Organopolysiloxane and method for producing same

Abstract

[Problem] The purpose of the present invention is to provide: a new organopolysiloxane which is useful for yielding a release coating agent capable of forming a cured coating film having a low peeling force during low speed and high speed peeling; and a method for producing same. [Solution] Provided is an organopolysiloxane represented by average compositional formula (1) (in the formula, R1 moieties are each independently an alkenyl group having 3-20 carbon atoms, R2 denotes a linking group and is a divalent hydrocarbon group having 1-10 carbon atoms, R3 moieties are each independently a group selected from among substituted or unsubstituted monovalent hydrocarbon groups having 1-20 carbon atoms, alkoxy groups having 1-20 carbon atoms, halogenated alkyl groups having 1-10 carbon atoms, hydroxyl group-containing organic groups and acyloxy group-containing organic groups, a, b, c, d, e, f and g satisfy that a≥0, b≥0, c≥0, d≥0, e≥0, f≥0 and g≥0, the value of a+c+e is 1 or more, and 2≤a+b+c+d+e+f+g≤15,000).

Description

Organopolysiloxanes and methods for producing the same

[0001] The present invention relates to a novel organopolysiloxane having an alkenyl-containing group with an ester structure as a reactive group, and a method for producing the same. The present invention also relates to a silicone curable composition and a release coating agent containing the organopolysiloxane.

[0002] Release paper and release film are obtained by applying a silicone-based release coating agent to the surface of a substrate such as paper or plastic film, and forming a hardened film through a cross-linking reaction. They are widely used as release agent films for adhesive or tacky substances.

[0003] The mainstream composition for release coatings is an addition-curing type silicone curable composition that primarily consists of a vinyl group-containing organopolysiloxane and an organohydrogenpolysiloxane having hydrogen atoms bonded to silicon atoms, and is cured by a hydrosilylation reaction. It has advantages such as a fast curing speed and relatively easy adjustment of release properties, and is therefore used in a wide range of applications. However, in vinyl group-containing organopolysiloxanes, the vinyl groups bonded to silicon atoms have low reactivity, which can lead to poor curing. Therefore, it is necessary to add a large amount of organohydrogenpolysiloxane.

[0004] Japanese Patent Publication No. 60-133051 describes an addition-reaction type release film-forming composition containing a non-reactive aryl group-containing polyorganosiloxane, which reduces the peeling force at both low and high speeds. Japanese Patent Publication No. 3-93858 describes a silicone composition for release paper containing a polyorganosiloxane having hydroxyl groups at its ends and containing aryl groups. Furthermore, Japanese Patent Publication No. 8-217980 describes a release composition containing a high molecular weight polydimethylsiloxane having hydroxyl groups and a polyorganosiloxane having hydroxyl groups and aryl groups.

[0005] JP-A-60-133051, JP-A-3-93858, JP-A-8-217980

[0006] However, the silicone compositions for release paper containing aryl group-containing polyorganosiloxanes described in Patent Documents 1 and 2 reduce the peeling force during high-speed peeling, but increase the amount of silicone migration, making it difficult to suppress the decrease in residual adhesion. Furthermore, the release composition described in Patent Document 3 has the problem of increased silicone migration and decreased residual adhesion. For these reasons, it is difficult to reduce both the peeling force during low-speed and high-speed peeling using compositions containing polyorganosiloxanes that use vinyl groups as functional groups. Therefore, there is a need to develop polyorganosiloxanes that exhibit higher reactivity compared to vinyl groups and have functional groups that allow sufficient curing to proceed even when the amount of organohydrogenpolysiloxane added is small.

[0007] The present invention has been made in view of the above circumstances, and aims to provide a novel organopolysiloxane and a method for producing the same, which are useful for providing a peelable coating agent capable of forming a cured film with low peeling force at both low and high speeds.

[0008] The present inventors conducted diligent research to solve the above problems and have succeeded in synthesizing a novel organopolysiloxane having an alkenyl group, wherein the linkage between the alkenyl group and the silicon atom of the siloxane has an ester structure. Furthermore, the inventors have found that this alkenyl group-containing organopolysiloxane having an ester structure improves the curability of silicone curable compositions and provides a cured film with reduced peeling force at both low and high speeds compared to conventional organopolysiloxanes having vinyl groups. Moreover, the present inventors have found that the organopolysiloxane of the present invention improves the effect of suppressing the phenomenon of severe peeling of the cured film due to exposure to the atmosphere (hereinafter referred to as exposure resistance) compared to conventional organopolysiloxanes having vinyl groups.

[0009] In other words, the present invention provides [1] an organopolysiloxane represented by the following average composition formula (1). (In the formula, R １ These are, independently of each other, alkenyl groups having 3 to 20 carbon atoms, and R ２represents a linking group, which is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ３ is, independently of one another, a group selected from a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an organic group having a hydroxyl group, and an organic group having an acyloxy group. Further, a, b, c, d, e, f and g satisfy a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, g≧0, and a + c + e is 1 or more, and 2≦a + b + c + d + e + f + g≦15000).

[0010] [2] In the above average composition formula (1), the number of siloxane units having the above R １ is 0.1 to 100% with respect to the total number of all siloxane units, and the organopolysiloxane according to [1] above. [3] In the above average composition formula (1), R １ is, independently of one another, an alkenyl group having 5 to 12 carbon atoms, and the organopolysiloxane according to [1] or [2] above. [4] In the above average composition formula (1), R ２ is a divalent hydrocarbon group having 1 to 7 carbon atoms, and the organopolysiloxane according to any one of [1] to [3] above. [5] In the above average composition formula (1), a = 0 and e = 0, and the organopolysiloxane according to any one of [1] to [4] above. [6] The organopolysiloxane according to any one of [1] to [5] above, represented by the following formula (1') (wherein, R １ , R ２ and R ３ are as described above, c is 1 or more, d is 0 or more, and 2≦c + d≦20. c is a value such that the number of siloxane units having the above R １ is 1 to 100% with respect to the total number of all siloxane units). [7] In the above average composition formula (1), a and b satisfy 2≦a + b≦20, c≧1, d≧0, and 1≦c + d≦15000, e = 0, and a + c is the above R １A linear organopolysiloxane according to any one of [1] to [6] above, wherein the number of siloxane units having the above value is 0.1 to 50% of the total number of siloxane units, and which may have branching. [8] A method for producing an organopolysiloxane according to any one of [1] to [7] above, comprising: (I) an organopolysiloxane containing an alkyl halogenated group represented by the following average composition formula (2) (In the formula, R ２ R represents a linking group, which is a divalent hydrocarbon group having 1 to 10 carbon atoms. ３’ These are groups independently selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and organic groups having a hydroxyl group, X １ (II) an alkenyl group-containing metal carboxylic acid salt, (III) reacting this with an alkenyl group-containing organopolysiloxane in the presence of a phase transfer catalyst selected from phosphonium salts, ammonium salts, and crown ethers. [9] (I) an organopolysiloxane containing a halogenated alkyl group represented by the following formula (2'), (In the formula, R ２ , R ３ ', X １ (II) an alkenyl group-containing metal carboxylate salt is reacted with (III) an alkenyl group-containing organopolysiloxane represented by the following formula (1') in the presence of a phase transfer catalyst selected from phosphonium salts, ammonium salts, and crown ethers. (In the formula, R １ These are, independently of each other, alkenyl groups having 3 to 20 carbon atoms, and R ２ and R ３The method for manufacturing according to [8] above, comprising the step of obtaining (where c and d are as defined in formula (1) above, c≧1, d≧0, and 2≦c+d≦20).

[10] The method for manufacturing according to [8] or [9] above, comprising the step of further polymerizing the alkenyl group-containing organopolysiloxane represented by formula (1') with at least one organo(poly)siloxane to obtain a linear organopolysiloxane represented by the average composition formula (1) which may have branching.

[11] (I) A linear organopolysiloxane which may be branched and is represented by the average composition formula (2) above and has a viscosity of 0.5 mPa·s or more and 5000 mPa·s or less at 25°C, and (II) an alkenyl group-containing metal carboxylate salt, (III) a phase transfer catalyst selected from phosphonium salts, ammonium salts and crown ethers, to obtain a linear organopolysiloxane which may be branched and is represented by the average composition formula (1) below. (In the formula, R １ These are, independently of each other, alkenyl groups having 3 to 20 carbon atoms, and R ２ R represents a linking group, which is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ３ (The organopolysiloxane is a group selected independently from a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an organic group having a hydroxyl group, and an organic group having an acyloxy group, and furthermore, a, b, c, d, e, f, and g satisfy a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, g≧0, a+c+e is 1 or more, and 2≦a+b+c+d+e+f+g≦500, and the organopolysiloxane has a viscosity of 0.5 mPa·s or more and 5000 mPa·s or less at 25°C.) The manufacturing method described in [8] above.

[12] A silicone curable composition comprising the organopolysiloxane described in any one of [1] to [7] above.

[13] A peeling coating agent comprising any one of the organopolysiloxanes described in [1] to [7] above.

[0011] The organopolysiloxane of the present invention is useful for curable silicone compositions, particularly for release coating agents, that provide release paper or release film that exhibits good curability and reduces peeling force at both low and high speeds.

[0012] Figure 1 shows the polyorganosiloxane having an alkenyl-containing group with an ester structure obtained in Example 1. １ This is an H-NMR chart. Figure 2 shows the polyorganosiloxane having an alkenyl-containing group with an ester structure obtained in Example 1. ２９ This is a Si-NMR chart. Figure 3 shows the polyorganosiloxane having an alkenyl-containing group with an ester structure obtained in Example 5. １ This is an H-NMR chart. Figure 4 shows the polyorganosiloxane having an alkenyl-containing group with an ester structure obtained in Example 5. ２９ This is a Si-NMR chart. Figure 5 shows the polyorganosiloxane having an alkenyl-containing group with an ester structure obtained in Example 10. １ This is an H-NMR chart. Figure 6 shows the polyorganosiloxane having an alkenyl-containing group with an ester structure obtained in Example 10. ２９ This is an Si-NMR chart.

[0013] The present invention will be described in detail below. <Polyorganosiloxane having an alkenyl-containing group with an ester structure> The organopolysiloxane according to the present invention is a novel organopolysiloxane having an alkenyl group and an ester structure at the linkage between the alkenyl group and the silicon atom of the siloxane. The organopolysiloxane is represented by the following average composition formula (1).

[0014] In the average empirical formula (1), R １ These are, independently of each other, alkenyl groups having 3 to 20 carbon atoms. ２ R represents a linking group and is a divalent hydrocarbon group having 1 to 10 carbon atoms. ３These are groups independently selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, alkyl halogenated groups having 1 to 10 carbon atoms, organic groups having a hydroxyl group, and organic groups having an acyloxy group. Furthermore, a, b, c, d, e, f, and g satisfy a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, and g≧0, and a+c+e≧1 and 2≦a+b+c+d+e+f+g≦15000.

[0015] R １ These are, independently of each other, alkenyl groups having 3 to 20 carbon atoms. The lower limit of the number of carbon atoms in the alkenyl group is 3 or more, preferably 4 or more, and preferably 5 or more. The upper limit of the number of carbon atoms in the alkenyl group may be 20 or less, preferably 19 or less, preferably 18 or less, preferably 17 or less, preferably 16 or less, and preferably 12 or less. Preferably, it is an alkenyl group having 3 to 19 carbon atoms, preferably 3 to 18, preferably 3 to 17, preferably 3 to 16 carbon atoms, more preferably an alkenyl group having 4 to 16 carbon atoms, and even more preferably an alkenyl group having 5 to 12 carbon atoms. When the organopolysiloxane of the present invention is applied to a curable silicone composition, particularly a release coating agent, from the viewpoint of curability, R １ It is preferable that R be a long chain. １ The larger the number of carbon atoms, the better.

[0016] R １ Examples of alkenyl groups include propenyl, butenyl, pentenyl, hexenyl, octenyl, decenyl, undecenyl, and dodecenyl groups. Due to the ease of obtaining the raw materials for the functional groups, butenyl, pentenyl, octenyl, nonenyl, and decenyl groups are preferred, with the decenyl group being more preferred. Furthermore, the double bond in the alkenyl group may be located either at the end or in the interior of the molecule, but its location at the end is preferred. １ This is represented, for example, by the following structure. In the following formula, the dotted lines indicate the bonds with the ester structure.

[0017] R ２R represents a linking group, which is a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably a divalent hydrocarbon group having 1 to 7 carbon atoms, and more preferably a divalent hydrocarbon group having 1 to 5 carbon atoms. ２ Examples include alkylene groups such as methylene groups, ethylene groups, trimethylene groups, and tetramethylene groups, and allylene groups such as phenylene groups. From the viewpoint of the availability of raw materials for functional groups, R ２ The alkylene group is preferred, and the methylene group, ethylene group, and trimethylene group are more preferred.

[0018] R ３ These are groups independently selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, alkyl halogenated groups having 1 to 10 carbon atoms, organic groups having a hydroxyl group, and organic groups having an acyloxy group. Examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, and propyl groups, cycloalkyl groups such as cyclohexyl groups, and aryl groups such as phenyl and tolyl groups. Examples of alkoxy groups having 1 to 20 carbon atoms include methoxy, ethoxy, isopropoxy, and butoxy groups. Examples of alkyl halogenated groups having 1 to 10 carbon atoms include chloromethyl, chloroethyl, chloropropyl, bromomethyl, bromoethyl, and bromopropyl groups. Examples of organic groups having a hydroxyl group include hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxybutyl groups. Examples of organic groups having an acyloxy group include acetoxymethyl group, 2-acetoxyethyl group, 3-acetoxypropyl group, and 6-acetoxyhexyl. ３ Preferably, this is a methyl group, ethyl group, methoxy group, ethoxy group, or hydroxyl group-containing organic group.

[0019] In the above average composition formula (1), the number of alkenyl groups (R) relative to the total number of siloxane units １ The ratio of siloxane units having an alkenyl group (R) is preferably 0.1 to 100%, more preferably 0.2 to 80%, and more preferably 0.3 to 60%. １If the content ratio of siloxane units having ) is above the above lower limit, the curability by heat curing will be good.

[0020] In the average composition formula (1), a, b, c, d, e, f, and g satisfy a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, g≧0, and a+c+e≧1. a+b+c+d+e+f+g satisfies 2≦a+b+c+d+e+f+g≦15000, preferably 2≦a+b+c+d+e+f+g≦10000, and more preferably 2≦a+b+c+d+e+f+g≦7500. If a+b+c+d+e+f+g is lower than the above lower limit, the composition tends to spread too easily when used as the main component of a silicone curable composition, resulting in insufficient coating on the substrate surface. If it is higher than the above upper limit, it becomes difficult to spread, reducing workability.

[0021] The organopolysiloxane of the present invention may be linear, branched, or cyclic. Preferably, it is a linear organopolysiloxane or a cyclic organopolysiloxane which may have branches.

[0022] In the above average composition formula (1), a, b, c, d, e, f, and g represent the number of M units of siloxane, c+d represents the number of D units of siloxane, e+f represents the number of T units of siloxane, and g represents the number of Q units of siloxane. c+d is preferably 1 to 10000, more preferably 2 to 7500, and more preferably 3 to 5000. a+b is 0 or 1 to 20, more preferably 2 to 16, and more preferably 2 to 12. e+f is preferably 0 to 14, more preferably 0 to 10. g is preferably 0 to 8, and more preferably 0 to 6.

[0023] The above alkenyl group (R １ Esters having the above R ２It may be bonded to any of M-unit, D-unit, or T-unit silicon atoms via the . Preferably, it is bonded to M-unit or D-unit silicon atoms, and more preferably to D-unit silicon atoms. Therefore, a, c, and e are preferably e=0 and a+c≧1, and more preferably a=0, e=0, and c≧1.

[0024] In the embodiment in which the organopolysiloxane of the present invention is cyclic, in the above average composition formula (1), a = 0, b = 0, e = 0, f = 0, and g = 0. c and d are such that d ≥ 0, c ≥ 1, 2 ≤ c + d ≤ 20, preferably 2 ≤ c + d ≤ 15, and more preferably 2 ≤ c + d ≤ 10. c is preferably 1 to 20, preferably 2 to 15, and more preferably 3 to 10. d is preferably 0 to 19, preferably 1 to 13, and more preferably 1 to 7.

[0025] In the embodiment where the organopolysiloxane is cyclic, in the above average composition formula (1), the alkenyl group (R) is relative to the total number of siloxane units. １ The ratio of siloxane units having ) is 0.1 to 100%, with an upper limit of 100% or less, preferably 90% or less, and more preferably 80% or less. The lower limit is 0.1% or more, preferably 1% or more, more preferably 10% or more, and more preferably 50% or more. Preferably 1% or more and 100% or less, preferably 10% or more and 100% or less, and preferably 50% or more and 100% or less. In the above average composition formula (1), c is R relative to the total number of all siloxane units. １ The ratio of siloxane units containing the above-mentioned properties falls within the above range.

[0026] A cyclic organopolysiloxane is preferably represented by the following formula (1'). (In the formula, R １ , R ２ , R ３ (c and d are as described above.)

[0027] Examples of organopolysiloxanes with a cyclic structure represented by formula (1') above include the compound shown in the following structure. In the formula, Me represents a methyl group and Ph represents a phenyl group. In the formula, 1 ≤ h, 0 ≤ i, 0 ≤ j, 0 ≤ k, 0 ≤ l, 2 ≤ h + l ≤ 20, preferably 2 ≤ h + l ≤ 15, and more preferably 2 ≤ h + l ≤ 10. 2 ≤ h + i ≤ 20, preferably 2 ≤ h + i ≤ 15, and more preferably 2 ≤ h + i ≤ 10. 2 ≤ h + k ≤ 20, preferably 2 ≤ h + k ≤ 15, and more preferably 2 ≤ h + k ≤ 10. 2 ≤ h + i + j ≤ 20, preferably 2 ≤ h + i + j ≤ 15, and more preferably 2 ≤ h + i + j ≤ 10. h is 1 ≤ h ≤ 20, preferably 1 ≤ h ≤ 15, and more preferably 1 ≤ h ≤ 10.

[0028] In the embodiment in which the organopolysiloxane of the present invention is a linear chain that may have branches, in the above average composition formula (1), 0 ≤ a, 0 ≤ b, and a + b is 2 to 20, more preferably 2 to 16, and more preferably 2 to 12. c and d are 0 ≤ d ≤ 15000, preferably 1 ≤ d ≤ 10000, more preferably 1 ≤ d ≤ 7500, even more preferably 1 ≤ d ≤ 5000, 1 ≤ c ≤ 1000, preferably 1 ≤ c ≤ 750, and even more preferably 1 ≤ c ≤ 500. 2 ≤ c + d ≤ 15000, preferably 2 ≤ c + d ≤ 10000, more preferably 2 ≤ c + d ≤ 7500, and even more preferably 2 ≤ c + d ≤ 5000. e, f, and g are such that 0 ≤ e ≤ 14, preferably 0 ≤ e ≤ 10, 0 ≤ f ≤ 14, preferably 0 ≤ f ≤ 10, and 0 ≤ g ≤ 8, preferably 0 ≤ g ≤ 6.

[0029] The embodiment in which the organopolysiloxane is linear or a linear chain which may have branches is, in the above average composition formula (1), the number of alkenyl groups (R) relative to the total number of siloxane units. １The ratio of siloxane units having ) is 0.1 to 100%. The upper limit is preferably 100% or less, preferably 80% or less, more preferably 60% or less, even more preferably 50% or less, more preferably 40% or less, more preferably 30% or less, more preferably 20% or less, and more preferably 10% or less. The lower limit is preferably 0.1% or more, preferably 0.2% or more, more preferably 0.3% or more, more preferably 0.4% or more, more preferably 0.5% or more, more preferably 0.8% or more, and more preferably 1% or more. More preferably 0.1% to 50%, 0.2% to 40%, 0.3% to 30%, 0.4% to 20%, or 0.5% to 10%. a+c is R relative to the total number of siloxane units. １ The ratio of siloxane units containing the above-mentioned properties falls within the above range.

[0030] More preferably, the chain is linear without branching, a + b = 2, more preferably a = 0 and b = 2, e = 0, f = 0, and g = 0.

[0031] Examples of linear organopolysiloxanes represented by the average composition formula (1) include the compound shown in the following structure. In the formula, Me represents a methyl group and Ph represents a phenyl group. (In the equation, h≧1, i≧0, j≧0, k≧0, l≧0, and 0≦i≦15000, 1≦h+i≦15000, 1≦h+i+j≦15000, 1≦h+k≦15000, 1≦h+l≦15000, 0≦i+j≦15000, and 1≦h+i+k+l≦15000.)

[0032] <Method for Producing Organopolysiloxane> Next, the method for producing the organopolysiloxane of the present invention will be described in detail. The production method of the present invention comprises (I) an organopolysiloxane containing an alkyl halogenated compound represented by the following average composition formula (2) and (In the formula, R ２ R represents a linking group, which is a divalent hydrocarbon group having 1 to 10 carbon atoms. ３’ These are groups independently selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and organic groups having a hydroxyl group, X１ (II) an alkenyl group-containing metal carboxylic acid salt is reacted with (III) an alkenyl group-containing organopolysiloxane in the presence of a phase transfer catalyst selected from phosphonium salts, ammonium salts, and crown ethers. The method is characterized by comprising the step of reacting (II) an alkenyl group-containing metal carboxylic acid salt with (III) an alkenyl group-containing organopolysiloxane in the presence of a phase transfer catalyst selected from phosphonium salts, ammonium salts, and crown ethers.

[0033] The manufacturing method of the present invention preferably involves (I) an organopolysiloxane containing an alkyl halogenated compound represented by the following formula (2'), (In the formula, R ２ , R ３ ', X １ (II) an alkenyl group-containing metal carboxylate salt is reacted with (III) an alkenyl group-containing organopolysiloxane represented by the following formula (1') in the presence of a phase transfer catalyst selected from phosphonium salts, ammonium salts, and crown ethers. (In the formula, R １ These are, independently of each other, alkenyl groups having 3 to 20 carbon atoms, and R ２ and R ３ The process includes obtaining the following: (as defined in formula (1) above, where c and d satisfy c≧1, d≧0, and 2≦c+d≦20).

[0034] Another preferred embodiment of the manufacturing method of the present invention includes the step of reacting (I) a linear organopolysiloxane, which may be branched, represented by the average composition formula (2) above and having a viscosity of 0.5 mPa·s or more and 5000 mPa·s or less at 25°C, with (II) an alkenyl group-containing metal carboxylate salt, in the presence of (III) a phase transfer catalyst selected from phosphonium salts, ammonium salts, and crown ethers, to obtain a linear organopolysiloxane, which may be branched, represented by the average composition formula (1) below. (In the formula, R１ These are, independently of each other, alkenyl groups having 3 to 20 carbon atoms, and R ２ R represents a linking group, which is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ３ The groups are independently selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, alkyl halogen groups having 1 to 10 carbon atoms, organic groups having a hydroxyl group, and organic groups having an acyloxy group, and furthermore, a, b, c, d, e, f, and g satisfy 0 ≤ a, 0 ≤ b, 0 ≤ c, 0 ≤ d, 0 ≤ e, 0 ≤ f, and 0 ≤ g, and a + c + e is 1 or greater, and 2 ≤ a + b + c + d + e + f + g ≤ 500, and the organopolysiloxane has a viscosity of 0.5 mPa·s or more and 5000 mPa·s or less at 25°C.

[0035] [(I) Organopolysiloxane containing halogenated alkyl group] In the above average composition formula (2), R ２ R represents a linking group and is a divalent hydrocarbon group having 1 to 10 carbon atoms. ３ R is a group independently selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and organic groups having a hydroxyl group. ２ This is as defined for the average composition formula (1) above. R ３’ These are groups independently selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and organic groups having a hydroxyl group. Examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, and propyl groups, cycloalkyl groups such as cyclohexyl groups, and aryl groups such as phenyl and tolyl groups. Examples of alkoxy groups having 1 to 20 carbon atoms include methoxy, ethoxy, isopropoxy, and butoxy groups. Examples of organic groups having a hydroxyl group include hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxybutyl groups. ３’ Preferably, this is a methyl group, ethyl group, methoxy group, ethoxy group, or hydroxyl group-containing organic group.

[0036] In the above-mentioned halogenated alkyl group-containing organopolysiloxane, X １ These are halogen atoms, independently of each other. １ Examples include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. From the standpoint of ease of reaction, X １ It is preferable that the atoms are chlorine atoms, bromine atoms, and iodine atoms. Also, due to the ease of obtaining the raw materials, X １ It is preferably a chlorine atom or a bromine atom, and is particularly preferably a chlorine atom.

[0037] In the average composition formula (2), a', b', c', d', e', f', and g' satisfy a'≧0, b'≧0, c'≧0, d'≧0, e'≧0, f'≧0, and g'≧0, and a'+c'+e'≧1 and 2≦a'+b'+c'+d'+e'+f'+g'≦15000. In the above average composition formula (2), c'+d' is preferably 1 to 10000, more preferably 2 to 7500, and more preferably 3 to 5000. a'+b' is 0 or 1 to 20, more preferably 2 to 16, and more preferably 2 to 12. e'+f' is preferably 0 to 14, more preferably 0 to 10. g' is preferably 0 to 8, and more preferably 0 to 6. a', b', c', d', e', f', and g' satisfy 2 ≤ a' + b' + c' + d' + e' + f' + g' ≤ 15000, preferably 2 ≤ a' + b' + c' + d' + e' + f' + g' ≤ 10000, and more preferably 2 ≤ a' + b' + c' + d' + e' + f' + g' ≤ 7500.

[0038] The alkyl halide-containing organopolysiloxane represented by average composition formula (2) may be linear, branched, or cyclic. Preferably, the alkyl halide-containing organopolysiloxane having a cyclic structure, represented by the following average composition formula (2'), is preferred. (In the formula, R ２ , R ３’ , and X １ As defined in equation (2) above, c' and d' satisfy 1 ≤ c', 0 ≤ d', and 2 ≤ c' + d' ≤ 20.

[0039] The linear organopolysiloxane represented by the above average composition formula (2), which may have branching, preferably has a viscosity of 0.5 mPa·s or more and 5000 mPa·s or less at 25°C, more preferably a viscosity of 3000 mPa·s or less, and even more preferably a viscosity of 1000 mPa·s or less. If the viscosity exceeds the above upper limit, handling performance will decrease, and the efficiency of the above reaction may decrease. The lower limit of the viscosity is preferably 0.5 mPa·s or more, more preferably 1 mPa·s or more, and even more preferably 5 mPa·s or more. Preferably, it has a viscosity of 0.5 mPa·s or more and 5000 mPa·s or less at 25°C, more preferably a viscosity of 1 mPa·s or more and 3000 mPa·s or less, and even more preferably a viscosity of 5 mPa·s or more and 1000 mPa·s or less. The total number of siloxane units in the branched linear organopolysiloxane is preferably a value that satisfies the above viscosity. The viscosity of the organopolysiloxane is a value measured at 25°C using a BM-type rotational viscometer. In the above average composition formula (2), a', b', c', d', e', f', and g' are values ​​that satisfy the above viscosity range for the organopolysiloxane, preferably 2 ≤ a + b + c + d + e + f + g ≤ 500, and more preferably 2 ≤ a + b + c + d + e + f + g ≤ 300.

[0040] Examples of organopolysiloxanes represented by the average composition formula (2) include compounds shown in the following structure. In the formula, Me represents a methyl group and Ph represents a phenyl group. (In the equation, h'≧1, i'≧0, j'≧0, k'≧0, l'≧0, m'≧1, and 2≦h'+i'≦20, 2≦h'+i'+j'≦20, 0≦k'≦500, 0≦k'+l'≦500, and 0≦k'+m'≦500.)

[0041] [(II) Alkenyl Group-Containing Carboxylic Acid Metal Salts] Alkenyl group-containing carboxylic acid metal salts are reaction reagents for introducing alkenyl groups into halogenated alkyl group-containing organopolysiloxanes. Preferably, they are alkali metal salts of alkenyl group-containing carboxylates, and more preferably, potassium salts of alkenyl group-containing carboxylates. The alkenyl group is an alkenyl group having 3 to 20 carbon atoms, preferably an alkenyl group having 4 to 16 carbon atoms, and more preferably an alkenyl group having 5 to 12 carbon atoms. Examples of alkenyl groups include propenyl, butenyl, pentenyl, hexenyl, octenyl, decenyl, undecenyl, and dodecenyl groups, and preferably, butenyl, pentenyl, octenyl, nonenyl, and decenyl groups, and more preferably, decenyl groups. The double bond in the alkenyl group may be located at the end or in the middle of the molecule, but it is preferable for it to be at the end.

[0042] Examples of alkenyl group-containing carboxylic acid metal salts include potassium pentenoate, sodium pentenoate, potassium hexenoate, sodium hexenoate, potassium nonenate, sodium nonenate, potassium decenoate, sodium decenoate, potassium undecenoate, sodium undecenoate, and preferably potassium pentenoate, potassium hexenoate, potassium nonenate, potassium decenoate, potassium undecenoate, and more preferably potassium undecenoate.

[0043] The amount of alkenyl group-containing carboxylate metal salt added is preferably 1 to 3 moles, more preferably 1 to 2 moles, and more preferably 1.01 to 1.5 moles, per mole of halogen atoms in the alkyl halide-containing organopolysiloxane to which the introduction of alkenyl groups is desired. If the amount of alkenyl group-containing carboxylate metal salt is greater than the lower limit, the introduction of alkenyl groups by the desalting reaction proceeds sufficiently. If the amount is less than the upper limit, the handling properties of the reaction mixture improve, and the pot yield also increases.

[0044] [(III) Phase transfer catalyst] A phase transfer catalyst selected from phosphonium salts, ammonium salts, and crown ethers is a catalyst that promotes the reaction between a halogen atom and a metal carboxylate salt. Preferably, it is a phosphonium salt represented by the following formula (3) or an ammonium salt represented by the following formula (4), and more preferably, it is a phosphonium salt represented by the following formula (3). R ４ ４ P ＋ X ２－ (3) (In the formula, R ４ is, independently of each other, a hydrogen atom or a linear or branched monovalent hydrocarbon group having 1 to 20 carbon atoms, and X ２－ is a halide ion) R ５ ４ N ＋ X ３－ (4) (In the formula, R ５ is, independently of each other, a hydrogen atom or a linear or branched monovalent hydrocarbon group having 1 to 20 carbon atoms, and X ３－ is a halide ion)

[0045] In formula (3), R ４ is, independently of each other, a hydrogen atom or a linear or branched monovalent hydrocarbon group having 1 to 20, preferably 1 to 18, more preferably 1 to 16 carbon atoms. Examples of R ４ include alkyl groups such as methyl group, ethyl group, propyl group, n-butyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, and octyl group, cycloalkyl groups such as cyclohexyl group, and phenyl group. Among them, from the viewpoint of the efficiency of the desalting reaction, R ４ is preferably an alkyl group having 4 to 1 (END) ４ is preferably a butyl group from the viewpoint of ease of removal after the reaction is completed.

[0046] X ２－ is a halide ion, and Br － or Cl － is preferred from the viewpoint of availability.

[0047] As the phase transfer catalyst represented by the formula (3), for example, compounds represented by the following structures can be mentioned.

[0048] In the formula (4), R ５ is, independently of each other, a hydrogen atom or a linear or branched monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 18 carbon atoms, more preferably 1 to 16 carbon atoms. As R ５ , for example, alkyl groups such as methyl group, ethyl group, propyl group, n-butyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, and octyl group, cycloalkyl groups such as cyclohexyl group, and phenyl group etc. can be mentioned. Among them, from the viewpoint of the efficiency of the desalting reaction, it is preferable that R ５ is an alkyl group having 4 to 16 carbon atoms. Further, from the viewpoint of ease of removal after the completion of the reaction, it is preferable that R ５ is a butyl group.

[0049] X ３－ is a halide ion, and Br － or Cl － is preferable from the viewpoint of availability.

[0050] As the phase transfer catalyst represented by the formula (4), for example, compounds represented by the following structures can be mentioned.

[0051] R ４ and R ５ When they are alkyl groups having 4 to 16 carbon atoms, the reason why the reaction efficiency improves is that by having a long-chain alkyl group, the compatibility of the phosphonium salt which is a phase transfer catalyst, and / or the alkenyl group-containing carboxylic acid phosphonium salt and / or alkenyl group-containing carboxylic acid ammonium salt produced by the ion exchange reaction between the ammonium salt and the metal salt of the alkenyl group-containing carboxylic acid with silicone is improved, and the reaction is likely to be promoted. Also, when R ４ and R ５ are butyl groups, since the phosphonium salt and / or the ammonium salt are excellent in solubility in water, they can be easily removed by washing with water after the completion of the reaction. <00>

[0052] Furthermore, the crown ether can be any ether capable of forming a complex with the metal ion in the (II) alkenyl group-containing carboxylate metal salt, such as 18-crown-6-ether, 15-crown-5-ether, 12-crown-4-ether, and dibenzo-18-crown-6-ether.

[0053] The amount of phase transfer catalyst is 0.05 to 15 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 0.3 to 8 parts by mass, per 100 parts by mass of alkyl halide-containing organopolysiloxane. If the amount is less than the lower limit, the reaction may not proceed sufficiently. If the amount exceeds the upper limit, the curability when curing by radiation may decrease. Furthermore, only one type of phase transfer catalyst may be used, or two or more types may be selected and used from the above.

[0054] [Solvent] The desalting reaction of the present invention may be carried out in a solvent or without a solvent, but it is preferable to carry it out in a solvent from the viewpoint of ease of handling and ease of reaction. As the solvent, it is preferable to select and use one or more highly polar organic solvents in addition to water. The amount of solvent is preferably 0 to 200 parts by mass, more preferably 0 or 1 to 150 parts by mass, per 100 parts by mass of component (I).

[0055] In this reaction, using water allows the alkenyl group-containing carboxylate metal salt to dissolve, improving its handling properties.

[0056] Furthermore, the reaction proceeds more efficiently by adding a highly polar solvent. Regarding the type of highly polar solvent, it is preferable to use an aprotic solvent because if a protic solvent is used, the alkyl halide may react with the solvent. In addition, it is preferable to use a solvent with a high boiling point that can be used as a solvent even at high reaction temperatures. Although the detailed mechanism of the reaction is not clear, it is thought that the addition of a highly polar solvent improves the solubility of the alkenyl group-containing carboxylate metal salt in the organic phase, thereby promoting the reaction between the organic alkyl halide-containing silicone and the inorganic salt, the alkenyl group-containing carboxylate metal salt. The amount of highly polar solvent is preferably 0 or 1 to 100 parts by mass, more preferably 5 to 80 parts by mass, and even more preferably 10 to 60 parts by mass, per 100 parts by mass of component (I).

[0057] Examples of the above-mentioned aprotic, highly polar solvents include ether-based solvents such as diethyl ether, tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether; ester-based solvents such as ethyl acetate and butyl acetate; nitrogen-containing solvents such as N,N-dimethylformamide, acetonitrile, and N-methyl-2-pyrrolidone; or mixtures thereof. These can be used individually or in appropriate combinations of two or more.

[0058] [Desalting Reaction] This invention involves desalting the acyl oxide moiety of the alkyl halide and alkenyl group-containing carboxylate metal salt contained in an alkyl halide-containing organopolysiloxane using a correlation transfer catalyst to obtain the target organopolysiloxane. The outline of the reaction is shown below. Note that ≡Si-R in the formula ２ -X １ Regarding this, specific examples can be given in the section on alkyl halide-containing organopolysiloxanes mentioned above. １ indicates a halogen atom, M ｍ＋ This indicates a metal ion.

[0059] The reaction temperature can be 50 to 150°C, but is preferably 60 to 145°C, more preferably 70 to 140°C. If the temperature is lower than the lower limit, the reaction may not proceed sufficiently. If the temperature is higher than the upper limit, there is a concern that the alkenyl groups in the alkenyl group-containing carboxylate metal salt may thicken and gel due to polymerization of the alkenyl groups. The reaction time can be in the range of 1 to 72 hours, but is not limited to this range. The reaction atmosphere can be a nitrogen atmosphere or air.

[0060] After the reaction is complete, the resulting salt can be removed by washing with water or filtration, and then the product can be obtained by dehydration with sodium sulfate or removal of low molecular weight components by vacuum stripping. The temperature during stripping can be 20°C to 130°C and the vacuum can be 1 to 200 mmHg, but it is not limited to these ranges.

[0061] A more preferred embodiment of the manufacturing method of the present invention is to use the cyclic organopolysiloxane represented by the following formula (1') obtained above, (In the formula, R １ , R ２ and R ３ (As described above, c and d satisfy 1 ≤ c, 0 ≤ d, and 2 ≤ c + d ≤ 20) The further step includes polymerizing with at least one organo(poly)siloxane to obtain a linear organopolysiloxane that may have branching and is represented by the above average composition formula (1).

[0062] Ring-opening polymerization of cyclic organopolysiloxanes and organo(poly)siloxanes can be carried out according to conventionally known methods. Examples of organo(poly)siloxanes to be polymerized with the alkenyl group-containing organopolysiloxane represented by formula (1') above include hexamethyldisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and linear or branched dimethylpolysiloxanes. The catalyst, solvent, reaction temperature, and reaction time used for ring-opening polymerization can be appropriately selected. As catalysts, acid catalysts or alkali catalysts commonly used in the equilibrium reaction of organopolysiloxanes can be used. Examples of acid catalysts include sulfuric acid, hydrochloric acid, methanesulfonic acid, and trifluoromethanesulfonic acid. Examples of alkali catalysts include potassium hydroxide, tetramethylammonium hydroxide, and tetrabutylphosphonium hydroxide. As a solvent, any solvent capable of dissolving organopolysiloxanes can be used, such as toluene or hexane. The reaction can also be carried out without a solvent. The reaction temperature and time are appropriately selected depending on the type of catalyst, but for example, the reaction can be carried out at a temperature of 25°C to 160°C for 1 to 70 hours.

[0063] <Silicone Curable Composition> The organopolysiloxane of the present invention can be suitably used for solvent-type or solvent-free silicone curable compositions. In a silicone curable composition containing the organopolysiloxane of the present invention, the content of the organopolysiloxane of the present invention is not particularly limited, but from the viewpoint of coating properties, 2 to 100% by mass of the total composition is preferred, and 4 to 100% by mass is more preferred.

[0064] Examples of silicone curable compositions include curable organopolysiloxane compositions comprising (A) the organopolysiloxane of the present invention, (B) a crosslinking agent, and (C) a catalyst.

[0065] (B) The crosslinking agent is, for example, an organohydrogenpolysiloxane having an average of two or more silicon-bonded hydrogen atoms in one molecule. The crosslinking agent should be one that forms a crosslinked structure with the alkenyl group-containing organopolysiloxane of the present invention and contributes to the formation of a cured film. Examples of organohydrogenpolysiloxanes include polysiloxanes containing hydrogensilyl groups at both ends, polysiloxanes containing hydrogensilyl groups in the side chains, polysiloxanes containing hydrogensilyl groups at one end and in the side chains, and polysiloxanes containing hydrogensilyl groups at both ends and in the side chains. The organohydrogenpolysiloxane may be linear, branched, or cyclic, or a mixture thereof. The SiH group content is preferably 0.1 to 3 moles / 100g in the polyorganosiloxane. Furthermore, the viscosity of this organohydrogenpolysiloxane at 25°C is preferably 0.1 to 1000 mPa·s. The viscosity is measured at 25°C using a BM-type rotational viscometer.

[0066] Examples of the organohydrogenpolysiloxane include, but are not limited to, the following compounds. In the following formulas, Me and Ph represent a methyl group and a phenyl group, respectively. (In the formula, 0 ≤ Z3 ≤ 200, 0 ≤ Z4 ≤ 200, and 0 ≤ Z6 ≤ 10. However, each molecule contains an average of two or more Si-H groups.)

[0067] The amount of organohydrogenpolysiloxane blended is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the alkenyl group-containing polyorganosiloxane of the present invention (A). Within this range, an appropriate crosslinking density can be obtained in the resulting cured product. The amount of component (B) blended is preferably such that the ratio of the number of moles of hydrogen atoms bonded to silicon atoms in component (B) to 1 mole of alkenyl groups in component (A) is in the range of 0.5 to 10, and more preferably in the range of 0.8 to 5.0. If the molar ratio is smaller than the lower limit, the curability of the composition will decrease, and the adhesion of the resulting cured product to the substrate may be poor. If the molar ratio is larger than the upper limit, the resulting release layer may undergo severe peeling.

[0068] (C) The catalyst can be any platinum group metal catalyst that is common as an addition reaction catalyst. Examples include platinum, platinum black, chloroplatinic acid, complexes of platinum or chloroplatinic acid with various olefins or vinylsiloxanes, chloroplatinic acid-alcohol coordination compounds, rhodium, and rhodium-olefin complexes. These may be used individually or in combination of two or more as appropriate. The amount of platinum group metal catalyst added should be a catalytic amount, that is, an effective amount for the crosslinking reaction to proceed. Preferably, the amount of platinum group metal should be 10 to 1000 ppm (mass ratio) of the total mass of components (A) and (B) in order to form a sufficiently hardened film.

[0069] The curable organopolysiloxane composition may be solvent-free or solvent-based. Diluting the composition with an organic solvent provides practical advantages such as improved workability, improved coating thickness, and improved surface finish. Examples of solvents include aromatic hydrocarbon compounds such as toluene and xylene, aliphatic hydrocarbon compounds such as hexane, heptane, and isoparaffin, ketone compounds such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester compounds such as ethyl acetate and butyl acetate, and organic solvents such as diisopropyl ether and 1,4-dioxane. Any compound capable of dissolving silicone may be used. The solvent may be used alone or in appropriate combination of two or more solvents. The amount of solvent is preferably 10 to 100,000 parts by mass, more preferably 100 to 20,000 parts by mass, and more preferably 200 to 2,000 parts by mass, per 100 parts by mass of the alkenyl group-containing polyorganosiloxane of the present invention.

[0070] Other optional components besides those listed above include reaction regulators. Examples of reaction regulators include acetylene alcohols such as 3-methyl-1-butyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 3-methyl-1-pentin-3-ol, and 2-phenyl-3-butyne-2-ol; acetylene compounds such as 3-methyl-3-penten-1-yine and 3,5-dimethyl-3-hexen-1-yine; reaction products of these acetylene compounds with alkoxysilanes, siloxanes, or hydrogensilanes; vinylsiloxanes such as tetramethylvinylsiloxane cyclic compounds; organic nitrogen compounds such as benzotriazole; maleic acid derivatives such as dimethyl maleate; and other organophosphorus compounds, oxime compounds, and organic chloro compounds. The amount of reaction regulator should be such that a good pot life can be obtained, and generally, 0.01 to 5 parts by mass per 100 parts by mass of (A) alkenyl group-containing polyorganosiloxane is preferred. In addition, other optional components such as known antioxidants, pigments, stabilizers, defoamers, adhesion enhancers, thickeners, and inorganic fillers such as silica can be included. The amount of these components included is preferably 0 to 30% by mass, and more preferably 0 to 15% by mass, in the total composition.

[0071] The preparation of the above-mentioned curable organopolysiloxane composition is not particularly limited, but a method is preferred in terms of pot life in which an alkenyl group-containing polyorganosiloxane, an organohydrogenpolysiloxane, an organic solvent if necessary, and an optional component are homogeneously mixed beforehand, and then a platinum group metal catalyst is added immediately before use.

[0072] The organopolysiloxane of the present invention is useful for a curable silicone composition, particularly a release coating agent, that provides release paper or release film exhibiting good curability and low release force at both low and high speeds. The release paper and release film have a paper substrate or film substrate and a release layer made of a cured product of the curable organopolysiloxane composition formed on the substrate. The release layer only needs to be formed on at least one surface of the substrate, and may be on one side or both sides. Examples of substrates include polyethylene laminate paper, glassine paper, fine paper, kraft paper, clay coated paper and other coated papers, synthetic paper such as Yupo, polyethylene film, polypropylene film such as CPP and OPP, polyester film such as polyethylene terephthalate film, polyamide film, polyimide film, polylactic acid film, polyphenol film, polycarbonate film, etc. To improve the adhesion between the substrate and the release layer, substrates that have been corona treated, etched, or plasma treated may be used.

[0073] The method for manufacturing release paper and release film is not particularly limited and can be manufactured according to conventionally known methods. For example, a method can be made which includes the steps of applying a curable organopolysiloxane composition to at least one surface of a substrate, for example, one or both surfaces, and drying and curing the curable organopolysiloxane composition to form a cured layer (i.e., a release layer). Examples of application methods include coating with a comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater, gravure coater, wire bar coater, etc., as well as screen coating, dipping coating, cast coating, etc. When applying the coating, the curable organopolysiloxane composition may be used as is, or it may be further diluted with the above-mentioned dilution solvent or water within the above-mentioned range.

[0074] There are no particular restrictions on the amount of curable organopolysiloxane composition that can be applied, but typically it is 0.01 to 100 g / m² as solid content. ２ Preferably, 0.03 to 10 g / m ２This is more preferable. As for drying methods, methods that remove volatile components and solvent components by heating are possible. For example, a hot air dryer, an IR dryer, etc. Alternatively, it may be dried by leaving it at room temperature. The curing method can be a conventionally known method. For example, the curing temperature is preferably 50 to 200°C, and more preferably 70 to 180°C. The curing time is preferably 1 to 120 seconds, and more preferably 5 to 90 seconds. When creating a release layer on both sides of the substrate, it is preferable to perform the cured film formation operation on one side of the substrate at a time.

[0075] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the examples, parts refer to parts by mass. Furthermore, the viscosity of the organopolysiloxane below is the value measured at 25°C using a BM-type rotational viscometer. ２９ Si-NMR measurements were performed using a JNM-ECX500II (manufactured by JEOL Ltd.). The measurement solvent was deuterated chloroform. １ ¹H-NMR measurements were performed using an AVANCE III 400 (Bruker BioSpin, Inc.). The measurement solvent was deuterated chloroform.

[0076] [Example 1] 51.23 g of 10-undecenoic acid and 29.80 g of N-methyl-2-pyrrolidinone were charged into a separable flask equipped with a stirrer, dropping funnel, thermometer, and Dean-Stark apparatus. 32.07 g of 48% potassium hydroxide aqueous solution was added to the dropping funnel and added dropwise to prepare a potassium 10-undecenoate solution (the amount of potassium 10-undecenoate being 0.75 equivalents of halogen groups in the organopolysiloxane (I-1) described below). Subsequently, 50.00 g of the organopolysiloxane shown in the following average composition formula (I-1) (viscosity 200 mPa·s at 25°C) and 5.00 g of tetrabutylphosphonium bromide were added, and the reaction was carried out by heating and stirring at a temperature of 120°C for 4 hours. To this reaction mixture, 17.97 g of potassium acetate (an amount equivalent to 0.50 equivalents relative to the halogen groups in (I-1)) was added, and the reaction was carried out by heating and stirring at a temperature of 120°C for 4 hours. After that, the salt was removed from the reaction mixture by washing with water, and then impurities were removed by tape stripping under reduced pressure at 15 mmHg at 70°C for 4 hours to obtain 80.24 g of a yellow, transparent organopolysiloxane. The obtained product was, ２９ Si-NMR and １ 1H-NMR measurement confirmed that it is an organopolysiloxane represented by the following average composition formula (a-1). １ The H-NMR chart is shown in Figure 1. ２９ The Si-NMR chart is shown in Figure 2. The obtained organopolysiloxane had a viscosity of 140 mPa·s at 25°C and an alkenyl group content of 0.295 mol / 100g.

[0077] [Example 2] The above Synthesis Example 1 was repeated except that 51.23 g of 10-undecenoic acid was replaced with 27.83 g of 4-pentenoic acid to obtain 60.25 g of pale yellow transparent organopolysiloxane. The obtained product was, ２９ Si-NMR and １ ¹H-NMR measurement confirmed that the substance was an organopolysiloxane represented by the average composition formula (a-2) shown below. The obtained organopolysiloxane had a viscosity of 120 mPa·s and an alkenyl group content of 0.394 mol / 100g.

[0078] [Example 3] The above Synthesis Example 1 was repeated except that (I-1) 50.00 g was replaced with (I-2) 65.40 g, and 93.56 g of pale yellow transparent organopolysiloxane was obtained. The obtained product was, ２９ Si-NMR and １ ¹H-NMR measurement confirmed that the substance was an organopolysiloxane represented by the average composition formula (a-3) shown below. The obtained organopolysiloxane had a viscosity of 150 mPa·s and an alkenyl group content of 0.253 mol / 100g.

[0079] [Example 4] 68.10 g of 10-undecenoic acid and 39.60 g of N-methyl-2-pyrrolidinone were charged into a separable flask equipped with a stirrer, dropping funnel, thermometer, and Dean-Stark apparatus. 43.19 g of 48% potassium hydroxide aqueous solution was added to the dropping funnel and added dropwise to prepare a potassium 10-undecenoate solution (the amount of potassium 10-undecenoate being 1.01 equivalents to the halogen groups in the organopolysiloxane (I-1) described below). Subsequently, 50.00 g of the organopolysiloxane shown in the following average composition formula (I-1) (viscosity 200 mPa·s at 25°C) and 5.00 g of tetrabutylphosphonium bromide were added, and the reaction was carried out by heating and stirring at a temperature of 120°C for 17 hours. Subsequently, the salt was removed from the reaction mixture by washing with water, and then impurities were removed by stripping under reduced pressure at 15 mmHg at 70°C for 4 hours, yielding 89.85 g of a yellow, transparent organopolysiloxane. The obtained product was, ２９ Si-NMR and １ ¹H-NMR measurement confirmed that the substance was an organopolysiloxane represented by the average composition formula (a-4) shown below. The obtained organopolysiloxane had a viscosity of 150 mPa·s and an alkenyl group content of 0.352 mol / 100g.

[0080] [Example 5] 11.45 g of organopolysiloxane represented by (a-1) synthesized in Example 1, 120.10 g of octamethylcyclotetrasiloxane, 0.10 g of hexamethyldisiloxane, and 0.17 g of trifluoromethanesulfonic acid were charged into a separable flask equipped with a stirrer and reflux tubing. The mixture was heated and stirred for 8 hours at a temperature of 50°C. 306.95 g of toluene and synthetic hydrotalcite Mg were added to this mixture. １－ｘ Al ｘ (OH) ２ (CO ３ ) ｘ／２ mH ２ 1.02 g of O (Kyowa Chemical Industry Co., Ltd., Kyoward® 500SH) was added and the mixture was stirred at room temperature for 2 hours to neutralize it. After removing the solid by filtration, 92.29 g of pale yellow transparent organopolysiloxane was obtained by vacuum stripping at 15 mmHg for 3 hours at 120°C. The obtained product was, ２９ Si-NMR and １ 1H-NMR measurement confirmed that it is an organopolysiloxane represented by the average composition formula (a-5) below. １ The H-NMR chart is shown in Figure 3. ２９ The Si-NMR chart is shown in Figure 4. The obtained organopolysiloxane had a viscosity of 262,000 mPa·s and an alkenyl group content of 0.028 mol / 100g. (In the equation, b = 2, c = 25, d1 = 8, and d2 = 1215.)

[0081] [Example 6] The process of Example 5 was repeated except that the amount of hexamethyldisiloxane was increased to 0.25 g, and 92.54 g of pale yellow transparent organopolysiloxane was obtained. The obtained product was, ２９ Si-NMR and １ ¹H-NMR measurement confirmed that the substance was an organopolysiloxane represented by the average composition formula (a-6) shown below. The obtained organopolysiloxane had a viscosity of 20,900 mPa·s and an alkenyl group content of 0.028 mol / 100g. (In the equation, b = 2, c = 15, d1 = 5, and d2 = 728.)

[0082] [Example 7] The process of Example 5 was repeated, except that 11.45 g of the organopolysiloxane represented by (a-1) in Example 5 was replaced with 8.60 g of the organopolysiloxane represented by (a-2) synthesized in Example 2, to obtain 89.70 g of a pale yellow transparent organopolysiloxane. The obtained product was, ２９ Si-NMR and １ ¹H-NMR measurement confirmed that the substance was an organopolysiloxane represented by the average composition formula (a-7) shown below. The obtained organopolysiloxane had a viscosity of 250,000 mPa·s and an alkenyl group content of 0.029 mol / 100g. (In the equation, b = 2, c = 24, d1 = 8, and d2 = 1190.)

[0083] [Example 8] The process of Example 5 was repeated, except that 11.45 g of the organopolysiloxane represented by (a-1) in Example 5 was replaced with 13.35 g of the organopolysiloxane represented by (a-3) synthesized in Example 3, to obtain 93.56 g of a pale yellow transparent organopolysiloxane. The obtained product was, ２９ Si-NMR and １ ¹H-NMR measurement confirmed that the substance was an organopolysiloxane represented by the average composition formula (a-8) shown below. The obtained organopolysiloxane had a viscosity of 283,000 mPa·s and an alkenyl group content of 0.028 mol / 100g. (In the equation, b = 2, c = 26, d1 = 9, and d2 = 1270.)

[0084] [Example 9] The process of Example 5 was repeated, except that 11.45 g of the organopolysiloxane represented by (a-1) in Example 5 was replaced with 9.64 g of the organopolysiloxane represented by (a-4) synthesized in Example 4, to obtain 89.88 g of a pale yellow transparent organopolysiloxane. The obtained product was, ２９ Si-NMR and １ ¹H-NMR measurement confirmed that the substance was an organopolysiloxane represented by the average composition formula (a-9) shown below. The obtained organopolysiloxane had a viscosity of 274,000 mPa·s and an alkenyl group content of 0.028 mol / 100g. (In the equation, b = 2, c = 24, and d = 1170.)

[0085] [Example 10] 11.7 g of 10-undecenoic acid (an amount equivalent to 1.01 equivalents relative to the halogen groups in organopolysiloxane (I-3) described below), 8.8 g of potassium carbonate (an amount equivalent to 1.0 equivalent relative to 10-undecenoic acid), 20.0 g of N,N-dimethylformamide, 3.0 g of tetrabutylammonium bromide, and 100.0 g of organopolysiloxane represented by the following average composition formula (I-3) (viscosity of 150 mPa·s at 25°C) were charged into a separable flask equipped with a stirrer, dropping funnel, thermometer, and Dean-Stark apparatus. The reaction was carried out by heating and stirring at a temperature of 120°C for 8 hours. Subsequently, 35.0 g of toluene was added to the reaction mixture, and after removing the salt by washing with water, impurities were removed by stripping under reduced pressure at 15 mmHg at 120°C for 4 hours, yielding 76.3 g of pale yellow, transparent organopolysiloxane. The obtained product was, ２９ Si-NMR and １ ¹H-NMR measurement confirmed that it is an organopolysiloxane represented by the following average composition formula (a-10). １ The H-NMR chart is shown in Figure 5. ２９ The Si-NMR chart is shown in Figure 6. The obtained organopolysiloxane had a viscosity of 120 mPa·s and an alkenyl group content of 0.063 mol / 100g. (In the equation, b' = 3, c' = 6, d' = 113, and f' = 1.) (In the equation, b = 3, c = 6, d = 96, and f = 1.)

[0086] [Example 11] 20.27 g of the organopolysiloxane represented by (a-1) synthesized in Example 1, 81.57 g of octamethylcyclotetrasiloxane, 1.62 g of hexamethyldisiloxane, and 0.17 g of trifluoromethanesulfonic acid were charged into a separable flask equipped with a stirrer and reflux tubing. The mixture was heated and stirred for 8 hours at a temperature of 50°C. 1.02 g of Kyoward® 500 was added to this mixture and the mixture was stirred at room temperature for 2 hours to neutralize it. Then, the low molecular weight siloxane was removed by tape stripping under reduced pressure of 15 mmHg at 120°C for 3 hours, and the solid was removed by filtration to obtain 82.77 g of a pale yellow, transparent organopolysiloxane. The obtained product was, ２９ Si-NMR and １ ¹H-NMR measurement confirmed that the substance was an organopolysiloxane represented by the average composition formula (a-11) shown below. The obtained organopolysiloxane had a viscosity of 200 mPa·s and an alkenyl group content of 0.058 mol / 100g. (In the equation, b = 2, c = 6, d1 = 2, and d2 = 110.)

[0087] [Example 12] The procedure in Example 11 was repeated, except that 20.27 g of the organopolysiloxane represented by (a-1) in Example 11 was replaced with 15.22 g of the organopolysiloxane represented by (a-2) synthesized in Example 2, to obtain 77.43 g of a pale yellow transparent organopolysiloxane. The obtained product was, ２９ Si-NMR and １ ¹H-NMR measurement confirmed that the substance was an organopolysiloxane represented by the average composition formula (a-12) shown below. The obtained organopolysiloxane had a viscosity of 190 mPa·s and an alkenyl group content of 0.061 mol / 100g. (In the equation, b = 2, c = 6, d1 = 2, and d2 = 108.)

[0088] [Example 13] The procedure in Example 11 was repeated, except that 20.27 g of the organopolysiloxane represented by (a-1) in Example 11 was replaced with 23.64 g of the organopolysiloxane represented by (a-3) synthesized in Example 3, to obtain 83.24 g of a pale yellow transparent organopolysiloxane. The obtained product was, ２９ Si-NMR and １ ¹H-NMR measurement confirmed that the substance was an organopolysiloxane represented by the average composition formula (a-13) shown below. The obtained organopolysiloxane had a viscosity of 210 mPa·s and an alkenyl group content of 0.056 mol / 100g. (In the equation, b = 2, c = 6, d1 = 2, and d2 = 112.)

[0089] [Example 14] The process of Example 11 was repeated, except that 20.27 g of the organopolysiloxane represented by (a-1) in Example 11 was replaced with 17.07 g of the organopolysiloxane represented by (a-4) synthesized in Example 4, to obtain 79.89 g of a pale yellow transparent organopolysiloxane. The obtained product was, ２９ Si-NMR and １ ¹H-NMR measurement confirmed that the substance was an organopolysiloxane represented by the average composition formula (a-14) shown below. The obtained organopolysiloxane had a viscosity of 190 mPa·s and an alkenyl group content of 0.059 mol / 100g. (In the equation, b = 2, c = 6, and d = 111.)

[0090] Curable silicone compositions were prepared using the following components, with the compositions shown in Tables 1 and 2.

[0091] The following alkenyl group-containing organopolysiloxanes were used as the main component of the solvent-curable silicone composition: (A-1): Compound synthesized in Example 5 (A-2): Compound synthesized in Example 9 (A'-3): Organopolysiloxane represented by the following average composition formula (In the formula, a = 2, b = 25, c = 1225.) (A'-4): Organopolysiloxane represented by the following average empirical formula (In the equation, a = 2, b = 32, and c = 8000.)

[0092] The following alkenyl group-containing organopolysiloxanes were used as the main component of the solvent-free curable silicone composition: (A-5): Compound synthesized in Example 10; (A'-6): Organopolysiloxane represented by the following average composition formula. (In the formula, a = 2, b = 6, c = 112.) (A'-7): Organopolysiloxane represented by the following average empirical formula (In the equation, a' = 2 and c = 100.)

[0093] Other components used in the examples and comparative examples are as follows: (B-1): Average unit formula: [(CH ３ ) ３ SiO １／２ ] ２ [H(CH ３ ) SiO ２／２ ] ３８ Organopolysiloxane represented by (B-2): Average unit formula: [(CH ３ ) ３ SiO １／２ ] ２ [(CH ３ ) ２ SiO ２／２ ] ２８ [H(CH ３ ) SiO ２／２ ] ７０ Organopolysiloxane represented by (C-1): A platinum group metal catalyst obtained by diluting the reaction product of platinum and 1,3-divinyltetramethyldisiloxane with toluene so that the platinum content is 0.50% by mass. (D-1) Toluene (D-2) Methyl ethyl ketone (E-1) 1-ethynyl-1-cyclohexanol

[0094] [Curing of Solvent-Type Curable Silicone Composition] The above solvent-type curable silicone composition is applied to polyethylene laminate paper using a bar coater and heated in a hot air dryer at 120°C for 30 seconds to a thickness of 0.6 to 0.8 g / m². ２ A release paper having a cured coating was obtained.

[0095] [Curing of Solvent-Free Curable Silicone Composition] The above solvent-free curable silicone composition was applied to a metal roll of an RI tester (manufactured by IHI Machinery Systems Co., Ltd.), the metal roll was pressed against a rubber roll, and the two rolls were rotated for 45 seconds to stretch the composition uniformly. The composition was then transferred from the rubber roll to polyethylene laminate paper. The polyethylene laminate paper on which the composition was transferred was heated in a 120°C hot air dryer for 30 seconds to a thickness of 0.9 to 1.1 g / m². ２ A release paper having a cured coating was obtained.

[0096] [Low-speed peeling force] After aging the release paper obtained by the above curing method at 25°C for 24 hours, a 25 mm wide acrylic adhesive tape TESA-7475 (tesa UK Ltd) was attached to the cured surface of the release paper, and it was cut to a size of 25 mm x 23 cm. This was sandwiched between glass plates and cured at 25°C at a rate of 70 g / cm². ２ The sample was prepared after aging under the specified load for 24 hours. The TESA-7475 tape sample was peeled off at a 180° angle at 0.3 m / min using a tensile testing machine (DSC-500, manufactured by Shimadzu Corporation), and the force required for peeling was measured.

[0097] [High-Speed ​​Peeling Force] After aging the release paper obtained by the above curing method at 25°C for 24 hours, a 25mm wide acrylic adhesive tape TESA-7475 (tesa UK Ltd) was attached to the cured surface of the release paper, and it was cut to a size of 25mm x 23cm. This was sandwiched between glass plates and cured at 25°C at a rate of 70g / cm². ２ The sample was prepared after aging under the specified load for 24 hours. The TESA-7475 tape sample was peeled off at a 180° angle at 60 m / min using a tensile testing machine (DSC-500, manufactured by Shimadzu Corporation), and the force required for peeling was measured.

[0098] [Percentage subsequent adhesion (according to FINAT test method no. 11)] A release layer is formed in the same manner as the curing evaluation described above, and a 25 mm wide acrylic adhesive tape TESA-7475 (tesa UK Ltd) is applied to the surface of the release layer. 70 g / cm² is dried in a 25°C oven. ２ The sample was subjected to a load and heat-treated for 20 hours. Afterward, a 25mm wide adhesive tape sample was peeled from the release layer and attached to a stainless steel plate. Next, using a tensile testing machine (AGS-50G, Shimadzu Corporation), the 25mm wide adhesive tape was peeled from the stainless steel plate, and the peel strength X was measured. Additionally, a 25mm wide adhesive tape not bonded to the release layer was attached to the stainless steel plate, and using the tensile testing machine, the 25mm wide adhesive tape was peeled from the stainless steel plate, and the peel strength Y was measured. The residual adhesion rate (Percentage subsequent adhesion) was then calculated using the formula (Peel strength X / Peel strength Y) × 100 (%). A higher residual adhesion rate indicates superior peelability of the release layer, suppressing the reduction in adhesive strength of the 25mm wide adhesive tape due to bonding to the release layer, i.e., suppressing bleed-out from the coating.

[0099] [Exposure Resistance] The release paper obtained by the curing method described above was aged for 24 hours indoors at 25°C with the release agent layer facing down (no exposure to air) and with the release agent layer facing up (exposure to air). Then, a 50 mm wide acrylic double-sided adhesive tape, Nitto Denko Corporation's Nitto 502, was attached to the cured surface of the release paper, and it was cut to a size of 50 mm x 23 cm. This was sandwiched between glass plates and aged at room temperature at a rate of 35 g / cm². ２ The sample was prepared after aging under a load for 24 hours. The Nitto 502 tape sample was peeled at a 180° angle of 0.3 m / min using a tensile testing machine (Shimadzu Corporation DSC-500 model), and the force required to peel off the sample with and without exposure to air was measured. A smaller difference in peeling force between the sample with and without exposure to air indicates superior exposure resistance.

[0100]

[0101]

[0102] The organopolysiloxane having an ester structure and an alkenyl-containing group according to the present invention is useful for curable silicone compositions, particularly for release coating agents. Compared to conventional vinyl-group-containing organopolysiloxanes, the organopolysiloxane of the present invention improves the curability of curable silicone compositions and can be used as a main component of a silicone curable composition that forms a cured film with low peeling force at both low and high speeds and good exposure resistance. Therefore, the alkenyl-group-containing organopolysiloxane of the present invention can be suitably used as a main component of a silicone curable composition for release sheets.

Claims

1. Organopolysiloxanes represented by the following average composition formula (1) (In the formula, R １ These are, independently of each other, alkenyl groups having 3 to 20 carbon atoms, and R ２ R represents a linking group, which is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ３ (These groups are independently selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, alkyl halogen groups having 1 to 10 carbon atoms, organic groups having a hydroxyl group, and organic groups having an acyloxy group, and furthermore, a, b, c, d, e, f, and g satisfy a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, g≧0, a+c+e is 1 or greater, and 2≦a+b+c+d+e+f+g≦15000.) 2. In the above average composition formula (1), R １ The organopolysiloxane according to claim 1, wherein the number of siloxane units having the above is 0.1 to 100% of the total number of siloxane units.

3. In the above average composition formula (1), R １ The organopolysiloxane according to claim 1, wherein each is an alkenyl group having 5 to 12 carbon atoms, independently of the others.

4. In the above average composition formula (1), R ２ The organopolysiloxane according to claim 1, wherein is a divalent hydrocarbon group having 1 to 7 carbon atoms.

5. The organopolysiloxane according to claim 1, wherein in the above average composition formula (1), a = 0 and e = 0.

6. The organopolysiloxane according to claim 1, represented by the following formula (1') (wherein R １ , R ２ and R ３ are as defined above, c is 1 or more, d is 0 or more, and 2 ≦ c + d ≦ 20, and c is a value such that the number of siloxane units having the R １ is 1 to 100% of the total number of all siloxane units).

7. In the above average composition formula (1), a and b are such that 2 ≤ a + b ≤ 20, c ≥ 1, d ≥ 0, and 1 ≤ c + d ≤ 15000, e = 0, and a + c is R １ The organopolysiloxane according to claim 1, which may have branching, wherein the number of siloxane units having the specified value is 0.1 to 50% of the total number of siloxane units.

8. A method for producing an organopolysiloxane according to any one of claims 1 to 7, comprising: (I) an organopolysiloxane containing an alkyl halogenated compound represented by the following average composition formula (2); (In the formula, R ２ R represents a linking group, which is a divalent hydrocarbon group having 1 to 10 carbon atoms. ３’ These are groups independently selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and organic groups having a hydroxyl group, X １ The production method comprising the step of reacting (II) an alkenyl group-containing metal carboxylate salt with (III) an alkenyl group-containing organopolysiloxane in the presence of a phase transfer catalyst selected from phosphonium salts, ammonium salts, and crown ethers. (II) are halogen atoms, and a', b', c', d', e', f', and g' satisfy a'≧0, b'≧0, c'≧0, d'≧0, e'≧0, f'≧0, and g'≧0, a'+c'+e' is 1 or greater, and 2≦a'+b'+c'+d'+e'+f'+g'≦15000.

9. (I) A halogenated alkyl group-containing organopolysiloxane represented by the following formula (2'), (In the formula, R ２ , R ３ ', X １ (II) an alkenyl group-containing metal carboxylate salt is reacted with (III) an alkenyl group-containing organopolysiloxane represented by the following formula (1') in the presence of a phase transfer catalyst selected from phosphonium salts, ammonium salts, and crown ethers. (In the formula, R １ These are, independently of each other, alkenyl groups having 3 to 20 carbon atoms, and R ２ and R ３ The manufacturing method according to claim 8, comprising the step of obtaining (where c and d are as defined in formula (1) above, c ≥ 1, d ≥ 0, and 2 ≤ c + d ≤ 20).

10. The manufacturing method according to claim 9, further comprising the step of polymerizing the alkenyl group-containing organopolysiloxane represented by formula (1') with at least one organo(poly)siloxane to obtain a linear organopolysiloxane represented by the average composition formula (1) which may have branching.

11. The process includes the step of (I) reacting a linear organopolysiloxane, which may be branched, represented by the average composition formula (2) above and having a viscosity of 0.5 mPa·s or more and 5000 mPa·s or less at 25°C, with (II) an alkenyl group-containing metal carboxylate salt, in the presence of (III) a phase transfer catalyst selected from phosphonium salts, ammonium salts, and crown ethers, to obtain a linear organopolysiloxane, which may be branched, represented by the average composition formula (1) below. (In the formula, R １ These are, independently of each other, alkenyl groups having 3 to 20 carbon atoms, and R ２ R represents a linking group, which is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ３ (The organopolysiloxane is a group selected independently from a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, an organic group having a hydroxyl group, and an organic group having an acyloxy group, and furthermore, a, b, c, d, e, f, and g satisfy a≧0, b≧0, c≧0, d≧0, e≧0, f≧0, g≧0, a+c+e is 1 or more, and 2≦a+b+c+d+e+f+g≦500, and the organopolysiloxane has a viscosity of 0.5 mPa·s or more and 5000 mPa·s or less at 25°C.) The manufacturing method according to claim 8.

12. A silicone curable composition comprising the organopolysiloxane described in any one of claims 1 to 7.

13. A peeling coating agent comprising the organopolysiloxane according to any one of claims 1 to 7.

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