FILM COMPRISING COPOLYMER OR COMPOSITION
[Technical Field]
[0001] The present invention relates to a film obtained from a hydrophilic copolymer or a composition containing the copolymer, provided with antifogging performance, antifouling performance, and antistatic performance, and superior in abrasion resistance and weather resistance; 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 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 monolayer film graduating (concentrating) anionic hydrophilic groups in a surface as a method for resolving the fogging and fouling problems {Patent Literature 1) . A 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 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 film. [Solution to Problem]
[0012] For attaining the object, the inventor, et al. have diligently investigated to find that films 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 [12].
[1] A film which is obtained from a copolymer (i) comprising constitutional units expressed by the following general formulas (1) , (2) , and (3) , or from a composition comprising the copolymer (i), and which has a thickness of not more than 100 nm {0.1 um) , [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 SO3M; ** represents an end bonding to an epoxy group; and *** represents an end bonding to a Si atom.

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[2] The film 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): 5 [0016] [Chem. Formula 3]


p6
H r
0 R5
ni /a (4)

*%^

b

(5)

OR4

(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;
ni 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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10

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 film according to [1] or [2] above, wherein
the weight-average molecular weight of the copolymer (i) measured
10 by GPC is from 500 to 3,000,000.
[4] The film according to any one of [1] to [3] above, which is obtained from a composition comprising the copolymer (i) and a silane compound (ii) expressed by the following general formula (7) :
15 [0018] [Chem. Formula 4]

(7)
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
20 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

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11
a halogen atom; and
q is an integer from 0 to 10,000.
[0019] [5] The film according to [4] above, wherein the
ratio of the weight of the copolymer (i) to the weight of the silane 5 compound (ii) reduced to a SiC>2 weight is in a range from 99.9/
0.1 to 0.1/ 99.9.
[0020] [6] The film according to any one of [1] to [5]
above, which is obtained by heating.
[7] A laminate comprising a layer (Z) that comprises the film 10 according to any one of [1] to [6] above and a substrate.
[8] The laminate according to [7] above, wherein the layer (Z)
is an outermost layer of the laminate.
[0021] [9] The laminate according to [7] or [8] above,
which comprises a hard coat layer between the layer (Z) and the 15 substrate.
[10] The laminate according to any one of [7] to [9] above,- which
comprises an antireflection layer between the layer (Z) and the
substrate.
[0022] [11] The laminate according to any one of [7] to [10] 20 above, wherein the layer (Z) has a change in a water contact angle
of 20° or less, the water contact angle being observed before and
after the layer (Z), immersed in 25°C water, is ultrasonically
treated for 10 minutes.
[12] An optical article or an optical device, comprising the

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12

laminate according to any one of [7] to [11] above. [Advantageous Effects of Invention]
[0023] A film obtained from a copolymer or a composition containing the copolymer, according to the present invention, is 5 superior in a balance between 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.
10 [Brief Description of Drawings]
[0024] [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 carbon-carbon double bond and having a sulfonic acid-containing
15 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 concentration, in measuring the degree of gradient in a sample
20 obtained in Example.
[Figure 3] Figure 3 is a diagram showing the reflectance in Example 2B*
[Figure 4] Figure 4 is a diagram showing the reflectance in Example 1A and Comparative Example 5A.

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13
[Description of Embodiments]
[0025] A copolymer (i) used for the preparation of the film according to the present invention is characterized by including constitutional units expressed by the following formulas (1) , (2) 5 and (3) .
[0026] [Chem. Formula 5]

AT-
A1—S03M

a

(1)

R2

O / b

(2)

OR4
A3—Sh-OR4
R10 ' c
(3)
In the formulas, each of a, b, and c represents the constitutional ratio of each constitutional unit, satisfying a 10 = 0.998 to 0.001, b = 0.001 to 0.998, c = 0.001 to 0.998, and a + b + c = 1.
[0027] In the formula, R1, R2 and R3 independently represent a hydrogen atom, or a methyl group; R4 independently represents

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14
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. 5 [0028] In the formula, M represents a hydrogen atom, an alkali metal ion, a semi-valent alkaline earth metal ion, an ammonium ion, or an amine ion.
In the formula, A1 is a single bond, a CI to C 10 divalent hydrocarbon group, a group expressed by the following formula
10 (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
15 formula (3-1) , or a group expressed by the following formula (3-2) . [0029] [Chem. Formula 6]

SF-2787

15

-*
n J

m

(1-D

HN'

R6R5
"1

(1-2)

**
n2j

mj

**

(2-1)

(2-2)


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) , 5 n2 is an integer from 1 to 10; and mi is an integer from 0 to 6. In the formulas (2-2), and (3-2), 1 is an integer from 0 to 4. [0030] 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 10 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.
[0031] A copolymer (i), by including the constitutional units, exhibits hydrophilicity and crosslinking reactivity; and 15 from the copolymer (i) or a composition containing the copolymer

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16
(i), 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. [0032] For A1 in the formula (1), a single bond, methylene, 5 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. [0033] When A2 in the formula (1) is a group expressed by the formula (1-2) , a constitutional unit expressed by the formula (1) 10 becomes a constitutional unit expressed by the following formula (4). [0034] [Chem. Formula 7]

►I/
N-A/ \zS03M
R V ;ai /a (4)
In the formula (4), a, R1, R5, R6, M, and ni have the same
15 meanings as in the formula (1).
[0035] In the formula (1) and (4), M represents a hydrogen 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, S03M is preferably
20 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

SF-2787
17
ion, and an amine ion are preferable.
[0036] 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 5 the ammonium ion, a tetrahydroammonium ion (NH4+) is preferable. 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
10 dihydro(dimethylamine) ion, a hydro(trimethylamine) ion, a
trihydro(ethanolamine) ion, a dihydro(diethanolamine) ion, and a hydro(triethanolamine) ion are preferable.
[0037] For A2 in the formula (2) , a group expressed by the formula (2-1), and a group expressed by the formula (2-2) are
15 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).
20 [0038] [Chem. Formula 8]

(5A)

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In the formula (5A) , b, R2, n, n2 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 5 which mi is 0, is a preferable mode. [0039] [Chem. Formula 9]

(5)
In the formula (5) , b, R2, and n have the same meanings as
in the formula (2). 10 [0040] 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 15 (3-1) , a constitutional unit expressed by the formula (3) becomes
a constitutional unit expressed by the following formula (6).
[0041] [Chem. Formula 10]


OR4
\ In R (6)

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19
In the formula (6) , c, R3, R4, R10, and n have the same meanings as in the formula (3).
[0042] With respect to the copolymer (i) , each of a, b, and c represents the constitutional ratio of each constitutional unit 5 (molar ratio of each constitutional unit), wherein a + b + c = 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. [0043] For enhancing the hydrophilicity of the copolymer (i) ,
10 the ratio "a" of a constitutional unit having a sulfonic
acid-containing group expressed by the formula (1) should be increased. However, when the ratio of a constitutional unit according to the formula (1) is increased excessively, the ratios of constitutional units according to the formulas (2) and (3)
15 having a group contributing to a crosslinking reaction are
decreased relatively, and as the result the crosslink density of a 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,
20 which may be sometimes undesirable.
[0044] Therefore, with respect to constitutional ratios of 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

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20
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, 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 5 from 0.010 to 0.150.
[0045] There exists the same tendency, even when each constitutional unit is expressed on weight basis, and expressing the weight-% of a constitutional unit according to the formula (1) as a' , the weight-% of a constitutional unit according to the
10 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 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 4 0.0
15 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-%, b1 is in a range of from 0.5 to 30.0 weight-%, and c' 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
20 1.0 to 20.0 weight-%, and c' is in a range of from 1.0 to 20.0 weight-%.
[0046] 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

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21
polymerizable functional group with a carbon-carbon double bond and having a S03M group, corresponding to a constitutional unit expressed by the formula (1) , a compound having a polymerizable functional group with a carbon-carbon double bond and having an 5 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 group, corresponding to a constitutional unit expressed by the formula (3).
10 [0047] 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 compound corresponding to a constitutional unit expressed by the formula (1), a compound corresponding to a constitutional unit
15 expressed by the formula (2), and a compound corresponding to a constitutional unit expressed by the formula (3) to be charged for polymerization.
[0048] Examples of a compound having a polymerizable functional group with a carbon-carbon double bond and having a
20 SO3M group, corresponding to a constitutional unit expressed by the formula (1) include a compound expressed by the following general the formula (l1). [0049] [Chem. Formula 11]

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22
R1
A1—SOoM
(l5)
In the formula (l')7 R1, A1, and M have the same meanings as in the formula (1), and a preferable mode thereof is also the same. 5 [0050] Among compounds expressed by the formula (1'), 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 acid-derivative compound having a styryl group, a sulfonic
10 acid-derivative compound having an acryloyloxy group or a 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
15 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. [0051] As a sulfonic acid-derivative compound having a vinyl
20 group, vinylsulfonic acid, lithium vinylsulfonate, sodium vinylsulfonate, potassium vinylsulfonate, rubidium

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vinylsulfonate, ammonium vinylsulfonate, etc. are preferable. [0052] As a sulfonic acid-derivative compound having an allyl group, allylsulfonic acid, sodium allylsulfonate, potassium allylsulfonate, etc. are preferable. 5 As a sulfonic acid-derivative compound having an
isopropenyl group, sodium isopropenylsulfonate, potassium isopropenylsulfonate, etc. are preferable.
[0053] As a sulfonic acid-derivative compound having a styryl group, 4-styrenesulfonic acid, lithium 4-styrenesulfonate,
10 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 4-styrenesulfonate, ammonium 4-styrenesulfonate, etc. are
15 preferable.
[0054] 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
20 (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,

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potassium 10-sulfodecyl (meth)acrylate, potassium
5-sulfo-3-oxapentyl (meth)acrylate, potassium
8-sulfo-3,6-dioxaoctyl (meth)acrylate, etc. are preferable.
[0055] As a sulfonic acid-derivative compound having a
(meth)acrylamide group, compounds expressed by the following
formula (4') are preferable.
[0056] [Chem. Formula 12]


N^M/S03M
R5 \ /in (4> j
In the formula (41), R1, R5, R6, M, and ru have the same 10 meanings as in the formula (4) , and a preferable mode thereof is also the same.
[0057] 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, 15 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, 20 2-(meth)acrylamide-2-methylpropanesulfonic acid ((meth)acrylamide-t-butyl sulfonic acid), sodium

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2-(meth)acrylamide-2-methylpropanesulfonate, potassium 2-(meth)acrylamide-2-methylpropanesulfonate, rubidium 2-(meth)acrylamide-2-methylpropanesulfonate,
calcium 2-(meth)acrylamide-2-methylpropanesulfonate, magnesium 5 2-(meth)acrylamide-2-methylpropanesulfonate, ammonium
2-(meth)acrylamide-2-methyl-propylsulfonate, and potassium 3-(meth)acrylamide-propanesulfonate.
[0058] Among the compounds (lr) an acid-derivative compound having a (meth)acrylamide group is preferable; a compound
10 expressed by the formula (4'} is more preferable; 2-(meth)acrylamide-2-methyl-propylsulfonic acid ( (meth) acrylamide-t-butylsulfonic acid) , an alkali metal salt of 2-(meth)acrylamide-2-methyl-propylsulfonic acid ( (meth) acrylamide-t-butylsulfonic acid) , an alkaline earth metal
15 salt of 2-(meth)acrylamide-2-methyl-propylsulfonic acid
((meth)acrylamide-t-butylsulfonic acid), an ammonium salt of 2-(meth)acrylamide-2-methyl-propylsulfonic acid ((meth)acrylamide-t-butylsulfonic acid), and an amine salt of 2-(meth)acrylamide-2-methyl-propylsulfonic acid
20 ( (meth) acrylamide-t-butylsulfonic acid) are further preferable; and an alkali metal salt of
2- (meth)acrylamide-2-methyl-propylsulfonic acid ((meth)acrylamide-t-butylsulfonic acid) is most preferable. [0059] A reason, why M in a compound according to the general

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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. [0060] When sulfonic acid is not neutralized (M is a hydrogen 5 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 (2')) to cause gelation during a polymerization reaction. A schematic reaction formula of the reaction between an epoxy group 10 and a sulfonic acid group will be described below. [0061] [Chem. Formula 13]

For suppressing the reaction and obtaining a high purity copolymer (i), it is preferable that a sulfonic acid group is 15 neutralized with a counter cation so as to suppress a reaction between a sulfonic acid group and an epoxy group (similarly, a schematic reaction formula will be described below.). [0062] [Chem. Formula 14]


20 y/~\ \ . / o V-OK
II
o
Neutralization
Reaction suppression

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27
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 5 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
10 reference, comparative data (DSC chart) in terms of the thermal stability of typical compounds having a polymerizable functional group with a carbon-carbon double bond, and having a sulfonic acid-containing group are shown in Figure 1. [0063] Examples of a compound having a polymerizable a
15 functional group with a carbon-carbon double bond and having an epoxy group corresponding to a constitutional unit according to the formula (2) include a compound expressed by the following general formula (2'). [0064] [Chem. Formula 15]
R2
A2^7
o (2.}
20

SF-2787
28
In the formula (2'), R2, and A2 have the same meanings as in the formula (2) , and a preferable mode thereof is also the same. [0065] Among compounds expressed by the formula (2'), an epoxy compound having a vinyl group, an epoxy compound having a 5 vinyl ether group, an epoxy compound having an allyl ether group, 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. [0066] As an epoxy compound having a vinyl group,
10 vinylcyclohexene monoxide, butadiene monoxide, pentadiene monoxide, hexadiene monoxide etc. are preferable. [0067] As an epoxy compound having a vinyl ether group, vinyl glycidyl ether, butanediol-divinyl ether monoxide, cyclohexane dimethanol-divinyl ether monoxide,
15 4-glycidyloxymethyl-l-vinyloxymethyl-cyclohexane, diethylene
glycol-divinyl ether monoxide, tripropylene glycol-divinyl ether
monoxide, 4-vinyloxy-l-glycidyloxy-butane, etc. are preferable.
[0068] As an epoxy compound having an allyl ether group,
allyl glycidyl ether, allyl epoxy ether, butanediol diallyl ether
20 monoxide, cyclohexane dimethanol diallyl ether monoxide,
4-glycidyloxymethyl-l-allyloxymethylcyclohexane, diethylene glycol diallyl ether monoxide, tripropylene glycol diallyl ether monoxide, 4-allyloxy-l-glycidyloxy-butane, etc. are preferable. [0069] As an epoxy compound having an isopropenyl ether group,

SF-2787
29
isopropenyl glycidyl ether, isopropenyl epoxy ether, butanediol diisopropenyl ether monooxide, cyclohexanedimethanol diisopropenyl ether monooxide, 4-glycidyloxy methyl-1-isopropenyloxymethyl-cyclohexane, diethylene glycol 5 diisopropenyl ether monooxide, tripropylene glycol diisopropenyl ether monooxide, 4-isopropenyloxy-l-glycidyloxy-butane, etc. are preferable.
[0070] As an epoxy compound having a styryl group, divinylbenzene monoxide, 4-(glycidyloxy)styrene,
10 3-(glycidyloxy)styrene, 2-(glycidyloxy)styrene,
4-(epoxyoxy)styrene, styryl carboxylic acid epoxy ester, styryl carboxylic acid glycidyl ester, etc. are preferable. [0071] As an epoxy compound having a (meth) acryloyloxy group, compounds expressed by the following formula (5') is preferable.
15 [0072] [Chem. Formula 16]
D2

V?
(5' ) In the formula (51), R2, and n have the same meanings as
in the formula (5).
[0073] Examples of compounds expressed by the formula (51)
20 include glycidyl (meth)acrylate, epoxy (meth)acrylate,
2-(glycidyloxy)ethyl (meth)acrylate, 3-(glycidyloxy)propyl

SF-2787
30
(meth)acrylate, 4-(glycidyloxy)butyl (meth)acrylate, 6-(glycidyloxy)hexyl (meth)acrylate, 5~(glycidyloxy)-3-oxapentyl (meth)acrylate, 3-(glycidyloxy)-2-hydroxypropyl (meth)acrylate, 5 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
10 (meth)acrylate.
[0074] Among compounds expressed by the formula (21), an epoxy compound having a (meth) acryloyloxy group, an epoxy compound having an allyl ether group, and an epoxy compound having a styryl group are preferable, and glycidyl (meth)acrylate,
15 4-glycidyloxybutyl (meth)acrylate, allyl glycidyl ether, and 4-glycidyloxystyrene are more preferable.
[0075] 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
20 expressed by the formula (3) include a compound expressed by the following general formula (3'). [0076] [Chem. Formula 17]

SF-2787

31

A3—SKOR4
R10 (3')
In the formula (3 ' ) , R3, R4, R10, and A3 have the same meanings
as in the formula (3) , and a preferable mode thereof is also the
same.
5 [0077] 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
alkoxysilyl compound having an allyl ether group, an alkoxysilyl
10 compound having an isopropenyl ether, an alkoxysilyl compound having a styryl group, and an alkoxysilyl compound having a (meth)acryloyloxy group are relatively preferable. [0078] As an alkoxysilyl compound having a vinyl group, vinyltrimethoxysilane, vinyltriethoxysilane,
15 vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, vinylphenyldimethoxysilane, vinylethyldiethoxysilane, vinyldiethylmonoethoxysilane, vinyldimethylmonobutoxysilane, etc. are preferable.
20 [0079] As an alkoxysilyl compound having a vinyl ether group, (vinyloxy)ethyl trimethoxysilane, (vinyloxy)propyl

SF-2787
32
trimethoxysilane, etc. are preferable.
As an alkoxysilyl compound having an allyl group,
allyltrimethoxysilane, allyltriethoxysilane,
allyltripropoxysilane, allyltriisopropoxysilane, 5 allyltributoxysilane, isopropenyltriethoxysilane,
allylmethyldimethoxysilane, allylphenyldimethoxysilane,
allylethyldiethoxysilane, allyldiethylmonoethoxysilane,
allyldimethylmonobutoxysilane, etc. are preferable.
[0080] As an alkoxysilyl compound having an allyl ether group, 10 (allyloxy)ethyl trimethoxysilane, (allyloxy)propyl
trimethoxysilane, (allyloxy)propyl triethoxysilane, etc. are
preferable.
[0081] As an alkoxysilyl compound having an isopropenyl
ether, (isopropenyloxy)propyltriethoxysilane, etc. are 15 preferable.
As an alkoxysilyl compound having a styryl group,
styryltrimethoxysilane, styryltriethoxysilane,
styryltributoxysilane, styrylmethyldimethoxysilane, etc. are
preferable. 20 [0082] As an alkoxysilyl compound having a (meth) acryloyloxy
group, compounds expressed by the following formula (61) are
preferable.
[0083] [Chem. Formula 18]

SF-2787

33


(6? )
In the formula (6'), R3, R4, Ri0, and n have the same meanings
as in the formula (6).
Examples of compounds expressed by the formula (6') include 5 (meth)acryloyloxyethyltrimethoxysilane,
(meth)acryloyloxypropyltrimethoxysilane,
(meth)acryloyloxybutyltrimethoxysilane,
(meth)acryloyloxyhexyltrimethoxysilane,
(meth)acryloyloxydecyltrimethoxysilane, 10 (meth)acryloyloxypropyltriethoxysilane,
(meth)acryloyloxypropyltripropoxysilane,
(meth)acryloyloxypropyltributoxysilane,
(meth)acryloyloxypropylmethyldimethoxysilane, and
(meth)acryloyloxypropylethyldiethoxysilane. 15 [0084] Among compounds expressed by the formula (3'), an
alkoxysilyl 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, 20 styryltrimethoxysilane, styryltriethoxysilane,

SF-2787
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(meth)acryloyloxypropyltrimethoxysilane, and (meth)acryloyloxypropyltriethoxysilane are more preferable. [0085] The copolymer (i) may include a constitutional unit other than constitutional units expressed by the general formulas 5 (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.
10 [0086] 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
15 (meth)acrylate, ethyl phosphate (meth)acrylate,
tetramethylpiperidyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, thioglycidyl (meth)acrylate, styrene, acrylonitrile, divinylbenzene, and allyl (meth)acrylate. When divinyl benzene or allyl (meth)acrylate is used, the same should
20 be desirably used in a small amount, such that gelation of a copolymer (i) should not occur.
[0087] The ratio (molar ratio) of the total amount of constitutional units expressed by the formula (1), (2), and (3) (a + b + c) to such other constitutional unit (d), namely (a +

SF-2787
35
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 5 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. Further, the ratio (mass ratio) of the total amount of
10 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.
15 [0088] 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 (1'), a compound expressed by the formula {2'), a compound expressed by the formula (31), and a compound corresponding to another
20 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 polymerization initiator is preferable. In that case, the

SF-2787
36
bonding form of a copolymer (i) is presumably a bonding form of
a random copolymer.
[0089] The number of recurring structural units and the
molecular weight of a copolymer (i) to be used according to the 5 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 10 a range of from 3 to 3,000, and more preferably in a range of from
30 to 1,500.
[0090] 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 15 preferably from 1000 to 1,000,000, and further preferably from
10,000 to 500,000.
[0091] The Mw/Mn of a copolymer (i) to be used according to
the present invention is ordinarily from 1 to 10, preferably from
1 to 6, and more preferably 1 to 4. When the Mw/Mn is in the range, 20 a copolymer (i) , or a composition containing a copolymer (i) is
superior in terms of solubility or dispersibility, and a film
obtained therefrom tends to be superior in terms of transparency,
smoothness, or the like.
[0092] As the polymerization initiator, a radical

SF-2787
37
polymerization initiator is preferable.
Examples of a radical polymerization initiator include:
nitriles, such as azobisisobutyronitrile;
ketone peroxides, such as methyl isobutyl ketone peroxide, 5 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; 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-cumyl peroxyneodecanoate, t-butyl peroxypivalate, 2,4,4-trimethylpentylperoxy-2-ethyl 15 hexanoate, t-butylperoxy-2-ethyl hexanoate, and t-butylperoxy-3,5,5-trimethyl hexanoate; and
percarbonates, such as di(3-methoxybutylperoxy)dicarbonate,
bis(4-t-butylcyclohexyl)peroxydicarbonate, fc-butylperoxy 20 isopropyl carbonate, and diethylene glycol bis{t-butylperoxycarbonate).
[0093] The addition amount of the polymerization initiator is with respect to the total mass of a compound expressed by the formula (1' ) , a compound expressed by the formula (2 ' ) , a compound

SF-2787
38
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 5 3 wt%.
[0094] 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
10 expressed by the formula (1' ) , a compound expressed by the formula (21), 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. [0095] Examples of such a polymerization solvent include
15 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 sulfoxide, W/AT-dimethylformamide (DMF) , ATyAT-dimethylacetamide
20 (DMAc), and N,W~dimethylimidazolidinone (DMI); water; and a mixture thereof.
[0096] The polymerization temperature is set mainly according to a 10 hour half-life temperature of a radical polymerization initiator, which is approx. in a range of from room

SF-2787
39
temperature to 200eC, preferably in a range of from 30 to 120°C, and more preferably in a range of from 4 0 to 100°C. [0097] Desirable properties and a higher order structure of a copolymer (i) to be used according to the present invention will 5 be described below.
Since the copolymer (i) is occasionally used as 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 cryptocrystalline polymer, in which
10 the crystallinity is low or the Tm (melting point) is not measurable, or the heat of fusion is small.) is preferable. [0098] Such a highly transparent copolymer (i) can be produced, for example, by regulating the ratios of the respective constitutional units according to the formula (1) to (3) within
15 desired ranges.
Meanwhile, when a higher order structure such as a core-shell structure is formed, such a core-shell structure generally tends to form large particles in a micrometer size, and even when small particles in a nano size are formed, they tend
20 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 beyond the 1/ 4 wavelength of light (approx. 100 nm), by which light is scattered to decrease transparency, and therefore is not

SF-2787
40
applicable to a use requiring high transparency. [0099] In other words, a copolymer (i) to be used according to the present invention should preferably not form a higher order structure such as core-shell. Further, such a core-shell 5 structure formed by 2 kinds of polymers, polymer source materials, or the like generally tends to exhibit 2 points of Tg (glass transition temperatures).
[0100] Such a copolymer (i), which does not form a higher order structure, can be produced, for example, by solution
10 polymerization, in which compounds (monomers) corresponding to the respective constitutional units are dissolved in a solvent. The thus produced copolymer (i) is ordinarily a polymer containing a large number of sulfonic acid-containing groups, and is in many cases only soluble in water. Therefore, in such a case,
15 a copolymer precipitates out of a polymerization solution in step with advancement of a polymerization reaction, unless a large amount of water is used as a polymerization solvent. [0101] Therefore, an objective copolymer can be obtained by simple filtration and drying after the polymerization reaction.
20 Meanwhile, in the case of a copolymer with a small number of sulfonic acid-containing groups, which hardly precipitates out of a polymerization solution, the solution is poured into a poor solvent for precipitation, or after removal of the solvent by distillation in an evaporator, etc., the concentrate is stirred

SF-2787
41
in a poor solvent, and then the polymer is filtered and dried to obtain an objective copolymer.
[0102] Since a copolymer (i) according to the present invention (the following general formula (10) shows a schematic 5 diagram of a typical copolymer) has an epoxy group and an
alkoxysilyl group having reactivity in a molecule, the copolymer (i) alone can be cured to form a film, by a reaction between the groups (for example, crosslinking reactions such as condensation reactions according to the following general formulas (11) to
10 (14)) . The reactions of an epoxy group and an alkoxysilyl group progress ordinarily by heating. Examples of a curing method other than heating include a curing method by irradiation with a microwave, which is a kind of radiation.
Reactions to occur with respect to the respective groups
15 will be described below in detail. [0103] [Chem. Formula 19]

SF-2787
42

(10)

^o

o

o

(11)

RO-Si-

mo

£o

HOSi-

D-SH OH

(12)

O
—O-Si-I O
?R
RO-^i-OR
A
?R
-ShOR
OR
-Si-O-Sj
O
i -O-^i-
O
(13) HO./
O
9R SrOR
6R
H20
9H
^i-OH
OH
OJHOY -f- oj

A
OH
O
(14)
[0104]
A reaction between epoxy groups is represented by the general formula (11) , which is preferably caused by heating. The

SF-2787
43
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.
[0105] A reaction between an epoxy group and an alkoxysilyl group is shown in the general formula (12) and the general formula (14) . [0106] 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 2508C, and more preferably in a range of from 100 to 200eC. [0107] 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.

SF-2787
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[0108]
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.
[0109] 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 150eC. [0110] 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.

SF-2787
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[0111] 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 (i). 5 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 range of from 99/ 1 to 1/ 99, and further preferably in a range of from 90/ 10
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 a copolymer (i), a compound having a hydroxy group, a compound
15 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 group or a halogen atom) convertible by hydrolysis to a hydroxy
20 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 (i) , are shown in the following general formula (20). Further,

SF-2787

46

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]



^S
OH
H
| H20
RO-Si HO-Si-
X-Si-
t
X)

-°H GZ) o:
(B)
V_y CF)

(2 0)

[0115]

[Chem. Formula 21]

SF-2787
47

Cr X>H

(21)

[0116] 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 5 of a copolymer (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. 10 [0117] As a compound having an epoxy group other than a copolymer (i) , a multivalent epoxy compound having 2 or more epoxy

SF-2787
48
groups in a molecule is preferable. Examples of a multivalent 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 5 polyglycidyl ether (TEPIC-PAS B22, TEPIC-PAS B26, Nissan Chemical Ind., Ltd.)j phenol novolac polyglycidyl ether (N-730, DIC Corporation; 152 Mitsubishi Chemical Corporation), 1.1.2.2.-tetrakis(4-glycidyloxyphenyl)ethane, N,N,N' ,N'-tetraqlycidyl diaminodiphenylmethane,
10 trimethylolpropane triglycidyl ether, neopentyl glycol
diglycidyl ether, butanediol diglycidyl ether, poly(ethylene glycol) diglycidyl ether (YDE205, Mitsubishi Chemical Corporation), diglycidyl cyclohexanedicarboxylate, diglycidyl phthalate, 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexane
15 carboxylate, and dicyclodecane poly(glycidyl ether) (EPICLON HP-7200L, EPICLON HP-7200H, DIC Corporation).
[0118] 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
20 reaction of the reaction route (B) 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 (G) occurs mainly, so that curing occurs. [0119] As the compound having a hydroxy group, a multivalent

SF-2787
49
hydroxy compound having 2 or more hydroxy groups is preferable. Examples of a multivalent hydroxy compound include ethylene glycol, diethylene glycol, 1,2-propylene glycol, glycerine, trimethylolpropane, pentaerythritol, dipentaerythritol, 5 xylylenediol , resorcinol, bisphenol A, a phenol formaldehyde 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
10 reaction product of urea, formaldehyde, and a lower alcohol. As 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
15 to generate a hydroxy group, they can be used as a compound having a hydroxy group according to the present invention. [0120] 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
20 reaction of the reaction route (C) 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 (H) occurs mainly, so that curing occurs. [0121] As a compound having a mercapto group, a multivalent

SF-2787
50
mercapto compound having 2 or more mercapto groups is preferable. Examples of a multivalent mercapto compound include glycerine dithioglycolate, trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), dipentaerythritol 5 hexakis(thioglycolate), glycerine di(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), ethanedithiol, bis(2-mercaptoethyl)sulfide, xylylenedithiol,
10 1,4-dithiane-2,5-dithiol,
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
15 [0122] When a compound having a carboxy 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 (D) occurs mainly, and with respect to the reaction of the formula (21) (a reaction with an alkoxysilyl
20 group of a copolymer (i) ) , the reaction of the reaction route (I) occurs mainly, so that curing occurs.
[0123] 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,

SF-2787
51
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. 5 [0124] 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
10 group of a copolymer (j)), the reaction of the reaction route (I) occurs mainly, so that curing occurs.
[0125] 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,
15 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,
20 L-arginine, L-alanine-L-glutamine, L-cystine, and L-citrulline. [0126] 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

SF-2787
52
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.
[0127] Examples of the acid anhydride include maleic 5 anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, oxydiphthalic anhydride, naphthalenedicarboxylic anhydride, trimellitic anhydride, and pyromellitic anhydride. [0128] When a silane compound having a hydrolyzable group
10 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)),
15 the reaction of the reaction route (K) occurs mainly, so that curing occurs.
[0129] 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.
20 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.
[0130] 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 (film) formed from the composition is enhanced and a tougher film, can be easily produced. [0131] [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.
[0132] In the formula (7) , 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.
[0133] 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 R11 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 Ru 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 Ru to Ri4 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.
[0134] When Ru 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 film, impartment of toughness, etc., decrease in the hardness of the film may also occur.
[0135] By regulating the kind and ratio of groups at X1, X2, and Rn to R14, the physical property, for example hardness, of an obtained film can be regulated.

CLAIMS
[Claim 1]
A film which is obtained from a copolymer (i) comprising constitutional units expressed by the following general formulas (1) , (2) , and (3) , or from a composition comprising the copolymer (i), and which has a thickness of not more than 100 nm, [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 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);
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 film 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; rii 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 film 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]
The film according to any one of claims 1 to 3, which is obtained from a composition comprising the copolymer (i) and a silane compound (ii) expressed by the following general formula (7):

[Chem. Formula 4]
wherein in the formula (7) , X1 and X2 independently represent a hydroxy group, a Cl to C4 aikoxy 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 aikoxy group, or a halogen atom; and
q is an integer from 0 to 10,000. [Claim 5]
The film according to claim 4, wherein 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. [Claim 6]
The film according to any one of claims 1 to 5, which is obtained by heating. [Claim 7]
A laminate comprising a layer (Z) that comprises the film according to any one of claims 1 to 6 and a substrate. [Claim 8]

The laminate according to claim 7, wherein the layer (Z) is an outermost layer of the laminate. [Claim 9]
The laminate according to claim 7 or 8, which comprises a hard coat layer between the layer (Z) and the substrate. [Claim 10] -
The. laminate according to any one of claims 7 to 9, which comprises an antireflection layer between the layer (Z) and the substrate. [Claim 11J
The laminate according to any one of claims 7 to 10, wherein the layer (Z) has a change in a water contact angle of 20° or less,
4
the. water contact angle being observed before and after the layer *
(Z), immersed in 25°C water, is ultrasonically treated for 10
minutes.
[Claim 12] _ , v
An optical article or an optical device, comprising the laminate according to any one of claims 7 to 11.