KR20150112851A - Silicone adhesive composition, method for making the same and adhesive film - Google Patents

Abstract

The present invention relates to a silicone adhesive composition with excellent adhesive properties and heat resistance, a manufacturing method thereof, and an adhesive film and, more specifically, to a silicone adhesive composition, in the case of an addition-curable composition, comprising (A1) diorgano polysiloxane having an alkenyl group, with viscosity greater than or equal to 100,000 mPa·s at 25°C, (B) organopolysiloxane having a unit of R^1_3SiO_0.5 (R^1 is a substituted or unsubstituted primary hydrocarbon radical with a carbon number of 1 to 10) and a SiO_2 unit, (C) organohydrogen polysiloxane having at least three SiH groups, (D) a random addition reaction control agent, (E) a platinum group metal-based addition reaction catalyst, and (F) an organic solvent. In the case of a peroxide-curable composition, the composition comprises (A2) diorgano polysiloxane which has or does not have an alkenyl group, with viscosity greater than or equal to 100,000 mPa·s at 25°C, (B) organo polysiloxane having a unit of R^1_3SiO_0.5 (R^1 is a substituted or unsubstituted primary hydrocarbon radical with a carbon number of 1 to 10) and a SiO_2 unit, (F) an organic solvent, and (G) organic peroxide.

Description

TECHNICAL FIELD [0001] The present invention relates to a silicone pressure-sensitive adhesive composition, a process for producing the same, and a pressure-

The present invention relates to a silicone pressure-sensitive adhesive composition, a method for producing the same, and an adhesive film and a pressure-sensitive adhesive tape having a layer of the silicone pressure-sensitive adhesive composition. The pressure-sensitive adhesive film and the pressure-sensitive adhesive tape are suitable for application for protecting or masking parts when heated for a long time at 260 ° C or higher in a processing step of precision parts, optical parts or electronic parts.

The silicone pressure-sensitive adhesive layer is excellent in heat resistance, cold resistance, weather resistance, electrical insulation and chemical resistance. For this reason, the pressure-sensitive adhesive tape or pressure-sensitive adhesive label having the silicone pressure-sensitive adhesive layer is used under a strict environment in which other pressure-sensitive adhesives such as acrylic, rubber, urethane and epoxy-based pressure-sensitive adhesives deteriorate or deteriorate.

As one of such environments, there is an environment exposed to a high temperature of 250 DEG C or higher. Applications involving such an environment include, for example, masking of components in a reflow process or a resin encapsulation process of a semiconductor component and provisional fixation of components. In recent years, heat treatment at a higher temperature than that of the prior art is performed, and it is necessary to improve the heat resistance of the silicone pressure-sensitive adhesive.

For example, with the commercialization of lead-free solder in the reflow process in electronic component mounting, the reflow temperature becomes higher than in the past, and the peak temperature in the reflow furnace reaches 280 캜 There is a case. Even under such a high temperature, the pressure-sensitive adhesive should not be peeled off during the reflow treatment. Further, after the end of the treatment, it is necessary to peel off the adherend without leaving any contaminants on the adherend. Recently, there is also a process involving a high temperature such as 300 ° C.

However, in the conventional adhesive tape using a silicone pressure-sensitive adhesive, there has been a case where the pressure-sensitive adhesive remains on the adherend or the pressure-sensitive adhesive layer is transferred from the pressure-sensitive adhesive tape to the adherend when peeling off after receiving a high temperature of 200 to 250 ° C. In the present invention, this phenomenon is referred to as adhesive residue.

In order to eliminate such adhesive residue, it is known to add an antioxidant to the siloxane-based binder of the adhesive tape (Patent Document 1).

Further, by adding a phenol-based antioxidant to the addition reaction curing type siloxane composition for a pressure-sensitive adhesive, a siloxane composition for a pressure-sensitive adhesive capable of being peeled off without remaining a pressure-sensitive adhesive even after heated to 150 to 250 캜, (Patent Document 2).

However, when these silicone pressure-sensitive adhesives are exposed to a high temperature of 270 占 폚 or more, the antioxidant deteriorates and the effect of preventing the adhesive residue from being obtained can not be obtained. Further, in the case where the adherend is a metal such as copper, a copper alloy or iron, the surface of the metal is oxidized and bonded more firmly to the silicon adhesive, resulting in the residual adhesive.

Further, the addition of a large amount of the antioxidant results in the opacity of the silicone pressure-sensitive adhesive composition, and in the case of the addition-curing silicone pressure-sensitive adhesive, the curing reaction is inhibited and the adhesive strength at the time of heating is lower than that when no antioxidant is added It involves a problem.

As another method for reducing the residual amount of the pressure-sensitive adhesive, there has been proposed an adhesive tape in which the amount of the low-molecular siloxane in the silicone pressure-sensitive adhesive composition is reduced (Patent Document 3). This composition is composed of an organopolysiloxane (a) having alkenyl groups at both ends of the molecular chain and having a viscosity of 10,500 mPa · s to 60,000 mPa · s and a reduced amount of low molecular siloxane, And addition reaction product (A) of diorganohydrogenpolysiloxane (b) having a hydrogen atom. According to the description of this document, the lowering of the amount of the low molecular weight siloxane in the component (a) is achieved by the thin film stripping, but if the viscosity exceeds the upper limit, it is difficult to sufficiently lower the low molecular siloxane amount even by using the thin film stripping Do. This composition has a structure in which the main chain of the component (A) is not -O-Si-O-Si-O- and has a structure of -O-Si-CH ₂ -CH ₂ -Si-O- It is disadvantageous in that heat resistance is low. In addition, since the viscosity of the component (a) is smaller than that used in conventional silicone pressure-sensitive adhesives, the pressure-sensitive adhesive tape may have poor adhesiveness. Further, since the component (A) is obtained by a reaction in the presence of a catalyst, the catalyst remains in the component (A) and discolored, and the composition may be poor in transparency.

Japanese Patent No. 4619486 Japanese Patent No. 4180353 Japanese Patent No. 5032767

Disclosure of the Invention The present invention has been made to solve the above problems and provides a silicone pressure-sensitive adhesive composition which not only has a sufficient tackiness and tackiness without blending an antioxidant but also has excellent heat resistance and is free from residual pressure- And a pressure-sensitive adhesive film and a pressure-sensitive adhesive tape having a cured layer of the composition.

DISCLOSURE OF THE INVENTION As a result of intensive investigations to achieve the above object, the inventors of the present invention have found that it is possible to remarkably improve residual adhesive property by reducing the amount of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane in the silicone pressure- And has reached the completion of the invention.

That is, the present invention relates to an addition-curable or peroxide curable silicone pressure-

In the case of addition curing type

(A1) a diorganopolysiloxane having an alkenyl group and a viscosity at 25 DEG C of 100,000 mPa.s or more,

^{_{(B) R 1 3 SiO 0}} .5 units of organopolysiloxane having a (R ¹ is a 1-substituted substituted or non-substituted hydrocarbon group having 1 to 10 carbon atoms) and SiO ₂ units,

(C) an organohydrogenpolysiloxane having at least three SiH groups,

(D) an optional addition reaction control agent,

(E) a platinum group metal addition reaction catalyst and

(F) Organic solvents

Lt; / RTI >

In the case of peroxide curing type

(A2) a diorganopolysiloxane having a viscosity at 25 DEG C of 100,000 mPa-s or more and optionally having an alkenyl group,

^{_{(B) R 1 3 SiO 0}} .5 units of organopolysiloxane having a (R ¹ is a 1-substituted substituted or non-substituted hydrocarbon group having 1 to 10 carbon atoms) and SiO ₂ units,

(F) an organic solvent and

(G) The organic peroxide

(A1) and / or (A2) may be accompanied by octamethylcyclotetrasiloxane and / or decamethylcyclopentasiloxane, and the component (A1) or the component (A2) and the component ) And a content of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane relative to the total amount of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane is less than 0.1% by mass, respectively. The present invention also provides a process for producing the silicone pressure-sensitive adhesive composition and an adhesive film and a pressure-sensitive adhesive tape having a cured layer of the silicone pressure-sensitive adhesive composition on at least one surface of the base film.

Since the silicone pressure sensitive adhesive composition of the present invention does not contain an antioxidant, it has excellent work efficiency upon curing, has required tackiness and tack, has excellent heat resistance, and has no adhesive residue in the tackiness residue test described later. When octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane is a volatile substance and these are present in a large amount in a pressure-sensitive adhesive composition, when the cured product of the composition is brought into contact with an electronic product, the volatile substance present in the composition slowly volatilizes, It causes disability. The silicon pressure-sensitive adhesive composition of the present invention can avoid contact trouble because of the small amount of the volatile substance, and thus can be suitably used for electronic parts. Further, in the silicone pressure-sensitive adhesive composition of the present invention, since the volatilization of the siloxane in the oven in which the thermosetting is performed is low, generation of dust such as silica in the oven is suppressed. As a result, cleaning work in the oven is alleviated, and adhesion of foreign matter such as silica to the surface of the cured product is suppressed. Further, the silicone pressure-sensitive adhesive composition, the pressure-sensitive adhesive film and the pressure-sensitive adhesive tape of the present invention can be suitably used in various applications because they can reduce the migration of the silicone pressure-sensitive adhesive to the adherend.

First, each component of the silicone pressure-sensitive adhesive composition of the present invention will be described.

The diorganopolysiloxane which is a component of the components (A1) and (A2) has a viscosity at 25 ° C of 100,000 mPa · s or more. If it is less than 100,000 mPa · s, the coating property is deteriorated to cause cratering on the coated surface or a sufficient holding force can not be obtained. The diorganopolysiloxane of the present invention is produced, for example, by ring-opening polymerization of cyclic siloxane. The above octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are produced in the manufacturing process or contained in the raw material compound. The diorganopolysiloxanes (A1) and (A2) of the present invention may be accompanied by the octamethylcyclotetrasiloxane and / or decamethylcyclopentasiloxane, and the present invention is also applicable to the octamethylcyclotetrasiloxane and / or decamethylcyclo And the amount of pentasiloxane is less than a predetermined amount. The amount of octamethylcyclotetrasiloxane and / or decamethylcyclopentasiloxane is measured by gas chromatography. The measurement conditions of the gas chromatography can be appropriately selected according to conventionally known methods.

The components (A1) and (A2) may be either oily or raw. When the viscosity is higher than 500,000 mPa · s, it is preferable that the viscosity (30% solubility viscosity) when dissolved in toluene is 30,000% by mass or less is 100,000 mPa · s or less. The 30% melt viscosity is preferably 1,000 to 60,000 mPa · s. If the 30% melt viscosity exceeds 100,000 mPa · s, the composition becomes too high in viscosity and it becomes difficult to stir at the time of production. In the present invention, the viscosity is a value at 25 캜 measured by a rotational viscometer.

The component (A1) is for an addition-curable pressure-sensitive adhesive composition and necessarily has an alkenyl group, but the component (A2) is for a peroxide curable pressure-sensitive adhesive composition and may or may not have an alkenyl group.

The components (A1) and (A2) are preferably at least one diorganopolysiloxane selected from the following formulas (1) to (3).

^{_{R 3 a R 2 (3-}} a) SiO (R 3 R 2 SiO) m (R 2 2 SiO) n SiR 2 (3-a) R 3 a (1)

HOR ² ₂ SiO (R ³ R ² SiO) _m (R ² ₂ SiO) _n SiR ² ₂ OH (2)

^{_{(R 3 a R 2 (3}} -a) SiO 1/2) o (R 3 R 2 SiO 2/2) p (R 2 2 SiO 2/2) q (R 4 SiO 3/2) r (SiO 4 _{/ 2} ) _s (3)

In the formulas (1) to (3), R ² is independently a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, R ³ is a monovalent organic group having an alkenyl group, a is a number that is an integer of 0 to 3, m is an integer of 0 or more, n is an integer of 100 or more, m + n has a viscosity at 25 ℃ of the diorganopolysiloxane that is adapted to be at least 100,000mPa · s, R ⁴ is a group each independently selected from the choices of R ² or R ^3, o is from 3 to 12 integer, p is an integer equal to or greater than zero, q is more than 100 integers, r + s is an integer from 1 to 5, o + p + q + r + s is such that the viscosity of the diorganopolysiloxane at 25 ° C is 100,000 mPa · s or more. In the case of the component (A1), when a is 0 in the formula (1) m is 2 or more, and m is 2 or more in the formula (2), and when a is 0 in the formula (3), p is 2 or more. In the case of the component (A1), it is preferable that a is 1.

R ² preferably has 1 to 10 carbon atoms, and examples thereof include alkyl groups such as methyl group, ethyl group, propyl group and butyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group and tolyl group, A compound in which some or all of the hydrogen atoms bonded to the atoms are substituted with other groups such as a halogen, an amino group, a hydroxyl group or a cyano group, such as 3-aminopropyl group, 3,3,3-trifluoropropyl group, Hydroxypropyl group, and 3-cyanopropyl group. Methyl group and phenyl group are particularly preferable.

R ³ preferably has 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, a hexenyl group, an octenyl group, an acryloylpropyl group, an acryloylmethyl group, a methacryloylpropyl group and a vinyloxypropyl And vinyl groups are particularly preferable industrially. When the pressure-sensitive adhesive composition is an addition curing type, it is preferable that the content of the alkenyl group in the component (A1) is 0.075 to 3.0 mol% of the total organic components in the diorganopolysiloxane in terms of adhesiveness. If the amount is less than the lower limit, sufficient curing can not be obtained, and adhesive residue is generated. If the upper limit is exceeded, the coating becomes excessively hard and the bonding becomes difficult. The component (A1) may be used in combination of two or more. In this case, the total amount of the alkenyl groups contained in the two or more species may be 0.075 to 3.0 mol%. In the case of the peroxide curable composition, the content of the alkenyl group in the component (A2) is not particularly limited, but if it is excessively large, it becomes economically disadvantageous.

Component (B) is R ¹ ₃ SiO _{0. 5} is an organopolysiloxane containing units and SiO ₂ units. Preferably R ¹ ₃ SiO _0. The number ratio of ₅ units / SiO ₂ units is 0.6 to 1.7. If the number ratio is less than the lower limit, the adhesive strength or the tack may be lowered. If the upper limit is exceeded, the adhesive force and the holding force may be lowered.

R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, an aryl group such as a cycloalkyl group and a phenyl group, And an alkenyl group such as a hexenyl group. Further, those in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with other groups such as halogen, amino group, hydroxyl group or cyano group, such as 3-aminopropyl group, 3,3,3-trifluoro Propyl group, 3-hydroxypropyl group and 3-cyanopropyl group are also exemplified. Methyl groups are preferred.

(B) may have an OH group, and the OH group content is preferably 0.01 to 4.0% by mass based on the total mass of the component (B). If the OH group content is less than the above lower limit, the cohesive force of the pressure-sensitive adhesive may be lowered, and if it exceeds the upper limit, the pressure of the pressure-sensitive adhesive may be lowered.

The component (B) may be used in combination of two or more. In addition, R < ₁ ^> SiO < _{1 & gt ; 5} units and / or R < ^{12 &} _gt; SiO units in the component (B).

The blending amount of the component (A1) or the component (A2) and the component (B) is such that the mass ratio of (A1) or (A2) / (B) is in the range of 99/1 to 25/75. Preferably, the mass ratio is 95/5 to 30/70, more preferably 90/10 to 35/65. When the amount of the component (B) is less than the above range, the amount of the component (A1) or (A2) becomes excessively large, which tends to cause oxidative deterioration and tends to cause residual adhesive. If the amount of the component (B) is larger than the above range, the excess component (B) precipitates on the surface of the pressure-sensitive adhesive to cause contamination. Particularly, when the mass ratio is 90/10 to 35/65, the adhesive force and the tack are required, and the adhesive residue can be reduced.

The component (C) is a crosslinking agent used in the case of the addition reaction curing composition, and is an organohydrogenpolysiloxane having three or more SiH groups in one molecule. It may be either straight-chain or branched.

As the component (C), there may be exemplified those of the following formulas, but are not limited thereto.

^{_{H b R 2 (3-b}} ) SiO (HR 2 SiO) t (R 2 2 SiO) u SiR 2 (3-b) H b

And

^{_{(H b R 2 (3-}} b) SiO 1/2) v (HR 2 SiO 2/2) w (R 2 2 SiO 2/2) x - (R 2 SiO 3/2) y (SiO 4/2 ) _z

(Wherein, R ² is independently a substituted or unsubstituted group unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond with each other, b is 0 or 1, t is an integer of at least 1, u is an integer of 0 or more, b is 0 T is an integer of 3 or more, t + u is the number of the organohydrogenpolysiloxane having a viscosity at 25 DEG C of 1 to 1,000 mPa.s, v is an integer of 3 to 12, w is an integer of 0 or more, y + z is an integer of 1 to 5, and v + w + x + y + z is the number of the organohydrogenpolysiloxane having a viscosity at 25 ° C of 1 to 1,000 mPa · s)

R ² is preferably a monovalent hydrocarbon group of 1 to 10 carbon atoms, and examples thereof include alkyl groups such as methyl group, ethyl group, propyl group and butyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group and tolyl group , And those in which some or all of hydrogen atoms bonded to the carbon atoms of these groups are substituted with other groups such as halogen, amino group, hydroxyl group or cyano group, such as 3-aminopropyl group, 3,3,3-trifluoro Propyl group, 3-hydroxypropyl group and 3-cyanopropyl group. Methyl group and phenyl group are particularly preferable.

The viscosity of the component (C) at 25 캜 is preferably 1 to 1,000 mPa · s, and more preferably 2 to 500 mPa · s. The component (C) may be a mixture of two or more. ^{_{Furthermore, [R 2 SiO 3/2}} ] units, [HSiO _3/2] may also be mentioned organohydrogenpolysiloxane having units of the structure and / or [SiO _4/2] units.

The amount of the component (C) is such that the number ratio of SiH groups in the component (C) to the total number of alkenyl groups in the components (A1) and (B) is in the range of 0.5 to 20, especially 0.8 to 15. If the number ratio is less than the lower limit, the crosslinking density is lowered, and accordingly, the cohesive force and the holding force may be lowered. In addition, even when blended in excess of the above-mentioned upper limit, the crosslinking density becomes saturated and becomes economically disadvantageous.

The component (D) is an addition reaction control agent optionally used in the case of an addition reaction curing composition, and is added in order to prevent the composition from causing thickening or gelation before the heat curing when the silicone pressure sensitive adhesive composition is applied to the combination or substrate will be. Specific examples include 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 3,5- 3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, -Trimethylsiloxycyclohexane, bis (2,2-dimethyl-3-butyoxy) dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and 1 , 1,3,3-tetramethyl-1,3-divinyldisiloxane, and the like.

The amount of the component (D) is preferably from 0 to 8.0 parts by mass, particularly preferably from 0.05 to 2.0 parts by mass based on 100 parts by mass of the total of the components (A1) and (B). If the upper limit is exceeded, the curability may be lowered.

The component (E) is an addition reaction catalyst used in the case of an addition reaction curable composition, and is a reaction product of chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and alcohol, a reaction product of chloroplatinic acid and olefin compound, A platinum group catalyst such as a rhodium complex and a ruthenium complex, and the like can be given. These catalysts may be dissolved in a solvent such as isopropanol or toluene, a siloxane oil, or the like.

The amount of the component (E) is an amount of 5 to 2,000 ppm, particularly 10 to 500 ppm, of the platinum group metal component with respect to the total mass of the components (A1) and (B). If the amount is less than the lower limit, the curability may be lowered, the crosslinking density may be lowered, and the holding force may be lowered. If the upper limit is exceeded, the usable time of the treatment bath may be shortened.

The component (G) is an organic peroxide used as a curing agent in the case of a peroxide curable composition, and is not particularly limited as long as it decomposes to generate free oxygen radicals. Specific examples thereof include dibenzoyl peroxide, 4,4'-dimethyl dibenzoyl peroxide, 3,3'-dimethyl dibenzoyl peroxide, 2,2'-dimethyl dibenzoyl peroxide, 2,2 ', 4,4 '- tetrachlorodibenzoyl peroxide and cumyl peroxide.

The form of the component (G) is not particularly limited. The component (G) may be used as it is, or the component (G) may be diluted with an organic solvent, dispersed in water, or dispersed in silicone oil to be used in a paste form. The component (G) may be used singly or in combination of two or more.

The amount of the component (G) may be an amount effective as a curing agent. The effective amount differs depending on the curing temperature and the decomposition temperature of the peroxide to be used and can not be uniformly defined. However, the amount of the component (G) is preferably 0.5 to 5 parts by mass per 100 parts by mass of the total of the components (A2) Mass part, particularly 0.8 to 3 mass parts. When the amount is less than the above lower limit, the curability is lowered, the holding force is lowered, and the pressure-sensitive adhesive is likely to remain. When the upper limit is exceeded, coloring may occur in the pressure-sensitive adhesive layer or the tack may be lowered.

The component (F) is an organic solvent used in the case of any of the addition reaction curing type and the peroxide curing type. Specific examples thereof include aromatic hydrocarbon solvents such as toluene and xylene; linear or branched aliphatic hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane and isoparaffins; Hydrocarbon solvents such as benzene, petroleum benzene and solvent naphtha; hydrocarbon solvents such as acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, Ketone solvents such as isobutyl ketone, acetonyl acetone and cyclohexanone, esters such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate and isobutyl acetate, diethyl ether, dipropyl ether, diisopropyl ether, Ether-based solvents such as ether, dibutyl ether, 1,2-dimethoxyethane and 1,4-dioxane, ether solvents such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl ether There may be mentioned a solvent, or a mixed solvent thereof or the like having a 2-lactate and an ester group and ether unit, such as ethoxy ethyl acetate.

Among them, aromatic hydrocarbon solvents such as toluene and xylene, and linear or branched aliphatic hydrocarbon solvents such as hexane, heptane, isooctane, octane, decane, cyclohexane, methylcyclohexane and isoparaffins are preferable. A mixed solvent of a linear or branched aliphatic hydrocarbon solvent and an ether solvent, an ester solvent, or a solvent having both an ether group and an ester group is also preferable.

In the silicone pressure sensitive adhesive composition of the present invention, an optional component other than the above components may be added. For example, an antioxidant such as organopolysiloxane, phenol-based, quinone-based, amine-based, phosphorus-based, phosphite-based, sulfur-based or thioether-based ones containing one or two SiH groups in one molecule, Light stabilizers such as a lysine and benzophenone series, antistatic agents such as phosphate ester series, halogen series, phosphorus series and antimony series flame retardants, cationic activators, anion activators and nonionic surfactants, dyes and pigments. In addition, in the case of the addition-curable composition, a non-reactive organopolysiloxane containing no alkenyl group such as dimethylpolysiloxane and dimethyldiphenylpolysiloxane may be added.

The pressure-sensitive adhesive composition of the present invention is prepared by mixing and dissolving the components (A1), (B), (C), (D) and (F) Component. ≪ / RTI > In the case of the peroxide curing type, it is prepared by mixing and dissolving the component (A2), the component (B), the component (F) and optionally an optional component, and then adding and mixing the component (G).

The component (A1) or (A2) and the component (B) are reacted for a predetermined time in the presence of a base catalyst and if necessary in the presence of a part or all of the component (F) (A1), (A2) and (B) may be used as a part or all of the component (A1) or the component (B) by removing the hydroxyl group bonded to the silicon atom present in the component (B) by dehydration condensation. Examples of the base catalyst include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, carbonates such as sodium carbonate and potassium carbonate, hydrogen carbonate such as sodium hydrogencarbonate, metal alkoxides such as sodium methoxide and potassium butoxide, , Complexes of potassium hydroxide and siloxane, ammonia gas, ammonia water, nitrogen compounds such as methylamine, trimethylamine and triethylamine, and the like. Of these, ammonia gas and ammonia water are preferable. The reaction temperature can be 20 to 150 캜, but it is usually carried out at room temperature to the reflux temperature of the component (F). The reaction time is not particularly limited, but may be 0.5 to 10 hours, preferably 1 to 6 hours.

After completion of the reaction, if necessary, a neutralizing agent for neutralizing the base catalyst may be added. 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 inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid.

As a means for imparting a desired adhesive force to the pressure-sensitive adhesive composition of the present invention, the addition curing type may include adjusting the amount of the alkenyl group in the component (A1) or adjusting the ratio of the amounts of the components (A1) and (B) have. In the peroxide curing type, the ratio of the amounts of the component (A2) and the component (B) is adjusted, the amount of the peroxide hardening agent is adjusted, or the hardening condition is adjusted.

The pressure-sensitive adhesive composition of the present invention is characterized in that the content of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane relative to the total amount of component (A1) or component (A2) and component (B) and octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane Are each less than 0.1 mass% (1000 ppm). Preferably, the amounts of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane relative to the total amount of the component (A1) or (A2) and octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are each less than 0.1 mass%.

The components (A1) and (A2) which are accompanied by the above-mentioned amounts of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane can be obtained by any one of the following stripping method and solvent extraction method.

The stripping method is a method in which a diorganopolysiloxane (hereinafter referred to as "diorganopolysiloxane (A ')") having a viscosity at 25 ° C. of 100,000 mPa · s or more and an alkenyl group or not Is dissolved in a solvent having a boiling point, and this is added to the stripping. Since the diorganopolysiloxane (A ') has a viscosity as high as 100,000 mPa · s or more, the amount of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane can not be sufficiently reduced in ordinary stripping without using a solvent. The diorganopolysiloxane (A ') can be dissolved in an organic solvent which is a component (F), and the diorganopolysiloxane (A') is dissolved in the component (F) ) And octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, which are subjected to the above-mentioned reaction, can be stripped together with the component (F) to obtain the objective component (A1) or (A2). The conditions of the stripping are not particularly limited, and can be carried out at a temperature and pressure at which octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are stripped together with the component (F), and generally 50 to 2000 ° C and 10 mmHg to 100 mmHg (1.333 kPa to 13.33 kPa).

Among the components (F) in which the diorganopolysiloxane (A ') is dissolved, a solvent having a boiling point of 100 占 폚 or higher, more preferably 100 占 폚 or higher and lower than 230 占 폚 is preferable. If the boiling point is less than 100 DEG C, the solvent is stripped quickly, and it is impossible to sufficiently remove octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. If the boiling point exceeds 230 캜, the stripping becomes insufficient, the heating energy is excessively required, or the solvent remains in the component (A1) or (A2), and the solvent is finally added to the adhesive film or the adhesive tape It is not preferable because there is a problem that it remains. Particularly preferred solvents are toluene and xylene.

The stripping operation may be repeated a plurality of times until each of the octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane accompanying the diorganopolysiloxane (A ') becomes less than 0.1% by mass.

The solvent extraction method is a method in which the diorganopolysiloxane (A ') is dissolved in an organic solvent capable of dissolving a high-molecular polysiloxane having a degree of polymerization of 100 or more, and subsequently the high-molecular polysiloxane can not be dissolved. In addition, octamethylcyclotetrasiloxane And octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are extracted and removed with an organic solvent capable of dissolving decamethylcyclopentasiloxane.

The diorganopolysiloxane (A ') is dissolved in an organic solvent which is a component (F). The high molecular weight polysiloxane having a degree of polymerization of 100 or more, which is the main component of the diorganopolysiloxane (A '), is not very soluble or completely soluble in polar solvents such as alcohols, polyethers and glycerin. On the other hand, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are low-molecular polysiloxanes having a degree of polymerization of 4 and 5, respectively, and are soluble in these polar solvents.

Therefore, by bringing the diorganopolysiloxane (A ') into contact with these polar solvents, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane adhered to the diorganopolysiloxane (A') are extracted and removed with a polar solvent, A1) or (A2).

The method of contacting the diorganopolysiloxane (A ') with the polar solvent for extraction is not particularly limited. It is preferable to use an organic solvent having low compatibility with the polar solvent for extraction such as an aromatic hydrocarbon solvent such as toluene and xylene and a solvent such as hexane, heptane, isooctane, octane, decane, cyclohexane, methylcyclohexane and isoparaffin (A ') is dissolved in an aliphatic hydrocarbon-based solvent, and this is contacted with a polar solvent for extraction. By using an organic solvent having low compatibility with the polar solvent for extraction, separation between the polar solvent for extraction after extraction of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane and the organic solvent becomes easy and loss is reduced.

For example, the diorganopolysiloxane (A ') dissolved in an organic solvent is mixed with a polar solvent for extraction, stirred, and then separated to separate the polar solvent for extraction. After the extraction operation is repeated for the appropriate number of times, further, operations such as heating may be carried out if necessary, and the polar solvent for extraction may be completely removed to use as the component (A1) or (A2).

The polar solvent for extraction is not particularly limited as long as it dissolves octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane without dissolving the polymer polysiloxane. Alcohols, polyethers, glycerin, and the like are suitably used. Among them, alcohols having a low boiling point are preferred.

As low-boiling alcohols, alcohols having 5 or less carbon atoms are preferable, alcohols having 3 or less carbon atoms are more preferable, and methanol, ethanol and isopropyl alcohol are particularly preferable, and methanol is particularly preferable. The use of a low boiling point alcohol having 5 or less carbon atoms is advantageous in that removal of the low boiling point alcohol is facilitated by heating the organic solvent in which the high molecular weight polysiloxane is dissolved after the polar solvent for extraction to the boiling point of the low boiling point alcohol, have.

The silicone pressure sensitive adhesive composition of the present invention is coated on at least one surface of a base film and cured under a predetermined condition to form a pressure sensitive adhesive layer to obtain a pressure sensitive adhesive film or a pressure sensitive adhesive tape.

Examples of the base film include polyester, poly (meth) acrylate, polycarbonate, polyethylene, polypropylene, polystyrene, polyamide, polyimide, polyphenylene sulfide, polytetrafluoroethylene, polyether ketone, (Trademark registered by JSR Corporation), cycloolefin resin (manufactured by Nippon Zeon Co., Ltd., "ZEONOR" (registered trademark)), polyvinyl chloride, polyurethane, triacetylcellulose, polyacetal, norbornene resin ), An epoxy resin, and a phenol resin. These films can be used as a single layer or as two or more laminated films. A film of polyester such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, a polyimide film, a film of polyacrylate such as polyacrylate and polymethacrylate, and a polyether ketone such as polyether ether ketone Films and polycarbonate films are preferred.

The thickness of the base film is not limited, but is 2 to 300 탆, preferably 10 to 150 탆.

The base film may be subjected to a primer treatment, a corona treatment, an etching treatment, a plasma treatment or a sandblast treatment in order to improve adhesion with the pressure-sensitive adhesive layer. Preferably, corona treatment or primer treatment is used.

The surface of the substrate film opposite to the pressure-sensitive adhesive layer may be subjected to surface treatment such as prevention of scratches, prevention of contamination, prevention of adhesion of fingerprints, prevention of reflection, prevention of reflection, and prevention of electrification. After the pressure-sensitive adhesive layer is formed on the base film, the surface treatment may be performed as described above, or the pressure-sensitive adhesive layer may be formed after the surface treatment.

Examples of the scratch-preventive treatment (hard coating treatment) include treatment with a hard coating agent such as an acrylate-based, siloxane-based, oxetane-based, inorganic or organic-inorganic hybrid system.

Examples of the antifouling treatment include treatment with an antifouling agent such as fluorine, siloxane, ceramic, and photocatalyst.

Examples of the antireflection treatment include a wet treatment by coating an antireflective agent such as a fluorine-based or siloxane-based agent, or a dry treatment by vapor deposition or sputtering.

Examples of the antistatic treatment include treatment with an antistatic agent such as a surfactant system, a siloxane system, an organic boron system, a conductive polymer system, a metal oxide system, and a vapor deposition metal system.

The coating method of the silicone pressure sensitive adhesive composition of the present invention can be applied using a known coating method, and can be applied to various types of coating materials such as a comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater, Coating, immersion coating, casting coating and spray coating.

The thickness of the pressure-sensitive adhesive layer is preferably 2 to 200 占 퐉, preferably 3 to 100 占 퐉, more preferably 30 to 100 占 퐉 after curing. If it is less than the lower limit, sufficient adhesive force can not be obtained, and if it exceeds the upper limit, the adhesive force becomes excessive and economically disadvantageous.

The curing condition may be set at 80 to 130 DEG C for 30 seconds to 3 minutes in the case of the addition curing type, but is not limited thereto. In the case of the peroxide curing type, it depends on the decomposition temperature of the peroxide to be used, and is, for example, 3 to 5 minutes at 130 to 200 DEG C, but is not limited thereto.

The pressure-sensitive adhesive film and the pressure-sensitive adhesive tape can be produced by directly coating the pressure-sensitive adhesive composition on the base film as described above. Alternatively, the pressure-sensitive adhesive composition and the pressure- . ≪ / RTI > In order to protect the pressure-sensitive adhesive layer when storing and transporting the pressure-sensitive adhesive film and the pressure-sensitive adhesive tape of the present invention, a protective film may be provided on the pressure-sensitive adhesive layer, if necessary.

The pressure-sensitive adhesive film and the pressure-sensitive adhesive tape having the cured layer of the silicone pressure-sensitive adhesive composition of the present invention can be suitably used for a protective film for producing various optical films and a protective film for producing electronic parts. For example, it can be used as a heat-resistant masking tape for protecting electronic components such as a polarizing plate and a light diffusing plate, as a pressure-sensitive adhesive film for masking, and for processing electronic components such as flexible printed wiring boards.

[Example]

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. Further, "part" and "%" mean "part by mass" and "mass%", respectively, Me represents a methyl group and Vi represents a vinyl group. In the following, the viscosity is a value at 25 DEG C measured by a rotational viscometer.

The measurement conditions of gas chromatography (GC) are as follows.

Gas Chromatography: Capillary gas chromatography (Hitachi G-3500)

Column: J & W DURABOND. DB-5MS (0.53 mm x 30 m x 1.0 m)

Detector: FID, temperature 300 ℃

Temperature increase program: 50 ° C → 10 ° C / minute → 280 ° C (17 minutes)

Inlet temperature: 270 DEG C

Carrier gas: helium (5 ml / min)

Injection volume: 2 μl

The following test methods were used.

Initial adhesion

The silicone pressure-sensitive adhesive composition was applied to a polyimide film having a thickness of 23 占 퐉 using an applicator so as to have a thickness of 30 占 퐉 after curing, and then heated and cured at 130 占 폚 for 1 minute to produce an adhesive film. A tape having a width of 25 mm was cut from the adhesive film, and the pressure-sensitive adhesive layer was brought into contact with a stainless steel plate (SUS 304 plate), and a roller having a weight of 2 kg covered with a rubber layer was reciprocated twice. After leaving for about 20 hours at room temperature, a force (N / 25 mm) required to peel the tape from the stainless steel plate at an angle of 180 ° at a rate of 300 mm / min using a tensile tester was measured.

Adhesive residue

A tape having a width of 25 mm was cut from a pressure-sensitive adhesive film produced by the same method as the initial adhesive force, and a pressure-sensitive adhesive layer was brought into contact with a stainless steel plate (SUS 304 plate) . After standing at room temperature for about 20 hours, it was allowed to stand in a dryer at a predetermined temperature (250 DEG C, 270 DEG C, and 290 DEG C) for 2 hours. Removed from the dryer and allowed to cool, and the tape was peeled off from the stainless steel plate. The surface of the stainless steel plate was visually observed and evaluated according to the following criteria.

○ Residue of adhesive is not visible (ie no residual adhesive).

C. Residue of the adhesive is observed (i.e., residual adhesive is present).

Manufacturing example  One: In stripping  (A1) or (A2)

100 parts by weight of a biomodified diorganopolysiloxane (A ') having a viscosity of 18000 mPa 시켰 and a vinyl group content of 0.15 mol% when dissolved in toluene so as to have a concentration of 30% represented by the following formula (4) was dissolved in toluene 100 By weight to obtain a toluene solution. This solution was stripped at 160 캜 and 20 mmHg while stirring, and the operation was performed once to obtain a component (A1). The vinyl group content represents the ratio (mol%) of the amount of the vinyl group to the total amount of the organic groups (methyl group and vinyl group) in the diorganopolysiloxane (A ').

_{XMe 2 SiO (ViMeSiO) m (} Me 2 SiO) n SiMe 2 X (4)

Herein, X in both ends is a Vi group or an OH group, m and n are as defined above, and m + n is in the range of 18000 mPs · m · l when dissolved in toluene so that the viscosity of the diorganopolysiloxane is 30% s.

The component (A1) thus obtained was again dissolved in toluene, and octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane adducted to the component (A1) were quantitatively determined by gas chromatography. The component (A1) thus obtained was used in the following Example 1. Similarly, the diorganopolysiloxane (A ') shown in Table 1 and the solvent and the number of stripping were used to prepare various components (A1) and (A2), and to prepare octamethylcyclotetrasiloxane and decamethyl And cyclopentasiloxane was quantified. The results are shown in Table 1.

Example  One

35 parts of the component (A1) obtained in Production Example 1,

Me ₃ SiO _{0 .} 108.3 parts of a 60% toluene solution of an organopolysiloxane (component (B)) (Me ₃ SiO _0.5 unit / SiO ₂ unit = 0.85) containing ₅ units and SiO ₂ units,

23.7 parts of toluene,

0.22 parts of an SiH group-containing organohydrogenpolysiloxane (component (C)) of the following formula:

Me ₃ SiO (HMeSiO) ₄₀ SiMe ₃

And

0.20 part of ethynylcyclohexanol (component (D))

Were mixed.

Toluene (0.5 part) of platinum-vinyl group-containing siloxane complex (component (E)) containing 50 parts of toluene and 0.5 mass% of platinum powder was added to 100 parts of the above mixture (siloxane content of about 60% And further mixed to prepare a silicone pressure sensitive adhesive composition having a siloxane content of about 40%. The obtained silicone pressure-sensitive adhesive composition was subjected to each test according to the above-mentioned method. The results are shown in Table 2 below.

Example  2 and Comparative Example  1 to 2

(A1) or (A2) described in Table 1 was used in the mass ratio of the component (A1) or (A2) / (B) shown in Table 2 in place of the component , And the component (C) was added in an amount shown in Table 2, a silicone pressure sensitive adhesive composition having a siloxane content of about 40% was prepared in the same manner as in Example 1, and each test was conducted according to the above-mentioned method. The results are shown in Table 2.

Example  3 to 4 and Comparative Example  3 to 5

(C) and (D) were used in place of the component (A1) in Example 1 in the mass ratio of the component (A1) or (A2) A silicone pressure sensitive adhesive composition having a siloxane content of about 40% was prepared in the same manner as in Example 1 except that 1.2 parts of benzoyl peroxide (component (G)) was used instead of the component (E) Each test was carried out according to the method. The results are shown in Table 2.

Manufacturing example  2: Preparation of (A1) or (A2) component by solvent extraction

100 parts by weight of the same diorganopolysiloxane (A ') as in Production Example 1 was dissolved in 100 parts by weight of toluene to obtain a toluene solution. Methanol was added to the toluene solution in an amount of 100 parts by weight, stirred at room temperature for 10 minutes, and then allowed to stand to separate the toluene layer and the methanol layer. The extraction operation was performed once to obtain a toluene solution of the component (A1). The obtained toluene solution of the component (A1) was subjected to gas chromatography to quantitatively determine the octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane accompanying the component (A1). The results are shown in Table 3 below. Thereafter, stripping was performed at 100 占 폚 and 20 mmHg to remove remaining methanol. The component (A1) thus obtained was used in the following Example 5. The results are shown in Table 3. Similarly, the diorganopolysiloxane (A ') shown in Table 3 and the solvent and the number of times of extraction were used to prepare various components (A1) and (A2), and the amounts of octamethylcyclotetrasiloxane and decamethylcyclo And pentasiloxane was quantified. The results are shown in Table 3.

Example  5

35 parts of the component (A1) obtained in Production Example 2,

Me ₃ SiO _{0 .} 108.3 parts of a 60% toluene solution of an organopolysiloxane (component (B)) (Me ₃ SiO _0.5 unit / SiO ₂ unit = 0.85) containing ₅ units and SiO ₂ units,

23.7 parts of toluene,

0.22 parts of an SiH group-containing organohydrogenpolysiloxane (component (C)) of the following formula:

Me ₃ SiO (HMeSiO) ₄₀ SiMe ₃

And

0.20 part of ethynylcyclohexanol (component (D))

Were mixed.

A toluene solution (0.5 part) of a toluene (50 parts) and a platinum-vinyl group-containing siloxane complex (component (E)) containing 0.5 mass% of a platinum powder was added to the mixture (siloxane 60% And further mixed to prepare a silicone pressure sensitive adhesive composition having a siloxane content of about 40%. The obtained silicone pressure-sensitive adhesive composition was subjected to each test according to the above-mentioned method. The results are shown in Table 4.

Example  6 and Comparative Example  6 to 7

The components listed in Table 3 were used in place of the component (A1) in Example 5 as the mass ratio of the component (A1) or (A2) / (B) shown in Table 4, A silicone pressure sensitive adhesive composition having a siloxane content of about 40% was prepared in the same manner as in Example 5 except that the silicone pressure sensitive adhesive composition was added in an amount as shown in Table 4, and each test was conducted according to the above-mentioned method. The results are shown in Table 4.

Example  7 to 8 and Comparative Example  8 to 9

(C) and (D) were used in place of the component (A1) in Example 5 in terms of the mass ratio of the component (A1) or (A2) Except that 1.2 parts of benzoyl peroxide (component (G)) was added instead of the component (E) in place of the component (B), and a silicone pressure sensitive adhesive composition having a siloxane content of about 40% Each test was performed according to one method. The results are shown in Table 4.

Comparative Example  10

An oil phase diorganopolysiloxane having a viscosity of 30,000 mPa · s and a vinyl group content of 0.33 mol% represented by the above formula (4) (X = Vi) was added to thin film stripping to obtain octamethylcyclotetrasiloxane and decamethyl To obtain a diorganopolysiloxane (comparative (A1) component) accompanied by cyclopentasiloxane in an amount of less than 10 ppm based on the total mass of diorganopolysiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. This comparative (A1) component was used in place of the component (A1) in Example 1, the mass ratio of the component (A1) / component (B) was 40/60, the amount of the component (C) , A pressure-sensitive adhesive composition was prepared and tested in the same manner as in Example 1. The pressure- As a result, the adhesive strength was as low as 1.5 N / 25 mm despite the high content of the component (B). In addition, the sticky agent remained? At 250 占 폚, but? At 270 占 and 290 占 폚.

As can be seen from Tables 2 and 4, the silicone pressure-sensitive adhesive composition of the present invention is excellent in tackiness and heat resistance, and has no adhesive residue in the pressure-sensitive adhesive residue test at 250 to 290 ° C.

Claims (13)

An addition-curable or peroxide curable silicone pressure sensitive adhesive composition,
In the case of addition curing type
(A1) a diorganopolysiloxane having an alkenyl group and a viscosity at 25 DEG C of 100,000 mPa.s or more,
^{_{(B) R 1 3 SiO 0}} .5 units of organopolysiloxane having a (R ¹ is a 1-substituted substituted or non-substituted hydrocarbon group having 1 to 10 carbon atoms) and SiO ₂ units,
(C) an organohydrogenpolysiloxane having at least three SiH groups,
(D) an optional addition reaction control agent,
(E) a platinum group metal addition reaction catalyst and
(F) Organic solvents
Lt; / RTI >
In the case of peroxide curing type
(A2) a diorganopolysiloxane having a viscosity at 25 DEG C of 100,000 mPa.s or more, which may or may not have an alkenyl group,
^{_{(B) R 1 3 SiO 0}} .5 units of organopolysiloxane having a (R ¹ is a 1-substituted substituted or non-substituted hydrocarbon group having 1 to 10 carbon atoms) and SiO ₂ units,
(F) an organic solvent and
(G) The organic peroxide
(A1) and / or (A2) may be accompanied by octamethylcyclotetrasiloxane and / or decamethylcyclopentasiloxane, and the component (A1) or the component (A2) and the component ) And a content of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane based on the total amount of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane is less than 0.1 mass%. The silicone pressure sensitive adhesive composition according to claim 1, wherein the component (A1) and the component (A2) are at least one selected from the following formulas (1) to (3)
^{_{R 3 a R 2 (3-}} a) SiO (R 3 R 2 SiO) m (R 2 2 SiO) n SiR 2 (3-a) R 3 a (1)
HOR ² ₂ SiO (R ³ R ² SiO) _m (R ² ₂ SiO) _n SiR ² ₂ OH (2)
^{_{(R 3 a R 2 (3}} -a) SiO 1/2) o (R 3 R 2 SiO 2/2) p (R 2 2 SiO 2/2) q (R 4 SiO 3/2) r (SiO 4 _{/ 2} ) _s (3)
(Wherein R ² is independently a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, R ³ is independently a monovalent organic group having an alkenyl group, and a is an integer of 0 to 3 m is an integer of 0 or more, n is an integer of 100 or more, m + n is a number such that the viscosity of the diorganopolysiloxane at 25 ° C is 100,000 mPa · s or more, R ⁴ is independently R ² or R ³ is an integer of 3 to 12, p is an integer of 0 or more, q is an integer of 100 or more, r + s is an integer of 1 to 5, o + p + q + r + s is (A1), m is 2 or more when a is 0 in the formula (1), and m is 2 or more when the value of a in the formula (1) is 0, and the viscosity of the diorganopolysiloxane at 25 ° C is 100,000 mPa · s or more. (2), m is 2 or more, and when a is 0 in the formula (3), p is 2 or more). According to claim 1, (B) component of the R ¹ ₃ SiO _{0. And} the number ratio of ₅ units / SiO ₂ unit is 0.6 to 1.7. The curable pressure sensitive adhesive composition according to claim 1, wherein when the silicone pressure sensitive adhesive composition is addition cure type
(A1) is 99 to 25 parts by mass,
(B) is 1 to 75 parts by mass,
The total amount of the component (A1) and the component (B) is 100 parts by mass,
The amount of the component (C) is such that the number ratio of SiH groups to the total number of alkenyl groups in the components (A1) and (B) is from 0.5 to 20,
(D) is 0 to 8.0 parts by mass based on 100 parts by mass in total of the components (A1) and (B)
The amount of the component (E) is such that the amount of the platinum group metal component is 5 to 2,000 ppm based on the total mass of the components (A1) and (B)
(F) is 25 to 900 parts by mass based on 100 parts by mass of the total of the components (A1) and (B)
When the silicone pressure-sensitive adhesive composition is a peroxide-curable type
(A2) is 99 to 25 parts by mass,
(B) is 1 to 75 parts by mass,
The total amount of the component (A2) and the component (B) is 100 parts by mass,
(F) is 25 to 900 parts by mass based on 100 parts by mass of the total of the components (A2) and (B)
(G) component is an amount effective to cure the components (A2) and (B)
Silicone pressure sensitive adhesive composition. The silicone pressure-sensitive adhesive composition according to claim 1, wherein the content of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane in the component (A1) or (A2) is less than 0.1 mass%, respectively. (A1) or the above-mentioned (A2) component by dissolving a diorganopolysiloxane having a viscosity at 25 DEG C of 100,000 mPa.s or more and having or not having an alkenyl group in a solvent having a boiling point of 100 DEG C or higher, ) Component of the silicone pressure-sensitive adhesive composition. A diorganopolysiloxane having a viscosity at 25 DEG C of 100,000 mPa.s or more and having or not having an alkenyl group is dissolved in an organic solvent capable of dissolving a polymer polysiloxane having a degree of polymerization of 100 or more and then the polymer polysiloxane is dissolved (A1) or the above-mentioned component (A2) can be obtained by extracting and removing octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane with an organic solvent capable of dissolving octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, To obtain a silicone pressure-sensitive adhesive composition. 8. The process according to claim 7, wherein the organic solvent used for the extraction and removal is selected from methanol, ethanol and isopropyl alcohol. The method according to claim 8, wherein the organic solvent used for the extraction and removal is methanol. Having a cured layer of the silicone pressure-sensitive adhesive composition according to any one of claims 1 to 5 or the silicone pressure-sensitive adhesive composition obtained by the method according to any one of claims 6 to 9 on at least one side of the base film Adhesive film. Having a cured layer of the silicone pressure-sensitive adhesive composition according to any one of claims 1 to 5 or the silicone pressure-sensitive adhesive composition obtained by the method according to any one of claims 6 to 9 on at least one side of the base film Adhesive tape. The pressure-sensitive adhesive film according to claim 10, wherein the pressure-sensitive adhesive remains on the stainless steel plate after the pressure-sensitive adhesive film is peeled off from the stainless steel plate in the pressure-sensitive adhesive residue test described below.
[Adhesive residue test]
A tape having a width of 25 mm was cut from the pressure sensitive adhesive film. The pressure sensitive adhesive layer was brought into contact with a stainless steel plate (SUS 304 plate), and a roller having a weight of 2 kg covered with a rubber layer was reciprocated twice. And then left in a drier at a predetermined temperature (250 DEG C, 270 DEG C, and 290 DEG C) for 2 hours. After removing the tape from the dryer and allowing it to cool, the tape was peeled off from the stainless steel plate and the surface of the stainless steel plate was visually observed, Observed whether or not The pressure-sensitive adhesive tape according to claim 11, wherein the pressure-sensitive adhesive tape is peeled off from the stainless steel plate in the pressure-sensitive adhesive residue test described below, and no adhesive substance remains on the stainless steel plate.
[Adhesive residue test]
A tape having a width of 25 mm was cut from the pressure sensitive adhesive film. The pressure sensitive adhesive layer was brought into contact with a stainless steel plate (SUS 304 plate), and a roller having a weight of 2 kg covered with a rubber layer was reciprocated twice. And then left in a drier at a predetermined temperature (250 DEG C, 270 DEG C, and 290 DEG C) for 2 hours. After removing the tape from the dryer and allowing it to cool, the tape was peeled off from the stainless steel plate and the surface of the stainless steel plate was visually observed, Observed whether or not