JP2006028311A - Silicone adhesive composition having excellent heat resistance and production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicone adhesive composition having excellent heat resistance and a production method thereof. <P>SOLUTION: The silicone adhesive composition comprises (A) a polydiorganosiloxane, (B) a polyorganosiloxane containing an R<SP>1</SP><SB>3</SB>SiO<SB>0.5</SB>unit and an SiO<SB>2</SB>unit regulated so that the molar ratio of the R<SP>1</SP><SB>3</SB>SiO<SB>0.5</SB>unit to the SiO<SB>2</SB>unit may be 0.6-1.7, (C) a dry-process silica having the surface subjected to hydrophobation treatment, (D) an organic peroxide curing agent and (E) an organic solvent, and is produced by adding the component (D) to a product obtained by mixing a part or the whole of the components (A), (B), (C) and (E) in the presence of a basic catalyst. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a silicone pressure-sensitive adhesive composition excellent in heat resistance and a production method.

  Adhesive tapes and labels that use silicone adhesives are acrylic adhesives, rubber adhesives, etc., because the silicone adhesive layer has excellent heat resistance, cold resistance, weather resistance, electrical insulation and chemical resistance. Organic adhesives are used in harsh environments where they are altered or deteriorated.

  For example, when heat treatment is performed at the time of manufacturing parts or during processing, it may be necessary to protect the entire surface or a part, masking or temporary fixing. For adhesive tapes used for such applications and adhesive tapes used for fixing and binding electronic / electrical parts exposed to high temperatures, those using a silicone adhesive that has heat resistance even after heating above 250 ° C are suitable. It is. However, in recent years, heat treatment at a higher temperature has been performed, and heat resistance at a higher temperature has been required. Further, even when used for fixing, bundling, etc., it has been desired that it can be used even at an ambient temperature exceeding 250 ° C.

  For example, with the practical application of lead-free solder in electronic component mounting, the reflow temperature for soldering electronic components to a substrate becomes higher than before, and the peak temperature may reach 280 ° C. Accordingly, the pressure-sensitive adhesive must not be peeled off even at such a high temperature, and it is necessary that the pressure-sensitive adhesive can be peeled off without being transferred to or remaining on the adherend when the treatment is completed.

  When an adhesive tape using a conventional silicone adhesive is affixed or masked to an adherend and receives a high temperature history of 200 to 250 ° C., the adhesive tape and the adherend may be displaced or peeled off. . Further, when the adhesive tape is peeled off and removed, the adhesive remains on the adherend, or the adhesive layer may be transferred from the base material of the adhesive tape to the adherend. This is called glue residue. This is because the silicone pressure-sensitive adhesive deteriorates by heating, and the cohesive force of the pressure-sensitive adhesive layer decreases accordingly, and the pressure-sensitive adhesive layer is destroyed.

Further, by adding a phenolic antioxidant to the addition reaction curable silicone pressure-sensitive adhesive composition, it is attached to or masked on an adherend such as metal, particularly copper, copper alloy, iron, etc., and has a high temperature of 150 to 250 ° C. It is known to provide a silicone pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape that can be peeled cleanly without causing adhesive residue even when receiving the above history (see Patent Document 1).
However, if a silicone adhesive containing such an antioxidant is given a high temperature history exceeding 250 ° C, the cohesive strength of the adhesive layer is reduced, or adhesive residue is generated when the adhesive tape is peeled off and removed. There are things to do.

The silicone pressure-sensitive adhesive composition containing silica filler contains powdered silica having a surface area of 100 m ² / g or more, and is a peroxide that undergoes a condensation reaction between silicone rubber and MQ resin at 80 to 150 ° C. in the presence of benzoyl peroxide. A product-curable pressure-sensitive adhesive composition is disclosed (see Patent Document 1). In this product, the condensation reaction of silicone rubber and MQ resin is performed using benzoyl peroxide, so that the reaction is difficult to control, the reaction is insufficient, the viscosity becomes too high, or the gelation occurs. is there. Furthermore, since the reactivity of MQ resin by benzoyl peroxide is inferior to that of silicone rubber, the MQ resin may be unreacted. Further, an addition-type pressure-sensitive adhesive composition containing silica having a specific surface area of less than 25 m ² / g has been disclosed (see Patent Document 2), and is characterized by having high adhesiveness and a low coefficient of thermal expansion. . This has the problem that the specific surface area of silica is small and the dispersibility in the composition is poor.

Furthermore, it is disclosed that a silica filler having a specific surface area of 50 to 400 m ² / g is added to an addition-type silicone pressure-sensitive adhesive composition for the purpose of imparting thixotropy (see Patent Document 4). However, this has a problem that the dispersibility of the silica in the composition is insufficient or the heat resistance is inferior due to the influence of the thixotropic agent.

  The present invention is an improvement of the above circumstances, and it is an object of the present invention to simply provide a silicone pressure-sensitive adhesive composition that can be suitably used for electronic and electrical parts even when subjected to a high temperature history of 280 ° C. And

JP 2000-96429 A Japanese Examined Patent Publication No. 46-13520 JP 2000-265150 A JP 2001-81436 A

As a result of intensive studies to achieve the above object, the present inventor has found that the silicone pressure-sensitive adhesive composition containing dry silica whose surface is hydrophobized has a heat resistance exceeding 280 ° C., It came to make this invention.
The silicone pressure-sensitive adhesive composition of the present invention may be either an organic peroxide curable type or an addition reaction curable type.

As the peroxide curable silicone pressure-sensitive adhesive composition, the following are used.
(A) Polydiorganosiloxane 20 to 80 parts by mass (B) R ¹ ₃ SiO _0.5 units and SiO ₂ units are contained, and the molar ratio of R ¹ ₃ SiO _0.5 units / SiO ₂ units is 0.6 to Polyorganosiloxane of 1.7 (R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms) 80-20 parts by mass (C) Dry silica (A), (B) whose surface has been hydrophobized 0.2-8.0 parts by mass with respect to a total of 100 parts by mass (D) 0.5-5.0 parts by mass with respect to a total of 100 parts by mass of the organic peroxide curing agent (A), (B) A peroxide-curable silicone pressure-sensitive adhesive composition is provided.

The following are used as the addition reaction curable silicone pressure-sensitive adhesive composition.
(A ′) 20 to 80 parts by mass of a polydiorganosiloxane having two or more alkenyl groups in one molecule (B) containing R ¹ ₃ SiO _0.5 unit and SiO ₂ unit, and R ¹ ₃ SiO _0.5 Polyorganosiloxane having a unit / SiO ₂ unit molar ratio of 0.6 to 1.7 (R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms) 80 to 20 parts by mass (C) Hydrophobized surface 0.2 to 8.0 parts by mass of (F) SiH group-containing polyorganosiloxane (A ′) alkenyl group in component (A ′) and 100 parts by mass of dry silica (A ′) and (B) treated The amount of SiH groups in the component (E) relative to the amount of 0.5 to 20 (G) 0 to 8.0 parts by mass with respect to a total of 100 parts by mass of the control agents (A ′) and (B) ( H) Platinum catalyst (A ') As a platinum content with respect to the total of (B) component, 5-2 000ppm
An addition reaction type silicone pressure-sensitive adhesive composition is provided.

  According to the present invention, it is attached to an adherend such as a metal, particularly stainless steel, masked, and even when subjected to a high temperature history of 280 ° C., it is not displaced or peeled off from the adherend, and it is clean without causing adhesive residue. A silicone pressure-sensitive adhesive composition that can be peeled can be obtained.

The following are used as the peroxide-curable silicone pressure-sensitive adhesive composition of the present invention.
(A) Polydiorganosiloxane 20 to 80 parts by mass (B) R ¹ ₃ SiO _0.5 units and SiO ₂ units are contained, and the molar ratio of R ¹ ₃ SiO _0.5 units / SiO ₂ units is 0.6 to Polyorganosiloxane of 1.7 (R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms) 80-20 parts by mass (C) Dry silica (A), (B) whose surface has been hydrophobized 0.2-8.0 parts by mass with respect to a total of 100 parts by mass (D) 0.5-5.0 parts by mass with respect to a total of 100 parts by mass of the organic peroxide curing agent (A), (B) A peroxide-curable silicone pressure-sensitive adhesive composition is provided. Moreover, this invention provides the manufacturing method of said silicone adhesive composition.

  In this case, these silicone pressure-sensitive adhesive compositions are effectively used for pressure-sensitive adhesive tapes, pressure-sensitive adhesive sheets, pressure-sensitive adhesive labels and the like that are particularly excellent in heat resistance.

  More specifically, the component (A) is polydiorganosiloxane and is represented by the following formula.

（式中、Ｒ^２は同一または異種の炭素数１から１０の炭化水素基。ｐはこのポリジオルガノシロキサンの２５℃における粘度を５００ｍＰａ・ｓ以上とする数である。）

(In the formula, R ² is the same or different hydrocarbon group having 1 to 10 carbon atoms. P is a number that makes this polydiorganosiloxane have a viscosity at 25 ° C. of 500 mPa · s or more.)

Here, as R ² , a monovalent hydrocarbon group having 1 to 10 carbon atoms is preferable. For example, an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, a cycloalkyl group such as a cyclohexyl group, phenyl Group, aryl group such as tolyl group, alkenyl group such as vinyl group, allyl group, hexenyl group and the like, and methyl group and phenyl group are particularly preferable.

  The polydiorganosiloxane may be in the form of oil or raw rubber. The viscosity of the component (A) is 500 mPa · s or more if it is oily at 25 ° C. In particular, 10,000 mPa · s or more is preferable. If it is 500 mPa · s or less, the curability is lowered or the cohesive force (holding force) is lowered, which is not suitable. Moreover, if it is a raw rubber-like thing, the viscosity when it melt | dissolves with toluene so that it may become a 30% density | concentration is preferable 100,000 mPa * s or less. If it exceeds 100,000 mPa · s, the composition becomes too viscous and stirring during production becomes difficult. Furthermore, (A) component may use 2 or more types together.

  The component (A) is usually produced by subjecting a monomer such as octamethylcyclotetrasiloxane to ring-opening polymerization using a catalyst. Since the polymer contains a cyclic low-molecular siloxane after polymerization, It is preferable to use a product obtained by distilling siloxane while heating and / or aerated with an inert gas under reduced pressure.

The component (B) contains R ¹ ₃ SiO _0.5 units (R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms) and SiO ₂ units, and R ¹ ₃ SiO _0.5 units / SiO ₂ It is a polyorganosiloxane having a unit molar ratio of 0.6 to 1.7. If the molar ratio of R ¹ ₃ SiO _0.5 unit / SiO ₂ unit is less than 0.6, the adhesive force and tack may be lowered, and if it exceeds 1.7, the adhesive force and holding force may be lowered. Examples of R ¹ include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, and a hexenyl group. A methyl group is preferred.

The component (B) may contain OH groups, and the OH group content is preferably 0.01 to 4.0% by mass. When the OH group is less than 0.01% by mass, the cohesive force of the pressure-sensitive adhesive may be lowered, and when it exceeds 4.0% by mass, the tackiness of the pressure-sensitive adhesive is not preferable. It is also possible to within a range that does not impair the characteristics of the present invention contains ^R 1 _{SiO 1.5} ^units, a _R 1 2 SiO units (B) component. In addition, (B) component may use 2 or more types together.

  The mixing ratio of the components (A) and (B) is preferably 20/80 to 80/20, particularly 30/70 to 70/30 as a mass ratio. When the blending ratio of the polydiorganosiloxane as the component (A) is lower than 20/80, the adhesive strength and holding power decrease, and when it exceeds 80/20, the adhesive strength and tack decrease.

  The component (C) used in the present invention is obtained by hydrophobizing the surface of dry process silica. The known silica is roughly classified into dry silica and wet silica, and there are untreated silica and treated silica for each. Among these, the silica that can be used in the present invention is dry silica whose surface is hydrophobized. When wet silica is used, the adhesive strength of the silicone pressure-sensitive adhesive composition may be too low for both untreated silica and treated silica. Further, when untreated silica is used even with dry silica, the dispersion of silica is extremely poor and a uniform composition cannot be obtained.

  The hydrophobization treatment of the surface of the dry method silica may be performed by a known method. That is, as a method of hydrophobizing dry silica, a method of adding an aliphatic alcohol to a silanol group (US Pat. No. 2,657,149), an organochlorosilane vapor is contacted, and the silanol group is converted to an organosiloxy group. Methods for conversion, methods of reacting with organosiloxanes (Japanese Patent Publication No. 38-22129), methods of reacting silazane compounds to convert silanol groups to organosiloxy groups (US Pat. No. 789,352), etc. are known. ing.

  The method for hydrophobizing a dry process silica used in the present invention may be performed by any method, but in the present invention, the surface of hydrophilic silica is treated with dimethyldisilane, which is a silicon compound having a hydrolyzable group. Hydrophobic treatments with organochlorosilanes such as chlorosilane and trimethylchlorosilane, silazane compounds such as hexamethyldisilazane, cyclic silazanes such as hexamethylcyclotrisilazane, polydimethylsiloxane, octamethylcyclotetrasiloxane and the like are preferred.

  In order to perform this hydrophobization treatment, the silica fine powder whose surface has been treated with a surface treatment agent is preferably pretreated directly in a powder state, and a generally well-known technique should be adopted as a normal treatment method. For example, the untreated silica fine powder and the treatment agent are put in a mechanical kneading apparatus sealed at normal pressure or in a fluidized bed, and mixed at room temperature or heat treatment in the presence of an inert gas as necessary. Treated, and optionally catalyst and water for accelerating hydrolysis may be used and can be adjusted by kneading and drying. The blending amount of the treatment agent may be equal to or more than the amount calculated from the coating area of the treatment agent.

  Usually, the amount of carbon on the surface of the hydrophobized filler (based on the entire hydrophobized silica) is preferably 0.3 to 8% by weight, particularly 0.8 to 7% by weight.

Further, the specific surface area of the hydrophobized silica needs to be at least 50 m ² / g or more, preferably 80 m ² / g or more in order to obtain dispersibility in the silicone pressure-sensitive adhesive composition. Furthermore, in order to ensure the fluidity | liquidity of a composition, it is necessary to set it as 300 m < ² > / g or less.

  Furthermore, the hydrophobized silica of component (C) has a pH of 3 to 11, particularly 3.5 to 8.5, when 4 g of this silica is dispersed in a mixed solution of 50 ml of pure water and 50 ml of methanol. It is preferable that If the pH is too low, the reaction under a basic catalyst is inhibited, which is not preferable. If the pH is too high, depolymerization of the polydiorganosiloxane may occur during the reaction.

  Examples of the silica whose surface of the dry process silica has been subjected to a hydrophobization treatment include Aerosil R972, R974, R202, R805, R812, and the like under the trade name of Nippon Aerosil Co., Ltd.

  (C) The compounding quantity of a component can be 0.2-8.0 mass parts with respect to a total of 100 mass parts of (A) and (B) component. It is preferably 1 to 4 parts by mass. If it is 0.2 parts by mass or less, sufficient cohesive force, holding power, and heat resistance cannot be obtained, and if it is 8.0 parts by mass or more, adhesive strength and tack may be reduced. In addition, (C) component may use 2 or more types together.

  Component (D) is an organic peroxide curing agent, specifically dibenzoyl peroxide, 4,4′-dimethyldibenzoyl peroxide, 3,3′-dimethyldibenzoyl peroxide, 2,2′-dimethyl. Examples include dibenzoyl peroxide, 2, 2 ′, 4, 4′-tetrachlorodibenzoyl peroxide, cumyl peroxide, and the like.

  (D) The compounding quantity of a component should just be the range of 0.5-5 mass parts with respect to a total of 100 mass parts of a component (A) and (B). 1 to 4 parts by mass is particularly preferable. If it is less than 0.5 part by mass, curability and holding power may be lowered. If it exceeds 5 parts by mass, the pressure-sensitive adhesive layer may be colored or the adhesive strength may be reduced. The form of (D) component is not specifically limited. Examples include (D) component alone, (D) component diluted in an organic solvent, dispersed in water, dispersed in silicone oil or the like and pasted. (D) A component may use 2 or more types together.

  Component (E) is an organic solvent, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, octane and isoparaffin, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate and acetic acid. Examples thereof include ester solvents such as isobutyl, ether solvents such as diisopropyl ether and 1,4-dioxane, and mixed solvents thereof. Aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as hexane, octane and isoparaffin are preferred.

The composition of the present invention is a product obtained by mixing a part or all of the components (A), (B), (C), and (E) in the presence of a basic catalyst at room temperature or under heating. It is manufactured by adding (D) component to. Basic catalysts include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, carbonates such as sodium carbonate and potassium carbonate, bicarbonates such as sodium bicarbonate, sodium methoxy And metal alkoxides such as potassium and potassium butoxide, organic metals such as butyllithium, potassium silanolate, ammonia gas, aqueous ammonia, nitrogen compounds such as methylamine, trimethylamine and triethylamine. Ammonia gas and aqueous ammonia are preferred. The temperature can be 20-150 ° C. Usually, it may be carried out at room temperature or the reflux temperature of an organic solvent. The time is not particularly limited, but may be 0.5 to 10 hours, preferably 1 to 6 hours.
Furthermore, a neutralizing agent that neutralizes the basic catalyst may be added as necessary after completion of the reaction. 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.

  This product is usually filled in a container for storage and transportation by adjusting the concentration of non-volatile components to, for example, 30 to 80% by mass. When producing adhesive tapes, adhesive sheets, adhesive labels, etc., this product is diluted with an organic solvent as necessary, and component (D) is added and mixed, and then applied to various substrates shown below. Is done.

  As another method, a part obtained by mixing and stirring a part of the component (A) and the component (C) under heating is added to the rest of the component (A), the component (B), and the component (E). It can manufacture by adding (D) component to the product obtained by adding a part or all, and heating and mixing these in presence of a basic catalyst.

  In order to stir and mix a part of the component (A) and the component (C) under heating, the temperature may be room temperature to 180 ° C. for 1 to 6 hours, preferably 120 to 160 ° C. for 2 to 4 hours. In this case, the ratio of the component (A) to the component (C) can be 50/50 to 95/5, preferably 60/40 to 90/10. At this time, for the purpose of improving the mixing / dispersibility of the component (A) and the component (C), a diorganosiloxane oligomer or organosilane having a silanol group is added to the components (A) and (C) as necessary. ) You may add 0.5-10 mass parts with respect to a total of 100 mass parts of a component.

  Next, the necessary amount of this and the remainder of component (A), component (B), and part or all of component (E) are added, and these are mixed in the presence of a basic catalyst. The basic catalyst is as described above. The mixing temperature and time are also as described above.

  Furthermore, a neutralizing agent that neutralizes the basic catalyst may be added as necessary after completion of the reaction. The neutralizing agent is as described above.

  This product is usually filled in a container for storage and transportation by adjusting the concentration of non-volatile components to, for example, 30 to 80% by mass. When producing adhesive tapes, adhesive sheets, adhesive labels, etc., this product is diluted with an organic solvent as necessary, and component (D) is added and mixed, and then applied to various substrates shown below. Is done.

According to the manufacturing method as described above, the silica particles can be uniformly dispersed in the silicone pressure-sensitive adhesive.
Regardless of the method as described above, the component (C) cannot be sufficiently dispersed only by adding and mixing the component (C) to the peroxide-curable silicone pressure-sensitive adhesive composition. In this case, since undispersed particles remain, when a silicone pressure-sensitive adhesive composition is applied to a substrate to produce a pressure-sensitive adhesive tape or the like, convex portions due to the particles are generated on the surface of the pressure-sensitive adhesive layer. Appearance is poor, and when it is attached to an adherend, air bubbles are produced at the convex portions and good adhesion cannot be achieved.

The following are used as the addition reaction curable silicone pressure-sensitive adhesive composition.
(A ′) 20 to 80 parts by mass of a polydiorganosiloxane having two or more alkenyl groups in one molecule (B) R ¹ ₃ SiO _0.5 unit and SiO ₂ unit with reduced low molecular siloxane content And a polyorganosiloxane having a R ¹ ₃ SiO _0.5 unit / SiO ₂ unit molar ratio of 0.6 to 1.7 (R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms) 80 to 80 Polyorgano containing 0.2 to 5.0 parts by mass (D) SiH group with respect to a total of 100 parts by mass of 20 parts by mass (C) of the dry silica (A ′) and (B) whose surface has been hydrophobized Siloxane (A ′) The amount of the molar ratio of SiH groups in component (E) to alkenyl groups in component (A) is 0.5-20. (E) Control agent (A ′), (B) total 100 parts by mass 0 to 8.0 parts by mass (G) platinum catalyst (A ′), (B 5~2000ppm as platinum amount based on the total of components
(G) Organic solvent (A ') The addition reaction type silicone adhesive composition which contains 25-900 mass parts with respect to a total of 100 mass parts of (B) is provided.

  In this case, these silicone pressure-sensitive adhesive compositions are effectively used for pressure-sensitive adhesive tapes, pressure-sensitive adhesive sheets, pressure-sensitive adhesive labels and the like having excellent heat resistance.

  More specifically, the component (A ′) is an alkenyl group-containing polydiorganosiloxane, and is preferably represented by the following formula.

（式中、Ｒ^３は脂肪属不飽和結合を有さない１価炭化水素基、Ｒ^４はアルケニル基含有有機基であり、ａは０〜３の整数、好ましくは１、ｍは０以上、ｎは１００以上の整数であり、ａが０のときｍは２以上。また、ｍ＋ｎはこのポリジオルガノシロキサンの２５℃における粘度を５００ ｍＰａ・ｓ以上とする数である。）

(In the formula, R ³ is a monovalent hydrocarbon group having no aliphatic unsaturated bond, R ⁴ is an alkenyl group-containing organic group, a is an integer of 0 to 3, preferably 1, m is 0 or more, n is an integer of 100 or more, and when a is 0, m is 2 or more, and m + n is a number that makes this polydiorganosiloxane have a viscosity at 25 ° C. of 500 mPa · s or more.)

Here, R ³ preferably has 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, phenyl group and tolyl group An aryl group such as a methyl group and a phenyl group are particularly preferable.

The alkenyl group-containing organic group represented by R ⁴ is preferably an organic group having 2 to 10 carbon atoms, such as vinyl group, allyl group, hexenyl group, octenyl group, acryloylpropyl group, acryloylmethyl group, methacryloylpropyl group, cyclohexenylethyl group, A vinyloxypropyl group and the like, and a vinyl group is particularly preferred industrially.

The polydiorganosiloxane may be in the form of oil or raw rubber.
The viscosity of the component (A ′) is at least 500 mPa · s if it is oily at 25 ° C. In particular, 10,000 mPa · s or more is preferable. If it is 500 mPa · s or less, the curability is lowered or the cohesive force (holding force) is lowered, which is not suitable. Moreover, if it is a raw rubber-like thing, the viscosity when it melt | dissolves with toluene so that it may become a density | concentration of 30% is preferable below 100,000 mPa * s. If it exceeds 100,000 mPa · s, the composition becomes too viscous and stirring during production becomes difficult. Furthermore, (A ') component may use 2 or more types together.

  The component (A ′) is usually produced by ring-opening polymerization of a monomer such as octamethylcyclotetrasiloxane using a catalyst. After polymerization, the cyclic low molecular weight siloxane is contained. It is preferable to use molecular siloxane distilled off while heating and reducing pressure while allowing an inert gas to pass through.

As described above, the component (B) contains R ¹ ₃ SiO _0.5 units and SiO ₂ units with a reduced low-molecular siloxane content, and a molar ratio of R ¹ ₃ SiO _0.5 units / SiO ₂ units. Is a polyorganosiloxane (R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms).

(B) 2 or more types of components may be used together. It is also possible to within a range that does not impair the characteristics of the present invention contains ^R 1 _{SiO 1.5} ^units, a _R 1 2 SiO units (B) component.

  The blending ratio of the components (A ′) and (B) may be 20/80 to 80/20. In particular, the ratio is preferably 30/70 to 70/30. When the blending ratio of the polydiorganosiloxane as the component (A ′) is lower than 20/80, the adhesive strength and holding power decrease, and when it exceeds 80/20, the adhesive strength and tack decrease.

  Component (C) is dry silica whose surface is hydrophobized and is the same as described above.

  Component (F) is a crosslinking agent, which is an organohydropolysiloxane having at least 2, preferably 3 or more hydrogen atoms bonded to silicon atoms in one molecule, and uses linear, branched, or cyclic ones. it can.

  Examples of the component (F) include the following formulas, but are not limited to these.

及び／または

And / or

（Ｒ^５は同一または異種の脂肪属不飽和結合を有さない１価炭化水素基であり、ｂは０または１、ｘ、ｙは０以上の整数。ｂが０のときは、ｘは２以上であり、このオルガノヒドロポリシロキサンの２５℃における粘度が１〜５，０００ｍＰａ・ｓとなる数を示す。また、ｓは２以上の整数、ｔは０以上の整数で、かつｓ＋ｔ≧３、好ましくは８≧ｓ＋ｔ≧３の整数を示す。）

(R ⁵ is a monovalent hydrocarbon group not having the same or different aliphatic unsaturated bond, b is 0 or 1, x and y are integers of 0 or more. When b is 0, x is 2 These are the numbers at which the viscosity of this organohydropolysiloxane at 25 ° C. is 1 to 5,000 mPa · s, s is an integer of 2 or more, t is an integer of 0 or more, and s + t ≧ 3, (It preferably represents an integer of 8 ≧ s + t ≧ 3.)

Here, R ⁵ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, a cycloalkyl group such as a cyclohexyl group, a phenyl group, An aryl group such as a tolyl group, and a methyl group and a phenyl group are particularly preferable.

  The viscosity of this organohydropolysiloxane at 25 ° C. is preferably 1 to 5,000 mPa · s, more preferably 5 to 500 mPa · s. A mixture of two or more kinds may be used.

  Component (F) is used so that the molar ratio of SiH groups in component (E) to alkenyl groups in component (A ′) is in the range of 0.5 to 20, particularly 0.8 to 15. It is preferable. If it is less than 0.5, the crosslinking density is lowered, and the holding force may be lowered accordingly. If it exceeds 20, the crosslinking density is increased, and sufficient adhesive force and tack may not be obtained.

  Component (G) is a control agent, and is added to prevent the treatment liquid from thickening or gelling prior to heat curing when the silicone pressure-sensitive adhesive composition is prepared or applied to the substrate. It is. Specific examples include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclohexanol, 3 -Methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethylsiloxycyclohexane, Bis (2,2-dimethyl-3-butynoxy) dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,1,3,3-tetramethyl -1,3-divinyldisiloxane and the like.

  (G) The compounding quantity of a component should just be the range of 0-8.0 mass parts with respect to a total of 100 mass parts of a component (A ') and (B) component, and especially 0.05-2.0 mass parts. Is preferred. If it exceeds 8.0 parts by mass, curability may be lowered.

  Component (H) is a platinum-based catalyst, containing chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and alcohol, a reaction product of chloroplatinic acid and an olefin compound, and containing chloroplatinic acid and a vinyl group Examples thereof include a reaction product with siloxane, a platinum-olefin complex, and a platinum-vinyl group-containing siloxane complex.

  The addition amount is preferably 5 to 2,000 ppm, particularly preferably 10 to 500 ppm in terms of platinum with respect to the total of components (A ′) and (B). If it is less than 5 ppm, the curability is lowered, the crosslinking density is lowered and the holding power may be lowered, and if it exceeds 2,000 ppm, the usable time of the treatment bath may be shortened.

  The composition of the present invention is obtained by mixing a part or all of the components (A ′), (B), (C), and (E) in the presence of a basic catalyst into (F), ( It is produced by adding the components G) and (H). The basic catalyst is the same as described above. Although the temperature of mixing can be 20-150 degreeC, what is necessary is just to carry out normally at the reflux temperature of room temperature-the organic solvent. The time is not particularly limited, but may be 0.5 to 10 hours, preferably 1 to 6 hours.

  Furthermore, a neutralizing agent that neutralizes the basic catalyst may be added as necessary after completion of the reaction. The neutralizing agent is the same as described above.

  This product is usually filled in a container for storage and transportation by adjusting the concentration of non-volatile components to, for example, 30 to 80% by mass. When manufacturing adhesive tapes, adhesive sheets, adhesive labels, etc., dilute this product with an organic solvent as necessary, add and mix component (H), and apply to various substrates shown below. Is done.

  As another method, in the mixture obtained by mixing and stirring a part of the component (A ′) and the component (C) under heating, the rest of the component (A ′), the component (B), and the component (E) Can be produced by adding the components (F), (G) and (H) to the product obtained by adding a part or all of the above and heating and mixing them in the presence of a basic catalyst.

  In order to stir and mix a part of the component (A ′) and the component (C) under heating, the temperature may be room temperature to 180 ° C. for 1 to 6 hours, preferably 120 to 160 ° C. for 2 to 4 hours. In this case, the ratio of the component (A ′) to the component (C) can be 50/50 to 95/5, preferably 60/40 to 90/10. At this time, for the purpose of improving the mixing / dispersibility of the component (A ′) and the component (C), a diorganosiloxane oligomer or organosilane having a silanol group is added to the component (A ′), if necessary. You may add 0.5-10 mass parts with respect to a total of 100 mass parts of (C) component.

  Next, the necessary amount of this and the remainder of the component (A ′), the component (B), and part or all of the component (E) are added, and these are mixed in the presence of a basic catalyst. The basic catalyst is as described above. The mixing temperature and time are also as described above.

  Furthermore, a neutralizing agent that neutralizes the basic catalyst may be added as necessary after completion of the reaction. The neutralizing agent is as described above.

  This product is usually filled in a container for storage and transportation by adjusting the concentration of non-volatile components to, for example, 30 to 80% by mass. When manufacturing adhesive tapes, adhesive sheets, adhesive labels, etc., dilute this product with an organic solvent as necessary, add and mix component (H), and apply to various substrates as shown below. Is done.

  According to the manufacturing method as described above, the silica particles can be uniformly dispersed in the silicone pressure-sensitive adhesive. Regardless of the method described above, the component (C) cannot be sufficiently dispersed only by adding and mixing the component (C) to the addition-type silicone pressure-sensitive adhesive composition. In this case, undispersed particles remain, so that when the silicone pressure-sensitive adhesive composition is applied to a substrate to produce a pressure-sensitive adhesive tape or the like, a convex portion is formed on the surface of the pressure-sensitive adhesive layer, resulting in a non-smooth appearance. In addition, when pasted on an adherend, bubbles are generated in the convex portion, and good adhesion cannot be achieved.

  In addition to the above components, optional components can be added to the silicone pressure-sensitive adhesive composition of the present invention. For example, non-reactive polyorganosiloxanes such as polydimethylsiloxane and polydimethyldiphenylsiloxane, antioxidants such as phenols, quinones, amines, phosphoruss, phosphites, sulfurs and thioethers, hindered amines -Based, triazole-based, benzophenone-based light stabilizers, phosphate ester-based, halogen-based, phosphorus-based, antimony-based flame retardants, cationic surfactants, anionic surfactants, non-ionic surfactants and other antistatic agents, As solvents for reducing the viscosity during coating, aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane, octane and isoparaffin, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate and acetic acid Ester solvents such as isobutyl, diisopropyl ether Ether, ether solvents such as 1,4-dioxane, or a mixed solvent, a dye, a pigment is used.

The silicone pressure-sensitive adhesive composition formulated as described above can be applied to various substrates and cured under predetermined conditions to obtain a pressure-sensitive adhesive layer.
As a base material, plastic films such as polyester, polytetrafluoroethylene, polyimide, polyphenylene sulfide, polyamide, polycarbonate, polystyrene, polypropylene, polyethylene, polyvinyl chloride, metal foil such as aluminum foil, copper foil, Japanese paper, synthetic paper, Examples thereof include paper such as polyethylene laminated paper, cloth, glass fiber, and a composite base material formed by laminating a plurality of these.

  In order to improve the adhesion between these substrates and the adhesive layer, a primer-treated, corona-treated, etched or plasma-treated material may be used.

The coating method may be applied using a known coating method, comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater, gravure coater, screen coating, dipping. Examples thereof include coating and cast coating.
The coating amount can be 2 to 200 μm, particularly 3 to 100 μm, as the thickness of the adhesive layer after curing.

  As curing conditions, the peroxide curing type may be 100 to 200 ° C. for 30 seconds to 10 minutes, and the addition reaction type may be 80 to 130 ° C. for 30 seconds to 3 minutes, but is not limited thereto. .

  As described above, it may be applied directly to the base material to produce an adhesive tape, etc., or applied to a release film or release paper that has been subjected to release coating, cured, and then applied to the above base material. You may manufacture an adhesive tape etc. with the transfer method to match.

  Although it does not specifically limit as an adherend which can be masked with the adhesive tape etc. which were manufactured using the silicone adhesive composition of this invention, The following can be illustrated. Metals and alloys such as stainless steel, copper, iron, aluminum, chromium, gold, etc., metal whose surface is plated or rust-proofed, coated, glass, ceramics, ceramics, polytetrafluoroethylene, polyimide, epoxy resin, A resin such as a novolac resin or a composite of a plurality of these resins.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, the part in an example shows the mass part, and a characteristic value shows the measured value by the following test method. Me represents a methyl group and Vi represents a vinyl group.

After applying the adhesive residue silicone pressure-sensitive adhesive composition solution to a polyimide film having a thickness of 25 μm and a width of 25 mm using an applicator so that the thickness after curing is 40 μm, the peroxide curing type is 165 ° C. The additional type was heated for 2 minutes at 130 ° C. for 1 minute and cured to prepare an adhesive tape. The pressure-sensitive adhesive tape was attached to a metal plate (polished stainless steel plate), pressed by reciprocating a roller covered with a rubber layer having a weight of 2 kg, and then left in a dryer at 280 ° C. After a predetermined time, the metal plate was taken out and cooled to room temperature, and then the pressure-sensitive adhesive tape was peeled off, and it was observed whether the pressure-sensitive adhesive layer cohesively failed and the pressure-sensitive adhesive remained on the surface of the metal plate. The ones that can be peeled without any adhesive residue are marked with ◯, the ones with a part of the glue remaining are marked with Δ, and the ones with almost the whole glue remaining are marked with ×.

A pressure-sensitive adhesive tape was prepared by the same method as in the evaluation of adhesive strength and adhesiveness. The pressure-sensitive adhesive tape was attached to a stainless steel plate and pressed by reciprocating a roller covered with a rubber layer having a weight of 2 kg. After standing at room temperature for about 20 hours, 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.

A pressure-sensitive adhesive tape was prepared in the same manner as in the evaluation of the holding power adhesive residue. This adhesive tape is affixed to the lower end of the stainless steel plate so that the adhesive area is 25 × 25 mm, and a weight of 1 kg is applied to the lower end of the adhesive tape. Reading was measured with a microscope.

A pressure-sensitive adhesive tape was prepared in the same manner as in the probe tack adhesive evaluation. The tack of this adhesive tape was measured using a probe tack tester manufactured by Polyken.

[Example 1]
Polydimethylsiloxane I (43.1 parts) having a viscosity of 33,000 mPa · s when dissolved in toluene to a concentration of 30% and having a molecular chain end blocked with an OH group, Me ₃ SiO _0. 60% toluene solution (93.2 parts) of polysiloxane II (Me ₃ SiO _0.5 unit / SiO ₂ unit = 0.80) consisting of ₅ units and SiO ₂ units, dry-treated silica R972 (product of Nippon Aerosil Co., Ltd.) Name, specific surface area 110 m ^{2 /} g, pH 5.0) (1.0 part), 28% aqueous ammonia (0.5 part) was added to toluene (29.4 parts) and stirred at room temperature for 6 hours. did. Thereafter, the mixture was heated for 4 hours while refluxing to distill off ammonia gas and water, then allowed to cool, and toluene corresponding to distilled toluene was added.

  The above product (siloxane content 60%) (100 parts) was mixed with benzoyl peroxide 50% silicone paste (2.4 parts) and toluene (50 parts) to obtain a silicone adhesive composition having a siloxane content of about 40%. A product solution was prepared. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.

[Example 2]
The composition was the same except that 42.2 parts of dimethylpolysiloxane I of Example 1, 91.3 parts of a 60% toluene solution of polysiloxane II, 3.0 parts of dry-treated silica R972, and 30.2 parts of toluene were used. Adjusted. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.

[Example 3]
The composition was the same except that 40.9 parts of dimethylpolysiloxane I of Example 1, 88.5 parts of a 60% toluene solution of polysiloxane II, 6.0 parts of dry-treated silica R972, and 31.3 parts of toluene were used. Adjusted. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.

[Comparative Example 1]
The composition was the same except that 39.2 parts of dimethylpolysiloxane I of Example 1, 84.8 parts of a 60% toluene solution of polysiloxane II, 10.0 parts of dry-treated silica R972, and 32.7 parts of toluene were used. Adjusted. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.

[Example 4]
In Example 2, instead of the dry-processed silica R972, another dry-processed silica R812 (trade name, specific surface area 260 m ^{2 /} g, pH 6.5, manufactured by Nippon Aerosil Co., Ltd.) (3.0 parts) was used. A product solution was prepared. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.

[Example 5]
Using a kneader, dimethylpolysiloxane I (98 parts), polydimethylsiloxane having a viscosity of 30 mPa · s whose molecular chain ends are blocked with OH groups (2.0 parts), dry-treated silica R972 (25.0 parts), The mixture was stirred and mixed at 160 ° C. for 2 hours. In a solution consisting of this mixture (15.0 parts), dimethylpolysiloxane I (30.2) parts, polysiloxane II 60% toluene solution (91.3 parts), toluene (30.2 parts), 28% Aqueous ammonia (0.5 parts) was added and stirred at room temperature for 6 hours. Thereafter, the mixture was heated for 4 hours while refluxing to distill off ammonia gas and water, then allowed to cool, and toluene corresponding to distilled toluene was added. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.

[Comparative Example 2]
28% aqueous ammonia (0.5 parts) was added to a solution consisting of polydimethylsiloxane I (43.5 parts), polysiloxane II 60% toluene solution (94.2 parts) and toluene (29.0 parts). And stirred at room temperature for 6 hours. Thereafter, the mixture was heated for 4 hours while refluxing to distill off ammonia gas and water, then allowed to cool, and toluene corresponding to distilled toluene was added. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.

[Comparative Example 3]
In Example 2, instead of dry-treated silica R972, dry-untreated silica A200 (trade name, specific surface area 200 m ^{2 /} g, pH 4.5) (3.0 parts) (3.0 parts) manufactured by Nippon Aerosil Co., Ltd. was used. A solution was prepared. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.

[Comparative Example 4]
Instead of dry-treated silica R972 in Example 2, wet-treated silica Nipsil SS-100 (Nippon Silica Industrial Co., Ltd. trade name, specific surface area 112m ² /G,pH8.5)(3.0 parts) was used, a silicone adhesive An agent composition solution was prepared. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.

[Comparative Example 5]
In Example 2, instead of dry-treated silica R972, wet untreated silica silicia-310 (trade name, specific surface area 300 m ^{2 /} g, pH 7.5) (3.0 parts) manufactured by Fuji Silysia Co., Ltd. (3.0 parts) was used, and a silicone adhesive was used. A composition solution was prepared. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.

[Example 6]
When dissolved in toluene to a concentration of 30%, the viscosity was 27,000 mPa · s, had 0.15 mol% of methylvinylsiloxane units, and the molecular chain ends were blocked with SiMe ₂ Vi groups. 60% of polysiloxane II (Me ₃ SiO _0.5 unit / SiO ₂ unit = 0.80) composed of vinyl group-containing polydimethylsiloxane III (39.6 parts), Me ₃ SiO _0.5 unit, SiO ₂ unit To a solution consisting of a toluene solution (99.0 parts), dry-treated silica R972 (1.0 part) and toluene (27.0 parts), 28% aqueous ammonia (0.5 parts) was added and stirred at room temperature for 6 hours. did. Thereafter, the mixture was heated for 4 hours while refluxing to distill off ammonia gas and water, then allowed to cool, and toluene corresponding to distilled toluene was added.

  To this product, a crosslinking agent of the following formula (0.25 part) and ethynylcyclohexanol (0.20 part) were added and mixed.

  To the above mixture (siloxane content 60%) (100 parts) was added toluene (50 parts) and a toluene solution (0.5 parts) of a platinum-vinyl group-containing siloxane complex containing 0.5% by mass of platinum. By mixing, a silicone pressure-sensitive adhesive composition solution having a siloxane content of about 40% was prepared. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.

[Example 7]
38.8 parts of dimethylpolysiloxane III of Example 6, 97.0 parts of a 60% toluene solution of polysiloxane II, 3.0 parts of dry-treated silica R972, 27.8 parts of toluene, and 0. The composition was similarly adjusted with 25 parts and ethynylcyclohexanol as 0.20 parts. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.

[Example 8]
37.6 parts of dimethylpolysiloxane III of Example 6, 94.0 parts of a 60% toluene solution of polysiloxane II, 6.0 parts of dry-treated silica R972, 29.0 parts of toluene, and 0.02 of a crosslinking agent. The composition was similarly adjusted with 24 parts and 0.20 parts of ethynylcyclohexanol. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.

[Comparative Example 6]
36.0 parts of dimethylpolysiloxane III of Example 6, 90.0 parts of a 60% toluene solution of polysiloxane II, 10.0 parts of dry-treated silica R972, 30.6 parts of toluene, and 0.02 of a crosslinking agent. The composition was similarly adjusted with 23 parts and 0.20 parts of ethynylcyclohexanol. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.

[Example 9]
Vinyl group-containing polydimethylsiloxane III (100 parts) and dry-treated silica R972 (25 parts) were mixed with stirring at 160 ° C. for 2 hours using a kneader. To a solution comprising this mixture (15 parts), a vinyl group-containing polydimethylsiloxane III (26.8) part, a polysiloxane II 60% toluene solution (97.0 parts), and toluene (27.9 parts) % Aqueous ammonia (0.5 parts) was added and stirred at room temperature for 6 hours. Thereafter, the mixture was heated for 4 hours while refluxing to distill off ammonia gas and water, then allowed to cool, and toluene corresponding to distilled toluene was added.

  To this product, a crosslinking agent of the following formula (0.25 part) and ethynylcyclohexanol (0.20 part) were added and mixed.

  To the product (siloxane content 60%) (100 parts), toluene (50 parts) and a platinum-vinyl group-containing siloxane complex toluene solution (0.5 parts) containing 0.5% by mass of platinum are added. Further mixing was performed to prepare a silicone pressure-sensitive adhesive composition solution having a siloxane content of about 40%. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.

[Comparative Example 7]
To a solution comprising vinyl group-containing polydimethylsiloxane III (40.0 parts), 60% toluene solution of polysiloxane II (100.0 parts) and toluene (26.7 parts), 28% aqueous ammonia (0.5 parts) ) Was added and stirred at room temperature for 6 hours. Thereafter, the mixture was heated for 4 hours while refluxing to distill off ammonia gas and water, then allowed to cool, and toluene corresponding to distilled toluene was added. To this product, a crosslinking agent (0.26 parts) and ethynylcyclohexanol (0.20 parts) were added and mixed. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.

[Comparative Example 8]
In Example 7, instead of dry-treated silica R972, dry untreated silica A200 (made by Nippon Aerosil Co., Ltd.) (3.0 parts) was used to prepare a silicone pressure-sensitive adhesive composition solution. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.

[Comparative Example 9]
In Example 2, instead of the dry-treated silica R972, a wet-treated silica nip seal SS-100 (manufactured by Nippon Silica Kogyo Co., Ltd.) (3.0 parts) was used to prepare a silicone pressure-sensitive adhesive composition solution. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.

[Comparative Example 10]
A silicone pressure-sensitive adhesive composition solution was prepared using wet untreated silica silicia-310 (manufactured by Fuji Silysia) (3.0 parts) instead of dry-treated silica R972 in Example 2. This silicone adhesive was measured for adhesive residue, adhesive strength, and holding power. The results are shown in Table 1.

[Table 1]

Claims (4)

(A) Polydiorganosiloxane 20 to 80 parts by mass (B) R ¹ ₃ SiO _0.5 units and SiO ₂ units are contained, and the molar ratio of R ¹ ₃ SiO _0.5 units / SiO ₂ units is 0.6 to Polyorganosiloxane of 1.7 (R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms) 80-20 parts by mass (C) Dry silica (A), (B) whose surface has been hydrophobized 0.2 to 8.0 parts by mass with respect to a total of 100 parts by mass (D) 0.5 to 5.0 parts by mass with respect to a total of 100 parts by mass of the organic peroxide curing agent (A) and (B) E) Organic solvent (A) A peroxide curable silicone pressure-sensitive adhesive composition containing 25 to 900 parts by mass with respect to 100 parts by mass in total of (B), comprising (A) component and (B) component , (C) component, and (E) part or all of the components are mixed in the presence of a basic catalyst. A silicone pressure-sensitive adhesive composition, which is produced by adding the component (D) to a product obtained. A peroxide-curing silicone pressure-sensitive adhesive composition containing the component (A), the component (B), the component (C), the component (D), and the component (E), wherein a part of the component (A) or A mixture obtained by mixing and stirring all of component (C) under heating, the rest of component (A), component (B), and part or all of component (E) are added, and these are added in the presence of a basic catalyst. The method for producing a silicone pressure-sensitive adhesive composition according to claim 1, wherein the product obtained by mixing in step (D) is produced by adding the component (D). (A ′) 20 to 80 parts by mass of a polydiorganosiloxane having two or more alkenyl groups in one molecule (B) containing R ¹ ₃ SiO _0.5 unit and SiO ₂ unit, and R ¹ ₃ SiO _0.5 Polyorganosiloxane having a unit / SiO ₂ unit molar ratio of 0.6 to 1.7 (R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms) 80 to 20 parts by mass (C) Hydrophobized surface 0.2 to 8.0 parts by mass of (F) SiH group-containing polyorganosiloxane (A ′) alkenyl group in component (A ′) and 100 parts by mass of dry silica (A ′) and (B) treated The amount of SiH groups in the component (E) relative to the amount of 0.5 to 20 (G) 0 to 8.0 parts by mass with respect to a total of 100 parts by mass of the control agents (A ′) and (B) ( H) Platinum catalyst (A ') As a platinum content with respect to the total of (B) component, 5-2 000ppm
(E) An organic solvent (A ′) is an addition reaction type silicone pressure-sensitive adhesive composition containing 25 to 900 parts by mass with respect to 100 parts by mass in total of (B), wherein (A ′) component, (B) Produced by adding components (F), (G), and (H) to a product obtained by mixing a part or all of components, (C) and (E) in the presence of a basic catalyst. The silicone adhesive composition characterized by the above-mentioned. An addition reaction type silicone pressure-sensitive adhesive composition containing the component (A ′), the component (B), the component (C), the component (F), the component (G), the component (H), and the component (E). , A mixture obtained by mixing and stirring part or all of component (A ′) and component (C) under heating, the rest of component (A ′) and component (B), part of component (E) or The product according to claim 3, wherein all of the components are added and the components (F), (G), and (H) are added to a product obtained by mixing them in the presence of a basic catalyst. A method for producing a silicone pressure-sensitive adhesive composition.