JP2011231915A - Heat retaining box and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat retaining material excellent in foamability, thermal weldability and heat resistance.SOLUTION: The heat retaining box as a heat insulating material comprises: a resin comprising a component derived from an ester obtained by a reaction of 10-20C polycyclic terpenol with methacrylic acid and a styrene monomer-derived component; and a volatile foaming agent. (1) The resin comprises the ester-derived component of >1 pts.wt. and <30 pts.wt. based on 100 pts.wt. of the total of the ester-derived component and the styrene monomer-derived component. (2) A foamable polystyrene-based resin particle has a surface layer of 0.35-6.00 absorbance ratio X (D1730/D1600) (wherein D1730 is the absorbance at 1730 cmpeak of an infrared absorption spectrum obtained by infrared spectroscopic analysis; D1600 is that at 1600 cmpeak thereof). (3) A central part of the absorbance ratio Y (D1730/D1600) smaller than the absorbance ratio X. The heat retaining box comprises an expansion-molded product of the foamable polystyrene-based resin particle.

Description

  The present invention relates to a heat insulation box and a method for manufacturing the same. ADVANTAGE OF THE INVENTION According to this invention, the heat insulation box excellent in foamability, heat-fusibility, and heat resistance and its manufacturing method can be provided.

  Synthetic resin products are often used as heat insulation boxes. Among them, in order to increase the heat retention and preserve the contents for a long period of time, a foamed molded body as a heat insulating material is often used (for example, JP-A-2005-225533). The foam molded body is obtained by in-mold foam molding of expandable resin particles. In-mold foam molding is a process in which expandable resin particles such as expandable polystyrene particles are heated and pre-expanded, and the pre-expanded particles thus obtained are filled into the mold cavity, and the pre-expanded particles are secondary It refers to a molding method in which a foamed molded article is molded by foaming and pre-expanded particles are thermally fused.

JP 2005-225533 A

  Since the heat insulation box is used in a state where heat is applied, it is required to have high heat resistance from the viewpoint of improving dimensional stability. Although the foam molded body of the above publication can secure a certain degree of heat resistance, further improvement in heat resistance has been desired in order to improve the dimensional stability of a heat insulating box used at higher temperatures.

  As a result of intensive studies, the inventors of the present invention have a resin component derived from an ester of a polycyclic terpenol having 10 to 20 carbon atoms and methacrylic acid richly present in the vicinity of the surface of the expandable styrene resin particles. It came to this invention by discovering unexpectedly that the heat resistance of a heat retention box can be improved.

Thus, according to the present invention, the heat insulation box as a heat insulating material is
A resin containing a component derived from an ester of a polycyclic terpenol having 10 to 20 carbon atoms and methacrylic acid and a component derived from a styrene monomer, and a volatile foaming agent,
(1) The monomer mixture has more than 30 parts by weight of the component derived from the ester with respect to 100 parts by weight in total of the component derived from the ester and the component derived from the styrene monomer. Including less than parts by weight,
(2) having a surface layer with an absorbance ratio X (D1730 / D1600) in the range of 0.35 to 6.00 (D1730 and D1600 are the absorbance at 1730 cm ⁻¹ in the infrared absorption spectrum by infrared spectroscopic analysis; Means absorbance at 1600 cm ⁻¹ ),
(3) There is provided a heat insulation box comprising a foamed molded body of expandable polystyrene resin particles having a central portion with an absorbance ratio Y (D1730 / D1600) smaller than the absorbance ratio X.

Moreover, it is a manufacturing method of the said heat insulation box,
A step of allowing a seed particle to absorb a monomer mixture containing an ester of the C10-20 polycyclic terpenol and methacrylic acid and a styrenic monomer in an aqueous medium;
A step of obtaining polystyrene resin particles by polymerizing the monomer mixture after absorbing or absorbing; and
A step of impregnating a polystyrene resin particle with a volatile foaming agent after polymerization or while polymerizing to obtain expandable polystyrene resin particles;
There is provided a method for producing a heat insulation box, which includes a step of pre-foaming expandable polystyrene resin particles and then foam-molding.

According to the present invention, a resin component derived from an ester of a polycyclic terpenol having 10 to 20 carbon atoms and methacrylic acid can be richly present in the vicinity of the surface of the expandable styrene resin particles. From the foamable styrenic resin particles, a heat insulation box having good heat resistance, heat-fusibility and moldability can be obtained.
In addition, when the ester is a component derived from a monomer selected from isobornyl methacrylate, bornyl methacrylate, norbornyl methacrylate, adamantyl methacrylate, and lower alkyl substituents thereof, further heat resistance Can be obtained.
Furthermore, when the absorbance ratio Y is in the range of 0 to 4.0, the ester is present more in the vicinity of the particle surface, so that the heat insulation box is improved in heat resistance without inhibiting foaming properties. Can be obtained.

2 is a mapping image of expandable styrene resin particles of Example 1. 2 is a graph showing the relationship between the distance from the center of the expandable styrene resin particles of Example 1 and the absorbance ratio.

The heat insulating box as the heat insulating material of the present invention is a foamable polystyrene in which a resin component derived from an ester of a polycyclic terpenol having 10 to 20 carbon atoms and methacrylic acid is present in the surface layer in a rich manner (locally distributed). It consists of a foamed molded body of resin particles.
(Ester of C10-20 polycyclic terpenol and methacrylic acid)
The polycyclic terpenol having 10 to 20 carbon atoms is not particularly limited as long as the heat resistance can be improved, and can also be referred to as a bridged alicyclic compound. The number of rings constituting terpenol is 2 or more, for example, 2 to 6. Furthermore, the number of bridges is set according to the number of rings, and is, for example, 1 to 3. The bridges may or may not intersect. Specific examples of terpenols include santenol, sabinol, pinocarbeol, myrtenol, berbenol, twill alcohol, pinocampheol, borneol, norborneol, isoborneol, fentil alcohol, isofentil alcohol, adamantanol and the like. Can be mentioned.

Further preferred esters include isobornyl methacrylate, bornyl methacrylate, norbornyl methacrylate, adamantyl methacrylate, and lower alkyl substituents thereof. Examples of the lower alkyl group include an alkyl group having 1 to 4 carbon atoms. These esters may be used alone or in combination.
The ester of methacrylic acid has good copolymerizability with styrene and has a higher glass transition temperature as a single resin compared to the same type of acrylic acid ester. Suitable for

The content of the component derived from the ester is more than 1 part by weight and less than 30 parts by weight with respect to a total of 100 parts by weight of the component derived from the ester and the component derived from the styrene monomer. If it is 1 part by weight or less, a foamed molded product having insufficient heat resistance may be produced, and if it is 30 parts by weight or more, foamability and heat-sealing property may be lowered. A preferable content is 2 to 25 parts by weight, and a more preferable content is 5 to 20 parts by weight.
In addition, content of each component which comprises an expandable polystyrene resin particle is substantially in agreement with the usage-amount of each monomer corresponding to each component used for manufacture of an expandable polystyrene resin particle.

(Styrene monomer)
Expandable styrene resin particles are composed of a resin containing a component derived from the ester and a component derived from a styrene monomer.
The styrene monomer is not particularly limited, and any known styrene or styrene derivative can be used. Examples of the styrene derivative include α-methyl styrene, vinyl toluene, chlorostyrene, ethyl styrene, i-propyl styrene, dimethyl styrene, bromostyrene, and the like. These styrenic monomers may be used alone or in combination.

(Other monomers)
A vinyl monomer copolymerizable with the styrene monomer may be used in combination. Examples of the vinyl monomer include divinylbenzene such as o-divinylbenzene, m-divinylbenzene and p-divinylbenzene, alkylene glycol di (meth) acrylate such as ethylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylate. Multifunctional monomers such as (meth) acrylate; α-methylstyrene, (meth) acrylonitrile, methyl (meth) acrylate and the like. These other monomers may be used alone or in combination.
When other monomers are used, the content of the components derived from the other monomers is such that the styrene monomer is the main component with respect to the sum of the other monomers (for example, 50% by weight or more). (Meth) acrylic means methacrylic or acrylic.

  Among the other monomers, the polyfunctional monomer can improve the appearance of the foamed molded product. As the polyfunctional monomer for improving the appearance, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate (the number of ethylene glycol is 4 to 16), divinylbenzene is more preferable, and divinylbenzene. Ethylene glycol di (meth) acrylate is preferred.

(Absorbance ratio)
(1) Absorbance ratio of surface layer The expandable polystyrene resin particles have 1730 cm ^{−1 in} the range of 0.35 to 6.00 from the infrared absorption spectrum obtained by measuring the surface layer by infrared spectroscopic analysis. It has an absorbance ratio X of 1600 cm ⁻¹ (D1730 / D1600). A preferable absorbance ratio is 0.40 to 5.50, and more preferably 1.00 to 4.50. The surface layer includes a region from the particle surface to a depth of several μm (for example, 6 μm).
When the absorbance ratio is less than 0.35, the ratio of the resin derived from the ester of polycyclic terpenol and methacrylic acid in the surface layer is lowered. As a result, the dimensional shrinkage of the foamed molded article at a high temperature may be large and desired heat resistance may not be obtained. When the absorbance ratio is greater than 4.50, the heat resistance of the surface layer is excessively increased, and it may not be softened by heat during foaming or molding, and fusion of the molded product may be hindered.

Here, the infrared spectroscopic analysis in the present invention is an analysis method in which an infrared absorption spectrum is measured by a single reflection type ATR method using total reflection absorption (Attenuated Total Reflectance). This analysis method is a method in which an ATR prism having a high refractive index is brought into close contact with a sample, infrared light is irradiated to the sample through the ATR prism, and light emitted from the ATR prism is spectrally analyzed.
ATR infrared spectroscopic analysis includes organic materials such as polymer materials because of the simplicity of being able to measure the spectrum simply by bringing the sample and the ATR prism into close contact with each other, and the ability to perform surface analysis up to a depth of several μm. It is widely used for surface analysis of various substances.

The absorbance D 1730 at 1730 cm ⁻¹ obtained from the infrared absorption spectrum refers to the height of a peak appearing in the vicinity of 1730 cm ⁻¹ derived from stretching vibration between C═O of the ester group contained in the ester. Further, the absorbance D1600 at 1600 cm ⁻¹ obtained from the infrared absorption spectrum refers to the height of a peak appearing in the vicinity of 1600 cm ⁻¹ derived from the in-plane vibration of the benzene ring contained in the polystyrene resin.

  It is possible to determine the composition ratio between the ester-derived resin and the styrene-based monomer-derived resin from the absorbance ratio. For example, when the absorbance ratio is 0.35, the ester-derived resin is about 1.2 to 1.7% by weight, the styrene monomer-derived resin is about 98.3 to 98.8% by weight, When the absorbance ratio is 2.00, the ester-derived resin is about 8.0 to 12.0% by weight, the styrene monomer-derived resin is about 88.0 to 92.0% by weight, and the absorbance ratio is In the case of 4.50, it can be calculated that the resin derived from the ester is about 18.0 to 22.0% by weight and the resin derived from the styrene monomer is about 78.0 to 82.0% by weight.

(2) Relationship between Absorbance Ratio of Surface Layer and Center Part The expandable polystyrene resin particles have a center part with an absorbance ratio Y smaller than the absorbance ratio X of the surface layer. The relationship between the absorbance ratios means that the amount of the resin derived from the ester component in the surface layer is larger (rich) than the amount of the resin derived from the ester component in the center. By having this relationship, heat resistance can be ensured with the resin derived from the ester component rich in the surface layer, and foamability can be ensured with the resin derived from the styrene monomer rich in the center. Absorbance ratio Y, as well as the absorbance ratio X, is meant absorbance ratio of 1730 cm ^-1 and 1600 cm ^-1 to (D1730 / D1600). The central portion means a region within a radius of 30% from the center in a cross section including the center of the particle.
The specific range of the absorbance ratio Y is preferably 0 to 4.0, and more preferably 0 to 2.0.

(Volatile foaming agent)
A volatile foaming agent will not be specifically limited if it is conventionally used for foaming of polystyrene-type resin. Examples thereof include volatile foaming agents (physical foaming agents) such as aliphatic hydrocarbons having 5 or less carbon atoms such as propane, isobutane, n-butane, isopentane, neopentane, and n-pentane. Of these, butane-based blowing agents such as isobutane and n-butane are preferred.

If the content of the volatile foaming agent in the expandable polystyrene resin particles is small, a foamed molded product having a desired density may not be obtained, and the effect of increasing the secondary foaming power during in-mold foam molding may be obtained. Since it becomes small, the external appearance property of a foaming molding may fall. Moreover, since the time which the cooling process in the manufacturing process of a foaming molding body requires will become long when there are many, productivity may fall. From these viewpoints, the content is preferably in the range of 2.5 to 7.0% by weight, and more preferably in the range of 2.7 to 6.0% by weight.
The content of the foaming agent in the expandable polystyrene resin particles is determined by placing the expandable polystyrene resin particles in a pyrolysis furnace at 150 ° C. and measuring the amount of hydrocarbon generated in the pyrolysis furnace with a chromatograph. Can be obtained.

(Other ingredients)
For the expandable polystyrene resin particles, foaming aids, plasticizers, flame retardants, flame retardant aids, anti-bonding agents, foam control agents, cross-linking agents, fillers, lubricants, and colorants are used as long as the physical properties are not impaired. Additives such as may be added.
Alternatively, powder metal soaps such as zinc stearate may be applied to the surface of the expandable styrene resin particles. By applying, in the pre-expansion step of the expandable polystyrene resin particles, the bonding between the pre-expanded particles can be reduced.

(Shape of expandable polystyrene resin particles)
The shape of the expandable polystyrene resin particles is not particularly limited, but is preferably spherical from the viewpoint of ease of molding. Further, the particle diameter is preferably 0.3 to 2.0 mm, more preferably 0.3 to 1.4 mm in consideration of the filling property in the mold. Furthermore, when using for a heat retention box, 0.5-1.0 mm is preferable.

(Method for producing expandable polystyrene resin particles)
The method for producing the expandable polystyrene resin particles is not particularly limited as long as the ester-derived resin and the styrene-based monomer-derived resin can be present at the specific absorbance ratio. For example, in an aqueous suspension, the polystyrene-based resin particles (seed particles) include a step of absorbing the monomer mixture and a step of polymerizing the monomer mixture after absorption or absorption. It is easy to produce by a so-called seed polymerization method. The monomer mixture is a mixture composed of the ester, the styrene monomer, and optionally other monomers.
In addition, when using a polystyrene-type resin particle for a seed particle, the quantity of a seed particle is also contained in content of the component derived from a styrene-type monomer.

(1) Polystyrene resin particles (seed particles)
The styrene monomer is not particularly limited, and any known styrene or styrene derivative can be used. Examples of the styrene derivative include α-methyl styrene, vinyl toluene, chlorostyrene, ethyl styrene, i-propyl styrene, dimethyl styrene, bromostyrene, and the like. These styrenic monomers may be used alone or in combination.

A vinyl monomer copolymerizable with the styrene monomer may be used in combination. Examples of the vinyl monomer include divinylbenzene such as o-divinylbenzene, m-divinylbenzene and p-divinylbenzene, alkylene glycol di (meth) acrylate such as ethylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylate. Multifunctional monomers such as (meth) acrylate; α-methylstyrene, (meth) acrylonitrile, methyl (meth) acrylate and the like. These other monomers may be used alone or in combination.
When other monomers are used, the amount of other monomers used is the amount by which the styrenic monomer is the main component with respect to the sum of the other monomers (for example, 50% by weight). Or more).

Of the other monomers, a polyfunctional monomer is preferable from the viewpoint of improving the appearance of the foamed molded product. As the polyfunctional monomer, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate (repetition number of ethylene glycol is 4 to 16), and divinylbenzene are more preferable, and divinylbenzene, ethylene glycol di (meth) ) Acrylate is particularly preferred.
In addition, a part of or all of the seed particles may be a polystyrene resin recovered product.

The average particle diameter of the seed particles can be appropriately adjusted according to the average particle diameter of the expandable polystyrene resin particles to be produced. For example, the average particle diameter of the seed particles can be 40 to 70% of the average particle diameter of the expandable polystyrene resin particles. Specifically, when producing expandable polystyrene resin particles having an average particle diameter of 1.0 mm, it is preferable to use seed particles having an average particle diameter of about 0.4 to 0.7 mm.
The weight average molecular weight of the seed particles is not particularly limited, but is preferably 150,000 to 700,000, more preferably 200,000 to 500,000.

The seed particles are not particularly limited and can be produced by a known method. For example, a suspension polymerization method or a method in which a raw material resin is melt-kneaded with an extruder, extruded into a strand shape, and cut with a desired particle diameter can be mentioned.
The seed particles may be particles obtained by impregnating and polymerizing particles obtained by suspension polymerization or cutting with a styrene monomer in an aqueous medium. Examples of the aqueous medium include water and a mixed medium of water and a water-soluble solvent (for example, lower alcohol). The amount of the styrenic monomer used in this method can be in the range of 7.0 to 100.0 parts by weight with respect to 100 parts by weight of the particles. If the amount is less than 7.0 parts by weight, the heat resistance during molding may decrease, and if it exceeds 100.0 parts by weight, the foaming property may decrease.

Examples of the styrenic monomer include styrene and styrene derivatives. Examples of the styrene derivative include α-methyl styrene, vinyl toluene, chlorostyrene, ethyl styrene, i-propyl styrene, dimethyl styrene, bromostyrene, and the like. Of these, styrene is preferred.
The polymerization of the styrene monomer can be performed, for example, by heating at 60 to 150 ° C. for 2 to 20 hours.

  Styrene monomers are usually polymerized in the presence of a polymerization initiator. The polymerization initiator is usually impregnated into particles obtained by a suspension polymerization method or a cutting method simultaneously with a styrene monomer. The polymerization initiator is not particularly limited as long as it is conventionally used for the polymerization of styrene monomers. 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 include azo compounds such as peroxide, azobisisobutyronitrile, azobisdimethylvaleronitrile, and the like to reduce residual monomers by adjusting the Z average molecular weight Mz and weight average molecular weight Mw of the resulting polystyrene resin. And decomposition to obtain a half-life of 10 hours Degrees it is preferable to use a different two or more polymerization initiators in the 80 to 120 ° C.. In addition, a polymerization initiator may be used independently or may be used together 2 or more types. The usage-amount of a polymerization initiator is the range of 0.01-2.00 weight part with respect to 100 weight part of styrene-type monomers, for example.

  In addition, suspension stabilizers may be used to disperse styrenic monomer droplets and seed particles in an aqueous medium. The suspension stabilizer is not particularly limited as long as it is conventionally used for suspension polymerization of a styrene monomer. 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 and magnesium pyrophosphate. The usage-amount of a suspension stabilizer is the range of 0.1-5.0 weight part with respect to 100 weight part of seed particles.

  And when using a sparingly soluble inorganic compound as a suspension stabilizer, it is preferable to use an anionic surfactant together. Examples of such anionic surfactants include fatty acid soaps, N-acyl amino acids or salts thereof, carboxylates such as alkyl ether carboxylates, alkylbenzene sulfonates, alkyl naphthalene sulfonates, and dialkyl sulfosuccinates. Sulfonates such as alkyl sulfoacetates and α-olefin sulfonates; sulfates such as higher alcohol sulfates, secondary higher alcohol sulfates, alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, etc. Salt: Phosphate ester salts such as alkyl ether phosphate ester salts and alkyl phosphate ester salts. The usage-amount of surfactant is the range of 0.5-20.0 weight part with respect to 100 weight part of suspension stabilizers, for example.

(2) Absorption / polymerization process of monomer mixture In an aqueous medium, the monomer mixture is absorbed by the seed particles. The polymerization of the monomer mixture may be performed after the monomer mixture is absorbed, or may be performed while the monomer mixture is absorbed. Polystyrene resin particles are obtained by polymerization.
Examples of the aqueous medium include water and a mixed medium of water and a water-soluble solvent (for example, lower alcohol). Moreover, you may use a polymerization initiator, a suspension stabilizer, and surfactant similarly to the said item (1). The polymerization of the monomer mixture can also be performed under the same conditions as in item (1) above.

(3) Impregnation process of a volatile foaming agent The foamable polystyrene resin particles are obtained by impregnating the polystyrene resin particles with a volatile foaming agent. The impregnation with the volatile foaming agent may be performed after polymerization or may be performed while polymerization.
Impregnation can be performed by a method known per se. For example, the impregnation during the polymerization can be performed by performing the polymerization reaction in a closed container and press-fitting a volatile foaming agent into the container. The impregnation after the completion of the polymerization is performed by press-fitting a volatile foaming agent in a closed container.

  In addition, if the temperature at which the polystyrene resin particles are impregnated with the foaming agent and the foaming aid is low, the time required for impregnating the polystyrene resin particles with the foaming agent and the foaming aid becomes long and the production efficiency is increased. When it is too high, polystyrene resin particles may be fused together to form a bonded particle. Therefore, 60 to 120 ° C. is preferable, and 70 to 100 ° C. is more preferable.

(Pre-expanded particles and foamed molded product)
Furthermore, expandable polystyrene resin particles can be made into pre-expanded particles by pre-expanding them to a predetermined bulk density (for example, 10 to 300 kg / m ³ ) by a known method.
Furthermore, pre-expanded particles are filled in a mold of a foam molding machine, and heated again to foam the pre-expanded particles while thermally fusing the expanded particles to obtain a foam-molded article having excellent heat resistance. be able to.

Water vapor is preferably used as the heating medium. The density of the foamed molded product is preferably 10 to 300 kg / m ³ . If the density is lower than 10 kg / m ³ , sufficient strength may not be obtained. When the density is higher than 300 kg / m ³ , the weight cannot be reduced, and the elasticity, which is one of the characteristics of the polyethylene resin foam molded article, may not be sufficiently exhibited. Furthermore, when used as a heat insulating material, 14 to 33 kg / m ³ is preferable.

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 weight unless otherwise specified.
In the following examples and comparative examples, the average particle diameter, absorbance ratio, foamability, heat-fusibility, heat resistance, and comprehensive evaluation of expandable polystyrene resin particles were measured and evaluated by the following measurement methods and evaluation criteria. .

<Measurement method of average particle diameter>
About 50 g of a sample was sieved using a low-tap type sieve shaker (manufactured by Iida Seisakusho Co., Ltd.) 3.35 mm, 2.80 mm, 2.36 mm, 2.00 mm, 1.70 mm, 1.40 mm, 1.18 mm , 1.00mm, 0.85mm, 0.71mm, 0.60mm, 0.50mm, 0.425mm, 0.355mm, 0.300mm, 0.250mm, 0.212mm, 0.180mm JIS standard sieve 5 Classify for a minute. The sample weight on the sieve mesh is measured, and the particle diameter (median diameter) at which the cumulative weight is 50% is determined as the average particle diameter based on the cumulative weight distribution curve obtained from the result.

<Absorbance ratio>
(1) The absorbance ratio X (D1730 / D1600) of the particle surface layer is measured in the following manner.
That is, the surface of 10 resin particles selected at random is subjected to particle surface layer analysis by ATR infrared spectroscopy to obtain an infrared absorption spectrum. In this analysis, an infrared absorption spectrum ranging from the particle surface to a depth of several μm is obtained.
The absorbance ratio (D1730 / D1600) is calculated from each infrared absorption spectrum, and the arithmetic average of the absorbance ratios calculated for the surface is defined as the absorbance ratio X.
The absorbances D1730 and D1600 are measured using a measuring device sold by Nicolet under the trade name “Fourier Transform Infrared Spectrometer MAGMA 560”.

The absorbance D1600 at 1600 cm ⁻¹ obtained from the infrared absorption spectrum refers to the height of a peak appearing in the vicinity of 1600 cm ⁻¹ derived from the in-plane vibration of the benzene ring contained in the polystyrene resin.
Further, the absorbance D1730 at 1730 cm ⁻¹ obtained from the infrared absorption spectrum refers to the height of a peak appearing in the vicinity of 1730 cm ⁻¹ derived from the stretching vibration between C═O of the ester group contained in the acrylate ester.

(2) The absorbance ratio Y (D1730 / D1600) at the center of the particle is measured as follows.
That is, for a particle slice sample cut through the centers of 10 resin particles selected at random, an absorbance ratio image of the infrared absorption spectrum of the entire particle slice sample is obtained by cross-sectional mapping measurement by microscopic IR imaging.
Absorbance ratios (D1730 / D1600) are calculated by extracting the absorbances D1730 and D1600 at the center from each infrared absorption spectrum. The arithmetic mean of the calculated absorbance ratio is defined as the absorbance ratio Y. The central part means a region within a radius of 30% from the center in the particle slice sample including the center of the particle.
Absorbances D1730 and D1600 were obtained by imaging the cross section of the particles using an apparatus sold under the trade name “High-speed IR Imaging System Spectrum Spotlight 300” from Perkin Elmer, and observed at the center of the particles in this imaging diagram. Obtained from the obtained infrared absorption spectrum.

<Foaming properties>
5 g of resin particles are heated with 0.02 MPa steam for 3 minutes, and the volume of the foamed particles obtained is measured with a graduated cylinder. The value obtained by dividing the measured bulk volume by the particle weight is defined as the bulk multiple of the expanded particles. If this bulk multiple is less than the desired expansion factor, foam particles with the desired expansion factor cannot be obtained, or it takes time to foam, the foaming agent inside the particles is insufficient during molding, and the appearance and fusion of the molded product Wear may worsen.
In this embodiment, 40 times or more is “◯”, and less than “×”.

<Heat sealability>
A plate-like foamed molded product having a length of 300 mm, a width of 400 mm, and a height of 30 mm is dried for 24 hours and then broken in half at the center in the length direction. With respect to the expanded particles on the fracture surface, the number (a) of particles broken in the particles and the number (b) of particles broken at the interface between the particles in an arbitrary range of 100 to 150 are counted. A value obtained by substituting the obtained numerical value into the formula [(a) / ((a) + (b))] × 100 is defined as a fusion rate (%).
Evaluation criteria are evaluated as good (◯) when the fusion rate is 70% or more and poor (×) when it is less than 70%.

<Heat resistance>
A test piece having a rectangular parallelepiped shape having a length of 120 mm, a width of 120 mm, and a height of 30 mm is cut out from the foam molded article. About this test piece, the heating dimensional change rate after leaving to stand at 90 degreeC for 168 hours is measured based on JISK6767: 1999 (dimensional stability at the time of high temperature: B method). In addition, the case where the heating dimensional change rate is within ± 1.0% is indicated as “◯”, and the case where the heating dimensional change rate is less than −1.0% or higher than 1.0% is indicated as “X”. .

<Comprehensive evaluation>
If there is at least one “×” in the evaluation of foamability, heat-fusibility and heat resistance, the overall evaluation is “×”, and if there is no “×”, the overall evaluation is “○”. To do.

Example 1
(Manufacture of seed particles)
Into a polymerization vessel equipped with a stirrer having a capacity of 100 liters, 40000 g of water, 100 g of calcium triphosphate as a suspension stabilizer and 2.0 g of calcium dodecylbenzenesulfonate as an anionic surfactant are stirred, and 40000 g of styrene and a polymerization initiator are stirred. After adding 96.0 g of benzoyl peroxide and 28.0 g of t-butylperoxybenzoate, the temperature was raised to 90 ° C. for polymerization. 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 polystyrene-type resin particle (a).
The polystyrene resin particles (a) were sieved to obtain polystyrene resin particles (b) having a particle diameter of 0.5 to 0.71 mm as seed particles.
Next, in a polymerization vessel equipped with a stirrer having an internal capacity of 5 liters, 2000 g of water, 500 g (100 parts by weight) of the polystyrene resin particles (b), 6.0 g of magnesium pyrophosphate as a suspension stabilizer and an anionic surfactant 0.3 g of calcium dodecylbenzenesulfonate was supplied and heated to 72 ° C. while stirring.

(First polymerization step)
Next, 4.5 g of benzoyl peroxide and 1.1 g of t-butylperoxybenzoate as a polymerization initiator dissolved in 210 g (42 parts by weight) of styrene were supplied to the 5 liter polymerization vessel, and then 72 The reaction solution was obtained by holding at 60 ° C. for 60 minutes.

(Second polymerization step)
After 60 minutes, the reaction solution was heated to 110 ° C. over 150 minutes, and a mixed monomer of styrene 1190 g (218 parts by weight) and isobornyl methacrylate 200 g (40 parts by weight) was pumped into the polymerization vessel in 150 minutes. A fixed amount was supplied. Subsequently, it heated up at 120 degreeC and cooled after 2 hours progress, and the polystyrene-type resin particle (c) was obtained.

(Volatile foaming agent impregnation)
Subsequently, 2200 g of water, 1800 g of polystyrene-based resin particles (C), 6.0 g of magnesium pyrophosphate and 0.4 g of calcium dodecylbenzenesulfonate are supplied as suspension stabilizers to another polymerization vessel with a stirrer having an internal volume of 5 liters. The temperature was raised to 70 ° C. with stirring. Next, 9.0 g of cyclohexane as a foaming aid was placed in a polymerization vessel, sealed and heated to 100 ° C. Next, 144 g of n-butane as a volatile foaming agent was pressed into a polymerization vessel containing polystyrene resin particles (C) and held for 3 hours to obtain expandable polystyrene resin particles. After holding, the flask was cooled to 30 ° C. or lower, and the expandable polystyrene resin particles were taken out from the polymerization container, dried, and left in a thermostatic chamber at 13 ° C. for 5 days.
The mapping image of the obtained expandable polystyrene resin particles is shown in FIG. 1, the relationship between the distance from the particle center, the absorbances D1720 and D1601, and the absorbance ratio is shown in Table 1, and the relationship between the distance from the particle center and the absorbance ratio. Is shown in FIG.

  1 and 2 and Table 1, it can be seen that the expandable polystyrene resin particles are rich in isobornyl methacrylate-derived components in the surface layer. In FIG. 1, the absorbance ratio decreases from the surface layer toward the center, and is color-coded.

(Pre-foaming)
Subsequently, the surface of the expandable polystyrene resin particles was coated with a surface treatment agent composed of zinc stearate and hydroxystearic acid triglyceride. After the treatment, the expandable polystyrene resin particles were foamed to a bulk density of 0.02 g / cm ³ using a pre-foaming apparatus, and then aged at 20 ° C. for 24 hours to obtain pre-foamed particles.

(Manufacture of foam moldings)
Pre-expanded particles were filled into the cavities of a foam bead automatic molding machine (trade name “ACE 3 type” manufactured by Sekisui Koki Co., Ltd.) equipped with a mold having a rectangular parallelepiped cavity with an inner dimension of 300 mm × 400 mm × 30 mm. After filling, the pre-expanded particles were subjected to thermoforming with water vapor having a gauge pressure of 0.07 Mpa for 15 seconds. Next, the foam in the cavity was water-cooled for 5 seconds and then allowed to cool under reduced pressure (cooling step) to obtain a foam-molded product.

Example 2
In the same manner as in Example 1 except that the amount of styrene monomer in the second polymerization step is 238 parts by weight and the amount of methacrylic acid ester is 20 parts by weight, expandable styrene resin particles, pre-expanded particles and A foamed molded product was obtained.
Example 3
In the same manner as in Example 1 except that the amount of styrene monomer in the second polymerization step is 178 parts by weight and the amount of methacrylic acid ester is 80 parts by weight, expandable styrene resin particles, pre-expanded particles and A foamed molded product was obtained.
Example 4
In the same manner as in Example 1 except that the amount of styrene monomer in the second polymerization step is 246 parts by weight and the amount of methacrylic acid ester is 12 parts by weight, expandable styrene resin particles, pre-expanded particles and A foamed molded product was obtained.

Example 5
(Manufacture of seed particles)
In the same manner as in Example 1, polystyrene resin particles (b) having a particle diameter of 0.5 to 0.71 mm were obtained.
Next, in a polymerization vessel equipped with a stirrer having an internal volume of 5 liters, 2000 g of water, 500 g of the polystyrene resin particles (b), 6.0 g of magnesium pyrophosphate as a suspension stabilizer and calcium dodecylbenzenesulfonate as an anionic surfactant. 0.3g was supplied and it heated up at 90 degreeC, stirring.

(Polymerization process)
Next, as a polymerization initiator, 4.5 g of benzoyl peroxide and 1.1 g of t-butylperoxybenzoate were dissolved in a mixed monomer of 1300 g (260 parts by weight) of styrene and 200 g (40 parts by weight) of isobornyl methacrylate. Was supplied to the 5-liter polymerization vessel by a constant amount in 210 minutes. After the supply, the temperature was further maintained at 90 ° C. for 90 minutes, and then the temperature was raised to 120 ° C. and cooled after 2 hours to obtain polystyrene resin particles (c).
In Example 1, styrene was polymerized in two stages (two-stage method), but in this example, styrene was polymerized in one stage (one-stage method).

(Volatile foaming agent impregnation)
In the same manner as in Example 1, expandable polystyrene resin particles were obtained by impregnating with a volatile foaming agent.
(Pre-foaming)
Subsequently, in the same manner as in Example 1, after coating, pre-foamed to a bulk density of 0.02 g / cm ³ with a pre-foaming apparatus, and then aged at 20 ° C. for 24 hours to obtain pre-foamed particles.
(Manufacture of foam moldings)
A foamed molded article was obtained from the pre-expanded particles obtained in the same manner as in Example 1.

Example 6
Expandable styrenic resin particles, pre-expanded particles, and expanded molded articles were obtained in the same manner as in Example 1 except that isobornyl methacrylate was changed to adamantyl methacrylate.
Example 7
Except that 42 parts by weight of styrene in the first polymerization step is a mixture of 20 parts by weight of styrene and 50 parts by weight of isobornyl methacrylate, 170 parts by weight of styrene in the second polymerization step and 60 parts by weight of isobornyl methacrylate. In the same manner as in Example 1, expandable styrenic resin particles, pre-expanded particles, and a foam-molded product were obtained.
Example 8
In the same manner as in Example 1 except that 42 parts by weight of styrene in the first polymerization step is a mixture of 22 parts by weight of styrene and 20 parts by weight of isobornyl methacrylate, expandable styrene resin particles, pre-expanded particles, and foam A molded body was obtained.

Comparative Example 1
In the same manner as in Example 1 except that the amount of styrene monomer in the second polymerization step is 138 parts by weight and the amount of methacrylic acid ester is 120 parts by weight, expandable styrene resin particles and pre-expanded particles are prepared. Obtained. Although an attempt was made to obtain a foamed molded article using the pre-expanded particles, a foamed molded article that had low fusion properties between the particles and could be evaluated for heat resistance could not be obtained.
Comparative Example 2
In the same manner as in Example 1 except that the amount of styrene monomer in the second polymerization step is 254 parts by weight and the amount of methacrylic acid ester is 4 parts by weight, expandable styrene resin particles, pre-expanded particles and A foamed molded product was obtained.

Comparative Example 3
Except that 42 parts by weight of styrene in the first polymerization step is a mixture of 10 parts by weight of styrene and 80 parts by weight of isobornyl methacrylate, 120 parts by weight of styrene in the second polymerization step and 90 parts by weight of isobornyl methacrylate. In the same manner as in Example 1, expandable styrenic resin particles, pre-expanded particles, and a foam-molded product were obtained.
Table 2 shows the results of evaluation of the absorbance ratio of the expandable styrene resin particles of Examples 1 to 8 and Comparative Examples 1 to 3, the foamability of the foamed molded product, the heat fusion property, and the heat resistance. In Table 2, the isobornyl methacrylate content in Example 6 means the adamantyl methacrylate content.

  From Table 2, the foamed molded products of Examples 1 to 8 had no shrinkage and had good heat-fusibility. In Comparative Examples 1 and 3 in which the amount of isobornyl methacrylate added is large, a foamed molded article having sufficient foamability, heat-fusibility and heat resistance cannot be obtained, and in Comparative Example 2 with a small amount of addition, sufficient A foamed molded product having heat resistance could not be obtained. In Comparative Example 3, since the amount of isobornyl methacrylate present in the surface layer and the center portion also increased, the desired expansion ratio could not be obtained.

Claims (4)

A thermal insulation box as an insulation material
A resin containing a component derived from an ester of a polycyclic terpenol having 10 to 20 carbon atoms and methacrylic acid and a component derived from a styrene monomer, and a volatile foaming agent,
(1) More than 1 part by weight and less than 30 parts by weight of the resin derived from the ester with respect to a total of 100 parts by weight of the component derived from the ester and the component derived from the styrene monomer Including
(2) having a surface layer with an absorbance ratio X (D1730 / D1600) in the range of 0.35 to 6.00 (D1730 and D1600 are the absorbance at 1730 cm ⁻¹ in the infrared absorption spectrum by infrared spectroscopic analysis; Means absorbance at 1600 cm ⁻¹ ),
(3) A heat retaining box comprising a foamed molded product of expandable polystyrene resin particles having a central portion with an absorbance ratio Y (D1730 / D1600) smaller than the absorbance ratio X.   The component derived from the ester is a component derived from a monomer selected from isobornyl methacrylate, bornyl methacrylate, norbornyl methacrylate, adamantyl methacrylate, and lower alkyl substituted products thereof. Heat insulation box as described in   The heat retention box according to claim 1 or 2, wherein the absorbance ratio Y is in a range of 0 to 4.0. It is a manufacturing method of the heat insulation box as described in any one of Claims 1-3,
A step of allowing a seed particle to absorb a monomer mixture containing an ester of the C10-20 polycyclic terpenol and methacrylic acid and a styrenic monomer in an aqueous medium;
A step of obtaining polystyrene resin particles by polymerizing the monomer mixture after absorbing or absorbing; and
A step of impregnating a polystyrene resin particle with a volatile foaming agent after polymerization or while polymerizing to obtain expandable polystyrene resin particles;
And a step of pre-foaming expandable polystyrene resin particles, followed by foam molding.