Silicone adhesive composition

Abstract

To provide a silicone adhesive having lower odor than conventional one.SOLUTION: There is provided a silicone adhesive composition comprising a component (A), an optional component (B) and a component (E). (A) A linear, branched or cyclic organopolysiloxane selected from (A1) and (A2), (A1) having at least two alkenyl group-containing organic groups in one molecule and having 0.0005 to 0.10 mol of an alkenyl group in 100 g of an organopolysiloxane and (A2) having at least two Si-OH groups at the terminal, (B) 0 to 80 pts.mass of a resinous organopolysiloxane based on 100 pts.mass of the total of the component (A) and the component (B), (E) 1 to 2000 pts.mass of at least one solvent selected from terpene and a terpene derivative based on 100 pts.mass of the total of the component (A) and the component (B). The silicone adhesive composition may optionally contain a curing agent and a curing catalyst in an effective amount for curing the silicone adhesive composition.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a silicone adhesive containing a plant-derived organic solvent.

Background Art

[0002] An adhesive is a type of bonding agent and is often used in the form of an adhesive tape or an adhesive label obtained by applying and curing an adhesive to a base material. It is a typical example of an article using an adhesive that we commonly see. These articles are used for labels for identifying things, for packing luggage, or for connecting a plurality of things, and their applications are diverse.

[0003] There are several types of base materials for constituting adhesives, which are roughly classified into rubber-based, acrylic-based, silicone-based, etc. Rubber-based adhesives are general-purpose base materials that have been used for a long time, and are inexpensive and used for products such as general-purpose tapes. Acrylic-based adhesives are based on polyacrylate and are used. Since their chemical properties are superior to those of rubber-based adhesives, they can also be applied to higher-functional adhesive products than rubber-based adhesives. Silicone-based adhesives mainly contain high-viscosity silicone raw rubber (gum) and silicone resin, and have various excellent characteristics because the main chain has a large number of siloxane bonds. Specifically, they have heat resistance, cold resistance, weather resistance, chemical resistance, and electrical insulation properties.

[0004] Silicone adhesives utilize the excellent properties as described above and are used for high-functional industrial tapes such as heat-resistant tapes, masking tapes for processes, and mica tapes having flame retardancy. They are used in scenarios where they can exhibit their properties even in an environment with severe usage conditions where acrylic-based adhesives and rubber-based adhesives cannot be applied.

[0005] Since silicone adhesives are mainly composed of high-molecular-weight gums and solid silicone resins, an organic solvent is required to dissolve them. When processing silicone adhesives, an amount of organic solvent equal to or greater than the solid content of the adhesive is used. From the perspective of compatibility with silicone materials, aromatic solvents such as toluene and xylene are the mainstream, but hydrocarbon solvents such as hexane and isoparaffin, and ester solvents such as ethyl acetate and butyl acetate can also be used (Patent Documents 1 to 5).

[0006] In the case of hydrosilylation addition-curing type silicone adhesives using platinum group catalysts, there are also some solvent-free silicone adhesives that do not contain organic solvents. However, since they are solvent-free, the scope of product design is limited, and sufficient properties are often not obtained (Patent Documents 6, 7). In any case, when used as adhesives or other coating applications in actual production sites, organic solvents are almost always used to adjust viscosity and impart leveling properties.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Summary of the Invention

Problems to be Solved by the Invention

[0008] Due to their unique odors and dangers, organic solvents require sufficient care in handling in the working environment. Although there are individual differences in odor, the odors of solvents such as toluene and xylene as described above are generally not preferred in many cases. Even for the same organic solvent, it is preferable to use a solvent with lower danger and lower odor.

[0009] Therefore, an object of the present invention is to provide a silicone adhesive with lower odor than conventional ones.

Means for Solving the Problems

[0010] As a result of intensive studies to achieve the above object, the present inventor has found a plant-derived organic solvent that is compatible with the base organopolysiloxane and can volatilize during heating to form a cured film, and has invented a silicone adhesive containing the organic solvent.

[0011] That is, the present invention [1] A silicone adhesive composition containing the following component (A), optional component (B), and component (E) is provided. (A) A linear, branched or cyclic organopolysiloxane selected from the following (A1) and (A2) (A1) A linear, branched or cyclic organopolysiloxane having at least two alkenyl group-containing organic groups in one molecule and having 0.0005 to 0.10 mol of alkenyl groups in 100 g of the organopolysiloxane (A2) A linear, branched or cyclic organopolysiloxane having Si-OH groups at at least two terminals (B) R 2 3SiO 1 / 2 units and SiO 4 / 2 units, and having (R 2 3SiO 1 / 2 units) / (SiO 4 / 2 units) with a molar ratio of 0.6 to 1.0, a resinous organopolysiloxane (in the above formula, R 2is, independently of each other, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a hydrolyzable group having 1 to 10 carbon atoms, or a hydroxyl group, which has no aliphatic unsaturated bond), 0 to 80 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B), and (E) at least one solvent selected from terpenes and derivatives of terpenes 1 to 2000 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). The silicone pressure-sensitive adhesive composition may optionally contain a curing agent and a curing catalyst in an effective amount for curing the silicone pressure-sensitive adhesive composition.

[0012] The silicone pressure-sensitive adhesive composition of the present invention preferably has at least one configuration of the following [2] and [3]. [2] The silicone pressure-sensitive adhesive composition, wherein the component (E) is at least one selected from a monoterpene compound having 10 carbon atoms and a terpenoid compound having a carbonyl group or a hydroxy group. [3] The silicone pressure-sensitive adhesive composition, wherein the component (E) has a boiling point of 220°C or lower.

[0013] One of the preferred embodiments of the present invention is [4] To provide an addition reaction-curable silicone pressure-sensitive adhesive composition containing the following component (A1), an optional component (B1), and the following components (C) to (E). (A1) A linear, branched or cyclic organopolysiloxane having at least two alkenyl group-containing organic groups in one molecule and having 0.0005 to 0.10 mol of alkenyl groups in 100 g of the organopolysiloxane, 30 to 100 parts by mass, (B1) R 2 3SiO 1 / 2 units and SiO 4 / 2 units, and (R 2 3SiO 1 / 2 units) / (SiO 4 / 2 units) is 0.6 to 1.0 in molar ratio, a resinous organopolysiloxane (in the above formula, R 2is, independently of each other, a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms that does not have an aliphatic unsaturated bond, and optionally R 2 (wherein a part of may be a hydrolyzable group having 1 to 10 carbon atoms or a hydroxyl group) 0 to 70 parts by mass with respect to 100 parts by mass in total of the components (A) and (B) (C) an amount such that the ratio of the number of moles of SiH groups in the component (C) to the number of moles of alkenyl groups in the components (A) and (B) of a polyorganohydrogensiloxane having at least 3 SiH groups in one molecule is 0.2 to 20 (D) a platinum group metal-based catalyst in a catalytic amount, and (E) at least one solvent selected from terpenes and terpene derivatives 1 to 2000 parts by mass with respect to 100 parts by mass in total of the components (A1) and (B)

[0014] The silicone adhesive composition of the present invention preferably has at least one configuration among the following [5] to

[11] . [5] The silicone adhesive composition, wherein the component (A1) is represented by the following average formula (1). [Chemical formula] (In formula (1), R 1 is, independently of each other, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms that may contain a hetero atom, and at least 2 of R 1 are alkenyl group-containing organic groups having 2 to 10 carbon atoms, a is a positive number of 2 or more, b is a positive number of 1 or more, c and d are positive numbers of 0 or more, and 50 ≤ a + b + c + d ≤ 15000) [6] The silicone adhesive composition, wherein the component (C) has an average composition formula: R 3 e H f SiO (4-e-f) / 2 (In the formula, R 3 is, independently of each other, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, e > 0, f > 0, and further 0 < e + f ≤ 3). [7] Furthermore, the silicone pressure-sensitive adhesive composition contains 0.01 to 5 parts by mass of an (F) addition reaction control agent with respect to 100 parts by mass in total of the components (A1), (B1), and (C). [8] The pressure-sensitive adhesive composition according to any one of the above items, wherein the component (E) is at least one selected from a monoterpene compound having 10 carbon atoms and a terpenoid compound having a carbonyl group or a hydroxy group. [9] The silicone pressure-sensitive adhesive composition according to any one of the above items, wherein the component (E) has a boiling point of 220°C or lower.

[10] The silicone pressure-sensitive adhesive composition according to any one of the above items, wherein the alkenyl group-containing organic group is selected from an alkenyl group, an acryloylalkyl group, a methacryloylalkyl group, a cycloalkenylalkyl group, and an alkenyloxyalkyl group.

[0015] One of the preferred embodiments of the present invention is

[11] Provided is a condensation reaction curable silicone pressure-sensitive adhesive composition containing the following component (A2), the following component (B2), and the following component (E). (A2) 20 to 80 parts by mass of a linear, branched, or cyclic organopolysiloxane having Si-OH groups at at least two terminals (B2) R 2 3SiO 1 / 2 units and SiO 4 / 2 units, and (R 2 3SiO 1 / 2 unit) / (SiO 4 / 2 unit) is 0.6 to 1.0 in molar ratio, a resinous organopolysiloxane (wherein R 2 are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a hydrolyzable group having 1 to 10 carbon atoms, or a hydroxy group, and at least one R 2 is a hydroxy group or a hydrolyzable group) 80 to 20 parts by mass with respect to 100 parts by mass in total of the components (A2) and (B2), and (E) At least one solvent selected from terpenes and terpene derivatives 1 to 2000 parts by mass with respect to 100 parts by mass in total of the components (A2) and (B2)

[0016] The silicone adhesive composition of the present invention preferably has at least one of the following constitutions

[12] to

[14] .

[12] The silicone adhesive composition, wherein the component (A2) is a polydiorganosiloxane having one Si-OH group at each end, represented by the following average formula (2). [Chemical formula] (R 4 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and a is a positive number of 100 or more)

[13] The silicone adhesive composition, wherein the component (E) is at least one selected from a monoterpene compound having 10 carbon atoms and a terpenoid compound having a carbonyl group or a hydroxy group.

[14] The silicone adhesive composition, wherein the component (E) has a boiling point of 220°C or lower.

[0017] Furthermore, the present invention provides an adhesive article having a base material and a cured product formed by curing the silicone adhesive composition on at least one surface of the base material surface. [Advantages of the Invention]

[0018] Since the silicone adhesive composition of the present invention has a low odor, it is possible to reduce the odor of the obtained adhesive article and reduce the burden on the operator. [Embodiments for Carrying Out the Invention]

[0019] As described above, the present invention provides a silicone adhesive composition containing (A) a linear, branched or cyclic organopolysiloxane, an optional (B) resinous organopolysiloxane, and (E) a terpene-based solvent.

[0020] The component (A) is one linear, branched or cyclic organopolysiloxane selected from the following (A1) and (A2), and is the main component of the silicone adhesive composition. (A1) A linear, branched or cyclic organopolysiloxane having at least two alkenyl group-containing organic groups in one molecule and having 0.0005 to 0.10 mol of alkenyl groups in 100 g of the organopolysiloxane (A2) A linear, branched or cyclic organopolysiloxane having Si-OH groups at at least two terminals The present invention is preferably an addition reaction curable silicone pressure-sensitive adhesive composition containing the component (A1) or a condensation reaction curable silicone pressure-sensitive adhesive composition containing the component (A2). Details of the components (A1) and (A2) are as described below. The silicone pressure-sensitive adhesive composition may optionally contain a curing agent and a curing catalyst in an effective amount for curing the silicone pressure-sensitive composition.

[0021] (Component (B) is R 2 3SiO 1 / 2 units and SiO 4 / 2 units, and (R 2 3SiO 1 / 2 units) / (SiO 4 / 2 units) is a resinous organopolysiloxane having a molar ratio of 0.6 to 1.0. In the above formula, R 2 is, independently of each other, a monovalent hydrocarbon group having 1 to 10 carbon atoms without an aliphatic unsaturated bond, an alkenyl group having 2 to 10 carbon atoms, a hydrolyzable group having 1 to 10 carbon atoms, or a hydroxyl group. More preferably, examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms include alkyl groups having 2 to 6 carbon atoms such as methyl group, ethyl group, propyl group, and butyl group, and aryl groups having 6 to 10 carbon atoms such as phenyl group and tolyl group. Examples of the alkenyl group having 2 to 6 carbon atoms include vinyl group, allyl group, and butenyl group. Examples of the hydrolyzable group having 1 to 10 carbon atoms include alkoxy groups such as methoxy group, ethoxy group, propoxy group, and butoxy group. Component (B) may be used in combination of two or more resinous organopolysiloxanes. Also, within a range not impairing the characteristics of the present invention, R 2 2SiO 3 / 2 units and R 2 SiO 2 / 2It may contain units. The (B) component includes the (B1) component and the (B2) component described later, and the details of the (B) component are as described in the explanations of the (B1) component and the (B2) component described later.

[0022] In the silicone pressure-sensitive adhesive composition of the present invention, based on 100 parts by mass in total of the (A) component and the (B) component, the amount of the (A) component is 30 to 100 parts by mass, preferably 32 to 98 parts by mass, and more preferably 65 to 80 parts by mass. The amount of the (B) component is 0 to 80 parts by mass, preferably 2 to 68 parts by mass, and more preferably 20 to 35 parts by mass. More preferably, the mass ratio of the (A1) and (B) components is (A1) / (B)=30 / 70 to 100 / 0, preferably 32 / 68 to 98 / 2, and more preferably 65 / 35 to 80 / 20. Also, the mass ratio of the (A2) component and the (B) component is (A2) / (B)=20 / 80 to 80 / 20, preferably 30 / 70 to 70 / 30, and more preferably 35 / 65 to 65 / 35. If the blending ratio of the (B) component is more than the above upper limit value, the resulting cured film becomes too hard, and there is a possibility that appropriate adhesive properties cannot be obtained.

[0023] (E) Terpene solvent The silicone pressure-sensitive adhesive composition of the present invention is characterized by using a terpene solvent as a plant-derived organic solvent that is compatible with organopolysiloxane and can volatilize upon heating to form a cured film. The (E) component is a terpene or a derivative of terpene (hereinafter collectively referred to as terpene solvent) that is compatible with the components contained in the silicone pressure-sensitive adhesive composition. The solvent compatible with the components contained in the silicone pressure-sensitive adhesive composition means a solvent that gives a transparent solution when the silicone pressure-sensitive adhesive composition and the solvent are mixed. When all of the above (A) to (D) components contained in the silicone pressure-sensitive adhesive composition are mixed, the viscosity becomes high and handling becomes difficult, but the (E) terpene solvent functions for diluting the above (A) to (D) components. The (E) terpene solvent also contributes to improving the wettability to the substrate during processing and the smoothness after curing.

[0024] In order for the solvent to volatilize during processing, (E) terpene solvents preferably have high volatility, and the boiling point of the solvent is preferably 220°C or lower, more preferably 200°C or lower. If the boiling point exceeds 220°C, the curability of the adhesive may deteriorate. A terpene derivative is, for example, a terpenoid compound having a carbonyl group or a hydroxy group. In the present invention, the terpene solvent is preferably at least one selected from a monoterpene compound having 10 carbon atoms and a terpenoid compound having a carbonyl group or a hydroxy group.

[0025] (E) More specifically, terpene solvents include pinene (boiling point: 156°C), limonene (boiling point: 178°C), terpineol (boiling point: 218°C), menthane (boiling point: 172°C), linalyl acetate (boiling point: 220°C), linalool (boiling point: 200°C), farnandrene (boiling point: 171°C), cymene (boiling point: 177°C), menthol (boiling point: 212°C), neomenthol (boiling point: 212°C), terpinene (boiling point: 173°C), terpinolene (boiling point: 185°C), fencon (boiling point: 193°C), camphene (boiling point: 159°C), etc. In addition, turpentine oil mainly composed of α-pinene can also be used. From the viewpoints of boiling point and compatibility with components (A) to (D), turpentine oil, α-pinene, and p-menthane are preferred. The terpene solvent may be used alone or in combination of two or more.

[0026] By using the above terpene solvent, the odor during handling can be reduced compared to the case of using a general-purpose solvent such as toluene. The amount of the terpene solvent in the silicone adhesive composition of the present invention is 1 to 2000 parts by mass, more preferably 10 to 1000 parts by mass, and even more preferably 40 to 500 parts by mass with respect to 100 parts by mass in total of the above components (A) and (B). Although the optimum viscosity of the coating liquid varies depending on the coating method, generally, if it is less than 1 part by mass or exceeds 2000 parts by mass, the coating workability deteriorates and the smoothness of the coating film surface also deteriorates.

[0027] Addition reaction curable silicone adhesive composition One preferred embodiment of the present invention is an addition reaction curable silicone adhesive composition containing the following component (A1), any of the following component (B1), and the following components (C) to (E). (A1) 30 to 100 parts by mass of a linear, branched or cyclic organopolysiloxane having at least two alkenyl group-containing organic groups in one molecule and having 0.0005 to 0.10 mol of alkenyl groups per 100 g of the organopolysiloxane, (B1) R 2 3SiO 1 / 2 units and SiO 4 / 2 units, and (R 2 3SiO 1 / 2 units) / (SiO 4 / 2 units) is 0.6 to 1.0 in molar ratio, a resinous organopolysiloxane (in the above formula, R 2 is, independently of each other, a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms that does not have an aliphatic unsaturated bond, and optionally a part of R 2 may be a hydrolyzable group having 1 to 10 carbon atoms or a hydroxyl group) 0 to 70 parts by mass based on 100 parts by mass of the total of the above components (A1) and (B1) (C) An amount such that the ratio of the number of moles of SiH groups in component (C) to the number of moles of alkenyl groups in components (A1) and (B1) of a polyorganohydrogensiloxane having at least 3 SiH groups in one molecule is 0.2 to 20 (D) A platinum group metal-based catalyst in a catalytic amount, and (E) At least one solvent selected from terpenes and terpene derivatives 1 to 2000 parts by mass based on 100 parts by mass of the total of components (A1) and (B1).

[0028] (E) Terpenes and terpene derivatives are as described above. The amount of the terpene-based solvent in the addition reaction curable silicone adhesive composition is 1 to 2000 parts by mass based on 100 parts by mass of the total of components (A1) and (B1), more preferably 10 to 1000 parts by mass, and even more preferably 40 to 500 parts by mass. Hereinafter, other components will be described in detail.

[0029] (A1) Alkenyl group-containing organopolysiloxane (A1) component is a linear, branched or cyclic organopolysiloxane having at least two alkenyl group-containing organic groups in one molecule. The alkenyl group-containing organic group preferably has 2 to 10 carbon atoms, and examples thereof include alkenyl groups such as vinyl group, allyl group, hexenyl group, octenyl group, acryloylalkyl groups such as acryloylpropyl group, acryloylmethyl group, methacryloylpropyl group, and methacryloylalkyl groups, cycloalkenylalkyl groups such as cyclohexenylethyl group, and alkenyloxyalkyl groups such as vinyloxypropyl group. Particularly, a vinyl group is preferred.

[0030] (A1) The amount of the alkenyl group contained in the component is 0.0005 to 0.10 mol per 100 g of the organopolysiloxane, preferably 0.0007 to 0.08 mol, and more preferably 0.0008 to 0.05 mol. If it is less than 0.0005 mol, the crosslinking density may be small and cohesive failure of the adhesive layer may occur. If it is more than 0.10 mol, the adhesive layer may become hard and appropriate adhesive strength and tack may not be obtained.

[0031] The alkenyl group-containing organopolysiloxane preferably has 50 to 15,000 siloxane units, preferably 200 to 12,000 siloxane units, and more preferably 2,000 to 10,000 siloxane units. When the number of siloxane units is less than the above lower limit, the reaction may be delayed due to too many crosslinking points. When the number of siloxane units is greater than the above upper limit, the viscosity of the silicone adhesive composition may become very high, which may deteriorate the handleability. (A1) component may be linear, branched or cyclic, but is preferably a linear or branched organopolysiloxane, and more preferably a linear organopolysiloxane.

[0032] The organopolysiloxane is preferably represented by the following average formula (1). [Chemical formula] In formula (1), R 1 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain a heteroatom, and R 1 At least two of the above are alkenyl-containing organic groups having 2 to 10 carbon atoms. a is a positive number of 2 or more, b is a positive number of 1 or more, c and d are positive numbers of 0 or more, and 50≦a+b+c+d≦15000. There are no particular limitations on the bonding sites of the alkenyl-containing organic groups, but R 1 3SiO 1 / 2 and R 1 2SiO 2 / 2 R bonded to unit 1 At least two of these are preferably alkenyl-containing organic groups.

[0033] In the above formula (1), R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain a heteroatom, R 1 At least two of the above are alkenyl-containing organic groups. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl, and aryl groups such as phenyl, and some or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with halogen atoms or other groups, such as trifluoromethyl and 3,3,3-trifluoropropyl groups. Among these, saturated aliphatic or aromatic groups are preferred, and methyl and phenyl groups are particularly preferred. The alkenyl-containing organic group is as described above.

[0034] Regarding a to d in the above formula (1), a is a positive number of 2 or more, preferably 2 to 100, more preferably 2 to 80, and even more preferably 2 to 50. b is a positive number of 1 or more, preferably 10 ≤ b ≤ 14,998, more preferably 100 ≤ b ≤ 12000, and even more preferably 1000 ≤ b ≤ 12000. c is a positive number of 0 or more, 0 ≤ c ≤ 20, preferably 0 ≤ c ≤ 15, and more preferably 0 ≤ c ≤ 10. d is a positive number of 0 or more, 0 ≤ d ≤ 10, preferably 0 ≤ c ≤ 8, and more preferably 0 ≤ c ≤ 5. 50 ≤ a + b + c + d ≤ 15000, preferably 200 ≤ a + b + c + d ≤ 12000, and even more preferably 2000 ≤ a + b + c + d ≤ 10000. When a + b + c + d is less than 50, the reaction is delayed due to too many crosslinking points, and when it is greater than 15000, the viscosity of the silicone adhesive composition becomes very high, resulting in poor handleability.

[0035] (Component (A1) is usually produced by ring-opening polymerization of cyclic low-molecular siloxanes such as octamethylcyclotetrasiloxane using a catalyst. Since it contains cyclic low-molecular siloxanes as raw materials after polymerization, it is preferable to use a product obtained by distilling off the cyclic low-molecular siloxanes while passing an inert gas through the reaction product under heating and reduced pressure.

[0036] Preferably, as component (A1), there may be mentioned, but not limited to, linear or branched organopolysiloxanes represented by the following general formula. R 1-1 R 1-2 2SiO(R 1-2 2SiO) L SiR 1-2 2R 1-1 R 1-1 R 1-2 2SiO(R 1-2 2SiO) L (R 1-1 R 1-2 SiO) m SiR 1-2 2R 1-1 R 1-13SiO(R 1-2 2SiO) L (R 1-1 R 1-2 SiO) m SiR 1-2 2R 1-1 3 R 1-2 3SiO(R 1-2 2SiO) L (R 1-1 R 1-2 SiO) k SiR 1-2 2R 1-2 3 In the formula, R 1-1 is, independently of each other, an alkenyl group-containing organic group having 2 to 10 carbon atoms, and R 1-2 is, independently of each other, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, L≧48, m≧1, and k≧2.

[0037] Details of the above R 1-1 and R 1-2 are as described for the above R 1 . L and m are preferably 48≦L≦11,998, more preferably 98≦L≦9,998, preferably 1≦m≦1,000, and more preferably 2≦m≦800. 2≦k≦1,000 is preferable, and 2≦k≦800 is more preferable.

[0038] As the component (A1), more specifically, organopolysiloxanes represented by the following general formula can be mentioned, but are not limited thereto. In the following formula, Me, Vi, and Ph represent a methyl group, a vinyl group, and a phenyl group, respectively. M Vi 2D n (48≦n≦11,998) M Vi 2D n D Vi o (47≦n≦11,997, 1≦o≦1,000) M2D n D Vi o (46≦n≦11,996, 2≦o≦1,000) M Vi3 2D n D Vi o (48 ≦ n ≦ 11,998, 0 ≦ o ≦ 1,000) M Vi 2D n D Ph p (48 ≦ n ≦ 11,998, 0 ≦ p ≦ 1,000) M Vi 2D n D Vi o D Ph p (46 ≦ n ≦ 11,997, 1 ≦ o ≦ 1,000, 1 ≦ p ≦ 4,000) M Vi (q+2) D n D Vi o T q (46 ≦ n ≦ 11,996, 1 ≦ o ≦ 1,000, 1 ≦ q ≦ 10) M Vi (q+2r+2) D n D Vi o T q Q r (46 ≦ n ≦ 11,996, 1 ≦ o ≦ 1,000, 0 ≦ q ≦ 10, 1 ≦ q ≦ 10)

[0039] The structure of each siloxane unit in the above formula is as follows.

Chemical formula

[0040] (B1) Resinous organopolysiloxane (Component (B1) is a resinous organopolysiloxane having R 2 3SiO 1 / 2 units and SiO 4 / 2 units, and (R 2 3SiO 1 / 2 units) / (SiO 4 / 2(The unit) is in a molar ratio of 0.6 to 1.0, preferably 0.65 to 0.9. More preferably, the component (B1) is R 2 3SiO 1 / 2 units and SiO 4 / 2 is a resinous organopolysiloxane consisting only of units. (R 2 3SiO 1 / 2 unit) / (SiO 4 / 2 unit) is less than the above lower limit, the adhesive strength and tack of the resulting cured product may decrease. Also, if it exceeds the above upper limit, the adhesive strength and holding power of the resulting cured product may decrease.

[0041] In the above, R 2 is, independently of each other, a monovalent hydrocarbon group having 1 to 10 carbon atoms without an aliphatic unsaturated bond or an alkenyl group having 2 to 10 carbon atoms, and optionally some of the R 2 may be a hydrolyzable group having 1 to 10 carbon atoms or a hydroxyl group. As the monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably, an alkyl group having 2 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group, and an aryl group having 6 to 10 carbon atoms such as a phenyl group and a tolyl group can be mentioned. As the alkenyl group having 2 to 6 carbon atoms, a vinyl group, an allyl group, a butenyl group, etc. can be mentioned. As the hydrolyzable group having 1 to 10 carbon atoms, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group can be mentioned.

[0042] (B1) component may be used in combination of two or more resinous organopolysiloxanes. Also, within a range not impairing the characteristics of the present invention, R 2 2SiO 3 / 2 units and R 2 SiO 2 / 2 units may be included. R 2 is as described above. R 2 2SiO 3 / 2 units and R 2 SiO 2 / 2 When units are included, it is preferably 10% or less, more preferably 5% or less, based on the total number of siloxane units.

[0043] The above-mentioned (B1) resinous organopolysiloxane preferably has a number average molecular weight (Mw) of 2,000 to 5,000, more preferably 2,500 to 4,500. The number average molecular weight (Mw) in the present invention is a value obtained using polystyrene as a standard substance by gel permeation chromatography (GPC).

[0044] Before mixing the above-mentioned (B1) component with the above-mentioned (A1) component, it may be previously subjected to a condensation reaction in the presence of a catalyst. This is an operation of reacting the hydrolyzable groups present on the surface of the (B1) component, and effects such as an improvement in adhesive strength can be expected. An alkaline catalyst may be used, and the reaction may be carried out at a temperature from 20°C to the reflux temperature of the organic solvent, and neutralization may be carried out as necessary.

[0045] Examples of the alkaline catalyst include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide; carbonates such as sodium carbonate and potassium carbonate; hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; metal alkoxides such as sodium methoxide and potassium butoxide; organometals such as butyllithium; potassium silanolate; nitrogen compounds such as ammonia gas, aqueous ammonia, methylamine, trimethylamine, and triethylamine. Among them, ammonia gas or aqueous ammonia is preferred. The temperature of the condensation reaction may be carried out at a temperature from 20°C to the reflux temperature of the organic solvent. The reaction time is not particularly limited, but it may be 0.5 to 20 hours, preferably 1 to 16 hours.

[0046] Furthermore, after completion of the reaction, a neutralizing agent for neutralizing the alkaline catalyst may be added as necessary. Examples of the neutralizing agent include acidic gases such as hydrogen chloride and carbon dioxide; organic acids such as acetic acid, octylic acid, and citric acid; and mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid. When ammonia gas, aqueous ammonia, or a low-boiling amine compound is used as the alkaline catalyst, an inert gas such as nitrogen may be bubbled and distilled off, or it may be distilled off together with the removal of the organic solvent.

[0047] In the silicone adhesive composition of the present invention, based on a total of 100 parts by mass of the components (A1) and (B1), the amount of the component (A1) is 30 to 100 parts by mass, preferably 32 to 98 parts by mass, and more preferably 65 to 80 parts by mass. The amount of the component (B1) is 0 to 70 parts by mass, preferably 2 to 68 parts by mass, and more preferably 20 to 35 parts by mass. That is, the mass ratio of the components (A1) and (B1) is (A1) / (B1) = 100 / 0 to 30 / 70, preferably 98 / 2 to 32 / 68, and more preferably 80 / 20 to 65 / 35. If the blending ratio of the component (B1) is more than the above upper limit value, the resulting cured film becomes too hard, and there is a risk that appropriate adhesive properties cannot be obtained.

[0048] (C) Polyorganohydrogensiloxane The component (C) is a polyorganohydrogensiloxane having at least 3 Si-H groups in one molecule and functions as a curing agent for the component (A1). The component (C) preferably has 5 to 200 siloxane units, and more preferably 100 siloxane units. The polyorganohydrogensiloxane is preferably linear or branched.

[0049] (C) The component is preferably represented by the following average composition formula. R 3 e H f SiO (4-e-f) / 2 In the above formula, R 3 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, e > 0, f > 0, and further 0 < e + f ≦ 3.

[0050] R 3is a monovalent hydrocarbon group having 1 to 10 carbon atoms. For example, alkyl groups such as methyl group, ethyl group, propyl group, and butyl group, cycloalkyl groups such as cyclohexyl group, alkenyl groups such as vinyl group, allyl group, hexenyl group, and octenyl group, and aryl groups such as phenyl group, etc. Some or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with halogen atoms or other groups. For example, trifluoromethyl group, 3,3,3-trifluoropropyl group, etc. are exemplified. A saturated aliphatic group or an aromatic group is preferable, and particularly a methyl group and a phenyl group are preferable.

[0051] In the above average composition formula, 0 < e, preferably 0.5 ≦ e ≦ 1.5, more preferably 1 ≦ e ≦ 2. Also, 0 < f, preferably 0.5 ≦ f ≦ 1.5, more preferably 1 ≦ f ≦ 2. In addition, it is a number that satisfies 0 < e + f < 4, preferably 1 ≦ e + f ≦ 2.5. If e is less than the above lower limit, the cured film may become too hard to obtain appropriate adhesion characteristics. If f is less than the above lower limit, a cured film may not be obtained. Component (C) preferably has 5 to 200 siloxane units, more preferably 8 to 100. The polyorganohydrogensiloxane is preferably linear or branched.

[0052] Component (C) more specifically includes, but is not limited to, those represented by the following general formula. R 3-1 R 3-2 2SiO(R 3-2 2SiO) s (R 3-1 R 3-2 SiO) t SiR 3-2 2R 3-1 R 3-2 3SiO(R 3-2 2SiO) s (R 3-1 R 3-2 SiO) p SiR 3-2 3 R 3-2 3SiO(R3-1 R 3-2 SiO p SiR 3-2 3 In the above formula, R 3-1 is a hydrogen atom, and R 3-2 is, independently of each other, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and s ≧ 8, t ≧ 1, p ≧ 3. R 3-1 , R 3-2 as, the groups exemplified for the above R 3 are mentioned. Incidentally, 8 ≦ s ≦ 98 is preferable, more preferably 12 ≦ s ≦ 88, 1 ≦ t ≦ 98 is preferable, and 3 ≦ t ≦ 98 is more preferable. p is preferably 3 ≦ p ≦ 98.

[0053] (C) The amount of the component is such that the ratio of the number of moles of SiH groups in the (C) component to the number of moles of alkenyl groups in the above (A1) and (B1) components is 0.2 to 20, and particularly preferably in the range of 0.5 to 15. If it is less than the above lower limit, the crosslinking density becomes low, and as a result, the cohesive force and the holding force may become low. If it exceeds the above upper limit, the crosslinking density becomes high, and appropriate adhesiveness and tack may not be obtained.

[0054] (C) The component is usually produced by ring-opening polymerization of a cyclic low-molecular siloxane such as octamethylcyclotetrasiloxane and a Si-H-containing siloxane such as tetramethylcyclotetrasiloxane using an acid catalyst. However, since it contains the cyclic low-molecular siloxane as a raw material after polymerization, it is preferable to use the one obtained by distilling off the cyclic low-molecular siloxane while passing an inert gas through the reaction product under heating and reduced pressure.

[0055] (C) Examples of those showing the detailed structure of the component include, but are not limited to, the following. In the following formula, Me represents a methyl group. M2D u D H v (1 ≦ u ≦ 95, 7 ≦ v ≦ 98) M2D H v (8 ≦ v ≦ 98) MH 2D u D H v (1 ≦ u ≦ 97, 7 ≦ v ≦ 98) M (w+2) D u D H v T w (1 ≦ u ≦ 95, 7 ≦ v ≦ 98, 1 ≦ w ≦ 5) M (w+2x+2) D u D H v T w Q x (1 ≦ u ≦ 95, 7 ≦ v ≦ 98, 0 ≦ w ≦ 5, 1 ≦ x ≦ 5)

[0056] The structure of each siloxane unit in the above formula is as follows.

Chemical formula

[0057] (D) Platinum group metal catalyst (D) component is a platinum group metal catalyst for hydrosilylation reaction of the alkenyl group in (A) component and the SiH group in (C) component to cause curing. Examples of the central metal include platinum, palladium, iridium, rhodium, osmium, ruthenium, etc., and platinum is particularly preferred. Examples of the platinum catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and alcohol, a platinum complex obtained by the reaction of chloroplatinic acid and an olefin compound, a complex of platinum and a vinyl group-containing siloxane, a complex of platinum and a vinyl group-containing polysiloxane, etc.

[0058] (D) The compounding quantity of the component may be a catalytic amount. The catalytic amount is an effective amount for the addition reaction of the above organopolysiloxane to proceed. Preferably, it is an amount such that the metal amount is 1 to 500 mass ppm with respect to the total mass of the components (A1), (B1), and (C), more preferably 2 to 450 mass ppm, and still more preferably 10 to 100 mass ppm. If it is less than the above lower limit, the reaction may be slow and insufficient hardening may occur, so that various properties such as adhesive strength and holding power may not be exhibited. If it exceeds the above upper limit, the flexibility of the cured product may be poor.

[0059] (F) Addition reaction controller (F) The component is a controller. The controller is added to prevent the addition reaction from starting before heat curing when formulating the silicone adhesive composition or coating it on a substrate, so that the treatment liquid does not thicken or gel. The reaction controller coordinates with the platinum group metal which is an addition reaction catalyst to suppress the addition reaction, and when heat cured, the coordination is released and the catalytic activity is expressed. Any of the reaction controllers conventionally used in addition reaction curable silicone compositions can be used. For example, acetylene alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyn-3-ol, 2-phenyl-3-butyn-2-ol, acetylene compounds such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, reaction products of these acetylene compounds with alkoxysilane or siloxane or hydrogen silane, vinyl siloxanes such as tetramethylvinylsiloxane cyclic body, organic nitrogen compounds such as benzotriazole and other organic phosphorus compounds, oxime compounds, organic chloro compounds, etc. can be mentioned.

[0060] (F) As the content of the component, 0.01 to 5 parts by mass is preferable with respect to 100 parts by mass in total of the components (A1), (B1), and (C), more preferably 0.02 to 4 parts by mass, and still more preferably 0.03 to 3 parts by mass. By blending the (F) component, it is possible to improve the workability by delaying the curing reaction and ensuring the pot life.

[0061] Condensation reaction-curing type silicone adhesive composition Another preferred embodiment of the present invention is a condensation reaction-curing type silicone adhesive composition containing the following component (A2), the following component (B2), and the following component (E). (A2) 20 to 80 parts by mass of a linear, branched or cyclic organopolysiloxane having Si-OH groups at at least two terminals (B2) R 2 3SiO 1 / 2 units and SiO 4 / 2 units, and (R 2 3SiO 1 / 2 unit) / (SiO 4 / 2 unit) is 0.6 to 1.0 in molar ratio, a resinous organopolysiloxane (wherein R 2 is, independently of one another, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a hydrolyzable group having 1 to 10 carbon atoms, or a hydroxyl group, and at least one R 2 is a hydroxyl group or a hydrolyzable group) 80 to 20 parts by mass based on 100 parts by mass of the total amount of the above-mentioned components (A2) and (B2), and (E) At least one solvent selected from terpenes and terpene derivatives 1 to 2000 parts by mass based on 100 parts by mass of the total of the above-mentioned components (A2) and (B2)

[0062] (E) At least one solvent selected from terpenes and terpene derivatives is as described above. The amount of the terpene-based solvent in the condensation reaction-curing type silicone adhesive composition is 1 to 2000 parts by mass based on 100 parts by mass of the total of components (A2) and (B2), more preferably 10 to 1000 parts by mass, still more preferably 40 to 500, and even more preferably 40 to 200 parts by mass. Hereinafter, other components will be described in detail.

[0063] (A2) SiOH group-containing organopolysiloxane Component (A2) is a linear, branched or cyclic organopolysiloxane having Si-OH groups at at least two terminals. Organopolysiloxane refers to a polymer having a plurality of Si-O bonds as the main chain, mainly R4 3SiO 1 / 2 The M unit represented by 4 2SiO 2 / 2 The D unit represented by 4 1SiO 3 / 2 The T unit represented by 4 / 2 and the Q unit represented by 4 In the above formula, R

[0064] (Component (A2) is preferably an oily or raw rubber-like substance, and the number of siloxane units is preferably from 100 to 10,000, more preferably from 150 to 8,000, and still more preferably from 200 to 5,000.) [Chemical formula]

[0065] R 4 are, independently of each other, substituted or unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, etc. Further, part or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with halogen atoms or other groups, and examples thereof include trifluoromethyl group, 3,3,3-trifluoropropyl group, etc. Saturated aliphatic groups or aromatic groups are preferred, and particularly methyl group and phenyl group are preferred.)

[0066] (The property of the component (A2) may be oily or raw rubber-like. In the above average formula (2), a is a positive number of 100 or more, preferably 150 or more, more preferably 200 or more. If a is less than 100, the film-forming property is poor, and the properties required for an adhesive such as adhesive strength and holding power may be insufficient. The upper limit of a may be 10,000 or less, preferably 8,000 or less, more preferably 5,000 or less.)

[0067] (The component (A2) is usually produced by ring-opening polymerization of a cyclic low-molecular siloxane such as octamethylcyclotetrasiloxane using a catalyst. However, since it contains the cyclic low-molecular siloxane as a raw material after polymerization, it is preferable to use the one obtained by distilling off the cyclic low-molecular siloxane while passing an inert gas through the reaction product under heating and reduced pressure.)

[0068] ((B2) Resinous organopolysiloxane) (The component (B2) is R 2 3SiO 1 / 2 unit and SiO 4 / 2 unit, and is a resinous organopolysiloxane having at least one hydroxyl group and / or hydrolyzable group bonded to a silicon atom, and (R 2 3SiO 1 / 2 unit) / (SiO 4 / 2 unit) is an organopolysiloxane having a molar ratio of 0.6 to 1.0, preferably 0.65 to 0.9. If this molar ratio is less than 0.6, the adhesive strength and tack may decrease, and if it exceeds 1.0, the adhesive strength and holding power may decrease. More preferably, the component (B2) is R 2 3SiO 1 / 2 unit and SiO 4 / 2 unit only consisting of a resinous organopolysiloxane.)

[0069] In the above, R 2is, independently of one another, a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms that does not have an aliphatic unsaturated bond, a hydrolyzable group having 1 to 10 carbon atoms, or a hydroxyl group. As the monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably, an alkyl group having 2 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group, and an aryl group having 6 to 10 carbon atoms such as a phenyl group and a tolyl group can be mentioned. As the alkenyl group having 2 to 6 carbon atoms, a vinyl group, an allyl group, a butenyl group, etc. can be mentioned. In the component (B2), at least one R 2 is a hydroxyl group or a hydrolyzable group.

[0070] (B2) component has at least one hydroxyl group and / or hydrolyzable group bonded to a silicon atom in one molecule. Examples of the hydrolyzable group bonded to the silicon atom include alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The content of the hydroxyl group and the hydrolyzable group is 0.005 to 0.5 mol, preferably 0.008 to 0.3 mol, and more preferably 0.01 to 0.2 mol per 100 g of the component (B2). If it is more than 0.5 mol, the cured film may become too hard to obtain appropriate adhesive properties. If it is less than 0.005 mol, the cohesive force of the adhesive film obtained by curing may be insufficient and the film strength may be weak.

[0071] (B2) component may use two or more resinous organopolysiloxanes in combination. Also, within a range that does not impair the characteristics of the present invention, R 2 2SiO 3 / 2 unit, R 2 SiO 2 / 2 unit may be included. R 2 is as described above. R 2 2SiO 3 / 2 unit and R 2 SiO 2 / 2 When including the unit, it is preferably 10% or less, more preferably 5% or less, based on the total number of siloxane units.

[0072] The above-mentioned (B2) resinous organopolysiloxane preferably has a number average molecular weight (Mw) of 2,000 to 5,000, more preferably 2,500 to 4,500. In the present invention, the weight average molecular weight (Mw) is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard substance.

[0073] Before mixing the above-mentioned (B2) component with the (A2) component, a condensation reaction may be carried out in advance in the presence of a catalyst. This is an operation to react the hydroxyl groups and / or hydrolyzable groups present on the surface, and effects such as improvement of adhesion can be expected. An alkaline catalyst is used, and the reaction is carried out at a temperature from 20°C to the reflux temperature of (C) described later, and neutralization may be carried out as necessary.

[0074] Examples of the alkaline catalyst include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide; carbonates such as sodium carbonate and potassium carbonate; hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; metal alkoxides such as sodium methoxide and potassium butoxide; organometals such as butyllithium; potassium silanolate; nitrogen compounds such as ammonia gas, aqueous ammonia, methylamine, trimethylamine, and triethylamine. Among them, ammonia gas or aqueous ammonia is preferred. The temperature of the condensation reaction may be carried out at a temperature from 20°C to the reflux temperature of the organic solvent. The reaction time is not particularly limited, but it may be 0.5 to 20 hours, preferably 1 to 16 hours.

[0075] Furthermore, after completion of the reaction, a neutralizing agent for neutralizing the alkaline catalyst may be added as necessary. Examples of the neutralizing agent include acidic gases such as hydrogen chloride and carbon dioxide; organic acids such as acetic acid, octylic acid, and citric acid; and mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid. When ammonia gas or aqueous ammonia or a low-boiling amine compound is used as the alkaline catalyst, an inert gas such as nitrogen may be passed through and distilled off, or it may be distilled off together with the removal of (C) described later.

[0076] In the silicone adhesive composition of the present invention, based on 100 parts by mass in total of the components (A2) and (B2), the amount of the component (A2) is 20 to 80 parts by mass, preferably 30 to 70 parts by mass, and more preferably 35 to 65 parts by mass. The amount of the component (B) is 80 to 20 parts by mass, preferably 70 to 30 parts by mass, and more preferably 65 to 35 parts by mass. That is, the mass ratio of the components (A2) and (B2) is (A2) / (B2)=20 / 80 to 80 / 20, preferably 30 / 70 to 70 / 30, and more preferably 35 / 65 to 65 / 35. If the amount ratio of the component (B2) is more than the above upper limit value, the resulting cured film becomes too hard, and appropriate adhesive properties may not be obtained. If the amount ratio of the component (B2) is less than the above lower limit value, the cohesive force of the adhesive film obtained by curing may be insufficient and the film strength may be weak.

[0077] (A2) component and (B2) component are not only simply mixed, but it is preferable to carry out a condensation reaction of the hydroxyl groups or hydrolyzable groups bonded to the respective Si atoms in the presence of a catalyst and use them as condensates. Thereby, the film-forming property of the composition is improved. Regarding the detailed conditions of the condensation, the same conditions as the condensation reaction of the above-mentioned (B2) component alone can be applied.

[0078] As a catalyst for crosslinking the hydrocarbon groups contained in the (A2) and (B2) components, an organic peroxide may be added. Thereby, the film becomes high-strength, the adhesive force becomes small but the holding force becomes strong. Specific examples of the organic peroxide include dibenzoyl peroxide, 4,4'-dimethyl dibenzoyl peroxide, 3,3'-dimethyl dibenzoyl peroxide, 2,2'-dimethyl dibenzoyl peroxide, 2,2',4,4'-tetrachloro dibenzoyl peroxide, cumyl peroxide and the like. The addition amount is 0.5 to 5 parts by mass, preferably 0.8 to 4 parts by mass, and more preferably 1 to 3 parts by mass with respect to 100 parts by mass in total of the (A2) and (B2) components. If it is less than the above lower limit value, there is a possibility that the effect of crosslinking by adding the catalyst is difficult to obtain. Also, if it is more than the above upper limit value, there is a possibility that the cured film becomes too hard and appropriate adhesive properties cannot be obtained.

[0079] Other components In addition to the components (A) to (F) above, the silicone adhesive composition of the present invention may contain optional components as long as the effects of the present invention are not impaired. Examples thereof include non-reactive organopolysiloxanes having no alkenyl group or Si-H group, silicone oligomers, silane compounds, and other organic compounds. From a functional aspect, there are anchor additives for improving adhesion to a substrate, fillers for increasing the strength of the cured product, antioxidants for enhancing stability, and in addition thereto, antistatic agents, lubricity imparting agents, leveling agents, pigments, dyes, phosphorescent agents, foaming agents, plasticizers, etc. may be added.

[0080] In addition to the above-mentioned (E) terpene-based solvent, if necessary, a general solvent used for diluting silicone may be used in combination. Specifically, aliphatic hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane, and isoparaffin, hydrocarbon solvents such as industrial gasoline, petroleum benzine, and solvent naphtha, ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, acetonylacetone, and cyclohexanone, ester solvents such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and isobutyl acetate, ether solvents such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1,2-dimethoxyethane, and 1,4-dioxane, solvents having an ester and ether moiety such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, and 2-butoxyethyl acetate, siloxane solvents such as hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tris(trimethylsiloxy)methylsilane, and tetrakis(trimethylsiloxy)silane, or a mixed solvent thereof. The blending amount of other solvents is preferably 0.5 to 1000 parts by mass with respect to 100 parts by mass in total of components (A) and (B). When using other solvents, the amount is preferably 50% or less with respect to the blending amount of the above-mentioned (E) terpene-based solvent.

[0081] Method for using silicone adhesive composition Generally, the catalyst is hardly mixed during the storage of the silicone adhesive composition. The catalyst is preferably uniformly mixed with the silicone adhesive composition immediately before actual use. The curing conditions may be 80 to 200 °C for 20 seconds to 10 minutes, but are not limited thereto.

[0082] As the base material to which the silicone adhesive is applied, paper, plastic film, glass, and metal are selected. Examples of paper include high-quality paper, coated paper, art paper, glassine paper, polyethylene laminated paper, kraft paper, etc. Examples of plastic films include polyethylene film, polypropylene film, polyester film, polyimide film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, polycarbonate film, polytetrafluoroethylene film, polystyrene film, ethylene-vinyl acetate copolymer film, ethylene-vinyl alcohol copolymer film, triacetyl cellulose film, polyether ether ketone film, polyphenylene sulfide film, etc. There are no particular restrictions on the thickness or type of glass, and it may be subjected to chemical strengthening treatment or the like. Also, glass fibers can be applied, and the glass fibers may be used alone or in combination with other resins. Examples of metals include aluminum foil, copper foil, gold foil, silver foil, nickel foil, etc. Among these base materials, the silicone adhesive is particularly often used with a plastic film as the base material.

[0083] Adhesive tapes and adhesive sheets made with various plastic films as the base material are used in various applications, such as protective films for various displays, electrical insulation tapes, masking tapes, splicing tapes, and for sticking to the skin. Examples of displays include television receivers, computer monitors, monitors for portable information terminals, monitors for surveillance, video cameras, digital cameras, mobile phones, portable information terminals, instrument panel displays for automobiles, etc., instrument panel displays for various equipment, devices, and instruments, liquid crystal displays, organic EL displays, various touch panels and flat panel displays (FPDs) for displaying characters, symbols, images, etc. such as automatic ticket vending machines and automated teller machines.

[0084] The coating method may be carried out using a known coating method. For example, comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater, gravure coater, screen coating, dip coating, cast coating, etc. can be mentioned. There is no particular limitation on the coating amount, but it can be 0.1 to 500 μm, preferably 0.5 to 300 μm.

Examples

[0085] Hereinafter, examples and comparative examples will be shown to explain the present invention in detail, but the present invention is not limited to the following examples. Also, in the following, Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group.

[0086] Preparation of Adhesive Tape Sample 1 A test solution of a silicone adhesive composition obtained by quickly adding and mixing a curing catalyst (D) to a mixture containing components (A1), (B1), (C), (E), and (F) prepared by the composition and method described below was applied to a polyimide film with a thickness of 25 μm and a width of 25 mm using an applicator and set so that the thickness of the cured adhesive layer was 30 μm. This was heated in a dryer at 130°C for 1 minute to prepare an adhesive tape.

[0087] Preparation of Adhesive Tape Sample 2 A test solution of a silicone adhesive composition containing components (A2), (B2), and (E) prepared by the composition and method described below was applied to a polyimide film with a thickness of 25 μm and a width of 25 mm using an applicator and set so that the thickness of the cured adhesive layer was 30 μm. This was heated in a dryer at 130°C for 1 minute to prepare an adhesive tape.

[0088] Measurement of Adhesive Force The prepared adhesive tape was attached to a stainless steel plate and crimped by reciprocating a roller coated with a rubber layer weighing 2 kg twice. This was left standing for one day, and the force (N / 25 mm) required to peel the tape from the stainless steel plate at an angle of 180° at a speed of 300 mm / min was measured using a tensile tester.

[0089] Measurement of holding force The prepared adhesive tape was cut into pieces 75 mm in length and 25 mm in width, attached to the end of a stainless steel plate so that the area of the adhesive part was 25 mm x 25 mm, a load of 1 kg was applied to the lower end of the adhesive tape, and the displacement distance after being vertically left at 200 °C for 1 hour was measured with a traveling microscope.

[0090] Evaluation of odor When the above adhesive tape was prepared, 10 professional panelists confirmed the odor in the state before putting the substrate coated with the adhesive into the dryer. Scoring was carried out according to the following criteria, and the average score was calculated. Criteria 5: Weak odor 4: Slightly weak odor 3: Slightly strong odor 2: Strong odor 1: Intense odor

[0091] Addition reaction-curing type silicone adhesive composition [Example 1-1] As the component (A1), 90.0 parts by mass of dimethylpolysiloxane represented by the following formula, in which both ends of the molecular chain are blocked with vinyl groups and which has an alkenyl group content of 0.002 mol / 100 g, is shown by the following formula

Chemical formula

[0092] [Example 1-2] (A1) component: 100.0 parts by mass of a dimethylpolysiloxane represented by the following formula, having vinyl groups blocking both ends of the molecular chain and an alkenyl group content of 0.002 mol / 100 g, [Chemical formula] (C) component: 1.28 parts by mass of a polyorganohydrogensiloxane represented by the above formula (C-1) and having an SiH group of 1.56 mol / 100 g (molar ratio of SiH group to the number of moles of alkenyl group of the above (A1-2) component = 10.0), and (F) component, 0.20 parts by mass of ethynylcyclohexanol, was mixed and dissolved in 236.76 parts by mass of (E-1) α-pinene which is the (E) component to obtain a 30% by mass mixture of the active ingredient. To 100 parts by mass of the obtained mixture, 0.1 part by mass of a silicone solution containing 0.5% by mass of platinum of a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum(0) complex as the (D) component was added to prepare a test solution of the silicone pressure-sensitive adhesive composition. The amount of platinum with respect to the total amount of the (A) and (C) components is 16.7 ppm by mass.

[0093] [Example 1-3] As the (A1) component, 35.0 parts by mass of dimethylpolysiloxane represented by the following formula where both ends of the molecular chain are blocked with vinyl groups and having an alkenyl group content of 0.0009 mol / 100 g, [Chemical formula] As the (B1) component, Me3SiO 1 / 2 units and SiO2 units, and 65.0 parts by mass of a powder of organopolysiloxane (B1-1) having a molar ratio of (Me3SiO 1 / 2 units) / (SiO2 units) of 0.85, As the (C) component, 0.24 part by mass of a polyorganohydrogensiloxane represented by the above formula (C-1) and having 1.56 mol / 100 g of Si-H groups (molar ratio of SiH groups to the molar number of alkenyl groups of the above (A1-3) component = 12.0), and 0.20 part by mass of ethynylcyclohexanol as the (F) component were mixed and dissolved in 66.95 parts by mass of (E-1) α-pinene which is the (E) component to obtain a 60% by mass mixture of the active ingredient. To 100 parts by mass of the obtained mixture, 50 parts by mass of (E-1) α-pinene was further added, and 0.5 part by mass of a silicone solution containing 0.5% by mass of platinum of a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum(0) complex as the (D) component was added to prepare a test solution of the silicone pressure-sensitive adhesive composition. The amount of platinum with respect to the total amount of the (A1), (B1) and (C) components is 41.7 ppm by mass.

[0094] [Example 1-4] In Example 1-1 above, a silicone pressure-sensitive adhesive composition was obtained by repeating the steps of Example 1-1 except that (E-1) α-pinene was replaced with (E-2) p-menthane.

[0095] [Example 1-5] In Example 1-2 above, a silicone pressure-sensitive adhesive composition was obtained by repeating the steps of Example 1-2 except that (E-1) α-pinene was replaced with (E-2) p-menthane.

[0096] [Example 1-6] In Example 1-3 above, a silicone pressure-sensitive adhesive composition was obtained by repeating the steps of Example 1-3 except that (E-1) α-pinene was replaced with (E-2) p-menthane.

[0097] [Comparative Example 1-1] In Example 1-1 above, a silicone pressure-sensitive adhesive composition was obtained by repeating the steps of Example 1-1 except that (E-1) α-pinene was replaced with (X) toluene.

[0098] [Comparative Example 1-2] In Example 1-2 above, a silicone pressure-sensitive adhesive composition was obtained by repeating the steps of Example 1-2 except that (E-1) α-pinene was replaced with (X) toluene.

[0099] [Comparative Example 1-3] In Example 1-3 above, a silicone pressure-sensitive adhesive composition was obtained by repeating the steps of Example 1-3 except that (E-1) α-pinene was replaced with (X) toluene.

[0100] Using the test solutions of the silicone pressure-sensitive adhesive compositions obtained in the above Examples and Comparative Examples, adhesive tapes were produced by the method described above. For the adhesive tapes, the adhesive force, holding power, and odor were evaluated according to the method described above. The results are shown in Tables 1 and 2 below.

[0101]

Table 1

[0102]

Table 2

[0103] As shown in Tables 1 and 2 above, the pressure-sensitive adhesive tapes (Examples 1-1 to 1-6) prepared using the addition reaction-curing type silicone pressure-sensitive adhesive composition using α-pinene or p-menthane as a solvent had the same adhesive force and holding force as the pressure-sensitive adhesive tapes prepared using the conventional type adhesive using toluene solvent of Comparative Examples 1-1 to 1-3. Further, the addition reaction-curing type silicone pressure-sensitive adhesive compositions of Examples 1-1 to 1-6 had a lower odor than the silicone pressure-sensitive adhesive compositions of Comparative Examples 1-1 to 1-3. Although the boiling points of α-pinene and p-menthane are higher than 130°C which is the curing temperature of the silicone pressure-sensitive adhesive composition, in the case of curing of the coating material, if the solvent has a certain degree of volatility, the solvent can be removed even at a temperature below the boiling point. The addition reaction-curing type silicone pressure-sensitive adhesive composition of the present invention has a low odor and can reduce the burden on the operator.

[0104] Condensation reaction-curing type silicone pressure-sensitive adhesive composition [Example 2-1] (Component (A2)) 50 parts by mass of polydimethylsiloxane (A2-1) having a viscosity of 1,500 mPa·s when dissolved in toluene to a concentration of 30% by mass and having Si-OH groups blocking the molecular chain ends, and (Component (B2)) Me3SiO 1 / 2 units and containing SiO2 units, (Me3SiO 1 / 250 parts by mass of a powder of organopolysiloxane (B2-1) having a molar ratio of (unit) / (SiO2 unit) of 0.85, containing 0.12 mol / 100 g of Si-OH groups and 0.015 mol / 100 g of Si-O-iPr and having a number average molecular weight of 2800 confirmed by GPC, and 42.86 parts by mass of p-menthane (E-1) as the (E) component were mixed and uniformly dissolved, and 0.5 part by mass of 28% by mass aqueous ammonia was added thereto, followed by mixing and stirring at 25°C for 15 hours. Then, ammonia and water were distilled off by heating under reflux at 150°C for 4 hours, and p-menthane was added so that the solid content became 70% by mass to prepare a silicone adhesive composition. A test solution was prepared by further adding 20 parts by mass of p-menthane to the silicone adhesive composition for dilution.

[0105] [Example 2-2] The steps of Example 2-1 were repeated except that the (A2-1) component was changed to 40 parts by mass and the (B2-1) component was changed to 60 parts by mass to obtain a test solution of the silicone adhesive composition.

[0106] [Example 2-3] 30 parts by mass of the (A2-1) component, 70 parts by mass of the (B2-1) component, and 33.33 parts by mass of the (E-1) component were mixed and uniformly dissolved, and 0.5 part by mass of 28% by mass aqueous ammonia was added thereto, followed by mixing and stirring at 25°C for 15 hours. Then, ammonia and water were distilled off by heating under reflux at 150°C for 4 hours, and p-menthane was added so that the solid content became 75% by mass to prepare a silicone adhesive composition. A test solution was prepared by further adding 20 parts by mass of p-menthane to the silicone adhesive composition for dilution.

[0107] [Example 2-4] As the (A2) component, 40 parts by mass of polydimethylsiloxane (A2-2) with a viscosity of 100,000 mPa·s at 25°C and its molecular chain ends blocked with Si-OH groups, 60 parts by mass of the above (B2-1) component, and 33.33 parts by mass of the above (E-1) component were mixed and uniformly dissolved. Then, 0.5 part by mass of 28% ammonia water was added thereto, and the mixture was stirred at 25°C for 15 hours. Thereafter, ammonia and water were distilled off by heating under reflux at 150°C for 4 hours, and p-menthane was added so that the solid content became 75% by mass to prepare a silicone adhesive composition. A test solution was prepared by further adding 20 parts by mass of p-menthane to dilute the silicone adhesive composition.

[0108] [Example 2-5] In Example 2 above, except that 40 parts by mass of polydimethylsiloxane (A2-3) with a viscosity of 5,000 mPa·s when dissolved in toluene to a concentration of 30% was used instead of the above (A2-1), the steps of Example 2-2 were repeated to prepare a test solution of the silicone adhesive composition.

[0109] [Example 2-6] As the (A2) component, 40 parts by mass of polydimethylsiloxane (A2-1) with a viscosity of 1,500 mPa·s when dissolved in toluene to a concentration of 30% and its molecular chain ends blocked with Si-OH groups, as the (B2) component, Me3SiO 1 / 2 units and SiO2 units are contained, and the molar ratio of (Me3SiO 1 / 2 units) / (SiO2 units) is 0.85, and 60 parts by mass of a powder of organopolysiloxane (B2-1) containing 0.12 mol / 100 g of Si-OH groups and 0.015 mol / 100 g of Si-O-iPr, and 42.86 parts by mass of α-pinene (E-2) as the (E) component were mixed and uniformly dissolved. Then, 0.5 part by mass of 28% ammonia water was added thereto, and the mixture was stirred at room temperature for 15 hours. Thereafter, ammonia and water were distilled off by heating under reflux at 150°C for 4 hours, and α-pinene was added so that the solid content became 70% by mass to prepare an adhesive composition. A test solution was prepared by further adding 20 parts by mass of α-pinene to dilute the silicone adhesive composition.

[0110] [Example 2-7] In Example 2-6, except that 40 parts by mass of polydimethylsiloxane (A2-2) having a viscosity at 25°C of 100,000 mPa·s and a molecular chain end blocked with an Si-OH group was used instead of the (A2-1) component, the steps of Example 2-6 were repeated to obtain a test solution of the silicone adhesive composition.

[0111] [Example 2-8] In Example 2-6, except that 40 parts by mass of polydimethylsiloxane (A2-3) having a viscosity of 5,000 mPa·s when dissolved in toluene to a concentration of 30% by mass and a molecular chain end blocked with an Si-OH group was used instead of the (A2-1) component, the steps of Example 2-6 were repeated to obtain a test solution of the silicone adhesive composition.

[0112] [Comparative Example 2-1] In Example 2-2 above, except that toluene (X) was used instead of (E-1) p-menthane, the steps of Example 2-2 were repeated to obtain a test solution of the silicone adhesive composition.

[0113] [Comparative Example 2-2] In Example 2-4 above, except that toluene (X) was used instead of (E-1) p-menthane, the steps of Example 2-4 were repeated to obtain a test solution of the silicone adhesive composition.

[0114] [Comparative Example 2-3] In Example 2-5 above, except that toluene (X) was used instead of (E-1) p-menthane, the steps of Example 2-5 were repeated to obtain a test solution of the silicone adhesive composition.

[0115] Using the test solutions of the silicone adhesive compositions obtained in the above Examples and Comparative Examples, adhesive tapes were produced by the method described above. For the adhesive tapes, the adhesive force and odor were evaluated according to the method described above. The results are shown in Table 3 below.

[0116]

Table 3

[0117] As shown in Table 3 above, the adhesive tapes (Examples 2-1 to 2-8) obtained using the condensation reaction-curing type silicone adhesive composition with p-menthane and α-pinene as solvents had the same adhesive force as the adhesive tapes made of the conventional adhesives of Comparative Examples 2-1 to 2-3 using toluene solvent. Also, the condensation reaction-curing type silicone compositions of Examples 1 to 8 had a lower odor than the silicone compositions of Comparative Examples 2-1 to 2-3. The boiling points of p-menthane and α-pinene are higher than the curing temperature of 130°C, but in the case of curing of the coating system material, if the solvent has a certain degree of volatility, the solvent can be removed even at a temperature below the boiling point. Therefore, the composition of the present invention has a low odor and can reduce the burden on workers.

[0118] Since the silicone adhesive composition of the present invention has a low odor, it is possible to reduce the odor of the resulting adhesive article such as an adhesive film. By manufacturing an adhesive article using the silicone adhesive composition of the present invention, the burden on workers can be reduced.

Claims

1. (A)A linear, branched or cyclic organopolysiloxane selected from the following (A1) and (A2): (A1)A linear, branched or cyclic organopolysiloxane having at least two alkenyl group-containing organic groups in one molecule and having 0.0005 to 0.10 mol of alkenyl groups per 100 g of the organopolysiloxane. (A2)A linear, branched or cyclic organopolysiloxane having Si-OH groups at at least two terminals. (B) R ２ ３ SiO １／２ units and SiO ４／２ units, and (R ２ ３ SiO １／２ units) / (SiO ４／２ units) has a molar ratio of 0.6 to 1.0, a resinous organopolysiloxane (in the above formula, R ２ is, independently of each other, a monovalent hydrocarbon group having 1 to 10 carbon atoms without an aliphatic unsaturated bond, an alkenyl group having 2 to 10 carbon atoms, a hydrolyzable group having 1 to 10 carbon atoms, or a hydroxyl group) 0 to 80 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B), and (E)At least one solvent selected from terpenes and terpene derivatives, in an amount of 1 to 2000 parts by mass based on 100 parts by mass in total of the above components (A) and (B). The silicone adhesive composition may optionally contain an effective amount for curing of a curing agent and a curing catalyst. Silicone adhesive composition.

2. The silicone adhesive composition according to claim 1, wherein the component (E) is at least one selected from a monoterpene compound having 10 carbon atoms and a terpenoid compound having a carbonyl group or a hydroxy group.

3. The silicone adhesive composition according to claim 1 or 2, wherein the component (E) has a boiling point of 220°C or lower.

4. 30 to 100 parts by mass of a linear, branched or cyclic organopolysiloxane (A1) having at least two alkenyl group-containing organic groups in one molecule and having 0.0005 to 0.10 mol of alkenyl groups per 100 g of the organopolysiloxane. (B1) R ２ ３ SiO １／２ units and SiO ４／２ units, and (R ２ ３ SiO １／２ units) / (SiO ４／２ units) has a molar ratio of 0.6 to 1.0, a resinous organopolysiloxane (in the above formula, R ２ is, independently of one another, a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms that does not have an aliphatic unsaturated bond, and optionally a part of R ２ may be a hydrolyzable group having 1 to 10 carbon atoms or a hydroxyl group) 0 to 70 parts by mass with respect to a total of 100 parts by mass of the components (A1) and (B1) An amount such that the ratio of the number of moles of SiH groups in the component (C) to the number of moles of alkenyl groups in the components (A1) and (B1) of a polyorganohydrosiloxane (C) having at least three SiH groups in one molecule is 0.2 to 20. (D)A platinum group metal-based catalyst in a catalytic amount, and (E)At least one solvent selected from terpenes and terpene derivatives, in an amount of 1 to 2000 parts by mass based on 100 parts by mass in total of the components (A1) and (B1). Silicone adhesive composition containing the same.

5. The silicone adhesive composition according to claim 4, wherein the component (A1) is represented by the following average formula (1). 【Chemical 1】 (In formula (1), R １ is, independently of one another, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom, and at least two of R １ are alkenyl group-containing organic groups having 2 to 10 carbon atoms, a is a positive number of 2 or more, b is a positive number of 1 or more, c and d are positive numbers of 0 or more, and 50 ≦ a + b + c + d ≦ 15000)

6. Component (C) has an average composition formula: R ３ ｅ H ｆ SiO （４－ｅ－ｆ）／２ (wherein R ３ are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, e > 0, f > 0, and further 0 < e + f ≦ 3) The silicone adhesive composition according to claim 4, represented by the following formula.

7. Furthermore, the silicone adhesive composition according to claim 4, containing an addition reaction control agent (F) in an amount of 0.01 to 5 parts by mass based on 100 parts by mass in total of the components (A1), (B1) and (C).

8. The silicone pressure-sensitive adhesive composition according to claim 4, wherein the component (E) is at least one selected from a monoterpene compound having 10 carbon atoms and a terpenoid compound having a carbonyl group or a hydroxy group.

9. The silicone pressure-sensitive adhesive composition according to claim 4, wherein the component (E) has a boiling point of 220°C or lower.

10. The silicone pressure-sensitive adhesive composition according to claim 1 or 4, wherein the alkenyl group-containing organic group is selected from an alkenyl group, an acryloylalkyl group, a methacryloylalkyl group, a cycloalkenylalkyl group, and an alkenyloxyalkyl group.

11. 20 to 80 parts by mass of a linear, branched or cyclic organopolysiloxane having Si-OH groups at at least two terminals (A2) (B2)R ２ ３ SiO １／２ units and SiO ４／２ units, and (R ２ ３ SiO １／２ units) / (SiO ４／２ units) has a molar ratio of 0.6 to 1.0, a resinous organopolysiloxane (wherein R ２ is, independently of one another, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a hydrolyzable group having 1 to 10 carbon atoms, or a hydroxyl group, and at least one R ２ is a hydroxyl group or a hydrolyzable group) 80 to 20 parts by mass based on 100 parts by mass of the total amount of the component (A2) and the component (B2), and At least one solvent selected from terpenes and terpene derivatives (E) 1 to 2000 parts by mass based on 100 parts by mass in total of the components (A2) and (B2) A silicone pressure-sensitive adhesive composition comprising.

12. The silicone pressure-sensitive adhesive composition according to claim 11, wherein the component (A2) is a polydiorganosiloxane having one Si-OH group at each of both ends represented by the following average formula (2). [Chemical Formula 2] (R ４ is, independently of one another, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and a is a positive number of 100 or more)

13. The silicone pressure-sensitive adhesive composition according to claim 11, wherein the component (E) is at least one selected from a monoterpene compound having 10 carbon atoms and a terpenoid compound having a carbonyl group or a hydroxy group.

14. The silicone pressure-sensitive adhesive composition according to claim 11, wherein the component (E) has a boiling point of 220°C or lower.

15. An adhesive article having a base material and a cured product formed by curing the silicone pressure-sensitive adhesive composition according to any one of claims 1 to 9 on at least one surface of the base material surface.

16. An adhesive article having a base material and a cured product formed by curing the silicone pressure-sensitive adhesive composition according to any one of claims 11 to 14 on at least one surface of the base material surface.