JP2012077115A - Heat insulator and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat insulator made of a polystyrene resin foam-molded body which has excellent heat insulating performance, and further has excellent mechanical strength such as bending strength, compressive strength and impact resistance and excellent heat insulating properties as well, and to provide a method for producing the heat insulator.SOLUTION: The heat insulator is composed of a polystyrene resin foam-molded body obtained by: filling polystyrene resin pre-foaming particles obtained by heating foaming polystyrene resin particles including a foaming agent into polystyrene resin particles; heating the pre-foaming particles; and subjecting the pre-foaming particles to foaming molding in a die. In a state of the pre-foaming particles obtained by heating the foaming polystyrene resin particles and foaming it to 50 times of bulk foam ratio, the inner part has an average cell diameter of 35 to 140 μm, the value of the surface-layer-part average cell diameter to the inner-part average cell diameter is 0.80 to 1.20, and the open cell ratio is 10% or less.

Description

  The present invention relates to a heat insulating material made of a polystyrene-based resin foam molded article that is excellent in heat insulating performance and mechanical strength such as bending strength, compressive strength, and impact resistance, and a method for producing the same.

  Polystyrene resin foam molded products obtained by foaming foamable polystyrene resin particles are excellent in heat insulation, compression resistance, light weight, economy, etc., food cold storage containers, residential insulation, coolers Widely used as a heat insulating material for boxes.

As one of the methods for producing expandable polystyrene resin particles, a foaming agent is press-fitted and kneaded into polystyrene resin melted in an extruder, and a small hole in a die provided with a foaming agent-containing molten resin at the tip of the extruder A so-called melt extrusion method in which extrudates are extruded directly into a cooling liquid from the same time, and at the same time the extrudate is cut with a high-speed rotary blade, and the extrudate is cooled and solidified by contact with the liquid to obtain expandable polystyrene resin particles. Are known.
Conventionally, for example, techniques disclosed in Patent Documents 1 to 3 have been proposed regarding methods for producing expandable polystyrene resin particles by a melt extrusion method.

  In Patent Document 1, (a) a step of extruding a foaming agent-containing polymer through a die head part into a water bath or a fluid bath maintained at a high temperature equal to or higher than the Tg value of the foamable polymer (b) In a water bath or fluid bath maintained at a high temperature equal to or higher than the Tg value, the polymer is immediately cut at the outlet of the die head to form granules. (C) The granules are cooled to a temperature not higher than the Tg value of the foamable polymer. In a continuous process, the cooling of the granules is slow cooling at a rate of less than 3 ° C. per minute from at least (Tg + 5) ° C. to (Tg−5) ° C., and the cutting of the polymer into granules and the cooling of the granules is 2 bar An extrusion-type production method of foamable granules of a non-oriented and stress-free thermoplastic styrene polymer, which is performed under the above pressure, is disclosed.

  In Patent Document 2, a thermoplastic resin and a foaming agent are melt-kneaded, and then this is heated and pressurized at a glass transition temperature (hereinafter abbreviated as Tg) of the foamable thermoplastic resin particles from the extrusion hole of the die head + 5 ° C or higher. A foamable thermoplastic resin, characterized in that particles obtained by extruding into a liquid and immediately cutting are maintained at the same temperature or higher in a heated and pressurized liquid to relieve residual stress in the particles, and then cooled. A method for making particles is disclosed.

  In Patent Document 3, a thermoplastic resin (A) and a foaming agent (B) are melt-kneaded (step 1), and the thermoplastic resin (A) and the foaming agent (B) are added from the extrusion hole of the die head. After being extruded into a heated and pressurized liquid heated and pressurized to a temperature and pressure at which the melt-kneaded product is not foamed, it is immediately cut (step 2), and the resulting particles are cooled to a temperature at which normal pressure does not cause foaming ( Step 3) When the foamable thermoplastic resin is measured with a differential thermal analyzer (DSC), of the two endothermic peaks appearing in the region of 40 to 120 ° C., the peak temperature on the low temperature side is T1 There is disclosed a process for producing expandable thermoplastic resin particles characterized by aging treatment in a normal pressure liquid heated to a temperature range of 30 to (T1 + 15) ° C. (Step 4).

Japanese Patent Publication No. 5-59138 JP-A-6-32932 JP 7-314438 A

However, the prior art has the following problems.
In the production method of Patent Document 1, when the resin extruded from the die head part is cut into granules, the resin is extruded and cut in a heated and pressurized liquid maintained at a high temperature equal to or higher than the Tg value of the foamable polymer. Therefore, there is a problem that the particles obtained by cutting are easily fused together, and there is a high incidence of defective products in which a large number of particles are bonded together to form a lump.

  In the production method of Patent Document 2, particles obtained by immediate cutting are maintained at the same temperature or higher in a heated and pressurized liquid to relieve residual stress in the particles, and then cooled to obtain expandable thermoplastic resin particles. Although it is manufactured, when foamable thermoplastic resin particles are manufactured under the manufacturing conditions described in the example of Patent Document 2, the particles obtained by cutting are easily fused, and a large number of particles are bonded together. There is a problem that the incidence of defective products that are combined into a lump is high. In addition, when the expandable polystyrene resin particles obtained by this production method were heated and pre-expanded, the resulting pre-expanded resin particles had a large average cell diameter, and the pre-expanded particles were subjected to in-mold foam molding. There was a problem that the mechanical strength of the foamed molded product thus obtained was lowered.

  The production method of Patent Document 3 is a method for obtaining pre-expanded particles having a large cell diameter. However, when the cell diameter in the cell structure of the pre-expanded particles is increased, there is a problem that the mechanical strength of the foam-molded product obtained by foam-molding the pre-expanded particles is lowered.

  The present invention has been made in view of the above circumstances, and has excellent heat insulation performance as well as heat insulation material made of a polystyrene-based resin foam molded article excellent in mechanical strength such as bending strength, compressive strength, and impact resistance, and a method for producing the same. The issue is to provide

  In order to achieve the above object, the present invention fills polystyrene resin pre-expanded particles obtained by heating expandable polystyrene resin particles containing a foaming agent in polystyrene resin particles into a mold cavity and heats them. In the heat insulating material comprising a polystyrene-based resin foam molded article obtained by in-mold foam molding, in the state of pre-expanded particles in which the expandable polystyrene-based resin particles are heated and expanded to a bulk expansion ratio of 50 times, The internal average bubble diameter is in the range of 35 to 140 μm, the value of the surface layer part average bubble diameter / internal average bubble diameter is in the range of 0.80 to 1.20, and the open cell ratio is 10% or less. Provided is a heat insulating material having a bubble structure.

In the heat insulating material of the present invention, the internal average cell diameter D ₁ ′ of the pre-expanded particles when expanded to the bulk expansion ratio X times is expressed by the following formula (1).

(In the formula, D ₁ represents the internal average cell diameter (μm) of the expanded particles converted to a bulk expansion ratio of 50 times, and D ₁ ′ represents the internal average cell diameter of the expanded particles when expanded to a bulk expansion ratio X times) It is preferable that the internal average cell diameter D _{1 of} the pre-expanded particles converted to a bulk expansion ratio of 50 times using (representing (μm)) satisfies the relationship of 35 μm ≦ D ₁ ≦ 140 μm.

  The heat insulating material of this invention WHEREIN: It is preferable that the said internal average bubble diameter exists in the range of 40-120 micrometers.

  In the heat insulating material of the present invention, the open cell ratio is preferably 8% or less.

  In the heat insulating material of the present invention, the surface layer part average bubble diameter / internal average bubble diameter value is preferably in the range of 0.90 to 1.10.

  The heat insulating material of the present invention preferably contains 5.0 parts by mass or less of an inorganic cell nucleating agent with respect to 100 parts by mass of the polystyrene resin.

  In the heat insulating material of the present invention, the inorganic cell nucleating agent is preferably talc.

The present invention also relates to a heat insulating material comprising a styrene resin foam molded article obtained by filling pre-expanded particles of styrene resin into a cavity of a mold, steam-heating the mold, and foam-molding in the mold. ,
In the state when foaming is performed at the expansion ratio X times, the internal average cell diameter D ₂ ′ of the foam particles fused together in the foamed molded product is expressed by the following formula (2):

(Wherein, D ₂ represents the average internal cell diameter of the expanded beads of foamed molded body in terms of 50-fold expansion ratio ([mu] m), D 2 _'is in the foamed molded product when foamed in expansion ratio X times the average internal cell diameter average internal cell diameter D ₂ of the expanded beads of foamed molded body in terms of expansion ratio 50 times using a representative of the ([mu] m)) is, satisfies the relationship of 35 [mu] m ≦ D ₂ ≦ 140 .mu.m of the foamed particles The foamed particles have a cell structure in which the value of the surface layer part average cell diameter / internal average cell diameter is in the range of 0.80 to 1.20, and the foamed molded product has an open cell ratio of 10% or less. A heat insulating material characterized by the above is provided.

Further, the present invention adds a foaming agent to a polystyrene resin in a resin supply device, kneads, and glass transition of expandable polystyrene resin particles from a small hole of a die attached to the tip of the resin supply device with a foaming agent-containing molten resin. Extruding into a cooling liquid having a temperature lower than Tg, cutting the extrudate at the same time as extruding, and cooling and solidifying the extrudate by contact with the liquid to obtain expandable polystyrene resin particles;
A step of obtaining the expandable polystyrene resin particles by subjecting the obtained expandable polystyrene resin particles to a heat treatment at a temperature of (glass transition temperature Tg-5 of the expandable polystyrene resin particles) ° C. or higher;
Then heated resulting expandable polystyrene resin particles, wherein the formula (1) is the average internal cell diameter D ₁ of the pre-expanded particles in terms of 50-fold volume expansion ratio by using, in the range of 35~140μm Yes, a polystyrene resin pre-expanded particle having a cell structure in which the value of the average cell diameter of the surface layer / the average cell diameter of the internal layer is in the range of 0.80 to 1.20 and the open cell ratio is 10% or less is prepared. The process of
Then, filling the polystyrene resin pre-expanded particles in a cavity of a mold, heating, and foam-molding in the mold to obtain a heat insulating material, a method for manufacturing a heat insulating material.

  In the manufacturing method of the heat insulating material of this invention, it is preferable that the temperature of the cooling liquid at the time of cut | disconnecting the said extrudate is in the range of 20-60 degreeC.

  In the manufacturing method of the heat insulating material of this invention, it is preferable to add an inorganic cell nucleating agent of 5.0 mass parts or less with respect to 100 mass parts of polystyrene resins.

  In the method for producing a heat insulating material of the present invention, the inorganic cell nucleating agent is preferably talc.

  The heat insulating material of the present invention is a state of pre-expanded particles obtained by heating expandable polystyrene resin particles to be expanded to a bulk expansion ratio of 50 times, and the internal average cell diameter is in the range of 35 to 140 μm, and the surface layer part average Obtained by in-mold foam molding of pre-expanded particles having a cell structure in which the value of cell diameter / internal average cell size is in the range of 0.80 to 1.20 and the open cell ratio is 10% or less. As a result, relatively small, uniform and independent bubbles are formed throughout the foam particles, and the foam molded product obtained by in-mold foam molding has excellent mechanical strength such as bending strength, compressive strength, and impact resistance. It will be a thing.

In the heat insulating material of the present invention, the internal average cell diameter D ₂ ′ of the foamed particles fused together in the foamed molded product in the state where the foaming molding is multiplied by X times is used by the above formula (2). Te average internal cell diameter D ₂ of the expanded beads of foamed molded body in terms of expansion ratio 50 times, satisfies the relationship of 35 [mu] m ≦ D ₂ ≦ 140 .mu.m, the surface layer portion average cell diameter / internal average cell diameter of the expanded particles Since the value is within the range of 0.80 to 1.20 and the foamed molded body has a cell structure in which the open cell ratio is 10% or less, relatively small, uniform and independent cells are formed throughout the heat insulating material. Therefore, it is excellent in mechanical strength such as bending strength, compressive strength, and impact resistance.

  In the method for producing a heat insulating material of the present invention, expandable polystyrene resin particles obtained by a melt extrusion method are subjected to heat treatment at a temperature of (glass transition temperature Tg-5 of expandable polystyrene resin particles) ° C. or higher. By obtaining expandable polystyrene resin particles, relatively small, uniform and independent bubbles are formed throughout the expanded particles when heated and foamed, and bending strength, compressive strength, and impact resistance are achieved by in-mold foam molding. It is possible to obtain a heat insulating material excellent in mechanical strength such as property.

It is a block diagram which shows an example of the manufacturing apparatus used for the manufacturing method of the heat insulating material of this invention.

(Insulation material)
The heat insulating material of the present invention fills and heats the polystyrene resin pre-expanded particles obtained by heating the expandable polystyrene resin particles containing a foaming agent in the polystyrene resin particles in the mold cavity. In a heat insulating material comprising a polystyrene-based resin foam molded article obtained by foam molding, in the state of pre-expanded particles obtained by heating the expandable polystyrene-based resin particles and foaming to a bulk foam multiple of 50 times, the internal average cell diameter Is in the range of 35 to 140 μm, the surface layer part average bubble diameter / internal average bubble diameter is in the range of 0.80 to 1.20, and the open cell ratio is 10% or less. It is characterized by that. In addition, the bulk foaming factor of the said pre-expanded particle means the bulk foaming factor measured by the measuring method of the bulk foaming factor of the polystyrene-type resin pre-expanded particle mentioned later.

In the expandable polystyrene resin particles, when the bulk expansion ratio of the pre-expanded particles heated and expanded is other than 50 times, the internal average cell diameter D ₁ ′ of the pre-expanded particles is expressed by the formula (1). It is preferable that the average foam cell diameter D ₁ satisfies the relationship of 35 μm ≦ D ₁ ≦ 140 μm. The same applies to the cell structure of a heat insulating material made of a polystyrene resin foam molded body obtained by in-mold foam molding of the pre-expanded particles.

  The expandable polystyrene resin particles are in the form of expanded particles that are heated and expanded to a bulk expansion ratio of 50 times, and have an internal average cell diameter in the range of 35 to 140 μm and in the range of 40 to 120 μm. When the internal average cell diameter is less than 35 μm, the polystyrene-based resin foam molded article obtained by in-mold foam molding increases the open cell ratio and decreases closed cells, bending strength, compressive strength, impact resistance, etc. The mechanical strength of this will decrease. When the internal average bubble diameter exceeds 140 μm, mechanical strength such as bending strength, compressive strength, and impact resistance is lowered.

  The expandable polystyrene resin particles are in the form of expanded particles heated to be expanded to a bulk expansion ratio of 50 times, and the value of the surface layer part average cell diameter / internal average cell diameter is in the range of 0.80 to 1.20. It is preferable that it is in the range of 0.90 to 1.10. When the value of the surface layer part average cell diameter / internal average cell diameter is out of the above range, the mechanical strength such as bending strength, compressive strength, and impact resistance of the polystyrene resin foam molded product obtained by in-mold foam molding is lowered. Resulting in. In the present invention, the “surface layer average cell diameter” is a state of pre-expanded particles in which expandable polystyrene resin particles are expanded to a bulk expansion ratio of 50 times, and the pre-expanded particles are cut through the center. In the cross section, a region where the depth from the surface of the pre-expanded particles is up to 1/4 of the diameter of the expanded particles is defined as “surface layer portion”, which means the average cell diameter of the bubbles in the surface layer portion, and The “inner average bubble diameter” is defined as “inner” in a region deeper than the surface layer portion of the same pre-expanded particle, and refers to the average bubble diameter of the bubbles inside.

  The expandable polystyrene resin particles are in the state of expanded particles heated to be expanded to a bulk expansion ratio of 50 times, and the open cell ratio is 10% or less, preferably 8% or less. If the open cell ratio exceeds 10%, the mechanical strength such as bending strength, compressive strength, impact resistance and the like of the heat insulating material obtained by in-mold foam molding will decrease.

  In the expandable polystyrene resin particles, the polystyrene resin is not particularly limited, and examples thereof include styrene, α-methylstyrene, vinyltoluene, chlorostyrene, ethylstyrene, i-propylstyrene, dimethylstyrene, bromostyrene, and the like. Examples include homopolymers of styrene monomers or copolymers thereof, and polystyrene resins containing 50% by mass or more of styrene are preferable, and polystyrene is more preferable.

  Further, the polystyrene resin may be a copolymer of the styrene monomer and a vinyl monomer copolymerizable with the styrene monomer, the main component of which is the styrene monomer. As, for example, alkyl (meth) acrylate such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate, (meth) acrylonitrile, dimethyl maleate, dimethyl fumarate, diethyl In addition to fumarate and ethyl fumarate, bifunctional monomers such as divinylbenzene and alkylene glycol dimethacrylate are exemplified.

  If a polystyrene resin is the main component, other resins may be added. Examples of the resin to be added include polybutadiene, styrene-butadiene copolymer to improve the impact resistance of the foam molded article. Examples thereof include rubber-modified polystyrene resins to which a diene rubbery polymer such as a polymer, ethylene-propylene-nonconjugated diene three-dimensional copolymer is added, so-called high impact polystyrene. Alternatively, a polyethylene resin, a polypropylene resin, an acrylic resin, an acrylonitrile-styrene copolymer, an acrylonitrile-butadiene-styrene copolymer, and the like can be given.

  As a polystyrene resin used as a raw material, a polystyrene resin (virgin polystyrene) that is not a recycled material, such as a commercially available ordinary polystyrene resin, a polystyrene resin newly produced by a method such as suspension polymerization, can be used. In addition, a recycled raw material obtained by regenerating a used polystyrene-based resin foam molded article can be used. As this recycled material, used polystyrene-based resin foam moldings such as fish boxes, heat insulating materials for household appliances, trays for food packaging, etc. are collected and recycled from the recycled materials recovered by the limonene dissolution method or heating volume reduction method. A raw material having a mass average molecular weight Mw in the range of 120,000 to 400,000 can be appropriately selected, or a plurality of recycled raw materials having different mass average molecular weights Mw can be used in appropriate combination.

The foaming agent used for the expandable polystyrene resin particles is not particularly limited. For example, aliphatic hydrocarbons such as propane, normal butane, isobutane, normal pentane, isopentane, neopentane, and cyclopentane, and ethers such as dimethyl ether and diethyl ether. , Various alcohols such as methanol and ethanol, carbon dioxide, nitrogen, water and the like can be used. Of these, aliphatic hydrocarbons are preferred, and normal butane, isobutane, normal pentane, isopentane alone or a mixture thereof is more preferred. Further, normal pentane, isopentane, neopentane, cyclopentane, cyclopentadiene alone or a mixture thereof, which is a hydrocarbon having 5 carbon atoms, is particularly suitable. Of these, a mixture of one or both of isopentane and normal pentane is preferable. Further, it mainly comprises the hydrocarbon having 5 carbon atoms and has a boiling point of 20 ° C. or higher, and may contain a blowing agent other than the hydrocarbon having 5 carbon atoms (for example, normal butane, isobutane, propane, carbon dioxide gas, etc.). .
The amount of the foaming agent added is preferably in the range of 2 to 15 parts by mass, more preferably in the range of 3 to 8 parts by mass, and particularly preferably in the range of 4 to 7 parts by mass with respect to 100 parts by mass of the polystyrene resin.

  To the expandable polystyrene resin particles, an inorganic fine powder or a chemical foaming agent such as talc, calcium silicate, synthetic or naturally produced silicon dioxide is added as a cell nucleating agent to 100 parts by mass of the polystyrene resin. It is preferable. As the bubble nucleating agent, talc is particularly preferable. The amount of the cell nucleating agent added is preferably 5 parts by mass or less, more preferably 0.05 to 2.0 parts by mass with respect to 100 parts by mass of the thermoplastic resin. Examples of the chemical foaming agent include azodicarbonamide, N, N′-dinitrosopentamethylenetetramine, 4,4′-oxybis (benzenesulfonylhydrazide), sodium hydrogen carbonate, and the like.

  As a preferred embodiment of the present invention, it is preferable to use a master batch type cell nucleating agent in which an inorganic powder such as talc or a chemical foaming agent is uniformly dispersed in a base resin, preferably a polystyrene resin, as the cell nucleating agent. . By using this master batch type cell nucleating agent, when mixing polystyrene resin and cell nucleating agent in the resin feeder, inorganic powder or chemical foaming agent is dispersed in polystyrene resin in a very uniform state. Can be made.

  In the expandable polystyrene resin particles, in addition to the foaming agent and the cell nucleating agent, in the range that does not impair the properties of the resulting expandable polystyrene resin particles and the foamed molded article, a binding inhibitor, a cell regulator, You may add additives, such as a crosslinking agent, a filler, a flame retardant, a flame retardant adjuvant, a lubricant, and a coloring agent.

  The heat insulating material of the present invention is a state of pre-expanded particles obtained by heating expandable polystyrene resin particles to be expanded to a bulk expansion ratio of 50 times, and the internal average cell diameter is in the range of 35 to 140 μm, and the surface layer part average Obtained by in-mold foam molding of pre-expanded particles having a cell structure in which the value of cell diameter / internal average cell size is in the range of 0.80 to 1.20 and the open cell ratio is 10% or less. As a result, relatively small, uniform and independent bubbles are formed throughout the foam particles, and the foam molded product obtained by in-mold foam molding has excellent mechanical strength such as bending strength, compressive strength, and impact resistance. It will be a thing.

(Insulation material manufacturing method)
Next, an embodiment of a method for manufacturing a heat insulating material according to the present invention will be described with reference to the drawings.
In the method for producing a heat insulating material according to the present invention, a foaming agent is added to and kneaded with a polystyrene-based resin in a resin supply device, and the foaming agent-containing molten resin is expanded from a small hole in a die attached to the tip of the resin supply device. Extruded into a cooling liquid having a temperature lower than the glass transition temperature Tg of the resin-based resin particles, and simultaneously extruding and cutting the extrudate, and cooling and solidifying the extrudate by contact with the liquid to obtain expandable polystyrene resin particles Grain process,
A reheating step of obtaining the expandable polystyrene resin particles by subjecting the obtained expandable polystyrene resin particles to a heat treatment at a temperature of (glass transition temperature Tg-5 of the expandable polystyrene resin particles) ° C. or higher.
Then heated resulting expandable polystyrene resin particles, wherein the formula (1) is the average internal cell diameter D ₁ of the pre-expanded particles in terms of 50-fold volume expansion ratio by using, in the range of 35~140μm Yes, a polystyrene resin pre-expanded particle having a cell structure in which the value of the average cell diameter of the surface layer / the average cell diameter of the internal layer is in the range of 0.80 to 1.20 and the open cell ratio is 10% or less is prepared. Pre-foaming process,
Next, the method includes a molding step of filling the polystyrene-based resin pre-expanded particles in a cavity of a molding die, heating the resultant, and foam-molding in the die to obtain a heat insulating material.

(Granulation process)
FIG. 1 is a configuration diagram showing an example of a production apparatus used for producing expandable polystyrene resin particles in the granulation step.
The manufacturing apparatus of this example includes an extruder 1 as a resin supply apparatus, a die 2 having a large number of small holes attached to the tip of the extruder 1, and a raw material supply hopper that inputs resin raw materials into the extruder 1. 3, a high-pressure pump 4 for press-fitting the foaming agent into the molten resin in the extruder 1 through the foaming agent supply port 5, and a resin discharge surface provided with a small hole in the die 2 so as to contact the cooling water. Cooling from the cutting chamber 7 into which the cooling water is circulated and supplied to the room, the cutter 6 rotatably provided in the cutting chamber 7 so as to cut the resin extruded from the small hole of the die 2, and the cutting chamber 7 A dehydrating dryer 10 with a solid-liquid separation function and a dehydrating dryer 10 with a solid-liquid separation function are obtained by separating foamable resin particles carried along with the flow of water from cooling water and dehydrating and drying to obtain expandable resin particles. The cooling water separated in A water tank 8, a high-pressure pump 9 for sending cooling water in the water tank 8 to the cutting chamber 7, and a storage container 11 for storing foamable resin particles dehydrated and dried by a dehydration dryer 10 with a solid-liquid separation function; It is configured with.

  As the extruder 1, either an extruder using a screw or an extruder not using a screw can be used. Examples of the extruder using a screw include a single-screw extruder, a multi-screw extruder, a vent-type extruder, and a tandem extruder. Examples of the extruder that does not use a screw include a plunger type extruder and a gear pump type extruder. Moreover, any extruder can use a static mixer. Among these extruders, an extruder using a screw is preferable from the viewpoint of productivity. Moreover, the conventionally well-known thing used in the granulation method by melt extrusion of resin can also be used for the cutting chamber 7 which accommodated the cutter 6. FIG.

  In order to produce expandable polystyrene resin particles using the production apparatus shown in FIG. 1, first, a desired additive such as a raw material polystyrene resin, a cell nucleating agent, and a flame retardant added if necessary is weighed. The raw material supply hopper 3 is then charged into the extruder 1. The raw polystyrene resin may be pelletized or granulated and mixed well in advance and then fed from one raw material supply hopper. For example, when multiple lots are used, the supply amount for each lot may be reduced. A plurality of adjusted raw material supply hoppers may be charged and mixed in an extruder. Also, when using a combination of recycled materials from multiple lots, mix the raw materials from multiple lots in advance and remove foreign matter using appropriate sorting methods such as magnetic sorting, sieving, specific gravity sorting, and air blowing sorting. It is preferable to keep it.

  After supplying polystyrene-based resin, bubble nucleating agent, and other optional additives into the extruder 1, the resin is heated and melted, and the molten resin is transferred to the die 2 side, and the high-pressure pump 4 is supplied from the blowing agent supply port 5. The foaming agent is pressed into the melted resin, and the foaming agent is mixed with the molten resin. Through the foreign matter removing screen provided in the extruder 1 as necessary, the melt is further kneaded and moved to the tip side, The added melt is extruded through a small hole in the die 2 attached to the tip of the extruder 1.

  The resin discharge surface in which the small holes of the die 2 are drilled is disposed in the cutting chamber 7 in which cooling water is circulated and supplied into the chamber, and the resin extruded from the small holes of the die 2 is placed in the cutting chamber 7. A cutter 6 is provided so as to be rotatable. When the melt with the blowing agent added is extruded through a small hole in the die 2 attached to the tip of the extruder 1, the melt is cut into granules and simultaneously cooled in contact with cooling water. can get.

  The obtained expandable polystyrene resin particles are transferred from the cutting chamber 7 to the flow of cooling water and carried to the dehydrating dryer 10 with a solid-liquid separation function, where the expandable polystyrene resin particles are separated from the cooling water. And dehydrated and dried. The dried expandable polystyrene resin particles are stored in the storage container 11.

  In the granulation step, the temperature of the cooling water is a temperature lower than the glass transition temperature Tg of the expandable polystyrene resin particles, and is preferably in the range of 20 to 60 ° C. When the temperature of the cooling water exceeds the glass transition temperature Tg of the expandable polystyrene resin particles, the expandable polystyrene resin particles are easily fused together, and a defective product in which a large number of particles are bonded to form a lump. Incidence increases. If the temperature of the cooling water is less than 20 ° C., the resulting expandable polystyrene resin particles may not be spheroidized and cracks may occur.

  The cooling water is preferably pressurized to 0.5 MPa or more. In order to pressurize the cooling water, a portion of the circulation path of the cooling water passing through the cutting chamber 7 from the discharge side of the high-pressure pump 9 to the inlet side of the dehydrating dryer 10 with a solid-liquid separation function is added. It can be executed by increasing the discharge pressure of the high-pressure pump 9 in the pressure region. The pressure of the cooling water is preferably in the range of 0.6 to 2.0 MPa, and more preferably in the range of 0.8 to 1.5 MPa.

(Reheating process)
The expandable polystyrene resin particles obtained in the granulation step are then subjected to a heat treatment at a temperature of (glass transition temperature Tg-5 of expandable polystyrene resin particles) ° C. or more, and the above-mentioned according to the present invention. Let it be an expandable polystyrene resin particle.
This reheating step may be carried out continuously immediately after producing the expandable polystyrene resin particles in the granulation step, or stored after producing the expandable polystyrene resin particles in the granulation step. In addition, it may be taken out after an arbitrary storage period and the reheating step may be performed.

  In this reheating step, for example, a heat medium such as water is placed in a pressure-resistant container having a temperature control function, and heated and kept at a temperature within the temperature range, and obtained in the granulation step. It can be carried out efficiently by introducing the expanded polystyrene resin particles.

  The heating temperature in the reheating step may be a temperature equal to or higher than (glass transition temperature Tg-5 of expandable polystyrene resin particles) ° C., and more specifically, the Tg used in Examples described later is 61. In the case of expandable polystyrene resin particles at 0 ° C., the temperature is set to 56 ° C. or higher. Although the upper limit of heating temperature is good also as 150 degreeC or more, it is preferable to make about 150 degreeC into an upper limit from a viewpoint of reducing fusion | melting of resin particles. In this case, the heating temperature is more preferably in the range of 60 to 90 ° C. If this heating temperature is less than (glass transition temperature Tg-5 of expandable polystyrene resin particles) ° C., the foamed foam bubbles obtained by heating and foaming the resulting expandable polystyrene resin particles do not become fine, There is a possibility that the mechanical strength of the foam molded product obtained by foam molding in the mold is lowered.

  The pressure in the reheating step is 1.5 MPa or less, preferably in the range of 0.1 to 1.0 MPa, and more preferably in the range of 0.1 to 0.5 MPa. When this pressure exceeds 1.5 MPa, the mechanical strength of the obtained foamed molded product may be lowered. Furthermore, it is necessary to make the container thicker in order to increase the pressure resistance of the pressure vessel used in the reheating process, which is not preferable because the mass becomes heavy.

  The heat treatment time in the reheating step is not particularly limited, but is preferably about 1 to 10 minutes, and more preferably about 1 to 5 minutes. If this heat treatment time is short, the effect of improving the cellular structure of the expandable polystyrene resin particles obtained in the granulation step and improving the mechanical strength of the foamed molded article cannot be sufficiently obtained. On the other hand, if the heat treatment time is lengthened, the production efficiency of expandable polystyrene resin particles is lowered, leading to an increase in cost, which is not preferable.

  The expandable polystyrene resin particles that have undergone this reheating step are used for the production of heat insulating materials after the necessary post-treatments such as addition of additives such as surface modifiers and drying treatments, and then through polystyrene resin pre-expanded particles. Used for

(Pre-foaming process)
The expandable polystyrene resin particles obtained by the reheating treatment are pre-foamed by heating by steam heating or the like using a well-known apparatus and method in the field of producing foamed resin moldings, and polystyrene resin pre-foamed particles ( Hereinafter referred to as pre-expanded particles). The pre-expanded particles are pre-expanded so as to have a bulk density equivalent to the density of the heat insulating material to be manufactured. In the present invention, the bulk density and the bulk foaming factor are not limited, but are usually in the range of 0.010 to 0.10 g / cm ³ (in the range of 10 to 100 times as the bulk foaming factor), 0.015 to It is preferable to be in the range of 0.050 g / cm ³ .

In the present invention, the bulk density and the bulk expansion ratio of the pre-expanded particles are those measured in accordance with JIS K6911: 1995 “General Test Method for Thermosetting Plastics”.
<Bulk density of pre-expanded particles>
Fill the graduated cylinder with pre-expanded particles to a scale of 500 cm ³ . However, the graduated cylinder is visually observed from the horizontal direction, and if at least one pre-expanded particle reaches the scale of 500 cm ³ , the filling is finished. Next, the mass of the pre-expanded particles filled in the graduated cylinder is weighed with two significant figures after the decimal point, and the mass is defined as W (g). The bulk density of the pre-expanded particles is calculated by the following formula.
Bulk density (g / cm ³ ) = W / 500

<Bulk expansion ratio of pre-expanded particles>
Moreover, the bulk expansion ratio of the pre-expanded particles is a numerical value calculated by the following equation.
Bulk foaming factor = 1 / bulk density (g / cm ³ )

  The pre-foamed particles are filled in the cavity of the mold using a well-known apparatus and method in the field of foamed resin moldings, heated by steam heating or the like, and foam-molded in the mold to insulate. Produce material.

In the heat insulating material of the present invention, the foamed molded body is foam-molded at a foaming magnification X times, and the internal average cell diameter D ₂ ′ of the fused particles in the foam-molded product is expressed by the above formula (2). Te terms of expansion ratio 50 times, average internal cell diameter D ₂ of the expanded beads of the in foam molding body, fully to the relationship 35 [mu] m ≦ D ₂ ≦ 140 .mu.m, the surface layer portion average cell diameter / average internal of the foamed particles It has a bubble structure in which the value of the bubble diameter is in the range of 0.80 to 1.20, and the open cell ratio of the foamed molded product is 10% or less.

In the heat insulating material of the present invention, the foamed molded body is foam-molded at a foaming magnification X times, and the internal average cell diameter D ₂ ′ of the fused particles in the foam-molded product is expressed by the above formula (2). Then, the expansion ratio is converted to 50 times, and the internal average cell diameter D ₂ of the expanded particles in the expanded molded product satisfies the relationship of 35 μm ≦ D ₂ ≦ 140 μm. When the average internal cell diameter D ₂ is less than 35 [mu] m, a polystyrene type resin foamed molded product obtained by mold foaming closed cell decreases with increasing open cell ratio, bending strength, compression strength, impact The mechanical strength such as property will decrease. Wherein the average internal cell diameter D ₂ is greater than 140 .mu.m, flexural strength, compressive strength, mechanical strength such as impact resistance is lowered. A preferable range of D ₂ is 40 μm ≦ D ₂ ≦ 120 μm, and a more preferable range is 45 μm ≦ D ₂ ≦ 115 μm.

  As for the heat insulating material of this invention, the value of the surface layer part average cell diameter / internal average cell diameter of the said foaming particle exists in the range of 0.80-1.20. When the value of the surface layer part average cell diameter / internal average cell diameter is out of the above range, the mechanical strength such as bending strength, compressive strength, and impact resistance of the polystyrene resin foam molded product obtained by in-mold foam molding is lowered. Resulting in.

  In the heat insulating material of the present invention, the open cell ratio of the foamed molded product is 10% or less, and preferably 8% or less. If the open cell ratio exceeds 10%, the mechanical strength such as bending strength, compressive strength, impact resistance and the like of the polystyrene-based resin foam molded product obtained by in-mold foam molding will decrease. A preferred range is 0.90 to 1.10, and a more preferred range is 0.93 to 1.06.

  In the styrene resin foam molded article of the present invention, the open cell ratio of the foam molded article is 10% or less, preferably 8% or less. If the open cell ratio exceeds 10%, the mechanical strength such as bending strength, compressive strength, impact resistance and the like of the polystyrene-based resin foam molded product obtained by in-mold foam molding will decrease.

Although the density of the heat insulating material of the present invention is not particularly limited, it is usually within a range of 0.010 to 0.10 g / cm ³ (10 to 100 times as a bulk foaming factor), and 0.015 to 0.050 g / cm ^3. It is preferable to be within the range.

In addition, in this invention, the density of a heat insulating material is a foaming molding density measured by the method of JISK7122: 1999 "Measurement of foamed plastics and rubber-apparent density".
<Density of foam molding>
A test piece of 50 cm ³ or more (100 cm ³ or more in the case of semi-rigid and soft materials) was cut so as not to change the original cell structure of the material, its mass was measured, and calculated by the following formula.
Density (g / cm ³ ) = Test piece mass (g) / Test piece volume (cm ³ )
Test piece condition adjustment and measurement test pieces were cut out from samples that had passed 72 hours or more after molding, and were subjected to atmospheric conditions of 23 ° C. ± 2 ° C. × 50% ± 5% or 27 ° C. ± 2 ° C. × 65% ± 5%. It has been left for more than an hour.

<Folding multiple of foamed molded product>
Further, the expansion factor of the foamed molded product is a numerical value calculated by the following equation.
Foaming factor = 1 / density (g / cm ³ )

  In the method for producing a heat insulating material of the present invention, expandable polystyrene resin particles obtained by melt extrusion are used at a temperature of (glass transition temperature Tg-5 of expandable polystyrene resin particles) ° C. or higher and a pressure of 0.5 MPa. By carrying out heat treatment at the following pressure to obtain expandable polystyrene resin particles, relatively small, uniform and independent bubbles are formed throughout the expanded particles when heated and foamed, and this is subjected to in-mold foam molding. Thus, a heat insulating material having excellent mechanical strength such as bending strength, compressive strength and impact resistance can be obtained.

[Example 1]
(Manufacture of expandable polystyrene resin particles)
What mixed 0.5 mass part of talc masterbatches (polystyrene resin 40 mass%, talc 60 mass%) beforehand with respect to polystyrene resin (The product name "HRM-10N" by Toyo Styrene Co., Ltd.) as base resin. After feeding into a single screw extruder having a diameter of 90 mm at a rate of 160 kg / hr per hour and heating and melting the resin, 6 parts by mass of isopentane as a blowing agent was injected from the middle of the extruder as a part of 100 parts by mass of the resin. Then, while kneading the resin and the foaming agent in the extruder, while cooling so that the resin temperature at the tip of the extruder is 170 ° C., the diameter is 0.6 mm, connected to the extruder and held at 290 ° C. by the heater. Then, through a granulation die having 200 nozzles with a land length of 3.0 mm, it was extruded into an underwater cutting chamber in which cooling water with a temperature of 50 ° C. and a water pressure of 1.5 MPa circulated, and at the same time, 10 blades in the circumferential direction. A high-speed rotating cutter having the above structure was brought into close contact with a die, cut at 3000 rpm, dehydrated and dried to obtain spherical expandable polystyrene resin particles. The obtained expandable polystyrene resin particles had an average particle size of 1.1 mm without the occurrence of deformation or beard.
Next, in order to perform the reheating treatment, 2000 g of the above expandable polystyrene resin particles, 2500 g of distilled water, and 0.5 g of sodium dodecylbenzenesulfonate were placed in an autoclave with a stirrer having an internal volume of 5.7 liters, and stirred and dispersed. . This dispersion was pressurized to 0.2 MPa with nitrogen, heated to 80 ° C., held for 3 minutes, then cooled, taken out, washed, dehydrated, and dried.
Polyethylene glycol 0.03 parts by mass, zinc stearate 0.05 parts by mass, stearic acid monoglyceride 0.05 parts by mass, hydroxystearic acid triglyceride 0.05 parts by mass with respect to 100 parts by mass of the obtained expandable polystyrene resin particles. The part was uniformly coated on the entire surface of the expandable polystyrene resin particles.

(Manufacture of insulation materials)
The expandable polystyrene resin particles obtained as described above (hereinafter may be referred to as beads) are supplied to a cylindrical batch type pre-foaming machine and heated with steam having a blowing pressure of 0.05 MPa. Obtained. The obtained pre-expanded particles had a bulk density of 0.020 g / cm ³ (bulk expansion ratio: 50 times).
Subsequently, the pre-expanded particles obtained were allowed to stand at room temperature for 24 hours, and then the pre-expanded particles were filled into a mold having a rectangular cavity of length 400 mm × width 300 mm × height 25 mm. , Molding steam pressure 0.08 MPa (gauge pressure), mold heating 3 seconds, one heating 10 seconds, reverse one heating 3 seconds, double side heating 10 seconds, water cooling 5 seconds, set extraction surface pressure 0.02 MPa went.

  For the beads, pre-expanded particles and heat insulating material, the amount of gas contained, Tg of expandable polystyrene resin particles, internal average cell diameter, surface layer average cell diameter, open cell ratio, bending strength, compressive strength according to the following measurement method And it measured about each test item of a drop test. The results are shown in Table 1.

<Contained gas amount>
With respect to the beads, the heating loss was measured at a heating temperature of 145 ° C. for 2 hours, and the amount of gas contained was calculated.

<Measurement of Tg of Expandable Polystyrene Resin Particle>
Tg was measured according to the test method of JIS K7121. Specifically, using a differential scanning calorimeter DSC6220 type (manufactured by SII NanoTechnology Co., Ltd.), 6.5 mg of a sample bead is filled in a measurement container, and a nitrogen gas flow rate of 25 ml / min is 20 ° C./min. The temperature was raised from 30 ° C. to 200 ° C. at a rate of temperature rise, and the midpoint glass transition temperature was taken as the glass transition temperature.

<Measurement of internal average cell diameter of pre-expanded particles>
The internal average cell diameter of pre-expanded particles refers to that measured in accordance with the test method of ASTM D2842-69. Specifically, it is cut with a razor tooth on a plane passing through the vicinity of the center of the pre-foamed particle, and the cut surface is enlarged 15 times using a scanning electron microscope (trade name “JSM-6360LV” manufactured by JOEL). To do.
Next, the photographed image is printed on A4 paper, and a first circle (inscribed circle) inscribed in the surface layer of the pre-expanded particles is drawn. A second concentric circle having a diameter of ½ (a radius of ¼) is drawn with respect to the diameter of the first circle, and a straight line having a length of 60 mm is placed at an arbitrary position inside the second circle. This drawing is performed, and the average chord length (t) of the bubbles is calculated from the number of bubbles existing on this straight line by the following formula.
Average string length t = 60 / (number of bubbles × photo magnification)
When drawing a straight line, the straight line should be penetrated as much as possible without making point contact with the bubbles. Also, if some of the bubbles come into point contact with a straight line, this bubble is included in the number of bubbles, and if both ends of the straight line are located in the bubble without penetrating the bubbles Includes the bubbles in which both ends of the straight line are located in the number of bubbles.
And based on the calculated average chord length t, the bubble diameter can be calculated by the following equation.
Average bubble diameter (mm) D = t / 0.616
Furthermore, the average bubble diameter is calculated in the same manner as described above at any five locations in the photographed image, and the arithmetic average value of these average bubble diameters is used as the internal average bubble diameter of the pre-expanded particles.

<Surface layer average cell diameter of pre-expanded particles>
The surface is cut with a razor tooth on a plane passing through the vicinity of the center of the pre-foamed particles, and the cut surface is photographed with a scanning electron microscope (trade name “JSM-6360LV” manufactured by JOEL) magnified 15 times.
Next, the photographed image is printed on A4 paper, and a first circle (inscribed circle) inscribed in the surface layer of the pre-expanded particles is drawn. A second concentric circle having a diameter of ½ (a radius of ¼) is drawn with respect to the diameter of the first circle, and a length of 60 mm is provided at an arbitrary position between the second circle from the surface layer. A straight line is drawn, and the average chord length (t) of the bubbles is calculated in the same manner as the internal average bubble diameter from the number of bubbles existing on the straight line, and is used as the surface layer average bubble diameter.

<Measurement of internal average bubble diameter of heat insulating material>
The heat insulating material is cut with a razor tooth, and the cut surface is photographed with a scanning electron microscope (trade name “JSM-6360LV” manufactured by JOEL) magnified 15 times.
Next, the photographed image is printed on A4 paper, and a first circle (inscribed circle) inscribed in the grain boundary portion of the fused foam particles existing on the cut surface is drawn. Draw a second concentric circle having a diameter of 1/2 (1/4 radius) with respect to the diameter of the first circle, and form a straight line with a length of 60 mm at any location inside the second circle. One was drawn and the average chord length (t) of the bubbles was calculated from the number of bubbles present on this straight line in the same manner as the internal average bubble size of the pre-expanded particles, and the internal average bubble size of the heat insulating material was obtained.

<Measurement of surface average bubble diameter of heat insulating material>
The heat insulating material is cut with a razor tooth, and the cut surface is photographed with a scanning electron microscope (trade name “JSM-6360LV” manufactured by JOEL) magnified 15 times.
Next, the photographed image is printed on A4 paper, and a first circle (inscribed circle) inscribed in the grain boundary portion of the fused foam particles existing on the cut surface is drawn. A second concentric circle having a diameter of ½ (a radius of ¼) is drawn with respect to the diameter of the first circle, and the length is set at an arbitrary position between the second circle from the grain boundary portion. A straight line of 60 mm is drawn, and the average chord length (t) of the bubbles is calculated from the number of bubbles existing on the straight line in the same manner as the internal average bubble diameter of the pre-expanded particles, and the average bubble diameter of the surface layer portion of the heat insulating material is calculated. Asked.

<Measurement of open cell ratio of pre-expanded particles>
The following tests (1) to (3) were performed to determine the open cell ratio (%) of the pre-expanded particles.
(1) Mass and volume measurement of pre-expanded particles The mass of the pre-expanded particles that are about 80% into the sample cup of an air-comparing hydrometer (1000 type, manufactured by Tokyo Science) was measured in advance [pre-expanded particle mass A (g )]].
Next, the pre-expanded particles were put in a cup, the cup was set in the above-mentioned specific gravity meter, and the volume was measured by the 1-1 / 2-1 atmospheric pressure method [volume B (cm ³ ) of the pre-expanded particles].
(2) Apparent volume measurement of pre-expanded particles Remove the weighing pan from the electronic balance (HB3000, manufactured by Daiwa Seikan Co., Ltd.) and immerse the container in water with the wire mesh container suspended from the mounting bracket. The mass of the container in water was measured [the container mass C (g) in water].
Next, the total amount of the pre-expanded particles measured in the above (1) was put in the same container, and the total mass of the container and the pre-expanded particles was measured in the same manner as described above [total mass D in water D ( g)].
And the apparent volume E (cm < ³ >) of the pre-expanded particle was calculated | required by following Formula. In addition, 1 g of water was converted as a volume of 1 cm ³ .
E = A + (CD)
(3) Open cell ratio From the results of (1) and (2) above, the open cell ratio [%] was determined by the following equation.
Open cell ratio (%) = (E−B) / E × 100

<Measurement of open cell ratio of heat insulating material>
About the heat insulating material, the open cell rate was measured according to the measuring method of ASTM D2856-87. That is, five specimens (25 mm cubes) made of a cut surface having no skin such as a six-surface co-molded surface were cut out, the apparent volume was measured using a caliper, and then the air comparison specific gravity system 1000 The volume was measured by the 1-1 / 2-atm method using a mold (manufactured by Tokyo Science).
Open cell ratio (%) = (apparent volume−volume measured with an air-based hydrometer) / apparent volume × 100

<Bending strength>
A test piece having a length of 300 mm, a width of 75 mm, and a thickness of 25 mm was cut out from the heat insulating material, and a bending test of the test piece was performed according to JIS-A9511 to calculate a bending strength.

<Compressive strength>
A test piece having a length of 50 mm, a width of 50 mm, and a thickness of 25 mm was cut out from the heat insulating material, and a bending test of the test piece was performed in accordance with JIS-A9511 to obtain a bending strength.

<Insulation (thermal conductivity)>
A rectangular parallelepiped test piece having a length of 200 mm, a width of 200 mm, and a thickness of 25 mm was cut out from the heat insulating material. Then, the thermal conductivity of this test piece was measured at a measurement temperature of 23 ° C. using a thermal conductivity meter (AUTO-Λ HC-072) manufactured by Eihiro Seiki Co., Ltd. according to JIS A1412.

[Example 2]
A heat insulating material was manufactured by the same method as in Example 1 except that the heating temperature during the reheating treatment was 150 ° C. and the pressure was 0.5 MPa, and the same measurement was performed. The results are shown in Table 1.

[Example 3]
A heat insulating material was manufactured by the same method as in Example 1 except that the heating temperature during the reheating treatment was 60 ° C., and the same measurement was performed. The results are shown in Table 1.

[Example 4]
A heat insulating material was manufactured in the same manner as in Example 1 except that the heating temperature at the reheating treatment was 57 ° C., and the same measurement was performed. The results are shown in Table 1.

[Example 5]
A heat insulating material was produced in the same manner as in Example 1 except that the same amount of butane was used as the foaming agent and the pressure during the reheating treatment was 0.5 MPa, and the same measurement was performed. The results are shown in Table 1.

[Comparative Example 1]
A heat insulating material was manufactured in the same manner as in Example 1 except that the heating temperature during the reheating treatment was 100 ° C., and the same measurement was performed. The results are shown in Table 1.

[Comparative Example 2]
The heat insulating material was treated in the same manner as in Example 1 except that the cooling water temperature in the underwater cut chamber was 70 ° C., the pressure during the reheating treatment was 1.5 MPa, and the reheating treatment time was heated for 5 minutes after the temperature was raised. The same measurement was carried out. The results are shown in Table 1.

[Comparative Example 3]
A heat insulating material was manufactured in the same manner as in Example 1 except that the reheating treatment was not performed, and the same measurement was performed. The results are shown in Table 1.

[Comparative Example 4]
A heat insulating material was manufactured in the same manner as in Example 1 except that the heating temperature at the time of the reheating treatment was 40 ° C., and the same measurement was performed. The results are shown in Table 1.

[Comparative Example 5]
A heat insulating material was manufactured in the same manner as in Example 1 except that the heating time after the temperature increase during the reheating treatment was 1 minute, and the same measurement was performed. The results are shown in Table 1.

  From the results shown in Table 1, the heat insulating materials obtained in Examples 1 to 5 according to the present invention are in the form of expanded particles expanded to a bulk expansion ratio of 50 times, and the internal average cell diameter is in the range of 35 to 140 μm. It has a cell structure in which the value of the surface layer part average bubble diameter / internal average bubble diameter is in the range of 0.80 to 1.20, and the open cell ratio is 10% or less, and bulk foaming. The heat insulating material obtained by in-mold foam molding of the pre-expanded particles expanded to a multiple of 50 times has a low open cell ratio and a large number of closed cells, compared with the heat insulating material of Comparative Example 3 in which reheating treatment is not performed. The flexural strength and compressive strength of the foamed molded product were high, and the heat insulation was good.

On the other hand, since the heat insulating material of Comparative Example 1 has a high open cell ratio and a small number of closed cells, the bending strength and the compressive strength were low.
Moreover, since the internal average bubble diameter of the heat insulating material of the comparative example 2 exceeded the range of this invention, bending strength and compressive strength were low.
Moreover, since the internal average bubble diameter exceeded the range of this invention as a result of not heat-treating the heat insulating material of the comparative example 3, bending strength and compressive strength were low.
Moreover, the heat insulating material of Comparative Example 4 was low in bending strength and compressive strength because the internal average bubble diameter exceeded the range of the present invention as a result of reheating treatment at a low temperature.
Moreover, the heat insulating material of Comparative Example 5 had a low bending strength and compressive strength as a result of the value of the surface layer portion average bubble diameter / internal average bubble diameter being outside the range of the present invention.

  The present invention relates to a heat insulating material made of a polystyrene-based resin foam molded article that is excellent in heat insulating performance and mechanical strength such as bending strength, compressive strength, and impact resistance, and a method for producing the same.

  DESCRIPTION OF SYMBOLS 1 ... Extruder (resin supply apparatus), 2 ... Die, 3 ... Raw material supply hopper, 4 ... High pressure pump, 5 ... Foam supply port, 6 ... Cutter, 7 ... Cutting chamber, 8 ... Water tank, 9 ... High pressure pump, 10: Dehydration dryer with solid-liquid separation function, 11: Storage container.

Claims (12)

The polystyrene resin pre-expanded particles obtained by heating the expandable polystyrene resin particles containing a foaming agent in the polystyrene resin particles were filled in the mold cavity and heated, and obtained by in-mold foam molding. In the heat insulating material made of polystyrene resin foam molding,
In the state of pre-expanded particles obtained by heating the expandable polystyrene-based resin particles and expanded to a bulk expansion ratio of 50 times, the internal average cell diameter is in the range of 35 to 140 μm, and the surface layer part average cell diameter / internal average cell A heat insulating material having a cell structure in which a value of a diameter is in a range of 0.80 to 1.20 and an open cell ratio is 10% or less. The internal average cell diameter D ₁ ′ of the pre-expanded particles when expanded to a bulk expansion ratio X times is expressed by the following formula (1)

(In the formula, D ₁ represents the internal average cell diameter (μm) of the expanded particles converted to a bulk expansion ratio of 50 times, and D ₁ ′ represents the internal average cell diameter of the expanded particles when expanded to a bulk expansion ratio X times) 2. The internal average cell diameter D _{1 of} the pre-expanded particles converted to a bulk expansion ratio of 50 times using (expressing (μm)) satisfies a relationship of 35 μm ≦ D ₁ ≦ 140 μm. Insulation.   The heat insulating material according to claim 1 or 2, wherein the internal average bubble diameter is within a range of 40 to 120 µm.   The heat insulating material according to any one of claims 1 to 3, wherein the open cell ratio is 8% or less.   5. The heat insulating material according to claim 1, wherein a value of the surface layer part average bubble diameter / internal average bubble diameter is in a range of 0.90 to 1.10.   The heat insulating material according to any one of claims 1 to 5, comprising an inorganic cell nucleating agent of 5.0 parts by mass or less with respect to 100 parts by mass of a polystyrene-based resin.   The heat insulating material according to claim 6, wherein the inorganic cell nucleating agent is talc. A heat insulating material made of a styrene resin foam molded article obtained by filling styrene resin pre-expanded particles in a cavity of a mold, steam heating the mold, and foam-molding in the mold,
In the state when foaming is performed at the expansion ratio X times, the internal average cell diameter D ₂ ′ of the foam particles fused together in the foamed molded product is expressed by the following formula (2):

(Wherein, D ₂ represents the average internal cell diameter of the expanded beads of foamed molded body in terms of 50-fold expansion ratio ([mu] m), D 2 _'is in the foamed molded product when foamed in expansion ratio X times the average internal cell diameter average internal cell diameter D ₂ of the expanded beads of foamed molded body in terms of expansion ratio 50 times using a representative of the ([mu] m)) is, satisfies the relationship of 35 [mu] m ≦ D ₂ ≦ 140 .mu.m of the foamed particles The foamed particles have a cell structure in which the value of the surface layer part average cell diameter / internal average cell diameter is in the range of 0.80 to 1.20, and the foamed molded product has an open cell ratio of 10% or less. Insulation material characterized by A foaming agent is added to and kneaded with the polystyrene resin in the resin supply device, and the temperature of the foaming agent-containing molten resin is less than the glass transition temperature Tg of the expandable polystyrene resin particles from the small hole of the die attached to the tip of the resin supply device. Extruding into the cooling liquid, cutting the extrudate at the same time as extrusion, and cooling and solidifying the extrudate by contact with the liquid to obtain expandable polystyrene resin particles,
A step of obtaining the expandable polystyrene resin particles by subjecting the obtained expandable polystyrene resin particles to a heat treatment at a temperature of (glass transition temperature Tg-5 of the expandable polystyrene resin particles) ° C. or higher;
Then heated resulting expandable polystyrene resin particles, wherein the formula (1) is the average internal cell diameter D ₁ of the pre-expanded particles in terms of 50-fold volume expansion ratio by using, in the range of 35~140μm Yes, a polystyrene resin pre-expanded particle having a cell structure in which the value of the average cell diameter of the surface layer / the average cell diameter of the internal layer is in the range of 0.80 to 1.20 and the open cell ratio is 10% or less is prepared. The process of
Then, filling the polystyrene resin pre-expanded particles in a cavity of a mold, heating, and foam-molding in the mold to obtain a heat insulating material, a method for manufacturing a heat insulating material.   The method for producing a heat insulating material according to claim 9, wherein the temperature of the cooling liquid when cutting the extrudate is in the range of 20 to 60 ° C.   The method for producing a heat insulating material according to claim 9 or 10, wherein an inorganic cell nucleating agent of 5.0 parts by mass or less is added to 100 parts by mass of a polystyrene-based resin.   The method for manufacturing a heat insulating material according to claim 11, wherein the inorganic cell nucleating agent is talc.

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