Organopolysiloxane having perfluoropolyether blocks and (meth)acryloyl groups, and method for producing same

Abstract

Provided are: an organopolysiloxane having a perfluoropolyether block and (meth)acryloyl groups, which has a perfluoropolyether group, has an excellent affinity for nonfluorinated organic compounds, and has (meth)acryloyl groups reactive with radical-polymerizable groups and in which the number of organosiloxy units and the number of siloxane units having (meth)acryloyl groups are easy to control; and a method for producing the organopolysiloxane.　This organopolysiloxane has a perfluoropolyether block and (meth)acryloyl groups. This method for producing the organopolysiloxane, which has a perfluoropolyether block and (meth)acryloyl groups, includes a step in which ingredient (a), which is a perfluoropolyether / organopolysiloxane block copolymer, is mixed with ingredient (b), which is a polysiloxane having a (meth)acryloyl group, and a siloxane exchange reaction between the ingredient (a) and the ingredient (b) is conducted in the presence of ingredient (c), which is an acid catalyst.

Description

[Technical field]

[0001] The present invention relates to a reactive organopolysiloxane that has a perfluoropolyether block, has organopolysiloxane blocks at both ends of the molecular chain, and further has (meth)acryloyl groups in the side chain portion of the organopolysiloxane, and whose compatibility and physical properties of the cured product can be easily adjusted, and to a method for producing the same. [Background technology]

[0002] In general, perfluoropolyether group-containing compounds have very low surface free energy and therefore have chemical resistance, lubricity, releasability, water and oil repellency, etc. Taking advantage of these properties, they are widely used industrially as lubricants for magnetic recording media, oil repellents and release agents for precision instruments, water and oil repellents and stain repellents for paper, fiber, glass, resin, etc., cosmetics, protective films, etc.

[0003] However, since the surface free energy of perfluoropolyether group-containing compounds is low, their compatibility and affinity with other substances is very low. When attempts are made to impart the above-mentioned properties by adding perfluoropolyether group-containing compounds to various industrial materials, etc., problems arise in terms of dispersion stability and reactivity, making it difficult to incorporate perfluoropolyether group-containing compounds into various industrial materials, etc. In view of this, a urethane acrylate consisting of a reaction product of a perfluoropolyether group-containing diol and 2-isocyanateethyl methacrylate has been proposed (Patent Document 1).

[0004] On the other hand, polysiloxane compounds also have properties such as water repellency, lubricity, and mold releasability due to their low surface free energy. However, polysiloxane compounds have a better affinity with other substances than perfluoropolyether compounds, and it is possible to further improve the dispersion stability by various modifications. Therefore, polysiloxane compounds can be easily added to various industrial materials to impart silicone properties, and are used as additives for improving performance in a wide range of fields. As a compound having a perfluoropolyether group and a polysiloxane chain, there is a perfluoropolyether-modified polysiloxane compound (Patent Document 2). However, when the fluorine modification rate of a polysiloxane compound is increased in an attempt to improve the properties of the perfluoropolyether group, the affinity for other industrial materials is significantly reduced, and problems may arise in terms of dispersion stability, reactivity, and the like. In view of this, perfluoropolyether-organopolysiloxane block copolymers have been developed that have the properties of both perfluoropolyether and polysiloxane and have excellent affinity with non-fluorinated organic compounds (Patent Documents 3 and 4). In addition, perfluoropolyether-organopolysiloxane block copolymers having (meth)acryloyl groups in the siloxane blocks have also been developed that can impart water and oil repellency, etc. by blending them with radical curable compositions (Patent Document 5). However, the number of siloxane units and polymerizable groups that can be introduced is limited, making it difficult to control the compatibility with the curable composition and the mechanical properties of the resulting cured product. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 11-349651 [Patent Document 2] JP 2006-321764 A [Patent Document 3] JP 2008-88412 A [Patent Document 4] JP 2011-21158 A [Patent Document 5] JP 2011-241190 A Summary of the Invention [Problem to be solved by the invention]

[0006] The perfluoropolyether-organopolysiloxane block copolymers disclosed in Patent Documents 3 and 4 have good affinity with non-fluorinated organic compounds, but since they do not have radically polymerizable groups, they cannot react with radically polymerizable compounds, and therefore cannot impart sustained water and oil repellency, etc., even when incorporated into a radically curable composition. On the other hand, the urethane acrylate consisting of a reaction product of a perfluoropolyether group-containing diol and 2-isocyanateethyl methacrylate disclosed in Patent Document 1 does not contain polysiloxane, and due to the water- and oil-repellent properties of the perfluoropolyether group, it has low affinity with non-fluorinated organic compounds, and the components that can be blended and the applications are limited. The perfluoropolyether-organopolysiloxane block copolymer having a radically polymerizable group disclosed in Patent Document 5 has good affinity with non-fluorinated organic compounds, but the number of organosiloxy units and (meth)acryloyl groups that can be introduced is limited, making it difficult to control the compatibility with the curable composition and the mechanical properties of the resulting cured product. Therefore, an object of the present invention is to provide an organopolysiloxane having a perfluoropolyether block and a (meth)acryloyl group, which has a perfluoropolyether group, has excellent affinity with non-fluorinated organic compounds, has a (meth)acryloyl group capable of reacting with a radically polymerizable group, and in which the number of organosiloxy units and the number of siloxane units having a (meth)acryloyl group are easily controlled, and a method for producing the same. [Means for solving the problem]

[0007] As a result of intensive research aimed at solving the above problems, the present inventors have found that the above-mentioned object can be achieved by the following organopolysiloxane having a perfluoropolyether block and a (meth)acryloyl group, and a method for producing the same, and have thus completed the present invention. That is, the present invention is as follows.

[0008] [1] An organopolysiloxane having a perfluoropolyether block and a (meth)acryloyl group, represented by the following formula (1): [ka] [In formula (1), Rf is expressed by the following formula (2) [ka] (In formula (2), z is a number from 1 to 4, v, w, x, and y are each independently a number from 0 to 200, and v+w+x+y=3 to 200. Each repeating unit may be linear or branched. The arrangement order of each repeating unit is not limited and may be random or block.) is a perfluoropolyether block represented by W1 is expressed by the following formula (A): [ka] (In formula (A), R 1 R is independently a group selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. 2 is a monovalent group having a (meth)acryloyl group. p1 and q1 are each a number from 0 to 1,000. The arrangement order of each repeating unit is not limited and may be random or block. is a divalent organopolysiloxane block represented by W2 is independently represented by the following formula (B): [ka] (In formula (B), R 1 R is independently a group selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. 2 R is a monovalent group having a (meth)acryloyl group. 1 Each ' is independently a group selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. p2 and q2 are each a number from 0 to 1,000. The arrangement order of each repeating unit is not limited and may be random or block. is a monovalent organopolysiloxane block represented by the formula: However, the number q1 of the siloxane units having a (meth)acryloyl group in the above formula (A) and the number q2 of the siloxane units having a (meth)acryloyl group in the above formula (B) are not 0 at the same time, Q is a divalent organic group having 2 to 12 carbon atoms, and in the above formula (1), Q is bonded to either the carbon atom at the end of Rf, the silicon atom at the end of W1, or the silicon atom at the end of W2; g is a number greater than or equal to 0.] [2] The organopolysiloxane having perfluoropolyether blocks and (meth)acryloyl groups according to [1], which has a number average molecular weight of 3,000 to 500,000 and an organopolysiloxane block content in one molecule of 50% or more. [3] R 2 The organopolysiloxane having a perfluoropolyether block and a (meth)acryloyl group according to [1] or [2], wherein the monovalent group having a (meth)acryloyl group represented by the following formula (3) is a group represented by the following formula (3): [ka] (In formula (3), R 3 is a hydrogen atom or a methyl group. X is an oxygen atom or a group represented by -NH-. R 4 is an alkylene group having 2 to 4 carbon atoms. m is a number from 0 to 60, and n is a number from 3 to 8. [4] The organopolysiloxane having a perfluoropolyether block and a (meth)acryloyl group according to any one of [1] to [3], wherein the perfluoropolyether block represented by Rf is a group represented by the following formula (4): [ka] (In formula (4), v and w are each a number from 0 to 200, with the proviso that v+w=3 to 200. The repeating unit of (OC2F4) may be linear or branched. The arrangement order of the repeating units is not limited, and may be random or block.) [5] Component (a): a perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (5), (b) component: polysiloxane having a (meth)acryloyl group is mixed, (c) component: in the presence of an acid catalyst A method for producing an organopolysiloxane having a perfluoropolyether block represented by the following formula (1) and a (meth)acryloyl group, comprising an exchange reaction step between the siloxanes of components (a) and (b): [ka] [In formula (1), Rf is expressed by the following formula (2) [ka] (In formula (2), z is a number from 1 to 4, v, w, x, and y are each independently a number from 0 to 200, and v+w+x+y=3 to 200. Each repeating unit may be linear or branched. The arrangement order of each repeating unit is not limited and may be random or block.) is a perfluoropolyether block represented by W1 is independently represented by the following formula (A): [ka] (In formula (A), R 1 R is independently a group selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. 2 are independently a monovalent group having a (meth)acryloyl group. p1 and q1 are each a number from 0 to 1,000. The arrangement order of each repeating unit is not limited and may be random or block. is a divalent organopolysiloxane block represented by W2 is independently represented by the following formula (B): [ka] (In formula (B), R 1 R is independently a group selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. 2 R is a monovalent group having a (meth)acryloyl group. 1 Each ' is independently a group selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. p2 and q2 are each a number from 0 to 1,000. The arrangement order of each repeating unit is not limited and may be random or block. is a monovalent organopolysiloxane block represented by the formula: However, the number q1 of the siloxane units having a (meth)acryloyl group in the above formula (A) and the number q2 of the siloxane units having a (meth)acryloyl group in the above formula (B) are not 0 at the same time, Q is the same as above, and in the above formula (1), Q is bonded to either the terminal carbon atom of Rf, the terminal silicon atom of W1, or the terminal silicon atom of W2; g is a number greater than or equal to 0.] [ka] [In formula (5), Rf is a perfluoropolyether block represented by formula (2) above, and W3 each independently represents a group represented by the following formula (A'): [ka] (In formula (A'), R 1 is the same as above. p' is a number between 0 and 1,000. is a divalent organopolysiloxane block represented by W4 each independently represents the following formula (B'): [ka] (In formula (B'), R 1 , R 1 ' is the same as above. p" is a number between 0 and 1,000. is a monovalent organopolysiloxane block represented by the formula: Q is the same as above. In addition, in the above formula (5), Q is bonded to either the carbon atom at the end of Rf, the silicon atom at the end of W3, or the silicon atom at the end of W4, g' is a number greater than or equal to 0.] [6] The method for producing an organopolysiloxane having a perfluoropolyether block and a (meth)acryloyl group according to [5], wherein the component (b) is one or more polysiloxanes having a (meth)acryloyl group represented by the following formula (6) or the following formula (7). [ka] (In formula (6), R 1 R is independently a group selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. 5 are independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -SiR 1 3(R 1 is the same as above.) R 3 is a hydrogen atom or a methyl group. X is an oxygen atom or a group represented by -NH-. R 4 is an alkylene group having 2 to 4 carbon atoms. m is a number from 0 to 60, and n is a number from 3 to 8. p3 is a number from 0 to 1,000, and q3 is a number from 1 to 100. [ka] (In formula (7), R 1 , R 3 , R 4 , X, m, and n are the same as above. p4 is a number from 0 to 6, and q4 is a number from 1 to 8, provided that 3≦p4+q4≦14. [7] The method for producing an organopolysiloxane having perfluoropolyether blocks and (meth)acryloyl groups according to [5] or [6], further comprising the step of adding component (d): one or more polysiloxanes selected from polysiloxanes represented by the following formula (8) and the following formula (9): [ka] (In formula (8), R 1 are independently selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. r1 is a number from 3 to 10. [ka] (In formula (9), R 1 is the same as above. r2 is a number between 0 and 5,000.) [8] The method for producing an organopolysiloxane having perfluoropolyether blocks and (meth)acryloyl groups according to any one of [5] to [7], wherein the component (c) is one or more acid catalysts selected from sulfuric acid, methanesulfonic acid, and trifluoromethanesulfonic acid. [9] The method for producing an organopolysiloxane having a perfluoropolyether block and a (meth)acryloyl group according to any one of [5] to [8], further comprising carrying out an exchange reaction step between the siloxanes of the components (a) and (b) in the presence of an organic solvent as the component (e). Effect of the Invention

[0009] The organopolysiloxane of the present invention has perfluoropolyether blocks and organopolysiloxane blocks at both ends of the molecular chain, and has a high organopolysiloxane block content, making it highly compatible with non-fluorine-based organic compounds. In addition, since it has (meth)acryloyl groups, it can react with radically polymerizable compounds, and the resulting cured product is less likely to produce non-uniform parts or cloudy parts. Furthermore, in the organopolysiloxane of the present invention, the number of organosiloxy units and the number of siloxane units having a (meth)acryloyl group can be easily controlled, and therefore it is also possible to easily control the compatibility with the curable composition and the mechanical properties of the resulting cured product. Therefore, the organopolysiloxane of the present invention is useful as a surface modifier for non-fluorine-containing organic resins. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present invention will now be described in more detail.

[0011] The organopolysiloxane of the present invention is represented by the following formula (1), in which perfluoropolyether blocks (Rf) and organopolysiloxane blocks (W2 or W1) exist alternately. [ka]

[0012] Since W2 and / or W1 have a (meth)acryloyl group, the organopolysiloxane of the present invention represented by formula (1) is capable of reacting with a radically polymerizable compound.

[0013] The organopolysiloxane of the above formula (1) preferably has an organopolysiloxane block content in one molecule of 50% or more and 99% or less, and more preferably 60% or more and 90% or less. When the organopolysiloxane block content is equal to or more than the above lower limit, the compatibility with non-fluorine-based organic compounds is excellent, and when it is equal to or less than the above upper limit, the properties of the perfluoropolyether group are easily expressed. The organopolysiloxane block content is determined by the following formula (1): 1 It is a value calculated by calculating the molar ratio of perfluoropolyether block Rf having a known molecular weight and organosiloxy unit from the integral ratio of the peak derived from alkylene of Q in the above formula (1) and the peak derived from organic group on silicon atom in W2 and W1 in H-NMR spectrum, and converting this molar ratio into the ratio of molecular weight. Note that, since organopolysiloxane of formula (1) usually has a distribution in structure, the above organopolysiloxane block content is the average value per molecule.

[0014] At least one of the organopolysiloxane blocks W1 and W2 has a siloxane unit having a (meth)acryloyl group represented by the following formula (10). [ka]

[0015] In formula (10), R 1 is a group selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms, and is preferably a methyl group or a phenyl group. L is a divalent linking group having 1 to 150 carbon atoms, which may contain one or more selected from an oxygen atom and a nitrogen atom, and is preferably a divalent linking group which may contain an oxygen atom having 2 to 5 carbon atoms. X is an oxygen atom or a group represented by -NH-, and is preferably an oxygen atom. R 3 is a hydrogen atom or a methyl group.

[0016] The siloxane unit having a (meth)acryloyl group is present in the above formula (1) at least one, and preferably three or more from the viewpoint of reactivity. The siloxane units of formula (10) in the organopolysiloxane blocks W1 and W2 may be different from each other. In the above formula (1), the organopolysiloxane block W1 is a divalent group represented by the following general formula (A). [ka]

[0017] In formula (A), R 1 R is independently a group selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms, and is preferably a methyl group or a phenyl group. 2 are independently a monovalent group having a (meth)acryloyl group, and are preferably a group represented by the following formula (3). [ka]

[0018] In the above formula (3), R 3 is a hydrogen atom or a methyl group. X is an oxygen atom or a group represented by -NH-, preferably an oxygen atom. R 4 is an alkylene group having 2 to 4 carbon atoms, and preferably an alkylene group having 2 or 3 carbon atoms. m is a number from 0 to 60, and preferably a number from 0 to 12. n is a number from 3 to 8, and preferably a number from 3 to 4.

[0019] Each of p1 and q1 is a number from 0 to 1,000, preferably a number from 0 to 500, and more preferably a number from 0 to 200. The arrangement order of the repeating units is not limited, and may be random or block.

[0020] Examples of the group represented by formula (A) include groups represented by the following formulae (11) to (14), etc. However, the group represented by formula (A) is not limited to the groups represented by the following formulae. [ka]

[0021] In the formula (1), the organopolysiloxane block W2 is a monovalent group represented by the following general formula (B). [ka]

[0022] In the above formula (B), R 1 R is independently a group selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. 2 R is a monovalent group having a (meth)acryloyl group. 1 R' is independently a group selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. 1 ' is preferably an alkyl group having 1 to 18 carbon atoms or an aralkyl group having 7 to 18 carbon atoms, more preferably an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, or an octyl group, or an aralkyl group such as a benzyl group, a 2-phenylethyl group, or a 2-phenylpropyl group. p2 and q2 are each a number from 0 to 1,000, preferably a number from 0 to 500, and more preferably a number from 0 to 200. The arrangement order of each repeating unit is not limited, and may be random or block. However, the number q1 of the siloxane unit having a (meth)acryloyl group in the above formula (A) and the number q2 of the siloxane unit having a (meth)acryloyl group in the above formula (B) are not 0 at the same time.

[0023] Examples of the group represented by formula (B) include groups represented by the following formulae (15) to (18), etc. However, the group represented by formula (B) is not limited to the groups represented by the following formulae. [ka]

[0024] The perfluoropolyether block Rf in the above formula (1) is represented by the following general formula (2). [ka]

[0025] In formula (2), z is a number from 1 to 4, v, w, x and y are each independently a number from 0 to 200, preferably a number from 0 to 50, provided that v+w+x+y=3 to 200, preferably 10 to 50, and each repeating unit may be linear or branched, and the arrangement order of each repeating unit is not limited and may be random or block.

[0026] Examples of the repeating units of the perfluoropolyether block Rf represented by the above formula (2) include the following repeating units. [ka]

[0027] Among these, a perfluoropolyether block of the following formula (4) in which z=1 and x and y are 0 in the above formula (2) is preferred because it has excellent compatibility with non-fluorine-based organic compounds. [ka]

[0028] In formula (4), v and w are each a number from 0 to 200, and preferably a number from 0 to 50, with the proviso that v+w=3 to 200, and preferably 10 to 50. The repeating unit of (OC2F4) may be linear or branched, and the arrangement order of each repeating unit is not limited and may be random or block.

[0029] The perfluoropolyether blocks represented by the above formulas usually have a distribution in structure, and v, w, x and y are each average values ​​per molecule.

[0030] In the formula (1), Q is a divalent organic group having 2 to 12 carbon atoms, preferably 3 to 6 carbon atoms. In addition, in the formula (1), Q is bonded to either the carbon atom at the end of Rf, the silicon atom at the end of W1, or the silicon atom at the end of W2. Q may contain an oxygen atom or a nitrogen atom. Specific examples include an ether bond, an ester bond, an amide bond, and a secondary amino group. Specific examples of Q include the following groups. [ka] (In the formula, * represents a free group bonded to Rf, and ** represents a free group bonded to W1 or W2.)

[0031] Among the specific examples of Q above, the following is particularly preferred in that it is easy to link the organopolysiloxane block and the perfluoropolyether block: * -CH2OCH2CH2CH2- ** is preferred.

[0032] The number average molecular weight of the organopolysiloxane of the formula (1) is preferably 3,000 to 500,000. When the number average molecular weight is within this range, the organopolysiloxane tends to have excellent solubility in non-fluorine-based organic compounds and is easy to handle. In this specification, the number average molecular weight is a polystyrene-equivalent value determined by GPC (gel permeation chromatography) measurement under the following conditions (the same applies hereinafter).

[0033] [Measurement conditions] Developing solvent: toluene Flow rate: 0.6mL / min Detector: Refractive index detector (RI) Column: TSK Guardcolumn SuperH-H TSKgel SuperH5000(6.0mmI.D.×15cm×1) TSKgel SuperH4000(6.0mmI.D.×15cm×1) TSKgel SuperH3000(6.0mmI.D.×15cm×1) TSKgel SuperH2000(6.0mmI.D.×15cm×1) (All manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 50 μL (toluene solution with a concentration of 0.3% by mass)

[0034] In the formula (1), g is a number of 0 or more, and is preferably a number such that the number average molecular weight of the organopolysiloxane of formula (1) is 3,000 to 500,000. Specifically, g is preferably a number of 0 to 50, and more preferably a number of 0 to 10.

[0035] [Method of producing organopolysiloxane] The present invention also relates to a method for producing the organopolysiloxane having the above-mentioned perfluoropolyether block and (meth)acryloyl group. The organopolysiloxane of the present invention can be produced by the following two methods.

[0036] [Manufacturing method 1] The organopolysiloxane represented by the above formula (1) can be obtained by mixing component (a): a perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (5), component (b): a polysiloxane having a (meth)acryloyl group, and component (c): an acid catalyst, and carrying out an exchange reaction between the siloxanes of components (a) and (b). [ka]

[0037] Component (a): The perfluoropolyether-organopolysiloxane block copolymer represented by formula (5) can be produced by using the method described in Japanese Patent No. 4,900,854, or the like. In detail, one or more of organohydrogenpolysiloxanes having one hydrosilyl group at one end for deriving W4 and organohydrogenpolysiloxanes having one hydrosilyl group at each end for deriving W3 and / or W4 are hydrosilylated with a compound having a group Q' having an unsaturated group at both ends of Rf represented by the following formula (19) in the presence of a platinum catalyst. When only an organohydrogenpolysiloxane having one hydrosilyl group at each end is hydrosilylated with a compound represented by the following formula (19), a non-substituted or substituted terminally unsaturated hydrocarbon having 1 to 18 carbon atoms is further hydrosilylated to inactivate the terminal hydrosilyl group. By inactivating the terminal hydrosilyl group, gelation during the exchange reaction between siloxanes can be prevented. [ka]

[0038] In the above formula (19), Rf is a perfluoropolyether block represented by the above formula (2), and Q' is, for example, a group containing an unsaturated group as shown below. [ka]

[0039] In the above formula (5), Rf is a perfluoropolyether block represented by the above formula (2), and m is a number of 0 or more. In the above formula (5), the organopolysiloxane blocks W3 are each independently a divalent group represented by the following general formula (A'). [ka] In the above formula (A'), R 1 is the same as above. p' is a number from 0 to 1,000, preferably a number from 0 to 500, and more preferably a number from 0 to 200.

[0040] In the above formula (5), the organopolysiloxane block W4 is a monovalent group represented by the following general formula (B'). [ka]

[0041] In the above formula (B'), R 1 , R 1 p'' is a number from 0 to 1,000, preferably a number from 0 to 500, and more preferably a number from 0 to 200.

[0042] In the above formula (5), examples of organohydrogenpolysiloxanes having one hydrosilyl group at one end for deriving W4 include, but are not limited to, the following siloxanes: [ka] (In the formula, the arrangement order of the repeating units is not limited, and may be random or block.)

[0043] In the above formula (5), examples of organohydrogenpolysiloxanes having one hydrosilyl group at each end for deriving W3 and / or W4 include, but are not limited to, the following siloxanes: [ka] (In the formula, the arrangement order of the repeating units is not limited, and may be random or block.)

[0044] In the above formula (5), Q is a divalent organic group having 2 to 12 carbon atoms, preferably 3 to 6 carbon atoms. In addition, in the above formula (5), Q is bonded to either the carbon atom at the end of Rf, the silicon atom at the end of W3, or the silicon atom at the end of W4. Q may contain an oxygen atom or a nitrogen atom. Specific examples of Q include an ether bond, an ester bond, an amide bond, and a secondary amino group. Specific examples of Q include the following groups. [ka] (In the formula, * represents a free group bonded to Rf, and ** represents a free group bonded to W3 or W4.)

[0045] Among the specific examples of Q above, the following is particularly preferred in that it is easy to link the organopolysiloxane block and the perfluoropolyether block: * -CH2OCH2CH2CH2- ** is preferred.

[0046] Component (b): polysiloxane having a (meth)acryloyl group is a polysiloxane represented by the following formula (6) or the following formula (7). [ka] (In formula (6), R 1 and R 4 is the same as that described in the above formula (A) and formula (3). 5 are independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -SiR 1 3(R 1 is the same as above. ) and is preferably a methyl group or -Si(CH3)3. R 3 is a hydrogen atom or a methyl group. X is an oxygen atom or a group represented by -NH-, preferably an oxygen atom. m is a number from 0 to 60, preferably 0 to 12. n is a number from 3 to 8, preferably 3 to 4. p3 is a number from 0 to 1,000, preferably 0 to 500. q3 is a number from 1 to 100, preferably 1 to 10. [ka] (In formula (7), R 1 , R 3 , R 4 X, m, and n are the same as those defined in the formula (6). p4 is a number from 0 to 6, and preferably 0. q4 is a number from 1 to 8, and preferably a number from 1 to 5, with the proviso that 3≦p4+q4≦14.

[0047] Examples of polysiloxanes represented by the above formula (6) include polysiloxanes of the following formula, but are not limited to these. [ka]

[0048] Examples of polysiloxanes represented by the above formula (7) include polysiloxanes of the following formula, but are not limited to these. [ka]

[0049] The acid catalyst (c) used in Production Method 1 is not particularly limited as long as it can hydrolyze the siloxane bonds in the above components (a) and (b). Preferred are sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, and the like.

[0050] In the method for producing the organopolysiloxane of formula (1) above (production method 1), component (d): one or more polysiloxanes represented by formulas (8) and (9) below may be added as necessary to carry out an exchange reaction between siloxanes. By adding and reacting component (d), it is possible to control the number of organosiloxy units in formula (1) above, making it easier to control the compatibility with non-fluorine-based organic compounds. [ka] (In formula (8), R 1is the same as above. r1 is a number from 3 to 10, and preferably a number from 3 to 8. [ka] (In formula (9), R 1 is the same as above. r2 is a number from 0 to 5,000, and preferably a number from 2 to 1,000.

[0051] Of the components (d), the cyclic polysiloxanes represented by the formula (8) are preferred, with octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane being particularly preferred.

[0052] In the method for producing the organopolysiloxane of the above formula (1) by the exchange reaction between the siloxanes (production method 1), the exchange reaction between the siloxanes may be carried out by optionally adding component (e): an organic solvent. This reaction can be carried out without a solvent, but by adding an organic solvent, the perfluoropolyether-organopolysiloxane block copolymer of component (a) and the polysiloxanes of components (b) and (d) become more compatible with each other, and the exchange reaction between the siloxanes can be efficiently carried out.

[0053] Examples of the organic solvent (e) above include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as pentane, hexane and heptane; ketones such as methyl ethyl ketone and diisopropyl ketone; alcohols such as 1-propanol, 2-propanol and 1-butanol; and fluorinated aromatic hydrocarbons such as (trifluoromethyl)benzene and 1,3-bis(trifluoromethyl)benzene. Among these, 1,3-bis(trifluoromethyl)benzene is preferred because it has good compatibility with the perfluoropolyether-organopolysiloxane block copolymer (a) represented by the above formula (5) and the polysiloxanes (b) and (d).

[0054] In the above-mentioned Production Method 1, the reaction temperature is not particularly limited as long as it is a temperature at which the exchange reaction of the siloxane of the above-mentioned component (a): the perfluoropolyether-organopolysiloxane block copolymer with the siloxanes of the components (b) and (d) proceeds, but is preferably 0 to 60° C. If the reaction temperature is equal to or higher than the above-mentioned lower limit, the reaction tends to proceed quickly, and if the reaction temperature is equal to or lower than the above-mentioned upper limit, side reactions are unlikely to occur. In the production method 1, the reaction time is not particularly limited as long as it is a time that allows the siloxane exchange reaction of the above component (a) with components (b) and (d) to reach an equilibrium state, but is preferably 4 to 24 hours.

[0055] The organopolysiloxane of formula (1) obtained by production method 1 above usually has a distribution in structure, and in formula (1), g is the average value per molecule.

[0056] [Manufacturing method 2] The organopolysiloxane of the present invention can also be produced by the method described below. The organopolysiloxane represented by the above formula (1) can be obtained by carrying out a hydrosilylation reaction between component (f): an organohydrogenpolysiloxane having a perfluoropolyether block represented by the following formula (20), and component (g): a compound having a (meth)acryloyl group and a terminal carbon-carbon double bond other than a (meth)acryloyl group, in the presence of component (h): a hydrosilylation reaction catalyst. [ka] In the above formula (20), Rf is the same as defined above, and each organopolysiloxane block W5 is independently a divalent group represented by the following general formula (A″). [ka]

[0057] In the above formula (A"), R 1is the same as above. Furthermore, a1 and b1 are each a number from 0 to 1,000, and preferably a number from 0 to 200. The arrangement order of each repeating unit is not limited, and may be random or block.

[0058] In formula (20), each organopolysiloxane block W6 is independently a monovalent group represented by the following general formula (B″). [ka]

[0059] In the above formula (B"), R 1 , R 1 and a2' are the same as above. Furthermore, a2 and b2 are each a number from 0 to 1,000, and preferably a number from 0 to 200. The arrangement order of each repeating unit is not limited, and may be random or block. However, the number b1 of hydrogensiloxane units in the above formula (A") and the number b2 of hydrogensiloxane units in the above formula (B") are not 0 at the same time.

[0060] In the above formula (20), Q is a divalent organic group having 2 to 12 carbon atoms. In addition, in the above formula (20), Q is bonded to either the carbon atom at the end of Rf, the silicon atom at the end of W5, or the silicon atom at the end of W6, and g'' is a number of 0 or more.

[0061] Component (f): Organohydrogenpolysiloxane having a perfluoropolyether block represented by formula (20) can be produced by the following method or the like. In detail, the above-mentioned (a) component: a perfluoropolyether-organopolysiloxane block copolymer represented by formula (5), (i) component: an organohydrogenpolysiloxane, (c) component: an acid catalyst, and, if necessary, (d) component: one or more polysiloxanes represented by formulas (8) and (9) are mixed together to carry out an exchange reaction between the siloxanes of the component (a), the component (i), and the component (d).

[0062] The above-mentioned component (i): organohydrogenpolysiloxane may be any of linear, branched, and cyclic, and examples thereof include the following siloxanes. [ka]

[0063] An example of the above component (g): a compound having a (meth)acryloyl group and a terminal carbon-carbon double bond other than the (meth)acryloyl group, is a compound represented by the following formula (21). [ka]

[0064] In formula (21), R 3 is a hydrogen atom or a methyl group. X is an oxygen atom or a group represented by -NH-, preferably an oxygen atom. R 4 is an alkylene group having 2 to 4 carbon atoms, and preferably an alkylene group having 2 or 3 carbon atoms. m' is a number from 0 to 60, and preferably a number from 0 to 12. n is a number from 3 to 8, and preferably a number from 3 to 4.

[0065] The above-mentioned component (h): hydrosilylation catalyst is, for example, a platinum, palladium, rhodium, or ruthenium catalyst, preferably a platinum catalyst. Examples of platinum catalysts include chloroplatinic acid, alcohol or aldehyde solutions of chloroplatinic acid, complexes of chloroplatinic acid with various olefins or vinylsiloxanes, and complexes of platinum with various olefins or vinylsiloxanes. The amount of the above component (h): hydrosilylation reaction catalyst used may be a so-called catalytic amount, and is preferably 0.1 to 200 ppm in terms of metal atom weight based on the total amount of the above components (f) and (g).

[0066] In the method for producing the organopolysiloxane of the above formula (1) (production method 2) by the hydrosilylation reaction of the above components (f) and (g), the hydrosilylation reaction may be carried out by optionally adding component (j): an organic solvent. This reaction can be carried out without a solvent, but adding an organic solvent is preferred because it makes the component (f): an organohydrogenpolysiloxane having a perfluoropolyether block and the component (g): a compound having a (meth)acryloyl group and a terminal unsaturated bond other than a (meth)acryloyl group more compatible with each other, allowing the hydrosilylation reaction to proceed efficiently. Examples of the organic solvent (j) above include aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol, 2-propanol and 1-butanol; and fluorinated aromatic hydrocarbons such as (trifluoromethyl)benzene and 1,3-bis(trifluoromethyl)benzene. Toluene is preferred because it has good compatibility with the organohydrogenpolysiloxane having a perfluoropolyether block represented by the above formula (8) (f) above, and the compound having a (meth)acryloyl group and a terminal unsaturated bond other than a (meth)acryloyl group (g). The amount of the organic solvent used as component (j) is not particularly limited as long as the components (f) and (g) are compatible with each other, but is preferably 10 to 300 mass % of the total of components (f) and (g).

[0067] In the above-mentioned Production Method 2, the quantitative ratio of component (f): an organohydrogenpolysiloxane having a perfluoropolyether block, and component (g): a compound having a (meth)acryloyl group and a terminal unsaturated bond other than a (meth)acryloyl group, is preferably such that the amount of component (g) relative to the hydrosilyl group in component (f) is 1.0 to 2.0 equivalents, and more preferably 1.0 to 1.5 equivalents. In Production Method 2, the reaction temperature is not particularly limited as long as it is a temperature at which the above components (f) and (g) react, but is preferably 50 to 100° C. If the reaction temperature is equal to or higher than the above lower limit, the reaction tends to proceed quickly, and if the reaction temperature is equal to or lower than the above upper limit, polymerization of the (meth)acryloyl group is unlikely to occur. EXAMPLES

[0068] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, the number average molecular weight is a polystyrene equivalent value determined by GPC measurement under the above-mentioned measurement conditions. In the following examples, the number of repeating units (g) is 29 In the Si-NMR spectrum, the Si(R 1' The integral value M derived from Si in the )3-O- structure and the -Q-Si(R 1 )2-O-structure Si-derived integral value M', and g = (M' / M)-1.

[0069] [Example 1] Synthesis of organopolysiloxane (1-1) In a reaction vessel, 6.7 g of perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (5-1) synthesized according to Patent No. 4,900,854, 0.86 g of polysiloxane having a methacryloyl group represented by the following formula (6-1), and 7.5 g of 1,3-bis(trifluoromethyl)benzene were added and stirred at 25°C for 5 minutes, 15 mg of trifluoromethanesulfonic acid was added, and the mixture was further stirred at 60°C for 7 hours. Next, 100 mg of Kyoward 500 (manufactured by Kyowa Chemical Industry Co., Ltd.), an adsorbent, was added for the purpose of neutralizing trifluoromethanesulfonic acid, and the mixture was stirred at 25°C for 3 hours. The resulting mixture was filtered, and the solvent 1,3-bis(trifluoromethyl)benzene was distilled off under reduced pressure to obtain 5.5 g of a liquid product. [ka] (In formula (5-1), v / w is 0.73 and v+w is 19.) [ka] (The formula (6-1) has a distribution in the structure, and q6 is a number from 2 to 8.) [Table 1] [Table 2] [Table 3]

[0070] From the above results, it was found that the obtained organopolysiloxane had a structure represented by the following formula (1-1), and the organopolysiloxane block content in the molecule was 68%. In addition, the number average molecular weight in terms of polystyrene measured by GPC was 4,900. [ka]

[0071] [Example 2] Synthesis of organopolysiloxane (1-2) In a reaction vessel, 11.3 g of a perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (5-2), 1.72 g of a polysiloxane having an acryloyl group represented by the following formula (6-2), and 11.3 g of 1,3-bis(trifluoromethyl)benzene were placed and stirred at 25° C. for 5 minutes, 40 mg of trifluoromethanesulfonic acid was added, and the mixture was further stirred at 55° C. for 5 hours. Next, 260 mg of Kyoward 500 (manufactured by Kyowa Chemical Industry Co., Ltd.), an adsorbent, was added for the purpose of neutralizing trifluoromethanesulfonic acid, and the mixture was stirred at 25° C. for 3 hours. The resulting mixture was filtered, and the solvent 1,3-bis(trifluoromethyl)benzene was distilled off under reduced pressure to obtain 8.8 g of a liquid product. [ka] [Table 4] [Table 5] [Table 6]

[0072] From the above results, it was found that the obtained organopolysiloxane had a structure represented by the following formula (1-2), and the organopolysiloxane block content in the molecule was 84%. In addition, the number average molecular weight in terms of polystyrene measured by GPC was 7,380. [ka]

[0073] [Example 3] Synthesis of organopolysiloxane (1-3) 0.76g of 2-allyloxyethyl methacrylate and 0.76g of toluene were placed in a reaction vessel and stirred at 80°C for 5 minutes, and 0.01g of a toluene solution of a platinum vinylsiloxane complex was added. Next, a mixed solution of 3.8g of an organohydrogenpolysiloxane having a perfluoropolyether block represented by the following formula (20-1) and 3.8g of toluene was added dropwise at 80°C over 1 hour, and further stirred at 80°C for 1.5 hours. Next, the toluene solvent was distilled off under reduced pressure to obtain 4.3g of a liquid product. [ka] [Table 7] [Table 8] [Table 9]

[0074] From the above results, it was found that the obtained organopolysiloxane had a structure represented by the following formula (1-3), and the organopolysiloxane block content in the molecule was 75%. In addition, the number average molecular weight in terms of polystyrene measured by GPC was 6,350. [ka]

[0075] [Example 4] Synthesis of organopolysiloxane (1-4) 4.1 g of organohydrogenpolysiloxane having a perfluoropolyether block represented by the following formula (20-2) and 0.23 g of 2-allyloxyethyl methacrylate were placed in a reaction vessel and stirred at 80°C for 5 minutes, and 0.01 g of a toluene solution of a platinum vinylsiloxane complex was added. After stirring at 80°C for 2 hours, the mixture was distilled under reduced pressure to obtain 4.2 g of a liquid product. [ka] [Table 10] [Table 11] [Table 12]

[0076] From the above results, it was found that the obtained organopolysiloxane had a structure represented by the following formula (1-4), and the organopolysiloxane block content in the molecule was 87%. In addition, the number average molecular weight in terms of polystyrene measured by GPC was 11,500. [ka]

[0077] [Comparative Example 1 (Organopolysiloxane Block Content in Molecule: 0%)] In the presence of dry air, 15.5 g of 2-isocyanate ethyl methacrylate and 0.005 g of dioctyltin laurate were placed in a reaction vessel and stirred at 25°C for 5 minutes. Then, 100 g of perfluoropolyether diol (manufactured by Solvay Specialty Polymers, trade name: Fomblin D2) was added dropwise at 50°C over 1 hour. After the dropwise addition, the mixture was stirred at 50°C for 5 hours. The IR spectrum of the reaction product showed that -1The peak derived from the -N=C=O group, which appears in the graph, disappeared, and a perfluoropolyether having methacryl groups at both ends was obtained.

[0078] [Comparative Example 2 (Organopolysiloxane Block Content in Molecule: 24%)] 0.68g of 2-allyloxyethyl methacrylate and 0.68g of 1,3-bis(trifluoromethyl)benzene were placed in a reaction vessel and stirred at 80°C for 5 minutes, and 0.01g of a toluene solution of a platinum vinylsiloxane complex was added. Next, a mixed solution of 4.0g of an organohydrogenpolysiloxane having a perfluoropolyether block represented by the following formula (22) and 4.0g of 1,3-bis(trifluoromethyl)benzene was added dropwise over 1 hour at 80°C, and further stirred at 80°C for 1.5 hours. Next, the solvent 1,3-bis(trifluoromethyl)benzene was distilled off under reduced pressure to obtain 4.4g of an organopolysiloxane represented by the following formula (23). [ka] (wherein v / w is 0.73 and v+w is 19.) [ka] (In the formula, Rf is the same as above.)

[0079] [Evaluation of solubility in non-fluorinated organic compounds] 1 g of each of the organopolysiloxanes in the above Examples and Comparative Examples was mixed with 9 g of the following non-fluorine-based organic compound, and the mixture was visually observed to evaluate the solubility according to the following criteria. Evaluation criteria ○: The mixture is transparent. ×: The mixture is separated into two phases or is cloudy.

[0080] [Table 13]

[0081] The results in Table 13 show that the organopolysiloxane of the present invention having a perfluoropolyether block and a (meth)acryloyl group has better solubility in non-fluorine-based organic compounds than the conventional organopolysiloxane having a low siloxane content. In addition, the organopolysiloxane of the present invention having a perfluoropolyether block and a (meth)acryloyl group can easily have the number of organosiloxy units or the number of siloxane units having a (meth)acryloyl group, and therefore it is possible to control the compatibility and the mechanical properties of the cured product, and the organopolysiloxane is useful as an additive for a resin composition, etc.

Claims

1. An organopolysiloxane having a perfluoropolyether block and a (meth)acryloyl group, represented by the following formula (1): 【Chemistry 1】 [In formula (1), Rf is represented by the following formula (2) 【Chemistry 2】 (In formula (2), z is a number from 1 to 4, v, w, x and y are each independently a number from 0 to 200, and v+w+x+y=3 to 200. Each repeating unit may be linear or branched. The arrangement order of each repeating unit is not limited and may be random or block.) is a perfluoropolyether block represented by W1 is represented by the following formula (A): 【Chemistry 3】 (In formula (A), R 1 are independently selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. 2 is a monovalent group having a (meth)acryloyl group. p1 and q1 are each numbers from 0 to 1,000. The arrangement order of each repeating unit is not limited and may be random or block. is a divalent organopolysiloxane block represented by Each W2 independently represents the following formula (B): 【Chemistry 4】 (In formula (B), R 1 are independently selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. 2 R is a monovalent group having a (meth)acryloyl group. 1 Each ' is independently a group selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. p2 and q2 are each a number from 0 to 1,000. The arrangement order of each repeating unit is not limited and may be random or block. is a monovalent organopolysiloxane block represented by However, the number q1 of the siloxane units having a (meth)acryloyl group in the above formula (A) and the number q2 of the siloxane units having a (meth)acryloyl group in the above formula (B) are not 0 at the same time, Q is a divalent organic group having 2 to 12 carbon atoms, and in the above formula (1), Q is bonded to either the carbon atom at the end of Rf, the silicon atom at the end of W1, or the silicon atom at the end of W2; g is a number equal to or greater than 0.

2. 2. The organopolysiloxane having perfluoropolyether blocks and (meth)acryloyl groups according to claim 1, having a number average molecular weight of 3,000 to 500,000 and a content of organopolysiloxane blocks in one molecule of 50% or more and 99% or less.

3. R 2 3. The organopolysiloxane having a perfluoropolyether block and a (meth)acryloyl group according to claim 1 or 2, wherein the monovalent group having a (meth)acryloyl group represented by the following formula (3) is a group represented by the following formula (3): 【Chemistry 5】 (In formula (3), R 3 is a hydrogen atom or a methyl group. X is an oxygen atom or a group represented by -NH-. 4 is an alkylene group having 2 to 4 carbon atoms; m is a number from 0 to 60, and n is a number from 3 to 8.

4. 3. The organopolysiloxane having a perfluoropolyether block and a (meth)acryloyl group according to claim 1 or 2, wherein the perfluoropolyether block represented by Rf is a group represented by the following formula (4): 【Chemistry 6】 In formula (4), v and w are each a number from 0 to 200, and v+w=3 to 200. 2 F 4 The repeating units of may be linear or branched. The arrangement order of the repeating units is not limited and may be random or block.

5. Component (a): a perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (5), (b) component: a polysiloxane having a (meth)acryloyl group is mixed, Component (c): in the presence of an acid catalyst A method for producing an organopolysiloxane having a perfluoropolyether block represented by the following formula (1) and a (meth)acryloyl group, comprising an exchange reaction step between the siloxanes of components (a) and (b): 【Chemistry 7】 [In formula (1), Rf is represented by the following formula (2) 【Chemistry 8】 (In formula (2), z is a number from 1 to 4, v, w, x and y are each independently a number from 0 to 200, and v+w+x+y=3 to 200. Each repeating unit may be linear or branched. The arrangement order of each repeating unit is not limited and may be random or block.) is a perfluoropolyether block represented by W1 independently represents the following formula (A): 【Chemistry 9】 (In formula (A), R 1 are independently selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. 2 are each independently a monovalent group having a (meth)acryloyl group. p1 and q1 are each a number from 0 to 1,000. The arrangement order of each repeating unit is not limited and may be random or block. is a divalent organopolysiloxane block represented by Each W2 independently represents the following formula (B): 【Chemistry 10】 (In formula (B), R 1 are independently selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. 2 R is a monovalent group having a (meth)acryloyl group. 1 Each ' is independently a group selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. p2 and q2 are each a number from 0 to 1,000. The arrangement order of each repeating unit is not limited and may be random or block. is a monovalent organopolysiloxane block represented by However, the number q1 of the siloxane units having a (meth)acryloyl group in the above formula (A) and the number q2 of the siloxane units having a (meth)acryloyl group in the above formula (B) are not 0 at the same time, Q is a divalent organic group having 2 to 12 carbon atoms, and in the above formula (1), Q is bonded to either the carbon atom at the end of Rf, the silicon atom at the end of W1, or the silicon atom at the end of W2; g is a number equal to or greater than 0. 【Chemistry 11】 In formula (5), Rf is a perfluoropolyether block represented by formula (2) above, and W3 is independently a group represented by the following formula (A'): 【Chemistry 12】 (In formula (A'), R 1 is the same as above. p' is a number from 0 to 1,000. is a divalent organopolysiloxane block represented by W4 each independently represents the following formula (B'): 【Chemistry 13】 (In formula (B'), R 1 , R 1 ' is the same as above. p" is a number from 0 to 1,000. is a monovalent organopolysiloxane block represented by Q is the same as above. In addition, in the above formula (5), Q is bonded to either the carbon atom at the end of Rf, the silicon atom at the end of W3, or the silicon atom at the end of W4, g' is a number equal to or greater than 0.

6. 6. The method for producing an organopolysiloxane having a perfluoropolyether block and a (meth)acryloyl group according to claim 5, wherein the component (b) is at least one polysiloxane having a (meth)acryloyl group represented by the following formula (6) or the following formula (7): 【Chemistry 14】 (In formula (6), R 1 are independently selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. 5 are independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -SiR 1 3 (R 1 is the same as above.) R 3 is a hydrogen atom or a methyl group. X is an oxygen atom or a group represented by -NH-. 4 is an alkylene group having 2 to 4 carbon atoms. m is a number from 0 to 60, and n is a number from 3 to 8. p3 is a number from 0 to 1,000, and q3 is a number from 1 to 100. 【Chemistry 15】 (In formula (7), R 1 , R 3 , R 4 , X, m, and n are the same as above. p4 is a number from 0 to 6, and q4 is a number from 1 to 8, provided that 3≦p4+q4≦14.)

7. 7. The method for producing an organopolysiloxane having perfluoropolyether blocks and (meth)acryloyl groups according to claim 5 or 6, further comprising the step of adding component (d): one or more polysiloxanes selected from the group consisting of polysiloxanes represented by the following formula (8) and the following formula (9): 【Chemistry 16】 (In formula (8), R 1 are independently selected from an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. r1 is a number from 3 to 10. 【Chemistry 17】 (In formula (9), R 1 is the same as above. r2 is a number between 0 and 5,000.)

8. 7. The method for producing an organopolysiloxane having perfluoropolyether blocks and (meth)acryloyl groups according to claim 5 or 6, wherein the component (c): acid catalyst is at least one selected from the group consisting of sulfuric acid, methanesulfonic acid, and trifluoromethanesulfonic acid.

9. 7. The method for producing an organopolysiloxane having perfluoropolyether blocks and (meth)acryloyl groups according to claim 5 or 6, further comprising carrying out an exchange reaction step between the siloxanes of components (a) and (b) in the presence of component (e): an organic solvent.

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