WO2020116532A1 - Matériau d'étanchéité expansé et procédé de production d'un matériau d'étanchéité expansé - Google Patents

Matériau d'étanchéité expansé et procédé de production d'un matériau d'étanchéité expansé Download PDF

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Publication number
WO2020116532A1
WO2020116532A1 PCT/JP2019/047489 JP2019047489W WO2020116532A1 WO 2020116532 A1 WO2020116532 A1 WO 2020116532A1 JP 2019047489 W JP2019047489 W JP 2019047489W WO 2020116532 A1 WO2020116532 A1 WO 2020116532A1
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WIPO (PCT)
Prior art keywords
foam
sealing material
flexible open
elastomer
cell body
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PCT/JP2019/047489
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English (en)
Japanese (ja)
Inventor
明彦 北澤
伊藤　智之
範幸 世良
草川　公一
Original Assignee
日本発條株式会社
ニッパツフレックス株式会社
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Priority claimed from JP2019064008A external-priority patent/JP7088512B2/ja
Application filed by 日本発條株式会社, ニッパツフレックス株式会社 filed Critical 日本発條株式会社
Priority to CN201980079810.1A priority Critical patent/CN113166631B/zh
Publication of WO2020116532A1 publication Critical patent/WO2020116532A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J15/00—Sealings
    • F16J15/02—Sealings between relatively-stationary surfaces
    • F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
    • F16J15/10—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing

Definitions

  • the present disclosure relates to a foam sealing material and a method for manufacturing the foam sealing material.
  • a long, flexible, open-cell foam made of polyurethane, rubber, polyolefin, etc. (hereinafter abbreviated as flexible open-cell body) is a foam sealing material because it can be compressed with low stress and has good resilience. It is used for etc.
  • flexible open-cell bodies since these flexible open-cell bodies have lower tensile strength and weaker surface strength than non-foamed bodies, they may be damaged due to scratches during processing or construction.
  • drawbacks such as tearing, abrasion, and damage in the application of repeated pressing.
  • contact with sunlight, rain, snow, etc. should be avoided.
  • the open-cell structure when the flexible open-cell body is sandwiched between two surfaces and used for waterproofing and sealing, the open-cell structure has an advantage that it is easy to compress with a low stress, but it has a closed-cell structure. Compared with the foam sealing material, it tends to contain water, and therefore the water-stopping property does not increase, and the sealing property (airtightness, moisture permeation resistance, etc.) tends to be inferior. Furthermore, when a flexible open-cell body is used as a foam sealing material provided on a joint of an outer wall or a lid of a refrigerator, the appearance of the material itself is inferior, so that the design is inferior and the weather resistance and durability are also inferior. is there.
  • Patent Document 1 discloses a method for producing a plastic foam body with a skin, in which vinyl plastisol is impregnated and applied onto the surface of an open-cell body, and then heated to form a film.
  • the plastisol has a high viscosity and is poor in workability, and it is necessary to heat it at a high temperature for a long time, resulting in deterioration of productivity.
  • the film thickness becomes as thick as about 0.4 mm.
  • Patent Document 2 discloses a sealing material in which a long foam is passed while being brought into contact with a heated die, and the surface of the foam is melted to form a film.
  • the composition of this sealing material is limited, such as ester polyurethane foam.
  • the resin of the molten coating is deteriorated due to oxidation, so that the waterproofness is lowered.
  • Patent Documents 3 to 4 disclose a method for producing a laminate produced by applying a non-foamed polyurethane undiluted solution onto release paper and placing a foam base material on the way of curing.
  • this manufacturing method it is difficult to apply a coating on multiple surfaces, and therefore there is a problem in weather resistance and designability.
  • Patent Document 1 Japanese Patent Laid-Open No. 53-16081
  • Patent Document 2 Japanese Patent Laid-Open No. 2006-97790
  • Patent Document 3 Japanese Patent Laid-Open No. 2003-225913
  • Patent Document 4 Japanese Patent Laid-Open No. 2008-138110
  • the present inventors have also examined a method for coating the surface of the flexible open-cell body, but since the coating agent contains an organic solvent, spraying the coating agent on the flexible open-cell body is It was found that the flexible open-cell foam swelled instantly, the flexible open-cell foam absorbed the liquid, did not form a film, did not dry easily even when dried, and shrank in shape and could not be a product.
  • an object of the present disclosure is to make use of the softness and the good resilience of the flexible open-cell foam, and to provide a foam sealing material having sufficient properties such as waterproofness, airtightness, weather resistance, and mechanical strength, and It is to provide the manufacturing method.
  • a long flexible open-cell structure foam At least a portion of the side surface of the flexible open-cell structure foam, an extrusion coating layer extrusion coating a soft thermoplastic resin or a thermosetting elastomer, Foam sealing material.
  • the extrusion coating layer is extrusion-coated on the entire range of at least one of the liquid/gas contact surfaces, which is the non-contact surface of the flexible open-cell structure foam with the material to be sealed. Foam sealing material.
  • ⁇ 3> At least one of the inside and the side surface of the flexible open-cell structure foam is provided so as to extend from one end to the other end in the longitudinal direction of the flexible open-cell structure foam,
  • the foam sealing material according to ⁇ 1> or ⁇ 2> which has an elongation-preventing member that prevents elongation of the cell structure foam in the longitudinal direction.
  • ⁇ 5> The foam sealing material according to any one of ⁇ 1> to ⁇ 4>, wherein the flexible open-cell structure foam is a water-repellent foam.
  • thermoplastic resin is a thermoplastic elastomer having an A hardness of 0 to 85
  • thermosetting elastomer is a thermosetting elastomer having an A hardness of 0 to 85.
  • thermoplastic elastomer is at least one selected from a vinyl chloride thermoplastic elastomer, an olefin thermoplastic elastomer, a styrene thermoplastic elastomer, a urethane thermoplastic elastomer, and an acrylic thermoplastic elastomer.
  • the foam sealing material described. ⁇ 9> The foam sealing material according to any one of ⁇ 1> to ⁇ 8>, wherein the thermosetting elastomer is a room temperature curable thermosetting elastomer.
  • ⁇ 10> Any one of ⁇ 1> to ⁇ 9>, which has an extrusion coating step in which at least a part of the side surface of the flexible open-cell structure foam is extrusion coated with a soft thermoplastic resin or a thermosetting elastomer to form an extrusion coating layer. 2. The method for producing a foam sealing material as described in 1 above. ⁇ 11> In the extrusion coating step, the extrusion coating layer is extrusion coated on the entire range of at least one of the liquid/gas contact surface body contact surface, which is the non-contact surface of the flexible open-cell structure foam with the material to be sealed. ⁇ 10> The method for producing a foam sealing material according to the item ⁇ 10>.
  • a foam sealing material having sufficient properties such as waterproofness, airtightness, weather resistance, and mechanical strength while utilizing the softness and good resilience of a flexible open-cell body, and the production thereof.
  • a method can be provided.
  • FIG. 1 It is a schematic perspective view which shows an example of the foam sealing material which concerns on this embodiment. It is a schematic sectional drawing which shows an example of the foam sealing material which concerns on this embodiment. It is a schematic sectional drawing which shows another example of the foam sealing material which concerns on this embodiment. It is a schematic sectional drawing which shows the state which sealed the gap
  • open-cell structure foam means “open-cell structure”. It may be abbreviated as “body”.
  • closed-cell structure foam may be abbreviated as “closed-cell foam”.
  • the foam sealing material 10 includes a flexible open cell body 12 (long flexible open cell structure foam body 12) and a flexible At least a part of the side surface of the open cell body 12 has an extrusion coating layer 14 obtained by extrusion coating a soft thermoplastic resin or a thermosetting elastomer.
  • the extrusion coating layer 14 is formed by extrusion of a thermoplastic resin or a thermosetting elastomer, the entire longitudinal surface of the flexible open-cell foam 12 can be extrusion-coated at a high speed. Further, if necessary, it is possible to uncover a part in the longitudinal direction or to provide a deformed part in a part of the covered part. Further, by coloring the thermoplastic resin or the thermosetting elastomer, it is possible to enhance the design of the foamed sealing material after coating.
  • the foam sealing material 10 according to the present embodiment has a large improvement in water blocking ability and airtightness by being coated with resin while taking advantage of the softness and good resilience of the flexible open-cell body 12.
  • the resulting foam sealing material has sufficient properties such as weather resistance and mechanical strength.
  • the foam sealing material 10 has the following advantages, for example. Even if the foam sealing material 10 is applied as a water blocking material, sufficient water blocking ability can be exhibited. Even if the foam sealing material 10 is applied as an opening/closing sealing material (a sealing material for a switchboard, a refrigerator, a cooler box, etc.), it does not easily wear. -It is difficult to cut even if the foam sealing material 10 is pulled, and workability is improved. Even when the foamed sealing material 10 is applied as a sealing material for civil engineering/construction (sealing material for outer wall joints, etc.), since it has high weather resistance, it does not easily deteriorate and can maintain various characteristics for a long period of time. -Waterproofness can be exhibited even if the flexible open-cell body 12 is non-water repellent.
  • the foam sealing material 10 according to the present embodiment also has various characteristics such as water resistance, moisture resistance, sound insulation, repeated durability, slidability, and designability.
  • the foam sealing material 10 may include a stretch preventing member 16 that prevents the flexible open cell body 12 from extending in the longitudinal direction, as shown in FIGS. 1 and 2, for example.
  • a stretch preventing member 16 that prevents the flexible open cell body 12 from extending in the longitudinal direction, as shown in FIGS. 1 and 2, for example.
  • the expansion preventing member 16 is included, the dimensional stability of the foam sealing material 10 is enhanced. In addition, self-supportability is improved and workability is improved.
  • the flexible open-cell body 12 (long flexible open-cell structure foam 12) is an open-cell structure-type foam that is soft at room temperature, bends when compressed, and restores when the compression is released. ..
  • the flexible open-cell body 12 may be a thermosetting foam.
  • the thermosetting type has a property that it does not melt even when heated because the resin is crosslinked.
  • the flexible open-cell body 12 is thermoplastic, the compression recovery property at the time of heat is poor, but when the flexible open-cell body 12 is a thermosetting type, it is difficult to heat-soften or heat-shrink, so the temperature setting during extrusion coating is set. Becomes wider.
  • a foam having an open-cell structure such as polyurethane foam, acrylic foam, rubber foam, silicone foam, olefin foam, and melamine foam can be used for extrusion coating. ..
  • a rubber foam or an olefin foam is likely to shrink due to high-temperature curing of the thermosetting elastomer.
  • polyurethane foam, acrylic foam, silicone foam and melamine foam are preferable.
  • the polyurethane foam is suitable for both soft thermoplastic resin and thermosetting elastomer, the open cell degree and the degree of flexibility can be easily changed, and the restorability is extremely good, which is preferable. It is a foam.
  • the flexible open-cell body 12 is preferably water repellent.
  • the flexible open-cell body 12 is water repellent, even if the longitudinal end portion of the foam sealing material not covered with the extrusion coating layer comes into contact with water, it becomes difficult for water to enter. Further, even when the extrusion coating layer 14 is scratched during construction or use, it is difficult for water to enter even if the extrusion coating layer 14 comes into contact with water from scratches. Therefore, the flexibility of construction of the foam sealing material 10 is increased.
  • the silicone foam, the rubber foam, and the olefin foam are water-repellent by themselves, and the polyurethane foam can be made water-repellent by adjusting the composition.
  • the water-repellent property of the flexible open-cell body 12 can be determined by measuring the contact angle with water. Specifically, for example, when the “contact angle to water” on the surface of the flexible open-cell body 12 is 90° or more, it is determined that the flexible open-cell body 12 is water repellent.
  • the contact angle with respect to water was measured by using a contact angle measuring device (Kyowa Interface Science Co., Ltd. full automatic contact angle meter DMo- 701) is used to measure the static contact angle by the sessile drop method.
  • the flexible open-cell body 12 is an open-cell type foam, and is preferably a plastic open-cell body having a closed cell rate of 5% or less.
  • the closed cell rate is measured by the Remington method (according to ASTM D 1940-62T). Specifically, the sample chamber volume R1 is measured using a mercury manometer. Next, the sample of which the volume V and the weight W have been measured is put into a sample chamber and sealed. In this state, a mercury manometer is used to measure the volume R2 of the sample chamber.
  • the closed cell rate (%) is calculated by the following formula.
  • the tensile modulus of the flexible open-cell foam 12 is preferably at least 2.5 kPa, more preferably at least 5 kPa, most preferably at least 10 kPa at 80°C.
  • the flexible open-cell foam 12 is introduced into an extruder, and is drawn out after extrusion-coating the soft thermoplastic resin or the thermosetting elastomer. Then, the extrusion-coated foam sealing material 10 is heated if necessary, cooled, and then wound or cut to a predetermined length. During this time, the flexible open cell body 12 is pulled with a constant stress. Therefore, in order to form a uniform extruded coating layer 14 without wrinkles, the flexible open-cell body 12 preferably has an appropriate tensile modulus within the above range.
  • the foam sealing material 10 has the expansion preventing member 16
  • the expansion preventing member 16 when the extrusion coating layer 14 is extrusion-coated on the flexible open cell body 12, even if the flexible open cell body 12 is pulled, the expansion preventing member 16 is formed. Thereby, the expansion of the flexible open-cell body 12 is prevented. Therefore, in this case, the tensile modulus of the flexible open cell body 12 may be less than 2.5 kPa at 80°C.
  • the method of measuring the tensile modulus is as follows. According to JIS K6400-5 (2012), the stress at 10% elongation at 80°C was measured. Specifically, the sample is punched out into a dumbbell No. 2 shape and stored in a thermostat at 80° C. for 2 hours or more. Then, the sample is pulled at a speed of 200 mm/min with a universal tester under the condition of 80°C. At this time, the stress when the sample is expanded by 10% is determined as the tensile modulus.
  • the cross-sectional shape of the flexible open-cell body 12 (the cross-sectional shape cut along the direction orthogonal to the longitudinal direction of the flexible open-cell body 12) is not particularly limited and is polygonal (triangular, quadrangular, hexagonal). Shape, star shape, etc.), circular shape, kamaboko shape, semicircular shape, shape having a recessed portion, and the like.
  • 1 and 2 show a foam sealing material 10 having a flexible open cell body 12 having a quadrangular cross section. Further, it is desirable that the corners of the sealing material have an R shape so as to form a stable interface with the contact surface of the sealing material during compression.
  • the extrusion coating layer 14 is a resin layer in which at least a part of the side surface of the flexible open-cell body 12 is extrusion-coated with a soft thermoplastic resin or a thermosetting elastomer by an extruder.
  • the extrusion coating layer 14 may be coated on all side surfaces of the flexible open cell body 12. 1 and 2 show a foam sealing material 10 in which an extruded coating layer 14 is coated on all side surfaces of a flexible open-cell body 12. When the stretch preventing member 16 is provided on the side surface of the flexible open cell body 12, the extrusion coating layer 14 covers the side surface of the flexible open cell body 12 via the stretch preventing member 16.
  • the extruded coating layer 14 has a plurality of divided sections. It may be formed on at least one of the side surfaces.
  • the extrusion coating layer 14 may be formed on three of the four surfaces defined by the four corners (FIG. 3( See A)).
  • the extrusion coating layer 14 may be extrusion-coated on the entire range of at least one of the liquid/gas contact surface, which is the non-contact surface of the flexible open-cell body 12 with the material to be sealed. Specifically, for example, as shown in FIG. 4, when a gap between a pair of sealed materials is sealed with a foam sealing material (see FIG. 4A) (see FIG. 4B), flexibility is obtained.
  • the open-cell body 12 can have two liquid/gas contact surfaces as non-contact surfaces with the material to be sealed.
  • the extrusion coating layer 14 may be extrusion-coated on the entire range of at least one of the two liquid/gas contact surfaces.
  • the extrusion coating layer 14 may be extrusion-coated on the entire range of both surfaces of the two surfaces contacting with liquid (gas).
  • 11 is a material to be sealed
  • 12A is a liquid/gas contact surface that is a non-contact surface of the flexible open-cell body 12 with the material to be sealed
  • 12B is a sealed object in the flexible open-cell body 12. The contact surface with the material is shown.
  • the extruded coating layer 14 exists on all of the liquid/gas contact surfaces that are the contact surface and the non-contact surface of the flexible open-cell body 12 with the material to be sealed (for example, the flexible open-cell body 12).
  • the cross-sectional shape is rectangular, the four-sided all-periphery coated product) is the most resistant foam sealing material 10 since no infiltration of water or gas will occur.
  • the extruded coating layer 14 includes all of the contact surfaces of the flexible open-cell body 12 with the material to be sealed and one side of the liquid/gas contact surface that is the non-contact surface (for example, the flexible open-cell body 12 has a contact surface).
  • the extrusion coating layer 14 has one side of the contact surface of the flexible open-cell foam 12 and both sides of the liquid/gas contact surface which is the non-contact surface.
  • the flexible open-cell body 12 has a rectangular cross-sectional shape and is a three-side coated product
  • infiltration of water or the like is suppressed, and thus the foam sealing material 10 has high resistance.
  • the soft thermoplastic resin for forming the extrusion coating layer 14 is from the viewpoint of improving various properties such as waterproofness, airtightness, moisture resistance, sound insulation, weather resistance, mechanical strength, repeated durability, and slidability. It is preferable that the soft thermoplastic resin has a Shore D hardness of 50 or less.
  • suitable resins include polyethylene, polyethylene-based copolymers, soft polyvinyl chloride, various thermoplastic elastomers, soft ester-based resins, soft polyamide-based resins, and soft polypropylene-based resins.
  • Particularly preferable resins are polyethylene, polyethylene-based copolymers (polyethylene vinyl acetate, polyethylene acrylic copolymer, etc.), soft polyvinyl chloride, and thermoplastic elastomers.
  • the soft thermoplastic resin further include hot-melt resins such as olefin-based, nylon-based, polyester-based, polyurethane-based, styrene-butadiene rubber-based, and styrene-isoprene-based resins.
  • hot-melt resins include polyurethane-based resins corresponding to thermosetting elastomers described below, in which isocyanate groups are reactively crosslinked with moisture in the air.
  • thermoplastic elastomer having a Shore A hardness of 0 to 85 is soft and has good adhesion to the contact surface with the material to be sealed (for example, the surface to be stopped), and moreover, the foam sealing material 10 is resistant to bending at the corners. Since wrinkles are hard to enter, it becomes easy to maintain various properties (waterproofness, airtightness, moisture permeability, sound insulation, etc.).
  • a Shore A hardness of the thermoplastic elastomer of 0 to 50 is particularly preferable because the water stopping property is improved.
  • the extruded coating layer 14 is made of a thermoplastic resin
  • its end faces are heat-sealed to each other to form an O-ring-shaped foam sealing material 10, or ultrasonic sealing is performed on a resin part of an automobile part by ultrasonic welding.
  • the material 10 can be assembled.
  • the method for measuring the Shore D hardness is based on JIS 6253-3 (2012). Specifically, with a durometer type D, the numerical value after 15 seconds from pressing the sample needle is measured as Shore D hardness.
  • the method for measuring the Shore A hardness is based on JIS 6253-3 (2012). Specifically, a durometer type A is used to measure the numerical value 15 seconds after pressing the sample needle as Shore A hardness.
  • thermoplastic elastomer examples include vinyl chloride-based thermoplastic elastomer, olefin-based thermoplastic elastomer, styrene-based thermoplastic elastomer, urethane-based thermoplastic elastomer, amide-based thermoplastic elastomer, ester-based thermoplastic elastomer, and acrylic-based thermoplastic elastomer.
  • vinyl chloride-based thermoplastic elastomer olefin-based thermoplastic elastomer
  • styrene-based thermoplastic elastomer urethane-based thermoplastic elastomer
  • amide-based thermoplastic elastomer amide-based thermoplastic elastomer
  • ester-based thermoplastic elastomer ester-based thermoplastic elastomer
  • acrylic-based thermoplastic elastomer examples include acrylic-based thermoplastic elastomer.
  • thermoplastic elastomer at least one selected from a vinyl chloride-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, a styrene-based thermoplastic elastomer, a urethane-based thermoplastic elastomer, and an acrylic-based thermoplastic elastomer. Is preferred.
  • the vinyl chloride thermoplastic elastomer is an elastomer having a polymer obtained by polymerizing at least vinyl chloride.
  • examples of the vinyl chloride-based thermoplastic elastomer include a blend type elastomer in which polyvinyl chloride and nitrile rubber (NBR) are mixed, and a blend type elastomer in which polyvinyl chloride or nitrile rubber is partially crosslinked.
  • the olefin-based thermoplastic elastomer is an elastomer having a polymer obtained by polymerizing at least an olefin.
  • Examples include blended elastomers of olefin rubber and polyolefin resin, partially crosslinked blend elastomer of partially crosslinked olefin rubber and polyolefin resin, and completely crosslinked blend elastomer of ethylene propylene diene rubber (EPDM) and polypropylene. ..
  • the styrene-based thermoplastic elastomer is an elastomer having a polymer obtained by polymerizing at least styrene.
  • the urethane-based thermoplastic elastomer is an elastomer having at least a polymer having a urethane structure.
  • Examples thereof include elastomers having a block structure of polyester and polyurethane, elastomers having a block structure of polyether and polyurethane, and the like.
  • acrylic thermoplastic elastomer a block copolymer of polymethylmethacrylate and acrylic ester can be exemplified.
  • thermosetting elastomer for forming the extrusion coating layer 14 examples include silicone rubber, fluororubber, acrylic rubber, EPDM rubber, butyl rubber, urethane rubber and fluororubber.
  • a room-temperature-curable thermosetting elastomer is preferable because it can be cured at a low temperature and thus has high productivity, and deterioration of the open cell body due to high temperature exposure can be suppressed, and the degree of freedom in selecting the open cell body is increased.
  • room temperature curable thermosetting elastomers include moisture curable rubbers (eg, silicone rubber, modified silicone rubber, polyurethane rubber, polysulfide rubber, etc.).
  • thermosetting elastomer a two-component curable rubber (for example, silicone rubber, modified silicone rubber, polyurethane rubber, acrylic urethane rubber, polysulfide rubber, fluororubber, etc.) can be exemplified.
  • silicone rubber, modified silicone rubber and fluororubber are suitable.
  • these elastomers are very soft coatings, they have excellent heat resistance, weather resistance, electrical characteristics, and flame retardancy. Therefore, the foamed sealing material having the extrusion coating layer containing these elastomers as the extrusion coating layer is particularly suitable as a sealing material for outdoor use or electric equipment.
  • the room temperature-curable thermosetting elastomer since the room temperature-curable thermosetting elastomer has a low raw material viscosity before curing, it is generally impossible to maintain the shape because the raw material is easily drawn down by extrusion molding. Since the uncured thermosetting elastomer discharged from the machine is thinly coated on the flexible open-cell body 12, the flexible open-cell body 12 can be cured while being attached to the long open-cell body without drawdown.
  • the Shore A hardness of the thermosetting elastomer is also preferably 0 to 85, more preferably 0 to 50.
  • the extruded coating layer 14 is soft and has good adhesion to the contact surface (for example, the water stop surface) with the material to be sealed, and moreover, the foam sealing material 10 has wrinkles when bent at the corners. Since it is difficult, various properties (waterproofness, airtightness, moisture permeability, sound insulation, etc.) are easily maintained.
  • the soft thermoplastic resin or the thermosetting elastomer may contain various additives.
  • a flame retardant is applied as an additive, it is possible to impart flame retardancy to the foam sealing material.
  • a coloring agent is applied as an additive, the foamed sealing material has the extrusion coating layer 14 colored in a desired color, and the designability is improved.
  • the thickness of the extruded coating layer 14 is preferably 10 to 1000 ⁇ m from the viewpoint of improving various characteristics such as waterproofness, airtightness, moisture permeability, sound insulation, weather resistance, mechanical strength, repetitive durability and slidability. , 50 to 500 ⁇ m is more preferable, and 50 to 200 ⁇ m is still more preferable.
  • the extension preventing member 16 is a member that prevents the flexible open-cell body 12 from extending in the longitudinal direction.
  • the stretch prevention member 16 is a member provided on the foam sealing material 10 as needed.
  • the stretch-preventing member 16 is not limited in mode as long as it can prevent the flexible open-cell body 12 from stretching in the longitudinal direction.
  • the extension-preventing member 16 is flexible, for example, on at least one of the inside and the side surface of the flexible open-cell body 12. It is preferable that the open cell body 12 extends from one end in the longitudinal direction toward the other end.
  • FIGS. 1 and 2 show the foam sealing material 10 in which the expansion preventing member 16 is provided on the side surface of the flexible open-cell body 12.
  • the cross-sectional shape of the flexible open-cell body 12 is a shape having a plurality of corners (polygonal shape, kamaboko shape, semi-circular shape, etc.)
  • the stretch-preventing member 16 is divided into a plurality of corners. It may be formed on at least one of the side surfaces.
  • the expansion preventing member 16 is provided inside the flexible open-cell body 12, for example, an aspect in which the expansion preventing member 16 is provided by penetrating the flexible open-cell body 12 in the longitudinal direction (see FIG. ))), and an embodiment in which the expansion preventing member 16 is provided in a state of being sandwiched by the divided flexible open cell bodies 12 (see FIG. 3C).
  • Examples of the elongation preventing member 16 include a wire material, a sheet material, and a self-skin layer of the flexible open cell body 12.
  • wire rods resin wire rods (polyester, polyolefin, hard polyvinyl chloride, polyamide, polyimide, polystyrene, polyurethane, etc., wire rods (threads) formed by twisting these fibers), metal wire rods (stainless steel, copper, tungsten, nickel) , Other wire rods of various alloys, etc., and aggregates thereof (aggregates in which wire rods are twisted, bundles in which wire rods are bundled, aggregates in which wire rods are arranged in parallel, etc.) can be exemplified.
  • resin sheet material sheet material such as polyester, polyolefin, hard polyvinyl chloride, polyamide, polyimide, polystyrene and polyurethane
  • metal sheet material sheet material such as stainless steel, copper, tungsten, nickel and other alloys
  • a woven fabric a knitted fabric, a non-woven fabric, a ginseng cloth, and the like.
  • an adhesive tape double-sided tape or the like
  • the sheet material includes a so-called ribbon-shaped material having a narrow width.
  • the self-skin layer is, for example, a film (skin) formed on the surface of a foamed product when foamed polyurethane is foamed in the mold as the flexible open-cell body 12, and as the flexible open-cell body 12.
  • a film (skin) is produced even when the foamed polyurethane is sandwiched between release papers or release films for production.
  • the self-skin layer can be similarly formed by using foamed rubber or foamed silicone as the flexible open-cell body 12.
  • the flexible open-cell body 12 having the self-skin layer has a higher tensile modulus and elasticity than the flexible open-cell body 12 having no self-skin layer. The elongation of the foam 12 is reduced.
  • the extruded resin coating surface is smooth due to the self-skin layer, the sealing property of the foam sealing material 10 is improved and the appearance is also improved.
  • the stretch prevention member 16 preferably has flexibility.
  • the deformed shape can be easily maintained after the foam sealing material 10 is deformed (deformed such as bent or folded). This improves workability.
  • the elongation-preventing member 16 has a size of, for example, a diameter of 10 to 500 ⁇ m for a wire material, a thickness of 5 to 500 ⁇ m for a sheet material, and a thickness of 0.1 to 500 ⁇ m for a self-skin layer, which is soft. Is preferably 0.1 to 100 ⁇ m.
  • the foam sealing material 10 has, for example, a soft thermoplastic resin or a thermosetting elastomer extruded on at least a part of the side surface of the flexible open cell body 12 (flexible long open cell body 12). It has an extrusion coating step of coating to form the extrusion coating layer 14.
  • a flexible thermoplastic resin or a thermosetting elastomer is extrusion-coated on at least a part of the side surface of the flexible open-cell body 12 having the stretch-preventing member 16 to form the extrusion coating layer 14. Good to do.
  • the foam sealing material manufacturing apparatus 100 is composed of an extruder 101, for example, as shown in FIGS. 4 to 6.
  • TR indicates a soft thermoplastic resin or a thermosetting elastomer.
  • the extruder 101 includes an extruder main body 110 that supplies a soft thermoplastic resin or a thermosetting elastomer, and a crosshead 120 that extrudes the soft thermoplastic resin or thermosetting elastomer supplied from the extruder main body 110 into a tubular shape. Is equipped with.
  • the extruder main body 110 includes a cylindrical cylinder 111, a screw 112 inserted in the cylinder 111, and a drive motor 113 that rotationally drives the screw 112.
  • a hopper 114 into which a soft thermoplastic resin or a thermosetting elastomer is charged is provided on the outer peripheral surface of one end of the cylinder 111 (the rear end of the screw 112).
  • a breaker plate 115 is provided on the other end surface of the cylinder 111 (on the tip side of the screw 112).
  • the cylinder 111 is provided with a heater 116 for heating the soft thermoplastic resin. However, when a thermosetting elastomer is applied, the heater 116 may not be provided.
  • the extruder main body 110 causes the melted soft thermoplastic resin or thermosetting elastomer to flow from one end of the cylinder 111 to the other end (from the rear end to the front end of the screw 112) by the rotation of the screw 112.
  • a soft thermoplastic resin or a thermosetting elastomer is supplied to the crosshead 120.
  • the soft thermoplastic resin or the thermosetting elastomer charged from the hopper 114 is heated inside the cylinder 111 by the heater 116 and is kneaded by the screw 112 while being screwed.
  • the fluid flows from the rear end 112 to the front end, passes through the breaker plate 115, and is delivered toward the crosshead 120.
  • a thermosetting elastomer when applied, it may not be heated by the heater 116.
  • the crosshead 120 includes a cylindrical case 121 connected to the extruder main body 110, a cylindrical nozzle 122 arranged at the center of the inside of the case 121, and a nozzle 122. And an extrusion die 123 arranged on the downstream side in the resin extrusion direction.
  • An insertion hole 122A through which the flexible open-cell body 12 (in FIG. 5 to FIG. 6, the flexible open-cell body 12 with the expansion preventing member 16) is inserted is formed in the center of the nozzle 122. ..
  • the tip of the nozzle 122 on the downstream side in the resin extrusion direction has a tapered shape.
  • the region of the nozzle 122 on the distal end side on the downstream side in the resin extrusion direction is formed of the flexible open-cell body 12 supplied from the insertion hole 122A and the soft thermoplastic resin or thermosetting elastomer supplied from the annular flow path 124A.
  • the soft thermoplastic resin or the thermosetting elastomer is extruded into a tubular shape in the confluence region 124B, and the soft thermoplastic resin or the thermosetting elastomer is tubular.
  • the flexible open-cell body 12 is fed into the central portion of the object through the insertion hole 122A of the nozzle 122.
  • the foam sealing material 10 in which the side surfaces (all side surfaces in the present embodiment) of the flexible open-cell body 12 are extrusion-coated with the soft thermoplastic resin or the thermosetting elastomer is extruded from the extrusion die 123.
  • the thermosetting elastomer may be heat-cured or humidified.
  • the foam seal material 10 continuously extruded from the extrusion die 123 is cut to a fixed length.
  • the extruded foam sealing material 10 or the cut foam sealing material 10 may be wound up.
  • the extruder 101 is used as the foam sealing material manufacturing apparatus 100, and at least a part of the side surface of the flexible open-cell foam 12 is made of soft thermoplastic. Extrusion coating of resin or thermosetting elastomer. Therefore, the foam sealing material 10 can be manufactured with high productivity. Further, the side surface of the flexible open-cell body 12 having various sectional shapes can be extrusion-coated with the soft thermoplastic resin or the thermosetting elastomer.
  • a soft thermoplastic resin or a thermosetting elastomer is provided on at least a part of the side surface of the flexible open-cell body 12 having the expansion preventing member 16.
  • the extrusion coating layer 14 is formed by extrusion coating, it is possible to prevent the expansion of the flexible open-cell body 12 during the extrusion coating of the soft thermoplastic resin or the thermosetting elastomer. Therefore, a uniform extruded coating layer 14 without wrinkles can be formed.
  • the flexible open-cell body 12 has a predetermined tensile modulus
  • the flexible open-cell body 12 in the state in which the elongation prevention member 16 is not provided is extrusion-coated with a soft thermoplastic resin or a thermosetting elastomer.
  • a uniform extruded coating layer 14 without wrinkles can be formed.
  • the method for manufacturing the foam sealing material 10 according to the present embodiment is not limited to the above manufacturing method.
  • a mode has been described in which the flexible open cell body 12 having the expansion preventing member 16 is supplied to the insertion hole 122A of the nozzle 122 in advance.
  • the expansion preventing member 16 may be brought into contact with the side surface of the flexible open-cell body 12 immediately before being supplied to the insertion hole 122A of the nozzle 122, and in that state, the expansion prevention member 16 may be supplied to the insertion hole 122A of the nozzle 122. ..
  • the mode in which the screw type extruder main body 110 is applied has been described, but the present invention is not limited to this.
  • a dynamic mixer, a static mixer or the like may be applied. This aspect is effective when a two-pack type thermosetting elastomer is applied.
  • thermosetting elastomer for example, a roller that continuously introduces a ribbon of unvulcanized rubber into a screw
  • a device such as a tank or a pump for introducing the two-liquid semi-solid raw material
  • the method for manufacturing the foam sealing material 10 according to the present embodiment is not limited to the above aspect.
  • the foam sealing material 10 can be manufactured using a known extruder. Further, by changing the extrusion shape of the soft thermoplastic resin or the thermosetting elastomer, it is possible to manufacture the foam sealing material 10 in which the extrusion coating layer 14 is formed on an arbitrary part of the side surface of the flexible open-cell body 12.
  • Example 1 Example of coating on four sides (entire circumference)
  • a crosshead type single screw extruder Japan Steel Works
  • L/D length/diameter ratio
  • polyvinyl chloride Boilica CE65DF A hardness 65 Mitsubishi Chemical
  • a long flexible open-cell foam (Supersheet HP manufactured by Nippon Seijo Co., Ltd., a foamed polyurethane with a self-skin layer having a square section (10 mm ⁇ 10 mm), a density of 0.045 g /Cm 3 , Thermosetting water-repellent polyurethane foam, Polyurethane foam out of 4 sides, PVC adhesive tape is attached to one side with PVC adhesive tape as a stretch prevention member; PVC adhesive tape is ESLON tape # 370 Sekisui Chemical Co., Ltd. was used).
  • Example 2 (Example of two-side coated product) A foam sealing material was obtained in the same manner as in Example 1 except that only one of the surface of the ESLON tape (extension preventing member) and its adjacent surface in the flexible open-cell body was extrusion-coated.
  • Example 3 (Example of three-side coated product) A foam sealing material was obtained in the same manner as in Example 1 except that the surface of the ESLON tape (extension preventing member) and the two adjacent surfaces of the flexible continuous foam were extrusion coated.
  • Example 4 (Example of non-water repellent foam) As a flexible open-cell body, Moltoprene SM-55 (Innoac density 0.055 g/cm 3 , thermosetting non-water-repellent polyurethane foam, non-self skin, polyurethane foam) Foam sealing material in the same manner as in Example 1 except that a vinyl chloride adhesive tape-attached product having a vinyl chloride adhesive tape attached as a member; an Eslon tape #370 manufactured by Sekisui Chemical Co., Ltd. is used as the vinyl adhesive tape.
  • a vinyl chloride adhesive tape-attached product having a vinyl chloride adhesive tape attached as a member
  • an Eslon tape #370 manufactured by Sekisui Chemical Co., Ltd. is used as the vinyl adhesive tape.
  • Example 5 (Example of EPDM foam) As a flexible open-cell body, Eptsealer 685 (manufactured by Nitto Denko KK, density 0.155 g/cm 3 thermosetting water-repellent EPDM-based foam, semi-closed-cell type, non-self-skin, EPDM-based foam A product with a vinyl chloride adhesive tape having a vinyl chloride adhesive tape adhered to one surface as a stretch preventing member; the same as in Example 1 except that Eslon Tape #370 manufactured by Sekisui Chemical Co., Ltd. was used as the vinyl chloride adhesive tape. To obtain a foam sealing material
  • Example 6 (Metal wire elongation prevention member) On one of the four side surfaces of the flexible open-cell body (urethane foam), a metal high-hard wire having a diameter of 0.2 mm is arranged along the longitudinal direction of the flexible open-cell body as an expansion preventing member. A foam sealing material was obtained in the same manner as in Example 1 except that the vinyl chloride adhesive tape was not used.
  • Example 7 (without extension preventing member) As the flexible open-cell body, Superseal WB (a density of 0.055 g/cm3 thermosetting water-repellent foamed polyurethane manufactured by Nippon Jojo Co., Ltd., non-self skin) was used, and no vinyl chloride adhesive tape was used. A foam sealing material was obtained in the same manner as in 1.
  • Examples 8 to 10> (Change in hardness of resin A) Other than using a styrene thermoplastic elastomer (low hardness products AR-SC-45 A hardness 41, AR-SC-15 A hardness 13, AR-SC-0 A hardness 0 manufactured by Aron Kasei Co., Ltd.) as the soft thermoplastic resin A foam sealing material was obtained in the same manner as in Example 1.
  • a styrene thermoplastic elastomer low hardness products AR-SC-45 A hardness 41, AR-SC-15 A hardness 13, AR-SC-0 A hardness 0 manufactured by Aron Kasei Co., Ltd.
  • Example 11> (Change in resin A hardness) A foam sealing material was obtained in the same manner as in Example 1 except that a TPO-based thermoplastic elastomer (low hardness product, Thermorun TT829B A hardness 88 manufactured by Mitsubishi Chemical Corporation) was used as the soft thermoplastic resin.
  • a TPO-based thermoplastic elastomer low hardness product, Thermorun TT829B A hardness 88 manufactured by Mitsubishi Chemical Corporation
  • Example 12 (Change in resin A hardness) A foam sealing material was obtained in the same manner as in Example 1 except that polyvinyl chloride (Binica CE85QB A hardness 85 manufactured by Mitsubishi Chemical Corporation) was used as the soft thermoplastic resin.
  • polyvinyl chloride Boica CE85QB A hardness 85 manufactured by Mitsubishi Chemical Corporation
  • Example 13 As a flexible open-cell body, Nippa Ray C (self-skin layer-made urethane foam with a self-skin layer made by Nihon-Harashi Co., Ltd., 5 mm ⁇ 5 mm, density 0.07 g/cm 3 , thermosetting), which has self-skin layers on both upper and lower sides Foamed sealing material was obtained in the same manner as in Example 1 except that a water-repellent non-water repellent urethane foam) was used and a vinyl chloride adhesive tape was not used.
  • Example 14 (Example of self-skin layer) Nippa Ray EM30 (self-skinned urethane foam 3 mm x 5 mm, density 0.30 g/cm 3 , thermosetting non-water repellent urethane foam manufactured by Nihonbaru Co., Ltd.) having self-skin layers (corresponding to stretch prevention members) on both upper and lower sides is used.
  • a foam sealing material was obtained in the same manner as in Example 1, except that the vinyl chloride adhesive tape was not used.
  • Example 15 (Example of difference in coating resin thickness) A foam sealing material was obtained in the same manner as in Example 1 except that the soft thermoplastic resin was extrusion-coated to a thickness of 500 ⁇ m.
  • ⁇ Comparative example 4> As a water-based coating agent, Permarin UA-300 (Urethane-based water emulsion manufactured by Sanyo Kasei Co., Ltd.) was sprayed on Supersheet HP (10 mm ⁇ 10 mm), which is the flexible open-cell body of Example 1, to form a film at 80° C. And dried for 30 minutes. Although the water-based coating agent was able to form a film that contracted even when it was impregnated into the foam, there was no water stopping property probably because the emulsion itself was hydrophilic.
  • Example 20 A cross-head type extruder equipped with a metering discharge pump and a screw diameter of 30 mm, and a liquid silicone rubber of addition polymerization type as a thermosetting elastomer (KEG-2003H-40-A/B two-component silicone rubber, A hardness 41 Shin-Etsu Chemical Industry Co., Ltd.) was supplied.
  • a thermosetting elastomer KEG-2003H-40-A/B two-component silicone rubber, A hardness 41 Shin-Etsu Chemical Industry Co., Ltd.
  • a long flexible open-cell foam (Supersheet HP manufactured by Nippon Seijo Co., Ltd., a foamed polyurethane with a self-skin layer having a square section (10 mm ⁇ 10 mm), a density of 0.045 g /Cm 3 , Thermosetting water-repellent polyurethane foam, Polyurethane foam out of 4 sides, PVC adhesive tape is attached to one side with PVC adhesive tape as a stretch prevention member; PVC adhesive tape is ESLON tape # 370 Sekisui Chemical Co., Ltd. was used).
  • thermosetting elastomer As the thermosetting elastomer, an addition polymerization type liquid fluororubber (SIFEL3405A/B two-component fluororubber A hardness 40 manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the liquid silicone rubber, and cured at a curing temperature of 150° C. for 8 minutes. Except for this, a foam sealing material having extruded coating layers on four side surfaces was obtained in the same manner as in Example 20.
  • SIFEL3405A/B two-component fluororubber A hardness 40 manufactured by Shin-Etsu Chemical Co., Ltd. was used instead of the liquid silicone rubber, and cured at a curing temperature of 150° C. for 8 minutes. Except for this, a foam sealing material having extruded coating layers on four side surfaces was obtained in the same manner as in Example 20.
  • thermosetting elastomer a moisture-curable one-component silicone rubber (sealant 72 1-component silicone sealant A hardness 30 manufactured by Shin-Etsu Chemical Co., Ltd.) was used in place of the liquid silicone rubber, in the same manner as in Example 20. A foam sealing material having extrusion coating layers formed on four side surfaces was obtained.
  • thermosetting elastomer instead of liquid silicone rubber, moisture-curable one-component acrylic urethane rubber (Bond AU Quick, A hardness 40, tensile stress 0.2 N/mm 2 /@23°C, manufactured by Konishi Bond Co., Ltd.) was used in the same manner as in Example 20 to obtain a foam seal material having extrusion coating layers formed on four side surfaces.
  • moisture-curable one-component acrylic urethane rubber (Bond AU Quick, A hardness 40, tensile stress 0.2 N/mm 2 /@23°C, manufactured by Konishi Bond Co., Ltd.) was used in the same manner as in Example 20 to obtain a foam seal material having extrusion coating layers formed on four side surfaces.
  • Example 24 A foam sealing material having extruded coating layers on four side surfaces was obtained in the same manner as in Example 20 except that the elongation preventing member was not provided.
  • the water stop was evaluated using a compression type water stop tester. Specifically, it is as follows. A double-sided adhesive tape (#5782, manufactured by Sekisui Chemical Co., Ltd.) is attached to one surface of a foam sealing material or a flexible foam (hereinafter referred to as a test body) having a length of 10 cm. At this time, in the case of the test body with the elongation-preventing material, the double-sided tape is attached to the same surface as the elongation-preventing material. Next, the test piece is fixed to the acrylic plate with the double-sided tape.
  • both ends of the test body were supersheet H3 of 10 mm thickness (manufactured by Nippon Seijo; double-sided skin type). Water-stop 30 cm pass) is adhered to form a U-shape. This is sandwiched by another acrylic plate via a spacer having a thickness of 50% of the test body. Then, water was injected from the upper opening so that a predetermined water pressure was obtained. The height of water stoppage (cm) represents the height of water pressure at which water does not leak for 24 hours. Water-stopping is judged to be good when the water-stopping pressure is 3 cm or more after the water-holding time is 24 hours.
  • the 70% compression-stopping property was measured by the same operation as the above method except that the test body was inserted through a spacer having a thickness of 70%.
  • the foam sealing material or flexible foam of each example is cut into a length of 10 cm, and the volume (cm 3 ) and weight W0 (g) are measured. This foam was fixed in a compressed state of 50%, and the weight W1 (g) was measured after it was kept at a water depth of 10 cm for 24 hours under room temperature conditions. The water absorption rate (vol%) was calculated by (W1 ⁇ W0)/volume ⁇ 100.
  • the 50% compressive stress of the foam sealing material or flexible foam of each example was evaluated.
  • the 50% compressive stress was measured by a measuring method according to JIS K6400-2 (2012). However, the sample length was 5 cm.
  • the compressive strain of the foam sealing material or flexible foam of each example was evaluated.
  • the compressive strain was measured by measuring the thickness T0 of a foam having a length of 10 cm, placing it in an oven at 70° C. for 22 hours in a 50% compressed state, and then measuring the thickness T1 after 30 minutes at room temperature after releasing the compression. Sought by.
  • the compressive strain (%) is calculated by (T0-T1)/T0X100.
  • the foam sealing material of the example shows a significant improvement in water blocking ability and water absorption rate as compared with the foam before coating, and even when compared to the closed-cell rubber of the comparative example, it exhibits the same or more water blocking ability.
  • the foam sealing material has almost no deterioration in compressive stress or compressive strain.
  • the resin is coated with sufficient mechanical strength and weather resistance, and it can be said that it is an ideal sealing material that is soft and has excellent durability.
  • Foam Sealing Material 11 Sealed Material 12 Thermosetting Flexible Long Open Cell (Flexible Open Cell) 12A Non-contact surface with sealed material (liquid/gas contact surface) 12B Contact surface with sealed material 14 Extrusion coating layer 16 Elongation prevention member 100 Foam sealing material manufacturing apparatus 101 Extruder 110 Extruder body 111 Cylinder 112 Screw 113 Drive motor 114 Hopper 115 Breaker plate 116 Heater 120 Crosshead 121 Case 122 Nozzle 122A Insertion hole 123 Extrusion die

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Abstract

L'invention concerne un matériau d'étanchéité expansé qui comprend un objet expansé long et flexible ayant une structure à cellules communicantes et une couche de revêtement extrudée formée, sur au moins certaines des surfaces latérales de l'objet expansé flexible ayant une structure à cellules communicantes, par revêtement par extrusion avec une résine thermoplastique flexible ou un élastomère thermodurcissable ; et un procédé de production du matériau d'étanchéité expansé.
PCT/JP2019/047489 2018-12-04 2019-12-04 Matériau d'étanchéité expansé et procédé de production d'un matériau d'étanchéité expansé WO2020116532A1 (fr)

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CN201980079810.1A CN113166631B (zh) 2018-12-04 2019-12-04 发泡密封材以及发泡密封材的制造方法

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JP2018-227666 2018-12-04
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JP2019064008A JP7088512B2 (ja) 2018-12-04 2019-03-28 発泡シール材、および発泡シール材の製造方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112940216A (zh) * 2021-02-05 2021-06-11 方必坤 一种用于高低温试验箱的弹性体及制作方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54150059U (fr) * 1978-04-10 1979-10-18
JPS5571777A (en) * 1978-11-24 1980-05-30 Nhk Spring Co Ltd Sealing material
JPS60137627A (ja) * 1983-12-27 1985-07-22 Nhk Spring Co Ltd 表皮付発泡柱状成形体からなるパッキング材及びその製造法
JPH0556939U (ja) * 1991-12-27 1993-07-30 信越ポリマー株式会社 高弾性低変形構造を有するパッキン材
JPH10505894A (ja) * 1994-09-21 1998-06-09 レイケム・リミテッド 封止部材

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54150059U (fr) * 1978-04-10 1979-10-18
JPS5571777A (en) * 1978-11-24 1980-05-30 Nhk Spring Co Ltd Sealing material
JPS60137627A (ja) * 1983-12-27 1985-07-22 Nhk Spring Co Ltd 表皮付発泡柱状成形体からなるパッキング材及びその製造法
JPH0556939U (ja) * 1991-12-27 1993-07-30 信越ポリマー株式会社 高弾性低変形構造を有するパッキン材
JPH10505894A (ja) * 1994-09-21 1998-06-09 レイケム・リミテッド 封止部材

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112940216A (zh) * 2021-02-05 2021-06-11 方必坤 一种用于高低温试验箱的弹性体及制作方法

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