JP7021775B2 - Laminated sheet for forming septum for sealing the opening of the headspace vial, its manufacturing method, septum and septum for sealing the opening of the headspace vial - Google Patents

Description

The present invention relates to a laminated sheet for manufacturing a polyimide vial for sealing an opening of a vial used in a headspace vial, that is, a headspace GC method or a headspace GC-MS method, a method for manufacturing the same, and an opening of a headspace vial. The present invention relates to a septum composed of a laminated sheet in which an aromatic polyimide film and a silicone rubber layer are laminated for sealing.

In the headspace GC method (gas chromatography using the headspace method for sampling) and the headspace GC-MS method (gas chromatography mass analysis method using the headspace method for sampling), the liquid sample is heated and the gas phase is used. It is useful for the analysis of volatile components expelled from the chromatograph and the analysis of volatile components generated by heating a solid sample, and has been widely used in recent years.

In the headspace GC method (headspace gas chromatography analysis method), a liquid sample or a solid sample is placed in a vial (sample bottle), sealed with a septum and a cap, and kept at a constant temperature (eg, 180 to 210 ° C.) for a certain period of time. After heating (about 30 to 60 minutes), insert the needle of a gas tight syringe into the septum, suck the gas phase (head space) containing the volatile components in the vial, or expel it with purge gas, and use it to expel the column of the gas chromatograph. It is an analytical method that is injected into the gas, separated and detected, identified and quantified. For high boiling point compounds, vials containing liquid or solid samples are heated at a maximum of 300 ° C.
In a conventional vial (sample bottle), for example, a disc-shaped septum made of silicone rubber is crimped and fastened to the mouth of a glass bottle with an aluminum clamp to enclose the sample. A vial (sample bottle) containing a sample is heated to a predetermined temperature for analysis, a pressurized gas is introduced into the vial through a needle (not shown) pierced by a septum, and the pressure is used in the vial. The gas in the upper space (head space gas) is taken out and introduced into the column of the gas chromatograph for analysis.

The headspace GC-MS method (headspace gas chromatography mass spectrometry) is an analysis that qualifies and quantifies components from mass information by using a mass spectrometer to detect components separated by gas chromatography (GC). It is a method.

Patent Document 1 (Japanese Patent Laid-Open No. 2012-73108) describes a collection container used for collecting volatile oils during identification activities, in which a bottle having an open upper surface and a bottle having the opening are sealed and a hole is formed in the upper surface. It is characterized by having a cap having a portion and the hole portion sealed with a partition member that can be pierced by a sampling needle, and an adsorbent that adsorbs the volatile oils and can be taken in and out of the bottle. The collection container to be collected is described in claim 1, and it is described in claims 2 and 3 that the bottle is a headspace vial and the partition wall member is a septum.

In the paragraph [0030] of the detailed description of the invention of Patent Document 1, "The bottle 1 may be a headspace vial that can be analyzed by a gas chromatograph mass spectrometer with a headspace sampler. In this case, the cap 2 is a top surface. A hole portion 21 penetrating the wall and a partition wall member 22 for sealing the hole portion 21 are provided. The partition wall member 22 is a rubber-like member capable of piercing a sampling needle, and even if it is attached to the cap 2. It may be configured as a separate body, or it may be configured as a separate body. ”In paragraph [0041],“ Cap 2 is a metal screw cap with a septum, having a diameter of 18 mm, a height of cap 2 of 10 mm, and a hole. The portion 21 has a diameter of 8 mm and has a partition member 22 made of blue silicon / white polytetrafluoroethylene (PTFE). "

Patent Document 2 (Japanese Unexamined Patent Publication No. 9-325100) describes that the sample bottle for analysis includes, for example, a septum made of a silicone resin coated with polytetrafluoroethylene.
Patent Document 3 (Japanese Patent Laid-Open No. 2011-106869) describes that the sample container used for headspace gas analysis includes a PTFE-coated silicone rubber septum to seal the container.

In Patent Document 4 (Japanese Patent Laid-Open No. 2012-528540), "a first layer containing a silicone-based polymer which is a polyalkyl siloxane, a hydride-containing siloxane, and a platinum catalyst, wherein the hydride-containing siloxane is the silicone-based polymer. In an article comprising a first layer present at about 0.1% by weight to about 5.0% by weight of; a second layer containing a fluoropolymer (eg, polytetrafluoroethylene, fluorinated ethylenepropylene copolymer). An article in which the first layer has a peel strength of at least about 10.0 ppi with respect to the second layer and a peel strength of about 7.0 ppi or less with respect to a metal ”(. 6) The method for producing the article by heating the article at about 125 ° C. to about 200 ° C. is described in claim 36 and the like, and the article may be used as an analytical septam used for a cap. (Paragraph [0021]). In Example 1, the first layer comprises a silicone-based polymer which is a vinyl group-containing polyalkylsiloxane, a hydride-containing polyalkylsiloxane, a platinum catalyst and a silica filler.

Patent Document 5 (WO2016 / 067627A1) describes a fluororesin film having a reactive functional group by surface treatment and an organic peroxide-containing mirabable type silicone rubber having a sheet-like half-life temperature in the range of 100 to 150 ° C. A method for producing a laminated sheet composed of a fluororesin film and a silicone rubber sheet, which comprises superimposing the compositions and heating the silicone rubber composition to 90 ° C. to 135 ° C. under pressure to cure the silicone rubber composition. The fluororesin film and the silicone rubber sheet are adhered to each other, and the peeling adhesive strength based on JIS K6854-2 (adhesive-peeling adhesive strength test method-Part 2: 180 degree peeling) is 3N or more, 120 mm. The four corners of the corner laminated sheet are not curved to the shape of one end of a semi-arc or the shape of one end of a C-shape, and the average warpage value of the four corners is 35 mm or less. The sheet is disclosed.

On the other hand, in <Example 7> of Patent Document 6 (Japanese Patent Laid-Open No. 2004-51099), "Liquid high thermal conductive silicone B is coated on a polyimide film and heated in a first heating furnace at 90 ° C. for 1 minute for half. The mat-like PET film on the surface of this semi-cured high thermal conductive liquid silicone B is pressure-bonded with a pressure-bonding roll, and heat-cured at 90 ° C. for 1 minute in a second heating furnace to cure the mat-like PET film. Was peeled off, and the surface shape of the matte PET film was transferred to obtain a multi-layered body of silicone rubber and a polyimide film having excellent thermal conductivity with a matte treatment on the surface. The total thickness of the multi-layered body was 250 μm. It was. "

Japanese Unexamined Patent Publication No. 2012-73108 Japanese Unexamined Patent Publication No. 9-325100 Japanese Unexamined Patent Publication No. 2011-106869 Special Table 2012-592540 Gazette WO2016 / 067627A1 Japanese Unexamined Patent Publication No. 2004-51099

However, the blue silicon / white polytetrafluoroethylene (PTFE) partition wall member disclosed in Patent Document 1 has a problem that it is easily peeled off between silicon and polytetrafluoroethylene.
Further, when the opening of the vial is sealed with the septum and heated at a high temperature (eg, 300 ° C.), the cyclic organosiloxane oligomer vapor generated from the silicone resin or silicone rubber permeates and mixes with the vapor generated from the analysis sample. There is a problem that the analysis accuracy is lowered.

The silicone resin septum coated with polytetrafluoroethylene disclosed in Patent Document 2 and the PTFE-coated silicon rubber septum disclosed in Patent Document 3 include polytetrafluoroethylene and PTFE (. Polytetrafluoroethylene) has a problem that it is easily peeled off from silicone resin or silicone rubber.
Further, the septum has a problem that the polytetrafluoroethylene membrane and the PTFE (polytetrafluoroethylene) membrane are easily torn when a sampling needle for collecting an analytical sample is inserted and pulled out.
Further, when the opening of the vial is sealed with the septum and heated at a high temperature (eg, 300 ° C.), the cyclic organosiloxane oligomer vapor generated from the silicone resin or silicone rubber permeates and mixes with the vapor generated from the analysis sample. There is a problem that the analysis accuracy is lowered.

Even if the adhesiveness between the first layer containing the silicone rubber and the second layer containing the fluoropolymer disclosed in Patent Document 4 is good, the first layer containing the silicone rubber contains the fluoropolymer. It shrinks more than the second layer, causing the laminated sheet to warp, that is, to curl. Therefore, there is a problem that it is difficult to punch out into a circular shape at the time of manufacturing a septum.

The laminated sheet disclosed in Patent Document 5 has a problem that it requires a special film called a fluororesin film having a reactive functional group by surface treatment.

In the manufacturing method described in <Example 7> of Patent Document 6, since the material is heat-cured in a state of being crimped with a crimping roll, it inevitably becomes a laminated body curled into a cylindrical shape. Therefore, there is a problem that it is difficult to punch out into a circular shape at the time of manufacturing a septum.

The present invention has been made in view of the above problems, and it is easy to punch a laminated sheet into a predetermined shape such as a disk shape at the time of manufacturing a septum, and the film does not peel off from the silicone rubber layer during the work, and the head As a septum that seals the opening of the vial for space gas chromatograph analysis or headspace gas chromatograph mass spectrometry, even if a sampling needle for analytical sampling is inserted and pressurized purged with inert gas. Cyclic organosiloxane oligomer vapor even when the opening of the vial is sealed and heated at high temperature (eg, 300 ° C.) as a septum for headspace gas chromatograph analysis or headspace gas chromatograph mass spectrometry without gas leakage. It is an object of the present invention to provide a laminated sheet in which an aromatic polyimide film and a silicone rubber layer are laminated in an bonded state so that the amount of generation is very small and the analysis accuracy is not deteriorated.

In particular, an aromatic polyimide film and a silicone rubber layer, which are suitable for producing a septum for sealing an opening of a vial for headspace gas chromatograph analysis or headspace gas chromatograph mass spectrometry, are adhered and laminated. It is an object of the present invention to provide a laminated sheet.

Further, it is an object of the present invention to provide a method for manufacturing a laminated sheet in which such an aromatic polyimide film and a silicone rubber layer are adhered and laminated.

Furthermore, it is an object of the present invention to provide a septum suitable for sealing an opening of a vial for headspace gas chromatography or a vial for headspace gas chromatography.

Furthermore, it is composed of a laminated sheet in which an aromatic polyimide film and a silicone rubber layer are laminated, and an object thereof is to provide a septum that does not reduce the analysis accuracy when used for gas chromatograph analysis or gas chromatograph-mass spectrometry. ..

The purpose is
"[1]
An aromatic polyimide film having a thickness of 10 to 200 μm and a thickness in a laminated sheet for producing a septum for sealing an opening of a vial for headspace gas chromatograph analysis or headspace gas chromatograph mass analysis. Is 1.2 to 5 mm, the content of cyclic dimethylsiloxane tetramer to 15 mer is 250 mass ppm or less, and (A) fumed silica as a reinforcing filler is contained, and in JIS K 6249. The hydrosilylation reaction cured silicone rubber layer (I) having a specified elongation of 380% or more and a tensile stress at 100% elongation of 0.20 to 1.35 MPa , or a thickness of 1.2 to 5 mm. The content of cyclic dimethylsiloxane tetramer to 15-mer is 250% by mass or less, and (A) fumed silica as a reinforcing filler and (B) organic functional organoalkoxysilane or a partial hydrolysis condensation thereof. The hydrosilylation reaction-cured silicone rubber layer (II) containing a substance, having an elongation of 380% or more specified by JIS K 6249, and having a tensile stress at 100% elongation of 0.20 to 1.35 MPa . It is laminated in a bonded state, and the peeling adhesive strength based on JIS K6854-2 (adhesive-peeling adhesive strength test method-Part 2: 180 degree peeling) is 4N / 20 mm or more, length 120 mm, width 120 mm. The square laminated sheet test piece is a laminated sheet characterized in that the average warpage value of the four corners is 35 mm or less.

[1-1]
The components (B) are (a) an alkenyl-functional organoalkoxysilane having two or three silicon atom-bonded alkoxy groups in one molecule and (b) two or three silicon atom-bonded alkoxy groups in one molecule. One to three selected from the group consisting of (meth) acrylic functional organoalkoxysilanes and (c) epoxy functional organoalkoxysilanes having two or three silicon atom-bonded alkoxy groups in one molecule. An organic-functional organoalkoxysilane, or a co-partial hydrolysis condensate of the organic-functional organoalkoxysilane and (d) an organic titanium compound catalyst, or two or three organic-functional organoalkoxysilanes. 1] The laminated sheet.
[1-2]
The laminated sheet according to [1] or [1-1], wherein the component (B) is contained in the hydrosilylation reaction-cured silicone rubber layer in an amount of 0.03 to 6% by mass.
[1-3]
(A) The laminated sheet according to [1], [1-1] or [1-2], which contains 10 to 24% by mass of fumed silica in the hydrosilylation reaction-cured silicone rubber layer.
[1-4]
The hydrosilylation reaction-curable silicone rubber layer is a cured product of a hydrosilylation reaction-curable silicone rubber composition containing both-terminal trimethylsiloxy group-blocking dimethylsiloxane / methylhydrogensiloxane copolymer as a cross-linking agent. The laminated sheet according to [1], [1-1], [1-2] or [1-3].
[1-5]
The hydrosilylation reaction-cured silicone rubber layer contains a methylhydrogenpolysiloxane having at least three hydrosilyl groups and a dimethylpolysiloxane (polymerization degree 10 or less) in which both ends of the molecular chain are sealed with a hydrodimethylsiloxy group. The laminated sheet according to [1], [1-1], [1-2] or [1-3], which is a cured product of a chemical reaction-curable silicone rubber composition.

[2]
The aromatic polyimide film having a thickness of 10 to 200 μm and the cyclic dimethylsiloxane tetramer to 15-mer have a content of 250 mass ppm or less, and contain (A) fumed silica as a reinforcing filler. A heat-curable liquid silicone rubber composition (I) by a hydrosilylation reaction in which the elongation specified by JIS K 6249 of the cured product is 380% or more and the tensile stress at 100% elongation is 0.20 to 1.35 MPa. Or , the content of the cyclic dimethylsiloxane tetramer to 15-mer is 250% by mass or less, and (A) fumed silica as a reinforcing filler and (B) organic functional organoalkoxysilane or its partial water addition. A heat-curable liquid by hydrosilylation reaction containing a decomposition condensate, the elongation of the cured product specified by JIS K 6249 is 380% or more, and the tensile stress at 100% elongation is 0.20 to 1.35 MPa. Opening of vials for headspace gas chromatograph analysis or headspace gas chromatograph mass analysis, characterized in that the silicone rubber composition (II) is brought into close contact with the silicone rubber composition (II) and heated at 145 ° C. or lower under pressure to cure. A laminated sheet for forming a septum for partial encapsulation, which is a polyimide film having a thickness of 10 to 200 μm and a heat-curable liquid silicone having a thickness of 1.2 to 5 mm by the hydrosilylation reaction. A cured product of the silicone rubber layer (I), which is a cured product of the rubber composition (I), or a cured product of the heat-curable liquid silicone rubber composition (II), which has a thickness of 1.2 to 5 mm and is heat-curable by the hydrosilylation reaction. The silicone rubber layer (II) is laminated in a bonded state, and the peeling adhesive strength based on JIS K6854-2 (adhesive-peeling adhesive strength test method-Part 2: 180 degree peeling) is 4N . A method for manufacturing a laminated sheet in which a square laminated sheet test piece having a length of 120 mm and a width of 120 mm has an average warp value of 35 mm or less at four corners of 20 mm or more.

[2-1]
The components (B) are (a) an alkenyl functional organoalkoxysilane having two or three silicon atom-bonded alkoxy groups in one molecule and (b) two or three silicon atom-bonded alkoxy groups in one molecule. One to three selected from the group consisting of (meth) acrylic functional organoalkoxysilanes and (c) epoxy functional organoalkoxysilanes having two or three silicon atom-bonded alkoxy groups in one molecule. An organic-functional organoalkoxysilane, or a co-partial hydrolysis condensate of the organic-functional organoalkoxysilane and (d) an organic titanium compound catalyst, or two or three organic-functional organoalkoxysilanes. 2] The method for manufacturing a laminated sheet.
[2-2]
In [2] or [2-1], the component (B) is contained in the hydrosilylation reaction heat-curable liquid silicone rubber composition and the hydrosilylation reaction-curable silicone rubber layer in an amount of 0.03 to 6% by mass. The method for manufacturing a laminated sea according to the description.
[2-3]
[2], [2-1] or [2], [2-1] or that the fumed silica is contained in the hydrosilylation reaction heat-curable liquid silicone rubber composition and the hydrosilylation reaction-curable silicone rubber layer in an amount of 10 to 24% by mass. The method for manufacturing a laminated sheet according to [2-2].
[2-4]
The hydrosilylation reaction-curable silicone rubber layer is a cured product of a hydrosilylation reaction-curable silicone rubber composition containing both-terminal trimethylsiloxy group-blocking dimethylsiloxane / methylhydrogensiloxane copolymer as a cross-linking agent. The method for producing a laminated sheet according to [2], [2-1], [2-2] or [2-3].
[2-5]
The heat-curable liquid silicone rubber composition obtained by the hydrosilylation reaction is a methylhydrogenpolysiloxane having at least three hydrosilyl groups as a cross-linking agent and a dimethylpolysiloxane having both ends of the molecular chain sealed with a hydrodimethylsiloxy group (polymerization). The method for producing a laminated sheet according to [2], [2-1], [2-2] or [2-3], which comprises (degree 10 or less).

[3]
It is an aromatic polyimide film having a thickness of 10 to 200 μm, a hydrosilylation reaction-cured silicone rubber, a thickness of 1.2 to 5 mm, and a content of cyclic dimethylsiloxane tetramer to 15-mer of 250 mass. It is ppm or less, contains (A) fumed silica as a reinforcing filler, has an elongation of 380% or more specified by JIS K 6249, and has a tensile stress of 0.20 to 1.35 MPa at 100% elongation. The content of cyclic dimethylsiloxane tetramer to 15-mer is 250% by mass or less, and (B) organic functional organoalkoxysilane or a partially hydrolyzed condensate thereof is contained between the silicone rubber sheet and the silicone rubber sheet. Heat-curable liquid silicone rubber composition by hydrosilylation reaction containing (A) fumed silica as a reinforcing filler A heat-curable liquid silicone rubber composition by heat-curable liquid silicone rubber composition by heating under pressure with a thin layer interposed therebetween. The polyimide film and the hydrosilyl for forming a septum for sealing the opening of a vial for headspace gas chromatograph analysis or headspace gas chromatograph mass analysis, which comprises curing a thin layer. A method for manufacturing a laminated sheet in which a chemical reaction-cured silicone rubber sheet is laminated in an adhered state, and a square laminated sheet test piece having a length of 120 mm and a width of 120 mm has an average warp value of 35 mm or less at four corners .
[4]
The components (B) are (a) an alkenyl functional organoalkoxysilane having two or three silicon atom-bonded alkoxy groups in one molecule and (b) two or three silicon atom-bonded alkoxy groups in one molecule. One to three selected from the group consisting of (meth) acrylic functional organoalkoxysilanes and (c) epoxy functional organoalkoxysilanes having two or three silicon atom-bonded alkoxy groups in one molecule. An organic-functional organoalkoxysilane, or a co-partial hydrolysis condensate of the organic-functional organoalkoxysilane and (d) an organic titanium compound catalyst, or two or three organic-functional organoalkoxysilanes. 3] The method for manufacturing a laminated sheet.
[4-1]
The method for producing a laminated sheet according to [3] or [4], wherein the component (B) is contained in a thin layer of a heat-curable liquid silicone rubber composition by the liquid hydrosilylation reaction in an amount of 0.1 to 6% by mass.
[4-2]
(A) The method for producing a laminated sheet according to [3], [4] or [4-1], wherein the hydrosilylation reaction-cured silicone rubber sheet contains 10 to 24% by mass of fumed silica.

[5]
An aromatic polyimide film having a thickness of 10 to 200 μm, and (A) fumed silica and (B) as a reinforcing filler having a content of cyclic dimethylsiloxane tetramer to 15-mer of more than 250 mass ppm. It contains organic functional organoalkoxysilane or a partially hydrolyzed condensate thereof , the elongation of the cured product specified by JIS K 6249 is 250% or more, and the tensile stress at 100% elongation specified by JIS K 6249 is 0. It is brought into close contact with a heat-curable silicone gel composition by a hydrosilylation reaction at 1 to 0.49 MPa and heated at 90 ° C. or higher and 240 ° C. or lower under pressure to primary cure the silicone gel composition, and then hot air. For headspace gas chromatograph analysis method or headspace gas chromatograph mass analysis, which comprises placing in it until the content of cyclic dimethylsiloxane tetramer to 15-mer is 250 mass ppm or less and performing secondary curing. A laminated sheet for forming a septum for sealing the opening of a legal vial, which is an aromatic polyimide film having a thickness of 10 to 200 μm and a cyclic dimethylsiloxane having a thickness of 1.2 to 5 mm. The content of tetramer to 15-mer is 250 mass ppm or less, and contains (A) fumed silica as a reinforcing filler and (B) organic functional organoalkoxysilane or a partially hydrolyzed condensate thereof. , The elongation of the cured product specified by JIS K 6249 is 250% or more, and the tensile stress at 100% elongation specified by JIS K 6249 is 0.15 to 0.49 MPa. A method for manufacturing a laminated sheet in which a square laminated sheet test piece having a length of 120 mm and a width of 120 mm is laminated in a bonded state and the average warpage value of the four corners is 35 mm or less.
[5-1]
[5] or [6], wherein the component (B) is contained in the hydrosilylation reaction heat-curable silicone gel composition and the hydrosilylation reaction-curable silicone gel layer in an amount of 0.03 to 6% by mass. A method for manufacturing a laminated sheet.
[5-2]
[5] or [5-1] containing (A) fumed silica in an amount of 10 to 24% by mass in the hydrosilylation reaction-curable silicone gel composition and the hydrosilylation reaction-curable silicone rubber layer. The method for manufacturing a laminated sheet according to the description.

[6]
An aromatic polyimide film having a thickness of 10 to 200 μm, a cyclic dimethylsiloxane tetramer to 15-mer having a content of more than 250 mass ppm, and containing (A) fumed silica as a reinforcing filler . A heat-curable liquid silicone rubber composition (I) or reinforcement by a hydrosilylation reaction in which the elongation specified by JIS K 6249 is 380% or more and the tensile stress at 100% elongation is 0.20 to 1.35 MPa. It contains (A) fumed silica as a sex filler and (B) organic functional organoalkoxysilane or a partially hydrolyzed condensate thereof, and the elongation specified by JIS K 6249 is 380% or more, and at 100% elongation. The silicone rubber is brought into close contact with the heat-curable liquid silicone rubber composition (II) by a hydrosilylation reaction having a tensile stress of 0.20 to 1.35 MPa and heated at 90 ° C. or higher and 145 ° C. or lower under pressure. The headspace gas chroma is characterized in that the composition is first cured and then placed in hot air until the content of cyclic dimethylsiloxane tetramer to 15 mer is 250% by mass or less and secondarily cured. A laminated sheet for forming a septum for sealing an opening of a vial for a tograph analysis method or a headspace gas chromatograph mass analysis method, which has an aromatic polyimide film having a thickness of 10 to 200 μm and a thickness of 10 to 200 μm. It is 1.2 to 5 mm, has a cyclic dimethylsiloxane tetramer to 15-mer content of 250 mass ppm or less, contains (A) fumed silica as a reinforcing filler, and is specified in JIS K 6249. A hydrosilylation reaction-cured silicone rubber layer (I) having an elongation of 380% or more and a tensile stress at 100% elongation of 0.20 to 1.35 MPa , or a thickness of 1.2 to 5 mm. The content of cyclic dimethylsiloxane tetramer to 15-mer is 250% by mass or less, and (A) fumed silica as a reinforcing filler and (B) organic functional organoalkoxysilane or a partially hydrolyzed condensate thereof. Adhesion with the hydrosilylation reaction-cured silicone rubber layer (II), which contains 380% or more of elongation specified by JIS K 6249 and has a tensile stress of 0.20 to 1.35 MPa at 100% elongation. A method for manufacturing a laminated sheet in which a square laminated sheet test piece having a length of 120 mm and a width of 120 mm is laminated in a state and the average warpage value of the four corners is 35 mm or less.

[6-1]
The components (B) are (a) an alkenyl functional organoalkoxysilane having two or three silicon atom-bonded alkoxy groups in one molecule and (b) two or three silicon atom-bonded alkoxy groups in one molecule. One to three selected from the group consisting of (meth) acrylic functional organoalkoxysilanes and (c) epoxy functional organoalkoxysilanes having two or three silicon atom-bonded alkoxy groups in one molecule. An organic-functional organoalkoxysilane, or a co-partial hydrolysis condensate of the organic-functional organoalkoxysilane and (d) an organic titanium compound catalyst, or two or three organic-functional organoalkoxysilanes. 6] The method for manufacturing a laminated sheet.
[6-2]
In [6] or [6-1], the component (B) is contained in the hydrosilylation reaction heat-curable liquid silicone rubber composition and the hydrosilylation reaction-curable silicone rubber layer in an amount of 0.03 to 6% by mass. The method for manufacturing a laminated sea according to the description.
[6-3]
[6], [6-1] or [6], [6-1] or that the fumed silica is contained in the hydrosilylation reaction heat-curable liquid silicone rubber composition and the hydrosilylation reaction-curable silicone rubber layer in an amount of 10 to 24% by mass. The method for manufacturing a laminated sheet according to [6-2].
[6-4]
The hydrosilylation reaction-curable silicone rubber layer is a cured product of a hydrosilylation reaction-curable silicone rubber composition containing both-terminal trimethylsiloxy group-blocking dimethylsiloxane / methylhydrogensiloxane copolymer as a cross-linking agent. The method for producing a laminated sheet according to [6], [6-1], [6-2] or [6-3].
[6-5]
The heat-curable liquid silicone rubber composition obtained by the hydrosilylation reaction is a methylhydrogenpolysiloxane having at least three hydrosilyl groups as a cross-linking agent and a dimethylpolysiloxane having both ends of the molecular chain sealed with a hydrodimethylsiloxy group (polymerization). The method for producing a laminated sheet according to [6], [6-1], [6-2] or [6-3], which comprises (degree 10 or less).

[7]
An aromatic polyimide film having a thickness of 10 to 200 μm, a thickness of 1.2 to 5 mm, a content of cyclic dimethylsiloxane tetramer to 15-mer, and a reinforcing filler having a thickness of 250 mass ppm or less. ( A ) Hydrosilylated reaction-cured silicone rubber layer containing fumed silica, having an elongation of 380% or more specified by JIS K 6249, and a tensile stress at 100% elongation of 0.20 to 1.35 MPa. (I) Or , the thickness is 1.2 to 5 mm, the content of the cyclic dimethylsiloxane tetramer to 15-mer is 250 mass ppm or less, and (A) fumed silica as a reinforcing filler. ( B) Contains organic functional organoalkoxysilane or a partially hydrolyzed condensate thereof, the elongation specified by JIS K 6249 is 380% or more, and the tensile stress at 100% elongation is 0.20 to 1.35 MPa. The hydrosilylation reaction-cured silicone rubber layer (II) is laminated in an adhesive state, and is peeled and bonded based on JIS K6854-2 (adhesive-peeling and bonding strength test method-Part 2: 180 degree peeling). A headspace gas chromatograph analysis is characterized in that a square laminated sheet test piece having a strength of 4 N / 20 mm or more and a length of 120 mm and a width of 120 mm is composed of a laminated sheet having an average warp value of 35 mm or less at four corners . Septum for sealing the opening of a vial for legal or headspace gas chromatograph mass analysis.

[7-1]
The components (B) are (a) an alkenyl-functional organoalkoxysilane having two or three silicon atom-bonded alkoxy groups in one molecule and (b) two or three silicon atom-bonded alkoxy groups in one molecule. One to three selected from the group consisting of (meth) acrylic functional organoalkoxysilanes and (c) epoxy functional organoalkoxysilanes having two or three silicon atom-bonded alkoxy groups in one molecule. An organic-functional organoalkoxysilane, or a co-partial hydrolysis condensate of the organic-functional organoalkoxysilane and (d) an organic titanium compound catalyst, or two or three organic-functional organoalkoxysilanes. 7].
[7-2]
The septum according to [7] or [7-1], wherein the component (B) is contained in the hydrosilylation reaction-cured silicone rubber layer in an amount of 0.03 to 6% by mass.
[7-3]
(A) The septum according to [7], [7-1] or [7-2], which contains 10 to 24% by mass of fumed silica in the hydrosilylation reaction-cured silicone rubber layer.
[7-4]
The heat-curable liquid silicone rubber composition obtained by the hydrosilylation reaction contains, as a cross-linking agent, a double-ended trimethylsiloxy group-blocking dimethylsiloxane / methylhydrogensiloxane copolymer, [7], [7-1. ], [7-2] or [7-3].
[7-5]
The cured silicone rubber layer obtained by the hydrosilylation reaction is a methylhydrogenpolysiloxane having at least three hydrosilyl groups as a cross-linking agent and a dimethylpolysiloxane having both ends of the molecular chain sealed with a hydrodimethylsiloxy group (polymerization degree 10 or less). The septum according to [7], [7-1], [7-2] or [7-3], which comprises.

[8]
It is a septum composed of a laminate of an aromatic polyimide film and a hydrosilylation reaction-curing silicone rubber layer, and the hydrosilylation reaction-curing silicone rubber contains (A) fumed silica as a reinforcing filler and at least as a cross-linking agent. It is a cured product of a hydrosilylation reaction-curable silicone rubber composition containing a methylhydrogenpolysiloxane having three hydrosilyl groups and a hydrodimethylsiloxy group-sealed dimethylpolysiloxane (polymerization degree 3 or less) at both ends of the molecular chain. Characteristic, septum.
[8-1]
The septum according to [8], wherein the hydrosilylation reaction-curable silicone rubber composition further contains (B) an organic functional organoalkoxysilane or a partially hydrolyzed condensate thereof. Is achieved by.

In the above [1] to [8-1], each component of the present invention can be taken alone or in combination of a plurality of embodiments described as preferable in [Mode for Carrying Out the Invention]. ..

The laminated sheet for producing the opening sealing septum for the headspace gas chromatography or the vial for headspace gas chromatography of the present invention can be punched from the laminated sheet into a predetermined shape such as a circular shape at the time of producing the septum. It is easy to do, and the aromatic polyimide film does not peel off from the silicone rubber layer during the work.
Even if the opening of the vial is sealed and heated at a high temperature (eg, 300 ° C.), the headspace gas is used as a septum for sealing the opening of the vial for headspace gas chromatography or headspace gas chromatography. Since the amount of the cyclic organosiloxane oligomer inside is very small, the analysis accuracy is not deteriorated. In addition, the silicone rubber layer strongly holds the sampling needle even when it is heated to a high temperature (eg, 300 ° C.) and the sampling needle for headspace gas sampling is inserted into the septum and the internal pressure of the vial increases due to the press-fitting of the inert gas. Therefore, it has excellent gas leakage resistance.

According to the method for producing a laminated sheet for producing a septum for sealing an opening of a vial for headspace gas chromatograph analysis or headspace gas chromatograph mass spectrometry according to the present invention, for headspace gas chromatograph analysis or head. An aromatic polyimide film and a silicone rubber layer, which are suitable for manufacturing septams for encapsulating the openings of vials for space gas chromatograph mass spectrometry, are bonded and laminated, making it easy and reliable to stack laminated sheets with a small degree of warpage. Can be manufactured.

The septum for sealing the opening of the vial for the headspace gas chromatograph analysis method or the headspace gas chromatograph mass analysis method of the present invention is the opening of the vial for the headspace gas chromatograph analysis method or the headspace gas chromatograph mass analysis method. It is easy to use for encapsulation, and even if the opening of the vial is sealed and heated at a high temperature (eg, 300 ° C.), the amount of cyclic organosiloxane oligomer in the headspace gas is very small, so the analysis accuracy is not reduced. The silicone rubber layer strongly holds the sampling needle even when the internal pressure of the vial is increased by inserting the sampling needle for headspace gas sampling into the septum when heated to a high temperature (eg, 300 ° C.) and press-fitting the inert gas. Therefore, it has excellent gas leakage resistance. Even if silicone rubber scraps fall into the vial, goust peaks are practically unlikely to appear in the gas chromatogram or mass spectrum.

In the septum of the present invention, a volatile component generated from a silicone rubber layer when heated at a high temperature (eg, 300 ° C.) was injected into a gas chromatograph (GC) column, and gas chromatograph analysis was performed under predetermined temperature conditions. Occasionally, the total area of each of the plurality of low degree of polymerization siloxane peaks in the displayed gas chromatogram is small, so that the accuracy of the gas chromatograph analysis is not substantially reduced.

FIG. 1 is a partial cross-sectional view of a laminated sheet 1 in which an aromatic polyimide resin film is adhered to one side of a silicone rubber layer according to an embodiment of the present invention. FIG. 2 is a partial cross-sectional view of a laminated sheet 2 in which an aromatic polyimide resin film is adhered to both sides of a silicone rubber layer according to an embodiment of the present invention. FIG. 3 is a photograph of a laminated sheet having an average warpage value of 6.8 mm in Example 10 (Table 4) of the present invention. FIG. 4 is a photograph of a septum produced by punching a laminated sheet having an average warp value of 15 mm in Example 8 (Table 3) into a circle. The left side of FIG. 5 is a photograph of a laminated sheet having an average warp value of 16 mm in Example 2 (Table 1) of the present invention. The right side of FIG. 5 is a photograph of the laminated sheet of Comparative Example 9 (5-1 in Table 5). From the side view, it can be seen that the front side and the back side are curved more than a semicircular shape. The left side of FIG. 6 is a photograph of a septum produced by punching a laminated sheet having an average warp value of 16 mm in Example 2 (Table 1) of the present invention into a circle. The right side of FIG. 6 is a photograph of a septum produced by punching a laminated sheet having an average warp value of Comparative Example 9 (Table 5) having a semicircular shape or more in a circular shape. FIG. 7 is a perspective view of a laminated sheet in which a polyimide resin film 3b is adhered to one side of a silicone rubber layer 3a, which is an embodiment of the present invention. FIG. 8 is a side view of a vial in which a screw cap with a septum fitted inside is attached to a screw vial opening and sealed according to an embodiment of the present invention. The aromatic polyimide film is located below the septum. The left side of FIG. 9 is a front view of the screw vial 5 in which the septum 3 is placed on the upper surface of the opening. The right side of FIG. 9 is a schematic view of a gas leak test device. FIG. 10 is a chart diagram of a gas chromatograph analysis of a pressurized headspace gas (a gas phase containing a component produced by heating the septum) in a vial for a septum composed of a laminated sheet of Example 4. FIG. 11 is a graph showing the relationship between the SiH / SiVi ratio and the hardness of the Asker rubber hardness tester C type, that is, the Asker C hardness. FIG. 12 shows the relationship between the mass% of RBL-9200-40B in the mixture of RBL-9200-40A and RBL-9200-40B and the hardness according to the type A durometer specified in JIS K6253, that is, the type A hardness. It is a graph which shows. FIG. 13 is a photograph of the laminated sheets (1), (2), and (3) of Example 20 in order from the left. FIG. 14 is a chart diagram of a gas chromatograph analysis of a pressurized headspace gas (a gas phase containing a component produced by heating the septum) in a vial for a septum composed of a laminated sheet of Comparative Example 17. FIG. 15 is a chart diagram of a gas chromatograph analysis of a pressurized headspace gas (a gas phase containing a component produced by heating the septum) in a vial for a septum composed of a laminated sheet of Example 21. FIG. 16 is a chart diagram of a gas chromatograph analysis of a pressurized headspace gas (a gas phase containing a component produced by heating the septum) in a vial for a septum composed of a laminated sheet of Reference Example 9. FIG. 17 is a chart diagram of a gas chromatograph analysis of a pressurized headspace gas (a gas phase containing a component produced by heating the septum) in a vial for a septum composed of a laminated sheet of Comparative Example 18. FIG. 18 is a chart diagram of a gas chromatograph analysis of a pressurized headspace gas (a gas phase containing a component produced by heating the septum) in a vial for a septum composed of a laminated sheet of Example 22. FIG. 19 is a chart diagram of a gas chromatograph analysis of a pressurized headspace gas (a gas phase containing a component produced by heating the septum) in a vial for a septum composed of a laminated sheet of Example 23.

The first invention of the present application is an aromatic sheet having a thickness of 10 to 200 μm in a laminated sheet for producing a septum for sealing an opening of a vial for headspace gas chromatograph analysis or headspace gas chromatograph mass analysis. The polyimide film has a thickness of 1.2 to 5 mm, the content of cyclic dimethylsiloxane tetramer to 15-mer is 250 mass ppm or less, and (A) fumed silica is contained as a reinforcing filler. , JIS K 6249 stretch is 380% or more, and the tensile stress at 100% stretch is 0.20 to 1.35 MPa. Hydrosilylation reaction-curing silicone rubber layer (I) or (B) organic functional The hydroxysilylated reaction-curable silicone rubber layer (II) containing the sex organoalkoxysilane or a partially hydrolyzed condensate thereof is laminated in an adhesive state, and JIS K6854-2 (adhesive-peeling adhesive strength test method-) The peeling adhesive strength based on (Part 2: 180 degree peeling) is 5N or more, and the four corners of a square laminated sheet test piece with a length of 120 mm and a width of 120 mm have the shape of one end of a semi-arc or the shape of one end of a C-shape. The present invention relates to a laminated sheet, which is characterized in that it does not bend and the average warpage value of the four corners is 35 mm or less.

The present invention comprises an aromatic polyimide film and a silicone rubber layer or a silicone gel layer for producing a septum for sealing an opening of a vial for headspace gas chromatograph analysis or headspace gas chromatograph mass analysis. The aromatic polyimide film and the aromatic polyimide resin film used in the laminated sheet are films made of the aromatic polyimide and the aromatic polyimide resin.

The aromatic polyimide and aromatic polyimide resin for that purpose are usually aromatic tetracarboxylic acid dianhydride (eg, pyromellitic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, etc. 2,2', 3,3'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyltetracarboxylic acid dianhydride) and aromatic diamine components (eg, 3,3'-dimethyl). Polycondensation containing -4,4'-diaminobiphenyl, 2,5-dimethyl-p-phenylenediamine, 4,4'-methylenedi-o-toluidine, 2,4-toluenediamine, p-phenylene-diamine) as the main components. Obtained from the reaction.

When aromatic tetracarboxylic acid dianhydride and aromatic diane are reacted in a polar solvent, a polyamic acid solution which is a precursor of polyimide is obtained.
The aromatic polyimide film and the aromatic polyimide resin film are usually cast from this polyamic acid solution on a support and dried, and then imidized at a high temperature or heated in the solution to carry out an imidization reaction. After that, the solution can be obtained by casting it on a support, drying it, and heat-treating it.

An aromatic polyimide film or an aromatic polyimide resin film in which an aromatic compound is directly linked by an imide bond is preferable in terms of film strength and normal heat resistance in the 300 ° C. class.

As a commercially available aromatic polyimide film and aromatic polyimide resin fi, manufactured by Toray DuPont Co., Ltd., trade name: Kapton H type (a standard type of Kapton, obtained by decomposition of aromatic tetrabasic acid and aromatic diamine). (It is a transparent golden film), Kapton V type (low heat shrink type), Kapton EN type (high dimension stable type), Kapton ENZT; manufactured by Ube Kosan Co., Ltd., trade name: Upirex-S (basic grade) , Upirex-RN (molding grade), Upirex-CA (thin film), etc .; trade names manufactured by Kaneka Co., Ltd .: Apical AH (general grade), Apical NPI (dimensional stability type) are exemplified. Kapton, Upirex, and Apical are registered trademarks. The thickness varies depending on the manufacturer and brand, but is usually 10 μm, 12.5 μm, 25 μm, 50 μm, 75 μm, 125 μm.
It is also preferable that the surfaces of these commercially available aromatic polyimide films and aromatic polyimide resin films are subjected to plasma treatment, corona discharge treatment, or the like.

The thickness of the aromatic polyimide film and the aromatic polyimide resin film is in the range of 10 to 200 μm, preferably 10 to 125 μm from the viewpoint of availability. From the viewpoint of film strength and reduction of warpage when formed into a laminated sheet, the range is preferably 20 to 125 μm.

The shape of the aromatic polyimide resin film is exemplified by a sheet shape, a tape shape, and a strip shape.

In the first invention of the present application, the content of cyclic dimethylsiloxane tetramer to 15-mer used for forming a silicone rubber layer in a laminated sheet in which an aromatic polyimide film and a silicone rubber layer are laminated in an adhesive state. The heat-curable liquid silicone rubber composition obtained by a hydrosilylation reaction containing 250% by mass or less contains (a) an alkenyl group-containing diorganopolysiloxane having at least two alkenyl groups in one molecule as a main component. , Contains (A) fumed silica as a reinforcing filler. The heat-curable liquid silicone rubber composition obtained by this hydrosilylation reaction is preferably (a) a liquid diorganopolysiloxane having at least two alkenyl groups in one molecule, and (b) at least two in one molecule. It consists of an organopolysiloxane having a silicon atom-bonded hydrogen atom, (c) a platinum-based catalyst, and (d) a hydrosilylation reaction inhibitor, and contains (A) fumed silica as a reinforcing filler.
The content of the component (A) is usually 10 to 24% by mass, preferably 12 to 23% by mass in the heat-curable liquid silicone rubber composition by the hydrosilylation reaction.

(A) The liquid diorganopolysiloxane having at least two alkenyl groups in one molecule is the main component of the heat-curable liquid silicone rubber composition by the hydrosilylation reaction, and (c) by the action of a platinum-based catalyst (c). B) Addition reaction with a silicon atom-bonded hydrogen atom in an organopolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule to crosslink.

When the heat-curable liquid silicone rubber composition by hydrosilylation reaction is cured only by heating under pressure during the production of the laminated sheet, the cyclic siloxane oligomer derived from the component (a) is reduced as much as possible. Ru. Preferably, the D4-D15 content is 250 ppm or less, more preferably 210 ppm or less, still more preferably 100 ppm or less in terms of mass.

(A) The alkenyl group in the component is bonded to a silicon atom, and a vinyl group, an allyl group, and a propenyl group are exemplified, and a vinyl group is preferable. As an organic group other than the alkenyl group, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group or a dodecyl group; an aryl group such as a phenyl group or a trill group; β- Aralkyl groups such as a phenylethyl group; halogen-substituted alkyl groups such as 3,3,3-trifluoropropyl group and 3-chloropropyl group are exemplified. Here, the number of carbon atoms of the alkyl group and the alkyl halide group is preferably 2 to 12, the number of carbon atoms of the aryl group is preferably 6 to 12, and the number of carbon atoms of the aralkyl group is preferably 7 to 12. It is preferable that all the silicon atom-bonded organic groups other than the alkenyl group are methyl groups, but 50 mol% or more are methyl groups, and the remainder is an alkyl group having 2 to 12 carbon atoms, a phenyl group or 2 to 2 carbon atoms. It may be 12 alkyl groups and phenyl groups.

(A) The alkenyl group-containing diorganopolysiloxane having at least two alkenyl groups in one molecule preferably contains 0.1 to 5.0 mol% of all silicon atom-bonded organic groups as alkenyl groups.

(A) The molecular structure of the component is usually linear, but it may be linear including branching.

(B) The properties of the ingredients are liquid at room temperature.
Those that are liquid at room temperature preferably have a viscosity at 25 ° C. of 100 mPa · s or more and 300,000 mPa · s or less. The degree of polymerization is usually preferably 50 to 2,000.

In the component (a), both ends of the molecular chain are usually sealed with a triorganosiloxy group such as a dimethylvinylsiloxy group, a methylphenylvinylsiloxy group, or a trimethylsiloxy group.

Typical examples of the component (a) are dimethylpolysiloxane having both ends of the molecular chain sealed with a dimethylvinylsiloxy group, which are liquid at room temperature, and dimethylsiloxane / methylvinyl having both ends of the molecular chain sealed with a dimethylvinylsiloxy group. A siloxane copolymer, a dimethylsiloxane / methylvinylsiloxane copolymer having both ends of the molecular chain sealed with a hydroxydimethylsiloxy group, and a dimethylsiloxane / methylphenylsiloxane copolymer having both ends of the molecular chain sealed with a dimethylvinylsiloxy group. , Dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer with both ends of the molecular chain sealed with a dimethylvinylsiloxy group, dimethylpolysiloxane with both ends of the molecular chain sealed with a methylphenylvinylsiloxy group, both ends of the molecular chain Examples thereof include a dimethylsiloxane / methylvinylsiloxane copolymer sealed with a methylphenylvinylsiloxy group.

Among these, dimethylpolysiloxane having both ends of the molecular chain sealed with a dimethylvinylsiloxy group, dimethylsiloxane / methylvinylsiloxane copolymer having both ends of the molecular chain sealed with a dimethylvinylsiloxy group, and molecules that are liquid at room temperature. A dimethylsiloxane / methylvinylsiloxane copolymer having both ends of the chain sealed with a trimethylsiloxy group is often put into practical use.
Two or more of these may be used in combination.

(B) Organopolysiloxane having at least two silicon atom-bonded hydrogens in one molecule is a cross-linking agent of (a) component, and (c) silicon atom-bonded hydrogen in this component by the catalytic action of a platinum-based catalyst. An atom is added to a silicon atom-bonded alkenyl group in the component (a), particularly a vinyl group, to crosslink the component (a) and cure it. This component has at least two silicon atom-bonded hydrogen atoms (hydrosilyl groups) in one molecule, but (a) three silicon atom-bonded alkenyl groups in the component, for example, when there are two vinyl groups. It is necessary to have the above-mentioned silicon atom-bonded hydrogen atom (hydrosilyl group).

(B) As the silicon atom-bonded organic group in the component, a methyl group; an alkyl group such as an ethyl group, a propyl group and a hexyl group; an aryl group such as a phenyl group and a trill group; a 3,3,3-trifluoropropyl group , An alkyl halide group such as a 3-chloropropyl group, and an aralkyl group are exemplified. Here, the number of carbon atoms of the alkyl group and the alkyl halide group is preferably 2 to 12, the number of carbon atoms of the aryl group is preferably 6 to 12, and the number of carbon atoms of the aralkyl group is preferably 7 to 12. From the viewpoint of ease of production and compatibility of the component (a) with the preferred example, at least 50 mol% is preferably a methyl group, and 100 mol% is more preferably a methyl group.

The molecular structure of the component (b) may be linear, branched, or cyclic. The degree of polymerization of this component is not particularly limited as long as it is 2 or more, but it is preferably liquid at room temperature. The viscosity at 25 ° C. is preferably 1 to 1,000 mPa · s.

Preferred examples of the component (b) include methylhydrogenpolysiloxanes. Typical examples thereof include (b) methylhydrogenpolysiloxane having at least three hydrosilyl groups in one molecule, and (b) bi-terminal hydrodimethylsiloxy group-blocking dimethylpolysiloxane.
(B) As a component, both-ended trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both-ended trimethylsiloxy group-blocked methylhydrogenpolysiloxane, and both-ended hydrodimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer are used. Illustrated.
The component (b2) functions as a chain extender, but the chain extension action decreases as the degree of polymerization increases, so the degree of polymerization is preferably 10 or less, more preferably 5 or less, still more preferably 4 or less, and 3 Is the best.

Of the components (b1), the two-terminal trimethylsiloxy group-blocked methylhydrogenpolysiloxane and the two-terminal hydrodimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer have excessively high modulus and low elongation of the cured product. Too much, there is a risk that the gas leakage resistance will decrease when septam is used, so a double-ended trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer is preferable.
However, the two-terminal trimethylsiloxy group-blocked methylhydrogenpolysiloxane and the two-terminal hydrodimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer can be used in combination with the component (b), particularly one having a degree of polymerization of 10 or less. , The above-mentioned adverse effects can be reduced.
The double-ended trimethylsiloxy group-sealed dimethylsiloxane / methylhydrogensiloxane copolymer can improve gas leakage resistance when used as a septum when used in combination with the component (b), especially one having a degree of polymerization of 10 or less. can.
The same applies to the case where the component (b) and the component (b) are blended in a heat-curable liquid silicone rubber composition by a hydrosilylation reaction and a heat-curable liquid silicone gel composition by a hydrosilylation reaction.

(B 1) Methylhydrogenpolysiloxane (pure cross-linking agent) having at least 3 hydrosyl groups in one molecule and (b) Dimethylpolysiloxane (chain extender) having 2 hydrosyl groups in 1 molecule ) Is preferably 8: 1 to 1: 8, and more preferably 4: 1 to 1: 4.
Both-terminal hydrodimethylsiloxy group-sealed dimethylpolysiloxane (preferably having a degree of polymerization of 10 or less) is preferably contained in a heat-curable liquid silicone rubber composition by a hydrosilylation reaction in an amount of 0.08 to 6% by mass, which is 0. It is more preferable that the content is .2 to 3% by mass.
The same applies to the case where the component (b) and the component (b) are blended in a heat-curable liquid silicone rubber composition by a hydrosilylation reaction and a heat-curable liquid silicone gel composition by a hydrosilylation reaction.
The mode of the combination is common to the second to seventh inventions of the present application.

In the case of a heat-curable liquid silicone rubber composition by a hydrosilylation reaction, the blending amount of the component (b) is the molar ratio of the silicon atom-bonded hydrogen atom in the component (b) to the silicon atom-bonded alkenyl group in the component (a). However, the amount is usually (0.7: 1) to (1.7: 1), preferably (0.90: 1) to (1.5: 1), and more. The amount is preferably (0.95: 1) to (1.4: 1).
This is because when this molar ratio is smaller than (0.7: 1), the rubber elasticity of the cured product decreases and it tends to become gel-like, and when it is larger than (1.7: 1), the modulus of the cured product becomes This is because the height may become too high and the needle stick resistance and gas leakage resistance may decrease when the septum is used. However, when the above-mentioned two-terminal hydrodimethylsiloxy group-blocked dimethylpolysiloxane or 1,3-dihydro-1,1,3,3-tetramethyldisiloxane is used in combination, even if the molar ratio is larger than (1.6: 1). , It is possible to suppress deterioration of needle stick resistance and gas leakage resistance.

(C) The platinum-based catalyst is a catalyst for addition-reacting the silicon atom-bonded hydrogen atom in the component (b) with the silicon atom-bonded alkenyl group in the component (a) to crosslink and cure the component (a). be. These include platinum fine powder, platinum black, platinum chloride acid, olefin complex of platinum chloride acid, complex of platinum chloride acid and divinyltetramethyldisiloxane, platinum complex of divinyltetramethyldisiloxane, platinum chloride acid and β-diketone. The above-mentioned complex and the platinum complex of β-diketone are exemplified.
(C) In the platinum-based catalyst, the silicon atom-bonded hydrogen atom in the component (b) and the silicon atom-bonded alkenyl group (for example, vinyl group) in the component (a) undergo an addition reaction to crosslink the component (a) and cure. A sufficient amount, a so-called catalytic amount, is used. Specifically, it is preferable that the hydrosilylation reaction-curable silicone rubber composition contains 1 to 1000 mass ppm in terms of platinum-based metal.

(A) Humed silica has an effect of imparting viscosity to a heat-curable liquid silicone rubber composition by a hydrosilylation reaction to facilitate molding work. Further, it has an action of imparting excellent mechanical strength and hardness to the silicone rubber obtained by heat-curing the heat-curable liquid silicone rubber composition by the hydrosilylation reaction.

(A) Humed silica is an amorphous silica in the form of ultrafine particles, and is a typical dry silica. The specific surface area by the BET method is usually 100 to 400 m ² / g. Those having a BET specific surface area of 110 to 300 m ² / g are put into practical use for silicone rubber. Commercially available products include Aerosil 200 (surface area 200 m ² / g), Aerosil 255 (specific surface area by BET method 255 m ² / g), Aerosil 300 (specific surface area by BET method 300 m ² / g), Aerosil 380 (specific surface area by BET method). 380m ² / g) [manufactured by Nippon Aerosil Co., Ltd., Aerosil is a registered trademark of Ebony Degusa Game M Beher], Leolosil [manufactured by Tokuyama Corporation, Leolosil is a registered trademark of the company].

Since (A) fumed silica is hydrophilic and difficult to mix with (a) components, (C) hydrophobic agents (for example, organochlorosilanes such as trimethylchlorosilane and dimethyldichlorosilane, organoalkoxysilanes such as trimethylmethoxysilane, etc.) Hexaorganodisilazane such as hexamethyldisilazane, silanol-terminated dimethylsiloxane oligomer, cyclic dimethylsiloxane oligomer) is preferable.
The specific surface area of the hydrophobized fumed silica by the BET method is usually 100 to 350 m ² / g.

Commercially available products of hydrophobized fumed silica include Aerosil R972 (specific surface area by BET method is 110 m ² / g), Aerosil RX200 (specific surface area by BET method is 140 m ² / g), Aerosil R974 (specific surface area by BET method is 170 m). ² / g), Aerosil R812 (specific surface area by BET method is 260 m ² / g) [manufactured by Nippon Aerosil Co., Ltd.] is exemplified.

The content of the component (A) is usually 10 to 24% by mass, preferably 12 to 23% by mass in the heat-curable liquid silicone rubber composition by the hydrosilylation reaction. It is not limited to these.

(D) The hydrosilylation reaction inhibitor has the effect of preventing gelation and curing during kneading, or preventing gelation and curing during storage at room temperature, and does not cure at room temperature, and the curing rate improves when the temperature rises. However, for example, at 90 ° C to 120, it has the effect of curing in 8 to 30 minutes.

Examples of the hydrosilylation reaction inhibitor include acetylene compounds, enyne compounds, organic nitrogen compounds, organic phosphorus compounds, and oxime compounds.

Specifically, acetylene alcohols such as 3-methyl-1-butyne-3-ol, 3,5-dimethyl-1-hexin-3-ol, phenylbutinol, 1-ethynyl-1-cyclohexanol; 3- Enin compounds such as methyl-3-pentene-1-in and 3,5-dimethyl-3-hexene-1-in, methyl-tris (3-methyl-1-butyne-3-oxy) silane, vinyl-tris ( Alkyne-containing silanes such as 3-methyl-1-butyne-3-oxy) silane; alkenyl group-containing oligosiloxanes such as tetramethyltetravinylcyclotetrasiloxane; benzotriazoles are exemplified.

The blending amount of this hydrosilylation reaction inhibitor is such that the hydrosilylation reaction heat-curable liquid silicone rubber composition is not cured at room temperature and room temperature, and is sufficiently cured by heat curability, particularly at 90 ° C. for 5 to 15 minutes. In the hydrosilylation reaction heat-curable liquid silicone rubber composition, the amount is usually in the range of 0.05 to 5% by mass, preferably in the range of 0.1 to 2% by mass. Is. It is preferable to appropriately select the component according to the type of this component, the type and content of the hydrosilylation reaction catalyst, (a) the amount of alkenyl groups in the component, and (b) the amount of silicon-bonded hydrogen atoms in the component.

Since the heat-curable liquid silicone rubber composition by the hydrosilylation reaction contains (A) fumed silica as a reinforcing filler, the cured product has excellent heat resistance and seals the opening of the headspace vial. It is suitable for manufacturing a laminated sheet for stopping. The heat resistance is not good when the wet silica is contained.

In the present invention, a heat-curable liquid silicone rubber composition by a hydrosilylation reaction, which is used for forming a silicone rubber layer in a laminated sheet in which an aromatic polyimide film and a silicone rubber layer are bonded and laminated, is usually used. The above-mentioned component (a) (however, the content of cyclic dimethylsiloxane tetramer to 15-mer is 250% by mass or less) and (A) a predetermined amount of hydrophobized fumed silica, or (a). A liquid silicone rubber base is produced by uniformly kneading the component (A), the component (A), and a predetermined amount of the hydrophobic agent with a planetary mixer or the like at room temperature or temperature rise.
Next, to the liquid silicone rubber base, (b) an organopolysiloxane having at least two silicon atom-bonded hydrogen atoms in one molecule, (c) a platinum-based catalyst, and (d) a hydrosilylation reaction inhibitor were added at room temperature. It can be manufactured by kneading it uniformly.

Alternatively, in the planetary mixer, the content of the cyclic dimethylsiloxane tetramer to 15-mer of the two-component type sold by the silicone manufacturer is 250 mass ppm or less, and a predetermined amount of (A) fumed. It can be easily produced by mixing the liquid A and the liquid B of the heat-curable liquid silicone rubber composition by a hydrosilylation reaction containing silica until they become uniform.

Alternatively, the content of cyclic dimethylsiloxane tetramer to 15-mer is 250% by mass or less, and a colorless and transparent hydrosilylation reaction crosslinkable liquid silicone gel composition containing no filler is applied at room temperature (b). Organopolysiloxanes having at least two silicon atom-bonded hydrogen atoms in one molecule, particularly the methylhydrogenpolysiloxanes, are blended to create a molar silicon atom-bonded hydrogen atom and a silicon atom-bonded alkenyl group, such as a vinyl group. It can be easily produced by increasing the ratio (SiH / SiVi ratio) to around 0.7 to 1.4 and blending (A) fumed silica, preferably hydrophobic fumed silica.
The content of the component (A) is usually 10 to 24% by mass, preferably 12 to 23% by mass in the heat-curable liquid silicone gel composition by the hydrosilylation reaction.
Commercially available hydrosilylation reaction crosslinkable liquid silicone gel compositions usually consist of vinyl group-containing dimethylpolysiloxane, methylhydrogenpolysiloxanes, platinum-based catalysts and hydrosilylation reaction inhibitors that are liquid at room temperature, but SiH / SiVi. This is because the ratio is much smaller than 1, for example 0.4 to 0.7. Further, since it does not contain a filler, it cannot be formed into a strong rubber-like substance even if it is cured.

The heat-curable liquid silicone rubber composition by the hydrosilylation reaction preferably further contains (B) an organic functional organoalkoxysilane or a partially hydrolyzed condensate thereof in order to improve the adhesiveness to the aromatic polyimide resin film. contains.
The components (B) are preferably (a) an alkenyl-functional organoalkoxysilane having two or three silicon atom-bonded alkoxy groups in one molecule and (b) (a) a silicon atom-bonded alkoxy group in one molecule. It is selected from the group consisting of (meth) acrylic functional organoalkoxysilane having 2 or 3 and (c) epoxy functional organoalkoxysilane having 2 or 3 silicon atom-bonded alkoxy groups in one molecule. It is composed of one or three kinds of organic functional organoalkoxysilanes, or the organic functional organoalkoxysilanes and (d) an organic titanium compound catalyst.

(a) As an alkenyl-functional organoalkoxysilane having two or three silicon atom-bonded alkoxy groups in one molecule, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, hexenyltrimethoxysilane, and methylvinyldimethoxy Examples thereof include silane and methylvinyldiethoxysilane.
(b) As the (meth) acrylic functional organoalkoxysilane having two or three silicon atom-bonded alkoxy groups in one molecule, γ-methacryloxypropyltrimethoxysilane, δ-methacryloxybutyltrimethoxysilane, γ- Examples thereof include methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, and γ-acryloxypropyltriethoxysilane.
(c) As an epoxy-functional organoalkoxysilane having two or three silicon atom-bonded alkoxy groups in one molecule, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-gli Sidoxypropylmethyldimethoxysilane, β- (3,4-epylcyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxy Silane is exemplified.

(d) Examples of the organic titanium compound catalyst include organic titanates such as tetrabutyl titanate, tetraisopropyl titanate, tetramethyl titanate, ethylmethyldibutyl titanate, tetraoctyl titanate, and tetraethylhexyl titanate.
As chelated organic titanates, titanium acetylacetonate, titaniumethylacetoneacetate, titaniumtetraacetylacetoneate, diisopropoxybis (acetylacetone) titanium, trimethylenedioxybis (acetylacetonate) titanium, diisopropoxybis ( Examples thereof include (ethylacetate acetate) titanium and trimethylenedioxybis (ethylacetoacetate) titanium.

(a) Alkenyl functional organoalkoxysilane having 2 or 3 silicon atom-bonded alkoxy groups in one molecule or (b) (meth) acrylic functionality having 2 or 3 silicon atom-bonded alkoxy groups in one molecule A co-partially hydrolyzed condensate of a sex organoalkoxysilane and (c) an epoxy functional organoalkoxysilane having two or three silicon atom-bonded alkoxy groups in one molecule is also useful as an additive.
Such co-partially hydrolyzed condensates may have (a) an alkenyl-functional organoalkoxysilane having two or three silicon atom-bonded alkoxy groups in one molecule or (b) two silicon atom-bonded alkoxy groups in one molecule. Alternatively, a (meth) acrylic functional organoalkoxysilane having three and (c) an epoxy functional organoalkoxysilane having two or three silicon atom-bonded alkoxy groups in one molecule, a small amount of water and a small amount of organic titanium. It can be easily produced by mixing with a compound catalyst, co-hydrolyzing and partially condensing.

Furthermore, (a) an alkenyl-functional organoalkoxysilane having two or three silicon atom-bonded alkoxy groups in one molecule, and (b) two or three silicon atom-bonded alkoxy groups in one molecule (b). Meta) A co-partially hydrolyzed condensate of acrylic functional organoalkoxysilane and (c) epoxy functional organoalkoxysilane having two or three silicon atom-bonded alkoxy groups in one molecule is also useful as an additive. The manufacturing method is the same as above.

When the component (B) is a combination of two kinds of organic functional organoalkoxysilanes, the mass ratio is not particularly limited, but is preferably 1:99 to 99: 1, more preferably 5:95 to 95: 5. Illustrated.
(B) When the component is a combination of two or three kinds of organic functional organoalkoxysilanes and an organic titanium compound catalyst, the total amount of two or three kinds of organic functional organoalkoxysilanes and the organic titanium compound catalyst are used. , 10: 0.02 to 10: 2 in mass ratio is exemplified.

The component (B) is not essential for the heat-curable liquid silicone rubber composition by the hydrosilylation reaction, but is more than 0% by mass in the composition in terms of the adhesiveness between the aromatic polyimide film and the silicone rubber layer. , 0.03 to 6% by mass is preferable, and 0.1 to 2% by mass is more preferable.
Even if it is contained in an amount of more than 6% by mass, the peeling adhesiveness is not further improved, and the silicone rubber property and the septum property may be impaired.

It is not possible to add various additives that are well known and commonly used to be added to and blended with a normal hydrosilylation reaction-curable liquid silicone rubber composition to the heat-curable liquid silicone rubber composition by the hydrosilylation reaction. There is no problem as long as the effect of the invention is not impaired. Such additives include increasing fillers such as wet silica, diatomaceous earth powder, quartz powder and carbon black; pigments such as titanium oxide powder, carbon black, petals and various organic pigments; rare earth oxide powder and cerium silanolate. , Heat resistant agents such as cerium fatty acid salts; flame retardant agents such as benzotriazole, fumed titanium dioxide, manganese carbonate, zinc carbonate, platinum compounds, and internal mold release agents such as calcium stearate.

Unless otherwise specified, the above description and embodiments of the aromatic polyimide film in the first invention of the present application, the heat-curable liquid silicone rubber composition by hydrosilylation reaction, its components, the silicone rubber layer and the like are described in the second invention of the present application. It is common to the eighth invention.

In the second invention of the present application, the content of the aromatic polyimide film having a thickness of 10 to 200 μm and the cyclic dimethylsiloxane tetramer to 15-mer is 250 mass ppm or less, and the (A) fume is used as a reinforcing filler. Heat-curable liquid silicone rubber by hydrosilylation reaction containing dosilica, the elongation of the cured product specified by JIS K 6249 is 380% or more, and the tensile stress at 100% elongation is 0.20 to 1.35 MPa. It is brought into close contact with the heat-curable liquid silicone rubber composition (II) by the hydrosilylation reaction containing the composition (I) or (B) an organic functional organoalkoxysilane or a partially hydrolyzed condensate thereof, and under pressure. A laminated sheet for forming a septum for sealing an opening of a vial for headspace gas chromatograph analysis or headspace gas chromatograph mass analysis, which is characterized by heating at 145 ° C. or lower. A polyimide film having a thickness of 10 to 200 μm, a thickness of 1.2 to 5 mm, and a content of cyclic dimethylsiloxane tetramer to 15-mer of 250 mass ppm or less are used as a reinforcing filler (A). ) Hydrosilylated reaction-cured silicone rubber layer (I) containing fumed silica, having an elongation of 380% or more specified by JIS K 6249, and a tensile stress at 100% elongation of 0.20 to 1.35 MPa. Further, (B) the hydrosilylated reaction-curable silicone rubber layer (II) containing the organically functional organoalkoxysilane or a partially hydrolyzed condensate thereof is laminated in an adhered state, and is a square having a length of 120 mm and a width of 120 mm. The present invention relates to a method for manufacturing a laminated sheet in which the four corners of the laminated sheet test piece are not curved into the shape of one end of a semi-arc or the shape of one end of a C-shape, and the average warpage value of the four corners is 35 mm or less.

A laminated sheet composed of an aromatic polyimide film and a silicone rubber layer for producing a septum for sealing an opening of a vial for a headspace gas chromatograph analysis method or a headspace gas chromatograph mass analysis method is an aromatic polyimide film. A heat-curable liquid silicone rubber composition obtained by a hydrosilylation reaction containing (A) fumed silica as a reinforcing filler having a content of cyclic dimethylsiloxane tetramer to 15-mer of 250 mass ppm or less (A). I) or (B) the heat-curable liquid silicone rubber composition (II) produced by the hydrosilylation reaction containing the organically functional organoalkoxysilane or a partially hydrolyzed condensate thereof is brought into close contact with the mixture, and the temperature is 145 ° C. under pressure. It can be easily manufactured by heating below.

From the viewpoint of preventing warping of the laminated sheet, the temperature is 145 ° C or lower under pressure, preferably 140 ° C or lower, and more preferably 135 ° C or lower.
The lower the heating temperature, the longer the curing time, so the temperature is preferably 90 ° C. or higher, more preferably 105 ° C. or higher. If it is not sufficiently cured at these temperatures, it can be cured by lengthening the heating time.
For heat curing under pressure, compression molding and press molding are suitable because the surface of the silicone rubber layer is extremely smooth and a silicone rubber layer having a predetermined thickness can be produced. Heat compression molding between the upper and lower flat plates of the press vulcanizer as described later is suitable. It is preferable to pressurize at 20 MPa plus 5 MPa and -19 MPa, and more preferably 20 MPa plus 5 MPa and -15 MPa.

The laminated sheet composed of the aromatic polyimide resin film and the silicone rubber layer may have the aromatic polyimide resin film adhered to both sides of the silicone rubber layer.
Such a laminated sheet is described in detail by interposing a heat-curable liquid silicone rubber composition by the hydrosilylation reaction between two aromatic polyimide resin films in a flat cavity of a mold and heating the laminated sheet under compression. Can be easily produced by [a method for producing a laminated sheet in which an aromatic polyimide resin film is laminated on both sides of a silicone rubber layer in an adhesive state], which will be described later.

The third invention of the present application is an aromatic polyimide film having a thickness of 10 to 200 μm, a hydrosilylation reaction-cured silicone rubber, a thickness of 1.2 to 5 mm, and a cyclic dimethylsiloxane tetramer to a 15-mer. The content is 250 mass ppm or less, (A) fumed silica is contained as a reinforcing filler, the elongation specified by JIS K 6249 is 380% or more, and the tensile stress at 100% elongation is 0. The content of cyclic dimethylsiloxane tetramer to 15-mer is 250% by mass or less between the silicone rubber sheet having a pressure of 20 to 1.35 MPa, and (B) organic functional organoalkoxysilane or its partial hydrolysis. A heat-curable liquid silicone rubber composition containing a condensate and containing (A) fumed silica as a reinforcing filler. A thin layer of a heat-curable liquid silicone rubber composition is interposed and heated under pressure to be heated by the liquid hydrosilylation reaction. Curable Liquid Silicone Rubber Composition The aforementioned for forming a septum for sealing an opening in a vial for headspace gas chromatograph analysis or headspace gas chromatograph mass analysis, which comprises curing a thin layer. The polyimide film and the hydrosilylated reaction-cured silicone rubber sheet are laminated in an bonded state, and the four corners of a square laminated sheet test piece having a length of 120 mm and a width of 120 mm are formed at one end of a semi-arc or at one end of a C-shape. The present invention relates to a method for manufacturing a laminated sheet in which the average warpage value of the four corners is 35 mm or less without being curved in a shape.

The polyimide film for forming a septum for sealing the opening of a vial for headspace gas chromatograph analysis method or headspace gas chromatograph mass analysis method and the hydrosilylation reaction-curing silicone rubber sheet are adhered and laminated. The four corners of a square laminated sheet test piece with a length of 120 mm and a width of 120 mm are not curved into the shape of one end of a semi-arc or the shape of one end of a C-shape, and the average warpage value of the four corners is 35 mm or less. The laminated sheet is an aromatic polyimide film having a thickness of 10 to 200 μm, a hydrosilylation reaction-cured silicone rubber, a thickness of 1.2 to 5 mm, and contains a cyclic dimethylsiloxane tetramer to a 15-mer. The amount is 250 mass ppm or less, (A) fumed silica is contained as a reinforcing filler, the elongation specified by JIS K 6249 is 380% or more, and the tensile stress at 100% elongation is 0.20 to 0. The content of cyclic dimethylsiloxane tetramer to 15mer is 250% by mass or less between the silicone rubber sheet at 1.35 MPa, and (B) organic functional organoalkoxysilane or a partial hydrolysis condensate thereof. Hydrosilylation reaction-curable liquid silicone rubber composition containing (A) fumed silica as a reinforcing filler. The hydrosilylation reaction-curable liquid silicone rubber composition is heated under pressure with a thin layer interposed therebetween. It can be produced by curing the thin layer.

The thickness of the heat-curable liquid silicone rubber composition thin layer by the hydrosilylation reaction may be significantly smaller than the thickness of the silicone rubber sheet, and is not particularly limited, but is preferably 1/7 to 1 of the thickness of the silicone rubber sheet. / 28. (B) The organic functional organoalkoxysilane or a partially hydrolyzed condensate thereof is preferably contained in the thin layer of the hydrosilylation reaction-curable liquid silicone rubber composition in an amount of 0.1 to 6% by mass. If too much pressure is applied during curing, the heat-curable liquid silicone rubber composition due to the hydrosilylation reaction will flow out, so 6 MPa or less is preferable, and 4 to 2 MPa is more preferable.

The thickness of the silicone rubber layer constituting the laminated sheet is 1.2 to 5.0 mm, preferably 1.3 to 5.0 mm, more preferably 1.4 to 5.0 mm, and further preferably. Is 1.6 to 2.2 mm. This is because if the thickness of the silicone rubber layer is too thin, gas may easily leak, and if the thickness of the silicone rubber layer is too large, it is meaningless.
The cured product of the heat-curable liquid silicone rubber composition by the hydrosilylation reaction has an elongation of 380 specified in JIS K 6249 from the viewpoint of gas leakage prevention when used as a septum for sealing the opening of a headspace vial. % Or more, more preferably 400% or more. In addition, the tensile stress at 100% elongation is preferably 0.20 to 1.35 MPa, more preferably 0.30 to 1.35 MPa.
The tear strength (angle type) defined in JIS K 6249 is preferably 10 N / mm or more, and more preferably 11 N / mm or more, from the same point of view.

In the laminated sheet made of the aromatic polyimide resin film and the silicone rubber layer thus manufactured (made), the aromatic polyimide resin film and the silicone rubber layer are well adhered to each other, and JIS K6854-2 (adhesive-peeling). The peeling adhesive strength based on the adhesive strength test method (Part 2: 180 degree peeling) is 5N / 25mm or more, preferably 8N / 25mm or more, more preferably 18N / 25mm or more, and most preferably. Even if a cut is made between the aromatic polyimide resin film and the silicone rubber layer using a cutting tool, the silicone rubber layer on the aromatic polyimide resin film cannot be peeled off. That is, the silicone rubber layer cannot be peeled off from the aromatic polyimide resin film, and cannot be peeled off.

The laminated sheet thus manufactured (made) in which the aromatic polyimide resin film is adhered to one side of the silicone rubber layer is the average of the four corners when the laminated sheet is made into a square laminated sheet test piece having a length of 120 mm and a width of 120 mm. It has flatness and flatness to the extent that the warp value is 35 mm or less . If even one corner (one corner) is curved to the shape of one end of a semi-arc or the shape of one end of a C-shape, it is not included in the average warp value of 35 mm or less, and is treated as a comparative example. The average warpage value of the four corners of a square laminated sheet test piece having a length of 120 mm and a width of 120 mm is preferably 32 mm or less, more preferably 20 mm or less, and further preferably 10 mm or less.
Needless to say, the shape and size of the laminated sheet in which the aromatic polyimide resin film is adhered to one side of the silicone rubber layer is not limited to a square having a length of 120 mm and a width of 120 mm and the size thereof.

The laminated sheet thus manufactured (made) in which the polyimide resin film is adhered to both sides of the silicone rubber layer is the average warp value of the four corners when it is made into a square laminated sheet test piece having a length of 120 mm and a width of 120 mm. It has flatness and flatness to the extent that the thickness is 5 mm or less . If even one corner (one corner) is curved to the shape of one end of a semi-arc or the shape of one end of a C-shape, it is not included in the average warp value of 35 mm or less, and is treated as a comparative example. The average warpage value of the four corners of a square laminated sheet test piece having a length of 120 mm and a width of 120 mm is preferably 2 mm or less, and more preferably completely flat. Needless to say, the shape and size of the laminated sheet in which the aromatic polyimide resin film is adhered to both sides of the silicone rubber layer is not limited to a square having a length of 120 mm and a width of 120 mm and the size thereof.

With such a laminated sheet having a small average warp value, the punching work into a small shape becomes easy, and the septum made of the laminated sheet punched into a small shape has flatness. Examples of the punched shape include a circle, a square, a regular hexagon, and a regular octagon, but the shape is preferably circular in terms of ease of fitting inside the headspace cap and ease of attachment to the circular opening of the headspace vial. The diameter is not particularly limited as long as it is larger than the diameter of the circular opening of the headspace vial and equal to or less than the inner diameter of the headspace cap. For example, it is 5 to 30 mm.

The fourth invention of the present application contains an aromatic polyimide film having a thickness of 10 to 200 μm, (A) fumed silica as a reinforcing filler, and (B) organic functional organoalkoxysilane or a partial hydrolysis condensation thereof. Due to the hydrosilylation reaction, the elongation of the cured product specified by JIS K 6249 is 250% or more, and the tensile stress at 100% elongation specified by JIS K 6249 is 0.1 to 0.49 MPa. The silicone gel composition is first cured by bringing it into close contact with a heat-curable silicone gel composition and heating it at 90 ° C. or higher and 240 ° C. or lower under pressure, and then, in hot air, cyclic dimethylsiloxane tetramer to For headspace gas chromatograph analysis or for sealing the opening of a vial for headspace gas chromatograph mass analysis, characterized in that the content of the 15-mer is placed to 250 mass ppm or less for secondary curing. A laminated sheet for forming a septum, which contains an aromatic polyimide film having a thickness of 10 to 200 μm and a cyclic dimethylsiloxane tetramer to a 15-mer having a thickness of 1.2 to 5 mm. Is 250 mass ppm or less, contains (A) fumed silica as a reinforcing filler, and the elongation of the cured product specified by JIS K 6249 is 250% or more, and at 100% elongation specified by JIS K 6249. The hydrosilylation reaction-cured silicone gel layer having a tensile stress of 0.1 to 0.49 MPa is laminated in an adhesive state, and the four corners of a square laminated sheet test piece having a length of 120 mm and a width of 120 mm are one end of a semi-arc. The present invention relates to a method for manufacturing a laminated sheet in which the average warpage value of the four corners is 35 mm or less without being curved into the shape of 1 or the shape of one end of a C shape.

The heat-curable silicone gel composition by a hydrosilylation reaction containing (A) fumed silica as a reinforcing filler has a content of cyclic dimethylsiloxane tetramer to 15-mer having a content of more than 250 mass ppm as described above. There is some overlap between the heat-curable liquid silicone rubber composition by hydrosilylation reaction containing fumed silica as a reinforcing filler and the elongation of the cured product and the tensile stress at 100% elongation. As can be seen by comparing the hardness of the silicone gel of No. 4 with the hardness of the silicone rubber of Table 1 to Table 3, the silicone gel is a type A durometer defined by JIS K 6249 and JIS K 6253, that is, type A hardness. Is less than 15, which is lower in hardness than silicone rubber.

The heat-curable silicone gel composition by hydrosilylation reaction containing (A) fumed silica as a reinforcing filler has a content of cyclic dimethylsiloxane tetramer to 15-mer having a content of more than 250 mass ppm as described above. It is almost the same as the heat-curable liquid silicone rubber composition by hydrosilylation reaction containing fumed silica as a reinforcing filler in terms of composition, production method and curability.
However, unlike the heat-curable liquid silicone rubber composition by the hydrosilylation reaction described above, the blending amount of the component (b) is the silicon atom bond hydrogen atom in the component (b) and the silicon atom bond in the component (a). The molar ratio with an alkenyl group, for example, a vinyl group is usually (0.53: 1) to (0.68: 1), preferably (0.54: 1) to (0). It is an amount such that .67: 1).
It is said that about 10,000 to 30,000 ppm of organosiloxane oligomer (for example, cyclic dimethylsiloxane oligomer) due to the component (a) remains in a commercially available normal grade silicone gel composition. ..

(A) Heat-curable silicone gel composition by hydrosilylation reaction containing fumed silica as a reinforcing filler The primary curing condition of the silicone gel composition is a heat-curing type by a hydrosilylation reaction containing fumed silica as a reinforcing filler. Unlike the primary curing conditions of the liquid silicone rubber composition, the temperature is not limited to 145 ° C or lower, and 90 ° C or higher and 240 ° C or lower are preferable.

When the laminated sheet composed of the primary cured product and the aromatic polyimide film is used as a septum for sealing a headspace vial, as described above, this primary cured product contains about several thousand ppm of cyclic organosiloxane oligomer. This may interfere with headspace gas chromatograph analysis and headspace gas chromatograph mass spectrometry. Therefore, by placing the laminated sheet composed of the primary cured product and the aromatic polyimide film in hot air, preferably hot air, the cyclic organosiloxane oligomer in the silicone gel which is the primary cured product, particularly cyclic dimethylsiloxane. Tetramers to 15-mer are volatilized and removed to a value of 250 ppm or less, preferably 210 ppm or less, more preferably 100 ppm or less.

Heating in hot air takes a long time when the heating temperature is low, so it is preferably 90 ° C or higher and 110 ° C or higher, and 240 ° C or lower and 220 ° C or lower in order to avoid an increase in warpage of the laminated sheet. It is preferably 250 ° C. or lower, and more preferably 250 ° C. or lower. The heating time may be shorter as the temperature increases, preferably 30 minutes to 6 hours, more preferably 1 hour to 5 hours. Needless to say, heating in hot air is under non-pressurization.
The gas for that purpose is preferably heated air, and may be an inert gas such as heated nitrogen gas.

As heating in hot air, a method of discontinuously heating in a hot air circulation type oven in a state where the heat-curable silicone gel composition layer by the hydrosilylation reaction is adhered to the aromatic polyimide resin film, horizontally or horizontally. An example is a method of continuously heating in a vertically long hot air oven.

The heat-curable silicone gel composition obtained by the hydrosilylation reaction containing (A) fumed silica as a reinforcing filler is liquid A of a general-purpose two-component liquid silicone rubber composition kit sold by a silicone manufacturer. It can be easily produced by changing the blending ratio of the liquid B and the liquid B so as to reduce the modulus and mixing them.

The fifth invention of the present application contains an aromatic polyimide film having a thickness of 10 to 200 μm, a cyclic dimethylsiloxane tetramer to 15-mer having a content of more than 250 mass ppm, and fumed silica as a reinforcing filler. The heat-curable silicone rubber composition (I) by a hydrosilylation reaction in which the elongation specified by JIS K 6249 of the cured product is 380% or more and the tensile stress at 100% elongation is 0.20 to 1.35 MPa. Alternatively, (B) the heat-curable liquid silicone rubber composition (II) produced by the hydrosilylation reaction containing (B) an organic functional organoalkoxysilane or a partially hydrolyzed condensate thereof is brought into close contact with the composition, and the temperature is 90 ° C. or higher at 145 ° C. or higher under pressure. The silicone rubber composition is first-cured by heating at a temperature of ° C. or lower, and then placed in hot air until the content of the cyclic dimethylsiloxane tetramer to 15-mer is 250 mass ppm or less for secondary curing. A laminated sheet for forming a septum for sealing an opening of a vial for headspace gas chromatograph analysis or headspace gas chromatograph mass analysis, which is characterized by a thickness of 10 to 200 μm. Aromatic polyimide film, thickness is 1.2 to 5 mm, content of cyclic dimethylsiloxane tetramer to 15-mer is 250 mass ppm or less, and (A) fumed silica is used as a reinforcing filler. Hydrosilylation reaction-cured silicone rubber layer (I) or further (B) containing and having an elongation of 380% or more and a tensile stress at 100% elongation of 0.20 to 1.35 MPa as defined by JIS K 6249. The hydrosilylated reaction-curable silicone rubber layer (II) containing the organically functional organoalkoxysilane or a partially hydrolyzed condensate thereof is laminated in an adhered state, and a square laminated sheet test piece having a length of 120 mm and a width of 120 mm is laminated. The four corners do not bend to the shape of one end of the semi-arc or the shape of one end of the C-shape, and the four corners do not bend to the shape of one end of the half-arc or the shape of one end of the C-shape, and the average of the four corners. The present invention relates to a method for manufacturing a laminated sheet having a warp value of 35 mm or less.

In the fifth invention of the present application, the heat-curable liquid silicone rubber composition by a hydrosilylation reaction used for forming a silicone rubber layer in a laminated sheet in which an aromatic polyimide film and a silicone rubber layer are adhered and laminated is It is the same as the heat-curable liquid silicone rubber composition by hydrosilylation reaction used in the second invention of the present application, except that the content of the cyclic dimethylsiloxane tetramer to 15-mer is more than 250 mass ppm.
Considering the D4-D15 content of 750 ppm in the silicone rubber in Comparative Example 14 of Table 10, the heat-curable liquid silicone rubber composition by the hydrosilylation reaction contains the cyclic dimethylsiloxane tetramer to 15-mer. Is more than 750 mass ppm.
The curing conditions of the heat-curable liquid silicone rubber composition by the hydrosilylation reaction are the same as the curing conditions of the heat-curable silicone gel composition by the hydrosilylation reaction in the fourth invention of the present application.

The laminated sheet specified in claim 1 of the present application can also be manufactured by the production methods shown in Examples 16 and 20.

The sixth invention of the present application is an aromatic polyimide film having a thickness of 10 to 200 μm, a thickness of 1.2 to 5 mm, and a content of cyclic dimethylsiloxane tetramer to 15-mer of 250 ppm or less, preferably 250 ppm or less. It is 100 mass ppm or less, contains (A) fumed silica as a reinforcing filler, has an elongation of 380% or more specified by JIS K 6249, and has a tensile stress of 0.20 to 1. The hydrosilylation reaction-curable silicone rubber layer (I) at 35 MPa or the hydrosilylation reaction-curable silicone rubber layer (II) containing (B) an organic functional organoalkoxysilane or a partially hydrolyzed condensate thereof are in an adhesive state. The peeling adhesive strength based on JIS K6854-2 (adhesive-peeling adhesive strength test method-Part 2: 180 degree peeling) is 5N or more, and a square lamination of 120 mm in length and 120 mm in width is laminated. The four corners of the sheet test piece are not curved into the shape of one end of a semi-arc or the shape of one end of a C-shape, and are made of a laminated sheet having an average warpage value of the four corners of 35 mm or less. The present invention relates to a septum for sealing an opening of a vial for a tograph analysis method or a headspace gas chromatograph mass analysis method.

A wide variety of products for headspace gas chromatograph analysis or headspace gas chromatograph mass spectrometry are sold by Agilent Technologies, Shimadzu GLC Co., Ltd., etc. in the United States. A typical example is shown in FIG.

Headspace vials are broadly divided into headspace crimp top vials and headspace screw vials. FIG. 8 is an example of a headspace screw vial.
Both vials are usually made of glass and are made of primary hydrolyzable class borosilicate glass according to the requirements of the United States Pharmacopeia and the European Pharmacopoeia. Flat-bottomed types with internal volumes of 10 ml and 20 ml are on the market, and round-bottomed types with internal volumes of 10 ml and 20 ml.
Caps that fit into the openings of the cylindrical body are roughly classified into headspace crimp caps and headspace screw caps. Both are usually made of light metals such as aluminum and silver-aluminum alloys.

Both the headspace crimp cap and the headspace screw cap have a circular hole 6 in the center of the upper surface as shown in FIG.
The disk-shaped septum 3 made of a laminated sheet composed of an aromatic polyimide film and a silicone rubber layer is fitted inside a cap 5 having a circular hole 6 in the center of the upper surface so that the aromatic polyimide film faces the front. That is, it is fitted internally.
The upper surface of the opening of the vial 4 is covered with the screw cap 5 with a septum and twisted well to seal the opening. Since the screw cap 5 has a circular hole 6 in the center of the upper surface, the needle 10 of the sample probe 9 can be inserted into the disc-shaped septum 3 to collect the headspace gas in the vial 4.

In FIG. 9, the septum for sealing the opening of the vial for the headspace gas chromatograph analysis method or the headspace gas chromatograph mass analysis method according to the sixth invention of the present application is heated to a high temperature (eg, 300 ° C.) and is an inert gas. When the needle 10 of the sample probe 9 is inserted into the septum 3 and the headspace gas in the vial 4 is collected while the internal pressure of the vial is increased by the press-fitting of the vial 4, the silicone rubber layer strongly holds the needle. It has excellent gas leakage prevention, that is, gas leakage resistance. The gas leak prevention property, that is, the gas leak resistance can be evaluated by the [gas leak test method from septum] in the example.

The septum for sealing the opening of the vial for the headspace gas chromatograph analysis method or the headspace gas chromatograph mass analysis method is "an aromatic polyimide resin film having a thickness of 10 to 200 μm and a thickness of 1.2 to 1. It is 5 mm, the content of cyclic dimethylsiloxane tetramer to 15-mer is 250 mass ppm or less, preferably 100 ppm or less, and (A) fumed silica is contained as a reinforcing filler, which is specified in JIS K 6249. Hydrosilylation reaction-cured silicone rubber layer (I) having an elongation of 380% or more and a tensile strength at 100% elongation of 0.20 to 1.35 MPa, or (B) an organic functional organoalkoxysilane or A laminated sheet in which the hydrosilylation reaction-curable silicone rubber layer (II) containing the partially hydrolyzed condensate is laminated in an adhered state can be produced by punching into a predetermined shape with a cutting tool.

Examples of the punched shape include a circle, a square, a regular hexagon, and a regular octagon, but the shape is preferably circular in terms of ease of fitting inside the headspace cap and ease of attachment to the circular opening of the headspace vial. The diameter is not particularly limited as long as it is larger than the inner diameter of the circular opening of the headspace vial and equal to or less than the inner diameter of the headspace cap. For example, it is 5 to 30 mm.

The 7th invention of the present application has an aromatic polyimide film having a thickness of 10 to 200 μm, a thickness of 1.2 to 5 mm, and a content of cyclic dimethylsiloxane tetramer to 15-mer of 250 mass ppm or less. Hydrosilylation, which contains (A) fumed silica as a reinforcing filler, has an elongation of 380% or more specified by JIS K 6249, and has a tensile stress of 0.20 to 1.35 MPa at 100% elongation. The reaction-cured silicone rubber layer (I) or (B) the hydrosilylated reaction-cured silicone rubber layer (II) containing the organically functional organoalkoxysilane or a partially hydrolyzed condensate thereof is laminated in an adhesive state. , JIS K6854-2 (Adhesive-Peeling Adhesive Strength Test Method-Part 2: 180 Degree Peeling) has a peeling adhesive strength of 5N or more, and the four corners of a square laminated sheet test piece with a length of 120 mm and a width of 120 mm. A septum made of laminated sheets that does not bend into the shape of one end of a semi-arc or the shape of one end of a C-shape and has an average warpage value of 35 mm or less at the four corners seals the vial used for headspace gas analysis. It is useful as a septum for.
This septum can be easily manufactured by punching the laminated sheet according to claim 1 into a circular shape or the like. Its shape is usually disc-shaped, but it is not limited as it is appropriately changed according to the shape of the opening of the vial.

The vials for headspace gas chromatograph analysis and vials for headspace gas chromatograph mass spectrometry in the first to seventh inventions of the present application are vials for barge & trap gas chromatograph analysis and for gas stripping gas chromatograph analysis. Vials, barges & traps Gas chromatographs Mass spectrometric vials. It may be a vial for gas stripping gas chromatograph mass spectrometry.

The septum of the eighth invention of the present application is a septum composed of a laminate of an aromatic polyimide film and a hydrosilylation reaction-curing silicone rubber layer, and the hydrosilylation reaction-curing silicone rubber is used as a reinforcing filler (A) fumed silica. Hydrosilylation reaction-curable silicone rubber composition containing methylhydrogenpolysiloxane having at least 3 hydrosilyl groups as a cross-linking agent and hydrodimethylsiloxy group-sealed dimethylpolysiloxane (polymerization degree 3 or less) at both ends of the molecular chain. It is characterized by being a cured product of an object.
The septum can further contain (B) an organically functional organoalkoxysilane or a partially hydrolyzed condensate thereof.
Among the components (b), the total peak area of the low molecular weight siloxane generated from the silicone rubber layer when the septams other than the septum for the headspace vial are heated at high temperature is small, so that the hydrodimethylsiloxy group-blocking dimethyltri at both ends is small. Siloxane is the best, followed by bi-terminal hydrodimethylsiloxy group-blocking dimethyldisiloxane.

This septum is provided at the sample inlet of the gas chromatograph that sends the headspace gas to the analytical column, and is a septum (partition wall) for separating the inside from the outside world, a septum in the sample vaporization chamber of the gas chromatograph, and a sample. It is also useful as a sample for vaporization units. This septum can be easily manufactured by punching the laminated sheet according to claim 1 into a circular shape or the like. In addition, a septum, which is a laminate having a predetermined shape, can be manufactured by using a mold having a predetermined internal shape.
The shape is exemplified by a disk shape, a disk shape, a prismatic shape, and a columnar shape, but the shape is not limited as it is appropriately changed depending on the application location. The thickness of the silicone rubber layer is exemplified by 1.2 to 50 mm, but is not limited as it is appropriately changed depending on the application location.

Hereinafter, the present invention will be described in detail with reference to Examples, Reference Examples, and Comparative Examples. A laminated sheet composed of an aromatic polyimide film and a silicone rubber layer was produced according to the method shown below, and the characteristics were measured according to the method shown below. In the examples, with respect to the blending amount, "parts" means "parts by mass" and "%" means "% by mass". Unless otherwise specified, work and measurements were performed in the air and at room temperature.

[Material used in the examples]
[1] Aromatic polyimide resin film manufactured by Toray DuPont Co., Ltd., trade name Kapton 200H / V was used.
Product description by the manufacturer: The film thickness is 50 μm, the tensile strength is 300 MPa (MD, TD), the tensile elongation is 85% (MD, TD), the tensile modulus is 3.3 GPa (MD, TD), and the tear propagation resistance is 6. 7N ・ mm ^-1 (MD), 6.9N ・ mm ^-1 (TD), thermal shrinkage (200 ° C.) 0.20% (MD), 0.05% (TD).

[2] [Heat-curable liquid silicone gel composition or heat-curable liquid silicone rubber composition by hydrosilylation reaction having a small content of cyclic dimethylsiloxane oligomer]
(a) DOW CORNING TORAY CY 52-276 Part A and Part B
Product description by manufacturer: Silicone gel, potting material, two-component type, 1: 1 mixture, additive heat curing, low temperature curing, low viscosity, CV type (cyclic dimethylsiloxane tetramer to cyclic dimethylsiloxane tetramer (D4-) D10) Content: 50% by mass ppm)
Needle insertion = 75 mm / 10 (W / 60)
Viscosity-Part A = 1Pa ・ s
Viscosity-Part B = 0.8Pa ・ s
Working Time at 25 ° C = 0.5hrs
Gel hardness = 70 Grams / Penetration
Note: It is understood that it does not contain a filler because it is colorless and transparent. Since it is an addition type heat curable, it is a curable type by a hydrosilylation reaction.
Working Time at 25 ° C = 0.5 hrs, it is understood that it contains a hydrosilylation reaction inhibitor.

(b) DOW CORNING EG-3100 KIT
Product description by manufacturer: Silicone gel, potting material, 2 liquids, 1: 1 mixture, additive heat curing, low viscosity, CV type.
Appearance: Transparent / Transparent, 1: 1 Viscosity after mixing (25 ° C): 325mPa · s, Pot life: 18 hours or more, Density: 0.98g / cm ³ , Hardness [JIS Type A]: NA, Needle penetration [ JIS K2220]: 85mm / 10, low molecular weight siloxane D4-D10 component amount: 0.012%
Note: It is understood that it does not contain a filler because it is colorless and transparent. Since it is an addition type heat curable, it is a curable type by a hydrosilylation reaction. Since it has a long pot life, it is understood that it contains a hydrosilylation reaction inhibitor.
DOW CORNING is a registered trademark.

(c) DOW CORNING SE1720CV KIT
Product description by manufacturer: 2 liquids, white, 1: 1 mixture, non-corrosive, self-adhesive, high strength, non-slump, less void generation, fast curing, CV grade characteristic value viscosity (Part A): 37,700 mPa ・s
Viscosity (Part B): 41,900 mPa ・ s
Working time: 360 minutes Usable time: 270 days Shear: 240psi
Durometer of 100 ° C. cured 1: 1 mixture A: 33 Shore A
1: 1 mixture 100 ° C, 60 minutes cure elongation: 375%
1: 1 mixture 100 ° C, 60 minutes Cured product tensile strength: 480psi
Note: Due to its high strength, it is understood that it contains a reinforcing silica filler, and it is understood as a liquid silicone rubber composition by a hydrosilylation reaction. It is understood that the amount of small molecule siloxane D4-D10 component per CV grade is small.

(D) XIAMETER ^TM RBL-9200-40 LSR
Made by US DOW CORNING CORPORATION.
Product description by the manufacturer: It is a general-purpose LSR and has excellent workability due to its improved rheological characteristics and long pot life.
Liquid silicone rubber composition with a hardness of 40 degrees, liquid A and liquid B 1: 1 mixture, for molds, for injection molding
Liquid A viscosity: 130 Pa ・ s, Liquid B viscosity: 120 Pa ・ s,
Pot life: The mixture of liquid A and liquid B can be used for 72 hours after mixing in an environment of 25 ° C.
Curing: Fast curing at high temperature. At 2 mm thickness, it cures at 196 ° C in 6-10 seconds. Curing time depends on the thickness of the final product and the curing temperature.
[Characteristics of 5 minutes / 150 ° C cured product]
Relative density: 1.12
Hardness (shore aA): 44
Tensile strength: 9MPa
Growth: 510%
Tear strength: 37N / mm
Note: Due to its high strength, it is understood to contain a reinforcing filler. Since it is not CV grade, it is estimated that several thousand to 30,000 ppm of cyclic dimethylsiloxane oligomer remains.
XIAMETER is a registered trademark.

[3] Fumed Silica Aerosil RX200: Sold by Nippon Aerosil Co., Ltd. Hydrophobic fumed silica post-treated with hexamethyldisilazane, BET specific surface area 140 m ² / g

[4] Vinyl group-containing diorganopolysiloxane for Example 16 Didimethylpolysiloxane having both ends sealed with dimethylvinylsiloxy groups (vinyl group content 0.23% by mass, viscosity 2,000 mPa · s)
[5] Hydrosilylation reaction cross-linking agent (having at least 3 hydrosilyl groups in one molecule)
Crosslinking agent A: Dimethylsiloxane / methylhydrogensiloxane copolymer with both ends of the molecular chain sealed with a trimethylsiloxy group, Me _3SiO (Me _2SiO ) ₅ (MeHSiO) ₃ SiMe ₃ , Si bond H content: 0.75 mass %, Viscosity: 5.1 mPa · s. (Me is a methyl group)
Crosslinking agent B: Dimethylsiloxane / methylhydrogensiloxane copolymer with both ends of the molecular chain sealed with a trimethylsiloxy group, Me _3SiO (Me _2SiO ) ₁₆ (MeHSiO) ₅ SiMe _3, Si bond H content: 0.3 mass %, Viscosity: 15 mPa · s.
Crosslinking agent B1: Didimethylsiloxane / methylhydrogensiloxane copolymer with both ends of the molecular chain sealed with a trimethylsiloxy group, Me _3SiO (Me _2SiO ) ₁₈ (MeHSiO) ₂₀ SiMe ₃
Content of Si bond H: 0.75% by mass, viscosity: 30 mPa · s.
Crosslinking agent C: Methylhydrogenpolysiloxane with both ends of the molecular chain sealed with a trimethylsiloxy group, Me 3SiO (MeHSiO) ₆₅ SiMe _{3 ,} Si bond H content: 1.6% by mass, viscosity: 20 mPa · s.
All of the above-mentioned cross-linking agents have at least three Si-bonded Hs (silicon-bonded hydrogen atoms, hydrosilyl groups) in one molecule.

[6] Hydrosilylation reaction cross-linking agent (chain extender)
Chain extender T: Content of dimethyltrisiloxane, HMe _2SiO (Me _2SiO ) ₃ SiMe ₂ H, Si bond H with _both ends of the molecular chain sealed with H (CH ₃ ) 2SiO: 0.56% by mass, viscosity : 2mPa · s.
Chain extender D: Content of dimethyltetrasiloxane, HMe _2SiO (Me _2SiO ) ₄ SiMe ₂ H, Si bond H with _both ends of the molecular chain sealed with H (CH ₃ ) 2SiO: 0.47% by mass, viscosity : 2.5mPa ・ s
Chain extender P: dimethylpolysiloxane with both ends of the molecular chain sealed with H (CH ₃ ) _2SiO , HMe _{2SiO (Me 2SiO) 19 SiMe 2 H , Si} bond H content: 0.13% by mass, viscosity : 13mPa · s.

[6] DOW CORNING TORAY SRX 212 CATALYST for Example 16 and Example 20
An organic platinum compound solution that is a platinum-based catalyst for the hydrosilylation reaction.

The above-mentioned heat-curable liquid silicone rubber composition by hydrosilylation reaction and heat-curable liquid silicone gel composition by hydrosilylation reaction manufactured by DOW CORNING CORPORATION include a platinum-based catalyst together with methylhydrogenpolysiloxane as a curing agent. Since it is presumed that it has been mixed, it is not necessary to mix it.
[7] Hydrosilylation reaction inhibitor ETCH for Example 16 and Example 20
10% by mass solution of 1-ethynyl-1-cyclohexanol

[7] AP-001
A mixture of 5 parts by mass of γ-glycidoxypropyltrimethoxysilane, 5 parts by mass of vinyltrimethoxysilane, and 0.2 parts by mass of tetrabutyl titanate.

[SiH / SiVi ratio estimation method]
1. Heat-curable liquid silicone gel composition
1) (a) Both-ended dimethylvinylsiloxy group-blocked dimethylpolysiloxane having a vinyl group content of 0.47% by mass, and (b) both-terminal trimethylsiloxy group-blocking dimethyl having a silicon atom-bonded hydrogen atom content of 0.75% by mass. A heat-curable liquid silicone gel composition comprising a siloxane / methylhydrogensiloxane copolymer, (c) a platinum-based catalyst, and (d) an ethylcyclohexinol as a hydrosilylation reaction inhibitor is prepared.
2) At that time, the total amount of (a) and (b) was 99.50% by mass, (c) was 7.5 ppm as the amount of platinum metal, and (d) was 0.5% by mass. Mixture 14 in which the compounding ratios of (a) and (b) are finely changed so that the SiH / SiVi ratio is 0.40,0.45,0.50,0.60,0.65,0.70,0.80,0.90,1.00,1.10,1.20,1.30,1.40. The seeds were prepared, defoamed, and then weighed in an aluminum dish so that the thickness was about 6 mm. Each heat-curable liquid silicone gel composition weighed in an aluminum dish was cured by heating at 120 ° C. for 30 minutes and then at 180 ° C. for 1 hour to obtain a silicone gel piece. The hardness of each silicone gel piece was measured with an Asker rubber hardness tester C type specified by SRIS 0101.
3) For each SiH / SiVi ratio, the hardness by the Asker rubber hardness tester C type, that is, the Asker C hardness is scaled on graph paper and shown in FIG. As the SiH / Vi ratio increased, the Asker C hardness increased, peaking at SiH / SiVi = 1.3, and the result was that the Asker C hardness did not increase any further.
4) The silicone gel piece obtained by mixing and curing EG-3100A solution and EG-3100B solution, which are heat-curable liquid silicone gel compositions, at a mass ratio of 1/1, had an Asker C hardness of 3.5. ..
The silicone gel piece obtained by mixing and curing the heat-curable liquid silicone gel composition CY52-276A solution and CY52-276B solution at a mass ratio of 1/1 had an Asker C hardness of 3.5.
5) In the graph of Fig. 11, SiH / SiVi = 0.4 and Asker C hardness is 3.5, so the mass ratio 1/1 mixture of EG-3100A liquid and EG-3100B liquid is SiH / SiVi ratio = 0.4. It is estimated that the mass ratio of CY52-276A solution and CY52-276B solution is 1/1, and the mixture is SiH / SiVi ratio = 0.4.

2. Heat-curable liquid silicone rubber composition
The mass% of RBL-9200-40B in the mixture of RBL-9200-40A and RBL-9200-40B was changed in 9 ways as shown in Fig. 12, and the mixture was manually mixed. After defoaming, it was poured into a 6 mm thick metal frame. , Press-cured at 150 ° C. for 10 minutes, and then secondarily cured at 180 ° C. for 1 hour in hot air to obtain a silicone rubber sheet. Hardness was measured by a type A durometer specified in JIS K 6249.
Liquid A: Liquid B = 50:50 and the hardness by the Type A durometer, that is, the Type A hardness is 44, but if the B liquid ratio is slightly reduced, the Type A hardness decreases slightly, and conversely, the B liquid ratio. When the amount was slightly increased, the type A hardness increased slightly and reached a peak.
1. 1. From the results of, it is known that the type A hardness peaks when SiH / SiVi = 1.3, so the RBL-9200-40 has SiH / Vi = 1.2 when A / B = 1/1. Can be estimated.

The basic characteristics of the cured product of the heat-curable liquid silicone rubber composition by the hydrosilylation reaction and the basic characteristics of the cured product of the heat-curable liquid silicone gel composition by the hydrosilylation reaction are the temperature and time shown in each table. , Press vulcanization, that is, a test piece having a thickness of 2 mm obtained by curing under pressure was measured.
Density, hardness, tensile strength, elongation and tear strength were measured according to JIS K 6249. A type A durometer was used to measure the hardness, and an angled test piece was used to measure the tear strength.
50% modulus is the tensile stress at 50% elongation when the elongation is measured according to JIS K 6249.
100% modulus is the tensile stress at 100% elongation when elongation is measured according to JIS K 6249.
The elongation at the start of tearing is the elongation at the start of tearing of the angled test piece when the tear strength is measured according to JIS K 6249.

[Conditions for quantitative analysis of cyclic dimethylsiloxane tetramer to cyclic dimethylsiloxane 15-mer (hereinafter abbreviated as D4 to D15) by GC-MS for a cured product of a heat-curable liquid silicone rubber composition by a hydrosilylation reaction. ]
・ Equipment used: Agilent 7890GC / 5977MSD
・ Temperature conditions for analysis: 1) Hold at 40 ° C for 2 minutes, 2) Heat up at 20 ° C / min, 3) Hold at 300 ° C for 3 minutes ・ Ion source: EI
・ MS range: 30-400
・ Ion mode: SIM

The molecular weight at which various cyclic dimethylsiloxane oligomers are easily ionized and the molecular weight of the internal standard were selected as follows.
D4 RT ~ 4m / z 43,57,156,281,282,341
D5 RT 4 ～ 6.5m / z 43,57,267,355,356
D6 RT 6.5 ～ 7.5m / z 43,57,325,341,342
D7 RT 7.5-8m / z 43,57,281,282,341
D8 RT 8-9m / z 43,57,281,355,356
D9 RT 9 ～ 9.5m / z 43,57,341,355,356
D10 ～ D15 RT 9.5 ～ m / z 43,57,281,355,356

[Method for preparing samples for quantitative analysis of D4 to D15 in silicone rubber]
The prepared silicone rubber sheet was chopped into pieces of about 1 mm square, 0.3 g was placed in a screw tube, 3 ml of an internal standard (n-undecane) 200 ppm hexane solution was added, and the mixture was cured at room temperature for 8 hours. Then, the screw tube was shaken well and 1.5 ml of the supernatant was taken into a vial to prepare a sample.

[Data processing method]
The concentration was converted by substituting it into the prepared calibration curve (prepared from the analysis of each solution of D4 to D7 50,5,0.5,0.05ppm at the internal standard of 200ppm under the same analysis conditions).
However, since D8 and later do not have a standard solution, it was calculated in terms of D4.

[Quantitative analysis method of D4 to D15 in headspace gas]
(1) A disk-shaped septum (diameter) punched from a laminated sheet composed of an aromatic polyimide resin film and a silicone rubber layer inside an aluminum screw cap (inner diameter: 17.5 mm) having a hole (inner diameter: 8 mm) on the upper surface. 17.5 mm) is fitted so that the aromatic polyimide resin film is in front.
(2) The septum is placed in the upper opening of a screw vial made of Hokei glass (outer diameter: 23 mm, body height: 60 mm, mouth internal diameter: 12 mm, mouth height: 15 mm) having an internal volume of 20 ml. Cover with an aluminum screw cap and twist well to seal the top opening.
(3) A screw vial with a sealed upper surface opening is fitted into the head space portion (heating portion) of the head space gas chromatograph, and heated at 300 ° C. for 10 minutes.
(4) Needle that is a sampling needle for a sample probe (manufactured by Agilent Technologies, product number G4556-60125) (outer diameter 1/32 inch (0.79 mm) of the cylindrical part, inner diameter 0.56 mm, tip is approximately truncated cone) Is punctured into the septum.
(5) Since the inside of the screw vial is in a pressurized state, the headspace gas (including the component that the silicone rubber of the septum is heated and volatilized) is sent to the sample probe and then the gas chromatograph below via the transfer line. It flows into the (GC) capillary column.
(6) Since D4-D15 in the headspace gas is separated into 12 peaks, the area of each peak is calculated. The area of each peak is applied to the calibration curve (horizontal axis: concentration, vertical axis: peak area) created in advance to calculate each concentration, and the total concentration of D4-D15, that is, the total content is calculated.

[Method I for producing a laminated sheet in which a hydrosilylation reaction-curing silicone rubber layer is laminated on one side of an aromatic polyimide resin film in an adhesive state]
1) Set a gold frame (capacity 13.0 cc) with an inner diameter of 120 mm x 120 mm x depth of 1.0 mm on a flat, distortion-free stainless steel plate (lower plate) of the press vulcanizer, and set the above-mentioned gold frame. An aromatic polyimide resin film was laid inside.
2) A heat-curable liquid silicone rubber composition by a hydrosilylation reaction was poured onto an aromatic polyimide resin film in a metal frame.
3) A clean fluororesin film (for example, PTFE film) is put on a heat-curable liquid silicone rubber composition by a hydrosilylation reaction in a metal frame, and a flat and distortion-free stainless steel plate is placed on the film. rice field.
4) The assembled product in 4) was placed on the lower plate of a press vulcanizer heated to a predetermined curing temperature, the lower plate was hydraulically pushed up to the upper plate, pressurized at 20 MPa, and heated for a predetermined time.
5) After a predetermined time, the lower plate was lowered and the pressurized assembly was taken out.
6) Remove the stainless steel plate and fluororesin film (for example, PTFE film) on the removed assembly, and make a laminated sheet in which a hydrosilylation reaction-curing silicone rubber layer is laminated on one side of the aromatic polyimide resin film in an adhesive state. I took it out of the frame.

[Method for producing a laminated sheet in which an aromatic polyimide resin film is laminated on a hydrosilylation reaction-cured silicone rubber layer via a thin layer of a silicone adhesive in an bonded state II]
1) Set a gold frame (capacity 13.0 cc) with an inner diameter of 120 mm x 120 mm x depth of 1.0 mm on a flat, distortion-free stainless steel plate (lower plate) of the press vulcanizer, and set the above-mentioned gold frame. A pre-molded hydrosilylation reaction-curing silicone rubber sheet was laid inside.
2) The heat-curable liquid silicone adhesive composition by hydrosilylation reaction was thinly and uniformly applied to the silicone rubber sheet in the metal frame to a thickness of about 100 μm.
3) An aromatic polyimide resin film was put on the liquid silicone adhesive composition, and a flat and distortion-free stainless steel plate was placed on the film.
4) Place the assembly in 3) on the lower plate of the press vulcanizer heated to the specified curing temperature, hydraulically push the lower plate up to the upper plate, pressurize at 3 MPa, and heat at 120 ° C for 10 minutes. did.
5) After a predetermined time, the lower plate was lowered and the pressurized assembly was taken out.
6) The stainless steel plate and fluororesin film (for example, PTFE film) on the removed assembly are removed, and the aromatic polyimide resin film is laminated on the hydrosilylation reaction-cured silicone rubber layer via the silicone adhesive thin layer in an adhesive state. The laminated sheet was taken out from the inside of the metal frame.

[Method for producing a laminated sheet in which an aromatic polyimide resin film is laminated on both sides of a silicone rubber layer in an adhesive state]
1) Set a gold frame (capacity 13.0 cc) with an inner diameter of 120 mm x 120 mm x depth of 1.0 mm on a flat, distortion-free stainless steel plate (lower plate) of the press vulcanizer, and set the above-mentioned gold frame. An aromatic polyimide resin film was laid inside.
2) A heat-curable liquid silicone rubber composition by a hydrosilylation reaction was poured onto an aromatic polyimide resin film in a metal frame.
3) An aromatic polyimide resin film was put on a heat-curable liquid silicone rubber composition by a hydrosilylation reaction in a metal frame, and a flat and distortion-free stainless steel plate was placed on the polyimide resin film.
4) The assembled product in 3) was placed on the lower plate of a press vulcanizer heated to a predetermined curing temperature, the lower plate was hydraulically pushed up to the upper plate, pressurized at 20 MPa, and heated for a predetermined time.
5) After a predetermined time, the lower plate was lowered and the pressurized assembly was taken out.
6) The stainless steel plate on the removed assembly was removed, and the laminated sheet in which the aromatic polyimide resin film was laminated on both sides of the silicone rubber layer in an adhesive state was taken out from the inside of the metal frame.

[Peeling adhesive strength test of laminated sheet]
The produced laminated sheet having a length of 120 mm and a width of 120 mm was cut into a tape so as to have a length of 115 mm and a width of 20 mm.
For the tip of this tape, use a knife to make a cut between the aromatic polyimide resin film and the silicone rubber layer, peel off the silicone rubber layer on the polyimide resin film by 3 cm in the length direction, and apply JIS K6854-2 (adhesive). Based on the agent-peeling adhesive strength test method-Part 2: 180 degree peeling), the tip of the polyimide resin film and the tip of the silicone rubber layer are grasped by the chuck of the tensile tester and pulled in the opposite direction by 180 degrees. A strength test was performed. The tensile speed was 80 mm / min. The acceptance criteria were 5N / 25mm , that is, 4N / 20mm . The adhesive strength between the aromatic polyimide resin film and the silicone rubber layer is large, and even if a cut is made between the aromatic polyimide resin film and the silicone rubber layer using a knife, the silicone rubber layer on the aromatic polyimide resin film is long. If it could not be peeled off in the direction, it was indicated that it could not be peeled off.

[Observation of the degree of warpage of laminated sheets]
In many cases, the laminated sheet taken out from the inside of the metal frame having an inner diameter of 120 mm × 120 mm × depth of 0.9 mm has at least one side and one corner slightly warped (curled), so that it should be concave on a flat surface. After being placed in place and allowed to cool, the degree of warpage and the degree of curvature of the four sides and corners were visually observed from the sides.

[Average warp value test of laminated sheet]
The laminated sheet taken out from the inside of the metal frame having an inner diameter of 120 mm × 120 mm × depth of 0.9 mm is allowed to stand on a flat surface so as to have a concave shape, and after allowing to cool, the distances from the flat surface at the four corners (h1, h2, h3, h4: Unit mm) was actually measured, and the average value was taken as the average warp value (mm), and specifically, it was calculated by the following equation.
Average warp value (mm) = (h1 + h2 + h3 + h4) / 4
If even one of the four corners is curved like the shape of one end of a semicircle , or if it is curved like the shape of one end of a C-shape, it is treated as a comparative example and the average warpage value is used. Without calculation, for example, it was displayed as curved more than a semicircular arc.

[Gas leak test method from septum]
1. Preparation 10 disc-shaped septums (17.5 mm in diameter) consisting of a laminated sheet consisting of an aromatic polyimide resin film and a silicone rubber layer, a screw vial made of Hokei glass with an internal volume of 20 ml (outer diameter: 23 mm, height of the body part) Prepare 10 aluminum screw caps (inner diameter: 17.5 mm) having a hole (inner diameter: 8 mm) on the upper surface, 10 pieces of 60 mm, internal diameter of the mouth part: 12 mm, height of the mouth part: 15 mm).

2. Procedure
(1) A disk-shaped septum (diameter) formed from a laminated sheet composed of an aromatic polyimide resin film and a silicone rubber layer inside an aluminum screw cap (inner diameter: 17.5 mm) having a hole (inner diameter: 8 mm) on the upper surface. 17.5 mm) is fitted so that the aromatic polyimide resin film is in front.
(2) The septum is placed in the upper opening of a screw vial made of Hokei glass (outer diameter: 23 mm, body height: 60 mm, mouth internal diameter: 12 mm, mouth height: 15 mm) having an internal volume of 20 ml. Cover with an aluminum screw cap and twist well to seal the top opening.
(3) The screw vial sealed with the septum and the screw cap is placed in the head space portion (heating portion) of the head space gas chromatograph and heated at 300 ° C. for 10 minutes.
(4) Insert the needle of the sample probe (manufactured by Agilent Technologies, product number G4556-60125) into the septum (the outer diameter of the cylindrical part is 1/32 inch (0.79 mm), the inner diameter is 0.56 mm, and the tip is approximately a truncated cone). , Open the switching valve and press the pressurized helium gas into the vial.
(5) When the internal pressure of the vial reaches 0.105 MPa, the switching valve is closed and the injection of helium gas is stopped. The pressurized headspace gas in the vial (the gas phase containing the component in which the septum is heated and volatilized) is filled in the sample loop.
(6) The pressurized headspace gas in the sample loop is injected into the column of the gas chromatograph (GC) via the transfer line. Meanwhile, the needle remains stuck in the septum of the vial.
(7) Perform gas chromatograph analysis and observe the peak in the chart.

3. Judgment If there is no gas leak at the puncture site of the septum, the peak of the cyclic dimethylsiloxane oligomer is present in the gas chromatogram, but if there is a gas leak, the peak of the cyclic dimethylsiloxane oligomer is not present. When the peak of the cyclic dimethylsiloxane oligomer was present in the gas chromatogram, it was determined that there was no gas leak, and when the peak of the cyclic dimethylsiloxane oligomer was not present in the gas chromatogram, it was determined that there was a gas leak.
4. Display in the table of Example and Comparative Example When there was no gas leak in all 10 lines, it was displayed as 0/10. For example, when 2 out of 10 gas leaked, it was displayed as 2/10. For example, if the second gas leaked, it was displayed as 1/2 without further testing.

[A screw vial whose mouth is sealed with a disk-shaped septum made of a laminated sheet consisting of an aromatic polyimide resin film and a silicone rubber layer and a screw cap is placed in the headspace part (heating part) of the headspace gas chromatograph and heated. The volatile components generated from the silicone rubber layer were injected into a gas chromatograph (GC) column, gas chromatograph analysis was performed under predetermined temperature conditions, and multiple low molecular weight siloxane peaks in the displayed chromatogram How to find the total area]

-Headspace gas chromatograph, which is an analytical instrument: Agilent 7890GC / 5977MSD. Agilent is a registered trademark.
・ Ion source: EI
-Column used: Agilent HP5MS (30m)
・ Loop size: 1 ml
・ Analysis conditions Split ratio 1:10
Analysis range 30-400 mass
HS section conditions 300 ° C, 10 minutes Analytical section conditions 40 ° C, 2 minutes hold → 20 ° C / min temperature rise → 300 ° C, 3 minutes hold

1. Preparation 10 disc-shaped septums (17.5 mm in diameter) consisting of a laminated sheet consisting of an aromatic polyimide resin film and a silicone rubber layer, a screw vial made of Hokei glass with an internal volume of 20 ml (outer diameter: 23 mm, height of the body part) Prepare 10 aluminum screw caps (inner diameter: 17.5 mm) having a hole (inner diameter: 8 mm) on the upper surface, 10 pieces of 60 mm, internal diameter of the mouth part: 12 mm, height of the mouth part: 15 mm).

2. Procedure
(1) A disk-shaped septum (diameter) formed from a laminated sheet composed of an aromatic polyimide resin film and a silicone rubber layer inside an aluminum screw cap (inner diameter: 17.5 mm) having a hole (inner diameter: 8 mm) on the upper surface. 17.5 mm) is fitted so that the aromatic polyimide resin film is in front.
(2) The septum is placed in the upper opening of a screw vial made of Hokei glass (outer diameter: 23 mm, body height: 60 mm, mouth internal diameter: 12 mm, mouth height: 15 mm) having an internal volume of 20 ml. Cover with an aluminum screw cap and twist well to seal the top opening.
(3) The screw vial sealed with the septum and the screw cap is placed in the head space portion (heating portion) of the head space gas chromatograph and heated at 300 ° C. for 10 minutes.
(4) Insert the needle of the sample probe (manufactured by Agilent Technologies, product number G4556-60125) into the septum (the outer diameter of the cylindrical part is 1/32 inch (0.79 mm), the inner diameter is 0.56 mm, and the tip is approximately a truncated cone). , Open the switching valve and press the pressurized helium gas into the vial.
(5) When the internal pressure of the vial reaches 0.105 MPa, the switching valve is closed and the injection of helium gas is stopped. The pressurized headspace gas in the vial (the gas phase containing the component in which the septum is heated and volatilized) is filled in the sample loop.
(6) The pressurized headspace gas in the sample loop is injected into the column of the gas chromatograph (GC) via the transfer line. Meanwhile, the needle remains stuck in the septum of the vial.
(7) Perform gas chromatograph analysis under the temperature conditions of 40 ° C., hold for 2 minutes → temperature rise at 20 ° C./min → hold at 300 ° C. for 3 minutes, and observe each peak of the displayed chromatogram.

3. 3. How to find the total area of multiple low-molecular-weight siloxane (low-polymerization siloxane) peaks Low-molecular-weight siloxane (low-polymerization siloxane) from the area values of each peak automatically calculated by the analysis software built into the above analysis equipment. ) Corresponds to the peak and sums those values.

[Example 1] (Table 1)
50 parts of the A solution of the DOW CORNING EG-3100 KIT and 10.0 parts of Aerosil RX200 were added to a planetary mixer and mixed until uniform to prepare a composition A.
50 parts of the B solution of the DOW CORNING EG-3100 KIT and 10.0 parts of Aerosil RX200 were added to a planetary mixer and mixed until uniform to prepare a fluid composition B.
60. To prepare a heat-curable liquid silicone rubber composition (containing 16.2% by mass of Aerosil RX200) by hydrosilylation reaction.

The heat-curable liquid silicone rubber composition obtained by this hydrosilylation reaction is heated at 120 ° C. for 10 minutes under a pressure of 20 MPa (the same applies to all Examples, Reference Examples, and Comparative Examples except the Examples in Table 7). Table 1 shows the rubber properties measured for the 2 mm thick test piece obtained by curing and the D4-D15 content in the silicone rubber.

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. is used, and the above-mentioned “hydrosilylation reaction cured silicone rubber layer is formed on one side of the aromatic polyimide resin film”. According to "Method I for Producing Laminated Sheets Laminated in Adhesive State", the capton 200H / V film and the hydrosilylation reaction-curable silicone rubber layer (thickness 1.4 mm) adhere to each other by heating at 120 ° C. for 10 minutes under pressure. A laminated sheet to be laminated was produced.

In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer were firmly adhered to each other, the degree of warpage was small, and the aromatic polyimide resin film was not wrinkled.
The average warpage value, peeling adhesive strength, D4-D15 content in headspace gas, and the number of gas leaks of this laminated sheet were measured and shown in Table 1.

[Example 2] (Table 1)
50 parts of solution A and 12.5 parts of Aerosil RX20012.5 parts of the above DOW CORNING EG-3100KIT were added to a planetary mixer and mixed until uniform to prepare a fluid composition A.
50 parts of solution B of the DOW CORNING EG-3100KIT and 12.5 parts of Aerosil RX20012.5 parts were added to a planetary mixer and mixed until uniform to prepare a fluid composition B.
62.5 parts of the fluid composition, 62.5 parts of the fluid composition, 1.1 parts of the cross-linking agent, 1.5 parts of the chain extender D, and 1.0 part of AP-001 are uniformly added to the planetary mixer. A heat-curable liquid silicone rubber composition (containing 19.4% by mass of Aerosil RX200) was prepared by mixing until it became a hydrosilylation reaction.

The rubber properties and the D4-D15 content in the silicone rubber measured for a 2 mm thick test piece obtained by curing the heat-curable liquid silicone rubber composition by this hydrosilylation reaction by heating at 120 ° C. for 10 minutes under pressure were measured. It is shown in Table 1.

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. is used, and the above-mentioned “hydrosilylation reaction cured silicone rubber layer is formed on one side of the aromatic polyimide resin film”. According to "Method I for Producing Laminated Sheets Laminated in Adhesive State", the film was heated at 120 ° C. for 10 minutes under pressure to form a Capton 200H / V film and a hydrosilylation reaction-cured silicone rubber layer (thickness of silicone rubber layer: 1.9 mm). A laminated sheet was produced in which and were adhered to each other.

In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer were firmly adhered to each other, the degree of warpage was small, and the aromatic polyimide resin film was not wrinkled.
The average warpage value, peeling adhesive strength, D4-D15 content in headspace gas, and the number of gas leaks of this laminated sheet were measured and shown in Table 1.

[Example 3] (Table 1)
In Example 1, a heat-curable liquid silicone rubber composition by a hydrosilylation reaction under the same conditions except that the thickness of the silicone rubber layer was 1.8 mm instead of 1.4 mm] (Aerosil RX200 was 16.2 mass%). (Contains) was prepared, and a laminated sheet was prepared.

The rubber properties and the D4-D15 content in the silicone rubber measured for a 2 mm thick test piece obtained by curing the heat-curable liquid silicone rubber composition by this hydrosilylation reaction by heating at 120 ° C. for 10 minutes under pressure were measured. It is shown in Table 1.
In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer were firmly adhered to each other, the degree of warpage was small, and the polyimide resin film was not wrinkled.
The average warpage value, peeling adhesive strength, D4-D15 content in headspace gas, and the number of gas leaks of this laminated sheet were measured and shown in Table 1.

[Comparative Example 1] (Table 1)
50 parts of the A solution of the DOW CORNING EG-3100 KIT and 10.0 parts of Aerosil RX200 were added to a planetary mixer and mixed until uniform to prepare a fluid composition A.
50 parts of the B solution of the DOW CORNING EG-3100 KIT and 10.0 parts of Aerosil RX200 were added to a planetary mixer and mixed until uniform to prepare a fluid composition B.
60.0 parts of the fluid composition, 60.0 parts of the fluid composition, 2.06 parts of the cross-linking agent A and AP-0011.0 are added to the planetary mixer and mixed until uniform, and the hydrosilylation reaction A heat-curable liquid silicone rubber composition (containing 16.3% by mass of Aerosil RX200) was prepared.

Table 1 shows the rubber properties measured for a 2 mm thick test piece obtained by curing the heat-curable liquid silicone rubber composition by this hydrosilylation reaction by heating at 120 ° C. for 10 minutes under pressure.

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. is used, and the above-mentioned “hydrosilylation reaction cured silicone rubber layer is formed on one side of the aromatic polyimide resin film”. According to "Method I for Producing Laminated Sheets Laminated in Adhesive State", the film was heated at 120 ° C. for 10 minutes under pressure to form a Capton 200H / V film and a hydrosilylation reaction-cured silicone rubber layer (thickness of silicone rubber layer: 1.4 mm). A laminated sheet was produced in which and were adhered to each other.

In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer were firmly adhered to each other, the degree of warpage was small, and the aromatic polyimide resin film was not wrinkled, but one out of three leaked gas. ..
The average warpage value, peeling adhesive strength, and number of gas leaks of this laminated sheet were measured and shown in Table 1.

[Comparative Example 2] (Table 1)
50 parts of solution A of the DOW CORNING EG-3100 KIT and 12.5 parts of Aerosil RX200 12.5 parts were added to a planetary mixer and mixed until uniform to prepare a fluid composition A.
50 parts of solution B of the DOW CORNING EG-3100 KIT and 12.5 parts of Aerosil RX200 12.5 parts were added to a planetary mixer and mixed until uniform to prepare a fluid composition B.
In a planetary mixer, 62.5 parts of the fluid composition, 62.5 parts of the fluid composition, 2.06 parts of the cross-linking agent A and AP-0011.0 are added and mixed until uniform, and a hydrosilylation reaction is carried out. A heat-curable liquid silicone rubber composition (containing 19.5% by mass of Aerosil RX200) was prepared.

Table 1 shows the rubber properties measured for a 2 mm thick test piece obtained by curing the heat-curable liquid silicone rubber composition by this hydrosilylation reaction by heating at 120 ° C. for 10 minutes under pressure.

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. is used, and the above-mentioned “hydrosilylation reaction cured silicone rubber layer is formed on one side of the aromatic polyimide resin film”. According to "Method I for Producing Laminated Sheets Laminated in Adhesive State", the film was heated at 120 ° C. for 10 minutes under pressure to form a Capton 200H / V film and a hydrosilylation reaction-cured silicone rubber layer (thickness of silicone rubber layer: 1.4 mm). A laminated sheet was produced in which and were adhered to each other.

In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer were firmly adhered to each other, the degree of warpage was small, and the aromatic polyimide resin film was not wrinkled, but 3 out of 3 leaked gas. ..
The average warpage value, peeling adhesive strength, and number of gas leaks of this laminated sheet were measured and shown in Table 1.

[Comparative Example 3] (Table 1)
In Example 3, the Capton 200H / V film and the hydrosilylation reaction-curing silicone rubber layer (thickness of the silicone rubber layer: 1.1 mm) adhere to each other under the same conditions except that the thickness of the silicone rubber layer is 1.1 mm. A laminated sheet was produced.
The rubber properties and the D4-D15 content in the silicone rubber measured for a 2 mm thick test piece obtained by curing the heat-curable liquid silicone rubber composition by this hydrosilylation reaction by heating at 120 ° C. for 10 minutes under pressure were measured. It is shown in Table 1.
In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer were firmly adhered to each other, the degree of warpage was small, and the polyimide resin film was not wrinkled, but two out of ten had gas leaks. The average warpage value, peeling adhesive strength, D4-D15 content in headspace gas, and the number of gas leaks of this laminated sheet were measured and shown in Table 1.

[Comparative Example 4] (Table 2)
50 parts of the DOW CORNING TORAY CY 52-276 Part A and 5.0 parts of Aerosil RX200 were added to a planetary mixer and mixed until uniform to prepare a fluid composition A.
50 parts of the DOW CORNING TORAY CY 52-276 Part B and 5.0 parts of Aerosil RX200 were added to a planetary mixer and mixed until uniform to prepare a fluid composition B.
To a planetary mixer, 55.0 parts of the fluid composition, 55.0 parts of the fluid composition, 1.15 parts of the cross-linking agent A and AP-0011.0 are added and mixed until uniform, and a hydrosilylation reaction is carried out. A heat-curable liquid silicone rubber composition (containing 8.9% by mass of Aerosil RX200) was prepared.

Table 2 shows the rubber properties measured for a 2 mm thick test piece obtained by curing the heat-curable liquid silicone rubber composition by this hydrosilylation reaction by heating at 100 ° C. for 20 minutes under pressure.

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. is used, and the above-mentioned “hydrosilylation reaction cured silicone rubber layer is formed on one side of the aromatic polyimide resin film”. According to "Method I for Producing Laminated Sheets Laminated in Adhesive State", the capton 200H / V film and the hydrosilylation reaction-cured silicone rubber layer (thickness of silicone rubber layer: 1.4 mm) are formed by heating at 100 ° C. for 20 minutes. A laminated sheet that was bonded and laminated was produced.

In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer (thickness 1.4 mm) were firmly adhered to each other, the degree of warpage was small, and the aromatic polyimide resin film was not wrinkled. One was leaking gas.
The average warpage value, peeling adhesive strength, and number of gas leaks of this laminated sheet were measured and shown in Table 3.

[Example 4] (Table 2)
50 parts of the DOW CORNING TORAY CY 52-276 Part A and 10 parts of Aerosil RX200 were added to a planetary mixer and mixed until uniform to prepare a fluid composition A.
50 parts of the DOW CORNING TORAY CY 52-276 Part B and 10 parts of Aerosil RX200 were added to a planetary mixer and mixed until uniform to prepare a fluid composition B.
60 parts of fluid composition A, 60 parts of fluid composition B, 1.15 parts of cross-linking agent A (methylhydrogenpolysiloxane) and AP-0011.0 are added to a planetary mixer and mixed until uniform. , A heat-curable liquid silicone rubber composition (containing 16.4% by mass of Aerosil RX200) by hydrosilylation reaction was prepared.

The rubber properties measured for a 2 mm thick test piece obtained by curing the heat-curable liquid silicone rubber composition by this hydrosilylation reaction at 100 ° C. for 20 minutes under pressure and the D4-D15 content in the silicone rubber are shown. Shown in 3.

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. is used, and the above-mentioned “hydrosilylation reaction cured silicone rubber layer is formed on one side of the aromatic polyimide resin film”. According to "Method I for Producing Laminated Sheets Laminated in Adhesive State", the capton 200H / V film and the hydrosilylation reaction-curable silicone rubber layer (thickness 1.4 mm) are adhered by heating at 100 ° C. for 20 minutes under pressure. A laminated sheet to be laminated was produced.

In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer were firmly adhered to each other, the degree of warpage was small, and the aromatic polyimide resin film was not wrinkled.
The average warpage value, peeling adhesive strength, D4-D15 content in headspace gas, and the number of gas leaks of this laminated sheet were measured and shown in Table 3.
No gas leaked out of 10 of them.

[Example 5] (Table 2)
In Example 4, 12.5 parts were put into DOW CORNING TORAY CY 52-276 Part A 50 parts instead of Aerosil RX200 10 parts, and Aerosil RX200 10 parts were put into DOW CORNING TORAY CY 52-276 Part B 50 parts. A heat-curable liquid silicone rubber composition (containing 19.7% by mass of RX200) was prepared by hydrosilylation reaction under the same conditions except that 12.5 parts were added instead of the above, and Capton 200H / V film and Hydrosilyl were prepared. A laminated sheet was prepared in which a chemical reaction-cured silicone rubber layer (thickness 1.4 mm) was adhered and laminated.
The rubber properties measured for a 2 mm thick test piece obtained by curing the heat-curable liquid silicone rubber composition by this hydrosilylation reaction at 100 ° C. for 20 minutes under pressure and the D4-D15 content in the silicone rubber are shown. Shown in 2.
In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer were firmly adhered to each other, the degree of warpage was moderate, and the aromatic polyimide resin film was not wrinkled.
The average warpage value, peeling adhesive strength, and number of gas leaks of this laminated sheet were measured and shown in Table 2.
No gas leaked out of 10 of them.

[Example 6] (Table 2)
In Example 4, 7.5 parts were put into 50 parts of DOW CORNING TORAY CY52-276 PartA instead of 10 parts of Aerosil RX200, and 7 parts were put into 50 parts of DOW CORNING TORAY CY52-276 PartB instead of 10 parts of Aerosil RX200. A heat-curable liquid silicone rubber composition by hydrosilylation reaction (Aerosil RX200 12.) under the same conditions except that .5 parts were added and 2.2 parts of cross-linking agent B was added instead of 1.15 parts of cross-linking agent A. (Containing 7% by mass) was prepared, and a laminated sheet was prepared in which a Capton 200H / V film and a hydrosilylated reaction-cured silicone rubber layer (thickness 1.4 mm) were adhered and laminated.

The rubber properties measured for a 2 mm thick test piece obtained by curing the heat-curable liquid silicone rubber composition by this hydrosilylation reaction at 100 ° C. for 20 minutes under pressure and the D4-D15 content in the silicone rubber are shown. Shown in 2.
In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer were firmly adhered to each other, the degree of warpage was small, and the aromatic polyimide resin film was not wrinkled.
The average warpage value, peeling adhesive strength, and number of gas leaks of this laminated sheet were measured and shown in Table 2.
No gas leaked out of 10 of them.

[Comparative Example 5] (Table 2)
In Example 6, a heat-curable liquid silicone rubber composition (Aerodil RX200 by 12.8 mass) by a hydrosilylation reaction under the same conditions except that 0.78 parts of the cross-linking agent C was added instead of 2.2 parts of the cross-linking agent A. %) Was prepared, and a laminated sheet was prepared in which a Capton 200H / V film and a hydrosilylation reaction-curing silicone rubber layer (thickness 1.4 mm) were adhered and laminated.
Table 2 shows the rubber properties measured for a 2 mm thick test piece obtained by curing the heat-curable liquid silicone rubber composition by this hydrosilylation reaction by heating at 100 ° C. for 20 minutes under pressure. The elongation is 206%, which is extremely small.
In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer were firmly adhered to each other, the degree of warpage was moderate, and the polyimide resin film was not wrinkled.
The average warpage value, peeling adhesive strength, and number of gas leaks of this laminated sheet were measured and shown in Table 2.
Eight out of ten leaked gas.

[Example 7] (Table 3)
In Example 4, a heat-curable liquid silicone rubber composition by a hydrosilylation reaction (16.2% by mass of the RX200) was prepared under the same conditions except that 2.2 parts of the cross-linking agent B was added instead of 1.15 parts of the cross-linking agent A. (Contains) was prepared, and a laminated sheet was prepared.
The rubber properties measured for a 2 mm thick test piece obtained by curing the heat-curable liquid silicone rubber composition by this hydrosilylation reaction at 100 ° C. for 10 minutes under pressure and the D4-D15 content in the silicone rubber are shown. Shown in 3.
In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer were firmly adhered to each other, the degree of warpage was small, and the aromatic polyimide resin film was not wrinkled.
The average warpage value, peeling adhesive strength, D4-D15 content in headspace gas, and the number of gas leaks of this laminated sheet were measured and shown in Table 3.
No gas leaked out of 10 of them.

[Example 8 (Table 3)
In Example 5, a heat-curable liquid silicone rubber composition (Aerosil RX200 was added in an amount of 19.5% by mass) by a hydrosilylation reaction under the same conditions except that 2.2 parts of the cross-linking agent B was added instead of 1.15 parts of the cross-linking agent A. (Contains) was prepared, and a laminated sheet was prepared.
The rubber properties measured for a 2 mm thick test piece obtained by curing the heat-curable liquid silicone rubber composition by this hydrosilylation reaction at 100 ° C. for 10 minutes under pressure and the D4-D15 content in the silicone rubber are shown. Shown in 3.
In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer were firmly adhered to each other, the degree of warpage was small, and the aromatic polyimide resin film was not wrinkled.
The average warpage value, peeling adhesive strength, D4-D15 content in headspace gas, and the number of gas leaks of this laminated sheet were measured and shown in Table 3.
No gas leaked out of 10 of them.

[Example 9] (Table 3)
In Example 4, 15 copies of Aerosil RX200 were added to 50 copies of DOW CORNING TORAY CY52-276 Part A, and 15 copies were added to 50 copies of DOW CORNING TORAY CY52-276 Part B instead of 10 copies of Aerosil RX200. A heat-curable liquid silicone rubber composition (containing 22.7% by mass of Aerosil RX200) by hydrosilylation reaction was prepared under the same conditions except that it was added, and Capton 200H / V film and hydrosilylation reaction-curing silicone rubber layer (thickness) were prepared. A laminated sheet was prepared by adhering to 1.9 mm) and laminating.

The rubber properties measured with a 2 mm thick test piece obtained by curing the heat-curable liquid silicone rubber composition by this hydrosilylation reaction at 100 ° C. for 20 minutes under pressure and the D4-D15 content in the silicone rubber are shown. Shown in 3.
In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer were firmly adhered to each other, the degree of warpage was small, and the aromatic polyimide resin film was not wrinkled.
The average warpage value, peeling adhesive strength, D4-D15 content in headspace gas, and the number of gas leaks of this laminated sheet were measured and shown in Table 3.
No gas leaked out of 10 of them.

[Comparative Example 6] (Table 3)
In Example 4, a heat-curable liquid silicone rubber composition (Aerodil RX200 by 16.4 mass) by a hydrosilylation reaction under the same conditions except that 0.78 parts of the cross-linking agent C was added instead of 1.15 parts of the cross-linking agent A. %) Was prepared, and a laminated sheet was prepared in which a Capton 200H / V film and a hydrosilylation reaction-curing silicone rubber layer (thickness 1.4 mm) were adhered and laminated.
Table 3 shows the rubber properties measured with a 2 mm thick test piece obtained by curing the heat-curable liquid silicone rubber composition by this hydrosilylation reaction by heating at 100 ° C. for 10 minutes under pressure. The elongation was 220%.
In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer were firmly adhered to each other, the degree of warpage was reasonable, and the polyimide resin film was not wrinkled. Since the second gas leaked, the gas leak test was stopped.
The average warpage value, peeling adhesive strength, and number of gas leaks of this laminated sheet were measured and shown in Table 3.

[Comparative Example 7] (Table 3)
In Example 5, a heat-curable liquid silicone rubber composition (Aerodil RX200 by 19.7 mass) by a hydrosilylation reaction under the same conditions except that 0.78 parts of the cross-linking agent C was added instead of 1.15 parts of the cross-linking agent A. %) Was prepared, and a laminated sheet was prepared in which a Capton 200H / V film and a hydrosilylation reaction-curing silicone rubber layer (thickness 1.4 mm) were adhered and laminated.
Table 3 shows the rubber properties measured with a 2 mm thick test piece obtained by curing the heat-curable liquid silicone rubber composition by this hydrosilylation reaction by heating at 100 ° C. for 10 minutes under pressure. The growth was 250%.
In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer were firmly adhered to each other, the degree of warpage was reasonable, and the aromatic polyimide resin film was not wrinkled. Since the second gas leaked, the gas leak test was stopped.
The average warpage value, peeling adhesive strength, and number of gas leaks of this laminated sheet were measured and shown in Table 3.

[Reference Example 1] (Table 4)
Add 31.6 parts of RBL-9200-40A, 8.4 parts of RBL-9200-40B and AP-0010.04 parts to a planetary mixer, mix until uniform, and heat-cure liquid by hydrosilylation reaction. A silicone gel composition (SiH / SiVi ratio = 0.50; containing 23% by mass of hydrosilica) was prepared. The heat-curable liquid silicone gel composition obtained by this hydrosilylation reaction was heated at 120 ° C. for 10 minutes under pressure to obtain a sheet-like gel having a thickness of 2 mm. Then, this sheet-shaped gel was secondarily cured in a hot air circulation oven at 200 ° C. for 4 hours, and then the characteristic values of the 2 mm-thick silicone gel pieces were measured and shown in Table 4.

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. is used, and the above-mentioned “hydrosilylation reaction cured silicone rubber layer is formed on one side of the aromatic polyimide resin film”. According to "Method I for Producing Laminated Sheets Laminated in Adhesive State", the laminated sheet is heated at 120 ° C. under pressure for 10 minutes, and the Capton 200H / V film and the hydrosilylation reaction-cured silicone gel layer are adhered and laminated. Was produced. This laminated sheet was secondarily cured in a hot air circulation oven at 200 ° C. for 4 hours.

In this laminated sheet, the aromatic polyimide resin film and the silicone gel layer (thickness 1.9 mm) were well adhered to each other, the degree of warpage was small, and the polyimide resin film was not wrinkled.
The average warpage value and the peeling adhesive strength of this laminated sheet were measured and shown in Table 4.

[Example 10] (Table 4)
Add 30.8 parts of RBL-9200-40A, 9.2 parts of RBL-9200-40B and AP-0010.04 parts to a planetary mixer, mix until uniform, and heat-cure liquid by hydrosilylation reaction. A silicone gel composition (SiH / SiVi ratio = 0.55, containing 23% by mass of hydrosilica) was prepared. The heat-curable liquid silicone gel composition obtained by this hydrosilylation reaction was heated at 120 ° C. for 10 minutes under pressure at 20 Pa to form a sheet having a thickness of 2 mm. Then, the sheet-shaped gel was secondarily cured in a hot air circulation oven at 200 ° C. for 4 hours, and then the characteristic values of the 2 mm-thick silicone gel pieces and the D4-D15 content in the silicone gel were measured. Table 4 It was shown to.

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. is used, and the above-mentioned “hydrosilylation reaction cured silicone rubber layer is formed on one side of the aromatic polyimide resin film”. According to "Method I for Producing Laminated Sheets Laminated in Adhesive State", the laminated sheet is heated at 120 ° C. under pressure for 10 minutes, and the Capton 200H / V film and the hydrosilylation reaction-cured silicone gel layer are adhered and laminated. Was produced. This laminated sheet was secondarily cured in a hot air circulation oven at 200 ° C. for 4 hours.

In this laminated sheet, the aromatic polyimide resin film and the silicone gel layer (thickness 1.9 mm) were well adhered to each other, the degree of warpage was small, and the aromatic polyimide resin film was not wrinkled.
The average warpage value, peeling adhesive strength, D4-D15 content in headspace gas, and the number of gas leaks of this laminated sheet were measured and shown in Table 4.
No gas leaked out of 10 of them.

[Reference Example 2] (Table 4)
30.0 parts of RBL-9200-40A, 10 parts of RBL-9200-40B and AP-0010.04 parts are put into a planetary mixer, mixed until uniform, and heat-curable liquid silicone gel by hydrosilylation reaction. A composition (SiH / SiVi ratio = 0.60; containing 23% by mass of hydrosilica) was prepared. The heat-curable liquid silicone gel composition obtained by this hydrosilylation reaction was heated at 120 ° C. for 10 minutes under pressure to obtain a sheet-like gel having a thickness of 2 mm. Then, this sheet-shaped gel was secondarily cured in a hot air circulation oven at 200 ° C. for 4 hours, and then the characteristic values of the 2 mm-thick silicone gel pieces were measured and shown in Table 4.

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. is used, and the above-mentioned “hydrosilylation reaction cured silicone rubber layer is formed on one side of the aromatic polyimide resin film”. According to "Method I for Producing Laminated Sheets Laminated in Adhesive State", the laminated sheet is heated at 120 ° C. under pressure for 10 minutes, and the Capton 200H / V film and the hydrosilylation reaction-cured silicone gel layer are adhered and laminated. Was produced. This laminated sheet was secondarily cured in a hot air circulation oven at 200 ° C. for 4 hours.

In this laminated sheet, the aromatic polyimide resin film and the silicone gel layer (thickness 1.9 mm) were well adhered to each other, the degree of warpage was small, and the polyimide resin film was not wrinkled.
The average warpage value and the peeling adhesive strength of this laminated sheet were measured and shown in Table 4.

[Example 11] (Table 4)
29.2 parts of RBL-9200-40A, 10.8 parts of RBL-9200-40B and AP-0010.04 parts are added to a planetary mixer, mixed until uniform, and heated and cured by a hydrosilylation reaction. A silicone gel composition (SiH / SiVi ratio = 0.65, containing 23% by mass of hydrosilica) was prepared. The heat-curable liquid silicone gel composition obtained by this hydrosilylation reaction was heated at 120 ° C. for 10 minutes under pressure to form a sheet, and then placed in a hot air circulation oven at 200 ° C. for 4 hours to be secondarily cured to a thickness of 2 mm. The characteristic values of the silicone gel pieces and the D4-D15 content in the silicone gel were measured and shown in Table 4.

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. is used, and the above-mentioned “hydrosilylation reaction cured silicone rubber layer is formed on one side of the aromatic polyimide resin film”. Using "Method I for producing laminated sheets laminated in a bonded state", the Capton 200H / V film and the hydrosilylated reaction-curing silicone gel layer (thickness 1.9 mm) are bonded by heating at 120 ° C. for 10 minutes under pressure. To prepare a laminated sheet to be laminated.

Then, this laminated sheet was placed in a hot air circulation type oven at 200 ° C. for 4 hours for secondary curing .
In this laminated sheet, the aromatic polyimide resin film and the silicone gel layer (thickness 1.9 mm) were firmly adhered to each other, the degree of warpage was small, and the aromatic polyimide resin film was not wrinkled.
The average warpage value, peeling adhesive strength, D4-D15 content in headspace gas, and the number of gas leaks of this laminated sheet were measured and shown in Table 4.
No gas leaked out of 10 of them.

[Comparative Example 8] (Table 4)
28.4 parts of RBL-9200-40A, 11.6 parts of RBL-9200-40B and AP-0010.04 parts are added to a planetary mixer, mixed until uniform, and heated and cured by a hydrosilylation reaction. A silicone gel composition (SiH / SiVi ratio = 0.70; containing 23% by mass of hydrosilica) was prepared. The heat-curable liquid silicone gel composition obtained by this hydrosilylation reaction was heated at 120 ° C. for 10 minutes under pressure to form a sheet, and then placed in a hot air circulation oven at 200 ° C. for 4 hours to be secondarily cured to a thickness of 2 mm. The characteristic values of the silicone gel pieces and the D4-D15 content were measured and shown in Table 4.

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. is used, and the above-mentioned “hydrosilylation reaction cured silicone rubber layer is formed on one side of the aromatic polyimide resin film”. According to "Method I for Producing Laminated Sheets Laminated in Adhesive State", the capton 200H / V film and the hydrosilylation reaction-curing silicone gel layer (thickness 1.9 mm) adhere to each other by heating at 120 ° C. for 10 minutes under pressure. A laminated sheet to be laminated was produced.

Then, this laminated sheet was placed in a hot air circulation type oven at 200 ° C. for 4 hours for secondary curing .
In this laminated sheet, the aromatic polyimide resin film and the silicone gel layer (thickness 1.9 mm) are firmly adhered to each other , but the front side and the back side are curved more than a semicircular shape in the side view. ..

[Comparative Example 9] (Table 5)
50 parts of CY52-276A and 12.5 parts of RX20012.5 parts were put into a planetary mixer and mixed until uniform to prepare a fluid composition A.
50 parts of CY52-276B and 12.5 parts of RX20012.5 parts were put into a planetary mixer and mixed until uniform to prepare a fluid composition B.
62.5 parts of the fluid composition A, 62.5 parts of the fluid composition B, 1.15 parts of the cross-linking agent A and 1.0 part of AP-001 are added to a planetary mixer and mixed until uniform, and a hydrosilylation reaction is carried out. A heat-curable liquid silicone rubber composition (containing 19.7% by mass of RX200) was prepared.

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. is used, and the above-mentioned “hydrosilylation reaction cured silicone rubber layer is formed on one side of the aromatic polyimide resin film”. According to "Method I for Producing Laminated Sheets Laminated in Adhesive State", the capton 200H / V film and the hydrosilylation reaction-curing silicone rubber layer (thickness 0.9 mm) are adhered by heating at 100 ° C. for 20 minutes under pressure. A laminated sheet to be laminated was produced.

In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer (thickness 0.9 mm) are firmly adhered, but as shown in the photograph on the right side of FIG. 5, the front side and the back side are sideways. It was curved more than a semi-arc .
Table 5 shows the average warpage value and the peeling adhesive strength of this laminated sheet.

[Comparative Example 10] (Table 5)
50 parts of EG3100A and 10 parts of Aerosil RX200 were added to a planetary mixer and mixed until uniform to prepare a fluid composition A.
50 parts of EG3100B and 10 parts of RX200 were added to a planetary mixer and mixed until uniform to prepare a fluid composition B.
60 parts of fluid composition A, 60 parts of fluid composition B, 2.06 parts of cross-linking agent A and 1.0 part of AP-001 are added to a planetary mixer, mixed until uniform, and heat-cured by hydrosilylation reaction. A liquid silicone rubber composition (containing 16.3% by mass of Aerosil RX200) was prepared.

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. is used, and the above-mentioned “hydrosilylation reaction cured silicone rubber layer is formed on one side of the aromatic polyimide resin film”. According to "Method I for Producing Laminated Sheets Laminated in Adhesive State", the capton 200H / V film and the hydrosilylation reaction-curing silicone rubber layer (thickness 0.9 mm) adhere to each other by heating at 120 ° C. for 10 minutes under pressure. A laminated sheet to be laminated was produced.

In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer (thickness 0.9 mm) are firmly adhered to each other , but in the side view, the front side and the back side are curved more than a semicircular arc. ..

[Comparative Example 11] (Table 5)
50 parts of EG3100A and 12.5 parts of Aerosil RX20012.5 parts were added to a planetary mixer and mixed until uniform to prepare a fluid composition A.
50 parts of EG3100B and 12.5 parts of Aerosil RX20012.5 parts were put into a planetary mixer and mixed until uniform to prepare a fluid composition B.
Add 62.5 parts of the fluid composition A, 62.5 parts of the fluid composition B, 1.1 parts of the cross-linking agent, 1.5 parts of the chain extender C, and 1.0 part of AP-001 to the planetary mixer to make it uniform. To prepare a heat-curable liquid silicone rubber composition (containing 19.4% by mass of Aerosil RX200) by hydrosilylation reaction.

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. is used, and the above-mentioned “hydrosilylation reaction cured silicone rubber layer is formed on one side of the aromatic polyimide resin film”. According to "Method I for Producing Laminated Sheets Laminated in Adhesive State", the capton 200H / V film and the hydrosilylation reaction-curing silicone rubber layer (thickness 0.9 mm) adhere to each other by heating at 120 ° C. for 10 minutes under pressure. A laminated sheet to be laminated was produced.

In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer (thickness 0.9 mm) are firmly adhered, and the average warp value is 13.5 mm, but the second one leaked gas, so a gas leak test was conducted. Was canceled.
Table 5 shows the average warpage value, the peeling adhesive strength, and the gas leakage property of this laminated sheet.

[Comparative Example 12] (Table 5)
50 parts of SE1720A and 7.5 parts of Aerosil RX200 were added to a planetary mixer and mixed until uniform to prepare a fluid composition A.
50 parts of SE1720B and 7.5 parts of Aerosil RX200 were added to a planetary mixer and mixed until uniform to prepare a fluid composition B.
57.5 parts of the fluid composition A, 57.5 parts of the fluid composition B, and 1.0 part of AP-001 are added to a planetary mixer, mixed until uniform, and heat-curable liquid silicone rubber by hydrosilylation reaction. A composition (containing 12.9 parts of Aerosil RX200) was prepared.

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. is used, and the above-mentioned “hydrosilylation reaction cured silicone rubber layer is formed on one side of the aromatic polyimide resin film”. According to "Method I for Producing Laminated Sheets Laminated in Adhesive State", the capton 200H / V film and the hydrosilylation reaction-curing silicone rubber layer (thickness 0.9 mm) adhere to each other by heating at 120 ° C. for 10 minutes under pressure. A laminated sheet to be laminated was produced.

In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer (thickness 0.9 mm) are firmly adhered, and the average warp value is 18.8 mm. Was canceled.
Table 5 shows the average warpage value, the peeling adhesive strength, and the gas leakage property of this laminated sheet.

[Reference Example 3] (Table 6)
50 parts of EG3100A and 12.5 parts of RX20012.5 parts were put into a planetary mixer and mixed until uniform to prepare a fluid composition A.
50 parts of EG3100B and 12.5 parts of RX20012.5 parts were put into a planetary mixer and mixed until uniform to prepare a fluid composition B.
62.5 parts of fluid composition A, 62.5 parts of fluid composition B, 1.1 parts of cross-linking agent A, 1.5 parts of chain extender D, and AP-001 not added, 0.1 part added to the planetary mixer, Four kinds of heat-curable liquid silicone rubber compositions (containing about 19.5% by mass of Aerosil RX200) by hydrosilylation reaction were prepared by adding 0.3 parts or 0.5 parts and mixing until uniform. ..

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. is used, and the above-mentioned “hydrosilylation reaction cured silicone rubber layer is formed on one side of the aromatic polyimide resin film”. According to "Method I for Producing Laminated Sheets Laminated in Adhesive State", the capton 200H / V film and the hydrosilylation reaction-curable silicone rubber layer (thickness 1.4 mm) are adhered by heating at 120 ° C. for 10 minutes under pressure. Four kinds of laminated sheets were prepared.

The average warpage value and the peeling adhesive strength of these laminated sheets were measured and shown in Table 6.
Even with the AP-001 non-input product, the peeling adhesive strength was 12.2 N / 20 mm. Even in the AP-100.01 part input product, the aromatic polyimide resin film and the silicone rubber layer (thickness 1.4 mm) were firmly adhered to each other.

[Reference Example 4] (Table 6)
50 parts of CY52-276A and 12.5 parts of Aerosil RX20012.5 parts were added to a planetary mixer and mixed until uniform to prepare a fluid composition A.
50 parts of CY52-276B and 12.5 parts of Aerosil RX20012.5 parts were added to a planetary mixer and mixed until uniform to prepare a fluid composition B.
62.5 parts of fluid composition A, 62.5 parts of fluid composition B, 1.15 parts of cross-linking agent A, AP-0010.1 part, AP-0010.3 part, AP-0010. 5 parts or 5 parts of AP-001 were added and mixed until uniform to prepare 4 kinds of heat-curable liquid silicone rubber compositions (containing about 19.5% by mass of Aerosil RX200) by a hydrosilylation reaction. Since curing was insufficient with 0.5 parts of AP-001, 5.2 parts of the cross-linking agent A was added.

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. is used, and the above-mentioned “hydrosilylation reaction cured silicone rubber layer is formed on one side of the aromatic polyimide resin film”. According to "Method I for Producing Laminated Sheets Laminated in Adhesive State", the capton 200H / V film and the hydrosilylation reaction-curable silicone rubber layer (thickness 1.4 mm) are adhered and laminated by heating at 100 ° C. for 20 minutes under pressure. Four kinds of laminated sheets were prepared.

The average warpage value and the peeling adhesive strength of these laminated sheets were measured and shown in Table 6.
Even in the AP-100.01 part input product, the aromatic polyimide resin film and the silicone rubber layer were firmly adhered to each other.

[Example 12] (Table 7)
50 parts of solution A of the DOW CORNING EG-3100 KIT and 10 parts of Aerosil RX200 were added to a planetary mixer and mixed until uniform to prepare a fluid composition A.
50 parts of solution B of the DOW CORNING EG-3100 KIT and Aerosil RX200 (10 parts) were added to a planetary mixer and mixed until uniform to prepare a fluid composition B.
60 parts of the fluid composition A, 60 parts of the fluid composition B, and 2.06 parts of the cross-linking agent A are added to a planetary mixer and mixed until uniform, and the heat-curable liquid silicone rubber composition by hydrosilylation reaction ( Aerosil RX200 containing 16.4% by mass) was prepared.

50 parts of solution A of the DOW CORNING EG-3100 KIT and 10 parts of Aerosil RX200 were added to a planetary mixer and mixed until uniform to prepare a fluid composition A.
50 parts of liquid B of DDOW CORNING EG-3100 KIT and 10 parts of Aerosil RX200 were added to a planetary mixer and mixed until uniform to prepare a fluid composition B.
In a planetary mixer, 60 parts of the fluid composition A, 60 parts of the fluid composition B, 1.1 parts of the cross-linking agent A, 1.5 parts of the chain extender D and 1.0 part of AP-001 are added and mixed until uniform. A heat-curable liquid silicone adhesive composition (containing 16.3% by mass of Aerosil RX200) was prepared by a hydrosilylation reaction.

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. was used, and the above-mentioned [aromatic polyimide resin film was hydrosilylated via a thin layer of silicone adhesive. The aromatic polyimide resin film is hydrosilylated via the silicone adhesive thin layer by heating at 120 ° C. for 10 minutes under a pressure of 3 MPa according to the method II] for producing a laminated sheet laminated on the reaction-cured silicone rubber layer in an adhesive state. A three-layer laminated sheet laminated on the reaction-cured silicone rubber layer in an adhesive state was produced.

In this three-layer laminated sheet, the aromatic polyimide resin film and the silicone rubber layer are firmly adhered to each other via a thin layer of the cured silicone adhesive, the degree of warpage is small, and the aromatic polyimide resin film is wrinkled. There wasn't.
Table 7 shows the D4-D15 content in the silicone rubber and the D4-D15 content in the headspace gas.
The average warpage value, peeling adhesive strength, and number of gas leaks of this three-layer laminated sheet were measured and shown in Table 7. No gas leaked out of 10 of them.

[Example 13] (Table 7)
In Example 12, 60 parts of the fluid composition A, 60 parts of the fluid composition B, and 2.06 parts of the cross-linking agent A were added and mixed until uniform to obtain a heat-curable liquid silicone rubber composition by a hydrosilylation reaction. Instead of preparing, 60 parts of the fluid composition A, 60 parts of the fluid composition B, 1.1 parts of the cross-linking agent A and 1.5 parts of the chain extender D are added, mixed until uniform, and heated by a hydrosilylation reaction. A curable liquid silicone rubber composition (containing 16.4% by mass of Aerodil RX200) was prepared, and a three-layer laminated sheet was prepared under the same conditions as in Example 12. In this three-layer laminated sheet, the aromatic polyimide resin film and the silicone rubber layer were firmly adhered to each other via the silicone adhesive cured product thin layer, the degree of warpage was small, and the polyimide resin film was not wrinkled. ..
Table 7 shows the D4-D15 content in the silicone rubber and the D4-D15 content in the headspace gas.
The average warpage value, peeling adhesive strength, and number of gas leaks of this three-layer laminated sheet were measured and shown in Table 7. No gas leaked out of 10 of them.

[Reference Example 5-1] (Table 8)
Using a heat-curable liquid silicone rubber composition produced by Toray DuPont Co., Ltd., trade name Capton 200H / V film (film thickness 50 μm) and hydrosilylation reaction prepared in [Example 1], the above-mentioned "fragrance" was used. Hydrosilylation on one side of the group polyimide resin film Hydrosilylation on one side of the aromatic polyimide resin film by heating at 120 ° C. for 10 minutes under pressure according to "Method I" for producing a laminated sheet in which a reaction-curing silicone rubber layer is laminated in an adhesive state. A laminated sheet in which a reaction-cured silicone rubber layer (thickness 1.4 mm) was laminated in an bonded state was produced.
The average warpage value of the laminated sheet was measured and shown in Table 8.
The average warpage value of the laminated sheet was 10 mm.

[Reference Example 5-2] (Table 8)
In [Reference Example 5-1], a hydrosilylation reaction-curable silicone rubber layer (thickness 1.4 mm) was formed on one side of an aromatic polyimide resin film by heating at 130 ° C. for 8 minutes instead of heating at 120 ° C. for 10 minutes under pressure. Made a laminated sheet laminated in a bonded state.
The average warpage value of the laminated sheet was measured and shown in Table 8.
The average warpage value of the laminated sheet was 13 mm.

[Reference Example 5-3] (Table 8)
In [Reference Example 5-1], a hydrosilylation reaction-curable silicone rubber layer (thickness 1.4 mm) was formed on one side of an aromatic polyimide resin film by heating at 150 ° C. for 7 minutes instead of heating at 120 ° C. for 10 minutes under pressure. Made a laminated sheet laminated in a bonded state.
The average warpage value of the laminated sheet was measured and shown in Table 8.
From the side view, the laminated sheet was found to be unsuitable as a curing temperature condition because the front side and the back side were curved more than a semicircular shape .

[Reference Example 5-4] (Table 8)
In [Reference Example 5-1], a hydrosilylation reaction-curable silicone rubber layer (thickness 1.4 mm) was formed on one side of an aromatic polyimide resin film by heating at 200 ° C. for 5 minutes instead of heating at 120 ° C. for 10 minutes under pressure. Made a laminated sheet laminated in a bonded state.
The average warpage value of the laminated sheet was measured and shown in Table 8.
It was found that the laminated sheet was rolled into a cylindrical shape and was unsuitable as a curing temperature condition.

[Reference Example 6-1] (Table 8)
Using a heat-curable liquid silicone rubber composition produced by Toray DuPont Co., Ltd., trade name Capton 200H / V film (film thickness 50 μm) and hydrosilylation reaction prepared in [Example 2], the above-mentioned "fragrance" was used. Hydrosilylation on one side of the group polyimide resin film Hydrosilylation on one side of the aromatic polyimide resin film by heating at 120 ° C. for 10 minutes under pressure according to "Method I" for producing a laminated sheet in which a reaction-curing silicone rubber layer is laminated in an adhesive state. A laminated sheet in which a reaction-cured silicone rubber layer (thickness 1.4 mm) was laminated in an bonded state was produced.
The average warpage value of the laminated sheet was measured and shown in Table 8.
The average warpage value of the laminated sheet was 16 mm.

[Reference Example 6-2] (Table 8)
In [Reference Example 6-1], a hydrosilylation reaction-curable silicone rubber layer (thickness 1.4 mm) was formed on one side of an aromatic polyimide resin film by heating at 140 ° C. for 7 minutes instead of heating at 120 ° C. for 10 minutes under pressure. Made a laminated sheet laminated in a bonded state.
The average warpage value of the laminated sheet was measured and shown in Table 8.
The average warpage value of the laminated sheet was 25.5 mm.

[Reference Example 6-3] (Table 8)
In [Reference Example 6-1], a hydrosilylation reaction-curable silicone rubber layer (thickness 1.4 mm) was formed on one side of an aromatic polyimide resin film by heating at 150 ° C. for 7 minutes instead of heating at 120 ° C. for 10 minutes under pressure. Made a laminated sheet laminated in a bonded state.
The average warpage value of the laminated sheet was measured and shown in Table 8.
From the side view, the laminated sheet was found to be unsuitable as a curing temperature condition because the front side and the back side were curved in a semicircular shape or more, and it was found to be unsuitable as a curing temperature condition.

[Example 14] (Table 9)
In Example 1, a heat-curable liquid silicone rubber composition (containing 19.6% by mass of Aerosil RX200) was prepared by a hydrosilylation reaction under the same conditions except that AP-001 was not added. The heat-curable liquid silicone rubber composition obtained by this hydrosilylation reaction was heated at 120 ° C. for 10 minutes under pressure to be cured. The characteristics of the cured product and the D4-D15 content in the silicone rubber are shown in Table 9. Is shown in Table 9.
Lamination in which the Capton 200H / V film and the hydrosilylation reaction-curing silicone rubber layer are adhered and laminated under the same conditions as in Example 1 except that the heat-curable liquid silicone rubber composition obtained by the hydrosilylation reaction is used. A sheet was prepared.
The average warpage value, peeling adhesive strength, D4-D15 content in headspace gas, and the number of gas leaks of this laminated sheet were measured and shown in Table 9.
In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer were well adhered to each other, the degree of warpage was small, and the polyimide resin film was not wrinkled. There was no gas leak in 1 out of 10 bottles.

[Example 15] (Table 9)
In Example 1, a heat-curable liquid silicone rubber composition (Aerosil RX200 19.6) was subjected to a hydrosilylation reaction under the same conditions except that 0.1 part of AP-001 was added instead of 1 part of AP-001. (Containing% by mass) was prepared. A heat-curable liquid silicone rubber composition by a hydrosilylation reaction was heated at 120 ° C. for 10 minutes under pressure to be cured. The characteristics of the cured product and the D4-D15 content in the silicone rubber are shown in Table 9.
Lamination in which the Capton 200H / V film and the hydrosilylation reaction-curing silicone rubber layer are adhered and laminated under the same conditions as in Example 1 except that the heat-curable liquid silicone rubber composition obtained by the hydrosilylation reaction is used. A sheet was prepared.
The average warpage value, peeling adhesive strength, D4-D15 content in headspace gas, and the number of gas leaks of this laminated sheet were measured and shown in Table 9.
In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer were well adhered to each other, the degree of warpage was small, and the aromatic polyimide resin film was not wrinkled. There was no gas leak in 1 out of 10 bottles.

[Example 16] (Table 10)
To a planetary mixer, 100 parts of dimethylpolysiloxane (vinyl group content 0.23% by mass, viscosity 2,000 mPa · s) in which both ends of the molecular chain are sealed with dimethylvinylsiloxy groups and 20 parts of Aerosil RX200 are uniformly added. A liquid silicone rubber base was prepared by mixing until it became. To this, add 0.65 part of the cross-linking agent A, 1.71 part of the chain extender D, 0.20 part of ETCH and 0.5 part of AP-001 and mix until uniform, and finally add 0.20 part of SRX212 CATALYST. The mixture was mixed until uniform to prepare a heat-curable liquid silicone rubber composition (SiH / SiVi ratio = 15.8; containing 16.3% by mass of Aerodil RX200) by a hydrosilylation reaction.
The heat-curable liquid silicone rubber composition obtained by this hydrosilylation reaction was heated at 120 ° C. for 10 minutes under pressure to form a sheet, and then secondarily cured in a hot air circulation oven at 200 ° C. for 4 hours. The characteristic values of the 2 mm thick silicone rubber pieces and the D4-D15 content in the silicone rubber were measured and shown in Table 10.

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. is used, and the above-mentioned “hydrosilylation reaction cured silicone rubber layer is formed on one side of the aromatic polyimide resin film”. According to "Method I for Producing Laminated Sheets Laminated in Adhesive State", the capton 200H / V film and the hydrosilylation reaction-curable silicone rubber layer (thickness 1.8 mm) are adhered by heating at 120 ° C. for 10 minutes under pressure. A laminated sheet to be laminated was produced.

Then, this laminated sheet was placed in a hot air circulation type oven at 200 ° C. for 4 hours for secondary curing.
In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer (thickness 1.8 mm) were firmly adhered to each other, the degree of warpage was small, and the aromatic polyimide resin film was not wrinkled.
The average warpage value, peeling adhesive strength, D4-D15 content in headspace gas, and the number of gas leaks of this laminated sheet were measured and shown in Table 10.
No gas leaked out of 10 of them.

[Example 17] (Table 10)
In Example 16, except that Aerosil RX200 15 parts was used instead of Aerosil RX200 20 parts, a heat-curable liquid silicone rubber composition (containing 13% by mass of Aerosil RX200) by a hydrosilylation reaction was prepared under the same conditions to prepare a laminated sheet. did.
In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer (thickness 1.8 mm) were firmly adhered to each other, the degree of warpage was small, and the aromatic polyimide resin film was not wrinkled.
The average warpage value, peeling adhesive strength, D4-D15 content in headspace gas, and the number of gas leaks of this laminated sheet were measured and shown in Table 10.
No gas leaked out of 10 of them.

[Example 18] (Table 10)
In Example 16, a heat-curable liquid silicone rubber composition (containing 16.3% by mass of Aerosil RX200) by a hydrosilylation reaction under the same conditions, except that AP-0010.1 part was used instead of AP-0010.5 part. ) Was prepared to prepare a laminated sheet.
In this laminated sheet, the aromatic polyimide resin film and the silicone rubber layer (thickness 1.8 mm) were firmly adhered to each other, the degree of warpage was small, and the aromatic polyimide resin film was not wrinkled.
The average warpage value, peeling adhesive strength, D4-D15 content in headspace gas, and the number of gas leaks of this laminated sheet were measured and shown in Table 10.
No gas leaked out of 10 of them.
[Example 19] (Table 11)
In Example 16, a laminated sheet was produced under the same conditions except that the temperature was 200 ° C. for 1 hour in hot air instead of 200 ° C. for 4 hours in hot air. The average warpage value, peeling adhesive strength, D4-D15 content in headspace gas, and the number of gas leaks of this laminated sheet were measured and shown in Table 11. The D4-D15 content in the silicone rubber was 235 ppm, but none of the 10 rubber leaked.
[Comparative Example 14] (Table 11)
In Example 16, a laminated sheet was prepared under the same conditions except that no secondary curing was performed instead of 200 ° C. for 4 hours in hot air. The D4-D15 content in the silicone rubber was measured, and the average warpage value and peeling adhesive strength of this laminated sheet, the D4-D15 content in the headspace gas, and the number of gas leaks were measured and shown in Table 11. The D4-D15 content in the silicone rubber was as large as 750 ppm.
[Comparative Example 15] (Table 11)
In Example 16, a heat-curable liquid silicone rubber composition (Aerosil) by a hydrosilylation reaction under the same conditions, except that 0.65 parts of the cross-linking agent and 1.71 parts of the chain extender were replaced with 1.79 parts of the cross-linking agent. RX200 (containing 16.3% by mass) was prepared to prepare a laminated sheet. Table 11 shows the silicone rubber characteristics, the degree of warpage, and the peeling adhesive strength. The D4-D15 content and the number of gas leaks were not measured because the degree of warpage was more than a semicircular arc .
[Comparative Example 16] (Table 11)
In Example 16, heat curing by hydrosilylation reaction under the same conditions except that 1.22 parts of the cross-linking agent and 0.86 parts of the chain extender were used instead of 0.65 parts of the cross-linking agent and 1.71 parts of the chain extender. A mold liquid silicone rubber composition (containing 16.3% by mass of Aerosil RX200) was prepared, and a laminated sheet was prepared. Table 11 shows the silicone rubber characteristics, the degree of warpage, and the peeling adhesive strength. The D4-D15 content and the number of gas leaks were not measured because the degree of warpage was more than a semicircular arc .

[Reference Example 7] (Table 12)
50 parts of EG3100A and 12.5 parts of RX20012.5 parts were put into a planetary mixer and mixed until uniform to prepare a fluid composition A.
50 parts of EG3100B and 12.5 parts of RX20012.5 parts were put into a planetary mixer and mixed until uniform to prepare a fluid composition B.
In a planetary mixer, 62.5 parts of the fluid composition A, 62.5 parts of the fluid composition B, 1.1 parts of the cross-linking agent A, 1.5 parts of the chain extender D, and (7-1) γ-glycidoxypropyltri. Methoxysilane, (7-2) vinyltrimethoxysilane, (7-3) γ-methacryloxypropyltrimethoxysilane, (7-4) γ-glycidoxypropyltrimethoxysilane 5 parts by mass and vinyltrimethoxysilane 5 Mix by mass) or (7-5) 0.3 parts by mass of a mixture of 5 parts by mass of γ-glycidoxypropyltrimethoxysilane and 5 parts by mass of γ-methacryloxypropyltrimethoxysilane becomes uniform. To prepare 5 kinds of heat-curable liquid silicone rubber compositions (containing about 19.5% by mass of Aerodil RX200) by hydrosilylation reaction.

As the aromatic polyimide resin film, a Capton 200H / V film (film thickness 50 μm) manufactured by Toray DuPont Co., Ltd. is used, and the above-mentioned “hydrosilylation reaction cured silicone rubber layer is formed on one side of the aromatic polyimide resin film”. According to "Method I for Producing Laminated Sheets Laminated in Adhesive State", the capton 200H / V film and the hydrosilylation reaction-curable silicone rubber layer (thickness 1.4 mm) are adhered by heating at 120 ° C. for 10 minutes under pressure. Five kinds of laminated sheets were prepared.

The average warpage value and the peeling adhesive strength of these laminated sheets were measured and shown in Table 12.
It can be seen that all of them are non-peelable and are remarkably superior to Reference Example 3-1 which does not contain the component (B).

The blending amount of each component in the table is by mass. (%) Of Aerosil RX200 is mass%.

注：
(7-1) γ－グリシドキシプロピルトリメトキシシラン
(7-2) ビニルトリメトキシシラン
(7-3) γ－メタクリロキシプロピルトリメトキシシラン
(7-4) γ－グリシドキシプロピルトリメトキシシラン５質量部とビニルトリメトキシシラン５質量部の混合物）
(7-5) γ－グリシドキシプロピルトリメトキシシラン５質量部とγ－メタクリロキシプロピルトリメトキシシラン５質量部の混合物

note:
(7-1) γ-glycidoxypropyltrimethoxysilane
(7-2) Vinyl trimethoxysilane
(7-3) γ-methacryloxypropyltrimethoxysilane
(7-4) Mixture of 5 parts by mass of γ-glycidoxypropyltrimethoxysilane and 5 parts by mass of vinyltrimethoxysilane)
(7-5) Mixture of 5 parts by mass of γ-glycidoxypropyltrimethoxysilane and 5 parts by mass of γ-methacryloxypropyltrimethoxysilane

[Example 20]
100. A liquid silicone rubber base was prepared by putting the parts together and mixing them. Then, the remaining components were added and kneaded until uniform to prepare liquid silicone rubber compositions (1), (2), (3) and (4).

Each composition was cured by heating at 120 ° C. for 10 minutes under pressure to prepare a 1.8 mm-thick silicone rubber sheet (1), (2), (3) and (4). Next, the silicone rubber sheets (1), (2), (3) and (4) were placed in a hot air circulation oven at 200 ° C. for 4 hours for secondary curing. The secondary cured silicone rubber sheets (1), (2), (3) and (4) are uniformly stacked on a Kapton 200H / V film (film thickness 50 μm), which is a polyimide film, and hot air circulation type at the following temperature is used. A laminated sheet was prepared by heating in an oven for the following time. The peeling adhesive strength (N / 20 mm) of the laminated sheets (1), (2), (3) and (4) was measured.

The average warpage value of the laminated sheet produced by heating at 200 ° C. for 6 hours was measured, and a photograph was taken. From the left, the laminated sheets (1), (2), and (3).
In each case, the average warp value is 0 mm.

Instead of placing in a hot air circulation oven at 200 ° C., the mixture was placed at room temperature to measure the peeling adhesive strength.

[Comparative Example 17] (Table 16)
In Example 1, instead of "1.1 parts of the cross-linking agent A, 1.5 parts of the chain extender D and 1.0 part of AP-001", "0.7 parts of the cross-linking agent B1 and AP-001". A heat-curable liquid silicone rubber composition (containing 16.5% by mass of Aerosil RX200) was prepared by a hydrosilylation reaction under the same conditions except that "0.3 parts" was blended. Various characteristics were measured in the same manner as in Example 1 and shown in Table 16. In addition, the total area of small molecule siloxane peaks was calculated and shown in Table 16. Since the strength and tear strength are small, there is concern about gas leakage. The total area of small molecule siloxane peaks is large.

[Example 21] (Table 16)
In Example 1, instead of "1.1 parts of the cross-linking agent A, 1.5 parts of the chain extender D and 1.0 part of AP-001", "0.36 parts of the cross-linking agent B1 and the chain extender" A heat-curable liquid silicone rubber composition (containing 16.5% by mass of Aerosil RX200) was prepared by a hydrosilylation reaction under the same conditions except that 0.69 parts of T and 0.3 parts of AP-001 were blended. Various characteristics were measured in the same manner as in Example 1 and shown in Table 16. In addition, the total area of small molecule siloxane peaks was calculated and shown in Table 16.
High elongation and tear strength, low D4-D15 content in headspace gas, no gas leaks, and small total area of small molecule siloxane peaks.

[Reference Example 9] (Table 17)
In Example 1, instead of "1.1 parts of the cross-linking agent A, 1.5 parts of the chain extender D and 1.0 part of AP-001", "0.6 parts of the cross-linking agent B-1", Heat-curable liquid silicone rubber composition by hydrosilylation reaction under the same conditions except that "0.6 parts of chain extender P, 0.2 parts of chain extender D, and 0.3 parts of AP-001" are blended. (Containing 16.5% by mass of Aerodil RX200) was prepared. Various characteristics were measured in the same manner as in Example 1 and shown in Table 17. In addition, the total area of small molecule siloxane peaks was calculated and shown in Table 17. Compared to Comparative Example 17, the rubber physical characteristics are better, and the total area of the small molecule siloxane peaks is smaller.

[Comparative Example 18] (Table 17)
In Example 1, instead of "1.1 parts of the cross-linking agent A, 1.5 parts of the chain extender D and 1.0 part of AP-001", "0.33 parts of the cross-linking agent C and AP-001". A heat-curable liquid silicone rubber composition (containing 16.5% by mass of Aerosil RX200) was prepared by a hydrosilylation reaction under the same conditions except that "0.3 parts" was blended. Various characteristics were measured in the same manner as in Example 1 and shown in Table 17. In addition, the total area of small molecule siloxane peaks was calculated and shown in Table 17.
Although the total area of the small molecule siloxane peak is small, the strength and elongation and tear strength are small, so there is concern about gas leakage.

[Example 22] (Table 17)
In Example 1, instead of "1.1 parts of the cross-linking agent A, 1.5 parts of the chain extender D and 1.0 part of AP-001", "0.36 parts of the cross-linking agent A and the chain extender" A heat-curable liquid silicone rubber composition (containing 16.5% by mass of Aerosil RX200) was prepared by a hydrosilylation reaction under the same conditions except that 0.69 parts of T and 0.3 parts of AP-001 were blended. Various characteristics were measured in the same manner as in Example 1 and shown in Table 17. In addition, the total area of small molecule siloxane peaks was calculated and shown in Table 17.
High elongation and tear strength, low D4-D15 content in headspace gas, no gas leaks, and small total area of small molecule siloxane peaks.

[Example 23] (Table 17)
In Example 1, instead of "1.1 parts of the cross-linking agent A, 1.5 parts of the chain extender D and 1.0 part of AP-001", "0.17 parts of the cross-linking agent C and the chain extender" A heat-curable liquid silicone rubber composition (containing 16.5% by mass of Aerosil RX200) was prepared by a hydrosilylation reaction under the same conditions except that 0.69 parts of T and 0.3 parts of AP-001 were blended. Various characteristics were measured in the same manner as in Example 1 and shown in Table 17. In addition, the total area of small molecule siloxane peaks was calculated and shown in Table 17.
High elongation and tear strength, low D4-D15 content in headspace gas, no gas leaks, and small total area of small molecule siloxane peaks.

The laminated sheet for manufacturing the polyimide for sealing the opening of the vial used in the headspace vial, that is, the headspace GC method and the headspace GC-MS method of the present invention, the manufacturing method thereof, and the opening sealing of the headspace vial. The septum made of a laminated sheet in which an aromatic polyimide film and a silicone rubber layer are laminated, and the septum made of a laminated sheet in which an aromatic polyimide film and a silicone rubber layer are laminated are industrially useful. be.

1a Silicone rubber layer 1b Aromatic polyimide resin film 1 Single-sided film-attached laminated sheet 2 Double-sided film-attached laminated sheet 3 Septam 4 Screw vial 5 Screw cap 6 Screw cap hole 7 Headspace sampler 8 Heater 9 Sample probe 10 Collection needle ( needle)
11 Helium gas 12 Switching valve 13 Transfer line 14 Gas chromatograph (GC)
15 Capillary column 16 Mass spectrometer (MS)
17 detector

Claims (7)

An aromatic polyimide film having a thickness of 10 to 200 μm and a thickness in a laminated sheet for producing a septum for sealing an opening of a vial for headspace gas chromatograph analysis or headspace gas chromatograph mass analysis. Is 1.2 to 5 mm, the content of cyclic dimethylsiloxane tetramer to 15 mer is 250 mass ppm or less, and (A) fumed silica as a reinforcing filler is contained, and in JIS K 6249. The hydrosilylation reaction cured silicone rubber layer (I) having a specified elongation of 380% or more and a tensile stress at 100% elongation of 0.20 to 1.35 MPa , or a thickness of 1.2 to 5 mm. The content of cyclic dimethylsiloxane tetramer to 15-mer is 250% by mass or less, and (A) fumed silica as a reinforcing filler and (B) organic functional organoalkoxysilane or a partial hydrolysis condensation thereof. A hydrosilylation reaction-cured silicone rubber layer (II) containing a substance, having an elongation of 380% or more specified by JIS K 6249, and having a tensile stress at 100% elongation of 0.20 to 1.35 MPa . It is laminated in a bonded state, and the peeling adhesive strength based on JIS K6854-2 (adhesive-peeling adhesive strength test method-Part 2: 180 degree peeling) is 4N / 20 mm or more, length 120 mm, width 120 mm. The square laminated sheet test piece is a laminated sheet characterized in that the average warpage value of the four corners is 35 mm or less. The aromatic polyimide film having a thickness of 10 to 200 μm and the cyclic dimethylsiloxane tetramer to 15-mer have a content of 250 mass ppm or less, and contain (A) fumed silica as a reinforcing filler. A heat-curable liquid silicone rubber composition (I) by a hydrosilylation reaction in which the elongation specified by JIS K 6249 of the cured product is 380% or more and the tensile stress at 100% elongation is 0.20 to 1.35 MPa. Or , the content of the cyclic dimethylsiloxane tetramer to 15-mer is 250% by mass or less, and (A) fumed silica as a reinforcing filler and (B) organic functional organoalkoxysilane or its partial water addition. A heat-curable liquid by hydrosilylation reaction containing a decomposition condensate, the elongation of the cured product specified by JIS K 6249 is 380% or more, and the tensile stress at 100% elongation is 0.20 to 1.35 MPa. Opening of vials for headspace gas chromatograph analysis or headspace gas chromatograph mass analysis, characterized in that the silicone rubber composition (II) is brought into close contact with the silicone rubber composition (II) and heated at 145 ° C. or lower under pressure to cure. A laminated sheet for forming a septum for partial encapsulation, a polyimide film having a thickness of 10 to 200 μm and a heat-curable liquid silicone having a thickness of 1.2 to 5 mm by the hydrosilylation reaction. A cured product of the silicone rubber layer (I), which is a cured product of the rubber composition (I), or a cured product of the heat-curable liquid silicone rubber composition (II), which has a thickness of 1.2 to 5 mm and is heat-curable by the hydrosilylation reaction. The silicone rubber layer (II) is laminated in a bonded state, and the peeling adhesive strength based on JIS K6854-2 (adhesive-peeling adhesive strength test method-Part 2: 180 degree peeling) is 4N . A method for manufacturing a laminated sheet in which a square laminated sheet test piece having a length of 120 mm and a width of 120 mm has an average warp value of 35 mm or less at four corners of 20 mm or more. It is an aromatic polyimide film having a thickness of 10 to 200 μm, a hydrosilylation reaction-cured silicone rubber, a thickness of 1.2 to 5 mm, and a content of cyclic dimethylsiloxane tetramer to 15-mer of 250 mass. It is ppm or less, contains (A) fumed silica as a reinforcing filler, has an elongation of 380% or more specified by JIS K 6249, and has a tensile stress of 0.20 to 1.35 MPa at 100% elongation. The content of the cyclic dimethylsiloxane tetramer to 15-mer is 250% by mass or less, and (B) organic functional organoalkoxysilane or a partially hydrolyzed condensate thereof is contained between the silicone rubber sheet and the silicone rubber sheet. Heat-curable liquid silicone rubber composition by hydrosilylation reaction containing (A) fumed silica as a reinforcing filler A heat-curable liquid silicone rubber composition by the liquid hydrosilylation reaction by interposing a thin layer and heating under pressure. The polyimide film and the hydrosilyl for forming a septum for sealing the opening of a vial for headspace gas chromatograph analysis or headspace gas chromatograph mass analysis, which comprises curing a thin layer. A method for manufacturing a laminated sheet in which a chemical reaction-cured silicone rubber sheet is laminated in an adhered state, and a square laminated sheet test piece having a length of 120 mm and a width of 120 mm has an average warp value of 35 mm or less at four corners . The components (B) are (a) an alkenyl-functional organoalkoxysilane having two or three silicon atom-bonded alkoxy groups in one molecule and (b) two or three silicon atom-bonded alkoxy groups in one molecule. One to three selected from the group consisting of (meth) acrylic functional organoalkoxysilanes and (c) epoxy functional organoalkoxysilanes having two or three silicon atom-bonded alkoxy groups in one molecule. Claimed to be an organic-functional organoalkoxysilane, or a co-partially hydrolyzed condensate of the organic-functional organoalkoxysilane and (d) an organic titanium compound catalyst, or the organic-functional organoalkoxysilanes of two or three. Item 3. The method for manufacturing a laminated sheet according to Item 3. An aromatic polyimide film having a thickness of 10 to 200 μm, and (A) fumed silica and (B) as a reinforcing filler having a content of cyclic dimethylsiloxane tetramer to 15-mer of more than 250 mass ppm. It contains organic functional organoalkoxysilane or a partially hydrolyzed condensate thereof , the elongation of the cured product specified by JIS K 6249 is 250% or more, and the tensile stress at 100% elongation specified by JIS K 6249 is 0. It is brought into close contact with a heat-curable silicone gel composition by a hydrosilylation reaction at 1 to 0.49 MPa and heated at 90 ° C. or higher and 240 ° C. or lower under pressure to primary cure the silicone gel composition, and then hot air. For headspace gas chromatograph analysis method or headspace gas chromatograph mass analysis, which comprises placing in it until the content of cyclic dimethylsiloxane tetramer to 15-mer is 250 mass ppm or less and performing secondary curing. A laminated sheet for forming a septum for sealing the opening of a legal vial, which is an aromatic polyimide film having a thickness of 10 to 200 μm and a cyclic dimethylsiloxane having a thickness of 1.2 to 5 mm. The content of tetramer to 15-mer is 250 mass ppm or less, and contains (A) fumed silica as a reinforcing filler and (B) organic functional organoalkoxysilane or a partially hydrolyzed condensate thereof. , The elongation of the cured product specified by JIS K 6249 is 250% or more, and the tensile stress at 100% elongation specified by JIS K 6249 is 0.15 to 0.49 MPa. A method for manufacturing a laminated sheet in which a square laminated sheet test piece having a length of 120 mm and a width of 120 mm is laminated in a bonded state and the average warpage value of the four corners is 35 mm or less. An aromatic polyimide film having a thickness of 10 to 200 μm, a cyclic dimethylsiloxane tetramer to 15-mer having a content of more than 250 mass ppm, and containing (A) fumed silica as a reinforcing filler . A heat-curable liquid silicone rubber composition (I) or reinforcement by a hydrosilylation reaction in which the elongation specified by JIS K 6249 is 380% or more and the tensile stress at 100% elongation is 0.20 to 1.35 MPa. It contains (A) fumed silica as a sex filler and (B) organic functional organoalkoxysilane or a partially hydrolyzed condensate thereof, and the elongation specified by JIS K 6249 is 380% or more, and at 100% elongation. The silicone rubber is brought into close contact with the heat-curable liquid silicone rubber composition (II) by a hydrosilylation reaction having a tensile stress of 0.20 to 1.35 MPa and heated at 90 ° C. or higher and 145 ° C. or lower under pressure. The headspace gas chroma is characterized in that the composition is first cured and then placed in hot air until the content of cyclic dimethylsiloxane tetramer to 15 mer is 250% by mass or less and secondarily cured. A laminated sheet for forming a septum for sealing an opening of a vial for a tograph analysis method or a headspace gas chromatograph mass analysis method, which has an aromatic polyimide film having a thickness of 10 to 200 μm and a thickness of 10 to 200 μm. It is 1.2 to 5 mm, has a cyclic dimethylsiloxane tetramer to 15-mer content of 250 mass ppm or less, contains (A) fumed silica as a reinforcing filler, and is specified in JIS K 6249. A hydrosilylation reaction-cured silicone rubber layer (I) having an elongation of 380% or more and a tensile stress at 100% elongation of 0.20 to 1.35 MPa , or a thickness of 1.2 to 5 mm. The content of cyclic dimethylsiloxane tetramer to 15-mer is 250% by mass or less, and (A) fumed silica as a reinforcing filler and (B) organic functional organoalkoxysilane or a partially hydrolyzed condensate thereof. Adhesion with the hydrosilylation reaction-cured silicone rubber layer (II), which contains 380% or more of elongation specified by JIS K 6249 and has a tensile stress of 0.20 to 1.35 MPa at 100% elongation. A method for manufacturing a laminated sheet in which a square laminated sheet test piece having a length of 120 mm and a width of 120 mm is laminated in a state and the average warpage value of the four corners is 35 mm or less. An aromatic polyimide film having a thickness of 10 to 200 μm, a thickness of 1.2 to 5 mm, a content of cyclic dimethylsiloxane tetramer to 15-mer, and a reinforcing filler having a thickness of 250 mass ppm or less. ( A ) Hydrosilylated reaction-cured silicone rubber layer containing fumed silica, having an elongation of 380% or more specified by JIS K 6249, and a tensile stress at 100% elongation of 0.20 to 1.35 MPa. (I) Or , the thickness is 1.2 to 5 mm, the content of the cyclic dimethylsiloxane tetramer to 15-mer is 250 mass ppm or less, and (A) fumed silica as a reinforcing filler. ( B) Contains organic functional organoalkoxysilane or a partially hydrolyzed condensate thereof, the elongation specified by JIS K 6249 is 380% or more, and the tensile stress at 100% elongation is 0.20 to 1.35 MPa. The hydrosilylation reaction-cured silicone rubber layer (II) is laminated in an adhesive state, and is peeled and bonded based on JIS K6854-2 (adhesive-peeling and bonding strength test method-Part 2: 180 degree peeling). A headspace gas chromatograph analysis is characterized in that a square laminated sheet test piece having a strength of 4 N / 20 mm or more and a length of 120 mm and a width of 120 mm is composed of a laminated sheet having an average warp value of 35 mm or less at four corners . Septum for sealing the opening of a vial for legal or headspace gas chromatograph mass analysis.

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