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WO2024219003A1 - Composition de silicone de protection contre les rayons x, et feuille de silicone de protection contre les rayons x et son procédé de production - Google Patents

Composition de silicone de protection contre les rayons x, et feuille de silicone de protection contre les rayons x et son procédé de production Download PDF

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WO2024219003A1
WO2024219003A1 PCT/JP2023/043124 JP2023043124W WO2024219003A1 WO 2024219003 A1 WO2024219003 A1 WO 2024219003A1 JP 2023043124 W JP2023043124 W JP 2023043124W WO 2024219003 A1 WO2024219003 A1 WO 2024219003A1
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ray shielding
vol
silicone
composition according
silicone composition
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Japanese (ja)
Inventor
小林真吾
長谷航希
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Fuji Polymer Industries Co Ltd
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Fuji Polymer Industries Co Ltd
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Priority to JP2024509448A priority Critical patent/JP7516694B1/ja
Priority to TW113106083A priority patent/TW202442801A/zh
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • the present invention relates to a silicone composition with high X-ray shielding properties, an X-ray shielding silicone sheet, and a method for producing the same.
  • thermally conductive silicone sheets are used to improve the adhesion between the semiconductor and the heat sink.
  • thermally conductive silicone sheets are required to be soft and have high thermal conductivity.
  • ionizing radiation such as X-rays or gamma rays is irradiated on MOSFETs and integrated circuits, which are representative semiconductors, positive charges accumulate in the silicon oxide film used as an insulating film, and negative charges are induced on the silicon surface. This causes the threshold voltage to shift in the negative direction.
  • Patent Document 1 proposes a radiation shielding sealant using condensation type silicone and barium sulfate.
  • Patent Document 2 proposes a radiation shielding composition using barium sulfate as an X-ray shielding material.
  • the silicone composition in the above patent document does not have sufficient X-ray shielding properties and thermal conductivity, and even higher X-ray shielding properties and thermal conductivity are required.
  • the present invention provides a silicone composition having high X-ray shielding properties and high thermal conductivity, an X-ray shielding silicone sheet, and a method for producing the same.
  • the X-ray shielding silicone composition of the present invention is an X-ray shielding silicone composition that contains a silicone component, X-ray shielding particles, and thermally conductive particles, and the silicone component is 15 to 60 vol.%, the X-ray shielding particles are 5 to 50 vol.%, and the thermally conductive particles are 30 to 80 vol.% per 100 vol.% of the composition.
  • the X-ray shielding silicone molded product of the present invention is molded into a sheet by at least one molding method selected from the group consisting of sheet molding, extrusion molding, and press molding, and then cured.
  • the method for producing an X-ray shielding silicone sheet of the present invention is characterized in that the silicone composition is mixed to form a compound, which is then molded by at least one molding method selected from the group consisting of sheet molding, extrusion molding, and press molding, and then cured.
  • the X-ray shielding silicone composition of the present invention contains a silicone component, X-ray shielding particles, and thermally conductive particles, and by containing 15-60 vol.% of the silicone component, 5-50 vol.% of the X-ray shielding particles, and 30-80 vol.% of the thermally conductive particles per 100 vol.% of the composition, it is possible to provide a silicone composition, an X-ray shielding silicone sheet, and a method for producing the same that have high X-ray shielding and thermal conductivity properties.
  • the X-ray shielding silicone composition of the present invention can reduce unnecessary X-rays leaking from an X-ray generating device, and can also protect electronic components inside the irradiated body from radiation such as that used in X-ray inspections.
  • FIG. 1 is a schematic cross-sectional view showing a method of using an X-ray shielding silicone sheet according to one embodiment of the present invention.
  • 2A and 2B are explanatory diagrams showing a method for measuring the thermal conductivity of a sample used in an embodiment of the present invention.
  • FIG. 3 is a microscope (SEM) photograph (magnification: 2000 times) of the precipitated barium sulfate particles used in the examples of the present invention.
  • FIG. 4 is a microscope (SEM) photograph (magnification: 5000 times) of the amorphous alumina used in the examples of the present invention.
  • FIG. 5 is a microscope (SEM) photograph (magnification: 500 times) of spherical alumina used in an embodiment of the present invention.
  • FIG. 6 is a microscope (SEM) photograph (magnification: 1000 times) of elutriated barium sulfate used in an embodiment of the present invention.
  • the present invention is an X-ray shielding silicone composition containing a silicone component, X-ray shielding particles, and thermally conductive particles, and the silicone component is 15-60 vol.%, preferably 17-55 vol.%, and more preferably 20-50 vol.%, per 100 vol.% of the composition.
  • the X-ray shielding particles are 5-50 vol.%, preferably 6-45 vol.%, and more preferably 7-40 vol.%.
  • the thermally conductive particles are 30-80 vol.%, preferably 32-78 vol.%, and more preferably 35-75 vol.%. This results in a composition with high X-ray shielding properties.
  • the X-ray shielding particles are less than 5 vol.%, the X-ray shielding properties will be low, and if they exceed 50 vol.%, the proportion of thermally conductive particles will be low and high thermal conductivity cannot be maintained, which is not preferable. Furthermore, if the thermally conductive particles are less than 30 vol.%, the thermal conductivity will be low, and if they exceed 80 vol.%, the proportion of X-ray shielding particles will be low and the X-ray shielding properties will be low, which is not preferable.
  • the silicone component is also called silicone polymer or organopolysiloxane, and is a thermosetting resin that is preferable because it is heat resistant.
  • the X-ray shielding rate of the composition is preferably 30% or more, more preferably 30 to 100%, and even more preferably 35 to 100%, as measured in accordance with JIS Z 4501:2011 and JIS T61331-1:2016. This results in a composition with high X-ray shielding properties.
  • the thermal conductivity of the composition is preferably 0.8 W/mK or more, more preferably 0.8 to 10 W/mK, and even more preferably 1.0 to 8.0 W/mK, as measured in accordance with the ISO/CD22007-2:2008 hot disk method. This results in a composition with high thermal conductivity, making it suitable as a heat sink between heat generating parts and heat dissipating parts of electronic components, etc.: TIM (Thermal Interface Material).
  • the silicone composition is preferably in at least one state selected from grease, putty, gel, and elastomer. With these properties, it is possible to reduce unnecessary X-rays leaking from an X-ray generating device, and also to protect electronic components inside the irradiated body from radiation such as X-ray inspection. Since the grease-like and putty-like compositions are liquid, they are preferably used by filling them into a dispenser. The grease-like and putty-like compositions may be uncured or cured. When they are uncured, they can efficiently follow between the heat generating part and the heat dissipating part, which have large irregularities, making it possible to minimize the contact thermal resistance, have a long pot life, and have stable properties.
  • the gel-like or rubber-like composition is preferably molded into a sheet by sheet molding, extrusion molding, or press molding, and then cured.
  • press molding each molded product may be press molded into a different shape. Press molding is also called mold clamping molding.
  • the X-ray shielding particles are preferably at least one particle selected from the group consisting of barium, tungsten, bismuth, molybdenum, tin, zirconium, tantalum, niobium, titanium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, and compounds thereof. These particles have high X-ray shielding properties.
  • barium sulfate is preferred.
  • Barium sulfate includes elutriated barium sulfate (baryte powder), which is a crushed product of barite mineral, a natural type known as barite, and precipitated barium sulfate produced by chemical reaction.
  • elutriated barium sulfate Precipitated barium sulfate has a uniform particle size, and precipitated barium sulfate is preferred.
  • the D50 (median diameter) of the cumulative particle size distribution of barium sulfate based on volume is preferably 0.1 to 30 ⁇ m, more preferably 0.5 to 25 ⁇ m, and even more preferably 1 to 20 ⁇ m.
  • the specific gravity of barium sulfate is 4.2 to 4.5, and the melting point is 1580°C.
  • the barium sulfate is preferably in an irregular or crushed shape.
  • the thermally conductive particles are preferably at least one inorganic particle selected from the group consisting of alumina (aluminum hydroxide), zinc oxide, magnesium oxide, aluminum nitride, boron nitride, aluminum hydroxide, and silicon carbide. These inorganic particles have high thermal conductivity and low electrical conductivity. Among these, alumina (aluminum oxide) is preferable because it is inexpensive and has a relatively high thermal conductivity.
  • the particles do not contain electrically conductive particles such as copper, gold, silver, aluminum, and tungsten. If electrically conductive particles are used as a heat sink (TIM) between a heat generating part and a heat dissipating part of an electronic component, there is a risk of an accident causing an electrical short circuit.
  • TIM heat sink
  • At least one inorganic particle selected from the group consisting of X-ray shielding particles and thermally conductive particles is preferably surface-treated at least in part with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or a zirconate coupling agent.
  • a silane coupling agent is preferred, and at least a part is preferably surface-treated with a silane compound represented by R a Si(OR') 4-a (R is an unsubstituted or substituted organic group having 1 to 20 carbon atoms, R' is an alkyl group having 1 to 4 carbon atoms, and a is 0 or 3), or a silane coupling agent of a partial hydrolyzate thereof.
  • the silane coupling agent may be mixed with the inorganic particles in advance and pretreated by heat treatment (pretreatment method), or may be added when mixing the base polymer, the curing catalyst, and the inorganic particles (integral blend method). In the case of the pretreatment method and the integral blend method, it is preferable to add 0.01 to 10 parts by mass of the silane coupling agent to 100 parts by mass of the inorganic particles.
  • the surface treatment makes it easier to fill the base polymer, and also prevents the inorganic particles from absorbing the curing catalyst (e.g., platinum-based catalyst), which prevents curing inhibition. This is useful for storage stability.
  • alkoxysilane compounds include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane
  • the silane compounds can be used alone or in combination of two or more.
  • alkoxysilane may be used in combination with one-terminated silanol siloxane or one-terminated trimethoxysilyl polysiloxane.
  • Surface treatment here includes not only covalent bonding but also adsorption.
  • the silicone component is preferably an organopolysiloxane with a viscosity of 10 to 1,000,000 mPa ⁇ s at 25°C. This makes it easier to obtain a composition with a uniform composition of X-ray shielding particles and thermally conductive particles.
  • the curing and crosslinking method is not limited. Examples include an addition reaction between alkenyl groups and SiH groups, a crosslinking method between alkenyl groups or alkyl groups using peroxides, a condensation method between silanols or alkoxy groups, and a combination of these methods for crosslinking and curing.
  • the method of curing by addition reaction between alkenyl groups and SiH groups using a catalyst such as platinum is preferred because it does not produce by-products associated with the reaction, the reaction rate can be controlled, and the curing reaction proceeds smoothly deep into the molded product.
  • peroxide curing reactions can be cured at higher temperatures, making them preferred for rubber and elastomers.
  • the manufacturing method of the present invention involves mixing the silicone composition to form a compound, molding it into a sheet, extrusion molding, or press molding, and curing it.
  • the thickness of the sheet is preferably in the range of 0.2 to 10 mm.
  • the curing conditions for the sheet are preferably a temperature of 70 to 250°C and a heating time of 1 to 15 minutes.
  • the silicone composition of the present invention can be molded into any shape and used as a heat sink between heat generating parts and heat dissipating parts of electronic components, etc.: a TIM (Thermal Interface Material).
  • the shape of at least one inorganic particle selected from the group consisting of the X-ray shielding particles and the thermally conductive particles can be various, such as spherical, irregular (fractured), scaly, polyhedral, etc.
  • the average particle size a range of 0.01 to 150 ⁇ m is preferable.
  • the particle size is measured by measuring the D50 (median diameter) of the cumulative particle size distribution based on volume using a laser diffraction light scattering method.
  • An example of an instrument for this purpose is the LA-950S2 laser diffraction/scattering particle distribution measuring instrument manufactured by Horiba, Ltd.
  • Inorganic particles may be used in combination with at least two particles with different average particle sizes. In this way, smaller particles are filled between larger particles, allowing for a state of nearly close packing, which improves properties such as thermal conductivity, insulation, electromagnetic wave absorption, and material strength.
  • composition of the present invention may contain other components than those mentioned above, if necessary.
  • heat resistance improvers such as red iron oxide or titanium oxide, flame retardant auxiliaries, and curing retarders may be added.
  • Organic or inorganic particle pigments may be added for the purpose of coloring or toning.
  • Alkoxy group-containing silicones may be added as materials added for the purpose of filler surface treatment, etc.
  • organopolysiloxanes that do not have addition curing reactive groups may be added. From the viewpoint of workability, it is desirable for the viscosity at 25°C to be 10 to 100,000 mPa ⁇ s, and particularly 100 to 10,000 mPa ⁇ s.
  • FIG. 1 is a schematic cross-sectional view of an X-ray shielding silicone sheet according to one embodiment of the present invention incorporated into a heat dissipation structure 10, and is an example of its use as a heat sink between a heat generating part and a heat dissipating part of an electronic component: a TIM (Thermal Interface Material).
  • the X-ray shielding silicone sheet dissipates heat generated by an electronic component 13 such as a semiconductor element, and is fixed to the main surface 12a of the heat spreader 12 facing the electronic component 13, and is sandwiched between the electronic component 13 and the heat spreader 12.
  • the X-ray shielding silicone sheet 11a is sandwiched between the heat spreader 12 and the heat sink 15.
  • the heat spreader 12 is formed, for example, in the shape of a rectangular plate, and has a main surface 12a facing the electronic component 13 and a side wall 12b erected along the outer periphery of the main surface 12a.
  • the heat spreader 12 has an X-ray shielding silicone sheet 11b provided on the main surface 12a surrounded by the side wall 12b, and a heat sink 15 provided on the other surface 12c opposite the main surface 12a via the X-ray shielding silicone sheet 11a.
  • the electronic component 13 is, for example, a semiconductor element such as a BGA, and is mounted on a wiring board 14.
  • the thermal conductivity of the thermally conductive silicone sheet was measured using a hot disk (ISO 22007-2: 2008 compliant). As shown in FIG. 2A, this thermal conductivity measuring device 1 sandwiches a polyimide film sensor 2 between two samples 3a and 3b, applies a constant power to the sensor 2, and generates a constant amount of heat to analyze the thermal characteristics from the temperature rise value of the sensor 2.
  • the sensor 2 has a tip 4 with a diameter of 7 mm, and as shown in FIG. 2B, has a double spiral electrode structure, with an applied current electrode 5 and a resistance value electrode (temperature measurement electrode) 6 arranged at the bottom.
  • the thermal conductivity is calculated using the following formula (Math. 1). ⁇ X-ray shielding rate, lead equivalent> The X-ray shielding factor and the lead equivalent were determined by measuring the amount of transmitted X-rays in accordance with JIS Z 4501:2011 (Test method for lead equivalent of X-ray protective equipment) and JIS T61331-1:2016 (Protective equipment for diagnostic X-rays - Part 1: Method for determining attenuation characteristics of materials).
  • X-ray device Comet Technologies Japan MGi-450 type X-ray tube voltage and tube current: 100 kV, 12.5 mA, additional filter plate 0.25 mm Cu X-ray tube focal point-sample distance: 1500 mm Distance between sample and measuring device: 50 mm Measuring device: Ionization chamber exposure dose rate meter, Toyo Medic Co., Ltd., RAMTEC-solo type, A4 type probe used X-ray beam: Narrow X-ray beam ⁇ Hardness> The following two hardness measurements were performed. (1) ASKER C (ASTM D2240:2021) (2) SHORE OO (JIS K 7312:1996)
  • Example 1 Raw material component (1) Base polymer A commercially available two-liquid addition curing type silicone polymer that becomes a silicone gel after curing was used. One liquid (liquid A) contains a base polymer component (component A) and a platinum group metal catalyst (component C), and the other liquid (liquid B) contains a base polymer component (component A) and a crosslinker component (component B) that is an organohydrogenpolysiloxane.
  • the viscosity of liquid A at 25°C is 400 mPa ⁇ s
  • the viscosity of liquid B at 25°C is 300 mPa ⁇ s.
  • (2) X-ray shielding inorganic particles Precipitable barium sulfate, having a D50 (median diameter) of 5 ⁇ m in the cumulative particle size distribution based on volume and an irregular shape as shown in FIG. 3, and surface-treated with decyltrimethoxysilane, was used in an amount of 450 g per 100 g of the base polymer (25 vol.% per 100 vol.% of the composition).
  • (3) Thermally Conductive Inorganic Particles The following thermally conductive inorganic particles were used.
  • Alumina D50 (median diameter) 0.3 ⁇ m, irregular shape as shown in FIG. 4, surface-treated with octyltriethoxysilane.
  • Alumina Alumina having a D50 (median diameter) of 35 ⁇ m and a spherical shape as shown in FIG. 5 was used in an amount of 320 g per 100 g of base polymer (20 vol.% per 100 vol.% of the composition).
  • composition The base polymer, thermally conductive inorganic particles, and X-ray shielding inorganic particles were mixed uniformly to form a compound (composition). This compound (composition) was sandwiched between polyester (PET) films and passed through rolls to form a sheet, which was then heated at 100°C for 10 minutes to obtain a silicone cured sheet with a thickness of 2 mm.
  • PET polyester
  • Example 1 The same procedure as in Example 1 was repeated except that no precipitated barium sulfate was added.
  • Example 2 The same procedure as in Example 1 was repeated except that precipitated barium sulfate surface-treated with decyltrimethoxysilane was used at 450 g per 100 g of base polymer (50 vol. % per 100 vol. % of the composition) and no alumina was added. The above results are shown in Table 1.
  • Example 1 has a higher X-ray shielding rate and lead equivalent than Comparative Example 1, and the thermal conductivity is sufficient for practical use.
  • Example 1 has a higher thermal conductivity than Comparative Example 2, and the X-ray shielding rate and lead equivalent are sufficient for practical use, confirming that the silicone composition has high properties in both X-ray shielding and thermal conductivity. It was also confirmed that it is possible to reduce unnecessary X-rays leaking from the X-ray generating device, and that it is suitable for protecting electronic components inside the irradiated body from radiation such as that used in X-ray inspections.
  • Example 2 Precipitated barium sulfate was surface-treated with decyltrimethoxysilane and used in an amount of 90 g per 100 g of base polymer (10 vol. % per 100 vol. % of the composition).
  • Alumina: D50 (median diameter) 35 ⁇ m, spherical shape, 128 g per 100 g of base polymer (16 vol.% per 100 vol.% of composition) was used.
  • Example 3 Precipitated barium sulfate was surface-treated with decyltrimethoxysilane and used in an amount of 200 g per 100 g of base polymer (10 vol. % per 100 vol. % of the composition).
  • Alumina: D50 (median diameter) 35 ⁇ m, spherical shape, 480 g per 100 g of base polymer (27 vol.% per 100 vol.% of composition) was used.
  • Example 4 Precipitated barium sulfate was surface-treated with decyltrimethoxysilane and used in an amount of 300 g per 100 g of base polymer (10 vol. % per 100 vol. % of the composition).
  • Alumina: D50 (median diameter) 35 ⁇ m, spherical shape, 800 g per 100 g of base polymer (30 vol.% per 100 vol.% of composition) was used.
  • Example 5 Precipitated barium sulfate surface-treated with decyltrimethoxysilane was used in an amount of 540 g per 100 g of base polymer (28.6 vol. % per 100 vol. % of the composition).
  • Table 2 The above results are summarized in Table 2.
  • Example 6 Precipitated barium sulfate: D50 (median diameter) 0.24 ⁇ m, amorphous shape as shown in FIG. 4 was used in an amount of 450 g per 100 g of base polymer (25 vol.% per 100 vol.% of the composition).
  • Example 7 Elutriated barium sulfate: D50 (median diameter) 9.5 ⁇ m, amorphous shape as shown in FIG. 6 was used in an amount of 450 g per 100 g of base polymer (25 vol.% per 100 vol.% of the composition).
  • Alumina D50 (median diameter) 75 ⁇ m, spherical alumina was used in an amount of 320 g per 100 g of base polymer (20 vol.% per 100 vol.% of the composition). The above results, together with the results of Example 1 for reference, are shown in Table 3.
  • Example 7 is submicron barium sulfate
  • Example 8 is elutriated barium sulfate, and the X-ray shielding factor and lead equivalent are high, and the thermal conductivity is sufficient for practical use. It was confirmed that there are no limitations on particle size or type.
  • Example 8 Except for using a non-curable silicone polymer, the same procedure as in Example 1 was carried out.
  • the non-curable silicone polymer had a viscosity of 300 mPa ⁇ s at 25° C.
  • Example 8 uses a non-curable silicone polymer, and therefore retains fluidity, and the hardness was less than 1 and could not be measured using a hardness tester.
  • the X-ray shielding factor and lead equivalent were the same as those of Example 1.
  • the thermal conductivity was sufficient for practical use.
  • the X-ray shielding silicone composition and X-ray shielding silicone sheet of the present invention can reduce unnecessary X-rays leaking from X-ray generating devices, and are also suitable for protecting electronic components inside the subject from radiation in X-ray inspections and the like.

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Abstract

Une composition de silicone de protection contre les rayons X selon la présente invention contient un composant de silicone, des particules de protection contre les rayons X et des particules thermoconductrices, la teneur en composant de silicone étant de 15 à 60 % en volume, la teneur en particules de protection contre les rayons X étant de 5 à 50 % en volume, et la teneur en particules thermiquement conductrices étant de 30 à 80 % en volume pour 100 % en volume de la composition. Un exemple d'un produit moulé de celui-ci est un produit moulé obtenu par moulage de feuille ou moulage à la presse de la composition en une feuille et durcissement de la feuille. Un exemple d'un procédé de production de la feuille comprend le mélange de la composition de silicone pour former un composé, le moulage du composé par moulage de feuille, le moulage par extrusion ou le moulage à la presse, et le durcissement du produit moulé. La présente invention concerne ainsi une composition de silicone ayant à la fois des propriétés de protection contre les rayons X et une conductivité thermique élevées ; une feuille de silicone de protection contre les rayons X ; et un procédé de production de la feuille de silicone de protection contre les rayons X.
PCT/JP2023/043124 2023-04-19 2023-12-01 Composition de silicone de protection contre les rayons x, et feuille de silicone de protection contre les rayons x et son procédé de production Pending WO2024219003A1 (fr)

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TW113106083A TW202442801A (zh) 2023-04-19 2024-02-21 X射線遮蔽性聚矽氧組成物、x射線遮蔽性聚矽氧片及其製造方法

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Citations (8)

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Publication number Priority date Publication date Assignee Title
JPH07207160A (ja) * 1994-01-11 1995-08-08 Toshiba Silicone Co Ltd シリコーン組成物およびその製造方法
JPH0812911A (ja) * 1994-06-29 1996-01-16 Dainippon Printing Co Ltd Ｘ線吸収性コート剤およびそれを用いたプレート材
WO2003029343A1 (fr) * 2001-09-28 2003-04-10 Nippon Tungsten Co., Ltd. Matiere composite a haute densite
JP2011099791A (ja) * 2009-11-06 2011-05-19 Kitagawa Ind Co Ltd 放射線遮蔽シート
JP2013234245A (ja) * 2012-05-08 2013-11-21 Shin-Etsu Chemical Co Ltd 放射線遮蔽構造物シール用室温硬化性オルガノポリシロキサン組成物及び放射線遮蔽構造物
JP2016030774A (ja) * 2014-07-28 2016-03-07 信越化学工業株式会社 熱伝導性シリコーン組成物及び熱伝導性シリコーン成型物
JP2017206645A (ja) * 2016-05-20 2017-11-24 株式会社ツーワン 放射線遮蔽、柔軟性に優れたゴム組成物。
JP2020003371A (ja) * 2018-06-29 2020-01-09 博文 船水 次世代ガンマ線遮蔽シート

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07207160A (ja) * 1994-01-11 1995-08-08 Toshiba Silicone Co Ltd シリコーン組成物およびその製造方法
JPH0812911A (ja) * 1994-06-29 1996-01-16 Dainippon Printing Co Ltd Ｘ線吸収性コート剤およびそれを用いたプレート材
WO2003029343A1 (fr) * 2001-09-28 2003-04-10 Nippon Tungsten Co., Ltd. Matiere composite a haute densite
JP2011099791A (ja) * 2009-11-06 2011-05-19 Kitagawa Ind Co Ltd 放射線遮蔽シート
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JP2017206645A (ja) * 2016-05-20 2017-11-24 株式会社ツーワン 放射線遮蔽、柔軟性に優れたゴム組成物。
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