JP2011093948A - Foamable polystyrene resin particles for production of heat-insulating material for building material and process for production thereof, prefoamed particles for production of heat-insulating material for building material, and heat-insulating material for building material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-insulating material for building materials having satisfactory flame retardant performance and excellent mechanical strength and dimensional stability with a flame retardant that is highly safe for environments and organisms. <P>SOLUTION: Foamable polystyrene resin particles for the production of a heat-insulating material for building materials are obtained by a melt extrusion method in which a flame retardant and a foaming agent are added to a polystyrene resin in a resin feed unit and kneaded, the resulting molten resin containing the flame retardant and foaming agent is directly extruded into a cooling liquid from small holes in a die attached to the leading end of the resin feed unit, and simultaneously with the extrusion, the extrudates are cut and solidified by cooling by contact with the liquid to obtain foamable polystyrene resin particles. The flame retardant contained in the foamable polystyrene resin particles contains a bromine atom in the molecule, has a bromine-containing component content of <70 mass%, has a benzene ring in the molecule, and has a 5 mass% decomposition temperature of 200-300°C. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a heat insulating material for building materials excellent in environmental compatibility and flame retardancy, an expandable polystyrene resin particle for manufacturing a heat insulating material for building materials used in the manufacture thereof, and a method for manufacturing the same. The heat insulating material for building materials according to the present invention is used by being disposed, for example, between joists or large pulls on the floor of a building, between columns and studs on walls, and between rafters on a roof.

  In order to improve the heat insulation performance in a house or the like, a heat insulation method is known in which a heat insulating material is disposed between joists on the floor or between support members such as pillars and studs on the wall. As a heat insulating material used in such a heat insulating method, glass wool has been widely used in general. However, since glass wool is likely to cause a decrease in heat insulation effect due to moisture absorption, a high heat insulation effect cannot be expected over a long period of time, and there is a problem in workability. For this reason, in recent years, this type of heat insulating material is shifting to a polystyrene-based resin foam molded article excellent in dimensional stability and heat insulating properties.

Insulating materials for building materials are usually required to have a certain level or more of flame retardancy from the viewpoints of preventing the occurrence of fire and the like, and preventing the spread of fire due to the spread of fire in the event of a fire. In order to impart sufficient flame retardancy to a polystyrene resin foam molded article, a flame retardant is added to the expandable polystyrene resin particles for producing the foam molded article.
Further, as a heat insulating material for building materials, in addition to waterproofness, moisture absorption resistance, moisture proofing, heat insulating properties, etc., it is required not to expand or contract due to temperature change (dimensional stability).
Furthermore, the heat insulating material for building materials is required to reduce the emission amount of volatile organic compounds such as formaldehyde, toluene, xylene, styrene and the like as a countermeasure against sick house syndrome, which has been increasing in recent years.

Conventionally, for example, the prior art disclosed in Patent Document 1 has been proposed as an expandable polystyrene resin particle used as a heat insulating material for building materials.
Patent Document 1 discloses that 100 parts by weight of expandable polystyrene resin particles have a styrene monomer of 350 to 1200 ppm and 250 ° C. when vacuum distillation is performed under a pressure of 6.666 × 10 ⁻⁴ MPa (5 mmHg). Expandable polystyrene-based resin particles characterized by containing 0.1 to 2 parts by mass of a plasticizer that cannot be distilled at the following temperatures and a foaming agent are disclosed.

JP 2003-64212 A

  Patent Document 1 describes a suspension polymerization method as a specific method for producing expandable polystyrene resin particles, and hexabromocyclododecane is present in the entire styrene polymerization process. Hexabromocyclododecane is a type 1 monitoring chemical substance in the Chemical Substances Control Regulation Law, and it has been pointed out that it is difficult to decompose and highly concentrated in the existing chemical substance safety inspection of the Ministry of Economy, Trade and Industry, and is also subject to European risk assessment assessment. Since there is a problem with its safety, it is desired to eliminate its use. Further, it is known that hexabromocyclododecane causes polymerization inhibition of styrene monomer when added to the polymerization process of styrene. As a result, the foamable polystyrene resin particles obtained contain a large amount of residual volatile organic compounds, making it difficult to cope with the recently demanded sick house syndrome. Not suitable.

Also, as a method of adding a flame retardant to the expandable polystyrene resin particles, when impregnating the polystyrene resin particles with the foaming agent, the flame retardant is added simultaneously with the foaming agent, and the polystyrene resin particles are impregnated with these to foam. In this impregnation method, when the flame retardant is dissolved in an organic solvent and added, the used organic solvent remains in the resin particles and the resulting foam is obtained. Since the residual polystyrene-based resin particles contain a large amount of residual volatile organic compounds, they are not suitable for use in the production of heat insulating materials for building materials.
In addition, in the method of adding the polystyrene resin particles impregnated with the flame retardant as described above, the flame retardant is impregnated near the surface of the polystyrene resin particles, but the flame retardant is not present or contained near the resin particle center. Only low-resin resin particles can be obtained, and polystyrene resin foam molded products obtained by pre-foaming such resin particles and further foam-molding the obtained pre-foamed particles are inferior in mechanical strength and moldability. , The dimensional stability is deteriorated, and it becomes unsuitable for the use for manufacturing a heat insulating material for building materials.

  The present invention is made in view of the above circumstances, and provides a heat insulating material for building materials that has sufficient flame retardancy using a flame retardant that is highly safe for the environment and living organisms, and that is also excellent in mechanical strength and dimensional stability. Objective.

In order to achieve the above object, the present invention is an expandable polystyrene resin particle for producing a heat insulating material for building materials, in which a polystyrene resin containing a flame retardant and a foaming agent is in the form of particles,
The flame retardant has a bromine atom in the molecule, a bromine content of less than 70% by mass, a benzene ring in the molecule, and a 5% by mass decomposition temperature of the flame retardant of 200 to 300 ° C. Within the range of
A flame retardant and foaming agent are added to and kneaded with polystyrene resin in the resin supply device, and the molten resin containing the flame retardant / foaming agent is extruded directly into the cooling liquid through a small hole in the die attached to the tip of the resin supply device. The extrudate is cut at the same time as it is extruded, and the extrudate is cooled and solidified by contact with a liquid to obtain an expandable polystyrene resin particle for manufacturing a heat insulating material for building materials. The present invention provides foamable polystyrene resin particles for manufacturing a heat insulating material for building materials.

  In the expandable polystyrene resin particles for manufacturing a heat insulating material for building materials of the present invention, the total content of aromatic organic compounds composed of styrene monomer, ethylbenzene, isopropylbenzene, normal propylbenzene, xylene, toluene, benzene is less than 500 ppm. Is preferred.

  In the expandable polystyrene resin particles for producing a heat insulating material for building materials of the present invention, the flame retardant is preferably one or more selected from the group consisting of tetrabromobisphenol A or a derivative thereof.

  In the expandable polystyrene resin particles for producing a heat insulating material for building materials of the present invention, the flame retardant is tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol A-bis (2 , 3-dibromopropyl ether), tetrabromobisphenol A-bis (allyl ether), and preferably one or more selected from the group consisting of tetrabromobisphenol A-bis (allyl ether).

  Moreover, this invention provides the pre-expanded particle for heat insulation materials for building materials obtained by heating the said expandable polystyrene-type resin particle for heat insulation materials for building materials.

Further, the present invention provides the building material having a density in the range of 0.010 to 0.050 g / cm ³ obtained by filling the pre-expanded particles for producing the heat insulating material for building material into the cavity of the mold and heating and foaming. Providing thermal insulation materials.

  Further, the present invention is obtained by filling the above pre-expanded particles for manufacturing a heat insulating material for building materials into a cavity of a molding die and heating and foaming. The foamed molded article having a foaming factor of 40 times has an average cell string length of 50. Provided is a heat insulating material for building materials in a range of ˜350 μm.

  Further, the present invention provides a polystyrene resin in a resin supply apparatus having a bromine atom in the molecule, a bromine content of less than 70% by mass, a benzene ring in the molecule, and the flame retardant. A flame retardant and a foaming agent having a 5 mass% decomposition temperature in the range of 200 to 300 ° C. are added and kneaded, and the flame retardant / foaming agent-containing molten resin is directly from the small hole of the die attached to the tip of the resin supply device. In the method of extruding into a cooling liquid, cutting the extrudate at the same time as extruding, and cooling and solidifying the extrudate by contact with the liquid to produce expandable polystyrene resin particles, styrene monomer, ethylbenzene, isopropylbenzene, A building material characterized by obtaining expandable polystyrene resin particles without using an aromatic organic compound composed of normal propylbenzene, xylene, toluene and benzene To provide a method of manufacturing a heat insulating material for producing expandable polystyrene resin particles.

  In the method for producing expandable polystyrene resin particles for producing a heat insulating material for building materials according to the present invention, the flame retardant is preferably one or more selected from the group consisting of tetrabromobisphenol A or a derivative thereof. .

  In the method for producing expandable polystyrene resin particles for producing a heat insulating material for building materials of the present invention, the flame retardant is tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol A-. One or more selected from the group consisting of bis (2,3-dibromopropyl ether) and tetrabromobisphenol A-bis (allyl ether) are preferred.

  In the method for producing expandable polystyrene resin particles for manufacturing a heat insulating material for building materials of the present invention, a master batch material containing the flame retardant at a predetermined concentration in a resin is supplied together with the polystyrene resin into a resin supply device, and the device It is preferable to melt and knead the inside.

The expandable polystyrene resin particles for producing a heat insulating material for building materials of the present invention have a bromine atom in the molecule, a bromine content of less than 70% by mass, a benzene ring in the molecule, and the difficulty. It contains a flame retardant having a 5 mass% decomposition temperature in the range of 200 to 300 ° C. The flame retardant is highly safe for the environment and organisms. In particular, the tetrabromobisphenol A derivative can impart sufficient flame retardant performance when added to a polystyrene resin foamed molded article, and is safe for the environment and organisms. Since the safety is high, it is possible to provide a heat insulating material for building materials that is excellent in safety. In addition, by using the flame retardant added to a polystyrene resin, it is possible to reduce the content of residual volatile organic compounds such as styrene monomers and to cope with sick house syndrome. .
The expandable polystyrene resin particles for manufacturing a heat insulating material for building materials according to the present invention are prepared by adding a flame retardant and a foaming agent to a polystyrene resin in a resin supply apparatus and kneading the resin, and supplying the flame retardant / foaming agent-containing molten resin to the resin supply apparatus. Extrusion directly into the cooling liquid from the small hole of the die attached to the tip, and simultaneously extruding, cutting the extrudate, and cooling and solidifying the extrudate by contact with the liquid to obtain expandable polystyrene resin particles Since the flame retardant is uniformly present in the resin particles, the mechanical strength of the resulting insulation for building materials is higher than that in which the flame retardant is unevenly present in the resin particles. The heat insulating material for building materials which becomes high and has excellent dimensional stability and moldability can be obtained.

The heat insulating material for building material of the present invention heats and expands the expandable polystyrene resin particles for manufacturing the heat insulating material for building materials, and further heats by filling the obtained pre-expanded particles in the cavity of the mold, Since it is obtained by foaming, it is possible to provide a heat insulating material for building materials that has sufficient flame resistance using a flame retardant that is highly safe for the environment and living organisms, and that has excellent mechanical strength and dimensional stability. it can.
In addition, since it is possible to provide a heat insulating material for building materials having a low content of aromatic organic compounds composed of styrene monomer, ethylbenzene, isopropylbenzene, normal propylbenzene, xylene, toluene, and benzene, it is possible to cope with sick house syndrome.

According to the method for producing expandable polystyrene resin particles for producing a heat insulating material for building materials of the present invention, it is possible to efficiently produce the expandable polystyrene resin particles for producing a heat insulating material for building materials having an excellent effect as described above. it can. In particular, according to the production method of the present invention, a foamable polystyrene system for producing a heat insulating material for building materials having a low content of an aromatic organic compound composed of a styrene monomer, ethylbenzene, isopropylbenzene, normal propylbenzene, xylene, toluene, and benzene. Resin particles can be produced with high efficiency.
Further, in the method for producing expandable polystyrene resin particles for manufacturing a heat insulating material for building materials of the present invention, a masterbatch material containing the flame retardant at a predetermined concentration in the resin is supplied into the resin supply apparatus together with the polystyrene resin. By melt-kneading in the apparatus, the flame retardant can be more uniformly contained in the resin particles.

It is a block diagram which shows an example of the manufacturing apparatus used for the manufacturing method of the expandable polystyrene-type resin particle for heat insulating material manufacture for building materials of this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
The method for producing expandable polystyrene resin particles for producing a heat insulating material for building materials according to the present invention has a bromine atom in the molecule and a bromine content of less than 70% by mass in the polystyrene resin in the resin supply apparatus. A flame retardant / foaming agent-containing molten resin having a benzene ring in the molecule and adding and kneading a flame retardant and a foaming agent having a 5 mass% decomposition temperature within the range of 200 to 300 ° C. Is extruded into the cooling liquid directly from the small hole of the die attached to the tip of the resin supply device, and at the same time the extrudate is cut, the extrudate is cooled and solidified by contact with the liquid, and expandable polystyrene resin particles Without using an aromatic organic compound consisting of styrene monomer, ethylbenzene, isopropylbenzene, normal propylbenzene, xylene, toluene, benzene. It is characterized by obtaining the foam polystyrene resin particles.

  FIG. 1 is a configuration diagram showing an example of a manufacturing apparatus used in the method for manufacturing expandable polystyrene resin particles for manufacturing a heat insulating material for building materials according to the present invention. The manufacturing apparatus of this example is an extruder as a resin supply apparatus. 1, a die 2 having a large number of small holes attached to the tip of an extruder 1, a raw material supply hopper 3 for introducing a resin raw material or the like into the extruder 1, and a foaming agent supply to the molten resin in the extruder 1 A high-pressure pump 4 for press-fitting a foaming agent through a port 5, a cutting chamber 7 provided so that cooling water is brought into contact with a resin discharge surface provided with a small hole in the die 2, and into which cooling water is circulated and supplied; The cutter 6 is rotatably provided in the cutting chamber 7 so that the resin extruded from the small hole of the die 2 can be cut, and the foamable particles carried along with the flow of cooling water from the cutting chamber 7 are cooled. Separation from water and dehydration A dehydrating dryer 10 with a solid-liquid separation function for drying to obtain expandable particles, a water tank 8 for storing cooling water separated by the dehydrating dryer 10 with a solid-liquid separation function, and the cooling water in the water tank 8 are cut. A high-pressure pump 9 for feeding to the chamber 7 and a storage container 11 for storing expandable particles dehydrated and dried by a dehydrator / dryer 10 with a solid-liquid separation function are provided.

  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 the expandable polystyrene resin particles for manufacturing a heat insulating material for building materials of the present invention, the polystyrene resin is not particularly limited. For example, styrene, α-methylstyrene, vinyltoluene, chlorostyrene, ethylstyrene, i-propylstyrene. Homopolymers of styrene monomers such as dimethyl styrene and bromo styrene or copolymers thereof, and the like. 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.

  In the expandable polystyrene resin particles for producing a heat insulating material for building materials of the present invention, as a polystyrene resin as a raw material, a polystyrene system newly produced by a method such as a commercially available ordinary polystyrene resin or suspension polymerization method. In addition to a polystyrene-based resin (virgin polystyrene) that is not a recycled material, such as a resin, a recycled material obtained by regenerating a used polystyrene-based resin foam molding can be used. As this recycled material, used polystyrene-based resin foam moldings such as fish boxes, household appliance cushioning materials, food packaging trays, 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 weight 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 weight average molecular weights Mw can be used in appropriate combination.

In the expandable polystyrene resin particles for producing a heat insulating material for building materials of the present invention, the flame retardant has a bromine atom in the molecule, a bromine content of less than 70% by mass, and a benzene ring in the molecule. In addition, a flame retardant having a 5 mass% decomposition temperature within the range of 200 to 300 ° C of the flame retardant is used, and one or more of the flame retardants are mixed, or the flame retardant is mainly used. As such, it may be used in combination with other flame retardants.
A flame retardant with a bromine content of more than 70% by mass and no benzene ring in the molecule is unlikely to be a flame retardant that is highly safe for the environment and organisms, and has excellent mechanical strength, moldability, and dimensional stability. It becomes difficult to achieve the effect of the present invention of providing a heat insulating material for building materials. The lower limit of the bromine content is not particularly limited, but 50% by mass or more is preferable because the flame retardancy is good. A more preferable range of bromine content is 55 to 69 mass%.
Further, when the 5 mass% decomposition temperature of the flame retardant is less than 200 ° C., when the flame retardant and polystyrene resin are melt-kneaded in the extruder 1, the flame retardant decomposes and a flame retardant effect is obtained. There is a risk of disappearing. When a flame retardant having a 5 mass% decomposition temperature exceeding 300 ° C. is used, the flame retardancy of the resulting building material heat insulating material is lowered. The preferable range of 5 mass% decomposition temperature of this flame retardant is 230-300 degreeC, The more preferable range is 240-295 degreeC, The most preferable range is 265-290 degreeC.

In the present invention, preferred flame retardants include one or more selected from the group consisting of tetrabromobisphenol A or derivatives thereof. Among these flame retardants, tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A- It is preferable that it is 1 type, or 2 or more types selected from the group consisting of bis (allyl ether). Tetrabromobisphenol A-bis (2,3-dibromopropyl ether) and tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether) having a high 5% decomposition temperature are more preferred, and tetrabromobisphenol A- Bis (2,3-dibromopropyl ether) is most preferred.
In the expandable polystyrene resin particles for manufacturing a heat insulating material for building materials of the present invention, the amount of the flame retardant added is 0.5 to 100 parts by mass of the resin content of the expandable polystyrene resin particles for manufacturing the heat insulating material for building materials. It is preferable to set it as the range of 8.0 mass%, and the range of 1.0-6.0 mass% is still more preferable. If the added amount of the flame retardant is less than the above range, the flame retardancy of the obtained building material heat insulating material is lowered. When the amount of the flame retardant added exceeds the above range, the mechanical strength, moldability, and dimensional stability of the resulting building material heat insulating material may be deteriorated.

  In the expandable polystyrene resin particles for manufacturing a heat insulating material for building materials of the present invention, the foaming agent is not particularly limited. For example, normal pentane, isopentane, cyclopentane, cyclopentadiene, etc. are used alone or in combination of two or more. Can be used. Further, normal butane, isobutane, propane and the like can be mixed and used with the pentane as a main component. In particular, pentanes are preferably used because they easily suppress foaming of the resin particles when discharged into the water stream from the small holes of the die. The amount of the foaming agent contained in the polystyrene resin is in the range of 3 to 10 parts by mass, more preferably in the range of 4 to 7 parts by mass with respect to 100 parts by mass of the polystyrene resin.

  In addition to the flame retardant and the foaming agent, the foamable polystyrene resin particles for producing a heat insulating material for building materials according to the present invention may include other additives generally used in the production of expandable polystyrene resin particles. Agents, for example, talc, calcium silicate, synthetic or naturally produced silicon dioxide, ethylene bisstearic acid amide, methacrylic acid ester copolymer and other foam nucleating agents, diphenylalkane, diphenylalkene and other flame retardant aids, Colorants such as carbon black, iron oxide and graphite, phenolic antioxidants, sulfur antioxidants, antioxidants such as phosphorus antioxidants, stabilizers such as hindered amines, UV absorbers, antioxidants, etc. These additives can be added to the polystyrene resin.

  In order to produce the expandable polystyrene resin particles for producing a heat insulating material for building materials of the present invention using the production apparatus shown in FIG. 1, first, the raw material polystyrene resin, the flame retardant, the foam nucleating agent, and as necessary. The desired additive to be added is weighed and charged into the extruder 1 from the raw material supply hopper 3. 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.

  In a preferred embodiment of the present invention, when the flame retardant is added, a masterbatch material containing a flame retardant at a predetermined concentration in the resin is used, and this is supplied into the resin supply apparatus together with the polystyrene-based resin. It is preferable to melt and knead. A master batch material containing the flame retardant at a predetermined concentration in the resin is supplied into the resin supply apparatus together with the polystyrene resin, and melt-kneaded in the apparatus so that the flame retardant is more uniformly contained in the resin particles. Can do.

  After supplying polystyrene-based resin and flame retardant, further foaming aid and other additives into the extruder 1, the resin is heated and melted, and the flame retardant-containing molten resin is transferred to the die 2 side while supplying the foaming agent supply port. The foaming agent is press-fitted with a high-pressure pump 4 from 5, the foaming agent is mixed with the flame retardant-containing molten resin, and the melt is further kneaded through a foreign matter removing screen provided in the extruder 1 as necessary. The melted material added with the blowing agent is pushed out from the small hole of 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. Extruding the melt with the blowing agent added through a small hole in the die 2 attached to the tip of the extruder 1 causes the melt to be cut into granules, and at the same time, brought into contact with cooling water and rapidly cooled to solidify while suppressing foaming. Thus, expandable polystyrene resin particles for manufacturing a heat insulating material for building materials are obtained.

  The formed expandable polystyrene resin particles for manufacturing the building material heat insulating material are transported from the cutting chamber 7 to the flow of the cooling water and carried to the dehydrating dryer 10 having a solid-liquid separation function. The expandable polystyrene resin particles are separated from the cooling water and dehydrated and dried. The dried expandable polystyrene resin particles for manufacturing a building insulation material are stored in a storage container 11.

  The expandable polystyrene resin particles for the production of heat insulating materials for building materials produced as described above are in the form of particles of a polystyrene resin containing a flame retardant and a foaming agent, and the flame retardant has bromine atoms in the molecule. The bromine content is less than 70 mass%, the molecule has a benzene ring, and the 5 mass% decomposition temperature of the flame retardant is in the range of 200 to 300 ° C.

  In the expandable polystyrene resin particles for producing a heat insulating material for building materials of the present invention, the flame retardant is uniformly contained in the resin particles. In the expandable polystyrene resin particles for manufacturing a heat insulating material for building materials of the present invention, if not contained uniformly, the mechanical strength, moldability, dimensional stability and Flame retardancy may be inferior.

The flame retardant used in the expandable polystyrene resin particles for producing the heat insulating material for building materials of the present invention has high safety to the environment and living organisms. In particular, the tetrabromobisphenol A derivative is applied to the polystyrene resin foam molded article. When added, it can provide sufficient flame retardancy and is highly safe for the environment and organisms.
The expandable polystyrene resin particles for producing a heat insulating material for building materials of the present invention are obtained in comparison with those in which the flame retardant is uniformly present in the resin particles and the flame retardant is non-uniformly present in the resin particles. The mechanical strength of the foamed molded article (the heat insulating material for building materials) is increased, and a heat insulating material for building materials having excellent moldability and dimensional stability can be obtained.

  In the production method according to the present invention, a resin raw material having a low content of an aromatic organic compound composed of a styrene monomer, ethylbenzene, isopropylbenzene, normal propylbenzene, xylene, toluene, and benzene is selected as a polystyrene resin as a raw material. For example, since the expandable polystyrene resin particles can be obtained without mixing the aromatic organic compound in the production process, the obtained expandable polystyrene resin particles for manufacturing a heat insulating material for building materials are the aromatic organic compounds. The total content of the compound can be less than 500 ppm. The total content of the aromatic organic compound is more preferably 450 ppm or less, and still more preferably 400 ppm or less. If the total content of the aromatic organic compound is low, it will be possible to cope with sick house syndrome, which has been recently requested, and it will be suitable for use in the production of heat insulating materials for building materials.

In the present invention, the total content of the aromatic organic compound is a value measured by the following <Measurement method of volatile organic compound (VOC) content>.
<Measurement method of volatile organic compound (VOC) content>
Weigh accurately 1 g of expandable polystyrene resin particles, add 1 ml of a dimethylformamide solution containing 0.1% by volume of cyclopentanol as an internal standard solution, and then add dimethylformamide to the dimethylformamide solution to measure 25 ml. A solution was prepared, and 1.8 μl of this measurement solution was supplied to a 230 ° C. sample vaporization chamber to obtain a chart of each volatile organic compound detected by a gas chromatograph. And based on the calibration curve of each volatile organic compound measured beforehand, the amount of volatile organic compounds was calculated from each chart, and the amount of volatile organic compounds in the expandable polystyrene resin particles was calculated.
In the present invention, among the volatile organic compound (VOC) contents described above, the total amount of each volatile organic compound corresponding to the aromatic organic compound is defined as “total amount of aromatic organic compound”.

The expandable polystyrene resin particles for manufacturing a building insulation material obtained by the manufacturing method according to the present invention are pre-expanded by heating by steam heating or the like using a well-known apparatus and method in the field of manufacturing a foamed resin molding. And pre-expanded particles for production of heat insulating materials for building materials (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 foamed molded article (building material heat insulating material) to be manufactured. In the present invention, its bulk density is not limited, usually in the range of 0.010~0.050g / cm ^3, it is preferable to be within a range of 0.015~0.033g / cm ^3.

In the present invention, the bulk density of the pre-expanded particles is measured as follows.
<Bulk density and bulk expansion ratio of pre-expanded particles>
First, Wg was sampled from pre-expanded particles as a measurement sample, and this measurement sample was allowed to fall naturally into a graduated cylinder, and then the apparent volume (V) cm ³ of the sample was made constant by tapping the bottom of the graduated cylinder. And the volume is measured, and the bulk density of the pre-expanded particles is measured based on the following formula.
Bulk density (g / cm ³ ) = mass of measurement sample (W) / volume of measurement sample (V)
The bulk expansion ratio of the pre-expanded particles is a numerical value calculated by the following formula.
Bulk foam multiple (times) = 1 / bulk density (g / cm ³ )

The pre-expanded particles can be obtained by filling the pre-expanded particles into a cavity of a molding die using a well-known apparatus and technique in the field of manufacturing a foamed resin molded body, and heating them by steam heating or the like to perform in-mold foam molding. Manufactures heat insulating materials for building materials consisting of flame-retardant polystyrene-based resin foam moldings.
Although the density of the building material for the heat insulating material of the present invention is not particularly limited, usually in the range of 0.010~0.050g / cm ^3, preferably in the range of 0.015~0.033g / cm ³ .

In addition, in this invention, the density of a foaming molding is a density measured by the method of JISK7122: 1999 "Measurement of foaming plastics and rubber-apparent density".
<Density and expansion ratio of foamed molded product>
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.
Further, the expansion factor of the foamed molded product is a numerical value calculated by the following equation.
Foaming multiple (times) = 1 / density (g / cm ³ )

In the heat insulating material for building materials of the present invention, the average chord length of the bubbles is preferably in the range of 50 to 350 μm, more preferably in the range of 60 to 300 μm, with respect to the foamed molded product having a foaming ratio of 40 times. In addition, in this invention, the average chord length of a bubble is an average chord length of the bubble of a foaming molding measured by the following method.
<Average string length>
The average chord length of the bubbles of the foam molded article refers to that measured according to the test method of ASTM D2842-69. Specifically, the foamed molded body is cut into approximately equal halves, and the cut surface is photographed at a magnification of 100 times using a scanning electron microscope (trade name “S-3000N” manufactured by Hitachi, Ltd.). The photographed image is printed on A4 paper, and a straight line having a length of 60 mm is drawn at an arbitrary position, and the average chord length (t) of the bubbles is calculated from the following formula from the number of bubbles existing on the straight line.
Average string length t = 60 / (number of bubbles × photo magnification)
When drawing a straight line, if the straight line is in point contact with the bubble, this bubble is included in the number of bubbles, and both ends of the straight line are not penetrating the bubble and are in the bubble. In this case, the bubbles in which both ends of the straight line are positioned are included in the number of bubbles. Further, the average chord length is calculated in the same manner as described above at any five locations in the photographed image, and the arithmetic mean value of these average chord lengths is set as the average chord length of the bubbles of the foam molded body.

[Example 1]
(Manufacture of expandable polystyrene resin particles)
Tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether) as a flame retardant with respect to 100 parts by mass of a polystyrene resin (trade name “HRM-10N” manufactured by Toyo Styrene Co., Ltd.) as a base resin 7 parts by mass of a polystyrene resin masterbatch (made by Daiichi Kogyo Seiyaku Co., Ltd.) containing 50% by mass (equivalent to 3.5 parts by mass of flame retardant) and 0.3 parts by mass of finely powdered talc are uniformly mixed in advance using a tumbler mixer. After being fed into a single-screw extruder with a diameter of 90 mm at a rate of 160 kg / hr per hour, the resin is heated and melted, and then 6 parts by mass of isopentane as a foaming agent is added to the resin in the middle of the extruder. More press fit. 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 190 ° C., it is connected to the extruder and held at 320 ° C. by a heater, diameter 0.6 mm Then, through a granulation die having 200 nozzles with a land length of 3.0 mm, it is extruded into a chamber in which cooling water at 30 ° C. circulates, and at the same time, a high-speed rotary cutter having 10 blades in the circumferential direction is used as the die Adhered, cut at 3000 rpm, dehydrated and dried to obtain spherical expandable polystyrene resin particles. The obtained expandable resin particles had no average deformation and no whisker, and had an average particle size of 1.1 mm.
Polyethylene glycol 0.03 parts by mass, zinc stearate 0.15 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 foam moldings)
The expandable polystyrene resin particles produced as described above are placed in a 15 ° C. cool box and allowed to stand for 72 hours, and then supplied to a cylindrical batch type pre-foaming machine to generate steam with a blowing pressure of 0.05 MPa. To obtain pre-expanded particles. The obtained pre-expanded particles had a bulk density of 0.015 g / cm ³ (bulk expansion ratio: 67 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 50 mm. Thereafter, the inside of the cavity of the mold is heated with water vapor at a gauge pressure of 0.08 MPa for 20 seconds, and then cooled until the pressure in the cavity of the mold reaches 0.01 MPa. Opened, a rectangular foam molded body having a length of 400 mm, a width of 300 mm, and a height of 50 mm was taken out. The obtained foamed molded product had a density of 0.015 g / cm ³ (foaming factor 67 times).

  The following evaluation tests were performed on the expandable polystyrene resin particles, pre-expanded particles, and expanded molded articles of Example 1 produced as described above.

<Measurement of flame retardant decomposition temperature>
20 mg of the flame retardant composition was sampled and used as a sample, using a differential heat and calorie simultaneous measurement device TG / DTA 300 type (manufactured by Seiko Denshi Kogyo Co., Ltd.), a nitrogen gas amount of 30 ml / min, a heating temperature of 10 ° C./min, The mass reduction rate of the sample is measured at a measurement temperature of 30 to 800 ° C., and a graph is obtained with the mass reduction rate of the sample on the vertical axis and the temperature on the horizontal axis. And based on the obtained graph, the temperature when the mass reduction rate of the sample reached 5% was defined as “5 mass% decomposition temperature”.

<Measurement of volatile organic compound (VOC) content in expandable polystyrene resin particles>
Weigh accurately 1 g of expandable polystyrene resin particles, add 1 ml of a dimethylformamide solution containing 0.1% by volume of cyclopentanol as an internal standard solution, and then add dimethylformamide to the dimethylformamide solution to measure 25 ml. A solution was prepared, and 1.8 μl of this measurement solution was supplied to a 230 ° C. sample vaporization chamber, and each volatile organic compound detected by a gas chromatograph (manufactured by Shimadzu Corporation, trade name “GC-14A”) under the following measurement conditions. Based on the calibration curve of each volatile organic compound measured in advance, the amount of volatile organic compound was calculated from each chart, and the volatile organic compound in the expandable polystyrene particles was obtained. The amount was calculated.
Detector: FID
Column: GL Sciences (3mmφ × 2.5m)
Liquid phase: PEG-20M PT 25%
Carrier; Chromosorb W AW-DMCS
Mesh: 60/80
Column temperature: 100 ° C
Detector temperature: 230 ° C
DET temperature: 230 ° C
Carrier gas (nitrogen)
Carrier gas flow rate (40ml / min)

<Evaluation of bead foamability>
After the expandable polystyrene resin particles obtained in the examples (and comparative examples) were stored in a 15 ° C. cool box for 72 hours, this was supplied to a cylindrical batch type pre-foaming machine, and the blowing vapor pressure was 0.05 MPa. The pre-expanded particles obtained were heated for 2 minutes with water vapor and the bulk expansion ratio of the pre-expanded particles was measured as follows, and the following evaluation criteria:
○ (good) when the foam expansion ratio is 60 times or more
△ (slightly good) when the bulk expansion ratio is 50 times or more and less than 60 times,
The bead foaming property was evaluated in light of x (defective) when the bulk expansion ratio was less than 50 times.

<Evaluation of flame retardancy>
It was measured by the method described in JIS A 9511: 1995 “Foamed plastic heat insulating material” measuring method A.
For the test piece, 5 pieces of 10 mm thickness, 200 mm length and 25 mm width are cut out from the foamed molded body sample, and a prescribed ignition limit instruction line and combustion limit instruction line are attached. After the test piece was burned to the ignition limit indicator line with a candle for a fire source, the flame was retreated, the time (seconds) from the moment to the extinguishing of the flame was measured, and the flame retardance was judged according to the following criteria.
○ (Good): Flames disappeared within 3 seconds for all five test specimens and there was no residual dust.
X (defect): The standard of ○ was not satisfied, or there was no self-extinguishing property.

<Appearance evaluation of foam molding>
The polystyrene resin pre-expanded particles were filled into a mold of a foam molding machine and subjected to secondary foaming using water vapor to obtain a rectangular foam-shaped foam molded body having a length of 400 mm, a width of 300 mm, and a thickness of 50 mm.
The appearance of the foamed molded product was visually observed and evaluated based on the following criteria.
A (very good): There is no gap between the expanded particles, and the surface is very smooth.
○ (good): There is no gap between the expanded particles, and the surface is smooth.
Δ (slightly good): There are few gaps between the expanded particles, and the surface smoothness is slightly inferior.
X (Poor): The gap between the expanded particles is large, and the smoothness of the surface is considerably inferior.

<Evaluation of heat insulation of foamed molded product>
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 foamed molded body. And the heat conductivity of this test piece was measured at the measurement temperature of 23 degreeC by the flat plate heat flow meter method based on JISA1412, and the following reference | standard determined.
○ ・ ・ ・ The thermal conductivity is less than 0.040 (W / m ・ k) × ・ ・ ・ The thermal conductivity is 0.040 (W / m ・ k) or more

<Comprehensive evaluation>
For each of the evaluation items <evaluation of bead foamability>, <evaluation of flame retardancy>, <appearance evaluation of foamed molded product>, and <evaluation of heat insulating property of foamed molded product> The evaluation was good (◯), and one having one or more defects (x) was comprehensively evaluated as a defect (x).

[Example 2]
As the flame retardant, foam molding with an expansion ratio of 67 times was performed in the same manner as in Example 1 except that the same amount of tetrabromobisphenol A-bis (2,3-dibromopropyl ether) (Daiichi Kogyo Seiyaku Co., Ltd.) was used. The body was manufactured.

[Example 3]
A foamed molded article having a foam expansion factor of 67 times was produced in the same manner as in Example 1 except that the same amount of tetrabromobisphenol A-bis (allyl ether) (Daiichi Kogyo Seiyaku Co., Ltd.) was used as the flame retardant.

[Example 4]
Except that 3.2 parts by mass of tetrabromobisphenol A-bis (2,3-dibromopropyl ether) and 0.3 parts by mass of tetrabromobisphenol A-bis (allyl ether) were used as flame retardants, In the same manner as in Example 1, a foamed molded article having a foam multiple of 67 times was produced.

[Example 5]
A foamed molded product was produced in the same manner as in Example 1 except that the bulk foaming factor of the pre-expanded particles was 40 times and the foaming factor of the foamed molded product was 40 times. The average chord length of bubbles in this foamed molded product was 183 μm.

[Comparative Example 1]
A foamed molded article was produced in the same manner as in Example 1 except that the same amount of hexabromocyclododecane (Daiichi Kogyo Seiyaku Co., Ltd.) was used as the flame retardant.

[Comparative Example 2]
A foamed molded article was produced in the same manner as in Example 1 except that the same amount of tris- (2,3-dibromopropyl) isocyanurate (Nihon Kasei Co., Ltd.) was used as the flame retardant.

[Comparative Example 3]
A foamed molded article was produced in the same manner as in Example 1 except that the same amount of pentabromobenzyl acrylate (Daiichi Kogyo Seiyaku Co., Ltd.) was used as the flame retardant.

[Comparative Example 4]
A foamed molded article was produced in the same manner as in Example 1 except that the same amount of tris (tribromoneopentyl) phosphate (manufactured by Daihachi Chemical Co., Ltd.) was used as a flame retardant.

Table 1 summarizes the bromine content of the flame retardants used in Examples 1 to 5 and Comparative Examples 1 to 4, the presence or absence of a benzene ring in the flame retardant molecule, and the 5 mass% decomposition temperature.
Moreover, the measurement and evaluation results of Examples 1 to 5 and Comparative Examples 1 to 4 are summarized in Table 2.

From the results of Tables 1 and 2, the examples have bromine atoms in the molecule, the bromine content is less than 70% by mass, the molecule has a benzene ring, and the flame retardant has a 5% by mass decomposition temperature. In Examples 1 to 5 according to the present invention using the flame retardants A to C in the range of 200 to 300 ° C., the bead foamability, flame retardancy, and the appearance of the foam were all good.
On the other hand, Comparative Example 1 using the flame retardant D having a high bromine content of 75% by mass and having no benzene ring in the molecule had poor bead foaming properties.
Moreover, the comparative example 2 which used the flame retardant E without a benzene ring in a molecule | numerator became bad in bead foaming property, the external appearance of a foam, and heat insulation.
In addition, Comparative Example 3 using the flame retardant F having a high bromine content of 75% by mass and a 5% by mass decomposition temperature exceeding 300 ° C. was poor in flame retardancy and heat insulation.
Comparative Example 4 using a flame retardant G having a high bromine content of 75% by mass, no benzene ring in the molecule and a 5% by mass decomposition temperature exceeding 300 ° C. Both the appearance and heat insulation of the foam were poor.

  The present invention relates to a heat insulating material for building materials that has sufficient flame retardancy using a flame retardant that is highly safe against the environment and living organisms, and that is excellent in mechanical strength and dimensional stability. The heat insulating material for building materials according to the present invention is used by being disposed, for example, between joists or large pulls on the floor of a building, between columns and studs on walls, and between rafters on a roof.

  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 (11)

Expandable polystyrene resin particles for building material insulation production, which is made into a particulate polystyrene resin containing a flame retardant and a foaming agent,
The flame retardant has a bromine atom in the molecule, a bromine content of less than 70% by mass, a benzene ring in the molecule, and a 5% by mass decomposition temperature of the flame retardant of 200 to 300 ° C. Within the range of
A flame retardant and foaming agent are added to and kneaded with polystyrene resin in the resin supply device, and the molten resin containing the flame retardant / foaming agent is extruded directly into the cooling liquid through a small hole in the die attached to the tip of the resin supply device. Insulating material for building materials characterized by being obtained by a melt extrusion method in which extrudate is cut simultaneously with extrusion and the extrudate is cooled and solidified by contact with a liquid to obtain expandable polystyrene resin particles Expandable polystyrene resin particles for production.   2. The expandable polystyrene resin particles for producing a heat insulating material for building materials according to claim 1, wherein the total content of aromatic organic compounds comprising styrene monomer, ethylbenzene, isopropylbenzene, normal propylbenzene, xylene, toluene and benzene is less than 500 ppm. .   The expandable polystyrene resin particles for manufacturing a heat insulating material for building materials according to claim 1 or 2, wherein the flame retardant is one or more selected from the group consisting of tetrabromobisphenol A or a derivative thereof.   The flame retardant is tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (allyl ether) The expandable polystyrene resin particles for manufacturing a heat insulating material for building materials according to any one of claims 1 to 3, wherein the expandable polystyrene resin particles are one type or two or more types selected from the group consisting of:   Pre-expanded particles for manufacturing heat insulating materials for building materials, obtained by heating the expandable polystyrene resin particles for manufacturing heat insulating materials for building materials according to any one of claims 1 to 4. A building material having a density in the range of 0.010 to 0.050 g / cm ³ obtained by filling the pre-expanded particles for producing a heat insulating material for building material according to claim 5 into a cavity of a mold and heating and foaming. Insulation.   The pre-expanded particles for producing a building material heat insulating material according to claim 5 are filled in a cavity of a molding die, heated and foamed, and an average chord length of bubbles is 50 for a foamed molded article having a expansion ratio of 40 times. A heat insulating material for building materials in a range of ˜350 μm.   In the resin feeder, the polystyrene-based resin has a bromine atom in the molecule, a bromine content of less than 70% by mass, a benzene ring in the molecule, and a 5% by mass decomposition temperature of the flame retardant. Add and knead the flame retardant and foaming agent in the range of 200 to 300 ° C., and add the flame retardant / foaming agent-containing molten resin directly into the cooling liquid from the small hole of the die attached to the tip of the resin feeder In the method of extruding, cutting the extrudate at the same time as extrusion, and cooling and solidifying the extrudate by contact with a liquid to produce expandable polystyrene resin particles, styrene monomer, ethylbenzene, isopropylbenzene, normal propylbenzene, xylene The expandable polystyrene resin particles for manufacturing a heat insulating material for building materials according to claim 1 or 2 without using an aromatic organic compound consisting of benzene, toluene and benzene Method of manufacturing a building material for insulation material for producing expandable polystyrene resin particles characterized by obtaining.   The method for producing expandable polystyrene resin particles for manufacturing a heat insulating material for building materials according to claim 8, wherein the flame retardant is one or more selected from the group consisting of tetrabromobisphenol A or a derivative thereof.   The flame retardant is tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (allyl ether) The method for producing expandable polystyrene resin particles for producing a heat insulating material for building materials according to claim 9, which is one or more selected from the group consisting of:   11. The building material according to claim 8, wherein a master batch material containing the flame retardant at a predetermined concentration in a resin is supplied into the resin supply apparatus together with the polystyrene resin, and is melt-kneaded in the apparatus. The manufacturing method of the expandable polystyrene-type resin particle for heat insulating material manufacture.

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