CN107365424A

CN107365424A - Compound resin expanded beads, its manufacture method, compound resin expanded beads formed body

Info

Publication number: CN107365424A
Application number: CN201710325890.7A
Authority: CN
Inventors: 岛昌臣; 西岛浩气
Original assignee: JSP Corp
Current assignee: JSP Corp
Priority date: 2016-05-13
Filing date: 2017-05-10
Publication date: 2017-11-21
Anticipated expiration: 2037-05-10
Also published as: CN107365424B; JP6701943B2; JP2017203144A

Abstract

The present invention, which provides one kind, can obtain that internal good knitting, compression rigidity and resistance to deflection are excellent, and compound resin expanded beads, its manufacture method and the formed body using compound resin expanded beads of the excellent formed body of antistatic property.The present invention is used as the compound resin expanded beads of substrate resin, its manufacture method and the formed body using the compound resin expanded beads using the compound resin that dipping polymerization (methyl) acrylic acid and styrenic monomers form in vinylite.Counted by 100 mass parts of vinylite, compound resin contains the construction unit from styrenic monomers of 100 1900 mass parts.The glass transition temperature Tg of acetone soluble ingredient is below 105 DEG C obtained from xylene soluble fraction in compound resin is further dissolved in acetone.The carbonyl amount on the surface of compound resin expanded beads is more than 0.03mol%.

Description

Compound resin expanded beads, its manufacture method, compound resin expanded beads formed body

Technical field

The present invention relates to be used as base material using the compound resin that dipping polymerization styrenic monomers form in vinylite The formed body that compound resin expanded beads, its manufacture method and the compound resin expanded beads of resin mutually merge.

Background technology

The compound of substrate resin is used as using the compound resin that dipping polymerization styrenic monomers form in vinylite Portion of the mould internal shaping body (that is, compound resin expanded beads formed body) of resin expanded particle as electronic equipment, precision equipment The packaging of part, amortizing packaging material are widely used.For the formed body of such purposes, sometimes for preventing the attached of dust The electrical damage caused by the generation of overcurrent such as, discharge, and typically assigning its antistatic property.

As obtaining the method for compound resin expanded beads, such as known there are following methods.Specifically, first, containing There are dipping polymerization styrenic monomers in the kind particle of vinylite, thus obtain with the dipping polymerization benzene in vinylite Composite resin particle of the compound resin that vinyl monomer forms as substrate resin.Then, impregnated in composite resin particle Foaming agent simultaneously makes the composite resin particle foam, and thus obtains compound resin expanded beads.In addition, as assign expanded beads into The method of body antistatic property, the method for the general antistatic additive being made up of using addition surfactant etc..Specifically, Known have when impregnating volatile foaming agent to composite resin particle or the dipping antistatic additive after impregnate volatile foaming agent Method.In addition, it is also known that have the method to compound resin expanded beads coating antistatic additive.

In the method that antistatic additive is impregnated when impregnating volatile foaming agent, resin particle is exceedingly moulded because of antistatic additive Change, the heat resistance thus with expanded beads during shaping reduces and makes formed body deforms, expanded beads are mutual to melt The possibility that conjunction property reduces.Therefore, as Patent Document 1, develop and ormal weight is coated on compound resin expanded beads The method of cation system antistatic additive.In addition, as shown in patent document 2, develop to the poly- second of composite resin particle dipping polymerization Glycol (methyl) acrylate, the method for antistatic additive is then impregnated when impregnating foaming agent.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2015-81274 publications

Patent document 2：Japanese Unexamined Patent Publication 10-147660 publications

The content of the invention

The problem to be solved in the present invention

But as described in Patent Document 1 as, to compound resin expanded beads coat antistatic additive method In, the anchorage deficiency of antistatic additive be present, according to heating condition during mould internal shaping, because of the steaming as heating medium The antistatic additive that vapour etc. adheres on expanded beads is possible to partly depart from.Therefore, it is desirable to further improve antistatic property. In addition, as described in patent document 2, composite resin particle dipping polymerization is being gathered as reactive surfactant In ethylene glycol (methyl) acrylate and the then method of dipping antistatic additive, it is possible to increase antistatic property.But due to poly- Ethylene glycol (methyl) acrylate is water-soluble higher reactive surfactant, therefore is difficult in dipping polymerization compound Impregnated in resin particle, and the polymerization of polyethylene glycol (methyl) acrylate occurs near the most surface of composite resin particle. Thus, because the polymer deviation of polyethylene glycol (methyl) acrylate is present in the near surface of composite resin particle, as Amalgamation during expanded beads reduces, and the compression rigidity of formed body, resistance to deflection equal strength physical property are possible to become deficiency.Separately Outside, in the method for patent document 2, due to impregnating antistatic additive when impregnating foaming agent, therefore as described above expanded beads it Between amalgamation be possible to reduce.

The present invention is to complete in view of the above problems, and it is an object of the present invention to provide one kind can obtain internal good knitting, pressure Contracting rigidity and resistance to deflection are excellent, and the compound resin expanded beads of the excellent formed body of antistatic property, its manufacturer Method and the formed body using the 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 the compound resin expanded beads are with ethene system tree The compound resin that dipping polymerization (methyl) acrylic acid and styrenic monomers form in fat as substrate resin,

Counted by 100 mass parts of vinylite, what above-mentioned compound resin contained 100-1900 mass parts derives from benzene second The construction unit of alkene monomer,

Acetone can melt into obtained from xylene soluble fraction in above-mentioned compound resin is further dissolved in acetone Point glass transition temperature Tg below 105 DEG C,

The carbonyl amount on the surface of above-mentioned compound resin expanded beads is more than 0.03mol%.

The another way of the present invention is a kind of compound resin expanded beads formed body, is above-mentioned compound resin expanded beads phase The formed body formed is mutually merged, the surface resistivity of the formed body is less than 1 × 10¹²Ω。

The another mode of the present invention is a kind of manufacture method of compound resin expanded beads, is had：

Modified process, it is dispersed with an aqueous medium in the dispersion liquid of vinylite kind particle, with above-mentioned ethene system tree Vinylite in fat kind particle is 100 mass parts meters, adds the styrenic monomers and (methyl) of 100-1900 mass parts Acrylic acid, impregnated in above-mentioned vinylite kind particle, polymerize above-mentioned styrenic monomers and above-mentioned (methyl) acrylic acid, obtained To composite resin particle；With

Foamed process, above-mentioned composite resin particle is foamed using foaming agent, obtain compound resin expanded beads,

Third obtained from xylene soluble fraction in above-mentioned compound resin expanded beads is further dissolved in acetone The glass transition temperature Tg of ketone soluble ingredient below 105 DEG C,

Invention effect

In above-mentioned compound resin expanded beads (hreinafter referred to as " expanded beads "), it will be impregnated in vinylite Polymerization (methyl) acrylic acid and the compound resin that forms of styrenic monomers are as substrate resin, and by compound resin expanded beads The carbonyl amount on surface be adjusted to more than ormal weight.Therefore, even if coating antistatic additive to compound resin expanded beads, also can The outflow of antistatic additive when suppressing to shape, it can obtain having the compound resin expanded beads of good antistatic property to shape Body (hreinafter referred to as " formed body ").Further, since the xylene soluble fraction in compound resin is further dissolved in acetone In obtained from acetone soluble ingredient glass transition temperature below setting, therefore formed body inside fusion, i.e. hair It is good to steep the mutual amalgamation of particle.Therefore, formed body can play the composition etc. based on vinylite, styrene resin The original excellent compression rigidity of compound resin and resistance to deflection equal strength characteristic.

In addition, the surface resistivity that expanded beads mutually merge is less than 1 × 10¹²Ω formed body, it is not only antistatic Excellent performance, as described above, compression rigidity and resistance to deflection equal strength physical property are also very excellent.Therefore, using above-mentioned compound tree Formed body obtained from fat particle is applied to the bundle of the part of the electronic equipments such as liquid crystal panel, solar panel or precision equipment In the purposes such as tundish vessel, amortizing packaging material.

Expanded beads can be manufactured by being modified process and foamed process.In modified process, by ethene system In the scattered dispersion liquid formed in an aqueous medium of resin kind particle, the styrenic monomers and (methyl) propylene of ormal weight are added Acid, dipping, polymerizing styrene system monomer and (methyl) acrylic acid in vinylite kind particle.Thus, obtain in ethene system The composite resin particle that dipping polymerization styrenic monomers and (methyl) acrylic acid form in resin.In foamed process, use Foaming agent makes composite resin particle foam, and obtains expanded beads.Even if antistatic additive is coated to the expanded beads so obtained, such as The outflow of antistatic additive when can also suppress to shape described in upper, can obtain the formed body with good antistatic property. In addition, the inside good knitting of formed body, compression rigidity and resistance to deflection equal strength excellent.

Brief description of the drawings

Fig. 1 is in embodiment, the graph of a relation of styrene amount and dulling luminosity ratio.

Fig. 2 is in embodiment, the graph of a relation of carbonyl amount and dulling luminosity ratio.

Embodiment

Next, the preferred embodiment of above-mentioned expanded beads is illustrated.Expanded beads, such as be used in its table Face coats the purposes of antistatic additive.The expanded beads of this purposes, it may be said that have on surface and be used to make what antistatic additive adhered to Antistatic additive contact surface.Further, in this manual, expanded beads are the particles, unattached for having antistatic additive in surface attachment The concept that the particle of antistatic additive is included.

Expanded beads by mould internal shaping in order to obtain formed body to use.That is, multiple expanded beads are filled in shaping In mould, composite resin particle is set to merge each other in finishing die, thus, it is possible to obtain the formed body of intended shape.

Expanded beads (below, will also with the dipping polymerization styrenic monomers in vinylite and (methyl) acrylic acid They are referred to as styrenic monomers etc..) compound resin that forms is as substrate resin.In this manual, it is as described above, compound Resin is the resin that dipping, polymerizing styrene system monomer etc. form in vinylite, is referred to containing vinylite composition With the resin of phenylethylene resin series composition.Phenylethylene resin series composition contain the styrenic monomers composition polymerized together formed and The composition that styrenic monomers and (methyl) acrylic acid copolymer form.Further, in the polymerization of styrenic monomers etc., no The only mutual polymerization of styrenic monomers, polystyrene list can also occur on the polymer chain for forming vinylite sometimes The graft polymerization of body.In this case, compound resin not only containing be made up of vinylite vinylite composition, with And the phenylethylene resin series composition that styrenic monomers are polymerized, further also there are styrenic monomers containing graft polymerization Vinylite composition (that is, PE-g-PS compositions).Therefore, compound resin with by after the vinylite after polymerizeing and polymerization The hybrid resin that mixes of phenylethylene resin series be 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 vinylite in compound resin, toughness, restoration raising be present, but just Property reduce tendency.On the other hand, in the case where improving from the ratio of the construction unit of styrenic monomers, exist Rigidity improves, but the tendency that toughness, restoration reduce.As described above, in compound resin, using vinylite as 100 mass Part meter, containing the construction unit from styrenic monomers more than 100 mass parts and below 1900 mass parts, accordingly, it is capable to Access the good formed body of toughness, restoration, rigid balance.In order to obtain toughness, restoration, rigid balance more Add good formed body, in compound resin, counted by 100 mass parts of vinylite, preferably contain more than 150 mass parts and The construction unit from styrenic monomers below 1900 mass parts.Go out from the further rigid viewpoint for improving formed body Hair, counted by 100 mass parts of vinylite, from styrenic monomers construction unit content more preferably more than 400 mass parts, more preferably more than 450 mass parts, particularly preferably more than 500 mass parts.In addition, in order to further carry Toughness, the restoration of high formed body, are counted by 100 mass parts of vinylite, from the construction unit of styrenic monomers Content be more preferably below 1000 mass parts, more preferably below 900 mass parts.Further, in this manual, with number The upper limit and the related preferred scope of lower limit, more preferably scope, further preferred scope for being worth scope can be by the upper limit and lower limits It is all combined to determine.

As vinylite, it is, for example, possible to use low density polyethylene (LDPE), straight-chain low density polyethylene (LDPE), branched are low Density polyethylene, high density polyethylene (HDPE), ethylene-acrylic acid copolymer, ethylene-acrylic acid alkyl ester copolymer, ethene-methyl-prop Olefin(e) acid alkyl ester copolymer, vinyl-vinyl acetate copolymer etc..As vinylite, a kind of polymer can be used, The mixture of two or more polymer can be used.

Above-mentioned vinylite preferably includes straight-chain low density polyethylene (LDPE) or straight-chain low density polyethylene (LDPE) and second Alkene-vinyl acetate copolymer.The content of vinyl-vinyl acetate copolymer in vinylite is preferably less than 10 matter % is measured, more preferably less than 5 mass %.Most preferably vinylite does not contain vinyl acetate copolymer.Further, preferably Vinylite is used as main component using straight-chain low density polyethylene (LDPE).Specifically, the straight-chain in vinylite is low close The content for spending polyethylene is preferably more than 50 mass % more preferably 70 mass %, special more preferably more than 80 mass % Only it You Xuanwei be made up of straight-chain low density polyethylene (LDPE).

Straight-chain low density polyethylene (LDPE), it is however preferred to have the Polyethylene Chain and carbon number of straight chain are 2-6 short chain shape The structure of side chain.Specifically, for example, can be enumerated as ethylene-butene copolymer, ethylene-hexene co-polymers, ethylene-octene copolymerization Thing etc..Especially, vinylite is preferably that the fusing point being polymerized using metallocene system polymerization catalyst is less than 105 DEG C Straight-chain low density polyethylene (LDPE).In this case, the vinylite composition in compound resin and styrenic monomers polymerization Compatibility between the phenylethylene resin series component formed further improves, it is possible to increase the toughness of compound resin.Further, since Can be while low molecular weight compositions be reduced, the aggregation strength between expanded beads when improving shaping, therefore can obtain low VOC (VOC) and it is difficult to the formed body ruptured.Further, it can obtain and styrene is had concurrently with higher level Be resin excellent rigidity and vinylite excellent bonding strength formed body.

In addition, the fusing point Tm of vinylite is preferably 95-105 DEG C.In this case, styrenic monomers can be made Be sufficiently impregnated in vinylite, therefore, it is possible to prevent polymerization when suspended system destabilization.As a result, it can obtain It is able to the formed body that higher level has the excellent rigidity of phenylethylene resin series and the excellent bonding strength of vinylite concurrently. From the same viewpoint, the fusing point Tm of vinylite is preferably 100-105 DEG C.Further, fusing point Tm can be based on JIS (days This industrial standard) K7121-1987, (that is, DSC) is determined by Differential Scanning Calorimeter and is measured with melting peak temperature.

Vinylite, preferably by fusing point Tm (units：DEG C) and Vicat softening point Tv (units：DEG C) meet Tm-Tv≤20 (unit：DEG C) relation straight-chain low density polyethylene (LDPE) form.Vinylite as supposition, show uniform molecule Structure, network structure is more evenly distributed in vinylite as caused by crosslinking.Therefore, in this case, can Improve the intensity and bonding strength of the expanded beads formed body obtained using above-mentioned expanded beads.From the strong of more raising formed body From the viewpoint of degree and bonding strength, straight-chain low density polyethylene (LDPE) more preferably meets Tm-Tv≤15 (unit：DEG C), further It is preferred that meet Tm-Tv≤10 (unit：℃).Generally, fusing point Tm is higher than Vicat softening point Tv., can be with further, Vicat softening point Tv Determined based on JIS K 7206 (2016) A50 methods.In addition, it is to be mixed by what two or more resins were formed in vinylite In the case of resin, fusing point, Vicat softening point to hybrid resin are measured and the fusing point as vinylite, Vicat softening point.

From the viewpoint of it further can improve foaminess, under conditions of temperature is 190 DEG C, load is 2.16kg The melt mass flow rate (that is, MFR) of vinylite is preferably 0.5-4.0g/10 minutes, more preferably 1.0-3.0g/10 Minute.The MFR of vinylite under conditions of temperature is 190 DEG C, load is 2.16kg is based on JIS K7210-1- The value of (2014) measure.Further, melt index apparatus (such as the model that precious industrial (strain) manufactures can be used as measure device L203 etc.).

Compound resin, the composition formed containing styrenic monomers and (methyl) acrylic acid copolymer.Further, in this specification In, sometimes by the styrene for forming phenylethylene resin series composition, be added as needed on can with styrene copolymerized monomer (but It is, except (methyl) acrylic acid) and referred to as styrenic monomers.The ratio of styrene in styrenic monomers, preferably 50 More than quality %, more preferably more than 80 mass %, more preferably more than 90 mass %.As can with it is styrene copolymerized Monomer, such as have following styrene derivatives, 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, the ethene containing hydroxyl can be enumerated as Based compound, the vinyl compound containing itrile group, organic acid vinyl compound, olefin(e) compound, diolefin compound, halo Vinyl compound, meta-halo ethylene based compound, maleimide compound etc..These vinyl monomers, can individually it make With two or more mixtures can also be used.

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 the viewpoint of foaminess is improved, as styrenic monomers, preferably styrene or and with styrene with Acrylic ester monomer.From it is further improve foaminess from the viewpoint of, preferably and with styrene and butyl acrylate.This In the case of, the content of the construction unit from butyl acrylate in compound resin, relative to compound resin generally 0.5- 10 mass %, more preferably 1-8 mass %, more preferably 2-5 mass %.

In addition, further contain the construction unit from (methyl) acrylic acid in phenylethylene resin series composition.In this theory In bright book, " (methyl) acrylic acid " is the concept containing " acrylic acid " and " methacrylic acid ", represents the side or double in them Side.(methyl) acrylic acid in structure due to having the double bond between carbon-to-carbon, therefore the energy in the dipping polymerization of styrenic monomers Enough and styrenic monomers are copolymerized.Moreover, the construction unit from (methyl) acrylic acid is present in such as table of expanded beads Face, thus, it is possible to while the confluent reduction of expanded beads is suppressed, improve the anchorage of antistatic additive.According to the consideration, its Reason is as follows.

That is, (methyl) acrylic acid has the water solubility of appropriateness, therefore polymerization stability is higher, and is difficult to produce condensation.Enter One step, according to the consideration, (methyl) acrylic acid is copolymerized with styrenic monomers, and thus compound resin, which contains to have, derives from styrene It is the copolymer composition of the construction unit of monomer and the construction unit from (methyl) acrylic acid, further, it is possible in particle table Contain the copolymer composition in face.Therefore, it is possible to improve the set of antistatic additive in the state of the amalgamation of expanded beads is maintained Property.

Preferably, compared with the central part of expanded beads, it is present in foaming from the structure of (methyl) acrylic acid is more The near surface of particle.In this case, the anchorage of the antistatic additive of expanded beads can further be improved.Described later In the manufacturing process of expanded beads, the opportunity of (methyl) acrylic acid is added by adjusting, easily makes to derive from (methyl) acrylic acid Structure be present in the near surfaces of expanded beads.Specifically, in the dipping polymerization of styrenic monomers, by polystyrene In the case that monomer is divided into repeatedly addition, by with adding (methyl) propylene together with the styrenic monomers of addition after second Acid, the structure easily made from (methyl) acrylic acid are present in the near surface of expanded beads.

It is highly preferred that as much as possible at least with (methyl) acrylic acid is added together with the styrenic monomers finally added, or Person, until adding in a period of untill the polymerization completion of the styrenic monomers after the styrenic monomers finally added of addition Add (methyl) acrylic acid.In this case, the carbonyl from (methyl) acrylic acid on the surface of expanded beads is easily improved Amount.

Moreover, the styrenic monomers finally added preferably do not contain acrylate as escribed above etc. can be with benzene second The monomer of alkene copolymerization.Specifically, the styrenic monomers finally added are more preferably styrene.In this case, can The anchorage of antistatic additive is correspondingly expeditiously improved with the addition of (methyl) acrylic acid.

Acetone soluble ingredient obtained from xylene soluble fraction in compound resin is further dissolved in acetone Glass transition temperature Tg is below 105 DEG C, preferably less than 102 DEG C.On the other hand, the lower limit of glass transition temperature Tg is excellent Elect more than substantially 85 DEG C as.In this case, the foaminess during foaming of composite resin particle can be further improved, can Further prevent contraction during foaming.Further, the expanded beads obtained after expanding it is in-molded when, can be further The mutual amalgamation of expanded beads is improved, can further improve the dimensional stability of expanded beads formed body.

Above-mentioned glass transition temperature Tg can for example determine in accordance with the following methods.First, by composite resin particle 1.0g It is put into the metal mesh bag of 150 mesh.Then, about 200ml dimethylbenzene is added into the round flask that volume is 200ml, will The sample being put into above-mentioned metal mesh bag is arranged in surname extraction pipe.Heated 8 hours, carried out using mantle heater Surname extraction.Xylene solution after extraction is put into 600ml acetone, is decanted, decompression steaming is carried out to supernatant It is dry dry, obtain acetone soluble ingredient.To resulting 2-4mg acetone soluble ingredient, TA INSTRUMENTS companies are used The DSC analyzer Q1000 of manufacture, hot-fluid beamforming means of differential scanning calorimetry measure is carried out for (1987) based on JIS K7121.Afterwards, The intermediate point glass transition temperature conduct in the DSC curve obtained under conditions of firing rate is 10 DEG C/minute can be obtained The Tg of acetone soluble ingredient, it is further dissolved in obtaining in acetone as by the xylene soluble fraction in compound resin Acetone soluble ingredient Tg.Further, the xylene soluble fraction in compound resin is further dissolved in obtaining in acetone Acetone soluble ingredient be mainly phenylethylene resin series.

The carbonyl amount (below, also known as surface carbonyl amount) on expanded beads surface is more than 0.03mol%.In deficiency In the case of 0.03mol%, the raising effect of the anchorage of antistatic additive is possible to become deficiency.As a result, formed body Antistatic property is possible to become deficiency.From the viewpoint of the further anchorage for improving antistatic additive, expanded beads surface Carbonyl amount be more preferably more than 0.07mol%, more preferably more than 0.1mol%.

On the other hand, if the carbonyl amount of expanded beads entirety is excessive, glass transition temperature Tg becomes more than 105 DEG C Height, the amalgamation of expanded beads are likely to decrease.From maintaining the amalgamation of expanded beads with not improving glass transition temperature While, further from the viewpoint of the anchorage of raising antistatic additive, the carbonyl amount on expanded beads surface is preferably Below 0.2mol%, more preferably below 0.16mol%, more preferably below 0.15mol%.

The infrared absorption spectroscopy that the carbonyl amount on expanded beads surface can be absorbed (ATR methods) by total reflection is obtained.It is specific and The product of the carbonyl amount of speech, the styrene amount by the surface of expanded beads and the styrene amount relative to surface is obtained.First, press Styrene amount and the carbonyl amount relative to styrene amount are determined according to following methods.

(a) styrene amount

When determining styrene amount, obtained using infrared spectrophotometer and total reflection absorption measurement device as measure device To the infrared absorption spectroscopy (wherein, being corrected without ATR) on the surface of expanded beads.Then, determine by infrared absorption spectroscopy (its In, corrected without ATR) obtained 698cm^-1The absorbance D at place₆₉₈、2850cm^-1The absorbance D at place₂₈₅₀, obtain dulling luminosity ratio D₆₉₈/D₂₈₅₀.Same measure, the dulling luminosity ratio using their average value as expanded beads are carried out for five expanded beads D₆₉₈/D₂₈₅₀.Above-mentioned dulling luminosity ratio D₆₉₈/D₂₈₅₀, turn into presumption foaminess modified resin particles thereof surface polystyrene amount finger Mark.Further, the absorbance D obtained by infrared absorption spectroscopy (wherein, being corrected without ATR)₆₉₈It is derived from mainly containing in benzene second Become the height of the peak value of angular oscillation outside the face of phenyl ring in alkene system resin.In addition, (wherein, there is no ATR schools by infrared absorption spectroscopy The absorbance D just) obtained₂₈₅₀It is derived from the C- of methylene contained in the both sides of vinylite and phenylethylene resin series The height of the peak value of stretching vibration between H.It is then possible to the styrene amount on expanded beads surface is obtained using calibration curve.

(b) relative to the carbonyl amount of styrene amount

When determining carbonyl amount, obtained using the measure device same with the measure of above-mentioned styrene amount, condition determination Carbonyl amount.Then, the 698cm obtained by infrared absorption spectroscopy (wherein, being corrected without ATR) is determined^-1The absorbance D at place₆₉₈、 1730cm^-1The absorbance D at place₁₇₃₀, obtain dulling luminosity ratio D₁₇₃₀/D₆₉₈.Same measure is carried out for five expanded beads, will Dulling luminosity ratio D of their average value as compound resin expanded beads₁₇₃₀/D₆₉₈.Further, by infrared absorption spectroscopy (wherein, There is no ATR corrections) obtained absorbance D₁₇₃₀It is derived from the height of the peak value of the carboxyl of (methyl) acrylic component unit.So Afterwards, the carbonyl amount relative to styrene amount is obtained using pre-made calibration curve.It is then possible to by above-mentioned styrene amount and The carbonyl amount on expanded beads surface is obtained relative to the product of the carbonyl amount of styrene amount.

Phenylethylene resin series composition has construction unit, the structure list from acrylic acid from methacrylic acid Member, or the construction unit from methacrylic acid and the construction unit from acrylic acid.Preferably, phenylethylene resin series Composition at least has the construction unit from methacrylic acid.In this case, it can more balance to improve well and resist The anchorage of electrostatic agent and the amalgamation of expanded beads.

In expanded beads, counted by 100 mass parts of compound resin, the construction unit from (methyl) acrylic acid contains Amount is preferably 0.1-2 mass parts.In this case, anchorage and the foaming for improving antistatic additive well can more be balanced The amalgamation of particle.From the viewpoint of the further anchorage for improving antistatic additive, counted by 100 mass parts of compound resin, Content from the construction unit of (methyl) acrylic acid is more preferably more than 0.2 mass parts, more preferably 0.5 mass parts More than.On the other hand, from the viewpoint of confluent reduction is further suppressed, counted by 100 mass parts of compound resin, source It is more preferably in the content of the construction unit of (methyl) acrylic acid below 1.5 mass parts, more preferably below 1 mass parts.

Can be in the surface attachment antistatic additive of expanded beads.Although the adhesion amount of antistatic additive additionally depend on use it is anti- The species of electrostatic agent, but counted by 100 mass parts of expanded beads, preferably 0.3-5 mass parts.In this case, can Antistatic property is fully obtained, and can further prevent confluent reduction.From more fully obtaining antistatic property Viewpoint is set out, and is counted by 100 mass parts of expanded beads, and the adhesion amount of antistatic additive is more preferably more than 0.5 mass parts.In addition, from From the viewpoint of confluent reduction can further being prevented, the adhesion amount of antistatic additive is more preferably below 3 mass parts, is entered One step is preferably below 2 mass parts.

Further, substrate resin is used as using the compound resin that dipping polymerization styrenic monomers form in vinylite Compound resin expanded beads substantially have hydrophobicity, therefore, be attached with anchorage during with hydrophilic antistatic additive compared with It is low, according to heating condition when expanded beads are carried out with mould internal shaping, because steam etc. as heating medium is there is a possibility that sending out The antistatic additive adhered on bubble particle partly departs from.But according to the consideration, as mentioned above due to above-mentioned expanded beads contain it is specific The construction unit from (methyl) acrylic acid of amount, therefore, makes near surface with not hindering the mutual amalgamation of expanded beads Moderately hydrophiling, so as to improve the anchorage of antistatic additive.That is, according to above-mentioned compound resin expanded beads, can obtain simultaneous The formed body of standby excellent mechanical strength and antistatic property.

As antistatic additive, it is not particularly limited, such as hydroxy alkyl amine, hydroxy alkyl monoether amine, polyoxy can be enumerated as The nonionic surfactants such as alkenylalkyl amine, fatty acid glyceride, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether；Alkane The anion surfactants such as base sulfonate, alkylbenzenesulfonate, alkylphosphonic；Octyldimethyl ethyl ammonium ethyl sulfuric acid Salt, dodecyl dimethyl ethyl ammonium sulfovinate, didecyl Dimethy ammonium chloride, tetraalkylammonium salt, trialkyl benzene first The cation such as base ammonium salt system surfactant etc..In addition, these antistatic additive can be used alone, or it can also mix and make With.It is, for example, possible to use various commercially available products are as antistatic additive.

Antistatic additive preferably at least contains cation system surfactant, more preferably at least using octyldimethyl ethyl ammonium Sulfovinate.In this case, antistatic additive is easier in the hair containing the construction unit from (methyl) acrylic acid Set on particle is steeped, can further improve the antistatic property of formed body.

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 5 × 10¹¹Below Ω, more preferably 2.5 × 10¹¹ Below Ω.

The water vapor adsorption amount of expanded beads is preferably 0.5cm³/ more than g.In this case, can it is relatively reliable and Fully improve the anchorage of the antistatic additive on expanded beads surface.From the above point of view, the water vapor adsorption of expanded beads Amount is more preferably 0.7cm³/ more than g, more preferably 0.8cm³/ more than g.Further, above-mentioned water vapor adsorption amount is to represent Expanded beads surface can adsorb the index of how much vapor.The water vapor adsorption amount is the hydrophilic index of expanded beads, The tendency that the steam vapour amount on expanded beads surface also uprises therewith is adsorbed in if in the presence of increasing if the carbonyl amount on expanded beads surface.

The measure of the water vapor adsorption amount of compound resin expanded beads, vapor sorption amount determining device can be used at 25 DEG C Under to adsorption isotherm (setting relative pressure：0.005-0.9) it is measured, and obtains water when maximum relative pressure is 0.9 Water vapor adsorption amount of the vapor sorption amount as the compound resin expanded beads of the present invention.Specifically, for example, can claim in advance About 0.2g composite resin particle is measured, then, the composite resin particle of weighing is put into sample unit, the water at 25 DEG C is steamed Adsorption isotherm (the setting relative pressure of gas：0.005-0.9) it is measured, and obtains water when maximum relative pressure is 0.9 Water vapor adsorption amount of the vapor sorption amount as the compound resin expanded beads of the present invention.

Then, the embodiment of the manufacture method of expanded beads is illustrated.By being modified process and foaming Process and obtain expanded beads.Hereinafter, each operation is described in detail.

In modified process, use using vinylite composition as main component vinylite kind particle (it is following, Referred to as " kind particle ").Kind particle, in addition to vinylite composition, it can further contain bladder regulator, coloring Agent, lubricant, scattered footpath expand the additives such as agent.Kind of particle can be by the above-mentioned additive and second that will add as needed Alkene system resin component manufactures with merging to carrying out grain refined after complex progress melting mixing.Melting mixing can be by extruder Come carry out.In order to be uniformly kneaded, extruded again after preferably resin component is mixed in advance.The mixing of resin component, Such as can use Henschel mixer, Ribbon Blender, V-mixer, sieve lattice mixer (The mixing such as mixer) Machine is carried out.Melting mixing, preferably possessing using the high decentralized such as Dulmadge types, Maddock types, Unimelt types The single screw extrusion machine or double screw extruder of screw rod is carried out.

The granulation of kind particle, for example, being extruded the complex after melting mixing while cutting off to enter with extruder etc. OK.It is granulated, such as can be carried out by wire cutting method, underwater cutting process, thermal cutting method etc..

In modified process, first by the way that kind of particle is disperseed in an aqueous medium to obtain dispersion liquid.As water-based Jie Matter, such as deionized water can be used.It is preferred that kind particle is disperseed in an aqueous medium together with suspension.In such case Under, styrenic monomers described later can be made equably suspended in the aqueous medium for being dispersed with kind of particle.As suspension, example Tricalcium phosphate, hydroxyapatite, magnesium pyrophosphate, magnesium phosphate, aluminium hydroxide, iron hydroxide, titanium hydroxide, hydrogen-oxygen can such as be used Change the microgranular nothings such as magnesium, barium phosphate, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, talcum, kaolin, bentonite Machine suspension.Also, such as polyvinylpyrrolidone, polyvinyl alcohol, ethyl cellulose, hydroxypropyl methyl fiber can also be used Organic suspension such as element.Preferably tricalcium phosphate, hydroxyapatite, magnesium pyrophosphate.These suspensions can be used alone or two Kind combination of the above uses.

The usage amount of suspension, the slurry containing reaction product (is specially included with the aqueous medium of suspended polymerization system Whole water in system including the water of material etc.) it is 100 mass parts meters, it is preferably 0.05-10 mass parts in terms of solid content.More Preferably 0.3-5 mass parts.In the case where suspension is very few, in modified process, it is difficult to make styrenic monomers stably It is suspended, it is possible to produce the block of resin.On the other hand, in the case where suspension is excessive, not only manufacturing cost increases, and And the particle diameter distribution of the composite resin particle obtained after modified process is possible to become big.

Can be to add the dispersant that is made up of surfactant in hydrotropism's medium.As surfactant, such as can be with It is preferred that use anion system surfactant, nonionic surfactants.These surfactants can be used alone or more Kind is applied in combination.

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 can use Ethylene nonyl phenyl ether, polyoxyethylene lauryl ether etc..As dispersant, it is 8-20 more preferably to use by carbon number The anion system surfactant that forms of alkyl sulfonic acid alkali metal salt (be preferably sodium salt).It is suspended fully steady thereby, it is possible to make Fixedization.

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..

Water-soluble polymerization inhibitor, it is difficult to be immersed in kind of particle, and be dissolved in aqueous medium.Therefore, although being immersed in Styrenic monomers in kind of particle can be polymerize, but can suppress to be not impregnated with kind of particle but in an aqueous medium Styrenic monomers the polymerization of fine droplet and the kind particle surface in being absorbed by kind of particle near styrene It is the polymerization of monomer.Speculate as a result, can be by the phenylethylene resin series composition near the most surface of composite resin particle Amount control is less, improves the obtained toughness of formed body.The addition of water-soluble polymerization inhibitor, (is specially wrapped with aqueous medium Include whole water in the system including the water of the slurry containing reaction product etc.) it is 100 mass parts meters, preferably 0.001- 0.1 mass parts, more preferably 0.005-0.06 mass parts.

In modified process, kind of particle is being scattered in the dispersion liquid that aqueous medium forms as described above, is making benzene Vinyl monomer and (methyl) acrylic acid impregnate in kind of particle, polymerize.Further, the polymerization of styrenic monomers etc. can be poly- Carried out in the presence of conjunction initiator.In this case, ethene is produced while the copolymerization of styrenic monomers etc. sometimes It is the crosslinking of resin.In addition, crosslinking agent can be used together as needed.When using polymerization initiator, crosslinking agent, preferably in advance will Polymerization initiator, crosslinking agent are dissolved in styrenic monomers.

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, it is preferably used under polymerization temperature and does not decompose, 10 decomposed under crosslinking temperature hour The material that 5 DEG C -50 DEG C higher than polymerization temperature of half life temperature.Specifically, for example, can use cumyl peroxide, 2,5- The peroxide such as tert butyl peroxy benzoate, 1,1- pairs-tert-butyl hydroperoxide hexamethylene.Crosslinking agent, it can be used alone Or two or more it is used in combination.The use level of crosslinking agent, counted by 100 mass parts of styrenic monomers, preferably 0.1-5 mass parts. Further, as polymerization initiator and crosslinking agent, identical compound can also be used.

Additionally, it is preferred that (methyl) acrylic acid is dissolved in styrenic monomers in advance.I.e., it is preferable that be scattered in water Property medium in kind particle in dipping, Polymeric dissolution have the styrenic monomers of (methyl) acrylic acid.In this case, in benzene It is more prone to introduce (methyl) acrylic acid during the polymerization of vinyl monomer.

, can be by the total amount of the styrene monomer of predetermined cooperation once in kind of particle during dipping polymerization styrenic monomers Property is added to the aqueous medium for being dispersed with kind of particle, can also for example split the total amount of the styrenic monomers of predetermined cooperation For more than two parts, and these monomers are added on different opportunitys.Specifically, can be by the styrenic monomers of predetermined cooperation A part in total amount is added to the aqueous medium for being dispersed with kind of particle, makes styrenic monomers dipping, polymerization, then, enters The remainder of the styrenic monomers of predetermined cooperation is divided into more than once or twice by one step is added to aqueous medium.As after Described in person, by dividedly adding styrenic monomers, it can further suppress the mutual condensation of resin particle in polymerization.

In addition, the total amount of the styrenic monomers of predetermined cooperation is being divided into more than two parts and different as described above In the case that opportunity adds these monomers, preferably with adding (methyl) propylene together with addition styrenic monomers after second Acid.More preferably at least with adding (methyl) acrylic acid together with the styrenic monomers finally added.In this case, easily make Phenylethylene resin series composition containing the construction unit from (methyl) acrylic acid is present in the near surface of expanded beads.Its As a result, it is possible to further improve the anchorage of the antistatic additive of expanded beads.

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, manufacturing During composite resin particle, styrenic monomers can be made fully to be immersed in vinylite, can prevent from hanging in polymerization Turbid system destabilization.As a result, it can obtain having the excellent rigidity of phenylethylene resin series and ethene system concurrently with higher level The formed body of the excellent bonding strength of resin.Also, as described above, make by a part for the styrenic monomers of predetermined cooperation , can be using the remainder in the total amount of the styrenic monomers of predetermined cooperation as second in the case of being added for the first monomer Monomer, the opportunity additions different from the first monomer after the first monomer is added.Addition second comonomer can also further be split.

Further, seed ratio (that is, the quality of the first monomer and kind particle of the styrenic monomers as the addition of the first monomer Than) it is preferably more than 0.5.In this case, it is easy to make the shape of composite resin particle closer to spherical.From same viewpoint Set out, seed ratio more preferably more than 0.7, more preferably more than 0.8.Also, seed ratio preferably less than 1.5.At this In the case of kind, styrenic monomers can be better protected from and be sufficiently impregnated before kind of particle just polymerizeing, can preferably be prevented Only produce the block of resin.From the same viewpoint, the seed ratio more preferably less than 1.3 of the first monomer, it is further excellent Elect less than 1.2 as.

The preferred satisfactions of polymerization temperature Tp (DEG C) in the fusing point Tm (DEG C) and modified process of vinylite in kind particle Tm-10≤Tp≤Tm+30 relation.In this case, when manufacturing composite resin particle, styrenic monomers can be filled It is immersed in vinylite with dividing, the destabilization of suspended system when can prevent from polymerizeing.As a result, it can obtain with more High level has the expanded beads formed body of the excellent rigidity of phenylethylene resin series and the excellent bonding strength of vinylite concurrently.And And dipping temperature, polymerization temperature in modified process, it is different and different according to the species of the polymerization initiator used, but it is excellent Elect 60-105 DEG C, more preferably 70-105 DEG C as.Also, 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 The additives such as agent, chain-transferring agent.In the case where adding these additives to styrenic monomers, above-mentioned first is preferably added at In monomer.Do not added in the above-mentioned styrenic monomers finally added preferably at least in these additives, with carbonyl Additive.

As plasticizer, such as fatty acid ester, acetylated monoglyceride, grease type, hydrocarbon compound etc. can be used.Make For fatty acid ester, such as glyceryl tristearate, tricaprylin, trilaurin, anhydro sorbitol can be used Tristearate, Arlacel-60, butyl stearate etc..Also, as acetylated monoglyceride, such as can be with Use biacetyl glyceryl monolaurate etc..As grease type, such as hydrogenated tallow, rilanit special etc. can be used.As Hydrocarbon compound, such as hexamethylene, atoleine etc. can be used.In addition, as oil-soluble polymerization inhibitor, such as can use to uncle Butyl-catechol, hydroquinones, benzoquinones etc..As fire retardant, such as HBCD, tetrabromobisphenol A system can be used Compound, trimethyl phosphate, brominated butadiene-styrene block copolymer, aluminium hydroxide etc..As colouring agent, can use Furnace black, channel black, thermals, acetylene black, Ketjen black, graphite, carbon fiber etc..As chain-transferring agent, such as can To use n-dodecyl mercaptan, α-methylstyrene dimer etc..Above-mentioned additive, can individually be added or two or more groups Close addition.

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 kind of 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.

In gas impregnated prefoam method, the compound resin in polymerization, after polymerization or in polymerization and after polymerization The foaming agents such as physical blowing agent are impregnated in particle.Hereinafter, by be impregnated with foaming agent composite resin particle referred to as " foaminess is multiple Resin particle ".Then, foaminess composite resin particle is put into pre-foaming machine, using vapor, hot blast or it The heating medium such as mixture heated, foaminess composite resin particle is foamed and is obtained expanded beads.In addition, Can also the composite resin particle as obtained from will polymerize in pressure vessel be filled into other pressure vessels and be pressed into hair Infusion and foaming agent is impregnated in composite resin particle and prepares 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.

As the shape of expanded beads, such as cylinder, rugby shape, spherical etc. can be enumerated as.In addition, though foaming The size of grain additionally depends on the amount of foaming agent, the size of resin particle, but a diameter of 0.5mm-5mm or so.

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 and character used in coating is not limited, can be that stoste can also be powder Body, it can also be the dilution of water or alcohol etc..Further, container when coating antistatic additive to expanded beads can be obturator System, open system it is any, as long as temperature during coating also for the heat resisting temperature of expanded beads below.It is preferred that coating When or expanded beads are sufficiently stirred after application and make antistatic additive be attached to composite foamed particle surface it is overall.Apply Coating method can be any of above method, or can also combine the above method.

In the working procedure of coating of antistatic additive, in order that the adhesion amount of antistatic additive is within the above range, with expanded beads For 100 mass parts meters, the antistatic additive of 0.3-5 mass parts is preferably coated with.In this case, can to assign expanded beads enough Excellent antistatic property, and can prevent the reduction of the mobility of expanded beads and prevent from filling during shaping bad.With multiple Resin expanded beads are 100 mass parts meters, and the coated weight of antistatic additive is more preferably 0.5-4 mass parts, more preferably 1-3 mass parts.Further, the cladding of antistatic additive, more preferably will hair as long as antistatic additive is present in the surface of expanded beads The surface of bubble particle is completely covered.Therefore, it is not absolutely required to surface being completely covered by the expanded beads that antistatic additive coats, There can be the part not covered by antistatic additive on expanded beads surface.

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】

Hereinafter, the embodiment of manufacture expanded beads, formed body is described in detail.

(embodiment 1)

(1) preparation of particle is planted

As vinylite, prepare the straight-chain low density polyethylene (LDPE) formed using metallocene polymerization polymerization catalyst (be specially Dong Cao companies manufacture " Nipolon-Z HF 210K ").The fusing point Tm of the vinylite is 103 DEG C.By the second Alkene system resin 20kg, Firebrake ZB (being specially the Firebrake ZB 2335 of rich field pharmacy (strain) manufacture) 0.144kg put into Henschel and mixed In conjunction machine (being specially the model FM-75E of the pond chemical industry machine (strain) of three well three manufacture), mix 5 minutes, obtain resin compound.

Then, existed using 26mm φ double screw extruder (being specially the model TEM-26SS that toshiba machine (strain) manufactures) Melting mixing is carried out to resin compound at a temperature of 230-250 DEG C.Melting mixing thing is extruded and by cutting mode in water Average 0.5mg/ are cut into, thus obtains kind of a particle.

(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 kind 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 1.72g, the tertiary own ester 0.86g of perbenzoic acid and α-methylstyrene Dimer 0.63g is dissolved in the first monomer (i.e. styrenic monomers).Then, while by dissolved matter with 500rpm stirring speed Degree is stirred while the aqueous medium put into autoclave.Further, as the first monomer, styrene 60g is used With 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.Temperature (being specially 100 DEG C) now is exactly polymerization temperature.In addition, reaching 100 DEG C of temperature , will be as the styrene 346.25g and methacrylic acid of second comonomer (being specially styrenic monomers) when after degree by 1 hour (that is, MAA) 3.75g was added in autoclave with 5 hours.Further, MAA to be dissolved in as in the styrene of second comonomer in advance State be added.

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 the composition of vinylite and from benzene The mass ratio of the composition of vinyl monomer.

For the composite resin particle obtained in the manner described above, by the use level of styrenic monomers, MAA amount, MAA Addition period, addition time, the quality of vinylite composition (that is, PE) and phenylethylene resin series component (that is, PS) compare table Show in table 1 described later.Further, MAA amount is adding up to relative to vinylite and styrenic monomers and MAA The amount of 100 mass parts.In addition, for composite resin particle, in such a way to by the xylene soluble in compound resin into (hreinafter referred to as " acetone is solvable for the glass transition temperature Tg of acetone soluble ingredient obtained from point being further dissolved in acetone The Tg " of composition) it is measured, and further carry out the evaluation of foaminess.It the results are shown in table 1.

" the 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, acetone soluble ingredient are carried out to supernatant.To gained The 2-4mg arrived acetone soluble ingredient, the DSC analyzer Q1000 manufactured using TA INSTRUMENTS companies, based on JIS K7121 carries out hot-fluid beamforming means of differential scanning calorimetry measure for (1987).Afterwards, it is 10 DEG C/minute that can obtain in firing rate Under the conditions of Tg of the intermediate point glass transition temperature as acetone soluble ingredient in obtained DSC curve.

" evaluation of foaminess "

It will be put into together with 3.5 liters of composite resin particle 1kg and water in the pressure vessel for the 5L for possessing mixer, further , the kaolin 5g as the dispersant and sodium alkyl benzene sulfonate 0.6g as surfactant is added into water.Then, one While with 300rpm mixing speed to being stirred in pressure vessel while 165 DEG C of blowing temperature will be warming up in pressure vessel Afterwards, into pressure vessel press-in as inorganic system's physical blowing agent carbon dioxide its pressure is changed into 4.0MPa (it is table Pressure), kept for 20 minutes under agitation.Afterwards, by the way that content is discharged under atmospheric pressure, composite resin particle is made to foam to obtain Expanded beads.The bulk density of obtained expanded beads is determined, and presses following benchmark evaluation foaminess.

That is, by bulk density less than 40kg/m³Situation be evaluated as " excellent ", by 40kg/m³Above and less than 50kg/m³'s Situation is evaluated as " good ", by 50kg/m³Situation above is evaluated as " bad ".It the results are shown in table 1 described later.Again Have, in table 1, the value of the bulk density in the evaluation of foaminess is shown, and its evaluation result is represented in bracket.Again Have, bulk density (unit：kg/m³), determine in such a way.First, prepare 1L graduated cylinder, fill and send out into the graduated cylinder of sky Bubble particle reaches at 1L graticule.Then, the quality (unit of the expanded beads per 1L is determined：g).Then, the hair to 1L is passed through Steep the quality (unit of particle：G) carry out unit conversion and calculate bulk density (unit：kg/m³)。

(3) preparation of expanded beads

The composite resin particle 500g prepared in the manner described above is put into together with the water 3500g as decentralized medium In the pressure vessel for possessing the 5L of mixer.Then, the height as dispersant is further added in the decentralized medium into container The ridge soil 5g and sodium alkyl benzene sulfonate 0.5g as surfactant.Then, while with 300rpm rotary speed in container It is stirred, while 165 DEG C of blowing temperature will be warming up in container.Afterwards, into container, press-in is used as inorganic system's physical blowing The carbon dioxide of agent, so that the pressure in container is changed into 3.9MPa (it is gauge pressure), and kept with same temperature (that is, 165 DEG C) 15 minutes.Thus carbonic maceration is made to obtain foaminess composite resin particle in composite resin particle.Then, pass through by Foaminess composite resin particle is discharged under atmospheric pressure together with decentralized medium from container, and it is 50kg/m to obtain bulk density³'s Expanded beads.Expanded beads are referred to as compound resin expanded beads due to being the foaming body of composite resin particle.Will Foaming condition is represented in table 1 described later.

For the carbonyl amount and vapor of the expanded beads prepared in the manner described above, in such a way measure surface Adsorbance.It the results are shown in table 1.

" carbonyl amount "

The carbonyl amount on expanded beads surface, the styrene amount by expanded beads surface and the styrene amount relative to surface The product of carbonyl amount represent.First, styrene amount and the carbonyl relative to styrene amount are determined in such a way Amount.

(a) styrene amount

When determining styrene amount, the infrared spectrophotometer " FT/ of Japanese light splitting company manufacture is used as measure device IR-460plus " and the total reflection absorption measurement device " ATR PRO 450-S types " with company's manufacture.In addition, total reflection absorbs The condition determination for determining device is prism：ZnSe, incidence angle：45°.Specifically, first, by expanded beads with 170kg/cm² Pressure extrusion and be close to total reflection absorption measurement device prism, the infrared spectrum on the surface of expanded beads is surveyed It is fixed, obtain infrared absorption spectroscopy (wherein, being corrected without ATR).

Then, to obtaining 698cm by infrared absorption spectroscopy (wherein, being corrected without ATR)^-1Neighbouring absorbance D₆₉₈、 2850cm^-1Neighbouring absorbance D₂₈₅₀It is measured, obtains dulling luminosity ratio D₆₉₈/D₂₈₅₀.Carried out for five expanded beads same Measure, the dulling luminosity ratio D using their average value as expanded beads₆₉₈/D₂₈₅₀.It the results are shown in table 1.

The absorbance D obtained by infrared absorption spectroscopy (wherein, being corrected without ATR)₆₉₈It is derived from mainly containing in benzene second Become the height of the peak value of angular oscillation outside the face of phenyl ring in alkene system resin.In addition, (wherein, there is no ATR schools by infrared absorption spectroscopy The absorbance D just) obtained₂₈₅₀It is derived from the C- of methylene contained in the both sides of vinylite and phenylethylene resin series The height of the peak value of stretching vibration between H.Moreover, the calibration curve of pre-made styrene, will be by above-mentioned infrared absorption spectroscopy The dulling luminosity ratio D for the expanded beads obtained₆₉₈/D₂₈₅₀It is updated in following (formulas 1) obtained by the calibration curve, thus obtains The styrene amount on expanded beads surface.It the results are shown in table 1.

(formula 1) styrene amount=0.7622 × (dulling luminosity ratio D₆₉₈/D₂₈₅₀)²+ 7.4831 × (dulling luminosity ratio D₆₉₈/D₂₈₅₀)+ 1.1635

Being made for the calibration curve of styrene is carried out in such a way.I.e., first, using extruder to polyethylene (tool Body be Dong Cao companies manufacture " Nipolon-Z HF 210K ") and polystyrene (be specially PS Japan companies manufacture " 680 ") according to 100/0,91.8/8.2,78.8/21.2,55.3/44.7,0/100 mol ratio, (it is polyethylene/polyphenyl second Alkene) carry out melting mixing prepare particle (pellet).Specifically, molal weight based on ethene is 28g/mol, styrene Molal weight is 104g/mol, after mol ratio is converted into mass ratio, reaches the poly- of specific mass ratio with weighing respectively Ethene, polystyrene, thus prepare the particle (pellet) with above-mentioned mol ratio.Then, the temperature heating with 180 DEG C is utilized The particle (pellet) is configured to film-form by press afterwards, thus obtains film.Filled using above-mentioned total reflection absorption measurement Put and the infrared absorption spectroscopy (wherein, being corrected without ATR) of film is measured.Then, surveyed according to method same as described above The fixed absorbance D obtained by infrared absorption spectroscopy (wherein, being corrected without ATR)₆₉₈With absorbance D₂₈₅₀, obtain dulling luminosity ratio D₆₉₈/D₂₈₅₀.Then, by the styrene amount (unit in standard specimen：Mol% transverse axis) is set to, by dulling luminosity ratio D₆₉₈/D₂₈₅₀If For the longitudinal axis, thus, it is possible to obtain as exemplified calibration curve such as Fig. 1.

(b) relative to the carbonyl amount of styrene amount

When determining carbonyl amount, device is determined using with the measure identical of above-mentioned styrene amount, total reflection, which absorbs, surveys The measuring condition for measuring device is also identical with the measure of styrene amount.Specifically, first, by expanded beads with 170kg/cm²'s Pressure extrusion and the prism for being close to total reflection absorption measurement device, are measured to the infrared spectrum on the surface of expanded beads, Obtain infrared absorption spectroscopy (wherein, being corrected without ATR).Then, to being obtained by infrared absorption spectroscopy (wherein, being corrected without ATR) To 698cm^-1Neighbouring absorbance D₆₉₈、1730cm^-1Neighbouring absorbance D₁₇₃₀It is measured, obtains dulling luminosity ratio D₁₇₃₀/D₆₉₈。 Same measure, the dulling luminosity ratio D using their average value as expanded beads are carried out for five expanded beads₁₇₃₀/D₆₉₈。 Further, the absorbance D obtained by infrared absorption spectroscopy (wherein, being corrected without ATR)₁₇₃₀It is derived from (methyl) acrylic component The height of the peak value of stretching vibration between the C=O of the carboxyl of unit.Moreover, pre-made calibration curve, will be by above-mentioned infrared suction Receive the dulling luminosity ratio D for the expanded beads that spectrum is obtained₁₇₃₀/D₆₉₈It is updated in following (formulas 2) obtained by the calibration curve, by This obtains the carbonyl amount relative to styrene amount.It the results are shown in table 1.

(formula 2) relative to styrene amount carbonyl amount=6.4838 × (dulling luminosity ratio D₁₇₃₀/D₆₉₈)-0.0523

Being made for the calibration curve of carbonyl amount is carried out in such a way.That is, passed through using styrene and butyl acrylate The amount that suspended polymerization prepares butyl acrylate is respectively 0mol%, 0.8mol%, 2.5mol%, 4.1mol% polymerization Grain.Then, utilize the press after the temperature heating with 180 DEG C that aggregated particles are configured into film-form, obtain film.Using upper Total reflection absorption measurement device is stated to be measured the infrared absorption spectroscopy (wherein, correcting without ATR) of film.Then, according to The absorbance D that method measure same as described above is obtained by infrared absorption spectroscopy (being corrected without ATR)₆₉₈With absorbance D₁₇₃₀, ask Go out dulling luminosity ratio D₁₇₃₀/D₆₉₈.Then, by the carbonyl amount (unit in standard specimen：Mol% transverse axis) is set to, by dulling luminosity ratio D₁₇₃₀/D₆₉₈The longitudinal axis is set to, thus, it is possible to the calibration curve shown as exemplified in fig. 2.

(c) surface carbonyl amount

It will be multiplied by the styrene amount on the expanded beads surface obtained according to the method described above divided by 100 obtained values relative Value, the surface carbonyl amount as compound resin expanded beads obtained from carbonyl amount in styrene amount.It the results are shown in In table 1.

" the water vapor adsorption amounts of compound resin expanded beads "

The measure of water vapor adsorption amount, use (BELSORP-max (the Japanese Baeyer strain formula meetings of vapor sorption amount determining device Society manufactures)), (setting relative pressure is measured to adsorption isotherm at 25 DEG C：0.005-0.9), maximum relative pressure is obtained Water vapor adsorption amount of the water vapor adsorption amount as the compound resin expanded beads of present invention when power is 0.9.Specifically, it is first About 0.2g composite resin particle is first weighed in advance.Then, the composite resin particle of weighing is put into sample unit, used BELSORP-max (Japanese Baeyer Co., Ltd. manufacture) is measured (setting phase to the adsorption isotherm of the vapor at 25 DEG C To pressure：0.005-0.9), water vapor adsorption amount when maximum relative pressure is 0.9 is obtained as compound resin expanded beads Water vapor adsorption amount.It the results are shown in table 1.

(4) the coating process 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 polybag together with antistatic additive, fully After rocking mixing, it is put into roller and mixes 30 minutes together with sack, antistatic additive is thus coated on expanded beads.With foaming Grain is 100 mass parts meters, and the addition of antistatic additive is 2 mass parts.Counted by 100 mass parts of expanded beads, as effectively into Component is 1 mass parts.Afterwards, expanded beads are dried 12 hours in the baking oven that temperature is 40 DEG C.So, obtain on surface It is attached with the expanded beads of antistatic additive.For the adhesion amount of the expanded beads, in such a way measure antistatic additive.

" adhesion amount of antistatic additive "

The about 5g foaming for being attached with antistatic additive expanded beads and about 5g unattached antistatic additive is weighed respectively Grain.The weight of the expanded beads of unattached antistatic additive is set to W₀(W₀≈5).Use 100cm³(ml) cleaning fluid (is specially second Alcohol) each expanded beads after weighing are cleaned three times.About 300cm after recovery and rinsing³Cleaning fluid, protected at a temperature of 40 DEG C Hold 24 hours, thus evaporate cleaning fluid.Then, it is residual after the evaporation to the cleaning fluid of the expanded beads that are attached with antistatic additive Slag thing weight W_AResidue weight W after evaporation with the cleaning fluid of the expanded beads of unattached antistatic additive_BIt is measured.Base In residue weight W_A、W_BAnd the weight W of expanded beads₀, the foaming relative to 100 mass parts is calculated by following (formulas 3) The adhesion amount A (mass parts) of the antistatic additive of grain.It the results are shown in table 1.

(formula 3) A=(W_A-W_B)/W₀×100

(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 being adjusted to load 12 hours in 60 DEG C of baking oven, so that the drying of body and maintenance is formed.So, multiple foaming are obtained The formed body that particle mutually merges.

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 1.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 the hair being internally broken respectively Steep the quantity of particle and the quantity of the expanded beads in interface peel.Then, calculate the expanded beads that are internally broken relative to The expanded beads that are internally broken and interface peel expanded beads total quantity ratio, its is expressed as a percentage Value is used as fusion rate (%).

" 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 K 6271-1-2015.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 cut out test film for the mode on expanded beads formed body surface (that is, skin surface).Then, using Mitsubishi Chemical " HirestaMCP-HT450 " of company's manufacture, the surface resistivity on the skin surface of determination test piece.As probe, use " UR100 " of Mitsubishi Chemical Ind's manufacture, in 23 DEG C, 50%RH, keeps 500V applied voltage to be surveyed under conditions of 30 seconds It is fixed.It is measured for any four position on same test film, and obtains its maximum, minimum value and arithmetic average Value.Further, 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, first, thickness is cut out in a manner of whole surface is cutting face from any part of formed body is for 20mm × width 25mm × length is 120mm five test films.Test film is put in the constant temperature and humidity room that room temperature is 23 DEG C, humidity is 50% After putting more than 24 hours, distance between the fulcrum is 100mm, the radius R of pressure head is 15.0mm, the radius R of supporting table be 15.0mm, Under conditions of test speed is 20mm/min, room temperature is 23 DEG C, humidity is 50%, with (strain), Shimadzu Seisakusho Ltd. manufactures AutographAGS-10kNG testing machines are measured to crooked elastic rate.Using the arithmetic mean of the measured value of five test films It is worth the measurement result as crooked elastic rate.

" bend fracture energy "

Carry out determining same three point bending test with above-mentioned crooked elastic rate, by amount of deflection (unit：M/m) and stress is (single Position：MPa relation) and energy (unit when reaching breakaway poing is obtained by the arithmetic average of the measured value of five test films： 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 bending Energy to fracture.

" compressive strength "

From the central element 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)

Embodiment 2-4 is the example for the proportioning for changing MAA.Specifically, in this example, using 345g styrene as The MAA of second comonomer and 5g, in addition, expanded beads, formed body is prepared according to the same manner as in Example 1.

(embodiment 3)

In this example, using 347.5g styrene as second comonomer and 2.5g MAA, in addition, according to reality Apply the identical mode of example 1 and prepare expanded beads, formed body.

(embodiment 4)

In this example, using 348.75g styrene as second comonomer and 1.25g MAA, in addition, according to The identical mode of embodiment 1 prepares expanded beads, formed body.

(embodiment 5)

Embodiment 5 and embodiment 6 are to change MAA proportioning, and further change addition MAA opportunity and addition institute The example of the time needed.Specifically, in this example, the natrium nitrosum amount used as water-soluble polymerization inhibitor is become from 0.21g More 0.15g, added when after the temperature of autoclave reaches 100 DEG C by 1 hour with 50 minutes 4 hours into autoclave The styrene of 348.75g second comonomer, 1.25g MAA was added into autoclave with 10 minutes after styrene is added, except this In addition, expanded beads, formed body are prepared according to the same manner as in Example 1.

(embodiment 6)

In this example, the natrium nitrosum amount used as water-soluble polymerization inhibitor is changed to 0.15g from 0.21g, in high pressure The temperature of kettle reaches after 100 DEG C by the benzene for the second comonomer for adding 347.5g at 1 hour into autoclave with 50 minutes 4 hours Ethene, 2.5g MAA was added into autoclave with 10 minutes after styrene is added, in addition, according to same as Example 1 Mode prepare expanded beads, formed body.

(embodiment 7)

Embodiment 7 and embodiment 8 are to change the mass ratio of vinylite and phenylethylene resin series in compound resin Example.Specifically, in this example, by the quantitative change more 150g of the kind particle added into autoclave, 135g benzene is used The mix monomer of ethene and 15g butyl acrylate is as the first monomer, using 196.25g styrene as second comonomer, In addition, expanded beads, formed body are prepared according to the same manner as in Example 1.

(embodiment 8)

In this example, the quantitative change more 50g for the kind particle that will be added into autoclave, uses 35g styrene and 15g The mix monomer of butyl acrylate, using 396.25g styrene as second comonomer, in addition, is pressed as the first monomer Expanded beads, formed body are prepared according to mode same as Example 1.

(embodiment 9)

This example is that MAA is changed to acrylic acid (that is, AA) example.Specifically, in this example, MAA is replaced using AA, In addition, expanded beads, formed body are prepared according to the same manner as in Example 1.

(comparative example 1)

This example is the expanded beads and the example of formed body prepared without using methacrylic acid and acrylic acid.Specifically For, in this example, do not add methacrylic acid, and use 350g styrene as second comonomer, in addition, according to The identical mode of embodiment 1 prepares expanded beads, formed body.

(comparative example 2)

This example is the very few example of the addition of methacrylic acid.Specifically, in this example, using 349.55g benzene Ethene is as second comonomer and 0.45g MAA, in addition, prepare according to the same manner as in Example 1 expanded beads, into Body.

(comparative example 3)

Comparative example 3 is the example that methacrylic acid excessively adds.Specifically, in this example, using 337.55g benzene second Alkene in addition, prepares expanded beads, shaping according to the same manner as in Example 1 as second comonomer and 12.5g MAA Body.

(comparative example 4)

This example is very few relative to the addition of the styrenic monomers of vinylite, and further with the first monomer The example of methacrylic acid is added together.Specifically, in this example, by the quantitative change of the kind particle added into autoclave more 260g.Also, the mix monomer of 221.25g styrene and 15g butyl acrylate is used as the first monomer, and will 3.75g methacrylic acids are added in autoclave together with first monomer.In addition, according to side same as Example 1 Formula prepares expanded beads, formed body.

(comparative example 5)

This example is relative to the excessive example of the addition of the styrenic monomers of vinylite.Specifically, at this In example, by the quantitative change more 24g of the kind particle added into autoclave.Also, use 9g styrene and 15g acrylic acid fourth The mix monomer of ester is as the first monomer.Also, 448.25g styrene is used as second comonomer.In addition, according to The identical mode of embodiment 1 prepares expanded beads, formed body.

(comparative example 6)

This example is that methacrylic acid (that is, MAA) is changed into methyl methacrylate (that is, MMA) as second comonomer Example.Specifically, in this example, will as the 346.25g of second comonomer (be specially styrenic monomers) styrene and 3.75g methyl methacrylate was added in autoclave with 5 hours.Further, MMA is used as second comonomer to be dissolved in advance State addition in styrene.In addition, expanded beads, formed body are prepared according to the same manner as in Example 1.

Evaluation same as Example 1 is also carried out for embodiment 2-9 and comparative example 1-6, the results are shown in table 1 And in table 2.

As shown in Table 1, table is shown using the formed body that antistatic additive is attached with obtained from the expanded beads of embodiment Surface resistivity is less than 1 × 10¹²This excellent antistatic properties of Ω.In addition, being attached with the expanded beads of antistatic additive, playing While above-mentioned excellent antistatic property, amalgamation is also very excellent.Therefore, it is possible to manufacture internal good knitting, compression rigidity And resistance to deflection is excellent and can prevent damaged formed body as caused by deformation.Therefore, using the expanded beads of embodiment and Obtained formed body is applied to electronic equipment as automobile component, liquid crystal panel, solar power generation panel etc., precision equipment Packing container etc..

On the other hand, as shown in Table 2, in the less comparative example 1 of the surface carbonyl amount of compound resin expanded beads and contrast In example 2, sufficient antistatic property can not be obtained.In addition, in the comparative example 3 of addition of (methyl) acrylic acid is added, The glass transition temperature of acetone soluble ingredient is higher, and foaminess, amalgamation become insufficient.In the addition of styrenic monomers Measure in less comparative example 4, because the rigidity of formed body declines, therefore compressive strength is smaller, crooked elastic rate is relatively low.Therefore, The formed body of comparative example 4 easily deforms because of flexure, and resistance to deflection is insufficient.On the other hand, in the addition of styrenic monomers Measure in more comparative example 5, although the compressive strength of formed body, crooked elastic rate uprise, bend fracture energy deficiency.Cause This, the breakage as caused by deformation easily occurs for the formed body of comparative example 5.In addition, in comparative example 6, can not obtain sufficiently anti- Antistatic property.

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, the compound resin expanded beads are with the dipping polymerization (methyl) third in vinylite The compound resin that olefin(e) acid and styrenic monomers form as substrate resin,

Counted by 100 mass parts of vinylite, what the compound resin contained 100-1900 mass parts derives from polystyrene The construction unit of monomer,

Acetone soluble ingredient obtained from xylene soluble fraction in the compound resin is further dissolved in acetone Glass transition temperature Tg below 105 DEG C,

The carbonyl amount on the surface of the compound resin expanded beads is more than 0.03mol%.

2. compound resin expanded beads according to claim 1, it is characterised in that using the compound resin as 100 mass Part meter, the content from the construction unit of (methyl) acrylic acid is 0.1-2 mass parts.

3. compound resin expanded beads according to claim 1 or 2, it is characterised in that the compound resin expanded beads Water vapor adsorption amount be 0.5cm³/ more than g.

4. the compound resin expanded beads according to any one of claim 1-3, it is characterised in that the vinylite Including straight-chain low density polyethylene (LDPE) or straight-chain low density polyethylene (LDPE) and vinyl-vinyl acetate copolymer, the second The content of vinyl-vinyl acetate copolymer in alkene system resin is less than 10 mass %.

5. the compound resin expanded beads according to any one of claim 1-4, it is characterised in that with ethene system tree Fat is 100 mass parts meters, and the compound resin contains have more than below 400 mass parts and 1900 mass parts described and derives from benzene second The construction unit of alkene monomer.

6. the compound resin expanded beads according to any one of claim 1-5, it is characterised in that the compound resin hair Bubble particle surface coated by antistatic additive, counted using the compound resin expanded beads as 100 mass parts, the antistatic additive it is attached The amount of wearing is 0.3-5 mass parts.

7. a kind of compound resin expanded beads formed body, it is that compound resin expanded beads according to claim 6 mutually melt The formed body formed is closed, the surface resistivity of the formed body is less than 1 × 10¹²Ω。

8. a kind of manufacture method of compound resin expanded beads, has：

Modified process, it is dispersed with an aqueous medium in the dispersion liquid of vinylite kind particle, with the vinylite kind Vinylite in particle is 100 mass parts meters, adds the styrenic monomers and (methyl) propylene of 100-1900 mass parts Acid, impregnated in the vinylite kind particle, polymerize the styrenic monomers and (methyl) acrylic acid, answered Resin particle；With

Foamed process, the composite resin particle is foamed using foaming agent, obtain compound resin expanded beads,

Acetone obtained from xylene soluble fraction in the compound resin expanded beads is further dissolved in acetone can The glass transition temperature Tg of melt into point below 105 DEG C,

9. the manufacture method of compound resin expanded beads according to claim 8, it is characterised in that in the modified process In, the styrenic monomers are divided into and are continually superimposed the aqueous medium, make described (methyl) acrylic acid at least with most The styrenic monomers added afterwards impregnate, are aggregated in the ethene system kind particle together.

10. the manufacture method of compound resin expanded beads according to claim 8 or claim 9 the, it is characterised in that with (first Base) acrylic acid and the total amount of the vinylite and the styrenic monomers be 100 mass parts meters, (methyl) The addition of acrylic acid is 0.1-2 mass parts.