CN101925647A - Expandable polystyrene resin beads, process for production thereof, pre-expanded beads and expanded moldings - Google Patents
Expandable polystyrene resin beads, process for production thereof, pre-expanded beads and expanded moldings Download PDFInfo
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- CN101925647A CN101925647A CN2009801032488A CN200980103248A CN101925647A CN 101925647 A CN101925647 A CN 101925647A CN 2009801032488 A CN2009801032488 A CN 2009801032488A CN 200980103248 A CN200980103248 A CN 200980103248A CN 101925647 A CN101925647 A CN 101925647A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
- C08J9/232—Forming foamed products by sintering expandable particles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
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Abstract
Expandable polystyrene resin beads which can give expanded moldings having beautiful surface appearance and high strength even when the molding steam pressure is low and which permit shorter molding time. The expandable polystyrene resin beads can be produced by conducting the first polymerization step (1) of introducing 7.0 to 80.0 parts by mass of a styrenic monomer and 2.0 to 12.0 parts by mass of an acrylic ester monomer into an aqueous dispersion of seed particles of polystyrene resin per 100 parts by mass of the seed particles and making these monomers absorbed by the seed particles and polymerized to grow the seed particles; the second polymerization step (2) of introducing only a styrenic monomer into the dispersion and making the monomer absorbed by the seed particles and polymerized to grow resin particles; and the impregnation step (3) of impregnating the resulting particles with a blowing agent after or during the step (2).
Description
Technical field
The present invention relates to a kind of manufacture method of expandable polystyrene resin beads, this resin particle is used to make as food product containers, packing, the useful polystyrene resin expanded moldings of cushioning material.And, in more detail, the present invention relates to the manufacture method of following expandable polystyrene resin beads, even the pressure of the water vapor that uses during this expandable polystyrene resin beads moulding also can obtain beautiful appearance and have high-intensity expanded moldings as low pressure, since can low pressure molding, so in molding procedure, can shorten the molding time of each injection.
The application is based on requiring right of priority Japanese Patent Application 2008-19000 number of Japanese publication on January 30th, 2008, and with its content quotation in this.
Background technology
In the past, as containers for food use, packing, the employed expanded plastic of cushioning material, used polystyrene resin expanded moldings mostly with excellent heat insulating ability, economy, wholesomeness.
Generally, the manufacture method of the industrial polystyrene resin expanded moldings that carries out is implemented following method: utilize thermal medium such as steam will contain the expandable polystyrene resin beads heating of volatile foaming agent etc., make its foaming (pre-frothing) to desired bulk density, this pre-expanded beads is filled in this die cavity of the shaping mould with the die cavity that forms required forming shape, utilize thermal medium such as steam to heat pre-expanded beads in this die cavity, carry out the foam-in-mould moulding, make expanded moldings.At this moment, the density of resulting polystyrene resin expanded moldings is roughly identical with bulk density under the pre-frothing.The desired intensity of set basis polystyrene resin expanded moldings of bulk density and the foam performance that expandable polystyrene resin beads is had decide.For example, the employed polystyrene resin expanded moldings of food product containers such as the wrapping material of household appliances etc., fish box is with about 0.02～0.017g/cm
3The density supply market.
In this molding procedure, the outward appearance of expanded moldings and intensity change according to the temperature (being heating steam pressure under the situation of water vapor) of heating mediums such as steam.For example, when heating with water vapor, if improve heated pressure, then the outward appearance of formed body, intensity have the tendency of raising, but because cooling time is elongated, so productivity reduces, are not preferred.
And then, if heated pressure increases, the surperficial melted by heat of expanded moldings then, thereby the degraded appearance of expanded moldings.
On the contrary, carry out moulding if reduce heated pressure, then the molding time of each injection shortens, but bonding the dying down between the pre-expanded beads, the outward appearance of expanded moldings, intensity variation.
So, free forming is to a certain extent pressed from low pressure to high pressure in the heating steam of steam in the molding procedure, and this is one of key property of expandable polystyrene resin beads.
Generally, relation in the manufacturing of polystyrene resin expanded moldings between the intensity of the molding time of each injection and expanded moldings is: when molding time is long, obtain having high-intensity expanded moldings, on the contrary in short-term in molding time, the tendency that the intensity of visible expanded moldings reduces.
As the prior art of the molding time that is used to shorten the polystyrene resin expanded moldings, can enumerate for example patent documentation 1～5.
In the patent documentation 1, proposed a kind of under the surface-coated normal temperature of expandable polystyrene resin beads the method for the ester of pulverous aliphatic carboxylic acid below solid 60 orders and fatty alcohol.Though this method can significantly shorten the cooling time in the molding time, and is effective to the cripetura of molding time, there is the tendency that reduces with intensity.
In addition, method in the emulsion of expandable polystyrene resin beads or the surface-coated paraffin of expanded particle has been proposed in the patent documentation 2, method at expandable polystyrene resin beads or the surface-coated whiteruss of expanded particle has been proposed in the patent documentation 3, proposed method in the patent documentation 4, proposed method in the patent documentation 5 at expandable polystyrene resin beads or the surface-coated polyethers of expanded particle at the surface-coated specific silicone compounds of expandable polystyrene resin beads or expanded particle.But, the reduction of intensity when these methods are not avoided making expanded moldings yet.
Patent documentation 1: Japanese Patent Publication 58-56568 communique
Patent documentation 2: Japanese kokai publication sho 60-195135 communique
Patent documentation 3: Japanese kokai publication sho 51-135969 communique
Patent documentation 4: Japanese kokai publication sho 52-865 communique
Patent documentation 5: Japanese kokai publication sho 59-202235 communique
Summary of the invention
The present invention In view of the foregoing makes, purpose provides a kind of expandable polystyrene resin beads, even the pressure of the water vapor that uses during this expandable polystyrene resin beads moulding is low pressure, also can access beautiful appearance and have high-intensity expanded moldings, since can low pressure molding, so in molding procedure, can shorten the molding time of each injection.
In order to reach above-mentioned purpose, the invention provides a kind of manufacture method of expandable polystyrene resin beads, wherein carry out following operation and obtain expandable polystyrene resin beads:
(1) polystyrene resin kind grain is scattered in the dispersion liquid that forms in the water, with respect to 100 mass parts polystyrene resin kind grains, supply with 7.0～80.0 mass parts styrenic monomers and 2.0～12.0 mass parts acrylic ester monomers, make kind of grain absorb these monomers and carry out polymerization and the 1st polymerization process that polystyrene resin kind grain is grown up;
(2) then, in this dispersion liquid, only supply with styrenic monomers, make kind of grain absorb this monomer and carry out polymerization and the 2nd polymerization process that polystyrene resin beads is grown up; With
(3) carrying out the operation that the 2nd polymerization process has been made behind the polystyrene resin beads or made it the impregnation whipping agent in the growth of polystyrene resin beads midway.
In addition, the invention provides a kind of expandable polystyrene resin beads, it is the expandable polystyrene resin beads that contains styrenic monomers and the monomeric multipolymer of acrylic ester, wherein, the absorbancy of described expandable polystyrene resin beads than (A) and absorbancy than (B) satisfied following relation:
(A)＜(B), and (A) be more than 0.05,
Described absorbancy is calculated than (A) is following: by ATR method infrared spectroscopic analysis the surface of above-mentioned expandable polystyrene resin beads being analyzed in the infrared absorption spectrum that obtains, obtain 1730cm
-1The absorbancy D1730 and the 1600cm at place
-1The absorbancy D1600 at place is calculated by D1730/D1600,
Described absorbancy is calculated than (B) is following: in the infrared absorption spectrum that the central part analysis of above-mentioned expandable polystyrene resin beads is obtained by ATR method infrared spectroscopic analysis, obtain 1730cm
-1The absorbancy D1730 and the 1600cm at place
-1The absorbancy D1600 at place is calculated by D1730/D1600.
In the above-mentioned expandable polystyrene resin beads, preferred above-mentioned absorbancy than (A) in 0.05～0.50 scope, and above-mentioned absorbancy than (B) in 0.20～0.60 scope.
In the above-mentioned expandable polystyrene resin beads, preferred above-mentioned absorbancy than (B) and (A) ratio (B/A) in 1.10～3.00 scope.
Above-mentioned expandable polystyrene resin beads preferably manufacture method by above-mentioned expandable polystyrene resin beads obtains.
In addition, the invention provides a kind of pre-expanded beads, it is that above-mentioned expandable polystyrene resin beads pre-frothing is become bulk density is 0.01～0.033g/cm
3Scope obtain.
In addition, the invention provides a kind of expanded moldings, it is to be filled in above-mentioned pre-expanded beads in the die cavity of shaping mould and to heat, and the foam-in-mould moulding obtains by carrying out.
Even the pressure of the water vapor that expandable polystyrene resin beads of the present invention uses when moulding is low pressure, also can obtains beautiful appearance and have high-intensity expanded moldings.
By the present invention,, also can obtain be difficult for to take place expanded moldings because of the formed body appearance degradation of thermotolerance due to reducing even under high vapor pressure, carry out moulding.
By the present invention, can provide a kind of non-constant width of condition and range, the expanded moldings of desirable quality when satisfying various moulding that can moulding.
Expandable polystyrene resin beads of the present invention is compared with currently available products with pre-expanded beads, foam performance through the time tail off, compared with currently available products, even after long-time the preservation, still have sufficient foam performance, the keeping quality excellence.
Description of drawings
Fig. 1 is illustrated in the mensuration of absorbancy ratio of the expandable polystyrene resin beads that is undertaken by ATR method infrared spectroscopic analysis the synoptic diagram of the absorbance measurement position on the surface of expandable polystyrene resin beads.
Fig. 2 is illustrated in the mensuration of absorbancy ratio of the expandable polystyrene resin beads that is undertaken by ATR method infrared spectroscopic analysis the synoptic diagram of the absorbance measurement position of the central part of expandable polystyrene resin beads.
Nomenclature
1... expandable polystyrene resin beads, A... surface, B... central part.
Embodiment
The manufacture method of expandable polystyrene resin beads of the present invention is characterised in that, carries out following operation, thereby obtains expandable polystyrene resin beads:
(1) polystyrene resin kind grain is scattered in the dispersion liquid that forms in the water, with respect to 100 mass parts polystyrene resin kind grains, supply with 7.0～80.0 mass parts styrenic monomers and 2.0～12.0 mass parts acrylic ester monomers, make kind of grain absorb these monomers and carry out polymerization and the 1st polymerization process that polystyrene resin kind grain is grown up;
(2) then, in this dispersion liquid, only supply with styrenic monomers, make kind of grain absorb this monomer and carry out polymerization and the 2nd polymerization process that polystyrene resin beads is grown up; With
(3) carrying out the operation that the 2nd polymerization process has been made behind the polystyrene resin beads or made it the impregnation whipping agent in the growth of polystyrene resin beads midway.
In the manufacture method of the present invention,, can enumerate the homopolymer of vinylbenzene or styrene derivatives for polystyrene resin as the material of polystyrene resin kind grain (being designated hereinafter simply as kind of a grain).At this,, can enumerate alpha-methyl styrene, p-methylstyrene, t-butyl styrene, chloro-styrene etc. as styrene derivatives.In addition, also can enumerate vinyl cyanide, dimethyl fumarate, ethyl fumarate etc. can with styrene copolymerized monomer and cinnamic multipolymer, the above-mentioned multipolymer that multi-functional monomers such as Vinylstyrene, alkylene glycol methacrylic ester is share and obtain, be added with the resin of an amount of rubber-like substance etc., the optimization styrene composition is above multipolymer or styrene homopolymers of 50 quality %.This polystyrene resin preferable weight-average molecular weight is 150,000～400,000 scope.And, plant grain and can part or all use the polystyrene resin recovery article.
And then, plant the particle diameter of grain and can suitably adjust according to the median size of the polystyrene resin beads of making etc., for example making median size when being the polystyrene resin beads of 1.0mm, preferably using median size is kind grain about 0.4～0.7mm.
In the manufacture method of the present invention,, can enumerate vinylbenzene or styrene derivatives as styrenic monomers.At this,, can enumerate alpha-methyl styrene, p-methylstyrene, t-butyl styrene, chloro-styrene etc. as styrene derivatives.Among the present invention, optimization styrene in these styrenic monomers.
In the manufacture method of the present invention,, can enumerate methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate etc., preferred ethyl propenoate, propyl acrylate, butyl acrylate as the acrylic ester monomer.
With respect to 100 mass parts polystyrene resin kind grains, used styrenic monomers in the 1st polymerization process of the present invention is set at 7.0～80.0 mass parts.During less than 7.0 mass parts, the thermotolerance during moulding reduces, and if above 80.0 mass parts, then low pressure molding variation.Be preferably 8.0～72.0 mass parts.
And,, used acrylate monomer in the 1st polymerization process of the present invention is set at 2.0～12.0 mass parts with respect to 100 mass parts polystyrene resin kind grains.If less than 2.0 mass parts, low pressure molding variation then, if surpass 12.0 mass parts, then thermotolerance reduces.Be preferably 2.0～11.2 mass parts.
As the whipping agent that adds in expandable polystyrene resin beads of the present invention, boiling point is that the following and normal pressure of the softening temperature of polystyrene resin is fit to for gaseous state or liquid organic compound down.For example, can use hydrocarbon such as propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, neopentane, pentamethylene, cyclopentadiene, normal hexane, sherwood oil; Ketone such as acetone, methyl ethyl ketone; Alcohols such as methyl alcohol, ethanol, Virahol; Lower boiling ether compounds such as dme, diethyl ether, dipropyl ether, methyl ethyl ether; Inorganic gass such as carbonic acid gas, nitrogen, ammonia etc.These whipping agents can only use a kind of, can also share two or more.Wherein, preferred blowing agent is that boiling point is-45～40 ℃ a hydrocarbon, preferably propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane etc.With respect to 100 mass parts polystyrene resin beads, the addition of this whipping agent is preferably the scope of 5～15 mass parts.
When making expandable polystyrene resin beads by manufacture method of the present invention, in reaction vessels such as autoclave, add aqueous medium, above-mentioned kind grain is dispersed in this aqueous medium, in this aqueous medium, in above-mentioned (1) the 1st polymerization process, supply with styrenic monomers and acrylic ester monomer continuously or discontinuously, then, in above-mentioned (2) the 2nd polymerization process, only supply with styrenic monomers continuously or discontinuously, in the presence of polymerization starter, make the surperficial and/or kind intragranular portion growth of cinnamic acrylic ester based copolymer and polystyrene resin, make the polystyrene resin beads of regulation particle diameter at kind of grain.
In above-mentioned (1) the 1st polymerization process and (2) the 2nd polymerization process, under the few situation of consumption of kind of grain, the polymerization of starting monomer can not be controlled at proper range, the extreme polymer of polystyrene resin quantizes or produces the polystyrene resin of a large amount of micronized, makes efficient and reduces.In addition, under the consumption situation how, the amount that 1 production obtains is few, produces rate variance.Therefore, as the suitable consumption of kind of grain, with respect to the polystyrene resin total amount, the scope of preferred 10～60 quality %, the more preferably scope of 15～50 quality %.
As spendable polymerization starter in above-mentioned (1) the 1st polymerization process and (2) the 2nd polymerization process, so long as be used for styrenic monomers polymeric initiator in the past, just can be not particularly limited to use, for example can enumerate benzoyl peroxide, peroxidized t-butyl perbenzoate, peroxide-2-ethyl hexanoic acid tert-butyl, lauryl peroxide, tert-butyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, tert-butylperoxy isopropyl carbonate, peroxide acetic acid butyl ester, 2,2-tert-butyl hydroperoxide butane, peroxidation-3,3, the 5-tri-methyl hexanoic acid tert-butyl ester, organo-peroxides such as peroxidation six hydrogen terephthalic acid di tert butyl carbonates; Diisopropyl azodicarboxylate, azo two azo-compounds such as (methyl pentane nitriles) etc.In these polymerization starters, the decomposition temperature that is particularly preferred for obtaining 10 hour transformation period is at 80～120 ℃ polymerization starter.This polymerization starter can either be used alone, and can also share different polymerization starters more than 2 kinds.
And then, make above-mentioned kind grain and monomeric droplet be dispersed in the suspension stabilizer of above-mentioned aqueous medium as being used for, so long as be used for the stablizer of the suspension polymerization of polystyrene resin in the past, just can be not particularly limited to use, for example can enumerate insoluble mineral compound such as water-soluble polymers such as polyvinyl alcohol, methylcellulose gum, polyacrylamide, polyvinylpyrrolidone, tricalcium phosphate, magnesium pyrophosphate etc.Suspension stabilizer can be used alone, and the suspension stabilizer more than 2 kinds can also be mixed and use.
Using under the situation of insoluble mineral compound as above-mentioned suspension stabilizer, preferably share anion surfactant.As such anion surfactant, can enumerate for example fatty acid soaps, N-acylamino acid or carboxylate salts such as its salt, alkyl ether carboxy acid salt; Sulfonate such as alkylbenzene sulfonate, sulfonated alkyl naphathalene, dialkyl sulfosuccinic salt, alkyl sulfoacetate, sulfonated; Sulfuric acids such as higher alcohol sulfate salt, senior secondary alcohol sulfuric acid, sulfated alkyl ether, polyoxyethylene alkylphenyl ether sulfate salt; Phosphate ester salt such as alkyl ether phosphate salt, alkyl phosphate salt etc.These anion surfactants can be used alone or mix two or more uses.
In above-mentioned (1) the 1st polymerization process, for styrenic monomers that is supplied in aqueous medium and the monomeric amount of acrylic ester, with respect to 100 mass parts kind grains, styrenic monomers is the scope of 7.0～80.0 mass parts, and the acrylic ester monomer is the scope of 2.0～12.0 mass parts.By styrenic monomers in (1) the 1st polymerization process and the monomeric amount of acrylic ester are set in the above-mentioned scope, can access following expandable polystyrene resin beads: even the pressure of the water vapor that uses during moulding is low pressure, also can access beautiful appearance and have high-intensity expanded moldings, because the energy low pressure molding is so can shorten the molding time of each injection in molding procedure.
In above-mentioned (2) the 2nd polymerization process, after above-mentioned (1) the 1st polymerization process finishes, only add styrenic monomers in the aqueous medium in reaction vessels such as autoclave, polystyrene resin is grown up, make polystyrene resin beads.Amount to the styrenic monomers used in this (2) the 2nd polymerization process is not particularly limited, and preferably resinous principle 100 mass parts with respect to the polystyrene resin beads that obtains behind the 2nd polymerization process are the scope of 30.0～80.0 mass parts.
In the manufacture method of the present invention, can use any following method when making polystyrene resin beads impregnation whipping agent:
(a) after having made polystyrene resin beads, make it the method for impregnation whipping agent,
(b) or, make it the method for impregnation whipping agent midway in the growth of polystyrene resin beads.
Behind the impregnation whipping agent, the resin particle of making is taken out, and clean and drying, obtain expandable polystyrene resin beads.
For expandable polystyrene resin beads of the present invention, except that above-mentioned whipping agent, can in polystyrene resin, be added on normally used other additives, for example tinting materials such as bladder regulator, softening agent, solvent, fire retardant, dyestuff etc. in the manufacturing of expandable polystyrene resin beads as required.
Surface for expandable polystyrene resin beads of the present invention, can be as the existing mode that expandable polystyrene resin beads is carried out usually, surface treatment agents such as coating fatty acid metal salt, fatty acid ester, static inhibitor, by carrying out the coating of surface treatment agent, also can improve flowability, pre-frothing characteristic of resin particle (pearl) etc.
Secondly, expandable polystyrene resin beads of the present invention is described.
Expandable polystyrene resin beads of the present invention contains styrenic monomers and the monomeric multipolymer of acrylic ester, it is characterized in that, the absorbancy of described expandable polystyrene resin beads than (A) and absorbancy than (B) satisfied following relation:
(A)＜(B), and (A) be more than 0.05,
Described absorbancy is calculated than (A) is following: by ATR method infrared spectroscopic analysis the surface of expandable polystyrene resin beads being analyzed in the infrared absorption spectrum that obtains, obtain 1730cm
-1The absorbancy D1730 and the 1600cm at place
-1The absorbancy D1600 at place is calculated by D1730/D1600,
Described absorbancy is calculated than (B) is following: in the infrared absorption spectrum that the central part analysis of expandable polystyrene resin beads is obtained by ATR method infrared spectroscopic analysis, obtain 1730cm
-1The absorbancy D1730 and the 1600cm at place
-1The absorbancy D1600 at place is calculated by D1730/D1600.
ATR method infrared spectroscopic analysis is an analytical procedure of measuring infrared absorption spectrum by the primary event type ATR method of utilizing total reflection to absorb.
This analytical procedure is to make ATR prism and the sample driving fit with high refractive index, sees through the ATR prism sample is shone infrared rays, the light that penetrates from the ATR prism is carried out the method for spectrum analysis.ATR method infrared spectroscopic analysis is owing to have only by making sample and the driving fit of ATR prism just can measure the spectrographic simplicity, and can carry out the degree of depth, so can extensively be used in surface analysis with the various materials headed by the organism such as macromolecular material until several microns reasons such as surface analysis.
Among the present invention,, the surface and the central part of expandable polystyrene resin beads are analyzed, obtained 1730cm in the resulting infrared absorption spectrum by ATR method infrared spectroscopic analysis
-1The absorbancy D1730 and the 1600cm at place
-1The absorbancy D1600 at place.Then, the absorbancy that calculates the resin particle surface by the value of above-mentioned each absorbancy than the absorbancy of (A) and particle central part than (B).
In addition, the 1600cm that obtains by infrared absorption spectrum
-1The absorbancy D1600 at place be meant the in plane vibration that derives from the phenyl ring that polystyrene resin contains at 1600cm
-1Near the height at the peak that occurs.
And, the 1730cm that obtains by infrared absorption spectrum
-1The absorbancy D1730 at place be meant stretching vibration between the C=O that derives from the ester group that acrylate contains at 1730cm
-1Near the height at the peak that occurs.
And, the absorbancy on surface is by ATR method infrared spectroscopic analysis the surfaces A of expandable polystyrene resin beads 1 to be measured the value of obtaining as shown in Figure 1, and the absorbancy of central part is that the central part B in the cross section that the center by expandable polystyrene resin beads 1 obtained its cut-out by ATR method infrared spectroscopic analysis as shown in Figure 2 measures the value of obtaining.
Expandable polystyrene resin beads of the present invention is characterised in that the absorbancy on the surface of the resin particle that as above calculates satisfies following relation than the absorbancy of the central part of (A) and particle than (B):
(A)＜(B), be more than 0.05 and (A).
That is, on the diametric(al) of particle, expandable polystyrene resin beads of the present invention has following tendency: the copolymer in cinnamic acrylic ester components in proportions that is contained is at central part concentration height, and side becomes lower concentration on the top layer.And, also have to a certain degree copolymer in cinnamic acrylic ester composition in the skin section of particle.
Expandable polystyrene resin beads of the present invention is owing to have the distributed architecture of copolymer in cinnamic acrylic ester composition as described above, so even the pressure of the water vapor that uses during moulding is low pressure, also can obtain beautiful appearance and have high-intensity expanded moldings, and, even under high vapor pressure, carry out moulding, also can obtain be difficult for to take place expanded moldings because of the formed body appearance degradation of thermotolerance due to reducing.Not satisfying above-mentioned (A)＜(B) and (A) being under the situation of the relation more than 0.05, be difficult to obtain above-mentioned effect.
Above-mentioned absorbancy than (A) preferably in 0.05～0.50 scope, more preferably in 0.08～0.47 scope.
And, above-mentioned absorbancy than (B) preferably in 0.20～0.60 scope, more preferably in 0.23～0.55 scope.
And then, above-mentioned absorbancy than (B) and (A) ratio (B/A) preferably in 1.10～3.00 scope, more preferably in 1.17～2.88 scope.
Expandable polystyrene resin beads of the present invention can be made by above-mentioned production process efficient of the present invention ground, but manufacture method is not limited to this.
It is 0.01～0.033g/cm that expandable polystyrene resin beads pre-frothing of the present invention is become bulk density
3Scope and form pre-expanded beads, and then, this pre-expanded beads being filled in the die cavity of shaping mould, the foam-in-mould moulding is carried out in heating, is used to make expanded moldings thus.
Embodiment
Below, provide concrete example of the present invention by embodiment, but following embodiment illustration of the present invention only, the present invention is not limited in following examples.And, in following embodiment, the comparative example, the coming to the same thing of the polystyrene resin beads absorbancy ratio before the result of the absorbancy of expandable polystyrene resin beads ratio and the impregnation whipping agent.
(planting the manufacturing of grain)
In the aggregation container of the band stirrer of 100 liters of internal volumes, supply with 40000g water, 100g as the tricalcium phosphate of suspension stabilizer and 2.0g calcium dodecylbenzene sulphonate as anion surfactant, add 40000g vinylbenzene while stirring and as the 96.0g benzoyl peroxide and the 28.0g peroxidized t-butyl perbenzoate of polymerization starter, be warmed up to 90 ℃ then, carry out polymerization.Then, kept 6 hours in this temperature, and then, be warmed up to 125 ℃ after, kept 2 hours, its postcooling obtains polystyrene resin beads (a).
Sieve above-mentioned polystyrene resin beads (a), obtaining as the particle diameter of kind of grain is the polystyrene resin beads (b) of 0.5～0.71mm scope.
Secondly, in the aggregation container of the band stirrer of 5 liters of internal volumes, supply with 2000g water, the above-mentioned polystyrene resin beads of 500g (b), 6.0g as the magnesium pyrophosphate of suspension stabilizer and 1.0g calcium dodecylbenzene sulphonate, warming while stirring to 75 ℃ as anion surfactant.
(the 1st polymerization process)
Then, make 6.8g benzoyl peroxide and 1.5g peroxidized t-butyl perbenzoate be dissolved in 180g (with respect to 100 mass parts kind grains as polymerization starter, being 36 mass parts) vinylbenzene, 30g is (with respect to 100 mass parts kind grains, be 6 mass parts) in the mixed solution of butyl acrylate, the liquid that obtains is supplied with in the above-mentioned 5 liters aggregation container, kept 60 minutes at 75 ℃.
(the 2nd polymerization process)
After 60 minutes, with 150 minutes reaction solution is warmed up to 110 ℃, and little by little quantitatively 1290g vinylbenzene was supplied in the aggregation container with pump, be warmed up to 120 ℃ then with 150 minutes, after 2 hours, cool off, obtain polystyrene resin beads (c).
(the absorbancy ratio of resin particle)
Mensuration by following＜absorbancy ratio〉polystyrene resin beads (c) that obtains measured the resin particle surface absorbancy than the absorbancy of (A) and central part than (B).Its result remembers in table 1.
And, calculate absorbancy than (B) and ratio ((B)/(A)) (A), also remember in table 1.
And,, also measure the absorbancy ratio by following " mensuration of absorbancy ratio " for resulting foaming polystyrene series resin.
(mensuration of absorbancy ratio)
Absorbancy is measured with following main points than (D1730/D1600).
Promptly, for the surface separately (the symbol A among Fig. 1) of elective 10 resin particles and the central part (the symbol B among Fig. 2) that particle is cut off the cross section that obtains by the center, utilize ATR method infrared spectroscopic analysis to carry out the particle surface analysis, obtain infrared absorption spectrum.Calculate absorbancy respectively than (D1730/D1600) by each infrared absorption spectrum, the arithmetical av of the absorbancy ratio that will calculate surfaces A as absorbancy than (A), the arithmetical av of the absorbancy ratio that will calculate central part B as absorbancy than (B).
Absorbancy D1730 and D1600 for example use, and Nicolet company measures with the determinator of trade(brand)name " Fourier Tranform infrared spectrophotometer MAGMA560 " sale.
In addition, the 1600cm that obtains by infrared absorption spectrum
-1The absorbancy D1600 at place be meant the in plane vibration that derives from the phenyl ring that polystyrene resin contains at 1600cm
-1Near the height at the peak that occurs.
And, the 1730cm that obtains by infrared absorption spectrum
-1The absorbancy D1730 at place be meant stretching vibration between the C=O that derives from the ester group that acrylate contains at 1730cm
-1Near the height at the peak that occurs.
(impregnation whipping agent)
Then, in the aggregation container of the band stirrer of 5 liters of other internal volumes, supply with 2200g water, 1800g polystyrene resin beads (c), 6.0g magnesium pyrophosphate and 1.0g calcium dodecylbenzene sulphonate, warming while stirring to 70 ℃ as suspension stabilizer.Secondly, in aggregation container, add 27.0g as the hexanaphthene of frothing aid and 12.6g diisobutyl adipate as softening agent, airtight, be warmed up to 100 ℃.Then, in having the aggregation container of polystyrene resin beads (c), adding is pressed into the normal butane of 90g as whipping agent, keep after 3 hours, be cooled to below 30 ℃, in aggregation container, take out then, carry out drying, in 13 ℃ thermostatic chamber, placed 5 days then, obtain expandable polystyrene resin beads.
Embodiment 2
In the 1st polymerization process, to be dissolved in 200g (with respect to 100 mass parts kind grains as the 6.8g benzoyl peroxide and the 1.5g peroxidized t-butyl perbenzoate of polymerization starter, being 40 mass parts) vinylbenzene, 10g is (with respect to 100 mass parts kind grains, be 2 mass parts) in the mixed solution of butyl acrylate, in addition, operation obtains expandable polystyrene resin beads similarly to Example 1.
Similarly to Example 1 the absorbancy that the polystyrene resin beads before the impregnation whipping agent (c) is measured the surface than the absorbancy of (A) and central part than (B), and, calculate their ratio ((B)/(A)).The result remembers in table 1.
Embodiment 3
In the 1st polymerization process, to be dissolved in 154g (with respect to 100 mass parts kind grains as the 6.8g benzoyl peroxide and the 1.5g peroxidized t-butyl perbenzoate of polymerization starter, being 30.8 mass parts) vinylbenzene, 56g is (with respect to 100 mass parts kind grains, be 11.2 mass parts) in the mixed solution of butyl acrylate, in addition, operation obtains expandable polystyrene resin beads similarly to Example 1.
The absorbancy that polystyrene resin beads before the impregnation whipping agent (c) is measured the surface than (B), and calculates their ratio ((B)/(A)) than the absorbancy of (A) and central part similarly to Example 1.The result remembers in table 1.
Embodiment 4
In the 1st polymerization process, to be dissolved in 40g (with respect to 100 mass parts kind grains as the 6.8g benzoyl peroxide and the 1.5g peroxidized t-butyl perbenzoate of polymerization starter, being 8 mass parts) vinylbenzene, 30g is (with respect to 100 mass parts kind grains, be 6 mass parts) in the mixed solution of butyl acrylate, and, in the 2nd polymerization process, the vinylbenzene that will little by little supply to quantitatively in the aggregation container with pump when will heat up with 150 minutes is set at 1430g, in addition, operation obtains expandable polystyrene resin beads similarly to Example 1.
The absorbancy that polystyrene resin beads before the impregnation whipping agent (c) is measured the surface than (B), and calculates their ratio ((B)/(A)) than the absorbancy of (A) and central part similarly to Example 1.The result remembers in table 1.
Embodiment 5
In the 1st polymerization process, to be dissolved in 360g (with respect to 100 mass parts kind grains as the 6.8g benzoyl peroxide and the 1.5g peroxidized t-butyl perbenzoate of polymerization starter, being 72 mass parts) vinylbenzene, 30g is (with respect to 100 mass parts kind grains, be 6 mass parts) in the mixed solution of butyl acrylate, and, in the 2nd polymerization process, the vinylbenzene that will little by little supply to quantitatively in the aggregation container with pump when will heat up with 150 minutes is set at 1110g, in addition, operation obtains expandable polystyrene resin beads similarly to Example 1.
The absorbancy that polystyrene resin beads before the impregnation whipping agent (c) is measured the surface than (B), and calculates their ratio ((B)/(A)) than the absorbancy of (A) and central part similarly to Example 1.The result remembers in table 1.
Embodiment 6
In the 1st polymerization process, the acrylate kind of using is set at ethyl propenoate, to be dissolved in 170g (with respect to 100 mass parts kind grains as the 6.8g benzoyl peroxide and the 1.5g peroxidized t-butyl perbenzoate of polymerization starter, be 34 mass parts) vinylbenzene, 40g is (with respect to 100 mass parts kind grains, be 8 mass parts) in the mixed solution of ethyl propenoate, and, the styrenic monomers that will little by little supply to quantitatively in the aggregation container with pump when will heat up with 150 minutes is set at 1290g, in addition, operation obtains expandable polystyrene resin beads similarly to Example 1.
The absorbancy that polystyrene resin beads before the impregnation whipping agent (c) is measured the surface than (B), and calculates their ratio ((B)/(A)) than the absorbancy of (A) and central part similarly to Example 1.The result remembers in table 1.
Embodiment 7
To be dissolved in the mixed solution of 180g styrenic monomers, 30g butyl acrylate as the 6.8g benzoyl peroxide and the 1.5g peroxidized t-butyl perbenzoate of polymerization starter, the styrenic monomers that will little by little supply to quantitatively in the aggregation container with pump when will heat up with 150 minutes is set at 750g, in addition, operation obtains expandable polystyrene resin beads similarly to Example 1.
The absorbancy that polystyrene resin beads before the impregnation whipping agent (c) is measured the surface than (B), and calculates their ratio ((B)/(A)) than the absorbancy of (A) and central part similarly to Example 1.The result remembers in table 1.
Embodiment 8
To be dissolved in the mixed solution of 180g styrenic monomers, 30g butyl acrylate as the 6.8g benzoyl peroxide and the 1.5g peroxidized t-butyl perbenzoate of polymerization starter, the styrenic monomers that will little by little supply to quantitatively in the aggregation container with pump when will heat up with 150 minutes is set at 2000g, in addition, operation obtains expandable polystyrene resin beads similarly to Example 1.
The absorbancy that polystyrene resin beads before the impregnation whipping agent (c) is measured the surface than (B), and calculates their ratio ((B)/(A)) than the absorbancy of (A) and central part similarly to Example 1.The result remembers in table 1.
Embodiment 9
To be dissolved in the mixed solution of 180g styrenic monomers, 30g butyl acrylate as the 6.8g benzoyl peroxide and the 1.5g peroxidized t-butyl perbenzoate of polymerization starter, the styrenic monomers that will little by little supply to quantitatively in the aggregation container with pump when will heat up with 150 minutes is set at 500g, in addition, operation obtains expandable polystyrene resin beads similarly to Example 1.
The absorbancy that polystyrene resin beads before the impregnation whipping agent (c) is measured the surface than (B), and calculates their ratio ((B)/(A)) than the absorbancy of (A) and central part similarly to Example 1.The result remembers in table 1.
Embodiment 10
To be dissolved in the mixed solution of 180g styrenic monomers, 30g butyl acrylate as the 6.8g benzoyl peroxide and the 1.5g peroxidized t-butyl perbenzoate of polymerization starter, the styrenic monomers that will little by little supply to quantitatively in the aggregation container with pump when will heat up with 150 minutes is set at 2750g, in addition, operation obtains expandable polystyrene resin beads similarly to Example 1.
The absorbancy that polystyrene resin beads before the impregnation whipping agent (c) is measured the surface than (B), and calculates their ratio ((B)/(A)) than the absorbancy of (A) and central part similarly to Example 1.The result remembers in table 1.
Comparative example 1
In the 1st polymerization process of embodiment 1, do not use acrylate, and 6.8g benzoyl peroxide and 1.5g peroxidized t-butyl perbenzoate changed to 210g (with respect to 100 mass parts kind grains, be 42 mass parts) vinylbenzene, in addition, similarly operate with embodiment, obtain expandable polystyrene resin beads.
The absorbancy that polystyrene resin beads before the impregnation whipping agent (c) is measured the surface than (B), and calculates their ratio ((B)/(A)) than the absorbancy of (A) and central part similarly to Example 1.The result remembers in table 1.
Comparative example 2
In the 1st polymerization process, to be dissolved in 202g (with respect to 100 mass parts kind grains as the 6.8g benzoyl peroxide and the 1.5g peroxidized t-butyl perbenzoate of polymerization starter, be 40.4 mass parts) vinylbenzene, 8g is (with respect to 100 mass parts kind grains, be 1.6 mass parts) in the mixed solution of butyl acrylate, and, in the 2nd polymerization process, the vinylbenzene that will little by little supply to quantitatively in the aggregation container with pump when will heat up with 150 minutes is set at 1290 mass parts, in addition, operation obtains expandable polystyrene resin beads similarly to Example 1.
The absorbancy that polystyrene resin beads before the impregnation whipping agent (c) is measured the surface than (B), and calculates their ratio ((B)/(A)) than the absorbancy of (A) and central part similarly to Example 1.The result remembers in table 1.
Comparative example 3
In the 1st polymerization process, to be dissolved in 140g (with respect to 100 mass parts kind grains as the 6.8g benzoyl peroxide and the 1.5g peroxidized t-butyl perbenzoate of polymerization starter, being 28 mass parts) vinylbenzene, 70g is (with respect to 100 mass parts kind grains, be 14 mass parts) in the mixed solution of butyl acrylate, and, in the 2nd polymerization process, the vinylbenzene that will little by little supply to quantitatively in the aggregation container with pump when will heat up with 150 minutes is set at 1290g, in addition, operation obtains expandable polystyrene resin beads similarly to Example 1.
The absorbancy that polystyrene resin beads before the impregnation whipping agent (c) is measured the surface than (B), and calculates their ratio ((B)/(A)) than the absorbancy of (A) and central part similarly to Example 1.The result remembers in table 1.
Comparative example 4
In the 1st polymerization process, to be dissolved in 30g (with respect to 100 mass parts kind grains as the 6.8g benzoyl peroxide and the 1.5g peroxidized t-butyl perbenzoate of polymerization starter, being 6 mass parts) vinylbenzene, 30g is (with respect to 100 mass parts kind grains, be 6 mass parts) in the mixed solution of butyl acrylate, and, in the 2nd polymerization process, the vinylbenzene that will little by little supply to quantitatively in the aggregation container with pump when will heat up with 150 minutes is set at 1440 mass parts, in addition, operation obtains expandable polystyrene resin beads similarly to Example 1.
The absorbancy that polystyrene resin beads before the impregnation whipping agent (c) is measured the surface than (B), and calculates their ratio ((B)/(A)) than the absorbancy of (A) and central part similarly to Example 1.The result remembers in table 1.
Comparative example 5
In the 1st polymerization process, to be dissolved in 460g (with respect to 100 mass parts kind grains as the 6.8g benzoyl peroxide and the 1.5g peroxidized t-butyl perbenzoate of polymerization starter, being 92 mass parts) vinylbenzene, 30g is (with respect to 100 mass parts kind grains, be 6 mass parts) in the mixed solution of butyl acrylate, and, in the 2nd polymerization process, the vinylbenzene that will little by little supply to quantitatively in the aggregation container with pump when will heat up with 150 minutes is set at 1010g, in addition, operation obtains expandable polystyrene resin beads similarly to Example 1.
The absorbancy that polystyrene resin beads before the impregnation whipping agent (c) is measured the surface than (B), and calculates their ratio ((B)/(A)) than the absorbancy of (A) and central part similarly to Example 1.The result remembers in table 1.
Comparative example 6
In the aggregation container of the band stirrer of 5 liters of internal volumes, supply with 2000 mass parts water, the above-mentioned styrene resin particles of 500 mass parts (B), 6.0 mass parts as the magnesium pyrophosphate of suspension stabilizer and 0.3 mass parts calcium dodecylbenzene sulphonate, warming while stirring to 75 ℃ as anion surfactant.
Secondly, make the mixed solution of 1470 mass parts vinylbenzene and 30 mass parts butyl acrylates in advance, use these mixed solution 210 mass parts (with respect to 100 mass parts kind grains, vinylbenzene is that 41.2 mass parts, butyl acrylate are 0.84 mass parts) dissolving 6.8 mass parts benzoyl peroxides and 1.5 mass parts peroxidized t-butyl perbenzoates, and supply in 5 liters of above-mentioned aggregation containers, kept 60 minutes in 75 ℃ then.
After 60 minutes, with 150 minutes reaction solution is warmed up to 110 ℃, and little by little quantitatively mixed solution 1290 mass parts of above-mentioned styrenic monomers and butyl acrylate were supplied in the aggregation container with pump with 150 minutes, be warmed up to 120 ℃ then, after 2 hours, cool off, obtain styrene resin particles (c).Then, operation obtains expandable polystyrene resin beads similarly to Example 1.
The absorbancy that polystyrene resin beads before the impregnation whipping agent (c) is measured the surface than (B), and calculates their ratio ((B)/(A)) than the absorbancy of (A) and central part similarly to Example 1.The result remembers in table 1.
[table 1]
As shown in table 1, in the embodiments of the invention 1～10, the absorbancy on the surface of polystyrene resin beads than (B) satisfied (A)＜(B) and (A) is a relation more than 0.05 than the absorbancy of (A) and central part.
And in embodiment 1～10, in 0.05～0.50 scope, and above-mentioned absorbancy is in 0.20～0.60 the scope than (B) to absorbancy than (A).
And then, among the embodiment 1～10, absorbancy than (B) and (A) ratio (B/A) in 1.10～3.00 scope.
On the other hand, in the comparative example 1,, do not derive from the 1730cm that ester group absorbs so be measured to owing to do not add acrylate
-1The absorbancy D1730 at place.
And, in the comparative example 2, because the butyl acrylate that uses is few in the 1st polymerization process, so the absorbancy on surface is 0.02 than (A), less than the surperficial absorbancy of the present invention's regulation lower limit (0.05) than (A).
And, in the comparative example 3 because the amount of the butyl acrylate that uses is many in the 1st polymerization process, so the absorbancy on surface than (A) greater than the absorbancy of central part than (B).
And, in the comparative example 4 because the cinnamic amount used is few in the 1st polymerization process, so the absorbancy on surface than (A) greater than the absorbancy of central part than (B).
And, in the comparative example 5, because the cinnamic amount used is many in the 1st polymerization process, so the absorbancy on surface is 0.04 than (A), less than the surperficial absorbancy of the present invention's regulation lower limit (0.05) than (A).
And, in the comparative example 6, in the 2nd polymerization process, use butyl acrylate with vinylbenzene, thus the absorbancy on surface than (A) greater than the absorbancy of central part than (B).
(pre-frothing and foaming)
For as above make, preserving 5 days embodiment 1～10 and each expandable polystyrene resin beads of comparative example 1～6 below 13 ℃, at the surface-coated processing of particle Zinic stearas and glycerine three (oxystearic acid) ester, become 0.0167g/cm with the pre-frothing of pre-frothing device then as surface treatment agent
3Bulk density, in 20 ℃ of slakings 24 hours, obtain pre-expanded beads then.
Then, in the die cavity of expanded beads automatic molder, fill above-mentioned pre-expanded beads, described expanded beads automatic molder possesses the shaping mould of the die cavity of the rectangular shape with interior dimensions 300mm * 400mm * 30mm, carries out density 0.0167g/cm with following two kinds of conditions (moulding vapour pressure)
3The moulding of polystyrene resin expanded moldings.
Condition of molding (shaper Co., Ltd. ponding worker mechanism is made made ACE-3SP)
Two kinds of conditions of moulding vapour pressure (gauge pressure: 0.04MPa, 0.09MPa)
Mold heated 5 seconds
One side heats (setting pressure 0.03MPa)
The opposing party heated 3 seconds
Sandwich heating 15 seconds
Water-cooled 5 seconds
Put cold (vacuum is put cold QS moulding pattern)
The setting face of taking-up is pressed 0.02MPa
Make for each expandable polystyrene resin beads that uses embodiment 1～10 and comparative example 1～6, water vapor pressure was the expanded moldings under the situation of 0.09MPa when water vapor pressure was as expanded moldings under the situation of 0.04MPa and moulding during moulding, with condition research flexural strength, expanded moldings outward appearance, the cooling time shown in following, estimate.Its result remembers in table 2.
(mensuration of flexural strength)
For the expanded moldings that obtains among the embodiment (and comparative example), measure flexural strength according to the method for JIS A9511:2006 " expanded plastic lagging material " record.
Promptly, use Tensilon universal testing machine UCT-10T (manufacturing of ORIENTEC company), measure with following condition, and calculate flexural strength with following formula, described condition is: test body size is set at 75mm * 300mm * 50mm, compression speed is set at 10mm/min, and the front end anchor clamps are pressurization chock 10R, brace table 10R, and length of support is from 200mm.The number of test film is 3, obtains its mean value.
Flexural strength (MPa)=3FL/2bh
2
(herein, F represents crooked maximum load (N), and L represents length of support from (mm), and b represents the width (mm) of test film, and h represents the thickness (mm) of test film.)
(evaluation of expanded moldings outward appearance)
The surface of Visual Confirmation expanded moldings is estimated based on following metewand.
Zero: beautiful appearance, very close to each other between expanded particle.
*: more gap is arranged between expanded particle, perhaps produce fusion.
(cooling time)
For cooling time of the present invention, foaming in the time of will carrying out moulding with the condition of molding of above-mentioned record, that the water-cooled operation finishes the formed body of back to the die cavity presses to the setting face of taking-up and presses and put cool time as cooling time till the 0.02MPa.Each moulding is 3 under each condition (moulding vapour pressure), and be its mean value cooling time.
(comprehensive evaluation)
Carry out comprehensive evaluation based on following metewand.
◎: the water vapor pressure during moulding is the situation of 0.04MPa and is the situation of 0.09MPa that the outward appearance of resulting expanded moldings is all beautiful.
*: the water vapor pressure during moulding is the situation of 0.04MPa and is the appearance poor of expanded moldings under at least a situation in the situation of 0.09MPa.
[table 2]
As shown in Table 2, supply with 7.0～80.0 mass parts vinylbenzene and 2.0～12.0 mass parts acrylate, make kind of grain absorb these monomers and carry out polymerization and make under the situation of the embodiment of the invention 1～10 that kind of grain grows up with respect to 100 mass parts kind grains in the 1st polymerization process, water vapor forces down and can both obtain beautiful appearance, expanded moldings that flexural strength is high under arbitrary condition of (0.04MPa) and water vapor pressure height (0.09MPa) during moulding.
On the other hand, the monomer that uses in the 1st polymerization process does not only add the comparative example 1 of acrylate as vinylbenzene, the appearance poor of the expanded moldings that obtains at low water vapor pressure (0.04MPa) compacted under, and flexural strength is low.
The comparative example 2 of the quantity not sufficient scope of the invention of the acrylate that adds in the 1st polymerization process, the appearance poor of the expanded moldings that obtains at low water vapor pressure (0.04MPa) compacted under, and flexural strength is low.
The amount of acrylate surpasses the comparative example 3 of the scope of the invention in the 1st polymerization process, the appearance poor of the expanded moldings that obtains at high water vapor pressure (0.09MPa) compacted under, and flexural strength is low.
The comparative example 4 of the cinnamic quantity not sufficient scope of the invention in the 1st polymerization process, the expanded moldings that obtains at low water vapor pressure (0.04MPa) and high these two kinds of condition compacted unders of water vapor pressure (0.09MPa) all is that appearance poor and flexural strength are low.
Cinnamic amount surpasses the comparative example 4 of the scope of the invention in the 1st polymerization process, the appearance poor of the expanded moldings that obtains at low water vapor pressure (0.04MPa) compacted under, and flexural strength is low.
In the 1st polymerization process and these two operations of the 2nd polymerization process, all used the comparative example 6 of the mixture of vinylbenzene and acrylate, the appearance poor of the expanded moldings that obtains at high water vapor pressure (0.09MPa) compacted under, and flexural strength is low.
(the conservatory comparison of pre-expanded beads)
Same with the situation of above-mentioned (pre-frothing and foaming), at the surface-coated processing of each expandable polystyrene resin beads of embodiment 1～10 and comparative example 1～6 Zinic stearas and glycerine three (oxystearic acid) ester, be bulk density 0.0167g/cm with the pre-frothing of pre-frothing device then as surface treatment agent
3
After the pre-frothing, resulting each pre-expanded beads was placed 7 days under 30 ℃, the environment of humidity 50%.
Then, in the die cavity of expanded beads automatic molder, fill above-mentioned pre-expanded beads, described expanded beads automatic molder possesses the shaping mould of the die cavity of the rectangular shape with interior dimensions 300mm * 400mm * 30mm, carries out density 0.0167g/cm with following condition
3The moulding of polystyrene resin expanded moldings.
Condition of molding (shaper Co., Ltd. ponding worker mechanism is made made ACE-3SP)
Moulding vapour pressure gauge pressure: 0.04MPa
Mold heated 5 seconds
One side heats (setting pressure 0.03MPa)
The opposing party heated 3 seconds
Sandwich heating 15 seconds
Water-cooled 5 seconds
Put cold (vacuum is put cold QS moulding pattern)
The setting face of taking-up is pressed 0.02MPa
For use with the state of pre-expanded beads place each pre-expanded beads after 7 days, water vapor pressure during with moulding is set at 0.04MPa and the embodiment 1～10 that makes and each expanded moldings of comparative example 1～6, similarly study flexural strength, expanded moldings outward appearance, cooling time with the situation of above-mentioned (pre-frothing and foaming), estimate.And, carry out comprehensive evaluation based on following metewand.Its result remembers in table 3.
(comprehensive evaluation)
◎: the beautiful appearance of the expanded moldings that obtains.
*: the appearance poor of expanded moldings.
[table 3]
As shown in Table 3, in the embodiments of the invention 1～10,, when the low moulding of 0.04MPa, also can obtain the expanded moldings of beautiful appearance under the water vapor pressure even placed 7 days pre-expanded beads after using pre-frothing.
On the other hand, in the comparative example 1～6, under the condition identical, can not obtain the expanded moldings of beautiful appearance with embodiment.Even comparative example 3 and the comparative example 6 that obtains the good expanded moldings of outward appearance with low water vapor pressure (0.04MPa) as shown in table 2 in above-mentioned (pre-frothing and foaming) particularly, after using pre-frothing, placed under 7 days the situation of pre-expanded beads, can not obtain the expanded moldings of beautiful appearance.
By this test-results as can be known, the pre-expanded beads that obtains in the embodiments of the invention 1～10 is excellence aspect the retentivity of foaming power, has good keeping qualities.
Utilizability on the industry
Expandable polystyrene resin beads of the present invention is suitable for making as food containers and packing, the useful polystyrene resin expanded moldings of padded coaming. Even the pressure of the water vapour that expandable polystyrene resin beads of the present invention uses when moulding is as also can obtaining beautiful appearance and have high-intensity expanded moldings in the situation of low pressure, so can realize the reduction of the manufacturing cost of expanded moldings, energy-conservation in making.
Claims (8)
1. the manufacture method of an expandable polystyrene resin beads, wherein, carry out following operation and obtain expandable polystyrene resin beads:
(1) polystyrene resin kind grain is scattered in the dispersion liquid that forms in the water, with respect to 100 mass parts polystyrene resin kind grains, supply with 7.0～80.0 mass parts styrenic monomers and 2.0～12.0 mass parts acrylic ester monomers, make kind of grain absorb these monomers and carry out polymerization and the 1st polymerization process that polystyrene resin kind grain is grown up;
(2) then, in this dispersion liquid, only supply with styrenic monomers, make kind of grain absorb this monomer and carry out polymerization and the 2nd polymerization process that polystyrene resin beads is grown up; With
(3) carrying out the operation that the 2nd polymerization process has been made behind the polystyrene resin beads or made it the impregnation whipping agent in the growth of polystyrene resin beads midway.
2. expandable polystyrene resin beads, it is the expandable polystyrene resin beads that contains styrenic monomers and the monomeric multipolymer of acrylic ester, wherein, the absorbancy of described expandable polystyrene resin beads than A and absorbancy than the satisfied following relation of B:
A＜B, and A is more than 0.05,
Described absorbancy is calculated than A is following: by ATR method infrared spectroscopic analysis the surface of described expandable polystyrene resin beads being analyzed in the infrared absorption spectrum that obtains, obtain 1730cm
-1The absorbancy D1730 and the 1600cm at place
-1The absorbancy D1600 at place is calculated by D1730/D1600,
Described absorbancy is calculated than B is following: in the infrared absorption spectrum that the central part analysis of described expandable polystyrene resin beads is obtained by ATR method infrared spectroscopic analysis, obtain 1730cm
-1The absorbancy D1730 and the 1600cm at place
-1The absorbancy D1600 at place is calculated by D1730/D1600.
3. expandable polystyrene resin beads as claimed in claim 2, wherein, described absorbancy than A in 0.05～0.50 scope, and described absorbancy than B in 0.20～0.60 scope.
4. expandable polystyrene resin beads as claimed in claim 2, wherein, described absorbancy than the ratio B/A of B and A in 1.10～3.00 scope.
5. expandable polystyrene resin beads as claimed in claim 3, wherein, described absorbancy than the ratio B/A of B and A in 1.10～3.00 scope.
6. expandable polystyrene resin beads, it is that manufacture method by the described expandable polystyrene resin beads of claim 1 obtains.
7. pre-expanded beads, it is that each described expandable polystyrene resin beads pre-frothing in the claim 2～6 is become bulk density is 0.01～0.033g/cm
3Scope obtain.
8. expanded moldings, it is to be filled in the described pre-expanded beads of claim 7 in the die cavity of shaping mould and to heat, the foam-in-mould moulding obtains by carrying out.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008019000 | 2008-01-30 | ||
| JP2008-019000 | 2008-01-30 | ||
| PCT/JP2009/051049 WO2009096327A1 (en) | 2008-01-30 | 2009-01-23 | Expandable polystyrene resin beads, process for production thereof, pre-expanded beads and expanded moldings |
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| CN201210151041.1A Division CN102675680B (en) | 2008-01-30 | 2009-01-23 | Expandable polystyrene resin beads, pre-expanded beads and expanded moldings |
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| CN101925647B CN101925647B (en) | 2013-01-23 |
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| CN201210151041.1A Active CN102675680B (en) | 2008-01-30 | 2009-01-23 | Expandable polystyrene resin beads, pre-expanded beads and expanded moldings |
| CN2009801032488A Active CN101925647B (en) | 2008-01-30 | 2009-01-23 | Expandable polystyrene resin beads, process for production thereof, pre-expanded beads and expanded moldings |
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| CN201210151041.1A Active CN102675680B (en) | 2008-01-30 | 2009-01-23 | Expandable polystyrene resin beads, pre-expanded beads and expanded moldings |
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| JP (1) | JP5284987B2 (en) |
| KR (2) | KR101297878B1 (en) |
| CN (2) | CN102675680B (en) |
| TW (2) | TWI490256B (en) |
| WO (1) | WO2009096327A1 (en) |
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2009
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- 2009-01-23 TW TW098102786A patent/TWI396707B/en active
- 2009-01-23 WO PCT/JP2009/051049 patent/WO2009096327A1/en active Application Filing
- 2009-01-23 KR KR1020127014816A patent/KR101297878B1/en active IP Right Grant
- 2009-01-23 CN CN201210151041.1A patent/CN102675680B/en active Active
- 2009-01-23 CN CN2009801032488A patent/CN101925647B/en active Active
- 2009-01-23 JP JP2009551492A patent/JP5284987B2/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103415559A (en) * | 2011-03-04 | 2013-11-27 | 积水化成品工业株式会社 | Expanded composite polystyrene resin particles and molded foam thereof |
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| CN109642042A (en) * | 2016-09-27 | 2019-04-16 | 积水化成品工业株式会社 | Expanded beads, foam molding, fiber-reinforced composite and Vehicle component |
| CN113330061A (en) * | 2019-03-12 | 2021-08-31 | 株式会社钟化 | Expandable resin particles, pre-expanded particles, and expanded molded article |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI490256B (en) | 2015-07-01 |
| CN102675680A (en) | 2012-09-19 |
| TWI396707B (en) | 2013-05-21 |
| CN101925647B (en) | 2013-01-23 |
| CN102675680B (en) | 2014-09-24 |
| KR20100099255A (en) | 2010-09-10 |
| TW201329140A (en) | 2013-07-16 |
| JP5284987B2 (en) | 2013-09-11 |
| WO2009096327A1 (en) | 2009-08-06 |
| KR20120083519A (en) | 2012-07-25 |
| TW200938572A (en) | 2009-09-16 |
| KR101218422B1 (en) | 2013-01-03 |
| KR101297878B1 (en) | 2013-08-19 |
| JPWO2009096327A1 (en) | 2011-05-26 |
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