COPOLYMER AND HYDROPHILIC MATERIAL COMPOSED OF THE SAME
[Technical Field]
[0001] The present invention relates to a hydrophilic copolymer provided with antifogging performance, antifouling performance, and antistatic performance, and superior in abrasion resistance, and weather resistance; a composition containing the copolymer; a cured product {for example, a film) obtained-therefrom; and a use thereof.
[Background Art]
[0002] Improvement of fogging and fouling to occur on a substrate surface, such as a plastic surface and a glass surface, has been demanded recently more strongly.
As a method for resolving a fogging problem, an antifogging paint containing a reactive surfactant in addition to an acrylic oligomer has been proposed, and a cured product (film) obtained from the antifogging paint has allegedly improved hydrophilicity and water absorbency (Non Patent Literature 1). Further, as a method for resolving a fouling problem, for example, an anti-tainting material having self-cleaning performance
(anti-tainting performance) has drawn an attention, which can remove efficiently dirt stuck to an exterior wall, etc. (a hydrophobic substance in the air, etc, ) by detaching the same with rainfall, sprinkled water, or the like, by means of enhancing the

hydrophilicity of the surface (Non Patent Literature 2 and 3). [0003] The inventor et al. have proposed a cured product (monolayer film) graduating (concentrating) anionic hydrophilic groups in a surface as a method for resolving the fogging and fouling problems (Patent Literature 1). A cured product (film) obtained according to the invention is transparent and highly hydrophilic; superior in antifogging performance, antifouling performance, antistatic performance, quick-drying property (high drying speed of adsorbed water), and chemical resistance; and further hard and superior in a scratch property. However, through investigations of the inventor et al. it has been found that there is a room for improvement in terms of abrasion resistance and weather resistance.
[0004] Generally, as a method for improving the weather resistance and abrasion resistance of a substrate surface, a method of coating the substrate surface with an inorganic compound has been known. One of representative examples is a method of coating a silica compound as a hard coat on a spectacle lens by a sol gel reaction (Non Patent Literature 4).
[0005] A hard coat from a silica compound is very hard and as resistant to abrasion as glass due to its dense structure, but, on the other hand the hard coat has drawbacks such as fragility, difficulty in coloring, fogging tendency, and sticking and fixing tendency of dirt.

[0006] Various methods have been heretofore proposed for eliminating the drawbacks. For example, as a method for imparting dyeability and toughness, a method, by which a condensation product of melamine and a polyhydric alcohol, and a silane compound having an epoxy group are added to silica (Patent Literature 2) , a method, by which an epoxy compound and an aluminum complex are added to silica (Patent Literature 3), and a method, by which an acrylic polymer having a hydroxy group is added to silica (Patent Literature 4) have been proposed.
[0007] As a method for imparting antifogging performance, a method, by which a styrenic sulfonic acid polymer is added to silica, has been proposed (Patent Literature 5).
Further, as a water dispersible resin composition for painting a steel plate, a composition composed of (A) a copolymer resin prepared by emulsion polymerization of a polymerizable unsaturated monomer having an epoxy group, a polymerizable unsaturated monomer having an acid radical such as a sulfonic acid group, a polymerizable unsaturated monomer having a hydroxy group, and a polymerizable unsaturated monomer having a hydrolyzable silyl group, each at a content in a range of from 0.1 to 10 wt% with respect to the total amount of the monomers; (B) a zirconium compound; and (C) a silane coupling agent, has been known (Patent Literature 6). [0008] Similarly, as a water dispersible resin treatment

agent for a metal surface, a treatment agent composed of (A) a core-shell type resin prepared by emulsion polymerization of a polymerizable unsaturated monomer not having an epoxy group, an acid radical or a hydroxy group, a polymerizable unsaturated monomer having an epoxy group, a polymerizable unsaturated monomer having an acid radical such as a sulfonic acid group, a polymerizable unsaturated monomer having a hydroxy group, a polymerizable unsaturated monomer having a hydrolyzable silyl group, and a polymerizable unsaturated monomer having a cyclic ureido group with a specific structure, each at a content in a range of from 0.1 to 5 wt% with respect to the total amount of the monomers; (B) a zirconium compound; and (C) a silane coupling agent, has been known (Patent Literature 7).
[Citation List]
[Patent Literature]
[0009]
[Patent Literature 1] International Publication No. WO 2007/064003
[Patent Literature 2] Japanese Unexamined Patent Application Publication No. S56-22365
[Patent Literature 3] Japanese Unexamined Patent Application Publication No. S61-166824
[Patent Literature 4] Japanese Unexamined Patent Application Publication No. H06-166847

[Patent Literature 5] Japanese Unexamined Patent Application Publication No. Hll-021512
[Patent Literature 6] Japanese Unexamined Patent Application Publication No. 2006-342221
[Patent Literature 7] Japanese Unexamined Patent Application Publication No. 2006-089589 [Non Patent Literature] [0010]
[Non Patent Literature 1] Toagosei Research Annual Report, TREND, 1999, February, page 39 to 44
[Non Patent Literature 2] High Polymers, Japan (Kobunshi) , 44(5), page 307, 1995
[Non Patent Literature 3] Expected Materials for the Future, 2 (1), page 36-41, 2002
[Non Patent Literature 4] Technology and Application of Plastic Lens System, page 165-166, CMC Publishing Co., Ltd., 30 June 2003 [Summary of Invention] [Technical Problem]
[0011] Although the proposal according to the Patent Literature 5 is a preferable one, which can easily attain high hydrophilicity, it has become clear through investigations by the inventor, et al* that a polymer is apt to leave from a film such that the hydrophilicity tends to decrease by water (which becomes more remarkable, for example, for a smaller film thickness), and

there remains a problem of inapplicability to a situation where practical antifogging performance and antifouling performance (self-cleaning by rain water, etc.) are required. An object of the present invention is to provide a cured product (for example, a film) , in which the balance between hydrophilicity and abrasion resistance is superior, decrease in hydrophilicity by water is minimal, and the weather resistance is also superior, as well as a polymer and a polymer composition that can yield such a cured product.
[Solution to Problem]
[0012] For attaining the object, the inventor, et al. have diligently investigated to find that a cured product (for example, film) obtained from a copolymer (i) having a sulfonic acid-containing group, an epoxy group and an alkoxysilyl group in a molecule, and from a composition containing the copolymer (i) , are superior in a; balance between hydrophilicity and abrasion resistance, minimal in decrease of hydrophilicity by water, and also superior in weather resistance, thereby accomplishing the present invention.
[0013] Namely, the present invention relates to the following [1] to [10].
[1] A copolymer (i) comprising constitutional units expressed by the following general formulas (1), (2), and (3), [0014] [Chem. Formula 1]

wherein in the formulas (1) , (2) and (3) , each of a, b, and c represents the constitutional ratio of each constitutional unit, satisfying a - 0.998 to 0.001, b = 0.001 to 0.998, c = 0.001 to 0.998, and a + b + c = 1;
A1 is a single bond, a CI to C 10 divalent hydrocarbon group, a group expressed by the following formula (1-1), or a group expressed by the following formula (1-2); A2 is a single bond, a CI to C 10 divalent hydrocarbon group, a group expressed by the following formula (2-1), or a group expressed by the following formula (2-2) ; A3 is a single bond, a CI to C 10 divalent hydrocarbon group, a group expressed by the following formula (3-1) , or a group expressed by the following formula (3-2);
R1, R2 and R3 independently represent a hydrogen atom, or a methyl group; R4 independently represents a hydrogen atom, a

methyl group, an ethyl group, a propyl group, or a butyl group; R10 represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group; and
M represents a hydrogen atom, an alkali metal ion, a semi-valent alkaline earth metal ion, an ammonium ion, or an amine ion; and [0015] [Chem. Formula 2]
wherein in the formulas (1-1), (1-2), (2-1), (2-2), (3-1), and (3-2), n and n2 independently are an integer from 1 to 10; ni is an integer from 0 to 10; m is an integer from 1 to 6; mi is an integer from 0 to 6; 1 is an integer from 0 to 4; R5 and R6 independently represent a hydrogen atom, or a methyl group; * represents an end bonding to S03M; ** represents an end bonding to an epoxy group; and *** represents an end bonding to a Si atom.

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[2] The copolymer (1) according to [1] above, wherein the constitutional units expressed by the general formulas (1) , (2) , and (3) comprise respectively constitutional units expressed by the following general formulas (4), (5) and (6):

0016]

[Chem. Formula 3]

■&C /

(4)


(5)

(6)
wherein in the formulas (4), (5) and (6), each of a, b, and c represents the constitutional ratio of each constitutional unit, satisfying a = 0.998 to 0.001, b = 0.001 to 0.998, c = 0.001 to 10 0.998, and a + b + c = 1;
rii is an integer from 0 to 10; n is an integer from 1 to
10;
R1, R2, R3, R5, and R6 independently represent a hydrogen atom,
or a methyl group; R4 independently represents a hydrogen atom,

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a methyl group, an ethyl group, a propyl group, or a butyl group;
R10 represents a hydrogen atom, a methyl group, an ethyl group,
a propyl group, a butyl group, a methoxy group, an ethoxy group,
a propoxy group, or a butoxy group; and 5 M represents a hydrogen atom, an alkali metal ion, a
semi-valent alkaline earth metal ion, an ammonium ion, or an amine
ion.
[0017] [3] The copolymer (i) according to [1] or [2] above,
wherein the weight-average molecular weight of the copolymer (i) 10 measured by GPC is from 500 to 3,000,000.
[4] A composition comprising the copolymer (i) according to any
one of [1] to [3] above.
[5] The composition according to [4] above comprising further
a silane compound (ii) expressed by the following general formula 15 (7):
[0018] [Chem. Formula 4]

X1—Si-
2 \ ©13 / _
(7)
wherein in the formula (7), X1 and X2 independently represent a hydroxy group, a CI to C4 alkoxy group, or a halogen atom;
R11 to R14 independently represent a hydroxy group, a hydrogen atom, a CI to C4 alkyl group, a vinyl group, an allyl group, a

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phenyl group, a 2-phenylethyl group, a Cl to C4 alkoxy group, or a halogen atom; and
q is an integer from 0 to 10,000. [0019] [6] The composition according to [5] above, wherein 5 the ratio of the weight of the copolymer (i) to the weight of the silane compound (ii) reduced to a Si02 weight is in a range from 99.9/ 0.1 to 0.1/ 99.9.
[7] A film (Zl) with a thickness exceeding 100 nm (0.1 urn) obtained from the polymer according to any one of [1] to [3] above, 10 or the composition according to any one of [4] to [6] above. [8] The film (Zl) according to [7] above obtained by heating. [9] A laminate comprising at least one layer of a layer (Zl) that comprises the film according to [7] above. [10] The laminate according to [9] above, wherein the layer (Zl) 15 is an outermost layer of the laminate. [Advantageous Effects of Invention]
[0020] A cured product (for example, film) obtained from a copolymer or a composition containing the copolymer, according to the present invention, is superior in a balance between 20 hydrophilicity and abrasion resistance, minimal in decrease of hydrophilicity by water, and also superior in weather resistance. Therefore, various laminates prepared by laminating the film according to the present invention onto a substrate, etc. can be also provided.

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[Brief Description of Drawings]
[0021] [Figure 1] Figure 1 is a diagram showing comparative data (DSC chart) in terms of the thermal stability of typical compounds having a polymerizable functional group with a 5 carbon-carbon double bond and having a sulfonic acid-containing group to give a structural unit expressed by the general formula
(1) constituting a copolymer (i) used in the present invention.
[Figure 2] Figure 2 is a diagram showing a cutting method, for a sample, and measurement positions for a sulfonic acid 10 concentration, in measuring the degree of gradient in a sample obtained in Example.
[Figure 3] Figure 3 is a diagram showing the reflectance in Reference Experimental Example 2B.
[Figure 4] Figure 4 is a diagram showing the reflectance in 15 Reference Experimental Example 1A and Reference Comparative Example 5A.
[Description of Embodiments]
[0022] A copolymer (i) according to the present invention is characterized by including constitutional units expressed by 20 the following formulas (1), (2) and (3).
[0023] [Chem. Formula 5]

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(D

(2)


3
OR'
.10

(3)

10

In the formulas, each of a, b, and c represents the constitutional ratio of each constitutional unit, satisfying a = 0.998 to 0.001, b = 0.001 to 0,998, c = 0.001 to 0.998, and a + b + c = 1.
[0024] In the formula, R1, R2 and R3 independently represent a hydrogen atom, or a methyl group; R4 independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group; and R10 represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. [0025] In the formula, M represents a hydrogen atom, an alkali metal ion, a semi-valent alkaline earth metal ion, an

SF-2786 14
ammonium ion, or an amine ion.
In the formula, A1 is a single bond, a Cl to C 10 divalent hydrocarbon group, a group expressed by the following formula (1-1), or a group expressed by the following formula (1-2); A2 is a single bond, a Cl to C 10 divalent hydrocarbon group, a group expressed by the following formula (2-1), or a group expressed by the following formula (2-2); A3 is a single bond, a Cl to C 10 divalent hydrocarbon group, a group expressed by the following formula (3-1), or a group expressed by the following formula (3-2). [0026] [Chem. Formula 6]




n J m

(1-1)

ni

(1-2)

xr"
n2j

**
mi n (2-1)

(2-2)

n J m

(3-1)

(3-2)

In the formulas (1-1), (2-1), (2-2), and (3-2), n is an integer from 1 to 10; and m is an integer from 1 to 6. In the formula (1-2) , ni is an integer from 0 to 10. In the formula (2-1) ,
r\2 is an integer from 1 to 10; and mi is an integer from 0 to 6

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In the formulas (2-2), and (3-2), 1 is an integer from 0 to 4. [0027] In the formula (1-2), R5 and R6 independently represent a hydrogen atom, or a methyl group.
In the formulas (1-1) , and (1-2) , * represents an end bonding 5 to S03M; in the formulas (2-1) and (2-2), ** represents an end bonding to an epoxy group; and in the formulas (3-1) and (3-2), *** represents an end bonding to a Si atom.
[0028] A copolymer (i), by including the constitutional units, exhibits hydrophilicity and crosslinking reactivity; and 10 from the copolymer (i) or a composition containing the copolymer (i), a cured product, for example a film, superior in a balance between hydrophilicity and abrasion resistance, minimal in decrease of hydrophilicity by water, and also superior in weather resistance can be produced. 15 [0029] For A1 in the formula (1), a single bond, methylene, phenylene, a group expressed by the formula (1-1), and a group expressed by the formula (1-2) are preferable, and a group expressed by the formula (1-2) is more preferable. [0030] When A2 in the formula (1) is a group expressed by the 20 formula (1-2), a constitutional unit expressed by the formula (1) becomes a constitutional unit expressed by the following formula (4) . [0031] [Chem. Formula 7]

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W»i /- (4)
In the formula (4), a, R1, R5, R6, M, and ni have the same meanings as in the formula (1),
[0032] In the formula (1) and (4), M represents a hydrogen 5 atom, an alkali metal ion, a semi-valent alkaline earth metal ion, an ammonium ion, or an amine ion, however, considering a handling property of a copolymer (i) to be obtained, SO3M is preferably not in a form of free acid, and therefore among the above an alkali metal ion, a semi-valent alkaline earth metal ion, an ammonium
10 ion, and an amine ion are preferable.
[0033] As the alkali metal ion, a sodium ion, a potassium ion, and a rubidium ion are preferable. As the alkaline earth metal ion, a calcium ion, and a magnesium ion are preferable. As the ammonium ion, a tetrahydroammonium ion (NH4 + ) is preferable.
15 As the amine ion, a trihydro(methylamine) ion, a
trihydro(ethylamine) ion, a trihydro(propylamine) ion, a trihydro(isopropylamine) ion, a trihydro(butylamine) ion, a trihydro(cyclohexylamine) ion, a trihydro(benzylamine) ion, a dihydro(dimethylamine) ion, a hydro(trimethylamine) ion, a
20 trihydro(ethanolamine) ion, a dihydro(diethanolamine) ion, and a hydro(triethanolamine) ion are preferable.

SF-2786 17
[0034] For A in the formula (2), a group expressed by the formula (2-1), and a group expressed by the formula (2-2) are preferable, and a group expressed by the formula (2-1) is more preferable.
When A2 in the formula (2) is a group expressed by the formula (2-1), a constitutional unit expressed by the formula (2) becomes a constitutional unit expressed by the following formula (5A) . [0035] [Chem. Formula 8]

(5A)
10 In the formula (5A) , b, R , n, ri2 and mi have the same meanings as in the formula (2).
Among constitutional units expressed by the formula (5A) , a constitutional unit expressed by the following formula (5) , for which mi is 0, is a preferable mode.

15 [0036]

[Chem. Formula 9]


(5)
In the formula (5) , b, R , and n have the same meanings as in the formula (2).

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[0037] For A3 in the formula (3), a single bond, methylene, phenylene, and a group expressed by the formula (3-1) are preferable, and a group expressed by the formula (3-1) is more preferable.
When A3 in the formula (3) is a group expressed by the formula (3-1), a constitutional unit expressed by the formula (3) becomes a constitutional unit expressed by the following formula (6). [0038] [Chem. Formula 10]

(6)
10 In the formula (6), c, R3, R4, R10, and n have the same meanings as in the formula (3).
[0039] With respect to the copolymer (i) , each of a, b, and c represents the constitutional ratio of each constitutional unit (molar ratio of each constitutional unit), wherein a + b + c =
15 1. In this regard, a is in a range of from 0.998 to 0.001, b is in a range of from 0.001 to 0.998, and c is in a range of from 0.001 to 0.998.
[0040] For enhancing the hydrophilicity of the copolymer (i) , the ratio "a" of a constitutional unit having a sulfonic
20 acid-containing group expressed by the formula (1) should be increased. However, when the ratio of a constitutional unit

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according to the formula (1) is increased excessively, the ratios of constitutional units according to the formulas (2) and (3) having a group contributing to a crosslinking reaction are decreased relatively, and as the result the crosslink density of 5 a cured product (for example, film) to be formed from a copolymer
(i) , or a composition containing a copolymer (i) is decreased, so that the toughness, abrasion resistance, chemical resistance, etc. tend to decrease, which may be sometimes undesirable.
[0041] Therefore, with respect to constitutional ratios of 10 the respective constitutional units, it is preferable that a is in a range of from 0.990 to 0.400, b is in a range of from 0.005 to 0 . 300, and c is in a range of from 0 . 005 to 0 . 300, more preferable that a is in a range of from 0.990 to 0.600, b is in a range of from 0.005 to 0.200, and c is in a range of from 0.005 to 0.200, 15 and most preferable that a is in a range of from 0.980 to 0.700, b is in a range of from 0.010 to 0.150, and c is in a range of from 0.010 to 0.150.
[0042] There exists the same tendency, even when each constitutional unit is expressed on weight basis, and expressing 20 the weight-% of a constitutional unit according to the formula
(1) as a', the weight-% of a constitutional unit according to the formula (2) as b', and the weight-% of a constitutional unit according to the formula (3) as c', wherein the total weight of constitutional units according to Formulas (1), (2) and (3) is

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set at 100 weight-%, it is preferable that a* is in a range of from 99.0 to 20.0. weight-%, b' is in a range of from 0.5 to 40.0 weight-%, and c' is in a range of from 0.5 to 40.0 weight-%, more preferable that a' is in a range of from 99.0 to 40.0 weight-%, 5 b' is in a range of from 0.5 to 30.0 weight-%, and c1 is in a range of from 0.5 to 30.0 weight-%, and most preferable that a' is in a range of from 98.0 to 60.0 weight-%, b' is in a range of from 1.0 to 20.0 weight-%, and c' is in a range of from 1.0 to 20.0 weight-%.
10 [0043] A polymer containing constitutional units expressed by the formulas (1) to (3) can be obtained, for example, by polymerizing a mixture containing a compound having a polymerizable functional group with a carbon-carbon double bond and having a S03M group, corresponding to a constitutional unit
15 expressed by the formula (1), a compound having a polymerizable functional group with a carbon-carbon double bond and having an epoxy group, corresponding to a constitutional unit expressed by the formula (2) , and a compound having a polymerizable functional group with a carbon-carbon double bond and having an alkoxysilyl
20 group, corresponding to a constitutional unit expressed by the formula (3).
[0044] Consequently, the ratios of constitutional units expressed by the formulas (1) to (3), or the weight-% of the constitutional units can be regulated by the percentage of a

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compound corresponding to a constitutional unit expressed by the formula (1), a compound corresponding to a constitutional unit expressed by the formula (2), and a compound corresponding to a constitutional unit expressed by the formula (3) to be charged 5 for polymerization.
[0045] Examples of a compound having a polymerizable functional group with a carbon-carbon double bond and having a S03M group, corresponding to a constitutional unit expressed by the formula (1) include a compound expressed by the following 10 general the formula (1T)-
[0046] [Chem. Formula 11]
. R1
A1—-SO3M
(1')
In the formula (I1), R1, A1, and M have the same meanings as in the formula (1), and a preferable mode thereof is also the
15 same.
[0047] Among compounds expressed by the formula (l1), a sulfonic acid-derivative compound having a vinyl group, a sulfonic acid-derivative compound having an allyl group, a sulfonic acid-derivative compound having an isopropenyl group, a sulfonic
20 acid-derivative compound having a styryl group, a sulfonic acid-derivative compound having an acryloyloxy group or a

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methacryloyloxy group (hereinafter, acryloyloxy and methacryloyloxy may be collectively referred to as " (meth) acryloyloxy", and further, acrylic and methacrylic may be collectively referred to as "(meth)acrylic"), and a sulfonic 5 acid-derivative compound having an acrylamide group or a
methacrylamide group (hereinafter, acrylamide and methacrylamide may be collectively referred to as (meth)acrylamide) are relatively preferable. [0048] As a sulfonic acid-derivative compound having a vinyl
10 group, vinylsulfonic acid, lithium vinylsulfonate, sodium vinylsulfonate, potassium vinylsulfonate, rubidium vinylsulfonate, ammonium vinylsulfonate, etc, are preferable. [0049] As a sulfonic acid-derivative compound having an allyl group, allylsulfonic acid, sodium allylsulfonate,
15 potassium allylsulfonate, etc. are preferable.
As a sulfonic "acid-derivative compound having an isopropenyl group, sodium isopropenylsulfonate, potassium isopropenylsulfonate, etc, are preferable. [0050] As a sulfonic acid-derivative compound having a
20 styryl group, 4-styrenesulf onic acid, lithium 4-styrenesulf onate, sodium 4-styrenesulfonate, sodium 3-styrenesulfonate, sodium 2-styrenesulfonate, potassium 4-styrenesulfonate, potassium 3-styrenesulfonate, potassium 2-styrenesulfonate, rubidium 4-styrenesulfonate, calcium 4-styrenesulfonate, magnesium

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4-styrenesulfonate, ammonium 4-styrenesulfonate, etc. are preferable.
[0051] As a sulfonic acid-derivative compound having a
(meth)acryloyloxy group, 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 (meth)acrylate, rubidium 3-sulfopropyl
(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, potassium 8-sulfo-3,6-dioxaoctyl (meth)acrylate, etc. are preferable.
[0052] As a sulfonic acid-derivative compound having a
(meth)acrylamide group, compounds expressed by the following formula (4') are preferable.
[0053] [Chem. Formula 12]

(4' )
In the formula (4')/ R1, R5, R6, M, and ni have the same meanings as in the formula (4), and a preferable mode thereof is

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also the same.
[0054] Examples of a compound expressed by the formula (41) include sulfonic acid compounds having a (meth)acryloylamide group, such as 1-(meth)acrylamide-methanesulfonic acid, 5 potassium 1-(meth)acrylamide-methanesulfonate, 2- (meth)acrylamide-ethanesulfonic acid, sodium 2-(meth)acrylamide-ethanesulfonate, 2- (meth)acrylamide-propanesulfonic acid, potassium
2- (meth)acrylamide-propanesulfonate,
10 2- (meth)acrylamide-2-methylpropanesulfonic acid ( (meth) acrylamide--t-butyl sulfonic acid), sodium 2-(meth)acrylamide-2-methylpropanesulfonate, potassium 2-(meth)acrylamide-2-methylpropanesulfonate, rubidium 2-(meth)acrylamide-2-methylpropanesulfonate,
15 calcium 2-(meth)acrylamide-2-methylpropanesulfonate, magnesium 2-(meth)acrylamide-2-methylpropanesulfonate, ammonium 2-(meth)acrylamide-2-methyl-propylsulfonate, and potassium
3- (meth)acrylamide-propanesulfonate.
[0055] Among the compounds (l1) an acid-derivative compound 20 having a (meth)acrylamide group is preferable; a compound expressed by the formula (4') is more preferable; 2- (meth)acrylamide-2-methyl-propylsulfonic acid
( (meth) acrylamide-t-butylsulf onic acid) , an alkali metal salt of 2- (meth)acrylamide-2-methyl-propylsulfonic acid

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( (meth) acrylamide-t-butylsulf onic acid) , an alkaline earth metal salt of 2-(meth)acrylamide-2-methyl-propylsulfonic acid
((meth)acryiamide-t-butylsulfonic acid), an ammonium salt of 2-(meth)acrylamide-2-methyl-propylsulfonic acid 5 ((meth)acrylamide-t-butylsulfonic acid), and an amine salt of 2-(meth)acrylamide-2-methyl-propylsulfonic acid
( (meth) acrylamide-t-butylsulfonic acid) are further preferable; and an alkali metal salt of
2- (meth)acrylamide-2-methyl-propylsulfonic acid 10 ((meth)acrylamide-t-butylsulfonic acid) is most preferable.
[0056] A reason, why M in a compound according to the general formula (1') is preferably an alkali metal ion, a semi-valent alkaline earth metal ion, an ammonium ion, or an amine ion other than a hydrogen atom, will be described below. 15 [0057] When sulfonic acid is not neutralized (M is a hydrogen atom), a sulfonic acid group may react with an epoxy group contained in a compound having an epoxy group described below
(typically a compound expressed by the following general formula
(21)) to cause gelation during a polymerization reaction. A 20 schematic reaction formula of the reaction between an epoxy group and a sulfonic acid group will be described below.
[0058] [Chem. Formula 13]

SF-2786 26

For suppressing the reaction and obtaining a high purity copolymer (i), it is preferable that a sulfonic acid group is neutralized with a counter cation so as to suppress a reaction 5 between a sulfonic acid group and an epoxy group (similarly, a schematic reaction formula will be described below.). [0059] [Chem. Formula 14]

Reaction suppression
Further, among counter cations, such as an alkali metal ion, an alkaline earth metal ion, an ammonium ion, and an amine ion, an alkali metal ion tends to be preferable, which has tendency
15 for higher reaction inhibitory power and stability. Among alkali metals, sodium and potassium are preferable, and potassium is more preferable. When the counter cation is potassium, the thermal stability is sometimes higher than the case with sodium, although the reason behind the above is not sufficiently clear. For
20 reference, comparative data (DSC chart) in terms of the thermal stability of typical compounds having a polymerizable functional

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group with a carbon-carbon double bond, and having a sulfonic acid-containing group are shown in Figure 1. [00 60] Examples of a compound having a polymerizable a functional group with a carbon-carbon double bond and having an 5 epoxy group corresponding to a constitutional unit according to the formula (2) include a compound expressed by the following general formula (2')„ [0061] [Chem. Formula 15]
R2
° (2')
10 In the formula {2')/ R r and A have the same meanings as in the formula (2) , and a preferable mode thereof is also the same. [0062] Among compounds expressed by the formula (21)/ an epoxy compound having a vinyl group, an epoxy compound having a vinyl ether group, an epoxy compound having an allyl ether group,
15 an epoxy compound having an isopropenyl ether group, an epoxy compound having a styryl group, and an epoxy compound having a (meth)acryloyloxy group are relatively preferable. [0063] As an epoxy compound having a vinyl group, vinylcyclohexene monoxide, butadiene monoxide, pentadiene
20 monoxide, hexadiene monoxide etc. are preferable.

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[0064] As an epoxy compound having a vinyl ether group, vinyl glycidyl ether, butanediol-divinyl ether monoxide, cyclohexane dimethanol-divinyl ether monoxide,
4-glycidyloxymethyl-l-vinyloxymethyl-cyclohexane, diethylene 5 glycol-divinyl ether monoxide, tripropylene glycol-divinyl ether monoxide, 4-vinyloxy-l-glycidyloxy-butane, etc. are preferable. [0065] As an epoxy compound having an ally! ether group, allyl glycidyl ether, allyl epoxy ether, butanediol diallyl ether monoxide, cyclohexane dimethanol diallyl ether monoxide,
10 4-glycidyloxymethyl-l-allyloxymethylcyclohexane, diethylene
glycol diallyl ether monoxide, tripropylene glycol diallyl ether
monoxide, 4-allyloxy-l-glycidyloxy-butane, etc. are preferable.
[0066] As an epoxy compound having an isopropenyl ether group,
isopropenyl glycidyl ether, isopropenyl epoxy ether, butanediol
15 diisopropenyl ether monooxide, cyclohexanedimethanol diisopropenyl ether monooxide, 4-glycidyloxy methyl-1-isopropenyloxymethyl-cyclohexane, diethylene glycol diisopropenyl ether monooxide, tripropylene glycol diisopropenyl ether monooxide, 4-isopropenyloxy-l-glycidyloxy-butane, etc.
20 are preferable.
[0067] As an epoxy compound having a styryl group,
divinylbenzene monoxide, 4-(glycidyloxy)styrene,
3-(glycidyloxy)styrene, 2-(glycidyloxy)styrene,
4-(epoxyoxy)styrene, styryl carboxylic acid epoxy ester, styryl

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carboxylic acid glycidyl ester, etc. are preferable. [00 68] As an epoxy compound having a (meth) acryloyloxy group, compounds expressed by the following formula (5' ) is preferable. [0069] [Chem. Formula 16]
^u?
(5' )
In the formula (5')/ R2, and n have the same meanings as
in the formula (5).
[0070] Examples of compounds expressed by the formula (5')
include glycidyl (meth)acrylate, epoxy (meth)acrylate, 10 2-(glycidyloxy)ethyl (meth)acrylate, 3-(glycidyloxy)propyl
(meth)acrylate, 4-(glycidyloxy)butyl (meth)acrylate,
6-(glycidyloxy)hexyl (meth)acrylate,
5-(glycidyloxy)-3-oxapentyl (meth)acrylate,
3-(glycidyloxy)-2-hydroxypropyl (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 20 (meth)acrylate.
[0071] Among compounds expressed by the formula (21)/ an

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epoxy compound having a (meth) acryloyloxy group, an epoxy compound having ah allyl ether group, and an epoxy compound having a styryl group are preferable, and glycidyl {meth)acrylate, 4-glycidyloxybutyl (meth)acrylate, allyl glycidyl ether, and 5 4-glycidyloxystyrene are more preferable.
[0072] Examples of a compound having a polymerizable a functional group with a carbon-carbon double bond and having an alkoxysilyl group, corresponding to a constitutional unit ■ expressed by the formula (3) include a compound expressed by the 10 following general formula {3'). [0073] [Chem. Formula 17]
RIU (3')
In the formula (3!)/ R3^ R% R10/- and A3 have the same meanings as in the formula (3) , and a preferable mode thereof is also the
15 same.
[007 4] Among compounds expressed by the formula (3'), an alkoxysilyl compound having a vinyl group, an alkoxysilyl compound having a vinyl ether group, an alkoxysilyl compound having an allyl group, an alkoxysilyl compound having an isopropenyl group, an
20 alkoxysilyl compound having an allyl ether group, an alkoxysilyl compound having an isopropenyl ether, an alkoxysilyl compound

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having a styryl group, and an alkoxysilyl compound having a (meth)acryloyloxy group are relatively preferable. [0075] As an alkoxysilyl compound having a vinyl group, vinyltrimethoxysilane, vinyltriethoxysilane, 5 vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, vinylphenyldimethoxysilane, vinylethyldiethoxysilane, vinyldiethylmonoethoxysilane, vinyldimethylmonobutoxysilane, etc. are preferable.
10 [0076] As an alkoxysilyl compound having a vinyl ether group, (vinyloxy)ethyl trimethoxysilane, (vinyloxy)propyl trimethoxysilane, etc. are preferable.
As an alkoxysilyl compound having an allyl group, allyltrimethoxysilane, allyltriethoxysilane,
15 allyltripropoxysilane, allyltriisopropoxysilane, allyltributoxysilane, isopropenyltriethoxysilane, allylmethyldimethoxysilane, allylphenyldimethoxysilane, allylethyldiethoxysilane, allyldiethylmonoethoxysilane, allyldimethylmonobutoxysilane, etc. are preferable.
20 [0077] As an alkoxysilyl compound having an allyl ether group, (allyloxy)ethyl trimethoxysilane, (allyloxy)propyl trimethoxysilane, (allyloxy)propyl triethoxysilane, etc. are preferable. [0078] As an alkoxysilyl compound having an isopropenyl

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ether, (isopropenyloxy)propyltriethoxysilane, etc. are preferable.
As an alkoxysilyl compound having a styryl group, styryltrimethoxysilane, styryltriethoxysilane, 5 styryltributoxysilane, styrylmethyldimethoxysilane, etc. are preferable.
[0079] As an alkoxysilyl compound having a (meth) acryloyloxy group, compounds expressed by the following formula (6') are preferable. 10 [0080] [Chem. Formula 18]

P10
R (63 )
In the formula (6* ) , R3, R4, R10, and n have the same meanings
as in the formula (6).
[0081] Examples of compounds expressed by the formula (6!) 15 include (meth)acryloyloxyethyltrimethoxysilane,
(meth)acryloyloxypropyltrimethoxysilane,
(meth)acryloyloxybutyltrimethoxysilane,
(meth)acryloyloxyhexyltrimethoxysilane,
(meth)acryloyloxydecyltrimethoxysilane, 20 (meth)acryloyloxypropyltriethoxysilane,

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(meth)acryloyloxypropyltripropoxysilane, (meth)acryloyloxypropyltributoxysilane, (meth)acryloyloxypropylmethyldimethoxysilane, and (meth)acryloyloxypropylethyldiethoxysilane. 5 [0082] Among compounds expressed by the formula (3'), an allcoxysilyl compound having a vinyl group, an alkoxysilyl compound having a styryl group, and an alkoxysilyl compound having a (meth)acryloyloxy group are preferable, and vinyltrimethoxysilane, vinyltriethoxysilane,
10 styryltrimethoxysilane, styryltriethoxysilane, (meth)acryloyloxypropyltrimethoxysilane, and (meth)acryloyloxypropyltriethoxysilane are more preferable. [0083] The copolymer (i) may include a constitutional unit other than constitutional units expressed by the general formulas
15 (1) to (3) .
Such other constitutional unit can be obtained, for example, by adding a compound corresponding to such other constitutional unit to a monomer mixture containing compounds expressed by the (l1) to (3'), and polymerizing the same.
20 [0084] Examples of a compound corresponding to such other constitutional unit include acrylic acid, methacrylic acid, methyl (meth)acrylate, butyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenyl (meth)acrylate, tribromophenyl (meth)acrylate, hydroxyethyl

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(meth)acrylate, ethyl phosphate (meth)acrylate, tetramethylpiperidyl (meth)acrylate, perfluorooctylethyl
(meth)acrylate, thioglycidyl (meth)acrylate, styrene, acrylonitrile, divinylbenzene, and allyl (meth)acrylate. When 5 divinyl benzene or allyl (meth)acrylate is used, the same should be desirably used in a small amount, such that gelation of a copolymer (i) should not occur.
[0085] The ratio (molar ratio) of the total amount of. constitutional units expressed by the formula (1) , (2) , and (3) 10 {a + b + c) to such other constitutional unit (d), namely (a + b + c) / d, is ordinarily in a range of from 100/ 0 to 30/ 70, more preferably from 100/ 0 to 50/ 50, and further preferably from 100/ 0 to 60/ 40. Further, when such other constitutional unit (d) is used, the molar ratio (a + b + c)/ d is ordinarily in a range 15 of from 99.9/ 0.1 to 30/ 70, more preferably in a range of from 99/ 1 to 50/ 50, and further preferably in a range of from 95/ 5 to 60/ 40. In this regard, (a + b + c)/ d is in some cases preferably 70/ 30 or higher, and desirably 80/ 20 or higher.
[0086] Further, the ratio (mass ratio) of the total amount 20 of constitutional units expressed by the formula (1), (2), and
(3) (a + b + c) to such other constitutional unit (d) , namely (Wa + Wb + Wc)/ Wd, is in some cases preferably from 100/ 0 to 30/ 70, and in such cases more preferably from 100/ 0 to 50/ 50, and further preferably from 100/ 0 to 60/ 40.

SF-2786 35
[0087] A copolymer (i) to be used according to the present
invention is obtained typically by solution polymerization of a
mixture containing a compound expressed by the formula {I1), a
compound expressed by the formula (2'), a compound expressed by
5 the formula (3'), and a compound corresponding to another
constitutional unit to be contained according to need, in the presence of a polymerization initiator. Although there is no particular restriction on the bonding form of the copolymer .(i) , a copolymer (i) produced by radical polymerization using a radical
10 polymerization initiator is preferable. In that case, the
bonding form of a copolymer (i) is presumably a bonding form of a random copolymer.
[0088] The number of recurring structural units and the molecular weight of a copolymer (i) to be used according to the
15 present invention are regulated mainly by the solvent type, the compound (monomer) concentration, the polymerization initiator amount, the reaction temperature, etc.
The number of recurring structural units of the copolymer (i) is ordinarily in a range of from 1 to 10,000, preferably in
20 a range of from 3 to 3, 000, and more preferably in a range of from 30 to 1,500.
[0089] The weight-average molecular weight (Mw) of the copolymer (i) by GPC is ordinarily in a range of from 500 to 3,000,000, and from a viewpoint of durability and solubility

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preferably from 1000 to 1,000,000, and further preferably from 10,000 to 500,000.
[0090] The Mw/Mn of a copolymer (i) to be used according to the present invention is ordinarily from 1 to 10, preferably from 5 1 to 6, and more preferably 1 to 4. When the Mw/Mn is in the range, a copolymer (i) , or a composition containing a copolymer (i) is superior in terms of solubility or dispersibility, and a cured product, for example a film, obtained therefrom tends to be superior in terms of transparency, smoothness, or the like. 10 [0091] As the polymerization initiator, a radical polymerization initiator is preferable,
Examples of a radical polymerization initiator include: nitriles, such as azobisisobutyronitrile; ketone peroxides, such as methyl isobutyl ketone peroxide, 15 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-butyl cumyl peroxide; 20 peroxyketals, such as
2,2-bis{4,4-di-t~butylperoxycyclohexyl)propane, and 2,2-di(t-butylperoxy)butane;
alkyl peresters, such as a-cumyl peroxyneodecanoate, t-butyl peroxypivalate, 2,4,4-trimethylpentylperoxy-2-ethyl

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hexanoate, t-butylperoxy-2-ethyl hexanoate, and t-butylperoxy-3,5,5-trimethyl hexanoate; and
percarbonates, such as di(3-methoxybutylperoxy)dicarbonate, 5 bis(4-t-butylcyclohexyl)peroxydicarbonate, t-butylperoxy isopropyl carbonate, and diethylene glycol bis(t-butylperoxycarbonate).
[0092] The addition amount of the polymerization initiator is with respect to the total mass of a compound expressed by the 10 formula (l1 ) , a compound expressed by the formula {21 } , a compound expressed by the formula (31), and a compound corresponding to another constitutional unit to be added according to need, approx. in a range of from 0.01 to 10 wt%, preferably in a range of from 0.1 to 5 wt%, and further preferably in a range of from 0.2 to 15 3 wt%.
[0093] There is; no particular restriction on a polymerization solvent, insofar as the same does not cause a trouble such as inhibition of a polymerization reaction. A high polarity solvent, which has high dissolving power for a compound 20 expressed by the formula (l!)e a compound expressed by the formula {2')/ a compound expressed by the formula (3'), and a compound corresponding to another constitutional unit to be added according to need, tends to exhibit favorable performance. [0094] Examples of such a polymerization solvent include

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alcohols, such as methanol, ethanol, isopropanol (IPA), 1-propanol, 1-butanol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, and propylene glycol monomethyl ether; aprotic polar solvents, such as acetonitrile, sulfolane, dimethyl 5 sulfoxide, A7,W-dimethylformamide (DMF) , 2\7,A7-dimethylacetamide (DMAc) , and Z\7,N-dimethylimidazolidinone (DMI) ; water; and a mixture thereof.
[0095] The polymerization temperature is set mainly according to a 10 hour half-life temperature of a radical 10 polymerization initiator, which is approx. in a range of from room temperature to 200°C, preferably in a range of from 30 to 120°C, and more preferably in a range of from 40 to 100DC. [0096] Desirable properties and a higher order structure of a copolymer (i) to be used according to the present invention will 15 be described below.
Since the copolymer (i) is occasionally used as a cured product, a film and a laminate in an application, where high transparency is required, an amorphous polymer enabling high transparency (corresponding to an amorphous polymer or a 20 cryptocrystalline polymer, in which the crystallinity is low or the Tm (melting point) is not measurable, or the heat of fusion is small.) is preferable.
[0097] Such a highly transparent copolymer (i) can be produced, for example, by regulating the ratios of the respective

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constitutional units according to the formula (1) to (3) within desired ranges.
Meanwhile, when a higher order structure such as a core-shell structure is formed, such a core-shell structure 5 generally tends to form large particles in a micrometer size, and even when small particles in a nano size are formed, they tend to form secondary particles by coagulation or otherwise to end up with large aggregates in a micrometer size. The core-shell structure, for example, in a micrometer size has a particle size
10 beyond the 1/ 4 wavelength of light (approx. 100 nm), by which light is scattered to decrease transparency, and therefore is not applicable to a use requiring high transparency. [0098] In other words, a copolymer (i) to be used according to the present invention should preferably not form a higher order
15 structure such as core-shell. Further, such a core-shell
structure formed by 2 kinds of polymers, polymer source materials, or the like generally tends to exhibit 2 points of Tg {glass transition temperatures). [0099] Such a copolymer (i), which does not form a higher
20 order structure, can be produced, for example, by solution
polymerization, in which compounds (monomers) corresponding to the respective constitutional units are dissolved in a solvent. The thus produced copolymer
A reaction between epoxy groups is represented by the general formula (11), which is preferably caused by heating. The

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heating temperature is approximately in a range of from 30 to 250 °C, preferably in a range of from 30 to 200°C, and more preferably in a range of from 30 to 150 °C. The reaction between epoxy groups tends to be accelerated in the presence of a catalyst represented 5 by a cation such as an acid, or an anion such as a base.
[0104] A reaction between an epoxy group and an alkoxysilyl group is shown in the general formula (12) and the general formula (14) . [0105] Generally, an epoxy group cannot easily react
10 directly with an alkoxysilyl group, and ordinarily a reaction takes place between a silanol group generated by hydrolysis of an alkoxysilyl group and an epoxy group. A reaction between an epoxy group and an alkoxysilyl group is preferably also caused by heating. The heating temperature is approximately in a range
15 of from 30 to 300°C, preferably in a range of from 50 to 250°C, and more preferably in a range of from 100 to 200DC. [0106] A hydrolysis reaction of an alkoxysilyl group, and a reaction between an epoxy group and a silanol group tend to be accelerated in the presence of a catalyst represented by a cation
20 such as an acid, or an anion such as a base. Even when a catalyst is used as above, heating is preferably conducted for a reaction. The heating temperature is approximately in a range of from 30 to 250 °C, preferably in a range of from 30 to 200 °C, and more preferably in a range of from 30 to 180°C.

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[0107]
A reaction between alkoxysilyl groups is shown in the general formula (13) , which is preferably caused by heating. The heating temperature is approximately in a range of from 30 to 250°C, 5 preferably in a range of from 30 to 200"C, and more preferably in a range of from 30 to 180 °C.
[0108] An alkoxysilyl group is relatively easily hydrolyzed by moisture to be changed to a silanol group. The silanol group is highly reactive, and a reaction between silanol groups occurs
10 easier than a reaction between alkoxysilyl groups. Therefore, a reaction between alkoxysilyl groups occurs ordinarily as a reaction between silanol groups generated by hydrolysis with moisture, and a reaction between a silanol group and an alkoxysilyl group. The reaction between silanol groups, and the reaction
15 between a silanol group and an alkoxysilyl group are preferably caused by heating. The heating temperature is approximately in a range of from 30 to 200 °C, preferably in a range of from 30. to 180°C, and more preferably in a range of from 30 to 150°C. [0109] A reaction between alkoxysilyl groups, a hydrolysis
20 reaction of an alkoxysilyl group, a reaction between a silanol group and an alkoxysilyl group, and a reaction between silanol groups tend to be accelerated in the presence of a catalyst represented by a cation such as an acid, an anion such as a base, and a metallic compound, such as an alkoxy titanium, and tin oxide.

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[0110] A cured product (for example, a film) according to the present invention can be produced from a copolymer (i) as described above, but may be also produced from a composition of a copolymer (i) and a reactive compound other than a copolymer 5 (i) .
[0111] The weight ratio of a copolymer (i) to a reactive compound other than a copolymer (i) in a composition is approximately in a range of from 99.9/ 0.1 to 0 .1/ 99.9, preferably in a range of from 99.1/ 0.1 to 0.1/ 99.9, more preferably in a 10 range of from 99/ 1 to 1/ 99, and further preferably in a range of from 90/ 10 to 10/ 90.
[0112] Examples of a reactive compound other than a copolymer
(i) include a silane compound having a hydrolyzable group other than a copolymer (i) , a compound having an epoxy group other than 15 a copolymer (i), a compound having a hydroxy group, a compound having a mercapto group, a compound having a carboxy group, a compound having an amino group, and a reactive compound such as an acid anhydride. The silane compound having a hydrolyzable group means a silane compound, in which 1 to 4 groups (an alkoxy 20 group or a halogen atom) convertible by hydrolysis to a hydroxy group (a silanol group) are bound to a Si atom. The acid anhydride means a compound having 1 or more carboxylic anhydride structures.
[0113] Some examples of a reaction, which may occur between the reactive compound and an epoxy group contained in a copolymer

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(i) , are shown in the following general formula (20) . Further, some examples of a reaction, which may occur between the reactive compound and an alkoxysilyl group contained in a copolymer (i), are shown in the following general formula (21).

[0114

[Chem. Formula 20]

(B)
I H20 -Si- — HO-Si
H
or
X-Sr

(20)

[0115] [Chem. Formula 21]

SF-2786

47


tAoH (2 1)
When a compound having an epoxy group other than a copolymer (i) is used as the reactive compound, with respect to the reaction of the formula (20) (a reaction with an epoxy group of a copolymer 5 (i)), the reaction of the reaction route (F) occurs mainly, and with respect to the reaction of the formula (21) (a reaction with an alkoxysilyl group of a copolymer (i)), the reaction of the reaction route (A1) occurs mainly, so that curing occurs. [0116] As a compound having an epoxy group other than a 10 copolymer (i) , a multivalent epoxy compound having 2 or more epoxy groups in a molecule is preferable. Examples of a multivalent

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epoxy compound include bisphenol A bis (glycidyl ether) , bisphenol F bis{glycidyl ether), hydrogenated bisphenol A bis(glycidyl ether), N,N',N'' -tris (glycidyl) isocyanurate., isocyanurate-type polyglycidyl ether (TEPIC-PAS B22, TEPIC-PAS B26, Nissan Chemical 5 Ind., Ltd.), phenol novolac polyglycidyl ether (N-730, DIC Corporation; 152 Mitsubishi Chemical Corporation), 1.1.2.2.-tetrakis(4-glycidyloxyphenyl)ethane, N,N,N' ,W-tetraglycidyl diaminodiphenylmethane, trimethylolpropane triglycidyl ether, neopentyl glycol
10 diglycidyl ether, butanediol diglycidyl ether, poly(ethylene glycol) diglycidyl ether (YDE205, Mitsubishi Chemical Corporation), diglycidyl cyclohexanedicarboxylate, diglycidyl phthalate, 3,4-epoxycyclohexylmethyl 3 f, 4 '-epoxycyclohexane carboxylate, and dicyclodecane poly(glycidyl ether) (EPICLON
15 HP-7200L, EPICLON HP-7200H, DIC Corporation).
[0117] When a compound having a hydroxy group is used as the reactive compound, with respect to the reaction of the formula (20) (a reaction with an epoxy group of a copolymer (i)), the reaction of the reaction route (B) occurs mainly, and with respect
20 to the reaction of the formula (21) (a reaction with an alkoxysilyl group of a copolymer (i) ) , the reaction of the reaction route (G) occurs mainly, so that curing occurs.
[0118] As the compound having a hydroxy group, a multivalent hydroxy compound having 2 or more hydroxy groups is preferable.

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Examples of a multivalent hydroxy compound include ethylene glycol, diethylene glycol, 1,2-propylene glycol, glycerine, trimethylolpropane, pentaerythritol, dipentaerythritol, xylylenediol , resorcinol, bisphenol A, a phenol formaldehyde 5 resin (Mitsui Chemicals, Inc.), a condensation reaction product of melamine and formaldehyde, a condensation reaction product of melamine, formaldehyde, and a lower alcohol, a condensation reaction product of urea and formaldehyde, and a condensation reaction product of urea, formaldehyde, and a lower alcohol. As
10 a compound having a hydroxy group, in addition to the above, a condensation reaction product of melamine and a lower alcohol, a condensation reaction product of urea and a lower alcohol, etc. can be used. Since the above are easily hydrolyzed with moisture to generate a hydroxy group, they can be used as a compound having
15 a hydroxy group according to the present invention.
[0119] When a compound having a mercapto group is used as the reactive compound, with respect to the reaction of the formula (20) {a reaction with an epoxy group of a copolymer (i)), the reaction of the reaction route (C) occurs mainly, and with respect
20 to the reaction of the formula (21) (a reaction with an alkoxysilyl group of a copolymer (i) ) , the reaction of the reaction route (H) occurs mainly, so that curing occurs.
[0120] As a compound having a mercapto group, a multivalent mercapto compound having 2 or more mercapto groups is preferable.

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Examples of a multivalent mercapto compound include glycerine dithioglycolate, trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), dipentaerythritol hexakis(thioglycolate), glycerine di(3-mercaptopropionate), 5 trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), ethanedithiol, bis(2-mercaptoethyl)sulfide, xylylenedithiol, 1,4-dithiane-2,5-dithiol,
10 1,4-dithiane-2,5-bis(mercaptomethyl),
4-mercaptomethyl-3,6-dithiaoctane-l,8-dithiol,
4,8-bis(mercaptomethyl)-3,6,9-trithiaundecane-l,11-dithiol,
and 1,1,3,3-tetrakis(mercaptomethylthio)propane
[0121] When a compound having a carboxy group is used as the
15 reactive compound, with respect to the reaction of the formula (20) (a reaction with an epoxy group of a copolymer (i)), the reaction of the reaction route (D) occurs mainly, and with respect to the reaction of the formula (21) (a reaction with an alkoxysilyl group of a copolymer (i) ) , the reaction of the reaction route (I)
20 occurs mainly, so that curing occurs.
[0122] As the compound having a carboxy group, a multivalent carboxy compound having 2 or more carboxy groups is preferable. Examples of a multivalent carboxy compound include maleic acid, malonic acid, succinic acid, itaconic acid, citraconic acid,

phthalic acid, isophthalic acid, 5-hydroxy-isophthalic acid, terephthalic acid, oxydiphthalic acid, naphthalenedicarboxylic acid, trimellitic acid, pyromellitic acid, and L-aspartic acid. [0123] When a compound having an amino group is used as the reactive compound, with respect to the reaction of the formula (20) (a reaction with an epoxy group of a copolymer (i)), the reaction of the reaction route (E) occurs mainly, and with respect to the reaction of the formula (21) (a reaction with an alkoxysilyl group of a copolymer (j)), the reaction of the reaction route (I) occurs mainly, so that curing occurs.
[0124] As the compound having an amino group, a multivalent amino compound having 2 or more amino groups is preferable. Examples of a multivalent amino compound include phenylenediamine, toluylenediamine, bis(aminodiphenyl)methane, 2.2-bis(aminodiphenyl)propane, naphthalenediamine, xylylenediamine, ethylendiamine, hexamethylenediamine, N,N'-bis(2-aminoethyl)amine, bis(aminomethyl)norbornane, isophoronediamine, bis{aminodicyclohexyl)methane, L-glutamine, L-arginine, L-alanine-L-glutamine, L-cystine, and L-c.itrulline. [0125] When an acid anhydride is used as the reactive compound, with respect to the reaction of the formula (20) (a reaction with an epoxy group of a copolymer (i) ) , the reaction of the reaction route (G) occurs mainly, and with respect to the reaction of the formula (21) (a reaction with an alkoxysilyl group

of a copolymer (j) ) , the reaction of the reaction route (L) occurs mainly,.so that curing occurs.
[0126] Examples of the acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, oxydiphthalic anhydride, naphthalenedicarboxylic anhydride, trimellitic anhydride, and pyromellitic anhydride.
[0127] When a silane compound having a hydrolyzable group other than a copolymer (i) is used as the reactive compound, with respect to the reaction of the formula (20) (a reaction with an epoxy group of a copolymer (i) ) , the reaction of the reaction route
(A) occurs mainly, and with respect to the reaction of the formula
(21) (a reaction with an alkoxysilyl group of a copolymer (i)), the reaction of the reaction route (K) occurs mainly, so that curing occurs.
[0128] Among the reactive compounds a silane compound having a hydrolyzable group is preferable, and a silane compound (ii) expressed by the following general formula (7) is more preferable. When a silane compound (ii) is used as a reactive compound, a mode in which a combination of a silane compound (ii) and at least one compound selected out of a silane compound having a hydrolyzable group other than a silane compound (ii), a compound having an epoxy group other than a copolymer (i) , a compound having a hydroxy group, a compound having a mercapto group, a compound

having a carboxy group, a compound having an amino group, and an acid anhydride, is also preferable.
[0129] By inclusion of such a silane compound (ii) with a specific structure in addition to a copolymer (i) , the crosslink density of a cured product formed from the composition is enhanced and a tougher cured product, for example a film, can be easily produced. [0130] [Chem. Formula 22]
In the formula (7), q is an integer from 0 to 10,000, preferably an integer from 0 to 100, and more preferably an integer from 0 to 10.
[0131] In the formula (7) , R11 to R14 independently represent a hydroxy group, a hydrogen atom, a CI to C4 alkyl group, a vinyl group, an allyl group, a phenyl group, a 2-phenylethyl group, a Cl to C4 alkoxy group, or a halogen atom.
[0132] In the formula (7) , X1 and X2 independently represent a hydroxy group, a Cl to C4 alkoxy group, or a halogen atom.
When any of X1, X2, and Ru to R14 is a hydroxy group, the hydroxy group is a silanol group bonding to a Si atom, and therefore highly reactive such that a reaction involving a silanol group,

such as a reaction forming a siloxane bond (Si-O-Si) by dehydration condensation between silanol groups contained respectively in a silane compound (ii) and a copolymer (i), or a reaction between a silanol group contained in a silane compound (ii) and an epoxy group in a copolymer (i) , can occur sometimes easily even at room temperature. Further, when any of X1, X2, and R11 to R14 is an alkoxy group or a halogen atom, the same has similar reactivity as a hydroxy group, and, for example, an alkoxy group or a halogen atom is hydrolyzed to form a hydroxy group (silanol group), and then a reaction involving a silanol group similar to that described above can take place. Further, although an alkoxy group is less reactive than a hydroxy group, a condensation reaction can take place directly, if heated to a relatively high temperature (approx. 100°C or higher), so that a reaction to form a siloxane bond
(Si-O-Si) , etc, can occur. Consequently, when X1, X2, and R11 to R14 bonded to a Si atom is a hydroxy group, an alkoxy group, or a halogen atom, a crosslinking reaction between a silane compound
(ii) and a copolymer (i), a crosslinking reaction between two silane compounds (ii), or the like, can occur, so that a composition containing a copolymer (i) and a silane compound (ii) can be cured.
[0133] When R11 to R14 are a hydrogen atom, a CI to C4 alkyl group, a vinyl group, an allyl group, a phenyl group, or a 2-phenylethyl group, they do not participate in a crosslinking

reaction by a siloxane bond, etc., and therefore although they can contribute to prevention of cracking of an obtained cured product, impartment of toughness, etc., decrease in the hardness of the cured product may also occur.
[0134] By regulating the kind and ratio of groups at X1, X2, and R11 to R14, the physical property, for example hardness, of an obtained cured product can be regulated.
From a, viewpoint of regulation of the hardness of a cured product, the total number of a hydrogen atom, a Cl to C4 alkyl group, a vinyl group, an allyl group, a phenyl group, and a 2-phenylethyl group, (groups unable to participate in a reaction involving a silanol group) is preferably 2 or less, more preferably 1 or less, with respect to a Si atom contained in a silane compound (ii) . Further, the total number of a hydroxy group, a Cl to C4 alkoxy group, and a halogen atom {groups or an atom able to participate in a reaction involving a silanol group) as well as a siloxane bond is preferably 2 to 4, more preferably 3 to 4, with respect to a Si atom contained in a silane compound (ii).

CLAIMS
[Claim 1]
A copolymer (i) comprising constitutional units expressed by the following general formulas (1), (2), and (3): [Chem. Formula 1]
wherein in the formulas (1), (2) and (3), each of a, b, and c represents the constitutional ratio of each constitutional unit, satisfying a - 0.998 to 0.001, b = 0.001 to 0.998, c = 0.001 to 0.998, and a + b + c = 1;
A1 is a single bond, a Cl to C 10 divalent hydrocarbon group, a group expressed by the following formula (1-1), or a group expressed by the following formula (1-2); A2 is a single bond, a Cl to C 10 divalent hydrocarbon group, a group expressed by the following formula (2-1), or a group expressed by the following

formula (2-2) ; A3 is a single bond, a CI to C 10 divalent hydrocarbon group, a group expressed by the following formula (3-1) , or a group expressed by the following formula (3-2);
R1, R2 and R3 independently represent a hydrogen atom, or a methyl group; R4 independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group; R10 represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group; and
M represents a hydrogen atom, an alkali metal ion, a semi-valent alkaline earth metal ion, an ammonium ion, or an amine ion; and [Chem. Formula 2]
wherein in the formulas (1-1) , (1-2), (2-1), (2-2), (3-1), and (3-2), n and n2 independently are an integer from 1 to 10;

ni is an integer from 0 to 10; m is an integer from 1 to 6; mi is an integer from 0 to 6; 1 is an integer from 0 to 4; R5 and R6 independently represent a hydrogen atom, or a methyl group; * represents an end bonding to SO3M; ** represents an end bonding to an epoxy group; and *** represents an end bonding to a Si atom. [Claim 2]
The copolymer (i) according to claim 1, wherein the constitutional units expressed by the general formulas (1) , .(2) , and (3) comprise respectively constitutional units expressed by the following general formulas (4), (5) and (6): [Chem. Formula 3]
wherein in the formulas (4), (5) and (6), each of a, b, and c represents the constitutional ratio of each constitutional unit,

satisfying a = 0.998 to 0.001, b = 0.001 to 0.998, c = 0.001 to 0.998, and a + b-+ c = 1;
n is an integer from 1 to 10; ni is an integer from 0 to 10;
R1, R2, R3, R5, and R6 independently represent a hydrogen atom, or a methyl group; R4 independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a butyl group; R10 represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group; and
M represents a hydrogen atom, an alkali metal ion, a semi-valent alkaline earth metal ion, an ammonium ion, or an amine ion. [Claim 3]
The copolymer (i) according to claim 1 or 2, wherein the weight-average molecular weight of the copolymer (i) measured by GPC is from 500 to 3,000,000. [Claim 4]
A composition comprising the copolymer (i) according to any one of claims 1 to 3. [Claim 5]
The composition according to claim 4 comprising further a silane compound (ii) expressed by the following general formula (7) :

[Chertu Formula 4]
wherein in the formula (7), X1 and X2 independently represent a hydroxy group, a Cl to C4 alkoxy group, or a halogen atom;
R11 to R14 independently represent a hydroxy group, a hydrogen atom, a Cl to C4 alkyl group, a vinyl group, an allyl group, a phenyl group, a 2-phenylethyl group, a Cl to C4 alkoxy group, or a halogen atom; and
q is an integer from 0 to 10,000. [Claim 6]
The composition according to claim 5, wherein the ratio of the weight of the copolymer (i) to the weight of the silane compound (ii) reduced to a SiO^ weight is in a range from 99.9/ 0.1 to 0.1/ 99.9. [Claim 7]
A film (Zl) with a thickness exceeding 100 nm obtained from the polymer according to any one of claims 1 to 3, or the composition according to any one of claims 4 to 6. [Claim 8]
The film (Zl) according to claim 7 obtained by heating. [Claim 9]

A laminate comprising at least one layer of a layer (Zl) that comprises the film according to claim 7. [Claim 10]
The laminate according to claim 9, wherein the layer (Zl) is an outermost layer of the laminate.