WO2009151141A1

WO2009151141A1 - Surface treatment composition, process for producing the same, and surface-treated article

Info

Publication number: WO2009151141A1
Application number: PCT/JP2009/060969
Authority: WO
Inventors: Tomohiro Yoshida; Masahiko Maeda; Tetsuya Masutani; Akinobu Wakabayashi; Kazunori Shirai
Original assignee: Daikin Industries Ltd; Moresco Corp
Current assignee: Daikin Industries Ltd; Moresco Corp
Priority date: 2008-06-10
Filing date: 2009-06-10
Publication date: 2009-12-17
Anticipated expiration: 2010-12-10

Abstract

In a surface treatment composition comprising a fluorine-containing polymer, a content of a non-reactive fluorine-containing polymer is less than 25 mol% (on the basis of the total amount) which may be present together with a reactive fluorine-containing polymer in the surface treatment composition and is expressed by a formula: Rf-R¹-R²-F (wherein Rf represents a perfluoroalkyl group having a carbon number of 1 to 16; R¹ is a group expressed by a formula: -(OC₃F₆)a-(OC₂F₄)_b-(OCF₂)_c-; R² is a group expressed by a formula: -(Y)_d-(OCF₂)_e-(CH₂)_f-; and Y is an oxygen atom or a divalent polar group). According to the surface treatment composition of the present invention, a surface-treated article obtained by applying it to a base material can have a hard-to-slip surface, so that the surface-treated article can be held with a chucking tool firmly and stably, and thereby processability is improved.

Description

DESCRIPTION

SURFACE TREATMENT COMPOSITION,

PROCESS FOR PRODUCING THE SAME, AND SURFACE-TREATED ARTICLE

Technical Field

[0001] The present invention relates to surface treatment composition comprising a fluorine-containing polymer, a process for producing the same, and surface- treated article to which the same is applied.

Background Art

[0002] It is known that some of fluorine-containing polymers provide a good property of antifouling when they are used for surface treatment of glass, plastic or the like. Such fluorine-containing polymers are, for example, a fluoropolymer having a part comprising a Si atom or a metal atom at its molecular end (see Patent Document 1 listed below) , or a compound prepared by combining a monomer having perfluoropolyether and a carbon-carbon double bond with a triisocyanate (see Patent Document 2 listed below) .

[0003] When a surface treatment composition comprising such fluorine-containing polymer (hereinafter which is also refereed to as a "fluorine-containing polymer surface treatment composition" or just as a "surface treatment composition") is used to, for example, improve a property of antifouling of a spectacle lens, the surface treatment composition is applied to a surface of the lens to form a antifouling layer (thin film) on the surface of the lens, and thus obtained surface-treated lens is subjected to a grinding process to fit into a desired frame shape while it is held with a chucking (or clamping) tool and rotated (see Patent Documents 3 and 4 listed below) . Patent Document 1: WO 98/49218

Patent Document 2: WO 03/002628

Patent Document 3: Japanese Patent Laid-open (Kokai) Publication No. 2006-95657

Patent Document 4: Japanese Patent Laid-open (Kokai) Publication No. 2007-152439

Summary of Invention

Technical Problem [0004] Conventionally, when a lens surface which has been treated by a commercially available fluorine- containing surface treatment composition is subjected to a grinding process, a tool is likely to slip on the lens surface to deviate a rotational axis with respect to the lens (so-called "axis deviation" readily is likely to occur) , so that there is a problem of difficulty in processing.

[0005] In order to address such problem, it is proposed to apply a porous adhesive sheet between the lens and the chucking tool (Patent Document 3) , and to control a chucking pressure depending on a load applied to the lens (Patent Document 4) .

[0006] However, all of the measures proposed heretofore relate to a processing apparatus, thus the problem of that application of a fluorine-containing polymer surface treatment composition makes a lens slippy and results in decreased processability (or workability) has not been solved fundamentally yet.

[0007] The present inventors has focused on a fluorine- containing surface treatment composition itself, and aimed to produce a surface treatment composition which can give a hard-to-slip surface when being applied and thus can improve processability, a process for producing such surface treatment composition, and a surface-treated article to which it is applied.

Solution to Problem

[0008] According to the first aspect of the present invention, there is provided a surface treatment composition comprising a fluorine-containing polymer, which comprises as a reactive fluorine-containing polymer a compound expressed by any of the following general formulas (I) and (II) :

[wherein Rf represents a perfluoroalkyl group having a carbon number of 1 to 16;

R¹ is a group expressed by the following formula:

- (OC₃F₆) a- (OC₂F₄) _b- (OCF₂) c-

(wherein a, b and c are integers not less than 0 but not larger than 200 independently; the sum of a, b and c is at least 1; and the presence order of the repeating units in parentheses is arbitrary in the formula) ;

R² is a group expressed by the following formula:

(wherein Y is an oxygen atom or a divalent polar group; d, e and f are integers not less than 0 but not larger than 50 independently; the sum of d, e and f is at least 1; and the presence order of the repeating units in parentheses is arbitrary in the formula) ;

P represents a hydrolyzable polar group; R³ represents an alkyl group having a carbon number of 1 to 22 ; n is an integer from 1 to 3;

R⁴ is a group expressed by the following formula:

(wherein g is an integer not less than 0 but not larger than 50) ;

X is a hydrogen atom, an alkyl group having a carbon number of 1 to 4, a bromine atom, or an iodine atom; m is an integer not less than 1 but not larger than 10], wherein a content of a compound of a non-reactive fluorine-containing polymer expressed by the following general formula (III) : Rf-R¹^-F (III) [wherein Rf, R¹ and R² are the same as described above] in the surface treatment composition is less than 25 mol% (on the basis of the total amount) .

[0009] According to a second aspect of the present invention, there is provided a surface treatment composition comprising a fluorine-containing polymer, which comprises as a reactive fluorine-containing polymer an alkene compound essentially consisting of the following (A) and (B) : (A) a triisocyanate of trimerized diisocyanate; and

(B) a combination of at least the following two of active hydrogen-containing compounds

(B-I) a compound expressed by any of the following general formulas (i-b) and (ii-b) :

Rf-R¹-R²-CH₂OH (i-b)

HOCH₂-R²-R¹-R²-CH₂OH (ii-b)

[wherein Rf, R¹ and R² are the same as described above] ; and (B-2) a monomer having an active hydrogen and a carbon-carbon double bond, wherein a content of a compound of a non-reactive fluorine-containing polymer expressed by a following general formula (III) : Rf-R^x-R²-F (III)

[wherein Rf, R¹ and R² are the same as described above] in the surface treatment composition is less than 25 mol%

(on the basis of the total amount) .

[0010] In the present invention, the "reactive" means that a component is able to chemically react with a surface of a base material, and/or by itself or with other component on the surface of the base material, and the

"non-reactive" means that a component does not bring about such reaction. What a material comprises a compound expressed by "any" of two general formulas means that the material comprises at least one of the compound expressed by one general formula and the compound expressed by the other general formula, and may comprise both of the compound expressed by one general formula and the compound expressed by the other general formula. The "content" means a content ratio.

[0011] The present inventors intensively studied components of the conventional fluorine-containing surface treatment composition and reactivity of each of the components when the surface treatment composition is applied to a base material such as a lens. As a result, it was found that the conventional fluorine-containing surface treatment composition contains, in addition to a reactive fluorine-containing polymer, a non-reactive fluorine- containing polymer at a large amount, generally about 30 to 40 mol% (on the basis of the total amount) , and the non- reactive fluorine-containing polymer is contained relatively freely in a layer of the fluorine-containing polymer surface treatment composition which layer is formed on the base material by a reaction of the reactive fluorine-containing polymer, and therefore make the surface being likely to slip.

[0012] On the contrary, according to the surface treatment composition in the first and the second aspects of the present invention, a content of the non-reactive fluorine-containing polymer in the composition is reduced to 25 mol% or less (on the basis of the total amount) , thereby use of this surface treatment composition can provide a hard-to-slip surface and thus can improve processability . The present invention has been accomplished based on the unique knowledge by the present inventors as described above.

[0013] A content of the non-reactive fluorine-containing polymer in the surface treatment composition of the present invention is, although the content of 25 mol% or less (on the basis of the total amount, which is also applied hereafter) can cause substantial effects, preferably about 20 mol% or less, more preferably about 15 mol% or less, and ideally substantially zero mol% (in other words, less than 1 mol%, which is a general lower limit of analysis) .

[0014] As to the surface treatment composition in the first aspect of the present invention, the non-reactive fluorine-containing polymer is a compound having a reactive part of silicon (Si) at one end or both ends, the compound having it at one end is expressed by the general formula (I), and the compound having it at both ends is expressed by the general formula (II) .

[0015] In these formulas, Rf represents a linear or branched perfluoroalkyl group having a carbon number of 1 to 16, and preferably a linear or branched perfluoroalkyl group having a carbon number of 1 to 3 (CF₃-, C₂F₅-, C3F7-) .

[0016] R¹ is a group expressed by the following formula:

- (OC₃F₆) _a- (OC₂F₄) _b- (OCF₂) c-

In this formula, a, b and c represent, respectively, the numbers of the three-type repeating units of perfluoropolyethers constituting the main skeleton of the fluorine-containing polymer, wherein a, b and c are integers independently not less than 0 but not larger than 200, preferably from 1 to 100, and the sum of a, b and c is at least 1, preferably 1 to 100. Although the presence order of the respective repeating units in parentheses with subscripts a, b and c is shown in the above formula according to a specific presence order for the purpose of convenience, the linkage order of these repeating units is arbitrary without being limited by this order. Among these repeating units, the unit -(OC₃F₆)- may be either (OCF₂CF₂CF₂)- or -(OCF(CF₃)CF₂)-, preferably -(OCF₂CF₂CF₂)-. The unit -(OC₂F₄)- may be either -(OCF₂CF₂)- or -(OCF(CF₃))-, preferably -(OCF₂CF₂)-.

[0017] R² is a group expressed by the following formula: - (Y) _d- (CF₂) _e- (CH₂) _f-

In this formula, Y is an oxygen atom or a divalent polar group. Examples of the divalent polar group may include - C00-, -0C0-, -CONH-, -OCH₂CH(OH)CH₂-, -CH₂CH(OH)CH₂O-, -COS-, -SCO- and -0-, and preferably Y is -COO-, -CONH-, CH₂CH(OH)CH₂O- or -0- . Also in this formula, d, e and f are integers independently not less than 0 but not larger than 50, preferably from 0 to 20, and the sum of d, e and f is at least 1, preferably 1 to 10. More preferably, d, e and f are integers from 0 to 2, and further more preferably d=0 or 1, e=2, f=0 or 1. Although the presence order of the respective repeating units in parentheses with subscripts d, e and f is shown in the above formula according to a specific presence order for the purpose of convenience, the linkage order of these repeating units is arbitrary without being limited by this order.

[0018] P and R³ are groups linked to Si, and n is an integer from 1 to 3.

[0019] P represents a hydrolyzable polar group. Examples of a hydrolyzable polar group may include halogen, -OA, -OCOA, -0-N=C(A)₂ [wherein A represents a linear or branched hydrocarbon group having a carbon number of 1 to 3 (CH₃-, C₂H₅-, C₃H7-) ] .

[0020] R³ represents a linear or branched alkyl group having a carbon number of 1 to 22, preferably a linear or branched alkyl group having a carbon number of 1 to 3 (CH3-,

[0021] R⁴ is a group expressed by the following formula:

In this formula, g is an integer not less than 0 but not larger than 50, preferably an integer not less than 1 but not larger than 20. A bond extending from the repeating units in parentheses with a subscript g is linked to Si.

[0022] X is a hydrogen atom, an alkyl group having a carbon number of 1 to 4, a bromine atom, or an iodine atom, preferably a hydrogen atom or an alkyl group having a carbon number of 1 to 4. ^•

[0023] Then, m is an integer not less than 1 but not larger than 10, preferably an integer not less than 1 but not larger than 5. [0024] In the present description, Rf, R¹, R², R³, R⁴, P,

X, Y, m and n are the same as described above, unless otherwise specified.

[0025] According to one mode of the present invention, there is provided a process for producing a surface treatment composition comprising a fluorine-containing polymer, which comprises the steps of:

(p) using a raw material mixture which comprises a compound expressed by any of the following general formulas (i) and (ii) :

Rf-R¹^-COF (i)

FOC-R²-R^X-R²-COF (ii)

[wherein Rf, R¹ and R² are the same as described above] ; and a compound expressed by the following general formula

(III) :

Rf-R¹-R²-F (III)

[wherein Rf, R¹ and R² are the same as described above] and subjecting the compound expressed by any of the general formulas (i) and (ii) to an iodination reaction to obtain a reaction mixture which comprises thus generated compound expressed by any of the following general formulas (i-a) and (ii-a) : Rf-R^x-R²-I (i-a)

I-R²-R¹-R²-I (ii-a)

[wherein Rf, R¹ and R² are the same as described above] , and the unreacted compound expressed by the general formula

(III); (q) subjecting the reaction mixture obtained from the step (p) to a purifying operation using column chromatography to remove at least part of the compound expressed by the general formula (III) and thereby obtain a purified material in which a content of the compound expressed by any of the general formulas (i-a) and (ii-a) is higher than that in the reaction mixture;

(r) using the purified material obtained from the step (q) and reacting the compound expressed by any of the general formulas (i-a) and (ii-a) with CH₂=CR⁵- (CH₂) _h-SiZ_nR³ ₃__n and P-H

[wherein P, R³ and n are the same as described above; z is a halogen atom; R⁵ is a hydrogen atom or an alkyl group having a carbon number of 1 to 4; h is an integer not less than 0 but not larger than 2] to obtain as a surface treatment composition a reaction mixture which comprises as a reactive fluorine-containing polymer, thus generated compound expressed by any of the following general formulas (I) and (II) :

[wherein Rf, R¹, R², P, R³, n, R⁴, X and m are the same as described above] , wherein a content of the unreacted compound of a non- reactive fluorine-containing polymer expressed by the general formula (III) in the surface treatment composition is less than 25 mol% (on the basis of the total amount) . [0026] -Step (p)

In the raw material mixture used for the step (p) , what is subjected to the reaction is the compound expressed by any of the above general formulas (i) and (ii) . However, the raw material mixture generally comprises not only the compound expressed by the formulas (i) and (ii) but also the compound expressed by the general formula (III) . In the raw material mixture, a ratio of the compound expressed by any of the general formulas (i) and (ii) (when it comprises both, the sum of ratios of the respective compounds) is, for example, about 65 to 75 mol%, and typically about 70 to 75 mol%, a ratio of the compound expressed by the general formula (III) is, for example, about 25 to 35 mol%, and typically about 25 to 30 mol% (with the proviso that they do not exceed 100 mol% in total), but the present invention does not limited to these. Since each of the compounds expressed by the general formulas (i) and (ii) has a boiling point close to that of the compound expressed by the general formula (III), it is very difficult to distill off the compound of the general formula (III) by subjecting the raw material mixture to a distillation operation.

[0027] In the step (p) , such raw material mixture is used, and the compound expressed by any of the general formulas (i) and (ii) is subjected to an iodination reaction to generate a compound expressed by any of the following general formulas (i-a) and (ii-a) : Rf-R¹^-I (i-a) I-R^R^R²-! (ii-a) [0028] The iodination reaction can proceed by reacting the compound expressed by any of the formulas (i) and (ii) with I₂ in the presence of, for example, K₂CO₃. The reaction conditions are not particularly limited, but may be, for example, at about 160 to 210⁰C in the stream of nitrogen.

[0029] The reaction mixture obtained by the iodination reaction comprises not only the compound expressed by any of the general formulas (i-a) and (ii-a) , but also the unreacted compound expressed by the general formula (III) . [0030] -Step (q)

Then, the reaction mixture obtained from the step (p) is subjected to a purifying operation using column chromatography. Since the iodinated compounds of the general formulas (i-a) and (ii-a) have a different polarity from that of the compound of the general formula (III), the compound of the general formula (III) can be removed off by the use of column chromatography. By such purifying operation, the compound expressed by the general formula (III) is at least partially removed, and the purified material in which .the content of the compound expressed by any of the general formulas (i-a) and (ii-a) is higher than that in the above reaction material can be obtained. In the purified material, a ratio of the compound expressed by any of the general formulas (i-a) and (ii-a) (when it comprises both, the sum of ratios of the respective compounds) is, for example, about 80 to 100 mol%, and typically about 90 to 100 mol%, a ratio of the compound expressed by the general formula (III) is, for example, about 0 to 20 mol%, and typically about 0 to 10 mol% (with the proviso that they do not exceed 100 mol% in total) , but the present invention does not limited to these. [0031] -Step (r)

Then, the purified material obtained from the step (q) is used, and the compound expressed by any of the general formulas (i-a) and (ii-a) reacts with CH₂=CR⁵- (CH₂) _h-SiZ_nR³ ₃-_n and P-H to generate a compound expressed by any of the following general formulas (I) and (II) :

[0032] In the above formulas, z is a halogen atom which is the same as or different from iodine (I), for example, Cl, Br, I, and preferably Cl. [0033] For example in a case of reaction with CH₂=CH- SiCl₃ and CH₃OH (which corresponds to a case where Z is Cl, n is 3, R⁵ is H, h is 0, and p is CH₃O) , the reaction may- proceed in two stages by reacting the compound expressed by any of the general formulas (i-a) and (ii-a) firstly with CH₂=CH-SiCl₃ and then reacting with CH₃OH in the presence of a catalyst such as Zn. The reaction conditions are not particularly limited, but the first stage reaction may be, for example, at about 100 to 150⁰C, and the second stage reaction may be, for example, at about 40 to 70⁰C. [0034] The reaction mixture obtained from the above reaction comprises not only the compound expressed by any of the general formulas (I) and (II), but also the unreacted compound expressed by the general formula (III) . Among them, the compound expressed by any of the general formulas (I) and (II) is a reactive fluorine-containing polymer, and the compound expressed by the general formula (III) is a non-reactive fluorine-containing polymer. A ratio of the compound expressed by any of the general formulas (I) and (II) in this reaction mixture (when it comprises both, the sum of ratios of the respective compounds) is similar to the ratio of the compound expressed by any of the general formulas (i-a) and (ii-a) in the above purified material (when it comprises both, the sum of ratios of the respective compounds) , and a ratio of the compound expressed by the general formula (III) in this reaction mixture is similar to its ratio in the purified material.

[0035] In this step (r) , the reaction mixture can be obtained as a surface treatment composition. In the surface treatment composition, a content of the unreacted compound expressed by the general formula (III) as the non- reactive fluorine-containing polymer is less than 25 mol%, and therefore the surface treatment composition according to the first aspect of the present invention can be produced.

[0036] However, a way of obtaining a surface treatment composition according to the first aspect of the present invention is not limited to that reaction, but it can also be obtained by a reaction of the above raw material mixture (i) , (ii) and (III) with, for example, a silane coupling agent (e.g. HOCH₂CH₂CH₂Si (OCH₃) 3) .

[0037] In a surface treatment composition according to the second aspect of the present invention, a reactive fluorine-containing polymer is a compound having a reactive part of a carbon-carbon double bond, which is an alkene compound essentially consisting of the following (A) and (B) :

(A) a triisocyanate of trimerized diisocyanate;

Rf-R¹^-CH₂OH (i-b)

HOCH₂-R²-R¹-R²-CH₂OH (ii-b) [wherein Rf, R¹ and R² are the same as described above] ;

(B-2) a monomer having an active hydrogen and a carbon-carbon double bond.

[0038] As to the compounds expressed by the above general formulas (i-b) and (ii-b), a hydrogen in a hydroxyl group (-0H) is an active hydrogen.

[0039] According to one mode of the present invention, there is provided a process for producing a surface treatment composition comprising a fluorine-containing polymer, which comprises the steps of: (s) using a raw material mixture which comprises a compound expressed by any of the following general formulas (i) and (ii) : Rf-R^-I^-COF (i) FOC-Ϊ^-I^-F^-COF (ii) [wherein Rf, R¹, and R² are the same as described above, which are also applied hereafter] ; and a compound expressed by the following general formula

(III) : Rf-R¹^-F (III) and subjecting the compound expressed by any of the general formulas (i) and (ii) to an alcohol-forming reaction to obtain a reaction mixture which comprises thus generated compound expressed by any of the following general formulas (i-b) and (ii-b) : Rf-R¹^-CH₂OH (i-b)

HOCHz-R^R^R^CHaOH (ii-b), and the unreacted compound expressed by the general formula

(in);

(t) subjecting the reaction mixture obtained from the step (s) to a purifying operation using column chromatography to remove at least part of the compound expressed by the general formula (III) and thereby obtain a purified material in which a content of the compound expressed by any of the general formulas (i-b) and (ii-b) is higher than that in the reaction mixture; (u) using the purified material obtained from the step

(t) , and reacting a combination of at least first and second active hydrogen-containing compounds with a triisocyanate of trimerized diisocyanate, wherein the first active hydrogen-containing compound is the compound expressed by any of the general formulas (i-b) and (ii-b) and the second active hydrogen-containing compound is a monomer having an active hydrogen and a carbon-carbon double bond, to obtain as a surface treatment composition a reaction mixture which comprises as a reactive fluorine- containing polymer, thus generated alkene compound, wherein a content of the unreacted compound of a non- reactive fluorine-containing polymer expressed by the general formula (III) in the surface treatment composition is less than 25 mol% (on the basis of the total amount) . [0040] -Step (s)

As the raw material mixture used for the step (p) , a similar raw material mixture to that explained in the above with respect to the step (p) can be used. [0041] In the step (s) , such raw material mixture is used, and the compound expressed by any of the general formulas (i) and (ii) is subjected to an alcohol-forming reaction to generate a compound expressed by any of the following general formulas (i-b) and (ii-b) : Rf-R^R^CHaOH (i-b) HOCH₂-R²-R¹-R²-CH₂OH (ii-b)

[0042] The alcohol-forming reaction can proceed by reducing the compound expressed by any of the formulas (i) and (ii) with, for example, NaBH₄. The reaction conditions are not particularly limited, but may be, for example, at about 90 to 130⁰C.

[0043] The reaction mixture obtained by the alcohol- forming reaction comprises not only the compound expressed by any of the general formulas (i-b) and (ii-b), but also the unreacted compound expressed by the general formula (III) • [0044] -Step (t)

Then, the reaction mixture obtained from the step (s) is subjected to a purifying operation using column chromatography. Since the alcoholic compounds of the general formulas (i-b) and (ii-b) have a different polarity from that of the compound of the general formula (III), the compound of the general formula (III) can be removed off by the use of column chromatography. By such purifying operation, the compound expressed by the general formula

(III) is at least partially removed, and the purified material in which the content of the compound expressed by any of the general formulas (i-b) and (ii-b) is higher than that in the above reaction material can be obtained. In the purified material, a ratio of the compound expressed by any of the general formulas (i-b) and (ii-b) (when it comprises both, the sum of ratios of the respective compounds) is, for example, about 80 to 100 mol%, and typically about 90 to 100 mol%, a ratio of the compound expressed by the general formula (III) is, for example, about 0 to 20 mol%, and typically about 0 to 10 mol% (with the proviso that they do not exceed 100 mol% in total) , but the present invention does not limited to these. [0045] -Step (u) Then, the purified material obtained from the step (t) is used, and a combination (B) of at least first and second active hydrogen-containing compounds wherein the first active hydrogen-containing compound (B-I) is the compound expressed by any of the general formulas (i-b) and (ii-b) and the second active hydrogen-containing compound (B-2) is a monomer having an active hydrogen and a carbon- carbon double bond, reacts with a triisocyanate (A) of trimerized diisocyanate to generate an alkene compound. [0046] This alkene compound is resulted by reacting the three isocyanate groups of the triisocyanate of the component (A) with active hydrogens of the active hydrogen- containing compounds of the component (B) , and has at least one carbon-carbon double bond. It is only necessary that two of the three isocyanate groups (a NCO group) in the triisocyanate (A) react respectively with two kinds of the active hydrogen-containing compounds (B-I) and (B-2) . The remaining one isocyanate group may react with the active hydrogen-containing compound (B-I) or (B-2), or may react with the third active hydrogen-containing compound (B-3) which is different from them.

[0047] The triisocyanate (A) is a triisocyanate prepared from trimerizing a diisocyanate . Examples of diisocyanate used for giving the triisocyanate (A) include diisocyanates having aliphatically bonded isocyanate groups, for example, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate and dicyclohexylmethane diisocyanate; and diisocyanates having aromatically bonded isocyanate groups, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylenepolyphenyl polyisocyanate, tolidine diisocyanate and naphthalene diisocyanate.

[0048] In the component (B), the compound (B-I) expressed by any of the general formulas (i-b) and (ii-b) :

Rf-R^R^CHzOH (i-b)

HOCH₂-R²-R¹-R²-CH₂OH (ii-b) is a fluorine-containing polymer wherein Rf, R¹ and R² are the same as described above.

[0049] In the component (B), the monomer (B-2) having an active hydrogen and a carbon-carbon double bond is preferably a (meth) acrylate ester or vinyl monomer having a hydroxyl group as a active hydrogen. Examples of the monomer (B-2) include the following: hydroxyethyl (meth) acrylate, aminoethyl (meth) acrylate,

HO(CH₂CH₂O)₁-COC(R)C=CH₂ (wherein R is H or CH₃, i = 2 to

10),

CH₃CH (OH) CH₂OCOC (R) C=CH₂ (wherein R is H or CH₃: 2- hydroxypropyl (meth) acrylate) ,

CH₃CH₂CH (OH) CH₂OCOC (R) C=CH₂ (wherein R is H or CH₃: 2- hydroxybutyl (meth) acrylate) ,

C₆H₅OCH₂CH (OH) CH₂OCOC (R) C=CH₂ (wherein R is H or CH₃: 2- hydroxy-3-phenoxypropyl (meth) acrylate) , allyl alcohol,

HO(CH₂)_kCH=CH₂ (k=2 to 20) ,

(CHs)₃SiCH(OH)CH=CH₂, and styryl phenol.

[0050] In the component (B), the third active hydrogen- containing compound (B-3) which is optionally used

(hereinafter, simply referred to as the third component) is preferably a compound which has neither a perfluoropolyether group nor a carbon-carbon double bond and which has at least one active hydrogen. Preferable examples of the third component (B-3) include the following: a monohydric alcohol composed of a linear or branched hydrocarbon having a carbon number of 1 to 16,

_YT^OH 0

a secondary amine composed of a linear or branched hydrocarbon having a carbon number of 1 to 16, a secondary amine containing an aromatic group, Q (CF₂)i (CH=CH) _m(CHI)_n (CH₂) _oOH (wherein Q is a hydrogen atom, a fluorine atom or a (CF₃) ₂CF- group, 1 is an integer of 1 to 10, m and n are integers of 0 to 1 independently, and o is an integer of 1 to 10) , a polyalkylene glycol monoester; for example, R(OCH₂CH₂) _p0H, R (OCH₂CH₂CH₂ )_q0H (wherein R is a linear or branched hydrocarbon, an acetyl group, or an alkylphenoxy group having a carbon number of 1 to 16, and p and q are integers of 1 to 20 independently) , an aromatic alcohol, a silane compound having an active hydrogen, (CH₃) ₃Si (CH₂) _s0H (wherein s is an integer of 1 to 20), [(CH₃) ₃] ₂NH, ^ ^-N-(CH₃)3-Si(OCH₃)3

[0051] The reaction for giving the alkene compound may be described as follows (PFPE means perfluoropolyether) :

~45°C

( 1 )

(2)

Isocyanurate type PFPE urethane acrylate

[0052] Specific examples of the alkene compound obtained by using the third component include a compound of the following chemical formula:

[0053] A reacting ratio of the component (A) and the component (B) (i.e. (B-I) and (B-2), and (B-3) when used) may be appropriately selected. The obtained alkene compound is preferably by reacting the first isocyanate group of the component (A) with the first component (B-I), reacting the second isocyanate group with the second component (B-2) , and reacting the third isocyanate group with any of the first component (B-I), the second component (B-2) and the third component (B-3) . It may be a mixture of different compounds obtained by reacting three isocyanate groups of the component (A) with any of the component (B) selected from the group consisting of the first component (B-I), the second component (B-2) and the third component (B-3) .

[0054] The reaction mixture obtained by the above reaction comprises not only the alkene compound, but also the unreacted compound expressed by the general formula (III) . Among them, the alkene compound is a reactive fluorine-containing polymer, and the compound expressed by the general formula (III) is a non-reactive fluorine- containing polymer. A ratio of the alkene compound in this reaction mixture is similar to the ratio of the compound expressed by any of the general formulas (i-b) and (ii-b) in the above purified material (when it comprises both, the sum of ratios of the respective compounds) , and a ratio of the compound expressed by the general formula (III) in this reaction mixture is similar to the ratio in the purified material. [0055] In this step (u) , the reaction mixture can be obtained as a surface treatment composition. In the surface treatment composition, a content of the unreacted compound expressed by the general formula (III) as the non- reactive fluorine-containing polymer is less than 25 mol%, and therefore the surface treatment composition according to the second aspect of the present invention can be produced.

[0056] The surface treatment composition according to the first or the second aspect of the present invention may include any suitable other component (s) such as a coupling agent, an antistatic agent, an ultraviolet absorber, a plasticizer, a leveling agent, a pigment, a catalyst and so on.

[0057] According to another mode of the present invention, there is provided a surface-treated article, which comprises a base material, and a layer (or a thin film) formed by the surface treatment composition in the first or the second aspect of the present invention on a surface of the base material.

[0058] The layer formed by the surface treatment composition on the surface of the base material has a good antifouling property. Further, since this layer shows a high transmittance, the surface treatment composition of the present invention is suitable to the use for optic materials which require transmittancy.

[0059] While the present invention is not limited to, but the layer formed by the surface treatment composition may have a thickness of, for example, about 0.001 to 0.03 μm.

[0060] In a case of applying the surface treatment composition according to the first aspect of the present invention, by applying or depositing the surface treatment composition on the base material, a reactive part of silicon (Si) in the reactive fluorine-containing polymer can be combined to a material consisting of the surface of the base material to form the layer derived from the surface treatment composition. [0061] In a case of applying the surface treatment composition according to the second aspect of the present invention, by applying the surface treatment composition on the base material and curing it by light or heat, a reactive part of the carbon-carbon double bond in the reactive fluorine-containing polymer can polymerize with each other (optionally, with other polymerizable component) to form the layer derived from the surface treatment composition.

[0062] In either case, materials suitably used for the base material may include glass, resin, metal, ceramic, wood, pottery, porcelain, stone, leather and so on. The base material may have any layer such as a hard coat layer or an antireflection layer on the surface of such material before the application of the surface treatment composition. The surface-treated article obtained thereby may be, for example, lens such as spectacle lens; a front protective panel, a antireflection plate, a polarizing plate, an antiglare plate of a display such as PDP and LCD; a touch panel sheet of an instrument such as a cellular phone and a personal digital assistance; a disc plane of an optical disc such as a DVD disc, a CD-R and an MO; and an optical fiber.

[0063] When applying the surface treatment composition, the composition may be applied in a state dissolved, suspended or dispersed in a fluorine-free solvent or a fluorine-containing solvent, and then the solvent may be removed off by drying and/or vaporization. Examples of the fluorine-free solvent include ketones (for example, methyl ethyl ketone and acetone), alcohols (for example, a monohydric alcohol such as ethanol and propanol, and polyhydric alcohol such as ethylene glycol, diethylene glycol and propylene glycol), esters (for example, ethyl acetate) , and ethers (for example, diethylene glycol monomethyl ether, diethylene glycol monomethyl acetate, and propylene glycol monomethyl ether) . Examples of the fluorine-containing solvent include fluoroalcohols, fluoroethers, ditrifluoromethyl benzene, and perfluorohexane .

[0064] The surface-treated article obtained as described above (by using the surface treatment composition either in the first or the second aspect) shows that, a deviation angle of the base material from a rotational axis holding the base material in processing (or shaping) of the surface-treated article is preferably 2 degrees or less. [0065] The "deviation angle" in the present invention is defined as an angular difference θ (degree) (shown in Fig. 1) of a basing point marked on a surface of a lens between before and after the lens is processed with an edger into a rectangle of 60 mm x 30 mm at a chucking pressure of 50 kg by using a lens processing tape (trade name: Leap lens blocking pad, from Sumitomo 3M Limited) and using SE9090 or LE9000 (both from NIDEK CO., LTD) as a processing apparatus. In Fig. 1, orthogonal coordinates of a basing point (the symbol O in the drawing) before the processing are shown in dotted lines, orthogonal coordinates of a basing point (the symbol 0' in the drawing) after the processing are shown in solid lines, and a deviation angle is shown as θ (degree) . [0066] When the conventional fluorine-containing surface treatment composition is applied, a deviation angle is generally 3 degrees or more. On the contrast, when the fluorine-containing surface treatment composition of the present invention is applied, a deviation angle is reduced to 2 degrees or less. The surface-treated article obtained in accordance with the present invention is hard to slip and readily processable (or workable) as compared with the conventional article.

Advantageous Effects of Invention

[0067] According to the present invention, there are provided a surface treatment composition which can give a hard-to-slip surface when being applied and thus can improve processability (or workability) , a process for producing such surface treatment composition, and a surface-treated article to which it is applied.

Brief Description of Drawings [0068] Fig. 1 is a graph for explaining a deviation angle referred to in the present invention.

Description of Embodiments [0069] The present invention is further explained specifically by the following examples, but the present invention is not limited to these examples only. [0070] A polymer composition in the present description is measured as follows. Polymer Composition (IH-NMR, 19F-NMR, IR)

NMR measurement apparatus : from BRUKER

Corporation

IH-NMR measuring conditions: 300 MHz (tetramethylsilane = 0 ppm) 19F-NMR measuring conditions: 282 MHz

(trichlorofluoromethane = 0 ppm)

IR measurement apparatus : from PerkinElmer Inc. An average molecular weight and molar ratios (mol%) of the respective components in a mixture are calculated from the results by the NMR measurement. The "average molecular weight" throughout the present description means a number average molecular weight.

A yield is calculated with the proviso that an ideal case with respect to both a precursor of a reactive fluorine-containing polymer and a non-reactive fluorine- containing polymer is set at 100% wherein the all of the precursor of a reactive fluorine-containing polymer is converted into an aimed reaction product.

Examples

[0071] Example 1

The present example relates to a surface treatment composition according to the first aspect of the present invention described above and to a process for producing the same. [0072] -Step (p)

A raw material mixture used was a mixture of 2800 g (0.72 mole) of ω-fluoro poly perfluorooxetane acyl fluoride (average molecular weight 3900) expressed by the following chemical formula:

CF₃CF₂CF₂- (OCF₂CF₂CF₂) _a-O-CF₂CF₂-COF and 1200 g (0.31 mole) of perfluoropolyoxetane (average molecular weight 3900) expressed by the following chemical formula: CF₃CF₂CF₂- (OCF₂CF₂CF₂) _a-O-CF₂CF₃

[0073] A 2.0 L four-neck flask equipped with a stirrer, a dropping funnel, a refluxing condenser and a thermometer was charged with 2617 g (10.3 mole) of iodine (I₂), 213.2 g

(1.54 mole) of potassium carbonate (K₂CO₃) and 9000 g of an organic solvent. Then, while a temperature of a liquid phase in the flask was maintained at about 160⁰C, under a nitrogen (N2) gas stream the raw material mixture described above was added dropwise thereto at a rate of 10 mL/min. After completion of the dropwise addition, the temperature of the liquid phase was raised to about 185°C and a reaction was allowed to proceed for 20 hours at this reaction temperature. Then, the flask content was cooled, the liquid phase filtered to remove a potassium salt (solid state) was separated into two (upper and lower) phases with the use of a separating funnel, and the lower phase (organic phase) was obtained separately. Thus obtained organic phase was washed with acetone several times, followed by being dissolved into 1 L of perfluorohexane and passed through a glass filter to remove undissolved residue. As a result of completely removing a volatile portion (the solvent and the like, whish is also applied hereafter) from the obtained solution by distillation under a reduced pressure, 3890 g (yield 95%) of a reaction mixture was obtained. [0074] According to IR analysis of the obtained reaction mixture, the absorption at 1890 cm^"1 derived from -C(=O)F disappeared completely, and the absorption at 910 cm^"1 derived from -CF₂I newly appeared. Therefore, the reaction mixture was recognized as a mixture of ω-fluoro poly perfluorooxetane iodide expressed by the following chemical formula:

CF₃CF₂CF₂- (OCF₂CF₂CF₂) _a-O-CF₂CF₂I and perfluoropolyoxetane expressed by the following chemical formula: CF₃CF₂CF₂- (OCF₂CF₂CF₂) _a-O-CF₂CF₃

[0075] In this reaction mixture, the content of ω-fluoro poly perfluorooxetane iodide (average molecular weight

3900) was 70 mol%, and the content of perfluoropolyoxetane

(average molecular weight 3900) was 30 mol%. [0076] -Step (q)

The reaction mixture obtained from the step (p) was subjected to chromatography separation by using a column filled with silica gel (solvent: Vertrel XF from

DuPont) , and thereby 2550 g (purity 95 mol%) of a purified material substantially consisting of ω-fluoro poly perfluorooxetane iodide expressed by the chemical formula below was obtained:

CF₃CF₂CF₂- (OCF₂CF₂CF₂) _a-O-CF₂CF₂I

In the purified material, the content of perfluoropolyoxetane expressed by the chemical formula below was 5 mol%:

CF₃CF₂CF₂- (OCF₂CF₂CF₂ ) _a-O-CF₂CF₃

[ 0077 ] - Step ( r)

(Reaction at the first stage) A 200 mL four-neck flask equipped with a stirrer, a dropping funnel, a refluxing condenser and a thermometer was charged with a solution prepared by dissolving 40 g of the purified material obtained from the step (q) in 80 g hexafluorotetrachlorobutane (trade name: Daiflon Solvent S- 316 from DAIKIN INDUSTRIES, LTD.), and with 1.5 g (IxIO^"2 mole) of di-t-butylperoxide. The atmosphere in the flask was sufficiently replaced with nitrogen. Then, under a nitrogen gas stream 16.1 g (0.10 mole) of vinyltrichlorosilane was added dropwise into the flask through the dropping funnel. After completion of the dropwise addition, the temperature of the liquid phase was raised to 120⁰C and a reaction was allowed to proceed for 4 hours at this reaction temperature. Then, as a result of completely removing a volatile portion from the mixture in the flask by distillation under a reduced pressure, 38.7 g (yield 90%) of a reaction mixture (A) was obtained. [0078] It was recognized by IR analysis and NMR analysis that this reaction mixture (A) contained a silicone- containing and fluorine-containing organic polymer which had iodine at its end.

[0079] (Reaction at the second stage)

A 200 mL four-neck flask equipped with a stirrer, a dropping funnel, a refluxing condenser and a thermometer was charged with a solution prepared by dissolving 34.4 g (8xlO^~3 mole) of the reaction mixture (A) obtained from the reaction at the first stage in 50 g perfluorohexane, and

2.1 g (3.2xlO^~2 mole) of zinc was dispersed therein by stirring. Then, while the flask was immersed in an ice water bath to cool its content, under a nitrogen (N₂) gas stream 10 g of anhydrous methanol was added dropwise thereto. After completion of the dropwise addition, the ice water bath was taken away, and a reaction was allowed to proceed for 2 hours while being heated to reflux. Then, the liquid phase filtered to remove undissolved residue was separated into two (upper and lower) phases with the use of a separating funnel, and the lower phase (organic phase) was obtained separately. Thus obtained organic phase was washed with anhydrous methanol three times. As a result of completely removing a volatile portion from it by distillation under a reduced pressure, 31.6 g (yield 92%) of a reaction mixture (B) was obtained.

[0080] According to IH-NMR analysis of thus obtained reaction mixture (B) , a broad absorption band appeared at

1.2 to 3.0 ppm which is derived from respective hydrogen atoms in the formula below. Thus, it was recognized that this reaction mixture (B) contained a silicone-containing and fluorine-containing organic polymer of which end was hydrogenated .

[0081] Adding to the obtained reaction mixture (B) 5.0 mol% of ω-fluoro poly perfluorooxetane hydride (formula:

CF₃CF₂CF₂- (OCF₂CF₂CF₂) ₃-0-CF₂CF₂H) as an internal standard, absorption intensity was measured. A polymerization degree m was 2.0 which was calculated from the following mathematical formula:

I/Is = [0.95(3m+l) ]/0.05

(wherein I means an integrated absorption intensity of 1.2 to 3.0 ppm;

Is means an integrated absorption intensity of the internal standard; and m means a polymerization degree)

[0082] In the reaction mixture (B), the content of a reactive fluorine-containing polymer having a reactive part of silicon was 95 mol%, and the content of perfluoropolyoxetane as a non-reactive fluorine-containing polymer, expressed by the chemical formula below, was 5 mol%: CF₃CF₂CF₂- (OCF₂CF₂CF₂) _a-O-CF₂CF₃

[0083] -Application to Surface Treatment and Evaluation The reaction mixture (B) obtained above was dissolved in perfluorohexane to prepare a treatment solution of 0.1 wt%.

[0084] The used base material was a double-sided aspheric lens with a diameter of 80 mm (composed of an acrylic resin of which surface was coated with oxidized silicon) . It was dipped into the treatment solution for 10 seconds, and pulled up at a velocity of 5 mm/sec, so that surface treatment was performed on the lens. [0085] Two surface-treated lenses were similarly prepared as Samples 1 and 2. These were evaluated with respect to contact angle, deviation angle, and ease in wiping off fingerprint as described below. The results are shown in Table 1. [0086] (Contact Angle) Using a contact angle meter (trade name: CA-DT, from Kyowa Interface Science Co., Ltd.), contact angles with purified water and with hexane each in a liquid volume of 1 μL were measured. [0087] (Deviation Angle) Using a lens processing tape (trade name: Leap lens blocking pad, from Sumitomo 3M Limited) and using SE9090 or LE9000 (both from NIDEK CO., LTD) as a processing apparatus, the lens was processed with an edger into a rectangle of 60 mm x 30 mm at a chucking pressure of 50 kg. An angular difference of a basing point marked on the surface of the lens between before and after the processing was measured.

[0088] (Ease in wiping off Fingerprint)

After the treated base material was pressed by an index finger, the fingerprint was wiped by one cycle of reciprocating movement with KIM Wipe (from Jujo Kimberley

Co., Ltd.) and ease in wiping off fingerprint was visually judged.

Good: Fingerprint can be completely removed. Average: Fingerprint wiping mark is left.

Failing: Fingerprint wiping mark is extended and removal of the mark is difficult.

[0089] Comparative Example 1

A reaction mixture (B) ' was obtained according to similar procedures to Example 1, except that the step (q) was not conducted and the reaction mixture obtained from the step (p) was used for the step (r) in place of the purified material obtained from the step (q) .

[0090] In the reaction mixture (B) ', the content of a reactive fluorine-containing polymer having a reactive part of silicon was 70 mol%, and the content of perfluoropolyoxetane as a non-reactive fluorine-containing polymer, expressed by the chemical formula below, was 30 mol%: CF₃CF₂CF₂- (OCF₂CF₂CF₂) _a-O-CF₂CF₃ [0091] Two surface-treated lenses were prepared as Samples 1 and 2 by performing surface treatment on the lenses according to similar procedures to Example 1, except that the reaction mixture (B) ' was used to prepare a treatment solution. These were evaluated with respect to contact angle, deviation angle, and ease in wiping off fingerprint. The results are shown in Table 1. [0092] Table 1

[0093] As understood from Table 1, Samples 1 and 2 of Example 1 showed a remarkably reduced deviation angle while maintaining contact angles with water and with hexadecane and ease in wiping off fingerprint at levels equal to Samples 1 and 2 of Comparative Example 1. [0094] Example 2

^•Step (s)

A raw material mixture used was a mixture of 700 g (0.28 mole) of ω-fluoro poly perfluorooxetane acyl fluoride (average molecular weight 2500) expressed by the following chemical formula: F- (CF₂CF₂CF₂O)_n-CF₂CF₂-COF and 300 g (0.12 mole) of perfluoropolyoxetane (average molecular weight 2500) expressed by the following chemical formula:

F- (CF₂CF₂CF₂O) H-CF₂CF₃

[0095] Under a nitrogen gas stream, a 3.0 L four-neck flask equipped with a stirrer, a dropping funnel, a refluxing condenser and a thermometer was charged with 330 g of diglyrrte, and 11.4 g (0.3 mole) of NaBH₄ was added thereto with stirring. The raw material mixture described above was added dropwise thereto at a rate of 10 mL/min. After completion of the dropwise addition, the temperature of the liquid phase was raised to about 110⁰C and a reaction was allowed to proceed for 8 hours at this reaction temperature. After the reaction, the flask content was cooled to 40⁰C or less, 700 g of perfluorohexane was added thereto followed by stirring for 10 minutes. It was further cooled to 5°C or less, 140 mL of ion-exchanged water was added dropwise. Then, after

1000 g of a 3N-HC1 solution was added dropwise, the liquid phase was separated into two (upper and lower) phases with the use of a separating funnel, and the lower phase

(organic phase) was obtained separately. Thus obtained organic phase was washed with a 3N-HC1 solution/acetone (340 g / 340 g) three times. As a result of completely removing a volatile portion by distillation under a reduced pressure, 950 g (yield 95%) of a reaction mixture was obtained. [0096] According to IR analysis of the obtained reaction mixture, the absorption at 1890 cm^"1 derived from -C(=O)F disappeared completely, and the absorption at 3300 cm^"1 derived from -CH₂OH newly appeared. Therefore, the reaction mixture was recognized as a mixture of perfluoropolyoxetane alcohol expressed by the following chemical formula:

CF₃CF₂CF₂- (OCF₂CF₂CF₂) _a-O-CF₂CF₂-CH₂OH and perfluoropolyoxetane expressed by the following chemical formula: CF₃CF₂CF₂- (OCF₂CF₂CF₂) _a-O-CF₂CF₃

[0097] In this reaction mixture, the content of perfluoropolyoxetane alcohol (average molecular weight 2500) was 70 mol%, and the content of perfluoropolyoxetane (average molecular weight 2500) was 30 mol%. [0098] -Step (t)

The reaction mixture obtained from the step (s) was subjected to chromatography separation by using a column filled with silica gel (solvent: Vertrel XF from DuPont) , and thereby 660 g (purity 95 mol%) of a purified material substantially consisting of perfluoropolyoxetane alcohol expressed by the chemical formula below was obtained:

CF₃CF₂CF₂- (OCF₂CF₂CF₂) _a-O-CF₂CF₂-CH₂OH

In the purified material, the content of perfluoropolyoxetane expressed by the chemical formula below was 5 mol%: CF₃CF₂CF₂- (OCF₂CF₂CF₂) _a-O-CF₂CF₃ [0099] -Step (U)

A l L four-neck flask equipped with a stirrer, a dropping funnel, a refluxing condenser and a thermometer was charged with a solution prepared by dissolving 144 g of SUMIDUR N3300 (from Sumika Bayer Urethane Co., Ltd., having a content rate of a NCO group of 21.9%) in 200 g of HCFC- 225 (a mixture of 45 mol% of 3, 3-dichloro-l, 1, 1, 2, 2- pentafluoropropane (HCFC-225ca) and 55 mol% of 1,3- dichloro-1, 1, 2, 2, 3-pentafluoropropane (HCFC-225cb) , which is also applied hereafter) . After adding 0.2 g of dibutyltin dilaurate (from Wako Pure Chemical Industries, Ltd., having (JIS) First grade), a solution prepared by dissolving 192 g of the purified material obtained from the step (t) in 300 g of HCFC-225 was added dropwise over 4.5 hours while stirring the content at a room temperature in air. Further, it was stirred for 6 hours at a room temperature. Then, the temperature of the liquid phase was raised to 40⁰C and 95 g of 2-hydroxyethyl acrylate was added dropwise over 10 minutes, and it was stirred for 3 hours. As a result of removing a volatile portion from thus obtained mixture by distillation under a reduced pressure, 560 g (yield 98%) of a reaction mixture (C) (having a solid portion of 50 wt%) was obtained.

[0100] According to IR analysis of the obtained reaction mixture (C) , it was confirmed that the absorption at 2275 cm^"1 derived from -NCO disappeared completely. Therefore, the reaction mixture (C) was considered as a 50 wt% HCFC- 225 solution of a perfluoropolyether urethane acrylate composition.

[0101] In the solid portion of the reaction mixture (C), the content of a reactive fluorine-containing polymer having a reactive part of a carbon-carbon double bond was 95 mol%, and the content of perfluoropolyoxetane as a non- reactive fluorine-containing polymer, expressed by the chemical formula below, was 5 mol%: CF₃CF₂CF₂- (OCF₂CF₂CF₂) _a-O-CF₂CF₃ [0102] -Application to Surface Treatment and Evaluation A curable composition (a treatment solution) was prepared by adding 50 wt% acrylic hard coat (trade name: Fulshade UV-S4 (50 wt% toluene solution) from TOYO INK MFG. CO., LTD) and propylene glycol monomethyl ether (which is hereinafter abbreviated as PGME) to the reaction mixture (C) (50 wt% HCFC-225 solution) obtained above, and stirring sufficiently. The curable compositions of No. 3 to 5 were obtained by varying ratios of Fulshade UV-S4, the reaction mixture (C) and PGME as shown in Curable Composition (part by weight) in Table 2. PMMA (polymethyl methacrylate) substrates ^' (lenses) of 100 mm x 100 mm were respectively dipped in these curable compositions for 10 seconds, and pulled up at a velocity of 5 mm/sec, so that they were applied on the surface of the substrates. Then, the substrates were dried for 5 minutes at 65°C, and irradiated with an ultraviolet ray of 1 J/cm², so that surface treatment was performed on the substrates. Thus, three surface-treated lenses were prepared as Samples 3 to 5. [0103] Table 2

In the table, the solid portion ratio is a ratio of the solid portion of the reaction mixture (C) (50 wt% HCFC-225 solution) to the solid portion of Fulshade UV-S4 (50 wt% toluene solution) .

[0104] The obtained surface-treated lenses of Samples 3 to 5 were evaluated with respect to contact angle, deviation angle, and ease in wiping off fingerprint of a surface-treated lens thereof similarly to Example 1, except that only SE9090 (from NIDEK CO., LTD) was used as a processing apparatus. The results are shown in Table 3. [0105] Comparative Example 2

A reaction mixture (C) ' was obtained according to similar procedures to Example 2, except that the step (t) was not conducted and the reaction mixture obtained from the step (s) was used for the step (u) in place of the purified material obtained from the step (t) . This reaction mixture (C) ' had a solid portion (50 wt%) similar to that of the reaction mixture (C) in Example 2, and a ratio of the solid portion of the reaction mixture (C) ' to the solid portion of Fulshade UV-S4 was also similar to the ratio of the solid portion of the reaction mixture (C) to the solid portion of Fulshade UV-S4 in Example 2 (Table 2) . [0106] In the reaction mixture (C) ', the content of a reactive fluorine-containing polymer having a reactive part of a carbon-carbon double bond was 70 mol%, and the content of perfluoropolyoxetane as a non-reactive fluorine- containing polymer, expressed by the chemical formula below, was 30 mol%:

CF₃CF₂CF₂- (OCF₂CF₂CF₂) _a-O-CF₂CF₃

[0107] Three surface-treated lenses were prepared as Samples 3 and 5 by performing surface treatment on the lenses according to similar procedures to Example 2, except that the reaction mixture (C) ' was used to prepare a treatment solution. These were evaluated with respect to contact angle, deviation angle, and ease in wiping off fingerprint. The results are shown in Table 3. [0108] Table 3

[0109] As understood from Table 3, Samples 3 to 5 of Example 2 showed a remarkably reduced deviation angle while maintaining contact angles with water and with hexadecane and ease in wiping off fingerprint at levels equal to Samples 3 to 5 of Comparative Example 2.

Industrial Applicability

[0110] A surface treatment composition obtained by the present invention can be suitably used as a surface treatment agent for giving an anti fouling property to a surface of various base materials, especially optic materials which require transmittancy.

Claims

1. A surface treatment composition comprising a fluorine- containing polymer, which comprises as a reactive fluorine- containing polymer a compound expressed by any of the following general formulas (I) and (II) :

[wherein Rf represents a perfluoroalkyl group having a carbon number of 1 to 16; R¹ is a group expressed by the following formula:

- (OC₃F₆) _a- (OC₂F₄) _b- (OCF₂) c-

R² is a group expressed by the following formula:

- (Y)d- (CF₂) _β- (CH₂) f-

P represents a hydrolyzable polar group;

R³ represents an alkyl group having a carbon number of 1 to 22; n is an integer from 1 to 3;

R⁴ is a group expressed by the following formula:

(wherein g is an integer not less than 0 but not larger than 50);

X is a hydrogen atom, an alkyl group having a carbon number of 1 to 4, a bromine atom, or an iodine atom; m is an integer not less than 1 but not larger than 10], wherein a content of a compound of a non-reactive fluorine-containing polymer expressed by the following general formula (III) : Rf-R^R^F (III)

[wherein Rf, R¹ and R² are the same as described above] in the surface treatment composition is less than 25 mol% (on the basis of the total amount) .

2. A surface treatment composition comprising a fluorine- containing polymer, which comprises as a reactive fluorine- containing polymer an alkene compound essentially consisting of the following (A) and (B) : (A) a triisocyanate of trimerized diisocyanate; and (B) a combination of at least the following two of active hydrogen-containing compounds

(B-I) a compound expressed by any of the following general formulas (i-b) and (ii-b) : Rf-R¹-R²-CH₂OH (i-b) HOCH₂-R²-R¹-Rf-R¹-R²-CH₂OH (ii-b)

R¹ is a group expressed by the following formula: - (OC₃F₆) _a- (OC₂F₄) _b- (OCF₂) c- (wherein a, b and c are integers not less than 0 but not larger than 200 independently; the sum of a, b and c is at least 1; and the presence order of the repeating units in parentheses is arbitrary in the formula) ;

R² is a group expressed by the following formula: - (Y)d- (CF₂) e- (CH₂) _f-

(wherein Y is an oxygen atom or a divalent polar group; d, e and f are integers not less than 0 but not larger than 50 independently; the sum of d, e and f is at least 1; and the presence order of the repeating units in parentheses is arbitrary in the formula) ] ; and (B-2) a monomer having an active hydrogen and a carbon-carbon double bond, wherein a content of a compound of a non-reactive fluorine-containing polymer expressed by a following general formula (III) : Rf-R¹^-F (III)

3. A process for producing a surface treatment composition comprising a fluorine-containing polymer, which comprises the steps of:

(p) using a raw material mixture which comprises a compound expressed by any of the following general formulas (i) and (ii) : Rf-R¹^-COF (i) FOC-R^R^R^COF (ii)

R¹ is a group expressed by the following formula: - (OC₃F₆) _a- (OC₂F₄) _b- (OCF₂) c-

R² is a group expressed by the following formula: - (Y) _d- (CF₂) _e- (CH₂) _f-

(wherein Y is an oxygen atom or a divalent polar group; d, e and f are integers not less than 0 but not larger than 50 independently; the sum of d, e and f is at least 1; and the presence order of the repeating units in parentheses is arbitrary in the formula) ] ; and a compound expressed by the following general formula (III) :

Rf-R¹^-F (III)

[wherein Rf, R¹ and R² are the same as described above] and subjecting the compound expressed by any of the general formulas (i) and (ii) to an iodination reaction to obtain a reaction mixture which comprises thus generated compound expressed by any of the following general formulas (i-a) and (ii-a) : Rf-R¹^-I (i-a) I-R²-R¹-R²-I (ii-a) [wherein Rf, R¹ and R² are the same as described above] , and the unreacted compound expressed by the general formula

(in);

(q) subjecting the reaction mixture obtained from the step (p) to a purifying operation using column chromatography to remove at least part of the compound expressed by the general formula (III) and thereby obtain a purified material in which a content of the compound expressed by any of the general formulas (i-a) and (ii-a) is higher than that in the reaction mixture; (r) using the purified material obtained from the step (q) and reacting the compound expressed by any of the general formulas (i-a) and (ii-a) with CH₂=CR⁵- (CH₂) _h-SiZ_nR³3-n and P-H

[wherein P represents a hydrolyzable polar group; R³ represents an alkyl group having a carbon number of 1 to 22; n is an integer from 1 to 3; z is a halogen atom;

R⁵ is a hydrogen atom or an alkyl group having a carbon number of 1 to 4; h is an integer not less than 0 but not larger than 2] to obtain as a surface treatment composition a reaction mixture which comprises as a reactive fluorine-containing polymer, thus generated compound expressed by any of the following general formulas (I) and (II) :

[wherein Rf, R¹, R², P, R³ and n are the same as described above ;

R⁴ is a group expressed by the following formula:

(wherein g is an integer not less than 0 but not larger than 50) ;

X is a hydrogen atom, an alkyl group having a carbon number of 1 to 4, a bromine atom, or an iodine atom; m is an integer not less than 1 but not larger than 10], wherein a content of the unreacted compound of a non- reactive fluorine-containing polymer expressed by the general formula (III) in the surface treatment composition is less than 25 mol% (on the basis of the total amount) .

4. A process for producing a surface treatment composition comprising a fluorine-containing polymer, which comprises the steps of:

(s) using a raw material mixture which comprises a compound expressed by any of the following general formulas (i) and (ii) : Rf-R¹^-COF (i)

FOC-R^R^R^COF (ii)

R¹ is a group expressed by the following formula: -(OC₃F₆) _a- (OC₂F₄ )_b- (OCF₂) c-

(wherein a, b and c are integers not less than 0 but not larger than 200 independently; the sum of a, b and c is at least 1; and the presence order of the repeating units in parentheses is arbitrary in the formula) ; R² is a group expressed by the following formula: - (Y)d- (CF₂) _β- (CH₂) _f-

Rf-R¹^-F (III) [wherein Rf, R¹ and R² are the same as described above] and subjecting the compound expressed by any of the general formulas (i) and (ii) to an alcohol-forming reaction to obtain a reaction mixture which comprises thus generated compound expressed by any of the following general formulas (i-b) and (ii-b) :

Rf-R¹-R²-CH₂OH (i-b)

HOCH₂-R²-R¹-R²-CH₂OH ( ii-b)

[wherein Rf , R¹ and R² are the same as described above] , and the unreacted compound expressed by the general formula ( I I I ) ;

(t) subjecting the reaction mixture obtained from the step (s) to a purifying operation using column chromatography to remove at least part of the compound expressed by the general formula (III) and thereby obtain a purified material in which a content of the compound expressed by any of the general formulas (i-b) and (ii-b) is higher than that in the reaction mixture;

(u) using the purified material obtained from the step (t) , and reacting a combination of at least first and second active hydrogen-containing compounds with a triisocyanate of trimerized diisocyanate, wherein the first active hydrogen-containing compound is the compound expressed by any of the general formulas (i-b) and (ii-b) and the second active hydrogen-containing compound is a monomer having an active hydrogen and a carbon-carbon double bond, to obtain as a surface treatment composition a reaction mixture which comprises as a reactive fluorine- containing polymer, thus generated alkene compound, wherein a content of the unreacted compound of a non- reactive fluorine-containing polymer expressed by the general formula (III) in the surface treatment composition is less than 25 mol% (on the basis of the total amount) .

5. A surface-treated article, which comprises a base material, and a layer formed by a surface treatment composition according to claim 1 or 2 on a surface of the base material.

6. The surface-treated article according to claim 5, wherein a deviation angle of the base material from a rotational axis holding the base material in processing of the surface-treated article is 2 degrees or less.