TWI883136B - Silicone oxide composition for peeling sheet and peeling sheet - Google Patents

Abstract

The present invention is a silicone composition for peeling sheets, which comprises: (A) an organic polysiloxane having at least two alkenyl groups in one molecule, and the alkenyl content is 0.001-0.2 mol/100 g; (B1) an organic polysiloxane having 10 mol% or more of siloxane units having glycidyl groups and/or glycidoxy groups bonded to silicon atoms via carbon atoms in one molecule, 0.002-0.02 mol/100 g of silanol groups, 0.5-2.5 mol/100 g of alkoxy groups, and an average degree of polymerization of 3-50; (B2) an organic hydrosiloxane having 1.3 mol/100 g of hydrochloric acid; and (B3) an organic hydrosiloxane having 1.3 mol/100 g of hydrochloric acid. g or more Si-H groups, and a polymerization degree of 10 to 100; and, (D) a platinum group metal catalyst. Thus, a silicon oxide composition for a peeling sheet is provided, which can form a hardened film, and the hardened film has excellent adhesion to the substrate, can maintain the adhesion even in a harsh environment, and imparts a smaller peeling force.

Description

Silicone oxide composition for peeling sheet and peeling sheet

The present invention relates to a silicone composition for a peeling sheet and a peeling sheet obtained by using the composition.

Conventionally, a hardened film of a silicone composition is formed on the surface of a sheet substrate such as paper or plastic film to impart peeling properties relative to adhesive materials.

As a method for forming a hardened film of a silicone composition on the surface of a substrate, for example, Patent Document 1 proposes a method in which a platinum compound is used as a catalyst to allow an organic polysiloxane containing an olefin group to undergo an addition reaction with an organic hydropolysiloxane to form a releasable film on the surface of the substrate. Although such a silicone composition is well bonded to a paper substrate, it has been pointed out in the past that it has the following defects: lack of adhesion to plastic films such as polyester films and polypropylene films, and the need for pretreatment of the substrate.

As a method for improving adhesion to a substrate, Patent Document 2 proposes a base polymer composition having a branched structure containing RSiO _3/2 units. However, this method lacks practicality because a large amount of branched organopolysiloxane containing alkenyl groups is used, which increases the manufacturing cost.

As a method of improving adhesion to a substrate by using a small amount of additives, Patent Document 3 proposes adding an organic polysiloxane having an epoxy group. However, this method only describes adhesion to the substrate under high temperature and high humidity conditions, and does not evaluate adhesion immediately after curing or when stored at room temperature. In addition, there is no description of the effect of the addition of an organic polysiloxane having an epoxy group on the peeling properties.

In Patent Document 4, the adhesion to the substrate is improved by adding a reaction product of a liquid polyorganosiloxane containing alkenyl and silanol groups and a hydrolyzable silane containing epoxy groups. However, this method does not discuss the effect of adding the above product on the peeling characteristics.

In Patent Document 5, low molecular weight siloxane containing alkenyl groups is added, and after irradiation with ultraviolet rays, the coating is cured by heating, thereby improving the substrate adhesion without affecting the peeling characteristics. However, this method requires a heating dryer and an ultraviolet (UV) irradiation device.

Recently, as the performance of peeling sheets, requirements have begun to be placed on lower peeling forces than previous products, as well as high durability: during the peeling sheet forming step, good substrate adhesion can be maintained even in harsh environments such as high temperature and high humidity. However, existing peeling sheet compositions tend to have the following characteristics: the smaller the peeling force, the worse the substrate adhesion; as for long-term adhesion in more harsh environments, there are almost no compositions that can meet the requirements. It is believed that the reason for this is that most materials that are effective for light peeling, such as various materials used as transition components, work in a way that reduces adhesion to the substrate. The reality is that it is difficult to take into account both light peeling and excellent substrate adhesion.

Thus, in the current technology, no suitable method has been found to take into account both the light peeling property of the silicon oxide composition and the excellent substrate adhesion. [Prior technical literature] (Patent literature)

Patent document 1: Japanese Patent Publication No. 47-32072 Patent document 2: Japanese Patent Publication No. 2965231 Patent document 3: Japanese Patent Publication No. 2011-132532 Patent document 4: Japanese Patent Publication No. 5507246 Patent document 5: Japanese Patent Publication No. 5626097

[The problem the invention is trying to solve]

The present invention is completed in view of the above situation, and its purpose is to provide a silicone composition for a peeling sheet, which has excellent adhesion to the substrate and almost no increase in peeling force due to improved adhesion, so a hardened film (peeling film) that imparts a smaller peeling force can be formed. The substrate adhesion of the film can be maintained for a long time not only at room temperature but also in harsh environments such as high temperature and high humidity.

Furthermore, the object is to provide a peeling sheet obtained from the composition of the present invention. [Technical means for solving the problem]

The present invention is completed to solve the above-mentioned problems, and provides a silicone composition for addition-curing peeling sheets, which is characterized in that it comprises: 100 parts by mass of (A) organic polysiloxane, which has at least two alkenyl groups in one molecule, the alkenyl content is 0.001-0.2 mol/100 g, and the 30% by mass toluene dilution viscosity at 25°C is 0.01-70 Pa.s; (B) component, which comprises the following (B1) compound and (B2) compound, 0.1-20 parts by mass of (B1) organic polysiloxane, which contains in one molecule more than 10 mol% of siloxane units having glycidyl and/or glycidoxy groups bonded to silicon atoms via carbon atoms, and contains 0.002-0.02 mol/100 g of glycidyl and/or glycidoxy groups. g of silanol groups, containing 0.5 to 2.5 mol/100 g of alkoxy groups, and an average degree of polymerization of 3 to 50; (B2) an organic hydrosiloxane having more than 1.3 mol/100 g of Si-H groups and a degree of polymerization of 10 to 100, the mass fraction of the (B2) organic hydrosiloxane being equivalent to 0.02 to 1 times the mass fraction of the aforementioned (B1) compound; a catalytic amount of (D) a platinum group metal catalyst; and, 0 to 20,000 mass fractions of (E) an organic solvent.

The silicone composition for a release sheet of the present invention can form a hardened film (release film) by containing specific amounts of the above-mentioned components (A), (B) and (D), and the hardened film (release film) has excellent adhesion to a substrate, especially a plastic film substrate such as a polyester film. In addition, the hardened film obtained from the silicone composition for a release sheet of the present invention can show a relatively small peeling force, and while showing such a small peeling force, it can also have good adhesion to the substrate, and can maintain good adhesion to the substrate for a long time not only at room temperature but also under severe conditions of high temperature and high humidity.

The silicone composition for peeling sheets of the present invention preferably further comprises: (C) an organic hydropolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule, and unlike the aforementioned compound (B2), the amount of the component (C) is an amount such that the total molar number of hydrogen atoms bonded to silicon atoms of the aforementioned compound (B2) and the aforementioned component (C) is equal to 0.5 to 10 times the molar number of alkenyl groups in the aforementioned composition.

By including such a component (C), better curability can be obtained.

The compound (B1) is preferably a partially hydrolyzed condensate of at least one of an organic alkoxysilane represented by the following general formula (1-1) and an organic alkoxysilane represented by the following general formula (1-2), (1-3) or (1-4), and is an organic polysiloxane having a linear, branched siloxane or cyclic siloxane structure, or a mixture thereof. In formulas (1-1), (1-2), (1-3) and (1-4), R1 may be the same or different and is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms and not having an aliphatic unsaturated bond, which may contain an oxygen atom, or a hydrogen atom; R12 is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; and n is an integer from 3 to 10.

By including such a compound (B1), the strength of the cured product can be increased and a higher adhesion-enhancing effect can be exhibited.

The aforementioned compound (B2) is preferably an organohydrogensiloxane represented by the following general formula (2-1) or (2-2), or a mixture thereof: (R12) ₃ Si-{(R12)HSiO} _m -Si(R12) ₃ ････(2-1) (R12) ₂ HSi-{(R12)HSiO} _m -SiH(R12) ₂ ････(2-2) (In formulas (2-1) and (2-2), R12 may be the same or different and is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, and m is an integer of 2 to 100).

By including such a (B2) compound in combination with the (B1) compound, the strength of the cured product can be increased and a higher adhesion-improving effect can be exerted. Since it is difficult to obtain a sufficient adhesion-improving effect even if the (B2) compound is used alone, it is speculated that the following effects may be caused: the (B1) compound increases the strength of the adhesion-improving layer formed at the interface between the silicone cured film and the substrate, and strengthens the bonding between the adhesion-improving layer and the silicone cured film.

The silicone composition for a peeling sheet of the present invention preferably further comprises 0.1 to 10 parts by mass of a component (B3) as the component (B), wherein the component (B3) is a compound having a viscosity of less than 0.5 Pa.s at 25°C, having at least two alkenyl groups in one molecule, the alkenyl content being 5 to 500 times the alkenyl content of the component (A), and having no epoxy group, and the molar number of hydrogen atoms bonded to silicon atoms in the aforementioned composition is 0.5 to 10 times the total molar number of alkenyl groups in the aforementioned components (A) and (B3).

By including such a component (B3), the curability of the composition can be further improved, and the light peeling effect can be maintained, and the adhesion of the obtained hardened film to the substrate just after curing can be improved. The mechanism of this effect is not yet clear, but compared with the component (A), the component (B3) has a higher alkenyl content and lower viscosity, and is less restricted in molecular movement in the composition, and has excellent reactivity with SiH groups, so the curability is improved, the residual SiH groups are reduced, and the light peeling effect can also be obtained. Furthermore, it is speculated that by performing a crosslinking reaction, the crosslinking density is increased, so the adhesion of the substrate just after curing is also improved.

The silicone composition for a peeling sheet of the present invention preferably further comprises 0.1 to 20 parts by weight of the following component (F1) and/or the following component (F2) as a peeling force control component (F) relative to 100 parts by weight of the component (A): (F1) The peeling force control component comprises an acrylic-silicone graft copolymer having a weight average molecular weight of 1,000 to 100,000, wherein the acrylic-silicone graft copolymer is obtained by free radical polymerization of (a) an organic polysiloxane compound having an acryl group and/or a methacryl group represented by the following general formula (3) and (b) a free radical polymerizable monomer having one free radical polymerizable group in one molecule. In formula (3), ^R2 is a hydrogen atom or a methyl group, X is a group selected from an oxygen atom, an NH group and a sulfur atom, Y is a divalent hydrocarbon group having 1 to 12 carbon atoms which may be mediated by an oxygen atom, ^R3 may be the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, or a substituent represented by the following general formula (4), f is an integer from 0 to 1000, In formula (4), ^R4 may be the same or different and is an unsubstituted or substituted monovalent alkyl group having 1 to 20 carbon atoms, a hydrogen atom, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms, and g is an integer of 0 to 300; (F2) linear phenylmethyl polysiloxane.

By including such component (F), it is possible to maintain excellent adhesion to the substrate and adjust the peeling force. In addition, it is possible to obtain an excellent peelable film having a high residual adhesion rate of the adhesive sheet after peeling.

The present invention also provides a release sheet, which is characterized in that the release sheet is obtained by coating the silicone composition of the release sheet of the present invention on a paper substrate or a film substrate and curing the coating.

The peeling sheet of the present invention is obtained by coating the peeling sheet of the present invention with a silicone composition on a substrate and hardening it. Therefore, the hardened film obtained by hardening can show a smaller peeling force and can show good substrate adhesion. Not only at room temperature, but also under harsh conditions of high temperature and high humidity, the good substrate adhesion can be maintained for a long time. (Effect of the invention)

According to the silicone composition for a release sheet of the present invention, a non-adhesive hardened film with excellent adhesion to a substrate can be obtained, and good release characteristics can be obtained without almost changing the non-adhesiveness of the hardened film before and after the adhesion improvement. In the previous adhesion improvement method, the impact on the release characteristics could not be avoided, but according to the release sheet formed with the hardened film of the silicone composition for a release sheet of the present invention, the adhesion to the substrate can be improved without almost affecting the release characteristics. Furthermore, the hardened film obtained by using the silicone composition for a release sheet of the present invention can maintain good substrate adhesion for a long period of time even when placed under severe conditions of high temperature and high humidity.

The present invention is described in detail below, but the present invention is not limited thereto. Furthermore, in the present invention, the release sheet may be, for example, a release paper including a paper substrate, or a release film including a film made of plastic or the like. Furthermore, the composition for the release sheet may be, for example, a silicone composition for release paper, or a silicone composition for release film.

In order to achieve the above-mentioned purpose, the inventors of the present invention have made great efforts to study and found that a hardened film with excellent adhesion to a substrate can be obtained by using a composition, wherein the composition is prepared by mixing the following components in specific amounts: (A) component, which is an organic polysiloxane having at least two alkenyl groups in one molecule, an alkenyl content of 0.001 to 0.2 mol/100 g, and a dilution viscosity of 0.01 to 70% in 30% toluene at 25°C; Pa.s; (B) component, which includes (B1) compound and (B2) compound, the (B1) compound is an organic polysiloxane, containing 10 mol% or more of siloxane units having glycidyl and/or glycidoxy groups bonded to silicon atoms via carbon atoms in one molecule, containing 0.002 to 0.02 mol/100 g of silanol groups, containing 0.5 to 2.5 mol/100 g of alkoxy groups, and an average degree of polymerization of 3 to 50, the (B2) compound is an organic hydrogen siloxane, having 1.3 mol/100 g or more of Si-H groups, and a degree of polymerization of 10 to 100; (D) platinum metal catalyst; and, (E) organic solvent.

Furthermore, in previous methods for improving adhesion, compositions with relatively small peeling forces could not achieve sufficient substrate adhesion, but it was found that the composition of the present invention can simultaneously achieve relatively small peeling forces and excellent substrate adhesion, and the excellent substrate adhesion can be sustained for a long time, thereby completing the present invention.

Furthermore, previously, the inventors of the present invention achieved the target effect by combining a composition obtained by combining a high alkenyl content siloxane and an epoxy-containing siloxane in Japanese Unexamined Patent Publication No. 2017-25135. However, in the present invention, a composition that uses a cheaper material to enhance the effect was found, thereby completing the present application.

[Silicone composition for peeling sheet] The addition-curing type peeling sheet silicone composition of the present invention comprises: 100 parts by mass of (A) organic polysiloxane, which has at least two alkenyl groups in one molecule, the alkenyl content is 0.001 to 0.2 mol/100 g, and the 30% by mass toluene dilution viscosity at 25°C is 0.01 to 70 Pa.s; (B) component, which comprises the following (B1) compound and (B2) compound, 0.1 to 20 parts by mass of (B1) organic polysiloxane, which contains in one molecule 10 mol% or more of siloxane units having a glycidyl group and/or a glycidoxy group bonded to a silicon atom via a carbon atom, and contains 0.002 to 0.02 mol/100 g of glycidyl group and/or glycidoxy group. g of silanol groups, containing 0.5 to 2.5 mol/100 g of alkoxy groups, and an average degree of polymerization of 3 to 50; (B2) an organic hydrosiloxane having more than 1.3 mol/100 g of Si-H groups and a degree of polymerization of 10 to 100, the mass fraction of the (B2) organic hydrosiloxane being equivalent to 0.02 to 1 times the mass fraction of the aforementioned (B1) compound; a catalytic amount of (D) a platinum group metal catalyst; and, 0 to 20,000 mass fractions of (E) an organic solvent.

In the silicone composition for a release sheet of the present invention, the (E) organic solvent is an optional component because the amount of the organic solvent can be 0 parts by mass relative to 100 parts by mass of the (A) component. In addition, the silicone composition for a release sheet of the present invention may also contain other optional components in addition to the components (A), (B) and (D). Specific examples of the optional components are described below.

Hereinafter, each component of the silicone composition for a peeling sheet of the present invention will be described in sequence.

[Component (A): Organic polysiloxane with alkenyl groups] The component (A) used in the present invention is an organic polysiloxane having at least two alkenyl groups in one molecule, an alkenyl content of 0.001 to 0.2 mol/100 g, and a 30 mass% toluene dilution viscosity at 25°C of 0.01 to 70 Pa.s, preferably represented by the following general formula (5).

In the above formula (5), R ⁵ may be the same or different and is an unsubstituted or substituted monovalent alkyl group having 1 to 20 carbon atoms and having no aliphatic unsaturated bond, or an alkenyl group having 2 to 12 carbon atoms which may have an oxygen atom interposed therein, and at least two R ⁵ are alkenyl groups.

The monovalent hydrocarbon group having 1 to 20 carbon atoms and having no aliphatic unsaturated bond may be specifically selected from the following groups: methyl, ethyl, propyl, butyl, etc. are preferably alkyl groups having 1 to 6 carbon atoms; cyclohexyl, etc. are preferably cycloalkyl groups having 5 to 8 carbon atoms; phenyl, tolyl, etc. are preferably aryl groups having 6 to 10 carbon atoms; benzyl, etc. are preferably aryl groups having 7 to 10 carbon atoms; and hydroxypropyl, cyanoethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, etc. obtained by replacing part or all of the hydrogen atoms bonded to the carbon atoms of these groups with hydroxyl, cyano, halogen atoms, etc.; in particular, from the viewpoint of releasability, the monovalent hydrocarbon group having 1 to 20 carbon atoms and having no aliphatic unsaturated bond is preferably an alkyl group or an aryl group, and more preferably a methyl group, an ethyl group, a propyl group or a phenyl group.

The alkenyl group with 2 to 12 carbon atoms which may be mediated by an oxygen atom is preferably a group represented by -(CH ₂ ) _x -CH=CH ₂ (x is 0 or an integer of 1 to 10), and specific examples thereof include vinyl, propenyl, butenyl, hexenyl, octenyl, and decenyl. In addition, the methylene chain may contain an ether bond, and examples thereof include -(CH ₂ ) ₂ -O-CH ₂ -CH=CH ₂ , -(CH ₂ ) ₃ -O-CH ₂ -CH=CH ₂ , etc. Among them, vinyl is preferred.

The number of alkenyl groups in one molecule of the organopolysiloxane of component (A) is two or more. That is, the organopolysiloxane of component (A) has at least two alkenyl groups in one molecule. If the number of alkenyl groups is less than two, there is a high possibility that uncrosslinked molecules will remain after curing, and the curability will be reduced, so it is not ideal. The organopolysiloxane of component (A) may, for example, have less than 2000 alkenyl groups in one molecule. In addition, the alkenyl content in each 100 g of the organopolysiloxane of component (A) is 0.001 to 0.2 mol, and more preferably 0.002 to 0.15 mol. If the content is less than 0.001 mol, the curability may be reduced; and if it exceeds 0.2 mol, heavy exfoliation may occur.

The viscosity of component (A) at 25°C is 0.01 to 70 Pa.s in 30% toluene dilution viscosity, preferably 0.01 to 60 Pa.s in 30% toluene dilution viscosity, and more preferably 0.01 to 50 Pa.s in 30% toluene dilution viscosity. If it is less than 0.01 Pa.s, the coating property of the composition is insufficient; and if it exceeds 70 Pa.s, the workability is reduced. The viscosity can be measured using a rotational viscometer (the same applies hereinafter).

In the above formula (5), h, i, j, and k are selected from positive numbers set within the above viscosity range, and in particular, h is an integer greater than or equal to 2, preferably an integer from 2 to 300, i is an integer greater than or equal to 100, preferably an integer from 148 to 19998, and more preferably an integer from 198 to 14700, j is an integer greater than or equal to 0, preferably an integer from 0 to 100, k is an integer greater than or equal to 0, preferably an integer from 0 to 100, 150≦h＋i＋j＋k≦20000, and preferably 200≦h＋i＋j＋k≦15000.

Specific examples of the component (A) include the following, but are not limited thereto. In the following formulae, Me, Vi, and Ph represent a methyl group, a vinyl group, and a phenyl group, respectively.

[Component (B)] The component (B) used in the present invention is a component for improving adhesion and is a component containing the following (B1) compound and (B2) compound.

(B1) Compound (B1) Compound is an organic polysiloxane, which has the effect of improving adhesion by being formulated into the composition of the present invention, and contains 10 mol% or more of a siloxane unit having a glycidyl group and/or a glycidoxy group bonded to a silyl atom via a carbon atom in one molecule, contains 0.002 to 0.02 mol/100 g of a silanol group, contains 0.5 to 2.5 mol/100 g of an alkoxy group, and has an average degree of polymerization of 3 to 50. The (B1) compound is used in an amount of 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) component.

The (B1) compound is a compound having the following high effect: even under heating and humidification conditions (under high temperature and high humidity environment), the substrate adhesion of the hardened film (peeling film) obtained by using the composition of the present invention can be maintained; the (B1) compound is a component formulated in anticipation of the adhesion improvement effect under particularly severe use conditions. In addition, the average degree of polymerization is the weight average degree of polymerization when converted to polystyrene obtained by gel permeation chromatography (GPC).

The organic polysiloxane as the compound (B1) is an organic polysiloxane containing 10 mol% or more of a siloxane unit having a glyoxypropyl group and/or a glyoxypropyloxy group bonded to a silyl atom via a carbon atom in one molecule. If the siloxane unit is less than 10 mol%, the adhesion effect to the substrate cannot be obtained. The upper limit of the content of the siloxane unit is not particularly limited, and can be set to 100 mol%, for example.

The organopolysiloxane as the compound (B1) contains 0.002 to 0.02 mol/100 g of silanol groups. When the content of the silanol groups is less than 0.002 mol/100 g, sufficient adhesion to the substrate cannot be obtained. On the other hand, when the content of the silanol groups exceeds 0.02 mol/100 g, it may have an adverse effect on the peeling properties. The content of the silanol groups is preferably 0.003 to 0.02 mol/100 g.

The organopolysiloxane as the compound (B1) contains 0.5 to 2.5 mol/100 g of alkoxy groups. When the content of the alkoxy groups is less than 0.5 mol/100 g, sufficient adhesion to the substrate cannot be obtained. On the other hand, when the content of the alkoxy groups exceeds 2.5 mol/100 g, the peeling properties may be adversely affected. The content of the alkoxy groups is preferably 0.6 to 2.5 mol/100 g.

The average degree of polymerization of the organopolysiloxane as the compound (B1) is 3 to 50, preferably 3 to 20. If the average degree of polymerization is less than 3, the adhesion effect to the substrate is insufficient, while if the average degree of polymerization exceeds 50, the adhesion effect to the substrate is reduced or the workability is reduced.

The organopolysiloxane of the compound (B1) may be any of linear, branched, and cyclic, and may also be a mixture thereof, and is preferably a partial hydrolysis condensate of an organoalkoxysilane. Among the organoalkoxysilanes used as raw materials, especially alkoxysilanes having a glycidyl group and/or a glycidoxy group bonded to a silicon atom via a carbon atom, a mono-trifunctional organoalkoxysilane is preferred, and an organoalkoxysilane represented by the following general formula (1-1) is more preferred. (In formula (1-1), R1 may be the same or different and is an unsubstituted or substituted alkyl group which may contain an oxygen atom or a hydrogen atom having 1 to 10 carbon atoms and having no aliphatic unsaturated bond. n is an integer from 3 to 10.)

As specific organoalkoxysilanes, the following organoalkoxysilanes can be listed.

As other organic alkoxysilanes to be co-hydrolyzed and condensed with the above-mentioned alkoxysilane, it is preferred to use at least one of the organic alkoxysilanes represented by the following general formulas (1-2), (1-3), and (1-4), and it is more preferred to use trifunctional and tetrafunctional alkoxysilanes of the following general formulas (1-3) and (1-4). It is considered that by including such a branched structure or a three-dimensional cross-linked structure in the molecule or by imparting a molding ability in the process of forming the cured product, the strength of the cured product is improved, and further, by appropriately reducing the solubility and dispersibility of the (B1) compound in the silicone cured film layer having excellent mold release properties and having a linear chain structure as the core, the (B1) compound is easily concentrated near the interface between the substrate and the silicone cured film, thereby exerting a higher adhesion improvement effect.

(R12) ₂ -Si(OR1) ₂ ････(1-2) R12-Si(OR1) ₃ ････(1-3) Si(OR1) ₄ ････(1-4) (In formulas (1-2) to (1-4), R1 may be the same or different and is an unsubstituted or substituted carbon group having 1 to 10 carbon atoms and which may contain an oxygen atom, or a hydrogen atom, and R12 is an unsubstituted or substituted carbon group having 1 to 20 carbon atoms).

As specific examples of the organic alkoxysilane to be co-hydrolyzed and condensed with an alkoxysilane having a glycidyl group and/or a glycidoxy group bonded to a silicon atom via a carbon atom (e.g., an organic alkoxysilane of the general formula (1-1)), the following organic alkoxysilanes can be cited.

In the above formula (1-1), the hydrogen atom on the monovalent organic group having a glycidoxy group may be substituted with a substituent. In terms of safety and economy, the substituent here is preferably a substituent other than an epoxycyclohexyl group. Examples of the epoxycyclohexyl group include 3,4-epoxycyclohexylmethyl, 2-(3,4-epoxycyclohexyl)ethyl, and 3-(3,4-epoxycyclohexyl)propyl.

Furthermore, R1 is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms and not having an aliphatic unsaturated bond, which may contain an oxygen atom, or a hydrogen atom. Specifically, the alkyl group of R1 includes, for example, alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl and tolyl; aralkyl groups such as benzyl and phenethyl; or groups obtained by replacing some or all of the hydrogen atoms bonded to the carbon atoms of these groups with hydroxyl groups, such as hydroxypropyl. Among these groups, R1 is preferably a hydrogen atom or an alkyl group, and more preferably an alkyl group having 1 to 5 carbon atoms.

The following siloxane units formed by partial hydrolysis and condensation reaction of the organoalkoxysilane represented by the above general formulas (1-1) to (1-4) can be represented by ^TE , D, T, _Q ^, respectively, and the compound ( _B1 ) can be represented by an average _formula of _DaTEbTcQd . Here, a+b+c+d is 3-50, b/(a+b+c+d) is 0.1-1, a, c and d are independently 0-35, and the molecular end that does not form a siloxane bond with other siloxane units is an alkoxy group or a silanol group.

The compound (B1) preferably does not have an alkenyl group in the molecule. By including such a compound (B1), the adhesion effect to the substrate can be improved.

The amount of the compound (B1) is in the range of 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, relative to 100 parts by mass of the organopolysiloxane of the component (A). If the amount is less than 0.1 parts by mass, the adhesion to the substrate cannot be improved, and if it exceeds 20 parts by mass, the peeling property may be affected or the strength of the hardened film may be reduced. Furthermore, if it exceeds 20 parts by mass, the excellent adhesion to the substrate may not be maintained for a long time in a harsh environment.

As specific examples of the compound (B1), the following compounds can be cited. Example 1 of the compound (B1) The molecules represented by the above formula and the mixture thereof, wherein a+b is 3 to 50, a is 1 or more, and the molecular ends are capped with (a+b+2) or less methoxy groups, ethoxy groups and/or propoxy groups, and a part of them is substituted with hydroxyl groups. (B2) Example 2 of the compound The molecules represented by the above formula and their mixtures, wherein a+b+c is 3 to 50, a is 1 to 50, and the molecular ends are capped with (a+b+2×c+2) or less methoxy groups, ethoxy groups and/or propoxy groups, a part of which are substituted with hydroxyl groups.

As a more preferred example, the following can be cited: (B1) Example 3 of compound The molecules represented by the above average hexamer formula and the mixture thereof, the molecular ends of which are capped with 8 or less methoxy groups, a part of which are substituted with hydroxyl groups; (B1) Example 4 of the compound The molecules represented by the above average hexamer formula and mixtures thereof have molecular terminals capped with 12 or less methoxy groups and/or ethoxy groups, some of which are substituted with hydroxyl groups.

(B2) Compound (B2) is an organohydrogensiloxane having 1.3 mol/100 g or more Si-H groups and a degree of polymerization of 10 to 100. When used in combination with (B1) compound, its adhesion-enhancing effect can be further enhanced. If the Si-H group of (B2) compound is less than 1.3 mol/100 g, the adhesion-enhancing effect cannot be obtained. There is no particular upper limit on the Si-H group of (B2) compound, and it can be set to 1.7 mol/100 g, for example.

Since it is difficult to obtain a sufficient adhesion improvement effect even if the (B2) compound is used alone, it is speculated that the following effects may be played: the (B1) compound increases the strength of the adhesion improvement layer formed at the interface between the silicone cured film and the substrate, and strengthens the bonding between the adhesion improvement layer and the silicone cured film.

The degree of polymerization is 10 to 100. If it is less than 10, the effect of improving adhesion is low, and if it exceeds 100, the stability is reduced, which is not preferred. The degree of polymerization of the compound (B2) is more preferably 15 to 100.

The preferred structure of the compound (B2) is a linear or branched organic hydrosiloxane whose main chain is mainly composed of siloxane units H(R12)SiO _2/2 . Here, R12 may be the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

More preferred is an organohydrogensiloxane represented by the following general formula (2-1) or (2-2), or a mixture thereof. (R12) ₃ Si-{(R12)HSiO} _m -Si(R12) ₃ ････(2-1) (R12) ₂ HSi-{(R12)HSiO} _m -SiH(R12) ₂ ････(2-2) (In formulas (2-1) and (2-2), R12 may be the same or different and is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, and m is an integer of 2 to 100)

The amount of compound (B2) to be added is adjusted according to the amount of compound (B1) to be used in combination. This can achieve an effect of improving adhesion. The specific amount to be added is 0.02 to 1 times the mass of compound (B1). If it is less than 0.02 times, the effect of improving adhesion is small; and if it exceeds 1 times, it may sometimes affect the peeling properties such as re-peeling. The amount of compound (B2) to be added is preferably 0.03 to 1 times the mass of compound (B1). Even if the amount is more than 1 times the mass, it is not expected that the adhesion-enhancing effect will be significantly improved. Furthermore, the amount of the following compound (B2) can be added arbitrarily: the molar number of hydrogen atoms bonded to silicon atoms of the compound (B2) is 0.5 to 10 times the molar number of alkenyl groups in the component (A). This can further improve the curability of the composition, which is more ideal.

As specific examples of the compound (B2), the following compounds can be cited.

(B2) Compound Example 1 wherein a' is 10 to 98, and b' is 0 to 17. (B2) Example 2 of Compound wherein a' is 8 to 98, and b' is 0 to 17. (B2) Example 3 of Compound Among them, a' is 22 to 97, b' is 0 to 13, and c' is 1 to 6.

(B2) Example 4 of Compound wherein a' is 11 to 97, b' is 0 to 15, and c' is 1 to 7. (B2) Example 5 of Compound Wherein, a'+b'+c'+d' is 10 to 100, c' is 13 or less, d' is 6 or less, and the molecular terminal is capped with Me ₃ SiO _1/2 unit. (B2) Example 6 of Compound Here, a'+b'+c'+d' is 10 to 100, c' is 15 or less, d' is 7 or less, and the molecular terminal is capped with a (Me) ₂ HSiO _1/2 unit.

The compounds of the following average structural formula can be more preferably listed.

(B3) component The (B3) component may be further included as the (B) component. The (B3) component is a compound having a viscosity of less than 0.5 Pa.s at 25°C, having at least two alkenyl groups in one molecule, the alkenyl content being 5 to 500 times the alkenyl content of the (A) component, and having no epoxy group.

The (B3) component is formulated as a component to improve the curability of the composition and the adhesion of the obtained cured film to the substrate immediately after curing. The effect of improving the curability and substrate adhesion by adding the (B3) component is obtained by the large difference in viscosity and olefin content with the (A) component. The (A) component is a high-viscosity organic polysiloxane, which can be converted to a high molecular weight through a slight cross-linking reaction. Therefore, as the reaction proceeds, the movement of molecules in the composition is restricted, and unreacted olefin groups and SiH groups may remain. On the other hand, compared to the (A) component, the (B3) component has a higher olefin content and a lower viscosity. Therefore, the movement of molecules in the composition is less restricted, and the reactivity with SiH groups is excellent, so the curability can be improved. In addition, since the residual SiH groups are reduced, a light peeling effect can be obtained. Furthermore, by the crosslinking reaction, the crosslinking density is increased, so it is estimated that the adhesion to the substrate just after curing is also improved.

The number of alkenyl groups in one molecule of component (B3) is two or more, and the amount thereof is 5 to 500 times, preferably 15 to 400 times, the amount of alkenyl groups contained in component (A). If the number of alkenyl groups in one molecule of component (B3) is 5 to 500 times the amount of alkenyl groups contained in component (A), the light peeling effect can be maintained, and the adhesion of the obtained cured film to the substrate immediately after curing can be sufficiently improved.

Here, the alkenyl group of component (B3) is preferably an alkenyl group having 2 to 12 carbon atoms, and more preferably a group represented by -(CH ₂ ) _x -CH=CH ₂ (x is 0 or an integer of 1 to 10), -(C=O)-CH=CH ₂ , or -O-(C=O)-CH=CH _2. Specific examples include vinyl, propenyl, butenyl, hexenyl, octenyl, decenyl, acrylyl, and acryloxy. The methylene chain may contain an ether bond, and examples thereof include -(CH ₂ ) ₂ -O-CH ₂ -CH=CH ₂ , -(CH ₂ ) ₃ -O-CH ₂ -CH=CH ₂ , and the like. In industry, vinyl and acryloxy are more preferably used.

The viscosity of the component (B3) at 25°C is less than 0.5 Pa.s, and more preferably less than 0.3 Pa.s. By less than 0.5 Pa.s, the effect of improving the adhesion to the substrate can be fully obtained. The lower limit of the viscosity of the component (B3) at 25°C is not particularly limited, and can be set to 0.005 Pa.s, for example.

The component (B3) is preferably a hydrocarbon compound having at least two alkenyl groups in one molecule, which may contain a hydroxyl group and may have an aromatic group or an oxygen atom (ether bond, ester bond, etc.), or an organic polysiloxane represented by the following general formula (6).

In the above formula (6), R ⁶ may be the same or different and are unsubstituted or substituted monovalent alkyl groups having 1 to 20 carbon atoms and having no aliphatic unsaturated bonds, or alkenyl groups having 2 to 12 carbon atoms which may have an oxygen atom interposed therein, and at least two R ⁶ are alkenyl groups.

The monovalent hydrocarbon group having 1 to 20 carbon atoms and having no aliphatic unsaturated bond may be specifically selected from the following groups: methyl, ethyl, propyl, butyl, etc. are preferably alkyl groups having 1 to 6 carbon atoms; cyclohexyl, etc. are preferably cycloalkyl groups having 5 to 8 carbon atoms; phenyl, tolyl, etc. are preferably aryl groups having 6 to 10 carbon atoms; benzyl, The group is preferably an aralkyl group having 7 to 10 carbon atoms; or a hydroxypropyl group, cyano group, halogen atom or the like which replaces part or all of the hydrogen atoms bonded to the carbon atom of the group with a hydroxyl group, a cyano group, a halogen atom or the like, such as a hydroxypropyl group, a cyanoethyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group or the like; in particular, from the viewpoint of the releasability, an alkyl group or an aryl group is preferred, and a methyl group, an ethyl group, a propyl group or a phenyl group is more preferred.

Examples of the alkenyl group having 2 to 12 carbon atoms which may have an oxygen atom therethrough include the same ones as those mentioned above for the alkenyl group having 2 to 12 carbon atoms. Among them, vinyl and alkenyloxy groups are preferred.

In the above formula (6), m', n', o', and p' are selected from positive numbers within the above viscosity range, and in particular, m' is an integer greater than 2, preferably an integer from 2 to 100, n' is an integer greater than 0, preferably an integer from 0 to 500, more preferably an integer from 0 to 300, and further preferably an integer from 0 to 140, o' is an integer greater than 0, preferably an integer from 0 to 30, p' is an integer greater than 0, preferably an integer from 0 to 30, 2≦m'+n'+o'+p'≦502, preferably 2≦m'+n'+o'+p'≦300, and more preferably 2≦m'+n'+o'+p'≦150. The organopolysiloxane represented by the above formula (6) may be linear, branched or cyclic.

More preferably, the component (B3) is a partially hydrolyzed condensate of an alkoxysilane mixture containing 10 mol% or more of an organic alkoxysilane represented by the following general formula (6-1), and is a compound having a linear or branched and/or cyclic siloxane structure, or a mixture thereof. Alkenyl-Si(OR11) ₃ ･･･(6-1) (In formula (6-1), Alkenyl is a monovalent organic group having an alkenyl group, and R11 may be the same or different and is an unsubstituted or substituted alkyl or hydroxyl group having 1 to 20 carbon atoms and not having an aliphatic unsaturated bond and may contain an oxygen atom.)

When the component (B3) is formulated, it is preferred that the molar number of hydrogen atoms bonded to silicon atoms in the composition of the present invention is an amount equivalent to 0.5 to 10 times the total molar number of alkenyl groups in the components (A) and (B3). Here, the hydrogen atoms bonded to silicon atoms may constitute Si-H groups, for example. Thus, the hydrogen atoms bonded to silicon atoms in the composition include hydrogen atoms of the Si-H groups of the (B2) compound. When the composition of the present invention includes the component (C) described below, the hydrogen atoms bonded to silicon atoms in the composition further include hydrogen atoms bonded to silicon atoms possessed by the component (C).

In addition, the amount of component (B3) can be set in the range of 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the organopolysiloxane of component (A). By setting the amount of component (B3) to 0.1 to 10 parts by mass relative to 100 parts by mass of component (A), the light peeling effect can be maintained and the substrate adhesion can be sufficiently improved.

Specific examples of the component (B3) include the following components. Example 1 of the component (B3) Wherein, a''+b'' is 2 to 150, a'' is 2 or more, and the molecular terminal is blocked with (a''+b''+2) or less methoxy groups, ethoxy groups, or propoxy groups, and a part of them may be substituted with hydroxyl groups. Example 2 of component (B3) Wherein, c''+d''+e'' is 2 to 150, e'' is 2 or more, and the molecular terminal is capped with (c''+2) or less methoxy groups, ethoxy groups, or propoxy groups, and a part of them may be substituted with hydroxyl groups. Example 3 of component (B3) Here, a''+b''+c''+d''+e'' is 2 to 150, a'' is 2 or more, and the molecular terminal is capped with (a''+b''+c''+2) or less methoxy groups, ethoxy groups, or propoxy groups, and a part of them may be substituted with hydroxy groups.

The following compounds can be more preferably listed. A compound represented by the above average formula and having 7 or less methoxy groups at the molecular ends. A compound represented by the above average formula and having 10 or less methoxy groups at the molecular ends.

[(C): Organic hydropolysiloxane] The silicone composition for peeling sheets of the present invention may further include (C) organic hydropolysiloxane, which has at least two hydrogen atoms bonded to silicon atoms in one molecule and is different from the aforementioned (B2) compound. For the composition of the present invention, component (C) is an arbitrary component.

The organohydropolysiloxane of the component (C) has at least two hydrogen atoms (hereinafter also referred to as "SiH groups") bonded to silicon atoms in one molecule, and the SiH groups react with the alkenyl groups in the component (A) and any of the components (B3) to form a hardened film.

The organohydropolysiloxane of the component (C) is not particularly limited as long as it has at least two hydrogen atoms bonded to silicon atoms in one molecule and is different from the compound (B2). As a specific difference from the compound (B2), for example, the amount of Si-H groups it has is less than 1.3 mol/100 g.

Examples of the component (C) include a component represented by the following average composition formula (7).

In the above formula (7), ^R7 may be the same or different and is an unsubstituted or substituted monovalent alkyl group having no aliphatic unsaturated bond. Specifically, examples include: methyl, ethyl, propyl, butyl, etc. are preferably alkyl groups having 1 to 6 carbon atoms; cyclohexyl, etc. are preferably cycloalkyl groups having 5 to 8 carbon atoms; phenyl, tolyl, etc. are preferably aryl groups having 6 to 10 carbon atoms; benzyl, etc. are preferably arylalkyl groups having 7 to 10 carbon atoms; or hydroxypropyl, cyanoethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, etc. obtained by replacing part or all of the hydrogen atoms bonded to the carbon atoms of these groups with hydroxyl, cyano, halogen atoms, etc. Among them, alkyl groups and aryl groups are preferred, and methyl groups are more preferred from the viewpoint of increasing the addition reaction rate.

s is a positive number of 0.1 to 2, preferably a positive number of 0.2 to 1.5, t is a positive number of 0.1 to 3, preferably a positive number of 0.2 to 2, s+t is less than 3.1, especially 0.5 to 2.7.

Examples of the organohydropolysiloxane represented by the above formula (7) include: a polymer or copolymer having at least one of R ⁷ HSiO _2/2 units (R ⁷ is the same as above, and the same applies hereinafter), HSiO _3/2 units, and R ⁷ ₂ HSiO _1/2 units, and further including at least one of R ⁷ ₂ SiO _2/2 units, R ⁷ SiO _3/2 units, and R ⁷ ₃ SiO _1/2 units as appropriate; preferably, a total of at least two, preferably 10 to 100, R ⁷ HSiO _2/2 units or R ⁷ ₂ HSiO _1/2 units are contained in one molecule. In addition, any amount of SiO _4/2 units may be contained.

The content of SiH groups in the organopolysiloxane of the component (C) is preferably 0.1 to less than 1.3 mol/100 g, and particularly preferably 0.2 to less than 1.3 mol/100 g.

The organohydropolysiloxane may be linear, branched, or cyclic, and may be a mixture thereof.

In addition, the viscosity of component (C) at 25°C is preferably 0.001 to 10 Pa.s, and particularly preferably 0.005 to 5 Pa.s. If the viscosity of component (C) is 0.001 to 10 Pa.s, both appropriate curability and workability can be achieved.

Specific examples of the component (C) include the following, but the present invention is not limited thereto. In the following formula, Me and Ph represent a methyl group and a phenyl group, respectively.

The amount of component (C) is preferably such that the molar number of hydrogen atoms bonded to silicon atoms is 0.5 to 10 times the molar number of olefinic groups in the composition, and particularly preferably 1 to 5 times the molar number of hydrogen atoms bonded to silicon atoms is 0.5 to 10 times the molar number of olefinic groups in the composition. In the composition, the light peeling property can be maintained, and the curing property and the adhesion to the substrate can be further improved.

As described above, the (B2) compound contains Si-H groups and therefore contains hydrogen atoms bonded to silicon atoms. Therefore, when the (C) component is included, the hydrogen atoms bonded to silicon atoms in the composition include the (C) component and the hydrogen atoms bonded to silicon atoms of the (B2) compound. Furthermore, as described above, when the composition of the present invention contains the (B3) component, it is preferred that the molar number of hydrogen atoms bonded to silicon atoms in the composition of the present invention is 0.5 to 10 times the total molar number of alkenyl groups in the (A) component and the (B3) component. That is, when the composition of the present invention comprises components (B3) and (C), it is preferred that the total molar number of hydrogen atoms bonded to silicon atoms of the components (C) and (B2) is in the range of 0.5 to 10 times, and particularly preferably in the range of 1 to 5 times, the total molar number of alkenyl groups of the components (A) and (B3).

In order to obtain a suitable crosslinking density, the amount of component (C) is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass per 100 parts by mass of component (A).

[(D): Platinum metal catalyst] The platinum metal catalyst of component (D) is a catalyst used to promote the addition reaction of component (A) and component (B3) with the compound (B2) and component (C). As a catalyst for promoting the so-called hydrosilylation reaction, any catalyst known to those skilled in the art to which the present invention belongs can be used. Examples of such platinum metal catalysts include platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts; among them, platinum-based catalysts are particularly preferred. As the platinum catalyst, for example, chloroplatinic acid, alcohol solution or aldehyde solution of chloroplatinic acid, complexes of chloroplatinic acid and various olefins or vinyl siloxanes, and various olefins or vinyl siloxane complexes of platinum, etc. The amount of component (D) is the amount of catalyst. In terms of obtaining a good hardened film, it is preferably set in the range of 10 to 1000 ppm when converted to platinum group metal by mass, and particularly preferably in the range of 20 to 500 ppm.

[(E): Organic solvent for dilution] In the silica composition of the present invention, an organic solvent for dilution can be formulated as an optional component. Specifically, an organic solvent of component (E) is used in an amount of 0 to 20,000 parts by mass relative to 100 parts by mass of component (A).

The silica composition of the present invention can also be a solvent-free composition obtained by mixing specific amounts of the above-mentioned components (A), (B) and (D) and any other components. By diluting the composition with an organic solvent, practical advantages such as improved coating workability, improved coating film thickness, surface polishing state, and other coating film conditions can be obtained.

As the organic solvents that can be used, there are aromatic hydrocarbon compounds such as toluene and xylene; aliphatic hydrocarbon compounds such as hexane, heptane, and isoparaffin; ketone compounds such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester compounds such as ethyl acetate and butyl acetate; ether compounds such as diisopropyl ether and 1,4-dioxane; any organic solvent can be used as long as it can dissolve silicon oxide. It can also be dispersed and diluted in water in any proportion and used.

The amount of component (E) to be added is preferably 100 to 20,000 parts by mass, and more preferably 200 to 10,000 parts by mass, relative to 100 parts by mass of component (A). By setting the amount of component (E) to 100 to 200,000 parts by mass, the above advantages can be fully obtained by dilution.

[(F) Peeling force control component] Furthermore, the composition of the present invention may contain a peeling force control component (F). As the (F) component, the following (F1) component and/or the following (F2) component may be used, and the amount thereof may be 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) component. By including the (F) component in this amount, the adhesion to the substrate can be maintained, and the peeling force can be appropriately controlled.

(F1) : Peel force control component containing acrylic acid - silicone graft copolymer. Component (F1) is a peel force control component containing acrylic acid-silicone graft copolymer. By formulating this component, a very small peel force can be obtained, thereby obtaining an excellent hardened film (peel film) with a high residual bonding rate of the adhesive sheet after peeling.

The acrylic-silicone graft copolymer used in the present invention is a copolymer having a weight average molecular weight of 1,000 to 100,000, which is obtained by free radical polymerization of an organic polysiloxane compound (a) having an acryl group and/or a methacryl group (hereinafter also referred to as a (meth)acryl group) and a free radical polymerizable monomer (b) having one free radical polymerizable group in one molecule.

According to the measurement results of gel permeation chromatography (hereinafter referred to as "GPC") using toluene as a developing solvent, the weight average molecular weight of the copolymer is 1,000 to 100,000, preferably 1,500 to 50,000, and more preferably 2,000 to 30,000 when converted to polystyrene. If the weight average molecular weight is 1,000 to 100,000, a high residual bonding rate and excellent dispersibility for the silicone composition can be taken into account.

[Component (a): an organic polysiloxane compound having a (meth)acryl group] The organic polysiloxane compound (a) used in the present invention is not particularly limited as long as it has a (meth)acryl group. In terms of ease of copolymerization with a radically polymerizable monomer (b) having one radically polymerizable group in one molecule, ease of synthesis of the organic polysiloxane compound itself, and the effect of the peeling force controlling component, it is preferably a radically polymerizable siloxane macromonomer represented by the following general formula (3).

In the above general formula (3), ^R2 is a hydrogen atom or a methyl group, and X is a group selected from an oxygen atom, an NH group and a sulfur atom (a divalent functional group).

Y is a divalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, which may be mediated by an oxygen atom. Specific examples include alkylene groups such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), hexamethylene, and octamethylene; arylene _groups such as phenylene; combinations of two or more of these groups (alkylene-arylene, etc.) _{; -CH2CH2} - _{O - CH2CH2-} ; -CH2CH2- _{O-CH2CH2 - O} -CH2CH2-; _-CH ( _{CH3 ) CH2 - O} -CH( _{CH3 ) CH2-;} -CH2CH2CH2CH2 _{-O -CH2CH2CH2-} . _Y is preferably ethylene, propylene, or _butylene . f is an integer ranging from 0 to 1000, preferably an integer ranging from 0 to 500, and more preferably an integer ranging from 0 to 200.

^R3 may be the same or different and is an unsubstituted or substituted monovalent alkyl group having 1 to 20 carbon atoms, preferably 1 to 18 carbon atoms, a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, or a substituent represented by the following general formula (4). (In formula (4), ^R4 may be the same or different and is an unsubstituted or substituted monovalent alkyl group having 1 to 20 carbon atoms, preferably 1 to 18 carbon atoms, a hydrogen atom, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and g is an integer of 0 to 300).

Here, as R ³ and R ⁴ , unsubstituted or substituted monovalent alkyl groups with 1 to 20 carbon atoms, specific examples include: alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl and tolyl; aralkyl groups such as benzyl and phenethyl; or hydroxypropyl groups obtained by replacing part or all of the hydrogen atoms bonded to the carbon atoms of these groups with hydroxyl, cyano, halogen atoms, etc.; cyanoethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, etc. Specific examples of alkoxy groups with 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, and butoxy. As R ³ , an alkyl group or an aryl group is preferred, and an alkyl group with 1 to 5 carbon atoms is more preferred. As R ⁴ , an alkyl group or an aryl group is preferred, and an alkyl group with 1 to 5 carbon atoms is more preferred. g is an integer of 0 to 300, preferably an integer of 0 to 100, and more preferably an integer of 0 to 50.

Specific examples of the component (a) include the following, but the present invention is not limited thereto. In the following formula, Me, Ome, and Ph represent a methyl group, a methoxy group, and a phenyl group, respectively.

[Component (b): Radically polymerizable monomer] The radically polymerizable monomer (b) used in the present invention may be used alone or in combination of two or more. There are no particular restrictions as long as the compound has one radically polymerizable group in one molecule.

As the component (b), there may be exemplified compounds having one radical polymerizable group such as an acryloyl group, a methacryloyl group, a styryl group, a cinnamate group, a vinyl group, an allyl group, etc. in one molecule. Specifically, there may be exemplified methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, 1,2-dimethyl ... Ester compounds of (meth)acrylic acid such as benzyl (meth)acrylate, isoborneol (meth)acrylate, trifluoropropyl (meth)acrylate, perfluorobutylethyl (meth)acrylate, perfluorooctylethyl (meth)acrylate; epoxy radical polymerizable monomers such as glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 3,4-epoxyhexylmethyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, etc.; γ-methacryloyloxypropyl trimethoxysilane, γ-methacryloyloxypropyl methyl dimethoxysilane, γ-methacryloyloxypropyl dimethyl methoxysilane, γ-methacryloyloxypropyl triethoxysilane, γ-methacryloyloxypropyl methyl diethoxysilane, γ-methacryloyloxypropyl tributoxysilane, γ-methyl Free radical polymerizable silane compounds such as acryloxypropyl triisoacryloxysilane, γ-acryloxypropyl trimethoxysilane, acryloxymethyl trimethoxysilane, γ-acryloxypropyl triethoxysilane, γ-acryloxypropyl methyl diethoxysilane, styryl trimethoxysilane, styryl triethoxysilane, α-methylstyryl trimethoxysilane; free radical polymerizable monomers containing polyoxyalkylene groups; glyceryl (meth)acrylate.

Considering the light peeling effect and high residual bonding rate effect obtained by the peeling force control component (F), it is preferred to contain a (meth)acrylic acid alkyl ester having a carbon number of 1 to 30, and more preferably to contain methyl (meth)acrylate.

[Ratio of component (a)/component (b)] The polymer mass ratio [(a)/(b)] of the organic polysiloxane compound (a) having a (meth)acryloyl group and the free radical polymerizable monomer (b) having one free radical polymerizable group in one molecule is preferably in the range of 30/70 to 99/1, more preferably 40/60 to 97/3, and further preferably 50/50 to 95/5. If the polymer mass ratio [(a)/(b)] is in the range of 30/70 to 99/1, the light peeling effect can be maintained, and sufficient compatibility with the silicone composition can be exhibited, thereby preventing the separation of the (F) peeling force control component.

[Synthesis method of acrylic-silicone graft copolymer] The copolymerization of monomer raw materials including an organic polysiloxane compound (a) having a (meth)acryl group and a free radical polymerizable monomer (b) having one free radical polymerizable group in one molecule is carried out in the presence of the following common free radical polymerization initiators: peroxides such as benzoyl peroxide, diisopropylbenzene peroxide, lauryl peroxide, and tert-butyl peroxy-2-ethylhexanoate; azo compounds such as 2,2'-azobis(2-methylbutyronitrile); any of the methods of solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization can also be applied.

In the present invention, among the polymerization methods, the solution polymerization method is preferred because it is easy to adjust the molecular weight of the obtained acrylic-silicone graft copolymer to the optimal range. The solvent used in this case can be exemplified by: aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; alcohols such as ethanol, isopropanol, n-butanol, and isobutanol, etc., or a mixture of two or more thereof.

The polymerization temperature is preferably in the range of 50 to 180°C, particularly preferably in the range of 60 to 120°C. Under this temperature condition, the polymerization reaction can be completed in about 1 to 10 hours. There is no particular limitation on the method of extracting the copolymer from the copolymerization solution, and examples thereof include: a method of evaporating the solvent, a method of adding a poor solvent such as water or methanol to the copolymerization solution to precipitate the copolymer, and a method of drying the copolymer.

The amount of component (F) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, relative to 100 parts by mass of component (A). When component (F) is included in the above preferred amount, both excellent light peeling effect and excellent curing property can be achieved.

(F2) : Linear phenylmethyl polysiloxane The component (F2) is a linear phenylmethyl polysiloxane, which may have no functional group or may have an alkoxy group and/or a silanol group at the terminal.

The component (F2) is preferably an organopolysiloxane having a viscosity of 0.01 to 70 Pa.s in 30% by mass toluene at 25°C. By including the component (F2) having a viscosity within this range, both excellent peeling force control effect and excellent productivity can be achieved.

[Other optional components] The silicon oxide composition of the present invention is obtained by mixing the above-mentioned component (A), the (B1) compound, the (B2) compound and the (D) component in specific amounts, and can further include the above-mentioned component (B3), the (C) component, the (E) component and the (F) component as optional components in the above-mentioned preferred amounts, and other components can be added in any amount as needed. As components commonly used in silicon oxide-based stripping agent compositions, known components can be added in normal mixing amounts.

As other optional components, for example, as an expiration date extender, various known components such as organic nitrogen compounds, organic phosphorus compounds, acetylene compounds, oxime compounds, and organic chlorine compounds can be used. Examples include: acetylene alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-penten-3-ol, and phenylbutynol; acetylene compounds such as 3-methyl-3-1-penten-1-yne, 3,5-dimethyl-1-hexyn-3-yne; reaction products of these acetylene compounds with alkoxysilanes, siloxanes, or hydrosilanes; vinyl siloxanes such as tetramethylvinylsiloxane cyclopentane; organic nitrogen compounds such as benzotriazole; and other organic phosphorus compounds, oxime compounds, and organic chromium compounds.

The amount of the compounds to be formulated may be an amount that can provide a good pot life, and is generally preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of component (A).

When the composition of the present invention is prepared as an emulsion composition, a surfactant or a high molecular weight emulsifier may be added, and the appropriate amount thereof is in the range of 0.1 to 10 parts by weight relative to 100 parts by weight of the component (A).

Furthermore, other known antioxidants, pigments, stabilizers, antistatic agents, defoaming agents, adhesion enhancers other than component (B), thickeners, and inorganic fillers such as silica may be formulated as optional components as necessary.

Regarding the preparation of the silicone composition for a release sheet, the following method is more preferable in terms of the applicable period: the above-mentioned (A) component, (B1) compound, (B2) compound, and optional components are mixed uniformly in advance, and then the (D) component is added immediately before use.

As another adjustment method, the following method is more advantageous for optimizing the peeling properties of the cured product: after uniformly mixing the component (A) and the optional components in advance, adding the component (B) (the (B1) compound and the (B2) compound, and the optional (B3) component) and the component (D) as the adhesion improving component immediately before use.

Furthermore, it is also preferable to use a method of adding (B1) compound and (B2) compound separately. (B1) and (B2) compounds have different effects on improving adhesion, so in terms of adhesion, peeling characteristics, and cost, it is more ideal to adjust the optimal addition amount of (B1) and (B2) compounds according to the use of the composition and use them. When used as an additive as described above, it is also possible to prepare an additive composition obtained by mixing (B1) and/or (B2) compounds with other components for use.

[Release sheet (coated product)] The release sheet of the present invention is obtained by coating the release sheet silicone composition of the present invention on a paper substrate or a film substrate and curing the coating.

The release sheet of the present invention may include, for example, a sheet-like substrate such as a paper substrate or a film substrate, and a cured product (cured film) of the silicone composition for a release sheet of the present invention formed on the substrate.

The hardened film can be formed on the substrate by the following method: the above-mentioned peeling sheet silicone composition of the present invention is directly diluted or further diluted with the above-mentioned diluting solvent or water within the above-mentioned range, and then coated with a coating method such as coating by a notch wheel coater, a die lip coater, a roll coater, a mold coater, a knife coater, a scraper coater, a rod coater, a contact coater, a gravure coater, a wire rod coater, etc., screen coating, immersion coating, casting coating, etc., at a coating weight of 0.01 to 100 g/m ^2. After applying to one or both sides of a sheet substrate such as paper or film, heat at 50-200°C for 1-120 seconds. When a hardened film (release layer) is formed on both sides of the substrate, it is preferred to form the hardened film on each side of the substrate.

Examples of substrates include: various coated papers such as polyethylene laminated paper, glassine paper, high-grade paper, kraft paper, and clay-coated paper; synthetic papers such as YUPO; polyethylene films, polypropylene films such as cast polypropylene (CPP) or oriented polypropylene (OPP); polyester films such as polyethylene terephthalate films (PET films); polyamide films, polyimide films, polylactic acid films, polyphenol films, polycarbonate films, etc. In order to improve the adhesion between the substrates and the hardened film (release layer), substrates that have been subjected to corona treatment, etching treatment, or plasma treatment on the surface of the substrate may also be used. [Example]

Hereinafter, the present invention will be specifically described by showing synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, parts represent parts by mass.

(Preparation of silicone composition and peeling film) <Raw materials> (A) Component (A-1) An organopolysiloxane composed of 0.04 mol% of trivinylsiloxane units represented by (CH ₂ =CH) ₃ SiO _1/2 , 0.4 mol% of methylvinylsiloxane units represented by (CH ₃ )(CH ₂ =CH)SiO _2/2 , and 99.56 mol% of dimethylsiloxane units represented by (CH ₃ ) ₂ SiO _2/2. The viscosity of the diluted solution in 30 mass% toluene at 25°C is 15 Pa.s. The olefin content is 0.01 mol/100 g.

(A-2) An organopolysiloxane composed of 0.02 mol% of dimethylvinylsiloxane units represented by (CH ₃ ) ₂ (CH ₂ =CH)SiO _1/2 , 3.4 mol% of methylvinylsiloxane units represented by (CH ₃ )(CH ₂ =CH)SiO _2/2 , and 96.58 mol% of dimethylsiloxane units represented by (CH ₃ ) ₂ SiO _2/2 , having a 30 mass% toluene dilution viscosity at 25°C of 10 Pa.s, and 0.04 mol/100 g of olefin content

(B) Components (B1-1) Compounds 118.2 parts by mass (0.5 mol) of 3-glycidoxypropyltrimethoxysilane, 68.1 parts by mass (0.5 mol) of methyltrimethoxysilane, and 15 parts by mass (0.83 mol) of water were partially hydrolyzed and condensed at 70°C for 5 hours in the presence of hydrochloric acid to obtain an epoxy-containing siloxane oligomer Viscosity at 25°C: 0.05 Pa.s Average degree of polymerization: 5 Siloxane units having epoxy groups bonded to silicon atoms via carbon atoms: 50 mol% Silanol group content: 0.012 mol/100 g, silanol content was determined by the Grignard method for quantifying the amount of methane generated using methylmagnesium iodide Alkoxy content: 0.9 mol/100 g

(B1-2) Compound 166.7 parts by mass (0.7 mol) of tetraethoxysilane, 47.3 parts by mass (0.2 mol) of 3-glycidoxypropyltrimethoxysilane, 17.8 parts by mass (0.1 mol) of methyltriethoxysilane, and 15 parts by mass (0.83 mol) of water were partially hydrolyzed and condensed at 80°C for 5 hours in the presence of hydrochloric acid to obtain an epoxy-containing siloxane oligomer Viscosity at 25°C: 0.02 Pa.s Average degree of polymerization: 5 Siloxane units having epoxy groups bonded to silicon atoms via carbon atoms: 20 mol% Silanol group content: 0.015 mol/100 g Alkoxy group content: 1.4 mol/100 g

(B1-3) Compound 236.3 parts by mass (1 mol) of 3-glycidoxypropyltrimethoxysilane and 9 parts by mass (0.5 mol) of water were partially hydrolyzed and condensed at 70°C for 5 hours in the presence of hydrochloric acid to obtain an epoxy-containing siloxane oligomer Viscosity at 25°C is 0.005 Pa.s Average degree of polymerization is 2 Siloxane units having epoxy groups bonded to silicon atoms via carbon atoms are 100 mol% Silanol group content is 0.015 mol/100 g Alkoxy group content is 0.9 mol/100 g

(B1-4) The compound is an organic polysiloxane represented by the following formula (w1=42, w2=33, Ep ¹ is 2-(3,4-epoxycyclohexyl)ethyl, Me is methyl).

(B1-5) The compound is an organic polysiloxane represented by the following formula (w=20, Ep ¹ is 2-(3,4-epoxycyclohexyl)ethyl, Me is methyl).

(B1-6) Compound (B1-4) wherein Ep ¹ is 3-(2,4-epoxypropoxy)propyl organic polysiloxane

(B1-7) Compound (B1-5) wherein Ep ¹ is 3-(2,4-epoxypropoxy)propyl organic polysiloxane

(B2-1) Compound: An organohydropolysiloxane composed of 5 mol% of trimethylsiloxane units represented by (CH ₃ ) ₃ SiO _1/2 and 95 mol% of methylhydrosiloxane units represented by (CH ₃ )HSiO _2/2 . Viscosity at 25°C: 0.02 Pa.s. Si-H group content: 1.5 mol/100 g. Degree of polymerization: 40

(B2-2) Compound: an organohydropolysiloxane composed of 2 mol% of trimethylsiloxane units represented by (CH ₃ ) ₃ SiO _1/2 , 78 mol% of methylhydrosiloxane units represented by (CH ₃ )HSiO _2/2 , and 20 mol% of dimethylsiloxane units represented by (CH ₃ ) ₂ SiO _2/2 . Viscosity at 25°C: 0.1 Pa.s. Si-H group content: 1.2 mol/100 g. Degree of polymerization: 100

(B3-1) Component 27.2 parts by mass (0.2 mol) of methyltrimethoxysilane, 187.5 parts by mass (0.8 mol) of 3-(acryloyloxy)propyltrimethoxysilane, and 15.0 parts by mass (0.83 mol) of water were partially hydrolyzed and condensed at 70°C for 5 hours in the presence of hydrochloric acid to obtain an alkenyl-containing siloxane oligomer The viscosity at 25°C is 0.04 Pa.s The average degree of polymerization is 6 The siloxane unit having an alkenyl group bonded to a silicon atom via a carbon atom is 80 mol% The alkenyl content is 0.24 mol/100 g The silanol content is 0.009 mol/100 g,

(B3-2) Component 54.1 parts by mass (0.45 mol) of dimethyldimethoxysilane, 73.3 parts by mass (0.3 mol) of diphenyldimethoxysilane, 37.1 parts by mass (0.25 mol) of vinyltrimethoxysilane, and 15.3 parts by mass (0.85 mol) of water were partially hydrolyzed and condensed at 70°C for 5 hours in the presence of hydrochloric acid to obtain an alkenyl-containing siloxane oligomer The viscosity at 25°C is 0.10 Pa.s The average degree of polymerization is 7 The siloxane unit having an alkenyl group bonded to a silicon atom via a carbon atom is 25 mol% The alkenyl content is 0.078 mol/100 g The silanol content is 0.011 mol/100 g

(C) Component (C-1) Organohydropolysiloxane composed of 2 mol% of trimethylsiloxane units represented by (CH ₃ ) ₃ SiO _1/2 , 70 mol% of methylhydrosiloxane units represented by (CH ₃ )HSiO _2/2 , and 28 mol% of dimethylsiloxane units represented by (CH ₃ ) ₂ SiO _2/2 . Viscosity at 25°C: 0.1 Pa.s. Si-H group content: 1.1 mol/100 g

(D) Component: Platinum-vinylsiloxane complex as catalyst

(E) Components Mixed solvent with a mass ratio of toluene and hexane of 1:1

(F) Component (F-1) Component Peeling force control component: Acrylic-silicone graft copolymer obtained by the following synthesis example 1

[Synthesis Example 1] 30.0 parts of toluene were fed into a glass reactor including a stirrer, a thermometer, a reflux cooler, and a dropping device. After heating to 90-100°C, a mixture of 55.7 parts (0.067 mol) of a radical polymerizable siloxane macromonomer represented by the following formula (8), 9.8 parts (0.098 mol) of methyl methacrylate, 2.5 parts (0.012 mol) of tert-butyl peroxy-2-ethylhexanoate, and 51.8 parts of toluene was added dropwise over 4 hours under nitrogen flow. After polymerization at 90-100°C for 2 hours, 0.4 parts (0.002 mol) of tert-butyl peroxy-2-ethylhexanoate was added and polymerization was carried out for 2 hours. Then, the mixture was dried in a vacuum dryer at 150°C/10 mmHg to obtain an acrylic-silicone graft copolymer. The weight average molecular weight of the copolymer measured by GPC was 12,000 when converted to polystyrene.

(F-2) Component: an organopolysiloxane composed of 0.7 mol% of trimethylsiloxane units represented by (CH ₃ ) ₃ SiO _1/2 , 94.3 mol% of dimethylsiloxane units represented by (CH ₃ ) ₂ SiO _2/2 , and 5 mol% of diphenylsiloxane units represented by (C ₆ H ₅ ) ₂ SiO _2/2 . The viscosity at 25°C is 3.00 Pa.s

(Component G) Expiration period extender: 3-methyl-1-butyn-3-ol

<Examples 1 to 20, Comparative Examples 1 to 20> Using the above-mentioned (A) to (E) and (G) components as raw materials, a coating composition was prepared in the following order. According to the mixing ratios in Tables 1 and 2, components (A) to (C) were taken into a flask, 3200 parts of component (E) and 3 parts of component (G) were added, and stirred to dissolve. Component (D) was added to the obtained solution in an amount of 100 ppm relative to component (A) when converted to platinum mass, and the mixture was stirred and mixed to obtain a coating composition. Using the composition, a release film (coating product) was prepared by the following method and evaluated.

<Examples 21 to 24> Using the above-mentioned (A) to (G) components as raw materials, a coating composition was prepared in the following order. According to the mixing ratio of Table 2, components (A) to (C) and (F) were taken into a flask, 3200 parts of component (E) and 3 parts of component (G) were added, and stirred to dissolve. Component (D) was added to the obtained solution in an amount of 100 ppm relative to component (A) when converted to platinum mass, and the mixture was stirred to obtain a coating composition. Using the composition, a peeling film (coating product) was prepared by the following method and evaluated.

＜Evaluation＞ [Hardening property (adhesion immediately after curing)] The obtained composition was applied to a PET film having a thickness of 38 μm at a solid content of 0.1 g/m ² using a bar coater, and heated in a hot air dryer at 100°C for a specified number of seconds (30 seconds or 60 seconds) to form a release agent layer (hardened film) to obtain a release film. The release agent layer was scratched 10 times with a finger, and the presence of turbidity and peeling was observed with the naked eye, and the evaluation was performed based on the following criteria. A: No turbidity or peeling was observed at 30 seconds. B: Turbidity and peeling were observed at 30 seconds, but no turbidity or peeling was observed at 60 seconds. C: Turbidity and shedding were observed at 60 seconds. The results are shown in Tables 1 and 2 below.

[Adhesion] The obtained composition was applied to a PET film having a thickness of 38 μm at a solid content of 0.1 g/m ² using a bar coater, and heated in a hot air dryer at 120°C for 40 seconds to form a release agent layer to obtain a release film. The obtained release film was stored at 25°C and 50% relative humidity (RH) for one week, or at 60°C and 90% RH for one week. After scratching the release agent layer 10 times with a finger, the presence of turbidity and peeling was observed with the naked eye, and evaluated based on the following standards. A: No turbidity or peeling was observed. B: Turbidity was observed, but no peeling was observed. C: Turbidity or shedding was observed. The results are shown in Tables 1 and 2 below.

[Peeling force] The compositions obtained in Examples 5 to 7, 13, 18 to 21 and 23 and Comparative Examples 1, 3 and 20 were coated on a 38 μm thick PET film at a solid content of 0.1 g/m ² using a bar coater, and heated in a hot air dryer at 120°C for 40 seconds to form a peeling agent layer (hardened film). Evaluation was performed according to the FINAT method in the following order.

A 25 mm wide tape (Tesa7475 tape, a trade name manufactured by Tesa Tape. Inc.) was attached to the surface of the release agent layer and treated under the following two pressing conditions: a load of 70 g/cm ² was applied at 25°C for 20 hours (pressing A); a load of 20 g/cm ² was applied in a 70°C dryer and heat treated for 20 hours (pressing B). After air cooling for about 30 minutes, the Tesa7475 tape was stretched at an angle of 180° and a peeling speed of 0.3 m/min using a tensile tester (Shimadzu Corporation, trade name DSC-500 tester), and the force required for peeling (N/25 mm) was measured. The results are shown in Table 3 below.

[Residual Adhesion Ratio] A release agent layer was formed in the same manner as in the above-mentioned evaluation of the release force, and a polyester tape (Nitto 31B, a trade name manufactured by Nitto Denko Corporation) with a width of 25 mm was attached to the surface of the release agent layer. A load of 20 g/cm ² was applied in a 70°C dryer and heat-treated for 20 hours. Thereafter, the polyester tape was peeled off from the release agent layer and attached to a SUS stainless steel plate. Next, the polyester tape was peeled off from the SUS stainless steel plate using a tensile tester, and the release force F was measured.

In addition, a polyester tape was attached to a polytetrafluoroethylene plate instead of a release agent layer, and the treatment was carried out in the same manner, and the release force F ₀ was measured. Then, the residual adhesion rate was calculated according to the formula of (release force F/release force F ₀ )×100(%). The higher the residual adhesion rate, the smaller the effect of the contact with the release agent layer on the adhesiveness of the tape adhesive surface, and thus it can be evaluated as an excellent release agent layer that can suppress the reduction of the adhesive force of the tape after peeling. The results are shown in the following Table 3.

[Table 1] No A ingredient B ingredient C ingredient F component Hardening Tightness Alkenyl content A+B3 Si-H content B2 + C Si-H/olefin molar ratio B1 B2 B3 25℃， 50% RH 60℃， 90% RH Embodiment 1 A-1 100 copies B1-1 0.2 parts B2-1 1.62 parts A A A 0.01 0.0245 2.5 Embodiment 2 A-1 100 copies B1-1 0.2 parts B2-1 0.02 parts C-1 2.2 parts A A A 0.01 0.0245 2.5 Embodiment 3 A-1 100 copies B1-1 1.0 B2-1 2.6 parts A A A 0.01 0.0392 3.9 Embodiment 4 A-1 100 copies B1-1 1.0 B2-1 1.0 C-1 2.2 parts A A A 0.01 0.0392 3.9 Embodiment 5 A-1 100 copies B1-1 1.5 parts B2-1 2.1 parts A A A 0.01 0.0317 3.2 Embodiment 6 A-1 100 copies B1-1 1.5 parts B2-1 0.5 parts C-1 2.2 parts A A A 0.01 0.0317 3.2 Embodiment 7 A-1 100 copies B1-1 1.5 parts B2-1 1.8 parts B3-1 1.5 parts A A A 0.0136 0.0272 2.0 Embodiment 8 A-1 100 copies B1-1 1.5 parts B2-1 0.2 parts B3-1 1.5 parts C-1 2.2 parts A A A 0.0136 0.0272 2.0 Embodiment 9 A-1 100 copies B1-1 3.0 copies B2-1 2.6 parts A A A 0.01 0.0392 3.9 Embodiment 10 A-1 100 copies B1-1 3.0 copies B2-1 1.0 C-1 2.2 parts A A A 0.01 0.0392 3.9 Embodiment 11 A-1 100 copies B1-1 10 sets B2-1 2.6 parts B3-2 2.0 parts A A A 0.01156 0.0392 3.4 Embodiment 12 A-1 100 copies B1-1 10 sets B2-1 1.0 B3-2 2.0 parts C-1 2.2 parts A A A 0.01156 0.0392 3.4 Embodiment 13 A-1 100 copies B1-2 1.5 parts B2-1 2.1 parts A B A 0.01 0.0317 3.2 Embodiment 14 A-1 100 copies B1-2 1.5 parts B2-1 0.5 parts C-1 2.2 parts A B A 0.01 0.0317 3.2 Embodiment 15 A-1 100 copies B1-2 5 servings B2-1 3.1 parts B3-1 0.5 parts A A A 0.0112 0.0467 4.2 Embodiment 16 A-1 100 copies B1-2 5 servings B2-1 1.5 parts B3-1 0.5 parts C-1 2.2 parts A A A 0.0112 0.0467 4.2 Embodiment 17 A-1 100 copies B1-2 10 sets B2-1 4.6 parts B3-2 2.0 parts A A A 0.01156 0.0692 6.0 Embodiment 18 A-1 100 copies B1-2 10 sets B2-1 3.0 copies B3-2 2.0 parts C-1 2.2 parts A A A 0.01156 0.0692 6.0 Embodiment 19 A-2 100 copies B1-1 1.5 parts B2-1 6.1 parts A A A 0.04 0.092 2.3 Embodiment 20 A-2 100 copies B1-1 1.5 parts B2-1 1.0 C-1 7.0 parts A A A 0.04 0.092 2.3

[Table 2] No A ingredient B ingredient C ingredient F component Hardening Tightness Alkenyl content A+B3 Si-H content B2 + C Si-H/olefin molar ratio B1 B2 B3 25℃， 50% RH 60℃， 90% RH Embodiment 21 A-1 100 copies B1-1 1.0 B2-1 1.9 parts — F-1 10 copies A A A 0.01 0.0287 2.9 Embodiment 22 A-1 100 copies B1-1 1.0 B2-1 0.3 parts — C-1 2.2 parts F-1 10 copies A A A 0.01 0.0287 2.9 Embodiment 23 A-1 100 copies B1-1 1.0 B2-1 1.9 parts — F-2 2.5 parts A A A 0.01 0.0287 2.9 Embodiment 24 A-1 100 copies B1-1 1.0 B2-1 0.3 parts — C-1 2.2 parts F-2 2.5 parts A A A 0.01 0.0287 2.9 Comparative example 1 A-1 100 copies — C-1 2.9 parts A C C 0.01 0.0319 3.2 Comparative example 2 A-1 100 copies — B2-1 2.1 parts A B C 0.01 0.0317 3.2 Comparative example 3 A-1 100 copies — B2-1 0.5 parts C-1 2.2 parts A C C 0.01 0.0317 3.2 Comparative example 4 A-1 100 copies B1-1 1.5 parts C-1 2.9 parts A C B 0.01 0.0319 3.2 Comparative example 5 A-1 100 copies B1-1 25 copies B2-1 4.1 parts B C B 0.01 0.0617 6.2 Comparative example 6 A-1 100 copies B1-1 25 copies B2-1 2.5 parts C-1 2.2 parts B C B 0.01 0.0617 6.2 Comparative example 7 A-1 100 copies B1-1 1.5 parts B2-2 2.1 parts A C A 0.01 0.0302 3.0 Comparative example 8 A-1 100 copies B1-1 1.5 parts B2-2 0.5 parts C-1 2.2 parts A C A 0.01 0.0302 3.0 Comparative example 9 A-1 100 copies B1-3 3.0 parts B2-1 2.1 parts A B C 0.01 0.0317 3.2 Comparative example 10 A-1 100 copies B1-3 3.0 parts B2-1 0.5 parts C-1 2.2 parts A C C 0.01 0.0317 3.2 Comparative example 11 A-1 100 copies B1-4 3.0 parts B2-1 2.1 parts A B C 0.01 0.0317 3.2 Comparative example 12 A-1 100 copies B1-4 3.0 parts B2-1 0.5 parts C-1 2.2 parts A C C 0.01 0.0317 3.2 Comparative example 13 A-1 100 copies B1-5 3.0 parts B2-1 2.1 parts A B C 0.01 0.0317 3.2 Comparative example 14 A-1 100 copies B1-5 3.0 parts B2-1 0.5 parts C-1 2.2 parts A C C 0.01 0.0317 3.2 Comparative example 15 A-1 100 copies B1-6 3.0 parts B2-1 2.1 parts A B C 0.01 0.0317 3.2 Comparative example 16 A-1 100 copies B1-6 3.0 parts B2-1 0.5 parts C-1 2.2 parts A C C 0.01 0.0317 3.2 Comparative example 17 A-1 100 copies B1-7 3.0 parts B2-1 2.1 parts A B B 0.01 0.0317 3.2 Comparative example 18 A-1 100 copies B1-7 3.0 parts B2-1 0.5 parts C-1 2.2 parts A C B 0.01 0.0317 3.2 Comparative example 19 A-2 100 copies B1-1 3.0 copies — C-1 7.0 parts B C A 0.04 0.077 1.9 Comparative example 20 A-2 100 copies B1-1 0.05 parts B2-1 0.05 parts C-1 7.0 parts B C C 0.04 0.0778 1.9

Peeling force: Peeling from the bonding surface at a peeling speed of 0.3m/min and 180 degrees

Pressing A: 70 g/ ^cm2 load, 25°C for 20 hours

Pressing B: 20g/ ^cm2 load, 70℃ for 20 hours

Residual Adhesion Rate: Nitto 31B tape was applied, and the tape was pressed at 70℃ for 20 hours with a load of 20g/ ^cm2 . The peeled tape was attached to a SUS plate, and pressed back and forth once with a 2kg tape roller. The adhesion was measured in the same way as the peeling force. The blank group was treated in the same way with a Teflon (registered trademark) plate and the measured value was set as 100%.

As shown in Tables 1 and 2, the compositions of Examples 1 to 24 of the present invention have excellent curing properties and can show excellent adhesion to the substrate, thereby forming a peeling agent layer (hardened film) that can maintain the excellent adhesion for a long time even in a harsh environment such as high temperature and high humidity. In addition, as shown in Table 3, the compositions of Examples 5 to 7, 13, 18 to 21 and 23 of the present invention can show that the peeling force will not be increased by the preparation of the adhesion enhancer, thereby providing a peeling agent layer that will not significantly damage the adhesion of the tape. The compositions of Examples 1 to 4, 8 to 12, 14 to 17, 22 and 24 of the present invention are also the same as the compositions of the Examples shown in Table 3. The peeling force will not be increased by the preparation of the adhesion enhancer, thereby providing a peeling agent layer that will not significantly impair the adhesion of the tape.

On the other hand, the composition of Comparative Example 1 contains neither the (B1) compound nor the (B2) compound. The compositions of Comparative Examples 2 and 3 contain no (B1) compound. The compositions of Comparative Examples 4 and 19 contain no (B2) compound. As a result, the stripping agent layer obtained from the respective compositions of Comparative Examples 1 to 4 and 19 cannot maintain adhesion to the substrate for a long time under a harsh environment. Furthermore, as can be seen from the comparison between Comparative Example 4 and Comparative Example 19, even if the amount of the (B1) compound is increased, if the (B2) compound is not included, adhesion to the substrate cannot be maintained for a long time under a harsh environment.

The amount of the (B1) compound in Comparative Examples 5 and 6 is 25 parts by mass relative to 100 parts by mass of the (A) component, which is too much. As a result, the peeling agent layer obtained from the compositions of Comparative Examples 5 and 6 cannot maintain the adhesion to the substrate for a long time under a harsh environment. On the other hand, the amount of the (B1) compound in the composition of Comparative Example 20 is 0.05 parts by mass relative to 100 parts by mass of the (A) component, which is too little. As a result, the peeling agent layer obtained from the composition of Comparative Example 20 cannot maintain the adhesion to the substrate for a long time under a harsh environment.

The Si-H content of the (B2-2) compound used in Comparative Examples 7 and 8 was 1.2 mol/100 g. As a result, the stripping agent layer obtained from the compositions of Comparative Examples 7 and 8 could not maintain adhesion to the substrate for a long period of time in a 25°C (harsh) environment.

The average degree of polymerization of the (B1-3) compound used in Comparative Examples 9 and 10 is 2. As a result, the stripping agent layer obtained from the compositions of Comparative Examples 9 and 10 cannot maintain adhesion to the substrate for a long period of time under a harsh environment.

The compounds (B1-4) to (B1-7) used in Comparative Examples 11 to 18 do not contain silanol groups and alkoxy groups. As a result, the stripping agent layers obtained from the compositions of Comparative Examples 11 to 18 cannot maintain adhesion to the substrate for a long time in a harsh environment.

Furthermore, the present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are merely examples, and any other embodiments having substantially the same structure and exerting the same effects as the technical concept described in the scope of the patent application of the present invention are included in the technical scope of the present invention.

without

without

Domestic storage information (please note in the order of storage institution, date, and number) None Foreign storage information (please note in the order of storage country, institution, date, and number) None

Claims (10)

A silicone composition for addition-curing peeling film, characterized in that it comprises: 100 parts by weight of (A) an organic polysiloxane having at least two alkenyl groups in one molecule, the alkenyl content being 0.001-0.2 mol/100 g, and the viscosity of 30% by weight toluene at 25° C. being 0.01-70 Pa.s; (B) a component comprising the following (B1) compound and (B2) compound, 0.1-20 parts by weight of (B1) an organic polysiloxane having at least 10 mol% of an epoxypropyl group bonded to a silicon atom via a carbon atom in one molecule. and/or a glycidoxy siloxane unit, containing 0.002-0.02 mol/100g of silanol groups, 0.5-2.5 mol/100g of alkoxy groups, and an average degree of polymerization of 3-50; (B2) an organic hydrosiloxane having more than 1.3 mol/100g of Si-H groups and a degree of polymerization of 10-100, the mass fraction of the (B2) organic hydrosiloxane being equivalent to 0.02-1 times the mass fraction of the aforementioned (B1) compound; a catalytic amount of (D) a platinum metal catalyst; and 0-20,000 mass fractions of (E) an organic solvent. The silicone composition for peeling sheets as described in claim 1 further comprises: (C) an organic hydropolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule, and different from the aforementioned (B2) compound, the amount of the (C) component is an amount in which the total molar number of hydrogen atoms bonded to silicon atoms of the aforementioned (B2) compound and the aforementioned (C) component is equal to 0.5 to 10 times the molar number of alkenyl groups in the aforementioned composition. The silicone composition for peeling sheet as claimed in claim 1, wherein the compound (B1) is a partially hydrolyzed condensate of at least one of an organic alkoxysilane represented by the following general formula (1-1) and an organic alkoxysilane represented by the following general formula (1-2), (1-3) or (1-4), and is an organic polysiloxane having a linear, branched siloxane or cyclic siloxane structure, or a mixture thereof.

(R12) ₂ -Si(OR1) ₂ ‧‧‧‧(1-2) R12-Si(OR1) ₃ ‧‧‧‧(1-3) Si(OR1) ₄ ‧‧‧‧(1-4)In formulas (1-1), (1-2), (1-3) and (1-4), R1 may be the same or different and is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms and which may contain an oxygen atom, or a hydrogen atom, which has no aliphatic unsaturated bond; R12 is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; and n is an integer from 3 to 10. The silicone composition for peeling sheets as claimed in claim 2, wherein the compound (B1) is a partially hydrolyzed condensate of at least one of an organic alkoxysilane represented by the following general formula (1-1) and an organic alkoxysilane represented by the following general formula (1-2), (1-3) or (1-4), and is an organic polysiloxane having a linear, branched siloxane or cyclic siloxane structure, or a mixture thereof.

(R12) ₂ -Si(OR1) ₂ ‧‧‧‧(1-2) R12-Si(OR1) ₃ ‧‧‧‧(1-3) Si(OR1) ₄ ‧‧‧‧(1-4)In formulas (1-1), (1-2), (1-3) and (1-4), R1 may be the same or different and is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms and which may contain an oxygen atom, or a hydrogen atom, which has no aliphatic unsaturated bond; R12 is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; and n is an integer from 3 to 10. The silicone composition for a peeling sheet as claimed in claim 1, wherein the compound (B2) is an organohydrogensiloxane represented by the following general formula (2-1) or (2-2), or a mixture thereof: (R12) ₃ Si-{(R12)HSiO} _m -Si(R12) ₃ ． ． ． (2-1) (R12) ₂ HSi-{(R12)HSiO} _m -SiH(R12) ₂ ． ． ． (2-2) In the formulas (2-1) and (2-2), R12 may be the same or different and is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, and m is an integer of 8 to 98. The silicone composition for a peeling sheet as claimed in claim 2, wherein the compound (B2) is an organohydrogensiloxane represented by the following general formula (2-1) or (2-2), or a mixture thereof: (R12) ₃ Si-{(R12)HSiO} _m -Si(R12) ₃ ． ． ． (2-1) (R12) ₂ HSi-{(R12)HSiO} _m -SiH(R12) ₂ ． ． ． (2-2) In the formulas (2-1) and (2-2), R12 may be the same or different and is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, and m is an integer of 8 to 98. The silicone composition for peeling sheets as described in claim 1 further comprises 0.1 to 10 parts by mass of component (B3) as component (B), wherein the component (B3) is a compound having a viscosity of less than 0.5 Pa.s at 25°C, having at least two alkenyl groups in one molecule, the alkenyl content being 5 to 500 times the alkenyl content of component (A), and having no epoxy group, and the molar number of hydrogen atoms bonded to silicon atoms in the composition is 0.5 to 10 times the total molar number of alkenyl groups in the components (A) and (B3). The silicone composition for peeling sheets as described in claim 2 further comprises 0.1 to 10 parts by mass of component (B3) as component (B), wherein the component (B3) is a compound having a viscosity of less than 0.5 Pa.s at 25°C, having at least two alkenyl groups in one molecule, the alkenyl content being 5 to 500 times the alkenyl content of component (A), and having no epoxy group, and the molar number of hydrogen atoms bonded to silicon atoms in the composition is 0.5 to 10 times the total molar number of alkenyl groups in the components (A) and (B3). The silicone composition for a peeling sheet as claimed in any one of claims 1 to 8, further comprising 0.1 to 20 parts by weight of the following component (F1) and/or the following component (F2) as a peeling force control component (F) relative to 100 parts by weight of the component (A): (F1) the peeling force control component comprises an acrylic-silicone graft copolymer having a weight average molecular weight of 1000 to 100000, wherein the acrylic-silicone graft copolymer is obtained by free radical polymerization of (a) an organic polysiloxane compound having an acryl group and/or a methacryl group represented by the following general formula (3) and (b) a free radical polymerizable monomer having one free radical polymerizable group in one molecule;

In formula (3), ^R2 is a hydrogen atom or a methyl group, X is a group selected from an oxygen atom, an NH group and a sulfur atom, Y is a divalent hydrocarbon group having 1 to 12 carbon atoms which may be mediated by an oxygen atom, ^R3 may be the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, or a substituent represented by the following general formula (4), f is an integer from 0 to 1000,

In formula (4), ^R4 may be the same or different and is an unsubstituted or substituted monovalent alkyl group having 1 to 20 carbon atoms, a hydrogen atom, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms, and g is an integer of 0 to 300; (F2) linear phenylmethyl polysiloxane. A peeling sheet is characterized in that the peeling sheet silicone composition described in any one of claims 1 to 9 is coated on a paper substrate or a film substrate and then cured.