CN107043513A - The manufacture method of compound resin expanded beads, compound resin expanded beads formed body and compound resin expanded beads - Google Patents

The manufacture method of compound resin expanded beads, compound resin expanded beads formed body and compound resin expanded beads Download PDF

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Publication number
CN107043513A
CN107043513A CN201710064269.XA CN201710064269A CN107043513A CN 107043513 A CN107043513 A CN 107043513A CN 201710064269 A CN201710064269 A CN 201710064269A CN 107043513 A CN107043513 A CN 107043513A
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expanded beads
compound resin
resin expanded
formed body
mass parts
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CN107043513B (en
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高木翔太
西岛浩气
岛昌臣
及川政春
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JSP Corp
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JSP Corp
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08K5/00—Use of organic ingredients
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    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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    • C08K2201/00—Specific properties of additives
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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Molding Of Porous Articles (AREA)

Abstract

【Problem】A kind of compound resin expanded beads and the manufacture method of the formed body and compound resin expanded beads that use the compound resin expanded beads for resulting in the anchorage of antistatic additive and the formed body that fillibility is excellent and amalgamation is excellent into finishing die are provided.【Solution】The present invention relates to the manufacture method of the compound resin expanded beads (1) using the compound resin of the dipping polymerization styrenic monomers in vinylite as substrate resin, the formed body using the compound resin expanded beads (1) and compound resin expanded beads (1).Compound resin expanded beads (1) contain the aliphatic acid (2) of defined mixing ratio.Preferably, the carbon number of aliphatic acid is 12 22, it is preferable that aliphatic acid is saturated fatty acid.

Description

Compound resin expanded beads, compound resin expanded beads formed body and compound resin The manufacture method of expanded beads
Technical field
The present invention relates to using the compound resin of the dipping polymerization styrenic monomers in vinylite as base material tree Formed body and the compound resin hair that the compound resin expanded beads and compound resin expanded beads of fat are mutually merged Steep the manufacture method of particle.
Background technology
The mould internal shaping body for the compound resin expanded beads being made up of olefin-based resin composition and phenylethylene resin series composition (that is, expanded beads formed body) extensively should as electronic equipment, the packaging of the part of precision equipment and amortizing packaging material With.In the formed body of this purposes, in order to prevent dust attachment, as electric discharge etc. overcurrent generation caused by electrically Damage, and typically assign antistatic property.
As the method for assigning antistatic property, such as in patent document 1, disclose and impregnating volatilization to resin particle The method of antistatic additive is impregnated during property foaming agent or again after impregnating.In addition, for example in patent document 2, disclosing and utilizing The method for coating antistatic additive formed by inorganic system's foaming agent foam on compound resin expanded beads.
Prior art literature
Patent document
The Japanese Unexamined Patent Publication 2009-242634 publications of patent document 1
The Japanese Unexamined Patent Publication 2015-81274 publications of patent document 2
The content of the invention
The problem to be solved in the present invention
But, as Patent Document 1, the side of antistatic additive is impregnated when impregnating volatile foaming agent into resin particle In method, probably it can reduce the amalgamation of expanded beads because causing resin particle exceedingly to be plastified antistatic additive.With its phase To, as shown in patent document 2, in the method for antistatic additive is coated to expanded beads, it can obtain with well antistatic The expanded beads formed body of performance.But according to the different purposes of formed body, it is desirable to further improve antistatic property.
Herein, if coating substantial amounts of antistatic additive on expanded beads in order to improve antistatic property, in the presence of into The possibility that mobility in shape mould during filling-foam particle reduces and the fillibility into finishing die is deteriorated.In addition, i.e. Make the coated weight of increase antistatic additive, the antistatic additive for being attached to expanded beads be also possible to steam during because of mould internal shaping etc. and Partly depart from.As a result, being easy to produce the deviation of surface resistivity according to the different parts of expanded beads formed body.Cause This, in order to obtain the formed body that antistatic property is excellent, expects the further improvement of expanded beads.
The present invention is to complete in view of the above problems, and its object is to provide a kind of set for resulting in antistatic additive The compound resin expanded beads of property and the formed body that fillibility is excellent and amalgamation is excellent into finishing die and use The formed body of the compound resin expanded beads and the manufacture method of compound resin expanded beads.
The means solved the problems, such as
The mode of the present invention is a kind of compound resin expanded beads, is with the dipping polymerization benzene second in vinylite The compound resin of alkene monomer is the compound resin expanded beads of substrate resin,
Counted by 100 mass parts of above-mentioned compound resin, the aliphatic acid containing 0.05-0.7 mass parts.
The another way of the present invention is a kind of compound resin expanded beads formed body, is multiple above-mentioned compound resin foaming Grain formed body mutually formed by fusion, the surface resistivity of the formed body is less than 1 × 1012Ω。
The another mode of the present invention is a kind of manufacture method of compound resin expanded beads, is had：
The nuclear particle containing vinylite is set to be scattered in the dispersion step of aqueous medium,
In above-mentioned aqueous medium, in above-mentioned nuclear particle dipping, polymerizing styrene system monomer and obtain compound resin The modified process of grain,
Foaming agent is impregnated in above-mentioned composite resin particle, and the above-mentioned composite resin particle containing the foaming agent is foamed Foamed process,
In above-mentioned foamed process, aliphatic acid is impregnated in above-mentioned composite resin particle.
Invention effect
Above-mentioned compound resin expanded beads, due to the aliphatic acid containing above-mentioned ormal weight, therefore the anchorage of antistatic additive It is excellent, while the reduction of mobility can be prevented, and show enough amalgamations.Therefore, by being foamed in compound resin Antistatic additive is coated on particle and mould internal shaping is carried out, can stably obtain and give play to surface resistivity less than 1 × 1012Ω this The excellent antistatic property of sample, and the antistatic property of the different parts based on formed body deviation it is small compound resin foaming Shaping particles body.
In addition, above-mentioned compound resin expanded beads, can both be foamed and be obtained using organic system physical blowing agent, It can be foamed and be obtained using inorganic system's foaming agent such as carbon dioxide.Above-mentioned compound resin expanded beads, even with In the case that inorganic system's foaming agent is foamed, as described above, the anchorage of antistatic additive is also very excellent.Therefore, by compound Obtained from the mould internal shaping of resin expanded particle, the shaping of compound resin expanded beads that compound resin expanded beads are mutually merged Body (hreinafter referred to as " formed body ") can give play to excellent antistatic property.
In above-mentioned manufacture method, by carrying out dispersion step, modified process and foamed process, compound resin can be obtained Expanded beads.Moreover, aliphatic acid is impregnated in composite resin particle in foamed process.By using the compound tree so obtained Fat expanded beads, can obtain the anchorage of antistatic additive and fillibility into finishing die is excellent and amalgamation is excellent Formed body.
Brief description of the drawings
Fig. 1 is the profile of the expanded beads in embodiment 1.
Fig. 2 is the explanation figure of the amplification profile of the near surface of the expression expanded beads in embodiment 1.
Fig. 3 is saying for the amplification profile of the near surface for the expanded beads that expression in embodiment 1 is attached with antistatic additive Bright figure.
Fig. 4 (a) is in embodiment 1, represents to be arranged at circles specified altitude, filled with expanded beads apart from table top The explanation figure of the cylinder of tubular, Fig. 4 (b) is the explanation figure for representing to fall to the expanded beads group of table top from cylindric cylinder.
【Symbol description】
1 compound resin expanded beads
11 surfaces
2 aliphatic acid
3 antistatic additive
Embodiment
Then, the embodiment to above-mentioned compound resin expanded beads is illustrated.In this manual, by compound resin Expanded beads are referred to as " expanded beads ".Expanded beads, for example, be used in and coat the purposes of antistatic additive on its surface.It is this to use The expanded beads on way, it may be said that there is the antistatic additive contact surface adhered to for antistatic additive on surface.Further, in this specification In, expanded beads are included in including surface attachment has both the particle of antistatic additive and a particle of unattached antistatic additive Concept.
Expanded beads, for obtaining formed body by mould internal shaping.That is, by the way that multiple expanded beads are filled into shaping In mould, and composite resin particle is merged each other in finishing die, be derived from the formed body of intended shape.
Expanded beads are using the compound resin of the dipping polymerization styrenic monomers in vinylite as substrate resin. In this manual, as described above, compound resin refers to dipping, the tree of polymerizing styrene system monomer in vinylite Fat, refers to the resin of phenylethylene resin series composition being polymerized containing vinylite composition and styrenic monomers, with inciting somebody to action The hybrid resin that the phenylethylene resin series after vinylite and polymerization after polymerization are mixed is different concepts.In benzene second During the polymerization of alkene monomer, the not only mutual polymerization of styrenic monomers can also constitute the polymerization of vinylite sometimes The graft polymerization of styrenic monomers occurs on thing chain.Therefore, compound resin is not only containing the ethene being made up of vinylite It is the phenylethylene resin series composition that resin component and styrenic monomers are polymerized, further can also has containing graft polymerization The vinylite composition (that is, PE-g-PS compositions) of styrenic monomers.
The amount for the styrenic monomers impregnated in vinylite, polymerizeing, can suitably enter according to desired physical property Row adjustment.Specifically, if improving the ratio of the vinylite in compound resin, there is toughness, restoration and improve, but just Property reduction tendency.On the other hand, in the case where improving from the ratio of the construction unit of styrenic monomers, exist Rigidity is improved, but the tendency of toughness, restoration reduction.For example, in compound resin, counted by 100 mass parts of vinylite, The construction unit from styrenic monomers more than 100 mass parts and below 1900 mass parts can be contained.In order to obtain The good formed body of toughness, restoration, rigid balance, in compound resin, is counted by 100 mass parts of vinylite, Preferably contain more than the construction unit from styrenic monomers below 400 mass parts and 1900 mass parts.From further From the viewpoint of the rigidity for improving formed body, counted by 100 mass parts of vinylite, from the structure of styrenic monomers The content of unit is more preferably more than 450 mass parts, more than more preferably 500 mass parts.In addition, in order to further improve Toughness, the restoration of formed body, count by 100 mass parts of vinylite, from the construction unit of styrenic monomers Content is more preferably below 1000 mass parts, below more preferably 900 mass parts.Further, in this manual, with numerical value The related preferred scope of the upper limit and lower limit of scope, more preferably scope, further preferred scope can be by the complete of the upper limit and lower limit Combine to determine in portion.
As vinylite, it is, for example, possible to use straight-chain low density polyethylene (LDPE), branched low density polyethylene (LDPE), height Density polyethylene, ethylene-acrylic acid copolymer, ethylene-acrylic acid alkyl ester copolymer, ethylene alkyl methacrylate are common Polymers, vinyl-vinyl acetate copolymer etc..As vinylite, a kind of polymer can be used, two kinds can also be used The mixture of polymer above.
Vinylite is preferably used as principal component using straight-chain low density polyethylene (LDPE).Specifically, in vinylite The content of straight-chain low density polyethylene (LDPE) is preferably more than 50 mass % more preferably more than 70 mass %, more preferably More than 80 mass %, are particularly preferably only made up of straight-chain low density polyethylene (LDPE).As other vinylites, second can be used Alkene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer etc..It is used as ethylene-acetate second The content of enoate copolymer, preferably below 20 mass %, more preferably below 10 mass %, more preferably 5 mass % Below.In addition, as the content of the vinyl acetate in vinyl-vinyl acetate copolymer, preferably below 5 mass %, more Preferably below 3 mass %.Straight-chain low density polyethylene (LDPE) preferably has following construction：Polyethylene Chain and carbon with straight chain are former Subnumber is the side chain of 2-6 short chain shape.Specifically, ethylene-butene copolymer, polyethylene-hexene copolymerization can be for example enumerated as Thing, ethylene-octene copolymer etc..Especially, vinylite is preferably what is be polymerized using metallocene system polymerization catalyst Fusing point is less than 105 DEG C of straight-chain low density polyethylene (LDPE).In this case, the vinylite composition in compound resin and Compatibility between the phenylethylene resin series composition that styrenic monomers are polymerized further is improved, it is possible to increase compound resin Toughness.Further, since can be while low molecular weight compositions are reduced, the fusion between expanded beads when improving shaping is strong Degree, therefore, it is possible to obtain low VOC (VOC) and be difficult to the formed body that ruptures.Further, result in Higher level has the formed body of the excellent rigidity of phenylethylene resin series and the excellent bonding strength of vinylite concurrently.
In addition, the fusing point Tm of vinylite is preferably 95-105 DEG C.In this case, styrenic monomers can be made It is sufficiently impregnated in vinylite, therefore, it is possible to prevent the destabilization of suspended system during polymerization.As a result, can obtain It is able to the formed body that higher level has the excellent rigidity of phenylethylene resin series and the excellent bonding strength of vinylite concurrently. From the same viewpoint, the fusing point Tm of vinylite is preferably 100-105 DEG C.In addition, fusing point Tm can be based on JIS (days This industrial standard) K7121 (1987), (DSC) is determined by Differential Scanning Calorimeter and is measured with melting peak temperature.
Compound resin contains the phenylethylene resin series component that styrenic monomers are polymerized.Further, in this manual, Sometimes by constitute phenylethylene resin series component styrene, be added as needed on can with styrene copolymerized monomer and be referred to as Styrenic monomers.The ratio of styrene in styrenic monomers, preferably more than 50 mass %, more preferably 80 mass % More than, more preferably more than 90 mass %.As can with styrene copolymerized monomer, for example have styrene derivative, Other vinyl monomers etc..
As phenylethylene resin series composition, from the viewpoint of foaminess is improved, preferably polystyrene, styrene and third The copolymer of olefin(e) acid system monomer.From the viewpoint of further raising foaminess, the benzene for constituting phenylethylene resin series composition is used as Vinyl monomer, preferably uses styrene and butyl acrylate.In this case, acrylic acid fourth is derived from compound resin The content of the construction unit of ester, overall relative to compound resin, preferably 0.5-10 mass %, more preferably 1-8 mass % enter One step is preferably 2-5 mass %.
Counted by 100 mass parts of compound resin, expanded beads contain the aliphatic acid of 0.05-0.7 mass parts.In aliphatic acid In the case that content is more than 0.7 mass parts, the amalgamation of expanded beads is possible to become not enough.Therefore, it is possible to make formed body Bonding strength reduction and easily rupture.In addition, in the case where the content of aliphatic acid is more than 0.7 mass parts, during shaping Recovery become not enough, it is possible to become to be difficult to obtain intended shape, the formed body of desired size, or make the outer of formed body See and be deteriorated.From the viewpoint of the further amalgamation for improving expanded beads, the further recovery improved when shaping, with compound Resin is 100 mass parts meters, and the content of aliphatic acid is preferably below 0.5 mass parts, below more preferably 0.3 mass parts.It is another Aspect, in the case that the content of aliphatic acid is less than 0.05 mass parts, the mobility of expanded beads, the anchorage of antistatic additive have It may become not enough.From the viewpoint of further raising mobility, anchorage, counted by 100 mass parts of compound resin, fat The content of acid is preferably more than 0.07 mass parts, more than more preferably 0.1 mass parts.
Preferred fatty acid deviation is present in the surface of expanded beads or the surface part including surface.By aftermentioned Expanded beads manufacturing process in adjustment addition aliphatic acid opportunity and the table to surface or including surface can be realized The deviation presenceization of layer segment.Specifically, by adding aliphatic acid in the dipping polymerization of styrenic monomers, or in hair Add aliphatic acid during bubble into pressure vessel together with the composite resin particle before foaming, or applied to the expanded beads after foaming Aliphatic acid is covered, and deviation presenceization of the aliphatic acid to surface can be realized.More preferably the surface of expanded beads is overall fatty Acid covering.In this case, the additive effect of above-mentioned aliphatic acid can be given full play to.
Aliphatic acid deviation is present in the surface of expanded beads or the situation of the surface part including surface, for example can be with Confirmed by infrared absorption spectrum.For example, obtained in the infrared absorption spectrum that (ATR methods) is absorbed by total reflection In the case of, the various pieces of the surface part including surface of middle body and expanded beads for expanded beads are asked Go out 1550cm-1Neighbouring absorbance D1550With 698cm-1Neighbouring absorbance D698The ratio between (D1550/D698), and by confirming with Entreat the dulling luminosity ratio D of part1550/D698Value compare surface part dulling luminosity ratio D1550/D698Value it is bigger, and be able to confirm that The deviation of aliphatic acid is present.Further, in dulling luminosity ratio D1550/D698In, absorbance D698Represent from mainly polystyrene It is the absorption for becoming angular oscillation outside the face of phenyl ring contained by resin, and absorbance D1550Represent from the carboxylic contained by aliphatic acid The absorption of base.
Aliphatic acid is the carboxylic acid of monovalence, and preferably carbon number is more than 12 long chain fatty acids (that is, higher fatty acids), The carbon number of aliphatic acid is more preferably 12-22, and further preferred carbon number is 16-20, and particularly preferred carbon number is 18. In this case, resin component (that is, the vinylite composition and polystyrene tree in expanded beads can further be improved Fat composition) with the compatibility of aliphatic acid.Thus, it is easy to make the additive effect of aliphatic acid be embodied in the whole surface of expanded beads. As a result, for example, antistatic additive is easily attached to the whole surface of expanded beads, and the anchorage of antistatic additive is improved, Therefore, it is possible to more reduce the deviation of antistatic property.Aliphatic acid can be a kind or mixture of more than two kinds.This Outside, aliphatic acid refers to acid itself, not including the soap such as zinc stearate.If using soap, merging Property etc. characteristic be possible to not enough.In addition, aliphatic acid does not preferably contain the alkyl in aliphatic acid such as hydroxy stearic acid Part has the derivative of fatty acid of functional group.
In addition, the viewpoint based on mechanical strength, the principal component of vinylite is preferably that straight-chain is low as described above Density polyethylene, but straight-chain low density polyethylene (LDPE) does not have polar group.Therefore, it is straight in vinylite is improved In the case of the content ratio of linear low density polyethylene, it is considered that antistatic additive is difficult to the set on vinylite.But It is, because above-mentioned compound resin expanded beads contain aliphatic acid as described above, even if therefore raising straight-chain low density polyethylene The content ratio of alkene, can also show the anchorage of excellent antistatic additive.That is, above-mentioned compound resin expanded beads, can Take into account excellent mechanical strength and antistatic property.
In addition, aliphatic acid can be saturated fatty acid or unrighted acid.Preferably saturated fatty acid. In this case, the mobility of expanded beads is further improved, and improves the fillibility into finishing die.Further, due to anti- The anchorage of electrostatic agent is further improved, and further suppress the outflow of antistatic additive caused by steam during by shaping etc., because This can obtain the more stable effect of surface resistivity.
In addition, the apparent density of the expanded beads containing aliphatic acid is preferably 10-300kg/m3, more preferably 20- 150kg/m3, more preferably 30-100kg/m3。
Furthermore it is possible to make antistatic additive be attached to the surfaces of expanded beads.Counted by 100 mass parts of expanded beads, by resisting The adhesion amount of antistatic additive on the expanded beads of electrostatic agent cladding is preferably 0.4-3.5 mass parts.In this case, can While antistatic property is fully obtained, confluent reduction is further prevented.From more fully obtaining antistatic behaviour From the viewpoint of energy, counted by 100 mass parts of expanded beads, the adhesion amount of antistatic additive is more preferably more than 0.5 mass parts, is entered One step is preferably more than 1 mass parts.In addition, from the viewpoint of it can further prevent confluent reduction, antistatic additive Adhesion amount be more preferably below 2.7 mass parts, below more preferably 2.5 mass parts.
As antistatic additive, for example, it can use cation system surfactant, nonionic surfactants, both sexes table Face activating agent etc..These surfactants be can be used alone or multiple combinations are used., for example can profit as antistatic additive Use various commercially available products.
It is preferred that antistatic additive at least contains cation system surfactant.In this case, antistatic additive is more easily The set on expanded beads, can further improve antistatic property.Because, expanded beads contain fat as described above Acid, surface carry come from aliphatic acid carboxyl negative electrostatic charge, therefore by cation system surfactant constitute it is antistatic Agent is easy to set.Even moreover, a small amount of antistatic additive can also show excellent antistatic property, and can more enter one Step prevents confluent reduction, to reduction of fillibility of finishing die etc..
In addition, as antistatic additive, preferably and with cation system surfactant and nonionic surfactants.At this In the case of kind, it can further reduce formed body obtained from the expanded beads coated to antistatic additive carry out mould internal shaping The deviation of the surface resistivity on surface.That is, the deviation of the antistatic property of formed body can further be reduced.Go out from above-mentioned viewpoint The usage amount of hair, cation system surfactant and nonionic surfactants is preferably following mass ratio：When cation system When the amount of surfactant is 1, the amount of nonionic surfactants is 0.1-1.0, more preferably nonionic system surface The amount of activating agent is 0.2-0.8, and particularly preferably the amount of nonionic surfactants is 0.4-0.6.
The formed body that the expanded beads of antistatic additive are mutually merged is attached with, based on the antistatic of different measurement site The deviation of performance (specifically, surface resistivity) is smaller, can stably show to meet surface resistivity less than 1 × 1012 Ω excellent antistatic property.
The coefficient of alteration Cv of the surface resistivity of formed body is preferably less than 3, more preferably less than 2, more preferably 1 Below.The coefficient of alteration Cv of surface resistivity, by the standard deviation V divided by the average value Tav of surface resistivity of surface resistivity The value of gained is represented, is the index for representing the extent of deviation relative to average value.In addition, the standard deviation V of surface resistivity can To be obtained by following formula (1).
V={ ∑s (Ti-Tav)2/(n-1)}1/2……(1)
In formula (1), Ti represents each measured value of surface resistivity, and Tav represents the average value of surface resistivity, and n is represented Number of times is determined, ∑ represents to calculate (Ti-Tav) for each measured value2All it is added.Coefficient of alteration Cv can pass through Following formula (2) is obtained.
Cv=V/Tav ... (2)
Then, the embodiment to the manufacture method of expanded beads is illustrated.By making containing vinylite composition Foamed with the composite resin particle of phenylethylene resin series composition and obtain expanded beads.Composite resin particle, such as by carrying out Following dispersion step and modified process and manufacture.In dispersion step, make the nuclear particle point using vinylite as principal component Dissipate in aqueous medium.In modified process, in an aqueous medium, in the presence of polymerization initiator, impregnated in nuclear particle, Polymerizing styrene system monomer.Also, foaming agent producing foamed composite resin particle is impregnated into composite resin particle, and is passed through Enter to exercise the foamed process of foaminess composite resin particle foaming, and expanded beads can be obtained.Hereinafter, each operation is carried out detailed Describe in detail bright.
In dispersion step, the nuclear particle using vinylite composition as principal component is used, nuclear particle can contain bubble Regulator, colouring agent, lubriation material, scattered footpath expand the additives such as agent.Nuclear particle, can pass through the addition by as needed Above-mentioned additive and vinylite components matching, carry out being granulated and being manufactured after melting mixing to complex.Melting is mixed Refining can be carried out by extruder.In order to uniformly be kneaded, extruded again after preferably resin component is mixed in advance.Resin The mixing of composition, with can for example using Henschel mixer, Ribbon Blender, V-mixer, sieve lattice mixerCarried out Deng mixer.Melting mixing is preferably used such as Dulmage types, Maddock types, Unimelt types The screw rod or double screw extruder of high dispersive type is carried out.
The granulation of nuclear particle, such as by by the complex after melting mixing while with extruder extrusion on one side cut off come Carry out.Granulation, such as can by wire cutting mode, imderwater cutting mode, thermal cutting mode carry out.
In dispersion step, the dispersion liquid that nuclear particle is scattered in aqueous medium can be obtained.As aqueous medium, for example Deionized water can be used.It is preferred that nuclear particle is scattered in aqueous medium together with suspension.In this case, benzene can be made Vinyl monomer is equably suspended in aqueous medium.It is used as suspension, preferably tricalcium phosphate, hydroxyapatite, pyrophosphoric acid Magnesium.These suspensions may be used singly or in combination of two or more.
The usage amount of suspension, with the aqueous medium in suspended polymerization system (specially including containing reaction product Whole water in system including the water of slurry etc.) it is 100 mass parts meters, it is preferably 0.05-10 mass parts in terms of solid content. More preferably 0.3-5 mass parts.In the case where suspension is very few, in modified process, it is difficult to make styrenic monomers stable Ground is suspended, it is possible to produce the block of resin.On the other hand, in the case where suspension is excessive, not only manufacturing cost increases, And the particle diameter distribution of the composite resin particle obtained after modified process is possible to broaden.
In order that suspension is stabilized, neopelex, sodium alkyl sulfonate etc. can be added in an aqueous medium Dispersing aid.The alkyl sulfonic acid alkali metal salt (being preferably sodium salt) that preferably carbon number is 8-20.Thereby, it is possible to make suspended fill Ground is divided to stabilize.
In addition, in an aqueous medium, as needed, can for example add by lithium chloride, potassium chloride, sodium chloride, sodium sulphate, The electrolyte that the inorganic salts such as sodium nitrate, sodium carbonate, sodium acid carbonate are constituted.In addition, more excellent in order to obtain toughness, mechanical strength Formed body, water-soluble polymerization inhibitor is preferably added in an aqueous medium.As water-soluble polymerization inhibitor, for example, it can use nitrous acid Sodium, potassium nitrite, ammonium nilrite, L-AA, citric acid etc..
Water-soluble polymerization inhibitor, it is difficult to be immersed in nuclear particle, and it is dissolved in aqueous medium.Therefore, although be immersed in Styrenic monomers in nuclear particle can be polymerize, but can suppress to be not impregnated with nuclear particle but in an aqueous medium Styrenic monomers fine droplet and the styrenic monomers of the nuclear particle near surface in being absorbed by nuclear particle Polymerization.Speculate as a result, the amount of the phenylethylene resin series on the top layer of composite resin particle can be reduced, improve obtain into The toughness of body.The addition of water-soluble polymerization inhibitor, with aqueous medium (specially including the slurry containing reaction product etc. Whole water in system including water) it is 100 mass parts meters, preferably 0.001-0.1 mass parts, more preferably 0.005- 0.06 mass parts.
In modified process, in an aqueous medium, dipping, polymerizing styrene system monomer in nuclear particle.Further, styrene It is the polymerization of monomer, is carried out in the presence of polymerization initiator.In this case, sometimes in the polymerization of styrenic monomers While produce vinylite crosslinking.Polymerization initiator is used in the polymerization of styrenic monomers, but as needed may be used With and use crosslinking agent.Also, when using polymerization initiator, crosslinking agent, preferably polymerization initiator, crosslinking agent are dissolved in advance In styrenic monomers.
, can be by the total amount of the styrene monomer of predetermined cooperation once in nuclear particle during dipping polymerization styrenic monomers Property is added to the aqueous medium for being dispersed with nuclear particle, can also for example split the total amount of the styrenic monomers of predetermined cooperation For more than two parts, these monomers are added on different opportunitys.Specifically, can be by the total amount of the styrenic monomers of predetermined cooperation In a part be added to the aqueous medium for being dispersed with nuclear particle, make styrenic monomers dipping, polymerization, then, further The remainder of the styrenic monomers of predetermined cooperation is divided into more than once or twice and is added to aqueous medium.Such as the latter institute State, by dividedly adding styrenic monomers, can further suppress the condensation between resin particle in polymerization.
In addition, polymerization initiator, aqueous medium can be added to be dissolved in the states of styrenic monomers.As above It is described, the styrenic monomers of predetermined cooperation are being divided into more than twice and in the case of different opportunity additions, can be with Make polymerization initiator be dissolved in it is in office when machine addition styrenic monomers in, polymerization initiator can also be added to not In each styrenic monomers added with opportunity.In the case of segmentation addition styrenic monomers, preferably make polymerization initiator At least it is first dissolved in advance in the styrenic monomers (hereinafter referred to as " the first monomer ") initially added.It is preferred that in the first monomer More than the 75% of the total amount of the predetermined polymerization initiator coordinated of dissolving, more preferably dissolves more than 80%.In this case, in system When making composite resin particle, styrenic monomers can be made fully to be immersed in vinylite, can prevented in polymerization Suspended system destabilization.As a result, can obtain having the excellent rigidity of phenylethylene resin series and ethene concurrently with higher level It is the formed body of the excellent bonding strength of resin.Also, as described above, by a part for the styrenic monomers of predetermined cooperation In the case of being added as the first monomer, the remainder in the total amount of the styrenic monomers of predetermined cooperation can be regard as the Two monomers, the opportunity additions different from the first monomer after the first monomer is added.Addition second can also further be split single Body.
Further, seed ratio (that is, the quality of the first monomer and nuclear particle for the styrenic monomers added as the first monomer Than) it is preferably more than 0.5.In this case, it is easy to make the shape of composite resin particle closer to spherical.From same viewpoint Set out, seed ratio more preferably more than 0.7, more preferably more than 0.8.Also, seed ratio preferably less than 1.5.At this In the case of kind, styrenic monomers can be better protected from and be sufficiently impregnated before nuclear particle just polymerizeing, can preferably be prevented Only produce the block of resin.From the same viewpoint, the seed ratio more preferably less than 1.3 of the first monomer, it is further excellent Elect less than 1.2 as.
The preferred satisfactions of polymerization temperature Tp (DEG C) in the fusing point Tm (DEG C) and modified process of vinylite in nuclear particle Tm-10≤Tp≤Tm+30 relation.In this case, when manufacturing composite resin particle, styrenic monomers can be filled It is immersed in vinylite with dividing, the destabilization of suspended system when can prevent from polymerizeing.As a result, can obtain with more High level has the expanded beads formed body of the excellent rigidity of phenylethylene resin series and the excellent bonding strength of vinylite concurrently.And And, dipping temperature, polymerization temperature in modified process are different according to the species of the polymerization initiator used difference, but excellent Elect 60-105 DEG C, more preferably 70-105 DEG C as.Also, crosslinking temperature is different according to the species difference of the crosslinking agent used, It is preferred that for 100-150 DEG C.
In addition, in styrenic monomers, plasticizer, oil-soluble polymerization inhibitor, fire retardant, coloring can be added as needed on Agent, chain-transferring agent etc..As plasticizer, for example, it can use fatty acid ester, acetylated monoglyceride, grease type, hydrocarbon Thing etc..
The additives such as above-mentioned plasticizer, oil-soluble polymerization inhibitor, fire retardant, colouring agent, chain-transferring agent can also be dissolved in molten Impregnated in agent in nuclear particle.As solvent, the fat such as aromatic hydrocarbon, heptane, octane such as can use ethylbenzene, toluene Race's hydrocarbon etc..
The foaming of composite resin particle, can pass through steaming in composite resin particle using in advance after dipping foaming agent Preparation foaming method that vapour, warm water, warm wind are heated, heated in pressure vessel together with foaming agent after be discharged under low pressure The direct foaming method for making it foam.As used foaming agent, the organic systems such as butane, pentane, propane can have both been used to send out Infusion, can also use inorganic system's foaming agent such as carbon dioxide, air, nitrogen.Preferably inorganic system's foaming agent, particularly preferably Carbon dioxide.In this case, foaming agent spreads from expanded beads after expanding, and foaming agent will not remain in expanded beads It is interior.Therefore, in shaping, it is difficult to occur the rising of particle internal pressure, can complete the cooling of formed body in a short time, and from into Taken out in shape mould.
The above-mentioned aliphatic acid contained in expanded beads, for example, can coordinate in nuclear particle.Furthermore it is also possible to by aliphatic acid It is dissolved in the styrenic monomers added in modified process.Further, by aliphatic acid and it can also be answered in foamed process Resin particle is added in pressure vessel together, and aliphatic acid can also be coated in the expanded beads obtained after foamed process On.It is preferred that aliphatic acid dissolving addition is added in styrenic monomers, or in foamed process or after foamed process.At this In the case of kind, aliphatic acid deviation can be made to be present in the surface of expanded beads, above-mentioned aliphatic acid can be significantly more obtained Additive effect.
In addition, in the case where being dissolved in and being added in styrenic monomers by aliphatic acid, by the styrene of predetermined cooperation It is that the total amount of monomer is divided into more than twice and in the case where different opportunitys adds these monomers, preferably dissolves aliphatic acid In the styrenic monomers added after second.Aliphatic acid is more preferably dissolved in the styrenic monomers finally added In.In this case, aliphatic acid deviation can be also made to be present in the surface of expanded beads.Further, being used as addition aliphatic acid Opportunity, never increase manufacturing process, make aliphatic acid additive effect become significantly from the viewpoint of, particularly preferably in foamed process Middle addition.
Formed body, can be manufactured by the known mould internal shaping method carried out by steam heating.I.e., it is possible to by inciting somebody to action Multiple expanded beads are filled in the finishing dies such as mould, and importing steam into the finishing die makes expanded beads mutually merge, from And formed body can be obtained.
Embodiment
(embodiment 1)
Hereinafter, the expanded beads involved by embodiment are illustrated.
Expanded beads involved by embodiment, with vinylite dipping polymerization styrenic monomers it is compound Resin is substrate resin.That is, compound resin contains the polystyrene that vinylite composition and styrenic monomers are polymerized Resin component.Counted by 100 mass parts of compound resin, the aliphatic acid (being specially stearic acid) that expanded beads contain 0.2 mass parts. Hereinafter, the manufacture method to the expanded beads of this example is illustrated.Further, in this example, by entering to obtained expanded beads One step carries out mould internal shaping and prepares formed body.
(1) preparation of nuclear particle
As vinylite, prepare the straight-chain low density polyethylene (LDPE) using metallocene polymerization polymerization catalyst (be specially Dong Cao companies manufacture " Nipolon-Z HF 210K ").The fusing point Tm of the vinylite is 103 DEG C.Also, make For foaming nucleation agent, prepare 10% masterbatch (being specially " CE-7335 " of POLYCOL (strain) manufactures) of Firebrake ZB.Further, make For antioxidant, 10% masterbatch for preparing antioxidant (is specially " TMB113 " of Dong Bang companies manufacture, phosphorus system stabilizer 6.5% and hindered phenol series antioxidant 3.5%).Then, by vinylite 8.58kg, the masterbatch 1.33kg of Firebrake ZB, anti- It (is specially the model FM- of the pond chemical industry machine company of three well three manufacture that the masterbatch 0.9kg of oxidant, which is put into Henschel mixer, 75E), mix 5 minutes, obtain resin compound.
Then, using extruder (be specially IKG (strain) manufacture model MS50-28,50mm φ single screw extrusion machines, Maddock types screw rod) melting mixing is carried out to resin compound at a temperature of 230-250 DEG C, and using patterning method in water, cut Average 0.5mg/ are broken into, so as to obtain nuclear particle.
(2) preparation of composite resin particle
It is further to add Jiao to the internal volume with agitating device in 3L autoclave, to add deionized water 1000g Sodium phosphate 6.0g.Afterwards, powdered magnesium nitrate hexahydrate 12.9g is added, is stirred at room temperature 30 minutes.Thus, it is prepared into It is used as the magnesium pyrophosphate slurry of suspension.Then, the dodecyl sodium sulfate (tool as dispersing aid is put into the suspension Body be 10 mass % the aqueous solution) 2.0g, natrium nitrosum 0.2g and nuclear particle 75g as water-soluble polymerization inhibitor.
Then, as polymerization initiator, it (is specially You companies to prepare peroxidating -2- ethylhexyl single carbons tert-butyl acrylate Manufacture " PERBUTYL E ") and the tertiary own ester of perbenzoic acid (be specially the manufacture of You companies " PERHEXYL Z "). Also, prepare α-methylstyrene dimer (be specially the manufacture of You companies " Nofmer MSD ") as chain-transferring agent.So Afterwards, by peroxidating -2- ethylhexyl single carbon tert-butyl acrylates 1.72g, the tertiary own ester 0.86g of perbenzoic acid and α-methylstyrene Dimer 0.63g is dissolved in the first monomer (styrenic monomers).Then, while by dissolved matter with 500rpm mixing speed It is stirred while being put into the suspension in autoclave.Further, as the first monomer, using styrene 70g and third Olefin(e) acid butyl ester 15g mix monomer.
Then, with after the air in nitrogen displacement autoclave, start to warm up, will be heated up with 30 minutes 1 hour in autoclave It it is 100 DEG C to temperature.After heating, kept for 1 hour with 100 DEG C of the temperature.Afterwards, mixing speed is dropped into 450rpm, with 100 DEG C of temperature is kept for 7.5 hours.Temperature (being specially 100 DEG C) now is exactly polymerization temperature.In addition, reaching 100 DEG C When after temperature by 1 hour, the styrene 350g as second comonomer (being specially styrenic monomers) was added to 5 hours In autoclave.
Then, temperature will be warming up in autoclave for 125 DEG C with 2 hours, be kept for 5 hours with 125 DEG C of temperature like this. Afterwards, make cooling in autoclave, take out content (being specially composite resin particle).Then, nitric acid is added, is made in compound resin The magnesium pyrophosphate dissolving of the surface attachment of particle.Afterwards, it is dehydrated and is cleaned by using centrifugal separator, and uses pneumatic conveying drying Device removes the moisture for being attached to surface, obtains with from the ratio of the construction unit of styrenic monomers and vinylite (being specially mass ratio) is 85:15 compound resin is the composite resin particle of substrate resin.Styrenic monomers should be derived from Construction unit and vinylite ratio, can be with the styrenic monomers and vinylite used during fabrication Obtained than (mass ratio).
(3) foamed process
Composite resin particle 500g is added to the 5L equipped with agitator together with the water 3500g as decentralized medium Pressure vessel.Then, the kaolin 3g as dispersant, the alkyl as dispersing aid are added in the decentralized medium in container Benzene sulfonic acid sodium salt 0.2g, stearic acid (being specially " 1 grade of the stearic acid deer " of Northeast chemistry manufacture) 1g as aliphatic acid.Hereinafter, will Aliphatic acid used in this example is referred to as aliphatic acid A.Then, while with 300rpm rotary speed to being stirred in container, While 165 DEG C of blowing temperature will be warming up in container.Afterwards, the dioxy as inorganic system's physical blowing agent is pressed into container Change carbon, the pressure in container is reached 3.5MPa (G：Gauge pressure), kept for 15 minutes at the temperature (i.e. 165 DEG C).Thus, multiple Carbon dioxide is impregnated in resin particle and obtains foaminess composite resin particle.Then, by by foaminess compound resin Grain is discharged under atmospheric pressure together with decentralized medium from container, is derived from expanded beads.
As shown in Figures 1 and 2, the expanded beads 1 obtained in the above described manner contain aliphatic acid 2, and surface 11 is with source In the negative electrostatic charge of the carboxyl of aliphatic acid 2.In this example, if adding aliphatic acid 2 in foaming process, aliphatic acid can be made 2 deviations are present in the surface 11 of expanded beads 1.In addition, Fig. 2 is the schematic diagram in the section of the near surface of expanded beads.
(4) the coating process of antistatic additive
As antistatic additive, prepare the first industrial pharmaceutical (strain) system using cation system surfactant as active ingredient " the CATIOGEN ES-O " (the mass % of active ingredient amount 50) made.Hereinafter, the antistatic additive used in this example is referred to as " anti- Electrostatic agent A ".Then, expanded beads are put into polybag together with antistatic additive, fully rocked after mixing, put together with sack Enter in roller and mix 30 minutes, antistatic additive is thus coated on expanded beads.Count, resist quiet by 100 mass parts of expanded beads The addition of electric agent is 2 mass parts (being 1 mass parts as active ingredient amount).Afterwards, it is 40 DEG C in temperature by expanded beads Dried 12 hours in baking oven.So, the expanded beads for having antistatic additive in surface attachment are obtained.
As shown in figure 3, in expanded beads 1, due to the presence of aliphatic acid 2, antistatic additive 3 is attached to electronegative surface 11.It is believed that antistatic additive 3 can be more securely attached to the surface 11 of expanded beads 1.In addition, Fig. 3 be attached with it is anti-quiet The schematic diagram in the section of the near surface of the expanded beads of electric agent.
The manufacturing condition of the expanded beads obtained in the above described manner is represented in table 3 described later.Specifically, in table 3 In show addition period of aliphatic acid, the species of aliphatic acid, relative to 100 mass parts compound resin aliphatic acid addition Amount, the species of antistatic additive, relative to 100 mass parts expanded beads antistatic additive coated weight.In addition, to expanded beads Apparent density, the adhesion amount of antistatic additive is measured, and further carries out the evaluation of the fillibility to finishing die.Should As a result it is shown in table 3.Assay method and evaluation method are as follows.
" apparent densities of expanded beads "
Using wire netting etc. be about 50ml by the stacking volume of advance weighed weight W (g) coating antistatic additive before Expanded beads sink in the graduated cylinder of the 200ml added with 100ml water, read with water level rise partial response volume V (ml).Obtain W/V and carry out unit conversion, thus calculate the apparent density (kg/m of expanded beads3)。
" adhesion amount of antistatic additive "
The adhesion amount of antistatic additive is determined using Soxhlet extraction device (being specially the B-811 that BUCHI companies manufacture).It is first First, precise expanded beads 1.0g.Then, 1.0g expanded beads are put into line footpath for 0.06mm, the stainless steel of 150 purposes Into wire netting basket in, and be arranged at the top of Soxhlet extraction device.The solvent manufactured to the BUCHI of Soxhlet extraction device bottom 170mL ethanol is added in container.Then, upper temp is set as 80 DEG C, temperature of lower is set as 320 DEG C, use sheathing formula Resistance heater is heated, and carries out the surname extraction of 2 hours.Afterwards, the residue of the dissolving residual in wire netting basket is taken out, It is separated by filtration, and is dried more than 8 hours for 80 DEG C of pressure Reduction Dryer with temperature with the wire netting of 100 mesh.Determine drying The weight W of the dried object obtained afterwards2.By weighing the weight 1.0g and W of expanded beads2Difference calculate extract weight (g).Should Extract weight as antistatic additive adhesion amount.Then, the antistatic additive of expanded beads relative to 100 mass parts is calculated Adhesion amount.
" to the fillibility of finishing die "
The evaluation of fillibility, is carried out by evaluating the mobility of expanded beads.Specifically, as Fig. 4 (a) is illustrated As, first, prepare the cylindric cylinder 9 of the opening portion 92 with a diameter of 35mm.With the cylindric cylinder 9 towards vertical State below direction, cylindric cylinder 9 is arranged at the height H=70mm of table top 90 position.With sealing plate In the state of the opening portion 92 of cylindric cylinder 9 is sealed, volume is filled to cylindrical shape for 600ml expanded beads 1 In cylinder 9.Then, removing sealing plate opens opening portion 92.Thus, expanded beads 1 fall because of deadweight, and such as Fig. 4 (b) illustrates As bright, the mountain heap formed by expanded beads group 100 is formed.Determine the height H of the mountain heap1.Three aforesaid operations are carried out, are calculated Come out of retirement and take up an official post the arithmetic mean of instantaneous value H of stack heightAVE, the average value of mountain stack height is evaluated as " good " for below 60mm situation, will be exceeded 60mm situation is evaluated as " bad ".
(5) mould internal shaping
Then, the expanded beads for being coated with antistatic additive are filled to being that 250mm, width are 200mm, thickness with length In mould for the die cavity of 50mm writing board shape.Then, expanded beads are added by importing vapor into mould Heat makes it mutually merge.Afterwards, made by water cooling after being cooled down in mould, be removed from the molds formed body.Further, will be into Body is being adjusted to load 12 hours in 60 DEG C of baking oven, so that the drying and maintenance of body is formed.So, multiple foaming are obtained The formed body that particle is mutually merged.
For the formed body prepared in the above described manner, shaping pressure when shaping is shown in table 3.In addition, to formed body Bulk density, surface resistivity are measured, and the evaluation of the amalgamation and recovery of body is further formed.This is tied Fruit is shown in table 3.Assay method and evaluation method are as follows.
" bulk density "
By be 23 DEG C in temperature, the appearance and size that relative humidity is formed body after placing 24 hours in the environment of 50% asks Go out volume.In addition, the weight to formed body is measured.Then, with weight divided by appearance and size and unit conversion is carried out, thus Calculate bulk density (kg/m3)。
" amalgamation "
Formed body is bent, it is substantially partially fractureed.The plane of disruption is observed, the hair being internally broken is measured respectively Steep the quantity of the quantity of particle and the expanded beads in interface peel.Then, calculate the expanded beads that are internally broken relative to The expanded beads that are internally broken and interface peel expanded beads total quantity ratio, its is expressed as a percentage Value is used as fusion rate (%).Fusion rate is evaluated as " good " for more than 80% situation, the situation by fusion rate less than 80% is commented Valency is " bad ".
" recovery "
The size on thickness direction by determining formed body carries out recovery evaluation.Specifically, first, measurement from Play the thickness T at the position of 10mm inner side in the end of formed body1In formed body is halved on longitudinal direction and transverse direction The thickness T of center portion2.Then, the thickness ratio T of formed body is calculated2/T1.Then, by thickness ratio T2/T1Commented for more than 0.95 situation Valency is " good ", and the situation less than 0.95 is evaluated as " bad ".
" surface resistivity "
By determining the surface resistivity of formed body, and the evaluation of the antistatic property of body is formed.Surface resistivity, With based on JIS K6271-1:The method of 2015 is measured.When determining, first, from being 23 DEG C, 50%RH in temperature Under the conditions of maintenance 1 day after formed body center near, cut-out length is that 100mm × width is that 100mm × thickness is 25mm's The test film of rectangular-shape.Now, in using the length that is present in cuboid as two surfaces that 100mm × width is 100mm A surface cut out test film for the mode of expanded beads formed body surface (that is, skin surface).Then, using Mitsubishi Chemical " the surface resistivity on Hiresta MCP-HT450 ", the skin surface of determination test piece of company's manufacture.As probe, make " UR100 " manufactured with Mitsubishi Chemical Ind, in 23 DEG C, 50%RH, keeps 500V applied voltage to be carried out under conditions of 30 seconds Determine.It is measured for four different positions, and obtains its average value and coefficient of alteration.In addition, skin surface refers to lead to The surface of expanded beads formed body obtained from crossing mould internal shaping.
In addition, manufacturing condition by changing embodiment 1 etc., and prepare the hair involved by embodiment 1-9, comparative example 1-4 Steep particle, formed body.It can confirm that aliphatic acid deviation is present in surface in embodiment.Represented in table 1 in each embodiment, contrast The species of the aliphatic acid and its derivative (being specially soap) that are used in example.In addition, represented in table 2 each embodiment, The species of the antistatic additive used in comparative example.In addition, represented in table 3 and table 4 each embodiment, the manufacturing condition of comparative example, Evaluation result etc..
Table 1
Table 2
Table 4
As shown in Table 3, the expanded beads of embodiment contain the aliphatic acid of ormal weight.Therefore, the antistatic additive of expanded beads Anchorage it is excellent, to be attached with antistatic additive expanded beads carry out mould internal shaping formed by formed body show be less than 1 ×1012This excellent antistatic properties of Ω.Further, additionally it is possible to reduce the deviation of antistatic property.In addition, being attached with anti- The expanded beads of electrostatic agent, while above-mentioned excellent antistatic property is played, will not also reduce mobility, to shaping mould Fillibility is excellent.In addition, the amalgamation of expanded beads is also very excellent, therefore melting between expanded beads can be obtained by shaping The excellent formed body of conjunction property.That is, the formed body mechanical strength of embodiment.Therefore, obtained using the expanded beads of embodiment The formed body arrived is applied to electronic equipment, the bag of precision equipment as automobile component, liquid crystal panel, solar power generation panel etc. Packaging container etc..
As described above, embodiment is illustrated, but the present invention is not limited to the various embodiments described above, can be not Depart from and carry out various changes in the range of its purport.

Claims (10)

1. a kind of compound resin expanded beads, are with the compound tree of the dipping polymerization styrenic monomers in vinylite Fat is the compound resin expanded beads of substrate resin, it is characterised in that counts, contains by 100 mass parts of the compound resin The aliphatic acid of 0.05-0.7 mass parts.
2. compound resin expanded beads according to claim 1, it is characterised in that the carbon number of the aliphatic acid is 12-22。
3. compound resin expanded beads according to claim 1 or 2, it is characterised in that the aliphatic acid is saturated fat Acid.
4. the compound resin expanded beads according to any one of claim 1-3, it is characterised in that using vinylite as 100 mass parts meters, the compound resin contains to have more than derives from styrenic monomers below 400 mass parts and 1900 mass parts Construction unit.
5. the compound resin expanded beads according to any one of claim 1-4, it is characterised in that the vinylite Principal component be straight-chain low density polyethylene (LDPE).
6. the compound resin expanded beads according to any one of claim 1-5, it is characterised in that the compound resin hair The surface of bubble particle is coated by antistatic additive, is counted using the compound resin expanded beads as 100 mass parts, the antistatic additive Adhesion amount is 0.4-3.5 mass parts.
7. compound resin expanded beads according to claim 6, it is characterised in that the antistatic additive at least containing sun from Subsystem surfactant.
8. compound resin expanded beads according to claim 6, it is characterised in that the antistatic additive contains cation system Surfactant and nonionic surfactants.
9. a kind of compound resin expanded beads formed body, is the compound resin foaming according to any one of claim 6-8 Particle mutually merge formed by formed body, it is characterised in that the surface resistivity of the formed body be less than 1 × 1012Ω。
10. a kind of manufacture method of compound resin expanded beads, has：
The nuclear particle containing vinylite is set to be scattered in the dispersion step of aqueous medium,
In the aqueous medium, in the nuclear particle dipping, polymerizing styrene system monomer and obtain composite resin particle Modified process,
Foaming agent is impregnated in the composite resin particle, and makes what the composite resin particle containing the foaming agent foamed Foamed process,
In the foamed process, aliphatic acid is impregnated in the composite resin particle.
CN201710064269.XA 2016-02-05 2017-02-04 Composite resin expanded particle, composite resin expanded particle molded body, and method for producing composite resin expanded particle Active CN107043513B (en)

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