JP4933812B2 - Styrenic resin extruded foam and method for producing the same - Google Patents

Description

  The present invention relates to a styrene resin extruded foam having high flame retardancy, and more particularly to a styrene resin extruded foam in which the flame retardant effect of a halogen flame retardant is improved and a method for producing the same.

  Styrenic resin extruded foam is used as a heat insulating material for structures, for example, because of good workability and heat insulating properties. Styrenic resin extruded foam is usually heated and melted in an extruder to form a gel, and then a foaming agent is added and kneaded to cool the gel-like styrene resin to a temperature suitable for foaming. Then, it is obtained by foaming by releasing the pressure to the low pressure region through the die and molding it into a plate shape.

  As the flame retardant added to the styrene resin, a halogen flame retardant such as hexabromocyclododecane is used. On the other hand, saturated hydrocarbons, halogenated hydrocarbons, and chlorofluorocarbons are known as foaming agents (see Patent Documents 1 and 2). In particular, halogenated hydrocarbons such as methyl chloride and ethyl chloride are easily permeable to styrenic resins and are widely used with other blowing agents. In particular, when a flammable gas such as hydrocarbon is used as a foaming agent, more flammable gas is required because the combustible gas remains in the extruded foam and combustion of the extruded foam is promoted. It tends to be said.

  However, when a large amount of the organic halogen flame retardant is added to the resin raw material, there are problems that the mechanical properties of the extruded foam are deteriorated and the metal portion of the extruder is corroded. In addition, there is a problem that the heat resistance of the extruded foam is lowered, and harmful substances are generated during molding and combustion. On the other hand, attempts have been made to reduce the amount of halogenated flame retardant added by using various additives in combination with halogenated flame retardants, but there has not yet been obtained a product that exhibits sufficient performance (patents) Literature 3 to Patent Literature 5). Furthermore, there exists knowledge that the molding defect of the flame-retardant thermoplastic resin composition containing a bromine-containing flame retardant arises by presence of metal oxides, such as iron oxide (patent documents 6, 7).

  By the way, in the global environment, the destruction of the ozone layer and the influence of chemical substances on the atmosphere or water quality are regarded as problems. For example, chlorofluorocarbons are considered as causative substances that destroy the ozone layer. In addition, methyl chloride and ethyl chloride are obligated to be notified when used as a Class 1 Designated Substance in the PRTR Law, and the emission amount is controlled. Accordingly, it is desired that a foaming agent used for producing a styrene resin extruded foam that does not adversely affect the global environment is employed. From this point of view, it has been proposed to use water as a foaming agent, but water is almost incompatible with styrenic resins and cannot be added in large quantities. If the amount of water added increases, there is a problem that water is not uniformly dispersed in the resin, and extrusion foaming is not stable or voids are generated in the extruded foam.

JP 52-17574 A JP-A-1-174540 JP 60-86143 A JP-A 62-199654 JP-A-3-265641 JP 2001-11322 A JP 2001-11323 A

  In view of such a background, an object of the present invention is to provide a means for obtaining a styrene resin extruded foam having a desired flame retardancy by adding a small amount of a halogen flame retardant. Another object of the present invention is to provide a means for obtaining a styrene resin extruded foam excellent in environmental compatibility.

  As a result of diligent research to solve the above-described problems, the present inventors have added a halogen-based flame retardant and a zeolite containing iron to a small amount of halogen-based flame retardant. The present inventors have found that an excellent flame retardant effect can be obtained with a flame retardant, and have completed the present invention.

(1) The present invention relates to 0.1 to 20 parts by weight of a halogen flame retardant, 5 to 15 parts by weight of a non-halogen foaming agent, and 0.01 to 9 parts by weight with respect to 100 parts by weight of a styrene resin. Of the styrene resin is obtained by extrusion foaming of the styrene resin, the zeolite containing 0.2 to 20% of iron element with respect to the zeolite. Ah is, less than the styrene resin extruded foam zinc element content contained in 0.03 wt%, the non-halogen blowing agents, a) dimethyl ether, diethyl ether, compounds selected from methyl ethyl ether And b) water, and optionally c) one or more saturated hydrocarbons having 3 to 5 carbon atoms, and d) carbon dioxide.

  (2) Natural zeolite or artificial zeolite can be considered as the zeolite.

(3) As the halogen flame retardant, one or both of hexabromocyclododecane and tetrabromocyclooctane can be considered.

(4) As the one or more saturated hydrocarbons having 3 to 5 carbon atoms, those selected from the group consisting of propane, n-butane, and i-butane are considered.

(5) It is considered that water as the foaming agent contains the iron oxide.

(6) The present invention is useful when the foam density of the extruded styrene resin foam is 20 to 40 kg / m ³ .

(7) The method for producing an extruded foam of a styrene resin according to the present invention comprises 0.1 to 20 parts by weight of a halogenated flame retardant and 5 to 15 parts by weight of a non-halogen based on 100 parts by weight of a styrene resin. A styrene resin having a foam density of 20 to 40 kg / m 3 is obtained by adding a foaming agent and 0.01 to 9 parts by weight of zeolite and extruding the styrene resin from a high pressure region to a low pressure region through a die. be those obtaining extruded foam, the zeolite are those containing from 0.2 to 20% of the iron element with respect to the zeolite, zinc element content contained in the styrene resin extruded foam Is less than 0.03% by weight, and the non-halogen-based blowing agent includes: a) a compound selected from dimethyl ether, diethyl ether, and methyl ethyl ether; b) water; and c) charcoal as necessary. The number is one which contains and one or more saturated hydrocarbon is 3 to 5, d) and carbon dioxide, a.

  Thus, according to the styrene resin extruded foam and the method for producing the same according to the present invention, a halogen-based flame retardant, a non-halogen-based foaming agent, and a zeolite containing at least iron are added to the styrene resin, Since the styrene resin is obtained by extrusion foaming, an excellent flame retardant effect can be obtained with a small amount of halogen flame retardant.

  In addition, according to the styrene resin extruded foam and the method for producing the same according to the present invention, the styrene resin has a halogen flame retardant, a non-halogen foam, zeolite, and 1 to 20 parts added to the zeolite. % Iron oxide is added, and the styrene resin is obtained by extrusion foaming. Therefore, an excellent flame retardant effect can be obtained with a small amount of halogen flame retardant.

  The styrene resin used in the present invention is not particularly limited, and is obtained from a styrene homopolymer obtained only from a styrene monomer, a monomer copolymerizable with styrene monomer and styrene, or a derivative thereof. Random copolymers, block copolymers or graft copolymers, modified polystyrenes such as brominated polystyrene and rubber-reinforced polystyrene are used. These are used alone or in admixture of two or more.

  Examples of monomers copolymerizable with styrene include methylstyrene, dimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, bromostyrene, dibromostyrene, tribromostyrene, chlorostyrene, dichlorostyrene, and trichlorostyrene. Polyfunctional vinyl compounds such as divinylbenzene, (meth) acrylic compounds such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylonitrile, diene compounds such as butadiene or the like Derivatives, unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride and the like. These are used alone or in admixture of two or more.

  Among styrenic resins, styrene homopolymer is preferable from the viewpoint of processability.

  The styrene resin used in the present invention may be a mixture of recycled polystyrene resin and virgin polystyrene resin. The mixing ratio of the recycled polystyrene resin and the virgin polystyrene resin is preferably 5 to 100% by weight of the recycled polystyrene resin and 95 to 0% by weight of the virgin polystyrene resin, more preferably the recycled polystyrene resin. Is 40 to 100% by weight, and virgin polystyrene resin is 60 to 0% by weight. If the mixing ratio of recycled polystyrene resin and virgin polystyrene resin exceeds the above range and the amount of recycled polystyrene resin increases, the physical properties (such as relative viscosity) of the resin raw material decrease, and the desired moldability and physical properties (flammability, There is a tendency that an extruded foam having a foam density or the like cannot be obtained. On the other hand, if the mixing ratio exceeds the above range and the amount of virgin polystyrene resin increases, the physical properties of the resin raw material and the extruded foam will be good, but the amount of recycled polystyrene resin used will be reduced. Can't contribute.

  Recycled polystyrene resin is obtained from general waste after being used as a molded product of styrene resin. Examples of general waste of molded products include trays, buffer materials, boxes, and the like. The recycled polystyrene resin can also be obtained from surplus materials such as mill ends generated when processing an extruded foam of a styrene resin, for example. Recycled polystyrene resin obtained from general waste is already used, so there is a risk that the resin will deteriorate or other types of resin molded products may be mixed during collection and separation. However, it has a large supply amount and is inexpensive. Recycled polystyrene-based resin obtained from the extruded foam surplus is unused but is less likely to be mixed with other types of resin molded products. However, the supply amount is small and expensive. In recycled polystyrene-based resins obtained from general waste, after used waste is separated and coarsely pulverized, it is reduced to pellets by heating, etc. Some are dissolved and gelled, then recovered, regenerated, and pelletized. Usually, the former is low quality, but the supply amount is large and inexpensive, and the latter is high quality, but the supply amount is small and expensive. On the other hand, virgin polystyrene resin is used for the first time as a raw material of a molded product.

  The halogen flame retardant used in the present invention may be a compound having a halogen atom. Examples of such halogen flame retardants include, as bromine flame retardants, hexabromocyclododecane, tetrabromocyclooctane, dibromoneopentyl glycol, tribromoneopentyl alcohol, tris (tribromoneopentyl) phosphate, tris (2 , 3-dibromopropyl) isocyanurate, bromides of aliphatic or alicyclic hydrocarbons such as tetrabromoethane, hexabromobenzene, ethylenebispentabromodiphenyl, decabromodiphenylethane, decabromodiphenyl ether, octabromodiphenyl ether, 2 Brominated aromatic compounds such as 1,3-dibromopropylpentabromophenyl ether, tetrabromobisphenol A, tetrabromobisphenol A bis (2,3-dibromopropyl ether) Ter), tetrabromobisphenol A (2-bromoethyl ether), tetrabromobisphenol A diglycidyl ether, tetrabromobisphenol A bis (allyl ether), adducts of tetrabromobisphenol A diglycidyl ether and tribromophenol, etc. Brominated bisphenols and derivatives thereof, tetrabromobisphenol A polycarbonate oligomers, brominated bisphenol derivatives oligomers such as epoxy oligomers of addition products of tetrabromobisphenol A diglycidyl ether and brominated bisphenol, ethylene bistetrabromophthalimide, bis ( 2,4,6-tribromophenoxy) ethane brominated aromatic compounds, brominated acrylic resins, ethylenebisdibromonorbornane dica Bokishiimido and the like.

Among such halogen-based flame retardants, it is a halogen-based flame retardant satisfying a 240% to 290 ° C. 5% weight loss temperature (° C.) under nitrogen at a temperature rising rate of 10 ° C./min. More preferably, the 5% weight loss temperature is 250 to 280 ° C. The 5% weight loss temperature can be measured by a thermogravimetric method or the like using a general thermogravimetric measuring device such as TGA-50 or DTG-50 manufactured by Shimadzu Corporation. More specifically, using a DTG-50 manufactured by Shimadzu Corporation, a nitrogen stream of 50 mL / min, a heating rate of 10 ° C./min, a sample of about 3.5 mg, a control Al ₂ O ₃ , 5% weight under nitrogen What is necessary is just to measure a decreasing temperature. Among such halogen flame retardants, hexabromocyclododecane and tetrabromocyclooctane are more preferable.

  Examples of the chlorinated flame retardant include chlorinated aliphatic compounds such as chlorinated paraffin, chlorinated naphthalene, and perchloropentadecane, chlorinated aromatic compounds, and chlorinated alicyclic compounds. Of these, brominated flame retardants are preferable from the viewpoint of flame retardancy, and hexabromocyclododecane and tetrabromocyclooctane are particularly preferable from the viewpoint of compatibility with styrene resins. These are used either alone or as a mixture of both.

  The addition amount of the halogen-based flame retardant is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 6.0 parts by weight with respect to 100 parts by weight of the styrene resin. If content of a halogenated flame retardant is the said range, a flame retardance will become favorable and the fall of the glass transition temperature of an extrusion foam will be suppressed, and heat resistance will be maintained.

  In the present invention, a flame retardant such as a phosphate ester compound or a nitrogen-containing compound may be further coexisted with the halogen flame retardant. Specific examples of phosphoric acid ester compounds include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate (preferably those having 1 to 12 carbon atoms as the alkyl group), tri Trialkoxyalkyl phosphates such as butoxyethyl phosphate (alkoxyalkyl groups preferably having 2 to 12 carbon atoms), dialkyl phosphates (alkyl groups preferably having 1 to 12 carbon atoms), monoisodecyl phosphate, etc. Fatty substances such as monoalkyl phosphates (alkyl groups having 1 to 12 carbon atoms are preferred), 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate Phosphates, triphenyl phosphate, tricresyl phosphate, trixyl phosphate, tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylyl diphenyl phosphate, di (isopropyl Triaryl phosphates such as phenyl) phenyl phosphate (the rule group may be substituted with an alkyl group, a phenyl group, etc.), diphenyl (2-ethylhexyl) phosphate, diphenyl (2-acryloyloxyethyl) phosphate, diphenyl (2- Methacryloyloxyethyl) phosphates such as diarylalkyl phosphates (aryl groups, alkyl groups may be substituted) Such group based phosphate esters. The content of the phosphoric ester compound is preferably 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the styrene resin in terms of obtaining a flame retardant synergistic effect with the halogen flame retardant and / or the nitrogen-containing compound. .

  Specific examples of the nitrogen-containing compound include monoalkyl cyanurates such as cyanuric acid and methyl cyanurate, dialkyl cyanurates such as diethyl cyanurate, trialkyl cyanurates such as trimethyl cyanurate and triethyl cyanurate, phenyl cyanurate, and diphenyl. Dialkyl phenyl cyanurates such as cyanurate, triphenyl cyanurate, dimethylphenyl cyanurate, monoalkyl isocyanurates such as isocyanuric acid and methyl isocyanurate, dialkyl isocyanurates such as diethyl isocyanurate, trimethyl isocyanurate, triethyl isocyanurate, etc. Trialkyl isocyanurate, phenyl isocyanurate, diphenyl isocyanurate, triphenyl isocyanurate, Dialkylphenyl isocyanurates such as methylphenyl isocyanurate, mono (aminoalkyl) isocyanurates such as mono (2-aminoethyl) isocyanurate, di (aminoalkyl) isocyanurates such as di (2-aminoethyl) isocyanurate, tri Tri (aminoalkyl) isocyanurate such as (2-aminoethyl) isocyanurate, tri (hydroxymethyl) isocyanurate, tri (2-hydroxyethyl) isocyanurate, tri (2-hydroxypropyl) isocyanurate Bis (carboxyl) such as di (hydroxyalkyl) isocyanurate such as alkyl) isocyanurate, di (hydroxymethyl) isocyanurate, and bis (2-carboxyethyl) isocyanurate Kill) isocyanurate, 1,3,5-tris (2-carboxyethyl) isocyanurate and the like 1,3,5-tris (carboxyalkyl) isocyanurate, tris (2,3-epoxypropyl) isocyanurate and the like It is done. The content of the nitrogen-containing compound is preferably 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the styrenic resin in terms of obtaining a flame retardant synergistic effect with the halogen-based flame retardant and / or the phosphate ester compound. .

  The non-halogen-based blowing agent used in the present invention is not particularly limited. Specifically, a) a compound selected from dimethyl ether, diethyl ether, and methyl ethyl ether, b) water, and, if necessary, c) carbon The thing containing 1 or more types of saturated hydrocarbons whose number is 3-5, and d) carbon dioxide is considered.

  The compound selected from the group consisting of dimethyl ether, diethyl ether, and methyl ether used as a foaming agent in the present invention can be arbitrarily used alone or as a mixture of two or more thereof. It is preferable to be used alone.

  The addition amount of dimethyl ether is preferably 1 to 5 parts by weight, more preferably 2 to 4 parts by weight with respect to 100 parts by weight of the styrene resin. When the addition amount of dimethyl ether is within the above range, the plasticizing action to the styrene resin by the foaming agent in the extrusion foaming is effectively exhibited, and the extruded foam can be stably molded. Moreover, sustained release by excess dimethyl ether is suppressed.

  In the present invention, the water used as the foaming agent is preferably 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight with respect to 100 parts by weight of the styrenic resin. By setting the amount of water to be in the above range, the amount of other foaming agent used can be relatively reduced, the amount of combustible gas can be reduced, and an extruded foam excellent in environmental performance can be obtained. In addition, compatibility with the styrene resin is maintained, good moldability is maintained without extrusion of water or steam during extrusion foaming, and molding defects such as voids do not occur.

  If necessary, the blowing agent may be confused with one or more saturated hydrocarbons having 3 to 5 carbon atoms and carbon dioxide. Examples of the one or more saturated hydrocarbons having 3 to 5 carbon atoms include propane, n (normal) -butane, and i (iso) -butane. From the viewpoint of foamability and heat insulating performance of the extruded foam, n-butane, i-butane, and a mixture of n-butane and i-butane are particularly preferable. Further, carbon dioxide is added to the foaming agent in place of the saturated hydrocarbon, so that combustible gas is reduced and an extruded foam having excellent environmental properties can be obtained. Of course, both saturated hydrocarbon and carbon dioxide may be mixed as a blowing agent.

The amount of foaming agent used is appropriately changed according to the setting value of the foaming ratio, etc., but when trying to obtain a lightweight foam having a foam density of 20 to 40 kg / m ³ , the total amount of foaming agent The amount is preferably 5 to 15 parts by weight, more preferably 6 to 12 parts by weight, based on 100 parts by weight of the styrenic resin. If the addition amount of the foaming agent is less than 5 parts by weight, the expansion ratio is low, and characteristics such as light weight and heat insulation as an extruded foam may be difficult to be exhibited. On the other hand, when the addition amount of the foaming agent exceeds 15 parts by weight, molding defects such as voids tend to occur in the extruded foam due to the excessive foaming agent amount.

  In the present invention, the following foaming agents may be used in addition to the above foaming agents. Examples of such foaming agents include dimethyl ketone, methyl ethyl ketone, diethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl i-butyl ketone, methyl n-amyl ketone, methyl n-hexyl ketone, ethyl n-propyl ketone, Ketones such as ethyl n-butyl ketone, formic acid methyl ester, formic acid ethyl ester, formic acid propyl ester, formic acid butyl ester, formic acid amyl ester, propionic acid methyl ester, propionic acid methyl ester and other carboxylic acid esters, and inorganic foam such as nitrogen And chemical foaming agents such as azo compounds. These foaming agents are appropriately added to such an extent that the production, appearance and physical properties of the extruded foam are not impaired.

  The zeolite used in the present invention contains at least iron, and specific examples include natural zeolite and artificial zeolite. Zeolite is a general term for crystalline aluminosilicates that have a unique three-dimensional framework structure and have many pores of angstrom units. Zeolite generally has (a) adsorption separation using the difference in polarity between molecules, (b) separation of molecules with slightly different sizes and shapes, and (c) pore exchange by ion exchange. It can be finely adjusted in diameter, (d) has a large cation exchange capacity and can be exchanged with Fe ions, and (e) has a large pore volume and therefore has a large amount of adsorption.

  Natural zeolites are mined as minerals mainly composed of mordenite and / or clinoptilolite. Artificial zeolite is made from coal ash fly ash as a raw material, dried, pulverized, and particle-size processed into industrially usable powder. Both natural zeolite and artificial zeolite have a large cation exchange capacity, and cations to be exchanged are generally Na ions, K ions, and Ca ions, but can be exchanged for Fe ions. Both natural zeolite and artificial zeolite are generally commercially available.

  The average particle size of the zeolite is not particularly limited, but a fine particle of 15 μm or less is preferable, more preferably 13 μm or less, and still more preferably 5 μm or less. By using a zeolite in this range, the dispersion in the styrene resin is improved, and an extruded foam without foreign matter generation tends to be obtained. In addition, the dispersion of water as a foaming agent into the styrene resin is improved, and the occurrence of voids and cell (bubble) unevenness tends to be reduced.

  In the zeolite containing iron exemplified in natural zeolite and artificial zeolite, the content of iron element is preferably 0.2 to 20%, more preferably 0.5 to 11%, still more preferably 0.5 to 6%. is there. The iron contained in the zeolite may contain Fe ions by ion exchange. By setting the iron element content of the zeolite within the above range, the flame retardant effect on the extruded foam is effectively exhibited. In addition, decomposition of the halogen flame retardant in the extrusion system (heating, melting, kneading) is suppressed, and the flame retardant effect is effectively exhibited. Furthermore, deterioration of the styrene resin in the extrusion system is prevented, and the combustibility of the extruded foam is improved.

In the present invention, a synthetic zeolite not containing iron and iron oxide may be used in combination. The iron oxide used in the present invention is an inorganic compound containing iron and oxygen. For example, FeO (ferrous oxide), Fe ₂ O ₃ (ferric oxide), Fe ₃ O ₄ (triiron tetraoxide) , FeOOH (ferric oxyhydroxide), Fe (OH) ₂ (ferrous hydroxide), Fe (OH) ₃ (ferric hydroxide), iron rust (red rust, yellow rust, black rust, etc.), FeSO ₄ (ferrous sulfate), Fe ₂ (SO ₄ ) ₃ (ferric oxide), Fe (NO ₃ ) ₂ (ferrous nitrate), Fe (NO ₃ ) ₃ (ferric nitrate), Fe ₃ (PO ₄ ) ₂ (ferrous phosphate), FePO ₄ (ferric phosphate), FeTiO ₃ (iron titanate), FeMoO ₄ (iron molybdate), FeWO ₄ (iron tungstate) and the like. It is done. Among these iron oxides, there are various types of crystal structures such as α-type, β-type, γ-type, and amorphous type, but these types are not particularly limited. These iron oxides may be hydrates. These are used individually or in mixture of 2 or more types.

  The amount of iron oxide added is preferably 1 to 20%, more preferably 3 to 15%, based on the number of zeolites added to the styrenic resin. By setting the addition amount of iron oxide within the above range, the flame-retardant effect on the extruded foam is effectively exhibited. Further, the halogen flame retardant is prevented from being decomposed in the extrusion system, and the flame retardant effect is effectively exhibited. Furthermore, deterioration of the styrene resin in the extrusion system is prevented, and the combustibility of the extruded foam is improved.

  The zeolite used in the present invention is preferably added in an amount of 0.01 to 9 parts by weight, more preferably 0.03 to 2 parts by weight, based on 100 parts by weight of the styrene resin. By making the amount of zeolite added in the above range, when water is used as a foaming agent, dispersibility in styrene-based resin is improved, and voids, molding defects such as water or steam being ejected during extrusion foaming, etc. Does not occur. In addition, the amount of contained iron or iron oxide accompanying the zeolite is suppressed, and the flame retardant effect is maintained by energizing the decomposition of the halogen flame retardant. Further, deterioration of the styrene resin in the extrusion system is prevented, and the combustibility of the extruded foam is improved. Furthermore, the wear of the mold for extrusion foam molding by zeolite is suppressed, the maintenance period of the mold is extended, and the long run property of the manufacturing is improved.

  In the present invention, a flame retardant aid is preferably added to the styrene-based resin composition. As the flame retardant aid, metal salt hydration having a crystal water dissociation temperature (temperature for dissociating crystal water) of 200 ° C. or less. Products or metal salts, but those other than zinc compounds are preferred. Compared to iron and iron oxide contained in zeolite, the zinc compound has a higher action of thermally decomposing halogen flame retardants, so it is assumed that the temperature at which the halogen flame retardant begins to thermally decompose is significantly reduced. As a result of the accelerated thermal decomposition of the halogen-based flame retardant in the extrusion system, it is considered that the amount of effective flame retardant is reduced and the flame retardant effect is lowered. Moreover, it is assumed that deterioration of the styrene resin is also caused in the extrusion system, and as a result, the styrene resin easily burns, and it is considered that the combustibility is deteriorated.

  Examples of the zinc compound include zinc stearate, zinc oxide, zinc borate, zinc stearate, zinc laurate, zinc palmitate, zinc benzoate, and zinc carbonate. Accordingly, the flame retardant aid is preferably a substance other than a zinc compound, for example, magnesium sulfate hydrate, sodium sulfate hydrate, calcium sulfate hydrate, aluminum sulfate hydrate, copper sulfate hydrate, sulfuric acid Examples thereof include iron hydrate, sodium phosphate hydrate, magnesium phosphate hydrate, sodium carbonate hydrate, magnesium carbonate hydrate, boric acid, and sodium metaborate hydrate. These are used alone or in admixture of two or more.

  The metal salt hydrate preferably has a crystal water dissociation temperature of 200 ° C. or less, and more preferably dissociates crystal water in a large amount at 100 to 200 ° C.

  Of the above metal salt hydrates, magnesium sulfate hydrate is particularly preferable from the viewpoints of extrusion stability, safety, and harmfulness. Regarding the extrusion stability, when there is a lot of water dissociation from the metal salt hydrate at room temperature to about 60 ° C, the inside of the extrusion system tends to become unstable, but magnesium sulfate hydrate is room temperature to 60 ° C. Since there is very little dissociation of water at a degree, the extrusion system tends to be stable. Magnesium sulfate hydrate has an advantage that it is easy to handle because it is highly safe and hardly harmful.

  The metal salt hydrate absorbs a large amount of heat when water is released at a temperature of 200 ° C. or lower. Therefore, when the metal salt hydrate is present in a certain amount or more in the styrene resin extruded foam, a flammable foaming agent is formed. When combustion is started, the combustion heat is absorbed. Thereby, since the combustion of the foaming agent is not sustained, it is considered that flame retardancy is imparted to the styrene resin extruded foam. On the other hand, when the crystal water dissociation temperature of the metal salt hydrate exceeds 200 ° C., the timing for absorbing the combustion heat when the foaming agent burns is delayed, so that it becomes difficult to exhibit flame retardancy.

  The metal salt hydrate is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the styrene resin. By setting the metal salt hydrate to the above range, the amount of water contained in the extruded foam is maintained, a sufficient endothermic amount is obtained for the combustion heat of the foaming agent, and the flame retardant effect is exhibited. . Moreover, the moldability in extrusion foaming is maintained well, and the productivity, closed cell ratio, and foam density are improved.

  The hydrate amount of the metal salt hydrate (total molecular weight of water in the hydrate) is not particularly limited, and may be an anhydride. However, when metal salt anhydrides are used, water is used as a foaming agent, or moisture necessary for imparting a flame retardant effect is applied to the extruded foam, such as steam curing the extruded foam after foaming. Must be retained. The amount of water present in the extruded foam is preferably 0.05 to 1.5% by weight with respect to 100% by weight of the styrene resin extruded foam.

  In the present invention, a stabilizer may be used as necessary. Examples of the stabilizer used in the present invention include light-resistant stabilizers such as phenolic antioxidants, phosphorus stabilizers, benzotriazoles and hindered amines.

  In the present invention, inorganic compounds such as silica, talc, calcium silicate, wollastonite, kaolin, clay, mica, calcium carbonate, sodium stearate, Water absorption or water swelling of processing aids such as calcium phosphate, magnesium stearate, barium stearate, liquid paraffin, olefin wax, stearylamide compound, antistatic agent, colorant, epoxy compound, smectite, swellable fluoromica Additives such as water-absorbing substances such as hydrophilic layered silicates or organically treated products thereof, water-absorbing polymers, anhydrous silica, and zeolite may be used. The stabilizers and additives are also preferably other than zinc compounds.

  In the present invention, the content of the elemental zinc content contained in the extruded foam is preferably 0.025% or less, more preferably 0.020% or less, and still more preferably 0.010% or less. By making the content of the zinc element content within the above range, thermal decomposition of the halogen-based flame retardant is prevented, and the flame retardant effect is effectively exhibited. Further, deterioration of the styrene resin in the extrusion system is prevented, and the combustibility of the extruded foam is improved. The elemental zinc content is not limited to flame retardant aids and other additives, but is also slightly contained in zeolites and styrenic resins, including these, the elemental zinc content contained in the extruded foam. The content only needs to satisfy the above range.

  The method for producing an extruded foam of a styrene resin according to the present invention supplies a styrene resin to a heating and melting means such as an extruder, and a halogen flame retardant, zeolite, and a non-halogen foaming agent to the heating and melting means. Supply and heat-melt under high temperature and high pressure to make a styrene resin composition, cool the styrene resin composition to a resin temperature suitable for extrusion foaming with a cooler etc., and lower the pressure from the high pressure area through a die such as a slit die An extruded foam is obtained by extrusion foaming in the region.

  As a procedure for adding an additive such as a halogen flame retardant, zeolite, and a non-halogen foaming agent to a styrene resin, for example, after adding a halogen flame retardant and zeolite to a styrene resin and mixing, extrusion Examples include a procedure of supplying to a machine and melting by heating, and further adding and mixing a non-halogen foaming agent. Moreover, when adding synthetic zeolite and iron oxide to a styrene resin, iron oxide may be contained in water as a foaming agent. The timing of adding the halogen-based flame retardant, zeolite, non-halogen-based foaming agent, and iron oxide is not limited to the above-described example, and the heating temperature and kneading time when the styrene-based resin is heated and melted are also particularly high. It is not limited.

  The heating temperature of the styrenic resin may be higher than the temperature at which the used styrenic resin melts, but the temperature at which the molecular degradation of the resin due to the influence of the flame retardant is suppressed as much as possible, for example, about 150 to 220 ° C. preferable. Examples of the heating and melting means and the kneading means include a screw type extruder, but are not particularly limited as long as they are used for ordinary extrusion foaming. However, in order to suppress the molecular degradation of the resin as much as possible, it is preferable that the screw shape of the extruder is of a low shear type.

  The foam molding method is, for example, a method in which an extruded foam obtained by releasing pressure from a high pressure region to a low pressure region through a slit die having a linear slit shape used for extrusion molding is closely attached to the slit die. A method of molding a plate-like foam having a large cross-sectional area is used by using a molding die placed in contact and a molding roll installed adjacent to the downstream side of the molding die. By adjusting the flow surface shape and the mold temperature of the molding die, a desired foam cross-sectional shape, foam surface property, and foam quality can be obtained.

  The thickness of the styrene resin extruded foam obtained by the present invention is not particularly limited and is appropriately selected depending on the application. For example, in the case of a heat insulating material used for a building material or the like, in order to give a preferable heat insulating property, bending strength and compressive strength, a material having a thickness like a plate is preferable to a thin material such as a sheet. Usually, the thickness is 20 to 150 mm, preferably 20 to 120 mm.

The foam density of the styrene resin extruded foam obtained according to the present invention is preferably 20 to 40 kg / m ³ in order to give light weight and excellent heat insulating properties, bending strength, and compressive strength. More preferably, it is 35 kg / m ³ . By setting the foam density within the above range, mechanical properties such as compressive strength are improved, heat insulation is maintained, and the extruded foam is light.

  Examples of the present invention will be described below. Needless to say, the present invention is not limited to the following examples. In the following examples, “%” represents “% by weight” unless otherwise specified.

  As the characteristics of the styrene resin extruded foams obtained in Examples 1 to 11 and Comparative Examples 1 to 5 shown below, the foam density, combustibility (combustion time, combustion distance), and oxygen index are as follows. It investigated according to the following method.

(1) Foam density (kg / m ³ )
The foam density was determined based on the following formula, and the unit was shown in terms of kg / m ³ .
Foam density (g / cm ³ ) = foam weight (g) / foam volume (cm ³ )
In this measurement, sampling was performed with a sample size of product thickness × width 100 mm × length 300 mm at the position of the center in the width direction of the foam (thickness: 20 to 40 mm, width: about 150 mm), and each sample was measured. The foam density was calculated as an average value of three points.

(2) Flammability Extruded foams that had passed 4 days after production were measured according to Japanese Industrial Standard (JIS A 9511). A test piece (n = 5) having a thickness of 25 mm, a length of 200 mm, and a width of 10 mm was used as a measurement sample, and the determination was made according to the following criteria.
(Burning time)
A: Flame extinguishing time of all five specimens is within 3 seconds.
○: The flame extinguishing time of at least one test piece out of 5 test pieces exceeds 3 seconds, but the flame extinguishing time of the remaining 3 or more test pieces is within 3 seconds.
Δ: The flame extinguishing time of at least 3 test pieces out of 5 test pieces exceeds 3 seconds, but the flame extinguishing time of the remaining one or more test pieces is within 3 seconds.
X: Flame extinguishing time of all five test pieces exceeds 3 seconds.
(Burning distance)
A: Combustion stops within the combustion limit line in all five test pieces.
○: At least one of the five test pieces burns over the combustion limit line, but the remaining three or more test pieces stop burning within the combustion limit support line.
Δ: At least three of the five test pieces burn over the combustion limit line, but the remaining one or more test pieces stop burning within the combustion limit support line.
X: In all five test specimens, combustion exceeds the combustion limit line.

(3) Oxygen index About the extruded foam which passed for 1 day after manufacture, according to Japanese Industrial Standard (JIS K7201: 1999), after measuring the measurement sample of a dimension 10 mm x 10 mm x 150 mm, 23 degreeC and relative humidity 50% For 4 days, and the oxygen index was measured according to Procedure A described in Japanese Industrial Standard (JIS K7201-2). However, in the procedure A, only the flame contact time for the upper end ignition was set to one flame contact for 3 seconds.

(4) Quantitative determination of iron element content and zinc element content Approximately 0.05 g of a powder sample of the material to be quantified is precisely weighed in a PTFE decomposition vessel, and 1.5 mL of sulfuric acid is added to the microwave decomposition apparatus (Milestone General Co., Ltd.) Pre-disassembly was performed using a company, MLS-1200MEGA). After cooling the sample, it was further decomposed by adding 3 mL of nitric acid. A 50 mL volume of this decomposition solution was measured, and an iron element or a zinc element was quantitatively analyzed using an inductively coupled plasma mass spectrometry (ICP-MS method) apparatus (Yokogawa Analytical System Co., Ltd., HP-4500). Quantitative analysis was performed under cool plasma conditions, and measurement was performed by an absolute calibration curve method using Co as an internal standard material.

Example 1
Hexabromocyclododecane (hereinafter abbreviated as HBCD) as a flame retardant with respect to 100 parts by weight of virgin polystyrene resin (PS Japan Co., Ltd., G9401) as styrene resin (Albemarle Asano Co., Ltd., HP900G) 2.5 parts by weight, natural zeolite (Nitto Flour Chemical Co., Ltd., SP # 2300 Iizaka product) 0.5 parts by weight, calcium stearate (Sakai Chemical Industry Co., Ltd., SC-) as a lubricant 100) 0.25 parts by weight, and as a nucleating agent, 0.1 part by weight of talc (Hayashi Kasei Co., Ltd., Talkan PK) is dry blended to obtain a styrene resin composition, and this styrene resin composition is tandem-type extruded. Supplied to the machine.

  The styrene resin composition supplied to the first extruder is heated to about 200 ° C. and melt-kneaded. As a foaming agent, 100 parts by weight of styrene resin is used as i-butane (Mitsui Chemicals, high purity). 1 part by weight of isobutane), 2.3 parts by weight of n-butane (Iwatanigas Co., Ltd., normal butane), 3 parts by weight of dimethyl ether (Sumitomo Seika Co., Ltd., dimethyl ether), and 1 part by weight of water are near the tip of the first extruder. Was pressed into the styrene resin composition. Thereafter, the resin temperature (actual temperature) is about 110 to 140 ° C. by transferring the styrene resin composition to a second extruder and a cooler sequentially connected in series to the first extruder while cooling and kneading. And after being extruded and foamed into the atmosphere from the slit die provided at the tip of the cooler, the cross-sectional shape is 40 mm thick by a molding die installed in close contact with the slit die and a molding roll installed downstream thereof. A plate-like extruded foam having a width of 150 mm was obtained.

As shown in Table 1, the foam density of the extruded foam was 28 kg / m ³ , and a desired lightweight extruded foam was obtained. As for combustibility, the combustion time was “◯” and the combustion distance was “◯”, and good results were obtained. The oxygen index was 29%, and non-combustibility was confirmed.

(Example 2)
Extruded foam of styrene resin was obtained in the same manner as in Example 1 except that 0.03 part by weight of natural zeolite was added to 100 parts by weight of styrene resin.

As shown in Table 1, the foam density of the extruded foam was 27 kg / m ³ , and a desired lightweight extruded foam was obtained. As for combustibility, the burning time was “「 ”and the burning distance was“ ◎ ”, and very good results were obtained. The oxygen index was 30%, and non-combustibility was confirmed. From this, it can be seen that if 0.03 part by weight of natural zeolite is added to 100 parts by weight of styrene resin and 2.5 parts by weight of HBCD, a sufficient flame retardant effect can be obtained.

(Example 3)
Natural zeolite iron element content 4.9% artificial zeolite (Omikenshi Co., f _A zeolite Ca) instead of, except adding 1 part by weight per 100 parts by weight of styrene resin, the above embodiments 1 In the same manner as above, an extruded foam of a styrene resin was obtained.

As shown in Table 1, the foam density of the extruded foam was 29 kg / m ³ , and a desired lightweight extruded foam was obtained. As for combustibility, the combustion time was “◯” and the combustion distance was “◯”, and good results were obtained. The oxygen index was 28%, and non-combustibility was confirmed. From this, it can be seen that the artificial flame can provide the same flame retarding effect as natural zeolite.

Example 4
Natural zeolite iron element content 6.7% artificial zeolite (Maeda Co., _{f A} zeolite Fe-typeA) instead of, except adding 0.2 part by weight per 100 parts by weight styrene resin In the same manner as in Example 1, an extruded foam of styrene resin was obtained.

As shown in Table 1, the foam density of the extruded foam was 28 kg / m ³ , and a desired lightweight extruded foam was obtained. As for combustibility, the burning time was “「 ”and the burning distance was“ ◎ ”, and very good results were obtained. The oxygen index was 28%, and non-combustibility was confirmed. This shows that the combustibility is improved by increasing the iron element content of the artificial zeolite.

(Example 5)
Synthetic zeolite (Nippon Chemical Industry Co., Ltd., ZEOSTAR NA-100P) having an iron element content of 0% instead of natural zeolite was added in an amount of 0.2 parts by weight based on 100 parts by weight of the styrenic resin. Extruded foam of styrenic resin was obtained in the same manner as in Example 1 except that 0.02 parts by weight of Kojun Pharmaceutical Co., Ltd., Fe ₂ O ₃ ) was added.

As shown in Table 1, the foam density of the extruded foam was 27 kg / m ³ , and a desired lightweight extruded foam was obtained. As for combustibility, the combustion time was “◯” and the combustion distance was “◯”, and good results were obtained. The oxygen index was 29%, and non-combustibility was confirmed. From this, it is understood that the same flame retardant effect as that of natural zeolite can be obtained by adding synthetic zeolite and iron oxide not containing iron.

(Example 6)
1.5 parts by weight of HBCD and 0.2 parts by weight of natural zeolite are added to 100 parts by weight of styrene resin, and 0.5 parts by weight of i-butane and 1.2 parts of n-butane are used as a blowing agent. Extruded foam of styrenic resin in the same manner as in Example 1 except that 3 parts by weight, 3 parts by weight of dimethyl ether, 1 part by weight of water and 2 parts by weight of carbon dioxide (Ohira Sangyo Co., Ltd.) are added. Obtained.

As shown in Table 1, the foam density of the extruded foam was 25 kg / m ³ , and a desired lightweight extruded foam was obtained. As for combustibility, the burning time was “「 ”and the burning distance was“ ◎ ”, and very good results were obtained. The oxygen index was 30%, and non-combustibility was confirmed. From this, it can be seen that due to the presence of natural zeolite, a good flame retardant effect can be obtained even if the amount of HBCD is reduced to 1.5 parts by weight.

(Example 7)
1.5 parts by weight of HBCD and 0.2 parts by weight of natural zeolite are added to 100 parts by weight of styrene resin, and 0.5 parts by weight of i-butane and 1.2 parts of n-butane are used as a blowing agent. Extruded foam of styrene resin was obtained in the same manner as in Example 1 except that 3 parts by weight, 3 parts by weight of dimethyl ether, 1 part by weight of water and 3 parts by weight of carbon dioxide were added.

As shown in Table 1, the foam density of the extruded foam was 28 kg / m ³ , and a desired lightweight extruded foam was obtained. As for combustibility, the burning time was “「 ”and the burning distance was“ ◎ ”, and very good results were obtained. The oxygen index was 30%, and non-combustibility was confirmed. From this, it can be seen that regardless of the content ratio of carbon dioxide in the foaming agent, a good flame retardant effect can be obtained even if the amount of HBCD is reduced to 1.5 parts by weight due to the presence of natural zeolite.

(Example 8)
As a styrene resin, 80 parts by weight of recycled polystyrene resin (Muto Kasei, SOP) was dry blended with 20 parts by weight of virgin polystyrene resin. Except for adding 4.5 parts by weight of HBCD and 0.2 parts by weight of natural zeolite to 100 parts by weight of this styrene resin, an extruded foam of styrene resin was obtained in the same manner as in Example 1 above. Obtained.

As shown in Table 1, the foam density of the extruded foam was 26 kg / m ³ , and a desired lightweight extruded foam was obtained. As for combustibility, the combustion time was “◯” and the combustion distance was “◯”, and good results were obtained. The oxygen index was 29%, and non-combustibility was confirmed. Even when a recycled polystyrene resin was mixed as the styrene resin, good flame retardancy similar to that of Example 1 was confirmed. On the other hand, even if the amount of HBCD is increased to 4.5 parts by weight, no further flame retardant effect is observed, so that it can be seen that a sufficient amount of flame retardant effect can be obtained with a small amount of HBCD due to the presence of natural zeolite.

Example 9
As a styrene resin, 80 parts by weight of recycled polystyrene resin was dry blended with respect to 20 parts by weight of virgin polystyrene resin. Extruded foam of styrene resin was obtained in the same manner as in Example 1 except that 4.5 parts by weight of HBCD and 2 parts by weight of natural zeolite were added to 100 parts by weight of styrene resin. .

As shown in Table 1, the foam density of the extruded foam was 27 kg / m ³ , and a desired lightweight extruded foam was obtained. As for the combustibility, the combustion time was “◎” and the combustion distance was “◯”, and good results were obtained. The oxygen index was 28%, and non-combustibility was confirmed. Even when a recycled polystyrene resin was mixed as the styrene resin, good flame retardancy similar to that of Example 1 was confirmed. Further, even if the amount of natural zeolite is increased to 2 parts by weight with respect to 4.5 parts by weight of HBCD, the same flame retarding effect as in Example 8 can be seen, so it is sufficient to increase the amount of natural zeolite to 2 parts by weight. It can be seen that a flame retardant effect is obtained.

(Example 10)
As a styrene resin, 80 parts by weight of recycled polystyrene resin was dry blended with respect to 20 parts by weight of virgin polystyrene resin. 0.2 parts by weight of natural zeolite is added to 100 parts by weight of this styrenic resin, and 0.5 parts by weight of i-butane, 1.2 parts by weight of n-butane and 3 parts by weight of dimethyl ether are used as a blowing agent. Except for adding 1 part by weight, 1 part by weight of water, and 2 parts by weight of carbon dioxide, an extruded foam of a styrenic resin was obtained in the same manner as in Example 1 above.

As shown in Table 1, the foam density of the extruded foam was 25 kg / m ³ , and a desired lightweight extruded foam was obtained. As for combustibility, the burning time was “「 ”and the burning distance was“ ◎ ”, and very good results were obtained. The oxygen index was 28%, and non-combustibility was confirmed. Even when a recycled polystyrene resin was mixed as the styrene resin, good flame retardancy similar to that of Example 1 was confirmed. Further, it can be seen that, regardless of the composition of the blowing agent, a good flame retardant effect can be obtained with a small amount of HBCD due to the presence of natural zeolite.

(Example 11)
As a styrene resin, 80 parts by weight of recycled polystyrene resin was dry blended with respect to 20 parts by weight of virgin polystyrene resin. 0.03 part by weight of natural zeolite is added to 100 parts by weight of this styrene resin, and 2 parts by weight of i-butane, 0 part by weight of n-butane, 3 parts by weight of dimethyl ether and water are added as a blowing agent. Extruded foams of styrenic resins were obtained in the same manner as in Example 1 except that 1 part by weight and 3 parts by weight of carbon dioxide were added.

As shown in Table 1, the foam density of the extruded foam was 27 kg / m ³ , and a desired lightweight extruded foam was obtained. As for the combustibility, the combustion time was “◎” and the combustion distance was “◯”, and good results were obtained. The oxygen index was 27%, and non-combustibility was confirmed. Even when a recycled polystyrene resin was mixed as the styrene resin, good flame retardancy similar to that of Example 1 was confirmed. In addition, regardless of the composition of the foaming agent, 0.03 parts by weight of natural zeolite is added to 100 parts by weight of styrene resin and 2.5 parts by weight of HBCD, so that a good flame retardant effect can be obtained. Recognize.

(Example 12)
1.0 part by weight of HBCD and 0.2 part by weight of natural zeolite are added to 100 parts by weight of styrene resin, and 3 parts by weight of dimethyl ether, 1 part by weight of water and 3 parts by weight of carbon dioxide are used as a blowing agent. Except for adding a part, an extruded foam of a styrene resin was obtained in the same manner as in Example 1 above.

As shown in Table 1, the foam density of the extruded foam was 29 kg / m ³ , and a desired lightweight extruded foam was obtained. As for combustibility, the burning time was “「 ”and the burning distance was“ ◎ ”, and very good results were obtained. The oxygen index was 30%, and non-combustibility was confirmed. From this, it can be seen that due to the presence of natural zeolite, a good flame retardant effect can be obtained even if the amount of HBCD is reduced to 1.0 parts by weight.

(Example 13)
As a styrene resin, 80 parts by weight of recycled polystyrene resin was dry blended with respect to 20 parts by weight of virgin polystyrene resin. As in Example 1 above, except that 3 parts by weight of dimethyl ether, 1 part by weight of water, and 3 parts by weight of carbon dioxide are added as a foaming agent to 100 parts by weight of this styrenic resin. An extruded foam of resin was obtained.

As shown in Table 1, the foam density of the extruded foam was 29 kg / m ³ , and a desired lightweight extruded foam was obtained. As for combustibility, the burning time was “「 ”and the burning distance was“ ◎ ”, and very good results were obtained. The oxygen index was 28%, and non-combustibility was confirmed. Even when a recycled polystyrene resin was mixed as the styrene resin, good flame retardancy similar to that of Example 1 was confirmed. Regardless of the composition of the foaming agent, a good flame retardant effect can be obtained by adding 0.2 parts by weight of natural zeolite to 100 parts by weight of styrene resin and 1.5 parts by weight of HBCD. Recognize.

(Comparative Example 1)
Extruded foam of styrenic resin in the same manner as in Example 1 except that instead of natural zeolite, 0.5 part by weight of synthetic zeolite not containing iron is added to 100 parts by weight of styrenic resin. Got.

As shown in Table 1, the foam density of the extruded foam was 28 kg / m ³ , and a desired lightweight extruded foam was obtained. The combustibility was poor because the combustion time was “x” and the combustion distance was “x”. The oxygen index was 27%, and non-combustibility was confirmed. This shows that the flame retardant effect by a small amount of HBCD cannot be obtained only in a synthetic zeolite containing no iron, that is, in an environment in which iron oxide does not exist.

(Comparative Example 2)
A styrene-based resin is added in the same manner as in Example 1 except that 1 part by weight of natural zeolite is added to 100 parts by weight of a styrene-based resin, and 0.3 parts by weight of zinc stearate is added instead of calcium stearate. An extruded foam of resin was obtained.

As shown in Table 1, the foam density of the extruded foam was 27 kg / m ³ , and a desired lightweight extruded foam was obtained. The combustibility was poor because the combustion time was “x” and the combustion distance was “x”. The oxygen index was 26%, and non-combustibility was confirmed. From this, it can be seen that the improvement in flame retardancy by natural zeolite is inhibited by zinc stearate.

(Comparative Example 3)
As a styrene resin, 80 parts by weight of recycled polystyrene resin was dry blended with respect to 20 parts by weight of virgin polystyrene resin. Extruded foam of styrene resin was obtained in the same manner as in Example 1 except that 10 parts by weight of artificial zeolite was added instead of natural zeolite to 100 parts by weight of styrene resin.

As shown in Table 1, the foam density of the extruded foam was 28 kg / m ³ , and a desired lightweight extruded foam was obtained. The combustibility was poor because the combustion time was “x” and the combustion distance was “x”. The oxygen index was 26%, and non-combustibility was confirmed. From this, it can be seen that when the amount of artificial zeolite added reaches 10 parts by weight, the effect of improving flame retardancy is not observed.

(Comparative Example 4)
As a styrene resin, 80 parts by weight of recycled polystyrene resin was dry blended with respect to 20 parts by weight of virgin polystyrene resin. Extruded foam of styrene resin was obtained in the same manner as in Example 1 except that 100 parts by weight of styrene resin was used instead of natural zeolite and 1 part by weight of synthetic zeolite was added.

As shown in Table 1, the foam density of the extruded foam was 26 kg / m ³ , and a desired lightweight extruded foam was obtained. The combustibility was poor because the combustion time was “x” and the combustion distance was “x”. The oxygen index was 23%, and some non-combustibility was seen, but it was a lower value than in each example. This shows that the effect of improving flame retardancy cannot be obtained even when the synthetic zeolite containing no iron content is increased to 1 part by weight.

(Comparative Example 5)
As a styrene resin, 80 parts by weight of recycled polystyrene resin was dry blended with respect to 20 parts by weight of virgin polystyrene resin. Extruded foam of a styrene resin was obtained in the same manner as in Example 1 except that 100 parts by weight of the styrene resin was added instead of 0.5 parts by weight of synthetic zeolite instead of natural zeolite.

As shown in Table 1, the foam density of the extruded foam was 27 kg / m ³ , and a desired lightweight extruded foam was obtained. The combustibility was poor because the combustion time was “x” and the combustion distance was “x”. The oxygen index was 25%, and non-combustibility was confirmed. From this, it can be seen that the synthetic zeolite containing no iron does not have the effect of improving the flame retardancy regardless of the composition of the blowing agent.

Claims (7)

0.1 to 20 parts by weight of a halogen flame retardant, 5 to 15 parts by weight of a non-halogen foaming agent, and 0.01 to 9 parts by weight of zeolite are added to 100 parts by weight of a styrene resin. A styrene resin extruded foam obtained by extrusion foaming of a styrene resin,
The zeolite, all SANYO containing 0.2 to 20% of the iron element with respect to the zeolite,
The zinc element content contained in the styrene resin extruded foam is less than 0.03% by weight,
The non-halogen-based blowing agent includes a) a compound selected from dimethyl ether, diethyl ether, and methyl ethyl ether, b) water, and, if necessary, c) one or more saturated carbonizations having 3 to 5 carbon atoms. A styrenic resin extruded foam containing hydrogen and d) carbon dioxide.   The styrene resin extruded foam according to claim 1, wherein the zeolite is natural zeolite or artificial zeolite. The styrene resin extruded foam according to claim 1 or 2 , wherein the halogen flame retardant is one or both of hexabromocyclododecane and tetrabromocyclooctane. The styrenic resin according to any one of claims 1 to 3, wherein the one or more saturated hydrocarbons having 3 to 5 carbon atoms are selected from the group consisting of propane, n-butane, and i-butane. Extruded foam. The styrene resin extruded foam according to any one of claims 1 to 4, wherein water as the foaming agent comprises the iron oxide. The styrene resin extruded foam according to any one of claims 1 to 5 , wherein the foam density of the styrene resin extruded foam is 20 to 40 kg / m ³ . 0.1 to 20 parts by weight of a halogen flame retardant, 5 to 15 parts by weight of a non-halogen foaming agent, and 0.01 to 9 parts by weight of zeolite are added to 100 parts by weight of a styrene resin, A method for producing a styrene resin extruded foam by extruding and foaming a styrene resin from a high pressure region to a low pressure region through a die to obtain a styrene resin extruded foam having a foam density of 20 to 40 kg / m3 ,
The zeolite contains 0.2 to 20% iron element with respect to the zeolite ,
The zinc element content contained in the styrene resin extruded foam is less than 0.03% by weight,
The non-halogen-based blowing agent includes a) a compound selected from dimethyl ether, diethyl ether, and methyl ethyl ether, b) water, and, if necessary, c) one or more saturated carbonizations having 3 to 5 carbon atoms. The manufacturing method of the styrene resin extruded foam which contains hydrogen and d) carbon dioxide.