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WO2005039863A1 - Procédé de production de mousse à base de résine oléfinique - Google Patents

Procédé de production de mousse à base de résine oléfinique 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
English (en)
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/ja
Publication of WO2005039863A1 publication Critical patent/WO2005039863A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B26—HAND CUTTING TOOLS; CUTTING; SEVERING
    • B26F—PERFORATING; PUNCHING; CUTTING-OUT; STAMPING-OUT; SEVERING BY MEANS OTHER THAN CUTTING
    • B26F1/00—Perforating; Punching; Cutting-out; Stamping-out; Apparatus therefor
    • B26F1/26—Perforating by non-mechanical means, e.g. by fluid jet
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/56—After-treatment of articles, e.g. for altering the shape
    • B29C44/5627—After-treatment of articles, e.g. for altering the shape by mechanical deformation, e.g. crushing, embossing, stretching
    • B29C44/5663—After-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

Landscapes

  • 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

L'invention concerne un procédé de production d'une mousse à base de résine oléfinique, dans lequel une chute du module d'élasticité de compression de mousse par perforation à l'aiguille conduite après moussage peut être supprimée tout en maintenant la capacité de remplacement rapide de gaz de moussage inflammable par un gaz inorganique tel que l'air et dans lequel une récupération d'épaisseur satisfaisante peut être assurée. L'invention concerne un procédé de production d'une mousse extrudée à base de résine oléfinique, comprenant l'étape consistant à perforer, à l'aide d'aiguilles, une mousse extrudée à base de résine oléfinique produite à l'aide d'un gaz inflammable en tant qu'agent de moussage dans le sens de l'épaisseur à partir de sa surface, un ensemble aiguille constitué d'un assemblage d'aiguilles en une forme de type fourchettes présentant chacune entre 3 et 8 lignes d'arête définies sous sa partie de tronc étant utilisé en tant qu'aiguilles. L'ensemble aiguille présente 1)des lignes d'arête constituées de bords à angles saillants s'étendant dans le sens longitudinal de la partie tronc d'aiguille, ainsi que 2) des sommets d'arête présents sur une section transversale perpendiculaire au sens longitudinal de la partie tronc d'aiguille présentant un angle intérieur compris entre 20° et 120°.
PCT/JP2004/015681 2003-10-23 2004-10-22 Procédé de production de mousse à base de résine oléfinique WO2005039863A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2005514974A JPWO2005039863A1 (ja) 2003-10-23 2004-10-22 オレフィン系樹脂発泡体の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003363697 2003-10-23
JP2003-363697 2003-10-23

Publications (1)

Publication Number Publication Date
WO2005039863A1 true WO2005039863A1 (fr) 2005-05-06

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Application Number Title Priority Date Filing Date
PCT/JP2004/015681 WO2005039863A1 (fr) 2003-10-23 2004-10-22 Procédé de production de mousse à base de résine oléfinique

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Country Link
JP (1) JPWO2005039863A1 (fr)
WO (1) WO2005039863A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS456782Y1 (fr) * 1966-05-20 1970-04-03
JPH06507129A (ja) * 1991-04-30 1994-08-11 ザ　ダウ　ケミカル　カンパニー 穴あきプラスチック発泡体およびその製造法
JPH06256556A (ja) * 1992-12-15 1994-09-13 Scriptoria Nv 発泡ポリオレフィン板及びその製造方法
JPH09193251A (ja) * 1996-01-19 1997-07-29 Sekisui Chem Co Ltd 発泡体およびその製造方法
EP1026194A2 (fr) * 1999-01-28 2000-08-09 Sealed Air Corporation Mousse partiellement perforée

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS456782Y1 (fr) * 1966-05-20 1970-04-03
JPH06507129A (ja) * 1991-04-30 1994-08-11 ザ　ダウ　ケミカル　カンパニー 穴あきプラスチック発泡体およびその製造法
JPH06256556A (ja) * 1992-12-15 1994-09-13 Scriptoria Nv 発泡ポリオレフィン板及びその製造方法
JPH09193251A (ja) * 1996-01-19 1997-07-29 Sekisui Chem Co Ltd 発泡体およびその製造方法
EP1026194A2 (fr) * 1999-01-28 2000-08-09 Sealed Air Corporation Mousse partiellement perforée

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