of such a method include a case where a silica compound prepared by sol-gel reaction is used as a hard coat of a spectacle lens (Non-patent Document 4). [0006] 5 A silica coating has a dense structure; therefore, it is extremely hard and its abrasion resistance reaches a level that is comparable to that of glass. However, at the same time, there are also problems, for example, that it is readily cracked and cannot be stained and that it readily allows dirt to adhere and
10 to be fixed thereon. As a method of solving these problems, a variety of proposals have been made. For example, as a method of imparting staining property and toughness, a method of incorporating a melamine-polyhydric alcohol condensate and an epoxy group-containing silane compound into silica (Patent
15 Document 2), a method of incorporating an epoxy compound and an aluminum complex into silica (Patent Document 3) and a method of incorporating a hydroxy group-containing acrylic polymer into silica (Patent Document 4) have been proposed. [0007]
20 As a method of imparting antifogging property by
hydrophilization, a method of incorporating a styrene-based sulfonic acid polymer into silica has been proposed (Patent Document 5).

SF-2582 4
CITATION LIST PATENT DOCUMENTS [0008]
[Patent Document 1] WO 2007/064003 5 [Patent Document 2] Japanese Laid-open Patent Application (Kokai) No. S56-22365
[Patent Document 3] Japanese Laid-open Patent Application (Kokai) No. S61-166824
[Patent Document 4] Japanese Laid-open Patent Application 10 (Kokai) No. H06-166847"
[Patent Document 5] Japanese Laid-open Patent Application (Kokai) No. Hll-021512 NON-PATENT DOCUMENTS [0009] 15 [Non-patent Document 1] Toagosei Annual Research Report, TREND 1999, February, p.39-44
[Non-patent Document 2] Polymer, 44(5), p.307, 1995 [Non-patent Document 3] Expected Materials for the Future, 2{1), p.36-41, 2002 20 [Non-patent Document 4] Technology and Application of Plastic Lens System, p.165-166, CMC Publishing Co., Ltd., published on June 30, 2003
SUMMARY OF THE INVENTION

SF-2582 5
PROBLEMS TO BE SOLVED BY THE INVENTION [0010]
The above-described proposal of Patent Document 5 is likely to improve the hydrophilicity and is thus preferred; however, the 5 polymer easily dissociates from the resulting film and the
hydrophilicity tends to be reduced by water. Particularly, these problems are more conspicuous as the film thickness increases and investigations by the present inventors have revealed that the film has a problem that it cannot withstand use in such a situation
10 where antifogging and antifouling properties (self-cleaning by rainwater and the like) are actually required. An object of the present invention is to provide a hydrophilic film having an excellent balance of hydrophilicity and abrasion resistance as well as excellent weather resistance, in which film a reduction
15 in the hydrophilicity caused by water is small.
MEANS FOR SOLVING THE PROBLEMS [0011]
The present inventors have intensively studied to solve the 20 above-described problems and discovered that a cured film which is obtained by allowing a polymer having an epoxy group reactive with silanol and a hydrophilic sulfonic acid group to react with a silane compound by sol-gel reaction can provide a hydrophilic film having an excellent balance of hydrophilicity and abrasion

SF-2582 6
resistance as well as excellent weather resistance, in which film a reduction in the hydrophilicity caused by water is small. [0012]
That is, the present invention relates to the following [1] 5 to [14]. [0013]
[1] A composition, comprising:
a polymer (i) which has a -SO3M group and an epoxy group, wherein M represents a hydrogen atom, an alkali metal, an alkaline 10 earth metal or an ammonium ion; and
a silane compound (ii) which has a total of two or more groups or atoms that are selected from the group consisting of a hydroxy group bound to a silane atom, an alkoxy group bound to a silane atom and a halogen atom bound to a silane atom. 15 [0014]
[2] The composition according to claim 1, wherein the above-described polymer (i) is a polymer comprising a structural unit represented by the following Formula (1) and a structural unit represented by the following Formula (2): 20 [0015]
[Chem. 1]

SF-2582


A^—hSOsM J
(1)


O /k/ b

(2)

(wherein, in the Formulae (1) and (2),
R^ and R^ independently represent a hydrogen atom or a methyl group; 5 M represents a hydrogen atom, an alkali metal, an alkaline earth metal or an ammonium ion;
the unit ratio, a/b, is 1,000/1 to 1/1,000; A-^ is represented by (Ql)f(Pl);
Ql is selected from -C00-, -CONH- and a phenylene 10 group which optionally has a substituent;
PI is selected from the group consisting of a single

SF-2582 8
bond and a divalent or higher valent hydrocarbon group having an
ether structure and 1 to 15 carbon atoms;
f is 0 or 1 and h is 1 to 5;
A^ is represented by (Q2}g(P2};
5 Q2 is selected from -C00-, a divalent or higher valent
hydrocarbon group having 1 to 5 carbon atoms, a phenylene group v-jhich optionally has a substituent, and -0-;
P2 is selected from the group consisting of a single
bond, -X-P3-, -P4-y- and -P5-;
10 P3 to P5 each independently represent a
divalent or higher valent hydrocarbon group having an ether structure and 1 to 15 carbon atoms;
X represents oxygen, sulfur or -C00-;
y represents oxygen or sulfur;
15 g is 0 or 1 and k is 1 to 5; and,
when g is 1 and Q2 is -0- or -C00-, P2 is not -X-P3-) . [0016]
[3] The composition according to [2], wherein, in the above-described Formula (1), A'^ represents a single 20 bond, -CH2-, -C6H4-, -COOCH2-, -COOCH2CH2-, -COOCH2CH2CH2-,
-CONH-C(CH3}2-CH2-, -CONH-CH(CH3)-CH2-, -CONH-CH2-, -CONH-CH2CH2-or -CONH-CH2CH2CH2-; and,
in the above-described Formula (2), A^ represents a single bond, -CH2-, -C6H4-, -0-, -CH2-0-, -CH2-O-CH2-, -C6H4-O-,

SF-2582
-C6H4-O-CH2-, -CO0-, -COOCH2-, -C6H4-COO- or -C6H4-COO-CH2-. [0017]
[4] The composition according to [1], wherein the above-described polymer (i) has a weight-average molecular weight, 5 which is measured by GPC, of 300 to 3,000,000. [0018]
[5] The composition according to [1], wherein the above-described silane compound (ii) is a compound represented by the following Formula (3): 10 [0019]
[Chem. 2]


R'
0—Si-
R'

m

X

(3)

(wherein, in the Formula (3),
X-^ and X^ each independently represent a hydroxy group, an 15 alkoxy group having 1 to 4 carbon atoms, or a halogen atom;
R^ to R^ each independently represent a hydroxy group, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group, a phenyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom; and

SF-2582 10
m represents an integer of 0 to 10,000). [0020]
[6] The composition according to [1], wherein the reduced weight ratio of the above-described polymer (i) and the 5 above-described silane compound (ii) is in a range of 99.1/0.1 to 0.1/99.9. [0021]
[7] A film, obtained by heat-curing the composition according to any one of [1] to [6]. 10 [0022]
[8] The film according to [7], which is formed on a substrate. [0023]
[9] The film according to [8], wherein the ratio (Sa/Da) 15 of the sulfonic acid concentration in the outer surface (Sa) and the sulfonic acid concentration at the midpoint between an interface in contact with the above-described substrate and the outer surface (Da) is 2 to 1,000. [0024] 20 [10] The film according to any one of [7] to [9], which has a surface water contact angle of 30° or smaller. [0025]
[11] A film, which is formed on a substrate and comprises a -SO3M group (wherein, M represents a hydrogen atom, an alkali

SF-2582 11
metal, an alkaline earth metal or an ammonium ion) and a Si-O-Si structure or a Si-O-C structure, wherein the ratio (Sa/Da) of the SO3M group concentration in the outer surface of the surface (Sa) and the SO3M group concentration at the midpoint between an 5 interface in contact with the substrate and the above-described outer surface (Da) is 2 to 1,000. [0026]
[12] The film according to [11], wherein the above-described ratio (Sa/Da) is 10 to 1,000. 10 [0027]
[13] The film according to [11] or [12] , which has a surface water contact angle of 30° or smaller. [0028]
[14] A laminate, produced by laminating the film according 15 to any one of [7] to [13] on a substrate. [0029]
A hydrophilic film can be obtained by curing any of the above-described compositions and a laminate can be obtained by laminating this film. These hydrophilic film and laminate can 20 be used as an antifogging material, an antifouling material, a quick-drying material, an antistatic material, an undercoat material and the like.
EFFECTS OF THE INVENTION

SF-2582 12
[0030]
The film of the present invention has an excellent balance of hydrophilicity and abrasion resistance and only a small reduction in the hydrophilicity caused by water, as well as 5 excellent weather resistance. Therefore, a variety of laminates formed by laminating the film of the present invention on a substrate or the like can also be provided.
BRIEF DESCRIPTION OF THE DRAWINGS 10 [0031]
[Fig. 1] Fig. 1 shows the thermal stability comparative data (DSC chart) of representative compounds having a carbon-carbon double bond-containing polymerizable functional group and a sulfonic acid group, which compounds yield a structural unit that 15 is represented by the Formula (1) and constitutes the polymer (i) used in the present invention.
[Fig. 2] Fig. 2 shows the method of cutting a sample and the sites at which the sulfonic acid concentration is measured for determination of the degree of gradient in the respective 20 samples obtained in examples.
[Fig. 3] Fig. 3 shows the reflectance of the AR coating obtained in Example 22.
[Fig. 4] Fig. 4 shows the transmittance of the AR coating obtained in Example 22.

SF-2582 13
[Fig. 5] Fig. 5 shows the results of measuring the reflectance of the hydrophilic coating film obtained in Example 23 and that of the substrate used for the hydrophilic coating.
5 MODE FOR CARRYING OUT THE INVENTION [0032]
The film of the present invention can be typically obtained by curing a polymerizable composition, which includes a polymer (i) having a sulfonic acid group and an epoxy group and a silane
10 compound (ii) having two or more groups or atoms that are selected from the group consisting of a hydroxy group bound to a silane atom, an alkoxy group bound to a silane atom and a halogen atom bound to a silane atom, by use of methods, for example, heating. Such film of the present invention is capable of functioning as
15 a hydrophilic film. [0033] Polymer (i) having a sulfonic acid group and an epoxy group
In the present invention, as a first component constituting the composition of the present invention, a polymer (i) having
20 a group represented by -SO3M (hereinafter, may be simply referred to as "-SO3M group") and an epoxy group, wherein M represents a hydrogen atom, an alJcali metal, an alkaline earth metal or an ammonium ion, is used. However, in the present specification, for convenience of description, such polymer (i) may also be

SF-2582 14
referred to as "polymer (i) having a sulfonic acid group and an epoxy group". Further, unless otherwise specified, the term "sulfonic acid group" used herein may also be used to mean "-SO3M group". 5 [0034]
The polymer (i) having a sulfonic acid group and an epoxy group to be used in the present invention may be formed through various condensation or polymerization reactions such as polymer formation by urethane reaction, polymer formation by Michael
10 addition reaction and polymer formation by esterification
reaction; however, from the standpoints of the purity, yield and the like of the resulting polymer, the polymer (i) is preferably obtained by polymerization reaction of a monomer including a carbon-carbon double bond-containing polymerizable functional
15 group. [0035]
Examples of the carbon-carbon double bond-containing polymerizable functional group include:
polymerizable functional groups having a carbon-carbon
20 double bond in which a polymerizable functional group such as a vinyl group, an allyl group, an isopropenyl group, a styryl group or an a-methylstyryl group is constituted only by carbon atoms and hydrogen atoms (excluding the below-described polymerizable functional groups having an ether structure and a carbon-carbon

SF-2582 15
double bond, polymerizable functional groups having a carbonate structure and a carbon-carbon double bond, polymerizable functional groups having an ester structure and a carbon-carbon double bond, and polymerizable functional groups having an amide 5 structure and a carbon-carbon double bond);
polymerizable functional groups having an ether structure, such as a vinyl ether group, an allyl ether group or an allyl thioether group, and a carbon-carbon double bond;
polymerizable functional groups having a carbonate 10 structure, such as a vinyl carbonate group, an allyl carbonate group or an allyl thiocarbonate group, and a carbon-carbon double bond;
polymerizable functional groups having an ester structure, such as a (meth) acrylate group or a thio (meth) acrylate group, and 15 a carbon-carbon double bond; and
polymerizable functional groups having an amide structure, such as a (meth) acrylamide group, and a carbon-carbon double bond. [0036]
Thereamong, a vinyl group, an allyl group, a styryl group, 20 a vinyl ether group, an allyl ether group, a (meth) acrylate group and a (meth)acrylamide group are preferred.
Meanwhile, in cases where the polymer (i) is formed by polymerization reaction of polymerizable functional groups having a carbon-carbon double bond, a side chain thereof typically

SF-2582 16
contains, on average, at least one sulfonic acid group and one epoxy group, more precisely, one group represented by -SO3M (wherein, M represents a hydrogen atom, an alkali metal, an alkaline earth metal or an ammonium ion) and one epoxy group, per 5 molecule of the polymer (i); however, the polymer (i) may also contain other side chain of any structure. For example, a side chain having a hydroxy group in addition to a sulfonic acid group or an epoxy group, a side chain having a carboxyl group, a side chain having an alkyl group, a side chain having an aryl group,
10 a side chain having two hydroxy groups resulting from ring-opening of an epoxy group with water, and/or a side chain having an alkoxy group and a hydroxy group that resulted from ring-opening of an epoxy group with an alcohol may also be bound to the polymer (i) . [0037]
15 Examples of preferred mode of the polymer (i) having a sulfonic acid group and an epoxy group include a polymer having a structural unit represented by the following Formula (1) and a structural unit represented by the following Formula (2). [0038]
20 [Chem. 3]

SF-2582

17

A^—f-SOsM

h

(1)

(2)
(wherein, in the Formulae (1) and (2),
R^ and R^ independently represent a hydrogen atom or a methyl group; 5 M represents a hydrogen atom, an alkali metal, an alkaline earth metal or an ammonium ion;
the structural unit ratio, a/b, is 1,000/1 to 1/1,000; A"^ is represented by (Ql)f(Pl);
Ql is selected from -C00-, -CONH- and a phenylene 10 group which optionally has a substituent;

SF-2582 18
Pi is selected from the group consisting of a single bond and a divalent or higher valent hydrocarbon group having 1 to 15 carbon atoms which optionally has an ether structure; f is 0 or 1 and h is 1 to 5; 5 A^ is represented by (Q2)g(P2);
Q2 is selected from -C00-, a divalent or higher valent hydrocarbon group having 1 to 5 carbon atoms, a phenylene group which optionally has a substituent and -0-;
P2 is selected from the group consisting of a single 10 bond, -X-P3-, -P4-y- and -P5-;
P3 to P5 each independently represent a divalent or higher valent hydrocarbon group having 1 to 15 carbon atoms which optionally has an ether structure;
X represents oxygen, sulfur or -C00-;
15 Y represents oxygen or sulfur;
g is 0 or 1 and k is 1 to 5; and
when g is 1 and Q2 is -0- or -C00-, P2 is not -X-P3-) . In Pi, the "divalent or higher valent hydrocarbon group having 1 to 15 carbon atoms which optionally has an ether 20 structure" may be any of an aliphatic hydrocarbon group, an
alicyclic hydrocarbon group and an aromatic hydrocarbon group, and it may be linear or branched. Further, for example", as in the case of a polyoxyethylene chain, it may also be a hydrocarbon group having an ether structure. The number of carbon atoms is

SF-2582 19
1 to 15; however, it is more preferably 1 to 12. When the hydrocarbon group contains no ether structure, the number of carbon atoms is preferably 1 to 10. [0039] 5 Further, the hydrocarbon may have any valency of 2 or higher; however, the valency is usually 2 to 6, preferably 2 to 4, more preferably 2 to 3. Moreover, in Pi, the hydrocarbon group optionally has a substituent as well. The substituent is not particularly restricted and it may be, for example, a hydroxy group
10 or a halogen group {e.g., a fluoro group or a chloro group). [0040]
P3, P4 and P5 in P2 each independently represent a divalent or higher valent hydrocarbon group having 1 to 15 carbon atoms which optionally has an ether structure. Specifically, the
15 hydrocarbon group is specifically the same as that for PI and may be any of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group, and it may be linear or branched. In addition, for example, as in the case of a polyoxyethylene chain, it may also be one which has an ether
20 structure. The number of carbon atoms is 1 to 15; however, it is more preferably 1 to 12. When the hydrocarbon group contains no ether structure, the number of carbon atoms is preferably 1 to 10.
Further, the hydrocarbon may have any valency of 2 or higher;

SF-2582 20
however, the valency is usually 2 to 6, preferably 2 to 4, more preferably 2 to 3. Moreover, in Pi, the hydrocarbon group optionally has a substituent as well. The substituent is not particularly restricted and it may be, for example, a hydroxy group 5 or a halogen group {e.g., a fluoro group or a chloro group). [0041]
Q2 is selected from -C00-, a divalent or higher valent hydrocarbon group having 1 to 5 carbon atoms, a phenylene group which optionally has a substituent and -0-. Here, the divalent
10 or higher valent hydrocarbon groups having 1 to 5 carbon atoms include, for example, alkylene groups, and specific examples thereof include a methylene group, an ethylene group and a propylene group. In the phenylene group which optionally has a substituent, each substituent may be a hydrocarbon group having
15 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and the substituents may be bound to each other to form a ring. [0042]
Alternatively, the above-described substituent may also be, for example, a hydroxy group, a halogen group (e.g., a fluoro group
20 or a chloro group) or an alkoxy or thioalkoxy group having 1 to 10 carbon atoms. [0043]
Examples of preferred structure of the above-described Formula (1) include the following modes:

SF-2582 21
(1-1) a structure derived from sulfonic acid having a (meth)acrylate structure, wherein R^ is hydrogen or methyl, Ql is -COO- and f = 1;
(1-2) a structure derived from sulfonic acid having a 5 (meth)acrylamide structure, wherein R^ is hydrogen or methyl, Ql is -CONH- and f = 1;
(1-3) a structure derived from sulfonic acid having a styryl group or an a-methylstyryl group, wherein R'^ is hydrogen or methyl, Ql is a phenylene group which optionally has a substituent and 10 f = 1; and
(1-4) a structure derived from sulfonic acid having a vinyl group, wherein R*^ is hydrogen and f = 0. [0044]
It is noted here that, including the above-described 15 structures (1-1) to (1-4), in the above-described Formula (1), h is 1 to 5, preferably 1 to 3, more preferably 1 to 2, and it may be, of course, 1. [0045]
In a more specific mode of the above-described Formula (1) , 20 A^ is preferably, in particular, a direct bond having no structure (that is, a single bond), -CH2-, -C6H4-, -COOCH2-, -COOCH2CH2-, -COOCH2CH2CH2-, -CONH-C(CH3)2-CH2-, -CONH-CH(CH3)-CH2-, -CONH-CH2-, -CONH-CH2CH2- or -CONH-CH2CH2CH2-. [0046]

SF-2582 22
Further, examples of preferred structure of the above-described Formula (2) include the following modes:
(2-1) a structure derived from an epoxy compound having (meth)acryla, wherein R^ is hydrogen or methyl, Q2 is -COO- and 5 g = 1;
(2-2) a structure derived from an epoxy compound having a styryl group or an a-methylstyryl group, wherein R^ is hydrogen or methyl, Q2 is a phenylene group which optionally has a substituent and g = 1; 10 (2-3) a structure derived from an epoxy compound having a vinyl ether group, wherein R^ is hydrogen, Q2 is -0- and g = 1;
(2-4) a structure derived from an epoxy compound having a vinyl group, wherein R^ is hydrogen and g = 0; and
(2-5) a structure derived from an epoxy compound having an 15 allyl group, wherein R^ is hydrogen, Q2 is a methylene group and g = 1. [0047]
In cases where the structure of the above-described Formula (2) is that described in the above (2-5), it is preferred that 20 P2 have a structure represented by -X-P3 and X be oxygen. [0048]
It is noted here that, including the above-described structures (2-1) to (2-5), in the above-described Formula (2), k is 1 to 5, preferably 1 to 3, more preferably 1 to 2, and it

SF-2582 23
may be, of course, 1. [0049]
In a more specific mode of the above-described Formula (2) , A^ is preferably, in particular, a direct bond having no structure 5 {that is, a single bond) , -CH2-, -C6H4-,-0-, -CH2-O-, -CH2-O-CH2-, -C6H4-O-, -C6H4-O-CH2-, -C00-, -COOCH2-, -C6H4-COO- or -C6H4-COO-CH2-.
M is preferably selected from: a hydrogen atom; alkali metals such as lithium, sodium, potassium and rubidium; alkaline
10 earth metals such as calcium and magnesium; and ammonium ions such as tetrahydroammonium ion, tetramethylammonium ion, tetraethylammonium ion, methyltrihydroammonium ion, ethyltrihydroammonium ion, cyclohexyltrihydroammonium ion, phenyltrihydroammonium ion and dimethyl-phenyl-hydro-ammonium
15 ion. Thereamong, the above-described group represented by SO3M is preferably not in the form of a free acid, but in the form of being neutralized with a counter-cation such as an alkali metal, an alkaline earth metal or an ammonium ion. [0050]
20 A polymer having a structural unit represented by the
Formula (1) and a structural unit represented by the Formula (2) can be obtained by, for example, adding a reaction solvent and a radical polymerization initiator such as peroxide to a compound having a carbon-carbon double bond-containing polymerizable

SF-2582 24
functional group and a sulfonic acid group and a compound having a carbon-carbon double bond-containing polymerizable functional group and an epoxy group and subsequently heating the resulting mixture with stirring. In the present invention, such a polymer 5 including a structural unit represented by the Formula (1) and a structural unit represented by the Formula (2) can be used as the polymer (i) constituting the composition of the present invention. [0051]
10 The structural unit ratio a/b {mol/mol), which is a ratio between the number of the structural unit represented by the Formula {1) , a, and the number of the structural unit represented by the Formula (2) , b, is controlled by adjusting, for example, the loading ratio of the compound having a carbon-carbon double
15 bond-containing polymerizable functional group and a sulfonic acid group, and the compound having a carbon-carbon double bond-containing polymerizable functional group and an epoxy group. [0052]
20 This structural unit ratio, a/b (mol/mol) , for the polymer (i) can be controlled by adjusting the loading ratio of the compound having a carbon-carbon double bond-containing polymerizable functional group and a sulfonic acid group, which corresponds to the structural unit represented by the Formula (1), and the

SF-2582 25
compound having a carbon-carbon double bond-containing polymerizable functional group and an epoxy group, v-zhich corresponds to the structural unit represented by the Formula (2) , at the time of performing polymerization reaction. The 5 structural unit ratio, a/b (mol/mol) , for the polymer (i) is not particularly restricted; however, from the standpoints of the hydrophilicity, performance retainability (durability) and the like, it is usually 1,000/1 to 1/1,000, that is, in a range of 99.9/0.1 to 0.1/99.9, preferably 99/1 to 1/99, more preferably
10 98/2 to 2/98. [0053]
In cases where importance is given to hydrophilicity, it is preferred that the number of the structural unit represented by the Formula (1), a, be relatively large, and the ratio is in
15 a range of, for example, 99.9/0.1 to 40/60, more preferably 99/1 to 50/50, particularly preferably 98/2 to 60/40. [0054]
In cases where importance is given to abrasion resistance, durability and the like, it is preferred that the number of the
20 structural unit represented by the Formula (2), b, be relatively large as compared to a case where importance is given to hydrophilicity, the ratio is in a range of, for example, 95/5 to 5/95, more preferably 90/10 to 10/90, particularly preferably 80/20 to 20/80.

SF-2582 26
[0055]
Examples of the compound having a carbon-carbon double bond group-containing polymerizable functional group and a sulfonic acid group, which is used to constitute a structural unit 5 represented by the Formula (1), that is, the compound having a carbon-carbon double bond-containing polymerizable functional group and a sulfonic acid group which corresponds to the structural unit represented by the Formula (1) , include those compounds that have a structure represented by the following Formula (1'): 10 [0056]
[Chem. 4]
A^—f-SOoM )
(wherein, in the Formula (1')/ R^, M, A^ and h are the same as those of the above-described Formula (1), respectively). 15 [0057]
Among such compounds having a carbon-carbon double bond group-containing polymerizable functional group and a sulfonic acid group, sulfonic acid compounds having a vinyl group, sulfonic acid compounds having a styryl group, sulfonic acid compounds 20 having a (meth)acrylate group and sulfonic acid compounds having

SF-2582 27
a (meth)acrylamide group are relatively preferred. [0058]
Here, preferably used sulfonic acid compounds having a vinyl group include, for example, a vinyl sulfonic acid, lithium 5 vinylsulfonate, sodium vinylsulfonate, potassium vinylsulfonate and ammonium vinylsulfonate. [0059]
Preferably used sulfonic acid compounds having a styryl group include, for example, styrene sulfonic acid, lithium styrene 10 sulfonate, sodium styrene sulfonate, potassium styrene sulfonate, calcium styrene sulfonate, magnesium styrene sulfonate and ammonium styrene sulfonate. [0060]
Preferably used sulfonic acid compounds having a 15 (meth)acrylate group include, for example, sodium sulfomethyl (meth)acrylate, 2-sulfoethyl (meth)acrylate, sodium 2-sulfoethyl (meth)acrylate, potassium 2-sulfoethyl (meth)acrylate, 3-sulfopropyl (meth)acrylate, sodium 3-sulfopropyl (meth)acrylate, potassium 3-sulfopropyl 20 (meth) acrylate, calcium 3-sulfopropyl (meth) acrylate, magnesium 3-sulfopropyl (meth)acrylate, ammonium 3-sulfopropyl (meth)acrylate, potassium 6-sulfohexyl (meth)acrylate, potassium 10-sulfodecyl (meth)acrylate, potassium 5-sulfo-3-oxapentyl (meth)acrylate and potassium

SF-2582 28
8-sulfo-3,6-dioxaoctyl (meth)acrylate. [0061]
Preferably used sulfonic acid compounds having a (meth)acrylamide group include, for example, sulfonic acid 5 compounds having a (meth)acryloylamide group such as 1-(meth)acrylamide-methanesulfonic acid, potassium 1-(meth)acrylamide-methanesulfonate, 2-(meth)acrylamide-ethanesulfonic acid, sodium 2-(meth)acrylamide-ethanesulfonate,
10 2-(meth)acrylamide-propanesulfonic acid, potassium 2-(meth)acrylamide-propanesulfonate, 2-(meth)acrylamide-2-methyl-propanesulfonic acid ((meth)acrylamide-t-butyl sulfonic acid), sodium 2-(meth)acrylamide-2-methyl-propanesulfonate, potassium
15 2-(meth)acrylamide-2-methyl-propanesulfonate, calcium 2-(meth)acrylamide-2-methyl-propanesulfonate, magnesium 2-(meth)acrylamide-2-methyl-propanesulfonate, ammonium 2-(meth)acrylamide-2-methyl-propylsulfonate and potassium 3-(meth)acrylamide-propanesulfonate.
20 [0062]
Among the above-described compounds having a carbon-carbon double bond group-containing polymerizable functional group and a sulfonic acid group, sulfonic acid compounds having a (meth)acrylamide group are most preferred and thereamong,

SF-2582 29
2-(meth)acrylamide-2-methyl-propyl sulfonic acid ((meth)acrylamide-t-butyl sulfonic acid) and counter-cation salts thereof are preferred and alkali metal salts of 2-(meth)acrylamide-2-methyl-propyl sulfonic acid 5 {(meth)acrylamide-t-butyl sulfonic acid) are most preferred. [0063]
With regard to the mode of the sulfonic acid group in the compound having a carbon-carbon double bond-containing polymerizable functional group and a sulfonic acid group, the
10 sulfonic acid group is more preferably in the form of an alkali metal salt, an alkaline earth metal circle or an ammonium salt in which sulfonic acid is neutralized with a counter-cation, rather than in a condition of free sulfonic acid where M constituting the Formula (1') is hydrogen. This is because, when
15 sulfonic acid is neutralized with a counter-cation, reaction between an epoxy group and a sulfonic acid group and the like is inhibited at the time of polymerization reaction and a polymer (i) having a high purity can thus be efficiently obtained. The details of this process will be described below.
20 [0064]
When sulfonic acid is not neutralized {M is a hydrogen atom) , it may react with the epoxy group of a compound having an epoxy group, which is the other starting material, and gelation of the resulting polymer may occur during co-polymerization reaction.

SF-2582

30

A schematic reaction formula of this reaction between an epoxy group and a sulfonic acid group is shown below. [0065] [Chem. 5]

As a method of obtaining a high-purity polymer (i) by inhibiting the above-described reaction, the present inventors have discovered that a method of neutralizing a sulfonic acid group with a counter-cation to inhibit reaction between the sulfonic 10 acid group and an epoxy group is effective. In the same manner, another schematic reaction formula is shown below. [0066] [Chem. 6]



o
SiOK
Neutralization
Inhibition of Reaction

15 Further, among alJcali metals, alkaline earth metals and ammonium ion, which are counter-cations, alkali metals, which tend to have high reaction-inhibiting ability and stability tend to

SF-2582 31
be preferred. Among alkali metals, sodium and potassium are preferred and the most preferred counter-cation is, for example, potassium. Potassium may provide superior thermal stability than sodium, although the reason therefor is not clear. For reference, 5 Fig. 1 shows the thermal stability comparative data (DSC chart) of representative compounds among the above-described compounds having a carbon-carbon double bond-containing polymerizable functional group and a sulfonic acid group.
A method of smoothly obtaining the polymer of the present
10 invention wherein M is a hydrogen atom is not particularly restricted as long as the method is capable of performing a polymerization reaction in such a condition that the above-described ring-opening of an epoxy group by a hydrogen atom does not occur, and examples of such a method include one in which,
15 after neutralizing sulfone groups constituting the
above-described compound having a carbon-carbon double bond-containing polymerizable functional group and a sulfonic acid group with a counter-cation to give a corresponding sulfonic acid salt, this sulfonic acid salt is copolymerized with the
20 below-described compound having a carbon-carbon double
bond-containing polymerizable functional group and an epoxy group, which compound corresponds to a structural unit represented by the Formula (2), and then treating (reacting) the thus obtained polymer (i) having a sulfonic acid counter-cation base and an epoxy

SF-2582 32
group with an acid such as hydrochloric acid or sulfuric acid to
convert it into a free sulfonic acid group.
[0067]
In order to form a structural unit represented by the Formula 5 (2) which is a structural unit of the polymer (i) of the present invention, as a compound having a carbon-carbon double bond-containing polymerizable functional group and an epoxy group which corresponds to a structural unit represented by the Formula (2), a compound having a carbon-carbon double bond 10 group-containing polymerizable functional group and an epoxy group, which is represented by the following Formula {2'), is preferably used: [0068] [Chem. 7]



15

0

(2')

{wherein, in the Formula {2'), R^, A^ and k are the same as those of the above-described Formula (2), respectively). [0069]

SF-2582 33
Among those compounds having a carbon-carbon double bond group-containing polymerizable functional group and an epoxy group, which are represented by the above-described Formula (2 ') , epoxy compounds having a vinyl group, epoxy compounds having a 5 vinyl ether group, epoxy compounds having an allyl ether group, epoxy compounds having a styryl group and epoxy compounds having a (meth}acrylate group are relatively preferred. [0070]
Here, examples of the epoxy compounds having a vinyl group
10 include butadiene-monoxide, pentadiene-monoxide and hexadiene-monoxide. [0071]
Examples of the epoxy compounds having a vinyl ether group include vinylglycidyl ether, butanediol-divinyl ether monoxide,
15 cyclohexane dimethanol-divinyl ether monoxide,
4-glycidyloxymethyl-l-vinyloxymethyl-cyclohexane, diethylene glycol-divinyl ether monoxide, tripropylene glycol-divinyl ether monoxide and 4-vinyloxy-l-glycidyloxy-butane. [0072]
20 Examples of the epoxy compounds having an allyl ether group include allyl-glycidyl ether, allyl-epoxy ether, butanediol-diallyl ether monoxide, cyclohexane dimethanol-diallyl ether monoxide, 4-glycidyloxymethyl-l-allyloxymethyl-cyclohexane, diethylene

SF-2582 34
glycol-diallyl ether monoxide, tripropylene glycol-diallyl ether
monoxide and 4-allyloxy-l-glycidyloxy-butane.
[0073]
Examples of the epoxy compounds having a styryl group 5 include divinylbenzene-monoxide, 4-glycidyloxy-styrene,
3-glycidyloxy-styrene, 2-glycidyloxy-styrene,
4-epoxyoxy-styrene, styryl carboxylic acid epoxy ester and styryl
carboxylic acid glycidyl ester.
[0074] 10 Examples of the epoxy compounds having a (meth)acrylate
group include glycidyl-(meth)acrylate, epoxy-(meth)acrylate,
2-glycidyloxy-ethyl-(meth)acrylate,
5-glycidyloxy-3-oxapentyl-(meth)acrylate,
3-glycidyloxy-2-hydroxy-propyl-(meth)acrylate, 15 2,3-bis(glycidyloxy)-propyl-(meth)acrylate,
trimethylolpropane-diglycidyl ether-(meth)acrylate,
{4-glycidyloxyphenyl}-{(4-(meth)acryloyloxy-3-hydroxy-l-oxabu
tyl)phenyl}-2,2-propane and
7-glycidyloxy-6,6-dimethyl-2-hydroxy-4-oxaheptyl-(meth)acryla 20 te.
Among those compounds having a carbon-carbon double
bond-containing polymerizable functional group and an epoxy group
that may be used in the production of the polymer (i), epoxy
compounds having a (meth)acrylate group, epoxy compounds having

SF-2582 35
an allyl ether group and epoxy compounds having a styryl group are preferred. Examples thereof include glycidyl (meth) acrylate, allylglycidyl ether and 4-glycidyloxystyrene. [0075] 5 In addition to a structural unit represented by the Formula (1) and a structural unit represented by the Formula (2), the polymer (i) of the present invention may also include a third structural unit which is neither the structural unit represented by the Formula (1) nor the structural unit represented by the
10 Formula (2) (hereinafter, referred to as "the third structural unit"). [0076]
Examples of such third structural unit include those structural units that are generated by copolymerization of
15 compounds having a carbon-carbon double bond-containing
polymerizable functional group, which are different from both a compound having a carbon-carbon double bond-containing polymerizable functional group and a sulfonic acid group and a compound having a carbon-carbon double bond-containing
20 polymerizable functional group and an epoxy group. [0077]
Examples of such structural units include structural units derived from (meth)acrylic acid; structural units derived from methyl (meth)acrylate; structural units derived from butyl

SF-2582 36
(meth)acrylate; structural units derived from isobornyl (meth) acrylate; structural units derived from tetrahydrofurfuryl (meth)acrylate; structural units derived from phenyl (meth)acrylate; structural units derived from tribromophenyl 5 (meth)acrylate; structural units derived from hydroxyethyl
(meth)acrylate; structural units derived from ethyl phosphate (meth)acrylate; structural units derived from
tetramethylpiperidyl (meth)acrylate; structural units derived from perfluorooctylethyl (meth)acrylate; structural units 10 derived from thioglycidyl (meth)acrylate; structural units derived from styrene; structural units derived from acrylonitrile; structural units derived from such a small amount of divinylbenzene that gelation does not occur; and structural units derived from such a small amount of allyl (meth)acrylate 15 that gelation does not occur. [0078]
Compounds which give such a third structural unit include compounds having a carbon-carbon double bond-containing polymerizable functional group that are neither compounds having 20 a carbon-carbon double bond-containing polymerizable functional group and a sulfonic acid group, which compound has a structure represented by the above-described Formula (1'), nor compounds having a carbon-carbon double bond-containing polymerizable functional group and an epoxy group, which compound has a structure

SF-2582 37
represented by the above-described Formula (2') {hereinafter, such compounds are referred to as "the third structural unit precursor compound"). Examples of compounds that correspond to the above-described structural units include (meth) acrylic acid, 5 methyl (meth)acrylate, butyl (meth)acrylate, isobornyl
(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenyl (meth)acrylate, tribromophenyl (meth)acrylate, hydroxyethyl (meth)acrylate, ethyl phosphate (meth)acrylate, tetramethylpiperidyl (meth)acrylate, perfluorooctylethyl 10 (meth)acrylate, thioglycidyl (meth)acrylate, styrene,
acrylonitrile, divinylbenzene in such a small amount that gelation does not occur, and allyl (meth)acrylate in such a small amount that gelation does not occur.
In the polymer (i) of the present invention, in cases where 15 the above-described third structural unit is introduced, it is blended at the belovz-described ratio or so. [0079]
For example, when the number of the above-described third structural unit, c, with respect to the number of the structural 20 unit represented by the Formula (1), a, and the number of the structural unit represented by the Formula (2), b, is represented by a ratio (a + b)/c (mol/mol), the ratio is in a range of, for example, 99.9/0.1 to 10/90, preferably 99/1 to 50/50, more preferably 95/5 to 60/40. Further, the ratio, (a + b) /c (mol/mol) ,

SF-2582 38
may also be 70/30 or higher, or 80/20 or higher. [0080]
In the polymer (i) of the present invention, the number of the repeating structural units (a + b) is mainly controlled by 5 the solvent type, the substrate (monomer) concentration, the amount of polymerization initiator, the reaction temperature and t,he like and it is usually in a range of 1 to 10,000, preferably 3 to 3,000, more preferably 30 to 1,500. Further, the molecular weight of the polymer (i) having a sulfonic acid group and an epoxy
10 group is also controlled in the same manner. The weight-average molecular weight (MW) of this polymer (i), which is determined by GPC, is usually in a range of 300 to 3,000,000; hov-zever, from the standpoints of the durability and solubility, it is preferably 1,000 to 1,000,000, more preferably 10,000 to 500,000.
15 Further, in the present invention, the ratio Mw/Mn of the polymer (i) is usually 1 to 10, preferably 1 to 6, more preferably 1 to 4. In this case, the resulting composition tends to have excellent solubility or dispersibility and the resulting cured film tends to have excellent transparency, smoothness or the like.
20 [0081]
In the polymer (i) of the present invention, the form of binding between a structural unit represented by the Formula (1) and a structural unit represented by the Formula (2) is not particularly restricted; however, as described below, the binding

SF-2582 39
is preferably formed by radical copolymerization and in that case, the polymer (i) is believed to be in the form of a so-called random copolymer.
As described above, the polymer (i) of the present invention 5 which includes a structural unit represented by the Formula (1) and a structural unit represented by the Formula (2) is obtained by adding a reaction solvent and a polymerization initiator to a compound having a carbon-carbon double bond-containing polymerizable functional group and a sulfonic acid group, which
10 has a structure represented by the above-described Formula {1") , and a compound having a carbon-carbon double bond-containing polymerizable functional group and an epoxy group, which has a structure represented by the above-described Formula (2'), and then allowing these compounds to copolymerize under heating with
15 stirring. In this process, as required, the above-described "third structural unit precursor compound" can also be copolymerized along with the compound having a carbon-carbon double bond-containing polymerizable functional group and a sulfonic acid group, which has a structure represented by the
20 above-described Formula {1'), and a compound having a
carbon-carbon double bond-containing polymerizable functional group and an epoxy group, which has a structure represented by the above-described Formula {2'). [0082]

SF-2582 40
As the polymerization initiator, a known radical initiator is preferably used, and examples thereof include: nitriles such as azobisisobutyronitrile; ketone peroxides such as methylisobutyl ketone peroxide and 5 cyclohexanone peroxide;
diacyl peroxides such as isobutyryl peroxide, o-chlorobenzoyl peroxide and benzoyl peroxide;
dialkyl peroxides such as tris(t-butylperoxy)triazine and t-nutylcumyl peroxide; 10 peroxyketals such as
2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane and 2,2-di(t-butylperoxy)butane;
alkyl peresters such as a-cumylperoxy neodecanoate, t-butylperoxypivalate, 15 2, 4, 4-trimethylpennylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate and t-butylperoxy-3,5,5-trimethylhexanoate; and
percarbonates such as di-3-methoxybutylperoxy dicarbonate, bis(4-t-butylcyclohexyl)peroxy dicarbonate, 20 t-butylperoxyisopropyl carbonate, diethylene glycol bis(t-butylperoxycarbonate). [0083]
The amount of the above-described polymerization initiator to be added is in a range of about 0.01 to 10 wt%, preferably 0.1

SF-2582 41
to 5 wt%, more preferably 0.2 to 3 wt%, with respect to the total weight of the compound having a carbon-carbon double bond-containing polymerizable functional group and a sulfonic acid group which is represented by the above-described Formula 5 (1') / the compound having a carbon-carbon double bond-containing polymerizable functional group and an epoxy group which is represented by the above-described Formula (2' ) and the optional above-described "third structural unit precursor compound".
The solvent to be used in the copolymerization of a compound
10 having a carbon-carbon double bond-containing polymerizable
functional group and a sulfonic acid group which is represented by the Formula (1')^ ^ compound having a carbon-carbon double bond-containing polymerizable functional group and an epoxy group which is represented by the Formula (2') and the optional
15 above-described "third structural unit precursor compound" is not particularly restricted as long as it does not cause any defect such as inhibition of polymerization reaction. A high-polarity solvent, which improves the solubilities of a compound having a carbon-carbon double bond-containing polymerizable functional
20 group and a sulfonic acid group which is represented by the Formula {!'), a compound having a carbon-carbon double bond-containing polymerizable functional group and an epoxy group which is represented by the Formula {2') and the optional above-described "third structural unit precursor compound", all of which compounds

SF-2582 42
are used as monomers, tends to be preferred. Specific examples of such a high-polarity solvent include alcohols such as methanol, ethanol, isopropanol (IPA), 1-propanol, 1-butanol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol and propylene 5 glycol monomethyl ether; ratio protic polar solvents such as acetonitrile, sulfolane, dimethyl sulfoxide,
N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc) and N,N-dimethylhoimidazolidinone (DMI); water; and mixed solvents thereof.
10 The reaction temperature in the copolymerization of a compound having a carbon-carbon double bond-containing polymerizable functional group and a sulfonic acid group which is represented by the Formula (1'), a compound having a carbon-carbon double bond-containing polymerizable functional
15 group and an epoxy group which is represented by the Formula (2' ) and the optional above-described "third structural unit precursor compound" which is used as required is primarily set based on the 10-hour half-life temperature of the polymerization initiator, and it is in a range of about room temperature to 200 °C, preferably
20 30 to 120°C, more preferably 40 to 100°C.
The polymer (i) of the present invention produced in this manner is usually a high-molecular-weight polymer including a large number of sulfonic acid groups and often has a property of being soluble only to water. Therefore, in this case, as long

SF-2582 43
as a large amount of water is not used as a reaction solvent, the polymer precipitates out of the reaction system as the reaction proceeds and a desired polymer can thus be obtained simply by filtering out the precipitate and drying it after the completion 5 of the reaction. Meanwhile, in the case of a polymer which includes only a small number of sulfonic acid groups and is thus not likely to precipitate, a method in which the polymer is placed in a poor solvent to be precipitated or a method in which, after distilling off the solvent using an evaporator or the like, the
10 resultant is stirred in a poor solvent and then filtered and dried is relatively preferably employed. Silane Compound (ii)
As a second component constituting the composition of the present invention, a silane compound (ii) which has a total of
15 two or more groups or atoms that are selected from the group consisting of a hydroxy group bound to a silane atom, an alkoxy group bound to a silane atom and a halogen atom bound to a silane atom is used. A hydroxy group bound to a silane atom is usually obtained by hydrolyzing an alkoxy group bound to a silane atom
20 or a halogen atom bound to a silane atom, and an alkoxy group bound to a silane atom is generally obtained by allowing a halogen atom bound to a silane atom to react with alcohol. The silane compound (ii) of the present invention may have any structure as long as it contains a total of at least two groups or atoms that are

SF-2582

44

selected from the group consisting of a hydroxy group bound to a silane atom, an alkoxy group bound to a silane atom and a halogen atom bound to a silane atom. For example, the silane compound (ii) may have two or more hydroxy groups, alkoxy groups or halogen atoms that are each bound to a silane atom. Among such structures, examples of preferred structure include the following Formula (3) : [0084] [Chem. 8]



0—Si
(3)

10 (wherein, in the Formula (3),
X"^ and X^ each independently represent a hydroxy group, an alkoxy group having 1 to 4 carbon atoms or a halogen atom;
R^ to R^ each independently represent a hydroxy group, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl 15 group, a phenyl group, an alkoxy group having 1 to 4 carbon atoms or a halogen atom; and
m represents an integer of 0 to 10,000).
Here, m is usually in a range of 0 to 10,000, preferably 0 to 100, more preferably 0 to 10.

SF-2582 45
[0085]
The phenyl groups represented by R^ to R^ may or may not have a substituent. [0086] 5 The hydroxy groups bound to a silane atom, which are represented by X^, X^ and R^ to R^, has high reactivity and, depending on the case, they are readily dehydrated and condensed even at room temperature to form a siloxane bond (Si-O-Si), thereby being polymerized and cured. 10 [0087]
Meanwhile, the alJcoxy groups or halogen atoms, which are represented by X^, X^ and R^ to R^, are readily hydrolyzed into hydroxy groups; therefore, polymerization and curing thereof usually proceed via hydroxy groups. However, although an alkoxy 15 group is less reactive than a hydroxy group, alkoxy groups can be directly condensed by, for example, heating at a relatively high temperature (about lOO^^C or higher) to form a siloxane bond, thereby being polymerized and cured. That is, the hydroxy groups, alkoxy groups or halogen atoms that are bound to a silane atom 20 are involved in cross-linking and curing reactions in the
composition of the present invention. On the other hand, in R^ to R^, the hydrogen atom, alkyl group having 1 to 4 carbon atoms, vinyl group and phenyl group are usually stable and thus not involved in the cross-linking reaction. They generate good

SF-2582 46
effects of, for example, inhibiting cracking and providing toughness; however, they also exert adverse effects such as reduction in the hardness. That is, by adjusting the types and ratios of these substituents that are directly bound to a silane 5 atom, the hardness of the resulting cured film can be controlled within a certain range. In the present invention, of those substituents that are bound to the 4 available dangling bonds of each silane atom, the number of substituents that are not involved in the cross-linking reaction {hydrogen atom, alkyl group having
10 1 to 4 carbon atoms, vinyl group and phenyl group) tends to be preferably 2 or less and more preferably not more than 1. The total number of hydroxy groups, alkoxy groups having 1 to 4 carbon atoms and halogen atoms, which are involved in the cross-linking reaction, and siloxane bonds that are already reacted tends to
15 be preferably 2 to 4 per silane atom and more preferably 3 to 4. [0088]
In the compound represented by the Formula (3) , for example, when m is 0, the number of substituents that are not involved in the cross-linking reaction {hydrogen atom, alkyl group having 1
20 to 4 carbon atoms, vinyl group and phenyl group) is usually 0 to 2, desirably 0 to 1, and it is 0 in a preferred mode. Further, when m is 1 or larger, the number of substituents that are not involved in the cross-linking reaction (hydrogen atom, alkyl group having 1 to 4 carbon atoms, vinyl group and phenyl group) is usually

SF-2582 47
0 to 2 X (m + 1), preferably 0 to (m + 1).
In this manner, taking advantage of the above-described properties, the silane compound (ii) of the present invention can be readily polymerized and cured usually by hydrolyzing 5 polyalkoxysilane or polyhalogenated silane v/ith an addition of water and subsequently heating the resultant; therefore, it is used as an indispensable component in the composition of the present invention. Examples of polyalkoxysilane or polyhalogenated silane that can be preferably used in the present 10 invention include the followings: [0089]
(A) tetraalkoxysilanes such as tetramethoxysilane,
tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane;
(B) trialkoxysilanes such as hydrotrimethoxysilane,
15 methyltrimethoxysilane, methyltriethoxysilane,
ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane; 20 (C) dialkoxysilanes such as dimethyldimethoxysilane, dihydrodimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diphenyldimethoxysilane, divinyldimethoxysilane, hydrophenyldimethoxysilane,

SF-2582 48
methylphenyldimethoxysilane, hydrovinyldimethoxysilane, methylvinyldimethoxysilane and phenylvinyldimethoxysilane;
(D) tetrahalogenated silanes such as tetrachlorosilane, tetrabromosilane and tetraiodosilane; 5 (E) trihalogenated silanes such as hydrotribromosilane, methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, butyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, vinyltribromosilane and vinyltriiodosilane; and
10 (F) dihalogenated silanes such as dihydrodibromosilane, dimethyldichlorosilane, dimethyldichlorosilane, dimethyldibromosilane, dimethyldiiodosilane, diphenyldichlorosilane, divinyldichlorosilane, hydrophenyldichlorosilane, methylphenyldichlorosilane,
15 hydrovinyldichlorosilane, methylvinyldichlorosilane and phenylvinyldichlorosilane.
In order to, for example, improve the hydrolysis reaction rate of above-described (A) to (F) , an acidic substance or a basic substance is usually added as a polycondensation catalyst.
20 [0090]
As a polycondensation catalyst of the silane compound (ii) , an acid catalyst or a base catalyst is commonly used. As an acid catalyst, for example, hydrochloric acid, sulfuric acid, nitric acid, trifluoroacetic acid, acetic acid, phosphoric acid, boric

SF-2582 49
acid, boron trifluoride, tin oxide or tetraalkoxy titanium is employed. As a base catalyst, for example, sodium hydroxide, sodium alkoxide, potassium hydroxide or ammonia is employed. [0091] 5 The amount of the above-described condensation catalyst to be added is preferably in a range of 0.1 to 10 wt%, more preferably 0.2 to 5 wt%, still more preferably 0.3 to 3 wt%, with respect to the total amount of the polymer (i) and silane compound (ii) of the present invention.
10 [0092]
From the standpoints of the hydrophilicity, hardness and abrasion resistance, the reduced weight ratio of the polymer (i) and the silane compound (ii) is about 99.1/0.1 to 0.1/99.9, preferably 99/1 to 1/99, more preferably 90/10 to 10/90 . In cases
15 where importance is given to hardness, the reduced weight ratio
is 60/40 to 10/90, more preferably 50/50 to 10/90. Further, in
cases where importance is given to hydrophilicity, the reduced
weight ratio is 90/10 to 20/80, more preferably 70/30 to 20/80.
Here, the reduced weight ratio of the polymer (i) and the
20 silane compound (ii) can be determined as a ratio between the weight of the polymer (i) and the weight calculated based on silica or an analogue thereof that corresponds to the silane compound (ii) . For example, when the silane compound (ii) is represented by the following Formula (3), the "weight calculated based on

SF-2582

50

silica or an analogue thereof that corresponds to the silane compound (ii)" is determined by the below-described equation [0093] [Chem. 9]



0—Si
(3)

(wherein, in the Formula (3) , X-^ and X^ each independently represent a hydroxy group, an alkoxy group having 1 to 4 carbon atoms or a halogen atom; R^ to R^ each independently represent a hydroxy group, a hydrogen atom, an alkyl group having 1 to 4 carbon
10 atoms, a vinyl group, a phenyl group, an alkoxy group having 1 to 4 carbon atoms or a halogen atom; and m represents an integer of 0 to 10,000)
In the total number of R^ to R^ (R^ + R^ + mR^ + mR^) , when w of these groups are substituted with R"^° (wherein, R"^° represents
15 a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group or a phenyl group; and w represents a number of 0 or larger) , the post-polycondensation "weight calculated based on silica or an analogue thereof that corresponds to the silane compound (ii) " is calculated with an assumption that "silica or an analogue

SF-2582 51
thereof that corresponds to the silane compound (ii)" is
represented by the following Formula (100).
[0094]
R „ ~ Si(i + m)0((4 + 4 X m - w)/2) (100)
5 The sulfonic acid group of the polymer (i) imparts high hydrophilicity to the resulting cured film and the silane compound (ii) is cross-linked by polycondensation to provide the resulting cured film with not only rigidity but also excellent weather resistance characteristic to inorganic substances. The epoxy 10 group of the polymer (i) reacts with the silanol group of this silane compound (ii) (the reaction formula is shown below as the Formula (4)) to give an effect of incorporating the polymer (i) into the network of the silane compound (ii). [0095]
Si-OH + o\—^-Si-O^Y
' ^ I OH (4)
15
Therefore, firm fixation of the highly hydrophilic polymer (i) on the cured film gives an effect that release of the highly hydrophilic polymer (i) out of the system is inhibited and high hydrophilicity is thus maintained over an extended period. In 20 addition, incorporation of the highly hydrophilic polymer (i) into the siloxane network of the silane compound provides toughness and improves the abrasion resistance. Moreover, there are also

SF-2582 52
advantages in that, for example, crystallization and generation of a layer-separated structure are likely to be inhibited by the network structure and the resulting film has excellent transparency. Furthermore, since the resulting film contains an 5 inorganic substance. Si, and has a network structure, the film has high stability and excellent weather resistance. That is, as an invention for producing a rigid cured film which maintains high hydrophilicity over an extended period, the method of the present invention in which a polymer (i) having a sulfonic acid
10 group and an epoxy group and a silane compound (ii) are allowed to react and thereby cure is an extremely useful. [0096]
Meanwhile, in cases where a cured film is produced by a method other than the method of the present invention, for example,
15 defects of the following (a) to (e) are likely to occur; therefore, such a method may not be considered as a preferred method. [0097]
(a) In cases where a polymer which has a sulfonic acid group and no epoxy group is used in place of the polymer (i) of the present
20 invention, high hydrophilicity is attained in the same manner; however, the polymer is released by washing with water or the like and the hydrophilicity is thus likely to be reduced. In addition, since the polymer is not incorporated into the silica network, the strength and the toughness are likely to be low and the abrasion

SF-2582 53
resistance tends to be poor. Also, the transparency may be reduced due to, for example, layer separation between the polymer and silica. [0098] 5 {b} In cases where an epoxy compound having no sulfonic acid group is used in place of the polymer (i) of the present invention, the resulting film is not readily hydrophilized. [0099]
{c} In cases where a monomer having a sulfonic acid group
10 and an epoxy group is used in place of the polymer (i) of the present invention, since it is difficult to incorporate a large number of sulfonic acid groups into the monomer having an epoxy group, the number of sulfonic acid groups is small and the hydrophilicity is likely to be lower than that of the present invention. In
15 addition, since the monomer {low molecular weight) migrates
readily and unreacted monomer is likely to bleed out or be released out of the system, the use of such a monomer is not preferred also from the standpoints of the performance degradation and the safety after film formation.
20 [0100]
{d} In cases where a compound having a sulfonic acid group and a compound having an epoxy group are mixed and used in place of the polymer {i} of the present invention, because
• the compound having a sulfonic acid group and the compound

SF-2582 54
having an epoxy group do not react with each other and
• since the compound having a sulfonic acid group does not
react with the silane compound (ii),
the resulting structure is not readily networked and defects
5 are likely to be generated in the resulting network. Therefore,
as compared to a case where the polymer (i) of the present invention
is used, the abrasion resistance is more likely to be reduced due
to reductions in the hardness and toughness . In addition, because
• the compound having an epoxy group tends to have a lower
10 molecular weight and a lower polarity as compared to the polymer
(i) of the present invention,
the hydrophobic compound having an epoxy group is more likely to migrate to the surface, so that high hydrophilicity is not likely to be attained.
15 [0101]
(e) In cases where the silane compound (ii) of the present invention is not used, the resulting cured film is soft and may thus be readily damaged, which is not practical. [0102]
20 That is, the hydrophilic cured film of the present invention is produced by binding a polymer (i) , which is highly hydrophilized by sulfonic acid groups, to a siloxane network that is formed at a high density by allowing epoxy groups of the polymer (i) to react with silanol groups of a silane compound (ii).

SF-2582 55
[0103]
Therefore, a curing catalyst or a curing agent which accelerates the reaction between an epoxy group and a silanol group may also be added to the composition of the present invention. 5 Examples of a commonly-used curing catalyst or curing agent include hydrochloric acid, sulfuric acid, trifluoroacetic acid, acetic acid, phosphoric acid, boric acid, alumina, trialkoxy aluminum, acetylacetone aluminum, triethylenediamine, 2-methylimidazole and
10 2,4-diamine-6-[2'-methylimidazole-(1')]-ethyl-s-triazine. [0104]
The amount of the above-described curing catalyst or curing agent to be added is preferably in a range of 0.01 to 30 wt%, more preferably 0.1 to 10 wt%, still more preferably 0.2 to 5 wt%, with
15 respect to the total weight of the loaded polymer (i) and the loaded silane compound (ii). [0105]
Surprisingly, the present inventors discovered that, in cured films produced by allowing a highly hydrophilic polymer (i)
20 having a sulfonic acid group and an epoxy group to react with a silane compound (ii), there are cases where the concentration of sulfonic acid groups originated from the polymer (i) is centralized (inclined) in such a mode that the concentration gradually increases from the inner part of the cured film toward

SF-2582 56
the outer surface. It is speculated that the hydrophilicity increases in accordance with the degree of this inclination. [0106]
The main principle for forming this gradient structure is 5 that, "when vaporizing a polar solvent added in advance, the vaporization of the polar solvent is made to accompany the hydrophilic polymer (i) having a sulfonic acid group, thereby the polymer (i) is concentrated to the surface and cured".
When the sulfonic acid group concentration in the outer
10 surface opposite to a substrate is defined as "Sa" and the sulfonic acid group concentration at the midpoint between the interface in contact with the substrate and the outer surface is defined as "Da", the degree of gradient in the polymer (i) of the present invention which has a sulfonic acid group is represented by a ratio
15 of the sulfonic acid group concentrations {Sa/Da). That is, a high ratio of the sulfonic acid group concentrations {Sa/Da) indicates that a large number of sulfonic acid groups are concentrated in the outer surface of the subject cured film. This means that the higher the ratio of the sulfonic acid group
20 concentrations (Sa/Da), the higher is the hydrophilicity of the cured film and the more advantageous is the film of the present invention used as a hydrophilic film. Here, with regard to the above-described Da, "the midpoint between the interface in contact with the substrate and the outer surface" is usually the point

SF-2582 57
at which the depth from the outer surface is 1/2 of the film thickness toward the interface in contact with the substrate (hereinafter, this point is also referred to as "the point of 1/2 film thickness"). In the descriptions of Sa and Da, the terms 5 "sulfonic acid group" and "sulfonic acid group concentration" mean "-SO3M group" and "-SO3M group concentration", respectively. [0107]
The degree of gradient (ratio of sulfonic acid concentrations (Sa/Da)) in the film of the present invention is
10 usually in a range of 2 to 1,000, preferably 3 to 100, more preferably 4 to 60, still more preferably 5 to 50. In any case, it is more preferred that the lower limit value be 10 or higher. When the degree of gradient is less than 2, there is a tendency that the water contact angle exceeds 30° and the hydrophilicity
15 is thus reduced. When the degree of gradient is greater than 1, 000, the reaction (netv/orking) between the silanol group of the silane compound (ii) and the highly hydrophilic polymer (i) is likely to be incomplete, so that the toughness, transparency and durability (hydrophilicity retainability) tend to be reduced.
20 [0108]
In the present invention, an inclined cured film shows even higher hydrophilicity. A non-inclined film (for example, the degree of gradient Sa/Da = 1) also shows high hydrophilicity; however, it is lower than the hydrophilicity shown by an inclined

SF-2582 154

CLAIMS
1. A composition, comprising:
a polymer (i) which has a -SO3M group and an epoxy group, wherein M represents a hydrogen atom, an alkali metal, an alkaline 5 earth metal or an ammonium ion; and
a silane compound (ii) which has a total of two or more groups or atoms that are selected from the group consisting of a hydroxy group bound to a silane atom, an alkoxy group bound to a silane atom and a halogen atom bound to a silane atom. 10 2. The composition according to claim 1, wherein said polymer (i) is a polymer comprising a structural unit represented by the following Formula (1) and a structural unit represented by the following Formula (2): [Chem. 1]

SF-2582

155

A^—t-SOsM

h

(1)

(2)
(wherein, in the Formulae (1) and (2),
R^ and R^ independently represent a hydrogen atom or a methyl group; 5 M represents a hydrogen atom, an alkali metal, an alkaline earth metal or an ammonium ion;
the unit ratio, a/b, is 1,000/1 to 1/1,000; A^ is represented by (Ql}fCPl);
Ql is selected from -C00-, -CONH- and a phenylene 10 group which optionally has a substituent;

SF-2582 156
Pi is selected from the group consisting of a single bond and a divalent or higher valent hydrocarbon group having 1 to 15 carbon atoms which optionally has an ether structure; f is 0 or 1 and h is 1 to 5; 5 A^ is represented by (Q2)g(P2);
Q2 is selected from -C00-, a divalent or higher valent hydrocarbon group having 1 to 5 carbon atoms, a phenylene group which optionally has a substituent, and -0-;
P2 is selected from the group consisting of a single 10 bond, -X-P3-, -P4-Y- and -P5-;
P3 to P5 each independently represent a divalent or higher valent hydrocarbon group having 1 to 15 carbon atoms which optionally has an ether structure;
X represents oxygen, sulfur or -C00-;
15 Y represents oxygen or sulfur;
g is 0 or 1 and k is 1 to 5; and
when g is 1 and Q2 is -0- or -C00-, P2 is not -X-P3-) . 3. The composition according to claim 2, wherein,
in said Formula (1), A-*" represents a single bond, -CH2-, 20 -C6H4-, -COOCH2-, -COOCH2CH2-, -COOCH2CH2CH2-, -CONH-C{CH3)2-CH2-, -CONH-CH{CH3)-CH2-, -CONH-CH2-, -CONH-CH2CH2- or -CONH-CH2CH2CH2-; and,
in said Formula (2), A^ represents a single bond, -CH2-, -C6H4-, -0-, -CH2-O-, -CH2-O-CH2-, -C5H4-O-, -C6H4-0-CH2-, -C00-,

SF-2582

157

-COOCH2-, -C6H4-COO- or -C6H4-COO-CH2-.
4. The composition according to claim 1, wherein said polymer
(i) has a weight-average molecular weight, which is measured by GPC, of 300 to 3,000,000. 5 5. The composition according to claim 1, wherein said silane compound (ii) is a compound represented by the following Formula
(3):
[Chem. 2]

(3)
10 (wherein, in the Formula (3),
X"^ and X^ each independently represent a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom;
R"^ to R^ each independently represent a hydroxy group, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl 15 group, a phenyl group, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom; and
m represents an integer of 0 to 10,000). 6. The composition according to claim 1, wherein the reduced weight ratio of said polymer (i) and said silane compound (ii)

SF-2582 158
is in a range of 99.1/0.1 to 0.1/99.9.
7. A film, obtained by curing the composition according to any
one of claims 1 to 6.
8. The film according to claim 1, which is formed on a
5 substrate.
9. The film according to claim 8, wherein the ratio (Sa/Da)
of the sulfonic acid concentration in the outer surface (Sa) and
the sulfonic acid concentration at the midpoint between an
interface in contact with said substrate and said outer surface
10 (Da) is 2 to 1,000.
10. The film according to any one of claims 7 to 9, which has a surface water contact angle of 30° or smaller.
11. A film, which is formed on a substrate and comprises a -SO3M group (wherein, M represents a hydrogen atom, an alkali metal,
15 an alkaline earth metal or an ammonium ion) and a Si-O-Si structure or a Si-O-C structure, wherein
the ratio (Sa/Da) of the SO3M group concentration in the outer surface of said film (Sa) and the SO3M group concentration at the midpoint between an interface in contact with said substrate
20 and said outer surface (Da) is 2 to 1,000.
12. The film according to claim 11, wherein said ratio (Sa/Da) is 10 to 1,000.
13. The film according to claim 11 or 12, which has a surface water contact angle of 30° or smaller.

SF-2582

159

14. A laminate, produced by laminating the film according to any one of claims 7 to 13 on a substrate.
Dated this 12.05.2014