CN104910408B - Foaming polystyrene series resin particle and its manufacturing method, polystyrene resin pre-expanded particles - Google Patents

Foaming polystyrene series resin particle and its manufacturing method, polystyrene resin pre-expanded particles Download PDF

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Publication number
CN104910408B
CN104910408B CN201510310212.4A CN201510310212A CN104910408B CN 104910408 B CN104910408 B CN 104910408B CN 201510310212 A CN201510310212 A CN 201510310212A CN 104910408 B CN104910408 B CN 104910408B
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foaming
polystyrene
resin
resin particle
particle
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CN104910408A (en
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远藤翔太
樽本裕之
地海良辅
佐藤和人
平井贤治
山下昌利
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Sekisui Kasei Co Ltd
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Sekisui Plastics Co Ltd
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Priority claimed from JP2010072319A external-priority patent/JP5603628B2/en
Priority claimed from JP2010072320A external-priority patent/JP5603629B2/en
Priority claimed from JP2010072321A external-priority patent/JP5704831B2/en
Application filed by Sekisui Plastics Co Ltd filed Critical Sekisui Plastics Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/02—Making preforms by dividing preformed material, e.g. sheets, rods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B29B7/826—Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
    • 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
    • B29C44/3461—Making or treating expandable particles
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/05—Filamentary, e.g. strands
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
    • 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
    • B29C2793/00—Shaping techniques involving a cutting or machining operation
    • B29C2793/009—Shaping techniques involving a cutting or machining operation after shaping
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/345—Extrusion nozzles comprising two or more adjacently arranged ports, for simultaneously extruding multiple strands, e.g. for pelletising
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2025/00—Use of polymers of vinyl-aromatic compounds or derivatives thereof as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2025/00—Use of polymers of vinyl-aromatic compounds or derivatives thereof as moulding material
    • B29K2025/04—Polymers of styrene
    • B29K2025/06—PS, i.e. polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The present invention provides foaming polystyrene series resin particle and its manufacturing method, polystyrene resin pre-expanded particles.The foaming polystyrene series resin particle be by polystyrene resin and foaming agent in resin feedway melting mixing, and the polystyrene resin containing foaming agent melted is squeezed out as the aperture of mold, resin particle obtained from cooling and cut-out, wherein, the whiteness of the foaming polystyrene series resin particle measured with integrating sphere type color difference meter is 75 or less.

Description

Foaming polystyrene series resin particle and its manufacturing method, polystyrene resin Pre-expanded particles
The application be the applying date be on March 24th, 2011, application No. is 201180026028.7, entitled " foaming Property polystyrene resin particle and its manufacturing method, polystyrene resin pre-expanded particles, polystyrene resin foaming The division Shen of the application of formed body, thermoplastic resin pre-expanded particles and its manufacturing method and foaming of thermoplastic resin formed body " Please.
Technical field
Even the present invention relates to one kind high-foaming multiples, and the machines such as bending strength, compressive strength, impact resistance also can be obtained The foaming polystyrene series resin particle of the polystyrene resin expanded moldings of tool excellent strength.
Moreover, it relates to it is a kind of for manufacture the foaming of thermoplastic resin such as polystyrene resin expanded moldings at The thermoplastic resin pre-expanded particles and its manufacturing method of type body are more specifically related to following technology：Contain what will be melted The thermoplastic resin of foaming agent cut off immediately after being squeezed out from the aperture of mold into the cooling medium such as water manufacture resin particle, During manufacturing foaminess thermoplastic resin particle by so-called extrusion by melting, make the resin particle cut off in cooling It foams in medium, the thermoplastic resin pre-expanded particles with direct manufacture for manufacturing expanded moldings.
Moreover, it relates to the polystyrene resin expanded moldings of excellent strength can be obtained and foaming agent from Loss in foaminess resin particle is stable and can the long foamable polystyrene of storage time (bead service life, beads life) It is resin particle.
The application adheres to Japanese Patent Application 2010-72319 based on March 26th, 2010 in Japanese publication, in March, 2010 26 days Japanese publication Japanese Patent Application 2010-72320 and on March 26th, 2010 Japanese publication Japanese Patent Application 2010- Its content is incorporated herein No. 72321 priority.
Background technology
By polystyrene resin expanded moldings obtained from foaming polystyrene series resin particle foaming Resistance against compression, light weight, thermal insulation, economy etc. are excellent, are widely used as heat-barrier material, packaging material etc..In recent years, poly- The field of phenylethylene resin series expanded moldings is strongly required that the high-foaming of expanded moldings can be coped with resin demand is few It multiplies, even the task of top priority is to develop the high-foaming multiple also polystyrene resin foaming with high intensity Body.
One of manufacturing method as foaming polystyrene series resin particle, it is known to so-called extrusion by melting, that is, Foaming agent is pressed into the polystyrene resin melted in extruder and is kneaded, by the molten resin containing foaming agent It is directly extruded from the aperture for the mold for being attached to extruder front end into cooling liquid, by extrudate height while squeezing out Fast rotating knife cut-out, and extrudate is cooled and solidified by the contact with liquid, to obtain foamable polystyrene It is resin particle.
In the past, about the method for manufacturing foaming polystyrene series resin particle by extrusion by melting, such as, it is proposed that Technology disclosed in patent document 1,2.
The manufacturing method of foaminess thermoplastic resin particle with the following process is disclosed in patent document 1.
Thermoplastic resin (A) and foaming agent (B) are subjected to melting mixing (process 1), by obtained melting mixing object from mould The extrusion cavities of head are vertical after being expressed into the heating pressurized fluid being forced under the temperature, pressure that melting mixing object does not foam (process 2) is cut off, obtained particle is cooled to the temperature (process 3) not foamed under normal pressure, with differential thermal analysis device (DSC) when measuring foaminess thermoplastic resin, by the peak temperature of the low temperature side in two endothermic peaks that 40~120 DEG C of region occurs In the case that degree is set as T1, maturation process (work is carried out in the liquid for being heated to 30~(T1+15) DEG C of the normal pressure of temperature range Sequence 4).
The side with the following process that foaminess particle is manufactured by phenylethylene resin series recovery article is disclosed in patent document 2 Method.
(a) recovery article of phenylethylene resin series is crushed, makes the batch of pulverized product, (b) determines in each batch resin The content of contained butadiene, (c) single batch with original state or will the different batch of butadiene content each other mix or New phenylethylene resin series are added wherein, the butadiene content in entirety is adjusted to 1~6 mass %, will (d) regulate Resin pulverized product, which is put into, to be attached in the extruder that effective aperture is 1.1mm metal meshes below, (e) by powder in extruder The melting of broken product removes foreign matter by metal mesh, and is pressed into foaming agent in fusant, and by fusant from being attached to extruder The aperture of the metal cover of front end squeezes out, and (f) cuts off fusant while squeezing out and is quenched, controls foaming, producing foamed Particle.
In addition, in the past about the method for manufacturing foaming polystyrene series resin particle by extrusion by melting, for example, carrying The technology disclosed in patent document 3,4 is gone out.
A kind of manufacturing method of the pre-expanded particles of thermoplastic resin is disclosed in patent document 3, which is characterized in that use and squeeze Go out machine to melt thermoplastic resin, and mixed foaming agent, be then cooled off and squeeze out, and foamed so that its diameter at It it is 1.5~10.5 times of the nozzle diameter of extrusion die, alternatively, will complete before the foaming that foaming obtains is completed or after the completion of foaming Extrusion foaming body cut-out and pre-expanded particles are made.
A kind of phenylethylene resin series foaminess particle is disclosed in patent document 4, is by resin combination and volatilization Property foaming agent mixture while squeeze out into liquid foaminess particle obtained from cut-out, the resin combination include 70 100 mass parts of hybrid resin and benzene second of the olefin-based resin of the phenylethylene resin series of~90 mass % and 10~30 mass % 0~15 mass parts of alkene based elastomers, the expansion ratio of the phenylethylene resin series foaminess particle are 1.5 times hereinafter, and waving The content of volatile organic compounds other than hair property foaming agent is 500ppm or less.And benzene second is disclosed in patent document 4 The manufacturing method of the based resin foamed property particle of alkene, that is, by the phenylethylene resin series of 70~90 mass % and 10~30 mass % 100 mass parts of hybrid resin and 0~15 mass parts of styrene series elastomer of olefin-based resin are supplied to extruder and it are made to add Heat fusing and resin combination is made, by extruder be pressed on the way relative to 100 mass parts resin combinations be 3~15 matter After the volatile foaming agent for measuring part, the molten resin containing foaming agent is squeezed out from porous mold into liquid, on one side by resin Foaming inhibit at 1.5 times hereinafter, on one side squeeze out while resin is cut off in a liquid, to obtain volatile foaming agent with The content of outer volatile organic compounds is 500ppm foaminess particles below.
In addition, in the past about the method for manufacturing foaming polystyrene series resin particle by extrusion by melting, for example, carrying The technology disclosed in patent document 5,6 is gone out.
A kind of manufacturing method of phenylethylene resin series foaminess particle is disclosed in patent document 5, that is, by polystyrene tree Fat is put into extruder and melts, and foaming agent is pressed into the resin melted, by the molten resin containing foaming agent directly extrude to In cooling liquid, squeeze out while by resin cut off and form foaminess particle, in the method, select using boiling point for 20~60 DEG C of relatively high hydrocarbon is as foaming agent, by molten resin more than 160 DEG C of low temperature below and 20 megapascal (MPa)s It is squeezed out from extruder under high pressure, 60 DEG C of temperature below being set as with liquid under normal pressure will be cooled down.
A kind of autofrettage of foaminess thermoplastic resin particle is disclosed in patent document 6, that is, by thermoplastics such as polystyrene Property foaming agents such as resin and butane and be that 1.5 talcums below mass part etc. are inorganic relative to 100 mass parts thermoplastic resins Matter powder melts are kneaded, and then squeeze out it into pressurized fluid from the extrusion cavities of die head, are cooled down after cutting off immediately.
In addition, color (especially whiteness) for polystyrene resin particle and be original with polystyrene resin particle The relationship of the mechanical strength of expanded moldings obtained from material, for example, as it is known that there is the prior art disclosed Patent Document 7.
A kind of polystyrene resin particle is disclosed in patent document 7, is the benzene second by making to be used as seed grain Alkene based polymer particle is suspended in aqueous medium and addition styrenic monomers are gathered while so that it is swollen wherein Close so-called seeded polymerization and manufacture, in the polystyrene resin for manufacturing foaming polystyrene series resin particle It is 40~60 with the whiteness that integrating sphere type color difference meter measures in particle.It should be noted that the polystyrene of the patent document 7 It is that resin particle is manufactured by seeded polymerization, with the foaming polystyrene series resin manufactured by extrusion by melting Particle is compared, and preparation method, the whiteness of resin particle are entirely different.
Existing technical literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 7-314438 bulletins
Patent document 2:Japanese Unexamined Patent Publication 2003-213030 bulletins
Patent document 3:Japanese Unexamined Patent Publication 7-11041 bulletins
Patent document 4:Japanese Unexamined Patent Publication 2004-244529 bulletins
Patent document 5:Japanese Unexamined Patent Publication 2004-115690 bulletins
Patent document 6:Japanese Unexamined Patent Publication 6-298983 bulletins
Patent document 7:Japanese Unexamined Patent Publication 11-60783 bulletins
Invention content
Problems to be solved by the invention
However, there are the following problems for the above-mentioned prior art.
The manufacturing method of patent document 1 is the method for obtaining the big pre-expanded particles of cell diameter.However, prefoam When cell diameter in the bubble structure of particle increases, it can make by pre-expanded particles send out obtained from foaming in mold Steep the strength reduction of formed body.In addition, thermal conductivity is got higher and deterioration of thermal insulation performance.
Described in the manufacturing method of patent document 2, when obtained foaminess particle is carried out prefoam, what is obtained is pre- Expanded beads have the bubble structure that small and number of bubbles is more in outer section bubble, big in internal central gas bubble and number of bubbles is few, It is excellent that the pre-expanded particles are subjected to the surface smoothness of expanded moldings, amalgamation obtained from foaming in mold.However, by In the bubble of the inside center of the pre-expanded particles obtained by the prior art, big and number of bubbles is few, therefore, carries out in mold The intensity of expanded moldings obtained from foaming is low.Even it is also poly- with high intensity that its result can not provide high-foaming multiple Phenylethylene resin series expanded moldings.
In addition, in the manufacturing method of the pre-expanded particles of patent document 3, it will be so that its diameter becomes the spray of extrusion die Foaming body obtained from 1.5~10.5 times of mode of outspoken diameter is foamed is cut off, and obtains pre-expanded particles.Thus, due to The foaming body of column (being cylindric when nozzle form is circle) is cut off, therefore, obtained pre-expanded particles be not it is spherical and It is column.Such column pre-expanded particles are filled than spherical particle difficulty, when being filled in the die cavity of molding die, it is difficult to fully It fills, gap is easy tod produce between particle.Accordingly, it is possible to foaming obtains in mold expanded moldings can be made to generate recess and Degraded appearance or mechanical strength reduce.
The manufacturing method of patent document 4 manufactures expanded moldings via following each process：(1) by extrusion by melting The process for obtaining foaminess resin particle；(2) heating of obtained foaminess resin particle is then obtained into pre-expanded particles Process；(3) then, obtained pre-expanded particles are filled in the die cavity of molding die, are heated, foaming in mold And the process for obtaining expanded moldings.Therefore, the low production efficiency of expanded moldings, and need foaminess resin particle, pre- The storage space of expanded beads.
For the manufacturing method of the foaming polystyrene series resin particle of patent document 5, passing through melting extrusion During legal system makes foaminess resin particle, molten resin is squeezed out into the cooling liquid of normal pressure.Therefore, it is impossible to inhibit Bubble in obtained foaming polystyrene series resin particle occurs, and bulk density is lower, and transfer efficiency reduces.In addition, also There are problems that resin particle is caused to rupture or be easy disintegration because producing foaming.
The expanded moldings of whiteness is high when in turn, for using foaming foaming polystyrene series resin particle manufacture and Speech, sometimes mechanical strength reduction.
In addition, when foaming for the high foaming polystyrene series resin particle of whiteness, due to the loss of foaming agent Soon, thus can storage time (hereinafter referred to as bead service life) it is short.Therefore, it is difficult to take care of for a long time.
For the manufacturing method of patent document 6, due to mainly using butane as foaming agent, foaming agent Loss is fast and the bead service life shortens, and can not take care of for a long time sometimes.
In addition, in the manufacturing method of patent document 6, mainly use butane as foaming agent, as recorded in embodiment 70~90 DEG C of pressurization coolant-temperature gage, manufacture under conditions of heating pressurization water pressure 10~15kg/cm2.In such a situa-tion When manufacturing foaming polystyrene series resin particle, due to carrying out being cut to completely after squeezing out molten resin into pressure (hydraulic) water Foaming is generated during solidification, therefore, can speculate to obtain bulk density less than 0.58g/cm3The high foamable polystyrene of whiteness It is resin particle.Thus, for the foaming polystyrene series resin particle of the patent document 6, it may be said that exist because of production It given birth to foaming and the bulk density of resin particle is caused to be lower, needed in keeping, transport due to the volume of certain mass increases Extra space, the machinery because producing the expanded moldings for causing resin particle to rupture or be easy disintegration and manufacture due to foaming The problems such as strength reduction.
It should be noted that the patent document 7 for manufacturing polystyrene resin particle by seeded polymerization, for this It is unrelated with the above problem of foaming polystyrene series resin particle is manufactured by extrusion by melting outside the object of invention.
Present invention is made in view of the above circumstances, even it is intended that high-foaming times can be manufactured by providing one kind Number also has foaming polystyrene series resin particle and its manufacturer of the polystyrene resin expanded moldings of high intensity Method.
It is foamed into addition, can directly be manufactured by extrusion by melting the object of the present invention is to provide one kind for manufacturing The pre-expanded particles of type body, and excellent, excellent strength the expanded moldings of the fillibility in molding die die cavity can be obtained The manufacturing method of thermoplastic resin pre-expanded particles.
In addition, the object of the present invention is to provide a kind of polystyrene resin foamings that excellent strength can be obtained Body and foaming agent stable, bead long lifespan the foaming polystyrene series resin particle from the loss in foaminess resin particle.
The solution to the problem
To achieve the goals above, the first invention of the invention provides a kind of bubbles foaming polystyrene series resin Grain, is the bubbles foaming polystyrene series resin for including foaming agent and bubble in polystyrene resin particle Grain, wherein by the section by resin particle center of bubbles foaming polystyrene series resin particle, remove particle surface It plays the number of bubbles in the presence of the section other than 200 μm and is set as n/mm2, bulk density be set as ρ g/cm3When, with formula (1)
N=n ÷ (1/ ρ) (1)
Calculated N values are 400 or more.
In the bubbles foaming polystyrene series resin particle, above-mentioned N values are preferably in the range of 400~2000.
In the bubbles foaming polystyrene series resin particle, bulk density is preferably 0.4g/cm3More than.
In addition, the second invention of the present invention provides a kind of manufacturer of bubbles foaming polystyrene series resin particle Method is to add foaming agent and hair kernel foaming agent into polystyrene resin in resin feedway and be kneaded, will be contained The molten resin of foaming agent is squeezed out from the aperture for the mold for being attached to resin feedway front end into cooling liquid, is being squeezed Extrudate is cut off while going out, and so that extrudate is cooled and solidified by making contact of the extrudate with liquid, to obtain The method of foaming polystyrene series resin particle, wherein make foaming polystyrene series resin particle in cooling and solidifying before Fretting map in particle, to obtain following bubbles foaming polystyrene series resin particle：By cuing open by resin particle center Number of bubbles in the presence of face, section in addition to particle surface plays 200 μm is set as n/mm2, bulk density is set as to ρ g/ cm3When, with formula (1)
N=n ÷ (1/ ρ) (1)
Calculated N values are 400 or more.
In the manufacturing method of the bubbles foaming polystyrene series resin particle, above-mentioned N values are preferably in 400~2000 In the range of.
In the manufacturing method of the bubbles foaming polystyrene series resin particle, bulk density is preferably 0.4g/cm3With On.
In the manufacturing method of the bubbles foaming polystyrene series resin particle, as above-mentioned hair kernel foaming agent, using making Masterbatch type obtained from inorganic powder or chemical foaming agent are dispersed in base resin sends out kernel foaming agent.
In addition, the present invention provides a kind of polystyrene resin pre-expanded particles, it is by above-mentioned the first invention or second Obtained from the bubbles foaming polystyrene series resin particle of invention is heated.
In addition, the present invention provides a kind of polystyrene resin expanded moldings, it is that the polystyrene resin is pre- Expanded beads are filled in the die cavity of molding die and heat to carry out in mold obtained from foaming.
In addition, the present invention provides a kind of polystyrene resin expanded moldings, it is by above-mentioned the first invention or second The bubbles foaming polystyrene series resin particle of invention is filled in the die cavity of molding die and heats to carry out mold Obtained from interior foaming.
In addition, the third invention of the present invention provides a kind of manufacturing method of thermoplastic resin pre-expanded particles, wherein will be hot Plastic resin and foaming agent carry out melting mixing in resin feedway, and the thermoplastic resin containing foaming agent melted is led to Cross mold aperture squeeze out into cooling medium after cut off immediately, and it is made to foam in cooling medium and volume foaming times is made Above-mentioned expanded beads are then detached from above-mentioned cooling medium, are obtained by the thermoplastic resin pre-expanded particles of 1.6 times of number or more To thermoplastic resin pre-expanded particles.
In the manufacturing method of the thermoplastic resin pre-expanded particles, the volume of above-mentioned thermoplastic resin pre-expanded particles foams Multiple is preferably in the range of 1.6~50 times.
In the manufacturing method of the thermoplastic resin pre-expanded particles, the above-mentioned thermoplastic resin containing foaming agent preferably comprises phase For the foaming agent that 100 mass parts thermoplastic resins are 1~10 mass parts.
In the manufacturing method of the thermoplastic resin pre-expanded particles, foaming agent is preferably one kind in isopentane and pentane Or two kinds of mixture.
In the manufacturing method of the thermoplastic resin pre-expanded particles, above-mentioned thermoplastic resin is preferably polystyrene tree Fat.
In addition, the present invention provides a kind of thermoplastic resin pre-expanded particles, it is the thermoplasticity invented by above-mentioned third Obtained from the manufacturing method of resin pre-expanded particles.
In addition, the present invention provides a kind of manufacturing method of foaming of thermoplastic resin formed body, wherein the thermoplasticity will be passed through The thermoplastic resin pre-expanded particles that the manufacturing method of resin pre-expanded particles obtains are filled in the die cavity of molding die and add Thus heat obtains foaming of thermoplastic resin formed body to carry out foaming in mold.
In addition, the present invention provides a kind of foaming of thermoplastic resin formed body, it is to be molded by the foaming of thermoplastic resin Obtained from the manufacturing method of body.
In addition, the 4th invention of the present invention provides a kind of foaming polystyrene series resin particle, it is by polystyrene It is resin and the foaming agent melting mixing in resin feedway, and the polystyrene resin containing foaming agent melted is led to Cross foaming polystyrene series resin particle obtained from aperture extrusion, cooling and the cut-out of mold, wherein use integrating sphere type color The whiteness for the foaming polystyrene series resin particle that poor instrument is measured is 75 or less.
In the foaming polystyrene series resin particle, preferably comprises and be relative to 100 mass parts polystyrene resins The powdered inorganic material of 1.0 amounts below mass part has as hair kernel foaming agent, the powdered inorganic material to polystyrene The refractive index of resin is ± 0.08 refractive index below.
In the foaming polystyrene series resin particle, the bulk density of resin particle is preferably 0.58g/cm3More than.
In the foaming polystyrene series resin particle, resin particle is preferably comprised relative to 100 mass parts polystyrene It is that the foaming agent that resin is 2~15 mass parts forms.
In the foaming polystyrene series resin particle, foaming agent is preferably one or both of isopentane and pentane Mixture.
In addition, the 5th invention of the present invention provides a kind of manufacturing method of foaming polystyrene series resin particle, it is By polystyrene resin and foaming agent in resin feedway melting mixing, and the polyphenyl second containing foaming agent that will have been melted Alkene system resin, which is squeezed out into cooling medium by the aperture of mold and cooled down and cut off, obtains foaming polystyrene series The manufacturing method of resin particle, wherein polystyrene serial resin extruded to the cooling pressurizeed containing foaming agent by what is melted It in medium, and is cooled down and is cut off, to obtain with the whiteness that integrating sphere type color difference meter is measured being 75 foaminess below Polystyrene resin particle.
In the manufacturing method of the foaming polystyrene series resin particle, relative to 100 mass parts polystyrene resins, It is preferred that the powdered inorganic material of 1.0 amounts below mass part of addition, as hair kernel foaming agent, the powdered inorganic material has to poly- The refractive index of phenylethylene resin series is ± 0.08 refractive index below.
In the manufacturing method of the foaming polystyrene series resin particle, it is preferably 0.58g/cm to obtain bulk density3With On foaming polystyrene series resin particle.
In the manufacturing method of the foaming polystyrene series resin particle, relative to 100 mass parts polystyrene resins, Preferably comprise 2~15 mass parts foaming agents.
In the manufacturing method of the foaming polystyrene series resin particle, foaming agent is preferably in isopentane and pentane One or two kinds of mixtures.
In addition, the present invention provides a kind of polystyrene resin pre-expanded particles, it is to make above-mentioned 4th invention or the 5th Obtained from the foaming polystyrene series resin particle foamable of invention.
In addition, the present invention provides a kind of polystyrene resin expanded moldings, it is that the polystyrene resin is pre- Expanded beads are filled in the die cavity of molding die and heat, carry out in mold obtained from foaming.
The effect of invention
The bubbles foaming polystyrene series resin particle of the first invention or the second invention for the present invention, even Beautiful appearance and the expanded moldings with excellent amalgamation, mechanical strength also can be obtained in high magnification.
In addition, since foaminess resin particle is foamed, it can be directly by bubbles foaming polystyrene series tree Fat it is particles filled in the die cavity of molding die carry out mold in foaming and obtain expanded moldings.As a result, can reduce The manufacturing process of expanded moldings can reduce cost.Moreover, it can be expected that reducing carrying capacity of environment due to can reduce energy consumption.
For the manufacturing method of the thermoplastic resin pre-expanded particles of the third invention of the present invention, by thermoplastic resin and hair Infusion carries out melting mixing in resin feedway, the aperture that the thermoplastic resin containing foaming agent melted is passed through mold It is cut off immediately after squeezing out into cooling medium, and it is made to foam in cooling medium and 1.6 times of volume coefficient of foaming is made or more Thermoplastic resin pre-expanded particles, the thermoplasticity for manufacturing expanded moldings thus can be directly manufactured by extrusion by melting Resin pre-expanded particles.Therefore, with previous manufacture foaminess resin particle and be heated and obtain the side of pre-expanded particles Method is compared, and expanded moldings can be manufactured with less process, and the production efficiency of expanded moldings improves.In addition, hair can be reduced The storage space of bubble property resin particle.
Moreover, the thermoplastic resin pre-expanded particles obtained by this method are spherical or substantially spherical, therefore, and it is made Columnar pre-expanded particles are compared, and the fillibility into the die cavity of molding die is good, can seamlessly be filled in die cavity.Separately Outside, it can be merged well between expanded beads when foaming in mold, being foamed into for excellent strength can be obtained Type body.
For the foaming polystyrene series resin particle of the 4th invention of the present invention, the bubble in resin particle is few, uses The whiteness that integrating sphere type color difference meter measures is shown as 75 or less.Therefore, gather with the foaminess obtained by extrusion by melting in the past Phenylethylene resin series particle is compared, and bulk density is high, and compared with the high previous product of whiteness, the volume of certain mass tails off.Its As a result, can subtract less granular storage space, the transport of particle also becomes easy.
In addition, the bubble in the resin particle of the foaming polystyrene series resin particle is few, excellent strength, it is not easy to produce Raw rupture or disintegration.
In addition, according to the foaming polystyrene series resin particle, when heating and carrying out prefoam, can equably send out Bubble, this makes it possible to obtain grain size, the uniform pre-expanded particles of bulk density.Therefore, which foam in mold The excellent strength of expanded moldings obtained from molding.
In addition, for the foaming polystyrene series resin particle, since the loss of foaming agent is slow, the bead service life Extend, can take care of for a long time.
In the manufacturing method of the foaming polystyrene series resin particle of the 5th invention of the present invention, passing through melting extrusion During legal system makes foaming polystyrene series resin particle, it will melt containing the polystyrene serial resin extruded of foaming agent It into the cooling medium to have pressurizeed, and is cooled down and is cut off, to obtain being with the whiteness that integrating sphere type color difference meter is measured 75 foaming polystyrene series resin particles below.Therefore, compared with previous product as described above, can high efficiency manufacture have The foaming polystyrene series resin particle of excellent effect.
In addition, for the foaming polystyrene series resin particle of the 4th invention of the present invention or the 5th invention is heated simultaneously Make polystyrene resin pre-expanded particles obtained from its prefoam, due to can equably foam in prefoam, can Obtain the uniform pre-expanded particles of grain size, bulk density.Therefore, which is subjected to foaming in mold and obtained Expanded moldings excellent strength.
Description of the drawings
Fig. 1 is to indicate manufacture used in the manufacturing method of the bubbles foaming polystyrene series resin particle of the present invention The figure of an example of device.
Specific implementation mode
In the following, with reference to the accompanying drawings, embodiments of the present invention will be described.
First embodiment
The bubbles foaming polystyrene series resin particle of present embodiment is characterized in that, polystyrene resin Include foaming agent and bubble in grain, by the cuing open by resin particle center of the bubbles foaming polystyrene series resin particle Number of bubbles in the presence of face, section in addition to particle surface plays 200 μm is set as n/mm2, bulk density be set as ρ g/cm3 When, with formula (1)
N=n ÷ (1/ ρ) (1)
Calculated N values are 400 or more.
For the bubbles foaming polystyrene series resin particle of present embodiment, due to being calculated with above-mentioned formula (1) The N values gone out are 400 or more, therefore, compared with common foaming polystyrene series resin particle, become to exist inside particle and be permitted The particle internal structure of more micro air bubbles.
It should be noted that so-called " bubble " in present specification and claims refers to, it is micro- with scanning electron It is present in 5 μm of diameter inside resin particle when the section of the amplifying observations bubbles foaming polystyrene series resin particle such as mirror Above bubble.
For the bubbles foaming polystyrene series resin particle of present embodiment, due to having with above-mentioned formula (1) Therefore the structure that calculated N values are 400 or more is foamed by what bubbles foaming polystyrene series resin particle obtained The bubble of type body causes dense and uniform.As a result, even high magnification also can be obtained beautiful appearance and with excellent amalgamation, machine The expanded moldings of tool excellent strength.
In addition, since foaminess resin particle is foamed, it can be directly by bubbles foaming polystyrene series tree Fat it is particles filled in the die cavity of molding die carry out mold in foaming and obtain expanded moldings.As a result, can reduce The manufacturing process of expanded moldings can reduce cost, moreover, it can be expected that reducing carrying capacity of environment due to can reduce energy consumption.
When above-mentioned N values are less than 400, the performance of obtained expanded moldings and previous foaming polystyrene series resin Particle does not have marked difference.Thus, even cannot fully obtain high magnification also can be obtained beautiful appearance and with excellent Amalgamation, mechanical strength expanded moldings effect.In addition, the upper limit to above-mentioned N values is not set especially, but if N values are too big, it is likely that can be difficult to the bubble for the expanded moldings for manufacturing foaming polystyrene series resin particle, and obtaining Wall is thinning, dies down.It is therefore preferable that the upper limit of N values is set as 2000 or so.Thus, above-mentioned N values are preferably in 400~2000 model Enclose interior, more preferably 500~1600 ranges.
In the bubbles foaming polystyrene series resin particle of present embodiment, bulk density is preferably 0.4g/cm3With Upper, more preferably 0.5g/cm3More than.
It should be noted that in present embodiment, the bulk density of bubbles foaming polystyrene series resin particle is With JIS K6911：The value measured on the basis of nineteen ninety-five " thermosetting plastics ordinary test method ".
The assay method of the bulk density of bubbles foaming polystyrene series resin particle is as described below.
Bubbles foaming polystyrene series resin particle is filled in graduated cylinder to 500cm3Scale.Wherein, from level Graduated cylinder is estimated in direction, as long as there is a bubbles foaming polystyrene series resin particle to reach 500cm3Scale, just terminate Filling.Then, the bubbles foaming polystyrene series resin being filled in graduated cylinder is weighed with 2 effective digitals after decimal point The quality of grain, W (g) is set as by its quality.Then, it is calculate by the following formula out bubbles foaming polystyrene series resin particle Bulk density.
Bulk density (g/cm3)=W/500
In the bubbles foaming polystyrene series resin particle of present embodiment, as polystyrene resin, do not have Especially limitation, for example, styrene, α-methylstyrene, vinyltoluene, chlorostyrene, ethyl styrene, isopropyl can be enumerated The homopolymer of the styrenic monomers such as base styrene, dimethyl styrene, bromstyrol or the copolymer of these monomers etc..Its In, the polystyrene resin of the 50 above styrene of mass % is preferably comprised, wherein more preferable polystyrene.
Can be with above-mentioned styrene monomer above-mentioned benzene as main component in addition, as above-mentioned polystyrene resin The copolymer of vinyl monomer and the vinyl monomer that can be copolymerized with the styrenic monomers.As above-mentioned vinyl monomer, example Such as, it can enumerate：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid ten Six Arrcostabs etc. (methyl) alkyl acrylate；(methyl) acrylonitrile, dimethyl maleate, dimethyl fumarate, fumaric acid two Ethyl ester, ethyl fumarate, in addition there are two functional monomers such as divinylbenzene, aklylene glycol dimethylacrylate etc..
In addition, as long as polystyrene resin is main component, then other resins can also be added.Tree as addition Fat can enumerate for example, in order to improve the impact resistance of expanded moldings and be added to polybutadiene, styrene butadiene copolymers The rubber modified polystyrene system tree of the diene series rubbers shaped polymers such as object, ethylene-propylene-non-conjugated diene three-dimensional copolymer Fat, so-called high impact polystyrene.Or polyethylene-based resin, polypropylene-based resin, acrylic acid (ester) system tree can be enumerated Fat, acrylonitritrile-styrene resin, acrylonitrile-butadiene-styrene copolymer etc..
As the polystyrene resin as raw material, commercially available common polystyrene resin can be used, with suspension Polystyrene resin (the non-polyphenyl second processed again of the non-renewable raw material such as the polystyrene resin that the methods of polymerization is remake Alkene, virgin polystyrene), used polystyrene resin expanded moldings are regenerated in addition it can use Regenerative raw materials obtained from processing.It, can be from by used polystyrene resin expanded moldings, example as the regenerative raw materials The padded coaming of conveying containers, the motor product of such as fish etc., food packaging disk etc. recycle and by limonene dissolution mechanism, Suitably select in the regenerative raw materials that are regenerated of heating volume reduction mode weight average molecular weight Mw for 120,000~300,000 range Raw material or the appropriately combined a variety of regenerative raw materials different using weight average molecular weight Mw.
Foaming agent used in bubbles foaming polystyrene series resin particle to present embodiment does not limit especially System can use for example：The aliphatic hydrocarbons such as propane, normal butane, iso-butane, pentane, isopentane, neopentane, pentamethylene；Diformazan The ethers such as ether, diethyl ether；The various alcohols such as methanol, ethyl alcohol；Carbon dioxide, nitrogen gas and water etc..Wherein, preferred aliphat hydrocarbon, into And more preferable normal butane, iso-butane, pentane, isopentane individually or their mixture.In addition, particularly preferable as carbon The pentane of the hydrocarbon of atomicity 5, isopentane, neopentane, pentamethylene, cyclopentadiene are individually or their mixture.Wherein, excellent It is selected as the mixture of one or both of isopentane and pentane.In addition, based on the hydrocarbon of above-mentioned carbon atom number 5, also may be used Be 20 DEG C or more containing boiling point, foaming agent other than the hydrocarbon of carbon atom number 5 (such as normal butane, iso-butane, propane, titanium dioxide Carbon etc.).
For the additive amount of the foaming agent, relative to 100 mass parts polystyrene resins, preferably 2~15 mass parts Range, more preferably 3~8 mass parts range, particularly preferably 4~7 mass parts range.
It is excellent relative to 100 mass parts polystyrene resins in the bubbles foaming polystyrene series resin particle Inorganic micro powders end or the chemistry hairs such as silica of the choosing addition as the talcum of hair kernel foaming agent, calcium silicates, synthesis or natural output Infusion.It is preferably 3 below mass part, more relative to 100 mass parts thermoplastic resins for the additive amount of above-mentioned hair kernel foaming agent The preferably range of 0.5~2.0 mass parts.As above-mentioned chemical foaming agent, for example, azodicarbonamide, N, N '-can be enumerated Dinitrosopentamethylene tetramine, 4,4 '-oxos bis- (benzene sulfonyl hydrazides), sodium bicarbonate etc..
In present embodiment, as above-mentioned hair kernel foaming agent, further preferred use makes the inorganic powders such as talcum or chemistry hair Masterbatch type hair kernel foaming agent obtained from infusion is dispersed in base resin, preferably polystyrene resin.By using The masterbatch type sends out kernel foaming agent, when mixing polystyrene resin and hair kernel foaming agent in resin feedway, can make inorganic powder End or chemical foaming agent are dispersed in highly uniform state in polystyrene resin, the mixed foaming agent in the molten resin When being squeezed out afterwards from the aperture of mold into water and cutting off to manufacture foaming polystyrene series resin particle, it can be readily derived The formation that above-mentioned N values are 400 or more has the bubbles foaming polystyrene series resin particle of fine bubble.
In the bubbles foaming polystyrene series resin particle of present embodiment, in addition to above-mentioned foaming agent and foaming core Except agent, in the range of the physical property of the bubbles foaming polystyrene series resin particle and expanded moldings that do not damage It is interior, anti-caking agent (anti-lumping agents), bubble conditioning agent, crosslinking agent, filler, fire retardant, resistance can also be added Fire the additives such as auxiliary agent, lubricant, colorant.
Then, it is described with reference to the reality of the manufacturing method of the bubbles foaming polystyrene series resin particle of the present invention Apply mode.
Fig. 1 is an example for indicating manufacturing device used in the manufacturing method of foaming polystyrene series resin particle Figure.The manufacturing device of this example has：Extruder 1 as resin feedway；It is many small to be installed on having for 1 front end of extruder The mold 2 in hole；Resin raw material etc. is put into the raw material feeding hopper 3 in extruder 1；It will be foamed by foaming agent supply mouth 5 Agent is pressed into the high-pressure pump 4 in the molten resin in extruder 1；So that the foraminate resin that is drilled with of cooling water and mold 2 is spat The mode for appearing to contact is arranged, indoor circulation is fed with the cutting chamber 7 of cooling water；Can cut off from mould in cutting chamber 7 The cutter 6 that the mode for the resin that the aperture of tool 2 squeezes out is rotatably arranged；Dehydrating drier 10 with solid-liquid separation function, It detaches the foaminess resin particle being transported from cutting chamber 7 with the flowing of cooling water with cooling water, and is taken off Water is dry and obtains foaminess resin particle；Accumulate the cooling water isolated with the dehydrating drier 10 with solid-liquid separation function Sink 8；Cooling water in the sink 8 is sent to the high-pressure pump 9 of cutting chamber 7；Store the dehydration and drying with solid-liquid separation function The hold-up vessel 11 for the foaminess resin particle that machine 10 is dehydrated.
It should be noted that as extruder 1, the extruder using screw rod or the extruder without using screw rod can make With.As the extruder for using screw rod, squeezed out for example, single screw extruder, multiscrew formula extruder, exhaust can be enumerated Machine, tandem extruder (tandem extruder) etc..As the extruder without using screw rod, for example, plunger type can be enumerated Extruder (plunger extruder), gear pump type extruder (gear pump extruder) etc..In addition, any extrusion Machine can use static mixer.In these extruders, it is preferable to use there is the extrusion of screw rod from the aspect of productivity Machine.In addition, the cutting chamber 7 of storage cutter 6 can also use resin by being used in method that melting extrusion is granulated Previous well-known cutting chamber.
When manufacturing bubbles foaming polystyrene series resin particle with manufacturing device shown in FIG. 1, first, weighs and make The desired additives such as polystyrene resin, hair kernel foaming agent, the fire retardant that is added as needed on for raw material, supply from raw material Feed hopper 3 is put into extruder 1.It is simultaneously abundant in advance that pellet or graininess can be made in polystyrene resin as raw material Put into from 1 raw material feeding hopper after mixing, or can also for example when using multiple batches of by each each batch from regulating Multiple raw material feeding hoppers of supply amount are put into, and mix them in extruder.In addition, former multiple batches of regeneration is applied in combination When material, preferably multiple batches of raw material is sufficiently mixed in advance, it is appropriate by magnetic separation or screening, gravity separation, pneumatic separating etc. Selection method removes foreign matter.
After supplying polystyrene resin, hair kernel foaming agent, other additives into extruder 1, resin is heated and is melted, one While the molten resin is transferred to 2 side of mold, foaming agent is pressed into from foaming agent supply mouth 5 using high-pressure pump 4 on one side, thus Mixed foaming agent in molten resin makes fusant by the sieve for removing foreign matter being arranged as required in extruder 1 It is moved to front end side while further be kneaded, by the fusant for being added to foaming agent from the mould for being attached to 1 front end of extruder The aperture of tool 2 squeezes out.
The foraminate resin spit face that is drilled with of mold 2 is configured at indoor circulation and is fed in the cutting chamber 7 of cooling water, and And the rotatable cutter 6 that the resin squeezed out from the aperture of mold 2 can be cut off is provided in cutting chamber 7.When will add When the fusant of complete foaming agent is squeezed out from the aperture for the mold 2 for being attached to 1 front end of extruder, fusant be cut into it is granular, together When contact and be quenched with cooling water, before this resin is fully cured be cut off resin particle inside generate fretting map.As a result, The bubbles foaming polystyrene series resin particle of the available present invention for being 400 or more with the calculated N values of above-mentioned formula (1).
Obtained bubbles foaming polystyrene series resin particle is transported to from cutting chamber 7 with the flowing of cooling water Dehydrating drier 10 with solid-liquid separation function, carries out while foaming polystyrene series resin particle is detached with cooling water Dehydration and drying.Dried bubbles foaming polystyrene series resin particle is stored in hold-up vessel 11.
In the manufacturing method of the bubbles foaming polystyrene series resin particle, above-mentioned cooling water is preferably forced into 0.2MPa or more.In order to pressurize to the cooling water, by by the circulation stream of above-mentioned cooling water from the discharge of high-pressure pump 9 Side is set as pressurised zone to the part of the entrance side of the dehydrating drier 10 with solid-liquid separation function by cutting chamber 7 and improves height The discharge pressure of press pump 9 is implemented.The pressure of above-mentioned cooling water be preferably set to 0.4~1.7MPa range, more preferably 0.5~ The range of 1.5MPa.
Using well-known device and gimmick in Foamex formed body manufacturing field, by vapor heating etc. to this The bubbles foaming polystyrene series resin particle of embodiment heat and prefoam, and it is pre- that polystyrene resin is made Expanded beads (hereinafter referred to as pre-expanded particles).Prefoam is carried out to the pre-expanded particles, so that the polyphenyl of itself and desired manufacture The density of vinylite expanded moldings (hereinafter referred to as expanded moldings) is same bulk density.In present embodiment, Its bulk density is not limited, 0.010~0.10g/cm is typically set to3In the range of, it is preferably set to 0.015~0.050g/ cm3In the range of.
It should be noted that the bulk density of pre-expanded particles is with JIS K6911 in present embodiment：Nineteen ninety-five " heat The value measured on the basis of solidity plastics ordinary test method ".
The assay method of the bulk density of pre-expanded particles is as described below.
Pre-expanded particles are filled in graduated cylinder to 500cm3Scale.Wherein, graduated cylinder is estimated from horizontal direction, as long as there is one Pre-expanded particles reach 500cm3Scale, just terminate to fill.Then, it is filled in graduated cylinder with 2 effective digital weighings after decimal point Its quality is set as W (g) by the quality of interior pre-expanded particles.Then, it is calculate by the following formula out the bulk density of pre-expanded particles.
Bulk density (g/cm3)=W/500
In addition, the volume coefficient of foaming of pre-expanded particles is the numerical value being calculate by the following formula out.
Bulk density (the g/cm of volume coefficient of foaming=1/3)
Then, using well-known device and gimmick in Foamex formed body manufacturing field, pre-expanded particles are filled out It fills in the die cavity of molding die, heats and carry out foaming in mold by vapor heating etc., manufacture polystyrene Resin molded foam body (hereinafter referred to as expanded moldings).
The density of the expanded moldings of present embodiment is not particularly limited, 0.010~0.10g/cm is typically set to3's In range, it is preferably set to 0.015~0.050g/cm3In the range of.
It should be noted that the density of expanded moldings is to use JIS K7122 in present embodiment：1999 " foamed plastics And the measurement of rubber-apparent density " record method measure foaming volume density.
The assay method of the density of expanded moldings is as described below.
By 50cm3(it is above 100cm in the case of semi-rigid and soft material3More than) test film not change material The mode of foam structure originally is cut off, and is measured its quality, is calculated by following formula.
Density (g/cm3)=experiment tablet quality (g)/test film volume (cm3)
Test film status adjustment, measurement with test film are cut by 72 hours or more samples after molding and at 23 DEG C ± 2 DEG C × 50% ± 5% or 27 DEG C ± 2 DEG C × 65% ± 5% of atmospheric condition under placed 16 hours or more test films.
In addition, the coefficient of foaming of expanded moldings is the numerical value being calculate by the following formula out.
Density (the g/cm of coefficient of foaming=1/3)
In addition, the bubbles foaming polystyrene series resin particle due to present embodiment is foamed, it can lead to It crosses bubbles foaming polystyrene series resin particle being directly filled in the die cavity of molding die and be foamed into mold Type and obtain the so-called former grain foaming method of expanded moldings to manufacture expanded moldings.
When obtaining expanded moldings by above-mentioned former grain foaming method, without above-mentioned prefoam process, at Bubbles foaming polystyrene series resin particle is directly filled in the die cavity of pattern tool and carries out foaming in mold.Cause This, with the die cavity for being filled in molding die by the prefoam of foaming polystyrene series resin particle and by obtained pre-expanded particles The method of foaming is compared in interior carry out mold, it is possible to reduce prefoam process can reduce cost, and because that can reduce energy Measure consumption and it can be expected that reduce carrying capacity of environment.
Embodiment
[embodiment 1]
(manufacture of bubbles foaming polystyrene series resin particle)
Relative to 100 mass parts as substrate resin polystyrene resin (TOYO STYRENE Co., Ltd.s manufacture, Trade name " HRM-10N "), by talc masterbatch (54 mass % of polystyrene resin, 40 mass % of talcum, 3 matter of magnesium stearate The mixture of amount %, 3 mass % of glyceryl monostearate) 1.0 mass parts uniformly mix with rotary drum mixer in advance, and it will thus Obtained mixture is supplied with the ratio of 160kg/hr per hour to the single screw extrusion machine of bore 90mm, keeps resin heating molten After melting, it will be pressed by extruder midway relative to the isopentane that 100 mass parts resins are 6 mass parts as foaming agent.Then, Resin and foaming agent are kneaded in extruder, while being carried out on one side cooling so that the resin temperature of extruder front end is 190 DEG C, on one side by be connected to extruder and by heater be maintained at 320 DEG C have 200 diameter 0.6mm, flat parts The granulation mold of the nozzle of length (land length) 3.0mm is squeezed out to hydraulic pressure 1.0MPa, 40 DEG C of cooling water circulation In slot, while the high speed rotation cutter for making circumferencial direction have 10 pieces of blades is fitted closely with mold, with 3000 turns per minute It is cut off, dehydrates and obtain spherical bubbles foaming polystyrene series resin particle.Obtained bubbles foaming Property polystyrene resin particle do not deform, long hair (shrinkage hole) etc., average grain diameter 1.1mm.
Relative to obtained 100 mass parts of bubbles foaming polystyrene series resin particle, by 0.03 matter of polyethylene glycol Measure part, 0.15 mass parts of zinc stearate, 0.05 mass parts of glyceryl monostearate, 0.05 mass parts of hydroxy stearic acid glyceryl ester It is evenly coated at entire resin particle surfaces.
(manufactures of expanded moldings)
The bubbles foaming polystyrene series resin particle manufactured as described above is put into 15 DEG C of freezer, places 72 After hour, supply to the intermittent pre-foaming machine of cylinder type, the vapor by being blown into pressure 0.05MPa is heated, and pre- hair is obtained Steep expanded beads.The bulk density of obtained pre-expanded particles is 0.02g/cm3(50 times of volume coefficient of foaming).Next, will After obtained pre-expanded particles are placed 24 hours under room temperature environment, pre-expanded particles are filled in long 400mm × wide In the molding die of the rectangular die cavity of 300mm × high 50mm, then, with vapor with the pressure of gauge pressure 0.08MPa at Heating 20 seconds in the die cavity of pattern tool, then, the pressure be cooled in the die cavity of molding die reaches 0.01MPa, then Molding die is opened, the rectangular expanded moldings of long 400mm × wide 300mm × high 50mm are taken out.Obtained foaming The density of body is 0.02g/cm3(50 times of coefficient of foaming).
Bubbles foaming polystyrene series resin particle, pre-expanded particles for the embodiment 1 manufactured as described above And expanded moldings, carry out following evaluation test.It should be noted that the body of bubbles foaming polystyrene series resin particle Product density and the coefficient of foaming of expanded moldings are found out according to above-mentioned assay method respectively.
In addition, finding out every 1mm as follows2Number of bubbles.
With scanning electron microscope observation cuing open by bubbles foaming polystyrene series resin particle immediate vicinity 70 times of photo is amplified in face, shooting.Particle is removed in the bubbles foaming polystyrene series resin particle from the photograph taking The section other than 200 μm is played on surface, takes 5 positions as unduplicated as possible, counting to be present in the range of 0.2mm × 0.2mm All number of bubbles (being counted containing a bladdery part) of each range, calculate the flat of the number of bubbles at 5 positions Mean, and then it is converted into every 1mm2Value find out.
In addition, finding out N values as follows.
To have used by above-mentioned<Per 1mm2Number of bubbles>Calculated bubbles foaming polystyrene series resin The following formula (1) of number of bubbles n and bulk density ρ of the grain per 1mm2 are calculated, to calculate N values.
N=n ÷ (1/ ρ) (1)
In addition, the bubble diameter (mean air bubble diameter) of expanded moldings on the basis of ASTM D-2842-69, following Under the conditions of be measured.
Scanning electron microscope uses the S-3000N that Hitachi Co., Ltd manufactures, shooting expanded moldings to cut open Photo (the shooting multiple in face：100 times), it is measured by number of bubbles existing on a straight line (60mm) for section on photo average Chord length (t) is calculate by the following formula out the diameter (d) of bubble.
Mean chord (t)=60/ (number of bubbles × shooting multiple)
Mean air bubble diameter (d)=t/0.616
In addition, for obtained expanded moldings, with JIS A9511：The side that 2006 " foamed plastic thermal insulation materials " are recorded Bending strength is measured on the basis of method.
That is, using TENSILON universal testing machines UCT-10T (manufacture of Orientec Co., Ltd.s), test body size is set For 75mm × 300mm × 30mm, compression speed is 10mm/min, front end fixture is pressurization chock 10R, supporting table 10R, fulcrum Between be measured under conditions of distance 200mm, calculate bending strength with following formula.The number of test film is set as 3, and it is flat to find out it Mean value.Bending strength (MPa)=3FL/2bh2(here, F indicates that bending maximum load (N), L indicate distance between the fulcrum (mm), b Indicate that the width (mm) of test film, h indicate the thickness (mm) of test film.)
In addition, expanded moldings are cut to long 50mm, thickness 2.5mm test pieces, on the basis of JIS Z0234, survey Determine 5% compressive strength of expanded moldings.
In addition, with JIS K7211：The ball drop values of the expanded moldings measured on the basis of 1976.That is, by foaming Body cut-out growth 200mm, width 40mm, thickness 25mm test pieces, make the steel ball of quality 255g vertically fall on the test film, ask Go out height of fall when expanded moldings 50% are destroyed.
[embodiment 2]
It is that 2.0 mass parts are used with used hair kernel foaming agent, in addition to this, operates, manufacture similarly to Example 1 Expanded moldings.
[embodiment 3]
As the manufacture of chemical conversion industry company of Yonghe County, trade name " POLYTHLENE ES275 " and made using used hair kernel foaming agent With 0.85 part, it is that 0.7MPa is operated similarly to Example 1 in addition to this to make hydraulic pressure, manufactures expanded moldings.
[embodiment 4]
It is that 4.0 mass parts are used with used hair kernel foaming agent, in addition to this, operates, manufacture similarly to Example 1 Expanded moldings.
[embodiment 5]
It is that 5.0 mass parts are used with used hair kernel foaming agent, in addition to this, operates, manufacture similarly to Example 1 Expanded moldings.
[embodiment 6]
It other than not using covering, operates similarly to Example 1, manufactures bubbles foaminess resin particle.Then, By particles filled die cavity (the long 400mm × wide 300mm in the molding die on molding machine of the bubbles foaminess resin × thickness 50mm) in, it is heated 35 seconds, is cooled down with the vapor of 0.08MPa, it is 0.641g/cm to obtain density3, coefficient of foaming For the low power expanded moldings that 1.6 times, size are 400mm × 300mm × 50mm.
[comparative example 1]
Using used hair kernel foaming agent as micropowder talcum and using 0.3 part, it is 0.3MPa to make hydraulic pressure, in addition to this, with Embodiment 1 equally operates, and manufactures expanded moldings.
[comparative example 2]
Using used hair kernel foaming agent as micropowder talcum and using 0.3 part, it is 1.0MPa to make hydraulic pressure, in addition to this, with Embodiment 1 equally operates, and manufactures expanded moldings.
The result that above-described embodiment 1~6 and comparative example 1~2 obtain is summarized shown in table 1.
[table 1]
As shown in Table 1, the N of the bubbles foaming polystyrene series resin particle of the embodiment of the present invention 1~6 Value is 400 or more, in Examples 1 to 5, by resin particle prefoam and by obtained pre-expanded particles foam in mold Molding and when the expanded moldings of 50 times of producing foamed multiple, and comparative example 1, the small previous product of N values described in 2 is compared, and is sent out The bending strength, compressive strength and ball drop values for steeping formed body are excellent, can obtain through the invention more excellent than previous product strength Expanded moldings.
In addition, embodiment 6 is that bubbles foaming polystyrene series resin particle is directly carried out foaming in mold The case where manufacturing low power expanded moldings, low power foam molded product can be obtained with less process and in a short time.
In addition, the N values of embodiment 5 are 2000 or more, intensity is in a slight decrease compared with the expanded moldings of Examples 1 to 4. Consider from this point, it is known that the upper limit of N values is preferably 2000 or less.
On the other hand, N value lower limit of the N values of the foaming polystyrene series resin particle of comparative example 1~2 less than the present invention (400), using the expanded moldings of its making compared with the embodiment of the present invention 1~5, intensity, especially ball drop values are low.
Second embodiment
The feature of the manufacturing method of the thermoplastic resin pre-expanded particles (hereinafter referred to as pre-expanded particles) of present embodiment It is, thermoplastic resin and foaming agent is subjected to melting mixing in resin feedway, and will have melted containing foaming agent Thermoplastic resin is cut off immediately after being squeezed out into cooling medium by the aperture of mold, and it is made to foam and make in cooling medium Then pre-expanded particles are detached from above-mentioned cooling medium at the pre-expanded particles of 1.6 times of volume coefficient of foaming or more, are led to It crosses extrusion by melting and directly manufactures pre-expanded particles.
In present embodiment, the type of thermoplastic resin is not limited, it can will such as polystyrene resin, poly- second Alkene system resin, polypropylene-based resin, polyester based resin, vinyl chloride-based resin, ABS resin, AS resins etc. individually or two or more It is used in mixed way.And then the recycling for the thermoplastic resin that can also be later recycled used as naval stores use Resin.Particularly preferably used as polystyrenes such as unbodied polystyrene (GPPS), high impact polystyrenes (HIPS) Resin.
As polystyrene resin, for example, styrene, α-methylstyrene, vinyltoluene, chlorobenzene second can be enumerated The homopolymer of the styrenic monomers such as alkene, ethyl styrene, isopropyl styrene, dimethyl styrene, bromstyrol or they Copolymer etc., preferably comprise the polystyrene resin of the 50 above styrene of mass %, more preferable polystyrene.In addition, making Can be with above-mentioned styrene monomer above-mentioned styrenic monomers as main component and can be with for above-mentioned polystyrene resin The copolymer of the vinyl monomer of styrenic monomers copolymerization.As above-mentioned vinyl monomer, for example, can enumerate：(first Base) (the first such as methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) aliphatic acrylate Base) alkyl acrylate, (methyl) acrylonitrile, dimethyl maleate, dimethyl fumarate, diethyl fumarate, fumaric acid second Ester, in addition there are two functional monomers such as divinylbenzene, aklylene glycol dimethylacrylate etc..
In addition, as long as polystyrene resin is main component, then other resins can also be added.Tree as addition Fat can enumerate for example, in order to improve the impact resistance of expanded moldings and be added to polybutadiene, styrene butadiene copolymers The rubber modified polystyrene system tree of the diene series rubbers shaped polymers such as object, ethylene-propylene-non-conjugated diene three-dimensional copolymer Fat, so-called high impact polystyrene.Or polyethylene-based resin, polypropylene-based resin, acrylic acid (ester) system tree can be enumerated Fat, acrylonitritrile-styrene resin, acrylonitrile-butadiene-styrene copolymer etc..In addition, as the polyphenyl second as raw material Commercially available common polystyrene resin, the polyphenyl second remake with the methods of suspension polymerization can be used in alkene system resin The polystyrene resin (non-polystyrene processed again) of the non-renewable raw materials such as alkene system resin, will be used poly- in addition it can use Phenylethylene resin series expanded moldings carry out regenerative raw materials obtained from regeneration treatment.As the regenerative raw materials, can use will Padded coaming, the food packet of used polystyrene resin expanded moldings, the conveying containers such as fish, motor product etc. The regenerative raw materials that dress disk etc. is recycled and regenerated by limonene dissolution mechanism, heating volume reduction mode.In addition, for The regenerative raw materials that can be used, in addition to carrying out used polystyrene resin expanded moldings obtained from regeneration treatment again Other than raw feedstock, can also use will be by household appliances (for example, television set, refrigerator, washing machine, air conditioner etc.), office with setting The non-foamed polystyrene resin formed body that standby (for example, duplicator, facsimile machine, printer etc.) is separately recovered is crushed and is carried out Regenerative raw materials obtained from melting mixing, granulation.
Foaming agent used in pre-expanded particles to present embodiment is not particularly limited, and can use for example：Propane, The aliphatic hydrocarbons such as normal butane, iso-butane, pentane, isopentane, neopentane, pentamethylene；The ethers such as dimethyl ether, diethyl ether；Methanol, The various alcohols such as ethyl alcohol；Carbon dioxide, nitrogen gas and water etc..
Wherein, preferred aliphat hydrocarbon, in turn, more preferable normal butane, iso-butane, pentane, isopentane individually or they Mixture.In addition, particularly preferable as the pentane of the hydrocarbon of carbon atom number 5, isopentane, neopentane, pentamethylene, cyclopentadiene Independent or their mixture.Wherein it is preferably the mixture of one or both of isopentane and pentane.More than in addition, Based on the hydrocarbon for stating carbon atom number 5, can also be 20 DEG C or more containing boiling point, foaming agent other than the hydrocarbon of carbon atom number 5 (such as Normal butane, iso-butane, propane, carbon dioxide etc.).
For the additive amount of the foaming agent, relative to 100 mass parts thermoplastic resins, the preferably model of 1~15 mass parts Range, the range of particularly preferably 2~6 mass parts enclosed, be more preferably 1~10 mass parts.
In the manufacturing method of the pre-expanded particles of the present invention, in above-mentioned thermoplastic resin, preferably addition is as foaming core Talcum, calcium silicates, synthesis or the naturally silica, ethylenebisstearamide of output, the methacrylate ester copolymerization of agent Object etc. is inorganic or organic micropowder is last.For the additive amount of above-mentioned hair kernel foaming agent, relative to 100 mass parts thermoplastic resins, preferably For 1.5 below mass part, more preferably 0.1~1.0 mass parts ranges.
In the manufacturing method of the pre-expanded particles of the present invention, in above-mentioned thermoplastic resin, in addition to foaming agent and foaming core Except agent, in the range of the physical property for the pre-expanded particles not damaged, can also add anti-caking agent, bubble conditioning agent, The additives such as crosslinking agent, filler, fire retardant, flame retardant, lubricant, colorant.
Fig. 1 is the figure for indicating an example of manufacturing device used in the manufacturing method of the pre-expanded particles of the present invention.This example Manufacturing device have：Extruder 1 as resin feedway；It is installed on having for 1 front end of extruder and is permitted lacunary mould Tool 2；Resin raw material etc. is put into the raw material feeding hopper 3 in extruder 1；Foaming agent is pressed by foaming agent supply mouth 5 To the high-pressure pump 4 in the molten resin in extruder 1；So that the foraminate resin spit face that is drilled with of cooling water and mold 2 connects Tactile mode is arranged, indoor circulation is fed with the cutting chamber 7 of cooling water；Can cut off from the small of mold 2 in cutting chamber 7 The cutter 6 that the mode for the resin that hole squeezes out is rotatably arranged；Dehydrating drier 10 with solid-liquid separation function, will be from cutting It cuts the pre-expanded particles that room 7 is transported with the flowing of cooling water to detach with cooling water, and is dehydrated and obtained Pre-expanded particles；Accumulate the sink 8 for the cooling water isolated with the dehydrating drier 10 with solid-liquid separation function；By the sink 8 Interior cooling water is sent to the high-pressure pump 9 of cutting chamber 7；Storage has carried out dehydration with the dehydrating drier 10 with solid-liquid separation function and has done The hold-up vessel 11 of dry pre-expanded particles.
It should be noted that as extruder 1, the extruder using screw rod or the extruder without using screw rod can make With.As the extruder for using screw rod, squeezed out for example, single screw extruder, multiscrew formula extruder, exhaust can be enumerated Machine, tandem extruder etc..As the extruder without using screw rod, for example, plunger-type extruder can be enumerated, gear pump type squeezes Go out machine etc..In addition, any extruder can use static mixer.In these extruders, examined in terms of productivity Consider, it is preferable to use there is the extruder of screw rod.In addition, the cutting chamber 7 of storage cutter 6 can also pass through melting extrusion using resin The previous well-known cutting chamber used in the method being granulated.
When manufacturing pre-expanded particles with manufacturing device shown in FIG. 1, first, the polystyrene tree as raw material is weighed The thermoplastic resins such as fat send out the desired additives such as kernel foaming agent, the fire retardant being added as needed on, from raw material feeding hopper 3 It puts into extruder 1.Thermoplastic resin as raw material pellet or graininess can be made and be sufficiently mixed in advance after from 1 Raw material feeding hopper is put into, or can also for example when using multiple batches of by each each batch from regulating the multiple of supply amount Raw material feeding hopper is put into, and mixes them in extruder.In addition, when multiple batches of regenerative raw materials are applied in combination, preferably will Multiple batches of raw material is sufficiently mixed in advance, is removed by the selection method appropriate such as magnetic separation or screening, gravity separation, pneumatic separating Foreign matter.
After supplying thermoplastic resin, hair kernel foaming agent, other additives into extruder 1, resin is heated and is melted, on one side will The molten resin is transferred to 2 side of mold, is on one side pressed into foaming agent from foaming agent supply mouth 5 using high-pressure pump 4, to melt Mixed foaming agent in resin, by being arranged as required in extruder 1 sieve for removing foreign matter, make fusant into Front end side is moved to while one-step melting, by the fusant for being added to foaming agent from the mold 2 for being attached to 1 front end of extruder Aperture squeezes out.
The foraminate resin spit face that is drilled with of mold 2 is configured at indoor circulation and is fed in the cutting chamber 7 of cooling water, and And the rotatable cutter 6 that the resin squeezed out from aperture can be cut off is provided in cutting chamber 7.When foaming agent will have been added Fusant when being squeezed out from the aperture for the mold 2 for being attached to 1 front end of extruder, fusant is cut into granular, is connect with cooling water It touches and is quenched, the foaming during being fully cured to resin after cut-out becomes the thermoplastic resin that volume coefficient of foaming is 1.6 times or more Fat pre-expanded particles.
The volume coefficient of foaming of thus obtained pre-expanded particles be preferably in 1.6~50 times in the range of, more preferably 1.6~40 times of range.
It should be noted that the volume coefficient of foaming of pre-expanded particles is with JIS K6911 in present embodiment：Nineteen ninety-five On the basis of " thermosetting plastics ordinary test method " after bulk density, the value that is found out by following assay method.
First, pre-expanded particles are filled in graduated cylinder to 500cm3Scale.Wherein, graduated cylinder is estimated from horizontal direction, only There are a pre-expanded particles to reach 500cm3Scale, just terminate to fill.Then, it is weighed with 2 effective digitals after decimal point It is filled in the quality of the pre-expanded particles in graduated cylinder, its quality is set as W (g).It is calculate by the following formula out the body of pre-expanded particles Product density.
Bulk density (g/cm3)=W/500
Then, it is calculate by the following formula out the volume coefficient of foaming of pre-expanded particles.
Volume coefficient of foaming (again)=1/ bulk density (g/cm3)
The volume coefficient of foaming of pre-expanded particles can be adjusted by the pressure and water temperature of cooling water.For example, low manufacturing When the pre-expanded particles of volume coefficient of foaming (high volume density), inhibit foaming one on one side under conditions of high pressure and low water temperature While being manufactured.On the other hand, when manufacturing the pre-expanded particles of high volume coefficient of foaming (low bulk density), in low-pressure and Under conditions of high water temperature, manufactured while being foamed to a certain degree.For the pressure of cooling water, for example, it is preferable to In the circulation stream of cooling water, with from the exhaust end of high-pressure pump 9 by cutting chamber 7 to the dehydrating drier with solid-liquid separation function The part of 10 entrance side is pressurised zone, is pressurizeed by the discharge pressure of high-pressure pump 9 suitably to adjust its pressure.It is pressed Power is not particularly limited, and usually carries out in the unpressurized condition, or pressurization when be set as 1.7MPa or less, preferably 1.5MPa with Under pressurization.In addition, for above-mentioned water temperature, preferably heater (or heating is set up at any position of the circulation stream of cooling water Both device and cooler) adjust water temperature.Water temperature is not particularly limited, in the range of being typically set to 20~80 DEG C, is preferably set In the range of 30~70 DEG C.
The pre-expanded particles of formation are transported to the dehydration with solid-liquid separation function from cutting chamber 7 with the flowing of cooling water Drying machine 10 herein detaches pre-expanded particles with cooling water, is carried out at the same time dehydration and drying.Dried pre-expanded particles storage In hold-up vessel 11.
For obtained pre-expanded particles, can the powdery metals soaps such as zinc stearate be coated on table as needed Face.Thus it can be prevented that adhesion (blocking) between pre-expanded particles, can keep well pre-expanded particles operation, Fillibility especially into the die cavity of molding die.
Obtained pre-expanded particles are spherical or substantially spherical.Therefore, compared with columnar pre-expanded particles are made, Xiang Cheng Fillibility in the die cavity of pattern tool is good, can seamlessly be filled in die cavity.In addition, foaming when foaming in mold Particle can be merged well each other, therefore the expanded moldings of excellent strength can be obtained.
The present invention pre-expanded particles manufacturing method in, by thermoplastic resin and foaming agent in resin feedway into Row melting mixing, after the thermoplastic resin containing foaming agent melted is squeezed out by the aperture of mold into cooling medium immediately Cut-out, and the thermoplastic resin pre-expanded particles for making it foam in cooling medium and 1.6 times of volume coefficient of foaming is made or more, Thus the pre-expanded particles for manufacturing expanded moldings can be directly manufactured by extrusion by melting.Therefore, with manufacture foaminess The previous methods that resin particle and being heated obtains pre-expanded particles are compared, and are had to manufacture with less process and be foamed Formed body, expanded moldings production efficiency improve, and the advantages of the storage space of foaminess resin particle can be reduced.
Using well-known device and gimmick in Foamex formed body manufacturing field, by the prefoam of present embodiment It is particles filled by heating such as vapor heating and to carry out foaming in mold in the die cavity of molding die, manufacture thermoplastic Property resin molded foam body (hereinafter referred to as expanded moldings).
The density and coefficient of foaming of the expanded moldings of present embodiment and the bulk density and volume of pre-expanded particles are sent out It is identical to steep multiple, density 0.625g/cm3(1.6 times of coefficient of foaming or more) below, density is preferably set to 0.020~0.625g/ cm3In the range of (1.6~50 times of coefficient of foaming).
It should be noted that the density and coefficient of foaming of expanded moldings are to use JIS K7122 in present embodiment：1999 The foaming volume density that the method that " measurement of foamed plastic and rubber-apparent density " is recorded measures.
The assay method of the density of expanded moldings is as described below.
By 50cm3(it is above 100cm in the case of semi-rigid and soft material3More than) test film not change material The mode of foam structure originally is cut off, and is measured its quality, is calculated by following formula.
Density (g/cm3)=experiment tablet quality (g)/test film volume (cm3)
It should be noted that said determination with test film is cut by 72 hours or more samples after molding and 23 DEG C ± 2 DEG C × 50% ± 5% or 27 DEG C ± 2 DEG C × 65% ± 5% of atmospheric condition under placed 16 hours or more test films.
In addition, the coefficient of foaming of expanded moldings is the numerical value being calculate by the following formula out.
Density (the g/cm of coefficient of foaming=1/3)
In the following, the effect of the present invention is further confirmed by embodiment, but embodiment below is the example of the present invention, The present invention is not limited by following embodiment record.
[embodiment 7]
(manufactures of pre-expanded particles)
Relative to 100 mass parts polystyrene resins, (TOYO STYRENE Co., Ltd.s manufacture, trade name " HRM10N "), 0.3 mass parts micropowder talcum is added, they are continuously fed into single spiral shell of bore 90mm with 130kg per hour Bar extruder.Squeeze out built-in temperature be set as 210 DEG C of maximum temperature, after making resin melting, by as foaming agent relative to 100 Mass parts resin is the pentane (isopentane of 3 mass parts:Pentane=20:80 (mass ratioes)) it is pressed by extruder midway.It is squeezing Go out in machine and resin and foaming agent are kneaded, is carried out at the same time cooling, the resin temperature of extruder front end is maintained at 170 DEG C, the pressure of the resin introduction part of mold be maintained at 15MPa, by configured with 200 diameter 0.6mm, flat part length 3.0mm Molten resin containing foaming agent is squeezed out 40 DEG C of the water cycle being connect to the exhaust end with the mold and hydraulic pressure by the mold of aperture It is set in the cutting chamber of 0.05MPa, while with circumferencial direction there is the rotary cutter of 10 pieces of blades will be squeezed out with 3000rpm Object is cut off.The particle of cut-out is transported to particle separator while being cooled with circulating water, particle is detached with recirculated water.Into And the drying of the particle dehydration of trapping is obtained into pre-expanded particles.Obtained pre-expanded particles do not deform, long hair Deng, substantially sphere, bulk density 0.6g/cm3, volume coefficient of foaming be 1.7 times, average grain diameter be about 1.3mm.
Relative to obtained 100 mass parts of pre-expanded particles, 0.03 mass parts of polyethylene glycol are uniformly coated on particle Whole surface.
(manufactures of expanded moldings)
After obtained pre-expanded particles are placed 24 hours under room temperature environment, which is filled in length In the molding die of the rectangular die cavity of 400mm × wide 300mm × high 25mm, then, with vapor with gauge pressure 0.08MPa's Pressure in the die cavity of molding die to heating 20 seconds, it is then cooled to the pressure in the die cavity of molding die reaches 0.01MPa, Then molding die is opened, the rectangular expanded moldings of long 400mm × wide 300mm × high 25mm are taken out.
The density of obtained expanded moldings is 0.6g/cm3(1.7 times of coefficient of foaming).
It is such as following for the pre-expanded particles manufactured as described above<The evaluation of mold fillibility>Described be measured is commented Valence evaluates mold fillibility.
In addition, for the expanded moldings manufactured as described above, the ocular estimate as described below for carrying out expanded moldings and The measurement of fusion rate.
In turn, according to the knot of the measurement of the evaluation of following mold fillibilities, the ocular estimate of expanded moldings and fusion rate Fruit compares following criterion and carries out comprehensive judgement.As a result it is shown in table 2.
Here, the evaluation of mold fillibility is carried out as follows.
The bulk density of the pre-expanded particles found out and the density of expanded moldings calculate filling by following formula Property, evaluate mold fillibility with following standards.
The bulk density of density/pre-expanded particles of mold fillibility=expanded moldings
The evaluation criterion of the mold fillibility is as described below.
Well (zero)：The situation that mold fillibility is 0.95 or more
Bad (×)：The case where mold fillibility is less than 0.95
In addition, carrying out the ocular estimate of expanded moldings as follows.
Pre-expanded particles are filled in the mold of foam forming machine, so that it is carried out foaming in mold with vapor, Thus the expanded moldings of the rectangular-shape of long 400mm, width 300mm, thickness 25mm are obtained.The expanded moldings that visual observations obtain Appearance, evaluated according to following standards.
Well (zero)：The smooth situation in part is merged between expanded beads
Bad (×)：Fusion part between expanded beads produces concave-convex situation
In addition, evaluating fusion rate as follows.
First, the cut line for forming deep 1mm with cutter in the arbitrary surfaces of expanded moldings, along the cut line hand Or expanded moldings are divided into two by hammer.Then, arbitrary 100~150 foaming exposed in the plane of fracture of expanded moldings In grain, ruptured in the granule number (a) of expanded beads implosion and hot melting interface between expanded beads is counted Grain number (b) calculates the fusion rate of expanded moldings according to following formula.
Fusion rate (%)=100 × granule number (a) of expanded moldings/(granule number (a)+granule number (b))
The evaluation criterion of the fusion rate is as described below.
Well：The situation that fusion rate is 70% or more
It is bad：The case where fusion rate is less than 70%
Then, the ocular estimate of evaluation, expanded moldings based on above-mentioned mold fillibility and the measurement of fusion rate this 3 A evaluation result compares following criterion and carries out comprehensive judgement.
Well (zero)：There is no the case where bad (×) in 3 evaluation results
Bad (×)：There is the case where 1 or more bad (×) in 3 evaluation results
[embodiment 8]
It is 5 mass parts to make the additive amount of pentane, and water temperature is made to be 50 DEG C, in addition to this, is carried out similarly to Example 7. To pre-expanded particles do not deform, long hair etc., substantially sphere, bulk density 0.2g/cm3, volume coefficient of foaming It is about 1.9mm for 5.1 times, average grain diameter.As a result it is shown in table 2.
[embodiment 9]
Using the mold of the aperture with diameter 0.5mm, flat part length 2.5mm, it is 7 mass to make the additive amount of pentane Part, and water temperature is made to be 50 DEG C, in addition to this, carry out similarly to Example 7.Obtained pre-expanded particles are not deformed, are grown Palpus is equal, substantially sphere, bulk density 0.03g/cm3, volume coefficient of foaming be 33.7 times, average grain diameter be about 3.2mm.Knot Fruit is shown in table 2.
[comparative example 3]
It is 5 mass parts to make the additive amount of pentane, and it is 85 DEG C to make water temperature, and by rodlike foaming body squeeze out in cutting chamber simultaneously It is cut off, in addition to this, is carried out similarly to Example 7 after expanding.Obtained pre-expanded particles are cylindric, bulk density For 0.04g/cm3, volume coefficient of foaming be 27.3 times, the diameter of cylinder is about 2.5mm, the height of cylinder is about 1.7mm.As a result It is shown in table 2.
[table 2]
According to table 2 as a result, the grain shape for the pre-expanded particles that the embodiment of the present invention 7~9 obtains is spherical, mold Fillibility is good.In addition, the appearance for the expanded moldings that embodiment 7~9 obtains is good, the fusion rate of expanded beads is also high, can Obtain the expanded moldings of high-quality.
On the other hand, it in comparative example 3, is cut off as after foamed state due to squeezing out to the molten resin in water, because The shape of this obtained pre-expanded particles is cylindric.The mold fillibility of the pre-expanded particles of the comparative example 1 reduces, and obtains The appearance and fusion rate of expanded moldings decline.
Third embodiment
The foaming polystyrene series resin particle of present embodiment is characterized in that, be by polystyrene resin and The polystyrene resin containing foaming agent melted melting mixing and is passed through mold by foaming agent in resin feedway Foaming polystyrene series resin particle obtained from aperture extrusion, cooling and cut-out, wherein surveyed with integrating sphere type color difference meter Fixed whiteness is 75 or less.
In present embodiment, the whiteness of foaming polystyrene series resin particle is asked by the result measured with following methods The value gone out becomes the index of the transparency of foaming polystyrene series resin particle.
The following measurement for carrying out whiteness.
Using foaming polystyrene series resin particle as sample, with JIS K-7105：On the basis of 1981, in the following conditions Lower measurement whiteness.
Device：Integrating sphere type color difference meter (Japanese electricity Se industrial groups manufacture, trade name " ZE2000 ")
Method：Quartz system sample container (× 13mm, Area of Sample) in filling-foam The tristimulus values of on-gauge plate is set as Y=94.95, X=92.94, Z=111.82, passes through reflection by polystyrene resin particle Method is measured.
The above-mentioned whiteness of the foaming polystyrene series resin particle of present embodiment be 75 or less, preferably 73 or less, More preferably 70 or less.When above-mentioned whiteness is more than 75, with the foaming polystyrene series manufactured by extrusion by melting in the past Similarly there are many fine bubbles in resin particle for resin particle.As a result, being possible to will produce because producing foaming And causes the bulk density of resin particle to be lower and need extra sky in keeping, transport due to the volume of certain mass increases Between the problem of, because produce foaming due to cause resin particle rupture or be easy disintegration the problem of, manufacture expanded moldings machine The problem of tool strength reduction and be difficult to because of bead short life for a long time keeping the problem of.
In the foaming polystyrene series resin particle of present embodiment, as polystyrene resin, do not limit especially System, for example, styrene, α-methylstyrene, vinyltoluene, chlorostyrene, ethyl styrene, cumene second can be enumerated The homopolymer of the styrenic monomers such as alkene, dimethyl styrene, bromstyrol or the copolymer of these monomers etc..Wherein, preferably Polystyrene resin containing the 50 above styrene of mass %, wherein more preferable polystyrene.
Can be with above-mentioned styrene monomer above-mentioned benzene as main component in addition, as above-mentioned polystyrene resin The copolymer of vinyl monomer and the vinyl monomer that can be copolymerized with the styrenic monomers.As above-mentioned vinyl monomer, example Such as, it can enumerate：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid ten Six Arrcostabs etc. (methyl) alkyl acrylate；(methyl) acrylonitrile, dimethyl maleate, dimethyl fumarate, fumaric acid two Ethyl ester, ethyl fumarate, in addition there are two functional monomers such as divinylbenzene, aklylene glycol dimethylacrylate etc..
In addition, as long as polystyrene resin is main component, then other resins can also be added.Tree as addition Fat can enumerate for example, in order to improve the impact resistance of expanded moldings and be added to polybutadiene, styrene butadiene copolymers The rubber modified polystyrene system tree of the diene series rubbers shaped polymers such as object, ethylene-propylene-non-conjugated diene three-dimensional copolymer Fat, so-called high impact polystyrene.Or polyethylene-based resin, polypropylene-based resin, acrylic acid (ester) system tree can be enumerated Fat, acrylonitritrile-styrene resin, acrylonitrile-butadiene-styrene copolymer etc..
As the polystyrene resin as raw material, commercially available common polystyrene resin can be used, with suspension Polystyrene resin (the non-polyphenyl second processed again of the non-renewable raw material such as the polystyrene resin that the methods of polymerization is remake Alkene), used polystyrene resin expanded moldings are carried out to regenerate original obtained from regeneration treatment in addition it can use Material.As the regenerative raw materials, can from by used polystyrene resin expanded moldings, the conveying containers such as fish, The padded coaming of motor product etc., food packaging disk etc. are recycled and are carried out by limonene dissolution mechanism, heating volume reduction mode Regenerate suitably selected in obtained regenerative raw materials weight average molecular weight Mw for 120,000~300,000 range raw material or appropriately combined make With the different a variety of regenerative raw materials of weight average molecular weight Mw.
For adding the foaming agent in the foaming polystyrene series resin particle, based on the hydrocarbon of carbon atom number 5, It it can also be 20 DEG C or more containing boiling point, the foaming agent other than the hydrocarbon of carbon atom number 5.
The foaming agent is preferably the one or more of the hydrocarbon of carbon atom number 5, wherein preferably isopentane and pentane One or both of mixture.
For the additive amount of the foaming agent, relative to 100 mass parts resins, the preferably range of 3~8 mass parts, more excellent It is selected as the range of 4~7 mass parts.
In the foaming polystyrene series resin particle, relative to 100 mass parts polystyrene resins, preferably comprise The powdered inorganic material as hair kernel foaming agent of 1.0 amounts below mass part, the more preferably range of 0.05~0.8 mass parts, The further preferably range of 0.1~0.5 mass parts, the powdered inorganic material have the refractive index to polystyrene resin For ± 0.08 or less, preferably 0.06 or less, more preferable 0.04 refractive index below.As with the folding to polystyrene resin The powdered inorganic material that rate is ± 0.08 refractive index below is penetrated, talcum, mica, magnesium silicate, magnesium hydroxide etc. can be enumerated, Middle preferably talc.
In the foaming polystyrene series resin particle, other than above-mentioned foaming agent and above-mentioned hair kernel foaming agent, not Damage physical property in the range of, can also add anti-caking agent, bubble conditioning agent, crosslinking agent, filler, fire retardant, flame retardant, The additives such as lubricant, colorant.In addition, gathering if the powdery metals soaps such as stearate zinc are coated on above-mentioned foaminess The surface of styrene resin particles then can reduce polyphenyl second in the prefoam process of foaming polystyrene series resin particle Combination between the resin pre-foamed particle of alkene, therefore it is preferred that.
The bulk density of the foaming polystyrene series resin particle is preferably 0.58g/cm3Above, more preferably 0.60g/cm3Above, it is more preferably 0.62g/cm3More than.When bulk density is less than 0.58g/cm3When, it is possible to tree can be made There are numerous air-bubbles in fat particle.As a result, being possible to will produce the bulk density for leading to resin particle because producing foaming Be lower and due to the volume of certain mass increases keeping, transport when need extra space the problem of, because produce foaming due to The problem of causing resin particle to rupture or be easy the problem of being disintegrated, the mechanical strength reduction of the expanded moldings of manufacture, Yi Jiyin Bead short life and be difficult to for a long time keeping the problem of.
It should be noted that in present embodiment, the bulk density of foaming polystyrene series resin particle refers to JIS K6911：The bulk density measured on the basis of nineteen ninety-five " thermosetting plastics ordinary test method ".
The assay method of the bulk density of pre-expanded particles is as described below.
Filling-foam polystyrene resin particle is to 500cm in graduated cylinder3Scale.Wherein, mesh from horizontal direction Measuring cylinder, as long as there is a foaming polystyrene series resin particle to reach 500cm3Scale, just terminate to fill.Then, with 2 effective digitals weigh the quality for being filled in the foaming polystyrene series resin particle in graduated cylinder after decimal point, by its quality It is set as W (g).It is calculate by the following formula out the bulk density of foaminess polystyrene resin particle.
Bulk density (g/cm3)=W/500
For the foaming polystyrene series resin particle of present embodiment, since bubble is few in resin particle, with integral The whiteness that ball-type color difference meter measures is shown as 75 hereinafter, therefore, with the foaminess polyphenyl second obtained by extrusion by melting in the past Alkene system resin particle is high compared to bulk density.As a result, the volume due to certain mass tails off, can compactly take care of, Transport also becomes easy.
In addition, for the foaming polystyrene series resin particle of present embodiment, since bubble is few in resin particle, because This has the advantages that excellent strength, does not allow to be also easy to produce rupture or disintegration.
In addition, for the foaming polystyrene series resin particle of present embodiment, due to heating and when carrying out prefoam It can equably foam, therefore the uniform pre-expanded particles of grain size, bulk density can be obtained.As a result, by the foaminess polyphenyl second Alkene system resin particle carries out the excellent strength of expanded moldings obtained from foaming in mold.
In addition, for the foaming polystyrene series resin particle of present embodiment, since the loss of foaming agent is slow, because This bead service life extends, and can take care of for a long time.
In the following, being described with reference to the embodiment party of the manufacturing method of the foaming polystyrene series resin particle of the present invention Formula.
The manufacturing method is characterized in that, is to manufacture foaming polystyrene series resin particle by extrusion by melting Method, wherein polystyrene resin and foaming agent are subjected to melting mixing in resin feedway, and contained what is melted The polystyrene resin of foaming agent is squeezed out into cooling medium by the aperture of mold and is cooled down and cut off, and is foamed Property polystyrene resin particle, wherein polystyrene serial resin extruded cold to what is pressurizeed containing foaming agent by what is melted But it in medium, and is cooled down and is cut off, to obtain with the whiteness that integrating sphere type color difference meter measures being 75 foaminess below Polystyrene resin particle.
Foaming agent used in the foaming polystyrene series resin particle is not particularly limited, can be used for example： The aliphatic hydrocarbons such as propane, normal butane, iso-butane, pentane, isopentane, neopentane, pentamethylene；The ethers such as dimethyl ether, diethyl ether； The various alcohols such as methanol, ethyl alcohol；Carbon dioxide, nitrogen, water etc..Wherein, preferred aliphat hydrocarbon, in turn, more preferable normal butane, isobutyl Alkane, pentane, isopentane individually or their mixture.In addition, particularly preferable as the hydrocarbon of carbon atom number 5 pentane, Isopentane, neopentane, pentamethylene, cyclopentadiene individually or their mixture.Wherein, preferably in isopentane and pentane One or two kinds of mixtures.In addition, based on the hydrocarbon of above-mentioned carbon atom number 5, can also be 20 DEG C or more containing boiling point, Foaming agent (such as normal butane, iso-butane, propane, carbon dioxide etc.) other than the hydrocarbon of carbon atom number 5.
For the additive amount of the foaming agent, relative to 100 mass parts polystyrene resins, preferably 2~15 mass parts Range, more preferably 3~8 mass parts range, particularly preferably 4~7 mass parts range.
In addition, as hair kernel foaming agent, preferably with relative to 100 mass parts polystyrene resins be it is 1.0 below mass part, It is preferred that the addition of the range of 0.05~0.8 mass parts, the range of more preferable 0.1~0.5 mass parts has to polystyrene resin Refractive index be ± 0.08 or less, preferably 0.06 or less, it is the powdered inorganic material of more preferable 0.04 refractive index below, for example sliding Stone.
Fig. 1 is an example for indicating manufacturing device used in the manufacturing method of the foaming polystyrene series resin particle Figure.The manufacturing device of this example has：Extruder 1 as resin feedway；It is many small to be installed on having for 1 front end of extruder The mold 2 in hole；Resin raw material etc. is put into the raw material feeding hopper 3 in extruder 1；It will be foamed by foaming agent supply mouth 5 Agent is pressed into the high-pressure pump 4 in the molten resin in extruder 1；So that pressurization cooling water and mold 2 are drilled with foraminate tree The mode of fat spit face contact is arranged and recycles the cutting chamber 7 of supply pressurization cooling water indoors；Can cut in cutting chamber 7 The cutter 6 that the mode of the disconnected resin squeezed out from the aperture of mold 2 is rotatably arranged；Dehydration and drying with solid-liquid separation function Machine 10 detaches the foaminess resin particle being transported from cutting chamber 7 with the flowing of cooling water with cooling water, and into Row dehydration and drying obtains foaminess resin particle；Accumulate the cooling isolated with the dehydrating drier 10 with solid-liquid separation function The sink 8 of water；Cooling water in the sink 8 is sent to the high-pressure pump 9 of cutting chamber 7；Store the dehydration with solid-liquid separation function The hold-up vessel 11 for the foaminess resin particle that drying machine 10 is dehydrated.
It should be noted that as extruder 1, the extruder using screw rod or the extruder without using screw rod can make With.As the extruder for using screw rod, squeezed out for example, single screw extruder, multiscrew formula extruder, exhaust can be enumerated Machine, tandem extruder etc..As the extruder without using screw rod, for example, plunger-type extruder can be enumerated, gear pump type squeezes Go out machine etc..In addition, any extruder can use static mixer.In these extruders, examined in terms of productivity Consider, it is preferable to use there is the extruder of screw rod.In addition, the cutting chamber 7 of storage cutter 6 can also pass through melting extrusion using resin The previous well-known cutting chamber used in the method being granulated.
In this manufacturing method, due to polystyrene serial resin extruded cold to what is pressurizeed containing foaming agent by what is melted But it in medium, therefore at least needs that pressurized environment will be maintained in cutting chamber 7.In this example, in the circulation stream of cooling water In from the exhaust end of high-pressure pump 9 by cutting chamber 7 to the part of the entrance side of the dehydrating drier 10 with solid-liquid separation function, will The pressure of cooling water is maintained at 0.4MPa or more, and but not limited to this, can also be set as pressurizeing to entire circulation stream Composition.
When manufacturing foaming polystyrene series resin particle with manufacturing device shown in FIG. 1, first, weighs and be used as raw material The desired additive such as polystyrene resin, hair kernel foaming agent, the fire retardant that is added as needed on, from raw material feeding hopper 3 put into extruder 1.After polystyrene resin as raw material can be made pellet or graininess and be sufficiently mixed in advance Put into from 1 raw material feeding hopper, or can also for example when using multiple batches of by each each batch from regulating supply amount Multiple raw material feeding hoppers input, they are mixed in extruder.In addition, when multiple batches of regenerative raw materials are applied in combination, It is preferred that multiple batches of raw material is sufficiently mixed in advance, pass through the side of selecting appropriate such as magnetic separation or screening, gravity separation, pneumatic separating Method removes foreign matter.
After supplying polystyrene resin, hair kernel foaming agent, other additives into extruder 1, resin is heated and is melted, one While the molten resin is transferred to 2 side of mold, foaming agent is pressed into from foaming agent supply mouth 5 using high-pressure pump 4 on one side, thus Mixed foaming agent in molten resin makes fusant by the sieve for removing foreign matter being arranged as required in extruder 1 It is moved to front end side while further be kneaded, by the fusant for being added to foaming agent from the mould for being attached to 1 front end of extruder The aperture of tool 2 squeezes out.
The foraminate resin spit face that is drilled with of mold 2 is configured at indoor circulation and is fed in the cutting chamber 7 of cooling water, and And the rotatable cutter 6 that the resin squeezed out from the aperture of mold 2 can be cut off is provided in cutting chamber 7.Above-mentioned cold But in the circulation stream of water, in the exhaust end from high-pressure pump 9 by cutting chamber 7 to the dehydrating drier 10 with solid-liquid separation function Entrance side part, cooling water is forced into 0.4MPa or more, is squeezed out when the fusant of foaming agent will have been added from being attached to When the aperture of the mold 2 of 1 front end of machine squeezes out, fusant is extruded in pressure (hydraulic) water, in the state to be foamed by its pressure restraining Under be cut into granular, contact and be quenched with pressure (hydraulic) water, become foaminess polyphenyl inhibiting the in the case of of foaming to be cured Vinylite particle.When the pressure of above-mentioned pressure (hydraulic) water is less than 0.4MPa, go forward side by side into cooling water squeezing out molten resin Row is cut to during resin is fully cured and easy tos produce foaming, it is possible to it is poly- to become the foaminess that whiteness is high, bulk density is low Phenylethylene resin series particle.The pressure of pressure (hydraulic) water is preferably the range of 0.6MPa or more, more preferably 0.6~1.7MPa.
The foaming polystyrene series resin particle of formation is from cutting chamber 7 as the flowing of cooling water is transported to band solid-liquid Foaming polystyrene series resin particle is detached with cooling water, is carried out at the same time de- by the dehydrating drier 10 of separation function herein Water is dried.Dried foaming polystyrene series resin particle is stored in hold-up vessel 11.
It is poly- manufacturing foaminess by extrusion by melting in the manufacturing method of the foaming polystyrene series resin particle It is polystyrene serial resin extruded to the cooling pressurizeed containing foaming agent by what is melted during phenylethylene resin series particle It in medium, and is cooled down and is cut off, to obtain with the whiteness that integrating sphere type color difference meter is measured being 75 foaminess below Polystyrene resin particle.Therefore, as described above compared with previous product, can high efficiency manufacture have the effect of excellent foaming Property polystyrene resin particle.
Using well-known device and gimmick in Foamex formed body manufacturing field, it incite somebody to action this by vapor heating etc. The foaming polystyrene series resin particle of embodiment heat and prefoam, and polystyrene resin prefoam is made Grain (hereinafter referred to as pre-expanded particles).Prefoam is carried out to the pre-expanded particles, so that the polystyrene of itself and desired manufacture The density of resin molded foam body (hereinafter referred to as expanded moldings) is same bulk density.In present embodiment, volume Density does not limit, and is typically set to 0.010~0.10g/cm3In the range of, it is preferably set to 0.015~0.050g/cm3Range It is interior.
It should be noted that the bulk density of pre-expanded particles is with JIS K6911 in present embodiment：Nineteen ninety-five " heat The value measured on the basis of solidity plastics ordinary test method ".
The assay method of the bulk density of pre-expanded particles is as described below.
Pre-expanded particles are filled in graduated cylinder to 500cm3Scale.Wherein, graduated cylinder is estimated from horizontal direction, as long as having one Grain pre-expanded particles reach 500cm3Scale, just terminate to fill.Then, it is filled in 2 effective digital weighings after decimal point Its quality is set as W (g) by the quality of the pre-expanded particles in graduated cylinder.It is calculate by the following formula out the bulk density of pre-expanded particles.
Bulk density (g/cm3)=W/500
In addition, the volume coefficient of foaming of pre-expanded particles is the numerical value being calculate by the following formula out.
Bulk density (the g/cm of volume coefficient of foaming=1/3)
The polystyrene resin pre-expanded particles of present embodiment are by above-mentioned foaming polystyrene series resin particle It heats and makes obtained from its prefoam.Moreover, because can be equably when the polystyrene resin pre-expanded particles prefoam Foaming, this makes it possible to obtain grain size, the uniform pre-expanded particles of bulk density, therefore, with the polystyrene resin prefoam Grain carries out the excellent strength of expanded moldings obtained from foaming in mold.
Using well-known device and gimmick in Foamex formed body manufacturing field, pre-expanded particles are filled in into In the die cavity of pattern tool, foaming in mold is heated and carried out by vapor heating etc., manufactures expanded moldings.
The density of the expanded moldings is not particularly limited, 0.010~0.10g/cm is typically set to3In the range of, it is excellent Choosing is set as 0.015~0.050g/cm3In the range of.
It should be noted that the density of expanded moldings is to use JIS K7122 in present embodiment：1999 " foamed plastics And the measurement of rubber-apparent density " record method measure foaming volume density.
The assay method of the density of expanded moldings is as described below.
By 50cm3(it is above 100cm in the case of semi-rigid and soft material3More than) test film not change material The mode of foam structure originally is cut off, and is measured its quality, is calculated by following formula.
Density (g/cm3)=experiment tablet quality (g)/test film volume (cm3)
It should be noted that said determination with test film is cut by 72 hours or more samples after molding and 23 DEG C ± 2 DEG C × 50% ± 5% or 27 DEG C ± 2 DEG C × 65% ± 5% of atmospheric condition under placed 16 hours or more test films.
In addition, the coefficient of foaming of expanded moldings is the numerical value being calculate by the following formula out.
Density (the g/cm of coefficient of foaming=1/3)
In the following, the effect of the present invention is further confirmed by embodiment, but embodiment below is the example of the present invention, The present invention is not limited by following embodiment record.
[embodiment 10]
(manufacture of foaming polystyrene series resin particle)
Relative to 100 mass parts polystyrene resins, (TOYO STYRENE Co., Ltd.s manufacture, trade name " HRM10N "), 0.3 mass parts micropowder talcum is added, they are continuously fed into single spiral shell of bore 90mm with 130kg per hour Bar extruder.Squeeze out built-in temperature be set as 210 DEG C of maximum temperature, after making resin melting, by as foaming agent relative to 100 Mass parts resin is the pentane (isopentane of 7 mass parts:Pentane=20:80 (mass ratioes)) it is pressed by extruder midway.It is squeezing Go out in machine and resin and foaming agent are kneaded, is carried out at the same time cooling, the resin temperature of extruder front end is maintained at 170 DEG C, the pressure of the resin introduction part of mold be maintained at 15MPa, by configured with 200 diameter 0.6mm, flat part length 2.5mm Molten resin containing foaming agent is squeezed out 40 DEG C of the water cycle being connect to the exhaust end with the mold and hydraulic pressure by the mold of aperture It is set in the cutting chamber of 1.2Mpa, while with circumferencial direction there is the high speed rotation cutter of 10 pieces of blades to cut extrudate It is disconnected.The particle of cut-out is transported to particle separator while being cooled with circulating water, particle is detached with recirculated water.In turn, The particle dehydration drying of trapping is obtained into the foaming polystyrene series resin particle containing pentane.Obtained foaminess is poly- Phenylethylene resin series particle do not deform, long hair etc., substantially sphere, and average grain diameter is about 1.1mm, bulk density is 0.64g/cm3。
Relative to obtained 100 mass parts of foaming polystyrene series resin particle, by 0.03 mass parts of polyethylene glycol, firmly 0.15 mass parts of resin acid zinc, 0.05 mass parts of glyceryl monostearate, 0.05 mass parts of hydroxy stearic acid glyceryl ester are equably It is coated on the whole surface of foaming polystyrene series resin particle.
(manufactures of expanded moldings)
The foaming polystyrene series resin particle manufactured as described above is put into 15 DEG C of freezer, it is small to place 72 When.Then, to the intermittent pre-foaming machine of cylinder type, the vapor by being blown into pressure 0.05MPa is heated, and pre- hair is obtained for supply Steep particle.The bulk density of obtained pre-expanded particles is 0.0166g/cm3(60 times of volume coefficient of foaming).
Next, after obtained pre-expanded particles are placed 24 hours under room temperature environment, pre-expanded particles are filled in In the molding die of rectangular die cavity with long 400mm × wide 300mm × high 50mm, then, with vapor with gauge pressure The pressure of 0.08MPa in the die cavity of molding die to heating 20 seconds, it is then cooled to which the pressure in the die cavity of molding die reaches Then 0.01MPa opens molding die, take out the rectangular expanded moldings of long 400mm × wide 300mm × high 50mm.
The density of obtained expanded moldings is 0.0166g/cm3(60 times of coefficient of foaming).
The survey of the measurement, bulk density of whiteness is carried out to the foaming polystyrene series resin particle manufactured as described above The fixed, evaluation in bead service life and the evaluation of the foaming deviation based on Cv values.The measurement of whiteness and the measurement of bulk density are pressed respectively Record according to said determination method is measured.In addition, carrying out the evaluation in bead service life according to following evaluation of measuring methods And the evaluation of the foaming deviation based on Cv values.
In addition, the expanded moldings manufactured as described above are carried out with the evaluation of bending strength.Assay method and evaluation criterion As described below.
In turn, comprehensive judgement is carried out according to the result that these are respectively measured and evaluated.Its criterion is for example following<Comprehensive judgement >It is described.The results are shown in tables 3.
Here, the evaluation in bead service life is carried out as follows.
The foaming polystyrene series resin particle that embodiment (and comparative example) is obtained takes care of 1 in 15 DEG C of freezer After a month, the intermittent pre-foaming machine of cylinder type is supplied it to, the vapor by being blown into vapour pressure 0.05MPa heats 2 minutes, The volume coefficient of foaming for measuring obtained pre-expanded particles compares following evaluation criterion, carries out the evaluation in bead service life.
Especially good (◎)：The situation that volume coefficient of foaming is 55 times or more
Well (zero)：Volume coefficient of foaming be 45 times less than 55 times the case where
Bad (×)：The case where volume coefficient of foaming is less than 45 times
In addition, for the pre-expanded particles that embodiment (and comparative example) obtains, the foaming deviation based on Cv values is evaluated.It is as follows Carry out the evaluation of the foaming deviation based on Cv values.
The coefficient of alteration Cv values of the size distribution of pre-expanded particles be by the standard deviation of the grain size of pre-expanded particles divided by It is worth obtained from the average grain diameter of pre-expanded particles, is calculated by following formula.
Coefficient of alteration Cv values=standard deviation/average grain diameter of the size distribution of pre-expanded particles
Here, for the coefficient of alteration Cv values of particle diameter distribution, as described above, by the average grain diameter and mark of the particle after being classified Quasi- deviation calculates, and first, the assay method of the average grain diameter as particle initially prepares have different pore size as defined in JIS A variety of sieves (aperture 8.00mm, aperture 6.70mm, aperture 5.60mm, aperture 4.75mm, aperture 4.00mm, aperture 3.35mm, Aperture 2.80mm, aperture 2.36mm, aperture 2.00mm, aperture, 1.70mm, aperture 1.40mm, aperture 1.18mm, aperture 1.00mm), it for pre-expanded particles 10g, is screened with sieve in a manner of from the big sieve in the aperture sieve small to aperture. Then, according to the grain size of each particle, becoming cannot be remained in for the sieve of prescribed level on each sieve particle by aperture State.
Then, the average grain diameter for remaining in the particle on each sieve is determined by the size in the aperture of the sieve, for example, residual The average grain diameter for the particle on sieve for being 3.35mm in aperture is set as 3.675mm.
It should be noted that the average grain diameter of the resin particle remained on each sieve is set as the aperture of the sieve and has The addition average value in the aperture of the sieve of the next big small-bore of the sieve.In the case where aperture is the sieve of 3.35mm, tool It is 4.00mm to have the aperture of sieve specified in the JIS of the next big small-bore of the sieve, therefore, using the aperture with the sieve The addition average value of 4.00mm.
Then, the quality W for remaining in the particle on each sieve is measured, it is opposite to calculate the particle remained on each sieve In the quality ratio R (quality %) of total particle, the mass ratio that the average grain diameter D of the particle of each each sieve is multiplied by particle is calculated The summation of the value is set as the average grain diameter of particle by the value of rate R.
The average grain diameter of pre-expanded particles
=Σ (the quality ratio R of average grain diameter D × particle of the particle on each sieve)
In addition, the standard deviation of pre-expanded particles in the measurement main points of the average grain diameter of above-mentioned pre-expanded particles to obtain Each sieve on particle average grain diameter D and remain in quality ratio R (matter of the particle on the sieve relative to total particle Amount %) on the basis of calculated.
Thus Cv values are found out, following evaluation criterion is compareed and is evaluated.
Well (zero)：The situation that Cv values are 0.05 or less
Bad (×)：The case where Cv values are more than 0.05
In addition, carrying out the evaluation of bending strength as follows.
The expanded moldings that corresponding embodiment (and comparative example) obtains, with JIS A9511：2006 " foamed plastic thermal insulating materials Bending strength is measured on the basis of the method that material " is recorded.
That is, using TENSILON universal testing machines UCT-10T (manufacture of Orientec Co., Ltd.s), test body size is set For 75mm × 300mm × 50mm, compression speed is 10mm/min, front end fixture is pressurization chock 10R, supporting table 10R, fulcrum Between be measured under conditions of distance 200mm, calculate bending strength with following formula.The number of test film is set as 3, and it is flat to find out it Mean value.
Bending strength (MPa)=3FL/2bh2
[here, F indicates that bending maximum load (N), L indicate that distance between the fulcrum (mm), b indicate the width (mm) of test film, H indicates the thickness (mm) of test film.]
Thus the average value for finding out bending strength compares following evaluation criterion evaluation intensity.
Especially good (◎)：Bending strength is the situation of 0.25MPa or more
Well (zero)：Bending strength is the case where 0.23MPa is less than 0.25MPa
Bad (×)：Bending strength is less than the case where 0.23MPa
Then, it is evaluated according to the evaluation in above-mentioned bead service life, the evaluation of foaming deviation based on Cv values and bending strength Evaluation result, compare following evaluation criterion and carry out comprehensive judgement.
Especially good (◎)：No bad (×) and have 2 or more especially good (◎) the case where
Well (zero)：No bad (×) and there is 1 particularly good situation
Bad (×)：There is 1 or more bad situation
[embodiment 11]
It is that 1.7MPa is carried out similarly to Example 10 in addition to this to make hydraulic pressure.As a result it is shown in table 3.
[embodiment 12]
It is that 0.7MPa is carried out similarly to Example 10 in addition to this to make hydraulic pressure.As a result it is shown in table 3.
[comparative example 4]
It is that 0.1MPa is carried out similarly to Example 10 in addition to this to make hydraulic pressure.As a result it is shown in table 3.
[comparative example 5]
Foaming agent is set as butane (iso-butane:Normal butane=30:70 (mass ratioes)), make hydraulic pressure be 1.7MPa, except this with Outside, it carries out similarly to Example 10.As a result it is shown in table 3.
[table 3]
According to the result of table 3, in the embodiment of the present invention 10~12, foaminess polyphenyl second is manufactured by extrusion by melting Alkene system resin particle, it is 62~72, with the transparency, a height of 0.61~0.65g/cm of bulk density that it is low that whiteness, which can be obtained,3Hair Bubble property polystyrene resin particle.The bead service life for the foaming polystyrene series resin particle that Examples 1 to 3 obtains comments Valence is especially good, can be taken care of for a long time.In addition, Examples 1 to 3 can be obtained, Cv values are small, size distribution deviation is small, epigranular Particle.In turn, the bending strength for the expanded moldings that Examples 1 to 3 obtains is got higher, even high-foaming multiple (60 times) Good intensity can be obtained.The bending strength of the especially expanded moldings of embodiment 10,11 is especially good.
On the other hand, the case where hydraulic pressure of comparative example 4 is than embodiment 10~12 are low, as a result, obtained foaminess polyphenyl The whiteness of vinylite particle is 78, is more than the standard (75 or less) of the whiteness of the present invention, and obtains bulk density and be lower For 0.52g/cm3White and light foaming polystyrene series resin particle.Cv values become larger in comparative example 4, it can be seen that grain size Deviation.In turn, the bending strength for the expanded moldings that comparative example 1 obtains is lower, and comprehensive judgement is bad (×).
In addition, for using comparative example 5 of the butane as foaming agent, although hydraulic pressure is improved to 1.7MPa, obtained hair The whiteness of bubble property polystyrene resin particle is 81, is more than the standard (75 or less) of the whiteness of the present invention, and obtains volume Density is lower as 0.35g/cm3White and light foaming polystyrene series resin particle.The foaminess that the comparative example 5 obtains The bead service life of polystyrene resin particle is bad (×), can not take care of for a long time.And Cv values become larger, it can be seen that grain size it is inclined Difference, comprehensive judgement are bad (×).
Industrial availability
Even the present invention relates to high-foaming multiples, and the machinery such as bending strength, compressive strength, impact resistance also can be obtained by force Spend the bubbles foaming polystyrene series resin particle of excellent polystyrene resin expanded moldings.The polyphenyl of the present invention Vinylite expanded moldings can be used for the various uses such as heat-barrier material, packaging material.
Moreover, it relates to for manufacturing the foaming of thermoplastic resin formed body such as polystyrene resin expanded moldings Thermoplastic resin pre-expanded particles and its manufacturing method be more specifically related to following technology：It will melt containing foaming The thermoplastic resin of agent cuts off to manufacture passing through for resin particle after squeezing out into the cooling medium such as water from the aperture of mold immediately During so-called extrusion by melting manufacture foaminess thermoplastic resin particle, make the resin particle cut off in cooling medium Middle foaming, the thermoplastic resin pre-expanded particles with direct manufacture for manufacturing expanded moldings.
According to the present invention it is possible to which the thermoplastic resin directly manufactured by extrusion by melting for manufacturing expanded moldings is pre- Expanded beads, therefore, compared with previous manufacture foaminess resin particle and being heated and obtain the method for pre-expanded particles, With the production efficiency raising that can manufacture expanded moldings, expanded moldings with less process and foaminess can be reduced The advantages of storage space of resin particle.The thermoplastic resin pre-expanded particles obtained by the method for the invention are spherical or substantially Spherical, compared with columnar pre-expanded particles are made, the fillibility into the die cavity of molding die is good, can be continuously into die cavity Unoccupied place is filled, and can be merged well between expanded beads when foaming in mold, and it is excellent that intensity can be obtained Different expanded moldings.
In addition, foaming polystyrene series resin particle provided by the invention is the foaminess manufactured by extrusion by melting Polystyrene resin particle, be can be obtained excellent strength expanded moldings and foaming agent from the ease of foaminess resin particle Dissipate the foaming polystyrene series resin particle of stabilization, bead long lifespan.
Reference numeral is translated
1 ... extruder (resin feedway), 2 ... molds, 3 ... raw material feeding hoppers, 4 ... high-pressure pumps, 5 ... foaming agents supply To mouth, 6 ... cutters, 7 ... cutting chambers, 8 ... sinks, 9 ... high-pressure pumps, 10 ... the dehydrating driers with solid-liquid separation function, 11 ... hold-up vessels.

Claims (10)

1. a kind of foaming polystyrene series resin particle of sphere is to supply polystyrene resin and foaming agent in resin To melting mixing in device, and by the polystyrene resin containing foaming agent melted by the aperture of mold squeeze out to institute State aperture contact and while be forced into 0.6MPa or more and 1.7MPa cooling media below, cooling and cut-out and obtain Resin particle, wherein
The whiteness of the foaming polystyrene series resin particle of the sphere measured with integrating sphere type color difference meter be 75 hereinafter, Bulk density is 0.58g/cm3More than.
2. the foaming polystyrene series resin particle of sphere according to claim 1, contains relative to 100 mass parts Polystyrene resin is the powdered inorganic material of 1.0 amounts below mass part as hair kernel foaming agent, the powdered inorganic material It is ± 0.08 refractive index below with the refractive index to polystyrene resin.
3. the foaming polystyrene series resin particle of sphere according to claim 1, contains relative to 100 mass parts Polystyrene resin is that the foaming agent of 2~15 mass parts forms.
4. the foaming polystyrene series resin particle of sphere according to claim 1, wherein foaming agent be isopentane and The mixture of one or both of pentane.
5. a kind of manufacturing method of the foaming polystyrene series resin particle of sphere is by polystyrene resin and foaming Agent melting mixing in resin feedway, and the aperture that the polystyrene resin containing foaming agent melted is passed through into mold It squeezes out into cooling medium and is cooled down and cut off and obtain the manufacturing method of foaming polystyrene series resin particle, In,
By melted containing foaming agent it is polystyrene serial resin extruded to contact with the aperture and be forced into 0.6MPa with While in upper and 1.7MPa cooling media below, is cooled down and cut off, to obtain being surveyed with integrating sphere type color difference meter Fixed whiteness is 75 or less, bulk density 0.58g/cm3The foaming polystyrene series resin particle of above sphere.
6. the manufacturing method of the foaming polystyrene series resin particle of sphere according to claim 5, wherein relative to 100 mass parts polystyrene resins, the powdered inorganic material of 1.0 amounts below mass part of addition are described as hair kernel foaming agent It is ± 0.08 refractive index below that powdered inorganic material, which has to the refractive index of polystyrene resin,.
7. the manufacturing method of the foaming polystyrene series resin particle of sphere according to claim 5, wherein relative to 100 mass parts polystyrene resins contain 2~15 mass parts foaming agents.
8. the manufacturing method of the foaming polystyrene series resin particle of sphere according to claim 5, wherein foaming agent For the mixture of one or both of isopentane and pentane.
9. a kind of polystyrene resin pre-expanded particles are the hairs for making the sphere described in any one of Claims 1 to 4 Obtained from bubble property polystyrene resin particle foamable.
10. a kind of polystyrene resin expanded moldings are by the polystyrene resin prefoam described in claim 9 It is particles filled in the die cavity of molding die and heating, carry out in mold obtained from foaming.
CN201510310212.4A 2010-03-26 2011-03-24 Foaming polystyrene series resin particle and its manufacturing method, polystyrene resin pre-expanded particles Active CN104910408B (en)

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