Perfluoropolyether-organopolysiloxane block copolymer

Abstract

To provide a perfluoropolyether-organopolysiloxane block copolymer that has a perfluoropolyether group, in which it is possible to control the number of siloxane units etc. in a molecule thereof, and that has excellent affinity with a non-fluorinated organic compound.SOLUTION: A perfluoropolyether-organopolysiloxane block copolymer has a perfluoropolyether block and an organopolysiloxane block. The organopolysiloxane block has a side chain with one or more groups selected from an aralkyl group and groups having oxyalkylene units.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to perfluoropolyether-organopolysiloxane block copolymers. [Background technology]

[0002] In general, perfluoropolyether group-containing compounds have extremely low surface free energy and therefore possess chemical resistance, lubricity, releasability, water and oil repellency, etc. Utilizing 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 resistant agents 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. Therefore, when attempts are made to impart the above 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 formed from a reaction product of a perfluoropolyether group-containing diol and 2-isocyanate ethyl methacrylate has been proposed (Patent Document 1).

[0004] On the other hand, polysiloxane compounds also have low surface free energy and therefore possess properties such as water repellency, lubricity, and mold releasability. Furthermore, polysiloxane compounds have better affinity with other substances than perfluoropolyether compounds, and various modifications can further improve dispersion stability. Therefore, polysiloxane compounds can be easily added to various industrial materials to impart silicone properties, and are used as additives to improve performance in a wide range of fields. Perfluoropolyether-modified polysiloxane compounds are compounds having a perfluoropolyether group and a polysiloxane chain (Patent Document 2). However, when the fluorine modification rate of this polysiloxane compound is increased in an attempt to enhance the properties of the perfluoropolyether group, the affinity for other industrial materials is significantly reduced, which can cause problems with dispersion stability and reactivity.

[0005] 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-fluorine-based organic compounds (Patent Documents 3 and 4). Furthermore, perfluoropolyether group-containing polyether-modified polysiloxane has been developed as a compound that has excellent affinity with non-fluorine-based organic compounds (Patent Document 5). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 11-349651 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-321764 [Patent Document 3] Japanese Patent Application Laid-Open No. 2008-088412 [Patent Document 4] Japanese Patent Application Laid-Open No. 2011-021158 [Patent Document 5] Japanese Patent Application Laid-Open No. 2012-007124 Summary of the Invention [Problem to be solved by the invention]

[0007] The perfluoropolyether-organopolysiloxane block copolymers disclosed in Patent Documents 3 and 4 have low affinity for highly polar non-fluorinated organic compounds, which can cause problems with dispersion stability, reactivity, and the like. Furthermore, the perfluoropolyether group-containing polyether-modified polysiloxane disclosed in Patent Document 5 has good affinity with highly polar non-fluorine-based organic compounds, but because its molecular structure is cyclic, the number of siloxane units and the number of polyether groups that can be introduced into the molecule are limited, making it difficult to control compatibility with non-fluorine-based organic compounds and to introduce reactive functional groups such as (meth)acryloyl groups. Therefore, an object of the present invention is to provide a perfluoropolyether-organopolysiloxane block copolymer (hereinafter sometimes simply referred to as block copolymer) that has a perfluoropolyether group, and whose molecular structure, such as the number of units constituting the block copolymer and the modification rate of groups introduced into the side chains of the organopolysiloxane blocks, can be controlled, and that has excellent affinity with non-fluorine-based organic compounds. [Means for solving the problem]

[0008] As a result of extensive research into solving the above problems, the present inventors have found that the following perfluoropolyether-organopolysiloxane block copolymer can achieve the above objects, and have thus completed the present invention. That is, the present invention is as follows.

[0009] [1] A perfluoropolyether-organopolysiloxane block copolymer having a perfluoropolyether block and an organopolysiloxane block, represented by the following formula (1), wherein the organopolysiloxane block has at least one group selected from an aralkyl group and a group having an oxyalkylene unit on a side chain thereof: [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 each independently are 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 are independently selected from alkyl groups having 1 to 18 carbon atoms, phenyl groups, and organic groups having 4 to 12 carbon atoms and a (meth)acryloyl group. 2 is an aralkyl group having 7 to 18 carbon atoms. 3 is a group having an oxyalkylene unit having 6 to 300 carbon atoms and represented by the following formula (3). [ka] (In formula (3), R 4 is an alkylene group having 2 to 4 carbon atoms, and R 5 is an alkyl group having 1 to 4 carbon atoms, m is a number from 3 to 4, and n is a number from 1 to 60. The oxyalkylene units bracketed by n are composed of one type or two or more types, and when composed of two or more types, the arrangement order of the units is not limited and may be random or block. p1, q1, and r1 are each a number from 0 to 1,000. The arrangement order of the repeating units 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 are independently selected from alkyl groups having 1 to 18 carbon atoms, phenyl groups, and organic groups having 4 to 12 carbon atoms and a (meth)acryloyl group. 2is an aralkyl group having 7 to 18 carbon atoms. 3 R is a group containing an oxyalkylene group having 6 to 300 carbon atoms and represented by the above formula (3). 1 ' are independently a group selected from an alkyl group having 1 to 18 carbon atoms, a phenyl group, and a group having a (meth)acryloyl group having 4 to 12 carbon atoms. p2, q2, and r2 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, q1 and r1 in the above formula (A) and q2 and r2 in the above formula (B) do not become 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, and g is a number of 0 or greater. [2] The perfluoropolyether-organopolysiloxane block copolymer according to [1], which has a number average molecular weight of 3,000 to 500,000 and an organopolysiloxane block content of 50% or more per molecule. [3] The perfluoropolyether-organopolysiloxane block copolymer according to [1] or [2], wherein in formula (A) and the above formula (B), q1+q2>1 and r1+r2=0. [4] The perfluoropolyether-organopolysiloxane block copolymer according to [1] or [2], wherein in formula (A) and the above formula (B), q1+q2=0 and r1+r2>1. [5] R in formula (A) or formula (B) 1 and R 1' The perfluoropolyether-organopolysiloxane block copolymer according to any one of [1] to [4], wherein at least one of the above is an organic group having 4 to 12 carbon atoms and a (meth)acryloyl group. [6] The perfluoropolyether-organopolysiloxane block copolymer according to any one of [1] to [5], 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, provided 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.) [Effects of the Invention]

[0010] The block copolymer of the present invention has a perfluoropolyether block, a high siloxane content, and organopolysiloxane blocks at both ends of the molecular chain. Furthermore, the side chains of the organopolysiloxane blocks contain one or more groups selected from aralkyl groups and groups containing oxyalkylene units, which have excellent affinity with non-fluorine-containing organic compounds. Therefore, despite containing perfluoropolyether blocks, the block copolymer is highly compatible with non-fluorine-containing organic compounds, and is less likely to produce non-uniform or opaque portions when added to curable compositions, etc. Furthermore, the block copolymer of the present invention allows for easy control of the number of organopolysiloxane units and the degree of modification of the groups in the side chains of the organopolysiloxane blocks, and also facilitates the introduction of reactive functional groups such as (meth)acryloyl groups. Therefore, the block copolymer of the present invention is useful as a surface modifier for non-fluorine-containing organic resins. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in more detail below.

[0012] The perfluoropolyether-organopolysiloxane block copolymer of the present invention is represented by the following formula (1): In the block copolymer, perfluoropolyether blocks (Rf) and organopolysiloxane blocks (W1 or W2) exist alternately. [ka]

[0013] The organopolysiloxane block contains one or more groups selected from aralkyl groups and groups containing an oxyalkylene unit, which have excellent affinity with non-fluorine-containing organic compounds. Therefore, the block copolymer of the present invention represented by formula (1) is highly compatible with non-fluorine-containing organic compounds, and is less likely to produce non-uniform portions when added to a curable composition or the like.

[0014] The block copolymer of formula (1) preferably has an organopolysiloxane block content in one molecule of 50% or more and 99% or less, more preferably 60% or more and 90% or less. If the organopolysiloxane block content is above the lower limit, the compatibility with non-fluorine-based organic compounds is excellent, and if it is below the upper limit, the properties of the perfluoropolyether group are easily expressed. The organopolysiloxane block content of the block copolymer of formula (1) 1 The molar ratio of the perfluoropolyether block Rf of known molecular weight to the organosiloxy unit is calculated from the integral ratio of the peak derived from the alkylene of Q in the above formula (1) to the peak derived from the organic groups on the silicon atoms in W1 and W2 in the H-NMR spectrum, and this molar ratio is converted into a molecular weight ratio. Note that, since the block copolymer of formula (1) usually has a distribution in structure, the organopolysiloxane block content is the average value per molecule.

[0015] At least one of the organopolysiloxane blocks W1 and W2 has a siloxane unit represented by the following formula (5) or (6). [ka]

[0016] In the above formula (5), R 2 is an aralkyl group having 7 to 18 carbon atoms, and in the above formula (6), R 3 is a group having an oxyalkylene unit having 6 to 300 carbon atoms and no hydroxy group.

[0017] R in equation (5) 2 is preferably an aralkyl group represented by the following formula (7). [ka] In formula (7), R 6 is a hydrogen atom, a methyl group or a phenyl group, preferably a methyl group.

[0018] R in equation (6) 3 is preferably a group having an oxyalkylene unit having 6 to 300 carbon atoms and represented by the following formula (3). [ka] In formula (3), R 4 is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms. 5 is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group. m is a number of 3 to 4, preferably 3. n is a number of 1 to 60, preferably 2 to 12. The repeating units of the oxyalkylene group bracketed by n are composed of one type or two or more types, and when composed of two or more types, the arrangement order of the units is not limited and may be random or block.

[0019] The siloxane units having one or more groups selected from aralkyl groups and groups having an oxyalkylene unit are present in the above formula (1) at least once, and preferably two or more, from the viewpoint of compatibility with non-fluorine-containing organic compounds. The siloxane units of formula (5) or (6) in organopolysiloxane blocks W1 and W2 may be the same or different.

[0020] In the above formula (1), the organopolysiloxane block W1 is a divalent group represented by the following formula (A). [ka]

[0021] In the above formula (A), R 1 are independently selected from alkyl groups having 1 to 18 carbon atoms, phenyl groups, and organic groups having 4 to 12 carbon atoms and having a (meth)acryloyl group. Examples of the alkyl groups having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, dodecyl, and octadecyl groups. Examples of the organic groups having 4 to 12 carbon atoms and having a (meth)acryloyl group include groups having a (meth)acryloyl group represented by the following formula (8). [ka] In the above formula (8), R 7 is a hydrogen atom or a methyl group. X is an oxygen atom or a group represented by -NH-, preferably an oxygen atom. h is a number from 1 to 8, preferably a number from 3 to 8. R 1 Preferred examples of include a methyl group, a phenyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group, and a methyl group is particularly preferred.

[0022] In the above formula (A), R 2 and R 3 An example of this is R in Eq. (5). 2 and R in formula (6) 3 Examples of the above-mentioned examples include the above-mentioned examples.

[0023] In the above formula (A), p1, q1, and r1 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 the repeating units is not limited and may be random or block.

[0024] Examples of the group represented by the above formula (A) include groups represented by the following formulae (9) to (17), but are not limited to these. [ka] [ka] [ka] [ka]

[0025] In the above formula (1), the organopolysiloxane block W2 is a monovalent group represented by the following formula (B). [ka]

[0026] In the above formula (B), R 1 are independently selected from alkyl groups having 1 to 18 carbon atoms, phenyl groups, and organic groups having 4 to 12 carbon atoms and a (meth)acryloyl group. 2 is an aralkyl group having 7 to 18 carbon atoms. 3 R is a group containing an oxyalkylene group having 6 to 300 carbon atoms and represented by the above formula (3). 1 , R 2 and R 3 The preferred embodiments of each of R are the same as those of formula (A). 1 ' are independently a group selected from an alkyl group having 1 to 18 carbon atoms, a phenyl group, and an organic group having 4 to 12 carbon atoms and a (meth)acryloyl group, and are preferably a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a dodecyl group, an octadecyl group, an acryloxymethyl group, a 3-acryloxypropyl group, a methacryloxymethyl group, or a 3-methacryloxypropyl group, and more preferably a butyl group, a hexyl group, an octyl group, or a dodecyl group.

[0027] In the above formula (B), p2, q2, and r2 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 the repeating units is not limited and may be random or block. However, q1 and r1 in the above formula (A), and q2 and r2 in the above formula (B), are not 0 at the same time.

[0028] Examples of the group represented by formula (B) include groups represented by the following formulae (18) to (26), but are not limited to these. [ka] [ka] [ka] [ka]

[0029] The perfluoropolyether block Rf in the above formula (1) is represented by the following formula (2). [ka]

[0030] 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.

[0031] Examples of the repeating units of the perfluoropolyether block Rf represented by the above formula (2) include the following repeating units. [ka]

[0032] Among these, the 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]

[0033] In formula (4), v and w are each a number from 0 to 200, preferably a number from 0 to 50, provided that v+w=3 to 200, preferably 10 to 50. The repeating unit of (OC2F4) may be linear or branched, and the arrangement order of the repeating units is not limited and may be random or block.

[0034] 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.

[0035] In the above formula (1), Q is a divalent organic group having 2 to 12 carbon atoms, preferably 3 to 6 carbon atoms. In addition, in the above formula (1), Q is bonded to either the carbon atom at the terminal of Rf, the silicon atom at the terminal of W1, or the silicon atom at the terminal of W2. Note that 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.)

[0036] Among the specific examples of Q above, the following is preferred in that it is easy to link the organopolysiloxane block and the perfluoropolyether block: * -CH2OCH2CH2CH2- ** is preferred.

[0037] The number-average molecular weight of the block copolymer of formula (1) is preferably 3,000 to 500,000. When the number-average molecular weight is within this range, the copolymer tends to have excellent solubility in non-fluorine-containing organic compounds and be 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).

[0038] [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)

[0039] In the above formula (1), g is a number of 0 or more, and is preferably a number such that the number average molecular weight of the block copolymer 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.

[0040] [Method for producing perfluoropolyether-organopolysiloxane block copolymer] The block copolymer of the present invention can be produced by the method described below. Component (a): an organohydrogenpolysiloxane having a perfluoropolyether block represented by the following formula (27): and, Component (b): one or more compounds selected from aralkyl compounds having a terminal carbon-carbon double bond and a carbon number of 7 to 18, and compounds having an oxyalkylene unit having a terminal carbon-carbon double bond and a carbon number of 6 to 300, represented by the following formula (28): And, Component (c): Hydrosilylation reaction catalyst The block copolymer represented by the above formula (1) can be obtained by carrying out a hydrosilylation reaction between the components (a) and (b) in the presence of the above formula (1).

[0041] [ka]

[0042] [ka] (In formula (28), R 4 , R 5 , m, and n are the same as those shown in the above formula (3). The arrangement order of the repeating units bounded by n is not limited, and may be random or block. The above oxyalkylene units are composed of one type or two or more types.

[0043] In the above formula (27), Rf is a perfluoropolyether block represented by the above formula (2), and g' is a number of 0 or more.

[0044] In formula (27), the organopolysiloxane blocks W3 are each independently a divalent group represented by the following formula (A'). [ka] In the above formula (A'), R 1 are the same as those in the above formula (A). p1' and s1' are each a number from 0 to 1,000, and preferably a number from 0 to 200. The arrangement order of the repeating units is not limited, and may be random or block.

[0045] In formula (27), the organopolysiloxane blocks W4 are each independently a monovalent group represented by the following formula (B'). [ka] In the above formula (B'), R 1 , and R 1 p2' and s2' are the same as those in the above formula (B). p2' and s2' are each a number from 0 to 1,000, and preferably a number from 0 to 200. The arrangement order of the repeating units is not limited, and may be random or block. However, the number s1' of the hydrogensiloxane units of the formula (A') and the number s2' of the hydrogensiloxane units of the formula (B') are not 0 at the same time.

[0046] In the above formula (27), Q is a divalent organic group having 2 to 12 carbon atoms. Q is bonded to either the terminal carbon atom of Rf, the terminal silicon atom of W3, or the terminal silicon atom of W4.

[0047] Component (b): an aralkyl compound having 7 to 18 carbon atoms and a terminal carbon-carbon double bond is preferably a compound represented by the following formula (29). [ka] (In formula (29), R 6 is the same as in the above formula (7).

[0048] Component (c): The 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.

[0049] The above-mentioned component (c): hydrosilylation reaction catalyst may be used in a so-called catalytic amount, preferably 0.1 to 200 ppm in terms of metal atom weight relative to the total of the above-mentioned components (a) and (b).

[0050] In the method for producing the organopolysiloxane of formula (1) above by the hydrosilylation reaction of components (a) and (b), the hydrosilylation reaction may be carried out by optionally adding component (d): an organic solvent. This reaction can be carried out without a solvent, but the addition of an organic solvent may improve the compatibility of components (a) and (b), and the hydrosilylation reaction may proceed more efficiently.

[0051] Examples of the organic solvent (d) 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 components (a) and (b).

[0052] The amount of component (d): organic solvent used is not particularly limited as long as the amount is such that the components (a) and (b) are compatible with each other, but it is preferably 10 to 300% by mass of the total of components (a) and (b).

[0053] The component (a): an organohydrogenpolysiloxane having a perfluoropolyether block represented by the formula (27) above, can be produced by the following method or the like.

[0054] In detail, component (e): a perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (30), component (f): an organohydrogenpolysiloxane, component (g): an acid catalyst, and, if necessary, component (h): one or more polysiloxanes selected from the group consisting of polysiloxanes represented by the following formulas (31) and (32), are mixed together to carry out an exchange reaction between the siloxanes of component (e), component (f), and component (h).

[0055] [ka]

[0056] [ka] (In formula (31), R 1 is the same as in the above formula (A'). t1 is a number from 3 to 10, preferably a number from 3 to 8.

[0057] [ka] (In formula (32), R 1 is the same as in the above formula (B'). 7 are independently a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and are preferably a hydroxy group, a methyl group, or a methoxy group. t2 is a number from 0 to 5,000, and preferably a number from 2 to 1,000.

[0058] In the above formula (30), Rf is the same as in the above formula (27), and g'' is a number of 0 or more. In formula (30), the organopolysiloxane blocks W5 are each independently a divalent group represented by the following formula (A″). [ka] In the above formula (A"), R 1 is the same as in the above formula (A'). 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.

[0059] In the above formula (30), the organopolysiloxane block W6 is a monovalent group represented by the following formula (B″). [ka] In the above formula (B"), R 1 is the same as in the above formula (B').1 " is independently an alkyl group having 1 to 18 carbon atoms or a phenyl group, and is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a dodecyl group, or an octadecyl group, and more preferably a butyl group, a hexyl group, an octyl group, or a dodecyl group. q" is a number from 0 to 1,000, preferably a number from 0 to 500, and more preferably a number from 0 to 200.

[0060] In the above formula (30), Q is a divalent organic group having 2 to 12 carbon atoms. Q is bonded to either the terminal carbon atom of Rf, the terminal silicon atom of W5, or the terminal silicon atom of W6.

[0061] The organohydrogenpolysiloxane (component (f)) may be linear, branched, or cyclic, and examples thereof include the following siloxanes. [ka]

[0062] There are no particular restrictions on the acid catalyst for component (g) above, provided it is capable of hydrolyzing the siloxane bonds in components (e) and (f) above, but sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, and the like are preferred.

[0063] Component (h): Examples of the polysiloxanes represented by formula (31) and formula (32) include the following siloxanes. [ka]

[0064] In the method for producing the organohydrogenpolysiloxane of formula (27) by the exchange reaction between siloxanes, the exchange reaction between siloxanes may be carried out by optionally adding component (i): an organic solvent. Although this reaction can be carried out without a solvent, adding an organic solvent improves the compatibility of component (e): a perfluoropolyether-organopolysiloxane block copolymer with the polysiloxanes of components (f) and (h), allowing the exchange reaction between siloxanes to proceed efficiently.

[0065] The amount of component (i): organic solvent used is not particularly limited as long as the components (e), (f), and (h) are compatible with each other, but is preferably 10 to 300 mass % of the total of components (e), (f), and (h). [Example]

[0066] 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, Si(R 3 The integral value M derived from Si in the )3-O- structure and the -Q-Si(R 1 The value g is calculated from the integral value M' derived from Si in the 2-O- structure, and is given by g=(M' / M)-1.

[0067] [Example 1] Synthesis of block copolymer (1-1) A reaction vessel was charged with 3.0 g of an organohydrogenpolysiloxane having a perfluoropolyether block represented by the following formula (27-1), 0.52 g of isopropenylbenzene, and 3.5 g of toluene as a solvent, and the mixture was stirred at 80°C for 5 minutes. Next, 0.01 g of a toluene solution of a platinum vinylsiloxane complex was added, and the mixture was stirred at 110°C for 4 hours. Next, the excess isopropenylbenzene and the toluene solvent were distilled off under reduced pressure, yielding 3.2 g of a liquid product.

[0068] [ka]

[0069] The NMR spectra of the resulting product were measured and the results were as follows: [Table 1]

[0070] [Table 2]

[0071] [Table 3]

[0072] From these results, it was found that the product had the structure represented by the following formula (1-1), and was a block copolymer with an organopolysiloxane block content of 77% in the molecule. Furthermore, the number average molecular weight of the block copolymer measured by GPC in terms of polystyrene was 6,950. [ka]

[0073] [Example 2] Synthesis of block copolymer (1-2) A reaction vessel was charged with 3.5 g of an organohydrogenpolysiloxane having a perfluoropolyether block represented by the following formula (27-2), 1.4 g of a polyether having a terminal carbon-carbon double bond represented by the following formula (28-2), and 4.9 g of toluene as a solvent, and the mixture was stirred at 80°C for 5 minutes. Next, 0.02 g of a toluene solution of a platinum vinylsiloxane complex was added, and the mixture was stirred at 100°C for 2 hours. The toluene solvent was then distilled off under reduced pressure, yielding 4.7 g of a liquid product.

[0074] [ka]

[0075] The NMR spectra of the resulting product were measured and the results were as follows: [Table 4]

[0076] [Table 5]

[0077] [Table 6]

[0078] From these results, it was found that the product had the structure represented by the following formula (1-2), and was a block copolymer with an organopolysiloxane block content of 50% in the molecule. Furthermore, the number average molecular weight of the block copolymer measured by GPC in terms of polystyrene was 4,070. [ka]

[0079] [Example 3] Synthesis of block copolymer (1-3) A reaction vessel was charged with 3.3 g of an organohydrogenpolysiloxane having a perfluoropolyether block represented by the following formula (27-3), 1.2 g of a polyether having a terminal carbon-carbon double bond represented by the following formula (28-3), and 6.8 g of toluene as a solvent, and the mixture was stirred at 80°C for 5 minutes. Next, 0.02 g of a toluene solution of a platinum vinylsiloxane complex was added, and the mixture was stirred at 80°C for 5 hours. The toluene solvent was then distilled off under reduced pressure, yielding 4.2 g of a liquid product.

[0080] [ka]

[0081] The NMR spectra of the resulting product were measured and the results were as follows: [Table 7]

[0082] [Table 8]

[0083] [Table 9]

[0084] From these results, it was determined that the product had the structure represented by the following formula (1-3), and was a block copolymer with an organopolysiloxane block content of 84% in the molecule. Furthermore, the number average molecular weight of the block copolymer measured by GPC in terms of polystyrene was 10,130.

[0085] [ka]

[0086] [Example 4] Synthesis of block copolymer (1-4) A reaction vessel was charged with 3.0 g of an organohydrogenpolysiloxane having a perfluoropolyether block represented by the above formula (27-1), 0.60 g of a polyether having a terminal carbon-carbon double bond represented by the above formula (28-3), and 3.6 g of toluene as a solvent, and the mixture was stirred at 80°C for 5 minutes. Next, 0.01 g of a toluene solution of a platinum vinylsiloxane complex was added, and the mixture was stirred at 80°C for 4 hours. Next, 0.26 g of isopropenylbenzene and 0.01 g of a toluene solution of a platinum vinylsiloxane complex were added, and the mixture was stirred at 100°C for 6 hours. Excess isopropenylbenzene and the toluene solvent were distilled off under reduced pressure, yielding 3.6 g of a liquid product.

[0087] The NMR spectra of the resulting product were measured and the results were as follows: [Table 10]

[0088] [Table 11]

[0089] [Table 12]

[0090] From these results, it was determined that the product had the structure represented by the following formula (1-4), and was a block copolymer with an organopolysiloxane block content of 80% in the molecule. Furthermore, the number average molecular weight of the block copolymer measured by GPC in terms of polystyrene was 8,440.

[0091] [ka]

[0092] Comparative Example 1 (organopolysiloxane block content in molecule: 71%) A perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (30-1) was synthesized according to Japanese Patent No. 4,900,854. The number average molecular weight of the block copolymer measured by GPC in terms of polystyrene was 7,110.

[0093] [ka]

[0094] Comparative Example 2 (organopolysiloxane block content in molecule: 68%) A reaction vessel was charged with 6.7 g of the perfluoropolyether-organopolysiloxane block copolymer represented by the above formula (30-1), 0.86 g of a methacryloyl-containing polysiloxane represented by the following formula (32-1), and 7.5 g of 1,3-bis(trifluoromethyl)benzene. The mixture was stirred at 25°C for 5 minutes, and 15 mg of trifluoromethanesulfonic acid was added. The mixture was then stirred at 60°C for an additional 7 hours. Next, 100 mg of Kyoward 500 (Kyowa Chemical Industry Co., Ltd.) adsorbent was added to neutralize the 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 yield 5.5 g of the perfluoropolyether-organopolysiloxane block copolymer represented by the following formula (30-2). The number-average molecular weight of the block copolymer measured by GPC in terms of polystyrene was 4,900.

[0095] [ka]

[0096] [ka]

[0097] [Evaluation of solubility in non-fluorinated organic compounds] 1 g of the block copolymer of the above Examples and Comparative Examples was mixed with 9 g of the following non-fluorine-based organic compound, and the resulting mixture was visually observed to evaluate the solubility according to the following criteria. Evaluation criteria ○: The mixture is transparent. △: The mixture is cloudy. ×: The mixture is separated into two phases.

[0098] [Table 13]

[0099] The results in Table 13 demonstrate that the perfluoropolyether-organopolysiloxane block copolymers of the present invention, which have one or more groups selected from aralkyl groups and groups containing oxyalkylene units in the side chains of the organopolysiloxane blocks, have superior solubility in non-fluorine-containing organic compounds to the block copolymers of the comparative examples, which have neither aralkyl groups nor groups containing oxyalkylene units in the side chains of the organopolysiloxane blocks. The block copolymers of the present invention are useful as additives for resin compositions and the like.

Claims

1. A perfluoropolyether-organopolysiloxane block copolymer having a perfluoropolyether block and an organopolysiloxane block, represented by the following formula (1), wherein the organopolysiloxane block has one or more groups selected from aralkyl groups and groups having an oxyalkylene unit on its side chain, and at least one of R 1 and R 1' in the following formula (A) or (B) is an organic group having 4 to 12 carbon atoms and having a (meth)acryloyl group. 【Chemical 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 each independently are 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 alkyl groups having 1 to 18 carbon atoms, phenyl groups, and organic groups having 4 to 12 carbon atoms and a (meth)acryloyl group. 2 is an aralkyl group having 7 to 18 carbon atoms. 3 is a group having an oxyalkylene unit having 6 to 300 carbon atoms and represented by the following formula (3): 【Chemistry 4】 (In formula (3), R 4 is an alkylene group having 2 to 4 carbon atoms, and R 5 is an alkyl group having 1 to 4 carbon atoms, m is a number from 3 to 4, and n is a number from 1 to 60. The oxyalkylene units bracketed by n are composed of one type or two or more types, and when composed of two or more types, the arrangement order of the units is not limited and may be random or block. p1, q1, and r1 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): 【Chemistry 5】 (In formula (B), R 1 are independently selected from alkyl groups having 1 to 18 carbon atoms, phenyl groups, and organic groups having 4 to 12 carbon atoms and a (meth)acryloyl group. 2 is an aralkyl group having 7 to 18 carbon atoms. 3 is a group containing an oxyalkylene group having 6 to 300 carbon atoms and represented by the above formula (3). 1 ' are independently a group selected from an alkyl group having 1 to 18 carbon atoms, a phenyl group, and an organic group having 4 to 12 carbon atoms and a (meth)acryloyl group. p2, q2, and r2 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, q1 and r1 in the above formula (A) and q2 and r2 in the above formula (B) do not become 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 terminal carbon atom of Rf, the terminal silicon atom of W1, or the terminal silicon atom of W2; g is a number equal to or greater than 0.

2. 2. The perfluoropolyether-organopolysiloxane block copolymer according to claim 1, which has a number average molecular weight of 3,000 to 500,000 and an organopolysiloxane block content of 50% or more per molecule.

3. 3. The perfluoropolyether-organopolysiloxane block copolymer according to claim 1, wherein in formula (A) and formula (B), q1+q2>1 and r1+r2=0.

4. 3. The perfluoropolyether-organopolysiloxane block copolymer according to claim 1, wherein in formula (A) and formula (B), q1+q2=0 and r1+r2>1.

5. 5. The perfluoropolyether-organopolysiloxane block copolymer according to claim 1, 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 numbers 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.

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