There is provided a material which is free from fading into white due to surface scattering and is useful as a laminated article having excellent adhesion and practical low reflection. A fluorine-containing compound which has a hydrolyzable metal alkoxide moiety and is represented by the formula (1):
##STR00001##
wherein X1 and X2 are the same or different, and each is H or F; X3 is H, F, CH3 or CF3; X4 and X5 are the same or different, and each is H, F or CF3; Rf1 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and ether bond, which is an organic group in which 1 to 3 hydrogen atoms are replaced by Y1 where Y1 is a functional group having, at its end, at least one hydrolyzable metal alkoxide moiety having 1 to 10 carbon atoms; a is 0 or an integer of 1 to 3; b and c are the same or different, and each is 0 or 1, a curable fluorine-containing polymer obtained from the above-mentioned compound, and a curable fluorine-containing resin composition comprising the polymer.
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1. A curable fluorine-containing polymer having a hydrolyzable metal alkoxide moiety which has a number average molecular weight of from 500 to 1,000,000 and is represented by the formula (2):
wherein the structural unit M is a structural unit derived from a fluorine-containing ethylenic monomer having a hydrolyzable metal alkoxide moiety and represented by the formula (M):
##STR00059##
in which X1 and X2 are the same or different, and each is H or F; X3 is H, F, CH3 or CF3; X4 and X5 are the same or different, and each is H, F or CF3; Rf1 is represented by the formula:
—D—Ry wherein —D— is a fluoroether unit represented by the formula (D):
in which n is an integer of 1 to 20; R is at least one selected from fluorine-containing divalent alkylene groups having 1 to 5 carbon atoms where at least one of hydrogen atoms is replaced by fluorine atom, and R may be the same or different when n is not less than two; Ry is a hydrocarbon group having 1 to 39 carbon atoms where a part or the whole of hydrogen atoms are may be replaced by fluorine atoms or a hydrocarbon group having 1 to 99 carbon atoms and ether bond where a part or the whole of hydrogen atoms are may be replaced by fluorine atoms, which is an organic group in which one to three of hydrogen atoms are replaced by Y1 where Y1 is a functional group having, at its end, at least one hydrolyzable metal alkoxide moiety having 1 to 50 carbon atoms; Ry may contain —CONH— bond; a is 0 or an integer of 1 to 3; b and c are the same or different, and each is 0 or 1,
the structural unit N is a structural unit derived from a fluorine-containing ethylenic monomer and represented by the formula (N):
##STR00060##
in which X1 and X2 are the same or different, and each is H or F; X3 is H, F, CH3 or CF3; X4 and X5 are the same or different, and each is H, F or CF3; Rf2 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and ether bond, which is an organic group in which 1 to 3 hydrogen atoms are replaced by Y2 where Y2 is a monovalent organic group having 2 to 10 carbon atoms and having, at its end, an ethylenic carbon-carbon double bond; a is 0 or an integer of 1 to 3; b and c are the same or different, and each is 0 or 1,
the structural unit A is a structural unit derived from a monomer being copolymerizable with the fluorine-containing ethylenic monomers providing the structural units represented by the formulae (M) and (N), and
the structural units M, N and A are contained in amounts of from 0.1 to 100% by mole, from 0 to 99.9% by mole and from 0 to 99.9% by mole, respectively,
wherein the formula (2), the structural unit M is a structural unit m1 derived from a fluorine-containing ethylenic monomer and represented by the formula (m1):
##STR00061##
wherein X1, X2, X3, X4, X5, Rf1, a and c are as defined above.
2. The curable fluorine-containing polymer of
0. 3. The curable fluorine-containing polymer of
##STR00062##
wherein X1, X2, X3, X4, X5, Rf1, a and c are as defined above.
4. The curable fluorine-containing polymer of
##STR00063##
wherein Rf1 is as defined above.
5. The curable fluorine-containing polymer of
##STR00064##
wherein Rf1 is as defined above.
6. The curable fluorine-containing polymer of
—O—Ry1 (Ry) wherein Ry1 is an organic-inorganic complex radical represented by the formula:
—(R11)pR12—(Y1a)m where p is 0 or 1; m is an integer of 1 to 3; R11 is —CONH—; R12 is a di-, tri- or tetra-valent hydrocarbon group having 1 to 39 carbon atoms where a part or the whole of hydrogen atoms are may be replaced by fluorine atoms or a di-, tri- or tetra-valent hydrocarbon group having 1 to 99 carbon atoms and ether bond where a part or the whole of hydrogen atoms are may be replaced by fluorine atoms; Y1a is a functional group represented by the formula:
—[M1O(R29)a(R30)b(R31)c(R32)d]n—M2(R33)e(R34)f(R35)g(R36)h(R37)i where M1 and M2 are the same or different and each is a di-, tri-, tetra-, penta- or hexa-valent metal atom; a, b, c and d are 0 or 1, and a+b+c+d+2 is equal to the number of valences of the metal atom M1; e, f, g, h and i are 0 or 1, and e+f+g+h+i+1 is equal to the number of valences of the metal atom M2; R29, R30, R31, R32, R33, R34, R35, R36 and R37 are the same or different and each is an organic group represented by the formula: OR38 or R38 where R38 is hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in which a part or the whole of hydrogen atoms may be replaced by fluorine atoms, and at least one of R29, R30, R31, R32, R33, R34, R35, R36 and R37 is OR38; n is 0 or an integer of 1 to 11.
7. A curable fluorine-containing resin composition comprising:
(a) the curable fluorine-containing polymer having a hydrolyzable metal alkoxide moiety of
(b) a curing agent.
9. A curable fluorine-containing resin composition for coating comprising:
(a) the curable fluorine-containing polymer having a hydrolyzable metal alkoxide moiety of
(b) a curing agent, and
(c) a solvent.
10. A cured coating film obtained by curing a coating film formed by applying the curable fluorine-containing resin composition for coating of
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The present invention relates to a novel fluorine-containing compound and polymer having a hydrolyzable metal alkoxide moiety, and a curable fluorine-containing resin composition prepared using the polymer.
In order to enhance visibility of an image of liquid crystal displays (LCD) and the like, measures to inhibit a reflection on the surface thereof are taken. One of such measures is to provide, on the surface, a light scattering layer having a fine uneven structure giving an anti-glaring property. However, when the light scattering layer is provided on the surface of LCD, there is a demerit such that surface scattering arises and when a black color is displayed, the displayed picture becomes whitish, namely, so-called “fading into white color” arises, which results in lowering of an image contrast.
For making improvement in reducing this “fading into white color”, there is a method of imparting a reflection reducing ability to prevent lowering of an image contrast by providing, on a surface of a resin coating layer having a fine uneven structure, a coating layer having a refractive index lower than that of the resin coating layer (for example, JP-A10-201043 and JP-A-2003-344614).
However, with respect to a coating layer to be provided on a surface of a conventional resin coating layer having a fine uneven structure, there have been proposed only materials having a high refractive index (for example, not less than 1.40). As a result, a displayed image contrast is lowered, and also durability is poor since such a coating layer is lacking in adhesion to the light scattering layer which is a substrate.
Such being the case, laminating materials having practical anti-glaring property and low reflection in which improvements are made in solving the mentioned problems are desired.
An object of the present invention is to provide a material which is useful for a laminated article having a practical low reflection, keeps an anti-glaring property, is free from “fading into white color” attributable to surface scattering and is excellent in adhesion.
Namely, the present invention relates to a curable fluorine-containing polymer (hereinafter referred to as “the first polymer”) having a hydrolyzable metal alkoxide moiety which has a number average molecular weight of from 500 to 1,000,000 and is represented by the formula (2):
M
N
A
(2)
wherein the structural unit M is a structural unit which is derived from a fluorine-containing ethylenic monomer having a hydrolyzable metal alkoxide moiety and is represented by the formula (M):
##STR00002##
in which X1 and X2 are the same or different, and each is H or F; X3 is H, F, CH3 or CF3; X4 and X5 are the same or different, and each is H, F or CF3; Rf1 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and ether bond, which is an organic group in which 1 to 3 hydrogen atoms are replaced by Y1 where Y1 is a functional group containing, at its end, at least one hydrolyzable metal alkoxide moiety and having 1 to 50 carbon atoms; a is 0 or an integer of 1 to 3; b and c are the same or different, and each is 0 or 1,
the structural unit N is a structural unit derived from a fluorine-containing ethylenic monomer and represented by the formula (N):
##STR00003##
in which X1 and X2 are the same or different, and each is H or F; X3 is H, F, CH3 or CF3; X4 and X5 are the same or different, and each is H, F or CF3; Rf2 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and ether bond, which is an organic group in which 1 to 3 hydrogen atoms are replaced by Y2 where Y2 is a monovalent organic group having 2 to 10 carbon atoms and containing, at its end, an ethylenic carbon-carbon double bond; a is 0 or an integer of 1 to 3; b and c are the same or different, and each is 0 or 1,
the structural unit A is a structural unit derived from a monomer being copolymerizable with the fluorine-containing ethylenic monomers providing the structural units represented by the formulae (M) and (N), and
the structural units M, N and A are contained in amounts of from 0.1 to 100% by mole, from 0 to 99.9% by mole and from 0 to 99.9% by mole, respectively.
Further the present invention relates to a curable fluorine-containing polymer (hereinafter referred to as “the second polymer”) having a hydrolyzable metal alkoxide moiety which has a number average molecular weight of from 500 to 1,000,000 and is represented by the formula (2-1):
M
N
A1
A2
(2-1)
wherein the structural unit M is a structural unit which is derived from a fluorine-containing ethylenic monomer having a hydrolyzable metal alkoxide moiety and is represented by the above-described formula (M), the structural unit N is a structural unit which is derived from a fluorine-containing ethylenic monomer and is represented by the above-described formula (N), the structural unit A1 is a structural unit represented by the formula (A1):
##STR00004##
in which X11, X12 and X13 are the same or different, and each is H or F; X14 is H, F or CF3; h is 0 or an integer of 1 or 2; i is 0 or 1; Rf4 is a fluorine-containing divalent alkylene group having 1 to 40 carbon atoms or a fluorine-containing divalent alkylene group having 2 to 100 carbon atoms and ether bond; Z1 is a group selected from the group consisting of —OH, —CH2OH, —COOH, a carboxylic acid derivative, —SO3H, a sulfonic acid derivative, an epoxy group and a cyano group, the structural unit A2 is a structural unit represented by the formula (A2):
##STR00005##
in which X15, X16 and X18 are the same or different, and each is H or F; X17 is H, F or CF3; h1, i1 and j are the same or different, and each is 0 or 1; Z2 is H, F, Cl or a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms; Rf5 is a fluorine-containing divalent alkylene group having 1 to 20 carbon atoms or a fluorine-containing divalent alkylene group having 2 to 100 carbon atoms and ether bond, the structural units M, N, A1 and A2 are contained in amounts of from 0.1 to 90% by mole, from 0 to 99.9% by mole, from 0 to 99.9% by mole and from 0 to 99.9% by mole, respectively, and
N+A1+A2 is contained in an amount of from 10 to 99.9% by mole.
In any of the curable fluorine-containing polymers, it is preferable that at least one of Y1 is bonded to the end of Rf1, and further in the second polymer, it is preferable that at least one of Y2 is bonded to the end of Rf2.
In the first and second polymers represented by the formulae (2) and (2-1), respectively, the structural unit M is preferably a structural unit M1 derived from a fluorine-containing ethylenic monomer and represented by the formula (M1):
##STR00006##
wherein X1, X2, X3, X4, X5, Rf1, a and c are as defined above.
Further the structural unit M is preferably a structural unit M2 derived from a fluorine-containing ethylenic monomer and represented by the formula (M2):
##STR00007##
wherein Rf1 is as defined above, or a structural unit M3 derived from a fluorine-containing ethylenic monomer and represented by the formula (M3):
##STR00008##
wherein Rf1 is as defined above.
Also in any of the curable fluorine-containing polymers, it is preferable that Rf1 is one represented by the formula:
—D—Ry
wherein —D— is a fluoroether unit represented by the formula (D):
O—R
n or
R—O
n (D)
in which n is an integer of 1 to 20; R is at least one selected from fluorine-containing divalent alkylene groups having 1 to 5 carbon atoms where at least one of hydrogen atoms is replaced by fluorine atom, and R may be the same or different when n is not less than two; Ry is a hydrocarbon group having 1 to 39 carbon atoms where a part or the whole of hydrogen atoms may be replaced by fluorine atoms, or a hydrocarbon group having 1 to 99 carbon atoms and ether bond where a part or the whole of hydrogen atoms may be replaced by fluorine atoms, which is an organic group in which 1 to 3 hydrogen atoms are replaced by Y1 (Y1 is as defined above), and more specifically Ry is preferably a group represented by the formula (Ry):
—O—Ry1 (Ry)
wherein Ry1 is an organic-inorganic complex radical represented by the formula:
—(R11)pR12—(Y1a)m
where p is 0 or 1; m is an integer of 1 to 3; R11 is —CONH—; R12 is a di-, tri- or tetra-valent hydrocarbon group having 1 to 39 carbon atoms where a part or the whole of hydrogen atoms may be replaced by fluorine atoms or a di-, tri- or tetra-valent hydrocarbon group having 1 to 99 carbon atoms and ether bond where a part or the whole of hydrogen atoms may be replaced by fluorine atoms; Y1a is a functional group represented by the formula:
—[M1O(R29)a(R30)b(R31)c(R32)d]n—M2(R33)e(R34)f(R35)g(R36)h(R37)i
where M1 and M2 are the same or different and each is a di-, tri-, tetra-, penta- or hexa-valent metal atom; a, b, c and d are 0 or 1, and a+b+c+d+2 is equal to the number of valences of the metal atom M1; e, f, g, h and i are 0 or 1, and e+f+g+h+i+1 is equal to the number of valences of the metal atom M2; R29, R30, R31, R32, R33, R34, R35, R36 and R37 are the same or different and each is an organic group represented by the formula OR38 or R38 where R38 is hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in which a part or the whole of hydrogen atoms may be replaced by fluorine atoms, and at least one of R29, R30, R31, R32, R33, R34, R35, R36 and R37 is OR38; n is 0 or an integer of 1 to 11.
In the second polymer, it is preferable that the structural unit (A1) is a structural unit represented by the formula (A1-1):
##STR00009##
where Rf4 and Z1 are as defined in the formula (A1), or a structural unit represented by the formula (A1-2):
##STR00010##
where Rf4 and Z1 are as defined in the formula (A1), or the structural unit (A2) is a structural unit derived from at least one monomer selected from the group consisting of tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene and hexafluoropropylene.
The present invention also relates to a curable fluorine-containing resin composition comprising:
(a) the above-described first or second curable fluorine-containing polymer having a hydrolyzable metal alkoxide moiety, and
(b) a curing agent.
Further the present invention relates to a curable fluorine-containing resin composition for coating comprising:
(a) the above-described first or second curable fluorine-containing polymer having a hydrolyzable metal alkoxide moiety,
(b) a curing agent, and
(c) a solvent.
By curing those curable compositions, a cured article and cured film having excellent characteristics can be provided.
The fluorine-containing compound which has a hydrolyzable metal alkoxide moiety, provides the structural unit M of the first and second polymers and is represented by the formula (1):
##STR00011##
in which X1 and X2 are the same or different, and each is H or F; X3 is H, F, CH3 or CF3; X4 and X5 are the same or different, and each is H, F or CF3; Rf1 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and ether bond, which is an organic group in which 1 to 3 hydrogen atoms are replaced by Y1 where Y1 is a functional group containing, at its end, at least one hydrolyzable metal alkoxide moiety and having 1 to 50 carbon atoms; a is 0 or an integer of 1 to 3; b and c are the same or different, and each is 0 or 1, is a novel compound.
[
[
The first polymer of the present invention is the curable fluorine-containing polymer having a hydrolyzable metal alkoxide moiety which has a number average molecular weight of from 500 to 1,000,000 and is represented by the formula (2):
M
N
A
(2)
wherein the structural unit M is a structural unit having a hydrolyzable metal alkoxide moiety, the structural unit N is a structural unit having an ethylenic carbon-carbon double bond and the structural unit A is an optional structural unit, and the structural units M, N and A are contained in amounts of from 0.1 to 100% by mole, from 0 to 99.9% by mole and from 0 to 99.9% by mole, respectively.
Then each structural unit is explained below.
The structural unit M is the structural unit which is derived from a fluorine-containing ethylenic monomer having a hydrolyzable metal alkoxide moiety and is represented by the formula (M):
##STR00012##
in which X1 and X2 are the same or different, and each is H or F; X3 is H, F, CH3 or CF3; X4 and X5 are the same or different, and each is H, F or CF3; Rf1 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and ether bond, which is an organic group in which 1 to 3 hydrogen atoms are replaced by Y1 where Y1 is a functional group containing, at its end, at least one hydrolyzable metal alkoxide moiety and having 1 to 50 carbon atoms; a is 0 or an integer of 1 to 3; b and c are the same or different, and each is 0 or 1.
The structural unit M is particularly preferably the structural unit M1 derived from a fluorine-containing ethylenic monomer and represented by the formula (M1):
##STR00013##
wherein X1, X2, X3, X4, X5, Rf1, a and c are as defined above.
The fluorine-containing polymer having this structural unit M1 is preferable because particularly a refractive index is low, adhesion to various substrates such as a light scattering layer is good and durability can be enhanced.
Further one of more preferable examples of the structural unit M1 is the structural unit M2 derived from a fluorine-containing ethylenic monomer and represented by the formula (M2):
##STR00014##
wherein Rf1 is as defined above.
This structural unit M2 is preferable because a refractive index is low, adhesion to various substrates such as a light scattering layer is good, durability can be enhanced, and in addition, copolymerizability with other fluorine-containing ethylenic monomers is good.
Also other preferable example of the structural unit M1 is the structural unit M3 derived from a fluorine-containing ethylenic monomer and represented by the formula (M3):
##STR00015##
wherein Rf1 is as defined above.
This structural unit M3 is preferable because a refractive index is low, adhesion to various substrates such as a light scattering layer is good, durability can be enhanced, and in addition, copolymerizability with other fluorine-containing ethylenic monomers is good.
In the present invention, Rf1 contained in the structural units M, M1, M2 and M3 is, as described above, an organic group having 1 to 3 functional groups Y1 which contains, at its end, at least one hydrolyzable metal alkoxide moiety and has 1 to 50 carbon atoms, and an upper limit of the number of carbon atoms is preferably 30, more preferably 20, particularly preferably 10.
The hydrolyzable metal alkoxide moiety in the Y1 functions to cause a hydrolysis and polycondensation reaction, thereby exhibiting an effect of enhancing good adhesion durability with a substrate having hydroxyl group.
It is preferable that Rf1 is one represented by the formula (Rf1):
—D—Ry (Rf1)
wherein —D— is a fluoroether unit represented by the formula (D):
O—R
n or
R—O
n (D)
in which n is an integer of 1 to 20; R is at least one selected from fluorine-containing divalent alkylene groups having 1 to 5 carbon atoms where at least one of hydrogen atoms is replaced by fluorine atom, and R may be the same or different when n is not less than two; Ry is a hydrocarbon group having 1 to 39 carbon atoms where a part or the whole of hydrogen atoms may be replaced by fluorine atoms or a hydrocarbon group having 1 to 99 carbon atoms and ether bond where a part or the whole of hydrogen atoms may be replaced by fluorine atoms, which is an organic group in which 1 to 3 hydrogen atoms are replaced by Y1 (Y1 is as defined above).
—R— is a fluorine-containing divalent alkylene group having 1 to 5 carbon atoms and has at least one fluorine atom, thereby being capable of contributing to further lowering of a viscosity of the compound, enhancement of heat resistance, lowering of a refractive index and enhancement of solubility in general purpose solvents as compared with conventional compounds having an alkylene ether unit or an alkoxyl group having no fluorine atom.
Examples of —(O—R)— or —(R—O)— in —D— are —(OCF2CF2CF2)—,
wherein Ry1 is an organic-inorganic complex radical represented by the formula (Ry1):
—(R11)pR12—(Y1a)m (Ry1)
where p is 0 or 1; m is an integer of 1 to 3; R11 is —CONH—; R12 is a di-, tri- or tetra-valent hydrocarbon group having 1 to 39 carbon atoms where a part or the whole of hydrogen atoms may be replaced by fluorine atoms or a di-, tri- or tetra-valent hydrocarbon group having 1 to 99 carbon atoms and ether bond where a part or the whole of hydrogen atoms may be replaced by fluorine atoms; Y1a is a functional group represented by the formula:
—[M1O(R29)a(R30)b(R31)c(R32)d]n—M2(R33)e(R34)f(R35)g(R36)h(R37)i
where M1 and M2 are the same or different and each is a di-, tri-, tetra-, penta- or hexa-valent metal atom; a, b, c and d are 0 or 1, and a+b+c+d+2 is equal to the number of valences of the metal atom M1; e, f, g, h and i are 0 or 1, and e+f+g+h+i+1 is equal to the number of valences of the metal atom M2; R29, R30, R31, R32, R33, R34, R35, R36 and R37 are the same or different and each is an organic group represented by the formula: OR38 or R38 where R38 is hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms in which a part or the whole of hydrogen atoms may be replaced by fluorine atoms, and at least one of R29, R30, R31, R32, R33, R34, R35, R36 and R37 is OR38; n is 0 or an integer of 1 to 11.
In the formula (Ry1), when p is 0, the end of Ry becomes an ether bond, and when p is 1, the end of Ry becomes a urethane bond.
Examples of —R12— in the formula (Ry1) are, for instance, as follows.
##STR00016##
(in the above described groups, m: 0 to 10, n: 0 to 5, m+n: 1 to 15)
##STR00017##
(in the above described groups, l: 1 to 10, m: 1 to 10, n: 0 to 5)
##STR00018##
(in the above described groups, each of X30 and X33 is F or CF3; each of X31 and X32 is H or F; o+p+q is 1 to 30; r is 0 or 1;
wherein Y2a is an alkenyl group or fluorine-containing alkenyl group having 2 to 5 carbon atoms and containing an ethylenic carbon-carbon double bond at its end; d and e are the same or different and each is 0 or 1.
A preferable example of Y2a is:
—CX6═CX7X8
wherein X6 is H, F, CH3 or CF3; X7 and X8 are the same or different and each is H or F, and this group is preferable because a curing reactivity by a contact with a radical or a cation is high.
Preferable examples of Y2a are:
##STR00028##
and the like.
A more preferable example of Y2 is:
—O(C═O)CX6═CX7X8
wherein X6 is H, F, CH3 or CF3; X7 and X8 are the same or different and each is H or F, and this group is preferable because a curing reactivity by a contact with a radical is high and a cured article can be obtained easily by photo-curing.
Examples of the more preferable Y2 described above are:
##STR00029##
and the like.
Examples of other preferable Y2 are:
##STR00030##
and the like.
Of the groups Y2, those having a structure of —O(C═O)CF═CH2 are preferable because near infrared transparency can be enhanced, a curing (crosslinking) reactivity is especially high and a cured article can be obtained efficiently.
The above described organic group Y2 having a carbon-carbon double bond in its side chain may be introduced into the end of the polymer trunk chain.
In the fluorine-containing polymer used in the present invention, —Rf2— (a group obtained by removing Y2 from the mentioned —Rf2) contained in the structural units N, N1, N2 and N3 is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond. In this Rf2 group, a fluorine atom is to be bonded to the carbon atom contained therein, and is generally a fluorine-containing alkylene group or a fluorine-containing alkylene group having ether bond, in which a fluorine atom and hydrogen atom or a chlorine atom are bonded to the carbon atom. Preferable is the Rf2 containing more fluorine atoms (a high fluorine content), and more preferable is a perfluoroalkylene group or a perfluoroalkylene group having ether bond. The fluorine content of the fluorine-containing polymer is not less than 25% by mass, preferably not less than 40% by mass. This fluorine content is preferable because not only a near infrared transparency of the fluorine-containing polymer can be enhanced but also a refractive index thereof can be decreased, and even if a curing degree (crosslinking density) is increased particularly for the purpose of enhancing heat resistance and elastic modulus of a cured article, a near infrared transparency can be maintained high or a refractive index can be maintained low.
When the number of carbon atoms of the —Rf2— group is too large, in the case of fluorine-containing alkylene groups, in some cases, solubility in a solvent is lowered and transparency is lowered, and in the case of fluorine-containing alkylene groups having ether bond, in some cases, a hardness and mechanical characteristics of the polymer itself and the cured article obtained therefrom are lowered. Therefore too large number of carbon atoms is not preferable. The number of carbon atoms of fluorine-containing alkylene groups is preferably 1 to 20, more preferably 1 to 10, and the number of carbon atoms of fluorine-containing alkylene groups having ether bond is preferably 2 to 30, more preferably 2 to 20.
Preferable examples of —Rf2— are:
##STR00031##
(In the above described groups, m: 0 to 10, n: 0 to 5)
##STR00032##
(in the above described groups, l: 1 to 10, m: 1 to 10, n: 0 to 5)
##STR00033##
(In the above described groups, each of X34 and X37 is F or CF3; each of X35 and X36 is H or F; o+p+q is 1 to 30; r is 0 or 1;
wherein Rf4 and Z1 are as defined above, and are represented by the formula (A1-1):
##STR00041##
wherein Rf4 and Z1 are as defined in the formula (A1).
Specific examples thereof are preferably structural units derived from fluorine-containing ethylenic monomers such as:
##STR00042##
wherein Z1 is as defined above.
Also there is preferably exemplified a structural unit which is derived from:
CF2═CFORf4—Z1
wherein Rf4 and Z1 are as defined above, and is represented by the formula (A1-2):
##STR00043##
where Rf4 and Z1 are as defined in the formula (A1).
Specific examples thereof are structural units derived from monomers such as:
##STR00044##
wherein Z1 is as defined above.
Other examples of the fluorine-containing ethylenic monomer having functional group are:
CF2═CFCF2—O—Rf2—Z1, CF2═CF—Rf2—Z1,
CH2═CH—Rf2—Z1, CH2═CHO—Rf2—Z1
and the like, wherein —Rf2— is the same as the above described —Rf2— and Z1 is as defined above. More specifically there are:
##STR00045##
and the like, wherein Z1 is as defined above.
(A2) Structural Units Derived from Fluorine-Containing Ethylenic Monomers Having no Functional Group
These structural units A2 are preferable from the point that a refractive index of the fluorine-containing polymer and the cured article obtained therefrom can be maintained low and because a refractive index can be further decreased. Also these structural units are preferable from the point that by selecting the monomer, mechanical characteristics and glass transition temperature of the polymer can be adjusted, and particularly the glass transition temperature can be increased by copolymerization with the structural units M and N.
Examples of the preferred structural units (A2) of the fluorine-containing ethylenic monomer are those represented by the formula (A2):
##STR00046##
wherein X15, X16 and X18 are the same or different and each is H or F; X17 is H, F or CF3; h1, i1 and j are the same or different and each is 0 or 1; Z2 is H, F, Cl or a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms; Rf5 is a fluorine-containing divalent alkylene group having 1 to 20 carbon atoms or a fluorine-containing divalent alkylene group having 2 to 100 carbon atoms and ether bond.
Examples thereof are preferably structural units derived from monomers such as:
##STR00047##
CH2═CFCF2
nZ2 (Z2 is as defined in the formula (A2), n is from 1 to 10) and
CH2═CHOCH2CF2
nZ2 (Z2 is as defined in the formula (A2), n is from 1 to 10).
It is particularly preferable that these structural units are structural units derived from at least one monomer selected from the group consisting of tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene and hexafluoropropylene because a refractive index of the curable fluorine-containing polymer and the cured article obtained therefrom can be maintained low.
(A3) Fluorine-Containing Aliphatic Ring Structural Units
Introduction of these structural units A3 is preferable since transparency can be increased, and also the fluorine-containing polymer having a high glass transition temperature can be obtained and a higher hardness of the cured article can be expected.
Examples of the preferred fluorine-containing aliphatic ring structural unit A3 are those represented by the formula (A3):
##STR00048##
wherein X19, X20, X23, X24, X25 and X26 are the same or different and each is H or F; X21 and X22 are the same or different and each is H, F, Cl or CF3; Rf6 is a fluorine-containing alkylene group having 1 to 10 carbon atoms or a fluorine-containing alkylene group having 2 to 10 carbon atoms and ether bond; n2 is 0 or an integer of from 1 to 3; n1, n3, n4 and n5 are the same or different and each is 0 or 1.
For example, there are structural units represented by:
##STR00049##
wherein Rf6, X21 and X22 are as defined above.
Specifically there are:
##STR00050##
and the like wherein X19, X20, X23 and X24 are as defined above.
Other examples of the fluorine-containing aliphatic ring structural units are, for instance,
##STR00051##
and the like.
(A4) Structural Units Derived from Ethylenic Monomers Having no Fluorine
The introduction of those structural units A4 can enhance solubility in general-purpose solvents and can improve compatibility with additives, for example, a photocatalyst and a curing agent to be added as case demands.
Examples of the non-fluorine-containing ethylenic monomer are as follows.
α-Olefins:
Ethylene, propylene, butene, vinyl chloride, vinylidene chloride and the like.
Vinyl Ether or Vinyl Ester Monomers:
CH2═CHOR, CH2═CHOCOR (R: hydrocarbon group having 1 to 20 carbon atoms) and the like.
Allyl Monomers:
CH2═CHCH2Cl, CH2═CHCH2OH, CH2═CHCH2COOH, CH2═CHCH2Br and the like.
Allyl Ether Monomers:
wherein the structural unit M and the structural unit N are the same as in the first polymer and the structural unit A1 and the structural unit A2 are as defined above,
the structural units M, N, A1 and A2 are contained in amounts of from 0.1 to 90% by mole, from 0 to 99.9% by mole, from 0 to 99.9% by mole and from 0 to 99.9% by mole, respectively, and
N+A1+A2 is contained in an amount of from 10 to 99.9% by mole.
The content of the structural unit M in the second fluorine-containing polymer is not less than 0.1% by mole based on the whole structural units constituting the fluorine-containing polymer. In order to obtain a cured article having a high hardness by curing (crosslinking) and excellent abrasion resistance, scratch resistance, chemical resistance and solvent resistance, it is preferable that the content is not less than 2.0% by mole, preferably not less than 5% by mole, more preferably not less than 10% by mole. Particularly in applications requiring formation of a cured film having excellent heat resistance and transparency and low water absorption, it is preferable that the content is not less than 10% by mole, preferably not less than 20% by mole, more preferably not less than 50% by mole. An upper limit of the content is less than 100% by mole.
The contents of the structural units N, A1 and A2 are each not more than 99.9% by mole. The total percent by mole of N+A1+A2 is from 10 to 99.9% by mole. When the total percent by mole is less than 10% by mole, a refractive index cannot be maintained low, and further a hardness of the cured film after the curing tends to become low, which is not preferable. A more preferable total percent by mole of N+A1+A2 is not less than 20% by mole, further preferably not less than 30% by mole, and not more than 60% by mole, further preferably not more than 50% by mole.
From the viewpoint that a strength and abrasion resistance of a cured film after the curing can be enhanced, a molar ratio (N/(N+A1+A2)) of the structural unit N to the sum of the structural units N, A1 and A2 in the second fluorine-containing polymer is preferably 1/100 to 100/100, more preferably 30/100 to 100/100, further preferably 50/100 to 100/100, particularly preferably 70/100 to 100/100.
Further from the viewpoint that adhesion of a cured film to a substrate and durability thereof can be enhanced, a molar ratio (A1/(N+A1+A2)) of the structural unit A1 to the sum of the structural units N, A1 and A2 in the second fluorine-containing polymer is preferably 1/100 to 50/100, more preferably 1/100 to 40/100, further preferably 1/100 to 30/100.
A molecular weight, for example, a number average molecular weight of the second fluorine-containing polymer can be selected within a range from 500 to 1,000,000, preferably from 1,000 to 500,000, particularly preferably from 2,000 to 200,000.
If the molecular weight is too low, mechanical properties tend to be insufficient even after the curing, and particularly a cured article and a cured coating film tend to be fragile and insufficient in a strength. If the molecular weight is too high, solubility in a solvent is lowered, particularly film forming property and leveling property are apt to be lowered at forming a thin film, and storage stability of the fluorine-containing polymer tends to be lowered. The number average molecular weight is most preferably selected within a range from 5,000 to 100,000.
As mentioned above, it can be said that the second polymer comprises, as essential structural units, the structural unit N and/or the structural unit A which are optional structural units of the first polymer, and is specifically so defined.
In the second fluorine-containing polymer of the present invention, with respect to combinations and proportions of the structural unit M (M1, M2 and M3), the structural unit N(N1, N2 and N3), and further the structural unit A (A1 and A2), various combinations of the structural unit M, the structural unit N and the structural unit A can be selected from the above described examples, depending on intended applications, physical properties (particularly glass transition temperature, hardness, etc.), functions (transparency) and the like.
Also the fluorine-containing polymer is preferably soluble in general purpose solvents, for example, in at least one of ketone solvents, acetic acid ester solvents, alcohol solvents and aromatic solvents or in solvent mixtures containing at least one of general purpose solvents.
The fluorine-containing polymer being soluble in general purpose solvents is preferable because film forming property and homogeneity are excellent particularly in forming a thin film having a thickness of not more than
and after sufficiently replacing the inside of the flask with nitrogen, stirring was carried out at 20° C. for 24 hours in a nitrogen gas stream, and a highly viscose solid was produced.
The obtained solid was dissolved in diethyl ether and poured into perfluorohexane, followed by separation and vacuum drying to obtain 35.2 g of a colorless transparent polymer.
According to 19F-NMR analysis, 1H-NMR analysis and IR analysis, this polymer was a copolymer comprising a fluorine-containing allyl ether having OH group and a fluorine-containing allyl ether having —Si(OR)3 group in a percent by mole ratio of 50:50.
Also according to GPC analysis using tetrahydrofuran (THF) as a solvent, a number average molecular weight of the polymer was 9,000, and a weight average molecular weight thereof was 22,000.
Into a 200 ml four-necked flask equipped with a reflux condenser, a thermometer, a stirrer and a dropping funnel were poured 80 ml of diethyl ether, 5.0 g of the polymer containing fluorine-containing allyl ether having silicon alkoxide and obtained in Example 2, and 1.0 g of pyridine, followed by cooling to 5° C. or lower with ice.
While stirring in a nitrogen gas stream, a solution prepared by dissolving 1.0 g of α-fluoroacrylic acid fluoride: CH2═CFCOF in 20 ml of diethyl ether was further added dropwise over about 30 minutes.
After completion of the addition, the temperature of the mixture was increased to room temperature, and stirring was continued for another 4.0 hours.
The ether solution after the reaction was poured into the dropping funnel, and after repeating washing with water, 2% hydrochloric acid solution, 5% NaCl solution and then water, was dried with anhydrous magnesium sulfate, and then the ether solution was separated by filtration.
According to 19F-NMR analysis, this ether solution was a copolymer comprising a fluorine-containing allyl ether having OCOCF═CH2 group, a fluorine-containing allyl ether having OH group, and a fluorine-containing allyl ether having —Si(OR)3 group in a percent by mole ratio of 40:10:50.
The obtained copolymer was coated on a silicon wafer, and formed into a cast film at room temperature. According to IR analysis of the cast film, an absorption of carbon-carbon double bond was observed at 1,661 cm−1, an absorption of C═O group, at 1,770 cm−1, and an absorption of Si(OCH3)3 group, at 1,100 cm−1. An IR chart is shown in
To the curable fluorine-containing polymer (ether solution) having silicon alkoxide and α-fluoroacryloyl group and obtained in Example 3 was added methyl isobutyl ketone (MIBK), and then ether was distilled off with an evaporator to adjust the polymer concentration to 3.75% by weight.
To 10 g of the obtained polymer solution was added 1.7 g of a solution prepared by dissolving 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one as an active energy curing initiator in MIBK in a concentration of 1% by weight.
A fluorine-containing resin composition for coating containing no silicon alkoxide was prepared in the same manner as in Example 4 except that the fluorine-containing allyl ether having —Si(OR)3 group was not contained in the fluorine-containing resin composition prepared by means of Examples 2 to 4.
The above-mentioned coating composition was applied to an un-coated PET film subjected to anti-glaring treatment with an applicator, and dried at 25° C. for five minutes.
(Light Irradiation)
The dried coating film was irradiated with ultraviolet light at an intensity of 3,000 mJ/cm2U at room temperature using a high pressure mercury lamp.
The 3.75% MIBK solution of the curable fluorine-containing polymer (the polymer solution before adding the curing catalyst in the above-mentioned (1) of Examples 4 and 5) was coated on a PET film with an applicator so that a coating thickness after the drying became about 100 μm. After drying at 50° C. for 10 minutes, an obtained cast film was peeled from the PET film, and a refractive index thereof was measured using an Abbe's refractometer at 25° C. with light having a wavelength of 550 nm. The results are shown in Table 1.
The coating compositions prepared in the above-mentioned (1) of Examples 4 and 5 were coated on an aluminum foil with an applicator so that a coating thickness became about 100 μm, followed by drying at 50° C. for 10 minutes. After the dried coating film was subjected to irradiation of light in the same manner as in (2) above, the aluminum foil was molten with diluted hydrochloric acid to make a sample film. A refractive index of the obtained cured film was measured in the same manner as in (3) above. The results are shown in Table 1.
The following physical properties of the laminated article obtained in (2) above were evaluated. The results are shown in Table 1.
(5-1) Dry to Touch
Tackiness was evaluated by touching with fingers according to JIS K4500.
The evaluation is made by:
◯: There is no tackiness.
X: There is tackiness.
(5-2) Pencil Hardness
Measured according to JIS K5400.
(5-3) Solvent Resistance
After the surface of the coating film is rubbed with a cotton cloth impregnated with acetone, condition (dissolved or peeled) of the coating film surface is evaluated.
When there is no change, it is evaluated as ◯, and when there is dissolution or peeling, it is evaluated as X.
(5-4) Abrasion Resistance Test
A cotton cloth (BEMCOT (Registered trademark) M-3 available from Asahi Chemical Co., Ltd.) is fitted to a rubbing tester, and the laminated article is rubbed by 100 rubbing cycles at a load of 100 gf/cm2. Then the condition of the film is observed.
The evaluation is made as follows.
◯: There is no change.
Δ: A flaw is found partly.
X: There is a portion where a film is peeled and a substrate is seen.
(5-5) Measurement of Reflectance of One Side of Film
A PET film provided with the laminated article was set on a thin film reflectance meter F-20 (available from Filmetrics Co.), and a reflectance was measured with light having a wavelength of 550 nm.
A one side reflection of an un-coated PET film subjected to anti-glaring treatment was measured, and the results thereof are shown in Table 1.
TABLE 1
Example 4
Example 5
Com. Ex. 1
Substrate film
Anti-glare PET
Anti-glare PET
Anti-glare PET
Curable fluorine-
Example 3
Un-coated
containing polymer
Content of
40
50
—O(C═O)CF═CH2
group (% by mole)
Solvent
MIBK
MIBK
Concentration of
3.75
3.75
polymer
(% by weight)
Active energy curing
Curing
Curing
initiator
initiator 1
initiator 1
Ratio to polymer
3
3
(% by weight)
Amount of ultraviolet
4200
4200
light (mJ/cm)
Refractive index
Before curing
1.380
1.367
After curing
1.387
1.375
Dry to touch
◯
◯
Un-coated
Solvent resistance
◯
X
Abrasion resistance
◯
X
Reflectance on
4.82
4.70
8.00
one side of film (%)
Curing initiator 1: 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one
The present invention can provide a material which is free from fading into white due to surface scattering while maintaining anti-glaring property and is useful as a laminated article having excellent adhesion and practical low reflection.
Sato, Kazuyuki, Itami, Yasuo, Itagaki, Tsuyoshi
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