Curable organopolysiloxane composition and release sheet

Abstract

A curable organopolysiloxane composition comprising the following components (A) to (D): (A) an organopolysiloxane having at least two alkenyl groups bonded to silicon in one molecule; (B) an organohydrogen polysiloxane having two or more hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule; (C) a composition comprising the following general formula (1) [wherein R...] 1 R 2 Each of the following is an independent monovalent hydrocarbon group consisting of 1 to 12 carbon atoms, either unsubstituted or substituted. 3 Each is represented by the following formula (1-1) or (1-2). ] Polybutadiene compounds, (D) platinum group metal catalysts: catalytic amount.

Description

Technical Field

[0001] This invention relates to curable organopolysiloxane compositions capable of forming a peelable cured film, specifically organopolysiloxane compositions characterized by excellent adhesion to a wide range of substrates, particularly paper substrates such as supercalendered kraft paper and clay-coated kraft paper, and suppressing changes in the peel force of the cured product due to the addition of adhesion enhancers. In particular, it relates to organopolysiloxane compositions exhibiting excellent adhesion to various substrates even with reduced platinum group metal catalysts, and to release sheets having cured films of such compositions. Background Technology

[0002] To date, in order to prevent adhesion to substrates such as paper and plastic films, as well as pressure-sensitive adhesives, a cured film of an organopolysiloxane composition is formed on the substrate surface to impart peel-off properties. As a method for forming a cured organopolysiloxane film on the aforementioned substrate surface, the addition reaction-based peel-off film formation method is widely used due to its excellent curing properties and the ability to vary the peel-off properties. In this addition reaction, platinum group metals, primarily platinum, are generally used as catalysts.

[0003] The cured film obtained from this addition reaction-cured organopolysiloxane composition must be peeled off from pressure-sensitive adhesive materials such as pressure-sensitive adhesive tapes with a small peeling force. On the other hand, it must adhere tightly to substrates such as paper and plastic films. Cured films with poor adhesion sometimes detach from the substrate several days after film formation or during storage under high temperature and humidity conditions (the cured film peels off like rubber residue).

[0004] It is believed that the adhesion between the cured film and the substrate is caused by SiH in the organopolysiloxane composition. The reasoning is that compositions with low SiH content often exhibit poor adhesion, and in such cases, increasing the SiH content improves the adhesion. However, it is known that increasing the SiH content increases the peel strength due to the interaction between SiH and the pressure-sensitive adhesive, resulting in high adhesion to the substrate, and in most cases, makes easy peeling more difficult.

[0005] Another method to improve the adhesion of organopolysiloxane compositions to substrates is to perform easy-adhesion treatment or primer treatment on the surface of the substrate. However, surface treatment of the substrate has the disadvantage of increasing the number of steps and is not preferred.

[0006] Therefore, compared to previous methods, a method for improving adhesion to a substrate was investigated by adding an adhesion enhancer to the organopolysiloxane composition. Patent documents 1 and 2 describe how, in addition-curing organopolysiloxane compositions comprising an alkenyl-containing organopolysiloxane and an organohydrosiloxane, adding a specific aryl-containing organohydrosiloxane as an adhesion enhancer improves the adhesion of solvent-free organopolysiloxane compositions to a film substrate. However, the specific aryl-containing organohydrosiloxane is a SiH-containing compound, thus exhibiting a problem of increased peel strength.

[0007] Patent document 3 describes a release composition comprising a curable alkenyl organosilicon with a branched structure and an adhesion enhancer for a release coating containing oxysilane or epoxy and SiH. This composition exhibits excellent adhesion to paper and polymer substrates, particularly PET films. However, the adhesion enhancer is also a compound containing SiH, thus increasing the peel strength upon its addition.

[0008] As an adhesion enhancer without SiH, Patent Document 4 describes the addition of an organopolysiloxane having epoxy groups and substantially lacking SiH to an organosilicon composition for peelable curing film formation. In the embodiments of Patent Document 4, improvements in adhesion relative to PET and PP films are described, but peel strength is not mentioned.

[0009] Patent document 5 describes a method for improving the adhesion of a cured film to a substrate by adding a reaction product of a liquid polyorganosiloxane having alkenyl and silanol groups and a hydrolyzable silane having epoxy groups as an adhesion enhancer to a solvent-free organosilicon composition. Specifically, it describes a method based on a film containing one or more Q units (SiO2). 4 / 2 ), D unit (R2SiO) 2 / 2 ) and multiple M units (R'R 2 SiO 1 / 2 A stripping coating composition of multiple branches of siloxanes, when combined with an adhesion enhancer described in Patent Document 5, exhibits good adhesion. Here, R and R' are selected from alkyl and alkenyl groups having 1 to 6 carbon atoms, with at least 3 R' being alkenyl groups. In the examples, it is described that a coating composition containing Q units (SiO2) is used. 4 / 2 Compositions consisting of specific organopolysiloxanes of the alkenyl group and adhesion enhancers, but no mention is made of peel strength.

[0010] On the other hand, Patent Document 6 discovered that by adding an organopolysiloxane compound containing (meth)acryloyl groups to an addition-reaction type organopolysiloxane composition, an addition reaction under a low platinum group metal catalyst can be carried out, forming a cured film with peel strength comparable to that of the past. Furthermore, Patent Document 7, 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)acryloyl groups as the base polymer of the addition-reaction type organopolysiloxane composition, the amount of platinum group metal catalyst used is similarly reduced. However, although peel strength is described in the examples of Patent Documents 6 and 7, adhesion is not mentioned in Patent Document 6, and adhesion to cellophane is not mentioned in Patent Document 7.

[0011] In recent years, in Europe and America, the mainstream paper substrates have been supercalendered kraft paper and clay-coated kraft paper. However, the aforementioned patent documents 1 to 7 do not mention the adhesion to these substrates, and there is a particular desire to develop curable organopolysiloxane compositions that can form a cured film with high adhesion to supercalendered kraft paper and clay-coated kraft paper.

[0012] Existing technical documents

[0013] Patent documents

[0014] Patent Document 1: Japanese Patent Application Publication No. 2018-012827

[0015] Patent Document 2: Japanese Patent Application Publication No. 2018-119056

[0016] Patent Document 3: Japanese Patent Publication No. 2006-519893

[0017] Patent Document 4: Japanese Patent Application Publication No. 2011-132532

[0018] Patent Document 5: Japanese Patent Publication No. 2010-500462

[0019] Patent Document 6: International Publication No. 2020 / 145151

[0020] Patent Document 7: International Publication No. 2021 / 251255 Summary of the Invention

[0021] The problem that the invention aims to solve

[0022] The inventors applied the release compositions containing adhesion enhancers described in Patent Documents 1 and 2 to various substrates and found that the adhesion to supercalendered kraft paper and clay-coated kraft paper was insufficient. Furthermore, since the adhesion enhancer is a compound containing SiH, the peel force increased. The adhesion enhancer described in Patent Document 3 improved the adhesion to supercalendered kraft paper and clay-coated kraft paper to some extent, but the peel force still increased. Furthermore, the adhesion enhancers described in Patent Documents 4 and 5, since they are not compounds containing SiH, showed little change in peel force, but no improvement in adhesion could be confirmed.

[0023] Furthermore, when the curable organopolysiloxane compositions described in Patent Documents 6 and 7 were coated on various substrates, it was found that a cured film could be obtained with a small amount of platinum group metal catalyst, but the adhesion was insufficient. Moreover, sometimes the adhesion was reduced compared to the amount of platinum group metal catalyst used, and higher adhesion was required when the amount of platinum group metal catalyst was less.

[0024] The present invention was made in view of the above-mentioned actual situation, and its object is to provide a curable organopolysiloxane composition that exhibits excellent adhesion to a wide range of substrates, particularly paper substrates such as supercalendered kraft paper and clay-coated kraft paper, and suppresses changes in the peel force of the cured product due to the addition of adhesion-enhancing agents, as well as a release sheet having the cured film of the composition. Furthermore, the present invention aims to provide a curable organopolysiloxane composition that yields a cured product with excellent adhesion to various substrates even with reduced platinum group metal catalysts.

[0025] Methods for solving problems

[0026] In order to achieve the above objectives, the inventors conducted in-depth research and found that by adding a polybutadiene compound represented by the general formula (1) described below to a curable organopolysiloxane composition, the change in peel force of the cured product caused by the addition of the adhesion enhancer was suppressed, and a cured film with excellent adhesion to a wide range of substrates, especially paper substrates such as supercalendered kraft paper and clay-coated kraft paper, was obtained, thus completing the present invention.

[0027] Therefore, the present invention provides the following curable organopolysiloxane composition and release sheet.

[0028] 1. A curable organopolysiloxane composition comprising the following components (A) to (D),

[0029] (A) An organopolysiloxane having at least two alkenyl groups bonded to silicon in one molecule: 100 parts by mass,

[0030] (B) Organohydrogen polysiloxanes having two or more hydrogen atoms bonded to silicon atoms (SiH groups) in one molecule: in an amount such that the ratio of the number of SiH groups in component (B) to the number of alken groups in component (A) is 0.5 to 10.

[0031] (C) A polybutadiene compound represented by the following general formula (1): 0.01 to 10 parts by mass relative to 100 parts by mass of component (A),

[0032] [Chemistry 1]

[0033]

[0034] [In the formula, R] 1 R 2 Each is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, R 3 Each is a group represented by formula (1-1) or (1-2) below.

[0035] [Chemistry 2]

[0036]

[0037] (where R) 5 Each group is an unsubstituted or substituted monovalent hydrocarbon group with 1 to 12 carbon atoms, where n represents a positive number from 1 to 100. An asterisk (*) indicates a bond with the -CH- group of the main chain.

[0038] R 4 Each is independently a hydrogen atom or a group represented by -CH2CH2OH.

[0039] a is a positive number that satisfies 0 < a ≤ 120.

[0040] b is 0 or a positive number satisfying 0 < b ≤ 100.

[0041] c is 0 or a positive number satisfying 0 < c ≤ 100.

[0042] d is 0 or a positive number satisfying 0 < d ≤ 20.

[0043] The condition is satisfied that 0 < b + c ≤ 200, where m is an integer from 1 to 3. The order of the repeating units is arbitrary.

[0044] (D) Platinum group metal catalysts: catalytic amount.

[0045] 2. The curable organopolysiloxane composition according to 1, wherein the number average molecular weight of the polybutadiene compound of component (C) is 1,000 to 1,000,000.

[0046] 3. The curable organopolysiloxane composition according to 1 or 2, wherein the polybutadiene compound of component (C) in general formula (1) a, b, c, d each independently satisfies the conditions of formulas (i), (ii), and (iii) below:

[0047]

[0048] 4. The curable organopolysiloxane composition according to any one of 1 to 3, wherein component (A) is an organopolysiloxane represented by the following formula (2),

[0049]

[0050] (where R) 6 Independently selected from alkenyl, hydroxyl, and unsubstituted or substituted monovalent hydrocarbon groups without aliphatic unsaturated bonds, R 6 At least two of the radicals are alkenyl groups, e is 2 or more, f is 0 or 0 < f, g is 0 or 0 < g, and h is a positive number that is 0 or 0 < h. The formula e + f + g + h is chosen so that the viscosity at 25°C is 1 mPa. A viscosity of 70,000 mPa is obtained when the concentration of the substance is greater than s and dissolved in toluene at 30% by mass. (Below s)

[0051] 5. The curable organopolysiloxane composition according to any one of 1 to 3, wherein component (A) is an organopolysiloxane represented by the following formula (3).

[0052]

[0053] (where R) 7 Independently selected from alkenyl, hydroxyl, unsubstituted or substituted monovalent hydrocarbon groups without aliphatic unsaturated bonds, and groups containing (meth)acryloyl groups, R 7 At least two of them are alkenyl groups, R 7 The number of groups in the middle ranges from 0.01 to 2.9, each containing a (meth)acryloyl group. v is 2 or more, w is 8 or more, x is 0 or 0 < x, and y is 0 or < y (positive numbers). The formula v + w + x + y is chosen to achieve a viscosity of 1 mPa at 25°C. A viscosity of 70,000 mPa is present when the concentration of s is greater than 30% by mass and the concentration in toluene is 30,000 mPa. Below s.

[0054] 6. The curable organopolysiloxane composition according to any one of 1 to 5, wherein component (B) is represented by the following average compositional formula (4).

[0055]

[0056] (where R) 8 Each component consists of 1 to 12 unsubstituted or substituted monovalent hydrocarbon groups without aliphatic unsaturated bonds, where t and u are positive numbers satisfying 0.7 ≤ t ≤ 2.1, 0.001 ≤ u ≤ 1.0, and 0.8 ≤ t + u ≤ 3.0, and component (B) has at least two hydrogen atoms bonded to silicon atoms.

[0057] 7. The curable organopolysiloxane composition according to any one of 1 to 6, wherein, relative to 100 parts by mass of component (A), it further comprises 0.01 to 20 parts by mass of (E) an organopolysiloxane represented by the following formula (5) having 0.1 to 20 groups containing (meth)acryloyl groups bonded to silicon atoms in one molecule.

[0058]

[0059] (where R) 9 Independently selected from alkenyl, hydroxyl, unsubstituted or substituted monovalent hydrocarbon groups without aliphatic unsaturated bonds, and groups containing (meth)acryloyl groups, R 9 Of these, 0.1 to 20 are groups containing (meth)acryloyl groups, where p to s are each positive numbers satisfying 2 ≤ p ≤ 202, 5 ≤ q ≤ 1000, r is 0 or 0 < r ≤ 100, and s is 0 or 0 < s ≤ 100, and 0 ≤ r + s ≤ 100.

[0060] 8. A release sheet having a substrate and a release agent layer disposed on at least one side of the substrate, the release agent layer being formed from a cured product formed by curing a curable organopolysiloxane composition according to any one of 1 to 7.

[0061] The effects of the invention

[0062] The curable organopolysiloxane composition of the present invention suppresses the change in peel force of the cured product caused by the addition of an adhesion enhancer, while obtaining a cured film with excellent adhesion to a wide range of substrates, especially paper substrates such as supercalendered kraft paper and clay-coated kraft paper, which is particularly useful as a release sheet for pressure-sensitive adhesive materials. Detailed Implementation

[0063] The present invention will now be described in more detail.

[0064] [(A)Component]

[0065] (A) is an organopolysiloxane having at least two alkenyl groups bonded to silicon in one molecule, and can be used alone or in combination of two or more. (A) has at least two alkenyl groups bonded to silicon in one molecule. If there are fewer than two alkenyl groups, there is a high probability of uncrosslinked molecules remaining after curing, resulting in reduced curability. More specifically, from the perspective of curability, the content of alkenyl groups bonded to silicon is preferably 0.001 mol / 100g or more; from the perspective of preventing excessive increase in peel force and potential difficulty in peeling pressure-sensitive adhesives, it is preferably 0.7 mol / 100g or less, more preferably 0.0015 to 0.6 mol / 100g, and even more preferably 0.002 to 0.5 mol / 100g.

[0066] (A) The viscosity of component A at 25°C is preferably 1 mPa. A viscosity of 70,000 mPa is present when the concentration of s is greater than 30% by mass and the concentration in toluene is 30,000 mPa. Below s, preferably 4 mPa A viscosity of 60,000 mPa is greater than s and soluble in 30% toluene. Below s, 7mPa is further preferred. A viscosity of 50,000 mPa and a solubility of 30% in toluene. Below the lower limit. If the viscosity of component (A) is lower than the aforementioned lower limit, the composition is excessively prone to wetting and spreading, potentially resulting in insufficient coating on the substrate surface. On the other hand, if it is higher than the aforementioned upper limit, wetting and spreading will be difficult, potentially reducing workability. Furthermore, in this invention, all viscosities are values ​​measured using a rotational viscometer at 25°C, and the rotor is appropriately selected within the range of No. 1 to 4, with a rotation speed of 3 to 60 rpm, depending on the viscosity. Furthermore, "viscosity dissolved in toluene at 30% by mass" refers to the viscosity of the solution when 30% by mass of the organopolysiloxane is dissolved in toluene.

[0067] As a component (A), for example, organopolysiloxanes represented by the following formula (2) can be listed.

[0068]

[0069] (where R) 6 Independently selected from alkenyl, hydroxyl, and unsubstituted or substituted monovalent hydrocarbon groups without aliphatic unsaturated bonds, R 6 In the formula, at least two are alkenyl groups, e is 2 or more, f is 0 or 0 < f (f is 0 or more), g is 0 or 0 < g (g is 0 or more), and h is 0 or 0 < h (h is 0 or more). The formula is chosen such that e + f + g + h equals 1 mPa. A viscosity of 70,000 mPa is obtained when the concentration of the substance is greater than s and dissolved in toluene at 30% by mass. (Below s)

[0070] In formula (2) above, examples of alkenyl groups with 2 to 12 carbon atoms include vinyl, allyl, butenyl, propenyl, 5-hexenyl, octenyl, and decenyl. From an industrial point of view, vinyl is preferred. As a monovalent hydrocarbon group that is unsubstituted or substituted and does not have aliphatic unsaturated bonds, a monovalent hydrocarbon group with 1 to 12 carbon atoms is preferred, and a monovalent hydrocarbon group with 1 to 10 carbon atoms is more preferred. Examples of monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, and octyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; and aralkyl groups such as benzyl and phenethyl. In addition, haloalkyl groups formed by substituting some or all of their hydrogen atoms with halogen atoms, such as chloropropyl and trifluoropropyl, are also examples. From the perspective of high curability and low peel strength, all R groups are preferred. 6 More than 80 mol% of it is methyl.

[0071] Given that e is 2 or higher, f is 0 or 0 < f, g is 0 or 0 < g, and h is 0 or 0 < h, choose e + f + g + h to make the viscosity at 25℃ 1 mPa. A viscosity of 70,000 mPa is obtained when the concentration of the substance is greater than s and dissolved in toluene at 30% by mass. s and below. e is a positive number from 2 to 300, f is a positive number from 60 to 20000, g is more preferably a positive number of 0 or 0 < g ≤ 100, and h is more preferably a positive number of 0 or 0 < h ≤ 100. More preferably 10 ≤ e + f + g + h ≤ 20000, and more preferably 60 ≤ e + f + g + h ≤ 15000.

[0072] As an organopolysiloxane represented by formula (2), for example, compounds represented by the following formula can be listed.

[0073] (R) 6 3SiO 1 / 2 )2(R 6 2SiO 2 / 2 ) f

[0074] (R) 6 3SiO 1 / 2 ) e (R) 6 2SiO 2 / 2 ) f (R) 6 SiO 3 / 2 ) g

[0075] (R) 6 3SiO 1 / 2 ) e (R) 6 2SiO 2 / 2 )f (SiO) 4 / 2 ) h

[0076] (R) 6 3SiO 1 / 2 ) e (R) 6 2SiO 2 / 2 ) f (R) 6 SiO 3 / 2 )g(SiO 4 / 2 ) h

[0077] In the above formulas, R 6 As described above, e to h.

[0078] As more detailed examples, compounds represented by the following formulas can be listed, but are not limited to these. Furthermore, the bonding order of the siloxane units indicated in parentheses is not limited to the following.

[0079] (ViMe2SiO) 1 / 2 )2(Me2SiO 2 / 2 ) α1

[0080] (1≤α1≤19998)

[0081] (Vi3SiO) 1 / 2 )2(Me2SiO 2 / 2 ) α2

[0082] (1≤α2≤19998)

[0083] (ViMe2SiO) 1 / 2 )2(Me2SiO 2 / 2 ) α3 (ViMeSiO) 2 / 2 ) α4

[0084] (0≤α3≤19997, 1≤α4≤2000, 1≤α3+α4≤19998)

[0085] (ViMe2SiO) 1 / 2 )2(Me2SiO 2 / 2 ) α5 (Ph2SiO) 2 / 2 ) α6

[0086] (0≤α5≤19997, 1≤α6≤2000, 1≤α5+α6≤19998)

[0087] (ViMe2SiO) 1 / 2 )2(Me2SiO 2 / 2 ) α7 (ViMeSiO) 2 / 2 ) α8 (Ph2SiO) 2 / 2 ) α9

[0088] (0≤α7≤19996, 1≤α8≤2000, 1≤α9≤2000, 2≤α7+α8+α9≤19998)

[0089] (ViMe2SiO) 1 / 2 ) α10 (Me2SiO) 2 / 2 ) α11 (MeSiO) 3 / 2 ) α12

[0090] (3≤α10≤102, 0≤α11≤19996, 1≤α12≤100, 4≤α10+α11+α12≤20000)

[0091] (ViMe2SiO) 1 / 2 ) α13 (Me2SiO) 2 / 2 ) α14 (MeSiO) 3 / 2 ) α15 (SiO) 4 / 2 ) α16

[0092] (4≤α13≤302, 0≤α14≤19995, 0≤α15≤100, 1≤α16≤100, 5≤α13+α14+α15+α16≤20000)

[0093] In the above formulas, Me, Vi, and Ph refer to methyl, vinyl, and phenyl, respectively.

[0094] In this invention, by mixing component (E) as described later, or by making component (A) an organopolysiloxane represented by formula (3) as described later, it is possible to reduce the use of platinum group metal catalysts (hereinafter sometimes referred to as low platinum). Component (E) and organopolysiloxane represented by formula (3) are components that have the effect of improving the reactivity of addition reactions in this invention. The reason for improving reactivity is not yet determined, but it is speculated that the above-mentioned effect is manifested by the coordination of groups containing (meth)acryloyl groups in any form to platinum group metal atoms.

[0095]

[0096] (where R)7 Independently selected from alkenyl, hydroxyl, unsubstituted or substituted monovalent hydrocarbon groups without aliphatic unsaturated bonds, and groups containing (meth)acryloyl groups, R 7 At least two of them are alkenyl groups, R 7 The number of groups ranging from 0.01 to 2.9 is a positive number containing (meth)acryloyl groups, where v is 2 or more, w is 8 or more, x is 0 or 0 < x (x is 0 or more), and y is 0 or 0 < y (y is 0 or more). The formula v + w + x + y is chosen to achieve a viscosity of 1 mPa at 25°C. A viscosity of 70,000 mPa is obtained when the concentration of the substance is greater than s and dissolved in toluene at 30% by mass. (Below s)

[0097] In formula (3) above, the same group as the alkenyl group specifically exemplified as the alkenyl group in formula (2) above can be listed as the alkenyl group. From an industrial point of view, vinyl groups are preferred. In formula (3) above, the same group as the same group as the unsubstituted or substituted monovalent hydrocarbon group with 2 to 12 carbon atoms without aliphatic unsaturated bonds specifically exemplified as the unsubstituted or substituted monovalent hydrocarbon group with 2 to 12 carbon atoms without aliphatic unsaturated bonds in formula (2) above can be listed as the alkenyl group. Among these, all R groups are preferred in cases of improving curability and reducing peel strength. 7 More than 80 mol% of it is methyl.

[0098] The organopolysiloxane represented by formula (3) above has 0.01 to 2.9 groups containing (meth)acryloyl groups bonded to silicon in one molecule. That is, R 7 The number of groups containing (meth)acryloyl groups is 0.01 to 2.9. By having 0.01 or more, the reactivity of the addition reaction can be further improved; by having 2.9 or less, a more suitable peeling force can be obtained. More specifically, the content of groups containing (meth)acryloyl groups bonded to silicon is preferably 0.0001 to 0.1 mol / 100g, more preferably 0.0003 to 0.08 mol / 100g, and even more preferably 0.0005 to 0.05 mol / 100g. By having the content of groups containing (meth)acryloyl groups at or above the lower limit of the above range, the reactivity of the addition reaction is further improved; on the other hand, by having it at or below the upper limit of the above range, a more suitable peeling force can be obtained.

[0099] Examples of groups containing a (meth)acryloyl group include CH2=CR. 10 COR 11 -

[0100] (where R) 10 R is a hydrogen atom or a methyl group.11 OR 12 (R) 12 (A divalent organic group having 1 to 20 carbon atoms) or composed of R 12 (This indicates a divalent group.)

[0101] R 10 It can be a hydrogen atom or a methyl group, preferably a hydrogen atom. R 11 OR 12 (R) 12 (A divalent organic group having 1 to 20 carbon atoms) or composed of R 12 The divalent group represented is preferably OR. 12 R 12 It is a divalent organic group with 1 to 20 carbon atoms, and can have branched or cyclic structures, and may contain epoxy groups, ester bonds, urethane bonds, ether bonds, isocyanate bonds, and hydroxyl groups. As R 12 Examples of divalent hydrocarbon groups include methylene, ethylene, propylene, butylene, hexamethylene, octamethylene, and decylene; linear alkylene groups; branched alkylene groups such as methyl ethylene and methyl propyleneene; cyclic alkylene groups such as cycloalkylene; alkenyl groups such as propenylene; aryl groups such as phenylene; and arylalkyl groups such as methylene phenylene and methylene phenylenemethylene. Ester bonds, carbamate bonds, ether bonds, and isocyanate bonds can be involved in these divalent hydrocarbon groups, and they can also be used in combination. Furthermore, some or all of the hydrogen atoms in these divalent hydrocarbon groups can be replaced by epoxy groups or hydroxyl groups. Among these, R... 12 Propylene group is preferred. From the viewpoint of improving reactivity, groups represented by CH2=CHCOOC3H6- are preferred.

[0102] Given v = 2 or higher, w = 8 or higher, x = 0 or 0 < x, and y = 0 or 0 < y, choose v + w + x + y to make the viscosity at 25℃ 1 mPa. A viscosity of 70,000 mPa is obtained when the concentration of the substance is greater than s and dissolved in toluene at 30% by mass. s is less than or equal to 0. v is preferably a positive number from 2 to 300, w is preferably a positive number from 60 to 20000, x is preferably a positive number of 0 or 0 < x ≤ 100, y is preferably a positive number of 0 or 0 < y ≤ 100, preferably 10 ≤ v + w + x + y ≤ 20000, and more preferably 60 ≤ v + w + x + y ≤ 15000.

[0103] As an organopolysiloxane represented by the above formula (3), for example, compounds represented by the following formula can be listed.

[0104] (R) 7 3SiO 1 / 2 )2(R 7 2SiO 2 / 2 ) w

[0105] (R) 7 3SiO 1 / 2 ) v (R) 7 2SiO 2 / 2 ) w (R) 7 SiO 3 / 2 ) x

[0106] (R) 7 3SiO 1 / 2 ) v (R) 7 2SiO 2 / 2 ) w (SiO) 4 / 2 ) y

[0107] (R) 7 3SiO 1 / 2 ) v (R) 7 2SiO 2 / 2 ) w (R) 7 SiO 3 / 2 ) x (SiO) 4 / 2 ) y

[0108] In the above formulas, R 7 As described above, v~y.

[0109] As more detailed examples, compounds represented by the following formulas can be listed, but are not limited to these. Furthermore, the bonding order of the siloxane units indicated in parentheses is not limited to the following.

[0110] (ViMe2SiO) 1 / 2 )2(Me2SiO 2 / 2 ) γ1 (AMeSiO) γ2

[0111] (5.1≤γ1<20000、0.01≤γ2≤2.9、8≤γ1+γ2≤19998)

[0112] (Vi3SiO) 1 / 2 )2(Me2SiO 2 / 2 ) γ3 (AMeSiO) 2 / 2 ) γ4

[0113] (5.1≤γ3<20000, 0.01≤γ4≤2.9, 8≤γ3+γ4≤19998)

[0114] (YouMe2SiO) 1 / 2 )2(Me2SiO 2 / 2 ) γ5 (ViMeSiO) 2 / 2 ) γ6 (Love) 2 / 2 ) γ7

[0115] (0≤γ5<19997、1≤γ6≤2000、0.01≤γ7≤2.9、8≤γ5+γ6+γ7≤19998)

[0116] (YouMe2SiO) 1 / 2 )2(Me2SiO 2 / 2 ) γ8 (Ph2SiO 2 / 2 ) γ9 (Love) 2 / 2 ) γ1 0

[0117] (0≤γ8<19997、1≤γ9≤2000、0.01≤γ10≤2.9、8≤γ8+γ9+γ10≤19998)

[0118] (YouMe2SiO) 1 / 2 )2(Me2SiO 2 / 2 ) γ11 (ViMeSiO) 2 / 2 ) γ12 (Ph2SiO 2 / 2 ) γ13 (Love) 2 / 2 ) γ14

[0119] (0≤γ11<19996、1≤γ12≤2000、1≤γ13≤2000、8≤γ11+γ12+γ13+γ14≤19998)

[0120] (YouMe2SiO) 1 / 2 ) γ15 (Me2SiO 2 / 2 ) γ16 (Love) 2 / 2 ) γ17 (MeSiO) 3 / 2 ) γ18

[0121] (3≤γ15≤102, 5.1≤γ16<19996, 0.01≤γ17≤2.9, 8≤γ16+γ17≤19996, 1≤γ18≤100, 12≤γ15+γ16+γ17+γ18≤20000)

[0122] (ViMe2SiO) 1 / 2 ) γ19 (Me2SiO) 2 / 2 ) γ20 (AMeSiO) 2 / 2 ) γ21 (MeSiO) 3 / 2 ) γ22 (SiO) 4 / 2 ) γ23

[0123] (4≤γ19≤302, 5.1≤γ20<19995, 0.01≤γ21≤2.9, 8≤γ20+γ21≤19995, 0≤γ22≤100, 1≤γ23≤100, 13≤γ19+γ20+γ21+γ22+γ23≤20000)

[0124] In the above formulas, Me, Vi, Ph, and A each refer to groups represented by methyl, vinyl, phenyl, and CH2=CHCOOC3H6-, respectively.

[0125] In this invention, as component (A), the organopolysiloxane represented by formula (2) and the organopolysiloxane represented by formula (3) can be used individually or in combination. Furthermore, the number of alkenyl groups and the viscosity are as described above.

[0126] [(B) Component]

[0127] (B) is an organohydrogen polysiloxane having two or more hydrogen atoms bonded to silicon atoms (SiH groups) in one molecule, and can be used alone or in combination of two or more. The SiH groups above react with the alkenyl groups of the above-mentioned component (A) to form a cured film.

[0128] (B) The component has at least two SiH groups per molecule. If there are fewer than two, there is a high probability that uncrosslinked molecules will remain after curing, resulting in reduced curability. More specifically, from the perspective of curability, the SiH group content is preferably 0.5 mol / 100g or more, and from the perspective of avoiding excessive increase in peel strength, it is preferably 2.0 mol / 100g or less. More preferably, it is 0.6 to 1.8 mol / 100g, and even more preferably, it is 0.8 to 1.6 mol / 100g.

[0129] (B) The viscosity of component B at 25°C is preferably 2–200 mPa. s, more preferably 5–180 mPa s, further preferred 10-150 mPa s. By making the viscosity of component (B) above the lower limit value mentioned above, the adhesion to the substrate is further improved, and by making it below the upper limit value mentioned above, the reactivity is further improved.

[0130] As component (B), examples of organohydrogen polysiloxanes represented by the following average composition formula (4) can be listed.

[0131] R 8 t H u SiO (4-t-u) / 2 (4)

[0132] (where R) 8 Each component is an independent monovalent hydrocarbon group with 1 to 12 unsubstituted or substituted carbon atoms, without aliphatic unsaturated bonds, and t and u are positive numbers satisfying 0.7 ≤ t ≤ 2.1, 0.001 ≤ u ≤ 1.0, and 0.8 ≤ t + u ≤ 3.0. However, component (B) has at least two hydrogen atoms bonded to silicon atoms.

[0133] In equation (4) above, R 8 Independently, these are monovalent hydrocarbon groups with 1 to 12, preferably 1 to 10, unsubstituted or substituted carbon atoms, without aliphatic unsaturated bonds. Examples include alkyl groups such as methyl, ethyl, propyl, butyl, and octyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups such as benzyl and phenethyl; or monovalent hydrocarbon groups in which some or all of the hydrogen atoms bonded to the carbon atoms are substituted with hydroxyl, halogen, alkoxysilyl, polyoxyalkylene, epoxy, carboxyl, etc. As R 8 Alkyl groups are preferred, and methyl groups are more preferred. From the perspectives of high curability and low peel strength, all R groups are preferred. 8 More than 50 mol% of the total, typically 60–100 mol%, is methyl. The proportion of methyl is higher than that of all R. 8 In cases where the content is less than 50 mol%, it may have poor compatibility with component (A), and the curable organopolysiloxane composition may become cloudy or separate into phases.

[0134] t and u are positive numbers satisfying 0.7≤t≤2.1, preferably 0.8≤t≤2.1, and more preferably 1.0≤t≤2.0. u is a positive number satisfying 0.001≤u≤1.0, more preferably 0.005≤u≤1.0, and even more preferably 0.01≤u≤0.98. t+u is a positive number satisfying 0.8≤t+u≤3.0, preferably 1.0≤t+u≤2.8, and more preferably 1.3≤t+u≤2.5. However, component (B) has at least two hydrogen atoms bonded to silicon atoms.

[0135] As for (B) organohydrogen polysiloxanes, examples include siloxanes with silyl groups at both ends, siloxanes with silyl groups in the side chain, siloxanes with silyl groups at both ends and in the side chain, and siloxanes with silyl groups at both ends and in the side chain. More specifically, the following organohydrogen polysiloxanes can be exemplified, but are not limited to these. Furthermore, the bonding order of the siloxane units shown in parentheses is not limited to the following.

[0136] (Me2SiO) 1 / 2 )2 (MeHSiO) δ1

[0137] (2≤δ1≤200)

[0138] (Me2SiO) 1 / 2 )2 (MeHSiO 2 / 2 ) δ2 (Me2SiO) 2 / 2 ) δ3

[0139] (2≤δ2≤199, 1≤δ3≤198, 3≤δ2+δ3≤200)

[0140] (Me2SiO) 1 / 2 ) δ4 (MeHSiO) 2 / 2 ) δ5 (Me2SiO) 2 / 2 ) δ6 (MeSiO) 3 / 2 ) δ7

[0141] (3≤δ4≤52, 2≤δ5≤200, 0≤δ6≤198, 2≤δ5+δ6≤200, 1≤δ7≤50)

[0142] (Me2SiO) 1 / 2 ) δ8 (MeHSiO) 2 / 2 ) δ9 (Me2SiO) 2 / 2 ) δ10 (MeSiO) 3 / 2 ) δ11 (SiO) 4 / 2 ) δ12

[0143] (4≤δ8≤102, 2≤δ9≤200, 0≤δ10≤198, 2≤δ9+δ10≤200, 0≤δ11≤50, 1≤δ12≤50, 1≤δ11+δ12≤50)

[0144] In the above formulas, Me and H refer to methyl and hydrogen atoms, respectively.

[0145] The amount of component (B) is such that the ratio of the number of SiH groups in component (B) to the number of alkenyl groups in component (A) is 0.5 to 10, preferably 0.8 to 8.0, and more preferably 1.0 to 5.0. If the amount of component (B) is less than the lower limit mentioned above, the curing property becomes insufficient. In addition, if it exceeds the upper limit mentioned above, the amount of residual SiH groups increases, thus causing the problem of excessively increased peel strength.

[0146] [(C) Component]

[0147] The polybutadiene compound of component (C) is a characteristic compound of this invention. By adding component (C) as an adhesion enhancer to a curable organopolysiloxane composition, adhesion to a wide range of substrates, particularly paper substrates such as supercalendered kraft paper and clay-coated kraft paper, can be improved. Furthermore, since it is a compound that does not contain SiH groups, it exhibits a small change in peel strength due to its addition. Component (C) is a polybutadiene compound represented by the following general formula (1), and can be used alone or in combination of two or more.

[0148] [Chemistry 3]

[0149]

[0150] [In the formula, R] 1 R 2 Each is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, R 3 Each is a group represented by formula (1-1) or (1-2) below.

[0151] [Chemistry 4]

[0152]

[0153] (where R) 5 Each group is an unsubstituted or substituted monovalent hydrocarbon group with 1 to 12 carbon atoms, where n represents a positive number from 1 to 100. An asterisk (*) indicates a bond with the -CH- group of the main chain.

[0154] R 4 Each repeating unit is independently a hydrogen atom or a group represented by -CH2CH2OH, where 'a' is a positive number satisfying 0 < a ≤ 120, 'b' is 0 or a positive number satisfying 0 < b ≤ 100, 'c' is 0 or a positive number satisfying 0 < c ≤ 100, 'd' is 0 or a positive number satisfying 0 < d ≤ 20, '0 < b + c ≤ 200', and 'm' is an integer from 1 to 3. However, the order of the repeating units is arbitrary.

[0155] The polybutadiene compound indicated can be used alone or in combination of two or more.

[0156] R 1 R 2 Each group is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms. Examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, and dodecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, and hexenyl; aryl groups such as phenyl, tolyl, xylyl, and α-, β-naphthyl; and aralkyl groups such as benzyl, 2-phenylethyl, and 3-phenylpropyl. Additionally, groups formed by substituting some or all of the hydrogen atoms of these groups with halogen atoms such as F, Cl, Br, or cyano groups, such as 3-chloropropyl, 3,3,3-trifluoropropyl, and 2-cyanoethyl, are also included. Among these, alkyl groups having 1 to 10 carbon atoms or aryl groups having 6 to 10 carbon atoms are preferred, alkyl groups such as methyl and ethyl are more preferred, and methyl is even more preferred.

[0157] R 3 Each is a group represented by the following formula (1-1) or (1-2).

[0158] [Chemistry 5]

[0159]

[0160] (where R) 5 Each group is an unsubstituted or substituted monovalent hydrocarbon group with 1 to 12 carbon atoms, where n represents a positive number from 1 to 100. An asterisk (*) indicates a bond with the -CH- group of the main chain.

[0161] By having groups represented by formula (1-1), the adhesion to the substrate can be further improved, and by having groups represented by formula (1-2), the compatibility with components (A) and (B) can be further improved.

[0162] R 5 Each is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and can be exemplified with R. 1 R 2 The same group is preferred, specifically methyl. n is a positive number from 1 to 100, and from the viewpoint of compatibility with components (A) and (B), a positive number from 4 to 100 is preferred, and a positive number from 8 to 100 is more preferred. R 4 Each is independently a hydrogen atom or a group represented by -CH2CH2OH, preferably a hydrogen atom.

[0163] (C) The number-average molecular weight of component (C) is preferably 1,000 to 1,000,000, more preferably 1,500 to 100,000, and even more preferably 2,000 to 10,000. By having a number-average molecular weight of 1,000 or more, the adhesion to the substrate is further improved. On the other hand, when it exceeds 1,000,000, the viscosity increases excessively, and workability may decrease. Furthermore, the number-average molecular weight (or degree of polymerization) can be determined by using toluene as an eluent, or by converting the number-average molecular weight (or degree of polymerization) of polystyrene in gel permeation chromatography (GPC) analysis, etc. (hereinafter the same).

[0164] a is a positive number that satisfies 0 < a ≤ 120, preferably a positive number from 1 to 80, more preferably a positive number from 1 to 60, and even more preferably a positive number from 1 to 40.

[0165] b is 0 or a positive number satisfying 0 < b ≤ 100 (0 ≤ b ≤ 100), preferably a positive number of 0 or 0 < b ≤ 70, more preferably a positive number of 0 or 0 < b ≤ 40, and even more preferably a positive number of 1 to 20.

[0166] c is 0 or a positive number satisfying 0 < c ≤ 100 (0 ≤ c ≤ 100), preferably a positive number from 1 to 70, more preferably a positive number from 2 to 40, and even more preferably a positive number from 3 to 20.

[0167] d is 0 or a positive number satisfying 0 < d ≤ 20 (0 ≤ d ≤ 20), preferably a positive number of 0 or 0 < d ≤ 15, more preferably a positive number of 0 or 0 < d ≤ 10, and even more preferably a positive number of 0 or 0 < d ≤ 5.

[0168] The condition satisfies 0 < b + c ≤ 200, preferably a positive number from 1 to 80, more preferably a positive number from 5 to 50, and even more preferably a positive number from 10 to 20.

[0169] m is an integer from 1 to 3, preferably an integer of 2 or 3.

[0170] (C) The components preferably satisfy the following conditions (i), (ii), and (iii):

[0171] ,

[0172] More preferably, all of the above conditions must be met.

[0173]

[0174] As described in the formula above, (i) represents the proportion of hydrolyzable silane, indicating the number of units containing 5 mol% or more of hydrolyzable silane relative to all units. Preferably, c / (a+b+c+d) is 0.07 or more, more preferably 0.10 or more. By making c / (a+b+c+d) 0.05 or more, the adhesion is further improved regardless of the type of substrate. c / (a+b+c+d) is preferably 0.07 to 0.90, more preferably 0.10 to 0.60, and even more preferably 0.10 to 0.30.

[0175]

[0176] As described in the formula above, this indicates that the sum of units containing hydrolyzable silane and units containing terminal vinyl groups contains 10 mol% or more of units containing hydrolyzable silane. c / (b+c) is preferably 0.15 or more, more preferably 0.20 or more. By making c / (b+c) 0.1 or more, the adhesion is further improved regardless of the type of substrate. c / (b+c) is preferably 0.10 to 1.0, more preferably 0.15 to 0.80, and even more preferably 0.20 to 0.50.

[0177]

[0178] The ratio of (b+c) / (a+b+c+d) is preferably 0.10 to 0.60, and more preferably 0.20 to 0.30.

[0179] The ratio of d / (a+b+c+d) is preferably 0.006 to 0.3, more preferably 0.008 to 0.2, and even more preferably 0.01 to 0.1.

[0180] The amount of component (C) relative to 100 parts by weight of component (A) is 0.01 to 10 parts by weight, preferably 0.03 to 8 parts by weight, more preferably 0.05 to 6 parts by weight, and particularly preferably 0.2 to 4 parts by weight. If the amount of component (C) is less than the above lower limit, the effect on improving the adhesion to the substrate is insufficient. On the other hand, if the amount of component (C) exceeds the above upper limit, the peel force will increase excessively, and the pressure-sensitive adhesive may become difficult to peel off, and the curing performance may decrease.

[0181] (C) Polybutadiene compounds are produced by the following general formula (I)

[0182] [Chemistry 6]

[0183]

[0184] (In the formula, a, b, c, d and R) 3 R 4 Same as above.

[0185] The polybutadiene compound represented by repeating units containing 1,2-vinyl structures (terminal vinyl groups) and the polybutadiene compound of the following general formula (II)

[0186] [Chemistry 7]

[0187]

[0188] (where R) 1 R 2 (And m is the same as above.)

[0189] This indicates the presence of hydrolyzable groups (-OR) in the molecule that are bonded to silicon atoms. 1 Organosilicon compounds, such as organosilicon compounds containing hydrogen atoms bonded to silicon atoms (SiH groups), are obtained by hydrosilylation in the presence of a platinum-containing catalyst and a co-catalyst.

[0190] In the above general formula (I), a, b, c, and d are the same as above. In addition, (b+c) / (a+b+c+d) is also the same as above, preferably 0.05 to 0.95, more preferably 0.10 to 0.60, and even more preferably 0.20 to 0.30.

[0191] The number-average molecular weight of the polybutadiene compound represented by the above general formula (I) is preferably 100 to 10,000, more preferably 500 to 8,000. The polybutadiene compound represented by the above general formula (I) comprises repeating units having a 1,2-vinyl structure and repeating units having a 2,3-vinyl structure (trans-1,4 structure) as isomers. It contains at least 5 mol%, preferably at least 7 mol%, and more preferably at least 10 mol% of repeating units having a 1,2-vinyl structure. By making the 1,2-vinyl structure at 5 mol% or more, the reduction in silane modification rate is suppressed, and regardless of the type of substrate, it can further exert its effect as a bonding improver. Furthermore, there is no particular upper limit to the content ratio of repeating units having a 1,2-vinyl structure; typically, it can be 98 mol% or less, preferably about 95 mol% or less. Moreover, the total amount of repeating units having a 1,2-vinyl structure and repeating units having a 2,3-vinyl structure is 100 mol%.

[0192] As polybutadiene compounds represented by the above general formula (I), NISSO-PB B-1000, NISSO-PB B-2000, NISSO-PB B-3000 (all manufactured by Nippon Soda Co., Ltd.), Ricon130, Ricon131, Ricon134, Ricon142, Ricon150, Ricon152, Ricon153, Ricon154, Ricon156, Ricon157 (all manufactured by CRAYVALLEY Co., Ltd.), LBR-302, LBR-307, LBR-305, LBR-300, LBR-352, and LBR-361 (all manufactured by Kuraray Co., Ltd.) are commercially available. Additionally, copolymers formed by epoxidizing a portion of the 1,2-vinyl structure using Ricon130 (manufactured by CRAY VALLEY Co., Ltd.) and other compounds represented by the following general formula (III) are also available.

[0193] [Chemistry 8]

[0194]

[0195] (where R) 5 (And n is the same as above.)

[0196] The copolymers represented are copolymers formed by the addition reaction of organohydrogen polysiloxanes with a portion of 1,2-vinyl structures.

[0197] Examples of organosilicon compounds represented by the above general formula (II) include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, and other hydroalkoxysilanes. In particular, trimethoxysilane, methyldimethoxysilane, and dimethylmethoxysilane are preferred in terms of high hydrolyticity, and trimethoxysilane is more preferred.

[0198] The reaction ratio of the polybutadiene compound represented by the above general formula (I) and the organosilicon compound represented by the above general formula (II) is preferably 10 to 400 parts by mass of the organosilicon compound represented by general formula (II) relative to 100 parts by mass of the polybutadiene compound represented by general formula (I). In addition, the SiH group in the organosilicon compound represented by general formula (II) is preferably 0.1 to 1.0 mol / mol, more preferably 0.2 to 1.0 mol / mol, relative to the vinyl group in the repeating unit having the 1,2-vinyl structure of the polybutadiene compound represented by general formula (I), so that the reaction can proceed.

[0199] There are no particular limitations on the catalysts containing platinum compounds. Examples include chloroplatinic acid, alcoholic solutions of chloroplatinic acid, toluene or xylene solutions of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complexes, tetra(triphenylphosphine)platinum, dichlorobis(triphenylphosphine)platinum, dichlorobis(acetonitrile)platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, platinum-carbon, platinum-alumina, platinum-silica, and other supported catalysts. From a selectivity perspective, platinum complexes with an 0 valence are preferred, and toluene or xylene solutions of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complexes are particularly preferred.

[0200] There is no particular limitation on the amount of catalyst containing platinum compounds used. However, from the perspective of reactivity and productivity, it is preferable to contain 1 × 10⁻¹⁰ platinum atoms per mole of organosilicon compound represented by general formula (II). -7 ~1×10 -2 moles, more preferably 1×10 -7 ~1×10 -3 The range of moles.

[0201] Examples of co-catalysts include ammonium salts of inorganic acids, amide compounds, and carboxylic acids. Examples of ammonium salts of inorganic acids include ammonium chloride, ammonium sulfate, ammonium sulfamate, ammonium nitrate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium diphosphite, ammonium carbonate, ammonium bicarbonate, ammonium sulfide, ammonium borate, and ammonium borofluoride. Ammonium salts of inorganic acids with a pKa of 2 or higher are preferred, with ammonium carbonate and ammonium bicarbonate being particularly preferred.

[0202] Examples of amide compounds include formamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, acrylamide, malondiamide, succinamide, maleamide, fumaramide, benzamide, phthalamide, palmitamide, and stearamide.

[0203] Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, methoxyacetic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, lactic acid, glycolic acid, etc., with formic acid, acetic acid, and lactic acid being particularly preferred, and acetic acid being the most preferred among them.

[0204] There is no particular limitation on the amount of co-catalyst used, but from the viewpoints of reactivity, selectivity, and cost, 1 × 10⁻⁶ is preferred relative to 1 mole of organosilicon compound represented by general formula (II). -5 ~1×10 -1 moles, more preferably 1×10 -4 ~5×10 -1The range of moles. Furthermore, the above reaction can proceed even without a solvent, but a solvent can also be used. Examples of solvents that can be used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene, and xylene; ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as N,N-dimethylformamide; and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents can be used alone or in combination of two or more.

[0205] There is no particular limitation on the reaction temperature, and it can be carried out at room temperature (23℃±10℃) or under heating. In order to obtain a suitable reaction rate, it is preferable to carry out the reaction under heating, and the reaction temperature is preferably 35~200℃, more preferably 40~110℃, and even more preferably 40~90℃. In addition, there is no particular limitation on the reaction time, which is preferably 1~60 hours, more preferably 1~30 hours, and even more preferably 1~20 hours.

[0206] [(D) component]

[0207] (D) The platinum group metal catalyst is a catalyst used to promote the addition reaction of the curable organopolysiloxane composition of the present invention. Catalysts known to those skilled in the art for promoting the so-called hydrosilylation reaction 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, alcoholic or aldehyde solutions of chloroplatinic acid, complexes of various olefins or vinylsiloxanes of chloroplatinic acid, and complexes of various olefins or vinylsiloxanes of platinum.

[0208] The amount of component (D) need only be the so-called effective amount as a catalyst. For example, from the viewpoint of obtaining a good cured film and being economical, the amount of platinum group metals converted from the total mass of components (A) and (B) is preferably 0.1 to 200 ppm (mass), more preferably 0.5 to 150 ppm, even more preferably 1 to 100 ppm, and particularly preferably 2 to 50 ppm. In the present invention, by blending component (E) or making component (A) an organopolysiloxane represented by the above formula (3), it is also possible to make it a low platinum amount of 30 ppm or less.

[0209] [(E) component]

[0210] (E) The component is an organopolysiloxane containing (meth)acryloyl groups bonded to silicon atoms in one molecule, and is an organopolysiloxane represented by the following formula (5), which can be used alone or in combination of two or more. (R) 9 3SiO 1 / 2 )p (R) 9 2SiO 2 / 2 ) q (R) 9 SiO 3 / 2 ) r (SiO) 4 / 2 )s (5)

[0211] (where R) 9 Independently selected from alkenyl, hydroxyl, and unsubstituted or substituted monovalent hydrocarbon groups without aliphatic unsaturated bonds, and groups containing (meth)acryloyl groups, R 9 Of these, 0.1 to 20 are groups containing (meth)acryloyl groups, where p to s are positive numbers satisfying 2 ≤ p ≤ 202, 5 ≤ q ≤ 10000, r is 0 or 0 < r ≤ 100, and s is 0 or 0 < s ≤ 100, but 0 ≤ r + s ≤ 100.

[0212] Component (E) has 0.1 to 20 silicon-bonded (meth)acryloyl groups per molecule. Using more than 0.1 of these groups further enhances the reactivity of the addition reaction. However, if the number of these groups exceeds 20, the compatibility between components (A) and (B) decreases, potentially leading to turbidity. More specifically, the content of silicon-bonded (meth)acryloyl groups is preferably 0.0001 to 0.6 mol / 100g, more preferably 0.005 to 0.4 mol / 100g, and even more preferably 0.01 to 0.2 mol / 100g. By ensuring the content of silicon-bonded (meth)acryloyl groups is at or above the lower limit mentioned above, the reactivity of the addition reaction is further enhanced, achieving sufficient curability even with a reduced catalyst amount. Furthermore, if the content of silicon-bonded (meth)acryloyl groups exceeds the upper limit mentioned above, the compatibility between components (A) and (B) decreases, potentially leading to turbidity.

[0213] In the above formula (5), as a group containing (meth)acryloyl, the described groups containing (meth)acryloyl in organopolysiloxanes represented by formula (3) can be listed. As a group containing (meth)acryloyl, a group represented by CH2=CHCOOC3H6- is preferred.

[0214] (E) The component preferably has at least 0.1 alkenyl groups bonded to silicon per molecule. 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. By setting the content of alkenyl groups bonded to silicon to the lower limit or above, the curability is further improved. In addition, by setting the content of alkenyl groups bonded to silicon to the upper limit or below, a suitable peel strength can be further obtained.

[0215] In formula (5) above, preferred groups include alkenyl groups, unsubstituted or substituted monovalent hydrocarbon groups that do not have aliphatic unsaturated bonds, and which are either unsubstituted or substituted. Examples of such groups can be found in formula (2) above. Among these, all R groups are preferred in terms of improving curability and reducing peel strength. 9 More than 80 mol% of it is methyl.

[0216] (E) The viscosity of component E at 25°C is preferably 10000 mPa. Below s, more preferably 5 to 5000 mPa s, further preferred 10~1000mPa If the viscosity of component (E) exceeds the above upper limit, the compatibility of components (A) and (B) decreases, and clouding may occur.

[0217] p to s are each a positive number satisfying 2≤p≤202, 5≤q≤1000, r is 0 or 0<r≤100 (0≤r≤100), and s is 0 or 0<s≤100 (0≤s≤100). p is preferably 2~102, q is preferably 10~500, r and s are mutually independent and preferably 0~50, and r+s is preferably 0≤r+s≤50.

[0218] As a component (E), organopolysiloxanes, for example, can be represented by compounds represented by the following formula.

[0219] (R) 9 3SiO 1 / 2 )2(R 9 2SiO 2 / 2 ) q

[0220] (R) 9 3SiO 1 / 2 ) p (R) 9 2SiO 2 / 2 ) q (R) 9 SiO 3 / 2 ) r

[0221] (R)9 3SiO 1 / 2 ) p (R) 9 2SiO 2 / 2 ) q (SiO) 4 / 2 ) s

[0222] (R) 9 3SiO 1 / 2 ) p (R) 9 2SiO 2 / 2 ) q (R) 9 SiO 3 / 2 ) r (SiO) 4 / 2 ) s

[0223] In the above formulas, R 9 p~s as described above

[0224] As more detailed examples, compounds represented by the following formulas can be listed, but are not limited to these. Furthermore, the bonding order of the siloxane units shown in parentheses is not limited to the following.

[0225] (ViMe2SiO) 1 / 2 )2(Me2SiO 2 / 2 ) β1 (AMeSiO) 2 / 2 ) β2

[0226] (0≤β1<1000, 0.1≤β2≤20, 5≤β1+β2≤1000)

[0227] (Me3SiO) 1 / 2 )2(Me2SiO) β3 (AMeSiO) β4

[0228] (0≤β3<1000, 0.1≤β4≤20, 5≤β3+β4≤1000)

[0229] (ViMe2SiO) 1 / 2 ) β5 (Me3SiO) 1 / 2 ) β6 (Me2SiO) 2 / 2 ) β7 (AMeSiO) β8

[0230] (0.1≤β5<2, 0<β6≤1.9, β5+β6=2, 0≤β7<1000, 0.1≤β8≤20, 5≤β7+β8≤1000)

[0231] (ViMe2SiO) 1 / 2 )2(Me2SiO 2 / 2 ) β9 (ViMeSiO) 2 / 2 ) β10 (AMeSiO) 2 / 2 ) β11

[0232] (0≤β9<1000, 0<β10<1000, 0.1≤β11≤20, 5≤β9+β10+β11≤1000)

[0233] (ViMe2SiO) 1 / 2 ) β12 (Me2SiO) 2 / 2 ) β13 (AMeSiO) 2 / 2 ) β14 (MeSiO) 3 / 2 ) β15

[0234] (3≤β12≤102, 0≤β13<1000, 0.1≤β14≤20, 5≤β13+β14≤1000, 1≤β15≤100)

[0235] (ViMe2SiO) 1 / 2 ) β16 (Me2SiO) 2 / 2 ) β17 (AMeSiO) 2 / 2 ) β18 (MeSiO) 3 / 2 ) β19 (SiO) 4 / 2 ) β20

[0236] (4≤β16≤202, 0≤β17<1000, 0.1≤β18≤20, 5≤β17+β18≤1000, 0≤β19≤100, 1≤β20≤100, 1≤β19+β20≤100)

[0237] In the above formulas, Me, Vi, and A each refer to groups represented by methyl, vinyl, and CA:CH2=CHCOOC3H6-.

[0238] The amount of component (E) relative to 100 parts by mass of component (A) is preferably 0.01 to 20 parts by mass, more preferably 0.05 to 15 parts by mass, and even more preferably 0.1 to 10 parts by mass. By making the amount of component (E) above or above the aforementioned lower limit, the reactivity of the addition reaction can be further improved; by making the amount below the aforementioned upper limit, more suitable binding properties can be obtained. When component (E) has alkenyl groups bonded to silicon, the ratio of the number of SiH groups in component (B) to the total number of alkenyl groups in components (A) and (E) is preferably 0.5 to 10, preferably 0.8 to 8.0, and more preferably 1.0 to 5.0.

[0239] [Other ingredients]

[0240] In the curable organopolysiloxane composition of the present invention, in addition to components (A) to (E) described above, other optional components can be formulated without impairing the effects of the present invention. These other components are simply those commonly used in addition-reaction cured organopolysiloxane compositions, and known components can be added in the usual formulation amounts. Examples include the following components. These other components can be used individually or in combination of two or more.

[0241] [(F)Component]

[0242] (F) Addition reaction control agent

[0243] To ensure a suitable shelf life, the curable organopolysiloxane composition of the present invention can be further formulated with an addition reaction control agent corresponding to the platinum group metal catalyst (F). The addition reaction control agent is not particularly limited to any compound that has a curing-inhibiting effect on the platinum group metal catalyst of component (D) described above, and conventionally known compounds can be used. Examples include various organonitrogen compounds, organophosphorus compounds, alkyne compounds, and oxime compounds. More specifically, examples include alkynyl alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyn-3-ol, 2-phenyl-3-butyn-2-ol, and 1-ethynylcyclohexanol; alkynyl compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; reaction products of these alkynyl compounds with alkoxysilanes, siloxanes, or hydrosilanes; vinylsiloxanes such as tetramethylvinylsiloxane cyclic compounds; organonitrogen compounds such as benzotriazole; and other organophosphorus compounds and oxime compounds.

[0244] When compounding component (F), any amount sufficient to obtain a good shelf life is acceptable. Generally, 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, are preferred relative to 100 parts by weight of total component (A).

[0245] [(G) component]

[0246] In the curable organopolysiloxane composition of the present invention, (G) organic solvent can be incorporated. The curable organopolysiloxane composition of the present invention can also be prepared as a solvent-free composition obtained by incorporating a specified amount of components (A) to (D) or (A) to (E) above, and can also be used as a solvent-based composition diluted with an organic solvent as needed. By diluting the composition with an organic solvent, practical advantages such as improved adhesion, improved coating workability, improved coating film thickness, and improved surface finish are obtained.

[0247] As organic solvents (G), examples include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, and isoalkanes; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate; and ethers such as diisopropyl ether and 1,4-dioxane. Any compound capable of dissolving components (A) through (F) can be used. They can be used individually or in appropriate combinations of two or more.

[0248] The amount of component (G) can be 0 parts by mass. If the risk and safety reduction caused by organic solvents are undesirable, component (G) can be omitted to produce a solvent-free release sheet manufacturing organopolysiloxane composition. When component (G) is mixed, the mixing amount relative to 100 parts by mass of component (A) is preferably 100 to 20,000 parts by mass, more preferably 200 to 10,000 parts by mass. By mixing component (G) in an amount of 100 parts by mass or more, the advantages resulting from dilution are more easily obtained. Even when mixing amounts exceeding 20,000 parts by mass, the improvement in dilution effect is not significantly improved.

[0249] Furthermore, without impairing the effects of the present invention, known antioxidants, light-release additives, heavy-release additives, pigments, stabilizers, antistatic agents, defoamers, adhesion enhancers, thickeners, and inorganic fillers such as silica can be formulated as needed. When these are formulated, their amounts are preferably in the range of 0.01 to 200 parts by mass relative to 100 parts by mass of component (A).

[0250] [Method for manufacturing curable organopolysiloxane compositions]

[0251] There are no particular limitations on the method of manufacturing the curable organopolysiloxane composition of the present invention. From the perspective of the pot life, it is preferable to add the component (D) immediately before using it after uniformly mixing (A), (B), (C), (E), (F), (G) and other components as needed.

[0252] [Curing Organopolysiloxane Composition]

[0253] The viscosity of the curable organopolysiloxane composition of the present invention at 25°C is preferably 0.1 to 1000 mPa, from the perspective of coatability on a substrate. s, more preferably 1 to 800 mPa s, further preferred 5-600 mPa s.

[0254] There are no particular limitations on the appearance of the cured organopolysiloxane composition; it can be selected from white, transparent, semi-transparent, slightly cloudy, etc., depending on the application.

[0255] There is no particular limitation on the residual adhesion rate of the cured product of the curable organopolysiloxane composition, which can be appropriately selected according to the purpose. For example, in the method of the embodiments described later, it can also be set to 50-120%, preferably 70-110%, and more preferably 90-100%.

[0256] [Peeling tablets]

[0257] The present invention provides a release sheet having a substrate and a release agent layer disposed on at least one side of the substrate, the release agent layer being formed from a cured product formed by curing the above-described curable organopolysiloxane composition.

[0258] The substrate is preferably a sheet substrate, which can be single-sided or double-sided. By coating the above-mentioned curable organopolysiloxane composition on one or both sides of the substrate surface and heating it, a cured film can be formed.

[0259] There are no particular restrictions on the coating method and heat curing conditions; appropriate methods can be selected. For example, a curable organopolysiloxane composition can be used directly, employing coating methods such as corner roller coaters, lip coaters, roller coaters, molding coaters, doctor blade coaters, scraper coaters, rod coaters, lick coaters, gravure coaters, and wire-wound rod coaters, as well as screen coating, dip coating, and casting coating, to coat one or both sides of sheet substrates such as paper and film with a coating density of 0.01–100 g / m². 2 Then, heating at 50–200°C for 1 to 120 seconds can form a cured film on the substrate. When release layers are formed on both sides of the substrate, it is preferable to perform the cured film formation operation on each single side of the substrate.

[0260] Besides paper as the substrate, the substrate can also be formed from various known films. Examples of substrates include various coated papers such as polyethylene laminated paper, cellophane, paper without groundwood pulp, supercalendered kraft paper, and clay-coated kraft paper; synthetic papers such as YUPO; polyethylene films; polypropylene films such as CPP and OPP; polyester films such as polyethylene terephthalate films; and polyamide films, polyimide films, polylactic acid films, polyphenolic films, and polycarbonate films. Additionally, engineering paper used in the manufacture of artificial leather, ceramic sheets, and double-sided partitions can also be used as the substrate. To improve the adhesion between these substrates and the release layer, products that have undergone corona treatment, etching treatment, primer treatment, or plasma treatment on the substrate surface can be used. In this invention, to obtain a cured film with high adhesion to supercalendered kraft paper and clay-coated kraft paper, it can also be used on supercalendered kraft paper and clay-coated kraft paper.

[0261] Example

[0262] The following examples and comparative examples illustrate the invention in detail, but the invention is not limited to the examples described below. Furthermore, unless otherwise specified in the examples below, "%" in the composition indicates mass %, and "ratio" indicates mass ratio. Viscosities are all values ​​measured using a rotational viscometer at 25°C, and vinyl and acryloyl values ​​are measured using... 1 The values ​​determined by H-NMR. Below, Me, n-Bu, Ph, Vi, and A represent groups represented by methyl, n-butyl, phenyl, vinyl, and CH2=CHCOOC3H6-, respectively.

[0263] The components used in the examples and comparative examples are as follows. Hereinafter, the vinyl value is the number of moles of vinyl groups per 100g of each component; the acryloyl value is the number of moles of groups represented by CH2=CHCOOC3H6- per 100g of each component; and the SiH group content is the number of moles of SiH groups per 100g of each component. Furthermore, the bonding order of the siloxane units shown in parentheses is not limited to the following.

[0264] In this invention, the number-average molecular weight is the value obtained by GPC (gel permeation chromatography) analysis using polystyrene as a standard substance under the following conditions.

[0265] [Measurement Conditions]

[0266] Elution solvent: toluene

[0267] Flow rate: 0.35 mL / min

[0268] Detector: Differential Refractive Index Detector (RI)

[0269] column:

[0270] TSKgel Guarccolumn SuperHZ-L (4.6mmI.D.×2cm×1)

[0271] TSKgel SuperHZ4000 (4.6mmI.D.×15cm×1)

[0272] TSKgel SuperHZ3000 (4.6mmI.D.×15cm×1)

[0273] TSKgel SuperHZ2000 (4.6mmI.D.×15cm×2)

[0274] (All are manufactured by Tosoh Corporation)

[0275] Column temperature: 40℃

[0276] Sample injection volume: 10 μL (0.5% by mass toluene solution)

[0277] [Synthetic Example 1] Synthesis of Silane-Modified Polybutadiene Compound 1

[0278] Ricon 130 (manufactured by CRAY VALLEY) was added to a 1L detachable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer. In the above formula (I), a = 33, b = 13, c = 0, d = 0, R... 4 =H) 100g, toluene 200g, toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (based on platinum atoms, 0.52 × 10⁻⁶) -4 0.31 g (0.52 × 10⁻⁶) of acetic acid (mol) and 0.31 g (0.52 × 10⁻⁶) of acetic acid. -2 (moles). 63 g (0.52 mol) of trimethoxysilane was added dropwise over an internal temperature of 75–85 °C for 1 hour, followed by stirring at 80 °C for 1 hour.

[0279] After stirring, the mixture was concentrated under reduced pressure and filtered to obtain a brown, transparent liquid with a number average molecular weight of 6500. The molecular weight of the product and... 1 The average structure obtained from H-NMR spectroscopy is given by the general formula (1) above, where a = 33, b = 0, c = 13, d = 0, and R... 1 =Methyl, R 4 The silane-modified polybutadiene compound shown is represented by H and m=3.

[0280] [Synthetic Example 2] Synthesis of Silane-Modified Polybutadiene Compound 2

[0281] In a 1L detachable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, add 100g Ricon 130, 200g toluene, and a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (0.24 × 10⁻⁶ atoms). -4 0.14 g (0.24 × 10⁻⁶) and 0.14 g (0.24 × 10⁻⁶) -2 (Molar) Acetic acid. In this mixture, 29 g (0.24 mol) of trimethoxysilane was added dropwise for 1 hour at an internal temperature of 75–85 °C, and then stirred at 80 °C for 1 hour.

[0282] After stirring, the mixture was concentrated under reduced pressure and filtered to obtain a brown, transparent liquid with a number average molecular weight of 5200. The molecular weight of the product and... 1 The average structure obtained from H-NMR spectroscopy is given by the above general formula (1) where a = 33, b = 7, c = 6, d = 0, and R... 1 =Methyl, R 4 =H, m=3 indicates silane-modified polybutadiene compounds.

[0283] [Synthetic Example 3] Synthesis of Silane-Modified Polybutadiene Compound 3

[0284] A toluene solution (0.12 × 10⁻⁶ atoms) of 100 g Ricon 130, 200 g toluene, and platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added to a 1 L detachable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer. -4 0.07 g (0.12 × 10⁻⁶) and 0.07 g (0.12 × 10⁻⁶) -2 (0.12 mol) acetic acid. In this mixture, 14 g (0.12 mol) of trimethoxysilane was added dropwise at an internal temperature of 75–85 °C for 1 hour, followed by stirring at 80 °C for 1 hour.

[0285] After stirring, the mixture was concentrated under reduced pressure and filtered to obtain a brown, transparent liquid with a number average molecular weight of 4900. The molecular weight of the product and... 1 The average structure obtained from H-NMR spectroscopy is given by the general formula (1) above, where a = 33, b = 10, c = 3, d = 0, and R... 1 =Methyl, R 4 The silane-modified polybutadiene compound shown is represented by H and m=3.

[0286] [Synthetic Example 4] Synthesis of Silane-Modified Polybutadiene Compound 4

[0287] In a 1L detachable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, add 100g Ricon 130, 200g toluene, and a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (0.08 × 10⁻⁶ atoms).-4 0.05 g (0.08 × 10⁻⁶) and 0.05 g (0.08 × 10⁻⁶) -2 9.7 g (0.08 mol) of trimethoxysilane was added dropwise to the mixture over an internal temperature of 75–85 °C for 1 hour, followed by stirring at 80 °C for 1 hour.

[0288] After stirring, the mixture was concentrated under reduced pressure to obtain a brown, transparent liquid with a number average molecular weight of 4900. The molecular weight of the product and... 1 The average structure obtained from H-NMR spectroscopy is given by the following formula (1): a = 33, b = 11, c = 2, d = 0, R 1 =Methyl, R 4 =H, m=3 indicates silane-modified polybutadiene compounds.

[0289] [Synthetic Example 5] Synthesis of Silane-Modified Polybutadiene Compound 5

[0290] In a 1L detachable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, a copolymer of partially epoxidized Ricon 130 (R in formula (1) above) is added. 3 Composed of the above equation (1-1), a = 33, b = 11, c = 0, d = 2, R 4 =H) 100g, a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (based on platinum atoms, 0.20 × 10⁻⁶). -4 (Moles). 24 g (0.20 mol) of trimethoxysilane was added dropwise over 1 hour at an internal temperature of 75–85 °C. Then, the mixture was stirred at 80 °C for 3 hours.

[0291] After stirring, the solution was concentrated under reduced pressure and filtered to obtain a pale yellow, transparent liquid with a number average molecular weight of 5100. The molecular weight of the product and... 1 The average structure obtained from H-NMR spectroscopy is given by the following formula (1): a = 33, b = 6, c = 5, d = 2, R 1 =Methyl, R 4 =H, m=3 indicates silane-modified polybutadiene compounds.

[0292] [Synthetic Example 6] Synthesis of Silane-Modified Polybutadiene Compound 6

[0293] In a 1L detachable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, add 100g Ricon 130, 31g (0.04 mol) of an organohydrogen polysiloxane represented by the following formula (6), 200g toluene, and a toluene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (0.1 × 10⁻⁶ atoms based on platinum atoms). -5The product (in moles) was stirred at 100°C for 8 hours. After stirring, the molecular weight and... 1 The average structure obtained from H-NMR spectroscopy is given by the formula (I) above, where a = 33, b = 12, c = 0, d = 1, and R... 3 =The group represented in the following formula (7), R 4 =H represents a polybutadiene compound. Next, a toluene solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (0.48 × 10⁻⁶ atoms) was added. -4 0.29 g (0.48 × 10⁻⁶) of acetic acid (mol) and 0.29 g (0.48 × 10⁻⁶) of acetic acid. -2 58 g (0.48 mol) of trimethoxysilane was added dropwise over an internal temperature of 75–85 °C for 1 hour, followed by stirring at 80 °C for 1 hour. After stirring, the mixture was concentrated under reduced pressure and filtered to obtain a pale yellow transparent liquid with a number average molecular weight of 7500. The molecular weight of the product and... 1 The average structure obtained from H-NMR spectroscopy is given by the general formula (1) above, where a = 33, b = 0, c = 12, d = 1, and R... 1 =Methyl, R 3 =The group represented by the following formula (7), R 4 =H, m=3 indicates silane-modified polybutadiene compounds.

[0294] [Chemistry 9]

[0295]

[0296] (The asterisk * indicates a bond with the main chain's -CH-.)

[0297] [Synthetic Example 7] Synthesis of Silane-Modified Polybutadiene Compound 7

[0298] Add 100g of B-1000 (manufactured by Nippon Soda Co., Ltd.) to a 1L detachable flask containing a stirrer, reflux condenser, dropping funnel, and thermometer. In the above formula (I), a = 2, b = 18, c = 0, d = 0, R... 4 =H), 200g toluene, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in toluene solution (calculated as platinum atoms, 1.6 × 10⁻⁶). -4 1.3g (1.6 × 10⁻⁶ moles) and 1.3g (1.6 × 10⁻⁶ moles) -2 263 g (1.6 mol) of triethoxysilane was added dropwise over 2 hours at an internal temperature of 75–85 °C, followed by stirring at 80 °C for 1 hour.

[0299] After stirring, the mixture was concentrated under reduced pressure and filtered to obtain a brown, transparent liquid with a number average molecular weight of 6400. The molecular weight of the product and... 1The average structure obtained from H-NMR spectroscopy is given by equation (1) above, where a = 2, b = 0, c = 18, d = 0, and R... 1 =Ethyl, R 4 =H, m=3 indicates silane-modified polybutadiene compounds.

[0300] [Synthetic Example 8] Synthesis of Silane-Modified Polybutadiene Compound 8

[0301] In a 1L detachable flask containing a stirrer, reflux condenser, dropping funnel, and thermometer, add 100g of B-1000, 200g of toluene, and a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (calculated as platinum atoms, 0.8 × 10⁻⁶). -4 0.63g (0.8 × 10⁻⁶) and 0.63g (0.8 × 10⁻⁶) -2 (0.8 mol) ammonium bicarbonate. In this mixture, 98 g (0.8 mol) of trimethoxysilane was added dropwise over 1 hour at an internal temperature of 75–85 °C, followed by stirring at 80 °C for 1 hour.

[0302] After stirring, the mixture was concentrated under reduced pressure and filtered to obtain a brown, transparent liquid with a number average molecular weight of 3500. The molecular weight of the product and... 1 The average structure obtained from H-NMR spectroscopy is given by equation (1) above, where a = 2, b = 9, c = 9, d = 0, and R... 1 =Methyl, R 4 =H, m=3 indicates silane-modified polybutadiene compounds.

[0303] (A) Ingredients

[0304] (A-1-1) The molecular chain is end-capped with dimethylvinylsilyloxy groups, vinyl number is 0.018 mol / 100 g, and viscosity is 380 mPa. s methyl vinyl polysiloxane

[0305] (ViMe2SiO) 1 / 2 )2(Me2SiO 2 / 2 ) 150

[0306] (A-1-2) The molecular chain is capped at both ends with dimethylvinylsiloxy groups, has acryloyl groups in the side chains, has a vinyl value of 0.018 mol / 100g, contains 0.0009 mol / 100g of acryloyl groups, and has a viscosity of 420 mPa. s-methyl vinyl polysiloxanes containing acryloyl groups:

[0307] (ViMe2SiO) 1 / 2 )2(Me2SiO 2 / 2 ) 150(AMeSiO) 2 / 2 ) 0.1

[0308] (A-1-3)

[0309] By (ViMe2SiO) 1 / 2 The organopolysiloxane composed of 0.025 mol% of dimethylvinylsiloxane units represented by (ViMeSiO), 1.46 mol% of methylvinylsiloxane units represented by (ViMeSiO), and 98.5 mol% of dimethylsiloxane units represented by (Me2SiO) has a viscosity of 15 Pa at 25°C for a 30% by mass toluene solution. s, Vinyl content is 0.020 mol / 100g

[0310] (B) Components

[0311] (B-1) The molecular chain is capped at both ends with trimethylsilyloxy groups, the SiH group content is 1.6 mol / 100 g, and the viscosity is 20 mPa. s methylhydropolysiloxane

[0312] (Me3SiO) 1 / 2 )2 (MeHSiO 2 / 2 ) 40

[0313] (B-2) The molecular chain is capped at both ends with trimethylsilyloxy groups, the SiH group content is 1.0 mol / 100 g, and the viscosity is 50 mPa. s methylhydropolysiloxane

[0314] (Me3SiO) 1 / 2 )2 (MeHSiO 2 / 2 ) 45 (Me2SiO) 2 / 2 ) 20

[0315] (B-3) The molecular chain is capped at both ends with trimethylsilyloxy groups, the SiH group content is 1.0 mol / 100 g, and the viscosity is 140 mPa. s methylhydropolysiloxane

[0316] (Me3SiO) 1 / 2 )2 (MeHSiO 2 / 2 ) 80 (Me2SiO) 2 / 2 ) 40

[0317] (C) Components

[0318] (C-1) Silane-modified polybutadiene compound 1 of Synthesis Example 1

[0319] (C-2) Silane-modified polybutadiene compound 2 of Synthesis Example 2

[0320] (C-3) Silane-modified polybutadiene compound 3 of Synthesis Example 3

[0321] (C-4) Silane-modified polybutadiene compound 4 of Synthesis Example 4

[0322] (C-5) Ricon130 (manufactured by CRAY VALLEY) number average molecular weight 4800

[0323] (C-6) Synthesis of Silane-Modified Polybutadiene Compound 5 of Example 5

[0324] (C-7) Synthesis of Silane-Modified Polybutadiene Compound 6 of Example 6

[0325] (C-8) Silane-modified polybutadiene compound 7 of Synthesis Example 7

[0326] (C-9) Synthesis of silane-modified polybutadiene compound 8 from Example 8

[0327] The information summarizing the structures for (C-1) to (C-9) is shown in Table 1 below.

[0328] [Table 1]

[0329]

[0330] (D) Component

[0331] The reaction product of hexachloroplatinic acid and 1,3-divinyltetramethyldisiloxane was diluted with the above-mentioned methylvinyl polysiloxane (A-1-1) to make the platinum content 0.50% by mass, thus preparing the platinum catalyst D used in this example and comparative example.

[0332] (E) Components

[0333] (E-1) The molecular chain is capped at both ends with dimethylvinylsiloxy groups, has acryloyl groups in the side chains, has a vinyl value of 0.016 mol / 100 g, contains 0.077 mol / 100 g of acryloyl groups, and has a viscosity of 450 mPa. s-methyl vinyl polysiloxanes containing acryloyl groups:

[0334] (ViMe2SiO) 1 / 2 )2(Me2SiO 2 / 2 ) 150 (AMeSiO) 2 / 2 ) 10

[0335] (E-2) The molecular chain is capped at both ends by trimethylsilyloxy groups, and the side chains contain acryloyl groups. The content of acryloyl groups is 0.21 mol / 100 g, and the viscosity is 50 mPa. s-containing methyl polysiloxanes with acryloyl groups:

[0336] (Me3SiO) 1 / 2 )2(Me2SiO 2 / 2 ) 40 (AMeSiO) 2 / 2 ) 10

[0337] (F) Ingredients

[0338] (F) 1-Ethynyl-1-cyclohexanol

[0339] (G) component

[0340] (G) A 1:1 mass ratio of toluene to hexane mixed solvent

[0341] Comparative example ingredients (comparative product)

[0342] (c-1) A phenyl-containing organohydrogen polysiloxane represented by the following formula

[0343] [Chemistry 10]

[0344]

[0345] (c-2) Organohydrogen polysiloxanes containing epoxy groups, represented by the following formula

[0346] [Chemistry 11]

[0347]

[0348] (c-3) Organopolysiloxanes containing epoxy, vinyl, and methoxy groups, represented by the following formula.

[0349] [Chemistry 12]

[0350]

[0351] (c-4) Organopolysiloxanes containing epoxy groups, represented by the following formula

[0352] [Chemistry 13]

[0353]

[0354] (c-5) Organopolysiloxanes containing epoxy groups and methoxy groups, represented by the following formula.

[0355] [Chemistry 14]

[0356]

[0357] [Examples 1-9, Comparative Examples 1-6 (solvent-free, typical platinum content)]

[0358] Components (A), (B), (F), and (C), or the comparative example components, were mixed in a flask according to the mixing ratios described in Tables 2, 3, and 5 below. While stirring until homogeneous, component (D) was added relative to the total mass of components (A) and (B) to achieve a platinum conversion of 50 ppm. The mixture was then stirred to obtain an organopolysiloxane composition for coating. The ratio of the number of SiH groups in component (B) to the number of alkenyl groups in component (A) (H / Vi) and the appearance (transparency) of the composition are shown in Tables 2, 3, and 5. Coated products were prepared using this composition according to the methods described later, and the results were evaluated.

[0359] [Examples 10-17, Comparative Examples 7-12 (solvent-free, low platinum content)]

[0360] Components (A), (B), (E), (F), and (C), or the comparative example components, were mixed in a flask according to the mixing ratios described in Tables 3, 4, and 6 below. Component (D) was added relative to the total mass of components (A) and (B) in the homogeneous mixture to obtain a platinum-converted 25 ppm. The mixture was stirred to obtain an organopolysiloxane composition for coating. The ratio of the number of SiH groups in component (B) to the number of alkenyl groups in component (A) (H / Vi) and the appearance (transparency) of the composition are shown in Tables 3, 4, and 6. Coated products were prepared using this composition and evaluated according to the methods described later.

[0361] [Cure of Solvent-Free Organopolysiloxane Compositions]

[0362] The solvent-free organopolysiloxane composition described above was coated onto the metal roller of an RI tester (manufactured by IHI Machinery Systems Co., Ltd.). While pressing the metal roller against the rubber roller, the two rollers were rotated for 45 seconds. After uniform stretching, the composition was transferred from the rubber roller onto polyethylene laminated paper. The polyethylene laminated paper with the transferred composition was heated in a hot air dryer at 120°C for 20 seconds to obtain a thickness of 0.9–1.1 g / m². 2 The release paper of the cured film.

[0363] [Examples 18-19, Comparative Examples 13-14 (solvent-based)]

[0364] Components (A), (B), (F), and (C), or the comparative example components, were mixed in the proportions described in Table 7 below and placed in a flask. 1900 parts by mass of component (G) were added, and the mixture was stirred until homogeneous. Component (D) was added to the mixture at a platinum equivalent of 150 ppm relative to the total mass of components (A) and (B), and the mixture was stirred to obtain an organopolysiloxane composition for coating. Table 7 shows the ratio of the number of SiH groups in component (B) to the number of alkenyl groups in component (A) (H / Vi) and the appearance (transparency) of the composition. Coated products were prepared using this composition according to the method described later, and the results were evaluated.

[0365] [Cure of Solvent-Based Organopolysiloxane Compositions]

[0366] The above-mentioned solvent-based organopolysiloxane composition was coated onto polyethylene laminated paper using a rod coater, and then heated in a hot air dryer at 120°C for 20 seconds to obtain a thickness of 0.9–1.1 g / m². 2 The release paper of the cured film.

[0367] [Peeling force]

[0368] After curing the release paper obtained using the above curing method at 25°C for 24 hours, a 25mm wide acrylic pressure-sensitive adhesive tape TESA-7475 (tesa UK Ltd.) was pasted onto the cured film surface of the release paper (from the transfer side of the rubber roller), and cut into 25mm × 23cm pieces. These were then clamped to a glass plate and cured at 70°C at 20g / cm². 2 The product cured under load for 24 hours was used as the test specimen. After natural cooling for 30 minutes, the TESA-7475 strip of the specimen was peeled at an angle of 180° and at a speed of 0.3 m / min using a tensile testing machine (Shimadzu Corporation DSC-500 testing machine), and the force required for peeling was measured. The results are shown in Tables 2 to 7.

[0369] [Peel force change rate (%)]

[0370] Using the peel force obtained by the above-described measurement method, the rate of change (%) of the peel force was calculated according to the following method.

[0371] Peel force of Examples 1-9 and Comparative Examples 2-6 / Peel force of Comparative Example 1 × 100

[0372] Peel force of Examples 10-17 and Comparative Examples 8-12 / Peel force of Comparative Example 7 × 100

[0373] Peel force of Examples 18-19 and Comparative Example 13 / Peel force of Comparative Example 13 × 100

[0374] Comparative Examples 1, 7, and 13 correspond to compositions without the addition of an adhesion enhancer. Using the calculations described above, the percentage change in peel force when the adhesion enhancer is added can be calculated. The results are shown in Tables 2-7.

[0375] [Residual Adhesion Rate]

[0376] The pressure-sensitive adhesive side of the TESA-7475 tape, after being peeled from the release layer as measured by the peel force test, was adhered to a stainless steel plate, and a 2 kg roller was applied under load for reciprocating motion. After 30 minutes, one end of the TESA-7475 tape was peeled off, and its end was stretched at a 180-degree angle relative to the stainless steel plate at a peel speed of 0.3 m / min. The force required for peeling at this point was measured: peel force A (gf / 25 mm).

[0377] In addition, unused TESA-7475 tape, which was not attached to the peeling layer, was adhered to a stainless steel sheet. Under the same conditions as above, the force required to peel the TESA-7475 tape from the stainless steel sheet was measured: peel force B (gf / 25mm). The results are shown in Tables 2-7.

[0378] The residual adhesive rate (%) was calculated using the formula (A / B) × 100.

[0379] [Seamlessness]

[0380] Similarly, a release layer was formed on polyethylene laminated paper (referred to as polyethylene laminated paper in the table) to obtain release paper. Furthermore, by changing the substrate, release layers were formed on supercalendered kraft paper (referred to as SCK in the table), clay-coated kraft paper (referred to as CCK in the table), and glassine paper (referred to as glassine paper in the table) to obtain release paper. The curing conditions for the supercalendered kraft paper, clay-coated kraft paper, and glassine paper were 150°C × 30 seconds, and the thickness was set to 1.0–1.2 g / m². 2 The obtained release paper was cured at 25°C for 24 hours. Then, after being stored under the following conditions, the release layer was rubbed 10 times with a finger, and its removal from the substrate was visually observed and evaluated using the following standards. The results are shown in Tables 2-7.

[0381] [Evaluation Criteria]

[0382] Cured products of solvent-free organopolysiloxane compositions

[0383] Polyethylene laminated paper

[0384] A: It will not fall off even after 15 hours at 85℃ and 85%RH.

[0385] B: No detachment was observed after 10 hours at 85℃ and 85%RH, but detachment occurred after 15 hours at 85℃ and 85%RH.

[0386] C: No detachment was observed after 5 hours at 85℃ and 85%RH, but detachment occurred after 10 hours at 85℃ and 85%RH.

[0387] D: It will detach after 5 hours at 85℃ and 85%RH.

[0388] Supercalendered kraft paper, clay-coated kraft paper and cellophane

[0389] A: No peeling occurred even after 48 hours at 85℃ and 85%RH.

[0390] B: No detachment was observed after 24 hours at 85℃ and 85%RH, but detachment occurred after 48 hours at 85℃ and 85%RH.

[0391] C: No peeling was observed after 24 hours of curing at 25℃, but peeling occurred after 24 hours at 85℃ and 85%RH.

[0392] D: Detached after curing at 25℃ for 24 hours.

[0393] Cured products of solvent-based organopolysiloxane compositions

[0394] Polyethylene laminated paper, supercalendered kraft paper, clay-coated kraft paper, and cellophane

[0395] A: No peeling occurred after 96 hours at 85℃ and 85%RH.

[0396] B: No detachment was observed after 48 hours at 85℃ and 85%RH, but detachment occurred after 96 hours at 85℃ and 85%RH.

[0397] C: No peeling was observed after 24 hours of curing at 25℃, but peeling occurred after 48 hours at 85℃ and 85%RH.

[0398] D: Detached after curing at 25℃ for 24 hours.

[0399] In this invention, for solvent-free organopolysiloxane compositions, an adhesion level of C or higher (A, B, C) is set as a qualified point, and for solvent-based organopolysiloxane compositions, an adhesion level of B or higher (A, B) is set as qualified.

[0400] [Table 2]

[0401]

[0402] [Table 3]

[0403]

[0404] [Table 4]

[0405]

[0406] [Table 5]

[0407]

[0408] [Table 6]

[0409]

[0410] [Table 7]

[0411]

[0412] [Table 8]

[0413]

[0414] As shown in the results above, the substrates with improved adhesion, including Comparative Examples 1, 7, and 13 (without component (C)) and Comparative Examples 2-6, 8-12, and 14 (with components other than component (C)), also showed improved adhesion, but the effect was insufficient. Furthermore, Comparative Examples 2-4, 8-10, and 14 (with components containing SiH) showed increased peel strength compared to the unadded cases.

[0415] Examples 1-19, which incorporate the adhesion enhancer shown in component (C) of the present invention, exhibit excellent adhesion to a wide range of substrates, and furthermore, show minimal change in peel force compared to the absence of the additive. Examples 10-17 are low-platinum compositions, which, by blending the organopolysiloxane of formula (3) as component (A) and component (E), maintain high adhesion to various substrates with low platinum content. Furthermore, these examples exhibit high residual adhesion rates.

[0416] Industrial availability

[0417] The curable organopolysiloxane composition of the present invention exhibits excellent adhesion to paper substrates such as supercalendered kraft paper and clay-coated kraft paper, and can form a cured film with good peel strength and residual adhesion. Therefore, the curable organopolysiloxane composition of the present invention is suitable for use as an organopolysiloxane composition for release sheets.

Claims

1. A curable organopolysiloxane composition comprising the following components (A) to (D), (A) An organopolysiloxane having at least two alkenyl groups bonded to silicon in one molecule: 100 parts by mass, (B) Organohydrogen polysiloxanes having two or more hydrogen atoms bonded to silicon atoms, i.e., SiH groups, in one molecule: the amount of which makes the ratio of the number of SiH groups in component (B) to the number of alken groups in component (A) 0.5 to 10. (C) A polybutadiene compound represented by the following general formula (1): 0.01 to 10 parts by mass relative to 100 parts by mass of component (A), [Chemistry 1] In the formula, R 1 R 2 Each is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, R 3 Each is a group represented by formula (1-1) or (1-2) below, R 4 Each is independently a hydrogen atom or a group represented by -CH2CH2OH. a is a positive number that satisfies 0 < a ≤ 120. b is 0 or a positive number satisfying 0 < b ≤ 100. c is 0 or a positive number satisfying 0 < c ≤ 100. d is 0 or a positive number satisfying 0 < d ≤ 20. The condition is satisfied that 0 < b + c ≤ 200, where m is an integer from 1 to 3. The order of the repeating units is arbitrary. [Chemistry 2] In the formula, R 5 Each group is an unsubstituted or substituted monovalent hydrocarbon group with 1 to 12 carbon atoms, where n represents a positive number from 1 to 100, and the asterisk * indicates a bond with the -CH- group of the main chain. (D) Platinum group metal catalysts: catalytic amount.

2. The curable organopolysiloxane composition according to claim 1, wherein, (C) The number average molecular weight of the polybutadiene compound is 1,000 to 1,000,000.

3. The curable organopolysiloxane composition according to claim 1, wherein, (C) The polybutadiene compounds of general formula (1) in which components a, b, c, and d independently satisfy the conditions of the following formulas (i), (ii), and (iii), 。 4. The curable organopolysiloxane composition according to claim 1, wherein, (A) The component is an organopolysiloxane represented by the following formula (2), In the formula, R 6 Independently selected from alkenyl, hydroxyl, and unsubstituted or substituted monovalent hydrocarbon groups without aliphatic unsaturated bonds, R 6 In the formula, at least two are alkenyl groups, e is 2 or more, f is 0 or 0 < f, g is 0 or 0 < g, and h is a positive number that is 0 or 0 < h. The formula is e + f + g + h, which makes the viscosity at 25°C 1 mPa. A viscosity of 70,000 mPa is obtained when the concentration of the substance is greater than s and dissolved in toluene at 30% by mass. Below s.

5. The curable organopolysiloxane composition according to claim 1, wherein, (A) The component is an organopolysiloxane represented by the following formula (3), In the formula, R 7 Independently selected from alkenyl, hydroxyl, unsubstituted or substituted monovalent hydrocarbon groups without aliphatic unsaturated bonds, and groups containing (meth)acryloyl groups, R 7 At least two of them are alkenyl groups, R 7 The number of groups in the formula is 0.01 to 2.9, which contain (meth)acryloyl groups. v is 2 or more, w is 8 or more, x is 0 or 0 < x, and y is 0 or 0 < y. The formula is chosen to make the viscosity at 25°C 1 mPa. A viscosity of 70,000 mPa is obtained when the concentration of the substance is greater than s and dissolved in toluene at 30% by mass. Below s.

6. The curable organopolysiloxane composition according to claim 1, wherein, (B) The components are represented by the following average composition formula (4), In the formula, R 8 Each component is a monovalent hydrocarbon group consisting of 1 to 12 unsubstituted or substituted carbon atoms that do not have aliphatic unsaturated bonds, and t and u are positive numbers that satisfy 0.7≤t≤2.1, 0.001≤u≤1.0, and 0.8≤t+u≤3.0, wherein component (B) has at least 2 hydrogen atoms bonded to silicon atoms.

7. The curable organopolysiloxane composition according to claim 1, wherein, Relative to 100 parts by mass of component (A), it also contains 0.01 to 20 parts by mass of (E), represented by the following formula (5), an organopolysiloxane having 0.1 to 20 groups containing (meth)acryloyl groups bonded to silicon atoms in one molecule. In the formula, R 9 Independently selected from alkenyl, hydroxyl, unsubstituted or substituted monovalent hydrocarbon groups without aliphatic unsaturated bonds, and groups containing (meth)acryloyl groups, R 9 0.1 to 20 of them are groups containing (meth)acryloyl groups, p to s are each positive numbers that satisfy 2≤p≤202, 5≤q≤1000, r is 0 or 0<r≤100, and s is 0 or 0<s≤100, and 0≤r+s≤100.

8. A release sheet having a substrate and a release agent layer disposed on at least one side of the substrate, the release agent layer being formed from a cured product of a curable organopolysiloxane composition according to claim 1.

Images