CN107778519A

CN107778519A - Compound resin expanded beads, antistatic behaviour compound resin expanded beads, compound resin expanded beads formed body

Info

Publication number: CN107778519A
Application number: CN201710724841.0A
Authority: CN
Inventors: 岛昌臣; 高木翔太
Original assignee: JSP Corp
Current assignee: JSP Corp
Priority date: 2016-08-23
Filing date: 2017-08-22
Publication date: 2018-03-09
Also published as: JP2018030923A; JP6855706B2; TW201819495A; TWI749014B

Abstract

【Problem】Compound resin expanded beads, antistatic behaviour compound resin expanded beads and the formed body using the antistatic behaviour compound resin expanded beads of a kind of higher ratio for the phenylethylene resin series composition that can stably obtain in compound resin and the excellent formed body of internal good knitting, antistatic property are provided.【Solution】The antistatic behaviour compound resin expanded beads and its formed body that compound resin expanded beads, expanded beads using the compound resin that dipping polymerization styrenic monomers form in vinylite as substrate resin are coated by antistatic additive.Compound resin contains the composition from vinylite and the composition from styrenic monomers with regulation ratio.Vinylite is straight-chain low density polyethylene (LDPE) and has the mixture of the vinyl copolymer of polar group, and the content of the vinyl copolymer with polar group in vinylite is adjusted in defined scope.The water vapor adsorption amount of compound resin expanded beads is 0.50cm³/ more than g.

Description

Compound resin expanded beads, antistatic behaviour compound resin expanded beads, compound resin hair Steep shaping particles body

Technical field

The present invention relates to using the compound resin that dipping polymerization styrenic monomers form in vinylite as base material tree Compound resin expanded beads, antistatic behaviour compound resin expanded beads and the antistatic behaviour compound resin expanded beads phase of fat Mutually merge the formed body formed.

Background technology

The mould internal shaping body of compound resin expanded beads containing vinylite composition and phenylethylene resin series composition (that is, compound resin expanded beads formed body) is as electronic equipment, the packing container of the part of precision equipment, amortizing packaging material And it is widely used.In the formed body of this purposes, in order to prevent the attachment of dust, by electric discharge etc. overcurrent generation and Caused electrical damage, and typically assign antistatic property.

As the method for obtaining compound resin expanded beads, such as known there are as below methods.Specifically, first, containing There are dipping, polymerizing styrene system monomer in the nuclear particle of vinylite composition, be derived from containing vinylite composition Compound resin with phenylethylene resin series composition is the composite resin particle of substrate resin.Then, soaked in composite resin particle Stain foaming agent simultaneously makes the composite resin particle foam, thus, it is possible to obtain compound resin expanded beads (with reference to patent document 1-3). As above-mentioned vinylite, it can be used straight-chain low density polyethylene (LDPE), vinyl-vinyl acetate copolymer etc. that there is polar group Vinyl copolymer, their mixture etc. of group.

In addition, as the method that antistatic property is assigned to expanded beads formed body, it is general to use addition by surface-active The method of the antistatic additive of the compositions such as agent.It is known that have to composite resin particle impregnate volatile foaming agent when or The method of antistatic additive is impregnated after dipping volatile foaming agent.In addition, it is also known that have the coating on compound resin expanded beads anti- The method of electrostatic agent.

In the method that antistatic additive is impregnated when impregnating volatile foaming agent, probably it can cause resin particle because of antistatic additive The heat resistance of expanded beads reduces when exceedingly being plastified, and then making shaping, formed body deformation, can probably make expanded beads each other it Between amalgamation reduce.Therefore, such as patent document 4, the cation that ormal weight is coated on compound resin expanded beads is developed It is the method for antistatic additive.

Prior art literature

Patent document

1 International Publication No. of patent document 2007/138916

The Japanese Unexamined Patent Publication 2015-189911 publications of patent document 2

The Japanese Unexamined Patent Publication 2005-97555 publications of patent document 3

The Japanese Unexamined Patent Publication 2015-81274 publications of patent document 4

The content of the invention

The problem to be solved in the present invention

On the other hand, in order to maintain compound resin expanded beads formed body toughness and restoration while, further Rigidity is improved, develops the technology for the ratio for improving the phenylethylene resin series composition in compound resin.But such as patent document 1- Compound resin expanded beads disclosed in 3 are such, have polar group using containing vinyl-vinyl acetate copolymer etc. In the case that the vinylite of vinyl copolymer is as nuclear particle, if improving the phenylethylene resin series composition in compound resin Ratio, then the amalgamation of expanded beads probably can reduce.In addition, in this case, reducing the ethene with polar group In the case of the content of based copolymer, although the amalgamation of expanded beads is in improved trend, but still there is further improvement Leeway.In the case of the content for further reducing the vinyl copolymer with polar group on this basis, antistatic additive Anchorage probably can reduce.Accordingly, it is difficult to the ratio for obtaining the phenylethylene resin series composition in compound resin is higher and amalgamation The excellent expanded beads with the anchorage of antistatic additive.

In addition, as described in patent document 4, the method for coating antistatic additive on compound resin expanded beads In, that the anchorage of antistatic additive is insufficient be present, according to heating condition during mould internal shaping, such as because as steam Heat medium, the antistatic additive being attached on expanded beads is possible to partly to flow out, the adhesion amount of antistatic additive according into The position of body difference and reduce etc., be thus difficult to stably obtain the formed body with the antistatic property expected.

The present invention be in view of above-mentioned background and complete, its object is to provide stably to obtain in compound resin The compound resin hair for the formed body that the ratio of phenylethylene resin series composition is higher and internal good knitting, antistatic property are excellent Steep particle, antistatic behaviour compound resin expanded beads and the formed body using the antistatic behaviour compound resin expanded beads.

The means used to solve the problem

The mode of the present invention is a kind of compound resin expanded beads, and it is with the dipping polymerization benzene second in vinylite The compound resin that alkene monomer forms is substrate resin,

Above-mentioned compound resin contains the composition from above-mentioned vinylite more than 5 mass % and less than 20 mass % With the composition from above-mentioned styrenic monomers more than 80 mass % and below 95 mass %, wherein, both adds up to 100 mass %,

Above-mentioned vinylite is the mixing of straight-chain low density polyethylene (LDPE) and the vinyl copolymer with polar group Thing,

The content of the above-mentioned vinyl copolymer with above-mentioned polar group in above-mentioned vinylite is 1-45 matter Measure %,

The water vapor adsorption amount of above-mentioned compound resin expanded beads is 0.50cm³/ more than g.

The another way of the present invention is a kind of antistatic behaviour compound resin expanded beads, above-mentioned compound resin expanded beads Surface is covered by the antistatic additive containing cation system surfactant.

The another mode of the present invention is a kind of compound resin expanded beads formed body, and it is above-mentioned antistatic behaviour compound resin The formed body that expanded beads mutually merge, its surface resistivity is less than 1 × 10¹²Ω。

Invention effect

Above-mentioned compound resin expanded beads (following, to be properly termed as " expanded beads "), with relative to vinylite with The compound resin that higher mixing ratio dipping polymerization styrenic monomers form is substrate resin, contains the upper of above-mentioned specified quantitative Specific vinyl copolymer is stated, and steam vapour amount, the i.e. water vapor adsorption amount that expanded beads can be adsorbed is adjusted to above-mentioned More than setting, the vinylite contains straight-chain low density polyethylene (LDPE) and the vinyl copolymer with polar group. Therefore, even for example coating antistatic additive on expanded beads, expanded beads also can fully adsorb holding antistatic additive, The outflow of antistatic additive when can suppress to shape, therefore the compound tree stably with good antistatic property can be obtained Fat expanded beads formed body (following, to be properly termed as " formed body ").Even the in addition, styrene in using compound resin Be resin component ratio it is higher and containing with polar group vinyl copolymer vinylite in the case of, into The inside fusion of body, i.e., the amalgamation between expanded beads is also very excellent.Therefore, formed body can have been given play to based on second Alkene system resin, phenylethylene resin series composition etc. the original excellent compression rigidity of compound resin and resistance to deflection equal strength it is special Property.In addition, above-mentioned antistatic behaviour compound resin expanded beads can also give play to the effect same with above-mentioned expanded beads.

In addition, antistatic behaviour compound resin expanded beads mutually merge, surface resistivity is less than 1 × 10¹²Ω's Not only antistatic property is excellent for formed body, and because the expanded beads for forming formed body fully merge each other, therefore Compression rigidity as described above and resistance to deflection equal strength characteristic are also very excellent.Therefore, using the foaming of antistatic behaviour compound resin Grain and obtain formed body be preferably applied to the electronic equipments such as liquid crystal panel, solar panel or precision equipment part bag The purposes such as packaging container, amortizing packaging material.

Embodiment

Then, the preferred embodiment of above-mentioned expanded beads is illustrated.Expanded beads, such as be used on its surface Coat purposes of antistatic additive etc..The expanded beads of this purposes, it may be said that have on surface for the anti-quiet of antistatic additive attachment Electric agent contact surface.

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 make in finishing die mutually to merge between composite resin particle, be derived from the formed body of intended shape.

Expanded beads are using the compound resin that dipping polymerization styrenic monomers form in vinylite as substrate resin. In this manual, as described above, compound resin refers to what in vinylite dipping, polymerizing styrene system monomer etc. formed Resin, refer to the resin containing the composition from vinylite and the composition from styrenic monomers.From benzene The composition of vinyl monomer, for example, phenylethylene resin series, generally, the main component from the composition of styrenic monomers is The phenylethylene resin series that styrenic monomers are polymerized.In addition, in the polymerization of styrenic monomers etc., not only styrene It is the polymerization between monomer, connecing for styrenic monomers can also occurs on the polymer chain for forming vinylite sometimes Branch polymerization.In this case, the benzene that compound resin is not only polymerized containing vinylite composition and styrenic monomers Vinylite composition, also further there is vinylite composition (that is, the PE-g-PS of styrenic monomers containing being graft-polymerized Composition).In addition, in the polymerization of styrenic monomers, it some times happens that the crosslinking of vinylite, in this case, In compound resin, as vinylite composition, including uncrosslinked vinylite and the vinylite of crosslinking.Therefore, Compound resin is with the hybrid resin for forming the phenylethylene resin series melting mixing after the vinylite after polymerizeing and polymerization Different concepts.

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 composition from vinylite in compound resin, there is the tough of formed body Property, restoration improve, but the trend rigidly reduced.On the other hand, the composition from styrenic monomers, i.e. structure are being improved Into the composition from styrenic monomers in the polymer chain of compound resin ratio in the case of, then have the firm of formed body Property improve, but toughness, restoration reduce trend.

In above-mentioned expanded beads, compound resin, which contains more than 5 mass % and less than 20 mass %, derives from ethene system The composition of resin and more than 80 mass % and below 95 mass % from styrenic monomers composition (wherein, both Add up to 100 mass %.), therefore can obtain while toughness, restoration is maintained, the especially excellent formed body of rigidity.From From the viewpoint of the rigidity for further improving formed body, more preferably compound resin contains derives from ethene system below 19 mass % (wherein, both add up to 100 matter to the composition of resin and more than 81 mass the % composition from styrenic monomers Measure %.), further preferably below 18 mass % from the composition of vinylite and more than 82 mass % source In the compositions of styrenic monomers, (wherein, both add up to 100 mass %.).In addition, in order to further improve formed body Toughness, restoration, more preferably compound resin contain the compositions and 90 mass % from vinylite more than 10 mass % (wherein, both add up to 100 mass % to the following composition from styrenic monomers.), further preferably 11 More than quality % from the composition of vinylite and below 89 mass % composition (its from styrenic monomers In, both adds up to 100 mass %.).Further, in this manual, related to the upper limit and lower limit of number range is preferred Scope, more preferably scope, further preferred scope can determine from whole combinations of the upper limit and lower limit.

Vinylite contains straight-chain low density polyethylene (LDPE) and the vinyl copolymer with polar group.In this explanation In book, straight-chain low density polyethylene (LDPE) is hereinafter properly termed as " LLDPE ", the ethene system with polar group is copolymerized Thing is hereinafter properly termed as " polar copolymer ".Optimal ethylene system resin using straight-chain low density polyethylene (LDPE) as mainly into Point, specifically, the content of the straight-chain low density polyethylene (LDPE) in vinylite is preferably more than 50 mass %, more preferably More than 55 mass %, more preferably more than 60 mass %.Further, as except straight-chain low density polyethylene (LDPE), polar co Vinylite beyond thing, it can illustrate as branched low density polyethylene (LDPE), high density polyethylene (HDPE).

Straight-chain low density polyethylene (LDPE) preferably has following construction：Polyethylene Chain and carbon number with straight chain are 2-6 Short chain shape side chain.Specifically, such as ethylene-butene copolymer, ethylene-hexene co-polymers, ethene-pungent can be enumerated as Alkene copolymer etc., in particular it is preferred to be the straight-chain low density polyethylene (LDPE) being polymerized using metallocene system polymerization catalyst. In this case, the vinylite composition in compound resin and the phenylethylene resin series that styrenic monomers are polymerized into / compatibility further improve, it is possible to increase the toughness of formed body.Further, the density of straight-chain low density polyethylene (LDPE) is excellent Select substantially 0.910-0.925g/cm³。

The melt mass flow rate (that is, MFR) of LLDPE under conditions of temperature is 190 DEG C, load is 2.16kg, from From the viewpoint of improving foaminess, preferably 0.5-4.0g/10 minutes, more preferably 1.0-3.0g/10 minutes.Further, LLDPE MFR Deng vinylite, vinyl-vinyl acetate copolymer isopolarity copolymer is to be based on JIS (Japanese Industrial Standards) Value under conditions of K7210-1 (2014) is determining, temperature is 190 DEG C, load is 2.16kg.In addition, as measurement apparatus, Melt index apparatus (such as model L203 of precious industrial (strain) manufacture etc.) can be used.

In addition, LLDPE fusing point Tm is preferably 80 DEG C -115 DEG C.In this case, styrenic monomers can be filled Point it is impregnated in vinylite, the destabilization of suspended system during therefore, it is possible to prevent polymerization.As a result, it can obtain Have the formed body of the excellent rigidity of phenylethylene resin series and the excellent bonding strength of vinylite concurrently with higher level.From From the viewpoint of same, LLDPE fusing point (Tm) is preferably 85-110 DEG C.Further, fusing point Tm can be based on JIS K7121 (1987), (DSC) is determined by Differential Scanning Calorimeter and is measured with melting peak temperature.

In addition, vinylite contains polar copolymer.As polar copolymer, ethane-acetic acid ethyenyl ester can be used Copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid alkyl ester copolymer, ethylene-methacrylic acid copolymer, ethene- One or more of methacrylate copolymer etc..As the polar group in polar copolymer, such as can be enumerated as The functional groups such as carboxyl, hydroxyl, carbonyl, nitro, amino, sulfo group., it can be said that by making compound resin contain polar copolymer, energy Enough improve the hydrophily of expanded beads, by increasing capacitance it is possible to increase the water vapor adsorption amount of expanded beads described later.As a result, it can be said that The outflow of antistatic additive when can improve the anchorage of antistatic additive so as to suppress shaping.As polar group, preferably have Carbonyl.

The content of polar copolymer in vinylite is 1-45 mass %.In the case of more than 45 mass %, carry The crosslinking of vinylite easily occurs during dipping polymerization, the amalgamation between expanded beads can probably reduced.Further , in this case, the content of the LLDPE in vinylite will necessarily be made reduce, therefore probably can make the curved of formed body Bent energy to fracture becomes insufficient.From the viewpoint of improving amalgamation and improving bend fracture energy, in vinylite The content of polar copolymer be preferably below 35 mass %, more preferably below 30 mass %.On the other hand, in polar co In the case that the content of thing is less than 1 mass %, it is impossible to improve the hydrophily on the surface of expanded beads, can probably make the guarantor of antistatic additive Holding property becomes insufficient.From the viewpoint of the further retentivity for improving antistatic additive, the polar co in vinylite The content of thing is preferably more than 2 mass %, more preferably more than 5 mass %.

The content of polar copolymer in compound resin is preferably 0.1-7 mass %.In this case, can be further Improve the bonding strength of formed body and further suppress the cracking of formed body, and can further improve the anti-quiet of expanded beads The retentivity of electric agent.From the viewpoint of the further cracking for suppressing formed body, polar copolymer in compound resin contains Amount is more preferably below 5 mass %, more preferably below 4.5 mass %.On the other hand, foaming is improved from further From the viewpoint of the retentivity of the antistatic additive of grain, the content of the polar copolymer in compound resin is more preferably 0.5 mass % More than, more preferably more than 1 mass %.

The content of the construction unit from the monomer containing polar group in polar copolymer is preferably 10-50 matter Measure %.In this case, the hydrophily of expanded beads is improved while mechanical properties when being formed as formed body can not be damaged, and The anchorage of antistatic additive can further be improved.From the viewpoint of the further outflow for suppressing antistatic additive, polar co The content of the construction unit from the monomer containing polar group in thing is more preferably 15-50 mass %.Further, polarity is total to The composition (that is, construction unit) from the monomer containing polar group in polymers, such as in polar copolymer be ethene-second In the case of vinyl acetate copolymer, for from the composition of vinyl acetate.

Polar copolymer is preferably vinyl-vinyl acetate copolymer.In this case, can obtain with higher level Have the formed body of the excellent rigidity of phenylethylene resin series and the excellent bonding strength of vinylite concurrently.Further, ethylene-acetate second Enoate copolymer is the polymer for obtaining the copolymerization such as polymerizeing by high-pressure free radical of ethene and vinyl acetate.Ethene- Vinyl acetate copolymer typically has the long-chain being made up of Polyethylene Chain and derives from vinyl acetate from the long chain branches Short chain.

The MFR of vinyl-vinyl acetate copolymer is preferably 1-120g/10 minutes (190 DEG C, load 2.16kg).At this In the case of kind, the compound resin expanded beads shaping for making compound resin expanded beads mould internal shaping and being formed can be further improved The fusion rate of body, it can further improve the toughness of compound resin expanded beads formed body.From the same viewpoint, ethene- The MFR (190 DEG C, load 2.16kg) of vinyl acetate copolymer is more preferably 2-30g/10 minutes, more preferably 2- 10g/10min。

Water vapor adsorption amount per 1g expanded beads is 0.50cm³/ more than g.In water vapor adsorption amount less than 0.50cm³/g In the case of, the anchorage of the antistatic additive of expanded beads becomes insufficient.As a result, for example in shaping, antistatic additive holds Easily outflow, the antistatic property of formed body can probably become deficiency.From the viewpoint of the anchorage for the antistatic additive for improving expanded beads Set out, the water vapor adsorption amount of expanded beads is preferably 0.60cm³/ more than g, more preferably 0.70cm³/ more than g, it is further excellent Elect 0.80cm as³/ more than g.In addition, the water vapor adsorption amount of expanded beads is preferably substantially 4cm³/ below g.

Using dipping polymerization styrenic monomers form in vinylite compound resin as the conventional of substrate resin Expanded beads substantially have hydrophobicity, thus, for example the anchorage when making there is hydrophilic antistatic additive to adhere to is relatively low. Heating condition when therefore, according to conventional expanded beads progress mould internal shaping, it is possible to because of the steam as heating medium Deng and the antistatic additive for being attached to expanded beads is partly departed from, the adhesion amount of antistatic additive according to the position of formed body not Reduce together etc., thus it is difficult to stably obtain the formed body with the antistatic property expected.In addition, in order to improve foaming The water vapor adsorption amount of particle, in the more second of the content using the polar copolymer as shown in above-mentioned patent document 1-3 In the case that alkene system resin is as nuclear particle, because of the toughness reduction of vinylite itself, the easy friendship for producing vinylite Join and reduce the amalgamation of expanded beads, thus there is a possibility that the physical property such as the compression rigidity of formed body, resistance to deflection reduces.Enter One step, in the method shown in patent document 1-3, in the case where improving the mixing ratio of styrenic monomers, in core The styrenic monomers amount of dipping polymerization increases in grain, therefore, it becomes difficult to be uniformly impregnated with styrenic monomers, in resin The skin section phenylethylene resin series composition of particle increases, and thus can probably make amalgamation, the anchorage of antistatic additive of expanded beads (water vapor adsorption amount) reduces.

On the other hand, such as by manufacture method described later and the expanded beads disclosed in this specification for obtaining, although The ratio of the composition from styrenic monomers in compound resin is higher and relative to the polar co of compound resin total amount The content of thing is less, but because the water vapor adsorption amount of expanded beads is higher, therefore the amalgamation of expanded beads can maintained In the state of improve antistatic additive anchorage.Therefore, according to above-mentioned expanded beads, can obtain can take into account excellent machinery The formed body of physical property and antistatic property.

Further, it is believed that by manufacturing above-mentioned expanded beads by manufacture method described later, with conventional expanded beads Compare, increase the amount of the polar copolymer on surface.It is accordingly, it is believed that total relative to compound resin without exceedingly increasing Mixing ratio, the content of polarity based component of the polar copolymer of amount, also, although the content of polar copolymer is less, also can Enough make the near surface hydrophiling of expanded beads.

In this manual, the water vapor adsorption amount of expanded beads is the steam vapour amount that expanded beads can adsorb.That is, exist On adsorption isotherm when temperature determined using vapor sorption amount determining device, expanded beads are 25 DEG C, maximum relative pressure Water vapor adsorption amount under power is the water vapor adsorption amount of expanded beads.Chatted in specific embodiment of the assay method below State.

Compound resin contains the phenylethylene resin series composition that styrenic monomers are polymerized.Further, in this manual, Sometimes by form phenylethylene resin series composition 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 such as can thering is following styrene to spread out with styrene copolymerized monomer Biology, other vinyl monomers etc..

As styrene derivative, can be enumerated as α-methylstyrene, o-methyl styrene, a methyl styrene, to first Base styrene, p -ethyl-styrene, 2,4- dimethyl styrenes, to methoxy styrene, to n-butylstyrene, to the tert-butyl group Styrene, ortho-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,4,6- phenylstilbene bromides, divinylbenzene, styrene sulphur Acid, SSS etc..These, which can be used alone, can also use two or more mixtures.

In addition, as other vinyl monomers, acrylate, methacrylate, acrylic acid, metering system can be enumerated as Acid, the vinyl compound containing hydroxyl, the vinyl compound containing itrile group, organic acid vinyl compound, olefinic compound Thing, diolefin compound, vinyl halides based compound, meta-halo ethylene based compound, maleimide compound etc..These ethene Base monomer, can be used alone can also use two or more mixtures.

As acrylate, such as there are methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, propylene Acid -2- ethylhexyls etc..As methacrylate, such as there are methyl methacrylate, EMA, metering system Propyl propionate, butyl methacrylate, methacrylic acid -2- ethylhexyls etc..These, which can be used alone, can also use two kinds Mixture above.

As the vinyl compound containing hydroxyl, such as there are hydroxy-ethyl acrylate, hydroxypropyl acrylate, methacrylic acid Hydroxyl ethyl ester, hydroxy propyl methacrylate etc..As the vinyl compound containing itrile group, such as there are acrylonitrile, methacrylonitrile Deng.As organic acid vinyl compound, such as there are vinyl acetate, propionate etc..These, which can be used alone, also may be used To use two or more mixtures.

As olefin(e) compound, such as there are ethene, propylene, 1- butylene, 2- butylene etc..As diolefin compound, such as have Butadiene, isoprene, chlorobutadiene etc..As vinyl halides based compound, such as there are vinyl chloride, bromine ethene etc..As inclined Vinyl halides based compound, such as have vinylidene chloride etc..As maleimide compound, such as there are N- benzyl maleimides Amine, N- methylycaconitine imines etc..These, which can be used alone, can also use two or more mixtures.

From improve foaminess from the viewpoint of, be preferably styrene as styrenic monomers, or and with styrene with Acrylic monomer.From it is further improve foaminess from the viewpoint of, preferably and with styrene and butyl acrylate.In this feelings Under condition, the content of the construction unit from butyl acrylate in compound resin is overall relative to compound resin, is preferably 0.5-10 mass %, more preferably 1-8 mass %, more preferably 2-5 mass %.

In addition, without prejudice to the present invention effect in the range of, compound resin can contain except above-mentioned vinylite into Point, beyond phenylethylene resin series composition, other resin components.As other resin components, for example, poly- methyl-prop can be enumerated as E pioic acid methyl ester, makrolon, polyvinyl alcohol etc..In this case, the content of other resin components, with compound resin (bag Including including other resin components) counted for 100 mass %, preferably below substantially 10 quality %, more preferably below 5 mass %, More preferably below 3 mass %.

Antistatic additive can be made to be attached to the surface of expanded beads.The adhesion amount of antistatic additive, although additionally depending on is made The species of antistatic additive, still, counted by 100 mass parts of expanded beads, preferably 0.4-3.5 mass parts.In this feelings Under condition, confluent reduction can be further prevented while antistatic property is fully obtained.From more fully obtaining From the viewpoint of antistatic property, counted by 100 mass parts of expanded beads, the adhesion amount of antistatic additive is more preferably 0.5 mass More than part, more preferably more than 0.6 mass parts.In addition, from can further prevent the viewpoint of confluent reduction from going out Hair, the adhesion amount of antistatic additive is more preferably below 2.7 mass parts, more preferably below 2.5 mass parts.

As antistatic additive, such as cation system surfactant, nonionic surfactants, both sexes table can be used Face activating agent etc..These surfactants can be used alone or multiple combinations use.As antistatic additive, such as can profit With various commercially available products.

As cation system surfactant, such as octyldimethyl ethyl ammonium sulfovinate, dodecane can be used Base dimethyl ethyl QAE quaternary aminoethyl sulfate, didecyl Dimethy ammonium chloride, tetraalkylammonium salt, trialkyl benzyl ammonium salt etc.. As nonionic surfactants, for example, can use hydroxy alkyl amine, hydroxy alkyl monoether amine, polyoxyalkylene alkyl amines, Fatty acid glyceride, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether etc..As anion system surfactant, such as can be with Use alkylsulfonate, alkylbenzenesulfonate, alkylphosphonic etc..

Antistatic additive preferably at least contains cation system surfactant.In this case, antistatic additive is easier to Set on expanded beads, it can further improve antistatic property.It is believed that the surface that this is due to expanded beads carries and born Electrostatic charge, therefore the antistatic additive containing cation system surfactant becomes prone to the reason of set.It is even moreover, few The antistatic additive of amount can also show excellent antistatic property, so as to further prevent it is confluent reduce, to Reduction of the fillibility of mould etc..

In addition, the foaming determined by using the infrared total reflection absorption measurement method (that is, ATR methods) of Ge (that is, germanium) prism Wave number 1740cm in the infrared absorption spectroscopy on the surface of particle^-1Place and wave number 2850cm^-1The dulling luminosity ratio at place D_1740/2850-GePreferably more than 0.2.In other words, in the above-mentioned compound resin foaming of the ATR methods measure by using Ge prisms In the infrared absorption spectroscopy on the surface of grain, in wave number 1740cm^-1The absorbance D at place_1740-Ge, wave number 2850cm^-1The absorbance at place D_2850-GeAnd dulling luminosity ratio D_1740/2850-GeIt is preferred that meet the relation of following Formulas I.

D_1740/2850-Ge=D_1740-Ge/D_2850-Ge>=0.2 ... (Formulas I)

According to the consideration, in the case where the polar group in as polar copolymer contains carbonyl, by meeting above-mentioned formula, The amount of the carbonyl on expanded beads surface is enough, therefore more reliably improves the hydrophily on expanded beads surface.As a result, It is believed that the anchorage of antistatic additive can be more reliably improved, it is antistatic when can more reliably suppress to shape The outflow of agent.From the viewpoint of the further hydrophily for improving expanded beads surface, the absorbance on the surface of expanded beads Compare D_1740/2850-GePreferably more than 0.23, more preferably more than 0.25.In addition, dulling luminosity ratio D_1740/2850-GeIt is preferably big Cause less than 0.5.Further, wave number 2850cm^-1The absorbance D at place₂₈₅₀It is derived from vinylite and phenylethylene resin series The height of the peak value of stretching vibration between the C-H of the methylene contained in both sides, wave number 1740cm^-1The absorbance D at place₁₇₄₀Come Come from mainly containing in the polar copolymer of the composition of vinyl acetate etc. in vinyl-vinyl acetate copolymer Carbonyl C=O stretching vibration peak value height.

In the manufacture method of expanded beads described later, by by the dipping temperature of styrenic monomers, in polymerization initial stage The styrenic monomers (that is, the first monomer) of input and the ratio of nuclear particle adjust to proper range and fill styrenic monomers Divide and be impregnated in vinylite nuclear particle, can be by dulling luminosity ratio D_1740/2850-GeIt is adjusted to more than above-mentioned setting.Its result It is that, although less relative to the content of the polar copolymer of compound resin total amount, can also increase the skin section of expanded beads The amount of polar copolymer.

The surface of the above-mentioned compound resin expanded beads determined by using the ATR methods of ZnSe (that is, zinc selenide) prism Wave number 1740cm in infrared absorption spectroscopy^-1Place and wave number 2850cm^-1The dulling luminosity ratio D at place_{1740/2850-ZnSe}With above-mentioned extinction Degree compares D_1740/2850-GeThe ratio between D_1740/2850-Ge/D_{1740/2850-ZnSe}Preferably greater than 1.In other words, in the ATR by using ZnSe prisms In the infrared absorption spectroscopy on the surface of the above-mentioned compound resin expanded beads of method measure, it is preferable that wave number 1740cm^-1The extinction at place Spend D_1740-ZnSe, wave number 2850cm^-1The absorbance D at place_2850-ZnSeAnd dulling luminosity ratio D_{1740/2850-ZnSe}Meet following formula II's Relation, above-mentioned dulling luminosity ratio D_1740/2850-GeWith above-mentioned dulling luminosity ratio D_{1740/2850-ZnSe}Meet following formula III relation.

D_{1740/2850-ZnSe}=D_1740-ZnSe/D_2850-ZnSe... (Formula II)

D_1740/2850-Ge/D_{1740/2850-ZnSe}>1 ... (formula III)

According to the consideration, in the case where the polar group in as polar copolymer contains carbonyl, by meeting above-mentioned formula, The amount of the carbonyl more near abutment surface of expanded beads is more, therefore more reliably improves the hydrophily on expanded beads surface. As a result, it is possible to think, the anchorage of antistatic additive can be more reliably improved, when can more reliably suppress shaping Antistatic additive outflow.From the viewpoint of the further hydrophily for improving expanded beads surface, dulling luminosity ratio D_1740/2850-GeWith dulling luminosity ratio D_{1740/2850-ZnSe}The ratio between D_1740/2850-Ge/D_{1740/2850-ZnSe}More preferably more than 1.1, further Preferably more than 1.2.In addition, dulling luminosity ratio D_1740/2850-GeWith dulling luminosity ratio D_{1740/2850-ZnSe}The ratio between D_1740/2850-Ge/ D_{1740/2850-ZnSe}Preferably below substantially 5.

In ATR methods, the difference according to prism material can be utilized and the different property of refractive index, changed for sample Infrared ray slips into depth and is measured.Specifically, in the case where using Ge as prism material, with using ZnSe's Situation is compared, and infrared ray slips into depth shallower, therefore being capable of more entering by the infrared absorption spectroscopy of skin section to expanded beads Row measure.Further, using in the case of Ge, can obtaining being in the range of 0.2-0.5 μm probably from most surface to depth Infrared absorption spectroscopy, using in the case of ZnSe, can obtaining being in the range of 0.6-1.5 μm probably from most surface to depth Infrared absorption spectroscopy.

In the manufacture method of expanded beads described later, by by dipping temperature (that is, the dipping polymerization of styrenic monomers Temperature), styrenic monomers (that is, the first monomer) and the nuclear particle of polymerization initial stage input ratio adjust to proper range and Styrenic monomers are made to be sufficiently impregnated in vinylite nuclear particle, can be by dulling luminosity ratio D_1740/2850-GeAnd ratio D_1740/2850-Ge/D_{1740/2850-ZnSe}It is adjusted to more than above-mentioned setting.

The content ratio of the composition insoluble in dimethylbenzene of expanded beads is preferably less than 20%.In this case, it is multiple The content of the vinylite of crosslinking in resin is less, it is possible to increase the foaminess during manufacture of expanded beads described later, The formability during manufacture of formed body.Further, the content ratio of the composition insoluble in dimethylbenzene is hereinafter properly termed as " XY gel contents ".From the viewpoint of further raising foaminess, formability, the XY gel contents of expanded beads are more preferably 18% Below.The assay method of the XY gel contents of expanded beads describes in the embodiment below.

The XY gel contents on the top layer of expanded beads are preferably less than 25%.In such a case, it is possible to think, due to foaming The content of the vinylite composition of the crosslinking on the top layer of particle is less, therefore can improve the fusion between expanded beads Property.I.e., it is possible to think, in above-mentioned expanded beads, although less relative to the content of the polar copolymer of compound resin total amount, But hydrophilic polar copolymer can be improved by containing on top layer, and XY gel contents (the ethene system being specially crosslinked on top layer The content of resin component) it is less.Therefore, expanded beads can have the excellent anchorage and hair of antistatic additive concurrently with higher level Steep the excellent amalgamation between particle.The assay method of the XY gel contents on the top layer of expanded beads is in embodiment below Middle narration, the skin section of the formed body formed by the fusion of multiple expanded beads is cut, is made skin section sample, and to the skin section The XY gel contents of sample are measured, and thus obtain the XY gel contents on the surface of expanded beads.It is confluent from further improving Viewpoint is set out, and the XY gel contents on the top layer of expanded beads are preferably less than 23%, and more preferably less than 21%, more preferably Less than 20%.

From the viewpoint of the light weight and mechanical properties when taking into account formability, being formed as formed body, the heap of expanded beads Product density is preferably substantially 5kg/m³More than, more preferably 10kg/m³More than.On the other hand, the bulk density of expanded beads is preferred For substantially 200kg/m³Hereinafter, more preferably 100kg/m³Below.

In addition, from the viewpoint of light weight and mechanical property is taken into account, formed body that expanded beads mutually merge Apparent density is preferably substantially 5kg/m³More than, more preferably 10kg/m³More than.On the other hand, the apparent density of formed body is preferred For substantially 200kg/m³Hereinafter, more preferably 100kg/m³Below.

The surface resistivity for the formed body that expanded beads mutually merge is preferably less than 1 × 10¹²Ω.If sheet resistance Rate within the above range, then can give full play to packing container, the amortizing packaging material institute of liquid crystal panel, solar panel etc. It is required that antistatic property.The surface resistivity of formed body is more preferably 7 × 10¹¹Below Ω, more preferably 5 × 10¹¹Ω Below.

Then, the embodiment of the manufacture method of expanded beads is illustrated.By carrying out dispersion step, modified process And foamed process and obtain expanded beads.Each operation is described in detail below.

In dispersion step, the vinylite containing LLDPE and polar copolymer is used as nuclear particle.Nuclear particle The additions such as other resins, foaming nucleation agent, bubble conditioning agent, colouring agent, lubricant, scattered footpath expansion agent can further be contained Agent.Nuclear particle, complex can be carried out by the way that above-mentioned additive added as needed etc. is coordinated with vinylite Grain refined is carried out after melting mixing and is manufactured.Melting mixing can be carried out by extruder.In order to be uniformly kneaded, preferably Extruded again after resin is mixed in advance.The mixing of resin, such as Henschel mixer, Ribbon Blender, V-type can be used Mixer, sieve lattice mixer () etc. mixer mixer is carried out.Melting mixing, preferably use such as Dulmadge The single screw extrusion machine for possessing screw rod or double screw extruder of the high decentralized such as type, Maddock types, Unimelt types is carried out.

The granulation of nuclear particle, for example, by by the complex after melting mixing with extrusions such as extruders and meanwhile cut-out come Carry out.It is granulated, such as can be carried out by wire cutting mode, imderwater cutting mode, thermal cutting mode etc..

In dispersion step, the dispersion liquid that nuclear particle is scattered in aqueous medium can be obtained.As aqueous medium, such as 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.As suspension, for example, can use tricalcium phosphate, hydroxyapatite, Magnesium pyrophosphate, magnesium phosphate, aluminium hydroxide, iron hydroxide, titanium hydroxide, magnesium hydroxide, barium phosphate, calcium carbonate, magnesium carbonate, carbonic acid The microgranular inorganic suspension such as barium, calcium sulfate, barium sulfate, talcum, kaolin, bentonite.Also, such as it can also use poly- Organic suspension such as vinylpyrrolidone, polyvinyl alcohol, ethyl cellulose, hydroxypropyl methyl cellulose.Preferably tricalcium phosphate, Hydroxyapatite, magnesium pyrophosphate.These suspensions may be used singly or in combination of two or more.

The usage amount of suspension, (specially include containing reaction product with the aqueous medium in suspended polymerization system 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.By the way that suspension is set in above range, in modified process, polystyrene list can be made Body is stably suspended, and the particle diameter distribution for the composite resin particle that can suppress to obtain after modified process broadens.

Can be with the dispersant such as addition surfactant in hydrotropism's medium.As surfactant, such as preferably using the moon Ionization series surfactant, nonionic surfactants.These surfactants can be used alone or multiple combinations use.

As anion surfactant, such as sodium alkyl sulfonate, sodium alkyl benzene sulfonate, dodecyl sulphate can be used Sodium, alpha-olefin sodium sulfonate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate etc..

As nonionic surfactants, such as ethylene nonyl phenyl ether, polyoxyethylene lauryl can be used Base ether etc..

In addition, in an aqueous medium, as needed, such as can 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 formed.It is in addition, more excellent in order to obtain toughness, mechanical strength Formed body, preferably add water-soluble polymerization inhibitor in an aqueous medium.As water-soluble polymerization inhibitor, such as nitrous acid can be used Sodium, potassium nitrite, ammonium nilrite, L-AA, citric acid etc..Benzene second near the most surface for reducing composite resin particle From the viewpoint of the amount of alkene system resin, the addition of water-soluble polymerization inhibitor, (specially included containing reaction generation with aqueous medium Whole water in system including the water of the slurry of thing etc.) it is 100 mass parts meters, preferably 0.001-0.1 mass parts, it is more excellent Elect 0.005-0.06 mass parts as.

In modified process, in an aqueous medium, dipping, polymerizing styrene system monomer in nuclear particle.Further, styrene It is the polymerization of monomer etc., can be carried out in the presence of polymerization initiator.In this case, sometimes in styrenic monomers Deng polymerization while produce vinylite crosslinking.In addition, crosslinking agent can be used together as needed.Trigger using polymerization When agent, crosslinking agent, preferably polymerization initiator, crosslinking agent are dissolved in styrenic monomers in advance.

As polymerization initiator, the material used in the suspended polymerization of styrenic monomers can be used.Such as can Using using dissolving in styrenic monomers and the half life temperature of 10 hours is 50-120 DEG C of polymerization initiator.As polymerization Initiator, such as cumyl hydroperoxide, cumyl peroxide, peroxide -2-ethyl hexanoic acid tert-butyl, mistake can be used Aoxidize t-butyl perbenzoate, benzoyl peroxide, tert-butylperoxy isopropyl carbonate, peroxidating -2- ethylhexyl carbonate uncles Butyl ester, peroxidating -2- ethylhexyl carbonates tert-pentyl ester, the own ester of peroxidating -2- ethylhexyl carbonates, lauroyl peroxide etc. have Machine peroxide.Also, as polymerization initiator, azo-compounds such as azodiisobutyronitrile etc. can be used.These polymerizations are drawn Hair agent can be applied in combination using one or more.Also, from the viewpoint of residual styrene system monomer is easily reduced, Preferably peroxide -2-ethyl hexanoic acid tert-butyl.Counted by 100 mass parts of styrenic monomers, preferably using 0.01-3 mass The polymerization initiator of part.

In addition, as crosslinking agent, 10 hours for not decomposing under polymerization temperature and being decomposed under crosslinking temperature are preferably used in 5 DEG C -50 DEG C higher than polymerization temperature of half life temperature material.Specifically, for example, can use cumyl peroxide, 2, The peroxide such as 5- tert butyl peroxy benzoates, 1,1- pairs-tert-butyl hydroperoxide hexamethylene.Crosslinking agent, can individually it make With or two or more be used in combination.The use level of crosslinking agent, counted by 100 mass parts of styrenic monomers, preferably 0.1-5 mass Part.Further, as polymerization initiator and crosslinking agent, identical compound can also be used.

In nuclear particle during dipping polymerization styrenic monomers, preferably by the total amount of the styrene monomer of predetermined cooperation for example More than two parts are divided into, and the addition of these monomers is being dispersed with nuclear particle aqueous medium on different opportunitys.Specifically, A part in the total amount of the styrenic monomers of predetermined cooperation can be added to the aqueous medium for being dispersed with nuclear particle, made Styrenic monomers dipping, polymerization, then, further by the remainder of the styrenic monomers of predetermined cooperation be divided into once or It is added to aqueous medium more than twice.As described in the latter, by dividedly adding styrenic monomers, when can suppress polymerization Resin particle between condensation, can increase compound resin expanded beads surface polar copolymer content.

In addition, polymerization initiator, can be added to aqueous medium to be dissolved in the state of styrenic monomers.As above institute State, the styrenic monomers of predetermined cooperation are being divided into more than twice and in the case of different opportunity additions, can made Polymerization initiator be dissolved in it is in office when machine addition styrenic monomers in, polymerization initiator can also be added in difference In each styrenic monomers of opportunity addition.In the case where styrenic monomers are added in segmentation, preferably make polymerization initiator extremely It is few to be first dissolved in advance in the styrenic monomers (hereinafter referred to as " the first monomer ") initially added.It is it is preferred that molten in the first monomer More than the 75% of the total amount of the predetermined polymerization initiator coordinated of solution, more preferably dissolves more than 80%.In this case, Neng Goufang The only suspended system destabilization in polymerization.As a result, it can obtain having phenylethylene resin series concurrently with higher level excellent The formed body of rigidity and the excellent bonding strength of vinylite.Also, as described above, by the polystyrene list of predetermined cooperation , can be by the residue in the total amount of the styrenic monomers of predetermined cooperation in the case that a part for body is added as the first monomer Part is used as second comonomer, the opportunity additions different from the first monomer after the first monomer is added.Further, can also be further Segmentation adds second comonomer, adds second comonomer with defined Time Continuous.

Further, seed ratio (that is, the quality of the first monomer and nuclear particle of the styrenic monomers as the addition of the first monomer Than) it is preferably more than 0.5.In this case, the ratio of the phenylethylene resin series composition in compound resin is higher In the case of, can also suppress the addition of second comonomer becomes excessive, therefore can be uniformly impregnated with styrene monomer, energy Enough reduce the phenylethylene resin series composition of particle surface.In addition, it is easy to make the shape of composite resin particle closer to spherical.From same From the viewpoint of sample, seed ratio more preferably more than 0.7, more preferably more than 0.8.Also, seed than preferably 1.5 with Under.In this case, in the case that the ratio of the phenylethylene resin series composition in compound resin is higher, can also make Styrene monomer is fully impregnated in nuclear particle.Fully it is being impregnated in addition, styrenic monomers can be better protected from Just it polymerize before nuclear particle, can be better protected from producing the block of resin.From the same viewpoint, the kind of the first monomer Sub- ratio more preferably less than 1.3, more preferably less than 1.2.By the way that the seed ratio of the first monomer is set in above range, In the case that the ratio of phenylethylene resin series composition in compound resin is higher, it can also increase the surface of expanded beads Polar co object amount, it is possible to increase the hydrophily on the surface of expanded beads.

Dipping polymerization temperature Tp (DEG C) in the fusing point Tm (DEG C) and modified process of vinylite in nuclear particle is preferred Meet Tm-10≤Tp≤Tm+30 relation.In this case, phenylethylene resin series composition in compound resin It in the case that ratio is higher, can also styrene monomer is fully impregnated in vinylite, can prevent from hanging during polymerization The destabilization of turbid system.Especially by by the scope group of the scope of above-mentioned polymerization temperature and the seed ratio of above-mentioned first monomer Close, in the case that the ratio of the phenylethylene resin series composition in compound resin is higher, can also increase expanded beads The polar co object amount on surface, even if the content of polar copolymer is less relative to compound resin total amount, it can also improve foaming The hydrophily on the surface of particle.As a result, it can obtain having the excellent rigidity and second of phenylethylene resin series concurrently with higher level The excellent bonding strength of alkene system resin and the excellent expanded beads formed body of the anchorage of antistatic additive.In modified process Dipping polymerization temperature, it is different and different according to the species of the polymerization initiator used, it is preferred that for 60-105 DEG C, more preferably 70-105℃.In addition, crosslinking temperature is different and different according to the species 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, such as fatty acid ester, acetylated monoglyceride, grease type, hydrocarbon can be used Thing etc..As fatty acid ester, such as glyceryl tristearate, tricaprylin, trilaurin, dehydration can be used Sorbierite tristearate, Arlacel-60, butyl stearate etc..Also, as acetylated monoglyceride, example Biacetyl glyceryl monolaurate can such as be used.As grease type, such as hydrogenated tallow, rilanit special can be used Deng.As hydrocarbon compound, such as hexamethylene, atoleine etc. can be used.In addition, as oil-soluble polymerization inhibitor, such as can be with Use p-tert-Butylcatechol, hydroquinones, benzoquinones etc..As fire retardant, such as HBCD, tetrabromo can be used Bisphenol-A based compound, trimethyl phosphate, brominated butadiene-styrene block copolymer, aluminium hydroxide etc.., can as colouring agent To use furnace black, channel black, thermals, acetylene black, Ketjen black, graphite, carbon fiber etc..As chain-transferring agent, Such as n-dodecyl mercaptan, α-methylstyrene dimer etc. can be used.Above-mentioned additive, can individually be added or two kinds Combination of the above is added.

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, such as the fat such as aromatic hydrocarbon, heptane, the octanes such as ethylbenzene, toluene can be used Race's hydrocarbon etc..

In foamed process, composite resin particle is set to foam.As foaming method, it is not particularly limited, such as can enumerates Foaming method or other foaming in these processes, based on principle are discharged for gas impregnated prefoam method, decentralized medium Method.

Physics hair is impregnated in gas impregnated prefoam method, in the composite resin particle in polymerization, and/or after polymerization The foaming agents such as infusion prepare foaminess composite resin particle.Afterwards, foaminess composite resin particle is put into pre-foaming machine In, heated using the heating medium such as vapor, hot blast or their mixture, thus make foaminess compound resin Grain foams and obtains expanded beads.Furthermore it is also possible to by the way that the composite resin particle after preparation is filled into pressure vessel simultaneously It is pressed into foaming agent and foaming agent is impregnated in composite resin particle to prepare foaminess composite resin particle.

On the other hand, in decentralized medium discharges foaming method, first, under heating, pressurization, it is being scattered in pressure vessel Foaming agent is impregnated in the composite resin particle of interior aqueous medium and prepares foaminess composite resin particle.Then, suitable Under the temperature conditionss of foaming, foaminess composite resin particle is discharged into from pressure vessel together with aqueous medium and compares pressure vessel Under the low low pressure of interior pressure, foaminess composite resin particle is thus set to foam and obtain expanded beads.

The dipping of foaming agent can suitably select liquid-phase impregnation process, gas-phase impregnation.As physical blowing agent, can be enumerated as The inorganic gas such as nitrogen, carbon dioxide, argon gas, air, helium gas and water；Methane, ethane, propane, normal butane, iso-butane, ring fourth Alkane, pentane, isopentane, neopentane, pentamethylene, n-hexane, hexamethylene, 2- methylpentanes, 3- methylpentanes, 2,2- dimethyl Volatile organic compoundses such as butane, 2,3- dimethylbutanes etc..Preferably inorganic system's foaming agent.In this case, foaming Rear foaming agent discharges from expanded beads, the not residual blowing agent in expanded beads.Therefore, the internal pressure of expanded beads is difficult during shaping Excessively to rise, and the cooling of formed body can be completed in a short time and is taken out from finishing die.

Painting method as from antistatic additive to expanded beads, can be enumerated as spray application, without gas coating, immersion coating, Mixing method or other painting methods in these processes, based on principle.Spray application is to be formed as antistatic agent solution It is vaporific and the method on expanded beads is injected in together with pressure-air.It is that antistatic agent solution is formed as into high pressure without gas coating And using the pressure from nozzle to the method for expanded beads spray application.Moreover, it is preferred that ground, expanded beads are in injection in flowing State or the surface entirety for being stirred after the injection and making antistatic agent solution be attached to expanded beads.Immersion coating is Expanded beads are impregnated in the method pulled out after antistatic agent solution.Mixing method, it is by resisting to expanded beads and a small amount of The method that electrostatic agent solution is stirred and is coated.

The concentration of antistatic additive to being used in coating does not limit, and can be the dilution of stoste, powder, water or alcohol etc. Liquid.Further, container when coating antistatic additive to expanded beads can be any, coating of enclosed system, open system As long as when temperature also for the heat resisting temperature of expanded beads below.It is preferred that in coating or expanded beads are entered after application The surface entirety that row is sufficiently stirred and makes antistatic additive be attached to composite foamed particle.Painting method can be in the above method It is any, or the above method can also be combined.

As antistatic additive, it is not particularly limited, such as hydroxy alkyl amine, hydroxy alkyl monoether amine, polyoxy can be enumerated as Change the nonionic surfactants such as allylic alkylation amine, fatty acid glyceride, polyoxyethylene alkyl ether；Alkylsulfonate, alkylbenzene The anion surfactants such as sulfonate, alkylphosphonic；Octyldimethyl ethyl ammonium sulfovinate, dodecyl dimethyl The cation system tables such as ethyl ammonium sulfovinate, didecyl Dimethy ammonium chloride, tetraalkylammonium salt, trialkyl benzyl ammonium salt Face activating agent etc..In addition, these antistatic additive can be used alone, or can also be used in mixed way.

From the viewpoint of it can play excellent antistatic property, antistatic additive preferably at least uses cation system surface Activating agent, more preferably at least using octyldimethyl ethyl ammonium sulfovinate.

In the working procedure of coating of antistatic additive, in order that the adhesion amount of antistatic additive is within the above range, with compound resin Expanded beads are 100 mass parts meters, are preferably coated with the antistatic additive of 0.4-4 mass parts.In this case, foaming can be assigned Particle antistatic property excellent enough, and the reduction of the mobility of expanded beads can be prevented and prevent from filling not during shaping It is good.Counted by 100 mass parts of compound resin expanded beads, the coated weight of antistatic additive is more preferably 0.5-3.5 mass parts, enters one Step is preferably 0.6-3 mass parts.Further, the attachment (cladding) of antistatic additive, as long as desired antistatic property can be obtained, It then it is not absolutely required to expanded beads surface being completely covered, can have on expanded beads surface and not covered by antistatic additive Part.

Formed body can heat the mould internal shaping method carried out to manufacture by known by steam.I.e., it is possible to pass through by Multiple expanded beads are filled in the finishing dies such as mould, and importing steam into the finishing die makes expanded beads mutually merge, by This obtains formed body.

Embodiment

(embodiment 1)

Hereinafter, the expanded beads involved by embodiment are illustrated.

Expanded beads involved by embodiment with vinylite dipping polymerization styrenic monomers form it is compound Resin is as substrate resin.That is, the styrene that compound resin contains vinylite composition and styrenic monomers are polymerized It is resin component.Hereinafter, the manufacture method of the expanded beads of this example is illustrated.In addition, in this example, to resulting hair Bubble particle further carries out mould internal shaping and prepares formed body.

(1) preparation of nuclear particle

As vinylite, be ready to pass through LLDPE that metallocene polymerization polymerization catalyst forms (eastern Cao's (strain) manufacture, Trade name：Nipolon-Z HF 210K), vinyl-vinyl acetate copolymer (Asahi Chemical Industry chemistry (strain) manufacture, trade name： The content of vinyl acetate content (that is, construction unit) in EF1531, vinyl-vinyl acetate copolymer is 15 mass %). Vinyl-vinyl acetate copolymer contains carbonyl as polar group, equivalent to above-mentioned polar copolymer.Below by ethene-second Vinyl acetate copolymer is properly termed as " EVA ".In addition, as foaming nucleation agent, prepare Firebrake ZB (rich field pharmacy (strain) system Make, Firebrake ZB 2335).

7.5kg LLDPE, 2.5kg EVA and 0.144kg Firebrake ZB are put into Henschel mixer (three wells Three pond chemical industry machines (strain) manufacture；Model：FM-75E in), mix 5 minutes, obtain resin compound.Then, using 26mm φ's Double screw extruder (being specially the model TEM-26SS of toshiba machine (strain) manufacture) mixes at a temperature of 230-250 DEG C to resin Compound carries out melting mixing.Melting mixing thing is extruded and cuts into average 0.5mg/ by cutting mode in water, thus To the nuclear particle containing vinylite.

(2) preparation of composite resin particle

In the autoclave for being 3L to the internal volume with agitating device, deionized water 1000g is added, it is further to add Jiao 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 Magnesium pyrophosphate slurry as suspension.Then, put into the aqueous medium containing the suspension as surfactant Dodecyl sodium sulfate (be specially 10 mass % the aqueous solution) 2.0g, as water-soluble polymerization inhibitor natrium nitrosum 0.21g with And nuclear particle 75g.

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 1.67g, the tertiary own ester 0.835g of perbenzoic acid and Alpha-Methyl benzene second Alkene dimer 0.665g is dissolved in the first monomer (that is, styrenic monomers).Then, while by dissolved matter with 500rpm rotation Rotary speed is stirred while being put into the above-mentioned autoclave for having put into nuclear particle etc..Further, as the first monomer, Use styrene 60g and butyl acrylate 15g mix monomer.

Then, with after the air of nitrogen displacement autoclave, start to warm up, will be warming up to 30 minutes 1 hour in autoclave Temperature is 100 DEG C.After heating, kept for 1 hour with 100 DEG C of the temperature.Afterwards, mixing speed is dropped into 450rpm, with 100 DEG C temperature keep 7.5 hours.In addition, when after reaching 100 DEG C of temperature by 1 hour, second comonomer will be used as (specially Styrenic monomers) styrene 350g be added to 5 hours in autoclave.

Then, temperature will be warming up in autoclave as 125 DEG C with 2 hours, be kept for 5 hours with 125 DEG C of temperature like this. Afterwards, make to cool down 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 composite resin particle.Further, can be by the styrenic monomers that use during fabrication With the match ratio (mass ratio) of vinylite obtain in compound resin from styrenic monomers composition and derive from The mass ratio of the composition of vinylite.

For the composite resin particle obtained as described above, proportioning, polymerizing condition are shown in table 1 described later.In addition, for Obtained composite resin particle, by from the composition of vinylite (that is, PE) and the composition from styrenic monomers The content of the mass ratio of (that is, PS), EVA content and vinyl acetate content is shown in table 2.In addition, for composite resin particle, XY gel contents, the glass transition temperature Tg of acetone soluble ingredient, acetone soluble ingredient is in such a way determined again to divide equally Son amount Mw, and the results are shown in table 2.

" dimethylbenzene insoluble component (XY gels) measures W_XY”

First, about 1g composite resin particle is taken, by its quality W₀Decimal point the 4th is weighed to, puts it into 150 In purpose metal mesh bag.Then, about 200ml dimethylbenzene is added into the round flask that capacity is 200ml, above-mentioned gold will be put into The sample of category mesh bag is arranged in surname extraction pipe.Heated 8 hours by using mantle heater, carry out surname extraction. After the completion of the extraction, cooled down by air cooling.After cooling, wire netting is taken out from extraction tube, is cleaned with about 600ml acetone Sample is together with wire netting.Then, acetone is made to be dried after volatilizing with 120 DEG C of temperature.Returned after the drying out of wire netting The sample of receipts is exactly " dimethylbenzene insoluble component ".By the weight W of the dimethylbenzene insoluble component obtained by aforesaid operations₁It is weighed to The 4th after decimal point.The content ratio of dimethylbenzene insoluble component, i.e. XY gel contents W_XYFor the weight W of dimethylbenzene insoluble component₁Phase For the weight W of composite resin particle₀Ratio (i.e. 100 × W₁/W₀, unit：%).Further, the XY gels of composite resin particle Measure and substantially the same using the XY gel contents of expanded beads obtained from composite resin particle and the XY gel contents of formed body, Therefore the value of the XY gel contents of composite resin particle can be considered as to XY gel contents, the XY gel contents of formed body of expanded beads. Furthermore it is also possible to composite resin particle is replaced to carry out operation similar to the above using expanded beads, formed body, thus, it is possible to straight Connect XY gel contents, the XY gel contents of formed body of measure expanded beads.

" glass transition temperature Tg of acetone soluble ingredient "

First, composite resin particle 1.0g is put into the metal mesh bag of 150 mesh.Then, to the circle that volume is 200ml About 200ml dimethylbenzene is added in shape flask, the sample (i.e. composite resin particle) being put into above-mentioned metal mesh bag is arranged at In surname extraction pipe.Heated 8 hours using mantle heater, carry out surname extraction.By the xylene solution after extraction Put into 600ml acetone, be decanted, reduction vaporization drying is carried out to supernatant, obtain acetone soluble ingredient.To gained The 2-4mg arrived acetone soluble ingredient, the DSC analyzer Q1000 manufactured using TA INSTRUMENTS companies, based on JIS (days This industrial standard) K7121-1987 progress hot-fluid beamforming means of differential scanning calorimetry measure.Afterwards, it can obtain and be in firing rate Vitrifying of the intermediate point glass transition temperature as acetone soluble ingredient in the DSC curve obtained under conditions of 10 DEG C/minute Transition temperature Tg.Further, acetone obtained from the xylene soluble fraction in compound resin is further dissolved in acetone can Melt into point predominantly phenylethylene resin series.

" the Mw " of acetone soluble ingredient

First, surname extraction is carried out according to the measure identical mode with above-mentioned glass transition temperature.Then, will carry The xylene solution taken is put into 600ml acetone, after decantation, is carried out reduction vaporization drying, is thus obtained acetone soluble ingredient. The Mw of acetone soluble ingredient is measured by the gel permeation chromatography (that is, GPC method) using polystyrene as standard substance. In the assay, the mixed gel column of macromolecule measure has been used.Specifically, the measure device (tool manufactured using eastern Cao (strain) Body is HLC-8320GPC EcoSEC), it is measured under the following conditions, eluent：Tetrahydrofuran (that is, THF), flow： 0.6ml/ minutes, sample solution concentration：0.1wt%.As chromatographic column, used a TSKguardcolumn SuperH-H and The chromatographic column that two TSK-GEL SuperHM-H are connected in series.That is, the acetone being dissolved in by GPC method measure in tetrahydrofuran The molecular weight of soluble ingredient, and be corrected with polystyrene standard to obtain Mw.

(3) preparation of expanded beads

Composite resin particle 500g is put into the pressure for the 5L for possessing mixer together with the water 3500g as decentralized medium In force container.Then, further addition is lived as the kaolin 5g of dispersant and as surface in the decentralized medium into container The sodium alkyl benzene sulfonate 0.5g of property agent.Then, while with 300rpm rotary speed to being stirred in container, while by container Inside it is warming up to 165 DEG C of blowing temperature.Afterwards, carbon dioxide of the press-in as inorganic system's physical blowing agent into container, so as to hold Pressure in device is changed into 3.6MPa (it is gauge pressure), and is kept for 15 minutes with same temperature (that is, 165 DEG C).Thus titanium dioxide is made Carbon is immersed in composite resin particle, obtains foaminess composite resin particle.Then, by by foaminess composite resin particle with Decentralized medium is discharged under atmospheric pressure from container together, and it is 50kg/m to obtain bulk density³Expanded beads.Expanded beads due to It is the foaming body of composite resin particle, therefore is referred to as compound resin expanded beads.Foaming condition is represented described later In table 2.

Reach 1L's further, the expanded beads that 24 hours are dried at a temperature of 23 DEG C are filled into empty 1L graduated cylinder At graticule, the quality (g) of the expanded beads per 1L is determined, carries out the bulk density that unit conversion obtains dried expanded beads (kg/m³)。

For the expanded beads obtained in the manner described above, the ATR methods by using Ge prisms are determined in such a way The dulling luminosity ratio D of measure_1740/2850-Ge, by using ZnSe prisms ATR methods determine dulling luminosity ratio D_{1740/2850-ZnSe}, they Ratio D_1740/2850-Ge/D_{1740/2850-ZnSe}, water vapor adsorption amount, top layer XY gel contents.It the results are shown in table 2 described later.

" the water vapor adsorption amounts of expanded beads "

The implication of the water vapor adsorption amount of expanded beads refers to that the adsorption isotherm at a temperature of 25 DEG C (wherein, is set relative Pressure：Water vapor adsorption amount during maximum relative pressure (be specially 0.9) 0.005-0.9).Further, relative pressure is meant that Refer to the pressure of measure atmosphere and the ratio of saturated vapour pressure.In addition, the saturated vapour pressure at a temperature of 25 DEG C is 3.169kPa.Adopt The vapor sorption amount determining device BELSORP-max manufactured with Japanese Bel Co., Ltd. is measured.First, each foaming is made The average grain diameter of particle be 4mm expanded beads group under atmospheric pressure, at a temperature of 60 DEG C dry 24 after, from expanded beads group Expanded beads 100 are taken, and are weighed.The gross weight of the expanded beads group obtained by weighing result is 0.20g.Then, will The expanded beads group of weighing is all put into the sample unit of device, relative pressure is set as into 0.005-0.9, in unit Expanded beads determine the adsorption isotherm of the vapor at a temperature of 25 DEG C.Then, by the maximum relative pressure of adsorption isotherm The adsorbance of the vapor of expanded beads group when (i.e. 0.9), obtain the water vapor adsorption amount (cm of every 1g expanded beads³/g)。 Water vapor adsorption amount using the adsorbance under the maximum relative pressure as expanded beads.Further, in the assay using each hair The average weight for steeping particle is 1-3mg, the expanded beads group that average grain diameter is 3-5mm.In addition, the average grain of each expanded beads Footpath is measured as follows.

First, prepare to be put into graduated cylinder of the temperature for 23 DEG C of water, will be in relative humidity using instruments such as wire nettings 50%th, temperature be 23 DEG C, placed 2 days under conditions of 1atm after the expanded beads group of any amount (quality of expanded beads group is W α) sink in the water in above-mentioned graduated cylinder.Then, it is contemplated that the volume of the instrument such as wire netting, determine what is read from water level rising part The volume V α (L) of expanded beads group, by the number of volume V α divided by the expanded beads being put into graduated cylinder (N) (V α/N), thus Calculate the average external volume of each expanded beads.Then, it is the imagination with the average external volume identical volume with obtaining is just spherical Average grain diameter of the diameter as each expanded beads.

" dulling luminosity ratio D_1740/2850-Ge, dulling luminosity ratio D_{1740/2850-ZnSe}, compare D_1740/2850-Ge/D_{1740/2850-ZnSe}”

The dulling luminosity ratio D on the surface of expanded beads_1740/2850-GeAnd dulling luminosity ratio D_{1740/2850-ZnSe}, can be by passing through ATR The infrared absorption spectroscopy of method measure is obtained.As measure device, the ir spectrophotometry manufactured using Japan Spectroscopy Corporation Count " FT/IR-460plus " and the total reflection absorption measurement device " ATR PRO 450-S types " of Japan Spectroscopy Corporation's manufacture. Dulling luminosity ratio D_1740/2850-GeDetermined using Ge prisms, dulling luminosity ratio D_{1740/2850-ZnSe}Determined using ZnSe prisms.Specifically Condition determination is prism：Ge or ZnSe, incidence angle：45 °, by expanded beads with 170kg/cm²Pressure press and be close to complete Reflection-absorption determines the prism of device, obtains the infrared absorption spectroscopy (wherein, being corrected without ATR) on the surface of expanded beads.

According to said determination device and condition determination, first, the infrared suction of the ATR methods measure by using Ge prisms is determined Spectrum (wherein, being corrected without ATR) is received, to the wave number 1740cm in the infrared absorption spectroscopy^-1Neighbouring absorbance D_1740-Ge, ripple Number 2850cm^-1Neighbouring absorbance D_2850-GeIt is measured.Then, absorbance D is calculated_1740-GeWith absorbance D_2850-GeRatio, i.e. Dulling luminosity ratio D_1740/2850-Ge.In addition, the infrared absorption spectroscopy that measure is determined by using the ATR methods of ZnSe prisms (wherein, does not have Have ATR corrections), to the wave number 1740cm in the infrared absorption spectroscopy^-1Neighbouring absorbance D_1740-ZnSe, wave number 2850cm^-1It is attached Near absorbance D_2850-ZnSeIt is measured.Then, absorbance D is calculated_1740-ZnSeWith absorbance D_2850-ZnSeRatio, i.e. absorbance Compare D_{1740/2850-ZnSe}.Further, dulling luminosity ratio D is calculated_1740/2850-GeWith dulling luminosity ratio D_{1740/2850-ZnSe}Ratio D_1740/2850-Ge/D_{1740/2850-ZnSe}.It the results are shown in table 2 described later.Further, when calculating each dulling luminosity ratio, for five Individual expanded beads carry out same measure, and obtain their average value.

" top layer dimethylbenzene insoluble component (top layer XY gels) amount "

First, using the expanded beads prepared in the manner described above, and formed body is prepared according to method described later.Then, The Super Deluxe Slicer WSD-2P＆3P of Watanabe Foodmach Co., Ltd.'s manufacture are used as slicer, from shaping The most surface of body cuts out the skin section in the region that depth is 0.1mm.Then, about 1g skin section sample is taken, by its weight W₀₀Claim 4th is measured after decimal point.Skin section sample after weighing is put into the metal mesh bag of 150 mesh.Then, it is to capacity About 200ml dimethylbenzene is added in 200ml round flask, the skin section sample for being put into above-mentioned metal mesh bag is arranged at Soxhlet In extraction tube.Heated 8 hours by using mantle heater, carry out surname extraction.After the completion of the extraction, entered by air cooling Row cooling.After cooling, wire netting is taken out from extraction tube, skin section sample is cleaned together with wire netting with about 600ml acetone.Connect , acetone is dried after volatilizing with 120 DEG C of temperature.The sample reclaimed after the drying out of wire netting is exactly " top layer Dimethylbenzene insoluble component ".By the weight W of the top layer dimethylbenzene insoluble component obtained by aforesaid operations₀₁After being weighed to decimal point 4th.The content ratio of top layer dimethylbenzene insoluble component, i.e. top layer XY gel contents W_XY-SFor the weight of top layer dimethylbenzene insoluble component Measure W₀₁Relative to the weight W of skin section sample₀₀Ratio (i.e. 100 × W₀₁/W₀₀, unit：%).Further, herein, to shaping The top layer XY gel contents of body are determined, but the top layer XY gel contents of expanded beads and formed body are same degree, therefore, The top layer XY gel contents of formed body can be measured as described above, and as the top layer XY gels of expanded beads Amount.

" adhesion amount of antistatic additive "

The foaming of the about 5g expanded beads for being attached with antistatic additive and about 5g unattached antistatic additive is weighed respectively Grain.The weight of the expanded beads of unattached antistatic additive is set to W₀₀₀(W₀₀₀≈5).Use 100cm³(ml) cleaning fluid is (specific For ethanol) each expanded beads after weighing are cleaned 3 times.By the about 300cm after cleaning³Cleaning fluid recovery, in 40 DEG C of temperature Degree is lower to be kept for 24 hours, evaporates cleaning fluid.Then, after measure is attached with the evaporation of the cleaning fluid of the expanded beads of antistatic additive Residue weight W_AResidue weight W after evaporation with the cleaning fluid of the expanded beads of unattached antistatic additive_B.Based on upper State residue weight W_A、W_BAnd the weight W of expanded beads₀₀₀, calculated by following (formula IVs) relative to the foaming of 100 mass parts The adhesion amount A (mass parts) of the antistatic additive of grain.It the results are shown in table 2.

A=(W_A-W_B)/W₀₀₀× 100 ... (formula IVs)

(4) coating of antistatic additive

As antistatic additive, it (is specially the first industrial pharmaceutical (strain) system to prepare octyldimethyl ethyl ammonium sulfovinate " the CATIOGEN ES-O " made；50%) active ingredient is.Expanded beads are put into the modeling that volume is 50L together with antistatic additive In pocket, the mouth of polybag is closed.Then, expanded beads are fully rocked in polybag with antistatic additive after mixing, even It is put into roller and mixes 30 minutes with sack, antistatic additive is thus coated on expanded beads.Compound resin after coating is sent out Particle is steeped to dry 12 hours in 40 DEG C of baking oven.So, the expanded beads for obtaining having antistatic additive in surface attachment are (antistatic Property expanded beads).Further, being counted by 100 mass parts of expanded beads, the addition of antistatic additive is 2 mass parts.As effectively into Component, counted by 100 mass parts of expanded beads, be 1 mass parts.

(5) mould internal shaping

Then, by the expanded beads for being coated with antistatic additive fill to be 250mm with length, width 200mm, thickness 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 to be loaded 12 hours in 60 DEG C of baking oven adjusting to temperature, so that the drying of body and maintenance is formed.So, obtain more The formed body that individual expanded beads mutually merge.

For the formed body prepared in the above described manner, to its apparent density, fusion rate, surface resistivity, crooked elastic rate, Energy to fracture, compressive strength are measured.It the results are shown in table 2.Assay method is as follows.

" apparent density "

Apparent density is calculated with the quality of formed body divided by its volume.

" fusion rate "

Formed body is bent, it is substantially partially fractureed.The plane of disruption is observed, measures internally be broken, i.e. respectively The quantity of the quantity of the expanded beads of material breakage and expanded beads in interface peel.Then, the hair being internally broken is calculated Steep particle relative to the expanded beads being internally broken and interface peel expanded beads total quantity ratio, by its with The value that percentage represents is as fusion rate (%).

" surface resistivity "

By determining the surface resistivity of formed body, and the evaluation of the antistatic property of body is formed.Surface resistivity, It is measured in the method based on JIS K6271-1-2015.In measure, first, from being 23 DEG C, 50%RH in temperature Under the conditions of conserve 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, to be present in the length in cuboid as in two surfaces that 100mm × width is 100mm A surface be expanded beads formed body surface (that is, skin surface), cut out test film.Then, using Mitsubishi Chemical Ind " Hiresta MCP-HT450 ", the surface resistivity on the skin surface of determination test piece of manufacture.As probe, three are used " UR100 " of water chestnut chemical company manufacture, in 23 DEG C, 50%RH, keeps 500V applied voltage to be measured under conditions of 30 seconds. It is measured for any four position on same experiment slice, and obtains its maximum, minimum value and arithmetic average.Again Have, skin surface refers to the surface of the expanded beads formed body as obtained from mould internal shaping.

" crooked elastic rate "

Crooked elastic rate, determined based on the three point bending test method described in JIS K7221-1-2006.Specifically For, using whole surface it is that to cut out thickness as 20mm × width be 25mm × length in cutting face from any part of formed body first Spend five test films for 120mm.Test film is placed 24 hours in the constant temperature and humidity room that room temperature is 23 DEG C, humidity is 50% More than after, distance between the fulcrum be 100mm, the radius R of pressure head is 15.0mm, the radius R of supporting table is 15.0mm, test speed Under conditions of for 20mm/min, room temperature be 23 DEG C, humidity is 50%, the Autograph AGS- that are manufactured with (strain) Shimadzu Seisakusho Ltd. 10kNG testing machines are measured to crooked elastic rate.Using the arithmetic average of 5 points of measured values as crooked elastic rate Measurement result.

" bend fracture energy "

Carry out determining same three point bending test with above-mentioned crooked elastic rate, according to amount of deflection (unit：) and stress m/m (unit：MPa relation), energy (unit when reaching breakaway poing is obtained by the arithmetic average of 5 points of measured value：MJ/ m³).Further, the area that the amount of deflection-stress curve and transverse axis (that is, amount of deflection) during by reaching breakaway poing are surrounded calculates bend fracture Energy.

" compressive strength "

From the middle body cut-out length of expanded beads formed body be 50mm, width 50mm, thickness be the rectangular of 25mm The test film of body shape.Then, compression load during 50% deformation is obtained based on JIS K6767-1999 to the test film.Pass through With the compression load divided by the compression area of test film, compressive strength (that is, 50% compression stress) is calculated.

(embodiment 2)

In this example, the LLDPE quantitative changes more 6kg that will be used in the preparation of nuclear particle, by EVA quantitative changes more 4kg, hair Foaming condition (the CO in container when specially foaming during bubble₂Pressure) be changed to the condition shown in table 2 described later, except this with Outside, expanded beads, formed body are prepared according to the same manner as in Example 1.

(embodiment 3)

In this example, the LLDPE quantitative changes more 9.8kg that will be used in the preparation of nuclear particle, by EVA quantitative changes more 0.2kg, the foaming condition (CO in container when specially foaming during foaming₂Pressure) it is changed to the bar shown in table 2 described later Part, in addition, expanded beads, formed body is prepared according to the same manner as in Example 1.

(embodiment 4)

In this example, by the quantitative change more 100g of the nuclear particle used in the preparation of composite resin particle, as first Monomer has used styrene 85g and butyl acrylate 15g, and has used styrene 300g as second comonomer, in addition, Composite resin particle is prepared according to the same manner as in Example 1.Then, except using the composite resin particle and will foam When foaming condition (specially foam when container in CO₂Pressure) it is changed to outside the condition shown in table 2 described later, according to Mode same as Example 1 prepares expanded beads, formed body.

(embodiment 5)

In this example, it is single as first by the quantitative change more 50g of the nuclear particle used in the preparation of composite resin particle Body has used styrene 35g and butyl acrylate 15g, and has used styrene 400g, in addition, press as second comonomer Composite resin particle is prepared according to mode same as Example 1.Then, except using the composite resin particle and when will foam Foaming condition (specially foam when container in CO₂Pressure) be changed to outside the condition shown in table 2 described later, according to The identical mode of embodiment 1 prepares expanded beads, formed body.

(embodiment 6)

In this example, first, as the foaming nucleation agent used in the preparation of nuclear particle, polytetrafluoroethylene (PTFE) has been used (Seishin enterprises (strain) manufacture, TFW 1000, average grain diameter：10 μm) 14g, in addition, according to same as Example 1 Mode prepares nuclear particle.Then, except having used styrene 52.5g and acrylic acid using the nuclear particle and as the first monomer Outside butyl ester 22.5g, composite resin particle is prepared according to the same manner as in Example 1.In addition, in foaming, to input In the container of the composite resin particle, kaolin 5g and sodium alkyl benzene sulfonate 0.5g is added, and further adds stearic acid and (closes " the stearic acid deer one-level " of eastern chemistry manufacture) 1g, and by the foaming condition (CO in container when specially foaming when foaming₂ Pressure) be changed to the condition shown in table 2 described later, in addition, prepare according to the same manner as in Example 1 expanded beads, Formed body.

(embodiment 7)

In this example, the LLDPE quantitative changes more 9kg that will be used in the preparation of nuclear particle, as EVA, uses acetic acid second The content of alkene ester composition is 46 mass %, three wells-DuPont Chemicals (strain) manufacture EVAFLEX EV-45LX and by EVA quantitative change More 1kg, in addition, nuclear particle is prepared according to the same manner as in Example 1.Then, except the use nuclear particle and general Foaming condition (the CO in container when specially foaming during foaming₂Pressure) it is changed to outside the condition shown in table 2 described later, Expanded beads, formed body are prepared according to the same manner as in Example 1.

(comparative example 1)

In this example, the LLDPE quantitative changes more 10kg that will be used in the preparation of nuclear particle, without using EVA, during by foaming Foaming condition (specially foam when container in CO₂Pressure) condition shown in table 4 described later is changed to, in addition, Expanded beads, formed body are prepared according to the same manner as in Example 1.

(comparative example 2)

In this example, the LLDPE quantitative changes more 5kg that will be used in the preparation of nuclear particle, by EVA quantitative changes more 5kg, hair Foaming condition (the CO in container when specially foaming during bubble₂Pressure) be changed to the condition shown in table 4 described later, except this with Outside, expanded beads, formed body are prepared according to the same manner as in Example 1.

(comparative example 3)

In this example, by the quantitative change more 150g of the nuclear particle used in the preparation of composite resin particle, as first Monomer has used styrene 135g and butyl acrylate 15g, and has used styrene 200g as second comonomer, except this with Outside, composite resin particle is prepared according to the same manner as in Example 1.Then, except using the composite resin particle and will send out Foaming condition (the CO in container when specially foaming during bubble₂Pressure) it is changed to outside the condition shown in table 4 described later, press Expanded beads, formed body are prepared according to mode same as Example 1.

(comparative example 4)

In this example, it is single as first by the quantitative change more 24g of the nuclear particle used in the preparation of composite resin particle Body has used styrene 9g and butyl acrylate 15g, and has used styrene 452g, in addition, press as second comonomer Composite resin particle is prepared according to mode same as Example 1.Then, except using the composite resin particle and when will foam Foaming condition (specially foam when container in CO₂Pressure) be changed to outside the condition shown in table 4 described later, according to The identical mode of embodiment 1 prepares expanded beads, formed body.

(comparative example 5)

In this example, expanded beads and formed body are prepared in such a way.Specifically, first, according to embodiment 1 Identical mode prepares nuclear particle.Then, the internal volume with agitating device be 3L autoclave in, according to embodiment 1 Identical mode prepares the magnesium pyrophosphate slurry as suspension.Then, put into the suspension as surfactant Dodecyl sodium sulfate (being specially the 10 mass % aqueous solution) 2.0g and nuclear particle 75g.

Then, as polymerization initiator, prepare benzoyl peroxide (be specially the manufacture of You companies " NYPER BW "), Peroxidating -2- ethylhexyl single carbons tert-butyl acrylate (be specially the manufacture of You companies " PERBUTYL E "), 1,1- be double-tert-butyl group Cyclohexane peroxide (being specially " Luperox331M70 " of Ah Ke Majifu companies manufacture).Then, by benzoyl peroxide 1.5g, the 0.25g and 1,1- couples-tert-butyl hydroperoxide hexamethylene 5.36g dissolvings of peroxidating -2- ethylhexyl single carbon tert-butyl acrylates In the first monomer (that is, styrenic monomers).Then, while dissolved matter is stirred with 500rpm rotary speed, one While put into the above-mentioned autoclave for having put into nuclear particle etc..Further, as the first monomer, using styrene 410g and Butyl acrylate 15g mix monomer.

Then, with after the air of nitrogen displacement autoclave, start to warm up, will be warming up to 30 minutes 1 hour in autoclave Temperature is 88 DEG C.After heating, kept for 1 hour with 88 DEG C of the temperature.Afterwards, mixing speed is dropped into 450rpm, with 88 DEG C Temperature keep 5 hours.Then, temperature will be warming up in autoclave as 130 DEG C with 2 hours, be protected like this with 130 DEG C of temperature Hold 10 hours.Afterwards, make to cool down in autoclave, take out content (being specially composite resin particle).Then, nitric acid is added, is made In the magnesium pyrophosphate dissolving of the surface attachment of composite resin particle.Afterwards, it is dehydrated and is cleaned by using centrifugal separator, and The moisture for being attached to surface is removed with Pneumatic drying device, obtains composite resin particle.Except using the compound tree so obtained Outside fat particle, expanded beads, formed body are prepared according to the same manner as in Example 1.

(comparative example 6)

In this example, when preparing composite resin particle, styrene 10g and butyl acrylate have been used as the first monomer 15g, and styrene 400g has been used as second comonomer, in addition, prepare according to the same manner as in Example 1 compound Resin particle.Then, except using the composite resin particle and by foam when foaming condition (specially foam when container Interior CO₂Pressure) it is changed to outside the condition shown in table 4 described later, foaming is prepared according to the same manner as in Example 1 Grain, formed body.

(comparative example 7)

In this example, as vinylite, without using straight-chain low density polyethylene (LDPE), using EVA, (eastern Cao's (strain) is made Make, trade name：The content of vinyl acetate content in Ultracene 515, EVA is 6 mass %) 10kg, in addition, is pressed Nuclear particle is prepared according to mode same as Example 1.Then, except (having using the nuclear particle and by foaming condition when foaming The CO in container when body is foams₂Pressure) it is changed to outside the condition shown in table 4 described later, according to same as Example 1 Mode prepares expanded beads, formed body.

For embodiment 2-7 and comparative example 1-7 also similarly to Example 1, evaluation result etc. is represented in table 1- tables 4 In.

From table 1 and table 2, the shaping body surface that antistatic additive is attached with obtained from the expanded beads of embodiment is used Reveal surface resistivity less than 1 × 10¹²This excellent antistatic properties of Ω.In addition, the expanded beads of antistatic additive are attached with, While above-mentioned excellent antistatic property is played, amalgamation is also very excellent.Therefore, it is possible to manufacture internal good knitting, pressure Contracting rigidity and resistance to deflection are excellent and can prevent damaged formed body as caused by deformation.Therefore, using the foaming of embodiment Formed body obtained from particle is applied to electronic equipment, precision as automobile component, liquid crystal panel, solar power generation panel etc. Packing container of equipment etc..

On the other hand, from table 3 and table 4, the content of polar copolymer be the antistatic property of 0 comparative example 1 not Foot.It is considered that this be the anchorage of cation system antistatic additive it is relatively low and fail obtain the antistatic additive based on polar copolymer Outflow inhibition reason.

In addition, in the amount of polar copolymer excessive comparative example 2 and comparative example 7, the fusion rate deficiency of formed body.Can With think itself main reason is that, easily produce the crosslinking of vinylite and make the top layer XY gel contents increase of expanded beads. As a result, the bend fracture energy deficiency of formed body, and easily cause the rupture as caused by deformation.

The rigidity deficiency of the formed body of the less comparative example 3 of styrenic monomers, compressive strength is low, and crooked elastic rate is low. Therefore, the formed body of comparative example 3 easily deforms because of flexure, resistance to deflection deficiency.On the other hand, styrenic monomers are more The compressive strength of the formed body of comparative example 4, crooked elastic rate uprise, but bend fracture energy is insufficient, easily causes by deforming Caused rupture.

In seed than in too high comparative example 5, the block of resin is generated in polymerization.In addition, the fusion of formed body Rate deficiency.It is considered that itself main reason is that, the addition of styrenic monomers is more and suspended system when making polymerization not It is stable, and fail to make styrenic monomers fully be impregnated in vinylite, therefore, the styrene on expanded beads surface It is that resin component becomes more.As a result, the bend fracture energy of the formed body of comparative example 5 is insufficient, easily causes and led by deformation The rupture of cause.In addition, in comparative example 5, dulling luminosity ratio D_1740/2850-Ge, compare D_1740/2850-Ge/D_{1740/2850-ZnSe}It is smaller, vapor Adsorbance is smaller, and antistatic property is insufficient.

On the other hand, in seed than in too low comparative example 6, generating flat composite resin particle.If particle is flat Change, then the filling for being prone to expanded beads in shaping is bad.In addition, the fusion rate deficiency of formed body.It is considered that it is led Reason is wanted to be, the addition of second comonomer is excessive, and makes styrenic monomers be difficult to be uniformly impregnated with, expanded beads surface Phenylethylene resin series become more.As a result, the bend fracture energy of formed body is insufficient, easily causes and broken as caused by deformation Split.In addition, in comparative example 7, dulling luminosity ratio D_1740/2850-Ge, compare D_1740/2850-Ge/D_{1740/2850-ZnSe}It is smaller, water vapor adsorption amount Smaller, antistatic property is insufficient.

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

1. a kind of compound resin expanded beads, it is with dipping polymerization styrenic monomers form in vinylite compound tree Fat is substrate resin,

The compound resin contains more than 5 mass % and less than compositions of the 20 mass % from the vinylite and super 80 mass % and below 95 mass the % composition from the styrenic monomers are crossed, wherein, both adds up to 100 matter Measure %,

The vinylite is the mixture of straight-chain low density polyethylene (LDPE) and the vinyl copolymer with polar group,

The content of the vinyl copolymer with the polar group in the vinylite is 1-45 mass %,

The water vapor adsorption amount of the compound resin expanded beads is 0.50cm³/ more than g.

2. compound resin expanded beads according to claim 1, it is characterised in that the source in the vinyl copolymer In the content of the construction unit of the monomer containing the polar group be 10-50 mass %.

3. compound resin expanded beads according to claim 1 or 2, it is characterised in that having in the compound resin The content of the vinyl copolymer of the polar group is 0.1-7 mass %.

4. the compound resin expanded beads according to any one of claim 1-3, it is characterised in that there is the polar group The vinyl copolymer of group contains carbonyl as the polar group.

5. the compound resin expanded beads according to any one of claim 1-4, it is characterised in that there is the polar group The vinyl copolymer of group is vinyl-vinyl acetate copolymer.

6. the compound resin expanded beads according to claim 4 or 5, it is characterised in that by using the infrared of Ge prisms The wave number 1740cm being totally reflected in the infrared absorption spectroscopy on the surface of the compound resin expanded beads of absorption measurement method measure^-1 Place and wave number 2850cm^-1The dulling luminosity ratio D at place_1740/2850-GeFor more than 0.2.

7. compound resin expanded beads according to claim 6, it is characterised in that by using the infrared complete of ZnSe prisms Wave number 1740cm in the infrared absorption spectroscopy on the surface of the compound resin expanded beads of reflection-absorption determination method measure^-1Place And wave number 2850cm^-1The dulling luminosity ratio D at place_{1740/2850-ZnSe}With the dulling luminosity ratio D_1740/2850-GeThe ratio between D_1740/2850-Ge/ D_{1740/2850-ZnSe}More than 1.

8. the compound resin expanded beads according to any one of claim 1-7, it is characterised in that the compound resin hair The content ratio for steeping the dimethylbenzene insoluble component in the top layer of particle is less than 25%.

9. the compound resin expanded beads according to any one of claim 1-8, it is characterised in that the compound resin contains Have 10-18 mass % from the composition of vinylite and the 82-90 mass % composition from styrene monomer, its In, both adds up to 100 mass %.

A kind of 10. antistatic behaviour compound resin expanded beads, in the compound resin foaming any one of claim 1-9 The surface of grain is covered by the antistatic additive containing cation system surfactant.

11. antistatic behaviour compound resin expanded beads according to claim 10, it is characterised in that with the compound resin Expanded beads are 100 mass parts meters, and the adhesion amount of the antistatic additive is 0.4-3.5 mass parts.

12. a kind of compound resin expanded beads formed body, it is the antistatic behaviour compound resin foaming described in claim 10 or 11 The formed body that particle mutually merges, the surface resistivity of the formed body is less than 1 × 10¹²Ω。