JP2012041504A - Silicone adhesive article for cosmic space, and method for using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silicone adhesive article for cosmic space, which has flexibility, adhesiveness and good tack, can be used for pasting and temporarily fixing members used in cosmic space in a spacecraft or the like, particularly can be used as an adhesive member for collecting samples from solid celestial body surfaces such as asteroids and the moon; and to provide a method for using the same.SOLUTION: The silicone adhesive article for cosmic space is obtained by curing a non-solvent addition-type silicone adhesive composition containing the following (A) to (D) components: (A) a polydiorganosiloxane containing an alkenyl group; (B) a condensation reaction product of (a) a polydiorganosiloxane having a hydroxyl group or an alkoxy group at both terminals of the molecular chain and (b) a polyorganosiloxane having an RSiOunit and a SiOunit as essential units, and a HOSiOunit in the molecule; (C1) a polyorganohydrosiloxane having at least three SiH groups in one molecule thereof; (C2) a polydiorganohydrosiloxane having a SiH group at both terminals thereof; and (D) a platinum group metal-based catalyst. Use of the silicone adhesive article can provide an adhesive article capable of withstanding cosmic radiation and temperature cycle in the cosmic environment.

Description

  The present invention relates to a silicone adhesive article for outer space obtained by curing a solvent-free addition-type silicone adhesive composition and a method for using the same.

  For spacecrafts such as artificial satellites, solar system astronomical probes, lunar landers, manned spacecrafts, and space structures such as manned space stations and inter-orbit transports, only ordinary welding is used to fix various members. Instead, a method such as fixing with screws or Velcro or fixing with an adhesive is used. However, when the strength of the member itself is low or when the member is chemically deteriorated due to the composition of the adhesive, other methods are necessary, for example, fixing by bonding using an adhesive or an adhesive tape. There is a way to do it. However, due to restrictions in use in outer space, the adhesive used for this purpose has little degassing and changes in physical properties in a high vacuum environment, and it can withstand thermal cycles with a wide temperature range from high temperature to low temperature. It is required to have a certain level of adhesiveness over the mission period, and to withstand a space environment where ultraviolet rays, space radiation, and the like exist. Considering these, any of organic resin-based pressure-sensitive adhesives such as acrylic pressure-sensitive adhesives and rubber pressure-sensitive adhesives cannot be used in terms of durability.

  Conventionally known silicone pressure-sensitive adhesives can be prepared on pressure-sensitive adhesive tapes and pressure-sensitive adhesive sheets by applying them to plastic substrates, etc. It was insufficient for use as a pressure-sensitive adhesive member having a buffering property capable of absorbing the expansion and contraction generated in the adherend in a temperature cycle repeated in outer space. Moreover, when it affixed on the adherend surface with a shape with unevenness, the surface of the pressure-sensitive adhesive layer could not follow the unevenness, and voids remained and could not be completely adhered. Conventional silicone pressure-sensitive adhesives are generally of a solvent type, and there is concern about the generation of bubbles due to residual solvent under high vacuum in outer space. Therefore, the solventless type is desirable for such applications.

Known silicone adhesives include polyorganosiloxanes having alkenyl groups and polyorganosiloxanes having no alkenyl groups, polyorganosiloxanes having R ₃ SiO _0.5 units and SiO ₂ units, and polyorganos containing SiH groups. A silicone composition for addition-curable pressure-sensitive adhesives containing siloxane is known (Japanese Patent Laid-Open No. 2008-24777: Patent Document 1). Although this composition is said to have strong adhesive strength to silicone rubber, it is a solvent type and is inflexible, so it is inconvenient for bonding a member having irregularities on the surface.

Further, (A) a raw rubber-like diorganopolysiloxane having a silicon-bonded hydroxyl group and no alkenyl group, (B) a raw rubber-like diorganopolysiloxane having an alkenyl group, (C) R ₃ SiO _1/2 unit and made of SiO ₂ units, a polyorganosiloxane having a 1.8 mass% or more silicon-bonded hydroxyl groups, (D) R ₃ consists SiO _1/2 units and SiO ₂ units, less than 1.8 wt% silicon-bonded hydroxyl groups An addition-type silicone pressure-sensitive adhesive composition containing a component obtained by combining a polyorganosiloxane having a partial condensation reaction and an organopolysiloxane having a silicon-bonded hydrogen atom is known (Japanese Patent Application Laid-Open No. 2004-231900). : Patent Document 2). This composition is said to have a large adhesive force and a small tack, but it is a solvent type and has insufficient flexibility and a tack is too small. Was inconvenient. Furthermore, it is necessary to correct the misalignment at the time of bonding when it is used for bonding members as an adhesive sheet with a side of several centimeters or more and an area of several tens of cm ² or more. In some cases, peeling due to re-working (rework) required according to the situation cannot be performed.

  Non-Earth celestial bodies that humans have sampled directly from the solid surface so far are only the moons visited by the US-Soviet Union in the 1970s until the Japanese spacecraft Hayabusa conducted on the asteroid Itokawa in 2005. It is. However, large solid celestial bodies such as planets and the moon like Earth and Mars have been thermally transformed and cannot acquire the initial material of the solar system. On the other hand, solar system asteroids such as comets and asteroids are said to be relatively well-maintained records of the primitive solar system when the planet was born. Therefore, if technology to bring back samples from small bodies was established, `` What was the material that made the planets and satellites? '', `` What about the state of the solar nebula when the planet was born? It is possible to obtain important knowledge about human history.

  As a method for sampling from the surface of a celestial body using a sample return probe on the assumption that it will be brought back to the earth, a method that has a proven track record in the past, such as the moon or Mars, is attached to the lander's robot arm. In the case of celestial bodies with small gravity like asteroids, metal bullets are launched from the spacecraft toward the surface of the celestial body at high speed to crush the surface, and the scattered pieces are collected in the collection box inside the spacecraft. There are only two types of methods to do.

  However, the above method for microgravity celestial bodies crushes the celestial surface, so the collected sample cannot know the size distribution of gravel on the celestial surface, and the difference in the composition distribution between the outermost surface of the sample and the internal composition. I can't even know. In order to know this, a method different from the above method is necessary. For example, a method of collecting the uppermost sample by pressing an adhesive substance on the celestial surface is considered.

  The function of an adhesive substance is an important key in order to collect more samples with a size of a fraction of 1 mm to several mm distributed on the celestial surface at the same time.

  Due to restrictions in use in outer space, the adhesive material used for this purpose must have a certain level of adhesiveness over a wide temperature range from high temperature to low temperature, and must withstand the space environment where cosmic radiation and space ultraviolet rays exist. To withstand temperature cycles during the navigation of the spacecraft over a long period of time, to minimize the contamination of samples collected by sticky substances, and to ensure a sample collection property of 0.1 to several centimeters in thickness It is required that it can be molded.

  Examples of adhesive substances available as industrial products include adhesives, greases, potting agents, etc. In consideration of these, organic resin adhesives such as acrylic adhesives and rubber adhesives, mineral oils, silicones, etc. Grease of organic type, organic resin type potting agent, etc., organic resin type can not be used in terms of durability against temperature cycle and space radiation, and silicone grease can not be used in terms of contamination.

For the purpose of sampling celestial surfaces, particularly important requirements for sticky materials are flexibility and low contamination of the sample.
For example, when a sticky substance is pressed against the surface of a celestial body where fine sand grains or pebbles are scattered, if the flexibility is insufficient, the sticky substance cannot reach the sand grains near the pebbles and cannot be collected at the same time. . Further, when the collected sample is brought back to the earth and then analyzed, the sample is peeled off from the adhesive substance. If the adhesive substance remains on the sample surface at this time, the analysis of the sample is hindered.

  For example, in a previous study of a sampling method for pressing an adhesive substance on the surface of a celestial body, there was one using grease (SAMPLE COLLECTION FROM SMALL AIRLESS BODIES: EXAMINATION OF TEMPERATURE CONSTRAINTS FOR THE TGIP SAMPLE COLLECTOR FOR THE HERA NEAR-EARTH ASTEROID SAMPLE RETURN MISSION: MA Franzen, LA Roe, JA Buffington, DWG Sears, WM Keck, Abstract of Lunar and Planetary Science XXXVI, 1467, (2005) .: Non-patent document 1). However, the reduction of contamination due to infiltration into rock samples has not been fully considered. In other words, since grease is a paste-like substance and not a cured product, when the adhered sample is peeled off, the grease cannot be removed because it adheres to the sample.

  Considering the above requirements, silicone gels and silicone pressure-sensitive adhesives that form polysiloxane cured products were considered candidates.

  As a gel material having adhesiveness and heat resistance, there is a silicone gel, and an adhesive silicone gel is also known (Japanese Patent Laid-Open No. 2007-126576: Patent Document 3). Since the silicone gel is a solvent-free type, it can be molded with a thickness of several centimeters. Although the cured product is flexible and has sufficient sample collection properties, the adhesive force to the adherend is insufficient, and if an external force is applied, it may be peeled off. Moreover, since many free oils which are non-reaction components are contained, this will permeate a sample. Further, when the sample is peeled off from the silicone gel, the cohesiveness is insufficient, so that the silicone gel remains on the surface of the sample due to cohesive failure and may be extremely contaminated.

  On the other hand, silicone adhesives can be applied to plastic substrates and formed into adhesive tapes and adhesive sheets with sufficient adhesiveness. However, since they are usually solvent-type, they can be applied to thick films when heat-cured. In this case, foaming due to the solvent occurs, and it is difficult to integrally mold to a thickness of 1 cm. In addition, even if a cured product is used as a thick film of about 100 μm coated on a substrate, the hardness is high, so there is no flexibility to follow the unevenness of the sample distributed on the celestial surface, and the sample collection property is It is insufficient.

  Known silicone pressure-sensitive adhesives include those mentioned above, but since all are solvent-type, they cannot be coated or molded to a thickness of 0.1 mm to several centimeters necessary for sample collection. Even if an attempt is made to apply a thick film, foaming due to the solvent will occur during heat curing. In addition, since the flexibility is insufficient, it is not possible to simultaneously collect astronomical surface samples of various sizes.

Also, as solvent-free silicone adhesive, alkenyl group-containing polydiorganosiloxane, polyorganohydrosiloxane having 3 SiH groups, low polymerization polydiorganosiloxane having alkenyl groups at both ends, SiH groups at both ends A composition comprising a polydiorganosiloxane having a low polymerization degree, a polyorganosiloxane composed of R ₃ SiO _1/2 units and SiO ₂ units, and a platinum-based catalyst is known (Patent Document 4: Japanese Patent Application Laid-Open No. 2008-274251). ). This composition is excellent in removability, has an appropriate adhesive strength, and is solventless, so that it has a coating property with a thick film, but has insufficient flexibility and buffering properties.
Similarly, the solventless silicone pressure sensitive adhesive disclosed in Japanese Patent Application Laid-Open No. 2006-160923 (Patent Document 5) has insufficient flexibility and buffering properties.

Furthermore, as another solvent-free or low-solvent type silicone pressure-sensitive adhesive, alkenyl group-terminated polydiorganosiloxane, silanol-terminated polydiorganosiloxane, resinous copolymer containing R ₃ SiO _1/2 units and SiO ₂ units, organohydrogen poly There is a low solvent type silicone pressure-sensitive adhesive containing siloxane, hydrosilylation catalyst, organic peroxide or organic azo compound (Patent Document 6: JP-T-2004-506778). Since this composition has strong adhesion and high tack, there is a possibility that the adherend may be deformed or destroyed during rework such as re-sticking. Since it hardens | cures using an organic peroxide or an organic azo compound etc., there existed a problem that the decomposition | disassembly residue remained in hardened | cured material and foamed when using hardened | cured material under high temperature or a vacuum.

As another solvent-free silicone pressure-sensitive adhesive, an organosiloxane polymer having an aliphatic unsaturated group, a resin having R ₃ SiO _1/2 units and SiO ₂ units, a reactive diluent, a SiH-containing cross-linking agent, a hydrosilylation catalyst, There is a solvent-free silicone pressure-sensitive adhesive containing an inhibitor (Patent Document 7: JP-T-2006-520838). This composition is also insufficient in flexibility and buffering properties. In addition, since it contains a reactive diluent such as an alkene having a terminal double bond, foaming occurs at the time of curing with a thick film, and bubbles remain in the cured product. There was a problem of foaming when used under high temperature or under vacuum.

JP 2008-24777 A Japanese Patent Laid-Open No. 2004-231900 JP 2007-126576 A JP 2008-274251 A JP 2006-160923 A JP-T-2004-506778 JP 2006-520838 A

SAMPLE COLLECTION FROM SMALL AIRLESS BODIES: EXAMINATION OF TEMPERATURE CONSTRAINTS FOR THE TGIP SAMPLE COLLECTOR FOR THE HERA NEAR-EARTH ASTEROID SAMPLE RETURN MISSION: MA Franzen, LA Roe, JA Buffington, DWG Sears, WM Keck, Abstract Science of LuXXX and Planetary Science 1467, (2005).

  The present invention is an improvement of the above circumstances, has flexibility, adhesiveness, good tack, and can be used as a material for bonding or temporarily fixing members used in outer space in a spacecraft or the like, In particular, it is an object to provide a silicone adhesive article for outer space that can be used as an adhesive member for sampling from the surface of a solid celestial body such as an asteroid or the moon, and a method for using the same.

  For the silicone-based adhesive material used for fixing the spacecraft member, the present inventors have particularly, a silicone-based adhesive for efficiently collecting a celestial surface sample having a size of a few millimeters to several millimeters. As a result of examining the substance in detail, as a silicone pressure-sensitive adhesive composition for space, which is obtained by curing a solvent-free addition-type silicone pressure-sensitive adhesive composition containing the following components (A) to (D) as a silicone pressure-sensitive adhesive composition: It has been found that it is effective in achieving the above-mentioned purpose.

Accordingly, the present invention provides the following silicone adhesive article for outer space and a method for using the same.
Claim 1:
A silicone adhesive article for outer space characterized by curing a solvent-free addition-type silicone adhesive composition containing the following components (A) to (D).
(A) a polydiorganosiloxane having at least two alkenyl group-containing organic groups in one molecule represented by the following general formula (1):
_{X b R 3-b SiO- [} R 2 SiO] a -SiX b R 3-b (1)
(Wherein X is an alkenyl group-containing organic group having 2 to 10 carbon atoms, R is a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be the same or different. A is an integer and 50 ≦ a ≦ 2,000, and b is an integer of 1 to 3.)
(B) a condensation reaction product obtained by condensing the SiOR ² group of the component (a) and the SiOH group of the component (b) shown below,
(A) a polydiorganosiloxane having a hydroxyl group or an alkoxy group at both ends of a molecular chain, represented by the following general formula (2):
(R ² O) R ¹ ₂ SiO— [R ¹ ₂ SiO] _c —SiR ¹ ₂ (OR ² ) (2)
(Wherein, R ¹ is a monovalent hydrocarbon group having same or different carbon atoms and optionally 1 to 10, .R ² containing no alkenyl group-containing organic group is a hydrogen atom or R ^1, c is an integer And 50 ≦ c ≦ 2,000.)
(B) containing R ¹ ₃ SiO _1/2 units, SiO ₂ units, and siloxane units having a hydroxyl group bonded to a silicon atom, wherein the molar ratio of R ¹ ₃ SiO _1/2 units / SiO ₂ units is 0.6. A polyorganosiloxane having a hydroxyl group content of 0.1% by mass or more and less than 1.8% by mass (R ¹ is the same as described above),
(However, (A) component is 10-60 mass parts with respect to a total of 100 mass parts of (A), (a), (b) component, and (a) component is 5-60 mass parts, (B) A component is 5-60 mass parts.)
(C1) a polyorganohydrosiloxane having at least 3 SiH groups in one molecule,
(C2) a polydiorganohydrosiloxane having SiH groups at both ends represented by the following general formula (3):
HR ¹ ₂ SiO— [R ¹ ₂ SiO] _d —SiR ¹ ₂ H (3)
(R ¹ is the same as above, d is an integer, and 5 ≦ d ≦ 500.)
(However, the ratio of the number of moles of the SiH group of the (C1) component to the alkenyl group of the (A) component is 0.2 to 10, and the ratio of the number of moles of the SiH group of the (C2) component is 0.2 to 3 .)
(D) Platinum group metal catalyst (1 to 500 ppm on a mass basis with respect to the total of components (A), (a), and (b) as platinum group metal components).
Claim 2:
The silicone pressure-sensitive adhesive article for outer space according to claim 1, wherein the viscosity of the silicone pressure-sensitive adhesive composition at 25 ° C is 5,000 to 500,000 mPa · s.
Claim 3:
On a pressure-sensitive adhesive sheet provided with a pressure-sensitive adhesive layer of a silicone pressure-sensitive adhesive composition on a polyimide film having a thickness of 50 μm and a thickness of 0.5 mm, a probe with a smooth tip of 5 mm in diameter is contacted at a speed of 1 cm / sec and a contact pressure of 20 g / cm. ^3. The universe according to claim 1 or 2, wherein the probe tack obtained by pressing the probe vertically so as to be ² and measuring the force when the probe is separated after 1 second of the stop time is 50 to 500 gf. Silicone adhesive article for space.
Claim 4:
A 25 mm wide adhesive tape provided with an adhesive layer of a silicone adhesive composition so as to have a thickness of 40 μm on a 25 μm thick polyimide film was bonded to a stainless steel plate, and this adhesive tape was fastened at a speed of 300 mm / min in the 180 ° direction. The silicone pressure-sensitive adhesive article for outer space according to any one of claims 1 to 3, wherein the adhesive strength when peeled off is 0.05 to 4.0 N / 25 mm.
Claim 5:
The silicone adhesive article for outer space according to any one of claims 1 to 4, which is used for sampling a surface sample of a solar system small body, a solid planet, or a solid satellite.
Claim 6:
Using the silicone adhesive article for outer space according to any one of claims 1 to 4 coated, cured or molded so as to have a thickness of 0.1 to 30 mm, a solar system celestial body such as an asteroid or comet, A method for collecting surface samples of solid planets such as Mercury or solid satellites such as the Moon.

  According to the present invention, it is possible to obtain a space-sensitive silicone adhesive article obtained by curing a solvent-free addition-type silicone adhesive composition containing no organic solvent. When this silicone adhesive article is used, an adhesive article that can withstand space radiation and temperature cycles in the space environment can be obtained. This adhesive article can be used for bonding members or temporarily fixing members used in outer space in an artificial satellite, space probe, or the like. Further, it is effective for collecting samples on the surface of celestial bodies such as solar system small bodies such as asteroids and comets, solid planets such as Mercury, and solid satellites such as the moon, and contamination of the samples can be reduced.

The present invention is described in further detail below.
[(A) component]
The component (A) is a substantially linear polydiorganosiloxane having an alkenyl group-containing organic group at the end of the molecular chain represented by the following general formula (1).
_{X b R 3-b SiO- [} R 2 SiO] a -SiX b R 3-b (1)

  X is an alkenyl group-containing organic group having 2 to 10 carbon atoms. Specifically, cycloalkenyl such as alkenyl group such as vinyl group, allyl group, hexenyl group, octenyl group, acryloylpropyl group, acryloylmethyl group, methacryloylpropyl group, methacryloylalkyl group, cyclohexenylethyl group, etc. Examples thereof include an alkenyloxyalkyl group such as an alkyl group and a vinyloxypropyl group, and a vinyl group is particularly preferred industrially.

  R is a C1-C10 monovalent hydrocarbon group which may be the same or different. Specifically, for example, alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, alkenyl groups such as vinyl groups, allyl groups, hexenyl groups, octenyl groups, phenyl groups, and tolyl groups. An aryl group such as a group, and some or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with a halogen atom such as a fluorine atom or other group, and a trifluoromethyl group 3,3,3-trifluoropropyl group and the like. A methyl group and a phenyl group are particularly preferable.

a is an integer, 50 ≦ a ≦ 2,000, and particularly preferably 50 ≦ a ≦ 1,500.
b is an integer, 1 to 3, and preferably 1.

  (A) It is preferable to contain an alkenyl group in 0.03-4 mol% of all the silicon atoms of a component, especially 0.03-1.5 mol%, Furthermore, 0.05-1 mol%. If it is less than 0.03 mol%, the curability of the resulting composition may be insufficient, and if it exceeds 4 mol%, the adhesive strength and tack of the resulting composition may be reduced.

This polydiorganosiloxane is substantially linear, but can contain 10 or less RSiO _3/2 units and SiO ₂ units in each molecule of component (A). When x RSiO _3/2 units are contained (x is an integer of 1 to 10), the number of terminal X _b R _3-b SiO _1/2 units is preferably x + 2. When x SiO ₂ units are included (x is an integer from 1 to 10), the number of terminal X _b R _3-b SiO _1/2 units is preferably 2x + 2.

  The polydiorganosiloxane is preferably oily. The viscosity of the component (A) is preferably 60 mPa · s or more and 200,000 mPa · s or less if it is oily at 25 ° C. If it is less than 60 mPa · s, the flexibility of the pressure-sensitive adhesive layer may be lowered, which is not suitable. If it exceeds 200,000 mPa · s, the composition may become too viscous and coating may be difficult. This viscosity can be measured with a rotational viscometer (hereinafter the same).

  Furthermore, (A) component may use 2 or more types together. In this case, an alkenyl group may be contained in 0.03 to 4 mol% of all silicon atoms included in the total of component (A).

  The component (A) usually uses a monomer such as octamethylcyclotetrasiloxane, a silane compound or siloxane compound having a dimethylvinylsiloxane unit, a silane compound or siloxane compound having a dimethylsiloxane unit or a methylvinylsiloxane unit, and a catalyst. However, since it contains cyclic low-molecular siloxane after polymerization, the cyclic low-molecular siloxane is distilled off while passing an inert gas under heating and / or reduced pressure. It is preferable.

  In the present invention, the component (A) is a component for reacting with the component (C1) to form a crosslinked structure. If the generation of the crosslinked structure is insufficient, the cohesiveness of the composition after curing is lowered. If the crosslinked structure is too strong, the composition flexibility after curing is lowered.

[Component (B)]
Component (B) is a component for simultaneously imparting tackiness and flexibility to the composition, and is a condensation reaction product obtained by condensing the SiOR ² group of component (a) and the SiOH group of component (b) shown below. It is.
The component (a) is a substantially linear polydiorganosiloxane having a hydroxyl group or an alkoxy group at both ends of the molecular chain represented by the following general formula (2).
(R ² O) R ¹ ₂ SiO— [R ¹ ₂ SiO] _c —SiR ¹ ₂ (OR ² ) (2)

R ¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be the same or different and does not include an alkenyl group-containing organic group. Specifically, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a 2-propyl group, a butyl group and a 2-butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group and a tolyl group Furthermore, some or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with a halogen atom such as a fluorine atom or other groups, such as a trifluoromethyl group, 3, 3, 3 -A trifluoropropyl group etc. are illustrated. A methyl group and a phenyl group are particularly preferable.
R ² is a hydrogen atom or R ¹ , and is preferably a hydrogen atom. c is an integer, 50 ≦ c ≦ 2,000, and preferably 50 ≦ c ≦ 1,500.

The polydiorganosiloxane is substantially linear, but may contain R ¹ SiO _3/2 units and SiO ₂ units in 2 mol% or less of the total siloxane units in component (a). it can.

The polydiorganosiloxane is preferably oily. The viscosity of the component (a) is preferably 100 mPa · s or more and 200,000 mPa · s or less if it is oily at 25 ° C. Less than 100 mPa · s is unsuitable because the flexibility of the pressure-sensitive adhesive layer may be lowered. On the other hand, if it exceeds 200,000 mPa · s, the composition may become too viscous and coating may be difficult.
Furthermore, (a) component may use 2 or more types together.

The component (b) is a polyorganosiloxane containing R ¹ ₃ SiO _1/2 units, SiO ₂ units, and a siloxane unit having a hydroxyl group bonded to a silicon atom. R ¹ is as described above. The molar ratio of R ¹ ₃ SiO _1/2 unit / SiO ₂ unit is 0.6 to 1.0, preferably 0.8 to 1.0. If it is less than 0.6, the adhesive strength and flexibility of the composition may be reduced, and if it exceeds 1.0, the adhesive strength may be reduced. The hydroxyl group content is 0.1% by mass or more and less than 1.8% by mass, preferably 0.3 to 1.7% by mass. When the hydroxyl group content is 1.8% by mass or more, the flexibility of the cured product is lowered. If the hydroxyl group content is less than 0.1% by mass, the coagulation of the cured product is insufficient, or the condensation reaction of the components (a) and (b) shown below does not proceed sufficiently, Contamination will increase.
The siloxane unit containing a hydroxyl group bonded to a silicon atom is mainly a (HO) SiO _3/2 unit. In addition to this, a (HO) (R ² O) SiO _2/2 unit, a (HO) (R ² O) unit. ₂ SiO _1/2 units.
Furthermore, some of the SiO ₂ units may be R ¹ OSiO _3/2 .

Further, R ¹ ₂ SiO units and R ¹ SiO _3/2 units may be contained in the component (b) in a proportion of 20 mol% or less of all silicon atoms within the range not impairing the characteristics of the present invention. is there. In addition, (b) component may use 2 or more types together.

  The mixing ratio of the component (A) is 10 to 60 parts by mass, preferably 15 to 50 parts by mass with respect to 100 parts by mass in total of the components (A), (a), and (b). When the mass ratio of the component (A) is less than 10 parts by mass, the curability decreases, and when it exceeds 60 parts by mass, the flexibility decreases. Moreover, the mixture ratio of (a) component is 5-60 mass parts, Preferably it is 15-50 mass parts. When the mass ratio of the component (a) is less than 5 parts by mass, the flexibility is lowered, and when it exceeds 60 parts by mass, the cohesiveness is lowered or the silicone is transferred to the adherend. Moreover, the mixture ratio of (b) component is 5-60 mass parts, Preferably it is 5-45 mass parts. When the mass ratio of the component (b) is less than 5 parts by mass, the adhesive strength is reduced, and when it exceeds 60 parts by mass, the adhesive strength becomes too strong and the peelability (reworkability) is reduced or the flexibility is reduced. The blending ratios of the components (a) and (b) are as described above, but it is preferable to blend the component (b) so that the number of molecules (number of moles) is larger than that of the component (a). It is preferable not to include the component (a). Even if there is an unreacted component (b), it does not flow in the cured product, so it does not affect the cohesiveness of the cured product and the contamination of the adherend.

  As the components (a) and (b), a product obtained by previously forming a condensation reaction product of the component (B) by a condensation reaction is used. Moreover, you may use what used (A), (a), and (b) component for a condensation reaction together, and made (a) and (b) component the condensation reaction product. In order to perform the condensation reaction, a mixture of the components (a) and (b) dissolved in an organic solvent such as toluene, xylene, heptane, and octane is allowed to react at room temperature to reflux using an alkaline catalyst. What is necessary is just to neutralize as needed.

  Examples of alkaline catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and other metal hydroxides, carbonates such as sodium carbonate and potassium carbonate, bicarbonates such as sodium bicarbonate and potassium bicarbonate, Examples thereof include metal alkoxides such as sodium methoxide and potassium butoxide, organic metals such as butyl lithium, potassium silanolate, ammonia gas, ammonia water, nitrogen compounds such as methylamine, trimethylamine and triethylamine. preferable. Although the temperature of a condensation reaction can be 20-150 degreeC, it should just carry out normally at the reflux temperature of room temperature-the organic solvent. The reaction time is not particularly limited, but may be 0.5 to 20 hours, preferably 1 to 10 hours.

  Furthermore, a neutralizing agent that neutralizes the alkaline 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. When ammonia gas or ammonia water or a low boiling point amine compound is used as the alkaline catalyst, an inert gas such as nitrogen may be vented and distilled off.

  In this invention, (B) component is a component for providing adhesiveness and a softness | flexibility simultaneously to this composition, suppressing the contamination to a to-be-adhered body. (A) When the amount of component increases, it becomes more flexible, and when the amount of (b) component increases, the tackiness becomes stronger. When the component (b) is not present, the cured product of the present composition is flexible, but the tackiness and cohesiveness are insufficient. When the component (a) is not present, the flexibility is insufficient. If the components (a) and (b) are not condensed, the component (a) is an oily polymer having fluidity, and therefore easily bleeds from the cured product and contaminates the adherend. When the component (a) and the component (b) are condensed, the component (b) having a bulky structure is bonded to both ends of the component (a) which is a linear polymer. For this reason, it is retained in the crosslinked network of the cured product due to steric hindrance and does not easily bleed, and can prevent penetration and contamination of the adherend. Furthermore, since the condensation reaction product of the component (B) does not contain an alkenyl group, it does not react with the component (A) and is not incorporated into the crosslinking network. For this reason, a certain amount of molecular movement is allowed in the cross-linking network, and the cured article can be given flexibility. The component (b) is used as a tackifier component in a normal silicone adhesive.

[Component (C)]
(C) component is the following (C1) component and (C2) component.
[(C1) component]
Component (C1) is a cross-linking agent, which is a polyorganohydrosiloxane having at least three hydrogen atoms bonded to silicon atoms in one molecule, and linear, branched or cyclic ones can be used. Specific examples of the component (C1) include those represented by the following general formula (4), but are not limited thereto, and are used alone or in combination of two or more. be able to.

^{_{H g R 1 3-g SiO-}} [HR 1 SiO] e - [R 1 2 SiO] f -SiH g R 1 3-g
(4)
(In Formula (4), R ¹ is the same as above, g is 0 or 1, e is an integer of 1 or more, and f is an integer of 0 or more, provided that e + 2g is 3 or more and 1 ≦ e + f ≦ 500, where e + 2g is preferably from 3 to 100, more preferably from 3 to 70. Further, a structure containing R ¹ SiO _3/2 units, HSiO _3/2 units, and SiO ₂ units. Can also be illustrated.)

  The viscosity of this polyorganohydrosiloxane at 25 ° C. is preferably 1 to 1,000 mPa · s. 2 to 500 mPa · s is particularly preferable. A mixture of two or more kinds may be used.

  The blending amount of the component (C1) is such that the molar ratio of the SiH group in the component (C1) to the alkenyl group in the component (A) (SiH group / alkenyl group) is 0.2 to 10, particularly 0. It is preferable to mix | blend so that it may become the range of 3-5. If the molar ratio is too small, the crosslinking density is lowered, and accordingly, the curability may be lowered or the holding power and cohesiveness of the resulting pressure-sensitive adhesive composition may be lowered. If the molar ratio is too large, Flexibility may be reduced.

[(C2) component]
Component (C2) is a polydiorganohydrosiloxane having hydrogen atoms bonded to silicon atoms at both ends, and has the effect of alternately reacting with component (A) to extend the chain length. What is represented by the following general formula (3) is used.
HR ¹ ₂ SiO— [R ¹ ₂ SiO] _d —SiR ¹ ₂ H (3)
(In Formula (3), R ¹ is the same as described above, d is an integer, and 5 ≦ d ≦ 500.)

  The viscosity of this polyorganohydrosiloxane at 25 ° C. is preferably 2 to 5,000 mPa · s. Furthermore, 3-100 mPa * s is preferable. A mixture of two or more kinds may be used.

The blending amount of the component (C2) is such that the molar ratio of the SiH group in the component (C2) to the alkenyl group in the component (A) (SiH group / alkenyl group) is 0.2 to 3, particularly 0. It is preferable to mix | blend so that it may become the range of 0.5-3. If it is less than 0.2, the crosslinking density is lowered, and accordingly, the curability may be lowered, or the holding power and the cohesiveness of the resulting pressure-sensitive adhesive composition may be lowered. If it exceeds 3, the flexibility of the composition may decrease.
In addition, the total molar ratio (SiH group / alkenyl group) of the SiH group of the (C1) component and the (C2) component to the alkenyl group in the component (A) is 0.4 to 13, particularly 0.5 to 8. It is preferable.

[(D) component]
Component (D) is a platinum group metal-based addition reaction catalyst. For example, 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, chloride Examples include a reaction product of platinum acid and a vinyl group-containing siloxane, a platinum-olefin complex, a platinum-vinyl group-containing siloxane complex, a rhodium complex, and the like, and a platinum-based catalyst is particularly preferable.

  Component (D) is preferably added in an amount of 1 to 500 ppm, particularly 2 to 100 ppm on a mass basis as a platinum group metal component with respect to the total of components (A), (a), and (b). If it is less than 1 ppm, the curability is lowered, the crosslinking density is lowered, and the holding power may be lowered. If it exceeds 500 ppm, the flexibility of the composition may be lowered.

[(E) component]
If necessary, the composition of the present invention may further contain a reaction control agent as component (E). This is added to prevent the treatment liquid from thickening or gelling when the silicone pressure-sensitive adhesive composition is prepared or applied to the substrate, so that the addition reaction starts before heat curing. is there. The reaction control agent coordinates to the platinum group metal which is an addition reaction catalyst to suppress the addition reaction, and when heated and cured, the coordination is lost and the catalytic activity is exhibited. Any reaction control agent conventionally used in addition reaction curable silicone compositions can be used. 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 Examples include -1,3-divinyldisiloxane, maleic acid ester, and adipic acid ester.

  The blending amount of the component (E) is preferably in the range of 0.005 to 5 parts by mass, particularly 0.005 to 2 parts by mass with respect to 100 parts by mass in total of the components (A), (a), and (b). Part is preferred. If it is less than 0.005 parts by mass, the treatment liquid may cause thickening or gelation. If it exceeds 5 parts by mass, the curability may be lowered.

The composition of the present invention is used as follows, for example, but is not limited thereto.
(I) Components (a) and (b) are subjected to a condensation reaction to produce a condensation reaction product of component (B). When the condensation reaction is performed using a solvent, the solvent is removed. (A) component, (C) component, (D) component, and (E) component as needed are mixed here and a solvent-free type composition is obtained.
(II) The components (a) and (b) are subjected to a condensation reaction in the presence of the component (A) to produce a condensation reaction product of the component (B). When the condensation reaction is performed using a solvent, the solvent is removed. The component (C), the component (D), and the component (E) if necessary are mixed here to obtain a solventless composition.

  The solvent may be removed by a conventional method by distilling off the solvent while passing an inert gas such as nitrogen as necessary under a normal pressure or a reduced pressure in a temperature range of room temperature to 200 ° C.

  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, thioethers, hindered amines -Based, triazole-based, benzophenone-based light stabilizers, phosphate ester-based, halogen-based, phosphorus-based, antimony-based flame retardants, cationic activators, anionic activators, nonionic activators, silicate systems, metal oxidation It is possible to use an antistatic agent such as a physical system or various ions, a colorant such as a dye or a pigment, a filler such as silica, alumina or a metal salt.

  The silicone pressure-sensitive adhesive composition of the present invention formulated as described above is preferably adjusted so that the viscosity at 25 ° C. is 5,000 to 500,000 mPa · s. What becomes 5,000-300,000 mPa * s is preferable. If it is less than 5,000 mPa · s, it is too low, and the composition is cast on the substrate to make the surface non-uniform, or the adhesive strength may be lowered. If it exceeds 500,000 mPa · s, the composition becomes too viscous, and stirring, casting and coating during production may be difficult.

  Furthermore, the solventless silicone pressure-sensitive adhesive composition of the present invention is preferably used as it is, but may be used after being diluted with a solvent depending on the convenience of the user. When this composition is diluted in a solvent and used, the diluent solvent is an aromatic hydrocarbon solvent such as toluene or xylene, aliphatic such as hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane, or isoparaffin. Hydrocarbon solvents, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, acetonyl acetone, cyclohexanone and other ketone solvents, ethyl acetate, Ester solvents such as propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1,2-dimethoxyethane, 1,4-dioxane Agents, multifunctional solvents such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, 2-butoxyethyl acetate, hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetra Siloxane solvents such as siloxane, decamethylcyclopentasiloxane, tris (trimethylsiloxy) methylsilane, tetrakis (trimethylsiloxy) silane, or a mixed solvent thereof can be used.

  The silicone pressure-sensitive adhesive composition prepared as described above can be applied to various substrates and cured under predetermined conditions to obtain a pressure-sensitive adhesive layer.

  As the base material, polyester, polytetrafluoroethylene, polyimide, polyphenylene sulfide, polyamide, polycarbonate, polystyrene, polypropylene, polyethylene, polyvinyl chloride and other plastic films, aluminum foil, copper foil and other metal foil, Japanese paper, synthetic paper, Examples thereof include paper such as kraft paper and polyethylene laminated paper, cloth, nonwoven fabric, glass cloth, and a composite base material formed by laminating and impregnating a plurality of these.

  In order to improve the adhesion between the base material and the pressure-sensitive adhesive layer, a base material that has been previously subjected to primer treatment, corona treatment, etching treatment, plasma treatment, sandblast treatment, or the like may be used. Primer treatment and corona treatment are preferred.

  Examples of primer compositions that can be used for primer treatment include polydiorganosiloxanes having SiOH groups at the ends, polysiloxanes having SiH groups and / or polysiloxanes having alkoxy groups, and condensation type silicone primer compositions containing a condensation reaction catalyst. And polydiorganosiloxanes having alkenyl groups such as vinyl groups, polysiloxanes having SiH groups, and addition-type silicone primer compositions containing an addition reaction catalyst.

  The coating method may be applied using a known coating method, such as a comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater, kiss coater, gravure coater, screen coating, Examples include dip coating and cast coating. As for the coating amount, it is preferable that the thickness of the pressure-sensitive adhesive layer after curing is 10 μm to 40 mm, particularly 20 μm to 10 mm. In particular, in order to collect surface samples of asteroids such as asteroids and comets, solid planets such as Mercury, or solid satellites such as the Moon as silicone adhesive articles for outer space, the thickness should be 0.1 to 30 mm. It is preferable to perform coating curing or molding. If it is less than 0.1 mm, it is difficult to collect a sample of a large size. Even if it exceeds 30 mm, the sample collection property does not change.

  Curing conditions may be 80 to 180 ° C. and 30 seconds to 120 minutes, but are not limited thereto.

  An adhesive tape or the like may be produced by directly applying the composition of the present invention to the substrate as described above, or the composition of the present invention may be applied to a release film or release paper provided with a peelable coating on the surface. After being worked and cured, an adhesive tape or the like may be produced by transferring the pressure-sensitive adhesive layer to the substrate by bonding the obtained pressure-sensitive adhesive layer side to the substrate. Further, after applying the composition of the present invention to a release film or release paper provided with a release coating on the surface and curing, another release film or release paper is bonded to the surface of the pressure-sensitive adhesive layer. You may manufacture the adhesive sheet without material.

  In addition, the silicone pressure-sensitive adhesive composition is poured or cast into a predetermined container or molding mold, and when it contains a solvent, a cured product is obtained by drying the solvent and then curing it under the above conditions. Can do.

  Examples of the container and mold include metals such as stainless steel and aluminum, ceramics, and plastics such as fluororesin. In addition, bubbles may be entrained when injected or cast into a container or mold. In this case, the bubbles may be removed by leaving them at room temperature, normal pressure, or reduced pressure. Furthermore, in order to make it easy to release from the mold, a release agent may be applied to the surface of the mold in advance. In this case, a fluorine release agent and a fluorine silicone release agent are preferable.

The probe tack of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet obtained by applying the composition of the present invention to a polyimide film having a thickness of 50 μm so as to have a thickness of 0.5 mm is preferably 50 to 500 gf, particularly preferably 60 to 500 gf. Furthermore, it is preferable that it is 70-400 gf. This probe tack is a force when a probe having a smooth tip with a diameter of 5 mm is pressed vertically at a speed of 1 cm / second so that the contact pressure is 20 g / cm ² and the probe is pulled away after a stop time of 1 second. When the adhesive tape or adhesive sheet is affixed to the adherend when it is less than 50 gf, it is necessary to press it with a strong force from the back, and workability at the time of adhering is reduced. Workability for re-sticking (rework) for correcting misalignment or the like is reduced. Such probe tack value can be achieved mainly by adjusting the amount of component (b).

  Adhesion when a 25 mm wide polyimide film with a thickness of 40 μm is attached to a stainless steel plate with a 25 μm thick polyimide film and the adhesive tape is peeled off at a rate of 300 mm / min in the 180 ° direction. The force is preferably 0.05 to 4.0 N / 25 mm. If it is less than 0.05 N / 25 mm, the end of the pressure-sensitive adhesive tape or pressure-sensitive adhesive sheet coated with the composition of the present invention may float or peel off from the adherend, and if it exceeds 4.0 N / 25 mm, bonding is performed. In some cases, peeling for re-sticking (rework) for correcting the positional displacement may not be possible. Such a value of adhesive strength can be achieved mainly by adjusting the amount of component (b).

  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.

Viscosity The viscosity was measured at 25 ° C. using a BH type rotational viscometer.
Adhesive strength After the silicone adhesive composition was applied 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 was 40 μm, it was heated and cured at 120 ° C. for 10 minutes, An adhesive tape was prepared. This adhesive tape was affixed to a stainless steel plate and pressed by reciprocating a 2 kg roller covered with a rubber layer. After leaving at room temperature for about 20 hours, the force (N / 25 mm) required to peel the adhesive tape from the stainless steel plate at an angle of 180 ° at a speed of 300 mm / min was measured using a tensile tester.

Probe tack The silicone pressure-sensitive adhesive composition was applied to a polyimide film having a thickness of 50 μm using an applicator so that the thickness after curing was 500 μm, and then heated and cured at 120 ° C. for 10 minutes to obtain a pressure-sensitive adhesive sheet. Produced. From this adhesive sheet, an adhesive sheet of about 25 × 25 mm was cut out, and this tack was measured using a Polyken probe tack tester manufactured by Testing Machines. A weight ring with a contact pressure of 20 g / cm ² was used, the probe speed was 1 cm / second, the stop time was 1 second, and the probe diameter was 5 mmφ.

Penetration The adhesive composition was cast so as to fill a glass petri dish with a diameter of 30 mm and a depth of 15 mm, and after defoaming, a cured product that was heat-cured under conditions of 120 ° C. for 30 minutes was used for JIS K2220. It was measured by the method with a 9.4 g load using the indicated 1/4 cone. In the case of using a solvent, the silicone pressure-sensitive adhesive composition solution is cast into a mold that has been subjected to a mold release treatment so that the thickness after curing is about 1.5 mm, and air-dried for about 12 hours to volatilize the solvent. After that, heat curing was performed at 120 ° C. for 30 minutes to prepare a sheet. Measurement was performed in the same manner as described above, using a stack of 10 sheets. It shows that hardened | cured material is flexible, so that a penetration is large, and it shows that hardened | cured material is so hard that penetration is small.

Silicone transfer amount An adhesive sheet was prepared in the same manner as probe tack. This was bonded to a polyester film having a thickness of 23 μm. After leaving at 25 ° C. for 7 days, the adhesive tape was peeled off from the polyester film. The amount of silicon on the polyester film surface was measured with a fluorescent X-ray analyzer, and the amount of silicone transferred to the polyester surface was converted to the amount of polydimethylsiloxane per square meter to obtain the amount of transferred silicone.

Cohesive failure during peeling An adhesive sheet was prepared in the same manner as probe tack. This was bonded to a porous alumina plate. After leaving at 25 ° C. for 7 days, the state of peeling when the adhesive tape was peeled off from the porous alumina plate was observed. When the adhesive layer was coherently broken and remained on the alumina plate, cohesive failure was observed, and when there was no residue, cohesive failure was not observed.

Sampling property The pressure-sensitive adhesive composition was cured in a glass petri dish in the same manner as the penetration. Molecular sieve 4A (1/8 inch pellet, length of about 3 to 8 mm) was laid down to a thickness of about 10 mm, and pressed with a load of about 1 kg for about 2 seconds so that the adhesive in the glass petri dish was in contact therewith. . For those using a solvent, a sheet having a thickness of about 1.5 mm was prepared, and the sheets were cut out into a circle having a diameter of about 30 mm, and 10 sheets were stacked. It was pressed for about 2 seconds with a load of about 1 kg on the molecular sieve 4A laid with the laminated adhesive sheet. Observe the amount of molecular sieve collected on the surface of the adhesive, ◎ when collected over almost the whole surface, ○ when collected over almost the whole surface to about 1/2 part, about half or less part The case where the sample was collected was indicated by Δ, and the case where the sample was hardly collected was indicated by ×.

[Example 1]
Vinyl group-containing polydimethylsiloxane (A-1) (viscosity 30,000 mPa · s) (45 parts) represented by the following average composition formula:
_{ViMe 2 SiO- [Me 2 SiO]} 740 -SiMe 2 Vi (A-1)
Hydroxyl group-containing polydimethylsiloxane (a-1) (viscosity 20,000 mPa · s) (15 parts) represented by the following average composition formula:
_{(HO) Me 2 SiO- [Me} 2 SiO] 610 -SiMe 2 (OH) (a-1)
It contains Me ₃ SiO _1/2 units and SiO ₂ units, the molar ratio of Me ₃ SiO _1/2 units / SiO ₂ units is 0.82, and the content of hydroxyl groups bonded to Si atoms is 1.2 mass. % 60% by weight toluene solution of polyorganosiloxane (b-1) (66.7 parts),
Toluene (6.6 parts)
Were added, aqueous ammonia (0.5 parts) was added, and the mixture was stirred at 25-30 ° C. for 12 hours. After the mixture of ammonia water and toluene was distilled off at 100 to 130 ° C., toluene was distilled off under reduced pressure at 120 ° C.
To this product (100 parts), polyorganohydrosiloxane (C1-1) represented by the following formula (0.18 parts),
_{Me 3 SiO- [Me 2 SiO]} 28 - [HMeSiO] 16 -SiMe 3 (C1-1)
Polydiorganohydrosiloxane (C2-1) represented by the following formula (1.17 parts)
_{HMe 2 SiO- [Me 2 SiO]} 18 -SiMe 2 H (C2-1)
And 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (0.05 parts), a platinum-vinyl group-containing siloxane complex containing 0.5% by mass of platinum. Of silicone solution (0.1 part) was added and mixed to prepare a silicone pressure-sensitive adhesive composition. The silicone adhesive composition was measured for viscosity, adhesive strength, probe tack, penetration, silicone transfer, presence or absence of cohesive failure during peeling, and sample collection. The results are shown in Table 1.

[Example 2]
Vinyl group-containing polydimethylsiloxane (A-1) (37.5 parts),
Hydroxyl group-containing polydimethylsiloxane (a-1) (32.5 parts),
A 60 mass% toluene solution of polyorganosiloxane (b-1) containing Me ₃ SiO _1/2 units and SiO ₂ units and having a molar ratio of Me ₃ SiO _1/2 units / SiO ₂ units of 0.82. 50)
Toluene (13.3 parts)
Were added, aqueous ammonia (0.5 parts) was added, and the mixture was stirred at 25-30 ° C. for 12 hours. After the mixture of ammonia water and toluene was distilled off at 100 to 130 ° C., toluene was distilled off under reduced pressure at 120 ° C.
To this product (100 parts), polyorganohydrosiloxane (C1-1) (0.16 parts), polydiorganohydrosiloxane (C2-1) (1.08 parts), and 1,3,5,7 -Tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (0.05 parts), a platinum-vinyl group-containing siloxane complex silicone solution containing 0.1% by mass of platinum (0.1 parts) Were added and mixed to prepare a silicone pressure-sensitive adhesive composition. The silicone adhesive composition was measured for viscosity, adhesive strength, probe tack, penetration, silicone transfer, presence or absence of cohesive failure during peeling, and sample collection. The results are shown in Table 1.

[Example 3]
Vinyl group-containing polydimethylsiloxane (A-1) (30 parts),
Hydroxyl group-containing polydimethylsiloxane (a-1) (40 parts),
A 60 mass% toluene solution of polyorganosiloxane (b-1) containing Me ₃ SiO _1/2 units and SiO ₂ units and having a molar ratio of Me ₃ SiO _1/2 units / SiO ₂ units of 0.82. 50)
Toluene (13.3 parts)
Were added, aqueous ammonia (0.5 parts) was added, and the mixture was stirred at 25-30 ° C. for 12 hours. After the mixture of ammonia water and toluene was distilled off at 100 to 130 ° C., toluene was distilled off under reduced pressure at 120 ° C.
To this product (100 parts), polyorganohydrosiloxane (C1-1) (0.20 parts), polydiorganohydrosiloxane (C2-1) (0.63 parts), and 1,3,5,7 -Tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (0.05 parts), a platinum-vinyl group-containing siloxane complex silicone solution containing 0.1% by mass of platinum (0.1 parts) Were added and mixed to prepare a silicone pressure-sensitive adhesive composition. The silicone adhesive composition was measured for viscosity, adhesive strength, probe tack, penetration, silicone transfer, presence or absence of cohesive failure during peeling, and sample collection. The results are shown in Table 1.

[Example 4]
Vinyl group-containing polydimethylsiloxane (A-2) (viscosity 1,000 mPa · s) (30 parts) represented by the following average composition formula:
_{ViMe 2 SiO- [Me 2 SiO]} 220 -SiMe 2 Vi (A-2)
Hydroxyl group-containing polydimethylsiloxane (a-2) (viscosity 100,000 mPa · s) (40 parts) represented by the following average composition formula:
_{(HO) Me 2 SiO- [Me} 2 SiO] 1080 -SiMe 2 (OH) (a-2)
A 60 mass% toluene solution of polyorganosiloxane (b-1) containing Me ₃ SiO _1/2 units and SiO ₂ units and having a molar ratio of Me ₃ SiO _1/2 units / SiO ₂ units of 0.82. 50)
Toluene (13.3 parts)
Were added, aqueous ammonia (0.5 parts) was added, and the mixture was stirred at 25-30 ° C. for 12 hours. After the mixture of ammonia water and toluene was distilled off at 100 to 130 ° C., toluene was distilled off under reduced pressure at 120 ° C.
To this product (100 parts), polyorganohydrosiloxane (C1-1) (0.39 parts), polydiorganohydrosiloxane (C2-1) (2.61 parts), and 1,3,5,7 -Tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (0.05 parts), a platinum-vinyl group-containing siloxane complex silicone solution containing 0.1% by mass of platinum (0.1 parts) Were added and mixed to prepare a silicone pressure-sensitive adhesive composition. The silicone adhesive composition was measured for viscosity, adhesive strength, probe tack, penetration, silicone transfer, presence or absence of cohesive failure during peeling, and sample collection. The results are shown in Table 1.

[Comparative Example 1]
Vinyl group-containing polydimethylsiloxane (A-2) (100 parts),
Polyorganohydrosiloxane (C1-1) (0.05 parts),
Polyorganohydrosiloxane (C2-1) (6.5 parts),
Polyorganohydrosiloxane (C3-1) (3.5 parts) represented by the following formula:
Me ₃ SiO— [Me ₂ SiO] ₂₇ — [HMeSiO] ₂ —SiMe ₃ (C3-1)
Silicone solution of 1,3,5,7-vinyl-1,3,5,7-cyclotetrasiloxane (0.01 part) and a platinum-vinyl group-containing siloxane complex containing 0.5% by mass of platinum (0 .1 part) was added and mixed to prepare a silicone pressure-sensitive adhesive composition. The silicone adhesive composition was measured for viscosity, adhesive strength, probe tack, penetration, silicone transfer, presence or absence of cohesive failure during peeling, and sample collection. The results are shown in Table 1.

[Comparative Example 2]
Raw rubber-like vinyl group-containing polydimethylsiloxane represented by the following average composition formula (vinyl group content is 0.075 mol% of all siloxane units) (A-3) (25 parts),
ViMe ₂ SiO- [MeViSiO] _1.5- [Me ₂ SiO] ₄₅₀₀ -SiMe ₂ Vi
(A-3)
Raw rubber-like hydroxyl group-containing polydimethylsiloxane (a-3) (25 parts) represented by the following average composition formula:
_{(HO) Me 2 SiO- [Me} 2 SiO] 4400 -SiMe 2 (OH) (a-3)
It contains Me ₃ SiO _1/2 units and SiO ₂ units, the molar ratio of Me ₃ SiO _1/2 units / SiO ₂ units is 0.74, and the content of hydroxyl groups bonded to Si atoms is 1.4% by mass. A 60 mass% toluene solution (83.3 parts) of polyorganosiloxane (b-2),
Toluene (33.4 parts)
Were added, aqueous ammonia (0.5 parts) was added, and the mixture was stirred at 25-30 ° C. for 12 hours. After the mixture of aqueous ammonia and toluene was distilled off at 100 to 110 ° C., toluene was added so that the concentration of siloxane was 40% by mass.
(In addition, what distilled toluene under reduced pressure at 120 ° C. became a solid having no fluidity at 25 ° C., and could not be applied, cured or molded in a solventless type.)
To this product (250 parts), polyorganohydrosiloxane (C1-2) (0.24 parts) represented by the following formula,
Me ₃ SiO— [HMeSiO] ₄₀ —SiMe ₃ (C1-2)
Then, ethynylcyclohexanol (0.16 parts) and a platinum-vinyl group-containing siloxane complex silicone solution (0.5 parts) containing 0.5% by mass of platinum are added and mixed to obtain a silicone pressure-sensitive adhesive composition. Prepared. The silicone adhesive composition was measured for viscosity, adhesive strength, probe tack, penetration, silicone transfer, presence or absence of cohesive failure during peeling, and sample collection. The results are shown in Table 1.

[Comparative Example 3]
A raw rubber-like polydimethylsiloxane (A-4) (7.2 parts) having both ends vinyl groups represented by the following average composition formula:
ViMe ₂ SiO- [Me ₂ SiO] ₄₄₀₀ -SiMe ₂ Vi (A-4)
Hydroxyl group-containing polydimethylsiloxane (a-3) (23.7 parts),
It contains Me ₃ SiO _1/2 units and SiO ₂ units, the molar ratio of Me ₃ SiO _1/2 units / SiO ₂ units is 0.8, and the content of hydroxyl groups bonded to Si atoms is 2.1% by mass. Containing 60 wt% toluene solution (104.2 parts) of polyorganosiloxane (b-3), Me ₃ SiO _1/2 units and SiO ₂ units, Me ₃ SiO _1/2 units / SiO ₂ units A 60 mass% toluene solution (7.7 parts) of polyorganosiloxane (b-4) having a molar ratio of 0.82 and a content of hydroxyl groups bonded to Si atoms of 0.5 mass%, toluene (20. 5 parts) was mixed, aqueous ammonia (0.5 parts) was added, and the mixture was stirred at 25-30 ° C. for 12 hours. After the mixture of aqueous ammonia and toluene was distilled off at 100 to 110 ° C., toluene was added so that the concentration of siloxane was 40% by mass.
(In addition, what distilled toluene under reduced pressure at 120 ° C. was a solid having no fluidity at 25 ° C.)
To this product (250 parts), polyorganohydrosiloxane (C1-2) (0.2 part) represented by the following formula, ethynylcyclohexanol (0.16 part), and platinum content of 0.5% by mass A silicone solution (0.5 part) of the contained platinum-vinyl group-containing siloxane complex was added and mixed to prepare a silicone pressure-sensitive adhesive composition. The silicone adhesive composition was measured for viscosity, adhesive strength, probe tack, penetration, silicone transfer, presence or absence of cohesive failure during peeling, and sample collection. The results are shown in Table 1.

[Comparative Example 4]
Vinyl group-containing polydimethylsiloxane (A-1) (45 parts),
Hydroxyl group-containing polydimethylsiloxane (a-1) (15 parts),
It contains Me ₃ SiO _1/2 units and SiO ₂ units, the molar ratio of Me ₃ SiO _1/2 units / SiO ₂ units is 0.82, and the content of hydroxyl groups bonded to Si atoms is 2.2 mass. % 60% by weight toluene solution of polyorganosiloxane (b-3) (66.7 parts),
Toluene (6.5 parts)
Were added, aqueous ammonia (0.5 parts) was added, and the mixture was stirred at 25-30 ° C. for 12 hours. After the mixture of ammonia water and toluene was distilled off at 100 to 130 ° C., toluene was distilled off under reduced pressure at 120 ° C.
To this product (100 parts), polyorganohydrosiloxane (C1-1) (0.18 parts), polydiorganohydrosiloxane (C2-1) (1.17 parts), and 1,3,5,7 -Tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (0.05 parts), a platinum-vinyl group-containing siloxane complex silicone solution containing 0.1% by mass of platinum (0.1 parts) Were added and mixed to prepare a silicone pressure-sensitive adhesive composition. The silicone adhesive composition was measured for viscosity, adhesive strength, probe tack, penetration, silicone transfer, presence or absence of cohesive failure during peeling, and sample collection. The results are shown in Table 1.

[Comparative Example 5]
Vinyl group-containing polydimethylsiloxane (A-1) (37.5 parts),
Hydroxyl group-containing polydimethylsiloxane (a-1) (32.5 parts),
A 60 mass% toluene solution of polyorganosiloxane (b-1) containing Me ₃ SiO _1/2 units and SiO ₂ units and having a molar ratio of Me ₃ SiO _1/2 units / SiO ₂ units of 0.82. 50)
Toluene (13.3 parts)
The toluene was distilled off at 100 to 130 ° C., and then the toluene was distilled off at 120 ° C. under reduced pressure. Accordingly, the components (a-1) and (b-1) are not substantially condensed.
To this product (100 parts), polyorganohydrosiloxane (C1-1) (0.16 parts), polydiorganohydrosiloxane (C2-1) (1.08 parts), and 1,3,5,7 -Tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (0.05 parts), a platinum-vinyl group-containing siloxane complex silicone solution containing 0.1% by mass of platinum (0.1 parts) Were added and mixed to prepare a silicone pressure-sensitive adhesive composition. The silicone adhesive composition was measured for viscosity, adhesive strength, probe tack, penetration, silicone transfer, presence or absence of cohesive failure during peeling, and sample collection. The results are shown in Table 1.

[Comparative Example 6]
The viscosity, penetration, presence / absence of cohesive failure at the time of peeling, and sample collection property of a commercially available vacuum silicone grease (trade name HIVAC-G, manufactured by Shin-Etsu Chemical Co., Ltd.) were measured. The results are shown in Table 1. This vacuum silicone grease is an oil compound obtained by kneading dimethylpolysiloxane whose end is blocked with a methyl group and fine powder silica whose surface is treated with silicone. Since the silicone grease for vacuum could not be cured and was a paste with no fluidity, measurements of adhesion, probe tack, and silicone migration were not performed. For cohesive failure during peeling, a vacuum silicone grease was applied to a polyimide film having a thickness of 50 μm with a spatula so as to have a thickness of about 1 mm to produce a sheet.

＊１ 溶剤を除去すると流動性のない固体となり、無溶剤型で塗工硬化することができなかった。
＊２ 流動性のないペースト状で粘度を測定できなかった。
＊３ ＢＭ型回転粘度計を用いた。

* 1 When the solvent was removed, it became a solid with no fluidity and could not be applied and cured without solvent.
* 2 Viscosity could not be measured in a paste with no fluidity.
* 3 A BM type rotational viscometer was used.

Claims (6)

A silicone adhesive article for outer space characterized by curing a solvent-free addition-type silicone adhesive composition containing the following components (A) to (D).
(A) a polydiorganosiloxane having at least two alkenyl group-containing organic groups in one molecule represented by the following general formula (1):
_{X b R 3-b SiO- [} R 2 SiO] a -SiX b R 3-b (1)
(Wherein X is an alkenyl group-containing organic group having 2 to 10 carbon atoms, R is a monovalent hydrocarbon group having 1 to 10 carbon atoms which may be the same or different. A is an integer and 50 ≦ a ≦ 2,000, and b is an integer of 1 to 3.)
(B) a condensation reaction product obtained by condensing the SiOR ² group of the component (a) and the SiOH group of the component (b) shown below,
(A) a polydiorganosiloxane having a hydroxyl group or an alkoxy group at both ends of a molecular chain, represented by the following general formula (2):
(R ² O) R ¹ ₂ SiO— [R ¹ ₂ SiO] _c —SiR ¹ ₂ (OR ² ) (2)
(Wherein, R ¹ is a monovalent hydrocarbon group having same or different carbon atoms and optionally 1 to 10, .R ² containing no alkenyl group-containing organic group is a hydrogen atom or R ^1, c is an integer And 50 ≦ c ≦ 2,000.)
(B) containing R ¹ ₃ SiO _1/2 units, SiO ₂ units, and siloxane units having a hydroxyl group bonded to a silicon atom, wherein the molar ratio of R ¹ ₃ SiO _1/2 units / SiO ₂ units is 0.6. A polyorganosiloxane having a hydroxyl group content of 0.1% by mass or more and less than 1.8% by mass (R ¹ is the same as described above),
(However, (A) component is 10-60 mass parts with respect to a total of 100 mass parts of (A), (a), (b) component, and (a) component is 5-60 mass parts, (B) A component is 5-60 mass parts.)
(C1) a polyorganohydrosiloxane having at least 3 SiH groups in one molecule,
(C2) a polydiorganohydrosiloxane having SiH groups at both ends represented by the following general formula (3):
HR ¹ ₂ SiO— [R ¹ ₂ SiO] _d —SiR ¹ ₂ H (3)
(R ¹ is the same as above, d is an integer, and 5 ≦ d ≦ 500.)
(However, the ratio of the number of moles of the SiH group of the (C1) component to the alkenyl group of the (A) component is 0.2 to 10, and the ratio of the number of moles of the SiH group of the (C2) component is 0.2 to 3 .)
(D) Platinum group metal catalyst (1 to 500 ppm on a mass basis with respect to the total of components (A), (a), and (b) as platinum group metal components).   The silicone pressure-sensitive adhesive article for outer space according to claim 1, wherein the viscosity of the silicone pressure-sensitive adhesive composition at 25 ° C is 5,000 to 500,000 mPa · s. On a pressure-sensitive adhesive sheet provided with a pressure-sensitive adhesive layer of a silicone pressure-sensitive adhesive composition on a polyimide film having a thickness of 50 μm and a thickness of 0.5 mm, a probe with a smooth tip of 5 mm in diameter is contacted at a speed of 1 cm / sec and a contact pressure of 20 g / cm. ^3. The universe according to claim 1 or 2, wherein the probe tack obtained by pressing the probe vertically so as to be ² and measuring the force when the probe is separated after 1 second of the stop time is 50 to 500 gf. Silicone adhesive article for space.   A 25 mm wide adhesive tape provided with an adhesive layer of a silicone adhesive composition so as to have a thickness of 40 μm on a 25 μm thick polyimide film was bonded to a stainless steel plate, and this adhesive tape was fastened at a speed of 300 mm / min in the 180 ° direction. The silicone pressure-sensitive adhesive article for outer space according to any one of claims 1 to 3, wherein the adhesive strength when peeled off is 0.05 to 4.0 N / 25 mm.   The silicone adhesive article for outer space according to any one of claims 1 to 4, which is used for sampling a surface sample of a solar system small body, a solid planet, or a solid satellite.   Using the silicone adhesive article for outer space according to any one of claims 1 to 4, which is coated, cured or molded so as to have a thickness of 0.1 to 30 mm, a solar system celestial body such as an asteroid or comet, A method for collecting surface samples of solid planets such as Mercury or solid satellites such as the Moon.