Method for producing epoxy group-containing organohydrogenpolysiloxane, curable organopolysiloxane composition, and release sheet

Abstract

Provided is an epoxy group-containing organohydrogenpolysiloxane having a sufficiently high effect as an adhesion improver. 【Solution】A method for producing an epoxy group-containing organohydrogenpolysiloxane, comprising: (a1) a linear, branched or cyclic organohydrogenpolysiloxane; (a2) an epoxy group-containing alkoxysilane; (a3) optionally, an alkoxysilane, wherein the components are blended such that the total molar ratio of components (a2) and (a3) to component (a1), [(a2)+(a3)] / (a1), is from 0.1 / 1 to 998 / 1; the following components (a4) and (a5): (a4) water in an amount such that the molar ratio thereof to 1 mole of alkoxy groups derived from components (a2) and (a3) is from 0.2 to 1, and (a5) an acid catalyst having an acid dissociation constant (pKa) of from -2 to 4, in an effective amount wherein the production method comprises a step of obtaining the epoxy group-containing organohydrogenpolysiloxane by a hydrolysis equilibration reaction in the presence of the above components.

Description

[Technical Field]

[0001] This invention relates to a method for producing epoxy group-containing organohydrogenpolysiloxanes. More specifically, it relates to a method for producing epoxy group-containing organohydrogenpolysiloxanes that exhibit less gelation and thickening during the reaction and over time by hydrolyzing and equilibrating an organohydrogenpolysiloxane and an epoxy group-containing alkoxysilane in the presence of water and a specific acid catalyst. Furthermore, it relates to a curable organopolysiloxane composition that provides a cured product suitable as a release sheet, and to a release sheet. [Background technology]

[0002] Conventionally, to prevent adhesion between substrates such as paper and plastic films and adhesive materials, a cured film of an organopolysiloxane composition is formed on the substrate surface to impart release properties. Among the methods for forming the above-mentioned organopolysiloxane cured film on the substrate surface, the release film formation method by addition reaction is widely used because it offers advantages such as excellent curability and the ability to vary the release properties. In this addition reaction, platinum group metals, including platinum, are generally used as catalysts.

[0003] The cured film obtained from this addition-curing type organopolysiloxane composition needs to be able to peel off adhesive materials such as tape with low peeling force, while also needing to adhere closely to substrates such as paper or plastic film. Cured films with poor adhesion may detach from the substrate (the cured film peels off like eraser shavings) a few days after formation, or during storage under high temperature and high humidity conditions.

[0004] The adhesion of the cured film to the substrate is thought to be due to the SiH in the organopolysiloxane composition. This is because compositions with a low SiH content often exhibit poor adhesion, and increasing the SiH content improves adhesion in such cases. Furthermore, the improvement of adhesion by epoxy groups has been known for some time, and epoxy group-containing organopolysiloxanes are used as adhesion enhancers.

[0005] Patent Document 1 describes a release composition comprising a curable alkenyl silicone having a branched structure and an adhesion enhancer for release coatings having oxirane or epoxide and SiH. This improves adhesion to PET films.

[0006] Patent Document 2 describes a silicone composition for peel-off coatings, comprising a silicone base consisting of an alkenyl organopolysiloxane, a SiH-containing crosslinking silicone oil, and a catalyst, to which an epoxy group-containing organohydrogenpolysiloxane is added. By defining the epoxy group-containing organohydrogenpolysiloxane to an appropriate structure, adhesion to glassine paper and PET film is improved.

[0007] Patent documents 3 and 4 also describe epoxy group-containing organopolysiloxane as an adhesion-promoting additive, but Patent document 3 specifies the epoxy group content to be 100 mmol or less per 100 g of epoxy group-containing organopolysiloxane, and Patent document 4 specifies the amount of SiH to be less than 1 unit per molecule of epoxy group-containing organopolysiloxane. This improves adhesion to glassine paper and PET film.

[0008] On the other hand, in recent years, from the perspective of the SDGs, there has been a growing demand for reducing the amount of platinum group metal catalysts used in addition reactions. Patent document 6 describes how adding an (meth)acrylic group-containing organopolysiloxane compound to an addition reaction type organopolysiloxane composition enables addition reactions with fewer platinum group metal catalysts and allows for the formation of a cured film with peeling strength equivalent to that of conventional methods.

[0009] Furthermore, Patent Document 7 describes how the amount of platinum group metal catalyst used is similarly reduced by using an organopolysiloxane having two or more alkenyl groups bonded to silicon in one molecule and an average of 0.01 to 2.9 (meth)acrylic groups as the base polymer for an addition reaction type organopolysiloxane composition. While efforts are being made to reduce the amount of platinum catalyst used in this way, there is also a desire for further improvement in adhesion. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] Special Publication No. 2006-519893 [Patent Document 2] Special Publication No. 2018-538372 [Patent Document 3] Special Publication No. 2013-527857 [Patent Document 4] Special Publication No. 2009-541559 [Patent Document 5] International Publication No. 2020-145151 [Patent Document 6] International Publication No. 2021-251255 [Overview of the project] [Problems that the invention aims to solve]

[0011] The epoxy group-containing organopolysiloxanes described in Patent Documents 1 to 4 are all produced by adding an epoxy compound such as allyl glycidyl ether to an organohydrogenpolysiloxane in the presence of a platinum catalyst. When some of the SiH groups of the organohydrogenpolysiloxane are left intact, a compound containing both epoxy and SiH groups is obtained, which is a production method that has been used for a long time.

[0012] However, when the inventors attempted to synthesize an epoxy group-containing organohydrogenpolysiloxane with a high proportion of SiH groups remaining via the above addition reaction, the reaction gelled during the process, preventing them from obtaining the desired product. Even when the reaction conditions were optimized to suppress gelation, the product exhibited significant thickening, and furthermore, when the product was stored at room temperature, it gelled again in a short period of time.

[0013] A similar description can be found in paragraph

[0023] of Patent Document 4, which describes how the storage stability of epoxy group-containing organopolysiloxanes is improved by substantially reducing the number of SiH units to zero. However, when the inventors used an epoxy group-containing organopolysiloxane without SiH groups as an additive, the improvement in adhesion was insufficient.

[0014] The present invention has been made in view of the above circumstances, and aims to provide an epoxy group-containing organohydrogenpolysiloxane that is sufficiently effective as an adhesion enhancer, and a manufacturing method that suppresses gelation and thickening of the organohydrogenpolysiloxane during reaction and over time. Furthermore, the present invention aims to provide an organopolysiloxane composition with excellent adhesion to various substrates by adding the organohydrogenpolysiloxane, and a release sheet having a cured film of the composition. [Means for solving the problem]

[0015] The present inventors, through diligent research to achieve the above objective, discovered that by hydrolyzing and equilibrating an organohydrogenpolysiloxane with an epoxy group-containing alkoxysilane in the presence of water and a specific acid catalyst, an epoxy group-containing organohydrogenpolysiloxane with less gelation and thickening during the reaction and over time can be obtained, leading to the present invention. The obtained epoxy group-containing organohydrogenpolysiloxane was found to have a high effect in improving adhesion, which led to the present invention.

[0016] Accordingly, the present invention provides the following invention. 1. A method for producing an epoxy group-containing organohydrogenpolysiloxane, (a1) a linear, branched or cyclic organohydrogenpolysiloxane represented by the following average composition formula (1), (R 1 3SiO 1 / 2 ) a (R 1 2SiO) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (1) (wherein, R 1 is each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or a hydrogen atom, and at least two of R 1 are hydrogen atoms. a is a number of 0 or more, b is a number of 0 or more, c is a number of 0 or more, d is a number of 0 or more, and 2≦a+b+c+d≦500.) (a2) an epoxy group-containing alkoxysilane represented by the following average composition formula (2), R 2 -SiR 3 x (OR 4 ) 3-x (2) (wherein, R 2 is each independently an epoxy group-containing monovalent organic group, R 3 and R 4 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and x is 0, 1 or 2.) (a3) as an optional component, an alkoxysilane represented by the following average composition formula (3), SiR 5 y (OR 6 ) 4-y (3) (wherein, R 5 and R 6 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and y is 0, 1, 2, or 3.) The mixture is prepared such that the molar ratio of the total of components (a2) and (a3) ​​to component (a1) [(a2)+(a3)] / (a1) is between 0.1 / 1 and 998 / 1. The following components (a4) and (a5) (a4) Water: an amount such that the molar ratio of alkoxy groups derived from component (a2) and component (a3) ​​to 1 mole is 0.2 to 1, (a5) Acid catalyst with an acid dissociation constant (pKa) of -2 to 4: effective amount A method for producing the epoxy group-containing organohydrogenpolysiloxane, comprising the step of carrying out a hydrolysis equilibration reaction in the presence of a substance to obtain the epoxy group-containing organohydrogenpolysiloxane. 2. (a1) The component is the following average composition formula (4) (R 7 (3-z) H z SiO 1 / 2 )2(R 7 HSiO) g (R 7 2SiO) h (4) (In the formula, R 7 These are, independently of each other, unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and z is 0 or 1. When z is 0, g is a number greater than or equal to 2, h is a number greater than or equal to 0, g > h, and 2 ≤ g + h ≤ 498. When z is 1, g is a number greater than or equal to 0, h is a number greater than or equal to 0, g ≥ h, and 0 ≤ g + h ≤ 498. A method for producing the epoxy group-containing organohydrogenpolysiloxane described in 1, which is a linear organohydrogenpolysiloxane represented by . 3. (a1) The component is the following average composition formula (5) (R 7 HSiO) j (R 7 2SiO) k (5) (In the formula, R 7 (Each of the three elements is an independent, unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, where j is a number greater than or equal to 2, k is a number greater than or equal to 0, where j > k and 2 ≤ j + k ≤ 10.) A method for producing an epoxy group-containing organohydrogenpolysiloxane according to 1 or 2, which is a cyclic organohydrogenpolysiloxane represented by . 4. Epoxy group-containing organohydrogenpolysiloxanes are given by the following average composition formula (6) (R 8 3SiO 1 / 2 ) p (R 8 2SiO) q (R 8 SiO 3 / 2 ) r (SiO 4 / 2 ) s (6) (In the formula, R 8 R is independently an unsubstituted or substituted monovalent hydrocarbon group, alkoxy group, hydroxyl group, hydrogen atom, or epoxy group-containing monovalent organic group having 1 to 12 carbon atoms, and 8 At least two of them are hydrogen atoms, R 8 At least 0.1 of these are monovalent organic groups containing epoxy groups, p is a number greater than or equal to 2, q is a number greater than or equal to 0.1, r is a number greater than or equal to 0, s is a number greater than or equal to 0, and 2.1 ≤ p + q + r + s ≤ 1,000. A method for producing an epoxy group-containing organohydrogenpolysiloxane as described in any of 1 to 3. 5. A curable organopolysiloxane composition containing the following components (A) to (D). (A) The following average composition formula (6) (R 8 3SiO 1 / 2 ) p (R 8 2SiO) q (R 8 SiO 3 / 2 ) r (SiO 4 / 2 ) s (6) (In the formula, R 8 These are, independently of each other, unsubstituted or substituted monovalent hydrocarbon groups, alkoxy groups, hydroxyl groups, hydrogen atoms, or epoxy group-containing monovalent organic groups having 1 to 12 carbon atoms, and R 8 At least two of them are hydrogen atoms, R 8At least 0.1 of these are monovalent organic groups containing epoxy groups, p is a number greater than or equal to 2, q is a number greater than or equal to 0.1, r is a number greater than or equal to 0, s is a number greater than or equal to 0, and 2.1 ≤ p + q + r + s ≤ 1,000. Represented as follows, the epoxy group-containing organohydrogen polysiloxane in component (A) has an epoxy group-containing monovalent organic group content of 80 mmol or more per 100 g of component (A): 0.01 to 10 parts by mass per 100 parts by mass of component (B), (B) Organopolysiloxane having at least two alkenyl groups bonded to silicon in one molecule: 100 parts by mass, (C) Organohydrogenpolysiloxane having at least two hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule: an amount such that the ratio of the number of SiH groups in component (C) to the number of alkenyl groups in component (B) is 0.5 to 10. (D) Platinum group metal catalyst: Catalyst amount 6. Component (A) has the following average composition formula (7) (R 9 3SiO 1 / 2 )2(R 10 R 11 SiO) t (R 9 HSiO) u (R 9 2SiO) v (7) (In the formula, R 9 R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, 10 R is independently an epoxy group-containing monovalent organic group, 11 is independently an unsubstituted or substituted monovalent hydrocarbon group, alkoxy group, or hydroxyl group having 1 to 12 carbon atoms, t is a number of 0.5 or more, u is a number of 2 or more, v is a number of 1 or more, and 3.5 <t+u+v≦998である。) The curable organopolysiloxane composition according to 5, wherein the content of epoxy group-containing monovalent organic groups in component (A) exceeds 100 mmol per 100 g of component (A). 7. Component (B) has the following average composition formula (8) [ka] (In the formula, R 12 R is independently a hydroxyl group, an alkenyl group having 2 to 12 carbon atoms, or an unsubstituted or substituted monovalent hydrocarbon group that does not have an aliphatic unsaturated bond. 12 At least two of these are alkenyl groups, and a1 is 2 or more, b1 is 8 or more, c1 is 0 or more, and d1 is 0 or more, such that a1+b1+c1+d1 is selected such that the viscosity at 25°C is between 60 mPa·s and 70,000 mPa·s (30% toluene solubility). A curable organopolysiloxane composition according to 5 or 6, wherein the content of alkenyl groups bonded to silicon is 0.001 to 0.2 mol / 100g. 8. Component (C) is the following average composition formula (9) [ka] (In the formula, R 13 Each of the elements is independently an unsubstituted or substituted monovalent hydrocarbon group having 2 to 12 carbon atoms and lacking aliphatic unsaturated bonds, or a hydrogen atom; component (C) has hydrogen atoms bonded to at least two silicon atoms; e1 is 2 or more, f1 is 2 or more, g1 is 0 or more, and h1 is an integer of 0 or more; e1 + f1 + g1 + h1 is selected such that the viscosity at 25°C falls between 2 and 200 mPa·s. A curable organopolysiloxane composition according to any one of 5 to 7, represented by [the formula shown]. 9. Furthermore, the curable organopolysiloxane composition according to any one of 5 to 8, comprising (E) an organopolysiloxane having 0.1 to 20 (meth)acrylic group-containing groups bonded to silicon atoms in one molecule: (B) 0.01 to 20 parts by mass per 100 parts by mass of component. 10. Furthermore, a curable organopolysiloxane composition according to any one of 5 to 9, comprising an organopolysiloxane having at least two alkenyl groups bonded to silicon in one molecule, with a content of 0.2 to 0.8 mol / 100g of alkenyl groups bonded to silicon, and a viscosity of 1 to 50 mPa·s: an amount such that the ratio of the number of SiH groups in component (A) to the number of alkenyl groups in component (F) is 0.5 to 10. 11. A release sheet comprising a substrate and a release agent layer provided on at least one surface of the substrate, wherein the release agent layer is formed from a cured product of the curable organopolysiloxane composition according to any one of items 5 to 10. [Advantages of the Invention]

[0017] The epoxy group-containing organohydrogenpolysiloxane of the present invention has a high adhesion improving effect, causes less gelation and thickening during reaction and over time, and is excellent in long-term storage stability. Furthermore, since it has an epoxy group and a high SiH content, it exhibits a high adhesion improving effect when added to a curable organopolysiloxane composition, and a release sheet obtained using the same is useful as a release sheet for adhesive materials. [Mode for Carrying Out the Invention]

[0018] Hereinafter, the present invention will be described in detail. The method for producing the epoxy group-containing organohydrogenpolysiloxane of the present invention comprises: (a1) a linear, branched or cyclic organohydrogenpolysiloxane represented by the following average compositional formula (1), and (R 1 3SiO 1 / 2 ) a (R 1 2SiO) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (1) (wherein R 1 each independently represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or a hydrogen atom, and at least two of R 1 are hydrogen atoms. a is a number of 0 or more, b is a number of 0 or more, c is a number of 0 or more, d is a number of 0 or more, and 2 ≤ a+b+c+d ≤ 500.) (a2) an epoxy group-containing alkoxysilane represented by the following average compositional formula (2), and R 2 -SiR 3 x(OR4 ) 3-x (2) (wherein R 2 each independently represent an epoxy group-containing monovalent organic group, and R 3 and R 4 each independently represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and x is 0, 1 or 2.) (a3) an alkoxysilane represented by the following average compositional formula (3) as an optional component, SiR 5 y (OR 6 ) 4-y (3) (wherein R 5 and R 6 each independently represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and y is 0, 1, 2 or 3.) compounding such that the total molar ratio of component (a2) and component (a3) to component (a1) [(a2)+(a3)] / (a1) is a ratio of 0.1 / 1 to 998 / 1, the following component (a4) and component (a5) (a4) water: in an amount such that the molar ratio relative to 1 mole of alkoxy groups derived from component (a2) and component (a3) is 0.2 to 1, and (a5) an acid catalyst having an acid dissociation constant (pKa) of -2 to 4: in an effective amount which is a production method comprising a step of carrying out hydrolysis and equilibration reaction in the presence of the above components to obtain the epoxy group-containing organohydrogenpolysiloxane.

[0019] [Component (a1)] Component (a1) is a linear, branched or cyclic organohydrogenpolysiloxane represented by the following average compositional formula (1), and can be used alone or in combination of two or more. (R 1 3SiO 1 / 2 ) a (R 1 2SiO) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (1) (In the formula, R 1 R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or a hydrogen atom. 1 At least two of them are hydrogen atoms, a is a number greater than or equal to 0, b is a number greater than or equal to 0, c is a number greater than or equal to 0, d is a number greater than or equal to 0, and 2 ≤ a + b + c + d ≤ 500. Note that SiO in the average composition formula is SiO 2 / 2 That is the case.

[0020] R 1 R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or a hydrogen atom. 1 At least two of them are hydrogen atoms. Examples of monovalent hydrocarbon groups having 1 to 12 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, and octyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl, tolyl, xyl, and naphthyl groups; aralkyl groups such as benzyl and phenethyl groups; and halogenated alkyl groups such as chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl groups, in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as chlorine, fluorine, and bromine atoms. 1 Hydrogen atoms, alkyl groups, and alkenyl groups are preferred, and hydrogen atoms, methyl groups, and vinyl groups are more preferred.

[0021] a is a number greater than or equal to 0, preferably between 0 and 32. b is a number greater than or equal to 0, preferably between 0 and 500, and more preferably between 0 and 150. c is a number greater than or equal to 0, preferably between 0 and 10. d is a number greater than or equal to 0, preferably between 0 and 10. 2 ≤ a + b + c + d ≤ 500, preferably between 2 and 300, and more preferably between 2 and 150. If a + b + c + d exceeds the above upper limit, the Si-O-Si bond becomes less likely to break with the acid catalyst, and the reactivity decreases.

[0022] (a1) The component is as shown in the average composition formula (4) below. (R 7 (3-z) Hz SiO 1 / 2 )2(R 7 HSiO) g (R 7 2SiO) h (4) (In the formula, R 7 These are, independently of each other, unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and z is 0 or 1. When z is 0, g is a number greater than or equal to 2, h is a number greater than or equal to 0, g > h, and 2 ≤ g + h ≤ 498. When z is 1, g is a number greater than or equal to 0, h is a number greater than or equal to 0, g ≥ h, and 0 ≤ g + h ≤ 498. A linear organohydrogenpolysiloxane represented by is preferred.

[0023] Also, the average composition formula (5) below (R 7 HSiO) j (R 7 2SiO) k (5) (In the formula, R 7 (Each of the three elements is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, where j is a number greater than or equal to 2, k is a number greater than or equal to 0, where j > k and 2 ≤ j + k ≤ 10.) A cyclic organohydrogenpolysiloxane represented by [formula] is preferred.

[0024] In equations (4) and (5), R 7 These are, independently of each other, unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms. Examples of monovalent hydrocarbon groups having 1 to 12 carbon atoms include those specifically exemplified in formula (1) above, with methyl groups and vinyl groups being preferred.

[0025] In equation (4), z is either 0 or 1. When z is 0, g is a number greater than or equal to 2, preferably between 4 and 300, and more preferably between 6 and 150. h is a number greater than or equal to 0, preferably between 0 and 200, and more preferably between 0 and 100. Also, g > h, 2 ≤ g + h ≤ 498, preferably between 5 and 300, and more preferably between 8 and 150. When z is 1, g is a number greater than or equal to 0, preferably between 0 and 300, and more preferably between 0 and 150. h is a number greater than or equal to 0, preferably between 0 and 200, and more preferably between 0 and 100. Also, g ≥ h, 0 ≤ g + h ≤ 498, preferably between 0 and 300, and more preferably between 0 and 100. If g+h exceeds the above upper limit, the Si-O-Si bond may become less cleavable by the acid catalyst, potentially leading to a decrease in reactivity.

[0026] In formula (5) above, j is a number greater than or equal to 2, preferably between 4 and 6. k is a number greater than or equal to 0, preferably between 0 and 2. However, j > k, 2 ≤ j + k ≤ 10, and 4 to 6 are preferred. When j + k is less than or equal to the above upper limit, the Si-O-Si bond is more easily broken by the acid catalyst, and the reactivity is further improved.

[0027] More specifically, the following organohydrogenpolysiloxanes are exemplified, but are not limited to them. Furthermore, the bonding order of each siloxane unit shown in parentheses is not limited to those listed below. (Me3SiO 1 / 2 )2(MeHSiO) α1 (2≦α1≦498) (Me2HSiO 1 / 2 )2(MeHSiO) α2 (0≦α2≦498) (Me3SiO 1 / 2 )2(MeHSiO) α3 (Me2SiO) α4 (2≦α3≦497, 1≦α4≦248, α3>α4, 3≦δ3+δ4≦498) (MeHSiO) α5 (Me2SiO) α6 (2≦α5≦10, 0≦α6≦4, α5>α6, 2≦δ5+δ6≦10) (Me3SiO 1 / 2 ) α7 (MeHSiO) α8 (Me2SiO) α9 (MeSiO 3 / 2 ) α10 (3≦α7≦12, 2≦α8≦497, 0≦α9≦247, 1≦α10≦10, α8>α9+α10, 6≦α7+α8+α9+α10≦500) (Me2SiO 1 / 2 ) α11 (MeHSiO) α12 (Me2SiO) α13 (MeSiO 3 / 2 ) α14 (SiO 4 / 2 ) α15 (4≦α11≦32, 2≦α12≦497, 0≦α13≦247, 0≦α14≦10, 1≦α15≦10, α12>α13+α14+α15, 7≦α11+α12+α13+α14≦500) In the above formulas, Me and H represent a methyl group and a hydrogen atom, respectively.

[0028] [(a2) component] (a2) The component is an epoxy group-containing alkoxysilane represented by the following average composition formula (2), and can be used alone or in combination of two or more types. R 2 -SiR 3 x(OR 4 ) 3-x (2) (In the formula, R 2 R is independently an epoxy group-containing monovalent organic group, 3 and R 4 Each of these is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and x is 0, 1, or 2.

[0029] In formula (2), R 2These are independently epoxy group-containing monovalent organic groups. Examples of such epoxy group-containing monovalent organic groups include glycidoxyalkyl groups, epoxycyclohexylalkyl groups, and oxyranylalkyl groups having 3 to 20 carbon atoms, preferably 3 to 16 carbon atoms, and even more preferably 4 to 10 carbon atoms. Among these, the group shown below is preferred. In the formula, the part indicated by * is a bond with the silicon atom of the organopolysiloxane.

[0030] [ka] The following bases are preferred due to their availability. [ka]

[0031] In formula (2), R 3 and R 4 Each of these is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms. Examples of monovalent hydrocarbon groups having 1 to 12 carbon atoms include those specifically exemplified in formula (1) above, with methyl and ethyl groups being preferred.

[0032] More specifically, the following epoxy group-containing alkoxysilanes are exemplified, but are not limited to, those listed below.

[0033] [ka] (In each of the above formulas, Me is a methyl group, R 4 (This is either a methyl group or an ethyl group.)

[0034] [(a3) component] As an optional component, component (a3) ​​is an alkoxysilane represented by the following average composition formula (3), and can be used alone or in combination of two or more types. SiR 5 y (OR 6 ) 4-y (3) (In the formula, R 5 and R 6 Each of these is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and y is 0, 1, 2, or 3.

[0035] R 5 and R 6 Each of these is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms. Examples of monovalent hydrocarbon groups having 1 to 12 carbon atoms include those specifically exemplified in formula (1) above, with methyl and ethyl groups being preferred. More specifically, the following alkoxysilanes are exemplified.

[0036] [ka] (In the above formula, Me is a methyl group, R 6 (This is either a methyl group or an ethyl group.)

[0037] The mixing ratio of components (a1), (a2), and (a3) ​​used in this invention can be changed according to the degree of polymerization of the epoxy group-containing organohydrogenpolysiloxane to be desired. Note that component (a3) ​​is an optional component and may or may not be included. It is preferable to blend the components so that the total molar ratio of components (a2) and (a3) ​​to component (a1) ([(a2)+(a3)] / (a1)) is between 0.1 / 1 and 998 / 1, more preferably between 0.4 / 1 and 500 / 1, and even more preferably between 0.8 / 1 and 100 / 1.

[0038] If (a3) ​​is included, the molar ratio of component (a2) to component (a3) ​​((a2) / (a3)) is preferably 0.0001 / 1 to 997 / 1, more preferably 0.001 / 1 to 500 / 1, and even more preferably 0.01 / 1 to 100 / 1. If there is too little component (a2), adhesion to the substrate may be insufficient, and if there is too much component (a2), the viscosity may become high and it may become difficult to handle.

[0039] [(a4) component] Component (a4) is water, which is used to hydrolyze the alkoxy groups of components (a2) and (a3). The amount of (a4) is such that the molar ratio of (a4) to 1 mole of alkoxy groups derived from components (a2) and (a3) ​​is 0.2 to 1, preferably 0.3 to 0.9, and more preferably 0.4 to 0.85. If the amount of (a4) is less than the lower limit, the alkoxy groups derived from components (a2) and (a3) ​​will not be sufficiently hydrolyzed, and an epoxy group-containing organohydrogen polysiloxane with the desired chain length (structure) will not be obtained. On the other hand, even if the amount of (a4) is greater than the upper limit, not much improvement in hydrolysis can be expected. By setting the molar ratio of water to 1 mole of alkoxy groups derived from components (a2) and (a3) ​​to 0.5 or more, all of the alkoxy groups of components (a2) and (a3) ​​can be hydrolyzed. On the other hand, by setting the molar ratio of water to 1 mole of alkoxy groups derived from components (a2) and (a3) ​​to less than 0.5, it is possible to leave the alkoxy groups without hydrolysis, and to introduce alkoxy groups into the resulting epoxy group-containing organohydrogenpolysiloxane.

[0040] [(a5) component] Component (a5) is an acid catalyst with an acid dissociation constant (pKa) of -2 to 4, and can be used alone or in combination of two or more. Component (a5) acts as a catalyst that promotes the cleavage and recombination (equilibriumization) of the Si-O-Si of component (a1), and the hydrolysis of the alkoxy groups derived from components (a2) and (a3). The key point of this patent is that the acid dissociation constant of the acid catalyst is set to -2 to 4. If a strong acid catalyst with an acid dissociation constant of less than -2 is used, although equilibration and hydrolysis proceed as described above, ring-opening of the epoxy also occurs simultaneously, making it impossible to obtain the target product with residual epoxy groups. On the other hand, if a weak acid catalyst with an acid dissociation constant greater than 4 is used, ring-opening of the epoxy group can be suppressed, but equilibration and hydrolysis, especially equilibration, do not proceed, and it becomes impossible to obtain an epoxy group-containing organohydrogenpolysiloxane with the desired chain length (structure). The acid dissociation constant (pKa) is between -2 and 4, preferably between -1 and 3.5, and more preferably between -0.5 and 3. The Evans pKa Table was used to determine the acid dissociation constant (pKa).

[0041] Such acid catalysts can be obtained from the market, for example, trifluoroacetic acid (CF3COOH), monofluoroacetic acid (CH2FCOOH), trichloroacetic acid (Cl3COOH), and dichloroacetic acid (CHC2FCOOH). l2 Examples include (COOH), chloroacetic acid (CH2ClCOOH), bromoacetic acid (CH2BrCOOH), and iodoacetic acid (CH2ICOOH).

[0042] (a5) The amount of component added is not limited as long as (a1) to (a3) ​​are within the range in which equilibrium and hydrolysis proceed, but preferably 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, even more preferably 0.3 to 5 parts by mass, and particularly preferably 0.6 to 2 parts by mass per 100 parts by mass of the total of components (a1) to (a3).

[0043] [Organic solvents] The hydrolysis equilibration reaction of the present invention may be carried out without a solvent or in an organic solvent. Examples of organic 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, ether compounds such as diisopropyl ether and 1,4-dioxane, or mixtures thereof. These can be used individually or in appropriate combinations of two or more.

[0044] The amount of organic solvent is preferably 0 to 200 parts by mass per 100 parts by mass of the total of components (a1) to (a5), preferably 1 to 200 parts by mass, more preferably 1 to 150 parts by mass, and even more preferably 5 to 100 parts by mass if used.

[0045] The hydrolysis equilibration reaction of the present invention can be carried out by mixing and stirring the above components (a1) to (a5) in the amounts described above. The reaction temperature is not particularly limited and can be carried out at room temperature (23°C ± 10°C) or under heating. In order to obtain a suitable reaction rate, it is preferable to carry out the reaction under heating, with 35 to 150°C being preferred, more preferably 40 to 120°C, and particularly preferably 50 to 90°C. The reaction time is also not particularly limited, but is preferably 0.5 to 48 hours, more preferably 1 to 24 hours, and even more preferably 1 to 10 hours.

[0046] The order in which the above components (a1) to (a5) are added is not particularly limited, but it is usually produced by mixing components (a1) to (a3), then adding the acid catalyst component (a5), and then slowly adding the water component (a4) dropwise. Other possible production methods include adding the acid catalyst component (a5) to (a1) and equilibrating it, then adding components (a2) to (a3), and then slowly adding the water component (a4), or adding the acid catalyst component (a5) and the water component (a4) to a mixture of components (a2) to (a3) ​​to induce a hydrolysis reaction, and then adding (a1).

[0047] [Epoxy group-containing organohydrogenpolysiloxane] The present invention provides a method for producing an epoxy group-containing organohydrogenpolysiloxane. The epoxy group-containing organohydrogenpolysiloxane is defined by the following average composition formula (6): (R 8 3SiO 1 / 2 ) p (R 8 2SiO) q (R 8 SiO 3 / 2 ) r (SiO 4 / 2 ) s (6) (In the formula, R 8 R is independently an unsubstituted or substituted monovalent hydrocarbon group, alkoxy group, hydroxyl group, hydrogen atom, or epoxy group-containing monovalent organic group having 1 to 12 carbon atoms, and 8 At least two of them are hydrogen atoms, R 8 At least 0.1 of these are monovalent organic groups containing epoxy groups, p is a number greater than or equal to 2, q is a number greater than or equal to 0.1, r is a number greater than or equal to 0, s is a number greater than or equal to 0, and 2.1 ≤ p + q + r + s ≤ 1,000. Examples include those represented by the following:

[0048] In formula (6), the monovalent hydrocarbon group having 1 to 12 carbon atoms is the same as the monovalent hydrocarbon group having 1 to 12 carbon atoms in formula (1) above, with the methyl group being preferred. Examples of alkoxy groups include the methoxy group, ethoxy group, propoxy group, and butoxy group, with the methoxy group and ethoxy group being preferred.

[0049] R 8At least two of these atoms are hydrogen atoms. If there are fewer than two, there is a high possibility that uncrosslinked molecules will remain in the cured film, and when an adhesive material is attached to the release layer made of the cured film and then peeled off, the adhesive strength of the adhesive material (hereinafter referred to as residual adhesive strength) may decrease. More specifically, the hydrogen atom content is preferably 0.001 to 1.7 moles, more preferably 0.01 to 1.6 moles, even more preferably 0.1 to 1.5 moles, and particularly preferably 0.5 to 1.4 moles per 100 g of epoxy group-containing organohydrogenpolysiloxane. Within the above numerical range, when used in a release agent composition, it is possible to ensure adhesion while maintaining the peeling force.

[0050] In formula (6) above, the epoxy group-containing monovalent organic group is the same as the epoxy group-containing monovalent organic group specifically exemplified in formula (2) above, and among these, the group shown below is preferred.

[0051] [ka] The areas marked with an asterisk (*) are the bonds between the organopolysiloxane and the silicon atom.

[0052] R 8 At least 0.1 of these are monovalent organic groups containing epoxy groups, and having 0.1 or more of these groups provides better adhesion. More specifically, the epoxy group content is preferably 0.1 to 600 mmol per 100 g of the epoxy group-containing organohydrogenpolysiloxane, more preferably 10 to 400 mmol, and even more preferably 50 to 200 mmol. 80 to 150 mmol is particularly preferred, and over 100 mmol and 150 mmol or less is most preferred. Within the above numerical range, a viscosity that is easy to handle can be achieved. Furthermore, when used in a release agent composition, it is possible to ensure adhesion while maintaining release force. The method for measuring the epoxy group content is as described in the examples.

[0053] The viscosity of epoxy group-containing organohydrogenpolysiloxane at 25°C is preferably 1 to 10,000 mPa·s, more preferably 3 to 1,000 mPa·s, even more preferably 5 to 500 mPa·s, and particularly preferably 10 to 300 mPa·s. In this invention, all viscosity values ​​are measured using a rotational viscometer at 25°C. Adhesion is more sufficiently improved by setting the viscosity above the lower limit. Workability is further improved by setting the viscosity below the upper limit.

[0054] The weight-average molecular weight of the epoxy group-containing organohydrogenpolysiloxane is preferably 200 to 40,000, more preferably 400 to 30,000, even more preferably 600 to 20,000, and particularly preferably 800 to 10,000. In this invention, all weight-average molecular weights are values ​​measured by the method described in the examples. By setting the viscosity above the lower limit, adhesion is more sufficiently improved. Conversely, by setting it below the upper limit, workability is further improved.

[0055] p is a number greater than or equal to 2, preferably between 2 and 32. q is a number greater than or equal to 0.1, preferably between 0.1 and 998, more preferably between 0.3 and 500, and even more preferably between 0.3 and 200. r is a number greater than or equal to 0, preferably between 0 and 10. s is a number greater than or equal to 0, preferably between 0 and 10. 2.1 ≤ p+q+r+s ≤ 1,000, with 5 ≤ p+q+r+s ≤ 500 preferred, 10 ≤ p+q+r+s ≤ 300 more preferred, and 15 ≤ p+q+r+s ≤ 150 even more preferred. However, the order of each repeating unit is arbitrary.

[0056] The epoxy group-containing organohydrogen polysiloxane of the present invention exhibits different epoxy group retention rates depending on the acid dissociation constant (pKa) of the acid catalyst used during synthesis, but the epoxy retention rate is 1This can be calculated using H-NMR. The proton of the methylene group bonded to the Si atom of the epoxy group-containing alkoxysilane (a2), which is the starting material (δ=0.42), remains unchanged before and after ring opening of the epoxy group, so this proton peak was used as the reference. The integral value of the methylene proton peak derived from the reference epoxy group-containing monovalent organic group is set to 2.00. If a starting material having a glycidyl group is used as component (a2), and the epoxy group remains 100% intact without ring opening, then the following H a The peak integral value (around δ=2.5, 2.7) is 2.00. On the other hand, if the epoxy group is ring-open, then H a The peak integral value decreases. From this, the remaining epoxy group percentage is calculated according to the following formula (X). Epoxy residue rate (%) = [(H a (Peak integral value of) / 2.00] × 100 (X) Similarly, if a raw material having an alicyclic epoxy group is used as component (a2), and 100% of the epoxy group remains without ring opening, then the following H b and H c The sum of the peak integral values ​​(around δ=3.1) is 2.00. From this, the remaining epoxy group percentage is calculated according to the following formula (Y). Epoxy residue rate (%) = [(H b +H c (Peak integral value of) / 2.00] × 100 (Y)

[0057] [ka]

[0058] The epoxy residue rate in the epoxy group-containing organohydrogenpolysiloxane of the present invention is preferably 50-100%, more preferably 55-100%, and even more preferably 60-100%. Within the above numerical range, sufficient adhesion can be ensured when used in a release agent composition.

[0059] The epoxy group-containing organohydrogen polysiloxane of the present invention is as follows: (R9 3SiO 1 / 2 )2(R 10 R 11 SiO) t (R 9 HSiO) u (R 9 2SiO) v (7) (wherein, R 9 is each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, R 10 is each independently an epoxy group-containing monovalent organic group, R 11 is each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group or a hydroxyl group, t is a number of 0.5 or more, u is a number of 2 or more, v is a number of 1 or more, and 3.5 < t+u+v ≤ 998.) include those represented by

[0060] In the above formula (7), examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms are the same as those specifically exemplified as the monovalent hydrocarbon group having 1 to 12 carbon atoms in the above formula (1), and a methyl group is preferred among them. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, among which a methoxy group and an ethoxy group are preferred. Examples of the epoxy group-containing monovalent organic group are the same as those specifically exemplified as the epoxy group-containing monovalent organic group in the above formula (2), and the groups shown below are preferred among them.

[0061]

Chemical Formula

[0062] In formula (7), t is a number of 0.5 or more, that is, the epoxy group-containing organohydrogenpolysiloxane has at least 0.5 epoxy group-containing monovalent organic group. More specifically, the content of the epoxy group-containing monovalent organic group per 100 g of the epoxy group-containing organohydrogenpolysiloxane is preferably more than 100 mmol and 600 mmol or less, more preferably more than 100 mmol and 400 mmol or less, still more preferably more than 100 mmol and 200 mmol or less, and most preferably more than 100 mmol and 150 mmol or less. When the content of the epoxy group-containing monovalent organic group is not less than the above lower limit, more sufficient adhesion can be obtained. When the content is not more than the above upper limit, handling becomes easier.

[0063] In the above formula (7), u is a number of 2 or more, that is, the epoxy group-containing organohydrogenpolysiloxane has at least 2 SiH groups. When the number of SiH groups is 2 or more, curability is further improved. More specifically, the content of hydrogen atoms per 100 g of the epoxy group-containing organohydrogenpolysiloxane is preferably 0.001 to 1.7 mol, more preferably 0.01 to 1.6 mol, still more preferably 0.1 to 1.5 mol, and particularly preferably 0.5 to 1.4 mol. When the content is not more than the above upper limit, it can be prevented that the peeling force becomes excessively high and the adhesive material is difficult to peel off.

[0064] t, u and v in formula (7) are selected from numbers falling within the above viscosity range, wherein t is a number of 0.5 or more, preferably 0.5 to 995, more preferably 0.6 to 100, and still more preferably 0.7 to 50. u is a number of 2 or more, preferably 2 to 996, more preferably 5 to 500, and still more preferably 10 to 200. v is a number of 1 or more, preferably 1 to 995, more preferably 1 to 100, and still more preferably 1 to 50. 3.5≤t+u+v≤998, preferably 5≤t+u+v≤500, more preferably 10≤t+u+v≤200, and still more preferably 15≤t+u+v≤100. Provided that the order of each repeating unit is arbitrary.

[0065] Examples of epoxy group-containing organohydrogen polysiloxanes obtained by the manufacturing method of the present invention include, but are not limited to, the following. The bonding order of each siloxane unit shown in parentheses is not limited to the following. (Me3SiO 1 / 2 )2(MeHSiO) β1 (MeEpSiO) β2 (Me2SiO) β3 (2≦β1≦997.9, 0.1≦β2≦996, 0≦β3≦995.9, 4.1≦β1+β2+β3≦1,000) (Me2HSiO 1 / 2 )2(MeEpSiO) β4 (Me2SiO) β5 (0.1 ≤ β4 ≤ 998, 0 ≤ β5 ≤ 997.9, 4.1 ≤ β4 + β5 ≤ 1,000) (Me2EpSiO 1 / 2 )2(MeHSiO) β6 (Me2SiO) β7 (2 ≤ β6 ≤ 998, 0 ≤ β7 ≤ 996, 4 ≤ β6 + β7 ≤ 1,000) (Me2HSiO 1 / 2 )2(MeHSiO) β8 (MeEpSiO) β9 (Me2SiO) β10 (1≦β8≦997.9, 0.1≦β9≦997, 0≦β10≦996.9, 3.1≦β8+β9+β10≦1,000) (Me2EpSiO 1 / 2 )2(MeHSiO) β11 (MeEpSiO) β12 (Me2SiO) β13 (2≦β11≦997.9, 0.1≦β12≦996, 0≦β13≦995.9, 4.1≦β11+β12+β13≦1,000) (Me3SiO 1 / 2 )2(MeHSiO) β14 (MeOEpSiO) β15 (Me2SiO) β16 (2≦β14≦997.9, 0.1≦β15≦996, 0≦β16≦995.9, 4.1≦β14+β15+β16≦1,000) (Me3SiO 1 / 2 ) β17 (MeHSiO) β18 (MeEpSiO) β19 (Me2SiO) β20 (MeSiO 3 / 2 ) β21 (3≦β17≦12, 2≦β18≦995.9, 0.1≦β19≦994, 0≦β20≦993.9, 1≦β21≦10, 6.1≦β17+β18+β19+β20+β21≦1,000) (Me3SiO 1 / 2 ) β22 (MeHSiO) β23 (MeEpSiO) β24 (Me2SiO) β25 (MeSiO 3 / 2 ) β26 (SiO 4 / 2 ) β27 (4≦β22≦32, 2≦β23≦994.9, 0.1≦β24≦993, 0≦β25≦992.9, 0≦β 26≦10, 1≦β27≦10, 7.1≦β22+β23+β24+β25+β26+β27≦1,000) In the above formulas, Me, H, MeO, and Ep represent a methyl group, a hydrogen atom, a methoxy group, and the group shown below, respectively. Either one of the groups shown below may be used alone, or both may be used in combination.

[0066] [ka] The areas marked with an asterisk (*) are the bonds between the organopolysiloxane and the silicon atom.

[0067] [Curable organopolysiloxane composition] The present invention provides a curable organopolysiloxane composition comprising the following components (A) to (D), and a release sheet comprising a cured product of the composition. (A) The following average composition formula (6) (R 83SiO 1 / 2 ) p (R 8 2SiO) q (R 8 SiO 3 / 2 ) r (SiO 4 / 2 ) s (6) (In the formula, R 8 These are, independently of each other, unsubstituted or substituted monovalent hydrocarbon groups, alkoxy groups, hydroxyl groups, hydrogen atoms, or epoxy group-containing monovalent organic groups having 1 to 12 carbon atoms, and R 8 At least two of them are hydrogen atoms, R 8 At least 0.1 of these are monovalent organic groups containing epoxy groups, p is a number greater than or equal to 2, q is a number greater than or equal to 0.1, r is a number greater than or equal to 0, s is a number greater than or equal to 0, and 2.1 ≤ p + q + r + s ≤ 1,000. Represented as follows, the epoxy group-containing organohydrogen polysiloxane in component (A) has an epoxy group-containing monovalent organic group content of 80 mmol or more per 100 g of component (A): 0.01 to 10 parts by mass per 100 parts by mass of component (B), (B) Organopolysiloxane having at least two alkenyl groups bonded to silicon in one molecule: 100 parts by mass, (C) Organohydrogenpolysiloxane having at least two hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule: an amount such that the ratio of the number of SiH groups in component (C) to the number of alkenyl groups in component (B) is 0.5 to 10. (D) Platinum group metal catalyst: Catalyst amount

[0068] [(A) component] Component (A) is the epoxy group-containing organohydrogenpolysiloxane described above, represented by the average composition formula (6), and the example shown above can be used. The epoxy group-containing organohydrogenpolysiloxane represented by the average composition formula (7) is preferred. In the present invention, component (A) is a component that improves the adhesion of the resulting cured film to various substrates. By having both an epoxy group and a SiH group in one molecule, it has a higher effect on improving adhesion than compounds having either an epoxy group or a SiH group individually. Furthermore, as this SiH group reacts with the alkenyl group of the subsequent component (B), component (A) is incorporated into the cured film, thus suppressing the reduction in residual adhesive strength due to unreacted components.

[0069] The viscosity of epoxy group-containing organohydrogenpolysiloxane at 25°C is preferably 1 to 10,000 mPa·s, more preferably 3 to 1,000 mPa·s, even more preferably 5 to 500 mPa·s, and particularly preferably 10 to 300 mPa·s. In this invention, all viscosity values ​​are measured using a rotational viscometer at 25°C. Adhesion is more sufficiently improved by setting the viscosity above the lower limit. Workability is further improved by setting the viscosity below the upper limit.

[0070] Examples of epoxy group-containing organohydrogen polysiloxanes of component (A) include, but are not limited to, the following. The bonding order of each siloxane unit shown in parentheses is not limited to the following. (Me3SiO 1 / 2 )2(MeHSiO) γ1 (MeEpSiO) γ2 (Me2SiO) γ3 (2≦γ1≦996.5, 0.5≦γ2≦995, 1≦γ3≦995.5, 3.5≦γ1+γ2+γ3≦1,000) (Me3SiO 1 / 2 )2(MeHSiO) γ4 (MeOEpSiO) γ5 (Me2SiO)γ6 (2≦γ4≦996.5, 0.5≦γ15≦995, 1≦γ16≦995.5, 3.5≦γ14+γ15+γ16≦1,000) In each of the above formulas, Me, H, MeO, and Ep each represent a methyl group, a hydrogen atom, a methoxy group, and a group shown below. Either one type of the group shown below may be used alone, or two types may be used in combination.

[0071]

Chemical Formula

[0072] The amount of component (A) is 0.01 to 10 parts by mass relative to 100 parts by mass of component (B), preferably 0.1 to 5 parts by mass, more preferably 0.2 to 2 parts by mass, and even more preferably 0.4 to 1 part by mass. When the amount of component (A) is at or above the above lower limit, the adhesion to a substrate is further improved. Further, by setting the amount of component (A) to be at or below the above upper limit, it is possible to prevent the peeling force from becoming too high and making it difficult to peel off the adhesive material.

[0073] [Component (B)] Component (B) is an organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule, and can be used alone or in combination of two or more.

[0074] Component (B) has at least two silicon-bonded alkenyl groups per molecule. If the number is less than two, uncrosslinked molecules are likely to remain even after curing, which reduces curability, so this is not preferred. The content of silicon-bonded alkenyl groups is preferably 0.001 to 0.2 mol / 100g, more preferably 0.0015 to 0.15 mol / 100g, and even more preferably 0.002 to 0.1 mol / 100g. If the content of silicon-bonded alkenyl groups is lower than the above lower limit, curability may decrease. Further, if the content of silicon-bonded alkenyl groups is higher than the above upper limit, the peeling force may become too high, making it difficult to peel off the adhesive material.

[0075] Component (B) preferably has a viscosity at 25°C of 60 mPa·s or more and a 30% toluene solubility (viscosity of the solution when organopolysiloxane is dissolved in toluene at a concentration of 30% by mass) of 70,000 mPa·s or less, more preferably 80 mPa·s or more and a 30% toluene solubility of 60,000 mPa·s or less, and particularly preferably 100 mPa·s or more and a 30% toluene solubility of 50,000 mPa·s or less. If the viscosity of component (B) is lower than the lower limit, the composition tends to spread too easily, resulting in insufficient coating on the substrate surface. Conversely, if it is higher than the upper limit, it may not spread easily, potentially reducing workability.

[0076] (B) The average composition formula is as follows (8) [ka] (In the formula, R 12 R is independently a hydroxyl group, an alkenyl group having 2 to 12 carbon atoms, or an unsubstituted or substituted monovalent hydrocarbon group that does not have an aliphatic unsaturated bond. 12 At least two of these are alkenyl groups, and a1 is 2 or more, b1 is 8 or more, c1 is 0 or more, and d1 is 0 or more, such that a1+b1+c1+d1 is selected such that the viscosity at 25°C is between 60 mPa·s and 70,000 mPa·s (30% toluene solubility). A representation of this is preferable.

[0077] In formula (8), examples of alkenyl groups include vinyl, allyl, butenyl, propenyl, 5-hexenyl, octenyl, and decenyl groups. Among these, vinyl groups are preferred from an industrial standpoint. Unsubstituted or substituted monovalent hydrocarbon groups that do not have aliphatic unsaturated bonds are preferred to have 1 to 12 carbon atoms, and more preferably 1 to 10 carbon atoms. Examples of monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, and octyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups, and aralkyl groups such as benzyl and phenethyl groups. Also, haloalkyl groups such as chloropropyl and trifluoropropyl groups, in which some or all of the hydrogen atoms are substituted with halogen atoms, are also included. Due to their high curability and low peeling strength, all R 12 It is preferable that 80 mol% or more of the group consists of methyl groups.

[0078] a1, b1, c1, and d1 are selected from integers that represent the viscosity range described above. a1 is 2 or greater, preferably 2 to 300, b1 is 8 or greater, preferably 40 to 20,000, c1 is 0 or greater, preferably 0 to 100, and d1 is 0 or greater, preferably 0 to 100. 40 ≤ a1 + b1 + c1 + d1 ≤ 20,000 is preferred, and 60 ≤ a1 + b1 + c1 + d1 ≤ 15,000 is more preferred.

[0079] Examples of the organopolysiloxane component (B) include compounds represented by the following formula. (R 12 3SiO 1 / 2 )2(R 12 2SiO) b1 (R 12 3SiO 1 / 2 ) a1 (R 12 2SiO) b1 (R 12 SiO 3 / 2 ) c1 (R 12 3SiO 1 / 2 ) a1 (R12 2SiO) b1 (SiO 4 / 2 ) d1 (R 12 3SiO 1 / 2 ) a1 (R 12 2SiO) b1 (R 12 SiO 3 / 2 ) c1 (SiO 4 / 2 ) d1

[0080] In each of the above formulas, R 12 a1 to d1 are as described above. More detailed examples include, but are not limited to, compounds represented by the following formulas. Furthermore, the bonding order of each siloxane unit shown in parentheses is not limited to the following. (ViMe2SiO 1 / 2 )2(Me2SiO) δ1 (40 ≤ δ1 ≤ 19,998) (Vi3SiO 1 / 2 )2(Me2SiO) δ2 (40 ≤ δ² ≤ 19,998) (ViMe2SiO 1 / 2 )2(Me2SiO) δ3 (ViMeSiO) δ4 (0 ≤ δ3 ≤ 19,997, 1 ≤ δ4 ≤ 2,000, 40 ≤ δ3 + δ4 ≤ 19,998) (ViMe2SiO 1 / 2 )2(Me2SiO) δ5 (Ph2SiO) δ6 (0 ≤ δ5 ≤ 19,997, 1 ≤ δ6 ≤ 2,000, 40 ≤ δ5 + δ6 ≤ 19,998) (ViMe2SiO 1 / 2 )2(Me2SiO) δ7 (ViMeSiO) δ8 (Ph2SiO) δ9 (0≦δ7≦19,996, 1≦δ8≦2,000, 1≦δ9≦2,000, 40≦δ7+δ8+δ9≦19,998) (ViMe2SiO 1 / 2 ) δ10 (Me2SiO) δ11 (MeSiO 3 / 2 ) δ12 (3≦δ10≦102, 8≦δ11≦19,996, 1≦δ12≦100, 40≦δ10+δ11+δ12≦20,000) (ViMe2SiO 1 / 2 ) δ13 (Me2SiO) δ14 (MeSiO 3 / 2 ) δ15 (SiO 4 / 2 ) δ16 (4≦δ13≦302, 8≦δ14≦19,995, 0≦δ15≦100, 1≦δ16≦100, 40≦δ13+δ14+δ15+δ16≦20,000) In the above formulas, Me, Vi, and Ph represent a methyl group, a vinyl group, and a phenyl group, respectively.

[0081] [(C) component] Component (C) is an organohydrogenpolysiloxane having at least two hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule, and can be used alone or in combination of two or more. The viscosity of component (C) at 25°C is preferably 2 to 200 mPa·s, more preferably 5 to 180 mPa·s, and even more preferably 10 to 150 mPa·s. When the viscosity of component (C) is above the lower limit, adhesion to the substrate is further improved. When it is below the upper limit, reactivity is further improved.

[0082] (C) The average composition formula is as follows (9) [ka] (In the formula, R 13Each of the elements is independently an unsubstituted or substituted monovalent hydrocarbon group having 2 to 12 carbon atoms and lacking aliphatic unsaturated bonds, or a hydrogen atom; component (C) has hydrogen atoms bonded to at least two silicon atoms; e1 is 2 or more, f1 is 2 or more, g1 is 0 or more, and h1 is an integer of 0 or more; e1 + f1 + g1 + h1 is selected such that the viscosity at 25°C falls between 2 and 200 mPa·s. Examples include those represented by the following:

[0083] In formula (9), the unsubstituted or substituted monovalent hydrocarbon group having 2 to 12 carbon atoms and not having an aliphatic unsaturated bond is the same as the monovalent hydrocarbon group specifically exemplified in formula (8) above, with alkyl groups being preferred and methyl groups being more preferred. Due to its high curability and low peeling strength, the total R 13 It is preferable that 50 mol% or more, particularly 60-100 mol%, of the total R 13 By setting the amount to 50 mol% or more, compatibility with component (B) is improved, and turbidity or phase separation of the curable organopolysiloxane composition can be further suppressed.

[0084] Component (C) has at least two SiH groups in one molecule. Having two or more SiH groups further improves curability. More specifically, the SiH group content is preferably 0.5 to 2.0 mol / 100g, more preferably 0.6 to 1.8 mol / 100g, and even more preferably 0.8 to 1.6 mol / 100g. The curability is further improved by setting the SiH group content above the lower limit. Conversely, by setting the SiH group content below the upper limit, it is possible to suppress excessive peeling force.

[0085] In formula (9), e1, f1, g1, and h1 are selected from integers that fall within the viscosity range described above, where e1 is 2 or greater, preferably 2 to 32; f1 is 2 or greater, preferably 8 to 200; g1 is 0 or greater, preferably 0 to 10; and h1 is 0 or greater, preferably 0 to 10. e1+f1+g1+h1 is selected such that the viscosity at 25°C falls within the range of 2 to 200 mPa·s, preferably 4≦e1+f1+g1+h1≦200, and more preferably 10≦e1+f1+g1+h1≦150.

[0086] Examples of component (C) include siloxanes containing hydrogensilyl groups at both ends, siloxanes containing hydrogensilyl groups in the side chain, siloxanes containing hydrogensilyl groups at one end and in the side chain, and siloxanes containing hydrogensilyl groups at both ends and in the side chain. More specifically, the organohydrogenpolysiloxanes listed below are examples, but are not limited to these. Furthermore, the bonding order of each siloxane unit shown in parentheses is not limited to those listed below. (Me3SiO 1 / 2 )2(MeHSiO) θ1 (2≦θ1≦200) (Me3SiO 1 / 2 )2(MeHSiO) θ2 (Me2SiO) θ3 (2≦θ2≦199, 1≦θ3≦198, 3≦θ2+θ3≦200) (Me3SiO 1 / 2 ) θ4 (MeHSiO) θ5 (Me2SiO) θ6 (MeSiO 3 / 2 ) θ7 (3≦θ4≦12, 2≦θ5≦196, 0≦θ6≦194, 1≦θ7≦10, 6≦θ5+θ6+θ7≦200) (Me2SiO 1 / 2 ) θ8 (MeHSiO) θ9 (Me2SiO) θ10 (MeSiO 3 / 2 ) θ11 (SiO 4 / 2 ) θ12 (4≦θ8≦22, 2≦θ9≦195, 0≦θ10≦193, 0≦θ11≦10, 1≦θ12≦10, 7≦θ8+θ9+θ10+θ11+θ12≦200) In the above formulas, Me and H represent a methyl group and a hydrogen atom, respectively.

[0087] The amount of component (C) is preferably such that the number ratio of SiH groups in component (C) to the number of alkenyl groups in component (B) is 0.5 to 10 times the molar amount, more preferably 0.8 to 8.0 times, and particularly preferably 1.0 to 5.0 times the molar amount. If the amount of component (C) is above the lower limit, the curability is further improved. If it is below the upper limit, it is possible to suppress the peeling force from becoming too high.

[0088] [(D) component] The platinum group metal catalyst of component (D) is a catalyst for promoting the addition reaction of the curable organopolysiloxane composition of the present invention, and any catalyst known to those skilled in the art for promoting so-called hydrosilylation reactions can be used. Examples of such platinum group metal catalysts include platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts, among which platinum-based catalysts are particularly preferred. Examples of such platinum-based catalysts include chloroplatinic acid, an alcohol solution or aldehyde solution of chloroplatinic acid, complexes of chloroplatinic acid with various olefins or vinylsiloxanes, and complexes of platinum with various olefins or vinylsiloxanes.

[0089] The amount of component (D) should be such that it is an effective amount as a catalyst. For example, from an economic standpoint as well as to obtain a good cured film, the amount of platinum group metals is preferably 0.1 to 200 ppm, more preferably 0.5 to 150 ppm, even more preferably 1 to 100 ppm, and particularly preferably 2 to 50 ppm, relative to the total mass of the entire composition. In the present invention, it is also possible to reduce the amount of platinum to 30 ppm or less by incorporating component (E) described later.

[0090] [(E) component] The curable organopolysiloxane composition of the present invention may further contain an organopolysiloxane having 0.1 to 20 (meth)acrylic group-containing groups bonded to silicon atoms in one molecule. Component (E) can be used alone or in combination of two or more. Component (E) is a component that enhances the reactivity of the addition reaction in the present invention. The reason for the increased reactivity is not clear, but it is presumed that the (meth)acrylic group-containing groups coordinate to the platinum group metal atoms in some way, thereby exhibiting the above effect. It becomes possible to use a reduced amount of the platinum group metal catalyst component (D).

[0091] The viscosity of component (E) at 25°C is preferably 1 to 10,000 mPa·s, more preferably 5 to 5,000 mPa·s, and even more preferably 10 to 1,000 mPa·s. If the viscosity of component (E) is below the above upper limit, it has good compatibility with components (A) and (B), and turbidity can be suppressed.

[0092] (E) Examples of component include organopolysiloxanes represented by the following average composition formula (10). [ka] (In the formula, R 14 Independently, R is a hydroxyl group, a C2-C12 alkenyl group or (meth)acrylic group-containing group, or an unsubstituted or substituted monovalent hydrocarbon group that does not have an aliphatic unsaturated bond. 14 Of these, 0.1 to 20 are (meth)acrylic group-containing groups, and j1 to n1 are integers satisfying 2 ≤ j1 ≤ 202, 5 ≤ k1 ≤ 1,000, 0 ≤ m1 ≤ 100, and 0 ≤ n1 ≤ 100, respectively, and j1 + k1 + m1 + n1 are selected so that the viscosity at 25°C falls between 1 and 10,000 mPa·s.

[0093] Component (E) has 0.1 to 20 (meth)acrylic group-containing groups bonded to silicon in one molecule. More specifically, the content of (meth)acrylic group-containing groups bonded to silicon is 0.0001 to 0.6 mol / 100g, preferably 0.005 to 0.4 mol / 100g, and more preferably 0.01 to 0.2 mol / 100g. When the content of (meth)acrylic group-containing groups bonded to silicon is above the lower limit, it has an excellent effect in increasing the reactivity of the addition reaction, and the curability does not decrease even when the amount of catalyst is reduced. Also, when the content of (meth)acrylic group-containing groups bonded to silicon is below the upper limit, it is possible to suppress the decrease in compatibility with components (A) and (B) and the resulting turbidity.

[0094] Component (E) more preferably has at least 0.1 alkenyl groups bonded to silicon per molecule. The presence of alkenyl groups in component (E) makes it easier for component (E) to be incorporated into the cured film, and suppresses the reduction in residual adhesive strength due to unreacted components of component (E). More specifically, the content of alkenyl groups bonded to silicon is preferably 0.0001 to 0.15 mol / 100g, more preferably 0.001 to 0.13 mol / 100g, and even more preferably 0.005 to 0.1 mol / 100g. If the content of alkenyl groups bonded to silicon is above the lower limit, the reduction in residual adhesive strength due to unreacted components can be suppressed. Also, if the content of alkenyl groups bonded to silicon is below the upper limit, it can suppress the peeling force from becoming too high, which would make it difficult to peel off the adhesive material.

[0095] In formula (10), the (meth)acrylic group-containing group is CH2=CR 15 COR 16 -Examples of (meth)acrylic group-containing groups include R 15 R is a hydrogen atom or a methyl group, and a hydrogen atom is preferred. 16 is OR 17 Or R 17 It is a divalent group represented by OR 17 R is preferable. 17R is a divalent organic group having 1 to 20 carbon atoms, which may have branched or cyclic structures, and may contain epoxy groups, ester bonds, urethane bonds, ether bonds, isocyanate bonds, and hydroxyl groups. 17 Examples of divalent hydrocarbon groups include linear alkylene groups such as methylene, ethylene, propylene, butylene, hexamethylene, octamethylene, and desilene groups; branched alkylene groups such as methylethylene and methylpropylene groups; cyclic alkylene groups such as cyclohexylene groups; alkenylene groups such as propenylene groups; arylene groups such as phenylene groups; methylenephenylene groups; and aralkylene groups such as methylenephenylmethylene groups. These divalent hydrocarbon groups may have ester bonds, urethane bonds, ether bonds, and isocyanate bonds interposed between them, and these can be used in combination. Furthermore, some or all of the hydrogen atoms of these divalent hydrocarbon groups may be substituted with epoxy or hydroxyl groups. Among these, R 17 A propylene group is preferred. In formula (10), the alkenyl group is the same as the one specifically exemplified as the alkenyl group in formula (8), and among these, a vinyl group is preferred from an industrial standpoint.

[0096] In formula (10), the unsubstituted or substituted monovalent hydrocarbon groups that do not have an aliphatic unsaturated bond with 2 to 12 carbon atoms are the same as those specifically exemplified as monovalent hydrocarbon groups in formula (8) above. Among these, when increasing curability and lowering peel strength, the total R 14 It is preferable that 80 mol% or more of the group consists of methyl groups.

[0097] In formula (10), 2 ≤ j1 ≤ 202, preferably 2 to 102; 5 ≤ k1 ≤ 1,000, preferably 10 to 500; 0 ≤ m1 ≤ 100, preferably 0 to 50; and 0 ≤ n1 ≤ 100, preferably 0 to 50. j1 + k1 + m1 + n1 are selected such that the viscosity at 25°C falls between 1 and 10,000 mPa·s. 40 ≤ j1 + k1 + m1 + n1 ≤ 600 is preferred.

[0098] Examples of the organopolysiloxane component (E) include compounds represented by the following formula. (R 14 3SiO 1 / 2 )2(R 14 3SiO) k1 (R 14 3SiO 1 / 2 ) j1 (R 14 3SiO) k1 (R 14 SiO 3 / 2 ) m1 (R 14 3SiO 1 / 2 ) j1 (R 14 3SiO) k1 (SiO 4 / 2 ) n1 (R 14 3SiO 1 / 2 ) j1 (R 14 3SiO) k1 (R 14 SiO 3 / 2 ) m1 (SiO 4 / 2 ) n1 In each of the above formulas, R 14 j1~n1 are as described above.

[0099] More detailed examples include, but are not limited to, the compounds represented by the following formulas. Furthermore, the bonding order of each siloxane unit shown in parentheses is not limited to those shown below. (ViMe2SiO 1 / 2 )2(Me2SiO) λ1 (AMeSiO) λ2 (0≦λ1≦997.9, 0.1≦λ2≦20, 10≦λ1+λ2≦998) (Me3SiO 1 / 2 )2(Me2SiO) λ3 (AMeSiO) λ4 (0 ≤ λ3 < 997.9, 0.1 ≤ λ4 ≤ 20, 10 ≤ λ3 + λ4 ≤ 998) (ViMe2SiO1 / 2 ) λ5 (Me3SiO 1 / 2 ) λ6 (Me2SiO) λ7 (AMeSiO) λ8 (0.1≦λ5<2, 0<λ6≦1.9, λ5+λ6=2, 0≦λ7≦997.9, 0.1≦λ8≦20, 10≦λ7+λ8≦998) (ViMe2SiO 1 / 2 )2(Me2SiO) λ9 (ViMeSiO) λ10 (AMeSiO) λ11 (0≦λ9≦996.9, 1≦λ10≦997.9, 0.1≦λ11≦20, 10≦λ9+λ10+λ11≦998) (ViMe2SiO 1 / 2 ) λ12 (Me2SiO) λ13 (AMeSiO) λ14 (MeSiO 3 / 2 ) λ15 (3≦λ12≦102, 0≦λ13≦995.9, 0.1≦λ14≦20, 1≦λ15≦100, 10≦λ12+λ13+λ14+λ15≦1,000) (ViMe2SiO 1 / 2 ) λ16 (Me2SiO) λ17 (AMeSiO) λ18 (MeSiO 3 / 2 ) λ19 (SiO 4 / 2 ) λ20 (4≦λ16≦302, 0≦λ17≦994.9, 0.1≦λ18≦20, 0≦λ19≦100, 1≦λ20≦100, 10≦λ16+λ17+λ18+λ19+λ20≦1,000) In the above formulas, Me, Vi, and A represent a methyl group, a vinyl group, and a group represented by CH2=CHCOOC3H6-, respectively.

[0100] When component (E) is included, the amount is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, even more preferably 0.1 to 6 parts by mass, and particularly preferably 0.1 to 2 parts by mass, per 100 parts by mass of component (B). If the amount of component (E) is above the lower limit, the effect of enhancing the reactivity of the addition reaction is more sufficiently obtained. Also, if the amount of component (E) is below the upper limit, the adhesion is further improved.

[0101] [(F) component] The curable organopolysiloxane composition of the present invention may further contain, as component (F), an organopolysiloxane having at least two alkenyl groups bonded to silicon in one molecule, with a content of silicon-bonded alkenyl groups of 0.2 to 0.8 mol / 100g, and a viscosity of 1 to 50 mPa·s. Component (F) can be used alone or in combination of two or more.

[0102] Component (F) has at least two alkenyl groups bonded to silicon in one molecule. Having two or more alkenyl groups further improves the residual adhesive strength. More specifically, the content of alkenyl groups bonded to silicon is preferably 0.2 to 0.8 mol / 100g, preferably 0.2 to 0.7 mol / 100g, and more preferably 0.2 to 0.6 mol / 100g. If the content of alkenyl groups bonded to silicon is lower than the above lower limit, the residual adhesive strength may decrease. Also, if the content of alkenyl groups bonded to silicon is higher than the above upper limit, the peeling force may become too high, making it difficult to peel off the adhesive material.

[0103] (F) Component is an organopolysiloxane represented by the following average composition formula (11). [ka] (In the formula, R 18 These are, independently of each other, a hydroxyl group, an alkenyl group having 2 to 12 carbon atoms, or an unsubstituted or substituted monovalent hydrocarbon group that does not have an aliphatic unsaturated bond, and R 18At least two of these are alkenyl groups, p1 is 2 or greater, q1 is 2 or greater, r1 is 0 or greater, and s1 is an integer greater than or equal to 0, and p1+q1+r1+s1 is selected such that the viscosity at 25°C falls between 1 and 50 mPa·s.

[0104] In formula (11), the alkenyl group can be the same as those specifically exemplified as the alkenyl group in formula (8) above, and among these, the vinyl group is preferred from an industrial standpoint. In formula (11) above, unsubstituted or substituted monovalent hydrocarbon groups that do not have an aliphatic unsaturated bond with 2 to 12 carbon atoms are the same as those specifically exemplified as monovalent hydrocarbon groups in formula (8) above. Among these, when increasing curability and lowering peel strength, the total R 18 It is preferable that 60 mol% or more of the group consists of methyl groups.

[0105] Component (F) has a viscosity of 1 to 50 mPa·s at 25°C, preferably 3 to 45 mPa·s, and more preferably 6 to 40 mPa·s. Setting the viscosity of component (F) above the lower limit makes it easier for component (F) to remain in the cured film, while setting it below the upper limit allows for more sufficient adjustment of the H / Vi ratio with small additions.

[0106] In formula (11), p1 is an integer between 2 and 32, q1 is an integer between 2 and 40, r1 is an integer between 0 and 20, and s1 is an integer between 0 and 10, where p1+q1+r1+s1 is selected such that the viscosity at 25°C falls between 1 and 50 mPa·s, preferably 4≦p1+q1+r1+s1≦40, and more preferably 10≦p1+q1+r1+s1≦30.

[0107] Examples of the organopolysiloxane component (F) include compounds represented by the following formula. (R 18 3SiO 1 / 2 )2(R 18 2SiO) q1 (R 18 3SiO 1 / 2 ) p1(R 18 2SiO) q1 (R 18 SiO 3 / 2 ) r1 (R 18 3SiO 1 / 2 ) p1 (R 18 2SiO) q1 (SiO 4 / 2 ) s1 (R 18 3SiO 1 / 2 ) p1 (R 18 2SiO) q1 (R 18 SiO 3 / 2 ) r1 (SiO 4 / 2 ) s1 In each of the above formulas, R 18 p1~s1 are as described above.

[0108] More detailed examples include, but are not limited to, the compounds represented by the following formulas. Furthermore, the bonding order of each siloxane unit shown in parentheses is not limited to those shown below. (ViMe2SiO 1 / 2 )2(Me2SiO) π1 (2 ≤ π ≤ 38) (Vi3SiO 1 / 2 )2(Me2SiO) π2 (2 ≤ π² ≤ 38) (ViMe2SiO 1 / 2 )2(Me2SiO) π3 (ViMeSiO) π4 (0≦π3≦37, 1≦π4≦38, 2≦ π3 (+π4≦37) (ViMe2SiO 1 / 2 )2(Me2SiO) π5 (Ph2SiO) π6 (0 ≤ π5 ≤ 37, 1 ≤ π6 ≤ 38, 2 ≤ π5 + π6 ≤ 37) (ViMe2SiO 1 / 2 )2(Me2SiO)π7 (ViMeSiO) π8 (Ph2SiO) π9 (0≦π7≦36, 1≦π8≦37, 1≦π9≦37, 2≦π7+π8+π9≦36) (ViMe2SiO 1 / 2 ) π 10(Me2SiO) π11 (MeSiO 3 / 2 ) π12 (3≦π10≦22, 2≦π11≦36, 1≦π12≦20, 6≦π10+π11+π12≦40) (ViMe2SiO 1 / 2 ) π13 (Me2SiO) π14 (MeSiO 3 / 2 ) π15 (SiO 4 / 2 ) π16 (4≦π13≦32, 2≦π14≦35, 0≦π15≦20, 1≦π16≦10, 7≦π13+π14+π15+π16≦40) In the above formulas, Me, Vi, and Ph represent a methyl group, a vinyl group, and a phenyl group, respectively.

[0109] Component (F) is a component used in the present invention to adjust the ratio (H / Vi) of the total number of SiH groups to the total number of alkenyl groups in the composition. When component (A) is added to a composition consisting of components (B) and (C), the number of SiH groups derived from component (A) increases, which may increase the peeling force. Therefore, by adding a small amount of component (F), which has a high alkenyl group content, it is possible to adjust the H / Vi ratio and suppress the increase in peeling force.

[0110] When component (F) is included, the amount is preferably such that the number ratio of SiH groups in component (A) to the number of alkenyl groups in component (F) is 0.5 to 10 times the molar amount, more preferably 0.8 to 8.0 times, and even more preferably 1.0 to 5.0 times. By setting the amount of component (F) to be above the lower limit, the above adjustment of H / Vi can be sufficiently achieved, and an increase in peeling force can be suppressed. If it is below the upper limit, problems such as a decrease in curability will not occur.

[0111] [Other ingredients] In addition to components (A) to (F) above, the curable organopolysiloxane composition of the present invention may contain any other components as long as they do not impair the effects of the present invention. The other components may be any components commonly used in addition reaction curing type organopolysiloxane compositions, and known components may be added in normal amounts. For example, the following components can be used. These other components may be used individually or in combination of two or more.

[0112] (G) Addition reaction regulator The curable organopolysiloxane composition of the present invention may further contain an addition reaction control agent for platinum group metal catalysts in order to ensure pot life. The addition reaction control agent is not particularly limited as long as it is a compound that has a curing inhibitory effect on the platinum group metal catalyst of component (D) above, and conventionally known compounds can be used. Examples include various organic nitrogen compounds, organophosphorus compounds, acetylene compounds, and oxime compounds. More specifically, examples include acetylene alcohols such as 3-methyl-1-butyne-3-ol, 3,5-dimethyl-1-hexyne-3-ol, 3-methyl-1-pentin-3-ol, 2-phenyl-3-butyne-2-ol, and 1-ethynylcyclohexanol; 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 and other organophosphorus compounds; and oxime compounds.

[0113] The amount of component (G) to be added should be such that a good pot life can be obtained, and generally, 0.01 to 10 parts by mass is preferred, and 0.05 to 5 parts by mass is more preferred, per 100 parts by mass of the total of components (B) and (C).

[0114] (H) Organic solvents The curable organopolysiloxane composition of the present invention may contain (H) an organic solvent. The curable organopolysiloxane composition of the present invention can be made into a solvent-free composition by incorporating predetermined amounts of the above components (A) to (G), thereby obtaining the effects of the present invention even without a solvent. However, it can also be used as a solvent-type composition by diluting it with an organic solvent as needed. Diluting the composition with an organic solvent provides practical advantages such as improved coating workability and improved coating film condition, including the thickness of the coating film and the surface finish.

[0115] Examples of usable (H) organic 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 ether compounds such as diisopropyl ether and 1,4-dioxane. Any compound capable of dissolving components (A) to (G) above is acceptable. These can be used individually or in appropriate combinations of two or more.

[0116] Component (H) is an optional component, and its amount can be any amount. That is, it may be 0 parts by mass. If the risk of danger or reduced safety due to organic solvents is undesirable, it is also possible to omit component (H) and produce a solvent-free organopolysiloxane composition for the manufacture of release sheets. When component (H) is included, the amount is preferably 100 to 20,000 parts by mass, and more preferably 200 to 10,000 parts by mass, per 100 parts by mass of component (B). If the amount of component (H) is less than 100 parts by mass, the benefits of dilution may not be obtained, and even if it exceeds 20,000 parts by mass, little improvement in effect can be expected.

[0117] • Other optional ingredients Furthermore, known antioxidants, light peeling additives, heavy peeling additives, pigments, stabilizers, antistatic agents, defoaming agents, adhesion enhancers, thickeners, solvents, and inorganic fillers such as silica may be added as needed, within the limits that do not impede the effects of the present invention.

[0118] The viscosity of the curable organopolysiloxane composition of the present invention, as measured by a rotational viscometer at 25°C, is preferably 1 to 1,000 mPa·s, more preferably 5 to 800 mPa·s, and even more preferably 10 to 600 mPa·s. If the viscosity falls outside the above upper and lower limits, the coating properties to the substrate may decrease.

[0119] [Method for producing a curable organopolysiloxane composition] The method for preparing the curable organopolysiloxane composition of the present invention is not particularly limited, but a method in which components (A), (B), (C), optionally (E), (F), (G), (H), and other components are uniformly mixed beforehand, and then component (D) is added immediately before use, is preferable in terms of pot life.

[0120] [Coated products (release sheets)] The present invention provides a release sheet comprising a substrate and a release agent layer provided on at least one surface of the substrate, wherein the release agent layer is formed from a cured product of the curable organopolysiloxane composition described in 5. A cured film can be formed by coating one or both surfaces of the substrate with the curable organopolysiloxane composition and heating it.

[0121] The coating method and heat curing conditions are not particularly limited and may be selected as appropriate. For example, the curable organopolysiloxane composition can be applied directly to one or both sides of a sheet-like substrate such as paper or film using a coating method such as a comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater, gravure coater, wire bar coater, screen coater, dipping coater, or cast coater, at a rate of 0.01 to 100 g / m². 2 After coating, a cured film can be formed on the substrate by heating at 50-200°C for 1-120 seconds. When creating release layers 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.

[0122] In this invention, the term "release sheet" includes not only sheets made of paper but also sheets made of various known films and the like. Examples of substrates include polyethylene laminated paper, glassine paper, fine paper, various coated papers such as supercalendered kraft paper and clay-coated kraft paper, 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, and polycarbonate film. It is also possible to use process paper used for manufacturing artificial leather, ceramic sheets, double-sided separators, etc., as substrates. To improve the adhesion between these substrates and the release layer, substrates that have been corona-treated, etched, primer-treated, or plasma-treated may be used. [Examples]

[0123] 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. Unless otherwise specified, "%" in the composition refers to "mass%", and the viscosities listed below are all values ​​measured using a rotational viscometer at 25°C. The epoxy group content refers to the number of millimoles of epoxy groups per 100g of component (A), and the SiH group content refers to the number of moles of SiH groups per 100g of component (A). Furthermore, the epoxy residue rate is determined according to the method described in the text. 1 Calculated from H-NMR

[0124] [Epoxy group content] The epoxy group content was determined using an automatic titrator (HIRANUMA COM-1750) by the following hydrochloric acid-dioxane method. Specifically, a sample was weighed into a 50 mL beaker to approximately 1 / 1000th of the theoretical value. 15 mL of hydrochloric acid-1,4-dioxane solution (1.5 g of hydrochloric acid pre-dissolved in 100 mL of 1,4-dioxane) and 20 mL of ethanol were added, the beaker was sealed with Parafilm, and stirred for 15 minutes. This procedure reacted all the epoxy groups in the sample with the hydrochloric acid, and the remaining hydrochloric acid was back-titrated with a 0.1 mol / L sodium hydroxide solution. A blank sample was measured using the same procedure, and the epoxy group content was determined using the following formula (12). Epoxy group content (millimoles / 100g) = (BA) × N × f / S × 100000 B: Titration volume of blank sodium hydroxide solution (mL) A; Titration volume (mL) of the sample sodium hydroxide solution N: Normality of the sodium hydroxide solution (0.1 in this invention) f: Factor of sodium hydroxide solution S: Sample volume

[0125] [Epoxy group residual rate] Epoxy retention rate 1 The calculation was performed using H-NMR. The proton of the methylene group bonded to the Si atom of the epoxy group-containing alkoxysilane (a2), which is the starting material (δ=0.42), remains unchanged before and after ring opening of the epoxy group, so this proton peak was used as the reference. The integral value of the methylene proton peak derived from the reference epoxy group-containing monovalent organic group is set to 2.00. If a starting material having a glycidyl group is used as component (a2), and the epoxy group remains 100% intact without ring opening, then the following H a The peak integral value (around δ=2.5, 2.7) is 2.00. On the other hand, if the epoxy group is ring-open, then H a The peak integral value decreases. From this, the remaining epoxy group percentage was calculated according to the following formula (X). Epoxy residue rate (%) = [(H a (Peak integral value of) / 2.00] × 100 (X) Similarly, if a raw material having an alicyclic epoxy group is used as component (a2), and 100% of the epoxy group remains without ring opening, then the following H b and H c The sum of the peak integral values ​​(around δ=3.1) is 2.00. From this, the remaining epoxy group percentage was calculated according to the following formula (Y). Epoxy residue rate (%) = [(H b +H c (Peak integral value of) / 2.00] × 100 (Y) [ka]

[0126] The weight-average molecular weight is the value obtained by GPC (gel permulation chromatography) analysis using polystyrene as the standard substance under the following conditions. [Measurement conditions] Developing solvent: Toluene Flow rate: 0.35mL / min Detector: Differential refractive index detector (RI) column: TSKgel Guardcolumn SuperHZ-L(4.6mmI.D.×2cm×1) TSKgel SuperHZ4000(4.6mmI.D.×15cm×1) TSKgel SuperHZ3000(4.6mmI.D.×15cm×1) TSKgel SuperHZ2000 (4.6mmI.D.×15cm×2) (All manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 100 μL (0.5% by mass toluene solution)

[0127] The following raw materials were used in the examples and comparative examples. Hereinafter, Me represents a methyl group. Furthermore, the bonding order of each siloxane unit shown in parentheses is not limited to the following. (a1) component (a1-1) Linear methylhydrogenpolysiloxane represented by the following formula [ka] (a1-2) Linear methylhydrogenpolysiloxane represented by the following formula [ka] (a1-3) Linear methylhydrogenpolysiloxane represented by the following formula [ka] (a1-4) Cyclic methylhydrogentetrasiloxane represented by the following formula [ka] (a1-5) Methylhydrogen disiloxane represented by the following formula [ka] (a2) Component (a2-1) 3-Glycidoxypropylmethyldimethoxysilane, represented by the following formula [ka] (a2-2) 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane represented by the following formula [ka] (a2-3) 3-glycidoxypropyltrimethoxysilane represented by the following formula [ka] (a3) Component (a3-1) Dimethyldimethoxysilane represented by the following formula [ka] (a5) Component (a5-1) Trifluoroacetic acid, pKa = -0.25 (a5-2) Trichloroacetic acid, pKa=0.65 (a5-3) Dichloroacetic acid, pKa=1.29 (a5-4) Chloroacetic acid, pKa=2.86

[0128] Comparative Example Components (h-1) Methanesulfonic acid, pKa = -2.6 (h-2) Sulfuric acid, pKa=-3.0 (h-3) hydrochloric acid, pKa = -8.0 (h-4) Trifluoromethanesulfonic acid, pKa=-14 (h-5) Acetic acid, pKa = 4.76

[0129] [Example 1] Equipped with a stirrer, thermometer, and condensate, a 300 mL separable flask was purged with nitrogen and contained 204.6 g (0.1 mol) of (a1-1) methylhydrogenpolysiloxane, 44.0 g (0.2 mol) of (a2-1) 3-glycidoxypropylmethyldimethoxysilane, and 12.0 g (0.1 mol) of (a3-1) dimethyldimethoxysilane. The mixture was stirred until homogeneous. Then, 2.7 g (0.024 mol) of (a5-1) trifluoroacetic acid (1.04% by mass relative to the total amount of components (a1) to (a3)) was added and the mixture was stirred further until homogeneous. Then, 5.8 g (0.32 mol) of (a4) deionized water (0.54 mol relative to 1 mole of alkoxy groups derived from components (a2) and (a3)) was slowly added dropwise, and the mixture was then heated and stirred at 70-75°C for 4 hours. When a portion of the reactant was extracted and its non-volatile content was measured, it was found to be 79% by mass, confirming that the reaction was proceeding. The reaction mixture was transferred to a 2 L separable flask with a stopcock, and 250 g of toluene was added and stirred until homogenized. Then, 150 g of 8% sodium bicarbonate solution, which had been pre-dissolved to a concentration of 8%, was added and the mixture was stirred at room temperature for 30 minutes to neutralize the trifluoroacetic acid. After stopping the stirring, the mixture was allowed to stand at room temperature for 30 minutes, separating it into an organic layer (upper layer) and an aqueous layer (lower layer). The aqueous layer was then removed through the stopcock. This neutralization process was repeated twice. To the remaining organic layer, 150 g of 10% sodium sulfate solution, which had been pre-dissolved to a concentration of 10%, was added, and the same procedure was repeated once. After transferring the organic layer to a 500 mL separable flask, it was stripped under reduced pressure at 80°C and 10 mmHg for 1 hour to obtain a colorless, transparent epoxy group-containing organohydrogenpolysiloxane (A-1) with the following characteristics. At 25°C, the viscosity was 31 mPa·s, the weight-average molecular weight was 4,500, the SiH group content was 1.35 mol / 100g, the epoxy group content was 112 mmol / 100g, and the epoxy retention rate was 78%. Furthermore, when stored in a sealed plastic bottle at room temperature for 4 months, the product remained liquid.

[0130] [Example 2] The process of Example 1 was repeated, except that the raw materials used in Example 1 were replaced as follows, to obtain a colorless, transparent epoxy group-containing organohydrogenpolysiloxane (A-2). (a1)(a1-1)122.8g (0.06 mol) + (a1-2)77.0g (0.12 mol) (a2)(a2-1)33.0g (0.15 mol) (a4) 2.9g of deionized water (0.16 moles, an amount such that the molar ratio of alkoxy groups derived from component (a2) to 1 mole is 0.54) (a5)(a5-1) 2.5g (0.022 moles, 1.04% by mass relative to the total amount of components (a1) to (a2))

[0131] [Example 3] The process of Example 1 was repeated, except that the raw materials used in Example 1 were replaced as follows, to obtain a colorless, transparent epoxy group-containing organohydrogenpolysiloxane (A-3). (a1)(a1-1)122.8g (0.06 mol) + (a1-3)98.2g (0.12 mol) (a2)(a2-1)39.6g (0.18 moles) (a4) 3.5g of deionized water (0.19 moles, an amount such that the molar ratio of alkoxy groups derived from component (a2) to 1 mole is 0.54) (a5)(a5-1) 2.8g (0.025 moles, 1.07% by mass relative to the total amount of components (a1) to (a2))

[0132] [Example 4] The process of Example 1 was repeated, except that the raw materials used in Example 1 were replaced as follows, to obtain a colorless, transparent epoxy group-containing organohydrogenpolysiloxane (A-4). (a1)(a1-4)75.6g (0.32 mol) + (a1-5)16.1g (0.12 mol) (a2)(a2-1)21.1g (0.10 moles) (a3)(a3-1) 72.0g (0.60 moles) (a4) 21.0 g of deionized water (1.17 moles, an amount such that the molar ratio of alkoxy groups derived from components (a2) and (a3) ​​to 1 mole is 0.84) (a5)(a5-1) 2.6g (0.023 moles, 1.41% by mass relative to the total amount of components (a1) to (a3))

[0133] [Example 5] The process of Example 1 was repeated, except that the raw materials used in Example 1 were replaced as follows, to obtain a colorless, transparent epoxy group-containing organohydrogenpolysiloxane (A-5). (a1)(a1-1)204.6g (0.10 moles) (a2)(a2-2)46.0g (0.20 moles) (a3)(a3-1) 12.0g (0.10 moles) (a4) 5.8 g of deionized water (0.32 moles, an amount such that the molar ratio of alkoxy groups derived from components (a2) and (a3) ​​to 1 mole is 0.54) (a5)(a5-1) 2.7g (0.024 moles, 1.03% by mass relative to the total amount of components (a1) to (a3))

[0134] [Example 6] Equipped with a stirrer, thermometer, and condensate, a 300 mL separable flask purged with nitrogen contained 20 g (0.1 mol) of (a1-1) methylhydrogenpolysiloxane, 47.2 g (0.2 mol) of (a2-3) 3-glycidoxypropyltrimethoxysilane, and 12.0 g (0.1 mol) of (a3-1) dimethyldimethoxysilane, and stirred until homogeneous. Then, 2.7 g (0.024 mol) of (a5-1) trifluoroacetic acid (an amount equivalent to 1.02% by mass of the total amount of components (a1) to (a3)) was added and stirred further until homogeneous. Then, 5.8 g (0.32 mol) of (a4) deionized water (an amount equivalent to 0.40 molar ratios of alkoxy groups derived from components (a2) and (a3)) was slowly added dropwise, and the mixture was then heated and stirred at 70-75°C for 4 hours. When a portion of the reactant was extracted and its non-volatile content was measured, it was found to be 76% by mass, confirming that the reaction was proceeding. 16.2 g of Kyoward 500SH (six times the amount of component (a5-1)) manufactured by Kyowa Chemical Industry Co., Ltd. was added to the reaction mixture, and the mixture was stirred at room temperature for 2 hours to neutralize the trifluoroacetic acid. After removing Kyoward 500SH by filtration, the reaction mixture was transferred to a 300 mL separable flask and stripped under reduced pressure at 80°C and 10 mmHg for 1 hour to obtain a colorless, transparent epoxy group-containing organohydrogenpolysiloxane (A-6) having the following characteristics. At 25°C, the viscosity was 38 mPa·s, the weight-average molecular weight was 4,800, the SiH group content was 1.25 mol / 100g, the epoxy group content was 106 mmol / 100g, and the epoxy retention rate was 81%. Furthermore, when stored in a sealed plastic bottle at room temperature for 4 months, the product remained liquid.

[0135] [Example 7] The process of Example 6 was repeated, except that the raw materials used in Example 6 were replaced as follows, to obtain a colorless, transparent epoxy group-containing organohydrogenpolysiloxane (A-7). (a1)(a1-1)204.6g (0.10 moles) (a2)(a2-1) 44.0g (0.20 moles) (a3)(a3-1) 12.0g (0.10 moles) (a4) 5.8 g of deionized water (0.32 moles, an amount such that the molar ratio of alkoxy groups derived from components (a2) and (a3) ​​to 1 mole is 0.54) (a5)(a5-2) 2.7g (0.017 moles, 1.04% by mass relative to the total amount of components (a1) to (a3))

[0136] [Example 8] The process of Example 6 was repeated, except that the raw materials used in Example 6 were replaced as follows, to obtain a colorless, transparent epoxy group-containing organohydrogenpolysiloxane (A-8). (a1)(a1-1)204.6g (0.10 moles) (a2)(a2-1) 44.0g (0.20 moles) (a3)(a3-1) 12.0g (0.10 moles) (a4) 5.8 g of deionized water (0.32 moles, an amount such that the molar ratio of alkoxy groups derived from components (a2) and (a3) ​​to 1 mole is 0.54) (a5)(a5-3) 2.7g (0.021 moles, 1.04% by mass relative to the total amount of components (a1) to (a3))

[0137] [Example 9] The process of Example 6 was repeated, except that the raw materials used in Example 6 were replaced as follows, to obtain a colorless, transparent epoxy group-containing organohydrogenpolysiloxane (A-9). (a1)(a1-1)204.6g (0.10 moles) (a2)(a2-1) 44.0g (0.20 moles) (a3)(a3-1) 12.0g (0.10 moles) (a4) 5.8 g of deionized water (0.32 moles, an amount such that the molar ratio of alkoxy groups derived from components (a2) and (a3) ​​to 1 mole is 0.54) (a5)(a5-4) 2.7g (0.029 moles, 1.04% by mass relative to the total amount of components (a1) to (a3))

[0138] [Comparative Example 1] Equipped with a stirrer, thermometer, and condensate, a 300 mL separable flask purged with nitrogen contained 204.6 g (0.1 mol) of (a1-1) methylhydrogenpolysiloxane, 44.0 g (0.2 mol) of (a2-1) 3-glycidoxypropylmethyldimethoxysilane, and 12.0 g (0.1 mol) of (a3-1) dimethyldimethoxysilane, and stirred until homogeneous. When 2.7 g (0.028 mol) of (h-1) methanesulfonic acid (an amount equivalent to 1.04% by mass of the total amount of components (a1) to (a3)) was added, a small amount of gel immediately formed, and the target product could not be obtained.

[0139] [Comparative Example 2] In Comparative Example 1, the catalyst was changed to 13.0 g of (h-2) sulfuric acid (0.13 moles, an amount representing 5% by mass of the total amount of components (a1) to (a3)), and the process of Comparative Example 1 was repeated. However, a small amount of gel material was formed immediately after the addition of the catalyst, and the target product could not be obtained.

[0140] [Comparative Example 3] In Comparative Example 1, the catalyst was changed to 8.9 g of a 35% (h-3) hydrochloric acid aqueous solution (0.085 moles of hydrochloric acid, amounting to 1.20% by mass relative to the total amount of components (a1) to (a3), and 0.32 moles of water, amounting to 0.54 moles of alkoxy groups derived from components (a2) and (a3)). The process of Comparative Example 1 was repeated, except that the catalyst was changed to 8.9 g of a 35% (h-3) hydrochloric acid aqueous solution (0.085 moles of hydrochloric acid, amounting to 1.20% by mass relative to the total amount of components (a1) to (a3), and 0.32 moles of water, amounting to 0.54 moles of alkoxy groups derived from components (a2) and (a3)). Since no gel formation was observed immediately after the addition of the catalyst, the mixture was heated and stirred at 70-75°C for 4 hours. When a portion of the reactant was extracted and its non-volatile content was measured, it was found to be 27% by mass, indicating that the reaction had not proceeded sufficiently.

[0141] [Comparative Example 4] In Comparative Example 1, the catalyst was changed to 2.7 g of (h-5)acetic acid (0.045 moles, an amount equivalent to 1.04% by mass relative to the total amount of components (a1) to (a3)), and the process of Comparative Example 1 was repeated. Since no gel formation was observed immediately after catalyst addition, 5.8 g of (a3) ​​ion-exchanged water (0.32 moles, an amount equivalent to a molar ratio of 0.54 to 1 mole of alkoxy groups derived from components (a2) and (a3)) was slowly added dropwise, and then the mixture was heated and stirred at 70-75°C for 4 hours. When a portion of the reactant was extracted and its non-volatile content was measured, it was 10% by mass, indicating that the reaction had not proceeded sufficiently.

[0142] [Comparative Example 5] Equipped with a stirrer, thermometer, and condensate, a 1 L separable flask purged with nitrogen contained 204.6 g (0.1 mol) of (a1-1) methylhydrogenpolysiloxane, 44.0 g (0.2 mol) of (a2-1) 3-glycidoxypropylmethyldimethoxysilane, 12.0 g (0.1 mol) of (a3-1) dimethyldimethoxysilane, and 260 g of isopropyl alcohol (IPA). The mixture was stirred until homogeneous. Then, 2.7 g (0.028 mol) of (h-1) methanesulfonic acid (an amount equivalent to 1.04% by mass of the total amount of components (a1) to (a3)) was added, and no gel formation was observed, resulting in a homogeneous reaction solution. To this, 5.8 g of (a4) deionized water (0.32 moles, an amount such that the molar ratio of alkoxy groups derived from components (a2) and (a3) ​​to 1 mole is 0.54) was slowly added dropwise, and the mixture was then heated and stirred at 70-75°C for 4 hours. A portion of the reactant was extracted and its non-volatile content was measured to be 47% by mass, confirming that the reaction was proceeding. 16.2 g of Kyoward 500SH (six times the amount of component (h-1)) manufactured by Kyowa Chemical Industry Co., Ltd. was added to the reaction product, and the mixture was stirred at room temperature for 2 hours to neutralize the methanesulfonic acid. After removing Kyoward 500SH by filtration, the reaction product was transferred to a 1 L separable flask and stripped under reduced pressure at 80°C and 15 mmHg for 1 hour to obtain a colorless, transparent epoxy group-containing organohydrogenpolysiloxane (A-10) having the following characteristics. At 25°C, the viscosity was 14 mPa·s, the weight-average molecular weight was 2,000, and the SiH group content was 1.33 mol / 100g. However, the epoxy group content was 40 mmol / 100g, and the epoxy retention rate was 32%, confirming ring-opening of the epoxy groups. Furthermore, when stored in a sealed plastic bottle at room temperature for 4 months, the product remained liquid.

[0143] [Comparative Example 6] In Comparative Example 5, the catalyst was changed to (h-4)trifluoromethanesulfonic acid 2.7 (0.018 mol, an amount equivalent to 1.04% by mass of the total amount of components (a1) to (a3)), and the steps of Comparative Example 5 were repeated to obtain a colorless, transparent epoxy group-containing organohydrogenpolysiloxane (A-11) having the following characteristics: viscosity at 25°C of 27 mPa·s, weight-average molecular weight of 7,100, and SiH group content of 1.30 mol / 100g. However, the epoxy retention rate was 0%, confirming that all epoxy groups had been ring-opened. Furthermore, when stored in a sealed poly bottle at room temperature for 4 months, the product remained liquid.

[0144] [Comparative Example 7] Equipped with a stirrer, thermometer, and condensate, a nitrogen-purged 300 mL separable flask was used to add 204.6 g (0.1 mol) of (a1-1) methylhydrogenpolysiloxane, 11.4 g (0.1 mol) of allyl glycidyl ether (AGE), and 56.9 g of toluene. The mixture was stirred until homogeneous and then heated to 60°C. To this, 0.74 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (0.19 × 10¹⁶ as platinum atoms) was added. -4 Upon adding (mol), a temperature increase of approximately 30°C was observed, confirming the progress of the addition reaction. Furthermore, 11.4 g (0.1 mol) of allyl glycidyl ether was slowly added dropwise, and the mixture was heated and stirred at 80-85°C for 1 hour. A portion of the reaction product was then extracted. 1 ¹H-NMR analysis revealed the disappearance of the peak for the allyl group of the allyl glycidyl ether, confirming that the addition reaction had proceeded completely. 2.3 g of activated carbon (1% by mass relative to the total amount of component (a1) and AGE) was added to the reaction mixture and stirred at room temperature for 1 hour to adsorb the platinum catalyst. After removing the activated carbon by filtration, the reaction mixture was transferred to a 300 mL separable flask and stripped under reduced pressure at 80°C and 14 mmHg for 1 hour to obtain a pale yellow, transparent epoxy group-containing organohydrogenpolysiloxane (A-12) with the following characteristics. At 25°C, the viscosity was 340 mPa·s, the weight-average molecular weight was 135,800, the SiH group content was 1.05 mol / 100g, the epoxy group content was 75 mmol / 100g, and the epoxy retention rate was 93%. However, gel material adhered to the wall of the separable flask after stripping, and the product was also of high viscosity (high molecular weight). Furthermore, when stored in a sealed plastic bottle at room temperature for 4 months, the product gelled.

[0145] Tables 1-4 below summarize the raw materials used in Examples 1-9 and Comparative Examples 1-7, the molar ratio of the total of components (a2) and (a3) ​​to component (a1) (silane / (a1) ratio), the molar ratio of component (a4) to 1 mole of methoxy groups derived from components (a2) and (a3) ​​(water / methoxy ratio), the amount of component (a5) blended relative to the total amount of components (a1)-(a3) (mass%), the set structure determined from the raw material charging ratio, and, if an epoxy group-containing organohydrogen polysiloxane was obtained, its physical properties. In Tables 1-4 below, the change over time refers to the properties (liquid or gelled) after the product was stored in a sealed poly bottle at room temperature for 4 months.

[0146] In the example below, the symbols indicating the average composition of organopolysiloxanes are as follows: M:(CH3)3SiO 1 / 2 M H :(CH3)2HSiO 1 / 2 D:(CH3)2SiO 2 / 2 D H :(CH3)HSiO 2 / 2 D GE :(CH3)(GE)SiO2 / 2 GE: [ka] (* indicates a site of binding to silicon) D Ep :(CH3)(EP)SiO 2 / 2 EP: [ka] (* indicates a site of binding to silicon) T GE :(GE)(OCH3)SiO 2 / 2 GE: [ka] (* indicates a site of binding to silicon)

[0147] [Table 1]

[0148] [Table 2]

[0149] [Table 3]

[0150] [Table 4]

[0151] As shown in Examples 1 to 9 in Tables 1 to 4 above, by following the manufacturing method of the present invention, ring-opening of epoxy groups is suppressed, and epoxy group-containing organohydrogenpolysiloxanes with a high SiH content can be obtained. There is no gelation or thickening during the reaction, and no gelation occurs over time. On the other hand, in Comparative Examples 1-4, the target product could not be obtained because gel formation occurred during catalyst addition or the reaction did not proceed sufficiently. The present invention's examples can achieve the above effects even without a solvent. In contrast, when IPA is used as a solvent, as in Comparative Examples 5 and 6, the product can be obtained while suppressing the formation of gel during catalyst addition, but the epoxy ring opens due to the strong acidity of the catalyst, resulting in a low epoxy retention rate. Furthermore, in the conventional addition reaction production method, as in Comparative Example 7, partial gelation and significant thickening (increased molecular weight) were observed during synthesis, and ultimately gelled over time.

[0152] [Production of curable organopolysiloxane compositions] The following are examples and comparative examples of curable organopolysiloxane compositions, but the present invention is not limited to the following examples. The vinyl value and acrylic value are 1 These values ​​were measured using 1H-NMR. Below, Me, Vi, and A represent a methyl group, a vinyl group, and a group represented by CH2=CHCOOC3H6-, respectively.

[0153] The following components were used in the examples and comparative examples. In the following, the vinyl value is the number of moles of vinyl groups per 100g of each component, and the acrylic value is the number of moles of the group represented by CH2=CHCOOC3H6- per 100g of each component. Furthermore, the bonding order of each siloxane unit shown in parentheses is not limited to the following.

[0154] (A) component Epoxy group-containing organohydrogenpolysiloxanes (A-1) to (A-9) obtained in Examples 1 to 9 (B) Component (B-1) Methylvinylpolysiloxane in which both ends of the molecular chain are sealed with dimethylvinylsiloxy groups, with a vinyl value of 0.018 mol / 100g and a viscosity of 380 mPa·s: (ViMe2SiO 1 / 2 )2(Me2SiO) 150 (B-2)(ViMe2SiO 1 / 2An organopolysiloxane composed of 0.025 mol% dimethylvinylsiloxane units (represented as (ViMeSiO)), 1.46 mol% methylvinylsiloxane units (represented as (ViMeSiO)), and 98.5 mol% dimethylsiloxane units (represented as (Me2SiO)): A 30% by mass toluene solution has a viscosity of 15 Pa·s at 25°C and a vinyl group content of 0.020 mol / 100g.

[0155] (C) Component (C-1) Methylhydrogenpolysiloxane in which both ends of the molecular chain are sealed with trimethylsiloxy groups, the SiH group content is 1.6 mol / 100 g, and the viscosity is 20 mPa·s: (Me3SiO 1 / 2 )2(MeHSiO) 40 (C-2) Methylhydrogenpolysiloxane in which both ends of the molecular chain are sealed with trimethylsiloxy groups, the SiH group content is 1.0 mol / 100 g, and the viscosity is 50 mPa·s: (Me3SiO 1 / 2 )2(MeHSiO) 45 (Me2SiO) 20

[0156] [Preparation Example 1] Preparation of Platinum Catalyst D The reaction product of hexachloroplatinic acid and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was diluted with the above-mentioned methylvinylpolysiloxane (B-1) to a platinum content of 0.50% by mass to prepare platinum catalyst D, which will be used in this example and comparative example.

[0157] (E) Component (E-1) Acrylic group-containing methylvinylpolysiloxane, in which both ends of the molecular chain are sealed with dimethylvinylsiloxy groups and the side chain has an acrylic group-containing group, with a vinyl value of 0.016 mol / 100g, an acrylic group-containing group content of 0.077 mol / 100g, and a viscosity of 450 mPa·s: (ViMe2SiO 1 / 2 )2(Me2SiO) 150 (AMeSiO) 10 (F) component (F-1) Methylvinylpolysiloxane in which both ends of the molecular chain are sealed with dimethylvinylsiloxy groups, with a vinyl value of 0.21 mol / 100g and a viscosity of 8 mPa·s: (ViMe2SiO 1 / 2 )2(Me2SiO) 10 (F-2) Methylvinylpolysiloxane in which all molecular chain ends are sealed with dimethylvinylsiloxy groups, with a vinyl value of 0.53 mol / 100g and a viscosity of 20 mPa·s: (ViMe2SiO 1 / 2 ) 12 (MeSiO 3 / 2 ) 10 (G) Component (G) 1-Ethynyl-1-cyclohexanol (H) Component (H) toluene and hexane mixed solvent in a mass ratio of 1:1

[0158] Comparative Example Components • Organohydrogenpolysiloxanes that do not contain epoxy groups: The above (C-1) component • Epoxy group-containing organopolysiloxanes that do not have the SiH group shown below: [ka] • Epoxy group-containing organohydrogenpolysiloxanes obtained in Comparative Examples 5-7 above: (A-10)~(A-12)

[0159] [Examples 10-20, Comparative Examples 8-13 (Solvent-free type)] Components (B), (C), (E), (F), and (G) above, and component (A) or comparative example component were placed in a flask according to the mixing ratios shown in Tables 5 to 7, and stirred until homogeneous. Component (D) was then added to the mixture in an amount of 50 ppm or 25 ppm of platinum equivalent relative to the total mass of the composition, and the mixture was mixed and stirred to obtain an organopolysiloxane composition for coating. The ratio of the total number of SiH groups to the total number of alkenyl groups in the composition (H / Vi: total), the ratio of the number of SiH groups in component (C) to the number of alkenyl groups in component (B) (H / Vi: (C) / (B)), and the appearance of the composition are shown in Tables 5 to 7. Coated products were also prepared and evaluated using this composition by the method described later.

[0160] [Curing of solvent-free organopolysiloxane compositions] The above solvent-free organopolysiloxane 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 supercalendered kraft paper (SCK). The supercalendered kraft paper with the transferred composition was heated in a 150°C hot air dryer for 30 seconds to a thickness of 0.9~1.1 g / m². 2 A release paper having a cured coating was obtained.

[0161] [Example 21, Comparative Example 14 (Solvent-type)] Components (B), (C), (G), and (A) were placed in a flask according to the mixing ratios shown in Tables 6-7 below. Component (H) was added in a quantity of 1900 parts by mass, and the mixture was stirred until homogeneous. Component (D) was then added to the flask in a quantity equivalent to 150 ppm of platinum relative to the total mass of the composition, and the mixture was stirred to obtain an organopolysiloxane composition for coating. The ratio of the total number of SiH groups to the total number of alkenyl groups (H / Vi) and the appearance of the composition are shown in Tables 6-7. Coated products were then prepared and evaluated using this composition according to the method described later.

[0162] [Curing of solvent-based organopolysiloxane compositions] The above solvent-based organopolysiloxane composition was coated onto supercalendered kraft paper (SCK) using a bar coater, and then heated in a hot air dryer at 150°C for 30 seconds to a thickness of 0.9-1.1 g / m². 2 A release paper having a cured coating was obtained.

[0163] [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 (the side transferred from the rubber roll), and the piece was cut to a size of 25mm x 23cm. This was sandwiched between glass plates and cured at 70°C at a rate of 20g / cm². 2 The sample was prepared after aging under the specified load for 24 hours. After air cooling for about 30 minutes, 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. The results are shown in Tables 5-7.

[0164] [Residual adhesion rate] The adhesive side of the TESA-7475 tape, peeled from the release layer in the above peeling force measurement, was attached to a stainless steel plate, and a load was applied by moving a 2kg roller back and forth. After 30 minutes, one end of the TESA-7475 tape was peeled off, and that end was pulled at a 180-degree angle to the stainless steel plate, peeling it off at a peeling speed of 0.3m / min. The force required to peel it off at that time, the peeling force A (gf / 25mm), was measured. In addition, unused TESA-7475 tape, which had not been bonded to a release layer, was attached to a stainless steel plate. Under the same conditions as above, the force required to peel the TESA-7475 tape from the stainless steel plate: peel force B (gf / 25mm) was measured. The results are shown in Tables 5-7. The residual adhesion rate (%) was calculated using the formula: Residual adhesion rate (%) = (A / B) × 100.

[0165] [Adhesion] The release paper and release film obtained by the curing method described above were aged at 25°C for 24 hours and then stored under the conditions described below. After that, the release layer of each was rubbed 10 times with a finger and visually observed to see if it detached from the substrate, and evaluated according to the following criteria. The results are shown in Tables 5 to 7. • Cured product of solvent-free organopolysiloxane composition A: No shedding was observed within 20 hours at 85℃ and 85%RH. B: No shedding observed within 10 hours at 85°C and 85% RH, but shedding occurred within 20 hours at 85°C and 85% RH. C: No shedding observed within 5 hours at 85°C and 85% RH, but shedding occurred within 10 hours at 85°C and 85% RH. D: Decomposes within 5 hours at 85℃ and 85%RH. • Cured product of solvent-based organopolysiloxane composition A: No shedding was observed within 96 hours at 85℃ and 85%RH. B: No shedding observed up to 48 hours at 85°C and 85% RH, but shedding occurred up to 96 hours at 85°C and 85% RH. C: No shedding observed within 24 hours at 85°C and 85% RH, but shedding occurred within 48 hours at 85°C and 85% RH. D: Dropped off within 24 hours at 85℃ and 85%RH.

[0166] [Table 5]

[0167] [Table 6]

[0168] [Table 7]

[0169] As shown in Table 7 above, Comparative Examples 8-10 and 14, which did not contain the adhesion enhancer of component (A) of the present invention, and Comparative Examples 11 and 12, which used organohydrogenpolysiloxanes with many opened epoxy groups, showed almost no improvement in adhesion. Furthermore, in Comparative Example 13, which used an epoxy group-containing organohydrogenpolysiloxane obtained by a conventional addition reaction, improvement in adhesion was confirmed, but the adhesion enhancer had poor compatibility and separation over time was observed. In contrast, as shown in Tables 5 and 6 above, Examples 10 to 21, in which the epoxy group-containing organohydrogenpolysiloxane represented by component (A) of the present invention was added, showed a significant improvement in adhesion. Even when the amount of platinum was small, as in Examples 11 to 20, high adhesion to the substrate was maintained. [Industrial applicability]

[0170] The manufacturing method of the present invention suppresses viscosity buildup and gelation during synthesis and over time compared to conventional methods for producing epoxy group-containing organohydrogenpolysiloxanes using addition reactions, and can be manufactured at low cost because it does not require the use of expensive platinum catalysts. Furthermore, the release sheet made from the curable organopolysiloxane composition of the present invention exhibits high adhesion to substrates such as supercalendered kraft paper, and can therefore be suitably used as a release sheet, such as release paper or release film.

Claims

1. A method for producing epoxy group-containing organohydrogenpolysiloxanes, (a1) A linear, branched, or cyclic organohydrogenpolysiloxane represented by the following average composition formula (1), (R 1 3 SiO 1 / 2 ) a (R 1 2 SiO) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (1) (In the formula, R 1 R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or a hydrogen atom. 1 At least two of them are hydrogen atoms. a is a number greater than or equal to 0, b is a number greater than or equal to 0, c is a number greater than or equal to 0, d is a number greater than or equal to 0, and 2 ≤ a + b + c + d ≤ 500. (a2) An epoxy group-containing alkoxysilane represented by the following average composition formula (2), R 2 -SiR 3 x (OR 4 ) 3-x (2) (In the formula, R 2 R is independently an epoxy group-containing monovalent organic group, 3 and R 4 Each of these is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and x is 0, 1, or 2. (a3) As an optional component, an alkoxysilane represented by the following average composition formula (3) SiR 5 y (OR 6 ) 4-y (3) (In the formula, R 5 and R 6 Each of these is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and y is 0, 1, 2, or 3. The mixture is formulated such that the molar ratio of the total of components (a2) and (a3) ​​to component (a1) [(a2) + (a3)] / (a1) is between 0.1 / 1 and 998 / 1. The following components (a4) and (a5) (a4) Water: an amount such that the molar ratio of alkoxy groups derived from component (a2) and component (a3) ​​to 1 mole is 0.2 to 1, (a5) Acid catalyst with an acid dissociation constant (pKa) of -2 to 4: effective amount A method for producing the epoxy group-containing organohydrogenpolysiloxane, comprising the step of carrying out a hydrolysis equilibration reaction in the presence of a substance to obtain the epoxy group-containing organohydrogenpolysiloxane.

2. (a1) The component is the following average composition formula (4) (R 7 (3-z) H z SiO 1 / 2 ) 2 (R 7 HSiO) g (R 7 2 SiO) h (4) (In the formula, R 7 These are, independently of each other, unsubstituted or substituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and z is 0 or 1. When z is 0, g is a number greater than or equal to 2, h is a number greater than or equal to 0, g > h, and 2 ≤ g + h ≤ 498. When z is 1, g is a number greater than or equal to 0, h is a number greater than or equal to 0, g ≥ h, and 0 ≤ g + h ≤ 498. A method for producing an epoxy group-containing organohydrogenpolysiloxane according to claim 1, wherein the linear organohydrogenpolysiloxane is represented by .

3. (a1) The component is the following average composition formula (5) (R 7 HSiO) j (R 7 2 SiO) k (5) (In the formula, R 7 (Each of the three elements is an independent, unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, where j is a number greater than or equal to 2, k is a number greater than or equal to 0, where j > k and 2 ≤ j + k ≤ 10.) A method for producing an epoxy group-containing organohydrogenpolysiloxane according to claim 1, wherein the cyclic organohydrogenpolysiloxane is represented by .

4. The epoxy group-containing organohydrogen polysiloxane is given by the following average composition formula (6) (R 8 3 SiO 1 / 2 ) p (R 8 2 SiO) q (R 8 SiO 3 / 2 ) r (SiO 4 / 2 ) s (6) (In the formula, R 8 R is independently an unsubstituted or substituted monovalent hydrocarbon group, alkoxy group, hydroxyl group, hydrogen atom, or epoxy group-containing monovalent organic group having 1 to 12 carbon atoms, and 8 At least two of them are hydrogen atoms, R 8 At least 0.1 of these are monovalent organic groups containing epoxy groups, p is a number of 2 or more, q is a number of 0.1 or more, r is a number of 0 or more, s is a number of 0 or more, and 2.1 ≤ p + q + r + s ≤ 1,000. The method for producing an epoxy group-containing organohydrogenpolysiloxane according to claim 1.

5. A curable organopolysiloxane composition containing the following components (A) to (D). (A) The following average composition formula (6) (R 8 3 SiO 1 / 2 ) p (R 8 2 SiO) q (R 8 SiO 3 / 2 ) r (SiO 4 / 2 ) s (6) (In the formula, R 8 These are, independently of each other, unsubstituted or substituted monovalent hydrocarbon groups, alkoxy groups, hydroxyl groups, hydrogen atoms, or epoxy group-containing monovalent organic groups having 1 to 12 carbon atoms, and R 8 At least two of them are hydrogen atoms, R 8 At least 0.1 of these are monovalent organic groups containing epoxy groups, p is a number of 2 or more, q is a number of 0.1 or more, r is a number of 0 or more, s is a number of 0 or more, and 2.1 ≤ p + q + r + s ≤ 1,000. Represented as follows, the epoxy group-containing organohydrogenpolysiloxane in component (A) has an epoxy group-containing monovalent organic group content of 80 mmol or more per 100 g of component (A): 0.01 to 10 parts by mass per 100 parts by mass of component (B), (B) Organopolysiloxane having at least two alkenyl groups bonded to silicon in one molecule: 100 parts by mass, (C) Organohydrogenpolysiloxane having at least two hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule: an amount such that the ratio of the number of SiH groups in component (C) to the number of alkenyl groups in component (B) is 0.5 to 10. (D) Platinum group metal catalyst: catalyst amount

6. (A) The component is the following average composition formula (7) (R 9 3 SiO 1 / 2 ) 2 (R 10 R 11 SiO) t (R 9 HSiO) u (R 9 2 SiO) v (7) (wherein R 9 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 10 are each independently an epoxy group-containing monovalent organic group, and R 11 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group or a hydroxyl group, t is a number of 0.5 or more, u is a number of 2 or more, v is a number of 1 or more, and 3.5 < t+u+v ≤ 998.) The curable organopolysiloxane composition according to claim 5, wherein the content of epoxy group-containing monovalent organic groups in component (A) exceeds 100 mmol per 100 g of component (A).

7. (B) Component is the following average composition formula (8) 【Chemistry 1】 (In the formula, R 12 R is independently a hydroxyl group, an alkenyl group having 2 to 12 carbon atoms, or an unsubstituted or substituted monovalent hydrocarbon group that does not have an aliphatic unsaturated bond. 12 At least two of these are alkenyl groups, and a1 is 2 or more, b1 is 8 or more, c1 is 0 or more, and d1 is 0 or more, and the number of a1 + b1 + c1 + d1 is selected such that the viscosity at 25°C is between 60 mPa·s and 70,000 mPa·s for 30% toluene solubility. The curable organopolysiloxane composition according to claim 5, wherein the content of alkenyl groups bonded to silicon is 0.001 to 0.2 mol / 100g.

8. (C) Component is the following average composition formula (9) 【Chemistry 2】 (In the formula, R 13 These are, independently of each other, unsubstituted or substituted monovalent hydrocarbon groups having 2 to 12 carbon atoms and lacking aliphatic unsaturated bonds, or hydrogen atoms; component (C) has hydrogen atoms bonded to at least two silicon atoms; e1 is 2 or more, f1 is 2 or more, g1 is 0 or more, and h1 is an integer of 0 or more; e1 + f1 + g1 + h1 is selected such that the viscosity at 25°C falls between 2 and 200 mPa·s. A curable organopolysiloxane composition according to claim 5, represented by [the specified formula].

9. Furthermore, the curable organopolysiloxane composition according to claim 5, comprising (E) an organopolysiloxane having 0.1 to 20 (meth)acrylic group-containing groups bonded to silicon atoms in one molecule: (B) 0.01 to 20 parts by mass per 100 parts by mass of component.

10. Furthermore, the curable organopolysiloxane composition according to claim 5, comprising an organopolysiloxane having at least two alkenyl groups bonded to silicon in one molecule, with a content of 0.2 to 0.8 mol / 100g of alkenyl groups bonded to silicon and a viscosity of 1 to 50 mPa·s: an amount such that the ratio of the number of SiH groups in component (A) to the number of alkenyl groups in component (F) is 0.5 to 10.

11. A release sheet comprising a base material and a release agent layer provided on at least one surface of the base material, wherein the release agent layer is formed from a cured product of the curable organopolysiloxane composition described in claim 5.

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