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WO2005039863A1 - Process for producing olefinic resin foam - Google Patents

Process for producing olefinic resin foam Download PDF

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Publication number
WO2005039863A1
WO2005039863A1 PCT/JP2004/015681 JP2004015681W WO2005039863A1 WO 2005039863 A1 WO2005039863 A1 WO 2005039863A1 JP 2004015681 W JP2004015681 W JP 2004015681W WO 2005039863 A1 WO2005039863 A1 WO 2005039863A1
Authority
WO
WIPO (PCT)
Prior art keywords
foam
needle
resin
extruded
needles
Prior art date
Application number
PCT/JP2004/015681
Other languages
French (fr)
Japanese (ja)
Inventor
Hiroshi Nosaka
Takeshi Yukawa
Original Assignee
Asahi Kasei Life & Living Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Life & Living Corporation filed Critical Asahi Kasei Life & Living Corporation
Priority to JP2005514974A priority Critical patent/JPWO2005039863A1/en
Publication of WO2005039863A1 publication Critical patent/WO2005039863A1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B26HAND CUTTING TOOLS; CUTTING; SEVERING
    • B26FPERFORATING; PUNCHING; CUTTING-OUT; STAMPING-OUT; SEVERING BY MEANS OTHER THAN CUTTING
    • B26F1/00Perforating; Punching; Cutting-out; Stamping-out; Apparatus therefor
    • B26F1/26Perforating by non-mechanical means, e.g. by fluid jet
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34Auxiliary operations
    • B29C44/56After-treatment of articles, e.g. for altering the shape
    • B29C44/5627After-treatment of articles, e.g. for altering the shape by mechanical deformation, e.g. crushing, embossing, stretching
    • B29C44/5663After-treatment of articles, e.g. for altering the shape by mechanical deformation, e.g. crushing, embossing, stretching by perforating the foam, e.g. to open the cells

Definitions

  • the present invention relates to a method for producing an oil-based resin foam capable of easily replacing a blowing agent gas remaining in a foam with air.
  • the foam produced by the production method of the present invention is used as a cushioning packaging material for industrial products and the like, a heat insulation beat board for houses and the like, a sporting tool core material for body boats and the like, a floating material such as a float and the like.
  • a foaming agent is used in producing a plastic foam.
  • the foaming agent is changed from a CFC-based foaming agent to a hydrocarbon (C3-C5) -based foaming agent. Is being converted into a drug.
  • hydrocarbon-based blowing agents are flammable. When such flammable blowing agents are used, they remain in the foam for a long time due to their low gas permeability. This increases the likelihood that the foam will ignite and burn if a fire source is nearby.
  • a method of storing the foam at a high temperature for a long period of time and lowering the concentration of the blowing agent inside the plastic foam to a safe concentration is generally used, but it is still several months or even longer. It is not very efficient because it requires the above storage period.
  • Patent Document 1 Patent No. 3431141
  • the present invention reduces the compression modulus of the foam due to perforation of the needle after foaming while maintaining the performance of replacing the combustible foaming gas with an inorganic gas such as air in a short period of time by performing perforation.
  • An object of the present invention is to provide a method for producing an oil-based resin foam which can be suppressed and can sufficiently recover the thickness.
  • the present inventors have found that the above problem can be solved by using a needle having a polygonal needle cross section when piercing in the thickness direction from the surface of the foam, and have accomplished the present invention. . That is, the present invention is as follows.
  • a method for producing an extruded resin-based resin foam which comprises a step of perforating a resin-based resin-extruded foam produced using a combustible gas as a foaming agent with a needle in the direction of its thickness.
  • the ridge line is a ridge that has a length in the length direction of the needle stem.
  • the interior angle of the apex of the ridge at the section perpendicular to the length direction of the needle stem is not less than 20 ° and not more than 120 °.
  • the method for producing an oil-based resin foam of the present invention has good volume recoverability by suppressing the distortion generated at the time of perforation even if the foam is perforated after foaming, and the foam is compressed.
  • a method for producing a resin foam which can obtain a good foam without lowering the elastic modulus and can replace the flammable foam gas remaining in the foam with an inorganic gas such as air in a short period of time. It is.
  • Examples of the olefin resin constituting the foam used in the production method of the present invention include polyethylene homopolymers such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene, polypropylene homopolymers, and the like. Examples thereof include polybutene homopolymer, ethylene-butyl acetate copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-butene-propylene copolymer, and ethylene-acrylic acid copolymer. These resins can be used alone or in combination as appropriate.
  • the combustible foaming gas in the present invention includes aliphatic hydrocarbons such as propane, n-butane, i-butane, n-pentane, i-pentane and hexane; and cycloaliphatic hydrocarbons such as cyclobutane and cyclopentane. And halogenated hydrocarbons such as 1-chloro-1,1-difluoroethane and chloroethane. Furthermore, a non-combustible foaming gas such as carbon dioxide, nitrogen, 1,1,1,2-tetrafluoroethane may be mixed with these combustible foaming gases. The density of the foam obtained can be arbitrarily controlled by adjusting the amount of the foaming agent.
  • a permeation modifier may be used! ⁇ .
  • permeation modifiers for example, fatty acid glycerides such as palmitic acid glyceride and stearic acid glyceride, fatty acid amides such as oleic acid amide and erlic acid amide, and alkyl fatty acid amides such as stearyl stearic acid amide. These gas permeation modifiers can be used alone or in combination as appropriate.
  • a generally used bubble nucleating agent may be used as necessary.
  • the cell nucleating agent include an inorganic substance such as talc, a chemical foaming agent that decomposes at the temperature of the extruder to generate a decomposition gas, or an acid that reacts at that temperature to generate carbon dioxide gas. And a mixture of alkalis.
  • the cell size of the foam obtained by using these cell nucleating agents can be controlled arbitrarily.
  • additives such as an antistatic agent, an antioxidant, an ultraviolet absorber, and a coloring agent can be added to the mixed resin.
  • the thickness of the foam of the present invention is preferably from 20 mm to 80 mm. Within this range, the effect of the perforation method of the present invention is remarkably obtained. If the foam is thicker than this, the contact area between the needle and the foam increases and the piercing resistance increases, so that the foam is compressed and damaged. However, by using the needle according to the method of the present invention, puncture resistance is reduced, and damage to the foam can be suppressed.
  • the configuration of the foam may be a single layer or a lamination by heat fusion or the like.
  • the density of the foam of the present invention is preferably 10-100 kgZm 3 , more preferably 20-70 kgZm 3 .
  • the density is 10- lOOkgZm 3, insulation, floating materials, it can be used as cushioning packaging material applications.
  • the closed cell ratio of the foam obtained by the present invention is preferably 80 to 100%, more preferably 90 to 100%, except for the portion of the pores formed by perforation.
  • the closed cell ratio is 80% or more, sufficient cushioning performance can be exhibited as a cushioning wrapping material, and the water absorption rate can be reduced because water hardly penetrates into the foam.
  • the cell size of the foam of the present invention is preferably from 0.3 mm to 3. Omm, more preferably from 0.5 mm to 2.5 mm.
  • the smaller the cell size is the more the radiation from the bubble film is suppressed, and the thermal insulation performance is improved even if it comes in contact with water. Water infiltration is suppressed, and a decrease in heat insulation performance can be prevented.
  • an extruder melt-kneads additives such as a resin, a foaming agent, a gas permeation modifier, and, if necessary, a cell nucleating agent, under pressure, and then performs an appropriate This involves extruding the foamable molten mixture, cooled to the foaming temperature, through a die attached to the extruder tip under atmospheric pressure to foam.
  • additives such as a resin, a foaming agent, a gas permeation modifier, and, if necessary, a cell nucleating agent
  • the perforation of the present invention may be performed after the temperature of the central part of the foam obtained as described above falls below the crystallization temperature of the added gas permeation modifier.
  • the gas barrier effect of the gas permeation modifier exerts a gas barrier effect, thereby preventing rapid escape of the foaming agent.
  • good volume recovery of the foam is possible.
  • the ridge line also refers to a ridge that is an exit angle extending in parallel with the needle length direction, and the inner angle of the ridge apex in a cross section perpendicular to the length direction of the needle trunk, that is, the body of the needle, is 20 ° or more. 120 ° or less. If the number of the ridge lines is less than 2, the force which deteriorates the durability of the needle or the resistance of the needle at the time of piercing increases.
  • the cross section perpendicular to the length direction of the needle has a shape close to a circle, so that when piercing, the periphery of the hole pierced by the needle is pushed out.
  • the number of the ridge lines is preferably four or more and six or less, and most preferably four. If the angle of the apex is less than 20 °, the thickness of the ridge portion becomes thin, and the needle has poor durability. If the angle exceeds 120 °, the cross-section becomes almost circular, so that the same drawbacks as in the case of perforating with a circular cross-section needle occur, and the compressive strain of the foam increases after perforation.
  • the ridge may be a curved surface. In this case, the angle formed by the tangent at the vertex is the angle of the vertex. Typical cross-sectional shapes of these needles are shown in Fig. 1 (a)-(e).
  • Perforation of the foam of the present invention is performed using a sword-shaped needle assembly having a large number of needles.
  • a sword-shaped needle assembly is one in which the needles are arranged so that multiple perforations in the foam can be made at one time.
  • a row of needles parallel to the width direction of the foam should have at least 8 needle forces, and a row of needles parallel to the extrusion direction of the foam should have at least 30 needle forces. Is preferred.
  • a row of needles parallel to the width direction of the foam also has at least 10 or more needle forces, and Z or the direction of extrusion of the foam.
  • each row of needles has a needle force of at least 60 needles, since the blur of the needle assembly in the pierced state is reduced. More preferably, a row of needles parallel to the extrusion direction of the foam has at least 90 or more needle forces.
  • the arrangement of the needles is, for example, a staggered grid or a square grid.
  • the needle assembly when the thickness of the foam is large, using a needle assembly in which needles are arranged vertically and horizontally, compared to a case where needles are provided on the roll surface, in addition to keeping the needle insertion angle constant and piercing the needles In this state, the needle assembly does not shake, and the shape of the hole formed is stable. Force!] In addition, since the perforation resistance is reduced, a strain suppressing effect can be obtained.
  • the length of the ridgeline of the needle is preferably not less than 1Z2 of the thickness of the foam to be pierced and not more than the length excluding the tip of the needle.
  • the length of the ridge is the length of the point where the ridge first occurs at the tip of the needle. If the length of the ridgeline of the needle is 1Z2 or more of the thickness of the foam, the effect of suppressing distortion at the time of perforation becomes sufficient.
  • the effect of the present invention can be more sufficiently obtained if the ridge extends over all portions except the tip of the needle.
  • the ridge line may have a length equal to or greater than the thickness of the foam.
  • the thickness of the needle refers to the diameter of the smallest circle capable of surrounding all the vertices in a cross section perpendicular to the length direction of the needle trunk, that is, the body of the needle.
  • a needle having a thickness of 0.8 mm or more and 5 mm or less is used.
  • the thickness of the needle is 0.8 mm or more, replacement of the combustible gas remaining in the foam with an inorganic gas such as air is performed promptly.
  • the thickness of the needle is 5 mm or less, the surface appearance of the foam after perforation becomes good, and at the same time, when it comes into contact with water, it is easy to suppress the intrusion of water into the hole.
  • it is not less than 1. Omm and not more than 4.
  • Omm more preferably not less than 1.5 mm and not more than 3. Omm.
  • All of the needles have a sharpened tip, and the pointed portion may have a circular cross section or the same shape as the stem. Titanium coating on needle surface Also, a surface treatment such as Teflon (registered trademark) coating may be performed.
  • the depth of the perforations in the thickness direction of the foam in the method of the present invention is preferably “the thickness of the foam is 5 mm” or more, that is, it completely penetrates or has a non-penetration allowance of 5 mm or less.
  • the depth of the perforations is “the thickness of the foam is 5 mm or more”
  • the residual combustible gas in the foam is promptly replaced with an inorganic gas such as air, and the gas from both surfaces of the foam is removed. Since the diffusion of gas proceeds uniformly, the distribution of residual stress in the foam due to gas dissipation is reduced, and deformation during foam processing can be suppressed.
  • the depth of the perforations is less than the thickness of the foam, that is, when the foam is non-penetrating, only the perforated surface is subjected to a heat treatment such as heating and melting, so that the non-penetrating surface has a good surface appearance and water absorption, Low permeability and foam.
  • the interval between the perforations on the foam surface of the present invention refers to the shortest distance between the centers of adjacent holes, preferably 5 mm or more, 20 mm or less, more preferably 10 mm or more, 15 mm or less.
  • the distance between the perforations is 5 mm or more, rapid escape of combustible foamed gas is easily suppressed, and the volume recovery of the foam is improved.
  • the interval between the perforations is 20 mm or less, the replacement of the residual flammable foaming agent in the foam with an inorganic gas such as air is performed quickly.
  • the interval between the perforations is 10 mm or more and 15 mm or less, the balance between the volume recovery property of the foam and the gas replacement promoting effect is excellent.
  • the foam after the perforation treatment has a temperature of 30 ° C or more and 50 ° C or less after the perforation treatment for 7 days or more. It is preferable to store for 30 days or less. If the temperature is 30 ° C or more, the replacement of the residual flammable gas with an inorganic gas such as air is promptly performed. When the temperature is 50 ° C or lower, the residual flammable gas can be prevented from being excessively released, so that the foam can be prevented from shrinking.
  • the resin foam After extrusion foaming, the resin foam is cut to a length of 1000 mm, and the dimension obtained by accurately measuring the thickness of the foam is T. Thereafter, the resin foam is perforated to remove the resin foam.
  • the thickness recovery rate (R) was calculated by the following equation, and based on the value, the thickness recovery was evaluated according to the following criteria.
  • the resin foam stored at 40 ° C in an environment shall be drawn out into a columnar shape in the thickness direction using a cork boiler with an inner diameter of 16 mm to make a test piece.
  • a cork boiler with an inner diameter of 16 mm to make a test piece.
  • a headspace bottle manufactured by GL Sciences
  • the bottle was naturally cooled to room temperature, and the gas in the bottle was separated and analyzed by gas chromatography (GC-14B, manufactured by Shimadzu Corporation).
  • the concentration of the residual blowing agent in the foam and the effect of promoting the replacement with the inorganic gas were evaluated according to the following criteria.
  • the residual flammable blowing agent concentration is less than the lower limit of the combustion range of the blowing agent
  • the residual flammable blowing agent concentration is equal to or higher than the lower limit of the flammable range of the flammable blowing agent.
  • the test piece was also cut at the center of the foam, and L (mm) straight lines were drawn on the cut surface along the extrusion, width, and thickness directions of the foam, and the number of air bubbles in contact with these straight lines was determined.
  • the cell size in the extrusion direction, width direction, and thickness direction was calculated by the following formula, and the average value in three directions was used as the cell size (grid line method).
  • a gas permeation modifier stearic acid monoglyceride
  • the barrel temperature of the extruder was adjusted to 190 ° C-210 ° C, and the foaming agent injection rocker attached to the extruder tip also foamed with 100% by weight of n-butane (lower limit of combustion range: 1.8 vol%) 7 parts by weight of the agent was injected into 100 parts by weight of this resin, and mixed with the molten resin composition to obtain a foamable molten mixture.
  • the temperature is increased from the orifice plate having an average thickness of about 3.4 mm and an opening shape of about 215 mm width to room temperature and large temperature.
  • the needle 2 in Table 1 (the cross-sectional shape of the stem is shown in Fig. 1 (b)) and the needle interval a in the needle row in the direction parallel to the extrusion direction c of the foam is 15.Omm as shown in Fig. 2. Therefore, the depth of the piercing is determined using a needle-shaped needle assembly (perforation interval: 15. Omm) arranged so that the needle spacing b in the row of needles parallel to the width direction d of the foam is 15. Omm.
  • a foam was obtained in the same manner as in Example 1, except that a perforation treatment was performed so as to be 59 mm. The same evaluation as in Example 1 was performed on the obtained foam. Table 2 shows the results.
  • Needle 3 in Table 1 (the cross-sectional shape of the stem is Fig. 1 (a)) is shown in Fig. 2.As shown in Fig. 2, the needle spacing a in the needle row parallel to the foam extrusion direction c is 10. The puncturing process was performed except that the needle spacing b in the needle row parallel to the width direction d was 20. Omm. A foam was obtained in the same manner as in Example 1. The same evaluation as in Example 1 was performed on the obtained foam. Table 2 shows the results.
  • Needle 4 in Table 1 (the cross-sectional shape of the trunk is (Fig. 1 (d))), as shown in Fig. 3, the needle spacing a in the needle row parallel to the extrusion direction c of the foam is 10.
  • Omm Perforation processing using a sword-shaped needle assembly (perforation interval: 10. Omm) arranged in a staggered grid so that the needle spacing b in the needle row parallel to the width direction d of the foam is 20.
  • Omm A foam was obtained in the same manner as in Example 1 except that the evaluation was carried out, and the obtained foam was evaluated in the same manner as in Example 1. The results are shown in Table 2.
  • a foam was obtained in the same manner as in Example 1 except that the piercing treatment was performed with the needle 5 shown in Table 1, and the same evaluation as in Example 1 was performed. Table 2 shows the results.
  • a foam was obtained in the same manner as in Example 2 except that the piercing treatment was performed with the needle 6 shown in Table 1, and the same evaluation as in Example 1 was performed. Table 2 shows the results.
  • a foam was prepared in the same manner as in Example 2 except that the perforation was performed with the needle 7 shown in Table 1. And the same evaluation as in Example 1 was performed. Table 2 shows the results.
  • a foam was obtained in the same manner as in Example 1 except that the perforation treatment was not performed, and the same evaluation as in Example 1 was performed. Table 2 shows the results.
  • the foam according to the present invention which can be easily replaced with air by a blowing agent gas remaining in the foam, is manufactured by a method for manufacturing an olefin resin foam, which is used for cushioning packaging materials for industrial products, housings, and the like.
  • Insulation material Core material for sports equipment such as beat boards and body boats, It is used as a floating material for boards and the like.
  • FIG. 1 is a view showing an example of a cross-sectional shape of a representative needle stem in the present invention, wherein (a) shows a cross-sectional shape of a needle stem used in Example 3, and (b) shows Examples 1 and 2.
  • the cross-sectional shape of the stem of the needle used in Example 2 shows an example of the cross-sectional shape of the needle used in Example 4, and (c) and (e) show examples of other cross-sectional shapes.
  • FIG. 2 is a needle arrangement diagram of a sword-like needle assembly in which needles are arranged in a square lattice used in an example of the present invention.
  • FIG. 3 is a needle arrangement diagram of a sword-shaped needle assembly tool in which needles are arranged in a houndstooth check pattern used in an example of the present invention.
  • A Needle spacing in a needle row in a direction parallel to the extrusion direction of the foam

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Forests & Forestry (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

A process for producing an olefinic resin foam, in which a drop of compressive elasticity modulus of foam by needle perforation conducted after foaming can be suppressed while maintaining the capability of speedy replacement of flammable foaming gas by an inorganic gas such as air and in which satisfactory thickness recovery can be ensured. There is provided a process for producing an olefinic resin extruded foam, comprising the step of perforating with needles an olefinic resin extruded foam produced with the use of a flammable gas as a foaming agent in the thickness direction from the surface thereof, wherein a needle assembly consisting of an assembly in frog-like form of needles each having 3 to 8 edge lines defined below on its trunk part is used as the needles: 1) edge lines composed of protruding-angle edges extending in the longitudinal direction of the needle trunk part, and 2) edge apexes on a cross section perpendicular to the longitudinal direction of the needle trunk part having an internal angle of 20° to 120°.

Description

明 細 書  Specification
ォレフィン系樹脂発泡体の製造方法  Method for producing olefin resin foam
技術分野  Technical field
[0001] 本発明は、発泡体内に残留する発泡剤ガスを容易に空気と置換させることのできる ォレフィン系榭脂発泡体の製造方法に関する。本発明の製造方法により製造される 発泡体は工業製品等の緩衝包装材、住宅等の断熱材ビート板やボディボート等のス ポーッ用具芯材、フロート等の浮き材などに使用される。  The present invention relates to a method for producing an oil-based resin foam capable of easily replacing a blowing agent gas remaining in a foam with air. The foam produced by the production method of the present invention is used as a cushioning packaging material for industrial products and the like, a heat insulation beat board for houses and the like, a sporting tool core material for body boats and the like, a floating material such as a float and the like.
背景技術  Background art
[0002] プラスチック発泡体を製造するにあたり、発泡剤が使用されるが、近年オゾン層破 壊や地球温暖化の見地から、その発泡剤がフロン系発泡剤から炭化水素(C3— C5 )系発泡剤に転換されつつある。炭化水素系の発泡剤は可燃性であることが知られ ており、この可燃性の発泡剤を使用した場合、そのガス透過性の低さから発泡体内 部に長期にわたり残留する。そのため火源が近くにある場合、発泡体が着火'燃焼す る可能性が高まる。この問題を解決する方法として、高温下で発泡体を長期間保存 し、プラスチック発泡体内部の発泡剤濃度を安全な濃度まで低下させる方法が一般 的にとられているが、それでも数ケ月あるいはそれ以上の保存期間を必要とするので あまり効率的ではない。  [0002] A foaming agent is used in producing a plastic foam. In recent years, from the viewpoint of destruction of the ozone layer and global warming, the foaming agent is changed from a CFC-based foaming agent to a hydrocarbon (C3-C5) -based foaming agent. Is being converted into a drug. It is known that hydrocarbon-based blowing agents are flammable. When such flammable blowing agents are used, they remain in the foam for a long time due to their low gas permeability. This increases the likelihood that the foam will ignite and burn if a fire source is nearby. As a method of solving this problem, a method of storing the foam at a high temperature for a long period of time and lowering the concentration of the blowing agent inside the plastic foam to a safe concentration is generally used, but it is still several months or even longer. It is not very efficient because it requires the above storage period.
[0003] 発泡体中に残存する可燃性発泡剤を空気等の不燃性の無機ガスで置換するため に要する時間を短縮する方法として、製造後の発泡体にその表面から針で穿孔する 方法 (特許文献 1)があり、穿孔用の針として剣山状の針集合具が用いられている。 し力しながら、特許文献 1の方法では、断面が円形の針を用いた場合、突刺した穴 を押し広げる様に穿孔が実施される。このため、針表面とフォーム表面との摩擦抵抗 が大きくなり、穿孔時に穴周辺が穿孔方向に引きずり込まれることで、圧縮歪が大きく なり、充分な体積回復が得られなくなるとともに、発泡体の圧縮弾性率をも低下させる という問題があった。  [0003] As a method of shortening the time required for replacing the combustible foaming agent remaining in the foam with a nonflammable inorganic gas such as air, a method of perforating the foam after manufacture with a needle from the surface thereof ( There is a patent document 1), and a sword-shaped needle assembly is used as a needle for perforation. However, in the method of Patent Document 1, when a needle having a circular cross section is used, perforation is performed so as to push open the pierced hole. As a result, the frictional resistance between the needle surface and the foam surface increases, and the perimeter of the hole is dragged in the perforating direction during perforation, thereby increasing the compressive strain, making it impossible to obtain a sufficient volume recovery and compressing the foam. There is a problem that the elastic modulus is also lowered.
特許文献 1 :特許第 3431141号公報  Patent Document 1: Patent No. 3431141
発明の開示 発明が解決しょうとする課題 Disclosure of the invention Problems the invention is trying to solve
[0004] 本発明は、穿孔を施すことで可燃性発泡ガスを短期間に空気等の無機ガスで置換 する性能を維持しつつ、発泡後の針の穿孔による発泡体の圧縮弾性率の低下を抑 えることができるとともに、かつ、充分に厚み回復が可能なォレフィン系榭脂発泡体の 製造方法を提供することを目的とする。  [0004] The present invention reduces the compression modulus of the foam due to perforation of the needle after foaming while maintaining the performance of replacing the combustible foaming gas with an inorganic gas such as air in a short period of time by performing perforation. An object of the present invention is to provide a method for producing an oil-based resin foam which can be suppressed and can sufficiently recover the thickness.
課題を解決するための手段  Means for solving the problem
[0005] 本発明者等は、発泡体の表面から厚み方向に穿孔する際、針断面が多角形である 針を用いることにより上記課題が解決されることを見出し、本発明をなすに至った。 すなわち、本発明は、下記の通りである。 The present inventors have found that the above problem can be solved by using a needle having a polygonal needle cross section when piercing in the thickness direction from the surface of the foam, and have accomplished the present invention. . That is, the present invention is as follows.
1.発泡剤として可燃性ガスを用いて製造されたォレフイン系榭脂押出発泡体に、そ の表面力 厚み方向に針によって穿孔を施す工程を含むォレフィン系榭脂押出発泡 体の製造方法において、  1. A method for producing an extruded resin-based resin foam, which comprises a step of perforating a resin-based resin-extruded foam produced using a combustible gas as a foaming agent with a needle in the direction of its thickness.
該針として、針幹部に下記に定義される稜線を 3本以上 8本以下有する針が剣山 状に集合してなる針集合具を用いる、ォレフィン系榭脂押出発泡体の製造方法: A method for producing an oil-refined extruded foam using a needle assembly in which needles having three or more and eight or less ridge lines defined below in a needle stem are gathered in a sword mountain shape as the needles:
1)稜線は針幹部の長さ方向に長さを有する出角である稜カ なる 1) The ridge line is a ridge that has a length in the length direction of the needle stem.
2)針幹部の長さ方向に垂直な断面における稜頂点の内角は 20° 以上 120° 以 下。  2) The interior angle of the apex of the ridge at the section perpendicular to the length direction of the needle stem is not less than 20 ° and not more than 120 °.
2.針の稜線の長さが、穿孔されるォレフイン系榭脂押出発泡体の厚みの 1Z2以上 である、請求項 1記載のォレフィン系榭脂押出発泡体の製造方法。  2. The process for producing an extruded resin-based resin foam according to claim 1, wherein the length of the ridge line of the needle is 1Z2 or more of the thickness of the extruded resin-based resin foam.
3.針幹部の長さ方向に垂直な断面において、全ての稜頂点を囲うことが可能な最小 の円の直径が、 0. 8mm以上 5mm以下である、請求項 1または 2に記載のォレフィン 系榭脂押出発泡体の製造方法。  3. The olefin system according to claim 1 or 2, wherein the diameter of the smallest circle capable of surrounding all the vertices in the cross section perpendicular to the length direction of the needle stem is 0.8 mm or more and 5 mm or less.方法 Manufacturing method of extruded fat.
4.ォレフィン系榭脂発泡体への穿孔の深さ力 「該発泡体の厚み 5mm」以上であ る、請求項 1に記載のォレフィン系榭脂押出発泡体の製造方法。  4. The method for producing an extruded olefin-based resin foam according to claim 1, wherein the depth force of perforation in the olefin-based resin foam is “the thickness of the foam is 5 mm” or more.
5.ォレフィン系榭脂発泡体の表面において、穿孔の間隔が 5mm以上 20mm以下 である、請求項 1記載のォレフィン系榭脂押出発泡体の製造方法。  5. The method for producing an extruded resin-based resin foam according to claim 1, wherein the interval between perforations on the surface of the resin-based resin foam is 5 mm or more and 20 mm or less.
6.発泡体の厚みが 20— 80mmである、請求項 1記載のォレフィン系榭脂押出発泡 体の製造方法。 7.針集合具が幅方向および長さ方向に針列を有し、幅方向の針列一列が 8本以上 の針力もなる、請求項 1に記載のォレフィン系榭脂押出発泡体の製造方法。 6. The method according to claim 1, wherein the foam has a thickness of 20 to 80 mm. 7. The method for producing an extruded resin-based resin foam according to claim 1, wherein the needle assembly has needle rows in the width direction and the length direction, and one row of the needle rows in the width direction also has a needle force of 8 or more. .
8.針集合具が幅方向および長さ方向に針列を有し、長さ方向の針列一列が 30本以 上の針力もなる、請求項 1に記載のォレフィン系榭脂押出発泡体の製造方法。  8. The olefin resin extruded foam according to claim 1, wherein the needle assembly has a row of needles in a width direction and a length direction, and each row of the lengthwise needle rows has a needle force of 30 or more. Production method.
発明の効果  The invention's effect
[0006] 本発明のォレフィン系榭脂発泡体の製造方法は、発泡後に発泡体への穿孔を施し ても穿孔時に発生する歪を抑制することで体積回復性が良好であり、発泡体の圧縮 弾性率を低下させることなく良好な発泡体を得られるとともに、発泡体中に残留した 可燃性発泡ガスを短期間で空気等の無機ガスで置換することができるォレフィン系 榭脂発泡体の製造方法である。  [0006] The method for producing an oil-based resin foam of the present invention has good volume recoverability by suppressing the distortion generated at the time of perforation even if the foam is perforated after foaming, and the foam is compressed. A method for producing a resin foam, which can obtain a good foam without lowering the elastic modulus and can replace the flammable foam gas remaining in the foam with an inorganic gas such as air in a short period of time. It is.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0007] 本発明について、特にその好ましい実施態様を中心に、以下具体的に説明する。 [0007] The present invention will be specifically described below, particularly focusing on its preferred embodiments.
まず、本発明で用いる発泡体について説明する。  First, the foam used in the present invention will be described.
本発明の製造方法において用いる発泡体を構成するォレフイン系榭脂としては、 高密度ポリエチレン、中密度ポリエチレン、低密度ポリエチレン、直鎖状低密度ポリエ チレン等のポリエチレン単独重合体、ポリプロピレン単独重合体、ポリブテン単独重 合体、エチレン 酢酸ビュル共重合体、エチレン プロピレン共重合体、エチレンーブ テン共重合体、エチレンーブテン プロピレン共重合体、エチレン アクリル酸共重合 体等が挙げられる。これらの榭脂は単独で用いるほか、適宜混合して用いることもで きる。  Examples of the olefin resin constituting the foam used in the production method of the present invention include polyethylene homopolymers such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene, polypropylene homopolymers, and the like. Examples thereof include polybutene homopolymer, ethylene-butyl acetate copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-butene-propylene copolymer, and ethylene-acrylic acid copolymer. These resins can be used alone or in combination as appropriate.
[0008] 本発明における可燃性発泡ガスとしては、プロパン、 n ブタン、 i ブタン、 n ペン タン、 i-ペンタン、へキサン等の脂肪族炭化水素、シクロブタン、シクロペンタン等の 環式脂肪族炭化水素、 1 クロロー 1, 1ージフルォロェタン、クロロェタン等のハロゲン 化炭化水素が挙げられる。さら〖こ、これら可燃性発泡ガスに炭酸ガス、窒素、 1, 1, 1 , 2—テトラフルォロェタン等の不燃性の発泡ガスを混合することも出来る。また、これ らの発泡剤の添加量を調節することで得られる発泡体の密度を任意に制御すること ができる。  [0008] The combustible foaming gas in the present invention includes aliphatic hydrocarbons such as propane, n-butane, i-butane, n-pentane, i-pentane and hexane; and cycloaliphatic hydrocarbons such as cyclobutane and cyclopentane. And halogenated hydrocarbons such as 1-chloro-1,1-difluoroethane and chloroethane. Furthermore, a non-combustible foaming gas such as carbon dioxide, nitrogen, 1,1,1,2-tetrafluoroethane may be mixed with these combustible foaming gases. The density of the foam obtained can be arbitrarily controlled by adjusting the amount of the foaming agent.
[0009] 前記の発泡体の製造には、透過調整剤を用いてもよ!ヽ。透過調整剤の例としては 、公知のガス透過調整剤、例えば、パルチミン酸グリセリド、ステアリン酸グリセリド等 の脂肪酸グリセリド、ォレイン酸アミド、エル力酸アミド等の脂肪酸アミド、ステアリルス テアリン酸アミド等のアルキル脂肪酸アミドが挙げられる。これらのガス透過調整剤は 単独で用いるほか、適宜混合して用いることができる。 [0009] In the production of the foam, a permeation modifier may be used!ヽ. Examples of permeation modifiers And known gas permeation modifiers, for example, fatty acid glycerides such as palmitic acid glyceride and stearic acid glyceride, fatty acid amides such as oleic acid amide and erlic acid amide, and alkyl fatty acid amides such as stearyl stearic acid amide. These gas permeation modifiers can be used alone or in combination as appropriate.
[0010] さらに、本発明の製造方法においては、必要に応じて一般に使用されている気泡 核形成剤を用いてもよい。この気泡核形成剤としては、例えば、タルクのような無機物 質、あるいは押出機の温度で分解して分解ガスを発生するような化学発泡剤、または その温度で反応して炭酸ガスを発生する酸とアルカリの混合物のようなものである。こ れらの気泡核形成剤を使用することで得られる発泡体のセルサイズの大きさを任意 に制御することができる。  [0010] Further, in the production method of the present invention, a generally used bubble nucleating agent may be used as necessary. Examples of the cell nucleating agent include an inorganic substance such as talc, a chemical foaming agent that decomposes at the temperature of the extruder to generate a decomposition gas, or an acid that reacts at that temperature to generate carbon dioxide gas. And a mixture of alkalis. The cell size of the foam obtained by using these cell nucleating agents can be controlled arbitrarily.
さらに、必要に応じて、混合樹脂に対し帯電防止剤、酸化防止剤、紫外線吸収剤、 着色剤等の添加剤も添加することもできる。  Further, if necessary, additives such as an antistatic agent, an antioxidant, an ultraviolet absorber, and a coloring agent can be added to the mixed resin.
[0011] 本発明の発泡体の厚みは 20mm— 80mmが好ましい。この範囲であると、本発明 の穿孔方法の効果が顕著に得られる。発泡体力この程度厚いものであると、針と発 泡体との接触面積が大きくなり穿孔抵抗が増すことにより、発泡体が圧縮され、ダメー ジを受ける。しかし、本発明の方法に係る針を用いることにより穿孔抵抗が減少し、発 泡体のダメージを抑制することが可能となる。発泡体の構成は,単層または熱融着等 による積層の 、ずれでも構わな 、。  [0011] The thickness of the foam of the present invention is preferably from 20 mm to 80 mm. Within this range, the effect of the perforation method of the present invention is remarkably obtained. If the foam is thicker than this, the contact area between the needle and the foam increases and the piercing resistance increases, so that the foam is compressed and damaged. However, by using the needle according to the method of the present invention, puncture resistance is reduced, and damage to the foam can be suppressed. The configuration of the foam may be a single layer or a lamination by heat fusion or the like.
本発明の発泡体の密度は、好ましくは 10— 100kgZm3、さらに好ましくは 20— 70 kgZm3である。密度が 10— lOOkgZm3であると、断熱材,浮き材、緩衝包装材料 用途として使用できる。 The density of the foam of the present invention is preferably 10-100 kgZm 3 , more preferably 20-70 kgZm 3 . When the density is 10- lOOkgZm 3, insulation, floating materials, it can be used as cushioning packaging material applications.
本発明で得られる発泡体の独立気泡率は、穿孔による孔の部分を除いて、好ましく は 80— 100%、より好ましくは 90— 100%である。独立気泡率が 80%以上であると、 緩衝包装材として充分な緩衝性能を発揮することができるとともに、発泡体内へ水が 浸入しにくいため吸水率を低くすることができる。  The closed cell ratio of the foam obtained by the present invention is preferably 80 to 100%, more preferably 90 to 100%, except for the portion of the pores formed by perforation. When the closed cell ratio is 80% or more, sufficient cushioning performance can be exhibited as a cushioning wrapping material, and the water absorption rate can be reduced because water hardly penetrates into the foam.
また、本発明の発泡体のセルサイズは、好ましくは 0. 3mm— 3. Omm、より好まし くは 0. 5mm— 2. 5mmである。断熱材用途においては、セルサイズは小さいほど気 泡膜からの輻射が抑制され断熱性能はよぐ水と接触した場合でもセル開口面への 水の浸入が抑えられ断熱性能の低下を防ぐことができ、好まし 、。 Further, the cell size of the foam of the present invention is preferably from 0.3 mm to 3. Omm, more preferably from 0.5 mm to 2.5 mm. In thermal insulation applications, the smaller the cell size is, the more the radiation from the bubble film is suppressed, and the thermal insulation performance is improved even if it comes in contact with water. Water infiltration is suppressed, and a decrease in heat insulation performance can be prevented.
[0012] 本発明の発泡体の製造方法は、押出機内で榭脂と発泡剤及びガス透過調整剤、 必要に応じて気泡核形成剤等の添加剤を加圧下で溶融混練した後、適正な発泡温 度まで冷却した発泡性溶融混合物を、押出機先端に取り付けたダイスを通して大気 圧下に押し出して発泡させることを含む。 [0012] In the method for producing a foam of the present invention, an extruder melt-kneads additives such as a resin, a foaming agent, a gas permeation modifier, and, if necessary, a cell nucleating agent, under pressure, and then performs an appropriate This involves extruding the foamable molten mixture, cooled to the foaming temperature, through a die attached to the extruder tip under atmospheric pressure to foam.
本発明の穿孔は、前記のようにして得られた発泡体の中心部温度が添加されてい るガス透過調整剤の結晶化温度以下に降下した後に行うとよい。発泡体中心部の温 度が添加されて ヽるガス透過調整剤の結晶化温度以下で穿孔を施すことで、ガス透 過調整剤のガスバリアー効果発現によって急激な発泡剤の逸散が抑止され、良好な 発泡体の体積回復が可能となる。  The perforation of the present invention may be performed after the temperature of the central part of the foam obtained as described above falls below the crystallization temperature of the added gas permeation modifier. By perforating at a temperature below the crystallization temperature of the gas permeation modifier to which the temperature at the center of the foam is added, the gas barrier effect of the gas permeation modifier exerts a gas barrier effect, thereby preventing rapid escape of the foaming agent. Thus, good volume recovery of the foam is possible.
[0013] 本発明の穿孔に用いる針としては、針幹部に 3本以上 8本以下の稜線を有する針 を用いる。ここで稜線とは、針長さ方向に平行に延びる出角である稜カもなり、針幹 部、すなわち針の胴体部での長さ方向に垂直な断面における稜頂点の内角が 20° 以上 120° 以下のものをいう。稜線が 2本以下であると、針の耐久性が劣る力、また は、穿孔時に針の抵抗が大きくなる。稜線が 9本以上の場合は、針の長さ方向と垂直 な断面が円形に近い形状となるため、穿孔する時に針が突刺した穴の周辺部を押し 広げるようになる。前記稜線の数は好ましくは 4本以上 6本以下であり、もっとも好まし いのは 4本である。該頂点の角度が 20° 未満の場合、稜の部分の肉厚が薄くなり、 針の耐久性が劣る。 120° 超過の場合はその断面が円形に近くなるため、断面円形 針で穿孔した場合と同じような欠点が生じ、穿孔後に発泡体の圧縮歪が大きくなる。 なお、稜部は曲面であってもよいが、この場合は当該頂点における接線の成す角を 頂点の角度とする。これら針の代表的な断面形状を図 1 (a)— (e)に示す。 [0013] As the needle used for the perforation of the present invention, a needle having three to eight ridge lines at the needle stem is used. Here, the ridge line also refers to a ridge that is an exit angle extending in parallel with the needle length direction, and the inner angle of the ridge apex in a cross section perpendicular to the length direction of the needle trunk, that is, the body of the needle, is 20 ° or more. 120 ° or less. If the number of the ridge lines is less than 2, the force which deteriorates the durability of the needle or the resistance of the needle at the time of piercing increases. When the number of ridges is nine or more, the cross section perpendicular to the length direction of the needle has a shape close to a circle, so that when piercing, the periphery of the hole pierced by the needle is pushed out. The number of the ridge lines is preferably four or more and six or less, and most preferably four. If the angle of the apex is less than 20 °, the thickness of the ridge portion becomes thin, and the needle has poor durability. If the angle exceeds 120 °, the cross-section becomes almost circular, so that the same drawbacks as in the case of perforating with a circular cross-section needle occur, and the compressive strain of the foam increases after perforation. The ridge may be a curved surface. In this case, the angle formed by the tangent at the vertex is the angle of the vertex. Typical cross-sectional shapes of these needles are shown in Fig. 1 (a)-(e).
[0014] 本発明の発泡体への穿孔は、多数の針を有する剣山状の針集合具を用いて実施 される。剣山状の針集合具とは、発泡体への多数の穿孔が 1回で実施できるように針 が配列されているものを指す。針集合具においては、発泡体の幅方向と平行な針列 一列が少なくとも 8本以上の針力 なり、発泡体の押出し方向と平行な針列一列が少 なくとも 30本以上の針力もなることが好ましい。さらに、発泡体の幅方向と平行な針列 一列が少なくとも 10本以上の針力もなり、および Zまたは、発泡体の押出し方向と平 行な針列一列が少なくとも 60本以上の針力もなると、突き刺した状態での針集合具 のブレがより少なくなる点から、より好ましい。さらに好ましくは、発泡体の押出し方向 と平行な針列一列は少なくとも 90本以上の針力 なる。針の配置は例えば、千鳥格 子状または正方格子状である。剣山状の針集合具を用いることで、発泡体への多数 の穿孔を一度に実施することができ、発泡体内からのガスの逸散が均一になるため、 ガス逸散に起因する発泡体の変形を抑制しやすくなる。また穿孔処理能力が高まる ので、相対的に穿孔速度を低下させることが可能となる上、針引き抜き時の発泡体表 面の毛羽立ちが無い表面外観が良好な発泡体が得られる。さらに、発泡体の厚みが 厚い場合、針が縦横に並んだ針集合具を用いると、ロール表面に針を設けた場合と くらべて、針の挿入角度を一定に保つことに加え、針を突き刺した状態での針集合具 のブレがなくなるため、形成される孔の形状が安定する。力!]えて、穿孔抵抗が減るこ とから歪抑制効果が得られる。 [0014] Perforation of the foam of the present invention is performed using a sword-shaped needle assembly having a large number of needles. A sword-shaped needle assembly is one in which the needles are arranged so that multiple perforations in the foam can be made at one time. For a needle assembly, a row of needles parallel to the width direction of the foam should have at least 8 needle forces, and a row of needles parallel to the extrusion direction of the foam should have at least 30 needle forces. Is preferred. In addition, a row of needles parallel to the width direction of the foam also has at least 10 or more needle forces, and Z or the direction of extrusion of the foam. It is more preferable that each row of needles has a needle force of at least 60 needles, since the blur of the needle assembly in the pierced state is reduced. More preferably, a row of needles parallel to the extrusion direction of the foam has at least 90 or more needle forces. The arrangement of the needles is, for example, a staggered grid or a square grid. By using a sword-shaped needle assembly, a large number of perforations can be made in the foam at one time, and the gas escapes from the foam uniformly. Deformation is easily suppressed. In addition, since the perforation processing ability is increased, the perforation speed can be relatively reduced, and a foam having a good surface appearance without fluffing of the foam surface at the time of needle withdrawal can be obtained. Furthermore, when the thickness of the foam is large, using a needle assembly in which needles are arranged vertically and horizontally, compared to a case where needles are provided on the roll surface, in addition to keeping the needle insertion angle constant and piercing the needles In this state, the needle assembly does not shake, and the shape of the hole formed is stable. Force!] In addition, since the perforation resistance is reduced, a strain suppressing effect can be obtained.
針の稜線の長さは穿孔される発泡体の厚みの 1Z2以上、針の先端部を除いた部 分の長さ以下が好ましい。稜線の長さは針の先端部において最初に稜が発生する 箇所力 針の後端部で稜が消失する箇所までの長さである。針の稜線の長さが発泡 体厚みの 1Z2以上であると穿孔時の歪抑制効果が充分となる。また、稜線が針の先 端部を除いた部分すべてにわたっていると本発明の効果はより充分に得られる。な お、稜線は発泡体の厚み以上の長さを有してもよい。  The length of the ridgeline of the needle is preferably not less than 1Z2 of the thickness of the foam to be pierced and not more than the length excluding the tip of the needle. The length of the ridge is the length of the point where the ridge first occurs at the tip of the needle. If the length of the ridgeline of the needle is 1Z2 or more of the thickness of the foam, the effect of suppressing distortion at the time of perforation becomes sufficient. The effect of the present invention can be more sufficiently obtained if the ridge extends over all portions except the tip of the needle. The ridge line may have a length equal to or greater than the thickness of the foam.
本発明において、針の太さとは、針の幹部すなわち、針の胴体部での長さ方向に 垂直な断面において、全ての稜頂点を囲うことが可能な最小の円の直径のことをいう 。本発明では針の太さが、 0. 8mm以上 5mm以下である針を用いる。針の太さが 0. 8mm以上であると、発泡体中の残留可燃性ガスと空気等の無機ガスとの置換が速 やかに行われる。また、針の太さが 5mm以下であると穿孔後の発泡体表面外観が良 好となると同時に、水と接触した場合に孔への水の浸入を抑制しやすくなる。好ましく は、 1. Omm以上 4. Omm以下であり、更に好ましくは 1. 5mm以上 3. Omm以下で ある。  In the present invention, the thickness of the needle refers to the diameter of the smallest circle capable of surrounding all the vertices in a cross section perpendicular to the length direction of the needle trunk, that is, the body of the needle. In the present invention, a needle having a thickness of 0.8 mm or more and 5 mm or less is used. When the thickness of the needle is 0.8 mm or more, replacement of the combustible gas remaining in the foam with an inorganic gas such as air is performed promptly. When the thickness of the needle is 5 mm or less, the surface appearance of the foam after perforation becomes good, and at the same time, when it comes into contact with water, it is easy to suppress the intrusion of water into the hole. Preferably, it is not less than 1. Omm and not more than 4. Omm, more preferably not less than 1.5 mm and not more than 3. Omm.
針は全て先端がとがった加工をされているものであり、そのとがった部位の断面形 状は円でも、幹部と同じ形状であっても構わない。針の表面には、チタンコーティング 、テフロン (登録商標)コーティング等の表面処理をしても構わな 、。 All of the needles have a sharpened tip, and the pointed portion may have a circular cross section or the same shape as the stem. Titanium coating on needle surface Also, a surface treatment such as Teflon (registered trademark) coating may be performed.
[0016] 本発明の方法における発泡体の厚み方向への穿孔の深さは、「該発泡体の厚み 5mm」以上、即ち、完全に貫通するか非貫通代が 5mm以下であることが好ましい。 穿孔の深さが「該発泡体の厚み 5mm」以上であると、発泡体中の残留可燃性ガス と空気等の無機ガスとの置換が速やかに行われるとともに、発泡体の両表面からのガ スの放散が均一に進行するため、ガス逸散に起因する発泡体内の残留応力分布が 小さくなり、発泡体加工時の変形を抑止できる。また穿孔の深さが該発泡体の厚み未 満、すなわち非貫通である場合は、穿孔面のみを加熱溶融等の熱処理に付すことで 非貫通面にぉ 、て表面外観が良好で吸水性、透水性の低!、発泡体が得られる。  The depth of the perforations in the thickness direction of the foam in the method of the present invention is preferably “the thickness of the foam is 5 mm” or more, that is, it completely penetrates or has a non-penetration allowance of 5 mm or less. When the depth of the perforations is “the thickness of the foam is 5 mm or more”, the residual combustible gas in the foam is promptly replaced with an inorganic gas such as air, and the gas from both surfaces of the foam is removed. Since the diffusion of gas proceeds uniformly, the distribution of residual stress in the foam due to gas dissipation is reduced, and deformation during foam processing can be suppressed. When the depth of the perforations is less than the thickness of the foam, that is, when the foam is non-penetrating, only the perforated surface is subjected to a heat treatment such as heating and melting, so that the non-penetrating surface has a good surface appearance and water absorption, Low permeability and foam.
[0017] 本発明の発泡体表面における穿孔の間隔とは、隣接する孔同士の孔の中心間距 離で最短のものを指し、好ましくは、 5mm以上、 20mm以下、さらに好ましくは、 10m m以上、 15mm以下である。穿孔の間隔が 5mm以上であると、急激な可燃性発泡ガ ス逸散が抑制しやすくなり、発泡体の体積回復が良好となる。また穿孔の間隔が 20 mm以下であると、発泡体中の残留可燃性発泡剤と空気等の無機ガスとの置換が速 やかに行われる。穿孔の間隔が 10mm以上、 15mm以下であると、発泡体の体積回 復性とガス置換促進効果のバランスに優れる。  [0017] The interval between the perforations on the foam surface of the present invention refers to the shortest distance between the centers of adjacent holes, preferably 5 mm or more, 20 mm or less, more preferably 10 mm or more, 15 mm or less. When the distance between the perforations is 5 mm or more, rapid escape of combustible foamed gas is easily suppressed, and the volume recovery of the foam is improved. If the interval between the perforations is 20 mm or less, the replacement of the residual flammable foaming agent in the foam with an inorganic gas such as air is performed quickly. When the interval between the perforations is 10 mm or more and 15 mm or less, the balance between the volume recovery property of the foam and the gas replacement promoting effect is excellent.
[0018] 穿孔処理後の発泡体は、残留可燃性ガスと空気等の無機ガスとの置換を促進させ るために、穿孔処理後に 30°C以上、 50°C以下の温度で 7日以上、 30日以下の期間 保存することが好ましい。 30°C以上であれば、残留可燃性ガスと空気等の無機ガス との置換が速やかに行われる。また、 50°C以下であると、残留可燃性ガスが過度に 抜けるのを防止できるので、発泡体が収縮するのを防ぐことができる。  [0018] In order to promote the replacement of the residual flammable gas with an inorganic gas such as air, the foam after the perforation treatment has a temperature of 30 ° C or more and 50 ° C or less after the perforation treatment for 7 days or more. It is preferable to store for 30 days or less. If the temperature is 30 ° C or more, the replacement of the residual flammable gas with an inorganic gas such as air is promptly performed. When the temperature is 50 ° C or lower, the residual flammable gas can be prevented from being excessively released, so that the foam can be prevented from shrinking.
実施例  Example
[0019] 以下、本発明を実施例に基づいて説明する力 本発明の内容をこれらの実施例に 限定するものではな 、。実施例に示された値は次の方法により測定したものである。 なお、実施例中、部及び%は特に断りのない限り、重量基準である。また、各種の評 価、測定は下記の方法に拠った。  Hereinafter, the ability to explain the present invention based on examples is not intended to limit the contents of the present invention to these examples. The values shown in the examples were measured by the following methods. In the examples, parts and% are by weight unless otherwise specified. Various evaluations and measurements were made according to the following methods.
(1) 5%圧縮強度  (1) 5% compressive strength
穿孔を施した発泡体を 40°Cの環境下で 2週間保存した後、 JIS Z0235に準拠し た圧縮試験方法を行!、、試験片元厚みに対して 5%の歪を生じた時の圧縮応力値を 5%圧縮強度 Sとし、同じ LOTで製造された発泡体で穿孔を施さない試験片の同条 件下での圧縮応力値 Sと比較し、以下の基準で評価した。 After storing the perforated foam at 40 ° C for 2 weeks, it conforms to JIS Z0235. , A compression test value of 5% with respect to the original thickness of the test piece and a compressive strength S of 5%, and a test in which a foam made of the same LOT is not perforated The specimen was compared with the compressive stress value S under the same conditions and evaluated according to the following criteria.
0  0
E (%) = (S -S) /S X 100  E (%) = (S -S) / S X 100
o o  o o
〇: E≤ 10 (穿孔による圧縮弾性率の低下が小さ!/、。 )  〇: E≤ 10 (Decrease in compression modulus due to perforation is small! / ,.)
X :E> 10 (穿孔による圧縮弾性率の低下が大きい。 )  X: E> 10 (Decrease in compression modulus due to perforation is large.)
(2)厚み回復性  (2) Thickness recovery
押出発泡後に榭脂発泡体の長さを 1000mmに切断し、当該発泡体の厚みを正確 に測定した寸法を Tとする。その後、該榭脂発泡体に穿孔を施し、該榭脂発泡体を  After extrusion foaming, the resin foam is cut to a length of 1000 mm, and the dimension obtained by accurately measuring the thickness of the foam is T. Thereafter, the resin foam is perforated to remove the resin foam.
0  0
発泡 1時間後から 2週間後まで 40°Cの環境下で保存した後、再び寸法を測定した厚 みを Tとする。厚み回復率 (R)を次式によって算出し、その値を基に厚み回復性を以 下の基準で評価した。  After 1 hour to 2 weeks after foaming, store at 40 ° C and then measure the thickness again. The thickness recovery rate (R) was calculated by the following equation, and based on the value, the thickness recovery was evaluated according to the following criteria.
R(%) =T/T X 100  R (%) = T / T X 100
0  0
〇:R≥95 (厚み回復性に優れ、製造時の厚み維持が容易)  〇: R≥95 (Excellent thickness recovery, easy to maintain thickness during manufacturing)
X :R< 95 (厚み回復性に乏しぐ製造時の厚み維持が困難)  X: R <95 (Thickness recovery is poor and it is difficult to maintain thickness during manufacturing)
[0020] (3)ガス置換促進効果 (3) Gas replacement promoting effect
穿孔処理後 2週間 40°Cの環境下で保存した榭脂発泡体を内径 16mmのコルクボ 一ラーを使用して厚み方向に円柱状に抜き出して試験片とする。この試験片の体積 と重量をすばやく測定後、直ちに、内容積を測定したヘッドスペースボトル (ジーエル サイエンス社製)に入れ密封し、 170°Cで 1. 5時間加熱溶融させる。その後、ボトル を室温まで自然冷却後、該ボトル内のガスを分取、ガスクロマトグラフ(島津製作所製 : GC-14B)にて分析した。予め既知のガス濃度測定より作成しておいた検量線と、 試験片の体積、試験片の榭脂部分容積、ボトル内容積を用いて発泡体中の残存発 泡剤濃度を n= 3の平均で算出した。発泡体内残存発泡剤濃度と無機ガスとの置換 促進効果は以下の基準で評価した。  Two weeks after the perforation process, the resin foam stored at 40 ° C in an environment shall be drawn out into a columnar shape in the thickness direction using a cork boiler with an inner diameter of 16 mm to make a test piece. Immediately after measuring the volume and weight of this test piece, immediately place it in a headspace bottle (manufactured by GL Sciences) whose internal volume has been measured, seal it, and heat and melt at 170 ° C for 1.5 hours. Thereafter, the bottle was naturally cooled to room temperature, and the gas in the bottle was separated and analyzed by gas chromatography (GC-14B, manufactured by Shimadzu Corporation). Using the calibration curve prepared in advance from the known gas concentration measurement, the volume of the test piece, the resin part volume of the test piece, and the volume in the bottle, average the residual foaming agent concentration in the foam as n = 3. Was calculated. The concentration of the residual blowing agent in the foam and the effect of promoting the replacement with the inorganic gas were evaluated according to the following criteria.
〇:残存可燃性発泡剤濃度が当該発泡剤の燃焼範囲下限未満  〇: The residual flammable blowing agent concentration is less than the lower limit of the combustion range of the blowing agent
X:残存可燃性発泡剤濃度が当該可燃性発泡剤の燃焼範囲下限以上  X: The residual flammable blowing agent concentration is equal to or higher than the lower limit of the flammable range of the flammable blowing agent.
[0021] (4)発泡体の独立気泡率 ASTM-D2856に記載されて 、るエアーピクノメーター法 (東京サイエンス (株)製 、空気比較式比重系 1000型使用)により測定し、 n= 5の平均で算出した。 (4) Closed cell rate of foam It was measured by the air pycnometer method described in ASTM-D2856 (manufactured by Tokyo Science Co., Ltd., using an air-comparison-type specific gravity system type 1000), and was calculated as an average of n = 5.
(5)発泡体のセルサイズ  (5) Cell size of foam
発泡体の中央部力も試験片をカットし、カット面に発泡体の押出方向、幅方向、厚 み方向に沿って L (mm)の直線を引き、これらの直線に接触している気泡の数を数え 、次式により押出方向、幅方向、厚み方向のセルサイズを算出し、更に 3方向の平均 値をセルサイズとした (グリッドライン法)。  The test piece was also cut at the center of the foam, and L (mm) straight lines were drawn on the cut surface along the extrusion, width, and thickness directions of the foam, and the number of air bubbles in contact with these straight lines was determined. The cell size in the extrusion direction, width direction, and thickness direction was calculated by the following formula, and the average value in three directions was used as the cell size (grid line method).
セルサイズ (mm) = 1. 626 X LZ気泡数  Cell size (mm) = 1.626 X LZ bubble count
[実施例 1]  [Example 1]
150mmのバレル内径を有するスクリュー型押出機の供給領域に、低密度ポリェチ レン (密度 0. 921gZcm3、 MI = 2. 9gZlO分)、およびこの榭脂 100重量部に対し 1. 0重量部の気泡調整剤(タルク)と 0. 5重量部のガス透過調整剤 (ステアリン酸モノ グリセリド)を 900kgZ時間の速度で、供給した。押出機のバレル温度を 190°C— 21 0°Cに調整し、押出機の先端に取り付けた発泡剤注入ロカも n—ブタン 100重量% ( 燃焼範囲下限値: 1. 8vol%)からなる発泡剤をこの榭脂 100重量部に対し 7重量部 を圧入し、当該溶融榭脂組成物と混合して発泡性溶融混合物とした。この発泡性溶 融混合物を押出機の出口に取り付けた冷却装置で 108°Cまで冷却した後、約 3. 4m mの平均厚みと約 215mm幅の開口部形状を有するオリフィスプレートより、常温、大 気圧下の雰囲気中に連続的に押し出して発泡させ、榭脂発泡体の引き取り速度を調 整しながら成形して、押出し発泡 1分後に厚み 62mm、幅 600mm、長さ 1000mm、 セルサイズ 1. lmm,密度 39kgZm3の板状榭脂発泡体を得た。 Low-density polyethylene (density 0.921gZcm3, MI = 2.9gZlO) and 1.0 parts by weight air bubble adjustment per 100 parts by weight of this resin in the supply area of a screw type extruder with a barrel inner diameter of 150mm (Talc) and 0.5 parts by weight of a gas permeation modifier (stearic acid monoglyceride) were supplied at a rate of 900 kgZ hours. The barrel temperature of the extruder was adjusted to 190 ° C-210 ° C, and the foaming agent injection rocker attached to the extruder tip also foamed with 100% by weight of n-butane (lower limit of combustion range: 1.8 vol%) 7 parts by weight of the agent was injected into 100 parts by weight of this resin, and mixed with the molten resin composition to obtain a foamable molten mixture. After cooling the foamable molten mixture to 108 ° C with a cooling device attached to the outlet of the extruder, the temperature is increased from the orifice plate having an average thickness of about 3.4 mm and an opening shape of about 215 mm width to room temperature and large temperature. It is extruded and foamed continuously in an atmosphere under atmospheric pressure, molded while adjusting the take-off speed of the resin foam, and after 1 minute of extrusion foaming, thickness 62 mm, width 600 mm, length 1000 mm, cell size 1.lmm Thus, a plate-like resin foam having a density of 39 kgZm 3 was obtained.
この発泡体の中心部温度が 50°Cまで降下した直後に、表 1に記載の針 1 (断面形 状は(図 1 (b) )を、図 2に示すような、発泡体の押出方向 cに平行な針列における針 間隔 aが 15. Omm、発泡体の幅方向 dに平行な針列における針間隔 bが 15. Ommと なるように配列した剣山状の針集合具 (穿孔の間隔: 15. Omm)を用いて、該榭脂発 泡体の上面から、貫通穿孔処理をした。この榭脂発泡体を穿孔処理後 2週間、 40°C の環境下で保存した後、圧縮弾性率の指標である 5%圧縮強度、独立気泡率、厚み 回復性及びガス置換促進効果の評価を行った。その結果を表 2に示す。 [0023] [実施例 2] Immediately after the temperature of the center of the foam has dropped to 50 ° C, the needle 1 shown in Table 1 (the cross-sectional shape is (Fig. 1 (b)) is pushed in the extrusion direction of the foam as shown in Fig. 2. Needle spacing a in needle rows parallel to c is 15.Omm, needle spacing b in needle rows parallel to the foam width direction d is 15.Omm. : 15. Omm), and perforated from the upper surface of the resin foam.After storing the resin foam in a 40 ° C environment for 2 weeks after the perforation, the compression elasticity The evaluation of 5% compressive strength, closed cell ratio, thickness recovery, and gas replacement promoting effect, which are indicators of the ratio, is shown in Table 2. [Example 2]
表 1に記載の針 2 (幹部の断面形状は図 1 (b) )を、図 2に示すように、発泡体の押 出方向 cに平行な方向の針列における針間隔 aが 15. Omm,発泡体の幅方向 dに平 行な針列における針間隔 bが 15. Ommとなるように配列した剣山状の針集合具 (穿 孔の間隔: 15. Omm)を用いて穿孔深さが 59mmとなるように穿孔処理を実施した他 は、実施例 1と同様の方法で発泡体を得た。得られた発泡体について実施例 1と同 様の評価を行った。結果を表 2に示す。  As shown in Fig. 2, the needle 2 in Table 1 (the cross-sectional shape of the stem is shown in Fig. 1 (b)) and the needle interval a in the needle row in the direction parallel to the extrusion direction c of the foam is 15.Omm as shown in Fig. 2. Therefore, the depth of the piercing is determined using a needle-shaped needle assembly (perforation interval: 15. Omm) arranged so that the needle spacing b in the row of needles parallel to the width direction d of the foam is 15. Omm. A foam was obtained in the same manner as in Example 1, except that a perforation treatment was performed so as to be 59 mm. The same evaluation as in Example 1 was performed on the obtained foam. Table 2 shows the results.
[0024] [実施例 3] [Example 3]
表 1に記載の針 3 (幹部の断面形状は図 1 (a) )を、図 2に示すように、発泡体の押出 方向 cに平行な針列における針間隔 aが 10. Omm,発泡体の幅方向 dに平行な針列 における針間隔 bが 20. Ommとなるように配列した剣山状の針集合具 (穿孔の間隔: 10. Omm)を用いて穿孔処理を実施した他は、実施例 1と同様の方法で発泡体を得 た。得られた発泡体について実施例 1と同様の評価を行った。結果を表 2に示す。  Needle 3 in Table 1 (the cross-sectional shape of the stem is Fig. 1 (a)) is shown in Fig. 2.As shown in Fig. 2, the needle spacing a in the needle row parallel to the foam extrusion direction c is 10. The puncturing process was performed except that the needle spacing b in the needle row parallel to the width direction d was 20. Omm. A foam was obtained in the same manner as in Example 1. The same evaluation as in Example 1 was performed on the obtained foam. Table 2 shows the results.
[0025] [実施例 4] [Example 4]
表 1に記載の針 4 (幹部の断面形状は(図 1 (d) )を、図 3に示すように、発泡体の押 出方向 cに平行な針列における針間隔 aが 10. Omm,発泡体の幅方向 dに平行な針 列における針間隔 bが 20. Ommとなるように千鳥格子状に配列した剣山状の針集合 具 (穿孔の間隔: 10. Omm)を用いて穿孔処理を実施した他は、実施例 1と同様の方 法で発泡体を得た。得られた発泡体について実施例 1と同様の評価を行った。結果 を表 2に示す。  Needle 4 in Table 1 (the cross-sectional shape of the trunk is (Fig. 1 (d))), as shown in Fig. 3, the needle spacing a in the needle row parallel to the extrusion direction c of the foam is 10. Omm, Perforation processing using a sword-shaped needle assembly (perforation interval: 10. Omm) arranged in a staggered grid so that the needle spacing b in the needle row parallel to the width direction d of the foam is 20. Omm A foam was obtained in the same manner as in Example 1 except that the evaluation was carried out, and the obtained foam was evaluated in the same manner as in Example 1. The results are shown in Table 2.
[0026] [比較例 1] [Comparative Example 1]
表 1に記載の針 5により穿孔処理を実施した他は、実施例 1と同様の方法で発泡体 を得て、実施例 1と同様の評価を行った。結果を表 2に示す。  A foam was obtained in the same manner as in Example 1 except that the piercing treatment was performed with the needle 5 shown in Table 1, and the same evaluation as in Example 1 was performed. Table 2 shows the results.
[比較例 2]  [Comparative Example 2]
表 1に記載の針 6により穿孔処理を実施した他は、実施例 2と同様の方法で発泡体 を得て、実施例 1と同様の評価を行った。結果を表 2に示す。  A foam was obtained in the same manner as in Example 2 except that the piercing treatment was performed with the needle 6 shown in Table 1, and the same evaluation as in Example 1 was performed. Table 2 shows the results.
[比較例 3]  [Comparative Example 3]
表 1に記載の針 7により穿孔処理を実施した他は、実施例 2と同様の方法で発泡体 を得て、実施例 1と同様の評価を行った。結果を表 2に示す。 A foam was prepared in the same manner as in Example 2 except that the perforation was performed with the needle 7 shown in Table 1. And the same evaluation as in Example 1 was performed. Table 2 shows the results.
[比較例 4]  [Comparative Example 4]
穿孔処理を実施しない他は、実施例 1と同様の方法で発泡体を得て、実施例 1と同 様の評価を行った。結果を表 2に示す。  A foam was obtained in the same manner as in Example 1 except that the perforation treatment was not performed, and the same evaluation as in Example 1 was performed. Table 2 shows the results.
[表 1] [table 1]
Figure imgf000014_0001
Figure imgf000014_0001
Figure imgf000015_0001
産業上の利用可能性
Figure imgf000015_0001
Industrial applicability
本発明に係る、発泡体内に残留する発泡剤ガスを容易に空気と置換させることので きるォレフィン系樹脂発泡体の製造方法により製造される発泡体は、工業製品等の 緩衝包装材、住宅等の断熱材ビート板やボディボート等のスポーツ用具芯材、フロ ート等の浮き材などに使用される。 図面の簡単な説明 The foam according to the present invention, which can be easily replaced with air by a blowing agent gas remaining in the foam, is manufactured by a method for manufacturing an olefin resin foam, which is used for cushioning packaging materials for industrial products, housings, and the like. Insulation material Core material for sports equipment such as beat boards and body boats, It is used as a floating material for boards and the like. Brief Description of Drawings
[0030] [図 1]本発明における代表的な針幹部の断面形状例を示す図であり、(a)は実施例 3 で用いた針の幹部の断面形状、(b)は実施例 1および 2で用いた針の幹部の断面形 状、(d)は実施例 4で用いた針の幹部の断面形状、(c)、(e)はその他の断面形状の 例を示す。  FIG. 1 is a view showing an example of a cross-sectional shape of a representative needle stem in the present invention, wherein (a) shows a cross-sectional shape of a needle stem used in Example 3, and (b) shows Examples 1 and 2. The cross-sectional shape of the stem of the needle used in Example 2, (d) shows an example of the cross-sectional shape of the needle used in Example 4, and (c) and (e) show examples of other cross-sectional shapes.
[図 2]本発明実施例で使用した正方格子状に針を配列した剣山状の針集合具の針 配列図である。  FIG. 2 is a needle arrangement diagram of a sword-like needle assembly in which needles are arranged in a square lattice used in an example of the present invention.
[図 3]本発明実施例で使用した千鳥格子状に針を配列した剣山状の針集合具の針 配列図である。  FIG. 3 is a needle arrangement diagram of a sword-shaped needle assembly tool in which needles are arranged in a houndstooth check pattern used in an example of the present invention.
符号の説明  Explanation of symbols
[0031] a:発泡体の押出方向に平行な方向の針列における針間隔  A: Needle spacing in a needle row in a direction parallel to the extrusion direction of the foam
b:発泡体の幅方向に平行な針列における針間隔  b: Needle spacing in a needle row parallel to the foam width direction
c :発泡体の押出し方向  c: Foam extrusion direction
d :発泡体の幅方向  d: Foam width direction

Claims

請求の範囲 The scope of the claims
[1] 発泡剤として可燃性ガスを用いて製造されたォレフイン系榭脂押出発泡体に、その 表面力 厚み方向に針によって穿孔を施す工程を含むォレフィン系榭脂押出発泡 体の製造方法において、  [1] A method for producing an extruded resin-based resin foam, which includes a step of perforating a resin-based resin-extruded foam produced using a combustible gas as a foaming agent with a needle in the surface direction in a thickness direction,
該針として、針幹部に下記に定義される稜線を 3本以上 8本以下有する針が剣山 状に集合してなる針集合具を用いる、ォレフィン系榭脂押出発泡体の製造方法: A method for producing an oil-refined extruded foam using a needle assembly in which needles having three or more and eight or less ridge lines defined below in a needle stem are gathered in a sword mountain shape as the needles:
1)稜線は針幹部の長さ方向に平行に延びる出角である稜カ なる 1) The ridge line is a ridge that has an exit angle that extends parallel to the length of the needle stem.
2)針幹部の長さ方向に垂直な断面における稜頂点の内角は 20° 以上 120° 以 下。  2) The interior angle of the apex of the ridge at the section perpendicular to the length direction of the needle stem is not less than 20 ° and not more than 120 °.
[2] 針の稜線の長さが、穿孔されるォレフイン系榭脂押出発泡体の厚みの 1Z2以上で ある、請求項 1記載のォレフィン系榭脂押出発泡体の製造方法。  [2] The process for producing an extruded resin-based resin foam according to claim 1, wherein the length of the ridgeline of the needle is 1Z2 or more of the thickness of the extruded resin-based resin extruded foam.
[3] 針幹部の長さ方向に垂直な断面において、全ての稜頂点を囲うことが可能な最小 の円の直径が、 0. 8mm以上 5mm以下である、請求項 1または 2に記載のォレフィン 系榭脂押出し発泡体の製造方法。 [3] The Orefin according to claim 1 or 2, wherein in a cross section perpendicular to the length direction of the needle stem, the diameter of the smallest circle capable of surrounding all the vertices is 0.8 mm or more and 5 mm or less. A method for producing a resin-based extruded foam.
[4] ォレフィン系榭脂押出発泡体への穿孔の深さが、「該発泡体の厚み 5mm」以上 である、請求項 1に記載のォレフィン系榭脂押出発泡体の製造方法。 [4] The process for producing an extruded olefin-based resin foam according to claim 1, wherein the depth of perforations in the olefin-based resin-extruded foam is not less than “the thickness of the foam is 5 mm”.
[5] ォレフィン系榭脂押出発泡体の表面において、穿孔の間隔が 5mm以上 20mm以 下である、請求項 1記載のォレフィン系榭脂押出発泡体の製造方法。 [5] The method for producing an extruded olefin resin foam according to claim 1, wherein the interval between perforations is 5 mm or more and 20 mm or less on the surface of the extruded olefin resin foam.
[6] 発泡体の厚みが 20— 80mmである、請求項 1記載のォレフィン系榭脂押出発泡体 の製造方法。 [6] The method for producing an olefin resin extruded foam according to claim 1, wherein the foam has a thickness of 20 to 80 mm.
[7] 針集合具が幅方向および長さ方向に針列を有し、幅方向の針列一列が 8本以上の 針力もなる、請求項 1に記載のォレフィン系榭脂押出発泡体の製造方法。  [7] The production of the resin-based expanded foam according to claim 1, wherein the needle assembly has a row of needles in the width direction and the length direction, and one row of the row of needles in the width direction also has a needle force of 8 or more. Method.
[8] 針集合具が幅方向および長さ方向に針列を有し、長さ方向の針列一列が 30本以 上の針力もなる、請求項 1に記載のォレフィン系榭脂押出発泡体の製造方法。  [8] The olefin-based resin-extruded foam according to claim 1, wherein the needle assembly has needle rows in the width direction and the length direction, and one row of the needle rows in the length direction has a needle force of 30 needles or more. Manufacturing method.
PCT/JP2004/015681 2003-10-23 2004-10-22 Process for producing olefinic resin foam WO2005039863A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS456782Y1 (en) * 1966-05-20 1970-04-03
JPH06507129A (en) * 1991-04-30 1994-08-11 ザ ダウ ケミカル カンパニー Perforated plastic foam and its manufacturing method
JPH06256556A (en) * 1992-12-15 1994-09-13 Scriptoria Nv Foam polyolefin board and its preparation
JPH09193251A (en) * 1996-01-19 1997-07-29 Sekisui Chem Co Ltd Foam and its production
EP1026194A2 (en) * 1999-01-28 2000-08-09 Sealed Air Corporation Partially perforated foam

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS456782Y1 (en) * 1966-05-20 1970-04-03
JPH06507129A (en) * 1991-04-30 1994-08-11 ザ ダウ ケミカル カンパニー Perforated plastic foam and its manufacturing method
JPH06256556A (en) * 1992-12-15 1994-09-13 Scriptoria Nv Foam polyolefin board and its preparation
JPH09193251A (en) * 1996-01-19 1997-07-29 Sekisui Chem Co Ltd Foam and its production
EP1026194A2 (en) * 1999-01-28 2000-08-09 Sealed Air Corporation Partially perforated foam

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