JP2014167062A - Expandable styrenic resin, method for producing the same, expanded particle and expanded molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide expandable styrenic resin particles capable of giving an expanded molding having excellent bending strength in a reduced vapor quantity.SOLUTION: Provided is expandable styrenic resin particles comprising: a styrenic resin component A; a component B derived from monofunctional acrylic ester; an ester group-containing plasticizer C; and an expanding agent, where the component B derived from monofunctional acrylic ester is comprised largely at the central part of the styrenic resin particles, and the ester group-containing plasticizer component C is comprised largely at the surface layer part of the styrenic resin particles.

Description

  The present invention relates to expandable styrenic resin particles, a method for producing the same, expanded particles, and an expanded molded body. More specifically, the present invention relates to an expandable styrene-based resin particle that can be molded with a small amount of steam and can provide a foamed molded article having excellent bending characteristics, a method for producing the same, a foamed particle, and a foamed molded article.

Conventionally, foamed molded articles have been used for transportation packaging materials such as fish boxes and food containers because they are lightweight and have excellent heat insulation properties. Among them, a foamed molded product produced by using a mold using foamable resin particles as a raw material is often used because of the advantage that a desired shape is easily obtained.
Expandable styrene resin particles are widely used as expandable resin particles, which are raw materials for producing expanded molded articles. For example, expanded molded articles are obtained as follows. That is, expandable styrene resin particles are heated with steam and pre-expanded to obtain expanded particles (pre-expanded particles). The obtained pre-expanded particles are filled into the mold cavity. Next, a foamed molded article can be obtained by integrating the pre-expanded particles by heat-sealing while pre-expanding the filled pre-expanded particles with steam. This method for producing a foam-molded product is called a bead method. In recent years, a reduction in the amount of heavy oil required for generating steam with a boiler or the like has been demanded from the viewpoint of energy saving, and there is a demand for expandable styrene resin particles capable of producing a foamed molded article with a small amount of steam.

In general, the foam molded body obtained by the bead method as described above has pre-expanded particles integrated by heat fusion, so that the strength of the fused surface is weaker than the portion other than the fused surface. This weak strength of the fused surface leads to the disadvantage that the bending strength and tensile strength of the box side in a box shape are inferior, especially with a large bending strength factor. In particular, when molding is performed with a small amount of steam, the strength of heat-sealing between the pre-expanded particles tends to be inferior, and as a result, a foamed molded product having sufficient bending strength is often not obtained. Therefore, it is desired to provide a foam molded body that is resistant to bending.
From the viewpoint of reducing the amount of steam, Japanese Patent Application Laid-Open No. 2011-26508 (Patent Document 1) proposes expandable styrene resin particles capable of providing a foamed molded article excellent in appearance and fusion with a small amount of steam. Yes.

JP 2011-26508 A

  Even with the technique described in the above publication, a foamed molded article having sufficient bending strength can be obtained with energy saving. However, from the viewpoint of further improving energy saving, it has been desired to provide expandable styrene resin particles capable of providing a foamed molded article having sufficient bending strength while maintaining moldability even with a smaller amount of steam.

  The inventor of the present invention reviewed the resin type and the surface modifier in the expandable styrene resin particles in order to reduce the amount of steam at the time of foam molding. As a result, the resin component derived from the monofunctional acrylate ester is richly contained in the central portion, and the ester layer-containing plasticizer is richly contained in the surface layer portion, thereby giving a foam molded article having sufficient bending strength even with a small amount of steam. The present inventors have found that expandable styrene resin particles can be provided, and have reached the present invention.

Thus, according to the present invention, expandable styrene resin particles containing a styrene resin component A, a component B derived from a monofunctional acrylic ester, an ester group-containing plasticizer C, and a foaming agent,
Component B derived from the monofunctional acrylate ester is contained in a large amount in the center of the styrene resin particles,
Expandable styrene resin particles characterized in that a large amount of the ester group-containing plasticizer component C is contained in the surface layer portion of the styrene resin particles are provided.

  According to this invention, the expandable particle | grains containing the said styrene resin particle and a foaming agent are provided. Furthermore, according to the present invention, there are provided expanded particles obtained by expanding the expandable styrene resin particles. Moreover, according to this invention, the foaming molding obtained by carrying out the foam molding of the said foaming particle is provided.

  Furthermore, according to the present invention, there is provided a method for producing the above expandable styrene resin particles, wherein seed particles composed of a styrene resin are impregnated with a monomer mixture containing a styrene monomer and a monofunctional acrylate ester. A first step, a second step of impregnating and polymerizing a styrene monomer on the particles obtained in the step, and a foaming agent in the presence of an ester group-containing plasticizer on the particles obtained in the step. A method for producing expandable styrenic resin particles comprising a third step of impregnation is provided.

  According to the present invention, it is possible to provide expandable styrene-based resin particles and expanded particles that can provide a foamed molded article having excellent bending strength even with a small amount of steam. The inventor believes that this effect is achieved by richly containing a resin component derived from a monofunctional acrylate ester in the central part and richly containing an ester group-containing plasticizer in the surface layer part. With the foamed molded article having excellent bending strength of the present invention, the bending strength of the foamed molded article can be improved while reducing the amount of steam during molding.

Further, (i) the expandable styrene resin particles contain 0.3 to 3.5% by mass of the component B derived from a monofunctional acrylate ester, and 0.3 to 1.8 of the ester group-containing plasticizer component C. (Ii) The center part of the expandable styrene resin particles containing mass% exhibits an absorbance ratio (D1735 / D1600) in the range of 0.4 to 0.8. (Iii) The expandable styrene resin particles are When the absorbance ratio (D1735 / D1600) is 1, the minimum value of the absorbance ratio (D1735 / D1600) is a particle showing a relative value in the range of 0.1 to 0.4. (Iv) Expandable styrene resin The particle is a particle having a relative value in which the minimum value of the absorbance ratio (D1735 / D1600) is in the range of 0.1 to 0.5 when the absorbance ratio (D1735 / D1600) of the surface layer portion is 1. (v ) Monofunctional acrylic acid ester (Vi) the ester group-containing plasticizer, which is a monomer having an alkyl group having 1 to 8 carbon atoms in the ester moiety, is selected from adipic acid ester, phthalic acid ester and glycerin fatty acid ester (vii) expandable styrene When the resin-based resin particles further include a hydrocarbon solvent component D (viii) The foamed molded product satisfies any one of the container-like shapes, the foamed molded product having excellent bending strength is reduced in the amount of steam. Expandable styrenic resin particles that can be provided by

2 is a graph showing changes in absorbance ratio from the center to the surface of expandable styrene resin particles of Example 1. FIG.

(Expandable styrene resin particles)
The expandable styrene resin particles (hereinafter, expandable particles) include a styrene resin component A, a component B derived from a monofunctional acrylate ester, an ester group-containing plasticizer component C, and a foaming agent. Are contained in the center part of the styrene resin particles, and the ester group-containing plasticizer component C is a particle contained in the surface layer part of the styrene resin particles (hereinafter simply referred to as Component A, Component B and Component C). Called).

(1) Component (a) Styrenic resin component A
The styrene resin component A is a resin component derived from a styrene monomer. The styrene monomer is not particularly limited, and any known monomer can be used. Examples thereof include styrene, α-methylstyrene, vinyl toluene, chlorostyrene, ethyl styrene, isopropyl styrene, dimethyl styrene, bromostyrene, and the like. These styrenic monomers may be one kind or a mixture of plural kinds. A preferred styrenic monomer is styrene.

(B) Component B derived from monofunctional acrylic acid ester
(I) Monofunctional acrylic acid ester Although monofunctional acrylic acid ester is not specifically limited, it is a monomer copolymerizable with a styrene-type monomer. The monofunctional acrylic ester is preferably a monomer having an alkyl group having 1 to 8 carbon atoms in the ester moiety. By using a monomer having an alkyl group having a carbon number in this range, it is possible to provide styrene-based resin particles that can give a foamed molded article with a small amount of steam and improved bending strength.

Specific monofunctional acrylic esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth) acrylic. Examples include hexyl acid, heptyl (meth) acrylate, octyl (meth) acrylate, and the like. The alkyl group having 3 or more carbon atoms includes not only a linear alkyl group but also an alkyl group having a structural isomer such as an iso structure, a sec structure or a tert structure.
Further, from the viewpoint of reducing the amount of vapor during foam molding, it is preferable to select a monofunctional acrylate ester whose corresponding polymer has a glass transition point (Tg) lower than that of polystyrene (Tg 100 ° C.). In this respect, the more preferable alkyl group has 3 to 5 carbon atoms, and the particularly preferable carbon number is 4.

(Ii) Styrene monomer The monofunctional acrylic ester may be copolymerized with a styrene monomer. As the styrenic monomer, any of the monomers mentioned in Component A can be used. A preferred styrenic monomer is styrene.
(C) Ester group-containing plasticizer As the ester group-containing plasticizer, a plasticizer that can ensure sufficient fusion of the foamed particles even with a small amount of steam is used by improving the flexibility of the surface layer of the foamable particles. It is preferable to do. Specific plasticizers include glycerol fatty acid esters such as glycerol diacetomonolaurate, glycerol tristearate, diacetylated glycerol monostearate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, etc. Phthalates, diisobutyl adipate, dioctyl adipate, and the like. Of these, adipic acid esters are preferred from the viewpoint of low-pressure moldability.

(D) Ratio of Component A to C The ratio of Component A, Component B, and Component C is only required as long as it can provide foamable particles that can provide a foamed molded product with superior bending strength with a small amount of steam. It is not limited.
The proportion of component B is preferably in a range where the proportion relative to the expandable particles can be 0.3 to 3.5% by mass. When the proportion of component B is less than 0.3% by mass, foam moldability with a small amount of steam may be difficult to obtain. If it is more than 3.5% by mass, the strength may be extremely lowered. A more desirable ratio is 0.5 to 3.0 mass%, and a still more desirable ratio is 0.5 to 2.5 mass%.

The proportion of component C is preferably in the range of 0.3 to 1.8% by mass with respect to the expandable particles. When the ratio of the component C is less than 0.3% by mass, it may be difficult to obtain sufficient fusing property. When the amount is more than 1.8% by mass, the heat resistance during molding is lowered, and the moldable temperature range may be narrowed. A more desirable ratio is 0.3 to 1.5 mass%, and a still more desirable ratio is 0.4 to 1.4 mass%.
In addition, the ratio of the component B and the component C is substantially in agreement with the addition amount of a corresponding raw material. These ratios mean values where the total amount of components A to C is 100% by mass.

(E) Foaming agent The foaming agent is not particularly limited, and any known foaming agent can be used. In particular, a gaseous or liquid organic compound having a boiling point equal to or lower than the softening point of the styrene resin is suitable. For example, hydrocarbons such as propane, n-butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane, cyclopentadiene, n-hexane, petroleum ether, ketones such as acetone and methyl ethyl ketone, methanol, ethanol, isopropyl alcohol, etc. Low boiling point ether compounds such as alcohols, dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, halogen-containing hydrocarbons such as trichloromonofluoromethane, dichlorodifluoromethane, inorganic gases such as carbon dioxide, nitrogen, ammonia, etc. Can be mentioned. These foaming agents may be used alone or in combination of two or more. Among these, it is preferable to use hydrocarbons from the viewpoint of preventing the destruction of the ozone layer and from the viewpoint of quickly replacing with the air and suppressing the time-dependent change of the foamed molded product. Of the hydrocarbons, hydrocarbons having a boiling point of −45 to 40 ° C. are more preferable, and propane, n-butane, isobutane, n-pentane, isopentane and the like are more preferable.

  Furthermore, it is preferable that content of a foaming agent is the range of 2-12 mass%. If it is less than 2% by mass, it may be difficult to obtain a foamed molded article having a desired density from the expandable particles. In addition, since the effect of increasing the secondary foaming power at the time of in-mold foam molding is reduced, the appearance of the foam molded article may not be good. When the amount is more than 12% by mass, the time required for the cooling step in the production process of the foamed molded product becomes long, and the productivity may decrease. A more preferable content of the blowing agent is 3 to 10% by mass.

(E) Other components Examples of other components include resin components derived from polyfunctional vinyl monomers such as polyolefin resins such as polyethylene and polypropylene, polycarbonate resins, and polyesters. The polyfunctional vinyl monomer is preferably a monomer having 2 to 15 vinyl groups. For example, bifunctional monomers such as divinylbenzene, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated And trifunctional monomers such as isocyanuric acid triacrylate. The content of the resin component as these other components is preferably 10% by mass or less in the expandable particles.

In addition, flame retardants, flame retardant aids, lubricants, anti-binding agents, fusion accelerators, antistatic agents, spreaders, bubble regulators, crosslinking agents, fillers, colorants, etc. The additive may be contained.
As flame retardants, tetrabromocyclooctane, hexabromocyclododecane, trisdibromopropyl phosphate, tetrabromobisphenol A, tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol A- Examples thereof include bis (2,3-dibromopropyl ether).

Examples of the flame retardant aid include organic peroxides such as 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, dicumyl peroxide, and cumene hydroperoxide. .
Examples of the lubricant include paraffin wax and zinc stearate.
Examples of the binding inhibitor include calcium carbonate, silica, zinc stearate, aluminum hydroxide, ethylene bis stearamide, tricalcium phosphate, dimethyl silicon and the like.

Examples of the fusion accelerator include stearic acid, stearic acid triglyceride, hydroxystearic acid triglyceride, stearic acid sorbitan ester, and polyethylene wax.
Examples of the antistatic agent include polyoxyethylene alkylphenol ether, stearic acid monoglyceride, polyethylene glycol and the like.
Examples of the spreading agent include polybutene, polyethylene glycol, and silicone oil.
Examples of the bubble regulator include methacrylic acid ester copolymer, ethylene bis stearamide, polyethylene wax, ethylene-vinyl acetate copolymer, and the like.

(2) Location of Component B and Component C Component B is contained in a large amount in the central part of the expandable particles. By containing a large amount in the center, it is possible to provide expandable particles that can provide a foamed molded article having sufficient bending strength even with a small amount of steam. Here, the central portion means a region within about 30% of the particle radius from the particle center.
A large amount of component C is contained in the surface layer portion of the expandable particles. By containing a large amount in the surface layer portion, it is possible to provide expandable particles that can provide a foamed molded article having sufficient bending strength even with a small amount of steam. Here, the surface layer means a region within about 30% of the particle radius from the particle surface.
The presence positions of components B and C can be confirmed by various methods, but in the present invention, confirmation is performed with an infrared absorption spectrum of the cross section of the expandable particle. That is, the absorbance 1600 at 1600 cm ⁻¹ , which is a peak derived from the in-plane vibration of the benzene ring contained in the styrene resin, and the peak 1735 cm derived from the stretching vibration between C═O of the ester groups contained in the components B and C. ^The position of components B and C can be confirmed by the ratio D1735 / D1600 (hereinafter, the absorbance ratio) of the absorbance D1735 at ^-1 .

It is preferable that the absorbance ratio tends to decrease once from the center of the expandable particle toward the surface and then increase in the surface layer portion. The former decreasing tendency is due to a decrease in the content of component B, and the latter increasing tendency is due to an increase in the content of component C. The tendency of the decrease may be, for example, a tendency to linearly decrease from the central portion toward the surface, or may decrease greatly in a region close to the central portion or a region close to the surface, and thereafter tend to become a substantially constant value. The tendency of the increase may be a tendency to increase linearly toward the surface after once decreasing, or to increase largely in a region near the center or in a region close to the surface and thereafter become a substantially constant value.
The absorbance ratio at the center of the expandable particles is preferably in the range of 0.4 to 0.8. When the absorbance ratio is less than 0.4, it is necessary to increase the amount of steam at the time of foam molding in order to obtain a foam molded article having a desired strength, which may be inferior in energy saving. When the absorbance ratio is larger than 0.8, a foamed molded article having a desired strength may not be obtained. A preferred absorbance ratio is in the range of 0.5 to 0.8, and a more preferred absorbance ratio is in the range of 0.55 to 0.75.

The presence of a large amount of component B in the center can be understood by comparing the absorbance ratio of the center with the minimum value of the absorbance ratio. The minimum value is a value that is less influenced by the components B and C, and is a value indicated between the center portion and the surface layer portion.
The minimum value of the absorbance ratio is preferably in the range of 0.10 to 0.15. Furthermore, the minimum value is preferably a relative value in the range of 0.1 to 0.4 when the absorbance ratio at the center is 1. This range of relative values indicates that the component B is contained in a large amount in the center.

The absorbance ratio of the surface layer portion of the expandable particles is preferably in the range of 0.3 to 0.6. When the absorbance ratio is less than 0.3, it is necessary to increase the amount of steam at the time of foam molding in order to obtain a foam molded article having a desired strength, which may be inferior in energy saving. When the absorbance ratio is larger than 0.6, a foamed molded article having a desired strength may not be obtained. A preferred absorbance ratio is in the range of 0.3 to 0.55, and a more preferred absorbance ratio is in the range of 0.35 to 0.55.
Furthermore, the minimum value is preferably a relative value in the range of 0.1 to 0.5 when the absorbance ratio of the surface layer portion is 1. This range of relative values indicates that the component C is contained in a large amount in the surface layer portion.

(3) Shape of expandable particle The shape of the expandable particle is not particularly limited. For example, spherical shape, cylindrical shape, etc. are mentioned. Of these, a spherical shape is preferable. The average particle diameter of the expandable particles can be appropriately selected according to the application, and for example, those having an average particle diameter of 0.2 mm to 5 mm can be used. In consideration of the filling ability into the mold, the average particle diameter is more preferably 0.3 mm to 2 mm, and still more preferably 0.3 mm to 1.4 mm.

(Method for producing expandable particles)
The method for producing the expandable particles is not particularly limited. For example, the first step of impregnating and polymerizing a monomer mixture containing a styrene monomer and a monofunctional acrylate into seed particles made of a styrene resin, and the particles obtained in the first step, Expandable particles are obtained by performing a second step of impregnating and polymerizing the monomer and a third step of impregnating the particles obtained in the second step with a foaming agent in the presence of an ester group-containing plasticizer. be able to.
(1) Seed particles Seed particles produced by a known method can be used. For example, (i) a styrene resin is melt-kneaded with an extruder, extruded into a strand, and the strand is cut. (Ii) An aqueous medium, a styrenic monomer and a polymerization initiator are fed into an autoclave, and the styrene monomer is subjected to suspension polymerization while heating and stirring in the autoclave to seed particles. (Iii) An aqueous medium and styrene resin particles are fed into an autoclave, and the styrene resin particles are dispersed in the aqueous medium, and then the styrene resin is heated and stirred in the autoclave. The monomer is continuously or intermittently supplied, and the styrene resin particles are absorbed in the styrene monomer and polymerized in the presence of a polymerization initiator to form seed particles. The seed polymerization method etc. to manufacture are mentioned.
In addition, the resin particles can be used for part or all of the seed particles. In the case of using a recovered product, production of seed particles by an extrusion method is suitable.

  The average particle diameter of the seed particles can be adjusted as appropriate according to the average particle diameter of the expandable particles. For example, when obtaining expandable particles having an average particle diameter of 1 mm, it is preferable to use seed particles having an average particle diameter of about 0.7 mm to 0.9 mm. Furthermore, the weight average molecular weight of the seed particles is not particularly limited, but is preferably 100,000 to 700,000, and more preferably 150,000 to 500,000.

(2) Impregnation step Each monomer is absorbed by the seed particles by supplying a monomer mixture or a styrene monomer into a dispersion obtained by dispersing the seed particles in an aqueous medium.
Examples of the aqueous medium include water and a mixed medium of water and a water-soluble solvent (for example, alcohol).

  Each monomer to be used may contain a polymerization initiator. The polymerization initiator is not particularly limited as long as it is conventionally used for monomer polymerization. For example, benzoyl peroxide, t-butyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, lauryl peroxide, t-butyl peroxide, t-butyl peroxypivalate, t-butyl peroxyisopropyl Organics such as carbonate, t-butyl peroxyacetate, 2,2-t-butylperoxybutane, t-butylperoxy-3,3,5-trimethylhexanoate, di-t-butylperoxyhexahydroterephthalate Examples thereof include peroxides, azo compounds such as azobisisobutyronitrile, azobisdimethylvaleronitrile, and the like. Among these initiators, in order to reduce the residual monomer, it is preferable to use two or more different polymerization initiators having a decomposition temperature of 80 to 120 ° C. for obtaining a half-life of 10 hours. In addition, a polymerization initiator may be used independently or 2 or more types may be used together.

  A suspension stabilizer may be included in the aqueous medium to stabilize the dispersion of monomer droplets and seed particles. The suspension stabilizer is not particularly limited as long as it is conventionally used for monomer suspension polymerization. Examples thereof include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, polyacrylamide, and polyvinyl pyrrolidone, and poorly soluble inorganic compounds such as tricalcium phosphate, magnesium pyrophosphate, and magnesium oxide. And when using a sparingly soluble inorganic compound as said suspension stabilizer, it is preferable to use an anionic surfactant together, and as such anionic surfactant, for example, fatty acid soap, N-acylamino acid or its Salts, carboxylates such as alkyl ether carboxylates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl sulfoacetates, sulfonates such as α-olefin sulfonates; higher alcohol sulfuric acid Ester salts, secondary higher alcohol sulfates, sulfates such as alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, etc .; phosphates such as alkyl ether phosphates, alkyl phosphates, etc. Is mentioned.

(3) Polymerization process Although a polymerization process changes with monomer types to be used, a polymerization initiator seed | species, a polymerization atmosphere seed | species, etc., it is normally performed by maintaining 70-130 degreeC heating for 1 to 10 hours. The polymerization step may be performed while impregnating the monomer.
In the polymerization step, the entire amount of the monomer to be used may be polymerized in one stage, or may be polymerized in two or more stages. It is easier to adjust the position of the resin component derived from the monofunctional acrylate ester by dividing into two or more stages. When polymerizing in two or more stages, the impregnation process is usually performed in two stages. The polymerization temperature and time of the polymerization process divided into two or more steps may be the same or different.

When performed in two stages, it is preferable to adjust the polymerization process as follows.
First, a monomer mixture containing a styrene monomer and a monofunctional acrylate is absorbed into seed particles of a styrene resin and polymerized in the seed particles (first step).
Next, the particles obtained through the first step are polymerized while absorbing the styrene monomer (second step).
Here, the monofunctional acrylic acid ester is preferably added to the polymerization vessel over 1 to 30 minutes.

Moreover, it is preferable that the usage-amount of the styrene-type monomer used at a 2nd process is 10 mass% or more with respect to the monomer whole quantity used at a 1st process and a 2nd process. When the amount is less than 10% by mass, resin components derived from monofunctional acrylates are included in the surface layer of the particles, and it may be difficult to obtain styrene resin particles having energy-saving formability and high strength. The amount of the styrene monomer used is more preferably 15% by mass or more, and further preferably 20% by mass or more.
Furthermore, although the weight average molecular weight of the styrene resin particle obtained through the said process is not specifically limited, 100,000-700,000 are preferable, More preferably, it is 150,000-500,000.
The expandable particles can be obtained by impregnating styrene resin particles with a foaming agent in the presence of an ester group-containing plasticizer. The impregnation may be performed wet simultaneously with the polymerization (for example, the second step), or may be performed wet or dry after the polymerization. When it is carried out in a wet manner, it may be carried out in the presence of a suspension stabilizer and a surfactant exemplified in the polymerization step.
The impregnation temperature of the foaming agent is preferably 60 to 120 ° C. When the temperature is lower than 60 ° C., the time required for impregnating the resin particles with the foaming agent becomes long, and the production efficiency may decrease. On the other hand, when the temperature is higher than 120 ° C., the resin particles may be fused to generate bonded particles. A more preferable impregnation temperature is 70 to 110 ° C.
A foaming aid may be used in combination with a foaming agent. Examples of the foaming aid include hydrocarbon solvent components D such as toluene, cyclohexane, and ethylbenzene. The hydrocarbon solvent component D may be included in an amount up to 2.0% by mass of expandable particles.

(Foamed particles)
The expanded particles are obtained by expanding the expandable particles to a desired bulk density using water vapor or the like. The foamed particles can be used as they are for applications such as cushioning fillers, and can be used as a raw material for foam molded articles for foaming in the mold. In the case of the raw material of the foam molded article, the expanded particles are generally referred to as pre-expanded particles, and the expansion to obtain the expanded particles is generally referred to as pre-expanded.
The bulk density of the expanded particles is preferably in the range of 0.01 to 0.04 g / cm ³ . When the bulk density of the expanded particles is less than 0.01 g / cm ³ , shrinkage may occur in the foamed molded product to be obtained next, and the appearance may be deteriorated. In addition, the heat insulation performance and mechanical strength of the foamed molded product may deteriorate. On the other hand, when the bulk density is larger than 0.04 g / cm ³ , the lightweight property of the foamed molded product may be lowered.
In addition, it is preferable to apply powder metal soaps such as zinc stearate to the surface of the expandable particles before foaming. By applying, the bonding between the foamed particles can be reduced in the foaming process of the foamable particles.

(Foamed molded product)
The foamed molded product can be used, for example, as a packaging material for fish, agricultural products, etc., a heat insulating material for floor insulation, a banking material, a tatami core material, and the like.
The density of the foam molded article is preferably in the range of 0.01 to 0.04 g / cm ³ . When the density of the foamed molded product is smaller than 0.01 g / cm ³ , the foamed molded product may shrink and the appearance may be deteriorated. In addition, the heat insulation performance and mechanical strength of the foamed molded product may deteriorate. On the other hand, when the density is larger than 0.04 g / cm ³ , the lightweight property of the foamed molded product may be lowered.

The foam molded article can be obtained, for example, by the following method.
By filling the expanded particles in a closed mold having a large number of small holes and heating and foaming with a heat medium (for example, pressurized water vapor) to fill the voids between the expanded particles and fuse the expanded particles to each other A foamed molded product can be produced by integrating the components. At that time, the density of the foamed molded product can be adjusted, for example, by adjusting the filling amount of the foamed particles in the mold.

  Heating foaming can be performed, for example, by heating with a heat medium of 110 to 150 ° C. for 5 to 50 seconds. Under these conditions, good fusing property between the particles can be ensured. More preferably, the heat foaming can be performed by heating for 10 to 50 seconds with a heat medium of 90 to 120 ° C. In the present invention, of this heating time, the time required for so-called one heating can be shortened to about half of the conventional time (about 8 seconds to 4 seconds). This one-side heating is the heating that requires the largest amount of steam during the entire heating. On the other hand, if the time required for the heating can be shortened, the manufacturing cost of the foamed molded product can be suppressed. Moreover, heating foaming can be performed under a pressure lower than a typical vapor pressure (for example, 0.06 to 0.08 MPa), which is a molding vapor pressure (gauge pressure) of the heat medium of 0.03 to 0.05 MPa. .

  The foamed particles may be aged, for example, at normal pressure before molding the foamed molded product. The aging temperature of the expanded particles is preferably 20 to 60 ° C. When the aging temperature is low, the aging time of the expanded particles may be long. On the other hand, if it is high, the foaming agent in the foamed particles may dissipate and the moldability may deteriorate.

  Hereinafter, specific examples of the present invention will be described by way of examples. However, the following examples are merely illustrative of the present invention, and the present invention is not limited to the following examples. In the following, “part” and “%” are based on mass unless otherwise specified.

<Average molecular weight>
A particle sample (0.003 g) is dissolved in 10 mL of tetrahydrofuran (THF) (completely dissolved), and filtered through a non-aqueous 0.45 μm chromatographic disk. The weight average molecular weight of the sample is obtained from a standard polystyrene calibration curve that has been measured and prepared in advance. The chromatographic conditions are as follows.
・ Device: High-speed GPC device ・ Product name: HLC-8320GPC EcoSEC-WorkStation (built-in RI detector) manufactured by Tosoh Corporation
・ Analysis conditions Column: TSKgel SuperHZM-H × 2 (4.6 mm ID × 15 cmL × 2)
Guard column: TSK guard column Super HZ-H x 1 (4.6 mm ID x 2 cm L)
Flow rate: Sample side 0.175 ml / min, Reference side 0.175 ml / min
Detector: Built-in RI detector Concentration: 0.3 g / L
Injection volume: 50 μL
Column temperature: 40 ° C
System temperature: 40 ° C
Eluent: THF

(Create a calibration curve)
Standard polystyrene samples for calibration curves include standard polystyrene samples having a weight-average molecular weight of 500, 2630, 9100, 37900, 102000, 355000, 3840000, and 5480000 as trade name “TSK standard POLYSYRENE” manufactured by Tosoh Corporation; A standard polystyrene sample having a weight average molecular weight of 1030000 with a trade name “Shodex STANDARD” manufactured by the company is used.
The method of creating a calibration curve is as follows. First, the standard polystyrene samples for calibration curves are group A (with a weight average molecular weight of 1030000), group B (with a weight average molecular weight of 500, 9100, 102000, and 3480000) and group C (with a weight average molecular weight of 2630, 37900). 355,000 and 5480000). 5 mg of a standard polystyrene sample belonging to group A having a weight average molecular weight of 1030000 is weighed and then dissolved in 20 mL of THF, and 50 μL of the resulting solution is injected into the sample side column. Standard polystyrene samples belonging to group B having weight average molecular weights of 500, 9100, 102000, and 3480000 are weighed 10 mg, 5 mg, 5 mg, and 5 mg, respectively, dissolved in 50 mL of THF, and 50 μL of the resulting solution is injected into the sample side column. . Standard polystyrene samples having a weight average molecular weight of 2630, 37900, 355000, and 5480000 belonging to group C were weighed 5 mg, 5 mg, 5 mg, and 1 mg, respectively, dissolved in 40 mL of THF, and 50 μL of the resulting solution was injected into the sample side column. . A calibration curve (tertiary equation) is prepared from the retention time of these standard polystyrene samples with a data analysis program GPC workstation (EcoSEC-WS) dedicated to HLC-8320GPC, and this is used as a calibration curve for polystyrene-equivalent weight average molecular weight measurement.

<Absorbance ratio of center part and surface layer part, minimum value of absorbance ratio>
(A) Preparation of measurement sample Ten particles selected at random are fixed to a plastic sample support (manufactured by Nissin EM). Next, a slice sample is obtained by slicing the particles with a diamond knife using an ultramicrotome (LEICA ULTRACUT UCT, manufactured by Leica Microsystems) to a thickness of about 10 μm through the center. The obtained slice sample is sandwiched between two barium fluoride crystals (manufactured by Pier Optics). This is used as a measurement sample. The image of the slice sample is captured by the CCD attached to the following measuring device. Image capture is performed with the advancing direction of the blade of the ultramicrotome as the Y axis and the vertical direction as the X axis. The particles in the slice sample are slightly crushed in the moving direction of the blade. By matching the Y-axis of the captured image with the direction of travel of the blade, the measured absorbance ratio is prevented from varying.
For the absorbances D1735 and D1600, an apparatus sold by Perkin Elmer under the trade name “High-Speed IR Imaging System Spectrum Spotlight 300” is used. Using this apparatus, a total absorbance image of the slice sample particle cross section is obtained under the following conditions, and an infrared absorption spectrum at each location of the slice sample particle cross section is obtained.

(Measurement condition)
Mode: Microscopic transmission imaging Pixel size: 6.25 μm
Measurement region: 4000 cm ^{−1 to} 650 cm ⁻¹
Detector: MCT
Resolution: 8cm ^-1
Scan / pixel: 2 times (background measurement condition)
Mode: Microscopic transmission imaging Pixel size: 6.25 μm
Measurement region: 4000 cm ^{−1 to} 650 cm ⁻¹
Detector: MCT
Resolution: 8cm ^-1
Scan / pixel: 60 times Others: A process that does not participate in the measurement spectrum is performed using the infrared absorption spectrum obtained by measuring the barium fluoride crystal in the vicinity of the sample without the sample as a background.

  From the captured image, as shown in FIG. 1, the minimum and maximum values of the X coordinate value and the minimum and maximum values of the Y coordinate value of the Y axis are connected by a line, and the intersection of the lines is set as the center point A. . In image processing, the X and Y coordinate values of the center point are set within a range of ± 20 μm from the center point A.

  Next, a straight line passing through the center point A and parallel to the X axis is drawn in the image. A point where this straight line intersects with the position of the end where the particle (resin) exists (maximum value on the X axis) is defined as a point D. An infrared absorption spectrum on a line connecting the points A and D is extracted every 12 ± 2 μm as an X coordinate value. The central portion in the present invention is a portion of 30% of the distance from the point A to the point D from the particle central portion toward the surface, and the surface layer portion is the distance from the point D to the point A toward the center from the surface. The 30% portion is said to be within a range of ± 20 μm.

  Absorbances D1735 and D1600 are read from the extracted infrared absorption spectrum, respectively, and the absorbance ratio (D1735 / D1600) at the center and 50% radius is calculated. The arithmetic average of the individual absorbance ratios calculated for 10 particles is taken as the absorbance ratio.

The absorbance D1735 at 1735 cm ⁻¹ obtained from the infrared absorption spectrum is the absorbance corresponding to the absorption spectrum derived from the stretching vibration between C═O of the ester group contained in the ester. In this absorbance measurement, peak separation is not performed even when other absorption spectra overlap at 1735 cm ⁻¹ . Absorbance D1735 is a straight line connecting the 1680 cm ^-1 and 1785 cm ^-1 as a baseline, means the maximum absorbance between 1680 cm ^-1 and 1785 cm ^-1. Further, the absorbance D1600 at 1600 cm ⁻¹ obtained from the infrared absorption spectrum is an absorbance corresponding to the absorption spectrum derived from the in-plane vibration of the benzene ring contained in the styrene resin. In this absorbance measurement, peak separation is not performed even when other absorption spectra overlap at 1600 cm ⁻¹ . Absorbance D1600 is a straight line connecting the 1565Cm ^-1 and 1640 cm ^-1 as a baseline, means the maximum absorbance between 1565cm ^-1 and 1640 cm ^-1.

<Bulk density of pre-expanded particles>
The bulk magnification of the pre-expanded particles is obtained by collecting Wg using the pre-expanded particles as a measurement sample, and allowing the measurement sample to fall naturally into a measuring cylinder. The bulk volume Vcm ³ of the measurement sample dropped into the measuring cylinder is measured according to JIS K6911. By substituting Wg and Vcm ³ into the following formula, the bulk density of the pre-expanded particles is calculated.
Bulk density of pre-expanded particles (g / cm ³ ) = mass of measurement sample (W) / volume of measurement sample (V)

<Density of foam molding>
The mass (a) and volume (b) of a test piece (example 75 × 300 × 30 mm) cut out from a foamed molded product (after being molded and dried at 40 ° C. for 20 hours or more) each have three or more significant figures. Then, the density (g / cm ³ ) of the foamed molded product is obtained by the formula (a) / (b).

<Average maximum bending strength>
The average maximum bending strength of the foam is measured according to the method described in JIS K7221-2 “Rigid Foamed Plastic—Bending Test”. Specifically, a rectangular parallelepiped test piece having a length of 75 mm × width of 300 mm × thickness of 30 mm is cut out from a foam having a density of 16.7 kg / m ³ . Thereafter, this test piece was subjected to a bending strength measuring instrument (trade name “UCT-10T” manufactured by Orientec Co., Ltd.) under the conditions of a test speed of 10 mm / min, a distance between fulcrums of 200 mm, a pressure wedge 10R and a support base 10R. Measure with Five test pieces are prepared, and the maximum load at which the test piece breaks is measured for each test piece as described above, and the bending strength is calculated.
Evaluation: Average maximum bending strength is 0.3 MPa or more: ○
Less than 0.3 MPa: ×
<Comprehensive evaluation>
At the time of molding of the foamed molded product, the case where the heating time is 5 seconds or less is marked as ◯, and the case where it is longer than 5 seconds is marked as x.
On the other hand, when both the evaluation of the heating time and the evaluation of the maximum bending strength are “good”, the comprehensive evaluation is “、”, and when either one is “×”, the comprehensive evaluation is “poor”.

Example 1
(Manufacture of seed particles)
A polymerization vessel equipped with a stirrer with an internal capacity of 100 liters is supplied with 40000 parts by mass of water, 100 parts by mass of magnesium pyrophosphate as a suspension stabilizer, and 5.0 parts by mass of sodium dodecylbenzenesulfonate as an anionic surfactant. After adding 40000 parts by mass and 96.0 parts by mass of benzoyl peroxide and 28.0 parts by mass of t-butylperoxybenzoate as polymerization initiators, the temperature was raised to 90 ° C. to polymerize. And it hold | maintained at this temperature for 6 hours, and also, after heating up to 125 degreeC, it cooled after 2 hours, and obtained the styrene-type resin particle (a).
The styrene resin particles (a) are sieved to obtain styrene resin particles (b) having a particle diameter of 0.5 to 0.71 mm, an average particle diameter of 0.63 mm, and a weight average molecular weight of 250,000 as seed particles. It was.

Next, 2350 g of styrene resin (b) (seed particles), 30 g of magnesium pyrophosphate and 10 g of sodium dodecylbenzenesulfonate are supplied to a polymerization vessel equipped with a stirrer with an internal volume of 25 L and heated to 72 ° C. while stirring. A dispersion was prepared.
Subsequently, a solution prepared by dissolving 45.9 g of benzoyl peroxide and 6.1 g of t-butylperoxybenzoate in a mixture of 850 g of styrene and 150 g of n-butyl acrylate was supplied to the dispersion while stirring.
And after supplying the said solution in a dispersion liquid, it maintained at 72 degreeC for 60 minute (1st process).

  Thereafter, while supplying 6650 g of styrene to this dispersion at a constant rate in 150 minutes, the dispersion was heated from 72 ° C. to 90 ° C. over 60 minutes, and maintained at 90 ° C. for 90 minutes (second step).

Further, the dispersion was heated to 125 ° C. and held for 30 minutes to react unreacted monomers. Subsequently, styrene resin particles having an average particle diameter of 1.0 mm were collected from the reaction vessel. The styrene resin particles had an Mw of 24,000,000.
Next, the dispersion is kept at 90 ° C., and then 70 g of diisobutyl adipate and 700 g of n-butane are pressed into the polymerization vessel and held for 3 hours, whereby n-butane is contained in the resin particles. Impregnated. Thereafter, the inside of the polymerization vessel was cooled to 25 ° C. to obtain expandable particles.
The expandable particles seek and absorbance D1600 at absorbance D1735 and 1600 cm ^-1 in 1735 cm ^-1, was calculated D1735 / D1600. As a result, the absorbance ratio at the center was 0.69, the minimum value of the absorbance ratio was 0.14, and the absorbance ratio at the surface layer was 0.45. The absorbance ratio of the surface layer portion of the styrene resin particles before impregnation with the blowing agent is 0.12, and the increase to 0.45 is derived from diisobutyl adipate.
FIG. 1 shows the change in absorbance ratio from the center to the surface of the obtained expandable particles.

Polyethylene glycol was applied as an antistatic agent to the surface of the expandable particles. Thereafter, zinc stearate and hydroxystearic acid triglyceride were further applied to the surface of the expandable particles. After coating, the expandable particles were left in a thermostatic chamber at 13 ° C. for 5 days.
The expandable particles were heated and pre-expanded to a bulk density of 0.0166 g / cm ³ to obtain pre-expanded particles. Pre-expanded particles were aged at 20 ° C. for 24 hours.
Next, the pre-expanded particles were filled in a mold and heated and foamed at a vapor pressure of 0.04 MPa to obtain a foamed molded product having a length of 400 mm × width of 300 mm × thickness of 30 mm. After the foamed molded product was dried in a drying chamber at 50 ° C. for 6 hours, the density was measured and found to be 0.0166 g / cm ³ (16.6 kg / m ³ ). The foamed molded article was excellent in appearance without shrinkage. In addition, the heating time required in the process of passing the pre-expanded particles filled from one mold, which is generally referred to as one heating, during heating and foaming, and passing water vapor through the other mold is 3 seconds, It was very short. The amount of water vapor required for one molding was 4.7 kg.
As a result of measuring the bending test of the obtained foamed molded product in accordance with JIS-A9511, the bending strength was excellent at 0.32 MPa.

(Example 2)
A foam molded article was obtained in the same manner as in Example 1 except that the amount of styrene used in the first step was 950 g and the amount of n-butyl acrylate was 50 g. The absorbance ratio of the center part of the expandable particles was 0.49, the minimum value of the absorbance ratio was 0.11, and the absorbance ratio of the surface layer part was 0.44. On the other hand, the heating time was 4 seconds, the amount of water vapor was 4.8 kg, and the bending strength of the foamed molded product was excellent at 0.32 MPa.
(Example 3)
A foamed molded article was obtained in the same manner as in Example 1 except that the amount of styrene used in the first step was 700 g and the amount of n-butyl acrylate was 300 g. The absorbance ratio of the central part of the expandable particles was 0.75, the minimum value of the absorbance ratio was 0.14, and the absorbance ratio of the surface layer part was 0.44. On the other hand, the heating time was 2 seconds, the amount of water vapor was 4.5 kg, and the bending strength of the foamed molded product was excellent at 0.32 MPa.

Example 4
A foam molded article was obtained in the same manner as in Example 1 except that the amount of diisobutyl adipate added was 40 g. The absorbance ratio of the central part of the expandable particles was 0.65, the minimum value of the absorbance ratio was 0.12, and the absorbance ratio of the surface layer part was 0.39. On the other hand, the heating time was 4 seconds, the water vapor amount was 5.1 kg, and the bending strength of the foamed molded product was excellent at 0.33 MPa.
(Example 5)
A foamed molded article was obtained in the same manner as in Example 1 except that the amount of diisobutyl adipate added was 150 g. The absorbance ratio of the central part of the expandable particles was 0.69, the minimum value of the absorbance ratio was 0.12, and the absorbance ratio of the surface layer part was 0.50. On the other hand, the heating time was 3 seconds, the water vapor amount was 4.8 kg, and the bending strength of the foamed molded product was excellent at 0.32 MPa.
(Example 6)
A foamed molded article was obtained in the same manner as in Example 1 except that propyl acrylate was used as the monofunctional acrylate. The absorbance ratio of the central part of the expandable particles was 0.71, the minimum value of the absorbance ratio was 0.11, and the absorbance ratio of the surface layer part was 0.48. On the other hand, the heating time was 4 seconds, the water vapor amount was 5.1 kg, and the bending strength of the foamed molded product was excellent at 0.33 MPa.
(Example 7)
A foamed molded article was obtained in the same manner as in Example 1 except that dioctyl phthalate was used as the plasticizer. The absorbance ratio of the central part of the expandable particles was 0.67, the minimum value of the absorbance ratio was 0.12, and the absorbance ratio of the surface layer part was 0.50. On the other hand, the heating time was 3 seconds, the amount of water vapor was 4.6 kg, and the bending strength of the foamed molded product was excellent at 0.33 MPa.
(Example 8)
A foamed molded article was obtained in the same manner as in Example 1 except that 80 g of cyclohexane as a hydrocarbon solvent was used in combination with 70 g of diisobutyl adipate. The absorbance ratio of the central part of the expandable particles was 0.68, the minimum value of the absorbance ratio was 0.12, and the absorbance ratio of the surface layer part was 0.48. On the other hand, the heating time was 3 seconds, the water vapor amount was 4.8 kg, and the bending strength of the foamed molded product was excellent at 0.32 MPa.

(Comparative Example 1)
In the first step, a foamed molded article was obtained in the same manner as in Example 1 except that styrene was used instead of butyl acrylate. The absorbance ratio at the center of the foamed molded product and the minimum value of the absorbance ratio were both 0.13, and the absorbance ratio of the surface layer portion was 0.40. On the other hand, the heating time was as long as 8 seconds, the amount of steam was 8.5 kg, and the amount of steam was large. The bending strength was 0.31 MPa.

(Comparative Example 2)
A foam molded article was obtained in the same manner as in Example 1 except that the amount of styrene used in the first step was 980 g and the amount of n-butyl acrylate was 20 g. The absorbance ratio of the central part of the expandable particles was 0.35, the minimum value of the absorbance ratio was 0.10, and the absorbance ratio of the surface layer part was 0.44. On the other hand, the heating time was as long as 8 seconds, the amount of steam was 8.5 kg, and the amount of steam was large. The bending strength of the foamed molded article was excellent at 0.32 MPa.
(Comparative Example 3)
A foamed molded article was obtained in the same manner as in Example 1 except that the amount of styrene used in the first step was 550 g and the amount of n-butyl acrylate was 450 g. The absorbance ratio of the central part of the expandable particles was 0.85, the minimum value of the absorbance ratio was 0.13, and the absorbance ratio of the surface layer part was 0.44. On the other hand, the heating time was 3 seconds and the water vapor amount was 4.7 kg, but the bending strength of the foamed molded product was reduced to 0.28 MPa.

(Comparative Example 4)
A foam molded article was obtained in the same manner as in Example 1 except that diisobutyl adipate was not used. The absorbance ratio of the surface layer portion of the foam molded article was 0.68, and both the minimum value of the absorbance ratio and the absorbance ratio of the surface layer portion were 0.12. On the other hand, although the heating time was 4 seconds and the amount of water vapor was 4.9 kg, the bending strength of the foamed molded product was lowered to 0.28 MPa because of the low fusibility between the foamed particles.
(Comparative Example 5)
A foamed molded article was obtained in the same manner as in Example 1 except that the amount of diisobutyl adipate added was 200 g. The absorbance ratio of the central part of the expandable particles was 0.67, the minimum value of the absorbance ratio was 0.11, and the absorbance ratio of the surface layer part was 0.65. On the other hand, although the heating time was 3 seconds and the amount of water vapor was 4.8 kg, the foamed molded product contracted due to heat, and the bending strength decreased to 0.27 MPa.
The results of Examples 1 to 8 and Comparative Examples 1 to 5 are summarized in Table 1.

In Comparative Example 4 of Table 1, the absorbance ratio of the surface layer portion of the expandable particles when no ester group-containing plasticizer (diisobutyl adipate) is used is shown. Since the absorbance ratio of the surface layer portions of Examples 1 to 8 is higher than the absorbance ratio of Comparative Example 4, it can be seen that the foamable particles of these Examples contain a large amount of ester group-containing plasticizer in the surface layer portion.
From Examples 1 to 8, the resin component derived from the monofunctional acrylic acid ester is contained in a large amount in the center part of the expandable particle, and the ester group-containing plasticizer is contained in a large amount in the surface layer part of the expandable particle. It can be seen that a foamed molded article with improved bending strength can be obtained even with the amount of steam.
From Comparative Example 1, it can be seen that when the resin component derived from the monofunctional acrylate ester is not included, the effect of reducing the vapor amount is insufficient.
From Comparative Example 2, it can be seen that when the resin component derived from the monofunctional acrylic ester is not contained in the center part, the effect of reducing the amount of vapor is insufficient.
From Comparative Example 3, it can be seen that when the resin component derived from the monofunctional acrylate ester is contained in a large amount other than the central portion, the effect of improving the bending strength of the foam molded article is inferior.
From Comparative Example 4, it can be seen that when the ester group-containing plasticizer is not included, the bond between the foamed particles during foam molding is weak, and the effect of improving the bending strength of the foam molded article is poor.
From Comparative Example 5, it can be seen that when the ester group-containing plasticizer is contained in a large amount other than the surface layer portion, the effect of improving the bending strength of the foamed molded article is inferior due to shrinkage during molding.

Claims (12)

Expandable styrene resin particles comprising a styrene resin component A, a component B derived from a monofunctional acrylic ester, an ester group-containing plasticizer C, and a foaming agent,
Component B derived from the monofunctional acrylate ester is contained in a large amount in the center of the styrene resin particles,
Expandable styrene resin particles, wherein the ester group-containing plasticizer component C is contained in a large amount in the surface layer portion of the styrene resin particles.   The expandable styrene resin particles contain 0.3 to 3.5% by mass of the component B derived from the monofunctional acrylate ester, and 0.3 to 1.8% by mass of the ester group-containing plasticizer component C. The expandable styrenic resin particle according to claim 1 comprising.   The expandable styrenic resin particles according to claim 1 or 2, wherein the center of the expandable styrene resin particles exhibits an absorbance ratio (D1735 / D1600) in a range of 0.4 to 0.8.   The foamable styrenic resin particles have a relative value in which the minimum value of the absorbance ratio (D1735 / D1600) is in the range of 0.1 to 0.4 when the absorbance ratio (D1735 / D1600) at the center is 1. The expandable styrene resin particle according to any one of claims 1 to 3, wherein the expandable styrene resin particle is a particle to be displayed.   The foamable styrene resin particles have a relative value in which the minimum value of the absorbance ratio (D1735 / D1600) is in the range of 0.1 to 0.5, where the absorbance ratio (D1735 / D1600) of the surface layer portion is 1. The expandable styrene resin particles according to any one of claims 1 to 4, wherein the expandable styrene resin particles.   The expandable styrenic resin particles according to any one of claims 1 to 5, wherein the monofunctional acrylic ester is a monomer having an alkyl group having 1 to 8 carbon atoms in an ester portion.   The expandable styrene resin particles according to any one of claims 1 to 6, wherein the ester group-containing plasticizer is selected from adipic acid esters, phthalic acid esters, and glycerin fatty acid esters.   The expandable styrenic resin particles according to any one of claims 1 to 7, wherein the expandable styrene resin particles further contain a hydrocarbon solvent component D.   Foamed particles obtained by foaming the expandable styrenic resin particles according to any one of claims 1 to 8.   A foam-molded product obtained by foam-molding the foamed particles according to claim 9.   The foamed molded product according to claim 10, wherein the foamed molded product has a container-like shape.   It is a manufacturing method of the expandable styrene resin particle as described in any one of the said Claims 1-8, Comprising: The seed particle | grains which consist of a styrene resin contain the styrene monomer and monofunctional acrylate ester. The first step of impregnating and polymerizing the monomer mixture, the second step of impregnating and polymerizing the styrene monomer on the particles obtained in the step, and the ester group-containing plasticizer on the particles obtained in the step And a third step of impregnating the foaming agent in the presence of the foaming styrene resin particles.