WO2015029761A1 - Hollow body and manufacturing method therefor - Google Patents

Hollow body and manufacturing method therefor Download PDF

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Publication number
WO2015029761A1
WO2015029761A1 PCT/JP2014/071144 JP2014071144W WO2015029761A1 WO 2015029761 A1 WO2015029761 A1 WO 2015029761A1 JP 2014071144 W JP2014071144 W JP 2014071144W WO 2015029761 A1 WO2015029761 A1 WO 2015029761A1
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WO
WIPO (PCT)
Prior art keywords
hollow body
crosslinking
hollow
thermoplastic elastomer
opening
Prior art date
Application number
PCT/JP2014/071144
Other languages
French (fr)
Japanese (ja)
Inventor
倉持　浩
Original Assignee
株式会社ポリテック・デザイン
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Publication date
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Publication of WO2015029761A1 publication Critical patent/WO2015029761A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
    • B29C69/004—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore making articles by joining parts moulded in separate cavities, said parts being in said separate cavities during said joining
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B39/00—Hollow non-inflatable balls, i.e. having no valves
    • A—HUMAN NECESSITIES
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    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B45/00—Apparatus or methods for manufacturing balls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/78—Means for handling the parts to be joined, e.g. for making containers or hollow articles, e.g. means for handling sheets, plates, web-like materials, tubular articles, hollow articles or elements to be joined therewith; Means for discharging the joined articles from the joining apparatus
    • B29C65/7841—Holding or clamping means for handling purposes
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    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
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    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/737—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined
    • B29C66/7375—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured
    • B29C66/73751—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured the to-be-joined area of at least one of the parts to be joined being uncured, i.e. non cross-linked, non vulcanized
    • B29C66/73752—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured the to-be-joined area of at least one of the parts to be joined being uncured, i.e. non cross-linked, non vulcanized the to-be-joined areas of both parts to be joined being uncured
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/80—General aspects of machine operations or constructions and parts thereof
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/80—General aspects of machine operations or constructions and parts thereof
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    • B29C66/81431—General aspects of the pressing elements, i.e. the elements applying pressure on the parts to be joined in the area to be joined, e.g. the welding jaws or clamps characterised by the design of the pressing elements, e.g. of the welding jaws or clamps characterised by the surface geometry of the part of the pressing elements, e.g. welding jaws or clamps, coming into contact with the parts to be joined comprising a single cavity, e.g. a groove
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/74—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by welding and severing, or by joining and severing, the severing being performed in the area to be joined, next to the area to be joined, in the joint area or next to the joint area
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/90—Measuring or controlling the joining process
    • B29C66/94—Measuring or controlling the joining process by measuring or controlling the time
    • B29C66/949—Measuring or controlling the joining process by measuring or controlling the time characterised by specific time values or ranges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/54—Balls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/54—Balls
    • B29L2031/548—Tennis balls

Definitions

  • the present invention relates to a hollow body used as various game balls such as table tennis balls, toy balls, decorative balls, various floats, valve bodies, roll-on balls, containers and the like, and a method for producing the same.
  • table tennis balls are made of celluloid (a resin produced by mixing camphor as a plasticizer with nitrocellulose).
  • the general manufacturing method is to form a hollow hemisphere by softening a circular celluloid sheet in warm water or hot air, and then fitting the opening edges of the two hemispheres so as to overlap each other.
  • a hollow sphere was obtained by bonding or welding. Therefore, the finished table tennis ball has a fitting seam between the two hemispheres (in addition, the two hemispheres are joined together and then subjected to a polishing process so that the outer surface side of the table tennis ball is The level difference between the two hemispheres disappears, but the level difference remains on the inner surface side).
  • Patent Document 1 and the like disclose a table tennis ball that does not use celluloid and has no fitting joint, and a method for manufacturing the same.
  • the conventional celluloid table tennis ball has the following problems.
  • Patent Document 1 discloses a table tennis ball that does not use celluloid and has no joint joint, and a method for manufacturing the table tennis ball, which is formed by a rotational molding method.
  • the rotational molding method has a problem that the productivity is poor because the mold is housed in the rotation mechanism and rotates, and the liquid or molten raw material is attached to the inner surface of the mold by the rotational centrifugal force. Therefore, there is a problem that the thickness accuracy is poor.
  • a blow molding method, a vacuum molding method, and the like can be considered as a method for producing a hollow sphere without a fitting joint, and these molding methods all have a uniform thickness of the hollow sphere. There is a problem that you can not.
  • the present invention has been made in view of such conventional circumstances, and one of the objects of the present invention is to provide a hollow body that does not use celluloid and a method for producing the same.
  • Another object of the present invention is to provide a hollow body that does not produce a fitting seam and a method for manufacturing the same.
  • Another object of the present invention is to provide a hollow body with good thickness accuracy and uniform thickness in all parts, and a method for manufacturing the same.
  • Another object of the present invention is to provide a hollow body with good productivity and a method for producing the same.
  • the method for producing a hollow body according to the present invention comprises: A thermoplastic elastomer that can be highly cross-linked by chemical cross-linking is placed in a mold with a cross-linking agent added and pressurized, and heated at a low temperature at which no cross-linking reaction takes place, or a cross-linking reaction will occur if the heating time increases.
  • a step of obtaining a hollow first half having an opening on one side by heating and pre-molding for a short time at which a crosslinking reaction does not occur or does not complete crosslinking even at a high heating temperature A thermoplastic elastomer that can be highly crosslinked by chemical crosslinking is placed in a mold with a crosslinking agent added and pressurized, and heated at a low temperature at which no crosslinking reaction occurs, or a crosslinking reaction occurs if the heating time is prolonged.
  • the edge of the opening of the first half and the edge of the opening of the second half are butted against each other and heated at a high temperature to cross-link the first half and the And integrating the second half to form one hollow body and making the hollow body have sufficient hardness.
  • thermoplastic elastomer that can be used as “a thermoplastic elastomer that can be highly crosslinked by chemical crosslinking”
  • a thermoplastic elastomer that can be highly crosslinked by chemical crosslinking 1,2-polybutadiene-based elastomer (manufactured by JSR Corporation, There are a trade name (registered trademark): JSR RB) and a styrene butadiene styrene block copolymer (SBS).
  • thermoplastic elastomer that can be highly crosslinked by chemical crosslinking
  • a hollow body can be constituted without using celluloid (note that the thermoplastic elastomer is crosslinked by being heated at a high temperature, Eventually it becomes a thermosetting resin).
  • first half and the second half are not fitted to each other but are integrated by bridging in a state where the edges of the openings are in contact with each other, a fitting seam does not occur. .
  • the raw material is not attached to the inner surface of the mold in a liquid or molten state as in the case of rotational molding, the raw material is preformed in the state of an elastomer, so that the thickness of the hollow body finally obtained is Can be managed with high accuracy.
  • the hollow body is manufactured regardless of blow molding or vacuum forming, so that the thickness can be made uniform in all parts.
  • the hollow body is manufactured without using rotational molding, the productivity is good.
  • the hardness of the finally obtained hollow body can be adjusted by adjusting the amount of the crosslinking agent.
  • thermoplastic elastomer that can be highly cross-linked by chemical cross-linking is blended with a polymer that can be cross-linked by chemical cross-linking but not as hard as the thermoplastic elastomer, and the blended raw material is preformed to form the first half If the second half is obtained, the hardness of the finally obtained hollow body can be adjusted more easily, and the strength of the finally obtained hollow body can be improved.
  • thermoplastic elastomer when such blending is performed, (i) when a 1,2-polybutadiene-based elastomer is used as a thermoplastic elastomer that can be highly crosslinked by chemical crosslinking, for example, a polyolefin-based thermoplastic elastomer can be blended as the polymer; ii) When a styrene butadiene styrene block copolymer (SBS) is used as a thermoplastic elastomer that can be highly crosslinked by chemical crosslinking, for example, styrene / ethylene / butylene / styrene block copolymer (SEBS) is blended as the polymer. it can.
  • SBS styrene butadiene styrene block copolymer
  • SEBS styrene block copolymer
  • the hollow body according to the present invention comprises a thermoplastic elastomer that can be highly crosslinked by chemical crosslinking, respectively, and a hollow first half and a hollow second half each having an opening on one side. And are integrated by chemical crosslinking in a state where the edges of the openings are butted.
  • the hollow body according to the present invention can be produced by the method for producing a hollow body according to the present invention.
  • the hollow body according to the present invention and the method for producing the same are as follows: (A) A hollow body can be constructed without using celluloid, (B) There is no fitting seam, (C) The thickness of the hollow body can be managed with high accuracy. (D) The thickness can be made uniform in all parts, (E) Productivity is good, It is possible to obtain excellent effects such as.
  • FIG. 2 is a cross-sectional view taken along line II-II in FIG. It is sectional drawing which shows the male type
  • FIG. It is sectional drawing which shows the process of preforming a 1st half body in the said Example 1.
  • FIG. It is sectional drawing which shows the process of integrating a 1st half body and a 2nd half body in the said Example 1.
  • FIG. It is an expanded sectional view which expands and shows a part of FIG. It is sectional drawing which shows the completed hollow body in the said Example 1.
  • Example 7 It is sectional drawing which shows the male type
  • FIG. It is an expanded sectional view which expands and shows a part of FIG. It is sectional drawing which shows the completed hollow body in the said Example 7.
  • Example 8 of this invention before integrating a 1st half and a 2nd half, it is sectional drawing which shows the state which accommodated the liquid in the 1st half.
  • FIGS. 1 to 7 show Example 1 of the present invention for producing a hollow sphere that can be used as a table tennis ball or the like as a hollow body.
  • FIGS. 1 and 2 show a female mold 1 used in this embodiment, and one female mold 1 is provided with four hemispherical recesses 2. The openings 2 a of these recesses 2 are opened on the upper surface of the female mold 1. The periphery of the opening 2a of each recess 2 is surrounded by an annular projection 3 having a triangular cross section.
  • FIG. 3 shows a male die 4 in this embodiment, and four hemispherical convex portions 5 are formed in one male die 4 corresponding to the hemispherical concave portion 2 of the female die 1.
  • a 1,2-polybutadiene elastomer (trade name (registered trademark): JSR RB810, manufactured by JSR Corporation) is used as a thermoplastic elastomer that can be highly crosslinked by chemical crosslinking.
  • Various compounding agents were blended at various ratios.
  • JSR RB810 100 parts by weight Dicumyl peroxide (peroxide crosslinking agent) 1.8 parts by weight Inorganic filler (manufactured by Tosoh Silica Co., Ltd., trade name (registered trademark): nip seal ER) 5 parts by weight Stearic acid (processing aid) Agent) 0.5 part by weight Phenol-based anti-aging agent 0.5 part by weight Titanium white (colorant) 1 part by weight
  • the thermoplastic elastomer 6 is blended with the various compounding agents in the form of a sheet, the sheet is supplied onto the female mold 1 disposed below the male mold 4, and as shown in FIG.
  • thermoplastic elastomer 6 is sandwiched between 1 and a male mold 4 and is preliminarily molded in a compression molding format by applying pressure and heating at 90 ° C. for 60 seconds at a low temperature at which no crosslinking reaction occurs. As a result, four hollow hemispherical first halves 7 each having an opening 7a are obtained.
  • annular protrusion 3 is provided on the female die 1, and these annular protrusions 3 are brought into contact with the lower surface of the male die 4, so that the thermoplastic elastomer outside the recess 2 indicated by reference numeral 8. 6 is separated from the first half 7 in a flat state.
  • the second half body 9 having a hollow hemisphere shape having an opening 9a on one side (see FIGS. 5 and 6). ) Separately. Therefore, in the present embodiment, the first half 7 and the second half 9 are completely the same shape and size.
  • the second half 9 is preformed.
  • the first half 7 and the second half 9 are respectively formed. Separately, it may be preformed simultaneously in parallel.
  • the female mold 1 in which the first half 7 is accommodated and the female mold 1 in which the second half 9 is accommodated are opposed to each other.
  • the film is crosslinked by heating at a high temperature and 170 ° C. for 5 minutes.
  • the two halves 9 are integrated into a single hollow sphere-shaped hollow body 10 and the hollow body 10 has sufficient hardness.
  • FIG. 7 shows a hollow sphere-like hollow body 10 obtained by this process, and can be used as a table tennis ball or the like. If necessary, the outer surface of the hollow body 10 may be polished by blasting or the like. Even if the portion corresponding to the joint surface between the first half 7 and the second half 9 of the outer surface of the hollow body 10 after integration looks like a streak, the streaks are obtained by polishing. Can be made invisible.
  • the hollow body 10 can be formed without using celluloid (note that the thermoplastic elastomer 6 is crosslinked by being heated at a high temperature). As a result, it becomes a thermosetting resin.
  • first half 7 and the second half 9 are not fitted to each other, but are integrated by bridging in a state where the edges of the openings 7a and 9a face each other. There is no seam. Therefore, particularly when used as a ping-pong ball, it is possible to obtain an extremely excellent characteristic that the same way of bouncing whatever part hits the ping-pong table or racket.
  • the raw material is not attached to the inner surface of the mold in a liquid or molten state as in the case of rotational molding, the raw material is preformed in the state of an elastomer, so that the meat of the hollow body 10 finally obtained is Thickness can be managed with high accuracy.
  • the fitting seam is not generated, and the hollow body 10 is manufactured regardless of blow molding or vacuum forming. Therefore, the thickness of the entire hollow body 10 can be made uniform.
  • the hollow body 10 is manufactured without using rotational molding, the productivity is good.
  • the hardness of the finally obtained hollow body 10 can be adjusted by adjusting the amount of the crosslinking agent.
  • thermoplastic elastomer 6 is supplied between the female mold 1 and the male mold 4 in the form of a sheet at the preliminary molding stage.
  • thermoplastic elastomer 6 is in the form of blocks or pellets. It may be supplied between the female mold 1 and the male mold 4 in other states.
  • the female mold 1 and the male mold 4 are four-piece molds, but a larger number than four-piece molds may be used, or three or less molds may be used.
  • titanium white is used as a colorant in order to make the product, that is, the hollow body 10 finally obtained, white.
  • the product is to be orange, a red pigment and a yellow pigment are used instead.
  • the table tennis ball color is white or orange according to the rules of the International Table Tennis Federation).
  • a colorant whose product has a color other than white and orange can be used.
  • Example 1 when crosslinking is performed by heating at a high temperature in a state where the edge of the opening 7a of the first half 7 and the edge of the opening 9a of the second half 9 are abutted, The air in the space surrounded by the first half 7 and the second half 9 expands and the pressure increases, and the first half 7 and the second half 9 are pressed against the inner surface of the female mold 1.
  • the first half body 7 and the second half body 9 function so as to be satisfactorily joined. In this embodiment, the first half body 7 and the second half body 9 Is better bonded.
  • the first half positioned on the lower side before the edge of the opening 7a of the first half 7 and the edge of the opening 9a of the second half 9 are abutted.
  • the pyrolytic chemical foaming agent By placing the pyrolytic chemical foaming agent in the body 7, the pyrolytic chemical foaming agent is accommodated in the space formed between the first half 7 and the second half 9.
  • Other points are the same as in the first embodiment.
  • the foaming agent when the first and second halves 7 and 9 are heated to a high temperature in a state where the edges of the openings 7a and 9a are abutted with each other, the foaming agent generates gas.
  • the pressure in the space surrounded by the first half 7 and the second half 9 can be increased, and the first half 7 and the second half 9 can be pressed more strongly against the inner surface of the female mold 1. Therefore, the 1st half body 7 and the 2nd half body 9 can be joined more favorably and can be integrated.
  • thermoplastic elastomer that can be highly crosslinked by chemical crosslinking is blended with a polymer that can be crosslinked by chemical crosslinking but does not become as hard as the thermoplastic elastomer.
  • thermoplastic elastomer that can be highly crosslinked by chemical crosslinking the same 1,2-polybutadiene elastomer as in Examples 1 and 2 was used, and as the polymer blended therewith, a polyolefin thermoplastic elastomer (DuPont Dow elastomer) Product name (registered trademark): Engage 8150) manufactured by LLC was used. Next, a blending table of raw materials is shown.
  • JSR RB810 75 parts by weight Engage 8150 25 parts by weight Dicumyl peroxide (peroxide crosslinking agent) 3 parts by weight Stearic acid (processing aid) 0.5 parts by weight Phenolic anti-aging agent 0.5 parts by weight Red pigment (coloring) Agent) 0.6 part by weight Yellow pigment (colorant) 0.3 part by weight Except for the blending of the polyolefin-based thermoplastic elastomer, the production method, heating time, heating temperature, and the like are the same as in Example 1, and the mold used is the same as in Example 1.
  • a red pigment and a yellow pigment are blended as colorants in order to make the product (the hollow body 10 finally obtained) orange.
  • the blend of the polymers can more easily adjust the hardness of the finally obtained hollow body and can improve the strength of the finally obtained hollow body.
  • thermoplastic elastomer that can be highly crosslinked by chemical crosslinking
  • SBS styrene butadiene styrene block copolymer
  • Various compounding agents were blended at such ratios.
  • Clayton D-KX414 100 parts by weight Peroxide crosslinking agent (trade name (registered trademark): Park Mill D, manufactured by NOF Corporation) 1 part by weight Stearic acid (processing aid) 0.5 part by weight Phenolic antioxidant 0 .5 parts by weight Inorganic filler (manufactured by Tosoh Silica Co., Ltd., trade name (registered trademark): nip seal ER 10 parts by weight titanium white (colorant) 1 part by weight
  • the mold used was the same as in Example 1, the production process was the same as in Example 1, but the heating temperature in the preforming was 120 ° C., the heating time was 30 seconds, and the heating temperature in the crosslinking process was 170 ° C. The heating time was 5 minutes.
  • thermoplastic elastomer that can be highly crosslinked by chemical crosslinking is blended with a polymer that can be crosslinked by chemical crosslinking but does not become as hard as the thermoplastic elastomer.
  • the same styrene butadiene styrene block copolymer (SBS) as in Example 4 is used as the thermoplastic elastomer that can be highly crosslinked by chemical crosslinking, and the polymer blended with this is styrene / ethylene.
  • Butylene / styrene block copolymer (SEBS) (manufactured by Kraton Polymer Japan Co., Ltd., trade name (registered trademark): Kraton G-1652) was used. Next, a blending table of raw materials is shown.
  • Clayton D-KX414 80 parts by weight Clayton G-1652 20 parts by weight Peroxide crosslinking agent (trade name (registered trademark): Park Mill D-40, manufactured by NOF Corporation) 2 parts by weight Stearic acid (processing aid) 0. 5 parts by weight Phenolic anti-aging agent 0.5 part by weight Red pigment (colorant) 0.6 part by weight Yellow pigment (colorant) 0.3 part by weight Except for the point where SEBS was blended, the production method, heating time, heating temperature, etc. were the same as in Example 4, and the mold used was the same as in Example 4 (and therefore the same as in Example 1). It is.
  • the blend of the polymers can more easily adjust the hardness of the finally obtained hollow body, and can improve the strength of the finally obtained hollow body.
  • thermoplastic elastomer 6 blended with various compounding agents is supplied in the form of a sheet to the female mold 1 disposed below the male mold 4 and is shown in FIG.
  • thermoplastic elastomer 6 is sandwiched between the female mold 1 and the male mold 4 and preliminarily molded in a compression molding format by heating at a high heating temperature of 170 ° C. for 5 seconds.
  • the thermoplastic elastomer 6 is cross-linked, but in this example, the heating time is as short as 5 seconds, so it is not cross-linked. Therefore, as in the case of Example 1, the first half body 7 in the form of a hollow hemisphere having an opening 7a on one side is obtained by the preforming step.
  • the second half 9 is preformed at a heating temperature of 170 ° C. and a heating time of 5 seconds as in the preforming step of the first half 7. Also in this case, although the heating temperature is high, since the heating time is short, the crosslinking reaction does not occur, and an uncrosslinked hollow hemispherical second half 9 having an opening 9a on one side is obtained.
  • the second half 9 is preformed.
  • the first half 7 and the second half 9 are respectively formed. Separately, it may be preformed simultaneously in parallel.
  • the female mold 1 in which the first half 7 is accommodated and the female mold 1 in which the second half 9 is accommodated In a state where the edge of the opening 7a of the first half 7 and the edge of the opening 9a of the second half 9 are butted together, heated at 170 ° C. for 5 minutes to crosslink, The first half body 7 and the second half body 9 are integrated into a single hollow sphere-shaped hollow body 10, and the hollow body 10 has sufficient hardness.
  • the heating temperature in the preforming process of the first and second halves 7 and 9 is also high, it is not necessary to repeatedly cool or heat the female mold 1, so that the work is efficient. Will be able to do.
  • the heating temperature in the preforming step is set to a high temperature
  • the heating time can be set to a time when the crosslinking reaction is completed but the crosslinking is not completed.
  • the degree of cross-linking performed in the preforming step in this case is stopped so as not to hinder as much as possible in the next step of integrating the first half 7 and the second half 9.
  • thermoplastic elastomer in addition, as described above, the method of heating and pre-molding thermoplastic elastomer at a high heating temperature only for a short time in which crosslinking reaction does not occur or crosslinking is not completed is possible.
  • the present invention can also be applied to a case where a polymer that can be crosslinked by chemical crosslinking but is not as hard as the thermoplastic elastomer is blended with the plastic elastomer.
  • FIG. 8 shows a female die 11 used in the present embodiment, and one female die 11 is provided with four semi-rotary ellipsoidal concave portions 12.
  • the openings 12 a of these recesses 12 are open on the upper surface of the female mold 11.
  • the periphery of the opening 12a of each recess 12 is surrounded by a protruding portion 13 having a triangular cross section and forming an annular shape.
  • FIG. 9 shows a male mold 14 in the present embodiment, and four male spheroidal ellipsoidal projections 15 correspond to the semicircular ellipsoidal concave section 12 of the female mold 11. Is formed.
  • thermoplastic elastomer 6 blended with the same various compounding agents as in Example 1 is supplied on the female mold 11 in a sheet form, and as shown in FIG.
  • the thermoplastic elastomer 6 is sandwiched between the male mold 14 and the male mold 14 and is preliminarily molded in a compression molding format by applying pressure and heating at 90 ° C. for 60 seconds at a low temperature at which no crosslinking reaction occurs.
  • four hollow half-spheroid first half bodies 16 having openings 16a on one side are obtained.
  • a second half 9 is obtained separately.
  • the female mold 11 in which the first half 16 is accommodated and the female mold 1 in which the second half 9 is accommodated are opposed to each other.
  • the film is cross-linked by heating at a high temperature of 170 ° C. for 5 minutes.
  • the second half 9 is integrated into one hollow body 17, and the hollow body 17 has sufficient hardness.
  • FIG. 14 shows an eighth embodiment of the present invention.
  • the same first half 16 and second half 9 as in Example 7 are manufactured by the same steps as in Example 7.
  • the edge of the opening 16 a of the first half 16 and the edge of the opening 9 a of the second half 9 are butted together.
  • the edge of the opening 7a of the first half 7 And the edge of the opening 9a of the second half 9 are brought into contact with each other and heated and cross-linked in the same manner as in Example 7 so that the first half 16 and the second half 9 are integrated.
  • the liquid 18 is sealed in the completed hollow body 17.
  • the work for integrating the halves 16 and 9 is performed with the first half 16 facing downward and the second half 9 facing upward, before the integration.
  • the liquid 18 is contained in the first half 16
  • the two halves 9 and 16 are integrated with the second half 9 downward and the first half 16 upward.
  • the liquid 18 is accommodated in the second half 9 before the integration.
  • the liquid 18 is sealed in the hollow body 17, but an object such as a solid, powder, or granule may be sealed instead of the liquid 18 by the same process. Good.
  • the hollow body obtained by the present invention can be used as various balls for competition, toys or decoration, various floats, valve bodies, roll-on balls, containers, etc. It is not particularly limited.
  • the shapes of the first and second halves in the present invention are not limited to the shapes of the respective embodiments.
  • the completed hollow bodies 10 and 17 have a completely closed shape.
  • the completed hollow body communicates with the inside and outside of the hollow body. You may have a hole.
  • thermoplastic elastomer that can be highly crosslinked by chemical crosslinking
  • various materials to be blended with the thermoplastic elastomer that can be highly crosslinked by chemical crosslinking are not limited to those shown in each example, and the hollow material finally obtained according to the use. In order to adjust the characteristics of the body, it can be changed as appropriate.
  • the female mold used at the time of preliminary molding is used as it is at the time of crosslinking. It is more efficient to use the female mold used at the time of preforming as it is at the time of crosslinking as in the embodiment).
  • the present invention provides a hollow body used as various game balls such as table tennis balls, toy balls, decorative balls, various floats, valve bodies, roll-on balls, containers and the like, and a method for producing the same. Useful for.

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  • Health & Medical Sciences (AREA)
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  • Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
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Abstract

Provided are a hollow body and a manufacturing method therefor, which do not use celluloid and with which advantages such as a fitting joint not being generated are obtained. A thermoplastic elastomer, which is able to crosslink to a high degree by chemical crosslinking, is placed in a mold with a crosslinking agent added. As a result of preforming by pressurizing and heating at a temperature and a time in which the crosslinking reaction does not occur or, if the crosslinking reaction does occur, the crosslinking is not completed, a hollow first half (7) with an opening (7a) on one side and a hollow second half (9) with an opening (9a) on one side are each separately obtained. Next, with the edge of the opening (7a) of the first half (7) abutted against the edge of the opening (9a) of the second half (9) inside the molds (1, 1), the halves are heated at a high temperature and crosslinked to unite the first half (7) with the second half (9) and form a hollow body (10), and to cause said hollow body (10) to have adequate hardness.

Description

中空体およびその製造方法Hollow body and method for producing the same
　本発明は、卓球ボール等の各種競技用ボール、玩具用ボール、装飾用ボール、各種浮子、弁体、ロールオン用ボール、容器等として使用される中空体およびその製造方法に関する。 The present invention relates to a hollow body used as various game balls such as table tennis balls, toy balls, decorative balls, various floats, valve bodies, roll-on balls, containers and the like, and a method for producing the same.
＜参照による引用＞
　本出願は、２０１３年９月２日付けで出願した日本国特願２０１３－１８１６８５号およぴ２０１３年９月２０日付けで出願した日本国特願２０１３－１９４７４８号に基づく優先権の主張を伴うものであって、その内容を援用するものである。 <Quotation by reference>
This application claims priority based on Japanese Patent Application No. 2013-18185 filed on September 2, 2013 and Japanese Patent Application No. 2013-194748 filed on September 20, 2013. It accompanies and uses its contents.
　従来より、卓球ボールは、セルロイド（ニトロセルロースに可塑剤として樟脳を混合して製造される樹脂）により製造されている。そして、その一般的な製造方法は、円形のセルロイドのシートを温水中または熱風中で軟化して中空の半球体を成形した後、２つの半球体の開口縁を互いに重なり合うように嵌合して接着または溶接することにより中空球体とするものであった。このため、完成品の卓球ボールには、前記２つの半球体の嵌合継ぎ目が残っている（なお、２つの半球体を接合後、研磨処理が行われることにより、卓球ボールの外面側においては、２つの半球体の段差はなくなっているが、内面側においては段差は残存している）。 Conventionally, table tennis balls are made of celluloid (a resin produced by mixing camphor as a plasticizer with nitrocellulose). The general manufacturing method is to form a hollow hemisphere by softening a circular celluloid sheet in warm water or hot air, and then fitting the opening edges of the two hemispheres so as to overlap each other. A hollow sphere was obtained by bonding or welding. Therefore, the finished table tennis ball has a fitting seam between the two hemispheres (in addition, the two hemispheres are joined together and then subjected to a polishing process so that the outer surface side of the table tennis ball is The level difference between the two hemispheres disappears, but the level difference remains on the inner surface side).
　また、特許文献１等には、セルロイドを用いないとともに、嵌合継ぎ目のない卓球ボールおよびその製造方法が開示されている。 In addition, Patent Document 1 and the like disclose a table tennis ball that does not use celluloid and has no fitting joint, and a method for manufacturing the same.
日本国特表２０１２－５１７２４８号公報（国際公開公報ＷＯ２０１０／１１１９２０）Japan Special Table of Contents 2012-517248 (International Publication WO2010 / 111920)
　前記従来のセルロイド製の卓球ボールにおいては、次のような問題があった。 The conventional celluloid table tennis ball has the following problems.
　（ａ）原材料であるセルロイドは極めて引火性が強く、また成形・乾燥工程での発火の危険性もある、
　（ｂ）セルロイドシートを半球体とする工程は、高度の熟練を要求する技術であるとともに、シートの半球化に際し肉厚を均一化することは極めて困難である、
　（ｃ）可塑剤として樟脳を使用しているため、その揮散により、ボールの弾性率や重量の経時変化が大きい、
　（ｄ）２つの半球体の嵌合継ぎ目から割れてしまうことが多い、
　（ｅ）２つの半球体の嵌合継ぎ目部分では肉厚が他の部分より著しく厚くなるので、嵌合継ぎ目が卓球台やラケットに当たった場合と嵌合継ぎ目以外の部分がそれらに当たった場合とでは、ボールの弾み方が異なる。 (A) Celluloid, which is a raw material, is extremely flammable, and there is a risk of ignition in the molding / drying process.
(B) The process of making the celluloid sheet into a hemisphere is a technique that requires a high degree of skill, and it is extremely difficult to make the thickness uniform when the sheet is hemispherical.
(C) Since camphor is used as a plasticizer, due to its volatilization, the elastic modulus and weight of the ball change over time.
(D) often breaks from the fitting seam of the two hemispheres,
(E) Since the thickness of the fitting seam of the two hemispheres is significantly thicker than other parts, the fitting seam hits the ping-pong table or racket and the part other than the fitting seam hits them. And the way the ball bounces is different.
　また、前述のように特許文献１には、セルロイドを用いないとともに、嵌合継ぎ目のない卓球ボールおよびその製造方法が開示されており、これは回転成形法により卓球ボールを成形するものである。しかし、回転成形法は、金型を回転機構内に収容して回転させる関係上、生産性が悪いという問題があるとともに、液状ないしは溶融状態の原料を回転の遠心力で金型の内面に付着させて成形するので、肉厚の精度が悪いという問題があった。 Further, as described above, Patent Document 1 discloses a table tennis ball that does not use celluloid and has no joint joint, and a method for manufacturing the table tennis ball, which is formed by a rotational molding method. However, the rotational molding method has a problem that the productivity is poor because the mold is housed in the rotation mechanism and rotates, and the liquid or molten raw material is attached to the inner surface of the mold by the rotational centrifugal force. Therefore, there is a problem that the thickness accuracy is poor.
　なお、嵌合継ぎ目のない中空球体を製造する方法としては、回転成形法の他にブロー成形法や真空成形法等が考えられるが、これらの成形方法はいずれも中空球体の肉厚を均一にすることができないという問題がある。 In addition to the rotational molding method, a blow molding method, a vacuum molding method, and the like can be considered as a method for producing a hollow sphere without a fitting joint, and these molding methods all have a uniform thickness of the hollow sphere. There is a problem that you can not.
　また、これまで、卓球ボールについてのみ述べてきたが、従来の他の各種競技用、玩具用および装飾用のボール、各種浮子、弁体、ロールオン用ボール、容器等として使用される中空体においても、肉厚の精度が悪かったり、肉厚が均一でなかったり、生産性が悪いという問題があった。 In addition, only table tennis balls have been described so far, but also in various other conventional competition, toy and decoration balls, various floats, valve bodies, roll-on balls, hollow bodies used as containers, etc. There is a problem that the accuracy of the wall thickness is poor, the wall thickness is not uniform, or the productivity is poor.
　本発明は、このような従来の事情に鑑みてなされたもので、本発明の目的の一つは、セルロイドを用いない中空体およびその製造方法を提供することにある。 The present invention has been made in view of such conventional circumstances, and one of the objects of the present invention is to provide a hollow body that does not use celluloid and a method for producing the same.
　本発明の他の目的は、嵌合継ぎ目を生じない中空体およびその製造方法を提供することにある。 Another object of the present invention is to provide a hollow body that does not produce a fitting seam and a method for manufacturing the same.
　本発明の他の目的は、肉厚の精度がよく、かつ全部分において肉厚を均一にすることができる中空体およびその製造方法を提供することにある。 Another object of the present invention is to provide a hollow body with good thickness accuracy and uniform thickness in all parts, and a method for manufacturing the same.
　本発明の他の目的は、生産性のよい中空体およびその製造方法を提供することにある。 Another object of the present invention is to provide a hollow body with good productivity and a method for producing the same.
　本発明のさらに他の目的は、以下の説明から明らかになろう。 Further objects of the present invention will become clear from the following description.
　本発明による中空体の製造方法は、
　化学架橋により高度に架橋できる熱可塑性エラストマーを架橋剤を添加した状態で型内に入れ、加圧するとともに、架橋反応が起きない低温で加熱するか、または加熱時間が長くなれば架橋反応が起きることとなる高温の加熱温度で、架橋反応が起きないか若しくは起きても架橋が完了しない短時間のみ加熱して予備成形することにより、一方に開口を有する中空の第一の半体を得る段階と、
　前記化学架橋により高度に架橋できる熱可塑性エラストマーを架橋剤を添加した状態で型内に入れ、加圧するとともに、架橋反応が起きない低温で加熱するか、または加熱時間が長くなれば架橋反応が起きることとなる高温の加熱温度で、架橋反応が起きないか若しくは起きても架橋が完了しない短時間のみ加熱して予備成形することにより、一方に開口を有する中空の第二の半体を得る段階と、
　型内において前記第一の半体の前記開口の縁部と前記第二の半体の前記開口の縁部とを突き合わせた状態で高温で加熱して架橋させ、前記第一の半体と前記第二の半体とを一体化して一つの中空体とするとともに該中空体が十分な硬度を有するようにする段階とを有してなるものである。 The method for producing a hollow body according to the present invention comprises:
A thermoplastic elastomer that can be highly cross-linked by chemical cross-linking is placed in a mold with a cross-linking agent added and pressurized, and heated at a low temperature at which no cross-linking reaction takes place, or a cross-linking reaction will occur if the heating time increases. A step of obtaining a hollow first half having an opening on one side by heating and pre-molding for a short time at which a crosslinking reaction does not occur or does not complete crosslinking even at a high heating temperature, ,
A thermoplastic elastomer that can be highly crosslinked by chemical crosslinking is placed in a mold with a crosslinking agent added and pressurized, and heated at a low temperature at which no crosslinking reaction occurs, or a crosslinking reaction occurs if the heating time is prolonged. A step of obtaining a hollow second half having an opening on one side by pre-molding by heating only for a short period of time when crosslinking reaction does not occur or crosslinking is not completed even if it occurs at a high heating temperature. When,
In the mold, the edge of the opening of the first half and the edge of the opening of the second half are butted against each other and heated at a high temperature to cross-link the first half and the And integrating the second half to form one hollow body and making the hollow body have sufficient hardness.
　本発明において、「化学架橋により高度に架橋できる熱可塑性エラストマー」として使用できる熱可塑性エラストマーとしては、本発明者が知る範囲では、今のところ、１，２－ポリブタジエン系エラストマー（ＪＳＲ株式会社製、商品名（登録商標）：ＪＳＲ　ＲＢ）およびスチレンブタジエンスチレンブロック共重合体（ＳＢＳ）がある。 In the present invention, as a thermoplastic elastomer that can be used as “a thermoplastic elastomer that can be highly crosslinked by chemical crosslinking”, as far as the present inventors know, at present, 1,2-polybutadiene-based elastomer (manufactured by JSR Corporation, There are a trade name (registered trademark): JSR RB) and a styrene butadiene styrene block copolymer (SBS).
　本発明においては、化学架橋により高度に架橋できる熱可塑性エラストマーを用いることにより、セルロイドを用いないで中空体を構成できる（なお、前記熱可塑性エラストマーは、高温で加熱されて架橋されることにより、最終的には熱硬化性樹脂となる）。 In the present invention, by using a thermoplastic elastomer that can be highly crosslinked by chemical crosslinking, a hollow body can be constituted without using celluloid (note that the thermoplastic elastomer is crosslinked by being heated at a high temperature, Eventually it becomes a thermosetting resin).
　また、第一の半体と第二の半体とを互いに嵌合するのではなく、それらの開口の縁部を互いに突き合わせた状態で架橋することにより一体化するので、嵌合継ぎ目は生じない。 In addition, since the first half and the second half are not fitted to each other but are integrated by bridging in a state where the edges of the openings are in contact with each other, a fitting seam does not occur. .
　また、回転成形の場合のように原料が液状ないしは溶融状態で型の内面に付着されるのではなく、原料がエラストマーの状態で予備成形が行われるので、最終的に得られる中空体の肉厚を高精度に管理することができる。 In addition, since the raw material is not attached to the inner surface of the mold in a liquid or molten state as in the case of rotational molding, the raw material is preformed in the state of an elastomer, so that the thickness of the hollow body finally obtained is Can be managed with high accuracy.
　また、前記のように嵌合継ぎ目が生じない上、ブロー成形や真空成形によらず中空体を製造するので、全部分において肉厚を均一にすることができる。 Further, as described above, there is no fitting seam, and the hollow body is manufactured regardless of blow molding or vacuum forming, so that the thickness can be made uniform in all parts.
　さらに、回転成形によらずに中空体を製造するので、生産性がよい。 Furthermore, since the hollow body is manufactured without using rotational molding, the productivity is good.
　なお、本発明においては、架橋剤量を調整することにより、最終的に得られる中空体の硬度を調整できる。 In the present invention, the hardness of the finally obtained hollow body can be adjusted by adjusting the amount of the crosslinking agent.
　ただし、化学架橋により高度に架橋できる熱可塑性エラストマーに、化学架橋により架橋できるが前記熱可塑性エラストマーほど硬くならないポリマーをブレンドし、このブレンドした原材料を予備成形することにより、第一の半体および第二の半体を得るようにすれば、最終的に得られる中空体の硬度をより容易に調整できるとともに、最終的に得られる中空体の強度を向上することができる。 However, a thermoplastic elastomer that can be highly cross-linked by chemical cross-linking is blended with a polymer that can be cross-linked by chemical cross-linking but not as hard as the thermoplastic elastomer, and the blended raw material is preformed to form the first half If the second half is obtained, the hardness of the finally obtained hollow body can be adjusted more easily, and the strength of the finally obtained hollow body can be improved.
　このようなブレンドを行うとき、（ｉ）化学架橋により高度に架橋できる熱可塑性エラストマーとして１，２－ポリブタジエン系エラストマーを用いる場合は、前記ポリマーとしては、例えばポリオレフィン系熱可塑性エラストマーをブレンドでき、（ｉｉ）化学架橋により高度に架橋できる熱可塑性エラストマーとしてスチレンブタジエンスチレンブロック共重合体（ＳＢＳ）を用いる場合は、前記ポリマーとしては、例えばスチレン・エチレン・ブチレン・スチレンブロック共重合体（ＳＥＢＳ）をブレンドできる。 When such blending is performed, (i) when a 1,2-polybutadiene-based elastomer is used as a thermoplastic elastomer that can be highly crosslinked by chemical crosslinking, for example, a polyolefin-based thermoplastic elastomer can be blended as the polymer; ii) When a styrene butadiene styrene block copolymer (SBS) is used as a thermoplastic elastomer that can be highly crosslinked by chemical crosslinking, for example, styrene / ethylene / butylene / styrene block copolymer (SEBS) is blended as the polymer. it can.
　本発明による中空体は、それぞれ化学架橋により高度に架橋できる熱可塑性エラストマーを有してなるとともに、それぞれ一方に開口を有する中空の第一の半体と中空の第二の半体とを、互いの前記開口の縁部を突き合わせた状態で化学架橋して一体化してなるものである。 The hollow body according to the present invention comprises a thermoplastic elastomer that can be highly crosslinked by chemical crosslinking, respectively, and a hollow first half and a hollow second half each having an opening on one side. And are integrated by chemical crosslinking in a state where the edges of the openings are butted.
　この本発明による中空体は、前記本発明による中空体の製造方法によって製造できる。 The hollow body according to the present invention can be produced by the method for producing a hollow body according to the present invention.
　本発明による中空体およびその製造方法は、
　（Ａ）セルロイドを用いないで中空体を構成できる、
　（Ｂ）嵌合継ぎ目が生じない、
　（Ｃ）中空体の肉厚を高精度に管理することができる、
　（Ｄ）全部分において肉厚を均一にすることができる、
　（Ｅ）生産性がよい、
等の優れた効果を得られるものである。 The hollow body according to the present invention and the method for producing the same are as follows:
(A) A hollow body can be constructed without using celluloid,
(B) There is no fitting seam,
(C) The thickness of the hollow body can be managed with high accuracy.
(D) The thickness can be made uniform in all parts,
(E) Productivity is good,
It is possible to obtain excellent effects such as.
本発明の実施例１における雌型を示す平面図である。It is a top view which shows the female type | mold in Example 1 of this invention. 図１のＩＩ－ＩＩ線における断面図である。FIG. 2 is a cross-sectional view taken along line II-II in FIG. 前記実施例１における雄型を示す断面図である。It is sectional drawing which shows the male type | mold in the said Example 1. FIG. 前記実施例１において第一の半体を予備成形する工程を示す断面図である。It is sectional drawing which shows the process of preforming a 1st half body in the said Example 1. FIG. 前記実施例１において第一の半体と第二の半体とを一体化する工程を示す断面図である。It is sectional drawing which shows the process of integrating a 1st half body and a 2nd half body in the said Example 1. FIG. 図５の一部を拡大して示す拡大断面図である。It is an expanded sectional view which expands and shows a part of FIG. 前記実施例１における完成した中空体を示す断面図である。It is sectional drawing which shows the completed hollow body in the said Example 1. FIG. 本発明の実施例７における第一の半体用の雌型を示す断面図である。It is sectional drawing which shows the female die for 1st half bodies in Example 7 of this invention. 前記実施例７における第一の半体用の雄型を示す断面図である。It is sectional drawing which shows the male type | mold for the 1st half bodies in the said Example 7. 前記実施例７において第一の半体を予備成形する工程を示す断面図である。It is sectional drawing which shows the process of preforming the 1st half body in the said Example 7. 前記実施例７において第一の半体と第二の半体とを一体化する工程を示す断面図である。It is sectional drawing which shows the process of integrating a 1st half body and a 2nd half body in the said Example 7. FIG. 図１１の一部を拡大して示す拡大断面図である。It is an expanded sectional view which expands and shows a part of FIG. 前記実施例７における完成した中空体を示す断面図である。It is sectional drawing which shows the completed hollow body in the said Example 7. 本発明の実施例８において、第一の半体と第二の半体とを一体化する前に、第一の半体内に液体を収容した状態を示す断面図である。In Example 8 of this invention, before integrating a 1st half and a 2nd half, it is sectional drawing which shows the state which accommodated the liquid in the 1st half.
　以下、本発明を図面に示す実施例に基づいて説明する。 Hereinafter, the present invention will be described based on embodiments shown in the drawings.
　図１～７は、中空体として、卓球ボール等として使用できる中空球体を製造する本発明の実施例１を示している。このうち図１および２は、本実施例において使用する雌型１を示しており、１つの雌型１に４つの半球状の凹部２が設けられている。これらの凹部２の開口２ａは該雌型１の上面に開口している。各凹部２の開口２ａの周囲は横断面三角形状で環状をなす突起部３により囲まれている。 FIGS. 1 to 7 show Example 1 of the present invention for producing a hollow sphere that can be used as a table tennis ball or the like as a hollow body. Among these, FIGS. 1 and 2 show a female mold 1 used in this embodiment, and one female mold 1 is provided with four hemispherical recesses 2. The openings 2 a of these recesses 2 are opened on the upper surface of the female mold 1. The periphery of the opening 2a of each recess 2 is surrounded by an annular projection 3 having a triangular cross section.
　図３は、本実施例における雄型４を示しており、前記雌型１の半球状の凹部２に対応して４つの半球状の凸部５が１つの雄型４に形成されている。 FIG. 3 shows a male die 4 in this embodiment, and four hemispherical convex portions 5 are formed in one male die 4 corresponding to the hemispherical concave portion 2 of the female die 1.
　本実施例においては、化学架橋により高度に架橋できる熱可塑性エラストマーとして、１，２－ポリブタジエン系エラストマー（ＪＳＲ株式会社製、商品名（登録商標）：ＪＳＲ　ＲＢ８１０）を使用し、これに次のような割合で各種配合剤を配合した。 In this example, a 1,2-polybutadiene elastomer (trade name (registered trademark): JSR RB810, manufactured by JSR Corporation) is used as a thermoplastic elastomer that can be highly crosslinked by chemical crosslinking. Various compounding agents were blended at various ratios.
　　ＪＳＲ　ＲＢ８１０　　　　　　　　　　　　　　　１００重量部
　　ジクミルパーオキサイド（過酸化物架橋剤）　　　　　　１．８重量部
　　無機充填剤（東ソー・シリカ株式会社製、商品名
　　　（登録商標）：ニップシール　ＥＲ）　　　　　　　  ５重量部
　　ステアリン酸（加工助剤）                  　　  　  ０．５重量部
　　フェノール系老化防止剤　　　　　　　　　　　　　　　０．５重量部
　　チタンホワイト（着色剤）　　　　　　　　　　　　　　１重量部

　前記熱可塑性エラストマー６に前記各種配合剤を配合したものをシート状とした状態で、雄型４の下方に配置された雌型１上に供給した上、図４に示されるように、雌型１と雄型４とで熱可塑性エラストマー６を挟み、圧縮成形形式で、加圧するとともに架橋反応が起きない低温、９０℃で６０秒加熱して予備成形する。これにより、一方に開口７ａを有する中空半球体状の第一の半体７が４個得られる。 JSR RB810 100 parts by weight Dicumyl peroxide (peroxide crosslinking agent) 1.8 parts by weight Inorganic filler (manufactured by Tosoh Silica Co., Ltd., trade name (registered trademark): nip seal ER) 5 parts by weight Stearic acid (processing aid) Agent) 0.5 part by weight Phenol-based anti-aging agent 0.5 part by weight Titanium white (colorant) 1 part by weight

In a state where the thermoplastic elastomer 6 is blended with the various compounding agents in the form of a sheet, the sheet is supplied onto the female mold 1 disposed below the male mold 4, and as shown in FIG. A thermoplastic elastomer 6 is sandwiched between 1 and a male mold 4 and is preliminarily molded in a compression molding format by applying pressure and heating at 90 ° C. for 60 seconds at a low temperature at which no crosslinking reaction occurs. As a result, four hollow hemispherical first halves 7 each having an opening 7a are obtained.
　なお、雌型１に環状の突起部３が設けられており、これらの環状の突起部３が雄型４の下面に当接されることにより、符号８で示される凹部２外の熱可塑性エラストマー６は平たい状態で第一の半体７から分離される。 An annular protrusion 3 is provided on the female die 1, and these annular protrusions 3 are brought into contact with the lower surface of the male die 4, so that the thermoplastic elastomer outside the recess 2 indicated by reference numeral 8. 6 is separated from the first half 7 in a flat state.
　次に、全く同じ形状かつ同じ大きさの雌型１および雄型４を用いて、全く同じ工程により、一方に開口９ａを有する中空半球体状の第二の半体９（図５および６参照）を別途に得る。したがって、本実施例では、第一の半体７と第二の半体９とは完全に同形同大である。 Next, by using the female mold 1 and the male mold 4 having the same shape and the same size, the second half body 9 having a hollow hemisphere shape having an opening 9a on one side (see FIGS. 5 and 6). ) Separately. Therefore, in the present embodiment, the first half 7 and the second half 9 are completely the same shape and size.
　なお、ここでは、第一の半体７を予備成形した後、第二の半体９を予備成形するものとしたが、勿論、第一の半体７と第二の半体９とをそれぞれ別途に同時並行的に予備成形してもよい。 Here, after the first half 7 is preformed, the second half 9 is preformed. Of course, the first half 7 and the second half 9 are respectively formed. Separately, it may be preformed simultaneously in parallel.
　次に、図５および６に示されるように、第一の半体７が収容されている雌型１と第二の半体９が収容されている雌型１とを対向させ、第一の半体７の開口７ａの縁部と第二の半体９の開口９ａの縁部とを突き合わせた状態で、高温、１７０℃で５分間加熱して架橋させ、第一の半体７と第二の半体９とを一体化して一つの中空球体状の中空体１０とするとともに、該中空体１０が十分な硬度を有するようにする。 Next, as shown in FIGS. 5 and 6, the female mold 1 in which the first half 7 is accommodated and the female mold 1 in which the second half 9 is accommodated are opposed to each other. In a state where the edge of the opening 7a of the half 7 and the edge of the opening 9a of the second half 9 are in contact with each other, the film is crosslinked by heating at a high temperature and 170 ° C. for 5 minutes. The two halves 9 are integrated into a single hollow sphere-shaped hollow body 10 and the hollow body 10 has sufficient hardness.
　図７は、この工程により得られた中空球体状の中空体１０を示しており、卓球ボール等として使用できる。なお、必要があれば、ブラスティング等により中空体１０の外面を研磨してもよい。一体化後の中空体１０の外面のうちの第一の半体７と第二の半体９との接合面に相当する部分が筋のように見えるような場合も、研磨を行うことにより筋が見えないようにすることができる。 FIG. 7 shows a hollow sphere-like hollow body 10 obtained by this process, and can be used as a table tennis ball or the like. If necessary, the outer surface of the hollow body 10 may be polished by blasting or the like. Even if the portion corresponding to the joint surface between the first half 7 and the second half 9 of the outer surface of the hollow body 10 after integration looks like a streak, the streaks are obtained by polishing. Can be made invisible.
　本発明においては、化学架橋により高度に架橋できる熱可塑性エラストマー６を用いることにより、セルロイドを用いないで中空体１０を構成できる（なお、熱可塑性エラストマー６は、高温で加熱されて架橋されることにより、最終的には熱硬化性樹脂となる）。 In the present invention, by using the thermoplastic elastomer 6 that can be highly crosslinked by chemical crosslinking, the hollow body 10 can be formed without using celluloid (note that the thermoplastic elastomer 6 is crosslinked by being heated at a high temperature). As a result, it becomes a thermosetting resin.
　また、第一の半体７と第二の半体９とを互いに嵌合するのではなく、それらの開口７ａ，９ａの縁部を互いに突き合わせた状態で架橋することにより一体化するので、嵌合継ぎ目は生じない。したがって、特に卓球ボールとして使用する場合は、どの部分が卓球台やラケットに当たっても同じ弾み方をするという極めて優れた特性を得ることができる。 In addition, the first half 7 and the second half 9 are not fitted to each other, but are integrated by bridging in a state where the edges of the openings 7a and 9a face each other. There is no seam. Therefore, particularly when used as a ping-pong ball, it is possible to obtain an extremely excellent characteristic that the same way of bouncing whatever part hits the ping-pong table or racket.
　また、回転成形の場合のように原料が液状ないしは溶融状態で型の内面に付着されるのではなく、原料がエラストマーの状態で予備成形が行われるので、最終的に得られる中空体１０の肉厚を高精度に管理することができる。 Further, since the raw material is not attached to the inner surface of the mold in a liquid or molten state as in the case of rotational molding, the raw material is preformed in the state of an elastomer, so that the meat of the hollow body 10 finally obtained is Thickness can be managed with high accuracy.
　また、前記のように嵌合継ぎ目が生じない上、ブロー成形や真空成形によらず中空体１０を製造するので、中空体１０の全部分において肉厚を均一にすることができる。 In addition, as described above, the fitting seam is not generated, and the hollow body 10 is manufactured regardless of blow molding or vacuum forming. Therefore, the thickness of the entire hollow body 10 can be made uniform.
　さらに、回転成形によらずに中空体１０を製造するので、生産性がよい。 Furthermore, since the hollow body 10 is manufactured without using rotational molding, the productivity is good.
　なお、この中空体製造方法では、架橋剤量を調整することにより、最終的に得られる中空体１０の硬度を調整できる。 In this hollow body manufacturing method, the hardness of the finally obtained hollow body 10 can be adjusted by adjusting the amount of the crosslinking agent.
　また、本実施例では、予備成形の段階で、熱可塑性エラストマー６をシート状の状態で雌型１と雄型４との間に供給しているが、熱可塑性エラストマー６をブロック状やペレット状等の他の状態で雌型１と雄型４との間に供給してもよい。 In this embodiment, the thermoplastic elastomer 6 is supplied between the female mold 1 and the male mold 4 in the form of a sheet at the preliminary molding stage. However, the thermoplastic elastomer 6 is in the form of blocks or pellets. It may be supplied between the female mold 1 and the male mold 4 in other states.
　また、本実施例では、雌型１および雄型４を４個取りの型としているが、４個取りより多数取りの型としてもよいし、３個取り以下の型としてもよい。 Further, in this embodiment, the female mold 1 and the male mold 4 are four-piece molds, but a larger number than four-piece molds may be used, or three or less molds may be used.
　また、本実施例では、製品すなわち最終的に得られる中空体１０を白色とするために、着色剤としてチタンホワイトを用いているが、製品をオレンジ色としたい場合は代わりに赤色顔料および黄色顔料を配合すればよい（国際卓球連盟の規定により、卓球ボールの色は白色またはオレンジ色とされている）。勿論、中空体１０を公式の卓球ボール以外の用途に用いる場合は、製品が白色およびオレンジ色以外の色となる着色剤を使用できる。 In this embodiment, titanium white is used as a colorant in order to make the product, that is, the hollow body 10 finally obtained, white. However, if the product is to be orange, a red pigment and a yellow pigment are used instead. (The table tennis ball color is white or orange according to the rules of the International Table Tennis Federation). Of course, when the hollow body 10 is used for purposes other than the official table tennis ball, a colorant whose product has a color other than white and orange can be used.
　前記実施例１においても、第一の半体７の開口７ａの縁部と第二の半体９の開口９ａの縁部とを突き合わせた状態で高温で加熱して架橋させる際には、第一の半体７と第二の半体９とで囲まれる空間の空気が膨張して圧力が増大し、第一の半体７および第二の半体９を雌型１の内面に押圧し、第一の半体７と第二の半体９とを良好に接合させるように機能するが、本実施例ではさらに発泡剤を用いて第一の半体７と第二の半体９とがより良好に接合されるようにする。 In Example 1 as well, when crosslinking is performed by heating at a high temperature in a state where the edge of the opening 7a of the first half 7 and the edge of the opening 9a of the second half 9 are abutted, The air in the space surrounded by the first half 7 and the second half 9 expands and the pressure increases, and the first half 7 and the second half 9 are pressed against the inner surface of the female mold 1. The first half body 7 and the second half body 9 function so as to be satisfactorily joined. In this embodiment, the first half body 7 and the second half body 9 Is better bonded.
　すなわち、本実施例においては、第一の半体７の開口７ａの縁部と第二の半体９の開口９ａの縁部とを突き合わせる前に、下側に位置される第一の半体７内に熱分解型化学的発泡剤を置くことにより、第一の半体７と第二の半体９との間に形成される空間に熱分解型化学的発泡剤を収容する。他の点は実施例１と同様である。 That is, in the present embodiment, the first half positioned on the lower side before the edge of the opening 7a of the first half 7 and the edge of the opening 9a of the second half 9 are abutted. By placing the pyrolytic chemical foaming agent in the body 7, the pyrolytic chemical foaming agent is accommodated in the space formed between the first half 7 and the second half 9. Other points are the same as in the first embodiment.
　本実施例においては、第一および第二の半体７，９がそれらの開口７ａ，９ａの縁部を突き合わされた状態で高温に加熱されたとき、発泡剤がガスを発生させるので、第一の半体７と第二の半体９とで囲まれる空間の圧力をより高くし、第一の半体７および第二の半体９を雌型１の内面により強く押圧させることができるため、より良好に第一の半体７と第二の半体９とを接合し、一体化することができる。 In this embodiment, when the first and second halves 7 and 9 are heated to a high temperature in a state where the edges of the openings 7a and 9a are abutted with each other, the foaming agent generates gas. The pressure in the space surrounded by the first half 7 and the second half 9 can be increased, and the first half 7 and the second half 9 can be pressed more strongly against the inner surface of the female mold 1. Therefore, the 1st half body 7 and the 2nd half body 9 can be joined more favorably and can be integrated.
　本実施例は、化学架橋により高度に架橋できる熱可塑性エラストマーに、化学架橋により架橋できるが前記熱可塑性エラストマーほど硬くならないポリマーをブレンドした例である。化学架橋により高度に架橋できる熱可塑性エラストマーとしては、実施例１および２の場合と同じ１，２－ポリブタジエン系エラストマーを用い、これにブレンドされるポリマーとしては、ポリオレフィン系熱可塑性エラストマー（デュポンダウエラストマーＬＬＣ社製、商品名（登録商標）：Ｅｎｇａｇｅ　８１５０）を用いた。次に、原材料の配合表を示す。 In this example, a thermoplastic elastomer that can be highly crosslinked by chemical crosslinking is blended with a polymer that can be crosslinked by chemical crosslinking but does not become as hard as the thermoplastic elastomer. As the thermoplastic elastomer that can be highly crosslinked by chemical crosslinking, the same 1,2-polybutadiene elastomer as in Examples 1 and 2 was used, and as the polymer blended therewith, a polyolefin thermoplastic elastomer (DuPont Dow elastomer) Product name (registered trademark): Engage 8150) manufactured by LLC was used. Next, a blending table of raw materials is shown.
　　ＪＳＲ　ＲＢ８１０　　　　　　　　　　　　　　　７５重量部
　　Ｅｎｇａｇｅ　８１５０　　　　　　　　　　　　　２５重量部
　　ジクミルパーオキサイド（過酸化物架橋剤）　　　　　３重量部
　　ステアリン酸（加工助剤）                  　　    ０．５重量部
　　フェノール系老化防止剤　　　　　　　　　　　　　　０．５重量部
　　赤色顔料（着色剤）　　　　　　　　　　　　　　　　０．６重量部
　　黄色顔料（着色剤）　　　　　　　　　　　　　　　　０．３重量部

　ポリオレフィン系熱可塑性エラストマーをブレンドした点を除いて、製造方法、加熱時間および加熱温度等は実施例１の場合と同様であり、用いた型も実施例１の場合と同じである。 JSR RB810 75 parts by weight Engage 8150 25 parts by weight Dicumyl peroxide (peroxide crosslinking agent) 3 parts by weight Stearic acid (processing aid) 0.5 parts by weight Phenolic anti-aging agent 0.5 parts by weight Red pigment (coloring) Agent) 0.6 part by weight Yellow pigment (colorant) 0.3 part by weight

Except for the blending of the polyolefin-based thermoplastic elastomer, the production method, heating time, heating temperature, and the like are the same as in Example 1, and the mold used is the same as in Example 1.
　なお、本実施例では、製品（最終的に得られる中空体１０）をオレンジ色とするため、着色剤として赤色顔料および黄色顔料を配合している。 In this example, a red pigment and a yellow pigment are blended as colorants in order to make the product (the hollow body 10 finally obtained) orange.
　本実施例では、前記ポリマーのブレンドにより、最終的に得られる中空体の硬度をより容易に調整できるとともに、最終的に得られる中空体の強度を向上することができる。 In this example, the blend of the polymers can more easily adjust the hardness of the finally obtained hollow body and can improve the strength of the finally obtained hollow body.
　化学架橋により高度に架橋できる熱可塑性エラストマーとして、スチレンブタジエンスチレンブロック共重合体（ＳＢＳ）（クレイトンポリマージャパン株式会社製、商品名（登録商標）：クレイトンＤ－ＫＸ４１４）を使用し、これに次のような割合で各種配合剤を配合した。 As a thermoplastic elastomer that can be highly crosslinked by chemical crosslinking, a styrene butadiene styrene block copolymer (SBS) (manufactured by Kraton Polymer Japan Co., Ltd., trade name (registered trademark): Kraton D-KX414) is used. Various compounding agents were blended at such ratios.
　　クレイトンＤ－ＫＸ４１４　　　　　　　　　　　　１００重量部
　　過酸化物架橋剤（日油株式会社製、商品名（登録
　　商標）：パークミルＤ）　　　　　　　　　　　　　　　１重量部
　　ステアリン酸（加工助剤）                  　　　　　０．５重量部
　　フェノール系老化防止剤　　　　　　　　　　　　　　　０．５重量部
　　無機充填剤（東ソー・シリカ株式会社製、商品名
　　　（登録商標）：ニップシール　ＥＲ　　　　　　　　１０重量部
　　チタンホワイト（着色剤）　　　　　　　　　　　　　　１重量部

　用いた型は実施例１の場合と同じ、製造工程も実施例１の場合と同様であるが、予備成形における加熱温度は１２０℃、加熱時間は３０秒、架橋工程における加熱温度は１７０℃、加熱時間は５分とした。 Clayton D-KX414 100 parts by weight Peroxide crosslinking agent (trade name (registered trademark): Park Mill D, manufactured by NOF Corporation) 1 part by weight Stearic acid (processing aid) 0.5 part by weight Phenolic antioxidant 0 .5 parts by weight Inorganic filler (manufactured by Tosoh Silica Co., Ltd., trade name (registered trademark): nip seal ER 10 parts by weight titanium white (colorant) 1 part by weight

The mold used was the same as in Example 1, the production process was the same as in Example 1, but the heating temperature in the preforming was 120 ° C., the heating time was 30 seconds, and the heating temperature in the crosslinking process was 170 ° C. The heating time was 5 minutes.
　本実施例においても、実施例１の場合と同様の作用効果を得ることができる。 Also in the present embodiment, the same operational effects as in the case of the first embodiment can be obtained.
　本実施例は、実施例３と同様に、化学架橋により高度に架橋できる熱可塑性エラストマーに、化学架橋により架橋できるが前記熱可塑性エラストマーほど硬くならないポリマーをブレンドした例である。 In this example, as in Example 3, a thermoplastic elastomer that can be highly crosslinked by chemical crosslinking is blended with a polymer that can be crosslinked by chemical crosslinking but does not become as hard as the thermoplastic elastomer.
　本実施例では、化学架橋により高度に架橋できる熱可塑性エラストマーとしては、実施例４の場合と同じスチレンブタジエンスチレンブロック共重合体（ＳＢＳ）を用い、これにブレンドされるポリマーとしては、スチレン・エチレン・ブチレン・スチレンブロック共重合体（ＳＥＢＳ）（クレイトンポリマージャパン株式会社製、商品名（登録商標）：クレイトンＧ－１６５２）を用いた。次に、原材料の配合表を示す。 In this example, the same styrene butadiene styrene block copolymer (SBS) as in Example 4 is used as the thermoplastic elastomer that can be highly crosslinked by chemical crosslinking, and the polymer blended with this is styrene / ethylene. Butylene / styrene block copolymer (SEBS) (manufactured by Kraton Polymer Japan Co., Ltd., trade name (registered trademark): Kraton G-1652) was used. Next, a blending table of raw materials is shown.
　　クレイトンＤ－ＫＸ４１４　　　　　　　　　　　　８０重量部
　　クレイトンＧ－１６５２　　　　　　　　　　　　　２０重量部
　　過酸化物架橋剤（日油株式会社製、商品名（登録
　　商標）：パークミルＤ－４０）　　　　　　　　　　　２重量部
　　ステアリン酸（加工助剤）                  　　　  ０．５重量部
　　フェノール系老化防止剤　　　　　　　　　　　　　　０．５重量部
　　赤色顔料（着色剤）　　　　　　　　　　　　　　　　０．６重量部
　　黄色顔料（着色剤）　　　　　　　　　　　　　　　　０．３重量部

　ＳＥＢＳをブレンドした点を除いて、製造方法、加熱時間および加熱温度等は実施例４の場合と同様であり、用いた型も実施例４の場合と同じ（したがって実施例１の場合と同じ）である。 Clayton D-KX414 80 parts by weight Clayton G-1652 20 parts by weight Peroxide crosslinking agent (trade name (registered trademark): Park Mill D-40, manufactured by NOF Corporation) 2 parts by weight Stearic acid (processing aid) 0. 5 parts by weight Phenolic anti-aging agent 0.5 part by weight Red pigment (colorant) 0.6 part by weight Yellow pigment (colorant) 0.3 part by weight

Except for the point where SEBS was blended, the production method, heating time, heating temperature, etc. were the same as in Example 4, and the mold used was the same as in Example 4 (and therefore the same as in Example 1). It is.
　本実施例においても、前記ポリマーのブレンドにより、最終的に得られる中空体の硬度をより容易に調整できるとともに、最終的に得られる中空体の強度を向上することができる。 Also in this example, the blend of the polymers can more easily adjust the hardness of the finally obtained hollow body, and can improve the strength of the finally obtained hollow body.
　本実施例においては、第一の半体７および第二の半体９の予備成形工程における加熱温度および加圧時間のみを実施例１から変更した。その他の点は実施例１と同様である。 In this example, only the heating temperature and pressurization time in the preforming step of the first half 7 and the second half 9 were changed from those in Example 1. Other points are the same as in the first embodiment.
　すなわち、本実施例では、熱可塑性エラストマー６に各種配合剤を配合したものをシート状とした状態で、雄型４の下方に配置された雌型１上に供給した上、図４に示されるように、雌型１と雄型４とで熱可塑性エラストマー６を挟み、圧縮成形形式で、高温の加熱温度１７０℃で５秒加熱して予備成形する。 That is, in the present example, the thermoplastic elastomer 6 blended with various compounding agents is supplied in the form of a sheet to the female mold 1 disposed below the male mold 4 and is shown in FIG. In this manner, the thermoplastic elastomer 6 is sandwiched between the female mold 1 and the male mold 4 and preliminarily molded in a compression molding format by heating at a high heating temperature of 170 ° C. for 5 seconds.
　もし仮に上記高温の加熱温度１７０℃で長時間加熱すると、熱可塑性エラストマー６が架橋してしまうが、本実施例では加熱時間が５秒と短いので、架橋しない。したがって、実施例１の場合と同様に、予備成形工程により、未架橋の、一方に開口７ａを有する中空半球体状の第一の半体７が得られる。 If it is heated for a long time at the high heating temperature of 170 ° C., the thermoplastic elastomer 6 is cross-linked, but in this example, the heating time is as short as 5 seconds, so it is not cross-linked. Therefore, as in the case of Example 1, the first half body 7 in the form of a hollow hemisphere having an opening 7a on one side is obtained by the preforming step.
　次に、第二の半体９を上記第一の半体７の予備成形工程と同じ加熱温度１７０℃および加熱時間５秒で予備成形する。この場合も、加熱温度は高いが、加熱時間が短いため、架橋反応は起こらず、未架橋の、一方に開口９ａを有する中空半球体状の第二の半体９が得られる。 Next, the second half 9 is preformed at a heating temperature of 170 ° C. and a heating time of 5 seconds as in the preforming step of the first half 7. Also in this case, although the heating temperature is high, since the heating time is short, the crosslinking reaction does not occur, and an uncrosslinked hollow hemispherical second half 9 having an opening 9a on one side is obtained.
　なお、ここでは、第一の半体７を予備成形した後、第二の半体９を予備成形するものとしたが、勿論、第一の半体７と第二の半体９とをそれぞれ別途に同時並行的に予備成形してもよい。 Here, after the first half 7 is preformed, the second half 9 is preformed. Of course, the first half 7 and the second half 9 are respectively formed. Separately, it may be preformed simultaneously in parallel.
　次に、実施例１の場合と同じく、図５および６に示されるように、第一の半体７が収容されている雌型１と第二の半体９が収容されている雌型１とを対向させ、第一の半体７の開口７ａの縁部と第二の半体９の開口９ａの縁部とを突き合わせた状態で、高温、１７０℃で５分間加熱して架橋させ、第一の半体７と第二の半体９とを一体化して一つの中空球体状の中空体１０とするとともに、該中空体１０が十分な硬度を有するようにする。 Next, as in the case of Example 1, as shown in FIGS. 5 and 6, the female mold 1 in which the first half 7 is accommodated and the female mold 1 in which the second half 9 is accommodated. In a state where the edge of the opening 7a of the first half 7 and the edge of the opening 9a of the second half 9 are butted together, heated at 170 ° C. for 5 minutes to crosslink, The first half body 7 and the second half body 9 are integrated into a single hollow sphere-shaped hollow body 10, and the hollow body 10 has sufficient hardness.
　本実施例では、第一および第二の半体７，９の予備成形工程の加熱温度も高温とするので、雌型１を繰り返し冷やしたり、加熱したりする必要がないため、作業を能率的に行えるようになる。 In this embodiment, since the heating temperature in the preforming process of the first and second halves 7 and 9 is also high, it is not necessary to repeatedly cool or heat the female mold 1, so that the work is efficient. Will be able to do.
　なお、予備成形工程における加熱温度を高温とする場合、加熱時間を、架橋反応は起きるが、架橋が完了しない時間とすることも可能である。勿論、この場合における予備成形工程で行われる架橋の程度は、次の第一の半体７と第二の半体９とを一体化する工程になるべく支障を与えない程度に止めることが好ましい。 When the heating temperature in the preforming step is set to a high temperature, the heating time can be set to a time when the crosslinking reaction is completed but the crosslinking is not completed. Of course, it is preferable that the degree of cross-linking performed in the preforming step in this case is stopped so as not to hinder as much as possible in the next step of integrating the first half 7 and the second half 9.
　また、上記のように熱可塑性エラストマーを高温の加熱温度で、架橋反応が起きないかまたは起きても架橋が完了しない短時間のみ加熱して予備成形する手法は、化学架橋により高度に架橋できる熱可塑性エラストマーに、化学架橋により架橋できるが前記熱可塑性エラストマーほど硬くならないポリマーをブレンドする場合にも適用できる。 In addition, as described above, the method of heating and pre-molding thermoplastic elastomer at a high heating temperature only for a short time in which crosslinking reaction does not occur or crosslinking is not completed is possible. The present invention can also be applied to a case where a polymer that can be crosslinked by chemical crosslinking but is not as hard as the thermoplastic elastomer is blended with the plastic elastomer.
　図８～１３は、本発明の実施例７を示している。本発明においては、第一の半体７と第二の半体９とが互いに同一形状や対称形状でなくてもよい。本実施例はそのような例である。図８は、本実施例において使用する雌型１１を示しており、１つの雌型１１に４つの半回転楕円体状の凹部１２が設けられている。これらの凹部１２の開口１２ａは該雌型１１の上面に開口している。各凹部１２の開口１２ａの周囲は横断面三角形状で環状をなす突起部１３により囲まれている。 8 to 13 show Embodiment 7 of the present invention. In the present invention, the first half 7 and the second half 9 do not have to have the same shape or symmetrical shape. This embodiment is such an example. FIG. 8 shows a female die 11 used in the present embodiment, and one female die 11 is provided with four semi-rotary ellipsoidal concave portions 12. The openings 12 a of these recesses 12 are open on the upper surface of the female mold 11. The periphery of the opening 12a of each recess 12 is surrounded by a protruding portion 13 having a triangular cross section and forming an annular shape.
　図９は、本実施例における雄型１４を示しており、前記雌型１１の半回転楕円体状の凹部１２に対応して４つの半回転楕円体状の凸部１５が１つの雄型１４に形成されている。 FIG. 9 shows a male mold 14 in the present embodiment, and four male spheroidal ellipsoidal projections 15 correspond to the semicircular ellipsoidal concave section 12 of the female mold 11. Is formed.
　本実施例においても、実施例１の場合と同じ各種配合剤を配合された熱可塑性エラストマー６をシート状の状態で雌型１１上に供給した上、図１０に示されるように、雌型１１と雄型１４とで熱可塑性エラストマー６を挟み、圧縮成形形式で、加圧するとともに架橋反応が起きない低温、９０℃で６０秒加熱して予備成形する。これにより、一方に開口１６ａを有する中空の半回転楕円体状の第一の半体１６が４個得られる。 Also in the present example, the thermoplastic elastomer 6 blended with the same various compounding agents as in Example 1 is supplied on the female mold 11 in a sheet form, and as shown in FIG. The thermoplastic elastomer 6 is sandwiched between the male mold 14 and the male mold 14 and is preliminarily molded in a compression molding format by applying pressure and heating at 90 ° C. for 60 seconds at a low temperature at which no crosslinking reaction occurs. As a result, four hollow half-spheroid first half bodies 16 having openings 16a on one side are obtained.
　その一方、実施例１の場合と全く同じ形状かつ同じ大きさの雌型１および雄型４を用いて、実施例１の場合と全く同じ予備成形工程により、一方に開口９ａを有する中空半球体状の第二の半体９を別途に得る。 On the other hand, a hollow hemisphere having an opening 9a on one side using a female mold 1 and a male mold 4 of exactly the same shape and size as in the case of Example 1 by the same preforming process as in Example 1. A second half 9 is obtained separately.
　次に、図１１および１２に示されるように、第一の半体１６が収容されている雌型１１と第二の半体９が収容されている雌型１とを対向させ、第一の半体１６の開口１６ａの縁部と第二の半体９の開口９ａの縁部とを突き合わせた状態で、高温、１７０℃で５分間加熱して架橋させ、第一の半体１６と第二の半体９とを一体化して一つの中空体１７とするとともに、該中空体１７が十分な硬度を有するようにする。 Next, as shown in FIGS. 11 and 12, the female mold 11 in which the first half 16 is accommodated and the female mold 1 in which the second half 9 is accommodated are opposed to each other. In a state where the edge of the opening 16a of the half 16 and the edge of the opening 9a of the second half 9 are in contact with each other, the film is cross-linked by heating at a high temperature of 170 ° C. for 5 minutes. The second half 9 is integrated into one hollow body 17, and the hollow body 17 has sufficient hardness.
　このような架橋工程により、図１３に示されるように、大略卵形の中空体１７が得られる。 By such a crosslinking step, a generally oval hollow body 17 is obtained as shown in FIG.
　図１４は、本発明の実施例８を示している。本実施例においては、実施例７と同じ工程により実施例７の場合と同じ第一の半体１６および第二の半体９を製造する。 FIG. 14 shows an eighth embodiment of the present invention. In the present example, the same first half 16 and second half 9 as in Example 7 are manufactured by the same steps as in Example 7.
　そして、第一の半体７と第二の半体９とを一体化するために第一の半体１６の開口１６ａの縁部と第二の半体９の開口９ａの縁部とを突き合わせる前に、第一の半体１６内に液体１８を収容し、しかる後に図１４に示されるように雌型１１および１内にそれぞれ収容したまま第一の半体７の開口７ａの縁部と第二の半体９の開口９ａの縁部とを突き合わせ、実施例７の場合と同様に加熱して架橋させ、第一の半体１６と第二の半体９とを一体化する。これにより、完成された中空体１７内には液体１８が封入されている状態になる。 Then, in order to integrate the first half 7 and the second half 9, the edge of the opening 16 a of the first half 16 and the edge of the opening 9 a of the second half 9 are butted together. Before the liquid 18 is contained in the first half 16 and then in the female molds 11 and 1 respectively as shown in FIG. 14, the edge of the opening 7a of the first half 7 And the edge of the opening 9a of the second half 9 are brought into contact with each other and heated and cross-linked in the same manner as in Example 7 so that the first half 16 and the second half 9 are integrated. As a result, the liquid 18 is sealed in the completed hollow body 17.
　なお、本実施例では、第一の半体１６を下方、第二の半体９を上方にした状態で両半体１６，９を一体化する作業を行っているので、一体化を行う前に第一の半体１６の方に液体１８を収容しているが、第二の半体９を下方、第一の半体１６を上方にした状態で両半体９，１６を一体化する作業を行う場合は、一体化を行う前に第二の半体９の方に液体１８を収容する。 In the present embodiment, since the work for integrating the halves 16 and 9 is performed with the first half 16 facing downward and the second half 9 facing upward, before the integration. Although the liquid 18 is contained in the first half 16, the two halves 9 and 16 are integrated with the second half 9 downward and the first half 16 upward. When working, the liquid 18 is accommodated in the second half 9 before the integration.
　また、本実施例では中空体１７内に液体１８が封入されるようにしているが、同様の工程により液体１８の代わりに固体や粉体や粒体等の物体が封入されるようにしてもよい。 In the present embodiment, the liquid 18 is sealed in the hollow body 17, but an object such as a solid, powder, or granule may be sealed instead of the liquid 18 by the same process. Good.
　なお、本発明によって得られる中空体は、卓球ボール以外に、他の競技用、玩具用または装飾用等の各種ボール、各種浮子、弁体、ロールオン用ボール、容器等として使用でき、その用途は特に限定されるものではない。 In addition to the table tennis ball, the hollow body obtained by the present invention can be used as various balls for competition, toys or decoration, various floats, valve bodies, roll-on balls, containers, etc. It is not particularly limited.
　また、本発明における第一および第二の半体の形状は、各実施例の形状に限定されるものではない。 Further, the shapes of the first and second halves in the present invention are not limited to the shapes of the respective embodiments.
　また、前記各実施例においては、完成された中空体１０，１７は完全に閉じられた形状をなしているが、本発明においては、完成された中空体が、該中空体の内外を連通する穴を有していてもよい。 In each of the embodiments, the completed hollow bodies 10 and 17 have a completely closed shape. However, in the present invention, the completed hollow body communicates with the inside and outside of the hollow body. You may have a hole.
　また、本発明において、化学架橋により高度に架橋できる熱可塑性エラストマーに配合する各種材料は、各実施例に示したものに限定されることはなく、用途に応じて、また最終的に得られる中空体の特性を調整するために、適宜変更できる。 Further, in the present invention, various materials to be blended with the thermoplastic elastomer that can be highly crosslinked by chemical crosslinking are not limited to those shown in each example, and the hollow material finally obtained according to the use. In order to adjust the characteristics of the body, it can be changed as appropriate.
　また、前記各実施例では、予備成形時に用いた雌型をそのまま架橋時にも使用しているが、場合によっては架橋時には、予備成形時に用いた型と違う型を用いてもよい（勿論、各実施例のように予備成形時に用いた雌型をそのまま架橋時にも使用する方が能率はよい）。 Further, in each of the above embodiments, the female mold used at the time of preliminary molding is used as it is at the time of crosslinking. It is more efficient to use the female mold used at the time of preforming as it is at the time of crosslinking as in the embodiment).
　以上のように本発明は、卓球ボール等の各種競技用ボール、玩具用ボール、装飾用ボール、各種浮子、弁体、ロールオン用ボール、容器等として使用される中空体およびその製造方法を提供するのに有用である。 As described above, the present invention provides a hollow body used as various game balls such as table tennis balls, toy balls, decorative balls, various floats, valve bodies, roll-on balls, containers and the like, and a method for producing the same. Useful for.
　　１　　雌型
　　４　　雄型
　　６　　熱可塑性エラストマー
　　７　　第一の半体
　　７ａ　第一の半体の開口
　　９　　第二の半体
　　９ａ　第二の半体の開口
　１０　　中空体
　１１　　雌型
　１４　　雄型
　１６　　第一の半体
　１６ａ　第一の半体の開口
　１７　　中空体
　１８　　液体 DESCRIPTION OF SYMBOLS 1 Female type | mold 4 Male type | mold 6 Thermoplastic elastomer 7 1st half body 7a Opening of 1st half body 9 2nd half body 9a Opening of 2nd half body 10 Hollow body 11 Female type | mold 14 Male type | mold 16 1st 16a Opening of the first half 17 Hollow body 18 Liquid

Claims (9)

  1. 　化学架橋により高度に架橋できる熱可塑性エラストマーを架橋剤を添加した状態で型内に入れ、加圧するとともに、架橋反応が起きない低温で加熱するか、または加熱時間が長くなれば架橋反応が起きることとなる高温の加熱温度で、架橋反応が起きないか若しくは起きても架橋が完了しない短時間のみ加熱して予備成形することにより、一方に開口を有する中空の第一の半体を得る段階と、
    　前記化学架橋により高度に架橋できる熱可塑性エラストマーを架橋剤を添加した状態で型内に入れ、加圧するとともに、架橋反応が起きない低温で加熱するか、または加熱時間が長くなれば架橋反応が起きることとなる高温の加熱温度で、架橋反応が起きないか若しくは起きても架橋が完了しない短時間のみ加熱して予備成形することにより、一方に開口を有する中空の第二の半体を得る段階と、
    　型内において前記第一の半体の前記開口の縁部と前記第二の半体の前記開口の縁部とを突き合わせた状態で高温で加熱して架橋させ、前記第一の半体と前記第二の半体とを一体化して一つの中空体とするとともに該中空体が十分な硬度を有するようにする段階とを有してなる中空体の製造方法。     A thermoplastic elastomer that can be highly cross-linked by chemical cross-linking is placed in a mold with a cross-linking agent added and pressurized, and heated at a low temperature at which no cross-linking reaction takes place, or a cross-linking reaction will occur if the heating time increases. A step of obtaining a hollow first half having an opening on one side by heating and pre-molding for a short time at which a crosslinking reaction does not occur or does not complete crosslinking even at a high heating temperature, ,
    A thermoplastic elastomer that can be highly crosslinked by chemical crosslinking is placed in a mold with a crosslinking agent added and pressurized, and heated at a low temperature at which no crosslinking reaction occurs, or a crosslinking reaction occurs if the heating time is prolonged. A step of obtaining a hollow second half having an opening on one side by pre-molding by heating only for a short period of time when crosslinking reaction does not occur or crosslinking is not completed even if it occurs at a high heating temperature. When,
    In the mold, the edge of the opening of the first half and the edge of the opening of the second half are butted against each other and heated at a high temperature to cross-link the first half and the A method for producing a hollow body comprising: integrating the second half body into a single hollow body and making the hollow body have sufficient hardness.
  2. 　前記化学架橋により高度に架橋できる熱可塑性エラストマーは、１，２－ポリブタジエン系エラストマーおよびスチレンブタジエンスチレンブロック共重合体（ＳＢＳ）からなる群から選択される請求項１記載の中空体の製造方法。 The method for producing a hollow body according to claim 1, wherein the thermoplastic elastomer that can be highly crosslinked by chemical crosslinking is selected from the group consisting of 1,2-polybutadiene elastomer and styrene butadiene styrene block copolymer (SBS).
  3. 　前記化学架橋により高度に架橋できる熱可塑性エラストマーに、化学架橋により架橋できるが前記熱可塑性エラストマーほど硬くならないポリマーをブレンドしたものを予備成形することにより、前記第一の半体および前記第二の半体を得る請求項１または２記載の中空体の製造方法。 By pre-molding a thermoplastic elastomer that can be highly crosslinked by chemical crosslinking with a polymer that can be crosslinked by chemical crosslinking but not as hard as the thermoplastic elastomer, the first half and the second half The manufacturing method of the hollow body of Claim 1 or 2 which obtains a body.
  4. 　前記化学架橋により高度に架橋できる熱可塑性エラストマーは１，２－ポリブタジエン系エラストマーであり、ブレンドされる前記ポリマーはポリオレフィン系熱可塑性エラストマーである請求項３記載の中空体の製造方法。 The method for producing a hollow body according to claim 3, wherein the thermoplastic elastomer that can be highly crosslinked by chemical crosslinking is a 1,2-polybutadiene elastomer, and the blended polymer is a polyolefin thermoplastic elastomer.
  5. 　前記化学架橋により高度に架橋できる熱可塑性エラストマーはスチレンブタジエンスチレンブロック共重合体（ＳＢＳ）であり、ブレンドされる前記ポリマーはスチレン・エチレン・ブチレン・スチレンブロック共重合体（ＳＥＢＳ）である請求項３記載の中空体の製造方法。 The thermoplastic elastomer that can be highly crosslinked by chemical crosslinking is a styrene butadiene styrene block copolymer (SBS), and the polymer to be blended is a styrene / ethylene / butylene / styrene block copolymer (SEBS). The manufacturing method of the hollow body of description.
  6. 　前記型内において前記第一の半体の前記開口の縁部と前記第二の半体の前記開口の縁部とを突き合わせた状態で高温で加熱して架橋させる前に、前記第一の半体と前記第二の半体との間に形成される空間に発泡剤を収容する段階を有する請求項１乃至５のいずれか１項に記載の中空体の製造方法。 Before heating and crosslinking at a high temperature with the edge of the opening of the first half and the edge of the opening of the second half abutted in the mold, the first half The method for producing a hollow body according to any one of claims 1 to 5, further comprising a step of accommodating a foaming agent in a space formed between the body and the second half.
  7. 　前記第一の半体と前記第二の半体とを一体化して一つの中空体とする前に、前記第一の半体と前記第二の半体との間に空気以外の物質を挿入する段階を有する請求項１乃至６のいずれか１項に記載の中空体の製造方法。 Before the first half and the second half are integrated into one hollow body, a substance other than air is inserted between the first half and the second half. The method for producing a hollow body according to any one of claims 1 to 6, further comprising:
  8. 　前記第一および第二の半体はそれぞれ中空の半球体状をなしており、前記第一の半体と前記第二の半体とを一体化して得られる前記中空体は中空球体である請求項１乃至７のいずれか１項に記載の中空体の製造方法。 The first and second halves each have a hollow hemispherical shape, and the hollow body obtained by integrating the first and second halves is a hollow sphere. Item 8. The method for producing a hollow body according to any one of Items 1 to 7.
  9. 　それぞれ化学架橋により高度に架橋できる熱可塑性エラストマーを有してなるとともに、それぞれ一方に開口を有する中空の第一の半体と中空の第二の半体とを、互いの前記開口の縁部を突き合わせた状態で化学架橋して一体化してなる中空体。 Each of them has a thermoplastic elastomer that can be highly crosslinked by chemical crosslinking, and the hollow first half and the hollow second half each having an opening on one side are connected to the edges of the openings. A hollow body that is integrated by chemical cross-linking in a butted state.
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CN113650210A (en) * 2021-08-25 2021-11-16 天长市富宝橡塑制品有限公司 Hollow plastic ball forming die

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