Curable organopolysiloxane composition

Abstract

The curable organopolysiloxane composition can perform an addition reaction with a small amount of a platinum group metal catalyst and has curability equivalent to that of conventional organopolysiloxane compositions, and is particularly used as release paper and a release film. Provided are: a curable organopolysiloxane composition which is capable of forming a cured coating film having a peel strength equivalent to that of conventional organopolysiloxane compositions, and which is also cured by an addition reaction on a base material containing a catalyst toxin component; the present invention relates to an organopolysiloxane composition containing (A) an organopolysiloxane having two or more alkenyl groups bonded to a silicon atom in one molecule and not having three or more (meth) acryloyl groups in one molecule; (B) an organohydrogenpolysiloxane having an average of two or more hydrogen atoms bonded to a silicon atom in one molecule and not having three or more (meth) acryloyl groups; (C) a compound having a molecular weight of 72-1000, excluding an organopolysiloxane, among compounds having one or more (meth) acryloyl groups in one molecule; and (D) a platinum group metal catalyst.

Description

Technical Field

[0001] This invention relates to curable organopolysiloxane compositions that can be cured with a small amount of platinum, particularly organopolysiloxane compositions for use in release paper or release film. Background Technology

[0002] To date, organopolysiloxane compositions cured by addition reaction using platinum catalysts can be cured at relatively low temperatures and in a short time, thus enabling their use in a wide range of applications as base polymers for various coatings, adhesives for molded products, pressure-sensitive adhesives, etc.

[0003] However, platinum group metals, used as catalysts, are rare and precious metals on Earth, resulting in high prices. Platinum catalysts account for a large proportion of manufacturing costs across all applications. Therefore, reducing the amount of platinum group metal catalysts used has become the most effective means of lowering prices.

[0004] Furthermore, the raw materials used in manufacturing may contain catalyst toxins such as nitrogen compounds, sulfur compounds, and phosphorus compounds, which can become catalyst toxins in platinum group metal catalysts. The problem arises because these catalyst toxins bind to the platinum group metals, preventing the curing process, which involves addition reactions, from proceeding. Therefore, there is a need for curable organopolysiloxane compositions that are less susceptible to the effects of catalyst toxins.

[0005] As an example of the use of such a curing feature of addition reaction using a platinum catalyst, applications such as release paper or release film are mentioned. In order to prevent the adhesion and fixation of sheet-like substrates such as paper and plastic to pressure-sensitive adhesive materials, it is known to form a cured film of an organopolysiloxane composition on the surface of the substrate, thereby imparting release properties.

[0006] Currently, platinum group metal catalysts, as expressed in terms of platinum group metal concentration, are often used in the range of 100–500 ppm by mass, relative to the organopolysiloxane compositions used for release paper or release film. This is because, at platinum concentrations below 100 ppm by mass, the curing reaction is not fully carried out, the cured film becomes soft, and there is a high amount of residual Si-H groups, thus increasing the release force. In addition, unreacted organopolysiloxane raw materials are present and become migrating components. Therefore, on the pressure-sensitive adhesive surface bonded to the release paper, organopolysiloxane migrates, causing a decrease in adhesion.

[0007] To date, methods for addressing these issues are being investigated. International Publication Nos. 2020 / 004254 and 2020 / 145151 disclose methods for adding compounds containing (meth)acryloyl groups to addition curing compositions employing platinum catalysts. According to these methods, even with a smaller amount of platinum catalyst added than previously possible, it is possible to form a cured film with good peel strength and residual adhesion.

[0008] International Publication No. 2021 / 020247 reported that even when using this method as a platinum catalyst composition, a good cured film can be formed with the same amount of platinum catalyst added as before.

[0009] However, for applications on substrates such as plastic film substrates where it is difficult to achieve a tight bond with the silicone-cured film, and for applications on substrates such as cellophane where the curing of addition-cured silicone compositions is difficult compared to other substrates, it cannot be said to satisfy sufficient curability and adhesion while simultaneously reducing the amount of platinum catalyst added. In the current market, there is potential demand for applications on these substrates, and technologies to address these issues need to be developed.

[0010] Existing technical documents

[0011] Patent documents

[0012] Patent Document 1: International Publication No. 2020 / 004254

[0013] Patent Document 2: International Publication No. 2020 / 145151

[0014] Patent Document 3: International Publication No. 2021 / 020247 Summary of the Invention

[0015] The problem that the invention aims to solve

[0016] The present invention was made in view of the above-mentioned actual situation, and its object is to provide a curable organopolysiloxane composition that can carry out addition reactions with a small amount of platinum group metal catalyst, can form a cured film with the same peel strength as before, and is equally applicable to substrates that are difficult to cure by addition reactions due to difficulties in obtaining adhesion to the silicone cured film, or substrates containing catalyst toxins, etc., such as plastic film substrates, and silicone compositions that are difficult to cure by addition reactions. It is particularly suitable for release paper or release film.

[0017] Methods for solving problems

[0018] In order to achieve the above-mentioned objective, the inventors conducted in-depth research and found that by incorporating an organopolysiloxane having a trivinylsiloxane unit at the molecule end as component (A) into an addition reaction-cured organopolysiloxane composition, and simultaneously incorporating a compound having one or more (meth)acryloyl groups in one molecule as component (C), the above-mentioned problem can be solved, and the present invention is completed.

[0019] Therefore, the present invention provides the following curable organopolysiloxane compositions, particularly curable organopolysiloxane compositions for use in release paper or release film (hereinafter sometimes simply referred to as organopolysiloxane compositions).

[0020] 1. A curable organopolysiloxane composition containing the following components (A) to (D):

[0021] (A) an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms in one molecule, with an alkenyl content of 0.001 to 0.7 mol / 100g, and having no more than three (meth)acryloyl groups in one molecule, wherein at least 50% by mass of the molecular end of component (A) is capped with a siloxane unit as shown in formula (1) below, and has a viscosity of 7 mPa·s or more at 25°C as measured by a rotational viscometer, and a 30% by mass toluene dissolution viscosity (the viscosity of a solution in which 30% by mass of the organopolysiloxane is dissolved in toluene) of 70,000 mPa·s or less: 100 parts by mass,

[0022] (CH2=CH-)3SiO 1 / 2 (1)

[0023] (B) An organohydrogen polysiloxane having an average of two or more hydrogen atoms (Si-H groups) bonded to silicon atoms in one molecule, and no more than three (meth)acryloyl groups in one molecule: the amount of which is such that, relative to the molar number of alkenes in component (A), the molar number of Si-H groups in component (B) is 1 to 10 times.

[0024] (C) is selected from one or more of (C-1) and (C-2) below: 0.01 to 5.0 parts by mass relative to 100 parts by mass of component (A).

[0025] (C-1) A non-organopolysiloxane compound having one or more (meth)acryloyl groups in one molecule and having a molecular weight of 72 to 1000.

[0026] (C-2) An organopolysiloxane having three or more (meth)acryloyl groups in one molecule, wherein the weight-average molecular weight of the organopolysiloxane, as determined by gel permeation chromatography (GPC) (solvent: toluene), is greater than 500 and less than 20,000 based on the polystyrene equivalent.

[0027] (D) Platinum group metal catalyst: in an amount such that the platinum concentration in the total mass of components (A), (B), (C) and (D) is 1 to 100 ppm by mass.

[0028] 2. The curable organopolysiloxane composition according to 1, wherein, relative to 100 parts by weight of component (A), it further contains 0 to 100,000 parts by weight of diluent (E).

[0029] 3. The curable organopolysiloxane composition according to 1 or 2, wherein, relative to 100 parts by weight of component (A), it further contains 0.01 to 5.0 parts by weight of reaction control agent (F).

[0030] 4. The curable organopolysiloxane composition according to any one of 1 to 3, wherein component (B) contains component (B) in which 5 to 30 mol% of the total number of substituents on the Si atoms are phenyl.

[0031] 5. The curable organopolysiloxane composition according to any one of 1 to 4, wherein component (A) contains component (A) in which 1 to 20 mol% of the total number of substituents on the Si atom are phenyl.

[0032] 6. The curable organopolysiloxane composition according to any one of 1 to 5, further comprising, relative to 100 parts by weight of component (A), 0.1 to 20.0 parts by weight of organopolysiloxane (G), having at least two alkenyl groups, wherein R 10 (3-g1) R 9 g1 SiO 1 / 2 Siloxane unit (M) R9R10 Unit), R 10 SiO 3 / 2 Siloxane unit (T R10 (Unit) (where R) 9 Each is an alkenyl group independently, R 10 Each is an independent monovalent hydrocarbon group, unsubstituted or halogenated, or cyano-substituted without aliphatic unsaturated bonds, where g1 is an integer from 1 to 3. As a necessary unit, M... R9R10 Unit / T R10 The molar ratio of the units satisfies 2 / 8 to 8 / 2, and the viscosity of (G) organopolysiloxane at 25°C ranges from 1 to 1000 mPa·s. The molecular terminus of (G) organopolysiloxane is M. R9R10 Unit, or M R9R10 The unit and part of it are silanol or alkoxy groups.

[0033] 7. The curable organopolysiloxane composition according to any one of 1 to 6, wherein component (C) is an organopolysiloxane having one or more difunctional and / or trifunctional siloxane units having (meth)acryloyl groups in one molecule.

[0034] 8. The curable organopolysiloxane composition according to any one of 1 to 7, wherein, relative to 100 parts by weight of component (A), it further contains 0.01 to 5.0 parts by weight of (H) organic peroxide.

[0035] 9. The curable organopolysiloxane composition according to 8, wherein the (H) component is a multifunctional organic peroxide having two or more peroxy bonds in the molecule.

[0036] 10. The curable organopolysiloxane composition according to any one of 1 to 9, wherein the platinum group metal catalyst (D) is contained in an amount of 1 to 40 ppm by mass of the total mass of components (A) to (D).

[0037] 11. The curable organopolysiloxane composition according to any one of 1 to 10, used for release paper or release film.

[0038] 12. A method for manufacturing a release paper or release film, wherein the organopolysiloxane composition for release paper or release film according to claim 11 is used.

[0039] The effects of the invention

[0040] According to the present invention, it is possible to provide a curable organopolysiloxane composition that can undergo an addition reaction with a small amount of platinum group metal catalyst, has curability comparable to that of the past, and in particular, an organopolysiloxane composition for release paper or release film that can form a cured film with peel strength comparable to that of the past.

[0041] Therefore, it is possible to form a cured silicone film even under conditions that were previously difficult to cure, which greatly reduces manufacturing costs. It is also possible to form a cured film using an addition reaction for substrates containing catalyst toxins. Detailed Implementation

[0042] The present invention will now be described in detail.

[0043] [(A) ingredient]

[0044] The (A) component of the present invention is an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms in one molecule, an alkenyl content of 0.001 to 0.7 mol / 100g, and not having three or more (meth)acryloyl groups in one molecule. At least 50% by mass of the molecular end of the (A) component is capped with a siloxane unit represented by the following formula (1).

[0045] (CH2=CH-)3SiO 1 / 2(1) An organopolysiloxane whose viscosity at 25°C, as measured by a rotational viscometer, is 7 mPa·s or higher and whose 30% by mass toluene dissolution viscosity (the viscosity of a solution in which 30% by mass of the organopolysiloxane is dissolved in toluene) is 70,000 mPa·s or lower. The above-mentioned organopolysiloxanes can be used alone or in appropriate combinations of two or more.

[0046] As component (A), examples of organopolysiloxanes having a structure represented by the following formula (2) can be listed.

[0047] M α M Vi β D γ D Vi δ T ε T Vi ζ Q η (2)

[0048] In the formula, M is R3SiO 1 / 2 M Vi For R a P (3-a) SiO 1 / 2 D is R2SiO 2 / 2 D Vi RPSiO 2 / 2 T is RSiO 3 / 2 T Vi For PSiO 3 / 2 Q is SiO 4 / 2 , where a is an integer from 0 to 3. The alpha, δ, ε, ζ, and η literals in the formula are each independently 0 or positive numbers, and β and γ are positive numbers.

[0049] The organopolysiloxane comprising more than 50% by mass of component (A) is an organopolysiloxane whose end is capped by at least one molecule using a monofunctional siloxane unit of formula (1) above, and at least one M in one molecule of formula (2) above. Vi For the case where a is 0, the above equation (1) is (CH2=CH-)3SiO 1 / 2 Unit. The organopolysiloxane preferably accounts for 60% or more by mass of component (A), more preferably 70% or more by mass. Furthermore, if the organopolysiloxane is less than 50% by mass of component (A), the curability decreases.

[0050] The remaining less than 50% by mass of component (A) may be an organopolysiloxane represented by formula (2) above, whose molecular ends are not capped by the monofunctional siloxane unit of formula (1) above. If more than 50% by mass is mixed, the curability is reduced.

[0051] In the above formula (2), R is an unsubstituted or substituted monovalent hydrocarbon group with 1 to 12 carbon atoms that does not have an aliphatic unsaturated bond, preferably a monovalent hydrocarbon group with 1 to 10 carbon atoms, and more preferably a monovalent hydrocarbon group with 1 to 8 carbon atoms.

[0052] Specific examples of R mentioned above include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, and dodecyl; cyclohexyl groups such as cyclohexyl; aryl groups such as phenyl, naphthyl, and tolyl; and aralkyl groups such as benzyl and phenethyl. These groups are formed by replacing a portion of the hydrogen atoms bonded to the carbon atom with halogen atoms, epoxy groups, amino groups, polyether groups, cyano groups, hydroxyl groups, etc.

[0053] In these cases, when reducing curability and peel strength of the cured product, it is preferable that 80 mol% or more of the total R is methyl. When further improvement in adhesion to the film substrate is required, it is preferable that 1 to 20 mol% of the total R is aryl, more preferably 1 to 15 mol%, even more preferably 1 to 10 mol%, and still more preferably 1 to 5 mol%. Industrially, phenyl is preferred as the aforementioned aryl group.

[0054] Additionally, a portion of R may be a group containing a (meth)acryloyl group, represented by the following formula (3).

[0055] CH2=CR 1 COR 2 - (3)

[0056] However, it cannot have more than three (meth)acryloyl groups in one molecule; if it does, the peelability of the cured film decreases. 1 It can be a hydrogen atom or a methyl group, preferably a hydrogen atom. R 2 OR 3 Or by R 3 The divalent group shown, R 3 It is a divalent organic group with 1 to 20 carbon atoms, which can have branched or cyclic structures and may contain epoxy groups, ester bonds, urethane bonds, ether bonds, isocyanate bonds, and hydroxyl groups. As R 3 Examples of divalent hydrocarbon groups include linear alkylene groups such as methylene, ethylene, propyleneene, butylene, hexamethylene, octamethylene, and decene; branched alkylene groups such as methyl ethylene and methyl propyleneene; cyclic alkylene groups such as cyclohexene; alkenyl groups such as propenylene; aryl groups such as phenylene; and arylalkyl groups such as methylene phenylene and methylene phenylene. These divalent hydrocarbon groups may have ester bonds, urethane bonds, ether bonds, and isocyanate bonds between their carbon atoms. Furthermore, various divalent hydrocarbon groups with these bond involvements may be included. In addition, some or all of the hydrogen atoms in these divalent hydrocarbon groups may be replaced by epoxy groups or hydroxyl groups. Among these, R... 3 Preferred propylidene.

[0057] Additionally, P is composed of -(CH2). n The alkenyl group represented by -CH=CH2 (n is an integer from 0 to 8). n is 0 to 8, preferably 0 to 6, and more preferably 0 to 4. Specifically, vinyl, allyl, butenyl, propenyl, 5-hexenyl, octenyl, decenyl, etc. can be listed, among which vinyl is preferred.

[0058] In formula (2), α, δ, ε, ζ, and η are each independently 0 or positive numbers, β and γ are positive numbers, and 2 ≤ β + δ + ζ ≤ 4000, preferably 2 ≤ β + δ + ζ ≤ 1000. α is preferably 0 or 1 to 100, more preferably 1 to 80, and even more preferably 1 to 60. β is preferably 1 to 100, more preferably 1 to 80, and even more preferably 1 to 60. α + β is preferably 2 to 200, more preferably 2 to 100, and even more preferably 2 to 50. δ is preferably 0 or 1 to 3000, more preferably 1 to 2000, and even more preferably 1 to 1500. ζ is preferably 0 or 1 to 100, more preferably 0 or 1 to 40, and even more preferably 0 or 1 to 20.

[0059] Furthermore, γ is 5 to 27,000, preferably 10 to 20,000, more preferably 40 to 20,000, even more preferably 100 to 20,000, more preferably 500 to 15,000, and even more preferably 1,000 to 15,000. When γ is less than 10, the kinematic viscosity of the organopolysiloxane composition is too low, and the coated surface may become rough. On the other hand, if γ exceeds 27,000, the kinematic viscosity of the organopolysiloxane composition is too high, the coatability decreases, and therefore the smoothness deteriorates, and the difference in coating amount may become larger depending on the application.

[0060] Furthermore, ε is a positive number from 0 to 200, preferably a positive number from 0 to 20, and more preferably a positive number from 0 to 10. η is a positive number from 0 to 1000, preferably a positive number from 0 to 10, and more preferably a positive number from 0 to 5.

[0061] (A) The alkenyl content of component (A) is 0.001–0.7 mol / 100g, more preferably 0.002–0.5 mol / 100g, even more preferably 0.003–0.1 mol / 100g, and even more preferably 0.005–0.07 mol / 100g. If the alkenyl content is less than 0.001 mol / 100g, the reaction sites are reduced excessively, sometimes resulting in poor curing. If the alkenyl content exceeds 0.7 mol / 100g, the crosslinking density may increase excessively, the low-speed peeling force may increase excessively, or it may become difficult to peel.

[0062] The number average molecular weight of component (A) is preferably 800 or more and 2 million or less, more preferably 3,000 or more and 1 million or less. When preparing a composition using a diluent of component (E), more favorable results are obtained by increasing the number average molecular weight of component (A) to 10,000 or more. If the number average molecular weight of component (A) is lower than 800, the coating amount on the substrate may sometimes become insufficient. Furthermore, if it exceeds 2 million, workability may sometimes decrease. Moreover, in this invention, the number average molecular weight can be determined as the number average molecular weight converted from polystyrene obtained by gel permeation chromatography (GPC) analysis (solvent: toluene) (hereinafter the same).

[0063] In this invention, the number-average molecular weight obtained by GPC analysis is the value measured under the following conditions.

[0064] Device: HLC-8320 high-speed GPC system manufactured by Tosoh Corporation

[0065] Analytical column: TSKgelSuperHZ manufactured by Tosoh Corporation

[0066] Developing solvent: Toluene

[0067] Flow rate: 0.35 mL / min

[0068] Column temperature: 40℃

[0069] Sample input: 2500 μL

[0070] Detector: RI

[0071] Molecular weight calculation: The converted molecular weight of polystyrene was calculated using a calibration curve derived from the analytical values ​​of standard polystyrene samples.

[0072] The viscosity of component (A) at 25°C, as measured by a rotational viscometer, is preferably 7 mPa·s or higher, and the viscosity at 30% by mass dissolved in toluene (the viscosity of a solution in which 30% by mass of the organopolysiloxane is dissolved in toluene) is 70,000 mPa·s or lower, more preferably 10 mPa·s or higher, and the viscosity at 30% by mass dissolved in toluene is 60,000 mPa·s or lower, even more preferably 30 mPa·s or higher, and the viscosity at 30% by mass dissolved in toluene is 50,000 mPa·s or lower, and even more preferably 50 mPa·s or higher, and the viscosity at 30% by mass dissolved in toluene is 40,000 mPa·s or lower. When preparing a composition using a diluent of component (E), more preferred results are obtained by increasing the viscosity of component (A) at 25°C, as measured by a rotational viscometer, to 30,000 mPa·s or higher, or the viscosity at 30% by mass dissolved in toluene to 100 mPa·s or higher. If the viscosity is less than 7 mPa·s, the coating amount may become insufficient. In addition, workability may be reduced when the viscosity of a 30% by mass toluene solution exceeds 70,000 mPa·s.

[0073] In this invention, the viscosity of component (A) is a value measured using a BM-type viscometer (e.g., manufactured by Tokyo Keiki Co., Ltd.). It should be noted that the rotor, rotational speed, and rotation time are appropriately selected based on conventional methods according to the viscosity.

[0074] The viscosity of a solution in which 30% by mass of organopolysiloxane is dissolved in toluene is determined by adding 150g of organopolysiloxane to 350g of toluene, mixing and stirring until the organopolysiloxane dissolves, and then measuring the viscosity as described above.

[0075] Specifically, examples of such component (A) include siloxanes containing two-terminal alkenyl groups, siloxanes containing side-chain alkenyl groups, siloxanes containing both single-terminal and side-chain alkenyl groups, siloxanes containing both two-terminal and side-chain alkenyl groups, siloxanes containing branched-terminal alkenyl groups, and siloxanes containing both branched-terminal and side-chain alkenyl groups.

[0076] As examples of the aforementioned organopolysiloxanes, organopolysiloxanes represented by the following structural formulas can be listed.

[0077] M Vi 2D γ MM Vi D γ M2D γ D Vi δ MM Vi D γ D Vi δ M Vi 3D γ T1, MM Vi 2Dγ T1, M Vi 4D γ T2, M Vi 2D γ D Vi δ M Vi 2D γ Q1, MM Vi D γ Q1, M α D γ D Vi δ T Vi ζ M α M Vi α D γ D Vi δ T Vi ζ

[0078] (M、M vi D, D Vi T, T vi Q, γ, δ, and ζ are the same as in equation (2) above. (The same applies below.)

[0079] Furthermore, the following examples can be cited as specific structural examples.

[0080] M Vi 2D 100 M2D 97 D Vi 3. MM Vi D 97 D Vi 3. M2D 26 D Vi 4. M2D 96 D Vi 4. M2D 95 D Vi 5. MM Vi D 95 D Vi 5. M Vi 3D 100 T1, M Vi 4D 100 T2, MM Vi D 100 T2, M Vi 2D 97 D Vi 1. MM Vi D 97 D Vi 1. M Vi 2D 95 DVi 3. MM Vi D 95 D Vi 3. M3D 93 D Vi 3T Vi 1. M2M Vi D 93 D Vi 3T Vi 1. M Vi 2D 20000 MM Vi D 20000 M2D 10000 D Vi 20 MM Vi D 10000 D Vi 20 M Vi 2D 100 γ Q 1 MM Vi D 200 Q1.

[0081] [(B) Component]

[0082] Component (B) is an organohydrogen polysiloxane having an average of two or more hydrogen atoms bonded to silicon atoms (Si-H groups) per molecule and no more than three (meth)acryloyl groups per molecule (i.e., excluding component (C) described later), and can be used alone or in appropriate combinations of two or more. An organohydrogen polysiloxane crosslink is formed by the addition reaction of the Si-H groups of this organohydrogen polysiloxane with the alkenyl groups of component (A).

[0083] In the organohydrogen polysiloxane of component (B), the number of hydrogen atoms (Si-H groups) bonded to silicon atoms in one molecule is preferably 3 to 100, more preferably 10 to 80.

[0084] Furthermore, the Si-H group content is preferably 0.001 to 3.5 mol / 100g, more preferably 0.01 to 2.5 mol / 100g, even more preferably 0.02 to 2.0 mol / 100g, and even more preferably 0.1 to 1.7 mol / 100g. If the Si-H group content is too low, the curing and adhesion may become poor; if it is too high, the peeling force may become heavy.

[0085] The organohydrogen polysiloxane as component (B) preferably has a structure represented by the following formula (4).

[0086] M ο M H π Dρ D H σ T τ T H φ Q χ (4)

[0087] In the formula, M is R'3SiO 1 / 2 M H R'2HSiO 1 / 2 D is R'2SiO 2 / 2 D H R'HSiO 2 / 2 T is R'SiO 3 / 2 T H HSiO 3 / 2 Q is SiO 4 / 2 R' is an unsubstituted or substituted monovalent hydrocarbon group with 1 to 12 carbon atoms that does not have aliphatic unsaturated bonds. ο, π, ρ, and τ are each independently 0 or positive numbers, with π being 0 or a positive number from 1 to 40, σ being a positive number from 0 to 100, φ being a positive number from 0 to 10, and χ being a positive number from 0 to 10. π, σ, and φ are not simultaneously 0; 2 ≤ π + σ + φ ≤ 100.

[0088] In the above formula (4), R' can represent the same group as R in the above formula (2), among which, a monovalent hydrocarbon group having 1 to 8 carbon atoms is preferred.

[0089] Specific examples of the aforementioned monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, and dodecyl; cyclohexyl groups such as cyclohexyl; aryl groups such as phenyl, naphthyl, and tolyl; and aralkyl groups such as benzyl and phenethyl. Groups in which some hydrogen atoms bonded to carbon atoms are replaced by halogen atoms, epoxy groups, or polyether groups are also included.

[0090] When further improved adhesion to the membrane substrate is required, it is preferable that 5 to 30 mol% of the total amount of R' and H is aryl, more preferably in the range of 6 to 25 mol%. Phenyl is industrially preferred as the aryl group.

[0091] In the above formula (4), ο, π, ρ, and τ are each independently 0 or a positive number. ο is preferably 0 or 1 to 10, more preferably 0 or 1 to 8, and even more preferably 0 or 1 to 5. π is preferably 0 or 1 to 10, more preferably 0 or 1 to 8, and even more preferably 0 or 1 to 5. ο+π is preferably 2 to 12, more preferably 2 to 10. ρ is preferably 0 or 1 to 100, more preferably 0 or 1 to 8, and even more preferably 0 or 1 to 5. τ is preferably 0 or 1 to 10, more preferably 1 to 8, and even more preferably 1 to 5. Additionally, σ is a positive number from 0 to 100, preferably 2 to 100, and even more preferably 10 to 80. φ is a positive number from 0 to 10, preferably 0 to 5, and χ is a positive number from 0 to 10, preferably 0 to 5. Furthermore, π, σ, and φ are not all 0 simultaneously; π+σ+φ is 3 to 100, preferably 10 to 80.

[0092] Specifically, the organohydrogen polysiloxanes that are component (B) include siloxanes containing two-terminal hydrosilyl groups, siloxanes containing side-chain hydrosilyl groups, siloxanes containing both single-terminal and side-chain hydrosilyl groups, siloxanes containing both two-terminal and side-chain hydrosilyl groups, siloxanes containing branched hydrosilyl terminal groups, and siloxanes containing both branched terminal and side-chain hydrosilyl groups.

[0093] As examples of the aforementioned organohydrogen polysiloxanes, organohydrogen polysiloxanes represented by the following structural formulas can be listed.

[0094] M H 2D ρ M2D H σ M2D ρ D H σ M H 2D ρ D H σ M H 3D ρ T1, M H 4D ρ T2, M ο D ρ D H σ T H φ M ο D ρ D H σ T H φ Q χ (M、M H D, D H T, T H Q, ο, ρ, σ, φ, χ are the same as in equation (4) above. (The same applies below.)

[0095] Furthermore, as specific structural examples, the following examples can be listed.

[0096] M H 2D 10 M H 2D 100 M2D H 80 M2D 27 D H 3. M2D 97 D H 3. M2D 26 D H 4. M2D 25 D H 5. M2D 24 D H 6. M2D 96 D H 4. M2D 95 D H 5. M H 3D 100 T1, M H 4D 100 T2, M H 2D 97 D H 1. M H 2D 95 D H 3. M3D 93 D H 3T H 1. M5D 10 D H 40 T1Q1, M5D 10 D H 40 T H 1Q1, M H 5D 10 D H 40 T1Q1, M2D H 30 M2D H 60

[0097] The number average molecular weight of component (B) is preferably 194 to 10,000, more preferably 874 to 5,000. If the number average molecular weight of component (B) is too small, the adhesion may deteriorate significantly. If it is too large, the reactivity will be poor and the curing properties will be reduced. Sometimes, a decrease in residual adhesion and an increase in peel strength due to insufficient curing are observed.

[0098] (B) The kinematic viscosity of the components, measured using an Orthocrites viscometer at 25°C, is preferably 2–500 mm³. 2 / s, more preferably 2 to 300 mm 2 / s, further optimized to 5-200mm 2 / s. If the kinematic viscosity at 25°C is less than 2 mm² / s. 2 If the molecular weight is low (e.g., 500 mm²), the reactivity is good, but sometimes the adhesion to the substrate deteriorates. Additionally, if the molecular weight exceeds 500 mm², the molecular weight may be low. 2 / s, reactivity deteriorates, curing properties decrease, and sometimes a decrease in residual adhesion rate and an increase in peel force due to insufficient curing are observed.

[0099] The amount of component (B) in the mixture is approximately 1.0 to 10.0 times the molar amount of alkenyl groups in component (A), preferably 1.2 to 6.0 times, more preferably 1.5 to 6.0 times, and even more preferably 2.0 to 6.0 times, relative to the molar amount of Si-H groups in component (B). If component (B) is too small, the curing and adhesion become insufficient; if it is too large, the amount of residual Si-H groups increases, thus increasing the peel strength. The duration of Si-H group reduction also leads to variations in peel strength over time.

[0100] [(C) Component]

[0101] The (C) component of this invention is a non-organopolysiloxane compound having one or more (meth)acryloyl groups in one molecule and a molecular weight of 72 to 1000, and / or an organopolysiloxane having three or more (meth)acryloyl groups in one molecule, wherein the organopolysiloxane is a compound whose weight-average molecular weight, calculated from polystyrene by gel permeation chromatography (GPC) analysis (solvent: toluene), is 500 or more and 20,000 or less. The above-mentioned (C) component can be used alone or in appropriate combinations of two or more. The upper limit of the weight-average molecular weight of the above-mentioned (C-2) component is preferably 10,000 or less, more preferably 5,000 or less. Furthermore, if the molecular weight of the (C) component is a siloxane, it can be used... 29 Si-NMR determination. For Si-NMR, the Win Lambda instrument manufactured by NEC Corporation can be used, for example. The determination method involves placing 1.5 g of sample and 3.5 g of d-chloroform in a 10 mm diameter Teflon (registered trademark) sample tube, stirring thoroughly, setting it to the Si-NMR spectrometer, and performing the determination with 600 cumulative measurements.

[0102] As compounds other than (C-1) organopolysiloxanes, compounds having one (meth)acryloyl group are shown, represented by the following formula (5).

[0103] CH2=CR 4COOR 5 (5)

[0104] (where R is in the formula) 4 R is a hydrogen atom or a methyl group. 5 It is a hydrogen atom, or an alkyl, aryl, or aralkyl group having 1 to 20 carbon atoms, and may have a branched or cyclic structure, and may contain epoxy groups, urethane bonds, ether bonds, isocyanate bonds, or hydroxyl groups.

[0105] As R 5 Specific examples include methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, phenyl, dicyclopentyl, dicyclopentenyl, furfuryl, tetrahydrofuryl, tetrahydropyranyl, -CH2CH2-OH, -CH2CH(CH3)-OH, -CH2CH2-NCO, etc. As R 5 Examples of compounds containing epoxy groups include the following. Furthermore, compounds containing both (meth)acryloyl and epoxy groups can be oligomers.

[0106] Specific examples of compounds having a molecular weight of 72 to 1000 and having one (meth)acryloyl group include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, acrylic acid, butyl acrylate, methyl acrylate, ethyl acrylate, etc.

[0107] Specific examples of compounds having (meth)acryloyl and epoxy groups include 4-hydroxybutyl acrylate glycidyl ether.

[0108] Specific examples of molecules with a molecular weight of 200 to 1000 having two (meth)acryloyl groups include tetraethylene glycol diacrylate, nonaethylene glycol diacrylate, tetradecylethylene glycol diacrylate, tricyclodecanediethanol diacrylate, 1,10-decanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, dipropylene glycol diacrylate, heptapropylene glycol diacrylate, and trimethylolpropane triacrylate.

[0109] When using a (C-2) organopolysiloxane as the (C) component, it is preferable that it does not have aliphatic unsaturated bonds other than the (meth)acryloyl group. It should be noted that the term (meth)acryloyl group refers to acryloyl or methacryloyl. Preferably, it contains an acryloyl group. More preferably, at least one (meth)acryloyl group exists as a substituent on a difunctional siloxane unit and / or a trifunctional siloxane unit.

[0110] Examples of organopolysiloxanes include cyclic siloxanes and organopolysiloxanes with straight-chain and branched structures.

[0111] Furthermore, the (C-2) organopolysiloxane preferably has three or more siloxane units with (meth)acryloyl groups, more preferably three to six. Moreover, it is preferable that it does not have Si-H groups or alkenyl groups.

[0112] As a cyclic siloxane, it is preferably represented by the following structural formula (6).

[0113] D 1A d' (6)

[0114] (where D is in the formula) 1A For R 6 ASiO 2 / 2 R 6 Each is independently an unsubstituted or substituted monovalent hydrocarbon group, or an alkoxy group, hydrogen atom, hydroxyl group, epoxy group, or polyoxyalkylene group, having 1 to 18 carbon atoms, and A is CH2=CR. 1 COR 2 -, R 1 R is a hydrogen atom or a methyl group. 1 OR 3 or R 3 R 3 It is a divalent 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. d' is 3 to 6.

[0115] As an organopolysiloxane having a straight-chain and branched structure, an organopolysiloxane having three or more (meth)acryloyl groups in the side chain, represented by the following formula (7), is preferred.

[0116] M 1 a M 1A b D 1 c D 1A d T 1 e T 1A f Q 1 g (7)

[0117] (where M is in the formula) 1 For R 6 3SiO 1 / 2 M 1A For R 6 2ASiO 1 / 2 D 1 For R 6 2SiO 2 / 2 D 1A For R 6 ASiO2 / 2 T 1 For R 6 SiO 3 / 2 T 1A AsiO 3 / 2 Q 1 SiO 4 / 2 R 6 Each group is independently an unsubstituted or substituted monovalent hydrocarbon group, or an alkoxy group, hydrogen atom, hydroxyl group, epoxy group, or polyoxyalkylene group, having 1 to 18 carbon atoms. A is CH2=CR 1 COR 2 -, R 1 R is a hydrogen atom or a methyl group. 2 OR 3 or R 3 R 3 This is a divalent group with 1 to 20 carbon atoms, which can have branched or cyclic structures and may contain epoxy groups, ester bonds, urethane bonds, ether bonds, isocyanate bonds, and hydroxyl groups. 'a' is an integer from 0 to 20, 'b' is an integer from 0 to 5, when 'a' is 0, 'b' is an integer from 2 to 5, when 'a' is 1, 'b' is an integer from 1 to 5, and when 'a' is 2 to 20, 'b' is an integer from 0 to 5. 'c' is an integer from 0 to 300, 'd' is an integer from 0 to 200, 'e' and 'f' are both integers from 0 to 10, 'g' is 0 to 5, and 'b+d+f' is 3 or more.

[0118] In equations (6) and (7) above, R 6 Each group is independently an unsubstituted or substituted monovalent hydrocarbon group, or an alkoxy group, a hydrogen atom, a hydroxyl group, an epoxy group, or a polyoxyalkylene group, having 1 to 18 carbon atoms. A monovalent hydrocarbon group with 1 to 12 carbon atoms is preferred, and a monovalent hydrocarbon group with 1 to 8 carbon atoms is more preferred. Specifically, examples of monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, and dodecyl; alkenyl groups such as vinyl, allyl, butenyl, propenyl, 5-hexenyl, octenyl, and decenyl; cyclohexyl groups such as cycloalkyl; aryl groups such as phenyl, naphthyl, and tolyl; and aralkyl groups such as benzyl and phenethyl. These groups are formed by substituting the hydrogen atoms bonded to the carbon atoms with halogen atoms, epoxy groups, amino groups, polyether groups, cyano groups, hydroxyl groups, etc. Specifically, examples of alkoxy groups include methoxy, ethoxy, propoxy, and butoxy. Examples of polyoxyalkylene groups include polyoxyvinyl and polyoxypropylene groups.

[0119] Among them, R 1 It can be a hydrogen atom or a methyl group, preferably a hydrogen atom. R 2 OR 3 or R 3 R 3It is a divalent 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 3 Specifically, examples include linear alkylene groups such as methylene, ethylene, propylene, butylene, hexamethylene, octamethylene, and decene; branched alkylene groups such as methyl ethylene and methyl propyleneene; cyclic alkylene groups such as cyclohexene; alkenyl groups such as propenylene; aryl groups such as phenylene; and divalent hydrocarbon groups such as methylene phenylene and methylene phenylmethylene. Furthermore, ester bonds, urethane bonds, ether bonds, and isocyanate bonds may exist in these divalent hydrocarbon groups, and they can be used in combination. In addition, some or all of the hydrogen atoms in these divalent hydrocarbon groups can be replaced by epoxy groups or hydroxyl groups. Among these, R... 3 Preferred propylidene.

[0120] In equation (7), a is an integer from 0 to 20, b is an integer from 0 to 5, b is an integer from 2 to 5 when a is 0, b is an integer from 1 to 5 when a is 1, and b is an integer from 0 to 5 when a is 2 to 20. a is preferably 2 or 3, and b is preferably 0 in this case.

[0121] c is an integer from 0 to 300, preferably an integer from 5 to 200, more preferably an integer from 10 to 100, and even more preferably an integer from 15 to 70.

[0122] d is an integer from 0 to 200, preferably an integer from 3 to 50, more preferably an integer from 3 to 30, and even more preferably an integer from 3 to 20. Even if d is less than 3, it can still be implemented, but due to factors such as a small amount of catalyst, the curing property may sometimes be reduced. In addition, when d exceeds 200, the curing property may also be reduced.

[0123] Both e and f are integers from 0 to 10, preferably integers from 0 to 6, and more preferably integers from 0 to 3. When e is 10 or higher, the curing property sometimes decreases, although the reason is unclear. Similarly, when f is 10 or higher, the curing property sometimes also decreases.

[0124] The g value is 0 to 5, preferably 0 or 1. When the g value exceeds 5, viscosity control during manufacturing becomes difficult, and the peeling force increases, so it is not preferred.

[0125] Specific examples of organopolysiloxane compounds with a molecular weight of 500 or more having 3 or more (meth)acryloyl groups at (C-2) can be listed below.

[0126] D 1A 3. D 1A 4. D 1A 5. M 1 2D 1A 3D 12、M 1 3D 1A 3T 1 1、M 1 3D 1A 2T 1A 、M 1 2D 1 5D 1A 3、M 1 2D 1 20 D 1A 5、M 1Vi 2D 1 20 D 1A 5、M 1 2D 1 30 D 1A 7、M 1φ 2D 1 30 D 1A 7、M 1 2D 1 25 D 1φ

[0127] 5D 1A 7、M 1 2D 1 65 D 1A 15 、M 1Vi 2D 1 65 D 1A 15 、M 1 2D 1 61 D 1OH 4D 1A 15 、M 1 2D 1 63 D 1OSiR’ 2D 1A 15 、M 1H 2D 1 65 D 1A 15 、M 1 1M 1A 1D 1 10 D 1A 3、M 1OSiR’ 2D 1 20 D 1A 5、M 1 2D1 20 D 1A 5. M 1 2D 1 32 D 1A 5. M 1A 2D 1 37 D 1A 8. M 1 3D 1 20 D 1A 5T 1 1. M 1 3D 1 110 D 1A 6T 1 1. M 1 2D 1 170 D 1A 22 M 1 2D 1 170 D 1A 20 Q 1 1. M 1 3D 1 180 D 1A 18 T 1 1 (where M is the formula) 1Vi For R 7 2(CH2=CH)SiO 1 / 2 M 1φ For R 7 2(C6H5)SiO 1 / 2 M 1H For R 7 2(H)SiO 1 / 2 M 1OSiR’ For R 7 2(OSiR 8 3) SiO 1 / 2 D 1φ For R 7 (C6H5)SiO 2 / 2 D 1OH For R 7 (OH)SiO 2 / 2 D 1OSiR’ For R 7 (OSiR 8 3) SiO 2 / 2 T 1 For R 7 SiO 3 / 2 T 1AAsiO 3 / 2 Q 1 SiO 4 / 2 R 7 R 8 Alkyl groups having 1 to 6 carbon atoms, such as methyl and ethyl, are used; (C6H5) represents a phenyl group. A is the same as in formula (7) above.

[0128] Regarding the amount of component (C), it is 0.01 to 5.0 parts by weight relative to 100 parts by weight of component (A), preferably 0.1 to 2.0 parts by weight. If it is less than 0.01 parts by weight, the curing promotion effect is not significant. On the other hand, if it exceeds 5.0 parts by weight, the migrating components increase, and therefore a decrease in residual adhesion and a deterioration in adhesion are sometimes observed.

[0129] (C) The manufacturing method of component (M) can be achieved by mixing M 1 2. M 1 2D 1 3. M 1A 2. D 1A 4. D 1 4(M 1 M 1A D 1 D 1A Same as formula (6) above. ) and other raw materials are balanced with acid and base catalysts and dried under reduced pressure to obtain the product. At this time, it is preferable to mix with antioxidants such as phenolic substances such as dibutylhydroxytoluene, hindered amines such as tetramethylpiperidine, and aromatic secondary amines. In addition, strong acids such as sulfuric acid, fluorosulfonic acid, and trifluoromethanesulfonic acid are preferred as catalysts.

[0130] [(D) component]

[0131] As the platinum group metal catalyst (D) of the present invention, known catalysts used as addition reaction catalysts 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 platinum compounds, complexes of platinum with vinylsiloxanes, alcoholic or aldehyde solutions of chloroplatinic acid, complex salts of chloroplatinic acid with various olefins, and complexes of chloroplatinic acid with vinylsiloxanes.

[0132] The amount of component (D) is the catalytic amount. Typically, in organopolysiloxane compositions used for release paper or release films, the concentration of platinum group metals mixed in to form a cured film is 100 to 500 ppm by mass in the organopolysiloxane composition used for release paper or release films. The amount of platinum group metal catalyst mixed in this invention, relative to the total mass of the organopolysiloxane composition (the total mass of components (A) to (D)), converted to platinum group metal mass, is 1 to 100 ppm, preferably 1 to 60 ppm, more preferably 1 to 40 ppm, and most preferably 1 to 30 ppm.

[0133] [(E) component]

[0134] The diluent for component (E) is optional. When using the composition of the present invention as a solvent-free type, component (E) is not used. However, when component (A) is a high-viscosity organopolysiloxane, the use of this diluent reduces the viscosity of the composition, thereby enabling easy film coating on a substrate. Furthermore, it acts as a compatibilizer and solvent, preventing the separation of the various components constituting the organopolysiloxane composition and providing a uniformly composed coating solution. By imparting good leveling and wetting properties to the organopolysiloxane composition layer coated on various substrates, a smooth, highly slip-resistant silicone-cured film with a uniform thickness can be formed.

[0135] Especially in coatings on plastic film substrates that require a smooth surface and high transparency, component (E) is often an essential component.

[0136] As a diluent, various organic solvents can be used, including aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane and heptane, ketone solvents such as acetone and methyl ethyl ketone (also known as 2-butanone), ester solvents such as ethyl acetate, and ether solvents such as diethyl ether, all of which are soluble in organopolysiloxanes (excluding siloxane solvents); low-viscosity cyclic siloxanes such as octamethyltetrasiloxane and decamethylpentasiloxane; and M2D. p (M and D are the same as in formula (2) above, p is a number from 0 to 200, preferably from 1 to 50) and other straight-chain siloxanes, M 2+q D p T q (M, D, T are the same as in formula (2) above, p is 0 to 200, preferably 1 to 50, q is 1 to 10, preferably 1 to 3) and other branched siloxanes and other organic polysiloxanes (siloxane solvents).

[0137] When using a diluent, the viscosity is 1 to 100,000 parts by mass relative to 100 parts by mass of the organopolysiloxane in component (A). If it is less than 1 part by mass, the viscosity is too high; if it is more than 1,000,000 parts by mass, the viscosity is too low, and the coatability is reduced. More preferably, it is 1,000 to 10,000 parts by mass.

[0138] [(F)INGREDIENT]

[0139] The (F) addition reaction control agent of this invention is a component that is mixed as needed to control the catalytic activity of a platinum group metal catalyst. Examples include various organonitrogen compounds, organophosphorus compounds, alkyne compounds, oxime compounds, and organochlorine compounds. Specifically, examples include alkyne alcohols such as 1-ethynyl-1-cyclohexanol, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-penten-3-ol, and phenylbutynol; alkyne compounds such as 3-methyl-3-1-penten-1-yne and 3,5-dimethyl-1-hexyn-3-yne; alkyne compounds such as 1,1-dimethylpropionyloxytrimethylsilane and reactants of alkoxysilanes, siloxanes, or hydrosilanes; vinylsiloxanes such as tetramethylvinylsiloxane cyclic compounds; organonitrogen compounds such as benzotriazole; other organophosphorus compounds, oxime compounds; maleic acid compounds such as diallyl maleate; and organochlorine compounds.

[0140] When mixing component (F), the mixing amount relative to 100 parts by weight of component (A) is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight.

[0141] [(G) component]

[0142] As component (G), it is a component that can be formulated to improve the adhesion of the substrate. Component (G) is (G) having at least two alkenyl groups, with R 10 (3-g1) R 9 g1 SiO 1 / 2 Siloxane unit (M) R9R10 Unit), R 10 SiO 3 / 2 Siloxane unit (T R10 (Unit) (where R) 9 Each is an alkenyl group independently, R 10 Each is an independent monovalent hydrocarbon group without aliphatic unsaturated bonds, unsubstituted or halogenated atoms, or cyano-substituted groups, where g1 is an integer from 1 to 3. ) is a necessary unit, M R9R10 Unit / T R10 The molar ratio of the units satisfies 2 / 8 to 8 / 2, the viscosity at 25°C is in the range of 1 to 1000 mPa·s, and the molecular ends are M. R9R10 Unit, or M R9R10Organopolysiloxanes with a unit and a portion consisting of silanol or alkoxy groups. Preferably, the molecular ends are bonded with M. R1R2 The unit can be a silanol group or an alkoxy group, but some of them can become silanol groups or alkoxy groups to form the end.

[0143] In the above formula, R 9 Examples of alkenyl groups that are the same as P in formula (2) above can be given, among which vinyl groups are industrially preferred. Additionally, as R... 10 Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, and dodecyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl, naphthyl, and tolyl; and aralkyl groups such as benzyl and phenethyl, which are monovalent hydrocarbon groups without aliphatic unsaturated bonds. Among these, methyl and phenyl are preferred industrially. g1 is an integer from 1 to 3, preferably 1 or 2.

[0144] (G) component is the above M R9R10 Unit / T R10 The molar ratio of the units is 2 / 8 to 8 / 2, preferably 3 / 7 to 7 / 3, for organopolysiloxanes. If the above molar ratio is less than 2 / 8, the effect of improving the adhesion is sometimes smaller; if it exceeds 8 / 2, industrial production becomes difficult.

[0145] Additionally, to the extent that the effects of component (G) are not impaired, difunctional R may be included. 10 (2-g2) R 9 g2 SiO 2 / 2 The siloxane unit (where g2 is 0, 1, or 2, denoted as D) R9R10 (Unit), tetrafunctional SiO 4 / 2 Siloxane units (Q units), particularly in release films where stronger adhesion is required, are preferably M units that do not contain them. R9R10 Unit / T R10 The molar ratio of the units is 2 / 8 to 8 / 2 of siloxanes. Furthermore, in the presence of D... R9R10 In the case of a unit or Q unit, it is essential to make it relative to M. R9R10 Unit and T R10 Use the method where each unit has a smaller quantity.

[0146] Furthermore, in T R10 Unit ratio D R9R10 In terms of the number of units, the (G) component differs from the (A) component.

[0147] The alkenyl content of the organopolysiloxane in component (G) is preferably 0.01 to 2.5 mol / 100g, more preferably 0.03 to 2.0 mol / 100g, and even more preferably 0.05 to 1.5 mol / 100g. If its content is too low, the effect of improving adhesion may be reduced; if it is too high, the pot life may be shortened.

[0148] The viscosity of the organopolysiloxane of component (G) at 25°C is preferably 1–1000 mPa·s, particularly preferably 5–500 mPa·s, more preferably 10–100 mPa·s, and even more preferably 10–50 mPa·s. It is preferable to have a degree of polymerization within this viscosity range. If the viscosity is less than 1 mPa·s, the effect of improving adhesion may be less significant; if it exceeds 1000 mPa·s, the solubility or dispersibility in the composition may be reduced.

[0149] As specific examples of component (G), the following examples can be cited.

[0150] [Chemistry 1]

[0151]

[0152] (In the formula, Me represents methyl, Vi represents vinyl, and Ph represents phenyl.)

[0153] When compounding component (G), the amount of component (G) is preferably 0.1 to 20 parts by mass, more preferably 0.15 to 10 parts by mass, relative to 100 parts by mass of component (A). If it is less than 0.1 parts by mass, the effect of improving the adhesion of the substrate may be smaller, and if it is more than 20 parts by mass, the release properties of the cured film may be reduced.

[0154] Furthermore, in the case of compounding component (G), from the viewpoint of preventing a decrease in the release properties of the cured film, it is preferable to add compounding component (C) in an amount such that the ratio of the number of moles of SiH groups in component (C) to the number of moles of alkenes in component (G) (SiH group / alkene group) is 1 or more, particularly 1 to 5.

[0155] [Optional Ingredients]

[0156] In the organopolysiloxane compositions of the present invention, components that are typically blended in organopolysiloxane compositions for release paper or release film can be incorporated without impairing the effects of the present invention.

[0157] It should be noted that its properties are not diminished when diluted in organic solvents.

[0158] As optional additives, for example, for the purpose of providing slip properties, high molecular weight linear organopolysiloxanes other than components (A) to (C) can be listed; for the purpose of adjusting peel force, organosilicon resins with aryl groups, organosilicon resins, silica, low molecular weight organopolysiloxanes that do not have hydrogen atoms bonded to silicon atoms or alkenyl groups can be listed.

[0159] [Manufacturing Method]

[0160] The organopolysiloxane composition of the present invention is obtained by mixing the above-mentioned components (A) to (D) with components (E) to (G) used as needed, and optional components in specified amounts.

[0161] The viscosity of the obtained organopolysiloxane composition at 25°C, as measured by an Orthocriteur viscometer, is preferably 1–100 mPa·s, more preferably 5–50 mPa·s.

[0162] [Purpose and Usage]

[0163] The organopolysiloxane composition of the present invention is applied to sheet substrates such as paper and plastic film using a coating roller (three-roller, five-roller, gravure roller, offset gravure roller, etc.) and then cured by heating using conventional methods. This forms an organosilicon-cured film of the organopolysiloxane composition of the present invention on one side of the sheet substrate, and is preferably used as a release liner, etc.

[0164] Examples of paper substrates include cellophane, polyethylene laminated paper, polyvinyl alcohol resin coated paper, and clay coated paper. Examples of plastic film substrates include films made of polyolefins such as polyethylene and polypropylene, and polyesters such as polyethylene terephthalate.

[0165] The coating amount of the organopolysiloxane composition only needs to be sufficient to form a cured silicone film on the surface of the sheet substrate, for example, 0.1 to 50.0 g / m². 2 Approximately. Excessive coating can sometimes lead to a decrease in peelability.

[0166] The conditions for heat curing vary depending on the type of substrate and the amount of coating. By heating at 80–200°C, preferably 100–180°C for 1–60 seconds, preferably 2–30 seconds, a cured film can be formed on the substrate.

[0167] The peel force of tesa7475 tape (tesa UK Ltd.) is preferably 0.4N or less, more preferably 0.10 to 0.40N. The peel force of BPS-5127 transfer method is preferably 0.1N or less, more preferably 0.04 to 0.1N.

[0168] The residual adhesion rate is preferably above 91%, and more preferably above 94%.

[0169] Example

[0170] The following examples and comparative examples illustrate the invention in detail, but the invention is not limited to the examples described below. Furthermore, the average molecular weights listed below are... 29 The viscosity was determined by Si-NMR, and the values ​​were measured using a rotational viscometer at 25°C. The kinematic viscosity was also measured using an Orthocriteur viscometer at 25°C.

[0171] [Ingredients Used]

[0172] (A)Ingredients

[0173] ·Methylvinyl polysiloxane (A1)

[0174] The following is a polysiloxane with a vinyl value of 0.0073 mol / 100 g and a viscosity of 20000 mPa·s at 25 °C in a 30% by mass toluene solution.

[0175] {(CH2=CH)3SiO 1 / 2}2{(CH2=CH)(CH3)SiO 2 / 2} 48 {(CH3)2SiO 2 / 2} 10000

[0176] • Methyl vinyl polysiloxane (A2): without a siloxane unit represented by formula (1)

[0177] The following is a polysiloxane with a vinyl value of 0.0067 mol / 100 g and a viscosity of 20000 mPa·s at 25 °C in a 30% by mass toluene solution.

[0178] {(CH2=CH)(CH3)2SiO 1 / 2}2{(CH2=CH)(CH3)SiO 2 / 2} 48 {(CH3)2SiO 2 / 2} 10000

[0179] • Methyl vinyl polysiloxane (A3)

[0180] The following is a polysiloxane with a vinyl content of 0.051 mol / 100 g and a viscosity of 400 mPa·s at 25 °C.

[0181] {(CH2=CH)3SiO 1 / 2}2{(CH3)2SiO 2 / 2} 155

[0182] • Methyl vinyl polysiloxane (A4): A polysiloxane with a vinyl value of 0.017 mol / 100 g and a viscosity of 400 mPa·s at 25 °C, without a siloxane unit represented by formula (1).

[0183] {(CH2=CH)(CH3)2SiO 1 / 2}2{(CH3)2SiO 2 / 2} 155

[0184] • Methylphenylvinyl polysiloxane (A5): No siloxane unit represented by formula (1)

[0185] The following polysiloxane has a vinyl value of 0.002 mol / 100 g, a phenyl content of 2 mol%, and a viscosity of 800 mPa·s at 25 °C in a 30% by mass toluene solution.

[0186] {(CH2=CH)(CH3)2SiO 1 / 2}2{(CH2=CH)(CH3)SiO 2 / 2}6{(CH3)2SiO 2 / 2} 5000 {(C6H5)2SiO 2 / 2} 77

[0187] ·Methylphenylvinyl polysiloxane (A6)

[0188] The following polysiloxane has a vinyl value of 0.018 mol / 100 g, a phenyl content of 10 mol%, and a viscosity of 10000 mPa·s at 25 °C in a 30% by mass toluene solution.

[0189] {(CH2=CH)3SiO 1 / 2}2{(CH2=CH)(CH3)SiO 2 / 2} 80 {(CH3)2SiO 2 / 2} 5000 {(C6H5)2SiO 2 / 2} 550

[0190] (B) Ingredients

[0191] • Methylhydropolysiloxane (B1)

[0192] The molecular chain is capped at both ends by trimethylsilyloxy groups, and is composed of (CH3)HSiO 2 / 2 Unit and (CH3)2SiO 2 / 2The unit cell has a Si-H group content of 1.42 mol / 100g and a kinematic viscosity of 110 mm. 2 / s of methylhydropolysiloxane

[0193] {(CH3)3SiO 1 / 2}2{(CH3)HSiO 2 / 2} 90 {(CH3)2SiO 2 / 2} 10

[0194] • Methylhydropolysiloxane (B2)

[0195] The molecular chain is capped at both ends by trimethylsilyloxy groups, and the Si-H group content, consisting entirely of (CH3)HSiO units except at both ends, is 1.59 mol / 100g. The kinematic viscosity is 35 mm. 2 / s of methylhydropolysiloxane

[0196] {(CH3)3SiO 1 / 2}2{(CH3)HSiO 2 / 2} 60

[0197] ·Methylphenylhydropolysiloxane (B3)

[0198] The molecular chain is capped at both ends by trimethylsilyloxy groups, and the remaining components are all composed of (CH3)HSiO units and (C6H5)2SiO units. The Si-H group content is 1.19 mol / 100g, the phenyl content is 10 mol%, and the kinematic viscosity is 100 mm. 2 / s of methylphenylhydropolysiloxane

[0199] {(CH3)3SiO 1 / 2}2{(CH3)HSiO 2 / 2} 73 {(C6H5)2SiO 2 / 2}8

[0200] ·Methylphenylhydropolysiloxane (B4)

[0201] The molecular chain is capped at both ends by trimethylsilyloxy groups, and the remaining components are all composed of (CH3)HSiO units and (C6H5)2SiO units. The Si-H group content is 0.84 mol / 100g, the phenyl content is 22 mol%, and the kinematic viscosity is 120 mm. 2 / s of methylphenylhydropolysiloxane

[0202] {(CH3)3SiO 1 / 2}2{(CH3)HSiO 2 / 2} 70{(C6H5)2SiO 2 / 2} 20

[0203] (C) Components

[0204] Acrylic acid (C1): HOOCH=CH2; Molecular weight 72

[0205] • 2-Ethylhexyl acrylate (C2):

[0206] CH2=CH-(CO)-O-CH2CH(C2H5)C4H9; Molecular weight 213.5

[0207] • 2-Hydroxyethyl acrylate (C3):

[0208] CH2=CH-(CO)-O-CH2CH2OH; Molecular weight 116

[0209] • 4-Hydroxybutyl acrylate glycidyl ether (C4):

[0210] A compound represented by the following formula having an acryloyl group at one end and a glycidyl ether group at the other end; molecular weight 200

[0211] [Chemistry 2]

[0212]

[0213] Polysiloxanes containing (meth)acryloyl groups

[0214] M 3 2D 3 170 D 3A 22 (C5); weight-average molecular weight 16526

[0215] M 3 3D 3 110 D 3A 6T 3 1(C6); weight-average molecular weight 9482

[0216] M 3 3D 3 180 D 3A 18 T 3 1(C7); weight-average molecular weight 16726

[0217] M 3A 2D 3 37 D 3A 8(C8); weight-average molecular weight 4472

[0218] M 3 2D 3 20 D 3A 5(C9); weight-average molecular weight 2502

[0219] M 3 2D 3 20 D 3MA 5 (C10); weight-average molecular weight 2516

[0220] D 3A 4(C11); weight-average molecular weight 689

[0221] T 3 0.6 T 3A 4.4 (OR 11 7(C12); weight-average molecular weight 928

[0222] (M in the chemical formula) 3 For R 11 3SiO 1 / 2 M 3A For R 11 2A 1 SiO 1 / 2 D 3 For R 11 2SiO 2 / 2 D 3A For R 11 A 1 SiO 2 / 2 D 3MA For R 11 (MA)SiO 2 / 2 T 3 For R 11 SiO 3 / 2 T 3A For A 1 SiO 3 / 2 R 11 A is a methyl group. 1 For CH2=CHCOO(CH2)3-, M A (It is CH2=CCH3COO(CH2)3-.)

[0223] Other added ingredients (comparative examples)

[0224] M 3A 2D 3 1(C13); weight-average molecular weight 432

[0225] (M in the chemical formula) 3A For R 112A 1 SiO 1 / 2 D 3 For R 11 2SiO 2 / 2 R 11 A is a methyl group. 1 (It is CH2=CHCOO(CH2)3-.)

[0226] (F)Ingredients

[0227] 3-Methyl-1-butyn-3-ol (F1)

[0228] 1-Ethynyl-1-cyclohexanol (F2)

[0229] (G) component

[0230] The viscosity at 25℃ is 30 mPa·s. The molecular chain is mainly capped with dimethylvinylsilyl groups and consists of (CH3)2CH2=CHSiO. 1 / 2 Unit 50 mol% and CH3SiO 3 / 2 Organopolysiloxane (G1) composed of 50 mol% units (vinyl content = 0.6 mol / 100g)

[0231] (H) component

[0232] Perhexa C (manufactured by Nippon Oils & Fats Co., Ltd., 1,1-di(tert-butylperoxy)cyclohexane (H1), 10-hour half-life temperature 90.7°C, heating start temperature 134°C)

[0233] 1)(C) Comparison of the effects of ingredients

[0234] 1-1) Evaluation using solvent-based composition

[0235] [Example 1]

[0236] 100 parts by weight of methyl vinyl polysiloxane (A1) as component (A), 1.54 parts by weight of methyl hydrogen polysiloxane (B1) as component (B), and polysiloxane D with acryloyl groups on the side chain as component (C) are added. 3A 1.3 parts by mass of 4(C11), 1200 parts by mass of toluene and hexane as component (E), and 3 parts by mass of 3-methyl-1-butyn-3-ol (F1) as component (F) were stirred until homogeneous. Then, a platinum-vinylsiloxane complex as component (D) was added so that the total mass of components (A), (B), (C), and (D), converted to platinum atomic mass, was 80 ppm. The mixture was stirred until homogeneous to prepare a product with a viscosity of 10 mm. 2An organopolysiloxane composition having a ratio of / s, H / Vi (the ratio of Si-H groups in component (B) to alkenes in component (A) is 3.)

[0237] [Example 2]

[0238] Except for being replaced by 1.3 parts by weight of 4-hydroxybutylacrylate glycidyl ether (C4) as component (C), a viscosity of 10 mm was prepared using the same method as in Example 1. 2 An organopolysiloxane composition with H / Vi = 3 / s and H / Vi = 3.

[0239] [Example 3]

[0240] In addition to changing component (C) to a polysiloxane M with acryloyl groups on the side chain... 3 2D 3 170 D 3A 22 Apart from (C5) 1.3 parts by weight, a viscosity of 10 mm was prepared using the same method as in Example 1. 2 An organopolysiloxane composition with H / Vi = 3 / s and H / Vi = 3.

[0241] [Example 4]

[0242] In addition to changing component (C) to a polysiloxane M with acryloyl groups on the side chain... 3 3D 3 180 D 3A 18 T 3 Apart from 1.3 parts by weight of (C7), a viscosity of 10 mm was prepared using the same method as in Example 1. 2 An organopolysiloxane composition with H / Vi = 3 / s and H / Vi = 3.

[0243] [Example 5]

[0244] In addition to changing component (C) to a polysiloxane M with acryloyl groups at the ends and side chains. 3A 2D 3 37 D 3A Apart from 1.3 parts by weight of 8(C8), a viscosity of 10 mm was prepared using the same method as in Example 1. 2 An organopolysiloxane composition with H / Vi = 3 / s and H / Vi = 3.

[0245] [Example 6]

[0246] In addition to changing component (C) to a polysiloxane M with acryloyl groups on the side chain... 3 2D 3 20 D3A Apart from 5 (C9) 4 parts by weight, a viscosity of 10 mm was prepared using the same method as in Example 1. 2 An organopolysiloxane composition with H / Vi = 3 / s and H / Vi = 3.

[0247] [Example 7]

[0248] In addition to changing component (C) to a polysiloxane M with acryloyl groups on the side chain... 3 2D 3 20 D 3A Apart from 0.3 parts by weight of 5 (C9), a viscosity of 10 mm was prepared using the same method as in Example 1. 2 An organopolysiloxane composition with H / Vi = 3 / s and H / Vi = 3.

[0249] [Example 8]

[0250] In addition to changing component (C) to a polysiloxane T containing acryloyl groups 3 0.6 T 3A 4.4 (OR 7 Apart from 0.3 parts by weight of 7 (C12), a viscosity of 10 mm was prepared using the same method as in Example 1. 2 An organopolysiloxane composition with H / Vi = 3 / s and H / Vi = 3.

[0251] [Example 9]

[0252] A platinum and vinylsiloxane complex was added as component (D) to make the total mass relative to components (A), (B), (C), (D), and (E), converted to platinum atomic mass, 30 ppm. The mixture was stirred until homogeneous, and a viscosity of 10 mm was prepared using the same method as in Example 1. 2 An organopolysiloxane composition with H / Vi = 3 / s and H / Vi = 3.

[0253] [Reference Example 1]

[0254] 100 parts by mass of methyl vinyl polysiloxane (A1) as component (A), 1.54 parts by mass of methyl hydrogen polysiloxane (B1) as component (B), 1200 parts by mass of toluene and hexane as component (E), and 3 parts by mass of 3-methyl-1-butyn-3-ol (F1) as component (F) were added. The mixture was stirred until homogeneous. Then, as component (D), a platinum-vinyl siloxane complex was added so that the total mass of components (A), (B), (C), and (D), converted to platinum atomic mass, was 160 ppm. The mixture was stirred until homogeneous to prepare a product with a viscosity of 10 mm. 2An organopolysiloxane composition having a ratio of Si-H groups in component (B) to alkenes in component (A) of 3.

[0255] [Comparative Example 1]

[0256] 100 parts by mass of methyl vinyl polysiloxane (A1) as component (A), 1.54 parts by mass of methyl hydrogen polysiloxane (B1) as component (B), 1200 parts by mass of toluene and hexane as component (E), and 3 parts by mass of 3-methyl-1-butyn-3-ol (F1) as component (F) were added. The mixture was stirred until homogeneous. Then, as component (D), a platinum-vinyl siloxane complex was added so that the total mass of components (A), (B), (C), and (D), converted to platinum atomic mass, was 80 ppm. The mixture was stirred until homogeneous to prepare a product with a viscosity of 10 mm. 2 An organopolysiloxane composition with H / Vi = 3 / s and H / Vi = 3.

[0257] [Comparative Example 2]

[0258] In addition to the addition of organosiloxane M with acryloyl groups at both ends as component (C), 3A 2D 3 Apart from 1.3 parts by weight of (C13), a viscosity of 10 mm was prepared using the same method as in Example 1. 2 An organopolysiloxane composition with H / Vi = 3 / s and H / Vi = 3.

[0259] [Comparative Example 3]

[0260] Except for using 100 parts by weight of methyl vinyl polysiloxane (A2) as component (A) and 1.42 parts by weight of methyl hydrogen polysiloxane (B1) as component (B), a viscosity of 10 mm was prepared using the same method as in Example 1. 2 An organopolysiloxane composition with H / Vi = 3 / s and H / Vi = 3.

[0261] The organopolysiloxane compositions obtained in the above examples (Examples 1-9, Reference Example 1, Comparative Examples 1-3) were evaluated as follows. These results, together with the above-described formulations, are listed in Tables 1-3.

[0262] [Peeling force]

[0263] An organopolysiloxane composition was coated onto a polyester film using a No. 14 rod coater and heated in a hot air dryer at 120°C for 20 seconds to obtain a film with a thickness of 0.3 g / m. 2 A peel-off film of a cured organic polysiloxane composition.

[0264] After aging the obtained release film at 25°C for 24 hours, tesa-7475 tape (tesa UK Ltd.) was adhered to the cured film surface and cut into 2.5cm × 18cm pieces to prepare test pieces. These test pieces were then clamped onto a glass plate and subjected to 20g / cm² temperature at 70°C. 2 After pressing under load for 20 hours, one end of the test piece was peeled off, and the substrate end of the tape with pressure-sensitive adhesive was stretched relative to the polyester film at an angle of 180 degrees at a peeling speed of 0.3 m / min. The force required for peeling at this time (i.e., "peel force") (N / 25 mm) was measured using a tensile testing machine (Shimadzu Corporation AGS-50G type).

[0265] [Residual Adhesion Rate]

[0266] After the peel force was measured, the tesa-7475 tape (tesa UK Ltd.) was pasted onto the SUS board, and a 2kg roller was pressed back and forth once. After 30 minutes, one end of the tesa-7475 tape was peeled off and stretched at an angle of 180 degrees relative to the SUS board. The peeling speed was 0.3m / min, and the force required for peeling was measured as the adhesion force A (N / 25mm).

[0267] As a blank, unused tesa-7475 tape was adhered to an SUS board. Similar to the above, a 2kg roller was used for one reciprocating motion to press the tape together. After 30 minutes, one end of the tesa-7475 tape was peeled off. This end was then stretched at a 180-degree angle relative to the SUS board at a peeling speed of 0.3 m / min. The force required for peeling was measured as the adhesive force B (N / 25 mm). The residual adhesion percentage (%) was calculated using (A / B) × 100.

[0268] [Curing properties]

[0269] Using a rod coater (No. 14), the organopolysiloxane composition was coated onto a polyester film, and then heated in a hot air dryer at 120°C for 20 seconds to obtain a film with a thickness of 0.3 g / m². 2 The release film of the cured film of the organopolysiloxane composition was removed from the dryer and immediately rubbed vigorously with the index finger 10 times. Red oily ink was then applied, and the staining of the ink and the state of the cured film were observed.

[0270] As a result, fingerprints that appear deep are indicated by "×", fingerprints that appear shallow are indicated by "△", and fingerprints that are almost invisible are indicated by "○".

[0271] [Migration of Organosilicon (Organopolysiloxane)]

[0272] Similar to the peel strength test, a polyester film was overlapped on the surface of a cured film of an organopolysiloxane composition formed on the surface of a polyester film. After pressing at 0.98 MPa for 20 hours at room temperature, the polyester film was separated from the cured film. A red oily ink was applied to the surface of the polyester film in contact with the cured film, and the silicone migration was evaluated based on its shrinkage.

[0273] The results of shrinkage without ink (no or very low silicone mobility) are represented by “○”, shrinkage with partial ink (low silicone mobility) is represented by “△”, and shrinkage with ink (high silicone mobility) is represented by “×”.

[0274] [Seamlessness]

[0275] After the peel film, prepared in the same manner as the peel strength test, was placed at 25°C and 50% RH for 3 days, the cured film of the organopolysiloxane composition formed on the surface of the polyester film was vigorously rubbed 10 times with the index finger, coated with red oily ink, and the staining of the ink and the state of the cured film were observed.

[0276] The results of staining without ink are indicated as follows: good adhesion is marked as "○", partial staining with ink is indicated as "△", and staining of the entire surface with ink is indicated as "×".

[0277] The release film was placed at 60°C and 90% RH for 1 day. After promoting the film under more stringent conditions in the direction of reduced adhesion, the adhesion was evaluated in the same way. In the absence of ink-induced staining, the film was specifically evaluated as having good adhesion and indicated by "◎".

[0278] [Table 1]

[0279]

[0280] [Table 2]

[0281]

[0282] [Table 3]

[0283]

[0284] *Without the siloxane unit shown in formula (1) above

[0285] 1-2) Evaluation using solvent-free composition (organic (C) components)

[0286] [Example 10]

[0287] 60 parts by mass of methyl vinyl polysiloxane (A3) and 40 parts by mass of methyl vinyl polysiloxane (A4) as component (A), 4.23 parts by mass of methyl hydropolysiloxane (B2) as component (B), 0.5 parts by mass of acrylic acid (C1) as component (C), and 0.3 parts by mass of 1-ethynyl-1-cyclohexanol (F2) as component (F) were added and stirred until homogeneous. Then, a complex of platinum and vinyl siloxane was added as component (D) so that the total mass of components (A), (B), (C), and (D), converted to platinum atomic mass, is 80 ppm. The mixture was stirred until homogeneous, and a kinematic viscosity of 401 mm was prepared. 2 A composition with a ratio of / s and H / Vi (the ratio of Si-H groups to alkenes in the composition) of 1.8.

[0288] [Example 11]

[0289] Except that component (C) was made into 0.5 parts by mass of 2-ethylhexyl acrylate (C2), a kinematic viscosity of 403 mm was prepared using the same method as in Example 11. 2 A composition with H / Vi = 1.8.

[0290] [Example 12]

[0291] Except that component (C) was made into 0.5 parts by mass of 2-hydroxyethyl acrylate (C3), a kinematic viscosity of 400 mm was prepared using the same method as in Example 11. 2 A composition with H / Vi = 1.8.

[0292] [Example 13]

[0293] Except that component (C) was made into 0.5 parts by weight of 4-hydroxybutyl acrylate glycidyl ether (C4), a kinematic viscosity of 405 mm was prepared using the same method as in Example 1. 2 A composition with H / Vi = 1.8.

[0294] [Reference Example 2]

[0295] 60 parts by mass of methyl vinyl polysiloxane (A3) and 40 parts by mass of methyl vinyl polysiloxane (A4) as component (A), 3.98 parts by mass of methyl hydropolysiloxane (B2) as component (B), and 0.3 parts by mass of 1-ethynyl-1-cyclohexanol (F2) as component (F) were added and stirred until homogeneous. Then, a complex of platinum and vinyl siloxane was added as component (D) so that the total mass of components (A), (B), and (D), converted to platinum atomic mass, was 120 ppm. The mixture was stirred until homogeneous, and a kinematic viscosity of 404 mm was prepared. 2A composition with H / Vi = 1.7.

[0296] [Comparative Example 4]

[0297] 60 parts by mass of methyl vinyl polysiloxane (A3) and 40 parts by mass of methyl vinyl polysiloxane (A4) as component (A), 4.23 parts by mass of methyl hydropolysiloxane (B2) as component (B), and 0.3 parts by mass of 1-ethynyl-1-cyclohexanol (F2) as component (F) were added and stirred until homogeneous. Then, a platinum and vinyl siloxane complex was added as component (D) so that the total mass of components (A), (B), and (D), converted to platinum atomic mass, was 80 ppm. The mixture was stirred until homogeneous, and a kinematic viscosity of 404 mm was prepared. 2 A composition with H / Vi = 1.8.

[0298] [Comparative Example 5]

[0299] 100 parts by mass of methyl vinyl polysiloxane (A4) as component (A), 1.92 parts by mass of methyl hydrogen polysiloxane (B2) as component (B), 0.5 parts by mass of acrylic acid (C1) as component (C), and 0.3 parts by mass of 1-ethynyl-1-cyclohexanol (F2) as component (F) were added and stirred until homogeneous. Then, a platinum and vinyl siloxane complex was added as component (D) so that the total mass of components (A), (B), (C), and (D), converted to platinum atomic mass, is 80 ppm. The mixture was stirred until homogeneous to prepare a product with a kinematic viscosity of 420 mm. 2 A composition with a ratio of / s and H / Vi (the ratio of Si-H groups to alkenes in the composition) of 1.8.

[0300] The organopolysiloxane compositions obtained in the above examples (Examples 10-15, Reference Example 2, Comparative Examples 4-5) were evaluated as follows. These results, together with the above-described formulations, are described in Tables 4-6.

[0301] [Peeling force]

[0302] An organopolysiloxane composition was coated onto the metal rollers of an RI tester (manufactured by IHI Machinery Systems, Ltd.). The two rollers in contact with the rubber roller were rotated for 45 seconds to uniformly stretch the composition onto the rollers. The composition was then transferred from the rubber rollers 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 Release paper of a cured film of an organopolysiloxane composition.

[0303] In this state, after aging at 25°C for 24 hours, a solvent-based acrylic pressure-sensitive adhesive BPS-5127 (manufactured by Toyo Ink Co., Ltd.) was applied to the cured film surface of the release paper (from the transfer side of the rubber roller) with a thickness of 130 μm, and then dried in a dryer at 100°C for 180 seconds. After drying, it was left at room temperature for more than 10 minutes, then high-quality paper was pasted on and cut into pieces of 5.0 cm × 18 cm. A 2 kg roller was used to apply a load to the cut pieces, and after aging at room temperature for 24 hours, one end of the test piece was peeled off. The end of the substrate with pressure-sensitive adhesive was stretched at a peel speed of 0.3 m / min at an angle of 180 degrees relative to the polyethylene laminate paper. The force required for peeling at this time (i.e., "peel force") (N / 50 mm) was measured using a tensile testing machine (Shimadzu Corporation AGS-50G model).

[0304] [Residual Adhesion Rate]

[0305] Using the same method as described above regarding peel strength, the silicone composition was transferred onto polyethylene laminated paper and cured in a dryer to obtain release paper. After aging at 23°C for 24 hours, Nitto Denko NO31B tape was pasted onto the release paper. Similarly, as a comparison, Nitto Denko NO31B tape was pasted onto a Teflon (registered trademark) board. Next, these pasted samples were subjected to a 20 g / cm³ test at 70°C. 2 The load was applied and the material was stored for 20 hours. After storage, the material was placed at 23°C for at least 30 minutes, then the strip was peeled off and bonded to a stainless steel plate. The strip was then pressed back and forth once with a 2kg roller, and the adhesion was measured using a tensile testing machine (Shimadzu Corporation AGS-50G model).

[0306] The adhesive force of the Teflon (registered trademark) board bonding tape was set as the blank value, and the ratio (%) of the measured value of the sample to the blank value was set as the residual adhesive rate (%).

[0307] [Curing properties]

[0308] Using the same method as described above for peel strength, a silicone composition was transferred onto polyethylene laminated paper and heated in a hot air dryer at 120°C for 20 seconds to obtain a product with a thickness of 0.9–1.1 g / m². 2 Release paper for the cured film of the organopolysiloxane composition. Remove the release paper from the dryer, immediately rub the cured film surface vigorously with your index finger 10 times, apply red oily ink, and observe the ink staining and the state of the cured film.

[0309] As a result, fingerprints that appear deep are indicated by "×", fingerprints that appear shallow are indicated by "△", and fingerprints that are almost invisible are indicated by "○".

[0310] [Migration of Organosilicon (Organopolysiloxane)]

[0311] A polyester film was overlapped on the surface of a cured film of an organopolysiloxane composition formed from release paper obtained in the same manner as in the peel force test. After pressing for 20 hours at room temperature under a pressure of 0.98 MPa, the polyester film was separated from the cured film. A red oily ink was applied to the surface of the polyester film in contact with the cured film, and the silicone migration was evaluated based on its shrinkage.

[0312] As a result, shrinkage without ink (silicon migration is zero or very small) is represented by “○”, shrinkage with partial ink (silicon migration is small) is represented by “△”, and shrinkage with ink (silicon migration is large) is represented by “×”.

[0313] [Seamlessness]

[0314] After the release paper, prepared in the same manner as the peel strength test, was placed at 25°C and 50% RH for 3 days, the cured film of the organopolysiloxane composition formed on the surface of the polyester film was vigorously rubbed 10 times with the index finger, and red oily ink was applied. The staining of the ink and the state of the cured film were observed.

[0315] As a result, the following classifications are applied to staining caused by no ink: good adhesion is indicated by "○", partial staining with ink is indicated by "△", and staining of the entire surface with ink is indicated by "×".

[0316] The release film was placed at 60°C and 90% RH for 1 day. After being promoted under more stringent conditions in the direction that reduces adhesion, the adhesion was evaluated in the same way. In the absence of ink-induced staining, the adhesion was particularly good and indicated by "◎".

[0317] [Table 4]

[0318]

[0319] * No siloxane unit as shown in formula (1) above

[0320] [Table 5]

[0321]

[0322] * No siloxane unit represented by the following formula (1)

[0323] 1-3) Evaluation using solvent-free composition (organosilicon (C) component)

[0324] [Example 14]

[0325] Add as component (C) an organosiloxane M having a methacryloyl group on the side chain 3 2D3 20 D 3MA 5 (C10) 1 part by mass of a complex of platinum and vinylsiloxane as component (D), such that the total mass of components (A), (B), (C) and (D), converted to platinum atomic mass, is 20 ppm. Otherwise, a viscosity of 401 mm was prepared using the same method as in Example 10. 2 An organopolysiloxane composition with H / Vi = 1.8 / s and H / Vi = 1.8.

[0326] [Example 15]

[0327] In addition to changing component (C) to a polysiloxane M with acryloyl groups on the side chain... 3 3D 3 110 D 3A 6T 3 Apart from 1 part by weight of (C6), a viscosity of 410 mm was prepared using the same method as in Example 14. 2 An organopolysiloxane composition with H / Vi = 1.8 / s and H / Vi = 1.8.

[0328] [Reference Example 3]

[0329] 60 parts by mass of methyl vinyl polysiloxane (A3) and 40 parts by mass of methyl vinyl polysiloxane (A4) as component (A), 3.98 parts by mass of methyl hydropolysiloxane (B2) as component (B), and 0.3 parts by mass of 1-ethynyl-1-cyclohexanol (F2) as component (F) were added. After stirring until homogeneous, a platinum-vinylsiloxane complex was added as component (D) so that the total mass of components (A), (B), and (D), converted to platinum atomic mass, is 120 ppm. The mixture was stirred until homogeneous, and a kinematic viscosity of 404 mm was prepared. 2 A composition with H / Vi = 1.7.

[0330] [Comparative Example 6]

[0331] 60 parts by mass of methyl vinyl polysiloxane (A3) and 40 parts by mass of methyl vinyl polysiloxane (A4) as component (A), 4.23 parts by mass of methyl hydropolysiloxane (B2) as component (B), and 0.3 parts by mass of 1-ethynyl-1-cyclohexanol (F2) as component (F) were added. After stirring until homogeneous, a platinum-vinylsiloxane complex was added as component (D) so that the total mass of components (A), (B), and (D), converted to platinum atomic mass, is 20 ppm. The mixture was stirred until homogeneous to prepare a product with a kinematic viscosity of 404 mm. 2 A composition with H / Vi = 1.8.

[0332] [Comparative Example 7]

[0333] 100 parts by weight of methyl vinyl polysiloxane (A4) as component (A), 1.92 parts by weight of methyl hydrogen polysiloxane (B2) as component (B), and an organosiloxane M having a methacrylamide group on the side chain as component (C) are added. 3 2D 3 20 D 3MA 5 parts by mass of (C10) and 0.3 parts by mass of 1-ethynyl-1-cyclohexanol (F2) as component (F) were stirred until homogeneous. Then, a complex of platinum and vinylsiloxane was added as component (D) so that the total mass of components (A), (B), (C) and (D), converted to platinum atomic mass, was 20 ppm. The mixture was stirred until homogeneous to prepare a product with a kinematic viscosity of 420 mm. 2 A composition with a ratio of / s and H / Vi (the ratio of Si-H groups to alkenes in the composition) of 1.8.

[0334] The organopolysiloxane compositions obtained in the above examples (Examples 14-15, Reference Example 3, Comparative Examples 6-7) were evaluated as follows. These results, together with the above-described formulations, are recorded in Table 6.

[0335] [Peeling force]

[0336] The above-obtained composition was coated onto the metal roller of an RI tester (manufactured by IHI Machinery Systems, Ltd.). Two rollers, consisting of a metal roller and a rubber roller, were rotated for 45 seconds to uniformly stretch the composition. The composition was then transferred from the rubber roller onto ASP cellophane (manufactured by Ahlstrom-Munksjo). The cellophane with the transferred composition was heated in a hot air dryer at 120°C for 20 seconds to obtain a cellophane with a thickness of 0.9–1.1 g / m². 2 The release paper is a cured film of the above composition. In this state, after aging at 25°C for 24 hours, tesa-7475 tape (tesa UK Ltd.) is pasted onto the surface of the cured film on the release paper (from the transfer side of the rubber roller), and cut into 2.5cm × 18cm pieces. It is then clamped to a glass plate and cured at 70°C at 20g / cm³. 2 After aging under load for 24 hours, one end of the test piece was peeled off, and the end of the substrate with pressure-sensitive adhesive was stretched relative to the cellophane at an angle of 180 degrees at a peeling speed of 0.3 m / min. The force required for peeling at this time (i.e., "peel force") (N / 50 mm) was measured using a tensile testing machine (Shimadzu Corporation AGS-50G type).

[0337] [Residual Adhesion Rate]

[0338] The tesa-7475 tape (tesa UK Ltd.) after the peel force was measured was adhered to a polyester film, and a 2kg roller was applied once to apply a load. After 30 minutes, one end of the tesa-7475 tape was peeled off, and its end was stretched relative to the polyester film at a 180-degree angle, peeling at a peeling speed of 0.3 m / min. The force required for peeling at this time was measured: peel force A (N / 25 mm).

[0339] As a blank, unused tesa-7475 tape was pasted onto the polyester film. As before, a 2kg roller was used to apply load once, and after 30 minutes, one end of the tesa-7475 tape was peeled off. This end was then stretched relative to the polyester film at a 180-degree angle at a peeling speed of 0.3 m / min. The peeling force required at this point was measured: peel force B (N / 25 mm). The residual adhesion percentage (%) was calculated using (A / B) × 100.

[0340] [Curing properties]

[0341] Take the release paper, which was made in the same manner as the release force test, out of the dryer and immediately rub the cured film surface vigorously with your index finger 10 times. Apply red universal ink and observe the ink depth and the state of the cured film.

[0342] As a result, fingerprints that appear deep are indicated by "×", fingerprints that appear shallow are indicated by "△", and fingerprints that are almost invisible are indicated by "○".

[0343] [Migration of Organosilicon (Organopolysiloxane)]

[0344] A 36 μm thick polyethylene terephthalate (PET) film was overlapped on the surface of release paper prepared in the same manner as in the peel force test. After pressing at 0.98 MPa for 20 hours at room temperature, the PET film was removed from the cured substrate. An oil-based ink (trade name: All-Purpose Ink, manufactured by Teranishi Chemical Industry Co., Ltd.) was applied to the surface of the PET film in contact with the cured substrate. The silicone migration was evaluated according to the following criteria based on its shrinkage.

[0345] As a result, shrinkage without ink: silicone migration is not present or is quite small is indicated by "○", and shrinkage with ink: silicone migration is mostly indicated by "×".

[0346] [Seamlessness]

[0347] After the release paper, prepared in the same manner as the peel strength test, was placed at 25°C and 50% RH for 3 days, the cured film of the organopolysiloxane composition formed on the surface of the polyethylene laminated paper was vigorously rubbed 10 times with the index finger, coated with red oily ink, and the staining of the ink and the state of the cured film were observed.

[0348] As a result, the following classifications are applied to staining caused by no ink: good adhesion is indicated by "○", partial staining with ink is indicated by "△", and staining of the entire surface with ink is indicated by "×".

[0349] [Table 6]

[0350]

[0351] * No siloxane unit represented by the following formula (1)

[0352] 2) Effects of ingredients containing phenyl groups

[0353] [Example 16]

[0354] 100 parts by weight of methyl vinyl polysiloxane (A1) as component (A), 1.04 parts by weight of methyl hydrogen polysiloxane (B1) as component (B), 0.60 parts by weight of methyl phenyl hydrogen polysiloxane (B3) as component (C), and a polysiloxane M having acryloyl groups on the side chain are added. 3 2D 3 20 D 3A 1.3 parts by mass of 5(C9), 1200 parts by mass of toluene and 1200 parts by mass of hexane as component (E), 3 parts by mass of 3-methyl-1-butyn-3-ol (F1) as component (F), and 0.60 parts by mass of organopolysiloxane (G1) as component (G) were stirred until homogeneous. Then, a complex of platinum and vinylsiloxane as component (D) was added so that the total mass of components (A), (B), (C), and (D), converted to platinum atomic mass, was 80 ppm. The mixture was stirred until homogeneous to prepare a product with a viscosity of 10 mm. 2 An organopolysiloxane composition with H / Vi = 2 / s.

[0355] [Example 17]

[0356] The following are added as components: 60 parts by weight of methyl vinyl polysiloxane (A1) and 40 parts by weight of methyl phenyl vinyl polysiloxane (A5) as component (A); 1.46 parts by weight of methyl hydrogen polysiloxane (B1) as component (B); and a polysiloxane M having acryloyl groups on its side chain as component (C). 3 2D 3 20 D 3A1.3 parts by mass of 5(C9), 1200 parts by mass of toluene and 1200 parts by mass of hexane as component (E), and 3 parts by mass of 3-methyl-1-butyn-3-ol (F1) as component (F) were stirred until homogeneous. Then, a complex of platinum and vinylsiloxane was added as component (D) so that the total mass relative to components (A), (B), (C), and (D), converted to platinum atomic mass, was 80 ppm. The mixture was stirred until homogeneous to prepare a product with a viscosity of 10 mm. 2 An organopolysiloxane composition with H / Vi = 4 / s.

[0357] [Example 18]

[0358] The following are added as components: 60 parts by weight of methyl vinyl polysiloxane (A1) and 40 parts by weight of methyl phenyl vinyl polysiloxane (A5) as component (A); 0.70 parts by weight of methyl hydrogen polysiloxane (B1) and 0.47 parts by weight of methyl phenyl hydrogen polysiloxane (B3) as component (B); and a polysiloxane M having acryloyl groups on its side chain as component (C). 3 2D 3 20 D 3A 1.3 parts by mass of 5(C9), 1200 parts by mass of toluene and 1200 parts by mass of hexane as component (E), 3 parts by mass of 3-methyl-1-butyn-3-ol (F1) as component (F), and 0.60 parts by mass of organopolysiloxane (G1) as component (G) were stirred until homogeneous. Then, a complex of platinum and vinylsiloxane as component (D) was added so that the total mass of components (A), (B), (C), and (D), converted to platinum atomic mass, was 80 ppm. The mixture was stirred until homogeneous to prepare a product with a viscosity of 10 mm. 2 An organopolysiloxane composition with H / Vi = 1.7.

[0359] [Example 19]

[0360] 100 parts by weight of methylphenylvinyl polysiloxane (A6) as component (A), 4.29 parts by weight of methylphenylhydropolysiloxane (B4) as component (B), and a polysiloxane M having acryloyl groups on the side chain as component (C) are added. 3 2D 3 20 D 3A1.3 parts by mass of 5(C9), 1200 parts by mass of toluene and 1200 parts by mass of hexane as component (E), 3 parts by mass of 3-methyl-1-butyn-3-ol (F1) as component (F), and 0.60 parts by mass of organopolysiloxane (G1) as component (G) were stirred until homogeneous. Then, a complex of platinum and vinylsiloxane as component (D) was added so that the total mass of components (A), (B), (C), and (D), converted to platinum atomic mass, was 80 ppm. The mixture was stirred until homogeneous to prepare a product with a viscosity of 10 mm. 2 An organopolysiloxane composition with H / Vi = 1.7.

[0361] The organopolysiloxane compositions obtained in the above examples (Examples 16-19) were evaluated under the same methods and conditions as those used for evaluating the solvent-based compositions according to 1-1) above. These results, together with the above-described compound compositions, are recorded in Table 7.

[0362] [Table 7]

[0363]

[0364] * No siloxane unit represented by the following formula (1)

[0365] 3)(H) component effect

[0366] 3-1) Evaluation based on solvent composition

[0367] [Example 20]

[0368] 100 parts by weight of methyl vinyl polysiloxane (A1) as component (A), 1.54 parts by weight of methyl hydrogen polysiloxane (B1) as component (B), and a polysiloxane M having acryloyl groups on the side chain as component (C) are added. 3 2D 3 20 D 3A 5 parts by mass of (C9), 156 parts by mass of toluene as component (E), 3 parts by mass of 3-methyl-1-butyn-3-ol (F1) as component (F), and 1 part by mass of Perhexa C(H1) as component (H) were stirred until homogeneous. Then, a complex of platinum and vinylsiloxane was added as component (D) so that the total mass relative to components (A), (B), (C), and (D), converted to platinum atomic mass, was 80 ppm. The mixture was stirred until homogeneous to prepare a product with a kinematic viscosity of 10 mm. 2 A composition with a ratio of 3 for Si-H groups to alkenyl groups in the composition.

[0369] [Example 21]

[0370] 100 parts by weight of methyl vinyl polysiloxane (A1) as component (A), 1.54 parts by weight of methyl hydrogen polysiloxane (B1) as component (B), and a polysiloxane M having acryloyl groups on the side chain as component (C) are added. 3 2D 3 20 D 3A 5 parts by mass of (C9), 156 parts by mass of toluene as component (E), and 3 parts by mass of 3-methyl-1-butyn-3-ol (F1) as component (F) were stirred until homogeneous. Then, a complex of platinum and vinylsiloxane was added as component (D) so that the total mass of components (A), (B), (C), and (D), converted to platinum atomic mass, was 80 ppm. The mixture was stirred until homogeneous to prepare a product with a kinematic viscosity of 10 mm. 2 A composition with a ratio of 3 for Si-H groups to alkenyl groups in the composition.

[0371] [Reference Example 4]

[0372] 100 parts by mass of methyl vinyl polysiloxane (A1) as component (A), 1.54 parts by mass of methyl hydrogen polysiloxane (B1) as component (B), 1561 parts by mass of toluene as component (E), and 3 parts by mass of 3-methyl-1-butyn-3-ol (F1) as component (F) were added. After stirring until homogeneous, a platinum-vinylsiloxane complex was added as component (D) so that the total mass of components (A), (B), (C), and (D), converted to platinum atomic mass, is 160 ppm. The mixture was stirred until homogeneous to prepare a product with a viscosity of 10 mm. 2 An organopolysiloxane composition having a ratio of 3 / s, H / Vi (the ratio of Si-H groups in component (B) to alkenes in component (A) (the same below)).

[0373] [Comparative Example 8]

[0374] 100 parts by mass of methyl vinyl polysiloxane (A1) as component (A), 1.54 parts by mass of methyl hydrogen polysiloxane (B1) as component (B), 1561 parts by mass of toluene as component (E), and 3 parts by mass of 3-methyl-1-butyn-3-ol (F1) as component (F) were added. After stirring until homogeneous, a platinum-vinylsiloxane complex was added as component (D) so that the total mass of components (A), (B), (C), and (D), converted to platinum atomic mass, is 80 ppm. The mixture was stirred until homogeneous to prepare a product with a viscosity of 10 mm. 2 An organopolysiloxane composition with H / Vi = 3 / s and H / Vi = 3.

[0375] The organopolysiloxane compositions obtained in the above examples (Examples 20-21, Reference Example 4, Comparative Example 8) were evaluated as follows. These results, together with the above-described formulations, are recorded in Table 8.

[0376] [Peeling force]

[0377] An organopolysiloxane composition was coated onto polyethylene laminated paper using a No. 14 rod coater, and then heated in a hot air dryer at 100°C for 30 seconds to obtain a thickness of 0.9–1.1 g / m². 2 Release paper of a cured film of an organopolysiloxane composition.

[0378] In this state, after aging at 25°C for 24 hours, a solvent-based acrylic pressure-sensitive adhesive BPS-5127 (manufactured by Toyo Ink Co., Ltd.) was applied to the surface of the cured film of the release paper, and then dried in a dryer at 100°C for 180 seconds. After drying, it was left at room temperature for more than 10 minutes, then high-quality paper was pasted on and cut into pieces of 5.0cm × 18cm. A 2kg roller was used to apply a load to the cut pieces, and after aging at room temperature for 24 hours, one end of the test piece was peeled off. The end of the substrate with pressure-sensitive adhesive was stretched at a peel speed of 0.3m / min at an angle of 180 degrees relative to the polyethylene laminate paper. The force required for peeling at this time (i.e., "peel force") (N / 50mm) was measured using a tensile testing machine (Shimadzu Corporation AGS-50G model).

[0379] [Residual Adhesion Rate]

[0380] Using the same method as described above regarding peel strength, an organosilicon composition was coated and cured onto a polyethylene laminate to obtain a release paper. After aging at 23°C for 24 hours, tesa-7475 tape (tesa UK Ltd.) was pasted onto the release paper, and cut into 2.5cm × 18cm pieces. These were then clamped to a glass plate and subjected to a 20g / cm² pressure test at 70°C. 2 After aging under load for 24 hours, the tesa-7475 tape was peeled off and bonded to a stainless steel plate. It was then pressed back and forth once with a 2kg roller and left to stand for 30 minutes. One end of the tape was then peeled off, and the end was stretched at a 180-degree angle relative to the SUS plate at a peeling speed of 0.3 m / min. The peeling force required was measured as the adhesion strength A (N / 25 mm). Tensile testing was performed using a Shimadzu Corporation AGS-50G model.

[0381] As a blank, unused tesa-7475 tape was adhered to an SUS board. Similar to the above, a 2kg roller was used for one reciprocating motion to press the tape together. After 30 minutes, one end of the tesa-7475 tape was peeled off. This end was then stretched at a 180-degree angle relative to the SUS board at a peeling speed of 0.3 m / min. The force required for peeling was measured as the adhesive force B (N / 25 mm). The residual adhesion percentage (%) was calculated using (A / B) × 100.

[0382] [Curing properties]

[0383] The silicone composition was coated onto polyethylene laminated paper using the same method as described above for peel strength, and then heated in a hot air dryer at 100°C for 30 seconds to obtain a thickness of 0.9–1.1 g / m². 2 Release paper for the cured film of the organopolysiloxane composition. Remove the release paper from the dryer, immediately rub the cured film surface vigorously with your index finger 10 times, apply red oily ink, and observe the ink staining and the state of the cured film.

[0384] As a result, fingerprints that appear deep are indicated by "×", fingerprints that appear shallow are indicated by "△", and fingerprints that are almost invisible are indicated by "○".

[0385] [Migration of Organosilicon (Organopolysiloxane)]

[0386] A polyester film was overlapped on the surface of a cured film of an organopolysiloxane composition formed from release paper obtained in the same manner as in the peel force test. After pressing for 20 hours at room temperature under a pressure of 0.98 MPa, the polyester film was separated from the cured film. A red oily ink was applied to the surface of the polyester film in contact with the cured film, and the silicone migration was evaluated based on its shrinkage.

[0387] As a result, shrinkage without ink (silicon migration is zero or very small) is represented by “○”, shrinkage with partial ink (silicon migration is small) is represented by “△”, and shrinkage with ink (silicon migration is large) is represented by “×”.

[0388] [Table 8]

[0389]

[0390] 3-2) Evaluation using solvent-free composition

[0391] [Example 22]

[0392] The following are added as components: 60 parts by weight of methyl vinyl polysiloxane (A3) as component (A), 40 parts by weight of methyl vinyl polysiloxane (A4), 4.23 parts by weight of methyl hydrogen polysiloxane (B2) as component (B), and polysiloxane M having acryloyl groups on the side chain as component (C). 3 2D 3 20 D 3A 5 parts by mass of 1-C9, 0.3 parts by mass of 1-ethynyl-1-cyclohexanol (F2) as component (F), and 1 part by mass of Perhexa C(H1) as component (H) were stirred until homogeneous. Then, a complex of platinum and vinylsiloxane was added as component (D) so that the total mass of components (A), (B), (C), and (D), converted to platinum atomic mass, was 60 ppm. The mixture was stirred until homogeneous to prepare a product with a kinematic viscosity of 406 mm. 2 A composition with a ratio of / s and H / Vi (the ratio of Si-H groups to alkenes in the composition) of 1.8.

[0393] [Example 23]

[0394] The following are added as components: 60 parts by weight of methyl vinyl polysiloxane (A3) as component (A), 40 parts by weight of methyl vinyl polysiloxane (A4), 4.23 parts by weight of methyl hydrogen polysiloxane (B2) as component (B), and polysiloxane M having acryloyl groups on the side chain as component (C). 3 2D 3 20 D 3A 5 (C9) 1 part by mass, 1-ethynyl-1-cyclohexanol (F2) as component (F), were stirred until homogeneous, and then a complex of platinum and vinylsiloxane was added as component (D) so that the total mass of components (A), (B), (C) and (D), converted to platinum atomic mass, was 60 ppm. The mixture was stirred until homogeneous to prepare a product with a kinematic viscosity of 405 mm. 2 A composition with a ratio of / s and H / Vi (the ratio of Si-H groups to alkenes in the composition) of 1.8.

[0395] [Reference Example 5]

[0396] 60 parts by mass of methyl vinyl polysiloxane (A3) and 40 parts by mass of methyl vinyl polysiloxane (A4) as component (A), 4.23 parts by mass of methyl hydropolysiloxane (B2) as component (B), and 0.3 parts by mass of 1-ethynyl-1-cyclohexanol (F2) as component (F) were added. After stirring until homogeneous, a platinum-vinylsiloxane complex was added as component (D) so that the total mass of components (A), (B), (C), and (D), converted to platinum atomic mass, is 120 ppm. The mixture was stirred until homogeneous to prepare a product with a kinematic viscosity of 400 mm. 2 A composition with a ratio of / s and H / Vi (the ratio of Si-H groups to alkenes in the composition) of 1.8.

[0397] [Comparative Example 9]

[0398] 60 parts by mass of methyl vinyl polysiloxane (A3) and 40 parts by mass of methyl vinyl polysiloxane (A4) as component (A), 4.23 parts by mass of methyl hydropolysiloxane (B2) as component (B), and 0.3 parts by mass of 1-ethynyl-1-cyclohexanol (F2) as component (F) were added. After stirring until homogeneous, a platinum-vinyl siloxane complex was added as component (D) so that the total mass of components (A), (B), (C), and (D), converted to platinum atomic mass, is 60 ppm. The mixture was stirred until homogeneous to prepare a product with a kinematic viscosity of 400 mm. 2 A composition with a ratio of / s and H / Vi (the ratio of Si-H groups to alkenes in the composition) of 1.8.

[0399] The organopolysiloxane compositions obtained in the above examples (Examples 22-23, Reference Example 5, Comparative Example 9) were evaluated using the same methods and conditions as those used for evaluating the solvent-free compositions (organosilicon (C) components) according to 1-3) above. These results, together with the above-described compound compositions, are recorded in Table 9.

[0400] [Table 9]

[0401]

[0402] Reference Example 1 illustrates a case where component (C) was not used and the platinum concentration of the catalyst (D) was as high as 160 ppm. In this case, curing proceeded sufficiently, resulting in good curing properties, silicone migration, and adhesion. The peel force was low, the residual adhesion was high, and the original characteristics of the release paper were revealed.

[0403] Comparative Example 1 involved reducing the platinum concentration of the catalyst in component (D) of Reference Example 1 to 80 ppm, i.e., half the composition. In this case, curing was insufficient even after heat treatment at 120°C for 30 seconds, resulting in high peel strength, reduced residual adhesion, and failure to obtain the original properties of silicone. If the surface was rubbed, fingerprints adhered clearly, and migration was also significant; therefore, curability, silicone migration, and adhesion were rated as ×, △, and ×, respectively.

[0404] Examples 1-9 are compositions in which a compound with an acryloyl group as component (C) is added in trace amounts to the composition of Comparative Example 1. With the addition of component (C), the curing is sufficient even though the platinum concentration of the catalyst in component (D) is 80 ppm, and there is no silicone migration. Regarding peel strength and residual adhesion, the values ​​obtained are not significantly different from those of Reference Example 1. It can be confirmed that the curing reaction was carried out at a low platinum concentration using component (C).

[0405] Comparing Comparative Example 2 and the Examples, in terms of the effect of component (C) being a siloxane compound, it can be seen that the acryloyl group on the side chain is more effective than the acryloyl group located at the end of the molecule. As shown in Example 8, it is equally effective not only in the case of having (meth)acryloyl groups on difunctional siloxane units, but also in the case of trifunctional siloxanes.

[0406] As can be seen from the comparison between Comparative Example 3 and Example 1, the effect of component (C) is improved by the fact that the molecular end of component (A) has a trivinyl structure.

[0407] Examples 10-13 evaluated the effects of compounds other than silicone as component (C) using a solvent-free composition (E). A comparison with Comparative Example 4 confirmed that component (C) reduced peel force and increased residual adhesion. Based on characteristics similar to Reference Example 2, which contained a large amount of component (D), it was confirmed that it promoted the curing reaction.

[0408] By comparing with the comparative example, it can be seen that in the composition without solvent (E), the effect of component (C) is improved because the molecular end of component (A) has a trivinyl structure.

[0409] Examples 14 and 15 similarly evaluated the effect of the organosilicon compound as component (C) using a solvent-free (E) composition. By reducing component (D) to 20 ppm and changing the substrate to cellophane, the evaluation was conducted under more stringent conditions regarding curability, migration, and adhesion. The same trend as described above was also confirmed, and the effect of component (C) in improving curability, adhesion, and reducing migration was also confirmed.

[0410] Examples 16-19 show the results of evaluating the effect of component (C) when components (A) and (B) used compounds containing phenyl groups. It can be seen that the improvement in adhesion is greater compared with Examples 6 and 7.

[0411] Examples 20-23 evaluate the effect of component (C) by adding component (H) to the formulation, confirming its role in reducing peel strength and improving residual adhesion. This effect is consistent in compositions containing or without solvent; in solvent-based compositions, the curing temperature is as low as 100°C, demonstrating a significant effect even under conditions where curing is difficult.

[0412] Based on the above results, the curing promotion effect of component (C) can be further improved by combining the terminal trivinyl structure of component (A), the phenyl-containing components (A) and / or (B), and the addition of (H) peroxide.

Claims

1. A curable organopolysiloxane composition containing the following components (A) to (D): (A) an organopolysiloxane having two or more alkenyl groups bonded to silicon atoms in one molecule, with an alkenyl content of 0.001 to 0.7 mol / 100g, and having no more than three (meth)acryloyl groups in one molecule, wherein at least 50% by mass of the molecular end of component (A) is capped with a siloxane unit as shown in formula (1) below, and having a viscosity of 7 mPa·s or more at 25°C as measured by a rotational viscometer, and a 30% by mass toluene dissolution viscosity (the viscosity of a solution in which 30% by mass of the organopolysiloxane is dissolved in toluene) of 70,000 mPa·s or less: 100 parts by mass, (CH2=CH-)3SiO 1 / 2 (1) (B) Organohydrogen polysiloxane, which has an average of more than two hydrogen atoms bonded to silicon atoms (i.e., Si-H groups) per molecule, and no more than three (meth)acryloyl groups per molecule: the amount of Si-H groups in component (B) is 1 to 10 times greater than the number of moles of alkenes in component (A). (C) is selected from one or more of (C-1) and (C-2) below: 0.01 to 5.0 parts by mass relative to 100 parts by mass of component (A). (C-1) A non-organopolysiloxane compound having one or more (meth)acryloyl groups in one molecule and a molecular weight of 72 to 1000. (C-2) An organopolysiloxane having three or more (meth)acryloyl groups in one molecule, wherein the weight-average molecular weight of the organopolysiloxane, as determined by gel permeation chromatography (GPC) (solvent: toluene), is greater than 500 and less than 20,000 based on the polystyrene equivalent. (D) Platinum group metal catalyst: in an amount such that the platinum concentration in the total mass of components (A), (B), (C) and (D) is 1 to 100 ppm by mass.

2. The curable organopolysiloxane composition according to claim 1, wherein, relative to 100 parts by weight of component (A), it further contains 0 to 100,000 parts by weight of diluent (E).

3. The curable organopolysiloxane composition according to claim 1, wherein, relative to 100 parts by weight of component (A), it further contains 0.01 to 5.00 parts by weight of reaction control agent (F).

4. The curable organopolysiloxane composition according to claim 1, wherein, Component (B) contains 5 to 30 mol% of the total number of substituents on the Si atoms that are phenyl.

5. The curable organopolysiloxane composition according to claim 1, wherein, (A) contains (A) component in which 1 to 20 mol% of the total number of substituents on the Si atom are phenyl.

6. The curable organopolysiloxane composition according to claim 1, further comprising, relative to 100 parts by weight of component (A), 0.1 to 20.0 parts by weight of organopolysiloxane (G), having at least two alkenyl groups, wherein R... 10 (3-g1) R 9 g1 SiO 1 / 2 The siloxane unit is M R9R10 Unit, R 10 SiO 3 / 2 Siloxane unit, i.e., T R10 As a necessary unit, R in the above formula 9 Each is an alkenyl group independently, R 10 Each is an independent monovalent hydrocarbon group that is unsubstituted or substituted with a halogen atom or cyano group without aliphatic unsaturated bonds, g1 is an integer from 1 to 3, M R9R10 Unit / T R10 The molar ratio of the units satisfies 2 / 8 to 8 / 2, and the viscosity of (G) organopolysiloxane at 25°C ranges from 1 to 1000 mPa·s. The molecular terminus of (G) organopolysiloxane is M. R9R10 The unit is M R9R10 The unit and part of it are silanol or alkoxy groups.

7. The curable organopolysiloxane composition according to claim 1, wherein, (C) is an organopolysiloxane having one or more difunctional and / or trifunctional siloxane units with (meth)acryloyl groups in one molecule.

8. The curable organopolysiloxane composition according to claim 1, wherein, relative to 100 parts by weight of component (A), it further contains 0.01 to 5.0 parts by weight of (H) organic peroxide.

9. The curable organopolysiloxane composition according to claim 8, wherein, (H) components are multifunctional organic peroxides with two or more peroxy bonds in the molecule.

10. The curable organopolysiloxane composition according to claim 1, wherein the platinum group metal catalyst (D) is contained in an amount of 1 to 40 ppm by mass of the total mass of components (A) to (D).

11. The curable organopolysiloxane composition according to any one of claims 1 to 10, used for release paper or release film.

12. A method for manufacturing a release paper or release film, wherein the method uses the organopolysiloxane composition for release paper or release film according to claim 11.

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