JP5134753B2 - Styrenic resin foam and method for producing the same - Google Patents

Description

  The present invention is a styrenic resin foam having excellent flame retardancy and high heat insulation properties, and particularly using one or more compounds having an ozone depletion coefficient of 0 as a foaming agent and excellent in thermal stability. Therefore, the present invention relates to a styrenic resin foam having excellent recyclability and excellent environmental compatibility, and a method for producing the same.

    A method of continuously producing a foam by heating and melting a styrenic resin with an extruder or the like, then adding a foaming agent, cooling it, and extruding it into a low pressure region is already known.

  In addition, a method using an aliphatic hydrocarbon, a chlorinated hydrocarbon, a fluorinated hydrocarbon, a chlorine fluorinated hydrocarbon, or the like as a blowing agent is also known.

  Among such blowing agents, in recent years, compounds such as chlorofluorocarbons and hydrochlorofluorocarbons among halogenated hydrocarbons have an ozone depleting action, and it is hoped that they will be replaced if possible from the viewpoint of protecting the ozone layer. It is rare. For this reason, hydrocarbons such as propane and butane, hydrofluorocarbons such as 1,1,1,2-tetrafluoroethane, or mixtures thereof are used as blowing agents having no ozone destructive action (so-called ozone depletion coefficient is 0). The styrenic resin foam used and its production method have been proposed.

  On the other hand, since such a styrene-based resin foam is used as a building material such as a heat insulating material for a house, for example, the combustibility defined in JIS A9511 may be required. Therefore, in order to satisfy such a requirement, for example, a flame retardant such as an organic bromine-based compound is used.

  Specifically, brominated alicyclic flame retardants typified by hexabromocyclododecane are widely used, and particularly excellent for styrene resin foams by using halogenated aromatic allyl ethers. It is known that flame retardancy can be imparted (for example, see Patent Document 1). However, the halogenated aromatic allyl ether-containing styrene resin has very poor thermal stability, and it is difficult to produce a foam by an extrusion method. For this reason, the addition of a stabilizer has been studied, but the flame retardancy tends to decrease due to the addition of the stabilizer, and it has been difficult to achieve both thermal stability and flame retardancy.

On the other hand, the present inventors, in a foam using saturated hydrocarbons such as propane and butane as a foaming agent, have a high degree of heat insulation such as flammability specified by JIS A9511 and two or three types of extruded polystyrene foam heat insulating plates. In order to achieve compatibility, it is necessary to suppress the combustion of saturated hydrocarbons remaining in the foam, and it has been found that there are problems that are difficult to achieve with conventional techniques. By using phosphorus-containing compounds, boron-containing compounds, nitrogen-containing compounds, etc., it is possible to suppress the combustion of saturated hydrocarbons and realize the flame retardancy specified by JIS A9511, and the bubble diameter is generally as the foam cell structure of the foam. Bubbles with a relatively small bubble diameter (small bubbles) of 0.25 mm or less and bubbles with a relatively large bubble diameter (large bubbles) with a bubble diameter of approximately 0.3 mm to 1 mm are in the shape of a sea island. By adopting a characteristic bubble structure that is mixed, it is possible to achieve high heat insulation properties such as two or three types of extruded polystyrene foam insulation plates even for foams containing relatively small amounts of saturated hydrocarbons. Thus, a technique capable of achieving both flame retardancy and heat insulation has been proposed (see, for example, Patent Documents 2 to 6).
JP-A-11-130898 JP 2001-121596 A JP 2001-131322 A JP 2001-131323 A JP 2001-131324 A JP 2002-30147 A

  However, in recent years, environmental compatibility has been regarded as important, and the resin foam product itself after use, or the end material generated when the foam is cut and finished into a product, etc. It is desired to recycle and use again for foams and other applications. In consideration of such recycling, even in the invention as described above that does not use a halogenated aromatic allyl ether, for example, when it is recycled as a foam, it is used for thermal decomposition of a flame retardant and other additives. As a result, there are cases where the resin deteriorates, discolors, or does not exhibit desired mechanical strength.

  In particular, in a foam using saturated hydrocarbons such as propane and butane as a foaming agent, in order to express high heat insulation properties such as two or three types of extruded polystyrene foam heat insulating plates specified in JIS A9511 as described above. In this case, it is desirable to have the characteristic bubble structure as described above, but it has been found that there is a case where the problem of affecting the formation of such a bubble structure may occur when recycled.

  In order to solve such problems, it is conceivable to limit the amount of flame retardant used or to add a stabilizer such as phenol or phosphorus to suppress deterioration of the resin. Flame retardancy is reduced and product costs are increased.

  Under such circumstances, the problem to be solved by the present invention is a styrene resin foam excellent in flame retardancy, which is one or more compounds having an ozone depletion coefficient of 0 and excellent environmental compatibility. Another object of the present invention is to provide a styrenic resin foam and a method for producing the same, which are excellent in recyclability, can be reused without being discarded, and have further improved environmental compatibility. In particular, in the foam using saturated hydrocarbons such as propane and butane as the foaming agent, the above-mentioned in order to satisfy both the flammability specified in JIS A9511 and the high heat insulation properties such as two or three types of extruded polystyrene foam heat insulating plates. A styrenic resin foam that can be stably realized even when the characteristic bubble structure is recycled and a method for producing the same are provided.

  As a result of diligent research to solve the above problems, the present inventors have made a styrene resin foam using a compound having an ozone depletion coefficient of 0 as a foaming agent, a halogenated aromatic alkylallyl ether as a flame retardant, and By including at least one compound selected from the group of halides, it has excellent flame retardancy and is excellent in recyclability, and can stably obtain a desired foamed cell structure even when recycled. The present inventors have found that a foam excellent in flame retardancy, environmental compatibility, thermal stability, and heat insulation, such as excellent heat insulation, can be obtained.

That is, the present invention
(1) A styrene resin foam obtained by extrusion foaming a styrene resin, which is a compound selected from the group of hydrocarbons and halogenated hydrocarbons as part or all of the foaming agent, and ozone It contains at least one compound having a destruction coefficient of 0, and further contains at least one compound selected from the group of halogenated aromatic alkylallyl ethers and halides thereof as a flame retardant. The present invention relates to a styrene resin foam.

(2)
2. The styrenic resin foam according to claim 1, wherein the bubbles forming the foam are mainly composed of bubbles having a bubble diameter of 0.25 mm or less and bubbles having a bubble diameter of 0.3 to 1 mm.

(3)
3. The styrenic resin foam according to claim 2, wherein, of the bubbles forming the foam, bubbles having a bubble diameter of 0.25 mm or less have an occupied area ratio of 5 to 95% per cross-sectional area of the foam.

(4)
As a foaming agent in the styrene resin foam, 100 or more compounds selected from the group of hydrocarbons and halogenated hydrocarbons and having an ozone depletion coefficient of 0 are used with respect to the total amount of the foaming agent. The styrenic resin foam according to any one of claims 1 to 3, which contains -1 wt% and other foaming agents in an amount of 0 to 99 wt%.

(5)
As a foaming agent in the styrene resin foam, one or more compounds selected from the group of hydrocarbons and halogenated hydrocarbons and having an ozone depletion coefficient of 0 are added to 100 parts by weight of the foam. The styrenic resin foam according to any one of claims 1 to 4, further comprising 0.1 to 10 parts by weight.

(6)
0.1 to 20 parts by weight of one or more compounds selected from the group of halogenated aromatic alkylallyl ethers and their halides as flame retardants per 100 parts by weight of styrene resin It is related with the styrene resin foam of any one of Claims 1-5.

(7)
The styrene according to any one of claims 1 to 6, comprising one or more compounds selected from halogenated aromatic alkyl allyl ethers, halogenated flame retardants of the halides thereof, and diphenylalkanes. The present invention relates to a resin foam.

(8)
A compound selected from the group of hydrocarbons and halogenated hydrocarbons, and at least one compound having an ozone depletion coefficient of 0 is selected from the group of saturated hydrocarbons and hydrofluorocarbons having 3 to 5 carbon atoms The styrenic resin foam according to any one of claims 1 to 7, wherein the styrenic resin foam is one or more kinds of compounds.

(9)
One or more compounds selected from the group of saturated hydrocarbons and hydrofluorocarbons having 3 to 5 carbon atoms are propane, n-butane, i-butane, 1,1,1,2-tetrafluoroethane (HFC- 134a: CH ₂ FCF ₃ ). The styrenic resin foam according to claim 8, wherein:

(10)
One or more compounds selected from the group consisting of hydrocarbons and halogenated hydrocarbons and having an ozone depletion coefficient of 0, or blowing agents other than saturated hydrocarbons and hydrofluorocarbons having 3 to 5 carbon atoms Is one or more compounds selected from dimethyl ether, diethyl ether, methyl ethyl ether, methyl chloride, ethyl chloride, water, and carbon dioxide. The present invention relates to a resin foam.

(11)
Halogenated aromatic alkyl allyl ethers and their halides are tetrabromobisphenol A-bis (2-methylallyl ether) and / or tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether). It is related with the styrene resin foam of any one of Claims 1-10 characterized by the above-mentioned.

(12)
The styrene according to any one of claims 7 to 11, wherein the diphenylalkane is 2,3-dimethyl-2,3-diphenylbutane and / or 3,4-dimethyl-3,4-diphenylhexane. The present invention relates to a resin foam.

(13)
Furthermore, the styrene type | system | group of any one of Claims 1-12 containing 1 or more types of compounds chosen from the group of a phosphorus-containing compound, a nitrogen-containing compound, a boron-containing compound, and a sulfur-containing compound. The present invention relates to a resin foam.

(14)
The styrenic resin contains a styrenic resin composition obtained by regenerating the styrenic resin foam according to any one of claims 1 to 13. This relates to a styrene resin foam.

(15)
A method for producing a styrene resin foam in which a styrene resin is heated and melted, a foaming agent is added to the styrene resin, and extrusion foaming is performed in a low-pressure region. The styrene resin includes hydrocarbons and halogenated hydrocarbons. A compound selected from the group consisting of one or more foaming agents having an ozone depletion coefficient of 0 and other foaming agents as required, and halogenated aromatic alkylallyl ethers, and their halides One or more halogen-based flame retardants selected and, if necessary, one or more compounds selected from the group consisting of other halogen-based flame retardants, diphenylalkanes, phosphorus-containing compounds, nitrogen-containing compounds, boron-containing compounds, and sulfur-containing compounds. The present invention relates to a method for producing a styrenic resin foam, characterized by coexistence and extrusion foaming.

(16)
The styrenic resin is a compound selected from the group consisting of hydrocarbons and halogenated hydrocarbons, and one or more blowing agents having an ozone depletion coefficient of 0 and other blowing agents as required, and halogenated aromatics One or more halogen-based flame retardants selected from the group of alkylallyl ethers and halides thereof and other halogen-based flame retardants as necessary, diphenylalkanes, phosphorus-containing compounds, nitrogen-containing compounds, boron-containing compounds, sulfur-containing 16. The styrene resin foam according to claim 15, comprising a styrene resin composition obtained by regenerating a styrene foam that has been extruded and foamed in the presence of one or more compounds selected from the group of compounds. It relates to the manufacturing method.

    According to the present invention, a foaming agent having excellent environmental compatibility is used, which is excellent in heat stability, heat insulation, flame retardancy, and hardly deteriorates due to heat history during recycling, that is, in recyclability. An excellent styrenic resin foam and a method for producing the same are provided. The styrenic resin foam of the present invention is useful for various uses, particularly for building heat insulating materials, because of its excellent flame retardancy and heat insulating properties.

    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. Examples thereof include random, block or graft copolymers, post-brominated polystyrene, modified polystyrene such as rubber-reinforced polystyrene, and the like. These can be used alone or in admixture of two or more.

  As monomers copolymerizable with styrene, styrene derivatives such as methylstyrene, dimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, bromostyrene, dibromostyrene, tribromostyrene, chlorostyrene, dichlorostyrene, 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 budadiene or the like Derivatives, unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride and the like. These can be used alone or in admixture of two or more.

  Of the styrene resins, styrene homopolymer, (meth) acrylic acid copolymerized polystyrene, maleic anhydride-modified polystyrene, impact-resistant polystyrene and the like are preferable from the viewpoint of processability.

The present invention relates to a compound selected from the group of hydrocarbons and halogenated hydrocarbons as a blowing agent, and one or more compounds having an ozone depletion coefficient of 0 (hereinafter, compounds having an ozone depletion coefficient of 0) And other foaming agents (hereinafter also referred to as other foaming agents) as required. The ozone depletion coefficient means a relative value when the ozone depletion amount per unit weight of trichloromonofluoromethane (CFC-11: CCl ₃ F) is 1, and the ozone depletion coefficient is 0 Even if there is no ozone destructive action or ozone destructive action, it means that the ozone depletion coefficient is 0.01 or less.

  Examples of the hydrocarbon used in the present invention and having an ozone depletion coefficient of 0 include saturated hydrocarbons having 3 to 5 carbon atoms, specifically, propane, n-butane, i-butane, n-pentane, i-pentane, c-pentane and the like can be mentioned. In the case of saturated hydrocarbons having 3 to 5 carbon atoms, propane, n-butane, i-butane or a mixture thereof is preferable from the viewpoint of foamability. Moreover, n-butane, i-butane or a mixture thereof is preferable from the viewpoint of the heat insulating performance of the foam, and i-butane is particularly preferable.

Examples of the halogenated hydrocarbons having an ozone depletion coefficient of 0 include hydrofluorocarbons having an ozone depletion coefficient of 0, specifically, trifluoromethane (HFC-23: CHF ₃ ), difluoromethane (HFC-32). : CH ₂ F ₂ ), 1,1,1,2,2-pentafluoroethane (HFC-125: CHF ₂ CF ₃ ), 1,1,1,2-tetrafluoroethane (HFC-134a: CH ₂ FCF) ₃ ), 1,1,1-trifluoroethane (HFC-143a: CH ₃ CF ₃ ), 1,1-difluoroethane (HFC-152a: CH ₃ CHF ₂ ), 1,1,1,2,3,3 , 3-heptafluoropropane _{(HFC-227ea: CF 3 CHFCF} 3), 1,1,1,3,3,3- hexafluoropropane (HFC-236fa: CF ₃ H ₂ CF _3), 1,1,2,2,3- pentafluoropropane _{(HFC-245ca: CH 2 FCF} 2 CHF 2), 1,1,1,2,2- pentafluoropropane (HFC-245cb: CF ₃ CF ₂ CH ₃ ), 1,1,1,3,3-pentafluoropropane (HFC-245fa: CF ₃ CH ₂ CHF ₂ ), 1,1,1,3,3-pentafluorobutane (HFC- 365mfc: CF ₃ CH ₂ CF ₂ CH ₃ ) and the like. From the viewpoint of foam moldability, 1,1,1,2-tetrafluoroethane (HFC-134a: CH ₂ FCF ₃ ) is more preferable.

  Furthermore, in the present invention, a saturated hydrocarbon having 3 to 5 carbon atoms, which is a hydrocarbon having an ozone depletion coefficient of 0, is particularly preferably used from the viewpoint of the global environment, and propane, n-butane, i-butane or a mixture thereof is used. More preferred. Further, when a saturated hydrocarbon having 3 to 5 carbon atoms is used, the bubble structure constituting the foam includes bubbles (small bubbles) having a bubble diameter of approximately 0.25 mm or less and bubbles having a relatively small bubble diameter. From the viewpoint of heat insulation, it is preferable to have a characteristic bubble structure in which bubbles having a relatively large bubble diameter (large bubbles) having a diameter of approximately 0.3 mm to 1 mm are mixed in a sea-island shape.

  A compound selected from the group of hydrocarbons and halogenated hydrocarbons and having an ozone depletion coefficient of 0 is used alone or in combination of two or more.

  In the present invention, by using a foaming agent other than a compound selected from the group of hydrocarbons and halogenated hydrocarbons and having an ozone depletion coefficient of 0, a plasticizing effect at the time of foam production And a foaming aid effect are obtained, the extrusion pressure is reduced, and the foam can be stably produced. However, depending on the various properties of the foam, such as the desired foaming ratio and flame retardancy, the amount used can be limited.

  Other foaming agents are not particularly limited. For example, ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, isopropyl ether, n-butyl ether, diisopropyl ether, furan, furfural, 2-methyl furan, tetrahydrofuran, tetrahydropyran, dimethyl ketone, methyl ethyl ketone, diethyl ketone, methyl n- Ketones such as propyl ketone, methyl n-butyl ketone, methyl i-butyl ketone, methyl n-amyl ketone, methyl n-hexyl ketone, ethyl n-propyl ketone, ethyl n-butyl ketone, methanol, ethanol, propyl alcohol, i-propyl alcohol , Alcohols such as butyl alcohol, i-butyl alcohol, t-butyl alcohol, formic acid methyl ester, formic acid ethyl ester, formic acid propylene Organic foaming agents such as esters, butyl formate, amyl formate, carboxylic acid esters such as methyl propionate and ethyl propionate, alkyl halides such as methyl chloride and ethyl chloride, such as nitrogen, water and carbon dioxide Inorganic foaming agents such as chemical foaming agents such as azo compounds and tetrazole can be used. These other foaming agents can be used alone or in admixture of two or more.

  Among other foaming agents, dimethyl ether, diethyl ether, methyl ethyl ether, methyl chloride, ethyl chloride, etc. are preferable from the viewpoint of foamability, foam moldability, etc., and the flammability of the foaming agent and flame retardancy of the foam Or water and a carbon dioxide are preferable from points, such as heat insulation mentioned later. Among other foaming agents, dimethyl ether, water, and carbon dioxide, which are excellent in environmental compatibility, are particularly preferable.

  If necessary, a foaming agent having an ozone depletion coefficient other than 0, such as chlorofluorocarbon and hydrochlorofluorocarbon, may be used as long as the amount is small.

  In the production of the styrene resin foam of the present invention, the amount of the foaming agent to be added or injected into the styrene resin is appropriately changed according to the setting value of the expansion ratio, etc. The total amount is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the styrene resin. When the amount of the foaming agent added is less than 1 part by weight, the foaming ratio is low, and the characteristics such as light weight and heat insulation as foams may be difficult to be exhibited. On the other hand, when the amount exceeds 20 parts by weight, foaming is caused by an excessive amount of foaming agent. There may be defects such as voids in the body, and flame retardancy may be reduced depending on the type of foaming agent.

  In the foaming agent to be added, the amount of the one or more compounds having an ozone depletion coefficient of 0 is 10% by weight or more, preferably 20% by weight or more with respect to 100% by weight of the total amount of the foaming agent. The amount is preferably 90% by weight or less, preferably 80% by weight or less, with respect to 100% by weight of the total amount of the blowing agent. If the amount of the one or more compounds having an ozone depletion coefficient of 0 is less than the above range, the resulting foam may have poor heat insulation. When the amount of the other blowing agent exceeds the above range, if the compatibility with the resin is high, the plasticity is too high, the kneading state of the styrene resin and the blowing agent in the extruder becomes uneven, and the pressure of the extruder If the control becomes difficult or the compatibility with the resin is low, pores or the like are generated in the foam, and a good foam cannot be obtained, or the pressure control of the extruder becomes difficult, and flammability Some foaming agents tend to reduce the flame retardancy of the foam.

  From the viewpoint of obtaining a foam of good quality such as stable foam production and appearance, the amount of the one or more compounds having an ozone depletion coefficient of 0 in the added foaming agent is 100% by weight of the total amount of the foaming agent. The amount of the other foaming agent is preferably 10% by weight or more, more preferably 20% with respect to 100% by weight of the total amount of the foaming agent. % By weight or more.

  When water is used as another foaming agent, processability, bubbles with a bubble diameter of 0.25 mm or less (hereinafter also referred to as small bubbles), and bubbles with a bubble diameter of 0.3 to 1 mm (hereinafter also referred to as large bubbles). From the viewpoint of production, the amount is preferably 1 to 80% by weight, more preferably 2 to 70% by weight, and particularly preferably 3 to 60% by weight with respect to 100% by weight of the total amount of the blowing agent. When water and other foaming agents other than water (such as at least one ether selected from the group consisting of dimethyl ether, diethyl ether and methyl ethyl ether) are used in combination, processability and small bubbles From the viewpoint of the formation of large bubbles, the total amount of the foaming agent is preferably 1 to 75% by weight and other foaming agents 79 to 5% by weight, more preferably 2 to 70% by weight It is 78 to 10% by weight of a foaming agent, particularly preferably 3 to 65% by weight of water and 77 to 15% by weight of another foaming agent.

  The pressure when adding or injecting the foaming agent is not particularly limited as long as it is higher than the internal pressure of an extruder or the like.

  The styrenic resin foam obtained by the present invention has at least one compound selected from the group of hydrocarbons and halogenated hydrocarbons as a foaming agent and having an ozone depletion coefficient of 0. A compound is contained. However, in the obtained styrene-based resin foam, the residual content of one or more compounds having an ozone depletion coefficient of 0 is the type and amount of the compound used, the permeability of the foaming agent in the foam, the foam It depends on the magnification or density of the material and the required heat insulation performance. In particular, depending on the permeability of the foaming agent in the foam, the remaining amount decreases with time, and the gas in the foam bubbles is replaced with air or the like. Therefore, a foam produced by using a compound having a high permeability and consequently having a very small amount of compound remaining in the foam is also included in the scope of the present invention.

  However, when a high degree of heat insulation performance is required, such as two types of extruded polystyrene foam heat insulating plates specified in JIS A 9511, and further three types, the composition of the foaming agent in the resulting styrene resin foam is the remaining One or more compounds selected from the group consisting of hydrocarbons and halogenated hydrocarbons and having an ozone depletion coefficient of 0 are preferably 100 to 1% by weight, more preferably based on the total amount of blowing agent Is 100 to 5% by weight, more preferably 100 to 10% by weight, particularly preferably 100 to 20% by weight, and other foaming agents are preferably 0 to 99% by weight, more preferably 0 to 95% by weight, still more preferably. It is 0 to 90% by weight, particularly preferably 0 to 80% by weight. When the amount of one or more compounds having an ozone depletion coefficient of 0 in the foaming agent remaining in the foam is less than the above range, two types of extruded polystyrene foam heat insulating plates specified by JISA 9511, and three more advanced types It tends to be difficult to obtain the heat insulation performance.

  Further, when two or three types of extruded polystyrene foam heat insulating plates require high heat insulation performance, they are compounds selected from the group of hydrocarbons and halogenated hydrocarbons in the foam, and In general, the residual content of one or more compounds having an ozone depletion coefficient of 0 is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the foam. In particular, when higher heat insulation performance is required, such as three types of extruded polystyrene foam insulation plates, 2-10 parts by weight are more preferable for one or more compounds that are hydrocarbons and have an ozone depletion potential of 0. Specifically, for propane, 2 to 9 parts by weight, particularly preferably 3 to 8 parts by weight, for n-butane and i-butane, 1.5 to 9 parts by weight, particularly preferably 2 to 8 parts by weight. , N-pentane, i-pentane, c-pentane is preferably 2 to 9 parts by weight, and one or more compounds that are halogenated hydrocarbons and have an ozone depletion coefficient of 0 are 2 to 10 parts by weight, Specifically, it is 2 to 10 parts by weight for hydrofluorocarbons such as 1,1,1,2-tetrafluoroethane.

  The remaining content of the foaming agent other than the one or more compounds selected from the group of hydrocarbons and halogenated hydrocarbons and having an ozone depletion coefficient of 0 is the type of foaming agent, foam In order to improve the heat insulation performance of the foam, it is preferably 0 to 18 parts by weight, and more preferably 0 to 10 parts by weight. In particular, depending on the permeability of the foaming agent in the foam, the residual amount decreases with time like the saturated hydrocarbon having 3 to 5 carbon atoms, and the gas in the foam bubbles is replaced with air or the like.

  In the present invention, a flame retardant for the purpose of obtaining a styrene resin foam having a flame retardancy and good recyclability, in particular, a styrene resin foam in which the characteristic cell structure is stably formed even when recycled. One or more compounds selected from the group consisting of halogenated aromatic alkyl allyl ethers and halides thereof are used.

  Specifically, 2-bromophenyl-2-methylallyl ether, 2,6-dibromophenyl-2-methylallyl ether, 2,6-dibromo-4-methylphenyl-2-methylallyl ether, 2,6-dibromo -4-t-butylphenyl-2-methylallyl ether, 2,4,6-tribromophenyl-2-methylallyl ether, 2,4,6-tribromophenyl-3-methylallyl ether, 2,4, Phenylalkyl allyl ethers such as 6-tribromophenyl-2-ethylallyl ether, tetrabromobisphenol A-bis (2-methylallyl ether), tetrabromobisphenol A-bis (3-methylallyl ether), tetrabromobisphenol A-bis (2-ethylallyl ether), tetrabromobisphenol F- bis (2-methyl allyl ether), di allyl ethers tetrabromobisphenol S- bis (2-methyl allyl ether) bisphenols such as, polyalkyl allyl ethers of novolak type phenol resin. Of these, tetrabromobisphenol A-bis (2-methylallyl ether) can be preferably used from the viewpoints of thermal stability, flame retardancy, availability, and the like.

  Further, the halogenated aromatic alkyl allyl ether halide in the present invention is not particularly limited, but is, for example, a halogenated allyl group of the halogenated aromatic acrylic allyl ether. Specifically, one or two halogen groups are added to the allyl group of the above-exemplified compounds. Among these, tetrabromobisphenol A- is used from the viewpoint of thermal stability, flame retardancy, availability, and the like. Tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether) which is a dibrominated product of bis (2-methylallyl ether) can be preferably used.

  The content of one or more compounds selected from the group of halogenated aromatic alkyl allyl ethers and their halides used in the present invention is added with a blowing agent so as to obtain flame retardancy as defined in JISA 9511. The amount, foam density, diphenylalkane described later, other halogen flame retardant, additive having a synergistic effect, etc. are appropriately adjusted according to the type or amount of addition, but generally 100 parts by weight of styrene resin The amount is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, and still more preferably 1 to 10 parts. When the content of one or more compounds selected from the group of halogenated aromatic alkyl allyl ethers and halides thereof is less than the above, good properties as a foam such as flame retardancy aimed at by the present invention are obtained. On the other hand, if the above range is exceeded, the moldability and surface properties at the time of foam production may be altered and impaired.

  In this invention, in the range which does not impair the effect of this invention, the 1 or more types of compound chosen from other halogenated flame retardants and diphenyl alkane can be contained as needed.

  As other halogen-based flame retardants, commonly used flame retardants can be used without any particular limitation. For example, tetrabromoethane, tetrabromocyclooctane, hexabromocyclododecane, dibromoethyldibromocyclohexane, dibromodimethylhexane, 2- (bromomethyl) -2- (hydroxymethyl) -1,3-propanediol, dibromoneopentyl glycol, Tribromoneopentyl alcohol, pentaerythrityl tetrabromide, monobromodipentaerythritol, dibromodipentaerythritol, tribromodipentaerythritol, tetrabromodipentaerythritol, pentabromodipentaerythritol, hexabromodipentaerythritol, hexabromotripenta Erythritol, polybrominated polypentaerythritol, tetrabromophthalic anhydride, tris (2,3-dibromopropyl Halogenated aliphatic compounds such as isocyanurates or derivatives thereof, or halogenated alicyclic compounds or derivatives thereof, hexabromobenzene, pentabromotoluene, bis (2-ethylhexyl) tetrabromophthalate, decabromodiphenyl ether, octa Bromodiphenyl ether, 2,2-bis (4′-hydroxy-3 ′, 5′-dibromophenyl) propane (common name tetrabromobisphenol A), bis (4-hydroxy-3,5-dibromophenyl) sulfone (common name tetrabromo) Bisphenol S), tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A diallyl ether, tetrabromobisphenol S-bis (2,3-dibromopropyl ether), Labromobisphenol A-bis (4-hydroxyethyl ether), tetrabromobisphenol A diglycidyl ether, or a brominated bisphenol adduct or a derivative thereof, tetrabromobisphenol A or a polycarbonate composed of this and bisphenol A, ethylene bis ( Pentabromophenyl), bis (2,4,6-tribromophenoxy) ethane, octabromotrimethylphenylindane, pentabromobenzyl acrylate or a polymer thereof, tetrabromobisphenol A-bis (2-bromoethyl ether), tetra Bromobisphenol S-bis (2-bromoethyl ether), ethylenebistetrabromophthalimide, ethylenebisdibromonorbornanedicarboximide, 2,4 , 6-tris (2,4,6-tribromophenoxy) 1,3,5-triazine, halogenated aromatic compounds such as perbromo (1,4-diphenoxybenzene), other halogen compounds, tris (tri Halogen and phosphorus atom-containing compounds such as bromoneopentyl) phosphate and tris (bromophenyl) phosphate, chlorinated paraffin, chlorinated naphthalene, perchloropentadecane, chlorinated aromatic compounds, chlorinated alicyclic compounds, ammonium bromide, etc. Examples thereof include brominated inorganic compounds. These compounds can be used individually or in mixture of 2 or more types. Furthermore, a brominated polystyrene resin which is one of the styrene resins of the present invention can also be used as a flame retardant.

  The content of other halogen-based flame retardants is such that the amount of foaming agent added, foam density, halogenated aromatic alkyl allyl ethers, and the group of halides thereof can be obtained so as to obtain flame retardancy as defined in JISA 9511. The addition amount of one or more compounds selected from the above, diphenylalkane, which will be described later, and the type or addition amount of a synergistic additive, etc., is appropriately adjusted, but generally with respect to 100 parts by weight of the styrene resin 0.1 to 10 parts by weight is preferable, more preferably 0.5 to 9 parts by weight, and still more preferably 1 to 8 parts by weight. In addition, the halogenated aromatic alkyl allyl ethers and one or more compounds selected from the group of halides thereof in a halogenated flame retardant combined with other halogenated flame retardants in excess of 50% by weight, It is preferably 80% by weight or more, and the total addition amount of the halogen-based flame retardant is preferably 0.1 to 10 parts by weight from the viewpoint of moldability at the time of foam production.

  The diphenylalkane can be used without any particular limitation. For example, the following general formula (Formula 2)

（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４は炭素数１以上のアルキル基を表す）
で表されるジフェニルアルカン（以下、単にジフェニルアルカンとも言う）を用いる。ジフェニルアルカンの具体例としては、２，３−ジメチル−２，３−ジフェニルブタン、３，４−ジメチル−３，４−ジフェニルヘキサンが挙げられる。２，３−ジメチル−２，３−ジフェニルブタンが難燃性および化合物自体の取り扱い性の点から好ましい。

(Wherein R1, R2, R3 and R4 represent an alkyl group having 1 or more carbon atoms)
The diphenylalkane represented by the following (hereinafter also simply referred to as diphenylalkane) is used. Specific examples of diphenylalkane include 2,3-dimethyl-2,3-diphenylbutane and 3,4-dimethyl-3,4-diphenylhexane. 2,3-dimethyl-2,3-diphenylbutane is preferred from the viewpoint of flame retardancy and handling of the compound itself.

  Diphenylalkane can be used alone or in combination of two or more.

  The content of diphenylalkane is a kind selected from the group of foaming agent addition amount, foam density, halogenated aromatic alkylallyl ethers, and halides thereof so that flame retardancy specified in JIS A 9511 can be obtained. The amount of the above compound added, other halogen flame retardants, and the type or amount of additive having a synergistic effect described later, etc. are appropriately adjusted. The amount is preferably 0.1 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, and still more preferably 0.3 to 1 part by weight. In particular, the addition amount of about 0.5 parts by weight is preferable because the effect may be exhibited specifically.

  In the present invention, one or more compounds selected from the group of halogenated aromatic alkyl allyl ethers and halides thereof, or other halogen-based flame retardants, phosphorus-containing compounds, nitrogen-containing compounds, boron-containing compounds A compound selected from the group of flammable hydrocarbons and halogenated hydrocarbons by using a compound and a sulfur-containing compound in combination, and one or more compounds having an ozone depletion coefficient of 0, specifically Uses a saturated hydrocarbon having 3 to 5 carbon atoms, such as propane, n-butane, i-butane, etc., as a foaming agent, and exhibits high heat insulation performance corresponding to two or three types of extruded polystyrene foam heat insulating plates. In some cases, one or more compounds selected from the group consisting of halogenated aromatic alkyl allyl ethers and halides thereof, and other halo compounds Without addition of a large amount of emission flame retardant, it is possible to achieve a high degree of flame retardancy as defined in JISA 9511.

  The phosphorus-containing compound used in the present invention is a compound containing a phosphorus atom, and one or more compounds selected from the group of halogenated aromatic alkylallyl ethers and halides thereof, or other halogen-based compounds. If it is a compound which can exhibit a synergistic effect with a flame retardant, there will be no restriction | limiting in particular. Examples thereof include phosphate, phosphonate, phosphinate, phosphite, phosphoric acid, phosphonic acid, phosphinic acid or derivatives thereof, metal salts, melamine salts, ammonium salts, and phosphazenes or derivatives thereof, phosphonitriles or derivatives thereof, and the like.

  Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxy Aliphatic hydrocarbon monophosphates such as ethyl acid phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, Xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropyl phosphate) Nyl) phenyl phosphate, diphenyl-2-acryloyloxyethyl phosphate, aromatic hydrocarbon monophosphates such as diphenyl-2-methacryloyloxyethyl phosphate, resorcinol diphenyl phosphate, resorcinol dixylenyl phosphate, resorcinol dicresyl phosphate, Bisphenol A / diphenyl phosphate, bisphenol A / dixylenyl phosphate, bisphenol A / dicresyl phosphate, hydroquinone / diphenyl phosphate, hydroquinone / dixylenyl phosphate, hydroquinone / dicresyl phosphate, resorcinol / polyphenyl phosphate, resorcinol / poly (di -2,6-Xylyl) phosphate bisphenol A Condensed phosphates such as licresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate, melamine phosphate, melamine phosphite, melamine pyrophosphate, ammonium phosphate, ammonium pyrophosphate, ammonium phosphate amide, phosphoric acid Amide, piperazine diphosphite, piperazine phosphite, piperazine pyrophosphate, guanazole phosphite, phosphazene, melamine polyphosphate, melamine polyphosphate, melem polyphosphate, ammonium polyphosphate, ammonium polyphosphate amide, polyphosphate amide, poly Examples thereof include phosphorus-containing nitrogen-containing compounds such as phosphazene and phosphonitrile. Furthermore, halogenated phosphate compounds such as the aforementioned tris (tribromoneopentyl) phosphate and tris (bromophenyl) phosphate may be used as the phosphorus-containing compound. Phosphorus-containing compounds can be used alone or in admixture of two or more.

  The amount of the phosphorus-containing compound added is one or more compounds selected from the group of halogenated aromatic alkyl allyl ethers and halides thereof, and other halogen-based flame retardants, foaming agent types and their contents, Although it is appropriately adjusted depending on the density of the foam to be produced, it is generally 0.1 to 10 parts by weight, preferably 0.3 to 9 parts by weight, more preferably, with respect to 100 parts by weight of the styrene resin. 0.5 to 8 parts by weight. If it is less than 0.1 part by weight, the synergistic effect of flame retardancy cannot be obtained, and if it exceeds 10 parts by weight, the moldability during the production of the foam may be impaired.

  The nitrogen-containing compound used in the present invention is a compound containing a nitrogen atom, and one or more compounds selected from the group of halogenated aromatic alkylallyl ethers and halides thereof, or other compounds thereof If it is a compound which can exhibit a synergistic effect with a halogenated flame retardant, there will be no restriction | limiting in particular. Examples thereof include triazine skeleton-containing compounds, cyanuric acid or isocyanuric acid and derivatives thereof, guanidine compounds, azo compounds, and tetrazole compounds.

  Specific examples of the nitrogen-containing compound include triazine skeleton-containing compounds such as melamine, melam, melem, melon, and methylolmelamine or derivatives thereof, cyanuric acid, methyl cyanurate, diethyl cyanurate, trimethyl cyanurate, triethyl cyanurate, Isocyanuric acid, methyl isocyanurate, N, N′-diethyl isocyanurate, trismethyl isocyanurate, trisethyl isocyanurate, bis (2-carboxyethyl) isocyanurate, 1,3,5-tris (2-carboxyethyl) isocyanate Cyanuric acid such as nurate, tris (2,3-epoxypropyl) isocyanurate, isocyanuric acid or derivatives thereof, triazine skeleton-containing compound such as melamine and cyanuric acid or isocyanuric acid Salts made of a conductor, include, for example melamine cyanurate. Furthermore, the aforementioned azo compounds such as hydrazodicarbonamide, azodicarbonamide, azoisobutyronitrile, tetrazoleamine salts such as tetrazole guanidine salt, tetrazole piperazine salt, tetrazole ammonium salt, tetrazole sodium salt, tetrazole manganese salt Tetrazole compounds such as tetrazole metal salts such as 5,5-bistetrazole diguanidine salt, 5,5-bistetrazole diammonium salt, 5,5-bistetrazole diaminoguanidine salt, 5,5-bistetrazole piperazine salt For example, a blowing agent used as a blowing agent other than saturated hydrocarbons may be used as the nitrogen-containing compound. Furthermore, the above-mentioned ethylenebistetrabromophthalimide, ethylenebisdibromonorbornanedicarboximide, 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine, tris (2 Halogen and nitrogen atom-containing compounds such as (, 3-dibromopropyl) isocyanurate may be used as the nitrogen-containing compound. A nitrogen-containing compound can be used individually or in mixture of 2 or more types.

  The amount of the nitrogen-containing compound added is one or more compounds selected from the group of halogenated aromatic alkyl allyl ethers and halides thereof, and other halogen-based flame retardants, blowing agent types and their contents, Although it is appropriately adjusted depending on the density of the foam to be produced, it is generally 0.1 to 10 parts by weight, preferably 0.3 to 9 parts by weight, more preferably, with respect to 100 parts by weight of the styrene resin. 0.5 to 8 parts by weight. If it is less than 0.1 part by weight, the synergistic effect of flame retardancy cannot be obtained, and if it exceeds 10 parts by weight, the moldability during the production of the foam may be impaired.

  The boron-containing compound used in the present invention is a compound containing a boron atom, and one or more compounds selected from the group of halogenated aromatic alkylallyl ethers and halides thereof, or other compounds thereof. If it is a compound which can exhibit a synergistic effect with a halogenated flame retardant, there will be no restriction | limiting in particular. For example, boric acid, borax, metal borate, boron oxide, boron phosphate, borosilicates and the like can be mentioned.

  Specific examples of the boron-containing compound include boric acid, borax, zinc borate, barium borate, magnesium borate, calcium borate, aluminum borate, strontium borate, zirconium borate, tin borate and the like. Examples thereof include acid metal salts, and derivatives such as hydrates of these compounds, and boron oxides such as diboron dioxide, diboron trioxide, tetraboron trioxide, and tetraboron pentoxide. Boron-containing compounds can be used alone or in admixture of two or more.

  The amount of boron-containing compound added is one or more compounds selected from the group of halogenated aromatic alkyl allyl ethers and halides thereof, and other halogen-based flame retardants, foaming agent types and their contents, Although it is appropriately adjusted depending on the density of the foam to be produced, it is generally 0.1 to 10 parts by weight, preferably 0.3 to 9 parts by weight, more preferably, with respect to 100 parts by weight of the styrene resin. 0.5 to 8 parts by weight. If it is less than 0.1 part by weight, the synergistic effect of flame retardancy cannot be obtained, and if it exceeds 10 parts by weight, the moldability during the production of the foam may be impaired.

  The sulfur-containing compound used in the present invention is a compound containing a sulfur atom, which is one or more compounds selected from the group of halogenated aromatic alkylallyl ethers and halides thereof, and other compounds. If it is a compound which can exhibit a synergistic effect with a halogenated flame retardant, there will be no restriction | limiting in particular. For example, sulfate compounds such as ammonium sulfate, melamine sulfate, sodium sulfate, magnesium sulfate, calcium sulfate, aluminum sulfate, and iron sulfate, sulfamic acid compounds such as sulfamic acid, ammonium sulfamate, guanidine sulfamate, benzenesulfonic acid, benzene Disulfonic acid, p-vinylbenzenesulfonic acid, p-toluenesulfonic acid, o-toluenesulfonic acid, p-octylbenzenesulfonic acid, o-octylbenzenesulfonic acid, p-dodecylbenzenesulfonic acid, m-dodecylbenzenesulfonic acid, alkylbenzenesulfonic acid such as o-dodecylbenzenesulfonic acid, fluorobenzenesulfonic acid, chlorobenzenesulfonic acid, bromobenzenesulfonic acid, iodobenzenesulfonic acid, phenolsulfuric acid Acid, phenol disulfonic acid, sulfanilic acid (aminobenzenesulfonic acid), naphthalenesulfonic acid, 2-naphthol-1-sulfonic acid, 2-methylnaphthalene-1-sulfonic acid or lithium, sodium of these aromatic sulfonic acids, Sulfonic acids such as salts with Group 1A metals such as potassium, salts with Group 2A metals such as magnesium, calcium, barium, salts with metals such as zinc, iron, copper, etc. Compounds and the like. The sulfur-containing compounds can be used alone or in admixture of two or more.

  The amount of the sulfur-containing compound added is one or more compounds selected from the group of halogenated aromatic alkyl allyl ethers and halides thereof, and other halogen-based flame retardants, blowing agent types and their contents, Although it is appropriately adjusted depending on the density of the foam to be produced, it is generally 0.1 to 10 parts by weight, preferably 0.3 to 9 parts by weight, more preferably, with respect to 100 parts by weight of the styrene resin. 0.5 to 8 parts by weight. If it is less than 0.1 part by weight, the synergistic effect of flame retardancy cannot be obtained, and if it exceeds 10 parts by weight, the moldability during the production of the foam may be impaired.

  The phosphorus-containing compound, nitrogen-containing compound, boron-containing compound and sulfur-containing compound are used alone or in combination of two or more.

  Further, the phosphorus-containing compound, nitrogen-containing compound, boron-containing compound, and sulfur-containing compound are selected from surface treatment agents such as various thermosetting resins, various thermoplastic resins, silane coupling agents, titanium-based compounds, and inorganic compounds. Even if it is surface-coated with a seed or two or more kinds of compounds, it can be suitably used.

  Further, in the case of phosphorus-containing compounds, nitrogen-containing compounds, boron-containing compounds, and sulfur-containing compounds, when water is used as another foaming auxiliary agent in order to obtain high heat insulating properties, the small bubbles and large bubbles are contained in the foam. The compound which does not inhibit the effect which this occurs is preferable. For example, a compound which is hardly soluble in water or has a solubility in water of 10% by weight or less in a temperature range near room temperature (about 10 to 30 ° C.) is preferable. When the solubility in water is high, the effect of generating the small bubbles and the large bubbles tends to be inhibited. If the solubility in water is high, or if there is a tendency to inhibit the effect of generating small bubbles and large bubbles, it may be improved by applying a surface coating treatment. It is preferable to use a compound.

  In the case of containing a relatively large amount of one or more compounds having a flammable ozone depletion coefficient of 0 as a foaming agent in order to exhibit high heat insulation performance corresponding to two or three types of extruded polystyrene foam heat insulating plates, When one or more compounds selected from the group of halogenated aromatic alkyl allyl ethers and their halides or only this and other halogen flame retardants are used as flame retardants, they are not necessarily stably flame retardant when added in small amounts. There is a tendency not to be obtained. Further, when the amount added is increased, the foam tends to peel or tear immediately after being extruded from the die, and the foam tends not to be obtained satisfactorily.

  In particular, when a saturated hydrocarbon is used as the foaming agent, the residual foaming agent is released from the foam into the atmosphere when the foam is burned, and the foaming agent burns, so that the foam is generated by the combustion heat of the foaming agent. There was a tendency for the surface to melt and spread.

  However, these tendencies also include phosphorus-containing compounds, nitrogen-containing compounds, halogenated aromatic alkyl allyl ethers, one or more compounds selected from the group of halides thereof, and other halogen-based flame retardants. The combined use of a boron compound and a sulfur-containing compound has an excellent effect that it can be reduced or eliminated by inhibiting the combustion of the residual foaming agent, and it is excellent when an appropriate amount is used. It is possible to obtain a foam molded article having high flame retardancy and molding process stability.

  When the cell structure of the styrene resin foam of the present invention is composed of bubbles having a cell diameter of about 0.01 to 1 mm, and most of the bubbles are composed of bubbles having similar cell diameters, the cell diameter of the bubbles Are roughly classified into two types or three or more types. In particular, in order to exhibit high heat insulation performance corresponding to two or three types of extruded polystyrene foam heat insulating plates, in the case where most of the bubbles are composed of cells with similar cell diameters, depending on the average cell diameter , A compound selected from the group consisting of hydrocarbons and halogenated hydrocarbons and having a relatively large amount of one or more compounds having an ozone depletion coefficient of 0. In particular, when the cell is classified into two types or three or more types, a cell having a relatively small cell diameter (small cell) having a cell diameter of approximately 0.25 mm or less as a foam cell structure of the foam, In a characteristic bubble structure in which bubbles having a relatively large bubble diameter (large bubbles) of approximately 0.3 mm to 1 mm are mixed in a sea-island shape, one or more types having a relatively small ozone depletion coefficient of 0 High heat insulation By containing the compound can be achieved. In particular, when using one or more compounds having a flammable ozone depletion coefficient of 0, the latter cell structure is preferable. Such a cell structure can be formed by using water as another foaming agent, for example.

  When water is used as the other foaming agent, water-absorbing or water-swelling layered silicates such as smectite and swellable fluorinated mica or organically treated products thereof, water-absorbing polymers, AEROSIL manufactured by Nippon Aerosil Co., Ltd. By adding one or more of anhydrous silica having a silanol group, etc. (in the present invention, these substances are collectively referred to as a water-absorbing substance), the above-mentioned small bubbles and large bubbles are added to the foam. Can further improve the moldability, productivity and heat insulation performance of the resulting foam.

  The water-absorbing substance used here is considered to absorb water that is not compatible with the styrenic resin to form a gel, which can be uniformly dispersed in the styrenic resin in the gel state. used.

  The content of the water-absorbing substance used in the present invention is appropriately adjusted depending on the amount of water added and the like, but is preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of the styrenic resin. Preferably it is 0.3-8 weight part, Most preferably, it is 0.5-7 weight part. If the content of the water-absorbing substance is less than the above range, the amount of water adsorbed by the water-absorbing substance may be insufficient, and pores may be generated due to poor dispersion of water in the extruder, resulting in a molded product failure. In some cases, poor dispersion of the water-absorbing substance occurs in the extruder, air bubbles become uneven, and the heat insulating performance of the foam deteriorates and varies.

  The layered silicate used in the present invention mainly comprises a tetrahedral sheet of silicon oxide and an octahedral sheet of mainly metal hydroxide, and the tetrahedral sheet and the octahedral sheet form a unit layer, and the unit layer alone In addition, a plurality of layers may be laminated between layers via a cation to form primary particles, or aggregate particles of primary particles (secondary particles) may be present. Examples of layered silicates include smectite clay and swellable mica.

The smectite clay is represented by the following general formula 6
X _0.2 to _0.6 Y ₂ to ₃ Z ₄ O ₁₀ (OH) ₂ · nH ₂ O ··· General formula 6
(However, X is at least one selected from the group consisting of K, Na, 1 / 2Ca, and 1 / 2Mg, and Y is a group consisting of Mg, Fe, Mn, Ni, Zn, Li, Al, and Cr. And Z is at least one selected from the group consisting of Si and Al, where H ₂ O represents a water molecule bonded to an interlayer ion, and n is an interlayer ion. And varies significantly depending on the relative humidity).

  Specific examples of the smectite group clay include, for example, montmorillonite, beidellite, nontronite, saponite, iron saponite, hectorite, soconite, stevensite, bentonite, or the like, or a substitution product, derivative thereof, or a mixture thereof. .

The swelling mica is represented by the following general formula 7
X _0.5 to _1.0 Y ₂ to ₃ (Z ₄ O ₁₀ ) (F, OH) ₂ ... General formula 7
(However, X is at least one selected from the group consisting of Li, Na, K, Rb, Ca, Ba, and Sr, and Y is selected from the group consisting of Mg, Fe, Ni, Mn, Al, and Li) And Z is one or more selected from the group consisting of Si, Ge, Al, Fe, and B.) or natural or synthesized.

  These are water, a polar organic compound that is compatible with water at an arbitrary ratio, and a substance that swells in a mixed solvent of water and the polar organic compound. For example, lithium teniolite, sodium Type teniolite, lithium type tetrasilicon mica, sodium type tetrasilicon mica and the like, or a substituted product, a derivative thereof, or a mixture thereof.

Some of the above swellable mica have a structure similar to vermiculites, and such vermiculites and the like can also be used. The vermiculite-equivalent products are classified into 3 octahedron type and 2 octahedron type.
_{(Mg, Fe, Al) 2} ~ 3 (Si 4-x Al x) O 10 (OH) 2 · (M +, M 2+ 1/2) x · nH 2 O ······ formula 8
(Wherein M is an exchangeable cation of an alkali or alkaline earth metal such as Na and Mg, x = 0.6 to 0.9, and n = 3.5 to 5). .

  Swellable layered silicates may be used alone or in combination of two or more. Among these, smectite group clay and swellable mica are preferable from the viewpoint of dispersibility in the obtained foam, and more preferably sodium between layers such as montmorillonite, bentonite, hectorite, synthetic smectite, and swellable fluorine mica. Swellable mica having ions is preferred.

  Typical examples of bentonite include natural bentonite and purified bentonite. Also, organic bentonite can be used. The smectite in the present invention includes montmorillonite-modified products such as anionic polymer-modified montmorillonite, silane-treated montmorillonite, and highly polar organic solvent composite montmorillonite.

  The content of smectite such as bentonite is appropriately adjusted depending on the amount of water added and the like, but is preferably 0.2 to 10 parts by weight, more preferably 0.8 parts per 100 parts by weight of the styrenic resin. 3 to 8 parts by weight, particularly preferably 0.5 to 7 parts by weight, most preferably 1 to 5 parts by weight. When the smectite content is within the above range, the amount of water adsorbed by the smectite is insufficient with respect to the amount of water injected, and pores are generated due to poor dispersion of the water in the extruder, which tends to result in defective molded articles. On the other hand, when the amount exceeds the above range, the amount of the inorganic powder present in the styrene resin becomes excessive, so that uniform dispersion in the styrene resin becomes difficult and bubble unevenness tends to occur. Furthermore, it tends to be difficult to maintain closed cells. Therefore, it becomes easy to produce deterioration and variation of the heat insulation performance of a foam. The mixing ratio of water / smectite (bentonite) is in a weight ratio, preferably 0.02 to 20, more preferably 0.1 to 10, particularly preferably 0.15 to 5, most preferably 0.25 to 2. Is ideal.

  The average cell diameter in the styrene resin foam obtained in the present invention is preferably 0.05 to 1 mm, more preferably 0.06 to 0.6 mm, and particularly preferably 0.08 to 0.4 mm.

  In addition, when water is used as the other foaming agent, in the foam, bubbles with a relatively small bubble diameter (small bubbles) having a bubble diameter of approximately 0.25 mm or less, and a bubble diameter of approximately 0.3 mm to 1 mm. It is preferable because a foam having a characteristic bubble structure in which bubbles having a relatively large bubble diameter (large bubbles) are mixed in a sea-island shape is obtained, and the heat insulating performance of the obtained foam is improved. When water is used as the other foaming agent, it may be used in combination with only one or more compounds having an ozone depletion coefficient of 0, but one or more compounds having an ozone depletion coefficient of 0 and other than water A foaming agent comprising three or more components in combination with other foaming agents (for example, dimethyl ether, carbon dioxide, etc.) is preferable because the foamability and moldability of the foam are further improved.

  Furthermore, in the foam having a specific cell structure in which small bubbles having a bubble diameter of 0.25 mm or less and large bubbles having a bubble diameter of 0.3 to 1 mm are mixed, the ratio of the area of the small bubbles to the cross-sectional area of the foam (Occupied area ratio per unit cross-sectional area) (hereinafter referred to as small bubble area ratio) is preferably 5 to 95%, more preferably 10 to 90%, particularly preferably 20 to 80%, and most preferably 25 to 70. %.

  In the present invention, various flame retardant assistants, silica, talc, calcium silicate, wollastonite, kaolin, clay, mica, zinc oxide, titanium oxide, carbonic acid, as long as the effects of the present invention are not inhibited as necessary. Inorganic compounds such as calcium, processing aids such as sodium stearate, magnesium stearate, barium stearate, liquid paraffin, olefin waxes, stearylamide compounds, phenolic antioxidants, phosphorus stabilizers, nitrogenous stabilizers Additives such as sulfur stabilizers, light-resistant stabilizers such as benzotriazoles and hindered amines, flame retardants other than those mentioned above, antistatic agents, colorants such as pigments, and the like can be added.

  As the flame retardant aid, it is particularly preferable that it is one or more compounds selected from the group of halogenated aromatic alkyl allyl ethers and halides thereof, or a substance that exhibits a synergistic effect with other halogen flame retardants. Although there is no restriction | limiting, the flame retardant adjuvant which decomposes | disassembles with a metal oxide, a metal complex, and a heat | fever, and generate | occur | produces is preferable.

  For more stable extrusion foaming, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis {3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate}, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-t-butyl-4- Hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxy-benzyl phosphate-diethyl ester, 1,3,5-trimethyl-2,4,6- Hindered phenol-based antioxidants such as lith (3,5-di-t-butyl-4-hydroxybenzyl) benzene and tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate; Phenylphosphite, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bisstearyl pentaerythritol diphosphite, bis (2 , 4-Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite Phosphorus stabilizers such as 2,2,4-trimethyl-1,2-dihydroquinoline polymer, alkylated diph Amine stabilizers such as nilamine, octylated diphenylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, 3,3-thiobispropionic acid didecyl ester, 3,3′-thiobispropionic acid diester It is preferable to add a sulfur-based stabilizer such as octadecyl ester.

The styrene resin foam of the present invention is
(Ii) One or more compounds selected from the group of halogenated aromatic alkyl allyl ethers and halides thereof in styrene resins, and other halogen flame retardants, diphenylalkanes, phosphorus-containing compounds, Nitrogen compound, boron-containing compound, sulfur-containing compound, and other additives are mixed and then heated and melted.
(B) One or more compounds selected from the group of styrene resins and halogenated aromatic alkyl allyl ethers and halides thereof, and if necessary, other halogen flame retardants, diphenylalkanes, phosphorus-containing compounds, One or more additives selected from nitrogen compounds, boron-containing compounds, sulfur-containing compounds and other additives are mixed and then heated and melted, and the remaining additives are liquefied or melted as they are or as necessary. Add and mix by heating.
(Ha) one or more compounds selected from the group of halogenated aromatic alkyl allyl ethers and halides thereof in advance in a styrene resin, and, if necessary, other halogen flame retardants, diphenylalkanes, phosphorus-containing compounds, After mixing one or more additives selected from nitrogen-containing compounds, boron-containing compounds, sulfur-containing compounds and other additives, a heated and melted composition is prepared, and then the composition and the remaining additives, If necessary, styrene resin is mixed again, supplied to the extruder and melted by heating.
One or more compounds selected from the group of styrene resins, halogenated aromatic alkyl allyl ethers, and halides thereof, and other halogen flame retardants, diphenylalkanes, phosphorus-containing compounds, nitrogen-containing as necessary A compound, boron-containing compound, sulfur-containing compound, and other additives are supplied to a heating and melting means such as an extruder, and a foaming agent is added to a styrenic resin under a high-pressure condition at any stage. It is produced by cooling to a temperature suitable for extrusion foaming and extrusion foaming the fluid gel through a die into the low pressure region to form a foam.

  There are no particular restrictions on the heating temperature, melt kneading time, and melt kneading means when heating and kneading the styrene resin and additives such as a foaming agent. The heating temperature may be equal to or higher than the temperature at which the styrenic resin used melts, but is preferably a temperature at which molecular degradation of the resin due to the influence of a flame retardant is suppressed as much as possible, for example, about 150 to 260 ° C. The melt-kneading time varies depending on the amount of extrusion per unit time, the melt-kneading means, etc., and thus cannot be determined unconditionally. However, the time required for uniformly dispersing and mixing the styrenic resin and the foaming agent is appropriately selected. Examples of the melt-kneading means include a screw-type extruder, but there is no particular limitation as long as it is used for ordinary extrusion foaming. However, in order to suppress the molecular degradation of the resin as much as possible, it is preferable to use a low shear type screw for the screw shape.

  Also, the foam molding method is not particularly limited. For example, the foam obtained by releasing the pressure from the slit die may be used, for example, a molding die and a molding roll installed in close contact with or in contact with the slit die. A general method for forming a plate-like foam can be used.

The thickness of the foam of 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, the thickness is not as thin as a sheet but as a normal plate. Is preferable, usually 10 to 150 mm, preferably 20 to 100 mm. Further, the density of the foam of the present invention is preferably lightweight and excellent heat insulating properties and bending strength, in order to allowed to impart compressive strength is 15~50kg / m ^3, in 20~45kg / m ³ More preferably.

  As a part or all of the foaming agent of the present invention, it contains one or more compounds selected from the group of hydrocarbons and halogenated hydrocarbons and having an ozone depletion coefficient of 0, and Styrenic resin foam characterized by containing one or more compounds selected from the group of halogenated aromatic alkyl allyl ethers and their halides as flame retardants is excellent in recyclability and has become a foam. Can be used again for molding. For example, the regenerated styrene resin composition obtained by pulverizing the styrene resin foam of the present invention and melting and pelletizing with an extruder is used as a part of the styrene resin, so-called new styrene resin. And extrusion foaming is possible. Even in such a case, a foam excellent in various physical properties such as a small bubble area ratio can be obtained. It is preferable to appropriately foam and mix and extrude. It is further preferable to add other additives. The upper limit amount of the regenerated styrene resin composition (recycled product) is, for example, 200 parts by weight, preferably 150 parts by weight per 100 parts by weight of a new styrene resin.

Next, although the manufacturing method of the thermoplastic resin extrusion foam of this invention is demonstrated in detail based on an Example, this invention is not restrict | limited only to this Example. Unless otherwise specified, “parts” represents parts by weight and “%” represents% by weight. (However, the small bubble area ratio (%) is the area ratio.)
The following evaluation was performed.
1) Combustibility The combustibility of the extruded foam was evaluated according to the following criteria using test pieces having a thickness of 10 mm, a length of 200 mm, and a width of 25 mm in accordance with JISA 9511. The measurement was carried out on foams that had passed 7 days after being cut into the above dimensions after production.

Burning time ◎: All 5 flame extinguishing times are within 3 seconds. ○: Out of 5 flame extinguishing times, at least one exceeds 3 seconds, but the remaining 3 or more are within 3 seconds. Δ: Flame extinguishing time. Of the five, at least three of them exceed 3 seconds, but the remaining one or more are within 3 seconds. X: All 5 flame extinguishing times exceed 3 seconds. Combustion distance ◎: All 5 are within the limit line. ○: Stops at least 1 out of 5 but the reduction exceeds the limit line, but the remaining 3 or more stop within the limit line. Δ: At least 3 out of 5 limit the combustion. Exceeds line but combustion stops within the limit line for the remaining one or more ×: Combustion exceeds the limit line with all five combustion conditions ◎: No combustion of foaming agent is observed ○: Combustion of foaming agent Δ: Combustion of the foaming agent is observed, but no complete burning is observed. ×: Combustion of the foaming agent is also observed. To 2) was measured according to thermal conductivity of the thermal conductivity extruded foam JISA 9511. The measurement was carried out on a foam that had passed 90 days after the production, after removing a 10 mm portion from the surface.
3) Area ratio of small bubbles For the extruded foam, the ratio of occupied area per cross-sectional area of the foam having a bubble diameter of 0.25 mm or less was determined as follows. Here, a bubble having a bubble diameter of 0.25 mm or less is a bubble having an equivalent circle diameter of 0.25 mm or less.
a) Magnify 30 times with a scanning electron microscope (manufactured by Hitachi, Ltd., product number: S-450) and photograph a longitudinal section of the foam.
b) An OHP sheet is placed on the photograph taken, and a portion corresponding to a bubble having a diameter in the thickness direction larger than 7.5 mm (corresponding to a bubble having an actual dimension larger than 0.25 mm) is black ink. Fill in and copy (primary processing).
c) The primary processing image is taken into an image processing apparatus (Pierce Co., Ltd., product number: PIAS-II), and a dark color portion and a light color portion, that is, a portion painted with black ink are identified.
d) Of the dark portion, a portion corresponding to the area of a circle having a diameter of 7.5 mm or less, that is, a portion having a long diameter in the thickness direction but only an area of a circle having a diameter of 7.5 mm or less. Is lightened to correct the dark portion.
e) Using “FRACTAREA (area ratio)” in the image analysis calculation function, the area ratio of the bubble diameter of 7.5 mm or less (light color portion divided by shading) in the entire image is obtained by the following equation.
Small bubble occupation area ratio (%) = (1−area of dark color portion / area of entire image) × 100
4) Specific viscosity η _{sp of} styrene resin constituting the foam
The specific viscosity η _sp was determined by the following procedure.

  a) About 1 g of the foam sample is put in a test tube with a stopper, and about 30 ml of methyl ethyl ketone is added and dissolved. In the case of a sample that is difficult to dissolve, it is sufficiently dissolved by heating at 60 ° C. or lower.

  b) Cap the test tube and let it stand for 6 hours or more to precipitate insoluble matter (solid matter, gel).

  c) After standing, gently transfer the supernatant in the test tube to a beaker with a capacity of 100 ml or more.

  d) While stirring the inside of the beaker using a magnetic stirrer, add several ml of ethanol and confirm that the resin precipitates. Further, ethanol is added in several ml, and when the precipitated resin does not redissolve, ethanol is slowly added dropwise and almost the entire resin can be precipitated.

  e) Mix the precipitated resin with a stir bar or the like to make a lump and sink it to the bottom of the beaker. Gently wash while pressing the resin on the bottom of the beaker.

  f) After washing, the supernatant in the beaker is discarded, and the resin content is placed on an aluminum foil and stretched to form a thin plate.

  g) Put the whole aluminum foil in an oven at 70 ° C. and leave it for 12 hours or more to completely evaporate the solvent.

  h) As a sample, the dried resin content of 250 mg (precise balance) is placed in a test tube with a stopper, and 25 ml (precise balance using a whole pipette) of toluene is added and dissolved. When it is difficult to dissolve, it is sufficiently dissolved by heating at 60 ° C. or lower.

  i) Using a 10 ml sample (precise balance using a whole pipette), measure the relative viscosity with respect to toluene (special grade) at 30 ° C. using an Ostwald viscosity tube (water 30 ° C./50 S type). The specific viscosity is calculated by the following formula.

Specific viscosity (η _sp ) = (sample passage time) / (toluene passage time) −1
5) Recyclability After the extruded foam was pulverized with a pulverizer, it was melted by heating at a cylinder temperature setting of 230 ° C. using a twin-screw extruder (manufactured by Nippon Steel Co., Ltd.) and pelletized.

  Recyclability was evaluated based on the following formula.

Specific viscosity (η _sp ) retention rate = (specific viscosity of styrene resin (η _sp ) divided by heat melting and pelletizing after pulverization (η _sp ) ÷ specific viscosity of styrene resin originally used (η _sp )) × 100 (%)
○: Specific viscosity (η _sp ) retention is 75% or more.
Δ: Specific viscosity (η _sp ) retention is 60 to 75%.
X: Specific viscosity (η _sp ) retention is less than 60%.
6) Density of foam The foam density of the extruded foam is the following formula: foam density (g / cm ³ ) = foam weight (g) / foam volume (cm ³ )
And the unit was expressed in terms of (kg / m ³ ).

The following raw materials were used.
A: Styrene resin A-1: Polystyrene (G9401 manufactured by PS Japan Co., Ltd.)
B: One or more compounds selected from the group of halogenated aromatic alkyl allyl ethers and halides thereof B-1: Tetrabromobisphenol A-bis (2-methylallyl ether) (manufactured by Daiichi FAR Co., Ltd.) )
B-2: Tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether) (manufactured by Daiichi FAR Co., Ltd.)
C: Other halogen flame retardant C-1: Tetrabromobisphenol A diallyl ether (Fireguard 3200 manufactured by Teijin Chemicals Ltd.)
C-2: Decabromodiphenyl oxide (Frame cut 110R manufactured by Tosoh Corporation)
C-2: Hexabromocyclododecane (SAYTEX HP-900 manufactured by ALBEMARLE CORPORATION)
D: Diphenylalkane D-1: 2,3-dimethyl-2,3-diphenylbutane (Parkadox 30 manufactured by Kayaku Akzo Co., Ltd.)
E: Phosphorus-containing compound, nitrogen-containing compound, boron-containing compound, sulfur-containing compound E-1: Triphenyl phosphate (TPP manufactured by Daihachi Chemical Industry Co., Ltd.)
E-2: Isocyanuric acid (ICA-P manufactured by Shikoku Kasei Co., Ltd.)
E-3: Boron oxide (reagent manufactured by Wako Pure Chemical Industries, Ltd.)
E-4: p-Toluenesulfonic acid monohydrate (Reagent manufactured by Wako Pure Chemical Industries, Ltd.)
F: foaming agent; one or more compounds selected from the group consisting of hydrocarbons and halogenated hydrocarbons and having an ozone depletion coefficient of 0 F-1: propane (odorless propane manufactured by Iwatani Corporation)
F-2: Isobutane (isobutane manufactured by Mitsui Chemicals, Inc.)
F-3: HFC-134a (HFC-134a manufactured by Daikin Industries, Ltd.)
G: Other blowing agent G-1: Dimethyl ether (dimethyl ether manufactured by Mitsui Chemicals, Inc.)
G-2: Water H: Other additives H-1: Talc (Talcan powder manufactured by Hayashi Kasei Co., Ltd.)
H-2: Barium stearate (barium stearate manufactured by Sakai Chemical Industry Co., Ltd.)
H-3: Bentonite (Benguel 23, Toyshun Mining Co., Ltd.)
H-4: AEROSIL (Nippon Aerosil Co., Ltd., AEROSIL)
J-5: Stabilizer (Ciba Specialty Chemicals Co., Ltd. IRGANOX B911 (hindered phenol antioxidant IRGANOX 1076: octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) Phosphorus stabilizer IRGAFOS 168: 1: 1 mixture of tris (2,4-di-t-butylphenyl) phosphite)
Example 1
Tetrabromobisphenol A-bis (2-methylallyl ether) as one or more compounds selected from the group of halogenated aromatic alkylallyl ethers and halides thereof with respect to 100 parts of styrene resin (A-1) (B-1) 3 parts, furthermore, a mixture comprising talc (H-1) 0.5 part and barium stearate (H-2) 0.25 part was dry blended, and the resulting mixture had a diameter of 65 mm and a diameter of A 90 mm-thick one was fed at a rate of about 70 kg / hr to an extruder connected vertically. The mixture supplied to the 65 mm-diameter extruder is heated to 200 ° C. and kneaded, and the resin temperature is cooled to 120 ° C. with the 90 mm-diameter extruder connected to the extruder, and is attached to the tip of the 90 mm-diameter extruder. Extruded into the atmosphere from the provided base having a rectangular cross section with a thickness direction of 2 mm and a width direction of 50 mm, a rectangular parallelepiped extruded foam was obtained. The density of the obtained foam was 27 kg / m ³ .

  At this time, as the foaming agent, the foaming agent composed of 50% propane (F-1) and 50% dimethyl ether (G-1) was 8 parts with respect to 100 parts of the styrene resin. The resin was press-fitted into the resin from the vicinity of the tip (the end connected to the end opposite to the end of the extruder having a diameter of 90 mm).

  The properties of the obtained extruded foam are shown in Table 1.

(Examples 2-9)
One or more compounds (B) selected from the group of halogenated aromatic alkyl allyl ethers and halides thereof, other halogen flame retardants (C), diphenylalkanes (D), blowing agents (F), other foams A foam was obtained in the same manner as in Example 1 except that the type and addition amount of the agent (G) were changed to the values shown in Table 1.

  The properties of the obtained extruded foam are shown in Table 1.

(Comparative Examples 1-3)
A foam was obtained in the same manner as in Example 1 except that other halogen flame retardant (C), foaming agent (F), other foaming agent (G), and addition amount were set to the values shown in Table 1.

本発明の実施例である実施例１〜９と比較例１〜３を比較して明らかなように、本発明によれば、難燃性と共にリサイクル性にも優れた発泡体が得られることが判る。

As is clear by comparing Examples 1 to 9, which are examples of the present invention, and Comparative Examples 1 to 3, according to the present invention, a foam having excellent flame retardancy and recyclability can be obtained. I understand.

(Example 10)
Tetrabromobisphenol A-bis (2-methylallyl ether) as one or more compounds selected from the group of halogenated aromatic alkylallyl ethers and halides thereof with respect to 100 parts of styrene resin (A-1) (B-1) 3 parts, furthermore, a mixture comprising talc (H-1) 0.5 part and barium stearate (H-2) 0.25 part was dry blended, and the resulting mixture had a diameter of 65 mm and a diameter of A 90 mm-thick one was fed at a rate of about 70 kg / hr to an extruder connected vertically. The mixture supplied to the 65 mm-diameter extruder is heated to 200 ° C. and kneaded, and the resin temperature is cooled to 120 ° C. with the 90 mm-diameter extruder connected to the extruder, and is attached to the tip of the 90 mm-diameter extruder. Extruded into the atmosphere from the provided base having a rectangular cross section with a thickness direction of 2 mm and a width direction of 50 mm, a rectangular parallelepiped extruded foam was obtained. The density of the obtained foam was 32 kg / m ³ .

  At this time, as the foaming agent, the foaming agent composed of 67% isobutane (F-2) and 33% dimethyl ether (G-1) was 6 parts with respect to 100 parts of the styrene-based resin. The resin was press-fitted into the resin from the vicinity of the tip (the end connected to the end opposite to the end of the extruder having a diameter of 90 mm).

  The properties of the obtained extruded foam are shown in Table 2.

(Examples 11 to 20)
One or more compounds (B) selected from the group of halogenated aromatic alkyl allyl ethers and halides thereof, other halogen flame retardants (C), phosphorus-containing compounds, nitrogen-containing compounds, boron-containing compounds, sulfur-containing compounds A foam was obtained in the same manner as in Example 11 except that (E), the type of foaming agent (F), the type of other foaming agent (G), and the amount added were changed to the values shown in Table 2.

  The properties of the obtained extruded foam are shown in Table 2.

(Comparative Examples 4-6)
Table 2 shows the types and amounts of other halogen flame retardants (C), phosphorus-containing compounds, nitrogen-containing compounds, boron-containing compounds, sulfur-containing compounds (E), blowing agents (F), and other blowing agents (G). A foam was obtained in the same manner as in Example 11 except that the values shown were used.

本発明の実施例である実施例１０〜２０と比較例４〜６を比較して明らかなように、本発明によれば、難燃性と共にリサイクル性にも優れた発泡体が得られることが判る。さらに、含燐化合物、含窒素化合物、含ホウ素化合物の添加されていない実施例１０および１３と含燐化合物、含窒素化合物、含ホウ素化合物が添加されている実施例１１〜１２および１５〜１７を比較して明らかなように、含燐化合物、含窒素化合物、含ホウ素化合物を添加することにより、発泡剤の燃焼が抑制され難燃性が向上することが判る。

As is clear by comparing Examples 10 to 20 and Comparative Examples 4 to 6 which are examples of the present invention, according to the present invention, a foam having excellent flame retardancy and recyclability can be obtained. I understand. Further, Examples 10 and 13 to which no phosphorus-containing compound, nitrogen-containing compound and boron-containing compound were added and Examples 11 to 12 and 15 to 17 to which phosphorus-containing compound, nitrogen-containing compound and boron-containing compound were added were used. As is clear from the comparison, it can be seen that by adding a phosphorus-containing compound, a nitrogen-containing compound, or a boron-containing compound, combustion of the foaming agent is suppressed and flame retardancy is improved.

(Example 21)
Tetrabromobisphenol A-bis (2-methylallyl ether) as one or more compounds selected from the group of halogenated aromatic alkylallyl ethers and halides thereof with respect to 100 parts of styrene resin (A-1) 3 parts of (B-1), 1 part of triphenyl phosphate (E-1) as the phosphorus-containing compound, 2 parts of isocyanuric acid (E-2) as the nitrogen-containing compound, talc (H-1) 0 as the other additive .2 parts, 0.25 part of barium stearate (H-2), 1 part of bentonite (H-3), 0.01 part of AEROSIL (H-4) were dry blended, and the resulting mixture was An extruder having a diameter of 65 mm and a diameter of 90 mm was vertically connected to an extruder at a rate of about 70 kg / hr. The mixture supplied to the 65 mm-diameter extruder is heated to 200 ° C. and kneaded, and the resin temperature is cooled to 120 ° C. with the 90 mm-diameter extruder connected to the extruder, and is attached to the tip of the 90 mm-diameter extruder. Extruded into the atmosphere from the provided base having a rectangular cross section with a thickness direction of 2 mm and a width direction of 50 mm, a rectangular parallelepiped extruded foam was obtained.

  At this time, as a foaming agent, a foaming agent composed of 59% isobutane (F-2), 29% dimethyl ether (G-1), and 12% water (G-2) was 6.8 parts with respect to 100 parts of styrene resin. Thus, the resin was press-fitted into the resin from the vicinity of the tip of the 65 mm diameter extruder (the end connected to the end opposite to the die of the 90 mm diameter extruder).

  The properties of the obtained extruded foam are shown in Table 3.

(Examples 22 to 28)
One or more compounds (B) selected from the group of halogenated aromatic alkyl allyl ethers and halides thereof, other halogen flame retardants (C), phosphorus-containing compounds, nitrogen-containing compounds (E), blowing agents (F ), A foam was obtained in the same manner as in Example 21 except that the types and addition amounts of the other foaming agents (G) were changed to the values shown in Table 3.

  The properties of the obtained extruded foam are shown in Table 3.

(Comparative Examples 7-9)
Examples except that other halogen flame retardants (C), phosphorus-containing compounds, nitrogen-containing compounds (E), foaming agents (F), types of other foaming agents (G), and addition amounts were set to the values shown in Table 3. In the same manner as in Example 21, a foam was obtained.

本発明の実施例である実施例２１〜２８と比較例７〜９を比較して明らかなように、本発明によれば、難燃性と共にリサイクル性にも優れた発泡体が得られることが判る。さらに、他の発泡剤として水の添加されていない実施例１２および１６と他の発泡剤として水を用い、さらに他の添加剤としてベントナイトおよびＡＥＬＯＳＩＬが添加されている実施例２１〜２２を比較して明らかなように、他の発泡剤として水を用い、さらに他の添加剤としてベントナイトおよびＡＥＬＯＳＩＬを添加することにより、発泡体の発泡セル構造として気泡径が概ね０．２５ｍｍ以下の比較的気泡径の小さい気泡（小気泡）と、気泡径が概ね０．３ｍｍから１ｍｍ程度の比較的気泡径の大きな気泡（大気泡）が海島状に混在してなる特徴的な気泡構造であって、その小気泡面積率が３５〜４０％の気泡構造となることで、熱伝導率も低減し、更に断熱性が向上していることが判る。
（実施例２９）
スチレン系樹脂（Ａ−１）５０部に対して、実施例２１で得られた発泡体のリサイクル品（リサイクル性を評価したペレット）５０部、その他の添加剤として、タルク（Ｈ−１）０．２部、ステアリン酸バリウム（Ｈ−２）０．２５部、ベントナイト（Ｈ−３）１部、ＡＥＲＯＳＩＬ（Ｈ−４）０．０１部とからなる混合物をドライブレンドし、得られた混合物を口径６５ｍｍと口径９０ｍｍのものを縦に連結した押出機へ約７０ｋｇ／ｈｒの割合で供給した。前記口径６５ｍｍの押出機に供給した混合物を、２００℃に加熱して混練し、これに連結された口径９０ｍｍの押出機で樹脂温度を１２０℃に冷却して、口径９０mmの押出機の先端に設けた厚さ方向２ｍｍ、幅方向５０ｍｍの長方形断面の口金より大気中へ押し出し、直方体状の押出発泡体を得た。

As is clear by comparing Examples 21 to 28 and Comparative Examples 7 to 9 which are examples of the present invention, according to the present invention, a foam having excellent flame retardancy and recyclability can be obtained. I understand. Further, Examples 12 and 16 in which water was not added as another blowing agent were compared with Examples 21 to 22 in which water was used as another blowing agent and bentonite and AELOSIL were added as other additives. As is clear from the above, by using water as the other foaming agent and further adding bentonite and AELOSIL as other additives, the foamed cell structure of the foam has a relatively bubble diameter of approximately 0.25 mm or less. A small bubble (small bubble) and a relatively large bubble (large bubble) with a bubble diameter of about 0.3 mm to about 1 mm mixed in a sea-island shape. It can be seen that the formation of a cell structure with a cell area ratio of 35 to 40% reduces the thermal conductivity and further improves the heat insulation.
(Example 29)
For 50 parts of styrene-based resin (A-1), 50 parts of a recycled product of the foam obtained in Example 21 (pellets evaluated for recyclability), and as other additives, talc (H-1) 0 .2 parts, 0.25 part of barium stearate (H-2), 1 part of bentonite (H-3), 0.01 part of AEROSIL (H-4) were dry blended, and the resulting mixture was An extruder having a diameter of 65 mm and a diameter of 90 mm was vertically connected to an extruder at a rate of about 70 kg / hr. The mixture supplied to the 65 mm-diameter extruder is heated to 200 ° C. and kneaded, and the resin temperature is cooled to 120 ° C. with the 90 mm-diameter extruder connected to the extruder, and is attached to the tip of the 90 mm-diameter extruder. Extruded into the atmosphere from the provided base having a rectangular cross section with a thickness direction of 2 mm and a width direction of 50 mm, a rectangular parallelepiped extruded foam was obtained.

  At this time, as a blowing agent, a foaming agent composed of 59% isobutane (F-2), 29% dimethyl ether (G-1), and 12% water (G-2) is 100 parts of a styrene resin (a total of recycled products). From the vicinity of the tip of the 65 mm diameter extruder (the end on the side connected to the end opposite to the die of the 90 mm diameter extruder) into the resin. Press-fitted.

  Table 4 shows the properties of the obtained extruded foam.

(Examples 30 to 34 and Comparative Example 10)
A foam was obtained in the same manner as in Example 29 except that the recycled product was changed to that shown in Table 4.

実施例２９〜３４と比較例１０を比較して明らかなように、リサイクル品を５０部用いた発泡体においても、小さい気泡（小気泡）と、大きな気泡（大気泡）が海島状に混在してなる特徴的な気泡構造が良好に形成されることが判る。

As is clear by comparing Examples 29 to 34 and Comparative Example 10, even in the foam using 50 parts of the recycled product, small bubbles (small bubbles) and large bubbles (large bubbles) are mixed in the shape of a sea island. It can be seen that the characteristic bubble structure is well formed.

Claims (9)

A method for producing a styrene resin foam in which a styrenic resin is heated and melted, a foaming agent is added to the styrenic resin, and extrusion foamed in a low pressure region, and the following (A) and (B) coexist, A method for producing a styrenic resin foam, characterized by extrusion foaming .
(A) is the following (A1) or (A2).
(A1) One or more foaming agents selected from the group of styrene-based resins, hydrocarbons and halogenated hydrocarbons, and having an ozone depletion coefficient of 0, and other foaming agents as required;
(A2) and a styrene resin, a compound selected from the group consisting of hydrocarbons and halogenated hydrocarbons, and ozone depletion is necessary and one or more blowing agents 0 other blowing agent, and Tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether) as halogen flame retardant;

(B) a styrenic resin, a compound selected from the group of hydrocarbons and halogenated hydrocarbons, and one or more foaming agents having an ozone depletion coefficient of 0 and other foaming agents as required; and A styrene-based resin composition obtained by regenerating a styrene-based foam extruded and foamed in the presence of tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether) as a halogen-based flame retardant;
The regenerated styrenic resin composition of (B) is a compound selected from the group consisting of hydrocarbons and halogenated hydrocarbons in the styrenic resin, and at least one ozone depletion coefficient is 0 A styrenic foam obtained by extrusion foaming in the presence of a foaming agent and, if necessary, another foaming agent and tetrabromobisphenol A-bis (2,3-dibromo-2-methylpropyl ether) as a halogen-based flame retardant, The method for producing a styrene resin foam according to claim 1, wherein the styrene resin composition is a styrene resin composition that has been pulverized and melted into pellets .
In (A) or (A) and (B), the foaming agent is a compound selected from the group consisting of hydrocarbons and halogenated hydrocarbons, and one or more ozone depletion coefficients are 0 Compound (a); and water (b); and at least one ether (c) selected from the group consisting of dimethyl ether, diethyl ether and methyl ethyl ether,
And (A), or (A) and (B), a water-absorbing substance is allowed to coexist.
3. The styrene resin foam according to claim 1, wherein the bubbles forming the obtained foam are mainly composed of bubbles having a bubble diameter of 0.25 mm or less and bubbles having a bubble diameter of 0.3 to 1 mm. Body manufacturing method.
Among the bubbles forming the foam obtained, bubbles with a bubble diameter of 0.25 mm or less are foam cross-sectional areas. The styrene-based tree according to claim 3, which has an occupied area ratio of 5 to 95% per unit. A method for producing a fat foam.
In the foaming agent in (A) or (A) and (B), the total amount of foaming agent is 100. The amount of the one or more compounds (a) having an ozone depletion coefficient of 0 to 10% by weight is 10 to 90%. % By weight, amount of water (b) 1 to 75% by weight, and dimethyl ether, diethyl ether And at least one ether (c) selected from the group consisting of methyl ethyl ether The styrene resin foam according to any one of claims 3 and 4, wherein the amount of the styrene resin is 79 to 5% by weight. Body manufacturing method.
Water absorbing material is Sumetaito group clay, production of styrene resins onset foam according to any one of swellable mica, claims 3 to 5 is at least one selected anhydrous silica or found having a silanol group Way .
A compound selected from the group consisting of hydrocarbons and halogenated hydrocarbons, and one or more blowing agents having an ozone depletion coefficient of 0 is a group of saturated hydrocarbons and hydrofluorocarbons having 3 to 5 carbon atoms The method for producing a styrenic resin foam according to any one of claims 1 to 6, wherein the foaming agent comprises one or more compounds selected from the group consisting of :
One or more compounds selected from the group of saturated hydrocarbons having 3 to 5 carbon atoms and hydrofluorocarbons are propane, n-butane, i-butane, 1,1,1,2-tetrafluoroethane (HFC). -134a: CH ₂ FCF ₃₎ manufacturing method of a styrene resin foam of claim 7 wherein the a.
Wherein (A) and / or (B) is any one of the preceding claims, further comprising a tetrabromobisphenol A- bis (2,3-di-bromo-2-methyl propyl ether) other halogen-based flame retardant other than A method for producing a styrene resin foam according to claim 1 .